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Sample records for perovskite related oxides

  1. Protons and lattice defects in perovskite-related oxides

    NASA Astrophysics Data System (ADS)

    Nowick, A. S.

    The recent work on this project has focused on two perovskite-structured materials: single crystalline KTaO3 doped with iron-group ions, and ceramic BaCeO3 doped with Nd, Gd, Sc and Ca. In the case of KTaO3, it is shown that protons are introduced into the crystal from H2O vapor so that it becomes primarily a protonic conductor. The defect reactions involved have been considered in detail with the aid of EPR and IR measurements. In the study of BaCeO3, it was found that the Nd-doped material is an excellent protonic conductor with activation energy for proton hopping of only 0.54 eV. In addition, weight-change measurements were used to determine the amount of water uptake, while Nernst-cell measurements gave values for the transport numbers of oxygen and of protons. In contrast to the case of Nd doping, Gd or Yb-doped material are not protonic conductors. Other studies include those of high-(Tc) superconductors, the first showing a large elastic constant and internal friction anomaly in La(2x)Sr(x)CuO4, and the second showing under what conditions degradation occurs due to H2O and CO2 annealing treatments. Finally, a study of dielectric loss in Li-borate glasses shows that the dielectric loss peak in glasses widely believed to be due to a bulk phenomenon, is actually an electrode blocking effect.

  2. The dielectric behavior of perovskite-related manganese oxides with stretched bonds or multiferroic properties

    NASA Astrophysics Data System (ADS)

    Denyszyn, Jonathan Charles

    This dissertation presents two investigations into the dielectric behavior of non-d0 perovskite-related manganese oxides: the first investigation probes the unique multiferroic properties of the hexagonal-perovskite series RMn1-xGaxO3 (R = Y, Ho) and the second explores the importance of lattice stress and the effect of the metal-cation d n-character on the dielectric properties of the perovskite series SryCa1-yMn1-xBxO3-delta (B = Ti, Zr). In the hexagonal-perovskite series, doping the Mn-site with Ga increased the c lattice constant and diluted the magnetic interactions in the ab plane. The interplay of these two effects perturbed the ferrielectric, antiferromagnetic, and multiferroic interactions. The change in these interactions demonstrated chemical control of the multiferroic interactions in the hexagonal-perovskite system for the first time and highlighted the structural mechanism behind the multiferroic properties. In the second investigation, the relationship between the tensile stress on the (Mn--O) bond and the ionic dielectric constant of SryCa 1-yMnO3-delta proved difficult to quantify because the small band gap and chemical activity of the Mn4+ cation made samples with y ≥ 0.5 too conducting to measure the dielectric relaxations. To explore the ionic contribution to the dielectric behavior by an alternate path, a doping scheme was devised to decrease the sample conductivity of SrMnO 3-delta at the expense of some of the tensile stress on the (Mn--O) bond. Doping the Mn site with larger 4+ cations (Ti and Zr) reduced the dielectric constant; however, the reduction of the dielectric constant cannot be explained by the effect of the tensile stress on the (Mn--O) bond alone.

  3. 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.

  4. 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.

  5. Interplay between spin-orbit coupling and Hubbard interaction in SrIrO3 and related Pbnm perovskite oxides

    NASA Astrophysics Data System (ADS)

    Zeb, M. Ahsan; Kee, Hae-Young

    2012-08-01

    There has been a rapidly growing interest in the interplay between spin-orbit coupling (SOC) and the Hubbard interaction U in correlated materials. A current consensus is that the stronger the SOC, the smaller is the critical interaction Uc required for a spin-orbit Mott insulator, because the atomic SOC splits a band into different total angular momentum bands, narrowing the effective bandwidth. It was further claimed that at large enough SOC, the stronger the SOC, the weaker the Uc, because in general the effective SOC is enhanced with increasing electron-electron interaction strength. Contrary to this expectation, we find that, in orthorhombic perovskite oxides (Pbnm), the stronger the SOC, the bigger the Uc. This originates from a line of Dirac nodes in Jeff=1/2 bands near the Fermi level, inherited from a combination of the lattice structure and a large SOC. Due to this protected line of nodes, there are small hole and electron pockets in SrIrO3, and such a small density of states makes the Hubbard interaction less efficient in building a magnetic insulator. The full phase diagram in U vs SOC is obtained, where nonmagnetic semimetal, magnetic metal, and magnetic insulator are found. Magnetic ordering patterns beyond Uc are also presented. We further discuss implications of our finding in relation to other perovskites such as SrRhO3 and SrRuO3.

  6. 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

  7. Crystal growth of incommensurate members of 2H-hexagonal perovskite related oxides: Ba4MzPt3-zO9 (M=Co, Ni, Cu, Zn, Mg, Pt)

    NASA Astrophysics Data System (ADS)

    Ferreira, Timothy; Morrison, Gregory; Yeon, Jeongho; zur Loye, Hans-Conrad

    2016-04-01

    Millimeter sized crystals of six oxides of approximate composition Ba4MzPt3-zO9 (M=Co, Ni, Cu, Zn, Mg, Pt) were grown from molten K2CO3 fluxes and found to crystallize in a 2H hexagonal perovskite-related structure type. The compositions of these incommensurate structures, which belong to the A3n+3mA‧nB3m+nO9m+6n family of 2H hexagonal perovskite related oxides, were characterized by X-ray diffraction, energy dispersive spectroscopy, and magnetic susceptibility measurements. The specific synthetic considerations, crystal growth conditions, and magnetic susceptibility measurements are discussed.

  8. 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.

  9. Electronic doping of transition metal oxide perovskites

    NASA Astrophysics Data System (ADS)

    Cammarata, Antonio; Rondinelli, James M.

    2016-05-01

    CaFeO3 is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO3. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

  10. 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).

  11. 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.

  12. 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.

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

    PubMed

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

    2013-05-28

    Generalized trends in the formation energies of several families of perovskite oxides (ABO3) and plausible explanations to their existence are provided in this study through a combination of DFT calculations, solid-state physics analyses and simple physical/chemical descriptors. The studied elements at the A site of perovskites comprise rare-earth, alkaline-earth and alkaline metals, whereas 3d and 5d metals were studied at the B site. We also include ReO3-type compounds, which have the same crystal structure of cubic ABO3 perovskites except without A-site elements. From the observations we extract the following four conclusions for the perovskites studied in the present paper: for a given cation at the B site, (I) perovskites with cations of identical oxidation state at the A site possess close formation energies; and (II) perovskites with cations of different oxidation states at the A site usually have quite different but ordered formation energies. On the other hand, for a given A-site cation, (III) the formation energies of perovskites vary linearly with respect to the atomic number of the elements at the B site within the same period of the periodic table, and the slopes depend systematically on the oxidation state of the A-site cation; and (IV) the trends in formation energies of perovskites with elements from different periods at the B site depend on the oxidation state of A-site cations. Since the energetics of perovskites is shown to be the superposition of the individual contributions of their constituent oxides, the trends can be rationalized in terms of A-O and B-O interactions in the ionic crystal. These findings reveal the existence of general systematic trends in the formation energies of perovskites and provide further insight into the role of ion-ion interactions in the properties of ternary compounds. PMID:23579382

  14. 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.

  15. 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.

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

    DOE PAGESBeta

    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

  17. Topological Oxide Insulator in Cubic Perovskite Structure

    PubMed Central

    Jin, Hosub; Rhim, Sonny H.; Im, Jino; Freeman, Arthur J.

    2013-01-01

    The emergence of topologically protected conducting states with the chiral spin texture is the most prominent feature at the surface of topological insulators. On the application side, large band gap and high resistivity to distinguish surface from bulk degrees of freedom should be guaranteed for the full usage of the surface states. Here, we suggest that the oxide cubic perovskite YBiO3, more than just an oxide, defines itself as a new three-dimensional topological insulator exhibiting both a large bulk band gap and a high resistivity. Based on first-principles calculations varying the spin-orbit coupling strength, the non-trivial band topology of YBiO3 is investigated, where the spin-orbit coupling of the Bi 6p orbital plays a crucial role. Taking the exquisite synthesis techniques in oxide electronics into account, YBiO3 can also be used to provide various interface configurations hosting exotic topological phenomena combined with other quantum phases. PMID:23575973

  18. Topological Oxide Insulator in Cubic Perovskite Structure

    NASA Astrophysics Data System (ADS)

    Jin, Hosub; Rhim, Sonny H.; Im, Jino; Freeman, Arthur J.

    2013-04-01

    The emergence of topologically protected conducting states with the chiral spin texture is the most prominent feature at the surface of topological insulators. On the application side, large band gap and high resistivity to distinguish surface from bulk degrees of freedom should be guaranteed for the full usage of the surface states. Here, we suggest that the oxide cubic perovskite YBiO3, more than just an oxide, defines itself as a new three-dimensional topological insulator exhibiting both a large bulk band gap and a high resistivity. Based on first-principles calculations varying the spin-orbit coupling strength, the non-trivial band topology of YBiO3 is investigated, where the spin-orbit coupling of the Bi 6p orbital plays a crucial role. Taking the exquisite synthesis techniques in oxide electronics into account, YBiO3 can also be used to provide various interface configurations hosting exotic topological phenomena combined with other quantum phases.

  19. Decomposition of Organometal Halide Perovskite Films on Zinc Oxide Nanoparticles.

    PubMed

    Cheng, Yuanhang; Yang, Qing-Dan; Xiao, Jingyang; Xue, Qifan; Li, Ho-Wa; Guan, Zhiqiang; Yip, Hin-Lap; Tsang, Sai-Wing

    2015-09-16

    Solution processed zinc oxide (ZnO) nanoparticles (NPs) with excellent electron transport properties and a low-temperature process is a viable candidate to replace titanium dioxide (TiO2) as electron transport layer to develop high-efficiency perovskite solar cells on flexible substrates. However, the number of reported high-performance perovskite solar cells using ZnO-NPs is still limited. Here we report a detailed investigation on the chemistry and crystal growth of CH3NH3PbI3 perovskite on ZnO-NP thin films. We find that the perovskite films would severely decompose into PbI2 upon thermal annealing on the bare ZnO-NP surface. X-ray photoelectron spectroscopy (XPS) results show that the hydroxide groups on the ZnO-NP surface accelerate the decomposition of the perovskite films. To reduce the decomposition, we introduce a buffer layer in between the ZnO-NPs and perovskite layers. We find that a commonly used buffer layer with small molecule [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) can slow down but cannot completely avoid the decomposition. On the other hand, a polymeric buffer layer using poly(ethylenimine) (PEI) can effectively separate the ZnO-NPs and perovskite, which allows larger crystal formation with thermal annealing. The power conversion efficiencies of perovskite photovoltaic cells are significantly increased from 6.4% to 10.2% by replacing PC61BM with PEI as the buffer layer. PMID:26280249

  20. Electronically conductive perovskite-based oxide nanoparticles and films for optical sensing applications

    DOEpatents

    Ohodnicki, Jr., Paul R; Schultz, Andrew M

    2015-04-28

    The disclosure relates to a method of detecting a change in a chemical composition by contacting a electronically conducting perovskite-based metal oxide material with a monitored stream, illuminating the electronically conducting perovskite-based metal oxide with incident light, collecting exiting light, monitoring an optical signal based on a comparison of the incident light and the exiting light, and detecting a shift in the optical signal. The electronically conducting perovskite-based metal oxide has a perovskite-based crystal structure and an electronic conductivity of at least 10.sup.-1 S/cm, where parameters are specified at the gas stream temperature. The electronically conducting perovskite-based metal oxide has an empirical formula A.sub.xB.sub.yO.sub.3-.delta., where A is at least a first element at the A-site, B is at least a second element at the B-site, and where 0.8perovskite-based oxides include but are not limited to La.sub.1-xSr.sub.xCoO.sub.3, La.sub.1-xSr.sub.xMnO.sub.3, LaCrO.sub.3, LaNiO.sub.3, La.sub.1-xSr.sub.xMn.sub.1-yCr.sub.yO.sub.3, SrFeO.sub.3, SrVO.sub.3, La-doped SrTiO.sub.3, Nb-doped SrTiO.sub.3, and SrTiO.sub.3-.delta..

  1. Transparent conducting oxide free backside illuminated perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Li, Jia; Yao, Jiexiong; Xia, Huarong; Sun, Wentao; Liu, Jian; Peng, Lianmao

    2015-07-01

    Recently, hybrid perovskites have attracted great attention because of their promising applications in solar cells. However, perovskite solar devices reported till now are mostly based on transparent conducting oxide (TCO) substrates which account for a large proportion in the total cost. Herein, TCO-free perovskite solar cells are fabricated. A photo-electricity conversion efficiency of 5.27% is obtained with short circuit current density (Jsc) of 10.7 mA/cm2, open circuit voltage (Voc) of 0.837 V, and fill factor of 0.588. This study points a feasible way of replacing TCO substrate by low cost substrates, indicating promising potentials in solar energy conversion applications.

  2. Copper catalysts for soot oxidation: alumina versus perovskite supports.

    PubMed

    López-Suárez, F E; Bueno-López, A; Illán-Gómez, M J; Adamski, A; Ura, B; Trawczynski, J

    2008-10-15

    Copper catalysts prepared using four supports (Mg- and Sr-modified Al2O3 and MgTiO3 and SrTiO3 perovskites) have been tested for soot oxidation by 02 and NOx/O2. Among the catalysts studied, Cu/SrTiO3 is the most active for soot oxidation by NOx/O2 and the support affects positively copper activity. With this catalyst, and under the experimental conditions used, the soot combustion by NOx/O2 presents a considerable rate from 500 degrees C (100 degrees C below the uncatalysed reaction). The Cu/ SrTiO3 catalyst is also the most effective for NOx chemisorption around 425 degrees C. The best activity of Cu/SrTiO3 can be attributed to the improved redox properties of copper originated by Cu-support interactions. This seems to be related to the presence of weakly bound oxygen on this sample. The copper species present in the catalyst Cu/SrTiO3 can be reduced more easily than those in other supports, and for this reason, this catalyst seems to be the most effective to convert NO into NO2, which explains its highest activity for soot oxidation. PMID:18983091

  3. Bifunctional Perovskite Oxide Catalysts for Oxygen Reduction and Evolution in Alkaline Media.

    PubMed

    Gupta, Shiva; Kellogg, William; Xu, Hui; Liu, Xien; Cho, Jaephil; Wu, Gang

    2016-01-01

    Oxygen electrocatalysis, namely of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), governs the performance of numerous electrochemical energy systems such as reversible fuel cells, metal-air batteries, and water electrolyzers. However, the sluggish kinetics of these two reactions and their dependency on expensive noble metal catalysts (e.g, Pt or Ir) prohibit the sustainable commercialization of these highly innovative and in-demand technologies. Bifunctional perovskite oxides have emerged as a new class of highly efficient non-precious metal catalysts (NPMC) for oxygen electrocatalysis in alkaline media. In this review, we discuss the state-of-the-art understanding of bifunctional properties of perovskites with regards to their OER/ORR activity in alkaline media and review the associated reaction mechanisms on the oxides surface and the related activity descriptors developed in the recent literature. We also summarize the present strategies to modify their electronic structure and to further improve their performance for the ORR/OER through highlighting the new concepts relating to the role of surface redox chemistry and oxygen deficiency of perovskite oxides for the ORR/OER activity. In addition, we provide a brief account of recently developed advanced perovskite-nanocarbon hybrid bifunctional catalysts with much improved performances. PMID:26247625

  4. 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

  5. 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.

  6. 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

  7. Non-volatile memory based on transition metal perovskite oxide resistance switching

    NASA Astrophysics Data System (ADS)

    Nian, Yibo

    Driven by the non-volatile memory market looking for new advanced materials, this dissertation focuses on the study of non-volatile resistive random access memory (RRAM) based on transition metal perovskite oxides. Pr0.7Ca0.3MnO3 (PCMO), one of the representative materials in this family, has demonstrated a large range of resistance change when short electrical pulses with different polarity are applied. Such electrical-pulse-induced resistance (EPIR), with attractive features such as fast response, low power, high-density and non-volatility, makes PCMO and related materials promising candidates for non-volatile RRAM application. The objective of this work is to investigate, optimize and understand the properties of this universal EPIR behavior in transition metal perovskite oxide, represented by PCMO thin film devices. The research work includes fabrication of PCMO thin film devices, characterization of these EPIR devices as non-volatile memories, and investigation of their resistive switching mechanisms. The functionality of this perovskite oxide RRAM, including pulse magnitude/width dependence, power consumption, retention, endurance and radiation-hardness has been investigated. By studying the "shuttle tail" in hysteresis switching loops of oxygen deficient devices, a diffusion model with oxygen ions/vacancies as active agents at the metal/oxide interface is proposed for the non-volatile resistance switching effect in transition metal perovskite oxide thin films. The change of EPIR switching behavior after oxygen/argon ion implantation also shows experiment support for the proposed model. Furthermore, the universality, scalability and comparison with other non-volatile memories are discussed for future application.

  8. 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

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

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

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

  10. Perovskite-supported palladium for methane oxidation - structure-activity relationships.

    PubMed

    Eyssler, Arnim; Lu, Ye; Matam, Santhosh Kumar; Weidenkaff, Anke; Ferri, Davide

    2012-01-01

    Palladium is the precious metal of choice for methane oxidation and perovskite-type oxides offer the possibility to stabilize it as PdO, considered crucial for catalytic activity. Pd can adopt different oxidation and coordination states when associated with perovskite-type oxides. Here, we review our work on the effect of perovskite composition on the oxidation and coordination states of Pd and its influence on catalytic activity for methane oxidation in the case of typical Mn, Fe and Co perovskite-based oxidation catalysts. Especially X-ray absorption near edge structure (XANES) spectroscopy is shown to be crucial to fingerprint the different coordination states of Pd. Pd substitutes Fe and Co in the octahedral sites but without modifying catalytic activity with respect to the Pd-free perovskite. On LaMnO(3) palladium is predominantly exposed at the surface thus bestowing catalytic activity for methane oxidation. However, the occupancy of B-cation sites of the perovskite structure by Pd can be exploited to cyclically activate Pd and to protect it from particle growth. This is explicitly demonstrated for La(Fe, Pd)O(3), where catalytic activity for methane oxidation is enhanced under oscillating redox conditions at 500 °C, therefore paving the way to the practical application in three-way catalysts for stoichiometric natural gas engines. PMID:23211725

  11. Structural transformations in cubic structure of Mn/Co perovskites in reducing and oxidizing atmospheres

    NASA Astrophysics Data System (ADS)

    Koponen, Markus J.; Suvanto, Mika; Kallinen, Kauko; Kinnunen, Toni-J. J.; Härkönen, Matti; Pakkanen, Tapani A.

    2006-05-01

    ABO ( A=La, Pr; B=Mn, Co), ABBx'O ( A=La, Pr; B=Mn, Co; B=Co, Pd), and ABCoPdO ( A=La, Pr; B=Fe, Mn) ( x=0.05, 0.37; y=0.38) perovskites were synthesized via malic acid complexation. O 2-TPD, O 2-TPO, and H 2-TPR treatments were carried out to study the oxidation and reduction behavior of the synthesized perovskites. LaCo 0.95Pd 0.05O 3, PrCo 0.95Pd 0.05O 3, and PrCoO 3 perovskites had the highest desorption, oxidation, and reduction activity within the studied perovskite series. Powder XRD studies revealed structural transformation of the cubic structure of all synthesized perovskites except LaFe 0.57Co 0.38Pd 0.05O 3 in H 2/Ar atmosphere when the temperature was over 400 °C. The decomposed structure reverted to the original perovskite structure under oxidizing atmosphere. This reversion was accompanied by increased oxygen desorption activity. It was noticed that the Co and Mn combinations in the B-site of the perovskites structure decreased the thermal stability of the synthesized perovskites.

  12. Electronic and Magnetic Properties of Double Perovskites and Oxide Interfaces

    NASA Astrophysics Data System (ADS)

    Erten, Onur

    Transition metal oxides exhibit a wide range of fascinating phenomena ranging from high Tc superconductivity to colossal magnetoresistance. In this thesis, we examine the novel electronic and magnetic properties of double perovskites and oxide interfaces. First we focus on Sr2FeMoO6 which has a half-metallic ground state and a ferrimagnetic Tc=420 K, well above the room temperature. There are very few half-metals in nature and along with its high Tc, Sr2FeMoO6 has enormous potential in spintronics applications. We develop a minimal model that couples the conduction electrons on Mo (4d1) to the core spins of Fe (3d5). Delocalization of conduction electrons and maximizing the kinetic energy drives the long-range magnetic order. "Integrating out" the conduction electrons, we derive a new effective Hamiltonian, H eff, only for the localized spins. Heff is unique to double perovskites, and with its peculiar double square root form, it is different from standard Heisenberg or Anderson-Hasegawa Hamiltonians. Using Heff, we perform the first 3D, finite temperature calculations of double perovskites, going well beyond previous mean field or small cluster calculations. Next we consider Sr2CrOsO6 which has the highest Tc among all perovskites with a net moment. Its insulating behavior is puzzling given that Cr and Os are in the 3d3 and 5d3 configurations, half filled in t2g orbitals. The net moment at low temperature is M(0)=0.75 muB and non-monotonic magnetization as a function of temperature are quite unusual. To address these questions, we organize the problem through the hierarchy of its energy scales. To deal with the highest energy scale, the charge sector, we develop a multi-band Hubbard model that has different on-site Coulomb correlations on the Cr and Os sites. We solve this model using slave-rotor mean field theory which captures the essentials of the metal-Mott insulator transition and goes well beyond Hartree-Fock. We find a new criterion for the Mott transition

  13. 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

  14. Infrared and transport properties of the layered perovskite related oxide Ba 5Nb 4O 15 and its oxygen deficient phases

    NASA Astrophysics Data System (ADS)

    Pagola, S.; Massa, N. E.; Polla, G.; Leyva, G.; Carbonio, R. E.

    1994-12-01

    Ba 5Nb 4O 15-x oxides were studied by infrared, electrical resistivity and thermogravimmetric analysis (TGA). FIR reflectivity measurementsreveal a strong ionic compound that has well defined features in groups that we assign to oxygen stretching, bending and lattice phonons splitted by the lower symmetry of this layered compound. For the sample with x = 0.56, oxygen vacancies do not affect phonon band profiles, indicating that carriers are not free enough to interact with longitudinal modes. Electrical resistivity vs. temperature measurements show that the oxygen deficient compounds, for low values of x, are small band gap semiconductors.

  15. Photocatalytic oxidation of VOC, nitrogen oxide and atrazine using titanium dioxide modified with perovskite materials

    NASA Astrophysics Data System (ADS)

    Vajifdar, Kayzad Jimmy

    Photocatalysis utilizes near-UV or visible light to break down organic pollutants into innocuous compounds at room temperatures and has gained much attention in air and water pollution control. Chapter 1 introduces the use of semiconducting optical crystals as an additive to a photocatalyst. The perovskite optical material BaTiO3 (band gap of 3.7-3.8 eV) is found to increase VOC destruction when black light is used. The best composition found is 0.1 wt% BaTiO3 with the balance being TiO2. This photocatalyst increases perchloroethylene (PCE) conversion by 12% to 32% for space times between 1.4 and 17.2 seconds and inlet concentrations of 40 to 130 ppm with a 4 W black light. The average enhancement is approximately 25%. For butyraldehyde conversion the maximum enhancement is 20% at 130 ppm in 3.6 seconds. The UV/Vis spectroscopy data indicate a lower absorbance with the additive. The reaction parameters studied are space velocity, inlet concentration and light source. Oxidation by-products are identified using a GCMS. Chapter 2 introduces photocatalysis as an emerging green technology for environmental protection to oxidize NOx. The experimental results indicate that the coating of photocatalytic materials on concrete pavements can harvest the light energy for NOx pollution control. The photocatalytic coating has the potential to reduce NOx concentration in the atmosphere economically, nearly maintenance-free. NOx will be oxidized to nitric acid, neutralized by the alkaline base materials in concrete, and washed away by rain. The reduction in the number of high ozone days can be significant to allow sustainable economic developments in the many ozone-non-attainment areas worldwide. One of the foci will be pavement coated with photocatalysts enhanced with perovskites/ferroelectric optical crystals such as BaTiO3 via increased transmission/scattering and electron-hole pair stabilization. The developed technology can be transferred to the cement and coating industries

  16. Activity and structure of perovskites as diesel reforming catalysts for solid oxide fuel cells.

    SciTech Connect

    Liu, D.-J.; Krumpelt, M.; Chemical Engineering

    2005-01-01

    Recent progress in developing perovskite materials as more cost-effective catalysts in autothermal reforming (ATR) of diesel fuel to hydrogen-rich reformate for solid oxide fuel cell (SOFC) application is reported. Perovskite-type metal oxides with B sites partially exchanged by ruthenium were prepared and evaluated under ATR reaction conditions. The hydrogen yield, reforming efficiency, and CO{sub x} selectivity of these catalysts were investigated using diesel surrogate fuel with 50 ppm sulfur. The catalyst performances have approached or exceeded a benchmark, high-cost rhodium-based material. In parallel with the reactivity study, we also investigated the physical properties of B-site doped perovskites and their impact on the reforming performance using various characterization techniques such as BET, X-ray powder diffraction, temperature programmable reduction, scanning electron microscopy, and synchrotron X-ray absorption spectroscopy. We found that ruthenium is highly dispersed into perovskite lattice and its redox behavior is directly associated with reforming activity.

  17. Charge Trapping in Photovoltaically Active Perovskites and Related Halogenoplumbate Compounds.

    PubMed

    Shkrob, Ilya A; Marin, Timothy W

    2014-04-01

    Halogenoplumbate perovskites (MeNH3PbX3, where X is I and/or Br) have emerged as promising solar panel materials. Their limiting photovoltaic efficiency depends on charge localization and trapping processes that are presently insufficiently understood. We demonstrate that in halogenoplumbate materials the holes are trapped by organic cations (that deprotonate from their oxidized state) and Pb(2+) cations (as Pb(3+) centers), whereas the electrons are trapped by several Pb(2+) cations, forming diamagnetic lead clusters that also serve as color centers. In some cases, paramagnetic variants of these clusters can be observed. We suggest that charge separation in the halogenoplumbates resembles latent image formation in silver halide photography. Electron and hole trapping by lead clusters in extended dislocations in the bulk may be responsible for accumulation of trapped charge observed in this photovoltaic material. PMID:26274450

  18. Low-temperature solution-processed p-type vanadium oxide for perovskite solar cells.

    PubMed

    Sun, Haocheng; Hou, Xiaomeng; Wei, Qiulong; Liu, Huawei; Yang, Kecheng; Wang, Wei; An, Qinyou; Rong, Yaoguang

    2016-06-21

    A low-temperature solution-processed inorganic p-type contact material of vanadium oxide (VOx) was developed to fabricate planar-heterojunction perovskite solar cells. Using a solvent-assisted process, high-quality uniform and compact perovskite (CH3NH3PbI3) films were deposited on VOx coated substrates. Due to the high transmittance and quenching efficiency of VOx layers, a power conversion efficiency of over 14% was achieved. PMID:27263631

  19. 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

  20. 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.

  1. Tailoring of Electron-Collecting Oxide Nanoparticulate Layer for Flexible Perovskite Solar Cells.

    PubMed

    Shin, Seong Sik; Yang, Woon Seok; Yeom, Eun Joo; Lee, Seon Joo; Jeon, Nam Joong; Joo, Young-Chang; Park, Ik Jae; Noh, Jun Hong; Seok, Sang Il

    2016-05-19

    Low-temperature-processed perovskite solar cells (PSCs), especially those fabricated on flexible substrates, exhibit device performance that is worse than that of high-temperature-processed PSCs. One of the main reasons for the inferior performance of low-temperature-processed PSCs is the loss of photogenerated electrons in the electron collection layer (ECL) or related interfaces, i.e., indium tin oxide/ECL and ECL/perovskite. Here, we report that tailoring of the energy level and electron transporting ability in oxide ECLs using Zn2SnO4 nanoparticles and quantum dots notably minimizes the loss of photogenerated electrons in the low-temperature-fabricated flexible PSC. The proposed ECL with methylammonium lead halide [MAPb(I0.9Br0.1)3] leads to fabrication of significantly improved flexible PSCs with steady-state power conversion efficiency of 16.0% under AM 1.5G illumination of 100 mW cm(-2) intensity. These results provide an effective method for fabricating high-performance, low-temperature solution-processed flexible PSCs. PMID:27117778

  2. Modeling of thermal expansion coefficient of perovskite oxide for solid oxide fuel cell cathode

    NASA Astrophysics Data System (ADS)

    Heydari, F.; Maghsoudipour, A.; Alizadeh, M.; Khakpour, Z.; Javaheri, M.

    2015-09-01

    Artificial intelligence models have the capacity to eliminate the need for expensive experimental investigation in various areas of manufacturing processes, including the material science. This study investigates the applicability of adaptive neuro-fuzzy inference system (ANFIS) approach for modeling the performance parameters of thermal expansion coefficient (TEC) of perovskite oxide for solid oxide fuel cell cathode. Oxides (Ln = La, Nd, Sm and M = Fe, Ni, Mn) have been prepared and characterized to study the influence of the different cations on TEC. Experimental results have shown TEC decreases favorably with substitution of Nd3+ and Mn3+ ions in the lattice. Structural parameters of compounds have been determined by X-ray diffraction, and field emission scanning electron microscopy has been used for the morphological study. Comparison results indicated that the ANFIS technique could be employed successfully in modeling thermal expansion coefficient of perovskite oxide for solid oxide fuel cell cathode, and considerable savings in terms of cost and time could be obtained by using ANFIS technique.

  3. Atomic layer deposition of perovskite oxides and their epitaxial integration with Si, Ge, and other semiconductors

    SciTech Connect

    McDaniel, Martin D.; Ngo, Thong Q.; Hu, Shen; Ekerdt, John G.; Posadas, Agham; Demkov, Alexander A.

    2015-12-15

    Atomic layer deposition (ALD) is a proven technique for the conformal deposition of oxide thin films with nanoscale thickness control. Most successful industrial applications have been with binary oxides, such as Al{sub 2}O{sub 3} and HfO{sub 2}. However, there has been much effort to deposit ternary oxides, such as perovskites (ABO{sub 3}), with desirable properties for advanced thin film applications. Distinct challenges are presented by the deposition of multi-component oxides using ALD. This review is intended to highlight the research of the many groups that have deposited perovskite oxides by ALD methods. Several commonalities between the studies are discussed. Special emphasis is put on precursor selection, deposition temperatures, and specific property performance (high-k, ferroelectric, ferromagnetic, etc.). Finally, the monolithic integration of perovskite oxides with semiconductors by ALD is reviewed. High-quality epitaxial growth of oxide thin films has traditionally been limited to physical vapor deposition techniques (e.g., molecular beam epitaxy). However, recent studies have demonstrated that epitaxial oxide thin films may be deposited on semiconductor substrates using ALD. This presents an exciting opportunity to integrate functional perovskite oxides for advanced semiconductor applications in a process that is economical and scalable.

  4. Layered oxygen-deficient double perovskite as an efficient and stable anode for direct hydrocarbon solid oxide fuel cells.

    PubMed

    Sengodan, Sivaprakash; Choi, Sihyuk; Jun, Areum; Shin, Tae Ho; Ju, Young-Wan; Jeong, Hu Young; Shin, Jeeyoung; Irvine, John T S; Kim, Guntae

    2015-02-01

    Different layered perovskite-related oxides are known to exhibit important electronic, magnetic and electrochemical properties. Owing to their excellent mixed-ionic and electronic conductivity and fast oxygen kinetics, cation layered double perovskite oxides such as PrBaCo2O5 in particular have exhibited excellent properties as solid oxide fuel cell oxygen electrodes. Here, we show for the first time that related layered materials can be used as high-performance fuel electrodes. Good redox stability with tolerance to coking and sulphur contamination from hydrocarbon fuels is demonstrated for the layered perovskite anode PrBaMn2O5+δ (PBMO). The PBMO anode is fabricated by in situ annealing of Pr0.5Ba0.5MnO3-δ in fuel conditions and actual fuel cell operation is demonstrated. At 800 °C, layered PBMO shows high electrical conductivity of 8.16 S cm(-1) in 5% H2 and demonstrates peak power densities of 1.7 and 1.3 W cm(-2) at 850 °C using humidified hydrogen and propane fuels, respectively. PMID:25532072

  5. Layered oxygen-deficient double perovskite as an efficient and stable anode for direct hydrocarbon solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Sengodan, Sivaprakash; Choi, Sihyuk; Jun, Areum; Shin, Tae Ho; Ju, Young-Wan; Jeong, Hu Young; Shin, Jeeyoung; Irvine, John T. S.; Kim, Guntae

    2015-02-01

    Different layered perovskite-related oxides are known to exhibit important electronic, magnetic and electrochemical properties. Owing to their excellent mixed-ionic and electronic conductivity and fast oxygen kinetics, cation layered double perovskite oxides such as PrBaCo2O5 in particular have exhibited excellent properties as solid oxide fuel cell oxygen electrodes. Here, we show for the first time that related layered materials can be used as high-performance fuel electrodes. Good redox stability with tolerance to coking and sulphur contamination from hydrocarbon fuels is demonstrated for the layered perovskite anode PrBaMn2O5+δ (PBMO). The PBMO anode is fabricated by in situ annealing of Pr0.5Ba0.5MnO3-δ in fuel conditions and actual fuel cell operation is demonstrated. At 800 °C, layered PBMO shows high electrical conductivity of 8.16 S cm-1 in 5% H2 and demonstrates peak power densities of 1.7 and 1.3 W cm-2 at 850 °C using humidified hydrogen and propane fuels, respectively.

  6. Structure-property relationships of nanoscale engineered perovskite oxides

    NASA Astrophysics Data System (ADS)

    Tian, Wei

    Recent advances in the synthesis of nanoscale customized structure have demonstrated that reactive molecular beam epitaxy (MBE) can be used to construct nanostructure of oxides with atomic control. The ability to engineer the structure and chemistry of oxides at the nanometer scale makes possible for the creation of new functional materials that can be designed to have exceptional properties. This thesis focused on understanding structure-property relationships of such nanoscale customized oxides utilizing state-of-the-art transmission electron microscopy (TEM). Epitaxial thin films of n = 1--5 members of Ruddlesden-Popper homologous series Srn+1Ti nO3n+1 were synthesized by reactive MBE. We investigated the structure and microstructure of these thin films by x-ray diffraction along with high-resolution transmission electron microscopy (HRTEM) in combination with computer image simulations. We found that the thin films of n = 1--3 members are nearly free of intergrowths, e.g. phase-pure, while n = 4 and 5 thin films contain noticeably more intergrowth defects and anti-phase boundaries in their perovskite sheets. We show that these results are consistent with what is known about the thermodynamics of Sr n+1TinO3 n+1 phases. We also investigated the atomic structure and interfacial structure of artificial PbTiO3/SrTiO3 and BaTiO3/SrTiO 3 superlattices grown by MBE both with and without digital compositional grading. Both of these systems form a solid solution over their entire composition range. Thus, these layered heterostructures are metastable. We demonstrated, however, that the thermodynamically metastable superlattices can be kinetically stabilized via layer-by-layer growth. In addition, we found that the interfaces between two constituents in the heterostructures are atomically-abrupt. The superlattice thin films were made fully coherent with the substrates, resulting in a homogeneous large strain in the BaTiO3 layers due to the lattice mismatch between BaTiO3

  7. Photocatalytic activity of layered perovskite-like oxides in practically valuable chemical reactions

    NASA Astrophysics Data System (ADS)

    Rodionov, I. A.; Zvereva, I. A.

    2016-03-01

    The photocatalytic properties of layered perovskite-like oxides corresponding to the Ruddlesen–Popper, Dion–Jacobson and Aurivillius phases are considered. Of the photocatalytic reactions, the focus is on the reactions of water splitting, hydrogen evolution from aqueous solutions of organic substances and degradation of model organic pollutants. Possibilities to conduct these reactions under UV and visible light in the presence of layered perovskite-like oxides and composite photocatalysts based on them are shown. The specific surface area, band gap energy, particle morphology, cation and anion doping and surface modification are considered as factors that affect the photocatalytic activity. Special attention is paid to the possibilities to enhance the photocatalytic activity by intercalation, ion exchange and exfoliation, which are inherent in this class of compounds. Conclusions are made about the prospects for the use of layered perovskite-like oxides in photocatalysis. The bibliography includes 253 references.

  8. 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

  9. Neutron diffraction studies of nickel-containing perovskite oxide catalysts exposed to autothermal reforming environments.

    SciTech Connect

    Mawdsley, J. R.; Vaughey, J. T.; Krause, T. R.; Chemical Sciences and Engineering Division

    2009-10-27

    Six nickel-containing perovskite oxides (La{sub 1-x}Sr{sub x})M{sub 0.9}Ni{sub 0.1}O{sub 3{+-}{delta}}, where x = 0 or 0.2 and M = Cr, Fe, or Mn were used to catalyze the autothermal reforming of isooctane (C{sub 8}H{sub 18}) into a hydrogen-rich gas during short-term tests at 700 C. To determine the phase stability of the samples in the reducing environment of the reforming reactor, characterization studies of the as-prepared and tested perovskite samples were conducted using powder X-ray diffraction, powder neutron diffraction, transmission electron microscopy, and scanning electron microscopy. We determined that the reducing conditions of the microreactor caused metallic nickel to form in all six compositions. However, the extent of the nickel loss from the perovskite lattices varied: the chromium-containing compositions lost the least nickel, compared to the manganese- and iron-containing compositions, and the strontium-free compositions lost more nickel than their strontium-containing analogs. Five of the six perovskite compositions tested showed no breakdown of the perovskite lattice despite the loss of nickel from the B-sites, producing only the third example of a B-cation-deficient, 3d transition-metal-containing perovskite.

  10. 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

  11. 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

  12. Improved air stability of perovskite solar cells via solution-processed metal oxide transport layers

    NASA Astrophysics Data System (ADS)

    You, Jingbi; Meng, Lei; Song, Tze-Bin; Guo, Tzung-Fang; Yang, Yang (Michael); Chang, Wei-Hsuan; Hong, Ziruo; Chen, Huajun; Zhou, Huanping; Chen, Qi; Liu, Yongsheng; De Marco, Nicholas; Yang, Yang

    2016-01-01

    Lead halide perovskite solar cells have recently attracted tremendous attention because of their excellent photovoltaic efficiencies. However, the poor stability of both the perovskite material and the charge transport layers has so far prevented the fabrication of devices that can withstand sustained operation under normal conditions. Here, we report a solution-processed lead halide perovskite solar cell that has p-type NiOx and n-type ZnO nanoparticles as hole and electron transport layers, respectively, and shows improved stability against water and oxygen degradation when compared with devices with organic charge transport layers. Our cells have a p-i-n structure (glass/indium tin oxide/NiOx/perovskite/ZnO/Al), in which the ZnO layer isolates the perovskite and Al layers, thus preventing degradation. After 60 days storage in air at room temperature, our all-metal-oxide devices retain about 90% of their original efficiency, unlike control devices made with organic transport layers, which undergo a complete degradation after just 5 days. The initial power conversion efficiency of our devices is 14.6 ± 1.5%, with an uncertified maximum value of 16.1%.

  13. Improved air stability of perovskite solar cells via solution-processed metal oxide transport layers.

    PubMed

    You, Jingbi; Meng, Lei; Song, Tze-Bin; Guo, Tzung-Fang; Yang, Yang Michael; Chang, Wei-Hsuan; Hong, Ziruo; Chen, Huajun; Zhou, Huanping; Chen, Qi; Liu, Yongsheng; De Marco, Nicholas; Yang, Yang

    2016-01-01

    Lead halide perovskite solar cells have recently attracted tremendous attention because of their excellent photovoltaic efficiencies. However, the poor stability of both the perovskite material and the charge transport layers has so far prevented the fabrication of devices that can withstand sustained operation under normal conditions. Here, we report a solution-processed lead halide perovskite solar cell that has p-type NiO(x) and n-type ZnO nanoparticles as hole and electron transport layers, respectively, and shows improved stability against water and oxygen degradation when compared with devices with organic charge transport layers. Our cells have a p-i-n structure (glass/indium tin oxide/NiO(x)/perovskite/ZnO/Al), in which the ZnO layer isolates the perovskite and Al layers, thus preventing degradation. After 60 days storage in air at room temperature, our all-metal-oxide devices retain about 90% of their original efficiency, unlike control devices made with organic transport layers, which undergo a complete degradation after just 5 days. The initial power conversion efficiency of our devices is 14.6 ± 1.5%, with an uncertified maximum value of 16.1%. PMID:26457966

  14. Thermal diffusivity of oxide perovskite compounds at elevated temperature

    NASA Astrophysics Data System (ADS)

    Hofmeister, Anne M.

    2010-05-01

    The phonon component of thermal diffusivity (D) for eleven compounds (synthetic SrTiO3, SrTiO3:Fe3+, BaTiO3, KTaO3, KNbO3, NdGaO3, YAlO3, YAlO3:Tm, LaAlO3, La0.29Sr0.66Al0.65Ta0.35O3, and natural Ca1.01Mn0.001Fe0.007Ti0.99O3) with various perovskite structures was measured from ambient temperature (T) up to ˜2000 K using contact-free, laser-flash analysis, from which effects of ballistic radiative transfer were removed. Structural transitions (e.g., orthorhombic to tetragonal) below 800 K were manifest as sharp steps in 1/D. Above 800 K, structural transitions occur over intervals of ˜150 K. Similarly broad peaks accompany changes from colorless to black, attributable to partial reduction in Ti, Nb, or Ta from contact with graphite coatings. Otherwise, D decreases with increasing T and, if substitutional disorder exists, approaches a constant (Dsat) near 1600 K. Our data are best described as D-1 following a low order polynomial in T. Ordered, cubic perovskites occupy a single trend for D(T )-1, defining the contribution of the ideal lattice. Distortion, disorder, and polymorphism affect D-1 in a manner that is consistent with the damped harmonic oscillator-phonon gas model which relates phonon lifetimes to infrared peak widths. Calculated D-values at ambient and high T agree with measurements. The behavior of D is simple compared to that of thermal conductivity, k =ρCPD, where ρ is density and CP is heat capacity. Combining our data with cryogenic measurements of YAlO3 and LaAlO3 shows that D-1 depends on T similarly to CP, consistent with phonon lifetime depending on the density of states but, the best description for D-1(T) is a proportionality to αT from ˜0 K up to the limit of measurements, where α is thermal expansivity, a strongly anharmonic property. At low T, D-1 due to phonon scattering follows that of CP, generally∝T3, so klat=k0+k1T. Defects being present preclude scattering at sample walls, adding a small constant D0-1 ˜0.0001 mm-2 s as T

  15. Co-operative and frustration effects in novel perovskite-related phases

    NASA Astrophysics Data System (ADS)

    Ebbinghaus, S. G.; Riegg, S.; Götzfried, T.; Reller, A.

    2009-12-01

    We report on magnetic and electronic properties of various perovskite-type oxides containing 4d- and 5d-transition metals. The compounds under investigation crystallize in (distorted) cubic, layered, and hexagonal perovskite-related structures. These changes in structural dimensionality are reflected by different ordering phenomena. (Pseudo-) cubic perovskites ACu3B4O12 (with A = alkali, alkaline earth or rare earth; B = Ru, Ti) possess an A-site ordered structure with copper on modified A-positions. Structural investigations as well as XANES (X-ray absorption near edge structure) measurements indicate a valence degeneracy, which is keeping the oxidation state of Ru close to +4. Upon replacing Ru by Ti, the itinerant magnetism and metallic conductivity of the pure ruthenates successively change to a localized magnetic moment and a semiconducting behavior. The pure titanates like Ln2/3Cu3Ti4O12 or CaCu3Ti4O12are insulators with colossal dielectric constants. The cation-deficient Cu2+xTa4O12+δ shows a large compositional flexibility with 0.125 ≤ x ≤ 0.500. Both copper content and cooling speed have a strong impact on the crystal structure and the observed magnetic ordering. This behavior can be explained by uncompensated Cu2+-moments resulting from different site occupations. Quasi-2D La2RuO5 undergoes a structural and magnetic phase transition at roughly 160 K, leading to a diminishing magnetic moment and a semiconductor-semiconductor transition. LDA calculations reveal an antiferromagnetic coupling within pairs of neighboring Ru4+-ions, leading to a spin-Peierls like transition. New hexagonal perovskites containing Ru, Ir, and Pt crystallize in the [AO1+δ][A2BO6] structure type and contain peroxide ions (O) in the [AO1+δ] layers. La1.2Sr2.7IrO7.33 exhibits a small temperature-independent paramagnetism, which can be explained on basis of the crystal-field splitting and the strong spin-orbit coupling. The isostructural La1.2Sr2.7RuO7.33 shows a frustrated

  16. A First Principles Investigation of Proton Chemistry in Perovskite-Type Oxides

    NASA Astrophysics Data System (ADS)

    Tauer, Tania Allison

    Certain acceptor-doped perovskite-type oxides show significant promise for deployment into a number of electrochemical device applications, including fuel cells, batteries, and electrolyzers, owing to their rapid proton conductivities at high temperatures. However, limitations in bulk material hydration and slow grain boundary conductivities have reduced the viability of these materials in intermediate temperatures applications. This thesis work uses density functional theory to gain a fundamental understanding of proton and defect chemistry within various perovskite environments in order to identify strategies to increase proton concentration and improve overall proton conductivity. First, material hydration was probed within yttrium-doped barium cerate (BCY) to examine how the thermodynamics of material hydration are influenced by dopant concentration. A model was derived from solely first principle techniques to describe hydration within BCY as a function of dopant concentration, temperature, and partial pressure of water. The resulting model can be used to screen for favorable perovskite-dopant combinations with enhanced hydration capabilities. Next, defect segregation was investigated in the more complex interfacial environment to probe the origin of low proton conductivity across perovskite grain boundaries (GB). The results of this study suggest that screening for perovskite-dopant combinations with strong dopant-oxygen bond strengths may reduce the segregation of dopant ions and oxygen vacancies to the GB interface, mitigating the development of a positive GB core and enhancing proton conduction across the GB. Finally, proton stability was assessed at various interfacial regions within the perovskite material. An examination of proton adsorption at the BaZrO3-vacuum interface reveals a destabilization of protons in the first subsurface layer of the perovskite, yielding a potential barrier for proton diffusion into and out of the perovskite membrane. An

  17. Iron-based perovskite cathodes for solid oxide fuel cells

    DOEpatents

    Ralph, James M.; Rossignol, Cecile C.R.; Vaughey, John T.

    2007-01-02

    An A and/or A' site deficient perovskite of general formula of (A.sub.1-xA'.sub.x).sub.1-yFeO.sub.3-.delta. or of general formula A.sub.1-x-yA'.sub.xFeO.sub.3-67, wherein A is La alone or with one or more of the rare earth metals or a rare earth metal other than Ce alone or a combination of rare earth metals and X is in the range of from 0 to about 1; A' is Sr or Ca or mixtures thereof and Y is in the range of from about 0.01 to about 0.3; .delta. represents the amount of compensating oxygen loss. If either A or A' is zero the remaining A or A' is deficient. A fuel cell incorporating the inventive perovskite as a cathode is disclosed as well as an oxygen separation membrane. The inventive perovskite is preferably single phase.

  18. p-type Mesoscopic Nickel Oxide/Organometallic Perovskite Heterojunction Solar Cells

    PubMed Central

    Wang, Kuo-Chin; Jeng, Jun-Yuan; Shen, Po-Shen; Chang, Yu-Cheng; Diau, Eric Wei-Guang; Tsai, Cheng-Hung; Chao, Tzu-Yang; Hsu, Hsu-Cheng; Lin, Pei-Ying; Chen, Peter; Guo, Tzung-Fang; Wen, Ten-Chin

    2014-01-01

    In this article, we present a new paradigm for organometallic hybrid perovskite solar cell using NiO inorganic metal oxide nanocrystalline as p-type electrode material and realized the first mesoscopic NiO/perovskite/[6,6]-phenyl C61-butyric acid methyl ester (PC61BM) heterojunction photovoltaic device. The photo-induced transient absorption spectroscopy results verified that the architecture is an effective p-type sensitized junction, which is the first inorganic p-type, metal oxide contact material for perovskite-based solar cell. Power conversion efficiency of 9.51% was achieved under AM 1.5 G illumination, which significantly surpassed the reported conventional p-type dye-sensitized solar cells. The replacement of the organic hole transport materials by a p-type metal oxide has the advantages to provide robust device architecture for further development of all-inorganic perovskite-based thin-film solar cells and tandem photovoltaics. PMID:24755642

  19. Ti-doped molybdenum-based perovskites as anodes for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    He, Beibei; Wang, Zhenbin; Zhao, Ling; Pan, Xin; Wu, Xiaojun; Xia, Changrong

    2013-11-01

    Ti doping is found to increase the stability of Sr2NiMoO6 perovskite oxides in reducing atmosphere. The composition Sr2TiNi0.5Mo0.5O6 (STNM) is further evaluated as a potential oxide anode for solid oxide fuel cells (SOFCs). Electrical conductivity, thermal expansion coefficient, surface exchange coefficient, chemical diffusion coefficient, and its electrochemical performance in single cells with La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM) electrolytes are investigated. STNM exhibits a high conductivity of 17.5 S cm-1 at 800 °C at anodic atmosphere. The material shows good chemical and thermal expansion compatibilities with LSGM. To investigate the effect of Ti doping on the conduction properties, first-principle calculations are performed using the Vienna Ab initio Simulation. The strong Ti-O bond is held responsible for the enhanced structural stability of STNM under humidified H2 atmospheres, relative to that of the undoped system. The remarkable cell performance with both H2 and dry CH4 as the fuel indicates the potential ability of STNM to be used as SOFC anodes. These results obtained indicate that Sr2TiNi0.5Mo0.5O6 is a promising material for use as anode for intermediate temperature SOFCs.

  20. Tailored surfaces of perovskite oxide substrates for conducted growth of thin films.

    PubMed

    Sánchez, Florencio; Ocal, Carmen; Fontcuberta, Josep

    2014-04-01

    Oxide electronics relies on the availability of epitaxial oxide thin films. The extreme flexibility of the chemical composition of ABO3 perovskites and the broad spectrum of properties they cover, inspire the creativity of scientists and place perovskites in the lead of functional materials for advanced technologies. Moreover, emerging properties are being discovered at interfaces between distinct perovskites that could not be anticipated on the basis of those of the adjacent epitaxial layers. All dreamed new prospects require the use of suitable substrates for epitaxial growth. Perovskite single crystals are the workhorses of this activity and understanding and controlling their surface properties have become critical. In this tutorial review we will chiefly focus on the impact of the morphology and composition of the surface of ABO3 perovskite substrates on the growth mechanisms and properties of thin films epitaxially grown on them. As SrTiO3 is the most popular substrate, we will mostly concentrate on describing the current understanding and achievements for it. Illustrative examples of other perovskite substrates (LaAlO3, LSAT and DyScO3) will be also included. We will show that distinct chemical terminations can exist on the surfaces used for growth and we will review methods employed either to select the most appropriate one for specific growth to allow, for instance, tailoring the ultimate outmost epilayer, or to induce self-ordering to engineer long-range nanoscale patterns of chemical terminations. We will demonstrate the capacity of this knowledge by the growth of low-dimensional organic and inorganic structures. PMID:24553667

  1. Reducibility of Co 3+ in perovskite-type LaCoO 3 and promotion of copper on the reduction of Co 3+ in perovskite-type oxides

    NASA Astrophysics Data System (ADS)

    Huang, Lin; Bassir, Mahbod; Kaliaguine, Serge

    2005-04-01

    The reducibility of Co 3+ in LaCoO 3 and the promotion of copper on the reduction of Co 3+ in perovskite-type oxides have been studied by temperature programmed reduction (TPR), temperature programmed oxidation (TPO), X-ray diffraction (XRD) and infrared spectroscopy (IR). Quantitative TPR and TPO analyses propose that the reduction of Co 3+ in LaCoO 3 to Co 0 belongs to a one-step process and that every TPR peak represents the reduction of every Co 3+ species to Co 0 in the crystallite structure. Accordingly, the produced Co 0 is assumed to be atomically located in the perovskite lattice provided the perovskite structure is retained after reduction. Quantitative TPR analyses also indicates that copper located in LaCo 0.85Cu 0.15O 3 promotes regularly the reduction of various Co 3+ species whereas copper doped on LaCoO 3 does irregularly. The action of the latter leads to more efficient reduction of Co 3+ to atomically dispersed Co 0 over a useful temperature range for catalytic purposes. TPR, XRD and IR studies show that the perovskite structure of LaCo 0.85Cu 0.15O 3 is somewhat less stable than that of LaCoO 3 and that the perovskite structural stability of LaCoO 3 is not weakened by the doping of copper.

  2. Transition Metal-Oxide Free Perovskite Solar Cells Enabled by a New Organic Charge Transport Layer.

    PubMed

    Chang, Sehoon; Han, Ggoch Ddeul; Weis, Jonathan G; Park, Hyoungwon; Hentz, Olivia; Zhao, Zhibo; Swager, Timothy M; Gradečak, Silvija

    2016-04-01

    Various electron and hole transport layers have been used to develop high-efficiency perovskite solar cells. To achieve low-temperature solution processing of perovskite solar cells, organic n-type materials are employed to replace the metal oxide electron transport layer (ETL). Although PCBM (phenyl-C61-butyric acid methyl ester) has been widely used for this application, its morphological instability in films (i.e., aggregation) is detrimental. Herein, we demonstrate the synthesis of a new fullerene derivative (isobenzofulvene-C60-epoxide, IBF-Ep) that serves as an electron transporting material for methylammonium mixed lead halide-based perovskite (CH3NH3PbI3-xClx) solar cells, both in the normal and inverted device configurations. We demonstrate that IBF-Ep has superior morphological stability compared to the conventional acceptor, PCBM. IBF-Ep provides higher photovoltaic device performance as compared to PCBM (6.9% vs 2.5% in the normal and 9.0% vs 5.3% in the inverted device configuration). Moreover, IBF-Ep devices show superior tolerance to high humidity (90%) in air. By reaching power conversion efficiencies up to 9.0% for the inverted devices with IBF-Ep as the ETL, we demonstrate the potential of this new material as an alternative to metal oxides for perovskite solar cells processed in air. PMID:26947400

  3. Spin-Orbital Superstructure in Strained Ferrimagnetic Perovskite Cobalt Oxide

    NASA Astrophysics Data System (ADS)

    Fujioka, J.; Yamasaki, Y.; Nakao, H.; Kumai, R.; Murakami, Y.; Nakamura, M.; Kawasaki, M.; Tokura, Y.

    2013-07-01

    We have investigated the Co-3d spin-orbital state in a thin film of perovskite LaCoO3 to clarify the origin of strain induced spontaneous magnetization (TC=94K) by means of x-ray diffraction, optical spectroscopy, and magnetization measurements. A lattice distortion with the propagation vector (1/4 -​​1/4 1/4) and an anomalous activation of optical phonons coupled to Co-3d orbital are observed below 126 K. Combined with the azimuthal angle analysis of superlattice reflection, we propose that the ordering of Co-3d orbital promoted by an epitaxial strain produces a unique ferrimagnetic structure.

  4. Catalytic combustion of methane by perovskite-type oxide nanoparticles as pollution prevention strategy

    NASA Astrophysics Data System (ADS)

    Zaza, F.; Luisetto, I.; Serra, E.; Tuti, S.; Pasquali, M.

    2016-06-01

    The transition from the existing brown economy towards the desired green economy drives the research efforts to the development of advanced technologies promoting the efficient utilization of energy sources. Catalysis science offers to combustion technology significant opportunity to increase the fuel efficiency by lowering the internal temperature gradients and reduce the environmental impact by lowering local peak temperature and, consequently, thermodynamically inhibiting the nitrogen oxides formation. Alternative catalytic materials are transition metals oxide, including complex oxides with perovskite crystalline structure. The aim of this work is to synthetize lanthanum ferrite perovskites with lanthanum ions partially substituted by strontium ions in order to study the substitution effects on structural properties and redox activity of the original oxide. Lanthanum ferrite oxides partially substituted with different Strontium amount were synthesized by solution combustion method. The perovskite nanopowders obtained were characterized by XRD, SEM, TPR analyses for defining crystalline structure, morphology and redox properties. Finally, the catalytic activity for methane combustion was tested. The most performing catalysts was La0.6Sr0.4FeO3 having the highest oxygen vacancy concentration as revealed by TPR analysis.

  5. Parasitic Absorption Reduction in Metal Oxide-Based Transparent Electrodes: Application in Perovskite Solar Cells.

    PubMed

    Werner, Jérémie; Geissbühler, Jonas; Dabirian, Ali; Nicolay, Sylvain; Morales-Masis, Monica; Wolf, Stefaan De; Niesen, Bjoern; Ballif, Christophe

    2016-07-13

    Transition metal oxides (TMOs) are commonly used in a wide spectrum of device applications, thanks to their interesting electronic, photochromic, and electrochromic properties. Their environmental sensitivity, exploited for gas and chemical sensors, is however undesirable for application in optoelectronic devices, where TMOs are used as charge injection or extraction layers. In this work, we first study the coloration of molybdenum and tungsten oxide layers, induced by thermal annealing, Ar plasma exposure, or transparent conducting oxide overlayer deposition, typically used in solar cell fabrication. We then propose a discoloration method based on an oxidizing CO2 plasma treatment, which allows for a complete bleaching of colored TMO films and prevents any subsequent recoloration during following cell processing steps. Then, we show that tungsten oxide is intrinsically more resilient to damage induced by Ar plasma exposure as compared to the commonly used molybdenum oxide. Finally, we show that parasitic absorption in TMO-based transparent electrodes, as used for semitransparent perovskite solar cells, silicon heterojunction solar cells, or perovskite/silicon tandem solar cells, can be drastically reduced by replacing molybdenum oxide with tungsten oxide and by applying a CO2 plasma pretreatment prior to the transparent conductive oxide overlayer deposition. PMID:27338079

  6. Resistivity control by solid-state reaction of perovskite-type oxides

    SciTech Connect

    Nagamoto, H.; Tanaka, H.; Koya, T.

    1995-10-01

    Resistivity control has been conducted by solid-state reaction of two different perovskite-type oxides. One is La{sub 0.5}Ba{sub 0.5}CoO{sub 3{minus}{delta}} (LBC) which showed metallic conduction, and its resistivity, {rho} was 10{sup {minus}3} {Omega} {center_dot} cm at 20 C. The other is Ba{sub 0.998}Sb{sub 0.002}TiO{sub 3} (BT) which showed positive temperature coefficient of resistivity (PTCR) effect. The sintered body of the mixture of the two oxides did not show PTCR effect. The logarithm of the resistivity of the sintered body, log {rho}{sub mix} was expressed using the resistivity of LBC, {rho}{sub LBC}, the molar ratio of BT, x, and temperature dependent constant, {alpha}(T) as log {rho}{sub mix} = (1 {minus} x) log {rho}{sub LBC} + x{alpha}(T), which holds for 0 {le} x {le} 0.8 at the temperature ranging from 20 to 240 C. {rho}{sub mix} changed by about 8 orders of magnitude at room temperature. X-ray diffraction analysis suggested that metal ions at the A-site move from one perovskite-type oxide to another and that the sintered body consisted of two perovskite-type oxides different from starting ones.

  7. Selective Deposition of Insulating Metal Oxide in Perovskite Solar Cells with Enhanced Device Performance.

    PubMed

    Yue, Youfeng; Yang, Xudong; Wu, Yongzhen; Salim, Noviana Tjitra; Islam, Ashraful; Noda, Takeshi; Han, Liyuan

    2015-08-24

    We report a simple methodology for the selective deposition of an insulating layer on the nanoparticulate TiO2 (np-TiO2) mesoporous layer of perovskite solar cells. The deposited MgO insulating layer mainly covered the bottom part of the np-TiO2 layer with less coverage at the top. The so-called quasi-top-open structure is introduced to act as an efficient hole-blocking layer to prevent charge recombination at the physical contact of the transparent conducting oxide with the perovskite. This leads to an open-circuit voltage higher than that of the reference cell with a compact TiO2 hole-blocking layer. Moreover, such a quasi-top-open structure can facilitate the electron injection from perovskite into the np-TiO2 mesoporous layer and improve the spectral response at longer wavelength because of the less covered insulating layer at the top. This work provides an alternative way to fabricate perovskite solar cells without the need to use a conventional compact TiO2 layer. PMID:26230988

  8. Atomic level observation of octahedral distortions at the perovskite oxide heterointerface

    PubMed Central

    Aso, Ryotaro; Kan, Daisuke; Shimakawa, Yuichi; Kurata, Hiroki

    2013-01-01

    For perovskite oxides, ABO3, slight octahedral distortions have close links to functional properties. While perovskite oxide heterostructures offer a good platform for controlling functionalities, atomistic understanding of octahedral distortion at the interface has been a challenge as it requires precise measurements of the oxygen atomic positions. Here we demonstrate an approach to clarify distortions at an atomic level using annular bright-field imaging in aberration-corrected scanning transmission electron microscopy, which provides precise mappings of cation and oxygen atomic positions from distortion-minimized images. This technique revealed significant distortions of RuO6 and ScO6 octahedra at the heterointerface between a SrRuO3 film and a GdScO3 substrate. We also found that structural mismatch was relieved within only four unit cells near the interface by shifting the oxygen atomic positions to accommodate octahedral tilt angle mismatch. The present results underscore the critical role of the oxygen atom in the octahedral connectivity at the perovskite oxide heterointerface. PMID:23856752

  9. Deposition and dielectric characterization of strontium and tantalum-based oxide and oxynitride perovskite thin films

    NASA Astrophysics Data System (ADS)

    Jacq, S.; Le Paven, C.; Le Gendre, L.; Benzerga, R.; Cheviré, F.; Tessier, F.; Sharaiha, A.

    2016-04-01

    We have synthesized the composition x = 0.01 of the (Sr1-xLax)2(Ta1-xTix)2O7 solid solution, mixing the ferroelectric perovskite phases Sr2Ta2O7 and La2Ti2O7. Related oxide and oxynitride materials have been produced as thin films by magnetron radio frequency sputtering. Reactive sputter deposition was conducted at 750 °C under a 75 vol.% (Ar) + 25 vol.% (N2,O2) mixture. An oxygen-free plasma leads to the deposition of an oxynitride film (Sr0.99La0.01) (Ta0.99Ti0.01)O2N, characterized by a band gap Eg = 2.30 eV and a preferential (001) epitaxial growth on (001) SrTiO3 substrate. Its dielectric constant and loss tangent are respectively Epsilon' = 60 (at 1 kHz) and tanDelta = 62.5 × 10-3. In oxygen-rich conditions (vol.%N2 ≤ 15%), (110) epitaxial (Sr0.99La0.01)2(Ta0.99Ti0.01)2O7 oxides films are deposited, associated to a larger band gap value (Eg = 4.55 eV). The oxide films permittivity varies from 45 to 25 (at 1 kHz) in correlation with the decrease in crystalline orientation; measured losses are lower than 5.10-3. For 20 ≤ vol.% N2 ≤ 24.55, the films are poorly crystallized, leading to very low permittivities (minimum Epsilon' = 3). A correlation between the dielectric losses and the presence of an oxynitride phase in the samples is highlighted.

  10. Electronic State of Fe in Double Perovskite Oxide Sr 2FeWO 6

    NASA Astrophysics Data System (ADS)

    Kawanaka, Hirofumi; Hase, Izumi; Toyama, Shunichiro; Nishihara, Yoshikazu

    1999-09-01

    The magnetic properties of double perovskite oxide Sr2FeWO6 have been reported. The magnetic susceptibility and Mössbauer effect of 57Fe show that this compound is an antiferromagnet with T N=37 K. The Mössbauer parameters below ˜20 K are the center shift of +1.2 mm/s relative to metallic iron, the quadrupole splitting of 1.9 mm/s and the hyperfine field of ˜110 kOe. The quadrupole splitting has a strong temperature dependence. From these data, we conclude that Fe in Sr2FeWO6 is in the Fe2+ high-spin state, while the hyperfine field seems to be quite small. The cell volume shows a large increase compared to other Sr2FeTO6 ( T= Mo, Re, etc.), which is in the Fe3+ high-spin state. These results suggest that these compounds have a strongly coupled charge and lattice systems.

  11. Bismuth doped lanthanum ferrite perovskites as novel cathodes for intermediate-temperature solid oxide fuel cells.

    PubMed

    Li, Mei; Wang, Yao; Wang, Yunlong; Chen, Fanglin; Xia, Changrong

    2014-07-23

    Bismuth is doped to lanthanum strontium ferrite to produce ferrite-based perovskites with a composition of La(0.8-x)Bi(x)Sr0.2FeO(3-δ) (0 ≤ x ≤ 0.8) as novel cathode material for intermediate-temperature solid oxide fuel cells. The perovskite properties including oxygen nonstoichiometry coefficient (δ), average valence of Fe, sinterability, thermal expansion coefficient, electrical conductivity (σ), oxygen chemical surface exchange coefficient (K(chem)), and chemical diffusion coefficient (D(chem)) are explored as a function of bismuth content. While σ decreases with x due to the reduced Fe(4+) content, D(chem) and K(chem) increase since the oxygen vacancy concentration is increased by Bi doping. Consequently, the electrochemical performance is substantially improved and the interfacial polarization resistance is reduced from 1.0 to 0.10 Ω cm(2) at 700 °C with Bi doping. The perovskite with x = 0.4 is suggested as the most promising composition as solid oxide fuel cell cathode material since it has demonstrated high electrical conductivity and low interfacial polarization resistance. PMID:24971668

  12. Iridium-based double perovskites for efficient water oxidation in acid media

    PubMed Central

    Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud; Kooyman, Patricia J.; Wezendonk, Tim; Gascon, Jorge; Fu, W. T.; Koper, Marc T. M.

    2016-01-01

    The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2. PMID:27498694

  13. Iridium-based double perovskites for efficient water oxidation in acid media

    NASA Astrophysics Data System (ADS)

    Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud; Kooyman, Patricia J.; Wezendonk, Tim; Gascon, Jorge; Fu, W. T.; Koper, Marc T. M.

    2016-08-01

    The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2.

  14. Iridium-based double perovskites for efficient water oxidation in acid media.

    PubMed

    Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud; Kooyman, Patricia J; Wezendonk, Tim; Gascon, Jorge; Fu, W T; Koper, Marc T M

    2016-01-01

    The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2. PMID:27498694

  15. Niobium doped lanthanum calcium ferrite perovskite as a novel electrode material for symmetrical solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kong, Xiaowei; Zhou, Xiaoliang; Tian, Yu; Wu, Xiaoyan; Zhang, Jun; Zuo, Wei

    2016-09-01

    Development of cost-effective and efficient electrochemical catalysts for the fuel cells electrode is of prime importance to emerging renewable energy technologies. Here, we report for the first time the novel La0.9Ca0.1Fe0.9Nb0.1O3-δ (LCFNb) perovskite with good potentiality for the electrode material of the symmetrical solid oxide fuel cells (SSOFC). The Sc0.2Zr0.8O2-δ (SSZ) electrolyte supported symmetrical cells with impregnated LCFNb and LCFNb/SDC (Ce0.8Sm0.2O2-δ) electrodes achieve relatively high power outputs with maximum power densities (MPDs) reaching up to 392 and 528.6 mW cm-2 at 850 °C in dry H2, respectively, indicating the excellent electro-catalytic activity of LCFNb towards both hydrogen oxidation and oxygen reduction. Besides, the MPDs of the symmetrical cells with LCFNb/SDC composite electrodes in CO and syngas (CO: H2 = 1:1) are almost identical to those in H2, implying that LCFNb material has similar catalytic activities to carbon monoxide compared with hydrogen. High durability in both H2, CO and syngas during the short term stability tests for 50 h are also obtained, showing desirable structure stability, and carbon deposition resistance of LCFNb based electrodes. The present results indicate that the LCFNb perovskite with remarkable cell performance is a promising electrode material for symmetrical SOFCs.

  16. Water-Gas Shift and Methane Reactivity on Reducible Perovskite-Type Oxides

    PubMed Central

    2015-01-01

    Comparative (electro)catalytic, structural, and spectroscopic studies in hydrogen electro-oxidation, the (inverse) water-gas shift reaction, and methane conversion on two representative mixed ionic–electronic conducting perovskite-type materials La0.6Sr0.4FeO3−δ (LSF) and SrTi0.7Fe0.3O3−δ (STF) were performed with the aim of eventually correlating (electro)catalytic activity and associated structural changes and to highlight intrinsic reactivity characteristics as a function of the reduction state. Starting from a strongly prereduced (vacancy-rich) initial state, only (inverse) water-gas shift activity has been observed on both materials beyond ca. 450 °C but no catalytic methane reforming or methane decomposition reactivity up to 600 °C. In contrast, when starting from the fully oxidized state, total methane oxidation to CO2 was observed on both materials. The catalytic performance of both perovskite-type oxides is thus strongly dependent on the degree/depth of reduction, on the associated reactivity of the remaining lattice oxygen, and on the reduction-induced oxygen vacancies. The latter are clearly more reactive toward water on LSF, and this higher reactivity is linked to the superior electrocatalytic performance of LSF in hydrogen oxidation. Combined electron microscopy, X-ray diffraction, and Raman measurements in turn also revealed altered surface and bulk structures and reactivities. PMID:26045733

  17. Alloy perovskite oxide thin film as resistance switching non-volatile memory

    NASA Astrophysics Data System (ADS)

    Wang, Yudi

    Nonvolatile memory that permanently stores data is indispensable for computers and hand-held devices. In the last few years, resistance memory (RRAM) has emerged as an intriguing possibility that might replace flash memory one day, which is widely used in hand-held and portable-storage devices. The newest, rapidly growing interest in resistance switching is focused on semiconducting oxides and other related materials. In this dissertation, a novel material system for oxide RRAM that offers unique advantages over all the other existing oxide RRAM materials was designed and systematically investigated. The primary aim of these studies is to obtain a material system with the intrinsic property that allows electrically-induced metal-insulator transition, which is regulated by electron trapping and release at some interval sites. A series of alloy perovskite oxides thin film systems were designed by combining a wide band gap insulator (CaZrO3 or LaAlO3) and a conductor with a narrow bandwidth (SrRuO3 or LaNiO3 ), with the conductor concentration near the percolation threshold. These alloy perovskite oxides thin films are almost atomically flat without any defects, such as cracks or crosshatches, which is achieved using well controlled deposition conditions that favor domain-boundary relaxation of the large misfit strain. The bottom electrode is a single crystalline SrRuO 3 thin film, deposited on a single crystal substrate of SrTiO3 which exhibits high conductivity and ferromagnetic transition at ˜150K. The alloy thin films manifest an anisotropic percolation phenomenon: below a critical thickness a metallic conducting path always exists across the film thickness direction but not along the in-plane direction, which ensures electrical isolation between neighboring memory cells. These initially conducting films present excellent resistance switching properties: low switching voltages (1-3 V), high switching ratio (˜100), fast switching speed (50 ns), good switching

  18. Ionic liquid-mediated synthesis of meso-scale porous lanthanum-transition-metal perovskites with high CO oxidation performance

    SciTech Connect

    Lu, Hanfeng; Zhang, Pengfei; Qiao, Zhen-An; Zhang, Jinshui; Zhu, Huiyuan; Chen, Jihua; Chen, Yinfei; Dai, Sheng

    2015-02-19

    Lanthanum-transition-metal perovskites with robust meso-scale porous frameworks (meso-LaMO3) are synthesized through use of ionic liquids. The resultant samples demonstrate a rather high activity for CO oxidation, by taking advantage of unique nanostructure-derived benefits. This synthesis strategy opens up a new opportunity for preparing functional mesoporous complex oxides of various compositions.

  19. Ionic liquid-mediated synthesis of meso-scale porous lanthanum-transition-metal perovskites with high CO oxidation performance

    DOE PAGESBeta

    Lu, Hanfeng; Zhang, Pengfei; Qiao, Zhen-An; Zhang, Jinshui; Zhu, Huiyuan; Chen, Jihua; Chen, Yinfei; Dai, Sheng

    2015-02-19

    Lanthanum-transition-metal perovskites with robust meso-scale porous frameworks (meso-LaMO3) are synthesized through use of ionic liquids. The resultant samples demonstrate a rather high activity for CO oxidation, by taking advantage of unique nanostructure-derived benefits. This synthesis strategy opens up a new opportunity for preparing functional mesoporous complex oxides of various compositions.

  20. Research Update: Interface-engineered oxygen octahedral tilts in perovskite oxide heterostructures

    SciTech Connect

    Kan, Daisuke Aso, Ryotaro; Kurata, Hiroki; Shimakawa, Yuichi

    2015-06-01

    Interface engineering of structural distortions is a key for exploring the functional properties of oxide heterostructures and superlattices. In this paper, we report on our comprehensive investigations of oxygen octahedral distortions at the heterointerface between perovskite oxides SrRuO{sub 3} and BaTiO{sub 3} on GdScO{sub 3} substrates and of the influences of the interfacially engineered distortions on the magneto-transport properties of the SrRuO{sub 3} layer. Our state-of-the-art annular bright-field imaging in aberration-corrected scanning transmission electron microscopy revealed that the RuO{sub 6} octahedral distortions in the SrRuO{sub 3} layer have strong dependence on the stacking order of the SrRuO{sub 3} and BaTiO{sub 3} layers on the substrate. This can be attributed to the difference in the interfacial octahedral connections. We also found that the stacking order of the oxide layers has a strong impact on the magneto-transport properties, allowing for control of the magnetic anisotropy of the SrRuO{sub 3} layer through interface engineering. Our results demonstrate the significance of the interface engineering of the octahedral distortions on the structural and physical properties of perovskite oxides.

  1. 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

  2. Structure-property relationships of BaCeO perovskites for the oxidative dehydrogenation of alkanes

    SciTech Connect

    Nenoff, T.M.; Jackson, N.B.; Miller, J.E.; Sault, A.G.; Trudell, D.

    1997-12-01

    The oxidative dehydrogenation (ODH) reactions for the formation of two important organic feedstocks ethylene and propylene are of great interest because of the potential in capital and energy savings associated with these reactions. Theoretically, ODH can achieve high conversions of the starting materials (ethane and propane) at lower temperatures than conventional dehydrogenation reactions. The important focus in this study of ODH catalysts is the development of a structure-property relationship for catalyst with respect to selectivity, so as to avoid the more thermodynamically favorable combustion reaction. Catalysts for the ODH reaction generally consist of mixed metal oxides. Since for the most selective catalyst lattice oxygen is known to participate in the reaction, catalysts are sought with surface oxygen atoms that are labile enough to perform dehydrogenation, but not so plentiful or weakly bound as to promote complete combustion. Also, catalysts must be able to replenish surface oxygen by transport from the bulk. Perovskite materials are candidates to fulfill these requirements. The authors are studying BaCeO{sub 3} perovskites doped with elements such as Ca, Mg, and Sr. During the ODH of the alkanes at high temperatures, the perovskite structure is not retained and a mixture of carbonates and oxides is formed, as revealed by XRD. While the Ca doped materials showed enhanced total combustion activity below 600 C, they only showed enhanced alkene production at 700 C. Bulk structural and surface changes, as monitored by powder X-ray diffraction, and X-ray photoelectron spectroscopy are being correlated with activity in order to understand the factors affecting catalyst performance, and to modify catalyst formulations to improve conversion and selectivity.

  3. Direct Observation of Electrostatically Driven Band Gap Renormalization in a Degenerate Perovskite Transparent Conducting Oxide.

    PubMed

    Lebens-Higgins, Z; Scanlon, D O; Paik, H; Sallis, S; Nie, Y; Uchida, M; Quackenbush, N F; Wahila, M J; Sterbinsky, G E; Arena, Dario A; Woicik, J C; Schlom, D G; Piper, L F J

    2016-01-15

    We have directly measured the band gap renormalization associated with the Moss-Burstein shift in the perovskite transparent conducting oxide (TCO), La-doped BaSnO_{3}, using hard x-ray photoelectron spectroscopy. We determine that the band gap renormalization is almost entirely associated with the evolution of the conduction band. Our experimental results are supported by hybrid density functional theory supercell calculations. We determine that unlike conventional TCOs where interactions with the dopant orbitals are important, the band gap renormalization in La-BaSnO_{3} is driven purely by electrostatic interactions. PMID:26824566

  4. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    NASA Astrophysics Data System (ADS)

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-10-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1-xSrxFeyMn1-yO3-d(0 ≤ x≤ 1, 0.2 ≤ y≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d and the Fe-K catalysts in aH2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3-d was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d perovskite oxide.

  5. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    PubMed Central

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-01-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 − xSrxFeyMn1 − yO3 − δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst with that of an industrial potassium promoted iron (Fe–K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ and the Fe–K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ perovskite oxide. PMID:24790949

  6. 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).

  7. Stable and null current hysteresis perovskite solar cells based nitrogen doped graphene oxide nanoribbons hole transport layer

    PubMed Central

    Kim, Jeongmo; Mat Teridi, Mohd Asri; Mohd Yusoff, Abd. Rashid bin; Jang, Jin

    2016-01-01

    Perovskite solar cells are becoming one of the leading technologies to reduce our dependency on traditional power sources. However, the frequently used component poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) has several shortcomings, such as an easily corroded indium-tin-oxide (ITO) interface at elevated temperatures and induced electrical inhomogeneity. Herein, we propose solution-processed nitrogen-doped graphene oxide nanoribbons (NGONRs) as a hole transport layer (HTL) in perovskite solar cells, replacing the conducting polymer PEDOT:PSS. The conversion efficiency of NGONR-based perovskite solar cells has outperformed a control device constructed using PEDOT:PSS. Moreover, our proposed NGONR-based devices also demonstrate a negligible current hysteresis along with improved stability. This work provides an effective route for substituting PEDOT:PSS as the effective HTL. PMID:27277388

  8. Stable and null current hysteresis perovskite solar cells based nitrogen doped graphene oxide nanoribbons hole transport layer

    NASA Astrophysics Data System (ADS)

    Kim, Jeongmo; Mat Teridi, Mohd Asri; Mohd Yusoff, Abd. Rashid Bin; Jang, Jin

    2016-06-01

    Perovskite solar cells are becoming one of the leading technologies to reduce our dependency on traditional power sources. However, the frequently used component poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) has several shortcomings, such as an easily corroded indium-tin-oxide (ITO) interface at elevated temperatures and induced electrical inhomogeneity. Herein, we propose solution-processed nitrogen-doped graphene oxide nanoribbons (NGONRs) as a hole transport layer (HTL) in perovskite solar cells, replacing the conducting polymer PEDOT:PSS. The conversion efficiency of NGONR-based perovskite solar cells has outperformed a control device constructed using PEDOT:PSS. Moreover, our proposed NGONR-based devices also demonstrate a negligible current hysteresis along with improved stability. This work provides an effective route for substituting PEDOT:PSS as the effective HTL.

  9. Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

    DOEpatents

    Rieke, Peter C.; Coffey, Gregory W.; Pederson, Larry R.; Marina, Olga A.; Hardy, John S.; Singh, Prabhaker; Thomsen, Edwin C.

    2010-07-20

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

  10. Remarkable effect of Pt nanoparticles on visible light-induced oxygen generation from water catalysed by perovskite oxides.

    PubMed

    Gupta, Uttam; Naidu, B S; Rao, C N R

    2015-01-14

    Oxidation of water is a challenging process with a positive free energy change and it is purposeful to find good catalysts to facilitate the process. While the perovskite oxides, LaCoO3 and LaMnO3, are good electron transfer catalysts in artificial photosynthesis to produce oxygen by the oxidation of water, the electron transfer is further favoured by the presence of platinum nanoparticles, causing a substantial increase in oxygen evolution. PMID:25407344

  11. Impact of hole doping on spin transition in perovskite-type cobalt oxides.

    PubMed

    Che, Xiangli; Li, Liping; Hu, Wanbiao; Li, Guangshe

    2016-06-28

    Series of perovskite PrCo1-xNixO3-δ (x = 0-0.4) were prepared and carefully investigated to understand the spin state transition driven by hole doping and further to reveal the effect of spin state transition on electronic conduction. It is shown that with increasing doping level, the transition temperature Ts for Co(3+) ions from low-spin (LS) to intermediate-spin (IS) reduces from 211.9 K for x = 0 to 190.5 K for x = 0.4. XPS and FT-IR spectra demonstrate that hole doping promoted this transition due to a larger Jahn-Teller distortion. Moreover, a thermal activation of spin disorder caused by thermal population of the spin states for Co ions has a great impact on the electrical transport of these perovskite samples. This work may shed light on the comprehension of spin transition in cobalt oxides through hole doping, which is promising for finding new strategies of enhancing electronic conduction, especially for energy and catalysis applications. PMID:27049837

  12. Oxides and oxide superconductors: Elastic and related properties

    SciTech Connect

    Lei, M.; Ledbetter, H.

    1991-08-01

    Using both measurements and modeling, the elastic and related properties of some oxides and oxide superconductors were studied. The polycrystal elastic constants were measured using a MHz-frequency pulse-echo method between 295 and 4 K and corrected to the void-free state by using a model for a composite material containing spherical particles. The elastic moduli of the high-T(c) superconductor Y1Ba2Cu3O7 (YBCO) were compared with that of oxides, especially the perovskites BaTiO3 and SrTiO3, which are crystal-structure building blocks for the YBCO superconductor. The bulk moduli were also calculated using a Born ionic model with two energy terms: electrostatic (Madelung) and ion-core-repulsion. The calculated bulk modulus of YBCO, 98 GPa, agrees well with measurement, 101 GPa. Based on monocrystal measurements combined with analysis-theory, elastic stiffnesses C(ij) for orthorhombic YBCO were estimated. The bulk modulus obtained from the estimated C(ij) by the Voigt-Reuss-Hill averaging method agrees with the monocrystal measurement. From the measured polycrystalline elastic constants, the Debye characteristic temperatures were calculated.

  13. Oxides and oxide superconductors: Elastic and related properties

    SciTech Connect

    Ming Lei.

    1991-01-01

    Using both measurements and modeling, the elastic and related properties of some oxides and oxide superconductors were studied. The polycrystal elastic constants were measured using a MHz-frequency pulse-echo method between 295 and 4 K and corrected to the void-free state by using a model for a composite material containing spherical particles. The elastic moduli of the high-{Tc} superconductor YBa{sub 2}Cu{sub 3}O{sub 7} (YBCO) were compared with that of oxides, especially the perovskites BaTiO{sub 3} and SrTiO{sub 3}, which are crystal-structure building blocks for the YBCO superconductor. The bulk moduli were also calculated using a Born ionic model with two energy terms: electrostatic (Madelung) and ion-core-repulsion. The calculated bulk modulus of YBCO, 98 GPa, agrees well with measurement, 101 GPa. Based on monocrystal measurements combined with analysis-theory, elastic stiffnesses C{sub ij} for orthorhombic YBCO were estimated. The bulk modulus obtained from the estimated C{sub ij} by the Voigt-Reuss-Hill averaging method agrees with the monocrystal measurement.

  14. Single-Layer Light-Emitting Diodes Using Organometal Halide Perovskite/Poly(ethylene oxide) Composite Thin Films.

    PubMed

    Li, Junqiang; Bade, Sri Ganesh R; Shan, Xin; Yu, Zhibin

    2015-09-16

    Organometal halide perovskite and poly(ethylene oxide) composite thin films are studied. Single-layer light-emitting diodes using the composite thin film sandwiched between indium tin oxide and indium-gallium eutectic alloy exhibit a low turn-on voltage and high brightness because of the ionic conductivity of the composite film and the formation of a p-i-n homojunction. PMID:26247326

  15. 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

  16. Rectifying characteristic in all-perovskite oxide film p-n junction with room temperature ferromagnetism

    NASA Astrophysics Data System (ADS)

    Zhang, Jun; Tanaka, Hidekazu; Kawai, Tomoji

    2002-06-01

    We fabricated an all-perovskite oxide p-n junction comprised of hole-doped (p-) manganite La0.9Ba0.1MnO3 and electron-doped (n-) titanate Sr0.99La0.01TiO3 films. The junction showed good rectifying properties at both room temperature and low temperature in a simple structure without inserting an insulating layer. By optimizing junction fabrication conditions, a thin La0.9Ba0.1MnO3 layer in the junction exhibited room temperature ferromagnetism and metallic conduction, which may be modulated by carrier injection from the n-type layer under an electric field. These results indicate that this p-n junction may be developed into functional, strongly correlated electronic devices able to work at room temperature.

  17. Metalloporphyrin-modified perovskite-type oxide for the electroreduction of oxygen

    NASA Astrophysics Data System (ADS)

    Nagai, Tsukasa; Yamazaki, Shin-ichi; Asahi, Masafumi; Siroma, Zyun; Fujiwara, Naoko; Ioroi, Tsutomu

    2015-10-01

    Perovskite-type oxide-carbon (Vulcan XC72) mixture (La0.6Sr0.4Mn0.6Fe0.4O3/C) was modified by a metalloporphyrin (cobalt octaethylporphyrin: Co-OEP) having two-electron O2 reduction activity, and its electrochemical reduction activity for O2 (ORR) was investigated in an alkaline solution by rotating ring disk electrode (RRDE) voltammetry. The Co-OEP/La0.6Sr0.4Mn0.6Fe0.4O3/C catalyst showed improved ORR activity, with a positive shift of the onset potential. In addition, a decreased ring current compared to Co-OEP/C suggested that the quasi-four-electron reduction of O2 was also enhanced. Further experiments showed that ORR activity was also enhanced by Co-OEP-modification of other types of carbon (Ketjenblack EC600JD, Denka Black) or perovskite-type oxide (La0.6Ca0.4Mn0.6Fe0.4O3, La0.8Sr0.2Co0.6Fe0.4O3). In the case of the addition of other porphyrin complexes (cobalt tetraphenylporphyrin (Co-TPP), iron octaethylporphyrin (Fe-OEP)) to a La0.6Sr0.4Mn0.6Fe0.4O3/C catalyst, the onset potential did not shift to the positive side due to the lower activity compared to Co-OEP.

  18. Partial conductivities in perovskites CaZr1- x Sc x O3-α ( x = 0.03-0.20) in an oxidation atmosphere

    NASA Astrophysics Data System (ADS)

    Gorelov, V. P.; Balakireva, V. B.; Kuz'min, A. V.

    2016-01-01

    Partial (ionic, proton, and hole) conductivities of oxides CaZr1- x Sc x O3-α( x = 0.03-0.20) with the perovskite structure in air atmosphere have been studied as functions of temperature in the range of 600-900°C and partial water-vapor pressure in the range of {P_{{H_2}O}}= 40-2500 Pa. The influence of the humidity of the atmosphere on the relative change in the concentration of oxygen vacancies as a function of temperature has been estimated.

  19. High-pressure stability relations, crystal structures, and physical properties of perovskite and post-perovskite of NaNiF{sub 3}

    SciTech Connect

    Shirako, Y.; Shi, Y.G.; Aimi, A.; Mori, D.; Kojitani, H.; Yamaura, K.; Inaguma, Y.; Akaogi, M.

    2012-07-15

    NaNiF{sub 3} perovskite was found to transform to post-perovskite at 16-18 GPa and 1273-1473 K. The equilibrium transition boundary is expressed as P (GPa)=-2.0+0.014 Multiplication-Sign T (K). Structure refinements indicated that NaNiF{sub 3} perovskite and post-perovskite have almost regular NiF{sub 6} octahedra consistent with absence of the first-order Jahn-Teller active ions. Both NaNiF{sub 3} perovskite and post-perovskite are insulators. The perovskite underwent a canted antiferromagnetic transition at 156 K, and the post-perovskite antiferromagnetic transition at 22 K. Magnetic exchange interaction of NaNiF{sub 3} post-perovskite is smaller than that of perovskite, reflecting larger distortion of Ni-F-Ni network and lower dimension of octahedral arrangement in post-perovskite than those in perovskite. - Graphical abstract: Perovskite-post-perovskite transition in NaNiF{sub 3} at high pressure Highlights: Black-Right-Pointing-Pointer NaNiF{sub 3} perovskite (Pv) transforms to post-perovskite (pPv) at 16 GPa and 1300 K. Black-Right-Pointing-Pointer The equilibrium transition boundary is expressed as P (GPa)=-2.0+0.014 T (K). Black-Right-Pointing-Pointer Antiferromagnetic transition occurs at 156 K in Pv and 22 K in pPv.

  20. A combinatorial chemistry method for fast screening of perovskite-based NO oxidation catalyst.

    PubMed

    Yoon, Dal Young; Lim, Eunho; Kim, Young Jin; Cho, Byong K; Nam, In-Sik; Choung, Jin Woo; Yoo, Seungbeom

    2014-11-10

    A fast parallel screening method based on combinatorial chemistry (combichem) has been developed and applied in the screening tests of perovskite-based oxide (PBO) catalysts for NO oxidation to hit a promising PBO formulation for the oxidation of NO to NO2. This new method involves three consecutive steps: oxidation of NO to NO2 over a PBO catalyst, adsorption of NOx onto the PBO and K2O/Al2O3, and colorimetric assay of the NOx adsorbed thereon. The combichem experimental data have been used for determining the oxidation activity of NO over PBO catalysts as well as three critical parameters, such as the adsorption efficiency of K2O/Al2O3 for NO2 (α) and NO (β), and the time-average fraction of NO included in the NOx feed stream (ξ). The results demonstrated that the amounts of NO2 produced over PBO catalysts by the combichem method under transient conditions correlate well with those from a conventional packed-bed reactor under steady-state conditions. Among the PBO formulations examined, La0.5Ag0.5MnO3 has been identified as the best chemical formulation for oxidation of NO to NO2 by the present combichem method and also confirmed by the conventional packed-bed reactor tests. The superior efficiency of the combichem method for high-throughput catalyst screening test validated in this study is particularly suitable for saving the time and resources required in developing a new formulation of PBO catalyst whose chemical composition may have an enormous number of possible variations. PMID:25321326

  1. Voltage-induced Metal-Insulator Transitions in Perovskite Oxide Thin Films Doped with Strongly Correlelated Electrons

    NASA Astrophysics Data System (ADS)

    Wang, Yudi; Gil Kim, Soo; Chen, I.-Wei

    2007-03-01

    We have observed a reversible metal-insulator transition in perovskite oxide thin films that can be controlled by charge trapping pumped by a bipolar voltage bias. In the as-fabricated state, the thin film is metallic with a very low resistance comparable to that of the metallic bottom electrode, showing decreasing resistance with decreasing temperature. This metallic state switches to a high-resistance state after applying a voltage bias: such state is non-ohmic showing a negative temperature dependence of resistance. Switching at essentially the same voltage bias was observed down to 2K. The metal-insulator transition is attributed to charge trapping that disorders the energy of correlated electron states in the conduction band. By increasing the amount of charge trapped, which increases the disorder relative to the band width, increasingly more insulating states with a stronger temperature dependence of resistivity are accessed. This metal-insulator transition provides a platform to engineer new nonvolatile memory that does not require heat (as in phase transition) or dielectric breakdown (as in most other oxide resistance devices).

  2. Effect of the filtration of PbI2 solution for zinc oxide nanowire based perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Mijanur Rahman, Md.; Uekawa, Naofumi; Shiba, Fumiyuki; Okawa, Yusuke; Sakai, Masatoshi; Yamamoto, Kazunuki; Kudo, Kazuhiro; Konishi, Takehisa

    2016-01-01

    Zinc oxide (ZnO) nanowires (NWs) are grown on fluorine-doped tin oxide (FTO) glass substrates via a simple reactive evaporation method without the presence of any catalysts or additives. The ZnO NWs show high crystallinity and preferential elongation along the c-axis of the hexagonal wurtzite crystal structure. The highly crystalline NWs as electron transporting layer have been used to fabricate the CH3NH3PbI3 perovskite solar cells and their photovoltaic performance were investigated. In this report, we studied the effect of filtration of PbI2-solution on surface morphology of CH3NH3PbI3 layer. Spin-coating of the filtered PbI2-solution leads to a better crystallization and relatively homogenous coverage of the CH3NH3PbI3 film, resulting in an enhancement of the solar cell efficiency compared to the cell fabricated using non-filtrated PbI2-solution. By synthesizing the CH3NH3PbI3 film using filtrated PbI2-solution, we achieved the best power conversion efficiency of 4.8% with a current density of 7.6 mA cm-2, the open circuit voltage of 0.79 V and fill factor of 0.63.

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

    NASA Astrophysics Data System (ADS)

    Bennett, Joseph W.

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

  4. Stability of tetravalent actinides in perovskites

    SciTech Connect

    Williams, C.W.; Morss, L.R.; Choi, I.K.

    1983-01-01

    This paper reports the first determination of the enthalpy of formation of a complex actinide(IV) oxide: ..delta..H/sup 0//sub f/ (BaUO/sub 3/, s, 298 K) = -1690 +- 10 kJ mol/sup -1/. The preparation and properties of this and other actinide(IV) complex oxides are described and are compared with other perovskites BaMO/sub 3/. The relative stabilities of tetravalent and hexavalent uranium in various environments are compared in terms of the oxidation-reduction behavior of uranium in geological nuclear waste storage media; in perovskite, uranium(IV) is very unstable in comparison with uranium(VI).

  5. Flexible high power-per-weight perovskite solar cells with chromium oxide-metal contacts for improved stability in air.

    PubMed

    Kaltenbrunner, Martin; Adam, Getachew; Głowacki, Eric Daniel; Drack, Michael; Schwödiauer, Reinhard; Leonat, Lucia; Apaydin, Dogukan Hazar; Groiss, Heiko; Scharber, Markus Clark; White, Matthew Schuette; Sariciftci, Niyazi Serdar; Bauer, Siegfried

    2015-10-01

    Photovoltaic technology requires light-absorbing materials that are highly efficient, lightweight, low cost and stable during operation. Organolead halide perovskites constitute a highly promising class of materials, but suffer limited stability under ambient conditions without heavy and costly encapsulation. Here, we report ultrathin (3 μm), highly flexible perovskite solar cells with stabilized 12% efficiency and a power-per-weight as high as 23 W g(-1). To facilitate air-stable operation, we introduce a chromium oxide-chromium interlayer that effectively protects the metal top contacts from reactions with the perovskite. The use of a transparent polymer electrode treated with dimethylsulphoxide as the bottom layer allows the deposition-from solution at low temperature-of pinhole-free perovskite films at high yield on arbitrary substrates, including thin plastic foils. These ultra-lightweight solar cells are successfully used to power aviation models. Potential future applications include unmanned aerial vehicles-from airplanes to quadcopters and weather balloons-for environmental and industrial monitoring, rescue and emergency response, and tactical security applications. PMID:26301766

  6. Flexible high power-per-weight perovskite solar cells with chromium oxide-metal contacts for improved stability in air

    NASA Astrophysics Data System (ADS)

    Kaltenbrunner, Martin; Adam, Getachew; Głowacki, Eric Daniel; Drack, Michael; Schwödiauer, Reinhard; Leonat, Lucia; Apaydin, Dogukan Hazar; Groiss, Heiko; Scharber, Markus Clark; White, Matthew Schuette; Sariciftci, Niyazi Serdar; Bauer, Siegfried

    2015-10-01

    Photovoltaic technology requires light-absorbing materials that are highly efficient, lightweight, low cost and stable during operation. Organolead halide perovskites constitute a highly promising class of materials, but suffer limited stability under ambient conditions without heavy and costly encapsulation. Here, we report ultrathin (3 μm), highly flexible perovskite solar cells with stabilized 12% efficiency and a power-per-weight as high as 23 W g-1. To facilitate air-stable operation, we introduce a chromium oxide-chromium interlayer that effectively protects the metal top contacts from reactions with the perovskite. The use of a transparent polymer electrode treated with dimethylsulphoxide as the bottom layer allows the deposition--from solution at low temperature--of pinhole-free perovskite films at high yield on arbitrary substrates, including thin plastic foils. These ultra-lightweight solar cells are successfully used to power aviation models. Potential future applications include unmanned aerial vehicles--from airplanes to quadcopters and weather balloons--for environmental and industrial monitoring, rescue and emergency response, and tactical security applications.

  7. Electrochemical properties of mixed conducting (La,M)(CoFe) oxide perovskites (M=3DSr, Ca, and Ba)

    SciTech Connect

    Stevenson, J.W.; Armstrong, T.R.; Bates, J.L.

    1996-04-01

    Electrical properties and oxygen permeation properties of solid mixed-conducting electrolytes (La,M)(CoFe) oxide perovskites (M=3DSr, Ca, and Ba) have been characterized. These materials are potentially useful as passive membranes to separate high purity oxygen from air and as the cathode in a fuel cell. Dilatometric linear expansion measurements were performed as a function of temperature and oxygen partial pressure to evaluate the stability.

  8. 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.

  9. Effect of relative humidity on crystal growth, device performance and hysteresis in planar heterojunction perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Gangishetty, Mahesh K.; Scott, Robert W. J.; Kelly, Timothy L.

    2016-03-01

    Due to the hygroscopic nature of organolead halide perovskites, humidity is one of the most important factors affecting the efficiency and longevity of perovskite solar cells. Although humidity has a long term detrimental effect on device performance, it also plays a key role during the initial growth of perovskite crystals. Here we demonstrate that atmospheric relative humidity (RH) plays a key role during the formation of perovskite thin films via the sequential deposition technique. Our results indicate that the RH has a substantial impact on the crystallization process, and hence on device performance. SEM and pXRD analysis show an increase in crystallite size with increasing humidity. At low RH, the formation of small cubic crystallites with large gaps between them is observed. The presence of these voids adversely affects device performance and leads to substantial hysteresis in the device. At higher RH, the perovskite crystals are larger in size, with better connectivity between the crystallites. This produced efficient planar heterojunction solar cells with low hysteresis. By careful control of the RH during the cell fabrication process, efficiencies of up to 12.2% are reached using P3HT as the hole-transport material.Due to the hygroscopic nature of organolead halide perovskites, humidity is one of the most important factors affecting the efficiency and longevity of perovskite solar cells. Although humidity has a long term detrimental effect on device performance, it also plays a key role during the initial growth of perovskite crystals. Here we demonstrate that atmospheric relative humidity (RH) plays a key role during the formation of perovskite thin films via the sequential deposition technique. Our results indicate that the RH has a substantial impact on the crystallization process, and hence on device performance. SEM and pXRD analysis show an increase in crystallite size with increasing humidity. At low RH, the formation of small cubic crystallites

  10. Solvothermal synthesis of perovskites and pyrochlores: crystallisation of functional oxides under mild conditions.

    PubMed

    Modeshia, Deena R; Walton, Richard I

    2010-11-01

    In this critical review we consider the large literature that has accumulated in the past 5-10 years concerning solution-mediated crystallisation of complex oxide materials using hydrothermal, or more generally solvothermal, reaction conditions. The aim is to show how the synthesis of dense, mixed-metal oxide materials, usually prepared using the high temperatures associated with solid-chemistry, is perfectly feasible from solution in one step reactions, typically at temperatures as low as 200 °C, and that important families of oxide materials have now been reported to crystallise using such synthetic approaches. We will focus on two common structures seen in oxide chemistry, ABO(3) perovskites and A(2)B(2)O(6)O' pyrochlores, and include a systematic survey of the variety of chemical elements now included in these two prototypical structure types, from transition metals, in families of materials that include titanates, niobates, manganites and ferrites, to main-group elements in stannates, plumbates and bismuthates. The significant advantages of solution-mediated crystallisation are well illustrated by the recent literature: examples are provided of elegant control of crystal form from the nanometre to the micron length scale to give thin films, anisotropic crystal morphologies, or hierarchical structures of materials with properties desirable for many important contemporary applications. In addition, new metastable materials have been reported, not stable once high temperatures and pressures are applied and hence not amenable using conventional synthesis. We critically discuss the possible control offered by solvothermal synthesis from crystal chemistry to crystal form and how the discovery of new materials may be achieved. Computer simulation, combinatorial synthesis approaches and in situ methods to follow crystallisation will be vital in providing the predictability in synthesis that is needed for rational design of new materials (232 references). PMID

  11. Atomic-Scale Chemical Imaging of Composition and Bonding at Perovskite Oxide Interfaces

    NASA Astrophysics Data System (ADS)

    Fitting Kourkoutis, L.

    2010-03-01

    Scanning transmission electron microscopy (STEM) in combination with electron energy loss spectroscopy (EELS) has proven to be a powerful technique to study buried perovskite oxide heterointerfaces. With the recent addition of 3^rd order and now 5^th order aberration correction, which provides a factor of 100x increase in signal over an uncorrected system, we are now able to record 2D maps of composition and bonding of oxide interfaces at atomic resolution [1]. Here, we present studies of the microscopic structure of oxide/oxide multilayers and heterostructures by STEM in combination with EELS and its effect on the properties of the film. Using atomic-resolution spectroscopic imaging we show that the degradation of the magnetic and transport properties of La0.7Sr0.3MnO3/SrTiO3 multilayers correlates with atomic intermixing at the interfaces and the presence of extended defects in the La0.7Sr0.3MnO3 layers. When these defects are eliminated, metallic ferromagnetism at room temperature can be stabilized in 5 unit cell thick manganite layers, almost 40% thinner than the previously reported critical thickness of 3-5 nm for sustaining metallic ferromagnetism below Tc in La0.7Sr0.3MnO3 thin films grown on SrTiO3.[4pt] [1] D.A. Muller, L. Fitting Kourkoutis, M. Murfitt, J.H. Song, H.Y. Hwang, J. Silcox, N. Dellby, O.L. Krivanek, Science 319, 1073-1076 (2008).

  12. Conductive Perovskite-type Metal Oxide Thin Films Prepared by Chemical Solution Deposition Technique

    NASA Astrophysics Data System (ADS)

    Sasajima, K.; Uchida, H.

    2011-10-01

    Metal oxide electrode have been widely developed for high-performance electric device because they possess some attractive characteristic such as thermal/chemical stabilities and change compensation for oxygen vacancies in interconnected dielectric layers, etc., which is often hardly achieved by convention metal electrodes. As almost all metal oxide electrodes were usually fabricated by some vapour deposition techniques which require large-scale equipments, power, resources and costs, film deposition via solution technique would be worthy for familiarizing the metal oxide electrodes. In this research, thin films of conductive perovskite-type oxides, (La,Sr)CoO3 [LSCO], were fabricated by chemical solution deposition technique. The precursor solution for LSCO was prepared using metal nitrate, acetates, and iso-propoxide and 2-methoxyethanol. The solution was spin-coated on substrates, followed by drying, pyrolysis and RTA-treatment for crystallization at 500-750°C, for 5 min in air. These processes were repeated to obtain desired film thickness. (100)Si and (100)SrTiO3 were used as substrate. XRD analysis indicated that both of LSCO films fabricated on (100)SrTiO3 and (100)Si substrates were crystallized at and above 600°C. The films on (100)SrTiO3 had preferential crystal orientation of (100)LSCO normal to the substrate surface, while random crystal orientation was confirmed for the films on (100)Si. Electrical resistivity of the both films fabricated at 700°C were 6.09 × 10-5 Ω cm and 1.12 × 10-4 Ω cm, respectively, which is almost same as the LSCO films fabricated by conventional vapour deposition technique.

  13. Perovskite LaRhO{sub 3} as a p-type active layer in oxide photovoltaics

    SciTech Connect

    Nakamura, Masao Krockenberger, Yoshiharu; Fujioka, Jun; Kawasaki, Masashi; Tokura, Yoshinori

    2015-02-16

    Perovskite-type transition-metal oxides have a wide variety of physical properties and triggered intensive research on functional devices in the form of heteroepitaxial junctions. However, there is a missing component that is a p-type conventional band semiconductor. LaRhO{sub 3} (LRO) is one of very few promising candidates having its bandgap between filled t{sub 2g} and empty e{sub g} of Rh in low-spin state, but there has been no report on the synthesis of large-size single crystals or thin films. Here, we report on the junction properties of single-crystalline thin films of LRO grown on (110) oriented Nb-doped SrTiO{sub 3} substrates. The external quantum efficiency of the photo-electron conversion exceeds 1% in the visible-light region due to the wide depletion layer and long diffusion length of minority carriers in LRO. Clear indication of p-type band semiconducting character in a perovskite oxide of LRO will pave a way to explore oxide electronics of perovskite heterostructures.

  14. On the behavior of Bronsted-Evans-Polanyi Relations for Transition Metal Oxides

    SciTech Connect

    Vojvodic, Aleksandra

    2011-08-22

    Versatile Broensted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strong intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a 'cyclic' behavior in the transition state characteristics upon change of the active transition metal of the oxide.

  15. On the behavior of Brønsted-Evans-Polanyi relations for transition metal oxides.

    PubMed

    Vojvodic, A; Calle-Vallejo, F; Guo, W; Wang, S; Toftelund, A; Studt, F; Martínez, J I; Shen, J; Man, I C; Rossmeisl, J; Bligaard, T; Noørskov, J K; Abild-Pedersen, F

    2011-06-28

    Versatile Brønsted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site, and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strong intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a "cyclic" behavior in the transition state characteristics upon change of the active transition metal of the oxide. PMID:21721645

  16. Oxygen transport in perovskite-type solid oxide fuel cell materials: insights from quantum mechanics.

    PubMed

    Muñoz-García, Ana B; Ritzmann, Andrew M; Pavone, Michele; Keith, John A; Carter, Emily A

    2014-11-18

    CONSPECTUS: Global advances in industrialization are precipitating increasingly rapid consumption of fossil fuel resources and heightened levels of atmospheric CO2. World sustainability requires viable sources of renewable energy and its efficient use. First-principles quantum mechanics (QM) studies can help guide developments in energy technologies by characterizing complex material properties and predicting reaction mechanisms at the atomic scale. QM can provide unbiased, qualitative guidelines for experimentally tailoring materials for energy applications. This Account primarily reviews our recent QM studies of electrode materials for solid oxide fuel cells (SOFCs), a promising technology for clean, efficient power generation. SOFCs presently must operate at very high temperatures to allow transport of oxygen ions and electrons through solid-state electrolytes and electrodes. High temperatures, however, engender slow startup times and accelerate material degradation. SOFC technologies need cathode and anode materials that function well at lower temperatures, which have been realized with mixed ion-electron conductor (MIEC) materials. Unfortunately, the complexity of MIECs has inhibited the rational tailoring of improved SOFC materials. Here, we gather theoretically obtained insights into oxygen ion conductivity in two classes of perovskite-type materials for SOFC applications: the conventional La1-xSrxMO3 family (M = Cr, Mn, Fe, Co) and the new, promising class of Sr2Fe2-xMoxO6 materials. Using density functional theory + U (DFT+U) with U-J values obtained from ab initio theory, we have characterized the accompanying electronic structures for the two processes that govern ionic diffusion in these materials: (i) oxygen vacancy formation and (ii) vacancy-mediated oxygen migration. We show how the corresponding macroscopic oxygen diffusion coefficient can be accurately obtained in terms of microscopic quantities calculated with first-principles QM. We find that the

  17. Perovskite Sr-Doped LaCrO3 as a New p-Type Transparent Conducting Oxide.

    PubMed

    Zhang, Kelvin H L; Du, Yingge; Papadogianni, Alexandra; Bierwagen, Oliver; Sallis, Shawn; Piper, Louis F J; Bowden, Mark E; Shutthanandan, Vaithiyalingam; Sushko, Peter V; Chambers, Scott A

    2015-09-16

    Epitaxial La1-x Srx CrO3 deposited on SrTiO3 (001) is shown to be a p-type transparent conducting oxide with competitive figures of merit and a cubic perovskite structure, facilitating integration into oxide electronics. Holes in the Cr 3d t2g bands play a critical role in enhancing p-type conductivity, while transparency to visible light is maintained because low-lying d-d transitions arising from hole doping are dipole forbidden. PMID:26248327

  18. Dielectric Relaxation of Rare Earth Ordered Double Perovskite Oxide Ba2ErTaO6

    NASA Astrophysics Data System (ADS)

    Mukherjee, Rajesh; Dutta, Alo; Sinha, T. P.

    2016-01-01

    The electrical properties of rare-earth based ordered double perovskite oxide barium erbium tantalate, Ba2ErTaO6 synthesized by solid-state reaction method are investigated. The x-ray diffraction pattern of the sample shows cubic Fm3m phase at room temperature with ordering of the B cations. Fourier transform infrared spectrum shows two primary phonon modes of the sample at around 350 cm-1 and 600 cm-1. The dielectric relaxation of the sample is investigated in the frequency range from 50 Hz to 1.1 MHz and in the temperature range from 303 K to 673 K. Electric modulus and electrical impedance data are fitted to the Cole-Cole equation. The frequency dependent conductivity spectra follow the power law. Summerfield scaling is used to explain the conduction mechanism. The scaling behavior of the imaginary part of the impedance spectra suggests that the relaxation shows the same mechanism at various temperatures. The complex impedance plane plots show that the relaxation (conduction) mechanism in this material is mainly due to grain boundary effect for all temperatures and grain effect for low temperature. The relaxation frequency corresponding to dielectric loss is found to obey Arrhenius law with activation energy of 0.50 eV. The values of activation energy indicate that the dielectric relaxation and the conduction mechanism are due to adiabatic small polaronic hole hopping mechanism.

  19. Perovskite Solar Cells Based on Low-Temperature Processed Indium Oxide Electron Selective Layers.

    PubMed

    Qin, Minchao; Ma, Junjie; Ke, Weijun; Qin, Pingli; Lei, Hongwei; Tao, Hong; Zheng, Xiaolu; Xiong, Liangbin; Liu, Qin; Chen, Zhiliang; Lu, Junzheng; Yang, Guang; Fang, Guojia

    2016-04-01

    Indium oxide (In2O3) as a promising n-type semiconductor material has been widely employed in optoelectronic applications. In this work, we applied low-temperature solution-processed In2O3 nanocrystalline film as an electron selective layer (ESL) in perovskite solar cells (PSCs) for the first time. By taking advantages of good optical and electrical properties of In2O3 such as high mobility, wide band gap, and high transmittance, we obtained In2O3-based PSCs with a good efficiency exceeding 13% after optimizing the concentration of the precursor solution and the annealing temperature. Furthermore, to enhance the performance of the In2O3-based PSCs, a phenyl-C61-butyric acid methyl ester (PCBM) layer was introduced to modify the surface of the In2O3 film. The PCBM film could fill up the pinholes or cracks along In2O3 grain boundaries to passivate the defects and make the ESL extremely compact and uniform, which is conducive to suppressing the charge recombination. As a result, the efficiency of the In2O3-based PSC was improved to 14.83% accompanied with VOC, JSC, and FF being 1.08 V, 20.06 mA cm(-2), and 0.685, respectively. PMID:26996215

  20. Dielectric relaxation in a new double perovskite oxide Ho 2MgZrO 6

    NASA Astrophysics Data System (ADS)

    Mahato, Dev K.; Dutta, Alo; Sinha, T. P.

    2012-01-01

    A new double perovskite oxide holmium magnesium zirconate Ho 2MgZrO 6 (HMZ) was prepared by solid state reaction technique. The crystal structure has been determined by powder X-ray diffraction which shows monoclinic phase at room temperature with cell parameters a = 9.3028 ± 0.0030 Å, b = 5.2293 ± 0.0008 Å, c = 4.4009 ± 0.0009 Å, β = 103.3746 ± 0.0166°. An analysis of complex permittivity with frequency was carried out assuming a distribution of relaxation times. The frequency dependent electrical data are analyzed in the framework of conductivity and electric modulus formalisms. At the high temperature range, conductivity data satisfy the variable range hopping (VRH) model. In this regime, the conductivity of sample obeys Mott's T1/4 law, characteristic of VRH. High temperature data indicates the formation of thermally activated small polarons. The scaling behaviour of imaginary part of electric modulus suggests that the relaxation describes the same mechanism at various temperatures.

  1. Thickness dependence of exchange coupling in (111)-oriented perovskite oxide superlattices

    NASA Astrophysics Data System (ADS)

    Jia, Yue; Chopdekar, Rajesh V.; Arenholz, Elke; Liu, Zhiqi; Biegalski, Michael D.; Porter, Zachary D.; Mehta, Apurva; Takamura, Yayoi

    2016-03-01

    Epitaxial L a0.7S r0.3Mn O3(LSMO )/L a0.7S r0.3Fe O3 (LSFO) superlattices on (111)-oriented SrTi O3 substrates with sublayer thicknesses ranging from 3 to 60 unit cells (u.c.) were synthesized and characterized. Detailed analysis of their structural, electronic, and magnetic properties were performed to explore the effect of sublayer thickness on the magnetic structure and exchange coupling at (111)-oriented perovskite oxide interfaces. In the ultrathin limit (3-6 u.c.), we find that the antiferromagnetic (AF) properties of the LSFO sublayers are preserved with an out-of-plane canting of the AF spin axis, while the ferromagnetic (FM) properties of the LSMO sublayers are significantly depressed. For thicker LSFO layers (>9 u.c.), the out-of-plane canting of the AF spin axis is only present in superlattices with thick LSMO sublayers. As a result, exchange coupling in the form of spin-flop coupling exists only in superlattices which display both robust ferromagnetism and out-of-plane canting of the AF spin axis.

  2. Effects of carbon on oxygen reduction and evolution reactions of gas-diffusion air electrodes based on perovskite-type oxides

    NASA Astrophysics Data System (ADS)

    Nishio, Koji; Molla, Sergio; Okugaki, Tomohiko; Nakanishi, Shinji; Nitta, Iwao; Kotani, Yukinari

    2015-12-01

    Electrochemical properties of three perovskite oxides with different B-site elements, LaMnO3, La0.6Sr0.4FeO3 and LaNiO3, are examined with and without carbon using gas-diffusion electrodes, in comparison with our previous results on La0.5Sr0.5CoO3. Cyclic voltammetry studies reveal very low oxygen reduction current density of carbon-free perovskite oxides, indicating their poor catalytic activity on oxygen reduction reactions. By mixing carbon with perovskite oxides, the oxygen reduction current density is increased by about two orders. The results are consistent with the peroxide pathway mechanism in which the perovskite oxide is highly active on either electrochemical reduction or chemical decomposition. Electrochemical properties of a three-layered gas diffusion electrode demonstrate the peroxide pathway mechanism works even the perovskite oxide and the carbon exist in separate layers. Oxygen evolution reactions are prominently dependent on the oxide species and also on an addition of carbon. The electrode based on carbon-free LaNiO3 or La0.5Sr0.5CoO3 show moderate oxygen evolution activity, and the activity is further enhanced by an addition of carbon, while LaMnO3 and La0.6Sr0.4FeO3 show poor activity even with an addition of carbon.

  3. Effect of relative humidity on crystal growth, device performance and hysteresis in planar heterojunction perovskite solar cells.

    PubMed

    Gangishetty, Mahesh K; Scott, Robert W J; Kelly, Timothy L

    2016-03-17

    Due to the hygroscopic nature of organolead halide perovskites, humidity is one of the most important factors affecting the efficiency and longevity of perovskite solar cells. Although humidity has a long term detrimental effect on device performance, it also plays a key role during the initial growth of perovskite crystals. Here we demonstrate that atmospheric relative humidity (RH) plays a key role during the formation of perovskite thin films via the sequential deposition technique. Our results indicate that the RH has a substantial impact on the crystallization process, and hence on device performance. SEM and pXRD analysis show an increase in crystallite size with increasing humidity. At low RH, the formation of small cubic crystallites with large gaps between them is observed. The presence of these voids adversely affects device performance and leads to substantial hysteresis in the device. At higher RH, the perovskite crystals are larger in size, with better connectivity between the crystallites. This produced efficient planar heterojunction solar cells with low hysteresis. By careful control of the RH during the cell fabrication process, efficiencies of up to 12.2% are reached using P3HT as the hole-transport material. PMID:26411485

  4. Green, Orange, and Magenta Luminescence in Strontium Stannates with Perovskite-Related Structures

    NASA Astrophysics Data System (ADS)

    Ueda, Kazushige; Yamashita, Takahiro; Nakayashiki, Kensuke; Goto, Katsuhiko; Maeda, Tsuyoshi; Furui, Koji; Ozaki, Koichiro; Nakachi, Yutaka; Nakamura, Satoshi; Fujisawa, Masaru; Miyazaki, Takato

    2006-09-01

    Intense green, orange or magenta luminescence was observed in rare-earth doped alkaline earth (Ca, Sr, and Ba) stannates, particularly strontium stannates with perovskite-related structures. Tb-Mg codoped SrSnO3 showed sharp emission lines corresponding to Tb ions as a green phosphor. Sm doped Sr3Sn2O7 exhibited sharp pairs of emission lines corresponding to Sm ions as an orange phosphor. Eu-Ti codoped Sr2SnO4 as a magenta phosphor showed sharp red luminescent lines corresponding to Eu ions as well as a broad blue emission band corresponding to Ti-related complexes. It was suggested that codoping and/or layered structures in these phosphors are closely related to the increase in luminescence intensity from these rare-earth ions.

  5. A perovskite oxide with high conductivities in both air and reducing atmosphere for use as electrode for solid oxide fuel cells.

    PubMed

    Lan, Rong; Cowin, Peter I; Sengodan, Sivaprakash; Tao, Shanwen

    2016-01-01

    Electrode materials which exhibit high conductivities in both oxidising and reducing atmospheres are in high demand for solid oxide fuel cells (SOFCs) and solid oxide electrolytic cells (SOECs). In this paper, we investigated Cu-doped SrFe0.9Nb0.1O3-δ finding that the primitive perovskite oxide SrFe0.8Cu0.1Nb0.1O3-δ (SFCN) exhibits a conductivity of 63 Scm(-1)and 60 Scm(-1) at 415 °C in air and 5%H2/Ar respectively. It is believed that the high conductivity in 5%H2/Ar is related to the exsolved Fe (or FeCu alloy) on exposure to a reducing atmosphere. To the best of our knowledge, the conductivity of SrFe0.8Cu0.1Nb0.1O3-δ in a reducing atmosphere is the highest of all reported oxides which also exhibit a high conductivity in air. Fuel cell performance using SrFe0.8Cu0.1Nb0.1O3-δ as the anode, (Y2O3)0.08(ZrO2)0.92 as the electrolyte and La0.8Sr0.2FeO3-δ as the cathode achieved a power density of 423 mWcm(-2) at 700 °C indicating that SFCN is a promising anode for SOFCs. PMID:27545200

  6. A perovskite oxide with high conductivities in both air and reducing atmosphere for use as electrode for solid oxide fuel cells

    PubMed Central

    Lan, Rong; Cowin, Peter I.; Sengodan, Sivaprakash; Tao, Shanwen

    2016-01-01

    Electrode materials which exhibit high conductivities in both oxidising and reducing atmospheres are in high demand for solid oxide fuel cells (SOFCs) and solid oxide electrolytic cells (SOECs). In this paper, we investigated Cu-doped SrFe0.9Nb0.1O3−δ finding that the primitive perovskite oxide SrFe0.8Cu0.1Nb0.1O3−δ (SFCN) exhibits a conductivity of 63 Scm−1and 60 Scm−1 at 415 °C in air and 5%H2/Ar respectively. It is believed that the high conductivity in 5%H2/Ar is related to the exsolved Fe (or FeCu alloy) on exposure to a reducing atmosphere. To the best of our knowledge, the conductivity of SrFe0.8Cu0.1Nb0.1O3−δ in a reducing atmosphere is the highest of all reported oxides which also exhibit a high conductivity in air. Fuel cell performance using SrFe0.8Cu0.1Nb0.1O3−δ as the anode, (Y2O3)0.08(ZrO2)0.92 as the electrolyte and La0.8Sr0.2FeO3−δ as the cathode achieved a power density of 423 mWcm−2 at 700 °C indicating that SFCN is a promising anode for SOFCs. PMID:27545200

  7. Oxygen reduction and evolution reactions of air electrodes using a perovskite oxide as an electrocatalyst

    NASA Astrophysics Data System (ADS)

    Nishio, Koji; Molla, Sergio; Okugaki, Tomohiko; Nakanishi, Shinji; Nitta, Iwao; Kotani, Yukinari

    2015-03-01

    The oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) of air electrodes consisting of La0.5Sr0.5CoO3 and/or carbon in the electrocatalyst layer are studied by using two types of gas diffusion electrodes. Cyclic voltammetry and square wave voltammetry studies reveal very low ORR activity of carbon-free perovskite and remarkably enhanced ORR of perovskite-carbon composites. The ORR current density at -0.5 V vs. Hg/HgO is higher than 200 mA cm-2 in a wide range of perovskite-carbon composition, suggesting good peroxide reducing capability of the perovskite. The ORR mechanisms of perovskite-carbon composites are consistent with the 2+2-electron mechanisms. The ORR and OER properties of perovskite-carbon composite electrodes are significantly influenced by the carbon species. The electrode exhibits a higher ORR current density, but inferior cycling performances when a carbon material with a higher specific surface area is used, and vice versa. Under a current density of 20 mA cm-2 and ORR and OER durations of 30 min, a gas diffusion type electrode consists of La0.5Sr0.5CoO3 and a low surface area carbon are capable of more than 150 cycles.

  8. Graphene oxide/PEDOT:PSS composite hole transport layer for efficient and stable planar heterojunction perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Lee, Da-Young; Na, Seok-In; Kim, Seok-Soon

    2016-01-01

    We investigated a graphene oxide (GO)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) composite as a promising candidate for the practical application of a 2-D carbonaceous hole transport layer (HTL) to planar heterojunction perovskite solar cells (PeSCs) consisting of a transparent electrode/HTL/perovskite/fullerene/metal electrode. Both the insulating properties of GO and the non-uniform coating of the transparent electrode with GO cause the poor morphology of perovskite induced low power conversion efficiency (PCE) of 6.4%. On the other hand, PeSCs with a GO/PEDOT:PSS composite HTL, exhibited a higher PCE of 9.7% than that of a device fabricated with conventional PEDOT:PSS showing a PCE of 8.2%. The higher performance is attributed to the decreased series resistance (RS) and increased shunt resistance (RSh). The well-matched work-function between GO (4.9 eV) and PEDOT:PSS (5.1 eV) probably results in more efficient charge transport and an overall decrease in RS. The existence of GO with a large bandgap of ~3.6 eV might induce the effective blocking of electrons, leading to an increase of RSh. Moreover, improvement in the long-term stability under atmospheric conditions was observed.

  9. Cobalt based layered perovskites as cathode material for intermediate temperature Solid Oxide Fuel Cells: A brief review

    NASA Astrophysics Data System (ADS)

    Pelosato, Renato; Cordaro, Giulio; Stucchi, Davide; Cristiani, Cinzia; Dotelli, Giovanni

    2015-12-01

    Nowadays, the cathode is the most studied component in Intermediate Temperature-Solid Oxide Fuel Cells (IT-SOFCs). Decreasing SOFCs operating temperature implies slow oxygen reduction kinetics and large polarization losses. Double perovskites with general formula REBaCo2O5+δ are promising mixed ionic-electronic conductors, offering a remarkable enhancement of the oxygen diffusivity and surface exchange respect to disordered perovskites. In this review, more than 250 compositions investigated in the literature were analyzed. The evaluation was performed in terms of electrical conductivity, Area Specific Resistance (ASR), chemical compatibility with electrolytes and Thermal Expansion Coefficient (TEC). The most promising materials have been identified as those bearing the mid-sized rare earths (Pr, Nd, Sm, Gd). Doping strategies have been analyzed: Sr doping on A site promotes higher electrical conductivity, but worsen ASR and TECs; B-site doping (Fe, Ni, Mn) helps lowering TECs, but is detrimental for the electrochemical properties. A promising boost of the electrochemical activity is obtained by simply introducing a slight Ba under-stoichiometry. Still, the high sensitivity of the electrochemical properties against slight changes in the stoichiometry hamper a conclusive comparison of all the investigated compounds. Opportunities for an improvement of double perovskite cathodes performance is tentatively foreseen in combining together the diverse effective doping strategies.

  10. Ultrafast Dynamics of Hole Injection and Recombination in Organometal Halide Perovskite Using Nickel Oxide as p-Type Contact Electrode.

    PubMed

    Corani, Alice; Li, Ming-Hsien; Shen, Po-Shen; Chen, Peter; Guo, Tzung-Fang; El Nahhas, Amal; Zheng, Kaibo; Yartsev, Arkady; Sundström, Villy; Ponseca, Carlito S

    2016-04-01

    There is a mounting effort to use nickel oxide (NiO) as p-type selective electrode for organometal halide perovskite-based solar cells. Recently, an overall power conversion efficiency using this hole acceptor has reached 18%. However, ultrafast spectroscopic investigations on the mechanism of charge injection as well as recombination dynamics have yet to be studied and understood. Using time-resolved terahertz spectroscopy, we show that hole transfer is complete on the subpicosecond time scale, driven by the favorable band alignment between the valence bands of perovskite and NiO nanoparticles (NiO(np)). Recombination time between holes injected into NiO(np) and mobile electrons in the perovskite material is shown to be hundreds of picoseconds to a few nanoseconds. Because of the low conductivity of NiO(np), holes are pinned at the interface, and it is electrons that determine the recombination rate. This recombination competes with charge collection and therefore must be minimized. Doping NiO to promote higher mobility of holes is desirable in order to prevent back recombination. PMID:26942559

  11. Towards enhancing two-dimensional electron gas quantum confinement effects in perovskite oxide heterostructures

    SciTech Connect

    Nazir, Safdar; Behtash, Maziar; Yang, Kesong

    2015-03-21

    We explore the possibility of achieving highly confined two-dimensional electron gas (2DEG) within one single atomic layer through a comprehensive comparison study on three prototypical perovskite heterostructures, LaAlO{sub 3}/ATiO{sub 3} (A = Ca, Sr, and Ba), using first-principles electronic structure calculations. We predict that the heterostructure LaAlO{sub 3}/BaTiO{sub 3} has a highly confined 2DEG within a single atomic layer of the substrate BaTiO{sub 3}, and exhibits relatively higher interfacial charge carrier density and larger magnetic moments than the well-known LaAlO{sub 3}/SrTiO{sub 3} system. The long Ti-O bond length in the ab-plane of the LaAlO{sub 3}/BaTiO{sub 3} heterostructure is responsible for the superior charge confinement. We propose BaTiO{sub 3} as an exceptional substrate material for 2DEG systems with potentially superior properties.

  12. Novel Combination of Efficient Perovskite Solar Cells with Low Temperature Processed Compact TiO2 Layer via Anodic Oxidation.

    PubMed

    Du, Yangyang; Cai, Hongkun; Wen, Hongbin; Wu, Yuxiang; Huang, Like; Ni, Jian; Li, Juan; Zhang, Jianjun

    2016-05-25

    In this work, a facile and low temperature processed anodic oxidation approach is proposed for fabricating compact and homogeneous titanium dioxide film (AO-TiO2). In order to realize morphology and thickness control of AO-TiO2, the theory concerning anodic oxidation (AO) is unveiled and the influence of relevant parameters during the process of AO such as electrolyte ingredient and oxidation voltage on AO-TiO2 formation is observed as well. Meanwhile, we demonstrate that the planar perovskite solar cells (p-PSCs) fabricated in ambient air and utilizing optimized AO-TiO2 as electron transport layer (ETL) can deliver repeatable power conversion efficiency (PCE) over 13%, which possess superior open-circuit voltage (Voc) and higher fill factor (FF) compared to its counterpart utilizing conventional high temperature processed compact TiO2 (c-TiO2) as ETL. Through a further comparative study, it is indicated that the improvement of device performance should be attributed to more effective electron collection from perovskite layer to AO-TiO2 and the decrease of device series resistance. Furthermore, hysteresis effect about current density-voltage (J-V) curves in TiO2-based p-PSCs is also unveiled. PMID:27150310

  13. “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.

  14. Novel perovskite-related barium tungstate Ba 11W 4O 23

    NASA Astrophysics Data System (ADS)

    Hong, Seung-Tae

    2007-11-01

    Ba 11W 4O 23 was synthesized at 1300 °C, followed by quenching with liquid nitrogen. The crystal structure, which was known to be cryolite-related but has remained unclear, was initially determined by single-crystal X-ray diffraction for the isostructural Ru-substituted compound Ba 11(W 3.1Ru 0.9)O 22.5, which was discovered during exploratory synthesis in the Ba-Ru-O system. The structure of Ba 11W 4O 23 was refined by a combined powder X-ray and neutron Rietveld method ( Fd-3 m, a=17.1823(1) Å, Z=8, Rp=3.09%, Rwp=4.25%, χ2=2.8, 23 °C). The structure is an example of A-site vacancy-ordered 4×4×4 superstructure of a simple perovskite ABO 3, and it may be written as (Ba 1.75□ 0.25)BaWO 5.75□ 0.25, emphasizing vacancies on both metal and anion sites. The local structure of one of two asymmetric tungsten ions is the WO 6 octahedron, typical of perovskite. The other tungsten, however, is surrounded by oxygen and anionic vacancies statistically distributed over three divided sites to form 18 partially occupied oxygen atoms (˜30% on average), represented as WO 18/3. The A-site cation-vacancies are ordered at the 8a ( {1}/{8}, {1}/{8}, {1}/{8}) site in between adjoining WO 18/3 polyhedra which form 1-D arrangements along [110] and equivalent directions. In situ high-temperature XRD data have shown that the quenched Ba 11W 4O 23 at room temperature is isostructural to the high-temperature phase at 1100 °C.

  15. Oxides and Oxide Superconductors: Elastic and Related Properties

    NASA Astrophysics Data System (ADS)

    Lei, Ming

    Using both measurements and modeling, the elastic and related properties of some oxides and oxide superconductors were studied. The polycrystal elastic constants were measured using a MHz-frequency pulse-echo method between 295 and 4 K and corrected to the void-free state by using a model for a composite material containing spherical particles. The elastic moduli of the high-T_{rm c} superconductor rm Y_1Ba _2Cu_3O_7 (YBCO) were compared with that of oxides, especially the perovskites BaTiO _3 and SrTiO_3, which are crystal-structure building blocks for the YBCO superconductor. The bulk moduli were also calculated using a Born ionic model with two energy terms: electrostatic (Madelung) and ion -core-repulsion. The calculated bulk modulus of YBCO, 98 GPa, agrees well with measurement, 101 GPa. Based on monocrystal measurements combined with analysis-theory, elastic stiffnesses C_{ij} for orthorhombic YBCO were estimated. The bulk modulus obtained from the estimated C_{ij} by the Voigt-Reuss-Hill averaging method agrees with the monocrystal measurement. From the measured polycrystalline elastic constants, the Debye characteristic temperatures, Theta_ D, were calculated. For YBCO, Theta_sp{D}{rm O} = 437 K. The electron-phonon parameters, lambda, were estimated from T _{c} and Theta_sp {D}{rm O} using Kresin's model, which is valid for all values of lambda . For YBCO, lambda = 2.24. By calculating the Madelung energy, two further features were studied: the valence of copper and the electron hole distribution. The results show that the hole prefers the CuO_2 plane at the oxygen sites. All the results are consistent with the assumption that all copper ions have valences near +2. Using a relationship between T _ c and Delta V_ A, the difference in Madelung site potentials for a hole at the apical and planar oxygens, the pressure derivative and stress and stain derivatives of T_ c were calculated. The results show that T _ c increases with decreasing a-axis, increasing b

  16. Studies of "reactive templated grain growth" in some complex-oxide perovskites

    NASA Astrophysics Data System (ADS)

    West, David Lawrence

    This thesis details research on "reactive-templated grain growth" (RTGG) processing of complex-oxide perovskites. Four independent yet interwoven investigations are described. In the first, molten-salt synthesis yielded plate-like (˜0.2 x 5 x 5 mum) Ruddlesden-Popper (Sr3Ti 2O7) and Aurivillius (Bi4Ti3O 12 (BiT) and BaBi2Nb2O9) phases which served as "templates" in the subsequent studies. "Chemical preparation" routes were designed to produce intimately mixed, fine-grain matrix powders for the second and third investigations. A "citrate gel" method was developed for Bi1/2Na 1/2TiO3 (BNT)-based powders and a "sequential precipitation" method for PbNi1/3Nb2/3O3 - PbTiO3 (PNNT)-based powders. Both methods were original to the present investigation and resulted in dense, mum to sub-mum scale microstructures when applied to un-templated compositions. Microstructure studies of templated, chemically-prepared mixtures indicated that both Aurivillius phases behaved similarly with BNT-based matrices: An initially heterogeneous microstructure evolved towards a dense assemblage of anisometric (˜1 x 5 x 5 mum) grains. Sr3Ti 2O7 exhibited consistent behavior with both BNT and PNNT-based matrices: The microstructure evolved towards an aggregation of equi-axed, mum-scale grains with larger, isolated pores. A qualitative model was proposed to account for the behavior. It considered the excess matrix constituents after reaction to ABO3 perovskite and predicted an A-excess matrix in BNT-based mixtures templated with the Aurivillius phases and a B-excess matrix in BNT-based mixtures templated with Sr3Ti2O7. Predictions for PNNT-based matrices were less definite but not contradictory. In the final phase of the investigation, the solids formulation for BiT-templated, RTGG-processed Bi1/2Na17/40K3/40TiO 3 (BNKT) was systematically varied. This approach, original to this thesis, involved pre-reacting to well-defined alkali and bismuth titanate precursors. Use of these in different BNKT

  17. One-Dimensional Perovskite Manganite Oxide Nanostructures: Recent Developments in Synthesis, Characterization, Transport Properties, and Applications.

    PubMed

    Li, Lei; Liang, Lizhi; Wu, Heng; Zhu, Xinhua

    2016-12-01

    One-dimensional nanostructures, including nanowires, nanorods, nanotubes, nanofibers, and nanobelts, have promising applications in mesoscopic physics and nanoscale devices. In contrast to other nanostructures, one-dimensional nanostructures can provide unique advantages in investigating the size and dimensionality dependence of the materials' physical properties, such as electrical, thermal, and mechanical performances, and in constructing nanoscale electronic and optoelectronic devices. Among the one-dimensional nanostructures, one-dimensional perovskite manganite nanostructures have been received much attention due to their unusual electron transport and magnetic properties, which are indispensable for the applications in microelectronic, magnetic, and spintronic devices. In the past two decades, much effort has been made to synthesize and characterize one-dimensional perovskite manganite nanostructures in the forms of nanorods, nanowires, nanotubes, and nanobelts. Various physical and chemical deposition techniques and growth mechanisms are explored and developed to control the morphology, identical shape, uniform size, crystalline structure, defects, and homogenous stoichiometry of the one-dimensional perovskite manganite nanostructures. This article provides a comprehensive review of the state-of-the-art research activities that focus on the rational synthesis, structural characterization, fundamental properties, and unique applications of one-dimensional perovskite manganite nanostructures in nanotechnology. It begins with the rational synthesis of one-dimensional perovskite manganite nanostructures and then summarizes their structural characterizations. Fundamental physical properties of one-dimensional perovskite manganite nanostructures are also highlighted, and a range of unique applications in information storages, field-effect transistors, and spintronic devices are discussed. Finally, we conclude this review with some perspectives/outlook and future

  18. One-Dimensional Perovskite Manganite Oxide Nanostructures: Recent Developments in Synthesis, Characterization, Transport Properties, and Applications

    NASA Astrophysics Data System (ADS)

    Li, Lei; Liang, Lizhi; Wu, Heng; Zhu, Xinhua

    2016-03-01

    One-dimensional nanostructures, including nanowires, nanorods, nanotubes, nanofibers, and nanobelts, have promising applications in mesoscopic physics and nanoscale devices. In contrast to other nanostructures, one-dimensional nanostructures can provide unique advantages in investigating the size and dimensionality dependence of the materials' physical properties, such as electrical, thermal, and mechanical performances, and in constructing nanoscale electronic and optoelectronic devices. Among the one-dimensional nanostructures, one-dimensional perovskite manganite nanostructures have been received much attention due to their unusual electron transport and magnetic properties, which are indispensable for the applications in microelectronic, magnetic, and spintronic devices. In the past two decades, much effort has been made to synthesize and characterize one-dimensional perovskite manganite nanostructures in the forms of nanorods, nanowires, nanotubes, and nanobelts. Various physical and chemical deposition techniques and growth mechanisms are explored and developed to control the morphology, identical shape, uniform size, crystalline structure, defects, and homogenous stoichiometry of the one-dimensional perovskite manganite nanostructures. This article provides a comprehensive review of the state-of-the-art research activities that focus on the rational synthesis, structural characterization, fundamental properties, and unique applications of one-dimensional perovskite manganite nanostructures in nanotechnology. It begins with the rational synthesis of one-dimensional perovskite manganite nanostructures and then summarizes their structural characterizations. Fundamental physical properties of one-dimensional perovskite manganite nanostructures are also highlighted, and a range of unique applications in information storages, field-effect transistors, and spintronic devices are discussed. Finally, we conclude this review with some perspectives/outlook and future

  19. Exclusion of metal oxide by an RF sputtered Ti layer in flexible perovskite solar cells: energetic interface between a Ti layer and an organic charge transporting layer.

    PubMed

    Ameen, Sadia; Akhtar, M Shaheer; Seo, Hyung-Kee; Nazeeruddin, Mohammad Khaja; Shin, Hyung-Shik

    2015-04-14

    In this work, the effects of a titanium (Ti) layer on the charge transport and recombination rates of flexible perovskite solar cells were studied. Ti as an efficient barrier layer was deposited directly on PET-ITO flexible substrates through RF magnetic sputtering using a Ti-source and a pressure of ∼5 mTorr. A Ti coated PET-ITO was used for the fabrication of a flexible perovskite solar cell without using any metal oxide layer. The fabricated flexible perovskite solar cell was composed of a PET-ITO/Ti/perovskite (CH3NH3PbI3)/organic hole transport layer of 2,2',7,7'-tetrakis [N,N'-di-p-methoxyphenylamine]-9,9'-spirobifluorene (spiro-OMeTAD)-Li-TFSI/Ag. A high conversion efficiency of ∼8.39% along with a high short circuit current (JSC) of ∼15.24 mA cm(-2), an open circuit voltage (VOC) of ∼0.830 V and a high fill factor (FF) of ∼0.66 was accomplished by the fabricated flexible perovskite solar cell under a light illumination of ∼100 mW cm(-2) (1.5 AM). Intensity-modulated photocurrent (IMPS)/photovoltage spectroscopy (IMVS) studies demonstrated that the fabricated flexible perovskite solar cell considerably reduced the recombination rate. PMID:25747794

  20. Stability Comparison of Perovskite Solar Cells Based on Zinc Oxide and Titania on Polymer Substrates.

    PubMed

    Dkhissi, Yasmina; Meyer, Steffen; Chen, Dehong; Weerasinghe, Hasitha C; Spiccia, Leone; Cheng, Yi-Bing; Caruso, Rachel A

    2016-04-01

    Device scale-up and long-term stability constitute two major hurdles that the emerging perovskite solar technology will have to overcome before commercialization. Here, a comparative study was performed between ZnO and TiO2 electron-selective layers, two materials that allow the low-temperature processing of perovskite solar cells on polymer substrates. Although the use of TiO2 is well established on glass substrates, ZnO was chosen because it can be readily printed at low temperature and offers the potential for the large-scale roll-to-roll manufacturing of flexible photovoltaics at a low cost. However, a rapid degradation of CH3 NH3 PbI3 was observed if it was deposited on ZnO, therefore, the influence of the perovskite film preparation conditions on its morphology and degradation kinetics was investigated. This study showed that CH3 NH3 PbI3 could withstand a higher temperature on TiO2 than ZnO and that TiO2 -based perovskite devices were more stable than their ZnO analogues. PMID:26893225

  1. Transport in proton conducting perovskite oxides and solid-state electrochemical devices

    NASA Astrophysics Data System (ADS)

    Wang, Wensheng

    The objective of this dissertation is to investigate the transport of H2O in perovskite type proton conducting oxides and their electrical conductivies due to protons, oxygen ions, and electron holes. In Chapter 2, polycrystalline samples in the system BaO-ZrO2-Y 2O3 (YO1.5), predominantly containing Y-doped BaZrO3, and yttria-stabilized zirconia (YSZ), were fabricated. The as-sintered samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and chemically analyzed by electron probe microanalysis (EPMA). A tentative phase diagram (isothermal section at 1600°C) of the BaO-ZrO2-YO1.5 system was established. In Chapter 3, H2O incorporation was investigated by means of electrical conductivity relaxation measurement using a 4 probe dc method. Several models were used to fit the experimental traces of conductivity vs. time, and to estimate the chemical diffusion coefficient of H 2O, D˜H2O , and the surface exchange constant, kexc, over a range of temperatures from 400°C to 900°C. In Chapter 4 and 5, the partial electrical conductivities in Ba 3Ca1.18Nb1.82O(9-delta) (BCN18) due to protons, oxygen ions, and electron holes were calculated and measured as functions of pO2,pH2 O , and temperature. Electrical conduction domains and the activation energies associated with the electrical conduction by oxygen ions and electron holes were determined. In Chapter 6, the change in electrical conductivity in response to the change of pH2O was investigated on BCN18 of both dense and porous samples at various pH2O . The empirical relationships between the change in electrical conductivity and pH2O were determined. Also, the response rate was characterized and analyzed as functions of sample porosity and temperature.

  2. Chemical vapor deposition and electric characterization of perovskite oxides LaMO{sub 3} (M=Co, Fe, Cr and Mn) thin films

    SciTech Connect

    Ngamou, Patrick Herve Tchoua; Bahlawane, Naoufal

    2009-04-15

    Oxides with a perovskite structure are important functional materials often used for the development of modern devices. In view of extending their applicability, it is necessary to efficiently control their growth as thin films using technologically relevant synthesis methods. Pulsed spray evaporation CVD was used to grow several perovskite-type oxides on planar silicon substrates at temperatures ranging from 500 to 700 deg. C. The optimization of the process control parameters allows the attainment of the perovskite structure as a single phase. The electrical characterization using the temperature-dependent conductivity and thermopower indicates the p-type conduction of the grown films and shows a decreasing concentration of the charge carrier, mobility and band gap energy in the sequence LaCoO{sub 3}>LaMnO{sub 3}>LaCrO{sub 3}>LaFeO{sub 3}. The investigation of the electric properties of the obtained perovskite thin films shows the versatility of CVD as a method for the development of innovative devices. - Graphical abstract: We report a single step deposition of perovskite thin films LaMO{sub 3} (M: Co, Mn, Cr, Fe) using pulsed spray evaporation chemical vapor deposition. Electrical and thermopower properties, similar to these of bulk materials, could promote the development of modern thermoelectric devices based on thin films technology.

  3. Incorporation effect of nanosized perovskite LaFe₀.₇Co₀.₃O₃ on the electrochemical activity of Pt nanoparticles-multi walled carbon nanotube composite toward methanol oxidation

    SciTech Connect

    Noroozifar, Meissam; Khorasani-Motlagh, Mozhgan; Khaleghian-Moghadam, Roghayeh; Ekrami-Kakhki, Mehri-Saddat; Shahraki, Mohammad

    2013-05-01

    Nanosized perovskite LaFe₀.₇Co₀.₃O₃ (LFCO) is synthesized through conventional co-precipitation method and characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques. The incorporation effect of the mentioned perovskite to catalytic activity of the PtNPs-MWCNTs-nafion (or -chitosan) catalyst toward methanol oxidation has been studied by cyclic voltammetry. Based on the electrochemical studies, all MWCNTs-PtNPs-nafion (or chitosan) and MWCNTs-PtNPs-LFCO-nafion (or chitosan) catalysts show a considerable activity for methanol oxidation. However, a synergistic effect is observed when LFCO is added to the catalyst by decreasing the poisoning rate of the Pt catalyst. - Graphical abstract: Nanosized perovskite LaFe₀.₇Co₀.₃O₃ is synthesized and characterized. The incorporation effect of the mentioned perovskite to catalytic activity of the PtNPS-MWCNTs-nafion (or -chitosan) catalyst toward methanol oxidation is studied. Highlights: • Nanocrystalline LaFe₀.₇Co₀.₃O₃ (LFCO) is prepared by a new simple co-precipitation method. • Effect of LFCO to catalytic activity of PtNPS for methanol oxidation is studied. • A synergistic effect is observed when LFCO is added to the Pt catalyst. • Oxygen of LFCO could be considered as active oxygen to remove CO intermediates.

  4. Rh promoted La0.75Sr0.25(Fe0.8Co0.2)1-xGaxO3-δ perovskite catalysts: Characterization and catalytic performance for methane partial oxidation to synthesis gas

    NASA Astrophysics Data System (ADS)

    Palcheva, R.; Olsbye, U.; Palcut, M.; Rauwel, P.; Tyuliev, G.; Velinov, N.; Fjellvåg, H. H.

    2015-12-01

    Synthesis gas production via selective oxidation of methane at 600 °C in a pulse reaction over La0.75Sr0.25(Fe0.8Co0.2)1-xGaxO3-δ (x = 0.1, 0.25, 0.4) perovskite-supported rhodium catalysts, was investigated. The perovskite oxides were prepared by sol-gel citrate method and characterized by X-ray Diffraction (XRD), Moessbauer Spectroscopy (MS), Temperature Programmed Reduction (TPR-H2), X-ray Photoelectron Spectroscopy (XPS) and High Resolution Transmission Electron Microscopy (HRTEM). According to XRD analysis, the synthesized samples were a single perovskite phase. The perovskite structure of Ga substituted samples remained stable after TPR-H2, as confirmed by XRD. Data of MS identified Fe3+ ions in two distinctive coordination environments, and Fe4+ ions. The Rh2O3 thin overlayer was detected by the HRTEM for the Rh impregnated perovskite oxides. During the interaction of methane with oxidized perovskite-supported Rh (0.5 wt.%) catalysts, besides CO, H2, and surface carbon, CO2 and H2O were formed. The Rh perovskite catalyst with x = 0.25 gallium exhibits the highest catalytic activity of 83% at 600 °C. The CO selectivity was affected by the reducibility of La0.75Sr0.25(Fe0.8Co0.2)1-xGaxO3-δ perovskite materials.

  5. 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.

  6. Spectroscopic study of mixed oxide SAT 1- x:LA x perovskite crystals

    NASA Astrophysics Data System (ADS)

    Runka, T.; Łapsa, K.; Łapiński, A.; Aleksiyko, R.; Berkowski, M.; Drozdowski, M.

    2004-10-01

    Mixed perovskite crystals have been grown from multicomponent melts using the Czochralski method. The Raman, FT-IR and Brillouin investigations of perovskite (1- x)Sr(Al 0.5Ta 0.5)O 3: xLaAlO 3 crystals are reported. The measurements have been performed for several LA concentrations in the range 0.22≤ x≤0.36 at room temperature. The assignment of vibrational modes of IR and Raman spectra was proposed. The experimental results were correlated with structural data, obtained from X-ray diffraction study. The dependence of hypersonic velocity of transverse and longitudinal modes as a function of LA content was also determined. Spectroscopic investigations confirmed the disordered Al/Ta distribution, which increases with the increase of LA content.

  7. 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.

  8. Steady state performance, photo-induced performance degradation and their relation to transient hysteresis in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Jena, Ajay Kumar; Kulkarni, Ashish; Ikegami, Masashi; Miyasaka, Tsutomu

    2016-03-01

    Hysteresis in current-voltage curves of perovskite solar cells is a serious concern as it creates confusions about actual cell performance and raises questions on its reliability. Although a lot of effort has been made to understand the origin of hysteresis, knowing whether hysteresis affects the cell performance while they are in practical use (operated constantly at maximum power point) is not yet examined. In the present study, we investigate steady state performance and performance stability of perovskite solar cells (planar architecture with varying perovskite film thickness and TiO2 mesoscopic structure with different TiO2 compact layer thickness exhibiting hysteresis of different magnitudes) operating across an external load in relation to hysteresis. The planar cells with larger hysteresis exhibit a steady state current that closely matches the value determined on forward voltage scan. Cyclic photocurrent-dark current measurements on cells with hysteresis of different magnitudes reveal that photo-induced electrical instability (not material degradation), which might be originated from ion migration or photo-induced traps formation, is not related to hysteresis. Performance of the cells is recovered partially or fully, depending on the device structure, on storage in dark. TiO2 meso-structure cells tend to show complete recovery while the planar cells recover partially.

  9. Electrocatalytic performances of LaNi1-xMgxO3 perovskite oxides as bi-functional catalysts for lithium air batteries

    NASA Astrophysics Data System (ADS)

    Du, Zhenzhen; Yang, Peng; Wang, Long; Lu, Yuhao; Goodenough, J. B.; Zhang, Jian; Zhang, Dawei

    2014-11-01

    Mg-doped perovskite oxides LaNi1-xMgxO3 (x = 0, 0.08, 0.15) electrocatalysts are synthesized by a sol-gel method using citric acid as complex agent and ethylene glycol as thickening agent. The intrinsic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity of as-prepared perovskite oxides in aqueous electrolyte are examined on a rotating disk electrode (RDE) set up. Li-air primary batteries on the basis of Mg-doped perovskite oxides LaNi1-xMgxO3 (x = 0, 0.08, 0.15) and nonaqueous electrolyte are also fabricated and tested. In terms of the ORR current densities and OER current densities, the performance is enhanced in the order of LaNiO3, LaNi0.92Mg0.08O3 and LaNi0.85Mg0.15O3. Most notably, partially substituting nickel with magnesium suppresses formation of Ni2+ and ensures high concentration of both OER and ORR reaction energy favorable Ni3+ (eg = 1) on the surface of perovskite catalysts. Nonaqueous Li-air primary battery using LaNi0.92Mg0.08O3 and LaNi0.85Mg0.15O3 as the cathode catalysts exhibit improved performances compared with LaNiO3 catalyst, which are consistent with the ORR current densities.

  10. 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.

  11. Effects of ion beam modification on absorption and transport of hydrogen in perovskite-type oxide ceramics

    NASA Astrophysics Data System (ADS)

    Tsuchiya, B.; Nagata, S.; Toh, K.; Shikama, T.

    2006-01-01

    Surface modification of proton conductive material (Yb-doped SrCeO3 perovskite-type ceramics) has been carried out by irradiation with 10 keV D2+ , He+ or Ar+ ions at room temperature. By exposure of Ar gas including H2O to the irradiated surface, the concentration of H in the projected range increased. The absorption of H is associated due to dissociation of H2O. The concentrations of the absorbed H by D+, He+ and Ar+ ion irradiations became about 2.0, 0.3 and 1.0 times, respectively, as much as the saturation concentration by H+ ion implantation. It was also found by isochronal annealing experiments that the thermal desorption rate of H retained in the irradiated surface was lower than that in the unirradiated one. These results show that the trapping and migration of hydrogen atoms in the proton conducting oxide ceramics are enhanced by ion beam modification.

  12. Vacancy-type defects and electronic structure of perovskite-oxide SrTiO3 from positron annihilation

    NASA Astrophysics Data System (ADS)

    Hamid, A. S.; Uedono, A.; Chikyow, T.; Uwe, K.; Mochizuki, K.; Kawaminami, S.

    2006-02-01

    The vacancy-type defects in Nb-doped SrTiO3 and in undoped SrTiO3, annealed in H2 flow, were investigated by means of positron lifetime and 2D angular correlation of annihilation radiation (ACAR) experiments. The calculations of the lifetime of positron were performed by using atomic superposition (AT-SUP) method. The results showed that positrons annihilate from a free state in the Nb-doped SrTiO3. The trapping centers in the annealed sample were found to be oxygen vacancies VO associated with relaxation of the surrounding ions. Moreover, the momentum distributions of the samples studied were correlated to the variation of their electronic structure. It was proposed from the drastic change in the momentum distribution upon introduction of VO, that 2D-ACAR technique is a sensitive tool for acquiring information on the electronic and bond structure of the perovskite-oxides.

  13. Doped Mott Insulators in (111) Bilayers of Perovskite Transition-Metal Oxides with a Strong Spin-Orbit Coupling

    SciTech Connect

    Okamoto, Satoshi

    2013-01-01

    The electronic properties of Mott insulators realized in (111) bilayers of perovskite transition-metal oxides are studied. The low-energy effective Hamiltonians for such Mott insulators are derived in the presence of a strong spin-orbit coupling. These models are characterized by the antiferromagnetic Heisenberg interaction and the anisotropic interaction whose form depends on the $d$ orbital occupancy. From exact diagonalization analyses on finite clusters, the ground state phase diagrams are derived, including a Kitaev spin liquid phase in a narrow parameter regime for $t_{2g}$ systems. Slave-boson mean-field analyses indicate the possibility of novel superconducting states induced by carrier doping into the Mott-insulating parent systems, suggesting the present model systems as unique playgrounds for studying correlation-induced novel phenomena. Possible experimental realizations are also discussed.

  14. 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.

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

    DOE PAGESBeta

    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

  16. Promotion of Oxygen Reduction by Exsolved Silver Nanoparticles on a Perovskite Scaffold for Low-Temperature Solid Oxide Fuel Cells.

    PubMed

    Zhu, Yinlong; Zhou, Wei; Ran, Ran; Chen, Yubo; Shao, Zongping; Liu, Meilin

    2016-01-13

    Solid oxide fuel cells (SOFCs) have potential to be the cleanest and most efficient electrochemical energy conversion devices with excellent fuel flexibility. To make SOFC systems more durable and economically competitive, however, the operation temperature must be significantly reduced, which depends sensitively on the development of highly active electrocatalysts for oxygen reduction reaction (ORR) at low temperatures. Here we report a novel silver nanoparticle-decorated perovskite oxide, prepared via a facile exsolution process from a Sr0.95Ag0.05Nb0.1Co0.9O3-δ (SANC) perovskite precursor, as a highly active and robust ORR electrocatalyst for low-temperature SOFCs. The exsolved Sr0.95Ag0.05Nb0.1Co0.9O3-δ (denoted as e-SANC) electrode is very active for ORR, achieving a very low area specific resistance (∼0.214 Ω cm(2) at 500 °C). An anode-supported cell with the new heterostructured cathode demonstrates very high peak power density (1116 mW cm(-2) at 500 °C) and stable operation for 140 h at a current density of 625 mA cm(-2). The superior ORR activity and stability are attributed to the fast oxygen surface exchange kinetics and the firm adhesion of the Ag nanoparticles to the Sr0.95Nb0.1Co0.9O3-δ (SNC0.95) support. Moreover, the e-SANC cathode displays improved tolerance to CO2. These unique features make the new heterostructured material a highly promising cathode for low-temperature SOFCs. PMID:26619096

  17. More Cu, more problems: Decreased CO2 conversion ability by Cu-doped La0.75Sr0.25FeO3 perovskite oxides

    NASA Astrophysics Data System (ADS)

    Daza, Yolanda A.; Maiti, Debtanu; Hare, Bryan J.; Bhethanabotla, Venkat R.; Kuhn, John N.

    2016-06-01

    The effect of Cu doping on the conversion of CO2 to CO was investigated on H2-reduced La0.75Sr0.25FeO3 perovskite oxides. Six La0.75Sr0.25Fe1 -YCuYO3 perovskites, labeled Cu100*Y (with Y = 0, 0.10, 0.25, 0.50, 0.75, and 1) were synthesized and characterized through X-ray diffraction (XRD), temperature-programmed oxygen vacancy formation, and temperature-programmed reduction (TPR). The incorporation of Cu facilitates the formation of oxygen vacancies at lower temperatures but also increased the instability of the perovskite. DFT simulations suggested that the Cu10 sample is favored to produce oxygen vacancies compared to Cu0 and Cu25 samples, which was consistent with experimental oxygen vacancy formation results. For the Cu0, Cu10, and Cu25 samples, temperature-programmed CO2 conversion (TPO-CO2) after isothermal H2-reduction at 450 °C and post-reduction XRD were performed to evaluate the ability of the materials to convert CO2 at low temperatures and to identify the crystalline phases active in the reaction. The peak conversion of CO2 to CO was achieved 30 °C lower on the Cu10 sample versus the Cu0, but less CO was produced, due to a decreased re-oxidation activity of the Cu-doped samples. CO production was inhibited in the Cu25 sample, likely due to a combined effect of poor CO2 dissociative chemisorption energies on metallic Cu and increased thermodynamic stability of the oxygen vacant perovskites. Control experiments (Cu deposited onto La0.75Sr0.25FeO3) indicated the stability of the copper-containing perovskite oxides phases was the primary limiting factor preventing CO formation from CO2.

  18. Efficient organic-inorganic hybrid perovskites and doped metal oxide heterojunction solar cells

    NASA Astrophysics Data System (ADS)

    Fan, Xiaojuan

    Organic-Inorganic hybrid perovskite CH3NH3PbI3 has recently attracted much attention for its high efficient solar energy conversion. This semiconducting pigment with a direct bandgap of 1.55 eV has made it an interesting optical and electronic material over the whole visible solar emission spectrum. The role of hole conducting has been found in this semiconductor that allows perovskite solar cell (PSC) to be formed by CH3NH3PbI3/TiO2 heterojunctions that use TiO2 as scaffold, and carbon as a back contact. We will report a double layer metal doped TiO2/Al2O3 mesoporous scaffold covered by the p-type semiconducting pigment to form a high efficient PSC through solution method. TiO2 and Al2O3 are both large band gap semiconductors that affect conducting and recombination rate in solar cells. One improvement work is doping other metal elements in TiO2 to raise the mobility while extend the recombination time. It has suggested that optimal amounts of doped metals such as Cu, Co, Mn can suppress the reduction of Ti4 + resulting better transportation. TiO2 thin films doped with metals are subjected to the EPR analysis and the results will be correlated with measurements of electronic-optical properties.

  19. Design of Perovskite Oxides as Anion-Intercalation-Type Electrodes for Supercapacitors: Cation Leaching Effect.

    PubMed

    Liu, Yu; Dinh, Jim; Tade, Moses O; Shao, Zongping

    2016-09-14

    Oxygen ions can be exploited as a charge carrier to effectively realize a new type of anion-intercalation supercapacitor. In this study, to get some useful guidelines for future materials development, we comparatively studied SrCoO3-δ (SC), Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), and Co3O4 as electrodes in supercapacitors with aqueous alkaline electrolyte. The effect of interaction between the electrode materials with the alkaline solution was focused on the structure and specific surface area of the electrode material, and ultimately the electrochemical performance was emphasized. Both BSCF and SC were found to experience cation leaching in alkaline solution, resulting in an increase in the specific surface area of the material, but overleaching caused the damage of perovskite structure of BSCF. Barium leaching was more serious than strontium, and the cation leaching was component dependent. Although high initial capacitance was achieved for BSCF, it was not a good candidate as intercalation-type electrode for supercapacitor because of poor cycling stability from serious Ba(2+) and Sr(2+) leaching. Instead, SC was a favorable electrode candidate for practical use in supercapacitors due to its high capacity and proper cation leaching capacity, which brought beneficial effect on cycling stability. It is suggested that cation leaching effect should be seriously considered in the development of new perovskite materials as electrodes for supercapacitors. PMID:27559826

  20. Industrial-grade rare-earth and perovskite oxide for high-performance electrolyte layer-free fuel cell

    NASA Astrophysics Data System (ADS)

    Xia, Chen; Wang, Baoyuan; Ma, Ying; Cai, Yixiao; Afzal, Muhammad; Liu, Yanyan; He, Yunjuan; Zhang, Wei; Dong, Wenjing; Li, Junjiao; Zhu, Bin

    2016-03-01

    In the present work, we report a composite of industrial-grade material LaCePr-oxide (LCP) and perovskite La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) for advanced electrolyte layer-free fuel cells (EFFCs). The microstructure, morphology, and electrical properties of the LCP, LSCF, and LCP-LSCF composite were investigated and characterized by XRD, SEM, EDS, TEM, and EIS. Various ratios of LCP to LSCF in the composite were modulated to achieve balanced ionic and electronic conductivities. Fuel cell with an optimum ratio of 60 wt% LCP to 40 wt% LSCF reached the highest open circuit voltage (OCV) at 1.01 V and a maximum power density of 745 mW cm-2 at 575 °C, also displaying a good performance stability. The high performance is attributed to the interfacial mechanisms and electrode catalytic effects. The findings from the present study promote industrial-grade rare-earth oxide as a promising new material for innovative low temperature solid oxide fuel cell (LTSOFC) technology.

  1. A novel perovskite based catalyst with high selectivity and activity for partial oxidation of methane for fuel cell applications.

    PubMed

    Staniforth, J; Evans, S E; Good, O J; Darton, R J; Ormerod, R M

    2014-10-28

    Solid oxide fuel cells (SOFCs) have the potential to revolutionise the present fuel economy due to their higher fuel conversion efficiency compared with standard heat engines and the possibility of utilizing the heat produced in a combined heat and power system. One of the reasons they have yet to fulfil this potential is that the conventional anode material of choice, a nickel/yttria-stabilised zirconia cermet, requires a high temperature production process and under operating conditions is susceptible to carbon and sulphur poisoning. Perovskite-based materials have been proposed as potential anode materials for SOFCs due to their potentially high electronic conductivity and catalytic properties. One of the problems in realizing this potential has been their low catalytic activity towards methane reforming compared to conventional nickel based cermet materials. A nickel doped strontium zirconate material produced by low temperature hydrothermal synthesis is described which has high activity for methane reforming and high selectivity towards partial oxidation of methane as opposed to total oxidation products. Initial studies show a very low level of carbon formation which does not increase over time. PMID:25069597

  2. 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

  3. 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

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

    NASA Astrophysics Data System (ADS)

    Misra, Sunasira

    2012-07-01

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

  5. 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.

  6. Interfaces in Perovskite Heterostructures

    SciTech Connect

    Christen, Hans M; Kim, Dae Ho; Rouleau, Christopher M

    2008-01-01

    Recent advances in film synthesis have made it possible to investigate the properties of well-controlled interfaces in perovskite metal-oxides. A review of published experimental data and computational results indicate that so far most interfaces that have been analyzed in ferroelectric materials - while necessary to impose large lattice strain on the polar material - contribute little to the ferroelectricity and may instead be detrimental to the desired properties. In contrast, a very different situation arises at interfaces that show changes in the electronic configuration as a consequence of a compositional discontinuity. Data is shown for LaMnO3/SrTiO 3 superlattices as an example of electronic effects that produce enhanced properties, further illustrating the richness of interfacial properties that can be obtained at interfaces (as shown in numerous published results for different but related interfaces).

  7. 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.

  8. Ion-exchangeable oxides with layered perovskite structures as photocatalysts for overall water splitting

    SciTech Connect

    Takata, T.; Hara, M.; Kondo, J.N.; Domen, K.; Shinohara, K.; Tanaka, A.

    1997-12-31

    A novel series of photocatalysts for an overall water splitting is reported. The catalysts have a layered perovskite type structure with a general formula of A{sub 2{minus}x}La{sub 2}Ti{sub 3{minus}x}Nb{sub x}O{sub 10} (A = K, Rb, Cs; x = 0, 0.5, 1.0). The catalysts, except for the one with x = 1.0, are spontaneously hydrated, and the band gap irradiation induced efficient evolution of H{sub 2} and O{sub 2} in a stoichiometric ratio from an aqueous alkaline solution when a proper amount of Ni loading was made. The reaction mechanism of water splitting on these catalysts is discussed on the bases of the structural study of the catalysts.

  9. Magnetoresistance in ordered and disordered double perovskite oxide, Sr 2FeMoO 6

    NASA Astrophysics Data System (ADS)

    Sarma, D. D.; Sampathkumaran, E. V.; Ray, Sugata; Nagarajan, R.; Majumdar, Subham; Kumar, Ashwani; Nalini, G.; Guru Row, T. N.

    2000-04-01

    We have prepared crystallographically ordered and disordered specimens of the double perovskite, Sr 2FeMoO 6, and investigated their magnetoresistance (MR) behaviour. The extent of ordering between the Fe and Mo sites in the two samples is determined by Rietveld analysis of powder X-ray diffraction patterns and reconfirmed by Mössbauer studies. While the ordered sample exhibits the sharp low-field response, followed by moderate changes in the MR at higher fields, the disordered sample is characterised by the absence of the spectacular low-field response. We argue that the low field response depends crucially on the half-metallic ferromagnetism, while the high-field response follows from the overall magnetic nature of the sample, even in absence of the half-metallic state.

  10. A half-metallic A- and B-site-ordered quadruple perovskite oxide CaCu3Fe2Re2O12 with large magnetization and a high transition temperature

    NASA Astrophysics Data System (ADS)

    Chen, Wei-Tin; Mizumaki, Masaichiro; Seki, Hayato; Senn, Mark S.; Saito, Takashi; Kan, Daisuke; Attfield, J. Paul; Shimakawa, Yuichi

    2014-05-01

    Strong correlation between spins and conduction electrons is key in spintronic materials and devices. A few ferro- or ferrimagnetic transition metal oxides such as La1-xSrxMnO3, Fe3O4, CrO2 and Sr2FeMoO6 have spin-polarized conduction electrons at room temperature, but it is difficult to find other spin-polarized oxides with high Curie temperatures (well above room temperature) and large magnetizations for spintronics applications. Here we show that an A- and B-site-ordered quadruple perovskite oxide, CaCu3Fe2Re2O12, has spin-polarized conduction electrons and is ferrimagnetic up to 560 K. The couplings between the three magnetic cations lead to the high Curie temperature, a large saturation magnetization of 8.7 μB and a half-metallic electronic structure, in which only minority-spin bands cross the Fermi level, producing highly spin-polarized conduction electrons. Spin polarization is confirmed by an observed low-field magnetoresistance effect in a polycrystalline sample. Optimization of CaCu3Fe2Re2O12 and related quadruple perovskite phases is expected to produce a new family of useful spintronic materials.

  11. Monitoring non-pseudomorphic epitaxial growth of spinel/perovskite oxide heterostructures by reflection high-energy electron diffraction

    SciTech Connect

    Schütz, P.; Pfaff, F.; Scheiderer, P.; Sing, M.; Claessen, R.

    2015-02-09

    Pulsed laser deposition of spinel γ-Al{sub 2}O{sub 3} thin films on bulk perovskite SrTiO{sub 3} is monitored by high-pressure reflection high-energy electron diffraction (RHEED). The heteroepitaxial combination of two materials with different crystal structures is found to be inherently accompanied by a strong intensity modulation of bulk diffraction patterns from inelastically scattered electrons, which impedes the observation of RHEED intensity oscillations. Avoiding such electron surface-wave resonance enhancement by de-tuning the RHEED geometry allows for the separate observation of the surface-diffracted specular RHEED signal and thus the real-time monitoring of sub-unit cell two-dimensional layer-by-layer growth. Since these challenges are essentially rooted in the difference between film and substrate crystal structure, our findings are of relevance for the growth of any heterostructure combining oxides with different crystal symmetry and may thus facilitate the search for novel oxide heterointerfaces.

  12. Research progress of perovskite materials in photocatalysis- and photovoltaics-related energy conversion and environmental treatment.

    PubMed

    Wang, Wei; Tadé, Moses O; Shao, Zongping

    2015-08-01

    Meeting the growing global energy demand is one of the important challenges of the 21st century. Currently over 80% of the world's energy requirements are supplied by the combustion of fossil fuels, which promotes global warming and has deleterious effects on our environment. Moreover, fossil fuels are non-renewable energy and will eventually be exhausted due to the high consumption rate. A new type of alternative energy that is clean, renewable and inexpensive is urgently needed. Several candidates are currently available such as hydraulic power, wind force and nuclear power. Solar energy is particularly attractive because it is essentially clean and inexhaustible. A year's worth of sunlight would provide more than 100 times the energy of the world's entire known fossil fuel reserves. Photocatalysis and photovoltaics are two of the most important routes for the utilization of solar energy. However, environmental protection is also critical to realize a sustainable future, and water pollution is a serious problem of current society. Photocatalysis is also an essential route for the degradation of organic dyes in wastewater. A type of compound with the defined structure of perovskite (ABX3) was observed to play important roles in photocatalysis and photovoltaics. These materials can be used as photocatalysts for water splitting reaction for hydrogen production and photo-degradation of organic dyes in wastewater as well as for photoanodes in dye-sensitized solar cells and light absorbers in perovskite-based solar cells for electricity generation. In this review paper, the recent progress of perovskites for applications in these fields is comprehensively summarized. A description of the basic principles of the water splitting reaction, photo-degradation of organic dyes and solar cells as well as the requirements for efficient photocatalysts is first provided. Then, emphasis is placed on the designation and strategies for perovskite catalysts to improve their

  13. Artificial layered perovskite oxides A(B{sub 0.5}B′{sub 0.5})O{sub 3} as potential solar energy conversion materials

    SciTech Connect

    Chen, Hungru; Umezawa, Naoto

    2015-02-07

    Perovskite oxides with a d{sup 0} electronic configuration are promising photocatalysts and exhibit high electron mobilities. However, their band gaps are too large for efficient solar energy conversion. On the other hand, transition metal cations with partially filled d{sup n} electronic configurations give rise to visible light absorption. In this study, by using hybrid density functional theory calculations, it is demonstrated that the virtues of the two categories of materials can be combined in perovskite oxide A(B{sub 0.5}B′{sub 0.5})O{sub 3} with a layered B-site ordering along the [001] direction. The electronic structures of the four selected perovskite oxide compounds, La(Ti{sub 0.5}Ni{sub 0.5})O{sub 3}, La(Ti{sub 0.5}Zn{sub 0.5})O{sub 3}, Sr(Nb{sub 0.5}Cr{sub 0.5})O{sub 3}, and Sr(Nb{sub 0.5}Fe{sub 0.5})O{sub 3} are calculated and discussed.

  14. Physical properties of transparent perovskite oxides (Ba,La)SnO3 with high electrical mobility at room temperature

    NASA Astrophysics Data System (ADS)

    Kim, Hyung Joon; Kim, Useong; Kim, Tai Hoon; Kim, Jiyeon; Kim, Hoon Min; Jeon, Byung-Gu; Lee, Woong-Jhae; Mun, Hyo Sik; Hong, Kwang Taek; Yu, Jaejun; Char, Kookrin; Kim, Kee Hoon

    2012-10-01

    Transparent electronic materials are increasingly in demand for a variety of optoelectronic applications, ranging from passive transparent conductive windows to active thin-film transistors. BaSnO3 is a semiconducting oxide with a large band gap of more than 3.1 eV. Recently, we discovered that BaSnO3 doped with a few percent of La exhibits an unusually high electrical mobility of 320cm2V-1s-1 at room temperature and superior thermal stability at high temperatures [H. J. Kim , Appl. Phys. ExpressAPECE41882-077810.1143/APEX.5.061102 5, 061102 (2012)]. Following that paper, here, we report various physical properties of (Ba,La)SnO3 single crystals and epitaxial films including temperature-dependent transport and phonon properties, optical properties, and first-principles calculations. We find that almost doping-independent mobility of 200-300cm2V-1s-1 is realized in the single crystals in a broad doping range from 1.0×1019 to 4.0×1020 cm-3. Moreover, the conductivity of ˜104Ω-1cm-1 reached at the latter carrier density is comparable to the highest value previously reported in the transparent conducting oxides. We attribute the high mobility to several physical properties of (Ba,La)SnO3: a small effective mass coming from the ideal Sn-O-Sn bonding in a cubic perovskite network, small disorder effects due to the doping away from the SnO6 octahedra, and reduced carrier scattering due to the high dielectric constant. The observation of the reduced mobility of ˜70cm2V-1s-1 in the epitaxial films is mainly attributed to additional carrier scattering due to dislocations and grain boundaries, which are presumably created by the lattice mismatch between the substrate SrTiO3 and (Ba,La)SnO3. The main optical gap coming from the charge transfer from O 2p to Sn 5s bands in (Ba,La)SnO3 single crystals remained at about 3.33 eV, and the in-gap states only slightly increased, thus, maintaining optical transparency in the visible spectral region. Based on all these results, we

  15. p-i-n heterojunctions with BiFeO3 perovskite nanoparticles and p- and n-type oxides: photovoltaic properties.

    PubMed

    Chatterjee, Soumyo; Bera, Abhijit; Pal, Amlan J

    2014-11-26

    We formed p-i-n heterojunctions based on a thin film of BiFeO3 nanoparticles. The perovskite acting as an intrinsic semiconductor was sandwiched between a p-type and an n-type oxide semiconductor as hole- and electron-collecting layer, respectively, making the heterojunction act as an all-inorganic oxide p-i-n device. We have characterized the perovskite and carrier collecting materials, such as NiO and MoO3 nanoparticles as p-type materials and ZnO nanoparticles as the n-type material, with scanning tunneling spectroscopy; from the spectrum of the density of states, we could locate the band edges to infer the nature of the active semiconductor materials. The energy level diagram of p-i-n heterojunctions showed that type-II band alignment formed at the p-i and i-n interfaces, favoring carrier separation at both of them. We have compared the photovoltaic properties of the perovskite in p-i-n heterojunctions and also in p-i and i-n junctions. From current-voltage characteristics and impedance spectroscopy, we have observed that two depletion regions were formed at the p-i and i-n interfaces of a p-i-n heterojunction. The two depletion regions operative at p-i-n heterojunctions have yielded better photovoltaic properties as compared to devices having one depletion region in the p-i or the i-n junction. The results evidenced photovoltaic devices based on all-inorganic oxide, nontoxic, and perovskite materials. PMID:25350523

  16. Design of a dual-layer ceramic interconnect based on perovskite oxides for segmented-in-series solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Park, Beom-Kyeong; Kim, Dae-Wi; Song, Rak-Hyun; Lee, Seung-Bok; Lim, Tak-Hyoung; Park, Seok-Joo; Park, Chong-Ook; Lee, Jong-Won

    2015-12-01

    A segmented-in series (SIS) SOFC consists of segmented unit cells connected in electrical series and shows improved stack efficiency over conventional SOFCs. In this design, a thin interconnect film provides both electrical contact and sealing between the anode of one cell and the cathode of the next; thus, it should have high conductivity and chemical/structural stability in both reducing and oxidizing atmospheres as well as impermeability to gases. Here, we report a dual-layer interconnect film for SIS-SOFCs comprising perovskite-type oxides, Sr0.7La0.2TiO3 (exposed to a reducing atmosphere) and La0.8Sr0.2FeO3 (exposed to an oxidizing atmosphere). The interconnect film is not only very dense but also highly conductive and stable under SOFC operating conditions; in particular, it shows an area-specific resistance of 19.6 mΩ cm2 at 800 °C, which is much lower than the generally accepted limit for SOFCs. A flat-tubular SIS-SOFC fabricated using these interconnect films exhibits a power density as high as 340 mW cm-2, which proves the feasibility of the dual-layer interconnect design.

  17. Polarity compensation in ultra-thin films of complex oxides: The case of a perovskite nickelate

    PubMed Central

    Middey, S.; Rivero, P.; Meyers, D.; Kareev, M.; Liu, X.; Cao, Y.; Freeland, J. W.; Barraza-Lopez, S.; Chakhalian, J.

    2014-01-01

    We address the fundamental issue of growth of perovskite ultra-thin films under the condition of a strong polar mismatch at the heterointerface exemplified by the growth of a correlated metal LaNiO3 on the band insulator SrTiO3 along the pseudo cubic [111] direction. While in general the metallic LaNiO3 film can effectively screen this polarity mismatch, we establish that in the ultra-thin limit, films are insulating in nature and require additional chemical and structural reconstruction to compensate for such mismatch. A combination of in-situ reflection high-energy electron diffraction recorded during the growth, X-ray diffraction, and synchrotron based resonant X-ray spectroscopy reveal the formation of a chemical phase La2Ni2O5 (Ni2+) for a few unit-cell thick films. First-principles layer-resolved calculations of the potential energy across the nominal LaNiO3/SrTiO3 interface confirm that the oxygen vacancies can efficiently reduce the electric field at the interface. PMID:25352069

  18. Polarity compensation in ultra-thin films of complex oxides: The case of a perovskite nickelate

    DOE PAGESBeta

    Middey, S.; Rivero, P.; Meyers, D.; Kareev, M.; Liu, X.; Cao, Y.; Freeland, J. W.; Barraza-Lopez, S.; Chakhalian, J.

    2014-10-29

    We address the fundamental issue of growth of perovskite ultra-thin films under the condition of a strong polar mismatch at the heterointerface exemplified by the growth of a correlated metal LaNiO3 on the band insulator SrTiO3 along the pseudo cubic [111] direction. While in general the metallic LaNiO3 film can effectively screen this polarity mismatch, we establish that in the ultra-thin limit, films are insulating in nature and require additional chemical and structural reconstruction to compensate for such mismatch. A combination of in-situ reflection high-energy electron diffraction recorded during the growth, X-ray diffraction, and synchrotron based resonant X-ray spectroscopy revealmore » the formation of a chemical phase La2Ni2O5 (Ni2+) for a few unit-cell thick films. First-principles layer-resolved calculations of the potential energy across the nominal LaNiO3/SrTiO3 interface confirm that the oxygen vacancies can efficiently reduce the electric field at the interface.« less

  19. Polarity compensation in ultra-thin films of complex oxides: The case of a perovskite nickelate

    SciTech Connect

    Middey, S.; Rivero, P.; Meyers, D.; Kareev, M.; Liu, X.; Cao, Y.; Freeland, J. W.; Barraza-Lopez, S.; Chakhalian, J.

    2014-10-29

    We address the fundamental issue of growth of perovskite ultra-thin films under the condition of a strong polar mismatch at the heterointerface exemplified by the growth of a correlated metal LaNiO3 on the band insulator SrTiO3 along the pseudo cubic [111] direction. While in general the metallic LaNiO3 film can effectively screen this polarity mismatch, we establish that in the ultra-thin limit, films are insulating in nature and require additional chemical and structural reconstruction to compensate for such mismatch. A combination of in-situ reflection high-energy electron diffraction recorded during the growth, X-ray diffraction, and synchrotron based resonant X-ray spectroscopy reveal the formation of a chemical phase La2Ni2O5 (Ni2+) for a few unit-cell thick films. First-principles layer-resolved calculations of the potential energy across the nominal LaNiO3/SrTiO3 interface confirm that the oxygen vacancies can efficiently reduce the electric field at the interface.

  20. Layed Perovskite PRBA0.5SR0.5CO205 as High Performance Cathode for Solid Oxide Fuels Using Photon Conducting Electrolyte

    SciTech Connect

    Brinkman, K.

    2010-05-05

    The layered perovskite PrBa{sub 0.5}Sr{sub 0.5}Co{sub 2}O{sub 5+{delta}} (PBSC) was investigated as a cathode material for a solid oxide fuel cell using a proton-conducting electrolyte based on BaCe{sub 0.7}Y{sub 0.2}Zr{sub 0.1}O{sub 3-{delta}} (BCYZ). The sintering conditions for the PBSC-BCYZ composite cathode were optimized resulting in the lowest area-specific resistance and apparent activation energy obtained with the cathode sintered at 1200 C for 2h. The maximum power densities of the PBSC-BCYZ/BZCY/NiO-BCYZ cell were 0.179, 0.274, 0.395, and 0.522 Wcm{sup -2} at 550, 600, 650, and 700 C, respectively with a 15{micro}m thick electrolyte. A relatively low cell interfacial polarization resistance of 0.132 {Omega}cm{sup 2} at 700 C indicated that the PBSC-BCYZ could be a good cathode candidate for intermediate temperature SOFCs with proton-conducting electrolyte.

  1. Epitaxial growth of highly-crystalline spinel ferrite thin films on perovskite substrates for all-oxide devices.

    PubMed

    Moyer, Jarrett A; Gao, Ran; Schiffer, Peter; Martin, Lane W

    2015-01-01

    The potential growth modes for epitaxial growth of Fe3O4 on SrTiO3 (001) are investigated through control of the energetics of the pulsed-laser deposition growth process (via substrate temperature and laser fluence). We find that Fe3O4 grows epitaxially in three distinct growth modes: 2D-like, island, and 3D-to-2D, the last of which is characterized by films that begin growth in an island growth mode before progressing to a 2D growth mode. Films grown in the 2D-like and 3D-to-2D growth modes are atomically flat and partially strained, while films grown in the island growth mode are terminated in islands and fully relaxed. We find that the optimal structural, transport, and magnetic properties are obtained for films grown on the 2D-like/3D-to-2D growth regime boundary. The viability for including such thin films in perovskite-based all-oxide devices is demonstrated by growing a Fe3O4/La0.7Sr0.3MnO3 spin valve epitaxially on SrTiO3. PMID:26030835

  2. Epitaxial growth of highly-crystalline spinel ferrite thin films on perovskite substrates for all-oxide devices

    PubMed Central

    Moyer, Jarrett A.; Gao, Ran; Schiffer, Peter; Martin, Lane W.

    2015-01-01

    The potential growth modes for epitaxial growth of Fe3O4 on SrTiO3 (001) are investigated through control of the energetics of the pulsed-laser deposition growth process (via substrate temperature and laser fluence). We find that Fe3O4 grows epitaxially in three distinct growth modes: 2D-like, island, and 3D-to-2D, the last of which is characterized by films that begin growth in an island growth mode before progressing to a 2D growth mode. Films grown in the 2D-like and 3D-to-2D growth modes are atomically flat and partially strained, while films grown in the island growth mode are terminated in islands and fully relaxed. We find that the optimal structural, transport, and magnetic properties are obtained for films grown on the 2D-like/3D-to-2D growth regime boundary. The viability for including such thin films in perovskite-based all-oxide devices is demonstrated by growing a Fe3O4/La0.7Sr0.3MnO3 spin valve epitaxially on SrTiO3. PMID:26030835

  3. An A-site-deficient perovskite offers high activity and stability for low-temperature solid-oxide fuel cells.

    PubMed

    Zhu, Yinlong; Chen, Zhi-Gang; Zhou, Wei; Jiang, Shanshan; Zou, Jin; Shao, Zongping

    2013-12-01

    Solid oxide fuel cells (SOFCs) directly convert fossil and/or renewable fuels into electricity and/or high-quality heat in an environmentally friendly way. However, high operating temperatures result in high cost and material issues, which have limited the commercialization of SOFCs. To lower their operating temperatures, highly active and stable cathodes are required to maintain a reasonable power output. Here, we report a layer-structured A-site deficient perovskite Sr0.95 Nb0.1 Co0.9 O3-δ (SNC0.95) prepared by solid-state reactions that shows not only high activity towards the oxygen reduction reaction (ORR) at operating temperatures below 600 °C, but also offers excellent structural stability and compatibility, and improved CO2 resistivity. An anode-supported fuel cell with SNC0.95 cathode delivers a peak power density as high as 1016 mW cm(-2) with an electrode-area-specific resistance of 0.052 Ω cm(2) at 500 °C. PMID:24155098

  4. Electrical transport mechanism in a newly synthesized rare earth double perovskite oxide Sr2CeTaO6

    NASA Astrophysics Data System (ADS)

    Bharti, Chandrahas; Chanda, Sadhan; Sinha, T. P.

    2013-01-01

    A rare earth double perovskite oxide strontium cerium tantalate, Sr2CeTaO6 (SCT) is synthesized by the solid state reaction technique for the first time. The determination of lattice parameters and the identification of phase are carried out by the Rietveld refinement method (RRM) using the Fullprof program in the space group P21/n (C52h). A structure of SCT is obtained from RRM. The bond angle and bond length are calculated and listed in Table 1 for SCT. A small amount of impurity of CeO2 is found in the refinement with space group Fm3m. The scanning electron micrograph shows the average grain size ∼2 μm. The ac electrical property is investigated in the temperature range from 303 to 703 K and in the frequency range from 0.1 kHz to 1 MHz using impedance spectroscopy. The relaxation mechanism of SCT is explained in detail by fitting experimental impedance and electric modulus data with the modified Debye (Cole-Cole) model. The frequency-dependent electrical data are analyzed in the framework of the conductivity and modulus formalisms. The σac data are fitted with Jonscher's universal power law. The dc conductivity (σdc) (calculated from σac) follows an Arrhenius law with the estimated conduction activation energy =0.78 eV. The scaling behavior of imaginary part of electrical impedance (Z″) shows that the relaxation describes the same mechanism at various temperatures.

  5. Electrical properties of double perovskite oxide Sr2LaSbO6: An impedance spectroscopic study

    NASA Astrophysics Data System (ADS)

    Dutta, Alo; Kumari, Premlata; Sinha, T. P.

    2015-09-01

    The Rietveld refinement of the room temperature x-ray diffraction pattern of double perovskite oxide, Sr2LaSbO6 (SLS) synthesized by the solid-state reaction technique shows monoclinic phase with P21/ n symmetry, which is substantiated by the Raman spectrum of the sample. The dielectric relaxation of SLS is investigated in the temperature range from 30°C to 300°C and in the frequency range from 50 Hz to 1 MHz. The Cole-Cole model is used to explain the dielectric relaxation of SLS. The most probable relaxation frequencies at various temperatures are found to obey the Arrhenius law with an activation energy of 0.36 eV, which indicates that the polaron hopping plays the main role in the dielectric relaxation of SLS. The complex impedance plane plots are analyzed by an electrical equivalent circuit consisting of a resistance and a constant phase element. The frequency dependent conductivity spectra obey the power law. [Figure not available: see fulltext.

  6. High-performance CH3NH3PbI3 perovskite solar cells fabricated under ambient conditions with high relative humidity

    NASA Astrophysics Data System (ADS)

    Lei, Binglong; Obiozo Eze, Vincent; Mori, Tatsuo

    2015-10-01

    Hygroscopic perovskite solar cells are commonly fabricated under conditions of inert atmosphere or low relative humidity (RH). To generate high-performance perovskite light-absorbing layers for super power conversion efficiency (PCE), we fabricated CH3NH3PbI3 solar cells under ambient conditions (RH = 42-48%) by a flowing gas directly from high-RH air. The primary advantage of this technique, together with the casting of a hot solution and quick conduction, enabled us to achieve the highest and average PCEs of 16.32 and 14.27% respectively, with an extremely small deviation of 0.49%. Our research will be of significance for fabricating highly efficient and reproducible perovskite photovoltaics.

  7. Mixed Metal Oxides with the Structure of Perovskite for Anticorrosion Organic Coatings

    NASA Astrophysics Data System (ADS)

    Kantorová, M.; Veselý, D.

    Mixed metal oxides pigments of TiO2.ZnO, 2TiO2.ZnO, Zn2TiO4, MgTiO3, CaTiO3, TiO2.ZnO.MgO, and TiO2.ZnO.SrO were synthesized from corresponding oxides or carbonates at high temperature. The obtained metal mixed oxides were characterized by means of X-fray diffraction analysis, measurement of particle sizes and scanning electron microscopy. The synthesized metal mixed oxides were used to produce epoxy-ester coatings with PVC = 10% for a synthesized pigment. The coatings were tested for physical-mechanical properties and in corrosion atmospheres. The results of corrosion tests were compared with standard alumino zinc phosphomolybdate.

  8. Using a low-temperature carbon electrode for preparing hole-conductor-free perovskite heterojunction solar cells under high relative humidity

    NASA Astrophysics Data System (ADS)

    Liu, Zhiyong; Shi, Tielin; Tang, Zirong; Sun, Bo; Liao, Guanglan

    2016-03-01

    We demonstrate the application of a low-temperature carbon counter electrode with good flexibility and high conductivity in fabricating perovskite solar cells. A modified two-step method was used for the deposition of nanocrystalline CH3NH3PbI3 under high relative humidity. The carbon counter electrode was printed on a perovskite layer directly, with different sizes of graphite powder being employed. The interfacial charge transfer and transport in solar cells were investigated through photoluminescence and impedance measurements. We find that the existence of nano-graphite powder in the electrode has a noticeable influence on the back contact and cell performance. The prepared devices of hole-conductor-free perovskite heterojunction solar cells without encapsulation exhibit advantageous stability in air in the dark, with the optimal power conversion efficiency reaching 6.88%. This carbon counter electrode has the features of low-cost and low-temperature preparation, giving it potential for application in the large-scale flexible fabrication of perovskite solar cells in the future.We demonstrate the application of a low-temperature carbon counter electrode with good flexibility and high conductivity in fabricating perovskite solar cells. A modified two-step method was used for the deposition of nanocrystalline CH3NH3PbI3 under high relative humidity. The carbon counter electrode was printed on a perovskite layer directly, with different sizes of graphite powder being employed. The interfacial charge transfer and transport in solar cells were investigated through photoluminescence and impedance measurements. We find that the existence of nano-graphite powder in the electrode has a noticeable influence on the back contact and cell performance. The prepared devices of hole-conductor-free perovskite heterojunction solar cells without encapsulation exhibit advantageous stability in air in the dark, with the optimal power conversion efficiency reaching 6.88%. This carbon

  9. Design Insights for Tuning the Electrocatalytic Activity of Perovskite Oxides for the Oxygen Evolution Reaction

    SciTech Connect

    Malkhandi, S; Trinh, P; Manohar, AK; Manivannan, A; Balasubramanian, M; Prakash, GKS; Narayanan, SR

    2015-04-16

    Rechargeable metal-air batteries and water electrolyzers based on aqueous alkaline electrolytes hold the potential to be sustainable solutions to address the challenge of storing large amounts of electrical energy generated from solar and wind resources. For these batteries and electrolyzers to be economically viable, it is essential to have efficient, durable, and inexpensive electrocatalysts for the oxygen evolution reaction. In this article, we describe new insights for predicting and tuning the activity of inexpensive transition metal oxides for designing efficient and inexpensive electrocatalysts. We have focused on understanding the factors determining the electrocatalytic activity for oxygen evolution in a strong alkaline medium. To this end, we have conducted a systematic investigation of nanophase calcium-doped lanthanum cobalt manganese oxide, an example of a mixed metal oxide that can be tuned for its electrocatalytic activity by varying the transition metal composition. Using X-ray absorption spectroscopy (XANES), X-ray photoelectron spectroscopy (XPS), electrochemical polarization experiments, and analysis of mechanisms, we have identified the key determinants of electrocatalytic activity. We have found that the Tafel slopes are determined by the oxidation states and the bond energy of the surface intermediates of Mn-OH and Co-OH bonds while the catalytic activity increased with the average d-electron occupancy of the sigma* orbital of the M-OH bond. We anticipate that such understanding will be very useful in predicting the behavior of other transition metal oxide catalysts.

  10. Purple photochromism in Sr2SnO4:Eu3+ with layered perovskite-related structure

    NASA Astrophysics Data System (ADS)

    Kamimura, Sunao; Yamada, Hiroshi; Xu, Chao-Nan

    2013-01-01

    We report photochromism (PC) in Sr2SnO4:Eu3+ with layered perovskite-related structure. The Sr2SnO4:Eu3+ turned purple upon irradiation with UV light (λ < 350 nm), and the colored Sr2SnO4:Eu3+ returned to its initial colorless state when visible light (λ = 400-700 nm) was irradiated. Furthermore, the PC was strongly dependent on the firing temperature; purple color upon UV irradiation can be enhanced by increasing the firing temperature, which was attributed to an increase of the Sr vacancies in the host lattice from the results of crystal structure analysis. This suggests that controlling the lattice defect plays an important role for enhancing the PC performance.

  11. Room temperature oxidative intercalation with chalcogen hydrides: Two-step method for the formation of alkali-metal chalcogenide arrays within layered perovskites

    SciTech Connect

    Ranmohotti, K.G. Sanjaya; Montasserasadi, M. Dariush; Choi, Jonglak; Yao, Yuan; Mohanty, Debasish; Josepha, Elisha A.; Adireddy, Shiva; Caruntu, Gabriel; Wiley, John B.

    2012-06-15

    Highlights: ► Topochemical reactions involving intercalation allow construction of metal chalcogenide arrays within perovskite hosts. ► Gaseous chalcogen hydrides serve as effect reactants for intercalation of sulfur and selenium. ► New compounds prepared by a two-step intercalation strategy are presented. -- Abstract: A two-step topochemical reaction strategy utilizing oxidative intercalation with gaseous chalcogen hydrides is presented. Initially, the Dion-Jacobson-type layered perovskite, RbLaNb{sub 2}O{sub 7}, is intercalated reductively with rubidium metal to make the Ruddlesden-Popper-type layered perovskite, Rb{sub 2}LaNb{sub 2}O{sub 7}. This compound is then reacted at room-temperature with in situ generated H{sub 2}S gas to create Rb-S layers within the perovskite host. Rietveld refinement of X-ray powder diffraction data (tetragonal, a = 3.8998(2) Å, c = 15.256(1) Å; space group P4/mmm) shows the compound to be isostructural with (Rb{sub 2}Cl)LaNb{sub 2}O{sub 7} where the sulfide resides on a cubic interlayer site surrounded by rubidium ions. The mass increase seen on sulfur intercalation and the refined S site occupation factor (∼0.8) of the product indicate a higher sulfur content than expected for S{sup 2−} alone. This combined with the Raman studies, which show evidence for an H-S stretch, indicate that a significant fraction of the intercalated sulfide exists as hydrogen sulfide ion. Intercalation reactions with H{sub 2}Se{sub (g)} were also carried out and appear to produce an isostructural selenide compound. The utilization of such gaseous hydride reagents could significantly expand multistep topochemistry to a larger number of intercalants.

  12. Perovskite electrodes and method of making the same

    DOEpatents

    Seabaugh, Matthew M.; Swartz, Scott L.

    2009-09-22

    The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

  13. Perovskite electrodes and method of making the same

    SciTech Connect

    Seabaugh, Matthew M.; Swartz, Scott L.

    2005-09-20

    The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

  14. Double Perovskite Anode Materials Sr2MMoO6 (M = Co, Ni) for Solid-Oxide Fuel Cells

    SciTech Connect

    Huang, Y.; Liang, G; Croft, M; Lehtimaki, M; Karppinen, M; Goodenough, J

    2009-01-01

    Double-perovskites Sr2MMoO6 (M = Co, Ni) have been investigated as anode materials for a solid oxide fuel cell. At room temperature, both Sr2CoMoO6 and Sr2NiMoO6 are tetragonal (I4/m). X-ray absorption spectroscopy confirmed the presence of Co2+/Mo6+ and Ni2+/Mo6+ pairs in the oxygen-stoichiometric compounds. The samples contain a limited concentration of oxygen vacancies in the reducing atmospheres at an anode. Reoxidation is facile below 600 C; they become antiferromagnetic at low temperatures TN = 37 and 80 K for M = Co and Ni, respectively. As an anode with a 300 em thick La0.8Sr0.2Ga0.83Mg0.17O2.815 electrolyte and SrFe0.2Co0.8O3-d as a cathode, Sr2CoMoO6 exhibited maximum power densities of 735 mW/cm2 in H2 and 527 mW/cm2 in wet CH4 at 800 C; Sr2NiMoO6 shows a notable power output only in dry CH4. The high performance of Sr2CoMoO6 in wet CH4 may be due to its catalytic effect on steam reforming of methane, but some degradation of the structure that occurred in CH4 obscures identification of the catalytic reaction processes at the surface. However, the stronger octahedral-site preference of Ni2+ versus Co2+ can account for the lower performance of the M = Ni anode.

  15. Synergistic bifunctional catalyst design based on perovskite oxide nanoparticles and intertwined carbon nanotubes for rechargeable zinc-air battery applications.

    PubMed

    Lee, Dong Un; Park, Hey Woong; Park, Moon Gyu; Ismayilov, Vugar; Chen, Zhongwei

    2015-01-14

    Advanced morphology of intertwined core-corona structured bifunctional catalyst (IT-CCBC) is introduced where perovskite lanthanum nickel oxide nanoparticles (LaNiO3 NP) are encapsulated by high surface area network of nitrogen-doped carbon nanotubes (NCNT) to produce highly active and durable bifunctional catalyst for rechargeable metal-air battery applications. The unique composite morphology of IT-CCBC not only enhances the charge transport property by providing rapid electron-conduction pathway but also facilitates in diffusion of hydroxyl and oxygen reactants through the highly porous framework. Confirmed by electrochemical half-cell testing, IT-CCBC in fact exhibits very strong synergy between LaNiO3 NP and NCNT demonstrating bifunctionality with significantly improved catalytic activities of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Furthermore, when compared to the state-of-art catalysts, IT-CCBC outperforms Pt/C and Ir/C in terms of ORR and OER, respectively, and shows improved electrochemical stability compared to them after cycle degradation testing. The practicality of the catalyst is corroborated by testing in a realistic rechargeable zinc-air battery utilizing atmospheric air in ambient conditions, where IT-CCBC demonstrates superior charge and discharge voltages and long-term cycle stability with virtually no battery voltage fading. These improved electrochemical properties of the catalyst are attributed to the nanosized dimensions of LaNiO3 NP controlled by simple hydrothermal technique, which enables prolific growth of and encapsulation by highly porous NCNT network. The excellent electrochemical results presented in this study highlight IT-CCBC as highly efficient and commercially viable bifunctional catalyst for rechargeable metal-air battery applications. PMID:25494945

  16. Screened Hybrid Exact Exchange Schemes to Adsorption Energies on Perovskite Oxides

    NASA Astrophysics Data System (ADS)

    Santos, Elton; Vojvodic, Aleksandra; Norskov, Jens K.

    The bond formation between an oxide surface and oxygen, which is one of the important intermediates for oxygen evolution reaction, is investigated using hybrid functionals. We show that there exists a linear correlation between the adsorption energies of oxygen on LaMO3 (M =Sc-Cu) oxides at hybrid calculations to those computed using semilocal density functionals through the magnetic properties of the bulk phase. The energetics of the spin-polarized surfaces follow the same trend as corresponding bulk systems, which can be treated at a much lower computational cost. The difference in adsorption energy due to magnetism is linearly correlated to the magnetization energy of bulk, i.e., the energy difference between the spin-polarized and the non spin-polarized solutions. This suggests that one could estimate the correction to the semilocal density functional adsorption energies directly from the hybrid bulk magnetization energy.

  17. The double perovskite oxide Sr2CrMoO(6-δ) as an efficient electrocatalyst for rechargeable lithium air batteries.

    PubMed

    Ma, Zhong; Yuan, Xianxia; Li, Lin; Ma, Zi-Feng

    2014-12-01

    A double perovskite oxide Sr2CrMoO6-δ (SCM), synthesized using the sol-gel and annealing method with the assistance of citric acid and ethylene diamine tetraacetic acid, was investigated for the first time as an efficient catalyst for rechargeable lithium air batteries. The SCM cathode enables higher specific capacity, lower overpotential and a much better cyclability compared to the pure Super P electrode owing to its excellent electrocatalytic activity towards the formation/decomposition of Li2O2. PMID:25325080

  18. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles.

    PubMed

    Suntivich, Jin; May, Kevin J; Gasteiger, Hubert A; Goodenough, John B; Shao-Horn, Yang

    2011-12-01

    The efficiency of many energy storage technologies, such as rechargeable metal-air batteries and hydrogen production from water splitting, is limited by the slow kinetics of the oxygen evolution reaction (OER). We found that Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than that of the state-of-the-art iridium oxide catalyst in alkaline media. The high activity of BSCF was predicted from a design principle established by systematic examination of more than 10 transition metal oxides, which showed that the intrinsic OER activity exhibits a volcano-shaped dependence on the occupancy of the 3d electron with an e(g) symmetry of surface transition metal cations in an oxide. The peak OER activity was predicted to be at an e(g) occupancy close to unity, with high covalency of transition metal-oxygen bonds. PMID:22033519

  19. A High-Performing Sulfur-Tolerant and Redox-Stable Layered Perovskite Anode for Direct Hydrocarbon Solid Oxide Fuel Cells.

    PubMed

    Ding, Hanping; Tao, Zetian; Liu, Shun; Zhang, Jiujun

    2015-01-01

    Development of alternative ceramic oxide anode materials is a key step for direct hydrocarbon solid oxide fuel cells (SOFCs). Several lanthanide based layered perovskite-structured oxides demonstrate outstanding oxygen diffusion rate, favorable electronic conductivity, and good oxygen surface exchange kinetics, owing to A-site ordered structure in which lanthanide and alkali-earth ions occupy alternate (001) layers and oxygen vacancies are mainly located in [LnOx] planes. Here we report a nickel-free cation deficient layered perovskite, (PrBa)0.95(Fe0.9Mo0.1)2O5 + δ (PBFM), for SOFC anode, and this anode shows an outstanding performance with high resistance against both carbon build-up and sulfur poisoning in hydrocarbon fuels. At 800 °C, the layered PBFM showed high electrical conductivity of 59.2 S cm(-1) in 5% H2 and peak power densities of 1.72 and 0.54 W cm(-2) using H2 and CH4 as fuel, respectively. The cell exhibits a very stable performance under a constant current load of 1.0 A cm(-2). To our best knowledge, this is the highest performance of ceramic anodes operated in methane. In addition, the anode is structurally stable at various fuel and temperature conditions, suggesting that it is a feasible material candidate for high-performing SOFC anode. PMID:26648509

  20. A High-Performing Sulfur-Tolerant and Redox-Stable Layered Perovskite Anode for Direct Hydrocarbon Solid Oxide Fuel Cells

    PubMed Central

    Ding, Hanping; Tao, Zetian; Liu, Shun; Zhang, Jiujun

    2015-01-01

    Development of alternative ceramic oxide anode materials is a key step for direct hydrocarbon solid oxide fuel cells (SOFCs). Several lanthanide based layered perovskite-structured oxides demonstrate outstanding oxygen diffusion rate, favorable electronic conductivity, and good oxygen surface exchange kinetics, owing to A-site ordered structure in which lanthanide and alkali-earth ions occupy alternate (001) layers and oxygen vacancies are mainly located in [LnOx] planes. Here we report a nickel-free cation deficient layered perovskite, (PrBa)0.95(Fe0.9Mo0.1)2O5 + δ (PBFM), for SOFC anode, and this anode shows an outstanding performance with high resistance against both carbon build-up and sulfur poisoning in hydrocarbon fuels. At 800 °C, the layered PBFM showed high electrical conductivity of 59.2 S cm−1 in 5% H2 and peak power densities of 1.72 and 0.54 W cm−2 using H2 and CH4 as fuel, respectively. The cell exhibits a very stable performance under a constant current load of 1.0 A cm−2. To our best knowledge, this is the highest performance of ceramic anodes operated in methane. In addition, the anode is structurally stable at various fuel and temperature conditions, suggesting that it is a feasible material candidate for high-performing SOFC anode. PMID:26648509

  1. A High-Performing Sulfur-Tolerant and Redox-Stable Layered Perovskite Anode for Direct Hydrocarbon Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Ding, Hanping; Tao, Zetian; Liu, Shun; Zhang, Jiujun

    2015-12-01

    Development of alternative ceramic oxide anode materials is a key step for direct hydrocarbon solid oxide fuel cells (SOFCs). Several lanthanide based layered perovskite-structured oxides demonstrate outstanding oxygen diffusion rate, favorable electronic conductivity, and good oxygen surface exchange kinetics, owing to A-site ordered structure in which lanthanide and alkali-earth ions occupy alternate (001) layers and oxygen vacancies are mainly located in [LnOx] planes. Here we report a nickel-free cation deficient layered perovskite, (PrBa)0.95(Fe0.9Mo0.1)2O5 + δ (PBFM), for SOFC anode, and this anode shows an outstanding performance with high resistance against both carbon build-up and sulfur poisoning in hydrocarbon fuels. At 800 °C, the layered PBFM showed high electrical conductivity of 59.2 S cm-1 in 5% H2 and peak power densities of 1.72 and 0.54 W cm-2 using H2 and CH4 as fuel, respectively. The cell exhibits a very stable performance under a constant current load of 1.0 A cm-2. To our best knowledge, this is the highest performance of ceramic anodes operated in methane. In addition, the anode is structurally stable at various fuel and temperature conditions, suggesting that it is a feasible material candidate for high-performing SOFC anode.

  2. Efficient and stable iron based perovskite La0.9Ca0.1Fe0.9Nb0.1O3-δ anode material for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kong, Xiaowei; Zhou, Xiaoliang; Tian, Yu; Wu, Xiaoyan; Zhang, Jun; Zuo, Wei; Gong, Xiaobo; Guo, Zhanhu

    2016-06-01

    A novel La0.9Ca0.1Fe0.9Nb0.1O3-δ (LCFNb) perovskite for solid oxide fuel cells (SOFCs) anode is prepared by means of the citrate-nitrate route and composited with Ce0.8Sm0.2O1.9 (SDC) by impregnation method to form nano-scaled LCFNb/SDC anode catalytic layers. The single cells with LCFNb and LCFNb/SDC impregnated anodes both achieve relatively high power output with maximum power densities (MPDs) reaching up to 610, 823 mW·cm-2 in H2 at 800 °C, respectively, presenting a high potential of LCFNb for use as SOFCs anode. The power outputs of the single cells with LCFNb/SDC composite anode in CO and syngas (COsbnd H2 mixture) are almost identical to that in H2 at each testing temperature. This composite anode also presents excellent durability in both H2 and CO for as long as 50 h, showing desirable anti-reduction and carbon deposition resistance abilities. Besides, the cell output is stable in 100 ppm H2Ssbnd H2 atmospheres for 20 h at a current density of 600 mA·cm-2 with negligible sulfur accumulation on the anode surface. Hence, a novel iron based perovskite LCFNb anode with remarkable cell performance, carbon deposition resistance and sulfur poisoning tolerance for SOFCs is successfully obtained.

  3. Efficient and stable iron based perovskite La0.9Ca0.1Fe0.9Nb0.1O3-δ anode material for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kong, Xiaowei; Zhou, Xiaoliang; Tian, Yu; Wu, Xiaoyan; Zhang, Jun; Zuo, Wei; Gong, Xiaobo; Guo, Zhanhu

    2016-06-01

    A novel La0.9Ca0.1Fe0.9Nb0.1O3-δ (LCFNb) perovskite for solid oxide fuel cells (SOFCs) anode is prepared by means of the citrate-nitrate route and composited with Ce0.8Sm0.2O1.9 (SDC) by impregnation method to form nano-scaled LCFNb/SDC anode catalytic layers. The single cells with LCFNb and LCFNb/SDC impregnated anodes both achieve relatively high power output with maximum power densities (MPDs) reaching up to 610, 823 mW·cm-2 in H2 at 800 °C, respectively, presenting a high potential of LCFNb for use as SOFCs anode. The power outputs of the single cells with LCFNb/SDC composite anode in CO and syngas (COsbnd H2 mixture) are almost identical to that in H2 at each testing temperature. This composite anode also presents excellent durability in both H2 and CO for as long as 50 h, showing desirable anti-reduction and carbon deposition resistance abilities. Besides, the cell output is stable in 100 ppm H2Ssbnd H2 atmospheres for 20 h at a current density of 600 mA·cm-2 with negligible sulfur accumulation on the anode surface. Hence, a novel iron based perovskite LCFNb anode with remarkable cell performance, carbon deposition resistance and sulfur poisoning tolerance for SOFCs is successfully obtained.

  4. Cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    DOEpatents

    Jacobson, Allan J; Wang, Shuangyan; Kim, Gun Tae

    2014-01-28

    Novel cathode, electrolyte and oxygen separation materials are disclosed that operate at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes based on oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  5. Electronic structure studies of high-T/sub c/ perovskites and related materials

    SciTech Connect

    Wachs, A.L.; Turchi, P.E.A.; Kaiser, J.H.; West, R.N.; Howell, R.H.; Jean, Y.C.; Merkle, K.L.; Revcolevschi, A.; Fluss, M.J.

    1988-10-01

    We have performed 2D-ACPAR measurements on La/sub 2/CuO/sub 4/ and NiO. The ACPAR distributions were very isotropic, with small anisotropic deviations on the order of 10% of the total counts. It was not possible to clearly discern a Fermi surface in either set of data, nor was it possible to identify any features with the symmetry and periodicity of the crystalline reciprocal lattices. Attempts to model both systems by starting with a localized ionic picture and allowing covalency overlap to take place among the atoms comprising an isolated metal atom-oxygen octahedral cluster have proven successful. This result suggests that it might be appropriate for analyses of the electronic structure for high-T/sub c/ perovskites to begin with the ansatz of localized electronic states. This approach has worked very well for the transition-metal monoxides. Finally, application of the LCW formalism to data from both systems yields a result very close to filled-band behavior. We believe the deviations from the latter are significant, but that they originate from positronic wavefunction mixing of the electronic states and not from a Fermi surface. 9 refs., 3 figs.

  6. Using a low-temperature carbon electrode for preparing hole-conductor-free perovskite heterojunction solar cells under high relative humidity.

    PubMed

    Liu, Zhiyong; Shi, Tielin; Tang, Zirong; Sun, Bo; Liao, Guanglan

    2016-04-01

    We demonstrate the application of a low-temperature carbon counter electrode with good flexibility and high conductivity in fabricating perovskite solar cells. A modified two-step method was used for the deposition of nanocrystalline CH3NH3PbI3 under high relative humidity. The carbon counter electrode was printed on a perovskite layer directly, with different sizes of graphite powder being employed. The interfacial charge transfer and transport in solar cells were investigated through photoluminescence and impedance measurements. We find that the existence of nano-graphite powder in the electrode has a noticeable influence on the back contact and cell performance. The prepared devices of hole-conductor-free perovskite heterojunction solar cells without encapsulation exhibit advantageous stability in air in the dark, with the optimal power conversion efficiency reaching 6.88%. This carbon counter electrode has the features of low-cost and low-temperature preparation, giving it potential for application in the large-scale flexible fabrication of perovskite solar cells in the future. PMID:26660267

  7. Low-temperature solution-processed tin oxide as an alternative electron transporting layer for efficient perovskite solar cells.

    PubMed

    Ke, Weijun; Fang, Guojia; Liu, Qin; Xiong, Liangbin; Qin, Pingli; Tao, Hong; Wang, Jing; Lei, Hongwei; Li, Borui; Wan, Jiawei; Yang, Guang; Yan, Yanfa

    2015-06-01

    Lead halide perovskite solar cells with the high efficiencies typically use high-temperature processed TiO2 as the electron transporting layers (ETLs). Here, we demonstrate that low-temperature solution-processed nanocrystalline SnO2 can be an excellent alternative ETL material for efficient perovskite solar cells. Our best-performing planar cell using such a SnO2 ETL has achieved an average efficiency of 16.02%, obtained from efficiencies measured from both reverse and forward voltage scans. The outstanding performance of SnO2 ETLs is attributed to the excellent properties of nanocrystalline SnO2 films, such as good antireflection, suitable band edge positions, and high electron mobility. The simple low-temperature process is compatible with the roll-to-roll manufacturing of low-cost perovskite solar cells on flexible substrates. PMID:25987132

  8. Proton conducting intermediate-temperature solid oxide fuel cells using new perovskite type cathodes

    NASA Astrophysics Data System (ADS)

    Li, Meiling; Ni, Meng; Su, Feng; Xia, Changrong

    2014-08-01

    Sr2Fe1.5Mo0.5O6-δ (SFM) is proposed as the electrodes for symmetric solid oxide fuel cells (SOFCs) based on oxygen-ion conducting electrolytes. In this work SFM is investigated as the cathodes for SOFCs with proton conducting BaZr0.1Ce0.7Y0.2O3-δ (BZCY) electrolyte. SFM is synthesized with a combined glycine and citric acid method and shows very good chemical compatibility with BZCY under 1100 °C. Anode-supported single cell (Ni-BZCY anode, BZCY electrolyte, and SFM-BZCY cathode) and symmetrical fuel cell (SFM-BZCY electrodes and BZCY electrolyte) are fabricated and their performances are measured. Impedance spectroscopy on symmetrical cell consisting of BZCY electrolyte and SFM-BZCY electrodes demonstrates low area-specific interfacial polarization resistance Rp, and the lowest Rp, 0.088 Ω cm2 is achieved at 800 °C when cathode is sintered at 900 °C for 2 h. The single fuel cell achieves 396 mW cm-2 at 800 °C in wet H2 (3 vol% H2O) at a co-sintering temperature of 1000 °C. This study demonstrates the potential of SFM-BZCY as a cathode material in proton-conducting intermediate-temperature solid oxide fuel cells.

  9. Oxidative Stress Related Diseases in Newborns.

    PubMed

    Ozsurekci, Yasemin; Aykac, Kubra

    2016-01-01

    We review oxidative stress-related newborn disease and the mechanism of oxidative damage. In addition, we outline diagnostic and therapeutic strategies and future directions. Many reports have defined oxidative stress as an imbalance between an enhanced reactive oxygen/nitrogen species and the lack of protective ability of antioxidants. From that point of view, free radical-induced damage caused by oxidative stress seems to be a probable contributing factor to the pathogenesis of many newborn diseases, such as respiratory distress syndrome, bronchopulmonary dysplasia, periventricular leukomalacia, necrotizing enterocolitis, patent ductus arteriosus, and retinopathy of prematurity. We share the hope that the new understanding of the concept of oxidative stress and its relation to newborn diseases that has been made possible by new diagnostic techniques will throw light on the treatment of those diseases. PMID:27403229

  10. Oxidative Stress Related Diseases in Newborns

    PubMed Central

    Aykac, Kubra

    2016-01-01

    We review oxidative stress-related newborn disease and the mechanism of oxidative damage. In addition, we outline diagnostic and therapeutic strategies and future directions. Many reports have defined oxidative stress as an imbalance between an enhanced reactive oxygen/nitrogen species and the lack of protective ability of antioxidants. From that point of view, free radical-induced damage caused by oxidative stress seems to be a probable contributing factor to the pathogenesis of many newborn diseases, such as respiratory distress syndrome, bronchopulmonary dysplasia, periventricular leukomalacia, necrotizing enterocolitis, patent ductus arteriosus, and retinopathy of prematurity. We share the hope that the new understanding of the concept of oxidative stress and its relation to newborn diseases that has been made possible by new diagnostic techniques will throw light on the treatment of those diseases. PMID:27403229

  11. The Post-Perovskite Transition and Mineralogical Changes in the Chemically Heterogeneous Lower Mantle

    NASA Astrophysics Data System (ADS)

    Shim, S. H. D.; Ye, Y.; Grocholski, B.; Xu, S.; Morgan, D.; Zhao, J.; Alp, E. E.

    2014-12-01

    The discovery of the post-perovskite transition in 2004 has made huge impact on our understanding on the structures and dynamics of the lowermost mantle. For the last 10 years, the post-perovskite transition has been related to major seismic structures in the region, including the D'' discontinuity, the D'' anisotropy, and the anti-correlation between the bulk sound speed and shear wave velocity. Whereas the post-perovskite phase appeared to provide a coherent framework to explain many of the major structures, more recent mineral physics studies have revealed that the compositional effects can be significant. High-resolution seismic imaging studies have reported complex structures which cannot be explained by the post-perovskite transition in chemically simple systems. Furthermore, recently proposed mineralogical changes in the lower mantle will affect the properties of post-perovskite and may provide alternative explanations for some seismic structures. In this talk, we will discuss the post-perovskite phase transition and other phase transitions in chemical heterogeneities in the lowermost mantle and their importance in understanding seismic structures. We will also report new data on the spin and oxidation state of iron in mantle silicate which can affect the post-perovskite transition.

  12. Insights into cationic ordering in Re-based double perovskite oxides

    PubMed Central

    Lim, Tae-Won; Kim, Sung-Dae; Sung, Kil-Dong; Rhyim, Young-Mok; Jeen, Hyungjeen; Yun, Jondo; Kim, Kwang-Ho; Song, Ki-Myung; Lee, Seongsu; Chung, Sung-Yoon; Choi, Minseok; Choi, Si-Young

    2016-01-01

    Cationic ordering in Sr2FeReO6 (SFRO) and Sr2CrReO6 (SCRO) is investigated using magnetic property measurement, atomic-scale imaging, and first-principles calculations. We find that the nature of cationic ordering strongly depends on the host oxides, although they have the same crystal symmetry and chemical formula. Firstly, adding Re is effective to enhance the cationic ordering in SFRO, but makes it worse in SCRO. Secondly, the microscopic structure of antisite (AS) defects, associated with the level of cationic ordering, is also distinguishable; the AS defects in SFRO are clustered in the form of an antiphase-boundary-like feature, while they are randomly scattered in SCRO. Interestingly, we observe that the clustered AS defects deteriorate the ferromagnetism more than the scattered defects. Our findings elevate the importance of the AS defect configuration as well as the amount of defects in terms of magnetic property. PMID:26804747

  13. Insights into cationic ordering in Re-based double perovskite oxides.

    PubMed

    Lim, Tae-Won; Kim, Sung-Dae; Sung, Kil-Dong; Rhyim, Young-Mok; Jeen, Hyungjeen; Yun, Jondo; Kim, Kwang-Ho; Song, Ki-Myung; Lee, Seongsu; Chung, Sung-Yoon; Choi, Minseok; Choi, Si-Young

    2016-01-01

    Cationic ordering in Sr2FeReO6 (SFRO) and Sr2CrReO6 (SCRO) is investigated using magnetic property measurement, atomic-scale imaging, and first-principles calculations. We find that the nature of cationic ordering strongly depends on the host oxides, although they have the same crystal symmetry and chemical formula. Firstly, adding Re is effective to enhance the cationic ordering in SFRO, but makes it worse in SCRO. Secondly, the microscopic structure of antisite (AS) defects, associated with the level of cationic ordering, is also distinguishable; the AS defects in SFRO are clustered in the form of an antiphase-boundary-like feature, while they are randomly scattered in SCRO. Interestingly, we observe that the clustered AS defects deteriorate the ferromagnetism more than the scattered defects. Our findings elevate the importance of the AS defect configuration as well as the amount of defects in terms of magnetic property. PMID:26804747

  14. Oxygen rocking aqueous batteries utilizing reversible topotactic oxygen insertion/extraction in iron-based perovskite oxides Ca1–xLaxFeO3−δ

    PubMed Central

    Hibino, Mitsuhiro; Kimura, Takeshi; Suga, Yosuke; Kudo, Tetsuichi; Mizuno, Noritaka

    2012-01-01

    Developments of large-scale energy storages with not only low cost and high safety but also abundant metals are significantly demanded. While lithium ion batteries are the most successful method, they cannot satisfy all conditions. Here we show the principle of novel lithium-free secondary oxygen rocking aqueous batteries, in which oxygen shuttles between the cathode and anode composed of iron-based perovskite-related oxides Ca0.5La0.5FeOz (2.5 ≤ z ≤ 2.75 and 2.75 ≤ z ≤ 3.0). Compound Ca0.5La0.5FeOz can undergo two kinds of reduction and reoxidation of Fe4+/Fe3+ and Fe3+/Fe2+, that are accompanied by reversible and repeatable topotactic oxygen extraction and reinsertion during discharge and charge processes. PMID:22924108

  15. Preparation and electrochemical properties of urchin-like La0.8Sr0.2MnO3 perovskite oxide as a bifunctional catalyst for oxygen reduction and oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Jin, Chao; Cao, Xuecheng; Zhang, Liya; Zhang, Cong; Yang, Ruizhi

    2013-11-01

    An urchin-like La0.8Sr0.2MnO3 (LSM) perovskite oxide has been synthesized through a co-precipitation method with urea as a precipitator, and characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET analysis. SEM results show that a micro/nanocomposite with an urchin-like morphology has been obtained. The as-synthesized LSM perovskite oxide has a high specific surface area of 48 m2 g-1. The catalytic activity of the oxide for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in 0.1 M KOH solution has been studied by using a rotating-ring-disk electrode (RRDE). In the ORR test, a maximum cathodic current density of 5.2 mA cm-2 at -1.0 V (vs. Ag/AgCl) with 2500 rpm was obtained, and the ORR mainly favors a direct four-electron pathway. The results of anodic linear scanning voltammograms indicate that the urchin-like LSM perovskite oxide exhibits an encouraging catalytic activity for the OER. All electrochemical measurements suggest that the urchin-like LSM perovskite oxide could be used as a bifunctional catalyst for the ORR and the OER.

  16. Dark ambient degradation of Bisphenol A and Acid Orange 8 as organic pollutants by perovskite SrFeO₃-δ metal oxide.

    PubMed

    Leiw, Ming Yian; Guai, Guan Hong; Wang, Xiaoping; Tse, Man Siu; Ng, Chee Mang; Tan, Ooi Kiang

    2013-09-15

    Current advanced oxidation processes (AOPs) are chemically and energetically intensive processes, which are undesirable for cost-effective and large-scale system water treatment and wastewater recycling. This study explored the Strontium Ferrite (SFO) metal oxide on the degradation of highly concentrated organic pollutants under dark ambient condition without any external stimulants. The SFO particles with single perovskite structure were successfully synthesized with a combined high temperature and high-energy ball milling process. An endocrine disruptor, Bisphenol A (BPA) and an azo dye, Acid Orange 8 (AO8) were used as probe organic pollutants. BPA was completely degraded with 83% of mineralization in 24 h while rapid decoloration of AO8 was achieved in 60 min and complete breakdown into primary intermediates and aliphatic acids occurred in 24 h under the treatment of dispersed SFO metal oxide in water. Such efficient degradation could be attributed to the enhanced adsorption of these anionic pollutants on positively charged ball-milled SFO metal oxide surface, resulted in higher degradation activity. Preliminary degradation mechanisms of BPA and AO8 under the action of SFO metal oxide were proposed. These results showed that the SFO metal oxide could be an efficient alternative material as novel advanced oxidation technology for low cost water treatment. PMID:23742952

  17. Methods for using novel cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    DOEpatents

    Jacobson, Allan J.; Wang, Shuangyan; Kim, Gun Tae

    2016-01-12

    Methods using novel cathode, electrolyte and oxygen separation materials operating at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes include oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  18. 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).

  19. Strain-based control of crystal anisotropy for perovskite oxides on semiconductor-based material

    DOEpatents

    McKee, Rodney Allen; Walker, Frederick Joseph

    2000-01-01

    A crystalline structure and a semiconductor device includes a substrate of a semiconductor-based material and a thin film of an anisotropic crystalline material epitaxially arranged upon the surface of the substrate so that the thin film couples to the underlying substrate and so that the geometries of substantially all of the unit cells of the thin film are arranged in a predisposed orientation relative to the substrate surface. The predisposition of the geometries of the unit cells of the thin film is responsible for a predisposed orientation of a directional-dependent quality, such as the dipole moment, of the unit cells. The predisposed orientation of the unit cell geometries are influenced by either a stressed or strained condition of the lattice at the interface between the thin film material and the substrate surface.

  20. Anomalous spin state of Fe in double perovskite oxide Sr 2FeWO 6

    NASA Astrophysics Data System (ADS)

    Kawanaka, H.; Hase, I.; Toyama, S.; Nishihara, Y.

    2000-07-01

    In the series of Sr 2FeTO 6 (T=4d or 5d), the valence of Fe is 3+ in most of the compounds. However, recently we have found that the Sr 2FeWO 6 has Fe 2+ state. Sr 2FeWO 6 is an insulator with an antiferromagnetic transition temperature of 37 K. From the Mössbauer experiment, below ∼20 K, a center shift of +1.2 mm/ s relative to metallic iron and a quadrupole splitting of 1.9 mm/ s are obtained. The quadrupole splitting has strong temperature dependence. The hyperfine field is ∼110 kOe which seems to be quite small. We concluded that the iron ground state of Sr 2FeWO 6 is Fe 2+ high-spin ( S=2) state.

  1. Large-Scale Synthesis of Highly Luminescent Perovskite-Related CsPb2 Br5 Nanoplatelets and Their Fast Anion Exchange.

    PubMed

    Wang, Kun-Hua; Wu, Liang; Li, Lei; Yao, Hong-Bin; Qian, Hai-Sheng; Yu, Shu-Hong

    2016-07-11

    All-inorganic cesium lead-halide perovskite nanocrystals have emerged as attractive optoelectronic nanomaterials owing to their stabilities and highly efficient photoluminescence. Herein we report a new type of highly luminescent perovskite-related CsPb2 Br5 nanoplatelets synthesized by a facile precipitation reaction. The layered crystal structure of CsPb2 Br5 promoted an anisotropic two-dimensional (2D) crystal growth during the precipitation process, thus enabling the large-scale synthesis of CsPb2 Br5 nanoplatelets. Fast anion exchange has also been demonstrated in as-synthesized CsPb2 Br5 nanoplatelets to extend their photoluminescence spectra to the entire visible spectral region. The large-scale synthesis and optical tunability of CsPb2 Br5 nanoplatelets will be advantageous in future applications of optoelectronic devices. PMID:27213688

  2. Lattice effects on ferromagnetism in perovskite ruthenates

    PubMed Central

    Cheng, J.-G.; Zhou, J.-S.; Goodenough, John B.

    2013-01-01

    Ferromagnetism and its evolution in the orthorhombic perovskite system Sr1–xCaxRuO3 have been widely believed to correlate with structural distortion. The recent development of high-pressure synthesis of the Ba-substituted Sr1–yBayRuO3 makes it possible to study ferromagnetism over a broader phase diagram, which includes the orthorhombic Imma and the cubic phases. However, the chemical substitutions introduce the A-site disorder effect on Tc, which complicates determination of the relationship between ferromagnetism and structural distortion. By clarifying the site disorder effect on Tc in several unique series of ruthenates in which the average bond length 〈A–O〉 remains the same but the bond-length variance varies, we are able to demonstrate a parabolic curve of Tc versus mean bond length 〈A–O〉. A much higher Tc ∼ 177 K than that found in orthorhombic SrRuO3 can be obtained from the curve at a bond length 〈A–O〉, which makes the geometric factor t = 〈A–O〉/(√2〈Ru–O〉) ∼ 1. This result reveals not only that the ferromagnetism in the ruthenates is extremely sensitive to the lattice strain, but also that it has an important implication for exploring the structure–property relationship in a broad range of oxides with perovskite or a perovskite-related structure. PMID:23904477

  3. Relative intensity calculations for nitrous oxide.

    NASA Technical Reports Server (NTRS)

    Young, L. D. G.

    1972-01-01

    A tabulation of calculated rotational line intensities, relative to the integrated intensity of a vibration-rotation band, is given for Sigma-Sigma, Pi-Sigma, Sigma-Pi, Pi-Pi, and Delta-Pi transitions of nitrous oxide. These calculations were made for temperatures of 250 K and 300 K. A summary of band-intensity measurements is also presented.

  4. Phase transitions in heated Sr{sub 2}MgTeO{sub 6} double perovskite oxide probed by X-ray diffraction and Raman spectroscopy

    SciTech Connect

    Manoun, Bouchaib Tamraoui, Y.; Lazor, P.; Yang, Wenge

    2013-12-23

    Double-perovskite oxide Sr{sub 2}MgTeO{sub 6} has been synthetized, and its crystal structure was probed by the technique of X-ray diffraction at room temperature. The structure is monoclinic, space group I2/m. Temperature-induced phase transitions in this compound were investigated by Raman spectroscopy up to 550 °C. Two low-wavenumber modes corresponding to external lattice vibrations merge at temperature of around 100 °C, indicating a phase transition from the monoclinic (I2/m) to the tetragonal (I4/m) structure. At 300 °C, changes in the slopes of temperature dependencies of external and O–Te–O bending modes are detected and interpreted as a second phase transition from the tetragonal (I4/m) to the cubic (Fm-3m) structure.

  5. Cantilever stress measurements for pulsed laser deposition of perovskite oxides at 1000 K in an oxygen partial pressure of 10{sup −4} millibars

    SciTech Connect

    Premper, J.; Sander, D.; Kirschner, J.

    2015-03-15

    An in situ stress measurement setup using an optical 2-beam curvature technique is described which is compatible with the stringent growth conditions of pulsed laser deposition (PLD) of perovskite oxides, which involves high substrate temperatures of 1000 K and oxygen partial pressures of up to 1 × 10{sup −4} millibars. The stress measurements are complemented by medium energy electron diffraction (MEED), Auger electron spectroscopy, and additional growth rate monitoring by a quartz microbalance. A shielded filament is used to allow for simultaneous stress and MEED measurements at high substrate temperatures. A computer-controlled mirror scans an excimer laser beam over a stationary PLD target. This avoids mechanical noise originating from rotating PLD targets, and the setup does not suffer from limited lifetime issues of ultra high vacuum (UHV) rotary feedthroughs.

  6. Cantilever stress measurements for pulsed laser deposition of perovskite oxides at 1000 K in an oxygen partial pressure of 10(-4) millibars.

    PubMed

    Premper, J; Sander, D; Kirschner, J

    2015-03-01

    An in situ stress measurement setup using an optical 2-beam curvature technique is described which is compatible with the stringent growth conditions of pulsed laser deposition (PLD) of perovskite oxides, which involves high substrate temperatures of 1000 K and oxygen partial pressures of up to 1 × 10(-4) millibars. The stress measurements are complemented by medium energy electron diffraction (MEED), Auger electron spectroscopy, and additional growth rate monitoring by a quartz microbalance. A shielded filament is used to allow for simultaneous stress and MEED measurements at high substrate temperatures. A computer-controlled mirror scans an excimer laser beam over a stationary PLD target. This avoids mechanical noise originating from rotating PLD targets, and the setup does not suffer from limited lifetime issues of ultra high vacuum (UHV) rotary feedthroughs. PMID:25832240

  7. Characterization and evaluation of double perovskites LnBaCoFeO5+δ (Ln = Pr and Nd) as intermediate-temperature solid oxide fuel cell cathodes

    NASA Astrophysics Data System (ADS)

    Jin, Fangjun; Xu, Huawei; Long, Wen; Shen, Yu; He, Tianmin

    2013-12-01

    Double perovskites LnBaCoFeO5+δ (Ln = Pr and Nd, PBCF and NBCF) are comparatively investigated as potential cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). LnBaCoFeO5+δ materials are chemically compatible with La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) electrolyte at temperatures below 1000 °C. Fe and Co ions in LnBaCoFeO5+δ exist in two oxidation states, 3+ and 4+. Pr ions are found in PBCF mostly as Pr3+. Thermal expansion coefficients (TECs) of PBCF and NBCF are 21.0 × 10-6 and 19.5 × 10-6 K-1, respectively, between 30 and 1000 °C; these are lower than the TECs of undoped LnBaCo2O5+δ. The best electrical conductivity for both materials is observed near 350 °C: 321 and 172 S cm-1 for PBCF and NBCF, respectively. Polarization resistances of PBCF and NBCF cathodes on LSGM electrolyte are 0.049 and 0.062 Ω cm2 at 800 °C, respectively. Maximum power densities of the single-cell with Ni/SDC as anode on a 0.3 mm-thick LSGM electrolyte reach 749 and 669 mW cm-2 for PBCF and NBCF cathodes at 800 °C, respectively. As cathodes for application in IT-SOFCs, the performance of PBCF and NBCF double perovskites is promising.

  8. Positional flexibility: syntheses and characterization of six uranium chalcogenides related to the 2H hexagonal perovskite family.

    PubMed

    Mesbah, Adel; Prakash, Jai; Beard, Jessica C; Pozzi, Eric A; Tarasenko, Mariya S; Lebègue, Sébastien; Malliakas, Christos D; Van Duyne, Richard P; Ibers, James A

    2015-03-16

    Six new uranium chalcogenides, Ba4USe6, Ba3FeUSe6, Ba3MnUSe6, Ba3MnUS6, Ba3.3Rb0.7US6, and Ba3.2K0.8US6, related to the 2H hexagonal perovskite family have been synthesized by solid-state methods at 1173 K. These isostructural compounds crystallize in the K4CdCl6 structure type in space group D3d6–R3̅c of the trigonal system with six formula units per cell. This structure type is remarkably flexible. The structures of Ba3FeUSe6, Ba3MnUSe6, and Ba3MnUS6 consist of infinite ∞1[MUQ66–] chains (M = Fe or Mn; Q = S or Se) oriented along the c axis that are separated by Ba atoms. These chains are composed of alternating M-centered octahedra and U-centered trigonal prisms sharing triangular faces; in contrast, in the structures of Ba4USe6, Ba3.3Rb0.7US6, and Ba3.2K0.8US6, there are U-centered octahedra alternating with Ba-, Rb-, or K-centered trigonal prisms. Moreover, the Ba4USe6, Ba3FeUSe6, Ba3MnUSe6, and Ba3MnUS6 compounds contain U4+, whereas Ba3.3Rb0.7US6 and Ba3.2K0.8US6 are mixed U4+/5+ compounds. Resistivity and μ-Raman spectroscopic measurements and DFT calculations provide additional insight into these interesting subtle structural variations. PMID:25697078

  9. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites.

    PubMed

    Petrie, Jonathan R; Cooper, Valentino R; Freeland, John W; Meyer, Tricia L; Zhang, Zhiyong; Lutterman, Daniel A; Lee, Ho Nyung

    2016-03-01

    Strain is known to greatly influence low-temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. However, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals such as Pt. We attribute the improved bifunctionality to strain-induced splitting of the eg orbitals, which can customize orbital asymmetry at the surface. Analogous to strain-induced shifts in the d-band center of noble metals relative to the Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides. PMID:26866808

  10. Controlling band alignments by artificial interface dipoles at perovskite heterointerfaces

    PubMed Central

    Yajima, Takeaki; Hikita, Yasuyuki; Minohara, Makoto; Bell, Christopher; Mundy, Julia A.; Kourkoutis, Lena F.; Muller, David A.; Kumigashira, Hiroshi; Oshima, Masaharu; Hwang, Harold Y.

    2015-01-01

    The concept ‘the interface is the device' is embodied in a wide variety of interfacial electronic phenomena and associated applications in oxide materials, ranging from catalysts and clean energy systems to emerging multifunctional devices. Many device properties are defined by the band alignment, which is often influenced by interface dipoles. On the other hand, the ability to purposefully create and control interface dipoles is a relatively unexplored degree of freedom for perovskite oxides, which should be particularly effective for such ionic materials. Here we demonstrate tuning the band alignment in perovskite metal-semiconductor heterojunctions over a broad range of 1.7 eV. This is achieved by the insertion of positive or negative charges at the interface, and the resultant dipole formed by the induced screening charge. This approach can be broadly used in applications where decoupling the band alignment from the constituent work functions and electron affinities can enhance device functionality. PMID:25849738

  11. Core-shell heterostructured metal oxide arrays enable superior light-harvesting and hysteresis-free mesoscopic perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Mahmood, Khalid; Swain, Bhabani Sankar; Amassian, Aram

    2015-07-01

    To achieve highly efficient mesoscopic perovskite solar cells (PSCs), the structure and properties of an electron transport layer (ETL) or material (ETM) have been shown to be of supreme importance. Particularly, the core-shell heterostructured mesoscopic ETM architecture has been recognized as a successful electrode design, because of its large internal surface area, superior light-harvesting efficiency and its ability to achieve fast charge transport. Here we report the successful fabrication of a hysteresis-free, 15.3% efficient PSC using vertically aligned ZnO nanorod/TiO2 shell (ZNR/TS) core-shell heterostructured ETMs for the first time. We have also added a conjugated polyelectrolyte polymer into the growth solution to promote the growth of high aspect ratio (AR) ZNRs and substantially improve the infiltration of the perovskite light absorber into the ETM. The PSCs based on the as-synthesized core-shell ZnO/TiO2 heterostructured ETMs exhibited excellent performance enhancement credited to the superior light harvesting capability, larger surface area, prolonged charge-transport pathways and lower recombination rate. The unique ETM design together with minimal hysteresis introduces core-shell ZnO/TiO2 heterostructures as a promising mesoscopic electrode approach for the fabrication of efficient PSCs.To achieve highly efficient mesoscopic perovskite solar cells (PSCs), the structure and properties of an electron transport layer (ETL) or material (ETM) have been shown to be of supreme importance. Particularly, the core-shell heterostructured mesoscopic ETM architecture has been recognized as a successful electrode design, because of its large internal surface area, superior light-harvesting efficiency and its ability to achieve fast charge transport. Here we report the successful fabrication of a hysteresis-free, 15.3% efficient PSC using vertically aligned ZnO nanorod/TiO2 shell (ZNR/TS) core-shell heterostructured ETMs for the first time. We have also added a

  12. Epitaxial synthesis and physical properties of double-perovskite oxide Sr2CoRuO6 thin films.

    PubMed

    Watarai, K; Yoshimatsu, K; Horiba, K; Kumigashira, H; Sakata, O; Ohtomo, A

    2016-11-01

    We report epitaxial structures and physical properties of double-perovskite Sr2CoRuO6 films grown using pulsed-laser deposition. Samples with a degree of Co/Ru order of 2-73% were obtained by changing growth temperature. X-ray absorption spectroscopy (XAS) on the highest ordered sample revealed that Co ions were trivalent with a high-spin configuration and Ru ions were pentavalent. We found large differences in magnetization and resistivity between the highest and lowest ordered samples as well as the absence of strong magnetism and metallicity, which are common characteristics of SrCoO3 and SrRuO3. Using resonant photoemission spectroscopy and XAS, dominant d-orbital components at the top of the occupied state (the bottom of the unoccupied state) were identified to be Ru 4d t 2g (Co 3d and Ru 4d t 2g ). These results suggest that the ground state of double-perovskite Sr2CoRuO6 is a ferrimagnetic insulator. PMID:27603328

  13. Core-shell heterostructured metal oxide arrays enable superior light-harvesting and hysteresis-free mesoscopic perovskite solar cells.

    PubMed

    Mahmood, Khalid; Swain, Bhabani Sankar; Amassian, Aram

    2015-08-14

    To achieve highly efficient mesoscopic perovskite solar cells (PSCs), the structure and properties of an electron transport layer (ETL) or material (ETM) have been shown to be of supreme importance. Particularly, the core-shell heterostructured mesoscopic ETM architecture has been recognized as a successful electrode design, because of its large internal surface area, superior light-harvesting efficiency and its ability to achieve fast charge transport. Here we report the successful fabrication of a hysteresis-free, 15.3% efficient PSC using vertically aligned ZnO nanorod/TiO2 shell (ZNR/TS) core-shell heterostructured ETMs for the first time. We have also added a conjugated polyelectrolyte polymer into the growth solution to promote the growth of high aspect ratio (AR) ZNRs and substantially improve the infiltration of the perovskite light absorber into the ETM. The PSCs based on the as-synthesized core-shell ZnO/TiO2 heterostructured ETMs exhibited excellent performance enhancement credited to the superior light harvesting capability, larger surface area, prolonged charge-transport pathways and lower recombination rate. The unique ETM design together with minimal hysteresis introduces core-shell ZnO/TiO2 heterostructures as a promising mesoscopic electrode approach for the fabrication of efficient PSCs. PMID:26159238

  14. Room-temperature solution-processed and metal oxide-free nano-composite for the flexible transparent bottom electrode of perovskite solar cells.

    PubMed

    Lu, Haifei; Sun, Jingsong; Zhang, Hong; Lu, Shunmian; Choy, Wallace C H

    2016-03-21

    The exploration of low-temperature and solution-processed charge transporting and collecting layers can promote the development of low-cost and large-scale perovskite solar cells (PVSCs) through an all solution process. Here, we propose a room-temperature solution-processed and metal oxide-free nano-composite composed of a silver nano-network and graphene oxide (GO) flawless film for the transparent bottom electrode of a PVSC. Our experimental results show that the amount of GO flakes play a critical role in forming the flawless anti-corrosive barrier in the silver nano-network through a self-assembly approach under ambient atmosphere, which can effectively prevent the penetration of liquid or gaseous halides and their corrosion against the silver nano-network underneath. Importantly, we simultaneously achieve good work function alignment and surface wetting properties for a practical bottom electrode by controlling the degree of reduction of GO flakes. Finally, flexible PVSC adopting the room-temperature and solution-processed nano-composite as the flexible transparent bottom electrode has been demonstrated on a polyethylene terephthalate (PET) substrate. As a consequence, the demonstration of our room-temperature solution-processed and metal oxide-free flexible transparent bottom electrode will contribute to the emerging large-area flexible PVSC technologies. PMID:26923479

  15. Controlling Octahedral Rotations in a Perovskite via Strain Doping.

    PubMed

    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

  16. 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

  17. Ab Initio Calculations on Spin Transitions in Perovskite

    NASA Astrophysics Data System (ADS)

    Brodholt, J. P.; Stackhouse, S.; Alfredsson, M.; Price, G. D.

    2006-05-01

    Spin transitions in perovskite and magnesiowustite have become the subject of considerable interest since they have been experimentally observed to occur under mantle conditions. Experimental results, however, are not always mutually consitent and a variety of transition pressures have been observed. We have, therefore, performed GGA, LDA, and hybrid-functional calculations on MgSiO3 perovskite containing 6%, 12% and 100% ferric and/or ferrous iron. Although the GGA and LDA calculations suffer from the well-know problem of predicting transition metal oxide insulators to be metallic, the hybrid-functionals do not do this. By using both methods we hope to increase confidence in the results. In agreement with previous work on Al3+ and Fe3+ bearing perovskites (Li et al, 2004) we find a wide range of transition pressures, which are related to the mechanism of iron incorporation. Compositions with just Fe2+ generally have the highest transition pressures, while compositions with just Fe3+ have the lowest. Using these results we are able to explain the spin transitions observed by different experimental groups. The spin state of iron has a small effect on the density, bulk and shear modulus of perovskite, but at the low concentrations expected in the mantle this is unlikely to be seismically visible.

  18. Controlling octahedral rotations in a perovskite via strain doping

    DOE PAGESBeta

    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

  19. 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.

  20. Surface properties and catalytic performance of La(1-x)Sr(x)FeO(3) perovskite-type oxides for methane combustion.

    PubMed

    Wang, Ching-Huei; Chen, Chun-Liang; Weng, Hung-Shan

    2004-12-01

    La(1-x)Sr(x)FeO(3) (x=0.0-1.0) perovskites were prepared and tested for the combustion of methane. X-ray diffraction (XRD) patterns revealed the presence of a single perovskite structure for substitutions 0x0.3, however Fe(2)O(3), SrCO(3) and SrFeO(3) phases were observed for substitutions x>0.3. The results of activity test indicate that with La(1-x)Sr(x)FeO(3) as the catalyst, the combustion of methane can take place at low temperatures around 400 degrees C. Partial substitution of La with Sr increases the activity and an optimal substitution fraction (x=0.5) exists in the La(1-x)Sr(x)FeO(3) catalysts. Catalyst activity can be well correlated to the product of the specific surface area and atomic ratio of Fe to La+Sr on the catalyst surface. Experimental results of O(2)-TPD and CH(4)-TPD in the range of 350-500 degrees C indicate that the amount of oxygen desorbed from the La(1-x)Sr(x)FeO(3) catalysts is far larger than that of methane. Therefore, it can be proposed that the catalytic oxidation of CH(4) over these catalysts proceeds with the surface reaction between CH(4) in the gas phase and the adsorbed O(2). Addition of water vapor or CO(2) to the feed inhibited catalyst activity, but the inhibition was reversible and became negligible at high reaction temperature. PMID:15504472

  1. Wet aerobic oxidation of lignin into aromatic aldehydes catalysed by a perovskite-type oxide: LaFe(1-x)Cu(x)O3 (x=0, 0.1, 0.2).

    PubMed

    Zhang, Junhua; Deng, Haibo; Lin, Lu

    2009-01-01

    The perovskite-type oxide catalyst LaFe(1-x)Cu(x)O(3 )(x=0, 0.1, 0.2) was prepared by the sol-gel method, and tested as a catalyst in the wet aerobic oxidation (WAO) of lignin into aromatic aldehydes. The lignin conversion and the yield of each aromatic aldehyde were significantly enhanced in the catalytic process, compared with the non-catalyzed process. Moreover, it was shown that the stability of activity and structure of LaFe(1-x)Cu(x)O(3 )(x=0, 0.1, 0.2) remained nearly unchanged after a series of successive recyclings of the catalytic reactions, indicating it was an efficient and recyclable heterogeneous catalyst for the conversion of lignin into aromatic aldehydes in the WAO process. PMID:19701121

  2. The relative radiation resistance of zirconolite, pyrochlore and perovskite to 1.5 MeV Kr{sup +} ions

    SciTech Connect

    Smith, K.L.; Zaluzec, N.J.; Lumpkin, G.R.

    1997-03-01

    Zirconolite (CaZrTi2O7), pyrochlore (VIIIA2 VIB2 IV X6Y) and perovskite (CaTiO3) are candidate phases for the immobilisation of rare earth elements (REEs) and actinides (ACTs) in various high level radioactive waste (HLW) forms 1. The effect of radiation damage on the structure and consequently on the durability of these phases is important to predictive modelling of their behaviour in the repository environment and risk assessment.

  3. Reduction process of Pd-containing La-Fe perovskite-type oxides by in-situ Dispersive X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Uchiyama, T.; Kamitani, K.; Kato, K.; Nishibori, M.

    2016-05-01

    Reduction process of Pd-containing La-Fe perovskites was investigated by in-situ Pd K-edge dispersive X-ray absorption fine structure as well as mass spectroscopy. The prepared perovskite was characterized by a conventional X-ray absorption spectra to confirm the incorporation of cationic Pd into perovskite matrix. Under the reductive atmosphere (5 vol%H2/He), we found the presence of three reduction processes of Pd cations in perovskite structure. The segregation of Pd metal particles was observed from 200-400 oC although the cationic Pd species remained at 700 oC due to the strong metal-support interaction.

  4. High-performance and environmentally stable planar heterojunction perovskite solar cells based on a solution-processed copper-doped nickel oxide hole-transporting layer.

    PubMed

    Kim, Jong H; Liang, Po-Wei; Williams, Spencer T; Cho, Namchul; Chueh, Chu-Chen; Glaz, Micah S; Ginger, David S; Jen, Alex K-Y

    2015-01-27

    An effective approach to significantly increase the electrical conductivity of a NiOx hole-transporting layer (HTL) to achieve high-efficiency planar heterojunction perovskite solar cells is demonstrated. Perovskite solar cells based on using Cu-doped NiOx HTL show a remarkably improved power conversion efficiency up to 15.40% due to the improved electrical conductivity and enhanced perovskite film quality. General applicability of Cu-doped NiOx to larger bandgap perovskites is also demonstrated in this study. PMID:25449020

  5. Surface plasmon resonances behavior in visible light of non-metal perovskite oxides AgNbO{sub 3}

    SciTech Connect

    Zhou, Fei; Zhu, Jingchuan Liu, Yong; Zhao, Xiaoliang; Lai, Zhonghong

    2014-12-08

    We investigate the surface plasmon resonances (SPRs) behavior of silver niobate (AgNbO{sub 3}) experimentally and theoretically. Result shows that the localized SPRs (LSPRs) of AgNbO{sub 3} combining with its interband transitions enlarge the absorption band across the whole ultraviolet-visible range. The LSPRs behavior in visible-light is mainly ascribed to the metal-like state of silver ion and self-assembled microstructures of AgNbO{sub 3} microcrystal. The ab initio density functional theory calculations are carried out to obtain the further insight of the SPRs behaviors. Theoretical study indicates that the Ag atoms are weakly bound in the perovskite structure, leading to a metal-like state, which was the key factor to SPRs behavior of AgNbO{sub 3}.

  6. A new family of Ce-doped SmFeO3 perovskite for application in symmetrical solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Fan, Weiwei; Sun, Zhu; Wang, Junkai; Zhou, Jun; Wu, Kai; Cheng, Yonghong

    2016-04-01

    Here, a nanoporous Sm0.95Ce0.05FeO3-δ (SCFO) perovskite-type oxide is assessed in regard to its possible use as an electrode material for symmetrical solid oxide fuel cells. It is found that SCFO has a good redox stability after characterizing the sample which is calcined at 850 °C in 5% H2/N2 for 10 h. Optimized electrochemical performances are obtained in both the nanoporous anode and cathode which are mainly due to the high catalytic activity of SCFO for redox reaction. The peak power density of SCFO|YSZ|SCFO symmetrical cell is as high as 130 mW cm-2 at 800 °C using pure, humidified H2 as the fuel. Moreover, the maximum power density of 193 mW cm-2 can be obtained for the SCFO:YSZ(7:3)|YSZ|SCFO:YSZ(7:3) symmetrical cell under the same conditions.

  7. A novel route to prepare LaNiO3 perovskite-type oxide nanofibers by electrospinning for glucose and hydrogen peroxide sensing.

    PubMed

    Wang, Bijun; Gu, Shuqing; Ding, Yaping; Chu, Yuliang; Zhang, Zhen; Ba, Xi; Zhang, Qiaolin; Li, Xinru

    2013-01-01

    Perovskite-type oxide LaNiO(3) nanofibers (LNFs) have been successfully synthesized by electrospinning and sequential calcinations. The electrospun LNFs modified carbon paste electrode was used to construct a nonenzymatic hydrogen peroxide (H(2)O(2)) sensor and glucose biosensor for the first time. The LNFs composition was verified by X-ray diffraction, and the morphologies were examined by scanning electron microscopy and transmission electron microscopy. Cyclic voltammetry and amperometry were used to evaluate the catalytic activity of the LNFs modified electrode towards H(2)O(2) and glucose. By using LNFs as electrocatalysts, the modified electrode showed high electrocatalytic activity for the oxidation of H(2)O(2) and glucose. Under the optimized conditions, the H(2)O(2) sensor exhibited a low detection limit down to 33.9 nM with a wide linear range from 0.05 to 1000 μM. The nonenzymatic sensor also showed fast response, long-term stability as well as a low detection limit for glucose. PMID:23154514

  8. (Thermochemistry of phases related to oxide superconductors)

    SciTech Connect

    Not Available

    1991-01-01

    The aim of this project has been to understand the crystal-chemical and energetic constraints on the stability of phases related to oxide superconductors, using high temperature reaction calorimetry, the unique expertise of this laboratory, coupled with synthesis and structural studies. The YBCO (Y{sub 2}O{sub 3}-BaO-Cu-O) system has been studied in detail by Zhou for his Ph.D. thesis, while DiCarlo has been studying alkaline earth doped lanthanium cuprates of the series La{sub 2-x}A{sub x}CuO{sub 4-y} having structures related to K{sub 2}NiF{sub 4}.

  9. Theoretical investigation of H2 oxidation on the Sr2Fe(1.5)Mo(0.5)O6 (001) perovskite surface under anodic solid oxide fuel cell conditions.

    PubMed

    Suthirakun, Suwit; Ammal, Salai Cheettu; Muñoz-García, Ana B; Xiao, Guoliang; Chen, Fanglin; zur Loye, Hans-Conrad; Carter, Emily A; Heyden, Andreas

    2014-06-11

    Periodic density functional theory (DFT) calculations and microkinetic modeling are used to investigate the electrochemical oxidation of H2 fuel on the (001) surface of Sr2Fe1.5Mo0.5O6 (SFMO) perovskite under anodic solid oxide fuel cell conditions. Three surface models with different Fe/Mo ratios in the topmost layer-identified by ab initio thermodynamic analysis-are used to investigate the H2 oxidation mechanism. A microkinetic analysis that considers the effects of anode bias potential suggests that a higher Mo concentration in the surface increases the activity of the surface toward H2 oxidation. At operating voltage and anodic SOFC conditions, the model predicts that water desorption is rate-controlling and that stabilizing the oxygen vacancy structure increases the overall rate for H2 oxidation. Although we find that Mo plays a crucial role in improving catalytic activity of SFMO, under fuel cell operating conditions, the Mo content in the surface layer tends to be very low. On the basis of these results and in agreement with previous experimental observations, a strategy for improving the overall electrochemical performance of SFMO is increasing the Mo content or adding small amounts of an active transition metal, such as Ni, to the surface to lower the oxygen vacancy formation energy of the SFMO surface. PMID:24826843

  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. 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.

  12. Relation between EPR spectra and electrical conductivity of Pr 1-xPb xMnO 3 perovskites

    NASA Astrophysics Data System (ADS)

    Cong, B. T.; Yu, S. C.; Tho, N. D.; Chau, N.; Huynh, T. N.; Phan, T. L.

    2006-09-01

    The correlation between structure, Curie temperature ( TC), line width of EPR spectra and electrical conductivity of Pr 1-xPb xMnO 3 ( x=0.1, 0.2, 0.3, 0.4, and 0.5) perovskites is discussed. It was shown that both adiabatic small polaron and variable range hopping models are good for description of conductivity in paramagnetic region but the first one is more suitable for interpretation of temperature dependence of EPR line width in temperature range 1.2 TC< T<1.3 TC.

  13. Room-temperature solution-processed and metal oxide-free nano-composite for the flexible transparent bottom electrode of perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Lu, Haifei; Sun, Jingsong; Zhang, Hong; Lu, Shunmian; Choy, Wallace C. H.

    2016-03-01

    The exploration of low-temperature and solution-processed charge transporting and collecting layers can promote the development of low-cost and large-scale perovskite solar cells (PVSCs) through an all solution process. Here, we propose a room-temperature solution-processed and metal oxide-free nano-composite composed of a silver nano-network and graphene oxide (GO) flawless film for the transparent bottom electrode of a PVSC. Our experimental results show that the amount of GO flakes play a critical role in forming the flawless anti-corrosive barrier in the silver nano-network through a self-assembly approach under ambient atmosphere, which can effectively prevent the penetration of liquid or gaseous halides and their corrosion against the silver nano-network underneath. Importantly, we simultaneously achieve good work function alignment and surface wetting properties for a practical bottom electrode by controlling the degree of reduction of GO flakes. Finally, flexible PVSC adopting the room-temperature and solution-processed nano-composite as the flexible transparent bottom electrode has been demonstrated on a polyethylene terephthalate (PET) substrate. As a consequence, the demonstration of our room-temperature solution-processed and metal oxide-free flexible transparent bottom electrode will contribute to the emerging large-area flexible PVSC technologies.The exploration of low-temperature and solution-processed charge transporting and collecting layers can promote the development of low-cost and large-scale perovskite solar cells (PVSCs) through an all solution process. Here, we propose a room-temperature solution-processed and metal oxide-free nano-composite composed of a silver nano-network and graphene oxide (GO) flawless film for the transparent bottom electrode of a PVSC. Our experimental results show that the amount of GO flakes play a critical role in forming the flawless anti-corrosive barrier in the silver nano-network through a self

  14. The performance of La0.6Sr1.4MnO4 layered perovskite electrode material for intermediate temperature symmetrical solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Zhou, Jun; Chen, Gang; Wu, Kai; Cheng, Yonghong

    2014-12-01

    A layered perovskite electrode material, La0.6Sr1.4MnO4+δ (LSMO4), has been studied for intermediate temperature symmetrical solid oxide fuel cells (IT-SSOFCs) on La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) electrolyte. The chemical compatibility tests indicate that no reaction occurred between LSMO4 oxide and LSGM electrolyte at temperature up to 1000 °C both in air and 5% H2. The lower conductivity in 5% H2 and higher conduction activation energy than those in air would be caused by poorer overlap of both σ and π bonds. DFT + U calculations also show that oxygen vacancies which formed in reducing atmosphere may block the 3D hopping path for electrons or holes through Mn-O-Mn chains. For LSMO4 electrode, SEM results indicate that the electrode formed good contact with the electrolyte after being sintered at 900 °C for 2 h. At 800 °C, the polarization resistance of the LSMO4 cathode is about 0.87 Ω cm2 in air, while the polarization resistance of the LSMO4 anode is about 2.07 Ω cm2 in 5% H2. LSMO4 exhibits better electrochemical activity for oxygen reduction than that for hydrogen oxidation. A cell with LSGM electrolyte, LSMO4-LSGM mixture as anode and cathode simultaneously displays a maximum power density of 59 mW cm-2 at 800 °C.

  15. EFFICIENCY PROBLEMS RELATED TO PERMANGANATE OXIDATION SCHEMES

    EPA Science Inventory

    Oxidation schemes for the in-situ destruction of chlorinated solvents, using potassium permanganate, are receiving considerable attention. Indication from field studies and from our own work are that permanganate oxidation schemes have inherent problems that could severely limit...

  16. 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).

  17. Structure and thermodynamic stability of hydrogen interstitials in BaZrO3 perovskite oxide from density functional calculations.

    PubMed

    Björketun, Mårten E; Sundell, Per G; Wahnström, Göran

    2007-01-01

    Density functional calculations have been used to study the electronic structure, preferred sites in the lattice, formation energies and vibrational frequencies for hydrogen interstitials in different charge states in the cubic phase of perovskite-structured BaZrO3. By combining ab initio results with thermodynamic modeling, defect formation at finite temperature and pressure has been investigated. We demonstrate how the site selectivity and spatial distribution of dopant atoms in the lattice can be affected by changes in the environmental conditions (atomic chemical potentials, oxygen partial pressure and temperature) used during processing of the material. In addition, we have calculated the thermodynamic parameters of the water uptake reaction for an acceptor-doped BaZrO3 crystal in equilibrium with a humid atmosphere. The interaction energies between a protonic defect and the investigated Ga, Gd, In, Nd, Sc, and Y dopants were found to be attractive, and we show that a simple model of defect association may reproduce an experimentally observed trend in the hydration enthalpy. PMID:17326572

  18. Electrical Conductivity of SrxVMoO6-y (x=0.0, 0.1, 0.2) Double Perovskite Solid Oxide Fuel Cell Anode

    NASA Astrophysics Data System (ADS)

    Childs, Nicholas; Weisenstein, Adam; Key, Camas; Sofie, Stephen; Smith, Richard

    2012-10-01

    Solid Oxide Fuel Cells (SOFCs) are suited for high efficiency power generation, fuel flexibility, high temperature electrolysis, closed loop regenerative systems, oxygen generation, and carbon dioxide reduction. These capabilities make the SOFC highly versatile for: primary/secondary power systems, advanced life support, and in-situ resource utilization which may all be desired for a forthcoming lunar return and Mars Exploration. A promising anode material for a SOFCs is the double perovskite Sr2-xVMoO6-y(x=0.0-0.2), due to its stability, electronic, and ionic conduction. Anodes of this material were prepared via a tape casting technique. Electrical conductivity was studied in reducing atmospheres at temperatures up to 800 ^oC. V and Mo valence states were indentified before and after annealing in a hydrogen environment. Samples exhibited metallic conduction with electrical conductivity of ˜10^4S/cm in a reducing atmosphere at 25 ^oC. A highly insulating SrMoO4 phase forms upon room temperature exposure to air. The SrMoO4 phase can be reduced above 400 ^oC resulting in an increase in conductivity.

  19. Perovskite Sr₁-xCexCoO₃-δ (0.05 ≤ x ≤ 0.15) as superior cathodes for intermediate temperature solid oxide fuel cells.

    PubMed

    Yang, Wei; Hong, Tao; Li, Shuai; Ma, Zhaohui; Sun, Chunwen; Xia, Changrong; Chen, Liquan

    2013-02-01

    Perovskite Sr(1-x)Ce(x)CoO(3-δ) (0.05 ≤ x ≤ 0.15) have been prepared by a sol-gel method and studied as cathodes for intermediate temperature solid oxide fuel cells. As SOFC cathodes, Sr(1-x)Ce(x)CoO(3-δ) materials have sufficiently high electronic conductivities and excellent chemical compatibility with SDC electrolyte. The peak power density of cells with Sr(0.95)Ce(0.05)CoO(3-δ) is 0.625 W cm(-2) at 700 °C. By forming a composite cathode with an oxygen ion conductor SDC, the peak power density of the cell with Sr(0.95)Ce(0.05)CoO(3-δ)-30 wt %SDC composite cathode, reaches 1.01 W cm(-2) at 700 °C, better than that of Sm(0.5)Sr(0.5)CoO(3)-based cathode. All these results demonstrates that Sr(1-x)Ce(x)CoO(3-δ) (0.05 ≤ x ≤ 0.15)-based materials are promising cathodes for an IT-SOFC. PMID:23336216

  20. “True” negative thermal expansion in Mn-doped LaCu{sub 3}Fe{sub 4}O{sub 12} perovskite oxides

    SciTech Connect

    Yamada, Ikuya; Marukawa, Shohei; Murakami, Makoto; Mori, Shigeo

    2014-12-08

    Negative and zero thermal expansion near room temperature have been achieved in a cubic A-site ordered perovskite oxide LaCu{sub 3}Fe{sub 4−x}Mn{sub x}O{sub 12}. A discontinuous volume change in the parent material LaCu{sub 3}Fe{sub 4}O{sub 12}, owing to a first-order intermetallic charge transfer transition (3Cu{sup 2+ }+ 4Fe{sup 3.75+} ⇄ 3Cu{sup 3+ }+ 4Fe{sup 3+}), is efficiently relaxed to a second-order-type negative thermal expansion with a linear thermal expansion coefficient (α{sub L}) of −2.2(1) × 10{sup −5 }K{sup −1} between 300 and 340 K at x = 0.75, followed by an almost zero thermal expansion [α{sub L} of −1.1(2) × 10{sup −6 }K{sup −1}] at x = 1 in a wide temperature range (240–360 K) including room temperature. Magnetic susceptibility measurements display substantial broadenings of the antiferromagnetic transition when x increases, supporting the relaxation of first-order electronic phase transition of the parent material. These findings indicate that the significant adjustability of thermal expansion properties can be achieved in first-order intermetallic charge-transfer transition.

  1. Functionalization of perovskite thin films with moisture-tolerant molecules

    NASA Astrophysics Data System (ADS)

    Yang, Shuang; Wang, Yun; Liu, Porun; Cheng, Yi-Bing; Zhao, Hui Jun; Yang, Hua Gui

    2016-02-01

    Organic-inorganic hybrid perovskites are particularly suited as light-harvesting materials in photovoltaic devices. The power conversion efficiency of perovskite solar cells has reached certified values of over 20% in just a few years. However, one of the major hindrances for application of these materials in real-world devices is the performance degradation in humid conditions, leading to a rapid loss of photovoltaic response. Here, we demonstrate that hydrophobic tertiary and quaternary alkyl ammonium cations can be successfully assembled on the perovskite surface as efficient water-resisting layers via a facile surface functionalization technique. Such layers can protect the perovskite film under high relative humidity (90 ± 5%) over 30 days. More importantly, devices based on such films can retain the photovoltaic capacities of bulk perovskites, with power conversion efficiencies over 15%. Improving the humidity tolerance of perovskite materials is a necessary step towards large-scale production of high-performance perovskite-based devices under ambient humidity.

  2. Neutral- and Multi-Colored Semitransparent Perovskite Solar Cells.

    PubMed

    Lee, Kyu-Tae; Guo, L Jay; Park, Hui Joon

    2016-01-01

    In this review, we summarize recent works on perovskite solar cells with neutral- and multi-colored semitransparency for building-integrated photovoltaics and tandem solar cells. The perovskite solar cells exploiting microstructured arrays of perovskite "islands" and transparent electrodes-the latter of which include thin metallic films, metal nanowires, carbon nanotubes, graphenes, and transparent conductive oxides for achieving optical transparency-are investigated. Moreover, the perovskite solar cells with distinctive color generation, which are enabled by engineering the band gap of the perovskite light-harvesting semiconductors with chemical management and integrating with photonic nanostructures, including microcavity, are discussed. We conclude by providing future research directions toward further performance improvements of the semitransparent perovskite solar cells. PMID:27077835

  3. 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.

  4. Rietveld refinement and dielectric relaxation of a new rare earth based double perovskite oxide: BaPrCoNbO{sub 6}

    SciTech Connect

    Bharti, Chandrahas; Das, Mrinmoy K.; Sen, A.; Chanda, Sadhan; Sinha, T.P.

    2014-02-15

    A new rare earth based double perovskite oxide barium praseodymium cobalt niobate, BaPrCoNbO{sub 6} (BPCN) is synthesized by solid-state reaction technique. Rietveld analysis of X-ray diffraction (XRD) data shows that the compound crystallizes in a perovskite like tetragonal structure which belongs to the I4/mmm space group with lattice parameters a=b=5.6828(9) Å, c=8.063(2) Å. Structural analysis reveals 1:1 ordered arrangement for the Co{sup 2+} and Nb{sup 5+} cations over the six-coordinate B-sites of BPCN. The superlattice line (1 0 1) at 2θ=19.10° arising from the alternate ordering of Co{sup 2+} and Nb{sup 5+} sites is observed in the XRD pattern which confirms the presence of cation ordering in BPCN. Fourier transform infrared spectrum shows two phonon modes of the sample due to the antisymmetric NbO{sub 6} stretching vibration. The relaxation dynamics of the conductive process in BPCN is investigated in the temperature range 303 to 503 K and in the frequency range 100 Hz to 1 MHz using impedance spectroscopy. The relaxation mechanism of the sample in the framework of electric modulus formalism is modeled by Davidson–Cole model (DCM). The values of α (distribution of relaxation time) for the DCM varies from 0.1 to 0.3 which suggests the asymmetric distribution of relaxation time for BPCN. The activation energy of the sample, calculated from both conductivity and modulus spectra, are found to be almost the same ∼0.4 eV, which indicates that the conduction mechanism for BPCN is polaron hopping. The scaling behaviour of the imaginary part of electric modulus suggests that the relaxation follows the same mechanism at various temperatures. - Graphical abstract: Rietveld refinement plot for BPCN. Inset shows the schematic presentation of the BPCN tetragonal unit cell. The Co{sup 2+} atoms are located at the centers of the CoO{sub 6} (blue) octahedra. The Nb{sup 5+} atoms are located at the centers of the NbO{sub 6} (green) octahedra. Display Omitted

  5. Phase transitions of BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} perovskite-type oxides under reducing environments

    SciTech Connect

    Rodríguez, G.C.Mondragón; Gönüllü, Y.; Ferri, Davide; Eyssler, Arnim; Otal, Eugenio; Saruhan, B.

    2015-01-15

    Highlights: • Solid solution formation BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} with a new wet chemical synthesis method. • Rhodium in the BaTiO{sub 3} perovskite stabilizes the hexagonal structure. • New Rh segregation mechanism for hexagonal BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} upon reduction. - Abstract: Perovskite-type oxides of composition BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} were prepared following a new chemical route that avoids the formation of hydroxyl species and precipitation, and allows the homogeneous distribution of Rh in the final mixed metal oxide. The high dispersion of Rh and the formation of the solid solution between Rh and the BaTiO{sub 3} perovskite is confirmed by means of X-ray diffraction (XRD) and extended X-ray absorption fine structure spectroscopy (EXAFS). The presence of Rh stabilized the hexagonal BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} phase, which decomposes into barium orthotitanate (BaTi{sub 2}O{sub 4}) and metallic Rh° in reducing environment. This phase transition starts already at 700 °C and is only partially completed at 900 °C suggesting that part of the Rh present in the perovskite lattice might not be easily reduced by hydrogen. These aspects and further open questions are discussed.

  6. Layered perovskite oxide: a reversible air electrode for oxygen evolution/reduction in rechargeable metal-air batteries.

    PubMed

    Takeguchi, Tatsuya; Yamanaka, Toshiro; Takahashi, Hiroki; Watanabe, Hiroshi; Kuroki, Tomohiro; Nakanishi, Haruyuki; Orikasa, Yuki; Uchimoto, Yoshiharu; Takano, Hiroshi; Ohguri, Nobuaki; Matsuda, Motofumi; Murota, Tadatoshi; Uosaki, Kohei; Ueda, Wataru

    2013-07-31

    For the development of a rechargeable metal-air battery, which is expected to become one of the most widely used batteries in the future, slow kinetics of discharging and charging reactions at the air electrode, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively, are the most critical problems. Here we report that Ruddlesden-Popper-type layered perovskite, RP-LaSr3Fe3O10 (n = 3), functions as a reversible air electrode catalyst for both ORR and OER at an equilibrium potential of 1.23 V with almost no overpotentials. The function of RP-LaSr3Fe3O10 as an ORR catalyst was confirmed by using an alkaline fuel cell composed of Pd/LaSr3Fe3O10-2x(OH)2x·H2O/RP-LaSr3Fe3O10 as an open circuit voltage (OCV) of 1.23 V was obtained. RP-LaSr3Fe3O10 also catalyzed OER at an equilibrium potential of 1.23 V with almost no overpotentials. Reversible ORR and OER are achieved because of the easily removable oxygen present in RP-LaSr3Fe3O10. Thus, RP-LaSr3Fe3O10 minimizes efficiency losses caused by reactions during charging and discharging at the air electrode and can be considered to be the ORR/OER electrocatalyst for rechargeable metal-air batteries. PMID:23802735

  7. XPS study of surface state of novel perovskite system Dy0.5Sr0.5Co0.8Fe0.2O3-δ as cathode for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Kautkar, Pranay R.; Acharya, Smita A.; Tumram, Priya V.; Deshpande, U. P.

    2016-05-01

    In the present attempt,novel perovskite oxide Dy0.5Sr0.5Co0.8Fe0.2O3-δ (DSCF) as cathode material has been synthesized by an Ethylene glycol-citrate combined sol-gel combustion route. Orthorhombic symmetry structure is confirmed by X-ray diffraction (XRD) and data is well fitted using Rietveld refinement by Full-Prof software suite. Chemical natureof surface of DSCF has been analyzed by using X-ray photoelectron spectroscopy (XPS). XPS result shows that Dy ions are in +3 oxidation state and Sr in +2 states. However Co2p and Fe2p spectra indicates partial change in oxidation state from Co3+/Fe3+ to Co4+/Fe4+. These attribute to develop active sites on the surface for oxygen ions. O1s XPS spectra shows two oxygen peaks relatedto lattice oxygen in perovskite and absorbed oxygen in oxygen vacancy are detected. O1s spectra demonstrate the existence of adsorbed oxygen species on the surface of DSCF oxide which is quite beneficial for intermediate temperature of Solid Oxide Fuel Cell.

  8. Crystal Structure of Calcium Silicate Perovskite Synthesized under Water Saturated Conditions at Mantle Related Pressure-Temperature

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    Perovskite-structured CaSiO3 (Ca-Pv) is the third most abundant mineral in the lower mantle. However, its crystal structure is still under debate and the solubility of H2O in Ca-Pv is not well constrained. We have conducted in situ X-ray diffraction measurements on Ca-Pv under H2O saturated conditions in the laser-heated diamond-anvil cell at the GSECARS and HPCAT sectors of the Advanced Photon Source. Glass starting materials were mixed with platinum powder (10 wt%) for laser coupling and internal pressure scale. Cold compressed foils of the mixtures were loaded in the diamond-anvil cell together with Ne or water. The X-ray diffraction patterns of the Ca-Pv sample synthesized in a Ne medium are consistent with a cubic perovskite structure at both 300 K and high temperatures up to 2,400 K at 50 GPa. No clear peak splittings were observed within the resolution of the angle-dispersive powder diffraction technique. However, in the experiments with water, clear splitting of the 200 diffraction line appears during heating to temperatures over 2000 K and remain after temperature quench at 32 GPa. The peak splittings were clearly observed at high temperatures to 2400 K, which is close to the melting point of water at the pressure. The different structural behaviors of Ca-Pv depending on media (Ne and water) may suggest that OH might enter into the crystal structure of nominally anhydrous Ca-Pv phase at high pressure and high temperature.

  9. Structural Investigations of Complex Oxides using Synchrotron Radiation

    SciTech Connect

    Hans-Conrad zur Loye

    2007-03-24

    The work is a collaborative effort between Prof. Hanno zur Loye at the University of South Carolina and Dr. Tom Vogt at Brookhaven National Laboratory. The collaborative research focuses on the synthesis and the structural characterization of perovskites and perovskite related oxides and will target new oxide systems where we have demonstrated expertise in synthesis, yet lack the experimental capabilities to answer important structural issues. Synthetically, we will focus on two subgroups of perovskite structures, the double and triple perovskites, and the 2H-perovskite related oxides belonging to the A3n+3mA’nB3m+nO9m+6n family. In the first part of the proposal, our goal of synthesizing and structurally characterizing new ruthenium, iridium, rhodium and ruthenium containing double and triple perovskites, with the emphasis on exercising control over the oxidation state(s) of the metals, is described. These oxides will be of interest for their electronic and magnetic properties that will be investigated as well.

  10. Hybrid Perovskite/Perovskite Heterojunction Solar Cells.

    PubMed

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

    2016-06-28

    Recently developed organic-inorganic hybrid perovskite solar cells combine low-cost fabrication and high power conversion efficiency. Advances in perovskite film optimization have led to an outstanding power conversion efficiency of more than 20%. Looking forward, shifting the focus toward new device architectures holds great potential to induce the next leap in device performance. Here, we demonstrate a perovskite/perovskite heterojunction solar cell. We developed a facile solution-based cation infiltration process to deposit layered perovskite (LPK) structures onto methylammonium lead iodide (MAPI) films. Grazing-incidence wide-angle X-ray scattering experiments were performed to gain insights into the crystallite orientation and the formation process of the perovskite bilayer. Our results show that the self-assembly of the LPK layer on top of an intact MAPI layer is accompanied by a reorganization of the perovskite interface. This leads to an enhancement of the open-circuit voltage and power conversion efficiency due to reduced recombination losses, as well as improved moisture stability in the resulting photovoltaic devices. PMID:27228558

  11. Perovskite Sr-doped LaCrO3 as a new p-type transparent conducting oxide

    SciTech Connect

    Zhang, Hongliang; Du, Yingge; Papadogianni, Alexandra; Bierwagen, Oliver; Sallis, Shawn; Piper, Louis F. J.; Bowden, Mark E.; Shutthanandan, V.; Sushko, Petr; Chambers, Scott A.

    2015-09-16

    Transparent conducting oxides (TCOs) constitute a unique class of materials which combine the seemingly mutually exclusive properties of electrical conductivity and optical transparency in a single material. TCOs are useful for a wide range of applications including solar cells, displays, light emitting diodes and transparent electronics. Simple post-transition metal oxides such as ZnO, In2O3 and SnO2 are wide gap insulators in which the ionic character generates an oxygen 2p-derived valence band (VB) and a metal s-derived conduction band (CB), resulting in large optical band gaps (>3.0 eV) and excellent n-type conductivity when donor doped. In contrast, the development of efficient p-type TCOs remains a global materials challenge. Converting n-type oxides to p-type analogs by acceptor doping is extremely difficult and these materials display poor conductivity.

  12. 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

  13. 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

  14. Structure and local structure of perovskite based materials

    NASA Astrophysics Data System (ADS)

    Rossell Abrodos, Marta Dacil

    Perovskites, with general formula ABX3, where A and B are cations and X is an anion, form a very important class of inorganic crystals whose physical properties are extensively used in many technological applications. The basic, so-called aristotype structure, consists of an infinite array of corner-linked anion octahedra, with the A cations in the spaces between the octahedra and a B cation at the center of each octahedron. Interesting physical properties are often related to the flexibility of the perovskite structure to deform or to form non-stoichiometric compositions. In this thesis, four perovskite-related systems are studied. Transmission electron microscopy (TEM) is of prime interest to analyze the influence of the structure and microstructure on the physical properties of these systems. (1) The anion-deficient Sr4Fe6O12+delta (delta < 1) derivatives. These materials are mixed conducting oxides with high oxygen and electronic conductivity. A complete characterization of the structure of these anion-deficient compounds is deduced from electron diffraction and high-resolution TEM. The presence of anion vacancies in the Sr4Fe6O12+delta (delta < 1) structure is suggested to have an influence on the transport properties. (2) The CaRMnSnO6 (R = La, Pr, Nd, Sm-Dy) double perovskites. A random distribution of the Ca and R cations over the A positions and Mn and Sn cations over the B positions is found. Due to a random distribution of the Mn 3+ and Sn4+ cations, a spin glass behavior was found for CaLaMnSnO6. (3) The K3AlF6 elpasolite-type (or ordered double perovskite) structure. This compound is of high technological importance since it is a basic component of the melts for low temperature electrolysis in aluminum smelting. A sequence of phase transitions at different temperatures in K3AlF6 along with the data on unit cell dimensions and space symmetry of three major polymorphs is reported. (4) Ca 2Fe2O5 brownmillerite-type thin films deposited on three different

  15. Conductivity and redox stability of perovskite oxide SrFe1-xTixO3-δ (x ≤ 0.3)

    NASA Astrophysics Data System (ADS)

    Cowin, Peter I.; Lan, Rong; Petit, Christophe T. G.; Tao, Shanwen

    2015-08-01

    A solid solution with the cubic perovskite structure was observed for SrFe1-xTixO3-δ (x = 0-0.3), with an increase in the lattice parameters noted upon increasing dopant concentration. Material stability in air was observed for all compounds, with a decrease in conductivity noted upon increasing dopant concentration attributed to a reduction in charge carrier concentration. A reduction in weight proportional to the titanium content was observed upon exposure to 5% H2/Ar, although reduction at 700 °C was observed to elicit a structural transitions and the formation of a secondary phase for samples SrFeO3-δ and SrFe0.9Ti0.1O3-δ respectively. Conductivity measurements at 600 °C demonstrated a larger decrease in the conductivity with increasing dopant concentration, while all investigated oxides are stable after reducing in 5%H2/Ar at 600 °C. It was found that the conductivity of SrFe0.8Ti0.2O3-δ and SrFe0.7Ti0.3O3-δ in 5%H2/Ar is insufficient to be used as anode for SOFCs. In the investigated compositions, SrFe0.9Ti0.1O3-δ exhibits desired conductivity and redox stability, reduced thermal expansion coefficient compared to SrFeO3-δ, which is a promising redox stable anode for IT-SOFCs.

  16. Interplay between size, composition, and phase transition of nanocrystalline Cr(3+)-doped BaTiO3 as a path to multiferroism in perovskite-type oxides.

    PubMed

    Ju, Ling; Sabergharesou, Tahereh; Stamplecoskie, Kevin G; Hegde, Manu; Wang, Ting; Combe, Nicole A; Wu, Hongyu; Radovanovic, Pavle V

    2012-01-18

    Multiferroics, materials that exhibit coupling between spontaneous magnetic and electric dipole ordering, have significant potential for high-density memory storage and the design of complex multistate memory elements. In this work, we have demonstrated the solvent-controlled synthesis of Cr(3+)-doped BaTiO(3) nanocrystals and investigated the effects of size and doping concentration on their structure and phase transformation using X-ray diffraction and Raman spectroscopy. The magnetic properties of these nanocrystals were studied by magnetic susceptibility, magnetic circular dichroism (MCD), and X-ray magnetic circular dichroism (XMCD) measurements. We observed that a decrease in nanocrystal size and an increase in doping concentration favor the stabilization of the paraelectric cubic phase, although the ferroelectric tetragonal phase is partly retained even in ca. 7 nm nanocrystals having the doping concentration of ca. 5%. The chromium(III) doping was determined to be a dominant factor for destabilization of the tetragonal phase. A combination of magnetic and magneto-optical measurements revealed that nanocrystalline films prepared from as-synthesized paramagnetic Cr(3+)-doped BaTiO(3) nanocrystals exhibit robust ferromagnetic ordering (up to ca. 2 μ(B)/Cr(3+)), similarly to magnetically doped transparent conducting oxides. The observed ferromagnetism increases with decreasing constituent nanocrystal size because of an enhancement in the interfacial defect concentration with increasing surface-to-volume ratio. Element-specific XMCD spectra measured by scanning transmission X-ray microscopy (STXM) confirmed with high spatial resolution that magnetic ordering arises from Cr(3+) dopant exchange interactions. The results of this work suggest an approach to the design and preparation of multiferroic perovskite materials that retain the ferroelectric phase and exhibit long-range magnetic ordering by using doped colloidal nanocrystals with optimized composition and

  17. Structure-property relations in the distorted ordered double perovskite Sr2InReO6

    NASA Astrophysics Data System (ADS)

    Gao, Haitao; Llobet, Anna; Barth, Joachim; Winterlik, Jürgen; Felser, Claudia; Panthöfer, Martin; Tremel, Wolfgang

    2011-04-01

    The rock-salt ordered type double perovskite Sr2InReO6 is systematically investigated by means of powder x-ray diffraction, neutron powder diffraction, temperature-dependent electrical transport, heat capacity and magnetic susceptibility measurements, and electronic band structure calculations. The crystal structure of Sr2InReO6 is revised to be monoclinic (cryolite structure type, space group P21/n) with all structural distortions according to the high-symmetry aristotype due to tilting of the InO6 and ReO6 octahedra, respectively. Sr2InReO6 is a Mott insulator with variable-range hopping. Two 5d electrons are unpaired and localized on the Re5+ ions. Although there are antiferromagnetic interactions, the fcc arrangement of the Re5+ cations (5d2) leads to a geometrically frustrated spin system that does not achieve full magnetic order. The experimental findings are in line with the results of electronic structure computation using the WIEN2K program within the GGA + U approximation exclusively on the basis of the revised crystal structure model.

  18. 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

  19. Transformation of proton-conducting Perovskite-type into fluorite-type fast oxide ion electrolytes using a CO2 capture technique and their electrical properties.

    PubMed

    Trobec, Francesca; Thangadurai, Venkataraman

    2008-10-01

    Fast oxide ion conducting Ce 1- x M x O 2-delta (M = In, Sm; x = 0.1, 0.2) and Ce 0.8Sm 0.05Ca 0.15O 1.825 were prepared from the corresponding perovskite-like structured materials with nominal chemical composition of BaCe 1- x M x O 3-delta and BaCe 0.8Sm 0.05Ca 0.15O 2.825, respectively, by reacting with CO 2 at 800 degrees C for 12 h. Powder X-ray diffraction (PXRD) analysis showed the formation of fluorite-type CeO 2 and BaCO 3 just after reaction with CO 2. The amount of CO 2 gained per ceramic gram was found to be consistent with the Ba content. The CO 2 reacted samples were washed with dilute HCl and water, and the resultant solid product was characterized structurally and electrically employing various solid-state characterization methods, including PXRD, and alternating current (ac) impedance spectroscopy. The lattice constant of presently prepared Ce 1- x M x O 2-delta and Ce 0.8Sm 0.05Ca 0. 15O 1.825 by a CO 2 capture technique follows the expected ionic radii trend. For example, In-doped Ce 0.9In 0.1O 1.95 (In (3+) (VIII) = 0.92 A) sample showed a fluorite-type cell constant of 5.398(1) A, which is lower than the parent CeO 2 (5.411 A, Ce (4+) (VIII) = 0.97 A). Our attempt to prepare single-phase In-doped CeO 2 samples at 800, 1000, and 1500 degrees C using the ceramic method was unsuccessful. However, we were able to prepare single-phase Ce 0.9In 0.1O 1.95 and Ce 0.8In 0.2O 1.9 by the CO 2 capture method from the corresponding barium perovskites. The PXRD studies showed that the In-doped samples are thermodynamically unstable above 800 degrees C. The ac electrical conductivity studies using Pt electrodes showed the presence of bulk, grain-boundary, and electrode contributions over the investigated temperature range in the frequency range of 10 (-2)-10 (7) Hz. The bulk ionic conductivity and activation energy for the electrical conductivity of presently prepared Sm- and (Sm + Ca)-doped CeO 2 samples shows conductivities similar to those of materials

  20. PrBa0.5Sr0.5Co2O5+δ layered perovskite cathode for intermediate temperature solid oxide fuel cells

    SciTech Connect

    Ding, Hanping; Xue, Xingjian

    2010-02-06

    Layered perovskite oxides have ordered A-cations localizing oxygen vacancies, and may potentially improve oxygen ion diffusivity and surface exchange coefficient. The A-site-ordered layered perovskite PrBa0.5Sr0.5Co2O5+δ (PBSC) was evaluated as new cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs). The material was characterized using electrochemical impedance spectroscopy in a symmetrical cell system (PBSC/Ce0.9Sm0.1O1.9 (SDC)/PBSC), exhibiting excellent performance in the intermediate temperature range of 500–700 °C. An area-specific-resistance (ASR) of 0.23 Ω cm2 was achieved at 650 °C for cathode polarization. The low activation energy (Ea) 124 kJ mol-1 is comparable to that of La0.8Sr0.2CoO3-δ. A laboratory-scaled SDC-based tri-layer cell of Ni-SDC/SDC/PBSC was tested in intermediate temperature conditions of 550 to 700 °C. A maximum power density of 1045 mW cm-2 was achieved at 700 °C. The interfacial polarization resistance is as low as 0.285, 0.145, 0.09 and 0.05 Ω cm2 at 550, 600, 650 and 700 °C, respectively. Layered perovskite PBSC shows promising performance as cathode material for IT-SOFCs.

  1. Enhanced performance in fluorene-free organometal halide perovskite light-emitting diodes using tunable, low electron affinity oxide electron injectors.

    PubMed

    Hoye, Robert L Z; Chua, Matthew R; Musselman, Kevin P; Li, Guangru; Lai, May-Ling; Tan, Zhi-Kuang; Greenham, Neil C; MacManus-Driscoll, Judith L; Friend, Richard H; Credgington, Dan

    2015-02-25

    Fluorene-free perovskite light-emitting diodes (LEDs) with low turn-on voltages, higher luminance and sharp, color-pure electroluminescence are obtained by replacing the F8 electron injector with ZnO, which is directly deposited onto the CH3NH3PbBr3 perovskite using spatial atmospheric atomic layer deposition. The electron injection barrier can also be reduced by decreasing the ZnO electron affinity through Mg incorporation, leading to lower turn-on voltages. PMID:25573086

  2. Oxygen-vacancy concentration in A{sub 2}MgMoO{sub 6-{delta}} double-perovskite oxides

    SciTech Connect

    Matsuda, Y.; Karppinen, M.; Yamazaki, Y.; Yamauchi, H.

    2009-07-15

    Accurate oxygen-content analysis by means of a coulometric redox titration method specially devised for the purpose shows that as-synthesized (in 5% H{sub 2}/Ar) samples of the recently reported novel solid oxide fuel cells anode material Sr{sub 2}MgMoO{sub 6-{delta}} contain oxygen vacancies with a concentration of {delta}{approx}0.05. Oxygen contents and the resultant Mo-valence values are also analyzed for various A{sub 2}MgMoO{sub 6-{delta}} samples in order to reveal both the isovalent and aliovalent A-site cation substitution effects. - Graphical Abstract: A highly reproducible coulometric redox titration method has been developed to accurately analyze the mixed V/VI valence state of molybdenum and thereby the oxygen content in the recently reported SOFC-anode materials of A{sub 2}MgMoO{sub 6-{delta}}.

  3. 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

  4. Highly efficient light management for perovskite solar cells

    NASA Astrophysics Data System (ADS)

    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.

  5. Recent Advances in Interface Engineering for Planar Heterojunction Perovskite Solar Cells.

    PubMed

    Yin, Wei; Pan, Lijia; Yang, Tingbin; Liang, Yongye

    2016-01-01

    Organic-inorganic hybrid perovskite solar cells are considered as one of the most promising next-generation solar cells due to their advantages of low-cost precursors, high power conversion efficiency (PCE) and easy of processing. In the past few years, the PCEs have climbed from a few to over 20% for perovskite solar cells. Recent developments demonstrate that perovskite exhibits ambipolar semiconducting characteristics, which allows for the construction of planar heterojunction (PHJ) perovskite solar cells. PHJ perovskite solar cells can avoid the use of high-temperature sintered mesoporous metal oxides, enabling simple processing and the fabrication of flexible and tandem perovskite solar cells. In planar heterojunction materials, hole/electron transport layers are introduced between a perovskite film and the anode/cathode. The hole and electron transporting layers are expected to enhance exciton separation, charge transportation and collection. Further, the supporting layer for the perovskite film not only plays an important role in energy-level alignment, but also affects perovskite film morphology, which have a great effect on device performance. In addition, interfacial layers also affect device stability. In this review, recent progress in interfacial engineering for PHJ perovskite solar cells will be reviewed, especially with the molecular interfacial materials. The supporting interfacial layers for the optimization of perovskite films will be systematically reviewed. Finally, the challenges remaining in perovskite solar cells research will be discussed. PMID:27347923

  6. Effects of solvent and chelating agent on synthesis of solid oxide fuel cell perovskite, La{sub 0.8}Sr{sub 0.2}CrO{sub 3-{delta}}

    SciTech Connect

    Lee, Byoung I.; Gupta, Ravindra K.; Whang, Chin M.

    2008-02-05

    Effects of solvent and chelating agent on synthesis of La{sub 0.8}Sr{sub 0.2}CrO{sub 3-{delta}} perovskite are reported. Samples are synthesized using a solvent (ethylene glycol or 2-methoxyethanol) and a chelating agent (acetylacetone, citric acid or ethylene diamine tetraacetic acid) by polymeric-gel method, and characterized by X-ray diffractometry and Fourier-transform infrared spectroscopy. Citric acid to metal cations molar ratio (Rc) is varied for ethylene glycol-citric acid system. Samples are mainly orthorhombic perovskite. SrCrO{sub 4} is appeared as a secondary phase and found to be the lowest for ethylene glycol-citric acid combination with Rc equal to 7. Crystallographic parameters of perovskite phase are determined and compared with those of LaCrO{sub 3}. A mechanism employing a partial-charge model, chelating effect and solvent-cage effect is proposed to explain the results. Effect of sintering temperature on phase, relative density and morphology of samples prepared using ethylene glycol and citric acid (Rc = 7) is also reported.

  7. Investigation of hyperfine interactions in RMO3 (R =La, Nd; M =Cr, Fe) antiferromagnetic perovskite oxides using PAC spectroscopy

    NASA Astrophysics Data System (ADS)

    Carbonari, A. W.; Cavalcante, F. H. M.; Junqueira, A. C.; Leite, D. M. T.; Saxena, R. N.; Mestnik-Filho, J.

    The local magnetic interaction at the transition metal sites in RMO3 (R=La, Nd; M=Cr, Fe) compounds has been investigated by perturbed angular correlation (PAC) technique using 181Hf→181Ta probe nuclei. The present measurements cover a temperature range from 10 K to 1000 K. Above the respective Neel temperature, each compound shows a unique quadrupolar frequency that decreases linearly with temperature. These interactions were assigned to the radioactive probe substituting Cr or Fe sites. Below TN, a combined electric plus magnetic hyperfine interaction was observed. The magnetic interaction revealed that the super transferred hyperfine fields on 181Ta at the Cr sites in (La,Nd)CrO3 extrapolated to 0 K, are much smaller than the corresponding values at Fe sites in (La,Nd)FeO3. This difference was attributed to different distribution of d electrons in Cr3+ (3d3) and Fe3+ (3d5) ions in each compound. As the fields for Nd compounds are smaller than those for La compounds, the role of rare-earth ions in the magnetism of these oxides is also discussed.

  8. Investigation of hyperfine interactions in RMO 3 (R = La, Nd; M = Cr, Fe) antiferromagnetic perovskite oxides using PAC spectroscopy

    NASA Astrophysics Data System (ADS)

    Carbonari, A. W.; Cavalcante, F. H. M.; Junqueira, A. C.; Leite, D. M. T.; Saxena, R. N.; Mestnik-Filho, J.

    2007-07-01

    The local magnetic interaction at the transition metal sites in RMO3 (R = La, Nd; M = Cr, Fe) compounds has been investigated by perturbed angular correlation (PAC) technique using 181Hf→181Ta probe nuclei. The present measurements cover a temperature range from 10 K to 1000 K. Above the respective Néel temperature, each compound shows a unique quadrupolar frequency that decreases linearly with temperature. These interactions were assigned to the radioactive probe substituting Cr or Fe sites. Below T N , a combined electric plus magnetic hyperfine interaction was observed. The magnetic interaction revealed that the super transferred hyperfine fields on 181Ta at the Cr sites in (La,Nd)CrO3 extrapolated to 0 K, are much smaller than the corresponding values at Fe sites in (La,Nd)FeO3. This difference was attributed to different distribution of d electrons in Cr3 + (3d3) and Fe3 + (3d5) ions in each compound. As the fields for Nd compounds are smaller than those for La compounds, the role of rare-earth ions in the magnetism of these oxides is also discussed.

  9. Pyrochlore and perovskite potassium tantalate: enthalpies of formation and phase transformation.

    PubMed

    Zlotnik, Sebastian; Sahu, Sulata K; Navrotsky, Alexandra; Vilarinho, Paula M

    2015-03-23

    Alkali niobates and tantalates are currently important lead-free functional oxides. The formation and decomposition energetics of potassium tantalum oxide compounds (K2 O-Ta2 O5 ) were measured by high-temperature oxide melt solution calorimetry. The enthalpies of formation from oxides of KTaO3 perovskite and defect pyrochlores with K/Ta ratio of less than 1 stoichiometry-K0.873 Ta2.226 O6 , K1.128 Ta2.175 O6 , and K1.291 Ta2.142 O6 -were experimentally determined, and the values are (-203.63 ± 2.92) kJ mol(-1) for KTaO3 perovskite, and (-339.54 ± 5.03) kJ mol(-1) , (-369.71 ± 4.84) kJ mol(-1) , and (-364.78 ± 4.24) kJ mol(-1) , respectively, for non-stoichiometric pyrochlores. That of stoichiometric defect K2 Ta2 O6 pyrochlore, by extrapolation, is (-409.87 ± 6.89) kJ mol(-1) . Thus, the enthalpy of the stoichiometric pyrochlore and perovskite at K/Ta=1 stoichiometry are equal in energy within experimental error. By providing data on the thermodynamic stability of each phase, this work supplies knowledge on the phase-formation process and phase stability within the K2 O-Ta2 O5 system, thus assisting in the synthesis of materials with reproducible properties based on controlled processing. Additionally, the relation of stoichiometric and non-stoichiometric pyrochlore with perovskite structure in potassium tantalum oxide system is discussed. PMID:25688734

  10. Do dislocations act as atomic autobahns for oxygen in the perovskite oxide SrTiO3?

    NASA Astrophysics Data System (ADS)

    Metlenko, Veronika; Ramadan, Amr H. H.; Gunkel, Felix; Du, Hongchu; Schraknepper, Henning; Hoffmann-Eifert, Susanne; Dittmann, Regina; Waser, Rainer; de Souza, Roger A.

    2014-10-01

    The transport properties of edge dislocations comprising a symmetrical 6° [001] tilt grain boundary in weakly acceptor-doped SrTiO3 were investigated by means of various experimental and computational techniques. Oxygen transport along the dislocation array was probed by means of 18O/16O exchange experiments under (standard) oxidising conditions (pO2 = 5 × 10-1 bar) and also under reducing conditions (pO2 = 7 × 10-22 bar) at T = 973 K. In both cases, isotope profiles obtained by Secondary Ion Mass Spectrometry (SIMS) indicated no evidence of fast diffusion along the dislocation array. Charge transport across the dislocation array was probed in equilibrium electrical conductivity measurements as a function of oxygen partial pressure, 10-23 <= pO2/bar <= 1 at temperatures of T/K = 950, 1050, 1100. A significant decrease in the conductivity of the bicrystal (relative to that of a single crystal) was observed under oxidising conditions, but not under reducing conditions. These studies were complemented by static lattice simulations employing empirical pair-potentials. The simulations predict, that the tilt boundary comprises two types of dislocation cores, that the formation of oxygen vacancies is energetically preferred at both cores relative to the bulk, and that the migration of oxygen ions along both cores is hindered relative to the bulk. Combining all results and literature reports, we present a comprehensive and consistent picture of the transport properties of dislocations in SrTiO3.

  11. Do dislocations act as atomic autobahns for oxygen in the perovskite oxide SrTiO3?

    PubMed

    Metlenko, Veronika; Ramadan, Amr H H; Gunkel, Felix; Du, Hongchu; Schraknepper, Henning; Hoffmann-Eifert, Susanne; Dittmann, Regina; Waser, Rainer; De Souza, Roger A

    2014-11-01

    The transport properties of edge dislocations comprising a symmetrical 6° [001] tilt grain boundary in weakly acceptor-doped SrTiO3 were investigated by means of various experimental and computational techniques. Oxygen transport along the dislocation array was probed by means of (18)O/(16)O exchange experiments under (standard) oxidising conditions (pO2 = 5 × 10(-1) bar) and also under reducing conditions (pO2 = 7 × 10(-22) bar) at T = 973 K. In both cases, isotope profiles obtained by Secondary Ion Mass Spectrometry (SIMS) indicated no evidence of fast diffusion along the dislocation array. Charge transport across the dislocation array was probed in equilibrium electrical conductivity measurements as a function of oxygen partial pressure, 10(-23) ≤ pO2/bar ≤ 1 at temperatures of T/K = 950, 1050, 1100. A significant decrease in the conductivity of the bicrystal (relative to that of a single crystal) was observed under oxidising conditions, but not under reducing conditions. These studies were complemented by static lattice simulations employing empirical pair-potentials. The simulations predict, that the tilt boundary comprises two types of dislocation cores, that the formation of oxygen vacancies is energetically preferred at both cores relative to the bulk, and that the migration of oxygen ions along both cores is hindered relative to the bulk. Combining all results and literature reports, we present a comprehensive and consistent picture of the transport properties of dislocations in SrTiO3. PMID:25263456

  12. A-site calcium-doped Pr1-xCaxBaCo2O5+δ double perovskites as cathodes for intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Fu, Dawei; Jin, Fangjun; He, Tianmin

    2016-05-01

    The LnBaCo2O5+δ (Ln = rare earth) double perovskite cathodes possess superior electrochemical performance in intermediate-temperature solid oxide fuel cells (IT-SOFCs). However, high thermal expansion coefficients (TECs) and material costs are major challenges to their widespread applications. In this paper, a novel A-site Ca doping strategy that can suppress the spin-state transition of Co3+ is proposed to reduce the TECs and material costs of Pr1-xCaxBaCo2O5+δ (x = 0.1-0.4; PCBCO). Substitution of Ca for Pr effectively reduces the TEC from 22.2 × 10-6 K-1 at x = 0.1 to 19.1 × 10-6 K-1 at x = 0.3 between 100 and 800 °C. PCBCO exhibits good chemical compatibility with the Sm0.2Ce0.8O1.9 (SDC) electrolyte. The area-specific resistances of PCBCO cathodes with x = 0.1, 0.2, and 0.3 are 0.081, 0.082, and 0.089 Ω cm2, respectively, at 700 °C on the SDC electrolyte. The maximum power densities of a single cell on a 0.3 mm-thick SDC electrolyte reach 646.5, 636.8, and 620.6 mW cm-2 at 800 °C for cathodes with x = 0.1, 0.2, and 0.3, respectively. The PCBCO double perovskites exhibit excellent chemical compatibility and electrochemical performance while reducing the TECs and material costs; thus, these double perovskites are promising cathode materials for applications in IT-SOFCs.

  13. Probing Photocurrent Generation, Charge Transport, and Recombination Mechanisms in Mesostructured Hybrid Perovskite through Photoconductivity Measurements.

    PubMed

    Sveinbjörnsson, Kári; Aitola, Kerttu; Zhang, Xiaoliang; Pazoki, Meysam; Hagfeldt, Anders; Boschloo, Gerrit; Johansson, Erik M J

    2015-11-01

    Conductivity of methylammonium lead triiodide (MAPbI3) perovskite was measured on different mesoporous metal oxide scaffolds: TiO2, Al2O3, and ZrO2, as a function of incident light irradiation and temperature. It was found that MAPbI3 exhibits intrinsic charge separation, and its conductivity stems from a majority of free charge carriers. The crystal morphology of the MAPbI3 was found to significantly affect the photoconductivity, whereas in the dark the conductivity is governed by the perovskite in the pores of the mesoporous scaffold. The temperature-dependent conductivity measurements also indicate the presence of states within the band gap of the perovskite. Despite a relatively large amount of crystal defects in the measured material, the main recombination mechanism of the photogenerated charges is bimolecular (band-to-band), which suggests that the defect states are rather inactive in the recombination. This may explain the remarkable efficiencies obtained for perovskite solar cells prepared with wet-chemical methods. PMID:26538041

  14. Kinetics of oxygen reduction in perovskite cathodes for solid oxide fuel cells: A combined modeling and experimental approach

    NASA Astrophysics Data System (ADS)

    Miara, Lincoln James

    Solid oxide fuel cells (SOFCs) have the potential to replace conventional stationary power generation technologies; however, there are major obstacles to commercialization, the most problematic of which is poor cathode performance. Commercialization of SOFCs will follow when the mechanisms occurring at the cathode are more thoroughly understood and adapted for market use. The catalytic reduction of oxygen occurring in SOFC cathodes consists of many elementary steps such as gas phase diffusion, chemical and/or electrochemical reactions which lead to the adsorption and dissociation of molecular oxygen onto the cathode surface, mass transport of oxygen species along the surface and/or through the bulk of the cathode, and full reduction and incorporation of the oxygen at the cathode/electrolyte two or three phase boundary. Electrochemical impedance spectroscopy (EIS) is the main technique used to identify the occurrence of these different processes, but when this technique is used without an explicit model describing the kinetics it is difficult to unravel the interdependence of each of these processes. The purpose of this dissertation is to identify the heterogeneous reactions occurring at the cathode of an SOFC by combining experimental EIS results with mathematical models describing the time dependent behavior of the system. This analysis is performed on two different systems. In the first case, experimental EIS results from patterned half cells composed of Ca-doped lanthanum manganite (LCM)| yttria-doped ZrO2 (YSZ) are modeled to investigate the temperature and partial pressure of oxygen, pO2, dependence of oxygen adsorption/dissociation onto the LCM surface, surface diffusion of atomic oxygen, and electrochemical reduction and incorporation of the oxygen into the electrolyte in the vicinity of the triple phase boundary (TPB). This model determines the time-independent state-space equations from which the Faradaic admittance transfer function is obtained. The

  15. Rational Strategies for Efficient Perovskite Solar Cells.

    PubMed

    Seo, Jangwon; Noh, Jun Hong; Seok, Sang Il

    2016-03-15

    A long-standing dream in the large scale application of solar energy conversion is the fabrication of solar cells with high-efficiency and long-term stability at low cost. The realization of such practical goals depends on the architecture, process and key materials because solar cells are typically constructed from multilayer heterostructures of light harvesters, with electron and hole transporting layers as a major component. Recently, inorganic-organic hybrid lead halide perovskites have attracted significant attention as light absorbers for the fabrication of low-cost and high-efficiency solar cells via a solution process. This mainly stems from long-range ambipolar charge transport properties, low exciton binding energies, and suitable band gap tuning by managing the chemical composition. In our pioneering work, a new photovoltaic platform for efficient perovskite solar cells (PSCs) was proposed, which yielded a high power conversion efficiency (PCE) of 12%. The platform consisted of a pillared architecture of a three-dimensional nanocomposite of perovskites fully infiltrating mesoporous TiO2, resulting in the formation of continuous phases and perovskite domains overlaid with a polymeric hole conductor. Since then, the PCE of our PSCs has been rapidly increased from 3% to over 20% certified efficiency. The unprecedented increase in the PCE can be attributed to the effective integration of the advantageous attributes of the refined bicontinuous architecture, deposition process, and composition of perovskite materials. Specifically, the bicontinuous architectures used in the high efficiency comprise a layer of perovskite sandwiched between mesoporous metal-oxide layer, which is a very thinner than that of used in conventional dye-sensitized solar cells, and hole-conducting contact materials with a metal back contact. The mesoporous scaffold can affect the hysteresis under different scan direction in measurements of PSCs. The hysteresis also greatly depends on

  16. Photoconductivity of transparent perovskite oxide semiconductors BaSnO3 and SrTiO3 epitaxial thin films

    NASA Astrophysics Data System (ADS)

    Park, Jisung; Kim, Useong; Char, Kookrin; Institute of Applied Physics, Department of Physics; Astronomy, Seoul National University, Seoul Team

    We have measured the photoconductivity (PC) of epitaxial thin films of transparent semiconductor BaSnO3 (BSO) and SrTiO3 (STO) at room temperature. The epitaxial thin films of BSO and STO were grown by pulsed laser ablation technique on the MgO substrates to exclude any conductance from the substrate owing to its large bandgap (~7.8 eV). Despite the same crystalline structure and similar band gap sizes (~3.2 eV), the PC of BSO behaved very differently. The slowly varying component in the PC of BSO is much larger than that of STO; the PC of BSO increased slowly, reached higher magnitude after the same duration of illumination, and persisted longer than many hours after the light was turned off, whereas the PC of STO showed little persistent conductivity. The spectral responses of the PC of BSO and STO showed their highest peaks below 400 nm when measured by a UV monochromator system, suggesting that the electron-hole pair generation is the main mechanism of the PC for both materials. The higher mobility of BSO should be partially responsible for the higher PC. The large persistent PC of BSO seems related to the dislocations that trap electrons easily.

  17. Computational Study of Oxygen Diffusion along a[100] Dislocations in the Perovskite Oxide SrTiO3.

    PubMed

    Waldow, Stephan P; De Souza, Roger A

    2016-05-18

    We used classical molecular-dynamics simulations to study the atomistic structure of, and the diffusion of oxygen ions along, the periodic array of edge dislocations comprising a symmetrical 6.0° [100] tilt grain boundary in SrTiO3. The results indicate that, at elevated temperatures, the two types of dislocation core (TiO2-type and SrO-type) that make up the boundary are stable and that oxygen-deficient cores maintain their dissociated structures. They also confirm that oxygen vacancies prefer to reside at the cores rather than in the bulk. Tracer diffusion coefficients of oxygen were obtained for oxygen-deficient bulk and grain-boundary simulation cells at temperatures in the range of 1000 ≤ T/K ≤ 2300. Calculated values of the oxygen-vacancy diffusion coefficient for the bulk phase agree extremely well with published experimental data. Tracer diffusion coefficients obtained for the grain-boundary cell are, in comparison to those for the bulk, lower in magnitude and have a higher activation enthalpy, indicating that, relative to the bulk, the migration of oxygen ions along a[100] dislocation cores in SrTiO3 is hindered. These results provide further support for the decoupled model of filament formation in resistively switching SrTiO3. PMID:27121113

  18. 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

    2016-06-01

    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. PMID:27279218

  19. 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.

  20. Structural study of a sol gel derived novel solid oxide fuel cell perovskite: (La1-xSrx)(Cr0.85Fe0.05Co0.05Ni0.05)O3-δ

    NASA Astrophysics Data System (ADS)

    Gupta, Ravindra K.; Whang, Chin Myung

    2007-05-01

    The effect of composition on the structure of the new solid oxide fuel cell (SOFC) perovskite (La1-xSrx)(Cr0.85Fe0.05Co0.05Ni0.05)O3-δ is studied using x-ray diffractometry, pycnometry, and Fourier-transform infrared and Raman spectroscopy. Samples were synthesized using the Pechini method via doping the La site with Sr2+, to a composition with x = 0-0.4 mole fraction, and at the Cr site with 0.05 mol of Co2+,Fe2+ and Ni2+, and the structural results were compared with those for orthorhombic LaCrO3. The samples were orthorhombic perovskite of the Pnma space group. A second phase, monoclinic SrCrO4, was also observed, whose content increased linearly with increasing x. A large decrease in the lattice and hence volume was observed for the sample with x = 0.1, which was accompanied by a sharp decrease in the Cr-O bond length, tilt angle and crystallite size. The structural parameters were almost invariant for x = 0.1-0.4, probably due to an increase in content of the high valence cations of smaller ionic radii, as suggested by an increase in the intensity of the defect band (~515 cm-1, IR). The octahedral CrO6 stretching, bending and tilting modes were found shifted accordingly. A mechanism employing a partial-charge model was proposed to explain the results.

  1. Perovskite-type catalytic materials for environmental applications

    NASA Astrophysics Data System (ADS)

    Labhasetwar, Nitin; Saravanan, Govindachetty; Megarajan, Suresh Kumar; Manwar, Nilesh; Khobragade, Rohini; Doggali, Pradeep; Grasset, Fabien

    2015-06-01

    Perovskites are mixed-metal oxides that are attracting much scientific and application interest owing to their low price, adaptability, and thermal stability, which often depend on bulk and surface characteristics. These materials have been extensively explored for their catalytic, electrical, magnetic, and optical properties. They are promising candidates for the photocatalytic splitting of water and have also been extensively studied for environmental catalysis applications. Oxygen and cation non-stoichiometry can be tailored in a large number of perovskite compositions to achieve the desired catalytic activity, including multifunctional catalytic properties. Despite the extensive uses, the commercial success for this class of perovskite-based catalytic materials has not been achieved for vehicle exhaust emission control or for many other environmental applications. With recent advances in synthesis techniques, including the preparation of supported perovskites, and increasing understanding of promoted substitute perovskite-type materials, there is a growing interest in applied studies of perovskite-type catalytic materials. We have studied a number of perovskites based on Co, Mn, Ru, and Fe and their substituted compositions for their catalytic activity in terms of diesel soot oxidation, three-way catalysis, N2O decomposition, low-temperature CO oxidation, oxidation of volatile organic compounds, etc. The enhanced catalytic activity of these materials is attributed mainly to their altered redox properties, the promotional effect of co-ions, and the increased exposure of catalytically active transition metals in certain preparations. The recent lowering of sulfur content in fuel and concerns over the cost and availability of precious metals are responsible for renewed interest in perovskite-type catalysts for environmental applications.

  2. Structural and superconducting properties of vanadium substituted Y Ba 2 (Cu 1-x V x) 3 O 9 perovskite oxide system

    NASA Astrophysics Data System (ADS)

    Al-Dallal, S.; Khan, M. N.; Memon, A.

    1991-12-01

    The superconducting properties YBaCuVO system has been studied. It was found that upon substituation of copper by vanadium, the critical temperature decreases linearly for the whole compositional range under investigation (0.2 ⩾ × ⩾ 0.001). X-ray diffraction analysis reveals that the structure of these compounds changes systematicaly from orthorhombic which corresponds to oxygen difficient perovskite to tetragonal.

  3. Perovskites for use as sulfur tolerant anodes

    NASA Astrophysics Data System (ADS)

    Howell, Thomas G.

    One of the major obstacles encountered when using solid oxide fuel cells with hydrocarbon fuels is sulfur poisoning. The current anode material used is Ni/YSZ and Ni is not sulfur tolerant; therefore, the performance of the cell will degrade over time due to the formation of NiS. Perovskites have demonstrated superior sulfur tolerance but lack the high conductivity and catalytic activity of Ni/YSZ cermets. One of the objectives of this effort is to explore the substitution of the A-site in an A2MgMoO 6 perovskite with Sr and Ba, to create Sr2MgMoO6 (SMMO) and Ba2MgMoO6 (BMMO), respectively, to improve the sulfur tolerance of solid oxide fuel cells (SOFCs). Sr2MgMoO 6, a double perovskite, has been previously studied and is suggested as a material of interest because of its relatively high conductivity and catalytic potential. Barium has not been previously studied and was selected as the dopant because the ionic radii (1.61 A) resulted in a calculated tolerance factor of 1.036 for BMMO when compared to SMMO, which has an ionic radii of 1.44 A and a calculated tolerance factor of 0.978. The tolerance factor for BaSrMgMoO6, a bi-substituted material synthesized for comparison as an intermediate formulation, was calculated to be 1.00. Another objective is to synthesize and characterize a series of lanthanum (La) doped Sr2MgMoO6 (SMMO) or La doped Sr2MgNbO 6 (SMNO) anode materials, which can be used in combination with electrolytes containing lanthanum to mitigate the effects of lanthanum poisoning in SOFCs. Currently, a La0.4Ce0.6O1.8 (LDC) transition layer is used with many perovskite-based anode materials to prevent La diffusion into the anode from the La0.8Sr0.2Ga0.8Mg 0.2O2.8 (LSGM) electrolyte, which can create a resistive La species that impedes electrochemical performance. To accomplish this, a new class of anode materials was synthesized with the goal of balancing La chemical potential between these neighboring materials. It was hypothesized that by

  4. 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.

  5. Mesoporous BaSnO3 layer based perovskite solar cells.

    PubMed

    Zhu, Liangzheng; Shao, Zhipeng; Ye, Jiajiu; Zhang, Xuhui; Pan, Xu; Dai, Songyuan

    2016-01-18

    One of the limitations of TiO2 based perovskite solar cells is the poor electron mobility of TiO2. Here, perovskite oxide BaSnO3 is used as a replacement. It has a higher electron mobility and the same perovskite structure as the light harvesting materials. After optimization, devices based on BaSnO3 showed the best performance of 12.3% vs. 11.1% for TiO2. PMID:26587570

  6. Defect Chemistry, Oxygen Ion Conduction, and Proton Conduction of Oxides with Brownmillerite and Related Structures.

    NASA Astrophysics Data System (ADS)

    Zhang, Guobin

    This dissertation presents a study on defect structure, oxygen ion conductivity, proton conductivity, electronic conductivity, and high temperature equilibrium redox properties of brownmillerite related oxides with general formula A _{rm n}B _{rm n}O_ {rm 3n-1} (n = 2 to infty ). A defect chemistry model is proposed for the brownmillerite oxides with high oxygen ion conductivity. Ba_2 In_2O_5 was chosen as the model material and its electrical conductivity and transport properties have been studied in detail. The oxygen ion conduction above the order-disorder temperature, T_{rm d} ~ 925^circC, and a mixed ionic-electronic conduction below T _{rm d}, was studied by conductivity and EMF measurements as a function of temperature and oxygen activity. The main defects are intrinsic anion Frenkel defects below T_{rm d}, and above T_{rm d} the oxide can be treated as acceptor doped perovskite with extrinsic oxygen vacancies. Charge compensation involves only ionic defects over the whole P(O_2 ) range used in this study. The formation and mobility enthalpies of the Frenkel defects, the redox enthalpies, and the band gap have been obtained for this oxide. A similar study has been done for other compositions in Ba _{rm n}In _2Zr_{rm n-2} O_{rm 3n-1} system. The proposed model is in good agreement with the experimental results. Evidence for protonic conduction was also found in these materials, especially at low temperatures. Three regions of protonic conduction in the Arrhenius plot have been observed and analyzed. The proton formation and mobility enthalpies have been obtained. The observed proton conductivity transition at the oxygen order-disorder transition temperature directly confirms the proton formation mechanism by incorporation of H_2O molecules into oxygen vacancies. A defect chemistry study was also conducted for the brownmillerite oxides with high electronic conductivity with Ca_2(Al_{ rm x}Fe_{rm 2-x})O_5 chosen as the model system. The main defects are

  7. Theory of hydrogen migration in organic-inorganic halide perovskites.

    PubMed

    Egger, David A; Kronik, Leeor; Rappe, Andrew M

    2015-10-12

    Solar cells based on organic-inorganic halide perovskites have recently been proven to be remarkably efficient. However, they exhibit hysteresis in their current-voltage curves, and their stability in the presence of water is problematic. Both issues are possibly related to a diffusion of defects in the perovskite material. By using first-principles calculations based on density functional theory, we study the properties of an important defect in hybrid perovskites-interstitial hydrogen. We show that differently charged defects occupy different crystal sites, which may allow for ionization-enhanced defect migration following the Bourgoin-Corbett mechanism. Our analysis highlights the structural flexibility of organic-inorganic perovskites: successive iodide displacements, combined with hydrogen bonding, enable proton diffusion with low migration barriers. These findings indicate that hydrogen defects can be mobile and thus highly relevant for the performance of perovskite solar cells. PMID:26073061

  8. Planar-integrated single-crystalline perovskite photodetectors

    PubMed Central

    Saidaminov, Makhsud I.; Adinolfi, Valerio; Comin, Riccardo; Abdelhady, Ahmed L.; Peng, Wei; Dursun, Ibrahim; Yuan, Mingjian; Hoogland, Sjoerd; Sargent, Edward H.; Bakr, Osman M.

    2015-01-01

    Hybrid perovskites are promising semiconductors for optoelectronic applications. However, they suffer from morphological disorder that limits their optoelectronic properties and, ultimately, device performance. Recently, perovskite single crystals have been shown to overcome this problem and exhibit impressive improvements: low trap density, low intrinsic carrier concentration, high mobility, and long diffusion length that outperform perovskite-based thin films. These characteristics make the material ideal for realizing photodetection that is simultaneously fast and sensitive; unfortunately, these macroscopic single crystals cannot be grown on a planar substrate, curtailing their potential for optoelectronic integration. Here we produce large-area planar-integrated films made up of large perovskite single crystals. These crystalline films exhibit mobility and diffusion length comparable with those of single crystals. Using this technique, we produced a high-performance light detector showing high gain (above 104 electrons per photon) and high gain-bandwidth product (above 108 Hz) relative to other perovskite-based optical sensors. PMID:26548941

  9. Effect of Cu doping on Ba0.5Sr0.5Fe1-xCuxO3-δ perovskites for solid oxide fuel cells: A first-principles study

    NASA Astrophysics Data System (ADS)

    Vázquez, Santiago; Suescun, Leopoldo; Faccio, Ricardo

    2016-04-01

    Nowadays a rational design of solid oxide fuel cells (SOFCs) cathodes is possible thanks to first-principles calculations based on density functional theory (DFT). We study the effect of Cu-doping in the bulk properties for the perovskite Ba0.5Sr0.5Fe1-xCuxO3-δ (with x = 0, 0.25 and 0.50) and correlate the results with previous experimental characterization. Bulk properties such as geometric structure, charge analysis, thermodynamic stability, vacancy formation energy, oxygen diffusion and electronic structure where studied in detail to provide an explanation of the oxygen reduction reaction (ORR) activity enhancement with Cu-doping. The results obtained here, using GGA+U, demonstrate the first-principles approach gives useful information that allows the prediction and explanation of experimental characterizations.

  10. 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}.

  11. Ab initio defect energetics of perovskite (001) surfaces for solid oxide fuel cells: A comparative study of LaMn O3 versus SrTi O3 and LaAl O3

    NASA Astrophysics Data System (ADS)

    Lee, Yueh-Lin; Morgan, Dane

    2015-05-01

    In this paper, we perform a comparative study based on ab initio modeling for perovskite A B O3 (001) surfaces and surface defect energetics in order to understand the influence of polarity and redox active Mn in the LaMn O3 system. We consider LaMn O3 ,LaAl O3 ,SrTi O3 , and briefly LaFe O3 systems for comparison, which illustrate the interplay between properties of polar surfaces and the varying d -electron shell of transition metals. We are motivated by the need to understand the surfaces of mixed electronic and ionic conductors typically used in solid oxide fuel cell cathodes and other ion conducting technologies, which are represented here by the LaMn O3 system. We focus on the influence of the metal character and surface polarity on the surface and surface defect chemistry in these selected systems. We demonstrate that the facile redox of the TM (3 d4 ) in LaMn O3 with partial eg orbital occupation (or specifically eg occupancy close to 1) allows the polar surfaces to be compensated by changes in charge density over relatively short length scales (3 to 4 unit cells or ˜1.5 nm) near the surface as compared to LaAl O3 . In contrast to LaAl O3 , this low-energy and short-range screening mechanism leads to low surface energies without any additional reconstruction, rapidly converging surface properties with film thickness (by ˜8 unit cells), bulklike defect chemistry more than ˜1.5 nm from the surface, and surface defect energetics that are primarily governed by the local charge doping or the created electric field near the polar surfaces. We show that LaMn O3 exhibits very different surface properties from LaAl O3 and SrTi O3 , thereby demonstrating that these properties are due to the presence of the redox active transition metal with partial eg orbital occupation and a polar surface, respectively. These understandings can help guide qualitative analysis, computational study, and design of surfaces of mixed electronic and ionic conductors.

  12. Anomalous perovskite PbRuO3 stabilized under high pressure

    PubMed Central

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

    2013-01-01

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

  13. Hypohalites and related oxidants as chemiluminescence reagents: a review.

    PubMed

    Francis, Paul S; Barnett, Neil W; Lewis, Simon W; Lim, Kieran F

    2004-01-01

    This review concerns the use of hypochlorite, hypobromite and related oxidants (such as N-bromosuccinimide and 1,3-dibromo-5,5-dimethylhydantoin) as chemiluminescence reagents and includes references to 249 papers that were published prior to mid-2003. Particular emphasis has been placed on proposed emitting species and the mechanisms of the light-producing pathways. The analytical applications of this chemistry have been summarized in three tables: (1) quantification of hypohalites and related compounds (including halides, which are initially oxidized); (2) enhancement or inhibition of luminol chemiluminescence; and (3) direct chemiluminescence reactions with hypohalite reagents. PMID:15098209

  14. Harnessing Defect-Tolerance at the Nanoscale: Highly Luminescent Lead Halide Perovskite Nanocrystals in Mesoporous Silica Matrixes.

    PubMed

    Dirin, Dmitry N; Protesescu, Loredana; Trummer, David; Kochetygov, Ilia V; Yakunin, Sergii; Krumeich, Frank; Stadie, Nicholas P; Kovalenko, Maksym V

    2016-09-14

    Colloidal lead halide perovskite nanocrystals (NCs) have recently emerged as a novel class of bright emitters with pure colors spanning the entire visible spectral range. Contrary to conventional quantum dots, such as CdSe and InP NCs, perovskite NCs feature unusual, defect-tolerant photophysics. Specifically, surface dangling bonds and intrinsic point defects such as vacancies do not form midgap states, known to trap carriers and thereby quench photoluminescence (PL). Accordingly, perovskite NCs need not be electronically surface-passivated (with, for instance, ligands and wider-gap materials) and do not noticeably suffer from photo-oxidation. Novel opportunities for their preparation therefore can be envisaged. Herein, we show that the infiltration of perovskite precursor solutions into the pores of mesoporous silica, followed by drying, leads to the template-assisted formation of perovskite NCs. The most striking outcome of this simple methodology is very bright PL with quantum efficiencies exceeding 50%. This facile strategy can be applied to a large variety of perovskite compounds, hybrid and fully inorganic, with the general formula APbX3, where A is cesium (Cs), methylammonium (MA), or formamidinium (FA), and X is Cl, Br, I or a mixture thereof. The luminescent properties of the resulting templated NCs can be tuned by both quantum size effects as well as composition. Also exhibiting intrinsic haze due to scattering within the composite, such materials may find applications as replacements for conventional phosphors in liquid-crystal television display technologies and in related luminescence down-conversion-based devices. PMID:27550860

  15. Metal halide perovskites for energy applications

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.

    2016-06-01

    Exploring prospective materials for energy production and storage is one of the biggest challenges of this century. Solar energy is one of the most important renewable energy resources, due to its wide availability and low environmental impact. Metal halide perovskites have emerged as a class of semiconductor materials with unique properties, including tunable bandgap, high absorption coefficient, broad absorption spectrum, high charge carrier mobility and long charge diffusion lengths, which enable a broad range of photovoltaic and optoelectronic applications. Since the first embodiment of perovskite solar cells showing a power conversion efficiency of 3.8%, the device performance has been boosted up to a certified 22.1% within a few years. In this Perspective, we discuss differing forms of perovskite materials produced via various deposition procedures. We focus on their energy-related applications and discuss current challenges and possible solutions, with the aim of stimulating potential new applications.

  16. 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.

  17. Thermodynamics of solid electrolytes and related oxide ceramics based on the fluorite structure

    SciTech Connect

    Navrotsky, Alexandra

    2010-01-01

    Oxides based on the fluorite structure are important as electrolytes in solid oxide fuel cells, thermal barrier coatings, gate dielectrics, catalysts, and nuclear materials. Though the parent fluorite structure is simple, the substitution of trivalent for tetravalent cations, coupled with the presence of charge-balancing oxygen vacancies, leads to a wealth of short-range and long-range ordered structures and complex thermodynamic properties. The location of vacancies and the nature of clusters affect the energetics of mixing in rare earth doped zirconia, hafnia, ceria, urania, and thoria, with systematic trends in energetics as a function of cation radius. High temperature oxide melt solution calorimetry has provided direct measurement of formation enthalpies of these refractory materials. Surface and interfacial energies have also been measured in yttria stabilized zirconia (YSZ) nanomaterials. Other ionic conductors having perovskite, apatite, and mellilite structures are discussed briefly.

  18. 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.

  19. Ferromagnetism in ruthenate perovskites

    NASA Astrophysics Data System (ADS)

    Dang, Hung T.; Mravlje, Jernej; Millis, Andrew J.

    2014-03-01

    In apparent contrast to the usual rule that stronger correlations favor magnetism and other forms of order, while weaker correlations lead to Fermi liquid metals, it has been experimentally established that CaRuO3, a more correlated material, is a paramagnetic metal with a Fermi liquid ground state while SrRuO3, which is less strongly correlated, is ferromagnetic below a Curie temperature of 160K. We present density functional plus dynamical mean field theory calculations which resolve this conundrum. We show that in these materials ferromagnetism occurs naturally for cubic perovskite systems at moderate correlations but is suppressed both by proximity to the Mott insulating phase and by increasing the amplitude of a GdFeO3 distortion. These factors are strongly related to the differences between Ca and Sr ruthenates and are used as the keys to solve the problem. Placement of the ruthenate materials on the metal-insulator phase diagram and comparison to previous works on the Ruddlesden-Popper materials are also discussed. Supported by the Basic Energy Sciences Program of the US Department of Energy under grant DOE ER046169 and the Columbia-Ecole Polytechnique Alliance program.

  20. Interaction of perovskite-like compounds based on transition-metal oxides with gas phase at T = 200-400°C

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

    The effect of the chemical composition of some perovskite-like cuprates, manganites, and cobaltite on their reactivity for oxygen and water vapor that are present in the annealing atmosphere, at 200-400°C has been studied. The partial substitution and alloying of LnBa2Cu3O y compounds lead to the increase in their stability with respect to aggressive components of gas phase (H2O, CO2). It was found that only compounds with structures characterized by several kinds of oxygen vacancies can absorb oxygen and water from the annealing atmosphere.

  1. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites

    DOE PAGESBeta

    Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W.; Meyer, Tricia L.; Zhang, Zhiyong; Lutterman, Daniel A.; Lee, Ho Nyung

    2016-02-11

    Strain is known to greatly influence low-temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. Still, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals such as Pt. We attribute the improved bifunctionality to strain-induced splitting of themore » eg orbitals, which can customize orbital asymmetry at the surface. Lastly, analogous to strain-induced shifts in the d-band center of noble metals relative to the Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides.« less

  2. SMOG CHAMBER EXPERIMENTS TO TEST OXIDANT RELATED CONTROL STRATEGY ISSUES

    EPA Science Inventory

    Outdoor smog chamber experiments were performed to address various issues relating to ozone (O3) production and oxidant control strategies. Temperature effects on single hydrocarbon-NOx systems were studied. Propylene-NOx systems were modeled with particular attention to peroxyni...

  3. AIR QUALITY CRITERIA FOR OZONE AND RELATED PHOTOCHEMICAL OXIDANTS

    EPA Science Inventory

    The Clean Air Act requires periodic (5-year) update revision of criteria and National Ambient Air Quality Standards (NAAQS) for Ozone. The previous revision of the criteria contained in the Air Quality Criteria Document (AQCD) for Ozone and Related Photochemical Oxidants was co...

  4. Molybdenum doped Pr0.5Ba0.5MnO3-δ (Mo-PBMO) double perovskite as a potential solid oxide fuel cell anode material

    NASA Astrophysics Data System (ADS)

    Sun, Yi-Fei; Zhang, Ya-Qian; Hua, Bin; Behnamian, Yashar; Li, Jian; Cui, Shao-Hua; Li, Jian-Hui; Luo, Jing-Li

    2016-01-01

    A layered Mo doped Pr0.5Ba0.5MnO3-δ (Mo-PBMO) double perovskite oxide was prepared by a modified sol-gel method and the properties of the fabricated material are characterized by various technologies. The results of X-ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR), NH3-temperature programmed desorption (NH3-TPD), and thermogravimetric analysis (TGA) demonstrate that the treatment in reducing atmosphere at high temperature lead to a significant phase transformation of the material to a single cubic phase as well as with the Mo in multiple oxidized states. Such character leads to the production of large amount of oxygen deficiency with facilitated oxygen diffusion. The electrochemical performance tests of half-cell and single cell SOFCs exhibit the promoted effect of Mo on catalytic activity for the oxidation of H2 and CH4, indicating that Mo-PBMO could serve as an anode material candidate for SOFCs.

  5. 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.

  6. Nitrous oxide related behavioral and histopathological changes may be related to oxidative stress.

    PubMed

    Singh, Sandeep Kumar; Misra, Usha Kant; Kalita, Jayantee; Bora, Himangsu K; Murthy, Ramesh C

    2015-05-01

    Nitrous oxide (N₂O) toxicity can result in myelin loss and hyperhomocysteinemia similar to cobalamin (Cbl) deficiency. Studies on N₂O exposure can help in understanding the mechanism of demyelination. In view of paucity of studies on N₂O toxicity in rats this study was undertaken. Six male wistar rats were exposed to 1.5L/min N₂O with 1:1 O₂ for 90 min daily for 1 month. After 1-month exposure blood homocysteine (HCY) and oxidative stress parameters glutathione (GSH) and total antioxidant capacity (TAC) were measured. Brain and spinal cord was subjected to histopathological examination. The neurobehavioral changes, oxidative stress parameters and histopathological changes were correlated with serum B12 and HCY level. After 1-month exposure, the rats appeared sluggish, lethargic and developed predominantly hind limb weakness for 1-1.5h. In the exposed group, the total distance traveled (2001.66 ± 118.27 cm; p=0.037), time moving (80.16 ± 5.7s; p=0.028), number of rearing (10.33 ± 1.45; p=0.014) and grip strength (1042.40 ± 51.3N; p=0.041) were significantly decreased whereas, resting time significantly increased (219.83 ± 5.7s; p=0.030) compared to controls. Serum HCY level was significantly increased (20.56 ± 1.296 μm/ml; p=0.0007) in the exposed group. However, serum B12 and folic acid levels were not significantly different. GSH significantly decreased (2.21 ± 0.60 mg/dl; p=0.018) along with TAC (0.76 ± 0.16 Trolox_Eq_mmol/l; p=0.036). The histopathological studies revealed shrinkage and vacuolation of neurons in cerebral cortex, focal myelin loss, vacuolation in subcortical white matter and spinal cord. N₂O exposure results in behavioral alterations, hyperhomocysteinemia, cortical and spinal cord demyelination which were associated with decrease GSH and TAC highlighting pathophysiological role of oxidative stress. PMID:25766523

  7. Dispersion relation data for methylammonium lead triiodide perovskite deposited on a (100) silicon wafer using a two-step vapour-phase reaction process

    PubMed Central

    Phillips, Laurie J.; Rashed, Atef M.; Treharne, Robert E.; Kay, James; Yates, Peter; Mitrovic, Ivona Z.; Weerakkody, Ayendra; Hall, Steve; Durose, Ken

    2015-01-01

    Ellipsometry was used to measure the amplitude ratio and phase difference of light undergoing a phase shift as it interacts with a thin film of organic–inorganic hybrid perovskite CH3NH3PbI3 (MAPI) deposited onto a (100) silicon wafer. The refractive index and extinction coefficient was extracted from a multi-oscillator model fit to the ellipsometry data, as a function of wavelength, from 300 to 1500 nm. PMID:26702423

  8. Praseodymium-deficiency Pr0.94BaCo2O6-δ double perovskite: A promising high performance cathode material for intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Meng, Fuchang; Xia, Tian; Wang, Jingping; Shi, Zhan; Zhao, Hui

    2015-10-01

    Praseodymium-deficiency Pr0.94BaCo2O6-δ (P0.94BCO) double perovskite has been evaluated as a cathode material for intermediate-temperature solid oxide fuel cells. X-ray diffraction pattern shows the orthorhombic structure with double lattice parameters from the primitive perovskite cell in Pmmm space group. P0.94BCO has a good chemical compatibility with Ce0.9Gd0.1O1.95 (CGO) electrolyte even at 1000 °C for 24 h. It is observed that the Pr-deficiency can introduce the extra oxygen vacancies in P0.94BCO, further enhancing its electrocatalytic activity for oxygen reduction reaction. P0.94BCO demonstrates the promising cathode performance as evidenced by low polarization are-specific resistance (ASR), e. g. 0.11 Ω cm2 and low cathodic overpotential e. g. -56 mV at a current density of -78 mA cm-2 at 600 °C in air. These features are comparable to those of the benchmark cathode Ba0.5Sr0.5Co0.8Fe0.2O3-δ. The fuel cell CGO-Ni|CGO|P0.94BCO presents the attractive peak power density of 1.05 W cm-2 at 600 °C. Furthermore, the oxygen reduction kinetics of P0.94BCO material is also investigated, and the rate-limiting steps for oxygen reduction reaction are determined.

  9. Age-related oxidative modifications of transthyretin modulate its amyloidogenicity

    PubMed Central

    Zhao, Lei; Buxbaum, Joel N; Reixach, Natàlia

    2013-01-01

    The transthyretin amyloidoses are diseases of protein misfolding characterized by the extracellular deposition of fibrils and other aggregates of the homotetrameric protein transthyretin (TTR) in peripheral nerves, heart and other tissues. Age is the major risk factor for the development of these diseases. We hypothesized that an age-associated increase in protein oxidation could be involved in the onset of the senile forms of the TTR amyloidoses. To test this hypothesis we have produced and characterized relevant age-related oxidative modifications of wild type (WT) and the Val122Ile (V122I) TTR variant, both involved in cardiac TTR deposition in the elderly. Our studies show that methionine/cysteine oxidized TTR and carbonylated TTR either from WT or the V122I variant, are thermodynamically less stable than their non-oxidized counterparts. Moreover, carbonylated WT and carbonylated V122I TTR have a greater propensity to form aggregates and fibrils than WT and V122I TTR, respectively, at physiologically attainable pH. It is well known that TTR tetramer dissociation, the limiting step for aggregation and amyloid fibril formation, can be prevented by small molecules that bind the TTR tetramer interface. Here, we report that carbonylated WT TTR is less amenable to resveratrol-mediated tetramer stabilization than WT TTR. All the oxidized forms of TTR tested are cytotoxic to a human cardiomyocyte cell line known to be a target for cardiac-specific TTR variants. Overall these studies demonstrate that age-related oxidative modifications of TTR can contribute to the onset of the senile forms of the TTR amyloidoses. PMID:23414091

  10. Elastic anisotropy of experimental analogues of perovskite and post-perovskite help to interpret D'' diversity.

    PubMed

    Yoneda, Akira; Fukui, Hiroshi; Xu, Fang; Nakatsuka, Akihiko; Yoshiasa, Akira; Seto, Yusuke; Ono, Kenya; Tsutsui, Satoshi; Uchiyama, Hiroshi; Baron, Alfred Q R

    2014-01-01

    Recent studies show that the D'' layer, just above the Earth's core-mantle boundary, is composed of MgSiO3 post-perovskite and has significant lateral inhomogeneity. Here we consider the D'' diversity as related to the single-crystal elasticity of the post-perovskite phase. We measure the single-crystal elasticity of the perovskite Pbnm-CaIrO3 and post-perovskite Cmcm-CaIrO3 using inelastic X-ray scattering. These materials are structural analogues to same phases of MgSiO3. Our results show that Cmcm-CaIrO3 is much more elastically anisotropic than Pbnm-CaIrO3, which offers an explanation for the enigmatic seismic wave velocity jump at the D'' discontinuity. Considering the relation between lattice preferred orientation and seismic anisotropy in the D'' layer, we suggest that the c axis of post-perovskite MgSiO3 aligns vertically beneath the Circum-Pacific rim, and the b axis vertically beneath the Central Pacific. PMID:24670790

  11. Human serum albumin and its relation with oxidative stress.

    PubMed

    Sitar, Mustafa Erinç; Aydin, Seval; Cakatay, Ufuk

    2013-01-01

    Human serum albumin, a negative acute phase reactant and marker of nutritive status, presents at high concentrations in plasma. Albumin has always been used in many clinical states especially to improve circulatory failure. It has been showed that albumin is involved in many bioactive functions such as regulation of plasma osmotic pressure, binding and transport of various endogenous or exogenous compounds, and finally extracellular antioxidant defenses. Molecules like transferrin, caeruloplasmin, haptoglobin, uric acid, bilirubin, alpha-tocopherol, glucose, and albumin constitute extracellular antioxidant defenses in blood plasma but albumin is the most potent one. Most of the antioxidant properties of albumin can be attributed to its unique biochemical structure. The protein possesses antioxidant properties such as binding copper tightly and iron weakly, scavenging free radicals, e.g., hypochlorous acid (HOCl) and Peroxynitrite (ONOOH) and providing thiol group (-SH). Whether it is chronic or acute, during many pathological conditions, biomarkers of oxidative protein damage increase and this observation continues with considerable oxidation of human serum albumin. There is an important necessity to specify its interactions with Reactive Oxygen Species. Generally, it may lower the availability of pro-oxidants and be preferentially oxidized to protect other macromolecules but all these findings make it necessary that researchers give a more detailed explanation of albumin and its relations with oxidative stress. PMID:24273915

  12. Accessing hidden isosymmetric phase transitions in perovskite thin films

    NASA Astrophysics Data System (ADS)

    Rondinelli, James; Coh, Sinisa

    2011-03-01

    Isosymmetric phase transitions (IPT), which show no change in occupied Wyckoff positions or crystallographic space group, are exceedingly rare in crystalline matter because most condensed systems respond to external stimuli by undergoing ``conventional'' symmetry-lowering displacive, martensitic or reconstructive transitions. In this work, we use first-principles density functional calculations to identify an elusive IPT in orthorhombic AB O3 perovskite oxides with tendency towards rhombohedral symmetry. Using perovskite LaGa O3 as our prototypical system, we show that the latent isosymmetric phase transition, which manifests as an abrupt change in the octahedral rotation axis, is accessible only with an external elastic constraint---bi-axial strain. We show the transition originates from a soft phonon that describes the geometric connectivity and relative phase of the Ga O6 polyhedra. By connecting the origin of IPT to a chemical and structural incompatibility between the lattice and the elastic constraints, we describe how subtle changes in bulk orthorhombic and monoclinic symmetries are critical to the complete engineering of structure-correlated electronic properties in thin films. Because bi-axial strain is the critical parameter controlling the IPT, we suggest heteroepitaxial synthesis of IPT materials is a plausible route to realize high- κ dielectric actuators with variable band gaps and dielectric anisotropies.

  13. 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.

  14. Microstructure dynamics in orthorhombic perovskites

    NASA Astrophysics Data System (ADS)

    Zhang, Zhiying; Koppensteiner, Johannes; Schranz, Wilfried; Betts, Jonathan B.; Migliori, Albert; Carpenter, Michael A.

    2010-07-01

    Anelastic loss mechanisms associated with phase transitions in BaCeO3 have been investigated at relatively high frequency ˜1MHz and low stress by resonant ultrasound spectroscopy (RUS), and at relatively low frequency ˜1Hz and high stress by dynamic mechanical analysis (DMA). Changes in the elastic moduli and dissipation behavior clearly indicate phase transitions due to octahedral tilting: Pnma↔Imma↔R3¯c↔Pm3¯m structures at 551 K, 670 K, and 1168 K, and strain analysis shows that they are tricritical, first-order, and second-order phase transitions, respectively. Structures with intermediate tilt states ( R3¯c and Imma structures) show substantial anelastic softening and dissipation associated with the mobility of twin walls under applied stress. The Pnma structure shows elastic stiffening which may be due to the simultaneous operation of two discrete order parameters with different symmetries. In contrast with studies of other perovskites, BaCeO3 shows strong dissipation at both DMA and RUS frequencies in the stability field of the Pnma structure. This is evidence that ferroelastic twin walls might become mobile in Pnma perovskites and suggests that shearing of the octahedra may be a significant factor.

  15. The characteristic of strontium-site deficient perovskites SrxFe1.5Mo0.5O6-δ (x = 1.9-2.0) as intermediate-temperature solid oxide fuel cell cathodes

    NASA Astrophysics Data System (ADS)

    Yang, Guoquan; Feng, Jie; Sun, Wang; Dai, Ningning; Hou, Mingyue; Hao, Xiaoming; Qiao, Jinshuo; Sun, Kening

    2014-12-01

    As the cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs), A-site deficient SrxFe1.5Mo0.5O6-δ (x = 1.9-2.0) (SxFM) materials have been successfully synthesized using the sol-gel combustion method. In the perovskite structure of these oxides, the unit cell varies from pseudocubic to cubic with increasing deficiency. Thermal expansion coefficient of SxFM has also been measured and compared with that of Scandium-stabilized zirconium (ScSZ) electrolyte. X-ray photoelectron spectroscopy (XPS) results indicate that the Sr-deficiency has changed the proportion of Fe2+/Fe3+ and Mo6+/Mo5+ ratios, which directly influences the conductivity of SxFM materials. S1.950FM possesses the largest electrical conductivity and the lowest polarization resistance (Rp) among all the samples. The maximum power densities of a single cell with the S1.950FM cathode reaches 1083 mW cm-2, and the area specific resistance value is 0.17 Ω cm2 at 800 °C. These results indicate that the A-site deficiency could promote the electrochemical performance of SFM materials as cathodes for IT-SOFCs.

  16. Age-related oxidative modifications of transthyretin modulate its amyloidogenicity.

    PubMed

    Zhao, Lei; Buxbaum, Joel N; Reixach, Natàlia

    2013-03-19

    The transthyretin amyloidoses are diseases of protein misfolding characterized by the extracellular deposition of fibrils and other aggregates of the homotetrameric protein transthyretin (TTR) in peripheral nerves, heart, and other tissues. Age is the major risk factor for the development of these diseases. We hypothesized that an age-associated increase in the level of protein oxidation could be involved in the onset of the senile forms of the TTR amyloidoses. To test this hypothesis, we have produced and characterized relevant age-related oxidative modifications of the wild type (WT) and the Val122Ile (V122I) TTR variant, both involved in cardiac TTR deposition in the elderly. Our studies show that methionine/cysteine-oxidized TTR and carbonylated TTR from either the WT or the V122I variant are thermodynamically less stable than their nonoxidized counterparts. Moreover, carbonylated WT and carbonylated V122I TTR have a stronger propensity to form aggregates and fibrils than WT and V122I TTR, respectively, at physiologically attainable pH values. It is well-known that TTR tetramer dissociation, the limiting step for aggregation and amyloid fibril formation, can be prevented by small molecules that bind the TTR tetramer interface. Here, we report that carbonylated WT TTR is less amenable to resveratrol-mediated tetramer stabilization than WT TTR. All the oxidized forms of TTR tested are cytotoxic to a human cardiomyocyte cell line known to be a target for cardiac-specific TTR variants. Overall, these studies demonstrate that age-related oxidative modifications of TTR can contribute to the onset of the senile forms of the TTR amyloidoses. PMID:23414091

  17. Pressure induced iron spin state changes in MgGeO3 Perovskite and Post-perovskite

    NASA Astrophysics Data System (ADS)

    Sarkar, Kanchan; Shukla, Gaurav; Topsakal, Mehmet; Wentzcovitch, Renata

    2015-03-01

    MgGeO3-perovskite is a low pressure analog of MgSiO3-perovskite, the main Earth forming phase, and is used to shed light on several phenomena that occur in MgSiO3, particularly the post-perovskite transition. As such, experimental investigations of spin state changes in Fe-bearing MgGeO3 might help to clarify some aspects of this phenomenon in MgSiO3. Using DFT+U calculations, we have investigated pressure induced spin state changes in Fe2+ and Fe3+ in MgGeO3 perovskite and post-perovskite and their effect on the post-perovskite transition. We uncover a direct relationship between average Fe-O bond-lengths and spin transition pressures in all cases. The effect of iron on the post-perovskite transitions in these phases can also be related to the average Fe-O bond lengths. Research supported by NSF/EAR and NSF/CAREER.

  18. Toxicological and pharmacological concerns on oxidative stress and related diseases

    SciTech Connect

    Saeidnia, Soodabeh; Abdollahi, Mohammad

    2013-12-15

    Although reactive oxygen species (ROS) such as superoxide, hydrogen peroxide and hydroxyl radical are generated as the natural byproduct of normal oxygen metabolism, they can create oxidative damage via interaction with bio-molecules. The role of oxidative stress as a remarkable upstream part is frequently reported in the signaling cascade of inflammation as well as chemo attractant production. Even though hydrogen peroxide can control cell signaling and stimulate cell proliferation at low levels, in higher concentrations it can initiate apoptosis and in very high levels may create necrosis. So far, the role of ROS in cellular damage and death is well documented with implicating in a broad range of degenerative alterations e.g. carcinogenesis, aging and other oxidative stress related diseases (OSRDs). Reversely, it is cleared that antioxidants are potentially able to suppress (at least in part) the immune system and to enhance the normal cellular protective responses to tissue damage. In this review, we aimed to provide insights on diverse OSRDs, which are correlated with the concept of oxidative stress as well as its cellular effects that can be inhibited by antioxidants. Resveratrol, angiotensin converting enzyme inhibitors, angiotensin receptor blockers, statins, nebivolol and carvedilol, pentaerythritol tetranitrate, mitochondria-targeted antioxidants, and plant-derived drugs (alone or combined) are the potential medicines that can be used to control OSRD.

  19. Predominant Intermediate-Spin Ferrous Iron in Lowermost Mantle Post-Perovskite and Perovskite

    NASA Astrophysics Data System (ADS)

    Lin, J.; Watson, H. C.; Vanko, G.; Alp, E. E.; Prakapenka, V.; Dera, P.; Struzhkin, V. V.; Kubo, A.; Zhao, J.; McCammon, C.; Evans, W. J.

    2008-12-01

    Silicate post-perovskite and perovskite are believed to be the dominant minerals of the lowermost mantle and the lower mantle, respectively, and their properties, which can be strongly influenced by the electronic state of iron in these phases, affect our understanding of the nature of the deep Earth. To date, in these minerals the electronic spin state of iron remains unknown under lowermost-mantle pressure-temperature conditions, although recent studies have showed an electronic spin crossover from high-spin to low-spin in ferropericlase over an extended pressure-temperature range of the lower mantle (i.e., Lin et al., Science, 2007) and from high-spin to intermediate-spin in silicate perovskite near the top of the lower mantle (McCammon et al., Nature Geoscience, 2008). Here we report the spin and valence states of iron in post-perovskite and perovskite at pressure-temperature conditions relevant to the lowermost mantle using in situ X-ray emission, X-ray diffraction, and synchrotron Mossbauer spectroscopies in a laser-heated diamond cell. Perovskite and post-perovskite display extremely high quadrupole splitting (QS) of approximately 4 mm/s and relatively high center shift in the synchrotron Mossbauer spectra at 110 GPa and 134 GPa, respectively. Our results show that Fe2+ exists predominantly in the intermediate-spin state with a total spin number of one in both phases (Lin et al., Nature Geoscience, 2008). Together with recent results on the effects of the spin transition in the lower-mantle ferropericlase (see a recent review by Lin and Tsuchiya, PEPI, 2008), here we will address how the electronic spin states in lower-mantle phases and their associated effects affect our understanding on the composition, geophysics, and dynamics of the lower mantle.. References: 1. Lin, J. F., H. C. Watson, G. Vanko, E. E. Alp, V. B. Prakapenka, P. Dera, V. V. Struzhkin, A. Kubo, J. Zhao, C. McCammon, W. J. Evans, Intermediate-spin ferrous iron in lowermost mantle post-perovskite

  20. Efficient methylammonium lead iodide perovskite solar cells with active layers from 300 to 900 nm

    SciTech Connect

    Momblona, C.; Malinkiewicz, O.; Soriano, A.; Gil-Escrig, L.; Bandiello, E.; Scheepers, M.; Bolink, H. J.; Edri, E.

    2014-08-01

    Efficient methylammonium lead iodide perovskite-based solar cells have been prepared in which the perovskite layer is sandwiched in between two organic charge transporting layers that block holes and electrons, respectively. This configuration leads to stable and reproducible devices that do not suffer from strong hysteresis effects and when optimized lead to efficiencies close to 15%. The perovskite layer is formed by using a dual-source thermal evaporation method, whereas the organic layers are processed from solution. The dual-source thermal evaporation method leads to smooth films and allows for high precision thickness variations. Devices were prepared with perovskite layer thicknesses ranging from 160 to 900 nm. The short-circuit current observed for these devices increased with increasing perovskite layer thickness. The main parameter that decreases with increasing perovskite layer thickness is the fill factor and as a result optimum device performance is obtained for perovskite layer thickness around 300 nm. However, here we demonstrate that with a slightly oxidized electron blocking layer the fill factor for the solar cells with a perovskite layer thickness of 900 nm increases to the same values as for the devices with thin perovskite layers. As a result the power conversion efficiencies for the cells with 300 and 900 nm are very similar, 12.7% and 12%, respectively.

  1. Structural, thermal and electrical conductivity characteristics of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm) complex perovskites as anode materials for solid oxide fuel cell

    SciTech Connect

    Jeong, Jihoon; Azad, Abul K.; Schlegl, Harald; Kim, Byungjun; Baek, Seung-Wook; Kim, Keunsoo; Kang, Hyunil; Kim, Jung Hyun

    2015-03-15

    The Ti and Mn replaced complex perovskites, Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm), were reported as potential anode materials for high temperature-operating solid oxide fuel cells (HT-SOFCs). For the present research study, synthesis, crystallographic, thermal and electrical conductivity properties of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} complex perovskites were investigated using X-ray diffraction (XRD), Rietveld method, thermogravimetric analysis (TGA) and electrical conductivity to apply these oxide materials for the HT-SOFC anode materials. XRD results showed that Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} oxide systems synthesized as single phases did not react with 8 mol% yttria stabilized zirconia (8YSZ) and 10 mol% Gd-doped cerium oxide (CGO91) up to 1500 °C and did not decompose under dry 3.9% hydrogen at 850 °C. The crystal structures of La{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (LSTM), Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (NSTM) and Sm{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (SSTM) showed orthorhombic symmetry with the space group Pbnm and SSTM showed a more distorted structure. Thermogravimetric analysis (TGA) proved weight gains in these three sample occurred under oxidizing conditions and weight loss under reducing conditions. Electrical conductivity values of NSTM were higher than those of LSTM and SSTM under oxidizing and reducing conditions. - Graphical abstract: The B-site cations (Ti/Mn) are surrounded by regular octahedra of oxygen in Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}(NSTM). These octahedra are linked together in a corner sharing three dimensional framework, while Nd/Sr ion occupies 12-coordinated A-site between these octahedra. The Ti/Mn–O{sub 6} octahedra are elongated along the c-axis. The crystal structure distortion was due to the smaller ionic radius of the A-site cations, which force the (Ti

  2. Effect of the A-site cation on methane oxidation of perovskite-type (La{sub 1-x}M{sub x})CoO{sub 3} (M=Ca, Sr, and Ba)

    SciTech Connect

    Taguchi, Hideki; Matsu-ura, Keiko; Takada, Masao; Hirota, Ken

    2012-06-15

    Perovskite-type (La{sub 1-x}M{sub x})CoO{sub 3} (M=Ca, Sr, and Ba) synthesized at 700 Degree-Sign C in air using the polymerizable complex method had a rhombohedral perovskite-type structure in the range of x{<=}0.06. The oxygen content of the samples was 2.98-2.99, and the specific surface area was 3.5-8.3 m{sup 2}/g regardless of the M ion or x. The Rietveld method indicated that the Co-O distance was also constant regardless of the M ion or x, and that the Co-O-Co angle between two CoO{sub 6} octahedra increased with an increase in the ionic radius of the M ion. The temperature corresponding to the 50% conversion (T{sub 1/2}) of CH{sub 4} oxidation was almost constant for the samples with x=0.04, while the T{sub 1/2} of the samples with x=0.06 was linearly lowered with increases in the ionic radius of the M ion. - Graphical abstract: The conversion from CH{sub 4} to CO{sub 2} and H{sub 2}O on (La{sub 0.94}M{sub 0.06})CoO{sub 3} (M=Ca, Sr, and Ba). Highlights: Black-Right-Pointing-Pointer (La{sub 1-x}M{sub x})CoO{sub 3} (M=Ca, Sr, and Ba) was synthesized using the polymerizable complex method. Black-Right-Pointing-Pointer The Co-O distance was constant regardless of the M ion or x. Black-Right-Pointing-Pointer The Co-O-Co angle increased with an increase in the ionic radius of the M ion. Black-Right-Pointing-Pointer CH{sub 4} oxidation started above 300 Degree-Sign C and finished at 700 Degree-Sign C. Black-Right-Pointing-Pointer The catalytic activity increased with increases in the ionic radius of the M ion.

  3. Phase Relations and Defect Chemistry of Bismuth Strontium Calcium Copper Oxide Superconducting Oxides at Elevated Temperature

    NASA Astrophysics Data System (ADS)

    Hong, Byungsun

    1992-01-01

    Subsolidus phase relations in the system (Bi-Sr -Ca-Cu)-O at 800^circC were investigated via powder X-ray diffraction and electron probe microanalysis of solid-state reaction products. The only truly quaternary compound detected is the superconducting phase of n = 2 in Bi_2(Sr _{rm x}Ca_ {rm 1-x})_{ rm n+1}Cu_{rm n}O_{rm y} . The n = 2 phase is compatible with eight different binary or ternary phases. Tie lines, tie triangles, and compatibility tetrahedra involving superconducting phases were determined. The cation solubility limits of the n = 2 and n = 3 superconducting phases were established along tie lines with compatible phases via EPMA on bi- (or poly -) phasic samples prepared at 860^circ C. In each case football-shaped volumes in composition space were established as the solubility limits which bordered on the nominal compositions 2212 or 2223 with the long axis parallel to the Sr-Ca side of the quaternary but also extending toward Bi and Cu. T_{rm c} variations could be correlated with variations in Sr or (Bi+Sr) content and the length of the c-axis parameter. Via in-situ high temperature (550-650 ^circC) electrical conductivity and Seebeck coefficient measurements in Bi_ {2.1}Sr_{1.9} (Ca_{rm 1-x}Y _{rm x})Cu _2O_{rm y} , a point defect model/diagram is presented which explains the variation of thermopower with composition in the system. The reference, insulating composition should be between Bi_{2.1}Sr _{1.9}Ca_ {0.2}Y_{0.8} Cu_2O_{8.45 } and Bi_{2.1}Sr _{1.9}Ca_ {0.3}Y_{0.7} Cu_2O_{8.4 }. Y-contents higher than x = 0.8 result in a second phase. A structural phase transition from pseudo -tetragonal to orthorhombic takes place at x = 0.5, and plays a major role in determining the physical properties. Oxygen transfer from the Bi-O block to the Cu-O based perovskite block is suggested at the phase boundary of x = 0.5. Jonker analysis and oxygen pressure dependence of carrier concentration confirm p-type behavior despite the change in sign of the thermopower

  4. Cobalt-free SrNbxFe1-xO3-δ (x = 0.05, 0.1 and 0.2) perovskite cathodes for intermediate temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Jiang, Shanshan; Sunarso, Jaka; Zhou, Wei; Shen, Jian; Ran, Ran; Shao, Zongping

    2015-12-01

    The development of high performance perovskite cathode for solid oxide fuel cells (SOFCs) relies upon the knowledge and understanding of the interplay between the metal oxide components, structure, redox properties and conductivity. In this work, we partially substituted Fe on SrFeO3-δ with Nb. In particular, 3 Nb-doped compositions were prepared, e.g. SrNb0.05Fe0.95O3-δ (SNF0.05), SrNb0.1Fe0.9O3-δ (SNF0.1) and SrNb0.2Fe0.8O3-δ (SNF0.2). Mössbauer spectroscopy revealed decreasing ratio of Fe4+ to Fe3+ at the higher Nb doping content which translates to the gradual decrease of the average Fe oxidation state from 3.403 (for SNF0.05) to 3.375 (for SNF0.1) and to 3.291 (for SNF0.2). Likewise, the oxygen desorption process and the thermal expansion coefficients decreased with increasing Nb content, therefore providing evidence on their correlation with the thermal reduction of Fe4+. The temperature-dependent oxygen nonstoichiometry displayed two different regimes separated by a transition temperature of 625 °C, below which SNF0.2 showed the highest nonstoichiometry and above which SNF0.05 provided the highest nonstoichiometry. The analogous shifting in trends was reproduced for oxygen reduction reaction (ORR) performance which signifies oxygen nonstoichiometry as the main variable affecting ORR performance.

  5. Triple-layered perovskite niobates CaRNb3O10 (R = La, Sm, Eu, Gd, Dy, Er, Yb, or Y): new self-activated oxides.

    PubMed

    Qin, Lin; Wei, Donglei; Huang, Yanlin; Kim, Sun Il; Yu, Young Moon; Seo, Hyo Jin

    2013-09-16

    Niobates CaRNb3O10 (R = La, Sm, Eu, Gd, Dy, Er, Yb, or Y) were prepared by conventional high-temperature solid-state reaction. The formation of a single-phase compound with triple-layered perovskite-type structure was verified through X-ray diffraction (XRD) studies. The luminescence characteristics such as photoluminescence excitation and emission spectra, X-ray-excited luminescence (XEL), Stokes shift, decay curves, and color coordinates were investigated. The niobates can be efficiently excited by UV light and present luminescence behaviors with rich luminescence colors. Under excitation by ultraviolet radiation, CaRNb3O10 (R = La, Gd, Yb, or Y) exhibits strong blue luminescence due to the self-activation center of the octahedral NbO6 groups, even at room temperature. For the materials of composition CaRNb3O10 (R = Sm, Eu, Dy, or Er), the excitation at the host band produces a characteristic luminescence of rare earth ions, indicating a host-guest energy transfer process. CaRNb3O10 (R = Eu) has the strongest luminescence intensity, which can be efficiently excitated by near UV wavelength. It could be suggested to be a potential candidate for the application on near-UV excited white LEDs. PMID:23977903

  6. 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.

  7. SrGa(0.7)Co(0.3)O(3-δ) perovskite-cobalt oxide-metal nanocomposite films: magnetic and optical properties.

    PubMed

    Sun, Xue Yin; Veis, Martin; Kousal, Jaroslav; Jesenska, Eva; Zhang, Chen; Aimon, Nicolas M; Goto, Taichi; Onbasli, Mehmet C; Kim, Dong Hun; Choi, Hong Kyoon; Ross, C A

    2015-03-20

    Two-phase nanocomposite films consisting of metallic Co nanoparticles below 50 nm diameter in a perovskite matrix were grown by pulsed laser deposition onto (LaAlO3)0.3(Sr2AlTaO6)0.7 (LSAT) and silicon substrates from a target of SrGa0.73Co0.27O3. The particles made up about 6% by volume of the film and were present within the film and at the substrate interface. The saturation magnetization of the film was up to 85 emu cm(-3) at 80 nm thickness and the Faraday rotation (FR) tracked the out-of-plane hysteresis loop, reaching 3000 deg cm(-1) at 10 kOe for 1550 nm wavelength. The magneto-optical figure of merit defined as FR divided by optical absorption was 0.04-0.06 deg dB(-1) due to the high optical absorption of the Co particles. PMID:25706414

  8. SrGa0.7Co0.3O3-δ perovskite-cobalt oxide-metal nanocomposite films: magnetic and optical properties

    NASA Astrophysics Data System (ADS)

    Sun, Xue Yin; Veis, Martin; Kousal, Jaroslav; Jesenska, Eva; Zhang, Chen; Aimon, Nicolas M.; Goto, Taichi; Onbasli, Mehmet C.; Kim, Dong Hun; Choi, Hong Kyoon; Ross, C. A.

    2015-03-01

    Two-phase nanocomposite films consisting of metallic Co nanoparticles below 50 nm diameter in a perovskite matrix were grown by pulsed laser deposition onto (LaAlO3)0.3(Sr2AlTaO6)0.7 (LSAT) and silicon substrates from a target of SrGa0.73Co0.27O3. The particles made up about 6% by volume of the film and were present within the film and at the substrate interface. The saturation magnetization of the film was up to 85 emu cm-3 at 80 nm thickness and the Faraday rotation (FR) tracked the out-of-plane hysteresis loop, reaching 3000 deg cm-1 at 10 kOe for 1550 nm wavelength. The magneto-optical figure of merit defined as FR divided by optical absorption was 0.04-0.06 deg dB-1 due to the high optical absorption of the Co particles.

  9. Ultimate efficiency limit of single-junction perovskite and dual-junction perovskite/silicon two-terminal devices

    NASA Astrophysics Data System (ADS)

    Almansouri, Ibraheem; Ho-Baillie, Anita; Green, Martin A.

    2015-08-01

    Theoretical calculation based on detailed balance and incorporating different realistic optical and electrical losses predicts conversion efficiency beyond 22% for single-junction perovskite devices. In dual-junction perovskite/silicon devices, theoretical conversion efficiency around 40% is been determined. However, dramatic drop in the conversion efficiency is shown to be due to the glass reflection and FTO parasitic absorption losses. Additionally, practical conversion efficiency limits of dual-junction two-terminal perovskite/silicon tandem solar cell of 30% are achievable as reported in this work using state-of-the-art demonstrated devices. Additionally, various crystalline silicon (industry and laboratory demonstrated) technologies are used as the bottom cell for the current matched tandem cell stacks with higher relative improvements when using commercial c-Si solar cells. Moreover, the effect of eliminating the parasitic resistances and enhancing the external radiative efficiency (ERE) in the perovskite junction on tandem performance are also investigated enhancing the stack efficiencies.

  10. Tunable perovskite microdisk lasers

    NASA Astrophysics Data System (ADS)

    Sun, Wenzhao; Wang, Kaiyang; Gu, Zhiyuan; Xiao, Shumin; Song, Qinghai

    2016-04-01

    Perovskite microdisk lasers have been intensively studied recently. But their lasing properties are usually fixed once the devices are synthesized. Here, for the first time, we demonstrated the switchable and tunable perovskite microdisk lasers by surrounding them with 5CB liquid crystals. With the increase of the environmental temperature from 24 °C to 34 °C, the lasing wavelength slightly changed from 552.91 nm to 552.11 nm at the beginning and suddenly shifted to around 552.54 nm at T = 32 °C, where the phase transition of liquid crystals occurs. Our numerical calculation shows that the wavelength shift is caused by the changes of the refractive index of liquid crystals. More than tuning of the wavelength, a more dramatic wavelength transition from ~554 nm to 550 nm has also been observed. This sudden transition is mainly induced by the reduction of scattering rather than the change in the refractive index when the liquid crystals are changed from the nematic phase to the isotropic phase. We believe that our research can shed light on the applications of perovskite optoelectronics.

  11. Tunable perovskite microdisk lasers.

    PubMed

    Sun, Wenzhao; Wang, Kaiyang; Gu, Zhiyuan; Xiao, Shumin; Song, Qinghai

    2016-04-28

    Perovskite microdisk lasers have been intensively studied recently. But their lasing properties are usually fixed once the devices are synthesized. Here, for the first time, we demonstrated the switchable and tunable perovskite microdisk lasers by surrounding them with 5CB liquid crystals. With the increase of the environmental temperature from 24 °C to 34 °C, the lasing wavelength slightly changed from 552.91 nm to 552.11 nm at the beginning and suddenly shifted to around 552.54 nm at T = 32 °C, where the phase transition of liquid crystals occurs. Our numerical calculation shows that the wavelength shift is caused by the changes of the refractive index of liquid crystals. More than tuning of the wavelength, a more dramatic wavelength transition from ∼554 nm to 550 nm has also been observed. This sudden transition is mainly induced by the reduction of scattering rather than the change in the refractive index when the liquid crystals are changed from the nematic phase to the isotropic phase. We believe that our research can shed light on the applications of perovskite optoelectronics. PMID:27064838

  12. Electronic, magnetic, and optical characteristics of half-semiconductor double perovskite oxide Sr2CrOsO6 governed by 3d (t2g3)-5d (t2g3) antiferromagnetic coupling

    NASA Astrophysics Data System (ADS)

    H.-E., M. Musa Saad

    2016-07-01

    In this study, motivated by observations of the remarkable magnetic insulating nature and high Curie temperature (TC=725 K) of double perovskite oxide Sr2CrOsO6, the electronic, magnetic, and optical characteristics of Sr2CrOsO6 were determined using the full potential linear muffin-tin orbital method according to density functional theory. The spin-orbit coupling contribution was included in the local spin density approximation (LSDA) and generalized gradient approximation (GGA). In addition, the Coulomb repulsion (U) and Hund's exchange (J) energies were considered in both methods (LSDA+U and GGA+U). Full structural optimization confirmed that the ground state of Sr2CrOsO6 is face-centered cubic (Fm-3m symmetry). Calculations predicted that Sr2CrOsO6 is ferrimagnetic half-semiconductive (HSC) due to the vertical hopping of t2g electrons via antiferromagnetic coupling [Cr3+ (t2g3↑)-O (2pπ)-Os5+ (t2g3↓)], which agreed with the experimental results. The HSC energy-gaps originate from the splitting of three partially occupied Os5+ (5d) bands into two fully filled bands and one empty spin-down band. The real ε1 (ω) and imaginary ε2 (ω) parts of the dielectric function ε (ω) and energy-loss spectrum L (ω) were calculated, analyzed, and compared with the electronic results.

  13. The effect of carbon-polyaniline hybrid coating on high-temperature electrochemical performance of perovskite-type oxide LaFeO3 for MH-Ni batteries.

    PubMed

    Pei, Yaru; Du, Wenkai; Li, Yuan; Shen, Wenzhuo; Wang, Yunchai; Yang, Shuqin; Han, Shumin

    2015-07-21

    An efficient carbon-polyaniline (PANI)-coated method was applied for perovskite-type oxide LaFeO3 to enhance its high-temperature electrochemical performance. Transmission electron microscopy (TEM) results reveal that LaFeO3 particles are evenly coated with carbon and PANI hybrid layers after carbon-PANI treatment. The carbon layers prevent the nanosized LaFeO3 particles from aggregation and allow the electrolyte to penetrate in every direction inside the particles. The PANI layers also enhance the electrocatalytic activity, facilitating hydrogen protons transferring from the electrolyte to the electrode interface. The cooperation of carbon and PANI hybrid layers results in a significant enhancement of the electrochemical performance at high temperatures. At an elevated temperature (60 °C), the maximum discharge capacity of the LaFeO3 electrodes remarkably increases from 231 mA h g(-1) to 402 mA h g(-1) and the high rate dischargeability at a discharge current density of 1500 mA g(-1) (HRD1500) increases from 22.7% to 44.3%. Moreover, the hybrid layers mitigate the corrosion of LaFeO3 electrodes by reducing the loss of active materials in the alkaline electrolyte, leading to increase in the capacity retention rate from 67.1% to 77.6% after 100 cycles (S100). PMID:26102361

  14. Nanoparticles of La{sub 0.8}Ca{sub 0.2}Fe{sub 0.8}Ni{sub 0.2}O{sub 3-{delta}} perovskite for solid oxide fuel cell application

    SciTech Connect

    Ortiz-Vitoriano, N.; Ruiz de Larramendi, I.; Gil de Muro, I.; Ruiz de Larramendi, J.I.

    2010-10-15

    Polycrystalline samples of La{sub 0.8}Ca{sub 0.2}Fe{sub 0.8}Ni{sub 0.2}O{sub 3-{delta}} (LCFN) with perovskite type structure have been prepared by combustion, freeze drying, citrate-gel process and liquid mix method. The analysis of X-ray powder diffraction indicated that the samples were single phase and crystallized in an orthorhombic (space group, Pnma no. 62) structure. Transmission electron microscopy (TEM) analysis on the synthesized powder at 600 {sup o}C by liquid mix method showed clusters of 150 nm formed by nanoparticles of 20 nm. Electrochemical performance of LCFN cathodes, which are used for intermediate temperature solid oxide fuel cells, were investigated. The polarization resistance was studied using two different electrolytes: Y-doped zirconia (YSZ) and Sm-doped ceria (SDC). The dc four-probe measurement exhibits a total electrical conductivity, over 100 S cm{sup -1} at T {>=} 600 {sup o}C, pointing out that strontium can be substituted for the cheaper calcium cation without destroying the electrochemical properties. Experimental results indicate that nanoparticles have more advantages in terms of smaller particle size and better electrochemical performance.

  15. Ferromagnetism in defect-ridden oxides and related materials

    NASA Astrophysics Data System (ADS)

    Coey, J. M. D.; Stamenov, P.; Gunning, R. D.; Venkatesan, M.; Paul, K.

    2010-05-01

    The existence of high-temperature ferromagnetism in thin films and nanoparticles of oxides containing small quantities of magnetic dopants remains controversial. Some regard these materials as dilute magnetic semiconductors, while others think they are ferromagnetic only because the magnetic dopants form secondary ferromagnetic impurity phases such as cobalt metal or magnetite. There are also reports in d0 systems and other defective oxides that contain no magnetic ions. Here, we investigate TiO2 (rutile) containing 1-5% of iron cations and find that the room temperature ferromagnetism of films prepared by pulsed-laser deposition is not due to magnetic ordering of the iron. The films are neither dilute magnetic semiconductors nor hosts to an iron-based ferromagnetic impurity phase. A new model is developed for defect-related ferromagnetism, which involves a spin-split defect band populated by charge transfer from a proximate charge reservoir—in the present case a mixture of Fe2+ and Fe3+ ions in the oxide lattice. The phase diagram for the model shows how inhomogeneous Stoner ferromagnetism depends on the total number of electrons Ntot, the Stoner exchange integral I and the defect bandwidth W; the band occupancy is governed by the d-d Coulomb interaction U. There are regions of ferromagnetic metal, half-metal and insulator as well as non-magnetic metal and insulator. A characteristic feature of the high-temperature Stoner magnetism is an anhysteretic magnetization curve, which is practically temperature independent below room temperature. This is related to a wandering ferromagnetic axis, which is determined by local dipole fields. The magnetization is limited by the defect concentration, not by the 3d doping. Only 1-2% of the volume of the films is magnetically ordered.

  16. Materials for Intermediate-Temperature Solid-Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Kilner, John A.; Burriel, Mónica

    2014-07-01

    Solid-oxide fuel cells are devices for the efficient conversion of chemical energy to electrical energy and heat. Research efforts are currently addressed toward the optimization of cells operating at temperatures in the region of 600°C, known as intermediate-temperature solid-oxide fuel cells, for which materials requirements are very stringent. In addition to the requirements of mechanical and chemical compatibility, the materials must show a high degree of oxide ion mobility and electrochemical activity at this low temperature. Here we mainly examine the criteria for the development of two key components of intermediate-temperature solid-oxide fuel cells: the electrolyte and the cathode. We limit the discussion to novel approaches to materials optimization and focus on the fluorite oxide for electrolytes, principally those based on ceria and zirconia, and on perovskites and perovskite-related families in the case of cathodes.

  17. Epitaxial heterojunctions of oxide semiconductors and metals on high temperature superconductors

    NASA Technical Reports Server (NTRS)

    Vasquez, Richard P. (Inventor); Hunt, Brian D. (Inventor); Foote, Marc C. (Inventor)

    1994-01-01

    Epitaxial heterojunctions formed between high temperature superconductors and metallic or semiconducting oxide barrier layers are provided. Metallic perovskites such as LaTiO3, CaVO3, and SrVO3 are grown on electron-type high temperature superconductors such as Nd(1.85)Ce(0.15)CuO(4-x). Alternatively, transition metal bronzes of the form A(x)MO(3) are epitaxially grown on electron-type high temperature superconductors. Also, semiconducting oxides of perovskite-related crystal structures such as WO3 are grown on either hole-type or electron-type high temperature superconductors.

  18. Spin reorientation and magnetization reversal in the perovskite oxides, YFe{sub 1-x}Mn{sub x}O{sub 3} (0{<=}x{<=}0.45): A neutron diffraction study

    SciTech Connect

    Mandal, P.; Serrao, C.R.; Suard, E.; Caignaert, V.; Raveau, B.; Sundaresan, A.; Rao, C.N.R.

    2013-01-15

    Members of the YFe{sub 1-x}Mn{sub x}O{sub 3} (0{<=}x{<=}0.45) family crystallize in the GdFeO{sub 3} type orthorhombic perovskite structure (space group Pnma) where the Fe and Mn ions are disordered at the 4b crystallographic site. Upon substitution of Mn at the Fe-site in the canted antiferromagnetic YFeO{sub 3} (T{sub N}=640 K), a first-order spin-reorientation transition occurs at a temperature, T{sub SR}, where the magnetic structure changes from the canted to a collinear state. With increasing Mn-concentration, T{sub SR} increases whereas T{sub N} decreases. Neutron diffraction studies on the x=0.4 sample reveal that the spin structure changes from {Gamma}{sub 4} to {Gamma}{sub 1} below T{sub SR}. Intriguingly, when x=0.4 and 0.45, a temperature-induced magnetization reversal is observed below a compensation temperature T{sup Low-Asterisk} (T{sup Low-Asterisk }perovskite oxides, YFe{sub 1-x}Mn{sub x}O{sub 3} and YCr{sub 1-x}Mn{sub x}O{sub 3}. Black-Right-Pointing-Pointer Presence of tunable positive and negative magnetocaloric effects in YFe{sub 1-x}Mn{sub x}O{sub 3}.

  19. Theoretical Investigation of H₂ Oxidation on the Sr2Fe1.5Mo0.5O6 (001) Perovskite Surface Under Anodic Solid Oxide Fuel Cell Conditions

    SciTech Connect

    Suthirakun, Suwit; Ammal, Salai Cheettu; Munoz-Garcia, Ana B.; Xiao, Guoliang; Chen, Fanglin; zur Loye, Hans-Conrad; Carter, Emily A.; Heyden, Andreas

    2014-06-11

    Periodic density functional theory (DFT) calculations and microkinetic modeling are used to investigate the electrochemical oxidation of H₂ fuel on the (001) surface of Sr2Fe1.5Mo0.5O6 (SFMO) perovskite under anodic solid oxide fuel cell conditions. Three surface models with different Fe/Mo ratios in the topmost layer-identified by ab initio thermodynamic analysis-are used to investigate the H₂ oxidation mechanism. A microkinetic analysis that considers the effects of anode bias potential suggests that a higher Mo concentration in the surface increases the activity of the surface toward H₂ oxidation. At operating voltage and anodic SOFC conditions, the model predicts that water desorption is rate-controlling and that stabilizing the oxygen vacancy structure increases the overall rate for H₂ oxidation. Although we find that Mo plays a crucial role in improving catalytic activity of SFMO, under fuel cell operating conditions, the Mo content in the surface layer tends to be very low. On the basis of these results and in agreement with previous experimental observations, a strategy for improving the overall electrochemical performance of SFMO is increasing the Mo content or adding small amounts of an active transition metal, such as Ni, to the surface to lower the oxygen vacancy formation energy of the SFMO surface.

  20. 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.

  1. Fabrication of organic-inorganic perovskite thin films for planar solar cells via pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Liang, Yangang; Yao, Yangyi; Zhang, Xiaohang; Hsu, Wei-Lun; Gong, Yunhui; Shin, Jongmoon; Wachsman, Eric D.; Dagenais, Mario; Takeuchi, Ichiro

    2016-01-01

    We report on fabrication of organic-inorganic perovskite thin films using a hybrid method consisting of pulsed laser deposition (PLD) of lead iodide and spin-coating of methylammonium iodide. Smooth and highly crystalline CH3NH3PbI3 thin films have been fabricated on silicon and glass coated substrates with fluorine doped tin oxide using this PLD-based hybrid method. Planar perovskite solar cells with an inverted structure have been successfully fabricated using the perovskite films. Because of its versatility, the PLD-based hybrid fabrication method not only provides an easy and precise control of the thickness of the perovskite thin films, but also offers a straightforward platform for studying the potential feasibility in using other metal halides and organic salts for formation of the organic-inorganic perovskite structure.

  2. [Thermochemistry of phases related to oxide superconductors]. Progresss report

    SciTech Connect

    Not Available

    1991-12-31

    The aim of this project has been to understand the crystal-chemical and energetic constraints on the stability of phases related to oxide superconductors, using high temperature reaction calorimetry, the unique expertise of this laboratory, coupled with synthesis and structural studies. The YBCO (Y{sub 2}O{sub 3}-BaO-Cu-O) system has been studied in detail by Zhou for his Ph.D. thesis, while DiCarlo has been studying alkaline earth doped lanthanium cuprates of the series La{sub 2-x}A{sub x}CuO{sub 4-y} having structures related to K{sub 2}NiF{sub 4}.

  3. NdBaCo2/3Fe2/3Cu2/3O5+δ double perovskite as a novel cathode material for CeO2- and LaGaO3-based solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Jin, Fangjun; Li, Lei; He, Tianmin

    2015-01-01

    Double perovskites LnBaCo2O5+δ (Ln = rare earth) are explored as cathode materials for intermediate-temperature solid oxide fuel cell. Barriers to the applicability of double perovskite cathodes include high thermal expansion coefficient (TEC) and poor chemical compatibility with common electrolytes. In this paper, we report the characteristics and applicability of a double perovskite NdBaCo2/3Fe2/3Cu2/3O5+δ (NBCFC) cathode on CeO2- and LaGaO3-based electrolytes. NBCFC is found to crystallize in a tetragonal structure. Partial substitution of Fe and Cu for cobalt in NBCFC demonstrates significantly decreased TEC and good chemical compatibility with both Gd0.1Ce0.9O1.95 (GDC) and La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) electrolytes, while maintaining its good electrochemical performance. The oxidation states of transition metal cations are Co3+/Co4+, Fe3+/Fe4+, and Cu+/Cu2+, respectively. The average TEC of NBCFC is 15.7 × 10-6 K-1 between 30 and 850 °C, and the polarization resistance values are 0.056 and 0.023 Ω cm2 at 800 °C with GDC and LSGM electrolytes, respectively. The absence of spin-state transition in copper contributes to the TEC reduction. Addition of appropriate amounts of GDC into NBCFC to form NBCFC-GDC composite cathodes further reduce the TEC and improve cathode performance. These results can be used to improve and develop novel double perovskite cathode materials.

  4. Synthesis and properties of Ba{sub 0.5}Sr{sub 0.5}(Co{sub 0.6}Zr{sub 0.2})Fe{sub 0.2}O{sub 3-{delta}} perovskite cathode material for intermediate temperature solid-oxide fuel cells

    SciTech Connect

    Meng Xiuxia; Meng Bo; Tan Xiaoyao; Yang Naitao; Ma Zifeng

    2009-06-03

    A highly stable perovskite cathode material, Ba{sub 0.5}Sr{sub 0.5}(Co{sub 0.6}Zr{sub 0.2})Fe{sub 0.2}O{sub 3-{delta}} (BSCZF) for intermediate temperature solid-oxide fuel cells (IT-SOFCs) was synthesized via the improved EDTA-citric acid complexing technique combined with high-temperature sintering. The product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectra (EIS) measurements. An electrolyte-supported BSCZF/SDC/Ni-SDC fuel cell was fabricated to evaluate the performance of the material. The XRD study indicates that the sintering temperature higher than 950 deg. C is sufficient to the formation of clean single BSCZF perovskite phase. Due to the incorporation of Zr ions, BSCZF perovskite exhibit lower electrical conductivity with higher activation energy but higher structural stability than the Ba{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} (BSCF) parent oxide. The maximum electrical conductivity of BSCZF attains 16.9 S cm{sup -1} at around 540 deg. C. Impedance spectra showed that the ASRs of BSCZF cathode on samaria doped ceria (Ce{sub 0.8}Sm{sub 0.2}O{sub 1.9}, SDC) electrolyte are low but are still slightly larger than those of BSCF at similar conditions. The BSCZF/SDC/Ni-SDC cell exhibited a stable output with the maximum power densities of 30, 75, 139 and 241 mW cm{sup -2} at 550, 600, 650 and 700 deg. C, respectively. Due to the high electrochemical performances as well as the excellent stability, BSCZF perovskite may be an attractive cathode material for IT-SOFCs.

  5. Two-step thermal annealing improves the morphology of spin-coated films for highly efficient perovskite hybrid photovoltaics

    NASA Astrophysics Data System (ADS)

    Hsu, Hsiang-Lin; Chen, Chih-Ping; Chang, Jia-Yaw; Yu, Yang-Yen; Shen, Yu-Kai

    2014-08-01

    In this paper, we describe relationships between the morphologies and the power conversion efficiencies (PCE) of perovskite photovoltaics having a conventional p-i-n heterojunction structure, indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS)/CH3NH3PbI3-xClx/PC61BM/Al. The PCE of such a device is highly dependent on the morphology of the perovskite film, which is governed by the concentrations of its precursors and the annealing conditions. A two-step annealing process allowed sufficient crystallization of the perovskite material, with a high coverage at a high precursor concentration. Relative to the device prepared using a one-step process (90 °C for 30 min), we observed a 60% increase in PCE for this optimized device. The corresponding devices exhibited extremely high stability after long-term storage (>1368 h) in the dark in a N2-filled glove box, with consistently high PCEs (AM 1.5G, 100 mW cm-2) of up to 9.1%.In this paper, we describe relationships between the morphologies and the power conversion efficiencies (PCE) of perovskite photovoltaics having a conventional p-i-n heterojunction structure, indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS)/CH3NH3PbI3-xClx/PC61BM/Al. The PCE of such a device is highly dependent on the morphology of the perovskite film, which is governed by the concentrations of its precursors and the annealing conditions. A two-step annealing process allowed sufficient crystallization of the perovskite material, with a high coverage at a high precursor concentration. Relative to the device prepared using a one-step process (90 °C for 30 min), we observed a 60% increase in PCE for this optimized device. The corresponding devices exhibited extremely high stability after long-term storage (>1368 h) in the dark in a N2-filled glove box, with consistently high PCEs (AM 1.5G, 100 mW cm-2) of up to 9.1%. Electronic supplementary information (ESI) available: UV

  6. Reactivity of perovskites with water: Role of hydroxylation in wetting and implications for oxygen electrocatalysis

    DOE PAGESBeta

    Stoerzinger, Kelsey A.; Hong, Wesley T.; Azimi, Gisele; Crumlin, Ethan J.; Biegalski, Michael D.; Bluhm, Hendrik; Varanasi, Kripa K.; Shao-Horn, Yang; Giordano, Livia; Lee, Yueh -Lin

    2015-07-15

    Oxide materials play an important role in technical applications such as gas sensing and catalysis, where they can react notably with water in vapor or liquid form. We find that the coverage of (*OH) measured at fixed relative humidity trends with the electron donor (basic) character of wetted perovskite oxide surfaces, corresponding to low contact angles when removing a droplet of water. We report for the first time that the affinity toward hydroxylation, coincident with strong adsorption energies calculated for dissociative and molecular adsorption of water, leads to strong H-bonding detrimental to catalysis of the oxygen reduction reaction (ORR). Furthermore,more » this suggests that hydrophobic oxides with low tendency to hydroxylate may demonstrate improved catalytic activity for the ORR.« less

  7. Oxidative stress, innate immunity, and age-related macular degeneration

    PubMed Central

    Shaw, Peter X.; Stiles, Travis; Douglas, Christopher; Ho, Daisy; Fan, Wei; Du, Hongjun; Xiao, Xu

    2016-01-01

    Age-related macular degeneration (AMD) is a leading cause of vision loss affecting tens of millions of elderly worldwide. Early AMD is characterized by the appearance of soft drusen, as well as pigmentary changes in the retinal pigment epithelium (RPE). These soft, confluent drusen can progress into two forms of advanced AMD: geographic atrophy (GA, or dry AMD) or choroidal neovascularization (CNV, or wet AMD). Both forms of AMD result in a similar clinical progression in terms of loss of central vision. The exact mechanism for developing early AMD, as well as triggers responsible for progressing to advanced stage of disease, is still largely unknown. However, significant evidence exists demonstrating a complex interplay of genetic and environmental factors as causes of AMD progression. Multiple genes and/or single nucleotide polymorphisms (SNPs) have been found associated with AMD, including various genes involved in the complement pathway, lipid metabolism and extracellular matrix (ECM) remodeling. Of the known genetic contributors to disease risk, the CFH Y402H and HTRA1/ARMS polymorphisms contribute to more than 50% of the genetic risk for AMD. Environmentally, oxidative stress plays a critical role in many aging diseases including cardiovascular disease, cancer, Alzheimer’s disease and AMD. Due to the exposure to sunlight and high oxygen concentration, the oxidative stress burden is higher in the eye than other tissues, which can be further complicated by additional oxidative stressors such as smoking. Increasingly, evidence is accumulating suggesting that functional abnormalities of the innate immune system incurred via high risk genotypes may be contributing to the pathogenesis of AMD by altering the inflammatory homeostasis in the eye, specifically in the handling of oxidation products. As the eye in non-pathological instances maintains a low level of inflammation despite the presence of a relative abundance of potentially inflammatory molecules, we have

  8. Oxidative stress, metabolism of ethanol and alcohol-related diseases.

    PubMed

    Zima, T; Fialová, L; Mestek, O; Janebová, M; Crkovská, J; Malbohan, I; Stípek, S; Mikulíková, L; Popov, P

    2001-01-01

    reactivity, liver disease progression, and they correlate significantly with the disease severity. The low-density lipoprotein (LDL) oxidation is supposed to be one of the most important pathogenic mechanisms of atherogenesis, and antibodies against oxidized LDL (oxLDL) are some kind of epiphenomenon of this process. We studied IgG oxLDL and four APA (anticardiolipin, antiphosphatidylserine, antiphosphatidylethanolamine and antiphosphatidylcholine antibodies). The IgG oxLDL (406.4 +/- 52.5 vs. 499.9 +/- 52.5 mU/ml) was not affected in alcoholic patients, but oxLDL was higher (71.6 +/- 4.1 vs. 44.2 +/- 2.7 micromol/l, p < 0.001). The prevalence of studied APA in alcoholics with mildly affected liver function was higher than in controls, but not significantly. On the contrary, changes of autoantibodies to IgG oxLDL revealed a wide range of IgG oxLDL titers in a healthy population. These parameters do not appear to be very promising for the evaluation of the risk of atherosclerosis. Free radicals increase the oxidative modification of LDL. This is one of the most important mechanisms, which increases cardiovascular risk in chronic alcoholic patients. Important enzymatic antioxidant systems - superoxide dismutase and glutathione peroxidase - are decreased in alcoholics. We did not find any changes of serum retinol and tocopherol concentrations in alcoholics, and blood and plasma selenium and copper levels were unchanged as well. Only the zinc concentration was decreased in plasma. It could be related to the impairment of the immune system in alcoholics. Measurement of these parameters in blood compartments does not seem to indicate a possible organ, e.g. liver deficiency. PMID:11173977

  9. Interface Effects in Perovskite Thin Films

    NASA Astrophysics Data System (ADS)

    Lepetit, Marie-Bernadette; Mercey, Bernard; Simon, Charles

    2012-02-01

    The control of matter properties (transport, magnetic, dielectric,…) using synthesis as thin films is strongly hindered by the lack of reliable theories, able to guide the design of new systems, through the understanding of the interface effects and of the way the substrate constraints are imposed on the material. The present Letter analyzes the energetic contributions at the interfaces, and proposes a model describing the microscopic mechanisms governing the interactions at an epitaxial interface between a manganite and another transition metal oxide in perovskite structure (as for instance SrTiO3). The model is checked against experimental results and literature analysis.

  10. 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

  11. Defects and Ion Migration in Complex Oxides

    NASA Astrophysics Data System (ADS)

    Islam, M. Saiful

    Ionic or mixed conductivity in complex ternary oxides has attracted considerable attention owing to both the range of applications (e.g., fuel cells, oxygen generators, oxidation catalysts) and the fundamental fascination of fast oxygen transport in solid state ionics [1, 2]. In particular, the ABO3 perovskite structure has been dubbed an "inorganic chameleon" since it displays a rich diversity of chemical compositions and properties. For instance, the mixed conductor La1-xSrxMnO3 finds use as the cathode material in solid oxide fuel cells (SOFCs) and also exhibits colossal magnetoresistance (CMR), whereas Sr/Mg doped LaGaO3 shows superior oxygen ion conductivity relative to the conventional zirconia-based electrolyte at moderate temperatures. A range of perovskite-structured ceramics, particularly cerates (ACeO3) and zirconates (AZrO3), also exhibit proton conductivity with potential fuel cell and sensor applications.

  12. 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.

  13. The interaction between hybrid organic-inorganic halide perovskite and selective contacts in perovskite solar cells: an infrared spectroscopy study.

    PubMed

    Idígoras, J; Todinova, A; Sánchez-Valencia, J R; Barranco, A; Borrás, A; Anta, J A

    2016-05-11

    The interaction of hybrid organic-inorganic halide perovskite and selective contacts is crucial to get efficient, stable and hysteresis-free perovskite-based solar cells. In this report, we analyze the vibrational properties of methylammonium lead halide perovskites deposited on different substrates by infrared absorption (IR) measurements (4000-500 cm(-1)). The materials employed as substrates are not only characterized by different chemical natures (TiO2, ZnO and Al2O3), but also by different morphologies. For all of them, we have investigated the influence of these substrate properties on perovskite formation and its degradation by humidity. The effect of selective-hole contact (Spiro-OmeTad and P3HT) layers on the degradation rate by moisture has also been studied. Our IR results reveal the existence of a strong interaction between perovskite and all ZnO materials considered, evidenced by a shift of the peaks related to the N-H vibrational modes. The interaction even induces a morphological change in ZnO nanoparticles after perovskite deposition, pointing to an acid-base reaction that takes place through the NH3(+) groups of the methylammonium cation. Our IR and X-ray diffraction results also indicate that this specific interaction favors perovskite decomposition and PbI2 formation for ZnO/perovskite films subjected to humid conditions. Although no interaction is observed for TiO2, Al2O3, and the hole selective contact, the morphology and chemical nature of both contacts appear to play an important role in the rate of degradation upon exposure to moisture. PMID:27138224

  14. Formability of ABX3 (X = F, Cl, Br, I) halide perovskites.

    PubMed

    Li, Chonghea; Lu, Xionggang; Ding, Weizhong; Feng, Liming; Gao, Yonghui; Guo, Ziming

    2008-12-01

    In this study a total of 186 complex halide systems were collected; the formabilities of ABX3 (X = F, Cl, Br and I) halide perovskites were investigated using the empirical structure map, which was constructed by Goldschmidt's tolerance factor and the octahedral factor. A model for halide perovskite formability was built up. In this model obtained, for all 186 complex halides systems, only one system (CsF-MnF2) without perovskite structure and six systems (RbF-PbF2, CsF-BeF2, KCl-FeCl2, TlI-MnI2, RbI-SnI2, TlI-PbI2) with perovskite structure were wrongly classified, so its predicting accuracy reaches 96%. It is also indicated that both the tolerance factor and the octahedral factor are a necessary but not sufficient condition for ABX3 halide perovskite formability, and a lowest limit of the octahedral factor exists for halide perovskite formation. This result is consistent with our previous report for ABO3 oxide perovskite, and may be helpful to design novel halide materials with the perovskite structure. PMID:19029699

  15. Ion-exchangeable, electronically conducting layered perovskite oxyfluorides.

    PubMed

    Kobayashi, Yoji; Tian, Mingliang; Eguchi, Miharu; Mallouk, Thomas E

    2009-07-22

    Cation-exchangeable d(0) layered perovskites are amenable to intercalation, exfoliation, and a variety of topochemical reactions, but they lack the interesting electronic and magnetic functionalities of mixed-valent perovskites. Conversely, electronically and magnetically interesting layered perovskites lack scope in terms of interlayer chemistry. To bridge this gap, the insulating, cation-exchangeable layered perovskites RbLaNb(2)O(7), KCa(2)Nb(3)O(10), and NaYTiO(4) were reacted with poly(tetrafluoroethylene) under inert atmosphere conditions to yield layer perovskites in which some of the oxygen is substituted by fluorine. In the fluorinated materials, the B-site cations are reduced to a mixed-valent state without introducing oxygen vacancies into the anion sublattice. The resulting electronically conducting solids can be exposed to air and water and even ion-exchanged in acid without oxidation of the B-site cations. Electronic transport measurements on the air-stable RbLaNb(2)O(6)F reveal room-temperature conductivity (2-7 x 10(2) ohms x cm) via a variable-range hopping mechanism, which is not substantially changed after aqueous proton exchange to H(1-x)Rb(x)LaNb(2)O(6)F (x approximately = 0.2). PMID:19548670

  16. Synthesis and Thermodynamic Stability of Ba2B‧B″O6 and Ba3B*B″2O9 Perovskites Using the Molten Salt Method

    NASA Astrophysics Data System (ADS)

    Meng, Wei; Virkar, Anil V.

    1999-12-01

    A number of mixed perovskites of the types Ba2B‧B″O6 (BaB‧1/2B″1/2O3) and Ba3B*B″2O9 (BaB*1/3B″2/3O3) where B‧=Gd, La, Nd, Sm, or Y; B″=Nb and B*=Ca were synthesized by a conventional calcination process, as well as by the molten salt method. The former consists of calcining appropriate mixtures of oxide or carbonate precursors in air at elevated temperatures (∼1250°C). The latter method consists of adding appropriate mixtures of oxide or carbonate precursors to a molten salt bath at relatively low temperatures (on the order of 300 to 500°C) so that the requisite compound is formed by dissolution-reprecipitation. X-ray diffraction confirmed the formation of a single-phase perovskite in each case with calcination at 1250°C. In a molten salt bath, however, all except Ba2LaNbO6 and Ba2NdNbO6 formed the perovskite structure. On the contrary, powders of Ba2LaNbO6 and Ba2NdNbO6 formed by a high-temperature calcination process readily decomposed when introduced into the molten salt bath. The formation of the requisite perovskite at a temperature as low as 350°C in a molten salt suggests that: (a) The perovskite is stable at 350°C. (b) The molten salt exhibits sufficient precursor solubility for the dissolution-reprecipitation process to occur in a reasonable time. Similarly, the decomposition of Ba2LaNbO6 and Ba2NdNbO6 in a molten salt bath shows that these materials are thermodynamically unstable at the temperature of the molten salt bath.

  17. Evaluation of Oxidative Stress Response Related Genetic Variants, Pro-oxidants, Antioxidants and Prostate Cancer

    PubMed Central

    Lavender, Nicole; Hein, David W.; Brock, Guy; Kidd, La Creis R.

    2015-01-01

    Background Oxidative stress and detoxification mechanisms have been commonly studied in Prostate Cancer (PCa) due to their function in the detoxification of potentially damaging reactive oxygen species (ROS) and carcinogens. However, findings have been either inconsistent or inconclusive. These mixed findings may, in part, relate to failure to consider interactions among oxidative stress response related genetic variants along with pro- and antioxidant factors. Methods We examined the effects of 33 genetic and 26 environmental oxidative stress and defense factors on PCa risk and disease aggressiveness among 2,286 men from the Cancer Genetic Markers of Susceptibility project (1,175 cases, 1,111 controls). Single and joint effects were analyzed using a comprehensive statistical approach involving logistic regression, multi-dimensionality reduction, and entropy graphs. Results Inheritance of one CYP2C8 rs7909236 T or two SOD2 rs2758331 A alleles was linked to a 1.3- and 1.4-fold increase in risk of developing PCa, respectively (p-value = 0.006–0.013). Carriers of CYP1B1 rs1800440GG, CYP2C8 rs1058932TC and, NAT2 (rs1208GG, rs1390358CC, rs7832071TT) genotypes were associated with a 1.3 to 2.2-fold increase in aggressive PCa [p-value = 0.04–0.001, FDR 0.088–0.939]. We observed a 23% reduction in aggressive disease linked to inheritance of one or more NAT2 rs4646247 A alleles (p = 0.04, FDR = 0.405). Only three NAT2 sequence variants remained significant after adjusting for multiple hypotheses testing, namely NAT2 rs1208, rs1390358, and rs7832071. Lastly, there were no significant gene-environment or gene-gene interactions associated with PCa outcomes. Conclusions Variations in genes involved in oxidative stress and defense pathways may modify PCa. Our findings do not firmly support the role of oxidative stress genetic variants combined with lifestyle/environmental factors as modifiers of PCa and disease progression. However, additional multi-center studies poised

  18. Glory of piezoelectric perovskites

    NASA Astrophysics Data System (ADS)

    Uchino, Kenji

    2015-08-01

    This article reviews the history of piezoelectric perovskites and forecasts future development trends, including Uchino’s discoveries such as the Pb(Mg1/3Nb2/3)O3-PbTiO3 electrostrictor, Pb(Zn1/3Nb2/3)O3-PbTiO3 single crystal, (Pb, La)(Zr, Ti)O3 photostriction, and Pb(Zr, Ti)O3-Terfenol magnetoelectric composites. We discuss five key trends in the development of piezomaterials: performance to reliability, hard to soft, macro to nano, homo to hetero, and single to multi-functional.

  19. Electrosynthesis and crystal structure of the new 15R hexagonal perovskite Ba 5MnNa 2V 2O 13

    NASA Astrophysics Data System (ADS)

    Bendraoua, Abdelaziz; Quarez, Eric; Abraham, Francis; Mentré, Olivier

    2004-04-01

    A new manganese oxide Ba 5MnNa 2V 2O 13 with an original structure closely related to the cubic perovskite has been prepared by electrosynthesis in molten NaOH. Its crystal structure has been refined from single crystal X-ray diffraction in the R 3¯m space group, a=5.8490(6) Å, c=36.856(5) Å, Z=3, R1=4.72%, w R2=10.56%. The crystal structure is a rhombohedral 15R polytype and exhibits a close packed structure built up from [BaO 3- δ] ( c) and [BaO 2] ( c') layers within a ( ccc' cc) 3 stacking sequence. The resulting three-dimensional edifice is formed by Ba(Mn 0.33Na 0.67)O 3 cubic perovskite blocks separated by double sheets of V 5+O 4 tetrahedra pointing towards the central [BaO 2] c' layer. In the perovskite blocks, 1/6 of oxygen deficient vacancies located on layers surrounding manganese involve a Mn(IV) valence, in square pyramids rather than octahedra. On the same layers along c, the barium atom split from a central (0,0, z) position to close ( x,- x, z) positions as a compensation of the oxygen deficiency. In this work, a review of the Mn-related perovskite materials found in the literature is reported showing the wide variety of materials adopting related structural polytypes. A building scheme from simple to more complex edifices is also presented by successive intercalation of [BaO n] ( n=1, 2) in order to visualize topological relationships between the number of possible hexagonal perovskite series members.

  20. Optimized energy conversion efficiency in solid-oxide fuel cells implementing SrMo1-xFexO3-δ perovskites as anodes

    NASA Astrophysics Data System (ADS)

    Martínez-Coronado, R.; Alonso, J. A.; Aguadero, A.; Fernández-Díaz, M. T.

    2012-06-01

    Oxides of composition SrMo1-xFexO3-δ (x = 0.1, 0.2) have been prepared, characterized and tested as anode materials in single solid-oxide fuel cells, yielding output powers close to 900 mW cm-2 at 850 °C with pure H2 as a fuel. This excellent performance is accounted for the results of an “in situ” neutron powder diffraction experiment, at the working temperature of the SOFC, showing the presence of a sufficiently high oxygen deficiency, with large displacement factors for oxygen atoms that suggest a large lability and mobility, combined with a huge metal-like electronic conductivity, as high as 340 S cm-1 at T = 50 °C for x = 0.1. The magnitude of the electronic conductivity decreases with increasing Fe-doping content. An adequate thermal expansion coefficient, reversibility upon cycling in oxidizing-reducing atmospheres and chemical compatibility with the electrolyte make these oxides good candidates for anodes in intermediate-temperature SOFC (IT-SOFCs).

  1. The controlled growth of perovskite thin films: Opportunities, challenges, and synthesis

    SciTech Connect

    Schlom, D.G.; Theis, C.D.; Hawley, M.E.

    1997-10-01

    The broad spectrum of electronic and optical properties exhibited by perovskites offers tremendous opportunities for microelectronic devices, especially when a combination of properties in a single device is desired. Molecular beam epitaxy (MBE) has achieved unparalleled control in the integration of semiconductors at the monolayer-level; its use for the integration of perovskites with similar nanoscale customization appears promising. Composition control and oxidation are often significant challenges to the growth of perovskites by MBE, but we show that these can be met through the use of purified ozone as an oxidant and real-time atomic absorption composition control. The opportunities, challenges, and synthesis of oxide heterostructures by reactive MBE are described, with examples taken from the growth of oxide superconductors and oxide ferroelectrics.

  2. Highly stable perovskite solar cells with an all-carbon hole transport layer.

    PubMed

    Wang, Feijiu; Endo, Masaru; Mouri, Shinichiro; Miyauchi, Yuhei; Ohno, Yutaka; Wakamiya, Atsushi; Murata, Yasujiro; Matsuda, Kazunari

    2016-06-01

    Nano-carbon materials (carbon nanotubes, graphene, and graphene oxide) have potential application for photovoltaics because of their excellent optical and electronic properties. Here, we demonstrate that a single-walled carbon nanotubes/graphene oxide buffer layer greatly improves the photovoltaic performance of organo-lead iodide perovskite solar cells. The carbon nanotubes/graphene oxide buffer layer works as an efficient hole transport/electron blocking layer. The photovoltaic conversion efficiency of 13.3% was achieved in the organo-lead iodide perovskite solar cell due to the complementary properties of carbon nanotubes and graphene oxide. Furthermore, the great improvement of photovoltaic performance stability in the perovskite solar cells using carbon nanotubes/graphene oxide/polymethyl methacrylate was demonstrated in comparison with that using a typical organic hole transport layer of 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene. PMID:27232674

  3. Oxidative stress and age-related neuronal deficits.

    PubMed

    Joseph, J A; Denisova, N; Villalobos-Molina, R; Erat, S; Strain, J

    1996-01-01

    Research from our laboratory has indicated that the loss of sensitivity that occurs in several receptor systems as a function of age may be an index of an increasing inability to respond to oxidative stress (OS). This loss occurs partially as a result of altered signal transduction (ST). Assessments have involved determining the nature of age-related reductions in oxotremorine enhancement of K(+)-evoked dopamine release (K(+)-ERDA) from superfused striatal slices. Using this model, we have found that 1. Reductions can be restored with in vivo administration of the free-radical trapping agent, N-tert-butyl-alpha-phenylnitrone (PBN); 2. Decrements in DA release induced by NO or H2O2 from striatal slices from both young and old animals could be restored with alpha-tocopherol or PBN; 3. ST decrements, such as those seen in aging, could be induced with radiation exposure; and 4. Pre-incubation of the striatal slices with cholesterol decreased subsequent deleterious effects of NO or OH. on DA release. Thus, cholesterol, which increases in neuronal membranes as a function of age, may function as a potent antioxidant and protectant against neuronal damage. These results suggest that therapeutic efforts to restore cognitive deficits in aging and age-related disease might begin with antioxidant reversal of ST decrements. PMID:8871939

  4. Magnetic properties of the Ca nFe 2Ti n-2 O 3 n-1 perovskite related series: An EPR study

    NASA Astrophysics Data System (ADS)

    Causa, M. T.; Zysler, R. D.; Tovar, M.; Vallet-Regí, M.; González-Calbet, J. M.

    1992-05-01

    We report here an EPR study of the perovskite-like family Ca nFe 2Ti n-2 O 3 n-1 , where Ti 4+ non-magnetic ions substitute for Fe 3+ in the brownmillerite structure ( n = 2). For terms n = 3 and 4, intense EPR spectra above ≈ 330 K associated with the resonance of paramagnetic Fe 3+ ions are observed. The integrated intensity of the EPR line presents a maximum at T0 = T( Imax) ≈ 330 K in both cases, becoming negligible for T < 275(5)K. Dc magnetic susceptibility measurements present a pronounced break in the slope of χdc ( T) vs T at 283(3) K in both compounds. These anomalies are taken as indications of the establishment of magnetic ordering in the materials. The depression of the ordering temperature found for the terms n = 3 and 4 of the series, as compared to the case of n = 2, is discussed in terms of the possible cationic order in these compounds. A reduction of the dimensionality of the magnetic behavior is suggested in going from n = 2 to n = 3 and 4.

  5. Features of Ferroelectric States in the Simple-Perovskite Mixed-Oxide System (1-x)Pb(Zn1/3Nb2/3)O3-xPbTiO3 with Lower Ti Contents

    NASA Astrophysics Data System (ADS)

    Tsukasaki, Hirofumi; Uneno, Yuka; Mori, Shigeo; Koyama, Yasumasa

    2016-03-01

    A mixed-oxide system (1 - x)Pb(Zn1/3Nb2/3)O3-xPbTiO3, which has a simple perovskite structure, has been reported to exhibit remarkable piezoelectric responses for 0 < x ≤ 0.08. To understand the ferroelectric states for 0 < x < 0.10, the crystallographic features of plate-shaped single crystals with various sample orientations have been examined by transmission electron microscopy. Owing to both the bending of specimens and the complicated nanometer-scale domain structures, it was difficult to obtain a contrast reversal due to the failure of Friedel’s law. In some cases, however, it was possible to analyze the ferroelectric domain structures of the sample. Although the typical 109° domain structure of the ferroelectric rhombohedral state was found for x = 0.02, as a major feature in [110]c-oriented single crystals, the ferroelectric states for 0 < x ≤ 0.08 were found to be characterized by an assembly of nanometer-scale polar (NP) domains with rhombohedral symmetry. In [210]c-oriented crystals, on the other hand, the so-called MC state with monoclinic symmetry was present for x ≈ 0.08. Furthermore, on the basis of in-situ observation, the evolution of a maze-pattern domain structure in the MC state upon cooling from the paraelectric state occurs via a local flip-flop between two polarization vectors, which are nearly parallel to the <210>c directions. It is likely that this behavior is directly associated with the ultrahigh piezoelectric deformations found for x ≈ 0.08.

  6. Critical behavior and non-universal low-field magnetic scaling in La{sub 1-x}Bi{sub x}MnO{sub 3} (x=0.4 & 0.6) perovskite manganite oxide

    SciTech Connect

    Punith Kumar, V.; Dayal, Vijaylakshmi

    2015-06-24

    We report on critical behavior in La{sub 1-x}Bi{sub x}MnO{sub 3} (x=0.4 & 0.6) perovskite manganite oxide by studying AC susceptibility, χ, measured at randomly chosen low magnetic fields (H=9.45 Oe to 0.95 Oe) at fixed frequency of f=131 Hz. The samples exhibit non-uniformity in their magnetic spin interactions around paramagnetic-to-ferromagnetic transition temperature (T{sub C}). By non-universal low-field magnetic scaling of AC χ given as, χ{sup −1}-χ{sup −1}(T{sub C}) ∼ (T/T{sub C}−1){sup γ} ≡ τ{sup γ} the magnetic interactions in the samples around T{sub C} has been studied. The linear fit to ln (χ{sup −1} - χ{sub C}{sup −1}) vs. ln (T/T{sub C}-1) gives the values of critical exponent ‘γ’ under applied magnetic fields. The values of γ is found to be ∼1.48±0.007 for the sample with x=0.4 and ∼1.36±0.004 for x=0.6 at 0.95 Oe lie in the context of 3D Heisenberg type spin interactions. The profound 3D Heisenberg type spin interactions arises due to the phase separation effect for x=0.4 and breaking of ferromagnetic order and induced Bi{sup 3+} (6S{sup 2}) − O{sup 2−} (2P{sup 6}) lattice distortions for x=0.6 as discussed in manuscript.

  7. Catalytic hydrogenation of carbon monoxide over nanostructured perovskite-like gadolinium and strontium ferrites

    NASA Astrophysics Data System (ADS)

    Sheshko, T. F.; Serov, Yu. M.; Dement'eva, M. V.; Shul'ga, A.; Chislova, I. V.; Zvereva, I. A.

    2016-05-01

    The catalytic properties of perovskite-like ferrites (A n + 1B n O3 n + 1, where n = 1, 2, 3, …, ∞; A = Gd, Sr; and B = Fe) synthesized via ceramic and sol-gel technology in the hydrogenation of carbon monoxide are studied. The interrelation between catalytic activity, selectivity to olefins and synthetic methods for complex oxide preparation, the number of perovskite layers, crystallite size, composition, and the valence state of iron is established.

  8. Highly stable perovskite solar cells with an all-carbon hole transport layer

    NASA Astrophysics Data System (ADS)

    Wang, Feijiu; Endo, Masaru; Mouri, Shinichiro; Miyauchi, Yuhei; Ohno, Yutaka; Wakamiya, Atsushi; Murata, Yasujiro; Matsuda, Kazunari

    2016-06-01

    Nano-carbon materials (carbon nanotubes, graphene, and graphene oxide) have potential application for photovoltaics because of their excellent optical and electronic properties. Here, we demonstrate that a single-walled carbon nanotubes/graphene oxide buffer layer greatly improves the photovoltaic performance of organo-lead iodide perovskite solar cells. The carbon nanotubes/graphene oxide buffer layer works as an efficient hole transport/electron blocking layer. The photovoltaic conversion efficiency of 13.3% was achieved in the organo-lead iodide perovskite solar cell due to the complementary properties of carbon nanotubes and graphene oxide. Furthermore, the great improvement of photovoltaic performance stability in the perovskite solar cells using carbon nanotubes/graphene oxide/polymethyl methacrylate was demonstrated in comparison with that using a typical organic hole transport layer of 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene.Nano-carbon materials (carbon nanotubes, graphene, and graphene oxide) have potential application for photovoltaics because of their excellent optical and electronic properties. Here, we demonstrate that a single-walled carbon nanotubes/graphene oxide buffer layer greatly improves the photovoltaic performance of organo-lead iodide perovskite solar cells. The carbon nanotubes/graphene oxide buffer layer works as an efficient hole transport/electron blocking layer. The photovoltaic conversion efficiency of 13.3% was achieved in the organo-lead iodide perovskite solar cell due to the complementary properties of carbon nanotubes and graphene oxide. Furthermore, the great improvement of photovoltaic performance stability in the perovskite solar cells using carbon nanotubes/graphene oxide/polymethyl methacrylate was demonstrated in comparison with that using a typical organic hole transport layer of 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene. Electronic supplementary information (ESI

  9. Ionic Charge Transfer Complex Induced Visible Light Harvesting and Photocharge Generation in Perovskite.

    PubMed

    Ng, Tsz-Wai; Thachoth Chandran, Hrisheekesh; Chan, Chiu-Yee; Lo, Ming-Fai; Lee, Chun-Sing

    2015-09-16

    Organometal trihalide perovskite has recently emerged as a new class of promising material for high efficiency solar cells applications. While excess ions in perovskites are recently getting a great deal of attention, there is so far no clear understanding on both their formation and relating ions interaction to the photocharge generation in perovskite. Herein, we showed that tremendous ions indeed form during the initial stage of perovskite formation when the organic methylammonium halide (MAXa, Xa=Br and I) meets the inorganic PbXb2 (Xb=Cl, Br, I). The strong charge exchanges between the Pb2+ cations and Xa- anions result in formation of ionic charge transfer complexes (iCTC). MAXa parties induce empty valence electronic states within the forbidden bandgap of PbXb2. The strong surface dipole provide sufficient driving force for sub-bandgap electron transition with energy identical to the optical bandgap of forming perovskites. Evidences from XPS/UPS and photoluminescence studies showed that the light absorption, exciton dissociation, and photocharge generation of the perovskites are closely related to the strong ionic charge transfer interactions between Pb2+ and Xa- ions in the perovskite lattices. Our results shed light on mechanisms of light harvesting and subsequent free carrier generation in perovskites. PMID:26305717

  10. Catalytic behavior of AMoO{sub x} (A = Ba, Sr) in oxidation of 2-propanol

    SciTech Connect

    Kubo, Jun Ueda, Wataru

    2009-04-02

    Perovskite-type oxides, BaMoO{sub 3} and SrMoO{sub 3}, were prepared by reduction of scheelite-type oxides, BaMoO{sub 4} and SrMoO{sub 4}, in H{sub 2} flow at 873 K and characterized by XRD, TG, SEM, TPR, NH{sub 3}-TPD, UV-vis DRS and BET measurement. The catalytic activity of these alkaline-earth molybdenum oxide catalysts was tested for oxidation of 2-propanol with gaseous oxygen under atmospheric pressure. Dehydration to propylene was mainly promoted over the scheelite-type with Mo{sup 6+}, while oxidative dehydrogenation to acetone was mainly promoted over the perovskite-type with Mo{sup 4+}, and selectivity to acetone was much higher over BaMoO{sub 3} than over SrMoO{sub 3}. Both perovskite-type oxide catalysts underwent oxidation to some degree during the catalytic reaction, so that they also contained some Mo{sup 6+}. We concluded that the high selectivity to acetone resulting from oxidative dehydrogenation during 2-propanol conversion is related to the constantly changing oxidation state of the catalyst, resulting in coexistence of Mo{sup 6+} octahedra and Mo{sup 4+} octahedra on the AMoO{sub 3} oxides.

  11. Oxygen vacancy formation characteristics in the bulk and across different surface terminations of La(1₋x)SrxFe(1₋y)CoyO(3₋δ) perovskite oxides for CO2 conversion

    SciTech Connect

    Maiti, Debtanu; Daza, Yolanda A.; Yung, Matthew M.; Kuhn, John N.; Bhethanabotla, Venkat R.

    2016-01-01

    Density functional theory (DFT) based investigation of two parameters of prime interest -- oxygen vacancy and surface terminations along (100) and (110) planes -- has been conducted for La(1-x)SrxFe(1-y)CoyO(3-..delta..) perovskite oxides in view of their application towards thermochemical carbon dioxide conversion reactions. The bulk oxygen vacancy formation energies for these mixed perovskite oxides are found to increase with increasing lanthanum and iron contents in the 'A' site and 'B' site, respectively. Surface terminations along (100) and (110) crystal planes are studied to probe their stability and their capabilities to accommodate surface oxygen vacancies. Amongst the various terminations, the oxygen-rich (110) surface and strontium-rich (100) surface are the most stable, while transition metal-rich terminations along (100) revealed preference towards the production of oxygen vacancies. The carbon dioxide adsorption strength, a key descriptor for CO2 conversion reactions, is found to increase on oxygen vacant surfaces thus establishing the importance of oxygen vacancies in CO2 conversion reactions. Amongst all the surface terminations, the lanthanum-oxygen terminated surface exhibited the strongest CO2 adsorption strength. The theoretical prediction of the oxygen vacancy trends and the stability of the samples were corroborated by the temperature-programmed reduction and oxidation reactions and in situ XRD crystallography.

  12. Relative rates of nitric oxide and nitrous oxide production by nitrifiers, denitrifiers, and nitrate respirers

    NASA Technical Reports Server (NTRS)

    Anderson, I. C.; Levine, J. S.

    1986-01-01

    An account is given of the atmospheric chemical and photochemical effects of biogenic nitric and nitrous oxide emissions. The magnitude of the biogenic emission of NO is noted to remain uncertain. Possible soil sources of NO and N2O encompass nitrification by autotropic and heterotropic nitrifiers, denitrification by nitrifiers and denitrifiers, nitrate respiration by fermenters, and chemodenitrification. Oxygen availability is the primary determinant of these organisms' relative rates of activity. The characteristics of this major influence are presently investigated in light of the effect of oxygen partial pressure on NO and N2O production by a wide variety of common soil-nitrifying, denitrifying, and nitrate-respiring bacteria under laboratory conditions. The results obtained indicate that aerobic soils are primary sources only when there is sufficient moisture to furnish anaerobic microsites for denitrification.

  13. Nanometer-Scale Epitaxial Strain Release in Perovskite Heterostructures Using 'SrAlOx' Sliding Buffer Layers

    SciTech Connect

    Bell, Christopher

    2011-08-11

    We demonstrate the strain release of LaAlO{sub 3} epitaxial film on SrTiO{sub 3} (001) by inserting ultra-thin 'SrAlO{sub x}' buffer layers. Although SrAlO{sub x} is not a perovskite, nor stable as a single phase in bulk, epitaxy stabilizes the perovskite structure up to a thickness of 2 unit cells (uc). At a critical thickness of 3 uc of SrAlO{sub x}, the interlayer acts as a sliding buffer layer, and abruptly relieves the lattice mismatch between the LaAlO{sub 3} filmand the SrTiO{sub 3} substrate, while maintaining crystallinity. This technique may provide a general approach for strain relaxation of perovskite film far below the thermodynamic critical thickness. A central issue in heteroepitaxial filmgrowth is the inevitable difference in lattice constants between the filmand substrate. Due to this lattice mismatch, thin film are subjected to microstructural strain, which can have a significan effect on the filmproperties. This challenge is especially prominent in the rapidly developing fiel of oxide electronics, where much interest is focused on incorporating the emergent physical properties of oxides in devices. Although strain can be used to great effect to engineer unusual ground states, it is often deleterious for bulk first-orde phase transitions, which are suppressed by the strain and symmetry constraints of the substrate. While there are some reports discussing the control of the lattice mismatch in oxides using thick buffer layers, the materials choice, lattice-tunable range, and control of misfit dislocations are still limited. In this Letter, we report the fabrication of strain-relaxed LaAlO{sub 3} (LAO) thin film on SrTiO{sub 3} (STO) (001) using very thin 'SrAlO{sub x}' (SAO) buffer layers. Whereas for 1 or 2 pseudo-perovskite unit cells (uc) of SAO, the subsequent LAO filmis strained to the substrate, at a critical thickness of 3 uc the SAO interlayer abruptly relieves the lattice mismatch between the LAO and the STO, although maintaining the

  14. Elastic anisotropy of experimental analogues of perovskite and post-perovskite help to interpret D′′ diversity

    PubMed Central

    Yoneda, Akira; Fukui, Hiroshi; Xu, Fang; Nakatsuka, Akihiko; Yoshiasa, Akira; Seto, Yusuke; Ono, Kenya; Tsutsui, Satoshi; Uchiyama, Hiroshi; Baron, Alfred Q. R.

    2014-01-01

    Recent studies show that the D′′ layer, just above the Earth's core–mantle boundary, is composed of MgSiO3 post-perovskite and has significant lateral inhomogeneity. Here we consider the D′′ diversity as related to the single-crystal elasticity of the post-perovskite phase. We measure the single-crystal elasticity of the perovskite Pbnm-CaIrO3 and post-perovskite Cmcm-CaIrO3 using inelastic X-ray scattering. These materials are structural analogues to same phases of MgSiO3. Our results show that Cmcm-CaIrO3 is much more elastically anisotropic than Pbnm-CaIrO3, which offers an explanation for the enigmatic seismic wave velocity jump at the D′′ discontinuity. Considering the relation between lattice preferred orientation and seismic anisotropy in the D′′ layer, we suggest that the c axis of post-perovskite MgSiO3 aligns vertically beneath the Circum-Pacific rim, and the b axis vertically beneath the Central Pacific. PMID:24670790

  15. 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.

  16. Reversal magnetization dependence with the Cr and Fe oxidation states in YFe1-xCrxO3 (0≤x≤1) perovskites

    NASA Astrophysics Data System (ADS)

    Fabian, F. A.; Pedra, P. P.; Moura, K. O.; Duque, J. G. S.; Meneses, C. T.

    2016-06-01

    In this work, we have carried out a detailed study of the magnetic and structural properties of YFe1-xCrxO3 (0≤x≤1) samples with orthorhombic structure obtained by co-precipitation method. Analysis of X-ray diffraction data using Rietveld refinement show that all samples present an orthorhombic crystal system with space group Pnma. Besides, we have observed a reduction of unit cell volume with increasing of the Cr concentration. SEM images show the formation of grains of micrometer order. X-ray Absorption near edge spectroscopy (XANES) measurements show a shift of absorption edge which can be indicate there is (i) different oxidation states to Fe and Cr ions and/or (ii) a changing in the point symmetry of Fe and Cr ions to the compounds. The magnetization measurements indicate a continuous decreasing of the magnetic transition temperature as function of chromium doping. The reversal magnetization effect was observed to concentrations around x=0.5. Besides, the deviation of the Curie-Weiss law and a weak ferromagnetic behavior observed at room temperature in the M vs H curves can be attributed to the strong magnetic interactions between the transition metals with different oxidation states.

  17. Electric-Field-Induced Degradation of Methylammonium Lead Iodide Perovskite Solar Cells.

    PubMed

    Bae, Soohyun; Kim, Seongtak; Lee, Sang-Won; Cho, Kyung Jin; Park, Sungeun; Lee, Seunghun; Kang, Yoonmook; Lee, Hae-Seok; Kim, Donghwan

    2016-08-18

    Perovskite solar cells have great potential for high efficiency generation but are subject to the impact of external environmental conditions such as humidity, UV and sun light, temperature, and electric fields. The long-term stability of perovskite solar cells is an important issue for their commercialization. Various studies on the stability of perovskite solar cells are currently being performed; however, the stability related to electric fields is rarely discussed. Here the electrical stability of perovskite solar cells is studied. Ion migration is confirmed using the temperature-dependent dark current decay. Changes in the power conversion efficiency according to the amount of the external bias are measured in the dark, and a significant drop is observed only at an applied voltage greater than 0.8 V. We demonstrate that perovskite solar cells are stable under an electric field up to the operating voltage. PMID:27462013

  18. Chitosan-Assisted Crystallization and Film Forming of Perovskite Crystals through Biomineralization.

    PubMed

    Yang, Yang; Sun, Chen; Yip, Hin-Lap; Sun, Runcang; Wang, Xiaohui

    2016-03-18

    Biomimetic mineralization is a powerful approach for the synthesis of advanced composite materials with hierarchical organization and controlled structure. Herein, chitosan was introduced into a perovskite precursor solution as a biopolymer additive to control the crystallization and to improve the morphology and film-forming properties of a perovskite film by way of biomineralization. The biopolymer additive was able to control the size and morphology of the perovskite crystals and helped to form smooth films. The mechanism of chitosan-mediated nucleation and growth of the perovskite crystals was explored. As a possible application, the chitosan-perovskite composite film was introduced into a planar heterojunction solar cell and increased power conversion efficiency relative to that observed for the pristine perovskite film was achieved. The biomimetic mineralization method proposed in this study provides an alternative way of preparing perovskite crystals with well-controlled morphology and properties and extends the applications of perovskite crystals in photoelectronic fields, including planar-heterojunction solar cells. PMID:26773727

  19. 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

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

    PubMed

    Yuan, Haifeng; Debroye, Elke; Janssen, Kris; Naiki, Hiroyuki; Steuwe, Christian; Lu, Gang; Moris, Michèle; Orgiu, Emanuele; Uji-I, Hiroshi; De Schryver, Frans; Samorì, Paolo; Hofkens, Johan; Roeffaers, Maarten

    2016-02-01

    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

  1. Planar-integrated single-crystalline perovskite photodetectors.

    PubMed

    Saidaminov, Makhsud I; Adinolfi, Valerio; Comin, Riccardo; Abdelhady, Ahmed L; Peng, Wei; Dursun, Ibrahim; Yuan, Mingjian; Hoogland, Sjoerd; Sargent, Edward H; Bakr, Osman M

    2015-01-01

    Hybrid perovskites are promising semiconductors for optoelectronic applications. However, they suffer from morphological disorder that limits their optoelectronic properties and, ultimately, device performance. Recently, perovskite single crystals have been shown to overcome this problem and exhibit impressive improvements: low trap density, low intrinsic carrier concentration, high mobility, and long diffusion length that outperform perovskite-based thin films. These characteristics make the material ideal for realizing photodetection that is simultaneously fast and sensitive; unfortunately, these macroscopic single crystals cannot be grown on a planar substrate, curtailing their potential for optoelectronic integration. Here we produce large-area planar-integrated films made up of large perovskite single crystals. These crystalline films exhibit mobility and diffusion length comparable with those of single crystals. Using this technique, we produced a high-performance light detector showing high gain (above 10(4) electrons per photon) and high gain-bandwidth product (above 10(8) Hz) relative to other perovskite-based optical sensors. PMID:26548941

  2. 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

  3. Oxidation processes in magneto-optic and related materials

    NASA Technical Reports Server (NTRS)

    Lee, Paul A.; Armstrong, Neal R.; Danzinger, James L.; England, Craig D.

    1992-01-01

    The surface oxidation processes of thin films of magneto-optic materials, such as the rare-earth transition metal alloys have been studied, starting in ultrahigh vacuum environments, using surface analysis techniques, as a way of modeling the oxidation processes which occur at the base of a defect in an overcoated material, at the instant of exposure to ambient environments. Materials examined have included FeTbCo alloys, as well as those same materials with low percentages of added elements, such a Ta, and their reactivities to both O2 and H2O compared with materials such as thin Fe films coated with ultrathin adlayers of Ti. The surface oxidation pathways for these materials is reviewed, and XPS data presented which indicates the type of oxides formed, and a critical region of Ta concentration which provides optimum protection.

  4. Superconducting and related oxides: Physics and nanoengineering 3

    SciTech Connect

    Pavuna, D.; Bozovic, I.

    1998-12-31

    This volume is composed of 51 papers presented at the symposium. Topics covered are: physical properties of oxide superconductors; thin film growth and properties; and device physics and new concepts.

  5. Efremovka 101.1: a CAI with ultrarefractory REE patterns and enormous enrichments of Sc, Zr, and Y in Fassaite and Perovskite

    NASA Astrophysics Data System (ADS)

    El Goresy, A.; Zinner, E.; Matsunami, S.; Palme, H.; Spettel, B.; Lin, Y.; Nazarov, M.

    2002-04-01

    Inclusion 101.1 from the CV3 carbonaceous chondrite Efremovka is a compact Type A Ca-Al-rich inclusion (CAI) highly enriched in ultrarefractory (UR) oxides. It is the first complete CAI with a UR rare earth element (REE) pattern found in a CV3 chondrite. The inclusion is petrographically complex and was formed in a multistage process. It consists of several lithologically unrelated units. The core contains abundant Y- and Zr-perovskite, Sc- and Zr-rich fassaite, and metallic FeNi enclosed in melilite. All mineral species (except spinel) in all lithological units exhibit the same basic UR REE pattern. Four different populations of perovskites are distinguished by different Y/Zr ratios. A few of the perovskites have Y/Zr ratios similar to those obtained from crystal/liquid fractionation experiments. Perovskites from the other three populations have either chondritic, lower than chondritic Y/Zr ratios or extremely low Zr contents. Ca isotopic ratios differ among three perovskites from different populations, demonstrating a variety of sources and formational processes. Most fassaites crystallized in situ through reaction between the CAI liquid and preexisting perovskites. This process induced redistribution of Zr, Y, Sc, and V between perovskite and fassaite, thus overprinting the original abundances in perovskite. Fassaite reaction rims around FeNi metals are also encountered. They are enriched in V, which was gained from the metal through oxidation of V in metal during fassaite crystallization. The relative abundances of Zr, Y, and Sc in perovskites are complementary to the abundances of these elements in Sc- and Zr-fassaite, indicating subsolidus partitioning of these elements between the two phases. Perovskites are enriched in Y and depleted in Sc and Zr in comparison to fassaites. The core contains two complete captured CAIs, several sinuous fragments, and fine-grained polygonal refractory fragments. An assemblage of andradite-wollastonite-hedenbergite and pure

  6. A polymer scaffold for self-healing perovskite solar cells

    PubMed Central

    Zhao, Yicheng; Wei, Jing; Li, Heng; Yan, Yin; Zhou, Wenke; Yu, Dapeng; Zhao, Qing

    2016-01-01

    Advancing of the lead halide perovskite solar cells towards photovoltaic market demands large-scale devices of high-power conversion efficiency, high reproducibility and stability via low-cost fabrication technology, and in particular resistance to humid environment for long-time operation. Here we achieve uniform perovskite film based on a novel polymer-scaffold architecture via a mild-temperature process. These solar cells exhibit efficiency of up to ∼16% with small variation. The unencapsulated devices retain high output for up to 300 h in highly humid environment (70% relative humidity). Moreover, they show strong humidity resistant and self-healing behaviour, recovering rapidly after removing from water vapour. Not only the film can self-heal in this case, but the corresponding devices can present power conversion efficiency recovery after the water vapour is removed. Our work demonstrates the value of cheap, long chain and hygroscopic polymer scaffold in perovskite solar cells towards commercialization. PMID:26732479

  7. A polymer scaffold for self-healing perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Zhao, Yicheng; Wei, Jing; Li, Heng; Yan, Yin; Zhou, Wenke; Yu, Dapeng; Zhao, Qing

    2016-01-01

    Advancing of the lead halide perovskite solar cells towards photovoltaic market demands large-scale devices of high-power conversion efficiency, high reproducibility and stability via low-cost fabrication technology, and in particular resistance to humid environment for long-time operation. Here we achieve uniform perovskite film based on a novel polymer-scaffold architecture via a mild-temperature process. These solar cells exhibit efficiency of up to ~16% with small variation. The unencapsulated devices retain high output for up to 300 h in highly humid environment (70% relative humidity). Moreover, they show strong humidity resistant and self-healing behaviour, recovering rapidly after removing from water vapour. Not only the film can self-heal in this case, but the corresponding devices can present power conversion efficiency recovery after the water vapour is removed. Our work demonstrates the value of cheap, long chain and hygroscopic polymer scaffold in perovskite solar cells towards commercialization.

  8. A polymer scaffold for self-healing perovskite solar cells.

    PubMed

    Zhao, Yicheng; Wei, Jing; Li, Heng; Yan, Yin; Zhou, Wenke; Yu, Dapeng; Zhao, Qing

    2016-01-01

    Advancing of the lead halide perovskite solar cells towards photovoltaic market demands large-scale devices of high-power conversion efficiency, high reproducibility and stability via low-cost fabrication technology, and in particular resistance to humid environment for long-time operation. Here we achieve uniform perovskite film based on a novel polymer-scaffold architecture via a mild-temperature process. These solar cells exhibit efficiency of up to ∼ 16% with small variation. The unencapsulated devices retain high output for up to 300 h in highly humid environment (70% relative humidity). Moreover, they show strong humidity resistant and self-healing behaviour, recovering rapidly after removing from water vapour. Not only the film can self-heal in this case, but the corresponding devices can present power conversion efficiency recovery after the water vapour is removed. Our work demonstrates the value of cheap, long chain and hygroscopic polymer scaffold in perovskite solar cells towards commercialization. PMID:26732479

  9. 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.

  10. Multifunctional MgO Layer in Perovskite Solar Cells.

    PubMed

    Guo, Xudong; Dong, Haopeng; Li, Wenzhe; Li, Nan; Wang, Liduo

    2015-06-01

    A multifunctional magnesium oxide (MgO) layer was successfully introduced into perovskite solar cells (PSCs) to enhance their performance. MgO was coated onto the surface of mesoporous TiO(2) by the decomposition of magnesium acetate and, therefore, could block contact between the perovskite and TiO(2). X-ray photoelectron spectroscopy and infrared spectroscopy showed that the amount of H(2)O/hydroxyl absorbed on the TiO(2) decreased after MgO modification. The UV/Vis absorption spectra of the perovskite with MgO modification revealed an enhanced photoelectric performance compared with that of unmodified perovskite after UV illumination. In addition to the photocurrent, the photovoltage and fill factor also showed an enhancement after modification, which resulted in an increase in the overall efficiency of the cell from 9.6 to 13.9 %. Electrochemical impedance spectroscopy (EIS) confirmed that MgO acts as an insulating layer to reduce charge recombination. PMID:25851999

  11. 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.

  12. 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.

  13. Relative rates of nitric oxide and nitrous oxide production by nitrifiers, denitrifiers, and nitrate respirers.

    PubMed

    Anderson, I C; Levine, J S

    1986-05-01

    Biogenic emissions of nitric and nitrous oxides have important impacts on the photochemistry and chemistry of the atmosphere. Although biogenic production appears to be the overwhelming source of N(2)O, the magnitude of the biogenic emission of NO is very uncertain. In soils, possible sources of NO and N(2)O include nitrification by autotrophic and heterotrophic nitrifiers, denitrification by nitrifiers and denitrifiers, nitrate respiration by fermenters, and chemodenitrification. The availability of oxygen determines to a large extent the relative activities of these various groups of organisms. To better understand this influence, we investigated the effect of the partial pressure of oxygen (pO(2)) on the production of NO and N(2)O by a wide variety of common soil nitrifying, denitrifying, and nitrate-respiring bacteria under laboratory conditions. The production of NO per cell was highest by autotrophic nitrifiers and was independent of pO(2) in the range tested (0.5 to 10%), whereas N(2)O production was inversely proportional to pO(2). Nitrous oxide production was highest in the denitrifier Pseudomonas fluorescens, but only under anaerobic conditions. The molar ratio of NO/N(2)O produced was usually greater than unity for nitrifiers and much less than unity for denitrifiers. Chemodenitrification was the major source of both the NO and N(2)O produced by the nitrate respirer Serratia marcescens. Chemodenitrification was also a possible source of NO and N(2)O in nitrifier cultures but only when high concentrations of nitrite had accumulated or were added to the medium. Although most of the denitrifiers produced NO and N(2)O only under anaerobic conditions, chemostat cultures of Alcaligenes faecalis continued to emit these gases even when the cultures were sparged with air. Based upon these results, we predict that aerobic soils are primary sources of NO and that N(2)O is produced only when there is sufficient soil moisture to provide the anaerobic microsites

  14. Relative oxidative stability of diacylglycerol and triacylglycerol oils.

    PubMed

    Qi, Jin F; Wang, Xiang Y; Shin, Jung-Ah; Lee, Young-Hwa; Jang, Young-Seok; Lee, Jeung Hee; Hong, Soon-Taek; Lee, Ki-Teak

    2015-03-01

    To compare the oxidative stability between diacylglycerol (DAG) oil and conventional triacylglycerol (TAG) oil (that is, soybean oil), the prepared stripped diacylglycerol oil (SDO) and soybean oil (SSBO) were stored at 60 °C in the dark for 144 h. During storage peroxide values (POVs), contents of aldehydes, unsaturated fatty acids were measured to evaluate the oxidative stabilities of the 2 oils. The results showed the content of C18:2, C18:3, and total unsaturated fatty acid decreased faster in DAG oil than in soybean oil, whereas the decreased rate of C18:1 was similar in 2 oils. Also, both rate constants (K1 and K2) obtained from POV (K1 ) and total aldehydes (K2 ) indicated that DAG oil (K1 = 3.22 mmol/mol FA h(-1) , K2 = 0.023 h(-1)) was oxidized more rapidly than soybean oil (K1 = 2.56 mmol/mol FA h(-1) , K2 = 0.021 h(-1)), which was mainly due to the difference of acylglycerol composition of the 2 oils along with higher C18:3 (9.6%) in SDO than SSBO (5.7%). It is concluded that DAG was more easily oxidized than soybean oil at 60 °C in the dark for 144 h. PMID:25678328

  15. Zinc oxide and related compounds: order within the disorder

    NASA Astrophysics Data System (ADS)

    Martins, R.; Pereira, Luisa; Barquinha, P.; Ferreira, I.; Prabakaran, R.; Goncalves, G.; Goncalves, A.; Fortunato, E.

    2009-02-01

    This paper discusses the effect of order and disorder on the electrical and optical performance of ionic oxide semiconductors based on zinc oxide. These materials are used as active thin films in electronic devices such as pn heterojunction solar cells and thin-film transistors. Considering the expected conduction mechanism in ordered and disordered semiconductors the role of the spherical symmetry of the s electron conduction bands will be analyzed and compared to covalent semiconductors. The obtained results show p-type c-Si/a-IZO/poly-ZGO solar cells exhibiting efficiencies above 14%, in device areas of about 2.34 cm2. Amorphous oxide TFTs based on the Ga-Zn-Sn-O system demonstrate superior performance than the polycrystalline TFTs based on ZnO, translated by ION/IOFF ratio exceeding 107, turn-on voltage below 1-2 V and saturation mobility above 25 cm2/Vs. Apart from that, preliminary data on p-type oxide TFT based on the Zn-Cu-O system will also be presented.

  16. Luminescence of perovskite-like niobates and tantalates

    SciTech Connect

    Blasse, G. . Fysisch Lab.); Brixner, L.H. and Co., Wilmington, DE . Central Research and Development Dept.)

    1989-03-01

    The luminescence of perovskite-like niobates and tantalates is compared and discussed in connection with that of titanates. The luminescence properties are strongly related to each other. Electronic delocalization in corner-sharing octahedra is shown to play an important role.

  17. Plasmonic-enhanced perovskite-graphene hybrid photodetectors

    NASA Astrophysics Data System (ADS)

    Sun, Zhenhua; Aigouy, Lionel; Chen, Zhuoying

    2016-03-01

    The surface plasmonic effect of metal nanostructures is a promising method to boost the performance of optoelectronic devices such as solar cells and photodetectors. In this report, gold nanoparticles with surface plasmon resonance localized at about 530 nm were synthesized and integrated into graphene/methylammonium lead iodide perovskite (CH3NH3PbI3) hybrid photodetectors. Compared with pristine graphene-CH3NH3PbI3 devices, a device with gold nanoparticles embedded has a doubly higher photo-responsivity as well as a faster photoresponse speed. The present devices adopt a unique configuration with gold nanoparticles physically separated from the light harvesting component, i.e., the perovskite layer by graphene. Advantages are revealed through a series of characterization techniques and analyses. First, thanks to the tiny thickness of graphene, the plasmonic effect of gold nanoparticles can effectively enhance the near-field of perovskite and thus facilitate light-harvesting. Second, the enhanced light-harvesting in perovskite happens very close to this interface where photo-induced carriers have relatively short paths to diffuse toward graphene, favoring a fast photo-response. This work demonstrates a feasible and inspiring strategy to improve the performance of photodetectors through the surface plasmonic effect of metallic nanostructures.The surface plasmonic effect of metal nanostructures is a promising method to boost the performance of optoelectronic devices such as solar cells and photodetectors. In this report, gold nanoparticles with surface plasmon resonance localized at about 530 nm were synthesized and integrated into graphene/methylammonium lead iodide perovskite (CH3NH3PbI3) hybrid photodetectors. Compared with pristine graphene-CH3NH3PbI3 devices, a device with gold nanoparticles embedded has a doubly higher photo-responsivity as well as a faster photoresponse speed. The present devices adopt a unique configuration with gold nanoparticles physically

  18. The influence of transition metal oxides on the kinetics of Li2O2 oxidation in Li-O2 batteries: high activity of chromium oxides.

    PubMed

    Yao, Koffi P C; Lu, Yi-Chun; Amanchukwu, Chibueze V; Kwabi, David G; Risch, Marcel; Zhou, Jigang; Grimaud, Alexis; Hammond, Paula T; Bardé, Fanny; Shao-Horn, Yang

    2014-02-14

    Reducing the energy loss associated with Li2O2 electrochemical oxidation is paramount to the development of efficient rechargeable lithium-oxygen (Li-O2) batteries for practical use. The influence of a series of perovskites with different eg filling on the kinetics of Li2O2 oxidation was examined using Li2O2-prefilled electrodes. While LaCrO3 is inactive for oxygen evolution upon water oxidation in alkaline solution, it was found to provide the highest specific current towards Li2O2 oxidation among all the perovskites examined. Further exploration of Cr-based catalysts showed that Cr nanoparticles (Cr NP) with an average particle size of 40 nm, having oxidized surfaces, had comparable surface area activities to LaCrO3 but much greater mass activities. Unlike Pt/C and Ru/C that promote electrolyte oxidation in addition to Li2O2 oxidation, no evidence of enhanced electrolyte oxidation was found for Cr NP relative to Vulcan carbon. X-ray absorption spectroscopy at the O K and Cr L edge revealed a redox process of Cr(3+) ↔ Cr(6+) on the surface of Cr NP upon Li2O2 oxidation, which might be responsible for the enhanced oxidation kinetics of Li2O2 and the reduced charging voltages of Li-O2 batteries. PMID:24352578

  19. Superconductivity and magnetism in rapidly solidified perovskites

    SciTech Connect

    O'Handley, R.C.; Kalonji, G.

    1991-01-01

    The report is divided into six parts, reflecting major thrusts of our work since 1987. The six areas are: molecular orbital theory of high {Tc} superconductivity; rapid solidification processing of oxide superconductors; time dependent magnetic and superconducting properties of these inhomogeneous materials; excess Gd in Gd{sub 1+x}Ba{sub 2-x}Cu{sub 3}O{sub 7-{delta}} perovskites; rapid solidification and directional annealing to achieve high Jc; and Mossbauer studies of T = Fe, Co and Ni site selection in YBa{sub 2}(CuT){sub 3}O{sub 7-{delta}} and GdBa{sub 2}(CuT){sub 3}O{sub 7-{delta}}.

  20. Predicting the Elastic Moduli of Perovskites in the Earth's Mantle

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

    Understanding the relationship between the elasticity of a mineral and its composition and structure is essential for building predictive models of mantle flow. Recent advances in laboratory-based single-crystal X- ray diffraction techniques for measuring the intensities of diffraction from crystals held in situ at high pressures in the diamond-anvil cell have been used to determine the role of polyhedral compression in the response of oxide perovskites to high pressure [1]. These new data clearly demonstrate that, contrary to previous belief that perovskites octahedra are essentially incompressible, the compression of the octahedral sites is significant and that the evolution of the perovskite structure with pressure is controlled by a new principle; that of equipartition of bond-valence strain between the A and B cation sites within the structure [2]. The structural response to pressure is thus determined by the compressibility ratio of the A and B cation sites within the structure which can be predicted as inverse of the ratio of the site parameters MA/MB [2] which are completely determined by the room-pressure structure. Further, we find that the bulk elastic properties of perovskites are strongly linearly correlated with this site parameter ratio, thus providing a way to predict the elastic moduli of lower-mantle perovskites from the composition alone. References [1] e.g. Zhao, Ross & Angel (2004) Phys Chem Miner. 31: 299; Ross, Zhao,. & Angel (2004). J. Solid State Chemistry 177:1276, Vanpeteghem CB, Zhao J, Angel RJ, Ross NL, Bolfan-Casanova N (2006) Geophysical Research Letters 33: L03306. [2] Zhao, Ross, & Angel (2004). Acta Cryst. B60:263

  1. Hydrogen pickup measurements in zirconium alloys: Relation to oxidation kinetics

    NASA Astrophysics Data System (ADS)

    Couet, Adrien; Motta, Arthur T.; Comstock, Robert J.

    2014-08-01

    The optimization of zirconium-based alloys used for nuclear fuel cladding aims to reduce hydrogen pickup during operation, and the associated cladding degradation. The present study focuses on precisely and accurately measuring hydrogen pickup fraction for a set of alloys to specifically investigate the effects of alloying elements, microstructure and corrosion kinetics on hydrogen uptake. To measure hydrogen concentrations in zirconium alloys two techniques have been used: a destructive technique, Vacuum Hot Extraction, and a non-destructive one, Cold Neutron Prompt Gamma Activation Analysis. The results of both techniques show that hydrogen pickup fraction varies significantly with exposure time and between alloys. A possible interpretation of the results is that hydrogen pickup results from the need to balance charge. That is, the pickup of hydrogen shows an inverse relationship to oxidation kinetics, indicating that, if transport of charged species is rate limiting, oxide transport properties such as oxide electronic conductivity play a key role in the hydrogen pickup mechanism. Alloying elements (either in solid solution or in precipitates) would therefore impact the hydrogen pickup fraction by affecting charge transport.

  2. 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

  3. Deciphering the physics and chemistry of perovskites with transmission electron microscopy.

    PubMed

    Polking, Mark J

    2016-03-17

    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. PMID:26762871

  4. Nonaqueous solution synthesis process for preparing oxide powders of lead zirconate titanate and related materials

    DOEpatents

    Voigt, James A.; Sipola, Diana L.; Tuttle, Bruce A.; Anderson, Mark T.

    1999-01-01

    A process for producing powders of perovskite-type compounds which comprises mixing a metal alkoxide solution with a lead acetate solution to form a homogeneous, clear metal solution, adding an oxalic acid/n-propanol solution to this metal solution to form an easily filterable, free-flowing precursor powder and then calcining this powder. This process provides fine perovskite-phase powders with ferroelectric properties which are particularly useful in a variety of electronic applications.

  5. Nonaqueous solution synthesis process for preparing oxide powders of lead zirconate titanate and related materials

    DOEpatents

    Voigt, J.A.; Sipola, D.L.; Tuttle, B.A.; Anderson, M.T.

    1999-06-01

    A process is disclosed for producing powders of perovskite-type compounds which comprises mixing a metal alkoxide solution with a lead acetate solution to form a homogeneous, clear metal solution, adding an oxalic acid/n-propanol solution to this metal solution to form an easily filterable, free-flowing precursor powder and then calcining this powder. This process provides fine perovskite-phase powders with ferroelectric properties which are particularly useful in a variety of electronic applications. 4 figs.

  6. Leaf photosynthetic and water-relations responses for 'Valencia' orange trees exposed to oxidant air pollution

    SciTech Connect

    Olszyk, D.M.; Takemoto, B.K.; Poe, M.

    1991-01-01

    Leaf responses were measured to test a hypothesis that reduced photosynthetic capacity and/or altered water relations were associated with reductions in yield for 'Valencia' orange trees (Citrus sinensis (L.), Osbeck) exposed to ambient oxidant air pollution. Exposures were continuous for 4 years to three levels of oxidants (in charcoal-filtered, half-filtered, and non-filtered air). Oxidants had no effect on net leaf photosynthetic rates or on photosynthetic pigment concentrations. A single set of measurements indicated that oxidants increased leaf starch concentrations (24%) prior to flowering, suggesting a change in photosynthate allocation. Leaves exposed to oxidants had small, but consistent, changes in water relations over the summer growing season, compared to trees growing in filtered air. Other changes included decreased stomatal conductance (12%) and transpiration (9%) rates, and increased water pressure potentials (5%). While all responses were subtle, their cumulative impact over 4 years indicated that 'Valencia' orange trees were subject to increased ambient oxidant stress.

  7. Improved Identification and Relative Quantification of Sites of Peptide and Protein Oxidation for Hydroxyl Radical Footprinting

    NASA Astrophysics Data System (ADS)

    Li, Xiaoyan; Li, Zixuan; Xie, Boer; Sharp, Joshua S.

    2013-11-01

    Protein oxidation is typically associated with oxidative stress and aging and affects protein function in normal and pathological processes. Additionally, deliberate oxidative labeling is used to probe protein structure and protein-ligand interactions in hydroxyl radical protein footprinting (HRPF). Oxidation often occurs at multiple sites, leading to mixtures of oxidation isomers that differ only by the site of modification. We utilized sets of synthetic, isomeric "oxidized" peptides to test and compare the ability of electron-transfer dissociation (ETD) and collision-induced dissociation (CID), as well as nano-ultra high performance liquid chromatography (nanoUPLC) separation, to quantitate oxidation isomers with one oxidation at multiple adjacent sites in mixtures of peptides. Tandem mass spectrometry by ETD generates fragment ion ratios that accurately report on relative oxidative modification extent on specific sites, regardless of the charge state of the precursor ion. Conversely, CID was found to generate quantitative MS/MS product ions only at the higher precursor charge state. Oxidized isomers having multiple sites of oxidation in each of two peptide sequences in HRPF product of protein Robo-1 Ig1-2, a protein involved in nervous system axon guidance, were also identified and the oxidation extent at each residue was quantified by ETD without prior liquid chromatography (LC) separation. ETD has proven to be a reliable technique for simultaneous identification and relative quantification of a variety of functionally different oxidation isomers, and is a valuable tool for the study of oxidative stress, as well as for improving spatial resolution for HRPF studies.

  8. 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

  9. Correlated electron perovskite films for optical sensing applications

    NASA Astrophysics Data System (ADS)

    Schultz, Andrew M.; Brown, Thomas D.; Ohodnicki, Paul R.

    2015-10-01

    Advanced power generation technologies including solid oxide fuel cells require advancements in sensor technologies for efficient operation. Gas sensors for SOFC anode streams must be stable in high temperature and under reducing atmospheres. Optical sensing technologies offer the potential for good stability and sensing response under harsh conditions but are relatively new as compared to alternative sensing approaches and require significant developments in underlying device and enabling materials technology. In this paper, the near infrared optical sensing response of La0.8Sr0.2MnO3, a representative correlated perovskite material, is presented. Hydrogen sensing performance was measured in laboratory scale sensing experiments in the range of 1-4% hydrogen. The effect of oxygen on sensor recovery behavior was also examined. The films show a large, recoverable response to the introduction of hydrogen to the gas stream. The results presented here suggest this unique class of materials is a strong candidate for future sensor development efforts targeted at optical sensor applications but also requires additional fundamental research to understand the mechanistic origin of observed optical sensing responses.

  10. Low-temperature sputtered nickel oxide compact thin film as effective electron blocking layer for mesoscopic NiO/CH3NH3PbI3 perovskite heterojunction solar cells.

    PubMed

    Wang, Kuo-Chin; Shen, Po-Shen; Li, Ming-Hsien; Chen, Shi; Lin, Ming-Wei; Chen, Peter; Guo, Tzung-Fang

    2014-08-13

    We introduce the use of low temperature sputtered NiOx thin film, which substitutes the PEDOT-PSS and solution-processed NiOx as an effective electron blocking layer for mesoscopic NiO/CH3NH3PbI3 perovskite solar cells. The influences of film thickness and oxygen doping on the photovoltaic performances are scrutinized. The cell efficiency has been improved from 9.51 to 10.7% for devices using NiOx fabricated under pure argon atmosphere. With adequate doping under 10% oxygen flow ratio, we achieved power conversion efficiency of 11.6%. The procedure is large area scalable and has the advantage for cost-effective perovskite-based photovoltaics. PMID:25054484

  11. Modeling the PbI2 formation in perovskite solar cells using XRD/XPS patterns

    NASA Astrophysics Data System (ADS)

    Sohrabpoor, Hamed; Elyasi, Majid; Aldosari, Marouf; Gorji, Nima E.

    2016-09-01

    The impact of prolonged irradiation and air humidity on the stability of perovskite solar cells is modeled using X-ray diffraction and X-ray photoelectron spectroscopy patterns reported in the literature. Light or air-moisture causes the formation of a thin PbI2 or oxide defective layers (in nanoscale) at the interface of perovskite/hole-transport-layer or at the junction with metallic back contact. This thin layer blocks the carrier transport/passivation at the interfaces and cause degradation of device parameters. Variation in thickness of defective layers, changes the XRD and XPS peaks. This allows detection and estimation of the type, crystallinity and thickness of the defective layer. A simple model is developed here to extract the thickness of such thin defective layers formed in nanometer scale at the back region of several perovskite devices. Based on this information, corrected energy band diagram of every device before and after degradation/aging is drawn and discussed in order to obtain insight into the carrier transport and charge collection at the barrier region. In addition, graphene contacted perovskite devices are investigated showing that honey-comb network of graphene contact reduces the effect of aging leading to formation of a thinner defective layer at the perovskite surface compared to perovskite devices with conventional inorganic contacts i.e. Au, Al.

  12. Reliable thermal processing of organic perovskite films deposited on ZnO

    NASA Astrophysics Data System (ADS)

    Zakhidov, Alex; Manspeaker, Chris; Lyashenko, Dmitry; Alex Zakhidov Team

    Zinc oxide (ZnO) is a promising semiconducting material to serve as an electron transport layer (ETL) for solar cell devices based on organo-halide lead perovskites. ZnO ETL for perovskite photovoltaics has a combination of attractive electronic and optical properties: i) the electron affinity of ZnO is well aligned with valence band edge of the CH3NH3PbI3, ii) electron mobility of ZnO is >1 cm2/(Vs), which is a few orders of magnitude higher than that of TiO2 (another popular choice of ETL for perovskite photovoltaic devices), and iii) ZnO has a large of band gap of 3.3 eV, which ensures optical transparency and large barrier for the hole injection. Moreover, ZnO nanostructures can be printed on flexible substrates at room temperatures in cost effective manner. However, it was recently found that organic perovskites deposited on ZnO are unstable and readily decompose at >90°C. In this work, we further investigate the mechanism of decomposition of CH3NH3PbI3 film deposited on ZnO and reveal the role of the solvent in the film during the annealing process. We also develop a restricted volume solvent annealing (RVSA) process for post annealing of the perovskite film on ZnO without decomposition. We demonstrate that RVSA enables reliable perovskite solar cell fabrication.

  13. Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber

    NASA Astrophysics Data System (ADS)

    Stranks, Samuel; Eperon, Giles; Grancini, Giulia; Menelaou, Christopher; Alcocer, Marcelo; Leijtens, Tomas; Herz, Laura; Petrozza, Annamaria; Snaith, Henry

    2014-03-01

    Organic-inorganic perovskites have shown promise as high-performance absorbers in solar cells, first as a coating on a mesoporous metal oxide scaffold and more recently as a solid layer in planar heterojunction architectures. Here, we report transient absorption and photoluminescence-quenching measurements to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide (CH3NH3PbI3-xClx) and triiodide (CH3NH3PbI3) perovskite absorbers. We found that the diffusion lengths are greater than 1 micrometer in the mixed halide perovskite, which is an order of magnitude greater than the absorption depth. In contrast, the triiodide absorber has electron-hole diffusion lengths of order 100 nanometers. Finally, we fabricated solution-processed thin-film planar heterojunction devices, achieving power conversion efficiencies of over 12% using the mixed halide absorber but only 4% with the triiodide perovskite. Our results show that the long diffusion lengths justify the high efficiency of planar heterojunction perovskite solar cells, and identify a critical parameter to optimize for future perovskite absorber development.

  14. "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.

  15. The effect of minor elements on H incorporation in MgSiO3 perovskite

    NASA Astrophysics Data System (ADS)

    Watson, H. C.; Fei, Y.; Hauri, E.; Reid, F.; Jacobsen, S. D.

    2006-12-01

    It has been predicted that silicate perovskite in the lower mantle may be a significant reservoir for hydrogen in the Earth's interior, although quantitative analysis of the hydrogen storage capacity has remained elusive. This is primarily due to difficulties in interpreting FTIR spectra of perovskite samples at room pressure [eg. Murakami et al. 2002, Science 295, 1885-1887, Bolfan-Casanova et al. 2003, Geophys. Res. Lett. 30, 1905, Litasov et al. 2003, EPSL 211, 189-203]. The mechanism by which H is thought to be incorporated into perovskite is through substitution of minor trivalent elements such as Al and Fe. This may open oxygen vacancies that are in turn, filled with OH groups for charge balance , although coupled substitution (e.g. 2Al3+ ----> Si^{4+}+Mg2+) is also a possibility [Navrotsky 1999, Science 284 5421, 1788 - 1789]. We have synthesized Al-bearing, and Al-Fe bearing perovskite samples under hydrous conditions in a multi-anvil apparatus at pressures ranging from 23-26 GPa and 1800°C and 1200°C. The starting materials consisted of either oxide powders with brucite as the source of H2O, or pre-synthesized Al, Fe bearing hydrous enstatite. The resulting perovskite crystals range in size from <20 microns to >100 microns in size. Their major element chemistry has been characterized by electron microprobe, and the H content of samples has been measured by secondary ion mass spectrometry using a 6f Cameca ion microprobe and is substantial (>1000ppm in some samples). Preliminary FTIR measurements support the idea that the H measured is structurally bound in the perovskite crystal. We find a linear correlation between Al and H content in the perovskite, and discussion follows on the substitution mechanisms for minor elements and H into perovskite at conditions relevant to the uppermost lower mantle.

  16. Relation between Endothelial Nitric Oxide Synthase Genotypes and Oxidative Stress Markers in Larynx Cancer

    PubMed Central

    Yanar, K.; Çakatay, U.; Aydın, S.; Verim, A.; Atukeren, P.; Özkan, N. E.; Karatoprak, K.; Cebe, T.; Turan, S.; Ozkök, E.; Korkmaz, G.; Cacına, C.; Küçükhüseyin, O.; Yaylım, İ.

    2016-01-01

    Nitric oxide synthase (eNOS/NOS3) is responsible for the endothelial synthesis of nitric oxide (NO•). G894T polymorphism leads to the amino acid substitution from Glu298Asp that causes lower NOS3 activity and basal NO• production in NOS3 894T (298Asp) allele carriers compared with the GG homozygotes. NO• acts as an antioxidant protecting against Fenton's reaction which generates highly reactive hydroxyl radicals. Allelic variation of NOS3 may influence an individual's risk of laryngeal cancer (LC). In the current study we have examined the possible relationship between NOS3 G894T genotypes and various systemic oxidative damage markers such as protein carbonyl, advanced oxidation protein products, Cu, Zn-superoxide dismutase, thiol group fractions, and lipid hydroperoxides in LC patients. Genotyping was carried out by PCR-RFLP. In LC patients with TT genotype, Cu, Zn-superoxide dismutase activities and nonprotein thiol levels were significantly higher than the controls. In patients with GT and GG genotype, high levels of lipid hydroperoxides showed statistical significance when compared to controls. Our results indicate a potential relationship among G894T polymorphism of NOS3, and impaired redox homeostasis. Further studies are required to determine the role of NOS3 gene polymorphism and impaired plasma redox homeostasis. PMID:26682008

  17. Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Cu/TEMPO and Related Catalyst Systems

    PubMed Central

    Ryland, Bradford L.; Stahl, Shannon S.

    2014-01-01

    Alcohol and amine oxidations are common reactions in laboratory and industrial synthesis of organic molecules. Aerobic oxidation methods have long been sought for these transformations, but few practical methods exist that offer advantages over traditional oxidation methods. Recently developed homogeneous Cu/TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) and related catalyst systems appear to fill this void. The reactions exhibit high levels of chemoselectivity and broad functional-group tolerance, and they often operate efficiently at room temperature with ambient air as the oxidant. These advances, together with their historical context and recent applications, are highlighted in this minireview. PMID:25044821

  18. Perovskite solar cell using a two-dimensional titania nanosheet thin film as the compact layer.

    PubMed

    Li, Can; Li, Yahui; Xing, Yujin; Zhang, Zelin; Zhang, Xianfeng; Li, Zhen; Shi, Yantao; Ma, Tingli; Ma, Renzhi; Wang, Kunlin; Wei, Jinquan

    2015-07-22

    The compact layer plays an important role in conducting electrons and blocking holes in perovskite solar cells (PSCs). Here, we use a two-dimensional titania nanosheet (TNS) thin film as the compact layer in CH3NH3PbI3 PSCs. TNS thin films with thicknesses ranging from 8 to 75 nm were prepared by an electrophoretic deposition method from a dilute TNS/tetrabutylammonium hydroxide solution. The TNS thin films contact the fluorine-doped tin oxide grains perfectly. Our results show that a 8-nm-thick TNS film is sufficient for acting as the compact layer. Currently, the PSC with a TNS compact layer has a high efficiency of 10.7% and relatively low hysteresis behavior. PMID:26158908

  19. Anion charge storage through oxygen intercalation in LaMnO3 perovskite pseudocapacitor electrodes.

    PubMed

    Mefford, J Tyler; Hardin, William G; Dai, Sheng; Johnston, Keith P; Stevenson, Keith J

    2014-07-01

    Perovskite oxides have attracted significant attention as energy conversion materials for metal-air battery and solid-oxide fuel-cell electrodes owing to their unique physical and electronic properties. Amongst these unique properties is the structural stability of the cation array in perovskites that can accommodate mobile oxygen ions under electrical polarization. Despite oxygen ion mobility and vacancies having been shown to play an important role in catalysis, their role in charge storage has yet to be explored. Herein we investigate the mechanism of oxygen-vacancy-mediated redox pseudocapacitance for a nanostructured lanthanum-based perovskite, LaMnO3. This is the first example of anion-based intercalation pseudocapacitance as well as the first time oxygen intercalation has been exploited for fast energy storage. Whereas previous pseudocapacitor and rechargeable battery charge storage studies have focused on cation intercalation, the anion-based mechanism presented here offers a new paradigm for electrochemical energy storage. PMID:24880729

  20. Anion charge storage through oxygen intercalation in LaMnO3 perovskite pseudocapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Mefford, J. Tyler; Hardin, William G.; Dai, Sheng; Johnston, Keith P.; Stevenson, Keith J.

    2014-07-01

    Perovskite oxides have attracted significant attention as energy conversion materials for metal-air battery and solid-oxide fuel-cell electrodes owing to their unique physical and electronic properties. Amongst these unique properties is the structural stability of the cation array in perovskites that can accommodate mobile oxygen ions under electrical polarization. Despite oxygen ion mobility and vacancies having been shown to play an important role in catalysis, their role in charge storage has yet to be explored. Herein we investigate the mechanism of oxygen-vacancy-mediated redox pseudocapacitance for a nanostructured lanthanum-based perovskite, LaMnO3. This is the first example of anion-based intercalation pseudocapacitance as well as the first time oxygen intercalation has been exploited for fast energy storage. Whereas previous pseudocapacitor and rechargeable battery charge storage studies have focused on cation intercalation, the anion-based mechanism presented here offers a new paradigm for electrochemical energy storage.

  1. Neutral color semitransparent microstructured perovskite solar cells.

    PubMed

    Eperon, Giles E; Burlakov, Victor M; Goriely, Alain; Snaith, Henry J

    2014-01-28

    Neutral-colored semitransparent solar cells are commercially desired to integrate solar cells into the windows and cladding of buildings and automotive applications. Here, we report the use of morphological control of perovskite thin films to form semitransparent planar heterojunction solar cells with neutral color and comparatively high efficiencies. We take advantage of spontaneous dewetting to create microstructured arrays of perovskite "islands", on a length-scale small enough to appear continuous to the eye yet large enough to enable unattenuated transmission of light between the islands. The islands are thick enough to absorb most visible light, and the combination of completely absorbing and completely transparent regions results in neutral transmission of light. Using these films, we fabricate thin-film solar cells with respectable power conversion efficiencies. Remarkably, we find that such discontinuous films still have good rectification behavior and relatively high open-circuit voltages due to the inherent rectification between the n- and p-type charge collection layers. Furthermore, we demonstrate the ease of "color-tinting" such microstructured perovksite solar cells with no reduction in performance, by incorporation of a dye within the hole transport medium. PMID:24467381

  2. Plasmonic-enhanced perovskite-graphene hybrid photodetectors.

    PubMed

    Sun, Zhenhua; Aigouy, Lionel; Chen, Zhuoying

    2016-04-14

    The surface plasmonic effect of metal nanostructures is a promising method to boost the performance of optoelectronic devices such as solar cells and photodetectors. In this report, gold nanoparticles with surface plasmon resonance localized at about 530 nm were synthesized and integrated into graphene/methylammonium lead iodide perovskite (CH3NH3PbI3) hybrid photodetectors. Compared with pristine graphene-CH3NH3PbI3 devices, a device with gold nanoparticles embedded has a doubly higher photo-responsivity as well as a faster photoresponse speed. The present devices adopt a unique configuration with gold nanoparticles physically separated from the light harvesting component, i.e., the perovskite layer by graphene. Advantages are revealed through a series of characterization techniques and analyses. First, thanks to the tiny thickness of graphene, the plasmonic effect of gold nanoparticles can effectively enhance the near-field of perovskite and thus facilitate light-harvesting. Second, the enhanced light-harvesting in perovskite happens very close to this interface where photo-induced carriers have relatively short paths to diffuse toward graphene, favoring a fast photo-response. This work demonstrates a feasible and inspiring strategy to improve the performance of photodetectors through the surface plasmonic effect of metallic nanostructures. PMID:26882839

  3. Structural stability and catalytic activity of lanthanum-based perovskites

    SciTech Connect

    Sergey N. Rashkeev; Lucia M. Petkovic

    2011-05-01

    Perovskite-type oxide materials with a general formula La(1-x)A(x)Fe(1-y)Co(y)O(3-delta), where A is an alkaline earth metal Sr or Ba have been studied as cathode materials for catalytic reduction of oxygen in solid oxide fuel cells (SOFC), as well as combustion catalysts. In this study, we use a combination of temperature programmed reduction measurements, X-ray diffraction, carbon black catalytic oxidation measurements, and first-principles, density-functional-theory (DFT) calculations to elucidate the main processes that contribute into the structural stability and catalytic activity for soot oxidation of these materials. In particular, we investigate the dynamics of the structure reconstruction with oxygen loss during the regulated increase of the temperature. The calculations are in good qualitative agreement with catalytic experiments and allow identify special combinations of the perovskite chemical composition and local surface structures for which one could expect the highest catalytic activity for the soot oxidation process.

  4. Design, synthesis, crystal structure and magnetic properties of novel osmium-based B-site ordered double perovskites

    NASA Astrophysics Data System (ADS)

    Russell, David D.

    Transition metal oxides (TMOs) with face centered cubic arrangement of magnetic ions are composed of triangular sub-lattices. When antiferromagnetic (AFM) interactions of the same strengths between all three pathways in triangular settings are in place, spin constraints cannot be fulfilled simultaneously and the system undergoes geometric magnetic frustration (GMF). The purpose of the work presented in this thesis is to better understand the criteria for a system to undergo GMF. To achieve this, the novel B-site ordered double perovskites Ca2ScOsO6 and Ca2.2Mg0.8 OsO6 were synthesized in polycrystalline form utilizing the conventional solid-state method. The crystal structure of these compounds were characterized through X-ray diffraction, and magnetic properties were explored through magnetic susceptibility measurements. Employing the spin-dimer analysis method, relative magnetic exchange interactions were calculated and modeled. These novel osmium-based B-site ordered double perovskites were then compared to isostructural compounds to study the effects of the osmium oxidation state on crystal structure and the exhibited properties.

  5. Assessment of perovskite-type La0.8Sr0.2ScxMn1-xO3-δ oxides as anodes for intermediate-temperature solid oxide fuel cells using hydrocarbon fuels

    NASA Astrophysics Data System (ADS)

    Sengodan, S.; Yeo, H. J.; Shin, J. Y.; Kim, G.

    2011-03-01

    Composites formed by the infiltration of 40 wt% La0.8Sr0.2ScxMn1-xO3-δ (LSSM) oxides (x = 0.1, 0.2, 0.3) into 65% porous yttria-stabilized zirconia (YSZ) are investigated as anode materials for intermediate-temperature solid oxide fuel cells for hydrocarbon oxidation. The oxygen non-stoichiometry and electrical conductivity of each LSSM-YSZ composite are determined by coulometric titration. As the concentration of Sc increases, the composites show higher phase stability and the electrical conductivity of LSSM is significantly affected by the Sc doping, the non-stoichiometric oxygen content, and oxygen partial pressure (p(O2)). To achieve better electrochemical performance, it is necessary to add ceria-supported palladium catalyst for operation with humidified CH4. Anode polarization resistance increases with Sc doping due to a decrease in electrical conductivity. An electrolyte-supported cell with a LSSM-YSZ composite anode delivers peak power densities of 395 and 340 mW cm-2 at 923 K in humidified (3% H2O) H2 and CH4, respectively, at a flow rate of 20 mL min-1.

  6. Promoting Photochemical Water Oxidation with Metallic Band Structures.

    PubMed

    Liu, Hongfei; Moré, René; Grundmann, Henrik; Cui, Chunhua; Erni, Rolf; Patzke, Greta R

    2016-02-10

    The development of economic water oxidation catalysts is a key step toward large-scale water splitting. However, their current exploration remains empirical to a large extent. Elucidating the correlations between electronic properties and catalytic activity is crucial for deriving general and straightforward catalyst design principles. Herein, strongly correlated electronic systems with abundant and easily tunable electronic properties, namely La(1-x)Sr(x)BO3 perovskites and La(2-x)Sr(x)BO4 layered perovskites (B = Fe, Co, Ni, or Mn), were employed as model systems to identify favorable electronic structures for water oxidation. We established a direct correlation between the enhancement of catalytic activity and the insulator to metal transition through tuning the electronic properties of the target perovskite families via the La(3+)/Sr(2+) ratio. Their improved photochemical water oxidation performance was clearly linked to the increasingly metallic character. These electronic structure-activity relations provide a promising guideline for constructing efficient water oxidation catalysts. PMID:26771537

  7. Gender-related differences in susceptibility to oxidative stress in healthy middle-aged Serbian adults.

    PubMed

    Topic, Aleksandra; Malic, Zivka; Francuski, Djordje; Stankovic, Marija; Markovic, Bojan; Soskic, Blagoje; Tomic, Branko; Ilic, Stefan; Dobrivojevic, Snezana; Drca, Sanja; Radojkovic, Dragica

    2016-03-01

    Gender-related differences in the association between polymorphism of xenobiotic-metabolising enzymes or non-genetic biomarkers and susceptibility to oxidative stress was assessed in healthy middle-aged Serbian adults, by urinary 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG/creatinine) and total antioxidant status in serum (TAOS). Females were more susceptible to oxidative stress. In both genders, positive predictor of the antioxidative protection was serum triglyceride, while BMI <25 kg/m(2) was associated with oxidative stress. Susceptibility to oxidative stress in males was associated with GSTT1*null allele and increased serum iron, but in females, it was decreased serum bilirubin. Early identification of the risk factors could be important in the prevention of oxidative stress-related diseases. PMID:26754535

  8. Ligand-Stabilized Reduced-Dimensionality Perovskites.

    PubMed

    Quan, Li Na; Yuan, Mingjian; Comin, Riccardo; Voznyy, Oleksandr; Beauregard, Eric M; Hoogland, Sjoerd; Buin, Andrei; Kirmani, Ahmad R; Zhao, Kui; Amassian, Aram; Kim, Dong Ha; Sargent, Edward H

    2016-03-01

    Metal halide perovskites have rapidly advanced thin-film photovoltaic performance; as a result, the materials' observed instabilities urgently require a solution. Using density functional theory (DFT), we show that a low energy of formation, exacerbated in the presence of humidity, explains the propensity of perovskites to decompose back into their precursors. We find, also using DFT, that intercalation of phenylethylammonium between perovskite layers introduces quantitatively appreciable van der Waals interactions. These drive an increased formation energy and should therefore improve material stability. Here we report reduced-dimensionality (quasi-2D) perovskite films that exhibit improved stability while retaining the high performance of conventional three-dimensional perovskites. Continuous tuning of the dimensionality, as assessed using photophysical studies, is achieved by the choice of stoichiometry in materials synthesis. We achieve the first certified hysteresis-free solar power conversion in a planar perovskite solar cell, obtaining a 15.3% certified PCE, and observe greatly improved performance longevity. PMID:26841130

  9. Cystic Fibrosis-Related Oxidative Stress and Intestinal Lipid Disorders

    PubMed Central

    Kleme, Marie-Laure

    2015-01-01

    Abstract Significance: Cystic fibrosis (CF) is the most common lethal genetic disorder in the Caucasian people. It is due to the mutation of cystic fibrosis transmembrane conductance regulator (CFTR) gene located on the long arm of the chromosome 7, which encodes for CFTR protein. The latter, an adenosine triphosphate binding cassette, is a transmembrane chloride channel that is also involved in glutathione transport. As glutathione/glutathione disulfide constitutes the most important pool of cellular redox systems, CFTR defects could thus disrupt the intracellular redox balance. Resulting multisystemic diseases are essentially characterized by a chronic respiratory failure, a pancreatic insufficiency, an essential fatty acid deficiency (EFAD), and inadequate levels of antioxidant vitamins. Recent Advances: The pathophysiology of CF is complex; however, several mechanisms are proposed, including oxidative stress (OxS) whose implication is recognized and has been clearly demonstrated in CF airways. Critical Issues: Little is known about OxS intrinsic triggers and its own involvement in intestinal lipid disorders. Despite the regular administration of pancreatic supplements, high-fat high-calorie diets, and antioxidant fat-soluble vitamins, there is a persistence of steatorrhea, EFAD, and harmful OxS. Intriguingly, several trials with elevated doses of antioxidant vitamins have not yielded significant improvements. Future Directions: The main sources and self-maintenance of OxS in CF should be clarified to improve treatment of patients. Therefore, this review will discuss the potential sources and study the mechanisms of OxS in the intestine, known to develop various complications, and its involvement in intestinal lipid disorders in CF patients. Antioxid. Redox Signal. 22, 614–631. PMID:25611180

  10. Room temperature synthesis of Bi25FeO39 and hydrothermal kinetic relations between sillenite- and distorted perovskite-type bismuth ferrites.

    PubMed

    Lopes, Armandina M L; Araújo, João P; Ferdov, Stanislav

    2014-12-28

    The time-dependent study at mild hydrothermal conditions revealed the kinetic relation between structurally unrelated bismuth ferrites. We report the synthetic conditions that disclose the in situ transformation of Bi25FeO39 into BiFeO3 by only extending the time for crystallization. We also demonstrate how a careful investigation of the early stages of multiferroics crystallization provides cheap and easy room-temperature access to the important sillenite-type of structure of Bi25FeO39. The crystal structure analysis by the Rietveld method and magnetization measurements provided detailed structure and magnetic relations between the synthesis conditions and the properties of the run product. The BiFeO3 antiferromagnetic behavior with a small ferromagnetic component arising from the particle's surface uncompensated spins is ascertained. PMID:25351519

  11. Oxidative damage of DNA by chromium(V) complexes: relative importance of base versus sugar oxidation.

    PubMed Central

    Bose, R N; Moghaddas, S; Mazzer, P A; Dudones, L P; Joudah, L; Stroup, D

    1999-01-01

    Chromium(V)-mediated oxidative damage of deoxy-ribonucleic acids was investigated at neutral pH in aqueous solution by utilizing bis(2-ethyl-2-hydroxy-butanato)oxochromate(V) (I) and bis(hydroxyethyl)-amino-tris(hydroxymethyl)methane)oxochromate(V) (II). Single-stranded and double-stranded (ds) calf thymus and human placenta DNA, as well as two oligomers, 5'-GATCTAGTAGGAGGACAAATAGTGTTTG-3' and 5'-GATCCAAGCAAACACTATTTGTCCTCCTACTA-3', were reacted with the chromium(V) complexes. Most products were separated and characterized by chroma-tographic and spectroscopic methods. Polyacrylamide gel electrophoresis experiments reveal more damage at G sites in comparison to other bases. Three primary oxidation products, 5-methylene-2-furanone (5-MF), furfural and 8-oxo-2'-deoxyguanosine, were characterized. A minor product, which appears to be thymine propenal, was also observed. The dsDNA produces more furfural than furanone. The formation of these two products resulted from hydrogen ion or hydride transfer from C1' and C5' positions of the ribose to the oxo-chromium(V) center. Since no enhancements of these products (except propenal) were observed in the presence of oxygen, mechanisms pertaining to the participation of activated oxygen species may be ruled out. The oxidation of the G base is most likely associated with an oxygen atom transfer from the oxo-metallates to the double bond between C8 and N7 of the purine ring. The formation of the propenal may be associated with an oxygen-activated species, since a marginal enhancement of this product was observed in the presence of oxygen. The formation of furfural in higher abundance over 5-MF for dsDNA was attributed to the ease of hydrogen ion (or hydride transfer) from the C5' compared to C1' position of the ribose within a Cr(V)-DNA intermediate in which the metal center is bound to the phosphate diester moiety. PMID:10219096

  12. Oxidative damage of DNA by chromium(V) complexes: relative importance of base versus sugar oxidation.

    PubMed

    Bose, R N; Moghaddas, S; Mazzer, P A; Dudones, L P; Joudah, L; Stroup, D

    1999-05-15

    Chromium(V)-mediated oxidative damage of deoxy-ribonucleic acids was investigated at neutral pH in aqueous solution by utilizing bis(2-ethyl-2-hydroxy-butanato)oxochromate(V) (I) and bis(hydroxyethyl)-amino-tris(hydroxymethyl)methane)oxochromate(V) (II). Single-stranded and double-stranded (ds) calf thymus and human placenta DNA, as well as two oligomers, 5'-GATCTAGTAGGAGGACAAATAGTGTTTG-3' and 5'-GATCCAAGCAAACACTATTTGTCCTCCTACTA-3', were reacted with the chromium(V) complexes. Most products were separated and characterized by chroma-tographic and spectroscopic methods. Polyacrylamide gel electrophoresis experiments reveal more damage at G sites in comparison to other bases. Three primary oxidation products, 5-methylene-2-furanone (5-MF), furfural and 8-oxo-2'-deoxyguanosine, were characterized. A minor product, which appears to be thymine propenal, was also observed. The dsDNA produces more furfural than furanone. The formation of these two products resulted from hydrogen ion or hydride transfer from C1' and C5' positions of the ribose to the oxo-chromium(V) center. Since no enhancements of these products (except propenal) were observed in the presence of oxygen, mechanisms pertaining to the participation of activated oxygen species may be ruled out. The oxidation of the G base is most likely associated with an oxygen atom transfer from the oxo-metallates to the double bond between C8 and N7 of the purine ring. The formation of the propenal may be associated with an oxygen-activated species, since a marginal enhancement of this product was observed in the presence of oxygen. The formation of furfural in higher abundance over 5-MF for dsDNA was attributed to the ease of hydrogen ion (or hydride transfer) from the C5' compared to C1' position of the ribose within a Cr(V)-DNA intermediate in which the metal center is bound to the phosphate diester moiety. PMID:10219096

  13. Neutron diffraction studies on ABO3 (A=Lanthanum, Strontium, B=Iron, Cobalt , Nickel, Copper, Manganese, Titanium) perovskite used in solid oxide fuel cell (SOFC) and double perovskite Barium2YttriumRuthenium0.85Copper0.15Oxygen6 superconductor

    NASA Astrophysics Data System (ADS)

    Cai, Qingsheng

    ABO3(A=La, Sr, B=Fe, Co, Ni, Cu, Mn, Ti) perovskites are of great interest due to their mixed electronic and oxygen ion conductivity. They are candidates for the electrodes of SOFCs. The mixed conductivity can be enhanced through the substitution of La3+ by Sr2+ at A sites, and the substitution of Fe3+ by other transition metal ions at B sites. The charge imbalance and overall charge neutrality can be maintained by the presence of charged oxygen vacancies and mixed valence state ions at the B sites. These point defects are the origin of the mixed electronic and oxygen ion conductivity. This study investigates the effects of substitutions at A sites and/or B sites on the crystal and magnetic structure, oxygen vacancies, and the thermal expansion coefficients at different temperatures and gaseous environment. The oxygen vacancy concentration can relax the perovskite distortion and has a close relationship with the magnetic properties. La0.6Sr0.4FeO3-delta, La0.6Sr0.4Fe0.8Co0.2O3-delta , and La0.8Sr0.2Fe0.8Co0.2O 3-delta can be good candidates for the cathodes of SOFCs at intermediate temperature. The double perovskite Ba2YRu0.85Cu0.15O 6 superconductor and a mixture of 5wt% YBa2Cu3O 7-delta and undoped Ba2YRuO6 were investigated with the aid of neutron diffraction. The 1:1 B site ordering is observed and long range antiferromagnetic ordering of the Ru sublattice with a type I magnetic structure appears when the temperature is below 38K. An incommensurate antiferromagnetic ordering of Cu is observed in the temperature range 38K-85K. This ordering is not seen in undoped material. The decomposition of Cu-doped Ba2YRuO6 into undoped Ba 2YRuO6 and YBa2Cu3O7-delta is not seen. YBa2Cu3O7-delta is not stable at the temperature used to prepare the Cu-doped Ba2YRuO6 superconductor. These results confirm the presence of superconductivity without CuO2 planes.

  14. Controlling the conduction band offset for highly efficient ZnO nanorods based perovskite solar cell

    NASA Astrophysics Data System (ADS)

    Dong, Juan; Shi, Jiangjian; Li, Dongmei; Luo, Yanhong; Meng, Qingbo

    2015-08-01

    The mechanism of charge recombination at the interface of n-type electron transport layer (n-ETL) and perovskite absorber on the carrier properties in the perovskite solar cell is theoretically studied. By solving the one dimensional diffusion equation with different boundary conditions, it reveals that the interface charge recombination in the perovskite solar cell can be suppressed by adjusting the conduction band offset (ΔEC) at ZnO ETL/perovskite absorber interface, thus leading to improvements in cell performance. Furthermore, Mg doped ZnO nanorods ETL has been designed to control the energy band levels. By optimizing the doping amount of Mg, the conduction band minimum of the Mg doped ZnO ETL has been raised up by 0.29 eV and a positive ΔEC of about 0.1 eV is obtained. The photovoltage of the cell is thus significantly increased due to the relatively low charge recombination.

  15. Electric Field Control of Jahn-Teller Distortions in Bulk Perovskites

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    The Jahn-Teller distortion, by its very nature, is often at the heart of the various electronic properties displayed by perovskites and related materials. Despite the Jahn-Teller mode being nonpolar, we devise and demonstrate, in the present Letter, an electric field control of Jahn-Teller distortions in bulk perovskites. The electric field control is enabled through an anharmonic lattice mode coupling between the Jahn-Teller distortion and a polar mode. We confirm this coupling and quantify it through first-principles calculations. The coupling will always exist within the P b 21m space group, which is found to be the favored ground state for various perovskites under sufficient tensile epitaxial strain. Intriguingly, the calculations reveal that this mechanism is not only restricted to Jahn-Teller active systems, promising a general route to tune or induce novel electronic functionality in perovskites as a whole.

  16. 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

  17. Iron partitioning between perovskite and post-perovskite: A transmission electron microscope study

    SciTech Connect

    Hirose, K.; Takafuji, N.; Shieh, S.R.; Duffy, T.S.

    2008-09-30

    The effect of iron on the post-perovskite phase transition has been controversial. We have performed direct chemical analyses of co-existing perovskite and post-perovskite that were synthesized from an (Mg{sub 0.91}Fe{sub 0.09})SiO{sub 3} bulk composition using a laser-heated diamond anvil cell at pressures above 100 GPa and temperatures of 1700-1800 K. Analysis on quenched samples was carried out using the transmission electron microscope (TEM). The results demonstrate that crystalline perovskite grains are enriched in iron compared to adjacent amorphous parts presumably converted from post-perovskite. This indicates that ferrous iron stabilizes perovskite to higher pressures. The ferrous and ferric irons are likely to have competing effects on the post-perovskite phase transition, and therefore the effect of iron may be controlled by aluminum.

  18. Lichen communities on conifers in Southern California mountains: an ecological survey relative to oxidant air pollution

    SciTech Connect

    Sigal, L.L.; Nash, T.H. III

    1983-01-01

    In comparison with collections from the early 1900's when oxidant air pollution was essentially absent, 50% fewer lichen species were found on conifers during 3 yr (1976-1979) of collecting and sampling in the mountains of Southern California. Among the five mountain ranges studied, the San Bernardino Mountains, the region with the highest oxidant levels, had lower lichen frequency and cover values. Within the San Bernardino study sites, lichen cover was inversely related to estimated oxidant doses. Furthermore, at sites with high oxidant levels, marked morphological deterioration of the common species Hypogymnia enteromorpha was documented. Transplants of this species from the relatively unpolluted Cuyamaca Rancho State Park into the San Bernardino Mountains exhibited similar deterioration after a year's exposure. 4 figures, 9 tables.

  19. Lichen communities on conifers in Southern California mountains: an ecological survey relative to oxidant air pollution

    SciTech Connect

    Sigal, L.L.; Nash T.H. III

    1983-01-01

    In comparison with collections from the early 1900's when oxidant air pollution was essentially absent, 50% fewer lichen species were found on conifers during 3 yr (1976-1979) of collecting and sampling in the mountains of Southern California. Among the five mountain ranges studied, the San Bernardino Mountains, the region with the highest oxidant levels, had lower lichen frequency and cover values. Within the San Bernardino study sites, lichen cover was inversely related to estimated oxidant doses. Furthermore, at sites with high oxidant levels, marked morphological deterioration of the common species Hypogymnia enteromorpha was documented. Transplants of this species from the relatively unpolluted Cuyamaca Rancho State Park in the San Bernardino Mountains exhibited similar deterioration after a year's exposure.

  20. Oxide film defects in Al alloys and the formation of hydrogen- related porosity

    NASA Astrophysics Data System (ADS)

    Griffiths, W. D.; Gerrard, A. J.; Yue, Y.

    2016-03-01

    Double oxide film defects have also been held responsible for the origins of hydrogen porosity, where hydrogen dissolved in the Al melt passes into the interior atmosphere of the double oxide film defect causing it to inflate. However, this is in opposition to long- established evidence that H cannot readily diffuse through aluminium oxide. To investigate this further, samples of commercial purity Al were first degassed to remove their initial H content, and then heated to above their melting point and held in atmospheres of air and nitrogen respectively, to determine any differences in H pick-up. The experiment showed that samples held in an oxidising atmosphere, and having an oxide skin, picked up significantly less H than when the samples were held in a nitrogen atmosphere, which resulted in the formation of AlN in cracks in the oxide skin of the sample. It is suggested that double oxide film defects can give rise to hydrogen-related porosity, but this occurs more quickly when the oxygen in the original oxide film defect has been consumed by reaction with the surrounding melt and nitrogen reacts to form AlN, which is more permeable to H than alumina, more easily allowing the oxide film defect to give rise to a hydrogen pore. This is used to interpret results from an earlier synchrotron experiment, in which a small pore was seen to grow into a larger pore, while an adjacent large pore remained at a constant size.

  1. 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

  2. Measurement of Quadrupole Interactions in LaMO3 (M = Cr, Fe, Co) Perovskites by TDPAC

    NASA Astrophysics Data System (ADS)

    Junqueira, A. C.; Dogra, R.; Carbonari, A. W.; Saxena, R. N.; Mestnik-Filho, J.; Moralles, M.

    2001-11-01

    The perturbed angular correlation (PAC) technique has been used to study the electric field gradient (EFG) in LaCoO3 perovskite. The results are compared with those for LaCrO3, LaFeO3 measured earlier. The PAC probe, 111In → 111Cd, was introduced in the oxide lattice by means of chemical reaction during sample preparation. In the present work, the temperature dependence of the electric quadrupole interaction parameters, for LaCoO3 was investigated. The resulting systematics of EFG at 111Cd, in La(Cr,Fe,Co)O3 perovskites, reveals a linear dependence with temperature.

  3. Ultrathin Cu2O as an efficient inorganic hole transporting material for perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Yu, Weili; Li, Feng; Wang, Hong; Alarousu, Erkki; Chen, Yin; Lin, Bin; Wang, Lingfei; Hedhili, Mohamed Nejib; Li, Yangyang; Wu, Kewei; Wang, Xianbin; Mohammed, Omar F.; Wu, Tom

    2016-03-01

    We demonstrate that ultrathin P-type Cu2O thin films fabricated by a facile thermal oxidation method can serve as a promising hole-transporting material in perovskite solar cells. Following a two-step method, inorganic-organic hybrid perovskite solar cells were fabricated and a power conversion efficiency of 11.0% was achieved. We found that the thickness and properties of Cu2O layers must be precisely tuned in order to achieve the optimal solar cell performance. The good performance of such perovskite solar cells can be attributed to the unique properties of ultrathin Cu2O, including high hole mobility, good energy level alignment with CH3NH3PbI3, and longer lifetime of photo-excited carriers. Combining the merits of low cost, facile synthesis, and high device performance, ultrathin Cu2O films fabricated via thermal oxidation hold promise for facilitating the developments of industrial-scale perovskite solar cells.We demonstrate that ultrathin P-type Cu2O thin films fabricated by a facile thermal oxidation method can serve as a promising hole-transporting material in perovskite solar cells. Following a two-step method, inorganic-organic hybrid perovskite solar cells were fabricated and a power conversion efficiency of 11.0% was achieved. We found that the thickness and properties of Cu2O layers must be precisely tuned in order to achieve the optimal solar cell performance. The good performance of such perovskite solar cells can be attributed to the unique properties of ultrathin Cu2O, including high hole mobility, good energy level alignment with CH3NH3PbI3, and longer lifetime of photo-excited carriers. Combining the merits of low cost, facile synthesis, and high device performance, ultrathin Cu2O films fabricated via thermal oxidation hold promise for facilitating the developments of industrial-scale perovskite solar cells. Electronic supplementary information (ESI) available: Experimental details, AFM images, XRD, hysteresis, XPS, EDAX, device stability and

  4. 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.

  5. Towards optical optimization of planar monolithic perovskite/silicon-heterojunction tandem solar cells

    NASA Astrophysics Data System (ADS)

    Albrecht, Steve; Saliba, Michael; Correa-Baena, Juan-Pablo; Jäger, Klaus; Korte, Lars; Hagfeldt, Anders; Grätzel, Michael; Rech, Bernd

    2016-06-01

    Combining inorganic–organic perovskites and crystalline silicon into a monolithic tandem solar cell has recently attracted increased attention due to the high efficiency potential of this cell architecture. Promising results with published efficiencies above 21% have been reported so far. To further increase the device performance, optical optimizations enabling device related guidelines are highly necessary. Here we experimentally show the optical influence of the ITO thickness in the interconnecting layer and fabricate an efficient monolithic tandem cell with a reduced ITO layer thickness that shows slightly improved absorption within the silicon sub-cell and a stabilized power output of 17%. Furthermore we present detailed optical simulations on experimentally relevant planar tandem stacks to give practical guidelines to reach efficiencies above 25%. By optimizing the thickness of all functional and the perovskite absorber layers, together with the optimization of the perovskite band-gap, we present a tandem stack that can yield ca 17.5 mA cm‑ 2 current in both sub-cells at a perovskite band-gap of 1.73 eV including losses from reflection and parasitic absorption. Assuming that the higher band-gap of the perovskite absorber directly translates into a higher open circuit voltage, the perovskite sub-cell should be able to reach a value of 1.3 V. With that, realistic efficiencies above 28% are within reach for planar monolithic tandem cells in which the thickness of the perovskite top-cell and the perovskite band-gap are highly optimized. When applying light trapping schemes such as textured surfaces and by reducing the parasitic absorption of the functional layers, for example in spiro-OMeTAD, this monolithic tandem can overcome 30% power conversion efficiency.

  6. 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.

  7. 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

  8. Direct monitoring of ultrafast electron and hole dynamics in perovskite solar cells.

    PubMed

    Piatkowski, Piotr; Cohen, Boiko; Javier Ramos, Francisco; Di Nunzio, Maria; Nazeeruddin, Mohammad Khaja; Grätzel, Michael; Ahmad, Shahzada; Douhal, Abderrazzak

    2015-06-14

    Organic-inorganic hybrid perovskite solar cells have emerged as cost effective efficient light-to-electricity conversion devices. Unravelling the time scale and the mechanisms that govern the charge carrier dynamics is of paramount importance for a clear understanding and further optimization of the perovskite based devices. For the classical FTO/bulk titania blocking layer/mesoporous titania/perovskite/Spiro-OMeTAD (FTO/TPS) cell, further detailed and systematic studies of the ultrafast events related to exciton generation, electron and hole transfer, ultrafast relaxation are still needed. We characterize the initial ultrafast processes attributed to the exciton-perovskite lattice interactions influenced by charge transfer to the electron and hole transporters that precede the exciton diffusion into free charge carriers occurring in the sensitizer. Time-resolved transient absorption studies of the FTO/perovskite and FTO/TPS samples under excitation at different wavelengths and at low fluence 2 (μJ cm(-2)) indicate the sub-picosecond electron and hole injection into titania and Spiro-OMeTAD, respectively. Furthermore, the power-dependent femtosecond transient absorption measurements support the ultrafast charge transfer and show strong Auger-type multiparticle interactions at early times. We reveal that the decays of the internal trap states are the same for both films, while those at surfaces differ. The contribution of the former in the recombination is small, thus increasing the survival probability of the charges in the excited perovskite. PMID:25972103

  9. Acetate Salts as Nonhalogen Additives To Improve Perovskite Film Morphology for High-Efficiency Solar Cells.

    PubMed

    Wu, Qiliang; Zhou, Pengcheng; Zhou, Weiran; Wei, Xiangfeng; Chen, Tao; Yang, Shangfeng

    2016-06-22

    A two-step method has been popularly adopted to fabricate a perovskite film of planar heterojunction organo-lead halide perovskite solar cells (PSCs). However, this method often generates uncontrollable film morphology with poor coverage. Herein, we report a facile method to improve perovskite film morphology by incorporating a small amount of acetate (CH3COO(-), Ac(-)) salts (NH4Ac, NaAc) as nonhalogen additives in CH3NH3I solution used for immersing PbI2 film, resulting in improved CH3NH3PbI3 film morphology. Under the optimized NH4Ac additive concentration of 10 wt %, the best power conversion efficiency (PCE) reaches 17.02%, which is enhanced by ∼23.2% relative to that of the pristine device without additive, whereas the NaAc additive does not lead to an efficiency enhancement despite the improvement of the CH3NH3PbI3 film morphology. SEM study reveals that NH4Ac and NaAc additives can both effectively improve perovskite film morphology by increasing the surface coverage via diminishing pinholes. The improvement on CH3NH3PbI3 film morphology is beneficial for increasing the optical absorption of perovskite film and improving the interfacial contact at the perovskite/spiro-OMeTAD interface, leading to the increase of short-circuit current and consequently efficiency enhancement of the PSC device for NH4Ac additive only. PMID:27253082

  10. Ambient Engineering for High-Performance Organic-Inorganic Perovskite Hybrid Solar Cells.

    PubMed

    Huang, Jiabin; Yu, Xuegong; Xie, Jiangsheng; Xu, Dikai; Tang, Zeguo; Cui, Can; Yang, Deren

    2016-08-24

    Considering the evaporation of solvents during fabrication of perovskite films, the organic ambience will present a significant influence on the morphologies and properties of perovskite films. To clarify this issue, various ambiences of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and chlorobenzene (CBZ) are introduced during fabrication of perovskite films by two-step sequential deposition method. The results reveal that an ambient CBZ atmosphere is favorable to control the nucleation and growth of CH3NH3PbI3 grains while the others present a negative effect. The statistical results show that the average efficiencies of perovskite solar cells processed in an ambient CBZ atmosphere can be significantly improved by a relatively average value of 35%, compared with those processed under air. The efficiency of the best perovskite solar cells can be improved from 10.65% to 14.55% by introducing this ambience engineering technology. The CH3NH3PbI3 film with large-size grains produced in an ambient CBZ atmosphere can effectively reduce the density of grain boundaries, and then the recombination centers for photoinduced carriers. Therefore, a higher short-circuit current density is achieved, which makes main contribution to the improvement in efficiency. These results provide vital progress toward understanding the role of ambience in the realization of highly efficient perovskite solar cells. PMID:27489961

  11. Perovskite LaTiO₃-Ag0.2 nanomaterials for nonenzymatic glucose sensor with high performance.

    PubMed

    Wang, Yin-zhu; Zhong, Hui; Li, Xiao-mo; Jia, Fei-fei; Shi, Yi-xiang; Zhang, Wei-guang; Cheng, Zhi-peng; Zhang, Li-li; Wang, Ji-kui

    2013-10-15

    In this paper, a nonenzymatic glucose biosensor based on perovskite LaTiO3-Ag0.2(LTA) modified electrode was presented. The morphology and the composition of the perovskite LaTiO₃-Ag0.2 nanomaterials were characterized by using scanning electron microscopy (SEM) and X-ray diffraction (XRD) respectively. The LaTiO₃-Ag0.2(LTA) composite was investigated by electrochemical characterization using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Under optimal conditions, CV and chronoamperometry (I-t) study revealed that, compared with the bare glassy carbon electrode (GCE), the modified electrode showed a remarkable increase in the efficiency of the electrocatalytic oxidation of glucose, starting at around +0.70 V (vs. Ag/AgCl). The prepared sensor exhibited a high sensitivity of 784.14 µAmM⁻¹ cm⁻², a low detection limit of 2.1×10⁻⁷ M and a wide linear range from 2.5 µM to 4 mM (R=0.9997). More importantly, the LTA modified electrode was also relatively insensitive to commonly interfering species such as ascorbic acid (AA), uric acid (UA), dopamine (DA) in high potential. Moreover, the nonenzymatic sensor was applied to the determination of glucose in human serum samples and the results were in good agreement with clinical data. Electrodes modified with perovskite nanomaterials are highly promising for nonenzymatic electrochemical detection of glucose because of their high sensitivity, fast response, excellent stability and good reproducibility. PMID:23648686

  12. A new perovskite-type NdFeO3 adsorbent: synthesis, characterization, and As(V) adsorption

    NASA Astrophysics Data System (ADS)

    Luu, Minh Dai; Nhiem Dao, Ngoc; Van Nguyen, Duc; Chuc Pham, Ngoc; Ninh Vu, The; Dung Doan, Trung

    2016-06-01

    Nanocrystalline NdFeO3 perovskite oxide was prepared by the combustion method using polyvinyl alcohol (PVA) and corresponding metal nitrate precursors under optimum process conditions, using a solution with a pH of 2, a metal/PVA molar ratio of 1:3, and a calcination temperature of 600 °C, and was characterized by x-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer–Emmett–Teller nitrogen adsorption and desorption, energy dispersive x-ray spectroscopy, Fourier transform infrared spectroscopy, laser Raman spectroscopy, and thermogravimetric and differential thermal analysis. The synthesized perovskite NdFeO3, which had an average size of 20 nm and a relatively high surface area of 20 m2 g‑1, was investigated for adsorbing hazardous arsenate from aqueous solution. Arsenate adsorption by perovskite NdFeO3 is a pH-dependent process with a high adsorption capacity at pH levels between 4 and 7 and a maximum As(V) adsorption capacity of 126.58 mg g‑1, higher than most arsenate adsorbents reported in the literature. Kinetic and equilibrium data of reaction under the experimental conditions are best described by a pseudo-second-order and the Langmuir isotherm equation. The values of enthalpy, Gibbs free energy and entropy changes (ΔH0 = +63.916 kJ mol‑1, ΔG0 = ‑6.551 kJ mol‑1 to ‑14.021 kJ mol‑1 at T = 283‑313 K, ΔS0 = +0.249 kJ mol‑1 K‑1) suggested that the reaction was endothermic, spontaneous, and took place with increasing entropy.

  13. Increased oxidative stress in pemphigus vulgaris is related to disease activity and HLA-association.

    PubMed

    Shah, Amit Aakash; Dey-Rao, Rama; Seiffert-Sinha, Kristina; Sinha, Animesh A

    2016-06-01

    Pemphigus vulgaris (PV) is a rare blistering skin disorder characterized by the disadhesion of keratinocytes due to autoantibody attack against epidermal targets including desmoglein (Dsg) 3, Dsg 1 and possibly other adhesion and non-adhesion molecules. The mechanisms leading to immune-mediated pathology in PV are multifactorial and not fully understood. Recently, oxidative stress (antioxidant/oxidant disequilibrium) has been proposed as a contributory mechanism of autoimmune skin diseases, including PV. In this study, we directly assessed oxidative stress via measurement of total antioxidant capacity (TAC) using ELISA in 47 PV patients, 25 healthy controls and 18 bullous pemphigoid (BP) patients. We also performed microarray gene expression analysis on a separate set of 21 PV patients and 10 healthy controls to evaluate transcriptional dysregulation in oxidative stress-related pathways. Our data indicate that there is a significant reduction in TAC levels in PV patients compared with healthy controls, as well as BP patients. Furthermore, PV patients with active disease have significantly lower TAC levels than PV patients in remission. We also find that HLA allele status has a significant influence on oxidative stress. These findings are corroborated by microarray analysis showing differentially expressed genes involved in oxidative stress between the aforementioned groups. Collectively, our findings provide support for a role of oxidative stress in PV. Whether increased oxidative stress leads to disease manifestation and/or activity, or if disease activity leads to increased oxidative stress remains unknown. Future longitudinal studies may help to further elucidate the relationship between PV and oxidative stress. PMID:26911801

  14. Stability of organometal perovskites with organic overlayers

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    The air-stability of vapour-phase-deposited methylammonium lead triiodide (CH3NH3PbI3) 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 (PbI2), 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.

  15. Efficient Luminescence from Perovskite Quantum Dot Solids.

    PubMed

    Kim, Younghoon; Yassitepe, Emre; Voznyy, Oleksandr; Comin, Riccardo; Walters, Grant; Gong, Xiwen; Kanjanaboos, Pongsakorn; Nogueira, Ana F; Sargent, Edward H

    2015-11-18

    Nanocrystals of CsPbX3 perovskites are promising materials for light-emitting optoelectronics because of their colloidal stability, optically tunable bandgap, bright photoluminescence, and excellent photoluminescence quantum yield. Despite their promise, nanocrystal-only films of CsPbX3 perovskites have not yet been fabricated; instead, highly insulating polymers have been relied upon to compensate for nanocrystals' unstable surfaces. We develop solution chemistry that enables single-step casting of perovskite nanocrystal films and overcomes problems in both perovskite quantum dot purification and film fabrication. Centrifugally cast films retain bright photoluminescence and achieve dense and homogeneous morphologies. The new materials offer a platform for optoelectronic applications of perovskite quantum dot solids. PMID:26529572

  16. Perovskite Superlattices as Tunable Microwave Devices

    NASA Technical Reports Server (NTRS)

    Christen, H. M.; Harshavardhan, K. S.

    2003-01-01

    Experiments have shown that superlattices that comprise alternating epitaxial layers of dissimilar paraelectric perovskites can exhibit large changes in permittivity with the application of electric fields. The superlattices are potentially useful as electrically tunable dielectric components of such microwave devices as filters and phase shifters. The present superlattice approach differs fundamentally from the prior use of homogeneous, isotropic mixtures of base materials and dopants. A superlattice can comprise layers of two or more perovskites in any suitable sequence (e.g., ABAB..., ABCDABCD..., ABACABACA...). Even though a single layer of one of the perovskites by itself is not tunable, the compositions and sequence of the layers can be chosen so that (1) the superlattice exhibits low microwave loss and (2) the interfacial interaction between at least two of the perovskites in the superlattice renders either the entire superlattice or else at least one of the perovskites tunable.

  17. 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. PMID:26912212

  18. 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

  19. 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.

  20. Research progress on electronic phase separation in low-dimensional perovskite manganite nanostructures

    PubMed Central

    2014-01-01

    Perovskite oxide manganites with a general formula of R1-x AxMnO3 (where R is a trivalent rare-earth element such as La, Pr, Sm, and A is a divalent alkaline-earth element such as Ca, Sr, and Ba) have received much attention due to their unusual electron-transport and magnetic properties, which are indispensable for applications in microelectronic, magnetic, and spintronic devices. Recent advances in the science and technology have resulted in the feature sizes of microelectronic devices based on perovskite manganite oxides down-scaling into nanoscale dimensions. At the nanoscale, low-dimensional perovskite manganite oxide nanostructures display novel physical properties that are different from their bulk and film counterparts. Recently, there is strong experimental evidence to indicate that the low-dimensional perovskite manganite oxide nanostructures are electronically inhomogeneous, consisting of different spatial regions with different electronic orders, a phenomenon that is named as electronic phase separation (EPS). As the geometry sizes of the low-dimensional manganite nanostructures are reduced to the characteristic EPS length scale (typically several tens of nanometers in manganites), the EPS is expected to be strongly modulated, leading to quite dramatic changes in functionality and more emergent phenomena. Therefore, reduced dimensionality opens a door to the new functionalities in perovskite manganite oxides and offers a way to gain new insight into the nature of EPS. During the past few years, much progress has been made in understanding the physical nature of the EPS in low-dimensional perovskite manganite nanostructures both from experimentalists and theorists, which have a profound impact on the oxide nanoelectronics. This nanoreview covers the research progresses of the EPS in low-dimensional perovskite manganite nanostructures such as nanoparticles, nanowires/nanotubes, and nanostructured films and/or patterns. The possible physical origins of the

  1. Origin of the kink in the band dispersion of the ferromagnetic perovskite SrRuO3: Electron-phonon coupling

    NASA Astrophysics Data System (ADS)

    Yang, H. F.; Liu, Z. T.; Fan, C. C.; Yao, Q.; Xiang, P.; Zhang, K. L.; Li, M. Y.; Li, H.; Liu, J. S.; Shen, D. W.; Jiang, M. H.

    2016-03-01

    Perovskite SrRuO3, a prototypical conductive ferromagnetic oxide, exhibits a kink in its band dispersion signaling the unusual electron dynamics therein. However, the origin of this kink remains elusive. By taking advantage of the combo of reactive molecular beam epitaxy and in situ angle-resolved photoemission spectroscopy, we systematically studied the evolution of the low-energy electronic structure of SrRuO3 films with thickness thinning down to a nearly two-dimensional limit in a well-controlled way. The kink structure persists even in the four-unit-cell-thick film. Moreover, through quantitative self-energy analysis, we observed the negligible thickness dependence of the binding energy of the kink, which is in sharp contrast to the downward trend of the Curie temperature with reducing the film thickness. Together with previously reported transport and Raman studies, this finding suggests that the kink of perovskite SrRuO3 should originate from the electron-phonon coupling rather than magnetic collective modes, and the in-plane phonons may play a dominant role. Considering such a kink structure of SrRuO3 is similar to those of many other correlated oxides, we suggest the possible ubiquity of the coupling of electrons to oxygen-related phonons in correlated oxides.

  2. 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.

  3. Competing interactions in ferromagnetic/antiferromagnetic perovskite superlattices

    SciTech Connect

    Takamura, Y.; Biegalski, M.B.; Christen, H.M.

    2009-10-22

    Soft x-ray magnetic dichroism, magnetization, and magnetotransport measurements demonstrate that the competition between different magnetic interactions (exchange coupling, electronic reconstruction, and long-range interactions) in La{sub 0.7}Sr{sub 0.3}FeO{sub 3}(LSFO)/La{sub 0.7}Sr{sub 0.3}MnO{sub 3}(LSMO) perovskite oxide superlattices leads to unexpected functional properties. The antiferromagnetic order parameter in LSFO and ferromagnetic order parameter in LSMO show a dissimilar dependence on sublayer thickness and temperature, illustrating the high degree of tunability in these artificially layered materials.

  4. Perovskite solar cell with an efficient TiO₂ compact film.

    PubMed

    Ke, Weijun; Fang, Guojia; Wang, Jing; Qin, Pingli; Tao, Hong; Lei, Hongwei; Liu, Qin; Dai, Xin; Zhao, Xingzhong

    2014-09-24

    A perovskite solar cell with a thin TiO2 compact film prepared by thermal oxidation of sputtered Ti film achieved a high efficiency of 15.07%. The thin TiO2 film prepared by thermal oxidation is very dense and inhibits the recombination process at the interface. The optimum thickness of the TiO2 compact film prepared by thermal oxidation is thinner than that prepared by spin-coating method. Also, the TiO2 compact film and the TiO2 porous film can be sintered at the same time. This one-step sintering process leads to a lower dark current density, a lower series resistance, and a higher recombination resistance than those of two-step sintering. Therefore, the perovskite solar cell with the TiO2 compact film prepared by thermal oxidation has a higher short-circuit current density and a higher fill factor. PMID:25166513

  5. Efficient organic-inorganic hybrid perovskite solar cells processed in air.

    PubMed

    Seetharaman S, Madhu; Nagarjuna, Puvvala; Kumar, P Naresh; Singh, Surya Prakash; Deepa, Melepurath; Namboothiry, Manoj A G

    2014-12-01

    Organic-inorganic hybrid perovskite solar cells with fluorine doped tin oxide/titanium dioxide/CH3NH3PbI3-xClx/poly(3-hexylthiophene)/silver were made in air with more than 50% humidity. The best devices showed an open circuit voltage of 640 mV, a short circuit current density of 18.85 mA cm(-2), a fill factor of 0.407 and a power conversion efficiency of 5.67%. The devices showed external quantum efficiency varying from 60 to 80% over a wavelength region of 350 nm to 750 nm of the solar spectrum. The morphology of the perovskite was investigated using scanning electron microscopy and it was found to be porous in nature. This study provides insights into air-stability of perovskite solar cells. PMID:25315711

  6. Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells.

    PubMed

    Zhang, Wei; Pathak, Sandeep; Sakai, Nobuya; Stergiopoulos, Thomas; Nayak, Pabitra K; Noel, Nakita K; Haghighirad, Amir A; Burlakov, Victor M; deQuilettes, Dane W; Sadhanala, Aditya; Li, Wenzhe; Wang, Liduo; Ginger, David S; Friend, Richard H; Snaith, Henry J

    2015-01-01

    Solution-processed metal halide perovskite semiconductors, such as CH3NH3PbI3, have exhibited remarkable performance in solar cells, despite having non-negligible density of defect states. A likely candidate is halide vacancies within the perovskite crystals, or the presence of metallic lead, both generated due to the imbalanced I/Pb stoichiometry which could evolve during crystallization. Herein, we show that the addition of hypophosphorous acid (HPA) in the precursor solution can significantly improve the film quality, both electronically and topologically, and enhance the photoluminescence intensity, which leads to more efficient and reproducible photovoltaic devices. We demonstrate that the HPA can reduce the oxidized I2 back into I(-), and our results indicate that this facilitates an improved stoichiometry in the perovskite crystal and a reduced density of metallic lead. PMID:26615763

  7. Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells

    DOE PAGESBeta

    Zhang, Wei; Pathak, Sandeep; Sakai, Nobuya; Stergiopoulos, Thomas; Nayak, Pabitra K.; Noel, Nakita K.; Haghighirad, Amir A.; Burlakov, Victor M.; deQuilettes, Dane W.; Sadhanala, Aditya; et al

    2015-11-30

    Solution-processed metal halide perovskite semiconductors, such as CH3NH3PbI3, have exhibited remarkable performance in solar cells, despite having non-negligible density of defect states. A likely candidate is halide vacancies within the perovskite crystals, or the presence of metallic lead, both generated due to the imbalanced I/Pb stoichiometry which could evolve during crystallization. Herein, we show that the addition of hypophosphorous acid (HPA) in the precursor solution can significantly improve the film quality, both electronically and topologically, and enhance the photoluminescence intensity, which leads to more efficient and reproducible photovoltaic devices. We demonstrate that the HPA can reduce the oxidized I2 backmore » into I-, and our results indicate that this facilitates an improved stoichiometry in the perovskite crystal and a reduced density of metallic lead.« less

  8. Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells

    SciTech Connect

    Zhang, Wei; Pathak, Sandeep; Sakai, Nobuya; Stergiopoulos, Thomas; Nayak, Pabitra K.; Noel, Nakita K.; Haghighirad, Amir A.; Burlakov, Victor M.; deQuilettes, Dane W.; Sadhanala, Aditya; Li, Wenzhe; Wang, Liduo; Ginger, David S.; Friend, Richard H.; Snaith, Henry J.

    2015-11-30

    Solution-processed metal halide perovskite semiconductors, such as CH3NH3PbI3, have exhibited remarkable performance in solar cells, despite having non-negligible density of defect states. A likely candidate is halide vacancies within the perovskite crystals, or the presence of metallic lead, both generated due to the imbalanced I/Pb stoichiometry which could evolve during crystallization. Herein, we show that the addition of hypophosphorous acid (HPA) in the precursor solution can significantly improve the film quality, both electronically and topologically, and enhance the photoluminescence intensity, which leads to more efficient and reproducible photovoltaic devices. We demonstrate that the HPA can reduce the oxidized I2 back into I-, and our results indicate that this facilitates an improved stoichiometry in the perovskite crystal and a reduced density of metallic lead.

  9. A Novel Silver Molybdenum Oxyfluoride Perovskite as a Cathode Material for Lithium Batteries

    SciTech Connect

    Yoon, W.S.; Tong, W.; Hagh, N.M.; Amatucci, G.G.

    2009-05-26

    Novel electroactive nanostructured silver molybdenum oxyfluoride (SMOF) perovskites Ag{sup 1+}{sub 3}Mo{sup 6+}(O{sub 3}F{sub 3}) have been successfully synthesized by a mechanochemical reaction. The formation of this perovskite was investigated throughout the Ag-Mo composition range with the use of either Ag{sup 1+} or Ag{sup 2+} in the form of AgF and AgF{sub 2} as the reactant, respectively. The compositional study combined with X-ray diffraction and extensive Raman investigation was utilized to determine structure and cation distribution and infer oxidation state. Finally, preliminary electrochemical characterization of the perovskites vs lithium was investigated.

  10. Fabrication of Planar Heterojunction Perovskite Solar Cells by Controlled Low-Pressure Vapor Annealing.

    PubMed

    Li, Yanbo; Cooper, Jason K; Buonsanti, Raffaella; Giannini, Cinzia; Liu, Yi; Toma, Francesca M; Sharp, Ian D

    2015-02-01

    A new method for achieving high efficiency planar CH3NH3I3-xClx perovskite photovoltaics, based on a low pressure, reduced temperature vapor annealing is demonstrated. Heterojunction devices based on this hybrid halide perovskite exhibit a top PCE of 16.8%, reduced J-V hysteresis, and highly repeatable performance without need for a mesoporous or nanocrystalline metal oxide layer. Our findings demonstrate that large hysteresis is not an inherent feature of planar heterojunctions, and that efficient charge extraction can be achieved with uniform halide perovskite materials with desired composition. X-ray diffraction, valence band spectroscopy, and transient absorption measurements of these thin films reveal that structural modifications induced by chlorine clearly dominate over chemical and electronic doping effects, without affecting the Fermi level or photocarrier lifetime in the material. PMID:26261969

  11. Double-layered ZnO nanostructures for efficient perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Mahmood, Khalid; S. Swain, Bhabani; Amassian, Aram

    2014-11-01

    To date, a single layer of TiO2 or ZnO has been the most successful implementations of any electron transport layer (ETL) in solution-processed perovskite solar cells. In a quest to improve the ETL, we explore a new nanostructured double-layer ZnO film for mesoscopic perovskite-based thin film photovoltaics. This approach yields a maximum power conversion efficiency of 10.35%, which we attribute to the morphology of oxide layer and to faster electron transport. The successful implementation of the low-temperature hydrothermally processed double-layer ZnO film as ETL in perovskite solar cells highlights the opportunities to further improve the efficiencies by focusing on the ETL in this rapidly developing field.

  12. Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells

    PubMed Central

    Zhang, Wei; Pathak, Sandeep; Sakai, Nobuya; Stergiopoulos, Thomas; Nayak, Pabitra K.; Noel, Nakita K.; Haghighirad, Amir A.; Burlakov, Victor M.; deQuilettes, Dane W.; Sadhanala, Aditya; Li, Wenzhe; Wang, Liduo; Ginger, David S.; Friend, Richard H.; Snaith, Henry J.

    2015-01-01

    Solution-processed metal halide perovskite semiconductors, such as CH3NH3PbI3, have exhibited remarkable performance in solar cells, despite having non-negligible density of defect states. A likely candidate is halide vacancies within the perovskite crystals, or the presence of metallic lead, both generated due to the imbalanced I/Pb stoichiometry which could evolve during crystallization. Herein, we show that the addition of hypophosphorous acid (HPA) in the precursor solution can significantly improve the film quality, both electronically and topologically, and enhance the photoluminescence intensity, which leads to more efficient and reproducible photovoltaic devices. We demonstrate that the HPA can reduce the oxidized I2 back into I−, and our results indicate that this facilitates an improved stoichiometry in the perovskite crystal and a reduced density of metallic lead. PMID:26615763

  13. Double-layered ZnO nanostructures for efficient perovskite solar cells.

    PubMed

    Mahmood, Khalid; S Swain, Bhabani; Amassian, Aram

    2014-12-21

    To date, a single layer of TiO2 or ZnO has been the most successful implementations of any electron transport layer (ETL) in solution-processed perovskite solar cells. In a quest to improve the ETL, we explore a new nanostructured double-layer ZnO film for mesoscopic perovskite-based thin film photovoltaics. This approach yields a maximum power conversion efficiency of 10.35%, which we attribute to the morphology of oxide layer and to faster electron transport. The successful implementation of the low-temperature hydrothermally processed double-layer ZnO film as ETL in perovskite solar cells highlights the opportunities to further improve the efficiencies by focusing on the ETL in this rapidly developing field. PMID:25373624

  14. 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.

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

    DOE PAGESBeta

    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

  16. Protective mechanisms of Cucumis sativus in diabetes-related modelsof oxidative stress and carbonyl stress

    PubMed Central

    Heidari, Himan; Kamalinejad, Mohammad; Noubarani, Maryam; Rahmati, Mokhtar; Jafarian, Iman; Adiban, Hasan; Eskandari, Mohammad Reza

    2016-01-01

    Introduction: Oxidative stress and carbonyl stress have essential mediatory roles in the development of diabetes and its related complications through increasing free radicals production and impairing antioxidant defense systems. Different chemical and natural compounds have been suggested for decreasing such disorders associated with diabetes. The objectives of the present study were to investigate the protective effects of Cucumis sativus (C. sativus) fruit (cucumber) in oxidative and carbonyl stress models. These diabetes-related models with overproduction of reactive oxygen species (ROS) and reactive carbonyl species (RCS) simulate conditions observed in chronic hyperglycemia. Methods: Cytotoxicity induced by cumene hydroperoxide (oxidative stress model) or glyoxal (carbonyl stress model) were measured and the protective effects of C. sativus were evaluated using freshly isolated rat hepatocytes. Results: Aqueous extract of C. sativus fruit (40 μg/mL) prevented all cytotoxicity markers in both the oxidative and carbonyl stress models including cell lysis, ROS formation, membrane lipid peroxidation, depletion of glutathione, mitochondrial membrane potential decline, lysosomal labialization, and proteolysis. The extract also protected hepatocytes from protein carbonylation induced by glyoxal. Our results indicated that C. sativus is able to prevent oxidative stress and carbonyl stress in the isolated hepatocytes. Conclusion: It can be concluded that C. sativus has protective effects in diabetes complications and can be considered a safe and suitable candidate for decreasing the oxidative stress and carbonyl stress that is typically observed in diabetes mellitus. PMID:27340622

  17. Garden-like perovskite superstructures with enhanced photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Ye, Meidan; Wang, Mengye; Zheng, Dajiang; Zhang, Nan; Lin, Changjian; Lin, Zhiqun

    2014-03-01

    By subjecting amorphous flower-like TiO2 to a facile hydrothermal synthesis in the presence of Sr2+, garden-like perovskite SrTiO3 superstructures were achieved. The amorphous TiO2 was preformed using ZnO flowers as templates. Different three-dimensional SrTiO3 architectures were coexisted in the garden, including SrTiO3 flowers composed of several hollow sword-shaped petals, many sheet-shaped petals or numerous flake-shaped petals, and SrTiO3 grass consisting of a number of long blades. These SrTiO3 superstructures were simultaneously grown on fluorine-doped tin oxide (FTO) substrates. On the basis of a comprehensive study on the effects of growth time, temperature, initial concentrations of precursor, and pH, the formation of these various hierarchical architectures was attributed primarily to the dissolution of amorphous TiO2 and precipitation of perovskite crystals, followed by the Ostwald ripening process of perovskite nanocrystals and self-organization of perovskite building blocks. Interestingly, this approach can be readily extended to create other perovskite structures, including dendritic BaTiO3 and nest-like CaTiO3, as well as PbTiO3 transformed from plate-like pyrochlore Pb2Ti2O6 after post-thermal treatment. Garden-like SrTiO3 superstructures showed a superior photocatalytic performance when compared to other as-prepared semiconductors and perovskite materials (i.e., ZnO, TiO2, BaTiO3, CaTiO3 and PbTiO3), probably due to their intrinsic photocatalytic activity and special garden-like features with a coexistence of various structures that significantly facilitated the adsorption and diffusion of methyl blue (MB) molecules and oxygen species in the photochemical reaction of MB degradation.By subjecting amorphous flower-like TiO2 to a facile hydrothermal synthesis in the presence of Sr2+, garden-like perovskite SrTiO3 superstructures were achieved. The amorphous TiO2 was preformed using ZnO flowers as templates. Different three-dimensional SrTiO3

  18. Open circuit potential build-up in perovskite solar cells from dark conditions to 1 sun.

    PubMed

    Gouda, Laxman; Gottesman, Ronen; Ginsburg, Adam; Keller, David A; Haltzi, Eynav; Hu, Jiangang; Tirosh, Shay; Anderson, Assaf Y; Zaban, Arie; Boix, Pablo P

    2015-11-19

    The high open-circuit potential (Voc) achieved by perovskite solar cells (PSCs) is one of the keys to their success. The Voc analysis is essential to understand their working mechanisms. A large number of CH3NH3PbI3-xClx PSCs were fabricated on single large-area substrates and their Voc dependencies on illumination intensity, I0, were measured showing three distinctive regions. Similar results obtained in Al2O3 based PSCs relate the effect to the compact TiO2 rather than the mesoporous oxide. We propose that two working mechanisms control the Voc in PSCs. The rise of Voc at low I0 is determined by the employed semiconductor n-type contact (TiO2 or MgO coated TiO2). In contrast, at I0 close to AM1.5G, the employed oxide does not affect the achieved voltage. Thus, a change of regime from an oxide-dominated EFn (as in the dye sensitized solar cells) to an EFn, directly determined by the CH3NH3PbI3-xClx absorber is suggested. PMID:26624787

  19. Enhancing Perovskite Electrocatalysis through Strain Tuning of the Oxygen Deficiency.

    PubMed

    Petrie, Jonathan R; Jeen, Hyoungjeen; Barron, Sara C; Meyer, Tricia L; Lee, Ho Nyung

    2016-06-15

    Oxygen vacancies in transition-metal oxides facilitate catalysis critical for energy storage and generation. However, promoting vacancies at the lower temperatures required for operation in devices such as metal-air batteries and portable fuel cells has proven elusive. Here we used thin films of perovskite-based strontium cobaltite (SrCoOx) to show that epitaxial strain is a powerful tool for manipulating the oxygen content under conditions consistent with the oxygen evolution reaction, yielding increasingly oxygen-deficient states in an environment where the cobaltite would normally be fully oxidized. The additional oxygen vacancies created through tensile strain enhance the cobaltite's catalytic activity toward this important reaction by over an order of magnitude, equaling that of precious-metal catalysts, including IrO2. Our findings demonstrate that strain in these oxides can dictate the oxygen stoichiometry independent of ambient conditions, allowing unprecedented control over oxygen vacancies essential in catalysis near room temperature. PMID:27232374

  20. A climate-related oxidizing event in deep-sea sediment from the Bering Sea

    USGS Publications Warehouse

    Gardner, J.V.; Dean, W.E.; Klise, D.H.; Baldauf, J.G.

    1982-01-01

    Many cores from the deep basins of the Bering Sea have a thin oxidized zone within otherwise reduced sediment. This oxidized zone began to form about 6000 yr ago and represents an interval of about 3200 yr. Mineralogically, the oxidized and reduced sediments are similar, but chemically they differ. Concentrations of Fe and C are lower, and concentrations of Mn, Ba, Co, Mo, and Ni are higher in the oxidized than in the reduced sediment. Mn is enriched about 10-fold in the oxidized zone relative to its concentration in the reduced sediment, Mo about threefold, and Ba, Co, and Ni about twofold. These data suggest that the oxidized zone developed diagenetically as the result of the balance between the flux of organic matter and the available dissolved oxygen in bottom and interstitial waters. We propose that the Bering Sea was substantially ice covered when global glacial conditions prevailed. during the transition to global interglacial conditions, seasonal meltwater from thawing sea ice formed a lens of fresh water that decreased organic productivity. During the winter seasons, however, sea ice reformed and caused downwelling of dense, oxygen-rich waters to recharge bottom waters. The combination of lower organic productivity and more oxygen-rich bottom water allowed oxidized sediment to accumulate. Once full interglacial conditions were established, the volume of sea ice produced was insufficient to affect either productivity or the supply of dissolved oxygen and so bottom conditions again became reducing. Similar events probably occurred during the onset of global glacial conditions, and similar oxidized layers probably formed at these times. Such oxidized zones are highly unstable, however, in a reducing environment and, once buried beyond the influence of bacterial and infaunal activities, are depleted of their available oxygen and converted to reduced sediment. ?? 1982.