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Sample records for a-site ordered perovskites

  1. 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).

  2. Antiferromagnetic interaction between A'-site Mn spins in A-site-ordered perovskite YMn3Al4O12.

    PubMed

    Tohyama, Takenori; Saito, Takashi; Mizumaki, Masaichiro; Agui, Akane; Shimakawa, Yuichi

    2010-03-01

    The A-site-ordered perovskite YMn(3)Al(4)O(12) was prepared by high-pressure synthesis. Structural analysis with synchrotron powder X-ray diffraction data and the Mn L-edges X-ray absorption spectrum revealed that the compound has a chemical composition Y(3+)Mn(3+)(3)Al(3+)(4)O(2-)(12) with magnetic Mn(3+) at the A' site and non-magnetic Al(3+) at the B site. An antiferromagnetic interaction between the A'-site Mn(3+) spins is induced by the nearest neighboring Mn-Mn direct exchange interaction and causes an antiferromagnetic transition at 34.3 K.

  3. Intermetallic charge transfer between A-site Cu and B-site Fe in A-site-ordered double perovskites

    NASA Astrophysics Data System (ADS)

    Long, Youwen; Shimakawa, Yuichi

    2010-06-01

    In this review article, we describe in detail the temperature-induced intermetallic charge transfer between A-site Cu and B-site Fe ions in the A-site-ordered double perovskites RCu3Fe4O12 (R=La, Bi). In these compounds, a very rare Cu3+ valence state at the square-planar-coordinated A sites was stabilized by high-pressure synthesis. By increasing the temperature, a Cu-Fe intermetallic charge transfer producing a high Fe3.75+ valence state occurred. This charge transfer gave rise to a first-order isostructural phase transition with unusual volume contraction, as well as to antiferromagnetism-to-paramagnetism and insulator-to-metal transitions. The substitution of Bi for La stabilized the low-temperature phase containing Cu3+ and increased the charge transfer transition temperature from 393 K for LaCu3Fe4O12 to 428 K for BiCu3Fe4O12.

  4. Competition between heavy fermion and Kondo interaction in isoelectronic A-site-ordered perovskites.

    PubMed

    Meyers, D; Middey, S; Cheng, J-G; Mukherjee, Swarnakamal; Gray, B A; Cao, Yanwei; Zhou, J-S; Goodenough, J B; Choi, Yongseong; Haskel, D; Freeland, J W; Saha-Dasgupta, T; Chakhalian, J

    2014-12-17

    With current research efforts shifting towards the 4d and 5d transition metal oxides, understanding the evolution of the electronic and magnetic structure as one moves away from 3d materials is of critical importance. Here we perform X-ray spectroscopy and electronic structure calculations on A-site-ordered perovskites with Cu in the A-site and the B-sites descending along the ninth group of the periodic table to elucidate the emerging properties as d-orbitals change from partially filled 3d to 4d to 5d. The results show that when descending from Co to Ir, the charge transfers from the cuprate-like Zhang-Rice state on Cu to the t(2g) orbital of the B site. As the Cu d-orbital occupation approaches the Cu(2+) limit, a mixed valence state in CaCu(3)Rh(4)O(12) and heavy fermion state in CaCu(3)Ir(4)O(12) are obtained. The investigated d-electron compounds are mapped onto the Doniach phase diagram of the competing RKKY and Kondo interactions developed for the f-electron systems.

  5. Competition between heavy fermion and Kondo interaction in isoelectronic A-site-ordered perovskites

    SciTech Connect

    Meyers, D.; Middey, S.; Cheng, J.-G.; Mukherjee, Swarnakamal; Gray, B. A.; Cao, Yanwei; Zhou, J.-S.; Goodenough, J. B.; Choi, Yongseong; Haskel, D.; Freeland, J. W.; Saha-Dasgupta, T.; Chakhalian, J.

    2014-12-17

    With current research efforts shifting towards the 4d and 5d transition metal oxides, understanding the evolution of the electronic and magnetic structure as one moves away from 3d materials is of critical importance. Here we perform X-ray spectroscopy and electronic structure calculations on A-site-ordered perovskites with Cu in the A-site and the B-sites descending along the ninth group of the periodic table to elucidate the emerging properties as d-orbitals change from partially filled 3d to 4d to 5d. The results show that when descending from Co to Ir, the charge transfers from the cuprate-like Zhang-Rice state on Cu to the t2g orbital of the B site. As the Cu d-orbital occupation approaches the Cu2þ limit, a mixed valence state in CaCu3Rh4O12 and heavy fermion state in CaCu3Ir4O12 are obtained. The investigated d-electron compounds are mapped onto the Doniach phase diagram of the competing RKKY and Kondo interactions developed for the f-electron systems.

  6. Zhang-Rice physics and anomalous copper states in A-site ordered perovskites.

    PubMed

    Meyers, D; Mukherjee, Swarnakamal; Cheng, J-G; Middey, S; Zhou, J-S; Goodenough, J B; Gray, B A; Freeland, J W; Saha-Dasgupta, T; Chakhalian, J

    2013-01-01

    In low dimensional cuprates several interesting phenomena, including high Tc superconductivity, are deeply connected to electron correlations on Cu and the presence of the Zhang-Rice (ZR) singlet state. Here, we report on direct spectroscopic observation of the ZR state responsible for the low-energy physical properties in two isostructural A-site ordered cuprate perovskites, CaCu(3)Co(4)O(12) and CaCu(3)Cr(4)O(12) as revealed by resonant soft x-ray absorption spectroscopy on the Cu L(3,2)- and O K-edges. These measurements reveal the signature of Cu in the high-energy 3+ (3d(8)), the typical 2+ (3d(9)), as well as features of the ZR singlet state (i.e., 3d(9)L, L denotes an oxygen hole). First principles GGA + U calculations affirm that the B-site cation controls the degree of Cu-O hybridization and, thus, the Cu valency. These findings introduce another avenue for the study and manipulation of cuprates, bypassing the complexities inherent to conventional chemical doping (i.e. disorder) that hinder the relevant physics.

  7. Zhang-Rice physics and anomalous copper states in A-site ordered perovskites

    PubMed Central

    Meyers, D.; Mukherjee, Swarnakamal; Cheng, J.-G.; Middey, S.; Zhou, J.-S.; Goodenough, J. B.; Gray, B. A.; Freeland, J. W.; Saha-Dasgupta, T.; Chakhalian, J.

    2013-01-01

    In low dimensional cuprates several interesting phenomena, including high Tc superconductivity, are deeply connected to electron correlations on Cu and the presence of the Zhang-Rice (ZR) singlet state. Here, we report on direct spectroscopic observation of the ZR state responsible for the low-energy physical properties in two isostructural A-site ordered cuprate perovskites, CaCu3Co4O12 and CaCu3Cr4O12 as revealed by resonant soft x-ray absorption spectroscopy on the Cu L3,2- and O K-edges. These measurements reveal the signature of Cu in the high-energy 3+ (3d8), the typical 2+ (3d9), as well as features of the ZR singlet state (i.e., 3d9L, L denotes an oxygen hole). First principles GGA + U calculations affirm that the B-site cation controls the degree of Cu-O hybridization and, thus, the Cu valency. These findings introduce another avenue for the study and manipulation of cuprates, bypassing the complexities inherent to conventional chemical doping (i.e. disorder) that hinder the relevant physics. PMID:23666066

  8. Zhang-Rice physics and anomalous copper states in A-site ordered perovskites

    NASA Astrophysics Data System (ADS)

    Meyers, D.; Mukherjee, Swarnakamal; Cheng, J.-G.; Middey, S.; Zhou, J.-S.; Goodenough, J. B.; Gray, B. A.; Freeland, J. W.; Saha-Dasgupta, T.; Chakhalian, J.

    2013-05-01

    In low dimensional cuprates several interesting phenomena, including high Tc superconductivity, are deeply connected to electron correlations on Cu and the presence of the Zhang-Rice (ZR) singlet state. Here, we report on direct spectroscopic observation of the ZR state responsible for the low-energy physical properties in two isostructural A-site ordered cuprate perovskites, CaCu3Co4O12 and CaCu3Cr4O12 as revealed by resonant soft x-ray absorption spectroscopy on the Cu L3,2- and O K-edges. These measurements reveal the signature of Cu in the high-energy 3+ (3d8), the typical 2+ (3d9), as well as features of the ZR singlet state (i.e., 3d9L, L denotes an oxygen hole). First principles GGA + U calculations affirm that the B-site cation controls the degree of Cu-O hybridization and, thus, the Cu valency. These findings introduce another avenue for the study and manipulation of cuprates, bypassing the complexities inherent to conventional chemical doping (i.e. disorder) that hinder the relevant physics.

  9. Characterization of Ordering in A-Site Deficient Perovskite Ca1-xLa2x/3TiO3 Using STEM/EELS.

    PubMed

    Danaie, Mohsen; Kepaptsoglou, Demie; Ramasse, Quentin M; Ophus, Colin; Whittle, Karl R; Lawson, Sebastian M; Pedrazzini, Stella; Young, Neil P; Bagot, Paul A J; Edmondson, Philip D

    2016-10-03

    The vacancy ordering behavior of an A-site deficient perovskite system, Ca1-xLa2x/3TiO3, was studied using atomic resolution scanning transmission electron microscopy (STEM) in conjunction with electron energy-loss spectroscopy (EELS), with the aim of determining the role of A-site composition changes. At low La content (x = 0.2), adopting Pbnm symmetry, there was no indication of long-range ordering. Domains, with clear boundaries, were observed in bright-field (BF) imaging, but were not immediately visible in the corresponding high-angle annular dark-field (HAADF) image. These boundaries, with the aid of displacement maps from A-site cations in the HAADF signal, are shown to be tilt boundaries. At the La-rich end of the composition (x = 0.9), adopting Cmmm symmetry, long-range ordering of vacancies and La(3+) ions was observed, with alternating La-rich and La-poor layers on (001)p planes, creating a double perovskite lattice along the c axis. These highly ordered domains can be found isolated within a random distribution of vacancies/La(3+), or within a large population, encompassing a large volume. In regions with a high number density of double perovskite domains, these highly ordered domains were separated by twin boundaries, with 90° or 180° lattice rotations across boundaries. The occurrence and characteristics of these ordered structures are discussed and compared with similar perovskite systems.

  10. Possible Kondo physics near a metal-insulator crossover in the a-site ordered perovskite CaCu3Ir4O12.

    PubMed

    Cheng, J-G; Zhou, J-S; Yang, Y-F; Zhou, H D; Matsubayashi, K; Uwatoko, Y; MacDonald, A; Goodenough, J B

    2013-10-25

    The A-site ordered perovskite (AA(3)')B(4)O(12) can accommodate transition metals on both A' and B sites in the crystal structure. Because of this structural feature, it is possible to have narrow-band electrons interacting with broadband electrons from different sublattices. Here we report a new A-site ordered perovskite (CaCu(3))Ir(4)O(12) synthesized under high pressure. The coupling between localized spins on Cu(2+) and itinerant electrons from the Ir-O sublattice makes Kondo-like physics take place at a temperature as high as 80 K. Results from the local density approximation calculation have confirmed the relevant band structure. The magnetization anomaly found at 80 K can be well rationalized by the two-fluid model.

  11. Characterization of ordering in A-site deficient perovskite Ca1–xLa 2x/3TiO3 using STEM/EELS

    DOE PAGES

    Danaie, Mohsen; Kepaptsoglou, Demie; Ramasse, Quentin M.; ...

    2016-09-15

    The vacancy ordering behavior of an A-site deficient perovskite system, Ca1–xLa2x/3TiO3, was studied using atomic resolution scanning transmission electron microscopy (STEM) in conjunction with electron energy-loss spectroscopy (EELS), with the aim of determining the role of A-site composition changes. At low La content (x = 0.2), adopting Pbnm symmetry, there was no indication of long-range ordering. Domains, with clear boundaries, were observed in bright-field (BF) imaging, but were not immediately visible in the corresponding high-angle annular dark-field (HAADF) image. These boundaries, with the aid of displacement maps from A-site cations in the HAADF signal, are shown to be tilt boundaries.more » At the La-rich end of the composition (x = 0.9), adopting Cmmm symmetry, long-range ordering of vacancies and La3+ ions was observed, with alternating La-rich and La-poor layers on (001)p planes, creating a double perovskite lattice along the c axis. These highly ordered domains can be found isolated within a random distribution of vacancies/La3+, or within a large population, encompassing a large volume. In regions with a high number density of double perovskite domains, these highly ordered domains were separated by twin boundaries, with 90° or 180° lattice rotations across boundaries. In conclusion, the occurrence and characteristics of these ordered structures are discussed and compared with similar perovskite systems.« less

  12. Temperature-induced A-B intersite charge transfer in an A-site-ordered LaCu(3)Fe(4)O(12) perovskite.

    PubMed

    Long, Y W; Hayashi, N; Saito, T; Azuma, M; Muranaka, S; Shimakawa, Y

    2009-03-05

    Changes of valence states in transition-metal oxides often cause significant changes in their structural and physical properties. Chemical doping is the conventional way of modulating these valence states. In ABO(3) perovskite and/or perovskite-like oxides, chemical doping at the A site can introduce holes or electrons at the B site, giving rise to exotic physical properties like high-transition-temperature superconductivity and colossal magnetoresistance. When valence-variable transition metals at two different atomic sites are involved simultaneously, we expect to be able to induce charge transfer-and, hence, valence changes-by using a small external stimulus rather than by introducing a doping element. Materials showing this type of charge transfer are very rare, however, and such externally induced valence changes have been observed only under extreme conditions like high pressure. Here we report unusual temperature-induced valence changes at the A and B sites in the A-site-ordered double perovskite LaCu(3)Fe(4)O(12); the underlying intersite charge transfer is accompanied by considerable changes in the material's structural, magnetic and transport properties. When cooled, the compound shows a first-order, reversible transition at 393 K from LaCu(2+)(3)Fe(3.75+)(4)O(12) with Fe(3.75+) ions at the B site to LaCu(3+)(3)Fe(3+)(4)O(12) with rare Cu(3+) ions at the A site. Intersite charge transfer between the A-site Cu and B-site Fe ions leads to paramagnetism-to-antiferromagnetism and metal-to-insulator isostructural phase transitions. What is more interesting in relation to technological applications is that this above-room-temperature transition is associated with a large negative thermal expansion.

  13. Effect of A-Site Cation Ordering on Chemical Stability, Oxygen Stoichiometry and Electrical Conductivity in Layered LaBaCo2O5+δ Double Perovskite

    PubMed Central

    Bernuy-Lopez, Carlos; Høydalsvik, Kristin; Einarsrud, Mari-Ann; Grande, Tor

    2016-01-01

    The effect of the A-site cation ordering on the chemical stability, oxygen stoichiometry and electrical conductivity in layered LaBaCo2O5+δ double perovskite was studied as a function of temperature and partial pressure of oxygen. Tetragonal A-site cation ordered layered LaBaCo2O5+δ double perovskite was obtained by annealing cubic A-site cation disordered La0.5Ba0.5CoO3-δ perovskite at 1100 °C in N2. High temperature X-ray diffraction between room temperature (RT) and 800 °C revealed that LaBaCo2O5+δ remains tetragonal during heating in oxidizing atmosphere, but goes through two phase transitions in N2 and between 450 °C and 675 °C from tetragonal P4/mmm to orthorhombic Pmmm and back to P4/mmm due to oxygen vacancy ordering followed by disordering of the oxygen vacancies. An anisotropic chemical and thermal expansion of LaBaCo2O5+δ was demonstrated. La0.5Ba0.5CoO3-δ remained cubic at the studied temperature irrespective of partial pressure of oxygen. LaBaCo2O5+δ is metastable with respect to La0.5Ba0.5CoO3-δ at oxidizing conditions inferred from the thermal evolution of the oxygen deficiency and oxidation state of Co in the two materials. The oxidation state of Co is higher in La0.5Ba0.5CoO3-δ resulting in a higher electrical conductivity relative to LaBaCo2O5+δ. The conductivity in both materials was reduced with decreasing partial pressure of oxygen pointing to a p-type semiconducting behavior. PMID:28773279

  14. Control of L-type ferrimagnetism by the Ce/vacancy ordering in the A-site-ordered perovskite Ce(1/2)Cu3Ti4O12.

    PubMed

    Saito, Takashi; Yamada, Ryuta; Ritter, Clemens; Senn, Mark S; Attfield, J Paul; Shimakawa, Yuichi

    2014-02-03

    A-site-ordered perovskite Ce1/2Cu3Ti4O12 has been found to crystallize in two different forms, one with random and the other with ordered Ce/vacancy distribution at the A site of the prototype AA'3B4O12 structure. The random phase is isostructural with CaCu3Ti4O12, and the ordered phase is a new ordered derivative of the AA'3B4O12-type perovskite with two crystallographically distinct Cu sites. Although both phases form a G-type antiferromagnetic arrangement of Cu(2+) spins below 24 K, their magnetisms are quite different. A typical antiferromagnetic transition is observed in the random phase, whereas a small ferromagnetic moment appears below 24 K in the ordered phase, which rapidly decreases upon further cooling. A mean-field approximation approach revealed that this unusual behavior in the ordered phase is an L-type ferrimagnetism driven by the nonequivalent magnetizations of the two ferromagnetic Cu(2+) spin sublattices in the G-type spin structure. This unusual ferrimagnetism is a direct consequence of the Ce/vacancy ordering.

  15. Magneto-orbital ordering in the divalent A -site quadruple perovskite manganites A Mn7O12 (A =Sr , Cd, and Pb)

    NASA Astrophysics Data System (ADS)

    Johnson, R. D.; Khalyavin, D. D.; Manuel, P.; Radaelli, P. G.; Glazkova, I. S.; Terada, N.; Belik, A. A.

    2017-08-01

    Through analysis of variable-temperature neutron powder-diffraction data, we present solutions for the magnetic structures of SrMn7O12 , CdMn7O12 , and PbMn7O12 in all long-range ordered phases. The three compounds were found to have magnetic structures analogous to that reported for CaMn7O12 . They all feature a higher-temperature lock-in phase with commensurate magneto-orbital coupling and a delocked multi-k magnetic ground state where incommensurate magneto-orbital coupling gives rise to a constant-moment magnetic helix with modulated spin helicity. CdMn7O12 represents a special case in which the orbital modulation is commensurate with the crystal lattice and involves stacking of fully and partially polarized orbital states. Our results provide a robust confirmation of the phenomenological model for magneto-orbital coupling previously presented for CaMn7O12 . Furthermore, we show that the model is universal to the A2 + quadruple perovskite manganites synthesized to date and that it is tunable by selection of the A -site ionic radius.

  16. Topotactic reductive synthesis of A-site cation-ordered perovskite YBaCo2O x (x = 4.5-5.5) epitaxial thin films

    NASA Astrophysics Data System (ADS)

    Katayama, Tsukasa; Chikamatsu, Akira; Fukumura, Tomoteru; Hasegawa, Tetsuya

    2016-04-01

    A-site cation-ordered perovskite YBaCo2O x epitaxial films were synthesized by combining pulsed-laser deposition and topotactic reduction using CaH2. The oxygen contents (x) of the films could be controlled in a range of 4.5-5.5 by adjusting the reaction temperature. The c-axis length of the YBaCo2O x films decreased with decreasing x when x ≥ 5.3 but drastically increased when x ˜ 4.5. In contrast, the in-plane lattice constants remained locked-in by the substrate after the reaction. The metal insulator transition observed in bulk YBaCo2O5.5 was substantially suppressed in the present film, likely because of the epitaxial strain effect. The resistivity of the films was significantly enhanced by changing the x value from ˜5.5 to ˜4.5, reflecting the distortion of the CoO x layers.

  17. Polar and magnetic layered A-site and rock salt B-site-ordered NaLnFeWO6 (Ln = La, Nd) perovskites.

    PubMed

    Retuerto, M; Li, M R; Ignatov, A; Croft, M; Ramanujachary, K V; Chi, S; Hodges, J P; Dachraoui, W; Hadermann, J; Tran, T Thao; Halasyamani, P Shiv; Grams, C P; Hemberger, J; Greenblatt, M

    2013-11-04

    We have expanded the double perovskite family of materials with the unusual combination of layered order in the A sublattice and rock salt order over the B sublattice to compounds NaLaFeWO6 and NaNdFeWO6. The materials have been synthesized and studied by powder X-ray diffraction, neutron diffraction, electron diffraction, magnetic measurements, X-ray absorption spectroscopy, dielectric measurements, and second harmonic generation. At room temperature, the crystal structures of both compounds can be defined in the noncentrosymmetric monoclinic P2(1) space group resulting from the combination of ordering both in the A and B sublattices, the distortion of the cell due to tilting of the octahedra, and the displacement of certain cations. The magnetic studies show that both compounds are ordered antiferromagnetically below T(N) ≈ 25 K for NaLaFeWO6 and at ∼21 K for NaNdFeWO6. The magnetic structure of NaNdFeWO6 has been solved with a propagation vector k = ((1/2) 0 (1/2)) as an antiferromagnetic arrangement of Fe and Nd moments. Although the samples are potential multiferroics, the dielectric measurements do not show a ferroelectric response.

  18. A-site ordering and its effect on tilting transition in perovskite La0.75Sr0.25FeO3-δ investigated by mechanical spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, C. C.; Ying, X. N.

    2017-05-01

    La0.75Sr0.25FeO3-δ polycrystalline samples were prepared by the solid state reaction at different sintering temperatures. An octahedral tilting Pnma ↔ R 3 ¯ c transition in La0.75Sr0.25FeO3-δ was detected by mechanical spectroscopy, where a dip of reduced modulus was observed and accompanied by a sharp internal friction peak. The modulus softening is due to the strain/order parameters coupling at this improper ferroelastic transition. The tilting transition shifts toward lower temperature with reducing sintering temperature in La0.75Sr0.25FeO3-δ samples, which is due to the detriment of A-site ordering in the ABO3 perovskite. A higher degree of A-site ordering favors more homogenous structural modulation, which stabilizes the low temperature Pnma phase and results in the shift of the transition to higher temperature. Another internal friction peak just below the tilting transition was observed, which is attributed to domain wall motions. A correlation between the mobility of ferroelastic domain walls in Pnma perovskite and the existence of the high temperature R 3 ¯ c phase was suggested.

  19. Synthesis of a polar ordered oxynitride perovskite

    NASA Astrophysics Data System (ADS)

    Vadapoo, Rajasekarakumar; Ahart, Muhtar; Somayazulu, Maddury; Holtgrewe, Nicholas; Meng, Yue; Konopkova, Zuzana; Hemley, Russell J.; Cohen, R. E.

    2017-06-01

    For decades, numerous attempts have been made to produce polar oxynitride perovskites, where some of the oxygen is replaced by nitrogen, but a polar ordered oxynitride has never been demonstrated. Caracas and Cohen [Appl. Phys. Lett. 91, 092902 (2007), 10.1063/1.2776370] studied possible ordered polar oxynitrides within density-functional theory (DFT) and found a few candidates that were predicted to be insulating and at least metastable. YSi O2N stood out with huge predicted polarization and nonlinear optic coefficients. In this study, we demonstrate the synthesis of perovskite-structured YSi O2N by using a combination of a diamond-anvil cell and in situ laser-heating techniques. Subsequent in situ x-ray diffraction, second-harmonic generation, and Raman-scattering measurements confirm that it is polar and a strong nonlinear optical material, with structure and properties similar to those predicted by DFT.

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

    PubMed

    Belik, Alexei A; Yi, Wei

    2014-04-23

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

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

    PubMed

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

    2016-03-01

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

  2. Topochemical synthesis of cation ordered double perovskite oxynitrides.

    PubMed

    Ceravola, Roberta; Oró-Solé, Judith; Black, Ashley P; Ritter, Clemens; Puente Orench, Inés; Mata, Ignasi; Molins, Elies; Frontera, Carlos; Fuertes, Amparo

    2017-03-27

    Topochemical nitridation in ammonia at moderate temperatures of cation ordered Sr2FeWO6 produces new antiferromagnetic double perovskite oxynitrides Sr2FeWO6-xNx with 0 < x ≤ 1. Nitrogen introduction induces the oxidation of Fe(2+) to Fe(3+) and decreases TN from 38 K (x = 0) to 13 K for Sr2FeWO5N which represents the first example of a double perovskite oxynitride with both high cationic order and nitrogen content. This synthetic approach can be extended to other cation combinations expanding the possibility of new materials in the large group of double perovskites.

  3. A-site layer terminated perovskite substrate: NdGaO3

    NASA Astrophysics Data System (ADS)

    Ohnishi, Tsuyoshi; Takahashi, Kazuhiro; Nakamura, Masashi; Kawasaki, Masashi; Yoshimoto, Mamoru; Koinuma, Hideomi

    1999-04-01

    A perovskite single-crystal substrate, NdGaO3 (001), was thermally annealed in air to give an atomically defined surface structure. From analysis with coaxial impact-collision ion scattering spectroscopy, the terminating atomic layer was identified to be NdO1+δ , i.e., the A-site oxide monolayer in perovskite ABO3. This result is contrary to the B-site oxide (BO2-δ) termination observed in other perovskite surfaces, such as wet etched SrTiO3 and LaAlO3 or annealed (LaAlO3)0.3-(Sr2AlTaO6)0.7 (LSAT).

  4. Interplay of Cation Ordering and Ferroelectricity in Perovskite Tin Iodides: Designing a Polar Halide Perovskite for Photovoltaic Applications.

    PubMed

    Gou, Gaoyang; Young, Joshua; Liu, Xian; Rondinelli, James M

    2017-01-03

    Owing to its ideal semiconducting band gap and good carrier-transport properties, the fully inorganic perovskite CsSnI3 has been proposed as a visible-light absorber for photovoltaic (PV) applications. However, compared to the organic-inorganic lead halide perovskite CH3NH3PbI3, CsSnI3 solar cells display very low energy conversion efficiency. In this work, we propose a potential route to improve the PV properties of CsSnI3. Using first-principles calculations, we examine the crystal structures and electronic properties of CsSnI3, including its structural polymorphs. Next, we purposefully order Cs and Rb cations on the A site to create the double perovskite (CsRb)Sn2I6. We find that a stable ferroelectric polarization arises from the nontrivial coupling between polar displacements and octahedral rotations of the SnI6 network. These ferroelectric double perovskites are predicted to have energy band gaps and carrier effective masses similar to those of CsSnI3. More importantly, unlike nonpolar CsSnI3, the electric polarization present in ferroelectric (CsRb)Sn2I6 can effectively separate the photoexcited carriers, leading to novel ferroelectric PV materials with potentially enhanced energy conversion efficiency.

  5. Interplay of Cation Ordering and Ferroelectricity in Perovskite Tin Iodides: Designing a Polar Halide Perovskite for Photovoltaic Applications

    SciTech Connect

    Gou, Gaoyang; Young, Joshua; Liu, Xian; Rondinelli, James M.

    2016-09-28

    Owing to its ideal semiconducting band gap and good carrier transport properties, the fully inorganic perovskite CsSnI3 has been proposed as a visible-light absorber for photovoltaic (PV) applications. However, compared to the organic inorganic lead halide perovskite CH3NH3PbI3, CsSnI3 solar cells display very low energy conversion efficiency. In this work, we propose a potential route to improve the PV properties of CsSnI3. Using first-principles calculations, we examine the crystal structures and electronic properties of CsSnI3, including its structural polymorphs. Next, we purposefully order Cs and Rb cations on the A site to create the double perovskite (CsRb)Sn2I6. We find that a stable ferroelectric polarization arises from the nontrivial coupling between polar displacements and octahedral rotations of the SnI6 network. These ferroelectric double perovskites are predicted to have energy band gaps and carrier effective masses similar to those of CsSnI3. More importantly, unlike nonpolar CsSnI3, the electric polarization present in ferroelectric (CsRb)Sn2I6 can effectively separate the photoexcited carriers, leading to novel ferroelectric PV materials with,potentially enhanced energy conversion efficiency.

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

    PubMed

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

    2016-08-01

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

  7. Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl6

    SciTech Connect

    Pilania, G.; Uberuaga, B. P.

    2015-03-19

    Here, we investigate the electronic structure, energetics of cation ordering, and effect of biaxial strain on double perovskite CsRbCaZnCl6 using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl3 and RbZnCl3) forming the double perovskite exhibit a stark contrast. While CsCaCl3 is known to exist in a cubic perovskite structure and does not show any epitaxial strain induced phase transitions within an experimentally accessible range of compressive strains, RbZnCl3 is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We show that combining the two compositions in a double perovskite structure not only improves overall stability but also the strain-polarization coupling of the material. Our calculations predict a ground state with P4/nmm space group for the double perovskite, where A-site cations (i.e., Cs and Rb) are layer-ordered and B-site cations (i.e., Ca and Zn) prefer a rocksalt type ordering. The electronic structure and bandgap in this system are shown to be quite sensitive to the B-site cation ordering and is minimally affected by the ordering of A-site cations. We find that at experimentally accessible compressive strains CsRbCaZnCl6 can be phase transformed from its paraelectric ground state to an antiferroelectric state, where Zn atoms contribute predominantly to the polarization. Furthermore, both energy difference and activation barrier for a transformation between this antiferroelectric state and the corresponding ferroelectric configuration are predicted to be small. As a result, the computational approach presented here opens a new pathway towards a rational design of novel double perovskites with improved strain response and functionalities.

  8. Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl{sub 6}

    SciTech Connect

    Pilania, G. Uberuaga, B. P.

    2015-03-21

    Here, we investigate the electronic structure, energetics of cation ordering, and effect of biaxial strain on double perovskite CsRbCaZnCl{sub 6} using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl{sub 3} and RbZnCl{sub 3}) forming the double perovskite exhibit a stark contrast. While CsCaCl{sub 3} is known to exist in a cubic perovskite structure and does not show any epitaxial strain induced phase transitions within an experimentally accessible range of compressive strains, RbZnCl{sub 3} is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We show that combining the two compositions in a double perovskite structure not only improves overall stability but also the strain-polarization coupling of the material. Our calculations predict a ground state with P4/nmm space group for the double perovskite, where A-site cations (i.e., Cs and Rb) are layer-ordered and B-site cations (i.e., Ca and Zn) prefer a rocksalt type ordering. The electronic structure and bandgap in this system are shown to be quite sensitive to the B-site cation ordering and is minimally affected by the ordering of A-site cations. We find that at experimentally accessible compressive strains CsRbCaZnCl{sub 6} can be phase transformed from its paraelectric ground state to an antiferroelectric state, where Zn atoms contribute predominantly to the polarization. Furthermore, both energy difference and activation barrier for a transformation between this antiferroelectric state and the corresponding ferroelectric configuration are predicted to be small. The computational approach presented here opens a new pathway towards a rational design of novel double perovskites with improved strain response and functionalities.

  9. Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl6

    DOE PAGES

    Pilania, G.; Uberuaga, B. P.

    2015-03-19

    Here, we investigate the electronic structure, energetics of cation ordering, and effect of biaxial strain on double perovskite CsRbCaZnCl6 using first-principles calculations based on density functional theory. The two constituents (i.e., CsCaCl3 and RbZnCl3) forming the double perovskite exhibit a stark contrast. While CsCaCl3 is known to exist in a cubic perovskite structure and does not show any epitaxial strain induced phase transitions within an experimentally accessible range of compressive strains, RbZnCl3 is thermodynamically unstable in the perovskite phase and exhibits ultra-sensitive response at small epitaxial strains if constrained in the perovskite phase. We show that combining the two compositionsmore » in a double perovskite structure not only improves overall stability but also the strain-polarization coupling of the material. Our calculations predict a ground state with P4/nmm space group for the double perovskite, where A-site cations (i.e., Cs and Rb) are layer-ordered and B-site cations (i.e., Ca and Zn) prefer a rocksalt type ordering. The electronic structure and bandgap in this system are shown to be quite sensitive to the B-site cation ordering and is minimally affected by the ordering of A-site cations. We find that at experimentally accessible compressive strains CsRbCaZnCl6 can be phase transformed from its paraelectric ground state to an antiferroelectric state, where Zn atoms contribute predominantly to the polarization. Furthermore, both energy difference and activation barrier for a transformation between this antiferroelectric state and the corresponding ferroelectric configuration are predicted to be small. As a result, the computational approach presented here opens a new pathway towards a rational design of novel double perovskites with improved strain response and functionalities.« less

  10. Frustration relieved ferrimagnetism in novel A- and B-site-ordered quadruple perovskite.

    PubMed

    Chen, Wei-tin; Mizumaki, Masaichiro; Saito, Takashi; Shimakawa, Yuichi

    2013-07-28

    A novel A- and B-site-ordered quadruple perovskite CaCu3Fe2Sb2O12 was obtained and it shows ferrimagnetism below about 170 K. The B-site Fe spin sublattice adapts a tetrahedral framework in a cubic structure and the Fe(3+)-Fe(3+) antiferromagnetic interaction can result in a geometrical spin frustration as seen in a simple perovskite Ca2FeSbO6. With the introduction of Cu(2+) into the A' site, the antiferromagnetic spin frustration is relieved by the strong Cu(2+)-Fe(3+) interaction, and a ferrimagnetic ordering appears at a much higher temperature than the spin-glass transition temperature.

  11. Local A-Site Layering in Rare-Earth Orthochromite Perovskites by Solution Synthesis.

    PubMed

    Daniels, Luke M; Kashtiban, Reza J; Kepaptsoglou, Demie; Ramasse, Quentin M; Sloan, Jeremy; Walton, Richard I

    2016-12-19

    Cation size effects were examined in the mixed A-site perovskites La0.5 Sm0.5 CrO3 and La0.5 Tb0.5 CrO3 prepared through both hydrothermal and solid-state methods. Atomically resolved electron energy loss spectroscopy (EELS) in the transmission electron microscope shows that while the La and Sm cations are randomly distributed, increased cation-radius variance in La0.5 Tb0.5 CrO3 results in regions of localised La and Tb layers, an atomic arrangement exclusive to the hydrothermally prepared material. Solid-state preparation gives lower homogeneity resulting in separate nanoscale regions rich in La(3+) and Tb(3+) . The A-site layering in hydrothermal La0.5 Tb0.5 CrO3 is randomised upon annealing at high temperature, resulting in magnetic behaviour that is dependent on synthesis route. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  12. Cationic order versus La-O covalency in La A (Ca,Ba)VMoO6 double perovskites

    NASA Astrophysics Data System (ADS)

    Bandyopadhyay, Abhisek; Neogi, Swarup Kumar; Paul, Atanu; Meneghini, Carlo; Dasgupta, Indra; Bandyopadhyay, Sudipta; Ray, Sugata

    2017-01-01

    We have investigated the structural and physical properties of double perovskite (DP) La A VMoO6 (A =Ca2 + , Ba2 +; abbreviated as LCVMO and LBVMO from now on) compounds, proposed to be possible half-metallic antiferromagnets (HMAFMs). Here we show that within La A VMoO6 double perovskite structure, La-O covalency competes against B -site as well A -site cationic order and this competition critically influences their physical properties. Evidently, the presence of Ca2 + or Ba2 + at the A site along with La3 + would offer a tool to modify the A -site ordering and consequently influence the La-O covalency as well. Our experimental results reveal that LCVMO lies at the extreme end of this family and accommodates large scale phase separation in terms of La, V, and Ca, Mo-rich phases as a result of dominant La-O covalency. On the other hand, LBVMO is more correctly described as a layered A -site ordered and nearly complete B -site disordered double perovskite where cationic order dominates the La-O covalency. The general trend of our experimental findings is in agreement with the ab initio electronic structure calculations, carried out on realistic structures based on local coordination obtained from extended x-ray-absorption fine-structure study.

  13. Structural refinement of Pbnm-type perovskite films from analysis of half-order diffraction peaks

    NASA Astrophysics Data System (ADS)

    Brahlek, M.; Choquette, A. K.; Smith, C. R.; Engel-Herbert, R.; May, S. J.

    2017-01-01

    Engineering structural modifications of epitaxial perovskite thin films is an effective route to induce new functionalities or enhance existing properties due to the close relation of the electronic ground state to the local bonding environment. As such, there is a necessity to systematically refine and precisely quantify these structural displacements, particularly those of the oxygen octahedra, which is a challenge due to the weak scattering factor of oxygen and the small diffraction volume of thin films. Here, we present an optimized algorithm to refine the octahedral rotation angles using specific unit-cell-doubling half-order diffraction peaks for the a-a-c+ Pbnm structure. The oxygen and A-site positions can be obtained by minimizing the squared-error between calculated and experimentally determined peak intensities using the (1/2 1/2 3/2) and (1/2 1/2 5/2) reflections to determine the rotation angle α about in-plane axes and the (1/2 5/2 1), (1/2 3/2 1), and (1/2 3/2 2) reflections to determine the rotation angle γ about the out-of-plane axis, whereas the convoluting A-site displacements associated with the octahedral rotation pattern can be determined using (1 1 1/2) and (1/2 1/2 1/2) reflections to independently determine A-site positions. The validity of the approach is confirmed by applying the refinement procedure to determine the A-site and oxygen displacements in a NdGaO3 single crystal. The ability to refine both the oxygen and A-site displacements relative to the undistorted perovskite structure enables a deeper understanding of how structural modifications alter functionality properties in epitaxial films exhibiting this commonly occurring crystal structure.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  15. Sc2NiMnO6: A Double-Perovskite with a Magnetodielectric Response Driven by Multiple Magnetic Orders.

    PubMed

    Yi, Wei; Princep, Andrew J; Guo, Yanfeng; Johnson, Roger D; Khalyavin, Dmitry; Manuel, Pascal; Senyshyn, Anatoliy; Presniakov, Igor A; Sobolev, Alexey V; Matsushita, Yoshitaka; Tanaka, Masahiko; Belik, Alexei A; Boothroyd, Andrew T

    2015-08-17

    Perovskite materials provide a large variety of interesting physical properties and applications. Here, we report on unique properties of a fully ordered magnetodielectric double-perovskite, Sc2NiMnO6 (space group P21/n, a = 4.99860 Å, b = 5.35281 Å, c = 7.34496 Å, and β = 90.7915°), exhibiting sequential magnetic transitions at T1 = 35 K and T2 = 17 K. The transition at T1 corresponds to a single-k antiferromagnetic phase with propagation vector k1 = (1/2, 0, 1/2), while the second transition at T2 corresponds to a 2-k magnetic structure with propagation vectors k1 = (1/2, 0, 1/2) and k2 = (0, 1/2, 1/2). Symmetry analysis suggests that the two ordering wave vectors are independent, and calculations imply that k1 is associated with the Mn sublattice and k2 with the Ni sublattice, suggesting that Mn-Ni coupling is very small or absent. A magnetodielectric anomaly at T2 likely arises from an antiferroelectric ordering that results from the exchange-striction between the two magnetic sublattices belonging to k1 and k2. The behavior of Sc2NiMnO6 demonstrates 3d double-perovskites with small A-site cations as a promising avenue in which to search for magnetoelectric materials.

  16. Perovskite solar cells: High voltage from ordered fullerenes

    NASA Astrophysics Data System (ADS)

    Yan, Yanfa

    2016-01-01

    The open-circuit voltage is one of the parameters determining the efficiency of solar cells in converting solar radiation to electricity. Reducing the structural disorder in fullerene electron-transport layers is now shown to significantly improve the open-circuit voltage of perovskite solar cells.

  17. Thermally induced A'-A site exchange in novel layered perovskites Ag2[Ca1.5M3O10] (M = Nb, Ta).

    PubMed

    Bhuvanesh, Nattamai S P; Woodward, Patrick M

    2002-12-04

    We have synthesized and characterized new layered perovskites Ag2[A1.5M3O10] (A = Ca, M = Nb, Ta), from their lithium analogues, by soft-chemical ion exchange. These oxides show topotactic irreversible thermally induced A'-A site exchange, resulting in Ag1.1Ca0.9[Ca0.6Ag0.9M3O10], conferred from our high-temperature X-ray and ionic conductivity studies. The latter phases are the first compounds where Ag+ ions reside in both A' and A sites in layered perovskites. The absence of similar phase transition for A = Sr suggests that these transitions strongly depend on the size, charge, and the coordination preference of A' and A cations. This result provides a new synthetic tool for modifying the occupation of the 12-coordinate A site of layered perovskites using soft chemical routes.

  18. Zener Polarons Ordering Variants Induced by A-Site Ordering in Half-Doped Manganites

    NASA Astrophysics Data System (ADS)

    Daoud-Aladine, Aziz

    2006-03-01

    Zener Polaron (ZP) ordering [1] provides a still polemic [2] and elusive interpretation of the charge ordering (CO) phenomenon in A site disordered half doped (A1/2Ca1/2) MnO3, which is classically pictured by the Goodenough model (GM) of Mn^3+ and Mn^4+ CO [3,4]. ZP ordering considers instead the ordering of pre-formed ferromagnetic Mn pairs sharing an charge and keeping Mn in a Mn^+3.5 valence state. The recently synthesized A site cation ordered ABaMn2O6 were shown to not present the generic magnetic CE state found of (A1/2Ca1/2)MnO3 [5]. We present our magnetic structure determination of YBaMn2O6: the non- collinear magnetic order obtained unexpectedly reveals ferromagnetic plaquettes of four Mn attributable to larger 4-Mn ZPs, whose presence additionally fits very well the effective paramagnetic moments inferred from susceptibility measurements. The results unambiguously reveal the possible existence of ZP ordering variant in charge ordered manganites. [1] A. Daoud-Aladine et al., Phys. Rev. Lett. 89, 097205 (2002) [2] S. Grenier et al., Phys. Rev. B 69, 134419 (2004) [3] J. B. Goodenough, Phys. Rev. 100, 564 (1955) [4] P.G. Radaelli et al., Phys. Rev. B, 55, 3015 (1997) [5] T. Arima et al., Phys. Rev. B 66, 140408 (2002)

  19. 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.

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

    DOE PAGES

    Uberuaga, Blas Pedro; Pilania, Ghanshyam

    2015-07-08

    Perovskite structured oxides (ABO3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA’BB’O6) provide even more flexibility for tailoring properties. Using accelerated molecular dynamics, we examine the role of cation ordering on oxygen vacancy mobility in one model double perovskite SrLaTiAlO6. We find that the mobility of the vacancy is very sensitive to the cation ordering, with a migration energy that varies from 0.6 to 2.7 eV. In the extreme cases, the mobility is both higher and lower than either of the two end member single perovskites.more » Further, the nature of oxygen vacancy diffusion, whether one-dimensional, two-dimensional, or three-dimensional, also varies with cation ordering. We correlate the dependence of oxygen mobility on cation structure to the distribution of Ti4+ cations, which provide unfavorable environments for the positively charged oxygen vacancy. The results demonstrate the potential of using tailored double perovskite structures to precisely control the behavior of oxygen vacancies in these materials.« less

  1. Orbital hybridization and magnetic coupling of the A-site Cu spins in CaCu3B4O12 (B = Ti, Ge, and Sn) perovskites.

    PubMed

    Mizumaki, M; Saito, T; Shiraki, H; Shimakawa, Y

    2009-04-20

    X-ray absorption spectroscopy (XAS) spectra near the O K-edge of A-site-ordered perovskite with A-site Cu(2+) (S = (1)/(2)) spins were measured. The spectra of ferromagnetic CaCu(3)Ge(4)O(12) and CaCu(3)Sn(4)O(12) showed hybridization between Cu 3d and O 2p orbitals, but magnetic circular dichroism measurement revealed that the O 2p orbital played a less important role in magnetic interaction. The XAS spectra of antiferromagnetic CaCu(3)Ti(4)O(12), on the other hand, showed strong hybridization of the Cu 3d, Ti 3d, and O 2p orbitals. These results demonstrated that direct exchange interaction of the Cu(2+) spins primarily determined the ferromagnetic ordering of CaCu(3)Ge(4)O(12) and CaCu(3)Sn(4)O(12), whereas the involvement of Ti 3d orbitals induced the antiferromagnetic property in CaCu(3)Ti(4)O(12).

  2. A-site substitution effect of perovskite-type cobalt and manganese oxides on two-step water splitting reaction for solar hydrogen production

    NASA Astrophysics Data System (ADS)

    Kaneko, Hiroshi; Hasegawa, Takumi; Mori, Kohei

    2017-06-01

    The perovskite type metal oxides (ABO3: A and B are metal elements) are attractive material for the two-step water splitting process to produce solar hydrogen, because the diversity of perovskite compound with substitution of metal ion makes its reducibility changeable. The perovskite-type cobalt and manganese oxides are prepared with substitution of metal ion in the A-site, and the performance of two-step water splitting reaction is investigated. The LaCoO3 and Ca0.45Sr0.4La0.15MnO3-δ, containing more trivalent metal ions in the A-site of perovskite structure, are most promising materials for solar hydrogen production. It is found that the two-step water-splitting reaction with Ca0.45Sr0.4La0.15MnO3-δ of the perovskite-type manganese oxide proceed stoichiometrically and Ca0.45Sr0.4La0.15MnO3-δ can produce much H2 gas (4cm3/g-sample) at the reduction temperature of 1400 °C.

  3. Structural and thermoelectric properties of A-site substituted (Sr1-x-yCaxNdy)TiO3 perovskites

    NASA Astrophysics Data System (ADS)

    Somaily, Hamoud H.

    Detailed structural results and models are reported for a special class of A-site substituted perovskites, (Sr1-x-yCaxNd y)TiO3, obtained with high resolution NPD data as a function of temperature and Nd composition. Two series with various A-site concentrations were synthesized and investigated. Each series was designed to have a nominally constant tolerance factor. At room temperature (RT), I determine the space groups of the Sr-rich and Sr poor series as being tetragonal I4/mcm and orthorhombic Pbnm, respectively. The RT structures remain unchanged upon increasing the Nd3+ content. However, three different orthorhombic phases, Pbnm, Ibmm, Pbcm, are determined for the Sr-rich series as a function of decreasing temperature; whereas, for the Sr-poor series the orthorhombic Pbnm structure is found to persist throughout the full range of measured temperatures. A phase diagram is constructed and proposed in the temperature range 0-1000 K. Thermoelectric properties of (Sr 1-x-yCaxNdy)TiO3 were also investigated and the best figure of merit ZT=0.07 was obtained with the Sr-rich series.

  4. 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.

  5. Efficient red phosphor double-perovskite Ca3WO6 with A-site substitution of Eu3+.

    PubMed

    Zhao, Xin; Wang, Jiajia; Fan, Li; Ding, Yufeng; Li, Zhaosheng; Yu, Tao; Zou, Zhigang

    2013-10-07

    Luminescent properties of Eu(3+) activated double perovskite structure Ca3WO6 were investigated. It emits an ideal red color centered at the wavelength of 618 nm with suitable excitation from f-f transitions of Eu(3+) ions (360-550 nm) matching the near ultraviolet and blue LEDs. Charge compensation effect of Li(+), Na(+), and K(+) was investigated, and K(+) proved to be the best. The co-doping ion K(+) has a great effect on the lattice distortion of the host matrix Ca3WO6, which facilitates the red emission of Eu(3+). The substitution site for Ca in Ca3WO6 was analyzed in detail by Raman spectra and calculation results. A-site substitution is responsible for the red emission of Eu(3+) activated Ca3WO6. The integrated emission intensity of optimal Ca3WO6:K(+),Eu(3+) excited at 395 nm is about 3.5 times greater than that of Y2O2S:Eu(3+) commercial phosphors, which makes it a promising red phosphor for white LEDs.

  6. (La1-xSrx)0.98MnO3 perovskite with A-site deficiencies toward oxygen reduction reaction in aluminum-air batteries

    NASA Astrophysics Data System (ADS)

    Xue, Yejian; Miao, He; Sun, Shanshan; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2017-02-01

    The strontium doped Mn-based perovskites have been proposed as one of the best oxygen reduction reaction catalysts (ORRCs) to substitute the noble metal. However, few studies have investigated the catalytic activities of LSM with the A-site deficiencies. Here, the (La1-xSrx)0.98MnO3 (LSM) perovskites with A-site deficiencies are prepared by a modified solid-liquid method. The structure, morphology, valence state and oxygen adsorption behaviors of these LSM samples are characterized, and their catalytic activities toward ORR are studied by the rotating ring-disk electrode (RRDE) and aluminum-air battery technologies. The results show that the appropriate doping with Sr and introducing A-site stoichiometry can effectively tailor the Mn valence and increase the oxygen adsorption capacity of LSM. Among all the LSM samples in this work, the (La0.7Sr0.3)0.98MnO3 perovskite composited with 50% carbon (50%LSM30) exhibits the best ORR catalytic activity due to the excellent oxygen adsorption capacity. Also, this catalyst has much higher durability than that of commercial 20%Pt/C. Moreover, the maximum power density of the aluminum-air battery using 50%LSM30 as the ORRC can reach 191.3 mW cm-2. Our work indicates that the LSM/C composite catalysts with A-site deficiencies can be used as a promising ORRC in the metal-air batteries.

  7. New routes to synthesizing an ordered perovskite CaCu3Fe2Sb2O12 and its magnetic structure by neutron powder diffraction.

    PubMed

    Larregola, Sebastian A; Zhou, Jianshi; Alonso, Jose A; Pomjakushin, Vladimir; Goodenough, John B

    2014-05-05

    The search for new double-perovskite oxides has grown rapidly in recent years because of their interesting physical properties like ferroelectricity, magnetism, and multiferroics. The synthesis of double perovskites, especially the A-site-ordered perovskites, in most cases needs to be made under high pressure, which is a drawback for applying these materials. Here we have demonstrated synthetic routes at ambient pressure by which we have obtained a high-quality duo-sites-ordered double perovskite, CaCu3Fe2Sb2O12, which has been previously synthesized under high pressure. The availability of a large quantity of the powder sample allows us to determine the crystal and magnetic structures by neutron powder diffraction (NPD) at 300 and 1.3 K. Measurements of the magnetization and heat capacity showed a ferrimagnetic transition at 160 K. A ferrimagnetic structure consisting of the uncompensated antiferromagnetic coupling between neighboring collinear copper and iron spins has been resolved from the low-temperature NPD data.

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

    SciTech Connect

    Dinamarca, Robinson; Garcia, Ximena; Jimenez, Romel; Fierro, J.L.G.; Pecchi, Gina

    2016-09-15

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

  9. Electrical properties and water incorporation in A-site deficient perovskite La1-xBaxNb3O9-0.5x

    NASA Astrophysics Data System (ADS)

    Animitsa, I.; Iakovleva, A.; Belova, K.

    2016-06-01

    Barium doped A-site deficient perovskites La1-xBaxNb3O9-0.5x (x=0-0.05) were synthesized by the solid state method, their structure, electrical properties and state of oxygen-hydrogen groups have been investigated. These phases were found to be able to incorporate water from the gas phase and to exhibit proton transport. Hydration is accompanied by the formation of different forms of oxygen-hydrogen groups: OH- - groups and H3O+ - ions. The total conductivities of doped samples increased in a wet atmosphere due to the appearance of proton current carriers (at the temperatures below 700 °C), but the conductivity increased insignificantly (~0.25 order of magnitude) because of a low doping level and, consequently, small concentration of protons. TG-measurements confirmed relatively low water content (below 0.2%). The total conductivity depends substantially on x and exhibits a minimum on σ-f(x) dependencies. It has been suggested that such behavior is a manifestation of a mixed cation effect.

  10. Vacancy ordering and superstructure formation in dry and hydrated strontium tantalate perovskites: a TEM perspective.

    PubMed

    Ashok, Anuradha M; Haavik, Camilla; Norby, Poul; Norby, Truls; Olsen, Arne

    2014-07-01

    Crystal structures of Sr4(Sr2Ta2)O11 and Sr4(Sr1.92Ta2.08)O11.12, synthesized by solid state reaction technique in dry and hydrated state have been studied mainly using Transmission Electron Microscopy. Due to the lesser ability of X-rays to probe details in oxygen sublattice, the change in crystal symmetry due to ordering of oxygen vacancies could be detected better using Transmission Electron Microscopy. After detailed analysis through TEM, it was observed that no major change occurs in the cation sublattice. The TEM observations are compared with XRD data and discussed. The crystal symmetries and corresponding unit cells of all the perovskites based on the ordering of oxygen vacancies is deduced. Crystal unit cells based on the observations are proposed with ideal atomic coordinates. Finally an attempt is made to explain the water uptake behaviour of these perovskites based on the proposed crystal structure.

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

    NASA Astrophysics Data System (ADS)

    Balachandran, Prasanna V.; Rondinelli, James M.

    2013-08-01

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

  12. B-site Cation Ordered Double Perovskites as Efficient and Stable Electrocatalysts for Oxygen Evolution Reaction.

    PubMed

    Sun, Hainan; Chen, Gao; Zhu, Yinlong; Liu, Bo; Zhou, Wei; Shao, Zongping

    2017-03-02

    Simple disordered perovskite oxides have been intensively exploited as promising electrocatalysts for catalysing the oxygen evolution reaction (OER) towards its application in water splitting, reversible fuel cells, and rechargeable metal-air batteries. Here, we demonstrated that B-site cation-ordered double perovskite Ba2BixSc0.2Co1.8-xO6-δ with two types of cobalt local environments are superior electrocatalysts for OER in alkaline solutions, demonstrating ultrahigh catalytic activity. In addition, no obvious performance degradation was observed for the Ba2Bi0.1Sc0.2Co1.7O6-δ sample after a continuous chronopotentiometry test. The critical role of the ordered [Co2+] and [Sc3+, Bi5+, Co3+] dual environments in improving OER activity was exhibited. The aforementioned results indicate that B-site cation-ordered double perovskite oxides may represent a new class of promising electrocatalysts for the OER in sustainable energy storage and conversion systems.

  13. Quantitative STEM Imaging of Order-Disorder Phenomena in Double Perovskite Thin Films.

    PubMed

    Esser, B D; Hauser, A J; Williams, R E A; Allen, L J; Woodward, P M; Yang, F Y; McComb, D W

    2016-10-21

    Using aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we investigate ordering phenomena in epitaxial thin films of the double perovskite Sr_{2}CrReO_{6}. Experimental and simulated imaging and diffraction are used to identify antiphase domains in the films. Image simulation provides insight into the effects of atomic-scale ordering along the beam direction on HAADF-STEM intensity. We show that probe channeling results in ±20% variation in intensity for a given composition, allowing 3D ordering information to be probed using quantitative STEM.

  14. Quantitative STEM Imaging of Order-Disorder Phenomena in Double Perovskite Thin Films

    NASA Astrophysics Data System (ADS)

    Esser, B. D.; Hauser, A. J.; Williams, R. E. A.; Allen, L. J.; Woodward, P. M.; Yang, F. Y.; McComb, D. W.

    2016-10-01

    Using aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we investigate ordering phenomena in epitaxial thin films of the double perovskite Sr2 CrReO6 . Experimental and simulated imaging and diffraction are used to identify antiphase domains in the films. Image simulation provides insight into the effects of atomic-scale ordering along the beam direction on HAADF-STEM intensity. We show that probe channeling results in ±20 % variation in intensity for a given composition, allowing 3D ordering information to be probed using quantitative STEM.

  15. Structure and cation distribution in perovskites with small cations at the A site: the case of ScCoO3

    NASA Astrophysics Data System (ADS)

    Yi, Wei; Presniakov, Igor A.; Sobolev, Alexey V.; Glazkova, Yana S.; Matsushita, Yoshitaka; Tanaka, Masahiko; Kosuda, Kosuke; Tsujimoto, Yoshihiro; Yamaura, Kazunari; Belik, Alexei A.

    2015-04-01

    We synthesize ScCoO3 perovskite and its solid solutions, ScCo1-xFexO3 and ScCo1-xCrxO3, under high pressure (6 GPa) and high temperature (1570 K) conditions. We find noticeable shifts from the stoichiometric compositions, expressed as (Sc1-xMx)MO3 with x = 0.05-0.11 and M = Co, (Co, Fe) and (Co, Cr). The crystal structure of (Sc0.95Co0.05)CoO3 is refined using synchrotron x-ray powder diffraction data: space group Pnma (No. 62), Z = 4 and lattice parameters a = 5.26766(1) Å, b = 7.14027(2) Å and c = 4.92231(1) Å. (Sc0.95Co0.05)CoO3 crystallizes in the GdFeO3-type structure similar to other members of the perovskite cobaltite family, ACoO3 (A3+ = Y and Pr-Lu). There is evidence that (Sc0.95Co0.05)CoO3 has non-magnetic low-spin Co3+ ions at the B site and paramagnetic high-spin Co3+ ions at the A site. In the iron-doped samples (Sc1-xMx)MO3 with M = (Co, Fe), Fe3+ ions have a strong preference to occupy the A site of such perovskites at small doping levels.

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

    PubMed Central

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

    2015-01-01

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

  17. Long-Range Antiferromagnetic Ordering in B-Site Ordered Double Perovskite Ca2ScOsO6.

    PubMed

    Russell, David D; Neer, Abbey J; Melot, Brent C; Derakhshan, Shahab

    2016-03-07

    A new Os-based B-site ordered double perovskite with the chemical composition of Ca2ScOsO6 was successfully synthesized. The crystal structure of the title compound was determined by employing the powder X-ray diffraction method and was found to crystallize in the monoclinic P21/n space group with the cell constants of a = 5.4716(1) Å, b = 5.6165(1) Å, c = 7.8168 (1) Å, and β = 89.889 (2)°. The temperature-dependent magnetic susceptibility data suggest that this novel S = (3)/2 compound undergoes an antiferromagnetic transition at ∼ 69 K. Fitting the high-temperature susceptibility data (100-300 K) to Currie-Weisse behavior showed C = 1.734 emu·K/mol (μeff = 3.72 bohr magnetons) and θ = -341 K, which is indicative of dominant antiferromagnetic interactions. Temperature-dependent specific heat measurements exhibit a λ shape anomaly at 69 K, which is consistent with a long-range ordering of the spins. Because of a triangular arrangement of antiferromagnetically ordered magnetic ions, the system exhibits some degree of geometric magnetic frustration (GMF), but not strongly. Spin-dimer analysis, employing extended Hückel theory, reveals that a dominant exchange interaction exists (along the a crystallographic axis in perovskite layer), which violates the perfect condition for GMF.

  18. Two-dimensional electron systems in A TiO3 perovskites (A =Ca , Ba, Sr): Control of orbital hybridization and energy order

    NASA Astrophysics Data System (ADS)

    Rödel, T. C.; Vivek, M.; Fortuna, F.; Le Fèvre, P.; Bertran, F.; Weht, R.; Goniakowski, J.; Gabay, M.; Santander-Syro, A. F.

    2017-07-01

    We report the existence of a two-dimensional electron system (2DES) at the (001 ) surface of CaTiO3. Using angle-resolved photoemission spectroscopy, we find a hybridization between the dx z and dy z orbitals, not observed in the 2DESs at the surfaces of other A TiO3 perovskites, e.g., SrTiO3 or BaTiO3. Based on a comparison of the 2DES properties in these three materials, we show how the electronic structure of the 2DES (bandwidth, orbital energy order, and electron density) is coupled to different typical lattice distortions in perovskites. The orbital hybridization in orthorhombic CaTiO3 results from the rotation of the oxygen octahedra, which can also occur at the interface of oxide heterostructures to compensate strain. More generally, the control of the orbital energy order in 2DES by choosing different A -site cations in perovskites offers a gateway toward 2DESs in oxide heterostructures beyond SrTiO3.

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

    SciTech Connect

    Clemens, Oliver

    2015-05-15

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

  20. Strong enhancement of spin ordering by A -site magnetic ions in the ferrimagnet CaC u3F e2O s2O12

    NASA Astrophysics Data System (ADS)

    Deng, Hongshan; Liu, Min; Dai, Jianhong; Hu, Zhiwei; Kuo, Changyang; Yin, Yunyu; Yang, Junye; Wang, Xiao; Zhao, Qing; Xu, Yuanji; Fu, Zhaoming; Cai, Jianwang; Guo, Haizhong; Jin, Kuijuan; Pi, Tunwen; Soo, Yunliang; Zhou, Guanghui; Cheng, Jinguang; Chen, Kai; Ohresser, Philippe; Yang, Yi-feng; Jin, Changqing; Tjeng, Liu-Hao; Long, Youwen

    2016-07-01

    A B O3 perovskite is a kind of very important functional material with versatile physical properties. Although B -site chemical substitution with various magnetic ions has been widely investigated, the A -site doping with magnetic transition metal is little known. Here we report A A3'B2B2'O12 -type A - and B -site ordered ferrimagnet CaC u3F e2O s2O12 with magnetic transition metals occupying three different atomic sites (A', B , and B' sites). This compound is synthesized by a special high-pressure annealing process. It possesses a much higher Curie temperature TC of 580 K compared with that of the B -site-only ordered C a2FeOs O6 (TC=320 K ) without magnetic ion at the A site. First-principles numerical calculations reveal that this enhancement primarily originates from the additional spin interaction between the A'-site C u2 + and the B'-site O s5 + , generating a strong C u2 +(↑) F e3 +(↑) O s5 +(↓) ferrimagnetic spin coupling. This work opens up an alternative way for enhancing the spin ordering temperature by introducing A -site magnetic ions.

  1. Competing antiferromagnetic orders in the double perovskite Mn2MnReO6 (Mn3ReO6).

    PubMed

    Arévalo-López, A M; Stegemann, F; Attfield, J P

    2016-04-25

    The new double perovskite Mn2MnReO6 has been synthesised at high pressure. Mn(2+) and Re(6+) spins order antiferromagnetically through two successive transitions that are coupled by magnetoelastic effects, as order of the Mn spins at 109 K leads to lattice distortions that reduce frustration prompting Re order at 99 K.

  2. Defect Tolerance to Intolerance in the Vacancy-Ordered Double Perovskite Semiconductors Cs2SnI6 and Cs2TeI6.

    PubMed

    Maughan, Annalise E; Ganose, Alex M; Bordelon, Mitchell M; Miller, Elisa M; Scanlon, David O; Neilson, James R

    2016-07-13

    Vacancy-ordered double perovskites of the general formula A2BX6 are a family of perovskite derivatives composed of a face-centered lattice of nearly isolated [BX6] units with A-site cations occupying the cuboctahedral voids. Despite the presence of isolated octahedral units, the close-packed iodide lattice provides significant electronic dispersion, such that Cs2SnI6 has recently been explored for applications in photovoltaic devices. To elucidate the structure-property relationships of these materials, we have synthesized solid-solution Cs2Sn1-xTexI6. However, even though tellurium substitution increases electronic dispersion via closer I-I contact distances, the substitution experimentally yields insulating behavior from a significant decrease in carrier concentration and mobility. Density functional calculations of native defects in Cs2SnI6 reveal that iodine vacancies exhibit a low enthalpy of formation, and that the defect energy level is a shallow donor to the conduction band rendering the material tolerant to these defect states. The increased covalency of Te-I bonding renders the formation of iodine vacancy states unfavorable and is responsible for the reduction in conductivity upon Te substitution. Additionally, Cs2TeI6 is intolerant to the formation of these defects, because the defect level occurs deep within the band gap and thus localizes potential mobile charge carriers. In these vacancy-ordered double perovskites, the close-packed lattice of iodine provides significant electronic dispersion, while the interaction of the B- and X-site ions dictates the properties as they pertain to electronic structure and defect tolerance. This simplified perspective based on extensive experimental and theoretical analysis provides a platform from which to understand structure-property relationships in functional perovskite halides.

  3. Ferromagnetism induced by entangled charge and orbital orderings in ferroelectric titanate perovskites

    PubMed Central

    Bristowe, N. C.; Varignon, J.; Fontaine, D.; Bousquet, E.; Ghosez, Ph.

    2015-01-01

    In magnetic materials, the Pauli exclusion principle typically drives anti-alignment between electron spins on neighbouring species resulting in antiferromagnetic behaviour. Ferromagnetism exhibiting spontaneous spin alignment is a fairly rare behaviour, but once materialized is often associated with itinerant electrons in metals. Here we predict and rationalize robust ferromagnetism in an insulating oxide perovskite structure based on the popular titanate series. In half-doped layered titanates, the combination of Jahn–Teller and oxygen breathing motions opens a band gap and creates an unusual charge and orbital ordering of the Ti d electrons. It is argued that this intriguingly intricate electronic network favours the elusive inter-site ferromagnetic (FM) ordering, on the basis of intra-site Hund's rules. Finally, we find that the layered oxides are also ferroelectric with a spontaneous polarization approaching that of BaTiO3. The concepts are general and design principles of the technologically desirable FM ferroelectric multiferroics are presented. PMID:25807180

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  5. Structure and magnetism in S r1 -xAxTc O3 perovskites: Importance of the A -site cation

    NASA Astrophysics Data System (ADS)

    Reynolds, Emily; Avdeev, Maxim; Thorogood, Gordon J.; Poineau, Frederic; Czerwinski, Kenneth R.; Kimpton, Justin A.; Yu, Michelle; Kayser, Paula; Kennedy, Brendan J.

    2017-02-01

    The S r1 -xB axTc O3 (x =0 , 0.1, 0.2) oxides were prepared and their solid-state and magnetic structure studied as a function of temperature by x-ray and neutron powder diffraction. The refined Tc moments at room temperature and Néel temperatures for B a0.1S r0.9Tc O3 and B a0.2S r0.8Tc O3 were 2.32 (14 ) μβ and 2.11 (13 ) μβ and 714 ∘C and 702 ∘C , respectively. In contrast to expectations, the Néel temperature in the series S r1 -xAxTc O3 decreases with increasing Ba content. This observation is consistent with previous experimental measurements for the two series A M O3 (M =Ru , Mn; A =Ca , Sr, Ba) where the maximum magnetic ordering temperature was observed for A =Sr . Taken with these previous results the current work demonstrates the critical role of the A -site cation in the broadening of the π* bandwidth and ultimately the magnetic ordering temperature.

  6. Critical competition between two distinct orbital-spin ordered states in perovskite vanadates

    NASA Astrophysics Data System (ADS)

    Fujioka, J.; Yasue, T.; Miyasaka, S.; Yamasaki, Y.; Arima, T.; Sagayama, H.; Inami, T.; Ishii, K.; Tokura, Y.

    2010-10-01

    We have investigated the spin/orbital phase diagram in the perovskite orthovanadate RVO3 ( R=Eu , Y, Dy, and Ho) by measurements of magnetization, dielectric constant, specific heat, Raman scattering spectra, and x-ray diffraction, focusing on the interplay between the V3d spin and the 4f moment of the R ion. The thermally induced phase transition between the C-type spin/G-type orbital ordered state and the G-type spin/C-type orbital ordered state is observed for Eu1-xYxVO3 (x=0-0.52) without 4f moment. By comparing this phase diagram with the spin/orbital ordering in TbVO3 , it is evident that the critical competition between the C-type spin/G-type orbital ordered phase and the G-type spin/C-type orbital ordered one depends not only on the GdFeO3 -type lattice distortion but also on the presence of the 4f moment of the R ion. The magnetic field induced phase transition of the spin/orbital ordering is achieved concomitantly with polarizing R4f moments for DyVO3 and HoVO3 . For DyVO3 , the G-type spin/C-type orbital ordered phase is switched to the C-type spin/G-type orbital ordered one by applying a moderate magnetic field around 3 T. By contrast, the G-type spin/C-type orbital ordering is rather favored under the magnetic field in HoVO3 . The results cannot be uniquely explained in terms of the exchange interaction between the V3d spin and the R -ion 4f moment. The coupling of the R4f moment polarization with the lattice distortion tied with the orbital ordering of the V3d sublattice may also be relevant to this field induced phase transition.

  7. Microstructure evolution and magnetoresistance of the A-site ordered Ba-doped manganites

    SciTech Connect

    Trukhanov, S. V. Lobanovski, L. S.; Bushinsky, M. V.; Khomchenko, V. A.; Fedotova, V. V.; Troyanchuk, I. O.; Szymczak, H.

    2007-05-15

    The microstructure, crystal structure, and magnetotransport properties of microsized and nanosized Badoped manganites have been investigated. A 'two-step' reduction-reoxidation procedure has been used to obtain nanosized ceramic manganite Nd{sub 0.70}Ba{sub 0.30}MnO{sub 3} (II). The parent microsized manganite Nd{sub 0.70}Ba{sub 0.30}MnO{sub 3} (I) was prepared by usual ceramic technology in air. Then the sample was annealed in vacuum. The grain size of the reduced sample, determined by scanning electron microscopy, decreased from {approx}5 {mu}m down to {approx}100 nm. To obtain the oxygen stoichiometry nanosized sample, the Nd{sub 0.70}Ba{sub 0.30}MnO{sub 2.60} was again annealed in air. It is established that the (I) sample is a pseudocubic perovskite, whereas (II) is tetrahedral as a consequence of Nd{sup 3+} and Ba{sup 2+} ions as well as the ordering of oxygen vacancies. The (I) sample is a ferromagnet with T{sub C} {approx} 140 K. It has metal-insulator transition at T{sub MI} {approx} 135 K and a peak of magnetoresistance {approx}50% in a field of 9 kOe. For the (II) sample, the critical points of phase transitions move to higher temperatures, T{sub C} {approx} 320 K and T{sub MI} {approx} 310 K. The magnetoresistance of the (II) sample at room temperature (T {approx} 293 K) is about 7% in a field of 9 kOe. The magnetotransport properties are interpreted in the framework of the nanosized effect.

  8. 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.

  9. Abnormal magnetic ordering and ferromagnetism in perovskite ScMnO3 film

    NASA Astrophysics Data System (ADS)

    Wang, F.; Zhang, Y. Q.; Liu, W.; Ning, X. K.; Bai, Y.; Dai, Z. M.; Ma, S.; Zhao, X. G.; Li, S. K.; Zhang, Z. D.

    2015-06-01

    Bulk multiferroic ScMnO3 is the stable hexagonal phase, and it is very difficult to prepare its perovskite orthorhombic phase even under high pressure. We fabricated the orthorhombic ScMnO3 thin film by pulsed laser deposition through suitable substrate LaAlO3 and found that nano-scale twin-like domains are naturally formed in the thin film. Magnetic properties of the orthorhombic ScMnO3 thin films show that, besides normal antiferromagnetic ordering at 47 K, an anomalous magnetic transition occurs at 27 K for 60 nm film and at 36 K for 150 nm film only along the c-axis, which is absent in the ab-plane. Moreover, the second magnetic transition for both films is suppressed when the applied field increases from 1 kOe to 10 kOe. In addition, the ferromagnetism shows up in both films at 10 K, and saturation magnetization increases dramatically in 60 nm film compared with 150 nm film. We propose that the second magnetic transition might be more of lattice strain effect and also related to magnetism-induced ferroelectric polarization in orthorhombic RMnO3 thin films and low-temperature ferromagnetic properties in our films originate from the nano-scale twin-like domain structure.

  10. Direct mapping of Li-enabled octahedral tilt ordering and associated strain in nanostructured perovskites

    NASA Astrophysics Data System (ADS)

    Zhu, Ye; Withers, Ray L.; Bourgeois, Laure; Dwyer, Christian; Etheridge, Joanne

    2015-11-01

    Self-assembled nanostructures with periodic phase separation hold great promise for creating two- and three-dimensional superlattices with extraordinary physical properties. Understanding the mechanism(s) driving the formation of such superlattices demands an understanding of their underlying atomic structure. However, the nanoscale structural fluctuations intrinsic to these superlattices pose a new challenge for structure determination methods. Here we develop an optimized atomic-level imaging condition to measure TiO6 octahedral tilt angles, unit-cell-by-unit-cell, in perovskite-based Li0.5-3xNd0.5+xTiO3, and thereby determine the mathematical formula governing this nanoscale superstructure. We obtain a direct real-space correlation of the octahedral tilt modulation with the superstructure geometry and lattice-parameter variations. This reveals a composition-dependent, self-ordered octahedral superlattice. Amazingly, we observe a reversible annihilation/reconstruction of the octahedral superlattice correlated with the delithiation/lithiation process in this promising Li-ion conductor. This approach to quantify local octahedral tilt and correlate it with strain can be applied to characterize complex octahedral behaviours in other advanced oxide systems.

  11. Electrical properties and water incorporation in A-site deficient perovskite La{sub 1−x}Ba{sub x}Nb{sub 3}O{sub 9−0.5x}

    SciTech Connect

    Animitsa, I.; Iakovleva, A.; Belova, K.

    2016-06-15

    Barium doped A-site deficient perovskites La{sub 1−x}Ba{sub x}Nb{sub 3}O{sub 9−0.5x} (x=0–0.05) were synthesized by the solid state method, their structure, electrical properties and state of oxygen-hydrogen groups have been investigated. These phases were found to be able to incorporate water from the gas phase and to exhibit proton transport. Hydration is accompanied by the formation of different forms of oxygen-hydrogen groups: OH{sup −} – groups and H{sub 3}O{sup +} – ions. The total conductivities of doped samples increased in a wet atmosphere due to the appearance of proton current carriers (at the temperatures below 700 °C), but the conductivity increased insignificantly (~0.25 order of magnitude) because of a low doping level and, consequently, small concentration of protons. TG-measurements confirmed relatively low water content (below 0.2%). The total conductivity depends substantially on x and exhibits a minimum on σ−f(x) dependencies. It has been suggested that such behavior is a manifestation of a mixed cation effect. - Highlights: • Barium doped perovskites La{sub 1−x}Ba{sub x}Nb{sub 3}O{sub 9−0.5x} (x=0–0.05) are capable to incorporate water from the gas phase and to exhibit proton transport. • The hydration is accompanied by the formation of OH{sup −} – groups and H{sub 3}O{sup +} – ions. • The total conductivity exhibits a minimum on σ−f(x) dependencies as a result of a mixed cation effect.

  12. Isolation of two-dimensional 2:1 cation-ordered perovskite units by anion vacancy ordering in Ba6Na2Nb2P2O17.

    PubMed

    Kuang, Xiaojun; Claridge, John B; Price, Tim; Iddles, David M; Rosseinsky, Matthew J

    2008-10-06

    A new six-layer perovskite-related structure Ba 6Na 2Nb 2M 2O 17 (M = P, V), which consists of cubic (c) BaO 3 layers and oxygen-deficient pseudocubic (c') BaO 2 layers stacked in the sequence c'ccccc, is presented. In Ba 6Na 2Nb 2M 2O 17, two-dimensional slabs of the well-known 2:1 octahedral cation-ordered perovskite motif are isolated between layers of tetrahedral units formed by anion vacancy ordering: two consecutive NbO 6 octahedral layers are sandwiched by two single NaO 6 octahedral layers, which, in turn, connect with two isolated MO 4 tetrahedral layers. Both oxides are derived from the 2:1 ordered perovskite structure (e.g., Ba 3ZnTa 2O 9) by ordered removal of O atoms in every sixth BaO 3 layer. Both materials exhibit a relative permittivity of approximately 20-23, Q x f 0 values of approximately 7800-10600 GHz, and negative temperature coefficients of the resonant frequency of approximately -23 to -7 ppm/ degrees C.

  13. Role of the A -site cation in determining the properties of the hybrid perovskite CH3NH3PbBr3

    NASA Astrophysics Data System (ADS)

    Sarkar, Sagar; Mahadevan, Priya

    2017-06-01

    The presence of a molecule at the A site of an organic perovskite leads to unusual behavior compared to its inorganic counterpart. Considering the case of CH3NH3 , we find that it is both the size of the molecule as well as its orientation in the cage formed by the Pb and Br atoms which determine the favored structure. At the microscopic level, the basic energetics which come into play are steric effects as well as hydrogen bonding. While the molecule is asymmetrically placed in the cuboctahedral cavity, a mapping of the ab initio band structure to a tight-binding model reveals that the movement of the amine end of the molecule towards the Br atoms is driven primarily by electrostatic considerations. While the hydrogen bonding is responsible for driving the octahedral tilts, the energy lowering considerations do not follow a simple prescription of minimizing H-Br bond lengths. The presence of several competing energetics results in a complex low-energy landscape with deep valleys and high barriers between them which could explain the glassy dynamics seen even at low temperatures in the orthorhombic structure where the dipoles are believed to be frozen.

  14. Statistical theory of orbital ordering in perovskites based on a three-minimum two-sublattice model

    NASA Astrophysics Data System (ADS)

    Ivliev, M. P.; Sakhnenko, V. P.

    2016-12-01

    The existence of tetragonally distorted octahedra found in a high-temperature cubic phase of some perovskites (LaMnO3, KCrF3, etc.) and the estimations performed make it possible to consider the observed orbital orderings as order-disorder phase transitions. The conditions of formation of ferro- and antiferrodistortive phase states described by the order parameters corresponding to reciprocal lattice vectors k = 0 and k 1/2( b 1 + b 2 + b 3), have been determined using a three-minimum two-sublattice model. The model is shown to be applicable for description of phase transitions in some ion-molecular crystals.

  15. Magnetic ordering of divalent europium in double perovskites Eu{sub 2}LnTaO{sub 6} (Ln=rare earths)

    SciTech Connect

    Misawa, Yoshitaka; Doi, Yoshihiro; Hinatsu, Yukio

    2011-06-15

    Structures and magnetic properties of double perovskite-type oxides Eu{sub 2}LnTaO{sub 6} (Ln=Eu, Dy-Lu) were investigated. These compounds adopt a distorted double perovskite structure with space group P2{sub 1}/n. Magnetic susceptibility, specific heat, and {sup 151}Eu Moessbauer spectrum measurements show that the Eu{sup 2+} ions at the 12-coordinate sites of the perovskite structure are antiferromagnetically ordered at {approx}4 K, and that Ln{sup 3+} ions at the 6-coordinate site are in the paramagnetic state down to 1.8 K. - Graphical abstract: Magnetic properties of double perovskite-type oxides Eu{sub 2}LnTaO{sub 6} (Ln=Eu, Dy-Lu) were investigated. Magnetic susceptibility, specific heat, and {sup 151}Eu Moessbauer spectrum measurements show that the Eu{sup 2+} ions at the 12-coordinate sites of the perovskite structure are antiferromagnetically ordered at {approx}4 K. Highlights: > Crystal structures of double perovskites Eu{sub 2}LnTaO{sub 6} (Ln=rare earth) were determined. > We found that these compounds show an antiferromagnetic ordering at {approx}4 K. > The magnetic ordering is due to the interactions of Eu{sup 2+} ions. > It was elucidated by specific heat and {sup 151}Eu Moessbauer spectrum measurements.

  16. Magnetization reversal in mixed ferrite-chromite perovskites with non magnetic cation on the A-site.

    PubMed

    Billoni, Orlando V; Pomiro, Fernando; Cannas, Sergio A; Martin, Christine; Maignan, Antoine; Carbonio, Raul E

    2016-11-30

    In this work, we have performed Monte Carlo simulations in a classical model for RFe1-x Cr x O3 with R  =  Y and Lu, comparing the numerical simulations with experiments and mean field calculations. In the analyzed compounds, the antisymmetric exchange or Dzyaloshinskii-Moriya (DM) interaction induced a weak ferromagnetism due to a canting of the antiferromagnetically ordered spins. This model is able to reproduce the magnetization reversal (MR) observed experimentally in a field cooling process for intermediate x values and the dependence with x of the critical temperatures. We also analyzed the conditions for the existence of MR in terms of the strength of DM interactions between Fe(3+) and Cr(3+) ions with the x values variations.

  17. Magnetization reversal in mixed ferrite-chromite perovskites with non magnetic cation on the A-site

    NASA Astrophysics Data System (ADS)

    Billoni, Orlando V.; Pomiro, Fernando; Cannas, Sergio A.; Martin, Christine; Maignan, Antoine; Carbonio, Raul E.

    2016-11-01

    In this work, we have performed Monte Carlo simulations in a classical model for RFe1-x Cr x O3 with R  =  Y and Lu, comparing the numerical simulations with experiments and mean field calculations. In the analyzed compounds, the antisymmetric exchange or Dzyaloshinskii-Moriya (DM) interaction induced a weak ferromagnetism due to a canting of the antiferromagnetically ordered spins. This model is able to reproduce the magnetization reversal (MR) observed experimentally in a field cooling process for intermediate x values and the dependence with x of the critical temperatures. We also analyzed the conditions for the existence of MR in terms of the strength of DM interactions between Fe3+ and Cr3+ ions with the x values variations.

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

    SciTech Connect

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

    2013-04-15

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

  19. New oxygen-deficient cationic-ordered perovskites containing turquoise-coloring Mn5+O4 tetrahedral layers

    NASA Astrophysics Data System (ADS)

    Han, Yifeng; Ye, Xuanhong; Zhu, Hong; Li, Yuexiang; Kuang, Xiaojun

    2017-03-01

    Ba6Na2M2Mn2O17 (M=Nb, Ta) oxides were synthesized by high-temperature solid-state reaction. The compounds adopt 6-layer perovskite-related structure (referred to as 6C) in P 3 ̅m1, analogous to Ba6Na2Nb2P2O17. The 6C structure consists of cubic (c) BaO3 layers and pseudo-cubic (c') oxygen-vacancy-ordered BaO2 layers stacked according to a sequence of c'ccccc. Ordering of oxygen vacancies in oxygen-deficient c'-BaO2 layers leads to two successive isolated tetrahedral layers, which stabilize an unusual +5 oxidation state for Mn cations in the tetrahedral sites. In Ba6Na2M2Mn2O17, these two Mn5+O4 layers are sandwiched by two single octahedral NaO6 layers that connected by two successive octahedral NbO6 layers, forming alternative 2:1-ordered (Ba3NaM2O9)- and (Ba3NaMn2O8)+ perovskite-like units along the stacking direction. The Mn5+O4 tetrahedral units act as a turquoise chromophore in Ba6Na2M2Mn2O17, making these two compounds potential turquoise-coloring materials for the cool pigments.

  20. Defect Tolerance to Intolerance in the Vacancy-Ordered Double Perovskite Semiconductors Cs 2 SnI 6 and Cs 2 TeI 6

    SciTech Connect

    Maughan, Annalise E.; Ganose, Alex M.; Bordelon, Mitchell M.; Miller, Elisa M.; Scanlon, David O.; Neilson, James R.

    2016-07-13

    Vacancy-ordered double perovskites of the general formula, A2BX6, are a family of perovskite derivatives composed of a face-centered lattice of nearly isolated [BX6] units with A-site cations occupying the cuboctahedral voids. Despite the presence of isolated octahedral units, the close-packed iodide lattice provides significant electronic dispersion, such that Cs2SnI6 has recently been explored for applications in photovoltaic devices. To elucidate the structure-property relationships of these materials, we have synthesized the solid solution Cs2Sn1-xTexI6. However, even though tellurium substitution increases electronic dispersion via closer I-I contact distances, the substitution experimentally yields insulating behavior from a significant decrease in carrier concentration and mobility. Density functional calculations of native defects in Cs2SnI6 reveal that iodine vacancies exhibit a low enthalpy of formation and the defect energy level is a shallow donor to the conduction band, rendering the material tolerant to these defect states. The increased covalency of Te-I bonding renders the formation of iodine vacancy states unfavorable, and is responsible for the reduction in conductivity upon Te substitution. Additionally, Cs2TeI6 is intolerant to the formation of these defects, as the defect level occurs deep within the band gap and thus localizes potential mobile charge carriers. In these vacancy-ordered double perovskites, the close-packed lattice of iodine provides significant electronic dispersion, while the interaction of the B- and X-site ions dictates the properties as they pertain to electronic structure and defect tolerance. This simplified perspective -- based on extensive experimental and theoretical analysis -- provides a platform from which to understand structure-property relationships in functional perovskite halides.

  1. Effect of Co Substitution on the Crystal and Magnetic Structure of SrFeO2.75-δ: Stabilization of the "314-Type" Oxygen Vacancy Ordered Structure without A-Site Ordering.

    PubMed

    Marik, Sourav; Chennabasappa, Madhu; Fernández-Sanjulián, Javier; Petit, Emmanuel; Toulemonde, Olivier

    2016-10-03

    A study of the structure-composition-properties correlation is reported for the oxygen-deficient SrFe1-xCoxO2.75-δ (x = 0.1-0.85) materials. The introduction of Co in the parent SrFeO2.75 (Sr4Fe4O11) structure revealed an interesting structural transformation. At room temperature (RT), an orthorhombic (space group Cmmm, 2√2ap × 2ap × √2ap type, ap = lattice parameter of the cubic perovskite) → tetragonal (space group P4/mmm, ap × ap × 2ap type) → tetragonal (space group I4/mmm, 2ap × 2ap × 4ap type) structural transformation is observed in parallel with increasing Co content and decreasing oxygen content in the structure. At the same time, a rich variation in the magnetic properties is explored. The samples with x = 0.25, 0.3 show temperature-induced magnetization reversal. With increasing Co content in the structure, magnetic interactions start to weaken due to the random distribution of Fe and Co in the structure; the x = 0.5 sample shows frustration in the magnetic behavior with much smaller magnetization value. With a further increase in the Co content in the structure, RT ferrimagnetic-type behavior is observed for the sample with x = 0.85. The nuclear and magnetic structure refinements using RT and low-temperature neutron powder diffraction (NPD, 10 K) patterns confirm the formation of a "314-type" novel oxygen vacancy ordered phase for the sample with x = 0.85, which is the first case of "314-type" novel oxygen vacancy ordering without A-site (ABO3-δ type perovskite) ordering. The magnetic structure is G-type antiferromagnetic starting at room temperature. Further, the stabilization of the "314-type" complex superstructure is related to the ordering of oxygen vacancies in the oxygen-deficient Co-O layers, and the same assists in building a network of Co ions with different coordination environments, each with different spin states, and forms the spin-state ordering.

  2. Weak orbital ordering of Ir t2 g states in the double perovskite Sr2CeIrO6

    NASA Astrophysics Data System (ADS)

    Kanungo, Sudipta; Mogare, Kailash; Yan, Binghai; Reehuis, Manfred; Hoser, Andreas; Felser, Claudia; Jansen, Martin

    2016-06-01

    The electronic and magnetic properties of distorted monoclinic double perovskite Sr2CeIrO6 were examined based on both experiments and first-principles density functional theory calculations. From the calculations we conclude that low-spin-state Ir4 + (5 d5 ) forms a rare weakly antiferromagnetic (AFM) orbital ordered state derived from alternating occupation of slightly mixed egπ symmetry states in the presence of spin-orbit coupling (SOC). This orbital ordering is caused due to the competition between the comparable strength of Jahn-Teller structural distortion and SOC. We found both electron-electron correlation and SOC are required to drive the experimentally observed AFM-insulating ground state. Electronic structure investigation suggests that this material belongs to the intermediate-SOC regime, by comparing our results with the other existing iridates. This single active site double perovskite provides a rare platform with a prototype geometrically frustrated fcc lattice where among the different degrees of freedom (i.e., spin, orbital, and lattice) SOC, structural distortion, and Coulomb correlation energy scales compete and interact with each other.

  3. The absence of ferroelectric polarization in layered and rock-salt ordered NaLnMnWO6 (Ln = La, Nd, Tb) perovskites.

    PubMed

    De, Chandan; Kim, Tai Hoon; Kim, Kee Hoon; Sundaresan, A

    2014-03-21

    The ordered perovskites, NaLnMnWO6 (Ln = La, Nd, Tb), are reported to exhibit simultaneous ordering of A-site cations (Na and Ln) in layered arrangement and B-site cations (Mn and W) in rock salt structure. They have been shown to crystallize in a monoclinic structure with the polar space group P21. Based on density functional calculations and group theoretical analysis, it has recently been proposed that NaLaMnWO6 should be ferroelectric with a relatively large polarization (16 μC cm(-2)). Contrary to this prediction, our electrical measurements such as conventional P-E loop, Positive-Up and Negative-Down (PUND), piezoelectric response and Second Harmonic Generation (SHG) reveal the absence of ferroelectric polarization in NaLnMnWO6 (Ln = La, Nd, Tb). A dielectric anomaly is observed just below room temperature (∼270 K) for all the three compounds, which is related to the change in conductivity as revealed by temperature dependent ac and dc resistivity. A pyrocurrent peak is also observed at the same temperature. However, its origin cannot be attributed to a ferroelectric transition.

  4. Multiferroicity in B-site ordered double perovskite Y2MnCrO6

    NASA Astrophysics Data System (ADS)

    Fang, Yong; Yan, Shi-Ming; Qiao, Wen; Wang, Wei; Wang, Dun-Hui; Du, You-Wei

    2014-11-01

    Double perovskite manganite Y2MnCrO6 ceramic is synthesized and its multiferroic properties are investigated. Novel multiferroic properties are displayed with respect to other multiferroics, such as high ferroelectric phase transition temperature, and the coexistence of ferrimagnetism and ferroelectricity. Moreover, the ferroelectric polarization of Y2MnCrO6 below the magnetic phase temperature can be effectively tuned by an external magnetic field, showing a remarkable magnetoelectric effect. These results open an effective avenue to explore magnetic multiferroics with spontaneous magnetization and ferroelectricity, as well as a high ferroelectric transition temperature.

  5. The ordered double perovskite PrBaCo2O6: Synthesis, structure, and magnetism

    NASA Astrophysics Data System (ADS)

    Motin Seikh, Md.; Pralong, V.; Lebedev, O. I.; Caignaert, V.; Raveau, B.

    2013-07-01

    The stoichiometric layered perovskite cobaltite PrBaCo2O6 has been synthesized using an oxidative reaction of PrBaCo2O5.80 by sodium hypochlorite. The ferromagnetic properties of this oxide, which exhibits the highest TC of 210 K among the "112" layered cobaltites, are interpreted by double exchange mechanism. In contrast, the creation of oxygen vacancies in this framework leads for the oxides PrBaCo2O5+δ (0.80 ≤ δ < 1) to a strong competition between ferromagnetism and antiferromagnetism due to the appearance of superexchange Co3+—O—Co3+ antiferromagnetic interactions.

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

    DOE PAGES

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

    2015-03-01

    The magnetic susceptibility, crystal and magnetic structures, and electronic structure of double perovskite Sr2ScOsO6 are reported. Using both neutron and x-ray powder diffraction we find that the crystal structure is monoclinic P21/n from 3.5 to 300 K. Magnetization measurements indicate an antiferromagnetic transition at TN=92 K, one of the highest transition temperatures of any double perovskite hosting only one magnetic ion. Type I antiferromagnetic order is determined by neutron powder diffraction, with an Os moment of only 1.6(1) muB, close to half the spin-only value for a crystal field split 5d electron state with t2g^3 ground state. Density functional calculationsmore » show that this reduction is largely the result of strong Os-O hybridization, with spin-orbit coupling responsible for only a ~0.1 muB reduction in the moment.« less

  7. Time-Dependent Mechanical Response of APbX3 (A = Cs, CH3NH3; X = I, Br) Single Crystals [The Dynamic Mechanical Properties of Lead-Halide Perovskite Single Crystals are Independent of A-site Cation Chemistry

    DOE PAGES

    Reyes-Martinez, Marcos A.; Abdelhady, Ahmed L.; Saidaminov, Makhsud I.; ...

    2017-05-02

    The ease of processing hybrid organic–inorganic perovskite (HOIPs) films, belonging to a material class with composition ABX3, from solution and at mild temperatures promises their use in deformable technologies, including flexible photovoltaic devices, sensors, and displays. To successfully apply these materials in deformable devices, knowledge of their mechanical response to dynamic strain is necessary. The authors elucidate the time- and rate-dependent mechanical properties of HOIPs and an inorganic perovskite (IP) single crystal by measuring nanoindentation creep and stress relaxation. The observation of pop-in events and slip bands on the surface of the indented crystals demonstrate dislocation-mediated plastic deformation. The magnitudesmore » of creep and relaxation of both HOIPs and IPs are similar, negating prior hypothesis that the presence of organic A-site cations alters the mechanical response of these materials. Moreover, these samples exhibit a pronounced increase in creep, and stress relaxation as a function of indentation rate whose magnitudes reflect differences in the rates of nucleation and propagation of dislocations within the crystal structures of HOIPs and IP. In conclusion, this contribution provides understanding that is critical for designing perovskite devices capable of withstanding mechanical deformations.« less

  8. K{sub 2}NaOsO{sub 5.5} and K{sub 3}NaOs{sub 2}O{sub 9}: The first osmium perovskites containing alkali cations at the 'A' site

    SciTech Connect

    Mogare, Kailash M.; Klein, Wilhelm; Jansen, Martin

    2012-07-15

    K{sub 2}NaOsO{sub 5.5} and K{sub 3}NaOs{sub 2}O{sub 9} were obtained from solid-state reactions of potassium superoxide, sodium peroxide and osmium metal at elevated oxygen pressures. K{sub 2}NaOsO{sub 5.5} crystallizes as an oxygen-deficient cubic double perovskite in space group Fm3{sup Macron }m with a=8.4184(5) A and contains isolated OsO{sub 6} octahedra. K{sub 3}NaOs{sub 2}O{sub 9} crystallizes hexagonally in P6{sub 3}/mmc with a=5.9998(4) A and c=14.3053(14) A. K{sub 3}NaOs{sub 2}O{sub 9} consists of face sharing Os{sub 2}O{sub 9} pairs of octahedra. According to magnetic measurements K{sub 2}NaOsO{sub 5.5} is diamagnetic, whereas K{sub 3}NaOs{sub 2}O{sub 9} displays strong antiferromagnetic coupling (T{sub N}=140 K), indicating enhanced magnetic interactions within the octahedral pair. - Graphical abstract: High oxidation states of Os, obtained by high oxygen pressure synthesis, are accommodated in double and triple perovskite matrices. K{sub 3}NaOs{sub 2}O{sub 9} displays enhanced magnetic interactions. Highlights: Black-Right-Pointing-Pointer New osmates containing highly oxidized Os were obtained by high O{sub 2} pressure synthesis. Black-Right-Pointing-Pointer High oxidation states of Os are accommodated in double and triple perovskite matrices. Black-Right-Pointing-Pointer Both compounds represent the first Os perovskites with an alkali metal at the A site. Black-Right-Pointing-Pointer K{sub 3}NaOs{sub 2}O{sub 9} displays enhanced magnetic interactions within the octahedral pair.

  9. Coupled Nd and B' spin ordering in the double perovskites Nd2NaB'O6 (B' = Ru, Os)

    SciTech Connect

    Aczel, Adam A; Bugaris, Dan; Yeon, Jeongho; Dela Cruz, Clarina R; Zur Loye, Hans-Conrad; Nagler, Stephen E

    2013-01-01

    We present a neutron powder diffraction study of the monoclinic double perovskite systems Nd$_2$NaB$'$O$_6$ (B$'$~$=$~Ru, Os), with magnetic atoms occupying both the A and B$'$ sites. Our measurements reveal coupled spin ordering between the Nd and B$'$ atoms with magnetic transition temperatures of 14~K for Nd$_2$NaRuO$_6$ and 16~K for Nd$_2$NaOsO$_6$. There is a Type I antiferromagnetic structure associated with the Ru and Os sublattices, with the ferromagnetic planes stacked along the c-axis and [110] direction respectively, while the Nd sublattices exhibit complex, canted antiferromagnetism with different spin arrangements in each system.

  10. It's All Business: A Site Visit Report on Working Order, Sharpsburg, Pennsylvania.

    ERIC Educational Resources Information Center

    Olney, Marjorie F.; Harris, Perri

    This report discusses the results of a case study of Working Order, a Pennsylvania program designed to develop entrepreneurs with and without disabilities by sharing the expertise, resources, and skills of small business owners. The strategy of the program is to invite competitive entrepreneurs, those who could likely produce and sell their…

  11. Elucidating the impact of A-site cation change on photocatalytic H2 and O2 evolution activities of perovskite-type LnTaON2 (Ln = La and Pr).

    PubMed

    Hojamberdiev, Mirabbos; Bekheet, Maged F; Hart, Judy N; Vequizo, Junie Jhon M; Yamakata, Akira; Yubuta, Kunio; Gurlo, Aleksander; Hasegawa, Masashi; Domen, Kazunari; Teshima, Katsuya

    2017-08-23

    Transition metal (oxy)nitrides with perovskite-type structures have been regarded as one of the promising classes of inorganic semiconductor materials that can be used in solar water splitting systems for the production of hydrogen as a renewable and storable energy carrier. The performance of transition metal (oxy)nitrides in solar water splitting is strongly influenced by the crystal structure-related dynamics of photogenerated charge carriers. Here, we have systematically assessed the influence of A-site cation exchange on the visible-light-induced photocatalytic H2 and O2 evolution activities, photoanodic response, and dynamics of photogenerated charge carriers of perovskite-type LnTaON2 (Ln = La and Pr). The structural refinement results reveal the orthorhombic Imma and Pnma structures for LaTaON2 and PrTaON2, respectively; the latter has a more distorted crystal structure from the ideal cubic perovskite due to the smaller size of Pr(3+) cations. Compared with LaTaON2, PrTaON2 exhibits lower photocatalytic H2 and O2 gas evolution activities and photoanodic response owing to an excessive amount of intrinsic defects associated with anionic vacancies and reduced tantalum species stemming from a long high-temperature nitridation process under reductive NH3 atmosphere. Transient absorption signals evidence the faster decay of photogenerated electrons (holes) in Pt (CoOx)-loaded LaTaON2 than that in Pt (CoOx)-loaded PrTaON2, consistent with the photocatalytic and photoelectrochemical performance of the two photocatalysts. This study suggests that in addition to selecting a suitable A-site cation, it is prerequisite to synthesize LnTaON2 (Ln = La and Pr) crystals with a low defect density to improve their photo-conversion efficiency for solar water splitting.

  12. Kitaev materials beyond iridates: Order by quantum disorder and Weyl magnons in rare-earth double perovskites

    NASA Astrophysics Data System (ADS)

    Li, Fei-Ye; Li, Yao-Dong; Yu, Yue; Paramekanti, Arun; Chen, Gang

    2017-02-01

    Motivated by the experiments on the rare-earth double perovskites, we propose a generalized Kitaev-Heisenberg model to describe the generic interaction between the spin-orbit-entangled Kramers doublets of the rare-earth moments. We carry out a systematic analysis of the mean-field phase diagram of this new model. In the phase diagram, there exist large regions with a continuous U (1 ) or O (3 ) degeneracy. Since no symmetry of the model protects such a continuous degeneracy, we predict that the quantum fluctuation lifts the continuous degeneracy and favors various magnetic orders in the phase diagram. From this order by quantum disorder mechanism, we further predict that the magnetic excitations of the resulting ordered phases are characterized by nearly gapless pseudo-Goldstone modes. We find that there exist Weyl magnon excitations for certain magnetic orders. We expect our prediction to inspire further study of Kitaev physics, the order by quantum disorder phenomenon, and topological spin-wave modes in the rare-earth magnets and the systems alike.

  13. Independent ordering of two interpenetrating magnetic sublattices in the double perovskite Sr2CoOsO6.

    PubMed

    Morrow, Ryan; Mishra, Rohan; Restrepo, Oscar D; Ball, Molly R; Windl, Wolfgang; Wurmehl, Sabine; Stockert, Ulrike; Büchner, Bernd; Woodward, Patrick M

    2013-12-18

    The insulating, fully ordered, double perovskite Sr2CoOsO6 undergoes two magnetic phase transitions. The Os(VI) ions order antiferromagnetically with a propagation vector k = (1/2, 1/2, 0) below TN1 = 108 K, while the high-spin Co(II) ions order antiferromagnetically with a propagation vector k = (1/2, 0, 1/2) below TN2 = 70 K. Ordering of the Os(VI) spins is accompanied by a structural distortion from tetragonal I4/m symmetry to monoclinic I2/m symmetry, which reduces the frustration of the face centered cubic lattice of Os(VI) ions. Density functional theory calculations show that the long-range Os-O-Co-O-Os and Co-O-Os-O-Co superexchange interactions are considerably stronger than the shorter Os-O-Co interactions. The poor energetic overlap between the 3d orbitals of Co and the 5d orbitals of Os appears to be responsible for this unusual inversion in the strength of short and long-range superexchange interactions.

  14. Synthesis, structure, and magnetic properties of novel B-site ordered double perovskites, SrLaMReO6 (M = Mg, Mn, Co and Ni).

    PubMed

    Thompson, Corey M; Chi, Lisheng; Hayes, John R; Hallas, Alannah M; Wilson, Murray N; Munsie, Timothy J S; Swainson, Ian P; Grosvenor, Andrew P; Luke, Graeme M; Greedan, John E

    2015-06-21

    Four new double perovskites, SrLaMReO(6) (M = Mg, Mn, Co, Ni) in which Re(5+) (5d(2)) is present, were prepared via conventional solid state reactions and characterized by X-ray and neutron powder diffraction, XANES, SQUID magnetometry, and muon spin relaxation (μSR). Synchrotron X-ray and neutron diffraction experiments confirmed that all compounds crystallize in the monoclinic P2(1)/n structure type, which consists of alternately corner-shared octahedra of MO(6) and ReO(6). Rietveld refinement results indicated anti-site mixing of less than 7% on the M/Re sites. Bond valence sum calculations (BVS) suggest all M and Re ions are 2+ and 5+, respectively, and for the Mn-containing phase this is also supported by XANES measurements. All of the materials are paramagnetic at room-temperature and their Curie-Weiss temperatures are positive (except for Mg) indicating net ferromagnetic interactions. No evidence for long-range magnetic order is evident in the dc magnetic susceptibility and μSR measurements for SrLaMgReO(6) to 2 K. The Mn-phase shows long-range order at T(C) = 190 K and neutron diffraction revealed a ferromagnetic structure with a refined net moment of ∼3.7μ(B). Both Co- and Ni-containing phases exhibit spin glass behavior at T(G) = 23 and 30 K, respectively, which is supported by neutron diffraction and a.c. susceptibility data. The structure and physical properties of these four new rhenium based ordered double perovskites are compared to the closely related "pillared perovskites", La(5)Re(3)MO(16), the isoelectronic Os(6+) (5d(2)) double perovskite Sr(2)CoOsO(6), and the Re(6+) (5d(1)) double perovskites, Sr(2)MReO(6), (M = Mg, Ca, Mn, Co, Ni).

  15. Superconducting double perovskite bismuth oxide prepared by a low-temperature hydrothermal reaction.

    PubMed

    Rubel, Mirza H K; Miura, Akira; Takei, Takahiro; Kumada, Nobuhiro; Mozahar Ali, M; Nagao, Masanori; Watauchi, Satoshi; Tanaka, Isao; Oka, Kengo; Azuma, Masaki; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro; Azharul Islam, A K M

    2014-04-01

    Perovskite-type structures (ABO3) have received significant attention because of their crystallographic aspects and physical properties, but there has been no clear evidence of a superconductor with a double-perovskite-type structure, whose different elements occupy A and/or B sites in ordered ways. In this report, hydrothermal synthesis at 220 °C produced a new superconductor with an A-site-ordered double perovskite structure, (Na(0.25)K(0.45))(Ba(1.00))3(Bi(1.00))4O12, with a maximum T(c) of about 27 K.

  16. Magnetic order and magnetoelectric properties of R2CoMn O6 perovskites (R =Ho , Tm, Yb, and Lu)

    NASA Astrophysics Data System (ADS)

    Blasco, J.; García-Muñoz, J. L.; García, J.; Subías, G.; Stankiewicz, J.; Rodríguez-Velamazán, J. A.; Ritter, C.

    2017-07-01

    We present a detailed study on the magnetic structure and magnetoelectric properties of several double perovskites R2CoMn O6 (R =Ho , Tm, Yb, and Lu). All of these samples show an almost perfect (˜94 %) ordering of C o2 + and M n4 + cations in the unit cell. Our research reveals that the magnetic ground state strongly depends on the R size. For samples with larger R (Ho and Tm), the ground state is formed by a ferromagnetic order (F type) of C o2 + and M n4 + moments, while R either remains mainly disordered (Ho) or is coupled antiferromagnetically (Tm) to the Co/Mn sublattice. For samples with smaller R (Yb or Lu), competitive interactions lead to the formation of an E -type arrangement for the C o2 + and M n4 + moments with a large amount of extended defects such as stacking faults. The Y b3 + is partly ordered at very low temperature. The latter samples undergo a metamagnetic transition from the E into the F type, which is coupled to a negative magnetodielectric effect. Actually, the real part of dielectric permittivity shows an anomaly at the magnetic transition for the samples exhibiting an E -type order. This anomaly is absent in samples with F -type order, and, accordingly, it vanishes coupled to the metamagnetic transition for R =Yb or Lu samples. At room temperature, the huge values of the dielectric constant reveal the presence of Maxwell-Wagner depletion layers. Pyroelectric measurements reveal a high polarization at low temperature, but the onset of pyroelectric current is neither correlated to the kind of magnetic ordering nor to the magnetic transition. Our study identified the pyroelectric current as thermally stimulated depolarization current and electric-field polarization curves show a linear behavior at low temperature. Therefore, no clear ferroelectric transition occurs in these compounds.

  17. Crystal, magnetic and electronic structures of 3d-5d ordered double perovskite Ba2CoReO6

    NASA Astrophysics Data System (ADS)

    Musa Saad H.-E., M.; Rammeh, N.

    2016-12-01

    A comprehensive study on crystal, magnetic and electronic structures of ordered double perovskite Ba2CoReO6 was carried out using X-ray powder diffraction (XRD) and superconducting quantum interference device (SQUID). Also, the density functional theory (DFT) calculations were performed by full potential linear muffin-tin orbital (FP-LMTO) method within the localized spin density approximation (LSDA+U) and generalized gradient approximation (GGA+U). At room temperature, the crystal structure of Ba2CoReO6 is face-centered cubic, space group Fm 3 bar m , containing an almost completely ordered arrangement of CoO6-ReO6 octahedra. Magnetic structure showed an antiferromagnetic (AF) behavior below TN=41 K. The magnetic and electronic structures are consistent with the electronic configurations Co2+(3d7)-Re6+(5d1) having a total spin magnetic moment of about 2.0 μB/f.u. DFT electronic structures predicted half-metallic yields from 3d-t2g↓ and 5d-t2g↓ through O2-.

  18. Commensurate structural modulation in the charge- and orbitally ordered phase of the quadruple perovskite (NaMn3)Mn4O12

    NASA Astrophysics Data System (ADS)

    Prodi, A.; Daoud-Aladine, A.; Gozzo, F.; Schmitt, B.; Lebedev, O.; van Tendeloo, G.; Gilioli, E.; Bolzoni, F.; Aruga-Katori, H.; Takagi, H.; Marezio, M.; Gauzzi, A.

    2014-11-01

    By means of synchrotron x-ray and electron diffraction, we studied the structural changes at the charge order transition TCO=176 K in the mixed-valence quadruple perovskite (NaMn3)Mn4O12. Below TCO we find satellite peaks indicating a commensurate structural modulation with the same propagation vector q =(1 /2 ,0 ,-1 /2 ) of the CE magnetic structure that orders at low temperatures, similarly to the case of simple perovskites such as La0.5Ca0.5MnO3. In the present case, the modulated structure, together with the observation of a large entropy change at TCO, gives evidence of a rare case of full Mn3 +/Mn4 + charge and orbital order, consistent with the Goodenough-Kanamori model.

  19. Structure and magnetism of the A site scandium perovskite (Sc0.94Mn0.06)Mn0.65Ni0.35O3 synthesized at high pressure.

    PubMed

    Thomas, Chris I; Suchomel, Matthew R; Duong, Giap V; Fogg, Andrew M; Claridge, John B; Rosseinsky, Matthew J

    2014-04-13

    Scandium perovskite (Sc0.94Mn0.06)Mn0.65Ni0.35O3, synthesized at high pressure and high temperature, has a triclinic structure (space group ) at room temperature and ambient pressure with a √2ap×√2ap×2ap structure with α≈90(°),β≈89(°),γ≈90(°). Magnetic measurements show that the material displays Curie-Weiss behaviour above 50 K with C=2.11 emu K mol(-1) (μeff=4.11 μB per formula unit) and θ=-95.27 K. Bond valence sum analysis of the crystal structure shows that manganese is present in three different oxidation states (+2, +3, +4), with the +2 oxidation state on the A site resulting in a highly tilted perovskite structure (average tilt 21.2(°) compared with 15.7(°) calculated for LaCaMnNbO6), giving the formula (Sc3+(0.94)Mn2+(0.06))(Mn4+(0.41)Mn3+(0.09))(Mn3+(0.15)Ni2+(0.35))O3.

  20. High-Pressure Synthesis and Ferrimagnetic Ordering of the B-Site-Ordered Cubic Perovskite Pb2FeOsO6.

    PubMed

    Zhao, Qing; Liu, Min; Dai, Jianhong; Deng, Hongshan; Yin, Yunyu; Zhou, Long; Yang, Junye; Hu, Zhiwei; Agrestini, Stefano; Chen, Kai; Pellegrin, Eric; Valvidares, Manuel; Nataf, Lucie; Baudelet, François; Tjeng, L H; Yang, Yi-Feng; Jin, Changqing; Long, Youwen

    2016-10-03

    Pb2FeOsO6 was prepared for the first time by using high-pressure and high-temperature synthesis techniques. This compound crystallizes into a B-site-ordered double-perovskite structure with cubic symmetry Fm3̅m, where the Fe and Os atoms are orderly distributed with a rock-salt-type manner. Structure refinement shows an Fe-Os antisite occupancy of about 16.6%. Structural analysis and X-ray absorption spectroscopy both demonstrate the charge combination to be Pb2Fe(3+)Os(5+)O6. A long-range ferrimagnetic transition is found to occur at about 280 K due to antiferromagnetic interactions between the adjacent Fe(3+) and Os(5+) spins with a straight (180°) Fe-O-Os bond angle, as confirmed by X-ray magnetic circular-dichroism measurements. First-principles theoretical calculations reveal the semiconducting behavior as well as the Fe(3+)(↑)Os(5+)(↓) antiferromagnetic coupling originating from the superexchange interactions between the half-filled 3d orbitals of Fe and t2g orbitals of Os.

  1. Energy-polarization behaviors of AA'BB'O6 perovskites with double rock-salt order

    NASA Astrophysics Data System (ADS)

    Roy, Anindya; Vanderbilt, David

    2010-03-01

    Using first-principles methods, we study the energy-polarization relation of double perovskites AA'BB'O6 where atoms in both A and B sites are arranged in rock-salt order. The high-symmetry structure in this case is the tetrahedral F43m space group. If a ferroelectric instability occurs, the energy-vs.-polarization landscape E(P) will tend to have minima for P along tetrahedral directions leading to a rhombohedral space group R3m, with two different values of spontaneous polarization and associated energy along opposite body-diagonal directions; or along Cartesian directions, leading to orthorhombic space group Imm2. We search for polar soft modes at the γ point of the high-symmetry F43m structure and analyze its eigenvectors to identify ferroelectric instabilities, which we find in CaBaTiZrO6, KCaZrNbO6 and PbSnTiZrO6. The results of the first-principle calculations are modeled with a Landau-Devonshire expansion that is truncated at either 4th or 5th order in P, and its predictions are found to agree favorably with our calculation. The 5th-order calculation improves the agreement further except in PSTZ. Recently, synthesis of SrCaTiMnO6 in rock-salt order has been reported.footnotetextJ.L Blok, G. Rijnders and D.H.A. Blank, private communication. Unfortunately, preliminary results do not seem to indicate any polarized structure.

  2. Ferrimagnetism as a consequence of cation ordering in the perovskite LaSr2Cr2SbO9

    NASA Astrophysics Data System (ADS)

    Hunter, Emily C.; Battle, Peter D.; Paria Sena, Robert; Hadermann, Joke

    2017-04-01

    A polycrystalline sample of LaSr2Cr2SbO9 has been synthesised using a standard ceramic method and characterized by x-ray and neutron diffraction, magnetometry and electron microscopy. The perovskite-related compound crystallises in the triclinic space group I 1 ̅ with unit cell parameters of a=5.5344(6) Å, b=5.5562(5) Å, c=7.8292(7) Å, α=89.986(12)°, β=90.350(5)° and γ=89.926(9)° at room temperature. The two crystallographically-distinct, six-coordinate cation sites are occupied by Cr3+ and Sb5+ in ratios of 0.868(2):0.132(2) and 0.462(2):0.538(2). Ac and dc magnetometry revealed that LaSr2Cr2SbO9 is ferrimagnetic below 150 K with a magnetisation of 1.25 μB per formula unit in 50 kOe at 5 K. Neutron diffraction showed that the cations on the two sites order in a G-type arrangement with a mean Cr3+ moment of 2.17(1) μB at 5 K, consistent with a magnetisation of 1.32 μB per formula unit.

  3. 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

    2016-01-25

    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.

  4. 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

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

    SciTech Connect

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

    2015-03-01

    The magnetic susceptibility, crystal and magnetic structures, and electronic structure of double perovskite Sr2ScOsO6 are reported. Using both neutron and x-ray powder diffraction we find that the crystal structure is monoclinic P21/n from 3.5 to 300 K. Magnetization measurements indicate an antiferromagnetic transition at TN=92 K, one of the highest transition temperatures of any double perovskite hosting only one magnetic ion. Type I antiferromagnetic order is determined by neutron powder diffraction, with an Os moment of only 1.6(1) muB, close to half the spin-only value for a crystal field split 5d electron state with t2g^3 ground state. Density functional calculations show that this reduction is largely the result of strong Os-O hybridization, with spin-orbit coupling responsible for only a ~0.1 muB reduction in the moment.

  6. Magnetic ordering and dielectric relaxation in the double perovskite YBaCuFeO5.

    PubMed

    Lai, Yen-Chung; Du, Chao-Hung; Lai, Chun-Hao; Liang, Yu-Hui; Wang, Chin-Wei; Rule, Kirrily C; Wu, Hung-Cheng; Yang, Hung-Duen; Chen, Wei-Tin; Shu, G J; Chou, F-C

    2017-04-12

    Using magnetization, dielectric constant, and neutron diffraction measurements on a high quality single crystal of YBaCuFeO5 (YBCFO), we demonstrate that the crystal shows two antiferromagnetic transitions at [Formula: see text] K and [Formula: see text] K, and displays a giant dielectric constant with a characteristic of the dielectric relaxation at T N2. It does not show the evidence of the electric polarization for the crystal used for this study. The transition at T N1 corresponds with a paramagnetic to antiferromagnetic transition with a magnetic propagation vector doubling the unit cell along three crystallographic axes. Upon cooling, at T N2, the commensurate spin ordering transforms to a spiral magnetic structure with a propagation vector of ([Formula: see text] [Formula: see text] [Formula: see text]), where [Formula: see text], [Formula: see text], and [Formula: see text] are odd, and the incommensurability δ is temperature dependent. Around the transition boundary at T N2, both commensurate and incommensurate spin ordering coexist.

  7. Magnetic ordering and dielectric relaxation in the double perovskite YBaCuFeO5

    NASA Astrophysics Data System (ADS)

    Lai, Yen-Chung; Du, Chao-Hung; Lai, Chun-Hao; Liang, Yu-Hui; Wang, Chin-Wei; Rule, Kirrily C.; Wu, Hung-Cheng; Yang, Hung-Duen; Chen, Wei-Tin; Shu, G. J.; Chou, F.-C.

    2017-04-01

    Using magnetization, dielectric constant, and neutron diffraction measurements on a high quality single crystal of YBaCuFeO5 (YBCFO), we demonstrate that the crystal shows two antiferromagnetic transitions at {{T}N1}∼ 475 K and {{T}N2}∼ 175 K, and displays a giant dielectric constant with a characteristic of the dielectric relaxation at T N2. It does not show the evidence of the electric polarization for the crystal used for this study. The transition at T N1 corresponds with a paramagnetic to antiferromagnetic transition with a magnetic propagation vector doubling the unit cell along three crystallographic axes. Upon cooling, at T N2, the commensurate spin ordering transforms to a spiral magnetic structure with a propagation vector of (\\frac{h}{2} \\frac{k}{2} \\frac{l}{2}+/- δ ), where h , k , and l are odd, and the incommensurability δ is temperature dependent. Around the transition boundary at T N2, both commensurate and incommensurate spin ordering coexist.

  8. Magnetic ordering in perovskites A1 - xMnO3 + y (A=La, Bi, rare earth ion) (abstract)

    NASA Astrophysics Data System (ADS)

    Troyanchuk, I. O.; Kasper, N. V.; Szymczak, H.; Nabialek, A.

    1997-04-01

    In order to clarify the mechanism of exchange interactions in orthomanganites with perovskite structure a magnetic study of parent compounds as a function of stoichiometry has been made. It was shown that the LaMnO2.99 is a weak ferromagnet with TN=147 K while LaMnO3.13 and La0.9MnO3.05 are ferromagnets with TC=160 and 240 K, respectively. The magnetic data indicate that the mixed magnetic state involving ferro- and antiferromagnetic domains is realized in the intermediate range of oxygen content. The RMnO3+y (R=Nd, Sm, Eu, Gd) are inhomogeneous antiferromagnets. The temperatures of start of magnetic moments freezing inside ferromagnetic clusters depend slightly on stoichiometry and for y˜0 are equal 83, 65, 47, and 22 K, respectively. The coercive field for LaMnO3 is 6 kOe at 4.2 K while that for EuMnO3 is much higher—26 kOe. It is worth noting that the Neel temperatures of RMnO3(R=Eu, Gd, Tb, Dy) are estimated to be about 40 K independently of the type of rare-earth ion. Magnetic moments of Gd, Tb, and Dy in the rare-earth sublattice are antiferromagnetically ordered below 6-7 K. Applying external fields induces the antiferromagnet-ferromagnet transition in rare-earth sublattice. Hcr at 2 K for RMnO3(R=Gd, Tb, Dy) are measured to be about 5, 12, and 10 kOe, respectively. In contrast to rare-earth compounds, the BiMnO3 is ferromagnet below 98 K. The deviation from stoichiometry as well as replacement of Bi ions by Sr, Ca, or La ions leads to the suppression of the long-range ferromagnetic order. Magnetic properties are discussed in terms of super exchange interactions between manganese ions via oxygen taking into account the 3d-orbital ordering that occurs in LaMnO3 and TbMnO3 at 400 and 1200°C, respectively.

  9. Methodologies for high efficiency perovskite solar cells.

    PubMed

    Park, Nam-Gyu

    2016-01-01

    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.

  10. 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.

  11. Mesostructured perovskite solar cells based on highly ordered TiO2 network scaffold via anodization of Ti thin film.

    PubMed

    Huang, Aibin; Zhu, Jingting; Zheng, Jianyun; Yu, Yu; Liu, Yan; Yang, Songwang; Bao, Shanhu; Lei, Lei; Jin, Ping

    2017-02-03

    An anodized TiO2 interconnected network was fabricated and utilized as a mesoporous scaffold and electron transporter in perovskite solar cells. By modifying the synthesis parameters, the morphological features of the interconnected TiO2 nanostructures can be widely tuned and precisely controlled. The functional properties of the anodized TiO2 network are found to be severely influenced by morphology as well as the extent of oxidation. The device with the optimized TiO2 network exhibits superior electron extraction and transferability, resulting in conspicuous enhancement of the photocurrent and power conversion efficiency (PCE). This work proposes a promising and facile method for improving the performance of perovskite solar cells.

  12. Mesostructured perovskite solar cells based on highly ordered TiO2 network scaffold via anodization of Ti thin film

    NASA Astrophysics Data System (ADS)

    Huang, Aibin; Zhu, Jingting; Zheng, Jianyun; Yu, Yu; Liu, Yan; Yang, Songwang; Bao, Shanhu; Lei, Lei; Jin, Ping

    2017-02-01

    An anodized TiO2 interconnected network was fabricated and utilized as a mesoporous scaffold and electron transporter in perovskite solar cells. By modifying the synthesis parameters, the morphological features of the interconnected TiO2 nanostructures can be widely tuned and precisely controlled. The functional properties of the anodized TiO2 network are found to be severely influenced by morphology as well as the extent of oxidation. The device with the optimized TiO2 network exhibits superior electron extraction and transferability, resulting in conspicuous enhancement of the photocurrent and power conversion efficiency (PCE). This work proposes a promising and facile method for improving the performance of perovskite solar cells.

  13. Relaxor or classical ferroelectric behavior in A-site substituted perovskite type Ba 1- x(Sm 0.5Na 0.5) xTiO 3

    NASA Astrophysics Data System (ADS)

    Abdelmoula, N.; Chaabane, H.; Khemakhem, H.; Von der Mühll, R.; Simon, A.

    2006-08-01

    New ferroelectric ceramics of ABO 3 perovskite type were synthetized in the Ba 1- x(Sm 0.5Na 0.5) xTiO 3 system by solid state reaction technique. The effect of the replacement of barium by samarium and sodium in the A cationic site on structural and physical properties was investigated. These compounds crystallize with tetragonal or cubic symmetry. The material is classical ferroelectric for 0⩽x⩽0.1 and x⩾0.5, and present a relaxor behavior for 0.2⩽x<0.4. The dielectric behavior depends upon the cationic disorder in the A-site and the cell size. Small rate substitution allows a ferroelectric-paraelectric transition. For higher rate of substitution the possible random position of the Sm-Na cations brings to a relaxor state and when the substitution rate x becomes higher than 0.5, the material comes back to a ferroelectric state due to the reduced cell size. Some of these new compositions are of interest for applications due to their physical properties and environmentally friendly character.

  14. Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3.

    PubMed

    Marini, C; Noked, O; Kantor, I; Joseph, B; Mathon, O; Shuker, R; Kennedy, B J; Pascarelli, S; Sterer, E

    2016-02-03

    Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb(5+) towards Nb(4+) above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ∼14.5 GPa.

  15. Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3

    NASA Astrophysics Data System (ADS)

    Marini, C.; Noked, O.; Kantor, I.; Joseph, B.; Mathon, O.; Shuker, R.; Kennedy, B. J.; Pascarelli, S.; Sterer, E.

    2016-02-01

    Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb5+ towards Nb4+ above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ˜14.5 GPa.

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

    SciTech Connect

    Vasala, Sami; Yamauchi, Hisao; Karppinen, Maarit

    2014-12-15

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

  17. Crystallographic and magnetic structure of the perovskite-type compound BaFeO2.5: unrivaled complexity in oxygen vacancy ordering.

    PubMed

    Clemens, Oliver; Gröting, Melanie; Witte, Ralf; Perez-Mato, J Manuel; Loho, Christoph; Berry, Frank J; Kruk, Robert; Knight, Kevin S; Wright, Adrian J; Hahn, Horst; Slater, Peter R

    2014-06-16

    We report here on the characterization of the vacancy-ordered perovskite-type structure of BaFeO2.5 by means of combined Rietveld analysis of powder X-ray and neutron diffraction data. The compound crystallizes in the monoclinic space group P2(1)/c [a = 6.9753(1) Å, b = 11.7281(2) Å, c = 23.4507(4) Å, β = 98.813(1)°, and Z = 28] containing seven crystallographically different iron atoms. The coordination scheme is determined to be Ba7(FeO4/2)1(FeO3/2O1/1)3(FeO5/2)2(FeO6/2)1 = Ba7Fe([6])1Fe([5])2Fe([4])4O17.5 and is in agreement with the (57)Fe Mössbauer spectra and density functional theory based calculations. To our knowledge, the structure of BaFeO2.5 is the most complicated perovskite-type superstructure reported so far (largest primitive cell, number of ABX2.5 units per unit cell, and number of different crystallographic sites). The magnetic structure was determined from the powder neutron diffraction data and can be understood in terms of "G-type" antiferromagnetic ordering between connected iron-containing polyhedra, in agreement with field-sweep and zero-field-cooled/field-cooled measurements.

  18. High magnetic ordering temperature in the perovskites Sr4-xLaxFe3ReO12 (x= 0.0, 1.0, 2.0)

    SciTech Connect

    Hodges, Jason P; Retuerto, Maria; Greenblatt, Martha; Li, Man-Rong; Croft, Mark; Ramanujachary, Kandalam V.; Go, Yong Bok; Nowik, Israel; Hadermann, Joke; Herber, R. H.; Ignatov, Alexander Y

    2012-01-01

    A series of perovskites Sr4-xLaxFe3ReO12 (x = 0.0, 1.0, 2.0) has been prepared by wet chemistry methods. The structure analyses by powder x-ray, neutron diffraction and electron microscopy show that these compounds adopt simple perovskite structures without cation ordering over the B sites: tetragonal (I4/mcm) for x = 0.0 and 1.0 and orthorhombic (Pbmn) for x = 2.0. The oxidation state of the cations in the compound with x = 0.0 appear to be Fe3+/4+ and Re7+ and decrease for both with La substitution as evidenced by x-ray absorption spectroscopy. All the compounds are antiferromagnetically ordered above room temperature, as demonstrated by M ssbauer spectroscopy and the magnetic structures, which were determined by powder neutron diffraction. The substitution of Sr by La strongly affects the magnetic properties with an increase of TN up to ~ 750 K.

  19. Crystal structure, thermal expansion and high-temperature electrical conductivity of A-site deficient La{sub 2−z}Co{sub 1+y}(Mg{sub x}Nb{sub 1−x}){sub 1−y}O{sub 6} double perovskites

    SciTech Connect

    Shafeie, S.; Dreyer, B.; Awater, R.H.P; Golod, T.; Grins, J.; Biendicho, J.J.; Istomin, S.Ya.; Svensson, G.

    2015-09-15

    New La-deficient double perovskites with P2{sub 1}/n symmetry, La{sub ∼1.90}(Co{sup 2+}{sub 1−x}Mg{sup 2+}{sub x})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} with x=0, 0.13 and 0.33, and La{sub 2}(Co{sup 2+}{sub 1/2}Mg{sup 2+}{sub 1/2}) (Co{sup 3+}{sub 1/2}Nb{sup 5+}{sub 1/2})O{sub 6} were prepared by solid state reaction at 1450 °C. Their crystal structures were refined using time-of-flight neutron powder diffraction data. Our results show that certain cations such as Nb{sup 5+}, with very strong B–O bonds in the perovskite structure, can induce A-site vacancies in double perovskites. Upon heating in N{sub 2} gas atmosphere at 1200 °C ∼1% O atom vacancies are formed together with a partial reduction of the Co{sup 3+} content. The average thermal expansion coefficient between 25 and 900 °C of La{sub 1.90}(Co{sup 2+}{sub 2/3}Mg{sup 2+}{sub 1/3})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} was determined to be 17.4 ppm K{sup −1}. Four-point electronic conductivity measurements showed that the compounds are semiconductors, with conductivities varying between 3.7·10{sup −2} and 7.7·10{sup −2} S cm{sup −1} at 600 °C and activation energies between 0.77 and 0.81 eV. Partial replacement of La{sup 3+} with Sr{sup 2+} does not lead to any increase of conductivity, while replacement of Mg{sup 2+} with Cu{sup 2+} in La{sub 1.9}CoCu{sub 1/3}Nb{sub 2/3}O{sub 6} and La{sub 1.8}CoCu{sub 1/2}Nb{sub 1/2}O{sub 6} leads to ∼100 times larger conductivities at 600 °C, 0.35 and 1.0 S cm{sup −1}, respectively, and lower activation energies, 0.57 and 0.73 eV, respectively. - Highlights: • Double perovskites, P2{sub 1}/n, La{sub 2−z}(Co{sup 2+}{sub 1−x}Mg{sup 2+}{sub x})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} have been synthesized. • Crystal structures have been refined using neutron powder diffraction data. • Strong Nb–O bond and size ordering of Mg{sup 2+}/Co{sup 2+} and Nb{sup 5+}/Co{sup ~3+} leads to La-deficiency. • The

  20. Anomalous dispersion X-ray diffraction study of Pb/Bi ordering/disordering states in PbTiO3-based perovskite oxides.

    PubMed

    Lin, Kun; Wang, Na; You, Li; Li, Qiang; Kato, Kenichi; Chen, Jun; Deng, Jinxia; Xing, Xianran

    2017-01-17

    Synchrotron radiation-based anomalous dispersion X-ray powder diffraction (ADSPD) was carried out to reveal the Pb/Bi ordering/disordering states in a series of PbTiO3-based negative thermal expansion materials (1 - x)PbTiO3 - xBiFeO3 (x = 0.1, 0.3, 0.5) and (1 - x)PbTiO3 - xBi(Zn1/2Ti1/2)O3 (x = 0.1, 0.2, 0.3). It gives strong evidence of the disordered Pb/Bi distributions in these compositions, which is consistent with electron diffraction studies. Combined with binding energy calculation, we show that the disordered nature of Pb/Bi distributions is likely to be attributed to the similar electron configurations of Pb(2+) and Bi(3+) as well as their comparable coordinate environments in perovskite structures. The results of this study may be helpful to better understand the structure-property relationship in Pb/Bi-containing perovskites and are useful for further developing underlying physics in relevant materials.

  1. High-pressure synthesis, structural and complex magnetic properties of the ordered double perovskite Pb2NiReO6.

    PubMed

    Stoyanova-Lyubenova, Teodora; Dos santos-García, Antonio J; Urones-Garrote, Esteban; Torralvo, María José; Alario-Franco, Miguel Á

    2014-01-21

    The ordered double perovskite Pb2NiReO6 has been prepared at 6 GPa and temperatures ranging from 1273 to 1373 K. Its crystal structure determined by X-ray powder diffraction and selected area electron diffraction shows monoclinic symmetry with centrosymmetric space group I2/m (a = 5.6021(1) Å, b = 5.6235(1) Å, c = 7.9286(1) Å and β = 90.284°(1)). High angle annular dark field microscopy studies reveal the existence of compositional microdomains. The compound displays a re-entrant spin-glass transition from a ferrimagnetic ordering below T(N) ~ 37 K between the Re(+5) and Ni(+3) (high spin configuration) magnetic sublattices to a spin-glass configuration. Magnetic field dependent magnetization measurements revealed wasp-waisted hysteresis loops at 5 K. These shaped features originate from the antiferromagnetic/ferromagnetic (AFM/FM) competing interactions.

  2. Double perovskite Sr{sub 2}FeMoO{sub 6-x}N{sub x} (x=0.3, 1.0) oxynitrides with anionic ordering

    SciTech Connect

    Retuerto, M.; Calle, C. de la; Martinez-Lope, M.J.; Porcher, F.; Menendez, N.; Alonso, J.A.

    2012-01-15

    Two new oxynitride double perovskites of composition Sr{sub 2}FeMoO{sub 6-x}N{sub x} (x=0.3, 1.0) have been synthesized by annealing precursor powders obtained by citrate techniques in flowing ammonia at 750 Degree-Sign C and 650 Degree-Sign C, respectively. The polycrystalline samples have been characterized by chemical analysis, x-ray and neutron diffraction (NPD), Moessbauer spectroscopy and magnetic measurements. They exhibit a tetragonal structure with a=5.5959(1) A, c=7.9024(2) A, V=247.46(2) A{sup 3} for Sr{sub 2}FeMoO{sub 5.7}N{sub 0.3}; and a=5.6202(2) A, c=7.9102(4) A, V=249.85(2) A{sup 3} for Sr{sub 2}FeMoO{sub 5}N; space group I4/m, Z=2. The nitridation process seems to extraordinarily improve the long-range Fe/Mo ordering, achieving 95% at moderate temperatures of 750 Degree-Sign C. The analysis of high resolution NPD data, based on the contrast existing between the scattering lengths of O and N, shows that both atoms are located at (O,N)2 anion substructure corresponding to the basal ab plane of the perovskite structure, whereas the O1 site is fully occupied by oxygen atoms. The evolution of the Left-Pointing-Angle-Bracket Fe-O Right-Pointing-Angle-Bracket and Left-Pointing-Angle-Bracket Mo-O Right-Pointing-Angle-Bracket distances suggests a shift towards a configuration close to Fe{sup 4+}(3d{sup 4}, S=2):Mo{sup 5+}(4d{sup 1}, S=1/2). The magnetic susceptibility shows a ferrimagnetic transition with a reduced saturation magnetization compared to Sr{sub 2}FeMoO{sub 6}, due to the different nature of the magnetic double exchange interactions through Fe-N-Mo-N-Fe paths in contrast to the stronger Fe-O-Mo-O-Fe interactions. Also, the effect observed by low-temperature NPD seems to reduce the ordered Fe moments and enhance the Mo moments, in agreement with the evolution of the oxidation states, thus decreasing the saturation magnetization. - Graphical Abstract: We have synthesized and studied the new oxinitride double perovskites Sr{sub 2}FeMoO{sub 6-x

  3. Structural and magnetic study of the cation-ordered perovskites Ba{sub 2-} {sub x} Sr {sub x} ErMoO{sub 6}

    SciTech Connect

    Cussen, Edmund J.

    2007-02-15

    A series of perovskite phases have been prepared from the appropriate carbonates and oxides by heating under reducing conditions at temperatures up to 1300 deg. C. Complete ordering between ErO{sub 6} and MoO{sub 6} octahedra and a disordered distribution of Sr{sup 2+} and Ba{sup 2+} occur in all compounds. Neutron powder diffraction experiments show that the substitution of Sr{sup 2+} into Ba{sub 2}ErMoO{sub 6} introduces a progressive reduction in symmetry from Fm3-barm (x=0) to I4/m (x=0.5, 0.8) to P2{sub 1}/n (x=1.25, 1.75, 2.0). Magnetic susceptibility measurements indicate that all of these compounds show Curie-Weiss paramagnetism and that for x<1.25 this behaviour persists down to 2 K. The monoclinically distorted compounds show magnetic transitions at low temperature and neutron diffraction has confirmed the presence of long-range antiferromagnetic order below 2.5 and 4 K in Ba{sub 0.25}Sr{sub 1.75}ErMoO{sub 6} and Sr{sub 2}ErMoO{sub 6}, respectively. Ba{sub 0.75}Sr{sub 1.25}ErMoO{sub 6}, Ba{sub 0.25}Sr{sub 1.75}ErMoO{sub 6} and Sr{sub 2}ErMoO{sub 6} do not undergo structural distortion on cooling from room temperature. - Graphical abstract: Introduction of Sr{sup 2+} into the double perovskite Ba{sub 2}ErMoO{sub 6} introduces increasingly large distortions from cubic symmetry and permits antiferromagnetic order at T {sub N}{<=}4 K.

  4. An x-ray diffraction and Raman spectroscopy investigation of A-site substituted perovskite compounds: the (Na1- xKx)0.5Bi0.5TiO3 (0≤ x≤1) solid solution

    NASA Astrophysics Data System (ADS)

    Kreisel, J.; Glazer, A. M.; Jones, G.; Thomas, P. A.; Abello, L.; Lucazeau, G.

    2000-04-01

    The (Na1 - x Kx )0.5 Bi0.5 TiO3 perovskite solid solution is investigated using x-ray diffraction (XRD) and Raman spectroscopy in order to follow the structural evolution between the end members Na0.5 Bi0.5 TiO3 (rhombohedral at 300 K) and K0.5 Bi0.5 TiO3 (tetragonal at 300 K). The Raman spectra are analysed with special regard to the hard modes and suggest the existence of nano-sized Bi3+ TiO3 and (Na1 - 2x K2x )+ TiO3 clusters. The complementary use of XRD and Raman spectroscopy suggests, in contrast to previous reported results, that the rhombohedral icons/Journals/Common/leftrightarrow" ALT="leftrightarrow" ALIGN="TOP"/> tetragonal phase transition goes through an intermediate phase, located at 0.5icons/Journals/Common/le" ALT="le" ALIGN="TOP"/> xicons/Journals/Common/le" ALT="le" ALIGN="TOP"/> 0.80. The structural character of the intermediate phase is discussed in the light of sub- and super-group relations.

  5. Chalcogenide Perovskites for Solar Energy Harvesting

    NASA Astrophysics Data System (ADS)

    Perera, Samanthe

    Methylammonium Lead halide perovskites have recently emerged as a promising candidate for realizing high efficient low cost photovoltaic modules. Charge transport properties of the solution processed halide perovskites are comparable to some of the existing absorbers used in the current PV industry which require sophisticated processing techniques. Due to this simple processing required to achieve high efficiencies, halide perovskites have become an active field of research. As a result, perovskite solar cells are rapidly reaching towards theoretical efficiency limit of close to 30%. It's believed that ionicity inherent to perovskite materials is one of the contributing factors for the excellent charge transport properties of perovskites. Despite the growing interest for solar energy harvesting purposes, these halide perovskites have serious limitations such as toxicity and instability that need to be addressed in order to commercialize the solar cells incorporating them. This dissertation focuses on a new class of ionic semiconductors, chalcogenide perovskites for solar energy harvesting purposes. Coming from the family perovskites they are expected to have same excellent charge transport properties inherent to perovskites due to the ionicity. Inspired by few theoretical studies on chalcogenide perovskites, BaZrS3 and its Ti alloys were synthesized by sulfurizing the oxide counterpart. Structural characterizations have confirmed the predicted distorted perovskite phase. Optical characterizations have verified the direct band gap suitable for thin film single junction solar cells. Anion alloying was demonstrated by synthesizing oxysulfides with widely tunable band gap suitable for applications such as solid state lighting and sensing.

  6. Critical behavior and long-range ferromagnetic order in perovskite manganite Nd0.55Sr0.45MnO3

    NASA Astrophysics Data System (ADS)

    Xu, Lisha; Fan, Jiyu; Shi, Yangguang; Zhu, Yan; Bärner, Klaus; Yang, Changping; Shi, Daning

    2015-10-01

    The critical behavior of perovskite manganite Nd0.55Sr0.45MnO3 has been investigated based on the static magnetization measurement around the paramagnetic-ferromagnetic transition temperature 273 K. A large critical exponent β = 0.4816 and a small one γ = 1.0846 have been obtained by calculating the magnetic-field dependence of the magnetic-entropy change and the Widom scaling relation. These critical exponents not only obey the scaling hypothesis, but also corroborate the results obtained from the Kouvel-Fisher method. In comparison with the values given by standard models, these obtained exponents are very close to those expected from the mean-field model (β = 0.5 and γ = 1 ) and its magnetic-coupling type belongs to nearly long-range interaction. We suggest that the A-site spin disorder and localized magnetic phase competition are the main reasons for the actual critical exponents to show a slight deviation from the theoretical model.

  7. Applying Capacitive Energy Storage for In Situ Manipulation of Magnetization in Ordered Mesoporous Perovskite-Type LSMO Thin Films.

    PubMed

    Reitz, Christian; Wang, Di; Stoeckel, Daniela; Beck, Andre; Leichtweiß, Thomas; Hahn, Horst; Brezesinski, Torsten

    2017-04-03

    Mesostructured non-silicate materials, particularly mixed-metal oxides, are receiving much attention in recent years due to their potential for numerous applications. Via polymer-templating method, perovskite-type lanthanum strontium manganese oxide (La1-xSrxMnO3, LSMO, with x ≈ 0.15 to 0.30) with a continuous 3D cubic network of 23 nm pores is prepared in thin film form for the first time. Characterization results from grazing incidence X-ray scattering, X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, and electron microscopy and tomography show that the dip-coated sol-gel-derived films are of high quality in terms of composition and morphology, and that they are stable to over 700 °C. Magnetic and magnetotransport measurements demonstrate that the material with the highest strontium concentration is ferromagnetic at room temperature and exhibits metallic resistivity behavior below 270 K. Besides, it behaves differently from epitaxial layers (e.g., enhanced low-field magnetoresistance effect). It is also shown that carriers (electrons and holes) can be induced into the polymer-templated mesostructured LSMO films via capacitive double-layer charging. This kind of electrostatic doping utilizing ionic liquid gating causes large relative changes in magnetic susceptibility at room temperature and is a viable technique to tune the magnetic phase diagram in situ.

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

    PubMed

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

    2016-06-01

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

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

    SciTech Connect

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

    2014-11-14

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

  10. Absence of significant structural changes near the magnetic ordering temperature in small-ion rare earth perovskite RMnO3

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  11. Absence of significant structural changes near the magnetic ordering temperature in small-ion rare earth perovskite RMnO3.

    PubMed

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

    2014-12-10

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

  12. Polaronic Charge Carrier-Lattice Interactions in Lead Halide Perovskites.

    PubMed

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

    2017-10-09

    Almost ten years after the renaissance of the popular perovskite-type semiconductors based on lead salts with the general formula AMX3 (A=organic or inorganic cation; M=divalent metal; X=halide), many facets of photophysics continue to puzzle researchers. In this Minireview, light is shed on the low mobilities of charge carriers in lead halide perovskites with special focus on the lattice properties at non-zero temperature. The polar and soft lattice leads to pronounced electron-phonon coupling, limiting carrier mobility and retarding recombination. We propose that the proper picture of excited charge carriers at temperature ranges that are relevant for device operations is that of a polaron, with Fröhlich coupling constants between 1<α<3. Under the aspect of light-emitting diode application, APbX3 perovskite show moderate second order (bimolecular) recombination rates and high third-order (Auger) rate constants. It has become apparent that this is a direct consequence of the anisotropic polar A-site cation in organic-inorganic hybrid perovskites and might be alleviated by replacing the organic moiety with an isotropic cation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. A neutron diffraction study of structural distortion and magnetic ordering in the cation-ordered perovskites Ba{sub 2}Nd{sub 1−x}Y{sub x}MoO{sub 6}

    SciTech Connect

    Collins, Oonagh M.; Cussen, Edmund J.

    2013-04-15

    The cation ordered perovskites Ba{sub 2}Nd{sub 1−x}Y{sub x}MoO{sub 6} (0.04≤x≤0.35) have been synthesised by solid-state techniques under reducing conditions at temperatures up to 1350 °C. Rietveld analyses of X-ray and neutron powder diffraction data show that these compounds adopt a tetragonally distorted perovskite structure. The tetragonal distortion is driven by the bonding requirements of the Ba{sup 2+} cation that occupies the central interstice of the perovskite; this cation would be underbonded if these compounds retained the cubic symmetry exhibited by the prototypical structure. The size and charge difference between the lanthanides and Mo{sup 5+} lead to complete ordering of the cations to give a rock-salt ordering of Nd{sup 3+}/Y{sup 3+}O{sub 6} and MoO{sub 6} octahedra. The I4/m space group symmetry is retained on cooling the x=0.1, 0.2 and 0.35 samples to low temperature ca. 2 K. Ba{sub 2}Nd{sub 0.90}Y{sub 0.10}MoO{sub 6} undergoes a gradual distortion of the MoO{sub 6} units on cooling from room temperature to give two long trans bonds (2.001(2) Å) along the z-direction and four shorter apical bonds (1.9563(13) Å) in the xy-plane. This distortion of the MoO{sub 6} units stabilises the 4d{sup 1} electron in the d{sub xz} and d{sub yz} orbitals whilst the d{sub xy} orbital is increased in energy due to the contraction of the Mo–O bonds in the xy-plane. This bond extension along z is propagated through the structure and gives a negative thermal expansion of −13×10{sup −6} K{sup −1} along c. The overall volumetric thermal expansion is positive due to conventional expansion along the other two crystallographic axes. With increasing Y{sup 3+} content this distortion is reduced in x=0.2 and eliminated in x=0.35 which contains largely regular MoO{sub 6} octahedra. The x=0.1 and x=0.2 show small peaks in the neutron diffraction profile due to long range antiferromagnetic order arising from ordered moments of ca. 2 μ{sub B}. - Graphical

  14. Perovskite fever

    NASA Astrophysics Data System (ADS)

    2014-09-01

    Staggering increases in the performance of organic-inorganic perovskite solar cells have renewed the interest in these materials. However, further developments and the support from academic and industrial partners will hinge on the reporting of accurate efficiency values.

  15. Magnetodielectric effects in A -site cation-ordered chromate spinels Li M C r4O8 (M =Ga and In)

    NASA Astrophysics Data System (ADS)

    Saha, Rana; Fauth, Francois; Avdeev, Maxim; Kayser, Paula; Kennedy, Brendan J.; Sundaresan, A.

    2016-08-01

    We report the occurrence of a magnetodielectric effect and its correlation with structure and magnetism in the A -site ordered chromate spinel oxides Li M C r4O8 (M =Ga , In). In addition to magnetic and dielectric measurements, temperature dependent synchrotron and neutron diffraction experiments have been carried out for the Ga compound. The results are compared and contrasted with that of a corresponding conventional B -site magnetic chromate spinel oxide, ZnC r2O4 . Like ZnC r2O4 , the A -site ordered chromate spinels exhibit a magnetodielectric effect at the magnetic ordering temperature (TN˜13 -15 K ), resulting from magnetoelastic coupling through a spin Jahn-Teller effect. While the presence of a broad magnetic anomaly, associated with a short-range magnetic ordering (TSO˜45 K ) in ZnC r2O4 , does not cause any dielectric anomaly, a sharp change in dielectric constant has been observed in LiInC r4O8 at the magnetic anomaly, which is associated with the opening of a spin gap (TSG˜60 K ). Contrary to the In compound, a broad dielectric anomaly exists at the onset of short-range antiferromagnetic ordering (TSO˜55 K ) in LiGaC r4O8 . The differences in dielectric behavior of these compounds have been discussed in terms of breathing distortion of the C r4 tetrahedra.

  16. Occurrence of magnetoelectric effect correlated to the Dy order in Dy{sub 2}NiMnO{sub 6} double perovskite

    SciTech Connect

    Masud, Md G.; Dey, K.; Ghosh, A.; Majumdar, S.; Giri, S.

    2015-08-14

    Magnetic, dielectric, and ac conductivity as well as room temperature structural and Raman studies are performed on double perovskite Dy{sub 2}NiMnO{sub 6}. The crystal structure of the compound adopts monoclinic P2{sub 1}/n space group, where alternate Mn and Ni distorted octahedral are arranged in anti-phase a{sup −} a{sup −} b{sup +} order in Glazer notation. Magnetization studies show two magnetic transitions around 100 K and 20 K which are related to the ordering of transition and rare earth cations moment, respectively. Temperature dependent dielectric permittivity shows Havriliak-Negami type thermally activated dielectric relaxation. The ac conductivity at different temperature is found to follow Jonscher power law behavior. Time-temperature scaling of the conductivity spectra reveals that the charge transport dynamics is independent of temperature. Intriguingly, an anomaly in the dielectric constant is observed close to the order of Dy moment which indicates intrinsic magnetoelectric coupling. The hybridization between Dy and Ni/Mn is suggested to be correlated with the magnetoelectric coupling.

  17. Rocksalt versus layered ordering in double perovskites: A case study with La2CuSnO6 and La2CuIrO6

    NASA Astrophysics Data System (ADS)

    Samanta, Kartik; Saha-Dasgupta, Tanusri

    2017-06-01

    The nature of ordering of B and B ' transition metal ions in double perovskite compounds of general composition A2BB 'O6 is an important topic, since the physical properties crucially depend on it. In the present study, considering the specific cases of La2CuSnO6 and La2CuIrO6 , we carry out first-principles calculations with an aim to obtain microscopic understanding on this issue. Our study reveals the presence of Jahn-Teller distorted B ion, like Cu2 + helps in band energy stabilization of the layered ordering over the rocksalt ordering. However, introduction of magnetism may reverse this trend, especially in the presence of a second magnetic ion at B ' site, which may introduce a strong superexchange path involving B-O-B ' , as found in the case of La2CuIrO6 . We further find the spin-orbit coupling at Ir site drives the La2CuIrO6 compound to be a spin-orbit assisted Mott insulator.

  18. Spontaneous bidirectional ordering of CH3NH3+ in lead iodide perovskites at room temperature: The origins of the tetragonal phase

    PubMed Central

    Deretzis, Ioannis; Di Mauro, Bruno N.; Alberti, Alessandra; Pellegrino, Giovanna; Smecca, Emanuele; La Magna, Antonino

    2016-01-01

    CH3NH3PbI3 is a hybrid organic-inorganic material with a perovskite structure and a temperature-dependent polymorphism whose origins are still unclear. Here we perform ab initio molecular dynamics simulations in order to investigate the structural properties and atom dynamics of CH3NH3PbI3 at room temperature. Starting from different initial configurations, we find that a single-crystalline system undergoes a spontaneous ordering process which brings the ions to alternately point towards the center of two out of the six faces of the cubic framework, i.e. towards the 〈100〉 and 〈010〉 directions. This bidirectional ordering gives rise to a preferential distortion of the inorganic lattice on the a-b plane, shaping the observed tetragonal symmetry of the system. The process requires tens of picoseconds for CH3NH3PbI3 supercells with just eight ions. PMID:27079383

  19. Magnetic ordering in double perovskites R2CoMnO6 (R = Y , Tb) investigated by high resolution neutron spectroscopy

    NASA Astrophysics Data System (ADS)

    Chatterji, Tapan; Frick, Bernhard; Nair, Harikrishnan S.

    2012-07-01

    We have investigated low energy nuclear spin excitations in double perovskite compounds R2CoMnO6 (R=Y, Tb) by inelastic neutron scattering with a high resolution back-scattering spectrometer. We observed inelastic signals at about 2.1 μeV for Y2CoMnO6 and also for Tb2CoMnO6 at T = 2 K in both energy-loss and energy-gain sides. We interpret these inelastic peaks to be due to the transitions between the hyperfine split nuclear levels of the 59Co nucleus. The inelastic peaks move towards the central elastic peak and finally merge with it at the magnetic ordering temperature TC. The energy of the low energy excitations decreases continuously and becomes zero at TC ≈ 75 K for Y2CoMnO6 and TC ≈ 100 K for Tb2CoMnO6. For Tb2CoMnO6, which contains magnetic rare earth ions, additional quasielastic scattering due presumably to the fluctuations of large Tb magnetic moments was observed. The present study reveals the magnetic ordering of the Co sublattice. The results of this investigation along with that obtained by us for other compounds indicate the presence of unquenched orbital moments in some of the Co compounds.

  20. Structural distortions, orbital ordering and physical properties of double perovskite R2CoMnO6 calculated by first-principles.

    PubMed

    Zhou, Hai Yang; Chen, Xiang Ming

    2017-04-12

    The structural distortions, orbital ordering, magnetic and electronic properties of double perovskite R2CoMnO6 (R  =  rare-earth element) have been systematically calculated by first-principles. Structural distortions, including Co-O and Mn-O bond length splitting, the antiferroelectric motions of R ions, the tilting of octahedral (the resulted Co-O-Mn bond angle) are obviously affected by the rare-earth ions' radius. The bond length splitting behavior of Co-O and Mn-O are rather different because of the Jahn-Teller active ion Co(2+) and the Jahn-Teller nonactive ion Mn(4+). Taking Gd2CoMnO6 as an example, the t 2g orbitals of Co ions are predicted to be orbital ordered. That is, the spin down channel of d xz orbital for one Co ion and d yz orbital for another Co ion are basically vacant. Finally, the physical properties, including the magnetic Curie temperature and electronic band gap of R2CoMnO6 are almost linear dependent on the average value of cos(2) θ (θ is the Co-O-Mn exchange-angle).

  1. Structural distortions, orbital ordering and physical properties of double perovskite R2CoMnO6 calculated by first-principles

    NASA Astrophysics Data System (ADS)

    Zhou, Hai Yang; Chen, Xiang Ming

    2017-04-01

    The structural distortions, orbital ordering, magnetic and electronic properties of double perovskite R2CoMnO6 (R  =  rare-earth element) have been systematically calculated by first-principles. Structural distortions, including Co–O and Mn–O bond length splitting, the antiferroelectric motions of R ions, the tilting of octahedral (the resulted Co–O–Mn bond angle) are obviously affected by the rare-earth ions’ radius. The bond length splitting behavior of Co–O and Mn–O are rather different because of the Jahn–Teller active ion Co2+ and the Jahn–Teller nonactive ion Mn4+. Taking Gd2CoMnO6 as an example, the t 2g orbitals of Co ions are predicted to be orbital ordered. That is, the spin down channel of d xz orbital for one Co ion and d yz orbital for another Co ion are basically vacant. Finally, the physical properties, including the magnetic Curie temperature and electronic band gap of R2CoMnO6 are almost linear dependent on the average value of cos2 θ (θ is the Co–O–Mn exchange-angle).

  2. Sr(4 + n)Mn(3+)(4)Mn(4+)(n)O(10 + 3n): a new homologous series of oxygen-vacancy-ordered perovskites built from Mn(3+)O(5) pyramids and Mn(4+)O(6) octahedra.

    PubMed

    Suescun, Leopoldo; Dabrowski, Bogdan

    2008-04-01

    A new homologous series of oxygen-vacancy-ordered perovskites with the formula Sr_{4+n}Mn;{3+}_4Mn;{4+}_nO_{10+3n} is proposed based on the structural trends found for the recently described Sr(4)Mn(4)O(10), Sr(5)Mn(5)O(13) and Sr(7)Mn(7)O(19) compounds. These compounds correspond to n = 0 (Sr(4)Mn;{3+}_4O(10)), n = 1 (Sr(5)Mn;{3+}_4Mn(4+)O(13)) and n = 3 (Sr(7)Mn;{3+}_4Mn;{4+}_3O(19)) members of the series. A linear set of four Mn(3+)O(5) pyramids placed on the ab plane and pointing along the +x, -y, +y, -x directions defines the n = 0 building block for the series. The nth members can be constructed from blocks containing four pyramids and n Mn(4+)O(6) octahedra with 2/m symmetry. Compounds in the related systems CaMnO(x) and LaCuO(x), containing Mn(3+) and Cu(2+) pyramids and Mn(4+) and Cu(3+) octahedra have also been found to be members of the series. The size and charge of the A-site cation and the apical distortion of the pyramidally coordinated B-site cation are shown to be important factors in the stabilization of certain members of the series. A qualitative explanation for the absence of some of the possible members of the series is presented based on these factors.

  3. Study of magnetic ordering in the perovskite manganites Pr0.6Sr0.4CrxMn1-xO3

    NASA Astrophysics Data System (ADS)

    Ge, X. S.; Wu, L. Q.; Li, S. Q.; Li, Z. Z.; Tang, G. D.; Qi, W. H.; Zhou, H. J.; Xue, L. C.; Ding, L. L.

    2017-04-01

    Powder samples of the ABO3 perovskite manganites Pr0.6Sr0.4CrxMn1-xO3 (0.00≤x≤0.30) were synthesized using the sol-gel method. X-ray diffraction analyses showed that all the samples had a single-phase orthorhombic structure. By analyzing magnetic parameters on the basis of the O2p itinerant electron model, we found that there are two magnetic transition temperatures, TCM and TCP, corresponding to changes in the magnetic ordering for the Mn and Pr cations, respectively. The magnetic moments of Mn3+ and Cr3+ cations within the B sublattice show canted ferromagnetic coupling, and the magnetic moments of the Pr cations within the A sublattice also show canted ferromagnetic coupling. However, the total magnetic moment of the A sublattice shows antiferromagnetic coupling against that of the B sublattice. The assumption of the canted ferromagnetic coupling within the B sublattice was confirmed using magnetoresistance experimental results.

  4. Mapping chemical/structural order in double perovskite Sr2-xGdxMnTiO6 by atomic resolution electron microscopy

    NASA Astrophysics Data System (ADS)

    Alvarez, Inmaculada; Biskup, Neven; Lopez, Maria; Garcia-Hernandez, Mar; Veiga, Luisa; Varela, Maria; UCM Collaboration; ORNL Collaboration; CSIC Collaboration

    2013-03-01

    We report on visualizing the chemical and structural order of double perovskite Sr2-xGdxMnTiO6. The antisite disorder of Mn and Ti is detected even at atomic scale at all x, resulting in Mn-rich and Ti-rich regions. For x ?0.75, the majority of manganese ions are in Mn3+ state and are centered in Jahn-Teller distorted MnO6octahedra. The Fourier transformation of atomic resolution images along the [110] zone axis reveals a superstructure that corresponds to the tilting of oxygen octahedra and that doubles the unit cell along [001]c. This superstructure is spatially inhomogeneous and coincides with the regions where B-site ion (Mn/Ti) is displaced along the [110] direction. We discuss these findings in the frame of possible local ferroelectricity and in the light of strong electroresistance observed in Sr1.25Gd0.75MnTiO6. Research at ORNL supported by the U.S. DOE-BES, Materials Sciences and Engineering Division, and also by ORNL's ShaRE User Program (sponsored by DOE-BES). Research at UCM supported by the ERC Starting Investigator Award and MAT2010-20117.

  5. La2SrCr2O7: Controlling the Tilting Distortions of n = 2 Ruddlesden-Popper Phases through A-Site Cation Order.

    PubMed

    Zhang, Ronghuan; Abbett, Brian M; Read, Gareth; Lang, Franz; Lancaster, Tom; Tran, T Thao; Halasyamani, P Shiv; Blundell, Stephen J; Benedek, Nicole A; Hayward, Michael A

    2016-09-06

    Structural characterization by neutron diffraction, supported by magnetic, SHG, and μ(+)SR data, reveals that the n = 2 Ruddlesden-Popper phase La2SrCr2O7 adopts a highly unusual structural configuration in which the cooperative rotations of the CrO6 octahedra are out of phase in all three Cartesian directions (ΦΦΦz/ΦΦΦz; a(-)a(-)c(-)/a(-)a(-)c(-)) as described in space group A2/a. First-principles DFT calculations indicate that this unusual structural arrangement can be attributed to coupling between the La/Sr A-site distribution and the rotations of the CrO6 units, which combine to relieve the local deformations of the chromium-oxygen octahedra. This coupling suggests new chemical "handles" by which the rotational distortions or A-site cation order of Ruddlesden-Popper phases can be directed to optimize physical behavior. Low-temperature neutron diffraction data and μ(+)SR data indicate La2SrCr2O7 adopts a G-type antiferromagnetically ordered state below TN ∼ 260 K.

  6. Perovskite Nanowire Extrusion.

    PubMed

    Oener, Sebastian Z; Khoram, Parisa; Brittman, Sarah; Mann, Sander A; Zhang, Qianpeng; Fan, Zhiyong; Boettcher, Shannon W; Garnett, Erik C

    2017-10-10

    The defect tolerance of halide perovskite materials has led to efficient optoelectronic devices based on thin-film geometries with unprecedented speed. Moreover, it has motivated research on perovskite nanowires because surface recombination continues to be a major obstacle in realizing efficient nanowire devices. Recently, ordered vertical arrays of perovskite nanowires have been realized, which can benefit from nanophotonic design strategies allowing precise control over light propagation, absorption, and emission. An anodized aluminum oxide template is used to confine the crystallization process, either in the solution or in the vapor phase. This approach, however, results in an unavoidable drawback: only nanowires embedded inside the AAO are obtainable, since the AAO cannot be etched selectively. The requirement for a support matrix originates from the intrinsic difficulty of controlling precise placement, sizes, and shapes of free-standing nanostructures during crystallization, especially in solution. Here we introduce a method to fabricate free-standing solution-based vertical nanowires with arbitrary dimensions. Our scheme also utilizes AAO; however, in contrast to embedding the perovskite inside the matrix, we apply a pressure gradient to extrude the solution from the free-standing templates. The exit profile of the template is subsequently translated into the final semiconductor geometry. The free-standing nanowires are single crystalline and show a PLQY up to ∼29%. In principle, this rapid method is not limited to nanowires but can be extended to uniform and ordered high PLQY single crystalline perovskite nanostructures of different shapes and sizes by fabricating additional masking layers or using specifically shaped nanopore endings.

  7. Novel Properties of Atomically Arranged Perovskites

    NASA Astrophysics Data System (ADS)

    Dabrowski, B.; Kolesnik, S.; Chmaissem, O.; Suescun, L.; Mais, J.

    2007-01-01

    Perovskites AMO3-δ attain unique electronic, magnetic, ferroelectric, thermoelectric, mixed-conducting, and other functional properties through selection of the A- and M-site ions, their fractions, ionic sizes and valences, spin states, and orbital orderings, as well as the oxygen content and vacancy ordering. We illustrate here our systematic exploration of the effects of composition, temperature, pressure, and oxygen content on the thermodynamic stability and magnetic properties for La1-x-ySrxBayMnO3 manganites. Parameters controlling magnetic transitions are identified through examples of single-valent compounds of RMnO3 (the Mn-O-Mn bond angles that can be equivalently described in terms of the tolerance factor) and Sr1-xCaxMnO3 (the tolerance factor and disorder described in terms of the variance of A-site ion sizes), and the mixed-valent La0.5Sr0.5-yBayMnO3 (the tolerance factor, variance of sizes, and the local strains described in terms of the elongated Mn-O bonds). By using an example of kinetically stable, atomically-ordered layered-perovskites we show that improved useful properties, such as the increase in the Curie temperature TC and enhancement of colossal magneto-resistive effect at room temperature, can be achieved through decreases in structural distortions such as variance of sizes and local strains.

  8. Order-disorder in In{sup 3+} perovskites: The example of A(In{sub 2/3}B''{sub 1/3})O{sub 3} (A=Ba, Sr; B''=W, U)

    SciTech Connect

    Larregola, S.A. Alonso, J.A.; Pinacca, R.M.; Viola, M.C.; Pedregosa, J.C.

    2008-10-15

    We describe the preparation and structural characterization of four In-containing perovskites from neutron powder diffraction (NPD) and X-ray powder diffraction (XRPD) data. Sr{sub 3}In{sub 2}B''O{sub 9} and Ba(In{sub 2/3}B''{sub 1/3})O{sub 3} (B''=W, U) were synthesized by standard ceramic procedures. The crystal structure of the W-containing perovskites and Ba(In{sub 2/3}U{sub 1/3})O{sub 3} have been revisited based on our high-resolution NPD and XRPD data, while for the new U-containing perovskite Sr{sub 3}In{sub 2}UO{sub 9} the structural refinement was carried out from high-resolution XRPD data. At room temperature, the crystal structure for the two Sr phases is monoclinic, space group P2{sub 1}/n, where the In atoms occupy two different sites Sr{sub 2}[In]{sub 2d}[In{sub 1/3}B''{sub 2/3}]{sub 2c}O{sub 6}, with a=5.7548(2) A, b=5.7706(2) A, c=8.1432(3) A, {beta}=90.01(1){sup o} for B''=W and a=5.861(1) A, b=5.908(1) A, c=8.315(2) A, {beta}=89.98(1){sup o} for B''=U. The two phases with A=Ba should be described in a simple cubic perovskite unit cell (S.G. Pm3-bar m) with In and B'' distributed at random at the octahedral sites, with a=4.16111(1) A and 4.24941(1) A for W and U compounds, respectively. - Graphical abstract: The structure of the new uranium-based double perovskite Sr{sub 3}In{sub 2}UO{sub 9} is described and the true symmetry of the other title compounds are revisited. The presence of long-range ordering in the Sr samples, by contrast with the Ba perovskites, is related with the smaller unit cell and B-B distances in the Sr oxides, promoting the electrostatic repulsions between highly charged W{sup 6+} and U{sup 6+} cations as driving force for the long-range B-site ordering.

  9. Structural and complex AC impedance spectroscopic studies of A 2CoNbO 6 (A = Sr, Ba) ordered double perovskites

    NASA Astrophysics Data System (ADS)

    Bashir, J.; Shaheen, R.

    2011-05-01

    Powder X-ray diffraction has been employed to study the crystal structures of Sr 2CoNbO 6 ( SCNO) and Ba 2CoNbO 6 ( BCNO) double perovskites. Rietveld fit to the X-ray diffraction data showed that Ba 2CoNbO 6 perovskites was monoclinic with space group P2 1/ n whereas Sr 2CoNbO 6 was found to be tetragonal with space group I4/ m. Like other cobalt based perovskites, both materials exhibit high values of dielectric constant at room temperature and low frequencies. Room temperature impedance and modulus spectra, measured over the 1 Hz to 10 MHz, reveal two relaxation processes with different relaxation times which were attributed to the grain and grain boundaries.

  10. Peculiar ferrimagnetism associated with charge order in layered perovskite GdBaMn2O5.0.

    PubMed

    Taskin, A A; Ando, Yoichi

    2007-05-18

    The magnetic properties of GdBaMn2O5.0, which exhibits charge ordering, are studied from 2 to 400 K using single crystals. In a small magnetic field applied along the easy axis, the magnetization M shows a temperature-induced reversal which is sometimes found in ferrimagnets. In a large magnetic field, on the other hand, a sharp change in the slope of M(T) coming from an unusual turnabout of the magnetization of the Mn sublattices is observed. Those observations are essentially explained by a molecular field theory which highlights the role of delicate magnetic interactions between Gd3+ ions and the antiferromagnetically coupled Mn2+/Mn3+ sublattices.

  11. Magnetic ordering in perovskites A{sub 1{minus}x}MnO{sub 3+y} (A=La, Bi, rare earth ion) (abstract)

    SciTech Connect

    Troyanchuk, I.O.; Kasper, N.V.; Szymczak, H.; Nabialek, A.

    1997-04-01

    In order to clarify the mechanism of exchange interactions in orthomanganites with perovskite structure a magnetic study of parent compounds as a function of stoichiometry has been made. It was shown that the LaMnO{sub 2.99} is a weak ferromagnet with T{sub N}=147 K while LaMnO{sub 3.13} and La{sub 0.9}MnO{sub 3.05} are ferromagnets with T{sub C}=160 and 240 K, respectively. The magnetic data indicate that the mixed magnetic state involving ferro- and antiferromagnetic domains is realized in the intermediate range of oxygen content. The RMnO{sub 3+y} (R=Nd, Sm, Eu, Gd) are inhomogeneous antiferromagnets. The temperatures of start of magnetic moments freezing inside ferromagnetic clusters depend slightly on stoichiometry and for y{approximately}0 are equal 83, 65, 47, and 22 K, respectively. The coercive field for LaMnO{sub 3} is 6 kOe at 4.2 K while that for EuMnO{sub 3} is much higher{emdash}26 kOe. It is worth noting that the Neel temperatures of RMnO{sub 3} (R=Eu, Gd, Tb, Dy) are estimated to be about 40 K independently of the type of rare-earth ion. Magnetic moments of Gd, Tb, and Dy in the rare-earth sublattice are antiferromagnetically ordered below 6{endash}7 K. Applying external fields induces the antiferromagnet{endash}ferromagnet transition in rare-earth sublattice. H{sub cr} at 2 K for RMnO{sub 3} (R=Gd, Tb, Dy) are measured to be about 5, 12, and 10 kOe, respectively. In contrast to rare-earth compounds, the BiMnO{sub 3} is ferromagnet below 98 K. The deviation from stoichiometry as well as replacement of Bi ions by Sr, Ca, or La ions leads to the suppression of the long-range ferromagnetic order. Magnetic properties are discussed in terms of super exchange interactions between manganese ions via oxygen taking into account the 3d-orbital ordering that occurs in LaMnO{sub 3} and TbMnO{sub 3} at 400 and 1200{degree}C, respectively. {copyright} {ital 1997 American Institute of Physics.}

  12. Orbital Ordering and the Cooperative Jahn-Teller Effect in Single Crystals of the Magnetic Perovskite La7/8Sr1/8MnO3

    NASA Astrophysics Data System (ADS)

    Gordon, I.; Wagner, P.; Moshchalkov, V. V.; Bruynseraede, Y.; Pinsard, L.; Revcolevschi, A.

    In the low-doped magnetic perovskite La7/8Sr1/8MnO3, a strong coupling exists between crystal structure and magnetic and electronic properties. At room temperature, the material is in a paramagnetic-semiconducting state, showing a dynamic Jahn-Teller (DJT) ordering of the Mn3+ ions. Below TJT=269 K however, the crystal goes into a cooperative Jahn-Teller (CJT) state, exhibiting antiferrodistorsive orbital ordering of the MnO6 octahedra. This leads to an increase in resistivity by a factor of 2 and to a drop of the paramagnetic susceptibility by about 20% [Physica B 155 (1989) 362; Phys. Rev. Lett. 71 (1993) 2331]. Around TC=188 K, a ferromagnetic transition occurs while the CJT effect becomes gradually weaker. Below TC the sample is metallic-like and shows a considerable colossal negative magnetoresistance (CMR) effect. Finally, the material goes into a charge-ordered, insulating state below TCO=147 K where the CJT effect completely vanishes. When crossing the phase boundary from the DJT to the CJT state, the resistivity shows a jump-like increase by a factor of roughly 2.15. This results from a frustration of the charge transport at the onset of orbital ordering. By assuming that each Mn4+ ion is surrounded only by Mn3+ nearest-neighbors and by taking into account only charge transport along the principal axes, the square-diagonals and the cube-diagonals, we are able to calculate a jump ratio of 2.26, corresponding well to the experimental value. The CJT transition also causes a sudden decrease in the magnetic moment, which has been studied by performing field-dependent SQUID measurements around TJT. Since the crystal is in a paramagnetic state around TJT, the magnetization M scales with the Brillouin function [beta](J), where J is the spin of small ferromagnetic clusters. Fitting the magnetization data with the Brillouin function results in a CJT-induced shrinking of magnetic clusters from roughly four Mn ions to three Mn ions. These cluster sizes can also be

  13. Rapid and robust spatiotemporal dynamics of the first-order phase transition in crystals of the organic-inorganic perovskite (C12H25NH3)2PbI4

    PubMed Central

    Yangui, Aymen; Sy, Mouhamadou; Li, Liang; Abid, Younes; Naumov, Panče; Boukheddaden, Kamel

    2015-01-01

    The dynamics of the thermally induced first-order structural phase transition in a high-quality single crystal of the organic-inorganic perovskite (C12H25NH3)2PbI4 was investigated by optical microscopy. The propagation of the straight phase front (habit plane) during the phase transition along the cooling and heating pathways of the thermal hysteresis was observed. The thermochromic character of the transition allowed monitoring of the thermal dependence of average optical density and aided the visualization of the interface propagation. The thermal hysteresis loop is 10 K wide, and the interface velocity is constant at V ≈ 1.6 mm s–1. The transition is accompanied with sizeable change in crystal size, with elongation of ~6% along the b axis and compression of ~ –2% along the a axis, in excellent agreement with previously reported X-ray diffraction data. The progression of the habit plane is at least 160 times faster than in spin-crossover materials, and opens new prospects for organic-inorganic perovskites as solid switching materials. Moreover, the crystals of (C12H25NH3)2PbI4 are unusually mechanically robust and present excellent resilience to thermal cycling. These hitherto unrecognized properties turn this and possibly similar hybrid perovskites into perspective candidates as active medium for microscopic actuation. PMID:26568147

  14. Rapid and robust spatiotemporal dynamics of the first-order phase transition in crystals of the organic-inorganic perovskite (C12H25NH3)2PbI4

    NASA Astrophysics Data System (ADS)

    Yangui, Aymen; Sy, Mouhamadou; Li, Liang; Abid, Younes; Naumov, Panče; Boukheddaden, Kamel

    2015-11-01

    The dynamics of the thermally induced first-order structural phase transition in a high-quality single crystal of the organic-inorganic perovskite (C12H25NH3)2PbI4 was investigated by optical microscopy. The propagation of the straight phase front (habit plane) during the phase transition along the cooling and heating pathways of the thermal hysteresis was observed. The thermochromic character of the transition allowed monitoring of the thermal dependence of average optical density and aided the visualization of the interface propagation. The thermal hysteresis loop is 10 K wide, and the interface velocity is constant at V ≈ 1.6 mm s-1. The transition is accompanied with sizeable change in crystal size, with elongation of ~6% along the b axis and compression of ~ -2% along the a axis, in excellent agreement with previously reported X-ray diffraction data. The progression of the habit plane is at least 160 times faster than in spin-crossover materials, and opens new prospects for organic-inorganic perovskites as solid switching materials. Moreover, the crystals of (C12H25NH3)2PbI4 are unusually mechanically robust and present excellent resilience to thermal cycling. These hitherto unrecognized properties turn this and possibly similar hybrid perovskites into perspective candidates as active medium for microscopic actuation.

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

    SciTech Connect

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

    2015-05-07

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

  16. Cationic ordering and role of the B-site lanthanide(III) and molybdenum(V) cations on the structure and magnetism of double perovskites Sr{sub 2}LnMoO{sub 6}

    SciTech Connect

    Pinacca, R.M.; Larrégola, S.A.; López, C.A.; Pedregosa, J.C.; Pomjakushin, Vladimir; Sánchez, R.D.; Alonso, J.A.

    2015-06-15

    Highlights: • Five new double perovskites of formula Sr{sub 2}LnMoO{sub 6} were synthesized. • All the samples crystallize in the monoclinic P2{sub 1}/n space group. • Strong reducing conditions were used in order to stabilized Mo(V) cations. • A complete ordering between the rare earth and molybdenum ions was observed. • Magnetism agrees with the crystal distortions observed from Rietveld analysis. - Abstract: We describe the preparation, crystal structure determination and magnetic properties of a new series of ordered double perovskite oxides Sr{sub 2}LnMoO{sub 6} (Ln = Eu, Gd, Dy, Ho, Er, Yb) with Mo{sup 5+} and Ln{sup 3+} electronic configurations. These compounds have been obtained by solid state reaction under reducing conditions in order to stabilize Mo{sup 5+} cations. Structural characterization by XRPD and NPD was performed when Ln = Ho, Er, Yb and just XRPD for absorbing Ln = Eu, Gd, Dy. At room temperature, an excellent Rietveld fit was obtained for all the samples in a monoclinic symmetry, space group P2{sub 1}/n, with long-range ordering of Ln and Mo atoms. Magnetic susceptibility measurements show that some of these materials present magnetic ordering below 25 K and the determined effective magnetic moments are consistent with those expected for the pair Ln{sup 3+}–Mo{sup 5+}. All the phases have negative values​​ of the Weiss temperature indicating dominance of antiferromagnetic interactions.

  17. Breathing Pyrochlore Lattice Realized in the A-Site Ordered Spinel Oxides LiGaCr4O8 and LiInCr4O8

    NASA Astrophysics Data System (ADS)

    Okamoto, Yoshihiko

    2014-03-01

    A Cr spinel oxide ACr2O4 with a nonmagnetic A2+ ion at the tetrahedral site provides an interesting playground for studying magnetic frustration in a pyrochlore lattice made of Cr3+ ions with an S = 3/2 spin. We found a novel type of frustrated lattice called ``breathing'' pyrochlore lattice, which is made of Cr3+ ions in two A-site ordered spinel oxides, LiGaCr4O8 and LiInCr4O8. Because of the large size mismatch between Li+ and Ga3+/In3+ ions, they alternately occupy the tetrahedral sites so as to form a Zinc Blende lattice. This transforms the conventional pyrochlore lattice into an alternating array of small and large tetrahedra, while keeping their shapes regular. LiGaCr4O8, with a lesser degree of alternation, shows similar magnetic properties to the conventional Cr spinel oxides such as ZnCr2O4. In contrast, LiInCr4O8 shows a spin-gap behavior in its magnetic susceptibility caused by a large alternation of magnetic interaction in the more breathing pyrochlore lattice. This suggests that LiInCr4O8 exists in a proximity to an exotic singlet ground state based on a tetramer singlet formed in the smaller tetrahedron, although it finally goes to a magnetically ordered state below 13 K, which may be triggered by a structural transition. We will also present NMR and neutron scattering measurements carried out to elucidate the nature of these compounds, and our recent results on solid solutions between the two compounds.

  18. Studies on polymorphic sequence during the formation of the 1:1 ordered perovskite-type BaCa(0.335)M(0.165)Nb(0.5)O(3-δ) (M = Mn, Fe, Co) using in situ and ex situ powder X-ray diffraction.

    PubMed

    Kan, Wang Hay; Lussier, Joey; Bieringer, Mario; Thangadurai, Venkataraman

    2014-10-06

    Here, we report a synthetic strategy to control the B-site ordering of the transition metal-doped perovskite-type oxides with the nominal formula of BaCa(0.335)M(0.165)Nb(0.5)O(3-δ) (M = Mn, Fe, Co). Variable temperature (in situ) and ex situ powder X-ray diffraction (PXRD), selected area electron diffraction (SAED), energy dispersive X-ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FTIR), scanning/transmission electron microscopy (SEM/TEM), and thermogravimetic analysis (TGA) were used to understand the B-site ordering as a function of temperature. The present study shows that BaCa(0.335)M(0.165)Nb(0.5)O(3-δ) crystallizes in the B-site disordered primitive perovskite (space group s.g. Pm3̅m) at 900 °C in air, which can be converted into the B-site 1:2 ordered perovskite (s.g. P3̅m1) at 1200 °C and the B-site 1:1 ordered perovskite phase (s.g. Fm3̅m) at 1300 °C. However, the reverse reaction is not feasible when the temperature is reduced. FTIR revealed that no carbonate species were present in all three polymorphs. The chemical stability of the investigated perovskites in CO2 and H2 highly depends on the B-site cation ordering. For example, TGA confirmed that the B-site disordered primitive perovskite phase is more readily reduced in dry and wet 10% H2/90% N2 and is less stable in pure CO2 at elevated temperature, compared to the B-site 1:1 ordered perovskite-type phase of the same nominal composition.

  19. Enhancement of Photoinduced Charge-Order Melting via Anisotropy Control by Double-Pulse Excitation in Perovskite Manganites: Pr_{0.6}Ca_{0.4}MnO_{3}.

    PubMed

    Yada, H; Ijiri, Y; Uemura, H; Tomioka, Y; Okamoto, H

    2016-02-19

    To control the efficiency of photoinduced charge-order melting in perovskite manganites, we performed femtosecond pump-probe spectroscopy using double-pulse excitation on Pr_{0.6}Ca_{0.4}MnO_{3}. The results revealed that the transfer of the spectral weight from the near-infrared to infrared region by the second pump pulse is considerably enhanced by the first pump pulse and that the suppression of crystal anisotropy, that is, the decrease of long-range lattice deformations due to the charge order by the first pump pulse is a key factor to enhance the charge-order melting. This double-pulse excitation method can be applied to various photoinduced transitions in complex materials with electronic and structural instabilities.

  20. B-site ordered double perovskite LaBa1-xSrxZnSbO6 (0 ≤ x ≤ 1): Sr(2+)-doping-induced symmetry evolution and structure-luminescence correlations.

    PubMed

    Jiang, Pengfei; Zhou, Zhengyang; Gao, Wenliang; Cong, Rihong; Yang, Tao

    2016-03-07

    The study of perovskites has been active for a long time. Here, we rationally designed and prepared a double perovskite, LaBaZnSbO6, by selecting Zn(2+) and Sb(5+) with large size and charge differences, and, indeed, complete B-site ordering can be achieved. Careful study using powder X-ray diffraction data pinpointed its space group to be I2/m, which has rarely been seen in double perovskites. Thereafter, an interesting observation of Sr(2+)-doping-induced symmetry evolution from I2/m to P21/n was confirmed in the complete solid solutions LaBa1-xSrxZnSbO6, where the tilting system also transferred from a(-)a(-)c(0) to a(-)a(-)c(+). The transition boundary is around x = 0.4. It can also be visualized by the variation of θ (defined as c/[(a + b)/2]), which is associated with the anisotropic shrinkage of the unit cell lattice and indeed shows a minimum at x = 0.4. Such a successive modulation of both the structural symmetry and the average La/Ba/Sr-O bond distances (revealed by Rietveld refinements) motivated us to study the Eu(3+) luminescence in La0.95Eu0.05Ba1-xSrxZnSbO6. Interestingly, the maximum of charge transfer absorption of Eu(3+) shows a precise changing tendency with the A-O bond distances along with the Sr(2+) doping, clearly revealing the structure-luminescence correlations.

  1. Changes in charge density vs changes in formal oxidation states: The case of Sn halide perovskites and their ordered vacancy analogues

    NASA Astrophysics Data System (ADS)

    Dalpian, Gustavo M.; Liu, Qihang; Stoumpos, Constantinos C.; Douvalis, Alexios P.; Balasubramanian, Mahalingam; Kanatzidis, Mercouri G.; Zunger, Alex

    2017-07-01

    Shifting the Fermi energy in solids by doping, defect formation, or gating generally results in changes in the charge density distribution, which reflect the ability of the bonding pattern in solids to adjust to such external perturbations. In the traditional chemistry textbook, such changes are often described by the formal oxidation states (FOS) whereby a single atom type is presumed to absorb the full burden of the perturbation (change in charge) of the whole compound. In the present paper, we analyze the changes in the position-dependence charge density due to shifts of the Fermi energy on a general physical basis, comparing with the view of the FOS picture. We use the halide perovskites CsSn X3 (X =F , Cl, Br, I) as examples for studying the general principle. When the solar absorber CsSn I3 (termed 113) loses 50 % of its Sn atoms, thereby forming the ordered vacancy compound C s2Sn I6 (termed 216), the Sn is said in the FOS picture to change from Sn(II) to Sn(IV). To understand the electronic properties of these two groups we studied the 113 and 216 compound pairs CsSnC l3 and C s2SnC l6 , CsSnB r3 and C s2SnB r6 , and CsSn I3 and C s2Sn I6 , complementing them by CsSn F3 and C s2Sn F6 in the hypothetical cubic structure for completing the chemical trends. These materials were also synthesized by chemical routes and characterized by x-ray diffraction, 119Sn-Mössbauer spectroscopy, and K -edge x-ray absorption spectroscopy. We find that indeed in going from 113 to 216 (equivalent to the introduction of two holes per unit) there is a decrease in the s charge on Sn, in agreement with the FOS picture. However, at the same time, we observe an increase of the p charge via downshift of the otherwise unoccupied p level, an effect that tends to replenish much of the lost s charge. At the end, the change in the charge on the Sn site as a result of adding two holes to the unit cell is rather small. This effect is theoretically explained as a "self-regulating response

  2. Formation and structural characterization of 1:1 ordered perovskites in the Ba(Zn{sub 1/3}Ta{sub 2/3})O{sub 3}-BaZrO{sub 3} system

    SciTech Connect

    Chai, L.; Davies, P.K.

    1997-12-01

    The phase stabilities in the (1{minus}x)Ba(Zn{sub 1/3}Ta{sub 2/3})O{sub 3} (BZT)-xBaZrO{sub 3} (BZ) system have been investigated using samples prepared by the mixed-oxide method. The substitution of Zr{sup 4+} destabilizes the 1:2 cation ordering in BZT and promotes the formation of a cubic, 1:1 ordered structure with a doubled perovskite repeat. The homogeneity range of the 1:1 phase extends from x = 0.04 to approximately x = 0.25; substitutions beyond this range stabilize a disordered perovskite. The limits of stability of the 1:1 ordering coincide with compositions previously found to exhibit anomalies in their dielectric loss. The range of homogeneity is consistent with a random layer model for the 1:1 ordered Ba{l_brace}{beta}{prime}{sub 1/2}{beta}{double_prime}{sub 1/2}{r_brace}O{sub 3} structure. In this model the {beta}{double_prime} positions are assumed to be occupied exclusively by Ta{sup 5+}, and the {beta}{prime} sites by a random distribution of Zn{sup 2+}, Zr{sup 4+}, and the remaining Ta{sup 5+} cations. The validity of the model, where the ordered solid solutions can be represented by Ba{l_brace}[Zn{sub (2{minus}y)/3}Ta{sub (1{minus}2y)/3}Zr{sub y}]{sub 1/2}[Ta]{sub 1/2}{r_brace}O{sub 3} (y = 2x) was confirmed by Rietveld refinements conducted using data collected with a synchrotron X-ray source.

  3. Evolution of Oxygen-Vacancy Ordered Crystal Structures in the Perovskite Series Sr nFe nO 3 n-1 ( n=2, 4, 8, and ∞), and the Relationship to Electronic and Magnetic Properties

    NASA Astrophysics Data System (ADS)

    Hodges, J. P.; Short, S.; Jorgensen, J. D.; Xiong, X.; Dabrowski, B.; Mini, S. M.; Kimball, C. W.

    2000-05-01

    Over the oxygen composition range 2.5≤x≤3.0, the SrFeOx system exists as four distinct compounds with the nominal composition SrnFenO3n-1 (n=2, 4, 8, and ∞). The end member SrFeO3 (n=∞) possesses a simple cubic perovskite crystal structure, whereas the oxygen-deficient (n=2, 4, and 8) members each adopt a different vacancy-ordered perovskite crystal structure. Using time-of-flight neutron powder diffraction, we show that previously proposed structures for the Sr4Fe4O11 (n=4) and Sr8Fe8O23 (n=8) compounds are incorrect. We determine the correct crystal structures for Sr4Fe4O11 (orthorhombic, space group Cmmm, a=10.974(1) Å, b=7.702(1) Å, and c=5.473(1) Å) and Sr8Fe8O23 (tetragonal, space group I4/mmm, a=10.929(1) Å and c=7.698(1) Å) through comparisons of the goodness of fit for Rietveld refinements of candidate models and bond-length distributions for each model. Using the correct crystal structures, we are able to assign valence states to the Fe crystallographic sites and to achieve consistency with published Mössbauer results for the same compounds.

  4. Large magnetization and frustration switching of magnetoresistance in the double-perovskite ferrimagnet Mn2FeReO6.

    PubMed

    Arévalo-López, Angel M; McNally, Graham M; Attfield, J Paul

    2015-10-05

    Ferrimagnetic A2 BB'O6 double perovskites, such as Sr2 FeMoO6 , are important spin-polarized conductors. Introducing transition metals at the A-sites offers new possibilities to increase magnetization and tune magnetoresistance. Herein we report a ferrimagnetic double perovskite, Mn2 FeReO6 , synthesized at high pressure which has a high Curie temperature of 520 K and magnetizations of up to 5.0 μB which greatly exceed those for other double perovskite ferrimagnets. A novel switching transition is discovered at 75 K where magnetoresistance changes from conventional negative tunneling behavior to large positive values, up to 265 % at 7 T and 20 K. Neutron diffraction shows that the switch is driven by magnetic frustration from antiferromagnetic Mn(2+) spin ordering which cants Fe(3+) and Re(5+) spins and reduces spin-polarization. Ferrimagnetic double perovskites based on A-site Mn(2+) thus offer new opportunities to enhance magnetization and control magnetoresistance in spintronic materials.

  5. Resonant halide perovskite nanoparticles

    NASA Astrophysics Data System (ADS)

    Tiguntseva, Ekaterina Y.; Ishteev, Arthur R.; Komissarenko, Filipp E.; Zuev, Dmitry A.; Ushakova, Elena V.; Milichko, Valentin A.; Nesterov-Mueller, Alexander; Makarov, Sergey V.; Zakhidov, Anvar A.

    2017-09-01

    The hybrid halide perovskites is a prospective material for fabrication of cost-effective optical devices. Unique perovskites properties are used for solar cells and different photonic applications. Recently, perovskite-based nanophotonics has emerged. Here, we consider perovskite like a high-refractive index dielectric material, which can be considered to be a basis for nanoparticles fabrication with Mie resonances. As a result, we fabricate and study resonant perovskite nanoparticles with different sizes. We reveal, that spherical nanoparticles show enhanced photoluminescence signal. The achieved results lay a cornerstone in the field of novel types of organic-inorganic nanophotonics devices with optical properties improved by Mie resonances.

  6. 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).

  7. Crystal structures and high-temperature phase transitions of the new ordered double perovskites Sr{sub 2}SmSbO{sub 6} and Sr{sub 2}LaSbO{sub 6}

    SciTech Connect

    Faik, A.; Iturbe-Zabalo, E.; Urcelay, I.; Igartua, J.M.

    2009-10-15

    In the present work we report X-ray powder diffraction measurements of Sr{sub 2}SmSbO{sub 6} and Sr{sub 2}LaSbO{sub 6}, at different temperatures. The crystal structures at room temperature of both compounds are determined; and results showing the existence of high-temperature phase transitions in them are presented. Both compounds have double perovskite structure with 1:1 ordered arrangement of the B site cations. At room temperature their symmetries are described with the P2{sub 1}/n space group, that correspond to the (a{sup +}b{sup -}b{sup -}) tilt system. The evolution with temperature of the structure of both compounds shows the presence of two phase transitions: a discontinuous one, at 885 and 945 K, for Sr{sub 2}SmSbO{sub 6} and Sr{sub 2}LaSbO{sub 6}, respectively; and a continuous one, at 1170 and 118 K, for Sr{sub 2}SmSbO{sub 6} and Sr{sub 2}LaSbO{sub 6}, respectively, with the following phase transition sequence: P2{sub 1}/n->R3-bar->Fm3-barm. - Clinographic projections of the structures of the new ordered double perovskites (a) Sr{sub 2}SmSbO{sub 6} and (b) Sr{sub 2}LaSbO{sub 6}, along the [001]{sub p} and [010]{sub p} directions, as indicated, in the upper and in the lower panels, respectively. SmO{sub 6} octahedra are shown green, LaO{sub 6} in cyan, SbO{sub 6} in blue and Sr cations in gray. Sr{sub 2}LaSbO{sub 6} is more distorted than Sr{sub 2}SmSbO{sub 6}, as can be appreciated in the upper panel in the projection of the cuboctahedral site occupied by the Sr. The angle of rotation of the octahedra around the simple perovskite cubic axis is greater in the more distorted Sr{sub 2}LaSbO{sub 6} phase.

  8. 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.

  9. Phase transition and chemical order in the ferroelectric perovskite (1-x)Bi(Mg3/4W1/4)O3-xPbTiO3 solid solution system

    NASA Astrophysics Data System (ADS)

    Stringer, C. J.; Eitel, R. E.; Shrout, T. R.; Randall, C. A.; Reaney, I. M.

    2005-01-01

    Building on the ferroelectric family based on the Bi(Me+3)O3-PbTiO3 solid solutions, the complex solid solution (1-x )Bi(Mg3/4W1/4)O3-xPbTiO3 [(1-x)BMW-xPT] was investigated. This system was found to exhibit a broad morphotropic phase boundary at x ˜0.48mol% PbTiO3 with a corresponding Curie temperature of 205°C separating pseudocubic and tetragonal ferroelectric phases. Based on dielectric, x-ray diffraction (XRD), and calorimetric data, a simple dielectric phase field diagram was established. On further structural analysis with diffraction contrast transmission electron microscopy along with XRD, evidence of B-site chemical ordering was found for the (1-x )Bi(Me'Me″)O3-xPbTiO3 perovskite family.

  10. Unraveling the effect of La A-site substitution on oxygen ion diffusion and oxygen catalysis in perovskite BaFeO3 by data-mining molecular dynamics and density functional theory.

    PubMed

    Chen, Chi; Baiyee, Zarah Medina; Ciucci, Francesco

    2015-10-07

    BaFeO3 (BFO) is a promising parent material for high-temperature oxygen catalysis. The effects of La substitution on the oxygen ion diffusion and oxygen catalysis in A-site La-substituted BFO are studied by combining data-driven molecular dynamics (MD) simulations and density functional theory (DFT) calculations. The data-driven MD simulations are capable of providing atomic level information regarding oxygen jumps at different sites, bridging the resolution gap of analysis between MD and DFT. The simulations identify several effects due to the introduction of La. First, according to simple electroneutrality considerations and DFT calculations, La tends to decrease the concentration of oxygen vacancies in BFO. Second, La substitution lowers the activation energy of local oxygen migration, providing faster paths for oxygen diffusion. The MD analysis predicts a higher hopping rate through La-containing bottlenecks as well as easier oxygen jumps from the La-rich cages and lower dwell times of oxygen in those cages. DFT calculations confirm a lower migration energy through La-containing bottlenecks. Third, the electrocatalytic activity of the material decreases with La, as indicated by a lower O p-band center and higher oxygen vacancy formation energies.

  11. High Efficiency Pb-In Binary Metal Perovskite Solar Cells.

    PubMed

    Wang, Zhao-Kui; Li, Meng; Yang, Ying-Guo; Hu, Yun; Ma, Heng; Gao, Xing-Yu; Liao, Liang-Sheng

    2016-08-01

    Mixed Pb-In perovskite solar cells are fabricated by using lead(II) chloride and indium(III) chloride with methylammonium iodide. A maximum power conversion efficiency as high as 17.55% is achieved owing to the high quality of perovskites with multiple ordered crystal orientations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Anomalous perovskite PbRuO3 stabilized under high pressure.

    PubMed

    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

    2013-12-10

    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.

  13. 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

  14. Evolution of oxygen-vacancy ordered crystal structures in the perovskite series SrnFenO3n-1 (n=2, 4, 8, and {infinity}), and the relationship to electronic and magnetic properties.

    SciTech Connect

    Hodges, J. P.; Jorgensen, J. D.; Xiong, X.; Dabrowski, B.; Mini, S. M.; Kimball, C. W.; Materials Science Division; Northern Illinois Univ.

    2000-05-01

    Over the oxygen composition range 2.5{<=}x{<=}3.0, the SrFeO{sub x} system exists as four distinct compounds with the nominal composition Sr{sub n}Fe{sub n}O{sub 3n-1} (n=2, 4, 8, and {infinity}). The end member SrFeO{sub 3} (n={infinity}) possesses a simple cubic perovskite crystal structure, whereas the oxygen-deficient (n=2, 4, and 8) members each adopt a different vacancy-ordered perovskite crystal structure. Using time-of-flight neutron powder diffraction, we show that previously proposed structures for the Sr{sub 4}Fe{sub 4}O{sub 11} (n=4) and Sr{sub 8}Fe{sub 8}O{sub 23} (n=8) compounds are incorrect. We determine the correct crystal structures for Sr{sub 4}Fe{sub 4}O{sub 11} (orthorhombic, space group Cmmm, a=10.974(1) {angstrom}, b=7.702(1) {angstrom}, and c=5.473(1) {angstrom}) and Sr{sub 8}Fe{sub 8}O{sub 23} (tetragonal, space group I4/mmm, a=10.929(1) {angstrom} and c=7.698(1) {angstrom}) through comparisons of the goodness of fit for Rietveld refinements of candidate models and bond-length distributions for each model. Using the correct crystal structures, we are able to assign valence states to the Fe crystallographic sites and to achieve consistency with published Moessbauer results for the same compounds.

  15. CaCu3Pt4O12: the first perovskite with the B site fully occupied by Pt(4+).

    PubMed

    Yamada, Ikuya; Takahashi, Yuka; Ohgushi, Kenya; Nishiyama, Norimasa; Takahashi, Ryoji; Wada, Kohei; Kunimoto, Takehiro; Ohfuji, Hiroaki; Kojima, Yohei; Inoue, Toru; Irifune, Tetsuo

    2010-08-02

    A novel A-site ordered perovskite CaCu(3)Pt(4)O(12) was synthesized under high pressure and high temperature of 12 GPa and 1250 degrees C. CaCu(3)Pt(4)O(12) is the first perovskite in which the B site is fully occupied by Pt(4+). The crystal structure refinement based on the synchrotron powder X-ray diffraction data shows that CaCu(3)Pt(4)O(12) crystallizes in the space group Im3 (cubic) with a lattice constant of a = 7.48946(10) A. The magnetic susceptibility data show the antiferromagnetic transition at T(N) = 40 K, which is attributed to the magnetic ordering of Cu(2+) spins with S = 1/2.

  16. Competing magnetic ground states in the A-site layer-ordered manganite La[subscript 1−x]Ba[subscript 1+x]Mn[subscript 2]O[subscript 6

    SciTech Connect

    Chmaissem, O.; Brown, D.E.; Ren, Y.; Kolesnik, S.; Mais, J.; Dabrowski, B.

    2010-10-06

    Using neutron and x-ray diffraction, we report the discovery of competing ground states near a multicritical point in A-site layer-ordered La{sub 1-x}Ba{sub 1+x}Mn{sub 2}O{sub 6} materials. We demonstrate the dual effects of deliberate disorder on the system's stability, the freezing of the competing states, and the drastic reduction in magnetic fields required for the suppression of charge- and orbital-ordered phases. Our work suggests that quenched disorder is not the primary reason for phase separation and magnetoresistance and that increased doping leads to electronic phase separation.

  17. Elastic properties of perovskite ATiO3 (A = Be, Mg, Ca, Sr, and Ba) and PbBO3 (B = Ti, Zr, and Hf): First principles calculations

    NASA Astrophysics Data System (ADS)

    Pandech, Narasak; Sarasamak, Kanoknan; Limpijumnong, Sukit

    2015-05-01

    The mechanical properties of perovskite oxides depend on two metal oxide lattices that are intercalated. This provides an opportunity for separate tuning of hardness, Poisson's ratio (transverse expansion in response to the compression), and shear strength. The elastic constants of series of perovskite oxides were studied by first principles approach. Both A-site and B-site cations were systematically varied in order to see their effects on the elastic parameters. To study the effects of A-site cations, we studied the elastic properties of perovskite ATiO3 for A being Be, Mg, Ca, Sr, or Ba, one at a time. Similarly, for B-site cations, we studied the elastic properties of PbBO3 for B being Ti, Zr, or Hf, one at a time. The density functional first principles calculations with local density approximation (LDA) and generalized gradient approximation (GGA) were employed. It is found that the maximum C11 elastic constant is achieved when the atomic size of the cations at A-site and B-site are comparable. We also found that C12 elastic constant is sensitive to B-site cations while C44 elastic constant is more sensitive to A-site cations. Details and explanations for such dependencies are discussed.

  18. Chalcogenide perovskites for photovoltaics.

    PubMed

    Sun, Yi-Yang; Agiorgousis, Michael L; Zhang, Peihong; Zhang, Shengbai

    2015-01-14

    Chalcogenide perovskites are proposed for photovoltaic applications. The predicted band gaps of CaTiS3, BaZrS3, CaZrSe3, and CaHfSe3 with the distorted perovskite structure are within the optimal range for making single-junction solar cells. The predicted optical absorption properties of these materials are superior compared with other high-efficiency solar-cell materials. Possible replacement of the alkaline-earth cations by molecular cations, e.g., (NH3NH3)(2+), as in the organic-inorganic halide perovskites (e.g., CH3NH3PbI3), are also proposed and found to be stable. The chalcogenide perovskites provide promising candidates for addressing the challenging issues regarding halide perovskites such as instability in the presence of moisture and containing the toxic element Pb.

  19. Oxygen-deficient and ordered perovskite-type solid-solution system Ba1+xBi1-xOy(0 <= x <= 0.5, 3.00 >= y >= 2.75)

    NASA Astrophysics Data System (ADS)

    Itoh, Mitsuru; Sawada, Tohru; Liang, Ruixing; Kawaji, Hitoshi; Nakamura, Tetsurō

    1990-07-01

    A new oxygen-deficient and ordered perovskite-type solid-solution system Ba1+xBi1-xOy(0 ≦ x ≦ 0.5, 3.00 ≧ y ≧ 2.75) was synthesized, with the estimated ionic configuration Ba(Ba 2+xBi 3+3.5-1.5 x-yBi 5+-3+0.5 x+y)(Bi 5+0.5)O y. The lattice parameters and mean valence of bismuth in the samples annealed in one atmosphere of oxygen at 773 K were determined by the powder X-ray diffraction method and iodometric titration method, respectively. Samples with the compositions 0 ≦ x ≦ 0.05, 0.10 ≦ x ≦ 0.15, 0.20 ≦ x ≦ 0.425, 0.45 ≦ x ≦ 0.475, and 0.475 < x ≦ 0.50 were found to be monoclinic, rhombohedral, cubic, tetragonal, and cubic, respectively. Oxygen deficiency was observed in the entire range of the composition; the ordering of the oxygen vacancies was confirmed in the range X ≧ 0.45.

  20. The distorted perovskite Sr(Na sub 1/4 Sb sub 3/4 )O sub 3 : A novel example of 1:3 B-cation ordering

    SciTech Connect

    Alonso, J.A.; Mzayek, E.; Rasines, I. )

    1990-01-01

    Powder neutron diffraction data ({lambda} = 1.909 {angstrom}), have been used to refine the crystal structure of the ordered perovskite Sr(Na{sub 1/4}Sb{sub 3/4})O{sub 3} at 295 K. This compound is monoclinic, a = 8.0913(2), b = 8.0871(1), c = 8.0918(2) {angstrom}, {beta} = 89.953(1){degree}, with space group P2{sub 1}/n, Z = 8. R{sub p} = 4.27, R{sub wp} = 5.43, and R{sub z} = 3.44. The fairly distorted NaO{sub 6} and SbO{sub 6} octahedra, ordered in a 1:3 three-dimensional arrangement, are titled according to a system similar to that of the GdFeO{sub 3} structure. The tilting angles for the four kinds of octahedra have been obtained from the atomic positional parameters. Sr atoms are in strongly asymmetrical environments, coordinated to 13 oxygens, in agreement with bond-valence calculations.

  1. Structural chemistry of the cation-ordered perovskites Sr{sub 2}CaMo{sub 1-x}Te{sub x}O{sub 6} (0=

    SciTech Connect

    Prior, Timothy J.; Couper, Victoria J.; Battle, Peter D. . E-mail: peter.battle@chem.ox.ac.uk

    2005-01-15

    The crystal structures of Sr{sub 2}CaMoO{sub 6} and Sr{sub 2}CaTeO{sub 6} have been determined at room temperature by neutron powder diffraction. Both compounds crystallize in the perovskite structure with a rock-salt ordered array of Ca{sup 2+} and M{sup 6+} cations (M=Mo, Te) on the six-coordinate sites (space group P2{sub 1}/n (no. 14); for M=Mo, a=5.76228(7), b=5.84790(7), c=8.18707(9)A, {beta}=90.194(1){sup o}, for M=Te, a=5.79919(9), b=5.83756(8), c=8.2175(1)A, {beta}=90.194(1){sup o}). Compositions in the solid solution Sr{sub 2}CaMo{sub 1-x}Te{sub x}O{sub 6} have been synthesized and shown by X-ray diffraction to adopt the same ordered structure. The results are used in a discussion of the cation oxidation states in Ca{sub 2}FeMoO{sub 6} and to establish the similarity between the structural chemistry of hexavalent Mo and Te.

  2. Two-Dimensional Perovskite Activation with an Organic Luminophore.

    PubMed

    Jemli, Khaoula; Audebert, Pierre; Galmiche, Laurent; Trippé-Allard, Gaelle; Garrot, Damien; Lauret, Jean-Sébastien; Deleporte, Emmanuelle

    2015-10-07

    A great advantage of the hybrid organic-inorganic perovskites is the chemical flexibility and the possibility of a molecular engineering of each part of the material (the inorganic part and the organic part respectively) in order to improve or add some functionalities. An adequately chosen organic luminophore has been introduced inside a lead bromide type organic-inorganic perovskite, while respecting the two-dimensional perovskite structure. A substantial increase of the brilliance of the perovskite is obtained. This activation of the perovskite luminescence by the adequate engineering of the organic part is an original approach, and is particularly interesting in the framework of the light-emitting devices such as organic light-emitting diodes (OLEDs) or lasers.

  3. Sr{sub 4+n}Mn{super III}{sub 4}Mn{super IV}{sub n} O{sub 10+3n} : A new homologous series of oxygen vacancy-ordered perovskite compounds built from Mn{sup III}-O pyramids and Mn{sup IV}-O octahedra.

    SciTech Connect

    Suescun, L.; Dabrowski, B.; Materials Science Division; Northern Illinois Univ.

    2008-01-01

    A new homologous series of oxygen-vacancy-ordered perovskites with the formula Sr{sub 4+n}Mn{sub 4}{sup 3+}Mn{sub n}{sup 4+}O{sub 10+3n} is proposed based on the structural trends found for the recently described Sr{sub 4}Mn{sub 4}O{sub 10}, Sr{sub 5}Mn{sub 5}O{sub 13} and Sr{sub 7}Mn{sub 7}O{sub 19} compounds. These compounds correspond to n = 0 (Sr{sub 4}Mn{sub 4}{sup 3+}O{sub 10}), n = 1 (Sr{sub 5}Mn{sub 4}{sup 3+}Mn{sup 4+}O{sub 13}) and n = 3 (Sr{sub 7}Mn{sub 4}{sup 3+}Mn{sub 3}{sup 4+}O{sub 19}) members of the series. A linear set of four Mn{sup 3+}O{sub 5} pyramids placed on the ab plane and pointing along the +x, -y, +y, -x directions defines the n = 0 building block for the series. The nth members can be constructed from blocks containing four pyramids and n Mn{sup 4+}O{sub 6} octahedra with 2/m symmetry. Compounds in the related systems CaMnO{sub x} and LaCuO{sub x}, containing Mn{sup 3+} and Cu{sup 2+} pyramids and Mn{sup 4+} and Cu{sup 3+} octahedra have also been found to be members of the series. The size and charge of the A-site cation and the apical distortion of the pyramidally coordinated B-site cation are shown to be important factors in the stabilization of certain members of the series. A qualitative explanation for the absence of some of the possible members of the series is presented based on these factors.

  4. 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

  5. Perovskites with the Framework-Forming Xenon.

    PubMed

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

    2015-11-23

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

  6. Trap states in lead iodide perovskites.

    PubMed

    Wu, Xiaoxi; Trinh, M Tuan; Niesner, Daniel; Zhu, Haiming; Norman, Zachariah; Owen, Jonathan S; Yaffe, Omer; Kudisch, Bryan J; Zhu, X-Y

    2015-02-11

    Recent discoveries of highly efficient solar cells based on lead iodide perovskites have led to a surge in research activity on understanding photo carrier generation in these materials, but little is known about trap states that may be detrimental to solar cell performance. Here we provide direct evidence for hole traps on the surfaces of three-dimensional (3D) CH3NH3PbI3 perovskite thin films and excitonic traps below the optical gaps in these materials. The excitonic traps possess weak optical transition strengths, can be populated from the relaxation of above gap excitations, and become more significant as dimensionality decreases from 3D CH3NH3PbI3 to two-dimensional (2D) (C4H9NH3I)2(CH3NH3I)(n-1)(PbI2)(n) (n = 1, 2, 3) perovskites and, within the 2D family, as n decreases from 3 to 1. We also show that the density of excitonic traps in CH3NH3PbI3 perovskite thin films grown in the presence of chloride is at least one-order of magnitude lower than that grown in the absence of chloride, thus explaining a widely known mystery on the much better solar cell performance of the former. The trap states are likely caused by electron-phonon coupling and are enhanced at surfaces/interfaces where the perovskite crystal structure is most susceptible to deformation.

  7. Structural Study of a Doubly Ordered Perovskite Family NaLnCoWO6 (Ln = Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb): Hybrid Improper Ferroelectricity in Nine New Members.

    PubMed

    Zuo, Peng; Colin, Claire V; Klein, Holger; Bordet, Pierre; Suard, Emmanuelle; Elkaim, Erik; Darie, Céline

    2017-07-17

    The compounds of the doubly ordered perovskite family NaLnCoWO6 (Ln = Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Yb) were synthesized by solid-state reaction, nine of which (Ln = Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Yb) are new phases prepared under high-temperature and high-pressure conditions. Their structural properties were investigated at room temperature by synchrotron X-ray powder diffraction and neutron powder diffraction. All of them crystallize in monoclinic structures, especially the nine new compounds have the polar space group P21 symmetry, as confirmed by second harmonic generation measurements. The P21 polar structures were decomposed and refined in terms of symmetry modes, demonstrating that the polar mode is induced by two nonpolar modes in a manner of Hybrid Improper Ferroelectricity. The amplitudes of these three major modes all increase with decreasing the Ln cation size. The spontaneous ferroelectric polarization is estimated from the neutron diffraction data of three samples (Ln = Y, Tb, and Ho) and can be as large as ∼20 μC/cm(2).

  8. Synthesis of solid solutions of perovskites

    SciTech Connect

    Dambekalne, M.Y.; Antonova, M.K.; Perro, I.T.; Plaude, A.V.

    1986-03-01

    The authors carry out thermographic studies, using a derivatograph, in order to understand the nature of the processes taking place during the synthesis of solid solutions of perovskites. Based on the detailed studies on the phase transformations occurring in the charges of the PSN-PMN solid solutions and on the selection of the optimum conditions for carrying out their synthesis, the authors obtained a powder containing a minimum quantity of the undesirable pyrochlore phase and by sintering it using the hot pressing method, they produced single phase ceramic specimens containing the perovskite phase alone with a density close to the theoretical value and showing zero apparent porosity and water absorption.

  9. Nanoimprinted Perovskite Solar Cells With Enhanced Photocurrent

    NASA Astrophysics Data System (ADS)

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

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

  10. Influence of void-free perovskite capping layer on the charge recombination process in high performance CH3NH3PbI3 perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Fu, Kunwu; Nelson, Christopher T.; Scott, Mary Cooper; Minor, Andrew; Mathews, Nripan; Wong, Lydia Helena

    2016-02-01

    The stunning rise of methylammonium lead iodide perovskite material as a light harvesting material in recent years has drawn much attention in the photovoltaic community. Here, we investigated in detail the uniform and void-free perovskite capping layer in the mesoscopic perovskite devices and found it to play a critical role in determining device performance and charge recombination process. Compared to the rough surface with voids of the perovskite layer, surface of the perovskite capping layer obtained from sequential deposition process is much more uniform with less void formation and distribution within the TiO2 mesoscopic scaffold is more homogeneous, leading to much improved photovoltaic parameters of the devices. The impact of void free perovskite capping layer surface on the charge recombination processes within the mesoscopic perovskite solar cells is further scrutinized via charge extraction measurement. Modulation of precursor solution concentrations in order to further improve the perovskite layer surface morphology leads to higher efficiency and lower charge recombination rates. Inhibited charge recombination in these solar cells also matches with the higher charge density and slower photovoltage decay profiles measured.The stunning rise of methylammonium lead iodide perovskite material as a light harvesting material in recent years has drawn much attention in the photovoltaic community. Here, we investigated in detail the uniform and void-free perovskite capping layer in the mesoscopic perovskite devices and found it to play a critical role in determining device performance and charge recombination process. Compared to the rough surface with voids of the perovskite layer, surface of the perovskite capping layer obtained from sequential deposition process is much more uniform with less void formation and distribution within the TiO2 mesoscopic scaffold is more homogeneous, leading to much improved photovoltaic parameters of the devices. The impact of

  11. 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.

  12. Evidence of spin-glass like ordering and exchange bias effect in antisite-disordered nanometric La1.5Ca0.5CoMnO6 double perovskite

    NASA Astrophysics Data System (ADS)

    Sahoo, R. C.; Paladhi, D.; Nath, T. K.

    2017-08-01

    Single-phase polycrystalline La1.5Ca0.5CoMnO6 double perovskite nanoparticles (∼25 nm) have been synthesized by chemical sol-gel method. We report here the structural, magnetic and transport properties using X-ray diffraction, dc magnetization, ac susceptibility, exchange bias and dc resistivity measurements. The Rietveld refinement of X-ray diffraction pattern reveals that the La1.5Ca0.5CoMnO6 (LCCMO) system crystallizes in orthorhombic structure with pbnm space group. Mn and Co ions are not completely ordered on the B sites due to the presence of about 30% antisite-disorder in the system. The ordering of Co2+ and Mn4+ gives rise to the ferromagnetism below 145 K. A spin glass like ground state has also been observed near 37.6(4) K, arising mainly due to the presence of competing magnetic interactions and antisite-disorder in the LCCMO nanoparticles. The frequency dependence peak shift of the Ac-susceptibility peak in the glassy state follows the critical slowing down model. The observed memory effect in ac susceptibility data reveals the existence of interacting clusters in a competing magnetic interactions state. The presence of noticeable exchange bias effect can be best explained on the basis of uncompensated interface (ferromagnetic/spin-glass) spins of antisite-disordered LCCMO system. This anti-site disordered nanocompound exhibits semiconducting behavior with variable range hopping kind of electronic conduction mechanism in the temperature range of 200-300 K. We have also observed large negative magnetoresistance (-30% at 100 K and 60 kOe) mainly due to the spin-polarized transport across the grain boundaries.

  13. 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.

  14. A structural study of the proton conducting B-site ordered perovskite Ba3Ca1.18Ta1.82O8.73.

    PubMed

    Verbraeken, Maarten C; Viana, Hermenegildo A L; Wormald, Philip; Irvine, John T S

    2011-06-15

    The proton conducting material Ba(3)Ca(1.18)Ta(1.82)O(8.73) (BCT18) was synthesized and characterized using diffraction methods and thermal analysis. It was shown that BCT18 is structurally similar to its niobium analogue (BCN18). At synthesis temperatures up to 1500 °C however, BCT18 forms a mixture of Ca- and Ta-site ordered phases, with both 1:1 type and 1:2 type ordering. The phase ratio seems to depend solely on the synthesis conditions, with 1:1 type ordering being the dominant form in most cases. Thermal treatment in vacuum, wet and dry hydrogen, and CO(2) suggests that both forms contain defects (Ca(Ta)(''') and V(O)(··)), allowing the material to absorb water and CO(2). The uptake and the release of H(2)O and of CO(2) are all reversible, as evidenced by x-ray diffraction studies and thermal analysis, suggesting that the molecules are present as structural defects (OH(O)(·) and CO(3O)(×)), rather than surface species or separate hydroxide or carbonate phases. Solid state (1)H nuclear magnetic resonance also confirms the presence of protons, and the peak broadening suggests that they are mobile at room temperature.

  15. A structural study of the proton conducting B-site ordered perovskite Ba3Ca1.18Ta1.82O8.73

    NASA Astrophysics Data System (ADS)

    Verbraeken, Maarten C.; Viana, Hermenegildo A. L.; Wormald, Philip; Irvine, John T. S.

    2011-06-01

    The proton conducting material Ba3Ca1.18Ta1.82O8.73 (BCT18) was synthesized and characterized using diffraction methods and thermal analysis. It was shown that BCT18 is structurally similar to its niobium analogue (BCN18). At synthesis temperatures up to 1500 °C however, BCT18 forms a mixture of Ca- and Ta-site ordered phases, with both 1:1 type and 1:2 type ordering. The phase ratio seems to depend solely on the synthesis conditions, with 1:1 type ordering being the dominant form in most cases. Thermal treatment in vacuum, wet and dry hydrogen, and CO2 suggests that both forms contain defects (CaTa''' and {V_O^{\\bdot \\bdot }} ), allowing the material to absorb water and CO2. The uptake and the release of H2O and of CO2 are all reversible, as evidenced by x-ray diffraction studies and thermal analysis, suggesting that the molecules are present as structural defects ( {OH_O^{\\bdot }} and CO3O × ), rather than surface species or separate hydroxide or carbonate phases. Solid state 1H nuclear magnetic resonance also confirms the presence of protons, and the peak broadening suggests that they are mobile at room temperature.

  16. Perovskite Solar Cells: High Efficiency Pb-In Binary Metal Perovskite Solar Cells (Adv. Mater. 31/2016).

    PubMed

    Wang, Zhao-Kui; Li, Meng; Yang, Ying-Guo; Hu, Yun; Ma, Heng; Gao, Xing-Yu; Liao, Liang-Sheng

    2016-08-01

    On page 6695, X. Y. Gao, L.-S. Liao, and co-workers describe the fabrication of mixed Pb-In perovskite solar cells, using indium (III) chloride and lead (II) chloride with methylammonium iodide. A maximum power conversion efficiency as high as 17.55% is achieved owing to the high quality of the perovskites with multiple ordered crystal orientations. This work demonstrates the possibility of substituting the Pb (II) by using In (III), which opens a broad route to fabricating alloy perovskite solar cells with mitigated ecological impact. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Low -Dimensional Halide Perovskites and Their Advanced Optoelectronic Applications

    NASA Astrophysics Data System (ADS)

    Zhang, Jian; Yang, Xiaokun; Deng, Hui; Qiao, Keke; Farooq, Umar; Ishaq, Muhammad; Yi, Fei; Liu, Huan; Tang, Jiang; Song, Haisheng

    2017-07-01

    Metal halide perovskites are crystalline materials originally developed out of scientific curiosity. They have shown great potential as active materials in optoelectronic applications. In the last 6 years, their certified photovoltaic efficiencies have reached 22.1%. Compared to bulk halide perovskites, low-dimensional ones exhibited novel physical properties. The photoluminescence quantum yields of perovskite quantum dots are close to 100%. The external quantum efficiencies and current efficiencies of perovskite quantum dot light-emitting diodes have reached 8% and 43 cd A-1, respectively, and their nanowire lasers show ultralow-threshold room-temperature lasing with emission tunability and ease of synthesis. Perovskite nanowire photodetectors reached a responsivity of 10 A W-1 and a specific normalized detectivity of the order of 1012 Jones. Different from most reported reviews focusing on photovoltaic applications, we summarize the rapid progress in the study of low-dimensional perovskite materials, as well as their promising applications in optoelectronic devices. In particular, we review the wide tunability of fabrication methods and the state-of-the-art research outputs of low-dimensional perovskite optoelectronic devices. Finally, the anticipated challenges and potential for this exciting research are proposed.

  18. Orientational Ordering, Tilting and Lone-pair Activity in the Perovskite Methylammonium Tin Bromide, CH3NH3SnBr3

    SciTech Connect

    Swainson, I.; Chi, L; Her, J; Cranswick, L; Stephens, P; Winkler, B; Wilson, D; Milman, V

    2010-01-01

    Synchrotron powder diffraction data from methylammonium tin bromide, CH{sub 3}NH{sub 3}SnBr{sub 3}, taken as a function of temperature, reveal the existence of a phase between 230 and 188 K crystallizing in Pmc2{sub 1}, a = 5.8941 (2), b = 8.3862 (2), c = 8.2406 (2) {angstrom}. Strong ferroelectric distortions of the octahedra, associated with stereochemical activity of the Sn 5s{sup 2} lone pair, are evident. A group analysis and decomposition of the distortion modes of the inorganic framework with respect to the cubic parent is given. The primary order parameters driving this upper transition appear to be an in-phase tilt (rotation) of the octahedra coupled to a ferroelectric mode. The precise nature of the lower-temperature phase remains uncertain, although it appears likely to be triclinic. Density-functional theory calculations on such a triclinic cell suggest that directional bonding of the amine group to the halide cage is coupled to the stereochemical activity of the Sn lone pair via the Br atoms, i.e. that the bonding from the organic component may have a strong effect on the inorganic sublattice (principally via switching the direction of the lone pair with little to no energy cost).

  19. Elastic properties of perovskite ATiO{sub 3} (A = Be, Mg, Ca, Sr, and Ba) and PbBO{sub 3} (B = Ti, Zr, and Hf): First principles calculations

    SciTech Connect

    Pandech, Narasak; Limpijumnong, Sukit; Sarasamak, Kanoknan

    2015-05-07

    The mechanical properties of perovskite oxides depend on two metal oxide lattices that are intercalated. This provides an opportunity for separate tuning of hardness, Poisson's ratio (transverse expansion in response to the compression), and shear strength. The elastic constants of series of perovskite oxides were studied by first principles approach. Both A-site and B-site cations were systematically varied in order to see their effects on the elastic parameters. To study the effects of A-site cations, we studied the elastic properties of perovskite ATiO{sub 3} for A being Be, Mg, Ca, Sr, or Ba, one at a time. Similarly, for B-site cations, we studied the elastic properties of PbBO{sub 3} for B being Ti, Zr, or Hf, one at a time. The density functional first principles calculations with local density approximation (LDA) and generalized gradient approximation (GGA) were employed. It is found that the maximum C{sub 11} elastic constant is achieved when the atomic size of the cations at A-site and B-site are comparable. We also found that C{sub 12} elastic constant is sensitive to B-site cations while C{sub 44} elastic constant is more sensitive to A-site cations. Details and explanations for such dependencies are discussed.

  20. Probing cation and vacancy ordering in the dry and hydrated yttrium-substituted BaSnO3 perovskite by NMR spectroscopy and first principles calculations: implications for proton mobility.

    PubMed

    Buannic, Lucienne; Blanc, Frédéric; Middlemiss, Derek S; Grey, Clare P

    2012-09-05

    Hydrated BaSn(1-x)Y(x)O(3-x/2) is a protonic conductor that, unlike many other related perovskites, shows high conductivity even at high substitution levels. A joint multinuclear NMR spectroscopy and density functional theory (total energy and GIPAW NMR calculations) investigation of BaSn(1-x)Y(x)O(3-x/2) (0.10 ≤ x ≤ 0.50) was performed to investigate cation ordering and the location of the oxygen vacancies in the dry material. The DFT energetics show that Y doping on the Sn site is favored over doping on the Ba site. The (119)Sn chemical shifts are sensitive to the number of neighboring Sn and Y cations, an experimental observation that is supported by the GIPAW calculations and that allows clustering to be monitored: Y substitution on the Sn sublattice is close to random up to x = 0.20, while at higher substitution levels, Y-O-Y linkages are avoided, leading, at x = 0.50, to strict Y-O-Sn alternation of B-site cations. These results are confirmed by the absence of a "Y-O-Y" (17)O resonance and supported by the (17)O NMR shift calculations. Although resonances due to six-coordinate Y cations were observed by (89)Y NMR, the agreement between the experimental and calculated shifts was poor. Five-coordinate Sn and Y sites (i.e., sites next to the vacancy) were observed by (119)Sn and (89)Y NMR, respectively, these sites disappearing on hydration. More five-coordinated Sn than five-coordinated Y sites are seen, even at x = 0.50, which is ascribed to the presence of residual Sn-O-Sn defects in the cation-ordered material and their ability to accommodate O vacancies. High-temperature (119)Sn NMR reveals that the O ions are mobile above 400 °C, oxygen mobility being required to hydrate these materials. The high protonic mobility, even in the high Y-content materials, is ascribed to the Y-O-Sn cation ordering, which prevents proton trapping on the more basic Y-O-Y sites.

  1. In-situ THz spectroscopy on lead halide perovskite film for monitoring transient crystallization phase (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Park, SaeJune; Ahn, Yeong Hwan

    2017-02-01

    In the past few years, perovskite film has been considered as a promising materials for solar cell devices due to its outstanding performance. To maximize the perovskite solar cell performance, it is necessary to understand the crystallization mechanism of perovskite film. In this study, we monitored the crystallization and decrystallization of the lead halide perovskite (MAPbI3-xClx) film under thermal annealing and UV-laser exposure processes by using in-situ terahertz time-domain spectroscopy. The strength of vibrational resonances in THz frequency range is found to be a good indicator of perovskite crystallinity. We measured the THz spectra as we annealed the perovskite film at various temperatures in order to achieve the degree of crystallization, i.e., the transition of perovskite structure from the intermediate phase to the tetragonal phase. In addition, we investigated the UV-laser-induced phase transition of the perovskite film. Because it is widely known that UV light illumination on perovskite film tends degrade the perovskite cell efficiency, its influence on the crystallization is our primary concern. Surprisingly, the crystallization phase increases for 10 min, until it starts to degrade over a couple of hours. We also studied the transient transport properties of the films under UV illumination. The correlation between the degree of crystallization (obtained from THz transmission) and the transport parameters exhibited the electric percolation threshold behaviors in the perovskite films. These information are expected to be crucial for optimizing the fabrication method of perovskite solar cell.

  2. 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.

  3. Electro-optics of perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Lin, Qianqian; Armin, Ardalan; Nagiri, Ravi Chandra Raju; Burn, Paul L.; Meredith, Paul

    2015-02-01

    Organohalide-perovskite solar cells have emerged as a leading next-generation photovoltaic technology. However, despite surging efficiencies, many questions remain unanswered regarding the mechanisms of operation. Here we report a detailed study of the electro-optics of efficient CH3NH3PbI3-perovskite-only planar devices. We report the dielectric constants over a large frequency range. Importantly, we found the real part of the static dielectric constant to be ∼70, from which we estimate the exciton-binding energy to be of order 2 meV, which strongly indicates a non-excitonic mechanism. Also, Jonscher's Law behaviour was consistent with the perovskite having ionic character. Accurate knowledge of the cell's optical constants allowed improved modelling and design, and using this information we fabricated an optimized device with an efficiency of 16.5%. The optimized devices have ∼100% spectrally flat internal quantum efficiencies and minimal bimolecular recombination. These findings establish systematic design rules to achieve silicon-like efficiencies in simple perovskite solar cells.

  4. Crystalline-amorphous transition in silicate perovskites

    SciTech Connect

    Hemmati, M.; Chizmeshya, A. |; Wolf, G.H.; Poole, P.H.; Shao, J.; Angell, C.A.

    1995-06-01

    CaSiO{sub 3} and MgSiO{sub 3} perovskites are known to undergo solid-state crystal to amorphous transitions near ambient pressure when decompressed from their high-pressure stability fields. In order to elucidate the mechanistic aspects of this transition we have performed detailed molecular-dynamics simulations and lattice-dynamical calculations on model silicate perovskite systems using empirical rigid-ion pair potentials. In the simulations at low temperatures, the model perovskite systems transform under tension to a low-density glass composed of corner shared chains of tetrahedral silicon. The amorphization is initiated by a thermally activated step involving a soft polar optic mode in the perovskite phase at the Brillouin zone center. Progression of the system along this reaction coordinate triggers, in succession, multiple barrierless modes of instability ultimately producing a catastrophic decohesion of the lattice. An important intermediary along the reaction path is a crystalline phase where silicon is in a five-coordinate site and the alkaline-earth metal atom is in eightfold coordination. At the onset pressure, this transitory phase is itself dynamically unstable to a number of additional vibrational modes, the most relevant being those which result in transformation to a variety of tetrahedral chain silicate motifs. These results support the conjecture that stress-induced amorphization arises from the near simultaneous accessibility of multiple modes of instability in the highly metastable parent crystalline phase.

  5. Electrospun Perovskite Nanofibers

    NASA Astrophysics Data System (ADS)

    Chen, Dongsheng; Zhu, Yanyan

    2017-02-01

    CH3NH3PbI3 perovskite nanofibers were synthesized by versatile electrospinning techniques. The synthetic CH3NH3PbI3 nanofibers were characterized by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and photoluminescence. As counter electrodes, the synthesized nanofibers increased the performance of the dye-sensitized solar cells from 1.58 to 2.09%. This improvement was attributed to the enhanced smoothness and efficiency of the electron transport path. Thus, CH3NH3PbI3 perovskites nanofibers are potential alternative to platinum counter electrodes in dye-sensitized solar cells.

  6. Superior Optical Properties of Perovskite Nanocrystals as Single Photon Emitters.

    PubMed

    Hu, Fengrui; Zhang, Huichao; Sun, Chun; Yin, Chunyang; Lv, Bihu; Zhang, Chunfeng; Yu, William W; Wang, Xiaoyong; Zhang, Yu; Xiao, Min

    2015-12-22

    The power conversion efficiency of photovoltaic devices based on semiconductor perovskites has reached ∼20% after just several years of research efforts. With concomitant discoveries of other promising applications in lasers, light-emitting diodes, and photodetectors, it is natural to anticipate what further excitement these exotic perovskites could bring about. Here we report on the observation of single photon emission from single CsPbBr3 perovskite nanocrystals (NCs) synthesized from a facile colloidal approach. Compared with traditional metal-chalcogenide NCs, these CsPbBr3 NCs exhibit nearly 2 orders of magnitude increase in their absorption cross sections at similar emission colors. Moreover, the radiative lifetime of CsPbBr3 NCs is greatly shortened at both room and cryogenic temperatures to favor an extremely fast output of single photons. The above superior optical properties have paved the way toward quantum-light applications of perovskite NCs in various quantum information processing schemes.

  7. 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

  8. Lattice effects on ferromagnetism in perovskite ruthenates.

    PubMed

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

    2013-08-13

    Ferromagnetism and its evolution in the orthorhombic perovskite system Sr(1-x)Ca(x)RuO3 have been widely believed to correlate with structural distortion. The recent development of high-pressure synthesis of the Ba-substituted Sr(1-y)Ba(y)RuO3 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 remains the same but the bond-length variance varies, we are able to demonstrate a parabolic curve of Tc versus mean bond length . A much higher Tc ∼ 177 K than that found in orthorhombic SrRuO3 can be obtained from the curve at a bond length , which makes the geometric factor t = /(√2) ∼ 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.

  9. Observation and Mediation of the Presence of Metallic Lead in Organic-Inorganic Perovskite Films.

    PubMed

    Sadoughi, Golnaz; Starr, David E; Handick, Evelyn; Stranks, Samuel D; Gorgoi, Mihaela; Wilks, Regan G; Bär, Marcus; Snaith, Henry J

    2015-06-24

    We have employed soft and hard X-ray photoelectron spectroscopies to study the depth-dependent chemical composition of mixed-halide perovskite thin films used in high-performance solar cells. We detect substantial amounts of metallic lead in the perovskite films, which correlate with significant density of states above the valence band maximum. The metallic lead content is higher in the bulk of the perovskite films than at the surface. Using an optimized postanneal process in air, we can reduce the metallic lead content in the perovskite film. This process reduces the amount of metallic lead and a corresponding increase in the photoluminescence quantum efficiency of the perovskite films can be observed. This correlation indicates that metallic lead impurities are likely a key defect whose concentration can be controlled by simple annealing procedures in order to increase the performance for perovskite solar cells.

  10. Magnetic ground states in the three O s6 + (5 d2 ) double perovskites B a2M Os O6 (M =Mg ,Zn,and Cd) from Néel order to its suppression

    NASA Astrophysics Data System (ADS)

    Marjerrison, C. A.; Thompson, C. M.; Sharma, A. Z.; Hallas, A. M.; Wilson, M. N.; Munsie, T. J. S.; Flacau, R.; Wiebe, C. R.; Gaulin, B. D.; Luke, G. M.; Greedan, J. E.

    2016-10-01

    Three closely related double perovskites (DP) based on the 5 d2 ion, O s6 +,B a2M Os O6 , with M =Mg , Zn, and Cd have been prepared and characterized using x-ray (XRD) and neutron diffraction (ND), dc magnetization, heat capacity, and muon spin relaxation (μ SR ) techniques. All three are cubic, Fm-3 m , at ambient temperature from XRD with Δ d /d ˜5 ×10-4 resolution. For both M =Mg and Zn, ND data at 3.5 K and lower, Δ d /d =2 ×10-3 , resolution show no signs of a distortion. The results are compared with the known DP material, B a2CaOs O6 , which shows antiferromagnetic (AF) order below TN=49 K and a moderate frustration index, f ˜4 , (f =| θCW|/ TN ), where θCW is the Curie-Weiss temperature. B a2MgOs O6 with a unit cell constant a0=8.0757 (1 ) Å , 3% smaller than for B a2CaOs O6 , also shows Néel order below TN=51 K with f ˜2 . However, B a2ZnOs O6,a0=8.0975 (1 ) Å , 0.27% larger than B a2MgOs O6 , does not show Néel order from either heat capacity or μ SR data. A zero field cooled/field cooled (ZFC/FC) irreversibility occurs near 30 K and a broad heat capacity anomaly is detected at a similar temperature. The μ SR data are consistent with a weak spin ordering with an onset below 28 K but with a coexisting dynamic component. B a2CdOs O6 with a0=8.3190 (1 ) Å , 0.5% smaller than B a2CaOs O6 , shows no evidence for any type of order/spin freezing to 0.47 K from any of the measurement techniques applied. The results for M =Zn and Cd appear to lie outside of the mean field theory of Chen and Balents [Phys. Rev. B 84, 094420 (2011), 10.1103/PhysRevB.84.094420] for cubic d2 DP with strong spin orbit coupling, but B a2MgOs O6 , along with B a2CaOs O6 , is likely one of the three predicted AF phases. The remarkable contrast between the doppelgänger pairs M =Mg /Zn and M =Ca /Cd may be traceable to differences in electronic structure of the diamagnetic M ions. All of the super-super exchange pathways in these DP materials involve Os-O-M -O-Os linkages.

  11. Long-range magnetic order in the 5d(2) double perovskite Ba2CaOsO6: comparison with spin-disordered Ba2YReO6.

    PubMed

    Thompson, C M; Carlo, J P; Flacau, R; Aharen, T; Leahy, I A; Pollichemi, J R; Munsie, T J S; Medina, T; Luke, G M; Munevar, J; Cheung, S; Goko, T; Uemura, Y J; Greedan, J E

    2014-07-30

    The B-site ordered double perovskite Ba2CaOsO6 was studied by dc magnetic susceptibility, powder neutron diffraction and muon spin relaxation methods. The lattice parameter is a = 8.3619(6) Å at 280 K and cubic symmetry [Formula: see text] is retained to 3.5 K with a = 8.3462(7) Å. Curie-Weiss susceptibility behaviour is observed for T > 100 K and the derived constants are C = 0.3361(3) emu K mol(-1) and ΘCW = -156.2(3) K, in excellent agreement with literature values. This Curie constant is much smaller than the spin-only value of 1.00 emu K mol(-1) for a 5d(2) Os(6+) configuration, indicating a major influence of spin-orbit coupling. Previous studies had detected both susceptibility and heat capacity anomalies near 50 K but no definitive conclusion was drawn concerning the nature of the ground state. While no ordered Os moment could be detected by powder neutron diffraction, muon spin relaxation (µSR) data show clear long-lived oscillations indicative of a continuous transition to long-range magnetic order below TC = 50 K. An estimate of the ordered moment on Os(6+) is ∼ 0.2 μB, based upon a comparison with µSR data for Ba2YRuO6 with a known ordered moment of 2.2 μB. These results are compared with those for isostructural Ba2YReO6 which contains Re(5+), also 5d(2), and has a nearly identical unit cell constant, a = 8.36278(2) Å-a structural doppelgänger. In contrast, Ba2YReO6 shows ΘCW = - 616 K, and a complex spin-disordered and, ultimately, spin-frozen ground state below 50 K, indicating a much higher level of geometric frustration than in Ba2CaOsO6. The results on these 5d(2) systems are compared to recent theory, which predicts a variety of ferromagnetic and antiferromagnetic ground states. In the case of Ba2CaOsO6, our data indicate that a complex four-sublattice magnetic structure is likely. This is in contrast to the spin-disordered ground state in Ba2YReO6, despite a lack of evidence for structural disorder

  12. High Performance Perovskite Solar Cells.

    PubMed

    Tong, Xin; Lin, Feng; Wu, Jiang; Wang, Zhiming M

    2016-05-01

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

  13. High Performance Perovskite Solar Cells

    PubMed Central

    Tong, Xin; Lin, Feng; Wu, Jiang

    2015-01-01

    Perovskite solar cells fabricated from organometal halide light harvesters have captured significant attention due to their tremendously low device costs as well as unprecedented rapid progress on power conversion efficiency (PCE). A certified PCE of 20.1% was achieved in late 2014 following the first study of long‐term stable all‐solid‐state perovskite solar cell with a PCE of 9.7% in 2012, showing their promising potential towards future cost‐effective and high performance solar cells. Here, notable achievements of primary device configuration involving perovskite layer, hole‐transporting materials (HTMs) and electron‐transporting materials (ETMs) are reviewed. Numerous strategies for enhancing photovoltaic parameters of perovskite solar cells, including morphology and crystallization control of perovskite layer, HTMs design and ETMs modifications are discussed in detail. In addition, perovskite solar cells outside of HTMs and ETMs are mentioned as well, providing guidelines for further simplification of device processing and hence cost reduction. PMID:27774402

  14. The Synthesis and Characterization of Some Fluoride Perovskites: An Undergraduate Experiment in Solid State Chemistry.

    ERIC Educational Resources Information Center

    Langley, Richard H.; And Others

    1984-01-01

    Describes a senior-level experiment dealing with the synthesis and characterization of a perovskite. Since most perovskites are cubic, their characterization by x-ray diffraction is simplified. In addition, magnetic ordering may be observed and the effects of a Jahn-Teller distortion seen. (JN)

  15. The Synthesis and Characterization of Some Fluoride Perovskites: An Undergraduate Experiment in Solid State Chemistry.

    ERIC Educational Resources Information Center

    Langley, Richard H.; And Others

    1984-01-01

    Describes a senior-level experiment dealing with the synthesis and characterization of a perovskite. Since most perovskites are cubic, their characterization by x-ray diffraction is simplified. In addition, magnetic ordering may be observed and the effects of a Jahn-Teller distortion seen. (JN)

  16. Oxygen deficient layered double perovskite as an active cathode for CO2 electrolysis using a solid oxide conductor.

    PubMed

    Shin, Tae Ho; Myung, Jae-Ha; Verbraeken, Maarten; Kim, Guntae; Irvine, John T S

    2015-01-01

    A-site ordered PrBaMn2O(5+δ) was investigated as a potential cathode for CO2 electrolysis using a La(0.9)Sr(0.1)Ga(0.8)Mg(0.2)O3 (LSGM) electrolyte. The A-site ordered layered double perovskite, PrBaMn2O(5+δ), was found to enhance electrocatalytic activity for CO2 reduction on the cathode side since it supports mixed valent transition metal cations such as Mn, which could provide high electrical conductivity and maintain a large oxygen vacancy content, contributing to fast oxygen ion diffusion. It was found that during the oxidation of the reduced PrBaMn2O(5+δ) (O5 phase) to PrBaMn2O(6-δ) (O6 phase), a reversible oxygen switchover in the lattice takes place. In addition, here the successful CO2 electrolysis was measured in LSGM electrolyte with this novel oxide electrode. It was found that this PrBaMn2O(5+δ), layered perovskite cathode exhibits a performance with a current density of 0.85 A cm(-2) at 1.5 V and 850 °C and the electrochemical properties were also evaluated by impedance spectroscopy.

  17. Two-Photon Absorption in Organometallic Bromide Perovskites.

    PubMed

    Walters, Grant; Sutherland, Brandon R; Hoogland, Sjoerd; Shi, Dong; Comin, Riccardo; Sellan, Daniel P; Bakr, Osman M; Sargent, Edward H

    2015-09-22

    Organometallic trihalide perovskites are solution-processed semiconductors that have made great strides in third-generation thin film light-harvesting and light-emitting optoelectronic devices. Recently, it has been demonstrated that large, high-purity single crystals of these perovskites can be synthesized from the solution phase. These crystals' large dimensions, clean bandgap, and solid-state order have provided us with a suitable medium to observe and quantify two-photon absorption in perovskites. When CH3NH3PbBr3 single crystals are pumped with intense 800 nm light, we observe band-to-band photoluminescence at 572 nm, indicative of two-photon absorption. We report the nonlinear absorption coefficient of CH3NH3PbBr3 perovskites to be 8.6 cm GW(-1) at 800 nm, comparable to epitaxial single-crystal semiconductors of similar bandgap. We have leveraged this nonlinear process to electrically autocorrelate a 100 fs pulsed laser using a two-photon perovskite photodetector. This work demonstrates the viability of organometallic trihalide perovskites as a convenient and low-cost nonlinear absorber for applications in ultrafast photonics.

  18. Metal halide perovskite light emitters

    PubMed Central

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

    2016-01-01

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

  19. A deconvoluted PL approach to probe the charge carrier dynamics of the grain interior and grain boundary of a perovskite film for perovskite solar cell applications.

    PubMed

    Mamun, Abdullah Al; Ava, Tanzila Tasnim; Jeong, Hyeon Jun; Jeong, Mun Seok; Namkoong, Gon

    2017-03-29

    We explore a new characterization approach capable of probing the grain interior (GI) and grain boundary (GB) of a CH3NH3PbI3-xClx perovskite thin film. In particular, we have found that the photoluminescence (PL) spectrum observed for a CH3NH3PbI3-xClx perovskite thin film is asymmetric, and can be deconvoluted using a bi-Gaussian function, representing the ordered and disordered phases of the perovskite film. In order to understand the origin of the ordered and disordered phases of the perovskite film, two-dimensional (2D) PL mapping was performed to resolve the PL spectra at the nanoscale level. Quantitative analysis of the local PL spectra revealed that the ordered phase originated from the GIs while the disordered phase mainly came from the GBs. In particular, power-dependent PL measurements of the deconvoluted PL spectra revealed that smaller grained perovskites showed defect-mediated recombination at GBs but exciton-like transitions at GIs. In contrast, perovskite films with large grains followed an excellent power law, showing exciton-like recombination at both GIs and GBs. As expected, perovskite solar cells fabricated with large grains showed an increased efficiency with higher light absorption and higher charge extraction efficiency.

  20. Synthesis, structural characterization and Mössbauer study of LnV{sub 0.5}Fe{sub 0.5}O{sub 3} perovskites (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er)

    SciTech Connect

    Ivashita, Flávio F.; Biondo, Valdecir; Bellini, Jusmar V.; Paesano, Andrea; Blanco, M. Cecilia; Fuertes, Valeria C.; Pannunzio-Miner, Elisa V.; Carbonio, Raúl E.

    2012-09-15

    Graphical abstract: Mössbauer spectra taken at 200 K for the Y(V{sub 0.5}Fe{sub 0.5})O{sub 3} orthoferrivanadate synthesized by arc-melting. Highlights: ► LnFe{sub 0.5}V{sub 0.5}O{sub 3} were synthesized by the first time for most of the rare-earth elements. ► These orthoferrivanadates crystallize metastably with the perovskite structure. ► Iron and vanadium are trivalent stabilized in these solid solutions. ► The Mössbauer quadrupolar splitting is correlated with the tolerance factor. ► Below 100 K, these perovskites undergo a crystallographic phase transformation. -- Abstract: Perovskites LnV{sub 0.5}Fe{sub 0.5}O{sub 3} (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Er) were synthesized by rapid solidification from arc-melted samples and characterized by the study of their crystal structure and hyperfine properties. These metastable solid solutions crystallized in the Pbnm symmetry, with the iron and vanadium cations randomly distributed in the transition metal octahedral sites. Depending on the lanthanide present at the A site of the perovskite, iron is present with two valences (i.e., Fe{sup 3+} and Fe{sup 2+}). The volume of the unit cell for these perovskites increases linearly with the lanthanide ionic radius, as the perovskite approaches its ideal structure. At room temperature, the quadrupolar splitting of the trivalent paramagnetic Mössbauer component works as an indirect measurement for the Goldshmidt tolerance factor. Close to or below 100 K, these perovskites undergo a crystallographic phase transformation, probably due to orbital ordering of the V{sup 3+} cations, originating two different magnetic iron sites.

  1. Band Gap Tuning via Lattice Contraction and Octahedral Tilting in Perovskite Materials for Photovoltaics

    DOE PAGES

    Prasanna, Rohit; Gold-Parker, Aryeh; Leijtens, Tomas; ...

    2017-07-13

    Tin and lead iodide perovskite semiconductors of the composition AMX3, where M is a metal and X is a halide, are leading candidates for high efficiency low cost tandem photovoltaics, in part because they have band gaps that can be tuned over a wide range by compositional substitution. We experimentally identify two competing mechanisms through which the A-site cation influences the band gap of 3D metal halide perovskites. Using a smaller A-site cation can distort the perovskite lattice in two distinct ways: by tilting the MX6 octahedra or by simply contracting the lattice isotropically. The former effect tends to raisemore » the band gap, while the latter tends to decrease it. Lead iodide perovskites show an increase in band gap upon partial substitution of the larger formamidinium with the smaller cesium, due to octahedral tilting. Perovskites based on tin, which is slightly smaller than lead, show the opposite trend: they show no octahedral tilting upon Cs-substitution but only a contraction of the lattice, leading to progressive reduction of the band gap. We outline a strategy to systematically tune the band gap and valence and conduction band positions of metal halide perovskites through control of the cation composition. Using this strategy, we demonstrate solar cells that harvest light in the infrared up to 1040 nm, reaching a stabilized power conversion efficiency of 17.8%, showing promise for improvements of the bottom cell of all-perovskite tandem solar cells. In conclusion, the mechanisms of cation-based band gap tuning we describe are broadly applicable to 3D metal halide perovskites and will be useful in further development of perovskite semiconductors for optoelectronic applications.« less

  2. Band Gap Tuning via Lattice Contraction and Octahedral Tilting in Perovskite Materials for Photovoltaics.

    PubMed

    Prasanna, Rohit; Gold-Parker, Aryeh; Leijtens, Tomas; Conings, Bert; Babayigit, Aslihan; Boyen, Hans-Gerd; Toney, Michael F; McGehee, Michael D

    2017-08-16

    Tin and lead iodide perovskite semiconductors of the composition AMX3, where M is a metal and X is a halide, are leading candidates for high efficiency low cost tandem photovoltaics, in part because they have band gaps that can be tuned over a wide range by compositional substitution. We experimentally identify two competing mechanisms through which the A-site cation influences the band gap of 3D metal halide perovskites. Using a smaller A-site cation can distort the perovskite lattice in two distinct ways: by tilting the MX6 octahedra or by simply contracting the lattice isotropically. The former effect tends to raise the band gap, while the latter tends to decrease it. Lead iodide perovskites show an increase in band gap upon partial substitution of the larger formamidinium with the smaller cesium, due to octahedral tilting. Perovskites based on tin, which is slightly smaller than lead, show the opposite trend: they show no octahedral tilting upon Cs-substitution but only a contraction of the lattice, leading to progressive reduction of the band gap. We outline a strategy to systematically tune the band gap and valence and conduction band positions of metal halide perovskites through control of the cation composition. Using this strategy, we demonstrate solar cells that harvest light in the infrared up to 1040 nm, reaching a stabilized power conversion efficiency of 17.8%, showing promise for improvements of the bottom cell of all-perovskite tandem solar cells. The mechanisms of cation-based band gap tuning we describe are broadly applicable to 3D metal halide perovskites and will be useful in further development of perovskite semiconductors for optoelectronic applications.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  4. Influence of void-free perovskite capping layer on the charge recombination process in high performance CH3NH3PbI3 perovskite solar cells.

    PubMed

    Fu, Kunwu; Nelson, Christopher T; Scott, Mary Cooper; Minor, Andrew; Mathews, Nripan; Wong, Lydia Helena

    2016-02-21

    The stunning rise of methylammonium lead iodide perovskite material as a light harvesting material in recent years has drawn much attention in the photovoltaic community. Here, we investigated in detail the uniform and void-free perovskite capping layer in the mesoscopic perovskite devices and found it to play a critical role in determining device performance and charge recombination process. Compared to the rough surface with voids of the perovskite layer, surface of the perovskite capping layer obtained from sequential deposition process is much more uniform with less void formation and distribution within the TiO2 mesoscopic scaffold is more homogeneous, leading to much improved photovoltaic parameters of the devices. The impact of void free perovskite capping layer surface on the charge recombination processes within the mesoscopic perovskite solar cells is further scrutinized via charge extraction measurement. Modulation of precursor solution concentrations in order to further improve the perovskite layer surface morphology leads to higher efficiency and lower charge recombination rates. Inhibited charge recombination in these solar cells also matches with the higher charge density and slower photovoltage decay profiles measured.

  5. Fabrication and Characterization of High-Quality Perovskite Films with Large Crystal Grains.

    PubMed

    Ma, Teng; Zhang, Qiwu; Tadaki, Daisuke; Hirano-Iwata, Ayumi; Niwano, Michio

    2017-02-16

    Solution-processable organometal perovskite materials have been widely used in various kinds of devices. In these devices, the perovskite materials normally act as active layers. Grain boundaries and structural disorder in the perovskite layer would interfere the charge transport and increase recombination probability. Here we proposed a novel fabrication method to dramatically increase the crystal size by more than 20 times as compared with previously reported values. Exceptional structural order in the large crystals is illustrated by nanoscale surface morphology and a simple recrystallization method. Because of reduced grain boundaries and increased crystal order in perovskite layers, the lateral charge transport is significantly improved, as demonstrated by conductive atomic-force microscopy and performance of photodetectors. This deposition technology paves the way for future high-performance devices based on perovskite thin films.

  6. 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.

  7. 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

  8. Organometal Halide Perovskite Artificial Synapses.

    PubMed

    Xu, Wentao; Cho, Himchan; Kim, Young-Hoon; Kim, Young-Tae; Wolf, Christoph; Park, Chan-Gyung; Lee, Tae-Woo

    2016-07-01

    Organometal halide perovskite synaptic devices are fabricated; they emulate important working principles of a biological synapse, including excitatory postsynaptic current, paired-pulse facilitation, short-term plasticity, long-term plasticity, and spike-timing dependent plasticity. These properties originate from possible ion migration in the ion-rich perovskite matrix. This work has extensive applicability and practical significance in neuromorphic electronics.

  9. Cationic disorder and Mn{sup 3+}/Mn{sup 4+} charge ordering in the B′ and B″ sites of Ca{sub 3}Mn{sub 2}NbO{sub 9} perovskite: a comparison with Ca{sub 3}Mn{sub 2}WO{sub 9}

    SciTech Connect

    López, C.A.; Saleta, M.E.; Pedregosa, J.C.; Sánchez, R.D.; Alonso, J.A.; and others

    2014-02-15

    We describe the preparation, crystal structure determination, magnetic and transport properties of two novel Mn-containing perovskites, with a different electronic configuration for Mn atoms located in B site. Ca{sub 3}Mn{sup 3+}{sub 2}WO{sub 9} and Ca{sub 3}Mn{sup 3+/4+}{sub 2}NbO{sub 9} were synthesized by standard ceramic procedures; the crystallographic structure was studied from X-ray powder diffraction (XRPD) and neutron powder diffraction (NPD). Both phases exhibit a monoclinic symmetry (S.G.: P2{sub 1}/n); Ca{sub 3}Mn{sub 2}WO{sub 9} presents a long-range ordering over the B sites, whereas Ca{sub 3}Mn{sub 2}NbO{sub 9} is strongly disordered. By “in-situ” NPD, the temperature evolution of the structure study presents an interesting evolution in the octahedral size (〈Mn–O〉) for Ca{sub 3}Mn{sub 2}NbO{sub 9}, driven by a charge ordering effect between Mn{sup 3+} and Mn{sup 4+} atoms, related to the anomaly observed in the transport measurements at T≈160 K. Both materials present a magnetic order below T{sub C}=30 K and 40 K for W and Nb materials, respectively. The magneto-transport measurements display non-negligible magnetoresistance properties in the paramagnetic regime. - Graphical abstract: Comparison between the octahedron size and the magnetic behaviour for Ca{sub 3}Mn{sub 2}NbO{sub 9} in the temperature region where the charge and magnetic order occur. Display Omitted - Highlights: • Two novel Mn-containing double perovskites were obtained by solid-state reactions. • Both double perovskites are monoclinic (P2{sub 1}/n) determined by XRPD and NPD. • Ca{sub 3}Mn{sub 2}WO{sub 9} contains Mn{sup 3+} while Ca{sub 3}Mn{sub 2}NbO{sub 9} includes mixed-valence cations Mn{sup 3+}/Mn{sup 4+}. • Ca{sub 3}Mn{sub 2}NbO{sub 9} presents a charge-ordering effect between Mn{sup 3+} and Mn{sup 4+} evidenced by NPD. • The magnetic and transport studies evidenced the charge ordering in Ca{sub 3}Mn{sub 2}NbO{sub 9}.

  10. Oxygen storage properties and catalytic activity of layer-ordered perovskites BaY1-xGdxMn2O5+δ

    SciTech Connect

    Klimkowicz, A.; Świerczek, K.; Rząsa, T.; Takasaki, A.; Dabrowski, B.

    2016-05-01

    Crystal structure, oxygen storage-related and preliminary anaerobic methane combustion studies were conducted for BaY1-xGdxMn2O5+δ (0, 0.25, 0.5, 0.75 and 1) series of oxides prepared by a sol–gel method. All samples were found to possess layered-type A-site cation ordering, with the unit cell volume linearly dependent on the average radius of Y1-xGdx for both the reduced and the oxidized materials. The oxygen content in the temperature range of 400 °C–600 °C indicates change on the order of 1 atomic mole, occurring when the sample's surrounding atmosphere was changed from air to 5 vol.% H2 in Ar. The time dependence of the reduction shows activated character on temperature, with an activation energy, which seems to be related to the oxygen diffusion in the bulk of the materials. Initial data concerning methane combustion in oxygen-free conditions show promising catalytic activity of BaYMn2O6 at elevated temperatures.

  11. Advances in Perovskite Solar Cells.

    PubMed

    Zuo, Chuantian; Bolink, Henk J; Han, Hongwei; Huang, Jinsong; Cahen, David; Ding, Liming

    2016-07-01

    Organolead halide perovskite materials possess a combination of remarkable optoelectronic properties, such as steep optical absorption edge and high absorption coefficients, long charge carrier diffusion lengths and lifetimes. Taken together with the ability for low temperature preparation, also from solution, perovskite-based devices, especially photovoltaic (PV) cells have been studied intensively, with remarkable progress in performance, over the past few years. The combination of high efficiency, low cost and additional (non-PV) applications provides great potential for commercialization. Performance and applications of perovskite solar cells often correlate with their device structures. Many innovative device structures were developed, aiming at large-scale fabrication, reducing fabrication cost, enhancing the power conversion efficiency and thus broadening potential future applications. This review summarizes typical structures of perovskite solar cells and comments on novel device structures. The applications of perovskite solar cells are discussed.

  12. Neutron and X-Ray Scattering Studies of Hybrid Perovskites for Photovoltaic Applications

    NASA Astrophysics Data System (ADS)

    Crawford, Michael; Whitfield, Pamela; Jalarvo, Niina; Ehlers, Georg; Tyagi, Madhusudan; Herron, Norman; Johnson, Lynda; Guise, William; Milas, Ivan; Cheng, Yongqiang; Daemen, Luke; Ramirez-Cuesta, Anibal; Page, Katharine; Wang, Xiaoping; Ye, Feng

    Hybrid perovskites (ABX3) have attracted a great deal of attention recently as light absorbers for photovoltaics. In these materials the A site is occupied by organic cations, for example methyl ammonium (MA) or formamidinium (FA) cations, the B site is occupied by metals, for example Pb or Sn, and the X anions are halogens (I, Br, or Cl). Typical of perovskites, these materials exhibit a series of structural phase transitions involving rotations or tilts of the BX6 octahedra, but with the added complexity that the inorganic framework is coupled to order-disorder transitions of the organic cations. We have used neutron scattering techniques to characterize the structures and dynamics of several of these compounds as a function of temperature. In addition, high resolution synchrotron x-ray diffraction measurements have been performed to investigate the structural phase transitions. These studies yield a detailed picture of the structures, dynamics, and structural phase transitions of these compounds, and provide a firm basis for understanding their excellent photovoltaic properties.

  13. Formulation of predictive models for use in first principles design of non-centrosymmetric perovskite oxides

    NASA Astrophysics Data System (ADS)

    Young, Joshua; Rondinelli, James

    2014-03-01

    Because many useful electronic properties such as ferroelectricity arise solely due to the lack of inversion in a material's crystal structure, predictive microscopic models describing how to deterministically remove this symmetry operation can allow for the rapid identification and design of new polar compounds. By understanding how structural distortions influence the connectivity between oxygen polyhedra in solid state oxides, we elucidate a series of geometric design rules necessary to develop polar materials. We then apply these criteria to the family of ABO3 perovskite oxides by systematically investigating how distortions of the corner-connected BO6 polyhedral network influence the A-site environments, resulting in a detailed description of the octahedral rotation patterns and A- and B-site cation ordering arrangements capable of producing centrosymmetric, polar, and enantiomorphic structures. Using this as a guide, we then show how such a method allows for the targeted design of new non-centrosymmetric oxides. We conclude by using these rules in combination with density functional theory calculations to predict a series of rhombohedral (A,A')B2O6 perovskites displaying electric polarizations in their ground state.

  14. Tracking the formation of methylammonium lead triiodide perovskite

    SciTech Connect

    Liu, Lijia E-mail: jmcleod@suda.edu.cn; McLeod, John A. E-mail: jmcleod@suda.edu.cn; Wang, Rongbin; Shen, Pengfei; Duhm, Steffen

    2015-08-10

    The formation mechanism of perovskite methylammonium lead triiodide (CH{sub 3}NH{sub 3}PbI{sub 3}) was studied with in situ X-ray photoelectron spectroscopy (XPS) on successive depositions of thermally evaporated methylammonium iodide (CH{sub 3}NH{sub 3}I) on a lead iodide (PbI{sub 2}) film. This deposition method mimics the “two-step” synthesis method commonly used in device fabrication. We find that several competing processes occur during the formation of perovskite CH{sub 3}NH{sub 3}PbI{sub 3}. Our most important finding is that during vapour deposition of CH{sub 3}NH{sub 3}I onto PbI{sub 2}, at least two carbon species are present in the resulting material, while only one nitrogen species is present. This suggests that CH{sub 3}NH{sub 3}I can dissociate during the transition to a perovskite phase, and some of the resulting molecules can be incorporated into the perovskite. The effect of partial CH{sub 3}NH{sub 3} substitution with CH{sub 3} was evaluated, and electronic structure calculations show that CH{sub 3} defects would impact the photovoltaic performance in perovskite solar cells. The possibility that not all A sites in the APbI{sub 3} perovskite are occupied by CH{sub 3}NH{sub 3} is therefore an important consideration when evaluating the performance of organometallic trihalide solar cells synthesized using typical approaches.

  15. Magnetic properties of Pr ions in perovskite-type oxides

    NASA Astrophysics Data System (ADS)

    Sekizawa, K.; Kitagawa, M.; Takano, Y.

    1998-01-01

    Magnetic properties of Pr ions with the controlled valence on the A and B sites of perovskite-type oxides (ABO 3) were investigated for two systems, PrSc 1 - xMg xO 3 and BaPr 1 - xBi xO 3. From the magnetic susceptibility χ versus temperature T curves of PrSc 1 - xMg xO 3, the χ-T curve for molar Pr 3+ ions on the A site and that of Pr 4+ ions were obtained. The 1/χ-T curves for both ions exhibit the crystalline electric field (CEF) effect and the effective magnetic moment μ eff above 100 K is 3.41 μ B for Pr 3+ and 2.58 μ B for Pr 4+, respectively. The χ-T curve of PrSc 0.8Mg 0.2O 3 is similar to that of PrBa 2Cu 3O y. In the BaPr 1 - xBi xO 3 system, only one intermediate phase BaPr 0.5Bi 0.5O 3 exists, in which Pr and Bi take an ordered arrangement on the B site. The magnetic susceptibility χ for Pr 4+ and that of Pr 3- in the ordered arrangement with Bi 5+ on the B site are much smaller than those for the A site, reflecting the strong CEF effect on the B site. Experimental χ-T curves can be well reproduced by the numerical calculation for Pr 3+ or Pr 4+ ions in the molecular field and the CEF with proper respective parameters.

  16. 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.

  17. Crystal and electronic structures of substituted halide perovskites based on density functional calculation and molecular dynamics

    NASA Astrophysics Data System (ADS)

    Takaba, Hiromitsu; Kimura, Shou; Alam, Md. Khorshed

    2017-03-01

    Durability of organo-lead halide perovskite are important issue for its practical application in a solar cells. In this study, using density functional theory (DFT) and molecular dynamics, we theoretically investigated a crystal structure, electronic structure, and ionic diffusivity of the partially substituted cubic MA0.5X0.5PbI3 (MA = CH3NH3+, X = NH4+ or (NH2)2CH+ or Cs+). Our calculation results indicate that a partial substitution of MA induces a lattice distortion, resulting in preventing MA or X from the diffusion between A sites in the perovskite. DFT calculations show that electronic structures of the investigated partially substituted perovskites were similar with that of MAPbI3, while their bandgaps slightly decrease compared to that of MAPbI3. Our results mean that partial substitution in halide perovskite is effective technique to suppress diffusion of intrinsic ions and tune the band gap.

  18. Magnetic Field-Assisted Perovskite Film Preparation for Enhanced Performance of Solar Cells.

    PubMed

    Wang, Haoxu; Lei, Jie; Gao, Fei; Yang, Zhou; Yang, Dong; Jiang, Jiexuan; Li, Juan; Hu, Xihong; Ren, Xiaodong; Liu, Bin; Liu, Jing; Lei, Hairui; Liu, Zhike; Liu, Shengzhong Frank

    2017-07-05

    Perovskite solar cells (PSCs) are promising low-cost photovoltaic technologies with high power conversion efficiency (PCE). The crystalline quality of perovskite materials is crucial to the photovoltaic performance of the PSCs. Herein, a simple approach is introduced to prepare high-quality CH3NH3PbI3 perovskite films with larger crystalline grains and longer carriers lifetime by using magnetic field to control the nucleation and crystal growth. The fabricated planar CH3NH3PbI3 solar cells have an average PCE of 17.84% and the highest PCE of 18.56% using an optimized magnetic field at 80 mT. In contrast, the PSCs fabricated without the magnetic field give an average PCE of 15.52% and the highest PCE of 16.72%. The magnetic field action produces an ordered arrangement of the perovskite ions, improving the crystallinity of the perovskite films and resulting in a higher PCE.

  19. Glory of piezoelectric perovskites

    PubMed Central

    Uchino, Kenji

    2015-01-01

    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. PMID:27877827

  20. Layered hybrid perovskites with micropores created by alkylammonium functional silsesquioxane interlayers.

    PubMed

    Kataoka, Sho; Banerjee, Subhabrata; Kawai, Akiko; Kamimura, Yoshihiro; Choi, Jun-Chul; Kodaira, Tetsuya; Sato, Kazuhiko; Endo, Akira

    2015-04-01

    Layered organic-inorganic hybrid perovskites that consist of metal halides and organic interlayers are a class of low-dimensional materials. Here, we report the fabrication of layered hybrid perovskites using metal halides and silsesquioxane with a cage-like structure. We used a silsesquioxane as an interlayer to produce a rigid structure and improve the functionality of perovskite layers. Propylammonium-functionalized silsesquioxane and metal halide salts (CuCl2, PdCl2, PbCl2, and MnCl2) were self-assembled to form rigid layered perovskite structures with high crystallinity. The rigid silsesquioxane structure produces micropores between the perovskite layers that can potentially be filled with different molecules to tune the dielectric constants of the interlayers. The obtained silsesquioxane-metal halide hybrid perovskites exhibit some characteristic properties of layered perovskites including magnetic ordering (CuCl4(2-) and MnCl4(2-)) and excitonic absorption/emission (PbCl4(2-)). Our results indicate that inserting silsesquioxane interlayers into hybrid perovskites retains and enhances the low-dimensional properties of the materials.

  1. NaIrO{sub 3}-A pentavalent post-perovskite

    SciTech Connect

    Bremholm, M.; Dutton, S.E.; Stephens, P.W.; Cava, R.J.

    2011-03-15

    Sodium iridium (V) oxide, NaIrO{sub 3,} was synthesized by a high pressure solid state method and recovered to ambient conditions. It is found to be isostructural with CaIrO{sub 3}, the much-studied structural analog of the high-pressure post-perovskite phase of MgSiO{sub 3}. Among the oxide post-perovskites, NaIrO{sub 3} is the first example with a pentavalent cation. The structure consists of layers of corner- and edge-sharing IrO{sub 6} octahedra separated by layers of NaO{sub 8} bicapped trigonal prisms. NaIrO{sub 3} shows no magnetic ordering and resistivity measurements show non-metallic behavior. The crystal structure, electrical and magnetic properties are discussed and compared to known post-perovskites and pentavalent perovskite metal oxides. -- Graphical abstract: Sodium iridium(V) oxide, NaIrO{sub 3}, synthesized by a high pressure solid state method and recovered to ambient conditions is found to crystallize as the post-perovskite structure and is the first example of a pentavalent ABO{sub 3} post-perovskite. Research highlights: {yields} NaIrO{sub 3} post-perovskite stabilized by pressure. {yields} First example of a pentavalent oxide post-perovskite. {yields} Non-metallic and non-magnetic behavior of NaIrO{sub 3}.

  2. Multidimensional Perovskites: A Mixed Cation Approach Towards Ambient Stable and Tunable Perovskite Photovoltaics.

    PubMed

    Koh, Teck Ming; Thirumal, Krishnamoorthy; Soo, Han Sen; Mathews, Nripan

    2016-09-22

    Although halide perovskites are able to deliver high power conversion efficiencies, their ambient stability still remains an obstacle for commercialization. Thus, promoting the ambient stability of perovskites has become a key research focus. In this review, we highlight the sources of instability in conventional 3 D perovskites, including water intercalation, ion migration, and thermal decomposition. Recently, the multidimensional perovskites approach has become one of the most promising strategies to enhance the stability of perovskites. As compared to pure 2 D perovskites, multidimensional perovskites typically possess more ideal band gaps, better charge transport, and lower exciton binding energy, which are essential for photovoltaic applications. The larger organic cations in multidimensional perovskites could also be more chemically stable at higher temperatures than the commonly used methylammonium cation. By combining 3 D and 2 D perovskites to form multidimensional perovskites, halide perovskite photovoltaics can attain both high efficiency and increased stability.

  3. A Direct Bandgap Copper-Antimony Halide Perovskite.

    PubMed

    Vargas, Brenda; Ramos, Estrella; Pérez-Gutiérrez, Enrique; Alonso, Juan Carlos; Solis-Ibarra, Diego

    2017-07-12

    Since the establishment of perovskite solar cells (PSCs), there has been an intense search for alternative materials to replace lead and improve their stability toward moisture and light. As single-metal perovskite structures have yielded unsatisfactory performances, an alternative is the use of double perovskites that incorporate a combination of metals. To this day, only a handful of these compounds have been synthesized, but most of them have indirect bandgaps and/or do not have bandgaps energies well-suited for photovoltaic applications. Here we report the synthesis and characterization of a unique mixed metal ⟨111⟩-oriented layered perovskite, Cs4CuSb2Cl12 (1), that incorporates Cu(2+) and Sb(3+) into layers that are three octahedra thick (n = 3). In addition to being made of abundant and nontoxic elements, we show that this material behaves as a semiconductor with a direct bandgap of 1.0 eV and its conductivity is 1 order of magnitude greater than that of MAPbI3 (MA = methylammonium). Furthermore, 1 has high photo- and thermal-stability and is tolerant to humidity. We conclude that 1 is a promising material for photovoltaic applications and represents a new type of layered perovskite structure that incorporates metals in 2+ and 3+ oxidation states, thus significantly widening the possible combinations of metals to replace lead in PSCs.

  4. 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

    2015-12-02

    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.

  5. Raman studies of A2MWO6 tungstate double perovskites.

    PubMed

    Andrews, R L; Heyns, A M; Woodward, P M

    2015-06-21

    The Raman spectra of seven A(2)MWO(6) tungstate double perovskites are analysed. Ba(2)MgWO(6) is a cubic double perovskite with Fm3[combining macron]m symmetry and its Raman spectrum contain three modes that can be assigned in a straightforward manner. A fourth mode, the asymmetric stretch of the [WO(6)](6-) octahedron, is too weak to be observed. The symmetry of Ba(2)CaWO(6) is lowered to tetragonal I4/m due to octahedral tilting, but the distortion is sufficiently subtle that the extra bands predicted to appear in the Raman spectrum are not observed. The remaining five compounds have additional octahedral tilts that lower the symmetry to monoclinic P2(1)/n. The further reduction of symmetry leads to the appearance of additional lattice modes involving translations of the A-site cations and librations of the octahedra. Comparing the Raman spectra of fourteen different A(2)MWO(6) tungstate double perovskites shows that the frequency of the symmetric stretch (ν(1)) of the [WO(6)](6-) octahedron is relatively low for cubic perovskites with tolerance factors greater than one due to underbonding of the tungsten and/or M cation. The frequency of this mode increases rapidly as the tolerance factor drops below one, before decreasing gradually as the octahedral tilting gets larger. The frequency of the oxygen bending mode (ν(5)) is shown to be dependent on the mass of the A-site cation due to coupling of the internal bending mode with external A-site cation translation modes.

  6. Multigap Semiconducting ferroelectric perovskites

    NASA Astrophysics Data System (ADS)

    Jiang, Lai; Grinberg, Ilya; Wang, Fenggong; Davies, Peter; Rappe, Andrew

    2013-03-01

    The energy conversion efficiency of a solar cell is directly related to the band gap of the material. By doping ferroelectric perovskites with Bi5+ on the B-site, we propose low band-gap materials suitable for bulk photovoltaic effect and related solar applications.Our DFT calculations indicate that the low-lying 6 s empty states of the electronegative Bi atom produce empty isolated bands in the gap of the parent materials, effectively lowering the band gap by 1 ~2eV in various perovskites. Ferroelectricity (and therefore inversion symmetry breaking) weakens but survives upon doping, which enables the ``shift current'' mechanism for photocurrent generation, while the decreased band gap helps absorb low energy photons in the visible range. Furthermore, the existence of multiple band gaps allows for solar conversion devices with efficiency beyond the traditional Shockly-Queisser limit, in which successive photon excitations result in carriers with higher energy than a single-step excitation would achieve.

  7. Electrical conductivity of (Mg,Fe)SiO3 Perovskite and a Perovskite-dominated assemblage at lower mantle conditions

    NASA Technical Reports Server (NTRS)

    Li, Xiaoyuan; Jeanloz, Raymond

    1987-01-01

    Electrical conductivity measurements of Perovskite and a Perovskite-dominated assemblage synthesized from pyroxene and olivine demonstrate that these high-pressure phases are insulating to pressures of 82 GPa and temperatures of 4500 K. Assuming an anhydrous upper mantle composition, the result provides an upper bound of 0.01 S/m for the electrical conductivity of the lower mantle between depths of 700 and 1900 km. This is 2 to 4 orders of magnitude lower than previous estimates of lower-mantle conductivity derived from studies of geomagnetic secular variations.

  8. Electrical conductivity of (Mg,Fe)SiO3 Perovskite and a Perovskite-dominated assemblage at lower mantle conditions

    NASA Technical Reports Server (NTRS)

    Li, Xiaoyuan; Jeanloz, Raymond

    1987-01-01

    Electrical conductivity measurements of Perovskite and a Perovskite-dominated assemblage synthesized from pyroxene and olivine demonstrate that these high-pressure phases are insulating to pressures of 82 GPa and temperatures of 4500 K. Assuming an anhydrous upper mantle composition, the result provides an upper bound of 0.01 S/m for the electrical conductivity of the lower mantle between depths of 700 and 1900 km. This is 2 to 4 orders of magnitude lower than previous estimates of lower-mantle conductivity derived from studies of geomagnetic secular variations.

  9. All-inorganic inverse perovskite solar cells using zinc oxide nanocolloids on spin coated perovskite layer.

    PubMed

    Shibayama, Naoyuki; Kanda, Hiroyuki; Yusa, Shin-Ichi; Fukumoto, Shota; Baranwal, Ajay K; Segawa, Hiroshi; Miyasaka, Tsutomu; Ito, Seigo

    2017-01-01

    We confirmed the influence of ZnO nanoparticle size and residual water on performance of all inorganic perovskite solar cells. By decreasing the size of the ZnO nanoparticles, the short-circuit current density (Jsc) and open circuit photovoltage (Voc) values are increased and the conversion efficiency is improved. Although the Voc value is not affected by the influence of residual water in the solution for preparing the ZnO layer, the Jsc value drops greatly. As a result, it was found that it is important to use the oxide nanoparticles with a small particle diameter and to reduce the water content in the oxide forming material in order to manufacture a highly efficient all inorganic perovskite solar cells.

  10. All-inorganic inverse perovskite solar cells using zinc oxide nanocolloids on spin coated perovskite layer

    NASA Astrophysics Data System (ADS)

    Shibayama, Naoyuki; Kanda, Hiroyuki; Yusa, Shin-ichi; Fukumoto, Shota; Baranwal, Ajay K.; Segawa, Hiroshi; Miyasaka, Tsutomu; Ito, Seigo

    2017-07-01

    We confirmed the influence of ZnO nanoparticle size and residual water on performance of all inorganic perovskite solar cells. By decreasing the size of the ZnO nanoparticles, the short-circuit current density ( Jsc) and open circuit photovoltage ( Voc) values are increased and the conversion efficiency is improved. Although the Voc value is not affected by the influence of residual water in the solution for preparing the ZnO layer, the Jsc value drops greatly. As a result, it was found that it is important to use the oxide nanoparticles with a small particle diameter and to reduce the water content in the oxide forming material in order to manufacture a highly efficient all inorganic perovskite solar cells.

  11. Perovskite photovoltaics: Slow recombination unveiled

    NASA Astrophysics Data System (ADS)

    Moser, Jacques-E.

    2017-01-01

    One of the most salient features of hybrid lead halide perovskites is the extended lifetime of their photogenerated charge carriers. This property has now been shown experimentally to originate from a slow, thermally activated recombination process.

  12. Advances in Perovskite Solar Cells

    PubMed Central

    Zuo, Chuantian; Bolink, Henk J.; Han, Hongwei; Huang, Jinsong

    2016-01-01

    Organolead halide perovskite materials possess a combination of remarkable optoelectronic properties, such as steep optical absorption edge and high absorption coefficients, long charge carrier diffusion lengths and lifetimes. Taken together with the ability for low temperature preparation, also from solution, perovskite‐based devices, especially photovoltaic (PV) cells have been studied intensively, with remarkable progress in performance, over the past few years. The combination of high efficiency, low cost and additional (non‐PV) applications provides great potential for commercialization. Performance and applications of perovskite solar cells often correlate with their device structures. Many innovative device structures were developed, aiming at large‐scale fabrication, reducing fabrication cost, enhancing the power conversion efficiency and thus broadening potential future applications. This review summarizes typical structures of perovskite solar cells and comments on novel device structures. The applications of perovskite solar cells are discussed. PMID:27812475

  13. The Bright Side of Perovskites.

    PubMed

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

    2016-11-03

    Incubating in the rise of perovskite photovoltaic era, the advances in material design encourage further promising optoelectronic exploitations. Here, we evaluate halide perovskite envisioning light-emitting applications, with a particular focus to the role that this material can effectively play in the field, discussing advantages and limitations with respect to state of art competing players. Specific benefits derive from the use of low dimensional and nanostructured perovskites, marginally exploited in photovoltaic devices, allowing for a tuning of the excited states properties and for the obtainment of intrinsic resonating structures. Thanks to these unique properties, halide perovskite ensure a great potential for the development of high-power applications, such as lighting and lasing.

  14. First principle research of possible HM-AFM in double perovskites A2MoOsO6 and A2TcReO6 (A = Si, Ge, Sn, and Pb) with group IVA elements set on the A-site position

    NASA Astrophysics Data System (ADS)

    Fuh, Huei-Ru; Liu, Yun-Ping; Wang, Yin-Kuo

    2013-05-01

    We calculated electronic structures of double perovskite structures of A2MoOsO6 and A2TcReO6 (A = Si, Ge, Sn, and Pb) based on the density functional theory which was carried out with a full structural optimization using generalized gradient approximation and taking into account the correlation effect (GGA + U). In GGA calculation, Pb2TcReO6 shows a half-metallic antiferromagnet (HM-AFM) characteristic, whereas Sn2MoOsO6, Pb2MoOsO6, and Sn2TcReO6 are nearly HM-AFMs. With GGA + U calculation, Sn2MoOsO6 and Pb2MoOsO6 become stable HM-AFM, but Sn2TcReO6 and Pb2TcReO6 changes HM-AFM into an antiferromagnetic insulator. The p-d hybridization between B(B')d-Op and double exchange interaction is the mean reason to result in the half-metallic and compensated ferrimagnetic phase.

  15. Octahedral Rotation Preferences in Perovskite Iodides and Bromides.

    PubMed

    Young, Joshua; Rondinelli, James M

    2016-03-03

    Phase transitions in ABX3 perovskites are often accompanied by rigid rotations of the corner-connected BX6 octahedral network. Although the mechanisms for the preferred rotation patterns of perovskite oxides are fairly well recognized, the same cannot be said of halide variants (i.e., X = Cl, Br, or I), several of which undergo an unusual displacive transition to a tetragonal phase exhibiting in-phase rotations about one axis (a(0)a(0)c(+) in Glazer notation). To discern the chemical factors stabilizing this unique phase, we investigated a series of 12 perovskite bromides and iodides using density functional theory calculations and compared them with similar oxides. We find that in-phase tilting provides a better arrangement of the larger bromide and iodide anions, which minimizes the electrostatic interactions, improves the bond valence of the A-site cations, and enhances the covalency between the A-site metal and Br(-) or I(-) ions. The opposite effect is present in the oxides, with out-of-phase tilting maximizing these factors.

  16. Perovskite solar cells: Stability lies at interfaces

    NASA Astrophysics Data System (ADS)

    Lira-Cantú, Mónica

    2017-07-01

    Perovskite solar cells are developing fast but their lifetimes must be extended. Now, large-area printed perovskite solar modules have been shown to be stable for more than 10,000 hours under continuous illumination.

  17. Simulation of an inverted perovskite solar cell with inorganic electron and hole transfer layers

    NASA Astrophysics Data System (ADS)

    Goudarzi, Mohamad; Banihashemi, Mehdi

    2017-04-01

    We use solar cell capacitance simulator-1D to simulate a fabricated inverted perovskite solar cell. The perovskite solar cell employs solution-processed inorganic hole and electron transfer layers. According to our simulations, surface defect densities at the interfaces of the perovskite active layer and inorganic hole/electron transfer materials in solution-based fabrication method are two orders of magnitude greater than that in the vapor deposition fabrication method. Increase of the surface defect densities reduces the circuit current, fill factor, and power conversion efficiency.

  18. Chemically diverse and multifunctional hybrid organic-inorganic perovskites

    NASA Astrophysics Data System (ADS)

    Li, Wei; Wang, Zheming; Deschler, Felix; Gao, Song; Friend, Richard H.; Cheetham, Anthony K.

    2017-02-01

    Hybrid organic-inorganic perovskites (HOIPs) can have a diverse range of compositions including halides, azides, formates, dicyanamides, cyanides and dicyanometallates. These materials have several common features, including their classical ABX3 perovskite architecture and the presence of organic amine cations that occupy the A-sites. Current research in HOIPs tends to focus on metal halide HOIPs, which show promise for use in solar cells and optoelectronic devices; however, the other subclasses also exhibit a diverse range of physical properties. In this Review, we summarize the chemical variability and structural diversity of all known HOIP subclasses. We also present a comprehensive account of their intriguing physical properties, including photovoltaic and optoelectronic properties, dielectricity, magnetism, ferroelectricity, ferroelasticity and multiferroicity. Moreover, we discuss the current challenges and future opportunities in this exciting field.

  19. 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.

  20. Perovskite-perovskite tandem photovoltaics with optimized band gaps

    NASA Astrophysics Data System (ADS)

    Eperon, Giles E.; Leijtens, Tomas; Bush, Kevin A.; Prasanna, Rohit; Green, Thomas; Wang, Jacob Tse-Wei; McMeekin, David P.; Volonakis, George; Milot, Rebecca L.; May, Richard; Palmstrom, Axel; Slotcavage, Daniel J.; Belisle, Rebecca A.; Patel, Jay B.; Parrott, Elizabeth S.; Sutton, Rebecca J.; Ma, Wen; Moghadam, Farhad; Conings, Bert; Babayigit, Aslihan; Boyen, Hans-Gerd; Bent, Stacey; Giustino, Feliciano; Herz, Laura M.; Johnston, Michael B.; McGehee, Michael D.; Snaith, Henry J.

    2016-11-01

    We demonstrate four- and two-terminal perovskite-perovskite tandem solar cells with ideally matched band gaps. We develop an infrared-absorbing 1.2-electron volt band-gap perovskite, FA0.75Cs0.25Sn0.5Pb0.5I3, that can deliver 14.8% efficiency. By combining this material with a wider-band gap FA0.83Cs0.17Pb(I0.5Br0.5)3 material, we achieve monolithic two-terminal tandem efficiencies of 17.0% with >1.65-volt open-circuit voltage. We also make mechanically stacked four-terminal tandem cells and obtain 20.3% efficiency. Notably, we find that our infrared-absorbing perovskite cells exhibit excellent thermal and atmospheric stability, not previously achieved for Sn-based perovskites. This device architecture and materials set will enable “all-perovskite” thin-film solar cells to reach the highest efficiencies in the long term at the lowest costs.

  1. Origin of superstructures in (double) perovskite thin films

    SciTech Connect

    Shabadi, V. Major, M.; Komissinskiy, P.; Vafaee, M.; Radetinac, A.; Baghaie Yazdi, M.; Donner, W.; Alff, L.

    2014-09-21

    We have investigated the origin of superstructure peaks as observed by X-ray diffraction of multiferroic Bi(Fe{sub 0.5}Cr{sub 0.5})O{sub 3} thin films grown by pulsed laser deposition on single crystal SrTiO{sub 3} substrates. The photon energy dependence of the contrast between the atomic scattering factors of Fe and Cr is used to rule out a chemically ordered double perovskite Bi{sub 2}FeCrO{sub 6} (BFCO). Structural calculations suggest that the experimentally observed superstructure occurs due to unequal cation displacements along the pseudo-cubic [111] direction that mimic the unit cell of the chemically ordered compound. This result helps to clarify discrepancies in the correlations of structural and magnetic order reported for Bi{sub 2}FeCrO{sub 6}. The observation of a superstructure in itself is not a sufficient proof of chemical order in double perovskites.

  2. Efficient light-emitting diodes based on nanocrystalline perovskite in a dielectric polymer matrix.

    PubMed

    Li, Guangru; Tan, Zhi-Kuang; Di, Dawei; Lai, May Ling; Jiang, Lang; Lim, Jonathan Hua-Wei; Friend, Richard H; Greenham, Neil C

    2015-04-08

    Electroluminescence in light-emitting devices relies on the encounter and radiative recombination of electrons and holes in the emissive layer. In organometal halide perovskite light-emitting diodes, poor film formation creates electrical shunting paths, where injected charge carriers bypass the perovskite emitter, leading to a loss in electroluminescence yield. Here, we report a solution-processing method to block electrical shunts and thereby enhance electroluminescence quantum efficiency in perovskite devices. In this method, a blend of perovskite and a polyimide precursor dielectric (PIP) is solution-deposited to form perovskite nanocrystals in a thin-film matrix of PIP. The PIP forms a pinhole-free charge-blocking layer, while still allowing the embedded perovskite crystals to form electrical contact with the electron- and hole-injection layers. This modified structure reduces nonradiative current losses and improves quantum efficiency by 2 orders of magnitude, giving an external quantum efficiency of 1.2%. This simple technique provides an alternative route to circumvent film formation problems in perovskite optoelectronics and offers the possibility of flexible and high-performance light-emitting displays.

  3. Modelling and loss analysis of meso-structured perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Xue, Hansong; Fu, Kunwu; Wong, Lydia Helena; Birgersson, Erik; Stangl, Rolf

    2017-08-01

    A mathematical model for meso-structured perovskite solar cells is derived and calibrated towards measured intensity dependent current-voltage characteristics. This steady-state device model describes the transport of free carriers, carrier recombination and optical generation. The optical part considers internal transmission, reflection, and absorption of light, using a transfer matrix approach. The carrier recombination in the form of radiative, Auger and Shockley-Read-Hall mechanisms is accounted for inside the perovskite capping layer, as well as interfacial recombination between the perovskite and electron/hole-transporting layers. After calibration by best-fitting the unknown parameters towards intensity dependent current-voltage measurements of an in-house fabricated meso-structured perovskite solar cell, we identify the dominant recombination mechanisms and their locations inside the cell. A subsequent loss analysis indicates that, in our fabricated solar cell, the interfacial recombination between the perovskite/mesoporous titanium dioxide within the mesoporous absorber layer constitutes the main loss channel. This interfacial recombination accounts for up to 46% of all recombination losses at maximum power, thereby exceeding the recombination inside the perovskite capping layer with 31% loss. Furthermore, the thickness of the perovskite capping layer and the mesoporous layer is varied by means of simulation between 50 and 500 nm, in order to predict the optimum device geometry for the calibrated recombination parameters.

  4. Graded bandgap perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Ergen, Onur; Gilbert, S. Matt; Pham, Thang; Turner, Sally J.; Tan, Mark Tian Zhi; Worsley, Marcus A.; Zettl, Alex

    2017-05-01

    Organic-inorganic halide perovskite materials have emerged as attractive alternatives to conventional solar cell building blocks. Their high light absorption coefficients and long diffusion lengths suggest high power conversion efficiencies, and indeed perovskite-based single bandgap and tandem solar cell designs have yielded impressive performances. One approach to further enhance solar spectrum utilization is the graded bandgap, but this has not been previously achieved for perovskites. In this study, we demonstrate graded bandgap perovskite solar cells with steady-state conversion efficiencies averaging 18.4%, with a best of 21.7%, all without reflective coatings. An analysis of the experimental data yields high fill factors of ~75% and high short-circuit current densities up to 42.1 mA cm-2. The cells are based on an architecture of two perovskite layers (CH3NH3SnI3 and CH3NH3PbI3-xBrx), incorporating GaN, monolayer hexagonal boron nitride, and graphene aerogel.

  5. Graded bandgap perovskite solar cells.

    PubMed

    Ergen, Onur; Gilbert, S Matt; Pham, Thang; Turner, Sally J; Tan, Mark Tian Zhi; Worsley, Marcus A; Zettl, Alex

    2017-05-01

    Organic-inorganic halide perovskite materials have emerged as attractive alternatives to conventional solar cell building blocks. Their high light absorption coefficients and long diffusion lengths suggest high power conversion efficiencies, and indeed perovskite-based single bandgap and tandem solar cell designs have yielded impressive performances. One approach to further enhance solar spectrum utilization is the graded bandgap, but this has not been previously achieved for perovskites. In this study, we demonstrate graded bandgap perovskite solar cells with steady-state conversion efficiencies averaging 18.4%, with a best of 21.7%, all without reflective coatings. An analysis of the experimental data yields high fill factors of ∼75% and high short-circuit current densities up to 42.1 mA cm(-2). The cells are based on an architecture of two perovskite layers (CH3NH3SnI3 and CH3NH3PbI3-xBrx), incorporating GaN, monolayer hexagonal boron nitride, and graphene aerogel.

  6. Tunable magnetocaloric effect in Sr1 - x Ca x Mn0.5Ti0.5O3 perovskites

    NASA Astrophysics Data System (ADS)

    Shanmugapriya, K.; Radheep, D. Mohan; Palanivel, Balan; Murugan, Ramaswamy

    2017-07-01

    Sr1 - x Ca x Mn0.5Ti0.5O3 ( x = 0.25, 0.5 and 0.75) polycrystalline samples were synthesized by conventional solid-state reaction. Magnetic characterizations of Sr1 - x Ca x Mn0.5Ti0.5O3 revealed signature of antiferromagnetic ordering at temperatures ( T N) 19, 25 and 29.5 K for x = 0.25, x = 0.5 and for x = 0.75, respectively. Sr1 - x Ca x Mn0.5Ti0.5O3 ( x = 0.75) exhibits field-induced antiferromagnetic to ferromagnetic transition at 30 K with applied magnetic field of 4 and 5 T. Magnetocaloric change (Δ S M) increases from 3.5 to 19 J/kg K by increasing calcium concentration in the A-site. Those Δ S M values are relatively very high in these classes of antiferromagnetic perovskite systems and equal to the magnetisation values of the ferromagnetic perovskite manganites. This is the first report for the Sr1 - x Ca x Mn0.5Ti0.5O3 ( x = 0.75) having large magnetic entropy changes induced by the low magnetic field.

  7. Hybrid Organic-Inorganic Perovskite Photodetectors.

    PubMed

    Tian, Wei; Zhou, Huanping; Li, Liang

    2017-09-12

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

  8. Huge positive magnetoresistance in antiferromagnetic double perovskite metals

    NASA Astrophysics Data System (ADS)

    Nand Singh, Viveka; Majumdar, Pinaki

    2014-07-01

    Metals with large positive magnetoresistance are rare. We demonstrate that antiferromagnetic metallic states, as have been predicted for the double perovskites, are excellent candidates for huge positive magnetoresistance. An applied field suppresses long range antiferromagnetic order leading to a state with short range antiferromagnetic correlations and strong electronic scattering. The field induced resistance ratio can be more than tenfold, at moderate field, in a structurally ordered system, and continues to be almost twofold even in systems with ˜25% antisite disorder. Although our explicit demonstration is in the context of a two- dimensional spin-fermion model of the double perovskites, the mechanism we uncover is far more general, complementary to the colossal negative magnetoresistance process, and would operate in other local moment metals that show a field driven suppression of non-ferromagnetic order.

  9. Huge positive magnetoresistance in antiferromagnetic double perovskite metals.

    PubMed

    Singh, Viveka Nand; Majumdar, Pinaki

    2014-07-23

    Metals with large positive magnetoresistance are rare. We demonstrate that antiferromagnetic metallic states, as have been predicted for the double perovskites, are excellent candidates for huge positive magnetoresistance. An applied field suppresses long range antiferromagnetic order leading to a state with short range antiferromagnetic correlations and strong electronic scattering. The field induced resistance ratio can be more than tenfold, at moderate field, in a structurally ordered system, and continues to be almost twofold even in systems with ∼ 25% antisite disorder. Although our explicit demonstration is in the context of a two- dimensional spin-fermion model of the double perovskites, the mechanism we uncover is far more general, complementary to the colossal negative magnetoresistance process, and would operate in other local moment metals that show a field driven suppression of non-ferromagnetic order.

  10. 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.

  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. Epitaxial thin films of novel multiferroic double perovskites.

    NASA Astrophysics Data System (ADS)

    Venimadhav, A.; Li, Qi

    2006-03-01

    Recently multiferroic materials have attracted great interest. However, relatively a few pure multiferroic compounds are currently known. Here we show the exploration of design of multiferroic properties in double perovskites by combining the ferrolectrisity driven by the Bi lone pairs and selectively choosing the 3d transition metals following Goodenough-Kanamori's rules to bring in ferromagnetism. We present growth issues in stabilizing the single phase, epitaxial thin films of new double perovskite multiferroic systems such as Bi2NiMnO6, Bi2FeCrO6 and La2NiMnO6 by pulsed laser deposition. Targets of these compositions were synthesized by solid state method with 15% of excess Bi in the composition to compensate the volatility of Bi during the deposition. We also present the synthesis of Bi2FeCrO6 by growing a superlattice structures from individual targets of Bi FeO3 and BiCrO3. In the cubic double perovskites, cations show rock salt kind of ordering in the (111) direction and hence growing these films on STO (111) substrates has an advantage. We present the growth, structural and multiferroic properties in these double perovskite thin films..

  13. Hysteresis, Stability, and Ion Migration in Lead Halide Perovskite Photovoltaics.

    PubMed

    Miyano, Kenjiro; Yanagida, Masatoshi; Tripathi, Neeti; Shirai, Yasuhiro

    2016-06-16

    Ion migration has been suspected as the origin of various irreproducible and unstable properties, most notably the hysteresis, of lead halide perovskite photovoltaic (PV) cells since the early stage of the research. Although many evidence of ionic movement have been presented both numerically and experimentally, a coherent and quantitative picture that accounts for the observed irreproducible phenomena is still lacking. At the same time, however, it has been noticed that in certain types of PV cells, the hysteresis is absent or at least within the measurement reproducibility. We have previously shown that the electronic properties of hysteresis-free cells are well represented in terms of the conventional inorganic semiconductors. The reproducibility of these measurements was confirmed typically within tens of minutes under the biasing field of -1 V to +1.5 V. In order to probe the effect of ionic motion in the hysteresis-free cells, we extended the time scale and the biasing rage in the electronic measurements, from which we conclude the following: (1) From various evidence, it appears that ion migration is inevitable. However, it does not cause detrimental effects to the PV operation. (2) We propose, based on the quantitative characterization, that the degradation is more likely due to the chemical change at the interfaces between the carrier selective layers and perovskite rather than the compositional change of the lead iodide perovskite bulk. Together, they give much hope in the use of the lead iodide perovskite in the use of actual application.

  14. Interfaces in perovskite solar cells.

    PubMed

    Shi, Jiangjian; Xu, Xin; Li, Dongmei; Meng, Qingbo

    2015-06-03

    The interfacial atomic and electronic structures, charge transfer processes, and interface engineering in perovskite solar cells are discussed in this review. An effective heterojunction is found to exist at the window/perovskite absorber interface, contributing to the relatively fast extraction of free electrons. Moreover, the high photovoltage in this cell can be attributed to slow interfacial charge recombination due to the outstanding material and interfacial electronic properties. However, some fundamental questions including the interfacial atomic and electronic structures and the interface stability need to be further clarified. Designing and engineering the interfaces are also important for the next-stage development of this cell.

  15. PbI2 platelets for inverted planar organolead Halide Perovskite solar cells via ultrasonic spray deposition

    NASA Astrophysics Data System (ADS)

    Chai, Gaoda; Wang, Shizhen; Xia, Zhonggao; Luo, Shiqiang; Teng, Chao; Yang, Tingbin; Nie, Zanxiang; Meng, Tiejun; Zhou, Hang

    2017-07-01

    Morphology control of organometal halide perovskite thin films is of importance in order to develop highly efficient perovskite solar cells. Here, a seeded growth method is introduced for the first time to deposit lead iodide (PbI2) with platelet structures on an organic hole transporting layer PEDOT:PSS. The PbI2 platelets are effectively converted into perovskite thin film when subject to sprayed droplets of methylammonium in isopropyl alcohol. Compared with evaporated compact PbI2 layers, the PbI2 platelet enables a thicker perovskite thin film to be formed with less unreacted PbI2. Using this technique, we have achieved pinhole-free and uniform perovskite thin film with root-mean-square roughness of 12.81 nm, and an average solar cell efficiency higher than those fabricated from compact PbI2 thin film.

  16. 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.

  17. Investigation of the hydrothermal crystallisation of the perovskite solid solution NaCe{sub 1−x}La{sub x}Ti{sub 2}O{sub 6} and its defect chemistry

    SciTech Connect

    Harunsani, Mohammad H.; Woodward, David I.; Peel, Martin D.; Ashbrook, Sharon E.; Walton, Richard I.

    2013-11-15

    Perovskites of nominal composition NaCe{sub 1−x}La{sub x}Ti{sub 2}O{sub 6} (0≤x≤1) crystallise directly under hydrothermal conditions at 240 °C. Raman spectroscopy shows distortion from the ideal cubic structure and Rietveld analysis of powder X-ray and neutron diffraction reveals that the materials represent a continuous series in rhombohedral space group R3-bar c. Ce L{sub III}-edge X-ray absorption near edge structure spectroscopy shows that while the majority of cerium is present as Ce{sup 3+} there is evidence for Ce{sup 4+}. The paramagnetic Ce{sup 3+} affects the chemical shift and line width of {sup 23}Na MAS NMR spectra, which also show with no evidence for A-site ordering. {sup 2}H MAS NMR of samples prepared in D{sub 2}O shows the inclusion of deuterium, which IR spectroscopy shows is most likely to be as D{sub 2}O. The deuterium content is highest for the cerium-rich materials, consistent with oxidation of some cerium to Ce{sup 4+} to provide charge balance of A-site water. - Graphical abstract: A multi-element A-site perovskite crystallises directly from aqueous, basic solutions at 240 °C; while the paramagnetic effect of Ce{sup 3+} on the {sup 23}Na NMR shows a homogeneous solid-solution, the incorporation of A-site water is also found from {sup 2}H NMR and IR, with oxidation of some cerium to charge balance proved by XANES spectroscopy. Display Omitted - Highlights: • Direct hydrothermal synthesis allows crystallisation of a perovskite solid-solution. • XANES spectroscopy shows some oxidation of Ce{sup 3+} to Ce{sup 4+}. • The paramagnetism of Ce{sup 3+} shifts and broadens the {sup 23}Na solid-state NMR. • The perovskite materials incorporate water as an A-site defect.

  18. Excitonic magnetism in d6 perovskites

    NASA Astrophysics Data System (ADS)

    Afonso, J. Fernández; Kuneš, J.

    2017-03-01

    We use the LDA+U method to study the possibility of exciton condensation in perovskites of transition metals with the d6 electronic configuration such as LaCoO3. For realistic interaction parameters we find several distinct solutions exhibiting a spin-triplet exciton condensate, which gives rise to a local spin density distribution while the ordered moments are vanishingly small. Rhombohedral distortion from the ideal cubic structure suppresses the ordered state, contrary to the spin-orbit coupling which enhances the excitonic condensation energy. We explain the trends observed in the numerical simulations with the help of a simplified strong-coupling model. Our results indicate that LaCoO3 is close to the excitonic instability and suggest ways how to achieve the exciton condensation.

  19. Compressibility of orthorhombic perovskites. The effect of transition metal ions (TMI)

    NASA Astrophysics Data System (ADS)

    Ardit, Matteo

    2015-12-01

    Interest in perovskites evenly spans Materials Science and Geophysics. Due to their inimitably lattice flexibility enabling small as well as large ions to be accommodated, perovskites have become a base structure for new technological applications. Understanding the mechanisms governing their evolution at non-ambient conditions (such as high-pressure and high-temperature) is fundamentally important both for devising functional materials and in order to provide the most reliable possible deep-Earth model. With particular attention being paid to the chemical nature of the constituent ions, a suite of orthorhombic perovskites has been selected and contrasted using several parameterizations and models. A new perspective on the pressure-induced distortion of orthorhombic perovskite structures has enabled their compressional behaviour to be redefined.

  20. Relationships between Lead Halide Perovskite Thin-Film Fabrication, Morphology, and Performance in Solar Cells.

    PubMed

    Sharenko, Alexander; Toney, Michael F

    2016-01-20

    Solution-processed lead halide perovskite thin-film solar cells have achieved power conversion efficiencies comparable to those obtained with several commercial photovoltaic technologies in a remarkably short period of time. This rapid rise in device efficiency is largely the result of the development of fabrication protocols capable of producing continuous, smooth perovskite films with micrometer-sized grains. Further developments in film fabrication and morphological control are necessary, however, in order for perovskite solar cells to reliably and reproducibly approach their thermodynamic efficiency limit. This Perspective discusses the fabrication of lead halide perovskite thin films, while highlighting the processing-property-performance relationships that have emerged from the literature, and from this knowledge, suggests future research directions.

  1. 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.

  2. Ultrathin Cu2O as an efficient inorganic hole transporting material for perovskite solar cells.

    PubMed

    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

    2016-03-21

    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.

  3. 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.

  4. Solvent-Mediated Crystallization of CH3NH3SnI3 Films for Heterojunction Depleted Perovskite Solar Cells.

    PubMed

    Hao, Feng; Stoumpos, Constantinos C; Guo, Peijun; Zhou, Nanjia; Marks, Tobin J; Chang, Robert P H; Kanatzidis, Mercouri G

    2015-09-09

    Organo-lead halide perovskite solar cells have gained enormous significance and have now achieved power conversion efficiencies of ∼20%. However, the potential toxicity of lead in these systems raises environmental concerns for widespread deployment. Here we investigate solvent effects on the crystallization of the lead-free methylammonium tin triiodide (CH3NH3SnI3) perovskite films in a solution growth process. Highly uniform, pinhole-free perovskite films are obtained from a dimethyl sulfoxide (DMSO) solution via a transitional SnI2·3DMSO intermediate phase. This high-quality perovskite film enables the realization of heterojunction depleted solar cells based on mesoporous TiO2 layer but in the absence of any hole-transporting material with an unprecedented photocurrent up to 21 mA cm(-2). Charge extraction and transient photovoltage decay measurements reveal high carrier densities in the CH3NH3SnI3 perovskite device which are one order of magnitude larger than CH3NH3PbI3-based devices but with comparable recombination lifetimes in both devices. The relatively high background dark carrier density of the Sn-based perovskite is responsible for the lower photovoltaic efficiency in comparison to the Pb-based analogues. These results provide important progress toward achieving improved perovskite morphology control in realizing solution-processed highly efficient lead-free perovskite solar cells.

  5. Parameters influencing the deposition of methylammonium lead halide iodide in hole conductor free perovskite-based solar cells

    SciTech Connect

    Cohen, Bat-El; Gamliel, Shany; Etgar, Lioz

    2014-08-01

    Perovskite is a promising light harvester for use in photovoltaic solar cells. In recent years, the power conversion efficiency of perovskite solar cells has been dramatically increased, making them a competitive source of renewable energy. An important parameter when designing high efficiency perovskite-based solar cells is the perovskite deposition, which must be performed to create complete coverage and optimal film thickness. This paper describes an in-depth study on two-step deposition, separating the perovskite deposition into two precursors. The effects of spin velocity, annealing temperature, dipping time, and methylammonium iodide concentration on the photovoltaic performance are studied. Observations include that current density is affected by changing the spin velocity, while the fill factor changes mainly due to the dipping time and methylammonium iodide concentration. Interestingly, the open circuit voltage is almost unaffected by these parameters. Hole conductor free perovskite solar cells are used in this work, in order to minimize other possible effects. This study provides better understanding and control over the perovskite deposition through highly efficient, low-cost perovskite-based solar cells.

  6. Systematic Study of Compositional and Synthetic Control of Vacancy and Magnetic Ordering in Oxygen-Deficient Perovskites Ca2Fe2 xMnxO5+yand CaSrFe2 xMnxO5+y (x = 1/2, 2/3, and 1; y = 0 1/2)

    SciTech Connect

    Ramezanipour, Farshid; Greedan, John E; Cranswick, Lachlan M.D.; Donaberger, R. L.; Garlea, Vasile O; Siewenie, Joan

    2012-01-01

    Ten compounds belonging to the series of oxygen-deficient perovskite oxides Ca2Fe2 xMnxO5 and CaSrFe2 xMnxO5+y, where x = 1/2, 2/3, and 1 and y 0 0.5, were synthesized and investigated with respect to the ordering of oxygen vacancies on both local and long-range length scales and the effect on crystal structure and magnetic properties. For the set with y 0 the oxygen vacancies always order in the long-range sense to form the brownmillerite structure containing alternating layers of octahedrally and tetrahedrally coordinated cations. However, there is a change in symmetry from Pnma to Icmm upon substitution of Sr for one Ca for all x, indicating local Td chain (vacancy) disorder. In the special case of CaSrFeMnO5 the neutron diffraction peaks broaden, indicating only short-range structural order on a length scale of 160 . This reveals a systematic progression from Ca2FeMnO5 (Pnma, well-ordered tetrahedral chains) to CaSrFeMnO5 (Icmm, disordered tetrahedral chains, overall short-range order) to Sr2FeMnO5 (Pm3m, destruction of tetrahedral chains in a long-range sense). Systematic changes occur in the magnetic properties as well. While long-range antiferromagnetic order is preserved, the magnetic transition temperature, Tc, decreases for the same x when Sr substitutes for one Ca. A review of the changes in Tc for the series Ca2Fe2 xMxO5, taking into account the tetrahedral/octahedral site preferences for the various M3+ ions, leads to a partial understanding of the origin of magnetic order in these materials in terms of a layered antiferromagnetic model. While in all cases the preferred magnetic moment direction is (010) at low temperatures, there is a cross over for x = 0.5 to (100) with increasing temperature for both the Ca2Fe2 xMnxO5 and the CaSrFe2 xMnxO5 series. For the y > 0 phases, while a brownmillerite ordering of oxygen vacancies is preserved for the Ca2 phases, a disordered Pm3m cubic perovskite structure is always found when Sr is substituted for one Ca

  7. Systematic study of compositional and synthetic control of vacancy and magnetic ordering in oxygen-deficient perovskites Ca2Fe(2-x)Mn(x)O(5+y)and CaSrFe(2-x)Mn(x)O(5+y) (x = 1/2, 2/3, and 1; y = 0-1/2).

    PubMed

    Ramezanipour, Farshid; Greedan, John E; Cranswick, Lachlan M D; Garlea, V Ovidiu; Donaberger, Ronald L; Siewenie, Joan

    2012-02-15

    Ten compounds belonging to the series of oxygen-deficient perovskite oxides Ca(2)Fe(2-x)Mn(x)O(5) and CaSrFe(2-x)Mn(x)O(5+y), where x = 1/2, 2/3, and 1 and y ≈ 0-0.5, were synthesized and investigated with respect to the ordering of oxygen vacancies on both local and long-range length scales and the effect on crystal structure and magnetic properties. For the set with y ≈ 0 the oxygen vacancies always order in the long-range sense to form the brownmillerite structure containing alternating layers of octahedrally and tetrahedrally coordinated cations. However, there is a change in symmetry from Pnma to Icmm upon substitution of Sr for one Ca for all x, indicating local T(d) chain (vacancy) disorder. In the special case of CaSrFeMnO(5) the neutron diffraction peaks broaden, indicating only short-range structural order on a length scale of ~160 Å. This reveals a systematic progression from Ca(2)FeMnO(5) (Pnma, well-ordered tetrahedral chains) to CaSrFeMnO(5) (Icmm, disordered tetrahedral chains, overall short-range order) to Sr(2)FeMnO(5) (Pm3m, destruction of tetrahedral chains in a long-range sense). Systematic changes occur in the magnetic properties as well. While long-range antiferromagnetic order is preserved, the magnetic transition temperature, T(c), decreases for the same x when Sr substitutes for one Ca. A review of the changes in T(c) for the series Ca(2)Fe(2-x)M(x)O(5), taking into account the tetrahedral/octahedral site preferences for the various M(3+) ions, leads to a partial understanding of the origin of magnetic order in these materials in terms of a layered antiferromagnetic model. While in all cases the preferred magnetic moment direction is (010) at low temperatures, there is a cross over for x = 0.5 to (100) with increasing temperature for both the Ca(2)Fe(2-x)Mn(x)O(5) and the CaSrFe(2-x)Mn(x)O(5) series. For the y > 0 phases, while a brownmillerite ordering of oxygen vacancies is preserved for the Ca(2) phases, a disordered Pm3m cubic

  8. Systems and methods for scalable perovskite device fabrication

    DOEpatents

    Huang, Jinsong; Dong, Qingfeng; Sao, Yuchuan

    2017-02-28

    Continuous processes for fabricating a perovskite device are described that include using a doctor blade for continuously forming a perovskite layer and using a conductive tape lamination process to form an anode or a cathode layer on the perovskite device.

  9. Monolithic Perovskite Silicon Tandem Solar Cells with Advanced Optics

    SciTech Connect

    Goldschmidt, Jan C.; Bett, Alexander J.; Bivour, Martin; Blasi, Benedikt; Eisenlohr, Johannes; Kohlstadt, Markus; Lee, Seunghun; Mastroianni, Simone; Mundt, Laura; Mundus, Markus; Ndione, Paul; Reichel, Christian; Schubert, Martin; Schulze, Patricia S.; Tucher, Nico; Veit, Clemens; Veurman, Welmoed; Wienands, Karl; Winkler, Kristina; Wurfel, Uli; Glunz, Stefan W.; Hermle, Martin

    2016-11-14

    For high efficiency monolithic perovskite silicon tandem solar cells, we develop low-temperature processes for the perovskite top cell, rear-side light trapping, optimized perovskite growth, transparent contacts and adapted characterization methods.

  10. Structure-Property Correlations in Double Perovskite Systems

    NASA Astrophysics Data System (ADS)

    Dixit, Manisha

    Double perovskite compounds of the type ABB'O3 where B and B' are transition elements, exhibit a wide range of properties that are useful for various applications. Double perovskites such as Sr2FeMoO 6 (SFMO), Sr2CrReO6 (SCRO) are ferrimagnetic materials with properties useful for spintronic applications. The ordering of Fe and Mo atoms in the case of SFMO and Cr and Re atoms in case of SCRO known as B-site ordering is very important. Sputter-deposited thin-films of SFMO and SCRO systems were characterized using various high resolution transmission electron microscopy (TEM) techniques. B-site disorders, other kinds of structural defects and variation in chemical composition were found in the thin-films studied. Valence state of Fe in SFMO system was studied using electron energy-loss spectroscopy (EELS). In order to interpret the EELS data, other comparative perovskite compounds were also utilized. In the case of SCRO system, multislice simulations were used to interpret information about B-site ordering from scanning transmission electron microscopy images acquired using the high-angle annular dark-field detector. It was found that presence of various kinds of structural defects and composition variations in these systems have an effect on the useful magnetic and electrical properties.

  11. perovskite up to 55 GPa

    NASA Astrophysics Data System (ADS)

    Gréaux, Steeve; Andrault, Denis; Gautron, Laurent; Bolfan-Casanova, Nathalie; Mezouar, Mohamed

    2014-06-01

    Compressibility of perovskite-structured Ca3Al2Si3O12 grossular (GrPv) was investigated at high pressure and high temperature by means of angle-dispersive powder X-ray diffraction using a laser-heated diamond anvil cell. We observed the Pbnm orthorhombic distortion for the pure phase above 50 GPa, whereas below this pressure, Al-bearing CaSiO3 perovskite coexists with an excess of corundum. GrPv has a bulk modulus ( K 0 = 229 ± 5 GPa; fixed to 4) almost similar to that reported for pure CaSiO3 perovskite. Its unit-cell volume extrapolated to ambient conditions ( V 0 = 187.1 ± 0.4 Å3) is found to be ~2.5 % larger than for the Al-free phase. We observe an increasing unit-cell anisotropy with increasing pressure, which could have implications for the shear properties of Ca-bearing perovskite in cold slabs subducted into the Earth's mantle.

  12. 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.

  13. 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.

  14. Ferroelectric Graphene-Perovskite Interfaces.

    PubMed

    Volonakis, George; Giustino, Feliciano

    2015-07-02

    Owing to their record-breaking energy conversion efficiencies, hybrid organometallic perovskites have emerged as the most promising light absorbers and ambipolar carrier transporters for solution-processable solar cells. Simultaneously, due to its exceptional electron mobility, graphene represents a prominent candidate for replacing transparent conducting oxides. Thus, it is possible that combining these wonder materials may propel the efficiency toward the Schokley-Queisser limit. Here, using first-principles calculations on graphene-CH3NH3PbI3 interfaces, we find that graphene suppresses the octahedral tilt in the very first perovskite monolayer, leading to a nanoscale ferroelectric distortion with a permanent polarization of 3 mC/m(2). This interfacial ferroelectricity drives electron extraction from the perovskite and hinders electron-hole recombination by keeping the electrons and holes separated. The interfacial ferroelectricity identified here simply results from the interplay between graphene's planar structure and CH3NH3PbI3's octahedral connectivity; therefore, this mechanism may be effective in a much broader class of perovskites, with potential applications in photovoltaics and photocatalysis.

  15. 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

  16. 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

    2016-03-02

    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.

  17. Inorganic perovskite photocatalysts for solar energy utilization.

    PubMed

    Zhang, Guan; Liu, Gang; Wang, Lianzhou; Irvine, John T S

    2016-10-24

    The development and utilization of solar energy in environmental remediation and water splitting is being intensively studied worldwide. During the past few decades, tremendous efforts have been devoted to developing non-toxic, low-cost, efficient and stable photocatalysts for water splitting and environmental remediation. To date, several hundreds of photocatalysts mainly based on metal oxides, sulfides and (oxy)nitrides with different structures and compositions have been reported. Among them, perovskite oxides and their derivatives (layered perovskite oxides) comprise a large family of semiconductor photocatalysts because of their structural simplicity and flexibility. This review specifically focuses on the general background of perovskite and its related materials, summarizes the recent development of perovskite photocatalysts and their applications in water splitting and environmental remediation, discusses the theoretical modelling and calculation of perovskite photocatalysts and presents the key challenges and perspectives on the research of perovskite photocatalysts.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    We report the results of neutron elastic-scattering measurements made between -250 °C and 620 °C on the lead-free relaxor (Na1/2Bi1/2)TiO3 (NBT). Strong, anisotropic, elastic diffuse scattering intensity decorates the (100), (110), (111), (200), (210), and (220) Bragg peaks at room temperature. The wave-vector dependence of this diffuse scattering is compared to that in the lead-based relaxor Pb(Mg1/3Nb2/3)O3 (PMN) to determine if any features might be common to relaxors. Prominent ridges in the elastic diffuse scattering intensity contours that extend along ⟨110⟩ are seen that exhibit the same zone dependence as those observed in PMN and other lead-based relaxors. These ridges disappear gradually on heating above the cubic-to-tetragonal phase transition temperature TCT = 523 °C, which is also near the temperature at which the dielectric permittivity begins to deviate from Curie-Weiss behavior. We thus identify the ⟨110⟩-oriented ridges as a relaxor-specific property. The diffuse scattering contours also display narrower ridges oriented along ⟨100⟩ that are consistent with the x-ray results of Kreisel [Phys. Rev. BPRBMDO1098-012110.1103/PhysRevB.68.014113 68, 014113 (2003)]; these vanish near 320 °C, indicating that they have a different physical origin. The ⟨100⟩-oriented ridges are not observed in PMN. We observe no equivalent relaxor-specific elastic diffuse scattering from the homovalent relaxor analogues K0.95Li0.05TiO3 (A-site disordered) and KTa0.95Nb0.05O3 (B-site disordered). This suggests that the ⟨110⟩-oriented diffuse scattering ridges are correlated with the presence of strong random electric fields and invites a reassessment of what defines the relaxor phase. We find that doping NBT with 5.6% BaTiO3, a composition close to the morphotropic phase boundary with enhanced piezoelectric properties, increases the room-temperature correlation length along [11¯0] from 40 to 60 Å while doubling the associated integrated diffuse

  19. Structural and Chemical Evolution of Methylammonium Lead Halide Perovskites during Thermal Processing from Solution

    SciTech Connect

    Nenon, David P.; Christians, Jeffrey A.; Wheeler, Lance M.; Blackburn, Jeffrey L.; Sanehira, Erin M.; Dou, Benjia; Olsen, Michele L.; Zhu, Kai; Berry, Joseph J.; Luther, Joseph M.

    2016-06-01

    Following the prominent success of CH3NH3PbI3 in photovoltaics and other optoelectronic applications, focus has been placed on better understanding perovskite crystallization from precursor and intermediate phases in order to facilitate improved crystallinity often desirable for advancing optoelectronic properties. Understanding of stability and degradation is also of critical importance as these materials seek commercial applications. In this study, we investigate the evolution of perovskites formed from targeted precursor chemistries by correlating in situ temperature-dependent X-ray diffraction, thermogravimetric analysis, and mass spectral analysis of the evolved species. This suite of analyses reveals important precursor composition-induced variations in the processes underpinning perovskite formation and degradation. The addition of Cl- leads to widely different precursor evolution and perovskite formation kinetics, and results in significant changes to the degradation mechanism, including suppression of crystalline PbI2 formation and modification of the thermal stability of the perovskite phase. This work highlights the role of perovskite precursor chemistry in both its formation and degradation.

  20. 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.

  1. 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.

  2. Strain effects on oxygen migration in perovskites.

    PubMed

    Mayeshiba, Tam; Morgan, Dane

    2015-01-28

    Fast oxygen transport materials are necessary for a range of technologies, including efficient and cost-effective solid oxide fuel cells, gas separation membranes, oxygen sensors, chemical looping devices, and memristors. Strain is often proposed as a method to enhance the performance of oxygen transport materials, but the magnitude of its effect and its underlying mechanisms are not well-understood, particularly in the widely-used perovskite-structured oxygen conductors. This work reports on an ab initio prediction of strain effects on migration energetics for nine perovskite systems of the form LaBO3, where B = [Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Ga]. Biaxial strain, as might be easily produced in epitaxial systems, is predicted to lead to approximately linear changes in migration energy. We find that tensile biaxial strain reduces the oxygen vacancy migration barrier across the systems studied by an average of 66 meV per percent strain for a single selected hop, with a low of 36 and a high of 89 meV decrease in migration barrier per percent strain across all systems. The estimated range for the change in migration barrier within each system is ±25 meV per percent strain when considering all hops. These results suggest that strain can significantly impact transport in these materials, e.g., a 2% tensile strain can increase the diffusion coefficient by about three orders of magnitude at 300 K (one order of magnitude at 500 °C or 773 K) for one of the most strain-responsive materials calculated here (LaCrO3). We show that a simple elasticity model, which assumes only dilative or compressive strain in a cubic environment and a fixed migration volume, can qualitatively but not quantitatively model the strain dependence of the migration energy, suggesting that factors not captured by continuum elasticity play a significant role in the strain response.

  3. Effect of the rare earth in the perovskite-type mixed oxides AMnO{sub 3} (A=Y, La, Pr, Sm, Dy) as catalysts in methanol oxidation

    SciTech Connect

    Levasseur, B.; Kaliaguine, S.

    2008-11-15

    The effect of the rare earth in the perovskite-type mixed oxides AMnO{sub 3} (A=Y, La, Pr, Sm, Dy) on catalytic properties in methanol oxidation was investigated in this work. The perovskites were prepared by reactive grinding in order to enhance the specific surface area in comparison with other classical synthesis procedures. These catalysts were characterized by N{sub 2} adsorption, X-ray diffraction, H{sub 2} temperature-programmed reduction (TPR-H{sub 2}), O{sub 2}-, CH{sub 3}OH- and CO{sub 2}-temperature-programmed desorption (TPD). The activity of the five catalysts under study in the methanol oxidation reaction was evaluated. The behaviour of the {alpha}-O{sub 2} from the surface of the perovskite was strongly related to the nature of the A-site cation and particularly to its electronegativity but also to its density. Concerning the {beta}-O{sub 2} from the bulk, the rare earth only induces an indirect effect notably due to structural modifications. As suggested in a previous study, the activity in methanol oxidation was directly linked with the surface oxygen density. Under an excess of {alpha}-oxygen, the reaction intermediate was found to be a monodentate carbonate that decomposes into CO{sub 2}. The stability of monodentate carbonates was also found to be related to the electronegativity of the rare earth during both CH{sub 3}OH- and CO{sub 2}-temperature-programmed desorption. However, as soon as a lack of {alpha}-oxygen was observed in the structure, the dominant reaction intermediate was a bidentate carbonate that induces a consumption of anion vacancies in spite of the production of CO{sub 2}. Nevertheless, the accumulation of these carbonates leads to a decrease in the oxidation rate since their desorption requires high temperatures. - Graphical abstract: Perovskite-type mixed oxides AMnO{sub 3} (with A=Y, La, Pr, Sm, Dy) with high specific surface area were prepared by reactive grinding. The influence of the rare earth on the two kinds of oxygen

  4. 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

    2016-04-07

    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).

  5. 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

  6. Nonlocal quartic interactions and universality classes in perovskite manganites.

    PubMed

    Singh, Rohit; Dutta, Kishore; Nandy, Malay K

    2015-07-01

    A modified Ginzburg-Landau model with a screened nonlocal interaction in the quartic term is treated via Wilson's renormalization-group scheme at one-loop order to explore the critical behavior of the paramagnetic-to-ferromagnetic phase transition in perovskite manganites. We find the Fisher exponent η to be O(ε) and the correlation exponent to be ν=1/2+O(ε) through epsilon expansion in the parameter ε=d(c)-d, where d is the space dimension, d(c)=4+2σ is the upper critical dimension, and σ is a parameter coming from the nonlocal interaction in the model Hamiltonian. The ensuing critical exponents in three dimensions for different values of σ compare well with various existing experimental estimates for perovskite manganites with various doping levels. This suggests that the nonlocal model Hamiltonian contains a wide variety of such universality classes.

  7. Fast Photoconductive Responses in Organometal Halide Perovskite Photodetectors.

    PubMed

    Wang, Fei; Mei, Jingjing; Wang, Yunpeng; Zhang, Ligong; Zhao, Haifeng; Zhao, Dongxu

    2016-02-03

    Inorganic semiconductor-based photodetectors have been suffering from slow response speeds, which are caused by the persistent photoconductivity of semiconductor materials. For realizing high speed optoelectronic devices, the organometal halide perovskite thin films were applied onto the interdigitated (IDT) patterned Au electrodes, and symmetrical structured photoconductive detectors were achieved. The detectors were sensitive to the incident light signals, and the photocurrents of the devices were 2-3 orders of magnitude higher than dark currents. The responsivities of the devices could reach up to 55 mA W(1-). Most importantly, the detectors have a fast response time of less than 20 μs. The light and bias induced dipole rearrangement in organometal perovskite thin films has resulted in the instability of photocurrents, and Ag nanowires could quicken the process of dipole alignment and stabilize the photocurrents of the devices.

  8. Double perovskite heterostructures: magnetism, Chern bands, and Chern insulators.

    PubMed

    Cook, Ashley M; Paramekanti, Arun

    2014-08-15

    Experiments demonstrating the controlled growth of oxide heterostructures have raised the prospect of realizing topologically nontrivial states of correlated electrons in low dimensions. Here, we study heterostructures consisting of {111} bilayers of double perovskites separated by inert band insulators. In bulk, these double perovskites have well-defined local moments interacting with itinerant electrons leading to high temperature ferromagnetism. Incorporating spin-orbit coupling in the two-dimensional honeycomb geometry of a {111} bilayer, we find a rich phase diagram with tunable ferromagnetic order, topological Chern bands, and a C=±2 Chern insulator regime. Our results are of broad relevance to oxide materials such as Sr_{2}FeMoO_{6}, Ba_{2}FeReO_{6}, and Sr_{2}CrWO_{6}.

  9. One-Dimensional Electron Transport Layers for Perovskite Solar Cells

    PubMed Central

    Thakur, Ujwal K.; Kisslinger, Ryan; Shankar, Karthik

    2017-01-01

    The electron diffusion length (Ln) is smaller than the hole diffusion length (Lp) in many halide perovskite semiconductors meaning that the use of ordered one-dimensional (1D) structures such as nanowires (NWs) and nanotubes (NTs) as electron transport layers (ETLs) is a promising method of achieving high performance halide perovskite solar cells (HPSCs). ETLs consisting of oriented and aligned NWs and NTs offer the potential not merely for improved directional charge transport but also for the enhanced absorption of incoming light and thermodynamically efficient management of photogenerated carrier populations. The ordered architecture of NW/NT arrays affords superior infiltration of a deposited material making them ideal for use in HPSCs. Photoconversion efficiencies (PCEs) as high as 18% have been demonstrated for HPSCs using 1D ETLs. Despite the advantages of 1D ETLs, there are still challenges that need to be overcome to achieve even higher PCEs, such as better methods to eliminate or passivate surface traps, improved understanding of the hetero-interface and optimization of the morphology (i.e., length, diameter, and spacing of NWs/NTs). This review introduces the general considerations of ETLs for HPSCs, deposition techniques used, and the current research and challenges in the field of 1D ETLs for perovskite solar cells. PMID:28468280

  10. One-Dimensional Electron Transport Layers for Perovskite Solar Cells.

    PubMed

    Thakur, Ujwal K; Kisslinger, Ryan; Shankar, Karthik

    2017-04-29

    The electron diffusion length (Ln) is smaller than the hole diffusion length (Lp) in many halide perovskite semiconductors meaning that the use of ordered one-dimensional (1D) structures such as nanowires (NWs) and nanotubes (NTs) as electron transport layers (ETLs) is a promising method of achieving high performance halide perovskite solar cells (HPSCs). ETLs consisting of oriented and aligned NWs and NTs offer the potential not merely for improved directional charge transport but also for the enhanced absorption of incoming light and thermodynamically efficient management of photogenerated carrier populations. The ordered architecture of NW/NT arrays affords superior infiltration of a deposited material making them ideal for use in HPSCs. Photoconversion efficiencies (PCEs) as high as 18% have been demonstrated for HPSCs using 1D ETLs. Despite the advantages of 1D ETLs, there are still challenges that need to be overcome to achieve even higher PCEs, such as better methods to eliminate or passivate surface traps, improved understanding of the hetero-interface and optimization of the morphology (i.e., length, diameter, and spacing of NWs/NTs). This review introduces the general considerations of ETLs for HPSCs, deposition techniques used, and the current research and challenges in the field of 1D ETLs for perovskite solar cells.

  11. Coherent intergrowth of simple cubic and quintuple tetragonal perovskites in the system Nd2-εBa3+ε(Fe,Co)5O15-δ

    NASA Astrophysics Data System (ADS)

    Kundu, Asish K.; Yu Mychinko, Mikhail; Caignaert, Vincent; Lebedev, Oleg I.; Volkova, Nadezhda E.; Deryabina, Ksenia M.; Cherepanov, Vladimir A.; Raveau, Bernard

    2015-11-01

    Investigation of the Nd2-εBa3+ε(Fe,Co)5O15-δ system, combining X-ray diffraction and electron microscopy, has allowed a tetragonal quintuple ordered perovskite "ap×ap×5ap" phasoid inter-grown within a single cubic perovskite matrix to be evidenced for ε=0. This nanoscale chemically twinned perovskite is compared with other members, Ln=Sm, Eu, Pr. The unusual long range ordering of the layers develops strains due to size mismatch between Ba2+ and Ln3+ cations. Importantly, two factors allow the strains to be decreased: (i) special intergrowths of double (LnBaFe2O6-δ) and triple (LnBa2Fe3O9-δ) perovskite ribbons/layers oriented at 90°, (ii) nanoscale chemical twinning. The spin locking effect of the nano-domain boundaries upon the magnetic properties of these perovskites is discussed.

  12. Crystalline orientation control using self-assembled TiO2 nanosheet scaffold to improve CH3NH3PbI3 perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Maitani, Masato M.; Satou, Hirokazu; Ohmura, Aoi; Tsubaki, Shuntaro; Wada, Yuji

    2017-08-01

    In perovskite solar cells with an organic inorganic hybrid metal halide perovskite crystalline semiconductor as the active layer, the properties of the n-type semiconductor scaffold, the materials used, and the morphology, wettability, and surface reactivity of the cells are important decisive factors affecting the overall device efficiency of the perovskite solar cells. We control the orientation of anatase titania nanosheets by a self-assembly technique to create the ordered mesoporous scaffolds with ordered voids. Differences between nanosheet orientations in each mesoporous scaffold indicate differences in the photoelectric properties of CH3NH3PbI3 perovskite crystals embedded in each scaffold. Although each scaffold consists of the same anatase TiO2 nanosheets, the properties of the solar cells are affected by the oxide scaffold nanomorphology, which determines the growth orientation of CH3NH3PbI3 perovskite crystals that affects the solar cell properties.

  13. Preparation of three-dimensionally ordered macroporous perovskite-type lanthanum-iron-oxide LaFeO{sub 3} with tunable pore diameters: High porosity and photonic property

    SciTech Connect

    Sadakane, Masahiro; Horiuchi, Toshitaka; Kato, Nobuyasu; Sasaki, Keisuke; Ueda, Wataru

    2010-06-15

    Three-dimensionally ordered macroporous (3DOM) lanthanum-iron-oxide (LaFeO{sub 3}) with different pore diameters was prepared using a colloidal crystal of polymer spheres with different diameters as templates. Ethylene glycol-methanol mixed solution of metal nitrates was infiltrated into the void of the colloidal crystal template of a monodispersed poly(methyl methacrylate) (PMMA) sphere. Heating of this PMMA-metal salt-ethylene glycol composite produced the desired well-ordered 3DOM LaFeO{sub 3} with a high pore fraction, which was confirmed by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), mercury (Hg) porosimetry, and ultraviolet-visible (UV-vis) diffuse reflectance spectra. 3DOM LaFeO{sub 3} with pore diameters of 281 and 321 nm shows opalescent colors because of photonic stop band properties. Catalytic activity of the 3DOM LaFeO{sub 3} for combustion of carbon particles was enhanced by a potassium cation, which was involved from K{sub 2}S{sub 2}O{sub 8} used as a polymerization initiator. - Graphical abstract: Well-ordered three-dimensionally ordered macroporous LaFeO{sub 3} materials with pore sizes ranging from 127 to 321 nm were obtained in a high pore fraction.

  14. 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

  15. New magnetic phase in the nickelate perovskite TlNiO3

    NASA Astrophysics Data System (ADS)

    Korosec, L.; Pikulski, M.; Shiroka, T.; Medarde, M.; Luetkens, H.; Alonso, J. A.; Ott, H. R.; Mesot, J.

    2017-02-01

    The RNiO3 perovskites are known to order antiferromagnetically below a material-dependent Néel temperature TN. We report experimental evidence indicating the existence of a second magnetically ordered phase in TlNiO3 above TN=104 K , obtained using nuclear magnetic resonance and muon spin rotation spectroscopy. The new phase, which persists up to a temperature T N*=202 K , is suppressed by the application of an external magnetic field of approximately 1 T. It is not yet known if such a phase also exists in other perovskite nickelates.

  16. 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.

  17. Perovskite solar cells: Danger from within

    NASA Astrophysics Data System (ADS)

    Wilks, Regan G.; Bär, Marcus

    2017-01-01

    Extensive efforts are under way to increase not only the efficiency but also the stability of organic-inorganic halide perovskite based solar cells. However, research shows that iodine-containing perovskites are vulnerable to a self-degradation pathway that may inherently limit their lifetime.

  18. Photocatalysis: HI-time for perovskites

    NASA Astrophysics Data System (ADS)

    Vesborg, Peter C. K.

    2017-01-01

    Organolead halide perovskite solar absorbers demonstrate high photovoltaic efficiencies but they are notorious for their intolerance to water. Now, methylammonium lead iodide perovskites are used to harvest solar energy — in water — via photocatalytic generation of hydrogen from solutions of hydriodic acid.

  19. 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.

  20. All-inorganic perovskite quantum dot/mesoporous TiO2 composite-based photodetectors with enhanced performance.

    PubMed

    Zhou, Lin; Yu, Kai; Yang, Fan; Zheng, Jun; Zuo, Yuhua; Li, Chuanbo; Cheng, Buwen; Wang, Qiming

    2017-02-14

    High-performance all-inorganic perovskite-based metal/semiconductor/metal (MSM) photodetectors with a bilayer composite film of mesoporous TiO2 and CsPbBr3 quantum dots as a photosensitizer were prepared. The photodetectors demonstrated significantly improved on/off ratios of nearly three orders of magnitude compared to those of pure bromine-based perovskite nanocrystal photodetectors with an MSM structure.

  1. 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.

  2. Cerium luminescence in nd0 perovskites

    NASA Astrophysics Data System (ADS)

    Setlur, A. A.; Happek, U.

    2010-05-01

    The luminescence of Ce 3+ in perovskite (ABO 3) hosts with nd0 B-site cations, specifically Ca(Hf,Zr)O 3 and (La,Gd)ScO 3, is investigated in this report. The energy position of the Ce 3+ excitation and emission bands in these perovskites is compared to those of typical Al 3+ perovskites; we find a Ce 3+ 5d 1 centroid shift and Stokes shift that are larger versus the corresponding values for the Al 3+ perovskites. It is also shown that Ce 3+ luminescence quenching is due to Ce 3+ photoionization. The comparison between these perovskites shows reasonable correlations between Ce 3+ luminescence quenching, the energy position of the Ce 3+ 5d 1 excited state with respect to the host conduction band, and the host composition.

  3. Understanding the photostability of perovskite solar cell

    NASA Astrophysics Data System (ADS)

    Joshi, Pranav H.

    Global climate change and increasing energy demands have led to a greater focus on cheaper photovoltaic energy solutions. Perovskite solar cells and organic solar cells have emerged as promising technologies for alternative cheaper photovoltaics. Perovskite solar cells have shown unprecedentedly rapid improvement in power conversion efficiency, from 3% in 2009 to more than 21% today. High absorption coefficient, long diffusion lengths, low exciton binding energy, low defect density and easy of fabrication has made perovskites near ideal material for economical and efficient photovoltaics. However, stability of perovskite and organic solar cells, especially photostability is still not well understood. In this work, we study the photostability of organic solar cells and of perovskite solar cells. (Abstract shortened by ProQuest.).

  4. 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.

  5. 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.

  6. Organohalide Lead Perovskites for Photovoltaic Applications.

    PubMed

    Yusoff, Abd Rashid Bin Mohd; Nazeeruddin, Mohammad Khaja

    2016-03-03

    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.

  7. 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.

  8. 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

    2015-12-09

    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.

  9. 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.

  10. 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

  11. 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..

  12. 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

  13. 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.

  14. Orbital Delocalization and Enhancement of Magnetic Interactions in Perovskite Oxyhydrides.

    PubMed

    Liu, Kai; Hou, Yusheng; Gong, Xingao; Xiang, Hongjun

    2016-01-25

    Recent experiments showed that some perovskite oxyhydrides have surprisingly high magnetic-transition temperature. In order to unveil the origin of this interesting phenomenon, we investigate the magnetism in SrCrO2H and SrVO2H on the basis of first-principles calculations and Monte Carlo simulations. Our work indicates that the Cr-O-Cr superexchange interaction in SrCrO2H is unexpectedly strong. Different from the previous explanation in terms of the H(-) ion substitution induced increase of the Cr-O-Cr bond angle, we reveal instead that this is mainly because the 3d orbitals in perovskite oxyhydrides becomes more delocalized since H(-) ions have weaker electronegativity and less electrons than O(2-) ions. The delocalized 3d orbitals result in stronger Cr-O interactions and enhance the magnetic-transition temperature. This novel mechanism is also applicable to the case of SrVO2H. Furthermore, we predict that SrFeO2H will have unprecedented high Neel temperature because of the extraordinarily strong Fe-H-Fe σ-type interactions. Our work suggests the anion substitution can be used to effectively manipulate the magnetic properties of perovskite compounds.

  15. Rapid Microwave Synthesis of Perovskite Oxide Nanostructures with Enhanced Functionality

    NASA Astrophysics Data System (ADS)

    Salazar, Gregory; Datta, Anuja; Mukherjee, Pritish

    2015-03-01

    Perovskite oxides are an important class of materials having high dielectric and piezoelectric coefficients, switchable ferroelectric (FE) polarization and interesting optical and electrical properties. Realization of functional devices based on classic perovskite oxides such as Pb(Zr0.52Ti0.48) O3 (PZT), and emerging Pb-free noncentrosymmetric (NCS) oxides, such as, ZnSnO3, ZnTiO3 and CaTiO3 have reinforced the investigation of these materials in multiple dimensions and length scales. However, large-scale synthesis and integration of ordered low-dimensional structures is a challenge, due to their complicated methodologies, high-cost and difficulties with phase stability. We discuss a generalized, cost-effective, rapid microwave synthesis route for size and shape selective nanostructure growth of these functional perovskite oxides on industrially viable flexible and hard substrates, stabilized by an enhanced ionic covalence. The rational synthesis approach allowed improved tunability of the size, shape, and orientation of the structures with improved electrical and FE properties. The facile fabrication route of these nanostructures may expand the outreach of probes for understanding the structure-property relationships in these hitherto unexplored and technologically important materials.

  16. Persistent Energetic Electrons in Methylammonium Lead Iodide Perovskite Thin Films.

    PubMed

    Niesner, Daniel; Zhu, Haiming; Miyata, Kiyoshi; Joshi, Prakriti P; Evans, Tyler J S; Kudisch, Bryan J; Trinh, M Tuan; Marks, Manuel; Zhu, X-Y

    2016-12-07

    In conventional semiconductor solar cells, carriers are extracted at the band edges and the excess electronic energy (E*) is lost as heat. If E* is harvested, power conversion efficiency can be as high as twice the Shockley-Queisser limit. To date, materials suitable for hot carrier solar cells have not been found due to efficient electron/optical-phonon scattering in most semiconductors, but our recent experiments revealed long-lived hot carriers in single-crystal hybrid lead bromide perovskites. Here we turn to polycrystalline methylammonium lead iodide perovskite, which has emerged as the material for highly efficient solar cells. We observe energetic electrons with excess energy ⟨E*⟩ ≈ 0.25 eV above the conduction band minimum and with lifetime as long as ∼100 ps, which is 2-3 orders of magnitude longer than those in conventional semiconductors. The energetic carriers also give rise to hot fluorescence emission with pseudo-electronic temperatures as high as 1900 K. These findings point to a suppression of hot carrier scattering with optical phonons in methylammonium lead iodide perovskite. We address mechanistic origins of this suppression and, in particular, the correlation of this suppression with dynamic disorder. We discuss potential harvesting of energetic carriers for solar energy conversion.

  17. Orbital Delocalization and Enhancement of Magnetic Interactions in Perovskite Oxyhydrides

    PubMed Central

    Liu, Kai; Hou, Yusheng; Gong, Xingao; Xiang, Hongjun

    2016-01-01

    Recent experiments showed that some perovskite oxyhydrides have surprisingly high magnetic-transition temperature. In order to unveil the origin of this interesting phenomenon, we investigate the magnetism in SrCrO2H and SrVO2H on the basis of first-principles calculations and Monte Carlo simulations. Our work indicates that the Cr-O-Cr superexchange interaction in SrCrO2H is unexpectedly strong. Different from the previous explanation in terms of the H− ion substitution induced increase of the Cr-O-Cr bond angle, we reveal instead that this is mainly because the 3d orbitals in perovskite oxyhydrides becomes more delocalized since H− ions have weaker electronegativity and less electrons than O2− ions. The delocalized 3d orbitals result in stronger Cr-O interactions and enhance the magnetic-transition temperature. This novel mechanism is also applicable to the case of SrVO2H. Furthermore, we predict that SrFeO2H will have unprecedented high Neel temperature because of the extraordinarily strong Fe-H-Fe σ-type interactions. Our work suggests the anion substitution can be used to effectively manipulate the magnetic properties of perovskite compounds. PMID:26804825

  18. Magnetic domain wall induced ferroelectricity in double perovskites

    NASA Astrophysics Data System (ADS)

    Zhou, Hai Yang; Zhao, Hong Jian; Zhang, Wen Qing; Chen, Xiang Ming

    2015-04-01

    Recently, a magnetically induced ferroelectricity occurring at magnetic domain wall of double perovskite Lu2CoMnO6 has been reported experimentally. However, there exists a conflict whether the electric polarization is along b or c direction. Here, by first-principles calculations, we show that the magnetic domain wall (with ↑↑↓↓ spin configuration) can lead to the ferroelectric displacements of R3+, Ni2+, Mn4+, and O2- ions in double perovskites R2NiMnO6 (R = rare earth ion) via exchange striction. The resulted electric polarization is along b direction with the P21 symmetry. We further reveal the origin of the ferroelectric displacements as that: (1) on a structural point of view, such displacements make the two out-of-plane Ni-O-Mn bond angles as well as Ni-Mn distance unequal, and (2) on an energy point of view, such displacements weaken the out-of-plane Ni-Mn super-exchange interaction obviously. Finally, our calculations show that such a kind of ferroelectric order is general in ferromagnetic double perovskites.

  19. Magnetic domain wall induced ferroelectricity in double perovskites

    SciTech Connect

    Zhou, Hai Yang; Zhao, Hong Jian E-mail: xmchen59@zju.edu.cn; Chen, Xiang Ming E-mail: xmchen59@zju.edu.cn; Zhang, Wen Qing

    2015-04-13

    Recently, a magnetically induced ferroelectricity occurring at magnetic domain wall of double perovskite Lu{sub 2}CoMnO{sub 6} has been reported experimentally. However, there exists a conflict whether the electric polarization is along b or c direction. Here, by first-principles calculations, we show that the magnetic domain wall (with ↑↑↓↓ spin configuration) can lead to the ferroelectric displacements of R{sup 3+}, Ni{sup 2+}, Mn{sup 4+}, and O{sup 2−} ions in double perovskites R{sub 2}NiMnO{sub 6} (R = rare earth ion) via exchange striction. The resulted electric polarization is along b direction with the P2{sub 1} symmetry. We further reveal the origin of the ferroelectric displacements as that: (1) on a structural point of view, such displacements make the two out-of-plane Ni-O-Mn bond angles as well as Ni-Mn distance unequal, and (2) on an energy point of view, such displacements weaken the out-of-plane Ni-Mn super-exchange interaction obviously. Finally, our calculations show that such a kind of ferroelectric order is general in ferromagnetic double perovskites.

  20. Order-disorder transition and weak ferromagnetism in the perovskite metal formate frameworks of [(CH3)2NH2][M(HCOO)3] and [(CH3)2ND2][M(HCOO)3] (M = Ni, Mn).

    PubMed

    Mączka, Mirosław; Gągor, Anna; Macalik, Bogusław; Pikul, Adam; Ptak, Maciej; Hanuza, Jerzy

    2014-01-06

    We report the synthesis, crystal structure, thermal, dielectric, Raman, infrared, and magnetic properties of hydrogen and deuterated divalent metal formates, [(CH3)2NH2][M(HCOO)3] and [(CH3)2ND2][M(HCOO)3], where M = Ni, Mn. On the basis of Raman and IR data, assignment of the observed modes to respective vibrations of atoms is proposed. The thermal studies show that for the Ni compounds deuteration leads to a decrease of the phase transition temperature Tc by 5.6 K, whereas it has a negligible effect on Tc in the Mn analogues. This behavior excludes the possibility of proton (deuteron) movement along the N-H···O (N-D···O) bonds as the microscopic origin of the first-order phase transition observed in these crystals below 190 K. According to single-crystal X-ray diffraction, the dimethylammonium (DMA) cations are dynamically disordered at room temperature, because the hydrogen bonds between the NH2 (ND2) groups and the metal-formate framework are disordered. The highly dynamic nature of hydrogen bonds in the high-temperature phases manifests in the Raman and IR spectra through very large bandwidth of modes involving vibrations of the NH2 (ND2) groups. The abrupt decrease in the bandwidth and shifts of modes near Tc signifies the ordering of hydrogen bonds and DMA(+) cations as well as significant distortion of the metal-formate framework across the phase transition. However, some amount of motion is retained by the DMA(+) cation in the ferroelectric phase and a complete freezing-in of this motion occurs below 100 K. The dielectric studies reveal pronounced dielectric dispersion that can be attributed to slow dynamics of large DMA(+) cations. The low-temperature studies also show that magnetic properties of the studied compounds can be explained assuming that they are ordered ferrimagnetically with nearly compensated magnetic moments of Ni and Mn. IR data reveal weak anomalies below 40 K that arise due to spin-phonon coupling. Our results also show that due to

  1. Dry (Mg,Fe)SiO3 perovskite in the Earth's lower mantle

    DOE PAGES

    Panero, Wendy R.; Pigott, Jeffrey S.; Reaman, Daniel M.; ...

    2015-02-26

    Combined synthesis experiments and first-principles calculations show that MgSiO3-perovskite with minor Al or Fe does not incorporate significant OH under lower mantle conditions. Perovskite, stishovite, and residual melt were synthesized from natural Bamble enstatite samples (Mg/(Fe+Mg) = 0.89 and 0.93; Al2O3 < 0.1 wt% with 35 and 2065 ppm wt H2O, respectively) in the laser-heated diamond anvil cell at 1600-2000 K and 25-65 GPa. Combined Fourier transform infrared (FTIR) spectroscopy, x-ray diffraction, and ex-situ transmission electron microscopy (TEM) analysis demonstrates little difference in the resulting perovskite as a function of initial water content. Four distinct OH vibrational stretching bands aremore » evident upon cooling below 100 K (3576, 3378, 3274, and 3078 cm-1), suggesting 4 potential bonding sites for OH in perovskite with a maximum water content of 220 ppm wt H2O, and likely no more than 10 ppm wt H2O. Complementary, Fe-free, first-principles calculations predict multiple potential bonding sites for hydrogen in perovskite, each with significant solution enthalpy (0.2 eV/defect). We calculate that perovskite can dissolve less than 37 ppm wt H2O (400 ppm H/Si) at the top of the lower mantle, decreasing to 31 ppm wt H2O (340 ppm H/Si) at 125 GPa and 3000 K in the absence of a melt or fluid phase. Here, we propose that these results resolve a long-standing debate of the perovskite melting curve and explain the order of magnitude increase in viscosity from upper to lower mantle.« less

  2. Dry (Mg,Fe)SiO3 perovskite in the Earth's lower mantle

    NASA Astrophysics Data System (ADS)

    Panero, Wendy R.; Pigott, Jeffrey S.; Reaman, Daniel M.; Kabbes, Jason E.; Liu, Zhenxian

    2015-02-01

    Combined synthesis experiments and first-principles calculations show that MgSiO3-perovskite with minor Al or Fe does not incorporate significant OH under lower mantle conditions. Perovskite, stishovite, and residual melt were synthesized from natural Bamble enstatite samples (Mg/(Fe + Mg) = 0.89 and 0.93; Al2O3 < 0.1 wt % with 35 and 2065 ppm weight H2O, respectively) in the laser-heated diamond anvil cell at 1600-2000 K and 25-65 GPa. Combined Fourier transform infrared spectroscopy, X-ray diffraction, and ex situ transmission electron microscopy analysis demonstrates little difference in the resulting perovskite as a function of initial water content. Four distinct OH vibrational stretching bands are evident upon cooling below 100 K (3576, 3378, 3274, and 3078 cm-1), suggesting four potential bonding sites for OH in perovskite with a maximum water content of 220 ppm weight H2O, and likely no more than 10 ppm weight H2O. Complementary, Fe-free, first-principles calculations predict multiple potential bonding sites for hydrogen in perovskite, each with significant solution enthalpy (0.2 eV/defect). We calculate that perovskite can dissolve less than 37 ppm weight H2O (400 ppm H/Si) at the top of the lower mantle, decreasing to 31 ppm weight H2O (340 ppm H/Si) at 125 GPa and 3000 K in the absence of a melt or fluid phase. We propose that these results resolve a long-standing debate of the perovskite melting curve and explain the order-of-magnitude increase in viscosity from upper to lower mantle.

  3. Dry (Mg,Fe)SiO3 perovskite in the Earth's lower mantle

    SciTech Connect

    Panero, Wendy R.; Pigott, Jeffrey S.; Reaman, Daniel M.; Kabbes, Jason E.; Liu, Zhenxian

    2015-02-26

    Combined synthesis experiments and first-principles calculations show that MgSiO3-perovskite with minor Al or Fe does not incorporate significant OH under lower mantle conditions. Perovskite, stishovite, and residual melt were synthesized from natural Bamble enstatite samples (Mg/(Fe+Mg) = 0.89 and 0.93; Al2O3 < 0.1 wt% with 35 and 2065 ppm wt H2O, respectively) in the laser-heated diamond anvil cell at 1600-2000 K and 25-65 GPa. Combined Fourier transform infrared (FTIR) spectroscopy, x-ray diffraction, and ex-situ transmission electron microscopy (TEM) analysis demonstrates little difference in the resulting perovskite as a function of initial water content. Four distinct OH vibrational stretching bands are evident upon cooling below 100 K (3576, 3378, 3274, and 3078 cm-1), suggesting 4 potential bonding sites for OH in perovskite with a maximum water content of 220 ppm wt H2O, and likely no more than 10 ppm wt H2O. Complementary, Fe-free, first-principles calculations predict multiple potential bonding sites for hydrogen in perovskite, each with significant solution enthalpy (0.2 eV/defect). We calculate that perovskite can dissolve less than 37 ppm wt H2O (400 ppm H/Si) at the top of the lower mantle, decreasing to 31 ppm wt H2O (340 ppm H/Si) at 125 GPa and 3000 K in the absence of a melt or fluid phase. Here, we propose that these results resolve a long-standing debate of the perovskite melting curve and explain the order of magnitude increase in viscosity from upper to lower mantle.

  4. Photoresponse of CsPbBr3 and Cs4PbBr6 Perovskite Single Crystals.

    PubMed

    Cha, Ji-Hyun; Han, Jae Hoon; Yin, Wenping; Park, Cheolwoo; Park, Yongmin; Ahn, Tae Kyu; Cho, Jeong Ho; Jung, Duk-Young

    2017-02-02

    High-quality and millimeter-sized perovskite single crystals of CsPbBr3 and Cs4PbBr6 were prepared in organic solvents and studied for correlation between photocurrent generation and photoluminescence (PL) emission. The CsPbBr3 crystals, which have a 3D perovskite structure, showed a highly sensitive photoresponse and poor PL signal. In contrast, Cs4PbBr6 crystals, which have a 0D perovskite structure, exhibited more than 1 order of magnitude higher PL intensity than CsPbBr3, which generated an ultralow photoresponse under illumination. Their contrasting optoelectrical characteristics were attributed to different exciton binding energies, induced by coordination geometry of the [PbBr6](4-) octahedron sublattices. This work correlated the local structures of lead in the primitive perovskite and its derivatives to PL spectra as well as photoconductivity.

  5. Extrinsic ion migration in perovskite solar cells

    DOE PAGES

    Li, Zhen; Xiao, Chuanxiao; Yang, Ye; ...

    2017-04-10

    In this study, the migration of intrinsic ions (e.g., MA+, Pb2+, I–) in organic–inorganic hybrid perovskites has received significant attention with respect to the critical roles of these ions in the hysteresis and degradation in perovskite solar cells (PSCs). Here, we demonstrate that extrinsic ions (e.g., Li+, H+, Na+), when used in the contact layers in PSCs, can migrate across the perovskite layer and strongly impact PSC operation. In a TiO2/perovskite/spiro-OMeTAD-based PSC, Li+-ion migration from spiro-OMeTAD to the perovskite and TiO2 layer is illustrated by time-of-flight secondary-ion mass spectrometry. The movement of Li+ ions in PSCs plays an importantmore » role in modulating the solar cell performance, tuning TiO2 carrier-extraction properties, and affecting hysteresis in PSCs. The influence of Li+-ion migration was investigated using time-resolved photoluminescence, Kelvin probe force microscopy, and external quantum efficiency spectra. Other extrinsic ions such as H+ and Na+ also show a clear impact on the performance and hysteresis in PSCs. Understanding the impacts of extrinsic ions in perovskite-based devices could lead to new material and device designs to further advance perovskite technology for various applications.« less

  6. Solvent-Mediated Crystallization of CH 3 NH 3 SnI 3 Films for Heterojunction Depleted Perovskite Solar Cells

    SciTech Connect

    Hao, Feng; Stoumpos, Constantinos C.; Guo, Peijun; Zhou, Nanjia; Marks, Tobin J.; Chang, Robert P. H.; Kanatzidis, Mercouri G.

    2015-09-09

    Organo-lead halide perovskite solar cells have gained enormous significance and have now achieved power conversion efficiencies of ~20%. However, the potential toxicity of lead in these systems raises environmental concerns for widespread deployment. Here we investigate solvent effects on the crystallization of the lead-free methylammonium tin triiodide (CH3NH3SnI3) perovskite films in a solution growth process. Highly uniform, pinhole-free perovskite films are obtained from a dimethyl sulfoxide (DMSO) solution via a transitional SnI2·3DMSO intermediate phase. This high-quality perovskite film enables the realization of heterojunction depleted solar cells based on mesoporous TiO2 layer but in the absence of any hole-transporting material with an unprecedented photocurrent up to 21 mA cm–2. Charge extraction and transient photovoltage decay measurements reveal high carrier densities in the CH3NH3SnI3 perovskite device which are one order of magnitude larger than CH3NH3PbI3-based devices but with comparable recombination lifetimes in both devices. The relatively high background dark carrier density of the Sn-based perovskite is responsible for the lower photovoltaic efficiency in comparison to the Pb-based analogues. These results provide important progress toward achieving improved perovskite morphology control in realizing solution-processed highly efficient lead-free perovskite solar cells.

  7. Dimensionality-driven insulator–metal transition in A-site excess non-stoichiometric perovskites

    PubMed Central

    Wang, Zhongchang; Okude, Masaki; Saito, Mitsuhiro; Tsukimoto, Susumu; Ohtomo, Akira; Tsukada, Masaru; Kawasaki, Masashi; Ikuhara, Yuichi

    2010-01-01

    Coaxing correlated materials to the proximity of the insulator–metal transition region, where electronic wavefunctions transform from localized to itinerant, is currently the subject of intensive research because of the hopes it raises for technological applications and also for its fundamental scientific significance. In general, this tuning is achieved by either chemical doping to introduce charge carriers, or external stimuli to lower the ratio of Coulomb repulsion to bandwidth. In this study, we combine experiment and theory to show that the transition from well-localized insulating states to metallicity in a Ruddlesden-Popper series, La0.5Srn+1−0.5TinO3n+1, is driven by intercalating an intrinsically insulating SrTiO3 unit, in structural terms, by dimensionality n. This unconventional strategy, which can be understood upon a complex interplay between electron–phonon coupling and electron correlations, opens up a new avenue to obtain metallicity or even superconductivity in oxide superlattices that are normally expected to be insulators. PMID:21045824

  8. Large grained perovskite solar cells derived from single-crystal perovskite powders with enhanced ambient stability

    SciTech Connect

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

    2016-05-25

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

  9. Large grained perovskite solar cells derived from single-crystal perovskite powders with enhanced ambient stability

    DOE PAGES

    Yen, Hung -Ju; Liang, Po -Wei; Chueh, Chu -Chen; ...

    2016-05-25

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

  10. Large grained perovskite solar cells derived from single-crystal perovskite powders with enhanced ambient stability

    SciTech Connect

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

    2016-05-25

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

  11. Facile preparation of smooth perovskite films for efficient meso/planar hybrid structured perovskite solar cells.

    PubMed

    Zhang, Meng; Yu, Hua; Yun, Jung-Ho; Lyu, Miaoqiang; Wang, Qiong; Wang, Lianzhou

    2015-06-21

    Smooth organolead halide perovskite films for meso/planar hybrid structured perovskite solar cells were prepared by a simple compressed air blow-drying method under ambient conditions. The resultant perovskite films show high surface coverage, leading to a device power conversion efficiency of over 10% with an open circuit voltage up to 1.003 V merely using pristine poly(3-hexylthiophene) (P3HT) as a hole transporter.

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

    PubMed Central

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

    2017-01-01

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

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

    PubMed

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

    2017-03-19

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

  14. Neutron Diffraction Study of Silicate Perovskites

    NASA Astrophysics Data System (ADS)

    Mao, H. K.; van Orman, J.; Fei, Y.; Hemley, R. J.; Loveday, J.; Nelmes, R.; Smith, R. I.

    2002-12-01

    The oxygen deficiency and cation-site distribution of silicate perovskite control its physical and chemical properties, including density, bulk modulus, defect mobility, ionic transport, flow behavior, oxidation states, hydration, and minor-element solubility. These properties of perovskite, in turn control the geophysical and geochemical processes of the Earth. The possibility of oxygen deficiency was first recognized in perovskite with minor amounts of Al replacing Mg and Si [1, 2], and its significance is compared to the analogous defect perovskite in ceramics [3]. Basic crystallographic characteristics of the silicate perovskite, including the lattice parameters of the orthorhombic unit cell, the Pbmn space group, and atomic positions, were previously determined by x-ray diffraction [4]. The defect crystallography of silicate perovskite, however, cannot be measured by x-rays because the relevant ions (Mg2+, Al3+, Si4+ and O2-) are isoelectronic. These ions have very different neutron cross-section and can be readily resolved by neutron diffraction. Using multianvil apparatus, we synthesized perovskite samples at 1700°C and 25-28 GPa. We perform multiple runs to accumulate 3 mm3 sample each for the MgSiO3 end member and MgSiO3 plus 5 weight %\\ Al2O3 in perovskite structure. Excellent powder diffraction data were collected at the POLARIS Beamline of ISIS, Rutherford Appleton Lab, and were subjected to Rietveld analysis. Neutron derived information sheds light on the unusual effects found for Al3+ substitution on the compressibility of the silicate perovskite [1]. 1. J. Zhang and D. J. Weidner, Science 284, 782 (1999). 2. J. P. Brodholt, Nature 407, 620 (2000). 3. A. Navrotsky, Science 284, 1788 (1999). 4. N. L. Ross and R. M. Hazen, Phys. Chem. Minerals 17, 228 (1990).

  15. Exciton Binding Energy in Organic-Inorganic Tri-Halide Perovskites.

    PubMed

    Askar, Abdelrahman M; Shankar, Karthik

    2016-06-01

    The recent dramatic increase in the power conversion efficiencies of organic-inorganic tri-halide perovskite solar cells has triggered intense research worldwide and created a paradigm shift in the photovoltaics field. It is crucial to develop a solid understanding of the photophysical processes underlying solar cell operation in order to both further improve the photovoltaic performance of perovskite solar cells as well as to exploit the broader optoelectronic applications of the tri-halide perovskites. In this short review, we summarize the main research findings about the binding energy of excitons in tri-halide perovskite materials and find that a value in the range of 2-22 meV at room temperature would be a safe estimate. Spontaneous free carrier generation is the dominant process taking place directly after photoexcitation in organic-inorganic tri-halide perovskites at room temperature, which eliminates the exciton diffusion bottleneck present in organic solar cells and constitutes a major contributing factor to the high photovoltaic performance of this material.

  16. Imaging the Long Transport Lengths of Photo-generated Carriers in Oriented Perovskite Films

    NASA Astrophysics Data System (ADS)

    Liu, Shuhao; Wang, Lili; Lin, Wei-Chun; Sucharitakul, Sukrit; Burda, Clemens; Gao, Xuan P. A.

    2016-12-01

    Organometal halide perovskite has emerged as a promising material for solar cells and optoelectronics. Although the long diffusion length of photo-generated carriers is believed to be a critical factor responsible for the material's high efficiency in solar cells, a direct study of carrier transport over long distances in organometal halide perovskites is still lacking. We fabricated highly oriented crystalline CH$_3$NH$_3$PbI$_3$ (MAPbI$_3$) thin film lateral transport devices with long channel length (~ 120 $\\mu$m). By performing spatially scanned photocurrent imaging measurements with local illumination, we directly show that the perovskite films prepared here have very long transport lengths for photo-generated carriers, with a minority carrier (electron) diffusion length on the order of 10 $\\mu$m. Our approach of applying scanning photocurrent microscopy to organometal halide perovskites may be further used to elucidate the carrier transport processes and vastly different carrier diffusion lengths (~ 100 nm to 100 $\\mu$m) in different types of organometal halide perovskites.

  17. High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites.

    PubMed

    Sutter-Fella, Carolin M; Li, Yanbo; Amani, Matin; Ager, Joel W; Toma, Francesca M; Yablonovitch, Eli; Sharp, Ian D; Javey, Ali

    2016-01-13

    Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH3NH3PbI3-xBrx perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamic range. The internal luminescence quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ Eg ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells.

  18. Investigation of the Interaction between Perovskite Films with Moisture via in Situ Electrical Resistance Measurement.

    PubMed

    Hu, Long; Shao, Gang; Jiang, Tao; Li, Dengbing; Lv, Xinlin; Wang, Hongya; Liu, Xinsheng; Song, Haisheng; Tang, Jiang; Liu, Huan

    2015-11-18

    Organometal halide perovskites have recently emerged as outstanding semiconductors for solid-state optoelectronic devices. Their sensitivity to moisture is one of the biggest barriers to commercialization. In order to identify the effect of moisture in the degradation process, here we combined the in situ electrical resistance measurement with time-resolved X-ray diffraction analysis to investigate the interaction of CH3NH3PbI(3-x)Cl(x) perovskite films with moisture. Upon short-time exposure, the resistance of the perovskite films decreased and it could be fully recovered, which were ascribed to a mere chemisorption of water molecules, followed by the reversible hydration into CH3NH3PbI(3-x)Cl(x)·H2O. Upon long-time exposure, however, the resistance became irreversible due to the decomposition into PbI2. The results demonstrated the formation of monohydrated intermediate phase when the perovskites interacted with moisture. The role of moisture in accelerating the thermal degradation at 85 °C was also demonstrated. Furthermore, our study suggested that the perovskite films with fewer defects may be more inherently resistant to moisture.

  19. Perovskites: transforming photovoltaics, a mini-review

    SciTech Connect

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

    2015-01-06

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

  20. Static and dynamic strain coupling behaviour of ferroic and multiferroic perovskites from resonant ultrasound spectroscopy.

    PubMed

    Carpenter, M A

    2015-07-08

    PrAlO3, and this is suppressed by application of an external magnetic field in the colossal magnetoresistive manganite Pr0.48Ca0.52MnO3 or by reducing grain size in La0.5Ca0.5MnO3. Spin state transitions for Co(3+) in LaCoO3, NdCoO3 and GdCoO3 produce changes in the shear modulus that scale with a spin state order parameter, which is itself coupled with the order parameter(s) for octahedral tilting in a linear-quadratic manner. A new class of phase transitions in perovskites, due to orientational or conformational ordering of organic molecules on the crystallographic A-site of metal organic frameworks, is illustrated for [(CH3)2NH2]Co(HCOO)3 and [(CH2)3NH2]Mn(HCOO)3 which also display elastic and anelastic anomalies due to the influence of intrinsic and extrinsic strain relaxation behaviour.

  1. Static and dynamic strain coupling behaviour of ferroic and multiferroic perovskites from resonant ultrasound spectroscopy

    NASA Astrophysics Data System (ADS)

    Carpenter, M. A.

    2015-07-01

    PrAlO3, and this is suppressed by application of an external magnetic field in the colossal magnetoresistive manganite Pr0.48Ca0.52MnO3 or by reducing grain size in La0.5Ca0.5MnO3. Spin state transitions for Co3+ in LaCoO3, NdCoO3 and GdCoO3 produce changes in the shear modulus that scale with a spin state order parameter, which is itself coupled with the order parameter(s) for octahedral tilting in a linear-quadratic manner. A new class of phase transitions in perovskites, due to orientational or conformational ordering of organic molecules on the crystallographic A-site of metal organic frameworks, is illustrated for [(CH3)2NH2]Co(HCOO)3 and [(CH2)3NH2]Mn(HCOO)3 which also display elastic and anelastic anomalies due to the influence of intrinsic and extrinsic strain relaxation behaviour.

  2. Co-doping Strategy for Developing Perovskite Oxides as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction.

    PubMed

    Xu, Xiaomin; Su, Chao; Zhou, Wei; Zhu, Yinlong; Chen, Yubo; Shao, Zongping

    2016-02-01

    A synergistic co-doping strategy is proposed to identify a series of BaCo0.9-x Fe x Sn0.1O3-δ perovskites with tunable electrocatalytic activity for the oxygen evolution reaction (OER). Simply through tailoring the relative concentrations of less OER-active tin and iron dopants, a cubic perovskite structure (BaCo0.7Fe0.2Sn0.1O3-δ) is stabilized, showing intrinsic OER activity >1 order of magnitude larger than IrO2 and a Tafel slope of 69 mV dec(-1).

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

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

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

  5. Critical behavior of Y2NiMnO6 double perovskite

    NASA Astrophysics Data System (ADS)

    Nhalil, Hariharan; Nair, Harikrishnan S.; Elizabeth, Suja

    2016-05-01

    Critical behavior of double perovskite Y2NiMnO6 near the second-order ferromagnetic transition is studied. Scaling exponents calculated frommodified Arrot plots are confirmed by Kouvel-Fisher method and satisfy the Widom's scaling relation. The exponents do not follow any conventional theoretical models.β values areconsistent with 3D-Ising model whileδconformsto TCMF and γ valueclosely relates to the 3D-Heisenberg model. Critical exponents are compared with similar R2NiMnO6 double perovskites which shows that a decrease in size of R ion changes exponents from mean-field to the 3D-Ising model.

  6. Improper electric polarization in simple perovskite oxides with two magnetic sublattices

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

    ABO3 perovskite oxides with magnetic A and B cations offer a unique playground to explore interactions involving two spin sublattices and the emergent effects they may drive. Of particular interest is the possibility of having magnetically driven improper ferroelectricity, as in the much studied families of rare-earth orthoferrites and orthochromites; yet, the mechanisms behind such effects remain to be understood in detail. Here we show that the strongest polar order corresponds to collinear spin configurations and is driven by non-relativistic exchange-strictive mechanisms. Our first-principles simulations reveal the dominant magnetostructural couplings underlying the observed ferroelectricity, including a striking magnetically driven piezoelectric effect. Further, we derive phenomenological and atomistic theories that describe such couplings in a generic perovskite lattice. This allows us to predict how the observed effects can be enhanced, and even how similar ones can be obtained in other perovskite families.

  7. Improper electric polarization in simple perovskite oxides with two magnetic sublattices.

    PubMed

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

    2017-01-20

    ABO3 perovskite oxides with magnetic A and B cations offer a unique playground to explore interactions involving two spin sublattices and the emergent effects they may drive. Of particular interest is the possibility of having magnetically driven improper ferroelectricity, as in the much studied families of rare-earth orthoferrites and orthochromites; yet, the mechanisms behind such effects remain to be understood in detail. Here we show that the strongest polar order corresponds to collinear spin configurations and is driven by non-relativistic exchange-strictive mechanisms. Our first-principles simulations reveal the dominant magnetostructural couplings underlying the observed ferroelectricity, including a striking magnetically driven piezoelectric effect. Further, we derive phenomenological and atomistic theories that describe such couplings in a generic perovskite lattice. This allows us to predict how the observed effects can be enhanced, and even how similar ones can be obtained in other perovskite families.

  8. Improper electric polarization in simple perovskite oxides with two magnetic sublattices

    PubMed Central

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

    2017-01-01

    ABO3 perovskite oxides with magnetic A and B cations offer a unique playground to explore interactions involving two spin sublattices and the emergent effects they may drive. Of particular interest is the possibility of having magnetically driven improper ferroelectricity, as in the much studied families of rare-earth orthoferrites and orthochromites; yet, the mechanisms behind such effects remain to be understood in detail. Here we show that the strongest polar order corresponds to collinear spin configurations and is driven by non-relativistic exchange-strictive mechanisms. Our first-principles simulations reveal the dominant magnetostructural couplings underlying the observed ferroelectricity, including a striking magnetically driven piezoelectric effect. Further, we derive phenomenological and atomistic theories that describe such couplings in a generic perovskite lattice. This allows us to predict how the observed effects can be enhanced, and even how similar ones can be obtained in other perovskite families. PMID:28106057

  9. Efficient Planar Heterojunction Perovskite Solar Cells Based on Formamidinium Lead Bromide.

    PubMed

    Hanusch, Fabian C; Wiesenmayer, Erwin; Mankel, Eric; Binek, Andreas; Angloher, Philipp; Fraunhofer, Christina; Giesbrecht, Nadja; Feckl, Johann M; Jaegermann, Wolfram; Johrendt, Dirk; Bein, Thomas; Docampo, Pablo

    2014-08-21

    The development of medium-bandgap solar cell absorber materials is of interest for the design of devices such as tandem solar cells and building-integrated photovoltaics. The recently developed perovskite solar cells can be suitable candidates for these applications. At present, wide bandgap alkylammonium lead bromide perovskite absorbers require a high-temperature sintered mesoporous TiO2 photoanode in order to function efficiently, which makes them unsuitable for some of the above applications. Here, we present for the first time highly efficient wide bandgap planar heterojunction solar cells based on the structurally related formamidinium lead bromide. We show that this material exhibits much longer diffusion lengths of the photoexcited species than its methylammonium counterpart. This results in planar heterojunction solar cells exhibiting power conversion efficiencies approaching 7%. Hence, formamidinium lead bromide is a strong candidate as a wide bandgap absorber in perovskite solar cells.

  10. 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

    2016-06-09

    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.

  11. 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.

  12. Strongly correlated perovskite fuel cells

    SciTech Connect

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

    2016-05-16

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines1, 2, 3, 4. 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 number5. 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 membranes6. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

  13. Strongly correlated perovskite fuel cells

    DOE PAGES

    Zhou, You; Guan, Xiaofei; Zhou, Hua; ...

    2016-05-16

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the 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.more » 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.« less

  14. Strongly correlated perovskite fuel cells

    SciTech Connect

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

    2016-05-16

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the 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.

  15. High-performance perovskite light-emitting diodes via morphological control of perovskite films

    NASA Astrophysics Data System (ADS)

    Yu, Jae Choul; Kim, Da Bin; Jung, Eui Dae; Lee, Bo Ram; Song, Myoung Hoon

    2016-03-01

    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).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

  16. Study on the development and stability of perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Xing, Shucheng

    2017-08-01

    Recently, the development of perovskite solar cells has aroused the concern of the majority of scholars, the current photoelectric conversion efficiency has reached 21%. So the thorough study of the principle of perovskite type solar cells will make better the use of its special performance. But so far, perovskite type solar cells still have many unstable factors. This paper first discusses the predecessor of perovskite solar cells, dye-sensitized batteries, and then study the working principle of the former, followed by the perovskite-type thermal instability and light instability to be discussed, at last talks about the current Major issues perovskite materials are facing and make a summary.

  17. A non-catalytic vapor growth regime for organohalide perovskite nanowires using anodic aluminum oxide templates.

    PubMed

    Tavakoli, Mohammad Mahdi; Waleed, Aashir; Gu, Leilei; Zhang, Daquan; Tavakoli, Rouhollah; Lei, Bingbing; Su, Wenjun; Fang, Fang; Fan, Zhiyong

    2017-05-11

    In this work, a novel and facile synthesis process to fabricate single crystalline organometal halide perovskite nanowires has been successfully developed. Nanowires were grown in a high density ordered array from metal nanoclusters inside anodic aluminum oxide templates using a non-catalytic chemical vapor deposition method. Specifically, perovskite NWs were grown as a result of the reaction between methylammonium iodide (MAI) and the Pb/Sn (Pb or Sn) metal in anodic aluminum oxide templates under optimal conditions. The characterization results show that there is a reaction zone at the interface between the perovskite material and metal, at the bottom of the anodic aluminum oxide nanochannels. In order to sustain perovskite NW growth, MAI molecules have to diffuse downward through the perovskite NWs to reach the reaction zone. In fact, the reaction is facilitated by the formation of an intermediate product of the metal iodide compound. This suggests that the Pb/Sn metal is converted to PbI2/SnI2 first and then perovskite NWs are formed as a result of the reaction between MAI and PbI2/SnI2 through a vapor-solid-solid process. The optical characterization results demonstrate that the as-synthesized NWs with an ultra-high nanostructure density can serve as ideal candidates for optoelectronic devices, such as solar cells, light-emitting didoes, photodetectors, etc. And the reported growth approach here is highly versatile combining the merits of excellent controllability, cost-effectiveness and tunability on material composition and physical properties.

  18. Selective enhancement of optical nonlinearity in two-dimensional organic-inorganic lead iodide perovskites.

    PubMed

    Saouma, F O; Stoumpos, C C; Wong, J; Kanatzidis, M G; Jang, J I

    2017-09-29

    Reducing the dimensionality of three-dimensional hybrid metal halide perovskites can improve their optoelectronic properties. Here, we show that the third-order optical nonlinearity, n 2, of hybrid lead iodide perovskites is enhanced in the two-dimensional Ruddlesden-Popper series, (CH3(CH2)3NH3)2(CH3NH3) n-1Pb n I3n+1 (n = 1-4), where the layer number (n) is engineered for bandgap tuning from E g = 1.60 eV (n = ∞; bulk) to 2.40 eV (n = 1). Despite the unfavorable relation, [Formula: see text], strong quantum confinement causes these two-dimensional perovskites to exhibit four times stronger third harmonic generation at mid-infrared when compared with the three-dimensional counterpart, (CH3NH3)PbI3. Surprisingly, however, the impact of dimensional reduction on two-photon absorption, which is the Kramers-Kronig conjugate of n 2, is rather insignificant as demonstrated by broadband two-photon spectroscopy. The concomitant increase of bandgap and optical nonlinearity is truly remarkable in these novel perovskites, where the former increases the laser-induced damage threshold for high-power nonlinear optical applications.Hybrid metal halide perovskites can exhibit improved optoelectronic properties when their dimensionality is reduced. Here, Saouma et al. study the enhancement of third-order nonlinearities in two-dimensional lead iodide perovskites in the Ruddlesden-Popper series.

  19. 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.

  20. Semitransparent Fully Air Processed Perovskite Solar Cells.

    PubMed

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

    2015-08-19

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

  1. Halide Perovskites for Tandem Solar Cells.

    PubMed

    Lee, Jin-Wook; Hsieh, Yao-Tsung; De Marco, Nicholas; Bae, Sang-Hoon; Han, Qifeng; Yang, Yang

    2017-05-04

    Perovskite solar cells have become one of the strongest candidates for next-generation solar energy technologies. A myriad of beneficial optoelectronic properties of the perovskite materials have enabled superb power conversion efficiencies (PCE) exceeding 22% for a single-junction device. The high PCE achievable via low processing costs and relatively high variability in optical properties have opened new possibilities for perovskites in tandem solar cells. In this Perspective, we will discuss current research trends in fabricating tandem perovskite-based solar cells in combination with a variety of mature photovoltaic devices such as organic, silicon, and Cu(In,Ga)(S,Se)2 (CIGS) solar cells. Characteristic features and present limitations of each tandem cell will be discussed and elaborated upon. Finally, key issues for further improvement and the future outlook will be discussed.

  2. Perovskite-Like Organic-Inorganic Hybrid Lead Iodide with a Large Organic Cation Incorporated within the Layers.

    PubMed

    Que, Chen-Jie; Mo, Chong-Jiao; Li, Zhao-Qi; Zhang, Guang-Lin; Zhu, Qin-Yu; Dai, Jie

    2017-03-06

    A great effort has been made to investigate 2D perovskites to improve the stability and controllability in the fabrication of photoelectronic devices. As far as we know, only small organic cations such as methylammonium can incorporate into the multilayered perovskite structure except the cations sandwiched between the inorganic layers. We report here a new layered lead iodide, (H2Aepz)3Pb4I14 (1), where larger organic cations, bis-protonated 2-(2-aminoethyl)pyrazole (Aepz), not only were sandwiched between the inorganic layers but also were incorporated within the perovskite-like PbI layered structure. Another 2D compound, (H2Aepz)PbI4 (2), was also prepared that was a one-layer perovskite. A simple Schottky device was prepared to investigate the photoelectroresponsive properties of the compounds in comparison with that of a typical organic-inorganic hybrid perovskite. In general, the energy gap is decreased with an increase in the perovskite layers, but the band gap of two-layered 1 is larger than that of one-layered 2. The photocurrent densities of the compounds are in the order of 1 < 2 < (CH3NH3)PbI3, which is discussed based on the crystal structures and band energy gaps.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  4. Inhibition of a structural phase transition in one-dimensional organometal halide perovskite nanorods grown inside porous silicon nanotube templates

    NASA Astrophysics Data System (ADS)

    Arad-Vosk, N.; Rozenfeld, N.; Gonzalez-Rodriguez, R.; Coffer, J. L.; Sa'ar, A.

    2017-02-01

    One-dimensional organo-metal halide perovskite (C H3N H3Pb I3 ) nanorods whose diameter and length are dictated by the inner size of porous silicon nanotube templates have been grown, characterized, and compared to bulk perovskites in the form of microwires. We have observed a structural phase transition for bulk perovskites, where the crystal structure changes from tetragonal to orthorhombic at about 160 K, as opposed to small diameter one-dimensional perovskite nanorods, of the order of 30-70 nm in diameter, where the phase transition is inhibited and the dominant phase remains tetragonal. Two major experimental techniques, infrared absorption spectroscopy and photoluminescence, were utilized to probe the temperature dependence of the perovskite phases over the 4-300 K temperature range. Yet, different characteristics of the phase transition were measured by the two spectroscopic methods and explained by the presence of small, tetragonal inclusions embedded in the orthorhombic phase. The inhibition of the phase transition is attributed to the large surface area of these one-dimensional perovskite nanorods, which gives rise to a large stress that, in turn, prevents the formation of the orthorhombic phase. The absence of phase transition enables the measurement of the tetragonal bandgap energy down to low temperatures.

  5. Perovskite solar cells: from materials to devices.

    PubMed

    Jung, Hyun Suk; Park, Nam-Gyu

    2015-01-07

    Perovskite solar cells based on organometal halide light absorbers have been considered a promising photovoltaic technology due to their superb power conversion efficiency (PCE) along with very low material costs. Since the first report on a long-term durable solid-state perovskite solar cell with a PCE of 9.7% in 2012, a PCE as high as 19.3% was demonstrated in 2014, and a certified PCE of 17.9% was shown in 2014. Such a high photovoltaic performance is attributed to optically high absorption characteristics and balanced charge transport properties with long diffusion lengths. Nevertheless, there are lots of puzzles to unravel the basis for such high photovoltaic performances. The working principle of perovskite solar cells has not been well established by far, which is the most important thing for understanding perovksite solar cells. In this review, basic fundamentals of perovskite materials including opto-electronic and dielectric properties are described to give a better understanding and insight into high-performing perovskite solar cells. In addition, various fabrication techniques and device structures are described toward the further improvement of perovskite solar cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Modeling hybrid perovskites by molecular dynamics.

    PubMed

    Mattoni, Alessandro; Filippetti, Alessio; Caddeo, Claudia

    2017-02-01

    The topical review describes the recent progress in the modeling of hybrid perovskites by molecular dynamics simulations. Hybrid perovskites and in particular methylammonium lead halide (MAPI) have a tremendous technological relevance representing the fastest-advancing solar material to date. They also represent the paradigm of an organic-inorganic crystalline material with some conceptual peculiarities: an inorganic semiconductor for what concerns the electronic and absorption properties with a hybrid and solution processable organic-inorganic body. After briefly explaining the basic concepts of ab initio and classical molecular dynamics, the model potential recently developed for hybrid perovskites is described together with its physical motivation as a simple ionic model able to reproduce the main dynamical properties of the material. Advantages and limits of the two strategies (either ab initio or classical) are discussed in comparison with the time and length scales (from pico to microsecond scale) necessary to comprehensively study the relevant properties of hybrid perovskites from molecular reorientations to electrocaloric effects. The state-of-the-art of the molecular dynamics modeling of hybrid perovskites is reviewed by focusing on a selection of showcase applications of methylammonium lead halide: molecular cations disorder; temperature evolution of vibrations; thermally activated defects diffusion; thermal transport. We finally discuss the perspectives in the modeling of hybrid perovskites by molecular dynamics.

  7. Modeling hybrid perovskites by molecular dynamics

    NASA Astrophysics Data System (ADS)

    Mattoni, Alessandro; Filippetti, Alessio; Caddeo, Claudia

    2017-02-01

    The topical review describes the recent progress in the modeling of hybrid perovskites by molecular dynamics simulations. Hybrid perovskites and in particular methylammonium lead halide (MAPI) have a tremendous technological relevance representing the fastest-advancing solar material to date. They also represent the paradigm of an organic-inorganic crystalline material with some conceptual peculiarities: an inorganic semiconductor for what concerns the electronic and absorption properties with a hybrid and solution processable organic-inorganic body. After briefly explaining the basic concepts of ab initio and classical molecular dynamics, the model potential recently developed for hybrid perovskites is described together with its physical motivation as a simple ionic model able to reproduce the main dynamical properties of the material. Advantages and limits of the two strategies (either ab initio or classical) are discussed in comparison with the time and length scales (from pico to microsecond scale) necessary to comprehensively study the relevant properties of hybrid perovskites from molecular reorientations to electrocaloric effects. The state-of-the-art of the molecular dynamics modeling of hybrid perovskites is reviewed by focusing on a selection of showcase applications of methylammonium lead halide: molecular cations disorder; temperature evolution of vibrations; thermally activated defects diffusion; thermal transport. We finally discuss the perspectives in the modeling of hybrid perovskites by molecular dynamics.

  8. Modeling Anomalous Hysteresis in Perovskite Solar Cells.

    PubMed

    van Reenen, Stephan; Kemerink, Martijn; Snaith, Henry J

    2015-10-01

    Organic-inorganic lead halide perovskites are distinct from most other semiconductors because they exhibit characteristics of both electronic and ionic motion. Accurate understanding of the optoelectronic impact of such properties is important to fully optimize devices and be aware of any limitations of perovskite solar cells and broader optoelectronic devices. Here we use a numerical drift-diffusion model to describe device operation of perovskite solar cells. To achieve hysteresis in the modeled current-voltage characteristics, we must include both ion migration and electronic charge traps, serving as recombination centers. Trapped electronic charges recombine with oppositely charged free electronic carriers, of which the density depends on the bias-dependent ion distribution in the perovskite. Our results therefore show that reduction of either the density of mobile ionic species or carrier trapping at the perovskite interface will remove the adverse hysteresis in perovskite solar cells. This gives a clear target for ongoing research effort and unifies previously conflicting experimental observations and theories.

  9. Ambipolar solution-processed hybrid perovskite phototransistors

    PubMed Central

    Li, Feng; Ma, Chun; Wang, Hong; Hu, Weijin; Yu, Weili; Sheikh, Arif D.; Wu, Tom

    2015-01-01

    Organolead halide perovskites have attracted substantial attention because of their excellent physical properties, which enable them to serve as the active material in emerging hybrid solid-state solar cells. Here we investigate the phototransistors based on hybrid perovskite films and provide direct evidence for their superior carrier transport property with ambipolar characteristics. The field-effect mobilities for triiodide perovskites at room temperature are measured as 0.18 (0.17) cm2 V−1 s−1 for holes (electrons), which increase to 1.24 (1.01) cm2 V−1 s−1 for mixed-halide perovskites. The photoresponsivity of our hybrid perovskite devices reaches 320 A W−1, which is among the largest values reported for phototransistors. Importantly, the phototransistors exhibit an ultrafast photoresponse speed of less than 10 μs. The solution-based process and excellent device performance strongly underscore hybrid perovskites as promising material candidates for photoelectronic applications. PMID:26345730

  10. Perovskite Solar Cells: Beyond Methylammonium Lead Iodide.

    PubMed

    Boix, Pablo P; Agarwala, Shweta; Koh, Teck Ming; Mathews, Nripan; Mhaisalkar, Subodh G

    2015-03-05

    Organic-inorganic lead halide based perovskites solar cells are by far the highest efficiency solution-processed solar cells, threatening to challenge thin film and polycrystalline silicon ones. Despite the intense research in this area, concerns surrounding the long-term stability as well as the toxicity of lead in the archetypal perovskite, CH3NH3PbI3, have the potential to derail commercialization. Although the search for Pb-free perovskites have naturally shifted to other transition metal cations and formulations that replace the organic moiety, efficiencies with these substitutions are still substantially lower than those of the Pb-perovskite. The perovskite family offers rich multitudes of crystal structures and substituents with the potential to uncover new and exciting photophysical phenomena that hold the promise of higher solar cell efficiencies. In addressing materials beyond CH3NH3PbI3, this Perspective will discuss a broad palette of elemental substitutions, solid solutions, and multidimensional families that will provide the next fillip toward market viability of the perovskite solar cells.

  11. Perovskite-based photodetectors: materials and devices.

    PubMed

    Wang, Huan; Kim, Dong Ha

    2017-08-29

    While the field of perovskite-based optoelectronics has mostly been dominated by photovoltaics, light-emitting diodes, and transistors, semiconducting properties peculiar to perovskites make them interesting candidates for innovative and disruptive applications in light signal detection. Perovskites combine effective light absorption in the broadband range with good photo-generation yield and high charge carrier mobility, a combination that provides promising potential for exploiting sensitive and fast photodetectors that are targeted for image sensing, optical communication, environmental monitoring or chemical/biological detection. Currently, organic-inorganic hybrid and all-inorganic halide perovskites with controlled morphologies of polycrystalline thin films, nano-particles/wires/sheets, and bulk single crystals have shown key figure-of-merit features in terms of their responsivity, detectivity, noise equivalent power, linear dynamic range, and response speed. The sensing region has been covered from ultraviolet-visible-near infrared (UV-Vis-NIR) to gamma photons based on two- or three-terminal device architectures. Diverse photoactive materials and devices with superior optoelectronic performances have stimulated attention from researchers in multidisciplinary areas. In this review, we provide a comprehensive overview of the recent progress of perovskite-based photodetectors focusing on versatile compositions, structures, and morphologies of constituent materials, and diverse device architectures toward the superior performance metrics. Combining the advantages of both organic semiconductors (facile solution processability) and inorganic semiconductors (high charge carrier mobility), perovskites are expected to replace commercial silicon for future photodetection applications.

  12. Strategic improvement of the long-term stability of perovskite materials and perovskite solar cells.

    PubMed

    Xu, Tingting; Chen, Lixin; Guo, Zhanhu; Ma, Tingli

    2016-10-05

    Perovskite solar cells (PSCs) have gained tremendous research interest in recent several years. To date the power conversion efficiency (PCE) of PSCs has been increased from 3.8% to over 22.1%, showing that they have a promising future as a renewable energy resource to compete with conventional silicon solar cells. However, a crucial challenge of PSCs currently is that perovskite materials and PSCs have limitations of easy degradation and inferior long-term stabilities, thus hampering their future commercial applications. In this review, the degradation mechanisms for instable perovskite materials and their corresponding solar cells are discussed. The stability study of perovskite materials and PSCs from the aspect of experimental tests and theoretical calculations is reviewed. The strategies for enhancing the stability of perovskite materials and PSCs are summarized from the viewpoints of perovskite material engineering, substituted organic and inorganic materials for hole transportation, alternative electrodes comprising mainly carbon and its relevant composites, interfacial modification, novel device structure construction and encapsulation, etc. Various approaches and outlooks on the future direction of perovskite materials and PSCs are highlighted. This review is expected to provide helpful insights for further enhancing the stability of perovskite materials and PSCs in this exciting field.

  13. Hybrid Perovskite Light-Emitting Diodes Based on Perovskite Nanocrystals with Organic-Inorganic Mixed Cations.

    PubMed

    Zhang, Xiaoli; Liu, He; Wang, Weigao; Zhang, Jinbao; Xu, Bing; Karen, Ke Lin; Zheng, Yuanjin; Liu, Sheng; Chen, Shuming; Wang, Kai; Sun, Xiao Wei

    2017-03-07

    Organic-inorganic hybrid perovskite materials with mixed cations have demonstrated tremendous advances in photovoltaics recently, by showing a significant enhancement of power conversion efficiency and improved perovskite stability. Inspired by this development, this study presents the facile synthesis of mixed-cation perovskite nanocrystals based on FA(1-x) Csx PbBr3 (FA = CH(NH2 )2 ). By detailed characterization of their morphological, optical, and physicochemical properties, it is found that the emission property of the perovskite, FA(1-x) Csx PbBr3 , is significantly dependent on the substitution content of the Cs cations in the perovskite composition. These mixed-cation perovskites are employed as light emitters in light-emitting diodes (LEDs). With an optimized composition of FA0.8 Cs0.2 PbBr3 , the LEDs exhibit encouraging performance with a highest reported luminance of 55 005 cd m(-2) and a current efficiency of 10.09 cd A(-1) . This work provides important instructions on the future compositional optimization of mixed-cation perovskite for obtaining high-performance LEDs. The authors believe this work is a new milestone in the development of bright and efficient perovskite LEDs.

  14. Constructing Efficient and Stable Perovskite Solar Cells via Interconnecting Perovskite Grains.

    PubMed

    Hou, Xian; Huang, Sumei; Ou-Yang, Wei; Pan, Likun; Sun, Zhuo; Chen, Xiaohong

    2017-09-29

    A high-quality perovskite film with interconnected perovskite grains was obtained by incorporating terephthalic acid (TPA) additive into the perovskite precursor solution. The presence of TPA changed the crystallization kinetics of the perovskite film and promoted lateral growth of grains in the vicinity of crystal boundaries. As a result, sheet-shaped perovskite was formed and covered onto the bottom grains, which made some adjacent grains partly merge together to form grains-interconnected perovskite film. Perovskite solar cells (PSCs) with TPA additive exhibited a power conversion efficiency (PCE) of 18.51% with less hysteresis, which is obviously higher than that of pristine cells (15.53%). PSCs without and with TPA additive retain 18 and 51% of the initial PCE value, respectively, aging for 35 days exposed to relative humidity 30% in air without encapsulation. Furthermore, MAPbI3 film with TPA additive shows superior thermal stability to the pristine one under 100 °C baking. The results indicate that the presence of TPA in perovskite film can greatly improve the performance of PSCs as well as their moisture resistance and thermal stability.

  15. Molecular dynamics simulations of organohalide perovskite precursors: solvent effects in the formation of perovskite solar cells.

    PubMed

    Gutierrez-Sevillano, Juan José; Ahmad, Shahzada; Calero, Sofía; Anta, Juan A

    2015-09-21

    The stability and desirable crystal formation of organohalide perovskite semiconductors is of utmost relevance to ensure the success of perovskites in photovoltaic technology. Herein we have simulated the dynamics of ionic precursors toward the formation of embryonic organohalide perovskite CH3NH3PbI3 units in the presence of solvent molecules using Molecular Dynamics. The calculations involved, a variable amount of Pb(2+), I(-), and CH3NH3(+) ionic precursors in water, pentane and a mixture of these two solvents. Suitable force fields for solvents and precursors have been tested and used to carry out the simulations. Radial distribution functions and mean square displacements confirm the formation of basic perovskite crystalline units in pure pentane - taken as a simple and archetypal organic solvent. In contrast, simulations in water confirm the stability of the solvated ionic precursors, which prevents their aggregation to form the perovskite compound. We have found that in the case of a water/pentane binary solvent, a relatively small amount of water did not hinder the perovskite formation. Thus, our findings suggest that the cause of the poor stability of perovskite films in the presence of moisture is a chemical reaction, rather than the polar nature of the solvents. Based on the results, a set of force-field parameters to study from first principles perovskite formation and stability, also in the solid phase, is proposed.

  16. Domain-dependent electronic structure and optical absorption property in hybrid organic-inorganic perovskite.

    PubMed

    Meng, Xiang; Zhang, Ruifeng; Fu, Zhongheng; Zhang, Qianfan

    2016-10-05

    Hybrid organic-inorganic perovskites, represented by materials in the CH3NH3PbI3 series, have become one of the most promising materials for solar cells with a high power conversion efficiency and low cost. The ordered Pb-I cage in such hybrid perovskites can induce the polarized cations to form a variety of polarization domains with long-range order, which will lead to the formation of specific atomic conformations or metastable crystalline phases, unique electronic band structures and optical absorption properties. Such domain-dependent characteristics play a critical role in the phase transition and service stability of such solar cells, and also open up the opportunity of tuning their electronic structure. In the present study, we systematically investigate the band structures and optical absorption properties of different electronically ordered domains in CH3NH3PbI3. By comparing different perovskites containing various cations, we have clarified the important influence of cation polarization on domain-dependent properties. Our results provide not only a possible pathway for the manipulation of band structure by applying an external field, but also a novel scheme for improving the performance and stability of hybrid perovskites.

  17. Structural chemistry and magnetic properties of the perovskite Sr3Fe2TeO9

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    A polycrystalline sample of perovskite-like Sr3Fe2TeO9 has been prepared in a solid-state reaction and studied by a combination of electron microscopy, Mössbauer spectroscopy, magnetometry, X-ray diffraction and neutron diffraction. The majority of the reaction product is shown to be a trigonal phase with a 2:1 ordered arrangement of Fe3+ and Te6+ cations. However, the sample is prone to nano-twinning and tetragonal domains with a different pattern of cation ordering exist within many crystallites. Antiferromagnetic ordering exists in the trigonal phase at 300 K and Sr3Fe2TeO9 is thus the first example of a perovskite with 2:1 trigonal cation ordering to show long-range magnetic order. At 300 K the antiferromagnetic phase coexists with two paramagnetic phases which show spin-glass behaviour below ~80 K.

  18. Phase stability study of Bi{sub 0.15}Sr{sub 0.85-x}Ae{sub x}CoO{sub 3-{delta}} (x = 0 and Ae = Ba{sub 0.28}; Ca{sub 0.17}) perovskites by in-situ neutron diffraction

    SciTech Connect

    Eriksson, A.K.; Eriksson, S.G.; Chapon, L.C.; Knee, C.S.

    2010-12-15

    The oxygen deficient perovskites, Bi{sub 0.15}Sr{sub 0.85-x}Ae{sub x}CoO{sub 3-{delta}}, x = 0 and Ae{sub x} = Ba{sub 0.28}, Ca{sub 0.17}, were studied with in-situ neutron powder diffraction and combined TGA/DSC in order to investigate their behaviour at elevated temperatures in oxidising conditions. The phase stability of the I4/mmm supercell structure adopted by Bi{sub 0.15}Sr{sub 0.85}CoO{sub 3-{delta}} is shown to be dependent on temperature and the oxygen content of the phase, with three structural events, at T {approx} 250, 590 and 880 {sup o}C, detected. The first transition occurs as the perovskite supercell vanishes due to oxygen absorption; the second transition is also associated with oxidation and involves the decomposition of the perovskite phase via an exothermic process to yield a dominant hexagonal phase. Finally, at T {approx} 900 {sup o}C the perovskite phase re-forms. For the Ba and Ca containing materials the decomposition to the hexagonal phase occurs at T {approx} 600 {sup o}C and {approx} 650 {sup o}C respectively. The presence of Ca at the A-site is found to stabilise the I4/mmm supercell structure in the range RT - 650 {sup o}C. The antiferromagnetic to paramagnetic transitions occur at T{sub N} {approx} 250 {sup o}C, T{sub N} {approx} 175 {sup o}C and T{sub N} {approx} 145 {sup o}C for the samples with Ae{sub x} = Ba{sub 0.28}, x = 0 and Ae{sub x} = Ca{sub 0.17}, respectively.

  19. Multiferroicity in Perovskite Manganite Superlattice

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  20. Electrochemical Doping of Halide Perovskites with Ion Intercalation.

    PubMed

    Jiang, Qinglong; Chen, Mingming; Li, Junqiang; Wang, Mingchao; Zeng, Xiaoqiao; Besara, Tiglet; Lu, Jun; Xin, Yan; Shan, Xin; Pan, Bicai; Wang, Changchun; Lin, Shangchao; Siegrist, Theo; Xiao, Qiangfeng; Yu, Zhibin

    2017-01-24

    Halide perovskites have recently been investigated for various solution-processed optoelectronic devices. The majority of studies have focused on using intrinsic halide perovskites, and the intentional incoporation of dopants has not been well explored. In this work, we discovered that small alkali ions, including lithium and sodium ions, could be electrochemically intercalated into a variety of halide and pseudohalide perovskites. The ion intercalation caused a lattice expansion of the perovskite crystals and resulted in an n-type doping of the perovskites. Such electrochemical doping improved the conductivity and changed the color of the perovskites, leading to an electrochromism with more than 40% reduction of transmittance in the 450-850 nm wavelength range. The doped perovskites exhibited improved electron injection efficiency into the pristine perovskite crystals, resulting in bright light-emitting diodes with a low turn-on voltage.

  1. Effect of tolerance factor and local distortion on magnetic properties of the perovskite manganites

    NASA Astrophysics Data System (ADS)

    Zhou, J. P.; McDevitt, J. T.; Zhou, J. S.; Yin, H. Q.; Goodenough, J. B.; Gim, Y.; Jia, Q. X.

    1999-08-01

    The substitutions of rare earths for La on the magnetic properties of the perovskites La0.7-xRxA0.3MnO3 (0A-site ionic radii rA of the AMnO3 perovskites proved detrimental. The optimal composition has been discussed for the half-metallic ferromagnet of a spin-switch device based on the manganese oxides.

  2. Highly Efficient Perovskite-Perovskite Tandem Solar Cells Reaching 80% of the Theoretical Limit in Photovoltage.

    PubMed

    Rajagopal, Adharsh; Yang, Zhibin; Jo, Sae Byeok; Braly, Ian L; Liang, Po-Wei; Hillhouse, Hugh W; Jen, Alex K-Y

    2017-09-01

    Organic-inorganic hybrid perovskite multijunction solar cells have immense potential to realize power conversion efficiencies (PCEs) beyond the Shockley-Queisser limit of single-junction solar cells; however, they are limited by large nonideal photovoltage loss (V oc,loss ) in small- and large-bandgap subcells. Here, an integrated approach is utilized to improve the V oc of subcells with optimized bandgaps and fabricate perovskite-perovskite tandem solar cells with small V oc,loss . A fullerene variant, Indene-C60 bis-adduct, is used to achieve optimized interfacial contact in a small-bandgap (≈1.2 eV) subcell, which facilitates higher quasi-Fermi level splitting, reduces nonradiative recombination, alleviates hysteresis instabilities, and improves V oc to 0.84 V. Compositional engineering of large-bandgap (≈1.8 eV) perovskite is employed to realize a subcell with a transparent top electrode and photostabilized V oc of 1.22 V. The resultant monolithic perovskite-perovskite tandem solar cell shows a high V oc of 1.98 V (approaching 80% of the theoretical limit) and a stabilized PCE of 18.5%. The significantly minimized nonideal V oc,loss is better than state-of-the-art silicon-perovskite tandem solar cells, which highlights the prospects of using perovskite-perovskite tandems for solar-energy generation. It also unlocks opportunities for solar water splitting using hybrid perovskites with solar-to-hydrogen efficiencies beyond 15%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Making and Breaking of Lead Halide Perovskites.

    PubMed

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

    2016-02-16

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

  4. “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.

  5. Stabilisation of Fe2O3-rich Perovskite Nanophase in Epitaxial Rare-earth Doped BiFeO3 Films

    PubMed Central

    Zhang, Huairuo; Reaney, Ian M.; Marincel, Daniel M.; Trolier-McKinstry, Susan; Ramasse, Quentin M.; MacLaren, Ian; Findlay, Scott D.; Fraleigh, Robert D.; Ross, Ian M.; Hu, Shunbo; Ren, Wei; Mark Rainforth, W.

    2015-01-01

    Researchers have demonstrated that BiFeO3 exhibits ferroelectric hysteresis but none have shown a strong ferromagnetic response in either bulk or thin film without significant structural or compositional modification. When remanent magnetisations are observed in BiFeO3 based thin films, iron oxide second phases are often detected. Using aberration-corrected scanning transmission electron microscopy, atomic resolution electron energy loss spectrum-mapping and quantitative energy dispersive X-ray spectroscopy analysis, we reveal the existence of a new Fe2O3-rich perovskite nanophase, with an approximate formula (Fe0.6Bi0.25Nd0.15)3+ Fe3+O3, formed within epitaxial Ti and Nd doped BiFeO3 perovskite films grown by pulsed laser deposition. The incorporation of Nd and Bi ions on the A-site and coherent growth with the matrix stabilise the Fe2O3-rich perovskite phase and preliminary density functional theory calculations suggest that it should have a ferrimagnetic response. Perovskite-structured Fe2O3 has been reported previously but never conclusively proven when fabricated at high-pressure high-temperature. This work suggests the incorporation of large A-site species may help stabilise perovskite-structured Fe2O3. This finding is therefore significant not only to the thin film but also to the high-pressure community. PMID:26272264

  6. Stabilisation of Fe2O3-rich Perovskite Nanophase in Epitaxial Rare-earth Doped BiFeO3 Films.

    PubMed

    Zhang, Huairuo; Reaney, Ian M; Marincel, Daniel M; Trolier-McKinstry, Susan; Ramasse, Quentin M; MacLaren, Ian; Findlay, Scott D; Fraleigh, Robert D; Ross, Ian M; Hu, Shunbo; Ren, Wei; Rainforth, W Mark

    2015-08-14

    Researchers have demonstrated that BiFeO3 exhibits ferroelectric hysteresis but none have shown a strong ferromagnetic response in either bulk or thin film without significant structural or compositional modification. When remanent magnetisations are observed in BiFeO3 based thin films, iron oxide second phases are often detected. Using aberration-corrected scanning transmission electron microscopy, atomic resolution electron energy loss spectrum-mapping and quantitative energy dispersive X-ray spectroscopy analysis, we reveal the existence of a new Fe2O3-rich perovskite nanophase, with an approximate formula (Fe0.6Bi0.25Nd0.15)(3+) Fe(3+)O3, formed within epitaxial Ti and Nd doped BiFeO3 perovskite films grown by pulsed laser deposition. The incorporation of Nd and Bi ions on the A-site and coherent growth with the matrix stabilise the Fe2O3-rich perovskite phase and preliminary density functional theory calculations suggest that it should have a ferrimagnetic response. Perovskite-structured Fe2O3 has been reported previously but never conclusively proven when fabricated at high-pressure high-temperature. This work suggests the incorporation of large A-site species may help stabilise perovskite-structured Fe2O3. This finding is therefore significant not only to the thin film but also to the high-pressure community.

  7. Patterning of perovskite-polymer films by wrinkling instabilities.

    PubMed

    Nasti, G; Sanchez, S; Gunkel, I; Balog, S; Roose, B; Wilts, B D; Teuscher, J; Gentile, G; Cerruti, P; Ambrogi, V; Carfagna, C; Steiner, U; Abate, A

    2017-02-22

    Organic-inorganic perovskites are semiconductors used for applications in optoelectronics and photovoltaics. Micron and submicron perovskite patterns have been explored in semitransparent photovoltaic and lasing applications. In this work, we show that a polymeric medium can be used to create a patterned perovskite, by using a novel and inexpensive approach.

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

    PubMed

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

    2016-09-01

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

  9. Electrochemical studies of perovskite mixed conductors

    SciTech Connect

    Brosha, E.L.; Chung, B.W.; Garzon, F.H.

    1994-12-01

    Research into the growth of high-quality single crystal thin films of high transition temperature {Tc} superconductors have stimulated interest in other perovskite metal oxides with a variety of physical properties. Thin films of perovskite materials are among the major focal research areas for optical, sensor, electronic, and superconducting applications. Two lanthanum-based oxygen/electronic conducting perovskite oxides of particular interest for high temperature fuel cell electrodes and interconnects and for other electrochemical applications such as oxygen separation devices are La{sub 1{minus}x}Sr{sub x}MnO{sub 3{minus}y} and La{sub 1{minus}x}Sr{sub x}CoO{sub 3{minus}y}. The La-based perovskites are valuable for these technologies because they reduce interfacial resistances by eliminating the need for a three phase contact area (gas, metal electrode, electrolyte). In addition, these oxides may also serve a valuable role as novel catalysts or catalytic supports; however, little is known about what catalytic properties they may possess. Fundamental study of the electrochemical, diffusional oxygen transport, and surface catalytic properties of these materials can be greatly simplified if the complications associated with the presence of grain boundaries and multiple crystallite orientations can be avoided. Therefore, single crystals of these La-based perovskites become highly desirable. In this work, the authors report the structural and electrical properties of highly oriented thin films of La{sub 0.84}Sr{sub 0.16}MnO{sub 3} and La{sub 0.8}Sr{sub 0.2}CoO{sub 3} grown on single crystal Y-ZrO{sub 2} substrates. An addition, the authors have demonstrated growing, in situ, epitaxial multilayer perovskite/fluorite/perovskite configurations for fundamental fuel cell modeling.

  10. Electrically insulating properties of the 5d double perovskite Sr2YOsO6

    NASA Astrophysics Data System (ADS)

    Li, Jinghua; Wang, Xia; Wang, Hongyuan; Matsushita, Yoshitaka; Alexei, Belik A.; Kolodiazhnyi, Taras; Xu, Gang; Shi, Youguo; Guo, Yanfeng; Yamaura, Kazunari; Chen, Ying

    2017-09-01

    A high-pressure-synthesized double perovskite Sr2YOsO6 was investigated by synchrotron X-ray diffraction and measurements of its magnetic susceptibility, specific heat capacity, complex impedance, and complex dielectric constant. It crystallized into a monoclinic double perovskite structure (P21/n) with complete ordering of the Y and Os atoms. Its magnetic behaviors, including the antiferromagnetic transition temperature (˜52 K), Curie-Weiss effective moment [3.48(5) μB/Os], and Weiss temperature [-350.1(7) K], were close to the respective values of Sr2YOsO6 previously synthesized without an applied pressure of 6 GPa. Transport property measurements revealed that the lower limit of the activation energy was 192(1) meV and the charge gap remained open regardless of the presence of magnetic order, conflicting with the electron delocalization predicted by theoretical calculations. Further consideration, including theoretical and experimental investigations of the roles of spin-orbit coupling and U of the 5d electrons of Os 5d-t2g3, may assist in understanding the general magnetic and insulating behaviors of quasi-half-filled 5d-t2g3oxides in the perovskite category toward the use of 5d double perovskite for magnetic applications.

  11. Enhancing the grain size of organic halide perovskites by sulfonate-carbon nanotube incorporation in high performance perovskite solar cells.

    PubMed

    Zhang, Yong; Tan, Licheng; Fu, Qingxia; Chen, Lie; Ji, Ting; Hu, Xiaotian; Chen, Yiwang

    2016-04-28

    The grain size of perovskites was enhanced and the grain boundary was filled with sulfonate carbon nanotubes (s-CNTs) during the CH3NH3PbI3 perovskite precursor solution spin-coating process with the incorporation of s-CNTs. The performance of s-CNT incorporated perovskite solar cells remarkably increased from 10.3% to 15.1% (best) compared with pristine CNT incorporated perovskite solar cells.

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

    PubMed

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

    2016-02-01

    The synthesis of previously unknown perovskite (CH3 NH3 )2 PdCl4 is reported. Despite using an organic cation with the smallest possible alkyl group, a 2D organic-inorganic layered Pd-based perovskites was still formed. This demonstrates that Pd-based 2D perovskites can be obtained even if the size of the organic cation is below the size limit predicted by the Goldschmidt tolerance-factor formula. The (CH3 NH3 )2 PdCl4 phase has a bulk resistivity of 1.4 Ω cm, a direct optical gap of 2.22 eV, and an absorption coefficient on the order of 10(4)  cm(-1) . XRD measurements suggest that the compound is moderately stable in air, an important advantage over several existing organic-inorganic perovskites that are prone to phase degradation problems when exposed to the atmosphere. Given the recent interest in organic-inorganic perovskites, the synthesis of this new Pd-based organic-inorganic perovskite may be helpful in the preparation and understanding of other organic-inorganic perovskites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Size-dependent one-photon- and two-photon-pumped amplified spontaneous emission from organometal halide CH3NH3PbBr3 perovskite cubic microcrystals.

    PubMed

    Zhang, Zhen-Yu; Wang, Hai-Yu; Zhang, Yan-Xia; Li, Kai-Jiao; Zhan, Xue-Peng; Gao, Bing-Rong; Chen, Qi-Dai; Sun, Hong-Bo

    2017-01-18

    In the past few years, organometal halide light-emitting perovskite thin films and colloidal nanocrystals (NCs) have attracted significant research interest in the field of highly purified illuminating applications. However, knowledge of photoluminescence (PL) characteristics, such as amplified spontaneous emission (ASE) of larger-sized perovskite crystals, is still relatively scarce. Here, we presented room-temperature size-dependent spontaneous emission (SE) and ASE of the organometal halide CH3NH3PbBr3 perovskite cubic microcrystals pumped through one-photon-(1P) and two-photon-(2P) excitation paradigms. The results showed that the optical properties of SE and ASE were sensitively dependent on the sizes of perovskite microcrystals irrespective of whether 1P or 2P excitation was used. Moreover, by comparing the spectral results of 1P- and 2P-pumped experiments, 2P pumping was found to be an effective paradigm to reduce thresholds by one order of magnitude. Finally, we carried out fluences-dependent time-resolved fluorescence dynamics experiments to study the underlying effects of these scale-dependent SE and ASE. We found that the photoluminescence (PL) recombination rates sensitively became faster with increasing carriers' densities, and that the ASE pumped from larger-sized CH3NH3PbBr3 perovskite cubic microcrystals showed faster lifetimes. This work shows that micro-sized perovskite cubic crystals could be the ideal patterns of perovskite materials for realizing ASE applications in the future.

  14. 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

  15. Nanoimprinted Perovskite Nanograting Photodetector with Improved Efficiency.

    PubMed

    Wang, Honglei; Haroldson, Ross; Balachandran, Balasubramaniam; Zakhidov, Alex; Sohal, Sandeep; Chan, Julia Y; Zakhidov, Anvar; Hu, Walter

    2016-12-27

    Recently, organolead halide-based perovskites have emerged as promising materials for optoelectronic applications, particularly for photovoltaics, photodetectors, and lasing, with low cost and high performance. Meanwhile, nanoscale photodetectors have attracted tremendous attention toward realizing miniaturized optoelectronic systems, as they offer high sensitivity, ultrafast response, and the capability to detect beyond the diffraction limit. Here we report high-performance nanoscale-patterned perovskite photodetectors implemented by nanoimprint lithography (NIL). The spin-coated lead methylammonium triiodide perovskite shows improved crystallinity and optical properties after NIL. The nanoimprinted metal-semiconductor-metal photodetectors demonstrate significantly improved performance compared to the nonimprinted conventional thin-film devices. The effects of NIL pattern geometries on the optoelectronic characteristics were studied, and the nanograting pattern based photodetectors demonstrated the best performance, showing approximately 35 times improvement on responsivity and 7 times improvement on on/off ratio compared with the nonimprinted devices. The high performance of NIL-nanograting photodetectors likely results from high crystallinity and favored nanostructure morphology, which contribute to higher mobility, longer diffusion length, and better photon absorption. Our results have demonstrated that the NIL is a cost-effective method to fabricate high-performance perovskite nanoscale optoelectronic devices, which may be suitable for manufacturing of high-density perovskite nanophotodetector arrays and to provide integration with state-of-the-art electronic circuits.

  16. Quantum-dot-in-perovskite solids.

    PubMed

    Ning, Zhijun; Gong, Xiwen; Comin, Riccardo; Walters, Grant; Fan, Fengjia; Voznyy, Oleksandr; Yassitepe, Emre; Buin, Andrei; Hoogland, Sjoerd; Sargent, Edward H

    2015-07-16

    Heteroepitaxy-atomically aligned growth of a crystalline film atop a different crystalline substrate-is the basis of electrically driven lasers, multijunction solar cells, and blue-light-emitting diodes. Crystalline coherence is preserved even when atomic identity is modulated, a fact that is the critical enabler of quantum wells, wires, and dots. The interfacial quality achieved as a result of heteroepitaxial growth allows new combinations of materials with complementary properties, which enables the design and realization of functionalities that are not available in the single-phase constituents. Here we show that organohalide perovskites and preformed colloidal quantum dots, combined in the solution phase, produce epitaxially aligned 'dots-in-a-matrix' crystals. Using transmission electron microscopy and electron diffraction, we reveal heterocrystals as large as about 60 nanometres and containing at least 20 mutually aligned dots that inherit the crystalline orientation of the perovskite matrix. The heterocrystals exhibit remarkable optoelectronic properties that are traceable to their atom-scale crystalline coherence: photoelectrons and holes generated in the larger-bandgap perovskites are transferred with 80% efficiency to become excitons in the quantum dot nanocrystals, which exploit the excellent photocarrier diffusion of perovskites to produce bright-light emission from infrared-bandgap quantum-tuned materials. By combining the electrical transport properties of the perovskite matrix with the high radiative efficiency of the quantum dots, we engineer a new platform to advance solution-processed infrared optoelectronics.

  17. Epitaxial Halide Perovskite Lateral Double Heterostructure.

    PubMed

    Wang, Yiping; Chen, Zhizhong; Deschler, Felix; Sun, Xin; Lu, Toh-Ming; Wertz, Esther A; Hu, Jia-Mian; Shi, Jian

    2017-03-28

    Epitaxial III-V semiconductor heterostructures are key components in modern microelectronics, electro-optics, and optoelectronics. With superior semiconducting properties, halide perovskite materials are rising as promising candidates for coherent heterostructure devices. In this report, spinodal decomposition is proposed and experimentally implemented to produce epitaxial double heterostructures in halide perovskite system. Pristine epitaxial mixed halide perovskites rods and films were synthesized via van der Waals epitaxy by chemical vapor deposition method. At room temperature, photon was applied as a knob to regulate the kinetics of spinodal decomposition and classic coarsening. By this approach, halide perovskite double heterostructures were created carrying epitaxial interfaces and outstanding optical properties. Reduced Fröhlich electron-phonon coupling was discovered in coherent halide double heterostructure, which is hypothetically attributed to the classic phonon confinement effect widely existing in III-V double heterostructures. As a proof-of-concept, our results suggest that halide perovskite-based epitaxial heterostructures may be promising for high-performance and low-cost optoelectronics, electro-optics, and microelectronics. Thus, ultimately, for practical device applications, it may be worthy to pursue these heterostructures via conventional vapor phase epitaxy approaches widely practised in III-V field.

  18. The Ca element effect on the enhancement performance of Sr2Fe1.5Mo0.5O6-δ perovskite as cathode for intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Qiao, Jinshuo; Chen, Wenjun; Wang, Wenyi; Wang, Zhenhua; Sun, Wang; Zhang, Jing; Sun, Kening

    2016-11-01

    In this paper, the partial substitution of atomic elements from the A site of a perovskite is investigated in order to develop cathode materials for solid oxide fuel cell (SOFC) applications. Herein, Sr2-xCaxFe1.5Mo0.5O6-δ (SCFM), compounds were investigated by characterizing structural properties, chemical compatibility, electrical properties, electrochemical performance and stability. Thermal expansion coefficients were found to decrease when increasing the Ca content. X-ray photoelectron spectroscopy analysis suggests that Ca doping significantly affects the Fe2+/Fe3+ and Mo6+/Mo5+ ratios. For a doping level of x = 0.4, the sample showed the lowest interface polarization (Rp), the highest conductivity and a maximum power density of 1.26 W cm-2 at 800 °C. These results suggest that SCFM cathode materials are excellent candidates for intermediate temperature solid oxide fuel cells applications.

  19. Crystallographic site swapping of La3+ ion in BaA'LaTeO6 (A' = Na, K, Rb) double perovskite type compounds: diffraction and photoluminescence evidence for the site swapping.

    PubMed

    Phatak, R; Gupta, S K; Krishnan, K; Sali, S K; Godbole, S V; Das, A

    2014-02-28

    Double perovskite type compounds of the formula BaA'LaTeO6 (A' = Na, K, Rb) were synthesized by solid state route and their crystal structures were determined by Rietveld analysis using powder X-ray diffraction and neutron diffraction data. Na compound crystallizes in the monoclinic system with P2₁/n space group whereas, K and Rb compounds crystallize in Fm3m space group. All the three compounds show rock salt type ordering at B site. Crystal structure analysis shows that La ion occupies A site in Na compound whereas, it occupies B site in K and Rb compounds according to the general formula of AA'BB'O6 for a double perovskite type compound. Effect of this crystallographic site swapping of the La ion was also observed in the photoluminescence study by doping Eu(3+) in La(3+) site. The large decrease in the intensity of the electric dipole ((5)D0-(7)F2) transition in the Rb compound compared to the Na compound indicates that Eu(3+) ion resides in the centrosymmetric octahedral environment in the Rb compound.

  20. Engineered spatial inversion symmetry breaking in an oxide hetero-structure built from isosymmetric room temperature magnetically ordered components

    NASA Astrophysics Data System (ADS)

    Claridge, John; Alaria, Jonathan; Dyer, Matthew; Rosseinsky, Matthew; Borisov, Pavel; Manning, Troy; Lepadatu, Serban; Cain, Markys; Mishina, Elena; Sherstyuck, Natalia; Ilyin, N. A.; Hadermann, Joke; Lederman, David

    2014-03-01

    The oxide heterostructure [(YFeO3)5(LaFeO3)5]40,which is magnetically ordered and piezoelectric at room temperature, has been constructed from two weak ferromagnetic AFeO3 perovskites with different A cations using RHEED-monitored pulsed laser deposition. The polarisation arises by combining ordering on the A site, imposed by the periodicity of the grown structure, with appropriate orientations of the octahedral tilting, according to simple symmetry-controlled rules. Magnetization and MOKE measurements show that the heterostructure's magnetic structure is similar to that of the individual components. Evidence of the polarity was obtained from second harmonic generation and piezoelectric force microscopy measurements. Modeling of the piezoresponse allows extraction of d33 (approximately 10 pC/N) of the heterostructure, which is in agreement with DFT calculations.

  1. Dissolution-recrystallization method for high efficiency perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Han, Fei; Luo, Junsheng; Wan, Zhongquan; Liu, Xingzhao; Jia, Chunyang

    2017-06-01

    In this work, a dissolution-recrystallization method (DRM) with chlorobenzene and dimethylsulfoxide treating the perovskite films during the spin-coating process is reported. This is the first time that DRM is used to control perovskite crystallization and improve the device performance. Furthermore, the DRM is good for reducing defects and grain boundaries, improving perovskite crystallization and even improving TiO2/perovskite interface. By optimizing, the DRM2-treated perovskite solar cell (PSC) obtains the best photoelectric conversion efficiency (PCE) of 16.76% under AM 1.5 G illumination (100 mW cm-2) with enhanced Jsc and Voc compared to CB-treated PSC.

  2. Ultrafast pulse generation from erbium-doped fiber laser modulated by hybrid organic-inorganic halide perovskites

    NASA Astrophysics Data System (ADS)

    Jiang, Guobao; Miao, Lili; Yi, Jun; Huang, Bin; Peng, Wei; Zou, Yanhong; Huang, Huihui; Hu, Wei; Zhao, Chujun; Wen, Shuangchun

    2017-04-01

    We report the nonlinear optical responses of organic-inorganic halide perovskite CH3NH3PbI3 and its application in ultrafast pulse generation from an erbium-doped fiber laser in the optical communication band. By adopting the Z-scan technique, the third-order nonlinear optical responses of the organic-inorganic halide perovskites have been characterized. An ultrafast optical pulse with a pulse width of 661 fs centered at a wavelength of 1555 nm has been delivered via the nonlinear optical material introduced into the fiber laser cavity. Our experimental results confirm that the organic-inorganic halide perovskite possesses obvious third-order nonlinear optical responses in the C-band window and manifests its application potential in nonlinear optoelectronic devices.

  3. Striction-Coupled Magnetoresistance in Perovskite-type Manganese Oxides (Nd,Sm)_1/2Sr_1/2MnO_3

    NASA Astrophysics Data System (ADS)

    Kuwahara, H.; Tomioka, Y.; Moritomo, Y.; Asamitsu, A.; Tokura, Y.

    1996-03-01

    Magnetoresistance (MR) of more than three orders of magnitude, which is strongly coupled to lattice striction, has been observed under a relatively low magnetic field (e.g., 0.4 T at 115 K) for a single crystal of perovskite-type manganese oxide with finely controlled ionic radii of the A-sites, (Nd,Sm)_1/2Sr_1/2MnO_3. The colossal MR phenomena are viewed as a first-order insulator-to-metal phase transition induced by a magnetic field, which accompanies a metamagnetic (antiferromagnetic-to-ferromagnetic) transition as well as a lattice-structural change. Clear hystereses as well as switching-like changes of magnetization, striction, and resistivity are observed in increasing and decreasing magnetic field at temperatures (113-160K) near above the Curie temperature. In this temperature region, the ferromagnetic double exchange interaction seems to be suppressed by localization of carriers and/or antiferromagnetic interaction. We speculate that this antiferromagnetic interaction is relevant to a charge-ordering instability, the real space ordering of doped holes, observed in many of the similar manganese oxides. This work was supported by New Energy and Industrial Technology Development Organization (NEDO) of Japan.

  4. Rhombohedral-cubic transition in Li 0.2Na 0.3La 0.5TiO 3 perovskite

    NASA Astrophysics Data System (ADS)

    Varez, Alejandro; Fernandez-Díaz, Maria T.; Sanz, Jesus

    2004-12-01

    High-temperature behavior of the fast ionic conductor Li 0.2Na 0.3La 0.5TiO 3 has been investigated by neutron powder diffraction between 300 and 1073 K. The Rietveld analysis of diffraction patterns showed around 1000 K a change from rhombohedral ( R3¯c) to cubic ( Pm3 m) symmetry. During the heating, the tilting of octahedra along the [111] direction of the cubic perovskite decreased and the rhombic distortion of oxygen square windows that relates contiguous A-sites of the perovskite was eliminated. The influence of the octahedral tilting on Li mobility is finally discussed.

  5. 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.

  6. Atomic Resolution Imaging of Halide Perovskites.

    PubMed

    Yu, Yi; Zhang, Dandan; Kisielowski, Christian; Dou, Letian; Kornienko, Nikolay; Bekenstein, Yehonadav; Wong, Andrew B; Alivisatos, A Paul; Yang, Peidong

    2016-12-14

    The radiation-sensitive nature of halide perovskites has hindered structural studies at the atomic scale. We overcome this obstacle by applying low dose-rate in-line holography, which combines aberration-corrected high-resolution transmission electron microscopy with exit-wave reconstruction. This technique successfully yields the genuine atomic structure of ultrathin two-dimensional CsPbBr3 halide perovskites, and a quantitative structure determination was achieved atom column by atom column using the phase information of the reconstructed exit-wave function without causing electron beam-induced sample alterations. An extraordinarily high image quality enables an unambiguous structural analysis of coexisting high-temperature and low-temperature phases of CsPbBr3 in single particles. On a broader level, our approach offers unprecedented opportunities to better understand halide perovskites at the atomic level as well as other radiation-sensitive materials.

  7. 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.

  8. A heteroepitaxial perovskite metal-base transistor.

    PubMed

    Yajima, Takeaki; Hikita, Yasuyuki; Hwang, Harold Y

    2011-03-01

    '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.

  9. 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.

  10. Organometallic perovskites for optoelectronic applications (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Levchuk, Levgen; Hoegl, Florian; Brandl, Marco; Osvet, Andres; Hock, Rainer; Herre, Patrick; Wolfgang, Wolfgang; Schweizer, Peter; Spiecker, Erdmann; Batentschuk, Miroslaw; Brabec, Christoph

    2016-09-01

    Organometallic halide perovskites CH3NH3BX3 (B= Pb, Sn, Ge; X = I, Br, Cl) have become one of the most promising semiconductors for solar cell applications, reaching power conversion efficiencies beyond 20%. Improving our ability to harness the full potential of organometal halide perovskites requires the development of more reliable synthesis routines of well defined, reproducible and defect free reference systems allowing to study the fundamental photo-physical processes. In this study we present size and band gap engineering for organo-lead perovskites crystallites with various shapes and sizes ranging from the 5 nm regime all the way to 1 cm. Colloidal nano-crystals, micro-crystlline particles as well as single crystals are demonstrated with excellent purity and control in shape and size are demonstrated. The structural, optical and photo-physical properties of these reference materials are investigated and analyzed as function of their size and shape.

  11. Machine learning bandgaps of double perovskites

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam; Mannodi-Kanakkithodi, Arun; Uberuaga, Blas; Ramprasad, Rampi; Gubernatis, James; Lookman, Turab

    The ability to make rapid and accurate predictions of bandgaps for double perovskites is of much practical interest for a range of applications. While quantum mechanical computations for high-fidelity bandgaps are enormously computation-time intensive and thus impractical in high throughput studies, informatics-based statistical learning approaches can be a promising alternative. Here we demonstrate a systematic feature-engineering approach and a robust learning framework for efficient and accurate predictions of electronic bandgaps for double perovskites. After evaluating a set of nearly 1.2 million features, we identify several elemental features of the constituent atomic species as the most crucial and relevant predictors. The developed models are validated and tested using the best practices of data science (on a dataset of more than 1300 double perovskite bandgaps) and further analyzed to rationalize their prediction performance. Los Alamos National Laboratory LDRD program and the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

  12. Electronic and Ionic Transport Dynamics in Organolead Halide Perovskites.

    PubMed

    Li, Dehui; Wu, Hao; Cheng, Hung-Chieh; Wang, Gongming; Huang, Yu; Duan, Xiangfeng

    2016-07-26

    Ion migration has been postulated as the underlying mechanism responsible for the hysteresis in organolead halide perovskite devices. However, the electronic and ionic transport dynamics and how they impact each other in organolead halide perovskites remain elusive to date. Here we report a systematic investigation of the electronic and ionic transport dynamics in organolead halide perovskite microplate crystals and thin films using temperature-dependent transient response measurements. Our study reveals that thermally activated ionic and electronic conduction coexist in perovskite devices. The extracted activation energies suggest that the electronic transport is easier, but ions migrate harder in microplates than in thin films, demonstrating that the crystalline quality and grain boundaries can fundamentally modify electronic and ionic transport in perovskites. These findings offer valuable insight on the electronic and ionic transport dynamics in organolead halide perovskites, which is critical for optimizing perovskite devices with reduced hysteresis and improved stability and efficiency.

  13. 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.

  14. A review on visible light active perovskite-based photocatalysts.

    PubMed

    Kanhere, Pushkar; Chen, Zhong

    2014-12-01

    Perovskite-based photocatalysts are of significant interest in the field of photocatalysis. To date, several perovskite material systems have been developed and their applications in visible light photocatalysis studied. This article provides a review of the visible light (λ > 400 nm) active perovskite-based photocatalyst systems. The materials systems are classified by the B site cations and their crystal structure, optical properties, electronic structure, and photocatalytic performance are reviewed in detail. Titanates, tantalates, niobates, vanadates, and ferrites form important photocatalysts which show promise in visible light-driven photoreactions. Along with simple perovskite (ABO3) structures, development of double/complex perovskites that are active under visible light is also reviewed. Various strategies employed for enhancing the photocatalytic performance have been discussed, emphasizing the specific advantages and challenges offered by perovskite-based photocatalysts. This review provides a broad overview of the perovskite photocatalysts, summarizing the current state of the work and offering useful insights for their future development.

  15. A-SITE-AND/OR B-SITE-MODIFIED PBZRTIO3 MATERIALS AND (PB, SR, CA, BA, MG) (ZR, TI,NB, TA)O3 FILMS HAVING UTILITY IN FERROELECTRIC RANDOM ACCESS MEMORIES AND HIGH PERFORMANCE THIN FILM MICROACTUATORS

    NASA Technical Reports Server (NTRS)

    Roeder, Jeffrey F. (Inventor); Chen, Ing-Shin (Inventor); Bilodeau, Steven (Inventor); Baum, Thomas H. (Inventor)

    2004-01-01

    A modified PbZrTiO.sub.3 perovskite crystal material thin film, wherein the PbZrTiO.sub.3 perovskite crystal material includes crystal lattice A-sites and B-sites at least one of which is modified by the presence of a substituent selected from the group consisting of (i) A-site substituents consisting of Sr, Ca, Ba and Mg, and (ii) B-site substituents selected from the group consisting of Nb and Ta. The perovskite crystal thin film material may be formed by liquid delivery MOCVD from metalorganic precursors of the metal components of the thin film, to form PZT and PSZT, and other piezoelectric and ferroelectric thin film materials. The thin films of the invention have utility in non-volatile ferroelectric memory devices (NV-FeRAMs), and in microelectromechanical systems (MEMS) as sensor and/or actuator elements, e.g., high speed digital system actuators requiring low input power levels.

  16. Perovskite oxide nanowires: synthesis, property and structural characterization.

    PubMed

    Zhu, Xinhua; Liu, Zhiguo; Ming, Naiben

    2010-07-01

    Perovskite oxide materials display a wide spectrum of functional properties, including switchable polarization, piezoelectricity, pyroelectricity, and non-linear dielectric behavior. These properties are indispensable for application in electronic devices such as non-volatile memories, sensors, microactuators, infrared detectors, microwave phase filters, and so on. Recent advances in science and technology of perovskite oxide materials have resulted in the feature sizes of perovskite oxides-based electronic devices entering into nanoscale dimensions. At nanoscale perovskite oxide materials exhibit a pronounced size effect manifesting itself in a significant deviation of the properties of low-dimensional structures from the bulk and film counterparts. In the last decade low-dimensional perovskite nanosized oxides have been received much attention because of their superior physical and chemical properties. Among them, perovskite oxide nanowires are especially attractive for nanoscience studies and nanotechnology applications. Compared to other low-dimensional perovskite oxide systems, perovskite oxide nanowires are not only used as the building blocks of future nanodevices, but also they offer fundamental scientific opportunities for investigating the intrinsic size effects of physical properties. In the recent years, much progress has been made both in synthesis and physical property testing of perovskite oxide nanowires, which have a profound impact on the nanoelectronics. In this work, an overview of the state of art in perovskite oxide nanowires is presented, which covers their synthesis, property, and structural characterization. In the first part, the recent literatures for fabricating perovskite oxide nanowires with promising features, are critically reviewed. The second part deals with the recent advances on the physical property testing of perovskite oxide nanowires. The third part summarizes the recent progress on microstructural characterizations of

  17. Research Update: Behind the high efficiency of hybrid perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Fakharuddin, Azhar; De Rossi, Francesca; Watson, Trystan M.; Schmidt-Mende, Lukas; Jose, Rajan

    2016-09-01

    Perovskite solar cells (PSCs) marked tremendous progress in a short period of time and offer bright hopes for cheap solar electricity. Despite high power conversion efficiency >20%, its poor operational stability as well as involvement of toxic, volatile, and less-abundant materials hinders its practical deployment. The fact that degradation and toxicity are typically observed in the most successful perovskite involving organic cation and toxic lead, i.e., CH3NH3PbX3, requires a deep understanding of their role in photovoltaic performance in order to envisage if a non-toxic, stable yet highly efficient device is feasible. Towards this, we first provide an overview of the basic chemistry and physics of halide perovskites and its correlation with its extraordinary properties such as crystal structure, bandgap, ferroelectricity, and electronic transport. We then discuss device related aspects such as the various device designs in PSCs and role of interfaces in origin of PV parameters particularly open circuit voltage, various film processing methods and their effect on morphology and characteristics of perovskite films, and the origin and elimination of hysteresis and operational stability in these devices. We then identify future perspectives for stable and efficient PSCs for practical deployment.

  18. Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals

    SciTech Connect

    Li, Dehui; Wang, Gongming; Cheng, Hung -Chieh; Chen, Chih -Yen; Wu, Hao; Liu, Yuan; Huang, Yu; Duan, Xiangfeng

    2016-04-21

    Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in perovskite can significantly alter its optical, electrical properties and impact the corresponding applications. Here, we report a systematic investigation of the size-dependent orthorhombic-to-tetragonal phase transition using a combined temperature-dependent optical, electrical transport and transmission electron microscopy study. Our studies of individual perovskite microplates with variable thicknesses demonstrate that the phase transition temperature decreases with reducing microplate thickness. The sudden decrease of mobility around phase transition temperature and the presence of hysteresis loops in the temperature-dependent mobility confirm that the orthorhombic-to-tetragonal phase transition is a first-order phase transition. Lastly, our findings offer significant fundamental insight on the temperature-and size-dependent structural, optical and charge transport properties of perovskite materials, and can greatly impact future exploration of novel electronic and optoelectronic devices from these materials.

  19. TiO2 Electron Transport Bilayer for Highly Efficient Planar Perovskite Solar Cell.

    PubMed

    Lu, Hao; Tian, Wei; Gu, Bangkai; Zhu, Yayun; Li, Liang

    2017-10-01

    In planar perovskite solar cells, it is vital to engineer the extraction and recombination of electron-hole pairs at the electron transport layer/perovskite interface for obtaining high performance. This study reports a novel titanium oxide (TiO2 ) bilayer with different Fermi energy levels by combing atomic layer deposition and spin-coating technique. Energy band alignments of TiO2 bilayer can be modulated by controlling the deposition order of layers. The TiO2 bilayer based perovskite solar cells are highly efficient in carrier extraction, recombination suppression, and defect passivation, and thus demonstrate champion efficiencies up to 16.5%, presenting almost 50% enhancement compared to the TiO2 single layer based counterparts. The results suggest that the bilayer with type II band alignment as electron transport layers provides an efficient approach for constructing high-performance planar perovskite solar cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Unravelling the low-temperature metastable state in perovskite solar cells by noise spectroscopy.

    PubMed

    Barone, C; Lang, F; Mauro, C; Landi, G; Rappich, J; Nickel, N H; Rech, B; Pagano, S; Neitzert, H C

    2016-10-05

    The hybrid perovskite methylammonium lead iodide CH3NH3PbI3 recently revealed its potential for the manufacturing of low-cost and efficient photovoltaic cells. However, many questions remain unanswered regarding the physics of the charge carrier conduction. In this respect, it is known that two structural phase transitions, occurring at temperatures near 160 and 310 K, could profoundly change the electronic properties of the photovoltaic material, but, up to now, a clear experimental evidence has not been reported. In order to shed light on this topic, the low-temperature phase transition of perovskite solar cells has been thoroughly investigated by using electric noise spectroscopy. Here it is shown that the dynamics of fluctuations detect the existence of a metastable state in a crossover region between the room-temperature tetragonal and the low-temperature orthorhombic phases of the perovskite compound. Besides the presence of a noise peak at this transition, a saturation of the fluctuation amplitudes is observed induced by the external DC current or, equivalently, by light exposure. This noise saturation effect is independent on temperature, and may represent an important aspect to consider for a detailed explanation of the mechanisms of operation in perovskite solar cells.

  1. Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals

    NASA Astrophysics Data System (ADS)

    Li, Dehui; Wang, Gongming; Cheng, Hung-Chieh; Chen, Chih-Yen; Wu, Hao; Liu, Yuan; Huang, Yu; Duan, Xiangfeng

    2016-04-01

    Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in perovskite can significantly alter its optical, electrical properties and impact the corresponding applications. Here, we report a systematic investigation of the size-dependent orthorhombic-to-tetragonal phase transition using a combined temperature-dependent optical, electrical transport and transmission electron microscopy study. Our studies of individual perovskite microplates with variable thicknesses demonstrate that the phase transition temperature decreases with reducing microplate thickness. The sudden decrease of mobility around phase transition temperature and the presence of hysteresis loops in the temperature-dependent mobility confirm that the orthorhombic-to-tetragonal phase transition is a first-order phase transition. Our findings offer significant fundamental insight on the temperature- and size-dependent structural, optical and charge transport properties of perovskite materials, and can greatly impact future exploration of novel electronic and optoelectronic devices from these materials.

  2. Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals

    PubMed Central

    Li, Dehui; Wang, Gongming; Cheng, Hung-Chieh; Chen, Chih-Yen; Wu, Hao; Liu, Yuan; Huang, Yu; Duan, Xiangfeng

    2016-01-01

    Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in perovskite can significantly alter its optical, electrical properties and impact the corresponding applications. Here, we report a systematic investigation of the size-dependent orthorhombic-to-tetragonal phase transition using a combined temperature-dependent optical, electrical transport and transmission electron microscopy study. Our studies of individual perovskite microplates with variable thicknesses demonstrate that the phase transition temperature decreases with reducing microplate thickness. The sudden decrease of mobility around phase transition temperature and the presence of hysteresis loops in the temperature-dependent mobility confirm that the orthorhombic-to-tetragonal phase transition is a first-order phase transition. Our findings offer significant fundamental insight on the temperature- and size-dependent structural, optical and charge transport properties of perovskite materials, and can greatly impact future exploration of novel electronic and optoelectronic devices from these materials. PMID:27098114

  3. Application of the Perovskite Ceramics to Conditioning of the Long-Lived Fraction of HLW

    SciTech Connect

    Cherniavskaya, N. E.; Chizhevskaya, S. V.; Ochkin, A. V.

    2002-02-25

    High level waste (HLW) partitioning concept includes separation of a long-lived fraction following by its immobilization in ceramics. Improved process flow sheet suggested for implementation at PA ''Mayak'' implies production of a long-lived HLW fraction with rare earth elements (REE) as major components, Am and Cm as minor constituents, and only traces of U, Pu, and corrosion products (iron group elements). Because most of the elements occurred are trivalent, one of the most promising host phase is supposed to be REE aluminate or ferrate with perovskite structure. Major advantages of the perovskite are incorporation of trivalent REEs and actinides, simultaneous incorporation of residual corrosion products, flexibility of perovskite structure allowing accommodation of traces of tetravalent actinides (U, Pu), high chemical durability, and high HLW volume reduction. High melting points of the perovskites makes problematic melting route, therefore, cold pressing and sintering method is more preferable. In order to reduce sintering temperature pre-treatment of ceramic batches with high mechanical energy has been studied.

  4. Self-assembled dynamic perovskite composite cathodes for intermediate temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Shin, J. Felix; Xu, Wen; Zanella, Marco; Dawson, Karl; Savvin, Stanislav N.; Claridge, John B.; Rosseinsky, Matthew J.

    2017-01-01

    Electrode materials for intermediate temperature (500-700 ∘C) solid oxide fuel cells require electrical and mechanical stability to maintain performance during the cell lifetime. This has proven difficult to achieve for many candidate cathode materials and their derivatives with good transport and electrocatalytic properties because of reactivity towards cell components, and the fuels and oxidants. Here we present Ba0.5Sr0.5(Co0.7Fe0.3)0.6875W0.3125O3-δ (BSCFW), a self-assembled composite prepared through simple solid state synthesis, consisting of B-site cation ordered double perovskite and disordered single perovskite oxide phases, as a candidate cathode material. These phases interact by dynamic compositional change at the operating temperature, promoting both chemical stability through the increased amount of W in the catalytically active single perovskite provided from the W-reservoir double perovskite, and microstructural stability through reduced sintering of the supported catalytically active phase. This interactive catalyst-support system enabled stable high electrochemical activity through the synergic integration of the distinct properties of the two phases.

  5. Three-Photon Absorption Induced Photoluminescence in Organo-Lead Mixed Halide Perovskites

    NASA Astrophysics Data System (ADS)

    Phan Vu, Thi Van; Nguyen, Minh Tu; Nguyen, Dam Thuy Trang; Vu, Tien Dung; Nguyen, Duc Long; An, Ngoc Mai; Nguyen, Minh Hieu; Sai, Cong Doanh; Bui, Van Diep; Hoang, Chi Hieu; Truong, Thanh Tu; Lai, Ngoc Diep; Nguyen-Tran, Thuat

    2017-03-01

    Organo-lead mixed halide perovskites have been showing remarkable performance for applications in solar cells and are very promising for numerous applications in optoelectronics and nonlinear optics. In this study, we report a room-temperature photoluminescence study of this material by using pulsed excitation laser sources at 1064 nm wavelength. Under our experimental conditions, strong photoluminescence was observed only for bromine-containing perovskites, CH3NH3Pb(I1-xBrx)3, thus suggesting an important role of bromine for photoluminescence of halide perovskites. The experimental results also showed that the photoluminescence peak was blue-shifted from 727 nm to 574 nm when x increased from 1/3 to 1. In particular, the photoluminescence peak featured a third-order dependence on the laser intensity. This direct observation of three-photon absorption-induced photoluminescence of organo-lead mixed halide perovskite materials thus opens up interesting applications in the field of optoelectronics and nonlinear optics.

  6. Perovskite-Erbium Silicate Nanosheet Hybrid Waveguide Photodetectors at the Near-Infrared Telecommunication Band.

    PubMed

    Zhang, Xuehong; Yang, Shuzhen; Zhou, Hong; Liang, Junwu; Liu, Huawei; Xia, Hui; Zhu, Xiaoli; Jiang, Ying; Zhang, Qinglin; Hu, Wei; Zhuang, Xiujuan; Liu, Hongjun; Hu, Weida; Wang, Xiao; Pan, Anlian

    2017-06-01

    Methylammonium lead halide perovskites have attracted enormous attentions due to their superior optical and electronic properties. However, the photodetection at near-infrared telecommunication wavelengths is hardly achievable because of their wide bandgaps. Here, this study demonstrates, for the first time, novel perovskite-erbium silicate nanosheet hybrid photodetectors with remarkable spectral response at ≈1.54 µm. Under the near-infrared light illumination, the erbium silicate nanosheets can give strong upconversion luminescence, which will be well confined in their cavities and then be efficiently coupled into and simultaneously excite the adjacent perovskite to realize photodetection. These devices own prominent responsivity and external quantum efficiency as high as previously reported microscale silicon-based subbandgap photodetectors. More importantly, the photoresponse speed (≈900 µs) is faster by five orders than the ever reported hot electron silicon-based photodetectors at telecommunication wavelengths. The realization of perovskite-based telecommunication band photodetectors will open new chances for applications in advanced integrated photonics devices and systems. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Three-Photon Absorption Induced Photoluminescence in Organo-Lead Mixed Halide Perovskites

    NASA Astrophysics Data System (ADS)

    Phan Vu, Thi Van; Nguyen, Minh Tu; Nguyen, Dam Thuy Trang; Vu, Tien Dung; Nguyen, Duc Long; An, Ngoc Mai; Nguyen, Minh Hieu; Sai, Cong Doanh; Bui, Van Diep; Hoang, Chi Hieu; Truong, Thanh Tu; Lai, Ngoc Diep; Nguyen-Tran, Thuat

    2017-06-01

    Organo-lead mixed halide perovskites have been showing remarkable performance for applications in solar cells and are very promising for numerous applications in optoelectronics and nonlinear optics. In this study, we report a room-temperature photoluminescence study of this material by using pulsed excitation laser sources at 1064 nm wavelength. Under our experimental conditions, strong photoluminescence was observed only for bromine-containing perovskites, CH3NH3Pb(I1-xBrx)3, thus suggesting an important role of bromine for photoluminescence of halide perovskites. The experimental results also showed that the photoluminescence peak was blue-shifted from 727 nm to 574 nm when x increased from 1/3 to 1. In particular, the photoluminescence peak featured a third-order dependence on the laser intensity. This direct observation of three-photon absorption-induced photoluminescence of organo-lead mixed halide perovskite materials thus opens up interesting applications in the field of optoelectronics and nonlinear optics.

  8. Unravelling the low-temperature metastable state in perovskite solar cells by noise spectroscopy

    NASA Astrophysics Data System (ADS)

    Barone, C.; Lang, F.; Mauro, C.; Landi, G.; Rappich, J.; Nickel, N. H.; Rech, B.; Pagano, S.; Neitzert, H. C.

    2016-10-01

    The hybrid perovskite methylammonium lead iodide CH3NH3PbI3 recently revealed its potential for the manufacturing of low-cost and efficient photovoltaic cells. However, many questions remain unanswered regarding the physics of the charge carrier conduction. In this respect, it is known that two structural phase transitions, occurring at temperatures near 160 and 310 K, could profoundly change the electronic properties of the photovoltaic material, but, up to now, a clear experimental evidence has not been reported. In order to shed light on this topic, the low-temperature phase transition of perovskite solar cells has been thoroughly investigated by using electric noise spectroscopy. Here it is shown that the dynamics of fluctuations detect the existence of a metastable state in a crossover region between the room-temperature tetragonal and the low-temperature orthorhombic phases of the perovskite compound. Besides the presence of a noise peak at this transition, a saturation of the fluctuation amplitudes is observed induced by the external DC current or, equivalently, by light exposure. This noise saturation effect is independent on temperature, and may represent an important aspect to consider for a detailed explanation of the mechanisms of operation in perovskite solar cells.

  9. Unravelling the low-temperature metastable state in perovskite solar cells by noise spectroscopy

    PubMed Central

    Barone, C.; Lang, F.; Mauro, C.; Landi, G.; Rappich, J.; Nickel, N. H.; Rech, B.; Pagano, S.; Neitzert, H. C.

    2016-01-01

    The hybrid perovskite methylammonium lead iodide CH3NH3PbI3 recently revealed its potential for the manufacturing of low-cost and efficient photovoltaic cells. However, many questions remain unanswered regarding the physics of the charge carrier conduction. In this respect, it is known that two structural phase transitions, occurring at temperatures near 160 and 310 K, could profoundly change the electronic properties of the photovoltaic material, but, up to now, a clear experimental evidence has not been reported. In order to shed light on this topic, the low-temperature phase transition of perovskite solar cells has been thoroughly investigated by using electric noise spectroscopy. Here it is shown that the dynamics of fluctuations detect the existence of a metastable state in a crossover region between the room-temperature tetragonal and the low-temperature orthorhombic phases of the perovskite compound. Besides the presence of a noise peak at this transition, a saturation of the fluctuation amplitudes is observed induced by the external DC current or, equivalently, by light exposure. This noise saturation effect is independent on temperature, and may represent an important aspect to consider for a detailed explanation of the mechanisms of operation in perovskite solar cells. PMID:27703203

  10. Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals

    DOE PAGES

    Li, Dehui; Wang, Gongming; Cheng, Hung -Chieh; ...

    2016-04-21

    Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in perovskite can significantly alter its optical, electrical properties and impact the corresponding applications. Here, we report a systematic investigation of the size-dependent orthorhombic-to-tetragonal phase transition using a combined temperature-dependent optical, electrical transport and transmission electron microscopy study. Our studies of individual perovskite microplates with variable thicknesses demonstrate that the phase transition temperature decreases with reducing microplate thickness. The sudden decrease of mobility around phase transition temperature and the presence of hysteresis loops in the temperature-dependent mobility confirmmore » that the orthorhombic-to-tetragonal phase transition is a first-order phase transition. Lastly, our findings offer significant fundamental insight on the temperature-and size-dependent structural, optical and charge transport properties of perovskite materials, and can greatly impact future exploration of novel electronic and optoelectronic devices from these materials.« less

  11. Highly Efficient Flexible Perovskite Solar Cells with Antireflection and Self-Cleaning Nanostructures.

    PubMed

    Tavakoli, Mohammad Mahdi; Tsui, Kwong-Hoi; Zhang, Qianpeng; He, Jin; Yao, Yan; Li, Dongdong; Fan, Zhiyong

    2015-10-27

    Flexible thin film solar cells have attracted a great deal of attention as mobile power sources and key components for building-integrated photovoltaics, due to their light weight and flexible features in addition to compatibility with low-cost roll-to-roll fabrication processes. Among many thin film materials, organometallic perovskite materials are emerging as highly promising candidates for high efficiency thin film photovoltaics; however, the performance, scalability, and reliability of the flexible perovskite solar cells still have large room to improve. Herein, we report highly efficient, flexible perovskite solar cells fabricated on ultrathin flexible glasses. In such a device structure, the flexible glass substrate is highly transparent and robust, with low thermal expansion coefficient, and perovskite thin film was deposited with a thermal evaporation method that showed large-scale uniformity. In addition, a nanocone array antireflection film was attached to the front side of the glass substrate in order to improve the optical transmittance and to achieve a water-repelling effect at the same time. It was found that the fabricated solar cells have reasonable bendability, with 96% of the initial value remaining after 200 bending cycles, and the power conversion efficiency was improved from 12.06 to 13.14% by using the antireflection film, which also demonstrated excellent superhydrophobicity.

  12. Pressure-induced phase transitions of hexagonal perovskite-like oxides

    SciTech Connect

    Aoba, Tomoya; Tiittanen, Taneli; Suematsu, Hisayuki; Karppinen, Maarit

    2016-01-15

    We have stabilized two new cubic (3C structured) A{sub 2}B′B′′O{sub 6}-type double-perovskite phases, Ba{sub 2}CoSbO{sub 6} and Ba{sub 2}ZnTeO{sub 6}, by means of a high-pressure heat-treatment of corresponding hexagonal (6H and 12R structured, respectively) non-perovskite phases at 4 GPa and 1000 °C. Similar treatments on hexagonal Ba{sub 2}TiMnO{sub 6} (12R) and Ba{sub 2}NiTeO{sub 6} (12R) phases did not yield the 3C double-perovskite structure but converted the 12R structure to the 6H structure. The pressure-induced phase conversion in each A{sub 2}B′B′′O{sub 6} system apparently goes from the 12R structure towards the 6H and 3C structures with increasing pressure, where the pressure ranges required most likely depend (among other possible factors) on the tolerance factor for the particular combination of A, B′ and B′′. We foresee that yet a number of novel B-site ordered double-perovskite compounds are to be discovered through the high-pressure high-temperature treatment. - Graphical abstract: High-pressure (HP) heat-treatment is an efficient tool to synthesize novel B-site ordered double-perovskite materials. This is demonstrated for two new cubic (3C structured) perovskite phases, Ba{sub 2}CoSbO{sub 6} and Ba{sub 2}ZnTeO{sub 6}, obtained through a HP conversion of corresponding hexagonal (6H and 12R structured, respectively) non-perovskite phases at 4 GPa and 1000 °C. Similar treatments on hexagonal Ba{sub 2}TiMnO{sub 6} (12R) and Ba{sub 2}NiTeO{sub 6} (12R) phases yield the intermediate 6H structure.

  13. Research Update: Luminescence in lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Srimath Kandada, Ajay Ram; Petrozza, Annamaria

    2016-09-01

    Efficiency and dynamics of radiative recombination of carriers are crucial figures of merit for optoelectronic materials. Following the recent success of lead halide perovskites in efficient photovoltaic and light emitting technologies, here we review some of the noted literature on the luminescence of this emerging class of materials. After outlining the theoretical formalism that is currently used to explain the carrier recombination dynamics, we review a few significant works which use photoluminescence as a tool to understand and optimize the operation of perovskite based optoelectronic devices.

  14. Nanoscale investigation of organic - inorganic halide perovskites

    NASA Astrophysics Data System (ADS)

    Cacovich, S.; Divitini, G.; Vrućinić, M.; Sadhanala, A.; Friend, R. H.; Sirringhaus, H.; Deschler, F.; Ducati, C.

    2015-10-01

    Over the last few years organic - inorganic halide perovskite-based solar cells have exhibited a rapid evolution, reaching certified power conversion efficiencies now surpassing 20%. Nevertheless the understanding of the optical and electronic properties of such systems on the nanoscale is still an open problem. In this work we investigate two model perovskite systems (based on iodine - CH3NH3PbI3 and bromine - CH3NH3PbBr3), analysing the local elemental composition and crystallinity and identifying chemical inhomogeneities.

  15. Large area perovskite solar cell module

    NASA Astrophysics Data System (ADS)

    Cai, Longhua; Liang, Lusheng; Wu, Jifeng; Ding, Bin; Gao, Lili; Fan, Bin

    2017-01-01

    The recent dramatic rise in power conversion efficiencies (PCE) of perovskite solar cells has triggered intense research worldwide. However, their practical development is hampered by poor stability and low PCE values with large areas devices. Here, we developed a gas-pumping method to avoid pinholes and eliminate local structural defects over large areas of perovskite film, even for 5 × 5 cm2 modules, the PCE reached 10.6% and no significant degradation was found after 140 days of outdoor testing. Our approach enables the realization of high performance large-area PSCs for practical application.

  16. Excited State Properties of Hybrid Perovskites.

    PubMed

    Saba, Michele; Quochi, Francesco; Mura, Andrea; Bongiovanni, Giovanni

    2016-01-19

    Metal halide perovskites have come to the attention of the scientific community for the progress achieved in solar light conversion. Energy sustainability is one of the priorities of our society, and materials advancements resulting in low-cost but efficient solar cells and large-area lighting devices represent a major goal for applied research. From a basic point of view, perovskites are an exotic class of hybrid materials combining some merits of organic and inorganic semiconductors: large optical absorption, large mobilities, and tunable band gap together with the possibility to be processed in solution. When a novel class of promising semiconductors comes into the limelight, lively discussions ensue on the photophysics of band-edge excitations, because just the states close to the band edge are entailed in energy/charge transport and light emission. This was the case several decades ago for III-V semiconductors, it has been up to 10 years ago for organics, and it is currently the case for perovskites. Our aim in this Account is to rationalize the body of experimental evidence on perovskite photophysics in a coherent theoretical framework, borrowing from the knowledge acquired over the years in materials optoelectronics. A crucial question is whether photon absorption leads to a population of unbound, conductive free charges or instead excitons, neutral and insulating bound states created by Coulomb interaction just below the energy of the band gap. We first focus on the experimental estimates of the exciton binding energy (Eb): at room temperature, Eb is comparable to the thermal energy kBT in MAPbI3 and increases up to values 2-3kBT in wide band gap MAPbBr3 and MAPbCl3. Statistical considerations predict that these values, even though comparable to or larger than thermal energy, let free carriers prevail over bound excitons for all levels of excitation densities relevant for devices. The analysis of photophysics evidence confirms that all hybrid halide

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

    PubMed

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

    2016-09-19

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

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

    PubMed Central

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

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  20. 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.

  1. Giant switchable photovoltaic effect in organometal trihalide perovskite devices

    DOE PAGES

    Xiao, Zhengguo; Yuan, Yongbo; Shao, Yuchuan; ...

    2014-12-08

    Organolead trihalide perovskite (OTP) materials are emerging as naturally abundant materials for low-cost, solution-processed and highly efficient solar cells. Here, we show that, in OTP-based photovoltaic devices with vertical and lateral cell configurations, the photocurrent direction can be switched repeatedly by applying a small electric field of <1 V μm–1. The switchable photocurrent, generally observed in devices based on ferroelectric materials, reached 20.1 mA cm–2 under one sun illumination in OTP devices with a vertical architecture, which is four orders of magnitude larger than that measured in other ferroelectric photovoltaic devices. This field-switchable photovoltaic effect can be explained by themore » formation of reversible p–i–n structures induced by ion drift in the perovskite layer. Furthermore, the demonstration of switchable OTP photovoltaics and electric-field-manipulated doping paves the way for innovative solar cell designs and for the exploitation of OTP materials in electrically and optically readable memristors and circuits.« less

  2. Photoinduced Giant Dielectric Constant in Lead Halide Perovskite Solar Cells.

    PubMed

    Juarez-Perez, Emilio J; Sanchez, Rafael S; Badia, Laura; Garcia-Belmonte, Germá; Kang, Yong Soo; Mora-Sero, Ivan; Bisquert, Juan

    2014-07-03

    Organic-inorganic lead trihalide perovskites have emerged as an outstanding photovoltaic material that demonstrated a high 17.9% conversion efficiency of sunlight to electricity in a short time. We have found a giant dielectric constant (GDC) phenomenon in these materials consisting on a low frequency dielectric constant in the dark of the order of ε0 = 1000. We also found an unprecedented behavior in which ε0 further increases under illumination or by charge injection at applied bias. We observe that ε0 increases nearly linearly with the illumination intensity up to an additional factor 1000 under 1 sun. Measurement of a variety of samples of different morphologies, compositions, and different types of contacts shows that the GDC is an intrinsic property of MAPbX3 (MA = CH3NH3(+)). We hypothesize that the large dielectric response is induced by structural fluctuations. Photoinduced carriers modify the local unit cell equilibrium and change the polarizability, assisted by the freedom of rotation of MA. The study opens a way for the understanding of a key aspect of the photovoltaic operation of high efficiency perovskite solar cells.

  3. Giant switchable photovoltaic effect in organometal trihalide perovskite devices

    NASA Astrophysics Data System (ADS)

    Xiao, Zhengguo; Yuan, Yongbo; Shao, Yuchuan; Wang, Qi; Dong, Qingfeng; Bi, Cheng; Sharma, Pankaj; Gruverman, Alexei; Huang, Jinsong

    2015-02-01

    Organolead trihalide perovskite (OTP) materials are emerging as naturally abundant materials for low-cost, solution-processed and highly efficient solar cells. Here, we show that, in OTP-based photovoltaic devices with vertical and lateral cell configurations, the photocurrent direction can be switched repeatedly by applying a small electric field of <1 V μm-1. The switchable photocurrent, generally observed in devices based on ferroelectric materials, reached 20.1 mA cm-2 under one sun illumination in OTP devices with a vertical architecture, which is four orders of magnitude larger than that measured in other ferroelectric photovoltaic devices. This field-switchable photovoltaic effect can be explained by the formation of reversible p-i-n structures induced by ion drift in the perovskite layer. The demonstration of switchable OTP photovoltaics and electric-field-manipulated doping paves the way for innovative solar cell designs and for the exploitation of OTP materials in electrically and optically readable memristors and circuits.

  4. Giant switchable photovoltaic effect in organometal trihalide perovskite devices

    SciTech Connect

    Xiao, Zhengguo; Yuan, Yongbo; Shao, Yuchuan; Wang, Qi; Dong, Qingfeng; Bi, Cheng; Sharma, Pankaj; Gruverman, Alexei; Huang, Jinsong

    2014-12-08

    Organolead trihalide perovskite (OTP) materials are emerging as naturally abundant materials for low-cost, solution-processed and highly efficient solar cells. Here, we show that, in OTP-based photovoltaic devices with vertical and lateral cell configurations, the photocurrent direction can be switched repeatedly by applying a small electric field of <1 V μm–1. The switchable photocurrent, generally observed in devices based on ferroelectric materials, reached 20.1 mA cm–2 under one sun illumination in OTP devices with a vertical architecture, which is four orders of magnitude larger than that measured in other ferroelectric photovoltaic devices. This field-switchable photovoltaic effect can be explained by the formation of reversible p–i–n structures induced by ion drift in the perovskite layer. Furthermore, the demonstration of switchable OTP photovoltaics and electric-field-manipulated doping paves the way for innovative solar cell designs and for the exploitation of OTP materials in electrically and optically readable memristors and circuits.

  5. 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.

  6. Giant switchable photovoltaic effect in organometal trihalide perovskite devices.

    PubMed

    Xiao, Zhengguo; Yuan, Yongbo; Shao, Yuchuan; Wang, Qi; Dong, Qingfeng; Bi, Cheng; Sharma, Pankaj; Gruverman, Alexei; Huang, Jinsong

    2015-02-01

    Organolead trihalide perovskite (OTP) materials are emerging as naturally abundant materials for low-cost, solution-processed and highly efficient solar cells. Here, we show that, in OTP-based photovoltaic devices with vertical and lateral cell configurations, the photocurrent direction can be switched repeatedly by applying a small electric field of <1 V μm(-1). The switchable photocurrent, generally observed in devices based on ferroelectric materials, reached 20.1 mA cm(-2) under one sun illumination in OTP devices with a vertical architecture, which is four orders of magnitude larger than that measured in other ferroelectric photovoltaic devices. This field-switchable photovoltaic effect can be explained by the formation of reversible p-i-n structures induced by ion drift in the perovskite layer. The demonstration of switchable OTP photovoltaics and electric-field-manipulated doping paves the way for innovative solar cell designs and for the exploitation of OTP materials in electrically and optically readable memristors and circuits.

  7. Lead iodide perovskite light-emitting field-effect transistor

    PubMed Central

    Chin, Xin Yu; Cortecchia, Daniele; Yin, Jun; Bruno, Annalisa; Soci, Cesare

    2015-01-01

    Despite the widespread use of solution-processable hybrid organic–inorganic perovskites in photovoltaic and light-emitting applications, determination of their intrinsic charge transport parameters has been elusive due to the variability of film preparation and history-dependent device performance. Here we show that screening effects associated to ionic transport can be effectively eliminated by lowering the operating temperature of methylammonium lead iodide perovskite (CH3NH3PbI3) field-effect transistors. Field-effect carrier mobility is found to increase by almost two orders of magnitude below 200 K, consistent with phonon scattering-limited transport. Under balanced ambipolar carrier injection, gate-dependent electroluminescence is also observed from the transistor channel, with spectra revealing the tetragonal to orthorhombic phase transition. This demonstration of CH3NH3PbI3 light-emitting field-effect transistors provides intrinsic transport parameters to guide materials and solar cell optimization, and will drive the development of new electro-optic device concepts, such as gated light-emitting diodes and lasers operating at room temperature. PMID:26108967

  8. Lead iodide perovskite light-emitting field-effect transistor

    NASA Astrophysics Data System (ADS)

    Chin, Xin Yu; Cortecchia, Daniele; Yin, Jun; Bruno, Annalisa; Soci, Cesare

    2015-06-01

    Despite the widespread use of solution-processable hybrid organic-inorganic perovskites in photovoltaic and light-emitting applications, determination of their intrinsic charge transport parameters has been elusive due to the variability of film preparation and history-dependent device performance. Here we show that screening effects associated to ionic transport can be effectively eliminated by lowering the operating temperature of methylammonium lead iodide perovskite (CH3NH3PbI3) field-effect transistors. Field-effect carrier mobility is found to increase by almost two orders of magnitude below 200 K, consistent with phonon scattering-limited transport. Under balanced ambipolar carrier injection, gate-dependent electroluminescence is also observed from the transistor channel, with spectra revealing the tetragonal to orthorhombic phase transition. This demonstration of CH3NH3PbI3 light-emitting field-effect transistors provides intrinsic transport parameters to guide materials and solar cell optimization, and will drive the development of new electro-optic device concepts, such as gated light-emitting diodes and lasers operating at room temperature.

  9. Ferroelastic switching in a layered-perovskite thin film

    NASA Astrophysics Data System (ADS)

    Wang, Chuanshou; Ke, Xiaoxing; Wang, Jianjun; Liang, Renrong; Luo, Zhenlin; Tian, Yu; Yi, Di; Zhang, Qintong; Wang, Jing; Han, Xiu-Feng; van Tendeloo, Gustaaf; Chen, Long-Qing; Nan, Ce-Wen; Ramesh, Ramamoorthy; Zhang, Jinxing

    2016-02-01

    A controllable ferroelastic switching in ferroelectric/multiferroic oxides is highly desirable due to the non-volatile strain and possible coupling between lattice and other order parameter in heterostructures. However, a substrate clamping usually inhibits their elastic deformation in thin films without micro/nano-patterned structure so that the integration of the non-volatile strain with thin film devices is challenging. Here, we report that reversible in-plane elastic switching with a non-volatile strain of approximately 0.4% can be achieved in layered-perovskite Bi2WO6 thin films, where the ferroelectric polarization rotates by 90° within four in-plane preferred orientations. Phase-field simulation indicates that the energy barrier of ferroelastic switching in orthorhombic Bi2WO6 film is ten times lower than the one in PbTiO3 films, revealing the origin of the switching with negligible substrate constraint. The reversible control of the in-plane strain in this layered-perovskite thin film demonstrates a new pathway to integrate mechanical deformation with nanoscale electronic and/or magnetoelectronic applications.

  10. Local lattice distortions and thermal transport in perovskite manganites

    SciTech Connect

    Cohn, J.L.; Neumeier, J.J.; Popoviciu, C.P.; McClellan, K.J.; Leventouri, T.

    1997-10-01

    Measurements of thermal conductivity versus temperature and magnetic field are reported for perovskite manganites that exhibit ferromagnetic (FM), charge-ordering (CO), antiferromagnetic, and/or structural phase transitions. The data reveal a dominant lattice contribution to the heat conductivity with {kappa}{approximately}1{minus}2 W/mK near room temperature. The rather low values, implying a phonon mean free path on the order of a lattice spacing, are shown to correlate with static local distortions of the MnO{sub 6} octahedra. Modifications of the local structure are responsible for abrupt anomalies in the zero-field {kappa} at the FM, CO, and structural transitions, and for colossal magnetothermal resistance near the FM transition. {copyright} {ital 1997} {ital The American Physical Society}

  11. Thermochemistry of Multiferroic Organic-Inorganic Hybrid Perovskites [(CH3)2NH2][M(HCOO)3] (M = Mn, Co, Ni, and Zn).

    PubMed

    Nagabhushana, G P; Shivaramaiah, Radha; Navrotsky, Alexandra

    2015-08-19

    Organic-inorganic hybrid materials have enormous potential for applications in catalysis, gas storage, sensors, drug delivery, and energy generation, among others. A class of hybrid materials adopts the ABX3 perovskite topology. We report here the synthesis and characterization of an isostructural series of dense hybrid perovskites, [(CH3)2NH2][M(HCOO)3], with M = Mn, Co, Ni, and Zn. These compounds have shown promising multiferroic behavior. Understanding their stability is crucial for their practical application. We report their formation enthalpies based on direct measurement by room-temperature acid solution calorimetry. The enthalpy of formation of this dimethylammonium metal formate series becomes less exothermic in the order Mn, Zn, Co, Ni. The stability of the hybrid perovskite decreases as the tolerance factor increases, unlike trends seen in inorganic perovskites. However, the trends are similar to those seen in a number of ternary transition metal oxides, suggesting that specific bonding interactions rather than geometric factors dominate the energetics.

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

    SciTech Connect

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

    2016-09-05

    Requisite to growing stoichiometric perovskite thin films of the solid-solution A′{sub 1-x}A{sub x}BO{sub 3} by hybrid molecular beam epitaxy is understanding how the growth conditions interpolate between the end members A'BO{sub 3} and ABO{sub 3}, which can be grown in a self-regulated fashion, but under different conditions. Using the example of La{sub 1-x}Sr{sub x}VO{sub 3}, the two-dimensional growth parameter space that is spanned by the flux of the metal-organic precursor vanadium oxytriisopropoxide and composition, x, was mapped out. The evolution of the adsorption-controlled growth window was obtained using a combination of X-ray diffraction, atomic force microscopy, reflection high-energy electron-diffraction (RHEED), and Rutherford backscattering spectroscopy. It is found that the stoichiometric growth conditions can be mapped out quickly with a single calibration sample using RHEED. Once stoichiometric conditions have been identified, the out-of-plane lattice parameter can be utilized to precisely determine the composition x. This strategy enables the identification of growth conditions that allow the deposition of stoichiometric perovskite oxide films with random A-site cation mixing, which is relevant to a large number of perovskite materials with interesting properties, e.g., high-temperature superconductivity and colossal magnetoresistance, that emerge in solid solution A′{sub 1-x}A{sub x}BO{sub 3}.

  13. First-principles exploration of ferromagnetic and ferroelectric double-perovskite transition-metal oxides

    NASA Astrophysics Data System (ADS)

    Uratani, Y.; Shishidou, T.; Ishii, F.; Oguchi, T.

    2006-08-01

    Possible ferromagnetic and ferroelectric phases are explored for bismuth transition-metal oxides with double-perovskite structure A2BB‧O6 on the basis of first-principles calculations within the local spin-density approximation (LSDA) and generalized gradient approximation (GGA). It is found that a lattice instability of the cubic to a non-centrosymmetric phase always happens in the all cases of lead and bismuth perovskite oxides with the 3d transition-metal ions at the B site. Placing bismuth ion at the A site in the double-perovskite structure, several sets of the 3d transition-metal ions are selected according to their total valence sum and the Goodenough-Kanamori rule for the superexchange coupling. Ferromagnetic solutions are actually obtained both within LSDA and GGA for Bi2CrFeO6, Bi2MnNiO6 and Bi2CrCuO6. For non-centrosymmetric monoclinic Bi2MnNiO6, the ferromagnetic and ferroelectric phase has the spin magnetic moment of 5μB and the electric polarization of 28 μC/cm2.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

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

    SciTech Connect

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

    2015-10-15

    The thermal evolution of the crystal structure of the prototypical orthorhombic perovskite LaFeO{sub 3} has been studied in detail by powder neutron diffraction in the temperature range 25A-site cation displacements) are shown to display relatively ‘normal’ behavior, increasing with decreasing temperature, which contrasts with the anomalous behavior previously shown by the derivative Bi{sub 0.5}La{sub 0.5}FeO{sub 3}. However, an unexpected behavior is seen in the nature of the intra-octahedral distortion, which is used to rationalize the unique occurrence of a temperature dependent crossover of the a and c unit cell metrics in this compound. - Graphical abstract: The unusual thermal evolution of lattice metrics in the perovskite LaFeO{sub 3} is rationalized from a detailed powder neutron diffraction study. - Highlights: • Crystal structure of the perovskite LaFeO{sub 3} studied in detail by powder neutron diffraction. • Unusual thermal evolution of lattice metrics rationalized. • Contrasting behavior to Bi-doped LaFeO{sub 3}. • Octahedral distortion/tilt parameters explain unusual a and c lattice parameter behavior.

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

    PubMed

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

    2017-09-06

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

  17. Light-Independent Ionic Transport in Inorganic Perovskite and Ultrastable Cs-Based Perovskite Solar Cells.

    PubMed

    Zhou, Wenke; Zhao, Yicheng; Zhou, Xu; Fu, Rui; Li, Qi; Zhao, Yao; Liu, Kaihui; Yu, Dapeng; Zhao, Qing

    2017-09-07

    Due to light-induced effects in CH3NH3-based perovskites, such as ion migration, defects formation, and halide segregation, the degradation of CH3NH3-based perovskite solar cells under maximum power point is generally implicated. Here we demonstrated that the effect of light-enhanced ion migration in CH3NH3PbI3 can be eliminated by inorganic Cs substitution, leading to an ultrastable perovskite solar cell. Quantitatively, the ion migration barrier for CH3NH3PbI3 is 0.62 eV under dark conditions, larger than that of CsPbI2Br (0.45 eV); however, it reduces to 0.07 eV for CH3NH3PbI3 under illumination, smaller than that for CsPbI2Br (0.43 eV). Meanwhile, photoinduced halide segregation is also suppressed in Cs-based perovskites. Cs-based perovskite solar cells retained >99% of the initial efficiency (10.3%) after 1500 h of maximum power point tracking under AM1.5G illumination, while CH3NH3PbI3 solar cells degraded severely after 50 h of operation. Our work reveals an uncovered mechanism for stability improvement by inorganic cation substitution in perovskite-based optoelectronic devices.

  18. Magnetic and charge ordering in nanosized manganites

    SciTech Connect

    Zhang, T. Wang, X. P.; Fang, Q. F.; Li, X. G.

    2014-09-15

    Perovskite manganites exhibit a wide range of functional properties, such as colossal magneto-resistance, magnetocaloric effect, multiferroic property, and some interesting physical phenomena including spin, charge, and orbital ordering. Recent advances in science and technology associated with perovskite oxides have resulted in the feature sizes of microelectronic devices down-scaling into nanoscale dimensions. The nanoscale perovskite manganites display novel magnetic and electronic properties that are different from their bulk and film counterparts. Understanding the size effects of perovskite manganites at the nanoscale is of importance not only for the fundamental scientific research but also for developing next generation of electronic and magnetic nanodevices. In this paper, the current understanding and the fundamental issues related to the size effects on the magnetic properties and charge ordering in manganites are reviewed, which covers lattice structure, magnetic and electronic properties in both ferromagnetic and antiferromagnetic based manganites. In addition to review the literatures, this article identifies the promising avenues for the future research in this area.

  19. Magnetic and charge ordering in nanosized manganites

    NASA Astrophysics Data System (ADS)

    Zhang, T.; Wang, X. P.; Fang, Q. F.; Li, X. G.

    2014-09-01

    Perovskite manganites exhibit a wide range of functional properties, such as colossal magneto-resistance, magnetocaloric effect, multiferroic property, and some interesting physical phenomena including spin, charge, and orbital ordering. Recent advances in science and technology associated with perovskite oxides have resulted in the feature sizes of microelectronic devices down-scaling into nanoscale dimensions. The nanoscale perovskite manganites display novel magnetic and electronic properties that are different from their bulk and film counterparts. Understanding the size effects of perovskite manganites at the nanoscale is of importance not only for the fundamental scientific research but also for developing next generation of electronic and magnetic nanodevices. In this paper, the current understanding and the fundamental issues related to the size effects on the magnetic properties and charge ordering in manganites are reviewed, which covers lattice structure, magnetic and electronic properties in both ferromagnetic and antiferromagnetic based manganites. In addition to review the literatures, this article identifies the promising avenues for the future research in this area.

  20. Formation enthalpies of LaLn'O3 (Ln'=Ho, Er, Tm and Yb) interlanthanide perovskites

    NASA Astrophysics Data System (ADS)

    Qi, Jianqi; Guo, Xiaofeng; Mielewczyk-Gryn, Aleksandra; Navrotsky, Alexandra

    2015-07-01

    High-temperature oxide melt solution calorimetry using 3Na2O·MoO3 at 802 °C was performed for interlanthanide perovskites LaLn'O3 (Ln'=Ho, Er, Tm and Yb) and lanthanide oxides (La2O3, Ho2O3, Er2O3, Tm2O3 and Yb2O3). The enthalpies of formation of these interlanthanide perovskites from binary lanthanide oxides at room temperature (25 °C) were determined to be -8.3±3.4 kJ/mol for LaHoO3, -9.9±3.0 kJ/mol for LaErO3, -10.8±2.7 kJ/mol for LaTmO3 and -12.3±2.9 kJ/mol for LaYbO3. There is a roughly linear relationships between these enthalpy values and the tolerance factor for these and for other LaM3+O3 (M=In, Sc, Ga, Al, Fe and Cr) perovskites, confirming that the distortion of the perovskites as results from ionic radius difference of A-site and B-site cations, is the main factor determining the stability of these compounds.

  1. Thermodynamic stability of perovskites and related compounds in some alkaline earth-transition metal-oxygen systems

    NASA Astrophysics Data System (ADS)

    Yokokawa, Harumi; Sakai, Natsuko; Kawada, Tatsuya; Dokiya, Masayuki

    1991-09-01

    The thermodynamic properties of some alkaline earth ( A)-transition metal ( M) perovskites and K 2NiF 4 compounds have been collected, analyzed, and utilized to examine their stabilities by constructing the chemical potential diagrams of a log [ {a(A)}/{a(M)}] vs log P(O 2) plot. A thermodynamic analysis was performed on the dissociation reaction of K 2NiF 4 compounds ( A2MO 4) into perovskites ( AMO 3) and alkaline earth oxides ( AO) using empirical correlations between stabilization energy and tolerance factor. It has been found that the softness of calcium ions, which shrink markedly with decreasing coordination number from 12 to 9, makes the calcium K 2NiF 4 compounds (Ca 2MO 4) relatively less stable with increasing radius of the transition metal ions, r( M4+). This destabilization related to the coordination-number-dependent radii implies that when compared with the strontium perovskites, the calcium analogous perovskites may have a smaller number of oxygen vacancies, because the formation of oxygen vacancies should be accompanied with a decrease in coordination number of A-site ions.

  2. Prospects of e-beam evaporated molybdenum oxide as a hole transport layer for perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Ali, F.; Khoshsirat, N.; Duffin, J. L.; Wang, H.; Ostrikov, K.; Bell, J. M.; Tesfamichael, T.

    2017-09-01

    Perovskite solar cells have emerged as one of the most efficient and low cost technologies for delivering of solar electricity due to their exceptional optical and electrical properties. Commercialization of the perovskite solar cells is, however, limited because of the higher cost and environmentally sensitive organic hole transport materials such as spiro-OMETAD and PEDOT:PSS. In this study, an empirical simulation was performed using the Solar Cell Capacitance Simulator software to explore the MoOx thin film as an alternative hole transport material for perovskite solar cells. In the simulation, properties of MoOx thin films deposited by the electron beam evaporation technique from high purity (99.99%) MoO3 pellets at different substrate temperatures (room temperature, 100 °C and 200 °C) were used as input parameters. The films were highly transparent (>80%) and have low surface roughness (≤2 nm) with bandgap energy ranging between 3.75 eV and 3.45 eV. Device simulation has shown that the MoOx deposited at room temperature can work in both the regular and inverted structures of the perovskite solar cell with a promising efficiency of 18.25%. Manufacturing of the full device is planned in order to utilize the MoOx as an alternative hole transport material for improved performance, good stability, and low cost of the perovskite solar cell.

  3. Controllable Growth of Perovskite Films by Room-Temperature Air Exposure for Efficient Planar Heterojunction Photovoltaic Cells

    SciTech Connect

    Yang, Bin; Dyck, Ondrej; Poplawsky, Jonathan; Keum, Jong; Das, Sanjib; Puretzky, Alexander; Aytug, Tolga; Joshi, Pooran C.; Rouleau, Christopher M.; Duscher, Gerd; Geohegan, David B.; Xiao, Kai

    2015-12-01

    A two-step-solution-processing approach has been established to grow void-free perovskite films for low-cost and high-performance planar heterojunction photovoltaic devices. We generally applied a high-temperature thermal annealing treatment in order to drive the diffusion of CH3NH3I precursor molecules into the compact PbI2 layer to form perovskite films. But, thermal annealing for extended periods would lead to degraded device performance due to the defects generated by decomposition of perovskite into PbI2. In this work, we explored a controllable layer-by-layer spin-coating method to grow bilayer CH3NH3I/PbI2 films, and then drive the interdiffusion between PbI2 and CH3NH3I layers by a simple room-temperature-air-exposure for making well-oriented, highly-crystalline perovskite films without thermal annealing. This high degree of crystallinity resulted in a carrier diffusion length of ~ 800 nm and high device efficiency of 15.6%, which is comparable to the reported values from thermally-annealed perovskite films based counterparts. Finally, the simplicity and high device performance of this processing approach is highly promising for direct integration into industrial-scale device manufacture.

  4. Controllable Growth of Perovskite Films by Room-Temperature Air Exposure for Efficient Planar Heterojunction Photovoltaic Cells

    DOE PAGES

    Yang, Bin; Dyck, Ondrej; Poplawsky, Jonathan; ...

    2015-12-01

    A two-step-solution-processing approach has been established to grow void-free perovskite films for low-cost and high-performance planar heterojunction photovoltaic devices. We generally applied a high-temperature thermal annealing treatment in order to drive the diffusion of CH3NH3I precursor molecules into the compact PbI2 layer to form perovskite films. But, thermal annealing for extended periods would lead to degraded device performance due to the defects generated by decomposition of perovskite into PbI2. In this work, we explored a controllable layer-by-layer spin-coating method to grow bilayer CH3NH3I/PbI2 films, and then drive the interdiffusion between PbI2 and CH3NH3I layers by a simple room-temperature-air-exposure for makingmore » well-oriented, highly-crystalline perovskite films without thermal annealing. This high degree of crystallinity resulted in a carrier diffusion length of ~ 800 nm and high device efficiency of 15.6%, which is comparable to the reported values from thermally-annealed perovskite films based counterparts. Finally, the simplicity and high device performance of this processing approach is highly promising for direct integration into industrial-scale device manufacture.« less

  5. Nanoscale study of perovskite solar cells for efficient charge transport

    NASA Astrophysics Data System (ADS)

    Adhikari, Nirmal

    The effect of temperature, humidity and water on the grain boundary potential and charge transport within the grains of pervoskite films prepared by sequential deposition technique. Grain boundary potential of perovskite films exhibited variation in electrical properties with humidity level, temperature and water concentration in methyl ammonium iodide solution. X-ray diffraction (XRD) indicates the formation of PbI2 phase in perovskite film with increasing temperature, humidity and adding larger quantity of water in methyl ammonium iodide solution. It is found that optimum amount of lead iodide helps for the passivation of perovskite film. Spatial mapping of surface potential in the perovskite film exhibits higher positive potential at grain boundaries compared to the surface of the grains. Back recombination barrier between TiO2- perovskite increases to 378 meV for perovskite film annealed at 100 ºC for 15 min. Grain boundary potential barrier were found to increase from ˜35 meV to 80 meV for perovskite film exposed to 75% RH level compared to perovskite film kept inside glove box. Optimum amount of water which increases the solar cell performance by increasing the crystallinity of perovskite film was found to be 5% by volume of IPA. Results show strong correlation between temperature, humidity level, electronic grain boundary properties and device performance of perovskite solar cells.

  6. Material and Device Stability in Perovskite Solar Cells.

    PubMed

    Kim, Hui-Seon; Seo, Ja-Young; Park, Nam-Gyu

    2016-09-22

    Organic-inorganic halide perovskite solar cells have attracted great attention because of their superb efficiency reaching 22 % and low-cost, facile fabrication processing. Nevertheless, stability issues in perovskite solar cells seem to block further advancements toward commercialization. Thus, device stability is one of the important topics in perovskite solar cell research. In the beginning, the poor moisture resistivity of the perovskite layer was considered as a main problem that hindered further development of perovskite solar cells, which encouraged engineering of the perovskite or protection of the perovskite by a buffer layer. Soon after, other parameters affecting long-term stability were sequentially found and various attempts have been made to enhance intrinsic and extrinsic stability. Here we review the recent progresses addressing stability issues in perovskite solar cells. In this report, we investigated factors affecting stability from material and device points of view. To gain a better understanding of the stability of the bulk perovskite material, decomposition mechanisms were investigated in relation to moisture, photons, and heat. Stability of full device should also be carefully examined because its stability is dependent not only on bulk perovskite but also on the interfaces and selective contacts. In addition, ion migration and current-voltage hysteresis were found to be closely related to stability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Spin-phonon coupling in Gd(Co1/2Mn1/2)O3 perovskite

    NASA Astrophysics Data System (ADS)

    Silva, R. X.; Reichlova, H.; Marti, X.; Barbosa, D. A. B.; Lufaso, M. W.; Araujo, B. S.; Ayala, A. P.; Paschoal, C. W. A.

    2013-11-01

    We have investigated the temperature-dependent Raman-active phonons and the magnetic properties of Gd(Co1/2Mn1/2)O3 perovskite ceramics in the temperature range from 40 K to 300 K. The samples crystallized in an orthorhombic distorted simple perovskite, whose symmetry belongs to the Pnma space group. The data reveal spin-phonon coupling near the ferromagnetic transition occurring at around 120 K. The correlation of the Raman and magnetization data suggests that the structural order influences the magnitude of the spin-phonon coupling.

  8. Anomalous Alloy Properties in Mixed Halide Perovskites.

    PubMed

    Yin, Wan-Jian; Yan, Yanfa; Wei, Su-Huai

    2014-11-06

    Engineering halide perovskite through mixing halogen elements, such as CH3NH3PbI3-xClx and CH3NH3PbI3-xBrx, is a viable way to tune its electronic and optical properties. Despite many emerging experiments on mixed halide perovskites, the basic electronic and structural properties of the alloys have not been understood and some crucial questions remain, for example, how much Cl can be incorporated into CH3NH3PbI3 is still unclear. In this Letter, we chose CsPbX3 (X = I, Br, Cl) as an example and use a first-principle calculation together with cluster-expansion methods to systematically study the structural, electronic, and optical properties of mixed halide perovskites and find that unlike conventional semiconductor alloys, they exhibit many anomalous alloy properties such as small or even negative formation energies at some concentrations and negligible or even negative band gap bowing parameters at high temperature. We further show that mixed-(I,Cl) perovskite is hard to form at temperature below 625 K, whereas forming mixed-(Br,Cl) and (I,Br) alloys are easy at room temperature.

  9. 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

  10. Research progress on electronic phase separation in low-dimensional perovskite manganite nanostructures.

    PubMed

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

    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

  11. 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

  12. Low surface recombination velocity in solution-grown CH3NH3PbBr3 perovskite single crystal

    PubMed Central

    Yang, Ye; Yan, Yong; Yang, Mengjin; Choi, Sukgeun; Zhu, Kai; Luther, Joseph M.; Beard, Matthew C.

    2015-01-01

    Organic-inorganic hybrid perovskites are attracting intense research effort due to their impressive performance in solar cells. While the carrier transport parameters such as mobility and bulk carrier lifetime shows sufficient characteristics, the surface recombination, which can have major impact on the solar cell performance, has not been studied. Here we measure surface recombination dynamics in CH3NH3PbBr3 perovskite single crystals using broadband transient reflectance spectroscopy. The surface recombination velocity is found to be 3.4±0.1 × 103 cm s−1, ∼2–3 orders of magnitude lower than that in many important unpassivated semiconductors employed in solar cells. Our result suggests that the planar grain size for the perovskite thin films should be larger than ∼30 μm to avoid the influence of surface recombination on the effective carrier lifetime. PMID:26245855

  13. Low Surface Recombination Velocity in Solution-Grown CH3NH3PbBr3 Perovskite Single Crystal

    DOE PAGES

    Yang, Ye; Yan, Yong; Yang, Mengjin; ...

    2015-08-06

    Organic-inorganic hybrid perovskites are attracting intense research effort due to their impressive performance in solar cells. While the carrier transport parameters such as mobility and bulk carrier lifetime shows sufficient characteristics, the surface recombination, which can have major impact on the solar cell performance, has not been studied. Here we measure surface recombination dynamics in CH3NH3PbBr3 perovskite single crystals using broadband transient reflectance spectroscopy. The surface recombination velocity is found to be 3.4±0.1 103 cm s-1, B2–3 orders of magnitude lower than that in many important unpassivated semiconductors employed in solar cells. Our result suggests that the planar grain sizemore » for the perovskite thin films should be larger thanB30 mm to avoid the influence of surface recombination on the effective carrier lifetime.« less

  14. High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites

    SciTech Connect

    Sutter-Fella, Carolin M.; Li, Yanbo; Amani, Matin; Ager, Joel W.; Toma, Francesca M.; Yablonovitch, Eli; Sharp, Ian D.; Javey, Ali

    2015-12-21

    Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH3NH3PbI3-xBrx perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamic range. The internal luminescence quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ Eg ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells. (Figure Presented).

  15. Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials

    DOE PAGES

    Neukirch, Amanda J.; Nie, Wanyi; Blancon, Jean-Christophe; ...

    2016-05-25

    Solution-processed organometallic perovskites have rapidly developed into a top candidate for the active layer of photovoltaic devices. In spite of the remarkable progress associated with perovskite materials, many questions about the fundamental photophysical processes taking place in these devices, remain open. High on the list of unexplained phenomena are very modest mobilities despite low charge carrier effective masses. Moreover, experiments elucidate unique degradation of photocurrent affecting stable operation of perovskite solar cells. These puzzles suggest that, while ionic hybrid perovskite devices may have efficiencies on par with conventional Si and GaAs devices, they exhibit more complicated charge transport phenomena. Wemore » report the results from an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies using both periodic boundary conditions and isolated structures. Using the hybrid density functional theory, we found that volumetric strain in a CsPbI3 cluster creates a polaron with binding energy of around 300 and 900 meV for holes and electrons, respectively. In the MAPbI3 (MA = CH3NH3) cluster, both volumetric strain and MA reorientation effects lead to larger binding energies at around 600 and 1300 meV for holes and electrons, respectively. Such large reorganization energies suggest appearance of small polarons in organometallic perovskite materials. Furthermore, the fact that both volumetric lattice strain and MA molecular rotational degrees of freedom can cooperate to create and stabilize polarons indicates that in order to mitigate this problem, formamidinium (FA = HC(NH2)2) and cesium (Cs) based crystals and alloys, are potentially better materials for solar cell and other optoelectronic applications.« less

  16. Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials

    SciTech Connect

    Neukirch, Amanda J.; Nie, Wanyi; Blancon, Jean-Christophe; Appavoo, Kannatassen; Tsai, Hsinhan; Sfeir, Matthew Y.; Katan, Claudine; Pedesseau, Laurent; Even, Jacky; Crochet, Jared J.; Gupta, Gautam; Mohite, Aditya D.; Tretiak, Sergei

    2016-05-25

    Solution-processed organometallic perovskites have rapidly developed into a top candidate for the active layer of photovoltaic devices. In spite of the remarkable progress associated with perovskite materials, many questions about the fundamental photophysical processes taking place in these devices, remain open. High on the list of unexplained phenomena are very modest mobilities despite low charge carrier effective masses. Moreover, experiments elucidate unique degradation of photocurrent affecting stable operation of perovskite solar cells. These puzzles suggest that, while ionic hybrid perovskite devices may have efficiencies on par with conventional Si and GaAs devices, they exhibit more complicated charge transport phenomena. We report the results from an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies using both periodic boundary conditions and isolated structures. Using the hybrid density functional theory, we found that volumetric strain in a CsPbI3 cluster creates a polaron with binding energy of around 300 and 900 meV for holes and electrons, respectively. In the MAPbI3 (MA = CH3NH3) cluster, both volumetric strain and MA reorientation effects lead to larger binding energies at around 600 and 1300 meV for holes and electrons, respectively. Such large reorganization energies suggest appearance of small polarons in organometallic perovskite materials. Furthermore, the fact that both volumetric lattice strain and MA molecular rotational degrees of freedom can cooperate to create and stabilize polarons indicates that in order to mitigate this problem, formamidinium (FA = HC(NH2)2) and cesium (Cs) based crystals and alloys, are potentially better materials for solar cell and other optoelectronic applications.

  17. High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites

    DOE PAGES

    Sutter-Fella, Carolin M.; Li, Yanbo; Amani, Matin; ...

    2015-12-21

    Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH3NH3PbI3-xBrx perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamic range. The internal luminescencemore » quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ Eg ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells. (Figure Presented).« less

  18. Polaron Stabilization by Cooperative Lattice Distortion and Cation Rotations in Hybrid Perovskite Materials

    SciTech Connect

    Neukirch, Amanda J.; Nie, Wanyi; Blancon, Jean-Christophe; Appavoo, Kannatassen; Tsai, Hsinhan; Sfeir, Matthew Y.; Katan, Claudine; Pedesseau, Laurent; Even, Jacky; Crochet, Jared J.; Gupta, Gautam; Mohite, Aditya D.; Tretiak, Sergei

    2016-05-25

    Solution-processed organometallic perovskites have rapidly developed into a top candidate for the active layer of photovoltaic devices. In spite of the remarkable progress associated with perovskite materials, many questions about the fundamental photophysical processes taking place in these devices, remain open. High on the list of unexplained phenomena are very modest mobilities despite low charge carrier effective masses. Moreover, experiments elucidate unique degradation of photocurrent affecting stable operation of perovskite solar cells. These puzzles suggest that, while ionic hybrid perovskite devices may have efficiencies on par with conventional Si and GaAs devices, they exhibit more complicated charge transport phenomena. We report the results from an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies using both periodic boundary conditions and isolated structures. Using the hybrid density functional theory, we found that volumetric strain in a CsPbI3 cluster creates a polaron with binding energy of around 300 and 900 meV for holes and electrons, respectively. In the MAPbI3 (MA = CH3NH3) cluster, both volumetric strain and MA reorientation effects lead to larger binding energies at around 600 and 1300 meV for holes and electrons, respectively. Such large reorganization energies suggest appearance of small polarons in organometallic perovskite materials. Furthermore, the fact that both volumetric lattice strain and MA molecular rotational degrees of freedom can cooperate to create and stabilize polarons indicates that in order to mitigate this problem, formamidinium (FA = HC(NH2)2) and cesium (Cs) based crystals and alloys, are potentially better materials for solar cell and other optoelectronic applications.

  19. Liquid-solid directional composites and anisotropic dipolar phases of polar nanoregions in disordered perovskites.

    PubMed

    Parravicini, Jacopo; DelRe, Eugenio; Agranat, Aharon J; Parravicini, Gianbattista

    2017-07-13

    Using temperature-resolved dielectric spectroscopy in the range of 75-320 K we have inspected the solid-like and liquid-like arrangements of nanometric dipoles (polar nanoregions) embedded in sodium-enriched potassium-tantalate-niobate (KNTN), a chemically-substituted complex perovskite crystal hosting inherent substitutional disorder. The study of order versus direction is carried out using Fröhlich entropy measurements and indicates the presence of four long-range symmetry phases, two of which are found to display profoundly anisotropic features. Exotic phases are found for which the dipoles at one fixed temperature manifest a liquid reorientational response along one crystal axis and a solid-like behavior along another axis. The macroscopic anisotropy observed in the sequence of different phases is found to match a microscopic order-disorder sequence typical of nominally pure perovskites. Moreover, experimental demonstration of the onset of a frozen state above transitions is provided.

  20. Phase separation and size effects in Pr(0.70)Ba(0.30)MnO(3+δ) perovskite manganites.

    PubMed

    Trukhanov, S V; Trukhanov, A V; Botez, C E; Adair, A H; Szymczak, H; Szymczak, R

    2007-07-04

    The crystal structure and magnetotransport properties of the A-site ionic ordered state in Pr(0.70)Ba(0.30)MnO(3+δ) (δ = 0, 0.025) have been investigated. It is shown that such a state can be formed in complex manganites with cation ratios [Formula: see text] by using a 'two-step' reduction-reoxidization method. The parent A-site ionic disordered Pr(0.70)Ba(0.30)MnO(3+δ) (δ = 0) compound is an orthorhombic (SG = Imma, Z = 4) ferromagnet with Curie temperature T(C)≈173 K and ground-state spontaneous magnetic moment σ(S)∼3.70 µ(B)/f.u. It exhibits two metal-insulator transitions, at T(I)∼128 K and T(II)∼173 K, as well as two peaks of magnetoresistance ∼74% and ∼79% in a field of 50 kOe. The parent A-site ionic disordered Pr(0.70)Ba(0.30)MnO(3+δ) (δ = 0) sample used in our studies has an average grain size [Formula: see text]. Successive annealing of this sample in vacuum P[O(2)]≈10(-4) Pa and then in air at T = 800 °C leads to the destruction of its initial grain structure and to its chemical separation into two phases: (i) oxygen stoichiometric A-site ordered PrBaMn(2)O(6) with a tetragonal (SG = P4/mmm, Z = 2) perovskite-like unit cell and Curie temperature T(C)≈313 K and (ii) oxygen superstoichiometric A-site disordered Pr(0.90)Ba(0.10)MnO(3.05) with an orthorhombic (SG = Pnma, Z = 4) perovskite-like unit cell and Curie temperature T(C)≈133 K. This processed sample has a spontaneous magnetic moment σ(S)∼2.82 µ(B)/f.u. in its ground state, and σ(S)∼0.59 μ(B)/f.u. at T∼300 K. It also exhibits a magnetoresistance of ∼14% at ∼313 K in a field of 50 kOe. This processed sample has a reduced average grain size [Formula: see text] nm. The two magnetic phases, Pr(0.90)Ba(0.10)MnO(3.05) and PrBaMn(2)O(6), are exchange-coupled. For Pr(0.90)Ba(0.10)MnO(3.05) the temperature hysteresis is ∼22 K in a field of 10 Oe and ∼5 K in a field of 1 kOe. The observed magnetic properties are interpreted in terms of chemical