Sample records for abo3 perovskite structure

  1. Machine Learning of ABO3 Crystalline Compounds

    NASA Astrophysics Data System (ADS)

    Gubernatis, J. E.; Balachandran, P. V.; Lookman, T.

    We apply two advanced machine learning methods to a database of experimentally known ABO3 materials to predict the existence of possible new perovskite materials and possible new cubic perovskites. Constructing a list of 625 possible new materials from charge conserving combinations of A and B atoms in known stable ABO3 materials, we predict about 440 new perovskites. These new perovskites are predicted most likely to occur when the A and B atoms are a lanthanide or actinide, when the A atom is a alkali, alkali earth, or late transition metal, and a when the B atom is a p-block atom. These results are in basic agreement with the recent materials discovery by substitution analysis of Hautier et al. who data-mined the entire ICSD data base to develop the probability that in any crystal structure atom X could be substituted for by atom Y. The results of our analysis has several points of disagreement with a recent high throughput DFT study of ABO3 crystalline compounds by Emery et al. who predict few, if any, new perovskites whose A and B atoms are both a lanthanide. They also predict far more new cubic perovskites than we do: We predict few, if any, with a high degree of probability. This work was supported by the LDRD DR program of the Los Alamos National Laboratory.

  2. Interfacial coupling and polarization of perovskite ABO3 heterostructures

    NASA Astrophysics Data System (ADS)

    Wu, Lijun; Wang, Zhen; Zhang, Bangmin; Yu, Liping; Chow, G. M.; Tao, Jing; Han, Myung-Geun; Guo, Hangwen; Chen, Lina; Plummer, E. W.; Zhang, Jiandi; Zhu, Yimei

    2017-02-01

    Interfaces with subtle difference in atomic and electronic structures in perovskite ABO3 heterostructures often yield intriguingly different properties, yet their exact roles remain elusive. In this article, we report an integrated study of unusual transport, magnetic, and structural properties of Pr0.67Sr0.33MnO3 (PSMO) films and La0.67Sr0.33MnO3 (LSMO) films of various thicknesses on SrTiO3 (STO) substrate. In particular, using atomically resolved imaging and electron energy-loss spectroscopy (EELS), we measured interface related local lattice distortion, BO6 octahedral rotation and cation-anion displacement induced polarization. In the very thin PSMO film, an unexpected interface-induced ferromagnetic polaronic insulator phase was observed during the cubic-to-tetragonal phase transition of the substrate STO, due to the enhanced electron-phonon interaction and atomic disorder in the film. On the other hand, for the very thin LSMO films we observed a remarkably deep polarization in non-ferroelectric STO substrate near the interface. Combining the experimental results with first principles calculations, we propose that the observed deep polarization is induced by an electric field originating from oxygen vacancies that extend beyond a dozen unit-cells from the interface, thus providing important evidence of the role of defects in the emergent interface properties of transition metal oxides.

  3. Investigations of Transition Metal Oxide with the Perovskite Structure as Potential Multiferroics

    DTIC Science & Technology

    2008-10-01

    the perovskite structure (ABO3) which are either ferromagnetic or ferroelectric, but relatively few that display both types of properties . This...novel material that displays the properties of both end members. 15. SUBJECT TERMS Multiferroics, perovskite , transition metal oxides 16. SECURITY...multiferroic properties (22). The compound has a simple cubic perovskite structure and is defined as a quantum paraelectric. It consists of Eu2+ ions

  4. First-principles study on the electronic, optical and thermodynamic properties of ABO 3 (A = La,Sr, B = Fe,Co) perovskites

    DOE PAGES

    Jia, Ting; Zeng, Zhi; Lin, H. Q.; ...

    2017-08-08

    The electronic, optical and thermodynamic properties of ABO 3 (A = La,Sr, B = Fe,Co) perovskites are investigated using first-principles calculations. The obtained results indicate that SrCoO 3 and SrFeO 3 are metals, while LaCoO 3 and LaFeO 3 are insulators and all of them exhibit strong hybridization of the Fe/Co-3d and O-2p orbitals. By correlating the energy band structures with the peaks of the imaginary part of the dielectric function, we obtained the origin of each electron excitation to provide information about the active bands for the corresponding optical transitions observed in the experiment. Moreover, the Debye temperatures θmore » D obtained from the phonon frequencies are comparable to the available data. In conclusion, the thermodynamic properties of the Helmholtz free energy F, entropy S, and constant-volume heat capacity C v are investigated based on the phonon spectra.« less

  5. Electronic and Structural Properties of ABO3: Role of the B-O Coulomb Repulsions for Ferroelectricity

    PubMed Central

    Miura, Kaoru; Azuma, Masaki; Funakubo, Hiroshi

    2011-01-01

    We have investigated the role of the Ti–O Coulomb repulsions in the appearance of the ferroelectric state in BaTiO3 as well as the role of the Zn–O Coulomb repulsions in BiZn0.5Ti0.5O3, using a first-principles calculation with optimized structures. In tetragonal BaTiO3, it is found that the Coulomb repulsions between Ti 3s and 3p states and O 2s and 2p states have an important role for the appearance of Ti ion displacement. In BiZn0.5Ti0.5O3, on the other hand, the stronger Zn–O Coulomb repulsions, which are due to the 3s, 3p, and 3d (d10) states of the Zn ion, have more important role than the Ti–O Coulomb repulsions for the appearance of the tetragonal structure. Our suggestion is consistent with the other ferroelectric perovskite oxides ABO3 in the appearance of tetragonal structures as well as rhombohedral structures. PMID:28879987

  6. Electronic and Structural Properties of ABO3: Role of the B-O Coulomb Repulsions for Ferroelectricity.

    PubMed

    Miura, Kaoru; Azuma, Masaki; Funakubo, Hiroshi

    2011-01-17

    We have investigated the role of the Ti-O Coulomb repulsions in the appearance of the ferroelectric state in BaTiO3 as well as the role of the Zn-O Coulomb repulsions in BiZn0.5Ti0.5O3, using a first-principles calculation with optimized structures. In tetragonal BaTiO3, it is found that the Coulomb repulsions between Ti 3s and 3p states and O 2s and 2p states have an important role for the appearance of Ti ion displacement. In BiZn0.5Ti0.5O3, on the other hand, the stronger Zn-O Coulomb repulsions, which are due to the 3s, 3p, and 3d (d10) states of the Zn ion, have more important role than the Ti-O Coulomb repulsions for the appearance of the tetragonal structure. Our suggestion is consistent with the other ferroelectric perovskite oxides ABO3 in the appearance of tetragonal structures as well as rhombohedral structures.

  7. Stabilization of highly polar BiFeO 3-like structure: a new interface design route for enhanced ferroelectricity in artificial perovskite superlattices

    DOE PAGES

    Wang, Hongwei; Wen, Jianguo; Miller, Dean; ...

    2016-03-14

    In ABO 3 perovskites, oxygen octahedron rotations are common structural distortions that can promote large ferroelectricity in BiFeO 3 with an R3c structure [1] but suppress ferroelectricity in CaTiO 3 with a Pbnm symmetry [2]. For many CaTiO3-like perovskites, the BiFeO 3 structure is a metastable phase. Here, we report the stabilization of the highly polar BiFeO 3-like phase of CaTiO 3 in a BaTiO 3/CaTiO 3 superlattice grown on a SrTiO 3 substrate. The stabilization is realized by a reconstruction of oxygen octahedron rotations at the interface from the pattern of nonpolar bulk CaTiO 3 to a different patternmore » that is characteristic of a BiFeO 3 phase. The reconstruction is interpreted through a combination of amplitude-contrast sub-0.1-nm high-resolution transmission electron microscopy and first-principles theories of the structure, energetics, and polarization of the superlattice and its constituents. We further predict a number of new artificial ferroelectric materials demonstrating that nonpolar perovskites can be turned into ferroelectrics via this interface mechanism. Therefore, a large number of perovskites with the CaTiO 3 structure type, which include many magnetic representatives, are now good candidates as novel highly polar multiferroic materials [3].« less

  8. Competition between structural instabilities in strained ABO3 nanostructures

    NASA Astrophysics Data System (ADS)

    Bousquet, E.

    2010-03-01

    In spite of their simple structure, the family of ABO3 compounds present a large variety of phase transitions involving polar and non polar distortions as well as magnetic orders. Here we will discuss the microscopic origin of these properties and how they are affected in nanostructures through the concept of structural instabilities. We will from the fact that the ferroelectric (FE) and the antiferrodistortive (AFD) instabilities are in competition at the bulk level and are strongly sensitive to pressure and strain. From these considerations we will describe the possibilities to tune this FE/AFD competition by playing with strain and interface engineering. To that end we will first consider the effect of epitaxial strain on BaTiO3, SrTiO3, PbTiO3 and CaTiO3 thin films. In all of these compounds, the epitaxial strain can strongly modify the phase diagrams giving rise to different pure or mixed FE/AFD ground states. We will also extend the discussion on magnetic perovskites like CaMnO3 and will present the different strategies to induce or tune multiferroic properties. Second we will focus on the interface effects as present in bicolor superlattices. As an example we will examine the case of PbTiO3/SrTiO3 superlattice and will show that it exhibits totally unique properties arising from unexpected FE/AFD couplings at the interface between the layers. We will then investigate to which extent similar types of FE/AFD couplings can be induced in other artificially layered systems. We will consider different bicolor superlattices obtained from the combination of PbTiO3, SrTiO3, CaTiO3 and BaTiO3 and discuss how the intrinsic tendency of these compounds to favor either the FE or the AFD instabilities shifts or even suppresses the FE/AFD coupling.

  9. Tailoring Electronic Properties in Semiconducting Perovskite Materials through Octahedral Control

    NASA Astrophysics Data System (ADS)

    Choquette, Amber K.

    Perovskite oxides, which take the chemical formula ABO 3, are a very versatile and interesting materials family, exhibiting properties that include ferroelectricity, ferromagnetism, mixed ionic/electronic conductivity, metal-insulator behavior and multiferroicity. Key to these functionalities is the network of BO6 corner-connected octahedra, which are known to distort and rotate, directly altering electronic and ferroic properties. By controlling the BO6 octahedral distortions and rotations through cationic substitutions, the use of strain engineering, or through the formation of superlattice structures, the functional properties of perovskites can be tuned. Motivating the use of structure-driven design in oxide heterostructures is the prediction of hybrid improper ferroelectricity in A'BO3/ABO3 superlattices. Two key design rules to realizing hybrid improper ferroelectricity are the growth of high quality superlattice structures with odd periodicities of the A / A' layers, and the control of the octahedral rotation pattern. My work explores the rotational response in perovskite oxides to strain and interface effects in thin films of RFeO3 ( R = La, Eu). I demonstrate a synchrotron x-ray diffraction technique to identify the rotation pattern that is present in the films. I then establish substrate imprinting as a key tool for controlling the rotation patterns in heterostructures, providing a means to realize the necessary structural variants of the predicted hybrid improper ferroelectricity in superlattices. In addition, by pairing measured diffraction data with a structure factor calculation, I demonstrate how one can extract both A-site and oxygen atomic positions in single crystal perovskite oxide films. Finally, I show results from (LaFeO 3)n/(EuFeO3)n superlattices (n = 1-5), synthesized to test the motivating predictions of hybrid improper ferroelectricity in oxide superlattices.

  10. Structure-property relationships: Synthesis and characterization of Perovskite-related transition metal oxides

    NASA Astrophysics Data System (ADS)

    Whaley, Louis

    The fundamental structural component of perovskite-related phases is the octahedrally coordinated transition metal ion, symbolized as BO6 . Corner-sharing networks of BO6 octahedra are present in perovskites and related Ruddlesden-Popper Phases, ABO3 and AO(ABO 3)n, respectively. Face-sharing octahedra arranged into columns are characteristic of hexagonal, perovskite-related phases, and the relationship will be described in detail in Chapter 1. Edge sharing octahedra are characteristic of Keggin- and Lindquist-type polyoxometallates, which at first glance, seem unconnected from perovskites. However, Chapter 1 will show the deep connections among all of the phases mentioned above, by starting with perovskite phases. Temperature- and field-dependent, magnetic and electronic transitions are linked to the structure by overlap of metal d-orbitals with oxygen 2p orbitals, and (in special cases) direct d-d overlap. A mixed-transition metal oxide with two or more type of B ions provides an environment in which dissimilar B-ion orbitals can interact via exchange of charge carriers (hole or electron transport). The general goal in choosing two B ions is to provide an opportunity for the large combined magnetic moment and a low barrier to hopping of charge carriers, achieved by pairing a 3d-ion having 3 to 5 unpaired d-electrons, with a 4d or 5d transition metal ion, having 1 or 2 unpaired electrons, such as Fe(III) and Mo(V), which have compatible reduction potentials (i.e., they can co-exist in the same oxide, and exchange takes place with a low barrier). This research includes the following systems: an n = 2 Ruddlesden-Popper (RP) phase, Sr3Fe5/4Mo3/4O6.9, containing 3-7% Sr2FeMoO6, as intergrowths (not separate crystal grains, by high-resolution transmission electron microscopy), and G-type antiferromagnetism below 150°K and a "partial spin-reorientation transition" by powder neutron diffraction (PND), not previously reported for n = 2 RP phases in the Sr-Fe-Mo-O system

  11. Anomalous perovskite PbRuO3 stabilized under high pressure

    PubMed Central

    Cheng, J.-G.; Kweon, K. E.; Zhou, J.-S.; Alonso, J. A.; Kong, P.-P.; Liu, Y.; Jin, Changqing; Wu, Junjie; Lin, Jung-Fu; Larregola, S. A.; Yang, Wenge; Shen, Guoyin; MacDonald, A. H.; Manthiram, Arumugam; Hwang, G. S.; Goodenough, John B.

    2013-01-01

    Perovskite oxides ABO3 are important materials used as components in electronic devices. The highly compact crystal structure consists of a framework of corner-shared BO6 octahedra enclosing the A-site cations. Because of these structural features, forming a strong bond between A and B cations is highly unlikely and has not been reported in the literature. Here we report a pressure-induced first-order transition in PbRuO3 from a common orthorhombic phase (Pbnm) to an orthorhombic phase (Pbn21) at 32 GPa by using synchrotron X-ray diffraction. This transition has been further verified with resistivity measurements and Raman spectra under high pressure. In contrast to most well-studied perovskites under high pressure, the Pbn21 phase of PbRuO3 stabilized at high pressure is a polar perovskite. More interestingly, the Pbn21 phase has the most distorted octahedra and a shortest Pb—Ru bond length relative to the average Pb—Ru bond length that has ever been reported in a perovskite structure. We have also simulated the behavior of the PbRuO3 perovskite under high pressure by first principles calculations. The calculated critical pressure for the phase transition and evolution of lattice parameters under pressure match the experimental results quantitatively. Our calculations also reveal that the hybridization between a Ru:t2g orbital and an sp hybrid on Pb increases dramatically in the Pbnm phase under pressure. This pressure-induced change destabilizes the Pbnm phase to give a phase transition to the Pbn21 phase where electrons in the overlapping orbitals form bonding and antibonding states along the shortest Ru—Pb direction at P > Pc. PMID:24277807

  12. Classification of AB O 3 perovskite solids: a machine learning study

    DOE PAGES

    Pilania, G.; Balachandran, P. V.; Gubernatis, J. E.; ...

    2015-07-23

    Here we explored the use of machine learning methods for classifying whether a particularABO 3chemistry forms a perovskite or non-perovskite structured solid. Starting with three sets of feature pairs (the tolerance and octahedral factors, theAandBionic radii relative to the radius of O, and the bond valence distances between theAandBions from the O atoms), we used machine learning to create a hyper-dimensional partial dependency structure plot using all three feature pairs or any two of them. Doing so increased the accuracy of our predictions by 2–3 percentage points over using any one pair. We also included the Mendeleev numbers of theAandBatomsmore » to this set of feature pairs. Moreover, doing this and using the capabilities of our machine learning algorithm, the gradient tree boosting classifier, enabled us to generate a new type of structure plot that has the simplicity of one based on using just the Mendeleev numbers, but with the added advantages of having a higher accuracy and providing a measure of likelihood of the predicted structure.« less

  13. Generalized trends in the formation energies of perovskite oxides.

    PubMed

    Zeng, ZhenHua; Calle-Vallejo, Federico; Mogensen, Mogens B; Rossmeisl, Jan

    2013-05-28

    Generalized trends in the formation energies of several families of perovskite oxides (ABO3) and plausible explanations to their existence are provided in this study through a combination of DFT calculations, solid-state physics analyses and simple physical/chemical descriptors. The studied elements at the A site of perovskites comprise rare-earth, alkaline-earth and alkaline metals, whereas 3d and 5d metals were studied at the B site. We also include ReO3-type compounds, which have the same crystal structure of cubic ABO3 perovskites except without A-site elements. From the observations we extract the following four conclusions for the perovskites studied in the present paper: for a given cation at the B site, (I) perovskites with cations of identical oxidation state at the A site possess close formation energies; and (II) perovskites with cations of different oxidation states at the A site usually have quite different but ordered formation energies. On the other hand, for a given A-site cation, (III) the formation energies of perovskites vary linearly with respect to the atomic number of the elements at the B site within the same period of the periodic table, and the slopes depend systematically on the oxidation state of the A-site cation; and (IV) the trends in formation energies of perovskites with elements from different periods at the B site depend on the oxidation state of A-site cations. Since the energetics of perovskites is shown to be the superposition of the individual contributions of their constituent oxides, the trends can be rationalized in terms of A-O and B-O interactions in the ionic crystal. These findings reveal the existence of general systematic trends in the formation energies of perovskites and provide further insight into the role of ion-ion interactions in the properties of ternary compounds.

  14. Bond length (Ti-O) dependence of nano ATO3-based (A = Pb, Ba, Sr) perovskite structures: Optical investigation in IR range

    NASA Astrophysics Data System (ADS)

    Ghasemifard, Mahdi; Ghamari, Misagh; Okay, Cengiz

    2018-01-01

    In the current study, ABO3 (A = Pb, Ba, Sr and B = Ti) perovskite structures are produced by the auto-combustion route by using citric acid (CA) and nitric acid (NA) as fuel and oxidizer. The X-ray diffraction (XRD) patterns confirmed the perovskite nanostructure with cubic, tetragonal, and rhombohedral for SrTiO3, PbTiO3, and BaTiO3, respectively. Using Scherrer’s equation and XRD pattern, the average crystallite size of the samples were acquired. The effect of Ti-O bond length on the structure of the samples was evaluated. The type of structures obtained depends on Ti-O bond length which is in turn influenced by A2+ substitutions. Microstructural studies of nanostructures calcined at 850∘C confirmed the formation of polyhedral particles with a narrow size distribution. The values of optical band gaps were measured and the impact of A2+ was discussed. The optical properties such as the complex refractive index and dielectric function were calculated by IR spectroscopy and Kramers-Kronig (K-K) relations. Lead, as the element with the highest density as compared to other elements, changes the optical constants, remarkably due to altering titanium and oxygen distance in TO6 groups.

  15. Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

    DOE PAGES

    Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.; ...

    2018-01-19

    The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

  16. Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.

    The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

  17. Cation Ordering within the Perovskite Block of a Six-layer Ruddlesden-Popper Oxide from Layer-by-layer Growth

    NASA Astrophysics Data System (ADS)

    Yan, Lei; Niu, H. J.; Rosseinsky, M. J.

    2011-03-01

    The (AO)(A BO3)n Ruddlesden-Popper structure is an archetypal complex oxide consisting of two distinct structural units, an (AO) rock salt layer separating an n-octahedra thick perovskite block. Conventional high-temperature oxide synthesis methods cannot access members with n > 3 , butlowtemperaturelayer - by - layerthinfilmmethodsallowthepreparationofmaterialswiththickerperovskiteblocks , exploitinghighsurfacemobilityandlatticematchingwiththesubstrate . Thispresentationdescribesthegrowthofann = 6 memberCaO / (ABO 3)n (ABO 3 : CaMnO 3 , La 0.67 Ca 0.33 MnO 3 orCa 0.85 Sm 0.15 MnO 3) epitaxialsinglecrystalfilmsonthe (001) SrTiO 3 substrates by pulsed laser deposition with the assistance of a reflection high energy electron diffraction (RHEED).

  18. Tailoring the Two Dimensional Electron Gas at Polar ABO3/SrTiO3 Interfaces for Oxide Electronics.

    PubMed

    Li, Changjian; Liu, Zhiqi; Lü, Weiming; Wang, Xiao Renshaw; Annadi, Anil; Huang, Zhen; Zeng, Shengwei; Ariando; Venkatesan, T

    2015-08-26

    The 2D electron gas at the polar/non-polar oxide interface has become an important platform for several novel oxide electronic devices. In this paper, the transport properties of a wide range of polar perovskite oxide ABO3/SrTiO3 (STO) interfaces, where ABO3 includes LaAlO3, PrAlO3, NdAlO3, NdGaO3 and LaGaO3 in both crystalline and amorphous forms, were investigated. A robust 4 unit cell (uc) critical thickness for metal insulator transition was observed for crystalline polar layer/STO interface while the critical thickness for amorphous ones was strongly dependent on the B site atom and its oxygen affinity. For the crystalline interfaces, a sharp transition to the metallic state (i.e. polarization catastrophe induced 2D electron gas only) occurs at a growth temperature of 515 °C which corresponds to a critical relative crystallinity of ~70 ± 10% of the LaAlO3 overlayer. This temperature is generally lower than the metal silicide formation temperature and thus offers a route to integrate oxide heterojunction based devices on silicon.

  19. A study on the thermal conversion of scheelite-type ABO4 into perovskite-type AB(O,N)3.

    PubMed

    Li, Wenjie; Li, Duan; Gao, Xin; Gurlo, Aleksander; Zander, Stefan; Jones, Philip; Navrotsky, Alexandra; Shen, Zhijian; Riedel, Ralf; Ionescu, Emanuel

    2015-05-07

    Phase-pure scheelite AMoO4 and AWO4 (A = Ba, Sr, Ca) were thermally treated under an ammonia atmosphere at 400 to 900 °C. SrMoO4 and SrWO4 were shown to convert into cubic perovskite SrMoO2N and SrWO1.5N1.5, at 700 °C and 900 °C respectively, and to form metastable intermediate phases (scheelite SrMoO4-xNx and SrWO4-xNx), as revealed by X-ray diffraction (XRD), elemental analysis and FTIR spectroscopy. High-temperature oxide melt solution calorimetry reveals that the enthalpy of formation for SrM(O,N)3 (M = Mo, W) perovskites is less negative than that of the corresponding scheelite oxides, though the conversion of the scheelite oxides into perovskite oxynitrides is thermodynamically favorable at moderate temperatures. The reaction of BaMO4 with ammonia leads to the formation of rhombohedral Ba3M2(O,N)8 and the corresponding binary metal nitrides Mo3N2 and W4.6N4; similar behavior was observed for CaMO4, which converted upon ammonolysis into individual oxides and nitrides. Thus, BaMO4 and CaMO4 were shown to not provide access to perovskite oxynitrides. The influence of the starting scheelite oxide precursor, the structure distortion and the degree of covalency of the B-site-N bond are discussed within the context of the formability of perovskite oxynitrides.

  20. Specific features of nonvalent interactions in orthorhombic perovskites

    NASA Astrophysics Data System (ADS)

    Serezhkin, V. N.; Pushkin, D. V.; Serezhkina, L. B.

    2014-07-01

    It is established that isostructural orthorhombic perovskites ABO3 (sp. gr. Pnma in different systems, no. 62, Z = 4), depending on the specificity of nonvalent interactions (which determine the combinatorial-topological type of the Voronoi-Dirichlet polyhedra (VDPs) of four basis atoms), are divided into ten different stereotypes. It is shown by the example of 259 perovskites belonging to the DyCrO3 stereotype that VDP characteristics can be used to quantitatively estimate the distortion of BO6 octahedra, including that caused by the Jahn-Teller effect. It is found that one of the causes of the distortion of the coordination polyhedra of atoms in the structure of orthorhombic perovskites is heteroatomic metal-metal interactions, for which the interatomic distances are much shorter than the sum of the Slater radii of A and B atoms.

  1. Effect of mechanical milling on barium titanate (BaTiO3) perovskite

    NASA Astrophysics Data System (ADS)

    Singh, Rajan Kumar; Sanodia, Sagar; Jain, Neha; Kumar, Ranveer

    2018-05-01

    Commercial Barium Titanate BaTiO3 (BT) is milled by planetary ball mill in acetone medium using stainless steel bowl & ball for different hours. BT is an important perovskite oxide with structure ABO3. BT has applications in electro-optic devices, energy storing devices such as photovoltaic cells, thermistors, multiceramic capacitors & DRAMs etc. BT is non-toxic & environment friendly ceramic with high dielectric and piezoelectric property so it can be used as the substitute of PZT & PbTiO3. Here, we have investigated the effect of milling time and temperature on particle size and phase transition of BT powder. We used use Raman spectroscopy for studying the spectra of BT; XRD is used for structural study. Intensity (height) of Raman spectra and XRD spectra continuously decrease with increasing the milling hours and width if these spectra increases which indicates, decrease in BT size.

  2. The origin of uniaxial negative thermal expansion in layered perovskites

    NASA Astrophysics Data System (ADS)

    Ablitt, Chris; Craddock, Sarah; Senn, Mark S.; Mostofi, Arash A.; Bristowe, Nicholas C.

    2017-10-01

    Why is it that ABO3 perovskites generally do not exhibit negative thermal expansion (NTE) over a wide temperature range, whereas layered perovskites of the same chemical family often do? It is generally accepted that there are two key ingredients that determine the extent of NTE: the presence of soft phonon modes that drive contraction (have negative Grüneisen parameters); and anisotropic elastic compliance that predisposes the material to the deformations required for NTE along a specific axis. This difference in thermal expansion properties is surprising since both ABO3 and layered perovskites often possess these ingredients in equal measure in their high-symmetry phases. Using first principles calculations and symmetry analysis, we show that in layered perovskites there is a significant enhancement of elastic anisotropy due to symmetry breaking that results from the combined effect of layering and condensed rotations of oxygen octahedra. This feature, unique to layered perovskites of certain symmetry, is what allows uniaxial NTE to persist over a large temperature range. This fundamental insight means that symmetry and the elastic tensor can be used as descriptors in high-throughput screening and to direct materials design.

  3. Evolution of Photoluminescence, Raman, and Structure of CH3NH3PbI3 Perovskite Microwires Under Humidity Exposure

    NASA Astrophysics Data System (ADS)

    Segovia, Rubén; Qu, Geyang; Peng, Miao; Sun, Xiudong; Shi, Hongyan; Gao, Bo

    2018-03-01

    Self-assembled organic-inorganic CH3NH3PbI3 perovskite microwires (MWs) upon humidity exposure along several weeks were investigated by photoluminescence (PL) spectroscopy, Raman spectroscopy, and X-ray diffraction (XRD). We show that, in addition to the common perovskite decomposition into PbI2 and the formation of a hydrated phase, humidity induced a gradual PL redshift at the initial weeks that is stabilized for longer exposure ( 21 nm over the degradation process) and an intensity enhancement. Original perovskite Raman band and XRD reflections slightly shifted upon humidity, indicating defects formation and structure distortion of the MWs crystal lattice. By correlating the PL, Raman, and XRD results, it is believed that the redshift of the MWs PL emission was originated from the structural disorder caused by the incorporation of H2O molecules in the crystal lattice and radiative recombination through moisture-induced subgap trap states. Our study provides insights into the optical and structural response of organic-inorganic perovskite materials upon humidity exposure.

  4. Effect of cation ordering on oxygen vacancy diffusion pathways in double perovskites

    DOE PAGES

    Uberuaga, Blas Pedro; Pilania, Ghanshyam

    2015-07-08

    Perovskite structured oxides (ABO 3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA’BB’O 6) provide even more flexibility for tailoring properties. Using accelerated molecular dynamics, we examine the role of cation ordering on oxygen vacancy mobility in one model double perovskite SrLaTiAlO 6. We find that the mobility of the vacancy is very sensitive to the cation ordering, with a migration energy that varies from 0.6 to 2.7 eV. In the extreme cases, the mobility is both higher and lower than either of the two endmore » member single perovskites. Further, the nature of oxygen vacancy diffusion, whether one-dimensional, two-dimensional, or three-dimensional, also varies with cation ordering. We correlate the dependence of oxygen mobility on cation structure to the distribution of Ti 4+ cations, which provide unfavorable environments for the positively charged oxygen vacancy. The results demonstrate the potential of using tailored double perovskite structures to precisely control the behavior of oxygen vacancies in these materials.« less

  5. High-pressure synthesis, crystal chemistry and physics of perovskites with small cations at the A site.

    PubMed

    Belik, Alexei A; Yi, Wei

    2014-04-23

    ABO3 perovskites with small cations at the A site (A = Sc(3+), In(3+) and Mn(2+) and B = Al(3+) and transition metals) are reviewed. They extend the corresponding families of perovskites with A(3+) = Y, La-Lu, and Bi and A(2+) = Cd, Ca, Sr and Ba and exhibit the largest structural distortions. As a result of these large distortions, they show, in many cases, distinct structural and magnetic properties. These are manifested in: B-site-ordered monoclinic structures of ScMnO3 and 'InMnO3'; an unusual superstructure of ScRhO3 and InRhO3; antiferromagnetic ground states and multiferroic properties of Sc2NiMnO6 and In2NiMnO6; two magnetic transitions in ScCrO3 and InCrO3 with very close transition temperatures; a Pnma-to-P-1 structural transition and k = (½, 0, ½) magnetic ordering in ScVO3; and incommensurate magnetic ordering of Mn(2+) spins in metallic MnVO3. A large number of simple ScBO3, InBO3 and MnBO3 perovskites has not been synthesized yet, and the number of experimental and theoretical works on each known ScBO3, InBO3 and MnBO3 perovskites counts to only one or two (except for ScAlO3). The synthesis, crystal chemistry and physics of perovskites with small cations at the A site is an emerging field in perovskite science.

  6. Topotactical growth of thick perovskite oxynitride layers by nitridation of single crystalline oxides

    NASA Astrophysics Data System (ADS)

    Ebbinghaus, Stefan G.; Aguiar, Rosiana; Weidenkaff, Anke; Gsell, Stefan; Reller, Armin

    2008-06-01

    Thick films of the perovskite-related oxynitrides LaTiO 2N, NdTiO 2N, SrNbO 2N and SrTaO 2N were synthesised by nitridation of single crystals of the corresponding oxides with general composition ABO 3.5. The oxide crystals were obtained by optical floating zone growth. They correspond to n = 4 member of the A nB nO 3 n+2 family of layered perovskites and were reacted at temperatures between 900 °C and 1050 °C to form the oxynitrides. Electron probe microanalysis proved the presence of nitrogen in a surface layer of a few micrometer thickness. Cross-section SEM revealed additional thin stripes of oxynitride within the bulk of the crystals, indicating that nitrogen is incorporated preferably parallel to the perovskite-type layers, which in turn are connected in a zipper-type mechanism. The formation of the desired perovskite-type oxynitrides was confirmed by X-ray diffraction. Pole figure measurements proved an epitaxial orientation ABO 2N (110)[001] ‖ ABO 3.5 (001)[100]. The mosaicity of the oxynitrides both in polar and azimuthal direction was very small (<2°) indicating a nearly single crystalline quality of the surface layer. The nitridation of the crystals results in a dramatic change in colour. Optical spectroscopy revealed shifts of the absorption edge by more than 200 nm to longer wavelengths with respect to the parent oxides, corresponding to a reduction of the band gap energies by 1.4-1.8 eV.

  7. Electrochemical sensing of modified ABO3 perovskite: LaFe0.8 R0.2O3(R= Cr, Co, Al)

    NASA Astrophysics Data System (ADS)

    Vidya Rajan, N.; Alexander, L. K.

    2017-06-01

    Perovskite LaFeO3 with orthorhombic structure has been synthesized by citric acid mediated solution method. The effectiveness of ionic radii and Oxidation state of the doping material on ionic conductivity of the host matrix was evaluated by B-site (Fe) doping on LaFeO3 with Cr, Co and Al, resulting LaFe0.8 R0.2O3 (R = Cr, Co, Al). XRD with Rietveld refinement and Raman spectroscopic analysis demonstrate successful synthesis. The effect of the 20% B site doping on electrochemical activity is reported. The doped materials exhibit a decrease in sensing activity towards the non enzymatic detection of H2O2.

  8. Efficiency enhancement of perovskite solar cells using structural and morphological improvement of CH3NH3PbI3 absorber layers

    NASA Astrophysics Data System (ADS)

    Alidaei, Maryam; Izadifard, Morteza; Ghazi, Mohammad E.; Ahmadi, Vahid

    2018-01-01

    Perovskite solar cells have been heavily investigated due to their unique properties such as high power conversion efficiency (PCE), low-cost fabrication by solution processes, high diffusion length, large absorption coefficient, and direct and tunable band gap. PCE of perovskite devices is strongly dependent on the absorber layer properties such as morphology, crystallinity, and compactness, which are required to be optimized. In this work, the CH3NH3PbI3 (170-480 nm) absorber layers with various methylammonium iodine (MAI) concentrations (7, 10, 20 and 40 mg ml-1) and perovskite solar cells with the fluorine-doped tin oxide (400 nm)/C-TiO2 (30 nm)/Meso-TiO2 (400 nm)/CH3NH3PbI3 (170-480 nm)/P3HT (30 nm)/Au (100 nm) structure were fabricated. A two-step solution process was used for deposition of the CH3NH3PbI3 absorber layers. The morphology, crystal structure, and optical properties of the perovskite layer grown on glass and also the photovoltaic properties of the fabricated solar cells were studied. The results obtained showed that by controlling the deposition conditions, due to the reduction in charge recombination, PCE enhancement of the perovskite solar cell (up to 11.6%) was accessible.

  9. Enhanced structural stability and photo responsiveness of CH 3NH 3SnI 3 perovskite via pressure-induced amorphization and recrystallization

    DOE PAGES

    Lu, Xujie; Wang, Yonggang; Stoumpos, Constantinos C.; ...

    2016-10-01

    An organic–inorganic halide CH 3NH 3SnI 3 perovskite with significantly improved structural stability is obtained via pressure-induced amorphization and recrystallization. In situ high-pressure resistance measurements reveal an increased electrical conductivity by 300% in the pressure-treated perovskite. Photocurrent measurements also reveal a substantial enhancement in visible-light responsiveness. In conclusion, the mechanism underlying the enhanced properties is shown to be associated with the pressure-induced structural modification.

  10. Enhanced Structural Stability and Photo Responsiveness of CH3 NH3 SnI3 Perovskite via Pressure-Induced Amorphization and Recrystallization.

    PubMed

    Lü, Xujie; Wang, Yonggang; Stoumpos, Constantinos C; Hu, Qingyang; Guo, Xiaofeng; Chen, Haijie; Yang, Liuxiang; Smith, Jesse S; Yang, Wenge; Zhao, Yusheng; Xu, Hongwu; Kanatzidis, Mercouri G; Jia, Quanxi

    2016-10-01

    An organic-inorganic halide CH 3 NH 3 SnI 3 perovskite with significantly improved structural stability is obtained via pressure-induced amorphization and recrystallization. In situ high-pressure resistance measurements reveal an increased electrical conductivity by 300% in the pressure-treated perovskite. Photocurrent measurements also reveal a substantial enhancement in visible-light responsiveness. The mechanism underlying the enhanced properties is shown to be associated with the pressure-induced structural modification. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. High-pressure synthesis, crystal structure and magnetic properties of TlCrO3 perovskite.

    PubMed

    Yi, Wei; Matsushita, Yoshitaka; Katsuya, Yoshio; Yamaura, Kazunari; Tsujimoto, Yoshihiro; Presniakov, Igor A; Sobolev, Alexey V; Glazkova, Yana S; Lekina, Yuliya O; Tsujii, Naohito; Nimori, Shigeki; Takehana, Kanji; Imanaka, Yasutaka; Belik, Alexei A

    2015-06-21

    TlMO(3) perovskites (M(3+) = transition metals) are exceptional members of trivalent perovskite families because of the strong covalency of Tl(3+)-O bonds. Here we report on the synthesis, crystal structure and properties of TlCrO(3) investigated by Mössbauer spectroscopy, specific heat, dc/ac magnetization and dielectric measurements. TlCrO(3) perovskite is prepared under high pressure (6 GPa) and high temperature (1500 K) conditions. The crystal structure of TlCrO(3) is refined using synchrotron X-ray powder diffraction data: space group Pnma (no. 62), Z = 4 and lattice parameters a = 5.40318(1) Å, b = 7.64699(1) Å and c = 5.30196(1) Å at 293 K. No structural phase transitions are found between 5 and 300 K. TlCrO(3) crystallizes in the GdFeO(3)-type structure similar to other members of the perovskite chromite family, ACrO(3) (A(3+) = Sc, In, Y and La-Lu). The unit cell volume and Cr-O-Cr bond angles of TlCrO(3) are close to those of DyCrO(3); however, the Néel temperature of TlCrO(3) (TN≈ 89 K) is much smaller than that of DyCrO(3) and close to that of InCrO(3). Isothermal magnetization studies show that TlCrO(3) is a fully compensated antiferromagnet similar to ScCrO(3) and InCrO(3), but different from RCrO(3) (R(3+) = Y and La-Lu). Ac and dc magnetization measurements with a fine step of 0.2 K reveal the existence of two Néel temperatures with very close values at T(N2) = 87.0 K and T(N1) = 89.3 K. Magnetic anomalies near T(N2 )are suppressed by static magnetic fields and by 5% iron doping.

  12. Influence of chromium hyperdoping on the electronic structure of CH3NH3PbI3 perovskite: a first-principles insight.

    PubMed

    García, Gregorio; Palacios, Pablo; Menéndez-Proupin, Eduardo; Montero-Alejo, Ana L; Conesa, José C; Wahnón, Perla

    2018-02-06

    Organic-inorganic hybrid halide perovskites compounds are emerging as new materials with great potential for efficient solar cells. This paper explores the possibility of increasing their photovoltaic efficiency through sub-bandgap absorption by way of the in gap band (IGB) concept. Thus, we assess the formation of an in gap band as well as its effect on the absorption features of Organic-inorganic hybrid halide perovskites CH 3 NH 3 PbI 3 (MAPI). For this task, we use density functional theory (DFT) as well as many-body perturbation methods along to spin-orbit coupling (SOC) to study structural, energetic and electronic properties of partially Cr-substituted MAPI perovskites (CH 3 NH 3 Pb 1-x Cr x I 3 ). Our results reveal that Cr replacement does not lead to an important cell distortion, while the energetic of the substitution process evidences the possibility of obtaining Cr-substituted perovskite. The analysis of the electronic structure shows that Cr 3d-orbitals induce new electronic states in the host semiconductor bandgap, which fulfill the requirements to be considered as an IGB. Precise many-body perturbation methods in G 0 W 0 approach provided an accurate description on the electronic structures as well as the position of the IGB. In short, Pb replacement by Cr could be useful for improved absorption features through new sub-bandgap transitions across the in gap band.

  13. Hybrid solar cells composed of perovskite and polymer photovoltaic structures

    NASA Astrophysics Data System (ADS)

    Phaometvarithorn, Apatsanan; Chuangchote, Surawut; Kumnorkaew, Pisist; Wootthikanokkhan, Jatuphorn

    2018-06-01

    Organic/inorganic lead halide perovskite solar cells have recently attracted much attention in photovoltaic research, due to the devices show promising ways to achieve high efficiencies. The perovskite devices with high efficiencies, however, are typically fabricated in tandem solar cell which is complicated. In this research work, we introduce a solar cell device with the combination of CH3NH3PbI3-xClx perovskite and bulk heterojunction PCDTBT:PC70BM polymer without any tandem structure. The new integrated perovskite/polymer hybrid structure of ITO/PEDOT:PSS/perovskite/PCDTBT:PC70BM/PC70BM/TiOx/Al provides higher power conversion efficiency (PCE) of devices compared with conventional perovskite cell structure. With the optimized PCDTBT:PC70BM thickness of ∼70 nm, the highest PCE of 11.67% is achieved. Variation of conducting donor polymers in this new structure is also preliminary demonstrated. This study provides an attractively innovative structure and a promising design for further development of the new-generation solar cells.

  14. Green perovskite light emitting diodes based on the ITO/Al2O3/CsPbBr3 heterojunction structure

    NASA Astrophysics Data System (ADS)

    Zhuang, Shiwei; Ma, Xue; Hu, Daqiang; Dong, Xin; Zhang, Yuantao; Zhang, Baolin

    2018-03-01

    Perovskite light emitting diodes (PeLEDs) now emerge as a promising new optoelectronic application field for these amazing semiconductors. For the purpose of investigating the device structures and light emission mechanisms of PeLEDs, we have fabricated green PeLEDs based on the ITO/Al2O3/CsPbBr3 heterojunction structure. The emission layer inorganic perovskite CsPbBr3 film with small grain sizes (∼28.9 nm) was prepared using a two-step method. The device exhibits a typical rectification behavior with turn-on voltage of ∼6 V. The EL emission band is narrow with the FWHM of ∼25 nm. The peak EQE of the device was ∼0.09%. The working mechanism of the device is also discussed. The result of the present work provides a feasible innovation idea of PeLEDs fabrication and great potentials for the development of perovskite based LEDs.

  15. Calculated high-pressure structural properties, lattice dynamics and quasi particle band structures of perovskite fluorides KZnF3, CsCaF3 and BaLiF3

    NASA Astrophysics Data System (ADS)

    Vaitheeswaran, G.; Kanchana, V.; Zhang, Xinxin; Ma, Yanming; Svane, A.; Christensen, N. E.

    2016-08-01

    A detailed study of the high-pressure structural properties, lattice dynamics and band structures of perovskite structured fluorides KZnF3, CsCaF3 and BaLiF3 has been carried out by means of density functional theory. The calculated structural properties including elastic constants and equation of state agree well with available experimental information. The phonon dispersion curves are in good agreement with available experimental inelastic neutron scattering data. The electronic structures of these fluorides have been calculated using the quasi particle self-consistent GW approximation. The GW calculations reveal that all the fluorides studied are wide band gap insulators, and the band gaps are significantly larger than those obtained by the standard local density approximation, thus emphasizing the importance of quasi particle corrections in perovskite fluorides.

  16. Calculated high-pressure structural properties, lattice dynamics and quasi particle band structures of perovskite fluorides KZnF3, CsCaF3 and BaLiF3.

    PubMed

    Vaitheeswaran, G; Kanchana, V; Zhang, Xinxin; Ma, Yanming; Svane, A; Christensen, N E

    2016-08-10

    A detailed study of the high-pressure structural properties, lattice dynamics and band structures of perovskite structured fluorides KZnF3, CsCaF3 and BaLiF3 has been carried out by means of density functional theory. The calculated structural properties including elastic constants and equation of state agree well with available experimental information. The phonon dispersion curves are in good agreement with available experimental inelastic neutron scattering data. The electronic structures of these fluorides have been calculated using the quasi particle self-consistent [Formula: see text] approximation. The [Formula: see text] calculations reveal that all the fluorides studied are wide band gap insulators, and the band gaps are significantly larger than those obtained by the standard local density approximation, thus emphasizing the importance of quasi particle corrections in perovskite fluorides.

  17. Low-Dimensional Organic-Inorganic Halide Perovskite: Structure, Properties, and Applications.

    PubMed

    Misra, Ravi K; Cohen, Bat-El; Iagher, Lior; Etgar, Lioz

    2017-10-09

    Three-dimensional (3 D) perovskite has attracted a lot of attention owing to its success in photovoltaic (PV) solar cells. However, one of its major crucial issues lies in its stability, which has limited its commercialization. An important property of organic-inorganic perovskite is the possibility of forming a layered material by using long organic cations that do not fit into the octahedral cage. These long organic cations act as a "barrier" that "caps" 3 D perovskite to form the layered material. Controlling the number of perovskite layers could provide a confined structure with chemical and physical properties that are different from those of 3 D perovskite. This opens up a whole new batch of interesting materials with huge potential for optoelectronic applications. This Minireview presents the synthesis, properties, and structural orientation of low-dimensional perovskite. It also discusses the progress of low-dimensional perovskite in PV solar cells, which, to date, have performance comparable to that of 3 D perovskite but with enhanced stability. Finally, the use of low-dimensional perovskite in light-emitting diodes (LEDs) and photodetectors is discussed. The low-dimensional perovskites are promising candidates for LED devices, mainly because of their high radiative recombination as a result of the confined low-dimensional quantum well. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. New Type of 2D Perovskites with Alternating Cations in the Interlayer Space, (C(NH 2 ) 3 )(CH 3 NH 3 ) n Pb n I 3n+1 : Structure, Properties, and Photovoltaic Performance

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Soe, Chan Myae Myae; Stoumpos, Constantinos C.; Kepenekian, Mikaël

    We present the new homologous series (C(NH2)3)(CH3NH3)nPbnI3n+1 (n = 1, 2, 3) of layered 2D perovskites. Structural characterization by single-crystal X-ray diffraction reveals that these compounds adopt an unprecedented structure type, which is stabilized by the alternating ordering of the guanidinium and methylammonium cations in the interlayer space (ACI). Compared to the more common Ruddlesden–Popper (RP) 2D perovskites, the ACI perovskites have a different stacking motif and adopt a higher crystal symmetry. The higher symmetry of the ACI perovskites is expressed in their physical properties, which show a characteristic decrease of the bandgap with respect to their RP perovskite counterpartsmore » with the same perovskite layer thickness (n). The compounds show a monotonic decrease in the optical gap as n increases: Eg = 2.27 eV for n = 1 to Eg = 1.99 eV for n = 2 and Eg = 1.73 eV for n = 3, which show slightly narrower gaps compared to the corresponding RP perovskites. First-principles theoretical electronic structure calculations confirm the experimental optical gap trends suggesting that the ACI perovskites are direct bandgap semiconductors with wide valence and conduction bandwidths. To assess the potential of the ACI perovskites toward solar cell applications, we studied the (C(NH2)3)(CH3NH3)3Pb3I10 (n = 3) compound. Compact thin films from the (C(NH2)3)(CH3NH3)3Pb3I10 compound with excellent surface coverage can be obtained from the antisolvent dripping method. Planar photovoltaic devices from optimized ACI perovskite films yield a power-conversion-efficiency of 7.26% with a high open-circuit voltage of ~1 V and a striking fill factor of ~80%.« less

  19. Pressure-induced metallization of the halide perovskite (CH 3NH 3)PbI 3

    DOE PAGES

    Jaffe, Adam; Lin, Yu; Mao, Wendy L.; ...

    2017-03-14

    We report the metallization of the hybrid perovskite semiconductor (MA)PbI 3 (MA = CH 3NH 3 +) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI 3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study ofmore » metallic properties in oxide perovskites has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Lastly, pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.« less

  20. Pressure-induced metallization of the halide perovskite (CH 3NH 3)PbI 3

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jaffe, Adam; Lin, Yu; Mao, Wendy L.

    We report the metallization of the hybrid perovskite semiconductor (MA)PbI 3 (MA = CH 3NH 3 +) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI 3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study ofmore » metallic properties in oxide perovskites has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Lastly, pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.« less

  1. Structural characterization of a new vacancy ordered perovskite modification found for Ba{sub 3}Fe{sub 3}O{sub 7}F (BaFeO{sub 2.333}F{sub 0.333}): Towards understanding of vacancy ordering for different perovskite-type ferrites

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Clemens, Oliver, E-mail: oliver.clemens@kit.edu; Karlsruher Institut für Technologie, Institut für Nanotechnologie, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen

    2015-05-15

    The new vacancy ordered perovskite-type compound Ba{sub 3}Fe{sub 3}O{sub 7}F (BaFeO{sub 2.33}F{sub 0.33}) was prepared by topochemical low-temperature fluorination of Ba{sub 2}Fe{sub 2}O{sub 5} (BaFeO{sub 2.5}) using stoichiometric amounts of polyvinylidene difluoride (PVDF). The vacancy order was found to be unique so far for perovskite compounds, and the connectivity pattern can be explained by the formula Ba{sub 3}(FeX{sub 6/2}) (FeX{sub 5/2}) (FeX{sub 3/2}X{sub 1/1}), with X=O/F. Mössbauer measurements were used to confirm the structural analysis and agree with the presence of Fe{sup 3+} in the above mentioned coordination environments. Group–subgroup relationships were used to build a starting model for themore » structure solution and to understand the relationship to the cubic perovskite structure. Furthermore, a comparison of a variety of vacancy-ordered iron-containing perovskite-type structures is given, highlighting the factors which favour one structure type over the other depending on the composition. - Graphical abstract: The crystal structure of Ba{sub 3}Fe{sub 3}O{sub 7}F in comparison to other perovskite type ferrites. - Highlights: • The crystal structure of Ba{sub 3}Fe{sub 3}O{sub 7}F in comparison to other perovskite type ferrites. • Ba{sub 3}Fe{sub 3}O{sub 7}F was synthesized by low temperature fluorination of Ba{sub 2}Fe{sub 2}O{sub 5}. • Ba{sub 3}Fe{sub 3}O{sub 7}F shows a unique vacancy order not found for other perovskite type compounds. • The structure of Ba{sub 3}Fe{sub 3}O{sub 7}F was solved using group–subgroup relationships. • A systematic comparison to other ferrite type compounds reveals structural similarities and differences. • The A-site coordination of the cation is shown to play an important role for the type of vacancy order found.« less

  2. Unraveling the Chemical Nature of the 3D "Hollow" Hybrid Halide Perovskites.

    PubMed

    Spanopoulos, Ioannis; Ke, Weijun; Stoumpos, Constantinos C; Schueller, Emily C; Kontsevoi, Oleg Y; Seshadri, Ram; Kanatzidis, Mercouri G

    2018-05-02

    The newly introduced class of 3D halide perovskites, termed "hollow" perovskites, has been recently demonstrated as light absorbing semiconductor materials for fabricating lead-free perovskite solar cells with enhanced efficiency and superior stability. Hollow perovskites derive from three-dimensional (3D) AMX 3 perovskites ( A = methylammonium (MA), formamidinium (FA); M = Sn, Pb; X = Cl, Br, I), where small molecules such as ethylenediammonium cations ( en) can be incorporated as the dication without altering the structure dimensionality. We present in this work the inherent structural properties of the hollow perovskites and expand this class of materials to the Pb-based analogues. Through a combination of physical and spectroscopic methods (XRD, gas pycnometry, 1 H NMR, TGA, SEM/EDX), we have assigned the general formula (A) 1- x ( en) x (M) 1-0.7 x (X) 3-0.4 x to the hollow perovskites. The incorporation of en in the 3D perovskite structure leads to massive M and X vacancies in the 3D [ MX 3 ] framework, thus the term hollow. The resulting materials are semiconductors with significantly blue-shifted direct band gaps from 1.25 to 1.51 eV for Sn-based perovskites and from 1.53 to 2.1 eV for the Pb-based analogues. The increased structural disorder and hollow nature were validated by single crystal X-ray diffraction analysis as well as pair distribution function (PDF) analysis. Density functional theory (DFT) calculations support the experimental trends and suggest that the observed widening of the band gap is attributed to the massive M and X vacancies, which create a less connected 3D hollow structure. The resulting materials have superior air stability, where in the case of Sn-based hollow perovskites it exceeds two orders of temporal magnitude compared to the conventional full perovskites of MASnI 3 and FASnI 3 . The hollow perovskite compounds pose as a new platform of promising light absorbers that can be utilized in single junction or tandem solar cells.

  3. Antiferroelectric Nature of CH3NH3PbI3-xClx Perovskite and Its Implication for Charge Separation in Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Sewvandi, Galhenage A.; Kodera, Kei; Ma, Hao; Nakanishi, Shunsuke; Feng, Qi

    2016-07-01

    Perovskite solar cells (PSCs) have been attracted scientific interest due to high performance. Some researchers have suggested anomalous behavior of PSCs to the polarizations due to the ion migration or ferroelectric behavior. Experimental results and theoretical calculations have suggested the possibility of ferroelectricity in organic-inorganic perovskite. However, still no studies have been concretely discarded the ferroelectric nature of perovskite absorbers in PSCs. Hysteresis of P-E (polarization-electric field) loops is an important evidence to confirm the ferroelectricity. In this study, P-E loop measurements, in-depth structural study, analyses of dielectric behavior and the phase transitions of CH3NH3PbI3-xClx perovskite were carried out and investigated. The results suggest that CH3NH3PbI3-xClx perovskite is in an antiferroelectric phase at room temperature. The antiferroelectric phase can be switched to ferroelectric phase by the poling treatment and exhibits ferroelectric-like hysteresis P-E loops and dielectric behavior around room temperature; namely, the perovskite can generate a ferroelectric polarization under PSCs operating conditions. Furthermore, we also discuss the implications of ferroelectric polarization on PSCs charge separation.

  4. Antiferroelectric Nature of CH3NH3PbI3-xClx Perovskite and Its Implication for Charge Separation in Perovskite Solar Cells.

    PubMed

    Sewvandi, Galhenage A; Kodera, Kei; Ma, Hao; Nakanishi, Shunsuke; Feng, Qi

    2016-07-29

    Perovskite solar cells (PSCs) have been attracted scientific interest due to high performance. Some researchers have suggested anomalous behavior of PSCs to the polarizations due to the ion migration or ferroelectric behavior. Experimental results and theoretical calculations have suggested the possibility of ferroelectricity in organic-inorganic perovskite. However, still no studies have been concretely discarded the ferroelectric nature of perovskite absorbers in PSCs. Hysteresis of P-E (polarization-electric field) loops is an important evidence to confirm the ferroelectricity. In this study, P-E loop measurements, in-depth structural study, analyses of dielectric behavior and the phase transitions of CH3NH3PbI3-xClx perovskite were carried out and investigated. The results suggest that CH3NH3PbI3-xClx perovskite is in an antiferroelectric phase at room temperature. The antiferroelectric phase can be switched to ferroelectric phase by the poling treatment and exhibits ferroelectric-like hysteresis P-E loops and dielectric behavior around room temperature; namely, the perovskite can generate a ferroelectric polarization under PSCs operating conditions. Furthermore, we also discuss the implications of ferroelectric polarization on PSCs charge separation.

  5. Planar structured perovskite solar cells by hybrid physical chemical vapor deposition with optimized perovskite film thickness

    NASA Astrophysics Data System (ADS)

    Wei, Xiangyang; Peng, Yanke; Jing, Gaoshan; Cui, Tianhong

    2018-05-01

    The thickness of perovskite absorber layer is a critical parameter to determine a planar structured perovskite solar cell’s performance. By modifying the spin coating speed and PbI2/N,N-dimethylformamide (DMF) solution concentration, the thickness of perovskite absorber layer was optimized to obtain high-performance solar cells. Using a PbI2/DMF solution of 1.3 mol/L, maximum power conversion efficiency (PCE) of a perovskite solar cell is 15.5% with a perovskite film of 413 nm at 5000 rpm, and PCE of 14.3% was also obtained for a solar cell with a perovskite film of 182 nm thick. It is derived that higher concentration of PbI2/DMF will result in better perovskite solar cells. Additionally, these perovskite solar cells are highly uniform. In 14 sets of solar cells, standard deviations of 11 sets of solar cells were less than 0.50% and the smallest standard deviation was 0.25%, which demonstrates the reliability and effectiveness of hybrid physical chemical vapor deposition (HPCVD) method.

  6. Structural and thermodynamic aspects of organic-inorganic mixed halide (CH3NH3PbI3-xBrx) perovskite

    NASA Astrophysics Data System (ADS)

    Singh, Rajan Kumar; Kumar, Ranveer; Jain, Neha; Singh, Jai; Mishra, S. K.

    2018-05-01

    Mixed Bromine and iodine lead halide perovskite CH3NH3PbI3-xBrx have been synthesized by solution phase method using CH3NH3I and PbBr2 precursors in ambient conditions. X-ray diffraction indicates the formation of cubic perovskite at room temperature with space group of Pm3m. The mixed perovskite improved crystallanity and grain contour which may significant improve photovoltaic performance of perovskite devices. Thermodynamic behavior of such type of material also indicates energy absorption nature of materials.

  7. Antiferroelectric Nature of CH3NH3PbI3−xClx Perovskite and Its Implication for Charge Separation in Perovskite Solar Cells

    PubMed Central

    Sewvandi, Galhenage A.; Kodera, Kei; Ma, Hao; Nakanishi, Shunsuke; Feng, Qi

    2016-01-01

    Perovskite solar cells (PSCs) have been attracted scientific interest due to high performance. Some researchers have suggested anomalous behavior of PSCs to the polarizations due to the ion migration or ferroelectric behavior. Experimental results and theoretical calculations have suggested the possibility of ferroelectricity in organic-inorganic perovskite. However, still no studies have been concretely discarded the ferroelectric nature of perovskite absorbers in PSCs. Hysteresis of P-E (polarization-electric field) loops is an important evidence to confirm the ferroelectricity. In this study, P-E loop measurements, in-depth structural study, analyses of dielectric behavior and the phase transitions of CH3NH3PbI3−xClx perovskite were carried out and investigated. The results suggest that CH3NH3PbI3−xClx perovskite is in an antiferroelectric phase at room temperature. The antiferroelectric phase can be switched to ferroelectric phase by the poling treatment and exhibits ferroelectric-like hysteresis P-E loops and dielectric behavior around room temperature; namely, the perovskite can generate a ferroelectric polarization under PSCs operating conditions. Furthermore, we also discuss the implications of ferroelectric polarization on PSCs charge separation. PMID:27468802

  8. Understanding the Origins of Large Negative Thermal Expansion in Ferroelectric Perovskites from First Principles

    NASA Astrophysics Data System (ADS)

    Ritz, Ethan; Benedek, Nicole

    Many of the functional properties of ABO3 perovskite oxides (for example, ferroelectricity) are strongly linked to particular phonon modes in the material. In addition, in many cases it is possible to formulate simple guidelines or `rules of thumb' that link crystal structure and chemistry to specific lattice dynamical characteristics. The thermal transport properties of perovskites are thus potentially highly tunable and dynamically controllable with external fields. We use first-principles density functional theory to reveal new details related to the origin of the large negative thermal expansion (NTE) observed for ferroelectric PbTiO3. Although the origin of NTE in this material is often ascribed to ferroelectricity (which arises from the freezing in of a soft, zone-center optical phonon), our results suggest that zone-boundary modes play a major role in driving NTE. In addition, hybridization between different electronic states has a significant effect on the lattice dynamics of PbTiO3 in general, and its NTE behavior in particular. Our work has implications for the understanding of, discovery and design of NTE in perovskites and other families of inorganic materials. This work was supported in part by a NASA Space Technology Research Fellowship.

  9. Layered structures of organic/inorganic hybrid halide perovskites

    NASA Astrophysics Data System (ADS)

    Huan, Tran Doan; Tuoc, Vu Ngoc; Minh, Nguyen Viet

    2016-03-01

    Organic-inorganic hybrid halide perovskites, in which the A cations of an ABX3 perovskite are replaced by organic cations, may be used for photovoltaic and solar thermoelectric applications. In this contribution, we systematically study three lead-free hybrid perovskites, i.e., methylammonium tin iodide CH3NH3SnI3 , ammonium tin iodide NH4SnI3 , and formamidnium tin iodide HC (NH2)2SnI3 by first-principles calculations. We find that in addition to the commonly known motif in which the corner-shared SnI6 octahedra form a three-dimensional network, these materials may also favor a two-dimensional (layered) motif formed by alternating layers of the SnI6 octahedra and the organic cations. These two motifs are nearly equal in free energy and are separated by low barriers. These layered structures features many flat electronic bands near the band edges, making their electronic structures significantly different from those of the structural phases composed of three-dimension networks of SnI6 octahedra. Furthermore, because the electronic structures of HC (NH2)2SnI3 are found to be rather similar to those of CH3NH3SnI3 , formamidnium tin iodide may also be promising for the applications of methylammonium tin iodide.

  10. Oxygen Vacancy-Tuned Physical Properties in Perovskite Thin Films with Multiple B-site Valance States

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Enriquez, Erik; Chen, Aiping; Harrell, Zach

    Controlling oxygen content in perovskite oxides with ABO 3 structure is one of most critical steps for tuning their functionality. Notably, there have been tremendous efforts to understand the effect of changes in oxygen content on the properties of perovskite thin films that are not composed of cations with multiple valance states. Here, we study the effect of oxygen vacancies on structural and electrical properties in epitaxial thin films of SrFeO 3-δ (SFO), where SFO is a compound with multiple valance states at the B site. Various annealing treatments are used to produce different oxygen contents in the films, whichmore » has resulted in significant structural changes in the fully strained SFO films. The out-of-plane lattice parameter and tetragonality increase with decreasing oxygen concentration, indicating the crystal structure is closely related to the oxygen content. Importantly, variation of the oxygen content in the films significantly affects the dielectric properties, leakage conduction mechanisms, and the resistive hysteresis of the materials. These results establish the relationship between oxygen content and structural and functional properties for a range of multivalent transition metal oxides.« less

  11. Oxygen Vacancy-Tuned Physical Properties in Perovskite Thin Films with Multiple B-site Valance States

    DOE PAGES

    Enriquez, Erik; Chen, Aiping; Harrell, Zach; ...

    2017-04-18

    Controlling oxygen content in perovskite oxides with ABO 3 structure is one of most critical steps for tuning their functionality. Notably, there have been tremendous efforts to understand the effect of changes in oxygen content on the properties of perovskite thin films that are not composed of cations with multiple valance states. Here, we study the effect of oxygen vacancies on structural and electrical properties in epitaxial thin films of SrFeO 3-δ (SFO), where SFO is a compound with multiple valance states at the B site. Various annealing treatments are used to produce different oxygen contents in the films, whichmore » has resulted in significant structural changes in the fully strained SFO films. The out-of-plane lattice parameter and tetragonality increase with decreasing oxygen concentration, indicating the crystal structure is closely related to the oxygen content. Importantly, variation of the oxygen content in the films significantly affects the dielectric properties, leakage conduction mechanisms, and the resistive hysteresis of the materials. These results establish the relationship between oxygen content and structural and functional properties for a range of multivalent transition metal oxides.« less

  12. Oxygen-vacancy-mediated dielectric property in perovskite Eu0.5Ba0.5TiO3-δ epitaxial thin films

    NASA Astrophysics Data System (ADS)

    Li, Weiwei; Gu, Junxing; He, Qian; Zhang, Kelvin H. L.; Wang, Chunchang; Jin, Kuijuan; Wang, Yongqiang; Acosta, Matias; Wang, Haiyan; Borisevich, Albina Y.; MacManus-Driscoll, Judith L.; Yang, Hao

    2018-04-01

    Dielectric relaxation in ABO3 perovskite oxides can result from many different charge carrier-related phenomena. Despite a strong understanding of dielectric relaxations, a detailed investigation of the relationship between the content of oxygen vacancies (VO) and dielectric relaxation has not been performed in perovskite oxide films. In this work, we report a systematic investigation of the influence of the VO concentration on the dielectric relaxation of Eu0.5Ba0.5TiO3-δ epitaxial thin films. Nuclear resonance backscattering spectrometry was used to directly measure the oxygen concentration in Eu0.5Ba0.5TiO3-δ films. We found that dipolar defects created by VO interact with the off-centered Ti ions, which results in the dielectric relaxation in Eu0.5Ba0.5TiO3-δ films. Activation energy gradually increases with the increasing content of VO. The present work significantly extends our understanding of relaxation properties in oxide films.

  13. Chemical Substitution-Induced and Competitive Formation of 6H and 3C Perovskite Structures in Ba3-xSrxZnSb2O9: The Coexistence of Two Perovskites in 0.3 ≤ x ≤ 1.0.

    PubMed

    Li, Jing; Jiang, Pengfei; Gao, Wenliang; Cong, Rihong; Yang, Tao

    2017-11-20

    6H and 3C perovskites are important prototype structures in materials science. We systemically studied the structural evolution induced by the Sr 2+ -to-Ba 2+ substitution to the parent 6H perovskite Ba 3 ZnSb 2 O 9 . The 6H perovskite is only stable in the narrow range of x ≤ 0.2, which attributes to the impressibility of [Sb 2 O 9 ]. The preference of 90° Sb-O-Sb connection and the strong Sb 5+ -Sb 5+ electrostatic repulsion in [Sb 2 O 9 ] are competitive factors to stabilize or destabilize the 6H structure when chemical pressure was introduced by Sr 2+ incorporation. Therefore, in the following, a wide two-phase region containing 1:2 ordered 6H-Ba 2.8 Sr 0.2 ZnSb 2 O 9 and rock-salt ordered 3C-Ba 2 SrZnSb 2 O 9 was observed (0.3 ≤ x ≤ 1.0). In the final, the successive symmetry descending was established from cubic (Fm3̅m, 1.3 ≤ x ≤ 1.8) to tetragonal (I4/m, 2.0 ≤ x ≤ 2.4), and finally to monoclinic (I2/m, 2.6 ≤ x ≤ 3.0). Here we proved that the electronic configurations of B-site cations, with either empty, partially, or fully filled d-shell, would also affect the structure stabilization, through the orientation preference of the B-O covalent bonding. Our investigation gives a deeper understanding of the factors to the competitive formation of perovskite structures, facilitating the fine manipulation on their physical properties.

  14. Pressure-Induced Metallization of the Halide Perovskite (CH 3 NH 3 )PbI 3

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jaffe, Adam; Lin, Yu; Mao, Wendy L.

    We report the metallization of the hybrid perovskite semiconductor (MA)PbI3 (MA = CH3NH3+) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study of metallic properties in oxide perovskitesmore » has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.« less

  15. Anion ordering, magnetic structure and properties of the vacancy ordered perovskite Ba{sub 3}Fe{sub 3}O{sub 7}F

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Clemens, Oliver, E-mail: oliver.clemens@nano.tu-darmstadt.de; Karlsruher Institut für Technologie, Institut für Nanotechnologie, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen; University of Birmingham, School of Chemistry, Birmingham B152TT

    2016-11-15

    This article describes a detailed investigation of the crystallographic and magnetic structure of perovskite type Ba{sub 3}Fe{sub 3}O{sub 7}F by a combined analysis of X-ray and neutron powder diffraction data. Complete ordering of vacancies within the perovskite lattice could be confirmed. In addition, the structure of the anion sublattice was studied by means of the valence bond method, which suggested partial ordering of the fluoride ions on two of the six crystallographically different anion sites. Moreover, the compound was found to show G-type antiferromagnetic ordering of Fe moments, in agreement with magnetometric measurements as well as previously recorded {sup 57}Femore » Mössbauer spectroscopy data. - Graphical abstract: The vacancy and anion ordered structure of Ba{sub 3}Fe{sub 3}O{sub 7}F is described together with its magnetic properties. - Highlights: • Ba{sub 3}Fe{sub 3}O{sub 7}F possesses a unique vacancy order not found for other perovskite type compounds. • The valence bond method was used to locate oxide and fluoride ions. • Fluoride ions are distributed only on two of the six anion sites in Ba{sub 3}Fe{sub 3}O{sub 7}F. • The compound shows G-type antiferromagnetic ordering of magnetic moments. • The magnetic structure could be refined in one of the maximal magnetic subgroups of the nuclear structure.« less

  16. Tunable anomalous orbital structure in a spinel-perovskite interface γ-Al2O3/SrTiO3

    NASA Astrophysics Data System (ADS)

    Cao, Yanwei; Liu, Xiaoran; Shafer, Padraic; Middey, Srimanta; Meyers, Derek; Kareev, Mikhail; Zhong, Zhicheng; Kim, Jong-Woo; Ryan, Philip; Arenholz, Elke; Chakhalian, Jak

    In all archetypical reported (001)-oriented perovskite heterostructures, for example LaTiO3/SrTiO3, LaAlO3/SrTiO3,YTiO3/SrTiO3 and so on, it has been deduced that the preferential occupation of two-dimensional electron gases is in-plane dxy state. In sharp contrast to this, the investigated electronic structure of a spinel-perovskite heterostructure γ-Al2O3/SrTiO3 by resonant soft X-ray linear dichroism, demonstrates that the preferential occupation is in out-of-plane dxz/dyz states for interfacial electrons. Moreover, the impact of strain further corroborates that this anomalous orbital structure can be linked to the altered crystal field at the interface and symmetry breaking of the interfacial structural units. Our findings provide another interesting route to engineer emergent quantum states with deterministic orbital symmetry. J.C. and Y.C. was supported by the Gordon and Betty Moore Foundation EPiQS Initiative through Grant No. GBMF4534. S.M. and M.K. were supported by the DOD-ARO under Grant No. 0402-172.

  17. Multiple-stage structure transformation of organic-inorganic hybrid perovskite CH 3 NH 3 PbI 3

    DOE PAGES

    Chen, Qiong; Liu, Henan; Kim, Hui -Seon; ...

    2016-09-15

    In this study, by performing spatially resolved Raman and photoluminescence spectroscopy with varying excitation wavelength, density, and data acquisition parameters, we achieve a unified understanding towards the spectroscopy signatures of the organic-inorganic hybrid perovskite, transforming from the pristine state (CH 3NH 3PbI 3) to the fully degraded state (i.e., PbI 2) for samples with varying crystalline domain size from mesoscopic scale (approximately 100 nm) to macroscopic size (centimeters), synthesized by three different techniques. We show that the hybrid perovskite exhibits multiple stages of structure transformation occurring either spontaneously or under light illumination, with exceptionally high sensitivity to the illumination conditionsmore » (e.g., power, illumination time, and interruption pattern). We highlight four transformation stages (stages I-IV, with stage I being the pristine state) along either the spontaneous or photoinduced degradation path exhibiting distinctly different Raman spectroscopy features at each stage, and point out that previously reported Raman spectra in the literature reflect highly degraded structures of either stage III or stage IV. Additional characteristic optical features of partially degraded materials under the joint action of spontaneous and photodegradation are also given. This study offers reliable benchmark results for understanding the intrinsic material properties and structure transformation of this unique category of hybrid materials, and the findings are pertinently important to a wide range of potential applications where the hybrid material is expected to function in greatly different environment and light-matter interaction conditions.« less

  18. Multiple-Stage Structure Transformation of Organic-Inorganic Hybrid Perovskite CH3NH3PbI3

    NASA Astrophysics Data System (ADS)

    Chen, Qiong; Liu, Henan; Kim, Hui-Seon; Liu, Yucheng; Yang, Mengjin; Yue, Naili; Ren, Gang; Zhu, Kai; Liu, Shengzhong; Park, Nam-Gyu; Zhang, Yong

    2016-07-01

    By performing spatially resolved Raman and photoluminescence spectroscopy with varying excitation wavelength, density, and data acquisition parameters, we achieve a unified understanding towards the spectroscopy signatures of the organic-inorganic hybrid perovskite, transforming from the pristine state (CH3NH3PbI3 ) to the fully degraded state (i.e., PbI2 ) for samples with varying crystalline domain size from mesoscopic scale (approximately 100 nm) to macroscopic size (centimeters), synthesized by three different techniques. We show that the hybrid perovskite exhibits multiple stages of structure transformation occurring either spontaneously or under light illumination, with exceptionally high sensitivity to the illumination conditions (e.g., power, illumination time, and interruption pattern). We highlight four transformation stages (stages I-IV, with stage I being the pristine state) along either the spontaneous or photoinduced degradation path exhibiting distinctly different Raman spectroscopy features at each stage, and point out that previously reported Raman spectra in the literature reflect highly degraded structures of either stage III or stage IV. Additional characteristic optical features of partially degraded materials under the joint action of spontaneous and photodegradation are also given. This study offers reliable benchmark results for understanding the intrinsic material properties and structure transformation of this unique category of hybrid materials, and the findings are pertinently important to a wide range of potential applications where the hybrid material is expected to function in greatly different environment and light-matter interaction conditions.

  19. Quantum anomalous Hall phase and half-metallic phase in ferromagnetic (111) bilayers of 4 d and 5 d transition metal perovskites

    NASA Astrophysics Data System (ADS)

    Chandra, Hirak Kumar; Guo, Guang-Yu

    2017-04-01

    Extraordinary electronic phases can form in artificial oxide heterostructures, which will provide a fertile ground for new physics and also give rise to novel device functions. Based on a systematic first-principles density functional theory study of the magnetic and electronic properties of the (111) superlattices (ABO3) 2/(AB'O3)10 of 4 d and 5 d transition metal perovskite (B = Ru, Rh, Ag, Re, Os, Ir, Au; AB'O3=LaAlO3 , SrTiO3) , we demonstrate that due to quantum confinement, bilayers (LaBO3)2 (B = Ru, Re, Os) and (SrBO3)2 (B = Rh, Os, Ir) are ferromagnetic with ordering temperatures up to room temperature. In particular, bilayer (LaOsO3)2 is an exotic spin-polarized quantum anomalous Hall insulator, while the other ferromagnetic bilayers are metallic with large Hall conductances comparable to the conductance quantum. Furthermore, bilayers (LaRuO3)2 and (SrRhO3)2 are half metallic, while the bilayer (SrIrO3)2 exhibits a peculiar colossal magnetic anisotropy. Our findings thus show that 4 d and 5 d metal perovskite (111) bilayers are a class of quasi-two-dimensional materials for exploring exotic quantum phases and also for advanced applications such as low-power nanoelectronics and oxide spintronics.

  20. Influence of transition metal electronegativity on the oxygen storage capacity of perovskite oxides.

    PubMed

    Liu, Lu; Taylor, Daniel D; Rodriguez, Efrain E; Zachariah, Michael R

    2016-08-16

    The selection of highly efficient oxygen carriers (OCs) is a key step necessary for the practical development of chemical looping combustion (CLC). In this study, a series of ABO3 perovskites, where A = La, Ba, Sr, Ca and B = Cr, Mn, Fe, Co, Ni, Cu, are synthesized and tested in a fixed bed reactor for reactivity and stability as OCs with CH4 as the fuel. We find that the electronegativity of the transition metal on the B-site (λB), is a convenient descriptor for oxygen storage capacity (OSC) of our perovskite samples. By plotting OSC for total methane oxidation against λB, we observe an inverted volcano plot relationship. These results could provide useful guidelines for perovskite OC design and their other energy related applications.

  1. Synthesis, structural and semiconducting properties of Ba(Cu1/3 Sb2/3)O3-PbTiO3 solid solutions

    NASA Astrophysics Data System (ADS)

    Singh, Chandra Bhal; Kumar, Dinesh; Prashant, Verma, Narendra Kumar; Singh, Akhilesh Kumar

    2018-05-01

    We report the synthesis and properties of a new solid solution 0.05Ba(Cu1/3Sb2/3)O3-0.95PbTiO3 (BCS-PT) which shows the semiconducting properties. In this study, we have designed new perovskite-type (ABO3) solid solution of BCS-PT that have tunable optical band gap. BCS-PT compounds were prepared by conventional solid-state reaction method and their structural, micro-structural and optical properties were analyzed. The calcination temperature for BCS-PT solid solutions has been optimized to obtain a phase pure system. The Reitveld analysis of X-ray data show that all samples crystallize in tetragonal crystal structure with space group P4mm. X-ray investigation revealed that increase in calcination temperature led to increase of lattice parameter `a' while `c' parameter value lowered. The band gap of PbTiO3 is reduced from 3.2 eV to 2.8 eV with BCS doping and with increasing calcination temperature it further reduces to 2.56 eV. The reduced band gap indicated that the compounds are semiconducting and can be used for photovoltaic device applications.

  2. High-Pressure Study of Perovskite-Like Organometal Halide: Band-Gap Narrowing and Structural Evolution of [NH 3 -(CH 2 ) 4 -NH 3 ]CuCl 4

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Qian; Li, Shourui; Wang, Kai

    Searching for nontoxic and stable perovskite-like alternatives to lead-based halide perovskites for photovoltaic application is one urgent issue in photoelectricity science. Such exploration inevitably requires an effective method to accurately control both the crystalline and electronic structures. This work applies high pressure to narrow the band gap of perovskite-like organometal halide, [NH 3-(CH 2) 4-NH 3]CuCl 4 (DABCuCl4), through the crystalline-structure tuning. The band gap keeps decreasing below ~12 GPa, involving the shrinkage and distortion of CuCl 4 2–. Inorganic distortion determines both band-gap narrowing and phase transition between 6.4 and 10.5 GPa, and organic chains function as the springmore » cushion, evidenced by the structural transition at ~0.8 GPa. The supporting function of organic chains protects DABCuCl 4 from phase transition and amorphization, which also contributes to the sustaining band-gap narrowing. This work combines crystal structure and macroscopic property together and offers new strategies for the further design and synthesis of hybrid perovskite-like alternatives.« less

  3. Annealing Effect on (FAPbI3)1−x(MAPbBr3)x Perovskite Films in Inverted-Type Perovskite Solar Cells

    PubMed Central

    Chen, Lung-Chien; Wu, Jia-Ren; Tseng, Zhong-Liang; Chen, Cheng-Chiang; Chang, Sheng Hsiung; Huang, Jun-Kai; Lee, King-Lien; Cheng, Hsin-Ming

    2016-01-01

    This study determines the effects of annealing treatment on the structure and the optical and electronic behaviors of the mixed (FAPbI3)1−x(MAPbBr3)x perovskite system. The experimental results reveal that (FAPbI3)1−x(MAPbBr3)x (x ~ 0.2) is an effective light-absorbing material for use in inverted planar perovskite solar cells owing to its large absorbance and tunable band gap. Therefore, good band-matching between the (FAPbI3)1−x(MAPbBr3)x and C60 in photovoltaic devices can be controlled by annealing at various temperatures. Accordingly, an inverted mixed perovskite solar cell with a record efficiency of 12.0% under AM1.5G irradiation is realized. PMID:28773874

  4. Phase Stability and Electronic Structure of Prospective Sb-Based Mixed Sulfide and Iodide 3D Perovskite (CH3NH3)SbSI2.

    PubMed

    Li, Tianyang; Wang, Xiaoming; Yan, Yanfa; Mitzi, David B

    2018-06-29

    Lead-free antimony-based mixed sulfide and iodide perovskite phases have recently been reported to be synthesized experimentally and to exhibit reasonable photovoltaic performance. Through a combination of experimental validation and computational analysis, we show no evidence of the formation of the mixed sulfide and iodide perovskite phase, MASbSI 2 (MA = CH 3 NH 3 + ), and instead that the main products are a mixture of the binary and ternary compounds (Sb 2 S 3 and MA 3 Sb 2 I 9 ). Density functional theory calculations also indicate that such a mixed sulfide and iodide perovskite phase should be thermodynamically less stable compared with binary/ternary anion-segregated secondary phases and less likely to be synthesized under equilibrium conditions. Additionally, band structure calculations show that this mixed sulfide and iodide phase, if possible to synthesize (e.g., under nonequilibrium conditions), should have a suitable direct band gap for photovoltaic application.

  5. Structural chemistry and magnetic properties of the perovskite Sr{sub 3}Fe{sub 2}TeO{sub 9}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tang, Yawei; Hunter, Emily C.; Battle, Peter D., E-mail: peter.battle@chem.ox.ac.uk

    2016-10-15

    A polycrystalline sample of perovskite-like Sr{sub 3}Fe{sub 2}TeO{sub 9} has been prepared in a solid-state reaction and studied by a combination of electron microscopy, Mössbauer spectroscopy, magnetometry, X-ray diffraction and neutron diffraction. The majority of the reaction product is shown to be a trigonal phase with a 2:1 ordered arrangement of Fe{sup 3+} and Te{sup 6+} cations. However, the sample is prone to nano-twinning and tetragonal domains with a different pattern of cation ordering exist within many crystallites. Antiferromagnetic ordering exists in the trigonal phase at 300 K and Sr{sub 3}Fe{sub 2}TeO{sub 9} is thus the first example of amore » perovskite with 2:1 trigonal cation ordering to show long-range magnetic order. At 300 K the antiferromagnetic phase coexists with two paramagnetic phases which show spin-glass behaviour below ~80 K. - Graphical abstract: Sr{sub 3}Fe{sub 2}TeO{sub 9} has a 2:1 ordered arrangement of Fe{sup 3+} and Te{sup 6+} cations over the octahedral sites of a perovskite structure and is antiferromagnetic at room temperature. - Highlights: • 2:1 Cation ordering in a trigonal perovskite. • Magnetically ordered trigonal perovskite. • Intergrowth of nanodomains in perovskite microstructure.« less

  6. (CH3 NH3 )2 PdCl4 : A Compound with Two-Dimensional Organic-Inorganic Layered Perovskite Structure.

    PubMed

    Huang, Tang Jiao; Thiang, Zhang Xian; Yin, Xuesong; Tang, Chunhua; Qi, Guojun; Gong, Hao

    2016-02-01

    The synthesis of previously unknown perovskite (CH 3 NH 3 ) 2 PdCl 4 is reported. Despite using an organic cation with the smallest possible alkyl group, a 2D organic-inorganic layered Pd-based perovskites was still formed. This demonstrates that Pd-based 2D perovskites can be obtained even if the size of the organic cation is below the size limit predicted by the Goldschmidt tolerance-factor formula. The (CH 3 NH 3 ) 2 PdCl 4 phase has a bulk resistivity of 1.4 Ω cm, a direct optical gap of 2.22 eV, and an absorption coefficient on the order of 10 4  cm -1 . XRD measurements suggest that the compound is moderately stable in air, an important advantage over several existing organic-inorganic perovskites that are prone to phase degradation problems when exposed to the atmosphere. Given the recent interest in organic-inorganic perovskites, the synthesis of this new Pd-based organic-inorganic perovskite may be helpful in the preparation and understanding of other organic-inorganic perovskites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Thermally Induced Structural Evolution and Performance of Mesoporous Block Copolymer-Directed Alumina Perovskite Solar Cells

    PubMed Central

    2015-01-01

    Structure control in solution-processed hybrid perovskites is crucial to design and fabricate highly efficient solar cells. Here, we utilize in situ grazing incidence wide-angle X-ray scattering and scanning electron microscopy to investigate the structural evolution and film morphologies of methylammonium lead tri-iodide/chloride (CH3NH3PbI3–xClx) in mesoporous block copolymer derived alumina superstructures during thermal annealing. We show the CH3NH3PbI3–xClx material evolution to be characterized by three distinct structures: a crystalline precursor structure not described previously, a 3D perovskite structure, and a mixture of compounds resulting from degradation. Finally, we demonstrate how understanding the processing parameters provides the foundation needed for optimal perovskite film morphology and coverage, leading to enhanced block copolymer-directed perovskite solar cell performance. PMID:24684494

  8. Crystal structure of guanidinium hexafluoridovanadate(III), (CN3H6)3[VF6]: an unusual hybrid compound related to perovskite.

    PubMed

    Black, Cameron; Lightfoot, Philip

    2017-03-01

    Vanadium fluorides with novel crystal-chemical features and interesting physical properties can be prepared by solvothermal synthetic routes. The title compound, guanidinium hexafluoridovanadate(III), has a cubic structure (space group Pa-3), exhibiting isolated regular VF 6 octahedral units, which are hydrogen bonded to protonated guanidinium moieties. Although the VF 6 octahedral units are not linked directly together, there are structural similarities between this crystal structure and those of the wider family of perovskite materials, in particular, hybrid perovskites based on extended ligands such as cyanide. In this context, the octahedral tilt system of the present compound is of interest and demonstrates that unusual tilt systems can be mediated via `molecular' linkers which allow only supramolecular rather than covalent interactions.

  9. Role of bromine doping on the photovoltaic properties and microstructures of CH{sub 3}NH{sub 3}PbI{sub 3} perovskite solar cells

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Suzuki, Atsushi; Okada, Hiroshi; Oku, Takeo

    Organic-inorganic hybrid heterojunction solar cells containing CH{sub 3}NH{sub 3}PbI{sub 3} perovskite compound were fabricated using mesoporous TiO{sub 2} as the electronic transporting layer and spirobifluorence as the hole-transporting layer. The purpose of the present study is to investigate role of bromine (Br) doping on the photovoltaic properties and microstructure of CH{sub 3}NH{sub 3}PbI{sub 3} perovskite solar cells. Photovoltaic, optical properties and microstructures of perovskite-based solar cells were investigated. The X-ray diffraction identified crystal structure of the perovskite layer doped with Br in the solar cell. Scanning electron microscopy observation showed a different behavior of surface morphology and the perovskite crystalmore » structure on the TiO{sub 2} mesoporous structure depending on extent amount of hydrogen doping of Br. The role of bromide halogen doping on the perovskite crystal structure and photovoltaic properties was due to improvement of carrier mobility, optimization of electron structure, band gap related with the photovoltaic parameters of V{sub oc}, J{sub sc} and η. Energy diagram and photovoltaic mechanism of the perovskite solar cells varied with halogen doping was discussed by experimental results.« less

  10. Effect of Different CH3NH3PbI3 Morphologies on Photovoltaic Properties of Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Chen, Lung-Chien; Lee, Kuan-Lin; Wu, Wen-Ti; Hsu, Chien-Feng; Tseng, Zong-Liang; Sun, Xiao Hong; Kao, Yu-Ting

    2018-05-01

    In this study, the perovskite layers were prepared by two-step wet process with different CH3NH3I (MAI) concentrations. The cell structure was glass/FTO/TiO2-mesoporous/CH3NH3PbI3 (MAPbI3)/spiro-OMeTAD/Ag. The MAPbI3 perovskite films were prepared using high and low MAI concentrations in a two-step process. The perovskite films were optimized at different spin coating speed and different annealing temperatures to enhance the power conversion efficiency (PCE) of perovskite solar cells. The PCE of the resulting device based on the different perovskite morphologies was discussed. The PCE of the best cell was up to 17.42%, open circuit voltage of 0.97 V, short current density of 24.06 mA/cm2, and fill factor of 0.747.

  11. Effect of Different CH3NH3PbI3 Morphologies on Photovoltaic Properties of Perovskite Solar Cells.

    PubMed

    Chen, Lung-Chien; Lee, Kuan-Lin; Wu, Wen-Ti; Hsu, Chien-Feng; Tseng, Zong-Liang; Sun, Xiao Hong; Kao, Yu-Ting

    2018-05-08

    In this study, the perovskite layers were prepared by two-step wet process with different CH 3 NH 3 I (MAI) concentrations. The cell structure was glass/FTO/TiO 2 -mesoporous/CH 3 NH 3 PbI 3 (MAPbI 3 )/spiro-OMeTAD/Ag. The MAPbI 3 perovskite films were prepared using high and low MAI concentrations in a two-step process. The perovskite films were optimized at different spin coating speed and different annealing temperatures to enhance the power conversion efficiency (PCE) of perovskite solar cells. The PCE of the resulting device based on the different perovskite morphologies was discussed. The PCE of the best cell was up to 17.42%, open circuit voltage of 0.97 V, short current density of 24.06 mA/cm 2 , and fill factor of 0.747.

  12. High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties.

    PubMed

    Jaffe, Adam; Lin, Yu; Beavers, Christine M; Voss, Johannes; Mao, Wendy L; Karunadasa, Hemamala I

    2016-04-27

    We report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX3 (MA = CH3NH3 (+), X = Br(-) or I(-)) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites' precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaque black with compression. Indeed, electronic conductivity measurements of (MA)PbI3 obtained within a diamond-anvil cell show that the material's resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(Br x I1-x )3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain the low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors.

  13. High-pressure crystal structure of elastically isotropic CaTiO3 perovskite under hydrostatic and non-hydrostatic conditions.

    PubMed

    Zhao, Jing; Ross, Nancy L; Wang, Di; Angel, Ross J

    2011-11-16

    The structural evolution of orthorhombic CaTiO3 perovskite has been studied using high-pressure single-crystal x-ray diffraction under hydrostatic conditions up to 8.1 GPa and under a non-hydrostatic stress field formed in a diamond anvil cell (DAC) up to 4.7 GPa. Under hydrostatic conditions, the TiO6 octahedra become more tilted and distorted with increasing pressure, similar to other 2:4 perovskites. Under non-hydrostatic conditions, the experiments do not show any apparent difference in the internal structural variation from hydrostatic conditions and no additional tilts and distortions in the TiO6 octahedra are observed, even though the lattice itself becomes distorted due to the non-hydrostatic stress. The similarity between the hydrostatic and non-hydrostatic cases can be ascribed to the fact that CaTiO3 perovskite is nearly elastically isotropic and, as a consequence, its deviatoric unit-cell volume strain produced by the non-hydrostatic stress is very small; in other words, the additional octahedral tilts relevant to the extra unit-cell volume associated with the deviatoric unit-cell volume strain may be totally neglected. This study further addresses the role that three factors--the elastic properties, the crystal orientation and the pressure medium--have on the structural evolution of an orthorhombic perovskite loaded in a DAC under non-hydrostatic conditions. The influence of these factors can be clearly visualized by plotting the three-dimensional distribution of the deviatoric unit-cell volume strain in relation to the cylindrical axis of the DAC and indicates that, if the elasticity of a perovskite is nearly isotropic as it is for CaTiO3, the other two factors become relatively insignificant.

  14. Critical Intermediate Structure That Directs the Crystalline Texture and Surface Morphology of Organo-Lead Trihalide Perovskite.

    PubMed

    Chia, Hao-Chung; Sheu, Hwo-Shuenn; Hsiao, Yu-Yun; Li, Shao-Sian; Lan, Yi-Kang; Lin, Chung-Yao; Chang, Je-Wei; Kuo, Yen-Chien; Chen, Chia-Hao; Weng, Shih-Chang; Su, Chun-Jen; Su, An-Chung; Chen, Chun-Wei; Jeng, U-Ser

    2017-10-25

    We have identified an often observed yet unresolved intermediate structure in a popular processing with dimethylformamide solutions of lead chloride and methylammonium iodide for perovskite solar cells. With subsecond time-resolved grazing-incidence X-ray scattering and X-ray photoemission spectroscopy, supplemental with ab initio calculation, the resolved intermediate structure (CH 3 NH 3 ) 2 PbI 2 Cl 2 ·CH 3 NH 3 I features two-dimensional (2D) perovskite bilayers of zigzagged lead-halide octahedra and sandwiched CH 3 NH 3 I layers. Such intermediate structure reveals a hidden correlation between the intermediate phase and the composition of the processing solution. Most importantly, the 2D perovskite lattice of the intermediate phase is largely crystallographically aligned with the [110] planes of the three-dimensional perovskite cubic phase; consequently, with sublimation of Cl ions from the organo-lead octahedral terminal corners in prolonged annealing, the zigzagged octahedral layers of the intermediate phase can merge with the intercalated methylammonium iodide layers for templated growth of perovskite crystals. Regulated by annealing temperature and the activation energies of the intermediate and perovskite, deduced from analysis of temperature-dependent structural kinetics, the intermediate phase is found to selectively mature first and then melt along the layering direction for epitaxial conversion into perovskite crystals. The unveiled epitaxial conversion under growth kinetics controls might be general for solution-processed and intermediate-templated perovskite formation.

  15. On the Role of Interfaces in Planar-Structured HC(NH2 )2 PbI3 Perovskite Solar Cells.

    PubMed

    Seol, Dong-Jin; Lee, Jin-Wook; Park, Nam-Gyu

    2015-07-20

    Planar-structured HC(NH2 )2 PbI3 (FAPbI3 ) perovskite solar cells were prepared via a two-step deposition process. To investigate the role of interface, the perovskite morphology was intentionally modified by varying HC(NH2 )2 I concentration. Surface and grain sizes of the deposited FAPbI3 became rougher and larger as the HC(NH2 )2 I concentration decreased from 58.2 to 40.7 mM. Average photocurrent was improved but photovoltage deteriorated slightly with decreasing concentration. Consequently, the average efficiency was improved from 7.82 % to 10.70 % and the best efficiency of 12.17 % was obtained at 40.7 mM. Photoluminescence (PL) at TiO2 /FAPbI3 interface was reduced with decreasing concentration, which was, however, reversed at FAPbI3 /spiro-MeOTAD one. By correlating PL data and the photovoltaic performance, we concluded that the TiO2 /perovskite interface plays a crucial role in determining photocurrent while the perovskite/spiro-MeOTAD interface is important in governing photovoltage. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Perovskite Oxide Thin Film Growth, Characterization, and Stability

    NASA Astrophysics Data System (ADS)

    Izumi, Andrew

    Studies into a class of materials known as complex oxides have evoked a great deal of interest due to their unique magnetic, ferroelectric, and superconducting properties. In particular, materials with the ABO3 perovskite structure have highly tunable properties because of the high stability of the structure, which allows for large scale doping and strain. This also allows for a large selection of A and B cations and valences, which can further modify the material's electronic structure. Additionally, deposition of these materials as thin films and superlattices through techniques such as pulsed laser deposition (PLD) results in novel properties due to the reduced dimensionality of the material. The novel properties of perovskite oxide heterostructures can be traced to a several sources, including chemical intermixing, strain and defect formation, and electronic reconstruction. The correlations between microstructure and physical properties must be investigated by examining the physical and electronic structure of perovskites in order to understand this class of materials. Some perovskites can undergo phase changes due to temperature, electrical fields, and magnetic fields. In this work we investigated Nd0.5Sr 0.5MnO3 (NSMO), which undergoes a first order magnetic and electronic transition at T=158K in bulk form. Above this temperature NSMO is a ferromagnetic metal, but transitions into an antiferromagnetic insulator as the temperature is decreased. This rapid transition has interesting potential in memory devices. However, when NSMO is deposited on (001)-oriented SrTiO 3 (STO) or (001)-oriented (LaAlO3)0.3-(Sr 2AlTaO6)0.7 (LSAT) substrates, this transition is lost. It has been reported in the literature that depositing NSMO on (110)-oriented STO allows for the transition to reemerge due to the partial epitaxial growth, where the NSMO film is strained along the [001] surface axis and partially relaxed along the [11¯0] surface axis. This allows the NSMO film enough

  17. Tracking BO6 Coupling in Perovskite Superlattices to Engineer Magnetic Interface Behavior

    NASA Astrophysics Data System (ADS)

    Borisevich, Albina; He, Qian; Ghosh, Saurabh; Moon, Eun Ju; May, Steve; Lupini, Andrew; Pantelides, Sokrates

    In the past several years, control of BO6 octahedral coupling at ABO3 perovskite interfaces has emerged as a new tool for engineering of interface properties due to its strong coupling to polar and magnetic properties. High resolution data on tilt transitions at interfaces is instrumental for evaluating the validity of existing theoretical models and developing predictive theories. Recently, we have developed a unique method to investigate BO6 rotation patterns in complex oxides with unit cell resolution. Our method involves column shape analysis in ABF-STEM images of the perovskite heterointerfaces taken in specific orientations. This method will allow us to determine local symmetry between adjacent unit cells, revealing the BO6 coupling behavior at heterointerfaces in 3D. This technique was used to characterize structure and predict properties via a combined STEM and DFT study of magnetic superlattice of La(Ca)MnO3/La(Sr)MnO3 with different periodicities, which exhibit a range of electromagnetic coupling behaviors. We will also discuss the prospects for tilted structure determination using electron ptychography. The correlations among the BO6 rotation, domain size, superlattice periodicity and the electromagnetic coupling will be discussed in detail. Research supported by the MSED of the U.S.DOE, and through a user project at ORNL's CNMS, sponsored by the SUFD of the U.S. DOE.

  18. ABO3, a WRKY transcription factor, mediates plant responses to abscisic acid and drought tolerance in Arabidopsis.

    PubMed

    Ren, Xiaozhi; Chen, Zhizhong; Liu, Yue; Zhang, Hairong; Zhang, Min; Liu, Qian; Hong, Xuhui; Zhu, Jian-Kang; Gong, Zhizhong

    2010-08-01

    The biological functions of WRKY transcription factors in plants have been widely studied, but their roles in abiotic stress are still not well understood. We isolated an ABA overly sensitive mutant, abo3, which is disrupted by a T-DNA insertion in At1g66600 encoding a WRKY transcription factor AtWRKY63. The mutant was hypersensitive to ABA in both seedling establishment and seedling growth. However, stomatal closure was less sensitive to ABA, and the abo3 mutant was less drought tolerant than the wild type. Northern blot analysis indicated that the expression of the ABA-responsive transcription factor ABF2/AREB1 was markedly lower in the abo3 mutant than in the wild type. The abo3 mutation also reduced the expression of stress-inducible genes RD29A and COR47, especially early during ABA treatment. ABO3 is able to bind the W-box in the promoter of ABF2in vitro. These results uncover an important role for a WRKY transcription factor in plant responses to ABA and drought stress. © 2010 The Authors. Journal compilation © 2010 Blackwell Publishing Ltd.

  19. Organic-Inorganic Perovskites: Structural Versatility for Functional Materials Design.

    PubMed

    Saparov, Bayrammurad; Mitzi, David B

    2016-04-13

    Although known since the late 19th century, organic-inorganic perovskites have recently received extraordinary research community attention because of their unique physical properties, which make them promising candidates for application in photovoltaic (PV) and related optoelectronic devices. This review will explore beyond the current focus on three-dimensional (3-D) lead(II) halide perovskites, to highlight the great chemical flexibility and outstanding potential of the broader class of 3-D and lower dimensional organic-based perovskite family for electronic, optical, and energy-based applications as well as fundamental research. The concept of a multifunctional organic-inorganic hybrid, in which the organic and inorganic structural components provide intentional, unique, and hopefully synergistic features to the compound, represents an important contemporary target.

  20. Interfacial B-site atomic configuration in polar (111) and non-polar (001) SrIrO3/SrTiO3 heterostructures

    NASA Astrophysics Data System (ADS)

    Anderson, T. J.; Zhou, H.; Xie, L.; Podkaminer, J. P.; Patzner, J. J.; Ryu, S.; Pan, X. Q.; Eom, C. B.

    2017-09-01

    The precise control of interfacial atomic arrangement in ABO3 perovskite heterostructures is paramount, particularly in cases where the subsequent electronic properties of the material exhibit geometrical preferences along polar crystallographic directions that feature inevitably complex surface reconstructions. Here, we present the B-site interfacial structure in polar (111) and non-polar (001) SrIrO3/SrTiO3 interfaces. The heterostructures were examined using scanning transmission electron microscopy and synchrotron-based coherent Bragg rod analysis. Our results reveal the preference of B-site intermixing across the (111) interface due to the polarity-compensated SrTiO3 substrate surface prior to growth. By comparison, the intermixing at the non-polar (001) interface is negligible. This finding suggests that the intermixing may be necessary to mitigate epitaxy along heavily reconstructed and non-stoichiometric (111) perovskite surfaces. Furthermore, this preferential B-site configuration could allow the geometric design of the interfacial perovskite structure and chemistry to selectively engineer the correlated electronic states of the B-site d-orbital.

  1. Pressure Induced Iron Spin Crossover in MgGeO3 Perovskite and Post-perovskite

    NASA Astrophysics Data System (ADS)

    Wentzcovitch, R. M.; Shukla, G.; Topsakal, M.

    2014-12-01

    MgGeO3-perovskite is known to be a low-pressure analog of MgSiO3-perovskite in many respects, but especially in regard to the post-perovskite transition. As such, investigation of spin state changes in Fe-bearing MgGeO3 might help to clarify some aspects of this type of state change in Fe-bearing MgSiO3. Using DFT+U calculations, we have investigated pressure induced state changes in Fe-bearing MgGeO3 perovskite and post-perovskite. Owing to the relatively larger atomic size of germanium compared to silicon, germanate phases have larger unit cell volume and interatomic distances than equivalent silicate phases at same pressures. As a result, all pressure induced state changes in iron occur at higher pressures in germanate phases than in the silicate ones, be it a spin state change or position change of (ferrous) iron in the perovskite cage. The effect of iron in the post-perovskite transition is also investigated.

  2. Ferromagnetic Phase Stability, Magnetic, Electronic, Elasto-Mechanical and Thermodynamic Properties of BaCmO3 Perovskite Oxide

    NASA Astrophysics Data System (ADS)

    Dar, Sajad Ahmad; Srivastava, Vipul; Sakalle, Umesh Kumar; Parey, Vanshree

    2018-04-01

    The structural, electronic, elasto-mechanical and thermodynamic properties of cubic ABO3 perovskites BaCmO3 has been successfully calculated within density functional theory via full potential linearized augmented plane wave. The structural study divulges ferromagnetic stability for the compound. For the precise calculation of electronic and magnetic properties a generalized gradient approximation (GGA), and a Hubbard approximation (GGA + U), (modified Becke Johnson approximation) mBJ have been incorporated. The electronic study portrays the half-metallic nature for the compound in all the approximations. The calculated magnetic moment with different approximations was found to be large and with an integer value of 6 μ b, this integer value of magnetic moment also proves the half-metallic nature for BaCmO3. The calculated elastic constants have been used to predict mechanical properties like the Young modulus (Y), the Shear modulus (G) and the Poisson ratio (ν). The calculated B/G and Cauchy pressure (C12-C44) present the brittle nature for BaCmO3. The thermodynamic parameters like heat capacity, thermal expansion, and Debye temperature have been calculated and examined in the temperature range of 0 K to 700 K and pressure between 0 GPa and 40 GPa. The melting temperature was also calculated and was found to be 1847 ± 300 K.

  3. Highly Stable, New, Organic-Inorganic Perovskite (CH3 NH3 )2 PdBr4 : Synthesis, Structure, and Physical Properties.

    PubMed

    Liu, Xixia; Huang, Tang Jiao; Zhang, Liuyang; Tang, Baoshan; Zhang, Nengduo; Shi, Diwen; Gong, Hao

    2018-04-03

    Lead halide perovskites have attracted striking attention recently, due to their appealing properties. However, toxicity and stability are two main factors restricting their application. In this work, a less toxic and highly stable Pd-based hybrid perovskite was experimentally synthesized, after exploring different experimental conditions. This new hybrid organic-inorganic perovskite (CH 3 NH 3 ) 2 PdBr 4 was found to be an orthorhombic crystal (Cmce, Z=4) with lattice parameters a=8.00, b=7.99, c=18.89 Å. The Cmce symmetry and lattice parameters were confirmed using Pawley refinement and the atoms positions were confirmed based on DFT calculation. This perovskite compound was determined to be a p-type semiconductor, with a resistivity of 102.9 kΩ cm, a carrier concentration of 3.4 ×10 12  cm -3 , and a mobility of 23.4 cm 2  (V s) -1 . Interestingly, XRD and UV/Vis measurements indicated that the phase of this new perovskite was maintained with an optical gap of 1.91 eV after leaving in air with a high humidity of 60 % for 4 days, and unchanged for months in N 2 atmosphere; much more stable than most existing organic-inorganic perovskites. The synthesis and various characterizations of this work further the understanding of this (CH 3 NH 3 ) 2 PdBr 4 organic-inorganic hybrid perovskite material. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells.

    PubMed

    Abdi-Jalebi, Mojtaba; Dar, M Ibrahim; Sadhanala, Aditya; Senanayak, Satyaprasad P; Grätzel, Michael; Friend, Richard H

    2017-03-19

    Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical properties. The possibility of doping was investigated by adding monovalent cation halides with similar ionic radii to Pb 2+ , including Cu + , Na + , and Ag + . A shift in the Fermi level and a remarkable decrease of sub-bandgap optical absorption, along with a lower energetic disorder in the perovskite, was achieved. An order-of-magnitude enhancement in the bulk hole mobility and a significant reduction of transport activation energy within an additive-based perovskite device was attained. The confluence of the aforementioned improved properties in the presence of these cations led to an enhancement in the photovoltaic parameters of the perovskite solar cell. An increase of 70 mV in open circuit voltage for AgI and a 2 mA/cm 2 improvement in photocurrent density for NaI- and CuBr-based solar cells were achieved compared to the pristine device. Our work paves the way for further improvements in the optoelectronic quality of CH3NH3PbI3 perovskite and subsequent devices. It highlights a new avenue for investigations on the role of dopant impurities in crystallization and controls the electronic defect density in perovskite structures.

  5. Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells

    PubMed Central

    Abdi-Jalebi, Mojtaba; Dar, M. Ibrahim; Sadhanala, Aditya; Senanayak, Satyaprasad P.; Grätzel, Michael; Friend, Richard H.

    2017-01-01

    Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical properties. The possibility of doping was investigated by adding monovalent cation halides with similar ionic radii to Pb2+, including Cu+, Na+, and Ag+. A shift in the Fermi level and a remarkable decrease of sub-bandgap optical absorption, along with a lower energetic disorder in the perovskite, was achieved. An order-of-magnitude enhancement in the bulk hole mobility and a significant reduction of transport activation energy within an additive-based perovskite device was attained. The confluence of the aforementioned improved properties in the presence of these cations led to an enhancement in the photovoltaic parameters of the perovskite solar cell. An increase of 70 mV in open circuit voltage for AgI and a 2 mA/cm2 improvement in photocurrent density for NaI- and CuBr-based solar cells were achieved compared to the pristine device. Our work paves the way for further improvements in the optoelectronic quality of CH3NH3PbI3 perovskite and subsequent devices. It highlights a new avenue for investigations on the role of dopant impurities in crystallization and controls the electronic defect density in perovskite structures. PMID:28362369

  6. An Exceptionally Narrow Band-Gap (∼4 eV) Silicate Predicted in the Cubic Perovskite Structure: BaSiO3.

    PubMed

    Hiramatsu, Hidenori; Yusa, Hitoshi; Igarashi, Ryo; Ohishi, Yasuo; Kamiya, Toshio; Hosono, Hideo

    2017-09-05

    The electronic structures of 35 A 2+ B 4+ O 3 ternary cubic perovskite oxides, including their hypothetical chemical compositions, were calculated by a hybrid functional method with the expectation that peculiar electronic structures and unique carrier transport properties suitable for semiconductor applications would be hidden in high-symmetry cubic perovskite oxides. We found unique electronic structures of Si-based oxides (A = Mg, Ca, Sr, and Ba, and B = Si). In particular, the unreported cubic BaSiO 3 has a very narrow band gap (4.1 eV) compared with conventional nontransition-metal silicates (e.g., ∼9 eV for SiO 2 and the calculated value of 7.3 eV for orthorhombic BaSiO 3 ) and a small electron effective mass (0.3m 0 , where m 0 is the free electron rest mass). The narrow band gap is ascribed to the nonbonding state of Si 3s and the weakened Madelung potential. The existence of the predicted cubic perovskite structure of BaSiO 3 was experimentally verified by applying a high pressure of 141 GPa. The present finding indicates that it could be possible to develop a new transparent oxide semiconductor of earth abundant silicates if the symmetry of its crystal structure is appropriately chosen. Cubic BaSiO 3 is a candidate for high-performance oxide semiconductors if this phase can be stabilized at room temperature and ambient pressure.

  7. Magnetic order and electronic structure of 5d 3 double perovskite Sr 2ScOsO 6

    DOE PAGES

    Taylor, A. E.; Morrow, R.; Singh, D. J.; ...

    2015-03-01

    The magnetic susceptibility, crystal and magnetic structures, and electronic structure of double perovskite Sr 2ScOsO 6 are reported. Using both neutron and x-ray powder diffraction we find that the crystal structure is monoclinic P21/n from 3.5 to 300 K. Magnetization measurements indicate an antiferromagnetic transition at TN=92 K, one of the highest transition temperatures of any double perovskite hosting only one magnetic ion. Type I antiferromagnetic order is determined by neutron powder diffraction, with an Os moment of only 1.6(1) muB, close to half the spin-only value for a crystal field split 5d electron state with t2g^3 ground state. Densitymore » functional calculations show that this reduction is largely the result of strong Os-O hybridization, with spin-orbit coupling responsible for only a ~0.1 muB reduction in the moment.« less

  8. Structural and magnetic properties of SrMn1-xRuxO3 perovskites

    NASA Astrophysics Data System (ADS)

    Dabrowski, B.; Kolesnik, S.; Chmaissem, O.; Maxwell, T.

    2007-03-01

    Ferromagnetism of SrRuO3 is unique among 4d transition metal based perovskite oxides. On substitution of Mn its TC decreases from 163 K to 0 for x˜0.5-0.6 followed by a formation of an antiferromagnetic insulating state at a quantum critical point. The other end member of the SrMn1-xRuxO3 family, a cubic perovskite SrMnO3 is a G-type antiferromagnet with TN=233 K. We have synthesized the complete SrMn1-xRuxO3 solid solution. The polycrystalline samples were characterized by neutron difraction, magnetic, and transport experiments. The incorporation of Ru in the SrMnO3 matrix (0.1<=x<=0.4) results in a phase transition to a C-type antiferromagnetic state accompanied by a cubic-tetragonal transition. The intermediate substitution level induces a spin-glass behavior, due to competing ferro- and antiferromagnetic interactions. Mixed valence Mn^3+/Mn^4+ and Ru^4+/Ru^5+ pairs introduce additional frustration to the magnetic states. The glassy behavior can be observed for x up to 0.7 in the tetragonal structure. Supported by NSF (DMR-0302617) and the U.S. Department of Education

  9. Tackling pseudosymmetry problems in electron backscatter diffraction (EBSD) analyses of perovskite structures

    NASA Astrophysics Data System (ADS)

    Mariani, Elisabetta; Kaercher, Pamela; Mecklenburgh, Julian; Wheeler, John

    2016-04-01

    Perovskite minerals form an important mineral group that has applications in Earth science and emerging alternative energy technologies, however crystallographic quantification of these minerals with electron backscatter diffraction (EBSD) is not accurate due to pseudosymmetry problems. The silicate perovskite Bridgmanite, (Mg,Fe)SiO3, is understood to be the dominant phase in the Earth's lower mantle. Gaining insight into its physical and rheological properties is therefore vital to understand the dynamics of the Earth's deep interior. Rock deformation experiments on analogue perovskite phases, for example (Ca,Sr)TiO3, combined with quantitative microstructural analyses of the recovered samples by EBSD, yield datasets that can reveal what deformation mechanisms may dominate the flow of perovskite in the lower mantle. Additionally, perovskite structures have important technological applications as new, suitable cathodes for the operation of more efficient and environmentally-friendly solid oxide fuel cells (SOFC). In recent years they have also been recognised as a potential substitute for silicon in the next generation of photovoltaic cells for the construction of economic and energy efficient solar panels. EBSD has the potential to be a valuable tool for the study of crystal orientations achieved in perovskite substrates as crystal alignment has a direct control on the properties of these materials. However, perovskite structures currently present us with challenges during the automated indexing of Kikuchi bands in electron backscatter diffraction patterns (EBSPs). Such challenges are represented by the pseudosymmetric character of perovskites, where atoms are subtly displaced (0.005 nm to 0.05 nm) from their higher symmetry positions. In orthorhombic Pbnm perovskites, for example, pseudosymmetry may be evaluated from the c/a unit cell parameter ratio, which is very close to 1. Two main types of distortions from the higher symmetry structure are recognised: a

  10. Low-Dimensional Organic Tin Bromide Perovskites and Their Photoinduced Structural Transformation.

    PubMed

    Zhou, Chenkun; Tian, Yu; Wang, Mingchao; Rose, Alyssa; Besara, Tiglet; Doyle, Nicholas K; Yuan, Zhao; Wang, Jamie C; Clark, Ronald; Hu, Yanyan; Siegrist, Theo; Lin, Shangchao; Ma, Biwu

    2017-07-24

    Hybrid organic-inorganic metal halide perovskites possess exceptional structural tunability, with three- (3D), two- (2D), one- (1D), and zero-dimensional (0D) structures on the molecular level all possible. While remarkable progress has been realized in perovskite research in recent years, the focus has been mainly on 3D and 2D structures, with 1D and 0D structures significantly underexplored. The synthesis and characterization of a series of low-dimensional organic tin bromide perovskites with 1D and 0D structures is reported. Using the same organic and inorganic components, but at different ratios and reaction conditions, both 1D (C 4 N 2 H 14 )SnBr 4 and 0D (C 4 N 2 H 14 Br) 4 SnBr 6 can be prepared in high yields. Moreover, photoinduced structural transformation from 1D to 0D was investigated experimentally and theoretically in which photodissociation of 1D metal halide chains followed by structural reorganization leads to the formation of a more thermodynamically stable 0D structure. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Depletion region effect of highly efficient hole conductor free CH3NH3PbI3 perovskite solar cells.

    PubMed

    Aharon, Sigalit; Gamliel, Shany; El Cohen, Bat; Etgar, Lioz

    2014-06-14

    The inorganic-organic perovskite is currently attracting a lot of attention due to its use as a light harvester in solar cells. The large absorption coefficients, high carrier mobility and good stability of organo-lead halide perovskites present good potential for their use as light harvesters in mesoscopic heterojunction solar cells. This work concentrated on a unique property of the lead halide perovskite, its function simultaneously as a light harvester and a hole conductor in the solar cell. A two-step deposition technique was used to optimize the perovskite deposition and to enhance the solar cell efficiency. It was revealed that the photovoltaic performance of the hole conductor free perovskite solar cell is strongly dependent on the depletion layer width which was created at the TiO2-CH3NH3PbI3 junction. X-ray diffraction measurements indicate that there were no changes in the crystallographic structure of the CH3NH3PbI3 perovskite over time, which supports the high stability of these hole conductor free perovskite solar cells. Furthermore, the power conversion efficiency of the best cells reached 10.85% with a fill factor of 68%, a Voc of 0.84 V, and a Jsc of 19 mA cm(-2), the highest efficiency to date of a hole conductor free perovskite solar cell.

  12. High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties

    PubMed Central

    2016-01-01

    We report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX3 (MA = CH3NH3+, X = Br– or I–) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites’ precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaque black with compression. Indeed, electronic conductivity measurements of (MA)PbI3 obtained within a diamond-anvil cell show that the material’s resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(BrxI1–x)3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain the low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors. PMID:27163050

  13. High-pressure single-crystal structures of 3D lead-halide hybrid perovskites and pressure effects on their electronic and optical properties

    DOE PAGES

    Jaffe, Adam; Lin, Yu; Beavers, Christine M.; ...

    2016-04-06

    Here, we report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX 3 (MA = CH 3NH 3 +, X = Br – or I –) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites’ precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaquemore » black with compression. Indeed, electronic conductivity measurements of (MA)PbI 3 obtained within a diamond-anvil cell show that the material’s resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(Br xI 1–x) 3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain the low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors.« less

  14. Autothermal reforming catalyst having perovskite structure

    DOEpatents

    Krumpel, Michael [Naperville, IL; Liu, Di-Jia [Naperville, IL

    2009-03-24

    The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

  15. Thermally evaporated hybrid perovskite for hetero-structured green light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Mariano, Fabrizio; Listorti, Andrea; Rizzo, Aurora; Colella, Silvia; Gigli, Giuseppe; Mazzeo, Marco

    2017-10-01

    Thermal evaporation of green-light emitting perovskite (MaPbBr3) films is reported. Morphological studies show that a soft thermal treatment is needed to induce an outstanding crystal growth and film organization. Hetero-structured light-emitting diodes, embedding as-deposited and annealed MAPbBr3 films as active layers, are fabricated and their performances are compared, highlighting that the perovskite evolution is strongly dependent on the growing substrate, too.

  16. New functional materials AC3B4O12 (Review)

    NASA Astrophysics Data System (ADS)

    Vasil'ev, A. N.; Volkova, O. S.

    2007-11-01

    The physical properties of perovskites of the type AC3B4O12, whose structure derives from simple perovskites ABO3, are reviewed. The A position is subject to strong structural distortions and splits into two new positions A and C. In the structure of AC3B4O12 vacancies and any cations with a large radius, irrespective of their charge state, can be present in the icosahedral environment of A: Na +, Cd2+, Ca2+, Sr2+, Y3+, Ln3+, and Nd4+. The C position in the square environment of oxygen can be occupied only by the Jahn-Teller cations Cu2+ and Mn3+. Transition and nontransition metal ions—Mn3+, Fe3+, Al3+, Cr3+, Ti4+, Mn4+, Ge4+, Ru4+, Ir4+, Ta5+, Nb5+, Ta5+, Sb5+—can occupy the B position in an octahedral environment. Some members of the family of complex perovskites possess properties which are characteristic for systems with heavy fermions; collinear and noncollinear magnetic structures with high ordering temperatures occur in these materials; tunneling magnetoresistance and high permittivity are observed. The diversity and unique properties make these materials attractive for practical applications.

  17. Structural State and Elastic Properties of Perovskites in the Earth's Mantle

    NASA Astrophysics Data System (ADS)

    Ross, N. L.; Angel, R. J.; Zhao, J.

    2005-12-01

    Recent advances in laboratory-based single-crystal X-ray diffraction techniques for measuring the intensities of diffraction from crystals held in situ at high pressures in the diamond-anvil cell have been used to determine the role of polyhedral compression in the response of 2:4 and 3:3 GdFeO3-type perovskites to high pressure [1]. These new data clearly demonstrate that, contrary to previous belief, the compression of the octahedral sites is significant and that the evolution of the perovskite structure with pressure is controlled by a new principle; that of equipartition of bond-valence strain across the structure [2]. This new paradigm, together with the minimal information available from high- pressure powder diffraction studies, may provide the possibility of predicting the structural state and elastic properties of perovskites of any composition at mantle pressures and temperatures. Cation partioning between silicate perovskites and other phases should then be predictable through the application of a Brice-style model [3]. The geochemical implications of this type of analysis will be presented as well as the possibility for extending these measurements to higher pressures. References [1] e.g. Zhao, Ross & Angel (2004) Phys Chem Miner. 31: 299; Ross, Zhao,. & Angel (2004). J. Solid State Chemistry 177:1276. [2] Zhao, Ross, & Angel (2004). Acta Cryst. B60:263 [3] e.g Walter et al. (2004) Geochim Cosmochim Acta 68:4267; Blundy & Wood (1994) Nature 372:452

  18. Molecularly Engineered Organic-Inorganic Hybrid Perovskite with Multiple Quantum Well Structure for Multicolored Light-Emitting Diodes

    PubMed Central

    Hu, Hongwei; Salim, Teddy; Chen, Bingbing; Lam, Yeng Ming

    2016-01-01

    Organic-inorganic hybrid perovskites have the potential to be used as a new class of emitters with tunable emission, high color purity and good ease of fabrication. Recent studies have so far been focused on three-dimensional (3D) perovskites, such as CH3NH3PbBr3 and CH3NH3PbI3 for green and infrared emission. Here, we explore a new series of hybrid perovskite emitters with a general formula of (C4H9NH3)2(CH3NH3)n−1PbnI3n+1 (where n = 1, 2, 3), which possesses a multiple quantum well structure. The quantum well thickness of these materials is adjustable through simple molecular engineering which results in a continuously tunable bandgap and emission spectra. Deep saturated red emission was obtained with a peak external quantum efficiency of 2.29% and a maximum luminance of 214 cd/m2. Green and blue LEDs were also demonstrated through halogen substitutions in these hybrid perovskites. We expect these results to open up the way towards high performance perovskite LEDs through molecular-structure engineering of these perovskite emitters. PMID:27633084

  19. Structural, optical and morphological studies of Cd2+ doping in CH3NH3PbI3 perovskite semiconductor at Pb2+ site for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Parrey, Khursheed; Warish, Mohd.; Devi, Nisha; Niazi, A.; Aziz, A.; Ansari, S. G.

    2018-05-01

    Doping of semiconductors in a controlled mannner have paramount technological importance as far as the optical and electronic properties of the devices are concerned. Hybrid organic-inorganic perovskites (HOPs) as intrinsic semiconductors have sensational properties required for both the solar photovoltaics and perovskite light emitting diodes. However, undoped and complexity in the dpoing process of HOPs have limited their exploitation in the field of elcronics. In this papper we present the synthesis of HOP semiconductor (CH3NH3PbI3) doped in Pb2+ position by Cd2+. We studied the effect of the incorporation of Cd2+ into the crystalline structure and analysed the changes in the properties like crystal structure, optical absorption and the surface morphology. The structure of HOPs confirmed by X-ray diffraction analysis is tetragonal perovskite type. It can be found that the crystallinity of the samples was enhanced with the doping concentration as the intensity of diffraction peaks were observed to increase with doping. The absorption spectra as obtained from UV-Visible spectrophotometry and Tauc plot analysis indicated that the band gap observed (1.73 eV) is direct type and gets reduced to 1.67 eV with the doping concentration. The red shift may be due to the increase in the size of nanocrystalline material with doping.

  20. The electronic and optical properties of CH3NH3MoI3 perovskite

    NASA Astrophysics Data System (ADS)

    Kansara, Shivam; Sonvane, Yogesh; Gupta, Sanjeev K.

    2018-05-01

    In this work, a first-principles theoretical study of hybrid perovskite CH3NH3MoI3 is performed using PBE exchange-correlation approximations in density functional theory. The results of electronic band structure are 0.90 eV (M-point: Direct) and 0.60 eV (R-X point: Indirect), respectively. We have also calculated the dielectric properties such as real, imaginary, extension coefficient (K) and reflectivity (R) properties of hybrid perovskite CH3NH3MoI3. The low-bandgap molecules are used to absorb near-IR range and typically having a bandgap smaller than 1.6 eV. This is particularly attractive in organic photovoltaics (OPV), photodetectors (PDs), and ambipolar field-effect transistors (FETs).

  1. Cryopreservation of Genotyped ABO Subgroup RBCs for Quality Assurance of ABO Grouping Reagents.

    PubMed

    Kim, Sinyoung; Song, Sungwook; Kim, Hyun Ok

    2018-03-01

    Quality assurance of newly developed or manufactured blood grouping reagents with reagent red blood cells (RBCs) is crucial in the process of product approval by governmental agency. However, RBCs with rare blood group are not easily available in the fresh state. We investigated the feasibility of cryopreserved and genotyped ABO subgroup RBC reagents for quality assurance purpose. We obtained RBCs from 10 volunteers with ABO subgroup phenotypes. The ABO genotypes and alleles were analyzed by the sequencing of ABO exon 6 and 7. Using the 40% wt/vol high-glycerol method, RBC units were cryopreserved as reagent RBCs into separate cryovials at -80°C. The potency titrations were performed before and after cryopreservation for 6 months and 2 years to evaluate the stability of ABO antigens. ABO genotypes of cryopreserved RBCs were cis-AB01/O01 (n=2), cis-AB01/B101 (n=1), Aw10/B101 (n=2), A201/A201 (n=1), A205/B101 (n=1), A102/B112 (n=1), and A101/B306 (n=1). These ABO subgroup alleles are exclusively present in East-Asian population except for the known ABO*A201 allele. The potency titers of cryopreserved RBCs were not significantly different between pre-freezing and post-freezing. The national performance evaluation of ABO blood grouping reagents could be performed with cryopreserved and genotyped reagent RBCs. © 2018 by the Association of Clinical Scientists, Inc.

  2. Perovskite-based solar cells with inorganic inverted hybrid planar heterojunction structure

    NASA Astrophysics Data System (ADS)

    Lai, Wei-Chih; Lin, Kun-Wei; Guo, Tzung-Fang; Chen, Peter; Liao, Yuan-Yu

    2018-01-01

    We demonstrated the good performance of inorganic inverted CH3NH3PbI3 perovskite-based solar cells (SCs) with glass/ITO/NiOx/CH3NH3PbI3 perovskite/C60/ room temperature (RT)-sputtered ZnO/Al structure. We adopted spin coating and RT sputtering for the deposition of NiOx and ZnO, respectively. The inorganic hole and electron transport layer of NiOx and RT-sputtered ZnO, respectively, could improve the open-circuit voltage (VOC), short-circuit current density (JSC), and power conversion efficiency (η%) of the SCs. We obtained inorganic inverted CH3NH3PbI3 perovskite-based SCs with a JSC of 21.96 A/cm2, a VOC of 1.02 V, a fill factor (FF%) of 68.2%, and an η% of 15.3% despite the sputtering damage of the RT-sputtered ZnO deposition. Moreover, the RT-sputtered ZnO could function as a diffusion barrier for Al, moisture, and O2. The inorganic inverted CH3NH3PbI3 perovskite-based SCs demonstrated improved storage reliability.

  3. Recent Advances in the Inverted Planar Structure of Perovskite Solar Cells.

    PubMed

    Meng, Lei; You, Jingbi; Guo, Tzung-Fang; Yang, Yang

    2016-01-19

    Inorganic-organic hybrid perovskite solar cells research could be traced back to 2009, and initially showed 3.8% efficiency. After 6 years of efforts, the efficiency has been pushed to 20.1%. The pace of development was much faster than that of any type of solar cell technology. In addition to high efficiency, the device fabrication is a low-cost solution process. Due to these advantages, a large number of scientists have been immersed into this promising area. In the past 6 years, much of the research on perovskite solar cells has been focused on planar and mesoporous device structures employing an n-type TiO2 layer as the bottom electron transport layer. These architectures have achieved champion device efficiencies. However, they still possess unwanted features. Mesoporous structures require a high temperature (>450 °C) sintering process for the TiO2 scaffold, which will increase the cost and also not be compatible with flexible substrates. While the planar structures based on TiO2 (regular structure) usually suffer from a large degree of J-V hysteresis. Recently, another emerging structure, referred to as an "inverted" planar device structure (i.e., p-i-n), uses p-type and n-type materials as bottom and top charge transport layers, respectively. This structure derived from organic solar cells, and the charge transport layers used in organic photovoltaics were successfully transferred into perovskite solar cells. The p-i-n structure of perovskite solar cells has shown efficiencies as high as 18%, lower temperature processing, flexibility, and, furthermore, negligible J-V hysteresis effects. In this Account, we will provide a comprehensive comparison of the mesoporous and planar structures, and also the regular and inverted of planar structures. Later, we will focus the discussion on the development of the inverted planar structure of perovskite solar cells, including film growth, band alignment, stability, and hysteresis. In the film growth part, several

  4. CaTiO.sub.3 Interfacial template structure on semiconductor-based material and the growth of electroceramic thin-films in the perovskite class

    DOEpatents

    McKee, Rodney Allen; Walker, Frederick Joseph

    1998-01-01

    A structure including a film of a desired perovskite oxide which overlies and is fully commensurate with the material surface of a semiconductor-based substrate and an associated process for constructing the structure involves the build up of an interfacial template film of perovskite between the material surface and the desired perovskite film. The lattice parameters of the material surface and the perovskite of the template film are taken into account so that during the growth of the perovskite template film upon the material surface, the orientation of the perovskite of the template is rotated 45.degree. with respect to the orientation of the underlying material surface and thereby effects a transition in the lattice structure from fcc (of the semiconductor-based material) to the simple cubic lattice structure of perovskite while the fully commensurate periodicity between the perovskite template film and the underlying material surface is maintained. The film-growth techniques of the invention can be used to fabricate solid state electrical components wherein a perovskite film is built up upon a semiconductor-based material and the perovskite film is adapted to exhibit ferroelectric, piezoelectric, pyroelectric, electro-optic or large dielectric properties during use of the component.

  5. Single-crystal perovskite CH3NH3PbBr3 prepared by cast capping method for light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Nguyen, Van-Cao; Katsuki, Hiroyuki; Sasaki, Fumio; Yanagi, Hisao

    2018-04-01

    In this study, electroluminescence from single crystals of CH3NH3PbBr3 perovskite is explored. The cast capping method was applied to fabricate simple devices with an ITO/CH3NH3PbBr3/ITO structure. The devices showed a low operation voltage of 2 V and a pure green luminescence with full width at half maximum of ∼20 nm. However, the emission occurring at the crystal edges demonstrated blinking with a subsecond time interval, which is similar to the previously reported photoluminescence behavior of nanocrystal perovskites. This electroluminescence blinking may provide new insight into the recombination processes depending on the carrier traps and defects of emission layers in perovskite light-emitting devices.

  6. Structural manipulation and tailoring of dielectric properties in SrTi1−xFexTaxO3 perovskites: Design of new lead free relaxors

    PubMed Central

    Shukla, R.; Patwe, S. J.; Deshpande, S. K.; Achary, S. N.; Krishna, P. S. R.; Shinde, A. B.; Gopalakrishnan, J.; Tyagi, A. K.

    2016-01-01

    We report composition dependent structure evolution from SrTiO3 to SrFe0.5Ta0.5O3 by powder X-ray and neutron diffraction studies of SrTi1−2xFexTaxO3 (0.00 ≤ × ≤ 0.50) compositions. Structural studies reveal cubic (Pm3m) perovskite-type structure of the parent SrTiO3 for x up to 0.075 and cation disordered orthorhombic (Pbnm) perovskite-type structure for x ≥ 0.33. A biphasic region consisting of a mixture of cubic and orthorhombic structures is found in the range for 0.10 ≤ × ≤ 0.25. Dielectric studies reveal transformation from a normal dielectric to relaxor like properties with increasing Fe3+ and Ta5+ concentration. Dielectric response is maximum at x = 0.33 in the series. The results establish a protocol for designing new lead-free relaxor materials based on the co-substitution of Fe3+ and Ta5+ for Ti4+ in SrTiO3. A complex interplay of strain effects arising from distribution of cations at the octahedral sites of the perovskite structure controls the dielectric properties. PMID:27514668

  7. Lead-free perovskite solar cells using Sb and Bi-based A3B2X9 and A3BX6 crystals with normal and inverse cell structures

    NASA Astrophysics Data System (ADS)

    Baranwal, Ajay Kumar; Masutani, Hideaki; Sugita, Hidetaka; Kanda, Hiroyuki; Kanaya, Shusaku; Shibayama, Naoyuki; Sanehira, Yoshitaka; Ikegami, Masashi; Numata, Youhei; Yamada, Kouji; Miyasaka, Tsutomu; Umeyama, Tomokazu; Imahori, Hiroshi; Ito, Seigo

    2017-09-01

    Research of CH3NH3PbI3 perovskite solar cells had significant attention as the candidate of new future energy. Due to the toxicity, however, lead (Pb) free photon harvesting layer should be discovered to replace the present CH3NH3PbI3 perovskite. In place of lead, we have tried antimony (Sb) and bismuth (Bi) with organic and metal monovalent cations (CH3NH3 +, Ag+ and Cu+). Therefore, in this work, lead-free photo-absorber layers of (CH3NH3)3Bi2I9, (CH3NH3)3Sb2I9, (CH3NH3)3SbBiI9, Ag3BiI6, Ag3BiI3(SCN)3 and Cu3BiI6 were processed by solution deposition way to be solar cells. About the structure of solar cells, we have compared the normal (n-i-p: TiO2-perovskite-spiro OMeTAD) and inverted (p-i-n: NiO-perovskite-PCBM) structures. The normal (n-i-p)-structured solar cells performed better conversion efficiencies, basically. But, these environmental friendly photon absorber layers showed the uneven surface morphology with a particular grow pattern depend on the substrate (TiO2 or NiO). We have considered that the unevenness of surface morphology can deteriorate the photovoltaic performance and can hinder future prospect of these lead-free photon harvesting layers. However, we found new interesting finding about the progress of devices by the interface of NiO/Sb3+ and TiO2/Cu3BiI6, which should be addressed in the future study.

  8. Structural and Thermal Disorder of Solution-Processed CH3NH3PbBr3 Hybrid Perovskite Thin Films.

    PubMed

    Wolf, Christoph; Kim, Joo-Sung; Lee, Tae-Woo

    2017-03-29

    We extracted the electronic disorder energy of the organic-inorganic lead-halide hybrid perovskite CH 3 NH 3 PbBr 3 from temperature-dependent absorption data. We showed that the disorder at room temperature is ∼30 meV and is due to strong electron-phonon coupling with the longitudinal-optical mode of energy 16 meV. This mode can be attributed to longitudinal-optical phonons of the inorganic PbBr 6 frame; this conclusion highlights the polaronic nature of electronic excitations in CH 3 NH 3 PbBr 3 . We showed that structural disorder is of the same impact as thermal disorder. A temperature-dependence of the exciton binding energy was observed close to the orthorhombic-to-tetragonal phase-transition temperature.

  9. Synthesis, structural and electron paramagnetic resonance studies on Pb0.9Bi0.1Fe0.7W0.3O3 ceramic

    NASA Astrophysics Data System (ADS)

    Shivaraja, I.; Matteppanvar, Shidaling; Dadami, Sunanda T.; Rayaprol, Sudhindra; Angadi, Basavaraj

    2018-04-01

    A single phase Pb0.9Bi0.1Fe0.7W0.3O3 (0.9Pb(Fe2/3W1/3)O3 - 0.1BiFeO3 or PBFW) polycrystalline ceramic was synthesized by the two step solid state reaction method, with low-temperature sintering at 800°C for 30 mins and slow cooling to room temperature (RT). Detailed studies of RT X-ray diffraction (XRD) and Raman spectroscopy measurements confirm the formation of high symmetry cubic structure with Pm-3m space group. The Rietveld refinement was carried out on RT XRD data and the obtained structural parameters are a = b = c = 3.97563(6) Å and unit cell volume = 62.837 (2) Å3. Scanning Electron Microscopy (SEM) images show the uniform distribution of grains with some agglomerated nature. RT Raman spectroscopy reveals the main broad peak at 770 cm-1, related to the A1g mode, which confirms the formation of cubic (ABO3 perovskite) structure. The single symmetric electron paramagnetic resonance (EPR) line shape with g = 2.13985 observed in PBFW was identified to be due to Fe3+ ions.

  10. Exotic magnetic structures in high-pressure synthesized perovskites

    NASA Astrophysics Data System (ADS)

    Manuel, Pascal; Khalyavin, Dmitry; Ding, Lei; Yi, Wei; Kumagai, Yu; Oba, Fumiyasu; Orlandi, Fabio; Belik, Alexei

    We present a neutron powder diffraction study of the crystal and magnetic structures of the high-pressure stabilized perovskite phases of TlMnO3, ScCrO3, InCrO3 and TlCrO3. These compounds exhibit original magnetic structures compared to other members of their respective manganite and orthochromite families with TlMnO3 also displaying unusual orbital ordering pattern. For both systems, we rationalise the structures through a combination of group theory and first principle calculations. We also highlight the dominant mechanism controlling the spin direction as being the single ion anisotropy.

  11. Enhanced photovoltaic performance and stability with a new type of hollow 3D perovskite {en}FASnI 3

    DOE PAGES

    Ke, Weijun; Stoumpos, Constantinos C.; Zhu, Menghua; ...

    2017-08-30

    Perovskite solar cells have revolutionized the fabrication of solution-processable solar cells. The presence of lead in the devices makes this technology less attractive, and alternative metals in perovskites are being researched as suitable alternatives. We demonstrate a new type of tin-based perovskite absorber that incorporates both ethylenediammonium (en) and formamidinium (FA), forming new materials of the type {en}FASnI 3. The three-dimensional ASnI 3 structure is stable only with methylammonium, FA, and Cs cations, and the bandgap can be tuned with solid solutions, such as ASnI 3-xBr x. We show that en can serve as a new A cation capable ofmore » achieving marked increases in the bandgap without the need for solid solutions. The en introduces a new bandgap tuning mechanism that arises from massive Schottky style defects. In addition, incorporation of the en cation in the structure markedly increases the air stability and improves the photoelectric properties of the tin-based perovskite absorbers. Our best-performing {en}FASnI 3 solar cell has the highest efficiency of 7.14%, which is achieved for a lead-free perovskite cell, and retains 96% of its initial efficiency after aging over 1000 hours with encapsulation. Our results introduce a new approach for improving the performance and stability of tin-based, lead-free perovskite solar cells.« less

  12. Enhanced photovoltaic performance and stability with a new type of hollow 3D perovskite {en}FASnI 3

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ke, Weijun; Stoumpos, Constantinos C.; Zhu, Menghua

    Perovskite solar cells have revolutionized the fabrication of solution-processable solar cells. The presence of lead in the devices makes this technology less attractive, and alternative metals in perovskites are being researched as suitable alternatives. We demonstrate a new type of tin-based perovskite absorber that incorporates both ethylenediammonium (en) and formamidinium (FA), forming new materials of the type {en}FASnI 3. The three-dimensional ASnI 3 structure is stable only with methylammonium, FA, and Cs cations, and the bandgap can be tuned with solid solutions, such as ASnI 3-xBr x. We show that en can serve as a new A cation capable ofmore » achieving marked increases in the bandgap without the need for solid solutions. The en introduces a new bandgap tuning mechanism that arises from massive Schottky style defects. In addition, incorporation of the en cation in the structure markedly increases the air stability and improves the photoelectric properties of the tin-based perovskite absorbers. Our best-performing {en}FASnI 3 solar cell has the highest efficiency of 7.14%, which is achieved for a lead-free perovskite cell, and retains 96% of its initial efficiency after aging over 1000 hours with encapsulation. Our results introduce a new approach for improving the performance and stability of tin-based, lead-free perovskite solar cells.« less

  13. Enhanced photovoltaic performance and stability with a new type of hollow 3D perovskite {en}FASnI3

    PubMed Central

    Ke, Weijun; Stoumpos, Constantinos C.; Zhu, Menghua; Mao, Lingling; Spanopoulos, Ioannis; Liu, Jian; Kontsevoi, Oleg Y.; Chen, Michelle; Sarma, Debajit; Zhang, Yongbo; Wasielewski, Michael R.; Kanatzidis, Mercouri G.

    2017-01-01

    Perovskite solar cells have revolutionized the fabrication of solution-processable solar cells. The presence of lead in the devices makes this technology less attractive, and alternative metals in perovskites are being researched as suitable alternatives. We demonstrate a new type of tin-based perovskite absorber that incorporates both ethylenediammonium (en) and formamidinium (FA), forming new materials of the type {en}FASnI3. The three-dimensional ASnI3 structure is stable only with methylammonium, FA, and Cs cations, and the bandgap can be tuned with solid solutions, such as ASnI3−xBrx. We show that en can serve as a new A cation capable of achieving marked increases in the bandgap without the need for solid solutions. The en introduces a new bandgap tuning mechanism that arises from massive Schottky style defects. In addition, incorporation of the en cation in the structure markedly increases the air stability and improves the photoelectric properties of the tin-based perovskite absorbers. Our best-performing {en}FASnI3 solar cell has the highest efficiency of 7.14%, which is achieved for a lead-free perovskite cell, and retains 96% of its initial efficiency after aging over 1000 hours with encapsulation. Our results introduce a new approach for improving the performance and stability of tin-based, lead-free perovskite solar cells. PMID:28875173

  14. Lone pair effect, structural distortions, and potential for superconductivity in Tl perovskites.

    PubMed

    Schoop, Leslie M; Müchler, Lukas; Felser, Claudia; Cava, R J

    2013-05-06

    Drawing the analogy to BaBiO3, we investigate via ab initio electronic structure calculations potential new superconductors of the type ATlX3 with A = Rb and Cs and X = F, Cl, and Br, with a particular emphasis on RbTlCl3. On the basis of chemical reasoning, supported by the calculations, we show that Tl-based perovskites have structural and charge instabilities driven by the lone pair effect, similar to the case of BaBiO3, effectively becoming A2Tl(+)Tl(3+)X6. We find that upon hole doping of RbTlCl3, structures without Tl(+) and Tl(3+) charge disproportionation become more stable, although the ideal cubic perovskite, often viewed as the best host for superconductivity, should not be the most stable phase in the system. The known superconductor (Sr,K)BiO3 and hole doped RbTlCl3, predicted to be most stable in the same tetragonal structure, display highly analogous calculated electronic band structures.

  15. Effect of Oblique-Angle Sputtered ITO Electrode in MAPbI3 Perovskite Solar Cell Structures.

    PubMed

    Lee, Kun-Yi; Chen, Lung-Chien; Wu, Yu-June

    2017-10-03

    This investigation reports on the characteristics of MAPbI 3 perovskite films on obliquely sputtered ITO/glass substrates that are fabricated with various sputtering times and sputtering angles. The grain size of a MAPbI 3 perovskite film increases with the oblique sputtering angle of ITO thin films from 0° to 80°, indicating that the surface properties of the ITO affect the wettability of the PEDOT:PSS thin film and thereby dominates the number of perovskite nucleation sites. The optimal power conversion efficiency (Eff) is achieved 11.3% in a cell with an oblique ITO layer that was prepared using a sputtering angle of 30° for a sputtering time of 15 min.

  16. Local structural distortion and electrical transport properties of Bi(Ni1/2Ti1/2)O3 perovskite under high pressure.

    PubMed

    Zhu, Jinlong; Yang, Liuxiang; Wang, Hsiu-Wen; Zhang, Jianzhong; Yang, Wenge; Hong, Xinguo; Jin, Changqing; Zhao, Yusheng

    2015-12-16

    Perovskite-structure materials generally exhibit local structural distortions that are distinct from long-range, average crystal structure. The characterization of such distortion is critical to understanding the structural and physical properties of materials. In this work, we combined Pair Distribution Function (PDF) technique with Raman spectroscopy and electrical resistivity measurement to study Bi(Ni1/2Ti1/2)O3 perovskite under high pressure. PDF analysis reveals strong local structural distortion at ambient conditions. As pressure increases, the local structure distortions are substantially suppressed and eventually vanish around 4 GPa, leading to concurrent changes in the electronic band structure and anomalies in the electrical resistivity. Consistent with PDF analysis, Raman spectroscopy data suggest that the local structure changes to a higher ordered state at pressures above 4 GPa.

  17. 2:1 Charge disproportionation in perovskite-structure oxide La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Guo, Haichuan; Hosaka, Yoshiteru; Seki, Hayato

    La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+} was synthesized at a high pressure and high temperature. The compound crystallizes in a √2a×2a×√2a perovskite cell in which the La and Ca ions at the A site are disordered. At 217 K the Fe{sup 3.67+} shows charge disproportionation to Fe{sup 3+} and Fe{sup 5+} in a ratio of 2:1, and this disproportionation is accompanied by transitions in magnetic and transport properties. The charge-disproportionated Fe{sup 3+} and Fe{sup 5+} are arranged along the <111> direction of the cubic perovskite cell. The local electronic and magnetic environments of Fe in La{sub 1/3}Ca{sub 2/3}FeO{submore » 3} are quite similar to those of Fe in La{sub 1/3}Sr{sub 2/3}FeO{sub 3}, and the 2:1 charge disproportionation pattern of Fe{sup 3+} and Fe{sup 5+} in La{sub 1/3}Ca{sub 2/3}FeO{sub 3} is also the same as that in La{sub 1/3}Sr{sub 2/3}FeO{sub 3}. - Graphical abstract: The perovskite-structure oxide La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+} shows charge disproportionation to Fe{sup 3+} and Fe{sup 5+} in a ratio of 2:1, and the charge-disproportionated Fe{sup 3+} and Fe{sup 5+} are arranged along the <111> direction of the cubic perovskite cell. - Highlights: • La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+} was synthesized at a high pressure and high temperature. • At 217 K the Fe{sup 3.67+} shows charge disproportionation (CD) to Fe{sup 3+} and Fe{sup 5+} in a ratio of 2:1. • The charge-disproportionated Fe{sup 3+} and Fe{sup 5+} are arranged along the <111> direction of the cubic perovskite cell. • The disproportionation is accompanied by transitions in magnetic and transport properties.« less

  18. CH3NH3PbI3 grain growth and interfacial properties in meso-structured perovskite solar cells fabricated by two-step deposition

    PubMed Central

    Yao, Zhibo; Wang, Wenli; Shen, Heping; Zhang, Ye; Luo, Qiang; Yin, Xuewen; Dai, Xuezeng; Li, Jianbao; Lin, Hong

    2017-01-01

    Abstract Although the two-step deposition (TSD) method is widely adopted for the high performance perovskite solar cells (PSCs), the CH3NH3PbI3 perovskite crystal growth mechanism during the TSD process and the photo-generated charge recombination dynamics in the mesoporous-TiO2 (mp-TiO2)/CH3NH3PbI3/hole transporting material (HTM) system remains unexploited. Herein, we modified the concentration of PbI2 (C (PbI2)) solution to control the perovskite crystal properties, and observed an abnormal CH3NH3PbI3 grain growth phenomenon atop mesoporous TiO2 film. To illustrate this abnormal grain growth mechanism, we propose that a grain ripening process is taking place during the transformation from PbI2 to CH3NH3PbI3, and discuss the PbI2 nuclei morphology, perovskite grain growing stage, as well as Pb:I atomic ratio difference among CH3NH3PbI3 grains with different morphology. These C (PbI2)-dependent perovskite morphologies resulted in varied charge carrier transfer properties throughout the mp-TiO2/CH3NH3PbI3/HTM hybrid, as illustrated by photoluminescence measurement. Furthermore, the effect of CH3NH3PbI3 morphology on light absorption and interfacial properties is investigated and correlated with the photovoltaic performance of PSCs. PMID:28458747

  19. CH3NH3PbI3 grain growth and interfacial properties in meso-structured perovskite solar cells fabricated by two-step deposition

    NASA Astrophysics Data System (ADS)

    Yao, Zhibo; Wang, Wenli; Shen, Heping; Zhang, Ye; Luo, Qiang; Yin, Xuewen; Dai, Xuezeng; Li, Jianbao; Lin, Hong

    2017-12-01

    Although the two-step deposition (TSD) method is widely adopted for the high performance perovskite solar cells (PSCs), the CH3NH3PbI3 perovskite crystal growth mechanism during the TSD process and the photo-generated charge recombination dynamics in the mesoporous-TiO2 (mp-TiO2)/CH3NH3PbI3/hole transporting material (HTM) system remains unexploited. Herein, we modified the concentration of PbI2 (C(PbI2)) solution to control the perovskite crystal properties, and observed an abnormal CH3NH3PbI3 grain growth phenomenon atop mesoporous TiO2 film. To illustrate this abnormal grain growth mechanism, we propose that a grain ripening process is taking place during the transformation from PbI2 to CH3NH3PbI3, and discuss the PbI2 nuclei morphology, perovskite grain growing stage, as well as Pb:I atomic ratio difference among CH3NH3PbI3 grains with different morphology. These C(PbI2)-dependent perovskite morphologies resulted in varied charge carrier transfer properties throughout the mp-TiO2/CH3NH3PbI3/HTM hybrid, as illustrated by photoluminescence measurement. Furthermore, the effect of CH3NH3PbI3 morphology on light absorption and interfacial properties is investigated and correlated with the photovoltaic performance of PSCs.

  20. CH3NH3PbI3 grain growth and interfacial properties in meso-structured perovskite solar cells fabricated by two-step deposition.

    PubMed

    Yao, Zhibo; Wang, Wenli; Shen, Heping; Zhang, Ye; Luo, Qiang; Yin, Xuewen; Dai, Xuezeng; Li, Jianbao; Lin, Hong

    2017-01-01

    Although the two-step deposition (TSD) method is widely adopted for the high performance perovskite solar cells (PSCs), the CH 3 NH 3 PbI 3 perovskite crystal growth mechanism during the TSD process and the photo-generated charge recombination dynamics in the mesoporous-TiO 2 (mp-TiO 2 )/CH 3 NH 3 PbI 3 /hole transporting material (HTM) system remains unexploited. Herein, we modified the concentration of PbI 2 ( C (PbI2) ) solution to control the perovskite crystal properties, and observed an abnormal CH 3 NH 3 PbI 3 grain growth phenomenon atop mesoporous TiO 2 film. To illustrate this abnormal grain growth mechanism, we propose that a grain ripening process is taking place during the transformation from PbI 2 to CH 3 NH 3 PbI 3 , and discuss the PbI 2 nuclei morphology, perovskite grain growing stage, as well as Pb:I atomic ratio difference among CH 3 NH 3 PbI 3 grains with different morphology. These C (PbI2) -dependent perovskite morphologies resulted in varied charge carrier transfer properties throughout the mp-TiO 2 /CH 3 NH 3 PbI 3 /HTM hybrid, as illustrated by photoluminescence measurement. Furthermore, the effect of CH 3 NH 3 PbI 3 morphology on light absorption and interfacial properties is investigated and correlated with the photovoltaic performance of PSCs.

  1. Planar-Structure Perovskite Solar Cells with Efficiency beyond 21.

    PubMed

    Jiang, Qi; Chu, Zema; Wang, Pengyang; Yang, Xiaolei; Liu, Heng; Wang, Ye; Yin, Zhigang; Wu, Jinliang; Zhang, Xingwang; You, Jingbi

    2017-12-01

    Low temperature solution processed planar-structure perovskite solar cells gain great attention recently, while their power conversions are still lower than that of high temperature mesoporous counterpart. Previous reports are mainly focused on perovskite morphology control and interface engineering to improve performance. Here, this study systematically investigates the effect of precise stoichiometry, especially the PbI 2 contents on device performance including efficiency, hysteresis and stability. This study finds that a moderate residual of PbI 2 can deliver stable and high efficiency of solar cells without hysteresis, while too much residual PbI 2 will lead to serious hysteresis and poor transit stability. Solar cells with the efficiencies of 21.6% in small size (0.0737 cm 2 ) and 20.1% in large size (1 cm 2 ) with moderate residual PbI 2 in perovskite layer are obtained. The certificated efficiency for small size shows the efficiency of 20.9%, which is the highest efficiency ever recorded in planar-structure perovskite solar cells, showing the planar-structure perovskite solar cells are very promising. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. ABO blood groups and psychiatric disorders: a Croatian study.

    PubMed

    Pisk, Sandra Vuk; Vuk, Tomislav; Ivezić, Ena; Jukić, Irena; Bingulac-Popović, Jasna; Filipčić, Igor

    2018-02-15

    The prevalence of ABO alleles is different in different populations, and many studies have shown a correlation between the occurrences of some diseases and different genotypes of ABO blood groups. The aim of this study was to determine whether there is a significant association between psychiatric syndromes and ABO blood groups. This case-control study involved 156 psychiatric patients and 303 healthy, unrelated, voluntary blood donors. Genomic DNA was isolated from blood on a QIAcube device using a QIAamp DNA Blood mini QIAcube kit. ABO genotyping on five basic ABO alleles was performed using allele-specific polymerase chain reaction analysis. Compared with healthy subjects, a significantly higher proportion of psychiatric patients had AB blood group (χ 2 =9.359, df=3, p=0.025) and, accordingly, a significantly higher incidence of A1B genotype (χ 2 =8.226, df=3, p=0.042). The odds ratio showed that psychiatric disorders occur almost three times more frequently in carriers of AB group compared to other blood groups. However, no statistically significant difference was found in the distribution of ABO blood groups among patients with different psychiatric diagnoses. Likewise, no correlations were found between ABO blood groups and other characteristics of the psychiatric patients (sex, psychiatric heredity, somatic comorbidity, suicidality). The results of this study support the hypothesis of an association between psychiatric disorders and ABO blood groups. The probability is that psychiatric disorders will occur almost three times more frequently in carriers of AB group compared to other ABO blood groups in the Croatian population.

  3. Structural Basis for the ABO Blood-Group Dependence of Plasmodium falciparum Rosetting

    PubMed Central

    Hessel, Audrey; Raynal, Bertrand; England, Patrick; Cohen, Jacques H.; Bertrand, Olivier; Peyrard, Thierry; Bentley, Graham A.; Lewit-Bentley, Anita; Mercereau-Puijalon, Odile

    2012-01-01

    The ABO blood group influences susceptibility to severe Plasmodium falciparum malaria. Recent evidence indicates that the protective effect of group O operates by virtue of reduced rosetting of infected red blood cells (iRBCs) with uninfected RBCs. Rosetting is mediated by a subgroup of PfEMP1 adhesins, with RBC binding being assigned to the N-terminal DBL1α1 domain. Here, we identify the ABO blood group as the main receptor for VarO rosetting, with a marked preference for group A over group B, which in turn is preferred to group O RBCs. We show that recombinant NTS-DBL1α1 and NTS-DBL1α1-CIDR1γ reproduce the VarO-iRBC blood group preference and document direct binding to blood group trisaccharides by surface plasmon resonance. More detailed RBC subgroup analysis showed preferred binding to group A1, weaker binding to groups A2 and B, and least binding to groups Ax and O. The 2.8 Å resolution crystal structure of the PfEMP1-VarO Head region, NTS-DBL1α1-CIDR1γ, reveals extensive contacts between the DBL1α1 and CIDR1γ and shows that the NTS-DBL1α1 hinge region is essential for RBC binding. Computer docking of the blood group trisaccharides and subsequent site-directed mutagenesis localized the RBC-binding site to the face opposite to the heparin-binding site of NTS-DBLα1. RBC binding involves residues that are conserved between rosette-forming PfEMP1 adhesins, opening novel opportunities for intervention against severe malaria. By deciphering the structural basis of blood group preferences in rosetting, we provide a link between ABO blood grouppolymorphisms and rosette-forming adhesins, consistent with the selective role of falciparum malaria on human genetic makeup. PMID:22807674

  4. Potassium doped methylammonium lead iodide (MAPbI3) thin films as a potential absorber for perovskite solar cells; structural, morphological, electronic and optoelectric properties

    NASA Astrophysics Data System (ADS)

    Muzammal uz Zaman, Muhammad; Imran, Muhammad; Saleem, Abida; Kamboh, Afzal Hussain; Arshad, Muhammad; Khan, Nawazish Ali; Akhter, Parvez

    2017-10-01

    In this article, we have demonstrated the doping of K in the light absorbing CH3NH3PbI3 perovskite i.e. (M = CH3, A = NH3; x = 0-1). One of the major merits of methylammonium lead iodide (CH3NH3PbI3) perovskites is that they act as efficient absorbing material of light in photovoltaic cell imparting long carrier lifetime and optimum band gap. The structural, morphological, electronic and optoelectric properties of potassium (K) doped light absorber methylammonium lead iodide (CH3NH3PbI3) perovskites are reported here i.e. Kx(MA)1-xPbI3 (M = CH3, A =NH3; x = 0-1). The thin films of perovskites (x = 0-1) were deposited by spin coating on cleaned FTO substrates and characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), current-voltage (IV), X-ray photoelectron spectroscopy (XPS) and Diffused reflectance spectroscopy (DRS) analysis. The organic constituents i.e. MA = CH3NH3, in perovskites solar cells induce instability even at the room temperature. To overcome such instabilities we have replaced the organic constituents by K because both of them have electropositive nature. Potassium successfully replaces the CH3NH3. Initially, this compound grows in a tetragonal crystal structure, however, beyond 30% doping of potassium orthorhombic distortions are induced in the parent tetragonal unit cell. Such phase transformation is microscopically visible in the electron micrographs of doped samples; cubic grains for MAPbI3 begin to transform into strip like structures in K-doped samples. The resistance of the samples is decreased for partial K-doping, which we suggested to be arising due to the electropositive nature of K. It is observed that the binding energy difference between Pb4f and I3d core levels are very similar in all the investigated systems and show formal oxidation states. Also, the partially doped samples showed increased absorption and bandgaps around 1.5 eV which is an optimum value for solar absorption.

  5. Local structural distortion and electrical transport properties of Bi(Ni 1/2Ti 1/2)O 3 perovskite under high pressure

    DOE PAGES

    Zhu, Jinlong; Yang, Liuxiang; Wang, Hsiu -Wen; ...

    2015-12-16

    Perovskite-structure materials generally exhibit local structural distortions that are distinct from long-range, average crystal structure. The characterization of such distortion is critical to understanding the structural and physical properties of materials. In this work, we combined Pair Distribution Function (PDF) technique with Raman spectroscopy and electrical resistivity measurement to study Bi(Ni 1/2Ti 1/2)O 3 perovskite under high pressure. PDF analysis reveals strong local structural distortion at ambient conditions. As pressure increases, the local structure distortions are substantially suppressed and eventually vanish around 4 GPa, leading to concurrent changes in the electronic band structure and anomalies in the electrical resistivity. Wemore » find, consistent with PDF analysis, Raman spectroscopy data suggest that the local structure changes to a higher ordered state at pressures above 4 GPa.« less

  6. The German version of the Anorectic Behavior Observation Scale (ABOS).

    PubMed

    Salbach-Andrae, Harriet; Klinkowski, Nora; Holzhausen, Martin; Frieler, Katja; Bohnekamp, Inga; Thiels, Cornelia; Bender, Caroline; Vandereycken, Walter

    2009-05-01

    To assess the performance of the German version of the Anorectic Behavior Observation Scale (ABOS) as a parent-report screening instrument for eating disorders (ED) in their children. Parents of 101 ED female patients (80 with Anorexia Nervosa; 21 with Bulimia Nervosa) and of 121 age- and socioeconomic status (SES)-matched female controls completed the ABOS. Confirmatory factor analysis supported the original three-factor structure model of the ABOS. Cronbach's alpha coefficients indicated good internal consistency for the three factors and the total score in the total sample. The best cut-off point (100% sensitivity and specificity) in the German version was >or=23. The ABOS may be a useful additional instrument for assessing ED.

  7. Analysis of the Results of ABO-Incompatible Kidney Transplantation: In Comparison with ABO-Compatible Kidney Transplantation

    PubMed Central

    Jeon, Byung Joo; Seong, Youl Keun; Han, Bo Hyun

    2010-01-01

    Purpose The number of patients waiting for kidney transplantation is incessantly increasing, but the number of cadaveric kidney transplantations or ABO-compatible donors is so insufficient that ABO-incompatible kidney transplantation is being performed as an alternative. There are overseas studies and research showing that the 5-year survival rate and 5-year graft survival rate of ABO-incompatible kidney transplantation are not much different from those of ABO-compatible kidney transplantation. However, domestic research on the subject is rare. Therefore, we report the results of 22 ABO-incompatible kidney transplantation cases performed in our hospital. Materials and Methods This research was from 22 patients in our hospital who underwent ABO-incompatible kidney transplantation from 15 February 2007 to 20 May 2010. Results As yet, there have been no donor graft losses and no deaths after transplantation. The results of the two groups were analyzed by analysis of covariance of the creatinine value of the recipients at 6 months after the operation, corrected for the preoperative value in order to statistically identify whether there were differences in renal function after the operation between ABO-compatible and ABO-incompatible kidney transplantation. The results of the analysis of covariance showed no statistical difference in renal function after the operation between the two groups. Conclusions Even though there were not many cases, our initial results for ABO-incompatible kidney transplantation were positive. Considering the increasing number of patients waiting for kidney transplantation, longer-term domestic research studies of ABO-incompatible kidney transplantation are necessary. PMID:21221208

  8. Sound velocity of MgSiO 3 perovskite to Mbar pressure

    NASA Astrophysics Data System (ADS)

    Murakami, Motohiko; Sinogeikin, Stanislav V.; Hellwig, Holger; Bass, Jay D.; Li, Jie

    2007-04-01

    Brillouin scattering measurements of the aggregate shear wave velocities in MgSiO 3 perovskite were conducted at high pressure conditions relevant to the Earth's lowermost mantle, approaching 1 Mbar. Infrared laser annealing of samples in a diamond anvil cell allowed us to obtain high quality Brillouin spectra and to drastically extend the upper limit of pressure for Brillouin measurements. We found that the pressure derivative of the shear modulus (d G / d P = G') of MgSiO 3 perovskite is 1.56 ± 0.04, which is distinctly lower than that of previous lower-pressure experiments below 9 GPa. Extrapolation of the high-pressure shear velocities of perovskite to ambient pressure, are in excellent agreement with earlier room pressure Brillouin measurements. The shear modulus, shear velocity and longitudinal velocity at ambient pressure were determined to be G0 = 172.9(15) GPa, VS = 6.49(3) and VP = 10.85(3) km/sec. The mineralogical model that provides a best fit to global seismological 1-D velocity profiles is one that contains 85-90 vol% perovskite in the lower mantle. The results of this study are the first to demonstrate that the elastic wave velocities for a near-adiabatic lower mantle with a bulk composition dominated by magnesium silicate perovskite are consistent with the average lower mantle seismic velocity structure. The large pressure range over which acoustic measurements of MgSiO 3 perovskite performed in this study has thus allowed us to put tighter constraints on compositional models of the Earth's lower mantle.

  9. Enhanced Crystalline Phase Purity of CH3NH3PbI3-xClx Film for High-Efficiency Hysteresis-Free Perovskite Solar Cells.

    PubMed

    Yang, Yingguo; Feng, Shanglei; Xu, Weidong; Li, Meng; Li, Li; Zhang, Xingmin; Ji, Gengwu; Zhang, Xiaonan; Wang, Zhaokui; Xiong, Yimin; Cao, Liang; Sun, Baoquan; Gao, Xingyu

    2017-07-12

    Despite rapid successful developments toward promising perovskite solar cells (PSCs) efficiency, they often suffer significant hysteresis effects. Using synchrotron-based grazing incidence X-ray diffraction (GIXRD) with different probing depths by varying the incident angle, we found that the perovskite films consist of dual phases with a parent phase dominant in the interior and a child phase with a smaller (110) interplanar space (d (110) ) after rapid thermal annealing (RTA), which is a widely used post treatment to improve the crystallization of solution-processed perovskite films for high-performance planar PSCs. In particular, the child phase composition gradually increases with decreasing depth till it becomes the majority on the surface, which might be one of the key factors related to hysteresis in fabricated PSCs. We further improve the crystalline phase purity of the solution-processed CH 3 NH 3 PbI 3-x Cl x perovskite film (referred as g-perovskite) by using a facile gradient thermal annealing (GTA), which shows a uniformly distributed phase structure in pinhole-free morphology with less undercoordinated Pb and I ions determined by synchrotron-based GIXRD, grazing incidence small-angle X-ray scattering, scanning electron microscopy, and X-ray photoelectron spectroscopy. Regardless of device structures (conventional and inverted types), the planar heterojunction PSCs employing CH 3 NH 3 PbI 3-x Cl x g-perovskite films exhibit negligible hysteresis with a champion power conversion efficiency of 17.04% for TiO 2 -based conventional planar PSCs and 14.83% for poly(3,4-ethylenedioxythiophene:poly(styrenesulfonate) (PEDOT:PSS)-based inverted planar PSCs. Our results indicate that the crystalline phase purity in CH 3 NH 3 PbI 3-x Cl x perovskite film, especially in the surface region, plays a crucial role in determining the hysteresis effect and device performance.

  10. Perovskite-related LaTiO3.41.

    PubMed

    Daniels, Peter; Lichtenberg, Frank; van Smaalen, Sander

    2003-02-01

    Crystals of pentalanthanum pentatitanium heptadecaoxide (La(5)Ti(5)O(17) with 0.3% oxygen excess, or LaTiO(3.41)) have been synthesized by floating-zone melting, and the structure has been solved using single-crystal X-ray diffraction intensities. The monoclinic (P2(1)/c) structure consists of perovskite-like slabs of vertex-sharing TiO(6) octahedra, which are separated by additional oxygen layers. The slabs are five octahedra wide. Due to the adjustment of the TiO(6) octahedra to meet the coordination requirements of the La(3+) cations, a superstructure develops along the a axis.

  11. Structures for the ABO(H) Blood Group: Which Textbook Is Correct?

    NASA Astrophysics Data System (ADS)

    Risley, John M.

    2007-09-01

    Six textbooks and two Internet sites show different structures for the A, B, and O(H) antigens of the ABO(H) blood group. However, none of the structures identified as the A, B, and O(H) antigens are correct. The O(H) antigen is a disaccharide, on which the trisaccharide A and B antigens are synthesized. The structures shown in the textbooks and at the Internet sites contain the O(H), A, and B antigens attached at the nonreducing end of various heterosaccharide cores of glycoproteins and glycolipids that are not a part of the specific blood group. This article emphasizes the correct molecular structures because it is important to distinguish between those carbohydrates that make up the antigens and those that are not part of the antigenic structures.

  12. High-Pressure Study of Perovskites and Postperovskites in the (Mg,Fe)GeO 3 System

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Stan, Camelia V.; Dutta, Rajkrishna; Cava, Robert J.

    2017-06-22

    The effect of incorporation of Fe 2+ on the perovskite (Pbnm) and postperovskite (Cmcm) structures was investigated in the (Mg,Fe)GeO 3 system at high pressures and temperatures using laser-heated diamond anvil cell and synchrotron X-ray diffraction. Samples with compositions of Mg# ≥ 48 were shown to transform to the perovskite (~30 GPa and ~1500 K) and postperovskite (>55 GPa, ~1600–1800 K) structures. Compositions with Mg# ≥ 78 formed single-phase perovskite and postperovskite, whereas those with Mg# < 78 showed evidence for partial decomposition. The incorporation of Fe into the perovskite structure causes a decrease in octahedral distortion as well asmore » a modest decrease in bulk modulus (K 0) and a modest increase in zero-pressure volume (V 0). It also leads to a decrease in the perovskite-to-postperovskite phase transition pressure by ~9.5 GPa over compositions from Mg#78 to Mg#100.« less

  13. First-principles analysis of ferroelectric transition in MnSnO3 and MnTiO3 perovskites

    NASA Astrophysics Data System (ADS)

    Kang, Sung Gu

    2018-06-01

    The ferroelectric instabilities of an artificially adopted Pnma structure in low tolerance perovskites have been explored (Kang et al., 2017) [4], where an unstable A-site environment was reported to be the major driving source for the low tolerance perovskites to exhibit ferroelectric instability. This study examined the ferroelectric transition of two magnetic perovskite materials, MnSnO3 and MnTiO3, in Pnma phase. Phase transitions to the Pnma phase at elevated pressures were observed. MnSnO3, which has a lower (larger) tolerance factor (B-site cation radius), showed a higher ferroelectric mode amplitude than MnTiO3. The distribution of the bond length of Mn-O and the mean quadratic elongation (QE) of octahedra (SnO6 or TiO6) were investigated for structural analysis. However, MnTiO3 showed a larger spontaneous polarization than MnSnO3 due to high Born effective charges of titanium. This study is useful because it provides a valuable pathway to the design of promising multiferroic materials.

  14. Reversible Structural Swell-Shrink and Recoverable Optical Properties in Hybrid Inorganic-Organic Perovskite.

    PubMed

    Zhang, Yupeng; Wang, Yusheng; Xu, Zai-Quan; Liu, Jingying; Song, Jingchao; Xue, Yunzhou; Wang, Ziyu; Zheng, Jialu; Jiang, Liangcong; Zheng, Changxi; Huang, Fuzhi; Sun, Baoquan; Cheng, Yi-Bing; Bao, Qiaoliang

    2016-07-26

    Ion migration in hybrid organic-inorganic perovskites has been suggested to be an important factor for many unusual behaviors in perovskite-based optoelectronics, such as current-voltage hysteresis, low-frequency giant dielectric response, and the switchable photovoltaic effect. However, the role played by ion migration in the photoelectric conversion process of perovskites is still unclear. In this work, we provide microscale insights into the influence of ion migration on the microstructure, stability, and light-matter interaction in perovskite micro/nanowires by using spatially resolved optical characterization techniques. We observed that ion migration, especially the migration of MA(+) ions, will induce a reversible structural swell-shrink in perovskites and recoverably affect the reflective index, quantum efficiency, light-harvesting, and photoelectric properties. The maximum ion migration quantity in perovskites was as high as approximately 30%, resulting in lattice swell or shrink of approximately 4.4%. Meanwhile, the evidence shows that ion migration in perovskites could gradually accelerate the aging of perovskites because of lattice distortion in the reversible structural swell-shrink process. Knowledge regarding reversible structural swell-shrink and recoverable optical properties may shed light on the development of optoelectronic and converse piezoelectric devices based on perovskites.

  15. Pressure-Induced Structural Evolution and Band Gap Shifts of Organometal Halide Perovskite-Based Methylammonium Lead Chloride.

    PubMed

    Wang, Lingrui; Wang, Kai; Xiao, Guanjun; Zeng, Qiaoshi; Zou, Bo

    2016-12-15

    Organometal halide perovskites are promising materials for optoelectronic devices. Further development of these devices requires a deep understanding of their fundamental structure-property relationships. The effect of pressure on the structural evolution and band gap shifts of methylammonium lead chloride (MAPbCl 3 ) was investigated systematically. Synchrotron X-ray diffraction and Raman experiments provided structural information on the shrinkage, tilting distortion, and amorphization of the primitive cubic unit cell. In situ high pressure optical absorption and photoluminescence spectra manifested that the band gap of MAPbCl 3 could be fine-tuned to the ultraviolet region by pressure. The optical changes are correlated with pressure-induced structural evolution of MAPbCl 3 , as evidenced by band gap shifts. Comparisons between Pb-hybrid perovskites and inorganic octahedra provided insights on the effects of halogens on pressure-induced transition sequences of these compounds. Our results improve the understanding of the structural and optical properties of organometal halide perovskites.

  16. ABO Mistyping of cis-AB Blood Group by the Automated Microplate Technique.

    PubMed

    Chun, Sejong; Ryu, Mi Ra; Cha, Seung-Yeon; Seo, Ji-Young; Cho, Duck

    2018-01-01

    The cis -AB phenotype, although rare, is the relatively most frequent of ABO subgroups in Koreans. To prevent ABO mistyping of cis -AB samples, our hospital has applied a combination of the manual tile method with automated devices. Herein, we report cases of ABO mistyping detected by the combination testing system. Cases that showed discrepant results by automated devices and the manual tile method were evaluated. These samples were also tested by the standard tube method. The automated devices used in this study were a QWALYS-3 and Galileo NEO. Exons 6 and 7 of the ABO gene were sequenced. 13 cases that had the cis -AB allele showed results suggestive of the cis -AB subgroup by manual methods, but were interpreted as AB by either automated device. This happened in 87.5% of these cases by QWALYS-3 and 70.0% by Galileo NEO. Genotyping results showed that 12 cases were ABO*cis-AB01/ABO*O01 or ABO*cis-AB01/ABO*O02 , and one case was ABO*cis-AB01/ ABO*A102. Cis -AB samples were mistyped as AB by the automated microplate technique in some cases. We suggest that the manual tile method can be a simple supplemental test for the detection of the cis -AB phenotype, especially in countries with relatively high cis- AB prevalence.

  17. Conducting tin halides with a layered organic-based perovskite structure

    NASA Astrophysics Data System (ADS)

    Mitzi, D. B.; Feild, C. A.; Harrison, W. T. A.; Guloy, A. M.

    1994-06-01

    THE discovery1 of high-temperature superconductivity in layered copper oxide perovskites has generated considerable fundamental and technological interest in this class of materials. Only a few other examples of conducting layered perovskites are known; these are also oxides such as (La1-xSrx)n+1 MnnO3n+1 (ref. 2), Lan+1NinO3n+1 (ref. 3) and Ban+1PbnO3n+1 (ref. 4), all of which exhibit a trend from semiconducting to metallic behaviour with increasing number of perovskite layers (n). We report here the synthesis of a family of organic-based layered halide perovskites, (C4H9NH3)2(CH3NH3)n-1Snnl3n+1 which show a similar transition from semiconducting to metallic behaviour with increasing n. The incorporation of an organic modulation layer between the conducting tin iodide sheets potentially provides greater flexibility for tuning the electrical properties of the perovskite sheets, and we suggest that such an approach will prove valuable for exploring the range of transport properties possible with layered perovskites.

  18. Enhancing the Performance of Perovskite Solar Cells by Hybridizing SnS Quantum Dots with CH3 NH3 PbI3.

    PubMed

    Han, Jianhua; Yin, Xuewen; Nan, Hui; Zhou, Yu; Yao, Zhibo; Li, Jianbao; Oron, Dan; Lin, Hong

    2017-08-01

    The combination of perovskite solar cells and quantum dot solar cells has significant potential due to the complementary nature of the two constituent materials. In this study, solar cells (SCs) with a hybrid CH 3 NH 3 PbI 3 /SnS quantum dots (QDs) absorber layer are fabricated by a facile and universal in situ crystallization method, enabling easy embedding of the QDs in perovskite layer. Compared with SCs based on CH 3 NH 3 PbI 3 , SCs using CH 3 NH 3 PbI 3 /SnS QDs hybrid films as absorber achieves a 25% enhancement in efficiency, giving rise to an efficiency of 16.8%. The performance improvement can be attributed to the improved crystallinity of the absorber, enhanced photo-induced carriers' separation and transport within the absorber layer, and improved incident light utilization. The generality of the methods used in this work paves a universal pathway for preparing other perovskite/QDs hybrid materials and the synthesis of entire nontoxic perovskite/QDs hybrid structure. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. First-principles calculations of structural, elastic, electronic, and optical properties of perovskite-type KMgH3 crystals: novel hydrogen storage material.

    PubMed

    Reshak, Ali H; Shalaginov, Mikhail Y; Saeed, Yasir; Kityk, I V; Auluck, S

    2011-03-31

    We report a first-principles study of structural and phase stability in three different structures of perovskite-types KMgH(3) according to H position. While electronic and optical properties were measured only for stable perovskite-type KMgH(3), our calculated structural parameters are found in good agreement with experiment and other theoretical results. We also study the electronic charge density space distribution contours in the (200), (101), and (100) crystallographic planes, which gives better insight picture of chemical bonding between K-H, K-Mg-H, and Mg-H. Moreover, we have calculated the electronic band structure dispersion, total, and partial density of electron states to study the band gap origin and the contribution of s-band of H, s and p-band of Mg in the valence band, and d-band of K in the conduction band. Furthermore, optical features such as dielectric functions, refractive indices, extinction coefficient, optical reflectivity, absorption coefficients, optical conductivities, and loss functions of stable KMgH(3) were calculated for photon energies up to 40 eV.

  20. Role of structure imperfection in the formation of the magnetotransport properties of rare-earth manganites with a perovskite structure

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pashchenko, A. V., E-mail: alpash@mail.ru; Pashchenko, V. P.; Prokopenko, V. K.

    2017-01-15

    The structure, the structure imperfection, and the magnetoresistance, magnetotransport, and microstructure properties of rare-earth perovskite La{sub 0.3}Ln{sub 0.3}Sr{sub 0.3}Mn{sub 1.1}O{sub 3–δ} manganites are studied by X-ray diffraction, thermogravimetry, electrical resistivity measurement, magnetic, {sup 55}Mn NMR, magnetoresistance measurement, and scanning electron microscopy. It is found that the structure imperfection increases, and the symmetry of a rhombohedrally distorted R3̅c perovskite structure changes into its pseudocubic type during isovalent substitution for Ln = La{sup 3+}, Pr{sup 3+}, Nd{sup 3+}, Sm{sup 3+}, or Eu{sup 3+} when the ionic radius of an A cation decreases. Defect molar formulas are determined for a real perovskite structure,more » which contains anion and cation vacancies. The decrease in the temperatures of the metal–semiconductor (T{sub ms}) and ferromagnet–paramagnet (T{sub C}) phase transitions and the increase in electrical resistivity ρ and activation energy E{sub a} with increasing serial number of Ln are caused by an increase in the concentration of vacancy point defects, which weaken the double exchange 3d{sup 4}(Mn{sup 3+})–2p{sup 6}(O{sup 2–})–3d{sup 3}(Mn{sup 4+})–V{sup (a)}–3d{sup 4}(Mn{sup 3+}). The crystal structure of the compositions with Ln = La contains nanostructured planar clusters, which induce an anomalous magnetic hysteresis at T = 77 K. Broad and asymmetric {sup 55}Mn NMR spectra support the high-frequency electronic double exchange Mn{sup 3+}(3d{sup 4}) ↔ O{sup 2–}(2p{sup 6}) ↔ Mn{sup 4+}(3d{sup 3}) and indicate a heterogeneous surrounding of manganese by other ions and vacancies. A correlation is revealed between the tunneling magnetoresistance effect and the crystallite size. A composition–structure imperfection–property experimental phase diagram is plotted. This diagram supports the conclusion about a strong influence of structure imperfection on the formation of the

  1. [(CH3)3NCH2CH2NH3]SnI4: a layered perovskite with quaternary/primary ammonium dications and short interlayer iodine-iodine contacts.

    PubMed

    Xu, Zhengtao; Mitzi, David B; Medeiros, David R

    2003-03-10

    The organic-inorganic hybrid [(CH(3))(3)NCH(2)CH(2)NH(3)]SnI(4) presents a layered perovskite structure, templated by an organic dication containing both a primary and a quaternary ammonium group. Due to the high charge density and small size of the organic cation, the separation of the perovskite layers is small and short iodine-iodine contacts of 4.19 A are formed between the layers. Optical thin-film measurements on this compound indicate a significant red shift of the exciton peak (630 nm) associated with the band gap, as compared with other SnI(4)(2)(-)-based layered perovskite structures.

  2. Photovoltaic properties of Cu-doped CH3NH3PbI3 with perovskite structure

    NASA Astrophysics Data System (ADS)

    Shirahata, Yasuhiro; Oku, Takeo

    2017-01-01

    Photovoltaic properties of copper (Cu)-doped perovskite (CH3NH3PbCuxI3+x) photovoltaic devices with different Cu content were investigated. The CH3NH3PbCuxI3+x films were polycrystalline with a tetragonal system, and their lattice constants and crystallite size varied with Cu doping. Compared to conversion efficiencies of non-doped CH3NH3PbI3 photovoltaic device, those of CH3NH3PbCuxI3+x photovoltaic devises increased. The improvement of photovoltaic properties was attributed to partial substitution of Cu at the Pb sites.

  3. Investigation of Thermally Induced Degradation in CH3NH3PbI3 Perovskite Solar Cells using In-situ Synchrotron Radiation Analysis.

    PubMed

    Kim, Nam-Koo; Min, Young Hwan; Noh, Seokhwan; Cho, Eunkyung; Jeong, Gitaeg; Joo, Minho; Ahn, Seh-Won; Lee, Jeong Soo; Kim, Seongtak; Ihm, Kyuwook; Ahn, Hyungju; Kang, Yoonmook; Lee, Hae-Seok; Kim, Donghwan

    2017-07-05

    In this study, we employ a combination of various in-situ surface analysis techniques to investigate the thermally induced degradation processes in MAPbI 3 perovskite solar cells (PeSCs) as a function of temperature under air-free conditions (no moisture and oxygen). Through a comprehensive approach that combines in-situ grazing-incidence wide-angle X-ray diffraction (GIWAXD) and high-resolution X-ray photoelectron spectroscopy (HR-XPS) measurements, we confirm that the surface structure of MAPbI 3 perovskite film changes to an intermediate phase and decomposes to CH 3 I, NH 3 , and PbI 2 after both a short (20 min) exposure to heat stress at 100 °C and a long exposure (>1 hour) at 80 °C. Moreover, we observe clearly the changes in the orientation of CH 3 NH 3 + organic cations with respect to the substrate in the intermediate phase, which might be linked directly to the thermal degradation processes in MAPbI 3 perovskites. These results provide important progress towards improved understanding of the thermal degradation mechanisms in perovskite materials and will facilitate improvements in the design and fabrication of perovskite solar cells with better thermal stability.

  4. Hierarchically porous LaFeO3 perovskite prepared from the pomelo peel bio-template for catalytic oxidation of NO

    NASA Astrophysics Data System (ADS)

    Zhao, Shaojun; Wang, Li; Wang, Ying; Li, Xing

    2018-05-01

    In this paper, pomelo peel was used as biological template to obtain hierarchically porous LaFeO3 perovskite for the catalytic oxidation of NO to NO2. In addition, X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption-desorption analyses, X-ray photoelectron spectra (XPS), NO temperature-programmed desorption (NO-TPD), oxygen temperature-programmed desorption (O2-TPD) and hydrogen temperature-programmed reduction (H2-TPR) were used to investigate the micro-structure and the redox properties of the hierarchically porous LaFeO3 perovskite prepared from pomelo peel biological template and the LaFeO3 perovskite without the biological template. The results indicated that the hierarchically porous LaFeO3 perovskite successfully replicated the porous structure of pomelo peel with high specific surface area. Compared to the LaFeO3 perovskite prepared without the pomelo peel template, the hierarchically porous LaFeO3 perovskite showed better catalytic oxidization of NO to NO2 under the same conditions. The maximum NO conversions for LaFeO3 prepared with and without template were 90% at 305 °C and 76% at 313 °C, respectively. This is mainly attributed to the higher ratio of Fe4+/Fe3+, the hierarchically porous structure with more adsorbed oxygen species and higher surface area for the hierarchically porous LaFeO3 perovskite compared with the sample prepared without the pomelo peel template.

  5. Structural and dielectric studies of Ce doped BaSnO3 perovskite nanostructures

    NASA Astrophysics Data System (ADS)

    Angel, S. Lilly; Deepa, K.; Rajamanickam, N.; Jayakumar, K.; Ramachandran, K.

    2018-04-01

    Undoped and Cerium (Ce) doped BaSnO3(BSO) nanostructures were synthesized by co-precipitation method. The cubic structure and perovskite phase were confirmed by X-ray diffraction (XRD). The crystallite size of BSO is 41nm and when Ce ion concentration is increased, the crystallite sizesdecreased. The nanocube, nanocuboids and nanorods are observed from SEM analysis. The purity of the undoped and doped samples are confirmed by EDS spectrum. For larger defects, wide band gap was obtained from UV-Vis and PL spectrum. The dielectric constants are increased at low frequencies when Ce impurities are introduced in the BSO matrix at Sn site.

  6. Predictions of new AB O3 perovskite compounds by combining machine learning and density functional theory

    NASA Astrophysics Data System (ADS)

    Balachandran, Prasanna V.; Emery, Antoine A.; Gubernatis, James E.; Lookman, Turab; Wolverton, Chris; Zunger, Alex

    2018-04-01

    We apply machine learning (ML) methods to a database of 390 experimentally reported A B O3 compounds to construct two statistical models that predict possible new perovskite materials and possible new cubic perovskites. The first ML model classified the 390 compounds into 254 perovskites and 136 that are not perovskites with a 90% average cross-validation (CV) accuracy; the second ML model further classified the perovskites into 22 known cubic perovskites and 232 known noncubic perovskites with a 94% average CV accuracy. We find that the most effective chemical descriptors affecting our classification include largely geometric constructs such as the A and B Shannon ionic radii, the tolerance and octahedral factors, the A -O and B -O bond length, and the A and B Villars' Mendeleev numbers. We then construct an additional list of 625 A B O3 compounds assembled from charge conserving combinations of A and B atoms absent from our list of known compounds. Then, using the two ML models constructed on the known compounds, we predict that 235 of the 625 exist in a perovskite structure with a confidence greater than 50% and among them that 20 exist in the cubic structure (albeit, the latter with only ˜50 % confidence). We find that the new perovskites are most likely to occur when the A and B atoms are a lanthanide or actinide, when the A atom is an alkali, alkali earth, or late transition metal atom, or when the B atom is a p -block atom. We also compare the ML findings with the density functional theory calculations and convex hull analyses in the Open Quantum Materials Database (OQMD), which predicts the T =0 K ground-state stability of all the A B O3 compounds. We find that OQMD predicts 186 of 254 of the perovskites in the experimental database to be thermodynamically stable within 100 meV/atom of the convex hull and predicts 87 of the 235 ML-predicted perovskite compounds to be thermodynamically stable within 100 meV/atom of the convex hull, including 6 of these to

  7. Annealing Induced Re-crystallization in CH3NH3PbI3−xClx for High Performance Perovskite Solar Cells

    PubMed Central

    Yang, Yingguo; Feng, Shanglei; Li, Meng; Xu, Weidong; Yin, Guangzhi; Wang, Zhaokui; Sun, Baoquan; Gao, Xingyu

    2017-01-01

    Using poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) as hole conductor, a series of inverted planar CH3NH3PbI3−xClx perovskite solar cells (PSCs) were fabricated based on perovskite annealed by an improved time-temperature dependent (TTD) procedure in a flowing nitrogen atmosphere for different time. Only after an optimum annealing time, an optimized power conversion efficiency of 14.36% could be achieved. To understand their performance dependence on annealing time, an in situ real-time synchrotron-based grazing incidence X-ray diffraction (GIXRD) was used to monitor a step-by-step gradual structure transformation from distinct mainly organic-inorganic hybrid materials into highly ordered CH3NH3PbI3 crystal during annealing. However, a re-crystallization process of perovskite crystal was observed for the first time during such an annealing procedure, which helps to enhance the perovskite crystallization and preferential orientations. The present GIXRD findings could well explain the drops of the open circuit voltage (Voc) and the fill factor (FF) during the ramping of temperature as well as the optimized power conversion efficiency achieved after an optimum annealing time. Thus, the present study not only illustrates clearly the decisive roles of post-annealing in the formation of solution-processed perovskite to better understand its formation mechanism, but also demonstrates the crucial dependences of device performance on the perovskite microstructure in PSCs. PMID:28429762

  8. Synthesis and Structure of A New Perovskite, SrCuO 2.5

    NASA Astrophysics Data System (ADS)

    Chen, Bai-Hao; Walker, Dave; Scott, Bruce A.; Mitzi, David B.

    1996-02-01

    A new oxygen-deficient perovskite, SrCuO2.5, was prepared at 950°C and 100 kbar pressure in a multianvil apparatus. Rietveld profile analysis, using X-ray powder diffraction data, was employed for the structural determination. SrCuO2.5is orthorhombic,Pbam(No. 55),Z= 4,a= 5.424(2) Â,b= 10.837(4) Â, andc= 3.731(1) Â, which is related to the perovskite subcell by root{2}ap× 2root{2}ap×ap, whereapis the simple cubic perovskite lattice parameter. It consists of corner-shared CuO5square pyramids with oxygen vacancy ordering in the CuO2layers. The ordered oxygen vacancies create parallel pseudo-hexagonal tunnels where the Sr atoms reside, forming SrO10polyhedra. Structural features with respect to oxygen vacancies, superstructures, and distortions are analogous to the type of ordering observed in Sr2CuO3+δ. Superconductivity was not observed in SrCuO2.5down to 5 K.

  9. Temperature Dependent Surface Structures and Electronic Properties of Organic-Inorganic Hybrid Perovskite Single Crystals

    NASA Astrophysics Data System (ADS)

    Jao, M.-H.; Teague, M. L.; Huang, J.-S.; Tseng, W.-S.; Yeh, N.-C.

    Organic-inorganic hybrid perovskites, arising from research of low-cost high performance photovoltaics, have become promising materials not only for solar cells but also for various optoelectronic and spintronic applications. An interesting aspect of the hybrid perovskites is that their material properties, such as the band gap, can be easily tuned by varying the composition, temperature, and the crystalline phases. Additionally, the surface structure is critically important for their optoelectronic applications. It is speculated that different crystalline facets could show different trap densities, thus resulting in microscopically inhomogeneous performance. Here we report direct studies of the surface structures and electronic properties of hybrid perovskite CH3NH3PbI3 single crystals by scanning tunneling microscopy and spectroscopy (STM/STS). We found long-range spatially homogeneous tunneling conductance spectra with a well-defined energy gap of (1.55 +/- 0.1) eV at 300 K in the tetragonal phase, suggesting high quality of the single crystals. The energy gap increased to (1.81 +/- 0.1) eV in the orthorhombic phase, below the tetragonal-to-orthorhombic phase transition temperature at 150 K. Detailed studies of the temperature evolution in the spatially resolved surface structures and local density of states will be discussed to elucidate how these properties may influence the optoelectronic performance of the hybrid perovskites. We thank the support from NTU in Taiwan and from NSF in the US.

  10. Tilts, dopants, vacancies and non-stoichiometry: Understanding and designing the properties of complex solid oxide perovskites from first principles

    NASA Astrophysics Data System (ADS)

    Bennett, Joseph W.

    Perovskite oxides of formula ABO3 have a wide range of structural, electrical and mechanical properties, making them vital materials for many applications, such as catalysis, ultrasound machines and communication devices. Perovskite solid solutions with high piezoelectric response, such as ferroelectrics, are of particular interest as they can be employed as sensors in SONAR devices. Ferroelectric materials are unique in that their chemical and electrical properties can be non-invasively and reversibly changed, by switching the bulk polarization. This makes ferroelectrics useful for applications in non-volatile random access memory (NVRAM) devices. Perovskite solid solutions with a lower piezoelectric response than ferroelectrics are important for communication technology, as they function well as electroceramic capacitors. Also of interest is how these materials act as a component in a solid oxide fuel cell, as they can function as an efficient source of energy. Altering the chemical composition of these solid oxide materials offers an opportunity to change the desired properties of the final ceramic, adding a degree of flexibility that is advantageous for a variety of applications. These solid oxides are complex, sometimes disordered systems that are a challenge to study experimentally. However, as it is their complexity which produces favorable properties, highly accurate modeling which captures the essential features of the disordered structure is necessary to explain the behavior of current materials and predict favorable compositions for new materials. Methodological improvements and faster computer speeds have made first-principles and atomistic calculations a viable tool for understanding these complex systems. Offering a combination of accuracy and computational speed, the density functional theory (DFT) approach can reveal details about the microscopic structure and interactions of complex systems. Using DFT and a combination of principles from both

  11. Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3

    DOE PAGES

    Wang, Yun; Huang, Jingsong; Sumpter, Bobby G.; ...

    2014-12-19

    Organic/inorganic hybrid perovskite materials are highly attractive for dye-sensitized solar cells as demonstrated by their rapid advances in energy conversion efficiency. In this work, the structures, energetics, and electronic properties for a range of stoichiometric surfaces of the orthorhombic perovskite CH3NH3PbI3 are theoretically studied using density functional theory. Various possible spatially and constitutionally isomeric surfaces are considered by diversifying the spatial orientations and connectivities of surface Pb-I bonds. The comparison of the surface energies for the most stable configurations identified for various surfaces shows that the stabilities of stoichiometric surfaces are mainly dictated by the coordination numbers of surface atoms,more » which are directly correlated with the numbers of broken bonds. Additionally, Coulombic interactions between I anions and organic countercations on the surface also contribute to the stabilization. Electronic properties are compared between the most stable (100) surface and the bulk phase, showing generally similar features except for the lifted band degeneracy and the enhanced bandgap energy for the surface. These studies on the stoichiometric surfaces serve as the first step toward gaining a fundamental understanding of the interfacial properties in the current structural design of perovskite based solar cells, in order to achieve further breakthroughs in solar conversion efficiencies.« less

  12. Single-Crystal Thin Films of Cesium Lead Bromide Perovskite Epitaxially Grown on Metal Oxide Perovskite (SrTiO 3)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chen, Jie; Morrow, Darien J.; Fu, Yongping

    High-quality metal halide perovskite single crystals have low defect densities and excellent photophysical properties, yet thin films are the most sought after material geometry for optoelectronic devices. Perovskite single-crystal thin films (SCTFs) would be highly desirable for high-performance devices, but their growth remains challenging, particularly for inorganic metal halide perovskites. Herein, we report the facile vapor-phase epitaxial growth of cesium lead bromide perovskite (CsPbBr 3) continuous SCTFs with controllable micrometer thickness, as well as nanoplate arrays, on traditional oxide perovskite SrTiO 3(100) substrates. Heteroepitaxial single-crystal growth is enabled by the serendipitous incommensurate lattice match between these two perovskites, and overcomingmore » the limitation of island-forming Volmer–Weber crystal growth is critical for growing large-area continuous thin films. Time-resolved photoluminescence, transient reflection spectroscopy, and electrical transport measurements show that the CsPbBr 3 epitaxial thin film has a slow charge carrier recombination rate, low surface recombination velocity (10 4 cm s –1), and low defect density of 10 12 cm –3, which are comparable to those of CsPbBr 3 single crystals. This work suggests a general approach using oxide perovskites as substrates for heteroepitaxial growth of halide perovskites. Furthermore, the high-quality halide perovskite SCTFs epitaxially integrated with multifunctional oxide perovskites could open up opportunities for a variety of high-performance optoelectronics devices.« less

  13. Single-Crystal Thin Films of Cesium Lead Bromide Perovskite Epitaxially Grown on Metal Oxide Perovskite (SrTiO 3)

    DOE PAGES

    Chen, Jie; Morrow, Darien J.; Fu, Yongping; ...

    2017-09-05

    High-quality metal halide perovskite single crystals have low defect densities and excellent photophysical properties, yet thin films are the most sought after material geometry for optoelectronic devices. Perovskite single-crystal thin films (SCTFs) would be highly desirable for high-performance devices, but their growth remains challenging, particularly for inorganic metal halide perovskites. Herein, we report the facile vapor-phase epitaxial growth of cesium lead bromide perovskite (CsPbBr 3) continuous SCTFs with controllable micrometer thickness, as well as nanoplate arrays, on traditional oxide perovskite SrTiO 3(100) substrates. Heteroepitaxial single-crystal growth is enabled by the serendipitous incommensurate lattice match between these two perovskites, and overcomingmore » the limitation of island-forming Volmer–Weber crystal growth is critical for growing large-area continuous thin films. Time-resolved photoluminescence, transient reflection spectroscopy, and electrical transport measurements show that the CsPbBr 3 epitaxial thin film has a slow charge carrier recombination rate, low surface recombination velocity (10 4 cm s –1), and low defect density of 10 12 cm –3, which are comparable to those of CsPbBr 3 single crystals. This work suggests a general approach using oxide perovskites as substrates for heteroepitaxial growth of halide perovskites. Furthermore, the high-quality halide perovskite SCTFs epitaxially integrated with multifunctional oxide perovskites could open up opportunities for a variety of high-performance optoelectronics devices.« less

  14. Highly Efficient 2D/3D Hybrid Perovskite Solar Cells via Low-Pressure Vapor-Assisted Solution Process.

    PubMed

    Li, Ming-Hsien; Yeh, Hung-Hsiang; Chiang, Yu-Hsien; Jeng, U-Ser; Su, Chun-Jen; Shiu, Hung-Wei; Hsu, Yao-Jane; Kosugi, Nobuhiro; Ohigashi, Takuji; Chen, Yu-An; Shen, Po-Shen; Chen, Peter; Guo, Tzung-Fang

    2018-06-08

    The fabrication of multidimensional organometallic halide perovskite via a low-pressure vapor-assisted solution process is demonstrated for the first time. Phenyl ethyl-ammonium iodide (PEAI)-doped lead iodide (PbI 2 ) is first spin-coated onto the substrate and subsequently reacts with methyl-ammonium iodide (MAI) vapor in a low-pressure heating oven. The doping ratio of PEAI in MAI-vapor-treated perovskite has significant impact on the crystalline structure, surface morphology, grain size, UV-vis absorption and photoluminescence spectra, and the resultant device performance. Multiple photoluminescence spectra are observed in the perovskite film starting with high PEAI/PbI 2 ratio, which suggests the coexistence of low-dimensional perovskite (PEA 2 MA n -1 Pb n I 3 n +1 ) with various values of n after vapor reaction. The dimensionality of the as-fabricated perovskite film reveals an evolution from 2D, hybrid 2D/3D to 3D structure when the doping level of PEAI/PbI 2 ratio varies from 2 to 0. Scanning electron microscopy images and Kelvin probe force microscopy mapping show that the PEAI-containing perovskite grain is presumably formed around the MAPbI 3 perovskite grain to benefit MAPbI 3 grain growth. The device employing perovskite with PEAI/PbI 2 = 0.05 achieves a champion power conversion efficiency of 19.10% with an open-circuit voltage of 1.08 V, a current density of 21.91 mA cm -2 , and a remarkable fill factor of 80.36%. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Engineering Interface Structure to Improve Efficiency and Stability of Organometal Halide Perovskite Solar Cells.

    PubMed

    Qiu, Longbin; Ono, Luis K; Jiang, Yan; Leyden, Matthew R; Raga, Sonia R; Wang, Shenghao; Qi, Yabing

    2018-01-18

    The rapid rise of power conversion efficiency (PCE) of low cost organometal halide perovskite solar cells suggests that these cells are a promising alternative to conventional photovoltaic technology. However, anomalous hysteresis and unsatisfactory stability hinder the industrialization of perovskite solar cells. Interface engineering is of importance for the fabrication of highly stable and hysteresis free perovskite solar cells. Here we report that a surface modification of the widely used TiO 2 compact layer can give insight into interface interaction in perovskite solar cells. A highest PCE of 18.5% is obtained using anatase TiO 2 , but the device is not stable and degrades rapidly. With an amorphous TiO 2 compact layer, the devices show a prolonged lifetime but a lower PCE and more pronounced hysteresis. To achieve a high PCE and long lifetime simultaneously, an insulating polymer interface layer is deposited on top of TiO 2 . Three polymers, each with a different functional group (hydroxyl, amino, or aromatic group), are investigated to further understand the relation of interface structure and device PCE as well as stability. We show that it is necessary to consider not only the band alignment at the interface, but also interface chemical interactions between the thin interface layer and the perovskite film. The hydroxyl and amino groups interact with CH 3 NH 3 PbI 3 leading to poor PCEs. In contrast, deposition of a thin layer of polymer consisting of an aromatic group to prevent the direct contact of TiO 2 and CH 3 NH 3 PbI 3 can significantly enhance the device stability, while the same time maintaining a high PCE. The fact that a polymer interface layer on top of TiO 2 can enhance device stability, strongly suggests that the interface interaction between TiO 2 and CH 3 NH 3 PbI 3 plays a crucial role. Our work highlights the importance of interface structure and paves the way for further optimization of PCEs and stability of perovskite solar cells.

  16. Polarized emission from CsPbX3 perovskite quantum dots

    NASA Astrophysics Data System (ADS)

    Wang, Dan; Wu, Dan; Dong, Di; Chen, Wei; Hao, Junjie; Qin, Jing; Xu, Bing; Wang, Kai; Sun, Xiaowei

    2016-06-01

    Compared to organic/inorganic hybrid perovskites, full inorganic perovskite quantum dots (QDs) exhibit higher stability. In this study, full inorganic CsPbX3 (X = Br, I and mixed halide systems Br/I) perovskite QDs have been synthesized and interestingly, these QDs showed highly polarized photoluminescence which is systematically studied for the first time. Furthermore, the polarization of CsPbI3 was as high as 0.36 in hexane and 0.40 as a film. The CsPbX3 perovskite QDs with high polarization properties indicate that they possess great potential for application in new generation displays with wide colour gamut and low power consumption.Compared to organic/inorganic hybrid perovskites, full inorganic perovskite quantum dots (QDs) exhibit higher stability. In this study, full inorganic CsPbX3 (X = Br, I and mixed halide systems Br/I) perovskite QDs have been synthesized and interestingly, these QDs showed highly polarized photoluminescence which is systematically studied for the first time. Furthermore, the polarization of CsPbI3 was as high as 0.36 in hexane and 0.40 as a film. The CsPbX3 perovskite QDs with high polarization properties indicate that they possess great potential for application in new generation displays with wide colour gamut and low power consumption. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01915c

  17. [Association of abo blood groups with gestational diabetes mellitus].

    PubMed

    Huidobro M, Andrea; Torres C, Demetrio; Paredes, Fabio

    2017-04-01

    ABO and Rhesus blood systems are associated with type 2 Diabetes Mellitus (DM2). Gestational Diabetes (GDM) is a model to study DM. To study the association between GDM and ABO and Rhesus groups. A retrospective cohort study was performed in 1,078 women who gave birth to a singleton in Talca Regional Hospital, Chile, during 2008. We analyzed personal, obstetric, medical data and ABO and Rh blood groups. GDM was diagnosed in 6.6% of women. Age and body mass index were significantly associated with GDM. There were no differences in Rh blood groups (p = 0.604), while ABO groups were different between GDM and controls. B antigen was present in 3% of GDM women and in 10.8% of controls (p = 0.037), with an odds ratio of 0.25 after adjusting for other associated risk factors (p = 0.06). ABO group is suggested as a possible protector marker for GDM.

  18. Copper-Substituted Lead Perovskite Materials Constructed with Different Halides for Working (CH3NH3)2CuX4-Based Perovskite Solar Cells from Experimental and Theoretical View.

    PubMed

    Elseman, Ahmed Mourtada; Shalan, Ahmed Esmail; Sajid, Sajid; Rashad, Mohamed Mohamed; Hassan, Ali Mostafa; Li, Meicheng

    2018-04-11

    Toxicity and chemical instability issues of halide perovskites based on organic-inorganic lead-containing materials still remain as the main drawbacks for perovskite solar cells (PSCs). Herein, we discuss the preparation of copper (Cu)-based hybrid materials, where we replace lead (Pb) with nontoxic Cu metal for lead-free PSCs, and investigate their potential toward solar cell applications based on experimental and theoretical studies. The formation of (CH 3 NH 3 ) 2 CuX 4 [(CH 3 NH 3 ) 2 CuCl 4 , (CH 3 NH 3 ) 2 CuCl 2 I 2 , and (CH 3 NH 3 ) 2 CuCl 2 Br 2 ] was discussed in details. Furthermore, it was found that chlorine (Cl - ) in the structure is critical for the stabilization of the formed compounds. Cu-based perovskite-like materials showed attractive absorbance features extended to the near-infrared range, with appropriate band gaps. Green photoluminescence of these materials was obtained because of Cu + ions. The power conversion efficiency was measured experimentally and estimated theoretically for different architectures of solar cell devices.

  19. High permeable microporous structured carbon counter electrode assisted by polystyrene sphere for fully printable perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Tao, Haijun; Li, Yongtao; Zhang, Chuanxiang; Wang, Kang; Wang, Jiayue; Tan, Bin; Han, Linxuan; Tao, Jie

    2018-03-01

    The permeability of the carbon counter electrode (CCE) is critical to the HTM-free fully printable perovskite solar cells. In this work, we report a CCE assisted by polystyrene spheres (PS-spheres) as pore-forming agent to gain microporous structure for a better permeability. Due to its decomposition temperature at 400 °C, the porous structure is obtained in the carbon layer easily. By optimization towards the contents of PS-spheres in CCE, the filling rate of perovskite solution and the photovoltaic performance of the device have been significantly improved. Using this method, an average efficiency enhancement of 22% has been obtained for HTM-free fully printable perovskite solar cells, resulting in a better fill rate of CH3NH3PbI3 and an efficiency of 4.49%. This kind of CCE with the advantages of simple, easy preparation process and well performance, show excellent potential application in perovskite solar cells.

  20. Chlorine Incorporation in the CH3NH3PbI3 Perovskite: Small Concentration, Big Effect.

    PubMed

    Quarti, Claudio; Mosconi, Edoardo; Umari, Paolo; De Angelis, Filippo

    2017-01-03

    The role of chlorine doping in CH 3 NH 3 PbI 3 represents an important open issue in the use of hybrid perovskites for photovoltaic applications. In particular, even if a positive role of chlorine doping on perovskite film formation and on material morphology has been demonstrated, an inherent positive effect on the electronic and photovoltaic properties cannot be excluded. Here we carried out periodic density functional theory and Car-Parrinello molecular dynamics simulations, going down to ∼1% doping, to investigate the effect of chlorine on CH 3 NH 3 PbI 3 . We found that such a small doping has important effects on the dynamics of the crystalline structure, both with respect to the inorganic framework and with respect to the cation libration motion. Together, we observe a dynamic spatial localization of the valence and conduction states in separated spatial material regions, which takes place in the 10 -1 ps time scale and which could be the key to ease of exciton dissociation and, likely, to small charge recombination in hybrid perovskites. Moreover, such localization is enhanced by chlorine doping, demonstrating an inherent positive role of chlorine doping on the electronic properties of this class of materials.

  1. ABO Blood Type and Personality Traits in Healthy Japanese Subjects.

    PubMed

    Tsuchimine, Shoko; Saruwatari, Junji; Kaneda, Ayako; Yasui-Furukori, Norio

    2015-01-01

    There is no scientific consensus that a relationship exists between the ABO blood group and personality traits. However, a recent study hypothesized that the dopamine beta-hydroxylase (DBH) gene is in linkage with the ABO gene. The sample population consisted of 1,427 healthy Japanese subjects who completed the Temperament and Character Inventory (TCI). Each subject's ABO blood type was determined by genotyping the rs8176719 and rs8176746 ABO gene single-nucleotide polymorphisms (SNPs) using a TaqMan genotyping assay. The relationships between the six ABO genotypes or four ABO phenotypes and personality traits were examined using a multivariate analysis of covariance (MANCOVA), controlling for age and sex. The MANCOVA data showed a significant difference in TCI scores among the ABO genotype groups (F [7, 1393] = 3.354, p = 0.001). A subsequent univariate analysis showed a significant difference in the mean scores for Persistence among the genotype groups (F = 2.680, partial η2 = 0.010, p = 0.020). Similarly, dividing the ABO blood type into four phenotypes revealed a significant difference among the phenotype groups (F [7, 1397] = 2.529, p = 0.014). A subsequent univariate analysis showed a significant difference among the phenotype groups in the mean scores for Persistence (F = 2.952, partial η2= 0.006, p = 0.032). We observed a significant association between ABO blood group genotypes and personality traits in a large number of healthy Japanese subjects. However, these results should be regarded as preliminary and should be interpreted with caution because it is possible that the association between ABO blood group genotype and the Persistence trait is relatively weak.

  2. Structural Investigation of Cesium Lead Halide Perovskites for High-Efficiency Quantum Dot Light-Emitting Diodes.

    PubMed

    Le, Quyet Van; Kim, Jong Beom; Kim, Soo Young; Lee, Byeongdu; Lee, Dong Ryeol

    2017-09-07

    We have investigated the effect of reaction temperature of hot-injection method on the structural properties of CsPbX 3 (X: Br, I, Cl) perovskite nanocrystals (NCs) using small- and wide-angle X-ray scattering. It is confirmed that the size of the NCs decreased as the reaction temperature decreased, resulting in stronger quantum confinement. The cubic-phase perovskite NCs formed despite the fact that the reaction temperatures increased from 140 to 180 °C; however, monodispersive NC cubes that are required for densely packing self-assembly film were formed only at lower temperatures. From the X-ray scattering measurements, the spin-coated film from more monodispersive perovskite nanocubes synthesized at lower temperatures resulted in more preferred orientation. This dense-packing perovskite film with preferred orientation yielded efficient light-emitting diode (LED) performance. Thus the dense-packing structure of NC assemblies formed after spin-coating should be considered for high-efficient LEDs based on perovskite quantum dots in addition to quantum confinement effect of the quantum dots.

  3. Structural origins of broadband emission from layered Pb-Br hybrid perovskites.

    PubMed

    Smith, Matthew D; Jaffe, Adam; Dohner, Emma R; Lindenberg, Aaron M; Karunadasa, Hemamala I

    2017-06-01

    Through structural and optical studies of a series of two-dimensional hybrid perovskites, we show that broadband emission upon near-ultraviolet excitation is common to (001) lead-bromide perovskites. Importantly, we find that the relative intensity of the broad emission correlates with increasing out-of-plane distortion of the Pb-(μ-Br)-Pb angle in the inorganic sheets. Temperature- and power-dependent photoluminescence data obtained on a representative (001) perovskite support an intrinsic origin to the broad emission from the bulk material, where photogenerated carriers cause excited-state lattice distortions mediated through electron-lattice coupling. In contrast, most inorganic phosphors contain extrinsic emissive dopants or emissive surface sites. The design rules established here could allow us to systematically optimize white-light emission from layered hybrid perovskites by fine-tuning the bulk crystal structure.

  4. Transition metal substituted SrTiO3 perovskite oxides as promising functional materials for oxygen sensor

    NASA Astrophysics Data System (ADS)

    Misra, Sunasira

    2012-07-01

    Modern industries employ several gases as process fluids. Leakage of these gases in the operating area could lead to undesirable consequences. Even in chemical industries, which use large quantities of inert gases in confined areas, accidental leakage of these process gases would result in the reduction of oxygen partial pressure in atmospheric air. For instance, large amounts of gaseous nitrogen and argon are used in pharmaceutical industries, gas filling/bottling plants, operating area of Fast Breeder reactors, etc. Fall of concentration of oxygen in air below 17% could lead to life risk (Asphyxiation) of the working personnel that has to be checked well in advance. Further, when the leaking gas is of explosive nature, its damage potential would be very high if its concentration level in air increases beyond its lower explosive limit. Surveillance of the ambient within these industries at the critical areas and also in the environment around them for oxygen therefore becomes highly essential. Sensitive and selective gas sensors made of advanced materials are required to meet this demand of monitoring environmental pollution. The perovskite class of oxides (ABO3) is chemically stable even at high temperatures and can tolerate large levels of dopants without phase transformations. The electronic properties of this parent functional material can be tailored by adding appropriate dopants that exhibit different valence states. Aliovalent transition metal substituted SrTiO3 perovskites are good mixed ionic and electronic conductors and potential candidates for sensing oxygen at percentage level exploiting their oxygen pressure dependent electrical conductivity. This paper presents the preparation, study of electrical conductivity and oxygen-sensing characteristics of iron and cobalt substituted SrTiO3.

  5. Thin-Film Transformation of NH4 PbI3 to CH3 NH3 PbI3 Perovskite: A Methylamine-Induced Conversion-Healing Process.

    PubMed

    Zong, Yingxia; Zhou, Yuanyuan; Ju, Minggang; Garces, Hector F; Krause, Amanda R; Ji, Fuxiang; Cui, Guanglei; Zeng, Xiao Cheng; Padture, Nitin P; Pang, Shuping

    2016-11-14

    Methylamine-induced thin-film transformation at room-temperature is discovered, where a porous, rough, polycrystalline NH 4 PbI 3 non-perovskite thin film converts stepwise into a dense, ultrasmooth, textured CH 3 NH 3 PbI 3 perovskite thin film. Owing to the beneficial phase/structural development of the thin film, its photovoltaic properties undergo dramatic enhancement during this NH 4 PbI 3 -to-CH 3 NH 3 PbI 3 transformation process. The chemical origins of this transformation are studied at various length scales. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. High-efficiency perovskite solar cells prepared by using a sandwich structure MAI-PbI2-MAI precursor film.

    PubMed

    Zhang, Xuhui; Ye, Jiajiu; Zhu, Liangzheng; Zheng, Haiying; Liu, Guozhen; Liu, Xuepeng; Duan, Bin; Pan, Xu; Dai, Songyuan

    2017-04-06

    Two-step deposition has been widely used in the perovskite layer preparation for perovskite solar cells due to its attractive morphology controllability. However, the limited diffusivity of CH 3 NH 3 I (MAI) might cause some PbI 2 to remain in the perovskite film. The residual PbI 2 in the perovskite film would lead to inferior performance of devices, such as, low power conversion efficiency (PCE), poor reproducibility and weak air stability. In this work, we developed a sandwich structure MAI-PbI 2 -MAI precursor film to prepare a PbI 2 -free CH 3 NH 3 PbI 3 perovskite film. In comparison to the two-step approach, the MAI-PbI 2 -MAI precursor film with a typical sandwich structure formed a uniform and pinhole-free perovskite film without any PbI 2 residue, which could significantly improve the performance of the devices. Moreover, the bottom MAI layer of the MAI-PbI 2 -MAI precursor film could improve the interfacial contact of the porous TiO 2 layer, leading to the promotion of the charge transfer and reduction of the recombination rate. Therefore, the devices fabricated from the sandwich structure MAI-PbI 2 -MAI precursor films showed dramatic improvements of open-circuit voltage (V oc ), short-circuit current density (J sc ), fill factor (FF) and PCE. As a result, a promising PCE of 17.8% with good long-term air stability was achieved for the MAI-PbI 2 -MAI precursor film based PSC, which is better than that prepared by a two-step approach.

  7. Room temperature three-photon pumped CH3NH3PbBr3 perovskite microlasers.

    PubMed

    Gao, Yisheng; Wang, Shuai; Huang, Can; Yi, Ningbo; Wang, Kaiyang; Xiao, Shumin; Song, Qinghai

    2017-03-28

    Hybrid lead halide perovskites have made great strides in next-generation light-harvesting and light emitting devices. Recently, they have also shown great potentials in nonlinear optical materials. Two-photon absorption and two-photon light emission have been thoroughly studied in past two years. However, the three-photon processes are rarely explored, especially for the laser emissions. Here we synthesized high quality CH 3 NH 3 PbBr 3 perovskite microstructures with solution processed precipitation method and studied their optical properties. When the microstructures are pumped with intense 1240 nm lasers, we have observed clear optical limit effect and the band-to-band photoluminescence at 540 nm. By increasing the pumping density, whispering-gallery-mode based microlasers have been achieved from CH 3 NH 3 PbBr 3 perovskite microplate and microrod for the first time. This work demonstrates the potentials of hybrid lead halide perovskites in nonlinear photonic devices.

  8. Room temperature three-photon pumped CH3NH3PbBr3 perovskite microlasers

    NASA Astrophysics Data System (ADS)

    Gao, Yisheng; Wang, Shuai; Huang, Can; Yi, Ningbo; Wang, Kaiyang; Xiao, Shumin; Song, Qinghai

    2017-03-01

    Hybrid lead halide perovskites have made great strides in next-generation light-harvesting and light emitting devices. Recently, they have also shown great potentials in nonlinear optical materials. Two-photon absorption and two-photon light emission have been thoroughly studied in past two years. However, the three-photon processes are rarely explored, especially for the laser emissions. Here we synthesized high quality CH3NH3PbBr3 perovskite microstructures with solution processed precipitation method and studied their optical properties. When the microstructures are pumped with intense 1240 nm lasers, we have observed clear optical limit effect and the band-to-band photoluminescence at 540 nm. By increasing the pumping density, whispering-gallery-mode based microlasers have been achieved from CH3NH3PbBr3 perovskite microplate and microrod for the first time. This work demonstrates the potentials of hybrid lead halide perovskites in nonlinear photonic devices.

  9. Effect of Thermal and Structural Disorder on the Electronic Structure of Hybrid Perovskite Semiconductor CH3NH3PbI3.

    PubMed

    Singh, Shivam; Li, Cheng; Panzer, Fabian; Narasimhan, K L; Graeser, Anna; Gujar, Tanaji P; Köhler, Anna; Thelakkat, Mukundan; Huettner, Sven; Kabra, Dinesh

    2016-08-04

    In this Letter, we investigate the temperature dependence of the optical properties of methylammonium lead iodide (MAPbI3 = CH3NH3PbI3) from room temperature to 6 K. In both the tetragonal (T > 163 K) and the orthorhombic (T < 163 K) phases of MAPbI3, the band gap (from both absorption and photoluminescence (PL) measurements) decreases with decrease in temperature, in contrast to what is normally seen for many inorganic semiconductors, such as Si, GaAs, GaN, etc. We show that in the perovskites reported here, the temperature coefficient of thermal expansion is large and accounts for the positive temperature coefficient of the band gap. A detailed analysis of the exciton line width allows us to distinguish between static and dynamic disorder. The low-energy tail of the exciton absorption is reminiscent of Urbach absorption. The Urbach energy is a measure of the disorder, which is modeled using thermal and static disorder for both the phases separately. The static disorder component, manifested in the exciton line width at low temperature, is small. Above 60 K, thermal disorder increases the line width. Both these features are a measure of the high crystal quality and low disorder of the perovskite films even though they are produced from solution.

  10. Photovoltaic switching mechanism in lateral structure hybrid perovskite solar cells

    DOE PAGES

    Yuan, Yongbo; Chae, Jungseok; Shao, Yuchuan; ...

    2015-06-05

    In this study, long range electromigration of methylammonium ions (MA +) in methyl ammonium lead tri-iodide (MAPbI 3) film is observed directly using the photo­thermal induced resonance technique. The electromigration of MA + leads to the formation of a lateral p-i-n structure, which is the origin of the switchable photovoltaic effect in MAPbI 3 perovskite devices.

  11. Influence of halide composition on the structural, electronic, and optical properties of mixed CH3NH3Pb (I1-xBrx) 3 perovskites calculated using the virtual crystal approximation method

    NASA Astrophysics Data System (ADS)

    Jong, Un-Gi; Yu, Chol-Jun; Ri, Jin-Song; Kim, Nam-Hyok; Ri, Guk-Chol

    2016-09-01

    Extensive studies have demonstrated the promising capability of the organic-inorganic hybrid halide perovskite CH3NH3PbI3 in solar cells with a high power conversion efficiency exceeding 20%. However, the intrinsic as well as extrinsic instabilities of this material remain the major challenge to the commercialization of perovskite-based solar cells. Mixing halides is expected to resolve this problem. Here, we investigate the effect of chemical substitution in the position of the halogen atom on the structural, electronic, and optical properties of mixed halide perovskites CH3NH3Pb (I1-xBrx) 3 with a pseudocubic phase using the virtual crystal approximation method within density functional theory. With an increase of Br content x from 0.0 to 1.0, the lattice constant decreases in proportion to x with the function of a (x )=6.420 -0.333 x (Å), while the band gap and the exciton binding energy increase with the quadratic function of Eg(x ) =1.542 +0.374 x +0.185 x2 (eV) and the linear function of Eb(x ) =0.045 +0.057 x (eV), respectively. The photoabsorption coefficients are also calculated, showing a blueshift of the absorption onsets for higher Br contents. We calculate the phase decomposition energy of these materials and analyze the electronic charge density difference to estimate the material stability. Based on the calculated results, we suggest that the best match between efficiency and stability can be achieved at x ≈0.2 in CH3NH3Pb (I1-xBrx) 3 perovskites.

  12. General working principles of CH3NH3PbX3 perovskite solar cells.

    PubMed

    Gonzalez-Pedro, Victoria; Juarez-Perez, Emilio J; Arsyad, Waode-Sukmawati; Barea, Eva M; Fabregat-Santiago, Francisco; Mora-Sero, Ivan; Bisquert, Juan

    2014-02-12

    Organometal halide perovskite-based solar cells have recently realized large conversion efficiency over 15% showing great promise for a new large scale cost-competitive photovoltaic technology. Using impedance spectroscopy measurements we are able to separate the physical parameters of carrier transport and recombination in working devices of the two principal morphologies and compositions of perovskite solar cells, viz. compact thin films of CH3NH3PbI(3-x)Clx and CH3NH3PbI3 infiltrated on nanostructured TiO2. The results show nearly identical spectral characteristics indicating a unique photovoltaic operating mechanism that provides long diffusion lengths (1 μm). Carrier conductivity in both devices is closely matched, so that the most significant differences in performance are attributed to recombination rates. These results highlight the central role of the CH3NH3PbX3 semiconductor absorber in carrier collection and provide a new tool for improved optimization of perovskite solar cells. We report for the first time a measurement of the diffusion length in a nanostructured perovskite solar cell.

  13. Hybrid Organic-Inorganic Perovskites: Structural Diversity and Opportunities for Semiconductor Design

    NASA Astrophysics Data System (ADS)

    Mitzi, David

    Photovoltaic (PV) devices based on three-dimensional perovskites, (Cs, MA, FA)Pb(I, Br)3 (MA =methylammonium, FA =formamidinium), have attracted substantial recent interest, because of the unprecedented rise in power conversion efficiency to values above 20%, which in turn is made possible by the near ideal band gap, strong optical absorption, high carrier mobilities, long minority carrier lifetimes, and relatively benign defects and grain boundaries for the absorbers. Some of the same properties that render these materials near-ideal for PV, also make them attractive for LED and other optoelectronic applications. Despite the high levels of device performance, the incorporation of the heavy metal lead, coupled with issues of device stability and electrical hysteresis pose challenges for commercializing these exciting technologies. This talk will provide a perspective on and discuss recent advances related to the broader perovskite family, focusing on the extraordinary structural/chemical diversity, including ability to control structural/electronic dimensionality, substitute on the organic cation, metal or halogen sites, and prospects of multi-functionality arising from separately engineered organic/inorganic structural components (e.g., see). Further exploration within this perovskite structural and chemical space offers exciting opportunities for future energy and electronic materials design. This work has been financially supported by the Office of Energy Efficiency and Renewable Energy (EERE), U.S. Dept. of Energy, under Award Number DE-EE0006712.

  14. Clinical evaluation of the endothelial tie-2 crossmatch in ABO compatible and ABO incompatible renal transplants.

    PubMed

    Kafetzi, Maria L; Boletis, John N; Melexopoulou, Christine A; Tsakris, Athanassios; Iniotaki, Aliki G; Doxiadis, Ilias I N

    2013-11-01

    The necessity of detection of other than the classical major histocompatibility complex (MHC) and MHC class I-related chain A (MICA) directed antibodies prior to organ transplantation has already been repeatedly reported. A commercial flow cytometric endothelial crossmatch (CM) using isolated peripheral blood tie-2 positive cells provides a tool to detect non-MHC antibodies in addition to antibodies directed to MHC class I and II. The vast majority of circulating tie-2 positive cells expresses HLA-DR but not the A, B blood group antigens. Tie-2 cells are circulating surrogate endothelial cells. In this retrospective study we evaluated the endothelial CM in 51 renal transplantations, 30 with ABO compatible grafts and 21 with ABO incompatible grafts. Fifteen of the ABO compatible recipients (group A) developed unexplained rejection episodes (RE) while the remaining 15 had no RE (group B). Five cases of group A and none of group B had a positive tie-2 CM before transplantation (p=0.042). A positive tie-2 CM was also correlated with graft failure in ABO compatible transplants (p=0.02). No significant correlation was found between a positive pre-transplant tie-2 CM and RE in the ABO incompatible group. This study strongly suggest that a positive tie-2 CM may predict post-transplantation complications in ABO compatible grafts while negative reactions are not predictive. The test is not significantly correlated with RE in ABO incompatible grafts possibly due to applied desensitization. Copyright © 2013 American Society for Histocompatibility and Immunogenetics. Published by Elsevier Inc. All rights reserved.

  15. Magnetic resonances in perovskite-type layer structures

    NASA Astrophysics Data System (ADS)

    Strobel, K.; Geick, R.

    1981-08-01

    We have studied the q=0 magnetic excitations of the perovskite-type layer structures A 2MnCl 4 with A=Rb, C nH 2n+1NH 3 (n=1,2,3), and NH 3(CH 2) mNH 3MnCl 4 (m=2,4,5) in the antiferromagnetic and in the spin flop regime by means of magnetic resonance in the mm-wave range (30-130GHz) and microwave range (9.2GHz). The length of the organic molecules determines the separation of the MnCl 6 octahedra. With increasing separation the Néel temperature and the antiferromagnetic resonance frequency decrease, which mainly originates from a decrease of the anisotropy field.

  16. Structural, magnetic and transport properties of 2D structured perovskite oxychalcogenides

    NASA Astrophysics Data System (ADS)

    Berthebaud, David; Lebedev, Oleg I.; Pelloquin, Denis; Maignan, Antoine

    2014-10-01

    We have been looking for new potential thermoelectric materials in the family of 2D structured perovskite oxychalcogenides containing [Cu2Ch2]2- blocks (Ch = S or Se). Using high temperature syntheses, a new oxyselenide Sr2CuFeO3Se has been isolated and its structure has been compared to the isotypes sulfides, Ca2CuFeO3S and Sr2CuFeO3S, prepared by the same technique. By combining powder XRD and TEM analyses their composition and structure were analyzed. They all three crystallize in the Sr2CuGaO3S-type structure, with only the oxyselenide showing a Fe deficiency which is related to the stacking faults evidenced by high resolution TEM. Transport and magnetic properties of the samples have been studied; especially their electrical resistivity is characterized by high values in the range from 1 to 10 kΩ cm at 300 K. Thermoelectric potential of these materials is also discussed.

  17. Growth of highly textured PbTiO3 films on conductive substrate under hydrothermal conditions

    NASA Astrophysics Data System (ADS)

    Tang, Haixiong; Zhou, Zhi; Bowland, Christopher C.; Sodano, Henry A.

    2015-08-01

    Perovskite structure (ABO3) thin films have wide applications in electronic devices due to their unique properties, including high dielectric permittivity, ferroelectricity and piezoelectric coupling. Here, we report an approach to grow highly textured thick lead titanate (PbTiO3) films on conductive substrates by a two-step hydrothermal reaction. Initially, vertically aligned TiO2 nanowire arrays are grown on fluorine-doped tin oxide (FTO) coated glass, which act as template crystals for conversion to the perovskite structure. The PbTiO3 films are then converted from TiO2 NW arrays by diffusing Pb2+ ions into the template through a second hydrothermal reaction. The dielectric permittivity and piezoelectric coupling coefficient (d33) of the PbTiO3 films are as high as 795 at 1 kHz and 52 pm V-1, respectively. The reported process can also potentially be expanded for the assembly of other complex perovskite ATiO3 (A = Ba, Ca, Cd, etc) films by using the highly aligned TiO2 NW arrays as templates. Therefore, the approach introduced here opens up a new door to synthesize ferroelectric thin films on conductive substrates for application in sensors, actuators, and ultrasonic transducers that are important in various industrial and scientific areas.

  18. Proximity to a ferroelectric instability in Ba1-xCaxZrO3

    NASA Astrophysics Data System (ADS)

    Kim, H. S.; Christen, H. M.; Biegalski, M. D.; Singh, D. J.

    2010-09-01

    Ferroelectricity in ABO3 perovskites driven by A-site disorder is seen as a powerful approach toward lead-free piezoelectrics and ferroelectrics as well as to forming multiferroic compounds. Here we investigate the Ba1-xCaxZrO3 solid solution by structural and dielectric measurements on pulsed laser deposition grown films and by first principles calculations. Films on SrRuO3-coated SrTiO3 substrates are studied for x between 0 and 0.44. Despite the expectation that the Ca-ions assume off-center positions in the perovskite lattice, dielectric measurements show no evidence for ferroelectricity. This behavior is explained by first principles supercell calculations that show ferroelectricity at expanded volume but a rapid suppression thereof as the volume is reduced, thus indicating that our paraelectric Ba1-xCaxZrO3 films are close to a ferroelectric instability. These results demonstrate the important interplay between unit cell volume and ferroelectricity arising from off-centered ions.

  19. 2D Ruddlesden-Popper Perovskites for Optoelectronics.

    PubMed

    Chen, Yani; Sun, Yong; Peng, Jiajun; Tang, Junhui; Zheng, Kaibo; Liang, Ziqi

    2018-01-01

    Conventional 3D organic-inorganic halide perovskites have recently undergone unprecedented rapid development. Yet, their inherent instabilities over moisture, light, and heat remain a crucial challenge prior to the realization of commercialization. By contrast, the emerging 2D Ruddlesden-Popper-type perovskites have recently attracted increasing attention owing to their great environmental stability. However, the research of 2D perovskites is just in their infancy. In comparison to 3D analogues, they are natural quantum wells with a much larger exciton binding energy. Moreover, their inner structural, dielectric, optical, and excitonic properties remain to be largely explored, limiting further applications. This review begins with an introduction to 2D perovskites, along with a detailed comparison to 3D counterparts. Then, a discussion of the organic spacer cation engineering of 2D perovskites is presented. Next, quasi-2D perovskites that fall between 3D and 2D perovskites are reviewed and compared. The unique excitonic properties, electron-phonon coupling, and polarons of 2D perovskites are then be revealed. A range of their (opto)electronic applications is highlighted in each section. Finally, a summary is given, and the strategies toward structural design, growth control, and photophysics studies of 2D perovskites for high-performance electronic devices are rationalized. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Modulated CH3NH3PbI3−xBrx film for efficient perovskite solar cells exceeding 18%

    PubMed Central

    Tu, Yongguang; Wu, Jihuai; Lan, Zhang; He, Xin; Dong, Jia; Jia, Jinbiao; Guo, Panfeng; Lin, Jianming; Huang, Miaoliang; Huang, Yunfang

    2017-01-01

    The organic-inorganic lead halide perovskite layer is a crucial factor for the high performance perovskite solar cell (PSC). We introduce CH3NH3Br in the precursor solution to prepare CH3NH3PbI3−xBrx hybrid perovskite, and an uniform perovskite layer with improved crystallinity and apparent grain contour is obtained, resulting in the significant improvement of photovoltaic performance of PSCs. The effects of CH3NH3Br on the perovskite morphology, crystallinity, absorption property, charge carrier dynamics and device characteristics are discussed, and the improvement of open circuit voltage of the device depended on Br doping is confirmed. Based on above, the device based on CH3NH3PbI2.86Br0.14 exhibits a champion power conversion efficiency (PCE) of 18.02%. This study represents an efficient method for high-performance perovskite solar cell by modulating CH3NH3PbI3−xBrx film. PMID:28303938

  1. Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 perovskites for solar cell applications.

    PubMed

    Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo

    2014-03-26

    Hybrid AMX3 perovskites (A = Cs, CH3NH3; M = Sn, Pb; X = halide) have revolutionized the scenario of emerging photovoltaic technologies, with very recent results demonstrating 15% efficient solar cells. The CH3NH3PbI3/MAPb(I(1-x)Cl(x))3 perovskites have dominated the field, while the similar CH3NH3SnI3 has not been exploited for photovoltaic applications. Replacement of Pb by Sn would facilitate the large uptake of perovskite-based photovoltaics. Despite the extremely fast progress, the materials electronic properties which are key to the photovoltaic performance are relatively little understood. Density Functional Theory electronic structure methods have so far delivered an unbalanced description of Pb- and Sn-based perovskites. Here we develop an effective GW method incorporating spin-orbit coupling which allows us to accurately model the electronic, optical and transport properties of CH3NH3SnI3 and CH3NH3PbI3, opening the way to new materials design. The different CH3NH3SnI3 and CH3NH3PbI3 electronic properties are discussed in light of their exploitation for solar cells, and found to be dominantly due to relativistic effects. These effects stabilize the CH3NH3PbI3 material towards oxidation, by inducing a deeper valence band edge. Relativistic effects, however, also increase the material band-gap compared to CH3NH3SnI3, due to the valence band energy downshift (~0.7 eV) being only partly compensated by the conduction band downshift (~0.2 eV).

  2. Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications

    PubMed Central

    Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo

    2014-01-01

    Hybrid AMX3 perovskites (A = Cs, CH3NH3; M = Sn, Pb; X = halide) have revolutionized the scenario of emerging photovoltaic technologies, with very recent results demonstrating 15% efficient solar cells. The CH3NH3PbI3/MAPb(I1−xClx)3 perovskites have dominated the field, while the similar CH3NH3SnI3 has not been exploited for photovoltaic applications. Replacement of Pb by Sn would facilitate the large uptake of perovskite-based photovoltaics. Despite the extremely fast progress, the materials electronic properties which are key to the photovoltaic performance are relatively little understood. Density Functional Theory electronic structure methods have so far delivered an unbalanced description of Pb- and Sn-based perovskites. Here we develop an effective GW method incorporating spin-orbit coupling which allows us to accurately model the electronic, optical and transport properties of CH3NH3SnI3 and CH3NH3PbI3, opening the way to new materials design. The different CH3NH3SnI3 and CH3NH3PbI3 electronic properties are discussed in light of their exploitation for solar cells, and found to be dominantly due to relativistic effects. These effects stabilize the CH3NH3PbI3 material towards oxidation, by inducing a deeper valence band edge. Relativistic effects, however, also increase the material band-gap compared to CH3NH3SnI3, due to the valence band energy downshift (~0.7 eV) being only partly compensated by the conduction band downshift (~0.2 eV). PMID:24667758

  3. ABO-Rh blood groups distribution in cardiac syndrome X patients.

    PubMed

    Kheradmand, Fatemeh; Rasmi, Yousef; Nemati, Mohaddeseh; Mohammadzad, Mir Hossein Seyed

    2012-07-01

    Data on frequency distribution of ABO-Rh blood groups in cardiac syndrome X (CSX) patients are not available. We aimed to investigate the distribution of ABO-Rh blood groups in these patients. A total of 247 CSX patients' records were reviewed in a cross-sectional study from 2006 to 2010. One hundred forty six patients (59.1%) were female, and the mean patient age was 52 ± 11 years. The frequency of ABO-Rh blood groups was compared to the frequency of these blood groups in the West-Azerbaijan province, Iran; general population. Blood groups distribution among CSX patients showed phenotypes A, B, AB, O and Rh negative as 33.1%, 21.9%, 9.3%, 35.8%, and 7.9%, respectively. According to our results, there were no differences in ABO-Rh blood groups distribution between CSX patients and normal population. These data suggest that ABO-Rh blood groups might be unassociated with CSX.

  4. Crystal structure, stability, and optoelectronic properties of the organic-inorganic wide-band-gap perovskite CH3NH3BaI3 : Candidate for transparent conductor applications

    NASA Astrophysics Data System (ADS)

    Kumar, Akash; Balasubramaniam, K. R.; Kangsabanik, Jiban; Vikram, Alam, Aftab

    2016-11-01

    Structural stability, electronic structure, and optical properties of CH3NH3BaI3 hybrid perovskite are examined from theory as well as experiment. Solution-processed thin films of CH3NH3BaI3 exhibited a high transparency in the wavelength range of 400-825 nm (1.5-3.1 eV for which the photon current density is highest in the solar spectrum) which essentially justifies a high band gap of 4 eV obtained by theoretical estimation. Also, the x-ray diffraction patterns of the thin films match well with the {00 l } peaks of the simulated pattern obtained from the relaxed unit cell of CH3NH3BaI3 , crystallizing in the I 4 /m c m space group, with lattice parameters, a =9.30 Å, c =13.94 Å. Atom projected density of state and band structure calculations reveal the conduction and valence band edges to be comprised primarily of barium d orbitals and iodine p orbitals, respectively. The larger band gap of CH3NH3BaI3 compared to CH3NH3PbI3 can be attributed to the lower electronegativity coupled with the lack of d orbitals in the valence band of Ba2 +. A more detailed analysis reveals the excellent chemical and mechanical stability of CH3NH3BaI3 against humidity, unlike its lead halide counterpart, which degrades under such conditions. We propose La to be a suitable dopant to make this compound a promising candidate for transparent conductor applications, especially for all perovskite solar cells. This claim is supported by our calculated results on charge concentration, effective mass, and vacancy formation energies.

  5. The effect of strontium and barium doping on perovskite-structured energy materials for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Wu, Ming-Chung; Chen, Wei-Cheng; Chan, Shun-Hsiang; Su, Wei-Fang

    2018-01-01

    Perovskite solar cell is a novel photovoltaic technology with the superior progress in efficiency and the simple solution processes. Develop lead-free or lead-reduced perovskite materials is a significant concern for high-performance perovskite solar cell. Among the alkaline earth metals, the Sr2+ and Ba2+ are suitable for Pb2+ replacement in perovskite film due to fitting Goldschmidt's tolerance factor. In this study, we adopted Ba-doped and Sr-doped perovskite structured materials with different doping levels, including 1.0, 5.0, and 10.0 mol%, to prepare perovskite solar cells. Both Ba-doped and Sr-doped perovskite structured materials have a related tendency in absorption behavior and surface morphology. At 10.0 mol% doping level, the power conversion efficiency (PCE) of Sr-doped perovskite solar cells is only ∼0.5%, but the PCE of Ba-doped perovskite solar cells can be achieved to ∼9.7%. Ba-doped perovskite solar cells showed the acceptable photovoltaic characteristics than Sr-doped perovskite solar cells. Ba dopant can partially replace the amount of lead in the perovskite solar cells, and it could be a potential candidate in the field of lead-free or lead-reduced perovskite energy materials.

  6. Large anisotropic thermoelectricity in perovskite related layered structure: SrnNbnO3n+2 (n = 4,5)

    NASA Astrophysics Data System (ADS)

    Sakai, Akihiro; Takahashi, Kouhei; Kanno, Tsutomu; Adachi, Hideaki

    2011-05-01

    We have systematically synthesized a series of perovskite related layered structures, Strontium-Niobates expressed as SrnNbnO3n+2 (n = 4 ~ 5) and focused on the thermoelectricity in n = 4 and 5 type materials here. To explore their thermoelectricities and anisotropic properties, we have measured the thermal and charge transport properties along all crystallographic axes. The values of thermoelectric parameters were strongly anisotropic and there exists a large anisotropy even in in-plane direction of the layered structure. As a result, the best performance of thermoelectricity is commonly observed in the a-axis. The respective ZT for Sr1.8La0.2Nb2O7 and Sr5Nb5O17 at room temperature is 3.5×10-2 and 3.6×10-3.

  7. Electrical and structural behaviour of the perovskite LaCr0.4Co0.4Fe0.2O3

    NASA Astrophysics Data System (ADS)

    Rativa-Parada, W.; Gómez-Cuaspud, J. A.; Vera-López, E.; Carda-Castelló, J. B.

    2017-12-01

    The electrical and structural properties of the LaCr0.4Co0.4Fe0.2O3 perovskite are investigated. The oxide is synthetized by polymerization-combustion method, using citric acid as a chelating agent and low calcination temperature. The X-ray diffraction, Raman spectroscopy and transmission electron microscopy analysis show conformation of a pure phase with rhombohedral (R-3c) structure and confirmed high structural crystallinity facilitated by synthesis method. The characterization by means of impedance spectroscopy is performed at room temperature. It is observed that the oxides behave as materials of the semiconductor type and that the conductivity increase in accordance to a thermal excitation phenomenon.

  8. Making and Breaking of Lead Halide Perovskites.

    PubMed

    Manser, Joseph S; Saidaminov, Makhsud I; Christians, Jeffrey A; Bakr, Osman M; Kamat, Prashant V

    2016-02-16

    kinetics can be tailored to yield improved thin film homogeneity. Because degradation of the as-formed perovskite film is in many ways analogous to its initial formation, the same suite of monitoring techniques reveals the moisture-induced transformation of low band gap methylammonium lead iodide (CH3NH3PbI3) to wide band gap hydrate compounds. The rate of degradation is increased upon exposure to light. Interestingly, the hydration process is reversible under certain conditions. This facile formation and subsequent chemical lability raises the question of whether CH3NH3PbI3 and its analogues are thermodynamically stable phases, thus posing a significant challenge to the development of transformative perovskite photovoltaics. Adequately addressing issues of structural and chemical stability under real-world operating conditions is paramount if perovskite solar cells are to make an impact beyond the benchtop. Expanding our fundamental knowledge of lead halide perovskite formation and degradation pathways can facilitate fabrication of stable, high-quality perovskite thin films for the next generation of photovoltaic and light emitting devices.

  9. Making and Breaking of Lead Halide Perovskites

    DOE PAGES

    Manser, Joseph S.; Saidaminov, Makhsud I.; Christians, Jeffrey A.; ...

    2016-01-20

    , crystallization kinetics can be tailored to yield improved thin film homogeneity. Because degradation of the as-formed perovskite film is in many ways analogous to its initial formation, the same suite of monitoring techniques reveals the moisture-induced transformation of low band gap methylammonium lead iodide (CH 3NH 3PbI 3) to wide band gap hydrate compounds. The rate of degradation is increased upon exposure to light. Interestingly, the hydration process is reversible under certain conditions. This facile formation and subsequent chemical lability raises the question of whether CH 3NH 3PbI 3 and its analogues are thermodynamically stable phases, thus posing a significant challenge to the development of transformative perovskite photovoltaics. Adequately addressing issues of structural and chemical stability under real-world operating conditions is paramount if perovskite solar cells are to make an impact beyond the benchtop. Expanding our fundamental knowledge of lead halide perovskite formation and degradation pathways can facilitate fabrication of stable, high-quality perovskite thin films for the next generation of photovoltaic and light emitting devices.« less

  10. Perovskite oxides: Oxygen electrocatalysis and bulk structure

    NASA Technical Reports Server (NTRS)

    Carbonio, R. E.; Fierro, C.; Tryk, D.; Scherson, D.; Yeager, Ernest

    1987-01-01

    Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

  11. Phase formation and UV luminescence of Gd3+ doped perovskite-type YScO3

    NASA Astrophysics Data System (ADS)

    Shimizu, Yuhei; Ueda, Kazushige

    2016-10-01

    Synthesis of pure and Gd3+doped perovskite-type YScO3 was attempted by a polymerized complex (PC) method and solid state reaction (SSR) method. Crystalline phases and UV luminescence of samples were examined with varying heating temperatures. The perovskite-type single phase was not simply formed in the SSR method, as reported in some literatures, and two cubic C-type phases of starting oxide materials remained forming slightly mixed solid solutions. UV luminescence of Gd3+ doped samples increased with an increase in heating temperatures and volume of the perovskite-type phase. In contrast, a non-crystalline precursor was crystallized to a single C-type phase at 800 °C in the PC method forming a completely mixed solid solution. Then, the phase of perovskite-type YScO3 formed at 1200 °C and its single phase was obtained at 1400 °C. It was revealed that high homogeneousness of cations was essential to generate the single perovskite-phase of YScO3. Because Gd3+ ions were also dissolved into the single C-type phase in Gd3+ doped samples, intense UV luminescence was observed above 800 °C in both C-type phase and perovskite-type phase.

  12. Structural, electronic, elastic, and thermal properties of CaNiH3 perovskite obtained from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Benlamari, S.; Bendjeddou, H.; Boulechfar, R.; Amara Korba, S.; Meradji, H.; Ahmed, R.; Ghemid, S.; Khenata, R.; Omran, S. Bin

    2018-03-01

    A theoretical study of the structural, elastic, electronic, mechanical, and thermal properties of the perovskite-type hydride CaNiH3 is presented. This study is carried out via first-principles full potential (FP) linearized augmented plane wave plus local orbital (LAPW+lo) method designed within the density functional theory (DFT). To treat the exchange–correlation energy/potential for the total energy calculations, the local density approximation (LDA) of Perdew–Wang (PW) and the generalized gradient approximation (GGA) of Perdew–Burke–Ernzerhof (PBE) are used. The three independent elastic constants (C 11, C 12, and C 44) are calculated from the direct computation of the stresses generated by small strains. Besides, we report the variation of the elastic constants as a function of pressure as well. From the calculated elastic constants, the mechanical character of CaNiH3 is predicted. Pertaining to the thermal properties, the Debye temperature is estimated from the average sound velocity. To further comprehend this compound, the quasi-harmonic Debye model is used to analyze the thermal properties. From the calculations, we find that the obtained results of the lattice constant (a 0), bulk modulus (B 0), and its pressure derivative ({B}0^{\\prime }) are in good agreement with the available theoretical as well as experimental results. Similarly, the obtained electronic band structure demonstrates the metallic character of this perovskite-type hydride.

  13. Intrinsic Mechanisms of Multi-Layer Ceramic Capacitor Failure.

    DTIC Science & Technology

    1984-04-01

    Properties on the Electric Transport in ABO Perovskites ", Phys. 3Stat. Sol. (a) 75, 143 (1983). [10] S. A. Long and R. N. Blumenthal, "Ti-Rich...Bauerle, "Influence Ed.), John Wiley and Sons (1981). of Bulk and Interface Properties on the Electric Transport in ABO Perovskites ", Phys. Stat. Sol...48 4. THERMOELECTRIC MEASUREMENTS ..... .............. .. 51 5. OTHER STUDIES ........ .................... 60 5.1 Impedance Dispersion

  14. Analysis of the local structure around Cr3+ centers in perovskite KMgF3 using both ab initio (DFT) and semi-empirical (SPM) calculations

    NASA Astrophysics Data System (ADS)

    Emül, Y.; Erbahar, D.; Açıkgöz, M.

    2014-11-01

    The local structure around Cr3+ centers in perovskite KMgF3 crystal have been investigated through the applications of both an ab-initio, density functional theory (DFT), and a semi empirical, superposition model (SPM), analyses. A supercell approach is used for DFT calculations. All the tetragonal (Cr3+-VMg and Cr3+-Li+), trigonal (Cr3+-VK), and CrF5O cluster centers have been considered with various structural models based on the previously suggested experimental inferences. The significant structural changes around the Cr3+ centers induced by Mg2+ or K+ vacancies and the Li substitution at those vacancy sites have been determined and discussed by means of charge distribution. This study provides insight on both the roles of Mg2+ and K+ vacancies and Li+ ion in the local structural properties around Cr3+ centers in KMgF3.

  15. Phase formation and UV luminescence of Gd{sup 3+} doped perovskite-type YScO{sub 3}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shimizu, Yuhei; Ueda, Kazushige, E-mail: kueda@che.kyutech.ac.jp

    Synthesis of pure and Gd{sup 3+}doped perovskite-type YScO{sub 3} was attempted by a polymerized complex (PC) method and solid state reaction (SSR) method. Crystalline phases and UV luminescence of samples were examined with varying heating temperatures. The perovskite-type single phase was not simply formed in the SSR method, as reported in some literatures, and two cubic C-type phases of starting oxide materials remained forming slightly mixed solid solutions. UV luminescence of Gd{sup 3+} doped samples increased with an increase in heating temperatures and volume of the perovskite-type phase. In contrast, a non-crystalline precursor was crystallized to a single C-type phasemore » at 800 °C in the PC method forming a completely mixed solid solution. Then, the phase of perovskite-type YScO{sub 3} formed at 1200 °C and its single phase was obtained at 1400 °C. It was revealed that high homogeneousness of cations was essential to generate the single perovskite-phase of YScO{sub 3}. Because Gd{sup 3+} ions were also dissolved into the single C-type phase in Gd{sup 3+} doped samples, intense UV luminescence was observed above 800 °C in both C-type phase and perovskite-type phase. - Graphical abstract: A pure perovskite-type YScO{sub 3} phase was successfully synthesized by a polymerized complex (PC) method. The perovskite-type YScO{sub 3} was generated through a solid solution of C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} with drastic change of morphology. The PC method enabled a preparation of the single phase of the perovskite-type YScO{sub 3} at lower temperature and in shorter heating time. Gd{sup 3+} doped perovskite-type YScO{sub 3} was found to show a strong sharp UV emission at 314 nm. - Highlights: • Pure YScO{sub 3} phase was successfully synthesized by polymerized complex (PC) method. • Pure perovskite-type YScO{sub 3} phase was generated from pure C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} one. • YScO{sub 3} was obtained at lower

  16. Molecular Self-Assembly Fabrication and Carrier Dynamics of Stable and Efficient CH3 NH3 Pb(1-x) Snx I3 Perovskite Solar Cells.

    PubMed

    Fan, Jiandong; Liu, Chong; Li, Hongliang; Zhang, Cuiling; Li, Wenzhe; Mai, Yaohua

    2017-10-09

    The Sn-based perovskite solar cells (PSCs) provide the possibility of swapping the Pb element toward developing toxic-free PSCs. Here, we innovatively employed a molecular self-assembly approach to obtain a series CH 3 NH 3 Pb (1-x) Sn x I 3 (0≤x≤1) perovskite thin films with full coverage. The optimized planar CH 3 NH 3 Pb 0.75 Sn 0.25 I 3 PSC with inverted structure was consequently realized with a maximum power conversion efficiency (PCE) over 14 %, which displayed a stabilized power output (SPO) over 12 % within 200 s at 0.6 V forward bias. Afterward, we investigated the factors that limited the efficiency improvement of hybrid Sn-Pb PSCs, and analyzed the possible reason of the hysteresis effect occurred even in the inverted structure cell. Particularly, the oxidation of hybrid Sn-Pb perovskite thin film was demonstrated to be the main reason that limited its further efficiency improvement. The imbalance of charge transport was intensified, which was associated with the increased hole defect-state density and decreased electron defect-state density after Sn was introduced. This study helps tackle the intractable issue regarding the toxic Pb in perovskite devices and is a step forward toward realizing lead-free PSCs with high stability and efficiency. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Allelic Prevalence of ABO Blood Group Genes in Iranian Azari Population.

    PubMed

    Nojavan, Mohammad; Shamsasenjan, Karrim; Movassaghpour, Ali Akbar; Akbarzadehlaleh, Parvin; Torabi, Seyd Esmail; Ghojazadeh, Morteza

    2012-01-01

    ABO blood group system is the most important blood group in transfusion and has been widely used in population studies. Several molecular techniques for ABO allele's detection are widely used for distinguishing various alleles of glycosyl transferase locus on chromosome 9. 744 randomly selected samples from Azari donors of East Azerbaijan province (Iran) were examined using well-adjusted multiplex allele- specific PCR ABO genotyping technique. The results were consistent for all individuals. The ABO blood group genotype of 744 healthy Azari blood donors was: 25.8% AA/AO (2), 7.6% AO (1), 1.6% BB, 11.3% B0 (1), 10% AB, 9.3% 0(1)0(1) and 15.3%0(1)0(2). The highest genotype frequency belonged to O01/O02 genotype (15.3%) and the lowest frequency belonged to A101/A102 genotype (0.4%). The frequencies of ABO alleles didn't show significant differences between East Azerbaijan province population and that of other areas of the country. Meanwhile, statistical analysis of frequencies of A and B alleles between East Azerbaijan province population and neighbor countries showed significant differences whereas the frequency of allele O between them did not show significant difference (P>0.05). The frequencies of ABO alleles didn't show significant differences between East Azerbaijan province population and that of other areas of the country. Meanwhile, statistical analysis of frequencies of A and B alleles between East Azerbaijan province population and neighbor countries showed significant differences whereas the frequency of allele O between them did not show significant difference (P>0.05).

  18. Transparent and flexible photodetectors based on CH3NH3PbI3 perovskite nanoparticles

    NASA Astrophysics Data System (ADS)

    Jeon, Young Pyo; Woo, Sung Jun; Kim, Tae Whan

    2018-03-01

    Transparent and flexible photodetectors (PDs) based on CH3NH3PbI3 perovskite nanoparticles (NPs) were fabricated by using co-evaporation of methyl ammonium iodide and lead iodide. X-ray diffraction patterns and high-resolution transmission electron microscopy images demonstrated the formation of perovskite NPs. The optical transmittance of the perovskite NPs/glass was above 80% over the entire range of visible wavelengths, indicative of high transparency. The PDs based on CH3NH3PbI3 perovskite NPs were sensitive to a broad range of visible light from 450 to 650 nm. The currents in the PDs under exposure to red, green, and blue light-emitting diodes were enhanced to 5, 10, and 20 times that of the PD in the dark, respectively. The rise and the decay times of the PDs were 50 and 120 μs. The current in the perovskite NP PD on a polyethylene terephthalate substrate was enhanced by approximately 69% when the NP PD was exposed to a blue LED emitting at a wavelength of 459 nm. Despite multiple bending, the transparent and flexible PDs based on methyl ammonium iodide and lead iodide NPs showed reproducibility and high stability in performance.

  19. Growth of MAPbBr3 perovskite crystals and its interfacial properties with Al and Ag contacts for perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Najeeb, Mansoor Ani; Ahmad, Zubair; Shakoor, R. A.; Alashraf, Abdulla; Bhadra, Jolly; Al-Thani, N. J.; Al-Muhtaseb, Shaheen A.; Mohamed, A. M. A.

    2017-11-01

    In this work, the MAPbBr3 perovskite crystals were grown and the interfacial properties of the poly-crystalline MAPbBr3 with Aluminum (Al) and Silver (Ag) contacts has been investigated. MAPbBr3 crystals are turned into the poly-crystalline pellets (PCP) using compaction technique and the Al/PCP, Al/interface layer/PCP, Ag/PCP, and Ag/interface layer/PCP contacts were investigated. Scanning Electron Microscopic (SEM), Energy-dispersive X-ray spectroscopy (EDX) and current-voltage (I-V) characteristic technique were used to have an insight of the degradation mechanism happening at the Metal/perovskite interface. The Ag/PCP contact appears to be stable, whereas Al is found to be highly reactive with the MAPbBr3 perovskite crystals due to the infiltration setback of Al in to the perovskite crystals. The interface layer showed a slight effect on the penetration of Al in to the perovskite crystals however it does not seem to be an appropriate solution. It is noteworthy that the stability of the underlying metal/perovskite contact is very crucial towards the perovskite solar cells with extended device lifetime.

  20. Effects of Fe-Enrichment on the Equation of State and Stability of (Mg,Fe)SiO3 Perovskite and Post-Perovskite

    NASA Astrophysics Data System (ADS)

    Dorfman, S. M.; Holl, C. M.; Meng, Y.; Prakapenka, V.; Duffy, T. S.

    2010-12-01

    Fe-enrichment in the deep lower mantle has been proposed as an explanation for seismic anomalies such as large low shear velocity provinces (LLSVPs) and ultralow velocity zones (ULVZs). In order to resolve the effect of Fe on the stability and equation of state of the lower mantle’s dominant constituent, (Mg,Fe)SiO3 perovskite, we have studied Fe-rich natural orthopyroxenes, (Mg0.61Fe0.37Ca0.02)SiO3 and (Mg0.25Fe0.70Ca0.05)SiO3 (compositions determined by microprobe analysis), at lower mantle P-T conditions. Pyroxene starting materials were mixed with Au (pressure calibrant and laser absorber) and loaded with NaCl or Ne (pressure medium and thermal insulator) in a symmetric diamond anvil cell. X-ray diffraction experiments at pressures up to 122 GPa with in-situ laser heating were performed at the GSECARS (13-ID-D) and HPCAT (16-ID-B) sectors of the Advanced Photon Source. Heating samples to 2000 K produced single-phase orthorhombic GdFeO3-type perovskite at 63 GPa for the Mg# 61 composition and at 72 GPa for the Mg# 25 composition. At lower pressures (56 GPa for Mg# 61, 67 GPa for Mg# 25), heating both compositions resulted in a mixture of perovskite, SiO2 and (Mg,Fe)O. These measurements provide new constraints on the dependence of (Mg,Fe)SiO3 perovskite stability on pressure and composition. Upon further compression to 93 GPa and higher pressures with laser heating, Mg# 25 perovskite transformed to a two-phase mixture of perovskite and post-perovskite. This is consistent with previous findings that Fe substitution destabilizes (Mg,Fe)SiO3 perovskite relative to (Mg,Fe)SiO3 post-perovskite (Mao et al. 2004, Caracas and Cohen 2005). The bulk modulus at 80 GPa (K80) is ~550 GPa for both Fe-rich perovskites, comparable to values measured for MgSiO3 perovskite (Lundin et al. 2008). However, the volume of Fe-rich perovskites increases linearly with Fe-content. The (Mg0.25Fe0.70Ca0.05)SiO3 perovskite is 3% greater at 80 GPa than V80 for the Mg end

  1. Hybrid Perovskite/Perovskite Heterojunction Solar Cells.

    PubMed

    Hu, Yinghong; Schlipf, Johannes; Wussler, Michael; Petrus, Michiel L; Jaegermann, Wolfram; Bein, Thomas; Müller-Buschbaum, Peter; Docampo, Pablo

    2016-06-28

    Recently developed organic-inorganic hybrid perovskite solar cells combine low-cost fabrication and high power conversion efficiency. Advances in perovskite film optimization have led to an outstanding power conversion efficiency of more than 20%. Looking forward, shifting the focus toward new device architectures holds great potential to induce the next leap in device performance. Here, we demonstrate a perovskite/perovskite heterojunction solar cell. We developed a facile solution-based cation infiltration process to deposit layered perovskite (LPK) structures onto methylammonium lead iodide (MAPI) films. Grazing-incidence wide-angle X-ray scattering experiments were performed to gain insights into the crystallite orientation and the formation process of the perovskite bilayer. Our results show that the self-assembly of the LPK layer on top of an intact MAPI layer is accompanied by a reorganization of the perovskite interface. This leads to an enhancement of the open-circuit voltage and power conversion efficiency due to reduced recombination losses, as well as improved moisture stability in the resulting photovoltaic devices.

  2. Transport Properties of La- doped SrTiO3 Ceramics Prepared Using Spark Plasma Sintering

    NASA Astrophysics Data System (ADS)

    Mehdizadeh Dehkordi, Arash; Bhattacharya, Sriparna; Tritt, Terry M.; Alshareef, Husam N.

    2012-02-01

    In this work, thermoelectric transport properties of La-doped SrTiO3 ceramics prepared using conventional solid state reaction and spark plasma sintering have been investigated. Room temperature power factor of single crystal strontium titanate (SrTiO3), comparable to that of Bi2Te3, has brought new attention to this perovskite-type transition metal-oxide as a potential n-type thermoelectric for high temperature applications. Electronic properties of this model complex oxide, SrTiO3 (ABO3), can be tuned in a wide range through different doping mechanisms. In addition to A site (La-doped) or B site (Nb-doped) substitutional doping, introducing oxygen vacancies plays an important role in electrical and thermal properties of these structures. Having multiple doping mechanisms makes the transport properties of these perovskites more dependent on preparation parameters. The effect of these synthesis parameters and consolidation conditions on the transport properties of these materials has been studied.

  3. Evidence for a different electronic configuration as a primary effect during compression of orthorhombic perovskites: The case of Nd M3 +O3 (M =Cr ,Ga )

    NASA Astrophysics Data System (ADS)

    Ardit, M.; Dondi, M.; Merli, M.; Cruciani, G.

    2018-02-01

    (Mg ,Fe ) Si O3 perovskite is the most abundant mineral of the Earth's lower mantle, and compounds with the perovskite structure are perhaps the most widely employed ceramics. Hence, they attract both geophysicists and material scientists. Several investigations attempted to predict their structural evolution at high pressure, and recent advancements highlighted that perovskites having ions with the same formal valence at both polyhedral sites (i.e., 3 +:3 + ) define different compressional patterns when transition metal ions (TMI) are involved. In this study, in situ high-pressure synchrotron XRD measurements coupled with ab initio simulations of the electronic population of NdCr O3 perovskite are compared with the compressional feature of NdGa O3 . Almost identical from a steric point of view (C r3 + and G a3 + have almost the same ionic radius), the different electronic configuration of octahedrally coordinated ions - which leads to a redistribution of electrons at the 3 d orbitals for C r3 + - allows the crystal field stabilization energy (CFSE) to act as a vehicle of octahedral softening in NdCr O3 or it turns octahedra into rigid units when CFSE is null as in NdGa O3 . Besides to highlight that different electronic configurations can act as a primary effect during compression of perovskite compounds, our findings have a deep repercussion on the way the compressibility of perovskites have to be modeled.

  4. Electronic Subband Reconfiguration in a d0-Perovskite Induced by Strain-Driven Structural Transformations

    NASA Astrophysics Data System (ADS)

    Laukhin, V.; Copie, O.; Rozenberg, M. J.; Weht, R.; Bouzehouane, K.; Reyren, N.; Jacquet, E.; Bibes, M.; Barthélémy, A.; Herranz, G.

    2012-11-01

    It is well known that transport in lightly n-doped SrTiO3 involves light and heavy electron bands. We have found that upon application of moderate quasi-isotropic pressures, the relative positions of these subbands are changed by a few meV and, eventually, a band inversion occurs at ˜1kbar. Such effects are, however, suppressed in the closely related KTaO3 perovskite. We show that the extremely subtle electronic reconfiguration in SrTiO3 is triggered by strain-induced structural transformations that are accompanied by remarkable mobility enhancements up to about Δμ/μ≈300%. Our results provide a microscopic rationale for the recently discovered transport enhancement under strain and underscore the role of the internal structural degrees of freedom in the modulation of the perovskite electronic properties.

  5. Observation of Nanoscale Morphological and Structural Degradation in Perovskite Solar Cells by In-Situ TEM

    DOE PAGES

    Yang, Bin; Dyck, Ondrej K.; Univ. of Tennessee, Knoxville, TN; ...

    2016-11-04

    The chemical stability of organometallic halide perovskites is a major barrier facing their application in the fast rising field of next generation photovoltaics. These materials were shown to undergo degradation due to the influence of heat or moisture, significantly limiting the lifetime of associated devices. To overcome this stability issue, a fundamental understanding of degradation mechanisms is of foremost importance. Here, high resolution in situ transmission electron microscopy and electron energy loss spectroscopy elemental mapping were applied to probe morphological and structural changes in perovskite films during controlled environmental exposure treatments. Both moisture and oxygen in ambient air are revealedmore » to facilitate degradation in CH 3NH 3PbI 3 perovskites through decomposition and oxidation pathways, respectively. In addition, even in moisture- and oxygen-free environment evident degradation could be induced by heating at the solar cell s real-field operating temperature and the degradation was found to originate from defect sites. These findings provide fundamental insight to prevent degradation of perovskite materials and associated devices for realistic applications.« less

  6. Observation of Nanoscale Morphological and Structural Degradation in Perovskite Solar Cells by In-Situ TEM

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yang, Bin; Dyck, Ondrej K.; Univ. of Tennessee, Knoxville, TN

    The chemical stability of organometallic halide perovskites is a major barrier facing their application in the fast rising field of next generation photovoltaics. These materials were shown to undergo degradation due to the influence of heat or moisture, significantly limiting the lifetime of associated devices. To overcome this stability issue, a fundamental understanding of degradation mechanisms is of foremost importance. Here, high resolution in situ transmission electron microscopy and electron energy loss spectroscopy elemental mapping were applied to probe morphological and structural changes in perovskite films during controlled environmental exposure treatments. Both moisture and oxygen in ambient air are revealedmore » to facilitate degradation in CH 3NH 3PbI 3 perovskites through decomposition and oxidation pathways, respectively. In addition, even in moisture- and oxygen-free environment evident degradation could be induced by heating at the solar cell s real-field operating temperature and the degradation was found to originate from defect sites. These findings provide fundamental insight to prevent degradation of perovskite materials and associated devices for realistic applications.« less

  7. Electronic Interfacial Effects in Epitaxial Heterostructures based on LaMnO3.

    NASA Astrophysics Data System (ADS)

    Christen, Hans M.; Varela, M.; Lee, H. N.; Kim, D. H.; Chisholm, M. F.; Cantoni, C.; Petit, L.; Schulthess, T. C.; Lowndes, D. H.

    2006-03-01

    Studies of chemically abrupt interfaces provide an ideal platform to study the effects of discontinuities and asymmetries of the electronic configuration on the transport and magnetic properties of complex oxides. In addition, the behavior of complex materials near interfaces plays the most crucial role not only in devices and nanostructures but also in complex structures in the form of composites and superlattices, including artificial multiferroics. Interfaces in the ABO3 perovskite system are particularly attractive because structurally similar oxides with fundamentally different physical properties can be integrated epitaxially. To explore the electronic effects at interfaces and to probe the physical properties that result from local electronic changes, we have synthesized structures containing LaMnO3 and insulating perovskites using pulsed laser deposition. The local electron energy loss spectroscopy (EELS) capability of a scanning transmission electron microscope (STEM) is used to probe the electronic configuration in the LaMnO3 films as a function of the distance from the interfaces. The results are compared to macroscopic measurements and theoretical predictions. Research sponsored by the U.S. Department of Energy under contract DE-AC05-00OR22725 with the Oak Ridge National Laboratory, managed by UT-Battelle, LLC.

  8. Effect of A-site deficiency in LaMn{sub 0.9}Co{sub 0.1}O{sub 3} perovskites on their catalytic performance for soot combustion

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dinamarca, Robinson; Garcia, Ximena; Jimenez, Romel

    Highlights: • A-site defective perovskites increases the oxidation state of the B-cation. • Not always non-stoichiometric perovskites exhibit higher catalytic activity in soot combustion. • The highly symmetric cubic crystalline structure diminishes the redox properties of perovskites. - Abstract: The influence of lanthanum stoichiometry in Ag-doped (La{sub 1-x}Ag{sub x}Mn{sub 0.9}Co{sub 0.1}O{sub 3}) and A-site deficient (La{sub 1-x}Mn{sub 0.9}Co{sub 0.1}O{sub 3-δ}) perovskites with x equal to 10, 20 and 30 at.% has been investigated in catalysts for soot combustion. The catalysts were prepared by the amorphous citrate method and characterized by XRD, nitrogen adsorption, XPS, O{sub 2}-TPD and TPR. The formationmore » of a rhombohedral excess-oxygen perovskite for Ag-doped and a cubic perovskite structure for an A-site deficient series is confirmed. The efficient catalytic performance of the larger Ag-doped perovskite structure is attributed to the rhombohedral crystalline structure, Ag{sub 2}O segregated phases and the redox pair Mn{sup 4+}/Mn{sup 3+}. A poor catalytic activity for soot combustion was observed with A-site deficient perovskites, despite the increase in the redox pair Mn{sup 4+}/Mn{sup 3+}, which is attributed to the cubic crystalline structure.« less

  9. Allelic Prevalence of ABO Blood Group Genes in Iranian Azari Population

    PubMed Central

    Nojavan, Mohammad; Shamsasenjan, Karrim; Movassaghpour, Ali Akbar; Akbarzadehlaleh, Parvin; Torabi, Seyd Esmail; Ghojazadeh, Morteza

    2012-01-01

    Introduction ABO blood group system is the most important blood group in transfusion and has been widely used in population studies. Several molecular techniques for ABO allele’s detection are widely used for distinguishing various alleles of glycosyl transferase locus on chromosome 9. Methods 744 randomly selected samples from Azari donors of East Azerbaijan province (Iran) were examined using well-adjusted multiplex allele- specific PCR ABO genotyping technique. Results The results were consistent for all individuals. The ABO blood group genotype of 744 healthy Azari blood donors was: 25.8% AA/AO (2), 7.6% AO (1), 1.6% BB, 11.3% B0 (1), 10% AB, 9.3% 0(1)0(1) and 15.3%0(1)0(2). The highest genotype frequency belonged to O01/O02 genotype (15.3%) and the lowest frequency belonged to A101/A102 genotype (0.4%). Conclusions: The frequencies of ABO alleles didn’t show significant differences between East Azerbaijan province population and that of other areas of the country. Meanwhile, statistical analysis of frequencies of A and B alleles between East Azerbaijan province population and neighbor countries showed significant differences whereas the frequency of allele O between them did not show significant difference (P>0.05). Conclusions The frequencies of ABO alleles didn’t show significant differences between East Azerbaijan province population and that of other areas of the country. Meanwhile, statistical analysis of frequencies of A and B alleles between East Azerbaijan province population and neighbor countries showed significant differences whereas the frequency of allele O between them did not show significant difference (P>0.05). PMID:23678461

  10. Sn2+-Stabilization in MASnI3 perovskites by superhalide incorporation.

    PubMed

    Xiang, Junxiang; Wang, Kan; Xiang, Bin; Cui, Xudong

    2018-03-28

    Sn-based hybrid halide perovskites are a potential solution to replace Pb and thereby reduce Pb toxicity in MAPbI 3 perovskite-based solar cells. However, the instability of Sn 2+ in air atmosphere causes a poor reproducibility of MASnI 3 , hindering steps towards this goal. In this paper, we propose a new type of organic metal-superhalide perovskite of MASnI 2 BH 4 and MASnI 2 AlH 4 . Through first-principles calculations, our results reveal that the incorporation of BH 4 and AlH 4 superhalides can realize an impressive enhancement of oxidation resistance of Sn 2+ in MASnI 3 perovskites because of the large electron transfer between Sn 2+ and [BH 4 ] - /[AlH 4 ] - . Meanwhile, the high carrier mobility is preserved in these superhalide perovskites and only a slight decrease is observed in the optical absorption strength. Our studies provide a new path to attain highly stable performance and reproducibility of Sn-based perovskite solar cells.

  11. Insights into the structure–photoreactivity relationships in well-defined perovskite ferroelectric KNbO 3 nanowires

    DOE PAGES

    Zhang, Tingting; Lei, Wanying; Liu, Ping; ...

    2015-04-23

    Structure–function correlations are a central theme in heterogeneous (photo)catalysis. In this study, the geometric and electronic structure of perovskite ferroelectric KNbO 3 nanowires with respective orthorhombic and monoclinic polymorphs have been systematically addressed. By virtue of aberration-corrected scanning transmission electron microscopy, we directly visualize surface photocatalytic active sites, measure local atomic displacements at an accuracy of several picometers, and quantify ferroelectric polarization combined with first-principles calculations. The photoreactivity of the as-prepared KNbO 3 nanowires is assessed toward aqueous rhodamine B degradation under UV light. A synergy between the ferroelectric polarization and electronic structure in photoreactivity enhancement is uncovered, which accountsmore » for the prominent reactivity order: orthorhombic > monoclinic. Additionally, by identifying new photocatalytic products, rhodamine B degradation pathways involving N-deethylation and conjugated structure cleavage are proposed. The findings not only provide new insights into the structure–photoreactivity relationships in perovskite ferroelectric photocatalysts, but also have broad implications in perovskite-based water splitting and photovoltaics, among others.« less

  12. Conducting Layered Organic-inorganic Halides Containing <110>-Oriented Perovskite Sheets.

    PubMed

    Mitzi, D B; Wang, S; Feild, C A; Chess, C A; Guloy, A M

    1995-03-10

    Single crystals of the layered organic-inorganic perovskites, [NH(2)C(I=NH(2)](2)(CH(3)NH(3))m SnmI3m+2, were prepared by an aqueous solution growth technique. In contrast to the recently discovered family, (C(4)H(9)NH(3))(2)(CH(3)NH(3))n-1SnnI3n+1, which consists of (100)-terminated perovskite layers, structure determination reveals an unusual structural class with sets of m <110>-oriented CH(3)NH(3)SnI(3) perovskite sheets separated by iodoformamidinium cations. Whereas the m = 2 compound is semiconducting with a band gap of 0.33 +/- 0.05 electron volt, increasing m leads to more metallic character. The ability to control perovskite sheet orientation through the choice of organic cation demonstrates the flexibility provided by organic-inorganic perovskites and adds an important handle for tailoring and understanding lower dimensional transport in layered perovskites.

  13. Outcomes after ABO-incompatible heart transplantation in adults: A registry study.

    PubMed

    Bergenfeldt, Henrik; Andersson, Bodil; Bućin, Dragan; Stehlik, Josef; Edwards, Leah; Rådegran, Göran; Nilsson, Johan

    2015-07-01

    In the past, ABO incompatibility was considered an absolute contraindication to heart transplantation (HT) in adults. Advances in ABO-incompatible HT in pediatric patients and ABO-incompatible abdominal transplantation in adult patients have led to clinical exploration of intentional ABO-incompatible HT in adults. However, it is not well known how outcomes in ABO-incompatible adult heart transplant recipients compare with outcomes in ABO-compatible recipients. We analyzed International Society for Heart and Lung Transplantation transplant registry data from heart donors and recipients ≥18 years old at the time of transplant for HT performed between 1988 and 2011. We compared baseline characteristics and post-transplant outcomes in ABO-incompatible and ABO-compatible HT. Death or retransplantation was the composite primary end-point. Among 76,663 adult patients undergoing HT between 1988 and June 30, 2011, 94 ABO-incompatible heart transplants were performed. The incidence of death or retransplantation in the ABO-incompatible group was higher than in the ABO-compatible group: 21% vs 9% at 30 days (hazard ratio = 2.38, p < 0.001) and 36% vs 19% at 1 year after transplant. However, ABO-incompatible grafts surviving past the first year after transplant had a similar incidence of failure compared with the ABO-compatible group. After 2005, the rate ABO-incompatible HT in adults increased, likely as a result of planned, intentional (rather than accidental) ABO-incompatible HT. In this group of patients, short-term and long-term incidence of death or retransplantation was similar to ABO-compatible recipients (p = 0.822): 7% at 30 days and 19% at 1 year after transplantation. We found no difference in incidence of death or retransplantation between ABO-compatible and ABO-incompatible HT in patients who underwent transplantation after 2005. Copyright © 2015 International Society for Heart and Lung Transplantation. Published by Elsevier Inc. All rights reserved.

  14. High-pressure crystal growth and electromagnetic properties of 5d double-perovskite Ca3OsO6

    NASA Astrophysics Data System (ADS)

    Feng, Hai Luke; Shi, Youguo; Guo, Yanfeng; Li, Jun; Sato, Akira; Sun, Ying; Wang, Xia; Yu, Shan; Sathish, Clastin I.; Yamaura, Kazunari

    2013-05-01

    Single crystals of the osmium-containing compound Ca3OsO6 have been successfully grown under high-pressure conditions, for the first time. The crystal structure of Ca3OsO6 were characterized as an ordered double-perovskite structure of space group P21/n with the Ca and Os atoms being fully ordered at the perovskite B-site. The electromagnetic analysis shows that the crystal exhibits a semiconductor-like behavior below 300 K and undergoes an antiferromagnetic transition at 50 K.

  15. Novel Solvent-free Perovskite Deposition in Fabrication of Normal and Inverted Architectures of Perovskite Solar Cells

    PubMed Central

    Nejand, Bahram Abdollahi; Gharibzadeh, Saba; Ahmadi, Vahid; Shahverdi, H. Reza

    2016-01-01

    We introduced a new approach to deposit perovskite layer with no need for dissolving perovskite precursors. Deposition of Solution-free perovskite (SFP) layer is a key method for deposition of perovskite layer on the hole or electron transport layers that are strongly sensitive to perovskite precursors. Using deposition of SFP layer in the perovskite solar cells would extend possibility of using many electron and hole transport materials in both normal and invert architectures of perovskite solar cells. In the present work, we synthesized crystalline perovskite powder followed by successful deposition on TiO2 and cuprous iodide as the non-sensitve and sensitive charge transport layers to PbI2 and CH3NH3I solution in DMF. The post compressing step enhanced the efficiency of the devices by increasing the interface area between perovskite and charge transport layers. The 9.07% and 7.71% cell efficiencies of the device prepared by SFP layer was achieved in respective normal (using TiO2 as a deposition substrate) and inverted structure (using CuI as deposition substrate) of perovskite solar cell. This method can be efficient in large-scale and low cost fabrication of new generation perovskite solar cells. PMID:27640991

  16. Determination of ABO blood grouping and Rhesus factor from tooth material.

    PubMed

    Kumar, Pooja Vijay; Vanishree, M; Anila, K; Hunasgi, Santosh; Suryadevra, Sri Sujan; Kardalkar, Swetha

    2016-01-01

    The aim of the study was to determine blood groups and Rhesus factor from dentin and pulp using absorption-elution (AE) technique in different time periods at 0, 3, 6, 9 and 12 months, respectively. A total of 150 cases, 30 patients each at 0, 3, 6, 9 and 12 months were included in the study. The samples consisted of males and females with age ranging 13-60 years. Patient's blood group was checked and was considered as "control." The dentin and pulp of extracted teeth were tested for the presence of ABO/Rh antigen, at respective time periods by AE technique. Data were analyzed in proportion. For comparison, Chi-square test or Fisher's exact test was used for the small sample. Blood group antigens of ABO and Rh factor were detected in dentin and pulp up to 12 months. For both ABO and Rh factor, dentin and pulp showed 100% sensitivity for the samples tested at 0 month and showed a gradual decrease in the sensitivity as time period increased. The sensitivity of pulp was better than dentin for both the blood grouping systems and ABO blood group antigens were better detected than Rh antigens. In dentin and pulp, the antigens of ABO and Rh factor were detected up to 12 months but showed a progressive decrease in the antigenicity as the time period increased. When compared the results obtained of dentin and pulp in ABO and Rh factor grouping showed similar results with no statistical significance. The sensitivity of ABO blood grouping was better than Rh factor blood grouping and showed a statistically significant result.

  17. Electron Transfer from Triplet State of TIPS-Pentacene Generated by Singlet Fission Processes to CH3NH3PbI3 Perovskite.

    PubMed

    Lee, Sangsu; Hwang, Daesub; Jung, Seok Il; Kim, Dongho

    2017-02-16

    To reveal the applicability of singlet fission processes in perovskite solar cell, we investigated electron transfer from TIPS-pentacene to CH 3 NH 3 PbI 3 (MAPbI 3 ) perovskite in film phase. Through the observation of the shorter fluorescence lifetime in TIPS-pentacene/MAPbI 3 perovskite bilayer film (5 ns) compared with pristine MAPbI 3 perovskite film (20 ns), we verified electron-transfer processes between TIPS-pentacene and MAPbI 3 perovskite. Furthermore, the observation of singlet fission processes, a faster decay rate, TIPS-pentacene cations, and the analysis of kinetic profiles of the intensity ratio between 500 and 525 nm in the TA spectra of the TIPS-pentacene/MAPbI 3 perovskite bilayer film indicate that electron transfer occurs from triplet state of TIPS-pentacene generated by singlet fission processes to MAPbI 3 perovskite conduction band. We believe that our results can provide useful information on the design of solar cells sensitized by singlet fission processes and pave the way for new types of perovskite solar cells.

  18. Disproportionation of (Mg,Fe)SiO 3 perovskite in Earth's deep lower mantle

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhang, L.; Meng, Y.; Yang, W.

    2014-05-22

    The mineralogical constitution of the Earth's mantle dictates the geophysical and geochemical properties of this region. Previous models of a perovskite-dominant lower mantle have been built on the assumption that the entire lower mantle down to the top of the D" layer contains ferromagnesian silicate [(Mg,Fe)SiO 3] with nominally 10 mole percent Fe. On the basis of experiments in laser-heated diamond anvil cells, at pressures of 95 to 101 gigapascals and temperatures of 2200 to 2400 kelvin, we found that such perovskite is unstable; it loses its Fe and disproportionates to a nearly Fe-free MgSiO 3 perovskite phase and anmore » Fe-rich phase with a hexagonal structure. This observation has implications for enigmatic seismic features beyond ~2000 kilometers depth and suggests that the lower mantle may contain previously unidentified major phases.« less

  19. Disproportionation of (Mg,Fe)SiO3 perovskite in Earth's deep lower mantle

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhang, L.; Meng, Y.; Yang, W.

    2014-05-22

    The mineralogical constitution of the Earth’s mantle dictates the geophysical and geochemical properties of this region. Previous models of a perovskite-dominant lower mantle have been built on the assumption that the entire lower mantle down to the top of the D'' layer contains ferromagnesian silicate [(Mg,Fe)SiO3] with nominally 10 mole percent Fe. On the basis of experiments in laser-heated diamond anvil cells, at pressures of 95 to 101 gigapascals and temperatures of 2200 to 2400 kelvin, we found that such perovskite is unstable; it loses its Fe and disproportionates to a nearly Fe-free MgSiO3 perovskite phase and an Fe-rich phasemore » with a hexagonal structure. This observation has implications for enigmatic seismic features beyond ~2000 kilometers depth and suggests that the lower mantle may contain previously unidentified major phases.« less

  20. Raman study of transition-metal oxides with perovskite-like structure

    NASA Astrophysics Data System (ADS)

    Kolev, Nikolay Iliev

    Perovskite-like oxides exhibit a rich variety of properties of fundamental scientific interest and potential application value. The motivation for this work is to contribute to our knowledge of perovskite-like systems and strongly correlated systems in general. The polarized Raman spectra of single crystal and thin film CaCu3Ti4O12, single crystal and thin film CaRuO3, microcrystals of La0.5Ca 0.5MnO3, and ceramic and thin film CaMnO3 have been investigated. In close comparison to results from lattice dynamics calculations most of the Raman lines in the CaCu3Ti4O12, CaRuO3, La0.5Ca0.5MnO3 and CaMnO 3 spectra, have been assigned to definite phonon modes. The validity of the model for twin orientation in the Pnma structure for CaRuO3 and La0.5Ca0.5MnO3 is confirmed. The analysis of the CaMnO3 spectra contributed to the development of a model, based on four basic distortions of the (distorted) perovskite structure. The temperature behavior of the CaCu3Ti4O 12 spectra shows that there is no evidence for structural phase transition in the temperature range 20--600 K, so such a transition cannot be responsible for the sharp drop in the dielectric constant below 100 K. The Raman spectra indirectly support the mechanism of formation of barrier layer capacitances in CaCu3Ti4O12.The observation of additional Raman mode of nominal Ag symmetry is discussed in terms of coexistence of domains of different atomic arrangement, or alternatively of non-stoichiometry (Cu deficiency). In the case of the thin film, the tetragonal distortions could be responsible for the greater separation of the additional Ag line. No anomalies in the temperature behavior of the Raman lines of CaRuO3 is observed, which is an indirect evidence for its lack of long-range magnetic ordering at low temperatures (depending on whether this ordering would be observable by Raman spectroscopy through spin-phonon coupling). In La0.5Ca0.5MnO 3 the appearance of several Raman lines below TN is analyzed in terms of

  1. The variation of polyhedral compressibilities between structures

    NASA Astrophysics Data System (ADS)

    Ross, N. L.; Angel, R. J.; Zhao, J.; Vanpeteghem, C.

    2006-05-01

    In their influential book "Comparative Crystal Chemistry" Hazen and Finger [1] concluded that "a given type of polyhedron has nearly constant bulk modulus within estimated experimental error, independent of structure". Advances in the precision of experimental high-pressure diffraction measurements over the ensuing two decades allow us to re-examine this hypothesis. In particular, the discovery that the response of the perovskite structure to high pressures is controlled by the equipartition of bond-valence strain between the A and B cation sites within the structure [2] explicitly implies that the octahedral compressibility depends not only upon the octahedral cation, but also upon the compressibility of the cation-oxygen bonds of the extra-framework (nominally dodecahedral) site. Thus the octahedral compressibility of a B cation changes with the A cation. For example, the compressibility of the Ga-O bonds in LaGaO3 is 2.43(7) x 10-3 GPa-1, whereas it is 1.81 x 10-3 GPa-1 in NdGaO3. The compressibilities of Al-O bonds in perovskites range between 1.62(9) and 1.87(13) x 10-3 GPa-1. A more extreme example is provided by the difference in octahedral compressibilities between ABO3 perovskites and their protonated analogues AB(OH)6. In CaSnO3 the average compressibility of the Sn- O bonds within the octahedra is 1.61(11) x 10-3 GPa-1, whereas the Sn-O bonds in MnSn(OH)6 are incompressible within the uncertainties of the measurement. References [1] Hazen, Finger (1982) Comparative Crystal Chemistry. John Wiley and Sons [2] Zhao, Ross, & Angel (2004). Acta Cryst. B60:263 [3] Vanpeteghem et al. (2006) Geophys. Res. Letts. 33: L03306. [4] Ross et al. (1990) Amer. Mineral. 75:739

  2. Light-absorption enhancement design of ultrathin perovskite solar cells with conformal structure

    NASA Astrophysics Data System (ADS)

    Tan, Xinyu; Sun, Lei; Deng, Can; Tu, Yiteng; Shen, Guangming; Tan, Fengxue; Guan, Li; Yan, Wensheng

    2018-06-01

    We report a structural design of ultrathin perovskite solar cells based on a conformal structure at the rear surface for potential applications in both single-junction and tandem cells. The light transmittances of the front and the rear surfaces are calculated in the wavelength range of 300–800 nm via the finite difference time domain numerical simulation method. Compared with the reference cell, significant photocurrent density enhancement of 27.5% and 29.7% are achieved when the ratios of height to width of the fluorine doped tin oxide nanoblock are 2 and 3, respectively. For the case with a hole transport material layer, the enhancements of photocurrent density enhancements are 19.2% and 29.0%, respectively. When back Au is removed, the photocurrent density also has notable enhancements of 23.3% and 45.9%, respectively. The achieved results are beneficial for the development of efficient ultrathin single-junction and tandem perovskite solar cells.

  3. Efficient Lead-Free Solar Cells Based on Hollow {en}MASnI3 Perovskites.

    PubMed

    Ke, Weijun; Stoumpos, Constantinos C; Spanopoulos, Ioannis; Mao, Lingling; Chen, Michelle; Wasielewski, Michael R; Kanatzidis, Mercouri G

    2017-10-18

    Tin-based perovskites have very comparable electronic properties to lead-based perovskites and are regarded as possible lower toxicity alternates for solar cell applications. However, the efficiency of tin-based perovskite solar cells is still low and they exhibit poor air stability. Here, we report lead-free tin-based solar cells with greatly enhanced performance and stability using so-called "hollow" ethylenediammonium and methylammonium tin iodide ({en}MASnI 3 ) perovskite as absorbers. Our results show that en can improve the film morphology and most importantly can serve as a new cation to be incorporated into the 3D MASnI 3 lattice. When the cation of en becomes part of the 3D structure, a high density of SnI 2 vacancies is created resulting in larger band gap, larger unit cell volume, lower trap-state density, and much longer carrier lifetime compared to classical MASnI 3 . The best-performing {en}MASnI 3 solar cell has achieved a high efficiency of 6.63% with an open circuit voltage of 428.67 mV, a short-circuit current density of 24.28 mA cm -2 , and a fill factor of 63.72%. Moreover, the {en}MASnI 3 device shows much better air stability than the neat MASnI 3 device. Comparable performance is also achieved for cesium tin iodide solar cells with en loading, demonstrating the broad scope of this approach.

  4. [Am]Mn(H2POO)3: A New Family of Hybrid Perovskites Based on the Hypophosphite Ligand.

    PubMed

    Wu, Yue; Shaker, Sammy; Brivio, Federico; Murugavel, Ramaswamy; Bristowe, Paul D; Cheetham, Anthony K

    2017-11-29

    A family of five hybrid ABX 3 perovskites has been synthesized using hypophosphite (H 2 POO) - as the X-site ion. These compounds adopt the general formula [Am]Mn(H 2 POO) 3 , where Am = guanidinium (GUA), formamidinium (FA), imidazolium, triazolium, and dabconium. We explore the diverse structural and phase transition behavior of these materials through single-crystal diffraction measurements and demonstrate contrasting magnetism in two of the phases, Am = GUA and FA, that arises from structural distortions. The results show that hypophosphite perovskites offer a promising platform for generating new functional materials.

  5. Anisotropy of Earth's D'' layer and stacking faults in the MgSiO3 post-perovskite phase.

    PubMed

    Oganov, Artem R; Martonák, Roman; Laio, Alessandro; Raiteri, Paolo; Parrinello, Michele

    2005-12-22

    The post-perovskite phase of (Mg,Fe)SiO3 is believed to be the main mineral phase of the Earth's lowermost mantle (the D'' layer). Its properties explain numerous geophysical observations associated with this layer-for example, the D'' discontinuity, its topography and seismic anisotropy within the layer. Here we use a novel simulation technique, first-principles metadynamics, to identify a family of low-energy polytypic stacking-fault structures intermediate between the perovskite and post-perovskite phases. Metadynamics trajectories identify plane sliding involving the formation of stacking faults as the most favourable pathway for the phase transition, and as a likely mechanism for plastic deformation of perovskite and post-perovskite. In particular, the predicted slip planes are {010} for perovskite (consistent with experiment) and {110} for post-perovskite (in contrast to the previously expected {010} slip planes). Dominant slip planes define the lattice preferred orientation and elastic anisotropy of the texture. The {110} slip planes in post-perovskite require a much smaller degree of lattice preferred orientation to explain geophysical observations of shear-wave anisotropy in the D'' layer.

  6. Insight into the CH3NH3PbI3/C interface in hole-conductor-free mesoscopic perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Li, Jiangwei; Niu, Guangda; Li, Wenzhe; Cao, Kun; Wang, Mingkui; Wang, Liduo

    2016-07-01

    Perovskite solar cells (PSCs) with hole-conductor-free mesoscopic architecture have shown superb stability and great potential in practical application. The printable carbon counter electrodes take full responsibility of extracting holes from the active CH3NH3PbI3 absorbers. However, an in depth study of the CH3NH3PbI3/C interface properties, such as the structural formation process and the effect of interfacial conditions on hole extraction, is still lacking. Herein, we present, for the first time, an insight into the spatial confinement induced CH3NH3PbI3/C interface formation by in situ photoluminescence observations during the crystallization process of CH3NH3PbI3. The derived reaction kinetics allows a quantitative description of the perovskite formation process. In addition, we found that the interfacial contact between carbon and perovskite was dominant for hole extraction efficiency and associated with the photovoltaic parameter of short circuit current density (JSC). Consequently, we conducted a solvent vapor assisted process of PbI2 diffusion to carefully control the CH3NH3PbI3/C interface with less unreacted PbI2 barrier. The improvement of interface conditions thereby contributes to a high hole extraction proved by the charge extraction resistance and PL lifetime change, resulting in the increased JSC valve.Perovskite solar cells (PSCs) with hole-conductor-free mesoscopic architecture have shown superb stability and great potential in practical application. The printable carbon counter electrodes take full responsibility of extracting holes from the active CH3NH3PbI3 absorbers. However, an in depth study of the CH3NH3PbI3/C interface properties, such as the structural formation process and the effect of interfacial conditions on hole extraction, is still lacking. Herein, we present, for the first time, an insight into the spatial confinement induced CH3NH3PbI3/C interface formation by in situ photoluminescence observations during the crystallization

  7. Thermoelectric Properties of Electron-Doped SrMnO3 Single Crystals with Perovskite Structure

    NASA Astrophysics Data System (ADS)

    Suzuki, T.; Sakai, H.; Taguchi, Y.; Tokura, Y.

    2012-06-01

    Thermoelectric properties have been investigated for single crystals of Sr(Mn1- x Mo x )O3 with the perovskite structure. Similar to (Sr1- x Ce x )MnO3, the Seebeck coefficient for lightly electron-doped compounds ( x ≤ 0.01) is enhanced upon G-type antiferromagnetic ordering, while maintaining metallic conduction. This results in enhancement of the figure of merit ( ZT). On the other hand, the Seebeck coefficient for the more electron-doped compound ( x = 0.025) changes sign from negative to positive within a spin and orbital ordered phase (with C-type antiferromagnetic configuration and Mn 3 z 2 - r 2 type orbital order) as the temperature is lowered, whereas the Hall coefficient remains negative in the whole temperature range. The enhancement of the ZT value in the G-type antiferromagnetic phase implies the possibility for improvement of the thermoelectric efficiency by using the coupling between charge, spin, orbital, and lattice degrees of freedom in strongly correlated electron systems.

  8. Electrical Stress Influences the Efficiency of CH3 NH3 PbI3 Perovskite Light Emitting Devices.

    PubMed

    Zhao, Lianfeng; Gao, Jia; Lin, YunHui L; Yeh, Yao-Wen; Lee, Kyung Min; Yao, Nan; Loo, Yueh-Lin; Rand, Barry P

    2017-06-01

    Organic-inorganic hybrid perovskite materials are emerging as semiconductors with potential application in optoelectronic devices. In particular, perovskites are very promising for light-emitting devices (LEDs) due to their high color purity, low nonradiative recombination rates, and tunable bandgap. Here, using pure CH 3 NH 3 PbI 3 perovskite LEDs with an external quantum efficiency (EQE) of 5.9% as a platform, it is shown that electrical stress can influence device performance significantly, increasing the EQE from an initial 5.9% to as high as 7.4%. Consistent with the enhanced device performance, both the steady-state photoluminescence (PL) intensity and the time-resolved PL decay lifetime increase after electrical stress, indicating a reduction in nonradiative recombination in the perovskite film. By investigating the temperature-dependent characteristics of the perovskite LEDs and the cross-sectional elemental depth profile, it is proposed that trap reduction and resulting device-performance enhancement is due to local ionic motion of excess ions, likely excess mobile iodide, in the perovskite film that fills vacancies and reduces interstitial defects. On the other hand, it is found that overstressed LEDs show irreversibly degraded device performance, possibly because ions initially on the perovskite lattice are displaced during extended electrical stress and create defects such as vacancies. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. High-pressure behavior of methylammonium lead iodide (MAPbI3) hybrid perovskite

    NASA Astrophysics Data System (ADS)

    Capitani, Francesco; Marini, Carlo; Caramazza, Simone; Postorino, Paolo; Garbarino, Gaston; Hanfland, Michael; Pisanu, Ambra; Quadrelli, Paolo; Malavasi, Lorenzo

    2016-05-01

    In this paper we provide an accurate high-pressure structural and optical study of the MAPbI3 hybrid perovskite. Structural data show the presence of a phase transition toward an orthorhombic structure around 0.3 GPa followed by full amorphization of the system above 3 GPa. After releasing the pressure, the system keeps the high-pressure orthorhombic phase. The occurrence of these structural transitions is further confirmed by pressure induced variations of the photoluminescence signal at high pressure. These variations clearly indicate that the bandgap value and the electronic structure of MAPI change across the phase transition.

  10. Bication lead iodide 2D perovskite component to stabilize inorganic α-CsPbI3 perovskite phase for high-efficiency solar cells

    PubMed Central

    Zhang, Taiyang; Dar, M. Ibrahim; Li, Ge; Xu, Feng; Guo, Nanjie; Grätzel, Michael; Zhao, Yixin

    2017-01-01

    Among various all-inorganic halide perovskites exhibiting better stability than organic-inorganic halide perovskites, α-CsPbI3 with the most suitable band gap for tandem solar cell application faces an issue of phase instability under ambient conditions. We discovered that a small amount of two-dimensional (2D) EDAPbI4 perovskite containing the ethylenediamine (EDA) cation stabilizes the α-CsPbI3 to avoid the undesirable formation of the nonperovskite δ phase. Moreover, not only the 2D perovskite of EDAPbI4 facilitate the formation of α-CsPbI3 perovskite films exhibiting high phase stability at room temperature for months and at 100°C for >150 hours but also the α-CsPbI3 perovskite solar cells (PSCs) display highly reproducible efficiency of 11.8%, a record for all-inorganic lead halide PSCs. Therefore, using the bication EDA presents a novel and promising strategy to design all-inorganic lead halide PSCs with high performance and reliability. PMID:28975149

  11. Does low post-perovskite viscosity have an effect on structures at the core-mantle boundary ?

    NASA Astrophysics Data System (ADS)

    Nakagawa, T.; Tackley, P. J.; Ammann, M. W.; Brodholt, J. P.; Dobson, D.

    2009-12-01

    According to recent high pressure experiments [e.g. Yamazaki et al., 2006], viscosity determination using geoid fitting [Tosi et al., 2009], and new ab initio DFT calculations [Ammann et al., 2009], the viscosity of the post-perovskite phase may be lower than the viscosity of the perovskite by up to 2-3 orders of magnitude. Both activation enthalpy and the pre-exponential factor in the viscosity law are expected to be different. Here we implement phase-dependent viscosity into 3-D spherical shell, thermo-chemical mantle convection model, to investigate an effect of low post-perovskite viscosity and its influence on the heterogeneous structures in the core-mantle boundary region, including lateral variations in heat flux across the core-mantle boundary. Rheological parameters are taken from first principle calculations for perovskite [Ammann et al., 2009] plus new calculations for post-perovskite, with post-perovskite viscosity being up to three orders of magnitude lower. A major finding from our simulations is that low PPV viscosity increases the lateral heterogeneity in CMB heat flux and stabilizes compositionally-dense anomalies by basaltic material above the CMB. In order to understand the relationship between local heat flux and seismic anomaly near the core-mantle boundary, the results of these mantle convection simulations are used to expand the simple theory for the scaling relationship between CMB heat flux and seismic anomalies found in our recent paper [Nakagawa and Tackley, 2008]. Stabilizing the dense piles above the CMB by low post-perovskite viscosity effects can explain the current inference of thermo-chemical-phase structures from both seismology and mineral physics . Here we also try to determine how seismic anomalies can predict heat flux across the CMB from our modeling results. References Ammann, M., J. P. Brodholt and D. P. Dobson, PCM, doi:10.1007/s00269-008-0265-z, 2009. Nakagawa, T., and P. J. Tackley, EPSL, 271, 348-358, 2008.

  12. High pressure structure studies of 6H-SrIrO3 and the octahedral tilting in 3C-SrIrO3 towards a post-perovskite

    NASA Astrophysics Data System (ADS)

    Kronbo, Camilla H.; Nielsen, Morten B.; Kevy, Simone M.; Parisiades, Paraskevas; Bremholm, Martin

    2016-06-01

    The high pressure behaviors of the two perovskite structures (hexagonal 6H-SrIrO3 and orthorhombic 3C-SrIrO3) have been studied in diamond anvil cells to 43 and 60 GPa, respectively, using synchrotron powder X-ray diffraction. 6H-SrIrO3 was first synthesized at ambient pressure and subsequently transformed into 3C-SrIrO3 in a large volume press at 8.8 GPa and 1000 °C. Both polymorphs were found to retain the initial symmetry up to the highest pressures measured, but in the case of 6H-SrIrO3, two anomalies were identified: a change in the axial compressibilities at 24 GPa and a change in both the axial and volume compressibilities at 32 GPa. Fitting a 3rd order Birch-Murnaghan equation of state to the obtained P-V data yielded bulk moduli of K0=151.5(12) GPa (fitted range 03 and K0=187.1(9) GPa for 3C-SrIrO3. Analysis of the structural parameters for 6H-SrIrO3 aided by F-f plots suggests the anomalies are caused by changes in the compression mechanism. Comparison of the two polymorphs reveals that 6H-SrIrO3 becomes less compressible than 3C-SrIrO3 above 32 GPa as a result of the mechanistic change, and a crossing of their P-V curves is avoided. For 3C-SrIrO3, analysis of the octahedral tilt angles shows that these increase monotonically from the ambient value of 7.23(6) to 23.0(2)° at 60 GPa suggesting that a transition to a post-perovskite is approached.

  13. Perovskite-type oxides - Oxygen electrocatalysis and bulk structure

    NASA Technical Reports Server (NTRS)

    Carbonio, R. E.; Fierro, C.; Tryk, D.; Scherson, D.; Yeager, E.

    1988-01-01

    Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

  14. Influence of Hybrid Perovskite Fabrication Methods on Film Formation, Electronic Structure, and Solar Cell Performance

    PubMed Central

    Schnier, Tobias; Emara, Jennifer; Olthof, Selina; Meerholz, Klaus

    2017-01-01

    Hybrid organic/inorganic halide perovskites have lately been a topic of great interest in the field of solar cell applications, with the potential to achieve device efficiencies exceeding other thin film device technologies. Yet, large variations in device efficiency and basic physical properties are reported. This is due to unintentional variations during film processing, which have not been sufficiently investigated so far. We therefore conducted an extensive study of the morphology and electronic structure of a large number of CH3NH3PbI3 perovskite where we show how the preparation method as well as the mixing ratio of educts methylammonium iodide and lead(II) iodide impact properties like film formation, crystal structure, density of states, energy levels, and ultimately the solar cell performance. PMID:28287555

  15. Determination of ABO blood grouping and Rhesus factor from tooth material

    PubMed Central

    Kumar, Pooja Vijay; Vanishree, M; Anila, K; Hunasgi, Santosh; Suryadevra, Sri Sujan; Kardalkar, Swetha

    2016-01-01

    Objective: The aim of the study was to determine blood groups and Rhesus factor from dentin and pulp using absorption-elution (AE) technique in different time periods at 0, 3, 6, 9 and 12 months, respectively. Materials and Methods: A total of 150 cases, 30 patients each at 0, 3, 6, 9 and 12 months were included in the study. The samples consisted of males and females with age ranging 13–60 years. Patient's blood group was checked and was considered as “control.” The dentin and pulp of extracted teeth were tested for the presence of ABO/Rh antigen, at respective time periods by AE technique. Statistical Analysis: Data were analyzed in proportion. For comparison, Chi-square test or Fisher's exact test was used for the small sample. Results: Blood group antigens of ABO and Rh factor were detected in dentin and pulp up to 12 months. For both ABO and Rh factor, dentin and pulp showed 100% sensitivity for the samples tested at 0 month and showed a gradual decrease in the sensitivity as time period increased. The sensitivity of pulp was better than dentin for both the blood grouping systems and ABO blood group antigens were better detected than Rh antigens. Conclusion: In dentin and pulp, the antigens of ABO and Rh factor were detected up to 12 months but showed a progressive decrease in the antigenicity as the time period increased. When compared the results obtained of dentin and pulp in ABO and Rh factor grouping showed similar results with no statistical significance. The sensitivity of ABO blood grouping was better than Rh factor blood grouping and showed a statistically significant result. PMID:27721625

  16. Structure of 18R shifted hexagonal perovskite La{sub 6}MgTi{sub 4}O{sub 18} revisited by neutron diffraction

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lu, Fengqi; Kuang, Xiaojun, E-mail: kuangxj@glut.edu.cn

    The structure of 18-layer shifted B-site deficient hexagonal perovskite La{sub 6}MgTi{sub 4}O{sub 18} compound has been re-examined by neutron powder diffraction. Structural analysis reveals that La{sub 6}MgTi{sub 4}O{sub 18} compound adopts a 18R octahedral-tilted structure with LaO{sub 3} layer stacking sequence of (hhcccc){sub 3} in space group R{sup {sup -}}3, in contrast with the previously proposed R3m. La{sub 6}MgTi{sub 4}O{sub 18} demonstrates partially ordered Mg cation distribution with a preference on the central octahedral sites over the outer octahedral sites in the cubic perovskite blocks isolated by the single vacant octahedral layers between the two consecutive hexagonal layers. The instabilitymore » of the La{sub 6}MgTi{sub 4}O{sub 18} on alumina ceramic substrate at high temperature and its dependencies of cell parameters and permittivity were characterized as well. - Graphical abstract: 18-layer shifted hexagonal perovskite La{sub 6}MgTi{sub 4}O{sub 18} adopts octahedral-tilted structure in R{sup {sup -}}3 and demonstrates partially ordered Mg distribution in the cubic perovskite blocks isolated by the vacant octahedral layers. - Highlights: • Neutron diffraction reveals an octahedra-tilted structure in R{sup {sup -}}3 for La{sub 6}MgTi{sub 4}O{sub 18}. • Mg/Ti distribution in La{sub 6}MgTi{sub 4}O{sub 18} is partially ordered in the perovskite blocks. • Instability of La{sub 6}MgTi{sub 4}O{sub 18} on alumina ceramic at high temperature is demonstrated.« less

  17. Ab-Initio Calculation of Electronic Structure of Lead Halide Perovskites with Formamidinium Cation as an Active Material for Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Indari, E. D.; Wungu, T. D. K.; Hidayat, R.

    2017-07-01

    Organic lead halide perovskite material based solar cells show impressive power conversion efficiencies, which can reach above 19 percent for perovskite solar cell with methyl-ammonium cations. These efficiencies are originated from efficient photoexcitation and charge carrier transport and not observed in conventional perovskite crystals. In this preliminary research work, we therefore performed Density Functional Theory (DFT) calculation of formamidinium lead iodide (FAPI), an alternative to methyl-ammonium lead iodide (MAPI), to predict their electronic structure and density of state (DOS). The calculation result at the most stable lattice parameters show a good agreement with the experiment results. The obtained band gap energy is 1.307 eV. The valence band is dominantly formed by the 5p orbitals of I- anions, while the conduction band is dominantly formed by the 6p orbitals of Pb2+ cations. The DOS of valence band of this perovskite seems smaller compared to the case of methyl-ammonium lead iodide perovskite, which then may explain the observation of smaller power conversion efficiencies in perovskite solar cells with this formamidinium cations.

  18. Effect of metal cation replacement on the electronic structure of metalorganic halide perovskites: Replacement of lead with alkaline-earth metals

    NASA Astrophysics Data System (ADS)

    Pazoki, Meysam; Jacobsson, T. Jesper; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

    2016-04-01

    Organic and inorganic lead halogen perovskites, and in particular, C H3N H3Pb I3 , have during the last years emerged as a class of highly efficient solar cell materials. Herein we introduce metalorganic halogen perovskite materials for energy-relevant applications based on alkaline-earth metals. Based on the classical notion of Goldschmidt's rules and quantum mechanical considerations, the three alkaline-earth metals, Ca, Sr, and Ba, are shown to be able to exchange lead in the perovskite structure. The three alkaline-earth perovskites, C H3N H3Ca I3,C H3N H3Sr I3 , and C H3N H3Ba I3 , as well as the reference compound, C H3N H3Pb I3 , are in this paper investigated with density functional theory (DFT) calculations, which predict these compounds to exist as stable perovskite materials, and their electronic properties are explored. A detailed analysis of the projected molecular orbital density of states and electronic band structure from DFT calculations were used for interpretation of the band-gap variations in these materials and for estimation of the effective masses of the electrons and holes. Neglecting spin-orbit effects, the band gap of MACa I3,MASr I3 , and MABa I3 were estimated to be 2.95, 3.6, and 3.3 eV, respectively, showing the relative change expected for metal cation exchange. The shifts in the conduction band (CB) edges for the alkaline-earth perovskites were quantified using scalar relativistic DFT calculations and tight-binding analysis, and were compared to the situation in the more extensively studied lead halide perovskite, C H3N H3Pb I3 , where the change in the work function of the metal is the single most important factor in tuning the CB edge and band gap. The results show that alkaline-earth-based organometallic perovskites will not work as an efficient light absorber in photovoltaic applications but instead could be applicable as charge-selective contact materials. The rather high CB edge and the wide band gap together with the large

  19. High-pressure synthesis and structural, physical properties of CaIr1-xPtxO3 and CaIr1-xRhxO3

    NASA Astrophysics Data System (ADS)

    Hirai, S.; Bromiley, G. D.; Klemme, S.; Irifune, T.; Ohfuji, H.; Attfield, P.; Nishiyama, N.

    2010-12-01

    Since the discovery of the perovskite to post-perovskite transition in MgSiO3 in a laser-heated DAC, wide attention has been focussed on the post-perovskite phase of MgSiO3. This is because the post-perovskite phase is likely to play a key role in Earth’s lowermost mantle, and because the perovskite to post-perovskite transition can explain many features of the D” seismic discontinuity. While it is meaningful to conduct further studies of MgSiO3, the post-perovskite phase of MgSiO3 cannot be quenched to ambient pressure/temperature conditions. Thus, further studies must be conducted using analogue compounds of MgSiO3 post-perovskite, which are quenchable to ambient pressure/temperature conditions. The post-perovskite phase of MgSiO3 crystallizes in a layered structure with CaIrO3-structure. Therefore, it is useful to investigate compounds with CaIrO3-structure. There are only four quenchable oxides with CaIrO3-structure reported to date: CaIrO3, CaPtO3, CaRhO3 and CaRuO3. CaIrO3 can be synthesized at ambient pressure, whilst the other three oxides can only be obtained at high pressure/temperature conditions using a multi-anvil apparatus. Further studies on these materials have revealed structural phase transitions at high P-T and a metal-insulator transition by hole doping. In the case of CaIrO3, The post-perovskite phase of CaIrO3 synthesized at 2GPa, 1373K transforms into a perovskite phase at 2GPa, 1673K. In other words, the perovskite phase can be synthesized at temperatures higher than those needed for synthesizing the post-perovskite phase. This is also the case for CaRhO3 (6GPa, 1873K) and CaRuO3 (23GPa, 1343K), while CaPtO3 remained post-perovskite at higher temperatures. We have succeeded in synthesizing solid solutions between CaIrO3, CaPtO3 and CaRhO3. We have found the systematic change in structural and physical properties of post-perovskite oxides, with composition and P-T, which broadens the future opportunity for studying post-perovskite systems

  20. Determination of the structural phase and octahedral rotation angle in halide perovskites

    NASA Astrophysics Data System (ADS)

    dos Reis, Roberto; Yang, Hao; Ophus, Colin; Ercius, Peter; Bizarri, Gregory; Perrodin, Didier; Shalapska, Tetiana; Bourret, Edith; Ciston, Jim; Dahmen, Ulrich

    2018-02-01

    A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurement of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). The approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.

  1. Determination of the structural phase and octahedral rotation angle in halide perovskites

    DOE PAGES

    dos Reis, Roberto; Yang, Hao; Ophus, Colin; ...

    2018-02-12

    A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr 3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr 3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurementmore » of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). Finally, the approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.« less

  2. Unusual Ferroelectricity in Two-Dimensional Perovskite Oxide Thin Films.

    PubMed

    Lu, Jinlian; Luo, Wei; Feng, Junsheng; Xiang, Hongjun

    2018-01-10

    Two-dimensional (2D) ferroelectricity have attracted much attention due to their applications in novel miniaturized devices such as nonvolatile memories, field effect transistors, and sensors. Since most of the commercial ferroelectric (FE) devices are based on ABO 3 perovskite oxides, it is important to investigate the properties of 2D ferroelectricity in perovskite oxide thin films. Here, based on density functional theory (DFT) calculations, we find that there exist three kinds of in-plane FE states that originate from different microscopic mechanisms: (i) a proper FE state with the polarization along [110] due to the second-order Jahn-Teller effect related to the B ion with empty d-orbitals; (ii) a robust FE state with the polarization along [100] induced by the surface effect; (iii) a hybrid improper FE state with the polarization along [110] that is induced by the trilinear coupling between two rotational modes and the A-site displacement. Interestingly, the ferroelectricity in the latter two cases becomes stronger along with decreasing the thin film thickness, in contrast to the usual behavior. Moreover, the latter two FE states are compatible with magnetism since their stability does not depend on the occupation of the d-orbitals of the B-ion. These two novel 2D FE mechanisms provide new avenues to design 2D multiferroics, as we demonstrated in SrVO and CaFeO thin film cases. Our work not only reveals new physical mechanisms of 2D ferroelectricity in perovskite oxide thin films but also provides a new route to design the high-performance 2D FE and multiferroics.

  3. Oxide perovskite crystals for HTSC film substrates microwave applications

    NASA Technical Reports Server (NTRS)

    Bhalla, A. S.; Guo, Ruyan

    1995-01-01

    The research focused upon generating new substrate materials for the deposition of superconducting yttrium barium cuprate (YBCO) has yielded several new hosts in complex perovskites, modified perovskites, and other structure families. New substrate candidates such as Sr(Al(1/2)Ta(1/2))O3 and Sr(Al(1/2)Nb(1/2))O3, Ba(Mg(1/3)Ta(2/3))O3 in complex oxide perovskite structure family and their solid solutions with ternary perovskite LaAlO3 and NdGaO3 are reported. Conventional ceramic processing techniques were used to fabricate dense ceramic samples. A laser heated molten zone growth system was utilized for the test-growth of these candidate materials in single crystal fiber form to determine crystallographic structure, melting point, thermal, and dielectric properties as well as to make positive identification of twin free systems. Some of those candidate materials present an excellent combination of properties suitable for microwave HTSC substrate applications.

  4. Spatially Resolved Imaging on Photocarrier Generations and Band Alignments at Perovskite/PbI2 Heterointerfaces of Perovskite Solar Cells by Light-Modulated Scanning Tunneling Microscopy.

    PubMed

    Shih, Min-Chuan; Li, Shao-Sian; Hsieh, Cheng-Hua; Wang, Ying-Chiao; Yang, Hung-Duen; Chiu, Ya-Ping; Chang, Chia-Seng; Chen, Chun-Wei

    2017-02-08

    The presence of the PbI 2 passivation layers at perovskite crystal grains has been found to considerably affect the charge carrier transport behaviors and device performance of perovskite solar cells. This work demonstrates the application of a novel light-modulated scanning tunneling microscopy (LM-STM) technique to reveal the interfacial electronic structures at the heterointerfaces between CH 3 NH 3 PbI 3 perovskite crystals and PbI 2 passivation layers of individual perovskite grains under light illumination. Most importantly, this technique enabled the first observation of spatially resolved mapping images of photoinduced interfacial band bending of valence bands and conduction bands and the photogenerated electron and hole carriers at the heterointerfaces of perovskite crystal grains. By systematically exploring the interfacial electronic structures of individual perovskite grains, enhanced charge separation and reduced back recombination were observed when an optimal design of interfacial PbI 2 passivation layers consisting of a thickness less than 20 nm at perovskite crystal grains was applied.

  5. Single Crystal Elasticity of Iron Bearing Perovskite and Post Perovskite Analog

    NASA Astrophysics Data System (ADS)

    Yoneda, A.; Fukui, H.; Baron, A. Q. R.

    2014-12-01

    We measured single crystal elasticity of (1) pure and iron bearing MgSiO3 perovskite, and (2) Pbnm-CaIrO3 and Cmcm-CaIrO3, a representative analog of MgSiO3 perovskite and post perovskite, respectively, by means of inelastic X ray scattering at BL35XU, SPring-8. The present results for MgSiO3 perovskite demonstrate that elastic anisotropy of magnesium perovskite is highly enhanced by iron incorporation. Furthermore anti-correlation between bulk sound velocity and shear wave velocity was confirmed with iron content, which is against the theoretical prediction. The anti-correlation found in this study is important, because it enables us to interpret the recent seismological observation of the anti-correlation in the deep lower mantle by means of iron content difference in perovskite. On the other hand, we can learn difference of elasticity between perovskite and post perovskite thorough measurement on CaIrO3, as analog of MgSiO3 perovskite and post perovskite. From a characteristics of the single crystal elasticity of CaIrO3 compounds, we interpreted the texture pattern in the D" layer consistent with recent seismic observation.

  6. Local structure in LaMnO3 and CaMnO3 perovskites: A quantitative structural refinement of Mn K -edge XANES data

    NASA Astrophysics Data System (ADS)

    Monesi, C.; Meneghini, C.; Bardelli, F.; Benfatto, M.; Mobilio, S.; Manju, U.; Sarma, D. D.

    2005-11-01

    Hole-doped perovskites such as La1-xCaxMnO3 present special magnetic and magnetotransport properties, and it is commonly accepted that the local atomic structure around Mn ions plays a crucial role in determining these peculiar features. Therefore experimental techniques directly probing the local atomic structure, like x-ray absorption spectroscopy (XAS), have been widely exploited to deeply understand the physics of these compounds. Quantitative XAS analysis usually concerns the extended region [extended x-ray absorption fine structure (EXAFS)] of the absorption spectra. The near-edge region [x-ray absorption near-edge spectroscopy (XANES)] of XAS spectra can provide detailed complementary information on the electronic structure and local atomic topology around the absorber. However, the complexity of the XANES analysis usually prevents a quantitative understanding of the data. This work exploits the recently developed MXAN code to achieve a quantitative structural refinement of the Mn K -edge XANES of LaMnO3 and CaMnO3 compounds; they are the end compounds of the doped manganite series LaxCa1-xMnO3 . The results derived from the EXAFS and XANES analyses are in good agreement, demonstrating that a quantitative picture of the local structure can be obtained from XANES in these crystalline compounds. Moreover, the quantitative XANES analysis provides topological information not directly achievable from EXAFS data analysis. This work demonstrates that combining the analysis of extended and near-edge regions of Mn K -edge XAS spectra could provide a complete and accurate description of Mn local atomic environment in these compounds.

  7. Insight into the CH3NH3PbI3/C interface in hole-conductor-free mesoscopic perovskite solar cells.

    PubMed

    Li, Jiangwei; Niu, Guangda; Li, Wenzhe; Cao, Kun; Wang, Mingkui; Wang, Liduo

    2016-08-07

    Perovskite solar cells (PSCs) with hole-conductor-free mesoscopic architecture have shown superb stability and great potential in practical application. The printable carbon counter electrodes take full responsibility of extracting holes from the active CH3NH3PbI3 absorbers. However, an in depth study of the CH3NH3PbI3/C interface properties, such as the structural formation process and the effect of interfacial conditions on hole extraction, is still lacking. Herein, we present, for the first time, an insight into the spatial confinement induced CH3NH3PbI3/C interface formation by in situ photoluminescence observations during the crystallization process of CH3NH3PbI3. The derived reaction kinetics allows a quantitative description of the perovskite formation process. In addition, we found that the interfacial contact between carbon and perovskite was dominant for hole extraction efficiency and associated with the photovoltaic parameter of short circuit current density (JSC). Consequently, we conducted a solvent vapor assisted process of PbI2 diffusion to carefully control the CH3NH3PbI3/C interface with less unreacted PbI2 barrier. The improvement of interface conditions thereby contributes to a high hole extraction proved by the charge extraction resistance and PL lifetime change, resulting in the increased JSC valve.

  8. Hybrid Organic-Inorganic Perovskite Photodetectors.

    PubMed

    Tian, Wei; Zhou, Huanping; Li, Liang

    2017-11-01

    Hybrid organic-inorganic perovskite materials garner enormous attention for a wide range of optoelectronic devices. Due to their attractive optical and electrical properties including high optical absorption coefficient, high carrier mobility, and long carrier diffusion length, perovskites have opened up a great opportunity for high performance photodetectors. This review aims to give a comprehensive summary of the significant results on perovskite-based photodetectors, focusing on the relationship among the perovskite structures, device configurations, and photodetecting performances. An introduction of recent progress in various perovskite structure-based photodetectors is provided. The emphasis is placed on the correlation between the perovskite structure and the device performance. Next, recent developments of bandgap-tunable perovskite and hybrid photodetectors built from perovskite heterostructures are highlighted. Then, effective approaches to enhance the stability of perovskite photodetector are presented, followed by the introduction of flexible and self-powered perovskite photodetectors. Finally, a summary of the previous results is given, and the major challenges that need to be addressed in the future are outlined. A comprehensive summary of the research status on perovskite photodetectors is hoped to push forward the development of this field. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Strain Accommodation By Facile WO6 Octahedral Distortion and Tilting During WO3 Heteroepitaxy on SrTiO3(001)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Du, Yingge; Gu, Meng; Varga, Tamas

    2014-08-27

    In this paper, we show that compared to other BO6 octahedra in ABO3 structured perovskite oxides, the WO6 octahedra in tungsten trioxide (WO3) can withstand a much larger degree of distortion and tilting to accommodate interfacial strain, which in turn strongly impact the nucleation, structure, and defect formation during the epitaxial growth of WO3 on SrTiO3(001). A meta-stable tetragonal phase can be stabilized by epitaxy and a thickness dependent phase transition (tetragonal to monoclinic) is observed. In contrast to misfit dislocations to accommodate the interfacial stain, the facial WO6 octahedral distortion and tilting give rise to three types of planarmore » defects that affect more than 15 monolayers from the interface. These atomically resolved, unusual interfacial defects may significantly alter the electronic, electrochromic, and mechanical properties of the epitaxial films.« less

  10. Sn2+—Stabilization in MASnI3 perovskites by superhalide incorporation

    NASA Astrophysics Data System (ADS)

    Xiang, Junxiang; Wang, Kan; Xiang, Bin; Cui, Xudong

    2018-03-01

    Sn-based hybrid halide perovskites are a potential solution to replace Pb and thereby reduce Pb toxicity in MAPbI3 perovskite-based solar cells. However, the instability of Sn2+ in air atmosphere causes a poor reproducibility of MASnI3, hindering steps towards this goal. In this paper, we propose a new type of organic metal-superhalide perovskite of MASnI2BH4 and MASnI2AlH4. Through first-principles calculations, our results reveal that the incorporation of BH4 and AlH4 superhalides can realize an impressive enhancement of oxidation resistance of Sn2+ in MASnI3 perovskites because of the large electron transfer between Sn2+ and [BH4]-/[AlH4]-. Meanwhile, the high carrier mobility is preserved in these superhalide perovskites and only a slight decrease is observed in the optical absorption strength. Our studies provide a new path to attain highly stable performance and reproducibility of Sn-based perovskite solar cells.

  11. Mechanism of biphasic charge recombination and accumulation in TiO2 mesoporous structured perovskite solar cells.

    PubMed

    Wang, Hao-Yi; Wang, Yi; Yu, Man; Han, Jun; Guo, Zhi-Xin; Ai, Xi-Cheng; Zhang, Jian-Ping; Qin, Yujun

    2016-04-28

    Organic-inorganic halide perovskite solar cells are becoming the next big thing in the photovoltaic field owing to their rapidly developing photoelectric conversion performance. Herein, mesoporous structured perovskite devices with various perovskite grain sizes are fabricated by a sequential dropping method, and the charge recombination dynamics is investigated by transient optical-electric measurements. All devices exhibit an overall power conversion efficiency around 15%. More importantly, a biphasic trap-limited charge recombination process is proposed and interpreted by taking into account the specific charge accumulation mechanism in perovskite solar cells. At low Fermi levels, photo-generated electrons predominately populate in the perovskite phase, while at high Fermi levels, most electrons occupy traps in mesoporous TiO2. As a result, the dynamics of charge recombination is, respectively, dominated by the perovskite phase and mesoporous TiO2 in these two cases. The present work would give a new perspective on the charge recombination process in meso-structured perovskite solar cells.

  12. Structure and Growth Control of Organic-Inorganic Halide Perovskites for Optoelectronics: From Polycrystalline Films to Single Crystals.

    PubMed

    Chen, Yani; He, Minhong; Peng, Jiajun; Sun, Yong; Liang, Ziqi

    2016-04-01

    Recently, organic-inorganic halide perovskites have sparked tremendous research interest because of their ground-breaking photovoltaic performance. The crystallization process and crystal shape of perovskites have striking impacts on their optoelectronic properties. Polycrystalline films and single crystals are two main forms of perovskites. Currently, perovskite thin films have been under intensive investigation while studies of perovskite single crystals are just in their infancy. This review article is concentrated upon the control of perovskite structures and growth, which are intimately correlated for improvements of not only solar cells but also light-emitting diodes, lasers, and photodetectors. We begin with the survey of the film formation process of perovskites including deposition methods and morphological optimization avenues. Strategies such as the use of additives, thermal annealing, solvent annealing, atmospheric control, and solvent engineering have been successfully employed to yield high-quality perovskite films. Next, we turn to summarize the shape evolution of perovskites single crystals from three-dimensional large sized single crystals, two-dimensional nanoplates, one-dimensional nanowires, to zero-dimensional quantum dots. Siginificant functions of perovskites single crystals are highlighted, which benefit fundamental studies of intrinsic photophysics. Then, the growth mechanisms of the previously mentioned perovskite crystals are unveiled. Lastly, perspectives for structure and growth control of perovskites are outlined towards high-performance (opto)electronic devices.

  13. [The kidney transplantation from the ABO-incompatible donors].

    PubMed

    Goriaĭnov, V A; Kaabak, M M; Babenko, N N; Shishlo, L A; Morozova, M M; Ragimov, A A; Dashkova, N G; Salimov, É L

    2012-01-01

    The experience of 28 allotransplantations of ABO-incompatible kidneys was compared with the treatment results of 38 ABO-compatible renal transplantations. The transplanted kidney function, morphological changes of the transplanted kidney and the comparative analysis of actuary survival in both groups showed no significant difference. The results of the study prove the validity of the kidney transplantation from the ABO-incompatible donors.

  14. Mixed Sn-Ge Perovskite for Enhanced Perovskite Solar Cell Performance in Air.

    PubMed

    Ito, Nozomi; Kamarudin, Muhammad Akmal; Hirotani, Daisuke; Zhang, Yaohong; Shen, Qing; Ogomi, Yuhei; Iikubo, Satoshi; Minemoto, Takashi; Yoshino, Kenji; Hayase, Shuzi

    2018-04-05

    Lead-based perovskite solar cells have gained ground in recent years, showing efficiency as high as 20%, which is on par with that of silicon solar cells. However, the toxicity of lead makes it a nonideal candidate for use in solar cells. Alternatively, tin-based perovskites have been proposed because of their nontoxic nature and abundance. Unfortunately, these solar cells suffer from low efficiency and stability. Here, we propose a new type of perovskite material based on mixed tin and germanium. The material showed a band gap around 1.4-1.5 eV as measured from photoacoustic spectroscopy, which is ideal from the perspective of solar cells. In a solar cell device with inverted planar structure, pure tin perovskite solar cell showed a moderate efficiency of 3.31%. With 5% doping of germanium into the perovskite, the efficiency improved up to 4.48% (6.90% after 72 h) when measured in air without encapsulation.

  15. Efficient Planar Structured Perovskite Solar Cells with Enhanced Open-Circuit Voltage and Suppressed Charge Recombination Based on a Slow Grown Perovskite Layer from Lead Acetate Precursor.

    PubMed

    Li, Cong; Guo, Qiang; Wang, Zhibin; Bai, Yiming; Liu, Lin; Wang, Fuzhi; Zhou, Erjun; Hayat, Tasawar; Alsaedi, Ahmed; Tan, Zhan'ao

    2017-12-06

    For planar structured organic-inorganic hybrid perovskite solar cells (PerSCs) with the poly(3,4-ethylenedioxythiophene:polystyrene sulfonate) (PEDOT:PSS) hole transport layer, the open-circuit voltage (V oc ) of the device is limited to be about 1.0 V, resulting in inferior performance in comparison with TiO 2 -based planar counterparts. Therefore, increasing V oc of the PEDOT:PSS-based planar device is an important way to enhance the efficiency of the PerSCs. Herein, we demonstrate a novel approach for perovskite film formation and the film is formed by slow growth from lead acetate precursor via a one-step spin-coating process without the thermal annealing (TA) process. Because the perovskite layer grows slowly and naturally, high-quality perovskite film can be achieved with larger crystalline particles, less defects, and smoother surface morphology. Ultraviolet absorption, X-ray diffraction, scanning electron microscopy, steady-state fluorescence spectroscopy (photoluminescence), and time-resolved fluorescence spectroscopy are used to clarify the crystallinity, morphology, and internal defects of perovskite thin films. The power conversion efficiency of p-i-n PerSCs based on slow-grown film (16.33%) shows greatly enhanced performance compared to that of the control device based on traditional thermally annealed perovskite film (14.33%). Furthermore, the V oc of the slow-growing device reaches 1.12 V, which is 0.1 V higher than that of the TA device. These findings indicate that slow growth of the perovskite layer from lead acetate precursor is a promising approach to achieve high-quality perovskite film for high-performance PerSCs.

  16. Photoluminescence characterisations of a dynamic aging process of organic-inorganic CH3NH3PbBr3 perovskite

    NASA Astrophysics Data System (ADS)

    Sheng, R.; Wen, X.; Huang, S.; Hao, X.; Chen, S.; Jiang, Y.; Deng, X.; Green, M. A.; Ho-Baillie, A. W. Y.

    2016-01-01

    After unprecedented development of organic-inorganic lead halide perovskite solar cells over the past few years, one of the biggest barriers towards their commercialization is the stability of the perovskite material. It is thus important to understand the interaction between the perovskite material and oxygen and/or humidity and the associated degradation process in order to improve device and encapsulation design for better durability. Here we characterize the dynamic aging process in vapour-assisted deposited (VASP) CH3NH3PbBr3 perovskite thin films using advanced optical techniques, such as time-resolved photoluminescence and fluorescence lifetime imaging microscopy (FLIM). Our investigation reveals that the perovskite grains grow spontaneously and the larger grains are formed at room temperature in the presence of moisture and oxygen. This crystallization process leads to a higher density of defects and a shorter carrier lifetime, specifically in the larger grains. Excitation-intensity-dependent steady-state photoluminescence shows both N2 stored and aged perovskite exhibit a super-linear increase of photoluminescence intensity with increasing excitation intensity; and the larger slope in aged sample suggests a larger density of defects is generated, consistent with time-resolved PL measurements.

  17. Structural and Magnetic Phase Coexistence in Oxygen Deficient Perovskites (Sr,Ca)FeO 2 . 5 + δ

    NASA Astrophysics Data System (ADS)

    Carlo, J. P.; Evans, M. E.; Anczarski, J. A.; Ock, J.; Boyd, K.; Pollichemi, J. R.; Leahy, I. A.; Vogel, W.; Viescas, A. J.; Papaefthymiou, G. C.

    A variety of compounds crystallize into perovskite and similar structures, making them versatile laboratories for many phenomena and applications, including multiferroicity, superconductivity, and photovoltaics. Oxygen-deficient perovskites ABOx have attracted interest for use in fuel cells and related applications due to high oxygen mobility and the possibility of charge disproportionation. Vast chemical flexibility is obtained through reductions in lattice symmetry and rotation/distortion of the BO6 octahedra, as well as ordering of oxygen vacancies. We have synthesized and studied the structural and magnetic properties of oxygen-deficient perovskites (Sr,Ca)FeO2 . 5 + δ using x-ray diffraction and Mossbauer spectroscopy. While the ideal perovskite has δ = 0.5, this requires Fe4+, and hence strongly oxidizing environments. When grown in air, Fe3+ is favored, yielding δ ~ 0. SrFeO2 . 5 + δ exhibits cubic symmetry and paramagnetism at 300K, but CaFeO2 . 5 + δ crystallizes into the orthorhombic brownmillerite structure, and is magnetically ordered at 300K. In the doped intermediaries we find coexistence of cubic/paramagnetic and orthorhombic/magnetic phases over a wide range of Ca content. Financial support from the Villanova Undergraduate Research Fellowship program and the Research Corporation for Science Advancement.

  18. In-situ neutron diffraction of LaCoO3 perovskite under uniaxial compression. I. Crystal structure analysis and texture development

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Aman, Amjad; Chen, Yan; Lugovy, Mykola

    2014-01-01

    The dynamics of texture formation, changes in crystal structure and stress accommodation mechanisms are studied in R3c rhombohedral LaCoO3 perovskite during in-situ uniaxial compression experiment by neutron diffraction. The neutron diffraction revealed the complex crystallographic changes causing the texture formation and significant straining along certain crystallographic directions during in-situ compression, which are responsible for the appearance of hysteresis and non-linear ferroelastic deformation in LaCoO3 perovskite. The irreversible strain after the first loading was connected with the appearance of non-recoverable changes in the intensity ratio of certain crystallographic peaks, causing non-reversible texture formation. However in the second loading/unloading cycle the hysteresismore » loop was closed and no irreversible strain appears after deformation. The significant texture formation is responsible for increase in the Young s modulus of LaCoO3 at high compressive loads, where the reported values of Young s modulus increase from 76 GPa measured at the very beginning of the loading to 194 GPa at 900 MPa applied compressive stress measured at the beginning of the unloading curve.« less

  19. Efficient Sky-Blue Perovskite Light-Emitting Devices Based on Ethylammonium Bromide Induced Layered Perovskites.

    PubMed

    Wang, Qi; Ren, Jie; Peng, Xue-Feng; Ji, Xia-Xia; Yang, Xiao-Hui

    2017-09-06

    Low-dimensional organometallic halide perovskites are actively studied for the light-emitting applications due to their properties such as solution processability, high luminescence quantum yield, large exciton binding energy, and tunable band gap. Introduction of large-group ammonium halides not only serves as a convenient and versatile method to obtain layered perovskites but also allows the exploitation of the energy-funneling process to achieve a high-efficiency light emission. Herein, we investigate the influence of the addition of ethylammonium bromide on the morphology, crystallite structure, and optical properties of the resultant perovskite materials and report that the phase transition from bulk to layered perovskite occurs in the presence of excess ethylammonium bromide. On the basis of this strategy, we report green perovskite light-emitting devices with the maximum external quantum efficiency of ca. 3% and power efficiency of 9.3 lm/W. Notably, blue layered perovskite light-emitting devices with the Commission Internationale de I'Eclairage coordinates of (0.16, 0.23) exhibit the maximum external quantum efficiency of 2.6% and power efficiency of 1 lm/W at 100 cd/m 2 , representing a large improvement over the previously reported analogous devices.

  20. Identification and characterization of the intermediate phase in hybrid organic-inorganic MAPbI3 perovskite.

    PubMed

    Guo, Xin; McCleese, Christopher; Kolodziej, Charles; Samia, Anna C S; Zhao, Yixin; Burda, Clemens

    2016-03-07

    Perovskite films were prepared using single step solution deposition at different annealing temperatures and annealing times. The crystal structure, phases and grain size were investigated with XRD, XPS and SEM/EDX. The prepared films show a typical orientation of tetragonal perovskite phase and a gradual transition at room temperature from the yellow intermediate phase to the black perovskite phase. Films with high purity were obtained by sintering at 100 °C. In addition, the chemical composition and crystal structure of intermediate phase were investigated in detail. FTIR, UV-vis and NMR spectra revealed the occurance of DMF complexes. Interestingly, the intermediate phase could be transformed to the black perovskite phase upon X-ray irradiation. In addition, the recovery of the aged perovskite films from a yellow intermediate phase back to the black perovskite was shown to be viable via heating and X-ray irradiation.

  1. Moessbauer spectroscopy of Mg(0.9)Fe(0.1)SiO3 perovskite

    NASA Technical Reports Server (NTRS)

    Jeanloz, Raymond; O'Neill, Bridget; Pasternak, Moshe P.; Taylor, R. D.; Bohlen, Steven R.

    1992-01-01

    Ambient pressure Moessbauer spectra of Mg(0.9)Fe-57(0.1)SiO3 perovskite synthesized at pressure-temperature conditions of about 50 GPa and 1700 K show that the iron is entirely high-spin Fe(2+) and appears to be primarily located in the octahedral site within the crystal structure. We observe broad Moessbauer lines, suggesting a distribution of electric-field gradients caused by disorder associated with the Fe ions. Also, the perovskite exhibits magnetic ordering at temperatures lower than 5 K, implying that there is a magnetic contribution to the absolute ('third-law') entropy of this phase.

  2. Strong Photonic-Band-Gap Effect on the Spontaneous Emission in 3D Lead Halide Perovskite Photonic Crystals.

    PubMed

    Zhou, Xue; Li, Mingzhu; Wang, Kang; Li, Huizeng; Li, Yanan; Li, Chang; Yan, Yongli; Zhao, Yongsheng; Song, Yanlin

    2018-03-25

    Stimulated emission in perovskite-embedded polymer opal structures is investigated. A polymer opal structure is filled with a perovskite, and perovskite photonic crystals are prepared. The spontaneous emission of the perovskite embedded in the polymer opal structures exhibits clear signatures of amplified spontaneous emission (ASE) via gain modulation. The difference in refractive-index contrast between the perovskite and the polymer opal is large enough for retaining photonic-crystals properties. The photonic band gap has a strong effect on the fluorescence emission intensity and lifetime. The stimulated emission spectrum exhibits a narrow ASE rather than a wide fluorescence peak in the thin film. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Crystal structure of tetra­wickmanite, Mn2+Sn4+(OH)6

    PubMed Central

    Lafuente, Barbara; Yang, Hexiong; Downs, Robert T.

    2015-01-01

    The crystal structure of tetra­wickmanite, ideally Mn2+Sn4+(OH)6 [mangan­ese(II) tin(IV) hexa­hydroxide], has been determined based on single-crystal X-ray diffraction data collected from a natural sample from Långban, Sweden. Tetra­wickmanite belongs to the octa­hedral-framework group of hydroxide-perovskite minerals, described by the general formula BB’(OH)6 with a perovskite derivative structure. The structure differs from that of an ABO3 perovskite in that the A site is empty while each O atom is bonded to an H atom. The perovskite B-type cations split into ordered B and B′ sites, which are occupied by Mn2+ and Sn4+, respectively. Tetra­wickmanite exhibits tetra­gonal symmetry and is topologically similar to its cubic polymorph, wickmanite. The tetra­wickmanite structure is characterized by a framework of alternating corner-linked [Mn2+(OH)6] and [Sn4+(OH)6] octa­hedra, both with point-group symmetry -1. Four of the five distinct H atoms in the structure are statistically disordered. The vacant A site is in a cavity in the centre of a distorted cube formed by eight octa­hedra at the corners. However, the hydrogen-atom positions and their hydrogen bonds are not equivalent in every cavity, resulting in two distinct environments. One of the cavities contains a ring of four hydrogen bonds, similar to that found in wickmanite, while the other cavity is more distorted and forms crankshaft-type chains of hydrogen bonds, as previously proposed for tetra­gonal stottite, Fe2+Ge4+(OH)6. PMID:25878828

  4. Photon Reabsorption in Mixed CsPbCl3:CsPbI3 Perovskite Nanocrystal Films for Light-Emitting Diodes

    PubMed Central

    2017-01-01

    Cesium lead halide nanocrystals, CsPbX3 (X = Cl, Br, I), exhibit photoluminescence quantum efficiencies approaching 100% without the core–shell structures usually used in conventional semiconductor nanocrystals. These high photoluminescence efficiencies make these crystals ideal candidates for light-emitting diodes (LEDs). However, because of the large surface area to volume ratio, halogen exchange between perovskite nanocrystals of different compositions occurs rapidly, which is one of the limiting factors for white-light applications requiring a mixture of different crystal compositions to achieve a broad emission spectrum. Here, we use mixtures of chloride and iodide CsPbX3 (X = Cl, I) perovskite nanocrystals where anion exchange is significantly reduced. We investigate samples containing mixtures of perovskite nanocrystals with different compositions and study the resulting optical and electrical interactions. We report excitation transfer from CsPbCl3 to CsPbI3 in solution and within a poly(methyl methacrylate) matrix via photon reabsorption, which also occurs in electrically excited crystals in bulk heterojunction LEDs. PMID:28316756

  5. Assessing ABO/Rh Blood Group Frequency and Association with Asymptomatic Malaria among Blood Donors Attending Arba Minch Blood Bank, South Ethiopia

    PubMed Central

    Alemu, Getaneh; Mama, Mohammedaman

    2016-01-01

    Background. Determination of the various ABO/Rh blood group distributions and their association with malaria infection has paramount importance in the context of transfusion medicine and malaria control. Methods. Facility based cross-sectional study was conducted from February to June, 2015, to assess ABO/Rh blood groups distribution and their association with asymptomatic malaria. A structured questionnaire was used to collect data. Blood grouping was done using monoclonal antibodies. Thin and thick blood films were examined for Plasmodium parasites. Data were analyzed using SPSS version 20.0. Results. A total of 416 blood donors participated with median age of 22 ± 0.29 (median ± standard error of the mean). Distribution of ABO phenotypes, in decreasing order, was O (175, 42.1%), A (136, 32.7%), B (87, 20.9%), and AB (18, 4.3%). Most of them were Rh+ (386, 92.8%). The overall malaria prevalence was 4.1% (17/416). ABO blood group is significantly associated with malaria infection (P = 0.022). High rate of parasitemia was seen in blood group O donors (6.899, P = 0.003) compared to those with other ABO blood groups. Conclusion. Blood groups O and AB phenotypes are the most and the least ABO blood groups, respectively. There is significant association between ABO blood group and asymptomatic malaria parasitemia. PMID:26925291

  6. Structure and magnetic properties of spinel-perovskite nanocomposite thin films on SrTiO3 (111) substrates

    NASA Astrophysics Data System (ADS)

    Kim, Dong Hun; Yang, Junho; Kim, Min Seok; Kim, Tae Cheol

    2016-09-01

    Epitaxial CoFe2O4-BiFeO3 nanocomposite thin films were synthesized on perovskite structured SrTiO3 (001) and (111) substrates by combinatorial pulsed laser deposition and characterized using scanning electron microscopy, x-ray diffraction, and vibrating sample magnetometer. Triangular BiFeO3 nanopillars were formed in a CoFe2O4 matrix on (111) oriented SrTiO3 substrates, while CoFe2O4 nanopillars with rectangular or square top surfaces grew in a BiFeO3 matrix on (001) substrates. The magnetic hysteresis loops of nanocomposites on (111) oriented SrTiO3 substrates showed isotropic properties due to the strain relaxation while those of films on SrTiO3 (001) substrates exhibited a strong out-of-plane anisotropy originated from shape and strain effects.

  7. ABO Blood Group and Endometrial Carcinoma: A Preliminary Single-Center Experience from Saudi Arabia.

    PubMed

    Abu-Zaid, Ahmed; Alsabban, Mohannad; Abuzaid, Mohammed; Alomar, Osama; Al-Badawi, Ismail A; Salem, Hany

    2017-12-18

    Inherited ABO blood groups have been shown to play possible contributions in the pathogenesis of various gynecologic and non-gynecologic carcinomas. With regard to gynecologic carcinomas, there is a confined number of studies that explored the relationship between ABO blood group and endometrial carcinoma (EC) in the PubMed-indexed literature. To the best of our knowledge, no such study has ever been conducted in Saudi Arabia. Our study has two objectives: (I) to determine the prevalence of ABO blood groups among Saudi patients with EC, and (II) to explore the relationship between ABO blood group and several clinico-pathological prognostic parameters (namely: menopausal status [age], body mass index [BMI], tumor grade, FIGO [Fédération Internationale de Gynécologie et d'Obstétrique] stage and recurrence) in Saudi patients with EC. A retrospective cross-sectional study from 01-January-2010 to 31-July-2014 was conducted at King Faisal Specialist Hospital & Research Centre, Riyadh, Saudi Arabia - a referral tertiary healthcare institute. One-hundred and fourteen patients (n=114) were included in the study. Clinico-pathological data were extrapolated from medical records, and their association with ABO blood groups were evaluated. Categorical data were presented as number of cases (n) and percentages (%). Two-tailed Chi-square test was used for univariate analysis. For all purposes, p values <0.05 were regarded as statistically significant. The mean age and BMI were 59.5 ± 10.8 years (range: 31 - 90) and 36.6 ± 8.6 kg/m 2 (range: 17 - 60), respectively. The vast majority of patients were post-menopausal (86%), had BMI >28 kg/m 2 (84.2%), diagnosed with early FIGO stage I-II (76.3%) and developed no recurrence (86.8%). The frequencies of ABO blood group types A, B, AB, and O were 28.1%, 12.3%, 3.5% and 56.1%, respectively. When ABO blood groups were analyzed as four different types (A, B, AB and O), O-type was the most common ABO blood group in pre- and post

  8. Broadband Emission in Two-Dimensional Hybrid Perovskites: The Role of Structural Deformation.

    PubMed

    Cortecchia, Daniele; Neutzner, Stefanie; Srimath Kandada, Ajay Ram; Mosconi, Edoardo; Meggiolaro, Daniele; De Angelis, Filippo; Soci, Cesare; Petrozza, Annamaria

    2017-01-11

    Only a selected group of two-dimensional (2D) lead-halide perovskites shows a peculiar broad-band photoluminescence. Here we show that the structural distortions of the perovskite lattice can determine the defectivity of the material by modulating the defect formation energies. By selecting and comparing two archetype systems, namely, (NBT) 2 PbI 4 and (EDBE)PbI 4 perovskites (NBT = n-butylammonium and EDBE = 2,2-(ethylenedioxy)bis(ethylammonium)), we find that only the latter, subject to larger deformation of the Pb-X bond length and X-Pb-X bond angles, sees the formation of V F color centers whose radiative decay ultimately leads to broadened PL. These findings highlight the importance of structural engineering to control the optoelectronic properties of this class of soft materials.

  9. Octahedral tilting instabilities in inorganic halide perovskites

    NASA Astrophysics Data System (ADS)

    Bechtel, Jonathon S.; Van der Ven, Anton

    2018-02-01

    Dynamic instabilities, stabilized by anharmonic interactions in cubic and tetragonal halide perovskites at high temperature, play a role in the electronic structure and optoelectronic properties of halide perovskites. In particular, inorganic and hybrid perovskite materials undergo structural phase transitions associated with octahedral tilts of the metal-halide octahedra. We investigate the structural instabilities present in inorganic Cs M X3 perovskites with Pb or Sn on the metal site and Br or I on the X site. Defining primary order parameters in terms of symmetry-adapted collective displacement modes and secondary order parameters in terms of symmetrized Hencky strain components, we unravel the coupling between octahedral tilt modes and macroscopic strains as well as the role of A -site displacements in perovskite phase stability. Symmetry-allowed secondary strain order parameters are enumerated for the 14 unique perovskite tilt systems. Using first-principles calculations to explore the Born-Oppenheimer energy surface in terms of symmetrized order parameters, we find coupling between octahedral tilting and A -site displacements is necessary to stabilize P n m a ground states. Additionally, we show that the relative stability of an inorganic halide perovskite tilt system correlates with the volume decrease from the high-symmetry cubic phase to the low-symmetry distorted phase.

  10. Structure and Growth Control of Organic–Inorganic Halide Perovskites for Optoelectronics: From Polycrystalline Films to Single Crystals

    PubMed Central

    Chen, Yani; He, Minhong; Peng, Jiajun; Sun, Yong

    2016-01-01

    Recently, organic–inorganic halide perovskites have sparked tremendous research interest because of their ground‐breaking photovoltaic performance. The crystallization process and crystal shape of perovskites have striking impacts on their optoelectronic properties. Polycrystalline films and single crystals are two main forms of perovskites. Currently, perovskite thin films have been under intensive investigation while studies of perovskite single crystals are just in their infancy. This review article is concentrated upon the control of perovskite structures and growth, which are intimately correlated for improvements of not only solar cells but also light‐emitting diodes, lasers, and photodetectors. We begin with the survey of the film formation process of perovskites including deposition methods and morphological optimization avenues. Strategies such as the use of additives, thermal annealing, solvent annealing, atmospheric control, and solvent engineering have been successfully employed to yield high‐quality perovskite films. Next, we turn to summarize the shape evolution of perovskites single crystals from three‐dimensional large sized single crystals, two‐dimensional nanoplates, one‐dimensional nanowires, to zero‐dimensional quantum dots. Siginificant functions of perovskites single crystals are highlighted, which benefit fundamental studies of intrinsic photophysics. Then, the growth mechanisms of the previously mentioned perovskite crystals are unveiled. Lastly, perspectives for structure and growth control of perovskites are outlined towards high‐performance (opto)electronic devices. PMID:27812463

  11. Carrier injection and recombination processes in perovskite CH3NH3PbI3 solar cells studied by electroluminescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Handa, Taketo; Okano, Makoto; Tex, David M.; Shimazaki, Ai; Aharen, Tomoko; Wakamiya, Atsushi; Kanemitsu, Yoshihiko

    2016-02-01

    Organic-inorganic hybrid perovskite materials, CH3NH3PbX3 (X = I and Br), are considered as promising candidates for emerging thin-film photovoltaics. For practical implementation, the degradation mechanism and the carrier dynamics during operation have to be clarified. We investigated the degradation mechanism and the carrier injection and recombination processes in perovskite CH3NH3PbI3 solar cells using photoluminescence (PL) and electroluminescence (EL) imaging spectroscopies. By applying forward bias-voltage, an inhomogeneous distribution of the EL intensity was clearly observed from the CH3NH3PbI3 solar cells. By comparing the PL- and EL-images, we revealed that the spatial inhomogeneity of the EL intensity is a result of the inhomogeneous luminescence efficiency in the perovskite layer. An application of bias-voltage for several tens of minutes in air caused a decrease in the EL intensity and the conversion efficiency of the perovskite solar cells. The degradation mechanism of perovskite solar cells under bias-voltage in air is discussed.

  12. A Long-Term View on Perovskite Optoelectronics.

    PubMed

    Docampo, Pablo; Bein, Thomas

    2016-02-16

    Recently, metal halide perovskite materials have become an exciting topic of research for scientists of a wide variety of backgrounds. Perovskites have found application in many fields, starting from photovoltaics and now also making an impact in light-emitting applications. This new class of materials has proven so interesting since it can be easily solution processed while exhibiting materials properties approaching the best inorganic optoelectronic materials such as GaAs and Si. In photovoltaics, in only 3 years, efficiencies have rapidly increased from an initial value of 3.8% to over 20% in recent reports for the commonly employed methylammonium lead iodide (MAPI) perovskite. The first light emitting diodes and light-emitting electrochemical cells have been developed already exhibiting internal quantum efficiencies exceeding 15% for the former and tunable light emission spectra. Despite their processing advantages, perovskite optoelectronic materials suffer from several drawbacks that need to be overcome before the technology becomes industrially relevant and hence achieve long-term application. Chief among these are the sensitivity of the structure toward moisture and crystal phase transitions in the device operation regime, unreliable device performance dictated by the operation history of the device, that is, hysteresis, the inherent toxicity of the structure, and the high cost of the employed charge selective contacts. In this Account, we highlight recent advances toward the long-term viability of perovskite photovoltaics. We identify material decomposition routes and suggest strategies to prevent damage to the structure. In particular, we focus on the effect of moisture upon the structure and stabilization of the material to avoid phase transitions in the solar cell operating range. Furthermore, we show strategies to achieve low-cost chemistries for the development of hole transporters for perovskite solar cells, necessary to be able to compete with other

  13. High transport and excellent optical property of a two-dimensional single-layered hybrid perovskite (C4H9NH3)2PbBr4: a theoretical study.

    PubMed

    Lei, Jun-Hui; Zhao, Yu-Qing; Tang, Qiong; Lin, Jian-Guo; Cai, Meng-Qiu

    2018-05-16

    Organic-inorganic hybrid perovskites are developed to pursue high charge carrier mobility and light absorption coefficient. In this study, we present a detailed comparative research of the atomic and electronic structures of single-layered perovskites (C4H9NH3)2PbBr4 with two-dimensional/three-dimensional (2D/3D) spatial arrangement to predict the in plane charge carrier mobility along with the charge effective mass, elastic constant, and deformation potential. The calculated results reveal that the intrinsic in plane carrier mobilities of 2D single-layered hybrid perovskite (C4H9NH3)2PbBr4 along the 100 and 010 directions are superior to those of the 3D structure. Furthermore, the optical properties are calculated from the electronic structure; it is found that the light absorption spectrum of 2D single-layered perovskite (C4H9NH3)2PbBr4 with a high absorption coefficient is wider than that of the 3D phase. We speculate that the superior mobility and wider absorption spectrum of the 2D mono-layered perovskite are due to high charge density and ferroelectricity originating from structure distortion upon 3D-to-2D structure transformation. These results indicate that the 2D single-layered hybrid perovskite (C4H9NH3)2PbBr4 is a potential candidate for application in the optoelectronic and photovoltaic fields.

  14. Influence of ABO blood group on sports performance.

    PubMed

    Lippi, Giuseppe; Gandini, Giorgio; Salvagno, Gian Luca; Skafidas, Spyros; Festa, Luca; Danese, Elisa; Montagnana, Martina; Sanchis-Gomar, Fabian; Tarperi, Cantor; Schena, Federico

    2017-06-01

    Despite being a recessive trait, the O blood group is the most frequent worldwide among the ABO blood types. Since running performance has been recognized as a major driver of evolutionary advantage in humans, we planned a study to investigate whether the ABO blood group may have an influence on endurance running performance in middle-aged recreational athletes. The study population consisted of 52 recreational, middle-aged, Caucasian athletes (mean age: 49±13 years, body mass index, 23.4±2.3 kg/m 2 ), regularly engaged in endurance activity. The athletes participated to a scientific event called "Run for Science" (R4S), entailing the completion of a 21.1 km (half-marathon) run under competing conditions. The ABO blood type status of the participants was provided by the local Service of Transfusion Medicine. In univariate analysis, running performance was significantly associated with age and weekly training, but not with body mass index. In multiple linear regression analysis, age and weekly training remained significantly associated with running performance. The ABO blood group status was also found to be independently associated with running time, with O blood type athletes performing better than those with non-O blood groups. Overall, age, weekly training and O blood group type explained 62.2% of the total variance of running performance (age, 41.6%; training regimen, 10.5%; ABO blood group, 10.1%). The results of our study show that recreational athletes with O blood group have better endurance performance compared to those with non-O blood group types. This finding may provide additional support to the putative evolutionary advantages of carrying the O blood group.

  15. Interface architecture between TiO2/perovskite, perovskite/hole transport layer, and perovskite grain boundary(Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Hayase, Shuzi; Hirotani, Daisuke; Moriya, Masahiro; Ogomi, Yuhei; Shen, Qing; Yoshino, Kenji; Toyoda, Taro

    2016-09-01

    In order to examine the interface structure of TiO2/perovskite layer, quartz crystal microbalance sensor (QCM) was used. On the QCM sensor, TiO2 layer was fabricated and the PbI2 solution in Dimethylformamide (DMF) was passed on the QCM sensor to estimate the adsorption density of the PbI2 on the titania2. The amount of PbI2 adsorption on TiO2 surface increased as the adsorption time and leveled off at a certain time. PbI2 still remained even after the solvent only (DMF) was passed on the TiO2 layer on QCM (namely rinsing with DMF), suggesting that the PbI2 was tightly bonded on the TiO2 surface. The bonding structure was found to be Ti-O-Pb linkage by XPS analysis. We concluded that the Ti-OH on the surface of TiO2 reacts with I-Pb-I to form Ti-O-Pb-I and HI (Fig.1 B). The surface trap density was measured by thermally stimulated current (TSC) method. Before the PbI2 passivation, the trap density of TiO2 was 1019 cm3. The trap density decreased to 1016/cm3 after the PbI2 passivation, suggesting that the TiO2 surface trap was passivated with I-Pb-I. The passivation density was tuned by the concentration of PbI2 in DMF, by which TiO2 layer was passivated. Perovskite solar cells were fabricated on the passivated TiO2 layer with various PbI2 passivation densities by one step process (mixture of PbI2 + MAI in DMF). It was found that Jsc increased with an increase in the Ti-O-Pb density. We concluded that the interface between TiO2 and perovskite layer has passivation structure consisting of Ti-O-Pb-I which decreases the trap density of the interfaces and supresses charge recombination. The effect of Cl anion on high efficiency is still controversial when perovskite layer is prepared by one step method from the mixture of MAI and PbCl2. It was found that adsorption density of PbCl2 on TiO2 surface was much higher than that of PbI2 from the experiment using QCM sensor. After the surface was washed with DMF, Cl and Pb were detected. These results suggest that the TiO2

  16. Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water.

    PubMed

    Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

    2018-06-08

    CH 3 NH 3 PbBr 3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH 3 NH 3 PbBr 3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH 3 NH 3 PbBr 3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

  17. Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water

    NASA Astrophysics Data System (ADS)

    Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

    2018-06-01

    CH3NH3PbBr3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH3NH3PbBr3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH3NH3PbBr3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

  18. Electronic structure and chemical bonding in La1-x Sr x MnO3 perovskite ceramics

    NASA Astrophysics Data System (ADS)

    Thenmozhi, N.; Sasikumar, S.; Sonai, S.; Saravanan, R.

    2017-04-01

    This study reports on the synthesis of La1-x Sr x MnO3 (x  =  0.3, 0.4 and 0.5) manganites by high temperature solid state reaction method using lanthanum oxide, strontium carbonate and manganese oxide as starting materials. The synthesized samples were characterized by XRD, UV-vis, SEM/EDS and VSM. Structural characterization shows that all the prepared samples have the perovskite rhombohedral structure. Influence of Sr doping on electron density distributions in the lattice structure of LaMnO3 were analyzed through maximum entropy method (MEM). Cell parameters are found to be decreasing with the addition of Sr content. The qualitative and quantitative analysis by MEM reveals that, incorporation of Sr into LaMnO3 lattice enhances the ionic nature between La and O ions and decreases the covalent nature between Mn and O ions. Optical band gap values are determined from the UV-visible absorption spectra. Particles with polygonal form are observed from the SEM micrographs. The elemental compositions of the synthesized samples are confirmed by EDS. The magnetic properties studied from the M-H plot taken at room temperature indicated that, the prepared samples are exhibited ferromagnetic behavior.

  19. Method for fabricating high aspect ratio structures in perovskite material

    DOEpatents

    Karapetrov, Goran T.; Kwok, Wai-Kwong; Crabtree, George W.; Iavarone, Maria

    2003-10-28

    A method of fabricating high aspect ratio ceramic structures in which a selected portion of perovskite or perovskite-like crystalline material is exposed to a high energy ion beam for a time sufficient to cause the crystalline material contacted by the ion beam to have substantially parallel columnar defects. Then selected portions of the material having substantially parallel columnar defects are etched leaving material with and without substantially parallel columnar defects in a predetermined shape having high aspect ratios of not less than 2 to 1. Etching is accomplished by optical or PMMA lithography. There is also disclosed a structure of a ceramic which is superconducting at a temperature in the range of from about 10.degree. K. to about 90.degree. K. with substantially parallel columnar defects in which the smallest lateral dimension of the structure is less than about 5 microns, and the thickness of the structure is greater than 2 times the smallest lateral dimension of the structure.

  20. CH3 NH3 PbI3 and HC(NH2 )2 PbI3 Powders Synthesized from Low-Grade PbI2 : Single Precursor for High-Efficiency Perovskite Solar Cells.

    PubMed

    Zhang, Yong; Kim, Seul-Gi; Lee, Do-Kyoung; Park, Nam-Gyu

    2018-05-09

    High-efficiency perovskite solar cells are generally fabricated by using highly pure (>99.99 %) PbI 2 mixed with an organic iodide in polar aprotic solvents. However, the use of such an expensive chemical may impede progress toward large-scale industrial applications. Here, we report on the synthesis of perovskite powders by using inexpensive low-grade (99 %) PbI 2 and on the photovoltaic performance of perovskite solar cells prepared from a powder-based single precursor. Pure APbI 3 [A=methylammonium (MA) or formamidinium (FA)] perovskite powders were synthesized by treating low-grade PbI 2 with MAI or FAI in acetonitrile at ambient temperature. The structural phase purity was confirmed by X-ray diffraction. The solar cell with a MAPbI 3 film prepared from the synthesized perovskite powder demonstrated a power conversion efficiency (PCE) of 17.14 %, which is higher than the PCE of MAPbI 3 films prepared by using both MAI and PbI 2 as precursors (PCE=13.09 % for 99 % pure PbI 2 and PCE=16.39 % for 99.9985 % pure PbI 2 ). The synthesized powder showed better absorption and photoluminescence, which were responsible for the better photovoltaic performance. For the FAPbI 3 powder, a solution with a yellow non-perovskite δ-FAPbI 3 powder synthesized at room temperature was found to lead to a black perovskite film, whereas a solution with the black perovskite α-FAPbI 3 powder synthesized at 150 °C was not transformed into a black perovskite film. The α↔δ transition between the powder and film was assumed to correlate with the difference in the iodoplumbates in the powder-dissolved solution. An average PCE of 17.21 % along with a smaller hysteresis [ΔPCE=PCE reverse -PCE forward )=1.53 %] was demonstrated from the perovskite solar cell prepared by using δ-FAPbI 3 powder; this PCE is higher than the average PCE of 17.05 % with a larger hysteresis (ΔPCE=2.71 %) for a device based on a conventional precursor solution dissolving MAI with high

  1. Magnetic properties of solid solutions between BiCrO3 and BiGaO3 with perovskite structures

    NASA Astrophysics Data System (ADS)

    Belik, Alexei A.

    2015-04-01

    Magnetic properties of BiCr1-xGaxO3 perovskite-type solid solutions are reported, and a magnetic phase diagram is established. As-synthesized BiCrO3 and BiCr0.9Ga0.1O3 crystallize in a monoclinic (m) C2/c structure. The Néel temperature (TN) decreases from 111 K in BiCrO3 to 98 K in BiCr0.9Ga0.1O3, and spin-reorientation transition temperature increases from 72 K in BiCrO3 to 83 K in BiCr0.9Ga0.1O3. o-BiCr0.9Ga0.1O3 with a PbZrO3-type orthorhombic structure is obtained by heating m-BiCr0.9Ga0.1O3 up to 573 K in air; it shows similar magnetic properties with those of m-BiCr0.9Ga0.1O3. TN of BiCr0.8Ga0.2O3 is 81 K, and TN of BiCr0.7Ga0.3O3 is 63 K. Samples with x = 0.4, 0.5, 0.6 and 0.7 crystallize in a polar R3c structure. Long-range antiferromagnetic order with weak ferromagnetism is observed below TN = 56 K in BiCr0.6Ga0.4O3, TN = 36 K in BiCr0.5Ga0.5O3 and TN = 18 K in BiCr0.4Ga0.6O3. BiCr0.3Ga0.7O3 shows a paramagnetic behaviour because the Cr concentration is below the percolation threshold of 31%.

  2. Semitransparent Fully Air Processed Perovskite Solar Cells.

    PubMed

    Bu, Lingling; Liu, Zonghao; Zhang, Meng; Li, Wenhui; Zhu, Aili; Cai, Fensha; Zhao, Zhixin; Zhou, Yinhua

    2015-08-19

    Semitransparent solar cells are highly attractive for application as power-generating windows. In this work, we present semitransparent perovskite solar cells that employ conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) ( PSS) film as the transparent counter electrode. The PSS electrode is prepared by transfer lamination technique using plastic wrap as the transfer medium. The use of the transfer lamination technique avoids the damage of the CH3NH3PbI3 perovskite film by direct contact of PSS aqueous solution. The semitransparent perovskite solar cells yield a power conversion efficiency of 10.1% at an area of about 0.06 cm(2) and 2.9% at an area of 1 cm(2). The device structure and the fabrication technique provide a facile way to produce semitransparent perovskite solar cells.

  3. Fabrication of Lead-Free (CH3 NH3 )3 Bi2 I9 Perovskite Photovoltaics in Ethanol Solvent.

    PubMed

    Li, Haijin; Wu, Congcong; Yan, Yongke; Chi, Bo; Pu, Jian; Li, Jian; Priya, Shashank

    2017-10-23

    The toxicity of lead present in organohalide perovskites and the hazardous solvent systems used for their synthesis hinder the deployment of perovskite solar cells (PSCs). Herein, an environmentally friendly route toward bismuth-based, lead-free (CH 3 NH 3 ) 3 Bi 2 I 9 perovskites that utilize ethanol as the solvent is described. Using this method, dense and homogeneous microstructures were obtained, compared to the porous, rough microstructures obtained using dimethylformamide. Photovoltaic performances were enhanced, with an open-circuit voltage of 0.84 V measured. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. First Principles Study of Electronic and Magnetic Structures in Double Perovskites

    NASA Astrophysics Data System (ADS)

    Ball, Molly

    At present, electronic devices are reaching their storage and processing limit causing a major push to find materials that can be used in the next generation of devices. Double perovskites with A2BB'O 6 stoichiometry form one of the leading classes of materials currently being studied as a potential candidate because of their extremely wide range and tunability of functional properties, along with economic and highly scalable synthesis routes. Having a thorough understanding of their electronic and magnetic structure and their dependence on composition and local structure is the basis for targeted development of novel and optimized double perovskites. While the body of knowledge and rules within the field of materials chemistry has enabled many previous discoveries, recent developments within density functional theory (DFT) allow by now a rather realistic description of the electronic and magnetic properties of materials and especially identification of their origin from geometry and orbital structure. This thesis details computational work based on DFT within several collaborative studies to better understand the electronic and magnetic properties of double perovskites and related materials that show promise for future use in multifunctional devices. First, we will begin with a general introduction to the double perovskite structure, their properties, and the computational methods used to study them. In the next section, we will look at the case of the antiferromagnetic, insulating double perovskite Sr2CoOsO6, where measurements showed that the transition metal ions in the two sublattices undergo magnetic ordering independently of each other, indicating weak magnetic short-range coupling and a dominance of longer-range interactions, which has previously not been observed. Here, we performed DFT calculations to extract the exchange strengths between the ions and explain this unique dominance of the long-range interactions. Then, we will look at studies done on thin

  5. Ionic and Optical Properties of Methylammonium Lead Iodide Perovskite across the Tetragonal-Cubic Structural Phase Transition

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hoque, Md Nadim Ferdous; Islam, Nazifah; Li, Zhen

    Practical hybrid perovskite solar cells (PSCs) must endure temperatures above the tetragonal-cubic structural phase transition of methylammonium lead iodide (MAPbI3). However, the ionic and optical properties of MAPbI3 in such a temperature range, and particularly, dramatic changes in these properties resulting from a structural phase transition, are not well studied. Herein, we report a striking contrast at approximately 45 degrees C in the ionic/electrical properties of MAPbl3 owing to a change of the ion activation energy from 0.7 to 0.5 eV, whereas the optical properties exhibit no particular transition except for the steady increase of the bandgap with temperature. Thesemore » observations can be explained by the 'continuous' nature of perovskite phase transition. We speculate that the critical temperature at which the ionic/electrical properties change, although related to crystal symmetry variation, is not necessarily the same temperature as when tetragonal-cubic structural phase transition occurs.« less

  6. The effect of moisture on the structures and properties of lead halide perovskites: a first-principles theoretical investigation.

    PubMed

    Zhang, Lei; Ju, Ming-Gang; Liang, WanZhen

    2016-08-17

    With efficiencies exceeding 20% and low production costs, lead halide perovskite solar cells (PSCs) have become potential candidates for future commercial applications. However, there are serious concerns about their long-term stability and environmental friendliness, heavily related to their commercial viability. Herein, we present a theoretical investigation based on the ab initio molecular dynamics (AIMD) simulations and the first-principles density functional theory (DFT) calculations to investigate the effects of sunlight and moisture on the structures and properties of MAPbI3 perovskites. AIMD simulations have been performed to simulate the impact of a few water molecules on the structures of MAPbI3 surfaces terminated in three different ways. The evolution of geometric and electronic structures as well as the absorption spectra has been shown. It is found that the PbI2-terminated surface is the most stable while both the MAI-terminated and PbI2-defective surfaces undergo structural reconstruction, leading to the formation of hydrated compounds in a humid environment. The moisture-induced weakening of photoabsorption is closely related to the formation of hydrated species, and the hydrated crystals MAPbI3·H2O and MA4PbI6·2H2O scarcely absorb the visible light. The electronic excitation in the bare and water-absorbed MAPbI3 nanoparticles tends to weaken Pb-I bonds, especially those around water molecules, and the maximal decrease of photoexcitation-induced bond order can reach up to 20% in the excited state in which the water molecules are involved in the electronic excitation, indicating the accelerated decomposition of perovskites in the presence of sunlight and moisture. This work is valuable for understanding the mechanism of chemical or photochemical instability of MAPbI3 perovskites in the presence of moisture.

  7. CH3NH3PbI3 perovskites: Ferroelasticity revealed.

    PubMed

    Strelcov, Evgheni; Dong, Qingfeng; Li, Tao; Chae, Jungseok; Shao, Yuchuan; Deng, Yehao; Gruverman, Alexei; Huang, Jinsong; Centrone, Andrea

    2017-04-01

    Ferroelectricity has been proposed as a plausible mechanism to explain the high photovoltaic conversion efficiency in organic-inorganic perovskites; however, convincing experimental evidence in support of this hypothesis is still missing. Identifying and distinguishing ferroelectricity from other properties, such as piezoelectricity, ferroelasticity, etc., is typically nontrivial because these phenomena can coexist in many materials. In this work, a combination of microscopic and nanoscale techniques provides solid evidence for the existence of ferroelastic domains in both CH 3 NH 3 PbI 3 polycrystalline films and single crystals in the pristine state and under applied stress. Experiments show that the configuration of CH 3 NH 3 PbI 3 ferroelastic domains in single crystals and polycrystalline films can be controlled with applied stress, suggesting that strain engineering may be used to tune the properties of this material. No evidence of concomitant ferroelectricity was observed. Because grain boundaries have an impact on the long-term stability of organic-inorganic perovskite devices, and because the ferroelastic domain boundaries may differ from regular grain boundaries, the discovery of ferroelasticity provides a new variable to consider in the quest for improving their stability and enabling their widespread adoption.

  8. Transfusion Support for ABO-Incompatible Progenitor Cell Transplantation

    PubMed Central

    Kopko, Patricia M.

    2016-01-01

    Summary ABO-incompatible transplants comprise up to 50% of allogeneic progenitor cell transplants. Major, minor and bidirectional ABO-incompatible transplants each have unique complications that can occur, including hemolysis at the time of progenitor cell infusion, hemolysis during donor engraftment, passenger lymphocyte syndrome, delayed red blood cell engraftment, and pure red cell aplasia. Appropriate transfusion support during the different phases of the allogeneic progenitor cell transplant process is an important part of ABO-incompatible transplantation. PMID:27022318

  9. Interplay of Cation Ordering and Ferroelectricity in Perovskite Tin Iodides: Designing a Polar Halide Perovskite for Photovoltaic Applications

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gou, Gaoyang; Young, Joshua; Liu, Xian

    2016-09-28

    Owing to its ideal semiconducting band gap and good carrier transport properties, the fully inorganic perovskite CsSnI 3 has been proposed as a visible-light absorber for photovoltaic (PV) applications. However, compared to the organic inorganic lead halide perovskite CH 3NH 3PbI 3, CsSnI 3 solar cells display very low energy conversion efficiency. In this work, we propose a potential route to improve the PV properties of CsSnI 3. Using first-principles calculations, we examine the crystal structures and electronic properties of CsSnI 3, including its structural polymorphs. Next, we purposefully order Cs and Rb cations on the A site to createmore » the double perovskite (CsRb)Sn 2I 6. We find that a stable ferroelectric polarization arises from the nontrivial coupling between polar displacements and octahedral rotations of the SnI 6 network. These ferroelectric double perovskites are predicted to have energy band gaps and carrier effective masses similar to those of CsSnI 3. More importantly, unlike nonpolar CsSnI 3, the electric polarization present in ferroelectric (CsRb)Sn 2I 6 can effectively separate the photoexcited carriers, leading to novel ferroelectric PV materials with,potentially enhanced energy conversion efficiency.« less

  10. Electron paramagnetic resonance of Cr{sup 3+} ions in ABO{sub 3} (A = Sc, Lu, In) diamagnetic crystals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Vorotynov, A. M., E-mail: sasa@iph.krasn.ru; Ovchinnikov, S. G.; Rudenko, V. V.

    2016-04-15

    A magnetic resonance method is applied to the investigation of a number of isostructural diamagnetic compounds ABO{sub 3} (A = Sc, Lu, In) with small additions of Cr{sup 3+} ions (S = 3/2) sufficient to observe single-ion spectra. It is shown that the resonance spectra for isolated Cr{sup 3+} ions can be described to a good accuracy by the ordinary axial spin Hamiltonian for 3d ions in octahedral oxygen environment. The parameters of the spin Hamiltonian are determined. It is established that Cr{sup 3+} ions in these crystals are characterized by easy-axis-type anisotropy.

  11. Tunable White-Light Emission in Single-Cation-Templated Three-Layered 2D Perovskites (CH3CH2NH3)4Pb3Br10-xClx.

    PubMed

    Mao, Lingling; Wu, Yilei; Stoumpos, Constantinos C; Traore, Boubacar; Katan, Claudine; Even, Jacky; Wasielewski, Michael R; Kanatzidis, Mercouri G

    2017-08-30

    Two-dimensional (2D) hybrid halide perovskites come as a family (B) 2 (A) n-1 Pb n X 3n+1 (B and A= cations; X= halide). These perovskites are promising semiconductors for solar cells and optoelectronic applications. Among the fascinating properties of these materials is white-light emission, which has been mostly observed in single-layered 2D lead bromide or chloride systems (n = 1), where the broad emission comes from the transient photoexcited states generated by self-trapped excitons (STEs) from structural distortion. Here we report a multilayered 2D perovskite (n = 3) exhibiting a tunable white-light emission. Ethylammonium (EA + ) can stabilize the 2D perovskite structure in EA 4 Pb 3 Br 10-x Cl x (x = 0, 2, 4, 6, 8, 9.5, and 10) with EA + being both the A and B cations in this system. Because of the larger size of EA, these materials show a high distortion level in their inorganic structures, with EA 4 Pb 3 Cl 10 having a much larger distortion than that of EA 4 Pb 3 Br 10 , which results in broadband white-light emission of EA 4 Pb 3 Cl 10 in contrast to narrow blue emission of EA 4 Pb 3 Br 10 . The average lifetime of the series decreases gradually from the Cl end to the Br end, indicating that the larger distortion also prolongs the lifetime (more STE states). The band gap of EA 4 Pb 3 Br 10-x Cl x ranges from 3.45 eV (x = 10) to 2.75 eV (x = 0), following Vegard's law. First-principles density functional theory calculations (DFT) show that both EA 4 Pb 3 Cl 10 and EA 4 Pb 3 Br 10 are direct band gap semiconductors. The color rendering index (CRI) of the series improves from 66 (EA 4 Pb 3 Cl 10 ) to 83 (EA 4 Pb 3 Br 0.5 Cl 9.5 ), displaying high tunability and versatility of the title compounds.

  12. Magnetism and the spin state in cubic perovskite CaCo O 3 synthesized under high pressure

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xia, Hailiang; Dai, Jianhong; Xu, Yuanji

    Cubic SrCo O 3 with an intermediate spin state can only be stabilized by high pressure and high temperature (HPHT) treatment. It is metallic and ferromagnetic with the highest Curie temperature of the transition-metal perovskites. The chemical substitution by Ca on Sr sites would normally lower crystal symmetry from cubic to orthorhombic as seen in the perovskite family of Ca M O 3 ( M = M 4 + of transition metals, G e 4 + , S n 4 + , and Z r 4 +) at room temperature. This structural change narrows the bandwidth, so as to furthermore » enhance the Curie temperature as the crossover to the localized electronic state is approached. Here, we report a successful synthesis of the perovskite CaCo O 3 with a HPHT treatment. Surprisingly, CaCo O 3 crystallizes in a simple cubic structure that remains stable down to 20 K, the lowest temperature in the structural study. The new perovskite has been thoroughly characterized by a suite of measurements including transport, magnetization, specific heat, thermal conductivity, and thermoelectric power. Furthermore, metallic CaCo O 3 undergoes two successive magnetic transitions at 86 K and 54 K as temperature decreases. The magnetization at 5 K is compatible with the intermediate spin state t 4 e 1 of C o 4 + at the octahedral site. The thermal expansion of the Co-O bond length indicates that the population of high spin state t 3 e 2 increases for T > 100 K . The shortest Co-O bond length in cubic CaCo O 3 is responsible for delocalizing electrons in the π * -band and itinerant-electron ferromagnetism at T < 54 K . In our comprehensive comparison between SrCo O 3 and CaCo O 3 and the justification of their physical properties by first-principles calculation were made in this report. Partially filled π * and σ * bands would make CaCo O 3 suitable to study the Hund's coupling effect in a metal.« less

  13. Magnetism and the spin state in cubic perovskite CaCo O 3 synthesized under high pressure

    DOE PAGES

    Xia, Hailiang; Dai, Jianhong; Xu, Yuanji; ...

    2017-07-17

    Cubic SrCo O 3 with an intermediate spin state can only be stabilized by high pressure and high temperature (HPHT) treatment. It is metallic and ferromagnetic with the highest Curie temperature of the transition-metal perovskites. The chemical substitution by Ca on Sr sites would normally lower crystal symmetry from cubic to orthorhombic as seen in the perovskite family of Ca M O 3 ( M = M 4 + of transition metals, G e 4 + , S n 4 + , and Z r 4 +) at room temperature. This structural change narrows the bandwidth, so as to furthermore » enhance the Curie temperature as the crossover to the localized electronic state is approached. Here, we report a successful synthesis of the perovskite CaCo O 3 with a HPHT treatment. Surprisingly, CaCo O 3 crystallizes in a simple cubic structure that remains stable down to 20 K, the lowest temperature in the structural study. The new perovskite has been thoroughly characterized by a suite of measurements including transport, magnetization, specific heat, thermal conductivity, and thermoelectric power. Furthermore, metallic CaCo O 3 undergoes two successive magnetic transitions at 86 K and 54 K as temperature decreases. The magnetization at 5 K is compatible with the intermediate spin state t 4 e 1 of C o 4 + at the octahedral site. The thermal expansion of the Co-O bond length indicates that the population of high spin state t 3 e 2 increases for T > 100 K . The shortest Co-O bond length in cubic CaCo O 3 is responsible for delocalizing electrons in the π * -band and itinerant-electron ferromagnetism at T < 54 K . In our comprehensive comparison between SrCo O 3 and CaCo O 3 and the justification of their physical properties by first-principles calculation were made in this report. Partially filled π * and σ * bands would make CaCo O 3 suitable to study the Hund's coupling effect in a metal.« less

  14. Magnetism and the spin state in cubic perovskite CaCo O3 synthesized under high pressure

    NASA Astrophysics Data System (ADS)

    Xia, Hailiang; Dai, Jianhong; Xu, Yuanji; Yin, Yunyu; Wang, Xiao; Liu, Zhehong; Liu, Min; McGuire, Michael A.; Li, Xiang; Li, Zongyao; Jin, Changqing; Yang, Yifeng; Zhou, Jianshi; Long, Youwen

    2017-07-01

    Cubic SrCo O3 with an intermediate spin state can only be stabilized by high pressure and high temperature (HPHT) treatment. It is metallic and ferromagnetic with the highest Curie temperature of the transition-metal perovskites. The chemical substitution by Ca on Sr sites would normally lower crystal symmetry from cubic to orthorhombic as seen in the perovskite family of Ca M O3 (M =M4 + of transition metals, G e4 + , S n4 + , and Z r4 + ) at room temperature. This structural change narrows the bandwidth, so as to further enhance the Curie temperature as the crossover to the localized electronic state is approached. We report a successful synthesis of the perovskite CaCo O3 with a HPHT treatment. Surprisingly, CaCo O3 crystallizes in a simple cubic structure that remains stable down to 20 K, the lowest temperature in the structural study. The new perovskite has been thoroughly characterized by a suite of measurements including transport, magnetization, specific heat, thermal conductivity, and thermoelectric power. Metallic CaCo O3 undergoes two successive magnetic transitions at 86 K and 54 K as temperature decreases. The magnetization at 5 K is compatible with the intermediate spin state t4e1 of C o4 + at the octahedral site. The thermal expansion of the Co-O bond length indicates that the population of high spin state t3e2 increases for T >100 K . The shortest Co-O bond length in cubic CaCo O3 is responsible for delocalizing electrons in the π*-band and itinerant-electron ferromagnetism at T <54 K . A comprehensive comparison between SrCo O3 and CaCo O3 and the justification of their physical properties by first-principles calculation have also been made in this report. Partially filled π* and σ* bands would make CaCo O3 suitable to study the Hund's coupling effect in a metal.

  15. Device simulation of lead-free CH3NH3SnI3 perovskite solar cells with high efficiency

    NASA Astrophysics Data System (ADS)

    Du, Hui-Jing; Wang, Wei-Chao; Zhu, Jian-Zhuo

    2016-10-01

    The lead-free perovskite solar cells (PSCs) have drawn a great deal of research interest due to the Pb toxicity of the lead halide perovskite. CH3NH3SnI3 is a viable alternative to CH3NH3PbX3, because it has a narrower band gap of 1.3 eV and a wider visible absorption spectrum than the lead halide perovskite. The progress of fabricating tin iodide PSCs with good stability has stimulated the studies of these CH3NH3SnI3 based cells greatly. In the paper, we study the influences of various parameters on the solar cell performance through theoretical analysis and device simulation. It is found in the simulation that the solar cell performance can be improved to some extent by adjusting the doping concentration of the perovskite absorption layer and the electron affinity of the buffer and HTM, while the reduction of the defect density of the perovskite absorption layer significantly improves the cell performance. By further optimizing the parameters of the doping concentration (1.3× 1016 cm-3) and the defect density (1× 1015 cm-3) of perovskite absorption layer, and the electron affinity of buffer (4.0 eV) and HTM (2.6 eV), we finally obtain some encouraging results of the J sc of 31.59 mA/cm2, V oc of 0.92 V, FF of 79.99%, and PCE of 23.36%. The results show that the lead-free CH3NH3SnI3 PSC is a potential environmentally friendly solar cell with high efficiency. Improving the Sn2 + stability and reducing the defect density of CH3NH3SnI3 are key issues for the future research, which can be solved by improving the fabrication and encapsulation process of the cell. Project supported by the Graduate Student Education Teaching Reform Project, China (Grant No. JG201512) and the Young Teachers Research Project of Yanshan University, China (Grant No. 13LGB028).

  16. [Yes, we should keep ABO agglutination test within bedside transfusion checks].

    PubMed

    Daurat, G

    2008-11-01

    ABO incompatible transfusions are still a frequent cause of serious adverse transfusion reactions. Bedside check is intended to detect patient errors and prevent ABO mismatch. France is one of the few countries that includes ABO agglutination test for red blood cells in bedside checks. Evaluation of this ABO agglutination test, performed with a special card, shows that, on the field, despite frequent users' mishandling, it can detect up to 93% of ABO incompatibilities. This is not enough to rely on this sole test for bedside checks. But, linking it with an another test, currently, checks that the right blood is given to the right patient, rises the sensitivity of the whole bedside procedure up to an estimated 99.65%, for detection of ABO incompatibilities. This linkage has been introduced in the French regulation in 2003. Since then, the incidence of ABO incompatible transfusions has decreased dramatically and faster than in any other country, so France has now, probably, the lowest rate of ABO incompatible transfusions. The investigation of the few ABO accidents that still occur, shows that professionals have always bypassed this linkage. On the other hand, introducing bedside recipient and blood products barcode or radio-chip checks in all the 1500 French hospitals, though technically possible, would provide very little enhancement and lead to major difficulties and expenses. Linkage of ABO agglutination test to patient and blood checks within the bedside procedure has proved to be efficient and should be kept.

  17. Enhancement of photoresponse property of perovskite solar cell by aluminium chloride (AlCl3)

    NASA Astrophysics Data System (ADS)

    Ghosh, S. S.; Sil, A.

    2018-05-01

    The fabrication of a three layer solar cell device is a new area of research. The formation of perovskite phase is evident from x-ray diffraction and its particle size is observed by microstructural analysis. A thin layer of gold coating over the device increases the surface conductivity. Direct contact between a SnCl2 or AlCl3 based perovskite with the gold coating increases the durability of the film but decreases the hole transport properties due to absence of an organic hole transport material. The absorbance spectroscopy analysis gives characteristic peaks showing the evidence of ITO, TiO2 (rutile) and Sn2+ complexes present in the Sn-perovskite film or Al3+ complexes present within the Al-perovskite cell. The desired absorbance near 550 nm due to Al3+ complexes causes a much higher flow of current on illumination and thus is also evidenced by the presence of comparatively high intensity PL spectra in the Al-perovskite system which occurred due to free exciton formation near band edge excitation. The fill factor of the devices is estimated as ∼0.83 and ∼0.65 for Sn-perovskite and Al-perovskite devices respectively. The PCE values of Sn-perovskite and Al-perovskite devices are calculated 0.39% and 0.96% respectively, which establish Al-perovskite film as a useful component for future solar cell device manufacturing.

  18. [C6 H14 N]PbBr3 : An ABX3 -Type Semiconducting Perovskite Hybrid with Above-Room-Temperature Phase Transition.

    PubMed

    Zhang, Jing; Liu, Xitao; Li, Xianfeng; Han, Shiguo; Tao, Kewen; Wang, Yuyin; Ji, Chengmin; Sun, Zhihua; Luo, Junhua

    2018-04-16

    Organic-inorganic hybrid perovskites, with the formula ABX 3 (A=organic cation, B=metal cation, and X=halide; for example, CH 3 NH 3 PbI 3 ), have diverse and intriguing physical properties, such as semiconduction, phase transitions, and optical properties. Herein, a new ABX 3 -type semiconducting perovskite-like hybrid, (hexamethyleneimine)PbBr 3 (1), consisting of one-dimensional inorganic frameworks and cyclic organic cations, is reported. Notably, the inorganic moiety of 1 adopts a perovskite-like architecture and forms infinite columns composed of face-sharing PbBr 6 octahedra. Strikingly, the organic cation exhibits a highly flexible molecular configuration, which triggers an above-room-temperature phase transition, at T c =338.8 K; this is confirmed by differential scanning calorimetry (DSC), specific heat capacity (C p ), and dielectric measurements. Further structural analysis reveals that the phase transition originates from the molecular configurational distortion of the organic cations coupled with small-angle reorientation of the PbBr 6 octahedra inside the inorganic components. Moreover, temperature-dependent conductivity and UV/Vis absorption measurements reveal that 1 also displays semiconducting behavior below T c . It is believed that this work will pave a potential way to design multifeatured perovskite hybrids by utilizing cyclic organic amines. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Crystal structure and magnetism of layered perovskites compound EuBaCuFeO5

    NASA Astrophysics Data System (ADS)

    Lal, Surender; Mukherjee, K.; Yadav, C. S.

    2018-04-01

    Layered perovskite compounds have interesting multiferroic properties.YBaCuFeO5 is one of the layered perovskite compounds which have magnetic and dielectric transition above 200 K. The multiferroic properties can be tuned with the replacement of Y with some other rare earth ions. In this manuscript, structural and magnetic properties of layered perovskite compound EuBaCuFeO5 have been investigated. This compound crystallizes in the tetragonal structure with P4mm space group and is iso-structural with YBaCuFeO5. The magnetic transition has been found to shift to 120 K as compared to YBaCuFeO5 which has the transition at 200 K. This shift in the magnetic transition has been ascribed to the decrease in the chemical pressure that relaxes the magnetic moments.

  20. Chemotherapy-induced B-cell depletion in hepatoblastoma patients undergoing ABO-incompatible living donor liver transplantation.

    PubMed

    Kanazawa, Hiroyuki; Fukuda, Akinari; Mali, Vidyadhar Padmakar; Rahayatri, Tri Hening; Hirata, Yoshihiro; Sasaki, Kengo; Uchida, Hajime; Shigeta, Takanobu; Sakamoto, Seisuke; Matsumoto, Kimikazu; Kasahara, Mureo

    2016-05-01

    LT from ABO-I donors requires preconditioning regimens to prevent postoperative catastrophic AMR. NAC for HBL is known to cause myelosuppression leading to a reduction in the number and function of lymphocytes. We investigated this chemotherapy-induced myelosuppression in HBL patients listed for LT from ABO-I donors with reference to the kinetics of B, T cells, and anti-ABO blood type isoagglutinin titers. Between 2005 and 2015, of the 319 patients who underwent LDLT at our institute, 12 were indicated for unresectable HBL. Three patients with unresectable HBL who underwent LDLT from ABO-I donors are included in this study. Immunosuppression consisted of a standard regime of tacrolimus and low-dose steroids as in ABO compatible/identical LDLT. No additional preoperative therapies for B-cell depletion were used. Absolute lymphocyte counts, lymphocyte subsets (including CD20+ B cells, CD3+CD4+ T cells and CD3+CD8+ T cells), and anti-ABO blood type isoagglutinin titers were measured before LDLT and postoperatively. The median age at diagnosis was 19 months (range, 3-31 months). The median follow-up was seven months (range, 6-15 months). The median interval from the last NAC to LDLT was 33 days (range, 25-52 days). The median interval from LDLT to adjuvant chemotherapy was 28 days (range, 22-36 days). The counts of CD20+ B cells before LDLT were depleted to median 5 cells/mm(3) (range, 0-6 cells/mm(3)). There was a transient rebound in the CD20+ B cell counts on day seven (maximum of 82 cells/mm(3)) followed by a decline starting at 14 days after LDLT that was sustained for the duration of adjuvant chemotherapy. Anti-ABO blood type isoagglutinin titers were lowered to between 1:1 and 1:16 before LDLT and remained low for the duration of follow-up in this study. All of the three patients remained in good health without either acute cellular or AMR after LDLT. The B-cell depletion that occurs after cisplatin-based chemotherapy for HBL may help accomplish safe ABO-I LDLT

  1. High Efficiency MAPbI3 Perovskite Solar Cell Using a Pure Thin Film of Polyoxometalate as Scaffold Layer.

    PubMed

    Sardashti, Mohammad Khaledi; Zendehdel, Mahmoud; Nia, Narges Yaghoobi; Karimian, Davud; Sheikhi, Mohammad

    2017-10-09

    Here, we successfully used a pure layer of [SiW 11 O 39 ] 8- polyoxomethalate (POM) structure as a thin-film scaffold layer for CH 3 NH 3 PbI 3 -based perovskite solar cells (PSCs). A smooth nanoporous surface of POM causes outstanding improvement of the photocurrent density, external quantum efficiency (EQE), and overall efficiency of the PSCs compared to mesoporous TiO 2 (mp-TiO 2 ) as scaffold layer. Average power conversion efficiency (PCE) values of 15.5 % with the champion device showing 16.3 % could be achieved by using POM and a sequential deposition method with the perovskite layer. Furthermore, modified and defect-free POM/perovskite interface led to elimination of the anomalous hysteresis in the current-voltage curves. The open-circuit voltage decay study shows promising decrease of the electron recombination in the POM-based PSCs, which is also related to the modification of the POM/ perovskite interface and higher electron transport inside the POM layer. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Loparite, a rare-earth ore (Ce, Na, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3

    USGS Publications Warehouse

    Hedrick, James B.; Sinha, Shyama P.; Kosynkin, Valery D.

    1997-01-01

    The mineral loparite (Ce, NA, Sr, Ca)(Ti, Nb, Ta, Fe+3)O3 is the principal ore of the light-group rare-earth elements (LREE) in Russia. The complex oxide has a perovskite (ABO3) structure with coupled substitutions, polymorphism, defect chemistry and a tendency to become metamict. The A site generally contains weakly bonded, easily exchanged cations of the LREE, Na and Ca. The B site generally contains smaller, highly charged cations of Ti, Nb or Fe+3. Mine production is from Russia's Kola Peninsula. Ore is beneficiated to produce a 95% loparite concentrate containing 30% rare-earth oxides. Loparite concentrate is refined by either a chlorination process or acid decomposition process to recover rare-earths, titanium, niobium and tantalum. Rare-earths are separated by solvent extraction and selective precipitation/dissolution. The concentrate is processed at plants in Russia, Estonia and Kazakstan.

  3. Structural and thermoelectric properties of n-type Sr1- x Ti x MnO3- δ perovskite system

    NASA Astrophysics Data System (ADS)

    Kim, C. M.; Seo, J. W.; Choi, S.-M.; Seo, W.-S.; Lee, S.; Lim, Y. S.; Park, K.

    2015-03-01

    A series of Sr1- x Ti x MnO3- δ (0.05 ≤ x ≤ 0.3) was fabricated by the solid-state reaction method. We studied the structural and thermoelectric properties of Sr1- x Ti x MnO3- δ , with respect to the partial substitution of Ti4+ for Sr2+. The sintered Sr1- x Ti x MnO3- δ crystallized in the hexagonal perovskite-type structure with a space group of P6 3 / mmc. For x ≤ 0.1, the partial substitution of Ti4+ for Sr2+ led to increases in the electrical conductivity and the absolute value of the Seebeck coefficient, thus enhancing the power factor. The highest power factor (2.5 × 10-5 Wm-1K-2) was obtained for Sr0.9Ti0.1MnO3- δ at 800°C. The partial substitution of Ti4+ for Sr2+ in SrMnO3- δ led to a significant improvement in the thermoelectric properties. [Figure not available: see fulltext.

  4. First-Principles Study of Novel Two-Dimensional (C4H9NH3)2PbX4 Perovskites for Solar Cell Absorbers.

    PubMed

    Wang, Da; Wen, Bo; Zhu, Ya-Nan; Tong, Chuan-Jia; Tang, Zhen-Kun; Liu, Li-Min

    2017-02-16

    Low-dimensional perovskites (A 2 BX 4 ), in which the A cations are replaced by different organic cations, may be used for photovoltaic applications. In this contribution, we systematically study the two-dimensional (2D) (C 4 H 9 NH 3 ) 2 PbX 4 (X═Cl, Br and I) hybrid perovskites by density functional theory (DFT). A clear structures-properties relationship, with the photophysical characteristics directly related to the dimensionality and material compositions, was established. The strong s-p antibonding couplings in both bulk and monolayer (C 4 H 9 NH 3 ) 2 PbI 4 lead to low effective masses for both holes (m h *) and electrons (m e *). However, m h * increases in proportion to the decreasing inorganic layer thickness, which eventually leads to a slightly shifted band edge emission found in 2D perovskites. Notably, the 2D (C 4 H 9 NH 3 ) 2 PbX 4 perovskites exhibit strong optical transitions in the visible light spectrum, and the optical absorption tunings can be achieved by varying the compositions and the layer thicknesses. Such work paves an important way to uncover the structures-properties relationship in 2D perovskites.

  5. CH3 NH3 PbBr3 Perovskite Nanocrystals as Efficient Light-Harvesting Antenna for Fluorescence Resonance Energy Transfer.

    PubMed

    Muthu, Chinnadurai; Vijayan, Anuja; Nair, Vijayakumar C

    2017-05-04

    Hybrid perovskites have created enormous research interest as a low-cost material for high-performance photovoltaic devices, light-emitting diodes, photodetectors, memory devices and sensors. Perovskite materials in nanocrystal form that display intense luminescence due to the quantum confinement effect were found to be particularly suitable for most of these applications. However, the potential use of perovskite nanocrystals as a light-harvesting antenna for possible applications in artificial photosynthesis systems is not yet explored. In the present work, we study the light-harvesting antenna properties of luminescent methylammonium lead bromide (CH 3 NH 3 PbBr 3 )-based perovskite nanocrystals using fluorescent dyes (rhodamine B, rhodamine 101, and nile red) as energy acceptors. Our studies revealed that CH 3 NH 3 PbBr 3 nanocrystals are an excellent light-harvesting antenna, and efficient fluorescence resonance energy transfer occurs from the nanocrystals to fluorescent dyes. Further, the energy transfer efficiency is found to be highly dependent on the number of anchoring groups and binding ability of the dyes to the surface of the nanocrystals. These observations may have significant implications for perovskite-based light-harvesting devices and their possible use in artificial photosynthesis systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Universal Approach toward Hysteresis-Free Perovskite Solar Cell via Defect Engineering.

    PubMed

    Son, Dae-Yong; Kim, Seul-Gi; Seo, Ja-Young; Lee, Seon-Hee; Shin, Hyunjung; Lee, Donghwa; Park, Nam-Gyu

    2018-01-31

    Organic-inorganic halide perovskite is believed to be a potential candidate for high efficiency solar cells because power conversion efficiency (PCE) was certified to be more than 22%. Nevertheless, mismatch of PCE due to current density (J)-voltage (V) hysteresis in perovskite solar cells is an obstacle to overcome. There has been much lively debate on the origin of J-V hysteresis; however, effective methodology to solve the hysteric problem has not been developed. Here we report a universal approach for hysteresis-free perovskite solar cells via defect engineering. A severe hysteresis observed from the normal mesoscopic structure employing TiO 2 and spiro-MeOTAD is almost removed or does not exist upon doping the pure perovskites, CH 3 NH 3 PbI 3 and HC(NH 2 ) 2 PbI 3 , and the mixed cation/anion perovskites, FA 0.85 MA 0.15 PbI 2.55 Br 0.45 and FA 0.85 MA 0.1 Cs 0.05 PbI 2.7 Br 0.3 , with potassium iodide. Substantial reductions in low-frequency capacitance and bulk trap density are measured from the KI-doped perovskite, which is indicative of trap-hysteresis correlation. A series of experiments with alkali metal iodides of LiI, NaI, KI, RbI and CsI reveals that potassium ion is the right element for hysteresis-free perovskite. Theoretical studies suggest that the atomistic origin of the hysteresis of perovskite solar cells is not the migration of iodide vacancy but results from the formation of iodide Frenkel defect. Potassium ion is able to prevent the formation of Frenkel defect since K + energetically prefers the interstitial site. A complete removal of hysteresis is more pronounced at mixed perovskite system as compared to pure perovskites, which is explained by lower formation energy of K interstitial (-0.65 V for CH 3 NH 3 PbI 3 vs -1.17 V for mixed perovskite). The developed KI doping methodology is universally adapted for hysteresis-free perovskite regardless of perovskite composition and device structure.

  7. Hybrid Dion-Jacobson 2D Lead Iodide Perovskites.

    PubMed

    Mao, Lingling; Ke, Weijun; Pedesseau, Laurent; Wu, Yilei; Katan, Claudine; Even, Jacky; Wasielewski, Michael R; Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2018-03-14

    The three-dimensional hybrid organic-inorganic perovskites have shown huge potential for use in solar cells and other optoelectronic devices. Although these materials are under intense investigation, derivative materials with lower dimensionality are emerging, offering higher tunability of physical properties and new capabilities. Here, we present two new series of hybrid two-dimensional (2D) perovskites that adopt the Dion-Jacobson (DJ) structure type, which are the first complete homologous series reported in halide perovskite chemistry. Lead iodide DJ perovskites adopt a general formula A'A n-1 Pb n I 3 n+1 (A' = 3-(aminomethyl)piperidinium (3AMP) or 4-(aminomethyl)piperidinium (4AMP), A = methylammonium (MA)). These materials have layered structures where the stacking of inorganic layers is unique as they lay exactly on top of another. With a slightly different position of the functional group in the templating cation 3AMP and 4AMP, the as-formed DJ perovskites show different optical properties, with the 3AMP series having smaller band gaps than the 4AMP series. Analysis on the crystal structures and density functional theory (DFT) calculations suggest that the origin of the systematic band gap shift is the strong but indirect influence of the organic cation on the inorganic framework. Fabrication of photovoltaic devices utilizing these materials as light absorbers reveals that (3AMP)(MA) 3 Pb 4 I 13 has the best power conversion efficiency (PCE) of 7.32%, which is much higher than that of the corresponding (4AMP)(MA) 3 Pb 4 I 13 .

  8. Sound velocity measurements of CaSiO3 perovskite under lower mantle pressures

    NASA Astrophysics Data System (ADS)

    Kudo, Y.; Hirose, K.

    2010-12-01

    The chemical composition of the lower mantle and the distribution of subducted crustal materials in the lower mantle can be constrained by the comparison of seismological observations with laboratory measurements of sound velocities of expected constituent minerals in lower mantle conditions. To date, sound velocities of two major constituent minerals of the lower mantle, namely magnesium silicate perovskite and ferropericlase have been well studied although the data are mostly limited to low temperature (300 K). On the other hand, another major mineral, CaSiO3-perovskite appears in both peridtite (~7 wt.%) and subducted basaltic crusts (~23 wt.%) at the lower mantle pressure-temperature conditions. In spite of its abundance in those rocks, little is known about acoustic velocity, mostly because it cannot be quenched to the ambient pressure. Synthesis and measurement should be made under pressure, which has been a challenging project for the current experimental techniques. We have conducted sound velocity measurements of polycrystalline CaSiO3 perovskite by a combination of a diamond anvil cell (DAC) and Brillouin scattering spectroscopy. High-pressure was generated by the DAC with a pair of 300-micron culet diamond anvils. Calcium silicate perovskite was synthesized from gel by laser annealing in the DAC with the CO2 laser. A tetragonal perovskite structure was confirmed by the X-ray diffraction at the station BL10XU, SPring-8. Brillouin scattering measurements were made at 300 K under pressures corresponding to the middle lower mantle conditions. Results demonstrate that the S-wave velocity is significantly lower than previous theoretical results. We will discuss the possible source for this discrepancy and resulting implications for the lower mantle materials.

  9. La 3+ doping of the Sr 2CoWO 6 double perovskite: A structural and magnetic study

    NASA Astrophysics Data System (ADS)

    López, C. A.; Viola, M. C.; Pedregosa, J. C.; Carbonio, R. E.; Sánchez, R. D.; Fernández-Díaz, M. T.

    2008-11-01

    La-doped Sr 2CoWO 6 double perovskites have been prepared in air in polycrystalline form by solid-state reaction. These materials have been studied by X-ray powder diffraction (XRPD), neutron powder diffraction (NPD) and magnetic susceptibility. The structural refinement was performed from combined XRPD and NPD data (D2B instrument, λ=1.594 Å). At room temperature, the replacement of Sr 2+ by La 3+ induces a change of the tetragonal structure, space group I4/ m of the undoped Sr 2CoWO 6 into the distorted monoclinic crystal structure, space group P2 1/ n, Z=2. The structure of La-doped phases contains alternating CoO 6 and (Co/W)O 6 octahedra, almost fully ordered. On the other hand, the replacement of Sr 2+ by La 3+ induces a partial replacement of W 6+ by Co 2+ into the B sites, i.e. Sr 2-xLa xCoW 1-yCo yO 6 ( y= x/4) with segregation of SrWO 4. Magnetic and neutron diffraction measurements indicate an antiferromagnetic ordering below TN=24 K independently of the La-substitution.

  10. A Direct Bandgap Copper-Antimony Halide Perovskite.

    PubMed

    Vargas, Brenda; Ramos, Estrella; Pérez-Gutiérrez, Enrique; Alonso, Juan Carlos; Solis-Ibarra, Diego

    2017-07-12

    Since the establishment of perovskite solar cells (PSCs), there has been an intense search for alternative materials to replace lead and improve their stability toward moisture and light. As single-metal perovskite structures have yielded unsatisfactory performances, an alternative is the use of double perovskites that incorporate a combination of metals. To this day, only a handful of these compounds have been synthesized, but most of them have indirect bandgaps and/or do not have bandgaps energies well-suited for photovoltaic applications. Here we report the synthesis and characterization of a unique mixed metal ⟨111⟩-oriented layered perovskite, Cs 4 CuSb 2 Cl 12 (1), that incorporates Cu 2+ and Sb 3+ into layers that are three octahedra thick (n = 3). In addition to being made of abundant and nontoxic elements, we show that this material behaves as a semiconductor with a direct bandgap of 1.0 eV and its conductivity is 1 order of magnitude greater than that of MAPbI 3 (MA = methylammonium). Furthermore, 1 has high photo- and thermal-stability and is tolerant to humidity. We conclude that 1 is a promising material for photovoltaic applications and represents a new type of layered perovskite structure that incorporates metals in 2+ and 3+ oxidation states, thus significantly widening the possible combinations of metals to replace lead in PSCs.

  11. Highly flexible InSnO electrodes on thin colourless polyimide substrate for high-performance flexible CH3NH3PbI3 perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Park, Jeong-Il; Heo, Jin Hyuck; Park, Sung-Hyun; Hong, Ki Il; Jeong, Hak Gee; Im, Sang Hyuk; Kim, Han-Ki

    2017-02-01

    We fabricated high-performance flexible CH3NH3PbI3 (MAPbI3) perovskite solar cells with a power conversion efficiency of 15.5% on roll-to-roll sputtered ITO films on 60 μm-thick colourless polyimide (CPI) substrate. Due to the thermal stability of the CPI substrate, an ITO/CPI sample subjected to rapid thermal annealing at 300 °C showed a low sheet resistance of 57.8 Ω/square and high transmittance of 83.6%, which are better values than those of an ITO/PET sample. Outer and inner bending tests demonstrated that the mechanical flexibility of the ITO/CPI was superior to that of the conventional ITO/PET sample owing to the thinness of the CPI substrate. In addition, due to its good mechanical flexibility, the ITO/CPI showed no change in resistance after 10,000 cycle outer and inner dynamic fatigue tests. Flexible perovskite solar cells with the structure of Au/PTAA/MAPbI3/ZnO/ITO/CPI showed a high power conversion efficiency of 15.5%. The successful operation of these flexible perovskite solar cells on ITO/CPI substrate indicated that the ITO film on thermally stable CPI substrate is a promising of flexible substrate for high-temperature processing, a finding likely to advance the commercialization of cost-efficient flexible perovskite solar cells.

  12. Humidity versus photo-stability of metal halide perovskite films in a polymer matrix.

    PubMed

    Manshor, Nurul Ain; Wali, Qamar; Wong, Ka Kan; Muzakir, Saifful Kamaluddin; Fakharuddin, Azhar; Schmidt-Mende, Lukas; Jose, Rajan

    2016-08-21

    Despite the high efficiency of over 21% reported for emerging thin film perovskite solar cells, one of the key issues prior to their commercial deployment is to attain their long term stability under ambient and outdoor conditions. The instability in perovskite is widely conceived to be humidity induced due to the water solubility of its initial precursors, which leads to decomposition of the perovskite crystal structure; however, we note that humidity alone is not the major degradation factor and it is rather the photon dose in combination with humidity exposure that triggers the instability. In our experiment, which is designed to decouple the effect of humidity and light on perovskite degradation, we investigate the shelf-lifetime of CH3NH3PbI3 films in the dark and under illumination under high humidity conditions (Rel. H. > 70%). We note minor degradation in perovskite films stored in a humid dark environment whereas upon exposure to light, the films undergo drastic degradation, primarily owing to the reactive TiO2/perovskite interface and also the surface defects of TiO2. To enhance its air-stability, we incorporate CH3NH3PbI3 perovskite in a polymer (poly-vinylpyrrolidone, PVP) matrix which retained its optical and structural characteristics in the dark for ∼2000 h and ∼800 h in room light soaking, significantly higher than a pristine perovskite film, which degraded completely in 600 h in the dark and in less than 100 h when exposed to light. We attribute the superior stability of PVP incorporated perovskite films to the improved structural stability of CH3NH3PbI3 and also to the improved TiO2/perovskite interface upon incorporating a polymer matrix. Charge injection from the polymer embedded perovskite films has also been confirmed by fabricating solar cells using them, thereby providing a promising future research pathway for stable and efficient perovskite solar cells.

  13. La{sup 3+} doping of the Sr{sub 2}CoWO{sub 6} double perovskite: A structural and magnetic study

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lopez, C.A.; Viola, M.C.; Pedregosa, J.C.

    2008-11-15

    La-doped Sr{sub 2}CoWO{sub 6} double perovskites have been prepared in air in polycrystalline form by solid-state reaction. These materials have been studied by X-ray powder diffraction (XRPD), neutron powder diffraction (NPD) and magnetic susceptibility. The structural refinement was performed from combined XRPD and NPD data (D2B instrument, {lambda}=1.594 A). At room temperature, the replacement of Sr{sup 2+} by La{sup 3+} induces a change of the tetragonal structure, space group I4/m of the undoped Sr{sub 2}CoWO{sub 6} into the distorted monoclinic crystal structure, space group P2{sub 1}/n, Z=2. The structure of La-doped phases contains alternating CoO{sub 6} and (Co/W)O{sub 6} octahedra,more » almost fully ordered. On the other hand, the replacement of Sr{sup 2+} by La{sup 3+} induces a partial replacement of W{sup 6+} by Co{sup 2+} into the B sites, i.e. Sr{sub 2-x}La{sub x}CoW{sub 1-y}Co{sub y}O{sub 6} (y=x/4) with segregation of SrWO{sub 4}. Magnetic and neutron diffraction measurements indicate an antiferromagnetic ordering below T{sub N}=24 K independently of the La-substitution. - Graphical abstract: La-doped Sr{sub 2}CoWO{sub 6} double perovskites have been prepared in polycrystalline form by solid-state reaction. The general formula of these compounds is Sr{sub 2-x}La{sub x}CoW{sub 1-y}Co{sub y}O{sub 6} (y=x/4). XRPD, NPD and magnetic susceptibility studies were performed. The structure of monoclinic La-doped phases contains alternating CoO{sub 6} and (Co/W)O{sub 6} octahedra, almost fully ordered. NPD and magnetic measurements indicate an antiferromagnetic ordering at low temperature.« less

  14. Phase equilibria and velocity discontinuities across the post-perovskite transition in (Mg,Fe)SiO3

    NASA Astrophysics Data System (ADS)

    Wentzcovitch, Renata; Shukla, Gaurav; Sarkar, Kanchan

    The enigmatic nature of the region above the Earth's core-mantle boundary known as the D'' region, is often characterized by a significant contrast in seismic wave velocities. The perovskite (Pv) to post-perovskite (PPv) transition in bridgmanite ((Mg,Fe)SiO3 perovskite) is one of the keys for understanding this region. In this study, we present DFT + USC calculations of phase equilibria in bridgmanite across the post-perovskite transition. Thermal effects are addressed within the quasi-harmonic approximation. By computing high-pressure and high-temperatures elastic/acoustic properties of Pv and PPv phases, we also investigate seismic signature of the PPv-transition, believed to cause the D'' discontinuity. Aggregate elastic moduli and sound velocities for the Mg-end member are successfully compared with limited experimental data available. Predicted velocity discontinuities across the PPv transition are consistent with seismic observations in some places of the global D'' discontinuity. Our robust estimates of the phase boundary and elastic properties of the perovskite and post-perovskite phases will help to clarify the origin of lateral velocity variations in the deep lower mantle region and constrain its composition and thermal structure. 1This research was supported primarily by NSF Grants EAR 1348066 and DMR 1503084. Computations are performed at the Minnesota Su- percomputing Institute (MSI).

  15. Charge-transport in tin-iodide perovskite CH3NH3SnI3: origin of high conductivity.

    PubMed

    Takahashi, Yukari; Obara, Rena; Lin, Zheng-Zhong; Takahashi, Yukihiro; Naito, Toshio; Inabe, Tamotsu; Ishibashi, Shoji; Terakura, Kiyoyuki

    2011-05-28

    The structural and electrical properties of a metal-halide cubic perovskite, CH(3)NH(3)SnI(3), have been examined. The band structure, obtained using first-principles calculation, reveals a well-defined band gap at the Fermi level. However, the temperature dependence of the single-crystal electrical conductivity shows metallic behavior down to low temperatures. The temperature dependence of the thermoelectric power is also metallic over the whole temperature range, and the large positive value indicates that charge transport occurs with a low concentration of hole carriers. The metallic properties of this as-grown crystal are thus suggested to result from spontaneous hole-doping in the crystallization process, rather than the semi-metal electronic structure. The present study shows that artificial hole doping indeed enhances the conductivity.

  16. Low Surface Recombination Velocity in Solution-Grown CH 3NH 3PbBr 3 Perovskite Single Crystal

    DOE PAGES

    Yang, Ye; Yan, Yong; Yang, Mengjin; ...

    2015-08-06

    Organic-inorganic hybrid perovskites are attracting intense research effort due to their impressive performance in solar cells. While the carrier transport parameters such as mobility and bulk carrier lifetime shows sufficient characteristics, the surface recombination, which can have major impact on the solar cell performance, has not been studied. Here we measure surface recombination dynamics in CH 3NH 3PbBr 3 perovskite single crystals using broadband transient reflectance spectroscopy. The surface recombination velocity is found to be 3.4±0.1 10 3 cm s -1, B2–3 orders of magnitude lower than that in many important unpassivated semiconductors employed in solar cells. Our result suggestsmore » that the planar grain size for the perovskite thin films should be larger thanB30 mm to avoid the influence of surface recombination on the effective carrier lifetime.« less

  17. Water electrolysis on La 1-xSr xCoO 3perovskite electrocatalysts

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.

    2016-03-23

    Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr 2+ substitution into La 1-xSr xCoO 3-δ. We attempt tomore » rationalize the high activities of La 1-xSr xCoO 3-δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO 2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.« less

  18. Water electrolysis on La 1-xSr xCoO 3perovskite electrocatalysts

    DOE PAGES

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; ...

    2016-03-23

    Here, perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr 2+ substitution into La 1–xSr xCoO 3–δ. We attemptmore » to rationalize the high activities of La 1–xSr xCoO 3–δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO 2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.« less

  19. Garden-like perovskite superstructures with enhanced photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Ye, Meidan; Wang, Mengye; Zheng, Dajiang; Zhang, Nan; Lin, Changjian; Lin, Zhiqun

    2014-03-01

    By subjecting amorphous flower-like TiO2 to a facile hydrothermal synthesis in the presence of Sr2+, garden-like perovskite SrTiO3 superstructures were achieved. The amorphous TiO2 was preformed using ZnO flowers as templates. Different three-dimensional SrTiO3 architectures were coexisted in the garden, including SrTiO3 flowers composed of several hollow sword-shaped petals, many sheet-shaped petals or numerous flake-shaped petals, and SrTiO3 grass consisting of a number of long blades. These SrTiO3 superstructures were simultaneously grown on fluorine-doped tin oxide (FTO) substrates. On the basis of a comprehensive study on the effects of growth time, temperature, initial concentrations of precursor, and pH, the formation of these various hierarchical architectures was attributed primarily to the dissolution of amorphous TiO2 and precipitation of perovskite crystals, followed by the Ostwald ripening process of perovskite nanocrystals and self-organization of perovskite building blocks. Interestingly, this approach can be readily extended to create other perovskite structures, including dendritic BaTiO3 and nest-like CaTiO3, as well as PbTiO3 transformed from plate-like pyrochlore Pb2Ti2O6 after post-thermal treatment. Garden-like SrTiO3 superstructures showed a superior photocatalytic performance when compared to other as-prepared semiconductors and perovskite materials (i.e., ZnO, TiO2, BaTiO3, CaTiO3 and PbTiO3), probably due to their intrinsic photocatalytic activity and special garden-like features with a coexistence of various structures that significantly facilitated the adsorption and diffusion of methyl blue (MB) molecules and oxygen species in the photochemical reaction of MB degradation.By subjecting amorphous flower-like TiO2 to a facile hydrothermal synthesis in the presence of Sr2+, garden-like perovskite SrTiO3 superstructures were achieved. The amorphous TiO2 was preformed using ZnO flowers as templates. Different three-dimensional SrTiO3

  20. ABO blood groups, Rhesus factor, and Behçet's disease.

    PubMed

    Ozyurt, Kemal; Oztürk, Perihan; Gül, Mustafa; Benderli, Yasemin Cihan; Cölgeçen, Emine; Inci, Rahime

    2013-09-01

    Recently, numerous studies have been carried out to explain the genetics and immunopathogenesis of Behçet's disease (BD). There is still insufficient understanding of its etiopathogenesis, but substantial genetic and immune system abnormalities have been suggested. Several studies have shown remarkable associations of ABO blood groups with various diseases. This study investigated the relationship between ABO and Rhesus (D) blood groups and Behçet's disease in Turkish patients. Clinical data on gender, ABO, and Rhesus blood type of patients with BD were collected at the Kayseri Education and Research Hospital from 2005 to 2012. A total of 115 patients with BD were assessed for their association with ABO or Rhesus (D) blood groups and compared with the distribution of the blood groups of 25,701 healthy donors admitted to the Kayseri Education and Research Hospital Blood Center in 2010 and 2011. The distribution of ABO and Rhesus blood groups in patients with BD was similar to the healthy donors. No relationship was found between ABO or Rhesus blood groups and BD at our hospital. Further studies with a larger series and in different centers may be valuable for identifying the association between ABO or Rhesus (D) blood groups and BD.

  1. Effect of sintering time on structural, microstructural and chemical composition of Ni-doped lanthanum gallate perovskites

    NASA Astrophysics Data System (ADS)

    Colomer, M. T.; Kilner, J. A.

    2015-08-01

    This work reports the effect of two different sintering times, 6 and 48 h on the structural, microstructural, and chemical features of Ni-doped La0.90Sr0.10GaO3.00-δ. Independently of the sintering time, La0.90Sr0.10Ga1-xNixO3.00-δ (where x=0.10, and 0.20 (mol)) presents a rhombohedral symmetry with a lattice volume that decreases when NiO dopant increases. Besides the perovskite, LaSrGa3.00O7.00 (nominal composition) is present as second phase in all cases. When the samples are doped with NiO, the peaks of this second phase are shifted with respect to the peaks of the pure phase. These shifts suggest that this second phase could admit some Ni ions in its structure. According to the XRD patterns, the amount of the latter phase is larger when sintering time is increased. Electron probe microanalysis (EPMA) indicated that the matrix of the samples sintered for 6 h is constituted by a perovskite with an experimental composition very close to the nominal one. However, when the samples are sintered for 48 h the matrix of each sample is constituted by two perovskites; both with compositional deviations with respect to their nominal one. In particular, a significant Sr depletion compensated by a La increment in the A site is observed. Those compositional deviations could be mainly due to the diffusion of the cations in the bulk and/or from the bulk to the surface of the samples. That diffusion can favour the formation, not only, of a second perovskite with a different composition in relation with the first one formed, but also, the formation of second phases. In addition, a very slight broadening of Bragg peaks of the perovskites sintered for 48 h is observed by XRD and can be related to the presence of two different perovskites in each sample according to EPMA results. By BSEM and EPMA analyses La4.00Ga2.00O9.00 (nominal composition) is also observed as second phase when samples are treated for 48 h.

  2. Hexamethylenetetramine-mediated growth of grain-boundary-passivation CH3NH3PbI3 for highly reproducible and stable perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Zheng, Yan-Zhen; Li, Xi-Tao; Zhao, Er-Fei; Lv, Xin-Ding; Meng, Fan-Li; Peng, Chao; Lai, Xue-Sen; Huang, Meilan; Cao, Guozhong; Tao, Xia; Chen, Jian-Feng

    2018-02-01

    Simultaneously achieving the long-term device stability and reproducibility has proven challenging in perovskite solar cells because solution-processing produced perovskite film with grain boundary is sensitive to moisture. Herein, we develop a hexamethylenetetramine (HMTA)-mediated one-step solution-processing deposition strategy that leads to the formation of high-purity and grain-boundary-passivation CH3NH3PbI3 film and thereby advances cell optoelectronic performance. Through morphological and structural characterizations and theoretical calculations, we demonstrate that HMTA fully occupies the moisture-exposed surface to build a bridge across grain boundary and coordinates with Pb ions to inhibit the formation of detrimental PbI2. Such HMTA-mediated grown CH3NH3PbI3 films achieves a decent augmentation of power conversion efficiency (PCE) from 12.70% to 17.87%. A full coverage of PbI2-free CH3NH3PbI3 surface on ZnO also boosts the device's stability and reproducibility.

  3. Phase transformation of Ca-perovskite in MORB at D" region

    NASA Astrophysics Data System (ADS)

    Nishitani, N.; Ohtani, E.; Sakai, T.; Kamada, S.; Miyahara, M.; Hirao, N.

    2012-12-01

    Seismological studies indicate the presence of seismic anomalies in the Earth's deep interior. To investigate the anomaly, the physical property of the major minerals in lower mantle such as MgSiO3-perovskite, MgSiO3 post-perovskite and MgO periclase were studied well. Other candidate, CaSiO3 perovskite (Ca-perovskite) exists in peridotitic mantle and basaltic oceanic crust (mid-ocean ridge basalt; MORB). Previous studies indicate the abundance of Ca-perovskite is up to ~9 vol.% in the pyrolite mantle and ~24 vol.% in the MORB oceanic crust. However, the pressure range of previous works are still not enough to understand the D" region. In this study, natural MORB was compressed in double sided laser heated DAC. Au was used as a pressure maker and a laser absorber. NaCl was used as the thermal insulator and pressure medium. The phase relation of Ca-perovskite in MORB was investigated from 36 to 156 GPa and 300 to 2600 K by the in situ X-ray diffraction measurements at SPring-8 (BL10XU). The transition of Ca-perovskite from a tetragonal structure to a cubic structure occurred at about 1800 K up to about 100 GPa and below 1500 K at pressures above 100 GPa. This suggests that the tetragonal-cubic transition of Ca-perovskite could occur in MORB, associating with Al2O3 contents. The present results suggest that the seismic anomaly at D" layer could be caused by the transition in Ca-perovskite.

  4. ABO-Incompatible Adult Living Donor Liver Transplantation Under the Desensitization Protocol With Rituximab.

    PubMed

    Song, G-W; Lee, S-G; Hwang, S; Kim, K-H; Ahn, C-S; Moon, D-B; Ha, T-Y; Jung, D-H; Park, G-C; Kim, W-J; Sin, M-H; Yoon, Y-I; Kang, W-H; Kim, S-H; Tak, E-Y

    2016-01-01

    ABO incompatibility is no longer considered a contraindication for adult living donor liver transplantation (ALDLT) due to various strategies to overcome the ABO blood group barrier. We report the largest single-center experience of ABO-incompatible (ABOi) ALDLT in 235 adult patients. The desensitization protocol included a single dose of rituximab and total plasma exchange. In addition, local graft infusion therapy, cyclophosphamide, or splenectomy was used for a certain time period, but these treatments were eventually discontinued due to adverse events. There were three cases (1.3%) of in-hospital mortality. The cumulative 3-year graft and patient survival rates were 89.2% and 92.3%, respectively, and were comparable to those of the ABO-compatible group (n = 1301). Despite promising survival outcomes, 17 patients (7.2%) experienced antibody-mediated rejection that manifested as diffuse intrahepatic biliary stricture; six cases required retransplantation, and three patients died. ABOi ALDLT is a feasible method for expanding a living liver donor pool, but the efficacy of the desensitization protocol in targeting B cell immunity should be optimized. © Copyright 2015 The American Society of Transplantation and the American Society of Transplant Surgeons.

  5. Synthesis and Characterization of the Rare-Earth Hybrid Double Perovskites: (CH3NH3)2KGdCl6 and (CH3NH3)2KYCl6.

    PubMed

    Deng, Zeyu; Wei, Fengxia; Brivio, Federico; Wu, Yue; Sun, Shijing; Bristowe, Paul D; Cheetham, Anthony K

    2017-10-19

    Two hybrid rare-earth double perovskites, (CH 3 NH 3 ) 2 KGdCl 6 and (CH 3 NH 3 ) 2 KYCl 6 , have been synthesized by a solution evaporation method and their structures determined by variable temperature single-crystal X-ray diffraction. The diffraction results show that at room temperature both perovskites adopt a rhombohedral structure with R3̅m symmetry, as found previously for (MA) 2 KBiCl 6 , and lattice parameters of a = 7.7704(5) Å and c = 20.945(2) Å for (MA) 2 KGdCl 6 and a = 7.6212(12) Å and c = 20.742(4) Å for (MA) 2 KYCl 6 . Both phases exhibit a rhombohedral-to-cubic phase transition on heating to ∼435 K for (MA) 2 KYCl 6 and ∼375 K for (MA) 2 KGdCl 6 . Density functional calculations on the rhombohedral phase indicate that both materials have large direct band gaps, are mechanically stable, and, in the case of (MA) 2 KGdCl 6 , could exhibit magnetic ordering at low temperatures.

  6. Unreliable patient identification warrants ABO typing at admission to check existing records before transfusion.

    PubMed

    Ferrera-Tourenc, V; Lassale, B; Chiaroni, J; Dettori, I

    2015-06-01

    This study describes patient identification errors leading to transfusional near-misses in blood issued by the Alps Mediterranean French Blood Establishment (EFSAM) to Marseille Public Hospitals (APHM) over an 18-month period. The EFSAM consolidates 14 blood banks in southeast France. It supplies 149 hospitals and maintains a centralized database on ABO types used at all area hospitals. As an added precaution against incompatible transfusion, the APHM requires ABO testing at each admission regardless of whether the patient has an ABO record. The study goal was to determine if admission testing was warranted. Discrepancies between ABO type determined by admission testing and records in the centralized database were investigated. The root cause for each discrepancy was classified as specimen collection or patient admission error. Causes of patient admission events were further subclassified as namesake (name similarity) or impersonation (identity fraud). The incidence of ABO discrepancies was 1:2334 including a 1:3329 incidence of patient admission events. Impersonation was the main cause of identity events accounting for 90.3% of cases. The APHM's ABO control policy prevented 19 incompatible transfusions. In relation to the 48,593 packed red cell units transfused, this would have corresponded to a risk of 1:2526. Collecting and storing ABO typing results in a centralized database is an essential public health tool. It allows crosschecking of current test results with past records and avoids redundant testing. However, as patient identification remains unreliable, ABO typing at each admission is still warranted to prevent transfusion errors. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  7. Perovskite-perovskite tandem photovoltaics with optimized band gaps

    NASA Astrophysics Data System (ADS)

    Eperon, Giles E.; Leijtens, Tomas; Bush, Kevin A.; Prasanna, Rohit; Green, Thomas; Wang, Jacob Tse-Wei; McMeekin, David P.; Volonakis, George; Milot, Rebecca L.; May, Richard; Palmstrom, Axel; Slotcavage, Daniel J.; Belisle, Rebecca A.; Patel, Jay B.; Parrott, Elizabeth S.; Sutton, Rebecca J.; Ma, Wen; Moghadam, Farhad; Conings, Bert; Babayigit, Aslihan; Boyen, Hans-Gerd; Bent, Stacey; Giustino, Feliciano; Herz, Laura M.; Johnston, Michael B.; McGehee, Michael D.; Snaith, Henry J.

    2016-11-01

    We demonstrate four- and two-terminal perovskite-perovskite tandem solar cells with ideally matched band gaps. We develop an infrared-absorbing 1.2-electron volt band-gap perovskite, FA0.75Cs0.25Sn0.5Pb0.5I3, that can deliver 14.8% efficiency. By combining this material with a wider-band gap FA0.83Cs0.17Pb(I0.5Br0.5)3 material, we achieve monolithic two-terminal tandem efficiencies of 17.0% with >1.65-volt open-circuit voltage. We also make mechanically stacked four-terminal tandem cells and obtain 20.3% efficiency. Notably, we find that our infrared-absorbing perovskite cells exhibit excellent thermal and atmospheric stability, not previously achieved for Sn-based perovskites. This device architecture and materials set will enable “all-perovskite” thin-film solar cells to reach the highest efficiencies in the long term at the lowest costs.

  8. An isopropanol-assisted fabrication strategy of pinhole-free perovskite films in air for efficient and stable planar perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Ren, Ziqiu; Zhu, Menghua; Li, Xin; Dong, Cunku

    2017-09-01

    As a promising photovoltaic device, perovskite solar cells have attracted numerous attention in recent years, where forming a compact and pinhole-free perovskite film in air is of great importance. Herein, we evaluate highly efficient and air stable planar perovskite solar cells in air (relative humidity over 50%) with the modified two-step sequential deposition method by adjusting the CH3NH3I (MAI) concentrations and regulating the crystallization process of the perovskite film. The optimum MAI concentration is 60 mg mL-1 in isopropanol. With a planar structure of FTO/TiO2/MAPbI3/spiro-OMeTAD/Au, the efficient devices composed of compact and pinhole-free perovskite films are constructed in air, achieving a high efficiency of up to 15.10% and maintaining over 80% after 20 days storing without any encapsulation in air. With a facile fabrication process and high photovoltaic performance, this work represents a promising method for fabricating low-cost, highly efficient and stable photovoltaic device.

  9. Structural and magnetic behavior of (Ni, Cu) substituted Nd0.67Sr0.33MnO3 perovskite compounds

    NASA Astrophysics Data System (ADS)

    Arun, B.; Sudakshina, B.; Akshay, V. R.; Chandrasekhar, K. Devi; Yang, H. D.; Vasundhara, M.

    2018-05-01

    Structural and magnetic phase transition of Ni and Cu substituted Nd0.67Sr0.33MnO3 perovskite compounds have been investigated. The Rietveld refinement of X-ray powder diffraction patterns confirms that both compounds have crystallized into an orthorhombic structure with Pbnm space group same as that of Nd0.67Sr0.33MnO3 compound. X-ray absorption spectra studies completely ruled out the possibility of existence of any impurities. Both compounds do not obey the Curie-Weiss law indicates the presence of some ferromagnetic clusters within the paramagnetic matrix. Ni substituted compound shows a lower value of TC and Cu substituted compound shows a higher value of TC than that of the parent. Non-saturating tendency of magnetization is more prominently seen in the case of Cu substituted compound, indicating an increase in the AFM component.

  10. Tunable White-Light Emission in Single-Cation-Templated Three-Layered 2D Perovskites (CH 3 CH 2 NH 3 ) 4 Pb 3 Br 10–x Cl x

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mao, Lingling; Wu, Yilei; Stoumpos, Constantinos C.

    Two-dimensional (2D) hybrid halide perovskites come as a family (B) 2(A) n-1PbnX 3n+1 (B and A= cations; X= halide). These perovskites are promising semiconductors for solar cells and optoelectronic applications. Among the fascinating properties of these materials is white-light emission, which has been mostly observed in single-layered 2D lead bromide or chloride systems (n = 1), where the broad emission comes from the transient photoexcited states generated by self-trapped excitons (STEs) from structural distortion. Here we report a multilayered 2D perovskite (n = 3) exhibiting a tunable white-light emission. Ethylammonium (EA+) can stabilize the 2D perovskite structure in EA 4Pbmore » 3Br 10–xCl x (x = 0, 2, 4, 6, 8, 9.5, and 10) with EA + being both the A and B cations in this system. Because of the larger size of EA, these materials show a high distortion level in their inorganic structures, with EA4Pb3Cl10 having a much larger distortion than that of EA 4Pb 3Br 10, which results in broadband white-light emission of EA 4Pb 3Cl 10 in contrast to narrow blue emission of EA4Pb3Br10. The average lifetime of the series decreases gradually from the Cl end to the Br end, indicating that the larger distortion also prolongs the lifetime (more STE states). The band gap of EA 4Pb 3Br 10–xCl x ranges from 3.45 eV (x = 10) to 2.75 eV (x = 0), following Vegard’s law. First-principles density functional theory calculations (DFT) show that both EA 4Pb 3Cl 10 and EA 4Pb 3Br 10 are direct band gap semiconductors. The color rendering index (CRI) of the series improves from 66 (EA 4Pb 3Cl 10) to 83 (EA 4Pb 3Br 0.5Cl 9.5), displaying high tunability and versatility of the title compounds.« less

  11. Synthesis, Resistivity, and Thermal Properties of the Cubic Perovskite NH 2CH=NH 2SnI 3and Related Systems

    NASA Astrophysics Data System (ADS)

    Mitzi, D. B.; Liang, K.

    1997-12-01

    Combining concentrated hydriodic acid solutions of tin(II) iodide and formamidine acetate in an inert atmosphere results in the precipitation of a new conducting organic-inorganic compound, NH 2CH=NH 2SnI 3, which at room temperature adopts a cubic perovskite structure. The lattice constant for NH 2CH=NH 2SnI 3is found to be a=6.316(1) Å, which is approximately 1.2% larger than that for the isostructural compound CH 3NH 3SnI 3. The electrical resistivity of a pressed pellet of the new compound exhibits semimetallic temperature dependence from 10 to 300 K, with evidence of a structural transition at approximately 75 K. NH 2CH=NH 2SnI 3begins to slowly decompose in an inert atmosphere at temperatures as low as 200°C, with bulk decomposition/melting occurring above 300°C. The properties of the formamidinium-based perovskite are compared with those of the related cubic (at room temperature) perovskite CH 3NH 3SnI 3and the mixed-cation system (CH 3NH 3) 1- x(NH 2CH=NH 2) xSnI 3.

  12. PbCl2-tuned inorganic cubic CsPbBr3(Cl) perovskite solar cells with enhanced electron lifetime, diffusion length and photovoltaic performance

    NASA Astrophysics Data System (ADS)

    Li, Bo; Zhang, Yanan; Zhang, Luyuan; Yin, Longwei

    2017-08-01

    Inorganic CsPbBr3 perovskite is arousing great interest following after organic-inorganic hybrid halide perovskites, and is found as a good candidate for photovoltaic devices for its prominent photoelectric property and stability. Herein, we for the first time report on PbCl2-tuned inorganic Cl-doped CsPbBr3(Cl) perovskite solar cells with adjustable crystal structure and Cl doping for enhanced carrier lifetime, extraction rate and photovoltaic performance. The effect of PbCl2 on the morphologies, structures, optical, and photovoltaic performance of CsPbBr3 perovskite solar cells is investigated systemically. Compared with orthorhombic CsPbBr3, cubic CsPbBr3 demonstrates a significant improvement for electron lifetime (from 6.7 ns to 12.3 ns) and diffusion length (from 69 nm to 197 nm), as well as the enhanced electron extraction rate from CsPbBr3 to TiO2. More importantly, Cl doping benefits the further enhancement of carrier lifetime (14.3 ns) and diffusion length (208 nm). The Cl doped cubic CsPbBr3(Cl) perovskite solar cell exhibits a Jsc of 8.47 mA cm-2 and a PCE of 6.21%, superior to that of pure orthorhombic CsPbBr3 (6.22 mA cm-2 and 3.78%). The improvement of photovoltaic performance can be attributed to enhanced carrier lifetime, diffusion length and extraction rates, as well as suppressed nonradiative recombination.

  13. Pin-Hole Free Perovskite Film for Solar Cells Application Prepared by Controlled Two-Step Spin-Coating Method

    NASA Astrophysics Data System (ADS)

    Bahtiar, A.; Rahmanita, S.; Inayatie, Y. D.

    2017-05-01

    Morphology of perovskite film is a key important for achieving high performance perovskite solar cells. Perovskite films are commonly prepared by two-step spin-coating method. However, pin-holes are frequently formed in perovskite films due to incomplete conversion of lead-iodide (PbI2) into perovskite CH3NH3PbI3. Pin-holes in perovskite film cause large hysteresis in current-voltage curve of solar cells due to large series resistance between perovskite layer-hole transport material. Moreover, crystal structure and grain size of perovskite crystal are also other important parameters for achieving high performance solar cells, which are significantly affected by preparation of perovskite film. We studied the effect of preparation of perovskite film using controlled spin-coating parameters on crystal structure and morphological properties of perovskite film. We used two-step spin-coating method for preparation of perovskite film with varied spinning speed, spinning time and temperature of spin-coating process to control growth of perovskite crystal aimed to produce high quality perovskite crystal with pin-hole free and large grain size. All experiment was performed in air with high humidity (larger than 80%). The best crystal structure, pin-hole free with large grain crystal size of perovskite film was obtained from film prepared at room temperature with spinning speed 1000 rpm for 20 seconds and annealed at 100°C for 300 seconds.

  14. Crack-free CH3NH3PbI3 layer via continuous dripping method for high-performance mesoporous perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Chen, Guo; Zheng, Jianghui; Zheng, LingLing; Yan, Xin; Lin, Huangding; Zhang, Fengyan

    2017-01-01

    The past five years have witnessed the uniquely rapid emergence of the mixed organic-inorganic halide perovskite solar cells. Here, a modified deposition process, continuous dripping method, is reported for fabricating high-performance and reproducible perovskite solar cells. We have systematically investigated the impact of different molar ratio of lead iodide (PbI2) to dimethylsulfoxide (DMSO) on the growth, morphology and crystallinity of CH3NH3PbI3 (MAPbI3) films obtained via this process. The high power conversion efficiency (PCE) perovskite solar cell originates in crack-free and highly crystallographic perovskite films prepared with optimized ratio of PbI2 to DMSO in first precursor solution. The best PCE of 17.76% and an average PCE of 16.37 ± 0.51% were obtained via this process. Moreover, the conventional solution two steps method was also carried out as a comparison to this process. This work provides a new simple solution approach to obtain high quality of perovskite thin films for high-performance and reproducible PSCs.

  15. Synthesis and structural properties of Ba(1-x)LaxTiO3 perovskite nanoparticles fabricated by solvothermal synthesis route

    NASA Astrophysics Data System (ADS)

    Puli, Venkata Sreenivas; Adireddy, Shiva; Elupula, Ravinder; Molugu, Sudheer; Shipman, Josh; Chrisey, Douglas B.

    2017-05-01

    We report the successful synthesis and structural characterization of barium lanthanum titanate Ba(1-x)LaxTiO3 (x=0.003,0.006,0.010) nanoparticles. The colloidal nanoparticles were prepared with high yield by a solvothermal method at temperatures as low as 150°C for 24h. The as-prepared nanopowders were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), and Raman spectroscopy. The XRD studies revealed pseudo-cubic crystalline structure, with no impurity phases at room temperature. However ferroelectric tetragonal modes were clearly observed using Raman spectroscopy measurements. From TEM measurements, uniformly sized BLT nanoparticles were observed. Selected area diffraction TEM images revealed polycrystalline perovskite ring patterns, identified as corresponding to the tetragonal phase.

  16. Extended x-ray absorption fine structure study of phase transitions in the piezoelectric perovskite K0.5Na0.5NbO3

    NASA Astrophysics Data System (ADS)

    Kodre, A.; Tellier, J.; Arčon, I.; Malič, B.; Kosec, M.

    2009-06-01

    Following an x-ray diffraction study of phase transitions of the piezoelectric perovskite K0.5Na0.5NbO3 the structural changes of the material are studied using extended x-ray absorption fine structure analysis, whereby the neighborhood of Nb atom is determined in the temperature range of monoclinic, tetragonal, and cubic phases. Within the entire range Nb atom is displaced from the center of the octahedron of its immediate oxygen neighbors, as witnessed by the splitting of Nb-O distance. The model shows high prevalence of the displacement in the (111) crystallographic direction of the simple perovskite cell. The corresponding splitting of the Nb-Nb distance is negligible. There is no observable disalignment of the linear Nb-O-Nb bonds from the ideal cubic arrangement, judging from the intensity of the focusing of the photoelectron wave on the Nb-Nb scattering path by the interposed oxygen atom. As a general result, the phase transitions are found as an effect of the long-range order, while the placement of the atoms in the immediate vicinity remains largely unaffected.

  17. Cation vacancies in ferroelectric PbTiO3 and Pb(Zr,Ti)O3 : A positron annihilation lifetime spectroscopy study

    NASA Astrophysics Data System (ADS)

    Keeble, D. J.; Singh, S.; Mackie, R. A.; Morozov, M.; McGuire, S.; Damjanovic, D.

    2007-10-01

    Positron annihilation lifetime spectroscopy measurements identify A - and B -site cation vacancies in ferroelectric perovskite oxides (ABO3) . Crystal PbTiO3 and ceramic lead zirconium titanate (PZT) were studied and gave consistent values for the lifetime resulting from positron localization at lead vacancies VPb . Positron trapping to B -site vacancies was inferred in PZT. Temperature dependent studies showed that the defect specific trapping rate was higher for VB compared to VPb , consistent with the larger negative charge. Doping PZT with Fe increased the fraction positron trapping to VB compared to VPb -type defects.

  18. “Ba{sub 6}Nb{sub 4}RuO{sub 18}” and “LaBa{sub 4}Nb{sub 3}RuO{sub 15}” – The structural consequences of substituting paramagnetic cations into A{sub n}B{sub n−1}O{sub 3n} cation-deficient perovskite oxides

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kamil, Elynor L.; Morgan, Harry W.T.; Hayward, Michael A., E-mail: michael.hayward@chem.ox.ac.uk

    The B-cation deficient perovskite phases Ba{sub 6}Nb{sub 4}RuO{sub 18} and LaBa{sub 4}Nb{sub 3}RuO{sub 15} were prepared by ceramic synthesis. Neutron powder diffraction analysis indicates that rather than the 6-layer and 5-layer cation-deficient perovskite structures expected for these phases (by analogy to the known structures of Ba{sub 6}Nb{sub 4}TiO{sub 18} and LaBa{sub 4}Nb{sub 3}TiO{sub 15}) they adopt 5-layer and 4-layer B-cation deficient perovskite structures respectively, and are better described as Ba{sub 5}Nb{sub 3.33}Ru{sub 0.81}O{sub 15} and Ba{sub 3.16}La{sub 0.84}Nb{sub 2.36}Ru{sub 0.72}O{sub 12}. The factors that lead to the compositionally analogous Nb/Ru and Nb/Ti phases adopting different structures are discussed on themore » basis of the difference between d{sup 0} and non-d{sup 0} transition metal cations. - Graphical abstract: The ruthenium-containing B-cation deficient perovskite phases, Ba{sub 5}Nb{sub 3.33}Ru{sub 0.81}O{sub 15} and Ba{sub 3.16}La{sub 0.84}Nb{sub 2.36}Ru{sub 0.72}O{sub 12}, adopt 5-layer and 4-layer structures respectively, rather than the 6-layer and 5-layer cation-deficient structures adopted by the analogous titanium-containing phases Ba{sub 6}Nb{sub 4}TiO{sub 18} and LaBa{sub 4}Nb{sub 3}TiO{sub 15}. Display Omitted - Highlights: • B-cation deficient perovskite containing paramagnetic cations. • B-cation deficient structure determined by neutron powder diffraction. • Low ‘solubility’ of BaRuO{sub 3} in Ba{sub 5}Nb{sub 4}O{sub 15} leads to novel structure.« less

  19. An experimental study of perovskite-structured mixed ionic- electronic conducting oxides and membranes

    NASA Astrophysics Data System (ADS)

    Zeng, Pingying

    In recent decades, ceramic membranes based on mixed ionic and electronic conducting (MIEC) perovskite-structured oxides have received many attentions for their applications for air separation, or as a membrane reactor for methane oxidation. While numerous perovskite oxide materials have been explored over the past two decades; there are hardly any materials with sufficient practical economic value and performance for large scale applications, which justifies continuing the search for new materials. The main purposes of this thesis study are: (1) develop several novel SrCoO3-delta based MIEC oxides, SrCoCo1-xMxO3-delta, based on which membranes exhibit excellent oxygen permeability; (2) investigate the significant effects of the species and concentration of the dopants M (metal ions with fixed valences) on the various properties of these membranes; (3) investigate the significant effects of sintering temperature on the microstructures and performance of oxygen permeation membranes; and (4) study the performance of oxygen permeation membranes as a membrane reactor for methane combustion. To stabilize the cubic phase structure of the SrCoO3-delta oxide, various amounts of scandium was doped into the B-site of SrCoO 3-delta to form a series of new perovskite oxides, SrScxCoCo 1-xO3-delta (SSCx, x = 0-0.7). The significant effects of scandium-doping concentration on the phase structure, electrical conductivity, sintering performance, thermal and structural stability, cathode performance, and oxygen permeation performance of the SSCx membranes, were systematically studied. Also for a more in-depth understanding, the rate determination steps for the oxygen transport process through the membranes were clarified by theoretical and experimental investigation. It was found that only a minor amount of scandium (5 mol%) doping into the B-site of SrCoO3-delta can effectively stabilize the cubic phase structure, and thus significantly improve the electrical conductivity and

  20. High-pressure synthesis of the cubic perovskite BaRuO3 and evolution of ferromagnetism in ARuO3 (A = Ca, Sr, Ba) ruthenates.

    PubMed

    Jin, C-Q; Zhou, J-S; Goodenough, J B; Liu, Q Q; Zhao, J G; Yang, L X; Yu, Y; Yu, R C; Katsura, T; Shatskiy, A; Ito, E

    2008-05-20

    The cubic perovskite BaRuO(3) has been synthesized under 18 GPa at 1,000 degrees C. Rietveld refinement indicates that the new compound has a stretched Ru-O bond. The cubic perovskite BaRuO(3) remains metallic to 4 K and exhibits a ferromagnetic transition at T(c) = 60 K, which is significantly lower than the T(c) approximately = 160 K for SrRuO(3). The availability of cubic perovskite BaRuO(3) not only makes it possible to map out the evolution of magnetism in the whole series of ARuO(3) (A = Ca, Sr, Ba) as a function of the ionic size of the A-site r(A,) but also completes the polytypes of BaRuO(3). Extension of the plot of T(c) versus r(A) in perovskites ARuO(3) (A = Ca, Sr, Ba) shows that T(c) does not increase as the cubic structure is approached, but has a maximum for orthorhombic SrRuO(3). Suppressing T(c) by Ca and Ba doping in SrRuO(3) is distinguished by sharply different magnetic susceptibilities chi(T) of the paramagnetic phase. This distinction has been interpreted in the context of a Griffiths' phase on the (Ca Sr)RuO(3) side and bandwidth broadening on the (Sr,Ba)RuO(3) side.

  1. High-pressure synthesis of the cubic perovskite BaRuO3 and evolution of ferromagnetism in ARuO3 (A = Ca, Sr, Ba) ruthenates

    PubMed Central

    Jin, C.-Q.; Zhou, J.-S.; Goodenough, J. B.; Liu, Q. Q.; Zhao, J. G.; Yang, L. X.; Yu, Y.; Yu, R. C.; Katsura, T.; Shatskiy, A.; Ito, E.

    2008-01-01

    The cubic perovskite BaRuO3 has been synthesized under 18 GPa at 1,000°C. Rietveld refinement indicates that the new compound has a stretched Ru–O bond. The cubic perovskite BaRuO3 remains metallic to 4 K and exhibits a ferromagnetic transition at Tc = 60 K, which is significantly lower than the Tc ≈ 160 K for SrRuO3. The availability of cubic perovskite BaRuO3 not only makes it possible to map out the evolution of magnetism in the whole series of ARuO3 (A = Ca, Sr, Ba) as a function of the ionic size of the A-site rA, but also completes the polytypes of BaRuO3. Extension of the plot of Tc versus rA in perovskites ARuO3 (A = Ca, Sr, Ba) shows that Tc does not increase as the cubic structure is approached, but has a maximum for orthorhombic SrRuO3. Suppressing Tc by Ca and Ba doping in SrRuO3 is distinguished by sharply different magnetic susceptibilities χ(T) of the paramagnetic phase. This distinction has been interpreted in the context of a Griffiths' phase on the (Ca Sr)RuO3 side and bandwidth broadening on the (Sr,Ba)RuO3 side. PMID:18480262

  2. Composition-dependent emission linewidth broadening in lead bromide perovskite (APbBr3, A = Cs and CH3NH3) nanoparticles.

    PubMed

    Ham, Sujin; Chung, Heejae; Kim, Tae-Woo; Kim, Jiwon; Kim, Dongho

    2018-02-01

    Lead halide perovskite nanoparticles (NPs) are attractive as they exhibit excellent color purity and have a tunable band gap, and can thus be applied in highly efficient photovoltaic and light-emitting diodes. Fundamental studies of emission linewidth broadening due to spectral shifts in perovskite NPs may suggest a way to improve their color purity. However, the carrier-induced Stark shift that causes spectral diffusion still requires investigation. In this study, we explore composition-related emission linewidth broadening by comparing CsPbBr3 and CH 3 NH 3 PbBr 3 (MAPbBr3) perovskite NPs. We find that the MAPbBr3 NPs are more sensitive to fluctuations in the local electric fields than the CsPbBr3 NPs due to an intrinsic difference in the dipole moment between the two A cations (Cs and MA), which shows a carrier-induced Stark shift. The results indicate that the compositions of perovskite NPs are closely associated with emission linewidth broadening and they also provide insights into the development of NP-based devices with high color purity.

  3. Electron–phonon coupling in hybrid lead halide perovskites

    PubMed Central

    Wright, Adam D.; Verdi, Carla; Milot, Rebecca L.; Eperon, Giles E.; Pérez-Osorio, Miguel A.; Snaith, Henry J.; Giustino, Feliciano; Johnston, Michael B.; Herz, Laura M.

    2016-01-01

    Phonon scattering limits charge-carrier mobilities and governs emission line broadening in hybrid metal halide perovskites. Establishing how charge carriers interact with phonons in these materials is therefore essential for the development of high-efficiency perovskite photovoltaics and low-cost lasers. Here we investigate the temperature dependence of emission line broadening in the four commonly studied formamidinium and methylammonium perovskites, HC(NH2)2PbI3, HC(NH2)2PbBr3, CH3NH3PbI3 and CH3NH3PbBr3, and discover that scattering from longitudinal optical phonons via the Fröhlich interaction is the dominant source of electron–phonon coupling near room temperature, with scattering off acoustic phonons negligible. We determine energies for the interacting longitudinal optical phonon modes to be 11.5 and 15.3 meV, and Fröhlich coupling constants of ∼40 and 60 meV for the lead iodide and bromide perovskites, respectively. Our findings correlate well with first-principles calculations based on many-body perturbation theory, which underlines the suitability of an electronic band-structure picture for describing charge carriers in hybrid perovskites. PMID:27225329

  4. Chalcogenide Perovskites for Solar Energy Harvesting

    NASA Astrophysics Data System (ADS)

    Perera, Samanthe

    Methylammonium Lead halide perovskites have recently emerged as a promising candidate for realizing high efficient low cost photovoltaic modules. Charge transport properties of the solution processed halide perovskites are comparable to some of the existing absorbers used in the current PV industry which require sophisticated processing techniques. Due to this simple processing required to achieve high efficiencies, halide perovskites have become an active field of research. As a result, perovskite solar cells are rapidly reaching towards theoretical efficiency limit of close to 30%. It's believed that ionicity inherent to perovskite materials is one of the contributing factors for the excellent charge transport properties of perovskites. Despite the growing interest for solar energy harvesting purposes, these halide perovskites have serious limitations such as toxicity and instability that need to be addressed in order to commercialize the solar cells incorporating them. This dissertation focuses on a new class of ionic semiconductors, chalcogenide perovskites for solar energy harvesting purposes. Coming from the family perovskites they are expected to have same excellent charge transport properties inherent to perovskites due to the ionicity. Inspired by few theoretical studies on chalcogenide perovskites, BaZrS3 and its Ti alloys were synthesized by sulfurizing the oxide counterpart. Structural characterizations have confirmed the predicted distorted perovskite phase. Optical characterizations have verified the direct band gap suitable for thin film single junction solar cells. Anion alloying was demonstrated by synthesizing oxysulfides with widely tunable band gap suitable for applications such as solid state lighting and sensing.

  5. Molecular genotyping of ABO blood groups in some population groups from India.

    PubMed

    Ray, Sabita; Gorakshakar, Ajit C; Vasantha, K; Nadkarni, Anita; Italia, Yazdi; Ghosh, Kanjaksha

    2014-01-01

    Indian population is characterized by the presence of various castes and tribal groups. Various genetic polymorphisms have been used to differentiate among these groups. Amongst these, the ABO blood group system has been extensively studied. There is no information on molecular genotyping of ABO blood groups from India. Therefore, the main objective of this study was to characterize the common A, B and O alleles by molecular analysis in some Indian population groups. One hundred samples from the mixed population from Mumbai, 101 samples from the Dhodia tribe and 100 samples from the Parsi community were included in this study. Initially, the samples were phenotyped by standard serologic techniques. PCR followed by single strand conformational polymorphsim (SSCP) was used for molecular ABO genotyping. Samples showing atypical SSCP patterns were further analysed by DNA sequencing to characterize rare alleles. Seven common ABO alleles with 19 different genotypes were found in the mixed population. The Dhodias showed 12 different ABO genotypes and the Parsis revealed 15 different ABO genotypes with six common ABO alleles identified in each of them. Two rare alleles were also identified. This study reports the distribution of molecular genotypes of ABO alleles among some population groups from India. Considering the extremely heterogeneous nature of the Indian population, in terms of various genotype markers like blood groups, red cell enzymes, etc., many more ABO alleles are likely to be encountered.

  6. Efficient CH3NH3PbI3 perovskite/fullerene planar heterojunction hybrid solar cells with oxidized Ni/Au/Cu transparent electrode

    NASA Astrophysics Data System (ADS)

    Lai, Wei-Chih; Lin, Kun-Wei; Guo, Tzung-Fang; Chen, Peter; Liao, Yuan-Yu

    2018-02-01

    We demonstrated the performance of inverted CH3NH3PbI3 perovskite-based solar cells (SCs) with a thermally oxidized nickel/gold/copper (Ni/Au/Cu) trilayer transparent electrode. Oxidized Ni/Au/Cu is a high transparent layer and has less resistance than the oxidized Ni/Au layer. Like the oxidized Ni/Au layer, oxidized Ni and Cu in oxidized Ni/Au/Cu could perform as a hole transport layer of the perovskite-based SCs. It leads to improved perovskite SC performance on an open circuit voltage of 1.01 V, a short circuit current density of 14.36 mA/cm2, a fill factor of 76.7%, and a power conversion efficiency (η%) of 11.1%. The η% of perovskite SCs with oxidized Ni (10 nm)/Au (6 nm)/Cu (1 nm) improved by approximately 10% compared with that of perovskite SCs with oxidized Ni/Au.

  7. Oxygen vacancy induced structural evolution of SrFeO3 -x epitaxial thin film from brownmillerite to perovskite

    NASA Astrophysics Data System (ADS)

    Roh, Seulki; Lee, Seokbae; Lee, Myounghoon; Seo, Yu-Seong; Khare, Amit; Yoo, Taesup; Woo, Sungmin; Choi, Woo Seok; Hwang, Jungseek; Glamazda, A.; Choi, K.-Y.

    2018-02-01

    We investigated SrFeO3 -x thin films on a SrTiO3 (001) substrate prepared via pulsed laser epitaxy using an optical spectroscopy technique. The oxygen vacancy level (x ) was controlled by post-annealing processes at different oxygen partial pressures. We achieved a brownmillerite (BM) structure at x =0.5 and observed the evolution of the crystal structure from BM into perovskite (PV) as the oxygen concentration increased. We observed the evolution of infrared-active phonons with respect to the oxygen concentration, which was closely related to the structural evolution observed via x-ray diffraction. We identified the phonons using the shell-model calculation. Furthermore, we studied temperature-dependent behaviors of the phonon modes of three representative samples: PV and two BMs (BMoop and BMip) with different orientations of the oxygen vacancy channel. In the BMoop sample, we observed a phonon mode, which exhibited an unusual redshift with decreasing temperature; this behavior may have been due to the apical oxygen instability in the FeO6 octahedron. Our results provide important information regarding the ionic conduction mechanism in SrFeO3 -x material systems.

  8. Structural and thermoelectric properties of A-site substituted (Sr1-x-yCaxNdy)TiO3 perovskites

    NASA Astrophysics Data System (ADS)

    Somaily, Hamoud H.

    Detailed structural results and models are reported for a special class of A-site substituted perovskites, (Sr1-x-yCaxNd y)TiO3, obtained with high resolution NPD data as a function of temperature and Nd composition. Two series with various A-site concentrations were synthesized and investigated. Each series was designed to have a nominally constant tolerance factor. At room temperature (RT), I determine the space groups of the Sr-rich and Sr poor series as being tetragonal I4/mcm and orthorhombic Pbnm, respectively. The RT structures remain unchanged upon increasing the Nd3+ content. However, three different orthorhombic phases, Pbnm, Ibmm, Pbcm, are determined for the Sr-rich series as a function of decreasing temperature; whereas, for the Sr-poor series the orthorhombic Pbnm structure is found to persist throughout the full range of measured temperatures. A phase diagram is constructed and proposed in the temperature range 0-1000 K. Thermoelectric properties of (Sr 1-x-yCaxNdy)TiO3 were also investigated and the best figure of merit ZT=0.07 was obtained with the Sr-rich series.

  9. A Strategy for Architecture Design of Crystalline Perovskite Light-Emitting Diodes with High Performance.

    PubMed

    Shi, Yifei; Wu, Wen; Dong, Hua; Li, Guangru; Xi, Kai; Divitini, Giorgio; Ran, Chenxin; Yuan, Fang; Zhang, Min; Jiao, Bo; Hou, Xun; Wu, Zhaoxin

    2018-06-01

    All present designs of perovskite light-emitting diodes (PeLEDs) stem from polymer light-emitting diodes (PLEDs) or perovskite solar cells. The optimal structure of PeLEDs can be predicted to differ from PLEDs due to the different fluorescence dynamics and crystallization between perovskite and polymer. Herein, a new design strategy and conception is introduced, "insulator-perovskite-insulator" (IPI) architecture tailored to PeLEDs. As examples of FAPbBr 3 and MAPbBr 3 , it is experimentally shown that the IPI structure effectively induces charge carriers into perovskite crystals, blocks leakage currents via pinholes in the perovskite film, and avoids exciton quenching simultaneously. Consequently, as for FAPbBr 3 , a 30-fold enhancement in the current efficiency of IPI-structured PeLEDs compared to a control device with poly(3,4ethylenedioxythiophene):poly(styrene sulfonate) as hole-injection layer is achieved-from 0.64 to 20.3 cd A -1 -while the external quantum efficiency is increased from 0.174% to 5.53%. As the example of CsPbBr 3 , compared with the control device, both current efficiency and lifetime of IPI-structured PeLEDs are improved from 1.42 and 4 h to 9.86 cd A -1 and 96 h. This IPI architecture represents a novel strategy for the design of light-emitting didoes based on various perovskites with high efficiencies and stabilities. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Clinical use of the ABO-Scoring Index: reliability and subtraction frequency.

    PubMed

    Lieber, William S; Carlson, Sean K; Baumrind, Sheldon; Poulton, Donald R

    2003-10-01

    This study tested the reliability and subtraction frequency of the study model-scoring system of the American Board of Orthodontists (ABO). We used a sample of 36 posttreatment study models that were selected randomly from six different orthodontic offices. Intrajudge and interjudge reliability was calculated using nonparametric statistics (Spearman rank coefficient, Wilcoxon, Kruskal-Wallis, and Mann-Whitney tests). We found differences ranging from 3 to 6 subtraction points (total score) for intrajudge scoring between two sessions. For overall total ABO score, the average correlation was .77. Intrajudge correlation was greatest for occlusal relationships and least for interproximal contacts. Interjudge correlation for ABO score averaged r = .85. Correlation was greatest for buccolingual inclination and least for overjet. The data show that some judges, on average, were much more lenient than others and that this resulted in a range of total scores between 19.7 and 27.5. Most of the deductions were found in the buccal segments and most were related to the second molars. We present these findings in the context of clinicians preparing for the ABO phase III examination and for orthodontists in their ongoing evaluation of clinical results.

  11. Associations between ABO blood groups and biochemical recurrence after radical prostatectomy.

    PubMed

    Ohno, Yoshio; Ohori, Makoto; Nakashima, Jun; Okubo, Hidenori; Satake, Naoya; Takizawa, Issei; Hashimoto, Takeshi; Hamada, Riu; Nakagami, Yoshihiro; Yoshioka, Kunihiko; Tachibana, Masaaki

    2015-01-01

    Recent studies have demonstrated associations between ABO blood groups and prognosis in various types of cancers. The aim of this study was to investigate the association between ABO blood groups and biochemical recurrence (BCR) after radical prostatectomy (RP). A total of 555 patients with prostate cancer who underwent RP were included in the study. No patients received neoadjuvant and/or adjuvant therapy. The effect of ABO blood groups on BCR was examined using univariate and multivariate analyses. During the follow-up period (mean, 52.0 months), 166 patients (29.9%) experienced BCR, with a 5-year BCR-free rate of 67.3%. Although the ABO blood group was not a significantly associated with BCR in the univariate analysis, it was an independent predictor of BCR in the multivariate analysis: blood type O patients had a significantly lower risk of BCR compared to type A patients (Hazard ratio, 0.608; 95% confidence interval, 0.410-0.902; P = 0.014). Further analyses revealed that surgical margin status confounded the assessment of the association between the ABO blood group and BCR. In the analyses of patients with a negative surgical margin, the 5-year BCR-free rate in blood type O patients was a significantly higher than that in type A patients (91.2% vs. 71.0%; P = 0.026). Blood type O is significantly associated with a decreased risk of biochemical recurrence after radical prostatectomy. Further studies are needed to clarify the nature of this association.

  12. Tunable inversion symmetry to control indirect-to-direct band gaps transitions

    NASA Astrophysics Data System (ADS)

    Lu, Xue-Zeng; Rondinelli, James M.

    2018-05-01

    Electric-field tunable indirect-to-direct band gap transitions occur in thin-film silicon and transition metal dichalcogenides; however, they remain challenging to access in three-dimensional transition metal oxides. Very recently, an unusual polar-to-nonpolar phase transition under epitaxial strain was discovered in A3B2O7 hybrid improper ferroelectrics (HIFs), which supports controllable dielectric anisotropy and magnetization. Here we examine HIF (ABO3) 1/(A'BO3) 1 superlattices and AA'BB' O6 double perovskites and predict a competing nonpolar antiferroelectric phase, demonstrating it is hidden in hybrid improper ferroelectrics exhibiting corner-connected B O6 octahedra. Furthermore, we show the transition between the polar and nonpolar phases enables an in-plane electric field to control the indirect-to-direct band gap transition at the phase boundary in the (ABO3) 1/(A'BO3) 1 superlattices and AA'BB' O6 double perovskites, which may be tuned through static strain or chemical substitution. Our findings establish HIFs as a functional electronics class from which to realize direct gap materials and enables the integration of a broader palette of chemistries and compounds for linear and nonlinear optical applications.

  13. Interfacial Electronic Structures of Photodetectors Based on C8BTBT/Perovskite.

    PubMed

    Li, Lin; Tong, Sichao; Zhao, Yuan; Wang, Can; Wang, Shitan; Lyu, Lu; Huang, Yingbao; Huang, Han; Yang, Junliang; Niu, Dongmei; Liu, Xiaoliang; Gao, Yongli

    2018-06-07

    Comprehensive measurements of ultraviolet photoemission spectroscopy, X-ray photoemission spectroscopy, X-ray diffraction, and atomic force microscopy are adopted to investigate the corelevance of energy level alignment, molecular orientation, and film growth of Au/C8BTBT/perovskite interfaces. A small energy offset of valence band maximum of 0.06 eV between perovskite and C8BTBT makes hole transportation feasible. About 0.65 eV upward shift of energy levels is observed with the deposition of the Au film on C8BTBT, which enhances hole transportation to the Au electrode. The observations from the interface analysis are supported by a prototype photodetector of Au (80 nm)/C8BTBT (20 nm)/perovskite (100 nm) that exhibits excellent performances whose responsivity can reach up to 2.65 A W -1 , 4 times higher than the best CH 3 NH 3 PbI 3 photodetectors.

  14. Enhanced photovoltaic properties of perovskite solar cells by TiO2 homogeneous hybrid structure.

    PubMed

    Su, Pengyu; Fu, Wuyou; Yao, Huizhen; Liu, Li; Ding, Dong; Feng, Fei; Feng, Shuang; Xue, Yebin; Liu, Xizhe; Yang, Haibin

    2017-10-01

    In this paper, we fabricated a TiO 2 homogeneous hybrid structure for application in perovskite solar cells (PSCs) under ambient conditions. Under the standard air mass 1.5 global (AM 1.5G) illumination, PSCs based on homogeneous hybrid structure present a maximum power conversion efficiency of 5.39% which is higher than that of pure TiO 2 nanosheets. The enhanced properties can be explained by the better contact of TiO 2 nanosheets/nanoparticles with CH 3 NH 3 PbI 3 and fewer pinholes in electron transport materials. The advent of such unique structure opens up new avenues for the future development of high-efficiency photovoltaic cells.

  15. The photocurrent response in the perovskite device based on coordination polymers: structure, topology, band gap and matched energy levels.

    PubMed

    Luo, Hai-Qiang; Xing, Xiao-Han; Zhang, Pan; Yan, Zhi-Shuo; Zhou, Qing-Feng; Gong, Yun; Lin, Jian-Hua

    2017-06-28

    Using a rigid ditopic ligand, 4,5-di(4'-carboxylphenyl)benzene (H 2 L), three coordination polymers (CPs) formulated as MnL(H 2 O) 2 (1), CdL(H 2 O) (2) and Mn 2 L 2 (DMF) 3 (3) have been synthesized and structurally characterized by single-crystal X-ray diffraction. These three CPs display 2D architectures but with different topologies. The experimental data and DFT calculation indicate that CP 2 is a semiconductor, and its CB/VB energy levels match with those of the perovskite CH 3 NH 3 PbI 3 . A FTO/TiO 2 /CH 3 NH 3 PbI 3 /CP 2 device is fabricated and the CP-based device shows much larger photoresponse under visible light illumination (650 nm > λ > 350 nm, 100 mW cm -2 ) than the individual CP 2. At 0 V vs. AgCl/Ag, the largest photocurrent density yielded by the CP-based perovskite device is ca. 200 times that of CP 2, which is due to the matched energy levels of all the materials in the device, leading the photogenerated electron-hole pairs to be separated effectively. Meanwhile, the coverage of the insoluble CP on the surface of the perovskite CH 3 NH 3 PbI 3 can improve the stability of the perovskite against water.

  16. Structure, magnetism and electronic properties in 3d-5d based double perovskite ({Sr_{1-x}} Y x )2FeIrO6

    NASA Astrophysics Data System (ADS)

    Kharkwal, K. C.; Pramanik, A. K.

    2017-12-01

    The 3d-5d based double perovskites are of current interest as they provide model systems to study the interplay between electronic correlation (U) and spin-orbit coupling (SOC). Here, we report detailed structural, magnetic and transport properties of doped double perovskite material (Sr1-x Y x )2FeIrO6 with x ≤slant 0.2 . With substitution of Y, the system retains its original crystal structure but structural parameters change with x in nonmonotonic fashion. The magnetization data for Sr2FeIrO6 show antiferromagnetic type magnetic transition around 45 K however, a close inspection of the data indicates a weak magnetic phase transition around 120 K. No change of structural symmetry has been observed down to low temperature, although the lattice parameters show sudden changes around the magnetic transitions. Sr2FeIrO6 shows an insulating behavior over the whole temperature range, which nevertheless does not change with Y substitution. The nature of charge conduction is found to follow thermally activated Mott’s variable range hopping and power law behavior for parent and doped samples, respectively. Interestingly, evolution of structural, magnetic and transport behavior in (Sr1-x Y x )2FeIrO6 is observed to reverse with x > 0.1 , which is believed to arise due to a change in the transition metal ionic state.

  17. Structure, magnetism and electronic properties in 3d-5d based double perovskite ([Formula: see text]Y x )2FeIrO6.

    PubMed

    Kharkwal, K C; Pramanik, A K

    2017-11-13

    The 3d-5d based double perovskites are of current interest as they provide model systems to study the interplay between electronic correlation (U) and spin-orbit coupling (SOC). Here, we report detailed structural, magnetic and transport properties of doped double perovskite material ([Formula: see text]Y x ) 2 FeIrO 6 with [Formula: see text]. With substitution of Y, the system retains its original crystal structure but structural parameters change with x in nonmonotonic fashion. The magnetization data for Sr 2 FeIrO 6 show antiferromagnetic type magnetic transition around 45 K; however, a close inspection of the data indicates a weak magnetic phase transition around 120 K. No change of structural symmetry has been observed down to low temperature, although the lattice parameters show sudden changes around the magnetic transitions. Sr 2 FeIrO 6 shows an insulating behavior over the whole temperature range, which nevertheless does not change with Y substitution. The nature of charge conduction is found to follow thermally activated Mott's variable range hopping and power law behavior for parent and doped samples, respectively. Interestingly, evolution of structural, magnetic and transport behavior in ([Formula: see text]Y x ) 2 FeIrO 6 is observed to reverse with [Formula: see text], which is believed to arise due to a change in the transition metal ionic state.

  18. Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts

    PubMed Central

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; Hardin, William G.; Dai, Sheng; Kolpak, Alexie M.; Johnston, Keith P.; Stevenson, Keith J.

    2016-01-01

    Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr2+ substitution into La1−xSrxCoO3−δ. We attempt to rationalize the high activities of La1−xSrxCoO3−δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis. PMID:27006166

  19. High-Performance CH3NH3PbI3-Inverted Planar Perovskite Solar Cells with Fill Factor Over 83% via Excess Organic/Inorganic Halide.

    PubMed

    Jahandar, Muhammad; Khan, Nasir; Lee, Hang Ken; Lee, Sang Kyu; Shin, Won Suk; Lee, Jong-Cheol; Song, Chang Eun; Moon, Sang-Jin

    2017-10-18

    The reduction of charge carrier recombination and intrinsic defect density in organic-inorganic halide perovskite absorber materials is a prerequisite to achieving high-performance perovskite solar cells with good efficiency and stability. Here, we fabricated inverted planar perovskite solar cells by incorporation of a small amount of excess organic/inorganic halide (methylammonium iodide (CH 3 NH 3 I; MAI), formamidinium iodide (CH(NH 2 ) 2 I; FAI), and cesium iodide (CsI)) in CH 3 NH 3 PbI 3 perovskite film. Larger crystalline grains and enhanced crystallinity in CH 3 NH 3 PbI 3 perovskite films with excess organic/inorganic halide reduce the charge carrier recombination and defect density, leading to enhanced device efficiency (MAI+: 14.49 ± 0.30%, FAI+: 16.22 ± 0.38% and CsI+: 17.52 ± 0.56%) compared to the efficiency of a control MAPbI 3 device (MAI: 12.63 ± 0.64%) and device stability. Especially, the incorporation of a small amount of excess CsI in MAPbI 3 perovskite film leads to a highly reproducible fill factor of over 83%, increased open-circuit voltage (from 0.946 to 1.042 V), and short-circuit current density (from 18.43 to 20.89 mA/cm 2 ).

  20. Synthesis and equation of state of post-perovskites in the (Mg,Fe)[subscript 3]Al[subscript 2]Si[subscript 3]O[subscript 12] system

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shieh, Sean R.; Dorfman, Susannah M.; Kubo, Atsushi

    The formation and properties of the post-perovskite (CaIrO{sub 3}-type) phase were studied in Fe-rich compositions along the pyrope-almandine ((Mg,Fe){sub 3}Al{sub 2}Si{sub 3}O{sub 12}) join. Natural and synthetic garnet starting materials with almandine fractions from 38 to 90 mol% were studied using synchrotron X-ray diffraction in the laser-heated diamond anvil cell. Single-phase post-perovskite could be successfully synthesized from garnet compositions at pressures above 148 GPa and temperatures higher than 1600 K. In some cases, evidence for a minor amount of Al{sub 2}O{sub 3} post-perovskite was observed for Alm38 and Alm54 compositions in the perovskite + post-perovskite two-phase region. Pressure-volume data formore » the post-perovskite phases collected during decompression show that incorporation of Fe leads to a systematic increase of unit cell volume broadly similar to the variation observed in the (Mg,Fe)SiO{sub 3} system. The presence of Al{sub 2}O{sub 3} increases the stability of perovskite relative to post-perovskite, requiring higher pressures (> 148 GPa) for synthesis of pure post-perovskites. Our data together with those of Tateno et al. (2005) also suggest that in the Al-rich system the presence of Fe has no strong effect on the pressure required to synthesize the pure post-perovskite phase, but the two-phase perovskite and post-perovskite region may be broad and its width dependent on Fe content. Our results suggest that any regions highly enriched in Al{sub 2}O{sub 3} may consist of either the perovskite phase or a mixture of perovskite and post-perovskite phases throughout the entire thickness of the D* region. The observed synthesis pressures (> 148 GPa) for a pure post-perovskite phase are beyond that at the Earth's core-mantle boundary ({approx} 135 GPa).« less

  1. Molecular genotyping of ABO blood groups in some population groups from India

    PubMed Central

    Ray, Sabita; Gorakshakar, Ajit C.; Vasantha, K.; Nadkarni, Anita; Italia, Yazdi; Ghosh, Kanjaksha

    2014-01-01

    Background & objectives: Indian population is characterized by the presence of various castes and tribal groups. Various genetic polymorphisms have been used to differentiate among these groups. Amongst these, the ABO blood group system has been extensively studied. There is no information on molecular genotyping of ABO blood groups from India. Therefore, the main objective of this study was to characterize the common A, B and O alleles by molecular analysis in some Indian population groups. Methods: One hundred samples from the mixed population from Mumbai, 101 samples from the Dhodia tribe and 100 samples from the Parsi community were included in this study. Initially, the samples were phenotyped by standard serologic techniques. PCR followed by single strand conformational polymorphsim (SSCP) was used for molecular ABO genotyping. Samples showing atypical SSCP patterns were further analysed by DNA sequencing to characterize rare alleles. Results: Seven common ABO alleles with 19 different genotypes were found in the mixed population. The Dhodias showed 12 different ABO genotypes and the Parsis revealed 15 different ABO genotypes with six common ABO alleles identified in each of them. Two rare alleles were also identified. Interpretation & conclusions: This study reports the distribution of molecular genotypes of ABO alleles among some population groups from India. Considering the extremely heterogeneous nature of the Indian population, in terms of various genotype markers like blood groups, red cell enzymes, etc., many more ABO alleles are likely to be encountered. PMID:24604045

  2. Enhancing Perovskite Solar Cell Performance by Interface Engineering Using CH3NH3PbBr0.9I2.1 Quantum Dots.

    PubMed

    Cha, Mingyang; Da, Peimei; Wang, Jun; Wang, Weiyi; Chen, Zhanghai; Xiu, Faxian; Zheng, Gengfeng; Wang, Zhong-Sheng

    2016-07-13

    To improve the interfacial charge transfer that is crucial to the performance of perovskite solar cells, the interface engineering in a device should be rationally designed. Here we have developed an interface engineering method to tune the photovoltaic performance of planar-heterojunction perovskite solar cells by incorporating MAPbBr3-xIx (MA = CH3NH3) quantum dots (QDs) between the MAPbI3 perovskite film and the hole-transporting material (HTM) layer. By adjustment of the Br:I ratio, the as-synthesized MAPbBr3-xIx QDs show tunable fluorescence and band edge positions. When the valence band (VB) edge of MAPbBr3-xIx QDs is located below that of the MAPbI3 perovskite, the hole transfer from the MAPbI3 perovskite film to the HTM layer is hindered, and hence, the power conversion efficiency decreases. In contrast, when the VB edge of MAPbBr3-xIx QDs is located between the VB edge of the MAPbI3 perovskite film and the highest occupied molecular orbital of the HTM layer, the hole transfer from the MAPbI3 perovskite film to the HTM layer is well-facilitated, resulting in significant improvements in the fill factor, short-circuit photocurrent, and power conversion efficiency.

  3. Unraveling the Role of Monovalent Halides in Mixed-Halide Organic-Inorganic Perovskites.

    PubMed

    Deepa, Melepurath; Ramos, F Javier; Shivaprasad, S M; Ahmad, Shahzada

    2016-03-16

    The performance of perovskite solar cells is strongly influenced by the composition and microstructure of the perovskite. A recent approach to improve the power conversion efficiencies utilized mixed-halide perovskites, but the halide ions and their roles were not directly studied. Unraveling their precise location in the perovskite layer is of paramount importance. Here, we investigated four different perovskites by using X-ray photoelectron spectroscopy, and found that among the three studied mixed-halide perovskites, CH3 NH3 Pb(I0.74 Br0.26 )3 and CH3 NH3 PbBr3-x Clx show peaks that unambiguously demonstrate the presence of iodide and bromide in the former, and bromide and chloride in the latter. The CH3 NH3 PbI3-x Clx perovskite shows anomalous behavior, the iodide content far outweighs that of the chloride; a small proportion of chloride, in all likelihood, resides deep within the TiO2 /absorber layer. Our study reveals that there are many distinguishable structural differences between these perovskites, and that these directly impact the photovoltaic performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Advances in Perovskite Solar Cells

    PubMed Central

    Zuo, Chuantian; Bolink, Henk J.; Han, Hongwei; Huang, Jinsong

    2016-01-01

    Organolead halide perovskite materials possess a combination of remarkable optoelectronic properties, such as steep optical absorption edge and high absorption coefficients, long charge carrier diffusion lengths and lifetimes. Taken together with the ability for low temperature preparation, also from solution, perovskite‐based devices, especially photovoltaic (PV) cells have been studied intensively, with remarkable progress in performance, over the past few years. The combination of high efficiency, low cost and additional (non‐PV) applications provides great potential for commercialization. Performance and applications of perovskite solar cells often correlate with their device structures. Many innovative device structures were developed, aiming at large‐scale fabrication, reducing fabrication cost, enhancing the power conversion efficiency and thus broadening potential future applications. This review summarizes typical structures of perovskite solar cells and comments on novel device structures. The applications of perovskite solar cells are discussed. PMID:27812475

  5. Nature of the octahedral tilting phase transitions in perovskites: A case study of CaMnO3

    NASA Astrophysics Data System (ADS)

    Klarbring, Johan; Simak, Sergei I.

    2018-01-01

    The temperature-induced antiferrodistortive (AFD) structural phase transitions in CaMnO3, a typical perovskite oxide, are studied using first-principles density functional theory calculations. These transitions are caused by tilting of the MnO6 octahedra that are related to unstable phonon modes in the high-symmetry cubic perovskite phase. Transitions due to octahedral tilting in perovskites normally are believed to fit into the standard soft-mode picture of displacive phase transitions. We calculate phonon-dispersion relations and potential-energy landscapes as functions of the unstable phonon modes and argue based on the results that the phase transitions are better described as being of order-disorder type. This means that the cubic phase emerges as a dynamical average when the system hops between local minima on the potential-energy surface. We then perform ab initio molecular dynamics simulations and find explicit evidence of the order-disorder dynamics in the system. Our conclusions are expected to be valid for other perovskite oxides, and we finally suggest how to predict the nature (displacive or order-disorder) of the AFD phase transitions in any perovskite system.

  6. Hybrid Lead Halide Layered Perovskites with Silsesquioxane Interlayers.

    PubMed

    Kataoka, Sho; Kaburagi, Wako; Mochizuki, Hiroyuki; Kamimura, Yoshihiro; Sato, Kazuhiko; Endo, Akira

    2018-01-01

    Hybrid organic-lead halide perovskites exhibit remarkable properties as semiconductors and light absorbers. Here, we report the formation of silsesquioxane-lead halide hybrid layered perovskites. We prepared silsesquioxane with a cubic cage-like structure and fabricated hybrid silsesquioxane-lead halide layered perovskites in a self-assembled manner. It is demonstrated that the silsesquioxane maintain their cage-like structure between lead halide perovskite layers. The silsesquioxane-lead halide perovskites also show excitonic absorption and emission in the visible light region similar to typical lead halide layered perovskites.

  7. High pressure luminescence of Nd3+ in YAlO3 perovskite nanocrystals: A crystal-field analysis

    NASA Astrophysics Data System (ADS)

    Hernández-Rodríguez, Miguel A.; Muñoz-Santiuste, Juan E.; Lavín, Víctor; Lozano-Gorrín, Antonio D.; Rodríguez-Hernández, Plácida; Muñoz, Alfonso; Venkatramu, Vemula; Martín, Inocencio R.; Rodríguez-Mendoza, Ulises R.

    2018-01-01

    Pressure-induced energy blue- and red-shifts of the 4F3/2 → 4I9/2,11/2 near-infrared emission lines of Nd3+ ions in YAlO3 perovskite nano-particles have been measured from ambient conditions up to 29 GPa. Different positive and negative linear pressure coefficients have been calibrated for the emission lines and related to pressure-induced changes in the interactions between those Nd3+ ions and their twelve oxygen ligands at the yttrium site. Potentiality of the simple overlap model, combined with ab initio structural calculations, in the description of the effects of these interactions on the energy levels and luminescence properties of the optically active Nd3+ ion is emphasized. Simulations show how the energies of the 4f3 ground configuration and the barycenters of the multiplets increase with pressure, whereas the Coulomb interaction between f-electrons decreases and the crystal-field strength increases. All these effects combined explain the wavelength blue-shifts of some near-infrared emission lines of Nd3+ ions. Large pressure rates of various emission lines suggest that a YAlO3 perovskite nano-crystal can be a potential candidate for near-infrared optical pressure sensors.

  8. Perovskite-Type Oxides. I. Structural, Magnetic, and Morphological Properties of LaMn 1- xCu xO 3 and LaCo 1- xCu xO 3 Solid Solutions with Large Surface Area

    NASA Astrophysics Data System (ADS)

    Porta, Piero; De Rossi, Sergio; Faticanti, Marco; Minelli, Giuliano; Pettiti, Ida; Lisi, Luciana; Turco, Maria

    1999-09-01

    Perovskite-type compounds of general formula LaMn1-xCuxO3 and LaCo1-xCuxO3 (x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0) were prepared by calcining the citrate gel precursors at 823, 923, and 1073 K. The decomposition of the precursors was followed by thermal analysis and the oxides were investigated by means of elemental analysis (atomic absorption and redox titration), X-ray powder diffraction, BET surface area, X-ray absorption (EXAFS and XANES), electron microscopy (SEM and TEM), and magnetic susceptibility. LaMn1-xCuxO3 samples are perovskite-like single phases up to x=0.6. At x=0.8 CuO and La2CuO4 phases are present in addition to perovskite. For x=1.0 the material is formed by CuO and La2CuO4. Mn(IV) was found by redox titration in all Mn-based perovskite samples, its fraction increasing with the increase in copper content. EXAFS and XANES analyses confirmed the presence of Mn(IV). Cation vacancies in equal amounts in the 12-coordinated A and octahedral B sites are suggested in the samples with x=0.0 and x=0.2, while for x=0.6 anionic vacancies are present. Materials with sufficiently high surface area (22-36 m2 g-1 for samples fired at 923 K and 14-22 m2 g-1 for those fired at 1073 K) were obtained. Crystallite sizes in the ranges 390-500 and 590-940 Å for samples calcined at 923 and 1073 K, respectively, were determined from the FWHM of the (102) X-ray diffraction peak. TEM patterns of LaMnO3 showed almost regular hexagonal prismatic crystals with sizes of the same order of magnitude (800 Å) of those drawn from X-ray diffraction, while no evidence of defect clustering was drawn out from TEM and electron diffraction images. For the sample with x=0.6, TEM and electron diffraction patterns revealed perturbation of the structure. Magnetic susceptibility studies show a ferromagnetic behavior that decreases with increase in x. LaCo1-xCuxO3 samples are perovskite-like single phases up to x=0.2. For x=0.4 a small amount of La2CuO4, in addition to perovskite, is detected. For

  9. Electrodeposition of organic-inorganic tri-halide perovskites solar cell

    NASA Astrophysics Data System (ADS)

    Charles, U. A.; Ibrahim, M. A.; Teridi, M. A. M.

    2018-02-01

    Perovskite (CH3NH3PbI3) semiconductor materials are promising high-performance light energy absorber for solar cell application. However, the power conversion efficiency of perovskite solar cell is severely affected by the surface quality of the deposited thin film. Spin coating is a low-cost and widely used deposition technique for perovskite solar cell. Notably, film deposited by spin coating evolves surface hydroxide and defeats from uncontrolled precipitation and inter-diffusion reaction. Alternatively, vapor deposition (VD) method produces uniform thin film but requires precise control of complex thermodynamic parameters which makes the technique unsuitable for large scale production. Most deposition techniques for perovskite require tedious surface optimization to improve the surface quality of deposits. Optimization of perovskite surface is necessary to significantly improve device structure and electrical output. In this review, electrodeposition of perovskite solar cell is demonstrated as a scalable and reproducible technique to fabricate uniform and smooth thin film surface that circumvents the need for high vacuum environment. Electrodeposition is achieved at low temperatures, supports precise control and optimization of deposits for efficient charge transfer.

  10. Electronic and optical properties of MAPbX3 perovskites (X = I, Br, Cl): a unified DFT and GW theoretical analysis.

    PubMed

    Mosconi, Edoardo; Umari, Paolo; De Angelis, Filippo

    2016-10-05

    Materials engineering is a key for the enhancement of photovoltaics technology. This is particularly true for the novel class of perovskite solar cells. Accurate theoretical modelling can help establish general trends of behavior when addressing structural changes. Here, we consider the effects due to halide substitution in organohalide CH 3 NH 3 PbX 3 perovskites exploring the halide series with X = Cl, Br, I. For this task, we use accurate DFT and GW methods including spin-orbit coupling. We find the expected band gap increase when moving from X = I to Cl, in line with the experimental data. Most notably, the calculated absorption coefficients for I, Br and Cl are nicely reproducing the behavior reported experimentally. A common feature of all the simulated band structures is a significant Rashba effect. This is similar for MAPbI 3 and MAPbBr 3 while MAPbCl 3 shows in general a reduced Rashba interaction coefficient. Finally, a monotonic increase of the exciton reduced masses is calculated when moving from I to Br to Cl, in line with the stronger excitonic character of the lighter perovskite halides.

  11. White-Light Emission and Structural Distortion in New Corrugated Two-Dimensional Lead Bromide Perovskites.

    PubMed

    Mao, Lingling; Wu, Yilei; Stoumpos, Constantinos C; Wasielewski, Michael R; Kanatzidis, Mercouri G

    2017-03-29

    Hybrid inorganic-organic perovskites are developing rapidly as high performance semiconductors. Recently, two-dimensional (2D) perovskites were found to have white-light, broadband emission in the visible range that was attributed mainly to the role of self-trapped excitons (STEs). Here, we describe three new 2D lead bromide perovskites incorporating a series of bifunctional ammonium dications as templates which also emit white light: (1) α-(DMEN)PbBr 4 (DMEN = 2-(dimethylamino)ethylamine), which adopts a unique corrugated layered structure in space group Pbca with unit cell a = 18.901(4) Å, b = 11.782(2) Å, and c = 23.680(5) Å; (2) (DMAPA)PbBr 4 (DMAPA = 3-(dimethylamino)-1-propylamine), which crystallizes in P2 1 /c with a = 10.717(2) Å, b = 11.735(2) Å, c = 12.127(2) Å, and β = 111.53(3)°; and (3) (DMABA)PbBr 4 (DMABA = 4-dimethylaminobutylamine), which adopts Aba2 with a = 41.685(8) Å, b = 23.962(5) Å, and c = 12.000(2) Å. Photoluminescence (PL) studies show a correlation between the distortion of the "PbBr 6 " octahedron in the 2D layer and the broadening of PL emission, with the most distorted structure having the broadest emission (183 nm full width at half-maximum) and longest lifetime (τ avg = 1.39 ns). The most distorted member α-(DMEN)PbBr 4 exhibits white-light emission with a color rendering index (CRI) of 73 which is similar to a fluorescent light source and correlated color temperature (CCT) of 7863 K, producing "cold" white light.

  12. ABO blood groups and rheumatic diseases.

    PubMed

    Çildağ, Songül; Kara, Yasemin; Şentürk, Taşkın

    2017-12-01

    Various genetic and environmental risk factors have been shown to be associated with the incidence of rheumatic diseases. However, the pathogenesis of rheumatic diseases poorly understood. Several studies have shown associations of ABO blood groups with various diseases. Our study aimed to determine whether there is an association between the types of rheumatic diseases and ABO and Rh blood groups. The study included the patients, followed up at the Immunology-Rheumatology clinic between January 2016 and December 2016 for diagnosis of rheumatic disease, who had an ABO Rh blood data. Age, gender, type of rheumatic disease, ABO Rh blood groups were recorded. When 823 patients were assessed for blood types, 42.5% patients had A type, 33.2% had O type, 15.4% had B type, and 8.9% had AB type. There was significant difference in the distribution of blood types in rheumatic diseases. While SpA, vasculitis, UCTD, Behçet's and RA were more common in the patients with A blood type; FMF, SLE, SSc and SjS were more common in the patients with O blood type. In addition, the blood type where all the diseases are observed the least commonly was AB. There was significant difference in the distribution of Rh factor in rheumatic diseases. 92.2% patients were Rh positive and 7.8% patients were Rh negative. In our study, we thought that the higher incidence of different rheumatic diseases in different blood types was associated with different genetic predisposition.

  13. Role of organic cations on hybrid halide perovskite CH3NH3PbI3 surfaces

    NASA Astrophysics Data System (ADS)

    Teng, Qiang; Shi, Ting-Ting; Tian, Ren-Yu; Yang, Xiao-Bao; Zhao, Yu-Jun

    2018-02-01

    Organic-inorganic hybrid halide perovskite CH3NH3PbI3 (MAPbI3) has received rapid progress in power conversion efficiency as promising photovoltaic materials, yet the surface structures and the role of MA cations are not well understood. In this work, we investigated the structural stability and electronic properties of (001) surface of cubic, (001) and (110) surfaces of tetragonal and orthorhombic phases of MAPbI3 with considering the orientation of MA cations, by density functional theory calculations. We demonstrate that the orientation of MA cations has profound consequences on the structural stability and the electronic properties of the surfaces, in contrast to the bulk phases. Compared with the MA-I terminated surfaces, the Pb-I2 terminated ones generally have smaller band gaps and the advantage to enable the photo-excited holes to transfer to the hole-transport materials in both tetragonal and orthorhombic phases. Overall, we suggest that the films with Pb-I2 terminated surfaces would prevail in high performance solar energy absorbers.

  14. ABO blood group antibody levels in infants exposed to mechanical circulatory support.

    PubMed

    Guynes, Anthony; Delaney, Meghan; McMullan, David M; Townsend-McCall, Dee; Kemna, Mariska; Boucek, Robert; Law, Yuk M

    2014-01-01

    ABO sensitization is a barrier to ABO-incompatible heart transplantation in infants. We investigate the development of ABO antibodies in infants with and without mechanical circulatory support (MCS) during their waiting period. Although the proportion of patients with antibodies was similar between the groups, the median age at antibody detection was only 9 days (6-198) for MCS vs. 223 days (28-367) for non-MCS patients (P = 0.028), suggesting MCS is associated with earlier ABO antibody detection.

  15. Design, Structure, and Optical Properties of Organic-Inorganic Perovskites Containing an Oligothiophene Chromophore.

    PubMed

    Mitzi, David B.; Chondroudis, Konstantinos; Kagan, Cherie R.

    1999-12-27

    A quaterthiophene derivative, 5,5' "-bis(aminoethyl)-2,2':5',2' ':5' ',2' "-quaterthiophene (AEQT), has been selected for incorporation within the layered organic-inorganic perovskite structure. In addition to having an appropriate molecular shape and two tethering aminoethyl groups to bond to the inorganic framework, AEQT is also a dye and can influence the optical properties of lead(II) halide-based perovskites. Crystals of C(20)H(22)S(4)N(2)PbBr(4) were grown from a slowly cooled aqueous solution containing lead(II) bromide and quaterthiophene derivative (AEQT.2HBr) salts. The new layered perovskite adopts a monoclinic (C2/c) subcell with the lattice parameters a = 39.741(2) Å, b = 5.8420(3) Å, c = 11.5734(6) Å, beta = 92.360(1) degrees, and Z = 4. Broad superstructure peaks are observed in the X-ray diffraction data, indicative of a poorly ordered, doubled supercell along both the a and b axes. The quaterthiophene segment of AEQT(2+) is nearly planar, with a syn-anti-syn relationship between adjacent thiophene rings. Each quaterthiophene chromophore is ordered between nearest-neighbor lead(II) bromide sheets in a herringbone arrangement with respect to neighboring quaterthiophenes. Room temperature optical absorption spectra for thermally ablated films of the perovskites (AEQT)PbX(4) (X = Cl, Br, I) exhibit an exciton peak arising from the lead(II) halide sheets, along with absorption from the quaterthiophene moiety. No evidence of the inorganic sheet excitonic transition is observed in the photoluminescence spectra for any of the chromophore-containing perovskites. However, strong quaterthiophene photoluminescence is observed for X = Cl, with an emission peak at approximately lambda(max) = 532 nm. Similar photoluminescence is observed for the X = Br and I materials, but with substantial quenching, as the inorganic layer band gap decreases relative to the chromophore HOMO-LUMO gap.

  16. A two-layer structured PbI2 thin film for efficient planar perovskite solar cells.

    PubMed

    Ying, Chao; Shi, Chengwu; Wu, Ni; Zhang, Jincheng; Wang, Mao

    2015-07-28

    In this paper, a two-layer structured PbI2 thin film was constructed by the spin-coating procedure using a 0.80 M PbI2 solution in DMF and subsequent close-spaced vacuum thermal evaporation using PbI2 powder as a source. The bottom PbI2 thin film was compact with a sheet-like appearance, parallel to the FTO substrate, and can be easily converted to a compact perovskite thin film to suppress the charge recombination of the electrons of the TiO2 conduction band and the holes of the spiro-OMeTAD valence band. The top PbI2 thin film was porous with nano-sheet arrays, perpendicular to the FTO substrate, and can be easily converted to a porous perovskite thin film to improve the hole migration from the perovskite to spiro-OMeTAD and the charge separation at the perovskite/spiro-OMeTAD interface. The planar perovskite solar cells based on the two-layer structured PbI2 thin film exhibited a photoelectric conversion efficiency of 11.64%, along with an open-circuit voltage of 0.90 V, a short-circuit photocurrent density of 19.29 mA cm(-2) and a fill factor of 0.67.

  17. One-Year stable perovskite solar cells by 2D/3D interface engineering

    NASA Astrophysics Data System (ADS)

    Grancini, G.; Roldán-Carmona, C.; Zimmermann, I.; Mosconi, E.; Lee, X.; Martineau, D.; Narbey, S.; Oswald, F.; de Angelis, F.; Graetzel, M.; Nazeeruddin, Mohammad Khaja

    2017-06-01

    Despite the impressive photovoltaic performances with power conversion efficiency beyond 22%, perovskite solar cells are poorly stable under operation, failing by far the market requirements. Various technological approaches have been proposed to overcome the instability problem, which, while delivering appreciable incremental improvements, are still far from a market-proof solution. Here we show one-year stable perovskite devices by engineering an ultra-stable 2D/3D (HOOC(CH2)4NH3)2PbI4/CH3NH3PbI3 perovskite junction. The 2D/3D forms an exceptional gradually-organized multi-dimensional interface that yields up to 12.9% efficiency in a carbon-based architecture, and 14.6% in standard mesoporous solar cells. To demonstrate the up-scale potential of our technology, we fabricate 10 × 10 cm2 solar modules by a fully printable industrial-scale process, delivering 11.2% efficiency stable for >10,000 h with zero loss in performances measured under controlled standard conditions. This innovative stable and low-cost architecture will enable the timely commercialization of perovskite solar cells.

  18. One-Year stable perovskite solar cells by 2D/3D interface engineering

    PubMed Central

    Grancini, G.; Roldán-Carmona, C.; Zimmermann, I.; Mosconi, E.; Lee, X.; Martineau, D.; Narbey, S.; Oswald, F.; De Angelis, F.; Graetzel, M.; Nazeeruddin, Mohammad Khaja

    2017-01-01

    Despite the impressive photovoltaic performances with power conversion efficiency beyond 22%, perovskite solar cells are poorly stable under operation, failing by far the market requirements. Various technological approaches have been proposed to overcome the instability problem, which, while delivering appreciable incremental improvements, are still far from a market-proof solution. Here we show one-year stable perovskite devices by engineering an ultra-stable 2D/3D (HOOC(CH2)4NH3)2PbI4/CH3NH3PbI3 perovskite junction. The 2D/3D forms an exceptional gradually-organized multi-dimensional interface that yields up to 12.9% efficiency in a carbon-based architecture, and 14.6% in standard mesoporous solar cells. To demonstrate the up-scale potential of our technology, we fabricate 10 × 10 cm2 solar modules by a fully printable industrial-scale process, delivering 11.2% efficiency stable for >10,000 h with zero loss in performances measured under controlled standard conditions. This innovative stable and low-cost architecture will enable the timely commercialization of perovskite solar cells. PMID:28569749

  19. One-Year stable perovskite solar cells by 2D/3D interface engineering.

    PubMed

    Grancini, G; Roldán-Carmona, C; Zimmermann, I; Mosconi, E; Lee, X; Martineau, D; Narbey, S; Oswald, F; De Angelis, F; Graetzel, M; Nazeeruddin, Mohammad Khaja

    2017-06-01

    Despite the impressive photovoltaic performances with power conversion efficiency beyond 22%, perovskite solar cells are poorly stable under operation, failing by far the market requirements. Various technological approaches have been proposed to overcome the instability problem, which, while delivering appreciable incremental improvements, are still far from a market-proof solution. Here we show one-year stable perovskite devices by engineering an ultra-stable 2D/3D (HOOC(CH 2 ) 4 NH 3 ) 2 PbI 4 /CH 3 NH 3 PbI 3 perovskite junction. The 2D/3D forms an exceptional gradually-organized multi-dimensional interface that yields up to 12.9% efficiency in a carbon-based architecture, and 14.6% in standard mesoporous solar cells. To demonstrate the up-scale potential of our technology, we fabricate 10 × 10 cm 2 solar modules by a fully printable industrial-scale process, delivering 11.2% efficiency stable for >10,000 h with zero loss in performances measured under controlled standard conditions. This innovative stable and low-cost architecture will enable the timely commercialization of perovskite solar cells.

  20. Probing magnetic transitions in (Mg,Fe)GeO3-perovskite with Mössbauer Spectroscopy

    NASA Astrophysics Data System (ADS)

    Wicks, J. K.; Tracy, S. J.; Stan, C. V.; Bi, W.; Alp, E. E.; Xiao, Y.; Chow, P.; Duffy, T. S.

    2016-12-01

    The effect of iron on the properties of major lower mantle minerals must be understood for proper interpretation of seismic and geodynamic data. The role of Fe in bridgmanite in the deep earth is complicated as Fe can occupy two different crystallographic sites (8-fold site or octahedral site) and adopt different valence states (2+,3+) and electronic configurations (high or low spin). Previous experimental and theoretical work on this material has reported a pressure-induced low- to high-QS (quadrupole splitting) transition at 30 GPa, explained by a small lateral displacement of the Fe2+ ion (e.g. Jackson et al., 2005, Hsu et al., 2010). Further insight into the nature of this transition can be obtained through the study of germanates which are well-known to be effective analogues for silicates. The perovskite (Pv) to post-perovskite (pPv) transition is reduced by 50 GPa in MgGeO3 compared with MgSiO3. Despite this, a recent theoretical study predicts that in the Ge analogue the low- to high-QS transition should be 20 GPa higher in the germanate due to its larger unit cell (Shukla et al., 2015). 57Fe-enriched (Mg0.8Fe0.2)GeO3 perovskite was synthesized at 40 GPa with laser heating at Sector 13-ID-D, as confirmed with X-ray diffraction. Conventional and synchrotron Mössbauer spectroscopy was conducted at Sector 3 and Sector 16 of the Advanced Photon source, Argonne National Laboratory over the stability field of germanate perovskite: 39-61 GPa. This study took advantage of the new capability of synchrotron Mössbauer spectroscopy conducted during the APS operations in hybrid mode, which expanded the experimental time window from 150 to 800 ns. Preliminary analysis indicates that iron is predominately Fe2+ with some Fe3+ contribution at low pressure. With increasing pressure, we find the appearance of a third high-QS site, consistent with similar observations in the silicate. Our results provide new insights into high-pressure behavior of Fe in perovskite-structured

  1. CsPbBr3 perovskites: Theoretical and experimental investigation on water-assisted transition from nanowire formation to degradation

    NASA Astrophysics Data System (ADS)

    Akbali, B.; Topcu, G.; Guner, T.; Ozcan, M.; Demir, M. M.; Sahin, H.

    2018-03-01

    Recent advances in colloidal synthesis methods have led to an increased research focus on halide perovskites. Due to the highly ionic crystal structure of perovskite materials, a stability issue pops up, especially against polar solvents such as water. In this study, we investigate water-driven structural evolution of CsPbBr3 by performing experiments and state-of-the-art first-principles calculations. It is seen that while an optical image shows the gradual degradation of the yellowish CsPbBr3 structure under daylight, UV illumination reveals that the degradation of crystals takes place in two steps: transition from a blue-emitting to green-emitting structure and and then a transition from a green-emitting phase to complete degradation. We found that as-synthesized CsPbBr3 nanowires (NWs) emit blue light under a 254 nm UV source. Before the degradation, first, CsPbBr3 NWs undergo a water-driven structural transition to form large bundles. It is also seen that formation of such bundles provides longer-term environmental stability. In addition theoretical calculations revealed the strength of the interaction of water molecules with ligands and surfaces of CsPbBr3 and provide an atomistic-level explanation to a transition from ligand-covered NWs to bundle formation. Further interaction of green-light-emitting bundles with water causes complete degradation of CsPbBr3 and the photoluminescence signal is entirely quenched. Moreover, Raman and x-ray-diffraction measurements revealed that completely degraded regions are decomposed to PbBr2 and CsBr precursors. We believe that the findings of this study may provide further insight into the degradation mechanism of CsPbBr3 perovskite by water.

  2. Specific issues in living donor kidney transplantation: ABO - incompatibility.

    PubMed

    Thaiss, Friedrich

    2009-12-29

    Pre-emptive living kidney transplantation is the best choice of therapy to treat patients with advanced renal insufficiency. Unfortunately in up to one third of all cases kidney donation was refused due to blood group incompatibility. Limitations in donor availability for kidney transplantation therefore require that ABO-incompatible transplantation is safely established. This has changed when a new protocol was introduced in Stockholm, Sweden, in 2001. Almost 400 ABO-incompatible transplantations have since been performed in more than 20 centers with this protocol in Europe. ABO-incompatible living kidney transplantation can now be offered to our patients with advanced kidney disease as a safe procedure. To get more insight into the role ABO-incompatible organ transplantation might play in the near future transplantation centers currently involved in these processes should share their data to answer the unresolved issues we are concerned. Copyright © 2009 Elsevier Ireland Ltd. All rights reserved.

  3. Cation-induced band-gap tuning in organohalide perovskites: interplay of spin-orbit coupling and octahedra tilting.

    PubMed

    Amat, Anna; Mosconi, Edoardo; Ronca, Enrico; Quarti, Claudio; Umari, Paolo; Nazeeruddin, Md K; Grätzel, Michael; De Angelis, Filippo

    2014-06-11

    Organohalide lead perovskites have revolutionized the scenario of emerging photovoltaic technologies. The prototype MAPbI3 perovskite (MA = CH3NH3(+)) has dominated the field, despite only harvesting photons above 750 nm (∼1.6 eV). Intensive research efforts are being devoted to find new perovskites with red-shifted absorption onset, along with good charge transport properties. Recently, a new perovskite based on the formamidinium cation ((NH2)2CH(+) = FA) has shown potentially superior properties in terms of band gap and charge transport compared to MAPbI3. The results have been interpreted in terms of the cation size, with the larger FA cation expectedly delivering reduced band-gaps in Pb-based perovskites. To provide a full understanding of the interplay among size, structure, and organic/inorganic interactions in determining the properties of APbI3 perovskites, in view of designing new materials and fully exploiting them for solar cells applications, we report a fully first-principles investigation on APbI3 perovskites with A = Cs(+), MA, and FA. Our results evidence that the tetragonal-to-quasi cubic structural evolution observed when moving from MA to FA is due to the interplay of size effects and enhanced hydrogen bonding between the FA cations and the inorganic matrix altering the covalent/ionic character of Pb-I bonds. Most notably, the observed cation-induced structural variability promotes markedly different electronic and optical properties in the MAPbI3 and FAPbI3 perovskites, mediated by the different spin-orbit coupling, leading to improved charge transport and red-shifted absorption in FAPbI3 and in general in pseudocubic structures. Our theoretical model constitutes the basis for the rationale design of new and more efficient organohalide perovskites for solar cells applications.

  4. Large anisotropic thermoelectricity in perovskite related layered structure: SrnNbnO3n+2 (n=4,5)

    NASA Astrophysics Data System (ADS)

    Sakai, Akihiro; Kanno, Tsutomu; Takahashi, Kouhei; Yamada, Yuka; Adachi, Hideaki

    2010-11-01

    We measured the thermal and charge transport properties of perovskite-related layered structures. Strontium-Niobates, which were expressed as SrnNbnO3n+2 (n =4: Sr1.8La0.2Nb2O7, n =5: Sr5Nb5O17), to explore their thermoelectricities and thermal anisotropies. The behaviors of the thermoelectric parameters (thermal conductivity, Seebeck coefficient, resistivity) were strongly anisotropic in all crystallographic axes (a, b, and c) and large anisotropy exists even in the in-plane direction of the layered structure. Especially, along the a-axis in which corner-sharing NbO6 octahedra aligned straightly, contrastive properties were observed between Sr1.8La0.2Nb2O7 and Sr5Nb5O17. For Sr1.8La0.2Nb2O7, a thermally activated charge conduction is pronounced in the temperature dependence of Seebeck coefficient and resistivity, on the other hand, it was a metallic nature for Sr5Nb5O17. In both compounds, ZT results in anisotropic due to the anisotropic properties of thermoelectric parameters, the best performance is commonly observed in the a-axis. The respective ZT values at room temperature are 3.5×10-2 and 3.6×10-3.

  5. Preparation and characterization of a possible topological insulator BiYO3: experiment versus theory.

    PubMed

    Zhang, Y; Deng, S; Pan, M; Lei, M; Kan, X; Ding, Y; Zhao, Y; Köhler, J

    2016-03-21

    The Bi-Y-O system has been investigated by X-ray powder diffraction, electron diffraction, UV-vis and IR experiments. A metastable cubic high temperature phase of BiYO3 with fluorite-type structure has been structurally characterized for the first time and shows a large band gap of ∼ 5.9 eV. A unified description for the numerous structural variants discovered in the Bi-Y-O system is established within the symmetry breaking approach. This rich structural phenomenon makes the Bi-Y-O system a promising candidate in the search for new topological insulators for applications. On this basis, a long standing controversy on the phase diagram of the Bi-Y-O system has been solved. Our DFT calculations predict a high pressure phase for BiYO3 with perovskite (ABO3) structure and ordering of Bi and Y on the A and B sites, respectively. However, our analysis of the nature of the low energy electronic structure shows that this phase is not a suitable candidate for a topological insulator.

  6. Alkali Metal Doping for Improved CH3NH3PbI3 Perovskite Solar Cells.

    PubMed

    Zhao, Wangen; Yao, Zhun; Yu, Fengyang; Yang, Dong; Liu, Shengzhong Frank

    2018-02-01

    Organic-inorganic hybrid halide perovskites are proven to be a promising semiconductor material as the absorber layer of solar cells. However, the perovskite films always suffer from nonuniform coverage or high trap state density due to the polycrystalline characteristics, which degrade the photoelectric properties of thin films. Herein, the alkali metal ions which are stable against oxidation and reduction are used in the perovskite precursor solution to induce the process of crystallization and nucleation, then affect the properties of the perovskite film. It is found that the addition of the alkali metal ions clearly improves the quality of perovskite film: enlarges the grain sizes, reduces the defect state density, passivates the grain boundaries, increases the built-in potential ( V bi ), resulting to the enhancement in the power conversion efficiency of perovskite thin film solar cell.

  7. Trapping charges at grain boundaries and degradation of CH3NH3Pb(I1-x Br x )3 perovskite solar cells.

    PubMed

    Nguyen, Bich Phuong; Kim, Gee Yeong; Jo, William; Kim, Byeong Jo; Jung, Hyun Suk

    2017-08-04

    The electrical properties of CH 3 NH 3 Pb(I 1-x Br x ) 3 (x = 0.13) perovskite materials were investigated under ambient conditions. The local work function and the local current were measured using Kelvin probe force microscopy and conductive atomic force microscopy, respectively. The degradation of the perovskite layers depends on their grain size. As the material degrades, an additional peak in the surface potential appears simultaneously with a sudden increase and subsequent relaxation of the local current. The potential bending at the grain boundaries and the intragrains is the most likely reason for the change of the local current surface of the perovskite layers. The improved understanding of the degradation mechanism garnered from this study helps pave the way toward an improved photo-conversion efficiency in perovskite solar cells.

  8. Trapping charges at grain boundaries and degradation of CH3NH3Pb(I1-x Br x )3 perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Phuong Nguyen, Bich; Kim, Gee Yeong; Jo, William; Kim, Byeong Jo; Jung, Hyun Suk

    2017-08-01

    The electrical properties of CH3NH3Pb(I1-x Br x )3 (x = 0.13) perovskite materials were investigated under ambient conditions. The local work function and the local current were measured using Kelvin probe force microscopy and conductive atomic force microscopy, respectively. The degradation of the perovskite layers depends on their grain size. As the material degrades, an additional peak in the surface potential appears simultaneously with a sudden increase and subsequent relaxation of the local current. The potential bending at the grain boundaries and the intragrains is the most likely reason for the change of the local current surface of the perovskite layers. The improved understanding of the degradation mechanism garnered from this study helps pave the way toward an improved photo-conversion efficiency in perovskite solar cells.

  9. Revealing the Self-Degradation Mechanisms in Methylammonium Lead Iodide Perovskites in Dark and Vacuum.

    PubMed

    Gunasekaran, Rajendra Kumar; Chinnadurai, Deviprasath; Selvaraj, Aravindha Raja; Rajendiran, Rajmohan; Senthil, Karuppanan; Prabakar, Kandasamy

    2018-06-19

    Organic-inorganic lead halide perovskite phases segregate (and their structures degrade) under illumination, exhibiting a poor stability with hysteresis and producing halide accumulation at the surface.In this work, we observed structural and interfacial dissociation in methylammonium lead iodide (CH 3 NH 3 PbI 3 ) perovskites even under dark and vacuum conditions. Here, we investigate the origin and consequences of self-degradation in CH 3 NH 3 PbI 3 perovskites stored in the dark under vacuum. Diffraction and photoelectron spectroscopic studies reveal the structural dissociation of perovskites into PbI 2 , which further dissociates into metallic lead (Pb 0 ) and I 2 - ions, collectively degrading the perovskite stability. Using TOF-SIMS analysis, AuI 2 - formation was directly observed, and it was found that an interplay between CH 3 NH 3 + , I 3 - , and mobile I - ions continuously regenerates more I 2 - ions, which diffuse to the surface even in the absence of light. Besides, halide diffusion causes a concentration gradient between Pb 0 and I 2 - and creates other ionic traps (PbI 2 - , PbI - ) that segregate as clusters at the perovskite/gold interface. A shift of the onset of the absorption band edge towards shorter wavelengths was also observed by absorption spectroscopy, indicating the formation of defect species upon aging in the dark under vacuum. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. A New Lead Iodide Perovskite based on Large Organic Cation for Solar Cell Application.

    PubMed

    Ma, Chunqing; Shen, Dong; Lo, Ming Fai; Lee, Chun-Sing

    2018-06-06

    Methylammonium (CH3NH3+) and formamidinium ((NH2)2CH+) based lead iodide perovskites are currently the two commonly used organic-inorganic lead iodide perovskites for solar cell application. Till now, there is still no alternative organic cations, which can produce perovskites with bandgaps spanning the visible spectrum (i.e. < 1.7 eV) for solar cell application. Here, a new perovskite using large propane-1,3-diammonium cation (n-Pr(NH3)22+) with a chemical structure of (n-Pr(NH3)2)0.5PbI3 is demonstrated. X-ray diffraction (XRD) result shows that the new perovskite exhibits a three-dimensional (3D), tetragonal phase. The bandgap of the new perovskite is ~ 1.6 eV, which is desirable for photovoltaic application. A (n-Pr(NH3)2)0.5PbI3 perovskite solar cell (PSC) yields a power conversion efficiency (PCE) of 5.1%. More importantly, this new perovskite is composed of larger hydrophobic cation that provides a better moisture resistance compared to CH3NH3PbI3 perovskite. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Enhanced photovoltaic properties of perovskite solar cells by TiO2 homogeneous hybrid structure

    PubMed Central

    Su, Pengyu; Yao, Huizhen; Liu, Li; Ding, Dong; Feng, Fei; Feng, Shuang; Xue, Yebin; Liu, Xizhe; Yang, Haibin

    2017-01-01

    In this paper, we fabricated a TiO2 homogeneous hybrid structure for application in perovskite solar cells (PSCs) under ambient conditions. Under the standard air mass 1.5 global (AM 1.5G) illumination, PSCs based on homogeneous hybrid structure present a maximum power conversion efficiency of 5.39% which is higher than that of pure TiO2 nanosheets. The enhanced properties can be explained by the better contact of TiO2 nanosheets/nanoparticles with CH3NH3PbI3 and fewer pinholes in electron transport materials. The advent of such unique structure opens up new avenues for the future development of high-efficiency photovoltaic cells. PMID:29134092

  12. Properties of Ferroelectric Perovskite Structures under Non-equilibrium Conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Qingteng

    Ferroelectric materials have received lots of attention thanks to their intriguing properties such as the piezoelectric and pyroelectric effects, as well as the large dielectric constants and the spontaneous polarization which can potentially be used for information storage. In particular, perovskite crystal has a very simple unit cell structure yet a very rich phase transition diagram, which makes it one of the most intensively studied ferroelectric materials. In this dissertation, we use effective Hamiltonian, a first-principles-based computational technique to study the finite-temperature properties of ferroelectric perovskites. We studied temperature-graded (BaxSr 1-x)TiO3 (BST) bulk alloys as well as the dynamics of nanodomain walls (nanowalls) in Pb(Zr xTi1-x)O 3 (PZT) ultra-thin films under the driving force of an AC field. Our computations suggest that, for the temperature-graded BST, the polarization responds to the temperature gradient (TG), with the "up" and "down" offset observed in polarization components along the direction of TG, in agreement with the findings from experiments. For the nanowalls in PZT, the dynamics can be described by the damped-harmonic-oscillator model, and we observed a size-driven transition from resonance to relaxational dynamics at a critical thickness of 7.2 nm. The transition originates from the change in the effective mass of a nanowall as a film thickness increases. Some of the findings may find potential applications in various devices, such as thermal sensors, energy converters, or novel memory units.

  13. Structure and Electrical-Transport Relations in Ba(Zr,Pr)O3Perovskites.

    PubMed

    Antunes, Isabel; Amador, Ulises; Alves, Adriana; Correia, Maria Rosário; Ritter, Clemens; Frade, Jorge Ribeiro; Pérez-Coll, Domingo; Mather, Glenn C; Fagg, Duncan Paul

    2017-08-07

    Members of the perovskite solid solution BaZr 1-x Pr x O 3-δ (0.2 ≤ x ≤ 0.8) with potential high-temperature electrochemical applications were synthesized via mechanical activation and high-temperature annealing at 1250 °C. Structural properties were examined by Rietveld analysis of neutron powder diffraction and Raman spectroscopy at room temperature, indicating rhombohedral symmetry (space group R3̅c) for members x = 0.2 and 0.4 and orthorhombic symmetry (Imma) for x = 0.6 and 0.8. The sequence of phase transitions for the complete solid solution from BaZrO 3 to BaPrO 3 is Pm3̅m → R3̅c → Imma → Pnma. The structural data indicate that Pr principally exists as Pr 4+ on the B site and that oxygen content increases with higher Pr content. Electrical-conductivity measurements in the temperature range of 250-900 °C in dry and humidified (pH 2 O ≈ 0.03 atm) N 2 and O 2 atmospheres revealed an increase of total conductivity by over 2 orders of magnitude in dry conditions from x = 0.2 to x = 0.8 (σ ≈ 0.08 S cm -1 at 920 °C in dry O 2 for x = 0.8). The conductivity for Pr contents x > 0.2 is attributable to positively charged electronic carriers, whereas for x = 0.2 transport in dry conditions is n-type. The change in conduction mechanism with composition is proposed to arise from the compensation regime for minor amounts of BaO loss changing from predominantly partitioning of Pr on the A site to vacancy formation with increasing Pr content. Conductivity is lower in wet conditions for x > 0.2 indicating that the positive defects are, to a large extent, charge compensated by less mobile protonic species. In contrast, the transport mechanism of the Zr-rich composition (x = 0.2), with much lower electronic conductivity, is essentially independent of moisture content.

  14. Photocatalyst of Perovskite CaTiO3 Nanopowder Synthesized from CaO derived from Snail Shell in Comparison with The Use of CaO and CaCO3

    NASA Astrophysics Data System (ADS)

    Fatimah, I.; Rahmadianti, Y.; Pudiasari, R. A.

    2018-04-01

    Calcium titanate belongs to the important group of compounds with a perovskite structure having high dielectric loss for various applications including photocatalysis mechanism. Refer to the principles of green chemistry, in this work preparation of CaTiO3 was conducted by using CaO derived from snail shell. Aim of this research are to study the physicochemical character of perovskite derived from snail shell and its comparison with CaO and CaCO3 as Ca sources. Material preparation was performed by solid reaction of Ca sources with TiO2 under comparison with CaO and CaCO3 precursors. Mixture of Ca sources with TiO2 in certain proportion were ground and calcined at the temperature of 200 °C for 2 hs. Materials were characterized by using X-ray diffractometer (XRD), Fourier Transform-Infra Red (FTIR) and the photocatalytic activity was tested by using methylene blue photooxidation. Perovskite synthesized using CaO derived from snail shell exhibits the similar XRD pattern with that were prepared by using CaO and CaCO3. From the photooxidation activity test, it is proven that CaTiO3 shows similar photocatalytic activity correspond to that were prepared by CaO and CaCO3. Utilazation of shell as agricultural waste of the synthesis of CaTiO3 perovskite is the novelty of this work. Furthermore, the study on material structure and photoactivity is the main focuses for the application in industry and environment.

  15. Efficient Bulk Heterojunction CH3NH3PbI3-TiO2 Solar Cells with TiO2 Nanoparticles at Grain Boundaries of Perovskite by Multi-Cycle-Coating Strategy.

    PubMed

    Shao, Jun; Yang, Songwang; Liu, Yan

    2017-05-17

    A novel bulk heterojunction (BHJ) perovskite solar cell (PSC), where the perovskite grains act as donor and the TiO 2 nanoparticles act as acceptor, is reported. This efficient BHJ PSC was simply solution processed from a mixed precursor of CH 3 NH 3 PbI 3 (MAPbI 3 ) and TiO 2 nanoparticles. With dissolution and recrystallization by multi-cycle-coating, a unique composite structure ranging from a MAPbI 3 -TiO 2 -dominated layer on the substrate side to a pure perovskite layer on the top side is formed, which is beneficial for the blocking of possible contact between TiO 2 and the hole transport material at the interface. Scanning electron microscopy clearly shows that TiO 2 nanoparticles accumulate along the grain boundaries (GBs) of perovskite. The TiO 2 nanoparticles at the GBs quickly extract and reserve photogenerated electrons before they transport into the perovskite phase, as described in the multitrapping model, retarding the electron-hole recombination and reducing the energy loss, resulting in increased V OC and fill factor. Moreover, the pinning effect of the TiO 2 nanoparticles at the GBs from the strong bindings between TiO 2 and MAPbI 3 suppresses massive ion migration along the GBs, leading to improved operational stability and diminished hysteresis. Photoluminescence (PL) quenching and PL decay confirm the efficient exciton dissociation on the heterointerface. Electrochemical impedance spectroscopy and open-circuit photovoltage decay measurements show the reduced recombination loss and improved carrier lifetime of the BHJ PSCs. This novel strategy of device design effectively combines the benefits of both planar and mesostructured architectures whilst avoiding their shortcomings, eventually leading to a high PCE of 17.42% under 1 Sun illumination. The newly proposed approach also provides a new way to fabricate a TiO 2 -containing perovskite active layer at a low temperature.

  16. Two-Dimensional CH3NH3PbI3 Perovskite Nanosheets for Ultrafast Pulsed Fiber Lasers.

    PubMed

    Li, Pengfei; Chen, Yao; Yang, Tieshan; Wang, Ziyu; Lin, Han; Xu, Yanhua; Li, Lei; Mu, Haoran; Shivananju, Bannur Nanjunda; Zhang, Yupeng; Zhang, Qinglin; Pan, Anlian; Li, Shaojuan; Tang, Dingyuan; Jia, Baohua; Zhang, Han; Bao, Qiaoliang

    2017-04-12

    Even though the nonlinear optical effects of solution processed organic-inorganic perovskite films have been studied, the nonlinear optical properties in two-dimensional (2D) perovskites, especially their applications for ultrafast photonics, are largely unexplored. In comparison to bulk perovskite films, 2D perovskite nanosheets with small thicknesses of a few unit cells are more suitable for investigating the intrinsic nonlinear optical properties because bulk recombination of photocarriers and the nonlinear scattering are relatively small. In this research, we systematically investigated the nonlinear optical properties of 2D perovskite nanosheets derived from a combined solution process and vapor phase conversion method. It was found that 2D perovskite nanosheets have stronger saturable absorption properties with large modulation depth and very low saturation intensity compared with those of bulk perovskite films. Using an all dry transfer method, we constructed a new type of saturable absorber device based on single piece 2D perovskite nanosheet. Stable soliton state mode-locking was achieved, and ultrafast picosecond pulses were generated at 1064 nm. This work is likely to pave the way for ultrafast photonic and optoelectronic applications based on 2D perovskites.

  17. Perovskite solar cells in N-I-P structure with four slot-die-coated layers

    PubMed Central

    Burkitt, Daniel; Searle, Justin

    2018-01-01

    The fabrication of perovskite solar cells in an N-I-P structure with compact titanium dioxide blocking, mesoporous titanium dioxide scaffold, single-step perovskite and hole-transport layers deposited using the slot-die coating technique is reported. Devices on fluorine-doped tin oxide-coated glass substrates with evaporated gold top contacts and four slot-die-coated layers are demonstrated, and best cells reach stabilized power conversion efficiencies of 7%. This work demonstrates the suitability of slot-die coating for the production of layers within this perovskite solar cell stack and the potential to transfer to large area and roll-to-roll manufacturing processes. PMID:29892402

  18. DFT analysis and FDTD simulation of CH3NH3PbI3-x Cl x mixed halide perovskite solar cells: role of halide mixing and light trapping technique

    NASA Astrophysics Data System (ADS)

    Saffari, Mohaddeseh; Mohebpour, Mohammad Ali; Rahimpour Soleimani, H.; Bagheri Tagani, Meysam

    2017-10-01

    Since perovskite solar cells have attracted a great deal of attention over the past few years, the enhancement of their optical absorption and current density are among the basic upcoming challenges. For this reason, first, we have studied the structural and optical properties of organic-inorganic hybrid halide perovskite CH3NH3PbI3 and the compounds doped by chlorine halogen CH3NH3PbI3-x Cl x in the cubic phase by using a density functional theory (DFT). Then, we model a single-junction perovskite solar cell based on a full solution to Maxwell’s equations, using a finite difference time domain (FDTD) technique, which helps us to investigate the light absorption efficiency and optical current density of the cell with CH3NH3PbI3-x Cl x (x  =  0, 1, 2, 3) as the active layer. The results suggest that increasing the amount of chlorine in CH3NH3PbI3-x Cl x compound leads to an increase in the bandgap energy, as well as a decrease in the lattice constants and optical properties, like the refractive index and extinction coefficient of the structure. Also, the results obtained by the simulation express that by taking advantage of the light trapping techniques of SiO2, a remarkable increase of light absorption will be achieved to the magnitude of 83.13%, which is noticeable.

  19. Characterization of ordering in A-site deficient perovskite Ca 1–xLa 2x/3TiO 3 using STEM/EELS

    DOE PAGES

    Danaie, Mohsen; Kepaptsoglou, Demie; Ramasse, Quentin M.; ...

    2016-09-15

    The vacancy ordering behavior of an A-site deficient perovskite system, Ca 1–xLa 2x/3TiO 3, was studied using atomic resolution scanning transmission electron microscopy (STEM) in conjunction with electron energy-loss spectroscopy (EELS), with the aim of determining the role of A-site composition changes. At low La content (x = 0.2), adopting Pbnm symmetry, there was no indication of long-range ordering. Domains, with clear boundaries, were observed in bright-field (BF) imaging, but were not immediately visible in the corresponding high-angle annular dark-field (HAADF) image. These boundaries, with the aid of displacement maps from A-site cations in the HAADF signal, are shown tomore » be tilt boundaries. At the La-rich end of the composition (x = 0.9), adopting Cmmm symmetry, long-range ordering of vacancies and La 3+ ions was observed, with alternating La-rich and La-poor layers on (001)p planes, creating a double perovskite lattice along the c axis. These highly ordered domains can be found isolated within a random distribution of vacancies/La 3+, or within a large population, encompassing a large volume. In regions with a high number density of double perovskite domains, these highly ordered domains were separated by twin boundaries, with 90° or 180° lattice rotations across boundaries. In conclusion, the occurrence and characteristics of these ordered structures are discussed and compared with similar perovskite systems.« less

  20. Enhanced photovoltaic performance of CH3NH3PbBrXI3-X-based perovskite solar cells via anti-solvent extraction

    NASA Astrophysics Data System (ADS)

    Jiang, Zhaoyi; Zhang, Weijia; Lu, Chaoqun; Ma, Denghao; Liu, Haixu; Yu, Wei; Zhang, Yu; Ma, Qiang; Zhang, Yulong

    2018-06-01

    In this paper, the two-step sequential deposition method was used to prepare the CH3NH3PbBrXI3-X films by introducing CH3NH3Br in the precursors. The surface morphology of the PbI2 films was controlled by anti-solvent extraction (ASE) to improve the microstructure and photo-physical properties of the perovskite films. It was noteworthy that, compared to the compact PbI2 films, the porous PbI2 films facilitated the growth of crystals and bromine incorporation in films, and the prepared perovskite films exhibited enlarged grain size, increased light absorption, enhanced Br incorporation and prolonged carrier lifetime, which resulted in excellent photo-electrical properties of the CH3NH3PbBrXI3-X films. With porous PbI2 templates, the inverted planar perovskite solar cells based on films with appropriate Br incorporation (CH3NH3Br/CH3NH3I mole ratio = 3/7) showed a photovoltaic conversion efficiency (PCE) of 14.9%, and the stability of the devices in air was elevated. Consequently, the high-quality CH3NH3PbBrXI3-X films can be obtained with porous PbI2 templates for improving the performance of the perovskite solar cells.

  1. Dry (Mg,Fe)SiO 3 perovskite in the Earth's lower mantle

    DOE PAGES

    Panero, Wendy R.; Pigott, Jeffrey S.; Reaman, Daniel M.; ...

    2015-02-26

    Combined synthesis experiments and first-principles calculations show that MgSiO 3-perovskite with minor Al or Fe does not incorporate significant OH under lower mantle conditions. Perovskite, stishovite, and residual melt were synthesized from natural Bamble enstatite samples (Mg/(Fe+Mg) = 0.89 and 0.93; Al 2O 3 < 0.1 wt% with 35 and 2065 ppm wt H 2O, respectively) in the laser-heated diamond anvil cell at 1600-2000 K and 25-65 GPa. Combined Fourier transform infrared (FTIR) spectroscopy, x-ray diffraction, and ex-situ transmission electron microscopy (TEM) analysis demonstrates little difference in the resulting perovskite as a function of initial water content. Four distinct OHmore » vibrational stretching bands are evident upon cooling below 100 K (3576, 3378, 3274, and 3078 cm -1), suggesting 4 potential bonding sites for OH in perovskite with a maximum water content of 220 ppm wt H 2O, and likely no more than 10 ppm wt H 2O. Complementary, Fe-free, first-principles calculations predict multiple potential bonding sites for hydrogen in perovskite, each with significant solution enthalpy (0.2 eV/defect). We calculate that perovskite can dissolve less than 37 ppm wt H 2O (400 ppm H/Si) at the top of the lower mantle, decreasing to 31 ppm wt H 2O (340 ppm H/Si) at 125 GPa and 3000 K in the absence of a melt or fluid phase. Here, we propose that these results resolve a long-standing debate of the perovskite melting curve and explain the order of magnitude increase in viscosity from upper to lower mantle.« less

  2. Adsorption of molecular additive onto lead halide perovskite surfaces: A computational study on Lewis base thiophene additive passivation

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Yu, Fengxi; Chen, Lihong; Li, Jingfa

    2018-06-01

    Organic additives, such as the Lewis base thiophene, have been successfully applied to passivate halide perovskite surfaces, improving the stability and properties of perovskite devices based on CH3NH3PbI3. Yet, the detailed nanostructure of the perovskite surface passivated by additives and the mechanisms of such passivation are not well understood. This study presents a nanoscopic view on the interfacial structure of an additive/perovskite interface, consisting of a Lewis base thiophene molecular additive and a lead halide perovskite surface substrate, providing insights on the mechanisms that molecular additives can passivate the halide perovskite surfaces and enhance the perovskite-based device performance. Molecular dynamics study on the interactions between water molecules and the perovskite surfaces passivated by the investigated additive reveal the effectiveness of employing the molecular additives to improve the stability of the halide perovskite materials. The additive/perovskite surface system is further probed via molecular engineering the perovskite surfaces. This study reveals the nanoscopic structure-property relationships of the halide perovskite surface passivated by molecular additives, which helps the fundamental understanding of the surface/interface engineering strategies for the development of halide perovskite based devices.

  3. Experimental search for high-temperature ferroelectric perovskites guided by two-step machine learning.

    PubMed

    Balachandran, Prasanna V; Kowalski, Benjamin; Sehirlioglu, Alp; Lookman, Turab

    2018-04-26

    Experimental search for high-temperature ferroelectric perovskites is a challenging task due to the vast chemical space and lack of predictive guidelines. Here, we demonstrate a two-step machine learning approach to guide experiments in search of xBi[Formula: see text]O 3 -(1 - x)PbTiO 3 -based perovskites with high ferroelectric Curie temperature. These involve classification learning to screen for compositions in the perovskite structures, and regression coupled to active learning to identify promising perovskites for synthesis and feedback. The problem is challenging because the search space is vast, spanning ~61,500 compositions and only 167 are experimentally studied. Furthermore, not every composition can be synthesized in the perovskite phase. In this work, we predict x, y, Me', and Me″ such that the resulting compositions have both high Curie temperature and form in the perovskite structure. Outcomes from both successful and failed experiments then iteratively refine the machine learning models via an active learning loop. Our approach finds six perovskites out of ten compositions synthesized, including three previously unexplored {Me'Me″} pairs, with 0.2Bi(Fe 0.12 Co 0.88 )O 3 -0.8PbTiO 3 showing the highest measured Curie temperature of 898 K among them.

  4. Ferroelectricity in d0 double perovskite fluoroscandates

    NASA Astrophysics Data System (ADS)

    Charles, Nenian; Rondinelli, James M.

    2015-08-01

    Ferroelectricity in strain-free and strained double perovskite fluorides, Na3ScF6 and K2NaScF6 , is investigated using first-principles density functional theory. Although the experimental room temperature crystal structures of these fluoroscandates are centrosymmetric, i.e., Na3ScF6 (P 21/n ) and K2NaScF6 (F m 3 ¯m ), lattice dynamical calculations reveal that soft polar instabilities exist in each prototypical cubic phase and that the modes harden as the tolerance factor approaches unity. Thus the double fluoroperovskites bear some similarities to A B O3 perovskite oxides; however, in contrast, these fluorides exhibit large acentric displacements of alkali metal cations (Na, K) rather than polar displacements of the transition metal cations. Biaxial strain investigations of the centrosymmetric and polar Na3ScF6 and K2NaScF6 phases reveal that the paraelectric structures are favored under compressive strain, whereas polar structures with in-plane electric polarizations (˜5 -18 μ C cm-2 ) are realized at sufficiently large tensile strains. The electric polarization and stability of the polar structures for both chemistries are found to be further enhanced and stabilized by a coexisting single octahedral tilt system. Our results suggest that polar double perovskite fluorides may be realized by suppression of octahedral rotations about more than one Cartesian axis; structures exhibiting in- or out-of-phase octahedral rotations about the c axis are more susceptible to polar symmetries.

  5. Structural phase transition causing anomalous photoluminescence behavior in perovskite (C6H11NH3)2[PbI4

    NASA Astrophysics Data System (ADS)

    Yangui, A.; Pillet, S.; Mlayah, A.; Lusson, A.; Bouchez, G.; Triki, S.; Abid, Y.; Boukheddaden, K.

    2015-12-01

    Optical and structural properties of the organic-inorganic hybrid perovskite-type (C6H11NH3)2[PbI4] (abbreviated as C6PbI4) were investigated using optical absorption, photoluminescence (PL), and x-ray diffraction measurements. Room temperature, optical absorption measurements, performed on spin-coated films of C6PbI4, revealed two absorption bands at 2.44 and 3.21 eV. Upon 325 nm (3.815 eV) laser irradiation, strong green PL emission peaks were observed at 2.41 eV (P1) and 2.24 eV (P2) and assigned to free and localized excitons, respectively. The exciton binding energy was estimated at 356 meV. At low temperature, two additional emission bands were detected at 2.366 eV (P3) and a large band (LB) at 1.97 eV. The former appeared only below 40 K and the latter emerged below 130 K. The thermal dependence of the PL spectra revealed an abnormal behavior accompanied by singularities in the peak positions and intensities at 40 and 130 K. X-ray diffraction studies performed on powder and single crystals as a function of temperature evidenced significant changes of the interlayer spacing at 50 K and ˜138 K. Around 138 K, a commensurate to incommensurate structural phase transition occurred on cooling. It involves a symmetry breaking leading to a distortion of the PbI6 octahedron. The resulting incommensurate spatial modulation of the Pb-I distances (and Pb-I-Pb angles) causes a spatial modulation of the band gap, which is at the origin of the emergence of the LB below ˜130 K and the anomalous behavior of the position of P1 below 130 K. The change of the interlayer spacing in the 40-50 K range may in turn be related to the significant decrease of the intensity of P2 and the maximum emission of the LB. These results underline the intricate character of the structural and the PL properties of the hybrid perovskites; understanding such properties should benefit to the design of optoelectronic devices with targeted properties.

  6. Structural phase transition causing anomalous photoluminescence behavior in perovskite (C6H11NH3)2[PbI4].

    PubMed

    Yangui, A; Pillet, S; Mlayah, A; Lusson, A; Bouchez, G; Triki, S; Abid, Y; Boukheddaden, K

    2015-12-14

    Optical and structural properties of the organic-inorganic hybrid perovskite-type (C6H11NH3)2[PbI4] (abbreviated as C6PbI4) were investigated using optical absorption, photoluminescence (PL), and x-ray diffraction measurements. Room temperature, optical absorption measurements, performed on spin-coated films of C6PbI4, revealed two absorption bands at 2.44 and 3.21 eV. Upon 325 nm (3.815 eV) laser irradiation, strong green PL emission peaks were observed at 2.41 eV (P1) and 2.24 eV (P2) and assigned to free and localized excitons, respectively. The exciton binding energy was estimated at 356 meV. At low temperature, two additional emission bands were detected at 2.366 eV (P3) and a large band (LB) at 1.97 eV. The former appeared only below 40 K and the latter emerged below 130 K. The thermal dependence of the PL spectra revealed an abnormal behavior accompanied by singularities in the peak positions and intensities at 40 and 130 K. X-ray diffraction studies performed on powder and single crystals as a function of temperature evidenced significant changes of the interlayer spacing at 50 K and ∼138 K. Around 138 K, a commensurate to incommensurate structural phase transition occurred on cooling. It involves a symmetry breaking leading to a distortion of the PbI6 octahedron. The resulting incommensurate spatial modulation of the Pb-I distances (and Pb-I-Pb angles) causes a spatial modulation of the band gap, which is at the origin of the emergence of the LB below ∼130 K and the anomalous behavior of the position of P1 below 130 K. The change of the interlayer spacing in the 40-50 K range may in turn be related to the significant decrease of the intensity of P2 and the maximum emission of the LB. These results underline the intricate character of the structural and the PL properties of the hybrid perovskites; understanding such properties should benefit to the design of optoelectronic devices with targeted properties.

  7. The prognostic value of ABO blood group in cancer patients

    PubMed Central

    Franchini, Massimo; Liumbruno, Giancarlo M.; Lippi, Giuseppe

    2016-01-01

    The antigens of the ABO system are expressed on red blood cell membranes as well as on the surface of several other normal and pathological cells and tissues. Following the first clinical observations more than 60 years ago, the role of ABO blood group in cancer biology has been intensely studied by several investigators, and it is now widely recognised that ABO antigens are associated with the risk of developing several types of tumours, namely pancreatic and gastric cancers. However, whether this association also affects the clinical outcome of cancer patients is less certain. In this narrative review, based on literature data, we discuss the role of ABO blood types as prognostic biomarkers in different types of cancers. The current knowledge of the underlying pathogenic mechanisms of the association is also analysed. PMID:26674825

  8. ABO blood groups and risk for obesity in Arar, Northern Saudi Arabia.

    PubMed

    Aboel-Fetoh, Nagah M; Alanazi, Arwa R; Alanazi, Abdullah S; Alruwili, Asma N

    2016-12-01

    ABO blood groups are associated with some important chronic diseases. Previous studies have observed an association between ABO blood group and risk for obesity. This study aimed to determine whether there is an association between ABO blood groups and obesity in apparently healthy attendees of primary healthcare (PHC) centers in Arar city, Northern Saudi Arabia. This cross-sectional study included 401 participants aged 15 years and older attending three randomly selected PHC centers in Arar city. Data were collected by means of personal interview using a predesigned questionnaire. Anthropometric examination included height and weight measurements with calculation of BMI. ABO and Rh blood groups were determined. The majority of the participants were female (70.8%). The mean±SD age was 28.6±9.1 years. Only 5.7% were underweight. Both normal and overweight participants were equal in number and constituted 28.4%, whereas obese individuals constituted 37.4% with a mean BMI of 28.56±8.0. Blood group O was the most common (44.1%), followed by A (30.9%), B (18.7%), and AB (6.2%). Rh-positive cases constituted 87.0%. Blood group O was the most common type among the obese individuals (44.7%), followed by A, B, and AB groups (30, 20, and 5.3%, respectively). BMI was highest (28.8±9.2) in blood group O. There were no statistically significant differences between different ABO blood groups as regards BMI, Rh, and sex. Moreover, there was no statistically significant difference between Rh type and BMI. The prevalence of obesity and overweight is high in the population attending PHC centers of Arar city, Northern Saudi Arabia. There is no association between overweight, obesity, and ABO blood groups or Rh.

  9. Fabrication and characterization of perovskite-based CH{sub 3}NH{sub 3}Pb{sub 1-x}Ge{sub x}I{sub 3}, CH{sub 3}NH{sub 3}Pb{sub 1-x}Tl{sub x}I{sub 3} and CH{sub 3}NH{sub 3}Pb{sub 1-x}In{sub x}I{sub 3} photovoltaic devices

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ohishi, Yuya; Oku, Takeo, E-mail: oku@mat.usp.ac.jp; Suzuki, Atsushi

    2016-02-01

    Perovskite-type CH{sub 3}NH{sub 3}PbI{sub 3}-based photovoltaic devices were fabricated and characterized. Doping effects of thallium (Tl), indium (In), or germanium (Ge) element on the photovoltaic properties and surface structures of the perovskite phase were investigated. The open circuit voltage increased by Ge addition, and fill factors were improved by adding a small amount of Ge, Tl or In. In addition, the wavelength range of incident photon conversion efficiencies was expanded by the Tl addition.

  10. Observation of Quantum Confinement in Monodisperse Methylammonium Lead Halide Perovskite Nanocrystals Embedded in Mesoporous Silica.

    PubMed

    Malgras, Victor; Tominaka, Satoshi; Ryan, James W; Henzie, Joel; Takei, Toshiaki; Ohara, Koji; Yamauchi, Yusuke

    2016-10-13

    Hybrid organic-inorganic metal halide perovskites have fascinating electronic properties and have already been implemented in various devices. Although the behavior of bulk metal halide perovskites has been widely studied, the properties of perovskite nanocrystals are less well-understood because synthesizing them is still very challenging, in part because of stability. Here we demonstrate a simple and versatile method to grow monodisperse CH 3 NH 3 PbBr x I x-3 perovskite nanocrystals inside mesoporous silica templates. The size of the nanocrystal is governed by the pore size of the templates (3.3, 3.7, 4.2, 6.2, and 7.1 nm). In-depth structural analysis shows that the nanocrystals maintain the perovskite crystal structure, but it is slightly distorted. Quantum confinement was observed by tuning the size of the particles via the template. This approach provides an additional route to tune the optical bandgap of the nanocrystal. The level of quantum confinement was modeled taking into account the dimensions of the rod-shaped nanocrystals and their close packing inside the channels of the template. Photoluminescence measurements on CH 3 NH 3 PbBr clearly show a shift from green to blue as the pore size is decreased. Synthesizing perovskite nanostructures in templates improves their stability and enables tunable electronic properties via quantum confinement. These structures may be useful as reference materials for comparison with other perovskites, or as functional materials in all solid-state light-emitting diodes.

  11. Outcomes Following ABO-Incompatible Kidney Transplantation Performed After Desensitization by Nonantigen-Specific Immunoadsorption.

    PubMed

    Becker, Luis E; Siebert, Daniela; Süsal, Caner; Opelz, Gerhard; Leo, Albrecht; Waldherr, Rüdiger; Macher-Goeppinger, Stephan; Schemmer, Peter; Schaefer, Sebastian Markus; Klein, Katrin; Beimler, Jörg; Zeier, Martin; Schwenger, Vedat; Morath, Christian

    2015-11-01

    For desensitization of ABO-incompatible kidney transplant recipients we recently proposed nonantigen-specific immunoadsorption (IA) and rituximab. We now compared clinical outcomes of 34 ABO-incompatible living-donor kidney recipients who were transplanted using this protocol with that of 68 matched ABO-compatible patients. In addition, we analyzed efficacy and cost of nonantigen-specific as compared to blood group antigen-specific IA. Before desensitization, the median isoagglutinin titer of 34 ABO-incompatible patients was 1:64 (Coombs technique). Patients received a median of 7 preoperative IA treatments. Twenty-four patients had a median of 2 additional plasmapheresis treatments to reach the preoperative target isoagglutinin titer of 1:8 or less. After a median postoperative follow-up of 22 months, overall graft survival in the ABO-incompatible group was not significantly different from that in ABO-compatible patients (log-rank P = 0.20), whereas patient survival tended to be lower (log-rank P = 0.05). The incidence of rejection episodes was 15% in both groups. The ABO-incompatible kidney recipients had a higher incidence of BK virus replication (P = 0.04) and nephropathy (P = 0.01) and showed more often colonization with multidrug resistant bacteria (P = 0.02). In comparison to blood group antigen-specific IA, nonantigen-specific IA showed equal efficacy but was associated with reduction in cost. Clinical outcomes of ABO-incompatible patients desensitized with a nonantigen-specific IA device and rituximab do not differ from that of matched ABO-compatible patients although a trend toward reduced patient survival was noted. Special attention must be paid to the higher incidence of BK virus infection in recipients of ABO-incompatible grafts.

  12. Ba3Fe1.56Ir1.44O9: A Polar Semiconducting Triple Perovskite with Near Room Temperature Magnetic Ordering.

    PubMed

    Ferreira, Timothy; Carone, Darren; Huon, Amanda; Herklotz, Andreas; Stoian, Sebastian A; Heald, Steve M; Morrison, Gregory; Smith, Mark D; Loye, Hans-Conrad Zur

    2018-05-29

    The crystal chemistry and magnetic properties for two triple perovskites, Ba 3 Fe 1.56 Ir 1.44 O 9 and Ba 3 NiIr 2 O 9 , grown as large, highly faceted single crystals from a molten strontium carbonate flux, are reported. Unlike the idealized A 3 MM 2 'O 9 hexagonal symmetry characteristic of most triple perovskites, including Ba 3 NiIr 2 O 9, Ba 3 Fe 1.56 Ir 1.44 O 9 possesses significant site-disorder, resulting in a noncentrosymmetric polar structure with trigonal symmetry. The valence of iron and iridium in the heavily distorted Fe/Ir sites was determined to be Fe(III) and Ir(V) by X-ray absorption near edge spectroscopy (XANES). Density functional theory calculations were conducted to understand the effect of the trigonal distortion on the local Fe(III)O 6 electronic structure, and the spin state of iron was determined to be S = 5/2 by Mössbauer spectroscopy. Conductivity measurements indicate thermally activated semiconducting behavior in the trigonal perovskite. Magnetic properties were measured and near room temperature magnetic ordering (T N = 270 K) was observed for Ba 3 Fe 1.56 Ir 1.44 O 9 .

  13. Modeling defects and plasticity in MgSiO3 post-perovskite: Part 2-screw and edge [100] dislocations.

    PubMed

    Goryaeva, Alexandra M; Carrez, Philippe; Cordier, Patrick

    In this study, we propose a full atomistic study of [100] dislocations in MgSiO 3 post-perovskite based on the pairwise potential parameterized by Oganov et al. (Phys Earth Planet Inter 122:277-288, 2000) for MgSiO 3 perovskite. We model screw dislocations to identify planes where they glide easier. We show that despite a small tendency to core spreading in {011}, [100] screw dislocations glide very easily (Peierls stress of 1 GPa) in (010) where only Mg-O bonds are to be sheared. Crossing the Si-layers results in a higher lattice friction as shown by the Peierls stress of [100](001): 17.5 GPa. Glide of [100] screw dislocations in {011} appears also to be highly unfavorable. Whatever the planes, (010), (001) or {011}, edge dislocations are characterized by a wider core (of the order of 2 b ). Contrary to screw character, they bear negligible lattice friction (0.1 GPa) for each slip system. The layered structure of post-perovskite results in a drastic reduction in lattice friction opposed to the easiest slip systems compared to perovskite.

  14. Controlling octahedral rotations in a perovskite via strain doping

    DOE PAGES

    Herklotz, Andreas; Biegalski, Michael D.; Lee, Ho Nyung; ...

    2016-05-24

    The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film canmore » be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO 3 films coherently grown on SrTiO 3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. Lastly, these results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials.« less

  15. DFT +U Modeling of Hole Polarons in Organic Lead Halide Perovskites

    NASA Astrophysics Data System (ADS)

    Welch, Eric; Erhart, Paul; Scolfaro, Luisa; Zakhidov, Alex

    Due to the ever present drive towards improved efficiencies in solar cell technology, new and improved materials are emerging rapidly. Organic halide perovskites are a promising prospect, yet a fundamental understanding of the organic perovskite structure and electronic properties is missing. Particularly, explanations of certain physical phenomena, specifically a low recombination rate and high mobility of charge carriers still remain controversial. We theoretically investigate possible formation of hole polarons adopting methodology used for oxide perovskites. The perovskite studied here is the ABX3structure, with A being an organic cation, B lead and C a halogen; the combinations studied allow for A1,xA2 , 1 - xBX1,xX2 , 3 - xwhere the alloy convention is used to show mixtures of the organic cations and/or the halogens. Two organic cations, methylammonium and formamidinium, and three halogens, iodine, chlorine and bromine are studied. Electronic structures and polaron behavior is studied through first principle density functional theory (DFT) calculations using the Vienna Ab Initio Simulation Package (VASP). Local density approximation (LDA) pseudopotentials are used and a +U Hubbard correction of 8 eV is added; this method was shown to work with oxide perovskites. It is shown that a localized state is realized with the Hubbard correction in systems with an electron removed, residing in the band gap of each different structure. Thus, hole polarons are expected to be seen in these perovskites.

  16. High-Quality In-Plane Aligned CsPbX3 Perovskite Nanowire Lasers with Composition-Dependent Strong Exciton-Photon Coupling.

    PubMed

    Wang, Xiaoxia; Shoaib, Muhammad; Wang, Xiao; Zhang, Xuehong; He, Mai; Luo, Ziyu; Zheng, Weihao; Li, Honglai; Yang, Tiefeng; Zhu, Xiaoli; Ma, Libo; Pan, Anlian

    2018-06-14

    Cesium lead halide perovskite nanowires have emerged as promising low-dimensional semiconductor structures for integrated photonic applications. Understanding light-matter interactions in a nanowire cavity is of both fundamental and practical interest in designing low-power-consumption nanoscale light sources. In this work, high-quality in-plane aligned halide perovskite CsPbX 3 (X = Cl, Br, I) nanowires are synthesized by a vapor growth method on an annealed M-plane sapphire substrate. Large-area nanowire laser arrays have been achieved based on the as-grown aligned CsPbX 3 nanowires at room temperature with quite low pumping thresholds, very high quality factors, and a high degree of linear polarization. More importantly, it is found that exciton-polaritons are formed in the nanowires under the excitation of a pulsed laser, indicating a strong exciton-photon coupling in the optical microcavities made of cesium lead halide perovskites. The coupling strength in these CsPbX 3 nanowires is dependent on the atomic composition, where the obtained room-temperature Rabi splitting energy is ∼210 ± 13, 146 ± 9, and 103 ± 5 meV for the CsPbCl 3 , CsPbBr 3 , and CsPbI 3 nanowires, respectively. This work provides fundamental insights for the practical applications of all-inorganic perovskite CsPbX 3 nanowires in designing light-emitting devices and integrated nanophotonic systems.

  17. Single Sublattice Endotaxial Phase Separation Driven by Charge Frustration in a Complex Oxide

    PubMed Central

    2013-01-01

    Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation. PMID:23750709

  18. Influence of Rb/Cs Cation-Exchange on Inorganic Sn Halide Perovskites: From Chemical Structure to Physical Properties.

    PubMed

    Jung, Young-Kwang; Lee, Ji-Hwan; Walsh, Aron; Soon, Aloysius

    2017-04-11

    CsSnI 3 is a potential lead-free inorganic perovskite for solar energy applications due to its nontoxicity and attractive optoelectronic properties. Despite these advantages, photovoltaic cells using CsSnI 3 have not been successful to date, in part due to low stability. We demonstrate how gradual substitution of Rb for Cs influences the structural, thermodynamic, and electronic properties on the basis of first-principles density functional theory calculations. By examining the effect of the Rb:Cs ratio, we reveal a correlation between octahedral distortion and band gap, including spin-orbit coupling. We further highlight the cation-induced variation of the ionization potential (work function) and the importance of surface termination for tin-based halide perovskites for engineering high-performance solar cells.

  19. Unique Trapped Dimer State of the Photogenerated Hole in Hybrid Orthorhombic CH3NH3PbI3 Perovskite: Identification, Origin, and Implications.

    PubMed

    Peng, Chao; Wang, Jinglin; Wang, Haifeng; Hu, P

    2017-12-13

    Revealing the innate character and transport of the photogenerated hole is essential to boost the high photovoltaic performance in the lead-based organohalide perovskite. However, knowledge at the atomic level is currently very limited. In this work, we systematically investigate the properties of the photogenerated hole in the orthorhombic CH 3 NH 3 PbI 3 using hybrid functional PBE0 calculations with spin-orbit coupling included. An unexpected trapping state of the hole, localized as I 2 - (I dimer), is uncovered, which was never reported in photovoltaic materials. It is shown that this localized configuration is energetically more favorable than that of the delocalized hole state by 191 meV and that it can highly promote the diffusion of the hole with an energy barrier as low as 131 meV. Furthermore, the origin of I dimer formation upon trapping of the hole is rationalized in terms of electronic and geometric effects, and a good linear correlation is found between the hole trapping capacity and the accompanying structural deformation in CH 3 NH 3 PbX 3 (X = Cl, Br, and I). It is demonstrated that good CH 3 NH 3 PbX 3 materials for the hole diffusion should have small structural deformation energy and weak hole trapping capacity, which may facilitate the rational screening of superior photovoltaic perovskites.

  20. Relationship between ABO blood group and pregnancy complications: a systematic literature analysis

    PubMed Central

    Franchini, Massimo; Mengoli, Carlo; Lippi, Giuseppe

    2016-01-01

    Given the expression of ABO blood group antigens on the surface of a wide range of human cells and tissues, the putative interplay of the ABO system in human biology outside the area of transfusion and transplantation medicine constitutes an intriguing byway of research. Thanks to evidence accumulated over more than 50 years, the involvement of the ABO system in the pathogenesis of several human diseases, including cardiovascular, infectious and neoplastic disorders, is now acknowledged. However, there is controversial information on the potential association between ABO blood type and adverse pregnancy outcomes, including pre-eclampsia and related disorders (eclampsia, HELLP syndrome and intrauterine growth restriction), venous thromboembolism, post-partum haemorrhage and gestational diabetes. To elucidate the role of ABO antigens in pregnancy-related complications, we performed a systematic review of the literature published in the past 50 years. A meta-analytical approach was also applied to the existing literature on the association between ABO status and pre-eclampsia. The results of this systematic review are presented and critically discussed, along with the possible pathogenic implications. PMID:27177402

  1. Atomically thin two-dimensional organic-inorganic hybrid perovskites

    NASA Astrophysics Data System (ADS)

    Dou, Letian; Wong, Andrew B.; Yu, Yi; Lai, Minliang; Kornienko, Nikolay; Eaton, Samuel W.; Fu, Anthony; Bischak, Connor G.; Ma, Jie; Ding, Tina; Ginsberg, Naomi S.; Wang, Lin-Wang; Alivisatos, A. Paul; Yang, Peidong

    2015-09-01

    Organic-inorganic hybrid perovskites, which have proved to be promising semiconductor materials for photovoltaic applications, have been made into atomically thin two-dimensional (2D) sheets. We report the solution-phase growth of single- and few-unit-cell-thick single-crystalline 2D hybrid perovskites of (C4H9NH3)2PbBr4 with well-defined square shape and large size. In contrast to other 2D materials, the hybrid perovskite sheets exhibit an unusual structural relaxation, and this structural change leads to a band gap shift as compared to the bulk crystal. The high-quality 2D crystals exhibit efficient photoluminescence, and color tuning could be achieved by changing sheet thickness as well as composition via the synthesis of related materials.

  2. Efficient ambient-air-stable solar cells with 2D-3D heterostructured butylammonium-caesium-formamidinium lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Wang, Zhiping; Lin, Qianqian; Chmiel, Francis P.; Sakai, Nobuya; Herz, Laura M.; Snaith, Henry J.

    2017-09-01

    Perovskite solar cells are remarkably efficient; however, they are prone to degradation in water, oxygen and ultraviolet light. Cation engineering in 3D perovskite absorbers has led to reduced degradation. Alternatively, 2D Ruddlesden-Popper layered perovskites exhibit improved stability, but have not delivered efficient solar cells so far. Here, we introduce n-butylammonium cations into a mixed-cation lead mixed-halide FA0.83Cs0.17Pb(IyBr1-y)3 3D perovskite. We observe the formation of 2D perovskite platelets, interspersed between highly orientated 3D perovskite grains, which suppress non-radiative charge recombination. We investigate the relationship between thin-film composition, crystal alignment and device performance. Solar cells with an optimal butylammonium content exhibit average stabilized power conversion efficiency of 17.5 ± 1.3% with a 1.61-eV-bandgap perovskite and 15.8 ± 0.8% with a 1.72-eV-bandgap perovskite. The stability under simulated sunlight is also enhanced. Cells sustain 80% of their 'post burn-in' efficiency after 1,000 h in air, and close to 4,000 h when encapsulated.

  3. Nb5+-Doped SrCoO3Perovskites as Potential Cathodes for Solid-Oxide Fuel Cells.

    PubMed

    Cascos, Vanessa; Alonso, José Antonio; Fernández-Díaz, María Teresa

    2016-07-15

    SrCoO 3- δ outperforms as cathode material in solid-oxide fuel cells (SOFC) when the three-dimensional (3C-type) perovskite structure is stabilized by the inclusion of highly-charged transition-metal ions at the octahedral positions. In a previous work we studied the Nb incorporation at the Co positions in the SrCo 1- x Nb x O 3- δ system, in which the stabilization of a tetragonal P4 / mmm perovskite superstructure was described for the x = 0.05 composition. In the present study we extend this investigation to the x = 0.10-0.15 range, also observing the formation of the tetragonal P4 / mmm structure instead of the unwanted hexagonal phase corresponding to the 2H polytype. We also investigated the effect of Nb 5+ doping on the thermal, electrical, and electrochemical properties of SrCo 1- x Nb x O 3- δ ( x = 0.1 and 0.15) perovskite oxides performing as cathodes in SOFC. In comparison with the undoped hexagonal SrCoO 3- δ phase, the resulting compounds present high thermal stability and an increase of the electrical conductivity. The single-cell tests for these compositions ( x = 0.10 and 0.15) with La 0.8 Sr 0.2 Ga 0.83 Mg 0.17 O 3- δ (LSGM) as electrolyte and SrMo 0.8 Fe 0.2 CoO 3- δ as anode gave maximum power densities of 693 and 550 mW∙cm -2 at 850 °C respectively, using pure H₂ as fuel and air as oxidant.

  4. Correlation between Geometrically Induced Oxygen Octahedral Tilts and Multiferroic Behaviors in BiFeO 3 Films

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lee, Sung Su; Kim, Young-Min; Lee, Hyun-Jae

    The equilibrium position of atoms in a unit cell is directly connected to crystal functionalities, e.g., ferroelectricity, ferromagnetism, and piezoelectricity. The artificial tuning of the energy landscape can involve repositioning atoms as well as manipulating the functionalities of perovskites (ABO 3), which are good model systems to test this legacy. Mechanical energy from external sources accommodating various clamping substrates is utilized to perturb the energy state of perovskite materials fabricated on the substrates and consequently change their functionalities; however, this approach yields undesired complex behaviors of perovskite crystals, such as lattice distortion, displacement of B atoms, and/or tilting of oxygenmore » octahedra. Owing to complimentary collaborations between experimental and theoretical studies, the effects of both lattice distortion and displacement of B atoms are well understood so far, which leaves us a simple question: Can we exclusively control the positions of oxygen atoms in perovskites for functionality manipulation? Here the artificial manipulation of oxygen octahedral tilt angles within multiferroic BiFeO 3 thin films using strong oxygen octahedral coupling with bottom SrRuO 3 layers is reported, which opens up new possibilities of oxygen octahedral engineering.« less

  5. Correlation between Geometrically Induced Oxygen Octahedral Tilts and Multiferroic Behaviors in BiFeO 3 Films

    DOE PAGES

    Lee, Sung Su; Kim, Young-Min; Lee, Hyun-Jae; ...

    2018-03-26

    The equilibrium position of atoms in a unit cell is directly connected to crystal functionalities, e.g., ferroelectricity, ferromagnetism, and piezoelectricity. The artificial tuning of the energy landscape can involve repositioning atoms as well as manipulating the functionalities of perovskites (ABO 3), which are good model systems to test this legacy. Mechanical energy from external sources accommodating various clamping substrates is utilized to perturb the energy state of perovskite materials fabricated on the substrates and consequently change their functionalities; however, this approach yields undesired complex behaviors of perovskite crystals, such as lattice distortion, displacement of B atoms, and/or tilting of oxygenmore » octahedra. Owing to complimentary collaborations between experimental and theoretical studies, the effects of both lattice distortion and displacement of B atoms are well understood so far, which leaves us a simple question: Can we exclusively control the positions of oxygen atoms in perovskites for functionality manipulation? Here the artificial manipulation of oxygen octahedral tilt angles within multiferroic BiFeO 3 thin films using strong oxygen octahedral coupling with bottom SrRuO 3 layers is reported, which opens up new possibilities of oxygen octahedral engineering.« less

  6. Dependence of Acetate-Based Antisolvents for High Humidity Fabrication of CH3NH3PbI3 Perovskite Devices in Ambient Atmosphere.

    PubMed

    Yang, Fu; Kapil, Gaurav; Zhang, Putao; Hu, Zhaosheng; Kamarudin, Muhammad Akmal; Ma, Tingli; Hayase, Shuzi

    2018-05-16

    High-efficiency perovskite solar cells (PSCs) need to be fabricated in the nitrogen-filled glovebox by the atmosphere-controlled crystallization process. However, the use of the glovebox process is of great concern for mass level production of PSCs. In this work, notable efficient CH 3 NH 3 PbI 3 solar cells can be obtained in high humidity ambient atmosphere (60-70% relative humidity) by using acetate as the antisolvent, in which dependence of methyl, ethyl, propyl, and butyl acetate on the crystal growth mechanism is discussed. It is explored that acetate screens the sensitive perovskite intermediate phases from water molecules during perovskite film formation and annealing. It is revealed that relatively high vapor pressure and high water solubility of methyl acetate (MA) leads to the formation of highly dense and pinhole free perovskite films guiding to the best power conversion efficiency (PCE) of 16.3% with a reduced hysteresis. The devices prepared using MA showed remarkable shelf life stability of more than 80% for 360 h in ambient air condition, when compared to the devices fabricated using other antisolvents with low vapor pressure and low water solubility. Moreover, the PCE was still kept at 15.6% even though 2 vol % deionized water was added in the MA for preparing the perovskite layer.

  7. Insight into Evolution, Processing and Performance of Multi-length-scale Structures in Planar Heterojunction Perovskite Solar Cells.

    PubMed

    Huang, Yu-Ching; Tsao, Cheng-Si; Cho, Yi-Ju; Chen, Kuan-Chen; Chiang, Kai-Ming; Hsiao, Sheng-Yi; Chen, Chang-Wen; Su, Chun-Jen; Jeng, U-Ser; Lin, Hao-Wu

    2015-09-04

    The structural characterization correlated to the processing control of hierarchical structure of planar heterojunction perovskite layer is still incomplete due to the limitations of conventional microscopy and X-ray diffraction. This present study performed the simultaneously grazing-incidence small-angle scattering and wide-angle scattering (GISAXS/GIWAXS) techniques to quantitatively probe the hierarchical structure of the planar heterojunction perovskite solar cells. The result is complementary to the currently microscopic study. Correlation between the crystallization behavior, crystal orientation, nano- and meso-scale internal structure and surface morphology of perovskite film as functions of various processing control parameters is reported for the first time. The structural transition from the fractal pore network to the surface fractal can be tuned by the chloride percentage. The GISAXS/GIWAXS measurement provides the comprehensive understanding of concurrent evolution of the film morphology and crystallization correlated to the high performance. The result can provide the insight into formation mechanism and rational synthesis design.

  8. Insight into Evolution, Processing and Performance of Multi-length-scale Structures in Planar Heterojunction Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Huang, Yu-Ching; Tsao, Cheng-Si; Cho, Yi-Ju; Chen, Kuan-Chen; Chiang, Kai-Ming; Hsiao, Sheng-Yi; Chen, Chang-Wen; Su, Chun-Jen; Jeng, U.-Ser; Lin, Hao-Wu

    2015-09-01

    The structural characterization correlated to the processing control of hierarchical structure of planar heterojunction perovskite layer is still incomplete due to the limitations of conventional microscopy and X-ray diffraction. This present study performed the simultaneously grazing-incidence small-angle scattering and wide-angle scattering (GISAXS/GIWAXS) techniques to quantitatively probe the hierarchical structure of the planar heterojunction perovskite solar cells. The result is complementary to the currently microscopic study. Correlation between the crystallization behavior, crystal orientation, nano- and meso-scale internal structure and surface morphology of perovskite film as functions of various processing control parameters is reported for the first time. The structural transition from the fractal pore network to the surface fractal can be tuned by the chloride percentage. The GISAXS/GIWAXS measurement provides the comprehensive understanding of concurrent evolution of the film morphology and crystallization correlated to the high performance. The result can provide the insight into formation mechanism and rational synthesis design.

  9. Formation Dynamics of CH3NH3PbI3 Perovskite Following Two-Step Layer Deposition.

    PubMed

    Patel, Jay B; Milot, Rebecca L; Wright, Adam D; Herz, Laura M; Johnston, Michael B

    2016-01-07

    Hybrid metal-halide perovskites have emerged as a leading class of semiconductors for optoelectronic devices because of their desirable material properties and versatile fabrication methods. However, little is known about the chemical transformations that occur in the initial stages of perovskite crystal formation. Here we follow the real-time formation dynamics of MAPbI3 from a bilayer of lead iodide (PbI2) and methylammonium iodide (MAI) deposited through a two-step thermal evaporation process. By lowering the substrate temperature during deposition, we are able to initially inhibit intermixing of the two layers. We subsequently use infrared and visible light transmission, X-ray diffraction, and photoluminescence lifetime measurements to reveal the room-temperature transformations that occur in vacuum and ambient air, as MAI diffuses into the PbI2 lattice to form MAPbI3. In vacuum, the transformation to MAPbI3 is incomplete as unreacted MAI is retained in the film. However, exposure to moist air allows for conversion of the unreacted MAI to MAPbI3, demonstrating that moisture is essential in making MAI more mobile and thus aiding perovskite crystallization. These dynamic processes are reflected in the observed charge-carrier lifetimes, which strongly fluctuate during periods of large ion migration but steadily increase with improving crystallinity.

  10. Organic-inorganic hybrid lead halide perovskites for optoelectronic and electronic applications.

    PubMed

    Zhao, Yixin; Zhu, Kai

    2016-02-07

    Organic and inorganic hybrid perovskites (e.g., CH(3)NH(3)PbI(3)), with advantages of facile processing, tunable bandgaps, and superior charge-transfer properties, have emerged as a new class of revolutionary optoelectronic semiconductors promising for various applications. Perovskite solar cells constructed with a variety of configurations have demonstrated unprecedented progress in efficiency, reaching about 20% from multiple groups after only several years of active research. A key to this success is the development of various solution-synthesis and film-deposition techniques for controlling the morphology and composition of hybrid perovskites. The rapid progress in material synthesis and device fabrication has also promoted the development of other optoelectronic applications including light-emitting diodes, photodetectors, and transistors. Both experimental and theoretical investigations on organic-inorganic hybrid perovskites have enabled some critical fundamental understandings of this material system. Recent studies have also demonstrated progress in addressing the potential stability issue, which has been identified as a main challenge for future research on halide perovskites. Here, we review recent progress on hybrid perovskites including basic chemical and crystal structures, chemical synthesis of bulk/nanocrystals and thin films with their chemical and physical properties, device configurations, operation principles for various optoelectronic applications (with a focus on solar cells), and photophysics of charge-carrier dynamics. We also discuss the importance of further understanding of the fundamental properties of hybrid perovskites, especially those related to chemical and structural stabilities.

  11. Novel catalytic properties of quadruple perovskites

    PubMed Central

    Yamada, Ikuya

    2017-01-01

    ABSTRACT Quadruple perovskite oxides AA′3 B 4O12 demonstrate a rich variety of structural and electronic properties. A large number of constituent elements for A/A′/B-site cations can be introduced using the ultra-high-pressure synthesis method. Development of novel functional materials consisting of earth-abundant elements plays a crucial role in current materials science. In this paper, functional properties, especially oxygen reaction catalysis, for quadruple perovskite oxides CaCu3Fe4O12 and AMn7O12 (A = Ca, La) composed of earth-abundant elements are reviewed. PMID:28970864

  12. Enhanced magnetism of perovskite oxides, Sr(Sn,Fe)O3- δ , by substitution of nonmagnetic Ca and Ti ions

    NASA Astrophysics Data System (ADS)

    Nomura, Kiyoshi; Suzuki, Shigeyo; Mizunuma, Tomoya; Koike, Yuya; Okazawa, Atsushi

    2017-11-01

    Magnetic properties of perovskite oxides, SrSn1- x Fe x O3- δ ( x ≤ 0.15), substituted with nonmagnetic Ca and Ti ions were studied. XRD patterns showed the orthorhombic structure (close to tetragonal) of (Sr1- y Ca y )(Sn1- x Fe x )O3- δ and Sr(Sn1- x- y Fe x Ti y )O3- δ . The cell volumes decreased with the increase of Ca and Ti doping rates. Although Ti-substituted Sr(Sn, Fe)O3- δ showed small saturation magnetizations as compared with non-Ti substituted one, the magnetization increased a little with Ti doping rates up to 15%. On the other hand, all Ca-substituted Sr(Sn, Fe)O3- δ showed larger saturation magnetization than non-Ca substituted one. Two doublets of Fe3+ and a doublet of Fe4+ were observed in Mössbauer spectra of Ca-substituted Sr(Sn, Fe)O3- δ with weak ferromagnetism, and two sextets of high spin Fe3+ were additionally observed in Mössbauer spectra of Ca-doped Sr(Sn, Fe)O3- δ with relatively strong ferromagnetism. When Sr(Sn, Fe)O3- δ were further codoped with Ca and Ti ions, they showed the stable and enhanced ferromagnetic properties. It is considered that magnetic polarons among high spin Fe3+ species are overlapped by shrinking or deforming the crystal structure of perovskite oxides. That is the magnetism induced by a chemical pressure of perovskite oxides.

  13. Highly Efficient Perovskite Solar Cells with Substantial Reduction of Lead Content.

    PubMed

    Liu, Chong; Fan, Jiandong; Li, Hongliang; Zhang, Cuiling; Mai, Yaohua

    2016-10-18

    Despite organometal halide perovskite solar cells have recently exhibited a significant leap in efficiency, the Sn-based perovskite solar cells still suffer from low efficiency. Here, a series homogeneous CH 3 NH 3 Pb (1-x) Sn x I 3 (0 ≤ x ≤ 1) perovskite thin films with full coverage were obtained via solvent engineering. In particular, the intermediate complexes of PbI 2 /(SnI 2 )∙(DMSO) x were proved to retard the crystallization of CH 3 NH 3 SnI 3 , thus allowing the realization of high quality Sn-introduced perovskite thin films. The external quantum efficiency (EQE) of as-prepared solar cells were demonstrated to extend a broad absorption minimum over 50% in the wavelength range from 350 to 950 nm accompanied by a noteworthy absorption onset up to 1050 nm. The CH 3 NH 3 Pb 0.75 Sn 0.25 I 3 perovskite solar cells with inverted structure were consequently realized with maximum power conversion efficiency (PCE) of 14.12%.

  14. Light-Independent Ionic Transport in Inorganic Perovskite and Ultrastable Cs-Based Perovskite Solar Cells.

    PubMed

    Zhou, Wenke; Zhao, Yicheng; Zhou, Xu; Fu, Rui; Li, Qi; Zhao, Yao; Liu, Kaihui; Yu, Dapeng; Zhao, Qing

    2017-09-07

    Due to light-induced effects in CH 3 NH 3 -based perovskites, such as ion migration, defects formation, and halide segregation, the degradation of CH 3 NH 3 -based perovskite solar cells under maximum power point is generally implicated. Here we demonstrated that the effect of light-enhanced ion migration in CH 3 NH 3 PbI 3 can be eliminated by inorganic Cs substitution, leading to an ultrastable perovskite solar cell. Quantitatively, the ion migration barrier for CH 3 NH 3 PbI 3 is 0.62 eV under dark conditions, larger than that of CsPbI 2 Br (0.45 eV); however, it reduces to 0.07 eV for CH 3 NH 3 PbI 3 under illumination, smaller than that for CsPbI 2 Br (0.43 eV). Meanwhile, photoinduced halide segregation is also suppressed in Cs-based perovskites. Cs-based perovskite solar cells retained >99% of the initial efficiency (10.3%) after 1500 h of maximum power point tracking under AM1.5G illumination, while CH 3 NH 3 PbI 3 solar cells degraded severely after 50 h of operation. Our work reveals an uncovered mechanism for stability improvement by inorganic cation substitution in perovskite-based optoelectronic devices.

  15. Fabrication of organic-inorganic perovskite thin films for planar solar cells via pulsed laser deposition

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liang, Yangang; Zhang, Xiaohang; Gong, Yunhui

    2016-01-15

    We report on fabrication of organic-inorganic perovskite thin films using a hybrid method consisting of pulsed laser deposition (PLD) of lead iodide and spin-coating of methylammonium iodide. Smooth and highly crystalline CH{sub 3}NH{sub 3}PbI{sub 3} thin films have been fabricated on silicon and glass coated substrates with fluorine doped tin oxide using this PLD-based hybrid method. Planar perovskite solar cells with an inverted structure have been successfully fabricated using the perovskite films. Because of its versatility, the PLD-based hybrid fabrication method not only provides an easy and precise control of the thickness of the perovskite thin films, but also offersmore » a straightforward platform for studying the potential feasibility in using other metal halides and organic salts for formation of the organic-inorganic perovskite structure.« less

  16. Factors Influencing the Mechanical Properties of Formamidinium Lead Halides and Related Hybrid Perovskites.

    PubMed

    Sun, Shijing; Isikgor, Furkan H; Deng, Zeyu; Wei, Fengxia; Kieslich, Gregor; Bristowe, Paul D; Ouyang, Jianyong; Cheetham, Anthony K

    2017-10-09

    The mechanical properties of formamidinium lead halide perovskites (FAPbX 3 , X=Br or I) grown by inverse-temperature crystallization have been studied by nanoindentation. The measured Young's moduli (9.7-12.3 GPa) and hardnesses (0.36-0.45 GPa) indicate good mechanical flexibility and ductility. The effects of hydrogen bonding were evaluated by performing ab initio molecular dynamics on both formamidinium and methylammonium perovskites and calculating radial distribution functions. The structural and chemical factors influencing these properties are discussed by comparison with corresponding values in the literature for other hybrid perovskites, including double perovskites. Our results reveal that bonding in the inorganic framework and hydrogen bonding play important roles in determining elastic stiffness. The influence of the organic cation becomes more important for structures at the limit of their perovskite stability, indicated by high tolerance factors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Common variation in the ABO glycosyltransferase is associated with susceptibility to severe Plasmodium falciparum malaria

    PubMed Central

    Fry, Andrew E.; Griffiths, Michael J.; Auburn, Sarah; Diakite, Mahamadou; Forton, Julian T.; Green, Angela; Richardson, Anna; Wilson, Jonathan; Jallow, Muminatou; Sisay-Joof, Fatou; Pinder, Margaret; Peshu, Norbert; Williams, Thomas N.; Marsh, Kevin; Molyneux, Malcolm E.; Taylor, Terrie E.; Rockett, Kirk A.; Kwiatkowski, Dominic P.

    2009-01-01

    There is growing epidemiological and molecular evidence that ABO blood group affects host susceptibility to severe Plasmodium falciparum infection. The high frequency of common ABO alleles means that even modest differences in susceptibility could have a significant impact on the health of people living in malaria endemic regions. We performed an association study, the first to utilize key molecular genetic variation underlying the ABO system, genotyping >9000 individuals across 3 African populations. Using population- and family-based tests we demonstrated that alleles producing functional ABO enzymes are associated with greater risk of severe malaria phenotypes (particularly malarial anemia) in comparison with the frameshift deletion underlying blood group O: Case-control allelic odds ratio (OR) 1.2, 95% confidence interval (CI) 1.09 – 1.32, P=0.0003; Family-studies allelic OR 1.19, CI 1.08 – 1.32, P=0.001; Pooled across all studies allelic OR 1.18, CI 1.11 - 1.26, P=2×10−7. Analyzing the family trios we found suggestive evidence of a parent-of-origin effect at the ABO locus. Non-O haplotypes inherited from mothers, but not fathers, are significantly associated with severe malaria (likelihood ratio test of Weinberg, P=0.046). Finally we used HapMap data to demonstrate a region of low FST (−0.001) between the three main HapMap population groups across the ABO locus, an outlier in the empirical distribution of FST across chromosome 9 (~99.5 – 99.9th centile). This low FST region may be a signal of longstanding balancing selection at the ABO locus, caused by multiple infectious pathogens including P. falciparum. PMID:18003641

  18. Nature of potential barrier in (Ca 1/4,Cu 3/4)TiO 3 polycrystalline perovskite

    NASA Astrophysics Data System (ADS)

    Marques, V. P. B.; Bueno, P. R.; Simões, A. Z.; Cilense, M.; Varela, J. A.; Longo, E.; Leite, E. R.

    2006-04-01

    The nonohmic electrical features of (Ca 1/4,Cu 3/4)TiO 3 perovskite ceramics, which have very strong gigantic dielectric is believed originate from potential barriers at the grain boundaries. In the present study, we used the admittance and impedance spectroscopy technique to investigate (Ca 1/4,Cu 3/4)TiO 3 perovskite ceramics with low nonohmic electrical properties. The study was conducted under two different conditions: on as-sintered ceramics and on ceramics thermally treated in an oxygen-rich atmosphere. The results confirm that thermal treatment in oxygen-rich atmospheres influence the nonohmic properties. Annealing at oxygen-rich atmospheres improve the nonohmic behavior and annealing at oxygen-poor atmospheres decrease the nonohmic properties, a behavior already reported for common metal oxide nonohmic devices and here firstly evidenced for the (Ca 1/4,Cu 3/4)TiO 3 perovskite related materials. The results show that oxygen also influences the capacitance values at low frequencies, a behavior that is indicative of the Schottky-type nature of the potential barrier.

  19. Local Polar Fluctuations in Lead Halide Perovskite Crystals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.

    2017-03-01

    Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH3NH3PbBr3) and all-inorganic (CsPbBr3) leadhalide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-tohead Cs motion coupledmore » to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr3.« less

  20. Oxygen Vacancy Linear Clustering in a Perovskite Oxide

    DOE PAGES

    Eom, Kitae; Choi, Euiyoung; Choi, Minsu; ...

    2017-07-14

    Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. We report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO 3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti 2+ valence state or corresponding Ti 3d 2 electronic configuration along with divacancymore » cluster model analysis and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO 3 was verified by further X-ray diffuse scattering analysis. And because SrTiO 3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.« less

  1. Oxygen Vacancy Linear Clustering in a Perovskite Oxide

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Eom, Kitae; Choi, Euiyoung; Choi, Minsu

    Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. We report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO 3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti 2+ valence state or corresponding Ti 3d 2 electronic configuration along with divacancymore » cluster model analysis and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO 3 was verified by further X-ray diffuse scattering analysis. And because SrTiO 3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.« less

  2. Interfacial electronic structures revealed at the rubrene/CH3NH3PbI3 interface.

    PubMed

    Ji, Gengwu; Zheng, Guanhaojie; Zhao, Bin; Song, Fei; Zhang, Xiaonan; Shen, Kongchao; Yang, Yingguo; Xiong, Yimin; Gao, Xingyu; Cao, Liang; Qi, Dong-Chen

    2017-03-01

    The electronic structures of rubrene films deposited on CH 3 NH 3 PbI 3 perovskite have been investigated using in situ ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). It was found that rubrene molecules interacted weakly with the perovskite substrate. Due to charge redistribution at their interface, a downward 'band bending'-like energy shift of ∼0.3 eV and an upward band bending of ∼0.1 eV were identified at the upper rubrene side and the CH 3 NH 3 PbI 3 substrate side, respectively. After the energy level alignment was established at the rubrene/CH 3 NH 3 PbI 3 interface, its highest occupied molecular orbital (HOMO)-valence band maximum (VBM) offset was found to be as low as ∼0.1 eV favoring the hole extraction with its lowest unoccupied molecular orbital (LUMO)-conduction band minimum (CBM) offset as large as ∼1.4 eV effectively blocking the undesired electron transfer from perovskite to rubrene. As a demonstration, simple inverted planar solar cell devices incorporating rubrene and rubrene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTLs) were fabricated in this work and yielded a champion power conversion efficiency of 8.76% and 13.52%, respectively. Thus, the present work suggests that a rubrene thin film could serve as a promising hole transport layer for efficient perovskite-based solar cells.

  3. Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3d–5d double perovskite Sr₂FeOsO₆

    DOE PAGES

    Veiga, L. S. I.; Fabbris, G.; van Veenendaal, M.; ...

    2015-06-19

    The ability to tune exchange (magnetic) interactions between 3d transition metals in perovskite structures has proven to be a powerful route to discovery of novel properties. Here we demonstrate that the introduction of 3d-5d exchange pathways in double perovskites enables additional tunability, a result of the large spatial extent of 5d wave functions. Using x-ray probes of magnetism and structure at high pressure, we show that compression of Sr₂FeOsO₆ drives an unexpected continuous change in the sign of Fe-Os exchange interactions and a transition from antiferromagnetic to ferrimagnetic order. We analyze the relevant electron-electron interactions, shedding light into fundamental differencesmore » with the more thoroughly studied 3d-3d systems.« less

  4. Inorganic perovskite photocatalysts for solar energy utilization.

    PubMed

    Zhang, Guan; Liu, Gang; Wang, Lianzhou; Irvine, John T S

    2016-10-24

    The development and utilization of solar energy in environmental remediation and water splitting is being intensively studied worldwide. During the past few decades, tremendous efforts have been devoted to developing non-toxic, low-cost, efficient and stable photocatalysts for water splitting and environmental remediation. To date, several hundreds of photocatalysts mainly based on metal oxides, sulfides and (oxy)nitrides with different structures and compositions have been reported. Among them, perovskite oxides and their derivatives (layered perovskite oxides) comprise a large family of semiconductor photocatalysts because of their structural simplicity and flexibility. This review specifically focuses on the general background of perovskite and its related materials, summarizes the recent development of perovskite photocatalysts and their applications in water splitting and environmental remediation, discusses the theoretical modelling and calculation of perovskite photocatalysts and presents the key challenges and perspectives on the research of perovskite photocatalysts.

  5. Perovskite-Perovskite Homojunctions via Compositional Doping.

    PubMed

    Dänekamp, Benedikt; Müller, Christian; Sendner, Michael; Boix, Pablo P; Sessolo, Michele; Lovrincic, Robert; Bolink, Henk J

    2018-05-11

    One of the most important properties of semiconductors is the possibility of controlling their electronic behavior via intentional doping. Despite the unprecedented progress in the understanding of hybrid metal halide perovskites, extrinsic doping of perovskite remains nearly unexplored and perovskite-perovskite homojunctions have not been reported. Here we present a perovskite-perovskite homojunction obtained by vacuum deposition of stoichiometrically tuned methylammonium lead iodide (MAPI) films. Doping is realized by adjusting the relative deposition rates of MAI and PbI 2 , obtaining p-type (MAI excess) and n-type (MAI defect) MAPI. The successful stoichiometry change in the thin films is confirmed by infrared spectroscopy, which allows us to determine the MA content in the films. We analyzed the resulting thin-film junction by cross-sectional scanning Kelvin probe microscopy (SKPM) and found a contact potential difference (CPD) of 250 mV between the two differently doped perovskite layers. Planar diodes built with the perovskite-perovskite homojunction show the feasibility of our approach for implementation in devices.

  6. Strong excitonic interactions in the oxygen K-edge of perovskite oxides.

    PubMed

    Tomita, Kota; Miyata, Tomohiro; Olovsson, Weine; Mizoguchi, Teruyasu

    2017-07-01

    Excitonic interactions of the oxygen K-edge electron energy-loss near-edge structure (ELNES) of perovskite oxides, CaTiO 3 , SrTiO 3 , and BaTiO 3 , together with reference oxides, MgO, CaO, SrO, BaO, and TiO 2 , were investigated using a first-principles Bethe-Salpeter equation calculation. Although the transition energy of oxygen K-edge is high, strong excitonic interactions were present in the oxygen K-edge ELNES of the perovskite oxides, whereas the excitonic interactions were negligible in the oxygen K-edge ELNES of the reference compounds. Detailed investigation of the electronic structure suggests that the strong excitonic interaction in the oxygen K-edge ELNES of the perovskite oxides is caused by the directionally confined, low-dimensional electronic structure at the Ti-O-Ti bonds. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Constructing Efficient and Stable Perovskite Solar Cells via Interconnecting Perovskite Grains.

    PubMed

    Hou, Xian; Huang, Sumei; Ou-Yang, Wei; Pan, Likun; Sun, Zhuo; Chen, Xiaohong

    2017-10-11

    A high-quality perovskite film with interconnected perovskite grains was obtained by incorporating terephthalic acid (TPA) additive into the perovskite precursor solution. The presence of TPA changed the crystallization kinetics of the perovskite film and promoted lateral growth of grains in the vicinity of crystal boundaries. As a result, sheet-shaped perovskite was formed and covered onto the bottom grains, which made some adjacent grains partly merge together to form grains-interconnected perovskite film. Perovskite solar cells (PSCs) with TPA additive exhibited a power conversion efficiency (PCE) of 18.51% with less hysteresis, which is obviously higher than that of pristine cells (15.53%). PSCs without and with TPA additive retain 18 and 51% of the initial PCE value, respectively, aging for 35 days exposed to relative humidity 30% in air without encapsulation. Furthermore, MAPbI 3 film with TPA additive shows superior thermal stability to the pristine one under 100 °C baking. The results indicate that the presence of TPA in perovskite film can greatly improve the performance of PSCs as well as their moisture resistance and thermal stability.

  8. Frequencies and ethnic distribution of ABO and RhD blood groups in China: a population-based cross-sectional study.

    PubMed

    Liu, Jue; Zhang, Shikun; Wang, Qiaomei; Shen, Haiping; Zhang, Yiping; Liu, Min

    2017-12-03

    ABO and RhD blood groups are key factors affecting blood transfusion safety. The distribution of ABO and RhD blood groups varies globally, but limited data exist for ethnic distributions of these blood groups in Asian populations. We aimed to evaluate the distribution of ABO and RhD blood groups among Chinese ethnic groups. A population-based cross-sectional study. Data on ABO groups and ethnicities were obtained from the National Free Preconception Health Examination Project (NFPHEP) with participants from 220 counties of 31 provinces in China PARTICIPANTS: There were 3 832 034 participants aged 21-49 years who took part in the NFPHEP from January 2010 to December 2012 and were included in this study. The proportion of ABO and RhD blood groups among different ethnic groups was calculated. ABO and RhD blood distribution was significantly different among nine ethnic groups (P<0.001). Compared with other ethnic groups, the Yi group had more A phenotypes (34.0%), and the Manchu (33.7%) and Mongolian (33.3%) ethnic groups had more B phenotypes. The Zhuang group had the greatest proportion of O phenotypes (41.8%), followed by the Miao group (37.7%). AB phenotypes were more frequent in the Uygur ethnic group (10.6%) but lower in the Zhuang group (5.5%). Meanwhile, RhD negativity (RhD-) was greater in the Uygur group (3.3%) than in the Mongolian (0.3%) and Manchu ethnic groups (0.4%). O RhD- blood groups were more frequent in the Uygur group (0.8%) than in the other ethnic groups (0.1%-0.4%, P<0.001). ABO and RhD blood phenotypes vary across different ethnic groups in China. The diversity in the distribution of the ABO and RhD blood groups in different ethnic groups should be considered when developing rational and evidence-based strategies for blood collection and management. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  9. Perovskite solar cells: from materials to devices.

    PubMed

    Jung, Hyun Suk; Park, Nam-Gyu

    2015-01-07

    Perovskite solar cells based on organometal halide light absorbers have been considered a promising photovoltaic technology due to their superb power conversion efficiency (PCE) along with very low material costs. Since the first report on a long-term durable solid-state perovskite solar cell with a PCE of 9.7% in 2012, a PCE as high as 19.3% was demonstrated in 2014, and a certified PCE of 17.9% was shown in 2014. Such a high photovoltaic performance is attributed to optically high absorption characteristics and balanced charge transport properties with long diffusion lengths. Nevertheless, there are lots of puzzles to unravel the basis for such high photovoltaic performances. The working principle of perovskite solar cells has not been well established by far, which is the most important thing for understanding perovksite solar cells. In this review, basic fundamentals of perovskite materials including opto-electronic and dielectric properties are described to give a better understanding and insight into high-performing perovskite solar cells. In addition, various fabrication techniques and device structures are described toward the further improvement of perovskite solar cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Al2 O3 Underlayer Prepared by Atomic Layer Deposition for Efficient Perovskite Solar Cells.

    PubMed

    Zhang, Jinbao; Hultqvist, Adam; Zhang, Tian; Jiang, Liangcong; Ruan, Changqing; Yang, Li; Cheng, Yibing; Edoff, Marika; Johansson, Erik M J

    2017-10-09

    Perovskite solar cells, as an emergent technology for solar energy conversion, have attracted much attention in the solar cell community by demonstrating impressive enhancement in power conversion efficiencies. However, the high temperature and manually processed TiO 2 underlayer prepared by spray pyrolysis significantly limit the large-scale application and device reproducibility of perovskite solar cells. In this study, lowtemperature atomic layer deposition (ALD) is used to prepare a compact Al 2 O 3 underlayer for perovskite solar cells. The thickness of the Al 2 O 3 layer can be controlled well by adjusting the deposition cycles during the ALD process. An optimal Al 2 O 3 layer effectively blocks electron recombination at the perovskite/fluorine-doped tin oxide interface and sufficiently transports electrons through tunneling. Perovskite solar cells fabricated with an Al 2 O 3 layer demonstrated a highest efficiency of 16.2 % for the sample with 50 ALD cycles (ca. 5 nm), which is a significant improvement over underlayer-free PSCs, which have a maximum efficiency of 11.0 %. Detailed characterization confirms that the thickness of the Al 2 O 3 underlayer significantly influences the charge transfer resistance and electron recombination processes in the devices. Furthermore, this work shows the feasibility of using a high band-gap semiconductor such as Al 2 O 3 as the underlayer in perovskite solar cells and opens up pathways to use ALD Al 2 O 3 underlayers for flexible solar cells. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Atomically thin two-dimensional organic-inorganic hybrid perovskites.

    PubMed

    Dou, Letian; Wong, Andrew B; Yu, Yi; Lai, Minliang; Kornienko, Nikolay; Eaton, Samuel W; Fu, Anthony; Bischak, Connor G; Ma, Jie; Ding, Tina; Ginsberg, Naomi S; Wang, Lin-Wang; Alivisatos, A Paul; Yang, Peidong

    2015-09-25

    Organic-inorganic hybrid perovskites, which have proved to be promising semiconductor materials for photovoltaic applications, have been made into atomically thin two-dimensional (2D) sheets. We report the solution-phase growth of single- and few-unit-cell-thick single-crystalline 2D hybrid perovskites of (C4H9NH3)2PbBr4 with well-defined square shape and large size. In contrast to other 2D materials, the hybrid perovskite sheets exhibit an unusual structural relaxation, and this structural change leads to a band gap shift as compared to the bulk crystal. The high-quality 2D crystals exhibit efficient photoluminescence, and color tuning could be achieved by changing sheet thickness as well as composition via the synthesis of related materials. Copyright © 2015, American Association for the Advancement of Science.

  12. Anisotropic plasticity of MgSiO3 post-perovskite from atomic scale modeling

    NASA Astrophysics Data System (ADS)

    Goryaeva, Alexandra; Carrez, Philippe; Cordier, Patrick

    2016-04-01

    In contrast to the lower mantle, the D″ layer exhibits significant seismic anisotropy both at the global and local scale [1]. Located right above the CMB, the D'' represents a very complex region and the causes of its pronounced anisotropy are still debated (CPO, oriented inclusions, layering, thermo-chemical heterogeneities etc). Among them, contribution of the post-perovskite rheology is commonly considered to be substantial. However, for this high-pressure phase, information about mechanical properties, probable slip systems, dislocations and their behavior under stress are still extremely challenging to obtain directly from experiments [3, 4]. Thus, we propose employing full atomistic modeling (based on the pairwise potential previously derived by [2]) to access the ability of MgSiO3 post-perovskite to deform by dislocation glide at 120 GPa. Lattice friction opposed to the dislocation glide in MgSiO3 post-perovskite is shown to be highly anisotropic. Thus, remarkably low values of Peierls stress (1 GPa) are found for the glide of [100] screw dislocations in (010), while glide in (001) requires almost 18 times larger stress values. In general, (010) plane is characterized by the lowest lattice friction which suggests (010) deformation textures. Comparison of our results with previous study of MgSiO3 perovskite (bridgmanite) [5], based on similar simulation approach, clearly shows that monotonous increase in Peierls stress of bridgmanite will be followed by a dramatic drop after the phase transition to the post-perovskite phase, which consequently suggests the D'' located at the CMB to be weaker than the overlying mantle. In addition to that, the observed evolution of CRSS with temperature clearly demonstrates that post-perovskite deforms in the athermal regime which backs up it to be a very weak phase and indicates its deformation by dislocation glide in contrast to high-lattice friction perovskite (bridgmanite) phase deformed by climb only. References [1

  13. ABO-incompatible heart transplants.

    PubMed

    Hageman, M; Michaud, N; Chinnappan, I; Klein, T; Mettler, B

    2015-04-01

    A month-old baby girl with blood type O positive received a donor heart organ from a donor with blood type B. This was the first institutional ABO-incompatible heart transplant. Infants listed for transplantation may be considered for an ABO-incompatible heart transplant based on their antibody levels and age. The United Network of Organ Sharing (UNOS) protocol is infants under 24 months with titers less than or equal to 1:4.(1) This recipient's anti-A and anti-B antibodies were monitored with titer assays to determine their levels; antibody levels less than 1:4 are acceptable pre-transplant in order to proceed with donor and transplant arrangements.1 Immediately prior to initiating cardiopulmonary bypass (CPB), a complete whole body exchange transfusion of at least two-times the patient's circulating blood volume was performed with packed red blood cells (pRBC), fresh frozen plasma (FFP) and 25% albumin. Titer assays were sent two minutes after initiation of full CPB and then hourly until the cross-clamp was removed. Institutionally, reperfusion of the donor heart is not restored until the antibody level from the titer assay is known and reported as less than 1:4; failing to achieve an immulogically tolerant recipient will provide conditions for hyperacute rejection. The blood collected during the transfusion exchange was immediately processed through a cell saver so the pRBC's could be re-infused to the patient during CPB, as necessary. The remainder of the transplant was performed in the same fashion as an ABO-compatible heart transplant. The patient has shown no signs of rejection following transplantation. © The Author(s) 2014.

  14. The thermal expansion of ScAlO3 — A silicate perovskite analogue

    NASA Astrophysics Data System (ADS)

    Hill, R. J.; Jackson, Ian

    1990-01-01

    The crystal structure of ScAlO3 has been refined at temperatures up to 1100° C on the basis of x-ray powder diffraction data. The thermal expansion is adequately described by a Grüneisen-Debye model with the elastic Debye temperature and an effective Grüneisen parameter of 1.6. The volumetric thermal expansion of 3.0% between 10 and 1100° C, corresponding to a mean thermal expansion coefficient of 2.7 × 10-5 K-1, is entirely attributable to the expansion of the AlO6 octahedra. The interoctahedral angles, though not fixed by symmetry, do not vary significantly with temperature —indicating that the expansivities of the constituent AlO6 and distorted ScO8 polyhedra are well matched. Similar considerations of polyhedral expansivity suggest thermal expansion coefficients of ˜2 × 10-5K-1 for cubic CaSiO3 perovskite and a value between 2 × 10-5 K-1 and 4 × 10-5 K-1 for MgSiO3 perovskite. The lower value is consistent with the reconnaissance measurements for Mg0.9Fe0.1SiO3 (Knittle et al. 1986) below 350° C, with low-temperature measurements of single-crystal MgSiO3 (Ross and Hazen 1989), and with the results of some recent calculations. The markedly greater expansivity ˜4 × 10-5 K-1 measured at higher temperatures (350 570° C) by Knittle et al. is inconsistent with the simple Grüneisen-Debye quasiharmonic model and may reflect the marginal metastability of the orthorhombic perovskite phase. Under these circumstances, extrapolation of the measured expansivity is hazardous and may result in the under-estimation of lower mantle densities and the drawing of inappropriate inferences concerning the need for chemical stratification of the Earth's mantle.

  15. Tailored Engineering of an Unusual (C4 H9 NH3 )2 (CH3 NH3 )2 Pb3 Br10 Two-Dimensional Multilayered Perovskite Ferroelectric for a High-Performance Photodetector.

    PubMed

    Li, Lina; Sun, Zhihua; Wang, Peng; Hu, Weida; Wang, Sasa; Ji, Chengmin; Hong, Maochun; Luo, Junhua

    2017-09-25

    Two-dimensional (2D) layered hybrid perovskites have shown great potential in optoelectronics, owing to their unique physical attributes. However, 2D hybrid perovskite ferroelectrics remain rare. The first hybrid ferroelectric with unusual 2D multilayered perovskite framework, (C 4 H 9 NH 3 ) 2 (CH 3 NH 3 ) 2 Pb 3 Br 10 (1), has been constructed by tailored alloying of the mixed organic cations into 3D prototype of CH 3 NH 3 PbBr 3 . Ferroelectricity is created through molecular reorientation and synergic ordering of organic moieties, which are unprecedented for the known 2D multilayered hybrid perovskites. Single-crystal photodetectors of 1 exhibit fascinating performances, including extremely low dark currents (ca. 10 -12  A), large on/off current ratios (ca. 2.5×10 3 ), and very fast response rate (ca. 150 μs). These merits are superior to integrated detectors of other 2D perovskites, and compete with the most active CH 3 NH 3 PbI 3 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Structure and interstitial iodide migration in hybrid perovskite methylammonium lead iodide

    NASA Astrophysics Data System (ADS)

    Minns, J. L.; Zajdel, P.; Chernyshov, D.; van Beek, W.; Green, M. A.

    2017-05-01

    Hybrid perovskites form an emerging family of exceptional light harvesting compounds. However, the mechanism underpinning their photovoltaic effect is still far from understood, which is impeded by a lack of clarity on their structures. Here we show that iodide ions in the methylammonium lead iodide migrate via interstitial sites at temperatures above 280 K. This coincides with temperature dependent static distortions resulting in pseudocubic local symmetry. Based on bond distance analysis, the migrating and distorted iodines are at lengths consistent with the formation of I2 molecules, suggesting a 2I--->I2+2e- redox couple. The actual formula of this compound is thus (CH3NH3)PbI3-2x(I2)x where x~0.007 at room temperature. A crucial feature of the tetragonal structure is that the methylammonium ions do not sit centrally in the A-site cavity, but disordered around two off-centre orientations that facilitate the interstitial ion migration via a gate opening mechanism.

  17. First principles study of structural, electronic and optical properties of perovskites CaZrO3 and CaHfO3 in cubic phase

    NASA Astrophysics Data System (ADS)

    Hoat, D. M.; Silva, J. F. Rivas; Blas, A. Méndez

    2018-07-01

    In this work, we present the first principles calculations for structural, electronic and optical properties of perovskites CaZrO3 and CaHfO3 using the full-potential linearized augmented plane wave method (FP-LAPW) within the framework of density functional theory (DFT) as implemented in WIEN2k package. The exchange-correlation potential is treated with local density approximation (LDA) and generalized gradient approximation (GGA-PBE and PBESol). Additionally, the Tran Blaha modified Becke-Johnson exchange potential (mBJ) also is employed for electronic and optical calculations due to that it gives very accurate band gap of solids. Our obtained structural parameters are in good agreement with experimental datas and other theoretical results. The energy band gap obtained with mBJ is 4.56 eV for CaZrO3 and 5.27 eV for CaHfO3. The hybridization of states of O atom with those of Zr and Hf atoms in CaZrO3 and CaHfO3, respectively, is observed. The spin-orbit coupling effect on electronic properties of considered compounds also is investigated. Finally, the linear optical properties of CaZrO3 and CaHfO3 are derived from their complex dielectric function calculated with mBJ potential for wide energy range up to 45 eV, and all of them analyzed in details.

  18. Retrospective analysis of forward and reverse ABO typing discrepancies among patients and blood donors in a tertiary care hospital.

    PubMed

    Makroo, R N; Kakkar, B; Agrawal, S; Chowdhry, M; Prakash, B; Karna, P

    2018-01-12

    The aim of our study was to determine the incidence and causes of ABO typing discrepancies among patients and blood donors at our centre. An accurate interpretation of the ABO blood group of an individual is of utmost importance to ensure patient safety and good transfusion practices. A retrospective observational study was carried out in the Department of Transfusion Medicine in our hospital from March 2013 to December 2015. Records of all patient and blood donor samples were retrieved and analysed for ABO typing discrepancies. In total, 135 853 patient and 62 080 donor samples were analysed for ABO typing discrepancies. The incidence among patients and blood donors was found to be 0·1% (138/135853) and 0·02% (14/62080), respectively. The mean age for patients and blood donors was 48·4 and 29·2 years, respectively. The most common cause of ABO typing discrepancies was due to cold autoantibodies among the patients (50·7%) and blood donors (57%) causing discrepant results in reverse typing. The various other causes of reverse typing discrepancies among patients were weak/missing antibody (25·4%), cold-reacting alloantibody (4·3%), warm autoantibody (2·2%), anti-A1 antibody (2·2%), Bombay phenotype (1·5%), transplantation (0·7%) and rouleaux (0·7%), whereas in blood donors, the causes were cold-reacting antibody (7%) and weak antibody (7%). The major cause of forward typing discrepancies among patients (12·3%) and blood donors (29%) was ABO subgroups. The resolution of ABO typing discrepancy is essential to minimise the chance of transfusion of ABO-incompatible blood. © 2018 British Blood Transfusion Society.

  19. Exceptional Morphology-Preserving Evolution of Formamidinium Lead Triiodide Perovskite Thin Films via Organic-Cation Displacement

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhou, Yuanyuan; Yang, Mengjin; Pang, Shuping

    Here we demonstrate a radically different chemical route for the creation of HC(NH2)2PbI3 (FAPbI3) perovskite thin films. This approach entails a simple exposure of as-synthesized CH3NH3PbI3 (MAPbI3) perovskite thin films to HC(=NH)NH2 (formamidine or FA) gas at 150 degrees C, which leads to rapid displacement of the MA+ cations by FA+ cations in the perovskite structure. The resultant FAPbI3 perovskite thin films preserve the microstructural morphology of the original MAPbI3 thin films exceptionally well. Importantly, the myriad processing innovations that have led to the creation of high-quality MAPbI3 perovskite thin films are directly adaptable to FAPbI3 through this simple, rapidmore » chemical-conversion route. Accordingly, we show that efficiencies of perovskite solar cells fabricated with FAPbI3 thin films created using this route can reach -18%.« less

  20. Curtailing Perovskite Processing Limitations via Lamination at the Perovskite/Perovskite Interface

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Van Hest, Marinus F; Moore, David; Klein, Talysa

    Standard layer-by-layer solution processing methods constrain lead-halide perovskite device architectures. The layer below the perovskite must be robust to the strong organic solvents used to form the perovskite while the layer above has a limited thermal budget and must be processed in nonpolar solvents to prevent perovskite degradation. To circumvent these limitations, we developed a procedure where two transparent conductive oxide/transport material/perovskite half stacks are independently fabricated and then laminated together at the perovskite/perovskite interface. Using ultraviolet-visible absorption spectroscopy, external quantum efficiency, X-ray diffraction, and time-resolved photoluminesence spectroscopy, we show that this procedure improves photovoltaic properties of the perovskite layer.more » Applying this procedure, semitransparent devices employing two high-temperature oxide transport layers were fabricated, which realized an average efficiency of 9.6% (maximum: 10.6%) despite series resistance limitations from the substrate design. Overall, the developed lamination procedure curtails processing constraints, enables new device designs, and affords new opportunities for optimization.« less

  1. Genetic and mechanistic evaluation for the mixed-field agglutination in B3 blood type with IVS3+5G>A ABO gene mutation.

    PubMed

    Chen, Ding-Ping; Tseng, Ching-Ping; Wang, Wei-Ting; Sun, Chien-Feng

    2012-01-01

    The ABO blood type B(3) is the most common B subtype in the Chinese population with a frequency of 1/900. Although IVS3+5G>A (rs55852701) mutation of B gene has been shown to associate with the development of B(3) blood type, genetic and mechanistic evaluation for the unique mixed-field agglutination phenotype has not yet been completely addressed. In this study, we analyzed 16 cases of confirmed B(3) individuals and found that IVS3+5G>A attributes to all cases of B(3). RT-PCR analyses revealed the presence of at least 7 types of aberrant B(3) splicing transcripts with most of the transcripts causing early termination and producing non-functional protein during translation. The splicing transcript without exon 3 that was predicted to generate functional B(3) glycosyltransferase lacking 19 amino acids at the N-terminal segment constituted only 0.9% of the splicing transcripts. Expression of the B(3) cDNA with exon 3 deletion in the K562 erythroleukemia cells revealed that the B(3) glycosyltransferase had only 40% of B(1) activity in converting H antigen to B antigen. Notably, the typical mixed-field agglutination of B(3)-RBCs can be mimicked by adding anti-B antibody to the K562-B(3) cells. This study thereby demonstrates that both aberrant splicing of B transcripts and the reduced B(3) glycosyltransferase activity contribute to weak B expression and the mixed-field agglutination of B(3), adding to the complexity for the regulatory mechanisms of ABO gene expression.

  2. Outcome of ABO-incompatible adult living-donor liver transplantation for patients with hepatocellular carcinoma.

    PubMed

    Yoon, Young-In; Song, Gi-Won; Lee, Sung-Gyu; Hwang, Shin; Kim, Ki-Hun; Kim, Seok-Hwan; Kang, Woo-Hyoung; Cho, Hwui-Dong; Jwa, Eun-Kyoung; Kwon, Jae-Hyun; Tak, Eun-Young; Kirchner, Varvara A

    2018-06-01

    Living-donor liver transplantation (LDLT) can simultaneously cure hepatocellular carcinoma (HCC) and underlying liver cirrhosis, improving long-term results in patients with HCC. ABO-incompatible LDLT could expand the living-donor pool, reduce waiting times for deceased-donor liver transplantation, and improve long-term survival for some patients with HCC. We retrospectively reviewed the medical records of patients undergoing LDLT for HCC from November 2008 to December 2015 at a single institution in Korea. In total, 165 patients underwent ABO-incompatible and 753 patients underwent ABO-compatible LDLT for HCC. ABO-incompatible recipients underwent desensitization to overcome the ABO blood group barrier, including pretransplant plasma exchange and rituximab administration (300-375 mg/m 2 /body surface area). We performed 1:1 propensity score matching and included 165 patients in each group. 82.4% of ABO-incompatible and 83.0% of -compatible LDLT groups had HCC within conventional Milan criteria, respectively, and 92.1% and 92.7% of patients in each group had a Child-Pugh score of A or B. ABO-incompatible and -compatible LDLT groups were followed up for 48.0 and 48.7 months, respectively, with both groups showing comparable recurrence-free survival rates (hazard ratio [HR] 1.14; 95% CI 0.68-1.90; p = 0.630) and overall patient-survival outcomes (HR 1.10; 95% CI 0.60-2.00; p = 0.763). These findings suggested that ABO-incompatible liver transplantation is a feasible option for patients with HCC, especially for those with compensated cirrhosis with HCC within conventional Milan criteria. Despite hypothetical immunological concerns that the desensitization protocol for breaking through the ABO blood group barrier might have a negative impact on the recurrence of hepatocellular carcinoma, our experience demonstrated no significant differences in the long-term overall survival and recurrence-free survival rates between patients receiving ABO-compatible or ABO

  3. In-situ measurement of texture development rate in CaIrO 3 post-perovskite

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hunt, Simon A.; Walker, Andrew M.; Mariani, Elisabetta

    The rate of crystallographic preferred orientation (CPO) development during deformation of post-perovskite is crucial in interpreting seismic anisotropy in the lowermost mantle but the stability field of MgSiO 3 post-perovskite prevents high-strain deformation experiments being performed on it. Therefore, to constrain the rate of CPO development in post-perovskite, we deformed CaIrO 3, a low-pressure analogue of MgSiO 3 post-perovskite, in simple shear at 3.2 GPa and 400 °C to a shear strain (γ) of 0.81. From X-ray diffraction patterns acquired during deformation, we invert for CPO as a function of strain. By comparing the CPO that develops with visco-plastic self-consistentmore » (VPSC) models we constrain the critical resolved shear stresses (CRSS) of the non-primary slip-systems in CaIrO 3 to be of order 6 times stronger than the primary [100] (010) slip system. This value is significantly less than has been assumed by previous studies and if applicable to MgSiO 3 implies that seismic anisotropy in the D" layer develops slower than has previously been assumed.« less

  4. Calcium doped MAPbI3 with better energy state alignment in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Lu, Chaojie; Zhang, Jing; Hou, Dagang; Gan, Xinlei; Sun, Hongrui; Zeng, Zhaobing; Chen, Renjie; Tian, Hui; Xiong, Qi; Zhang, Ying; Li, Yuanyuan; Zhu, Yuejin

    2018-05-01

    The organic-inorganic perovskite material with better energy alignment in the solar cell device will have a profound impact on the solar cell performance. It is valuable to tune the energy states by element substitution and doping in perovskites. Here, we present that Ca2+ is incorporated into CH3NH3PbI3, which up-shifts the valence band maximum and the conduction band minimum, leading to a difference between the bandgap and the Fermi level in the device. Consequently, Ca2+ incorporation results in an enhancement of the photovoltage and photocurrent, achieving a summit efficiency of 18.3% under standard 1 sun (AM 1.5). This work reveals the doped perovskite to improve the solar cell performance by tuning the energy state.

  5. Local polar fluctuations in lead halide perovskite crystals

    DOE PAGES

    Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; ...

    2017-03-28

    Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH 3NH 3PbBr 3) and all-inorganic (CsPbBr 3) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. Furthermore, MD simulations indicatemore » that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr 3.« less

  6. Thorough analysis of unorthodox ABO deletions called by the 1000 Genomes project.

    PubMed

    Möller, M; Hellberg, Å; Olsson, M L

    2018-02-01

    ABO remains the clinically most important blood group system, but despite earlier extensive research, significant findings are still being made. The vast majority of catalogued ABO null alleles are based on the c.261delG polymorphism. Apart from c.802G>A, other mechanisms for O alleles are rare. While analysing the data set from the 1000 Genomes (1000G) project, we encountered two previously uncharacterized deletions, which needed further exploration. The Erythrogene database, complemented with bioinformatics software, was used to analyse ABO in 2504 individuals from 1000G. DNA samples from selected 1000G donors and African blood donors were examined by allele-specific PCR and Sanger sequencing to characterize predicted deletions. A 5821-bp deletion encompassing exons 5-7 was called in twenty 1000G individuals, predominantly Africans. This allele was confirmed and its exact deletion point defined by bioinformatic analyses and in vitro experiments. A PCR assay was developed, and screening of African samples revealed three donors heterozygous for this deletion, which was thereby phenotypically established as an O allele. Analysis of upstream genetic markers indicated an ancestral origin from ABO*O.01.02. We estimate this deletion as the 3rd most common mechanism behind O alleles. A 24-bp deletion was called in nine individuals and showed greater diversity regarding ethnic distribution and allelic background. It could neither be confirmed by in silico nor in vitro experiments. A previously uncharacterized ABO deletion among Africans was comprehensively mapped and a genotyping strategy devised. The false prediction of another deletion emphasizes the need for cautious interpretation of NGS data and calls for strict validation routines. © 2017 International Society of Blood Transfusion.

  7. ABO blood groups, Rhesus factor, and anaphylactic reactions due to Hymenoptera stings.

    PubMed

    Pałgan, Krzysztof; Bartuzi, Zbigniew; Chrzaniecka, Elżbieta

    2017-09-21

    Numerous publications indicate that the prevalence of some infectious, neoplastic and immunological diseases are associated with ABO blood groups. The aim of this study was to verify whether ABO and Rh blood groups are associated with severe anaphylactic reactions after Hymenoptera stings. A study was undertaken of 71,441 Caucasian subjects living in the same geographic area. The study group included 353 patients with diagnosed systemic anaphylaxis to Hymenoptera venom. Control group included 71,088 healthy blood donors. Frequencies of ABO and Rhesus groups in the study and control groups were compared using univariate and multivariate analyses. No statistically significant interactions were observed between the ABO blood group and anaphylactic reactions to Hymenoptera.

  8. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

    DOE PAGES

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; ...

    2016-06-13

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less

  9. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less

  10. Phase transitions of BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} perovskite-type oxides under reducing environments

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Rodríguez, G.C.Mondragón, E-mail: guillermo.mondragon-rodriguez@dlr.de; Gönüllü, Y.; Ferri, Davide

    2015-01-15

    Highlights: • Solid solution formation BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} with a new wet chemical synthesis method. • Rhodium in the BaTiO{sub 3} perovskite stabilizes the hexagonal structure. • New Rh segregation mechanism for hexagonal BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} upon reduction. - Abstract: Perovskite-type oxides of composition BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} were prepared following a new chemical route that avoids the formation of hydroxyl species and precipitation, and allows the homogeneous distribution of Rh in the final mixed metal oxide. The high dispersion of Rh and the formation of the solid solution between Rh and the BaTiO{sub 3} perovskite is confirmedmore » by means of X-ray diffraction (XRD) and extended X-ray absorption fine structure spectroscopy (EXAFS). The presence of Rh stabilized the hexagonal BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} phase, which decomposes into barium orthotitanate (BaTi{sub 2}O{sub 4}) and metallic Rh° in reducing environment. This phase transition starts already at 700 °C and is only partially completed at 900 °C suggesting that part of the Rh present in the perovskite lattice might not be easily reduced by hydrogen. These aspects and further open questions are discussed.« less

  11. Synthesis, structures, and phase transitions of barium bismuth iridium oxide perovskites Ba{sub 2}BiIrO{sub 6} and Ba{sub 3}BiIr{sub 2}O{sub 9}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ling, Chris D., E-mail: c.ling@chem.usyd.edu.a; Bragg Institute, ANSTO, PMB 1, Menai 2234; Kennedy, Brendan J.

    The Ba-Bi-Ir-O system is found to contain two distinct perovskite-type phases: a rock-salt ordered double perovskite Ba{sub 2}BiIrO{sub 6}; and a 6H-type hexagonal perovskite Ba{sub 3}BiIr{sub 2}O{sub 9}. Ba{sub 2}BiIrO{sub 6} undergoes a series of symmetry-lowering phase transitions on cooling Fm3-barm->R3-barc->12/m(C2/m)->I1-bar(P1-bar), all of which are second order except the rhombohedral->monoclinic one, which is first order. The monoclinic phase is only observed in a 2-phase rhombohedral+monoclinic regime. The transition and 2-phase region lie very close to 300 K, making the room-temperature X-ray diffraction patterns extremely complex and potentially explaining why Ba{sub 2}BiIrO{sub 6} had not previously been identified and reported. Amore » solid solution Ba{sub 2}Bi{sub 1+x}Ir{sub 1-x}O{sub 6}, analogous to Ba{sub 2}Bi{sub 1+x}Ru{sub 1-x}O{sub 6}, 0<=x<=2/3, was not observed. The 6H-type phase Ba{sub 3}BiIr{sub 2}O{sub 9} undergoes a clean second-order phase transition P6{sub 3}/mmc->C2/c at 750 K, unlike 6H-type Ba{sub 3}LaIr{sub 2}O{sub 9}, the P6{sub 3}/mmc structure of which is highly strained below {approx}750 K but fails to distort coherently to the monoclinic phase. - Graphical abstract: Structure of Ba{sub 3}BiIr{sub 2}O{sub 9} at 300 K. BiO{sub 6} octahedra are purple, IrO{sub 6} octahedra are gold, and Ba atoms are green. Thermal ellipsoids at 90% probability.« less

  12. Arctic Boreal Vulnerability Experiment (ABoVE) Science Cloud

    NASA Astrophysics Data System (ADS)

    Duffy, D.; Schnase, J. L.; McInerney, M.; Webster, W. P.; Sinno, S.; Thompson, J. H.; Griffith, P. C.; Hoy, E.; Carroll, M.

    2014-12-01

    The effects of climate change are being revealed at alarming rates in the Arctic and Boreal regions of the planet. NASA's Terrestrial Ecology Program has launched a major field campaign to study these effects over the next 5 to 8 years. The Arctic Boreal Vulnerability Experiment (ABoVE) will challenge scientists to take measurements in the field, study remote observations, and even run models to better understand the impacts of a rapidly changing climate for areas of Alaska and western Canada. The NASA Center for Climate Simulation (NCCS) at the Goddard Space Flight Center (GSFC) has partnered with the Terrestrial Ecology Program to create a science cloud designed for this field campaign - the ABoVE Science Cloud. The cloud combines traditional high performance computing with emerging technologies to create an environment specifically designed for large-scale climate analytics. The ABoVE Science Cloud utilizes (1) virtualized high-speed InfiniBand networks, (2) a combination of high-performance file systems and object storage, and (3) virtual system environments tailored for data intensive, science applications. At the center of the architecture is a large object storage environment, much like a traditional high-performance file system, that supports data proximal processing using technologies like MapReduce on a Hadoop Distributed File System (HDFS). Surrounding the storage is a cloud of high performance compute resources with many processing cores and large memory coupled to the storage through an InfiniBand network. Virtual systems can be tailored to a specific scientist and provisioned on the compute resources with extremely high-speed network connectivity to the storage and to other virtual systems. In this talk, we will present the architectural components of the science cloud and examples of how it is being used to meet the needs of the ABoVE campaign. In our experience, the science cloud approach significantly lowers the barriers and risks to organizations

  13. Tuning the band gap in hybrid tin iodide perovskite semiconductors using structural templating.

    PubMed

    Knutson, Jeremy L; Martin, James D; Mitzi, David B

    2005-06-27

    Structural distortions within the extensive family of organic/inorganic hybrid tin iodide perovskite semiconductors are correlated with their experimental exciton energies and calculated band gaps. The extent of the in- and out-of-plane angular distortion of the SnI4(2-) perovskite sheets is largely determined by the relative charge density and steric requirements of the organic cations. Variation of the in-plane Sn-I-Sn bond angle was demonstrated to have the greatest impact on the tuning of the band gap, and the equatorial Sn-I bond distances have a significant secondary influence. Extended Hückel tight-binding band calculations are employed to decipher the crystal orbital origins of the structural effects that fine-tune the band structure. The calculations suggest that it may be possible to tune the band gap by as much as 1 eV using the templating influence of the organic cation.

  14. Relative Risks of Thrombosis and Bleeding in Different ABO Blood Groups.

    PubMed

    Franchini, Massimo; Lippi, Giuseppe

    2016-03-01

    The ABO blood group system is composed of complex carbohydrate molecules (i.e., the A, B, and H determinants) that are widely expressed on the surface of red blood cells and in a variety of other cell and tissues. Along with their pivotal role in transfusion and transplantation medicine, the ABO antigens participate in many other physiological processes and, in particular, are important determinants of von Willebrand factor and factor VIII circulating plasma levels. The precise influence of the ABO system on hemostasis has led the way to the investigation of a putative implication in the risk of developing cardiovascular disorders. Along with the underlying molecular mechanisms, the current knowledge on the role of ABO blood group antigens in both the thrombotic and hemorrhagic risk will be summarized in this narrative review. Thieme Medical Publishers 333 Seventh Avenue, New York, NY 10001, USA.

  15. A and B antigen levels acquired by group O donor-derived erythrocytes following ABO-non-identical transfusion or minor ABO-incompatible haematopoietic stem cell transplantation.

    PubMed

    Hult, A K; Dykes, J H; Storry, J R; Olsson, M L

    2017-06-01

    ABO-incompatible haematopoietic stem cell transplantation (HSCT) presents a challenge to blood component transfusion. The aim of this study was to investigate the weak blood group A or B antigen expression by donor-derived group O red blood cells (RBC) observed following transfusion or minor ABO-incompatible HSCT. In addition, in vitro experiments were performed to elucidate possible mechanisms underlying this phenomenon. A sensitive flow cytometry assay for the semi-quantification of RBC A/B antigen levels was used to assess patient samples and evaluate in vitro experiments. Analysis of blood samples from patients, originally typed as A, B and AB but recently transplanted or transfused with cells from group O donors, revealed the A antigen expression on donor-derived RBC, ranging from very low levels in non-secretor individuals to almost subgroup A x -like profiles in group A secretors. The B antigen expression was less readily detectable. In vitro experiments, in which group O donor RBC were incubated with (i) group A/B secretor/non-secretor donor plasma or (ii) group A/B donor RBC in the absence of plasma, supported the proposed adsorption of A/B antigen-bearing glycolipids from secretor plasma but also indicated a secretor-independent mechanism for A/B antigen acquisition as well as direct cell-to-cell transfer of ABO antigens. The in vivo conversion of donor-derived blood group O RBC to ABO subgroup-like RBC after transfusion or minor ABO-incompatible HSCT raises the question of appropriate component selection. Based on these data, AB plasma should be transfused following ABO-incompatible HSCT. © 2017 British Blood Transfusion Society.

  16. Layer-by-layer deposition of nanostructured CsPbBr3 perovskite thin films

    NASA Astrophysics Data System (ADS)

    Reshetnikova, A. A.; Matyushkin, L. B.; Andronov, A. A.; Sokolov, V. S.; Aleksandrova, O. A.; Moshnikov, V. A.

    2017-11-01

    Layer-by-layer deposition of nanostructured perovskites cesium lead halide thin films is described. The method of deposition is based on alternate immersion of the substrate in the precursor solutions or colloidal solution of nanocrystals and methyl acetate/lead nitrate solution using the device for deposition of films by SILAR and dip-coating techniques. An example of obtaining a photosensitive structure based on nanostructures of ZnO nanowires and layers of CsBbBr3 nanocrystals is also shown.

  17. Relation of ABO blood groups to the severity of coronary atherosclerosis: an Gensini score assessment.

    PubMed

    Gong, Ping; Luo, Song-Hui; Li, Xiao-Lin; Guo, Yuan-Lin; Zhu, Cheng-Gang; Xu, Rui-Xia; Li, Sha; Dong, Qian; Liu, Geng; Chen, Juan; Zeng, Rui-Xiang; Li, Jian-Jun

    2014-12-01

    Although the study on the relationship between ABO blood groups and coronary atherosclerosis has a long history, few data is available regarding ABO to severity of coronary atherosclerosis in a large cohort study. Therefore, the present study aimed to investigate the relation of the ABO blood groups to the severity of coronary atherosclerosis assessed by Gensini score (GS) in a large Chinese cohort undergoing coronary angiography. A total of 2919 consecutive patients undergoing coronary angiography were enrolled, and their baseline characteristics and ABO blood groups were collected. The GS was calculated as 1st tertile (0-10), 2nd tertile (11-36), 3rd tertile (>36) according to angiographic results. The relation of the ABO blood groups to GS was investigated. The frequency of blood group A was significantly higher in the upper GS tertiles (24.4% vs. 28.2% vs. 29.5%, p = 0.032). Multivariable linear regression analysis revealed that blood group A was independently associated with GS (β = 0.043, p = 0.017). Likewise, multivariable logistic regression analysis showed that group A remained significantly associated with mid-high GS (OR = 1.44, 95% CI 1.16-1.80, p = 0.001), and the group O was showed as a protective factor (OR = 0.77, 95% CI = 0.65-0.92, p = 0.004). In this large Chinese cohort study, the data indicated that there was an association between ABO blood groups and the severity of coronary atherosclerosis. Moreover, the blood group A was an independent risk factor for serious coronary atherosclerosis. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

  18. Inkjet printable-photoactive all inorganic perovskite films with long effective photocarrier lifetimes

    NASA Astrophysics Data System (ADS)

    Ilie, C. C.; Guzman, F.; Swanson, B. L.; Evans, I. R.; Costa, P. S.; Teeter, J. D.; Shekhirev, M.; Benker, N.; Sikich, S.; Enders, A.; Dowben, P. A.; Sinitskii, A.; Yost, A. J.

    2018-05-01

    Photoactive perovskite quantum dot films, deposited via an inkjet printer, have been characterized by x-ray diffraction and x-ray photoelectron spectroscopy. The crystal structure and bonding environment are consistent with CsPbBr3 perovskite quantum dots. The current–voltage (I–V) and capacitance–voltage (C–V) transport measurements indicate that the photo-carrier drift lifetime can exceed 1 ms for some printed perovskite films. This far exceeds the dark drift carrier lifetime, which is below 50 ns. The printed films show a photocarrier density 109 greater than the dark carrier density, making these printed films ideal candidates for application in photodetectors. The successful printing of photoactive-perovskite quantum dot films of CsPbBr3, indicates that the rapid prototyping of various perovskite inks and multilayers is realizable.

  19. Inkjet printable-photoactive all inorganic perovskite films with long effective photocarrier lifetimes.

    PubMed

    Ilie, C C; Guzman, F; Swanson, B L; Evans, I R; Costa, P S; Teeter, J D; Shekhirev, M; Benker, N; Sikich, S; Enders, A; Dowben, P A; Sinitskii, A; Yost, A J

    2018-05-10

    Photoactive perovskite quantum dot films, deposited via an inkjet printer, have been characterized by x-ray diffraction and x-ray photoelectron spectroscopy. The crystal structure and bonding environment are consistent with CsPbBr 3 perovskite quantum dots. The current-voltage (I-V) and capacitance-voltage (C-V) transport measurements indicate that the photo-carrier drift lifetime can exceed 1 ms for some printed perovskite films. This far exceeds the dark drift carrier lifetime, which is below 50 ns. The printed films show a photocarrier density 10 9 greater than the dark carrier density, making these printed films ideal candidates for application in photodetectors. The successful printing of photoactive-perovskite quantum dot films of CsPbBr 3 , indicates that the rapid prototyping of various perovskite inks and multilayers is realizable.

  20. Recent advances of flexible hybrid perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Shin, Dong Hee; Heo, Jin Hyuck; Im, Sang Hyuk

    2017-11-01

    Recently, hybrid perovskite solar cells have attracted great interest because they can be fabricated to low cost, flexible, and highly efficient solar cells. Here, we introduced recent advances of flexible hybrid perovskite solar cells. We introduced research background of flexible perovskite solar cells in introduction part. Then we composed the main body to i) structure and properties of hybrid perovskite solar cells, ii) why flexible hybrid perovskite solar cells are important?, iii) transparent conducting oxide (TCO) based flexible hybrid perovskite solar cells, and iv) TCO-free transparent conducting electrode (TCE) based flexible hybrid perovskite solar cells. Finally, we summarized research outlook of flexible hybrid perovskite solar cells.

  1. Recent patents on perovskite ferroelectric nanostructures.

    PubMed

    Zhu, Xinhua

    2009-01-01

    Ferroelectric oxide materials with a perovskite structure have promising applications in electronic devices such as random access memories, sensors, actuators, infrared detectors, and so on. Recent advances in science and technology of ferroelectrics have resulted in the feature sizes of ferroelectric-based electronic devices entering into nanoscale dimensions. At nanoscale perovskite ferroelectric materials exhibit a pronounced size effect manifesting itself in a significant deviation of the properties of low-dimensional structures from the bulk and film counterparts. One-dimensional perovskite ferroelectric nanotube/nanowire systems, offer fundamental scientific opportunities for investigating the intrinsic size effects in ferroelectrics. In the past several years, much progress has been made both in fabrication and physical property testing of perovskite ferroelectric nanostructures. In the first part of this paper, the recent patents and literatures for fabricating ferroelectric nanowires, nanorods, nanotubes, and nanorings with promising features, are reviewed. The second part deals with the recent advances on the physical property testing of perovskite ferroelectric nanostructures. The third part summarizes the recently patents and literatures about the microstructural characterizations of perovskite ferroelectric nanostructures, to improve their crystalline quality, morphology and uniformity. Finally, we conclude this review with personal perspectives towards the potential future developments of perovskite ferroelectric nanostructures.

  2. Correlation of ABO blood groups with spontaneous recanalization in acute myocardial infarction.

    PubMed

    Lin, Xian-Liang; Zhou, Bing-Yang; Li, Sha; Li, Xiao-Lin; Luo, Zhu-Rong; Li, Jian-Jun

    2017-08-01

    Although previous studies have demonstrated the relationship between ABO blood groups and cardiovascular disease, the association of ABO blood type with spontaneous recanalization (SR) in patients with acute myocardial infarction (AMI) has not been previously investigated. We performed an initial exploratory study on the association of ABO blood groups with the presence of SR in 1209 patients with AMI. They were divided into two groups according to the thrombolysis in myocardial infarction (TIMI) grades: no-SR group (TIMI 0-1, n = 442) and SR group (TIMI 2-3, n = 767). To confirm our primary findings, data from a second AMI population (n = 200) was analyzed. In the initial data, SR group had a significantly higher percentage of blood type O and a lower percentage of blood type A compared to the no-SR group. Multivariate logistic regression analysis showed that blood type O was positively associated with SR (odds ratio: 1.40, 95% confidence interval: 1.05-1.87, p = .02), and this finding was confirmed in our second population. The present study demonstrates that blood type O was independently and positively associated with an open culprit artery in patients with AMI, suggesting that the ABO blood type is not only associated with the susceptibility to coronary artery disease but also to spontaneous reperfusion in AMI patients.

  3. Material properties of perovskites in the quasi-ternary system LaFeO3-LaCoO3-LaNiO3

    NASA Astrophysics Data System (ADS)

    Tietz, F.; Arul Raj, I.; Ma, Q.; Baumann, S.; Mahmoud, A.; Hermann, R. P.

    2016-05-01

    An overview is presented on the variation of electrical conductivity, oxygen permeation, and thermal expansion coefficient as a function of the composition of perovskites in the quasi-ternary system LaFeO3-LaCoO3-LaNiO3. Powders of thirteen nominal perovskite compositions were synthesized under identical conditions by the Pechini method. The powder X-ray diffraction data of two series, namely La(Ni0.5Fe0.5)1-xCoxO3 and LaNi0.5-xFexCo0.5O3, are presented after the powders had been sintered at 1100 °C for 6 h in air. The measurements revealed a rhombohedral structure for all compositions except LaNi0.5Fe0.5O3 for which 60% rhombohedral and 40% orthorhombic phase was found. The maximum DC electrical conductivity value of the perovskites at 800 °C was 1229 S cm-1 for the composition LaCoO3 and the minimum was 91 S cm-1 for the composition LaCo0.5Fe0.5O3. The oxygen permeation of samples with promising conductivities at 800 °C was one order of magnitude lower than that of La0.6Sr0.4Co0.8Fe0.2O3 (LSCF). The highest value of 0.017 ml cm-2 min-1 at 950 °C was obtained with LaNi0.5Co0.5O3. The coefficients of thermal expansion varied in the range of 13.2×10-6 K-1 and 21.9×10-6 K-1 for LaNi0.5Fe0.5O3 and LaCoO3, respectively. 57Fe Mössbauer spectroscopy was used as probe for the oxidation states, local environment and magnetic properties of iron ions as a function of chemical composition. The substitution had a great influence on the chemical properties of the materials.

  4. Investigating Recombination and Charge Carrier Dynamics in a One-Dimensional Nanopillared Perovskite Absorber.

    PubMed

    Kwon, Hyeok-Chan; Yang, Wooseok; Lee, Daehee; Ahn, Jihoon; Lee, Eunsong; Ma, Sunihl; Kim, Kyungmi; Yun, Seong-Cheol; Moon, Jooho

    2018-05-22

    Organometal halide perovskite materials have become an exciting research topic as manifested by intense development of thin film solar cells. Although high-performance solar-cell-based planar and mesoscopic configurations have been reported, one-dimensional (1-D) nanostructured perovskite solar cells are rarely investigated despite their expected promising optoelectrical properties, such as enhanced charge transport/extraction. Herein, we have analyzed the 1-D nanostructure effects of organometal halide perovskite (CH 3 NH 3 PbI 3- x Cl x ) on recombination and charge carrier dynamics by utilizing a nanoporous anodized alumina oxide scaffold to fabricate a vertically aligned 1-D nanopillared array with controllable diameters. It was observed that the 1-D perovskite exhibits faster charge transport/extraction characteristics, lower defect density, and lower bulk resistance than the planar counterpart. As the aspect ratio increases in the 1-D structures, in addition, the charge transport/extraction rate is enhanced and the resistance further decreases. However, when the aspect ratio reaches 6.67 (diameter ∼30 nm), the recombination rate is aggravated due to high interface-to-volume ratio-induced defect generation. To obtain the full benefits of 1-D perovskite nanostructuring, our study provides a design rule to choose the appropriate aspect ratio of 1-D perovskite structures for improved photovoltaic and other optoelectrical applications.

  5. Site Redistribution, Partial Frozen-in Defect Chemistry, and Electrical Properties of Ba1-x(Zr,Pr)O3-δ.

    PubMed

    Antunes, Isabel; Mikhalev, Sergey; Mather, Glenn Christopher; Kharton, Vladislav Vadimovich; Figueiras, Fábio Gabriel; Alves, Adriana; Rodrigues, Joana; Correia, Maria Rosário; Frade, Jorge Ribeiro; Fagg, Duncan Paul

    2016-09-06

    Changes in nominal composition of the perovskite (ABO3) solid solution Ba1-x(Zr,Pr)O3-δ and adjusted firing conditions at very high temperatures were used to induce structural changes involving site redistribution and frozen-in point defects, as revealed by Raman and photoluminescence spectroscopies. Complementary magnetic measurements allowed quantification of the reduced content of Pr. Weak dependence of oxygen stoichiometry with temperature was obtained by coulometric titration at temperatures below 1000 °C, consistent with a somewhat complex partial frozen-in defect chemistry. Electrical conductivity measurements combined with transport number and Seebeck coefficient measurements showed prevailing electronic transport and also indicated trends expected for partial frozen-in conditions. Nominal Ba deficiency and controlled firing at very high temperatures allows adjustment of structure and partial frozen-in defect chemistry, opening the way to engineer relevant properties for high-temperature electrochemical applications.

  6. The Effect of Molar Ratio on Crystal Structure and Morphology of Nd1+XFeO3 (X=0.1, 0.2, and 0.3) Oxide Alloy Material Synthesized by Solid State Reaction Method

    NASA Astrophysics Data System (ADS)

    Zharvan, V.; Kamaruddin, Y. N. I.; Samnur, S.; Sujiono, E. H.

    2017-05-01

    Perovskite is an oxide alloy which has a structure of ABO3 (A = La, Nd, Sm, Gd; B = Fe, CO, Ni) and has an excellent catalytic activity and gas-sensitive properties. NdFeO3 and its derivatives are important candidates for gas sensors. In this study, the effect of molar ratio (x=0.1, 0.2 and 0.3) on crystal structure and morphology of Nd1+xFeO3 synthesized by solid state reaction method has been studied. Nd1+xFeO3 samples were prepared using Nd2O3 (99.99 %) and Fe2O3 (99.99 %) as precursors. All of the samples were characterized using XRD to identify the phase and using SEM to identify the morphology. The synthesized Nd1+xFeO3 samples showed that molar ratio strongly influences the intensity, FWHM, and crystalline size. The samples of Nd1+xFeO3 have homogenous morphology and have three major phases, i.e. NdFeO3, Nd(OH)3 and Nd2O3 with crystalline sizes of NdFeO3 of 137.0±0.1 nm, 152.2±0.1 nm and 137.0±0.1 nm for Nd1.1FeO3, Nd1.2FeO3, and Nd1.3FeO3, respectively. These results indicated that the sample of Nd1.2FeO3 was a good candidate for a gas sensor material.

  7. 4d Electronic structure analysis of ruthenium in the perovskite oxides by Ru K- and L-edge XAS.

    PubMed

    Kim, J Y; Hwang, S H; Kim, S J; Demazeau, G; Choy, J H; Shimada, H

    2001-03-01

    The 4d electronic structure of ruthenium in the perovskite oxides, La2MRuIVO6 (M = Zn, Mg, and Li) and Ba2YRuVO6, has been investigated by the Ru K-and L-edge XANES and EXAFS analyses. Such X-ray absorption spectroscopic results clarify that the RuIV (d4) and RuV (d3) ions are stabilized in nearly regular Oh site. Comparing the Ru L-edge XANES spectra of perovskites containing isovalent ruthenium, it has been found that the t2g state is mainly influenced by A site cation, whereas the eg is mainly affected by neighboring B site cation. The experimental EXAFS spectra in the range of R < or = approximately 4.5 A are well reproduced by ab-initio calculation based on crystallographic data, which supports the long-range structure presented by Rietveld refinement.

  8. Crystallite size strain analysis of nanocrystalline La0.7Sr0.3MnO3 perovskite by Williamson-Hall plot method

    NASA Astrophysics Data System (ADS)

    Kumar, Dinesh; Verma, Narendra Kumar; Singh, Chandra Bhal; Singh, Akhilesh Kumar

    2018-04-01

    The nanocrystalline Sr-doped LaMnO3 (La0.7Sr0.3MnO3 = LSMO) perovskite manganites having different crystallite size were synthesized using the nitrate-glycine auto-combustion method. The phase purity of the manganites was checked by X-ray diffraction (XRD) measurement. The XRD patterns of the sample reveal that La0.7S0.3MnO3 crystallizes into rhombohedral crystal structure with space group R-3c. The size-dependence of structural lattice parameters have been investigated with the help of Rietveld refinement. The structural parameters increase as a function of crystallite size. The crystallite-size and internal strain as a function of crystallite-size have been calculated using Williamson-Hall plot.

  9. Large grained perovskite solar cells derived from single-crystal perovskite powders with enhanced ambient stability

    DOE PAGES

    Yen, Hung -Ju; Liang, Po -Wei; Chueh, Chu -Chen; ...

    2016-05-25

    In this study, we demonstrate the large grained perovskite solar cells prepared from precursor solution comprising single-crystal perovskite powders for the first time. Here, the resultant large grained perovskite thin film possesses negligible physical (structural) gap between each large grain and are highly crystalline as evidenced by its fan-shaped birefringence observed under polarized light, which is very different to the thin film prepared from the typical precursor route (MAI + PbI 2).

  10. A High Pressure Post-Perovskite Phase Transition in NaMgF3--a MgSiO3 Analog Material

    NASA Astrophysics Data System (ADS)

    Martin, C.; Liu, H.; Crichton, W.; Parise, J. B.

    2005-12-01

    Since Murakami et al. (2004) identified a perovskite (pv, Pbnm) to post-perovskite (ppv, Cmcm) structural phase transition in MgSiO3, the transition has been reported to occur in many oxides at ultra-high pressures (>60 GPa). The layered ppv structure is rapidly shaping a better understanding of seismic anisotropy in the controversial D" region of the lower mantle. While the ppv unit cell may be derived from indexing of the powder pattern, the structure adopted at high pressure is experimentally ill-constrained due to compromised powder diffraction statistics typically obtained from small sample volumes at extreme conditions in the diamond anvil cell. NaMgF3, a structural analog material to MgSiO3 pv, exhibits a large compressibility and presents the possibility of reducing the pv-ppv transition pressure, allowing for improved powder statistics from a larger sample volume. In accordance with our previous theoretical and experimental evidence (Liu et al., 2005; Parise et al., 2004), we have observed a phase transition in NaMgF3 during two recent independent high pressure trials utilizing monochromatic x-ray diffraction and in-situ laser heating in the diamond anvil cell at pressures as low as 30 GPa. From our analysis thus far, we have found the unit cell of the high pressure phase cannot be indexed according to pv (Pbnm) or close permutations of ppv (Cmcm) unit cells predicted for NaMgF3 or unit cells observed for ppv MgSiO3 and MgGeO3. In addition, we have precluded a breakdown to high pressure phases of NaF and MgF3 as an explanation for the observed data. Upon pressure release, we observe diffraction peaks from the high pressure phase in the absence of pv NaMgF3, suggesting the high pressure structure is quenchable to ambient conditions. The results of the work in progress will be presented at the meeting.

  11. CD144+ endothelial microparticles as a marker of endothelial injury in neonatal ABO blood group incompatibility.

    PubMed

    Awad, Hisham A E; Tantawy, Azza A G; El-Farrash, Rania A; Ismail, Eman A; Youssif, Noha M

    2014-04-01

    ABO antigens are expressed on the surfaces of red blood cells and the vascular endothelium. We studied circulating endothelial microparticles (EMP) in ABO haemolytic disease of the newborn (ABO HDN) as a marker of endothelial activation to test a hypothesis of possible endothelial injury in neonates with ABO HDN, and its relation with the occurrence and severity of haemolysis. Forty-five neonates with ABO HDN were compared with 20 neonates with Rhesus incompatibility (Rh HDN; haemolytic controls) and 20 healthy neonates with matched mother and infant blood groups (healthy controls). Laboratory investigations were done for markers of haemolysis and von Willebrand factor antigen (vWF Ag). EMP (CD144(+)) levels were measured before and after therapy (exchange transfusion and/or phototherapy). vWF Ag and pre-therapy EMP levels were higher in infants with ABO HDN or Rh HDN than in healthy controls, and were significantly higher in babies with ABO HDN than in those with Rh HDN (p<0.05). In ABO HDN, pre-therapy EMP levels were higher in patients with severe hyperbilirubinaemia than in those with mild and moderate disease or those with Rh HDN (p<0.001). Post-therapy EMP levels were lower than pre-therapy levels in both the ABO HDN and Rh HDN groups; however, the decline in EMP levels was particularly evident after exchange transfusion in ABO neonates with severe hyperbilirubinaemia (p<0.001). Multiple regression analysis revealed that the concentrations of haemoglobin, lactate dehydrogenase and indirect bilirubin were independently correlated with pre-therapy EMP levels in ABO HDN. Elevated EMP levels in ABO HDN may reflect an IgG-mediated endothelial injury parallel to the IgG-mediated erythrocyte destruction and could serve as a surrogate marker of vascular dysfunction and disease severity in neonates with this condition.

  12. Synthesis and applications of nanoporous perovskite metal oxides

    PubMed Central

    Huang, Xiubing; Zhao, Guixia

    2018-01-01

    Perovskite-type metal oxides have been widely investigated and applied in various fields in the past several decades due to their extraordinary variability of compositions and structures with targeted physical and chemical properties (e.g., redox behaviour, oxygen mobility, electronic and ionic conductivity). Recently, nanoporous perovskite metal oxides have attracted extensive attention because of their special morphology and properties, as well as superior performance. This minireview aims at summarizing and reviewing the different synthesis methods of nanoporous perovskite metal oxides and their various applications comprehensively. The correlations between the nanoporous structures and the specific performance of perovskite oxides are summarized and highlighted. The future research directions of nanoporous perovskite metal oxides are also prospected. PMID:29862001

  13. Distribution of ABO Blood Groups and Coronary Artery Calcium.

    PubMed

    Wang, Yao; Zhou, Bing-Yang; Zhu, Cheng-Gang; Guo, Yuan-Lin; Wu, Na-Qiong; Qing, Ping; Gao, Ying; Liu, Geng; Dong, Qian; Li, Jian-Jun

    2017-06-01

    ABO blood groups have been confirmed to be associated with cardiovascular diseases such as coronary artery disease. However, whether ABO blood group is correlated with coronary artery calcium (CAC) is still unknown. 301 patients with coronary artery calcium score (CACS) assessed by computed tomography were consecutively enrolled and divided into two groups: with calcium group (CACS>0, n=104) and without calcium group (CACS=0, n=197). Distribution of ABO blood groups was evaluated between the two groups. The percentage of A blood type was significantly higher (p=0.008) and O blood type was significantly lower (p=0.037) in the calcium group. Univariate regression analysis showed that age, total cholesterol, low density lipoprotein cholesterol, high-sensitivity C-reactive protein, A blood type were positively correlated with CAC, and O blood type was inversely associated with CAC. Multivariate regression analysis showed that A blood type was independently associated with CAC (odds ratio: 2.217, 95% confidence interval: 1.260-3.900, p=0.006) even after further adjustment for variables that were clearly different between the two groups. Our data has suggested for the first time that A blood type was an independent risk marker for CAC. Copyright © 2016 Australian and New Zealand Society of Cardiac and Thoracic Surgeons (ANZSCTS) and the Cardiac Society of Australia and New Zealand (CSANZ). Published by Elsevier B.V. All rights reserved.

  14. Graded bandgap perovskite solar cells.

    PubMed

    Ergen, Onur; Gilbert, S Matt; Pham, Thang; Turner, Sally J; Tan, Mark Tian Zhi; Worsley, Marcus A; Zettl, Alex

    2017-05-01

    Organic-inorganic halide perovskite materials have emerged as attractive alternatives to conventional solar cell building blocks. Their high light absorption coefficients and long diffusion lengths suggest high power conversion efficiencies, and indeed perovskite-based single bandgap and tandem solar cell designs have yielded impressive performances. One approach to further enhance solar spectrum utilization is the graded bandgap, but this has not been previously achieved for perovskites. In this study, we demonstrate graded bandgap perovskite solar cells with steady-state conversion efficiencies averaging 18.4%, with a best of 21.7%, all without reflective coatings. An analysis of the experimental data yields high fill factors of ∼75% and high short-circuit current densities up to 42.1 mA cm -2 . The cells are based on an architecture of two perovskite layers (CH 3 NH 3 SnI 3 and CH 3 NH 3 PbI 3-x Br x ), incorporating GaN, monolayer hexagonal boron nitride, and graphene aerogel.

  15. Design Principles for the Atomic and Electronic Structure of Halide Perovskite Photovoltaic Materials: Insights from Computation.

    PubMed

    Berger, Robert F

    2018-02-09

    In the current decade, perovskite solar cell research has emerged as a remarkably active, promising, and rapidly developing field. Alongside breakthroughs in synthesis and device engineering, halide perovskite photovoltaic materials have been the subject of predictive and explanatory computational work. In this Minireview, we focus on a subset of this computation: density functional theory (DFT)-based work highlighting the ways in which the electronic structure and band gap of this class of materials can be tuned via changes in atomic structure. We distill this body of computational literature into a set of underlying design principles for the band gap engineering of these materials, and rationalize these principles from the viewpoint of band-edge orbital character. We hope that this perspective provides guidance and insight toward the rational design and continued improvement of perovskite photovoltaics. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Histone deacetylase inhibitors suppress ABO transcription in vitro, leading to reduced expression of the antigens.

    PubMed

    Takahashi, Yoichiro; Kubo, Rieko; Sano, Rie; Nakajima, Tamiko; Takahashi, Keiko; Kobayashi, Momoko; Handa, Hiroshi; Tsukada, Junichi; Kominato, Yoshihiko

    2017-03-01

    The ABO system is of fundamental importance in the fields of transfusion and transplantation and has apparent associations with certain diseases, including cardiovascular disorders. ABO expression is reduced in the late phase of erythroid differentiation in vitro, whereas histone deacetylase inhibitors (HDACIs) are known to promote cell differentiation. Therefore, whether or not HDACIs could reduce the amount of ABO transcripts and A or B antigens is an intriguing issue. Quantitative polymerase chain reactions were carried out for the ABO transcripts in erythroid-lineage K562 and epithelial-lineage KATOIII cells after incubation with HDACIs, such as sodium butyrate, panobinostat, vorinostat, and sodium valproate. Flow cytometric analysis was conducted to evaluate the amounts of antigen in KATOIII cells treated with panobinostat. Quantitative chromatin immunoprecipitation (ChIP) assays and luciferase assays were performed on both cell types to examine the mechanisms of ABO suppression. HDACIs reduced the ABO transcripts in both K562 and KATOIII cells, with panobinostat exerting the most significant effect. Flow cytometric analysis demonstrated a decrease in B-antigen expression on panobinostat-treated KATOIII cells. ChIP assays indicated that panobinostat altered the modification of histones in the transcriptional regulatory regions of ABO, and luciferase assays demonstrated reduced activity of these elements. ABO transcription seems to be regulated by an epigenetic mechanism. Panobinostat appears to suppress ABO transcription, reducing the amount of antigens on the surface of cultured cells. © 2016 AABB.

  17. Influence of the Preparation Method on Planar Perovskite CH3NH3PbI3-xClx Solar Cell Performance and Hysteresis

    NASA Astrophysics Data System (ADS)

    Ivanova, A.; Tokmakov, A.; Lebedeva, K.; Roze, M.; Kaulachs, I.

    2017-08-01

    Organometal halide perovskites are promising materials for lowcost, high-efficiency solar cells. The method of perovskite layer deposition and the interfacial layers play an important role in determining the efficiency of perovskite solar cells (PSCs). In the paper, we demonstrate inverted planar perovskite solar cells where perovskite layers are deposited by two-step modified interdiffusion and one-step methods. We also demonstrate how PSC parameters change by doping of charge transport layers (CTL). We used dimethylsupoxide (DMSO) as dopant for the hole transport layer (PEDOT:PSS) but for the electron transport layer [6,6]-phenyl C61 butyric acid methyl ester (PCBM)) we used N,N-dimethyl-N-octadecyl(3-aminopropyl)trimethoxysilyl chloride (DMOAP). The highest main PSC parameters (PCE, EQE, VOC) were obtained for cells prepared by the one-step method with fast crystallization and doped CTLs but higher fill factor (FF) and shunt resistance (Rsh) values were obtained for cells prepared by the two-step method with undoped CTLs.

  18. Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl 6

    DOE PAGES

    Pilania, G.; Uberuaga, B. P.

    2015-03-19

    Here, we investigate the electronic structure, energetics of cation ordering, and effect of biaxial strain on double perovskite CsRbCaZnCl 6 using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl 3 and RbZnCl 3) forming the double perovskite exhibit a stark contrast. While CsCaCl 3 is known to exist in a cubic perovskite structure and does not show any epitaxial strain induced phase transitions within an experimentally accessible range of compressive strains, RbZnCl 3 is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We showmore » that combining the two compositions in a double perovskite structure not only improves overall stability but also the strain-polarization coupling of the material. Our calculations predict a ground state with P4/nmm space group for the double perovskite, where A-site cations (i.e., Cs and Rb) are layer-ordered and B-site cations (i.e., Ca and Zn) prefer a rocksalt type ordering. The electronic structure and bandgap in this system are shown to be quite sensitive to the B-site cation ordering and is minimally affected by the ordering of A-site cations. We find that at experimentally accessible compressive strains CsRbCaZnCl 6 can be phase transformed from its paraelectric ground state to an antiferroelectric state, where Zn atoms contribute predominantly to the polarization. Furthermore, both energy difference and activation barrier for a transformation between this antiferroelectric state and the corresponding ferroelectric configuration are predicted to be small. As a result, the computational approach presented here opens a new pathway towards a rational design of novel double perovskites with improved strain response and functionalities.« less

  19. Colloidally prepared La-doped BaSnO3 electrodes for efficient, photostable perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Shin, Seong Sik; Yeom, Eun Joo; Yang, Woon Seok; Hur, Seyoon; Kim, Min Gyu; Im, Jino; Seo, Jangwon; Noh, Jun Hong; Seok, Sang Il

    2017-04-01

    Perovskite solar cells (PSCs) exceeding a power conversion efficiency (PCE) of 20% have mainly been demonstrated by using mesoporous titanium dioxide (mp-TiO2) as an electron-transporting layer. However, TiO2 can reduce the stability of PSCs under illumination (including ultraviolet light). Lanthanum (La)-doped BaSnO3 (LBSO) perovskite would be an ideal replacement given its electron mobility and electronic structure, but LBSO cannot be synthesized as well-dispersible fine particles or crystallized below 500°C. We report a superoxide colloidal solution route for preparing a LBSO electrode under very mild conditions (below 300°C). The PSCs fabricated with LBSO and methylammonium lead iodide (MAPbI3) show a steady-state power conversion efficiency of 21.2%, versus 19.7% for a mp-TiO2 device. The LBSO-based PSCs could retain 93% of their initial performance after 1000 hours of full-Sun illumination.

  20. Synthesis, structural and optical properties of (ALa)(FeMn)O6 (A = Ba and Sr) double perovskites

    NASA Astrophysics Data System (ADS)

    Kumar, Dinesh; Sudarshan, V.; Singh, Akhilesh Kumar

    2018-05-01

    Here, we report structural and optical properties of ALaFeMnO6 (A = Ba and Sr) double perovskite synthesized via auto-combustion followed by calcinations process. Rietveld refinement of structure using x-ray diffraction data reveals that BaLaFeMnO6 crystallizes into cubic crystal structure with space group Pm-3m while SrLaFeMnO6 crystallizes into rhombohedral crystal structure having space group R-3c. The absorption spectrum measurement using UV-Vis spectroscopy reveals that these samples are prefect insulator having energy band gap between conduction and valence band of the order of 6 eV.