Science.gov

Sample records for abo3 perovskite structure

  1. First Principles Studies of ABO3 Perovskite Surfaces and Nanostructures

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam

    Perovskite-type complex oxides, with general formula ABO 3, constitute one of the most prominent classes of metal oxides which finds key applications in diverse technological fields. In recent years, properties of perovskites at reduced dimensions have aroused considerable interest. However, a complete atomic-level understanding of various phenomena is yet to emerge. To fully exploit the materials opportunities provided by nano-structured perovskites, it is important to characterize and understand their bulk and near-surface electronic structure along with the electric, magnetic, elastic and chemical properties of these materials in the nano-regime, where surface and interface effects naturally play a dominant role. In this thesis, state-of-the-art first principles computations are employed to systematically study properties of one- and two-dimensional perovskite systems which are of direct technological significance. Specifically, our bifocal study targets (1) polarization behavior and dielectric response of ABO3 ferroelectric nanowires, and (2) oxygen chemistry relevant for catalytic properties of ABO3 surfaces. In the first strand, we identify presence of novel closure or vortex-like polarization domains in PbTIO3 and BaTiO3 ferroelectric nanowires and explore ways to control the polarization configurations by means of strain and surface chemistry in these prototypical model systems. The intrinsic tendency towards vortex polarization at reduced dimensions and the underlying driving forces are discussed and previously unknown strain induced phase transitions are identified. Furthermore, to compute the dielectric permittivity of nanostructures, a new multiscale model is developed and applied to the PbTiO3 nanowires with conventional and vortex-like polarization configurations. The second part of the work undertaken in this thesis is comprised of a number of ab initio surface studies, targeted to investigate the effects of surface terminations, prevailing chemical

  2. Classification of ABO3 perovskite solids: a machine learning study.

    PubMed

    Pilania, G; Balachandran, P V; Gubernatis, J E; Lookman, T

    2015-10-01

    We explored the use of machine learning methods for classifying whether a particular ABO3 chemistry forms a perovskite or non-perovskite structured solid. Starting with three sets of feature pairs (the tolerance and octahedral factors, the A and B ionic radii relative to the radius of O, and the bond valence distances between the A and B ions 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 the A and B atoms to this set of feature pairs. 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.

  3. A-site ion vibrational modes in ABO3 polar perovskites

    NASA Astrophysics Data System (ADS)

    Hlinka, Jiri

    2012-02-01

    It is well known that Pb(B'B'')O3 family of complex perovskites contains materials with very useful dielectric, piezoelectric and ferroelectric properties. The overall electromechanical response of these system is believed to be related to their characteristic micro- to nanoscale structural correlations (chemical clusters, polar nanoregions or nanotwins). At the level of the ABO3 unit cell, the remarkable polarizability of these materials originates from lead-ion displacements, and the anharmonic motion of these ions, loosely linked to the core oxygen octahedra network, largely dominates in the low-frequency phonon modes in the system. Therefore, the investigation of the low-frequency phonon modes in these systems is of a great importance. The aim of this contribution is to report recent experimental studies of such low-frequency vibrations by inelastic X-ray, neutron and light scattering techniques, in materials like lead zirconate titanate, lead magnesium niobium titanate or lead titanate. In particular, attention will be payed to our recent inelastic X-ray scattering studies of PZT lattice dynamics.

  4. ABO3 (A = La, Ba, Sr, K; B = Co, Mn, Fe) perovskites for thermochemical energy storage

    NASA Astrophysics Data System (ADS)

    Babiniec, Sean M.; Coker, Eric N.; Ambrosini, Andrea; Miller, James E.

    2016-05-01

    The use of perovskite oxides as a medium for thermochemical energy storage (TCES) in concentrating solar power systems is reported. The known reduction/oxidation (redox) active perovskites LaxSr1-xCoyMn1-yO3 (LSCM) and LaxSr1-xCoyFe1-yO3 (LSCF) were chosen as a starting point for such research. Materials of the LSCM and LSCF family were previously synthesized, their structure characterized, and thermodynamics reported for TCES operation. Building on this foundation, the reduction onset temperatures are examined for LSCM and LSCF compositions. The reduction extents and onset temperatures are tied to the crystallographic phase and reaction enthalpies. The effect of doping with Ba and K is discussed, and the potential shortcomings of this subset of materials families for TCES are described. The potential for long-term stability of the most promising material is examined through thermogravimetric cycling, scanning electron microscopy, and dilatometry. The stability over 100 cycles (450-1050 °C) of an LSCM composition is demonstrated.

  5. Electric-field-induced local structural phenomena in Pb-based ABO3-type relaxor ferroelectrics.

    PubMed

    Mihailova, Boriana; Maier, Bernd J; Steilmann, Thomas; Dul'kin, Evgeniy; Roth, Michael

    2015-01-01

    Lead-based ABO3-type relaxors and related systems have numerous applications in modern technical devices because of their remarkably high dielectric permittivity and piezoelectric/electroelastic and electro-optic coefficients. However, lead is not desired from an environmental point of view, and to switch to alternative alkali-, Ba-, or Bi-based relaxor systems, one must understand in great detail the structural mesoscopic order and coupling processes responsible for the outstanding performance and multifunctionality of the exemplar Pb-based compounds. To elucidate the type of ferroic coupling, three relaxor compounds PbSc0.5Ta0.5O3 (PST), Pb0.78Ba0.22Sc0.5Ta0.5O3 (PST-Ba), and PbSc0.5Nb0.5O3 (PSN), were studied by polarized Raman scattering and acoustic emission at different temperatures and under an external electric field. The results reveal the coexistence of mesoscopic-scale ferroelectric and antiferroelectric coupling, which are predominantly related to B-site cations and A-site Pb cations, respectively. This suggests that the polar structural state of relaxors is frustrated ferrielectric. The presence of A-site cations with affinity to off-center is significant for the development of mesoscopic-scale antiferroelectric order coexisting with the mesoscopic-scale ferroelectric order. PMID:25585386

  6. Stability of interlanthanide perovskites ABO3 (A ≡ La-Pr; B ≡ Y, Ho-Lu)

    NASA Astrophysics Data System (ADS)

    Artini, Cristina; Pani, Marcella; Lausi, Andrea; Costa, Giorgio A.

    2016-04-01

    The existence fields of the 11 known interlanthanide perovskites have been assessed as a function of temperature on the basis of experimental and literature data, and studied by means of the bond valence method using the software SPuDS. The role of geometrical factors in driving the enthalpic and entropic contributions to the Gibbs free energy of the phase is discussed, and a criterion is proposed to derive the formability likelihood of interlanthanide perovskites. The reliability of the software SPuDS has been checked by comparing the cell parameters and atomic distances optimized by the program to the ones experimentally obtained by high temperature in situ synchrotron X-ray diffraction performed on perovskitic LaErO3, LaTmO3 and LaYbO3.

  7. Selective Dissolution of A-Site Cations in ABO3 Perovskites: A New Path to High-Performance Catalysts.

    PubMed

    Si, Wenzhe; Wang, Yu; Peng, Yue; Li, Junhua

    2015-06-26

    Selective dissolution is a common corrosion process in dealloying in which an alloy is immersed in acid to remove the active element, leaving behind an inert constituent. We introduce this technique into the treatment of oxide catalysts. A three-dimensionally ordered macroporous LaMnO3 perovskite has been prepared and treated with diluted HNO3 to selectively remove La cations, acquiring a novel γ-MnO2-like material. LaMnO3 is not a satisfactory catalyst on CO oxidation. Upon the removal of La cations, the obtained sample showed a significantly higher CO oxidation catalytic activity (T50=89 °C) than the initial precursor LaMnO3 (T50=237 °C) and ordinary γ-MnO2 (T50=148 °C). A large surface area, a high degree of mesoporosity, excellent low-temperature reducibility, and especially improved surface oxygen species are deduced to be responsible for CO oxidation at lower temperatures.

  8. Selective Dissolution of A-Site Cations in ABO3 Perovskites: A New Path to High-Performance Catalysts.

    PubMed

    Si, Wenzhe; Wang, Yu; Peng, Yue; Li, Junhua

    2015-06-26

    Selective dissolution is a common corrosion process in dealloying in which an alloy is immersed in acid to remove the active element, leaving behind an inert constituent. We introduce this technique into the treatment of oxide catalysts. A three-dimensionally ordered macroporous LaMnO3 perovskite has been prepared and treated with diluted HNO3 to selectively remove La cations, acquiring a novel γ-MnO2-like material. LaMnO3 is not a satisfactory catalyst on CO oxidation. Upon the removal of La cations, the obtained sample showed a significantly higher CO oxidation catalytic activity (T50=89 °C) than the initial precursor LaMnO3 (T50=237 °C) and ordinary γ-MnO2 (T50=148 °C). A large surface area, a high degree of mesoporosity, excellent low-temperature reducibility, and especially improved surface oxygen species are deduced to be responsible for CO oxidation at lower temperatures. PMID:25967677

  9. Designing rules and probabilistic weighting for fast materials discovery in the Perovskite structure

    NASA Astrophysics Data System (ADS)

    Castelli, I. E.; Jacobsen, K. W.

    2014-07-01

    High-throughput electronic-structure calculations are becoming increasingly popular in materials science and in the design of new compounds. Electronic-structure theory, for example, in the form of density-functional theory, can be used to calculate stabilities and electronic properties as bandgaps of new compounds. However, in practice, the methods are often limited to rather small atomic-scale systems or periodic crystals with only a limited number of atoms in the unit cell. It is therefore of interest to be able to derive generally useful information from simple systems to be applied in other, more complex, crystals. Here, we consider a large database of calculated stabilities and bandgaps of oxides and oxynitrides in the perovskite structure. We use the database as a testing ground for existing ideas about the behavior of these types of compounds and we derive some new simple chemical-based rules which combine structural information, like the ionic radii of the chemical elements, with electronic data, like the number of electrons and the valences of the pure elements. The rules extracted from the ABO3 cubic perovskite are then tested using the ABO2N and A2BO4 stoichiometry in the cubic and layered perovskite structure, respectively. These rules allow a saving in computer time of around 80%.

  10. Autothermal reforming catalyst having perovskite structure

    DOEpatents

    Krumpel, Michael; Liu, Di-Jia

    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.

  11. 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.

  12. 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. PMID:23579382

  13. Universal collaborative couplings between oxygen-octahedral rotations and antiferroelectric distortions in perovskites

    NASA Astrophysics Data System (ADS)

    Bellaiche, L.; Íñiguez, Jorge

    2013-07-01

    We identify two elemental interatomic couplings that control the collaborative (as opposed to competing) interaction between the O6 octahedral rotations (usually called antiferrodistortive or AFD modes) and the antiferroelectric (AFE) displacement patterns of the A-site cations in oxides with the ABO3 perovskite structure. Straightforward analytical derivations allow us to reproduce and explain the origin of various long-range AFE orders that have been previously found in different phases of several perovskite compounds, all possessing simple or even complex long-range AFD patterns. Our analysis also leads to the prediction of original peculiar combinations of AFD and AFE orders that are awaiting to be observed.

  14. 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.

  15. 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.

  16. Analysis of electrostatic stability and ordering in quaternary perovskite solid solutions

    NASA Astrophysics Data System (ADS)

    Caetano, Clovis; Butler, Keith T.; Walsh, Aron

    2016-04-01

    There are three distinct classes of perovskite structured metal oxides, defined by the charge states of the cations: AIBVO3,AIIBIVO3 , and AIIIBIIIO3 . We investigated the stability of cubic quaternary solid solutions A B O3-A'B'O3 using a model of point-charge lattices. The mixing enthalpies were calculated and compared for the three possible types of combinations of the compounds, both for the random alloys and the ground-state-ordered configurations. The mixing enthalpy of the (I,V)O3-(III,III)O3 alloy is always larger than the other alloys. We found that, different from homovalent alloys, for these heterovalent alloys a lattice constant mismatch between the constituent compounds could contribute to stabilize the alloy. At low temperatures, the alloys present a tendency to spontaneous ordering, forming superlattices consisting of alternated layers of AB O 3 and A'B'O3 along the [110 ] direction.

  17. Special quasirandom structures for perovskite solid solutions.

    PubMed

    Jiang, Zhijun; Nahas, Yousra; Xu, Bin; Prosandeev, Sergey; Wang, Dawei; Bellaiche, Laurent

    2016-11-30

    Special quasirandom structures (SQS) are presently generated for disordered (A'1-x [Formula: see text] x )BX3 and A(B'1-x [Formula: see text] x )X3 perovskite solid solutions, with x  =  1/2 as well as 1/3 and 2/3. These SQS configurations are obtained by imposing that the so-called Cowley parameters are as close to zero as possible for the three nearest neighboring shells. Moreover, these SQS configurations are slightly larger in size than those available in the literature for x  =  1/2, mostly because of the current capabilities of atomistic techniques. They are used here within effective Hamiltonian schemes to predict various properties, which are then compared to those associated with large random supercells, in a variety of compounds, namely (Ba1-x Sr x )TiO3, Pb(Zr1-x Ti x )O3, Pb(Sc0.5Nb0.5)O3, Ba(Zr1-x Ti x )O3, Pb(Mg1/3Nb2/3)O3 and (Bi1-x Nd x )FeO3. It is found that these SQS configurations can reproduce many properties of large random supercells of most of these disordered perovskite alloys, below some finite material-dependent temperature. Examples of these properties are electrical polarization, anti-phase and in-phase octahedral tiltings, antipolar motions, antiferromagnetism, strain, piezoelectric coefficients, dielectric response, specific heat and even the formation of polar nanoregions (PNRs) in some relaxors. Some limitations of these SQS configurations are also pointed out and explained. PMID:27661191

  18. Special quasirandom structures for perovskite solid solutions

    NASA Astrophysics Data System (ADS)

    Jiang, Zhijun; Nahas, Yousra; Xu, Bin; Prosandeev, Sergey; Wang, Dawei; Bellaiche, Laurent

    2016-11-01

    Special quasirandom structures (SQS) are presently generated for disordered (A‧1-x {{\\text{A}}\\prime \\prime} x )BX3 and A(B‧1-x {{\\text{B}}\\prime \\prime} x )X3 perovskite solid solutions, with x  =  1/2 as well as 1/3 and 2/3. These SQS configurations are obtained by imposing that the so-called Cowley parameters are as close to zero as possible for the three nearest neighboring shells. Moreover, these SQS configurations are slightly larger in size than those available in the literature for x  =  1/2, mostly because of the current capabilities of atomistic techniques. They are used here within effective Hamiltonian schemes to predict various properties, which are then compared to those associated with large random supercells, in a variety of compounds, namely (Ba1-x Sr x )TiO3, Pb(Zr1-x Ti x )O3, Pb(Sc0.5Nb0.5)O3, Ba(Zr1-x Ti x )O3, Pb(Mg1/3Nb2/3)O3 and (Bi1-x Nd x )FeO3. It is found that these SQS configurations can reproduce many properties of large random supercells of most of these disordered perovskite alloys, below some finite material-dependent temperature. Examples of these properties are electrical polarization, anti-phase and in-phase octahedral tiltings, antipolar motions, antiferromagnetism, strain, piezoelectric coefficients, dielectric response, specific heat and even the formation of polar nanoregions (PNRs) in some relaxors. Some limitations of these SQS configurations are also pointed out and explained.

  19. 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).

  20. Atomistic theory of hybrid improper ferroelectricity in perovskites

    NASA Astrophysics Data System (ADS)

    Zhao, Hong Jian; Íñiguez, Jorge; Ren, Wei; Chen, Xiang Ming; Bellaiche, L.

    2014-05-01

    We discuss the so-called hybrid improper ferroelectricity (HIF) appearing in A'BO3/A''BO3 perovskite superlattices. By means of straightforward analytical derivations and/or associated graphical analysis, we demonstrate that two previously-proposed elemental interatomic couplings between the O6 octahedral rotations and the displacements of the A-site cations [Bellaiche and Íñiguez, Phys. Rev. B 88, 014104 (2013), 10.1103/PhysRevB.88.014104] naturally reproduce and explain HIF in (A'BO3)1/(A''BO3)1 superlattices composed of layers that are only one unit cell thick. Further, we show that our approach permits an easy treatment of superlattices of arbitrary stacking direction and layer thickness. In particular, this allows us to predict (i) other previously overlooked types of HIF in (A'BO3)1/(A''BO3)1 superlattices and (ii) original and striking effects, such as the possibility of discretizing the magnitude of the spontaneous polarization in (A'BO3)m/(A''BO3)n systems when varying the m and n layer thicknesses. We further show first-principles results confirming the latter predictions.

  1. New Generation Perovskite Thermal Barrier Coating Materials

    NASA Astrophysics Data System (ADS)

    Ma, W.; Jarligo, M. O.; Mack, D. E.; Pitzer, D.; Malzbender, J.; Vaßen, R.; Stöver, D.

    2008-12-01

    Advanced ceramic materials of perovskite structure have been developed for potential application in thermal barrier coating systems, in an effort to improve the properties of the pre-existing ones like yttria-stabilized zirconia. Yb2O3 and Gd2O3 doped strontium zirconate (SrZrO3) and barium magnesium tantalate (Ba(Mg1/3Ta2/3)O3) of the ABO3 and complex A(B'1/3B''2/3)O3 systems, respectively, have been synthesized using ball milling prior to solid state sintering. Thermal and mechanical investigations show desirable properties for high-temperature coating applications. On atmospheric plasma spraying, the newly developed thermal barrier coatings reveal promising thermal cycle lifetime up to 1350 °C.

  2. 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.

  3. Nanoscale Atomic Displacements Ordering for Enhanced Piezoelectric Properties in Lead-Free ABO3 Ferroelectrics.

    PubMed

    Pramanick, Abhijit; Jørgensen, Mads R V; Diallo, Souleymane O; Christianson, Andrew D; Fernandez-Baca, Jaime A; Hoffmann, Christina; Wang, Xiaoping; Lan, Si; Wang, Xun-Li

    2015-08-01

    In situ synchrotron X-ray diffuse scattering and inelastic neutron scattering measurements from a prototype ABO3 ferroelectric single-crystal are used to elucidate how electric fields along a nonpolar direction can enhance its piezoelectric properties. The central mechanism is found to be a nanoscale ordering of B atom displacements, which induces increased lattice instability and therefore a greater susceptibility to electric-field-induced mechanical deformation.

  4. Electronic structure of the superconducting layered perovskite niobate

    NASA Astrophysics Data System (ADS)

    Hase, Izumi; Nishihara, Yoshikazu

    1998-07-01

    The electronic energy-band structure for RbLaNb2O7, which is closely related to the layered perovskite niobate superconducting KCa2Nb3O10 and metallic KLaNb2O7 with Li intercalation, has been calculated by using the scalar-relativistic full-potential linearized augmented-plane-wave method within the local-density approximation. The result of the calculation shows that this compound is a band insulator with a small gap, and its conduction band is a typical two-dimensional one and the valence band is rather three dimensional. We can conclude that the layered perovskite niobate KCa2Nb3O10 is a band insulator that can be superconducting with electron doping, and have the highly two-dimensional electronic structure.

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

    DOE PAGES

    Yuan, Yongbo; Chae, Jungseok; Shao, Yuchuan; Wang, Qi; Xiao, Zhengguo; Centrone, Andrea; Huang, Jinsong

    2015-06-05

    In this study, long range electromigration of methylammonium ions (MA+) in methyl ammonium lead tri-iodide (MAPbI3) 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 MAPbI3 perovskite devices.

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

    SciTech Connect

    Yuan, Yongbo; Chae, Jungseok; Shao, Yuchuan; Wang, Qi; Xiao, Zhengguo; Centrone, Andrea; Huang, Jinsong

    2015-06-05

    In this study, long range electromigration of methylammonium ions (MA+) in methyl ammonium lead tri-iodide (MAPbI3) 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 MAPbI3 perovskite devices.

  7. 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 (ABO3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA’BB’O6) 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 SrLaTiAlO6. 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 end member single perovskites.more » 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 Ti4+ 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

  8. X-ray absorption spectroscopy of Ru-doped relaxor ferroelectrics with a perovskite-type structure

    NASA Astrophysics Data System (ADS)

    Vitova, T.; Mangold, S.; Paulmann, C.; Gospodinov, M.; Marinova, V.; Mihailova, B.

    2014-04-01

    X-ray absorption near-edge structure and extended x-ray absorption fine structure spectroscopy at the Ru K edge of Ru-doped PbSc0.5Ta0.5O3 (PST-Ru), PbSc0.5Nb0.5O3 (PSN-Ru), and 0.9PbZn1/3Nb2/3O3-0.1PbTiO3 (PZN-0.1PT-Ru) as well as at the Ta L3 edge of PST-Ru and the Nb K edge of PSN-Ru was applied to study the short- and intermediate-range atomic arrangements in perovskite-type (ABO3) relaxor ferroelectrics. The compounds were also analyzed by complementary Raman scattering, visible/near-visible absorption spectroscopy, and synchrotron x-ray single-crystal diffraction. The results show that Ru is octahedrally coordinated in all three relaxor host matrices but the average oxidation state of Ru in PST-Ru and PSN-Ru is ˜4.4, whereas it is ˜3.8 in PZN-0.1PT-Ru. In PbSc0.5B''0.5O3 (B'' = Ta, Nb) Ru substitutes for the B'' cations in the form of isolated point defects, while in PZN-0.1PT-Ru Ru replaces adjacent A and B sites, forming a chainlike structural species of face-sharing elongated octahedra. Chemical 1:1 B-site order as well as dynamic BO6 tilting is observed around both the Ru dopant and the major B'' cation in PST-Ru and PSN-Ru regardless of the fact that according to x-ray diffraction at ambient conditions, the average structure is cubic with weak or no long-range chemical order. Pb cations are off-center displaced from the prototypic cubic A site for all three compounds and in Ru-doped PbSc0.5B''0.5O3 the BO6 tilt angle correlates with the degree of coherent B-Pb distances.

  9. Fluorination of epitaxial oxides: synthesis of perovskite oxyfluoride thin films.

    PubMed

    Moon, Eun Ju; Xie, Yujun; Laird, Eric D; Keavney, David J; Li, Christopher Y; May, Steven J

    2014-02-12

    While the synthesis of ABO3 perovskite films has enabled new strategies to control the functionality of this material class, the chemistries that have been realized in thin film form constitute only a fraction of those accessible to bulk chemists. Here, we report the synthesis of oxyfluoride films, where the incorporation of F may provide a new means to tune physical properties in thin films by modifying electronic structure. Fluorination is achieved by spin coating a poly(vinylidene fluoride) (PVDF) solution onto oxygen-deficient films. The film/polymer bilayer is then annealed, promoting the diffusion of F into the film. We have used this method to synthesize SrFeO(3-α)Fγ films, as confirmed by X-ray photoemission spectroscopy and X-ray absorption spectroscopy. PMID:24443775

  10. Lateral-Structure Single-Crystal Hybrid Perovskite Solar Cells via Piezoelectric Poling.

    PubMed

    Dong, Qingfeng; Song, Jingfeng; Fang, Yanjun; Shao, Yuchuan; Ducharme, Stephen; Huang, Jinsong

    2016-04-13

    Single-crystal perovskite solar cells with a lateral structure yield an efficiency enhancement 44-fold that of polycrystalline thin films, due to the much longer carrier diffusion length. A piezoelectric effect observed in perovskite single-crystal and the strain-generated grain-boundaries enable ion migration to form a p-i-n structure. PMID:26836224

  11. Lateral-Structure Single-Crystal Hybrid Perovskite Solar Cells via Piezoelectric Poling.

    PubMed

    Dong, Qingfeng; Song, Jingfeng; Fang, Yanjun; Shao, Yuchuan; Ducharme, Stephen; Huang, Jinsong

    2016-04-13

    Single-crystal perovskite solar cells with a lateral structure yield an efficiency enhancement 44-fold that of polycrystalline thin films, due to the much longer carrier diffusion length. A piezoelectric effect observed in perovskite single-crystal and the strain-generated grain-boundaries enable ion migration to form a p-i-n structure.

  12. Magnetic coupling at perovskite and rock-salt structured interfaces

    SciTech Connect

    Matvejeff, M.; Ahvenniemi, E.; Takahashi, R.; Lippmaa, M.

    2015-10-05

    We study magnetic coupling between hole-doped manganite layers separated by either a perovskite or a rock-salt barrier of variable thickness. Both the type and the quality of the interface have a strong impact on the minimum critical barrier thickness where the manganite layers become magnetically decoupled. A rock-salt barrier layer only 1 unit cell (0.5 nm) thick remains insulating and is able to magnetically de-couple the electrode layers. The technique can therefore be used for developing high-performance planar oxide electronic devices such as magnetic tunnel junctions and quantum well structures that depend on magnetically and electronically sharp heterointerfaces.

  13. 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.

  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. PMID:27386731

  15. Autothermal reforming of propane over Ni catalysts supported on a variety of perovskites.

    PubMed

    Lim, SeungSoo; Moon, DongJu; Kim, JongHo; Kim, YoungChul; Park, NamCook; Shin, JaeSoon

    2007-11-01

    Autothermal reforming of propane for hydrogen over Ni catalysts supported on a variety of perovskites was performed in an atmospheric flow reactor. Perovskite is known for its higher thermal stability and oxygen storage capacity, but catalytic activity of itself is low. A sites of the ABO3 structured perovskites were occupied by La while B sites by one of Fe, Co, Ni, and Al by citrate method. The composition of the reactant mixture was H2O/C/O2 = 8.96/1.0/1.1. The changes in the states of the catalysts after reaction were analyzed by XRD, TPD, and TGA. Ni/LaAlO3 catalyst maintained the perovskite structure after reaction. It showed higher hydrogen yield and thermal stability compared to those of the catalysts with Fe, Co, or Ni in B sites. Catalysts prepared by deposition-precipitation (DP) method showed higher activity than those prepared by impregnation method, presumably due to the smaller sizes of the NiO crystal particles.

  16. Double Double Cation Order in the High-Pressure Perovskites MnRMnSbO6.

    PubMed

    Solana-Madruga, Elena; Arévalo-López, Ángel M; Dos Santos-García, Antonio J; Urones-Garrote, Esteban; Ávila-Brande, David; Sáez-Puche, Regino; Attfield, J Paul

    2016-08-01

    Cation ordering in ABO3 perovskites adds to their chemical variety and can lead to properties such as ferrimagnetism and magnetoresistance in Sr2 FeMoO6 . Through high-pressure and high-temperature synthesis, a new type of "double double perovskite" structure has been discovered in the family MnRMnSbO6 (R=La, Pr, Nd, Sm). This tetragonal structure has a 1:1 order of cations on both A and B sites, with A-site Mn(2+) and R(3+) cations ordered in columns and Mn(2+) and Sb(5+) having rock salt order on the B sites. The MnRMnSbO6 double double perovskites are ferrimagnetic at low temperatures with additional spin-reorientation transitions. The ordering direction of ferrimagnetic Mn spins in MnNdMnSbO6 changes from parallel to [001] below TC =76 K to perpendicular below the reorientation transition at 42 K at which Nd moments also order. Smaller rare earths lead to conventional monoclinic double perovskites (MnR)MnSbO6 for Eu and Gd. PMID:27312417

  17. Double Double Cation Order in the High-Pressure Perovskites MnRMnSbO6.

    PubMed

    Solana-Madruga, Elena; Arévalo-López, Ángel M; Dos Santos-García, Antonio J; Urones-Garrote, Esteban; Ávila-Brande, David; Sáez-Puche, Regino; Attfield, J Paul

    2016-08-01

    Cation ordering in ABO3 perovskites adds to their chemical variety and can lead to properties such as ferrimagnetism and magnetoresistance in Sr2 FeMoO6 . Through high-pressure and high-temperature synthesis, a new type of "double double perovskite" structure has been discovered in the family MnRMnSbO6 (R=La, Pr, Nd, Sm). This tetragonal structure has a 1:1 order of cations on both A and B sites, with A-site Mn(2+) and R(3+) cations ordered in columns and Mn(2+) and Sb(5+) having rock salt order on the B sites. The MnRMnSbO6 double double perovskites are ferrimagnetic at low temperatures with additional spin-reorientation transitions. The ordering direction of ferrimagnetic Mn spins in MnNdMnSbO6 changes from parallel to [001] below TC =76 K to perpendicular below the reorientation transition at 42 K at which Nd moments also order. Smaller rare earths lead to conventional monoclinic double perovskites (MnR)MnSbO6 for Eu and Gd.

  18. Crystal structure of Ba9La2W4O24 and Sr9Gd2W4O24: A new B-site vacancy ordered 4×4×4 cubic perovskite

    NASA Astrophysics Data System (ADS)

    IJdo, D. J. W.; Fu, W. T.; Akerboom, S.

    2016-06-01

    The crystal structure of Ba9La2W4O24 and the high-temperature modification Sr9Gd2W4O24 has been investigated by the Rietveld method using X-ray powder diffraction data. They crystalize in a 4×4×4 cubic superstructure of the simple cubic perovskite ABO3 with the space group Fm 3 bar and lattice parameter a≈4ap, where ap denotes the lattice constant of the primitive cubic perovskite. The structure consists of the ordered B-site vacancies (☐) and the structure formula can be written as Ba2(Ba1/4La1/2)☐1/4WO6 and (Sr/Gd)2((Sr/Gd)3/4)☐1/4WO6 due to a partial disorder between one of the Sr at A-site and the Gd at B-site. The three crystallographically different W and the randomly distributed Ba/La or (Sr/Gd) ions occupy the B-sites. Two W ions are coordinated with 6 oxygens and arranged as octahedra, but the third one is surrounded by 12 partially occupied (50%) oxygens, which can be viewed as a combination of four tetrahedra. The coordination geometry of the larger B-cations (Ba/La and Sr/Gd) is not octahedral; they coordinate with seven oxygens instead. In addition, the Ba/LaO7 or (Sr/GdO7) polyhedron shares some oxygen atoms with four neighbours. The B-site vacancies form a primitive cube with a≈2ap, and are surrounded by six equal but differently orientated WO6 octahedra being caused by a rotation about a twofold axis.

  19. 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.

  20. 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

  1. Significant enhancement of photovoltage in artificially designed perovskite oxide structures

    NASA Astrophysics Data System (ADS)

    Zhou, Wen-jia; Jin, Kui-juan; Guo, Hai-zhong; He, Xu; He, Meng; Xu, Xiu-lai; Lu, Hui-bin; Yang, Guo-zhen

    2015-03-01

    La0.9Sr0.1MnO3/insulator/SrNb0.007Ti0.993O3 multilayer and La0.9Sr0.1MnO3/SrNb0.007Ti0.993O3/In2O3:SnO2(ITO)/La0.9Sr0.1MnO3/SrNb0.007Ti0.993O3 multilayer structures were designed to enhance the photovoltage. The photovoltages of these two structures under an illumination of 308 nm laser are 410 and 600 mV, respectively. The latter is 20 times larger than that (30 mV) observed in La0.9Sr0.1MnO3/SrNb0.007Ti0.993O3 single junction. The origin of such significant enhancement of photovoltage is discussed in this letter. These results suggest that the photoelectric property of perovskite oxides could be much improved by artificial structure designing. The enhanced photovoltaic effects have potential applications in the ultraviolet photodetection and solar cells.

  2. Highly Efficient Perovskite Solar Cells with Tunable Structural Color

    PubMed Central

    2015-01-01

    The performance of perovskite solar cells has been progressing over the past few years and efficiency is likely to continue to increase. However, a negative aspect for the integration of perovskite solar cells in the built environment is that the color gamut available in these materials is very limited and does not cover the green-to-blue region of the visible spectrum, which has been a big selling point for organic photovoltaics. Here, we integrate a porous photonic crystal (PC) scaffold within the photoactive layer of an opaque perovskite solar cell following a bottom-up approach employing inexpensive and scalable liquid processing techniques. The photovoltaic devices presented herein show high efficiency with tunable color across the visible spectrum. This now imbues the perovskite solar cells with highly desirable properties for cladding in the built environment and encourages design of sustainable colorful buildings and iridescent electric vehicles as future power generation sources. PMID:25650872

  3. Highly efficient perovskite solar cells with tunable structural color.

    PubMed

    Zhang, Wei; Anaya, Miguel; Lozano, Gabriel; Calvo, Mauricio E; Johnston, Michael B; Míguez, Hernán; Snaith, Henry J

    2015-03-11

    The performance of perovskite solar cells has been progressing over the past few years and efficiency is likely to continue to increase. However, a negative aspect for the integration of perovskite solar cells in the built environment is that the color gamut available in these materials is very limited and does not cover the green-to-blue region of the visible spectrum, which has been a big selling point for organic photovoltaics. Here, we integrate a porous photonic crystal (PC) scaffold within the photoactive layer of an opaque perovskite solar cell following a bottom-up approach employing inexpensive and scalable liquid processing techniques. The photovoltaic devices presented herein show high efficiency with tunable color across the visible spectrum. This now imbues the perovskite solar cells with highly desirable properties for cladding in the built environment and encourages design of sustainable colorful buildings and iridescent electric vehicles as future power generation sources.

  4. Crystal Structure of a Layered Perovskite Niobate KCa 2Nb 3O 10

    NASA Astrophysics Data System (ADS)

    Fukuoka, Hiroshi; Isami, Toshiyuki; Yamanaka, Shoji

    2000-04-01

    The crystal structure of a layered perovskite niobate KCa2Nb3O10 was investigated through single-crystal X-ray analysis. The niobate crystallized in the orthorhombic system Cmcm with lattice constants of a=3.8802(9) Å, b=29.508(6) Å, c=7.714(1) Å, V=883.2(2) Å3. The final refinement using the 908 independent reflections converged into R=4.1%, and Rw=4.7%. The structure of KCa2Nb3O10 was composed of triple-layered perovskite slabs, potassium ions being situated between the slabs. The adjacent perovskite slabs, stacking along the c axis, were mutually displaced with a displacement vector of a→/2. The potassium ions were coordinated by six oxygen atoms to form two short and four long bonds. Apparent disordering was observed in the equatorial oxygen sites of the central niobium atoms in the triple perovskite slabs.

  5. Coordination Chemistry Dictates the Structural Defects in Lead Halide Perovskites.

    PubMed

    Rahimnejad, Sara; Kovalenko, Alexander; Forés, Sergio Martí; Aranda, Clara; Guerrero, Antonio

    2016-09-19

    We show the influence of species present in precursor solution during formation of lead halide perovskite materials on the structural defects of the films. The coordination of lead by competing solvent molecules and iodide ions dictate the type of complexes present in the films. Depending on the processing conditions all PbIS5 (+) , PbI2 S4, PbI3 S3 (-) , PbI4 S2 (2-) , PbI5 S2 (3-) , PbI6 (4-) and 1D (Pb2 I4 )n chains are observed by absorption measurements. Different parameters are studied such as polarity of the solvent, concentration of iodide ions, concentration of solvent molecules and temperature. It is concluded that strongly coordinating solvents will preferentially form species with a low number of iodide ions and less coordinative solvents generate high concentration of PbI6 (-) . We furthermore propose that all these plumbate ions may act as structural defects determining electronic properties of the photovoltaic films.

  6. Interplay of octahedral rotations and breathing distortions in charge-ordering perovskite oxides

    NASA Astrophysics Data System (ADS)

    Balachandran, Prasanna V.; Rondinelli, James M.

    2013-08-01

    We investigate the structure-property relationships in ABO3 perovskites exhibiting octahedral rotations and cooperative octahedral breathing distortions (CBD) using group theoretical methods. Rotations of octahedra are ubiquitous in the perovskite family, while the appearance of breathing distortions—oxygen displacement patterns that lead to approximately uniform dilation and contraction of the BO6 octahedra—are rarer in compositions with a single, chemically unique B site. The presence of a CBD relies on electronic instabilities of the B-site cations, either orbital degeneracies or valence-state fluctuations, and often appear concomitant with charge order metal-insulator transitions or B-site cation ordering. We enumerate the structural variants obtained from rotational and breathing lattice modes and formulate a general Landau functional describing their interaction. We use this information and combine it with statistical correlation techniques to evaluate the role of atomic scale distortions on the critical temperatures in representative charge ordering nickelate and bismuthate perovskites. Our results provide microscopic insights into the underlying structure-property interactions across electronic and magnetic phase boundaries, suggesting plausible routes to tailor the behavior of functional oxides by design.

  7. Swift heavy ion-induced amorphization of CaZrO3 perovskite

    NASA Astrophysics Data System (ADS)

    Lang, Maik; Zhang, Fuxiang; Li, Weixing; Severin, Daniel; Bender, Markus; Klaumünzer, Siegfried; Trautmann, Christina; Ewing, Rodney C.

    2012-09-01

    Perovskite, ABO3, structures are an important class of ceramics with a large variety of derivative structure-types (cubic, tetragonal, hexagonal, orthorhombic, and rhombohedral). Radiation damage in perovskites is of interest due to their potential as actinide waste forms and to understand radiation effects in uranium- and thorium-bearing phases. Powder CaZrO3 perovskite was irradiated with 940-MeV Au ions up to 1.5 × 1013 ions/cm2. Changes in the crystal structure were followed in situ as function of fluence by means of a sequence of X-ray diffraction (XRD) measurements. Ion-induced amorphization is evidenced by a decrease in diffraction intensity and an increase in diffuse scattering. Based on XRD measurements, as well as transmission electron microscopy (TEM), CaZrO3 is completely amorphized at a fluence of 1.5 × 1013 ions/cm2. From the evolution of the integrated XRD-maxima intensities with fluence, the diameter of the amorphous tracks is estimated to be 6.0 ± 0.6 nm, which is independently confirmed by bright-field TEM images: 6.7 ± 0.4 nm. Changes in the positions of diffraction maxima may be caused by at least two processes. Broadening of the diffraction maxima is analyzed using a Williamson-Hall plot. Strain-induced broadening is the dominant process.

  8. 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

  9. Structure, Growth Process, and Growth Mechanism of Perovskite in High-Titanium-Bearing Blast Furnace Slag

    NASA Astrophysics Data System (ADS)

    Liu, Lu; Hu, Meilong; Xu, Yuzhou; Bai, Chenguang; Gan, Yunhua

    2015-08-01

    The isothermal crystallization of perovskite in TiO2-CaO-SiO2-Al2O3-MgO high-titanium-bearing blast furnace slag was observed in situ at 1698 K (1425 °C) using a confocal scanning laser microscope. The dendrite structure of perovskite (CaTiO3) thus obtained showed vividly the primary dendrite trunks and secondary dendrite arms. Furthermore, the dendritic growth of perovskite in liquid slag was clearly observed on line. The results showed that the dendrite arrays in which the primary dendrite trunks observed on slag surface were parallel with each other grew toward the same direction. The secondary dendrite arms grew in the perpendicular direction with the primary trucks and stopped growing when they encounter. The perovskite dendrites showed a linear growth at two stages. The dendrites grew faster at early stage at about 5 to 7 μm/s and grew with a lower growth rate at about 1 to 2 μm/s in later stage. Finally, the growth mechanism of perovskite in melt was analyzed with the solidification theory. Based on the theoretical calculation of equilibrium phases in slag, the initial slag could be considered as a binary component system. One component was perovskite and the other component was the sum of all the other species that did not attend the crystallization of perovskite (included SiO2, Al2O3, and MgO, as well as CaO and TiO2 that were not involved in the solid formation). The formation of perovskite required the diffusion of CaO and TiO2 to the solid/liquid interface and the rejection of the other species from the interface. The solid/liquid equilibrium schematic diagram was made based on the calculation.

  10. Structure Investigation of CaSiO3 Perovskite at 91 GPa

    NASA Astrophysics Data System (ADS)

    Martin, C.; Prakapenka, V.; Parise, J. B.

    2007-12-01

    The crystallographic structure of CaSiO3 perovskite at 91(2) GPa is investigated using monochromatic X-ray diffraction and the laser-heated diamond anvil cell with a graphite gasket-insert to increase the volume of the sample under diffraction conditions. We report observations of weak X-ray reflections at d-spaces matching a perovskite super-structure, which appear in addition to splitting of diffraction from the cubic sub-structure. Considering this data in context with the space groups (SGs) of all perovskite structures observed experimentally and recorded in the Inorganic Crystal Structure Database, CaSiO3 perovskite adopts one of two possible tetragonal structures ( P4/ mbm, SG #127, rather than I4/ mcm, SG #123) after cooling from 2000(300) K at this pressure if an orthorhombic or monoclinic unit cell is discounted. When an orthorhombic perovskite structure is considered, reflections from the perovskite super-structure discount Imam (SG #74) and could favor Cmcm (SG #74) above Pbnm (SG #62). The raw diffraction data from CaSiO3 and our analysis are presented in addition to a detailed procedure for the construction of the graphite gasket-insert used during the high pressure experiment. In brief, graphite is machined from a monochromator by electronic discharge and placed within a conventional tungsten gasket. Oriented with its a-axis perpendicular to the direction of force in the diamond anvil cell, a sample chamber is machined within the graphite-insert after indenting with the diamond anvils.

  11. 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

  12. Syntheses, structures, and ionic conductivities of perovskite-structured lithium–strontium–aluminum/gallium–tantalum-oxides

    SciTech Connect

    Phraewphiphat, Thanya; Iqbal, Muhammad; Suzuki, Kota; Matsuda, Yasuaki; Yonemura, Masao; Hirayama, Masaaki; Kanno, Ryoji

    2015-05-15

    The ionic conductivities of new perovskite-structured lithium–strontium–aluminum/gallium–tantalum oxides were investigated. Solid solutions of the new perovskite oxides, (Li{sub x}Sr{sub 1−x})(Al{sub (1−x)/2}Ta{sub (1+x)/2})O{sub 3} and (Li{sub x}Sr{sub 1−x})(Ga{sub (1−x)/2}Ta{sub (1+x)/2})O{sub 3}, were synthesized using a ball-milled-assisted solid-state method. The partial substitution of the smaller Ga{sup +3} for Ta{sup +5} resulted in new compositions, the structures of which were determined by neutron diffraction measurements using a cubic perovskite structural model with the Pm−3m space group. Vacancies were introduced into the Sr(Li) sites by the formation of solid solutions with compositions (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3}, where the composition range of 0≤y≤0.20 was examined for x=0.2 and 0.25. The highest conductivity, 1.85×10{sup −3} S cm{sup −1} at 250 °C, was obtained for (Li{sub 0.25}Sr{sub 0.625}☐{sub 0.125})(Ga{sub 0.25}Ta{sub 0.75})O{sub 3} (x=0.25, y=0.125). Enhanced ionic conductivities were achieved by the introduction of vacancies at the A-sites. - Graphical abstract: Novel lithium-conducting oxides with the cubic perovskite structure (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3} provide a specific solid-solution region with various x and y values, exhibiting the highest ionic conductivity (1.85 S cm{sup −1} at 250 °C) for (Li{sub 0.25}Sr{sub 0.625}☐{sub 0.125})(Ga{sub 0.25}Ta{sub 0.75})O{sub 3} (x=0.25, y=0.125 in (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3}). The vacancies (☐) introduced into the A-sites contribute to the enhancement of lithium diffusion in the perovskite structure because of the enlargement of the bottleneck size and suppression of the interaction between lithium and oxygen. - Highlights: • The perovskite-structured novel Li

  13. Composition and crystal structure of perovskite films attained from electrodes of used car battery

    NASA Astrophysics Data System (ADS)

    Dhiaputra, Ilham; Permana, Bayu; Maulana, Yusep; Inayatie, Yuniar Dwi; Purba, Yonatan R.; Bahtiar, Ayi

    2016-02-01

    Perovskite solar cells have been intensively investigated for high performance and low-cost solid-state solar cells. Perovskite based-lead materials are commonly used as active material for high power conversion efficiency solar cells. Herein, we report our study on the development of used electrodes car battery as a cheap raw lead material to be converted into lead (II) iodide PbI2 by using simple chemical method. We have successfully obtained PbI2 material with purity higher than 85% and its crystal structure is comparable with that of commercial product. The perovskite CH3NH3PbI3 film was prepared by spin-coating of PbI2 solution and followed by spin-coating two-times of methylamonium iodide (MAI) solution. In this paper, the crystal structure of perovskite film attained from used car battery is shown and compared with that of prepared from commercial PbI2. By utilizing the used car battery into perovskite valuable material for high performance solar cells, we can not only improve the economical value (added-value) of wasted car battery but also we can simultaneously save the environment.

  14. High-Throughput Density Functional Theory Categorization of Ferroelectric Ternary Perovskite Oxides for Use as High-Performance Piezoelectrics

    NASA Astrophysics Data System (ADS)

    Armiento, Rickard; Kozinsky, Boris; Fornari, Marco; Ceder, Gerbrand

    2011-03-01

    We present a nearly exhaustive density functional theory (DFT) survey over the chemical space of perovskite compounds on ABO3 form, with the aim of identifying alloy end points for new piezoelectric materials. Our screening criteria on the DFT results selects 85 relevant compounds, among which all well known alloy end points for high performance piezoelectrics are present. We analyze the compounds with respect to macroscopic polarization, born effective charges, and energy differences between different structure distortions. We discuss the energy features that cause the high piezoelectric performance of the well known piezoelectric lead zirconate titanate (PZT), and to what extent these features are rare among the found compounds. The results are used to discuss relevant isovalent alloys of the selected compounds.

  15. Tuning bipolar resistive switching by forming defect dipoles in A-site-deficient perovskite calcium titanate thin films

    NASA Astrophysics Data System (ADS)

    Xie, Wei; Hu, Wei; Zou, Lilan; Chen, Ruqi; Li, Baojun; Bao, Dinghua

    2015-04-01

    If we intentionally make the A-site in an ABO3 perovskite structure deficient, it is possible to tune the resistive switching effect by forming defect dipoles. In this study, an A-site-deficient calcium titanate (Ca0.95TiO3, CTO) thin film was fabricated on a Pt/Ti/SiO2/Si substrate as an active layer for resistive random-access memory. The Pt/CTO/Pt device exhibited stable bipolar resistive switching performance with good endurance and long retention. The resistive switching may be attributable to the formation and rupture of the conduction filaments due to the O vacancies and defect dipoles resulting from the interaction between the Ca and O vacancies.

  16. Exploring the Electronic Band Structure of Organometal Halide Perovskite via Photoluminescence Anisotropy of Individual Nanocrystals.

    PubMed

    Täuber, Daniela; Dobrovolsky, Alexander; Camacho, Rafael; Scheblykin, Ivan G

    2016-08-10

    Understanding electronic processes in organometal halide perovskites, flourishing photovoltaic, and emitting materials requires unraveling the origin of their electronic transitions. Light polarization studies can provide important information regarding transition dipole moment orientations. Investigating individual methylammonium lead triiodide perovskite nanocrystals enabled us to detect the polarization of photoluminescence intensity and photoluminescence excitation, hidden in bulk samples by ensemble averaging. Polarization properties of the crystals were correlated with their photoluminescence spectra and electron microscopy images. We propose that distortion of PbI6 octahedra leads to peculiarities of the electronic band structure close to the band-edge. Namely, the lowest band transition possesses a transition dipole moment along the apical Pb-I-Pb bond resulting in polarized photoluminescence. Excitation of photoluminescence above the bandgap is unpolarized because it involves molecular orbitals delocalized both in the apical and equatorial directions of the perovskite octahedron. Trap-assisted emission at 77 K, rather surprisingly, was polarized similar to the bandgap emission.

  17. Structural, Optical, and Electronic Properties of Wide Bandgap Perovskites: Experimental and Theoretical Investigations.

    PubMed

    Kumawat, Naresh K; Tripathi, Madhvendra Nath; Waghmare, Umesh; Kabra, Dinesh

    2016-06-01

    Wide bandgap hybrid halide perovskites based on bromine and chlorine halide anions have emerged as potential candidates for various optoelectronic devices. However, these materials are relatively less explored than the iodine-based perovskites for microscopic details. We present experiment and first-principles calculations to understand the structural, optical, and electronic structure of wide bandgap CH3NH3Pb(Br1-xClx)3 (x = 0, 0.33, 0.66, and 1) 3D hybrid perovskite materials. We substituted Br(-) with Cl(-) to tune the bandgap from 2.4 eV (green emissive) to 3.2 eV (blue (UV) emissive) of these materials. We correlate our experimental results with first-principles theory and provide an insight into important parameters like lattice constants, electronic structure, excitonic binding energy (EX), dielectric constant, and reduced effective mass (μr) of charge carriers in these perovskite semiconductors. Electronic structure calculations reveal that electronic properties are mainly governed by Pb 6p and halide p orbitals. Our estimates of EX within a hydrogen model suggest that an increase in EX by increasing the Cl(-) (chlorine) concentration is mainly due to a decrease in the dielectric constant with x and almost constant value of μr close to the range of 0.07me. PMID:27203800

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

    DOE PAGES

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

    2015-07-23

    Here we explored the use of machine learning methods for classifying whether a particularABO3chemistry 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 theAandBatoms tomore » 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

  19. Luminescence studies of perovskite structured titanates: A review

    NASA Astrophysics Data System (ADS)

    Nag Bhargavi, G.; Khare, Ayush

    2015-06-01

    Apart from widely known dielectric and ferroelectric properties, the perovskite type materials also constitute a class of materials, which are recently investigated for their optical properties. These materials are being used for fabrication of various microelectronics and optoelectronic devices. Photoluminescence (PL), mechanoluminescence (ML) and thermoluminescence (TL) are such phenomena offering numerous applications in different fields like electro-optics, flat panel displays, LED technology, sensors, dynamic visualization etc. This paper briefly reviews the status and new progress in luminescence studies of ferroelectric materials like barium titanate (BT), barium zirconate titanate (BZT), calcium titanate (CT), calcium zirconate titanate (CZT), lead titanate (PT), lead zirconate titanate (PZT), etc., prepared through various methods.

  20. Energetics of perovskite-type materials applied in solid oxide fuel cells (SOFCs): Electrolytes, cathodes and interconnects

    NASA Astrophysics Data System (ADS)

    Cheng, Jihong

    Perovskite-type oxides (ABO3) find a great variety of applications in solid oxide fuel cells (SOFCs), including solid electrolytes, cathodes and interconnects, which are closely related to the defect chemistry involved. Thermodynamic studies are needed to systematically understand the nature of the structure-property relations and provide guidance to predict and/or select proper materials. High temperature solution calorimetry in molten oxide solvents is a powerful tool and has been applied for several perovskite systems that have simple (undoped) and complex (doped) compositions. LaBO3 perovskites (B = Al, Ga, Sc, In, Cr, Fe, Co, Ni) represent a group of excellent parent materials for electrolytes, cathodes, and interconnects in SOFCs. Their enthalpies of formation from oxides generally exhibit a relationship between stability and the major structural parameter for perovskites, the tolerance factor. As the tolerance factor deviates more from unity, the enthalpy of formation from oxides becomes less exothermic. This work verifies this general trend for A3+B3+O3 type perovskites, joining other two types, i.e., A1+B5+O 3 and A2+B4+O3. In alkaline earth doped perovskites, though structural parameters are likely to continue affecting stability, defects, which are introduced upon doping, actually play a more profound role in defining energetic trends. In the newly developed electrolyte materials, Mg, Sr, and Ba-doped LaGaO 3 perovskites, oxygen vacancies are created to compensate the charge imbalance between dopant and host ions. Oxygen vacancies have a destabilization effect on the structure due to the partial disconnection of the corner-shared BO6 octahedral framework. On the other hand, they tend to order at the short-range scale, forming vacancy-dopant clusters, as evidenced by neutron diffraction. In alkaline earth doped perovskites that contain transition metals, two charge compensation scenarios are possible: oxidation of the transition metal or creation of

  1. Di-hydrogen contact induced lattice instabilities and structural dynamics in complex hydride perovskites.

    PubMed

    Schouwink, P; Hagemann, H; Embs, J P; D'Anna, V; Černý, R

    2015-07-01

    The structural phase transitions occurring in a series of perovskite-type complex hydrides based on the tetrahydroborate anion BH4(-) are investigated by means of in situ synchrotron x-ray powder diffraction, vibrational spectroscopy, thermal methods and ab initio calculations in the solid state. Structural dynamics of the BH4 anion are followed with quasi-elastic neutron scattering. We show that unexpected temperature-induced lattice instabilities in perovskite-type ACa(BH4)3 (A = K, Rb, Cs) have their origin in close hydridic di-hydrogen contacts. The rich lattice dynamics lead to coupling between internal B-H vibrations and phonons, resulting in distortions in the high-temperature polymorph that are identical in symmetry to well-known instabilities in oxide perovskites, generally condensing at lower temperatures. It is found that anion-substitution BH4(-) <-> (X = Halide) can relax distortions in ACa(BH4)3 by eliminating coulomb repulsive H(-)···H(-) effects. The interesting nature of phase transition in ACa(BH4)3 enters an unexplored field of weak interactions in ceramic-like host lattices and is the principal motivation for this study. Close di-hydrogen contacts suggest new concepts to tailor crystal symmetries in complex hydride perovskites in the future. PMID:26076047

  2. Flexible perovskite solar cells based on the metal-insulator-semiconductor structure.

    PubMed

    Wei, Jing; Li, Heng; Zhao, Yicheng; Zhou, Wenke; Fu, Rui; Pan, Huiyue; Zhao, Qing

    2016-09-14

    The metal-insulator-semiconductor (MIS) structure is applied to perovskite solar cells, in which the traditional compact layer TiO2 is replaced by Al2O3 as the hole blocking material to realize an all-low-temperature process. Flexible devices based on this structure are also realized with excellent flexibility, which hold 85% of their initial efficiency after bending 100 times. PMID:27524362

  3. Entropy-driven structural transition and kinetic trapping in formamidinium lead iodide perovskite

    PubMed Central

    Chen, Tianran; Foley, Benjamin J.; Park, Changwon; Brown, Craig M.; Harriger, Leland W.; Lee, Jooseop; Ruff, Jacob; Yoon, Mina; Choi, Joshua J.; Lee, Seung-Hun

    2016-01-01

    A challenge of hybrid perovskite solar cells is device instability, which calls for an understanding of the perovskite structural stability and phase transitions. Using neutron diffraction and first-principles calculations on formamidinium lead iodide (FAPbI3), we show that the entropy contribution to the Gibbs free energy caused by isotropic rotations of the FA+ cation plays a crucial role in the cubic-to-hexagonal structural phase transition. Furthermore, we observe that the cubic-to-hexagonal phase transition exhibits a large thermal hysteresis. Our first-principles calculations confirm the existence of a potential barrier between the cubic and hexagonal structures, which provides an explanation for the observed thermal hysteresis. By exploiting the potential barrier, we demonstrate kinetic trapping of the cubic phase, desirable for solar cells, even at 8.2 K by thermal quenching.

  4. Self-assembled single-phase perovskite nanocomposite thin films.

    PubMed

    Kim, Hyun-Suk; Bi, Lei; Paik, Hanjong; Yang, Dae-Jin; Park, Yun Chang; Dionne, Gerald F; Ross, Caroline A

    2010-02-10

    Thin films of perovskite-structured oxides with general formula ABO(3) have great potential in electronic devices because of their unique properties, which include the high dielectric constant of titanates, (1) high-T(C) superconductivity in cuprates, (2) and colossal magnetoresistance in manganites. (3) These properties are intimately dependent on, and can therefore be tailored by, the microstructure, orientation, and strain state of the film. Here, we demonstrate the growth of cubic Sr(Ti,Fe)O(3) (STF) films with an unusual self-assembled nanocomposite microstructure consisting of (100) and (110)-oriented crystals, both of which grow epitaxially with respect to the Si substrate and which are therefore homoepitaxial with each other. These structures differ from previously reported self-assembled oxide nanocomposites, which consist either of two different materials (4-7) or of single-phase distorted-cubic materials that exhibit two or more variants. (8-12) Moreover, an epitaxial nanocomposite SrTiO(3) overlayer can be grown on the STF, extending the range of compositions over which this microstructure can be formed. This offers the potential for the implementation of self-organized optical/ferromagnetic or ferromagnetic/ferroelectric hybrid nanostructures integrated on technologically important Si substrates with applications in magnetooptical or spintronic devices.

  5. 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.

  6. 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. PMID:27076212

  7. Computational Study of Structural and Electrical Properties of Methylammonium Lead Iodide Perovskite

    NASA Astrophysics Data System (ADS)

    Boinapally, Vamshidhar Rao

    Methyl ammonium lead iodide perovskite (CH3NH3PbI 3) plays an important role in light absorption in perovskite solar cells. The main aim of this thesis is to investigate the structural and electrical properties of cubic and tetragonal phases of CH3NH3PbI 3. The optimized structure and minimum energy lattice constants of relaxed cubic unit cells were initially computed. The most stable orientation of methylammonium cation was found to be in the [1 1 -1] direction. This directional preference is described by bonding analysis of the atomic cage of PbI3 with the C≡N dimer. The variation of c/a ratio with the distortion angle of PbI6 underlies the understanding of the transition from the cubic to the tetragonal phase. For the equilibrium structures band structures and effective masses were computed. The computed effective masses of both holes and electrons of CH 3NH3PbI3 are comparable to the widely used silicon in commercial inorganic solar cells. These results describe the light absorption nature of methylammonium lead iodide perovskite and its importance in future solar cell technology.

  8. 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

  9. Research Update: The electronic structure of hybrid perovskite layers and their energetic alignment in devices

    NASA Astrophysics Data System (ADS)

    Olthof, Selina

    2016-09-01

    In recent years, the interest in hybrid organic-inorganic perovskites has increased at a rapid pace due to their tremendous success in the field of thin film solar cells. This area closely ties together fundamental solid state research and device application, as it is necessary to understand the basic material properties to optimize the performances and open up new areas of application. In this regard, the energy levels and their respective alignment with adjacent charge transport layers play a crucial role. Currently, we are lacking a detailed understanding about the electronic structure and are struggling to understand what influences the alignment, how it varies, or how it can be intentionally modified. This research update aims at giving an overview over recent results regarding measurements of the electronic structure of hybrid perovskites using photoelectron spectroscopy to summarize the present status.

  10. Surface Tuning of La0.5Sr0.5CoO3 Perovskite Catalysts by Acetic Acid for NOx Storage and Reduction.

    PubMed

    Peng, Yue; Si, Wenzhe; Luo, Jinming; Su, Wenkang; Chang, Huazhen; Li, Junhua; Hao, Jiming; Crittenden, John

    2016-06-21

    Selective dissolution of perovskite A site (A of ABO3 structure) was performed on the La1 - xSrxCoO3 catalysts for the NOx storage and reduction (NSR) reaction. The surface area of the catalysts were enhanced using dilute HNO3 impregnation to dissolve Sr. Inactive SrCO3 was removed effectively within 6 h, and the catalyst preserved the perovskite framework after 24 h of treatment. The tuned catalysts exhibited higher NSR performance (both NOx storage and NO-to-NO2 oxidation) under lean-burn and fuel-rich cycles at 250 °C. Large amounts of NOx adsorption were due to the increase of nitrate/nitrite species bonding to the A site and the growth of newly formed monodentate nitrate species. Nitrate species were stored stably on the partial exposed Sr(2+) cations. These exposed Sr(2+) cations played an important role on the NOx reduction by C3H6. High NO-to-NO2 oxidation ability was due to the generation of oxygen defects and Co(2+)-Co(3+) redox couples, which resulted from B-site exsolution induced by A-site dissolution. Hence, our method is facile to modify the surface structures of perovskite catalysts and provides a new strategy to obtain highly active catalysts for the NSR reaction.

  11. Surface Tuning of La0.5Sr0.5CoO3 Perovskite Catalysts by Acetic Acid for NOx Storage and Reduction.

    PubMed

    Peng, Yue; Si, Wenzhe; Luo, Jinming; Su, Wenkang; Chang, Huazhen; Li, Junhua; Hao, Jiming; Crittenden, John

    2016-06-21

    Selective dissolution of perovskite A site (A of ABO3 structure) was performed on the La1 - xSrxCoO3 catalysts for the NOx storage and reduction (NSR) reaction. The surface area of the catalysts were enhanced using dilute HNO3 impregnation to dissolve Sr. Inactive SrCO3 was removed effectively within 6 h, and the catalyst preserved the perovskite framework after 24 h of treatment. The tuned catalysts exhibited higher NSR performance (both NOx storage and NO-to-NO2 oxidation) under lean-burn and fuel-rich cycles at 250 °C. Large amounts of NOx adsorption were due to the increase of nitrate/nitrite species bonding to the A site and the growth of newly formed monodentate nitrate species. Nitrate species were stored stably on the partial exposed Sr(2+) cations. These exposed Sr(2+) cations played an important role on the NOx reduction by C3H6. High NO-to-NO2 oxidation ability was due to the generation of oxygen defects and Co(2+)-Co(3+) redox couples, which resulted from B-site exsolution induced by A-site dissolution. Hence, our method is facile to modify the surface structures of perovskite catalysts and provides a new strategy to obtain highly active catalysts for the NSR reaction. PMID:27233105

  12. The Structural Disorder and Lattice Stability of (Ba,Sr)(Co,Fe)O3 Complex Perovskites

    SciTech Connect

    S.N.Rashkeev

    2011-05-01

    The structural disorder and lattice stability of complex perovskite (Ba,Sr)(Co,Fe)O3, a promising cathode material for solid oxide fuel cells and oxygen permeation membranes, is explored by means of first principles DFT calculations. It is predicted that Ba and Sr ions easily exchange their lattice positions (A-cation disorder) similarly to Co and Fe ions (B-cation disorder). The cation antisite defects (exchange of A- and B-type cations) have a relatively high formation energy. The BSCF is predicted to exist in an equilibrium mixture of several phases and can decompose exothermically into the Ba- and Co-rich hexagonal (Ba,Sr)CoO3 and Sr- and Fe-rich cubic (Ba,Sr)FeO3 perovskites.

  13. Lattice dynamics and the nature of structural transitions in organolead halide perovskites

    DOE PAGES

    Comin, Riccardo; Crawford, Michael K.; Said, Ayman H.; Herron, Norman; Guise, William E.; Wang, Xiaoping; Whitfield, Pamela S.; Jain, Ankit; Gong, Xiwen; McGaughey, Alan J. H.; et al

    2016-09-09

    Organolead halide perovskites are a family of hybrid organic-inorganic compounds whose remark- able optoelectronic properties have been under intensive scrutiny in recent years. Here we use inelastic X-ray scattering to study low-energy lattice excitations in single crystals of methylammonium lead iodide and bromide perovskites. Our ndings conrm the displacive nature of the cubic-to- tetragonal phase transition, which is further shown, using neutron and x-ray diraction, to be close to a tricritical point. The experimental sound speed, around 100-200 m/s, suggests that electron- phonon scattering is likely a limiting factor for further improvements in carrier mobility. Lastly, we detect quasistatic symmetry-breakingmore » nanodomains persisting well into the high-temperature cubic phase, possibly stabilized by local defects. These ndings reveal key structural properties of these materials, but also bear important implications for carrier dynamics across an extended temperature range relevant for photovoltaic applications.« less

  14. Thermal evolution of the crystal structure of the orthorhombic perovskite LaFeO{sub 3}

    SciTech Connect

    Dixon, Charlotte A.L.; Kavanagh, Christopher M.; Knight, Kevin S.; Kockelmann, Winfried; Morrison, Finlay D.; Lightfoot, Philip

    2015-10-15

    The thermal evolution of the crystal structure of the prototypical orthorhombic perovskite LaFeO{sub 3} has been studied in detail by powder neutron diffraction in the temperature range 25perovskite LaFeO{sub 3} is rationalized from a detailed powder neutron diffraction study. - Highlights: • Crystal structure of the perovskite LaFeO{sub 3} studied in detail by powder neutron diffraction. • Unusual thermal evolution of lattice metrics rationalized. • Contrasting behavior to Bi-doped LaFeO{sub 3}. • Octahedral distortion/tilt parameters explain unusual a and c lattice parameter behavior.

  15. 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.

  16. Lead-free and lead-based ABO3 perovskite relaxors with mixed-valence A-site and B-site disorder: Comparative neutron scattering structural study of (Na1/2Bi1/2)TiO3 and Pb(Mg1/3Nb2/3)O3

    NASA Astrophysics Data System (ADS)

    Ge, Wenwei; Devreugd, Christopher P.; Phelan, D.; Zhang, Qinhui; Ahart, Muhtar; Li, Jiefang; Luo, Haosu; Boatner, Lynn A.; Viehland, Dwight; Gehring, Peter M.

    2013-11-01

    We report the results of neutron elastic-scattering measurements made between -250 °C and 620 °C on the lead-free relaxor (Na1/2Bi1/2)TiO3 (NBT). Strong, anisotropic, elastic diffuse scattering intensity decorates the (100), (110), (111), (200), (210), and (220) Bragg peaks at room temperature. The wave-vector dependence of this diffuse scattering is compared to that in the lead-based relaxor Pb(Mg1/3Nb2/3)O3 (PMN) to determine if any features might be common to relaxors. Prominent ridges in the elastic diffuse scattering intensity contours that extend along ⟨110⟩ are seen that exhibit the same zone dependence as those observed in PMN and other lead-based relaxors. These ridges disappear gradually on heating above the cubic-to-tetragonal phase transition temperature TCT = 523 °C, which is also near the temperature at which the dielectric permittivity begins to deviate from Curie-Weiss behavior. We thus identify the ⟨110⟩-oriented ridges as a relaxor-specific property. The diffuse scattering contours also display narrower ridges oriented along ⟨100⟩ that are consistent with the x-ray results of Kreisel [Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.68.014113 68, 014113 (2003)]; these vanish near 320 °C, indicating that they have a different physical origin. The ⟨100⟩-oriented ridges are not observed in PMN. We observe no equivalent relaxor-specific elastic diffuse scattering from the homovalent relaxor analogues K0.95Li0.05TiO3 (A-site disordered) and KTa0.95Nb0.05O3 (B-site disordered). This suggests that the ⟨110⟩-oriented diffuse scattering ridges are correlated with the presence of strong random electric fields and invites a reassessment of what defines the relaxor phase. We find that doping NBT with 5.6% BaTiO3, a composition close to the morphotropic phase boundary with enhanced piezoelectric properties, increases the room-temperature correlation length along [11¯0] from 40 to 60 Å while doubling the associated integrated diffuse scattering. Similar behavior was reported by Matsuura [Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.74.144107 74, 144107 (2006)] for morphotropic compositions of PMN doped with PbTiO3. Finally, we comment on the recent observation of monoclinicity in NBT at room temperature by placing a strict bound on the strength of the (½½½) superlattice reflection associated with the Cc space group based on the atomic coordinates published in the x-ray study by Aksel [Appl. Phys. Lett.APPLAB0003-695110.1063/1.3573826 98, 152901 (2011)] for NBT. We show that a skin effect, analogous to that reported in the relaxors PZN-xPT and PMN-xPT, can reconcile our neutron single-crystal data with the x-ray powder data of Aksel [Appl. Phys. Lett.APPLAB0003-695110.1063/1.3573826 98, 152901 (2011)]. Our finding of a skin effect in a lead-free, A-site disordered, heterovalent relaxor supports the idea that it arises in the presence of strong random electric fields.

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

    PubMed

    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/m(2). 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    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.

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

    PubMed

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

    2016-09-16

    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/m(2). 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.

  1. Topotactic synthesis of strontium cobalt oxyhydride thin film with perovskite structure

    SciTech Connect

    Katayama, Tsukasa; Chikamatsu, Akira Kamisaka, Hideyuki; Yokoyama, Yuichi; Hirata, Yasuyuki; Wadati, Hiroki; Fukumura, Tomoteru; Hasegawa, Tetsuya

    2015-10-15

    The substitution of hydride anions (H{sup −}) into transition metal oxides has recently become possible through topotactic reactions or high-pressure synthesis methods. However, the fabrication of oxyhydrides is still difficult because of their inherently less-stable frameworks. In this study, we successfully fabricated perovskite SrCoO{sub x}H{sub y} thin films via the topotactic hydride doping of brownmillerite SrCoO{sub 2.5} epitaxial thin films with CaH{sub 2}. The perovskite-type cation framework was maintained during the topotactic treatment owing to epitaxial stabilization. Structural and chemical analyses accompanied by X-ray absorption spectroscopy measurements revealed that the doped hydride ions form a two-dimensional network of Co-H{sup −}-Co bonds, in contrast to other reported perovskite oxyhydrides, SrMO{sub 3−x}H{sub x} (M = Cr, Ti, V). The SrCoO{sub x}H{sub y} thin film exhibited insulating behavior and had a direct band gap of 2.1 eV. Thus, topotactic hydride doping of transition-metal-oxide thin films on suitable substrates is a promising method for the synthesis of new transition metal oxyhydrides.

  2. First-principles Calculations of Nuclear Magnetic Resonance Chemical Shielding Tensors in Complex Ferroelectric Perovskites

    NASA Astrophysics Data System (ADS)

    Pechkis, Daniel Lawrence

    Nuclear magnetic resonance (NMR) spectroscopy is one of the most important experimental probes of local atomistic structure, chemical ordering, and dynamics. Recently, NMR has increasingly been used to study complex ferroelectric perovskite alloys, where spectra can be difficult to interpret. First-principles calculations of NMR spectra can greatly assist in this task. In this work, oxygen, titanium, and niobium NMR chemical shielding tensors, ŝ , were calculated with first-principles methods for ferroelectric transition metal prototypical ABO3 perovskites [SrTiO3, BaTiO 3, PbTiO3 and PbZrO3] and A(B,B')O3 perovskite alloys Pb(Zr1/2Ti1/2)O3 (PZT) and Pb(Mg1/3Nb2/3)O3 (PMN). The principal findings are 1) a large anisotropy between deshielded sigma xx(O) ≃ sigmayy(O) and shielded sigma zz(O) components; 2) a nearly linear dependence on nearest-distance transition-metal/oxygen bond length, rs, was found for both isotropic deltaiso(O) and axial deltaax(O) chemical shifts ( d̂=ŝ reference- ŝ ), across all the systems studied, with deltaiso(O) varying by ≃ 400 ppm; 3) the demonstration that the anisotropy and linear variation arise from large paramagnetic contributions to sigmaxx(O) and sigmayy(O), due to virtual transitions between O(2p) and unoccupied B(nd) states. Using these results, an argument against Ti clustering in PZT, as conjectured from recent 17O NMR magic-angle-spinning measurements, is made. The linear dependence of the chemical shifts on rs provides a scale for determining transition-metal/oxygen bond lengths from experimental 17O NMR spectra. As such, it can be used to assess the degree of local tetragonality in perovskite solid solutions for piezoelectric applications. Results for transition metal atoms show less structural sensitivity, compared to 17O NMR, in homovalent B-site materials, but could be more useful in heterovalent B-site perovskite alloys. This work shows that both 17O and B-site NMR spectroscopy, coupled with first principles

  3. Identifying the Molecular Structures of Intermediates for Optimizing the Fabrication of High-Quality Perovskite Films.

    PubMed

    Cao, Jing; Jing, Xiaojing; Yan, Juanzhu; Hu, Chengyi; Chen, Ruihao; Yin, Jun; Li, Jing; Zheng, Nanfeng

    2016-08-10

    During the past two years, the introduction of DMSO has revolutionized the fabrication of high-quality pervoskite MAPbI3 (MA = CH3NH3) films for solar cell applications. In the developed DMSO process, the formation of (MA)2Pb3I8·2DMSO (shorted as Pb3I8) has well recognized as a critical factor to prepare high-quality pervoskite films and thus accomplish excellent performances in perovskite solar cells. However, Pb3I8 is an I-deficient intermediate and must further react with methylammonium iodide (MAI) to be fully converted into MAPbI3. By capturing and solving the molecular structures of several intermediates involved in the fabrication of perovskite films, we report in this work that the importance of DMSO is NOT due to the formation of Pb3I8. The use of different PbI2-DMSO ratios leads to two different structures of PbI2-DMSO precursors (PbI2·DMSO and PbI2·2DMSO), thus dramatically influencing the quality of fabricated perovskite films. However, such an influence can be minimized when the PbI2-DMSO precursor films are thermally treated to create mesoporous PbI2 films before reacting with MAI. Such a development makes the fabrication of high-quality pervoskite films highly reproducible without the need to precisely control the PbI2:DMSO ratio. Moreover, the formation of ionic compound (MA)4PbI6 is observed when excess MAI is used in the preparation of perovskite film. This I-rich phase heavily induces the hysteresis in PSCs, but is readily removed by isopropanol treatment. On the basis of all these findings, we develop a new effective protocol to fabricate high-performance PSCs. In the new protocol, high-quality perovskite films are prepared by simply treating the mesoporous PbI2 films (made from PbI2-DMSO precursors) with an isopropanol solution of MAI, followed by isopropanol washing. The best efficiency of fabricated MAPbI3 PSCs is up to 19.0%. As compared to the previously reported DMSO method, the devices fabricated by the method reported in this work

  4. The electronic structure of metal oxide/organo metal halide perovskite junctions in perovskite based solar cells

    PubMed Central

    Dymshits, Alex; Henning, Alex; Segev, Gideon; Rosenwaks, Yossi; Etgar, Lioz

    2015-01-01

    Cross-sections of a hole-conductor-free CH3NH3PbI3 perovskite solar cell were characterized with Kelvin probe force microscopy. A depletion region width of about 45 nm was determined from the measured potential profiles at the interface between CH3NH3PbI3 and nanocrystalline TiO2, whereas a negligible depletion was measured at the CH3NH3PbI3/Al2O3 interface. A complete solar cell can be realized with the CH3NH3PbI3 that functions both as light harvester and hole conductor in combination with a metal oxide. The band diagrams were estimated from the measured potential profile at the interfaces, and are critical findings for a better understanding and further improvement of perovskite based solar cells. PMID:25731963

  5. First-principles calculations of the OH- adsorption energy on perovskite oxide

    NASA Astrophysics Data System (ADS)

    Ohzuku, Hideo; Ikeno, Hidekazu; Yamada, Ikuya; Yagi, Shunsuke

    2016-08-01

    The oxygen evolution reaction (OER) that occurs during water oxidation is of considerable importance as an essential energy conversion reaction for rechargeable metal-air batteries and direct solar water splitting. ABO3 perovskite oxides have been extensively studied because of their high catalytic OER activity. In the present study, the OH- adsorption process on the perovskite surface about different B site cations was investigated by the first-principles calculations. We concluded that the adsorption energy of SrFeO3 surface is larger than that of SrTiO3.

  6. New hybrid lead iodides: From one-dimensional chain to two-dimensional layered perovskite structure

    SciTech Connect

    Xiong, Kecai; Liu, Wei; Teat, Simon J.; An, Litao; Wang, Hao; Emge, Thomas J.; Li, Jing

    2015-10-15

    Two new hybrid lead halides (H{sub 2}BDA)[PbI{sub 4}] (1) (H{sub 2}BDA=1,4-butanediammonium dication) and (HNPEIM)[PbI{sub 3}] (2) (HNPEIM=N-​phenyl-ethanimidamidine cation) have been synthesized and structurally characterized. X-ray diffraction analyses reveal that compound 1 features a two-dimensional corner-sharing perovskite layer whereas compound 2 contains one-dimensional edge-sharing double chains. The N-​phenyl-ethanimidamidine cation within compound 2 was generated in-situ under solvothermal conditions. The optical absorption spectra collected at room temperature suggest that both compounds are semiconductors having direct band gaps, with estimated values of 2.64 and 2.73 eV for 1 and 2, respectively. Results from the density functional theory (DFT) calculations are consistent with the experimental data. Density of states (DOS) analysis reveals that in both compounds 1 and 2, the energy states in the valence band maximum region are iodine 5p atomic orbitals with a small contribution from lead 6s, while in the region of conduction band minimum, the major contributions are from the inorganic (Pb 6p atomic orbitals) and organic components (C and N 2p atomic orbitals) in compound 1 and 2, respectively. - Graphical abstract: Two new hybrid lead halides built on one-dimensional edge-sharing double chains and two-dimensional corner-sharing perovskite layers are synthesized and their structural and electronic properties are analyzed. - Highlights: • Two new hybrid lead iodides are designed, synthesized, and characterized. • They are closely related to, but different from, perovskite structures. • The electronic properties of both compounds are analyzed by DFT calculations.

  7. Stability limits of the perovskite structure in the Y-Ba-Cu-O system

    NASA Astrophysics Data System (ADS)

    Bormann, R.; Nölting, J.

    1989-05-01

    The equilibrium (molecular) oxygen partial pressure of the Y1Ba2Cu3O7-x phase has been measured by an electrochemical method. The investigations are focused on the low-temperature range between 560 and 750 °C and on oxygen stoichiometries close to the oxygen-poor phase boundary. In particular, the oxygen partial pressure has been determined below which the perovskite structure becomes thermodynamically unstable. This critical value should be considered during the preparation of high Tc Y1Ba2Cu3O7-x superconductors, especially in the case of an in situ preparation of thin films.

  8. An Ultrahigh-Performance Photodetector based on a Perovskite-Transition-Metal-Dichalcogenide Hybrid Structure.

    PubMed

    Kang, Dong-Ho; Pae, Seong Ryul; Shim, Jaewoo; Yoo, Gwangwe; Jeon, Jaeho; Leem, Jung Woo; Yu, Jae Su; Lee, Sungjoo; Shin, Byungha; Park, Jin-Hong

    2016-09-01

    An ultrahigh performance MoS2 photodetector with high photoresponsivity (1.94 × 10(6) A W(-1) ) and detectivity (1.29 × 10(12) Jones) under 520 nm and 4.63 pW laser exposure is demonstrated. This photodetector is based on a methyl-ammonium lead halide perovskite/MoS2 hybrid structure with (3-aminopropyl)triethoxysilane doping. The performance degradation caused by moisture is also minimized down to 20% by adopting a new encapsulation bilayer of octadecyltrichlorosilane/polymethyl methacrylate.

  9. Temperature and Pressure Sensors Based on Spin-Allowed Broadband Luminescence of Doped Orthorhombic Perovskite Structures

    NASA Technical Reports Server (NTRS)

    Eldridge, Jeffrey I. (Inventor); Chambers, Matthew D. (Inventor)

    2014-01-01

    Systems and methods that are capable of measuring pressure or temperature based on luminescence are discussed herein. These systems and methods are based on spin-allowed broadband luminescence of sensors with orthorhombic perovskite structures of rare earth aluminates doped with chromium or similar transition metals, such as chromium-doped gadolinium aluminate. Luminescence from these sensors can be measured to determine at least one of temperature or pressure, based on either the intense luminescence of these sensors, even at high temperatures, or low temperature techniques discussed herein.

  10. Revised structural phase transitions in the archetype KMnF3 perovskite crystal

    NASA Astrophysics Data System (ADS)

    Kapusta, Joanna; Daniel, Philippe; Ratuszna, Alicja

    1999-06-01

    Reinvestigation of the structural and vibrational properties of the typical perovskite KMnF3, exhibiting two antiferrodistortive structural phase transitions, was performed using x-ray powder diffraction and Raman spectroscopy in the range between 30 and 300 K. The x-ray-diffraction work has unambiguously shown that a monoclinic distortion (ra-b+c- tilt system P21/m space group) is observed at low temperature below TC2=91 K. This result corresponds with the Raman temperature study which shows that this transition, in spite of its first-order character, can be associated with a group-subgroup relation between tetragonal and monoclinic symmetries. Additionally, existence of a large structural disorder far above the cubic to tetragonal transition (TC1=186 K) is suggested by the two following experimental indications: (i) persistence of hard modes of the tetragonal phase in the cubic symmetry, and (ii) existence of Raman broad bands in normally inactive ideal cubic phase, which are interpreted by the folding of the whole phonons branches of the cubic Brillouin zone. This last observation allows us to follow the evolution of the cubic R'15 soft mode versus temperature, based only on the Raman-scattering data, in full agreement with previous inelastic neutron data. The results of Raman investigations into KMnF3 are discussed in more general framework of structural disorder in perovskite systems which exhibit anisotropic correlation between octahedra.

  11. New hexagonal perovskite with Mn4+ and Mn5+ at distinct structural positions

    NASA Astrophysics Data System (ADS)

    Tarakina, N. V.; Tyutyunnik, A. P.; Bazuev, G. V.; Vasiliev, A. D.; Berger, I. F.; Gould, C.; Nikolaenko, I. V.

    2015-10-01

    A new hexagonal perovskite, Ba7Li1.75Mn3.5O15.75, has been synthesised using microwave-assisted solid-state synthesis. Its crystal structure has elements typical for the layered hexagonal perovskites and quasi-one-dimensional oxides, hence representing a new polytype. Structural solution based on simultaneous refinement of X-ray and neutron diffraction data shows that Ba7Li1.75Mn3.5O15.75 crystallizes in a hexagonal unit cell with parameters a = 5.66274(2) Å and c = 16.7467(1) Å (V = 465.063(4) Å3). Columns of face- shared octahedra occupied by Mn4+, Li+ cations and vacancies along the c axis are separated in the ab plane by barium atoms, so that every sixth layer, the coordination of Mn5+ and Li+ changes to tetrahedral. Separation of Mn4+ and Mn5+ cations in two distinct structural positions makes the structure unique. A scanning transmission electron microscopy study revealed the formation of a rhombohedrally centered supercell, which might be attributed to the ordering of manganese and lithium atoms among cationic sites.

  12. Structural and electric evidence of ferrielectric state in Pb₂MnWO₆ double perovskite system.

    PubMed

    Orlandi, Fabio; Righi, Lara; Cabassi, Riccardo; Delmonte, Davide; Pernechele, Chiara; Bolzoni, Fulvio; Mezzadri, Francesco; Solzi, Massimo; Merlini, Marco; Calestani, Gianluca

    2014-10-01

    In this paper we describe the new ferri-electric compound Pb2MnWO6 (PMW), a double perovskite that can be considered as a novel structural prototype showing complex nuclear structure and interesting electric properties. According to single-crystal synchrotron data, PMW crystallizes in the noncentrosymmetric polar group Pmc21, in which the two symmetry-independent lead atoms give rise to a ferrielectric arrangement. The accurate crystallographic characterization indicates the presence of a complex distortion of the perovskite lattice driven by the local instability induced by the 6s(2) lone pair of the lead atoms. These peculiar structural features are confirmed by the complete electrical characterization of the system. Dielectric and transport measurements indicate an insulating character of the sample, while pyroelectric measurements point out a ferrielectric state characterized by different contributions. The magnetic transition at 45 K is accompanied by a magnetostrictive effect indicating a probable spin-lattice coupling. The characterizations carried out on PMW, showing the evidence of a coexistence of antiferromagnetism and ferrielectricity at low temperature, could lead to the definition of a new class of multiferroic materials. PMID:25197959

  13. Anion ordering, magnetic structure and properties of the vacancy ordered perovskite Ba3Fe3O7F

    NASA Astrophysics Data System (ADS)

    Clemens, Oliver; Reitz, Christian; Witte, Ralf; Kruk, Robert; Smith, Ronald I.

    2016-11-01

    This article describes a detailed investigation of the crystallographic and magnetic structure of perovskite type Ba3Fe3O7F 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 57Fe Mössbauer spectroscopy data.

  14. A two-layer structured PbI2 thin film for efficient planar perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Ying, Chao; Shi, Chengwu; Wu, Ni; Zhang, Jincheng; Wang, Mao

    2015-07-01

    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.

  15. 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. PMID:26118756

  16. Real-Space Imaging of the Atomic Structure of Organic-Inorganic Perovskite.

    PubMed

    Ohmann, Robin; Ono, Luis K; Kim, Hui-Seon; Lin, Haiping; Lee, Michael V; Li, Youyong; Park, Nam-Gyu; Qi, Yabing

    2015-12-30

    Organic-inorganic perovskite is a promising class of materials for photovoltaic applications and light emitting diodes. However, so far commercialization is still impeded by several drawbacks. Atomic-scale effects have been suggested to be possible causes, but an unequivocal experimental view at the atomic level is missing. Here, we present a low-temperature scanning tunneling microscopy study of single crystal methylammonium lead bromide CH3NH3PbBr3. Topographic images of the in situ cleaved perovskite surface reveal the real-space atomic structure. Compared to the bulk we observe modified arrangements of atoms and molecules on the surface. With the support of density functional theory we explain these by surface reconstruction and a substantial interplay of the orientation of the polar organic cations (CH3NH3)(+) with the position of the hosting anions. This leads to structurally and electronically distinct domains with ferroelectric and antiferroelectric character. We further demonstrate local probing of defects, which may also impact device performance.

  17. Local and distant charge compensation of iron ions in ABO3 ferroelectrics

    NASA Astrophysics Data System (ADS)

    Malovichko, Galina; Petersen, Robert; Grachev, Valentin

    2011-10-01

    The determination of the lattice sites and charge compensators of non-isovalent impurities are vitally important for both fundamental science and tailoring material properties for various applications. Results of our study of Fe^3+ centers in LiNbO3, LiTaO3 and KTaO3 (LN, LT and KT) with the help of Electron Paramagnetic Resonance (EPR) and Electron Nuclear Double Resonance (ENDOR) have shown significant difference in spectroscopic characteristics and, correspondingly, structures of these centers. Two Fe^3+ dominant centers in cubic KT crystals have axial <100> symmetry caused by the presence of local charge compensators (oxygen vacancy for Ta^5+ substitution and interstitial oxygen for K^+ substitution). In Li-deficient congruent LT and LN crystals the Fe^3+ ions substitute only for Li^+. Since no disorder in the nearest surrounding was found, the distant charge compensation by intrinsic defects in cation sublattice is supposed. In stoichiometric samples of LT and LN the iron ions randomly substitute for both Li^+ and Ta^5+ (Nb^5+) having average self-compensation of excess charges.

  18. Structures of ordered tungsten- or molybdenum-containing quaternary perovskite oxides

    SciTech Connect

    Day, Bradley E.; Bley, Nicholas D.; Jones, Heather R.; McCullough, Ryan M.; Eng, Hank W.; Porter, Spencer H.; Woodward, Patrick M.; Barnes, Paris W.

    2012-01-15

    The room temperature crystal structures of six A{sub 2}MMoO{sub 6} and A{sub 2}MWO{sub 6} ordered double perovskites were determined from X-ray and neutron powder diffraction data. Ba{sub 2}MgWO{sub 6} and Ba{sub 2}CaMoO{sub 6} both adopt cubic symmetry (space group Fm3-bar m, tilt system a{sup 0}a{sup 0}a{sup 0}). Ba{sub 2}CaWO{sub 6} has nearly the same tolerance factor (t=0.972) as Ba{sub 2}CaMoO{sub 6} (t=0.974), yet it surprisingly crystallizes with I4/m symmetry indicative of out-of-phase rotations of the MO{sub 6} octahedra about the c-axis (a{sup 0}a{sup 0}c{sup -}). Sr{sub 2}ZnMoO{sub 6} (t=0.979) also adopts I4/m symmetry; whereas, Sr{sub 2}ZnWO{sub 6} (t=0.976) crystallizes with monoclinic symmetry (P2{sub 1}/n) with out-of-phase octahedral tilting distortions about the a- and b-axes, and in-phase tilting about the c-axis (a{sup -}a{sup -}c{sup +}). Ca{sub 2}CaWO{sub 6} (t=0.867) also has P2{sub 1}/n symmetry with large tilting distortions about all three crystallographic axes and distorted CaO{sub 6} octahedra. Analysis of 93 double perovskites and their crystal structures showed that while the type and magnitude of the octahedral tilting distortions are controlled primarily by the tolerance factor, the identity of the A-cation acts as the secondary structure directing factor. When A=Ba{sup 2+} the boundary between cubic and tetragonal symmetries falls near t=0.97, whereas when A=Sr{sup 2+} this boundary falls somewhere between t=1.018 and t=0.992. - Graphical abstract: A survey of the tolerance factor of 41 Mo/W- and 52 Nb/Ta-containing quaternary perovskites plotted as a function of the difference between the two six-coordinate M-cation ionic radii. Compounds with cubic symmetry are represented by diamonds, those with tetragonal symmetry are represented by squares, those with I2/m monoclinic symmetry are represented by Multiplication-Sign , and those with P2{sub 1}/n monoclinic symmetry are represented by triangles. White symbols represent

  19. Oxide-Ion Conduction in Anion-Deficient Perovskites.

    NASA Astrophysics Data System (ADS)

    Feng, Man

    1995-01-01

    Strategies for the design of an improved oxide -ion electrolyte for medium-temperature fuel cells, sensors, and oxygen pumps are outlined. Anion-deficient oxides with the perovskite structure were chosen for study. Stoichiometric oxides contain a high fraction of vacancies, but vacancy ordering suppresses ionic conductivity. Nevertheless, the brownmillerite rm Ba_2In_2O _5 undergoes an order-disorder transition at 930^circC that allows an estimate of the motional enthalpy of the disordered vacancy. Substitution of both aliovalent and isovalent cations were investigated as a means of suppressing the long-range ordering. Substitution of Nb^{5+}, Ti ^{4+}, Sn^{4+ } could be made for In^{3+ } at the B sites of the ABO_ {3-delta} perovskite structure, and this strategy did suppress long-range ordering of the oxygen vacancies for more than 10 mole % dopant. However, it was found that these dopants have a sufficient preference for octahedral anion coordination that water is introduced into the vacancies below 400^circ C; the protons introduced with the water became dominant conductive species below 400^circ C. At high temperature, the oxide-ion conduction is dominant and, below 930^circC, is enhanced by two orders of magnitude for about 20% dopant whether quadravalent or pentavalent dopants are used. Substitution of La^{3+} for Ba ^{2+} suppressed the introduction of water at low temperature, and the best oxide-ion conduction was achieved in rm Ba_{0.6}La _{0.4}InO_{2.7} isovalent doping of Y for In in rm Ba_2In _2O_5<=ad to the discovery of an extremely high ionic conduction in rm Ba _3Y_4O_9 stabilized at room temperature by quenching from above 1200^ circC. On heating in air, it first decomposes into rm Y_2O_3 and a Ba(OH)_2-BaO_2 mix that becomes an immobilized melt and a fast ionic conductor above 370^circC. With time in air, the melt is transformed to BaCO_3 , which is not conductive. Superior oxide-ion conduction was discovered in the Sr and Mg doped perovskite La

  20. A First-Principles Study on the Structural and Electronic Properties of Sn-Based Organic-Inorganic Halide Perovskites

    NASA Astrophysics Data System (ADS)

    Ma, Zi-Qian; Pan, Hui; Wong, Pak Kin

    2016-11-01

    Organic-inorganic halide perovskites have attracted increasing interest on solar-energy harvesting because of their outstanding electronic properties. In this work, we systematically investigate the structural and electronic properties of Sn-based hybrid perovskites MASnX3 and FASnX3 (X = I, Br) based on density-functional-theory calculations. We find that their electronic properties strongly depend on the organic molecules, halide atoms, and structures. We show that there is a general rule to predict the band gap of the Sn-based hybrid perovskite: its band gap increases as the size of halide atom decreases as well as that of organic molecule increase. The band gap of high temperature phase (cubic structure) is smaller than that of low temperature phase (orthorhombic structure). The band gap of tetragonal structure (medium-temperature phase) may be larger or smaller than that of cubic phase, depending on the orientation of the molecule. Tunable band gap within a range of 0.73-1.53 eV can be achieved by choosing halide atom and organic molecule, and controlling structure. We further show that carrier effective mass also reduces as the size of halide atom increases and that of molecule decreases. By comparing with Pb-based hybrid perovskites, the Sn-based systems show enhanced visible-light absorption and carrier mobility due to narrowed band gap and reduced carrier effective mass. These Sn-based organic-inorganic halide perovskites may find applications in solar energy harvesting with improved performance.

  1. A First-Principles Study on the Structural and Electronic Properties of Sn-Based Organic-Inorganic Halide Perovskites

    NASA Astrophysics Data System (ADS)

    Ma, Zi-Qian; Pan, Hui; Wong, Pak Kin

    2016-08-01

    Organic-inorganic halide perovskites have attracted increasing interest on solar-energy harvesting because of their outstanding electronic properties. In this work, we systematically investigate the structural and electronic properties of Sn-based hybrid perovskites MASnX3 and FASnX3 (X = I, Br) based on density-functional-theory calculations. We find that their electronic properties strongly depend on the organic molecules, halide atoms, and structures. We show that there is a general rule to predict the band gap of the Sn-based hybrid perovskite: its band gap increases as the size of halide atom decreases as well as that of organic molecule increase. The band gap of high temperature phase (cubic structure) is smaller than that of low temperature phase (orthorhombic structure). The band gap of tetragonal structure (medium-temperature phase) may be larger or smaller than that of cubic phase, depending on the orientation of the molecule. Tunable band gap within a range of 0.73-1.53 eV can be achieved by choosing halide atom and organic molecule, and controlling structure. We further show that carrier effective mass also reduces as the size of halide atom increases and that of molecule decreases. By comparing with Pb-based hybrid perovskites, the Sn-based systems show enhanced visible-light absorption and carrier mobility due to narrowed band gap and reduced carrier effective mass. These Sn-based organic-inorganic halide perovskites may find applications in solar energy harvesting with improved performance.

  2. A systematic study of ideal and double layer reconstructions of ABO3(001) surfaces (A = Sr, Ba; B = Ti, Zr) from first principles.

    PubMed

    Iles, N; Finocchi, F; Khodja, K Driss

    2010-08-01

    We conducted a comparative study of various reconstructions for the (001) surfaces of SrTiO(3), BaTiO(3), SrZrO(3) and BaZrO(3) perovskites through calculations within the density functional theory. The atomic structure, the thermodynamic stability and the charge distribution of ideal AO or BO(2) terminations, as well as the so-called AO or BO(2) double layer reconstructions were analysed, and it was found that of all the BO(2) double layer reconstructions the most stable are the (2 × 2) and the (√2 × √2) ones. This is mainly due to stress release through the formation of long B-chains. On Ti-based perovskites, these double layer reconstructions were found to be thermodynamically stable, which was not the case for Zr-based perovskites, for which AO terminations dominated most of the stability domain. We also found that the BO(2) double layer reconstructions are accompanied by a substantial charge redistribution, with an almost neutral surface plane. This charge redistribution has important consequences for the reactivity and the behaviour of the electric field close to the surface.

  3. Prediction of a potential high-pressure structure of FeSiO3

    NASA Astrophysics Data System (ADS)

    Cohen, R. E.; Lin, Yangzheng

    2014-10-01

    We predict a candidate high-temperature, high-pressure structure of FeSiO3 with space-group symmetry Cmmm by applying an evolutionary algorithm within density functional theory (DFT)+U that we call post-perovskite II (PPv-II). An exhaustive search found no other competitive candidate structures with ABO3 composition. We compared the x-ray diffraction pattern of FeSiO3 PPv-II with experimental results of the recently reported "H phase" of (Fe,Mg)SiO3. The intensities and positions of two main x-ray diffraction peaks of PPv-II FeSiO3 compare well with those of the H phase. We also calculated the static equation of state, the enthalpy, and the bulk modulus of the PPv-II phase and compared it with those of the perovskite (Pv) and post-perovskite (PPv) phases of FeSiO3. According to the static DFT+U computations, the PPv-II phase of FeSiO3 is less stable than the Pv and PPv phases under lower mantle pressure conditions at T =0 K and has a higher volume. PPv-II may be entropically stabilized, and may be a stable phase in Earth's lower mantle, coexisting with -PbO2 (columbite-structure) silica and perovskite, or with magnesiowustite and/or ferropericlase, depending on the bulk composition.

  4. Synthesis, crystal structure, and properties of a perovskite-related bismuth phase, (NH4)3Bi2I9

    NASA Astrophysics Data System (ADS)

    Sun, Shijing; Tominaka, Satoshi; Lee, Jung-Hoon; Xie, Fei; Bristowe, Paul D.; Cheetham, Anthony K.

    2016-03-01

    Organic-inorganic halide perovskites, especially methylammonium lead halide, have recently led to remarkable advances in photovoltaic devices. However, due to environmental and stability concerns around the use of lead, research into lead-free perovskite structures has been attracting increasing attention. In this study, a layered perovskite-like architecture, (NH4)3Bi2I9, is prepared from solution and the structure solved by single crystal X-ray diffraction. The band gap, which is estimated to be 2.04 eV using UV-visible spectroscopy, is lower than that of CH3NH3PbBr3. The energy-minimized structure obtained from first principles calculations is in excellent agreement with the X-ray results and establishes the locations of the hydrogen atoms. The calculations also point to a significant lone pair effect on the bismuth ion. Single crystal and powder conductivity measurements are performed to examine the potential application of (NH4)3Bi2I9 as an alternative to the lead containing perovskites.

  5. 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.

  6. Exploring a Lead-free Semiconducting Hybrid Ferroelectric with a Zero-Dimensional Perovskite-like Structure.

    PubMed

    Sun, Zhihua; Zeb, Aurang; Liu, Sijie; Ji, Chengmin; Khan, Tariq; Li, Lina; Hong, Maochun; Luo, Junhua

    2016-09-19

    Perovskite lead halides (CH3 NH3 PbI3 ) have recently taken a promising position in photovoltaics and optoelectronics because of remarkable semiconducting properties and possible ferroelectricity. However, the potential toxicity of lead arouses great environmental concern for widespread application. A new chemically tailored lead-free semiconducting hybrid ferroelectric is reported, N-methylpyrrolidinium)3 Sb2 Br9 (1), which consists of a zero-dimensional (0-D) perovskite-like anionic framework connected by corner- sharing SbBr6 coordinated octahedra. It presents a large ferroelectric spontaneous polarization of approximately 7.6 μC cm(-2) , as well as notable semiconducting properties, including positive temperature-dependent conductivity and ultraviolet-sensitive photoconductivity. Theoretical analysis of electronic structure and energy gap discloses a dominant contribution of the 0-D perovskite-like structure to the semiconducting properties of the material. This finding throws light on the rational design of new perovskite-like hybrids, especially lead-free semiconducting ferroelectrics.

  7. Optical and Structural Study of Organometal Halide Materials for Applications in Perovskite-Based Solar Cells

    NASA Astrophysics Data System (ADS)

    Nguyen, Minh Tu; Phan Vu, Thi Van; Bui, Bao Thoa; Luong, Thu Trang; Nguyen, Minh Hieu; Hoang Ngoc, Lam Huong; Bui, Van Diep; Truong, Thanh Tu; Nguyen-Tran, Thuat

    2016-05-01

    CH3NH3PbI3 and CH3NH3PbI2Br crystal powders and thin films with chemical formula CH3NH3PbI3- x Br x have been synthesized by reacting methylammonium bromide/iodide with lead iodide. The films were fabricated by a low-temperature solution process using the spin-coating method followed by thermal annealing, which is an effective means for controlling the composition and morphology of the CH3NH3PbI3- x Br x thin films. The resulting perovskite films exhibit good optical absorption and crystalline structure, being promising for potential application as light absorbers in future solar cells.

  8. Structural and optical characterization of DyAlO3 perovskite powders obtained by combustion synthesis

    NASA Astrophysics Data System (ADS)

    Saji S., K.; Raju, K.; Wariar, P. R. S.

    2016-05-01

    Phase pure Dysprosium monoaluminate has been prepared from Dysprosium oxide and Aluminium nitrate by auto-ignition citrate complex combustion process. The phase formation has been investigated using X-ray diffraction analysis (XRD), Thermo-Gravimetric/Differential Thermal Analysis (TGA/DTA) and Fourier Transform Infrared (FT-IR) spectroscopy analysis. X-ray diffraction analysis (XRD) revealed that DyAlO3 has an orthorhombic perovskite structure. From Transmission Electron Microscopy (TEM) studies, average particle-size has been found to be as low as 45 nm. The absorption spectrum of the DyAlO3 nanoparticles shows characteristic absorption bands of Dy atom. The optical band gap of the material was found to be 5.15eV, which corresponds to direct allowed transitions.

  9. Thermal evolution of the crystal structure of the orthorhombic perovskite LaFeO3

    NASA Astrophysics Data System (ADS)

    Dixon, Charlotte A. L.; Kavanagh, Christopher M.; Knight, Kevin S.; Kockelmann, Winfried; Morrison, Finlay D.; Lightfoot, Philip

    2015-10-01

    The thermal evolution of the crystal structure of the prototypical orthorhombic perovskite LaFeO3 has been studied in detail by powder neutron diffraction in the temperature range 25

  10. 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

  11. Crystal Structure of Pure and Aluminous Calcium Silicate Perovskites at Mantle Related Pressure and Temperature

    NASA Astrophysics Data System (ADS)

    Chen, H.; Shim, S. H.; Leinenweber, K. D.; Meng, Y.; Prakapenka, V.

    2015-12-01

    CaSiO3-perovskite (CaPv) is believed to be the third most abundant mineral (5 wt%) in the Earth's lower mantle (LM). Subducted slabs contain 23 wt% CaPv at the LM related pressure (P) and temperature (T), where Al2O3 could be incorporated into the crystal structure of CaPv (AlCaPv). However, there remains important discrepancy between computations and experiments on the crystal structure of CaPv at high P and low T. Some computations have predicted a tetragonal I4/mcm structure with a pseudo-cubic axial ratio (cp/ap) greater than 1, while X-ray diffraction (XRD) studies have suggested a tetragonal P4/mmm structure with cp/ap ~ 0.995. Using Ne as a pressure medium, we conducted in-situ XRD of CaSiO3 and 5 wt% Al-bearing CaSiO3 in the laser heated diamond anvil cell at the GSECARS and HPCAT sectors of the Advanced Photon Source. Rietveld refinements are performed on the diffraction patterns of CaPv at 300 K and 20-60 GPa. Similar to previous studies, we observed splitting of the 200 and 211 peaks after T-quench in pure CaPv. However, unlike previous experiments, diffraction patterns were more consistent with a tetragonal I4/mcm structure with cp/ap ~ 1.005 than P4/mmm. All the previous diffraction patterns have been measured with an Ar or MgO medium, or even without a medium, while we used more hydrostatic Ne medium. Considering the small free energy differences among different perovskite structures, the crystal structure of CaPv may be very sensitive to non-hydrostatic stresses. In runs with AlCaPv, asymmetrical 200 peaks are found up to 60 GPa and 2200 K, showing that non-cubic could be still stable at mantle geotherm temperatures in AlCaPv. The extreme sensitivity of CaPv on deviatoric stresses may have important implications for the elastic properties of the mantle regions with strong deformations, because the elastic anisotropy can change with the crystal structure of CaPv.

  12. Degradation of Methylammonium Lead Iodide Perovskite Structures through Light and Electron Beam Driven Ion Migration

    PubMed Central

    2016-01-01

    Organometal halide perovskites show promising features for cost-effective application in photovoltaics. The material instability remains a major obstacle to broad application because of the poorly understood degradation pathways. Here, we apply simultaneous luminescence and electron microscopy on perovskites for the first time, allowing us to monitor in situ morphology evolution and optical properties upon perovskite degradation. Interestingly, morphology, photoluminescence (PL), and cathodoluminescence of perovskite samples evolve differently upon degradation driven by electron beam (e-beam) or by light. A transversal electric current generated by a scanning electron beam leads to dramatic changes in PL and tunes the energy band gaps continuously alongside film thinning. In contrast, light-induced degradation results in material decomposition to scattered particles and shows little PL spectral shifts. The differences in degradation can be ascribed to different electric currents that drive ion migration. Moreover, solution-processed perovskite cuboids show heterogeneity in stability which is likely related to crystallinity and morphology. Our results reveal the essential role of ion migration in perovskite degradation and provide potential avenues to rationally enhance the stability of perovskite materials by reducing ion migration while improving morphology and crystallinity. It is worth noting that even moderate e-beam currents (86 pA) and acceleration voltages (10 kV) readily induce significant perovskite degradation and alter their optical properties. Therefore, attention has to be paid while characterizing such materials using scanning electron microscopy or transmission electron microscopy techniques. PMID:26804213

  13. Magnetic order and electronic structure of the 5 d3 double perovskite Sr2ScOsO6

    NASA Astrophysics Data System (ADS)

    Taylor, A. E.; Morrow, R.; Singh, D. J.; Calder, S.; Lumsden, M. D.; Woodward, P. M.; Christianson, A. D.

    2015-03-01

    The magnetic susceptibility, crystal and magnetic structures, and electronic structure of the double perovskite Sr2ScOsO6 are reported. Using both neutron and x-ray powder diffraction we find that the crystal structure is monoclinic P 21/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 ) μB , close to half the spin-only value for a crystal field split 5 d electron state with a t2g 3 ground state. Density 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 μB reduction in the moment.

  14. Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide

    PubMed Central

    Whitfield, P. S.; Herron, N.; Guise, W. E.; Page, K.; Cheng, Y. Q.; Milas, I.; Crawford, M. K.

    2016-01-01

    We have examined the crystal structures and structural phase transitions of the deuterated, partially deuterated and hydrogenous organic-inorganic hybrid perovskite methyl ammonium lead iodide (MAPbI3) using time-of-flight neutron and synchrotron X-ray powder diffraction. Near 330 K the high temperature cubic phases transformed to a body-centered tetragonal phase. The variation of the order parameter Q for this transition scaled with temperature T as Q ∼ (Tc−T)β, where Tc is the critical temperature and the exponent β was close to ¼, as predicted for a tricritical phase transition. However, we also observed coexistence of the cubic and tetragonal phases over a range of temperature in all cases, demonstrating that the phase transition was in fact first-order, although still very close to tricritical. Upon cooling further, all the tetragonal phases transformed into a low temperature orthorhombic phase around 160 K, again via a first-order phase transition. Based upon these results, we discuss the impact of the structural phase transitions upon photovoltaic performance of MAPbI3 based solar cells. PMID:27767049

  15. Local structure of the metal-organic perovskite dimethylammonium manganese(ii) formate.

    PubMed

    Duncan, Helen D; Dove, Martin T; Keen, David A; Phillips, Anthony E

    2016-03-14

    We report total neutron scattering measurements on the metal-organic perovskite analogue dimethylammonium manganese(ii) formate, (CD3)2ND2[Mn(DCO2)3]. Reverse Monte Carlo modelling shows that, in both the disordered high-temperature and ordered low-temperature phases, the ammonium moiety forms substantially shorter hydrogen bonds (N...O = 2.4 Å and 2.6 Å) than are visible in the average crystal structures. These bonds result from a pincer-like motion of two adjacent formate ions about the dimethylammonium ion in such a way that the framework can adjust independently to the positions of nearest-neighbour dimethylammonium ions. At low temperatures the shortest hydrogen bond is less favourable, apparently because it involves a greater distortion of the framework. Furthermore, in the high-temperature phase, in addition to the three disordered nitrogen positions expected from the average crystal structure, there appear to be also smaller probability maxima between these positions, corresponding to orientations in which the dimethylammonium is hydrogen-bonded to the two oxygen atoms of a single formate ion. The spontaneous strain across the phase transition reveals a contraction of the framework about the dimethylammonium cation, continuing as the material is cooled below the transition temperature. These results provide direct evidence of the local atomic structure of the guest-framework hydrogen bonding, and in particular the distortions of the framework responsible for the phase transition in this system. PMID:26763144

  16. Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide

    DOE PAGES

    Whitfield, P. S.; Herron, N.; Guise, W. E.; Page, K.; Cheng, Y. Q.; Milas, I.; Crawford, M. K.

    2016-10-21

    Here, we examine the crystal structures and structural phase transitions of the deuterated, partially deuterated and hydrogenous organic-inorganic hybrid perovskite methyl ammonium lead iodide (MAPbI3) using time-of-flight neutron and synchrotron X-ray powder diffraction. Near 330 K the high temperature cubic phases transformed to a body-centered tetragonal phase. The variation of the order parameter Q for this transition scaled with temperature T as Q (Tc-T) , where Tc is the critical temperature and the exponent was close to , as predicted for a tricritical phase transition. We also observed coexistence of the cubic and tetragonal phases over a range of temperaturemore » in all cases, demonstrating that the phase transition was in fact first-order, although still very close to tricritical. Upon cooling further, all the tetragonal phases transformed into a low temperature orthorhombic phase around 160 K, again via a first-order phase transition. Finally, based upon these results, we discuss the impact of the structural phase transitions upon photovoltaic performance of MAPbI3 based solar cells.« less

  17. 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. PMID:27499005

  18. 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. PMID:27478888

  19. Correlating structure and electronic band-edge properties in organolead halide perovskites nanoparticles.

    PubMed

    Zhu, Qiushi; Zheng, Kaibo; Abdellah, Mohamed; Generalov, Alexander; Haase, Dörthe; Carlson, Stefan; Niu, Yuran; Heimdal, Jimmy; Engdahl, Anders; Messing, Maria E; Pullerits, Tonu; Canton, Sophie E

    2016-06-01

    After having emerged as primary contenders in the race for highly efficient optoelectronics materials, organolead halide perovskites (OHLP) are now being investigated in the nanoscale regime as promising building blocks with unique properties. For example, unlike their bulk counterpart, quantum dots of OHLP are brightly luminescent, owing to large exciton binding energies that cannot be rationalized solely on the basis of quantum confinement. Here, we establish the direct correlation between the structure and the electronic band-edge properties of CH3NH3PbBr3 nanoparticles. Complementary structural and spectroscopic measurements probing long-range and local order reveal that lattice strain influences the nature of the valence band and modifies the subtle stereochemical activity of the Pb(2+) lone-pair. More generally, this work demonstrates that the stereochemical activity of the lone-pair at the metal site is a specific physicochemical parameter coupled to composition, size and strain, which can be employed to engineer novel functionalities in OHLP nanomaterials. PMID:27189431

  20. Structural and magnetic properties of double perovskite oxide Ba2CeSbO6

    NASA Astrophysics Data System (ADS)

    Dutta, Alo; Mukhopadhyay, P. K.; Sinha, T. P.; Das, Dipankar; Shannigrahi, Santiranjan

    2016-08-01

    The structural and magnetic properties of a double perovskite oxide Ba2CeSbO6 (BCSO) synthesized by solid state reaction technique have been investigated. The Rietveld refinement of the X-ray diffraction pattern of BCSO suggests the monoclinic crystal structure at room temperature with P21/n space group. The vibrational properties of BCSO are investigated by the Fourier transform Infrared and Raman spectroscopy. The Raman spectrum confirms the B-site ordering of cations in BCSO. The temperature dependent magnetic susceptibility data in the field cooled mode show the anti-ferromagnetic behaviour of BCSO below 59 K. The core level X-ray photoemission (XPS) spectrum of Ce-3d and Sb-3d states confirms the presence of multiple oxidation states of these cations. The presence of both the Ce3+ and Ce4+ ions in BCSO gives the 4f4-δ intermediate valence state which may reduce the effective magnetic moment with respect to the system having single valence Ce3+ ion.

  1. Pressure-Induced Structural and Optical Properties of Organometal Halide Perovskite-Based Formamidinium Lead Bromide.

    PubMed

    Wang, Lingrui; Wang, Kai; Zou, Bo

    2016-07-01

    Organometal halide perovskites (OMHPs) are attracting an ever-growing scientific interest as photovoltaic materials with moderate cost and compelling properties. In this Letter, pressure-induced optical and structural changes of OMHP-based formamidinium lead bromide (FAPbBr3) were systematically investigated. We studied the pressure dependence of optical absorption and photoluminescence, both of which showed piezochromism. Synchrotron X-ray diffraction indicated that FAPbBr3 underwent two phase transitions and subsequent amorphization, leading directly to the bandgap evolution with redshift followed by blueshift during compression. Raman experiments illustrated the high pressure behavior of organic cation and the surrounding inorganic octahedra. Additionally, the effect of cation size and the different intermolecular interactions between organic cation and inorganic octahedra result in the fact that FAPbBr3 is less compressible than the reported methylammonium lead bromide (MAPbBr3). High pressure studies of the structural evolution and optical properties of OMHPs provide important clues in optimizing photovoltaic performance and help to design novel OMHPs with higher stimuli-resistant ability. PMID:27321024

  2. Mapping growth windows in quaternary perovskite oxide systems by hybrid molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Brahlek, Matthew; Zhang, Lei; Zhang, Hai-Tian; Lapano, Jason; Dedon, Liv R.; Martin, Lane W.; Engel-Herbert, Roman

    2016-09-01

    Requisite to growing stoichiometric perovskite thin films of the solid-solution A'1-xAxBO3 by hybrid molecular beam epitaxy is understanding how the growth conditions interpolate between the end members A'BO3 and ABO3, which can be grown in a self-regulated fashion, but under different conditions. Using the example of La1-xSrxVO3, the two-dimensional growth parameter space that is spanned by the flux of the metal-organic precursor vanadium oxytriisopropoxide and composition, x, was mapped out. The evolution of the adsorption-controlled growth window was obtained using a combination of X-ray diffraction, atomic force microscopy, reflection high-energy electron-diffraction (RHEED), and Rutherford backscattering spectroscopy. It is found that the stoichiometric growth conditions can be mapped out quickly with a single calibration sample using RHEED. Once stoichiometric conditions have been identified, the out-of-plane lattice parameter can be utilized to precisely determine the composition x. This strategy enables the identification of growth conditions that allow the deposition of stoichiometric perovskite oxide films with random A-site cation mixing, which is relevant to a large number of perovskite materials with interesting properties, e.g., high-temperature superconductivity and colossal magnetoresistance, that emerge in solid solution A'1-xAxBO3.

  3. Electronic structure and band alignment at an epitaxial spinel/perovskite heterojunction.

    PubMed

    Qiao, Liang; Li, Wei; Xiao, Haiyan; Meyer, Harry M; Liang, Xuelei; Nguyen, N V; Weber, William J; Biegalski, Michael D

    2014-08-27

    The electronic properties of solid-solid interfaces play critical roles in a variety of technological applications. Recent advances of film epitaxy and characterization techniques have demonstrated a wealth of exotic phenomena at interfaces of oxide materials, which are critically dependent on the alignment of their energy bands across the interface. Here we report a combined photoemission and electrical investigation of the electronic structures across a prototypical spinel/perovskite heterojunction. Energy-level band alignment at an epitaxial Co3O4/SrTiO3(001) heterointerface indicates a chemically abrupt, type I heterojunction without detectable band bending at both the film and substrate. The unexpected band alignment for this typical p-type semiconductor on SrTiO3 is attributed to its intrinsic d-d interband excitation, which significantly narrows the fundamental band gap between the top of the valence band and the bottom of the conduction band. The formation of the type I heterojunction with a flat-band state results in a simultaneous confinement of both electrons and holes inside the Co3O4 layer, thus rendering the epitaxial Co3O4/SrTiO3(001) heterostructure to be a very promising material for high-efficiency luminescence and optoelectronic device applications.

  4. Aluminum in magnesium silicate perovskite: Formation, structure, and energetics of magnesium-rich defect solid solutions

    NASA Astrophysics Data System (ADS)

    Navrotsky, Alexandra; Schoenitz, Mirko; Kojitani, Hiroshi; Xu, Hongwu; Zhang, Jianzhong; Weidner, Donald J.; Jeanloz, Raymond

    2003-07-01

    MgSiO3-rich perovskite is expected to dominate Earth's lower mantle (pressures >25 GPa) with iron and aluminum as significant substituents. The incorporation of trivalent ions, M3+, may occur by two competing mechanisms: MgA + SiB = MA + MB and SiB = AlB + 0.5 (vacancy)O. Phase synthesis studies show that both substitutions do occur and the nonstoichiometric or defect substitution is prevalent along the MgSiO3-MgAlO2.5 join. Lattice parameters associated with the first substitution (stoichiometric) show more rapid increases with increasing Al content than those for the second substitution (nonstoichiometric), consistent with the differences in size of substituting ions. Oxide melt solution calorimetry has been used to compare the energetics of both substitutions. The stoichiometric substitution, represented by the reaction 0.95 MgSiO3 (perovskite) + 0.05 Al2O3 (corundum) = Mg0.95Al0.10Si0.95O3 (perovskite), has an enthalpy of -0.8 ± 2.2 kJ/mol. The nonstoichiometric reaction, 0.90 MgSiO3 (perovskite) + 0.10 MgO (rocksalt) + 0.05 Al2O3 (corundum) = MgSi0.9Al0.1O2.95 (perovskite) has a small positive enthalpy of 8.5 ± 4.6 kJ/mol. Configurational T ΔS terms play a role in both substitutions. The defect substitution is not prohibitive in enthalpy, entropy, or volume, is favored in perovskite coexisting with magnesiowüstite and may significantly affect the elasticity, rheology, and water retention of silicate perovskite in Earth.

  5. Metal halide perovskite light emitters

    PubMed Central

    Kim, Young-Hoon; Cho, Himchan; Lee, Tae-Woo

    2016-01-01

    Twenty years after layer-type metal halide perovskites were successfully developed, 3D metal halide perovskites (shortly, perovskites) were recently rediscovered and are attracting multidisciplinary interest from physicists, chemists, and material engineers. Perovskites have a crystal structure composed of five atoms per unit cell (ABX3) with cation A positioned at a corner, metal cation B at the center, and halide anion X at the center of six planes and unique optoelectronic properties determined by the crystal structure. Because of very narrow spectra (full width at half-maximum ≤20 nm), which are insensitive to the crystallite/grain/particle dimension and wide wavelength range (400 nm ≤ λ ≤ 780 nm), perovskites are expected to be promising high-color purity light emitters that overcome inherent problems of conventional organic and inorganic quantum dot emitters. Within the last 2 y, perovskites have already demonstrated their great potential in light-emitting diodes by showing high electroluminescence efficiency comparable to those of organic and quantum dot light-emitting diodes. This article reviews the progress of perovskite emitters in two directions of bulk perovskite polycrystalline films and perovskite nanoparticles, describes current challenges, and suggests future research directions for researchers to encourage them to collaborate and to make a synergetic effect in this rapidly emerging multidisciplinary field. PMID:27679844

  6. Device modeling of perovskite solar cells based on structural similarity with thin film inorganic semiconductor solar cells

    NASA Astrophysics Data System (ADS)

    Minemoto, Takashi; Murata, Masashi

    2014-08-01

    Device modeling of CH3NH3PbI3-xCl3 perovskite-based solar cells was performed. The perovskite solar cells employ a similar structure with inorganic semiconductor solar cells, such as Cu(In,Ga)Se2, and the exciton in the perovskite is Wannier-type. We, therefore, applied one-dimensional device simulator widely used in the Cu(In,Ga)Se2 solar cells. A high open-circuit voltage of 1.0 V reported experimentally was successfully reproduced in the simulation, and also other solar cell parameters well consistent with real devices were obtained. In addition, the effect of carrier diffusion length of the absorber and interface defect densities at front and back sides and the optimum thickness of the absorber were analyzed. The results revealed that the diffusion length experimentally reported is long enough for high efficiency, and the defect density at the front interface is critical for high efficiency. Also, the optimum absorber thickness well consistent with the thickness range of real devices was derived.

  7. The Electronic Structure of Iron in Aluminous (Mg,Fe)SiO3 Perovskite at High-Pressures and Temperatures

    NASA Astrophysics Data System (ADS)

    Jackson, J. M.; Sturhahn, W.; Lerche, M.; Li, J.

    2006-12-01

    Knowledge of iron valences and spin states in silicate perovskite is relevant to our understanding of the physical and chemical properties of Earth's lower mantle such as transport properties, mechanical behavior, and element partitioning. Recent studies have proposed that aluminous ferromagnesium silicate perovskite (Al- Pv) is the principle sink for ferric iron in Earth's lower mantle [e.g. 1]. Also of geophysical interest is the electronic spin state of Al-Pv under lower mantle conditions. To date, simultaneous high-pressure and high- temperature measurements of the hyperfine parameters to identify the valence and spin states of iron in Al-Pv have not been reported. In this study, we have measured the electronic structure of the iron component of an aluminous Fe-bearing silicate perovskite sample, (Mg0.88Fe0.09)(Si0.94Al0.10)O3, close to a pyrolite composition, using synchrotron Mössbauer spectroscopy (SMS) and laser heated diamond anvil cells. Recent developments in SMS have enabled in situ measurements of small samples (< 10 μm) with relatively low 57Fe contents (< 10 at.%) to Mbar pressures [e.g. 2,3]. The samples were first synthesized in a multi-anvil apparatus [3], and the perovskite structure was confirmed by X-ray diffraction. The sample was loaded into a diamond anvil cell sandwiched between NaCl insulating layers. Measurements were carried out to 65 GPa and up to 2000 K at beamline 3-ID of the Advanced Photon Source. Spectra were collected before, during, and after laser heating, at each pressure point. Synchrotron Mössbauer spectra were also collected on decreasing pressure. Evaluation of the spectra provided the isomer shift (relative to stainless steel) and the quadrupole splitting of the iron component in silicate perovskite, which gives information on valence and spin states under lower mantle conditions. This work is supported by NSF through COMPRES and the U.S. DOE-BES, Office of Science, under Contract No. W-31-109-ENG-38. [1] Mc

  8. Scaling Effects in Perovskite Ferroelectrics: Fundamental Limits and Process-Structure-Property Relations

    DOE PAGES

    Ihlefeld, Jon F.; Harris, David T.; Keech, Ryan; Jones, Jacob L.; Maria, Jon-Paul; Trolier-McKinstry, Susan

    2016-07-05

    Ferroelectric materials are well-suited for a variety of applications because they can offer a combination of high performance and scaled integration. Examples of note include piezoelectrics to transform between electrical and mechanical energies, capacitors used to store charge, electro-optic devices, and non-volatile memory storage. Accordingly, they are widely used as sensors, actuators, energy storage, and memory components, ultrasonic devices, and in consumer electronics products. Because these functional properties arise from a non-centrosymmetric crystal structure with spontaneous strain and a permanent electric dipole, the properties depend upon physical and electrical boundary conditions, and consequently, physical dimension. The change of properties withmore » decreasing physical dimension is commonly referred to as a size effect. In thin films, size effects are widely observed, while in bulk ceramics, changes in properties from the values of large-grained specimens is most notable in samples with grain sizes below several microns. It is important to note that ferroelectricity typically persists to length scales of about 10 nm, but below this point is often absent. Despite the stability of ferroelectricity for dimensions greater than ~10 nm, the dielectric and piezoelectric coefficients of scaled ferroelectrics are suppressed relative to their bulk counterparts, in some cases by changes up to 80%. The loss of extrinsic contributions (domain and phase boundary motion) to the electromechanical response accounts for much of this suppression. In this article the current understanding of the underlying mechanisms for this behavior in perovskite ferroelectrics are reviewed. We focus on the intrinsic limits of ferroelectric response, the roles of electrical and mechanical boundary conditions, grain size and thickness effects, and extraneous effects related to processing. Ultimately, in many cases, multiple mechanisms combine to produce the observed scaling

  9. Structural and magnetic properties of perovskite Ca{sub 3}Fe{sub 2}WO{sub 9}

    SciTech Connect

    Ivanov, Sergey A. . E-mail: ivan@cc.nifhi.ac.ru; Eriksson, Sten Gunnar . E-mail: stene@inoc.chalmers.se; Tellgren, Roland . E-mail: rte@mkem.uu.se; Rundloef, Haekan

    2005-12-15

    A complex perovskite with composition Ca{sub 3}Fe{sub 2}WO{sub 9} has been synthesised, and the temperature evolution of nuclear and magnetic structures investigated by neutron powder diffraction. It was shown that at room temperature this compound adopts a monoclinic perovskite structure belonging to space group P12{sub 1}/n1 (a=5.4180(5)A, b=5.5093(5)A, c=7.7031(7)A), {beta}=90.04(2){sup o}). The partial B-site ordering, of the Fe{sup +3} and W{sup +6} cations, at (2c) and (2d) sites was determined. At low temperatures the magnetic diffraction peaks were registered and a possible model for the magnetic structure was proposed in accordance with the ferrimagnetic properties of the title compound. The magnetic structure is defined by a propagation vector k=(1/2,1/2,0) and can be described as an array of ferromagnetic (20-1) layers, which couple antiferromagnetically to each other. All the Fe moments within a layer are aligned parallel (or anti-parallel) to the c-axis. The structural and magnetic features of this compound are discussed and compared with those of some other quaternary oxides A{sub 3}Fe{sub 2}WO{sub 9} (A=Ba, Sr, Pb)

  10. Lattice instability and competing spin structures in the double perovskite insulator Sr2FeOsO6.

    PubMed

    Paul, Avijit Kumar; Reehuis, Manfred; Ksenofontov, Vadim; Yan, Binghai; Hoser, Andreas; Többens, Daniel M; Abdala, Paula M; Adler, Peter; Jansen, Martin; Felser, Claudia

    2013-10-18

    The semiconductor Sr2FeOsO6, depending on temperature, adopts two types of spin structures that differ in the spin sequence of ferrimagnetic iron-osmium layers along the tetragonal c axis. Neutron powder diffraction experiments, 57Fe Mössbauer spectra, and density functional theory calculations suggest that this behavior arises because a lattice instability resulting in alternating iron-osmium distances fine-tunes the balance of competing exchange interactions. Thus, Sr2FeOsO6 is an example of a double perovskite, in which the electronic phases are controlled by the interplay of spin, orbital, and lattice degrees of freedom. PMID:24182298

  11. Electronic band structure trends of perovskite halides: Beyond Pb and Sn to Ge and Si

    NASA Astrophysics Data System (ADS)

    Huang, Ling-yi; Lambrecht, Walter R. L.

    2016-05-01

    The trends in electronic band structure are studied in the cubic A B X3 halide perovskites for A =Cs ; B =Pb , Sn, Ge, Si; and X =I , Br, Cl. The gaps are found to decrease from Pb to Sn and from Ge to Si, but increase from Sn to Ge. The trend is explained in terms of the atom s levels of the group-IV element and the atomic sizes which changes the amount of hybridization with X -p and hence the valence bandwidth. Along the same series spin-orbit coupling also decreases and this tends to increase the gap because of the smaller splitting of the conduction band minimum. Both effects compensate each other to a certain degree. The trend with halogens is to reduce the gap from Cl to I, i.e., with decreasing electronegativity. The role of the tolerance factor in avoiding octahedron rotations and octahedron edge sharing is discussed. The Ge containing compounds have tolerance factor t >1 and hence do not show the series of octahedral rotation distortions and the existence of edge-sharing octahedral phases known for Pb and Sn-based compounds, but rather a rhombohedral distortion. CsGeI3 is found to have a suitable gap for photovoltaics both in its cubic (high-temperature) and rhombohedral (low-temperature) phases. The structural stability of the materials in the different phases is also discussed. We find the rhombohedral phase to have lower total energy and slightly larger gaps but to present a less significant distortion of the band structure than the edge-sharing octahedral phases, such as the yellow phase in CsSnI3. The corresponding silicon based compounds have not yet been synthesized and therefore our estimates are less certain but indicate a small gap for cubic CsSiI3 and CsSiBr3 of about 0.2 ±0.2 eV and 0.8 ±0.6 eV for CsSiCl3. The intrinsic stability of the Si compounds is discussed.

  12. Magnetic order and electronic structure of 5d3 double perovskite Sr2ScOsO6

    DOE PAGES

    Taylor, A. E.; Morrow, R.; Singh, D. J.; Calder, S.; Lumsden, M. D.; Woodward, P. M.; Christianson, A. D.

    2015-03-01

    The magnetic susceptibility, crystal and magnetic structures, and electronic structure of double perovskite Sr2ScOsO6 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. Density functional calculationsmore » 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

  13. Structural and transport properties of double perovskite Dy{sub 2}NiMnO{sub 6}

    SciTech Connect

    Chanda, Sadhan Saha, Sujoy; Dutta, Alo; Sinha, T.P.

    2015-02-15

    Highlights: • Sol–gel citrate method is used to prepare the double perovskite Dy{sub 2}NiMnO{sub 6}. • Structure and dielectric relaxation of the sample are studied for nano and bulk phases. • The relaxation mechanism of the sample is modeled by Cole–Cole equation. • With increasing sintering temperature conductivity increases. • Electronic structures and magnetic properties have been studied by DFT calculations. - Abstract: The double perovskite oxide Dy{sub 2}NiMnO{sub 6} (DNMO) is synthesized in nano and bulk phase by the sol–gel citrate method. The Rietveld refinement of X-ray diffraction pattern of the sample at room temperature shows the monoclinic P2{sub 1}/n phase. Dielectric relaxation of the sample is investigated in the impedance and electric modulus formalisms in the frequency range from 50 Hz to 1 MHz and in the temperature range from 253 to 415 K. The Cole–Cole model is used to explain the relaxation mechanism in DNMO. The frequency-dependent maxima in the imaginary part of impedance are found to obey an Arrhenius law with activation energy of 0.346 and 0.344 eV for nano and bulk DNMO, respectively. A significant increase in conductivity of bulk DNMO has been observed than that of the nanoceramic. Electronic structures and magnetic properties of DNMO have been studied by performing first principles calculation based on density functional theory.

  14. Synthesis of novel perovskite crystal structure phase of strontium doped rare earth manganites using sol gel method

    NASA Astrophysics Data System (ADS)

    Abdel-Latif, I. A.; Ismail, Adel A.; Bouzid, Houcine; Al-Hajry, A.

    2015-11-01

    In the present work, polycrystalline perovskites of R0.6Sr0.4MnO3 nanocomposites (R=La, Nd, or Sm) were synthesized using the sol-gel method in the presence of citric acid and polyethylene glycol as chelating and structure directing agents respectively. The synthesized gel was calcined at 800 °C for 5 h. The XRD revealed that the obtained nanocrystalline R0.6Sr0.4MnO3 is monoclinic crystal structure of space group (I2/a). TEM images showed that the prepared perovskites are homogeneous and uniform with particle sizes in a range 20-40 nm and the HR-TEM images and lattice fringes displayed the monoclinic structure. IV measurements showed that Nd0.6Sr0.4MnO3 has semiconducting properties at room temperature. With applying low magnetic field, a transition from semiconductor behavior to Ohmic resistivity was observed. The static resistance of Nd0.6Sr0.4MnO3 was calculated to be ~2.985 TΩ for semiconductor phase and the resistance increased 1000 times that gives rise to negative magnetoresistance (MR). The value of MR of Nd0.6Sr0.4MnO3 equals to 99.84%, which leads to the use of these materials in fabrication of magnetic devices in the industrial scale.

  15. Quasiparticle band gap of organic-inorganic hybrid perovskites: Crystal structure, spin-orbit coupling, and self-energy effects

    NASA Astrophysics Data System (ADS)

    Gao, Weiwei; Gao, Xiang; Abtew, Tesfaye; Sun, Yiyang; Zhang, Shengbai; Zhang, Peihong

    The quasiparticle band gaps of organic-inorganic hybrid perovskites are often determined (and can be controlled) by various factors, complicating predictive materials optimization. Here we report a comprehensive investigation on the band gap formation mechanism in CH3NH3PbI3 by decoupling various contributing factors which ultimately determine their electronic structure and quasiparticle band gap. Four major factors, namely, quasiparticle self-energy, spin-orbit coupling, volume (lattice constant) effects, and structural distortions due to the presence of organic molecules, and their influences on the quasiparticle band structure of organometal hybrid perovskites are illustrated. We find that although methylammonium cations do not contribute directly to the electronic states near band edges, they play an important role in defining the band gap through a lattice distortion mechanism and by controlling the overall lattice constants (thus the chemical bonding of the optically active PbI3-). The spin-orbit coupling effects drastically reduce the electron and hole effective masses in these systems, which is beneficial for high carrier mobilities and small exciton binding energies. This work is supported by the National Natural Science Foundation of China (Grant No. 11328401), NSF (Grant No. DMR-0946404 and DMR-1506669), and the SUNY Networks of Excellence.

  16. Electronic structure of ferromagnetic semiconductor material on the monoclinic and rhombohedral ordered double perovskites La{sub 2}FeCoO{sub 6}

    SciTech Connect

    Fuh, Huei-Ru; Chang, Ching-Ray; Weng, Ke-Chuan; Wang, Yin-Kuo

    2015-05-07

    Double perovskite La{sub 2}FeCoO{sub 6} with monoclinic structure and rhombohedra structure show as ferromagnetic semiconductor based on density functional theory calculation. The ferromagnetic semiconductor state can be well explained by the superexchange interaction. Moreover, the ferromagnetic semiconductor state remains under the generalized gradient approximation (GGA) and GGA plus onsite Coulomb interaction calculation.

  17. Mechanism of charge recombination in meso-structured organic-inorganic hybrid perovskite solar cells: A macroscopic perspective

    NASA Astrophysics Data System (ADS)

    Yang, Wenchao; Yao, Yao; Wu, Chang-Qin

    2015-04-01

    In the currently popular organic-inorganic hybrid perovskite solar cells, the slowness of the charge recombination processes is found to be a key factor for contributing to their high efficiencies and high open circuit voltages, but the underlying recombination mechanism remains unclear. In this work, we investigate the bimolecular recombination (BR) and the trap-assisted monomolecular recombination (MR) in meso-structured perovskite solar cells under steady state working condition, and try to reveal their roles on determining the device performance. Some interfacial effects such as the injection barriers at the selective contacts are examined as well. Based on the macroscopic device modeling, the recombination resistance-voltage (Rrec-V) and the current density-voltage (J-V) curves are calculated to characterize the recombination mechanism and describe the device performance, respectively. Through comparison with the impedance spectroscopy extracted Rrec data, it is found that under the typical BR reduction factor and deep trap densities observed in experiments, the MR dominates the charge recombination in the low voltage regime, while the BR dominates in the high voltage regime. The short circuit current and the fill factor could be reduced by the significant MR but the open circuit voltage is generally determined by the BR. The different electron injection barriers at the contact can change the BR rate and induce different patterns for the Rrec-V characteristics. For the perovskites of increased band gaps, the Rrec's are significantly enhanced, corresponding to the high open circuit voltages. Finally, it is revealed that the reduced effective charge mobility due to the transport in electron and hole transporting material makes the Rrec decrease slowly with the increasing voltage, which leads to increased open circuit voltage.

  18. Mechanism of charge recombination in meso-structured organic-inorganic hybrid perovskite solar cells: A macroscopic perspective

    SciTech Connect

    Yang, Wenchao; Yao, Yao Wu, Chang-Qin

    2015-04-21

    In the currently popular organic-inorganic hybrid perovskite solar cells, the slowness of the charge recombination processes is found to be a key factor for contributing to their high efficiencies and high open circuit voltages, but the underlying recombination mechanism remains unclear. In this work, we investigate the bimolecular recombination (BR) and the trap-assisted monomolecular recombination (MR) in meso-structured perovskite solar cells under steady state working condition, and try to reveal their roles on determining the device performance. Some interfacial effects such as the injection barriers at the selective contacts are examined as well. Based on the macroscopic device modeling, the recombination resistance-voltage (R{sub rec}−V) and the current density-voltage (J–V) curves are calculated to characterize the recombination mechanism and describe the device performance, respectively. Through comparison with the impedance spectroscopy extracted R{sub rec} data, it is found that under the typical BR reduction factor and deep trap densities observed in experiments, the MR dominates the charge recombination in the low voltage regime, while the BR dominates in the high voltage regime. The short circuit current and the fill factor could be reduced by the significant MR but the open circuit voltage is generally determined by the BR. The different electron injection barriers at the contact can change the BR rate and induce different patterns for the R{sub rec}–V characteristics. For the perovskites of increased band gaps, the R{sub rec}'s are significantly enhanced, corresponding to the high open circuit voltages. Finally, it is revealed that the reduced effective charge mobility due to the transport in electron and hole transporting material makes the R{sub rec} decrease slowly with the increasing voltage, which leads to increased open circuit voltage.

  19. Structural chemistry and magnetic properties of the perovskite Sr3Fe2TeO9

    NASA Astrophysics Data System (ADS)

    Tang, Yawei; Hunter, Emily C.; Battle, Peter D.; Sena, Robert Paria; Hadermann, Joke; Avdeev, Maxim; Cadogan, J. M.

    2016-10-01

    A polycrystalline sample of perovskite-like Sr3Fe2TeO9 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 Fe3+ and Te6+ 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 Sr3Fe2TeO9 is thus the first example of a 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.

  20. Structural properties of PbVO3 perovskites under hydrostatic pressure conditions up to 10.6 GPa.

    PubMed

    Zhou, Wei; Tan, Dayong; Xiao, Wansheng; Song, Maoshuang; Chen, Ming; Xiong, Xiaolin; Xu, Jian

    2012-10-31

    High-pressure synchrotron x-ray powder diffraction experiments were performed on PbVO(3) tetragonal perovskite in a diamond anvil cell under hydrostatic pressures of up to 10.6 GPa at room temperature. The compression behavior of the PbVO(3) tetragonal phase is highly anisotropic, with the c-axis being the soft direction. A reversible tetragonal to cubic perovskite structural phase transition was observed between 2.7 and 6.4 GPa in compression and below 2.2 GPa in decompression. This transition was accompanied by a large volume collapse of 10.6% at 2.7 GPa, which was mainly due to electronic structural changes of the V(4+) ion. The polar pyramidal coordination of the V(4+) ion in the tetragonal phase changed to an isotropic octahedral coordination in the cubic phase. Fitting the observed P-V data using the Birch-Murnaghan equation of state with a fixed [Formula: see text] of 4 yielded a bulk modulus K(0) = 61(2) GPa and a volume V(0) = 67.4(1) Å(3) for the tetragonal phase, and the values of K(0) = 155(3) GPa and V(0) = 58.67(4) Å(3) for the cubic phase. The first-principles calculated results were in good agreement with our experiments. PMID:23041755

  1. Sputtered lead scandium tantalate thin films: Pb{sup 4+} in B sites in the perovskite structure

    SciTech Connect

    Whatmore, R.W.; Huang, Z.; Todd, M.

    1997-12-01

    Perovskite lead scandium tantalate (PST){emdash}PbSc{sub 1/2}Ta{sub 1/2}O{sub 3}{emdash}thin films have been prepared from lead-rich targets by rf magnetron sputtering onto a variety of substrates (e.g., MgO-on-sapphire and platinized silicon). Detailed microstructural chemical analysis of the films using transmission electron microscopy and energy dispersive x-ray spectroscopy techniques showed that they contained large amounts of excess lead, ranging from 7 to over 70 at.{percent} and that this was located within the crystallite grains making up the films rather than solely at grain boundaries. Measurement of the lattice parameters of the films using x-ray diffraction and using the underlying materials as internal standards have shown that the lattice parameters of the films are consistently larger than those for bulk PST. Comparison of the film lattice parameters with composition and with the lattice parameter/composition trend of a large number of lead containing perovskites strongly suggests that the excess lead is present on the B sites of the structure as Pb{sup 4+}. The consequences for this on the structural and electrical properties of these films and PST films deposited by other workers are discussed. {copyright} {ital 1997 American Institute of Physics.}

  2. Novel Carbazole-Based Hole-Transporting Materials with Star-Shaped Chemical Structures for Perovskite-Sensitized Solar Cells.

    PubMed

    Kang, Min Soo; Sung, Sang Do; Choi, In Taek; Kim, Hyoungjin; Hong, MunPyo; Kim, Jeongho; Lee, Wan In; Kim, Hwan Kyu

    2015-10-14

    Novel carbazole-based hole-transporting materials (HTMs), including extended π-conjugated central core units such as 1,4-phenyl, 4,4'-biphenyl, or 1,3,5-trisphenylbenzene for promoting effective π-π stacking as well as the hexyloxy flexible group for enhancing solubility in organic solvent, have been synthesized as HTM of perovskite-sensitized solar cells. A HTM with 1,3,5-trisphenylbenzene core, coded as SGT-411, exhibited the highest charge conductivity caused by its intrinsic property to form crystallized structure. The perovskite-sensitized solar cells with SGT-411 exhibited the highest PCE of 13.00%, which is 94% of that of the device derived from spiro-OMeTAD (13.76%). Time-resolved photoluminescence spectra indicate that SGT-411 shows the shortest decay time constant, which is in agreement with the trends of conductivity data, indicating it having fastest charge regeneration. In this regard, a carbazole-based HTM with star-shaped chemical structure is considered to be a promising candidate HTM.

  3. Hierarchically Structured Hole Transport Layers of Spiro-OMeTAD and Multiwalled Carbon Nanotubes for Perovskite Solar Cells.

    PubMed

    Lee, Jiyong; Menamparambath, Mini Mol; Hwang, Jae-Yeol; Baik, Seunghyun

    2015-07-20

    The low electrical conductivity of spiro-OMeTAD hole transport layers impedes further enhancements of the power conversion efficiency (PCE) of perovskite solar cells. We embedded multiwalled carbon nanotubes (MWNTs) in spiro-OMeTAD (spiro-OMeTAD/MWNTs) to increase carrier mobility and conductivity. However, direct electrical contact between CH3 NH3 PbI3 and the MWNTs created pathways for undesirable back-electron transfer, owing to the large work function of MWNTs, limiting enhancements of the PCE. A hierarchical structure of pure spiro-OMeTAD and spiro-OMeTAD/MWNTs was designed to block back-electron transfer and fully exploit the enhanced charge transport of spiro-OMeTAD/MWNTs. The enhanced fill factor, short-circuit current density, open-circuit voltage, and PCE (15.1 %) were achieved by using this hierarchical hole transport layer structure (MWNT concentration=2 wt %). The perovskite solar cells were fabricated by a low-temperature solution process, further decreasing their per-Watt cost.

  4. Structural properties of PbVO3 perovskites under hydrostatic pressure conditions up to 10.6 GPa.

    PubMed

    Zhou, Wei; Tan, Dayong; Xiao, Wansheng; Song, Maoshuang; Chen, Ming; Xiong, Xiaolin; Xu, Jian

    2012-10-31

    High-pressure synchrotron x-ray powder diffraction experiments were performed on PbVO(3) tetragonal perovskite in a diamond anvil cell under hydrostatic pressures of up to 10.6 GPa at room temperature. The compression behavior of the PbVO(3) tetragonal phase is highly anisotropic, with the c-axis being the soft direction. A reversible tetragonal to cubic perovskite structural phase transition was observed between 2.7 and 6.4 GPa in compression and below 2.2 GPa in decompression. This transition was accompanied by a large volume collapse of 10.6% at 2.7 GPa, which was mainly due to electronic structural changes of the V(4+) ion. The polar pyramidal coordination of the V(4+) ion in the tetragonal phase changed to an isotropic octahedral coordination in the cubic phase. Fitting the observed P-V data using the Birch-Murnaghan equation of state with a fixed [Formula: see text] of 4 yielded a bulk modulus K(0) = 61(2) GPa and a volume V(0) = 67.4(1) Å(3) for the tetragonal phase, and the values of K(0) = 155(3) GPa and V(0) = 58.67(4) Å(3) for the cubic phase. The first-principles calculated results were in good agreement with our experiments.

  5. An efficient electron transport material of tin oxide for planar structure perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Murugadoss, Govindhasamy; Kanda, Hiroyuki; Tanaka, Soichiro; Nishino, Hitoshi; Ito, Seigo; Imahoric, Hiroshi; Umeyama, Tomokazu

    2016-03-01

    The photovoltaic performance of a perovskite solar cell based on a new electron conducting SnO2 film prepared at low temperature using different solvents was investigated. SnO2 was selected as an electron conducting medium due to its superior properties over TiO2, such as better antireflective properties, higher electron mobility, more suitable band edges and a wider band gap. A SnO2 layer was developed by spin-coating SnCl2 solution followed by annealing at 200 °C in air. The low-temperature (200 °C) annealed SnO2 layer exhibits enhanced crystallization, high transmittance, and uniform surface morphology using ethanol as a solvent rather than water. Solid state CuSCN hole conductor was used as HTM for reducing the device cost. A planar solar cell fabricated with CH3NH3PbI3 perovskite infiltrated SnO2 showed a power conversion efficiency of 8.38% with short-circuit current density of 18.99 mA cm-2, an open-circuit voltage of 0.96 mV and a fill factor of 45%. The devices were fabricated at >60% humidity level at room temperature. The results suggest that SnO2 is an effective charge collection system for CH3NH3PbI3 based planar perovskite solar cells. In addition, these results provide a new direction for the future improvement of perovskite solar cells using new electron conducting layers.

  6. Coupling and electrical control of structural, orbital and magnetic orders in perovskites

    PubMed Central

    Varignon, Julien; Bristowe, Nicholas C.; Bousquet, Eric; Ghosez, Philippe

    2015-01-01

    Perovskite oxides are already widely used in industry and have huge potential for novel device applications thanks to the rich physical behaviour displayed in these materials. The key to the functional electronic properties exhibited by perovskites is often the so-called Jahn-Teller distortion. For applications, an electrical control of the Jahn-Teller distortions, which is so far out of reach, would therefore be highly desirable. Based on universal symmetry arguments, we determine new lattice mode couplings that can provide exactly this paradigm, and exemplify the effect from first-principles calculations. The proposed mechanism is completely general, however for illustrative purposes, we demonstrate the concept on vanadium based perovskites where we reveal an unprecedented orbital ordering and Jahn-Teller induced ferroelectricity. Thanks to the intimate coupling between Jahn-Teller distortions and electronic degrees of freedom, the electric field control of Jahn-Teller distortions is of general relevance and may find broad interest in various functional devices. PMID:26482414

  7. Solid oxide fuel cell composite cathodes based on perovskite and fluorite structures

    NASA Astrophysics Data System (ADS)

    Sadykov, Vladislav; Mezentseva, Natalia; Usoltsev, Vladimir; Sadovskaya, Ekaterina; Ishchenko, Arkady; Pavlova, Svetlana; Bespalko, Yulia; Kharlamova, Tamara; Zevak, Ekaterina; Salanov, Aleksei; Krieger, Tamara; Belyaev, Vladimir; Bobrenok, Oleg; Uvarov, Nikolai; Okhlupin, Yury; Smorygo, Oleg; Smirnova, Alevtina; Singh, Prabhakar; Vlasov, Aleksandr; Korobeynikov, Mikhail; Bryazgin, Aleksandr; Kalinin, Peter; Arzhannikov, Andrei

    This work presents the results related to the functionally graded fluorite (F)-perovskite (P) nanocomposite cathodes for IT SOFC. Nanocrystalline fluorites (GDC, ScCeSZ) and perovskites (LSrMn, LSrFNi) were synthesized by Pechini method. Nanocomposites were prepared by the ultrasonic dispersion of F and P powders in isopropanol with addition of polyvinyl butyral. Different techniques for deposition and sintering of functionally graded cathode materials were applied including traditional approaches as well as original methods, such as radiation-thermal sintering under electron beam or microwave radiation. Morphology, microstructure and elemental composition of nanocomposites was characterized by XRD and HRTEM/SEM with EDX. Even for dense composites, the sizes of perovskite and fluorite domains remain in the nanorange providing developed P-F interfaces. Oxygen isotope heteroexchange and conductivity/weight relaxation studies demonstrated that these interfaces provide a path for fast oxygen diffusion. The redistribution of the elements between P and F phases in nanocomposites occurs without formation of insulating zirconate phases. Button-size fuel cells with nanocomposite functionally graded cathodes, thin YSZ layers and anode Ni/YSZ cermet (either bulk or supported on Ni-Al foam substrates) were manufactured. For optimized composition and functionally graded design of P-F nanocomposite cathodes, a stable performance in the intermediate temperature range with maximum power density up to 0.5 W cm -2 at 700 °C in wet H 2/air feeds was demonstrated.

  8. Normal mode determination of perovskite crystal structures with octahedral rotations: theory and applications.

    PubMed

    Islam, Mohammad A; Rondinelli, James M; Spanier, Jonathan E

    2013-05-01

    Nuclear site analysis methods are used to enumerate the normal modes of ABX3 perovskite polymorphs with octahedral rotations. We provide the modes of the 14 subgroups of the cubic aristotype describing the Glazer octahedral tilt patterns, which are obtained from rotations of the BX6 octahedra with different sense and amplitude about high-symmetry axes. We tabulate all normal modes of each tilt system and specify the contribution of each atomic species to the mode displacement pattern, elucidating the physical meaning of the symmetry unique modes. We have systematically generated 705 schematic atomic displacement patterns for the normal modes of all 15 (14 rotated + 1 unrotated) Glazer tilt systems. We show through some illustrative examples how to use these tables to identify the octahedral rotations, symmetric breathing, and first-order Jahn-Teller anti-symmetric breathing distortions of the BX6 octahedra, and the associated Raman selection rules. We anticipate that these tables and schematics will be useful in understanding the lattice dynamics of bulk perovskites and could serve as a reference point in elucidating the atomic origins of a wide range of physical properties of synthetic perovskite thin films and superlattices. PMID:23567868

  9. Structural and Optoelectronic Properties of X3ZN (X = Ca, Sr, Ba; Z = As, Sb, Bi) Anti-Perovskite Compounds

    NASA Astrophysics Data System (ADS)

    Ullah, Imran; Murtaza, G.; Khenata, R.; Mahmood, Asif; Muzzamil, M.; Amin, N.; Saleh, M.

    2016-06-01

    We employed first-principles calculations to predict the structural and optoelectronic properties of X3ZN (X = Ca, Sr, Ba; Z = As, Sb, Bi) anti-perovskite compounds using an all-electron full-potential linearized augmented plane-wave method. Optimized structural parameters are found to be in good agreement with the available experimental measurements. The electronic band structure is calculated using different exchange-correlation potentials which reveal that the investigated compounds are narrow direct band gap semiconductors. A direct narrow band gap at the center of the Brillouin zone emphasises the optical activity of these compounds. Prediction of the optical properties, such as the real and imaginary parts of the dielectric function and refractive index along with reflectivity and optical conductivity, reveals the importance of these compounds in the visible and near UV optoelectronic devices industry.

  10. 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

  11. Impact of Film Stoichiometry on the Ionization Energy and Electronic Structure of CH3 NH3 PbI3 Perovskites.

    PubMed

    Emara, Jennifer; Schnier, Tobias; Pourdavoud, Neda; Riedl, Thomas; Meerholz, Klaus; Olthof, Selina

    2016-01-20

    The electronic structure of a large sample set of CH3 NH3 PbI3 -based perovskites is studied. Combined investigations by UV/X-ray photoelectron spectroscopy and X-ray diffraction reveal that interstitials present in the film lead to changes in the occupied density of states close to the valence band, which in turn influences the performance of solar cells. Changes in elemental composition tune the ionization energy of the perovskite film by almost 1 eV without introducing significant amounts of gap states.

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

    DOE PAGES

    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. We find, consistent withmore » PDF analysis, Raman spectroscopy data suggest that the local structure changes to a higher ordered state at pressures above 4 GPa.« less

  13. 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

    2015-01-01

    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. PMID:26671171

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

    PubMed Central

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

    2015-01-01

    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. PMID:26671171

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    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.

  16. The Impact of the Crystallization Processes on the Structural and Optical Properties of Hybrid Perovskite Films for Photovoltaics.

    PubMed

    Grancini, Giulia; Marras, Sergio; Prato, Mirko; Giannini, Cinzia; Quarti, Claudio; De Angelis, Filippo; De Bastiani, Michele; Eperon, Giles E; Snaith, Henry J; Manna, Liberato; Petrozza, Annamaria

    2014-11-01

    We investigate the relationship between structural and optical properties of organo-lead mixed halide perovskite films as a function of the crystallization mechanism. For methylammonium lead tri-iodide, the organic cations rearrange within the inorganic cage, moving from crystals grown in a mesoporous scaffold to larger, oriented crystals grown on a flat substrate. This reduces the strain felt by the bonds forming the cage and affects the motion of the organic cation in it, influencing the electronic transition at the onset of the optical absorption spectrum of the semiconductor. Moreover, we demonstrate that in mixed-halide perovskite, though Cl(-) ions are not present in a detectable concentration in the unit cell, they drive the crystallization dynamics. This induces a preferential order during crystallization, from a molecular, i.e., organic-inorganic moieties arrangement, to a nano-mesoscopic level, i.e., larger crystals with anisotropic shape. Finally, we show that while Cl is mainly expelled from flat films made of large crystals, in the presence of an oxide mesoporous scaffold they are partially retained in the composite.

  17. New structure and spin state of iron-rich (Mg,Fe)SiO[subscript 3] post-perovskite

    SciTech Connect

    Yamanaka, T.; Mao, W.L.; Mao, H.-K.; Hemley, R.J.; Shen, G.

    2010-05-24

    There was a discrepancy between the seismic tomography and the elastic property of MgSiO{sub 3} perovskite at near the D{double_prime} zone and core boundary. Since a discovery of post-perovskite (ppv) of MgSiO{sub 3}, many investigations have made to explain the presence of low seismic velocity of the lower mantle and D{double_prime} zone. However, precise experimental structure analysis of ppv-(Mg{sub 1-x}Fe{sub x})SiO{sub 3} has never been reported because of the experimental difficulty. Fe and Mg cation distribution and ordering in ppv-(Mg,Fe)SiO{sub 3} in consideration of spins states are significant subject in lower mantle electronic and magnetic states. The present experiment aims X-ray emission study and structure analysis by Rietveld profile fitting of ppv-(Mg{sub 0.6},Fe{sub 0.4})SiO{sub 3} by the precise powder diffraction measurement. Monte Carlo calculation proposed the reliable structures of iron-rich phase of ppv-(Mg,Fe)SiO{sub 3}: Pmmn, Pmma, and Cm2m and Cmcm proposed by. The best-fit structure model with the highest reliability in the Rietveld fitting of ppv-(Mg{sub 0.6}Fe{sub 0.4})SiO{sub 3} is the structure of space group Pmma, in which Fe and Mg occupy two different sites of M1 and M2: the site occupancies are (Fe{sub 0.25}Mg{sub 0.75}) in the larger M1 site and (Fe{sub 0.55}, Mg{sub 0.45}) in the smaller M2 site. The two-site model is consistence with the previous results of X-ray emission and X-ray Moessbauer experiments.

  18. Efficient Visible Quasi-2D Perovskite Light-Emitting Diodes.

    PubMed

    Byun, Jinwoo; Cho, Himchan; Wolf, Christoph; Jang, Mi; Sadhanala, Aditya; Friend, Richard H; Yang, Hoichang; Lee, Tae-Woo

    2016-09-01

    Efficient quasi-2D-structure perovskite light-emitting diodes (4.90 cd A(-1) ) are demonstrated by mixing a 3D-structured perovskite material (methyl ammonium lead bromide) and a 2D-structured perovskite material (phenylethyl ammonium lead bromide), which can be ascribed to better film uniformity, enhanced exciton confinement, and reduced trap density. PMID:27334788

  19. Efficient Visible Quasi-2D Perovskite Light-Emitting Diodes.

    PubMed

    Byun, Jinwoo; Cho, Himchan; Wolf, Christoph; Jang, Mi; Sadhanala, Aditya; Friend, Richard H; Yang, Hoichang; Lee, Tae-Woo

    2016-09-01

    Efficient quasi-2D-structure perovskite light-emitting diodes (4.90 cd A(-1) ) are demonstrated by mixing a 3D-structured perovskite material (methyl ammonium lead bromide) and a 2D-structured perovskite material (phenylethyl ammonium lead bromide), which can be ascribed to better film uniformity, enhanced exciton confinement, and reduced trap density.

  20. Single Cesium Lead Halide Perovskite Nanocrystals at Low Temperature: Fast Single-Photon Emission, Reduced Blinking, and Exciton Fine Structure

    PubMed Central

    2016-01-01

    Metal-halide semiconductors with perovskite crystal structure are attractive due to their facile solution processability, and have recently been harnessed very successfully for high-efficiency photovoltaics and bright light sources. Here, we show that at low temperature single colloidal cesium lead halide (CsPbX3, where X = Cl/Br) nanocrystals exhibit stable, narrow-band emission with suppressed blinking and small spectral diffusion. Photon antibunching demonstrates unambiguously nonclassical single-photon emission with radiative decay on the order of 250 ps, representing a significant acceleration compared to other common quantum emitters. High-resolution spectroscopy provides insight into the complex nature of the emission process such as the fine structure and charged exciton dynamics. PMID:26771336

  1. 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

  2. Crystal structure of tetra-wickmanite, Mn(2+)Sn(4+)(OH)6.

    PubMed

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

    2015-02-01

    The crystal structure of tetra-wickmanite, ideally Mn(2+)Sn(4+)(OH)6 [mangan-ese(II) tin(IV) hexa-hydroxide], has been determined based on single-crystal X-ray diffraction data collected from a natural sample from Långban, Sweden. Tetra-wickmanite belongs to the octa-hedral-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 Mn(2+) and Sn(4+), respectively. Tetra-wickmanite exhibits tetra-gonal symmetry and is topologically similar to its cubic polymorph, wickmanite. The tetra-wickmanite structure is characterized by a framework of alternating corner-linked [Mn(2+)(OH)6] and [Sn(4+)(OH)6] octa-hedra, 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 octa-hedra 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 tetra-gonal stottite, Fe(2+)Ge(4+)(OH)6. PMID:25878828

  3. Effect of sintering time on structural, microstructural and chemical composition of Ni-doped lanthanum gallate perovskites

    SciTech Connect

    Colomer, M.T.

    2015-08-15

    This work reports the effect of two different sintering times, 6 and 48 h on the structural, microstructural, and chemical features of Ni-doped La{sub 0.90}Sr{sub 0.10}GaO{sub 3.00−δ}. Independently of the sintering time, La{sub 0.90}Sr{sub 0.10}Ga{sub 1−x}Ni{sub x}O{sub 3.00−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, LaSrGa{sub 3.00}O{sub 7.00} (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 La{sub 4.00}Ga{sub 2.00}O{sub 9.00} (nominal composition) is also observed as second phase when samples are

  4. Synthesis, structural and dielectric properties of double perovskite Ho2FeMnO6

    NASA Astrophysics Data System (ADS)

    Chakraborty, Tirthankar; Elizabeth, Suja

    2016-05-01

    A new double perovskite Ho2FeMnO6 was grown by nitrate route. Temperature dependent dielectric response was recorded at different frequencies. Relaxor-like-behavior is observed whose activation energy was calculated using Arrhenius equation. The dispersion is very small at room temperature. The Nyquist plot over a broad frequency range at room temperature provides evidence for the presence of three relaxations from sample electrode interface, grain boundary and grain. The corresponding values of resistance and capacitance were calculated from the equivalent circuit model analysis of the Nyquist plot.

  5. Activity and stability trends of perovskite oxides for oxygen evolution catalysis at neutral pH.

    PubMed

    Han, Binghong; Risch, Marcel; Lee, Yueh-Lin; Ling, Chen; Jia, Hongfei; Shao-Horn, Yang

    2015-09-21

    Perovskite oxides (ABO3) have been studied extensively to promote the kinetics of the oxygen evolution reaction (OER) in alkaline electrolytes. However, developing highly active catalysts for OER at near-neutral pH is desirable for many photoelectrochemical/electrochemical devices. In this paper, we systematically studied the activity and stability of well-known perovskite oxides for OER at pH 7. Previous activity descriptors established for perovskite oxides at pH 13, such as having an eg occupancy close to unity or having an O p-band center close to Fermi level, were shown to scale with OER activity at pH 7. Stability was a greater challenge at pH 7 than at pH 13, where two different modes of instability were identified from combined transmission electron microscopy and density functional theory analyses. Perovskites with O p-band close to Fermi level showed leaching of A-site atoms and surface amorphization under all overpotentials examined at pH 7, while those with O p-band far from Fermi level were stable under low OER current/potential but became unstable at high current/potential accompanied by leaching of B-site atoms. Therefore, efforts are needed to enhance the activity and stability of perovskites against A-site or B-site loss if used at neutral pH. PMID:26271910

  6. Activity and stability trends of perovskite oxides for oxygen evolution catalysis at neutral pH.

    PubMed

    Han, Binghong; Risch, Marcel; Lee, Yueh-Lin; Ling, Chen; Jia, Hongfei; Shao-Horn, Yang

    2015-09-21

    Perovskite oxides (ABO3) have been studied extensively to promote the kinetics of the oxygen evolution reaction (OER) in alkaline electrolytes. However, developing highly active catalysts for OER at near-neutral pH is desirable for many photoelectrochemical/electrochemical devices. In this paper, we systematically studied the activity and stability of well-known perovskite oxides for OER at pH 7. Previous activity descriptors established for perovskite oxides at pH 13, such as having an eg occupancy close to unity or having an O p-band center close to Fermi level, were shown to scale with OER activity at pH 7. Stability was a greater challenge at pH 7 than at pH 13, where two different modes of instability were identified from combined transmission electron microscopy and density functional theory analyses. Perovskites with O p-band close to Fermi level showed leaching of A-site atoms and surface amorphization under all overpotentials examined at pH 7, while those with O p-band far from Fermi level were stable under low OER current/potential but became unstable at high current/potential accompanied by leaching of B-site atoms. Therefore, efforts are needed to enhance the activity and stability of perovskites against A-site or B-site loss if used at neutral pH.

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

    SciTech Connect

    Lu, Fengqi; Kuang, Xiaojun

    2015-01-15

    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 instability 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.

  8. Cycling Performance of a Columnar-Structured Complex Perovskite in a Temperature Gradient Test

    NASA Astrophysics Data System (ADS)

    Schlegel, N.; Sebold, D.; Sohn, Y. J.; Mauer, G.; Vaßen, R.

    2015-10-01

    To increase the efficiency of turbines for the power generation and the aircraft industry, advanced thermal barrier coatings (TBCs) are required. They need to be long-term stable at temperatures higher than 1200 °C. Nowadays, yttria partially stabilized zirconia (YSZ) is applied as standard TBC material. But its long-term application at temperatures higher than 1200 °C leads to detrimental phase changes and sintering effects. Therefore, new materials have to be investigated, for example, complex perovskites. They provide high melting points, high thermal expansion coefficients and thermal conductivities of approx. 2.0 W/(m K). In this work, the complex perovskite La(Al1/4Mg1/2Ta1/4)O3 (LAMT) was investigated. It was deposited by the suspension plasma spraying (SPS) process, resulting in a columnar microstructure of the coating. The coatings were tested in thermal cycling gradient tests and they show excellent results, even though some phase decomposition was found.

  9. 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. PMID:27163050

  10. 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.

  11. Investigation on structural, optical and magnetic properties of double perovskite Gd{sub 2}NiMnO{sub 6}

    SciTech Connect

    Mohapatra, S. R.; Sahu, B.; Raut, S.; Singh, A. K.; Kaushik, S. D.

    2015-06-24

    Single phase double perovskite Gd{sub 2}NiMnO{sub 6} was prepared by conventional solid state reaction route. X-ray diffraction (XRD) result reveals that the compound possess monoclinic structure with space group P2{sub 1}/n. Optical characterization performed at room temperature via UV-visible spectroscopy confirms Gd{sub 2}NiMnO{sub 6} as a direct band-gap material with band gap of ∼1.5 eV. Magnetization measurement in Zero field cooled (ZFC) condition at H = 100 Oe shows magnetic transition at ∼ 125 K. Due to competing interactions between magnetic ions (Ni{sup 2+} and Mn{sup 4+}), we could observe two magnetic transition below 40 K.

  12. 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.

  13. Dominance of interface chemistry over the bulk properties in determining the electronic structure of epitaxial metal/perovskite oxide heterojunctions

    SciTech Connect

    Chambers, Scott A.; Du, Yingge; Gu, Meng; Droubay, Timothy C.; Hepplestone, Steven; Sushko, Petr

    2015-06-09

    We show that despite very similar crystallographic properties and work function values in the bulk, epitaxial Fe and Cr metallizations on Nb:SrTiO3(001) generate completely different heterojunction electronic properties. Cr is Ohmic whereas Fe forms a Schottky barrier with a barrier height of 0.50 eV. This contrast arises because of differences in interface chemistry. In contrast to Cr [Chambers, S. A. et al., Adv. Mater. 2013, 25, 4001.], Fe exhibits a +2 oxidation state and occupies Ti sites in the perovskite lattice, resulting in negligible charge transfer to Ti, upward band bending, and Schottky barrier formation. The differences between Cr and Fe are understood by performing first-principles calculations of the energetics of defect formation which corroborate the observed interface chemistry and structure.

  14. 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

  15. Synthesis of LaYbO3 perovskite through modified Pechini method: Structural, electric and magnetic characterization

    NASA Astrophysics Data System (ADS)

    Jaramillo P, J. A.; Landínez Téllez, D. A.; Roa-Rojas, J.; Parra Vargas, C. A.; Barrera, E. W.

    2015-10-01

    Single phase LaYbO3 lanthanide-based perovskite powder was synthesized by modified Pechini method, which is based on polyesterification of metal-citrate complexes in aqueous solution. Complexes were formed in aqueous solution and after polyalcohol addition and slow water evaporation, bond formation is allowed and a macroscopic polymeric network was produced, where cations are embedded and uniformly distributed. Finally, through several pyrolysis steps, microcrystalline oxide particles were obtained. Structural characterization was performed by means the powder X-ray diffraction (XRD) technique. The obtained patterns were indexed and refined to reveal that the LaYbO3 simple perovskite crystallizes in an orthorhombic structure, belonging to the Pnma (#62) space group, with lattice constants a = 6.0327 Å, b = 8.4138 Å and c = 5.8307 Å. Studies of electron dispersive X-ray spectroscopy show that the LaYbO3 is free of impurities. Electric response was evaluated by electric polarization measurements as a function of applied electric fields. Obtained curves show evidence of a hysteretic behavior related with dielectric losses which are characteristics of insulator materials. From the saturation values of electric charge, the relative dielectric constant was determined to be 22.6. The magnetic behavior was examined by means of the curves of magnetic susceptibility as a function of temperature. The fit with the Curie equation is in agreement with a typical paramagnetic feature with effective magnetic moment μ = 4.9 μB, which is close to the theoretical expected value from the Hund’s rules.

  16. 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.

  17. Solid State Structure-Reactivity Studies on Bixbyites, Fluorites and Perovskites Belonging to the Vanadate, Titanate and Cerate Families

    NASA Astrophysics Data System (ADS)

    Shafi, Shahid P.

    This thesis primarily focuses on the systematic understanding of structure-reactivity relationships in two representative systems: bixbyite and related structures as well as indium doped CeO2. Topotactic reaction routes have gained significant attention over the past two decades due to their potential to access kinetically controlled metastable materials. This has contributed substantially to the understanding of solid state reaction pathways and provided first insights into mechanisms. Contrary to the widely used ex-situ methods, in-situ techniques including powder x-ray diffraction and thermogravimetric-differential thermal analysis have been employed extensively throughout this work in order to follow the reaction pathways in real time. Detailed analysis of the AVO3 (A = In, Sc) bixbyite reactivity under oxidative conditions has been carried out and a variety of novel metastable oxygen defect phases have been identified and characterized. The novel metastable materials have oxygen deficient fluorite structures and consequently are potential ion conductors. Structural aspects of the topotactic vs. reconstructive transformations are illustrated with this model system. The structure-reactivity study of AVO3 phases was extended to AVO3 perovskite family. Based on the research methodologies and results from AVO3 bixbyite reactivity studies a generalized mechanistic oxidation pathway has been established with a non-vanadium phase, ScTiO3 bixbyite. However, there is stark contrast in terms of structural stability and features beyond this stability limit during AVO3 and ScTiO3 bixbyite reaction pathways. A series of complex reaction sequences including phase separation and phase transitions were identified during the investigation of ScTiO3 reactivity. The two-step formation pathway for the fluorite-type oxide ion conductor Ce1-xInxO2-delta (0 ≤ x ≤ 0.3) is being reported. The formation of the BaCe1-xInxO 3-delta perovskites and the subsequent CO2-capture reaction

  18. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    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.

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

    PubMed

    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 Fe(3+) and Ta(5+) 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 Fe(3+) and Ta(5+) for Ti(4+) 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

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

    PubMed

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

    2016-08-12

    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 Fe(3+) and Ta(5+) 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 Fe(3+) and Ta(5+) for Ti(4+) 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.

  2. Magnetic order and electronic structure of 5d3 double perovskite Sr2ScOsO6

    SciTech Connect

    Taylor, A. E.; Morrow, R.; Singh, D. J.; Calder, S.; Lumsden, M. D.; Woodward, P. M.; Christianson, A. D.

    2015-03-01

    The magnetic susceptibility, crystal and magnetic structures, and electronic structure of double perovskite Sr2ScOsO6 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. Density 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.

  3. Structure and dehydration of layered perovskite niobate with bilayer hydrates prepared by exfoliation/self-assembly process

    SciTech Connect

    Chen Yufeng; Zhao Xinhua; Ma Hui; Ma Shulan; Huang Gailing; Makita, Yoji; Bai Xuedong; Yang Xiaojing

    2008-07-15

    The crystals of an H-form niobate of HCa{sub 2}Nb{sub 3}O{sub 10}.xH{sub 2}O (x=0.5) being tetragonal symmetry (space group P4/mbm) with unit cell parameters a=5.4521(6) and c=14.414(2) A were exfoliated into nanosheets with the triple-layered perovskite structure. The colloid suspension of the nanosheets was put into dialysis membrane tubing and allowed self-assembly in a dilute KCl solution. By this method, a novel layered K-form niobate KCa{sub 2}Nb{sub 3}O{sub 10}.xH{sub 2}O (x=1.3, typically) with bilayer hydrates in the interlayer was produced. The Rieveld refinement and transmission electron microscope (TEM)/selected-area electron diffraction (SAED) observation indicated that the orientations of the a-/b-axis of each nanosheet as well as the c-axis are uniform, and the self-assembled compound had the same symmetry, tetragonal (P4/mbm) with a=5.453(2) and c=16.876(5) A, as the H-form precursor; the exfoliation/self-assembly process does not markedly affect the two-dimensional lattice of the layer. The large basal spacing resulted from the interlayer K{sup +} ions solvated by two layers of water molecules. The interlayer bilayers-water was gradually changed to monolayer when the temperatures higher than 100 deg. C, and all the water molecules lost when over 600 deg. C. Accompanying the dehydration, the crystal structure transformed from tetragonal to orthorhombic symmetry. Water molecules may take an important role for the layer layered compound to adjust the unit cell to tetragonal symmetry. - Graphical abstract: The structure of layered perovskite niobate KCa{sub 2}Nb{sub 3}O{sub 10}.xH{sub 2}O (x=1.3) having a bilayers-hydrates interlayer, obtained via the exfoliation of an H-form precursor and the self-assembly of Ca{sub 2}Nb{sub 3}O{sub 10}{sup -} nanosheets, was first discussed in detail and determined to be tetragonal symmetry (P4/mbm). The dehydration resulted in the structural transformation to orthorhombic structure.

  4. High-pressure synthesis, crystal structure and magnetic properties of double perovskite oxide Ba{sub 2}CuOsO{sub 6}

    SciTech Connect

    Feng, Hai L.; Arai, Masao; Matsushita, Yoshitaka; Tsujimoto, Yoshihiro; Yuan, Yahua; Sathish, Clastin I.; He, Jianfeng; Tanaka, Masahiko; Yamaura, Kazunari

    2014-09-15

    A new compositional double perovskite oxide Ba{sub 2}CuOsO{sub 6} was synthesized under high-pressure (6 GPa) and high-temperature (1500 °C) conditions. The polycrystalline Ba{sub 2}CuOsO{sub 6} was characterized by synchrotron X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility, isothermal magnetization, and specific heat measurements. The oxide crystallizes in a double-perovskite structure with an I4/m space group, in which Os(VI) and Cu(II) are ordered in the perovskite B-site. Ba{sub 2}CuOsO{sub 6} is electrically insulating with an activation energy of 0.813(2) eV and shows antiferromagnetic-like characteristics at temperatures of ∼55 K and ∼70 K. The results of the first-principle calculation suggested that the spin–orbit interaction of Os(VI) plays a substantial role in the insulating state. The Jahn–Teller distortion of CuO{sub 6} octahedra influences the magnetic characteristics with regard to possible two-dimensional magnetic correlations. - Graphical abstract: A new compositional double perovskite oxide Ba{sub 2}CuOsO{sub 6} synthesized by a high-pressure (6 GPa) and high-temperature (1500 °C) method. - Highlights: • A new compositional double perovskite oxide Ba{sub 2}CuOsO{sub 6} was synthesized. • Ba{sub 2}CuOsO{sub 6} is electrically insulating and antiferromagnetic below ∼70 K. • The Jahn–Teller distortion of CuO{sub 6} has relevance to possible magnetic anisotropy.

  5. Hybrid functional band gap calculation of SnO{sub 6} containing perovskites and their derived structures

    SciTech Connect

    Lee, Hyewon; Cheong, S.W.; Kim, Bog G.

    2015-08-15

    We have studied the properties of SnO{sub 6} octahedra-containing perovskites and their derived structures using ab initio calculations with different density functionals. In order to predict the correct band gap of the materials, we have used B3LYP hybrid density functional, and the results of B3LYP were compared with those obtained using the local density approximation and generalized gradient approximation data. The calculations have been conducted for the orthorhombic ground state of the SnO{sub 6} containing perovskites. We also have expended the hybrid density functional calculation to the ASnO{sub 3}/A'SnO{sub 3} system with different cation orderings. We propose an empirical relationship between the tolerance factor and the band gap of SnO{sub 6} containing oxide materials based on first principles calculation. - Graphical abstract: (a) Structure of ASnO{sub 3} for orthorhombic ground state. The green ball is A (Ba, Sr, Ca) cation and the small (red) ball on edge is oxygen. SnO{sub 6} octahedrons are plotted as polyhedron. (b) Band gap of ASnO{sub 3} as a function of the tolerance factor for different density functionals. The experimental values of the band gap are marked as green pentagons. (c) ASnO{sub 3}/A'SnO{sub 3} superlattices with two types cation arrangement: [001] layered structure and [111] rocksalt structure, respectively. (d) B3LYP hybrid functional band gaps of ASnO{sub 3}, [001] ordered superlattices, and [111] ordered superlattices of ASnO{sub 3}/A'SnO{sub 3} as a function of the effective tolerance factor. Note the empirical linear relationship between the band gap and effective tolerance factor. - Highlights: • We report the hybrid functional band gap calculation of ASnO{sub 3} and ASnO{sub 3}/A'SnO{sub 3}. • The band gap of ASnO{sub 3} using B3LYP functional reproduces the experimental value. • We propose the linear relationship between the tolerance factor and the band gap.

  6. Low temperature thermoelastic and structural properties of LaGaO3 perovskite in the Pbnm phase

    NASA Astrophysics Data System (ADS)

    Knight, Kevin S.

    2012-10-01

    The thermoelastic and structural properties of LaGaO3 perovskite have been studied using high resolution neutron diffractometry at 158 temperatures between 11 K and 548 K. Data collected in 2 K intervals between 410 K and 430 K show no evidence for an intermediate phase between the low temperature phase in space group Pbnm and the high temperature phase in space group F3¯2/n. From a simultaneous fit of the unit cell volume and the isochoric heat capacity, the phonon density of states in the Pbnm phase is shown to be approximated by a two-term Debye model, with characteristic temperatures 294(1) K and 831(1) K. Vibrational Debye temperatures, determined from fitting the temperature variation of the atomic displacement parameters, show the cations to be more associated with the lower characteristic temperature, whilst that for the anions, is closer to the higher characteristic temperature. Structural parameters are presented as the amplitudes of the seven symmetry-adapted basis-vectors of the aristotype phase, and a structural basis for the temperature-dependence of the bond lengths is outlined. The phase transition in both temperature and pressure arises when a non-bonded La-O distance approaches the La coordination sphere.

  7. Post-perovskite transitions in CaB4+O3 at high pressure

    NASA Astrophysics Data System (ADS)

    Akaogi, M.; Shirako, Y.; Kojitani, H.; Takamori, S.; Yamaura, K.; Takayama-Muromachi, E.

    2010-03-01

    High-pressure phase transitions in CaRhO3 were examined using a multianvil apparatus up to 27 GPa and 1930 oC. CaRhO3 perovskite transforms to post-perovskite via a monoclinic intermediate phase with increasing pressure. Volume changes for the transitions of perovskite - intermediate phase and of intermediate phase - post-perovskite are -1.1 and -0.7 %, respectively. CaRhO3 post-perovskite is the fourth quenchable post-perovskite oxide found so far. By high-temperature calorimetric experiments, enthalpy of the perovskite - post-perovskite transition in CaRuO3 was measured as 15.2±3.3 kJ/mol. Combining the datum with those of CaIrO3, it is shown that CaIrO3 perovskite is energetically less stable than CaRuO3 perovskite. This is consistent with the fact that orthorhombic distortion of CaIrO3 perovskite is larger than CaRuO3, as indicated with the tilt-angle of octahedral framework of perovskite structure. The transition pressure from perovskite to post-perovskite in CaBO3 (B = Ru, Rh, Ir) increases almost linearly with decreasing the tilt-angle, suggesting that the perovskite - post-perovskite transition may result from instability of the perovskite structure with pressure.

  8. Highly stable solution processed metal-halide perovskite lasers on nanoimprinted distributed feedback structures

    NASA Astrophysics Data System (ADS)

    Brenner, Philipp; Stulz, Mareike; Kapp, Dorothee; Abzieher, Tobias; Paetzold, Ulrich W.; Quintilla, Aina; Howard, Ian A.; Kalt, Heinz; Lemmer, Uli

    2016-10-01

    We report on the performance and stability of distributed feedback lasers based on the solution-processed methylammonium lead iodide perovskite (CH3NH3PbI3). The CH3NH3PbI3 layers are processed via solution-casting in ambient atmosphere onto nanoimprinted second order Bragg gratings. This way, we achieve highly polarized surface-emitted lasing at room temperature with a linewidth of less than 0.2 nm and a laser threshold of 120 kW/cm2. The lasing is stable; no change in the laser emission within 15 h of pulsed excitation with a repetition rate of 1 kHz (corresponding to >5 × 107 pulses) is observed, exceeding the stability achieved for solution processed organic semiconductor lasers. Furthermore, adjustment of the grating period allowed the lasing wavelength to be varied over the entire bandwidth of the amplified spontaneous emission (between 781 and 794 nm). The fabrication process of nanoimprinting followed by solution-casting of the gain material demonstrates that stable CH3NH3PbI3 lasers are compatible with scalable production technologies and offers a route towards electrically pumped diode architectures.

  9. Electronic structure and exchange interactions of insulating double perovskite La2CuRuO6

    NASA Astrophysics Data System (ADS)

    Panda, S. K.; Kvashnin, Y. O.; Sanyal, B.; Dasgupta, I.; Eriksson, O.

    2016-08-01

    We have performed first-principles calculations of the electronic and magnetic properties of insulating double perovskite compound La2CuRuO6 (LCRO) which has recently been reported to exhibit intriguing magnetic properties. We derived a tight-binding Hamiltonian for LCRO based on the N th -order muffin-tin orbital (NMTO) downfolding technique. The computed on-site energies and hopping integrals are used to estimate the dominant exchange interactions employing an extended Kugel-Khomskii model. This way the dominant exchange paths were identified and a low-energy spin model was proposed. The Green function method based on the magnetic force theorem has also been used to extract the exchange interactions to provide a more accurate estimation and to justify the model calculations. Our results show that the nearest neighbor (NN) Cu-Ru magnetic interactions are very much direction dependent and a strong antiferromagnetic next nearest neighbor Ru-Ru interaction along the crystallographic b axis is responsible for the magnetic frustration observed experimentally in this system. We argue that due to the broken symmetry, NN Cu-Ru interaction becomes stronger along one direction than the other, which essentially reduces the amount of frustration and helps the system to achieve an antiferromagnetic ground state at low temperature. A detailed microscopic explanation of the exchange mechanism is discussed. We also find that spin-orbit coupling effect is significant and causes a canting of the Ru spin with respect to the Cu moments.

  10. 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

  11. Nano-structured CuO-Cu2O Complex Thin Film for Application in CH3NH3PbI3 Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Chen, Lung-Chieh; Chen, Cheng-Chiang; Liang, Kai-Chieh; Chang, Sheng Hsiung; Tseng, Zhong-Liang; Yeh, Shih-Chieh; Chen, Chin-Ti; Wu, Wen-Ti; Wu, Chun-Guey

    2016-09-01

    Nano-structured CuO-Cu2O complex thin film-based perovskite solar cells were fabricated on an indium tin oxide (ITO)-coated glass and studied. Copper (Cu) thin films with a purity of 99.995 % were deposited on an ITO-coated glass by magnetron reactive sputtering. To optimize the properties of the nano-structured CuO-Cu2O complex thin films, the deposited Cu thin films were thermally oxidized at various temperatures from 300 to 400 °C. A CH3NH3PbI3 perovskite absorber was fabricated on top of CuO-Cu2O complex thin film by a one-step spin-coating process with a toluene washing treatment. Following optimization, the maximum power conversion efficiency (PCE) exceeded 8.1 %. Therefore, the low-cost, solution-processed, stable nano-structured CuO-Cu2O complex thin film can be used as an alternative hole transport layer (HTL) in industrially produced perovskite solar cells.

  12. Nano-structured CuO-Cu2O Complex Thin Film for Application in CH3NH3PbI3 Perovskite Solar Cells.

    PubMed

    Chen, Lung-Chieh; Chen, Cheng-Chiang; Liang, Kai-Chieh; Chang, Sheng Hsiung; Tseng, Zhong-Liang; Yeh, Shih-Chieh; Chen, Chin-Ti; Wu, Wen-Ti; Wu, Chun-Guey

    2016-12-01

    Nano-structured CuO-Cu2O complex thin film-based perovskite solar cells were fabricated on an indium tin oxide (ITO)-coated glass and studied. Copper (Cu) thin films with a purity of 99.995 % were deposited on an ITO-coated glass by magnetron reactive sputtering. To optimize the properties of the nano-structured CuO-Cu2O complex thin films, the deposited Cu thin films were thermally oxidized at various temperatures from 300 to 400 °C. A CH3NH3PbI3 perovskite absorber was fabricated on top of CuO-Cu2O complex thin film by a one-step spin-coating process with a toluene washing treatment. Following optimization, the maximum power conversion efficiency (PCE) exceeded 8.1 %. Therefore, the low-cost, solution-processed, stable nano-structured CuO-Cu2O complex thin film can be used as an alternative hole transport layer (HTL) in industrially produced perovskite solar cells. PMID:27637894

  13. Structural and magnetic properties of RTiNO{sub 2} (R=Ce, Pr, Nd) perovskite nitride oxides

    SciTech Connect

    Porter, Spencer H.; Huang, Zhenguo; Cheng, Zhenxiang; Avdeev, Maxim; Chen, Zhixin; Dou, Shixue; Woodward, Patrick M.

    2015-03-15

    Neutron powder diffraction indicates that CeTiNO{sub 2} and PrTiNO{sub 2} crystallize with orthorhombic Pnma symmetry (Ce: a=5.5580(5), b=7.8369(7), and c=5.5830(4) Å; Pr: a=5.5468(5), b=7.8142(5), and c=5.5514(5) Å) as a result of a{sup –}b{sup +}a{sup –} tilting of the titanium-centered octahedra. Careful examination of the NPD data, confirms the absence of long range anion order in both compounds, while apparent superstructure reflections seen in electron diffraction patterns provide evidence for short range anion order. Inverse magnetic susceptibility plots reveal that the RTiNO{sub 2} (R=Ce, Pr, Nd) compounds are paramagnetic with Weiss constants that vary from −28 to −42 K. Effective magnetic moments for RTiNO{sub 2} (R=Ce, Pr, Nd) are 2.43 μ{sub B}, 3.63 μ{sub B}, and 3.47 μ{sub B}, respectively, in line with values expected for free rare-earth ions. Deviations from Curie–Weiss behavior that occur below 150 K for CeTiNO{sub 2} and below 30 K for NdTiNO{sub 2} are driven by magnetic anisotropy, spin–orbit coupling, and crystal field effects. - Graphical abstract: The structure and magnetism of the oxide nitride perovskites RTiNO{sub 2} (R=Ce, Pr, Nd) have been explored. The average symmetry is shown to be Pnma with a random distribution of oxide and nitride ions and a{sup −}b{sup +}a{sup −} tilting of the titanium-centered octahedra, but electron diffraction shows evidence for short range anion order. All three compounds are paramagnetic but deviations from the Curie Weiss law are seen below 150 K for R=Ce and below 30 K for R=Nd. - Highlights: • The oxide nitride perovskites RTiNO{sub 2} (R=Ce, Pr) have been prepared and their structures determined. • Diffraction measurements indicate short range cis-order of O and N, but no long range order. • Compounds are paramagnetic with Weiss constants that vary from −28 to −42 K. • CeTiO{sub 2}N and NdTiO{sub 2}N deviate from Curie–Weiss behavior below 150 and 30 K, respectively.

  14. Effects of Bi doping on structural and magnetic properties of double perovskite oxides Sr2FeMoO6

    NASA Astrophysics Data System (ADS)

    Lan, Yaohai; Feng, Xiaomei; Zhang, Xin; Shen, Yifu; Wang, Ding

    2016-08-01

    A new series of double perovskite compounds Sr2 - δBixFeMoO6 have been synthesized by solid-state reaction. δ refers to the nominal doping content of Bi (δ = 0, 0.1, 0.2, 0.3, 0.4, 0.5), while the Bi content obtained by the Rietveld refinement is x = 0, 0.01, 0.05, 0.08, 0.10 and 0.12. Their crystal structure and magnetic properties are investigated. Rietveld analysis of the room temperature XRD data shows all the samples crystallize in the cubic crystal structure with the space group Fm 3 ‾ m and have no phase transition. SEM images show that substituted samples present a denser microstructure and bigger grains than Sr2FeMoO6, which is caused by a liquid sintering process due to the effumability of Bi. The unit cell volume increases with augment of Bi3+ concentration despite the smaller ionic radius Bi3+ compared with the Sr2+, which is attributed to the electronic effect. The degree of Fe/Mo order (η) increases first and then decreases to almost disappearance with augment of Bi doping, which is the result of contribution from electronic effect. Calculated saturation magnetization Ms(3) according to our phase separation likeness model matches well with the experimental ones. The observed variations of magnetoresistance (MR) are consistent with the Fe/Mo order (η) due to the internal connection with anti-site defect (ASD).

  15. Ab initio study of structural, mechanical, thermal and electronic properties of perovskites Sr(Li,Pd)H3

    NASA Astrophysics Data System (ADS)

    Benlamari, S.; Amara Korba, S.; Lakel, S.; Meradji, H.; Ghemid, S.; El Haj Hassan, F.

    2016-01-01

    The structural, elastic, thermal and electronic properties of perovskite hydrides SrLiH3 and SrPdH3 have been investigated using the all-electron full-potential linear augmented plane wave (FP-LAPW) method based on the density functional theory (DFT). For the exchange-correlation potential, local-density approximation (LDA) and generalized gradient approximation (GGA) have been used to calculate theoretical lattice parameters, bulk modulus, and its pressure derivative. The present results are in good agreement with available theoretical and experimental data. The three independent elastic constants (C11, C12 and C44) are also reported. From electronic band structure and density of states (DOSs), it is found that SrLiH3 is an insulator characterized by an indirect gap of 3.48 eV, while SrPdH3 is metallic with a calculated DOSs at Fermi energy of 0.745 states/eV-unit cell. Poisson’s ratio (σ), Young’s modulus (E), shear modulus (G), anisotropy factor (A), average sound velocities (vm) and density (ρ) of these compounds are also estimated for the first time. The Debye temperature is deduced from the average sound velocity. Variation of elastic constants and bulk modulus of these compounds as a function of pressure is also reported. Pressure and thermal effects on some macroscopic properties are predicted using the quasi-harmonic Debye model.

  16. Molecular dynamics of MgSiO 3 perovskite at high pressures: Equation of state, structure, and melting transition

    NASA Astrophysics Data System (ADS)

    Belonoshko, Anatoly B.

    1994-10-01

    Molecular dynamics (MD) simulations of MgSiO 3-perovskite and melt with the MATSUI (1988) interatomic potential are used to resolve the problem of inconsistency between modeled and experimental melting curves. Equations of state for solid and liquid MgSiO 3-perovskite are in agreement with experimental data and are useful for calculating densities at experimentally inaccessible temperatures and pressures. Comparison with the Preliminary Earth Model ( DZIEWONSKI and ANDERSON, 1981) shows that the equation of state of MgSiO 3-perovskite is consistent with seismic parameter for lower mantle. Two-phase MD simulations at constant pressure were also performed to calculate a melting curve of MgSiO 3-perovskite in agreement with the recent experiments. Overheating does not exceed 400 K in accord with the theoretical estimate for finite systems. Extrapolation of meltings temperature to the coremantle boundary pressure (134 GPa) with the Simon equation gives temperature of ≈6400 K for MgSiO 3-perovskite and shows that, according to accepted estimates of temperature at core-mantle boundary, MgSiO 3-perovskite remains solid.

  17. Large Grained Perovskite Solar Cells Derived from Single-Crystal Perovskite Powders with Enhanced Ambient Stability.

    PubMed

    Yen, Hung-Ju; Liang, Po-Wei; Chueh, Chu-Chen; Yang, Zhibin; Jen, Alex K-Y; Wang, Hsing-Lin

    2016-06-15

    In this study, we demonstrate the large grained perovskite solar cells prepared from precursor solution comprising single-crystal perovskite powders for the first time. The resultant large grained perovskite thin film possesses a negligible physical (structural) gap between each large grain and is highly crystalline as evidenced by its fan-shaped birefringence observed under polarized light, which is very different from the thin film prepared from the typical precursor route (MAI + PbI2).

  18. Electroluminescence from perovskite LEDs with the structure of Ag/Spiro-OMeTAD/CH3NH3PbI3/TiO2/FTO

    NASA Astrophysics Data System (ADS)

    Wang, Minhuan; Shi, Yantao; Bian, Jiming; Dong, Qingshun; Sun, Hongjun; Liu, Hongzhu; Luo, Yingmin; Zhang, Yuzhi

    2016-10-01

    The perovskite light-emitting diodes (Pe-LEDs) with the structure of Ag/Spiro-OMeTAD/CH3NH3PbI3/TiO2/FTO were synthesized, where the CH3NH3PbI3 perovskite layer was deposited by a two-step spin-coating process. A dominant near-infrared electroluminescence (EL) at 773 nm was detected from the Pe-LEDs under forward bias at room temperature. The origin and mechanism of the EL were discussed in comparison with the photoluminescence (PL) spectra, and it was attributed to the radiative recombination of electrons and holes confined in the CH3NH3PbI3 emissive layer. Moreover, the corresponding energy band diagrams was proposed to illustrate the carrier transport mechanism in the Pe-LED device.

  19. Compositional and Structural Versatility in an Unusual Family of anti-Perovskite Fluorides: [Cu(H2O)4]3[(MF6)(M'F6)].

    PubMed

    Felder, Justin B; Yeon, Jeongho; Smith, Mark D; Zur Loye, Hans-Conrad

    2016-07-18

    A series of six anti-perovskite fluorides of the type [Cu(H2O)4]3(M1-xM'xF6)2 (where M and M' = V, Cr, Mn, Fe as well as M = Fe and M' = V and Cr) was synthesized as high-quality single crystals via a mild hydrothermal route. These materials belong to a class of perovskite-based structures in which the anions and cations of the regular ABX3 perovskite structure have exchanged positions. Two complex anions, MF6(3-) and M'F6(3-), occupy the normal A and B cation positions, while three complex cations, [Cu(H2O)4](2+), occupy the normally anionic X positions. As in the ABX3 compositions, the A and B positions can be occupied by different complex anions, allowing for the preparation of a wide range of compositions. Magnetic property measurements were performed on all six phases, and complex magnetic behavior was observed at low temperatures in the Mn, Fe, and bimetallic Fe/V and Fe/Cr phases. PMID:27367900

  20. Stability of organometal perovskites with organic overlayers

    SciTech Connect

    Tran, Catherine D. T.; Liu, Yi; Thibau, Emmanuel S.; Llanos, Adrian; Lu, Zheng-Hong

    2015-08-15

    The air-stability of vapour-phase-deposited methylammonium lead triiodide (CH{sub 3}NH{sub 3}PbI{sub 3}) perovskite thin films has been studied using X-ray diffraction. It is found that the perovskite structure without organic coating decomposes completely within a short period of time (∼two days) upon exposure to ambient environment. The degradation of the perovskite structure is drastically reduced when the perovskite films are capped with thin N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) films. We discovered that the amount of lead iodide (PbI{sub 2}), a product of the degradation, grows as a function of time in a sigmoidal manner. Further mathematical modeling analysis shows that the perovskite degradation follows the Avrami equation, a kinetics theory developed for quantifying phase transformations in solid-state materials.

  1. Atomic structure of metal-halide perovskites from first principles: The chicken-and-egg paradox of the organic-inorganic interaction

    NASA Astrophysics Data System (ADS)

    Li, Jingrui; Rinke, Patrick

    2016-07-01

    We have studied the prototype hybrid organic-inorganic perovskite CH3NH3PbI3 and its three close relatives, CH3NH3SnI3 ,CH3NH3PbCl3 , and CsPbI3, using relativistic density function theory. The long-range van der Waals (vdW) interactions were incorporated into the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional using the Tkatchenko-Scheffler pairwise scheme. Our results reveal that hydrogen bonding, which is well described by the PBE functional, plays a decisive role for the structural parameters of these systems, including the position and orientation of the organic cation as well as the deformation of the inorganic framework. The magnitude of the inorganic-framework deformation depends sensitively on the orientation of the organic cation, and directly influences the stability of the hybrid perovskites. Our results suggest that the organic and the inorganic components complement each other; the low symmetry of the organic cation is the origin of the inorganic-framework deformation, which then aids the overall stabilization of the hybrid perovskite structure. This stabilization is indirectly affected by vdW interactions, which lead to smaller unit-cell volumes than in PBE and therefore modulate the interaction between the organic cation and the inorganic framework. The vdW-induced lattice-constant corrections are system dependent and lead to PBE+vdW lattice constants in good agreement with experiment. Further insight is gained by analyzing the vdW contributions. In all iodide-based hybrid perovskites, the interaction between the organic cation and the iodide anions provides the largest lattice-constant change, followed by iodine-iodine and the organic cation—heavy-metal cation interaction. These corrections follow an almost linear dependence on the lattice constant within the range considered in our study and are therefore approximately additive.

  2. Elucidating the band structure and free charge carrier dynamics of pure and impurities doped CH3NH3PbI(3-x)Cl(x) perovskite thin films.

    PubMed

    Zhang, Zhen-Yu; Chen, Xin; Wang, Hai-Yu; Xu, Ming; Gao, Bing-Rong; Chen, Qi-Dai; Sun, Hong-Bo

    2015-11-28

    CH3NH3PbI3-xClx perovskite material has been commonly used as the free charge generator and reservoir in highly efficient perovskite-based solid-state solar photovoltaic devices. However, many of the underlying fundamental photophysical mechanisms in this material such as the perovskite transition band structure as well as the dependent relationship between the carrier properties and lattice properties still lack sufficient understanding. Here, we elucidated the fundamental band structure of the pure CH3NH3PbI3-xClx pervoskite lattice, and then reported about the dependent relationship between the free charge carrier characteristic and the different CH3NH3PbI3-xClx pervoskite lattice thin films utilizing femtosecond time-resolved pump-probe technologies. The data demonstrated that the pure perovskite crystal band structure should only have one conduction and one valence band rather than dual valences, and the pure perovskite lattice could trigger more free charge carriers with a slower recombination rate under an identical pump intensity compared with the impurities doped perovskite crystal. We also investigated the perovskite film performance when exposed to moisture and water, the corresponding results gave us a dip in the optimization of the performance of perovskite based devices, and so as a priority this material should be isolated from moisture (water). This work may propose a deeper perspective on the comprehension for this material and it is useful for future optimization of applications in photovoltaic and light emission devices. PMID:26497219

  3. Low temperature thermoelastic and structural properties of LaGaO{sub 3} perovskite in the Pbnm phase

    SciTech Connect

    Knight, Kevin S.

    2012-10-15

    The thermoelastic and structural properties of LaGaO{sub 3} perovskite have been studied using high resolution neutron diffractometry at 158 temperatures between 11 K and 548 K. Data collected in 2 K intervals between 410 K and 430 K show no evidence for an intermediate phase between the low temperature phase in space group Pbnm and the high temperature phase in space group F3{sup Macron }2/n. From a simultaneous fit of the unit cell volume and the isochoric heat capacity, the phonon density of states in the Pbnm phase is shown to be approximated by a two-term Debye model, with characteristic temperatures 294(1) K and 831(1) K. Vibrational Debye temperatures, determined from fitting the temperature variation of the atomic displacement parameters, show the cations to be more associated with the lower characteristic temperature, whilst that for the anions, is closer to the higher characteristic temperature. Structural parameters are presented as the amplitudes of the seven symmetry-adapted basis-vectors of the aristotype phase, and a structural basis for the temperature-dependence of the bond lengths is outlined. The phase transition in both temperature and pressure arises when a non-bonded La-O distance approaches the La coordination sphere. - Graphical abstract: The weight fraction of the rhombohedral phase of LaGaO{sub 3} from the onset of the phase transition at 408 K to its completion at 430 K. Highlights: Black-Right-Pointing-Pointer Thermoelastic properties of LaGaO{sub 3} analyzed as a two-term Debye model. Black-Right-Pointing-Pointer Crystal structure and bonding analyzed in terms of symmetry-adapted basis-vectors. Black-Right-Pointing-Pointer Consistency between calorimetric and crystallographic measurements.

  4. Structural chemistry and magnetic properties of the perovskite SrLa2Ni2TeO9

    NASA Astrophysics Data System (ADS)

    Paria Sena, Robert; Hadermann, Joke; Chin, Chun-Mann; Hunter, Emily C.; Battle, Peter D.

    2016-11-01

    A polycrystalline sample of SrLa2Ni2TeO9 has been synthesized using a standard ceramic method and characterized by neutron diffraction, magnetometry and electron microscopy. The compound adopts a monoclinic, perovskite-like structure with space group P21/n and unit cell parameters a=5.6008(1), b=5.5872(1), c=7.9018(2) Å, β=90.021(6)° at room temperature. The two crystallographically-distinct B sites are occupied by Ni2+ and Te6+ in ratios of 83:17 and 50:50. Both ac and dc magnetometry suggest that the compound is a spin glass below 35 K but the neutron diffraction data show that some regions of the sample are antiferromagnetic. Electron microscopy revealed twinning on a nanoscale and local variations in composition. These defects are thought to be responsible for the presence of two distinct types of antiferromagnetic ordering. The magnetic properties of SrLa2Ni2TeO9 are discussed in terms of cation ordering in the microstructure.

  5. Structures, magnetic and dielectric properties of the ordered double perovskites LnPbNiSbO6 (Ln = La, Pr)

    NASA Astrophysics Data System (ADS)

    Han, Lin; Bai, Yijia; Liu, Xiaojuan; Yao, Chuangang; Meng, Junling; Liang, Qingshuang; Wu, Xiaojie; Meng, Jian

    2014-09-01

    The crystal structures, magnetic and dielectric properties for the ordered double perovskites LnPbNiSbO6 (Ln = La, Pr) have been investigated. Rietveld refinements of x-ray diffraction data have been indexed for the monoclinic symmetry in space group P21/n (No. 14) and a highly rock-salt ordered arrangement of NiO6 and SbO6 octahedra. The B-site lattices are distorted strongly due to the substitution of rare Earth ions at the A-site. The magnetization measurements show an antiferromagnetic ordering. The effective magnetic moments μ eff are larger than the spin-only values, suggesting that the orbital component for Ni2+ is significant. The maximum values of isothermal magnetization increase due to the lattice distortion of BO6 octahedra, which may weaken the antiferromagnetic interaction via Ni2+-O-Sb5+-O-Ni2+ paths. The dielectric constants for LaPbNiSbO6 present frequency dependence and the tan δ curves exhibit relaxor-like dielectric response. The ɛ‧ decreases with the reduction of the magnetic moments of B-site transition metal ions, which reveals a relationship between the dielectric and magnetic properties.

  6. Structural phase transition in perovskite metal-formate frameworks: a Potts-type model with dipolar interactions.

    PubMed

    Šimėnas, Mantas; Balčiūnas, Sergejus; Ma Combining Cedilla Czka, Mirosław; Banys, Jūras; Tornau, Evaldas E

    2016-07-21

    We propose a combined experimental and numerical study to describe an order-disorder structural phase transition in perovskite-based [(CH3)2NH2][M(HCOO)3] (M = Zn(2+), Mn(2+), Fe(2+), Co(2+) and Ni(2+)) dense metal-organic frameworks (MOFs). The three-fold degenerate orientation of the molecular (CH3)2NH2(+) (DMA(+)) cation implies a selection of the statistical three-state model of the Potts type. It is constructed on a simple cubic lattice where each lattice point can be occupied by a DMA(+) cation in one of the available states. In our model the main interaction is the nearest-neighbor Potts-type interaction, which effectively accounts for the H-bonding between DMA(+) cations and M(HCOO)3(-) cages. The model is modified by accounting for the dipolar interactions which are evaluated for the real monoclinic lattice using density functional theory. We employ the Monte Carlo method to numerically study the model. The calculations are supplemented with the experimental measurements of electric polarization. The obtained results indicate that the three-state Potts model correctly describes the phase transition order in these MOFs, while dipolar interactions are necessary to obtain better agreement with the experimental polarization. We show that in our model with substantial dipolar interactions the ground state changes from uniform to the layers with alternating polarization directions. PMID:27341447

  7. X-ray Absorption Fine Structure Studies of Mn Coordination in Doped Perovskite SrTiO3

    SciTech Connect

    Levin, I.; Krayzman, V; Woicik, J; Tkach, A; Vilarinho, P

    2010-01-01

    The coordination of Mn in doped SrTiO{sub 3} ceramics having nominal compositions SrTi{sub 0.98}Mn{sub 0.02}O{sub 3} and Sr{sub 0.98}Mn{sub 0.02}TiO{sub 3} was analyzed using x-ray absorption fine structure (XAFS) measurements. As expected, Mn{sup 4+} substitution for Ti{sup 4+} leads to Mn occupancy of the octahedral B-sites of ABO{sub 3} perovskite lattice with a Mn-O bond distance of 1.902 {angstrom} (compared to 1.953 {angstrom} for Ti-O) and no significant local distortions around the Mn atoms. In contrast, for the composition Sr{sub 0.98}Mn{sup 0.02}TiO{sub 3}, Mn segregates to both the A-sites (as Mn{sup 2+}) and the B-sites (predominantly as Mn{sup 4+}). Extended XAFS confirms strong ({approx} 0.77 {angstrom}) displacements of Mn{sup 2+} cations off the ideal A-site positions along <001> directions with a significant distortion of several coordination shells around the dopant atoms.

  8. Spectroscopy and structural characteristics of Eu3+-activated perovskite tungstate Ba2La2ZnW2O12

    NASA Astrophysics Data System (ADS)

    Yang, Li; Huang, Yanlin; Cheng, Han; Seo, Hyo Jin

    2015-11-01

    Eu3+-doped tungstate Ba2La2ZnW2O12 was prepared by the high-temperature solid-state reaction method. The x-ray powder diffraction (XRD) patterns indicate that the matrix has a perovskite structure. The samples were characterized by the scanning electron microscope (SEM), by optical diffuse reflection, photoluminescence (PL) spectra and by their decay curves. Eu3+-activated Ba2La2ZnW2O12 shows red luminescence under the excitation of near-ultraviolet and blue light. Laser site-selective excitation and emission spectroscopy technology was applied to investigate the spectroscopic and microstructural properties. The excitation spectra were tested by monitoring the emission from 5D0  →  7F0-4 transitions. Accordingly the emission spectra and decay curves (lifetime) were measured by the excitation in the 5D0  →  7F0 wavelength region using a pulsed, tunable, and narrow-band dye laser. We have detected two Eu3+ sites in Ba2La2ZnW2O12 with the temperature region ranging from 10 K to below 300 K. On the spectra data of the site-selective emission and decay, the Stark energy levels of Eu3+ at two different sites were determined. The lifetimes of Eu3+ ions at the two sites were compared. The energy transfer and crystallographic assignments for the Eu3+ sites were discussed.

  9. The thermal equation of state of (Mg, Fe)SiO3 bridgmanite (perovskite) and implications for lower mantle structures

    NASA Astrophysics Data System (ADS)

    Wolf, Aaron S.; Jackson, Jennifer M.; Dera, Przemeslaw; Prakapenka, Vitali B.

    2015-11-01

    The high-pressure/high-temperature equation of state (EOS) of synthetic 13% Fe-bearing bridgmanite (Mg silicate perovskite) is measured using powder X-ray diffraction in a laser-heated diamond anvil cell with a quasi-hydrostatic neon pressure medium. We compare these results, which are consistent with previous 300 K sound speed and compression studies, with a reanalysis of Fe-free Mg end-member data from Tange et al. (2012) to determine the effect of iron on bridgmanite's thermoelastic properties. EOS parameters are incorporated into an ideal lattice mixing model to probe the behavior of bridgmanite at deep mantle conditions. With this model, a nearly pure bridgmanite mantle composition is shown to be inconsistent with density and compressibility profiles of the lower mantle. We also explore the buoyant stability of bridgmanite over a range of temperatures and compositions expected for Large Low-Shear Velocity Provinces, concluding that bridgmanite-dominated thermochemical piles are more likely to be passive dense layers externally supported by convection, rather than internally supported metastable domes. The metastable dome scenario is estimated to have a relative likelihood of only 4-7%, given the narrow range of compositions and temperatures consistent with seismic constraints. If buoyantly supported, such structures could not have remained stable with greater thermal contrast early in Earth's history, ruling out formation scenarios involving a large concentration of heat producing elements.

  10. Influence of surface and finite size effects on the structural and magnetic properties of nanocrystalline lanthanum strontium perovskite manganites

    SciTech Connect

    Žvátora, Pavel; Veverka, Miroslav; Veverka, Pavel; Knížek, Karel; Závěta, Karel; Pollert, Emil; Goglio, Graziella; Duguet, Etienne; Kaman, Ondřej

    2013-08-15

    Syntheses of nanocrystalline perovskite phases of the general formula La{sub 1−x}Sr{sub x}MnO{sub 3+δ} were carried out employing sol–gel technique followed by thermal treatment at 700–900 °C under oxygen flow. The prepared samples exhibit a rhombohedral structure with space group R3{sup ¯}c in the whole investigated range of composition 0.20≤x≤0.45. The studies were aimed at the chemical composition including oxygen stoichiometry and extrinsic properties, i.e. size of the particles, both influencing the resulting structural and magnetic properties. The oxygen stoichiometry was determined by chemical analysis revealing oxygen excess in most of the studied phases. The excess was particularly high for the samples with the smallest crystallites (12–28 nm) while comparative bulk materials showed moderate non-stoichiometry. These differences are tentatively attributed to the surface effects in view of the volume fraction occupied by the upper layer whose atomic composition does not comply with the ideal bulk stoichiometry. - Graphical abstract: Evolution of the particle size with annealing temperature in the nanocrystalline La{sub 0.70}Sr{sub 0.30}MnO{sub 3+δ} phase. Display Omitted - Highlights: • The magnetic behaviour of nanocrystalline La{sub 1−x}Sr{sub x}MnO{sub 3+δ} phases was analyzed on the basis of their crystal structure, chemical composition and size of the particles. • Their Curie temperature and magnetization are markedly affected by finite size and surface effects. • The oxygen excess observed in the La{sub 1−x}Sr{sub x}MnO{sub 3+δ} nanoparticles might be generated by the surface layer with deviated oxygen stoichiometry.

  11. Tetrastrontium-digalliumoxide (Sr{sub 4}Ga{sub 2}O{sub 7})-synthesis and crystal structure of a mixed anion strontium gallate related to perovskite

    SciTech Connect

    Kahlenberg, Volker . E-mail: volker.kahlenberg@uibk.ac.at; Lazic, Biljana; Krivovichev, Sergey V.

    2005-05-15

    Crystal growth experiments yielded single crystals of Sr{sub 4}Ga{sub 2}O{sub 7}. The title compound is monoclinic, space group P1c1, a=13.0822(7)A, b=15.7967(6)A, c=15.8586(8)A, {beta}=90.643(6){sup o}, V=3277.1(3)A{sup 3}, Z=16 (R1=0.041 for 7155 observed reflections and 660 parameters). The crystals showed twinning by pseudo-merohedry. Furthermore, the diffraction data exhibited the typical features of a superstructure. Sr{sub 4}Ga{sub 2}O{sub 7} can be classified as a mixed anion gallate comprising insular [GaO{sub 4}]-groups and [Ga{sub 3}O{sub 10}]-trimers. Both anion groups are located in layers perpendicular to [100]. 32 symmetrically independent Sr-cations crosslink between the tetrahedral anion groups. Alternatively, the compound can be described as a 3x4x4 superstructure of ABO{sub 3} perovskite, with 22.2% vacancies in the oxygen sublattice. The relationship with perovskite can be expressed in the following crystal chemical formula: Sr(Ga{sub 2/3}Sr{sub 1/3})(O{sub 7/9}-bar {sub 2/9}){sub 3}. A discussion of the structure in the context with other similar defect perovskites in presented.

  12. Selective hydrogen oxidation in the presence of C3 hydrocarbons using perovskite oxygen reservoirs.

    PubMed

    Beckers, Jurriaan; Drost, Ruben; van Zandvoort, Ilona; Collignon, Paul F; Rothenberg, Gadi

    2008-05-16

    Perovskite-type oxides, ABO(3), can be successfully applied as solid "oxygen reservoirs" in redox reactions such as selective hydrogen combustion. This reaction is part of a novel process for propane oxidative dehydrogenation, wherein the lattice oxygen of the perovskite is used to combust hydrogen selectively from the dehydrogenation mixture at 550 degrees C. This gives three key advantages: it shifts the dehydrogenation equilibrium to the side of the desired products, heat is generated, thus aiding the endothermic dehydrogenation, and it simplifies product separation (H(2)O vs H(2)). Furthermore, the process is safer since it uses the catalysts' lattice oxygen instead of gaseous O(2). We screened fourteen perovskites for activity, selectivity and stability in selective hydrogen combustion. The catalytic properties depend strongly on the composition. Changing the B atom in a series of LaBO(3) perovskites shows that Mn and Co give a higher selectivity than Fe and Cr. Replacing some of the La atoms with Sr or Ca also affects the catalytic properties. Doping with Sr increases the selectivity of the LaFeO(3) perovskite, but yields a catalyst with low selectivity in the case of LaCrO(3). Conversely, doping LaCrO(3) with Ca increases the selectivity. The best results are achieved with Sr-doped LaMnO(3), with selectivities of up to 93 % and activities of around 150 mumol O m(-2). This catalyst, La(0.9)Sr(0.1)MnO(3), shows excellent stability, even after 125 redox cycles at 550 degrees C (70 h on stream). Notably, the activity per unit surface area of the perovskite catalysts is higher than that of doped cerias, the current benchmark of solid oxygen reservoirs.

  13. Non-collinear magnetism in multiferroic perovskites.

    PubMed

    Bousquet, Eric; Cano, Andrés

    2016-03-31

    We present an overview of the current interest in non-collinear magnetism in multiferroic perovskite crystals. We first describe the different microscopic mechanisms giving rise to the non-collinearity of spins in this class of materials. We discuss, in particular, the interplay between non-collinear magnetism and ferroelectric and antiferrodistortive distortions of the perovskite structure, and how this can promote magnetoelectric responses. We then provide a literature survey on non-collinear multiferroic perovskites. We discuss numerous examples of spin cantings driving weak ferromagnetism in transition metal perovskites, and of spin-induced ferroelectricity as observed in the rare-earth based perovskites. These examples are chosen to best illustrate the fundamental role of non-collinear magnetism in the design of multiferroicity.

  14. Crystal structure of post-perovskite-type CaIrO3 reinvestigated: new insights into atomic thermal vibration behaviors

    PubMed Central

    Nakatsuka, Akihiko; Sugiyama, Kazumasa; Yoneda, Akira; Fujiwara, Keiko; Yoshiasa, Akira

    2015-01-01

    Single crystals of the title compound, the post-perovskite-type CaIrO3 [calcium iridium(IV) trioxide], have been grown from a CaCl2 flux at atmospheric pressure. The crystal structure consists of an alternate stacking of IrO6 octa­hedral layers and CaO8 hendeca­hedral layers along [010]. Chains formed by edge-sharing of IrO6 octa­hedra (point-group symmetry 2/m..) run along [100] and are inter­connected along [001] by sharing apical O atoms to build up the IrO6 octa­hedral layers. Chains formed by face-sharing of CaO8 hendeca­hedra (point-group symmetry m2m) run along [100] and are inter­connected along [001] by edge-sharing to build up the CaO8 hendeca­hedral layers. The IrO6 octa­hedral layers and CaO8 hendeca­hedral layers are inter­connected by sharing edges. The present structure refinement using a high-power X-ray source confirms the atomic positions determined by Hirai et al. (2009 ▸) [Z. Kristallogr. 224, 345–350], who had revised our previous report [Sugahara et al. (2008 ▸). Am. Mineral. 93, 1148–1152]. However, the displacement ellipsoids of the Ir and Ca atoms based on the present refinement can be approximated as uniaxial ellipsoids elongating along [100], unlike those reported by Hirai et al. (2009 ▸). This suggests that the thermal vibrations of the Ir and Ca atoms are mutually suppressed towards the Ir⋯Ca direction across the shared edge because of the dominant repulsion between the two atoms. PMID:26396860

  15. Crystal structure of post-perovskite-type CaIrO3 reinvestigated: new insights into atomic thermal vibration behaviors.

    PubMed

    Nakatsuka, Akihiko; Sugiyama, Kazumasa; Yoneda, Akira; Fujiwara, Keiko; Yoshiasa, Akira

    2015-09-01

    Single crystals of the title compound, the post-perovskite-type CaIrO3 [calcium iridium(IV) trioxide], have been grown from a CaCl2 flux at atmospheric pressure. The crystal structure consists of an alternate stacking of IrO6 octa-hedral layers and CaO8 hendeca-hedral layers along [010]. Chains formed by edge-sharing of IrO6 octa-hedra (point-group symmetry 2/m..) run along [100] and are inter-connected along [001] by sharing apical O atoms to build up the IrO6 octa-hedral layers. Chains formed by face-sharing of CaO8 hendeca-hedra (point-group symmetry m2m) run along [100] and are inter-connected along [001] by edge-sharing to build up the CaO8 hendeca-hedral layers. The IrO6 octa-hedral layers and CaO8 hendeca-hedral layers are inter-connected by sharing edges. The present structure refinement using a high-power X-ray source confirms the atomic positions determined by Hirai et al. (2009 ▸) [Z. Kristallogr. 224, 345-350], who had revised our previous report [Sugahara et al. (2008 ▸). Am. Mineral. 93, 1148-1152]. However, the displacement ellipsoids of the Ir and Ca atoms based on the present refinement can be approximated as uniaxial ellipsoids elongating along [100], unlike those reported by Hirai et al. (2009 ▸). This suggests that the thermal vibrations of the Ir and Ca atoms are mutually suppressed towards the Ir⋯Ca direction across the shared edge because of the dominant repulsion between the two atoms.

  16. 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.

  17. 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. PMID:27300494

  18. Room-Temperature Solution-Processed NiOx:PbI2 Nanocomposite Structures for Realizing High-Performance Perovskite Photodetectors.

    PubMed

    Zhu, Hugh Lu; Cheng, Jiaqi; Zhang, Di; Liang, Chunjun; Reckmeier, Claas J; Huang, He; Rogach, Andrey L; Choy, Wallace C H

    2016-07-26

    While methylammonium lead iodide (MAPbI3) with interesting properties, such as a direct band gap, high and well-balanced electron/hole mobilities, as well as long electron/hole diffusion length, is a potential candidate to become the light absorbers in photodetectors, the challenges for realizing efficient perovskite photodetectors are to suppress dark current, to increase linear dynamic range, and to achieve high specific detectivity and fast response speed. Here, we demonstrate NiOx:PbI2 nanocomposite structures, which can offer dual roles of functioning as an efficient hole extraction layer and favoring the formation of high-quality MAPbI3 to address these challenges. We introduce a room-temperature solution process to form the NiOx:PbI2 nanocomposite structures. The nanocomposite structures facilitate the growth of the compact and ordered MAPbI3 crystalline films, which is essential for efficient photodetectors. Furthermore, the nanocomposite structures work as an effective hole extraction layer, which provides a large electron injection barrier and favorable hole extraction as well as passivates the surface of the perovskite, leading to suppressed dark current and enhanced photocurrent. By optimizing the NiOx:PbI2 nanocomposite structures, a low dark current density of 2 × 10(-10) A/cm(2) at -200 mV and a large linear dynamic range of 112 dB are achieved. Meanwhile, a high responsivity in the visible spectral range of 450-750 nm, a large measured specific detectivity approaching 10(13) Jones, and a fast fall time of 168 ns are demonstrated. The high-performance perovskite photodetectors demonstrated here offer a promising candidate for low-cost and high-performance near-ultraviolet-visible photodetection. PMID:27340899

  19. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, K.D.

    1991-06-25

    Perovskites of the structure A[sub 2]B[sub 2]C[sub 3]O[sub 10] are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  20. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, Kenneth D.

    1991-01-01

    Perovskites of the structure A.sub.2 B.sub.2 C.sub.3 O.sub.10 are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  1. Improper Ferroelectric Contributions in the Double Perovskite Pb2Mn0.6Co0.4WO6 System with a Collinear Magnetic Structure.

    PubMed

    Orlandi, Fabio; Righi, Lara; Mezzadri, Francesco; Manuel, Pascal; Khalyavin, Dmitry D; Delmonte, Davide; Pernechele, Chiara; Cabassi, Riccardo; Bolzoni, Fulvio; Solzi, Massimo; Calestani, Gianluca

    2016-05-01

    The physical characterization and the extended crystallographic study of the double perovskite system Pb2Mn0.6Co0.4WO6 indicate an improper ferroelectric contribution to the polarization induced by the magnetic ordering. In the paramagnetic phase, the compound displays a centrosymmetric orthorhombic double perovskite structure with the Pmcn1' symmetry. The structure is strongly distorted by the lead stereoactivity. Magnetization measurements show two magnetic transitions at 188 and 9 K, but the time-of-flight neutron diffraction data provide evidence for a long-range magnetic ordering only below the second transition. Quantitative structure refinements combined with a comprehensive symmetry analysis indicate the Pm'c21' magnetic space group to be the adequate symmetry to describe the structural distortions and spin ordering in the ground state of the system. The symmetry implies a coexistence of a spontaneous ferromagnetic moment and a ferroelectric polarization along the orthogonal b- and c-axes, respectively, in the long-range ordered structure. Macroscopic measurements confirm the presence of the spontaneous polarization also below the first transition at 188 K, where only short-range magnetic correlations are evidenced by diffuse scattering in neutron diffraction. PMID:27078522

  2. 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

    SciTech Connect

    Clemens, Oliver

    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 the 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.

  3. Synthesis, crystal structure and magnetic properties of a new B-site ordered double perovskite Sr{sub 2}CuIrO{sub 6}

    SciTech Connect

    Vasala, Sami; Yamauchi, Hisao; Karppinen, Maarit

    2014-12-15

    Here we synthesize and characterize a new double-perovskite oxide Sr{sub 2}CuIrO{sub 6}. The synthesis requires the use of high oxygen pressure to stabilize the VI oxidation state of iridium. The compound has a tetragonally-distorted crystal structure due to the Jahn–Teller active Cu{sup II} ion, and a high degree of B-site cation order. Magnetic transition is apparent at 15 K, but the zero-field-cooled and field-cooled susceptibilities diverge below this temperature. The high degree of cation order would exclude the possibility of a typical spin-glass, indicating that the divergence is probably due to a frustration of the magnetic interactions between Cu and Ir, with a high frustration factor of f≈25. - Graphical abstract: A new member of the A{sub 2}B′B″O{sub 6} double-perovskite family with JT-active Cu{sup II} at the B′ site and Ir{sup VI} at the B″ site is synthesized through high pressure synthesis and characterized for the structural and magnetic properties. - Highlights: • New member of the A{sub 2}CuB″O{sub 6} double-perovskite family is synthesized with B″=Ir. • Stabilization of Ir{sup VI} requires the use of high oxygen pressure synthesis. • Crystal structure is tetragonally distorted due to JT-active Cu{sup II}. • Divergence of ZFC and FC curves is seen below the T{sub N} of 15 K. • This is presumably due to a frustration effect.

  4. Synthesis and structure of Ba{sub 6}Co{sub 6}ClO{sub 16}, a new cobalt oxychloride with a layered perovskite-related structure

    SciTech Connect

    Tancret, Nathalie; Roussel, Pascal; Abraham, Francis . E-mail: francis.abraham@ensc-lille.fr

    2005-10-15

    Well-developed single crystals of the title compound were prepared using a BaCl{sub 2} flux and investigated by X-ray diffraction methods using Mo(K{alpha}) radiation and a Charge Coupled Device (CCD) detector. The crystal structure was solved and refined in the hexagonal symmetry with P6-bar m2 space group, a=5.6698(2)A and c=14.4654(5)A to a final R{sub 1}=0.022 for 44 parameters with 1418 individual reflections. The structure of Ba{sub 6}Co{sub 6}ClO{sub 16}, which is related to the 6H-perovkite-type structure of BaMnO{sub 2.88}, is formed by the periodic stacking along [001] of five [BaO{sub 3}] layers separated by a [BaOCl] with a (hhhchc) stacking sequence. The [BaO{sub 3}] stacking creates tetranuclear face sharing octahedra units Co{sub 4}O{sub 15} containing Co(III) connected by dimers of corner-sharing CoO{sub 4} tetrahedra. This new oxychloride belongs to the family of compounds formulated as [BaOCl]M'{sub 2}[Ba{sub n+1}M{sub n}O{sub 3n+3}] where n represents the thickness of the octahedral string in hexagonal perovskite slabs.

  5. Perovskite LaPbMSbO{sub 6} (M=Co, Ni): Structural distortion, magnetic and dielectric properties

    SciTech Connect

    Bai, Yijia; Han, Lin; Liu, Xiaojuan; Deng, Xiaolong; Wu, Xiaojie; Yao, Chuangang; Liang, Qingshuang; Meng, Junling; Meng, Jian

    2014-09-15

    The B-site ordered double perovskite oxides LaPbMSbO{sub 6} (M=Co, Ni) have been synthesized via the modified Sol–Gel precursor two-step route. Rietveld refinements reveal strong abnormal structural distortion and BO{sub 6} octahedral deformation appearing along the ab plane. Owing to the cooperative Jahn–Teller effect of Co{sup 2+} and Pb{sup 2+} ions, the Co-related compound exhibits almost complete Co{sup 2+}–Sb{sup 5+} order. For magnetic properties, spin-canted antiferromagnetic state with high extent of magnetic frustration is confirmed. The Ni-related compound presents heavier magnetic frustration for introducing tiny disorder on site occupation accompanied with valence state and further enhancing the complexity of magnetic competition. Dielectric measurements present a considerable temperature dependent dielectric relaxation with great dc-like loss feature in the LaPbCoSbO{sub 6}. For LaPbNiSbO{sub 6}, however, the permittivity with low dielectric loss is shown to be insensitive to either temperature or frequency. The corresponding electronic active energy manifests that the weakly bounded 3d-electron is prone to hop in a more distorted Co–Sb sublattice. - Graphical abstract: XRD Rietveld refinement result of LaPbCoSbO{sub 6} presented a large BO{sub 6} octahedral distortion along the ab plane. Based upon the variations from Co–O–Sb bond angles, a fierce competition from many extended magnetic coupling routes (M–O–O–M) would induce a considerably large magnetic frustration and electron hopping restriction. - Highlights: • Highly ordered LaPbMSbO{sub 6} (M=Co, Ni) were synthesized. • Abnormal structural distortion appeared in the ab plane. • Strong magnetic frustration was confirmed via M{sup 2+}–O–O–M{sup 2+} route. • Dielectric measurements presented a large difference between Co and Ni samples. • 3d-electronic structure determines lattice distortion and physical properties.

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

    PubMed

    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.

  7. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    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.

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

    PubMed

    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

  10. Effect of hydration on the structure of perovskite-like cuprates

    NASA Astrophysics Data System (ADS)

    Bobylev, I. B.; Naumov, S. V.; Zyuzeva, N. A.

    2016-09-01

    The effect of hydration at T = 150 and 200°C on the structures of YBa2Cu3O y (123) and a number of binary cuprates has been studied. It has been shown that the compounds containing oxygen vacancies in their structures interact with hydrogen significantly more strongly than cuprates without vacancies. Depending on the cuprate structure, hydrogen can be embedded in interstitial sites with the formation of hydrides and be attached to oxygen with the formation of hydroxides. The phase transition of the 123 phase to a defect tetragonal 124-type phase occurs only for the compounds with a high oxygen content. All the cuprates under study are more stable to reduction as compared to CuO.

  11. The defect structure and chemical lattice strain of the double perovskites Sr2BMoO6-δ (B = Mg, Fe).

    PubMed

    Tsvetkov, D S; Ivanov, I L; Malyshkin, D A; Steparuk, A S; Zuev, A Yu

    2016-08-01

    The defect structure of B-site ordered double perovskites Sr2BMoO6-δ was analyzed. The defect structure model was proposed and successfully verified using data on oxygen nonstoichiometry of Sr2MgMoO6-δ and Sr2FeMoO6-δ. As a result, equilibrium constants of the defect reactions involved were estimated. Fe and Mo in Sr2FeMoO6-δ were found to be in the mixed oxidation state close to +2.5 and +5.5, respectively. Chemical strain of the Sr2FeMoO6-δ double perovskite lattice was studied by in situ high temperature XRD at 1100 °C depending on pO2. Parameter a of the Sr2FeMoO6-δ cubic cell was found to increase with decreasing pO2 because of lattice chemical expansion. The tetragonal polymorph of Sr2FeMoO6-δ was shown to exhibit transversal isotropy with respect to chemical expansion. It was also found that its crystal lattice expands in the ab-plane and simultaneously contracts along the c-axis when the oxygen content in the double perovskite decreases. In order to describe the degree of anisotropy of chemical strain a new phenomenological coefficient was introduced. This coefficient was shown to affect both the magnitude and change direction of an oxide cell volume caused by its reduction/oxidation. Excellent agreement between the chemical expansion along the a-axis calculated for both polymorphs of Sr2FeMoO6-δ according to the model recently developed and that measured experimentally was shown. Chemical contraction observed along the c-axis with a decreasing oxygen content in the tetragonal polymorph was also found to coincide completely with that calculated using the approach developed in the present study. PMID:27476830

  12. Crystal structure, phase transitions, and magnetic properties of titanium doped La0.5Sr0.5MnO3 perovskites

    NASA Astrophysics Data System (ADS)

    Hazzez, M.; Ihzaz, N.; Boudard, M.; Oumezzine, M.

    2016-04-01

    The current paper investigates the effect of titanium substitution on the structure as well as the magnetic properties of La0.5Sr0.5Mn1-xTixO3 (0≤x≤0.5) polycrystalline powder. The samples studied crystallize in a distorted perovskite structures of tetragonal (space group I4/mcm) symmetry with octahedral tilting scheme (a0a0c-), leading to the absence of octahedral tilting all along two perovskite main directions and to an out-of-phase along the third direction, or rhombohedral (space group R 3 bar c) symmetry with octahedral tilting scheme (a-a-a-) yielding to out-of-phase along the three perovskite main directions. As the Ti content increases, a better matching of the (Mn/Ti)-O distances and (Mn/Ti)-O-(Mn/Ti) bond angle occurs. This phenomenon is created by an elongation of the (Mn/Ti)-O distance, as Mn4+ is substituted by the larger ion Ti4+. In the whole compositional range, the symmetry-adapted to atomic displacements, responsible for the out-of-phase tilting of the (Mn/Ti)O6 octahedra, stays active, anticipating tetragonal-to-rhombohedral phase transition. Taking in to account what has been explained above, measurements of magnetic properties show a decrease of magnetic ordering temperature when Ti content increases, which in turn leads to the diminution of the exchange interaction caused by reducing the FM coupling and the replacement of neighboring manganese Mn3+-O-Mn4+ by Mn3+-O-Ti4+ bonds. This phenomenon results in broadening of the paramagnetic to ferromagnetic phase transition range. Further changes in magnetic properties with the increase in Ti concentration are studied.

  13. The defect structure and chemical lattice strain of the double perovskites Sr2BMoO6-δ (B = Mg, Fe).

    PubMed

    Tsvetkov, D S; Ivanov, I L; Malyshkin, D A; Steparuk, A S; Zuev, A Yu

    2016-08-01

    The defect structure of B-site ordered double perovskites Sr2BMoO6-δ was analyzed. The defect structure model was proposed and successfully verified using data on oxygen nonstoichiometry of Sr2MgMoO6-δ and Sr2FeMoO6-δ. As a result, equilibrium constants of the defect reactions involved were estimated. Fe and Mo in Sr2FeMoO6-δ were found to be in the mixed oxidation state close to +2.5 and +5.5, respectively. Chemical strain of the Sr2FeMoO6-δ double perovskite lattice was studied by in situ high temperature XRD at 1100 °C depending on pO2. Parameter a of the Sr2FeMoO6-δ cubic cell was found to increase with decreasing pO2 because of lattice chemical expansion. The tetragonal polymorph of Sr2FeMoO6-δ was shown to exhibit transversal isotropy with respect to chemical expansion. It was also found that its crystal lattice expands in the ab-plane and simultaneously contracts along the c-axis when the oxygen content in the double perovskite decreases. In order to describe the degree of anisotropy of chemical strain a new phenomenological coefficient was introduced. This coefficient was shown to affect both the magnitude and change direction of an oxide cell volume caused by its reduction/oxidation. Excellent agreement between the chemical expansion along the a-axis calculated for both polymorphs of Sr2FeMoO6-δ according to the model recently developed and that measured experimentally was shown. Chemical contraction observed along the c-axis with a decreasing oxygen content in the tetragonal polymorph was also found to coincide completely with that calculated using the approach developed in the present study.

  14. Perovskites: transforming photovoltaics, a mini-review

    DOE PAGES

    Chilvery, Ashwith Kumar; Batra, Ashok K.; Yang, Bin; Xiao, Kai; Guggilla, Padmaja; Aggarwal, Mohan D.; Surabhi, Raja; Lal, Ravi B.; Currie, James R.; Penn, Benjamin G.

    2015-01-06

    The recent power-packed advent of perovskite solar cells is transforming photovoltaics (PV) with their superior efficiencies, ease of fabrication, and cost. This perovskite solar cell further boasts of many unexplored features that can further enhance its PV properties and lead to it being branded as a successful commercial product. This paper provides a detailed insight of the organometal halide based perovskite structure, its unique stoichiometric design, and its underlying principles for PV applications. Finally, the compatibility of various PV layers and its fabrication methods is also discussed.

  15. Band gap engineering strategy via polarization rotation in perovskite ferroelectrics

    SciTech Connect

    Wang, Fenggong Grinberg, Ilya; Rappe, Andrew M.

    2014-04-14

    We propose a strategy to engineer the band gaps of perovskite oxide ferroelectrics, supported by first principles calculations. We find that the band gaps of perovskites can be substantially reduced by as much as 1.2 eV through local rhombohedral-to-tetragonal structural transition. Furthermore, the strong polarization of the rhombohedral perovskite is largely preserved by its tetragonal counterpart. The B-cation off-center displacements and the resulting enhancement of the antibonding character in the conduction band give rise to the wider band gaps of the rhombohedral perovskites. The correlation between the structure, polarization orientation, and electronic structure lays a good foundation for understanding the physics of more complex perovskite solid solutions and provides a route for the design of photovoltaic perovskite ferroelectrics.

  16. The anionic superconductor Bi[sub 3]BaO[sub 5. 5]: A bcc structure closely related to the perovskite. Relationships with anti [alpha]-AgI

    SciTech Connect

    Michel, C.; Pelloquin, D.; Hervieu, M.; Raveau, B. ); Abbattista, F.; Vallino, M. )

    1994-03-01

    The average bcc structure of Bi[sub 3]BaO[sub 5.5] (a = 4.3822(2) [angstrom]) has been determined by powder neutron diffraction. The calculations performed in the space group Im3m have shown that the Bi and Ba atoms are statistically distributed over the 2(a) sites (0,0,0), whereas oxygen and anionic vacancies are statistically distributed over the 6(b) sites (1/2,0,0). The cationic positions and the large anisotropic thermal factors of the oxygen atoms resemble the anti [alpha]-AgI structure. However, the anionic positions correspond to those observed in the perovskite. Thus, contrary to Cd[sub 0.79]Cd[sub 0.21]O[sub 1.39], this phase cannot be considered as an anti [alpha]-AgI structure. It can better be described as the coexistence of the two configurations of the perovskite inside the crystals. Ionic conductivity measurements show that this phase is an anionic conductor with an activation energy of 0.90 eV and T[sub 673 K] [approximately] 10[sup [minus]3] [Omega][sup [minus]1] cm[sup [minus]1].

  17. Synthesis, crystal structures, and magnetic properties of double perovskites SrLaNiOsO6 and BaLaNiOsO6

    NASA Astrophysics Data System (ADS)

    Feng, Hai L.; Schnelle, Walter; Tjeng, Liu Hao; Jansen, Martin

    2016-10-01

    New double perovskite oxides SrLaNiOsO6 and BaLaNiOsO6 were synthesized by solid state reactions from the respective binary metal oxides, and their crystal structures and magnetic properties were characterized. At room temperature SrLaNiOsO6 and BaLaNiOsO6 crystallize in ordered double perovskite structures with space groups of P21/n (monoclinic) and I4/m (tetragonal), respectively. They are electrically semiconducting with an activation energy of ≈0.35 eV. Specific heat and magnetic measurements indicate that SrLaNiOsO6 shows predominantly antiferromagnetic correlations and displays antiferromagnetic transition around 60 K. However, for the isoelectronic BaLaNiOsO6 ferromagnetic correlations are predominant and there is no clear feature of a magnetic transition detectable. The remarkable change in magnetic properties of ALaNiOsO6 (A = Sr and Ba) can be related to the degree of structure distortions, i.e. the bending of the O-B-O (B = Ni,Os) links.

  18. Magnetic and structural properties of CaMn0.9Mo0.1O3 perovskite synthesized in abnormal glow discharge

    NASA Astrophysics Data System (ADS)

    Sarmiento Santos, Armando; Parra Vargas, Carlos Arturo; Supelano García, Ivan

    2015-09-01

    In this work we use the abnormal glow discharge (AGD) to produce the CaMn0.9Mo0.1O3 perovskite through decarbonize, calcination and sintering steps. Structural characterization was carry out by Rietveld refinement of X-ray diffraction on samples after sintering step. The magnetic properties was analysed through magnetization curves as a function of temperature for applied magnetic fields in the range of 20 Oe to 20 kOe by the ZFC-FC method and magnetization curves in function of the applied field at 50 K and 300 K temperatures. The CaMn0.9Mo0.1O3 perovskite was also produced by conventional method in resistive furnace and its behaviour was compared with those of the plasma synthesized. The X-ray analysis reveals that the samples produced by both methods crystalized in a Pnma structure, the lattice parameters change and one second phase appears when the AGD is applied in the last production steps. The magnetization measurements allow analysing the behaviour of the sample at low temperatures and comparing the magnetic transitions in the samples produced by both methods; these are influenced according to production method employed. The results shows that the use of AGD is an alternative method to produce ceramic materials, which reduced ostensibly the production time and allow to obtain similar magnetic and structural properties with respect to conventional method.

  19. First principles study of the structural and electronic properties of double perovskite Ba2YTaO6 in cubic and tetragonal phases

    NASA Astrophysics Data System (ADS)

    Deluque Toro, C. E.; Rodríguez M., Jairo Arbey; Landínez Téllez, D. A.; Moreno Salazar, N. O.; Roa-Rojas, J.

    2014-12-01

    The Ba2YTaO6 double perovskite presents a transition from cubic (Fm-3m) to tetragonal structure (I4/m) at high temperature. In this work, we present a detailed study of the structural and electronic properties of the double perovskite Ba2YTaO6 in space group Fm-3m and I4/m. Calculations were made with the Full-Potential Linear Augmented Plane Wave method (FP-LAPW) within the framework of the Density Functional Theory (DFT) with exchange and correlation effects in the Generalized Gradient (GGA) and Local Density (LDA) approximations. From the minimization of energy as a function of volume and the fitting of the Murnaghan equation some structural characteristics were determined as, for example, total energy, lattice parameter (a=8.50 Å in cubic phase and a=5.985 Å and c=8.576 Å in tetragonal), bulk modulus (135.6 GPa in cubic phase and 134.1 GPa in tetragonal phase) and its derivative. The study of the electronic characteristics was performed from the analysis of the electronic density of states (DOS). We find a non-metallic behavior for this with a direct band gap of approximately 3.5 eV and we found that the Ba2YTaO6 (I4/m) phase is the most stable one. © 2013 Elsevier Science.

  20. The electronic structure of the high-symmetry perovskite iridate Ba2IrO4

    NASA Astrophysics Data System (ADS)

    Moser, S.; Moreschini, L.; Ebrahimi, A.; Dalla Piazza, B.; Isobe, M.; Okabe, H.; Akimitsu, J.; Mazurenko, V. V.; Kim, K. S.; Bostwick, A.; Rotenberg, E.; Chang, J.; Rønnow, H. M.; Grioni, M.

    2014-01-01

    We report angle-resolved photoemission (ARPES) measurements, density functional and model tight-binding calculations on Ba2IrO4 (Ba-214), an antiferromagnetic (TN = 230 K) insulator. Ba-214 does not exhibit the rotational distortion of the IrO6 octahedra that is present in its sister compound Sr2IrO4 (Sr-214), and is therefore an attractive reference material to study the electronic structure of layered iridates. We find that the band structures of Ba-214 and Sr-214 are qualitatively similar, hinting at the predominant role of the spin-orbit interaction in these materials. Temperature-dependent ARPES data show that the energy gap persists well above TN, and favor a Mott over a Slater scenario for this compound.

  1. Epitaxial Ba-Y-Cu-O ceramic superconducting film on perovskite structure substrate

    SciTech Connect

    Chai, B.H.

    1991-07-09

    This patent describes a superconducting structure. It comprises a crystal substrate having a superconducting film epitaxially deposited thereon, wherein the substrate is a crystal selected from the group consisting of LaAlO{sub 3}, LaGaO{sub 3}, PrGaO{sub 3} and NdGaO{sub 3}, and wherein the superconducting film is a Ba- Y- Cu- O superconductor.

  2. Effect of Perovskite Overlayers on TiO2 Electrodes in Perovskite-Sensitized Solar Cells.

    PubMed

    Kim, Kang-Pil; Kim, Jeong-Hwa; Hwang, Dae-Kue

    2016-05-01

    In this paper, we have studied the effect of the thickness of a CH3NH3PbI3 perovskite overlayer on mesoporous TiO2 electrodes in perovskite solar cells. The overlayers were prepared by spin coating PbI2 films on the electrodes, which were subsequently exposed to a CH3NH3I/2-propanol solution. We controlled the thickness of the perovskite overlayer by changing the PbI2 solution concentration. The thicknesses of the overlayers spin-coated from 0.5, 0.75, 0.9, and 1 M PbI2 solutions were approximately 179, 262, 316, and 341 nm, respectively. Perovskite solar cells with an approximately 316-nm-thick overlayer showed the highest efficiency of 9.11%. We conclude that optimization of the perovskite overlayer thickness in the solar cell structure is necessary to improve the cell efficiency. PMID:27483921

  3. Electronic structure of ordered double perovskite Ba{sub 2}CoWO{sub 6}

    SciTech Connect

    Ray, Rajyavardhan; Choudhary, B. K.; Kumar, Uday; Sinha, T. P.

    2014-04-24

    Ba{sub 2}CoWO{sub 6} (BCoW) has been synthesized in polycrystalline form by solid state reaction at 1200 °C. Structural characterization of the compound was done through X-ray diffraction (XRD) followed by Rietveld analysis of the XRD pattern. The crystal structure is cubic, space group Fm-3m (No. 225) with the lattice parameter, a = 8.210. Optical band-gap of the present system has been calculated using the UV-Vis Spectroscopy and Kubelka-Munk function, it’s value being 2.45 eV. A detailed study of the electronic properties has also been carried out using the density functional theory (DFT) techniques implemented on WIEN2k. Importance of electron-electron interaction between the Co ions leading to half-metallic behavior, crystal and exchange splitting together with the hybridization between O and Co, W has been investigated using the total and partial density of states.

  4. Defect structure of the high-dielectric-constant perovskite Ca Cu3 Ti4 O12

    NASA Astrophysics Data System (ADS)

    Wu, L.; Zhu, Y.; Park, S.; Shapiro, S.; Shirane, G.; Tafto, J.

    2005-01-01

    Using transmission electron microscopy (TEM) we studied CaCu3Ti4O12 , an intriguing material that exhibits a huge dielectric response, up to kilohertz frequencies, over a wide range of temperature. Neither in single crystals, nor in polycrystalline samples, including sintered bulk and thin films, did we observe the twin domains suggested in the literature. Nevertheless, in the single crystals, we saw a very high density of dislocations with a Burger vector of [110], as well as regions with cation disorder and planar defects with a displacement vector (1)/(4)[110] . In the polycrystalline samples, we observed many grain boundaries with oxygen deficiency, in comparison with the grain interior. The defect-related structural disorders and inhomogeneity, serving as an internal barrier layer capacitance in a semiconducting matrix, might explain the very large dielectric response of the material. Our TEM study of the structure defects in CaCu3Ti4O12 supports a recently proposed morphological model with percolating conducting regions and blocking regions.

  5. Structural and magnetic properties of the 5d2 double perovskites Sr2BReO6 (B = Y, In)

    DOE PAGES

    Aczel, A. A.; Zhao, Z.; Calder, S.; Adroja, D. T.; Baker, P. J.; Yan, J. -Q.

    2016-06-01

    With this study, we have performed magnetic susceptibility, heat capacity, neutron powder diffraction, and muon spin relaxation experiments to investigate the magnetic ground states of the 5$d^2$ double perovskites Sr$_2$YReO$_6$ and Sr$_2$InReO$_6$. We find that Sr$_2$YReO$_6$ is a spin glass, while Sr$_2$InReO$_6$ hosts a non-magnetic singlet state. By making detailed comparisons with other 5$d^2$ double perovskites, we argue that a delicate interplay between spin-orbit coupling, non-cubic crystal fields, and exchange interactions plays a key role in the great variation of magnetic ground states observed for this family of materials.

  6. Composition dependence of photoluminescence properties of poly(9,9-di-n-hexylfluorenyl-2,7-diyl) with perovskite-structured SrTiO3 nanocomposites

    NASA Astrophysics Data System (ADS)

    Din, U. K. N.; Salleh, M. M.; Aziz, T. H. T.; Umar, A. A.

    2016-05-01

    Nanocomposite thin films of poly(9,9-di-n-hexylfluorenyl-2,7-diyl) (PHF) with 10-50 wt% perovskite-structured SrTiO3 nanoparticles (designated as PHF:SrTiO3) were prepared by spin coating. The photoluminescence (PL) properties of the nanocomposites thin films were studied. The incorporation of SrTiO3 nanoparticles into the nanocomposite thin films enhanced the original PL intensities of the host PHF thin films. The intensities of the PL peak for the nanocomposite thin films were dependent on the amount of SrTiO3 nanoparticles in the films and the homogeneity of the nanoparticle distribution. The distribution of the SrTiO3 nanoparticles contributed to the overlapping molecular orbital sites in PHF:SrTiO3, which promoted the excited electrons from the conduction band of SrTiO3 transferred to the excited energy level of the PHF host material. In this case, the perovskite-structured SrTiO3 nanoparticles act as sensitizers.

  7. Perovskite LaFeO3 nanoparticles synthesized by the reverse microemulsion nanoreactors in the presence of aerosol-OT: Morphology, crystal structure, and their optical properties

    NASA Astrophysics Data System (ADS)

    Abazari, Reza; Sanati, Soheila

    2013-12-01

    Orthorhombic structure of lanthanum ferrite nanoparticles (LaFeO3 NPs) with perovskite type phase has been synthesized with water-in-oil (W/O) microemulsion consisted of water/dioctyl sulfosuccinate sodium (aerosol-OT)/isooctane at room temperature. It has been shown that aerosol-OT reverse microemulsion solution is appropriate for synthesizing perovskite LaFeO3 NPs in the absence of any co-surfactants. Field emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), energy dispersive analysis of X-ray (EDAX), X-ray diffraction (XRD), ultraviolet-visible absorption spectroscopy (UV-Vis), and Fourier transform infrared spectroscopy (FT-IR) have been adopted for characterization of surface morphology, size, phase composition, structure, and optical properties of the considered NPs. Furthermore, the optical properties of LaFeO3 NPs have been further analyzed via photoluminescence (PL) spectroscopy. As shown by the physicochemical characterizations, our prepared NPs via aerosol-OT reverse microemulsion solution are spherical and nearly uniform (with a size of about 24.65 nm). Besides, they include an orthorhombic phase while no impurities are observed. Single phase lanthanum ferrite NPs have successfully been prepared at 500 °C. Moreover, UV-Vis spectrum indicates that the LaFeO3 NPs synthesized through this technique can be considered as a type of photo-catalytic materials.

  8. Modeling functional piezoelectricity in perovskite superlattices with competing instabilities

    NASA Astrophysics Data System (ADS)

    Swartz, Charles; Wu, Xifan

    2012-02-01

    Multi-component Perovskite Superlattices (SLs) of the form ABO3, provide a very promising avenue for the design of materials with multifunctional properties. Furthermore the interfaces of such multi-component SLs are home to competing anti-ferrodistortive and ferroelectric instabilities which can produce unexpected functionalities. However, at present first principles calculations exceeding more than 10 units cells, are particularly costly as they scale with the valence electrons as N^3. We present a first-principles modeling technique that allows us to accurately model the piezoelectric strains of paraelectric/ferroelectric SLs, BaTiO3/CaTiO3 and PbTiO3/SrTiO3, under a fixed displacement field. The model is based on a maximally localized wannier center layer polarization technique, as well as a truncated cluster expansion, that makes use of the fact that such PE/FE SLs have been shown to have highly localized ionic and electronic interface effects. The prediction of the piezoelectricity for a SL of an arbitrary stacking sequence will be demonstrated. We also use our model to conduct a systemic study of the interface effects on piezoelectric response in the above SLs paying special attention to a strong non-linear effect observed in Bulk SrTiO3.

  9. Synthesis and Characterization of Complex Metal Oxides with Perovskite-Related Structure

    NASA Astrophysics Data System (ADS)

    Liu, Chia-Jyi

    A series of materials rm La_ {2-x}Sr_ xNiO_{4-delta } were synthesized via a basic carbonates coprecipitation route. They possess the tetragonal rm K _2NiF_4 structure up to x = 1.5, and undergo a composition dependent metal-nonmetal transition. The materials are nonmetals for x <=q 1.0 and are metals for x >=q 1.1. For compositions near the transition the conductivity type is also dependent on delta. The temperature dependence of the electrical conductivity for nonmetallic rm La_{2-x}Sr _ xNiO_{4-delta} shows two conduction mechanisms: a phonon-assisted variable-range hopping as a result of disorder, and an impurity band conduction. The domination of one of these two mechanisms likely depends upon the composition and the temperature range. The sign and magnitude of the thermoelectric power, as a function of temperature, for the rm La_{2-x}Sr_ xNiO_{4 -delta} materials is a sum of the contributions due to holes and electrons. The negative contribution which increases as the temperature increases (due to diffusive electrons) is determined by the variable-range hopping mechanism for nonmetals and by metallic conduction for the metals. For both lightly doped metals and nonmetals the positive contribution to the thermoelectric power increases and then decreases as the temperature increases. This contribution could be due to a phonon drag mechanism where the holes are created by excitation of electrons from the mobility edge of the sigma^ {*1}_{x^2-y^2 } band to impurity states. In the heavily doped metallic material, where S becomes more negative with increasing doping, the thermoelectric power strongly indicates that electrons and not holes are the majority carriers. A series of solid solutions rm La _{2-x}Sr_ xCu_{1-y} Ni_ yO_{4-delta} were synthesized using a basic carbonate coprecipitation technique. All the resulting powders are single phase solids which exhibit I4/mmm symmetry. Disappearance of the superconductivity at higher Ni content usually accompanies the

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

    SciTech Connect

    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. We find, consistent with PDF analysis, Raman spectroscopy data suggest that the local structure changes to a higher ordered state at pressures above 4 GPa.

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

    SciTech Connect

    Aman, Amjad; Orlovskaya, Nina; Chen, Yan; Lugovy, Mykola; Reece, Michael J.; Ma, Dong; Stoica, Alexandru D.; An, Ke

    2014-07-07

    The dynamics of texture formation, changes in crystal structure, and stress accommodation mechanisms have been studied in perovskite-type R3⁻c rhombohedral LaCoO₃ during uniaxial compression using in-situ neutron diffraction. The in-situ neutron diffraction revealed the complex crystallographic changes causing the texture formation and significant straining along certain crystallographic directions during compression, which are responsible for the appearance of hysteresis and non-linear ferroelastic deformation in the 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 hysteresis loop was closed and no further irrecoverable strain appeared after deformation. The significant texture formation is responsible for an increase in the Young's modulus of LaCoO₃ at high compressive stresses, ranging from 76 GPa at the very beginning of the loading to 194 GPa at 900 MPa at the beginning of the unloading curve.

  12. High-pressure synthesis, crystal structure, and unusual valence state of novel perovskite oxide CaCu3Rh4O12.

    PubMed

    Yamada, Ikuya; Ochi, Mikiko; Mizumaki, Masaichiro; Hariki, Atsushi; Uozumi, Takayuki; Takahashi, Ryoji; Irifune, Tetsuo

    2014-07-21

    A novel perovskite oxide, CaCu3Rh4O12, has been synthesized under high-pressure and high-temperature conditions (15 GPa and 1273 K). Rietveld refinement of synchrotron X-ray powder diffraction data indicates that this compound crystallizes in a cubic AA'3B4O12-type perovskite structure. Synchrotron X-ray absorption and photoemission spectroscopy measurements reveal that the Cu and Rh valences are nearly trivalent. The spectroscopic analysis based on calculations suggests that the appropriate ionic model of this compound is Ca(2+)Cu(∼2.8+)3Rh(∼3.4+)4O12, as opposed to the conventional Ca(2+)Cu(2+)3Rh(4+)4O12. The uncommon valence state of this compound is attributed to the relative energy levels of the Cu 3d and Rh 4d orbitals, in which the large crystal-field splitting energy of the Rh 4d orbitals is substantial.

  13. Crystal growth, structure and magnetic properties of the double perovskites Ln{sub 2}MgIrO{sub 6} (Ln=Pr, Nd, Sm-Gd)

    SciTech Connect

    Mugavero, Samuel J. III; Fox, Adam H.; Smith, Mark D.; Loye, Hans-Conrad zur

    2010-02-15

    Single crystals of double-perovskite type lanthanide magnesium iridium oxides, Ln{sub 2}MgIrO{sub 6} (Ln=Pr, Nd, Sm-Gd) have been grown in a molten potassium hydroxide flux. The compounds crystallize in a distorted 1:1 rock salt lattice, space group P2{sub 1}/n, consisting of corner shared MO{sub 6} (M=Mg{sup 2+} and Ir{sup 4+}) octahedra, where the rare earth cations occupy the eight-fold coordination sites formed by the corner shared octahedra. Pr{sub 2}MgIrO{sub 6}, Nd{sub 2}MgIrO{sub 6}, Sm{sub 2}MgIrO{sub 6}, and Eu{sub 2}MgIrO{sub 6} order antiferromagnetically around 10-15 K. - Graphical abstract: A SEM image of a typical crystal of Ln{sub 2}MgIrO{sub 6}, which forms in the monoclinic double perovskite structure, is shown.

  14. Core/Shell Structured TiO2/CdS Electrode to Enhance the Light Stability of Perovskite Solar Cells.

    PubMed

    Hwang, Insung; Baek, Minki; Yong, Kijung

    2015-12-23

    In this work, enhanced light stability of perovskite solar cell (PSC) achieved by the introduction of a core/shell-structured CdS/TiO2 electrode and the related mechanism are reported. By a simple solution-based process (SILAR), a uniform CdS shell was coated onto the surface of a TiO2 layer, suppressing the activation of intrinsic trap sites originating from the oxygen vacancies of the TiO2 layer. As a result, the proposed CdS-PSC exhibited highly improved light stability, maintaining nearly 80% of the initial efficiency after 12 h of full sunlight illumination. From the X-ray diffraction analyses, it is suggested that the degradation of the efficiency of PSC during illumination occurs regardless of the decomposition of the perovskite absorber. Considering the light-soaking profiles of the encapsulated cells and the OCVD characteristics, it is likely that the CdS shell had efficiently suppressed the undesirable electron kinetics, such as trapping at the surface defects of the TiO2 and preventing the resultant charge losses by recombination. This study suggests that further complementary research on various effective methods for passivation of the TiO2 layer would be highly meaningful, leading to insight into the fabrication of PSCs stable to UV-light for a long time.

  15. Structure and magnetism in the oxygen-deficient perovskites Ce{sub 1-x}Sr {sub x}CoO{sub 3-{delta}} (x {>=} 0.90)

    SciTech Connect

    James, M. . E-mail: mja@ansto.gov.au; Wallwork, K.S.; Withers, R.L.; Goossens, D.J.; Wilson, K.F.; Horvat, J.; Wang, X.L.; Colella, M.

    2005-08-11

    We have examined the structure and phase behaviour of strontium-doped Ce{sub 1-x}Sr {sub x}CoO{sub 3-{delta}} and found that the perovskite form is stabilised over a relatively narrow solid solution range (x > 0.85). A combination of electron, powder X-ray and neutron diffraction has revealed tetragonal superstructures of the basic perovskite unit; (I4/mmm) 2a {sub p} x 2a {sub p} x 4a {sub p} (x = 0.90) and (P4/mmm) a {sub p} x a {sub p} x 2a {sub p} (x = 0.95). Magnetisation measurements show ferromagnetic behaviour under applied magnetic fields. Low temperature neutron diffraction of Ce{sub 0.10}Sr{sub 0.90}CoO{sub 2.80} in zero field reveals a magnetic cell of dimension 2a {sub p} x 2a {sub p} x 4a {sub p} with an ordered cobalt moment of 1.7 B.M. at 25 K.

  16. Influence of Ni/Mo ratio on structural and electrical properties of double perovskite system Sr2Ni1+ x Mo1- x O6- δ

    NASA Astrophysics Data System (ADS)

    Kumar, Pravin; Singh, Nitish Kumar; Singh, Rajesh Kumar; Singh, Prabhakar

    2015-11-01

    Technologically important double perovskite system Sr2Ni1+ x Mo1- x O6- δ with x = 0.00, 0.05, 0.10, and 0.15 was prepared by solution combustion method. The structural and the Rietveld analysis of compositions revealed the formation of double perovskite tetragonal phase Sr2NiMoO6 with space group I4/m as a major phase. SrMoO4 and NiO were also observed as minor phases. Microstructural studies depicted the formation of uniform grains for all the samples. The average grain size was found to lie between the ranges of 1-4 μm. XPS analysis of the synthesized compositions showed the decreasing ratio of Mo5+ to Mo6+ ions in the system with increasing Ni content, which played an important role in the conduction mechanism. The thermal expansion coefficient (TEC) of all compositions indicated that it is more compatible to the TEC of standard electrolytes. The electrical conductivity for all the compositions was studied using impedance spectroscopy in the temperature range 200-600 °C. Composition with x = 0.05 showed better electrical conductivity with good catalytic activity.

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

    SciTech Connect

    Aman, Amjad; Chen, Yan; Lugovy, Mykola; Orlovskaya, Nina; Reece, Michael John; Ma, Dong; Stoica, Alexandru Dan; An, Ke

    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 hysteresis 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.

  18. Structural evolution of the double perovskites Sr{sub 2}B'UO{sub 6} (B' = Mn, Fe, Co, Ni, Zn) upon reduction: Magnetic behavior of the uranium cations

    SciTech Connect

    Pinacca, R.M.; Viola, M.C.; Pedregosa, J.C.; Carbonio, R.E.; Lope, M.J. Martinez; Alonso, J.A.

    2011-11-15

    Highlights: {yields} Evolution of the double perovskites Sr{sub 2}B'UO{sub 6} upon reduction were studied by XRPD. {yields} Orthorhombic (Pnma) disordered perovskites SrB'{sub 0.5-x}U{sub 0.5+x}O{sub 3} were obtained at 900 {sup o}C. {yields} U{sup 5+/4+} and Zn{sup 2+} cations are distributed at random over the octahedral positions. {yields} AFM ordering for the perovskite with B' = Zn appears below 30 K. -- Abstract: We describe the preparation of five perovskite oxides obtained upon reduction of Sr{sub 2}B'UO{sub 6} (B' = Mn, Fe, Co, Ni, Zn) with H{sub 2}/N{sub 2} (5%/95%) at 900 {sup o}C during 8 h, and their structural characterization by X-ray powder diffraction (XRPD). During the reduction process there is a partial segregation of the elemental metal when B' = Co, Ni, Fe, and the corresponding B'O oxide when B' = Mn, Zn. Whereas the parent, oxygen stoichiometric double perovskites Sr{sub 2}B'UO{sub 6} are long-range ordered concerning B' and U cations. The crystal structures of the reduced phases, SrB'{sub 0.5-x}U{sub 0.5+x}O{sub 3} with 0.37 < x < 0.27, correspond to simple, disordered perovskites; they are orthorhombic, space group Pnma (No. 62), with a full cationic disorder at the B site. Magnetic measurements performed on the phase with B' = Zn, indicate uncompensated antiferromagnetic ordering of the U{sup 5+}/U{sup 4+} sublattice below 30 K.

  19. Synthesis, crystal structure and magnetic properties of a new pillared perovskite La{sub 5}Mo{sub 2.75}V{sub 1.25}O{sub 16}

    SciTech Connect

    Ramezanipour, Farshid; Derakhshan, Shahab; Greedan, John E. Cranswick, Lachlan M.D.

    2008-12-15

    A new pillared perovskite compound La{sub 5}Mo{sub 2.76(4)}V{sub 1.25(4)}O{sub 16}, has been synthesized by solid-state reaction and its crystal structure has been characterized using powder X-ray and neutron diffraction. The magnetic properties of this compound have been investigated using SQUID magnetometry, and the magnetic structure has been studied using neutron diffraction data. A theoretical calculation of relative strengths of spin interactions among different magnetic ions and through different pathways has been performed using extended Hueckel, spin dimer analysis. The crystal structure of this material contains perovskite-type layers that are connected through edge-sharing dimeric units of octahedra. The structure is described in space group C2/m with unit cell parameters a=7.931(2) A, b=7.913(2) A, c=10.346(5) A and {beta}=95.096(5){sup o}. The material shows both short-range ferrimagnetic correlations from {approx}200 to 110 K and long-range antiferromagnetic order below T{sub c}{approx}100 K. The magnetic structure was investigated by neutron diffraction and is described by k=(0 0 1/2 ) as for other pillared perovskites. It consists of a ferrimagnetic arrangement of Mo and V within the layers that are coupled antiferromagnetically between layers. This is the first magnetic structure determination for any Mo-based pillared perovskite. - Graphical abstract: Long-range magnetic order below 100 K in the pillared perovskite La{sub 5}Mo{sub 2.75}V{sub 1.25}O{sub 16}. The magnetic structure is shown in the inset.

  20. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    PubMed

    Chen, Kun; Tüysüz, Harun

    2015-11-01

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. PMID:26376773

  1. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    PubMed

    Chen, Kun; Tüysüz, Harun

    2015-11-01

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites.

  2. First-principles study of crystal structure, electronic structure, and second-harmonic generation in a polar double perovskite Bi2ZnTiO6.

    PubMed

    Ju, Sheng; Guo, Guang-Yu

    2008-11-21

    Within the density functional theory with the generalized gradient approximation, we present a systematic ab initio investigation of crystal structure, electronic structure, and linear and nonlinear optical responses in a polar double perovskite Bi(2)ZnTiO(6). The effect of B-site ordering is explored by comparing three possible configurations: A-type with alternative Zn and Ti layers stacking along the c axis; C-type with Zn and Ti c axis chains; and G-type with every Zn(Ti) atoms is surrounded by its nearby six Ti(Zn) atoms. It is found that the system with G-type B-site ordering is energetically favorable, which is lower in the total energies of 0.055 and 0.133 eV/formula unit than C-type and A-type, respectively. Optical calculations indicate that all the three configurations show large second-harmonic generation (SHG) coefficients, and the largest static SHG observed in the C-type system reaches 123 (10(-9) esu), the value of which is much larger than ever known polar oxides, e.g., 72 (10(-9) esu) in LiNbO(3). The predicted significant nonlinear optical properties are consistent with the calculated high tetragonality as well as the large off-center displacement of Zn, Ti, and Bi atoms. In particular, a large off-center displacement greater than 0.5 A in Zn atoms is revealed for the first time. A further microscopic picture is presented via the successful connection of the prominent feature of SHG in Bi(2)ZnTiO(6) with that of the linear optical dielectric function in terms of single-photon and double-photon resonances. Our calculations demonstrate the promising application of Bi(2)ZnTiO(6) in optoelectronics.

  3. A structural study of the perovskite series CaTi{sub 1{minus}2x}Fe{sub x}Nb{sub x}O{sub 3}

    SciTech Connect

    Chakhmouradian, A.R.; Mitchell, R.H.

    1998-07-01

    An X-ray powder diffraction study of the series CaTi{sub 1{minus}2x}Fe{sub x}Nb{sub x}O{sub 3} is presented. The series comprises orthorhombic perovskites (Pbnm, a {approx} b {approx} {radical}2a{sub p}, c {approx} 2a{sub p}, Z = 4) in the range 0 {le} x {le} 0.3, and monoclinic perovskites (P2{sub 1}/n, a {approx} b {approx} {radical}2a{sub p}, c {approx} 2a{sub p}, {beta} {ne} 90{degree}, Z = 4) in the range 0.4 {le} x {le} 0.5. The structure of the orthorhombic members is derived from the cubic aristotype by octahedral rotation a{sup {minus}}a{sup {minus}}c{sup +}. The structural distortion in the monoclinic members involves octahedral rotation and short-range cation ordering at the B-site (4c and 4d). In the series CaTi{sub 1{minus}2x}Fe{sub x}Nb{sub x}O{sub 3}, the unit-cell parameters and degree of octahedral rotation increase with x. The [111]{sub p} tilt angle increases from 16.1{degree} in CaTiO{sub 3} to 17.6--18.9{degree} in CaFe{sub 1/2}Nb{sub 1/2}O{sub 3} (for the NbO{sub 6} and FeO{sub 6} octahedra, respectively). In contrast to previous studies, here the diffraction pattern of the end-member CaFe{sub 1/2}Nb{sub 1/2}O{sub 3} is interpreted to exhibit splitting of the hkl and h0l lines indicative of a monoclinic derivative of the CaTiO{sub 3}-type structure.

  4. A Structural Study of the Perovskite Series CaTi 1-2 xFe xNb xO 3

    NASA Astrophysics Data System (ADS)

    Chakhmouradian, Anton R.; Mitchell, Roger H.

    1998-07-01

    An X-ray powder diffraction study of the series CaTi1-2xFexNbxO3is presented. The series comprises orthorhombic perovskites (Pbnm,a≈b≈√2ap,c≈2ap,Z=4) in the range 0≤x≤0.3, and monoclinic perovskites (P21/n,a≈b≈√2ap,c≈2ap,β≠90°,Z=4) in the range 0.4≤x≤0.5. The structure of the orthorhombic members is derived from the cubic aristotype by octahedral rotationa-a-c+. The structural distortion in the monoclinic members involves octahedral rotation and short-range cation ordering at theB-site (4cand 4d). In the series CaTi1-2xFexNbxO3, the unit-cell parameters and degree of octahedral rotation increase withx. The [111]ptilt angle increases from 16.1° in CaTiO3to 17.6-18.9° in CaFe1/2Nb1/2O3(for the NbO6and FeO6octahedra, respectively). In contrast to previous studies, here the diffraction pattern of the end-member CaFe1/2Nb1/2O3is interpreted to exhibit splitting of thehklandh0llines indicative of a monoclinic derivative of the CaTiO3-type structure.

  5. BiNb{sub 3}O{sub 9}, a metastable perovskite phase with Bi/vacancy ordering: Crystal structure and dielectric properties

    SciTech Connect

    Mumme, William G.; Grey, Ian E.; Edwards, Bryce; Turner, Christopher; Nino, Juan; Vanderah, Terrell A.

    2013-04-15

    The perovskite, BiNb{sub 3}O{sub 9}, is a metastable phase in the Bi{sub 2}O{sub 3}:Nb{sub 2}O{sub 5} system that forms only when cooled from a liquid phase. Crystals of BiNb{sub 3}O{sub 9} prepared in this way display pseudocubic 2a×2a×2a diffraction patterns, due to non-merohedral twinning of a tetragonal a×a×2a cell, with the doubled axis oriented along all three pseudocubic axes. The structure was refined using data collected on a twinned crystal to R{sub 1}=0.034 for 318 observed reflections. BiNb{sub 3}O{sub 9} has tetragonal symmetry, P4/mmm with a=3.9459(3) Å, c=7.8919(6) Å. Partial ordering of Bi atoms and vacancies occurs, with alternate (0 0 1) planes having 28% and 42% Bi occupancies. The Bi atoms are displaced from the A-site special positions by up to 0.4 Å. The compound exhibits a relatively high permittivity value of ∼230 at room temperature, and shows a sharp increase with increasing temperature towards an apparent diffuse phase transition above ∼180 °C, with an associated frequency dependent peak in the dielectric loss. - Graphical abstract: Structure for BiNb{sub 3}O{sub 9}, showing split Bi atoms. Highlights: ► First characterisation of a new perovskite phase with potentially useful dielectric properties. ► Solving of the structure using single crystal data on a multiply twinned crystal. ► Measurement of dielectric properties that show the phase has a high dielectric permittivity.

  6. Perovskite solar cells: from materials to devices.

    PubMed

    Jung, Hyun Suk; Park, Nam-Gyu

    2015-01-01

    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.

  7. Structural Transformations in Ceramics: Perovskite-like Oxides and Group III, IV, and V Nitrides”

    SciTech Connect

    James P. Lewis , Dorian M. Hatch , and Harold T. Stokes

    2006-12-31

    1 Overview of Results and their Significance Ceramic perovskite-like oxides with the general formula (A. A0. ...)(B. B0. ...)O3and titanium-based oxides are of great technological interest because of their large piezoelectric and dielectric response characteristics.[1] In doped and nanoengineered forms, titantium dioxide finds increasing application as an organic and hydrolytic photocatalyst. The binary main-group-metal nitride compounds have undergone recent advancements of in-situ heating technology in diamond anvil cells leading to a burst of experimental and theoretical interest. In our DOE proposal, we discussed our unique theoretical approach which applies ab initio electronic calculations in conjunction with systematic group-theoretical analysis of lattice distortions to study two representative phase transitions in ceramic materials: (1) displacive phase transitions in primarily titanium-based perovskite-like oxide ceramics, and (2) reconstructive phase transitions in main-group nitride ceramics. A sub area which we have explored in depth is doped titanium dioxide electrical/optical properties.

  8. Synthesis, structure, and magnetism of BaVO[sub 2. 8]: A new perovskite-related vanadate with V[sup III]/V[sup IV] ordering

    SciTech Connect

    Chen, B.H.; Eichhorn, B.W.; Ju, H.L.; Greene, R.L. )

    1993-12-08

    A new barium vanadium oxide, BaVO[sub 2.8], was prepared from BaO and VO[sub 2] in an evacuated silica ampule at 1100[angstrom]C for 10 h with excess Zr getter. The compound consists of interleaving perovskite layers (two corner-sharing VO[sub 6] octahedra) and BaNiO[sub 3] type layers (three face-sharing CO[sub 6] octahedra) along the c-axis. Curie-Weiss magnetic behavior was observed with [mu][sub eff] = 1.96[mu][sub B]/ The structural and magnetic data reveal ordering of V[sup III] and V[sup IV] cations at the corner-sharing and face-shring octahedral holes, respectively. Qualitative molecular orbital analysis indicates M-M bonding in the face sharing [V[sub 3]O[sub 12

  9. Crystal structure study of dielectric oxynitride perovskites La1-xSrxTiO2+xN1-x (x=0, 0.2)

    NASA Astrophysics Data System (ADS)

    Habu, Daiki; Masubuchi, Yuji; Torii, Shuki; Kamiyama, Takashi; Kikkawa, Shinichi

    2016-05-01

    As is the case with SrTaO2N, both cis-ordering of nitride anions and octahedral titling are also preferable in La1-xSrxTiO2+xN1-x (x=0, 0.2) oxynitride perovskites. A larger dielectric constant of εr≈5.0×103 was estimated for the pure oxynitride with x=0.2, compared with εr≈750 for the product with x=0, by extrapolating the εr values obtained from powders mixed with paraffin at various mixing ratios. The crystal structure of x=0.2 with larger tolerance factor than x=0 increased the octahedral tilting, which contributes to the increased dielectric constant. The increased dielectric constant supports the exchange mechanism for the dielectric property between two kinds of -Ti-N- helical coils (clockwise and anticlockwise) derived from the above cis-ordering of nitride anions.

  10. p-i-n/n-i-p type planar hybrid structure of highly efficient perovskite solar cells towards improved air stability: synthetic strategies and the role of p-type hole transport layer (HTL) and n-type electron transport layer (ETL) metal oxides.

    PubMed

    Mali, Sawanta S; Hong, Chang Kook

    2016-05-19

    There has been fast recent progress in perovskite solar cells (PSCs) towards low cost photovoltaic technology. Organometal mixed halide (MAPbX or FAPbX) perovskites are the most promising light absorbing material sandwiched between the electron transport layer (ETL) and hole transport layer (HTL). These two layers play a critical role in boosting the power conversion efficiency (PCE) and maintaining air stability. However, the device stability is a serious issue in regular as well as p-i-n inverted type perovskite solar cells. This mini-review briefly outlines the state-of-art of p-i-n/n-i-p type planar hybrid perovskite solar cells using MAPbX/FAPbX perovskite absorbing layers. Later, we will focus on recent trends, progress and further opportunities in exploring the air stable hybrid planar structure PSCs.

  11. p-i-n/n-i-p type planar hybrid structure of highly efficient perovskite solar cells towards improved air stability: synthetic strategies and the role of p-type hole transport layer (HTL) and n-type electron transport layer (ETL) metal oxides

    NASA Astrophysics Data System (ADS)

    Mali, Sawanta S.; Hong, Chang Kook

    2016-05-01

    There has been fast recent progress in perovskite solar cells (PSCs) towards low cost photovoltaic technology. Organometal mixed halide (MAPbX or FAPbX) perovskites are the most promising light absorbing material sandwiched between the electron transport layer (ETL) and hole transport layer (HTL). These two layers play a critical role in boosting the power conversion efficiency (PCE) and maintaining air stability. However, the device stability is a serious issue in regular as well as p-i-n inverted type perovskite solar cells. This mini-review briefly outlines the state-of-art of p-i-n/n-i-p type planar hybrid perovskite solar cells using MAPbX/FAPbX perovskite absorbing layers. Later, we will focus on recent trends, progress and further opportunities in exploring the air stable hybrid planar structure PSCs.

  12. Structural, mechanical, electronic and thermal properties of KZnF3 and AgZnF3 Perovskites: FP-(L)APW+lo calculations

    NASA Astrophysics Data System (ADS)

    Hiadsi, S.; Bouafia, H.; Sahli, B.; Abidri, B.; Bouaza, A.; Akriche, A.

    2016-08-01

    This study presents a theoretical prediction of the structural, mechanical, electronic and thermal properties of the zinc-based Perovskites (AgZnF3 and KZnF3) within the framework of Density Functional Theory (DFT) using All-electron self consistent Full Potential Augmented Plane Waves plus local orbital FP-(L)APW + lo method. To make our work comparable and reliable, several functional were used for the exchange-correlation potential. Also, this study intends to provide a basis and an improvement for updating either the values already predicted by other previous work (by using obsolete functional) or to predict them for the first time. GGA-PBE and GGA-PBEsol were used to predict the structural properties of AgZnF3 and KZnF3 Perovskites such as lattice parameter, bulk modulus and its pressure derivative and the cohesive energy. For these properties, the found values are in very good agreement; also those found by GGA-PBEsol are closer to other available previous and experimental results. The electronic properties of these materials are investigated and compared to provide a consolidated prediction by using the modified Becke Johnson potential TB-mBJ with other functional; the values found by this potential are closer to the available proven results and show that these materials exhibit an indirect gap from R to Γ point. The charge densities plot for [110] direction and QTAIM (Quantum Theory of Atoms in Molecules) theory indicate that ionic character is predominate for (K, Ag, Zn)sbnd F bonds. Finally, the effect of temperature and pressure on the unit cell volume, the heat capacity CV and entropy were studied using the quasi-harmonic Debye model.

  13. 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

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  14. Two Dimensional Organometal Halide Perovskite Nanorods with Tunable Optical Properties.

    PubMed

    Aharon, Sigalit; Etgar, Lioz

    2016-05-11

    Organo-metal halide perovskite is an efficient light harvester in photovoltaic solar cells. Organometal halide perovskite is used mainly in its "bulk" form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halide perovskite, as well as the nanoscale properties. In this paper, we present facile low-temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g., octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. The 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light-emitting diodes, lasing, solar cells, and sensors. PMID:27089497

  15. Perovskites with the Framework-Forming Xenon.

    PubMed

    Britvin, Sergey N; Kashtanov, Sergei A; Krzhizhanovskaya, Maria G; Gurinov, Andrey A; Glumov, Oleg V; Strekopytov, Stanislav; Kretser, Yury L; Zaitsev, Anatoly N; Chukanov, Nikita V; Krivovichev, Sergey V

    2015-11-23

    The Group 18 elements (noble gases) were the last ones in the periodic system to have not been encountered in perovskite structures. We herein report the synthesis of a new group of double perovskites KM(XeNaO6) (M = Ca, Sr, Ba) containing framework-forming xenon. The structures of the new compounds, like other double perovskites, are built up of the alternating sequence of corner-sharing (XeO6) and (NaO6) octahedra arranged in a three-dimensional rocksalt order. The fact that xenon can be incorporated into the perovskite structure provides new insights into the problem of Xe depletion in the atmosphere. Since octahedrally coordinated Xe(VIII) and Si(IV) exhibit close values of ionic radii (0.48 and 0.40 Å, respectively), one could assume that Xe(VIII) can be incorporated into hyperbaric frameworks such as MgSiO3 perovskite. The ability of Xe to form stable inorganic frameworks can further extend the rich and still enigmatic chemistry of this noble gas. PMID:26429762

  16. Crystal phase structure investigation in the process of radiation-thermal transformations in systems SrO-Fe2O3, SrCO3-Fe2O3 (perovskite) and garnet Y2O3-Fe2O3

    NASA Astrophysics Data System (ADS)

    Ancharova, U. V.; Mikhailenko, M. A.; Tolochko, B. P.; Lyakhov, N. Z.; Korobeinikov, M. V.; Bryazgin, A. A.; Vinokurov, Z. S.; Selyutin, A. G.

    2016-02-01

    Chemical reactions products structural investigations during thermal and radiation- thermal processes are presented. The reaction mixtures were prepared by mechanical activation of stoichiometric compounds corresponding to synthesis reaction of strontium ferrite with perovskite structure (SrFeO3-s) or ferro-garnet (Y3Fe5O12). The phase formation staging changes dramatically depending on the temperature and the way of the high-temperature treatment.

  17. Role of Temperature and Pressure on the Multisensitive Multiferroic Dicyanamide Framework [TPrA][Mn(dca)3] with Perovskite-like Structure.

    PubMed

    Bermúdez-García, Juan M; Sánchez-Andújar, Manuel; Yáñez-Vilar, Susana; Castro-García, Socorro; Artiaga, Ramón; López-Beceiro, Jorge; Botana, Luis; Alegría, Ángel; Señarís-Rodríguez, María A

    2015-12-21

    A multistimuli response to temperature and pressure is found in the hybrid inorganic-organic perovskite-like [TPrA][Mn(dca)3] compound, which is related to a first-order structural phase transition near room temperature, Tt ≈ 330 K. This phase transition involves a transformation from room temperature polymorph I, with the noncentrosymmetric space group P4̅21c, to the high temperature polymorph II, with the centrosymmetric space group I4/mcm, and it implies ionic displacements, order-disorder phenomena, and a large and anisotropic thermal expansion (specially along the c-axis). As a consequence, [TPrA][Mn(dca)3] exhibits a dielectric anomaly, associated with the change from a cooperative to a noncooperative electric behavior (antiferroelectric (AFE)-paraelectric (PE) transition). The former implies an AFE distribution of electric dipoles in polymorph I, related to the described off-shift of the apolar TPrA cations and the order-disorder of the polar dca ligands mechanisms, that are different from those reported, up to now, for others perovskite-type hybrid compounds. Such cooperative electric order, below Tt ≈ 330 K, coexisting with long-range antiferromagnetic ordering below T = 2.1 K render the [TPrA][Mn(dca)3] a new type-I multiferroic material. In addition, the obtained experimental results reveal that this compound is also a multistimuli-responsive material, with a very large sensitivity toward temperature and applied external pressure, δTt/δP ≈ 24 K kbar(-1), even for small values of pressure (P < 2 kbar). Therefore, this material opens up a potential interest for future technological applications, such as temperature/pressure sensing. PMID:26652059

  18. Preparation, crystal structure and magnetic behavior of new double perovskites Sr{sub 2} B'UO{sub 6} with B'=Mn, Fe, Ni, Zn

    SciTech Connect

    Pinacca, R.M.; Viola, M.C.; Pedregosa, J.C.; Martinez-Lope, M.J.; Carbonio, R.E.; Alonso, J.A.

    2007-05-15

    Sr{sub 2} B'UO{sub 6} double perovskites with B'=Mn, Fe, Ni, Zn have been prepared in polycrystalline form by solid-state reaction, in air or reducing conditions. These new materials have been studied by X-ray diffraction (XRD), magnetic susceptibility and magnetization measurements. The room-temperature crystal structure is monoclinic (space group P2{sub 1}/n), and contains alternating B'O{sub 6} and UO{sub 6} octahedra sharing corners, tilted along the three pseudocubic axes according to the Glazer notation a {sup -} a {sup -} b {sup +}. The magnetic measurements show a spontaneous magnetic ordering below T {sub N}=21 K for B'=Mn, Ni, and T {sub C}=150 K for B'=Fe. From a Curie-Weiss fit, the effective paramagnetic moment for B'=Mn (5.74 {mu}{sub B}/f.u.) and B'=Ni(3.51 {mu}{sub B}/f.u.) are significantly different from the corresponding spin-only moments for the divalent cations, suggesting the possibility of a partial charge disproportionation B'{sup 2+}+U {sup 6+}{r_reversible}B'{sup 3+}+U {sup 5+}, also accounting for plausible ferrimagnetic interactions between B' and U sublattices. The strong curvature of the reciprocal susceptibility for B'=Fe precludes a Curie-Weiss fit but also suggests the presence of ferrimagnetic interactions in this compound. This charge disproportionation effect is also supported by the observed B'-O distances, which are closer to the expected values for high-spin, trivalent Mn, Fe and Ni cations. - Graphical abstract: The title double perovskites are monoclinic, space group P2{sub 1}/n, and the magnetic properties suggest the possibility of a partial charge disproportionation B'{sup 2+}+U {sup 6+}{r_reversible}B'{sup 3+}+U {sup 5+}, accounting for plausible ferrimagnetic interactions between B' and U sublattices.

  19. Anion order in perovskites: a group-theoretical analysis.

    PubMed

    Talanov, M V; Shirokov, V B; Talanov, V M

    2016-03-01

    Anion ordering in the structure of cubic perovskite has been investigated by the group-theoretical method. The possibility of the existence of 261 ordered low-symmetry structures, each with a unique space-group symmetry, is established. These results include five binary and 14 ternary anion superstructures. The 261 idealized anion-ordered perovskite structures are considered as aristotypes, giving rise to different derivatives. The structures of these derivatives are formed by tilting of BO6 octahedra, distortions caused by the cooperative Jahn-Teller effect and other physical effects. Some derivatives of aristotypes exist as real substances, and some as virtual ones. A classification of aristotypes of anion superstructures in perovskite is proposed: the AX class (the simultaneous ordering of A cations and anions in cubic perovskite structure), the BX class (the simultaneous ordering of B cations and anions) and the X class (the ordering of anions only in cubic perovskite structure). In most perovskites anion ordering is accompanied by cation ordering. Therefore, the main classes of anion order in perovskites are the AX and BX classes. The calculated structures of some anion superstructures are reported. Comparison of predictions and experimentally investigated anion superstructures shows coherency of theoretical and experimental results. PMID:26919374

  20. Multiferroic crossover in perovskite oxides

    NASA Astrophysics Data System (ADS)

    Weston, L.; Cui, X. Y.; Ringer, S. P.; Stampfl, C.

    2016-04-01

    The coexistence of ferroelectricity and magnetism in A B O3 perovskite oxides is rare, a phenomenon that has become known as the ferroelectric "d0 rule." Recently, the perovskite BiCoO3 has been shown experimentally to be isostructural with PbTiO3, while simultaneously the d6Co3 + ion has a high-spin ground state with C -type antiferromagnetic ordering. It has been suggested that the hybridization of Bi 6 s states with the O 2 p valence band stabilizes the polar phase, however, we have recently demonstrated that Co3 + ions in the perovskite structure can facilitate a ferroelectric distortion via the Co 3 d -O 2 p covalent interaction [L. Weston, et al., Phys. Rev. Lett. 114, 247601 (2015), 10.1103/PhysRevLett.114.247601]. In this paper, using accurate hybrid density functional calculations, we investigate the atomic, electronic, and magnetic structure of BiCoO3 to elucidate the origin of the multiferroic state. To begin with, we perform a more general first-principles investigation of the role of d electrons in affecting the tendency for perovskite materials to exhibit a ferroelectric distortion; this is achieved via a qualitative trend study in artificial cubic and tetragonal La B O3 perovskites. We choose La as the A cation so as to remove the effects of Bi 6 s hybridization. The lattice instability is identified by the softening of phonon modes in the cubic phase, as well as by the energy lowering associated with a ferroelectric distortion. For the La B O3 series, where B is a d0-d8 cation from the 3 d block, the trend study reveals that increasing the d orbital occupation initially removes the tendency for a polar distortion, as expected. However, for high-spin d5-d7 and d8 cations a strong ferroelectric instability is recovered. This effect is explained in terms of increased pseudo-Jahn-Teller (PJT) p -d vibronic coupling. The PJT effect is described by the competition between a stabilizing force (K0) that favors the cubic phase, and a vibronic term that

  1. La{sup 3+} doping of the Sr{sub 2}CoWO{sub 6} double perovskite: A structural and magnetic study

    SciTech Connect

    Lopez, C.A.; Viola, M.C.; Pedregosa, J.C. Carbonio, R.E.; Sanchez, R.D.; Fernandez-Diaz, M.T.

    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, 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.

  2. Ab initio study of the structural phase transitions of the double perovskites Sr2MWO6 (M=Zn, Ca, Mg)

    NASA Astrophysics Data System (ADS)

    Petralanda, U.; Etxebarria, I.

    2014-02-01

    We study the interplay of structural distortions in double perovskites Sr2MWO6 (M = Zn, Ca, Mg) by means of first-principles calculations and group theoretical analysis. Structure relaxations of the cubic, tetragonal, and monoclinic phases show that the ground states of the three compounds are monoclinic, although the energy difference between the monoclinic and tetragonal structures is very small in the case of Sr2MgWO6. The symmetry analysis of the distortions involved in the experimental and calculated low-temperature structures shows that the amplitude of two primary distortions associated to rigid rotations of the MX6 and WO6 octahedra are dominant, although the amplitude of a third mode related to deformations of the MX6 groups can not be neglected. The energy maps of the space spanned by the three relevant modes are calculated, and the couplings among the modes are evaluated, showing that the role of a hard secondary mode (in the Landau sense) coupled trilinearly to the two primary instabilities is crucial to stabilize the monoclinic ground state. Results suggest that the key role of the trilinear coupling among three modes could be rather common. A phenomenological theory including the effects of the chemical pressure is also developed. We find that the evolution of the stiffness constants in terms of the atomic substitution follows an accurate linear dependence and that the influence of quantum saturation of the order parameters could stabilize the tetragonal phase of Sr2MgWO6.

  3. Structure distortion and magnetism in double perovskites Ca{sub 2-x}La{sub x}FeReO{sub 6} (0{<=}x{<=}0.8)

    SciTech Connect

    Lue, Minfeng; Li, Junjie; Zou, Heng; Wu, Zhijian; Meng, Jian

    2010-12-15

    The crystal structure and magnetism of Ca{sub 2-x}La{sub x}FeReO{sub 6} (0{<=}x{<=}0.8) double perovskites have been investigated. The samples with low doping (x{<=}0.4) are found to crystallize with the monoclinic P2{sub 1}/n superstructure, while those in the high doping ones (x{>=}0.6) have orthorhombic Pbnm superstructure. With the increase of an La doping, the anti-site defects increases, giving rise to highly disordered samples at the Fe and Re positions. At the low doping region (x{<=}0.4), the compounds undergo a simultaneous structural and magnetic transition accompanying a slight increase of the Curie temperature. The increase of Curie temperature is discussed in terms of the structural change with doping. -- Graphical abstract: The crystal structures of Ca{sub 2-x}La{sub x}FeReO{sub 6} transform from monoclinic to orthorhombic; meanwhile, high degree of anti-site disorder was present at B/B' position, which promotes AFM correlations as an La increases. Display Omitted

  4. Research Update: Challenges for high-efficiency hybrid lead-halide perovskite LEDs and the path towards electrically pumped lasing

    NASA Astrophysics Data System (ADS)

    Li, Guangru; Price, Michael; Deschler, Felix

    2016-09-01

    Hybrid lead-halide perovskites have emerged as promising solution-processed semiconductor materials for thin-film optoelectronics. In this review, we discuss current challenges in perovskite LED performance, using thin-film and nano-crystalline perovskite as emitter layers, and look at device performance and stability. Fabrication of electrically pumped, optical-feedback devices with hybrid lead halide perovskites as gain medium is a future challenge, initiated by the demonstration of optically pumped lasing structures with low gain thresholds. We explain the material parameters affecting optical gain in perovskites and discuss the challenges towards electrically pumped perovskite lasers.

  5. NREL Studies Carrier Separation and Transport in Perovskite Solar Cells

    SciTech Connect

    2016-01-01

    NREL scientists studied charge separation and transport in perovskite solar cells by determining the junction structure across the solar device using the nanoelectrical characterization technique of Kelvin probe force microscopy. The distribution of electrical potential across both planar and porous devices demonstrates a p-n junction structure at the interface between titanium dioxide and perovskite. In addition, minority-carrier transport within the devices operates under diffusion/drift. Clarifying the fundamental junction structure provides significant guidance for future research and development. This NREL study points to the fact that improving carrier mobility is a critical factor for continued efficiency gains in perovskite solar cells.

  6. Review on palladium-containing perovskites: synthesis, physico-chemical properties and applications in catalysis.

    PubMed

    Essoumhi, Abdellatif; El Kazzouli, Saïd; Bousmina, Mosto

    2014-02-01

    This review reports on the recent advances in the synthesis and physico-chemical properties of palladium-containing perovskites. Initially, the perovskite structure is briefly reviewed, then palladium-containing perovskites synthesis and physico-chemical properties are detailed. The applications of palladium-containing perovskites in catalysis; namely, NO reduction, methane combustion, methanol as well as ethanol oxidation, are briefly highlighted. The involvement and the important contribution of palladium-containing perovskites in cross-coupling reactions, especially Suzuki-Miyaura, Sonogashira, Ulmann and Grignard, are discussed. PMID:24749470

  7. Ferroelectric ultrathin perovskite films

    DOEpatents

    Rappe, Andrew M; Kolpak, Alexie Michelle

    2013-12-10

    Disclosed herein are perovskite ferroelectric thin-film. Also disclosed are methods of controlling the properties of ferroelectric thin films. These films can be used in a variety materials and devices, such as catalysts and storage media, respectively.

  8. "Ba6Nb4RuO18" and "LaBa4Nb3RuO15" - The structural consequences of substituting paramagnetic cations into AnBn-1O3n cation-deficient perovskite oxides

    NASA Astrophysics Data System (ADS)

    Kamil, Elynor L.; Morgan, Harry W. T.; Hayward, Michael A.

    2016-06-01

    The B-cation deficient perovskite phases Ba6Nb4RuO18 and LaBa4Nb3RuO15 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 Ba6Nb4TiO18 and LaBa4Nb3TiO15) they adopt 5-layer and 4-layer B-cation deficient perovskite structures respectively, and are better described as Ba5Nb3.33Ru0.81O15 and Ba3.16La0.84Nb2.36Ru0.72O12. The factors that lead to the compositionally analogous Nb/Ru and Nb/Ti phases adopting different structures are discussed on the basis of the difference between d0 and non-d0 transition metal cations.

  9. Structures and magnetic properties of rare earth double perovskites containing antimony or bismuth Ba{sub 2}LnMO{sub 6} (Ln=rare earths; M=Sb, Bi)

    SciTech Connect

    Otsuka, Shumpei Hinatsu, Yukio

    2015-07-15

    A series of double perovskite-type oxides Ba{sub 2}LnMO{sub 6} (Ln=lanthanides; M=Sb, Bi) were synthesized and their structures were studied. The Ln and M are structurally ordered in the rock-salt type at the B-site of the perovskite ABO{sub 3}. For Ba{sub 2}PrBiO{sub 6} and Ba{sub 2}TbBiO{sub 6}, it has been found that the disordering between Ln ion and Bi ion occurs at the B-site of the double perovskite and both the Pr (Tb) and Bi exist in two oxidation state in the same compound from the analysis of the X-ray diffraction and magnetic susceptibility data. Magnetic susceptibility measurements show that all these compounds are paramagnetic and have no magnetic ordering down to 1.8 K. - Graphical abstract: Tolerance factor for Ba{sub 2}LnMO{sub 6} (M=Sb, Bi) plotted against the ionic radius of Ln{sup 3+}. We have found that there is a clear relation between crystal structures and tolerance factors. - Highlights: • The Ln and M ions are structurally ordered in the rock-salt type at the B-site. • The disordering between Pr (Tb) ion and Bi ion occurs at the B-site. • Ba{sub 2}LnMO{sub 6} (M=Sb, Bi) have no magnetic ordering down to 1.8 K.

  10. Stable ferroelectric perovskite structure with giant axial ratio and polarization in epitaxial BiFe0.6Ga0.4O3 thin films.

    PubMed

    Fan, Zhen; Xiao, Juanxiu; Liu, Huajun; Yang, Ping; Ke, Qingqing; Ji, Wei; Yao, Kui; Ong, Khuong P; Zeng, Kaiyang; Wang, John

    2015-02-01

    Ferroelectric perovskites with strongly elongated unit cells (c/a > 1.2) are of particular interest for realizing giant polarization induced by significant ionic off-center displacements. Here we show that epitaxial BiFe0.6Ga0.4O3 (BFGO) thin films exhibit a stable super-tetragonal-like structure with twinning domains regardless of film thickness and substrate induced strain, evidenced with high resolution X-ray diffractometry (HR-XRD), transmission electron microscopy (TEM) and piezoresponse force microscopy (PFM). The origin of the structural stability of BFGO is investigated by the first-principles calculation. The ferroelectric properties of BFGO are studied by PFM, first-principles calculation and macroscopic polarization-electric field (P-E) hysteresis measurement. A giant ferroelectric polarization of ∼150 μC/cm(2) is revealed by the first-principles calculations and confirmed by experiments. Our studies provide an alternative pathway of employing Ga-substitution other than the extensively studied strain engineering to stabilize the supertetragonal structure in BiFeO3-based epitaxial thin films.

  11. Absence of Significant Structural Changes Near the Magnetic Ordering Temperature in Small-ion Rare Earth Perovskite RMnO3

    SciTech Connect

    Yu, T.; Ty, T.; Chen, H.; Abeykoon, A. M. M.; Chen, Y. -S.; Ahn, K. H.

    2014-11-14

    The detailed structural measurements on multiple length scales were conducted on a new perovskite phase of ScMnO3, and on orthorhombic LuMnO3 as a benchmark. Complementary density functional theory (DFT) calculations were carried out, and predict that ScMnO3 possesses E-phase magnetic order at low temperature with displacements of the Mn sites (relative to the high temperature state) of ~0.07 Å, compared to ~0.04 Å predicted for LuMnO3. However, detailed local, intermediate and long-range structural measurements by x-ray pair distribution function analysis, single crystal x-ray diffraction and x-ray absorption spectroscopy, find no local or long-range distortions on crossing into the low temperature E-phase of the magnetically ordered state. Our measurements place upper limits on any structural changes to be at most one order of magnitude lower than DFT predictions and suggest that this theoretical approach does not properly account for the spin–lattice coupling in these oxides and may possibly predict the incorrect magnetic order at low temperatures. The results suggest that the electronic contribution to the electrical polarization dominates and should be more accurately treated in theoretical models.

  12. Electron diffraction and microscopy study of the structure and microstructure of the hexagonal perovskite Ba3Ti2MnO9.

    PubMed

    Maunders, Christian; Whitfield, Harold J; Hay, David G; Etheridge, Joanne

    2007-06-01

    This paper reports a structural and microstructural investigation of the hexagonal perovskite Ba(3)Ti(2)MnO(9) using electron microscopy and diffraction. Convergent-beam electron diffraction (CBED) revealed the structure has the non-centrosymmetric space group P6(3)mc (186) at room temperature and at approximately 110 K. Compared with the centrosymmetric parent structure BaTiO(3), with space group P6(3)/mmc, this represents a break in mirror symmetry normal to the c axis. This implies the Ti and Mn atoms are ordered on alternate octahedral sites along the 0001 direction in Ba(3)Ti(2)MnO(9). Using high-resolution electron microscopy (HREM), we observed occasional 6H/12R interfaces on (0001) planes, however, no antiphase boundaries were observed, as were seen in Ba(3)Ti(2)RuO(9). Using powder X-ray Rietveld refinement we have measured the lattice parameters from polycrystalline samples to be a = 5.6880 +/- 0.0005, c = 13.9223 +/- 0.0015 A at room temperature. PMID:17507751

  13. Highly efficient light management for perovskite solar cells

    PubMed Central

    Wang, Dong-Lin; Cui, Hui-Juan; Hou, Guo-Jiao; Zhu, Zhen-Gang; Yan, Qing-Bo; Su, Gang

    2016-01-01

    Organic-inorganic halide perovskite solar cells have enormous potential to impact the existing photovoltaic industry. As realizing a higher conversion efficiency of the solar cell is still the most crucial task, a great number of schemes were proposed to minimize the carrier loss by optimizing the electrical properties of the perovskite solar cells. Here, we focus on another significant aspect that is to minimize the light loss by optimizing the light management to gain a high efficiency for perovskite solar cells. In our scheme, the slotted and inverted prism structured SiO2 layers are adopted to trap more light into the solar cells, and a better transparent conducting oxide layer is employed to reduce the parasitic absorption. For such an implementation, the efficiency and the serviceable angle of the perovskite solar cell can be promoted impressively. This proposal would shed new light on developing the high-performance perovskite solar cells. PMID:26733112

  14. Highly efficient light management for perovskite solar cells.

    PubMed

    Wang, Dong-Lin; Cui, Hui-Juan; Hou, Guo-Jiao; Zhu, Zhen-Gang; Yan, Qing-Bo; Su, Gang

    2016-01-06

    Organic-inorganic halide perovskite solar cells have enormous potential to impact the existing photovoltaic industry. As realizing a higher conversion efficiency of the solar cell is still the most crucial task, a great number of schemes were proposed to minimize the carrier loss by optimizing the electrical properties of the perovskite solar cells. Here, we focus on another significant aspect that is to minimize the light loss by optimizing the light management to gain a high efficiency for perovskite solar cells. In our scheme, the slotted and inverted prism structured SiO2 layers are adopted to trap more light into the solar cells, and a better transparent conducting oxide layer is employed to reduce the parasitic absorption. For such an implementation, the efficiency and the serviceable angle of the perovskite solar cell can be promoted impressively. This proposal would shed new light on developing the high-performance perovskite solar cells.

  15. Perovskite ferroelectric nanomaterials

    NASA Astrophysics Data System (ADS)

    Nuraje, Nurxat; Su, Kai

    2013-09-01

    In this review, the main concept of ferroelectricity of perovskite oxides and related materials at nanometer scale and existing difficulties in the synthesis of those nanocrystals are discussed. Important effects, such as depolarization field and size effect, on the existence of ferroelectricity in perovskite nanocrystals are deliberated. In the discussion of modeling works, different theoretical calculations are pinpointed focusing on their studies of lattice dynamics, phase transitions, new origin of ferroelectricity in nanostructures, etc. As the major part of this review, recent research progress in the facile synthesis, characterization and various applications of perovskite ferroelectric nanomaterials, such as BaTiO3, PbTiO3, PbZrO3, and BiFeO3, are also scrutinized. Perspectives concerning the future direction of ferroelectric nanomaterials research and its potential applications in renewable energy, etc., are presented. This review provides an overview in this area and guidance for further studies in perovskite ferroelectric nanomaterials and their applications.In this review, the main concept of ferroelectricity of perovskite oxides and related materials at nanometer scale and existing difficulties in the synthesis of those nanocrystals are discussed. Important effects, such as depolarization field and size effect, on the existence of ferroelectricity in perovskite nanocrystals are deliberated. In the discussion of modeling works, different theoretical calculations are pinpointed focusing on their studies of lattice dynamics, phase transitions, new origin of ferroelectricity in nanostructures, etc. As the major part of this review, recent research progress in the facile synthesis, characterization and various applications of perovskite ferroelectric nanomaterials, such as BaTiO3, PbTiO3, PbZrO3, and BiFeO3, are also scrutinized. Perspectives concerning the future direction of ferroelectric nanomaterials research and its potential applications in renewable

  16. Structural phase transition causing anomalous photoluminescence behavior in perovskite (C{sub 6}H{sub 11}NH{sub 3}){sub 2}[PbI{sub 4}

    SciTech Connect

    Yangui, A.; Pillet, S.; Mlayah, A.; Lusson, A.; Bouchez, G.; Boukheddaden, K. E-mail: kbo@physique.uvsq.fr; Triki, S.; Abid, Y. E-mail: kbo@physique.uvsq.fr

    2015-12-14

    Optical and structural properties of the organic-inorganic hybrid perovskite-type (C{sub 6}H{sub 11}NH{sub 3}){sub 2}[PbI{sub 4}] (abbreviated as C{sub 6}PbI{sub 4}) were investigated using optical absorption, photoluminescence (PL), and x-ray diffraction measurements. Room temperature, optical absorption measurements, performed on spin-coated films of C{sub 6}PbI{sub 4}, 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 PbI{sub 6} 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

  17. 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.

  18. Structural and electrical characterizations of cerium (Ce3+)-doped double perovskite system Sr2NiMoO6- δ

    NASA Astrophysics Data System (ADS)

    Kumar, Pravin; Singh, Nitish Kumar; Sinha, A. S. K.; Singh, Prabhakar

    2016-09-01

    The double perovskite system Sr2- x Ce x NiMoO6- δ (SCNM) with 0.01 ≤ x ≤ 0.05 was synthesized by the citrate-nitrate auto-combustion synthesis route. Thermal studies were carried out by simultaneous differential scanning calorimetry and thermal gravimetry. Phase constitution was analyzed by powder X-ray diffraction (XRD). Rietveld refinement showed that the major phase exists in tetragonal form with space group I4/m. Microstructural investigations revealed the formation of uniform grains. The electrical conductivity studied by impedance spectroscopy in the temperature range 300-600 °C was found to follow a thermally activated process. The sample with x = 0.01 showed the highest conductivity with lowest activation energy. The electrical conductivity of the system was discussed in terms of identified impurity phases and charge density [{{{Mo}}_{{{{Mo}}^{6 +}}}^{5 +} {}^' ]. The variation of electrical conductivity with composition was explained on the basis of X-ray photoelectron spectroscopy and XRD studies.

  19. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface.

    PubMed

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; Crumlin, Ethan J; Yildiz, Bilge

    2016-09-01

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (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 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. PMID:27295099

  20. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

    NASA Astrophysics Data System (ADS)

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; Crumlin, Ethan J.; Yildiz, Bilge

    2016-09-01

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (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 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.

  1. Thermochemistry of perovskites in the lanthanum-strontium-manganese-iron oxide system

    NASA Astrophysics Data System (ADS)

    Marinescu, Cornelia; Vradman, Leonid; Tanasescu, Speranta; Navrotsky, Alexandra

    2015-10-01

    The enthalpies of formation from binary oxides of perovskites (ABO3) based on lanthanum strontium manganite La(Sr)MnO3 (LSM) and lanthanum strontium ferrite La(Sr)FeO3 (LSF) and mixed lanthanum strontium manganite ferrite La(Sr)Mn(Fe)O3 (LSMF) were measured by high temperature oxide melt solution calorimetry. Using iodometric titration, the oxygen content was derived. The perovskites with A-site cation deficiency have greater oxygen deficiency than the corresponding A-site stoichiometric series. Stability of LSMF decreases with increasing iron content. Increasing oxygen deficiency clearly destabilizes the perovskites. The results suggest an enthalpy of oxygen incorporation that is approximately independent of composition. 0.35La2O3 (xl, 25 °C)+Mn2O3 (xl, 25 °C)+0.3SrO (xl, 25 °C)+Fe2O3 (xl, 25 °C)+O2 (g, 25 °C)→La0.7Sr0.3Mn1-yFeyO3-δ (xl, 25 °C). (b) ∆ Hf,ox* (La0.7Sr0.3Mn1-yFeyO3-δ) .0.35 La2O3 (xl, 25 ººC) + (0.7-y+ 2δ)/2 Mn2O3 (xl, 25 ºC) + 0.3 SrO (xl, 25 ºC) + y/2Fe2O3 (xl, 25 ºC) + (0.3-2δ) MnO2 (xl, 25 ºC)→La0.7Sr0.3Mn1-yFeyO3-δ (xl, 25 ºC).

  2. A-site deficient perovskites in the SrO-ZrO{sub 2}-Nb{sub 2}O{sub 5} system: Composition dependent structures from neutron powder diffraction data

    SciTech Connect

    Schmid, Siegbert; Withers, Ray L.

    2012-07-15

    A series of A-site deficient perovskite-type phases was synthesised and characterised in the SrO-ZrO{sub 2}-Nb{sub 2}O{sub 5} system. The composition range was established as Sr{sub 0.70+x}Zr{sub 0.40+2x}Nb{sub 0.60-2x}O{sub 3}, {approx}0.02{<=}x{<=}0.30, and the resulting structures refined using high resolution neutron powder diffraction data. While structures in this composition range are closely related to the cubic perovskite parent, the symmetry for all investigated compositions is lowered to tetragonal or orthorhombic. For x<0.15 the resulting space group is tetragonal I4/mcm, for x>0.15 it is orthorhombic Pnma and for x=0.15 two phases co-exist, in space groups I4/mcm and Pnma. - Graphical abstract: Structured diffuse intensity indicating additional short range order in the defect perovskite Sr{sub 0.72}Zr{sub 0.44}Nb{sub 0.56}O{sub 3}. Highlights: Black-Right-Pointing-Pointer A-site deficient perovskites synthesised in Sr{sub 0.70+x}Zr{sub 0.40+2x}Nb{sub 0.60-2x}O{sub 3}, {approx}0.02 {<=}x{<=}0.30. Black-Right-Pointing-Pointer Space groups established from X-ray, electron and neutron powder diffraction. Black-Right-Pointing-Pointer Structures refined and phase transition established from neutron diffraction data.

  3. Pseudo Jahn-Teller origin of ferroelectric instability in BaTiO3 type perovskites: The Green's function approach and beyond

    NASA Astrophysics Data System (ADS)

    Polinger, V.; Garcia-Fernandez, P.; Bersuker, I. B.

    2015-01-01

    The local origin of dipolar distortions in ABO3 perovskite crystals is reexamined by means of a novel approach, the Green's function method augmented by DFT computations. The ferroelectric distortions are shown to be induced by the pseudo Jahn-Teller effect (PJTE). The latter involves vibronic hybridization (admixture) of the ground state to same-spin opposite-parity excited electronic bands. Similar to numerous molecular calculations, the PJT approach provides a deeper insight into the nature of chemical bonding in the octahedral cluster [BO6] and, in particular, reveals the local origin of its polar instability. This allows predicting directly which transition ions can create ferroelectricity. In particular, the necessary conditions are established when an ABO3 perovskite crystal with an electronic dn configuration of the complex ion [BO6] can possess both proper ferroelectric and magnetic properties. Distinguished from the variety of cluster approaches to local properties, the Green's function method includes the influence of the local vibronic-coupling perturbation on the whole crystal via the inter-cell interaction responsible for creation of electronic and vibrational bands. Calculated Green's functions combined with the corresponding numeric estimates for the nine electronic bands, their density of states, and the local adiabatic potential energy surface (APES) confirm the eight-minimum form of this surface and feasibility of the PJT origin of the polar instability in BaTiO3. We show also that multicenter long-range dipole-dipole interactions critically depend on the PJTE largely determining the magnitude of the local dipoles. DFT calculations for the bulk crystal and its clusters confirm that the dipolar distortions are of local origin, but become possible only when their influence on (relaxation of) the whole lattice is taken into account. The results are shown to be in full qualitative and semiquantitative agreement with the experimental data for this

  4. A Heteroepitaxial Perovskite Metal-Base Transistor

    SciTech Connect

    Yajima, T.; Hikita, Y.; Hwang, H.Y.; /Tokyo U. /JST, PRESTO /SLAC

    2011-08-11

    'More than Moore' captures a concept for overcoming limitations in silicon electronics by incorporating new functionalities in the constituent materials. Perovskite oxides are candidates because of their vast array of physical properties in a common structure. They also enable new electronic devices based on strongly-correlated electrons. The field effect transistor and its derivatives have been the principal oxide devices investigated thus far, but another option is available in a different geometry: if the current is perpendicular to the interface, the strong internal electric fields generated at back-to-back heterojunctions can be used for oxide electronics, analogous to bipolar transistors. Here we demonstrate a perovskite heteroepitaxial metal-base transistor operating at room temperature, enabled by interface dipole engineering. Analysis of many devices quantifies the evolution from hot-electron to permeable-base behaviour. This device provides a platform for incorporating the exotic ground states of perovskite oxides, as well as novel electronic phases at their interfaces.

  5. Nanoimprinted Perovskite Solar Cells With Enhanced Photocurrent

    NASA Astrophysics Data System (ADS)

    Haroldson, Ross; Balachandran, Balasubramaniam?; Ren, Yixin; Zakhidov, Anvar; Hu, Wenchuang; UTD Nanoimprint Team

    We have developed a new method of Nanoimprint Lithography (NIL) to shape the morphology of organolead trihalide perovskite. With this hot stamping process we created ordered gratings or other micro or nanostructures of perovskite resembling 2D photonic crytals on the scale of 200 to 600 nm from a starting small grain spin-coated film of the same scale. With this new method of nanoimprinting, we demonstrate that perovskite PV device performance can be improved and controlled. Initial results comparing flat vs. NIL-PV structure devices show dramatic increase in photocurrent as well as better crystallinity. The origin of Isc enhancement is explained in terms of better morphology and larger grains, resulting in longer diffusion length of carriers, while better light absorption by photonic crystal nanopatterns cannot be excluded.

  6. High-pressure synthesis, crystal structures, and magnetic properties of 5d double-perovskite oxides Ca2MgOsO6 and Sr2MgOsO6.

    PubMed

    Yuan, Yahua; Feng, Hai L; Ghimire, Madhav Prasad; Matsushita, Yoshitaka; Tsujimoto, Yoshihiro; He, Jianfeng; Tanaka, Masahiko; Katsuya, Yoshio; Yamaura, Kazunari

    2015-04-01

    Double-perovskite oxides Ca2MgOsO6 and Sr2MgOsO6 have been synthesized under high-pressure and high-temperature conditions (6 GPa and 1500 °C). Their crystal structures and magnetic properties were studied by a synchrotron X-ray diffraction experiment and by magnetic susceptibility, specific heat, isothermal magnetization, and electrical resistivity measurements. Ca2MgOsO6 and Sr2MgOsO6 crystallized in monoclinic (P21/n) and tetragonal (I4/m) double-perovskite structures, respectively; the degree of order of the Os and Mg arrangement was 96% or higher. Although Ca2MgOsO6 and Sr2MgOsO6 are isoelectric, a magnetic-glass transition was observed for Ca2MgOsO6 at 19 K, while Sr2MgOsO6 showed an antiferromagnetic transition at 110 K. The antiferromagnetic-transition temperature is the highest in the family. A first-principles density functional approach revealed that Ca2MgOsO6 and Sr2MgOsO6 are likely to be antiferromagnetic Mott insulators in which the band gaps open, with Coulomb correlations of ∼1.8-3.0 eV. These compounds offer a better opportunity for the clarification of the basis of 5d magnetic sublattices, with regard to the possible use of perovskite-related oxides in multifunctional devices. The double-perovskite oxides Ca2MgOsO6 and Sr2MgOsO6 are likely to be Mott insulators with a magnetic-glass (MG) transition at ∼19 K and an antiferromagnetic (AFM) transition at ∼110 K, respectively. This AFM transition temperature is the highest among double-perovskite oxides containing single magnetic sublattices. Thus, these compounds offer valuable opportunities for studying the magnetic nature of 5d perovskite-related oxides, with regard to their possible use in multifunctional devices. PMID:25751088

  7. Investigations of the magnetic properties and structures of the pillared perovskites, La{sub 5}Re{sub 3}MO{sub 16} (M=Co, Ni)

    SciTech Connect

    Cuthbert, Heather L. . E-mail: cuthbehl@mcmaster.ca; Greedan, John E.; Cranswick, Lachlan

    2006-07-15

    La{sub 5}Re{sub 3}CoO{sub 16} and La{sub 5}Re{sub 3}NiO{sub 16} were synthesized by solid-state reaction and studied by SQUID magnetometry, heat capacity and powder neutron diffraction measurements. These two compounds belong to a series of isostructural Re-based pillared perovskites [Chi et al. J. Solid State Chem. 170 (2003) 165]. Magnetic susceptibility measurements indicate apparent short-range ferri or ferromagnetic correlations and possible long-range antiferromagnetic order for La{sub 5}Re{sub 3}CoO{sub 16} at 35K, and at 38 and 14K for La{sub 5}Re{sub 3}NiO{sub 16}. Heat capacity measurements of the Co compound show a lambda anomaly, typical of long-range magnetic order, at 32K. In contrast, the Ni compound displays a broader, more symmetric feature at 12K in the heat capacity data, indicative of short-range magnetic order. Low-temperature powder neutron diffraction revealed contrasting magnetic structures. While both show an ordering wave vector, k=(0,0,1/2), in La{sub 5}Re{sub 3}CoO{sub 16}, the Co{sup 2+} and Re{sup 5+} moments are ordered ferrimagnetically within the corner-shared octahedral layers, while the layers themselves are coupled antiferromagnetically along the c-axis, as also found in La{sub 5}Re{sub 3}MnO{sub 16} and La{sub 5}Re{sub 3}FeO{sub 16}. In the case of the Ni material, the Re{sup 5+} and Ni{sup 2+} moments in the perovskite layers couple ferromagnetically and are canted 30 deg. away from the c-axis, angled 45 deg. in the ab-plane. The layers then couple antiferromagnetically at low temperature, a unique magnetic structure for this series. The properties of the La{sub 5}Re{sub 3}MO{sub 16} series, with M=Mn, Fe, Co, Ni and Mg are also reviewed.

  8. Ab initio investigation of the structural, electronic, magnetic and optical properties of the perovskite TlMnX3 (X = F, Cl) compounds

    NASA Astrophysics Data System (ADS)

    Hamioud, Farida; Alghamdi, Ghadah S.; Al-Omari, Saleh; Mubarak, A. A.

    2016-03-01

    We have performed ab initio investigation of some physical properties of the perovskite TlMnX3 (X = F, Cl) compounds using the full-potential linearized augmented plane wave (FP-LAPW) method. The generalized gradient approximation (GGA) is employed as exchange-correlation potential. The calculated lattice constant and bulk modulus agree with previous studies. Both compounds are found to be elastically stable. TlMnF3 and TlMnCl3 are classified as anisotropic and ductile compounds. The calculations of the band structure of the studied compounds showed the semiconductor behavior with the indirect (M-X) energy gap. Both compounds are classified as a ferromagnetic due to the integer value of the total magnetic moment of the compounds. The different optical spectra are calculated from the real and the imaginary parts of the dielectric function and connected to the electronic structure of the compounds. The static refractive index n(0) is inversely proportional to the energy bandgap of the two compounds. Beneficial optics technology applications are predicted based on the optical spectra.

  9. Structural and Electrical Properties of Rare Earth Double Perovskite Oxides Ba2CeMO6 (M = Ta5+ and Nb5+)

    NASA Astrophysics Data System (ADS)

    Bharti, Chandrahas; Sinha, T. P.

    2011-07-01

    We have synthesized rare earth double perovskite oxides barium cerium niobate Ba2CeNbO6 (BCN) and barium cerium tantalate Ba2CeNbO6 (BCT) by solid state reaction technique and studied the structural and electrical properties. The x-ray diffraction pattern at room temperature (25° C) shows monoclinic structure with the lattice parameters, a = 5.9763 Å, b = 5.975 Å and c = 8.48 Å and β = 90.04° for BCN and a = 5.9763 Å, b = 5.975 Å and c = 8.48 Å and β = 90.034° for BCT. Scanning electron micrograph (SEM) shows the formation of grains with different shape and size The AC electrical conductivity (σ) ( = ωɛoΕ″) is obtained from the temperature dependence of the real (Ε') and imaginary (e") components of the complex dielectric constant Ε* ( = Ε--jΕ″). The frequency dependent conductivity spectra follow the universal power law.

  10. Cs{sub 3}Zr{sub 6}Br{sub 15}Z (Z = C, B): A stuffed rhombohedral perovskite structure of linked clusters

    SciTech Connect

    Qi, Ru-Yi; Corbett, J.D.

    1995-03-29

    The isostructural title compounds are synthesized in good yields form reactions of Zr, ZrBr{sub 4}, CsBr, and Z in sealed Ta tubing for {approximately}3 weeks at 850 {degrees}C. Their single-crystal data refinements established the products as Cs{sub 3.02(7)-}Zr{sub 6}Br{sub 14}C and Cs{sub 3.39(5)}Zr{sub 6}br{sub 15}B (R3c, Z = 6, a = 13.1031 (6), 13.116(1) {angstrom}, c = 35.800(3), 35.980(6) {angstrom}, R(F)/R{sub w} = 5.4/5.9, 5.4/4.4%, respectively). The structure is derived form a three-dimensional [Zr{sub 6}(Z)Br{sub 12}]Br{sub 6/2} network of four-rings (as in ReO{sub 6/2}) twisted into a rhombohedral perovskite analogous to VF{sub 3}. The three necessary Cs{sup +} cations are fractionally distributed over five sites that are far from optimal or common, with either eight asymmetric or only three close bromide neighbors. Refinement of a third Cs{sub 3.18(5)}Zr{sub 6}Br{sub 15}C structure at {minus}50 {degrees}C gave the same result with somewhat smaller positional distributions of the atoms.

  11. Structure, stability, and photoluminescence in the anti-perovskites Na3W1-xMoxO4F (0≤x≤1)

    NASA Astrophysics Data System (ADS)

    Sullivan, Eirin; Avdeev, Maxim; Blom, Douglas A.; Gahrs, Casey J.; Green, Robert L.; Hamaker, Christopher G.; Vogt, Thomas

    2015-10-01

    Single-phase ordered oxyfluorides Na3WO4F, Na3MoO4F and their mixed members Na3W1-xMoxO4F can be prepared via facile solid state reaction of Na2MO4·2H2O (M=W, Mo) and NaF. Phases produced from incongruent melts are metastable, but lower temperatures allow for a facile one-step synthesis. In polycrystalline samples of Na3W1-xMoxO4F, the presence of Mo stabilizes the structure against decomposition to spinel phases. Photoluminescence studies show that upon excitation with λ=254 nm and λ=365 nm, Na3WO4F and Na3MoO4F exhibit broad emission maxima centered around 485 nm. These materials constitute new members of the family of self-activating ordered oxyfluoride phosphors with anti-perovskite structures which are amenable to doping with emitters such as Eu3+.

  12. Coexistence of Three Ferroic Orders in the Multiferroic Compound [(CH3 )4 N][Mn(N3 )3 ] with Perovskite-Like Structure.

    PubMed

    Gómez-Aguirre, L Claudia; Pato-Doldán, Breogán; Stroppa, Alessandro; Yang, Li-Ming; Frauenheim, Thomas; Mira, Jorge; Yáñez-Vilar, Susana; Artiaga, Ramón; Castro-García, Socorro; Sánchez-Andújar, Manuel; Señarís-Rodríguez, María Antonia

    2016-06-01

    The perovskite azido compound [(CH3 )4 N][Mn(N3 )3 ], which undergoes a first-order phase change at Tt =310 K with an associated magnetic bistability, was revisited in the search for additional ferroic orders. The driving force for such structural transition is multifold and involves a peculiar cooperative rotation of the [MnN6 ] octahedral as well as order/disorder and off-center shifts of the [(CH3 )4 N](+) cations and bridging azide ligands, which also bend and change their coordination mode. According to DFT calculations the latter two give rise to the appearance of electric dipoles in the low-temperature (LT) polymorph, the polarization of which nevertheless cancels out due to their antiparallel alignment in the crystal. The conversion of this antiferroelectric phase to the paraelectric phase could be responsible for the experimental dielectric anomaly detected at 310 K. Additionally, the structural change involves a ferroelastic phase transition, whereby the LT polymorph exhibits an unusual and anisotropic thermal behavior. Hence, [(CH3 )4 N][Mn(N3 )3 ] is a singular material in which three ferroic orders coexist even above room temperature. PMID:27072487

  13. The local post-perovskite structure and its temperature dependence : atom-pair distances in CalrO{sub 3} revealed through analysis of the total x-ray scattering at high temperatures.

    SciTech Connect

    Martin, C. D.; X-Ray Science Division

    2008-08-01

    The temperature-dependent post-perovskite structure model of MgSiO{sub 3} is reinvestigated through analysis of the atom-pair distances observed experimentally via Fourier transformation of X-ray diffraction and diffuse scattering, the total X-ray scattering, from CaIrO{sub 3}. In contrast to the results of a previous Rietveld structure refinement, which shows a negative or null thermal expansion of Ir-O and Ca-O bond lengths within the average long-range structure, visual inspection of these atom-pair distances in the pair-distribution function, in addition to structure models fitted through least-squares refinement to this local-structure data, strongly suggests that these distances between atom pairs increase with temperature. The average long-range structure of CaIrO{sub 3}, visible from Rietveld structure refinement, is distinct from the short-range structure ({le} 18 {angstrom}) at all of the temperatures examined in this study (325-1114 K) and is reproduced in structure models fitted to the pair-distribution function extending to sufficiently long atom-pair distances ({ge} 50 {angstrom}). While previous data obtained with Rietveld structure refinement show the iridium coordination octahedra to distort with increasing temperature, models of the short-range structure demonstrate that these polyhedra instead reduce distortion and rotate in a manner similar to that occurring in the perovskite structure.

  14. Perovskite solid electrolytes for SOFC

    SciTech Connect

    Sammells, A.F.

    1992-09-01

    Selected perovskite solid electrolytes incorporated into research size fuel cells have shown stability for > 4000 hours at 600{degrees}C. Perovskite lattice requirements which favor low E{sub a} for ionic conduction include (i) that the perovskite lattice possess a moderate enthalpy of formation, (ii) perovskite lattice possess large free volumes, (iii) that the lattice minimally polarizes the mobile ion and (iv) that the crystallographic saddle point r{sub c} for ionic conduction is {approx_equal} 1.

  15. Perovskite solid electrolytes for SOFC

    SciTech Connect

    Sammells, A.F.

    1992-01-01

    Selected perovskite solid electrolytes incorporated into research size fuel cells have shown stability for > 4000 hours at 600{degrees}C. Perovskite lattice requirements which favor low E{sub a} for ionic conduction include (i) that the perovskite lattice possess a moderate enthalpy of formation, (ii) perovskite lattice possess large free volumes, (iii) that the lattice minimally polarizes the mobile ion and (iv) that the crystallographic saddle point r{sub c} for ionic conduction is {approx equal} 1.

  16. The Coulombic Lattice Potential of Ionic Compounds: The Cubic Perovskites.

    ERIC Educational Resources Information Center

    Francisco, E.; And Others

    1988-01-01

    Presents coulombic models representing the particles of a system by point charges interacting through Coulomb's law to explain coulombic lattice potential. Uses rubidium manganese trifluoride as an example of cubic perovskite structure. Discusses the effects on cluster properties. (CW)

  17. Interfacial structure of multi-layered thin-films produced by pulsed laser deposition for use in small-scale ceramic capacitors

    NASA Astrophysics Data System (ADS)

    Araki, Takao; Hino, Takanori; Ohara, Masahiro

    2014-08-01

    The aim of this study was to develop thin film capacitors with superior properties that could provide an alternative to materials currently used in conventional multi-layer ceramic capacitors fabricated by sintering. To this end, an artificial dielectric super lattice technique, incorporating pulsed laser deposition, was applied to improving the dielectric properties of thin film capacitors. This method permits the A-site atoms of a perovskite ABO3 structure to be selected layer by layer at a nanoscopic scale; consequently, multi-layer BaTiO3- SrTiO3 thin films were produced on Pt(111)/Ti/SiO2/Si(100) and SrTiO3(111) substrates. Hetero-epitaxial grain growth was observed between BaTiO3 and SrTiO3, with the lattice mismatch between them introducing a compressive residual strain at the interface. The dielectric properties of these multi-layer thin-film capacitors were found to be superior to those of conventional solid-solution thin films once the thickness of the layers and the ratio of the two oxides were optimized.

  18. 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

    2016-08-01

    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. PMID:27435936

  19. Ultrathin efficient perovskite solar cells employing a periodic structure of a composite hole conductor for elevated plasmonic light harvesting and hole collection

    NASA Astrophysics Data System (ADS)

    Long, Mingzhu; Chen, Zefeng; Zhang, Tiankai; Xiao, Yubin; Zeng, Xiaoliang; Chen, Jian; Yan, Keyou; Xu, Jianbin

    2016-03-01

    We developed a molecule/polymer composite hole transporting material (HTM) with a periodic microstructure for morphology replication of a corrugated Au electrode, which in combination plays a dual role in the optical and electronic enhancement of high performance perovskite solar cells (PSCs). The electro-optics revealed that perovskite couldn't readily extinct the red light even though the thickness increased to 370 nm, but we found that the quasi periodic microstructure composite (PMC) HTM in combination with the conformal Au electrode could promote the absorption through the enhanced cavity effects, leading to comparable absorption even using much thinner perovskite (240 nm). We identified that the cavity was the combination of Fabry-Pérot interferometer and surface plasmonic resonance, with light harvesting enhancement through surface plasmon polariton or waveguide modes that propagate in the plane of the perovskite layer. On the other hand, the PMC HTM increased hole conductivity by one order of magnitude with respect to standard spiro-OMeTAD HTM due to molecular packing and self-assembly, embodying traceable hole mobility and density elevation up to 3 times, and thus the hysteresis was greatly avoided. Owing to dual optical and electronic enhancement, the PMC PSC afforded high efficiency PSC using as thin as 240 nm perovskite layer, delivering a Voc of 1.05 V, Jsc of 22.9 mA cm-2, FF of 0.736, and efficiency amounting to 17.7% PCE, the highest efficiency with ultrathin perovskite layer.We developed a molecule/polymer composite hole transporting material (HTM) with a periodic microstructure for morphology replication of a corrugated Au electrode, which in combination plays a dual role in the optical and electronic enhancement of high performance perovskite solar cells (PSCs). The electro-optics revealed that perovskite couldn't readily extinct the red light even though the thickness increased to 370 nm, but we found that the quasi periodic microstructure

  20. Reduced thermal conductivity by nanoscale intergrowths in perovskite like layered structure La{sub 2}Ti{sub 2}O{sub 7}

    SciTech Connect

    Khaliq, Jibran; Chen, Kan; Li, Chunchun; Shi, Baogui; Ye, Haitao; Grande, Antonio M.; Yan, Haixue; Reece, Michael J.

    2015-02-21

    The effect of substitution and oxidation-reduction on the thermal conductivity of perovskite-like layered structure (PLS) ceramics was investigated in relation to mass contrast and non-stoichiometry. Sr (acceptor) was substituted on the A site, while Ta (donor) was substituted on the B site of La{sub 2}Ti{sub 2}O{sub 7}. Substitution in PLS materials creates atomic scale disorders to accommodate the non-stoichiometry. High resolution transmission electron microscopy and X ray diffraction revealed that acceptor substitution in La{sub 2}Ti{sub 2}O{sub 7} produced nanoscale intergrowths of n = 5 layered phase, while donor substitution produced nanoscale intergrowths of n = 3 layered phase. As a result of these nanoscale intergrowths, the thermal conductivity value reduced by as much as ∼20%. Pure La{sub 2}Ti{sub 2}O{sub 7} has a thermal conductivity value of ∼1.3 W/m K which dropped to a value of ∼1.12 W/m K for Sr doped La{sub 2}Ti{sub 2}O{sub 7} and ∼0.93 W/m K for Ta doped La{sub 2}Ti{sub 2}O{sub 7} at 573 K.

  1. Synthesis, structural characterization, and magnetic properties of the antiferromagnetic double perovskites Ln {sub 2}LiOsO{sub 6} (Ln=La, Pr, Nd, Sm)

    SciTech Connect

    Gemmill, William R.; Smith, Mark D.; Loye, Hans-Conrad zur . E-mail: jssc@mail.chem.sc.edu

    2006-06-15

    A series of osmium double perovskite oxides, Ln {sub 2}LiOsO{sub 6} (Ln=La, Pr, Nd, Sm), has been prepared as single crystals from acidic molten hydroxide. All four oxides crystallize in the monoclinic space group P2{sub 1}/n (Glazer tilt system no. 10, a {sup -} a {sup -} b {sup +}), forming a 1:1 ordered rock salt lattice of Li{sup +} and Os{sup 5+} cations. Magnetic susceptibility measurements show that these compounds are antiferromagnetic at low temperature with ordering temperatures of 39, 35, 23, and 32 K for Ln {sub 2}LiOsO{sub 6} (Ln=La, Pr, Nd, Sm), respectively. - Graphical abstract: Approximate (110) view of the crystal structure of Pr{sub 2}LiOsO{sub 6} (representative of the series Ln {sub 2}LiOsO{sub 6} (Ln=La, Pr, Nd, Sm) consisting of OsO{sub 6} octahedra (striped) and LiO{sub 6} octahedra (gray). Praseodymium cations are shown as gray spheres and oxygen atoms as black spheres.

  2. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth.

    PubMed

    Yang, Bin; Keum, Jong; Ovchinnikova, Olga S; Belianinov, Alex; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

    2016-04-20

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films, a major unresolved question is the competition between multiple halide species (e.g., I(-), Cl(-), Br(-)) in the formation of the mixed-halide perovskite crystals. Whether Cl(-) ions are successfully incorporated into the perovskite crystal structure or, alternatively, where they are located is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br(-) or Cl(-) ions can promote crystal growth, yet reactive I(-) ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl(-) ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performing and cost-effective optoelectronic devices. PMID:26931634

  3. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    DOE PAGES

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher; Geohegan, David B.; Xiao, Kai

    2016-03-01

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films a major unresolved question is the competition between multiple halide species (e.g. I-, Cl-, Br-) in the formation of the mixed halide perovskite crystals. Whether Cl- ions are successfully incorporated into the perovskite crystal structure or alternatively, where they are located, is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br- or Cl- ions can promote crystal growth, yet reactive I- ionsmore » prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl- ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites, and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performance and cost-effective optoelectronic devices.« less

  4. Structure and high-temperature properties of the (Sr,Ca,Y)(Co, Mn)O{sub 3-y} perovskites - perspective cathode materials for IT-SOFC

    SciTech Connect

    Napolsky, Ph.S.; Drozhzhin, O.A.; Istomin, S.Ya.; Kazakov, S.M.; Antipov, E.V.; Galeeva, A.V.; Gippius, A.A.; Svensson, G.; Abakumov, A.M.; Van Tendeloo, G.

    2012-08-15

    Oxygen deficient perovskites Sr{sub 0.75}Y{sub 0.25}Co{sub 1-x}Mn{sub x}O{sub 3-y}, x=0.5 and 0.75, were prepared by using the citrate route at 1373-1573 K for 48 h. The cubic Pm-3m perovskite structure for x=0.5 was confirmed by electron diffraction study and refined using neutron powder diffraction (NPD) data. For x=0.75, the superstructure corresponding to a={radical}(2) Multiplication-Sign a{sub per}, b=2 Multiplication-Sign a{sub per}, c={radical}(2) Multiplication-Sign a{sub per} (a{sup 0}b{sup -}b{sup -} tilt system, space group Imma) was revealed by electron diffraction. The solid solution Sr{sub 0.75-x}Ca{sub x}Y{sub 0.25}Co{sub 0.25}Mn{sub 0.75}O{sub 3-y}, 0.1{<=}x{<=}0.6 and compound Ca{sub 0.75}Y{sub 0.25}Mn{sub 0.85}Co{sub 0.15}O{sub 2.92} were prepared in air at 1573 K for 48 h. The crystal structure of Ca{sub 0.75}Y{sub 0.25}Mn{sub 0.85}Co{sub 0.15}O{sub 2.92} was refined using NPD data (S.G. Pnma, a=5.36595(4), b=7.5091(6), c=5.2992(4) A, R{sub p}=0.057, R{sub wp}=0.056, {chi}{sup 2}=4.26). High-temperature thermal expansion properties of the prepared compounds were studied in air using both dilatometry and high-temperature X-ray powder diffraction data (HTXRPD). They expanding non-linearly at 298-1073 K due to the loss of oxygen at high temperatures. Calculated average thermal expansion coefficients (TECs) for Sr{sub 0.75}Y{sub 0.25}Co{sub 1-x}Mn{sub x}O{sub 3-y}, x=0.5, 0.75 and Ca{sub 0.75}Y{sub 0.25}Mn{sub 0.85}Co{sub 0.15}O{sub 2.92(1)} are 15.5, 15.1, and 13.8 ppm K{sup -1}, respectively. Anisotropy of the thermal expansion along different unit cell axes was observed for Sr{sub 0.15}Ca{sub 0.6}Y{sub 0.25}Co{sub 0.25}Mn{sub 0.75}O{sub 3-y} and Ca{sub 0.75}Y{sub 0.25}Mn{sub 0.85}Co{sub 0.15}O{sub 2.92}. Conductivity of Sr{sub 0.75}Y{sub 0.25}Co{sub 1-x}Mn{sub x}O{sub 3-y}, x=0.5 and 0.75 increases with the temperature reaching 110 S/cm for x=0.5 and 44 S/cm for x=0.75 at 1173 K. Samples of Sr{sub 0.75-x}Ca{sub x}Y{sub 0.25}Co{sub 0.25}Mn{sub 0

  5. Multiferroicity in Perovskite Manganite Superlattice

    NASA Astrophysics Data System (ADS)

    Tao, Yong-Mei; Jiang, Xue-Fan; Liu, Jun-Ming

    2016-08-01

    Multiferroic properties of short period perovskite type manganite superlattice ((R1MnO3)n/(R2MnO3)n (n=1,2,3)) are considered within the framework of classical Heisenberg model using Monte Carlo simulation. Our result revealed the interesting behaviors in Mn spins structure in superlattice. Apart from simple plane spin cycloid structure which is shown in all manganites including bulk, film, and superlattice here in low temperature, a non-coplanar spiral spin structure is exhibited in a certain temperature range when n equals 1, 2 or 3. Specific heat, spin-helicity vector, spin correlation function, spin-helicity correlation function, and spin configuration are calculated to confirm this non-coplanar spiral spin structure. These results are associated with the competition among exchange interaction, magnetic anisotropy, and Dzyaloshinskii-Moriya interaction. Supported by the National Natural Science Foundation of China (NSFC) under Grant No. 11447136

  6. Perovskite photonic sources

    NASA Astrophysics Data System (ADS)

    Sutherland, Brandon R.; Sargent, Edward H.

    2016-05-01

    The field of solution-processed semiconductors has made great strides; however, it has yet to enable electrically driven lasers. To achieve this goal, improved materials are required that combine efficient (>50% quantum yield) radiative recombination under high injection, large and balanced charge-carrier mobilities in excess of 10 cm2 V-1 s-1, free-carrier densities greater than 1017 cm-3 and gain coefficients exceeding 104 cm-1. Solid-state perovskites are -- in addition to galvanizing the field of solar electricity -- showing great promise in photonic sources, and may be the answer to realizing solution-cast laser diodes. Here, we discuss the properties of perovskites that benefit light emission, review recent progress in perovskite electroluminescent diodes and optically pumped lasers, and examine the remaining challenges in achieving continuous-wave and electrically driven lasing.

  7. 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.

  8. Modeling of optical losses in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Taghavi, M. Javad; Houshmand, Mohammad; Zandi, M. Hossein; Gorji, Nima E.

    2016-09-01

    The optical losses within the structure of hybrid perovskite solar cells are investigated using only the optical properties of each layer e.g. refractive index and extinction coefficient. This model allows calculating the transmission/reflection rates at the interfaces and absorption loss within any layer. Then, the short circuit current density and loss percentage are calculated versus the perovskite and TiO2 thicknesses from 50 nm to 150 nm. To make our calculations closer to reality, we extracted the optical properties of each device component from the literature reports on glass/TCO/TiO2/perovskite/metal. The simulations were fitted with the experimental results of some relevant references. Our simulations show that ITO transmits the light better than SnO2 as the TCO front electrode, and the light reflection at both sides of the perovskite layer, e.g. at TiO2/perovskite and perovskite/Spiro-OMeTAD, is lower than 25%. The light interference and multiple reflections have been accounted in our calculations and finally we showed that a thicker TiO2 and perovskite cause more optical loss in current density due to stronger absorption.

  9. Perovskite Materials for Light-Emitting Diodes and Lasers.

    PubMed

    Veldhuis, Sjoerd A; Boix, Pablo P; Yantara, Natalia; Li, Mingjie; Sum, Tze Chien; Mathews, Nripan; Mhaisalkar, Subodh G

    2016-08-01

    Organic-inorganic hybrid perovskites have cemented their position as an exceptional class of optoelectronic materials thanks to record photovoltaic efficiencies of 22.1%, as well as promising demonstrations of light-emitting diodes, lasers, and light-emitting transistors. Perovskite materials with photoluminescence quantum yields close to 100% and perovskite light-emitting diodes with external quantum efficiencies of 8% and current efficiencies of 43 cd A(-1) have been achieved. Although perovskite light-emitting devices are yet to become industrially relevant, in merely two years these devices have achieved the brightness and efficiencies that organic light-emitting diodes accomplished in two decades. Further advances will rely decisively on the multitude of compositional, structural variants that enable the formation of lower-dimensionality layered and three-dimensional perovskites, nanostructures, charge-transport materials, and device processing with architectural innovations. Here, the rapid advancements in perovskite light-emitting devices and lasers are reviewed. The key challenges in materials development, device fabrication, operational stability are addressed, and an outlook is presented that will address market viability of perovskite light-emitting devices.

  10. Perovskite Materials for Light-Emitting Diodes and Lasers.

    PubMed

    Veldhuis, Sjoerd A; Boix, Pablo P; Yantara, Natalia; Li, Mingjie; Sum, Tze Chien; Mathews, Nripan; Mhaisalkar, Subodh G

    2016-08-01

    Organic-inorganic hybrid perovskites have cemented their position as an exceptional class of optoelectronic materials thanks to record photovoltaic efficiencies of 22.1%, as well as promising demonstrations of light-emitting diodes, lasers, and light-emitting transistors. Perovskite materials with photoluminescence quantum yields close to 100% and perovskite light-emitting diodes with external quantum efficiencies of 8% and current efficiencies of 43 cd A(-1) have been achieved. Although perovskite light-emitting devices are yet to become industrially relevant, in merely two years these devices have achieved the brightness and efficiencies that organic light-emitting diodes accomplished in two decades. Further advances will rely decisively on the multitude of compositional, structural variants that enable the formation of lower-dimensionality layered and three-dimensional perovskites, nanostructures, charge-transport materials, and device processing with architectural innovations. Here, the rapid advancements in perovskite light-emitting devices and lasers are reviewed. The key challenges in materials development, device fabrication, operational stability are addressed, and an outlook is presented that will address market viability of perovskite light-emitting devices. PMID:27214091

  11. Lanthanide contraction effect on crystal structures, magnetic, and dielectric properties in ordered double perovskites LnPbCoSbO{sub 6} (Ln = La, Pr, Nd)

    SciTech Connect

    Han, L.; Yao, C. G.; Meng, J. L.; Liang, Q. S.; Bai, Y. J.; Meng, F. Z.; Liu, X. J. E-mail: jmeng@ciac.ac.cn; Wu, X. J.; Meng, J. E-mail: jmeng@ciac.ac.cn

    2014-04-28

    The crystal structures, magnetic, and dielectric properties for the ordered double perovskites LnPbCoSbO{sub 6} (Ln = La, Pr, Nd) have been investigated. The crystal structure has been solved by Rietveld refinements of X-ray diffraction data in the monoclinic space group P2{sub 1}/n (No. 14). The Co{sup 2+} and Sb{sup 5+} ions are almost fully ordered over the B-site, and the octahedral framework displays significant tilting distortion according to the Glazer's tilt system a{sup –}a{sup –}c{sup +}. As the result of lanthanide contraction from La{sup 3+} to Nd{sup 3+}, the B-site sublattice distortions become stronger accompanying with the reduction of the tolerance factor and coordination number. The magnetization measurements show an antiferromagnetic ordering with large effective magnetic moments (μ{sub eff}) suggesting that the orbital component is significant. The maximum values of isothermal magnetization increase with the decrease in radii of rare earth ions, which is attributed to the weakening of antiferromagnetic interaction via Co{sup 2+}–O–Sb{sup 5+}–O–Co{sup 2+} paths. The dielectric constants present frequency dependence and monotonically decrease with the ionic radii reduction from La{sup 3+} to Nd{sup 3+} due to the suppression of electron transfer. These results indicate that the magnetic and dielectric properties can be tuned by controlling the degree of lattice distortion, which is realized by introducing different Ln{sup 3+} ions at the A-site.

  12. Two-Dimensional Organic-Inorganic Hybrid Perovskite Photonic Films.

    PubMed

    Meng, Ke; Gao, Shanshan; Wu, Longlong; Wang, Geng; Liu, Xin; Chen, Gang; Liu, Zhou; Chen, Gang

    2016-07-13

    Organic-inorganic hybrid perovskites have created enormous expectations for low-cost and high-performance optoelectronic devices. In prospect, future advancements may derive from reaping novel electrical and optical properties beyond pristine perovskites through microscopic structure design and engineering. Herein, we report the successful preparation of two-dimensional inverse-opal perovskite (IOP) photonic films, featuring unique nanostructures and vivid colors. Further compositional and structural managements promise optical property and energy level tunability of the IOP films. They are further functionalized in solar cells, resulting in colorful devices with respectable power conversion efficiency. Such concept has not been previously applied for perovskite-based solar cells, which could open a route for more versatile optoelectronic devices.

  13. Two-Dimensional Organic-Inorganic Hybrid Perovskite Photonic Films.

    PubMed

    Meng, Ke; Gao, Shanshan; Wu, Longlong; Wang, Geng; Liu, Xin; Chen, Gang; Liu, Zhou; Chen, Gang

    2016-07-13

    Organic-inorganic hybrid perovskites have created enormous expectations for low-cost and high-performance optoelectronic devices. In prospect, future advancements may derive from reaping novel electrical and optical properties beyond pristine perovskites through microscopic structure design and engineering. Herein, we report the successful preparation of two-dimensional inverse-opal perovskite (IOP) photonic films, featuring unique nanostructures and vivid colors. Further compositional and structural managements promise optical property and energy level tunability of the IOP films. They are further functionalized in solar cells, resulting in colorful devices with respectable power conversion efficiency. Such concept has not been previously applied for perovskite-based solar cells, which could open a route for more versatile optoelectronic devices. PMID:27267266

  14. Ultrathin efficient perovskite solar cells employing a periodic structure of a composite hole conductor for elevated plasmonic light harvesting and hole collection.

    PubMed

    Long, Mingzhu; Chen, Zefeng; Zhang, Tiankai; Xiao, Yubin; Zeng, Xiaoliang; Chen, Jian; Yan, Keyou; Xu, Jianbin

    2016-03-28

    We developed a molecule/polymer composite hole transporting material (HTM) with a periodic microstructure for morphology replication of a corrugated Au electrode, which in combination plays a dual role in the optical and electronic enhancement of high performance perovskite solar cells (PSCs). The electro-optics revealed that perovskite couldn't readily extinct the red light even though the thickness increased to 370 nm, but we found that the quasi periodic microstructure composite (PMC) HTM in combination with the conformal Au electrode could promote the absorption through the enhanced cavity effects, leading to comparable absorption even using much thinner perovskite (240 nm). We identified that the cavity was the combination of Fabry-Pérot interferometer and surface plasmonic resonance, with light harvesting enhancement through surface plasmon polariton or waveguide modes that propagate in the plane of the perovskite layer. On the other hand, the PMC HTM increased hole conductivity by one order of magnitude with respect to standard spiro-OMeTAD HTM due to molecular packing and self-assembly, embodying traceable hole mobility and density elevation up to 3 times, and thus the hysteresis was greatly avoided. Owing to dual optical and electronic enhancement, the PMC PSC afforded high efficiency PSC using as thin as 240 nm perovskite layer, delivering a V(oc) of 1.05 V, J(sc) of 22.9 mA cm(-2), FF of 0.736, and efficiency amounting to 17.7% PCE, the highest efficiency with ultrathin perovskite layer. PMID:26377231

  15. Magnetic and electrical properties of quadruple perovskites with 12 layer structures Ba{sub 4}LnM{sub 3}O{sub 12} (Ln=rare earths; M=Ru, Ir): The role of metal-metal bonding in perovskite-related oxides

    SciTech Connect

    Shimoda, Yuki; Doi, Yoshihiro; Wakeshima, Makoto; Hinatsu, Yukio

    2010-09-15

    Structures and magnetic and electrical properties of quadruple perovskites containing rare earths Ba{sub 4}LnM{sub 3}O{sub 12} (Ln=rare earths; M=Ru, Ir) were investigated. They crystallize in the 12L-perovskite-type structure. Three MO{sub 6} octahedra are connected to each other by face-sharing and form a M{sub 3}O{sub 12} trimer. The M{sub 3}O{sub 12} trimers and LnO{sub 6} octahedra are alternately linked by corner-sharing, forming the perovskite-type structure with 12 layers. For Ln=Ce, Pr, and Tb, both the Ln and M ions are in the tetravalent state (Ba{sub 4}Ln{sup 4+}M{sup 4+}{sub 3}O{sub 12}), and for other Ln ions, Ln ions are in the trivalent state and the mean oxidation state of M ions is +4.33 (Ba{sub 4}Ln{sup 3+}M{sup 4.33+}{sub 3}O{sub 12}). All the Ba{sub 4}Ln{sup 3+}Ru{sup 4.33+}{sub 3}O{sub 12} compounds show magnetic ordering at low temperatures, while any of the corresponding iridium-containing compounds Ba{sub 4}Ln{sup 3+}Ir{sup 4.33+}{sub 3}O{sub 12} is paramagnetic down to 1.8 K. Ba{sub 4}Ce{sup 4+}Ir{sup 4+}{sub 3}O{sub 12} orders antiferromagnetically at 10.5 K, while the corresponding ruthenium-containing compound Ba{sub 4}Ce{sup 4+}Ru{sup 4+}{sub 3}O{sub 12} is paramagnetic. These magnetic results were well understood by the magnetic behavior of M{sub 3}O{sub 12}. The effective magnetic moments and the entropy change for the magnetic ordering show that the trimers Ru{sup 4.33+}{sub 3}O{sub 12} and Ir{sup 4+}{sub 3}O{sub 12} have the S=1/2 ground state, and in other cases there is no magnetic contribution from the trimers Ru{sup 4+}{sub 3}O{sub 12} or Ir{sup 4.33+}{sub 3}O{sub 12}. Measurements of the electrical resistivity of Ba{sub 4}LnM{sub 3}O{sub 12} and its analysis show that these compounds demonstrate two-dimensional Mott-variable range hopping behavior. - Graphical abstract: Structures and magnetic and electrical properties of quadruple perovskites containing rare earths Ba{sub 4}LnM{sub 3}O{sub 12} (Ln=rare earths; M = Ru, Ir

  16. Research Update: Physical and electrical characteristics of lead halide perovskites for solar cell applications

    NASA Astrophysics Data System (ADS)

    Bretschneider, Simon A.; Weickert, Jonas; Dorman, James A.; Schmidt-Mende, Lukas

    2014-04-01

    The field of thin-film photovoltaics has been recently enriched by the introduction of lead halide perovskites as absorber materials, which allow low-cost synthesis of solar cells with efficiencies exceeding 16%. The exact impact of the perovskite crystal structure and composition on the optoelectronic properties of the material are not fully understood. Our progress report highlights the knowledge gained about lead halide perovskites with a focus on physical and optoelectronic properties. We discuss the crystal and band structure of perovskite materials currently implemented in solar cells and the impact of the crystal properties on ferroelectricity, ambipolarity, and the properties of excitons.

  17. Structure and high-temperature properties of the (Sr,Ca,Y)(Co, Mn)O3-y perovskites — perspective cathode materials for IT-SOFC

    NASA Astrophysics Data System (ADS)

    Napolsky, Ph. S.; Drozhzhin, O. A.; Istomin, S. Ya.; Kazakov, S. M.; Antipov, E. V.; Galeeva, A. V.; Gippius, A. A.; Svensson, G.; Abakumov, A. M.; Van Tendeloo, G.

    2012-08-01

    Oxygen deficient perovskites Sr0.75Y0.25Co1-xMnxO3-y, x=0.5 and 0.75, were prepared by using the citrate route at 1373-1573 K for 48 h. The cubic Pm-3m perovskite structure for x=0.5 was confirmed by electron diffraction study and refined using neutron powder diffraction (NPD) data. For x=0.75, the superstructure corresponding to a=√{2}×aper, b=2×aper, c=√{2}×aper (a0b-b- tilt system, space group Imma) was revealed by electron diffraction. The solid solution Sr0.75-xCaxY0.25Co0.25Mn0.75O3-y, 0.1≤x≤0.6 and compound Ca0.75Y0.25Mn0.85Co0.15O2.92 were prepared in air at 1573 K for 48 h. The crystal structure of Ca0.75Y0.25Mn0.85Co0.15O2.92 was refined using NPD data (S.G. Pnma, a=5.36595(4), b=7.5091(6), c=5.2992(4) Å, Rp=0.057, Rwp=0.056, χ2=4.26). High-temperature thermal expansion properties of the prepared compounds were studied in air using both dilatometry and high-temperature X-ray powder diffraction data (HTXRPD). They expanding non-linearly at 298-1073 K due to the loss of oxygen at high temperatures. Calculated average thermal expansion coefficients (TECs) for Sr0.75Y0.25Co1-xMnxO3-y, x=0.5, 0.75 and Ca0.75Y0.25Mn0.85Co0.15O2.92(1) are 15.5, 15.1, and 13.8 ppm K-1, respectively. Anisotropy of the thermal expansion along different unit cell axes was observed for Sr0.15Ca0.6Y0.25Co0.25Mn0.75O3-y and Ca0.75Y0.25Mn0.85Co0.15O2.92. Conductivity of Sr0.75Y0.25Co1-xMnxO3-y, x=0.5 and 0.75 increases with the temperature reaching 110 S/cm for x=0.5 and 44 S/cm for x=0.75 at 1173 K. Samples of Sr0.75-xCaxY0.25Co0.25Mn0.75O3-y, 0.1≤y≤0.6 were found to be n-type conductors at room temperature with the similar temperature dependence of the conductivity and demonstrated the increase of the σ value from ˜1 to ˜50 S/cm as the temperature increases from 300 to 1173 K. Their conductivity is described in terms of the small polaron charge transport with the activation energy (Ep) increasing from 340 to 430 meV with an increase of the calcium content from x=0

  18. Structure and redox properties of perovskite Y0.9Sr0.1Cr1-xFexO3-δ

    NASA Astrophysics Data System (ADS)

    Xu, Dandan; Bu, Yunfei; Tan, Wenyi; Zhong, Qin

    2013-03-01

    The aim of this paper is to examine the feasibility of Y0.9Sr0.1Cr1-xFexO3-δ for potential use as anode materials in solid oxide fuel cells (SOFCs) fed with fuel gas containing H2S, as well as other electrochemical devise. Y0.9Sr0.1Cr1-xFexO3-δ (x = 0.1, 0.3, 0.5) were synthesized by gel combustion method and had single-phase orthorhombic perovskite structure. These materials were all stable in reducing atmosphere (10%, v/v H2/N2) up to 800 °C. By the comparison of the O 1s peaks assigned to Y0.9Sr0.1Cr1-xFexO3-δ before and after reduction in H2/N2, lower content of lattice oxygen and higher content of adsorbed oxygen were observed for Y0.9Sr0.1Cr0.9Fe0.1O3-δ, while others appeared opposite results. This phenomenon suggested that reduced Y0.9Sr0.1Cr0.9Fe0.1O3-δ could capture oxygen when exposure to air, which is essential for anode materials. Moreover, Y0.9Sr0.1Cr0.9Fe0.1O3-δ maintained good chemical stability under H2S-containing atmosphere through XRD and FT-IR analysis. So Y0.9Sr0.1Cr0.9Fe0.1O3-δ was suggested as a promising anode material for SOFCs fed with fuel gas containing H2S.

  19. Structural, magnetotransport and morphological studies of Sb-doped La2/3Ba1/3MnO3 ceramic perovskites

    NASA Astrophysics Data System (ADS)

    Sen, Vikram; Panwar, Neeraj; Bhalla, G. L.; Agarwal, S. K.

    2007-09-01

    We report here the structural, magnetotransport and morphological studies of Sb-doped La2/3Ba1/3Mn1-xSbxO3 perovskite manganites. Pristine material La2/3Ba1/3MnO3 (LBMO) shows two insulator metal (I M) transitions in the electrical resistivity temperature (ρ T) behavior. While the higher temperature transition (TP1) at ˜340 K is reminiscent of the usual I M transition in manganites, the lower temperature transition (TP2) at ˜250 K has been ascribed to the grain boundary (GB) effects arising out of the ionic size mismatch between the ions present at the rare-earth site (La3+ and Ba2+). With Sb-doping TP1 shifts to lower temperatures while TP2 remains invariant up to 3% and shifts to lower temperature for 5%. Room temperature electrical resistivity and the peak values also increase successively with Sb-doping. Scanning electron micrographs of the samples exhibit a gradual increase in their grain sizes with Sb indicating a gradual decrease in the GB density. Shift of TP1 with doping is explained on the basis of a competition between double-exchange and super-exchange mechanisms. The overall electrical resistivity increases and the shift in the electrical resistivity hump (TP2) with Sb-doping is found related to be gradually decreasing GB density and the ensuing lattice strain increase at the GBs. The intrinsic magnetoresistance (MR) gets suppressed and extrinsic MR gets enhanced with Sb-doping. At T>TP1, the electrical resistivity is found to follow the adiabatic polaron hopping model whereas the electron magnon scattering is found to dominate in the metallic regime (T

  20. Recent advances of lanthanum-based perovskite oxides for catalysis

    SciTech Connect

    Zhu, Huiyuan; Zhang, Pengfei; Dai, Sheng

    2015-09-21

    There is a need to reduce the use of noble metal elements especially in the field of catalysis, where noble metals are ubiquitously applied. To this end, perovskite oxides, an important class of mixed oxide, have been attracting increasing attention for decades as potential replacements. Benefiting from the extraordinary tunability of their compositions and structures, perovskite oxides can be rationally tailored and equipped with targeted physical and chemical properties e.g. redox behavior, oxygen mobility, and ion conductivity for enhanced catalysis. Recently, the development of highly efficient perovskite oxide catalysts has been extensively studied. This review article summarizes the recent development of lanthanum-based perovskite oxides as advanced catalysts for both energy conversion applications and traditional heterogeneous reactions.

  1. Recent advances of lanthanum-based perovskite oxides for catalysis

    DOE PAGES

    Zhu, Huiyuan; Zhang, Pengfei; Dai, Sheng

    2015-09-21

    There is a need to reduce the use of noble metal elements especially in the field of catalysis, where noble metals are ubiquitously applied. To this end, perovskite oxides, an important class of mixed oxide, have been attracting increasing attention for decades as potential replacements. Benefiting from the extraordinary tunability of their compositions and structures, perovskite oxides can be rationally tailored and equipped with targeted physical and chemical properties e.g. redox behavior, oxygen mobility, and ion conductivity for enhanced catalysis. Recently, the development of highly efficient perovskite oxide catalysts has been extensively studied. This review article summarizes the recent developmentmore » of lanthanum-based perovskite oxides as advanced catalysts for both energy conversion applications and traditional heterogeneous reactions.« less

  2. High Performance Perovskite Solar Cells

    PubMed Central

    Tong, Xin; Lin, Feng; Wu, Jiang

    2015-01-01

    Perovskite solar cells fabricated from organometal halide light harvesters have captured significant attention due to their tremendously low device costs as well as unprecedented rapid progress on power conversion efficiency (PCE). A certified PCE of 20.1% was achieved in late 2014 following the first study of long‐term stable all‐solid‐state perovskite solar cell with a PCE of 9.7% in 2012, showing their promising potential towards future cost‐effective and high performance solar cells. Here, notable achievements of primary device configuration involving perovskite layer, hole‐transporting materials (HTMs) and electron‐transporting materials (ETMs) are reviewed. Numerous strategies for enhancing photovoltaic parameters of perovskite solar cells, including morphology and crystallization control of perovskite layer, HTMs design and ETMs modifications are discussed in detail. In addition, perovskite solar cells outside of HTMs and ETMs are mentioned as well, providing guidelines for further simplification of device processing and hence cost reduction.

  3. 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. PMID:27432518

  4. Chlorine Insertion Promoting Iron Reduction in Ba-Fe Hexagonal Perovskites: Effect on the Structural and Magnetic Properties.

    PubMed

    Serrador, Laura; Hernando, María; Martínez, José L; González-Calbet, José M; Varela, Aurea; García-García, F Javier; Parras, Marina

    2016-06-20

    BaFeCl0.13(2)O2.48(2) has been synthesized and studied. A proper tuning of the synthetic route has been designed to stabilize this compound as a single phase. The thermal stability and evolution, along with the magnetic and structural properties are reported here. The crystal structure has been refined from neutron powder diffraction data, and it is of the type (hhchc)2-10H. It is stable up to a temperature of 900 °C, where the composition reads BaFeCl0.13(2)O2.34(2). The study by electron microscopy shows that the crystal structure suffers no changes in the whole BaFeCl0.13(1)O3-y (2.34 ≤ 3 - y ≤ 2.48) compositional range. Refinement of the magnetic structure shows that the Fe is antiferromagneticaly ordered, with the magnetic moment parallel to the ab plane of the hexagonal structure. At higher temperature, a nonreversible phase transition into a (hchc)-4H structure type takes place with overall composition BaFeCl0.13(1)O2.26(1). Microstructural characterization shows that, in some crystals, this phase intergrows with a seemingly cubic related phase. Differences between these two crystalline phases reside in the chlorine content, which keeps constant through the phase transition for the former and disappears for the latter. PMID:27276508

  5. Chlorine Insertion Promoting Iron Reduction in Ba-Fe Hexagonal Perovskites: Effect on the Structural and Magnetic Properties.

    PubMed

    Serrador, Laura; Hernando, María; Martínez, José L; González-Calbet, José M; Varela, Aurea; García-García, F Javier; Parras, Marina

    2016-06-20

    BaFeCl0.13(2)O2.48(2) has been synthesized and studied. A proper tuning of the synthetic route has been designed to stabilize this compound as a single phase. The thermal stability and evolution, along with the magnetic and structural properties are reported here. The crystal structure has been refined from neutron powder diffraction data, and it is of the type (hhchc)2-10H. It is stable up to a temperature of 900 °C, where the composition reads BaFeCl0.13(2)O2.34(2). The study by electron microscopy shows that the crystal structure suffers no changes in the whole BaFeCl0.13(1)O3-y (2.34 ≤ 3 - y ≤ 2.48) compositional range. Refinement of the magnetic structure shows that the Fe is antiferromagneticaly ordered, with the magnetic moment parallel to the ab plane of the hexagonal structure. At higher temperature, a nonreversible phase transition into a (hchc)-4H structure type takes place with overall composition BaFeCl0.13(1)O2.26(1). Microstructural characterization shows that, in some crystals, this phase intergrows with a seemingly cubic related phase. Differences between these two crystalline phases reside in the chlorine content, which keeps constant through the phase transition for the former and disappears for the latter.

  6. Laser Crystallization of Organic-Inorganic Hybrid Perovskite Solar Cells.

    PubMed

    Jeon, Taewoo; Jin, Hyeong Min; Lee, Seung Hyun; Lee, Ju Min; Park, Hyung Il; Kim, Mi Kyung; Lee, Keon Jae; Shin, Byungha; Kim, Sang Ouk

    2016-08-23

    Organic-inorganic hybrid perovskites attract enormous research interest for next generation solar energy harvest. Synergistic crystalline structures comprising organic and inorganic components enable solution processing of perovskite films. A reliable crystallization method for perovskites, compatible with fast continuous process over large-area flexible substrates, is crucial for high performance solar cell production. Here, we present laser crystallization of hybrid perovskite solar cells using near-infrared (NIR) laser (λ = 1064 nm). Crystalline morphology of CH3NH3PbI3 (MAPbI3) perovskite films are widely controllable with laser irradiation condition while maintaining film uniformity. Photothermal heating effectively assisted by interfacial photoconversion layers is critical for phase transformation without beam damage of multilayered device structures. Notably, laser crystallization attains higher device performances than conventional thermal annealing. Fast laser crystallization with manufacture level scan rate (1 m min(-1)) demonstrates inverted-type perovskite solar cells with 11.3 and 8.0% efficiencies on typical glass and flexible polymer substrates, respectively, without rigorous device optimization.

  7. Laser Crystallization of Organic-Inorganic Hybrid Perovskite Solar Cells.

    PubMed

    Jeon, Taewoo; Jin, Hyeong Min; Lee, Seung Hyun; Lee, Ju Min; Park, Hyung Il; Kim, Mi Kyung; Lee, Keon Jae; Shin, Byungha; Kim, Sang Ouk

    2016-08-23

    Organic-inorganic hybrid perovskites attract enormous research interest for next generation solar energy harvest. Synergistic crystalline structures comprising organic and inorganic components enable solution processing of perovskite films. A reliable crystallization method for perovskites, compatible with fast continuous process over large-area flexible substrates, is crucial for high performance solar cell production. Here, we present laser crystallization of hybrid perovskite solar cells using near-infrared (NIR) laser (λ = 1064 nm). Crystalline morphology of CH3NH3PbI3 (MAPbI3) perovskite films are widely controllable with laser irradiation condition while maintaining film uniformity. Photothermal heating effectively assisted by interfacial photoconversion layers is critical for phase transformation without beam damage of multilayered device structures. Notably, laser crystallization attains higher device performances than conventional thermal annealing. Fast laser crystallization with manufacture level scan rate (1 m min(-1)) demonstrates inverted-type perovskite solar cells with 11.3 and 8.0% efficiencies on typical glass and flexible polymer substrates, respectively, without rigorous device optimization. PMID:27377145

  8. Synthesis, Crystal Structure, and Magnetic Properties of Sr1.31Co0.63Mn0.37O3: A Derivative of the Incommensurate Composite Hexagonal Perovskite Structure

    SciTech Connect

    Mandal,T.; Abakumov, A.; Hadermann, J.; Van Tendeloo, G.; Croft, M.; Greenblatt, M.

    2007-01-01

    We report the synthesis, structural investigation, and magnetic property studies of Sr1.31Co0.63Mn0.37O3 that adopts an incommensurate composite hexagonal perovskite-related structure. The crystal structure has been solved using a (3 + 1)-dimensional superspace approach from powder X-ray and neutron diffraction data (SSG Rm(00 )0s, a = 9.5548(1) Angstroms, c = 2.5599(1) Angstroms, q = 0.65581(4)c*, RB = 0.041, RP = 0.059). The structure consists of face-sharing chains of octahedra and trigonal prisms, wherein the trigonal prismatic sites are preferentially occupied by Co with some cation disorder. A combination of electron diffraction and high-resolution electron microscopic analysis has demonstrated that the compound possesses a complicated microstructure related to the formation of domains with slightly different lengths of the modulation vector. X-ray absorption near-edge spectroscopic (XAS) studies clearly indicate the presence of Mn in the 4+ and Co in the 3+ oxidation state. While the magnetic susceptibility data indicates the presence of antiferromagnetic correlations in the system, the calculation of effective paramagnetic moment ({mu}cal = 3.561 {mu}B), assuming the metal oxidation states as obtained from XAS and the cation distribution as obtained from neutron refinement, is in agreement with the value obtained experimentally ({mu}exp = 3.676 {mu}B).

  9. Synthesis, structure and magnetic properties of La{sub 3}Co{sub 2}SbO{sub 9}: A double perovskite with competing antiferromagnetic and ferromagnetic interactions

    SciTech Connect

    Franco, D.G.; Fuertes, V.C.; Blanco, M.C.; Fernandez-Diaz, M.T.; Sanchez, R.D.; Carbonio, R.E.

    2012-10-15

    The synthesis, structural characterization, and magnetic properties of La{sub 3}Co{sub 2}SbO{sub 9} double perovskite are reported. The crystal structure has been refined by X-ray and neutron powder diffraction data in the monoclinic space group P2{sub 1}/n. Co{sup 2+} and Sb{sup 5+} have the maximum order allowed for the La{sub 3}Co{sub 2}SbO{sub 9} stoichiometry. Rietveld refinements of powder neutron diffraction data show that at room temperature the cell parameters are a=5.6274(2) A, b=5.6842(2) A, c=7.9748(2) A and {beta}=89.999(3) Degree-Sign . Magnetization measurements indicate the presence of ferromagnetic correlations with T{sub C}=55 K attributed to the exchange interactions for non-linear Co{sup 2+}-O-Sb{sup 5+}-O-Co{sup 2+} paths. The effective magnetic moment obtained experimentally is {mu}{sub exp}=4.38 {mu}{sub B} (per mol Co{sup 2+}), between the theoretical one for spin only (3.87 {mu}{sub B}) and spin-orbit value (6.63 {mu}{sub B}), indicating partially unquenched contribution. The low magnetization value at high magnetic field and low temperature (1 {mu}{sub B}/f.u., 5 T and 5 K) and the difference between ZFC and FC magnetization curves (at 5 kOe) indicate that the ferromagnetism do not reach a long range order and that the material has an important magnetic frustration. - Graphical abstract: Co-O-Co (Yellow octahedra only) rich zones (antiferromagnetic) are in contact with Co-O-Sb-O-Co (Red and yellow octahedra) rich zones (Ferromagnetic) to give the peculiar magnetic properties, as a consequence, a complex hysteresis loop can be observed composed by a main and irreversible curve in all the measured range, superimposed with a ferromagnetic component at low fields. Highlights: Black-Right-Pointing-Pointer La{sub 3}Co{sub 2}SbO{sub 9} has small Goldschmidt Tolerance Factor (t) due to the small size of La{sup 3+}. Black-Right-Pointing-Pointer Small t determines an angle for the path Co{sup 2+}-O-Sb{sup 5+}-O-Co{sup 2+} of 153 Degree-Sign . Black

  10. Structural and magnetic properties of the La{sub 2−x}Ca{sub x}CoIrO{sub 6} double perovskite series

    SciTech Connect

    Coutrim, L.T.; Freitas, D.C.; Fontes, M.B.; Baggio-Saitovitch, E.; Bittar, E.M.; Granado, E.; Pagliuso, P.G.; Bufaiçal, L.

    2015-01-15

    Polycrystalline samples of the series La{sub 2−x}Ca{sub x}CoIrO{sub 6} (0≤x≤1.2) have been synthesized and its structural and magnetic properties were investigated using experiments of X-ray powder diffraction, temperature dependent magnetic susceptibility and magnetization as a function of applied magnetic field. All grown polycrystalline compounds form in a monoclinic structure (space group P2{sub 1}/n) with a partially ordered distribution of transition metal cations Co/Ir over the six-coordinate sites. Our results indicate variation of the magnetic interactions between Co and Ir magnetic sublattices possibly due to valence changes of the transition metals, induced by doping. The undoped La{sub 2}CoIrO{sub 6} presents magnetic ordering at ∼97K, while for Ca-doped compounds a decrease of net magnetization and ordering temperatures was observed. For x=0.2 and 0.5 the emergence of a second magnetic interaction, due to the presence of high spin Co{sup 3+}, becomes evident. Interestingly, for x=0.8 the large effective magnetic moment indicates strong orbital contribution and spin-orbit coupling and/or the presence of Co{sup 4+} in high spin state. - Graphical abstract: Field cooling M vs.T curves for La{sub 2−x}Ca{sub x}CoIrO{sub 6} shows the suppression of magnetism with increasing La content. Zero field cooled curves indicate a second magnetic phase induced by the appearance of Co{sup 3+}. - Highlights: • Novel double perovskite series La{sub 2−x}Ca{sub x}CoIrO{sub 6} were synthesized by solid state reaction. • La{sup 3+} to Ca{sup 2+} substitution leads to Co valence and possibly spin state changes. • For some doped compounds, the emergence of a second magnetic phase, due to the presence of high spin Co{sup 3+}, becomes evident. • Physical properties of each compound can be well correlated to the electronic and magnetic evolution of the system.

  11. First-principles study of the structural, electronic, and magnetic properties of double perovskite Sr2FeReO6 containing various imperfections

    NASA Astrophysics Data System (ADS)

    Yan, Zhang; Li, Duan; Vincent, Ji; Ke-Wei, Xu

    2016-05-01

    The structural, electronic, and magnetic properties of double perovskite Sr2FeReO6 containing eight different imperfections of FeRe or ReFe antisites, Fe1-Re1 or Fe1-Re4 interchanges, VFe, VRe, VO or VSr vacancies have been studied by using the first-principles projector augmented wave (PAW) within generalized gradient approximation as well as taking into account the on-site Coulomb repulsive interaction (GGA+U). No obvious structural changes are observed for the imperfect Sr2FeReO6 containing FeRe or ReFe antisites, Fe1-Re1 or Fe1-Re4 interchanges, or VSr vacancy defects. However, the six (eight) nearest oxygen neighbors of the vacancy move away from (close to) VFe or VRe (VO) vacancies. The half-metallic (HM) character is maintained for the imperfect Sr2FeReO6 containing FeRe or ReFe antisites, Fe1-Re4 interchange, VFe, VO or VSr vacancies, while it vanishes when the Fe1-Re1 interchange or VRe vacancy is presented. So the Fe1-Re1 interchange and the VRe vacancy defects should be avoided to preserve the HM character of Sr2FeReO6 and thus usage in spintronic devices. In the FeRe or ReFe antisites, Fe1-Re1 or Fe1-Re4 interchanges cases, the spin moments of the Fe (Re) cations situated on Re (Fe) antisites are in an antiferromagnetic coupling with those of the Fe (Re) cations on the regular sites. In the VFe, VRe, VO, or VSr vacancies cases, a ferromagnetic coupling is obtained within each cation sublattice, while the two cation sublattices are coupled antiferromagnetically. The total magnetic moments μ tot (μ B/f.u.) of the imperfect Sr2FeReO6 containing eight different defects decrease in the sequence of VSr vacancy (3.50), VRe vacancy (3.43), FeRe antisite (2.74), VO vacancy (2.64), VFe vacancy (2.51), ReFe antisite (2.29), Fe1-Re4 interchange (1.96), Fe1-Re1 interchange (1.87), and the mechanisms of the saturation magnetization reduction have been analyzed. Project supported by the National Natural Science Foundation of China (Grant No. 51501017).

  12. Tracking the formation of methylammonium lead triiodide perovskite

    NASA Astrophysics Data System (ADS)

    Liu, Lijia; McLeod, John A.; Wang, Rongbin; Shen, Pengfei; Duhm, Steffen

    2015-08-01

    The formation mechanism of perovskite methylammonium lead triiodide (CH3NH3PbI3) was studied with in situ X-ray photoelectron spectroscopy (XPS) on successive depositions of thermally evaporated methylammonium iodide (CH3NH3I) on a lead iodide (PbI2) film. This deposition method mimics the "two-step" synthesis method commonly used in device fabrication. We find that several competing processes occur during the formation of perovskite CH3NH3PbI3. Our most important finding is that during vapour deposition of CH3NH3I onto PbI2, at least two carbon species are present in the resulting material, while only one nitrogen species is present. This suggests that CH3NH3I can dissociate during the transition to a perovskite phase, and some of the resulting molecules can be incorporated into the perovskite. The effect of partial CH3NH3 substitution with CH3 was evaluated, and electronic structure calculations show that CH3 defects would impact the photovoltaic performance in perovskite solar cells. The possibility that not all A sites in the APbI3 perovskite are occupied by CH3NH3 is therefore an important consideration when evaluating the performance of organometallic trihalide solar cells synthesized using typical approaches.

  13. Perovskite-related oxynitrides in photocatalysis.

    PubMed

    Pokrant, Simone; Maegli, Alexandra E; Chiarello, Gian Luca; Weidenkaff, Anke

    2013-01-01

    Over the last decades photocatalytic water splitting has become of increasing importance for fundamental and applied research, since the direct conversion of sunlight into chemical energy via the production of H2 has the potential to contribute to the world's energy needs without CO2 generation. One of the unsolved challenges consists of finding a highly efficient photocatalyst that is cheap, environmentally friendly, contains exclusively abundant elements, is (photo)chemically stable and absorbs visible light. Photocatalytic efficiency is closely connected to both structural properties like crystallinity, particle size and surface area and to electronic properties like the band gap and the quantum efficiency. Hence extensive control over a large parameter field is necessary to design a good photocatalyst. A material class where the structure-composition-property relations and the influence of substitution effects are well studied is the perovskite-type family of compounds. The perovskite-related oxynitrides belong to this very flexible compound family where many of the necessary characteristics for a photocatalyst are already given and some of the intrinsic properties like the band gap can be tuned within the same crystal structure by substitution. In this work we present materials' design concepts to improve the photocatalytic efficiency of a perovskite-type catalyst and describe their effects on the photocatalytic activity. PMID:23574956

  14. Organohalide Perovskites for Solar Energy Conversion.

    PubMed

    Lin, Qianqian; Armin, Ardalan; Burn, Paul L; Meredith, Paul

    2016-03-15

    Lead-based organohalide perovskites have recently emerged as arguably the most promising of all next generation thin film solar cell technologies. Power conversion efficiencies have reached 20% in less than 5 years, and their application to other optoelectronic device platforms such as photodetectors and light emitting diodes is being increasingly reported. Organohalide perovskites can be solution processed or evaporated at low temperatures to form simple thin film photojunctions, thus delivering the potential for the holy grail of high efficiency, low embedded energy, and low cost photovoltaics. The initial device-driven "perovskite fever" has more recently given way to efforts to better understand how these materials work in solar cells, and deeper elucidation of their structure-property relationships. In this Account, we focus on this element of organohalide perovskite chemistry and physics in particular examining critical electro-optical, morphological, and architectural phenomena. We first examine basic crystal and chemical structure, and how this impacts important solar-cell related properties such as the optical gap. We then turn to deeper electronic phenomena such as carrier mobilities, trap densities, and recombination dynamics, as well as examining ionic and dielectric properties and how these two types of physics impact each other. The issue of whether organohalide perovskites are predominantly nonexcitonic at room temperature is currently a matter of some debate, and we summarize the evidence for what appears to be the emerging field consensus: an exciton binding energy of order 10 meV. Having discussed the important basic chemistry and physics we turn to more device-related considerations including processing, morphology, architecture, thin film electro-optics and interfacial energetics. These phenomena directly impact solar cell performance parameters such as open circuit voltage, short circuit current density, internal and external quantum efficiency

  15. Organohalide Perovskites for Solar Energy Conversion.

    PubMed

    Lin, Qianqian; Armin, Ardalan; Burn, Paul L; Meredith, Paul

    2016-03-15

    Lead-based organohalide perovskites have recently emerged as arguably the most promising of all next generation thin film solar cell technologies. Power conversion efficiencies have reached 20% in less than 5 years, and their application to other optoelectronic device platforms such as photodetectors and light emitting diodes is being increasingly reported. Organohalide perovskites can be solution processed or evaporated at low temperatures to form simple thin film photojunctions, thus delivering the potential for the holy grail of high efficiency, low embedded energy, and low cost photovoltaics. The initial device-driven "perovskite fever" has more recently given way to efforts to better understand how these materials work in solar cells, and deeper elucidation of their structure-property relationships. In this Account, we focus on this element of organohalide perovskite chemistry and physics in particular examining critical electro-optical, morphological, and architectural phenomena. We first examine basic crystal and chemical structure, and how this impacts important solar-cell related properties such as the optical gap. We then turn to deeper electronic phenomena such as carrier mobilities, trap densities, and recombination dynamics, as well as examining ionic and dielectric properties and how these two types of physics impact each other. The issue of whether organohalide perovskites are predominantly nonexcitonic at room temperature is currently a matter of some debate, and we summarize the evidence for what appears to be the emerging field consensus: an exciton binding energy of order 10 meV. Having discussed the important basic chemistry and physics we turn to more device-related considerations including processing, morphology, architecture, thin film electro-optics and interfacial energetics. These phenomena directly impact solar cell performance parameters such as open circuit voltage, short circuit current density, internal and external quantum efficiency

  16. Structural and magnetic properties of the 5 d2 double perovskites Sr2B ReO6 (B =Y , In)

    NASA Astrophysics Data System (ADS)

    Aczel, A. A.; Zhao, Z.; Calder, S.; Adroja, D. T.; Baker, P. J.; Yan, J.-Q.

    2016-06-01

    We have performed magnetic susceptibility, heat capacity, neutron powder diffraction, and muon spin relaxation experiments to investigate the magnetic ground states of the 5 d2 double perovskites Sr2YReO6 and Sr2InReO6 . We find that Sr2YReO6 is a spin glass, while Sr2InReO6 hosts a nonmagnetic singlet state. By making detailed comparisons with other 5 d2 double perovskites, we argue that a delicate interplay between spin-orbit coupling, noncubic crystal fields, and exchange interactions plays a key role in the great variation of magnetic ground states observed for this family of materials.

  17. Cationic ordering and role of the B-site lanthanide(III) and molybdenum(V) cations on the structure and magnetism of double perovskites Sr{sub 2}LnMoO{sub 6}

    SciTech Connect

    Pinacca, R.M.; Larrégola, S.A.; López, C.A.; Pedregosa, J.C.; Pomjakushin, Vladimir; Sánchez, R.D.; Alonso, J.A.

    2015-06-15

    Highlights: • Five new double perovskites of formula Sr{sub 2}LnMoO{sub 6} were synthesized. • All the samples crystallize in the monoclinic P2{sub 1}/n space group. • Strong reducing conditions were used in order to stabilized Mo(V) cations. • A complete ordering between the rare earth and molybdenum ions was observed. • Magnetism agrees with the crystal distortions observed from Rietveld analysis. - Abstract: We describe the preparation, crystal structure determination and magnetic properties of a new series of ordered double perovskite oxides Sr{sub 2}LnMoO{sub 6} (Ln = Eu, Gd, Dy, Ho, Er, Yb) with Mo{sup 5+} and Ln{sup 3+} electronic configurations. These compounds have been obtained by solid state reaction under reducing conditions in order to stabilize Mo{sup 5+} cations. Structural characterization by XRPD and NPD was performed when Ln = Ho, Er, Yb and just XRPD for absorbing Ln = Eu, Gd, Dy. At room temperature, an excellent Rietveld fit was obtained for all the samples in a monoclinic symmetry, space group P2{sub 1}/n, with long-range ordering of Ln and Mo atoms. Magnetic susceptibility measurements show that some of these materials present magnetic ordering below 25 K and the determined effective magnetic moments are consistent with those expected for the pair Ln{sup 3+}–Mo{sup 5+}. All the phases have negative values​​ of the Weiss temperature indicating dominance of antiferromagnetic interactions.

  18. Perovskite-Type LaSrMnO Electrocatalyst with Uniform Porous Structure for an Efficient Li-O2 Battery Cathode.

    PubMed

    Yang, Yanbing; Yin, Wei; Wu, Shiting; Yang, Xiangdong; Xia, Wei; Shen, Yue; Huang, Yunhui; Cao, Anyuan; Yuan, Quan

    2016-01-26

    Perovskite is an excellent candidate as low cost catalyst for Li-O2 cells. However, the limited porosity, which impedes molecular transport, and the inherent low electronic conductivity are the main barriers toward production of high-performance electrodes. Here, we designed a hierarchical porous flexible architecture by coating thin mesoporous yet crystalline LaSrMnO layers throughout a graphene foam to form graphene/meso-LaSrMnO sandwich-like nanosheets. In this well-designed system, the macropore between nanosheets facilitates O2 and Li(+) diffusion, the mesopore provides large surface area for electrolyte immersion and discharge products deposition, the perovskite phase catalyst decreases reactive overpotential, and the graphene serves as conductive network for electrons transport. When used as a freestanding electrode of Li-O2 cell, it shows high specific capacity, superior rate capability, and cyclic stability. Combination of mesoporous perovskites with conductive graphene networks represents an effective strategy for developing efficient electrodes in various energy storage systems. PMID:26679735

  19. Perovskite-Type LaSrMnO Electrocatalyst with Uniform Porous Structure for an Efficient Li-O2 Battery Cathode.

    PubMed

    Yang, Yanbing; Yin, Wei; Wu, Shiting; Yang, Xiangdong; Xia, Wei; Shen, Yue; Huang, Yunhui; Cao, Anyuan; Yuan, Quan

    2016-01-26

    Perovskite is an excellent candidate as low cost catalyst for Li-O2 cells. However, the limited porosity, which impedes molecular transport, and the inherent low electronic conductivity are the main barriers toward production of high-performance electrodes. Here, we designed a hierarchical porous flexible architecture by coating thin mesoporous yet crystalline LaSrMnO layers throughout a graphene foam to form graphene/meso-LaSrMnO sandwich-like nanosheets. In this well-designed system, the macropore between nanosheets facilitates O2 and Li(+) diffusion, the mesopore provides large surface area for electrolyte immersion and discharge products deposition, the perovskite phase catalyst decreases reactive overpotential, and the graphene serves as conductive network for electrons transport. When used as a freestanding electrode of Li-O2 cell, it shows high specific capacity, superior rate capability, and cyclic stability. Combination of mesoporous perovskites with conductive graphene networks represents an effective strategy for developing efficient electrodes in various energy storage systems.

  20. Pyrophanite pseudomorphs after perovskite in Perkupa serpentinites (Hungary): a microtextural study and geological implications

    NASA Astrophysics Data System (ADS)

    Zajzon, N.; Váczi, T.; Fehér, B.; Takács, Á.; Szakáll, S.; Weiszburg, T. G.

    2013-09-01

    Pyrophanite in serpentinite at Perkupa (Hungary) is described in detail for the first time as a replacement product of perovskite. It occurs as a 20- to 30-μm-wide rim, mantling a remnant core composed of perovskite or its alteration products. The pyrophanite rim consists of an inner zone, representing a pseudomorph after perovskite, and an outer overgrowth zone. Raman mapping and electron backscatter diffraction data show that the pyrophanite rims typically represent single crystals rather than being composed of multiple domains in different crystallographic orientations. Perovskite occurs exclusively in the core of pyrophanite and was identified as the orthorhombic CaTiO3 phase, based on Raman spectra. Heterogeneous, polyphase mineral cores, consisting of calcite, anatase and/or brookite, kassite, and Mn-bearing kassite, in some cases in association with relict perovskite, are typical in the larger pyrophanite-rimmed grains. The crystallographically coherent pyrophanite rims could have formed through a process where the precursor perovskite crystal acted as a structural template for the newly forming phase, that is, by interface-coupled dissolution reprecipitation during serpentinization of the precursor rock. This alteration of perovskite to pyrophanite was not complete, resulting in the presence of perovskite fragments enclosed in pyrophanite. During the metamorphic evolution of the rock, some of the remnant perovskite cores further altered to TiO2 polymorphs (anatase and brookite) and calcite, via transitional alteration products.

  1. NaIrO{sub 3}-A pentavalent post-perovskite

    SciTech Connect

    Bremholm, M.; Dutton, S.E.; Stephens, P.W.; Cava, R.J.

    2011-03-15

    Sodium iridium (V) oxide, NaIrO{sub 3,} was synthesized by a high pressure solid state method and recovered to ambient conditions. It is found to be isostructural with CaIrO{sub 3}, the much-studied structural analog of the high-pressure post-perovskite phase of MgSiO{sub 3}. Among the oxide post-perovskites, NaIrO{sub 3} is the first example with a pentavalent cation. The structure consists of layers of corner- and edge-sharing IrO{sub 6} octahedra separated by layers of NaO{sub 8} bicapped trigonal prisms. NaIrO{sub 3} shows no magnetic ordering and resistivity measurements show non-metallic behavior. The crystal structure, electrical and magnetic properties are discussed and compared to known post-perovskites and pentavalent perovskite metal oxides. -- Graphical abstract: Sodium iridium(V) oxide, NaIrO{sub 3}, synthesized by a high pressure solid state method and recovered to ambient conditions is found to crystallize as the post-perovskite structure and is the first example of a pentavalent ABO{sub 3} post-perovskite. Research highlights: {yields} NaIrO{sub 3} post-perovskite stabilized by pressure. {yields} First example of a pentavalent oxide post-perovskite. {yields} Non-metallic and non-magnetic behavior of NaIrO{sub 3}.

  2. Layered hybrid perovskites with micropores created by alkylammonium functional silsesquioxane interlayers.

    PubMed

    Kataoka, Sho; Banerjee, Subhabrata; Kawai, Akiko; Kamimura, Yoshihiro; Choi, Jun-Chul; Kodaira, Tetsuya; Sato, Kazuhiko; Endo, Akira

    2015-04-01

    Layered organic-inorganic hybrid perovskites that consist of metal halides and organic interlayers are a class of low-dimensional materials. Here, we report the fabrication of layered hybrid perovskites using metal halides and silsesquioxane with a cage-like structure. We used a silsesquioxane as an interlayer to produce a rigid structure and improve the functionality of perovskite layers. Propylammonium-functionalized silsesquioxane and metal halide salts (CuCl2, PdCl2, PbCl2, and MnCl2) were self-assembled to form rigid layered perovskite structures with high crystallinity. The rigid silsesquioxane structure produces micropores between the perovskite layers that can potentially be filled with different molecules to tune the dielectric constants of the interlayers. The obtained silsesquioxane-metal halide hybrid perovskites exhibit some characteristic properties of layered perovskites including magnetic ordering (CuCl4(2-) and MnCl4(2-)) and excitonic absorption/emission (PbCl4(2-)). Our results indicate that inserting silsesquioxane interlayers into hybrid perovskites retains and enhances the low-dimensional properties of the materials.

  3. Structural, electrochemical and magnetic characterization of the layered-type PrBa{sub 0.5}Sr{sub 0.5}Co{sub 2}O{sub 5+δ} perovskite

    SciTech Connect

    Azad, Abul K.; Kim, Jung H.; Irvine, John T.S.

    2014-05-01

    Structural, electrical and magnetic properties of the layered cobaltite PrBa{sub 0.5}Sr{sub 0.5}Co{sub 2}O{sub 5+δ} have been investigated by means of neutron diffraction, electron diffraction, thermogravimetric analysis and SQUID magnetometry. Rietveld analysis of neutron diffraction data shows the ordered distribution of oxygen vacancies in [PrO{sub δ}] planes which doubles the lattice parameters from the simple perovskite cell parameter as a≈2a{sub p} and c≈2a{sub p} (a{sub p} is the cell parameter of the simple Perovskite) yielding tetragonal symmetry in the P4/mmm space group. On heating, above 573 K in air, structural rearrangement takes place and the structure can be defined as a≈a{sub p} and c≈2a{sub p} in the same space group. Oxygen occupancies have been determined as a function of temperature from neutron diffraction results. Initially (≥373 K), oxygen occupancy was increased and then decreased with increasing temperature. It was found that at 973 K the total oxygen loss is calculated about 0.265 oxygen/formula unit. Oxygen vacancy ordering was observed below 573 K, and the oxygen occupancy decreases as cell volume increases with increasing temperature. Area specific resistance (ASR) measurements show a resistance of 0.153 Ωcm{sup 2} and 0.286 Ωcm{sup 2} at 973 K and 923 K, respectively. On cooling, paramagnetic to ferromagnetic and an incomplete ferromagnetic to antiferromagnetic transition takes place. Different behaviours in field cooled and zero-field-cooled measurements leads to a coexistence of ferromagnetic and antiferromagnetic order. - Graphical abstract: Structural phase changes in PrBa{sub 0.5}Sr{sub 0.5}Co{sub 2}O{sub 5+δ} at elevated temperatures determined by neutron powder diffraction. Depending on oxygen occupancy it form different phases at different temperatures. This pictures show the schematic 3D diagram of PrBa{sub 0.5}Sr{sub 0.5}Co{sub 2}O{sub 5+δ} at 295 K (a), 373 K (b) and 573 K (c). Co atoms are inside the

  4. Substitution effect of pentavalent bismuth ions on the electronic structure and physicochemical properties of perovskite-structured Ba(In{sub 0.5}Ta{sub 0.5-x}Bi{sub x})O{sub 3} semiconductors

    SciTech Connect

    Kim, Tae Woo; Hur, Su Gil; Hwang, Seong-Ju Park, Hyunwoong; Park, Yiseul; Choi, Wonyong; Choy, Jin-Ho

    2007-11-06

    We have investigated the substitution effect of pentavalent bismuth ions on the electronic structure and physicochemical properties of barium indium tantalate. X-ray diffraction, X-ray absorption spectroscopic, and energy dispersive spectroscopic microprobe analyses reveal that, under oxygen atmosphere of 1 atm, pentavalent Bi ions are successfully stabilized in the octahedral site of the perovskite tantalate lattice. According to diffuse reflectance UV-vis spectroscopic analysis, the Bi substitution gives rise to the significant narrowing of band gap of barium indium tantalate even at a low Bi content of {approx}5%, underscoring a high efficiency of Bi substitution in the band gap engineering. Such an effective narrowing of the band gap upon the Bi substitution would be attributable to the lowering of conduction band position due to the high electronegativity of Bi{sup V} substituent. As a result of band gap engineering, the Ba(In{sub 0.5}Ta{sub 0.5-x}Bi{sub x})O{sub 3} compounds with x {>=} 0.03 can generate photocurrents under visible light irradiation ({lambda} > 420 nm). Based on the present experimental findings, it becomes clear that the substitution of highly electronegative p-block element like Bi{sup V} ion can provide a very powerful tool for tailoring the electronic structure and physicochemical properties of wide band gap semiconductors.

  5. Resistance switching memory in perovskite oxides

    SciTech Connect

    Yan, Z.B. Liu, J.-M.

    2015-07-15

    The resistance switching behavior has recently attracted great attentions for its application as resistive random access memories (RRAMs) due to a variety of advantages such as simple structure, high-density, high-speed and low-power. As a leading storage media, the transition metal perovskite oxide owns the strong correlation of electrons and the stable crystal structure, which brings out multifunctionality such as ferroelectric, multiferroic, superconductor, and colossal magnetoresistance/electroresistance effect, etc. The existence of rich electronic phases, metal–insulator transition and the nonstoichiometric oxygen in perovskite oxide provides good platforms to insight into the resistive switching mechanisms. In this review, we first introduce the general characteristics of the resistance switching effects, the operation methods and the storage media. Then, the experimental evidences of conductive filaments, the transport and switching mechanisms, and the memory performances and enhancing methods of perovskite oxide based filamentary RRAM cells have been summarized and discussed. Subsequently, the switching mechanisms and the performances of the uniform RRAM cells associating with the carrier trapping/detrapping and the ferroelectric polarization switching have been discussed. Finally, the advices and outlook for further investigating the resistance switching and enhancing the memory performances are given.

  6. Elasticity of AlFeO3 and FeAlO3 perovskite and post-perovskite from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Caracas, R.

    2010-10-01

    We use state-of-the-art ab initio calculations based on the generalized gradient approximation of the density functional theory in the planar augmented wavefunction formalism to determine the elastic constants tensor of perovskite and post-perovskite with formulas AlFeO3 and FeAlO3 in which Fe or Al respectively occupy only octahedral sites, for the stable magnetic configurations. The phase transition between perovskite and post-perovskite is associated with a site exchange, during which Fe from the inter-octahedral site in perovskite moves into the octahedral site in post-perovskite. Following this transition path the elastic moduli show positive jumps, considerably larger than for MgSiO3. The phase transition is marked by a positive jump of 0.04 km/s (0.33%) in the velocity of the compressional waves and by a negative jump of -0.15 km/s (-1.87%) in shear wave velocity. We find that the effects of the Mg + Si <=> Al + Fe substitution on the seismic properties of MgSiO3 perovskite and post-perovskite depend on the crystallography of the substitution, namely the position the exchanged cations take in the structure.

  7. Structure and properties of epitaxial perovskite Pb(Zr0.52Ti0.48)O3/La0.7Sr0.3MnO3 heterostructures

    NASA Astrophysics Data System (ADS)

    Zou, Cheng; Chen, Yuan-Fu; Li, Ping-Jian; Fan, Rui; Peng, Bing; Zhang, Wen-Xu; Wang, Ze-Gao; Hao, Xin; Liu, Jing-Bo; Zhang, Wan-Li; Li, Yan-Rong; Li, Run-Wei

    2012-04-01

    The morphology, crystalline structure of epitaxial heterostructures of Pb(Zr0.52Ti0.48)O3/La0.7Sr0.3MnO3 (PZT/LSMO) grown on single crystalline SrTiO3 substrates by pulse laser deposition (PLD), have been investigated. The morphology results show that the LSMO layers and PZT layers are smooth and homogenous. The crystalline structure measurements indicate that good epitaxial relationships between LSMO and PZT and STO were obtained. The effects of applied electric and magnetic fields on the physical properties of epitaxial perovskite ferroelectric/ferromagnetic heterostructures were investigated. The results show that the polarized electric field has a very significant influence on the transport properties of LSMO layers while has little influence on the magnetization, and the magnetic field has an obvious influence on the ferroelectric behavior of the PZT layer.

  8. A-site ordered quadruple perovskite oxides

    NASA Astrophysics Data System (ADS)

    Youwen, Long

    2016-07-01

    The A-site ordered perovskite oxides with chemical formula display many intriguing physical properties due to the introduction of transition metals at both A‧ and B sites. Here, research on the recently discovered intermetallic charge transfer occurring between A‧-site Cu and B-site Fe ions in LaCu3Fe4O12 and its analogues is reviewed, along with work on the magnetoelectric multiferroicity observed in LaMn3Cr4O12 with cubic perovskite structure. The Cu-Fe intermetallic charge transfer leads to a first-order isostructural phase transition accompanied by drastic variations in magnetism and electrical transport properties. The LaMn3Cr4O12 is a novel spin-driven multiferroic system with strong magnetoelectric coupling effects. The compound is the first example of cubic perovskite multiferroics to be found. It opens up a new arena for studying unexpected multiferroic mechanisms. Project supported by the National Basic Research Program of China (Grant No. 2014CB921500), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB07030300), and the National Natural Science Foundation of China (Grant No. 11574378).

  9. Structural and magnetic characterisation of the novel spin frustrated double perovskite Sr{sub 2}ScMoO{sub 6}

    SciTech Connect

    Wallace, Thomas K.; Mclaughlin, Abbie C.

    2014-11-15

    A novel Mo{sup 5+} double perovskite, Sr{sub 2}ScMoO{sub 6}, has been synthesised. This material crystallises in the tetragonal I4/m symmetry space group and considerable cation disorder between Sc{sup 3+} and Mo{sup 5+} is observed. Magnetic susceptibility measurements show no evidence of a magnetic transition down to 6 K and no evidence of the valence bond glass state previously reported for A{sub 2}YMoO{sub 6} (A=Ba, Sr). The inverse susceptibility data cannot be fit to the Curie–Weiss law at any temperature range between 6 and 300 K. This deviation from Curie–Weiss law suggests that strong antiferromagnetic correlations are still present in Sr{sub 2}ScMoO{sub 6}. - Graphical abstract: A novel double perovskite Sr{sub 2}ScMoO{sub 6} has been synthesised which has corner sharing MoO{sub 6} and ScO{sub 6} octahedra. The Sr{sup 2+} cations reside in the cavities and exhibit anisotropic thermal motion. There is no evidence of magnetic order down to 6 K. - Highlights: • The novel perovskite Sr{sub 2}ScMoO{sub 6} has been synthesised. • Disorder of the Mo{sup 5+} and Sc{sup 3+} cations is observed. • There is no evidence of a magnetic transition down to 6 K. • There is likely frustrated short range magnetic order or spin liquid behaviour.

  10. Atomistic mechanism leading to complex antiferroelectric and incommensurate perovskites

    NASA Astrophysics Data System (ADS)

    Patel, Kinnary; Prosandeev, Sergey; Yang, Yurong; Xu, Bin; Íñiguez, Jorge; Bellaiche, L.

    2016-08-01

    An atomic interaction is identified in all perovskite compounds, such as A B O3 oxides, that can potentially result in unconventional structures. The term is harmonic in nature and couples the motions of the A cations with the rotations of the oxygen octahedra in the perovskite lattice. When strong enough, this coupling leads to hybrid normal modes that present both (anti)polar and rotational characters, which are keys to understand a variety of exotic phases. For example, we show that not only does this new coupling explain the long-period soft phonons characterizing prototype antiferroelectric PbZrO3, but it also provides us with an unified description of the complex antipolar structures of a variety of perovskites, including the possible occurrence of incommensurate phases. This coupling is further demonstrated to result, in the continuum limit, in an energy invariant adopting an analytical form that has been previously overlooked, to the best of our knowledge.

  11. Selective Precipitation and Concentrating of Perovskite Crystals from Titanium-Bearing Slag Melt in Supergravity Field

    NASA Astrophysics Data System (ADS)

    Gao, Jintao; Zhong, Yiwei; Guo, Zhancheng

    2016-08-01

    Selective precipitation and concentrating of perovskite crystals from titanium-bearing slag melt in the supergravity field was investigated in this study. Since perovskite was the first precipitated phase from the slag melt during the cooling process, and a greater precipitation quantity and larger crystal sizes of perovskite were obtained at 1593 K to 1563 K (1320 °C to 1290 °C), concentrating of perovskite crystals from the slag melt was carried out at this temperature range in the supergravity field, at which the perovskite transforms into solid particles while the other minerals remain in the liquid melt. The layered structures appeared significantly in the sample obtained by supergravity treatment, and all the perovskite crystals moved along the supergravity direction and concentrated as the perovskite-rich phase in the bottom area, whereas the molten slag concentrated in the upper area along the opposite direction, in which it was impossible to find any perovskite crystals. With the gravity coefficient of G = 750, the mass fraction of TiO2 in the perovskite-rich phase was up to 34.65 wt pct, whereas that of the slag phase was decreased to 12.23 wt pct, and the recovery ratio of Ti in the perovskite-rich phase was up to 75.28 pct. On this basis, an amplification experimental centrifugal apparatus was exploited and the continuous experiment with larger scale was further carried out, the results confirming that selective precipitation and concentrating of perovskite crystals from the titanium-bearing slag melt by supergravity was a feasible method.

  12. Methodologies for high efficiency perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Park, Nam-Gyu

    2016-06-01

    Since the report on long-term durable solid-state perovskite solar cell in 2012, perovskite solar cells based on lead halide perovskites having organic cations such as methylammonium CH3NH3PbI3 or formamidinium HC(NH2)2PbI3 have received great attention because of superb photovoltaic performance with power conversion efficiency exceeding 22 %. In this review, emergence of perovskite solar cell is briefly introduced. Since understanding fundamentals of light absorbers is directly related to their photovoltaic performance, opto-electronic properties of organo lead halide perovskites are investigated in order to provide insight into design of higher efficiency perovskite solar cells. Since the conversion efficiency of perovskite solar cell is found to depend significantly on perovskite film quality, methodologies for fabricating high quality perovskite films are particularly emphasized, including various solution-processes and vacuum deposition method.

  13. New Physical Deposition Approach for Low Cost Inorganic Hole Transport Layer in Normal Architecture of Durable Perovskite Solar Cells.

    PubMed

    Nejand, Bahram Abdollahi; Ahmadi, Vahid; Shahverdi, Hamid Reza

    2015-10-01

    In this work we reported sputter deposited NiOx/Ni double layer as an HTM/contact couple in normal architecture of perovskite solar cell. A perovskite solar cell that is durable for more than 60 days was achieved, with increasing efficiency from 1.3% to 7.28% within 6 days. Moreover, low temperature direct deposition of NiOx layer on perovskite layer was introduced as a potential hole transport material for an efficient cost-effective solar cell applicable for various morphologies of perovskite layers, even for perovskite layers containing pinholes, which is a notable challenge in perovskite solar cells. The angular deposition of NiOx layers by dc reactive magnetron sputtering showed uniform and crack-free coverage of the perovskite layer with no negative impact on perovskite structure that is suitable for nickel back contact layer, surface shielding against moisture, and mechanical damages. Replacing the expensive complex materials in previous perovskite solar cells with low cost available materials introduces cost-effective scalable perovskite solar cells.

  14. 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.

  15. First-principles hybrid functional study of the electronic structure and charge carrier mobility in perovskite CH3NH3SnI3

    NASA Astrophysics Data System (ADS)

    Wu, Li-Juan; Zhao, Yu-Qing; Chen, Chang-Wen; Wang, Lin-Zhi; Liu, Biao; Cai, Meng-Qiu

    2016-10-01

    We calculate the electronic properties and carrier mobility of perovskite CH3NH3SnI3 as a solar cell absorber by using the hybrid functional method. The calculated result shows that the electron and hole mobilities have anisotropies with a large magnitude of 1.4 × 104 cm2·V-1·s-1 along the y direction. In view of the huge difference between hole and electron mobilities, the perovskite CH3NH3SnI3 can be considered as a p-type semiconductor. We also discover a relationship between the effective mass anisotropy and electronic occupation anisotropy. The above results can provide reliable guidance for its experimental applications in electronics and optoelectronics. Project supported by the National Natural Science Foundation of China (Grant No. 51172067), the Hunan Provincial Natural Science Fund for Distinguished Young Scholars, China (Grant No. 13JJ1013), the Specialized Research Fund for the Doctoral Program of Higher Education, China (Grant No. 20130161110036), and the New Century Excellent Talents in University, China (Grant No. NCET-12-0171.D).

  16. Mixed metallic Ba(Co,Fe)X(0.2)O(3-δ) (X = F, Cl) hexagonal perovskites: drastic effect of Fe-incorporation on structural and electronic features.

    PubMed

    Iorgulescu, Mihaela; Roussel, Pascal; Tancret, Nathalie; Renault, Nicolas; Porcher, Florence; André, Gilles; Kabbour, Houria; Mentré, Olivier

    2012-07-16

    Starting from the parent 10H-Ba(5)Co(5)X(1-x)O(13-δ) (trimeric strings of face-sharing CoO(6) octahedra with terminal CoO(4) tetrahedra, stacking sequence (chhch')(2)) and 6H-Ba(6)Co(6)X(1-x)O(16-δ) (similar with tetrameric strings, stacking sequence chhhch') hexagonal perovskites forms (X = F, Cl; c, h = [BaO(3)] layers ; h' = [BaOX(1-y)] layers), we show here that the Fe incorporation leads to large domains of solid solutions for both X = F and Cl but exclusively stabilizes the 10H-form independently of the synthesis method. In this form, the lowest concentration of h-layers is stabilized by a sensitive metal reduction with increasing the Fe ratio. In a more general context of competition between several hexagonal perovskite polymorphs available for most of the transition metals, this redox change is most probably the key factor driving 1D (face-sharing chains) to 3D (corner-sharing) connectivities. Strikingly, ND data evidence the location of oxygen deficiencies in the tetrahedral (Co/Fe) coordination. This effect is exaggerated at high temperature, while (Co/Fe)O(4-δ) coordinations are completed by the displacement of X(-) anions toward the (Co/Fe) sphere of coordination following a "push-and-pull" mechanism within h'-[BaOX(1-y)] layers. The Fe-incorporation is also accompanied by increasing conduction gaps with predominant 1D variable range hopping. The full series show antiferromagnetic behavior with increasing T(N) as [Fe] increases. For Fe-rich compounds T(N) is estimated about 600 K, as rarely observed for hexagonal perovskite compounds. Finally, magnetic structures of all iron-doped compounds show a site-to-site AFM ordering, different of the magnetic structure of Co-only parent compounds. Here, DFT calculations predict low-spin octahedral Co configurations, but high-spin Fe species in the same sites.

  17. Perovskite Solar Cells with Large-Area CVD-Graphene for Tandem Solar Cells.

    PubMed

    Lang, Felix; Gluba, Marc A; Albrecht, Steve; Rappich, Jörg; Korte, Lars; Rech, Bernd; Nickel, Norbert H

    2015-07-16

    Perovskite solar cells with transparent contacts may be used to compensate for thermalization losses of silicon solar cells in tandem devices. This offers a way to outreach stagnating efficiencies. However, perovskite top cells in tandem structures require contact layers with high electrical conductivity and optimal transparency. We address this challenge by implementing large-area graphene grown by chemical vapor deposition as a highly transparent electrode in perovskite solar cells, leading to identical charge collection efficiencies. Electrical performance of solar cells with a graphene-based contact reached those of solar cells with standard gold contacts. The optical transmission by far exceeds that of reference devices and amounts to 64.3% below the perovskite band gap. Finally, we demonstrate a four-terminal tandem device combining a high band gap graphene-contacted perovskite top solar cell (Eg = 1.6 eV) with an amorphous/crystalline silicon bottom solar cell (Eg = 1.12 eV). PMID:26266857

  18. Perovskite Solar Cells with Large-Area CVD-Graphene for Tandem Solar Cells.

    PubMed

    Lang, Felix; Gluba, Marc A; Albrecht, Steve; Rappich, Jörg; Korte, Lars; Rech, Bernd; Nickel, Norbert H

    2015-07-16

    Perovskite solar cells with transparent contacts may be used to compensate for thermalization losses of silicon solar cells in tandem devices. This offers a way to outreach stagnating efficiencies. However, perovskite top cells in tandem structures require contact layers with high electrical conductivity and optimal transparency. We address this challenge by implementing large-area graphene grown by chemical vapor deposition as a highly transparent electrode in perovskite solar cells, leading to identical charge collection efficiencies. Electrical performance of solar cells with a graphene-based contact reached those of solar cells with standard gold contacts. The optical transmission by far exceeds that of reference devices and amounts to 64.3% below the perovskite band gap. Finally, we demonstrate a four-terminal tandem device combining a high band gap graphene-contacted perovskite top solar cell (Eg = 1.6 eV) with an amorphous/crystalline silicon bottom solar cell (Eg = 1.12 eV).

  19. Structural characterisation of the perovskite series Sr{sub x}Ca{sub 1-x-y}Nd{sub y}MnO{sub 3}: Influence of the Jahn-Teller effect

    SciTech Connect

    Kennedy, Brendan J.; Saines, Paul J.; Ting, Jimmy; Zhou Qingdi; Kimpton, Justin A.

    2009-10-15

    The crystal structures of the perovskite manganites Sr{sub x}Ca{sub 1-x-y}Nd{sub y}MnO{sub 3} with y=0.1 or 0.2 have been investigated using synchrotron X-ray powder diffraction. At room temperature the structures change from Pm3-barmreversibleI4/mcmreversiblePbnm depending on the cation distribution, the different structures exhibiting different tilts of the MnO{sub 6} octahedra. High temperature diffraction measurements demonstrate the presence of, an apparently continuous, isosymmetric I4/mcm to I4/mcm phase transition associated with the removal of long range orbital ordering. Heating the manganites to still higher temperatures results in a continuous transition to the cubic Pm3-barm structure. A feature of such transitions is the continuous evolution of the octahedral tilt angle through the I4/mcm to I4/mcm phase transition. The orthorhombic structures do not exhibit orbital ordering and although a first order transition to the tetragonal structure is observed in Sr{sub 0.4}Ca{sub 0.5}Nd{sub 0.1}MnO{sub 3}, this high temperature tetragonal structure does not exhibit orbital ordering. - Graphical abstract: Structural studies of oxides of the type Sr{sub x}Ca{sub 1-x-y}Nd{sub y}MnO{sub 3} series illustrate the continuous removal of the octahedral tilting, despite the loss of orbital ordering.

  20. Comprehensive design of omnidirectional high-performance perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Zhang, Yutao; Xuan, Yimin

    2016-07-01

    The comprehensive design approach is established with coupled optical-electrical simulation for perovskite-based solar cell, which emerged as one of the most promising competitors to silicon solar cell for its low-cost fabrication and high PCE. The selection of structured surface, effect of geometry parameters, incident angle-dependence and polarization-sensitivity are considered in the simulation. The optical modeling is performed via the finite-difference time-domain method whilst the electrical properties are obtained by solving the coupled nonlinear equations of Poisson, continuity, and drift-diffusion equations. The optical and electrical performances of five different structured surfaces are compared to select a best structured surface for perovskite solar cell. The effects of the geometry parameters on the optical and electrical properties of the perovskite cell are analyzed. The results indicate that the light harvesting is obviously enhanced by the structured surface. The electrical performance can be remarkably improved due to the enhanced light harvesting of the designed best structured surface. The angle-dependence for s- and p-polarizations is investigated. The structured surface exhibits omnidirectional behavior and favorable polarization-insensitive feature within a wide incident angle range. Such a comprehensive design approach can highlight the potential of perovskite cell for power conversion in the full daylight.

  1. Comprehensive design of omnidirectional high-performance perovskite solar cells.

    PubMed

    Zhang, Yutao; Xuan, Yimin

    2016-01-01

    The comprehensive design approach is established with coupled optical-electrical simulation for perovskite-based solar cell, which emerged as one of the most promising competitors to silicon solar cell for its low-cost fabrication and high PCE. The selection of structured surface, effect of geometry parameters, incident angle-dependence and polarization-sensitivity are considered in the simulation. The optical modeling is performed via the finite-difference time-domain method whilst the electrical properties are obtained by solving the coupled nonlinear equations of Poisson, continuity, and drift-diffusion equations. The optical and electrical performances of five different structured surfaces are compared to select a best structured surface for perovskite solar cell. The effects of the geometry parameters on the optical and electrical properties of the perovskite cell are analyzed. The results indicate that the light harvesting is obviously enhanced by the structured surface. The electrical performance can be remarkably improved due to the enhanced light harvesting of the designed best structured surface. The angle-dependence for s- and p-polarizations is investigated. The structured surface exhibits omnidirectional behavior and favorable polarization-insensitive feature within a wide incident angle range. Such a comprehensive design approach can highlight the potential of perovskite cell for power conversion in the full daylight. PMID:27405419

  2. Comprehensive design of omnidirectional high-performance perovskite solar cells

    PubMed Central

    Zhang, Yutao; Xuan, Yimin

    2016-01-01

    The comprehensive design approach is established with coupled optical-electrical simulation for perovskite-based solar cell, which emerged as one of the most promising competitors to silicon solar cell for its low-cost fabrication and high PCE. The selection of structured surface, effect of geometry parameters, incident angle-dependence and polarization-sensitivity are considered in the simulation. The optical modeling is performed via the finite-difference time-domain method whilst the electrical properties are obtained by solving the coupled nonlinear equations of Poisson, continuity, and drift-diffusion equations. The optical and electrical performances of five different structured surfaces are compared to select a best structured surface for perovskite solar cell. The effects of the geometry parameters on the optical and electrical properties of the perovskite cell are analyzed. The results indicate that the light harvesting is obviously enhanced by the structured surface. The electrical performance can be remarkably improved due to the enhanced light harvesting of the designed best structured surface. The angle-dependence for s- and p-polarizations is investigated. The structured surface exhibits omnidirectional behavior and favorable polarization-insensitive feature within a wide incident angle range. Such a comprehensive design approach can highlight the potential of perovskite cell for power conversion in the full daylight. PMID:27405419

  3. 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

  4. 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. PMID:26717046

  5. Aluminum-Doped Zinc Oxide as Highly Stable Electron Collection Layer for Perovskite Solar Cells.

    PubMed

    Zhao, Xingyue; Shen, Heping; Zhang, Ye; Li, Xin; Zhao, Xiaochong; Tai, Meiqian; Li, Jingfeng; Li, Jianbao; Li, Xin; Lin, Hong

    2016-03-01

    Although low-temperature, solution-processed zinc oxide (ZnO) has been widely adopted as the electron collection layer (ECL) in perovskite solar cells (PSCs) because of its simple synthesis and excellent electrical properties such as high charge mobility, the thermal stability of the perovskite films deposited atop ZnO layer remains as a major issue. Herein, we addressed this problem by employing aluminum-doped zinc oxide (AZO) as the ECL and obtained extraordinarily thermally stable perovskite layers. The improvement of the thermal stability was ascribed to diminish of the Lewis acid-base chemical reaction between perovskite and ECL. Notably, the outstanding transmittance and conductivity also render AZO layer as an ideal candidate for transparent conductive electrodes, which enables a simplified cell structure featuring glass/AZO/perovskite/Spiro-OMeTAD/Au. Optimization of the perovskite layer leads to an excellent and repeatable photovoltaic performance, with the champion cell exhibiting an open-circuit voltage (Voc) of 0.94 V, a short-circuit current (Jsc) of 20.2 mA cm(-2), a fill factor (FF) of 0.67, and an overall power conversion efficiency (PCE) of 12.6% under standard 1 sun illumination. It was also revealed by steady-state and time-resolved photoluminescence that the AZO/perovskite interface resulted in less quenching than that between perovskite and hole transport material. PMID:26960451

  6. Aluminum-Doped Zinc Oxide as Highly Stable Electron Collection Layer for Perovskite Solar Cells.

    PubMed

    Zhao, Xingyue; Shen, Heping; Zhang, Ye; Li, Xin; Zhao, Xiaochong; Tai, Meiqian; Li, Jingfeng; Li, Jianbao; Li, Xin; Lin, Hong

    2016-03-01

    Although low-temperature, solution-processed zinc oxide (ZnO) has been widely adopted as the electron collection layer (ECL) in perovskite solar cells (PSCs) because of its simple synthesis and excellent electrical properties such as high charge mobility, the thermal stability of the perovskite films deposited atop ZnO layer remains as a major issue. Herein, we addressed this problem by employing aluminum-doped zinc oxide (AZO) as the ECL and obtained extraordinarily thermally stable perovskite layers. The improvement of the thermal stability was ascribed to diminish of the Lewis acid-base chemical reaction between perovskite and ECL. Notably, the outstanding transmittance and conductivity also render AZO layer as an ideal candidate for transparent conductive electrodes, which enables a simplified cell structure featuring glass/AZO/perovskite/Spiro-OMeTAD/Au. Optimization of the perovskite layer leads to an excellent and repeatable photovoltaic performance, with the champion cell exhibiting an open-circuit voltage (Voc) of 0.94 V, a short-circuit current (Jsc) of 20.2 mA cm(-2), a fill factor (FF) of 0.67, and an overall power conversion efficiency (PCE) of 12.6% under standard 1 sun illumination. It was also revealed by steady-state and time-resolved photoluminescence that the AZO/perovskite interface resulted in less quenching than that between perovskite and hole transport material.

  7. Interface and Composition Analysis on Perovskite Solar Cells.

    PubMed

    Matteocci, Fabio; Busby, Yan; Pireaux, Jean-Jacques; Divitini, Giorgio; Cacovich, Stefania; Ducati, Caterina; Di Carlo, Aldo

    2015-12-01

    Organometal halide (hybrid) perovskite solar cells have been fabricated following four different deposition procedures and investigated in order to find correlations between the solar cell characteristics/performance and their structure and composition as determined by combining depth-resolved imaging with time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and analytical scanning transmission electron microscopy (STEM). The interface quality is found to be strongly affected by the perovskite deposition procedure, and in particular from the environment where the conversion of the starting precursors into the final perovskite is performed (air, nitrogen, or vacuum). The conversion efficiency of the precursors into the hybrid perovskite layer is compared between the different solar cells by looking at the ToF-SIMS intensities of the characteristic molecular fragments from the perovskite and the precursor materials. Energy dispersive X-ray spectroscopy in the STEM confirms the macroscopic ToF-SIMS findings and allows elemental mapping with nanometer resolution. Clear evidence for iodine diffusion has been observed and related to the fabrication procedure.

  8. Halide Perovskites: Poor Man's High-Performance Semiconductors.

    PubMed

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2016-07-01

    Halide perovskites are a rapidly developing class of medium-bandgap semiconductors which, to date, have been popularized on account of their remarkable success in solid-state heterojunction solar cells raising the photovoltaic efficiency to 20% within the last 5 years. As the physical properties of the materials are being explored, it is becoming apparent that the photovoltaic performance of the halide perovskites is just but one aspect of the wealth of opportunities that these compounds offer as high-performance semiconductors. From unique optical and electrical properties stemming from their characteristic electronic structure to highly efficient real-life technological applications, halide perovskites constitute a brand new class of materials with exotic properties awaiting discovery. The nature of halide perovskites from the materials' viewpoint is discussed here, enlisting the most important classes of the compounds and describing their most exciting properties. The topics covered focus on the optical and electrical properties highlighting some of the milestone achievements reported to date but also addressing controversies in the vastly expanding halide perovskite literature. PMID:27174223

  9. 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

  10. Interface and Composition Analysis on Perovskite Solar Cells.

    PubMed

    Matteocci, Fabio; Busby, Yan; Pireaux, Jean-Jacques; Divitini, Giorgio; Cacovich, Stefania; Ducati, Caterina; Di Carlo, Aldo

    2015-12-01

    Organometal halide (hybrid) perovskite solar cells have been fabricated following four different deposition procedures and investigated in order to find correlations between the solar cell characteristics/performance and their structure and composition as determined by combining depth-resolved imaging with time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and analytical scanning transmission electron microscopy (STEM). The interface quality is found to be strongly affected by the perovskite deposition procedure, and in particular from the environment where the conversion of the starting precursors into the final perovskite is performed (air, nitrogen, or vacuum). The conversion efficiency of the precursors into the hybrid perovskite layer is compared between the different solar cells by looking at the ToF-SIMS intensities of the characteristic molecular fragments from the perovskite and the precursor materials. Energy dispersive X-ray spectroscopy in the STEM confirms the macroscopic ToF-SIMS findings and allows elemental mapping with nanometer resolution. Clear evidence for iodine diffusion has been observed and related to the fabrication procedure. PMID:26523427

  11. Halide Perovskites: Poor Man's High-Performance Semiconductors.

    PubMed

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2016-07-01

    Halide perovskites are a rapidly developing class of medium-bandgap semiconductors which, to date, have been popularized on account of their remarkable success in solid-state heterojunction solar cells raising the photovoltaic efficiency to 20% within the last 5 years. As the physical properties of the materials are being explored, it is becoming apparent that the photovoltaic performance of the halide perovskites is just but one aspect of the wealth of opportunities that these compounds offer as high-performance semiconductors. From unique optical and electrical properties stemming from their characteristic electronic structure to highly efficient real-life technological applications, halide perovskites constitute a brand new class of materials with exotic properties awaiting discovery. The nature of halide perovskites from the materials' viewpoint is discussed here, enlisting the most important classes of the compounds and describing their most exciting properties. The topics covered focus on the optical and electrical properties highlighting some of the milestone achievements reported to date but also addressing controversies in the vastly expanding halide perovskite literature.

  12. Cuprous Oxide as a Potential Low-Cost Hole-Transport Material for Stable Perovskite Solar Cells.

    PubMed

    Nejand, Bahram Abdollahi; Ahmadi, Vahid; Gharibzadeh, Saba; Shahverdi, Hamid Reza

    2016-02-01

    Inorganic hole-transport materials are commercially desired to decrease the fabrication cost of perovskite solar cells. Here, Cu2O is introduced as a potential hole-transport material for stable, low-cost devices. Considering that Cu2O formation is highly sensitive to the underlying mixture of perovskite precursors and their solvents, we proposed and engineered a technique for reactive magnetron sputtering. The rotational angular deposition of Cu2O yields high surface coverage of the perovskite layer for high rate of charge extraction. Deposition of this Cu2O layer on the pinhole-free perovskite layer produces devices with power conversion efficiency values of up to 8.93%. The engineered Cu2O layers showed uniform, compact, and crack-free surfaces on the perovskite layer without affecting the perovskite structure, which is desired for deposition of the top metal contact and for surface shielding against moisture and mechanical damages. PMID:26748959

  13. Formation and structural characterization of 1:1 ordered perovskites in the Ba(Zn{sub 1/3}Ta{sub 2/3})O{sub 3}-BaZrO{sub 3} system

    SciTech Connect

    Chai, L.; Davies, P.K.

    1997-12-01

    The phase stabilities in the (1{minus}x)Ba(Zn{sub 1/3}Ta{sub 2/3})O{sub 3} (BZT)-xBaZrO{sub 3} (BZ) system have been investigated using samples prepared by the mixed-oxide method. The substitution of Zr{sup 4+} destabilizes the 1:2 cation ordering in BZT and promotes the formation of a cubic, 1:1 ordered structure with a doubled perovskite repeat. The homogeneity range of the 1:1 phase extends from x = 0.04 to approximately x = 0.25; substitutions beyond this range stabilize a disordered perovskite. The limits of stability of the 1:1 ordering coincide with compositions previously found to exhibit anomalies in their dielectric loss. The range of homogeneity is consistent with a random layer model for the 1:1 ordered Ba{l_brace}{beta}{prime}{sub 1/2}{beta}{double_prime}{sub 1/2}{r_brace}O{sub 3} structure. In this model the {beta}{double_prime} positions are assumed to be occupied exclusively by Ta{sup 5+}, and the {beta}{prime} sites by a random distribution of Zn{sup 2+}, Zr{sup 4+}, and the remaining Ta{sup 5+} cations. The validity of the model, where the ordered solid solutions can be represented by Ba{l_brace}[Zn{sub (2{minus}y)/3}Ta{sub (1{minus}2y)/3}Zr{sub y}]{sub 1/2}[Ta]{sub 1/2}{r_brace}O{sub 3} (y = 2x) was confirmed by Rietveld refinements conducted using data collected with a synchrotron X-ray source.

  14. Synthesis, crystal structure and characterization of new 12H hexagonal perovskite-related oxides Ba 6M2Na 2X2O 17 ( M=Ru, Nb, Ta, Sb; X=V, Cr, Mn, P, As)

    NASA Astrophysics Data System (ADS)

    Quarez, Eric; Abraham, Francis; Mentré, Olivier

    2003-11-01

    The new Ba 6Ru 2Na 2X2O 17 ( X=V, Mn) compounds have been prepared by electrosynthesis in molten NaOH and their crystal structures have been refined from single crystals X-ray diffraction, space group P6 3/ mmc, Z=2, for X=V: a =5.8506(1) Å, c =29.6241(4) Å, R1=4.76%, for X=Mn : a =5.8323(1) Å, c =29.5299(3) Å, R1=3.48%. The crystal structure is a 12H-type perovskite with a ( c' cchcc) 2 stacking sequence of [BaO 3] c, [BaO 3] h and [BaO 2] c' layers. The tridimensional edifice is formed by blocks of Ru 2O 9 dimers that share corners with NaO 6 octahedra. These blocks sandwich double sheets of X5+O 4 tetrahedra. Several isotypic Ba 6M5+2Na 2X5+2O 17 materials ( X=V, Cr, Mn, P, As) and ( M=Ru, Nb, Ta, Sb) have been prepared by solid state reaction and characterized by Rietveld analysis. The magnetic and electric properties have been investigated and show besides the Ru 5+2O 9 typical intradimer antiferromagnetic couplings, discrepancies of both χ and ρ versus T at 50 and 100 K for Ba 6Ru 2Na 2X2O 17 ( X=V, As). In this work, a review of the identified Ru-hexagonal perovskite materials is also reported in order to overview the wide variety of possibilities in the field of new compounds synthesis.

  15. 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 0structural 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.

  16. A neutron diffraction study of structural distortion and magnetic ordering in the cation-ordered perovskites Ba{sub 2}Nd{sub 1−x}Y{sub x}MoO{sub 6}

    SciTech Connect

    Collins, Oonagh M.; Cussen, Edmund J.

    2013-04-15

    The cation ordered perovskites Ba{sub 2}Nd{sub 1−x}Y{sub x}MoO{sub 6} (0.04≤x≤0.35) have been synthesised by solid-state techniques under reducing conditions at temperatures up to 1350 °C. Rietveld analyses of X-ray and neutron powder diffraction data show that these compounds adopt a tetragonally distorted perovskite structure. The tetragonal distortion is driven by the bonding requirements of the Ba{sup 2+} cation that occupies the central interstice of the perovskite; this cation would be underbonded if these compounds retained the cubic symmetry exhibited by the prototypical structure. The size and charge difference between the lanthanides and Mo{sup 5+} lead to complete ordering of the cations to give a rock-salt ordering of Nd{sup 3+}/Y{sup 3+}O{sub 6} and MoO{sub 6} octahedra. The I4/m space group symmetry is retained on cooling the x=0.1, 0.2 and 0.35 samples to low temperature ca. 2 K. Ba{sub 2}Nd{sub 0.90}Y{sub 0.10}MoO{sub 6} undergoes a gradual distortion of the MoO{sub 6} units on cooling from room temperature to give two long trans bonds (2.001(2) Å) along the z-direction and four shorter apical bonds (1.9563(13) Å) in the xy-plane. This distortion of the MoO{sub 6} units stabilises the 4d{sup 1} electron in the d{sub xz} and d{sub yz} orbitals whilst the d{sub xy} orbital is increased in energy due to the contraction of the Mo–O bonds in the xy-plane. This bond extension along z is propagated through the structure and gives a negative thermal expansion of −13×10{sup −6} K{sup −1} along c. The overall volumetric thermal expansion is positive due to conventional expansion along the other two crystallographic axes. With increasing Y{sup 3+} content this distortion is reduced in x=0.2 and eliminated in x=0.35 which contains largely regular MoO{sub 6} octahedra. The x=0.1 and x=0.2 show small peaks in the neutron diffraction profile due to long range antiferromagnetic order arising from ordered moments of ca. 2 μ{sub B}. - Graphical

  17. Guest-Activated Forbidden Tilts in a Molecular Perovskite Analogue.

    PubMed

    Duyker, Samuel G; Hill, Joshua A; Howard, Christopher J; Goodwin, Andrew L

    2016-09-01

    The manipulation of distortions in perovskite structures is critical to tailoring the properties of these materials for a variety of applications. Here we demonstrate a violation of established octahedral tilt rules in the double perovskite analogue (NH4)2SrFe(CN)6·2H2O. The forbidden tilt pattern we observe arises through coupling to hydration-driven Jahn-Teller-like distortions of the Sr coordination environment. Access to novel distortion mechanisms and the ability to switch these distortions on and off through chemical modification fundamentally expands the toolbox of techniques available for engineering symmetry-breaking processes in solid materials. PMID:27533044

  18. Toward Revealing the Critical Role of Perovskite Coverage in Highly Efficient Electron-Transport Layer-Free Perovskite Solar Cells: An Energy Band and Equivalent Circuit Model Perspective.

    PubMed

    Huang, Like; Xu, Jie; Sun, Xiaoxiang; Du, Yangyang; Cai, Hongkun; Ni, Jian; Li, Juan; Hu, Ziyang; Zhang, Jianjun

    2016-04-20

    Currently, most efficient perovskite solar cells (PVKSCs) with a p-i-n structure require simultaneously electron transport layers (ETLs) and hole transport layers (HTLs) to help collecting photogenerated electrons and holes for obtaining high performance. ETL free planar PVKSC is a relatively new and simple structured solar cell that gets rid of the complex and high temperature required ETL (such as compact and mesoporous TiO2). Here, we demonstrate the critical role of high coverage of perovskite in efficient ETL free PVKSCs from an energy band and equivalent circuit model perspective. From an electrical point of view, we confirmed that the low coverage of perovskite does cause localized short circuit of the device. With coverage optimization, a planar p-i-n(++) device with a power conversion efficiency of over 11% was achieved, implying that the ETL layer may not be necessary for an efficient device as long as the perovskite coverage is approaching 100%. PMID:27020395

  19. Toward Revealing the Critical Role of Perovskite Coverage in Highly Efficient Electron-Transport Layer-Free Perovskite Solar Cells: An Energy Band and Equivalent Circuit Model Perspective.

    PubMed

    Huang, Like; Xu, Jie; Sun, Xiaoxiang; Du, Yangyang; Cai, Hongkun; Ni, Jian; Li, Juan; Hu, Ziyang; Zhang, Jianjun

    2016-04-20

    Currently, most efficient perovskite solar cells (PVKSCs) with a p-i-n structure require simultaneously electron transport layers (ETLs) and hole transport layers (HTLs) to help collecting photogenerated electrons and holes for obtaining high performance. ETL free planar PVKSC is a relatively new and simple structured solar cell that gets rid of the complex and high temperature required ETL (such as compact and mesoporous TiO2). Here, we demonstrate the critical role of high coverage of perovskite in efficient ETL free PVKSCs from an energy band and equivalent circuit model perspective. From an electrical point of view, we confirmed that the low coverage of perovskite does cause localized short circuit of the device. With coverage optimization, a planar p-i-n(++) device with a power conversion efficiency of over 11% was achieved, implying that the ETL layer may not be necessary for an efficient device as long as the perovskite coverage is approaching 100%.

  20. Controlling Octahedral Rotations in a Perovskite via Strain Doping

    PubMed Central

    Herklotz, A.; Wong, A. T.; Meyer, T.; Biegalski, M. D.; Lee, H. N.; Ward, T. Z.

    2016-01-01

    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 can be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO3 films coherently grown on SrTiO3 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. 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. PMID:27215804

  1. Controlling octahedral rotations in a perovskite via strain doping

    DOE PAGES

    Herklotz, Andreas; Biegalski, Michael D.; Lee, Ho Nyung; Ward, Thomas Zac; Wong, A. T.; Meyer, T.

    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 SrRuO3 films coherently grown on SrTiO3 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

  2. Controlling Octahedral Rotations in a Perovskite via Strain Doping

    NASA Astrophysics Data System (ADS)

    Herklotz, A.; Wong, A. T.; Meyer, T.; Biegalski, M. D.; Lee, H. N.; Ward, T. Z.

    2016-05-01

    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 can be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO3 films coherently grown on SrTiO3 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. 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.

  3. Crystal structures and high-temperature phase-transitions in SrNdMRuO{sub 6} (M=Zn,Co,Mg,Ni) new double perovskites studied by symmetry-mode analysis

    SciTech Connect

    Iturbe-Zabalo, E.; Larranaga, A.; Cuello, G.J.

    2013-02-15

    Crystal structures of SrNdZnRuO{sub 6}, SrNdCoRuO{sub 6}, SrNdMgRuO{sub 6} and SrNdNiRuO{sub 6} double perovskites have been studied by X-ray, synchrotron radiation and neutron powder diffraction method, at different temperatures, and using the symmetry-mode analysis. All compounds adopt the monoclinic space group P2{sub 1}/n at room-temperature, and contain a completely ordered array of the tilted MO{sub 6} and RuO{sub 6} octahedra, whereas Sr/Nd cations are completely disordered. The analysis of the structures in terms of symmetry-adapted modes of the parent phase allows the identification of the modes responsible for the phase-transition. The high-temperature study (300-1250 K) has shown that the compounds present a temperature induced structural phase-transition: P2{sub 1}/n{yields}P4{sub 2}/n{yields}Fm3{sup Macron }m. - Graphical abstract: Representation of the dominant distortion modes of the symmetry mode decomposition of the room-temperature (P2{sub 1}/n), intermediate (P4{sub 2}/n) and cubic (Fm-3m) phase SrNdMRuO{sub 6} (M=Zn,Co,Mg,Ni), with respect to the parent phase Fm-3m. The dominant distortion modes are: in the monoclinic phase-GM{sub 4}{sup +} (blue arrow), X{sub 3}{sup +} (green arrow) and X{sub 5}{sup +} acting on A-site cations (red arrow); in the tetragonal phase-GM{sub 4}{sup +} (pink arrow), X{sub 3}{sup +} (light blue arrow) and X{sub 5}{sup +} acting on A-site cations (brown arrow). Highlights: Black-Right-Pointing-Pointer Structural study of four ruthenate double perovskites. Black-Right-Pointing-Pointer Room-temperature structural determination using symmetry-mode procedure. Black-Right-Pointing-Pointer Determination of temperature induced structural phase-transitions. Black-Right-Pointing-Pointer Symmetry adapted-mode analysis.

  4. General study on the crystal, electronic and band structures, the morphological characterization, and the magnetic properties of the Sr{sub 2}DyRuO{sub 6} complex perovskite

    SciTech Connect

    Triana, C.A.; Landínez Téllez, D.A.; Roa-Rojas, J.

    2015-01-15

    A comprehensive investigation of the general properties of the Sr{sub 2}DyRuO{sub 6} complex perovskite was undertaken. Crystal structure characterization performed by X-ray diffraction measurements and Rietveld analysis allowed establishing that the material crystallizes in a distorted monoclinic perovskite-like structure belonging to the P2{sub 1}/n (#14) space group, with alternating distribution of Dy{sup 3} {sup +} (2c: 0, 0.5, 0) and Ru{sup 5} {sup +} (2d: 0.5, 0, 0). Because of the mismatch in the ionic radii, the DyO{sub 6} and RuO{sub 6} octahedra are forced to tilt around the cubic directions so as to optimize the Sr–O inter-atomic bond lengths. Morphological characterization carried out by scanning electron microscopy indicated a particle size D = 37.17 nm and an activation energy Q = 109.8 kJ/mol. Semi-quantitative compositional study, performed through energy-dispersive X-ray experiments, corroborated that the pure phase of the Sr{sub 2}DyRuO{sub 6} was correctly obtained. Magnetic properties determined from the fit of the Curie–Weiss law to the curves of magnetic susceptibility as a function of temperature showed that Sr{sub 2}DyRuO{sub 6} exhibits an antiferromagnetic-like behavior at low temperatures as a consequence of a magnetic transition at T = 38 K. Data collected with respect to the field dependence of the magnetization showed the existence of a weak ferromagnetic moment relationship with antiferromagnetic-like behavior. Density functional theory allowed establishing the optimum electronic structure for Sr{sub 2}DyRuO{sub 6}, and the study of the density of states showed that Dy{sup 3} {sup +} and Ru{sup 5} {sup +} are responsible for the magnetic character of the compound, with the prediction that at T = 0 K it behaves as a half-metallic material. The spin magnetic moment of the cell is close to 16 μ{sub B}, and the integer number of Bohr magneton is a signature of half-metallic character. Evolution of crystal structure at high

  5. Organic-inorganic hybrid lead halide perovskites for optoelectronic and electronic applications.

    PubMed

    Zhao, Yixin; Zhu, Kai

    2016-02-01

    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. PMID:26645733

  6. The effect of chemical variations on the structural polarity of relaxor ferroelectrics studied by resonance Raman spectroscopy.

    PubMed

    Rohrbeck, A; de la Flor, G; Aroyo, M I; Gospodinov, M; Bismayer, U; Mihailova, B

    2016-11-30

    Resonance Raman spectroscopy was applied to doped PbSc0.5Ta0.5O3 and PbSc0.5Nb0.5O3 relaxor ferroelectrics, to better understand the effect of composition disorder on the mesoscopic-scale polar order in complex perovskite-type (ABO3) ferroelectrics. The excitation photon energy used was 3.8 eV, which is slightly above the energy gap and corresponds to the maximum of the optical dielectric permittivity. Group-theory analysis reveals that the resonance Raman scattering (RRS) observed under these conditions is allowed only in polar crystal classes. Therefore, RRS is dominated by the atomic dynamics of nanoregions with coherent polar distortions, which considerably facilitates the comparison of polar order in various compounds. The results show that A-site doping (Ba(2+), Sr(2+), La(3+), Bi(3+)) has significantly stronger effect on the structural polarity than the introduction of a third element at the B site (Nb(5+) or Sn(4+) doped in PbSc0.5Ta0.5O3). The A-site substitution by cations that in contrast to Pb(2+) have isotropic outermost electron shells disturbs the system of lone-pair electrons, thus reducing the correlation length of coupled polar distortions and the strength of the electric field associated with the mean polarization of polar nanoregions. A-site doping with larger cations (Ba(2+)) augments the polar deformation of the individual BO6 octahedra due to local elastic fields. As a result, such A-site doping intensifies the initial structural polarity at high temperatures and prevails the enlargement of the polar fraction at low temperatures. A-site doping with smaller cations (Sr(2+), La(3+)), regardless if they are isovalent or aliovalent to Pb(2+), increases the correlation length of antiferrodistortive order (BO6 tilts), which in turn assists the development of double-perovskite structure with coherent local polar distortions. A-site doping with aliovalent cations (Bi(3+)) having the same outermost electron shell and ionic radius as the host A

  7. The effect of chemical variations on the structural polarity of relaxor ferroelectrics studied by resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Rohrbeck, A.; de la Flor, G.; Aroyo, M. I.; Gospodinov, M.; Bismayer, U.; Mihailova, B.

    2016-11-01

    Resonance Raman spectroscopy was applied to doped PbSc0.5Ta0.5O3 and PbSc0.5Nb0.5O3 relaxor ferroelectrics, to better understand the effect of composition disorder on the mesoscopic-scale polar order in complex perovskite-type (ABO3) ferroelectrics. The excitation photon energy used was 3.8 eV, which is slightly above the energy gap and corresponds to the maximum of the optical dielectric permittivity. Group-theory analysis reveals that the resonance Raman scattering (RRS) observed under these conditions is allowed only in polar crystal classes. Therefore, RRS is dominated by the atomic dynamics of nanoregions with coherent polar distortions, which considerably facilitates the comparison of polar order in various compounds. The results show that A-site doping (Ba2+, Sr2+, La3+, Bi3+) has significantly stronger effect on the structural polarity than the introduction of a third element at the B site (Nb5+ or Sn4+ doped in PbSc0.5Ta0.5O3). The A-site substitution by cations that in contrast to Pb2+ have isotropic outermost electron shells disturbs the system of lone-pair electrons, thus reducing the correlation length of coupled polar distortions and the strength of the electric field associated with the mean polarization of polar nanoregions. A-site doping with larger cations (Ba2+) augments the polar deformation of the individual BO6 octahedra due to local elastic fields. As a result, such A-site doping intensifies the initial structural polarity at high temperatures and prevails the enlargement of the polar fraction at low temperatures. A-site doping with smaller cations (Sr2+, La3+), regardless if they are isovalent or aliovalent to Pb2+, increases the correlation length of antiferrodistortive order (BO6 tilts), which in turn assists the development of double-perovskite structure with coherent local polar distortions. A-site doping with aliovalent cations (Bi3+) having the same outermost electron shell and ionic radius as the host A-site Pb2+ cations leads to

  8. The effect of chemical variations on the structural polarity of relaxor ferroelectrics studied by resonance Raman spectroscopy.

    PubMed

    Rohrbeck, A; de la Flor, G; Aroyo, M I; Gospodinov, M; Bismayer, U; Mihailova, B

    2016-11-30

    Resonance Raman spectroscopy was applied to doped PbSc0.5Ta0.5O3 and PbSc0.5Nb0.5O3 relaxor ferroelectrics, to better understand the effect of composition disorder on the mesoscopic-scale polar order in complex perovskite-type (ABO3) ferroelectrics. The excitation photon energy used was 3.8 eV, which is slightly above the energy gap and corresponds to the maximum of the optical dielectric permittivity. Group-theory analysis reveals that the resonance Raman scattering (RRS) observed under these conditions is allowed only in polar crystal classes. Therefore, RRS is dominated by the atomic dynamics of nanoregions with coherent polar distortions, which considerably facilitates the comparison of polar order in various compounds. The results show that A-site doping (Ba(2+), Sr(2+), La(3+), Bi(3+)) has significantly stronger effect on the structural polarity than the introduction of a third element at the B site (Nb(5+) or Sn(4+) doped in PbSc0.5Ta0.5O3). The A-site substitution by cations that in contrast to Pb(2+) have isotropic outermost electron shells disturbs the system of lone-pair electrons, thus reducing the correlation length of coupled polar distortions and the strength of the electric field associated with the mean polarization of polar nanoregions. A-site doping with larger cations (Ba(2+)) augments the polar deformation of the individual BO6 octahedra due to local elastic fields. As a result, such A-site doping intensifies the initial structural polarity at high temperatures and prevails the enlargement of the polar fraction at low temperatures. A-site doping with smaller cations (Sr(2+), La(3+)), regardless if they are isovalent or aliovalent to Pb(2+), increases the correlation length of antiferrodistortive order (BO6 tilts), which in turn assists the development of double-perovskite structure with coherent local polar distortions. A-site doping with aliovalent cations (Bi(3+)) having the same outermost electron shell and ionic radius as the host A

  9. 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.

  10. Tracking the formation of methylammonium lead triiodide perovskite

    SciTech Connect

    Liu, Lijia E-mail: jmcleod@suda.edu.cn; McLeod, John A. E-mail: jmcleod@suda.edu.cn; Wang, Rongbin; Shen, Pengfei; Duhm, Steffen

    2015-08-10

    The formation mechanism of perovskite methylammonium lead triiodide (CH{sub 3}NH{sub 3}PbI{sub 3}) was studied with in situ X-ray photoelectron spectroscopy (XPS) on successive depositions of thermally evaporated methylammonium iodide (CH{sub 3}NH{sub 3}I) on a lead iodide (PbI{sub 2}) film. This deposition method mimics the “two-step” synthesis method commonly used in device fabrication. We find that several competing processes occur during the formation of perovskite CH{sub 3}NH{sub 3}PbI{sub 3}. Our most important finding is that during vapour deposition of CH{sub 3}NH{sub 3}I onto PbI{sub 2}, at least two carbon species are present in the resulting material, while only one nitrogen species is present. This suggests that CH{sub 3}NH{sub 3}I can dissociate during the transition to a perovskite phase, and some of the resulting molecules can be incorporated into the perovskite. The effect of partial CH{sub 3}NH{sub 3} substitution with CH{sub 3} was evaluated, and electronic structure calculations show that CH{sub 3} defects would impact the photovoltaic performance in perovskite solar cells. The possibility that not all A sites in the APbI{sub 3} perovskite are occupied by CH{sub 3}NH{sub 3} is therefore an important consideration when evaluating the performance of organometallic trihalide solar cells synthesized using typical approaches.

  11. Multilayer Transparent Top Electrode for Solution Processed Perovskite/Cu(In,Ga)(Se,S)2 Four Terminal Tandem Solar Cells.

    PubMed

    Yang, Yang Michael; Chen, Qi; Hsieh, Yao-Tsung; Song, Tze-Bin; Marco, Nicholas De; Zhou, Huanping; Yang, Yang

    2015-07-28

    Halide perovskites (PVSK) have attracted much attention in recent years due to their high potential as a next generation solar cell material. To further improve perovskites progress toward a state-of-the-art technology, it is desirable to create a tandem structure in which perovskite may be stacked with a current prevailing solar cell such as silicon (Si) or Cu(In,Ga)(Se,S)2 (CIGS). The transparent top electrode is one of the key components as well as challenges to realize such tandem structure. Herein, we develop a multilayer transparent top electrode for perovskite photovoltaic devices delivering an 11.5% efficiency in top illumination mode. The transparent electrode is based on a dielectric/metal/dielectric structure, featuring an ultrathin gold seeded silver layer. A four terminal tandem solar cell employing solution processed CIGS and perovskite cells is also demonstrated with over 15% efficiency.

  12. Structural stability of anhydrous proton conducting SrZr0.9Er0.1O3-δ perovskite ceramic vs. protonation/deprotonation cycling: Neutron diffraction and Raman studies

    NASA Astrophysics Data System (ADS)

    Slodczyk, Aneta; Colomban, Philippe; Upasen, Settakorn; Grasset, Frédéric; André, Gilles

    2015-08-01

    Long-term chemical and structural stability of an ion conducting ceramic is one of the main criteria for its selection as an electrolytic membrane in energy plant devices. Consequently, medium density SrZr0.9Er0.1O3-δ (SZE) anhydrous proton conducting ceramic - a potential electrolyte of SOFC/PCFC, was analysed by neutron diffraction between room temperature and 900 °C. After the first heating/cooling cycle, the ceramic pieces were exposed to water vapour pressure in an autoclave (500 °C, 40 bar, 7 days) in order to incorporate protonic species; the protonated compound was then again analysed by neutron diffraction. This procedure was repeated two times. At each step, the sample was also controlled by TGA and Raman spectroscopy. These studies allow the first comprehensive comparison of structural and chemical stability during the protonation/deprotonation cycling. The results reveal good structural stability, although an irreversible small contraction of the unit-cell volume and local structure modifications near Zr/ErO5[] octahedra are detected after the first protonation. After the second protonation easy ceramic crumbling under a stress is observed because of the presence of secondary phases (SrCO3, Sr(OH)2) well detected by Raman scattering and TGA. The role of crystallographic purity, substituting element and residual porosity in the proton conducting perovskite electrolyte stability is discussed.

  13. Structural characterisation of the perovskite series Sr{sub 0.9-x}Ca{sub x}Ce{sub 0.1}MnO{sub 3}: Influence of the Jahn-Teller effect

    SciTech Connect

    Kennedy, Brendan J.; Ting, Jimmy; Zhou Qingdi; Zhang Zhaoming; Matsuda, Motohide; Miyake, Michihiro

    2009-04-15

    Fifteen perovskite-type compounds Sr{sub 0.9-x}Ca{sub x}Ce{sub 0.1}MnO{sub 3}, x=0-0.9 in steps as fine as 0.05, have been synthesised by solid state methods, and the room temperature structures characterised using X-ray synchrotron powder diffraction. At low Ca contents (x<=0.45) the structures are tetragonal in space group I4/mcm and at high Ca contents (x>=0.55) the compounds are orthorhombic in space group Pbnm. At room temperature these two phases co-exist in the compound with x=0.5. XANES measurements show the Ce to be present as Ce{sup 4+} in all the oxides. High temperature structures are reported for selected members. - Graphical abstract: At room temperature the oxides with x<=0.45 in the series Sr{sub 0.9-x}Ca{sub x}Ce{sub 0.1}MnO{sub 3} are tetragonal in I4/mcm with a large Jahn-Teller distortion, and those with x>=0.55 are orthorhombic, in Pbnm. Heating the tetragonal samples results in two transitions, ultimately the structure becomes cubic.

  14. NaIrO3—A Pentavalent Post-perovskite

    SciTech Connect

    M Bremholm; S Dutton; P Stephens; R Cava

    2011-12-31

    Sodium iridium (V) oxide, NaIrO{sub 3}, was synthesized by a high pressure solid state method and recovered to ambient conditions. It is found to be isostructural with CaIrO{sub 3}, the much-studied structural analog of the high-pressure post-perovskite phase of MgSiO{sub 3}. Among the oxide post-perovskites, NaIrO{sub 3} is the first example with a pentavalent cation. The structure consists of layers of corner- and edge-sharing IrO{sub 6} octahedra separated by layers of NaO{sub 8} bicapped trigonal prisms. NaIrO{sub 3} shows no magnetic ordering and resistivity measurements show non-metallic behavior. The crystal structure, electrical and magnetic properties are discussed and compared to known post-perovskites and pentavalent perovskite metal oxides.

  15. Perovskites: transforming photovoltaics, a mini-review

    NASA Astrophysics Data System (ADS)

    Chilvery, Ashwith Kumar; Batra, Ashok K.; Yang, Bin; Xiao, Kai; Guggilla, Padmaja; Aggarwal, Mohan D.; Surabhi, Raja; Lal, Ravi B.; Currie, James R.; Penn, Benjamin G.

    2015-01-01

    The recent power-packed advent of perovskite solar cells is transforming photovoltaics (PV) with their superior efficiencies, ease of fabrication, and cost. This perovskite solar cell further boasts of many unexplored features that can further enhance its PV properties and lead to it being branded as a successful commercial product. This article provides a detailed insight of the organometal halide based perovskite structure, its unique stoichiometric design, and its underlying principles for PV applications. The compatibility of various PV layers and its fabrication methods is also discussed.

  16. Organometal Trihalide Perovskite Spintronics

    NASA Astrophysics Data System (ADS)

    Sun, Dali

    The family of organometal trihalide perovskite (OTP), CH3NH3PbX3 (where X is halogen) has recently revolutionized the photovoltaics field, and shows promise in applications such as solar energy harnessing, light emitting diodes, field effect transistors and laser action. The OTP spin characteristic properties are influenced by the large spin-orbit-coupling of the Pb atoms, and thus may offer a new class of semiconductors for spin-based applications. In this talk we will summarize the `magnetic field effect' on photocurrent and electroluminescence in OTP optoelectronic devices, and photoluminescence from OTP films; and report more recent studies of pure spin-current and spin-aligned carrier injection in OTP spintronics devices using `spin-pumping' and `spin-injection', respectively. We measured relatively large inverse-spin-Hall effect using pulsed microwave excitation in OTP devices at resonance with a ferromagnetic (FM) layer, and giant magnetoresistance in OTP-based spin-valves. Our studies launch the field of OTP spintronics. Research sponsored by the DOE, Office of Science, Grant DE-SC0014579. Work done in collaboration with Chuang Zhang, Marzieh Kavand, Kipp J. van Schooten, Hans Malissa, Matthew Groesbeck, Ryan Mclaughlin, Christoph Boehme, and Z. Valy Vardeny.

  17. Structure, stability, and photoluminescence in the anti-perovskites Na{sub 3}W{sub 1−x}Mo{sub x}O{sub 4}F (0≤x≤1)

    SciTech Connect

    Sullivan, Eirin; Avdeev, Maxim; Blom, Douglas A.; Gahrs, Casey J.; Green, Robert L.; Hamaker, Christopher G.; Vogt, Thomas

    2015-10-15

    Single-phase ordered oxyfluorides Na{sub 3}WO{sub 4}F, Na{sub 3}MoO{sub 4}F and their mixed members Na{sub 3}W{sub 1−x}Mo{sub x}O{sub 4}F can be prepared via facile solid state reaction of Na{sub 2}MO{sub 4}·2H{sub 2}O (M=W, Mo) and NaF. Phases produced from incongruent melts are metastable, but lower temperatures allow for a facile one-step synthesis. In polycrystalline samples of Na{sub 3}W{sub 1−x}Mo{sub x}O{sub 4}F, the presence of Mo stabilizes the structure against decomposition to spinel phases. Photoluminescence studies show that upon excitation with λ=254 nm and λ=365 nm, Na{sub 3}WO{sub 4}F and Na{sub 3}MoO{sub 4}F exhibit broad emission maxima centered around 485 nm. These materials constitute new members of the family of self-activating ordered oxyfluoride phosphors with anti-perovskite structures which are amenable to doping with emitters such as Eu{sup 3+}. - Graphical abstract: Directed synthesis of the ordered oxyfluorides Na{sub 3}W{sub 1−x}Mo{sub x}O{sub 4}F (0≤x≤1) has shown that a complete solid solution is attainable and provides the first example of photoluminescence in these materials. - Highlights: • Na{sub 3}W{sub 1−x}Mo{sub x}O{sub 4}F is a complete solid solution with hexagonal anti-perovskite structure. • The presence of even small amounts of Mo stabilizes the structure against decomposition. • Na{sub 3}W{sub 1−x}Mo{sub x}O{sub 4}F has broad emissions centered ≈485 nm (λ{sub ex}=254 nm and λ{sub ex}=365 nm). • These materials constitute a new family of self-activated oxyfluoride phosphors. • Na{sub 3}W{sub 1−x}Mo{sub x}O{sub 4}F materials are amenable to doping with emitters such as Eu{sup 3+}.

  18. The Effect of Al on the Compressibility of Silicate Perovskite

    NASA Astrophysics Data System (ADS)

    Walter, M. J.; Kubo, A.; Yoshino, T.; Koga, K. T.; Ohishi, Y.

    2003-12-01

    Experimental data on compressibility of aluminous silicate perovskite show widely disparate results. Several studies show that Al causes a dramatic increase in compressibility1-3, while another study indicates a mild decrease in compressibility4. Here we report new results for the effect of Al on the room-temperature compressibility of perovskite using in situ X-ray diffraction in the diamond anvil cell from 30 to 100 GPa. We studied compressibility of perovskite in the system MgSiO3-Al2O3 in compositions with 0 to 25 mol% Al. Perovskite was synthesized from starting glasses using laser-heating in the DAC, with KBr as a pressure medium. Diffraction patterns were obtained using monochromatic radiation and an imaging plate detector at beamline BL10XU, SPring8, Japan. Addition of Al into the perovskite structure causes systematic increases in orthorhombic distortion and unit cell volume at ambient conditions (V0). Compression of the perovskite unit cell is anisotropic, with the a axis about 25% and 3% more compressive than the b and c axes, respectively. The magnitude of orthorhombic distortion increases with pressure, but aluminous perovskite remains stable to at least 100 GPa. Our results show that Al causes only a mild increase in compressibility, with the bulk modulus (K0) decreasing at a rate of 0.7 GPa/0.01 XAl. This increase in compressibility is consistent with recent ab initio calculations if Al mixes into both the 6- and 8-coordinated sites by coupled substitution5, where 2 Al3+ = Mg2+ + Si4+. Our results together with those of [4] indicate that this substitution mechanism predominates throughout the lower mantle. Previous mineralogic models indicating the upper and lower mantle are compositionally similar in terms of major elements remain effectively unchanged because solution of 5 mol% Al into perovskite has a minor effect on density. 1. Zhang & Weidner (1999). Science 284, 782-784. 2. Kubo et al. (2000) Proc. Jap. Acad. 76B, 103-107. 3. Daniel et al

  19. Additive to regulate the perovskite crystal film growth in planar heterojunction solar cells

    SciTech Connect

    Song, Xin; Sun, Po; Chen, Zhi-Kuan E-mail: iamzkchen@njtech.edu.cn; Wang, Weiwei; Ma, Wanli E-mail: iamzkchen@njtech.edu.cn

    2015-01-19

    We reported a planar heterojunction perovskite solar cell fabricated from MAPbI{sub 3−x}Cl{sub x} perovskite precursor solution containing 1-chloronaphthalene (CN) additive. The MAPbI{sub 3−x}Cl{sub x} perovskite films have been characterized by UV-vis, SEM, XRD, and steady-state photoluminescence (PL). UV-vis absorption spectra measurement shows that the absorbance of the film with CN additive is significantly higher than the pristine film and the absorption peak is red shift by 30 nm, indicating the perovskite film with additive possessing better crystal structures. In-situ XRD study of the perovskite films with additive demonstrated intense diffraction peaks from MAPbI{sub 3−x}Cl{sub x} perovskite crystal planes of (110), (220), and (330). SEM images of the films with additive indicated the films were more smooth and homogenous with fewer pin-holes and voids and better surface coverage than the pristine films. These results implied that the additive CN is beneficial to regulate the crystallization transformation kinetics of perovskite to form high quality crystal films. The steady-state PL measurement suggested that the films with additive contained less charge traps and defects. The planar heterojunction perovskite solar cells fabricated from perovskite precursor solution containing CN additive demonstrated 30% enhancement in performance compared to the devices with pristine films. The improvement in device efficiency is mainly attributed to the good crystal structures, more homogenous film morphology, and also fewer trap centers and defects in the films with the additive.

  20. Finding New Perovskite Halides via Machine learning

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-01

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning) via building a support vector machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  1. Finding new perovskite halides via machine learning

    DOE PAGES

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-26

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach toward rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning, henceforth referred to as ML) via building a support vectormore » machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br, or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 185 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor, and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. As a result, the trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.« less

  2. The effect of Co doping on structural, magnetic and magnetocaloric properties of La0.8Ca0.2Mn1-xCoxO3 perovskites (0 ≤ x ≤ 0.3)

    NASA Astrophysics Data System (ADS)

    Turki, D.; Cherif, R.; Hlil, E. K.; Ellouze, M.; Elhalouani, F.

    2014-09-01

    Studies of the structural, magnetic and magnetocaloric properties of polycrystalline La0.8Ca0.2Mn1-xCoxO3 compounds (0 ≤ x ≤0.3) perovskite manganites were carried out. Samples were synthesized by sol-gel process and then heated at 1000°C for 3 h. X-ray powder diffraction and magnetic measurements were used to investigate the structural and magnetic properties. Rietveld analysis shows that the samples crystallize in the orthorhombic structure with Pnma space group. Crystallographic analysis shows a variation in lattice parameters as cobalt substitution increases, accompanied by a variation in the interatomic distances and a small increase in MT-O-MT angles (MT = cobalt and manganese). Magnetocaloric studies on La0.8Ca0.2Mn1-xCoxO3 compounds with x = 0 and x = 0.2 have been investigated by measuring the magnetization as a function of temperature. At 2 T, the maximum magnetic entropy \\vert Δ SMmax\\vert is about 3.09 JṡKg-1ṡK-1 and 1.123 JṡKg-1ṡK-1 for x = 0 and 0.2, respectively. Besides, the RCP value decreases with increasing Co content from 55.845 JṡKg-1 to 49.971 JṡKg-1. Also, the existence of Griffiths Phase and its influence in the phase transition is discussed.

  3. Surface coverage enhancement of a mixed halide perovskite film by using an UV-ozone treatment

    NASA Astrophysics Data System (ADS)

    Lee, Hyunho; Rhee, Seunghyun; Kim, Jaeyoul; Lee, Changhee; Kim, Hyeok

    2016-08-01

    Recently, a significant breakthrough in emerging photovoltaics occurred. Now, perovskite solar cells, hybrid types of organic and inorganic solar cells, are considered as reliable next-generation solar cells due to their outstanding photovoltaic performance. Records of the National Renewable Energy Laboratory (NREL) on cell efficiency research indicates a prominent growth in the power conversion efficiency (PCE) of a perovskite solar cells which is now approaching 20.1%. Perovskite solar cells are, in general, classified into three types based on their structures; the mesoporous type with TiO2 nanoparticles, the meso-superstructure type with Al2O3 and the planar hetero-junction type. Among them, planar-structured perovskite solar cells have strong advantages due to their easy processibility and flexibility. We can replace the materials in the electron transport layer (ETL) and the hole transport layer (HTL) with common materials that are available in organic solar cells. However, a great challenge is to fabricate a high-quality perovskite film because the perovskite morphology is highly sensitive to its fabrication conditions. For control of the film's morphology, some experiments, such as changing the annealing temperature or time and adding some additives, have been done to increase the surface coverage of perovskite films. In this work, we introduce normal, planar, perovskite solar cells with a hetero-junction structure based on compact TiO2 and a mixed halide perovskite (CH3NH3PbI3- x Cl x ). To enlarge the surface coverage of perovskite film, we used an UV-ozone treatment on top of the compact TiO2, which made the surface of TiO2 hydrophilic. Because a perovskite precursor is hydrophilic, an UV-ozone treatment is expected to improve the wettability between the compact TiO2 and the perovskite film. Here, we present the photovoltaic performance, along with the surface coverage difference, for various UV-ozone treatment time. In addition, the effect of the UV

  4. Efficient light-emitting diodes based on nanocrystalline perovskite in a dielectric polymer matrix.

    PubMed

    Li, Guangru; Tan, Zhi-Kuang; Di, Dawei; Lai, May Ling; Jiang, Lang; Lim, Jonathan Hua-Wei; Friend, Richard H; Greenham, Neil C

    2015-04-01

    Electroluminescence in light-emitting devices relies on the encounter and radiative recombination of electrons and holes in the emissive layer. In organometal halide perovskite light-emitting diodes, poor film formation creates electrical shunting paths, where injected charge carriers bypass the perovskite emitter, leading to a loss in electroluminescence yield. Here, we report a solution-processing method to block electrical shunts and thereby enhance electroluminescence quantum efficiency in perovskite devices. In this method, a blend of perovskite and a polyimide precursor dielectric (PIP) is solution-deposited to form perovskite nanocrystals in a thin-film matrix of PIP. The PIP forms a pinhole-free charge-blocking layer, while still allowing the embedded perovskite crystals to form electrical contact with the electron- and hole-injection layers. This modified structure reduces nonradiative current losses and improves quantum efficiency by 2 orders of magnitude, giving an external quantum efficiency of 1.2%. This simple technique provides an alternative route to circumvent film formation problems in perovskite optoelectronics and offers the possibility of flexible and high-performance light-emitting displays.

  5. Synthesis and structural properties of (Y, Sr)(Ti, Fe, Nb)O3-δ perovskite nanoparticles fabricated by modified polymer precursor method

    NASA Astrophysics Data System (ADS)

    Miruszewski, T.; Gdaniec, P.; Karczewski, J.; Bochentyn, B.; Szaniawska, K.; Kupracz, P.; Prześniak-Welenc, M.; Kusz, B.

    2016-09-01

    The yttrium, iron and niobium doped-SrTiO3 powders have been successfully fabricated by a modified low-temperature synthesis method from a polymer complex. The usage of strontium hydroxide precursor instead of conventional strontium nitrate or strontium carbonate provides to the possibility of significant decrease of annealing temperature. It allows to prepare a material with sphere-shape grains of nanometric size (15-70 nm). The results of thermal analysis indicate that the crystallization of precursor takes place at different stages. The product after heat treatment at 600 °C for 3 h in air was also characterized by X-Ray diffraction method (XRD) and Fourier transform - infrared spectroscopy (FT-IR). After the crystallization and the impurity removal process, a single-phase material was obtained in case of all analyzed samples. The morphology of obtained nano-powders was also studied by a scanning electron microscopy (SEM). It can be concluded, that this method allows obtaining a perovskite phase of a metal doped SrTiO3 with nanometric particles.

  6. Layering fabrication, structure, and electromagnetic properties of perovskite phases by hybrid process: self-propagated high-temperature synthesis and selective laser sintering

    NASA Astrophysics Data System (ADS)

    Shishkovsky, I.; Morozov, Yu.; Kuznetsov, M.

    2013-11-01

    The paper discusses the fundamentals and the requirements for layer-by-layer manufacturing of three-dimensional porous parts from complex metal oxide systems (piezoceramics PbTi1-xZrxO3; hexaferrites - BaFe12-xCrxO19 and SrFe12O19; spinels - Li0.5Fe2.5-xCrxO4 and high-temperature superconducting ceramics (HTSC) - YBa2Cu3O7-y) and examines the main aspects of the overlapped processes associated with the self-propagated high-temperature synthesis (SHS) and selective laser sintering (SLS). These two techniques presently offered are joined as the original solutions in this external magnetic field. The perovskite phase compositions, morphology, and element distribution of the fabricated samples were analyzed by the X-ray diffraction (XRD), scanning electron microscopy (SEM) equipped the EDX analysis. Optimal regimes for the three-dimensional (3D) parts laser synthesis and some of their electro physical properties were estimated for conducting the concurrent SHS-SLS reactions, both for the case with the applied dc magnetic field and without it.

  7. The effect of chemical pressure on the structure and properties of A2CrOsO6 (A=Sr, Ca) ferrimagnetic double perovskite

    NASA Astrophysics Data System (ADS)

    Morrow, Ryan; Soliz, Jennifer R.; Hauser, Adam J.; Gallagher, James C.; Susner, Michael A.; Sumption, Michael D.; Aczel, Adam A.; Yan, Jiaqiang; Yang, Fengyuan; Woodward, Patrick M.

    2016-06-01

    The ordered double perovskites Sr2CrOsO6 and Ca2CrOsO6 have been synthesized and characterized with neutron powder diffraction, electrical transport measurements, and high field magnetization experiments. As reported previously Sr2CrOsO6 crystallizes with R 3 bar symmetry due to a-a-a- octahedral tilting. A decrease in the tolerance factor leads to a-a-b+ octahedral tilting and P21/n space group symmetry for Ca2CrOsO6. Both materials are found to be ferrimagnetic insulators with saturation magnetizations near 0.2 μB. Sr2CrOsO6 orders at 660 K while Ca2CrOsO6 orders at 490 K. Variable temperature magnetization measurements suggest that the magnetization of the Cr3+ and Os3+ sublattices have different temperature dependences in Sr2CrOsO6. This leads to a non-monotonic temperature evolution of the magnetic moment. Similar behavior is not seen in Ca2CrOsO6. Both compounds have similar levels of Os/Cr antisite disorder, with order parameters of η=80.2(4)% for Sr2CrOsO6 and η=76.2(5)% for Ca2CrOsO6, where η=2θ-1 and θ is the occupancy of the osmium ion on the osmium-rich Wyckoff site.

  8. Growth of (Sr,La)-(Ta,Ti)-O-N perovskite oxide and oxynitride films by radio frequency magnetron sputtering: Influence of the reactive atmosphere on the film structure

    NASA Astrophysics Data System (ADS)

    Le Paven, C.; Le Gendre, L.; Benzerga, R.; Cheviré, F.; Tessier, F.; Jacq, S.; Traoré-Mantion, S.; Sharaiha, A.

    2015-03-01

    In the search for new dielectric and ferroelectric compounds, we were interested in the perovskite (Sr1-xLax)2(Ta1-xTix)2O7 solid solution with ferroelectric end members Sr2Ta2O7 (TCurie=-107 °C) and La2Ti2O7 (TCurie=1461 °C). In order to achieve a Curie temperature close to room temperature, the formulation with x=0.01 was chosen and synthetized as thin films by reactive radio-frequency magnetron sputtering. In oxygen rich plasma, a (Sr0.99La0.01)2(Ta0.99Ti0.01)2O7 film is deposited, characterized by a band-gap Eg=4.75 eV and an (1 1 0) epitaxial growth on (0 0 1)MgO substrate. The use of nitrogen rich plasma allows to synthesize (Sr0.99La0.01)(Ta0.99Ti0.01)O2N oxynitride films, with band gap Eg~2.10 eV and a polycrystalline, textured or epitaxial growth on (0 0 1)MgO substrate. Nitrogen-substoichiometric oxynitride films with larger lattice cells are produced for low dinitrogen percentages in the sputtering plasma.

  9. Cs{sub 3}Zr{sub 7}Cl{sub 20}Mn: A zirconium cluster network compound with isolated ZrCl{sub 5}{sup {minus}} units in a stuffed perovskite structure

    SciTech Connect

    Zhang, Jie; Corbett, J.D.

    1995-03-29

    Reactions of Zr, ZrCl{sub 4}, and MnCl{sub 2} in welded Ta containers at 800 {degrees}C produce the title phase in major amounts. A comparable electronic and structural configuration is also found with interstitial boron, but not in isostructural compounds with other interstitial or alkali metal atoms. The crystal structure of Cs{sub 3}(ZrCl{sub 5})[Zr{sub 6}(Mn)Cl{sub 12}]Cl{sub 6/2} was established by single-crystal diffraction (R3c, Z = 6, a = 12.8924(1) {angstrom}, c = 35.187 (6) {angstrom}, R/R{sub w} = 1.9/2.3% for 920 data to 20 = 60{degrees}). The structure contains a three-dimensional array of 18-electron Zr{sub 6}(Mn)Cl{sub 12} clusters interbridged by 6/2 Cl{sup a-a} atoms at zirconium vertices. This represents a sixth independent structure type for M{sub 6}X{sub 15} bridged cluster networks. The structure derives from a ReO{sub 3}-like primitive lattice of the cubic Nb{sub 6}F{sub 15} structure with linear bridges that has been given a {open_quotes}trigonal twist{close_quotes} about [111] to form a rhombohedral (tilted) perovskite arrangement with the novel ZrCl{sub 5}{sup {minus}} at the body center. This new D{sub 3h} anion does not share halogen with the rest of the structure and appears to be stabilized by a particularly good fit within the network. A double ccp cluster arrangement along c{sub H} provides for a coherent intercluster bridging arrangement. The cesium cations necessitated by the anionic network and by the CsZrCl{sub 5} component are bound in well-suited 12-coordinate sites among the chlorines.

  10. 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.

  11. Solvent-Assisted Gel Printing for Micropatterning Thin Organic-Inorganic Hybrid Perovskite Films.

    PubMed

    Jeong, Beomjin; Hwang, Ihn; Cho, Sung Hwan; Kim, Eui Hyuk; Cha, Soonyoung; Lee, Jinseong; Kang, Han Sol; Cho, Suk Man; Choi, Hyunyong; Park, Cheolmin

    2016-09-27

    While tremendous efforts have been made for developing thin perovskite films suitable for a variety of potential photoelectric applications such as solar cells, field-effect transistors, and photodetectors, only a few works focus on the micropatterning of a perovskite film which is one of the most critical issues for large area and uniform microarrays of perovskite-based devices. Here we demonstrate a simple but robust method of micropatterning a thin perovskite film with controlled crystalline structure which guarantees to preserve its intrinsic photoelectric properties. A variety of micropatterns of a perovskite film are fabricated by either microimprinting or transfer-printing a thin spin-coated precursor film in soft-gel state with a topographically prepatterned elastomeric poly(dimethylsiloxane) (PDMS) mold, followed by thermal treatment for complete conversion of the precursor film to a perovskite one. The key materials development of our solvent-assisted gel printing is to prepare a thin precursor film with a high-boiling temperature solvent, dimethyl sulfoxide. The residual solvent in the precursor gel film makes the film moldable upon microprinting with a patterned PDMS mold, leading to various perovskite micropatterns in resolution of a few micrometers over a large area. Our nondestructive micropatterning process does not harm the intrinsic photoelectric properties of a perovskite film, which allows for realizing arrays of parallel-type photodetectors containing micropatterns of a perovskite film with reliable photoconduction performance. The facile transfer of a micropatterned soft-gel precursor film on other substrates including mechanically flexible plastics can further broaden its applications to flexible photoelectric systems.

  12. Solvent-Assisted Gel Printing for Micropatterning Thin Organic-Inorganic Hybrid Perovskite Films.

    PubMed

    Jeong, Beomjin; Hwang, Ihn; Cho, Sung Hwan; Kim, Eui Hyuk; Cha, Soonyoung; Lee, Jinseong; Kang, Han Sol; Cho, Suk Man; Choi, Hyunyong; Park, Cheolmin

    2016-09-27

    While tremendous efforts have been made for developing thin perovskite films suitable for a variety of potential photoelectric applications such as solar cells, field-effect transistors, and photodetectors, only a few works focus on the micropatterning of a perovskite film which is one of the most critical issues for large area and uniform microarrays of perovskite-based devices. Here we demonstrate a simple but robust method of micropatterning a thin perovskite film with controlled crystalline structure which guarantees to preserve its intrinsic photoelectric properties. A variety of micropatterns of a perovskite film are fabricated by either microimprinting or transfer-printing a thin spin-coated precursor film in soft-gel state with a topographically prepatterned elastomeric poly(dimethylsiloxane) (PDMS) mold, followed by thermal treatment for complete conversion of the precursor film to a perovskite one. The key materials development of our solvent-assisted gel printing is to prepare a thin precursor film with a high-boiling temperature solvent, dimethyl sulfoxide. The residual solvent in the precursor gel film makes the film moldable upon microprinting with a patterned PDMS mold, leading to various perovskite micropatterns in resolution of a few micrometers over a large area. Our nondestructive micropatterning process does not harm the intrinsic photoelectric properties of a perovskite film, which allows for realizing arrays of parallel-type photodetectors containing micropatterns of a perovskite film with reliable photoconduction performance. The facile transfer of a micropatterned soft-gel precursor film on other substrates including mechanically flexible plastics can further broaden its applications to flexible photoelectric systems. PMID:27571339

  13. Layered-structural monoclinic–orthorhombic perovskite La{sub 2}Ti{sub 2}O{sub 7} to orthorhombic LaTiO{sub 3} phase transition and their microstructure characterization

    SciTech Connect

    Herrera, G.; Jiménez-Mier, J.; Chavira, E.

    2014-03-01

    The layered-structural ceramics, such as lanthanum titanate (La{sub 2}Ti{sub 2}O{sub 7}), have been known for their good temperature and low dielectric loss at microwave frequencies that make them good candidate materials for high frequency applications. However, few studies have been conducted on the synthesis optimization by sol gel reaction, in particular by acrylamide polymerization route. The interest in La{sub 2}Ti{sub 2}O{sub 7} ceramic has been greatly increased recently due to the effect of oriented grains. This anisotropy of the microstructure leads to anisotropy in dielectric, electrical and mechanical properties. In this study, grain oriented lanthanum titanate was produced by the sol–gel acrylamide polymerization route. The characterizations of the samples were achieved by thermal analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and transmission electron microscopy (TEM). X-ray diffraction indicates that the formation of monoclinic perovskite La{sub 2}Ti{sub 2}O{sub 7} nanocrystals is a necessary first step to obtain orthorhombic LaTiO{sub 3} nanocomposites (with space group Pbnm). In this work we identified that the monoclinic perovskite La{sub 2}Ti{sub 2}O{sub 7} with space group P2{sub 1} transforms its structure into one with the orthorhombic space group Cmc2{sub 1} at approximately 1073 K. The microstructure associated consisted of flaky monoclinic La{sub 2}Ti{sub 2}O{sub 7} nanocomposites in comparison with round-shaped LaTiO{sub 3} nanocomposites. - Highlights: • The flaky-like La{sub 2}Ti{sub 2}O{sub 7} compound was synthesized by sol–gel acrylamide route. • Simultaneous monitoring of the DTA and XRD with temperature was performed. • Phase transformation characterization of La{sub 2}Ti{sub 2}O{sub 7} has been carried out. • The variation of the La{sub 2}Ti{sub 2}O{sub 7} and LaTiO{sub 3} grain morphology has been compared.

  14. Structural characterization, magnetic behavior and high-resolution EELS study of new perovskites Sr{sub 2}Ru{sub 2-} {sub x} Co {sub x} O{sub 6-} {sub {delta}} (0.5{<=}x{<=}1.5)

    SciTech Connect

    Lozano-Gorrin, A.D. Greedan, J.E.; Nunez, P.; Gonzalez-Silgo, C.; Botton, G.A.; Radtke, G.

    2007-04-15

    New oxides of general formula Sr{sub 2}Ru{sub 2-} {sub x} Co {sub x} O{sub 6-} {sub {delta}} (0.5{<=}x{<=}1.5) have been synthesized as polycrystalline materials and characterized structurally by X-ray diffraction. For 0.5{<=}x<0.67 the orthorhombic, Pnma, perovskite structure of the end member, SrRuO{sub 3}, is found. At x=0.67 a phase separation into an Ru-rich Pnma phase and a Co-rich I2/c phase occurs. The I2/c form is also found for x=1.0 but another orthorhombic phase, Imma, obtains for x=1.33 and 1.5. Reductive weight losses indicate negligible oxygen non-stoichiometry, i.e., {delta}{approx}0, for all compositions even those rich in Co. High-resolution electron energy loss spectroscopy (EELS) indicates that cobalt is high-spin Co{sup 3+} or high-spin Co{sup 4+} for all x. Appropriate combinations of Ru{sup 4+}, Ru{sup 5+}, HS Co{sup 3+} and HS Co{sup 4+} are proposed for each x which are consistent with the observed Ru(Co)-O distances. Significant amounts of Co{sup 4+} must be present for large x values to explain the short observed distances. Broad maxima in the d.c. susceptibilities are found between 78 and 97 K with increasing x, along with zero-field-cooled (ZFC) and field-cooled (FC) divergences suggesting glassy magnetic freezing. A feature near 155 K for all samples indicates a residual amount of ferromagnetic SrRuO{sub 3} not detected by X-ray diffraction. - Graphical abstract: Correlation between the average B-site radius, the Goldschmidt tolerance factor and the sequence of space groups and Glazer tilt systems found for the perovskite solid solution Sr{sub 2}Ru{sub 2-} {sub x} Co {sub x} O{sub 6}.

  15. Structural, optical and dielectric relaxor properties of neodymium doped cubic perovskite (Ba1-xNd2x/3)(Zr0.3Ti0.7)O3

    NASA Astrophysics Data System (ADS)

    Ghosh, S. K.; Ganguly, M.; Rout, S. K.; Chanda, S.; Sinha, T. P.

    2014-04-01

    Neodymium doped Barium Zirconate Titanate (Ba1-xNd2x/3)(Zr0.3Ti0.7)O3 (x = 0.00, 0.02, 0.04, 0.06, 0.08, 0.10) ceramics were prepared using the solid state reaction route. Structural characterizations of the materials were done by using X-ray diffraction and Raman spectroscopy. XRD study suggested that all the compositions were of single phase cubic perovskite structure with space group Pm-3m while Raman spectra revealed that the replacement of the Ba2+ ions by Nd3+ ions significantly reduced the intensity of the Raman active modes and shifted them towards higher energy side. Room temperature optical property was analyzed by photoluminescence spectroscopy, which confirmed formation of shallow defects in the band gap. Photoluminescence property was attributed to the presence of polar [TiO6] distorted clusters in the globally cubic matrix. As a result PL emission spectra of these materials were found to belong to violet-blue regions. Microstructural study of sintered pellets revealed that the grain sizes increase with increase in doping concentration. The temperature dependence of the dielectric properties was investigated in the frequency range 1 kHz to 1 MHz. The broadening in the dielectric constant peak around the phase transition temperature and shifting of the temperature maximum towards higher temperatures with increase in frequency indicated a relaxor type of behavior.

  16. 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

    2016-01-01

    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

  17. 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

  18. 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.

  19. Hybrid halide perovskite solar cell precursors: colloidal chemistry and coordination engineering behind device processing for high efficiency.

    PubMed

    Yan, Keyou; Long, Mingzhu; Zhang, Tiankai; Wei, Zhanhua; Chen, Haining; Yang, Shihe; Xu, Jianbin

    2015-04-01

    The precursor of solution-processed perovskite thin films is one of the most central components for high-efficiency perovskite solar cells. We first present the crucial colloidal chemistry visualization of the perovskite precursor solution based on analytical spectra and reveal that perovskite precursor solutions for solar cells are generally colloidal dispersions in a mother solution, with a colloidal size up to the mesoscale, rather than real solutions. The colloid is made of a soft coordination complex in the form of a lead polyhalide framework between organic and inorganic components and can be structurally tuned by the coordination degree, thereby primarily determining the basic film coverage and morphology of deposited thin films. By utilizing coordination engineering, particularly through employing additional methylammonium halide over the stoichiometric ratio for tuning the coordination degree and mode in the initial colloidal solution, along with a thermal leaching for the selective release of excess methylammonium halides, we achieved full and even coverage, the preferential orientation, and high purity of planar perovskite thin films. We have also identified that excess organic component can reduce the colloidal size of and tune the morphology of the coordination framework in relation to final perovskite grains and partial chlorine substitution can accelerate the crystalline nucleation process of perovskite. This work demonstrates the important fundamental chemistry of perovskite precursors and provides genuine guidelines for accurately controlling the high quality of hybrid perovskite thin films without any impurity, thereby delivering efficient planar perovskite solar cells with a power conversion efficiency as high as 17% without distinct hysteresis owing to the high quality of perovskite thin films.

  20. Degradation mechanism for planar heterojunction perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Yamamoto, Kouhei; Furumoto, Yoshikazu; Shahiduzzaman, M.; Kuwabara, Takayuki; Takahashi, Kohshin; Taima, Tetsuya

    2016-04-01

    Organic-inorganic hybrid perovskite materials have recently emerged as a promising cost- and energy-efficient light absorber material for photovoltaic applications. Unfortunately, perovskite solar cells have a problem with decreasing power conversion efficiency owing to their degradation in air. To clarify the cause of the degradation of perovskite solar cells, we exposed deposited CH3NH3PbI3 and HC(NH2)2PbI3 films to an O2 or (H2O+N2) atmosphere condition. Analysis of these films revealed that a large energy band gap was observed as a result of the influence of the H2O molecule in CH3NH3PbI3 and HC(NH2)2PbI3. Under the (H2O+N2) atmosphere condition, the existence of CH3NH3I and HC(NH2)2I molecules was found to affect the morphology and as well as the crystalline diffraction peak. The resultant perovskite crystalline structure was degraded by H2O molecules under the air exposure condition.

  1. Krypton irradiation damage in Nd-doped zirconolite and perovskite

    NASA Astrophysics Data System (ADS)

    Davoisne, C.; Stennett, M. C.; Hyatt, N. C.; Peng, N.; Jeynes, C.; Lee, W. E.

    2011-08-01

    Understanding the effect of radiation damage and noble gas accommodation in potential ceramic hosts for plutonium disposition is necessary to evaluate their long-term behaviour during geological disposal. Polycrystalline samples of Nd-doped zirconolite and Nd-doped perovskite were irradiated ex situ with 2 MeV Kr + at a dose of 5 × 10 15 ions cm -2 to simulate recoil of Pu nuclei during alpha decay. The feasibility of thin section preparation of both pristine and irradiated samples by Focused Ion Beam sectioning was demonstrated. After irradiation, the Nd-doped zirconolite revealed a well defined amorphous region separated from the pristine material by a thin (40-60 nm) damaged interface. The zirconolite lattice was lost in the damaged interface, but the fluorite sublattice was retained. The Nd-doped perovskite contained a defined irradiated layer composed of an amorphous region surrounded by damaged but still crystalline layers. The structural evolution of the damaged regions is consistent with a change from orthorhombic to cubic symmetry. In addition in Nd-doped perovskite, the amorphisation dose depended on crystallographic orientation and possibly sample configuration (thin section or bulk). Electron Energy Loss Spectroscopy revealed Ti remained in the 4+ oxidation state but there was a change in Ti coordination in both Nd-doped perovskite and Nd-doped zirconolite associated with the crystalline to amorphous transition.

  2. Temperature-independent sensors based on perovskite-type oxides

    NASA Astrophysics Data System (ADS)

    Zaza, F.; Frangini, S.; Leoncini, J.; Luisetto, I.; Masci, A.; Pasquali, M.; Tuti, S.

    2014-06-01

    The need of energy security and environment sustainability drives toward the development of energy technology in order to enhance the performance of internal combustion engines. Gas sensors play a key role for controlling the fuel oxygen ratio and monitoring the pollution emissions. The perovskite-type oxides can be synthesized for an extremely wide variety of combinations of chemical elements, allowing to design materials with suitable properties for sensing application. Lanthanum strontium ferrites, such as La0.7Sr0.3FeO3, are suitable oxygen sensing materials with temperature-independence conductivity, but they have low chemical stability under reducing conditions. The addition of aluminum into the perovskite structure improves the material properties in order to develop suitable oxygen sensing probes for lean burn engine control systems. Perovskite-type oxides with formula (La0.7Sr0.3)(AlxFe1-x)O3 was synthesized by the citrate-nitrate combustion synthesis method. XRD analyses, show that it was synthesized a phase-pure powder belonging to the perovskite structure. Aluminum affects both the unit cell parameters, by shrinking the unit cell, and the powder morphology, by promoting the synthesis of particles with small crystallite size and large specific surface area. The partial substitution of iron with aluminum improves the chemical stability under reducing gas conditions and modulates the oxygen sensitivity by affecting the relative amount of Fe4+ and Fe3+, as confirmed from TPR profiles. In the same time, the addition of aluminum does not affects the temperature-independent properties of lanthanum strontium ferrites. Indeed, the electrical measurements show that (La0.7Sr0.3)(AlxFe1-x)O3 perovskites have temperature-independence conductivity from 900 K.

  3. Temperature-independent sensors based on perovskite-type oxides

    SciTech Connect

    Zaza, F.; Frangini, S.; Masci, A.; Leoncini, J.; Pasquali, M.; Luisetto, I.; Tuti, S.

    2014-06-19

    The need of energy security and environment sustainability drives toward the development of energy technology in order to enhance the performance of internal combustion engines. Gas sensors play a key role for controlling the fuel oxygen ratio and monitoring the pollution emissions. The perovskite-type oxides can be synthesized for an extremely wide variety of combinations of chemical elements, allowing to design materials with suitable properties for sensing application. Lanthanum strontium ferrites, such as La{sub 0.7}Sr{sub 0.3}FeO{sub 3}, are suitable oxygen sensing materials with temperature-independence conductivity, but they have low chemical stability under reducing conditions. The addition of aluminum into the perovskite structure improves the material properties in order to develop suitable oxygen sensing probes for lean burn engine control systems. Perovskite-type oxides with formula (La{sub 0.7}Sr{sub 0.3})(Al{sub x}Fe{sub 1−x})O{sub 3} was synthesized by the citrate-nitrate combustion synthesis method. XRD analyses, show that it was synthesized a phase-pure powder belonging to the perovskite structure. Aluminum affects both the unit cell parameters, by shrinking the unit cell, and the powder morphology, by promoting the synthesis of particles with small crystallite size and large specific surface area. The partial substitution of iron with aluminum improves the chemical stability under reducing gas conditions and modulates the oxygen sensitivity by affecting the relative amount of Fe{sup 4+} and Fe{sup 3+}, as confirmed from TPR profiles. In the same time, the addition of aluminum does not affects the temperature-independent properties of lanthanum strontium ferrites. Indeed, the electrical measurements show that (La{sub 0.7}Sr{sub 0.3})(Al{sub x}Fe{sub 1−x})O{sub 3} perovskites have temperature-independence conductivity from 900 K.

  4. Towards better analogues for MgSiO 3 post-perovskite: NaCoF 3 and NaNiF 3, two new recoverable fluoride post-perovskites

    NASA Astrophysics Data System (ADS)

    Dobson, David P.; Hunt, Simon A.; Lindsay-Scott, Alexander; Wood, Ian G.

    2011-12-01

    We present details of two new quenchable post-perovskite-structured NaBF 3 compounds, where B is Co or Ni. Both post-perovskites are readily synthesised in the multi-anvil-press pressure range and have unit cells with axial ratios similar to MgSiO 3 post-perovskite (NaCoF 3a = 3.07035(7) Å, b = 10.1291(3) Å, c = 7.4664(1) Å, V = 232.20(1) Å 3; NaNiF 3a = 3.0247(2) Å, b = 10.0543(7) Å, c = 7.3989(3) Å, V = 225.01(3) Å 3). For NaCoF 3, we have synthesised post-perovskite single crystals and determined the phase diagram: the perovskite-post-perovskite transition occurs at 18 GPa and 700 °C, with a Clapeyron slope of 15.5 MPa/K. On the basis of the above factors, combined with (1) the fact that ABF 3 compositions also have stable perovskite phases and (2) the relatively small differences in the mass ratios of their constituent atoms, we suggest that these systems might prove to be better analogues for MgSiO 3 post-perovskite than the currently used CaBO 3 (where B is Ir, Pt, Rh, Ru) compositions.

  5. Stability of MgSio[subscript 3] Perovskite in the Lower Mantle

    SciTech Connect

    Shim, D.

    2006-01-19

    As it is expected to be the dominant phase in the lower mantle, any pressure-induced phase changes in MgSiO{sub 3} could require significant modifications in current models of the dynamics and structures of Earth's deep mantle. Studies to date have yielded discrepant results regarding the high-pressure stability of MgSiO{sub 3} perovskite. Understanding the source of discrepancy is essential, both to resolving the stability of perovskite and to developing more reliable techniques for understanding the Earth's deep interior. In this report, we give an overview of previous studies on the stability of MgSiO{sub 3} perovskite and recent observations on the post-perovskite transition. We also summarize our measurements on MgSiO{sub 3} perovskite to core-mantle boundary pressure-temperature (P-T) conditions using in-situ X-ray diffraction. Major peaks in our diffraction patterns are best explained by those of MgSiO{sub 3} perovskite at 1200-2500-km depth conditions. No evidence of dissociation to MgO + SiO, and a transition to a cubic perovskite structure has been found to core-mantle boundary P-T conditions. We have also observed a new peak at 2.62-2.57 {angstrom} at 88-145 GPa, the existence of which may be relevant to a modification in perovskite crystal structure. However, the possibility that this peak may be from a chemical reaction among gasket, anvil materials, and sample cannot be ruled out. More significant changes are observed during heating above 2500 K at 135-145 GPa: appearance of new peaks, splitting of a peak, and intensity changes of some diffraction peaks. The recently proposed post-perovskite phase explains dominant new diffraction features. Based on the results available as of May 2005, the post-perovskite transition appears to be relevant to the D seismic discontinuity. Furthermore, depth of the post-perovskite transition may be very sensitive to variations in chemical composition as well as temperature.

  6. The Renaissance of Halide Perovskites and Their Evolution as Emerging Semiconductors.

    PubMed

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2015-10-20

    The recent re-emergence of the halide perovskites, of the type AMX3, derives from a sea-changing breakthrough in the field of photovoltaics that has led to a whole new generation of solar devices with remarkable power conversion efficiency. The success in the field of photovoltaics has led to intense, combined research efforts to better understand these materials both from the fundamental chemistry and physics points of view and for the improvement of applied functional device engineering. This groundswell of activity has breathed new life into this long-known but largely "forgotten" class of perovskites. The impressive achievements of halide perovskites in photovoltaics, as well as other optoelectronic applications, stem from an unusually favorable combination of optical and electronic properties, with the ability to be solution processed into films. This defines them as a brand new class of semiconductors that can rival or exceed the performance of the venerable classes of III-V and II-IV semiconductors, which presently dominate the industries of applied optoelectronics. Our aim in this Account is to highlight the basic pillars that define the chemistry of the halide perovskites and their unconventional electronic properties through the prism of structure-property relationships. We focus on the synthetic requirements under which a halide perovskite can exist and emphasize how the synthetic conditions can determine the structural integrity and the bulk properties of the perovskites. Then we proceed to discuss the origins of the optical and electronic phenomena, using the perovskite crystal structure as a guide. Some of the most remarkable features of the perovskites dealt with in this Account include the evolution of a unique type of defect, which gives rise to superlattices. These can enhance or diminish the fluorescence properties of the perovskites. For example, the exotic self-doping ability of the Sn-based perovskites allows them to adopt electrical

  7. 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.

  8. 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.

  9. Fused Perovskite Tunnel Structures in Ba5 Fe6+x S4+x O8 (0.44≤x≤0.55) with x-Dependent Two-Stage Magnetizations.

    PubMed

    Wright, Taylor; Prots, Yurii; Valldor, Martin

    2016-08-01

    Ba5 Fe6+x S4+x O8 was synthesized through a solid-state reaction, and pure powders of nominal compositions x=0.44-0.55 were obtained after being rinsed with water. The crystal structures (P4/mmm, a=10.13, c=4.03 Å) and sample purities were investigated by powder synchrotron X-ray diffraction and were found to be composed of a tunnel lattice (Ba5 Fe6 S4 O8 ), built from fused perovskite units and the tunnel filling (Fex Sx ). The variable composition, that is, the tunnel filling (x), causes partially occupied sites as well as crystallographic split positions. Ba5 Fe6+x S4+x O8 (x=0.525) is semiconducting and all investigated compositions exhibit magnetic ground states that could be described as either semi-spin-glass-like (x>0.5) or canted antiferromagnetic (x<0.5). The spin-glass in x=0.525 exhibits magnetic relaxations that are affected by ageing. PMID:27359247

  10. Fused Perovskite Tunnel Structures in Ba5 Fe6+x S4+x O8 (0.44≤x≤0.55) with x-Dependent Two-Stage Magnetizations.

    PubMed

    Wright, Taylor; Prots, Yurii; Valldor, Martin

    2016-08-01

    Ba5 Fe6+x S4+x O8 was synthesized through a solid-state reaction, and pure powders of nominal compositions x=0.44-0.55 were obtained after being rinsed with water. The crystal structures (P4/mmm, a=10.13, c=4.03 Å) and sample purities were investigated by powder synchrotron X-ray diffraction and were found to be composed of a tunnel lattice (Ba5 Fe6 S4 O8 ), built from fused perovskite units and the tunnel filling (Fex Sx ). The variable composition, that is, the tunnel filling (x), causes partially occupied sites as well as crystallographic split positions. Ba5 Fe6+x S4+x O8 (x=0.525) is semiconducting and all investigated compositions exhibit magnetic ground states that could be described as either semi-spin-glass-like (x>0.5) or canted antiferromagnetic (x<0.5). The spin-glass in x=0.525 exhibits magnetic relaxations that are affected by ageing.

  11. Chemical and radiation stability of 244Cm-doped aluminate perovskite

    NASA Astrophysics Data System (ADS)

    Livshits, T. S.; Lizin, A. A.; Tomilin, S. V.

    2014-11-01

    Aluminate perovskite with a 75% simulator of actinide-REE (Nd, Sm, Ce) fraction of high-level radioactive wastes (HLW) from reprocessing of spent nuclear fuel (SNF) has been synthesized and studied. The radiation stability of perovskite in the process of 244Cm decay ( T 1/2 = 18 yr) was investigated. Its structure has been amorphized at accumulated dose of 2.3 × 1018 α-decays/g, or 0.26 displacements per atom (dpa). The critical temperature above which amorphization does not occur at any dose is estimated to be 500°C. Radiation resistance of aluminate perovskite is close to previously studied titanate pyrochlore and ferrite garnet. The stability of perovskite in water before and after amorphization has been studied as well. The leach rate of Cm by water (90°C) from crystalline perovskite in runs 3-14 days long was 10-2-10-3 g/m2. This value is close to the stability of titanate pyrochlore and aluminate garnet. The intensity of element leaching from perovskite after amorphization of its structure increases 10-100 times and thus is higher than for other previously studied actinide phases.

  12. Emergence of Hysteresis and Transient Ferroelectric Response in Organo-Lead Halide Perovskite Solar Cells.

    PubMed

    Chen, Hsin-Wei; Sakai, Nobuya; Ikegami, Masashi; Miyasaka, Tsutomu

    2015-01-01

    Although there has been rapid progress in the efficiency of perovskite-based solar cells, hysteresis in the current-voltage performance is not yet completely understood. Owing to its complex structure, it is not easy to attribute the hysteretic behavior to any one of different components, such as the bulk of the perovskite or different heterojunction interfaces. Among organo-lead halide perovskites, methylammonium lead iodide perovskite (CH3NH3PbI3) is known to have a ferroelectric property. The present investigation reveals a strong correlation between transient ferroelectric polarization of CH3NH3PbI3 induced by an external bias in the dark and hysteresis enhancement in photovoltaic characteristics. Our results demonstrate that the reverse bias poling (-0.3 to -1.1 V) of CH3NH3PbI3 photovoltaic layers prior to the photocurrent-voltage measurement generates stronger hysteresis whose extent changes significantly by the cell architecture. The phenomenon is interpreted as the effect of remanent polarization in the perovskite film on the photocurrent, which is most enhanced in planar perovskite structures without mesoporous scaffolds.

  13. Theoretical insights into hybrid perovskites for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Even, Jacky; Boyer-Richard, Soline; Carignano, Marcelo; Pedesseau, Laurent; Jancu, Jean-Marc; Katan, Claudine

    2016-03-01

    In this paper, we examine recent theoretical investigations on 3D hybrid perovskites (HOP) that combine concepts developed for classical bulk solid-state physics and empirical simulations of their optoelectronic properties. In fact, the complexity of HOP calls for a coherent global view that combines usually disconnected concepts. For the pseudocubic high temperature reference perovskite structure that plays a central role for 3D HOP, we introduce a new tight-binding Hamiltonian, which specifically includes spin-orbit coupling. The resultant electronic band structure is compared to that obtained using state of the art density functional theory (DFT). Next, recent experimental investigations of excitonic properties in HOP will be revisited within the scope of theoretical concepts already well implemented in the field of conventional semiconductors. Last, possible plastic crystal and orientational glass behaviors of HOP will be discussed, building on Car-Parrinello molecular dynamics simulations.

  14. Polarization twist in perovskite ferrielectrics

    PubMed Central

    Kitanaka, Yuuki; Hirano, Kiyotaka; Ogino, Motohiro; Noguchi, Yuji; Miyayama, Masaru; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

    2016-01-01

    Because the functions of polar materials are governed primarily by their polarization response to external stimuli, the majority of studies have focused on controlling polar lattice distortions. In some perovskite oxides, polar distortions coexist with nonpolar tilts and rotations of oxygen octahedra. The interplay between nonpolar and polar instabilities appears to play a crucial role, raising the question of how to design materials by exploiting their coupling. Here, we introduce the concept of ‘polarization twist’, which offers enhanced control over piezoelectric responses in polar materials. Our experimental and theoretical studies provide direct evidence that a ferrielectric perovskite exhibits a large piezoelectric response because of extended polar distortion, accompanied by nonpolar octahedral rotations, as if twisted polarization relaxes under electric fields. The concept underlying the polarization twist opens new possibilities for developing alternative materials in bulk and thin-film forms. PMID:27586824

  15. Polarization twist in perovskite ferrielectrics.

    PubMed

    Kitanaka, Yuuki; Hirano, Kiyotaka; Ogino, Motohiro; Noguchi, Yuji; Miyayama, Masaru; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

    2016-09-02

    Because the functions of polar materials are governed primarily by their polarization response to external stimuli, the majority of studies have focused on controlling polar lattice distortions. In some perovskite oxides, polar distortions coexist with nonpolar tilts and rotations of oxygen octahedra. The interplay between nonpolar and polar instabilities appears to play a crucial role, raising the question of how to design materials by exploiting their coupling. Here, we introduce the concept of 'polarization twist', which offers enhanced control over piezoelectric responses in polar materials. Our experimental and theoretical studies provide direct evidence that a ferrielectric perovskite exhibits a large piezoelectric response because of extended polar distortion, accompanied by nonpolar octahedral rotations, as if twisted polarization relaxes under electric fields. The concept underlying the polarization twist opens new possibilities for developing alternative materials in bulk and thin-film forms.

  16. Polarization twist in perovskite ferrielectrics.

    PubMed

    Kitanaka, Yuuki; Hirano, Kiyotaka; Ogino, Motohiro; Noguchi, Yuji; Miyayama, Masaru; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

    2016-01-01

    Because the functions of polar materials are governed primarily by their polarization response to external stimuli, the majority of studies have focused on controlling polar lattice distortions. In some perovskite oxides, polar distortions coexist with nonpolar tilts and rotations of oxygen octahedra. The interplay between nonpolar and polar instabilities appears to play a crucial role, raising the question of how to design materials by exploiting their coupling. Here, we introduce the concept of 'polarization twist', which offers enhanced control over piezoelectric responses in polar materials. Our experimental and theoretical studies provide direct evidence that a ferrielectric perovskite exhibits a large piezoelectric response because of extended polar distortion, accompanied by nonpolar octahedral rotations, as if twisted polarization relaxes under electric fields. The concept underlying the polarization twist opens new possibilities for developing alternative materials in bulk and thin-film forms. PMID:27586824

  17. High-performance perovskite light-emitting diodes via morphological control of perovskite films.

    PubMed

    Yu, Jae Choul; Kim, Da Bin; Jung, Eui Dae; Lee, Bo Ram; Song, Myoung Hoon

    2016-04-01

    Solution-processable perovskite materials have garnered tremendous attention because of their excellent charge carrier mobility, possibility of a tunable optical bandgap, and high photoluminescence quantum efficiency (PLQE). In particular, the uniform morphology of a perovskite film is the most important factor in realizing perovskite light-emitting diodes (PeLEDs) with high efficiency and full-coverage electroluminescence (EL). In this study, we demonstrate highly efficient PeLEDs that contain a perovskite film with a uniform morphology by introducing HBr into the perovskite precursor. The introduction of HBr into the perovskite precursor results in a perovskite film with a uniform, continuous morphology because the HBr increases the solubility of the inorganic component in the perovskite precursor and reduces the crystallization rate of the perovskite film upon spin-coating. Moreover, PeLEDs fabricated using perovskite films with a uniform, continuous morphology, which were deposited using 6 vol% HBr in a dimethylformamide (DMF)/hydrobromic acid (HBr) cosolvent, exhibited full coverage of the green EL emission. Finally, the optimized PeLEDs fabricated with perovskite films deposited using the DMF/HBr cosolvent exhibited a maximum luminance of 3490 cd m(-2) (at 4.3 V) and a luminous efficiency of 0.43 cd A(-1) (at 4.3 V). PMID:26607474

  18. From Morphology to Interfaces to Tandem Geometries: Enhancing the Performance of Perovskite/Polymer Solar Cells

    NASA Astrophysics Data System (ADS)

    Russell, Thomas

    We have taken a new approach to develop mesoporous lead iodide scaffolds, using the nucleation and growth of lead iodide crystallites in a wet film. A simple time-dependent growth control enabled the manipulation of the mesoporous lead iodide layer quality in a continuous manner. The morphology of lead iodide is shown to influence the subsequent crystallization of methyamoniumleadiodide film by using angle-dependent grazing incidence x-ray scattering. The morphology of lead iodide film can be fine-tuned, and thus the methyamoniumleadiodide film quality can be effectively controlled, leading to an optimization of the perovskite active layer. Using this strategy, perovskite solar cells with inverted PHJ structure showed a PCE of 15.7 per cent with little hysteresis. Interface engineering is critical for achieving efficient solar cells, yet a comprehensive understanding of the interface between metal electrode and electron transport layer (ETL) is lacking. A significant power conversion efficiency (PCE) improvement of fullerene/perovskite planar heterojunction solar cells was achieved by inserting a fulleropyrrolidine interlayer between the silver electrode and electron transport layer. The interlayer was found to enhance recombination resistance, increases electron extraction rate and prolongs free carrier lifetime. We also uncovered a facile solution-based fabrication of high performance tandem perovskite/polymer solar cells where the front sub-cell consists of perovskite and the back sub-cell is a polymer-based layer. A record maximum PCE of 15.96 per cent was achieved, demonstrating the synergy between the perovskite and semiconducting polymers. This design balances the absorption of the perovskite and the polymer, eliminates the adverse impact of thermal annealing during perovskite fabrication, and affords devices with no hysteresis. This work was performed in collaboration with Y. Liu, Z. Page, D. Venkataraman and T. Emrick (UMASS), F. Liu (LBNL) and Q. Hu and R

  19. Wafer-scale growth of large arrays of perovskite microplate crystals for functional electronics and optoelectronics

    PubMed Central

    Wang, Gongming; Li, Dehui; Cheng, Hung-Chieh; Li, Yongjia; Chen, Chih-Yen; Yin, Anxiang; Zhao, Zipeng; Lin, Zhaoyang; Wu, Hao; He, Qiyuan; Ding, Mengning; Liu, Yuan; Huang, Yu; Duan, Xiangfeng

    2015-01-01

    Methylammonium lead iodide perovskite has attracted intensive interest for its diverse optoelectronic applications. However, most studies to date have been limited to bulk thin films that are difficult to implement for integrated device arrays because of their incompatibility with typical lithography processes. We report the first patterned growth of regular arrays of perovskite microplate crystals for functional electronics and optoelectronics. We show that large arrays of lead iodide microplates can be grown from an aqueous solution through a seeded growth process and can be further intercalated with methylammonium iodide to produce perovskite crystals. Structural and optical characterizations demonstrate that the resulting materials display excellent crystalline quality and optical properties. We further show that perovskite crystals can be selectively grown on prepatterned electrode arrays to create independently addressable photodetector arrays and functional field effect transistors. The ability to grow perovskite microplates and to precisely place them at specific locations offers a new material platform for the fundamental investigation of the electronic and optical properties of perovskite materials and opens a pathway for integrated electronic and optoelectronic systems. PMID:26601297

  20. Effect of Mesostructured Layer upon Crystalline Properties and Device Performance on Perovskite Solar Cells.

    PubMed

    Listorti, Andrea; Juarez-Perez, Emilio J; Frontera, Carlos; Roiati, Vittoria; Garcia-Andrade, Laura; Colella, Silvia; Rizzo, Aurora; Ortiz, Pablo; Mora-Sero, Ivan

    2015-05-01

    One of the most fascinating characteristics of perovskite solar cells (PSCs) is the retrieved obtainment of outstanding photovoltaic (PV) performances withstanding important device configuration variations. Here we have analyzed CH3NH3PbI3-xClx in planar or in mesostructured (MS) configurations, employing both titania and alumina scaffolds, fully infiltrated with perovskite material or presenting an overstanding layer. The use of the MS scaffold induces to the perovskite different structural properties, in terms of grain size, preferential orientation, and unit cell volume, in comparison to the ones of the material grown with no constraints, as we have found out by X-ray diffraction analyses. We have studied the effect of the PSC configuration on photoinduced absorption and time-resolved photoluminescence, complementary techniques that allow studying charge photogeneration and recombination. We have estimated electron diffusion length in the considered configurations observing a decrease when the material is confined in the MS scaffold with respect to a planar architecture. However, the presence of perovskite overlayer allows an overall recovering of long diffusion lengths explaining the record PV performances obtained with a device configuration bearing both the mesostructure and a perovskite overlayer. Our results suggest that performance in devices with perovskite overlayer is mainly ruled by the overlayer, whereas the mesoporous layer influences the contact properties. PMID:26263326

  1. High-Efficiency Light-Emitting Diodes of Organometal Halide Perovskite Amorphous Nanoparticles.

    PubMed

    Xing, Jun; Yan, Fei; Zhao, Yawen; Chen, Shi; Yu, Huakang; Zhang, Qing; Zeng, Rongguang; Demir, Hilmi Volkan; Sun, Xiaowei; Huan, Alfred; Xiong, Qihua

    2016-07-26

    Organometal halide perovskite has recently emerged as a very promising family of materials with augmented performance in electronic and optoelectronic applications including photovoltaic devices, photodetectors, and light-emitting diodes. Herein, we propose and demonstrate facile solution synthesis of a series of colloidal organometal halide perovskite CH3NH3PbX3 (X = halides) nanoparticles with amorphous structure, which exhibit high quantum yield and tunable emission from ultraviolet to near-infrared. The growth mechanism and photoluminescence properties of the perovskite amorphous nanoparticles were studied in detail. A high-efficiency green-light-emitting diode based on amorphous CH3NH3PbBr3 nanoparticles was demonstrated. The perovskite amorphous nanoparticle-based light-emitting diode shows a maximum luminous efficiency of 11.49 cd/A, a power efficiency of 7.84 lm/W, and an external quantum efficiency of 3.8%, which is 3.5 times higher than that of the best colloidal perovskite quantum-dot-based light-emitting diodes previously reported. Our findings indicate the great potential of colloidal perovskite amorphous nanoparticles in light-emitting devices.

  2. The efficiency limit of CH3NH3PbI3 perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Sha, Wei E. I.; Ren, Xingang; Chen, Luzhou; Choy, Wallace C. H.

    2015-06-01

    With the consideration of photon recycling effect, the efficiency limit of methylammonium lead iodide (CH3NH3PbI3) perovskite solar cells is predicted by a detailed balance model. To obtain convincing predictions, both AM 1.5 spectrum of Sun and experimentally measured complex refractive index of perovskite material are employed in the detailed balance model. The roles of light trapping and angular restriction in improving the maximal output power of thin-film perovskite solar cells are also clarified. The efficiency limit of perovskite cells (without the angular restriction) is about 31%, which approaches to Shockley-Queisser limit (33%) achievable by gallium arsenide (GaAs) cells. Moreover, the Shockley-Queisser limit could be reached with a 200 nm-thick perovskite solar cell, through integrating a wavelength-dependent angular-restriction design with a textured light-trapping structure. Additionally, the influence of the trap-assisted nonradiative recombination on the device efficiency is investigated. The work is fundamentally important to high-performance perovskite photovoltaics.

  3. High-Efficiency Light-Emitting Diodes of Organometal Halide Perovskite Amorphous Nanoparticles.

    PubMed

    Xing, Jun; Yan, Fei; Zhao, Yawen; Chen, Shi; Yu, Huakang; Zhang, Qing; Zeng, Rongguang; Demir, Hilmi Volkan; Sun, Xiaowei; Huan, Alfred; Xiong, Qihua

    2016-07-26

    Organometal halide perovskite has recently emerged as a very promising family of materials with augmented performance in electronic and optoelectronic applications including photovoltaic devices, photodetectors, and light-emitting diodes. Herein, we propose and demonstrate facile solution synthesis of a series of colloidal organometal halide perovskite CH3NH3PbX3 (X = halides) nanoparticles with amorphous structure, which exhibit high quantum yield and tunable emission from ultraviolet to near-infrared. The growth mechanism and photoluminescence properties of the perovskite amorphous nanoparticles were studied in detail. A high-efficiency green-light-emitting diode based on amorphous CH3NH3PbBr3 nanoparticles was demonstrated. The perovskite amorphous nanoparticle-based light-emitting diode shows a maximum luminous efficiency of 11.49 cd/A, a power efficiency of 7.84 lm/W, and an external quantum efficiency of 3.8%, which is 3.5 times higher than that of the best colloidal perovskite quantum-dot-based light-emitting diodes previously reported. Our findings indicate the great potential of colloidal perovskite amorphous nanoparticles in light-emitting devices. PMID:27284993

  4. Structurally modulated magnetic properties in the A(3)MnRu(2)O(9) phases (A = Ba, Ca): the role of metal-metal bonding in perovskite-related oxides.

    PubMed

    Gönen, Z S; Gopalakrishnan, J; Eichhorn, B W; Greene, R L

    2001-09-10

    Ca(3)MnRu(2)O(9) and Ba(3)MnRu(2)O(9) were synthesized from transition metal dioxides and alkaline earth metal carbonates at 1100-1300 degrees C. Ca(3)MnRu(2)O(9) adopts the prototypical GdFeO(3)-type perovskite structure with Mn and Ru statistically disordered over the single metal atom site. The susceptibility shows Curie-Weiss behavior above 240 K with mu(eff) = 3.14 micro(B)/metal atom, which is in excellent agreement with the expected spin-only moment of 3.20 micro(B). Below 150 K, the compound shows spin-glass-like short-range ferrimagnetic correlations. The high-temperature region of the electrical resistivity reveals a small activation energy of 17(1) meV whereas the low-temperature region is nonlinear and does not fit a variable range hopping model. Ba(3)MnRu(2)O(9) crystallizes in the 9-layer BaRuO(3)-type structure containing M(3)O(12) face-shared trioctahedral clusters in which Mn and Ru are statistically disordered. Ba(3)MnRu(2)O(9) shows nonlinear reciprocal susceptibility at all temperatures and is described by a variable-spin cluster model with an S = (1)/(2) ground state with thermally populated excited states. The low spin value of this system (S = (1)/(2)) is attributed to direct metal-metal bonding. Below 30 K, the compound shows short-range magnetic correlations and spin-glass-like behavior. The high-temperature region of the electrical resistivity indicates a small activation energy of 8.8(1) meV whereas the low-temperature region is nonlinear. The importance of metal-metal bonding and the relationships to other related compounds are discussed.

  5. Rapid Microwave Synthesis of Perovskite Oxide Nanostructures with Enhanced Functionality

    NASA Astrophysics Data System (ADS)

    Salazar, Gregory; Datta, Anuja; Mukherjee, Pritish

    2015-03-01

    Perovskite oxides are an important class of materials having high dielectric and piezoelectric coefficients, switchable ferroelectric (FE) polarization and interesting optical and electrical properties. Realization of functional devices based on classic perovskite oxides such as Pb(Zr0.52Ti0.48) O3 (PZT), and emerging Pb-free noncentrosymmetric (NCS) oxides, such as, ZnSnO3, ZnTiO3 and CaTiO3 have reinforced the investigation of these materials in multiple dimensions and length scales. However, large-scale synthesis and integration of ordered low-dimensional structures is a challenge, due to their complicated methodologies, high-cost and difficulties with phase stability. We discuss a generalized, cost-effective, rapid microwave synthesis route for size and shape selective nanostructure growth of these functional perovskite oxides on industrially viable flexible and hard substrates, stabilized by an enhanced ionic covalence. The rational synthesis approach allowed improved tunability of the size, shape, and orientation of the structures with improved electrical and FE properties. The facile fabrication route of these nanostructures may expand the outreach of probes for understanding the structure-property relationships in these hitherto unexplored and technologically important materials.

  6. Greater functionality of bismuth and lead based perovskites

    NASA Astrophysics Data System (ADS)

    Suchomel, Matthew R.

    Novel Bi and Pb-based perovskite oxide chemistries have been investigated through bulk solid-state synthesis methods with a goal of increasing the dielectric, ferroelectric, and magnetic functionality of these materials. Although the Pb+2 and Bi+3 canons are chemically similar, Pb-based perovskites have historically received greater commercial and scientific attention. However, recent experimental and theoretical progress in studies of Bi containing systems has prompted a renewed interest in their potential. As such, particular focus was given to the Bi+3 containing systems in the current work. An investigation of the Bi-based perovskite compounds, emphasizing multiferroic BiFeO3 and related solid solutions, has explored the limitations of bulk synthesis methods for these systems. Numerous cation and anion substitution routes are experimentally studied and a comprehensive review of previous work examining B' site cation substitution in Bi-based perovskites is performed. This has resulted in an improved understanding of phase competition within these systems. These findings were used to engineer new chemistries, particularly those of mixed cation site occupancy, with improved perovskite stability. New low tolerance factor Bi-based perovskites with mixed B ' site cation chemistries have been used to induce morphotropic phase boundary (MPB) formation in solid solutions with PbTiO3. Moreover, a new qualitative relationship correlating the tolerance factor of Bi and Pb-based end members in PbTiO3 solid solutions to the compositional position of the system's MPB has been developed and experimentally validated. This relationship has been used to explore novel end members with very low tolerance factors including (Pb1/2Th1/2)ScO 3, for PbTiO3-based MPB solid solutions. A new category of Bi-based chemistries which enhance tetragonality and Curie temperature (Tc) in solid solutions with PbTiO3 has been identified. This effect is particularly dramatic for the (x)PbTiO 3

  7. Modelling dislocation cores in MgSiO3 perovskite

    NASA Astrophysics Data System (ADS)

    Cordier, P.; Carrez, P.; Gouriet, K.; Kraych, A.

    2012-12-01

    MgSiO3 perovskite is the most abundant mineral of the Earth's lower mantle (i.e. between 700 and 2900 km depth) and accounts for half of Earth's mass. At lower mantle pressures (25-135 GPa) MgSiO3 crystallises in a distorted (orthorhombic) perovskite structure (described in the following using the Pbnm space group). In this structure, SiO6 octahedra are tilted with tilt angles increasing with increasing pressure. Since it is very difficult to perform deformation experiments under the extreme P, T conditions of the lower mantle, little is known about plastic deformation of MgSiO3 perovskite and its slip systems are still a matter of debate. To overcome this difficulty, we model dislocation core structures in this mineral taking into account the influence of pressure. In this study, we focus on dislocation core structures of dislocations with [100] and [010] Burgers vectors (which derive from <110> Burgers vectors of the underlying pseudo-cubic structure). Atomistic calculations are performed using pair-wise potentials as implemented in the LAMMPS code. The choice of potentials was initially validated by comparing generalized stacking fault (GSF) energies to similar calculations performed with the density functional theory (DFT). The core structures of screw dislocations are calculated using two independent methods. The first one is based on Peierls-Nabarro-Galerkin simulations involving GSF as an input. Direct calculations have also bee performed using cluster approach. It turns out that screw dislocations with [100] Burgers vector are characterised by a core mostly spread in the (010) plane. The core exhibits two edge-sharing octahedra in a configuration very similar to that modelled in SrTiO3 cubic perovskite. The structure of [010] screw dislocations is more complex with dissociation into two, non-collinear partial dislocations with a significant non-screw component. Both dislocations exhibit high Peierls stresses. This illustrates the effect of orthorhombic

  8. Flexible Hybrid Organic-Inorganic Perovskite Memory.

    PubMed

    Gu, Chungwan; Lee, Jang-Sik

    2016-05-24

    Active research has been done on hybrid organic-inorganic perovskite materials for application to solar cells with high power conversion efficiency. However, this material often shows hysteresis, which is undesirable, shift in the current-voltage curve. The hysteresis may come from formation of defects and their movement in perovskite materials. Here, we utilize the defects in perovskite materials to be used in memory operations. We demonstrate flexible nonvolatile memory devices based on hybrid organic-inorganic perovskite as the resistive switching layer on a plastic substrate. A uniform perovskite layer is formed on a transparent electrode-coated plastic substrate by solvent engineering. Flexible nonvolatile memory based on the perovskite layer shows reproducible and reliable memory characteristics in terms of program/erase operations, data retention, and endurance properties. The memory devices also show good mechanical flexibility. It is suggested that resistive switching is done by migration of vacancy defects and formation of conducting filaments under the electric field in the perovskite layer. It is believed that organic-inorganic perovskite materials have great potential to be used in high-performance, flexible memory devices. PMID:27093096

  9. Achieving High Performance Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Yang, Yang

    2015-03-01

    Recently, metal halide perovskite based solar cell with the characteristics of rather low raw materials cost, great potential for simple process and scalable production, and extreme high power conversion efficiency (PCE), have been highlighted as one of the most competitive technologies for next generation thin film photovoltaic (PV). In UCLA, we have realized an efficient pathway to achieve high performance pervoskite solar cells, where the findings are beneficial to this unique materials/devices system. Our recent progress lies in perovskite film formation, defect passivation, transport materials design, interface engineering with respect to high performance solar cell, as well as the exploration of its applications beyond photovoltaics. These achievements include: 1) development of vapor assisted solution process (VASP) and moisture assisted solution process, which produces perovskite film with improved conformity, high crystallinity, reduced recombination rate, and the resulting high performance; 2) examination of the defects property of perovskite materials, and demonstration of a self-induced passivation approach to reduce carrier recombination; 3) interface engineering based on design of the carrier transport materials and the electrodes, in combination with high quality perovskite film, which delivers 15 ~ 20% PCEs; 4) a novel integration of bulk heterojunction to perovskite solar cell to achieve better light harvest; 5) fabrication of inverted solar cell device with high efficiency and flexibility and 6) exploration the application of perovskite materials to photodetector. Further development in film, device architecture, and interfaces will lead to continuous improved perovskite solar cells and other organic-inorganic hybrid optoelectronics.

  10. Organohalide Lead Perovskites for Photovoltaic Applications.

    PubMed

    Yusoff, Abd Rashid Bin Mohd; Nazeeruddin, Mohammad Khaja

    2016-03-01

    Perovskite solar cells have recently exhibited a significant leap in efficiency due to their broad absorption, high optical absorption coefficient, very low exciton binding energy, long carrier diffusion lengths, efficient charge collection, and very high open-circuit potential, similar to that of III-IV semiconductors. Unlike silicon solar cells, perovskite solar cells can be developed from a variety of low-temperature solutions processed from inexpensive raw materials. When the perovskite absorber film formation is optimized using solvent engineering, a power conversion efficiency of over 21% has been demonstrated, highlighting the unique photovoltaic properties of perovskite materials. Here, we review the current progress in perovskite solar cells and charge transport materials. We highlight crucial challenges and provide a summary and prospects. PMID:26885884

  11. Bandgap calculations and trends of organometal halide perovskites

    SciTech Connect

    Castelli, Ivano E. Thygesen, Kristian S.; Jacobsen, Karsten W.; García-Lastra, Juan María

    2014-08-01

    Energy production from the Sun requires a stable efficient light absorber. Promising candidates in this respect are organometal perovskites (ABX{sub 3}), which have been intensely investigated during the last years. Here, we have performed electronic structure calculations of 240 perovskites composed of Cs, CH{sub 3}NH{sub 3}, and HC(NH{sub 2}){sub 2} as A-cation, Sn and Pb as B-ion, and a combination of Cl, Br, and I as anions. The calculated gaps span over a region from 0.5 to 5.0 eV. In addition, the trends over bandgaps have been investigated: the bandgap increases with an increase of the electronegativities of the constituent species, while it reduces with an increase of the lattice constants of the system.

  12. Structures, phase transitions and microwave dielectric properties of the 6H perovskites Ba{sub 3}BSb{sub 2}O{sub 9}, B=Mg, Ca, Sr, Ba

    SciTech Connect

    Ling, Chris D. Rowda, Budwy; Avdeev, Maxim; Pullar, Robert

    2009-03-15

    We present a complete temperature-composition phase diagram for Ba{sub 3}BSb{sub 2}O{sub 9}, B=Mg, Ca, Sr, Ba, along with their electrical behavior as a function of B. These compounds have long been recognized as 6H-type perovskites, but (with the exception of B=Mg) their exact structures and properties were unknown due to their low symmetries, temperature-dependent phase transitions, and difficulties in synthesizing pure samples. The full range of possible space group symmetries is observed, from ideal hexagonal P6{sub 3}/mmc to monoclinic C2/c to triclinic P1-bar. Direct second-order transitions between these phases are plausible according to group theory, and no evidence was seen for any further intermediate phases. The phase diagram with respect to temperature and the effective ionic radius of B is remarkably symmetrical for B=Mg, Ca, and Sr. For B=Ba, a first-order phase transition to a locally distorted phase allows a metastable hexagonal phase to persist to lower temperatures than expected before decomposing around 600 K. Electrical measurements revealed that dielectric permittivity corrected for porosity does not change significantly as a function of B and is in a good agreement with the values predicted by the Clausius-Mossotti equation. - Graphical abstract: Thermodynamic phase diagram for Ba{sub 3}BSb{sub 2}O{sub 9}, B=Mg, Ca, and Sr, as a function of temperature T and effective ionic radius (IR) of the B{sup 2+} cation.

  13. Synthesis, Average Structure, and Magnetic Properties of Oxygen Deficient Perovskites (Ba 2-3 xBi 3 x-1 )(Fe 2 xBi 1-2 x)O 2+3/2 x

    NASA Astrophysics Data System (ADS)

    Boullay, Ph.; Hervieu, M.; Nguyen, N.; Raveau, B.

    1999-10-01

    A new family of oxygen deficient perovskite [Ba2-3xBi3x-1] [Fe2xBi1-2x]O2+3x/2 has been synthesized for 1/3≤x≤1/2. The average structure of these phases is determined using a combination of X-ray, neutron powder diffraction, and electron diffraction. The compounds exhibit a cubic subcell (a=ap) for x≤0.43 and a tetragonal subcell (a≈c≈ap) for 0.43

  14. The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site

    PubMed Central

    Evans, Christopher D.; Smith, Paul J.; Manning, Troy D.; Miedziak, Peter J.; Brett, Gemma L.; Armstrong, Robert D.; Bartley, Jonathan K.; Taylor, Stuart H.; Rosseinsky, Matthew J.; Hutchings, Graham J.

    2016-01-01

    Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology. PMID:27074316

  15. The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site.

    PubMed

    Evans, Christopher D; Kondrat, Simon A; Smith, Paul J; Manning, Troy D; Miedziak, Peter J; Brett, Gemma L; Armstrong, Robert D; Bartley, Jonathan K; Taylor, Stuart H; Rosseinsky, Matthew J; Hutchings, Graham J

    2016-07-01

    Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology. PMID:27074316

  16. Super-ion inspired colorful hybrid perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Fang, Hong; Jena, Puru

    Organic-inorganic hybrid perovskites, with the general formula AMX3 (A =cation; M =metal; X =halogen), have emerged as a new generation of efficient yet inexpensive photovoltaic cells. These materials show record high conversion efficiency as solar cells and have excellent light-emission properties that can also be used in other optoelectronic devices. They can be processed easily from solution with optic band gaps, tunable from visible to infrared regions and are considered to be ``the next big thing in photovoltaics''. However, several important issues such as the relationship between their photoexcitation properties and the chemical structures, their stability under ambient conditions, as well as the possibility to invent their environment-friendly analogues remain unsolved. In this work, our aim is not only to gain a fundamental understanding of the structure-property relationship of organic-inorganic hybrid perovskites, but also to rationally design a new class of hybrid perovskites that have desired electronic band gaps for solar cell applications. This is accomplished by using super-ions that can mimic the properties of elementary alkali and halogen ions as building blocks. These super-ions include superalkalis - CH3NH3+,HC(NH2) 2 + , and Li3O+ as cations and hyperhalogens - Ge(BH4) 3 - and Sn(BH4) 3 - as anions. The results are compared with perovskites composed of GeCl3-,GeBr3-,GeI3-,SnCl3-,SnBr3-,and SnI3-superhalogen anions. We develop a strategy to assemble these super-ions to form environment-friendly solar cells with adjustable band gaps (covering the visible range and beyond) and with improved resistance to moisture.

  17. Role of the chemical substitution on the structural and luminescence properties of the mixed halide perovskite thin MAPbI3 - xBrx (0 ≤ x ≤ 1) films

    NASA Astrophysics Data System (ADS)

    Atourki, Lahoucine; Vega, Erika; Marí, Bernabé; Mollar, Miguel; Ait Ahsaine, Hassan; Bouabid, Khalid; Ihlal, Ahmed

    2016-05-01

    Mixed bromide iodide lead perovskites were prepared from methylamine, lead nitrate and the corresponding hydroX acid (X = I, Br), they were then deposited as thin films on ITO substrate by the spin coating process. X-ray diffraction analyses indicated the formation of a tetragonal phase I4/mcm up to x = 0.4 and a cubic perovskite with space group Pm3 m in the composition range of 0.6 ≤ x ≤ 1. Mixed lead perovskites showed a high absorbance in the UV-vis range. The band gap energy of thin films were estimated from absorbance spectral measurements, it was found that the onset of the absorption edge for MAPbI3 - xBrx (x < 1) thin films is ranging between 1.58 to 1.72 eV. Photoluminescence emission energies for mixed halide perovskites presented intermediate values from 781 nm (MAPbI3) to 545 nm (MAPbBr3).

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

    SciTech Connect

    Uberuaga, Blas Pedro; Pilania, Ghanshyam

    2015-07-08

    Perovskite structured oxides (ABO3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA’BB’O6) 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 SrLaTiAlO6. 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 end 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 Ti4+ 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.

  19. Magnetic domain wall induced ferroelectricity in double perovskites

    SciTech Connect

    Zhou, Hai Yang; Zhao, Hong Jian E-mail: xmchen59@zju.edu.cn; Chen, Xiang Ming E-mail: xmchen59@zju.edu.cn; Zhang, Wen Qing

    2015-04-13

    Recently, a magnetically induced ferroelectricity occurring at magnetic domain wall of double perovskite Lu{sub 2}CoMnO{sub 6} has been reported experimentally. However, there exists a conflict whether the electric polarization is along b or c direction. Here, by first-principles calculations, we show that the magnetic domain wall (with ↑↑↓↓ spin configuration) can lead to the ferroelectric displacements of R{sup 3+}, Ni{sup 2+}, Mn{sup 4+}, and O{sup 2−} ions in double perovskites R{sub 2}NiMnO{sub 6} (R = rare earth ion) via exchange striction. The resulted electric polarization is along b direction with the P2{sub 1} symmetry. We further reveal the origin of the ferroelectric displacements as that: (1) on a structural point of view, such displacements make the two out-of-plane Ni-O-Mn bond angles as well as Ni-Mn distance unequal, and (2) on an energy point of view, such displacements weaken the out-of-plane Ni-Mn super-exchange interaction obviously. Finally, our calculations show that such a kind of ferroelectric order is general in ferromagnetic double perovskites.

  20. Interfacial Charge Transfer Anisotropy in Polycrystalline Lead Iodide Perovskite Films.

    PubMed

    Yin, Jun; Cortecchia, Daniele; Krishna, Anurag; Chen, Shi; Mathews, Nripan; Grimsdale, Andrew C; Soci, Cesare

    2015-04-16

    Solar cells based on organic-inorganic lead iodide perovskite (CH3NH3PbI3) exhibit remarkably high power conversion efficiency (PCE). One of the key issues in solution-processed films is that often the polycrystalline domain orientation is not well-defined, which makes it difficult to predict energy alignment and charge transfer efficiency. Here we combine ab initio calculations and photoelectron spectroscopy to unravel the electronic structure and charge redistribution at the interface between different surfaces of CH3NH3PbI3 and typical organic hole acceptor Spiro-OMeTAD and electron acceptor PCBM. We find that both hole and electron interfacial transfer depend strongly on the CH3NH3PbI3 surface orientation: while the (001) and (110) surfaces tend to favor hole injection to Spiro-OMeTAD, the (100) surface facilitates electron transfer to PCBM due to surface delocalized charges and hole/electron accumulation at the CH3NH3PbI3/organic interfaces. Molecular dynamic simulations indicate that this is due to strong orbital interactions under thermal fluctuations at room temperature, suggesting the possibility to further improve charge separation and extraction in perovskite-based solar cells by controlling perovskite film crystallization and surface orientation.

  1. Deciphering the physics and chemistry of perovskites with transmission electron microscopy.

    PubMed

    Polking, Mark J

    2016-03-28

    Perovskite oxides exhibit rich structural complexity and a broad range of functional properties, including ferroelectricity, ferromagnetism, and superconductivity. The development of aberration correction for the transmission electron microscope and concurrent progress in electron spectroscopy, electron holography, and other techniques has fueled rapid progress in the understanding of the physics and chemistry of these materials. New techniques based on the transmission electron microscope are first surveyed, and the applications of these techniques for the study of the structure, chemistry, electrostatics, and dynamics of perovskite oxides are then explored in detail, with a particular focus on ferroelectric materials.

  2. Calculated transport and magnetic properties of some perovskite metallic oxides AMO{sub 3}

    SciTech Connect

    Santi, G.; Jarlborg, T.

    1998-12-31

    The authors study some compounds of the perovskite (or pseudo-cubic perovskite) series AMO{sub 3}, where M is a transition metal and A is Ca, Sr, or Nd, by LSDA self-consistent electronic structure calculations with the LMTO method. Transport and magnetic properties, as well as Fermi surfaces are calculated. These materials exhibit sharp density of states features in the vicinity of the Fermi level that strongly affect their transport and magnetic properties and make them very sensitive to structural deformation and stoichiometry. Calculated total energies are very close for anti-ferromagnetic and ferromagnetic solutions. This explains qualitatively the magnetoresistive anomalies shown by this family of compounds.

  3. Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl6

    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 CsRbCaZnCl6 using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl3 and RbZnCl3) forming the double perovskite exhibit a stark contrast. While CsCaCl3 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, RbZnCl3 is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We show that combining the two compositionsmore » 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 CsRbCaZnCl6 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

  4. Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl6

    SciTech Connect

    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 CsRbCaZnCl6 using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl3 and RbZnCl3) forming the double perovskite exhibit a stark contrast. While CsCaCl3 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, RbZnCl3 is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We show 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 CsRbCaZnCl6 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.

  5. Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl{sub 6}

    SciTech Connect

    Pilania, G. Uberuaga, B. P.

    2015-03-21

    Here, we investigate the electronic structure, energetics of cation ordering, and effect of biaxial strain on double perovskite CsRbCaZnCl{sub 6} using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl{sub 3} and RbZnCl{sub 3}) forming the double perovskite exhibit a stark contrast. While CsCaCl{sub 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{sub 3} is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We show 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{sub 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. The computational approach presented here opens a new pathway towards a rational design of novel double perovskites with improved strain response and functionalities.

  6. Effects of water molecules on the chemical stability of MAGeI3 perovskite explored from a theoretical viewpoint.

    PubMed

    Sun, Ping-Ping; Chi, Wei-Jie; Li, Ze-Sheng

    2016-09-21

    The stability of perovskite in humid environments is one of the biggest obstacles for its potential applications in light harvesting and electroluminescent displays. Understanding the detailed degradation mechanism of MAGeI3 in moisture is a critical way to explore the practicability of MAGeI3 perovskite. In this study, we report a quantitative and systematic investigation of MAGeI3 degradation processes by exploring the effects of H2O molecules on the structural and electronic properties of the most stable MAGeI3(101) surface under various simulated environmental conditions with different water coverage based on first-principles calculations. The results show that H2O molecules can easily diffuse into the inner side of the perovskite and gradually corrode the structure as the number of H2O molecules increases. As a result of the interactions between perovskite and H2O molecules, a hydrated intermediate will be generated as the first step in the degradation mechanism; the perovskite will further decompose to HI and GeI2. In terms of one MAGeI3 molecule, it will be dissociated completely to GeI2 as a result of hydrolysis reactions with a minimum of 4H2O molecules. In addition, the degradation of the perovskite will also affect the electronic structure, causing a decrease in optical absorption across the visible region of the spectrum and a distinct deformation change in the crystal structure of the material. These findings further illustrate the degradation of the hydrolysis process of MAGeI3 perovskite in humid environments, which should be helpful to inspire experimentalists to take action to prolong the lifetimes of perovskite solar cells to achieve high conversion efficiency in their applications. PMID:27539944

  7. Halide-Substituted Electronic Properties of Organometal Halide Perovskite Films: Direct and Inverse Photoemission Studies.

    PubMed

    Li, Chi; Wei, Jian; Sato, Mikio; Koike, Harunobu; Xie, Zhong-Zhi; Li, Yan-Qing; Kanai, Kaname; Kera, Satoshi; Ueno, Nobuo; Tang, Jian-Xin

    2016-05-11

    Solution-processed perovskite solar cells are attracting increasing interest due to their potential in next-generation hybrid photovoltaic devices. Despite the morphological control over the perovskite films, quantitative information on electronic structures and interface energetics is of paramount importance to the optimal photovoltaic performance. Here, direct and inverse photoemission spectroscopies are used to determine the electronic structures and chemical compositions of various methylammonium lead halide perovskite films (MAPbX3, X = Cl, Br, and I), revealing the strong influence of halide substitution on the electronic properties of perovskite films. Precise control over halide compositions in MAPbX3 films causes the manipulation of the electronic properties, with a qualitatively blue shift along the I → Br → Cl series and showing the increase in ionization potentials from 5.96 to 7.04 eV and the change of transport band gaps in the range from 1.70 to 3.09 eV. The resulting light absorption of MAPbX3 films can cover the entire visible region from 420 to 800 nm. The results presented here provide a quantitative guide for the analysis of perovskite-based solar cell performance and the selection of optimal carrier-extraction materials for photogenerated electrons and holes. PMID:27101940

  8. A Strategy to Achieve High-Efficiency Organolead Trihalide Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Andalibi, Shabnam; Rostami, Ali; Darvish, Ghafar; Moravvej-Farshi, Mohammad Kazem

    2016-11-01

    Recent theoretical and experimental reports have shown that organometal lead halide perovskite solar cells have attracted attention as a low-cost photovoltaic technology offering high power conversion efficiency. However, the photovoltaic efficiency of these materials is still limited by poor chemical and structural stability in the case of methylammonium lead triiodide and by large bandgap in the case of methylammonium lead tribromide or trichloride. To obtain high-performance devices, we have investigated the computationally optimal efficiency for these materials using the detailed-balance method and present optimal intermediate-band perovskite solar cells with high open-circuit voltage. We model different halide perovskites using density function theory calculations and study their bandgap and absorption coefficient. Based on calculation results, surprisingly Hg doping in different halide perovskites introduces a narrow partially filled intermediate band in the forbidden bandgap. We investigate electrical and optical properties of MAPb0.97Hg0.03I3, MAPb0.96Hg0.04Br3, and MAPb0.96Hg0.04Cl3 and calculate the high absorption efficiency of the different perovskite structures to create thin films suitable for photovoltaic devices.

  9. A Strategy to Achieve High-Efficiency Organolead Trihalide Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Andalibi, Shabnam; Rostami, Ali; Darvish, Gafar; Moravvej-Farshi, Mohammad Kazem

    2016-07-01

    Recent theoretical and experimental reports have shown that organometal lead halide perovskite solar cells have attracted attention as a low-cost photovoltaic technology offering high power conversion efficiency. However, the photovoltaic efficiency of these materials is still limited by poor chemical and structural stability in the case of methylammonium lead triiodide and by large bandgap in the case of methylammonium lead tribromide or trichloride. To obtain high-performance devices, we have investigated the computationally optimal efficiency for these materials using the detailed-balance method and present optimal intermediate-band perovskite solar cells with high open-circuit voltage. We model different halide perovskites using density function theory calculations and study their bandgap and absorption coefficient. Based on calculation results, surprisingly Hg doping in different halide perovskites introduces a narrow partially filled intermediate band in the forbidden bandgap. We investigate electrical and optical properties of MAPb0.97Hg0.03I3, MAPb0.96Hg0.04Br3, and MAPb0.96Hg0.04Cl3 and calculate the high absorption efficiency of the different perovskite structures to create thin films suitable for photovoltaic devices.

  10. Templated Synthesis of Uniform Perovskite Nanowire Arrays.

    PubMed

    Ashley, Michael J; O'Brien, Matthew N; Hedderick, Konrad R; Mason, Jarad A; Ross, Michael B; Mirkin, Chad A

    2016-08-17

    While the chemical composition of semiconducting metal halide perovskites can be precisely controlled in thin films for photovoltaic devices, the synthesis of perovskite nanostructures with tunable dimensions and composition has not been realized. Here, we describe the templated synthesis of uniform perovskite nanowires with controlled diameter (50-200 nm). Importantly, by providing three examples (CH3NH3PbI3, CH3NH3PbBr3, and Cs2SnI6), we show that this process is composition general and results in oriented nanowire arrays on transparent conductive substrates. PMID:27501464

  11. Average and local structure of the Pb-free ferroelectric perovskites (Sr,Sn)TiO3 and (Ba,Ca,Sn)TiO3

    DOE PAGES

    Laurita, Geneva; Page, Katharine; Suzuki, Shoichiro; Seshadri, Ram

    2015-12-16

    The characteristic structural off -centering of Pb2+ in oxides, associated with its 6s2 lone pair, allows it to play a dominant role in polar materials, and makes it a somewhat ubiquitous component of ferroelectrics. In this work, we examine the compounds Sr0.9Sn0.1TiO3 and Ba0.79Ca0.16Sn0.05TiO3 using neutron total scattering techniques with data acquired at di erent temperatures. In these compounds, previously reported as ferroelectrics, Sn2+ appears to display some of the characteristics of Pb2+. We compare the local and long-range structures of the Sn2+-substituted compositions to the unsubstituted parent compounds SrTiO3 and BaTiO3. Lastly, we find that even at these smallmore » substitution levels, the Sn2+ lone pairs drive the local ordering behavior, with the local structure of both compounds more similar to the structure of PbTiO3 rather than the parent compounds.« less

  12. Strongly correlated perovskite fuel cells

    NASA Astrophysics Data System (ADS)

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

    2016-06-01

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

  13. Strongly correlated perovskite fuel cells.

    PubMed

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

    2016-05-16

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the materi