Science.gov

Sample records for a-site substituted perovskite

  1. 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.

  2. 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.

  3. 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.

  4. 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).

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Stabilized wide bandgap perovskite solar cells by tin substitution

    DOE PAGES

    Yang, Zhibin; Rajagopal, Adharsh; Jo, Sae Byeok; ...

    2016-11-16

    Wide bandgap MAPb(I1-yBry)3 perovskites show promising potential for application in tandem solar cells. However, unstable photovoltaic performance caused by phase segregation has been observed under illumination when y is above 0.2. Herein, we successfully demonstrate stabilization of the I/Br phase by partially replacing Pb2+ with Sn2+ and verify this stabilization with X-ray diffractometry and transient absorption spectroscopy. The resulting MAPb0.75Sn0.25(I1-yBry)3 perovskite solar cells show stable photovoltaic performance under continuous illumination. Among these cells, the one based on MAPb0.75Sn0.25(I0.4Br0.6)3 perovskite shows the highest efficiency of 12.59% with a bandgap of 1.73 eV, which make it a promising wide bandgap candidate formore » application in tandem solar cells. The engineering of internal bonding environment by partial Sn substitution is believed to be the main reason for making MAPb0.75Sn0.25(I1-yBry)3 perovskite less vulnerable to phase segregation during the photostriction under illumination. Furthermore, this study establishes composition engineering of the metal site as a promising strategy to impart phase stability in hybrid perovskites under illumination.« less

  10. Stabilized Wide Bandgap Perovskite Solar Cells by Tin Substitution.

    PubMed

    Yang, Zhibin; Rajagopal, Adharsh; Jo, Sae Byeok; Chueh, Chu-Chen; Williams, Spencer; Huang, Chun-Chih; Katahara, John K; Hillhouse, Hugh W; Jen, Alex K-Y

    2016-12-14

    Wide bandgap MAPb(I1-yBry)3 perovskites show promising potential for application in tandem solar cells. However, unstable photovoltaic performance caused by phase segregation has been observed under illumination when y is above 0.2. Herein, we successfully demonstrate stabilization of the I/Br phase by partially replacing Pb(2+) with Sn(2+) and verify this stabilization with X-ray diffractometry and transient absorption spectroscopy. The resulting MAPb0.75Sn0.25(I1-yBry)3 perovskite solar cells show stable photovoltaic performance under continuous illumination. Among these cells, the one based on MAPb0.75Sn0.25(I0.4Br0.6)3 perovskite shows the highest efficiency of 12.59% with a bandgap of 1.73 eV, which make it a promising wide bandgap candidate for application in tandem solar cells. The engineering of internal bonding environment by partial Sn substitution is believed to be the main reason for making MAPb0.75Sn0.25(I1-yBry)3 perovskite less vulnerable to phase segregation during the photostriction under illumination. Therefore, this study establishes composition engineering of the metal site as a promising strategy to impart phase stability in hybrid perovskites under illumination.

  11. 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.

  12. Stabilized wide bandgap perovskite solar cells by tin substitution

    SciTech Connect

    Yang, Zhibin; Rajagopal, Adharsh; Jo, Sae Byeok; Chueh, Chu -Chen; Williams, Spencer; Huang, Chun -Chih; Katahara, John K.; Hillhouse, Hugh W.; Jen, Alex K. -Y.

    2016-11-16

    Wide bandgap MAPb(I1-yBry)3 perovskites show promising potential for application in tandem solar cells. However, unstable photovoltaic performance caused by phase segregation has been observed under illumination when y is above 0.2. Herein, we successfully demonstrate stabilization of the I/Br phase by partially replacing Pb2+ with Sn2+ and verify this stabilization with X-ray diffractometry and transient absorption spectroscopy. The resulting MAPb0.75Sn0.25(I1-yBry)3 perovskite solar cells show stable photovoltaic performance under continuous illumination. Among these cells, the one based on MAPb0.75Sn0.25(I0.4Br0.6)3 perovskite shows the highest efficiency of 12.59% with a bandgap of 1.73 eV, which make it a promising wide bandgap candidate for application in tandem solar cells. The engineering of internal bonding environment by partial Sn substitution is believed to be the main reason for making MAPb0.75Sn0.25(I1-yBry)3 perovskite less vulnerable to phase segregation during the photostriction under illumination. Furthermore, this study establishes composition engineering of the metal site as a promising strategy to impart phase stability in hybrid perovskites under illumination.

  13. 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.

  14. Transition metal-substituted lead halide perovskite absorbers

    DOE PAGES

    Sampson, M. D.; Park, J. S.; Schaller, R. D.; ...

    2017-01-27

    Here, lead halide perovskites have proven to be a versatile class of visible light absorbers that allow rapid access to the long minority carrier lifetimes and diffusion lengths desirable for traditional single-junction photovoltaics. We explore the extent to which the attractive features of these semiconductors may be extended to include an intermediate density of states for future application in multi-level solar energy conversion systems capable of exceeding the Shockley–Queisser limit. We computationally and experimentally explore the substitution of transition metals on the Pb site of MAPbX3 (MA = methylammonium, X = Br or Cl) to achieve a tunable density ofmore » states within the parent gap. Computational screening identified both Fe- and Co-substituted MAPbBr3 as promising absorbers with a mid-gap density of states, and the later films were synthesized via conventional solution-based processing techniques. First-principles density functional theory (DFT) calculations support the existence of mid-gap states upon Co incorporation and enhanced sub-gap absorption, which are consistent with UV-visible-NIR absorption spectroscopy. Strikingly, steady state and time-resolved PL studies reveal no sign of self-quenching for Co-substitution up to 25%, which suggest this class of materials to be a worthy candidate for future application in intermediate band photovoltaics.« less

  15. 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).

  16. (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.

  17. 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.

  18. 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.

  19. 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.

  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. 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.

  2. 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

  3. 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.

  4. Stability of Perovskite Solar Cells: A Prospective on the Substitution of the A Cation and X Anion.

    PubMed

    Wang, Ze; Shi, Zejiao; Li, Taotao; Chen, Yonghua; Huang, Wei

    2017-01-24

    In recent years, organometal trihalide perovskites have emerged as promising materials for low-cost, flexible, and highly efficient solar cells. Despite their processing advantages, before the technology can be commercialized the poor stability of the organic-inorganic hybrid perovskite materials with regard to humidity, heat, light, and oxygen has be to overcome. Herein, we distill the current state-of-the-art and highlight recent advances in improving the chemical stability of perovskite materials by substitution of the A-cation and X-anion. Our hope is to pave the way for the rational design of perovskite materials to realize perovskite solar cells with unprecedented improvement in stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. An oxygen-deficiency modulated multiferroic: Cobalt-substituted perovskite

    NASA Astrophysics Data System (ADS)

    Florez, Juan Manuel

    In this work, we use density functional theory to model recently demonstrated room temperature ferromagnetism and ferroelectricity in polycrystalline and single crystal Cobalt-substituted SrTiO3 thin films (SrTi0.70Co0.30O3-d), deposited at different oxygen pressures to change their oxygen vacancy concentration. The modeling indicates an origin for both magnetism and electric polarization in the interactions between oxygen vacancies and the B-site cations. The magnetization saturation increases with the oxygen deficiency as a result of valence spin states changes, which depend on whether the oxygen octahedral of the respective local B-site cations are complete or not. On the other hand, a finite electric polarization appears as a result of a non-centrosymmetric distribution of different resulting local charges and such a polarization increases when the oxygen vacancies increase. Increasing of both order parameters, magnetic and ferroelectric, are analyzed respect to all possible Co-sites and O-vacancies distributions, showing that these results suggest a class of multiferroic materials with properties controlled by their oxygen stoichiometry. Agreement and discrepancies between experiments and modeling are discussed. 1J M Florez and P Vargas thank Fondecyt 1130950 and 11130128, all authors thank the MISTI MIT-Chile, and CAR thanks the (S3TEC) and DoE under DE-SC0001299.

  6. 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.

  7. 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.

  8. Stabilizing Cesium Lead Halide Perovskite Lattice through Mn(II) Substitution for Air-Stable Light-Emitting Diodes.

    PubMed

    Zou, Shenghan; Liu, Yongsheng; Li, Jianhai; Liu, Caiping; Feng, Rui; Jiang, Feilong; Li, Yongxiang; Song, Jizhong; Zeng, Haibo; Hong, Maochun; Chen, Xueyuan

    2017-08-23

    All-inorganic cesium lead halide perovskite (CsPbX3, X = Cl, Br, and I) quantum dots (QDs), possessing high photoluminescence quantum yields and tunable color output, have recently been endowed great promise for high-performance solar cells and light-emitting diodes (LEDs). Although moisture stability has been greatly improved through separating QDs with a SiO2 shell, the practical applications of CsPbX3 QDs are severely restricted by their poor thermal stability, which is associated with the intrinsically low formation energies of perovskite lattices. In this regard, enhancing the formation energies of perovskite lattices of CsPbX3 QDs holds great promise in getting to the root of their poor thermal stability, which hitherto remains untouched. Herein, we demonstrate an effective strategy through Mn(2+) substitution to fundamentally stabilize perovskite lattices of CsPbX3 QDs even at high temperatures up to 200 °C under ambient air conditions. We employ first-principle calculations to confirm that the significantly improved thermal stability and optical performance of CsPbX3:Mn(2+) QDs arise primarily from the enhanced formation energy due to the successful doping of Mn(2+) in CsPbX3 QDs. Benefiting from such an effective substitution strategy, these Mn(2+)-doped CsPbX3 QDs can function well as efficient light emitters toward the fabrication of high-performance perovskite LEDs.

  9. Chemical and electronic characterization of cobalt in a lanthanum perovskite. Effects of strontium substitution

    SciTech Connect

    Hueso, Jose L.; Holgado, Juan P.; Pereniguez, Rosa; Mun, Simon; Salmeron, Miquel; Caballero, Alfonso

    2010-01-15

    Two different cobaltites, LaCoO{sub 3} and La{sub 0.5}Sr{sub 0.5}CoO{sub 3-{delta}}, have been prepared and characterized by means of high energy Co K-edge and low energy O K-edge X-ray absorption spectroscopy (XAS). Even though half of the La(III) is substituted by Sr(II), little or no changes can be detected in the formal oxidation state of cobalt atoms. The presence of strontium cations induces two main effects in the chemical and electronic state of the perovskite. The charge balance with Sr(II) species is reached by the formation of oxygen vacancies throughout the network, which explains the well-known increase in the reactivity of this substituted perovskite. O K-edge XAS experiments show that the Sr(II) species induce the transitions of d electrons of cobalt cations from low to high spin configuration. We propose that this change in spin multiplicity is induced by two cooperative effects: the oxygen vacancies, creating five coordinated cobalt atoms, and the bigger size of Sr(II) cations, aligning the Co-O-Co atoms, and favoring the overlapping of pi-symmetry cobalt and oxygen orbitals, reducing the splitting energy of e{sub g} and t{sub 2g} levels. - Graphical abstract: Change in spin multiplicity induced by the bigger size of Sr(II) cations, aligning the Co-O-Co atoms, and favoring the overlapping of pi-symmetry cobalt and oxygen orbitals.

  10. Fluorine-substituted benzothiadiazole-based hole transport materials for highly efficient planar perovskite solar cells with a FF exceeding 80.

    PubMed

    Wu, Fei; Ji, Yu; Zhong, Cheng; Liu, Yuan; Tan, Luxi; Zhu, Linna

    2017-08-11

    Fluorine-substituted benzothiadiazole (BT) was introduced as a core structure to construct new hole transport materials. Planar perovskite solar cells with conventional materials (CH3NH3PbI3-xClx) were fabricated. The perovskite solar cells using monofluorinated BT exhibit a leading efficiency of 18.54% with a FF as high as 81%.

  11. Synthesis and characterization of substituted garnet and perovskite-based lithium-ion conducting solid electrolytes

    DOE PAGES

    Abreu-Sepúlveda, Maria; Huq, Ashfia; Dhital, Chetan; ...

    2015-09-30

    In this study, titanium, tantalum-substituted Li7La3Zr2-xAxO12 (LLZO, A = Ta, Ti) garnets, and chromium-substituted La(2/3)-xLi3xTi1-yCryO3 (LLTO) perovskites were prepared by a conventional solid-state reaction and the Pechini processes. The desired crystal phases were obtained by varying the calcination temperature and time, as well as the substitution concentration. All samples indicated decomposition of the precursors when heated above 750 °C and formation of the desired phase after heat treatment at higher temperatures. Neutron diffraction data shows the formation of a predominant cubic phase in the case of Ta-LLZO, and monoclinic phase with minor impurity phases for Cr-LLTO. Ionic conductivity for Ti-LLZOmore » (Li7La3Zr1.4Ti0.6O12), Ta-LLZO (Li6.03La3Zr1.533Ta0.46O12), and Cr-LLTO (La(2/3)-xLi3xTi0.9Cr0.1O3) at room temperature were found to be 5.21 × 10–6, 1.01 ×10–6, and 1.2 × 10–4 S cm–1, respectively. The activation energies of the compounds were determined from the Arrhenius plot and were 0.44 eV (Ti0.6-LLZO), 0.54 eV (Ta0.5-LLZO), and 0.20 eV (Cr0.1-LLTO).« less

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

    DOEpatents

    Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

    2010-07-20

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

  13. Tetra methyl substituted Cu(II) phthalocyanine as alternative hole transporting material for organometal halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Sfyri, Georgia; Kumar, Challuri Vijay; Wang, Yu-Long; Xu, Zong-Xiang; Krontiras, C. A.; Lianos, Panagiotis

    2016-01-01

    Copper phthalocyanine is a promising hole transporting material, which can be employed with solid state perovskite solar cells. Tetra methyl substituted copper phthalocyanine was presently studied as a hole transporting material and demonstrated improved performance with respect to unsubstituted copper phthalocyanine. This material shows a strong absorption in the Visible and Near IR part of the electromagnetic spectrum contributing to the absorption of photons. Its LUMO and HOMO level are favourably positioned for injecting electrons and scavenging holes. Methyl substitution facilitates closer molecular packing leading to a stronger extinction coefficient, stronger Ͽ⿿Ͽ interaction and higher charge carrier mobility.

  14. 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.

  15. 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.

  16. Synthesis and characterization of substituted garnet and perovskite-based lithium-ion conducting solid electrolytes

    SciTech Connect

    Abreu-Sepúlveda, Maria; Huq, Ashfia; Dhital, Chetan; Dominique E. Williams; Li, Yunchao; Paranthaman, M. Parans; Zaghib, Karim; Manivannan, A.

    2015-09-30

    In this study, titanium, tantalum-substituted Li7La3Zr2-xAxO12 (LLZO, A = Ta, Ti) garnets, and chromium-substituted La(2/3)-xLi3xTi1-yCryO3 (LLTO) perovskites were prepared by a conventional solid-state reaction and the Pechini processes. The desired crystal phases were obtained by varying the calcination temperature and time, as well as the substitution concentration. All samples indicated decomposition of the precursors when heated above 750 °C and formation of the desired phase after heat treatment at higher temperatures. Neutron diffraction data shows the formation of a predominant cubic phase in the case of Ta-LLZO, and monoclinic phase with minor impurity phases for Cr-LLTO. Ionic conductivity for Ti-LLZO (Li7La3Zr1.4Ti0.6O12), Ta-LLZO (Li6.03La3Zr1.533Ta0.46O12), and Cr-LLTO (La(2/3)-xLi3xTi0.9Cr0.1O3) at room temperature were found to be 5.21 × 10–6, 1.01 ×10–6, and 1.2 × 10–4 S cm–1, respectively. The activation energies of the compounds were determined from the Arrhenius plot and were 0.44 eV (Ti0.6-LLZO), 0.54 eV (Ta0.5-LLZO), and 0.20 eV (Cr0.1-LLTO).

  17. 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.

  18. 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.

  19. A Methoxydiphenylamine-Substituted Carbazole Twin Derivative: An Efficient Hole-Transporting Material for Perovskite Solar Cells.

    PubMed

    Gratia, Paul; Magomedov, Artiom; Malinauskas, Tadas; Daskeviciene, Maryte; Abate, Antonio; Ahmad, Shahzada; Grätzel, Michael; Getautis, Vytautas; Nazeeruddin, Mohammad Khaja

    2015-09-21

    The small-molecule-based hole-transporting material methoxydiphenylamine-substituted carbazole was synthesized and incorporated into a CH3NH3PbI3 perovskite solar cell, which displayed a power conversion efficiency of 16.91%, the second highest conversion efficiency after that of Spiro-OMeTAD. The investigated hole-transporting material was synthesized in two steps from commercially available and relatively inexpensive starting reagents. Various electro-optical measurements (UV/Vis, IV, thin-film conductivity, hole mobility, DSC, TGA, ionization potential) have been carried out to characterize the new hole-transporting material.

  20. 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

  1. Lead-Free Halide Double Perovskites via Heterovalent Substitution of Noble Metals.

    PubMed

    Volonakis, George; Filip, Marina R; Haghighirad, Amir Abbas; Sakai, Nobuya; Wenger, Bernard; Snaith, Henry J; Giustino, Feliciano

    2016-04-07

    Lead-based halide perovskites are emerging as the most promising class of materials for next-generation optoelectronics; however, despite the enormous success of lead-halide perovskite solar cells, the issues of stability and toxicity are yet to be resolved. Here we report on the computational design and the experimental synthesis of a new family of Pb-free inorganic halide double perovskites based on bismuth or antimony and noble metals. Using first-principles calculations we show that this hitherto unknown family of perovskites exhibits very promising optoelectronic properties, such as tunable band gaps in the visible range and low carrier effective masses. Furthermore, we successfully synthesize the double perovskite Cs2BiAgCl6, perform structural refinement using single-crystal X-ray diffraction, and characterize its optical properties via optical absorption and photoluminescence measurements. This new perovskite belongs to the Fm3̅m space group and consists of BiCl6 and AgCl6 octahedra alternating in a rock-salt face-centered cubic structure. From UV-vis and photoluminescence measurements we obtain an indirect gap of 2.2 eV.

  2. 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.

  3. 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.

  4. Theoretical insights into a potential lead-free hybrid perovskite: substituting Pb2+ with Ge2+

    NASA Astrophysics Data System (ADS)

    Sun, Ping-Ping; Li, Quan-Song; Yang, Li-Na; Li, Ze-Sheng

    2016-01-01

    In recent years, perovskite solar cells have been considerably developed, however the lead in the absorber MAPbI3 is a potential threat to the environment. To explore potential alternatives, the structural and electronic properties of MAGeX3 (X = Cl, Br, I) were investigated using different density functional theory methods, including GGA-PBE, PBE-SOC, HSE06 and HSE-SOC. The results implied that MAGeI3 exhibits an analogous band gap, substantial stability, remarkable optical properties, and significant hole and electron conductive behavior compared with the so far widely used absorber MAPbI3. Moreover, the calculations revealed that the energy splitting resulting from the spin-orbit coupling is evident on Pb, moderate on Ge, I and Br, and negligible on Cl. Our work not only sheds some light on screening novel absorbers for perovskite solar cells but also deepens the understanding of these functional materials.In recent years, perovskite solar cells have been considerably developed, however the lead in the absorber MAPbI3 is a potential threat to the environment. To explore potential alternatives, the structural and electronic properties of MAGeX3 (X = Cl, Br, I) were investigated using different density functional theory methods, including GGA-PBE, PBE-SOC, HSE06 and HSE-SOC. The results implied that MAGeI3 exhibits an analogous band gap, substantial stability, remarkable optical properties, and significant hole and electron conductive behavior compared with the so far widely used absorber MAPbI3. Moreover, the calculations revealed that the energy splitting resulting from the spin-orbit coupling is evident on Pb, moderate on Ge, I and Br, and negligible on Cl. Our work not only sheds some light on screening novel absorbers for perovskite solar cells but also deepens the understanding of these functional materials. Electronic supplementary information (ESI) available: Optimized structures of the MAPbI3 and MASnI3 perovskites, band structures of the different

  5. 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

  6. Reversible Changes in Resistance of Perovskite Nickelate NdNiO3 Thin Films Induced by Fluorine Substitution.

    PubMed

    Onozuka, Tomoya; Chikamatsu, Akira; Katayama, Tsukasa; Hirose, Yasushi; Harayama, Isao; Sekiba, Daiichiro; Ikenaga, Eiji; Minohara, Makoto; Kumigashira, Hiroshi; Hasegawa, Tetsuya

    2017-03-08

    Perovskite nickel oxides are of fundamental as well as technological interest because they show large resistance modulation associated with phase transition as a function of the temperature and chemical composition. Here, the effects of fluorine doping in a perovskite nickelate NdNiO3 epitaxial thin films are investigated through a low-temperature reaction with polyvinylidene fluoride as the fluorine source. The fluorine content in the fluorinated NdNiO3-xFx films is controlled with precision by varying the reaction time. The fully fluorinated film (x ≈ 1) is highly insulating and has a bandgap of 2.1 eV, in contrast to NdNiO3, which exhibits metallic transport properties. Hard X-ray photoelectron and soft X-ray absorption spectroscopies reveal the suppression of the density of states at the Fermi level as well as the reduction of nickel ions (valence state changes from 3+ to 2+) after fluorination, suggesting that the strong Coulombic repulsion in the Ni 3d orbitals associated with the fluorine substitution drives the metal-to-insulator transition. In addition, the resistivity of the fluorinated films recovers to the original value for NdNiO3 after annealing in an oxygen atmosphere. By applying the reversible fluorination process to transition-metal oxides, the search for resistance-switching materials could be accelerated.

  7. Effects of Ru substitution for Mn on La0.7Sr0.3MnO3 perovskites

    NASA Astrophysics Data System (ADS)

    Wang, L. M.; Lai, Jian-Hong; Wu, Jyh-Iuan; Kuo, Y.-K.; Chang, C. L.

    2007-07-01

    We report the investigations of crystal structure, electrical resistivity (ρ), magnetization (M), x-ray photoelectron spectroscopy (XPS), specific heat (CP), thermal conductivity (κ), and thermoelectric power (TEP) on La0.7Sr0.3(Mn1-xRux)O3 (LSMRO) compounds with x =0 to 0.90. From the analyzes of crystal structure and magnetization measurements, it is inferred that Ru should have a mixed valence of Ru3+ and Ru4+ for LSMRO with low level of Ru substitution, and an additional mixed valence of Ru4+ and Ru5+ with higher Ru substitution. Such a finding is further confirmed by the XPS measurements. Besides, it is found that all measured physical properties undergo pronounced anomalies due to the ferromagnetic-paramagnetic phase transition, and the observed transport properties of LSMRO can be reasonably understood from the viewpoint of polaronic transport. The Curie temperatures TC determined from the magnetization measurements are consistently higher than those of the metal-insulator transitions TMI determined from the transport measurements. By replacing Mn with Ru, both TC and TMI decrease concurrently and the studied materials are driven toward the insulating phase with larger value of x. It is also found that the entropy change during the phase transition is reduced with more Ru substitution. These observations indicate that the existence of Ru has the effect of weakening the ferromagnetism and metallicity of the LSMRO perovskites.

  8. Theoretical insights into a potential lead-free hybrid perovskite: substituting Pb(2+) with Ge(2.).

    PubMed

    Sun, Ping-Ping; Li, Quan-Song; Yang, Li-Na; Li, Ze-Sheng

    2016-01-21

    In recent years, perovskite solar cells have been considerably developed, however the lead in the absorber MAPbI3 is a potential threat to the environment. To explore potential alternatives, the structural and electronic properties of MAGeX3 (X = Cl, Br, I) were investigated using different density functional theory methods, including GGA-PBE, PBE-SOC, HSE06 and HSE-SOC. The results implied that MAGeI3 exhibits an analogous band gap, substantial stability, remarkable optical properties, and significant hole and electron conductive behavior compared with the so far widely used absorber MAPbI3. Moreover, the calculations revealed that the energy splitting resulting from the spin-orbit coupling is evident on Pb, moderate on Ge, I and Br, and negligible on Cl. Our work not only sheds some light on screening novel absorbers for perovskite solar cells but also deepens the understanding of these functional materials.

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

    NASA Astrophysics Data System (ADS)

    Misra, Sunasira

    2012-07-01

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

  10. Diphenylpyridine Amine-Substituted Porphyrins as Hole-Transporting Materials for Perovskite Solar Cells.

    PubMed

    Lee, Un-Hak; Azmi, Randi; Sinaga, Septy; Hwang, Sunbin; Eom, Seung Hun; Kim, Tae-Wook; Yoon, Sung Cheol; Jang, Sung-Yeon; Jung, In Hwan

    2017-09-05

    The susceptibility of porphyrin derivatives to light-harvesting and charge-transport operations have enabled these materials to be employed in solar cell applications. The potential of porphyrin derivatives as hole-transporting materials (HTMs) for perovskite solar cells (PSCs) has recently been demonstrated, but research on the relationships between the porphyrin structure and device performance remains insufficient. In this work, a series of novel porphyrin derivatives, PZn-TPA-O, PZn-TPA, PZn-DPPA-O and PZn-DPPA, are developed and employed as HTMs for low-temperature processed PSCs. In our key design strategy, the electron deficient pyridine moiety was incorporated to down-shift HOMO levels of porphyrin HTMs. The porphyrin HTMs containing diphenylpyridine amine (DPPA) possess HOMO levels which are in good agreement with the perovskite active layers, thus facilitating hole transfers from the perovskite to the HTMs. The DPPA-containing PZn-DPPA based PSCs showed the best performance, with efficiency levels comparable to those of PSCs using spiro-OMeTAD, a current state-of-the-art HTM. In particular, PZn-DPPA based PSCs show superior air-stability in both doped and undoped forms, compared to spiro-OMeTAD based devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. First principle study of electronic and optical properties of molecular ion (BF4- ) substituted hybrid perovskite (CH3NH3PbI3)

    NASA Astrophysics Data System (ADS)

    Rani, Shalu; Singh, Poorva

    2017-05-01

    Hybrid organic/inorganic perovskites have garnered significant research interest due to the extraordinary increase in energy conversion efficiency as witnessed in photovoltaic devices based on CH3NH3PbI3. An experimental report has shown that the substitution of BF4- in the perovskite CH3NH3PbI3 can lead to the high efficiency for solar cell. Employing first-principles calculations based on density functional theory, we have studied several different perovskites CH3NH3PbI3 , CH3NH3PbI2BF4, CH3NH3PbI(BF4)2, CH3NH3Pb(BF4)3 and examined their electronic structure and optical properties.

  12. CsPbxMn1-xCl3 Perovskite Quantum Dots with High Mn Substitution Ratio.

    PubMed

    Liu, Huiwen; Wu, Zhennan; Shao, Jieren; Yao, Dong; Gao, Hang; Liu, Yi; Yu, Weili; Zhang, Hao; Yang, Bai

    2017-02-28

    CsPbX3 (X = Cl, Br, I) perovskite quantum dots (QDs) are potential emitting materials for illumination and display applications, but toxic Pb is not environment- and user-friendly. In this work, we demonstrate the partial replacement of Pb with Mn through phosphine-free hot-injection preparation of CsPbxMn1-xCl3 QDs in colloidal solution. The Mn substitution ratio is up to 46%, and the as-prepared QDs maintain the tetragonal crystalline structure of the CsPbCl3 host. Meaningfully, Mn substitution greatly enhances the photoluminescence quantum yields of CsPbCl3 from 5 to 54%. The enhanced emission is attributed to the energy transfer of photoinduced excitons from the CsPbCl3 host to the doped Mn, which facilitates exciton recombination via a radiative pathway. The intensity and position of this Mn-related emission are also tunable by altering the experimental parameters, such as reaction temperature and the Pb-to-Mn feed ratio. A light-emitting diode (LED) prototype is further fabricated by employing the as-prepared CsPbxMn1-xCl3 QDs as color conversion materials on a commercially available 365 nm GaN LED chip.

  13. Cluster glass behaviour in Co-substituted double perovskite Ca{sub 2}FeMoO{sub 6}

    SciTech Connect

    Poddar, Asok; Mazumdar, Chandan

    2011-05-15

    Research highlights: {yields} We have presented the crystallographic, electrical transport and dc and ac magnetic measurements on double perovskite Ca{sub 2}Fe{sub 1-x}Co{sub x}MoO{sub 6} (0.1 {<=} x {<=} 0.4) system. {yields} Co exists in divalent state in these compounds. {yields} The substituted system exhibits cluster-glass like behaviour, close to that observed earlier in Sr{sub 2}Fe{sub 1-x}Co{sub x}MoO{sub 6} compatible with an electronic phase segregation scenario (Phys. Rev. B 73 (2006) 104417). -- Abstract: The transport and magnetic properties of the double perovskite compounds Ca{sub 2}Fe{sub 1-x}Co{sub x}MoO{sub 6} (0.1 {<=} x {<=} 0.4) have been explored through resistivity [{rho}(T)], dc magnetisation [M(H, T)] and ac susceptibility [{chi}(T, f)] measurements. Introduction of Co increases the lattice volume implying the divalent nature of cobalt in this system. For all the samples, {rho}(T) behaviour over the temperature range (25-273 K) can be adequately described by considering possible disorder-enhanced electron-electron interaction effect as well as spin-wave contribution. Our results reveal that with the increase of Co concentration, the ferromagnetic Curie temperatures (T{sub C}) gradually reduced due to the incorporation of antiferromagnetic Co{sup 2+}-Mo{sup 6+} pairs replacing ferromagnetic Fe{sup 3+}-Mo{sup 5+} pairs. A cluster-glass like behaviour is also observed in the system due to the presence of highly spin-disordered regions.

  14. Thermal properties of Ni-substituted LaCoO{sub 3} perovskite

    SciTech Connect

    Thakur, Rasna Thakur, Rajesh K. Gaur, N. K.; Srivastava, Archana

    2014-04-24

    With the objective of exploring the unknown thermodynamic behavior of LaCo{sub 1−x}Ni{sub x}O{sub 3} family, we present here an investigation of the temperature-dependent (10K ≤ T ≤ 300K) thermodynamic properties of LaCo{sub 1−x}Ni{sub x}O{sub 3} (x=0.1, 0.3, 0.5). The specific heat of LaCoO3 with Ni doping in the perovskite structure at B-site has been studied by means of a Modified Rigid Ion Model (MRIM). This replacement introduces large cation variance at B-site hence the specific heat increases appreciably. We report here probably for the first time the cohesive energy, Reststrahlen frequency (υ) and Debye temperature (θ{sub D}) of LaCo{sub 1−x}Ni{sub x}O{sub 3} compounds.

  15. Red Shifted Absorbance of A-site Substituted Bismuth Titanate Pyrochlore: Characterization and Stability Analysis from First Principles

    NASA Astrophysics Data System (ADS)

    Mayfield, Cedric; Huda, Muhammad

    2015-03-01

    Transition metal inclusion has enhanced photocatalytic activity of bismuth titanate (Bi2Ti2O7) up to an impurity threshold concentration. Beyond the threshold, spectral absorbance is continually red shifted but increased photocurrent is not reciprocated. We investigated, from first principles, the origin of decreased photocurrent in modified Bi2Ti2O7 (BTO) by calculating the electronic structures of a representative set of doping configurations and by performing a phase stability analysis of the doping. We report our theoretical/computational strategy of analyzing free energy space and show an explicit dependence of pure phase synthesis on changes in free energy. Also, we present a probability distribution of the doping configurations based on formation enthalpy to better understand the nature of doping in BTO. We found that transition metal substitutions are favorable at the A-sites due to unchanging coordination with O ions. This work is supported by National Science Foundation, Award No. 1133672.

  16. 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).

  17. Effects of Mn Substitution on the Thermoelectric Properties and Thermal Excitations of the Electron-doped Perovskite Sr1-xLaxTiO3

    NASA Astrophysics Data System (ADS)

    Okuda, Tetsuji; Hata, Hiroto; Eto, Takahiro; Sobaru, Shogo; Oda, Ryosuke; Kaji, Hiroki; Nishina, Kousuke; Kuwahara, Hideki; Nakamura, Mitsutaka; Kajimoto, Ryoichi

    2016-09-01

    We studied how Mn substitution affects the thermoelectric properties and thermal excitations of the electron-doped perovskite Sr1-xLaxTiO3 by measuring its electrical and thermal transport properties, magnetization, specific heat, and inelastic neutron scattering. Slight Mn substitution with the lattice defects enhanced the Seebeck coefficient, perhaps because of coupling between itinerant electrons and localized spins or between itinerant electrons and local lattice distortion around Mn3+ ions, while it enhanced anharmonic lattice vibrations, which effectively suppressed thermal conductivity in a state of high electrical conductivity. Consequently, slight Mn substitution increased the dimensionless thermoelectric figure of merit for Sr1-xLaxTiO3 near room temperature.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Effects of cation disorder and size on metamagnetism in A-site substituted Pr0.5Ca0.5MnO3 system

    NASA Astrophysics Data System (ADS)

    Mavani, K. R.; Paulose, P. L.

    2005-04-01

    The effects of A-site cation disorder and size on metamagnetism of ABO3 type charge and orbital ordered Pr0.5Ca0.5MnO3 system have been studied by substituting Ba+2 for Ca+2 or La+3 for Pr+3. Substitution of 5% Ba+2 or 5% La+3 drastically reduces the critical magnetic field (Hc) for metamagnetism and induces successive steplike metamagnetic transitions at low temperatures. Interestingly, with further increase in substitution, Hc rises. We find that there is a sharp decrease in electrical resistivity corresponding to the metamagnetic transitions, which is indicative of strongly correlated magnetic and electronic transitions in these manganites.

  3. Size dependent mechanical and magnetic properties of Zn substituted cobalt ferrite below A-site percolation threshold

    NASA Astrophysics Data System (ADS)

    Acharya, Prashant; Parmar, Harshida

    2017-05-01

    Nanomagnetic particles of Co0.3Zn0.7Fe2O4 were synthesized using chemicalcoprecipitation technique followed by hydrothermal treatment and by controlling the preparative parameters pH and digestion time (td). Polydispersed nature and clear grain boundaries of the particles have been observed from the typical SEM image. EDX results confirmed the stoichiometric composition of the samples. XRD analysis shows the formation of a single phase spinel structure. Particle size ranging 5.5nm-9.0nm, calculated using Scherrer's formula, observed to be a function of pH and td. Cation distribution (Zn0.7Fe0.3)A[Co0.3Fe1.7]B is obtained from Rietveld analysis of XRD patterns. Lattice parameters and oxygen parameters are observed almost same showing the present synthesis technique is found to be effective to prepare particles of different size without changing the cation distribution and structural parameters. FTIR analysis and magnetic measurements reveals size dependent mechanical and magnetic properties of Zn substituted cobalt ferrite below A-site percolation threshold.

  4. 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.

  5. Crystal structures and microwave dielectric properties of Zn,W co-substituted BaTiO{sub 3} perovskite ceramics

    SciTech Connect

    Tian Cailan; Yue Zhenxing; Zhou Yuanyuan; Li Longtu

    2013-01-15

    Zn,W co-substituted BaTiO{sub 3} perovskite ceramics with compositions of Ba[Ti{sub 1-x}(Zn{sub 1/2}W{sub 1/2}){sub x}]O{sub 3} (x=0.40-1.00) were synthesized by the conventional solid-state reaction method and studied by X-ray diffraction and dielectric measurements. Their structures transferred from cubic (x=0.40) with space group Pm3{sup Macron }m to hexagonal (x=0.55-0.60) with P6{sub 3}/mmc, and then to cubic double pervoskite (x=1.00) with Fm3{sup Macron }m. The refinement results of sample (x=0.60) revealed that the negative and positive charge centers are not consistent with each other in the face-sharing oxygen octahedra. Compared with the cubic perovskites, the hexagonal ones had the increased quality factor (Q Multiplication-Sign f), the decreased dielectric constant ({epsilon}{sub r}), and especially the near-zero temperature coefficient of resonant frequency ({tau}{sub f}), whose absolute values were less than 5 ppm/ Degree-Sign C. The relationships between structures and properties were discussed. - Graphical abstract: The departure of the negative and positive charge centers in the face-sharing oxygen octahedra of hexagonal unit cell. Highlights: Black-Right-Pointing-Pointer A phase transition from simple cubic to hexagonal and then to cubic double pervoskite occurred. Black-Right-Pointing-Pointer Refinement results prove that spontaneous dipoles present in face-sharing oxygen octahedra. Black-Right-Pointing-Pointer Hexagonal perovskites had higher Q Multiplication-Sign f, nearer-zero {tau}{sub f}, and lower {epsilon}{sub r} than the cubic ones. Black-Right-Pointing-Pointer On the presence of the hexagonal perovskite, |{tau}{sub f}| was less than 5 ppm/ Degree-Sign C.

  6. 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

  7. 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.

  8. A computational view of the change in the geometric and electronic properties of perovskites caused by the partial substitution of Pb by Sn.

    PubMed

    Ju, Ming-Gang; Sun, Guangxu; Zhao, Yi; Liang, WanZhen

    2015-07-21

    Recently, solar cells with hybrid organic-inorganic lead halide perovskites have achieved a great success and their power conversion efficiency reaches about 17.9%. For practical applications, one has to avoid the toxicology issue of lead, to develop lead-free perovskite solar cells by using metal substitution. It has been shown that tin is one of possible candidates as a replacement for lead. Herein, a step-by-step protocol based on the first-principles calculations is performed to investigate the geometrical and electronic properties of mixed Sn and Pb perovskite MAPbxSn1-xI3 with different crystal symmetries. At first, a GGA functional with the inclusion of the van der Waals interaction, vdW-DF3, is used to optimize the geometries and it reproduces closely the unit cell volume. Then, a more accurate hybrid functional PBE0 combined with the spin-orbit coupling effect is used to perform electronic-structure calculations. The calculated results reveal that the band gaps of MAPbxSn1-xI3 are sensitive to the ratio of Sn/Pb, and are proportional to the x component, consistent with the previous reports. Further investigations show that the crystal symmetry can also modify the band gap in an order of Pnma > I4cm > P4mm at x = 0.5. The random rotation of organic cations, which makes the band alignments in the compounds, facilitates the separation and transfer of holes and electrons. Interestingly, the computed binding energies of the unrelaxed exciton have the same trend as band gaps, which decreases with decreasing x, the binding energies of MAPb0.5Sn0.5I3 also decrease as the crystal symmetry decreases, implying a faster exciton dissociation with lower x and lower symmetry at an ambient temperature.

  9. A-Site (MCe) Substitution Effects on the Structures and Properties of CaBi4Ti4O15 Ceramics

    NASA Astrophysics Data System (ADS)

    Yan, Haixue; Li, Chengen; Zhou, Jiaguang; Zhu, Weimin; He, Lianxin; Song, Yuxin

    2000-11-01

    We investigated the effect of A-site compound substitution on the structures and properties of Ca0.8(MCe)0.1Bi4Ti4O15 (M denotes Li, Na and K) ceramics. The samples were prepared by the conventional ceramic technique. Sintering characteristics of Ca0.8(MCe)0.1Bi4Ti4O15 and CaBi4Ti4O15 ceramics were discussed. X-ray powder diffraction patterns of the three modified CBT-based compounds show a single phase of bismuth oxide layer type structure with m=4. The hysteresis loops of polarization versus electric field of the four compounds were also measured. A-site compound substitution improves the piezoelectric properties and the high-temperature resistivity of these materials. A-site (LiCe) and (KCe) substitution not only improves the Curie temperature but also decreases the temperature coefficient of dielectric constant (TK\\varepsilon). Among the three modified ceramics, only the Curie temperature of Ca0.8(NaCe)0.1Bi4Ti4O15 is lower than that of CaBi4Ti4O15; however, its TK\\varepsilon is the lowest. As a result, all the three modified CBT-based ceramics were found to be excellent high-temperature piezoelectric materials.

  10. Magnetism, hysteresis cycle, and Ir-substitution doping of Sr2CrIrO6 double perovskite: A Monte Carlo simulation

    NASA Astrophysics Data System (ADS)

    El Rhazouani, O.; El Khatabi, M.; Zarhri, Z.; Slassi, A.; Benyoussef, A.; El Kenz, A.

    2016-12-01

    Iridium-based double perovskite (DP) Sr2CrIrO6 is expected to have the highest Curie temperatures (Tc) among all DPs and a high spin-polarization at room temperature, thanks to the more extended 5d orbitals of Ir, which makes it potential candidate in spintronic applications. Several publications have appeared in recent years documenting Ir-based double perovskites, but very few have explored the promising compound Sr2CrIrO6. In this paper, a Monte Carlo simulation has been carried out in the framework of Ising model to make an exploratory study of Sr2CrIrO6. Thermal magnetization, magnetic susceptibility, internal energy and specific heat have been studied. Effect of crystal field of Ir on the magnetic properties has been explored. Magnetic hysteresis cycle has been studied in relation to the exchange coupling values. Effects of Ir-substitution doping by Os "Sr2CrIrxOs1 - xO6" and by Re "Sr2CrIrxRe1 - xO6" (0.1 ≤ x ≤ 0.5) on the magnetic behavior have been investigated.

  11. Stabilization of Organic-Inorganic Perovskite Layers by Partial Substitution of Iodide by Bromide in Methylammonium Lead Iodide.

    PubMed

    Ruess, Raffael; Benfer, Felix; Böcher, Felix; Stumpp, Martina; Schlettwein, Derck

    2016-05-18

    Thin films of the methylammonium lead halides CH3 NH3 Pb(I1-x Brx )3 are prepared on fluorine-doped tin oxide substrates and exposed to humid air in the dark and under illumination. To characterize the stability of the materials, UV/Vis spectra are acquired at fixed intervals, accompanied by XRD, energy-dispersive X-ray spectroscopy, SEM, and confocal laser scanning microscopy. Different degradation mechanisms are observed depending on the environmental conditions. It is found that bromide can successfully suppress the transformation of the perovskite into the monohydrate, presumably owing to stronger hydrogen-bonding interactions with the organic cation. However, under illumination in humid air, rather rapid decomposition of the perovskites was still observed, which is due to phase segregation. The use of increased bromide content in methylammonium lead halide absorbers is discussed in terms of their application in perovskite solar cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. High pressure synthesis and study of magnetic and transport properties of Pb-substituted manganites with perovskite structure

    SciTech Connect

    Troyanchuk, I.O.; Khalyavin, D.D.; Szymczak, H.

    1997-12-01

    The stoichiometric La{sub 1{minus}x}Pb{sub x}MnO{sub 3} (x {le} 0.6) and La{sub 0.56}Pb{sub 0.44}MnO{sub 2.56}F{sub 0.44} as well as nonstoichiometric La{sub 1{minus}x}Pb{sub x}MnO{sub 3{minus}y} (x {le} 0.44) solid solutions with perovskite structure have been obtained under high pressure conditions. It was demonstrated that these compounds are ferromagnetic in a wide range of Pb concentrations and exhibit large magnetoresistance in spite of the absence of Mn{sup 4+} ions. It is supposed that magnetic ordering in these materials is governed by superexchange interaction via oxygen.

  18. 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

  19. 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.

  20. 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.

  1. Enhancement of charge transport properties of small molecule semiconductors by controlling fluorine substitution and effects on photovoltaic properties of organic solar cells and perovskite solar cells.

    PubMed

    Yun, Jae Hoon; Park, Sungmin; Heo, Jin Hyuck; Lee, Hyo-Sang; Yoon, Seongwon; Kang, Jinback; Im, Sang Hyuk; Kim, Hyunjung; Lee, Wonmok; Kim, BongSoo; Ko, Min Jae; Chung, Dae Sung; Son, Hae Jung

    2016-11-01

    We prepared a series of small molecules based on 7,7'-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(4-(5'-hexyl-[2,2'-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole) with different fluorine substitution patterns (0F-4F). Depending on symmetricity and numbers of fluorine atoms incorporated in the benzo[c][1,2,5]thiadiazole unit, they show very different optical and morphological properties in a film. 2F and 4F, which featured symmetric and even-numbered fluorine substitution patterns, display improved molecular packing structures and higher crystalline properties in a film compared with 1F and 3F and thus, 2F achieved the highest OTFT mobility, which is followed by 4F. In the bulk heterojunction solar cell fabricated with PC71BM, 2F achieves the highest photovoltaic performance with an 8.14% efficiency and 0F shows the lowest efficiency of 1.28%. Moreover, the planar-type perovskite solar cell (PSC) prepared with 2F as a dopant-free hole transport material shows a high power conversion efficiency of 14.5% due to its high charge transporting properties, which were significantly improved compared with the corresponding PSC device obtained from 0F (8.5%). From the studies, it is demonstrated that low variation in the local dipole moment and the narrow distribution of 2F conformers make intermolecular interactions favorable, which may effectively drive crystal formations in the solid state and thus, higher charge transport properties compared with 1F and 3F.

  2. Study of Arylamine-Substituted Porphyrins as Hole-Transporting Materials in High-Performance Perovskite Solar Cells.

    PubMed

    Chen, Song; Liu, Peng; Hua, Yong; Li, Yuanyuan; Kloo, Lars; Wang, Xingzhu; Ong, Beng; Wong, Wai-Kwok; Zhu, Xunjin

    2017-04-19

    To develop new hole-transporting materials (HTMs) for efficient and stable perovskite solar cells (PSCs), 5,10,15,20-tetrakis{4-[N,N-di(4-methoxylphenyl)amino-phenyl]}-porphyrin was prepared in gram scale through the direct condensation of pyrrole and 4-[bis(4-methoxyphenyl)amino]benzaldehyde. Its Zn(II) and Cu(II) complexes exhibit excellent thermal and electrochemical stability, specifically a high hole mobility and very favorable energetics for hole extraction that render them a new class of HTMs in organometallic halide PSCs. As expected, ZnP as HTM in PSCs affords a competitive power conversion efficiency (PCE) of 17.78%, which is comparable to that of the most powerful HTM of Spiro-MeOTAD (18.59%) under the same working conditions. Meanwhile, the metal centers affect somewhat the photovoltaic performances that CuP as HTM produces a lower PCE of 15.36%. Notably, the PSCs employing ZnP show a much better stability than Spiro-OMeTAD. Moreover, the two porphyrin-based HTMs can be prepared from relatively cheap raw materials with a facile synthetic route. The results demonstrate that ZnP and CuP can be a new class of HTMs for efficient and stable PSCs. To the best of our knowledge, this is the best performance that porphyrin-based solar cells could show with PCE > 17%.

  3. Low-Cost Perovskite Solar Cells Employing Dimethoxydiphenylamine-Substituted Bistricyclic Aromatic Enes as Hole Transport Materials.

    PubMed

    Rakstys, Kasparas; Paek, Sanghyun; Grancini, Giulia; Gao, Peng; Jankauskas, Vygintas; Asiri, Abdullah M; Nazeeruddin, Mohammad Khaja

    2017-06-26

    The synthesis, characterization and photovoltaic performance of series of novel molecular hole transport materials (HTMs) based on bistricyclic aromatic enes (BAEs) are presented. The new derivatives were obtained following a simple and straightforward procedure from inexpensive starting reagents mimicking the synthetically challenging 9,9'-spirobifluorene moiety of the well-studied spiro-OMeTAD. The novel HTMs were tested in mixed cations and anions perovskite solar cells (PSCs) yielding a power conversion efficiency (PCE) of 19.2 % under standard global 100 mW cm(-2) AM1.5G illumination using 9-{2,7-bis[bis(4-methoxyphenyl)amino]-9H-fluoren-9-ylidene}-N(2) ,N(2) ,N(7) ,N(7) -tetrakis(4-methoxyphenyl)-9H-thioxanthene-2,7-diamine (coded as KR374). The power conversion efficiency data confirms the easily attainable heteromerous fluorenylidenethioxanthene structure as valuable core for low-cost and highly efficient HTM design and paves the way towards cost-effective PSC technology. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Dopant-Free Hole-Transport Materials Based on Methoxytriphenylamine-Substituted Indacenodithienothiophene for Solution-Processed Perovskite Solar Cells.

    PubMed

    Liu, Xiaoyuan; Zheng, Xiaolu; Wang, Yulong; Chen, Zhiliang; Yao, Fang; Zhang, Qi; Fang, Guojia; Chen, Zhi-Kuan; Huang, Wei; Xu, Zong-Xiang

    2017-07-10

    Solution-processed hole transporting materials (HTMs) that are dopant-free show promise for use in low-cost, high-performance perovskite solar cells (PSCs). The highest-efficiency PSCs use organic HTMs, many of which have low mobilities and therefore require doping, which lowers the device stability. Additionally, these materials are not easily scaled because they often require complicated synthesis. Two new HTMs (IDT-TPA and IDTT-TPA) were synthesized, which contained either an extended fused-ring indacenodithiophene (IDT) or indacenodithienothiophene (IDTT) core and strong electron-donating methoxytriphenylamine (TPA) groups as the end-capping units. The extended conjugation in the backbone of IDTT-TPA resulted in stronger π-π interactions (3.321 Å) and a higher hole mobility of 6.46×10(-4)  cm(2)  V(-1)  s(-1) when compared with that of IDT-TPA (9.53×10(-5)  cm(2)  V(-1)  s(-1) ). A dopant-free, planar PSC that contained IDTT-TPA was fabricated and exhibited a high power conversion efficiency (PCE) of 15.7 %. This cell exhibited a higher PCE and less hysteresis than devices that contained IDT-TPA. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. The influence of A-site rare-earth for barium substitution on the chemical structure and ferroelectric properties of BZT thin films

    SciTech Connect

    Ostos, C.; Martinez-Sarrion, M.L.; Mestres, L.; Prieto, P.

    2009-10-15

    Rare-earth (RE) doped Ba(Zr,Ti)O{sub 3} (BZT) thin films were prepared by rf-magnetron sputtering from a Ba{sub 0.90}Ln{sub 0.067}Zr{sub 0.09}Ti{sub 0.91}O{sub 3} (Ln=La, Nd) target. The films were deposited at a substrate temperature of 600 deg. C in a high oxygen pressure atmosphere. X-ray diffraction (XRD) patterns of RE-BZT films revealed a <001> epitaxial crystal growth on Nb-doped SrTiO{sub 3}, <001> and <011> growth on single-crystal Si, and a <111>-preferred orientation on Pt-coated Si substrates. Scanning electron microscopy (SEM) showed uniform growth of the films deposited, along with the presence of crystals of about half-micron size on the film's surface. Transmission electron microscopy (TEM) evidenced high crystalline films with thicknesses of about 100 nm for 30 min of sputtering. Electron-probe microanalysis (EPMA) corroborated the growth rate (3.0-3.5 nm/min) of films deposited on Pt-coated Si substrates. X-ray photoelectron spectroscopy (XPS), in depth profile mode, showed variations in photoelectron Ti 2p doublet positions at lower energies with spin-orbital distances characteristic of BaTiO{sub 3}-based compounds. The XPS analysis revealed that lanthanide ions positioned onto the A-site of the BZT-perovskite structure increasing the MO{sub 6}-octahedra distortion (M=Ti, Zr) and, thereby, modifying the Ti-O binding length. Polarization-electric field hysteresis loops on Ag/RE-doped BZT/Pt capacitor showed good ferroelectric behavior and higher remanent polarization values than corresponding non-doped system. - Graphical abstract: XPS narrow-scan spectra of Ti 2p doublets of the Nd-doped BZT films deposited on Pt-coated Si substrate.

  6. The influence of A-site rare-earth for barium substitution on the chemical structure and ferroelectric properties of BZT thin films

    NASA Astrophysics Data System (ADS)

    Ostos, C.; Martínez-Sarrión, M. L.; Mestres, L.; Delgado, E.; Prieto, P.

    2009-10-01

    Rare-earth ( RE) doped Ba(Zr,Ti)O 3 (BZT) thin films were prepared by rf-magnetron sputtering from a Ba 0.90Ln0.067Zr 0.09Ti 0.91O 3 ( Ln=La, Nd) target. The films were deposited at a substrate temperature of 600 °C in a high oxygen pressure atmosphere. X-ray diffraction (XRD) patterns of RE-BZT films revealed a <001> epitaxial crystal growth on Nb-doped SrTiO 3, <001> and <011> growth on single-crystal Si, and a <111>-preferred orientation on Pt-coated Si substrates. Scanning electron microscopy (SEM) showed uniform growth of the films deposited, along with the presence of crystals of about half-micron size on the film's surface. Transmission electron microscopy (TEM) evidenced high crystalline films with thicknesses of about 100 nm for 30 min of sputtering. Electron-probe microanalysis (EPMA) corroborated the growth rate (3.0-3.5 nm/min) of films deposited on Pt-coated Si substrates. X-ray photoelectron spectroscopy (XPS), in depth profile mode, showed variations in photoelectron Ti 2 p doublet positions at lower energies with spin-orbital distances characteristic of BaTiO 3-based compounds. The XPS analysis revealed that lanthanide ions positioned onto the A-site of the BZT-perovskite structure increasing the MO 6-octahedra distortion ( M=Ti, Zr) and, thereby, modifying the Ti-O binding length. Polarization-electric field hysteresis loops on Ag/ RE-doped BZT/Pt capacitor showed good ferroelectric behavior and higher remanent polarization values than corresponding non-doped system.

  7. Multi-Enhanced-Phonon Scattering Modes in Ln-Me-A Sites co-substituted LnMeA11O19 Ceramics

    PubMed Central

    Lu, Haoran; Wang, Chang-An; Huang, Yong; Xie, Huimin

    2014-01-01

    Authors reported an effective path to decrease the thermal conductivity while to increase the coefficient of thermal expansion, thus enhancing the thermo-physical properties of the LnMeA11O19-type magnetoplumbite LaMgAl11O19 by simultaneously substituting La3+, Mg2+ and Al3+ ions with large ionic radius Ba2+, Zn2+ and Ti4+, respectively. The mechanism behind the lowered thermal conductivity was mainly due to the multi-enhanced-phonon scattering modes in Ln-Me-A sites co-substituted LnMeA11O19 ceramics. These modes involve the following four aspects, namely, point defect mechanism, the intrinsic scattering in the complex crystal cell and materials with stepped surface to localize phonon vibrational modes, as well as nano-platelet-like structure to incorporate additional grain boundary scattering. This study provides novel thoughts for promising candidate materials of even lower thermal conductivity for the next generation thermal barrier coatings. PMID:25351166

  8. Multi-enhanced-phonon scattering modes in Ln-Me-A sites co-substituted LnMeA11O19 ceramics.

    PubMed

    Lu, Haoran; Wang, Chang-An; Huang, Yong; Xie, Huimin

    2014-10-29

    Authors reported an effective path to decrease the thermal conductivity while to increase the coefficient of thermal expansion, thus enhancing the thermo-physical properties of the LnMeA11O19-type magnetoplumbite LaMgAl11O19 by simultaneously substituting La(3+), Mg(2+) and Al(3+) ions with large ionic radius Ba(2+), Zn(2+) and Ti(4+), respectively. The mechanism behind the lowered thermal conductivity was mainly due to the multi-enhanced-phonon scattering modes in Ln-Me-A sites co-substituted LnMeA11O19 ceramics. These modes involve the following four aspects, namely, point defect mechanism, the intrinsic scattering in the complex crystal cell and materials with stepped surface to localize phonon vibrational modes, as well as nano-platelet-like structure to incorporate additional grain boundary scattering. This study provides novel thoughts for promising candidate materials of even lower thermal conductivity for the next generation thermal barrier coatings.

  9. 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.

  10. 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.

  11. 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 (0substitution of Pr slightly increases the coercive field Hc and magnetization M, and strongly improves the magnetoresistance (MR) while lowering Tc. On the other hand, the substitution of Gd lowers Hc, M and Tc, however, increases MR of the system La0.7-xGdxSr0.3MnO3 at temperature A-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.

  12. Tuning optical absorption and photoexcited recombination dynamics in La1-xSrxFeO3-δ through A-site substitution and oxygen vacancies

    NASA Astrophysics Data System (ADS)

    Smolin, Sergey; Scafetta, Mark; Choquette, Amber; Sfeir, Matthew; Baxter, Jason; May, Steven

    We study optical absorption and recombination dynamics in La1-xSrxFeO3-δ thin films, uncovering the effects of tuning nominal Fe valence via A-site substitution and oxygen stoichiometry. Variable angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and a red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy, revealing similar nanosecond photoexcited carrier lifetimes for oxygen deficient and stoichiometric films with the same nominal Fe valence. These results demonstrate that while the static optical absorption is strongly dependent on Fe valence tuned through cation or anion stoichiometry, oxygen vacancies do not appear to play a significantly detrimental role in the recombination kinetics. Nsf: ECCS-1201957, MRI DMR-0922929, MRI DMR-1040166. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.

  13. 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.

  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. Amorphous Hole-Transporting Material based on 2,2'-Bis-substituted 1,1'-Biphenyl Scaffold for Application in Perovskite Solar Cells.

    PubMed

    Magomedov, Artiom; Sakai, Nobuya; Kamarauskas, Egidijus; Jokubauskaitė, Gabrielė; Franckevičius, Marius; Jankauskas, Vygintas; Snaith, Henry J; Getautis, Vytautas

    2017-03-16

    Perovskite solar cells are considered a promising technology for solar-energy conversion, with power conversion efficiencies currently exceeding 20 %. In most of the reported devices, Spiro-OMeTAD is used for positive-charge extraction and transport layer. Although a number of alternative hole-transporting materials with different aromatic or heteroaromatic fragments have already been synthesized, a cheap and well-performing hole-transporting material is still in high demand. In this work, a two-step synthesis of a carbazole-based hole-transporting material is presented. Synthesized compounds exhibited amorphous nature, good solubility and thermal stability. The perovskite solar cells employing the newly synthesized material generated a power conversion efficiency of 16.5 % which is slightly lower than that obtained with Spiro-OMeTAD (17.5 %). The low-cost synthesis and high performance makes our hole-transport material promising for applications in perovskite-based optoelectronic devices.

  17. Fabrication of nanofibrous A- or B-sites substituted LaCoO{sub 3} perovskites with macroscopic structures and their catalytic applications

    SciTech Connect

    Wu, Qiang; Zhao, Li; Wu, Meixia; Yao, Weifeng; Qi, Meixue; Shi, Xiaoyan

    2014-03-01

    Graphical abstract: Fabrication of nanofibrous La{sub 1−x}Ce{sub x}CoO{sub 3} (x = 0.05, 0.1, 0.2) and LaMn{sub x}Co{sub 1−x}O{sub 3} (x = 0.2, 0.5, 0.8) perovskite-type oxides with macroscopic structures can be successfully achieved by using carbon nanofibers (CNFs) as templates. Furthermore, their application for the combustion of carbon black (CB), which is a model of particulate matter exhausted from diesel engines, was demonstrated. - Highlights: • Nanofibrous perovskites with macroscopic shapes were successfully obtained. • CNFs template method used here is facile, effective and reproducible. • This method might be applicable to other novel material fabrication. • The obtained materials show superior catalytic activity in soot combustion. - Abstract: Fabrication of nanofibrous La{sub 1−x}Ce{sub x}CoO{sub 3} (x = 0.05, 0.1, 0.2) and LaMn{sub x}Co{sub 1−x}O{sub 3} (x = 0.2, 0.5, 0.8) perovskite-type oxides with macroscopic structures can be successfully achieved by using carbon nanofibers (CNFs) as templates. Field emission scanning electron microscopy (FE-SEM), coupled with X-ray diffraction (XRD) analysis confirmed the template effect and formation of the perovskite-type oxides on the macroscopic substrate. It turned out that this facile method can ensure the desired single-phase perovskite-type oxides formation by controlling the corresponding metal ratio during the preparation procedure. In addition, the immobilized nanofibrous La{sub 1−x}Ce{sub x}CoO{sub 3} (x = 0.05) and LaMn{sub x}Co{sub 1−x}O{sub 3} (x = 0.5) perovskite-type oxides can greatly decrease the combustion temperature of nanosized carbon black particles, which has the high potential application prospects in the treatment of diesel soot particles.

  18. Superconducting properties of the Fe-substituted La 2.5Y 0.5CaBa 3(Cu 1- xFe x) 7O z perovskite

    NASA Astrophysics Data System (ADS)

    Subbarao, M. V.; Kuberkar, D. G.; Kulkarni, R. G.

    1999-02-01

    The structural and superconducting properties of single-phase Fe-substituted La 2.5Y 0.5CaBa 3(Cu 1- xFe x) 7O z [LYCBCuFe] with 0≤ x≤0.15 compounds having triple-perovskite structure are investigated using X-ray diffraction, resistivity, AC Susceptibility, oxygen content and Mössbauer effect measurements. The observed reduction of Tc with increasing x in LYCBCuFe supports the view that magnetic pair breaking by local moments contributes predominantly to the suppression of superconductivity by Fe. The observed Fe-dopant site occupancies and the Cu(2) plane to the Cu(1) chain site ratio in the LYCBCuFe obtained from Mössbauer spectral analysis of x=0.02 sample are quite different from those of the usual Fe-doped YBa 2Cu 3O z.

  19. 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.

  20. Origin of the magnetic susceptibility maximum in CaCu3Ru4O12 and electronic states in the A-site substituted compounds

    NASA Astrophysics Data System (ADS)

    Kao, Ting-Hui; Sakurai, Hiroya; Yu, Shan; Kato, Harukazu; Tsujii, Naohito; Yang, Hung-Duen

    2017-07-01

    CaCu3Ru4O12 shows a broad maximum at around 200 K in temperature dependence of magnetic susceptibility, whose origin is under debate. The present study addresses this problem, using high-quality samples of Ca1 -xAxCu3Ru4O12 (A = La, Na, and Sr) made by high-pressure synthesis technique. Unlike in a previous report, the maximum shifts to lower temperatures for the La substitution, becomes obscure by the Na substitution, and is less influenced by the Sr substitution. This behavior strongly suggests that the susceptibility maximum is caused by a sharp peak in the density of states just above the Fermi level, which induces strong spin fluctuations. Furthermore, the nature of electronic states of LaCu3Ru4O12 and NaCu3Ru4O12 are discussed; the former likely bears a Kondo character, and the latter has spin fluctuations of different origin below approximately 150 K.

  1. Investigation of the Properties of Ba-Substituted La0.7Sr0.3- x Ba x MnO3 Perovskite Manganite Films for Resistive Switching Applications

    NASA Astrophysics Data System (ADS)

    Choi, Sun Gyu; Lee, Hong-Sub; Yeom, Geun Young; Park, Hyung-Ho

    2013-06-01

    La0.7Sr0.3- x Ba x MnO3 (LSBMO: x = 0.09, 0.18, and 0.27) thin films were prepared on Pt-coated Si substrates using a radiofrequency magnetron sputtering technique at a substrate heating temperature of 450°C. The effects of varying the amount of substituted Ba2+ on the physical, chemical, and electrical properties of the perovskite manganite films were systematically investigated. X-Ray diffraction showed that the growth orientation and crystallinity of films were not affected by the amount of substituted Ba cations. Raman spectroscopy was used to determine the tilt of MnO6 octahedra and the Jahn-Teller-type distortion variation of the manganite films. The change in covalent characteristics of Mn-O bonds with increasing amounts of Ba2+ substituent was analyzed by x-ray photoelectron spectroscopy, specifically to examine the effects of bond characteristics on the resistive switching properties of LSBMO. The resistance of the LSBMO films increased with increasing Ba2+ content due to an increase in the covalent nature of Mn-O bonds. The resistive switching ratio increased with increasing Ba2+ amount, and relationships among resistive switching, Jahn-Teller distortion, and Mn-O bond character of LSBMO films were interpreted.

  2. Electrochemical studies of water insertion and proton - Ceramic interaction in substituted perovskite SrZr0.9Ln0.1O2.95

    NASA Astrophysics Data System (ADS)

    Lacroix, O.; Rahmouni, K.; Sirat, A.; Takenouti, H.; Deslouis, C.; Keddam, M.; Sala, B.

    2014-12-01

    Because of their high ionic conduction even at relatively low temperatures, proton conducting ceramics are one of the most promising electrolytes for fuel cell. In contrast to oxide-ion conductors, proton-conducting systems, especially in an electrolyser plant, could operate below 600 °C, critical temperature for mechanical and hot corrosion resistance of common stainless steels. Proton conduction in perovskite type ceramic was analysed under the water molecules insertion to maximize proton conduction. To this end, the SrZr0.9Ln0.1O2.95 electrolyte and its microstructure, particularly grain size was investigated. The insertion and release of water in the perovskite structure was followed by impedance spectroscopy and by using the so-called Brick Layer Model (BLM) to separate the bulk and grain boundary conductivities. It was found that the conductivity in both zones increases namely with steam pressure. It was also verified that the bulk conductivity is higher than that of grain boundaries. Consequently both the operating steam pressure and the grain size appear as the main parameters that can be tuned to enhance the proton conduction.

  3. 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.

  4. The electronic structure of RbTiOPO4 and the effects of the A-site cation substitution in KTiOPO4-family crystals.

    PubMed

    Atuchin, V V; Kesler, V G; Meng, Guangsi; Lin, Z S

    2012-10-10

    The electronic structure of RbTiOPO(4) has been investigated with x-ray photoemission spectroscopy. Detailed photoemission spectra of the element core levels have been recorded under excitation by nonmonochromatic Al Kα radiation (1486.6 eV). The chemical bonding parameters are compared to those reported for complex titanates and phosphates. The band structures of KTiOPO(4), RbTiOPO(4), K(0.535)R(0.465)TiOPO(4) and TlTiOPO(4) have been calculated by ab initio methods and compared to available experimental results. It is found that the band structure of KTP-type phosphate crystals is weakly dependent on the nature of the A-site (A=K, Rb, Tl) element.

  5. La0.67Pb0.33- x K x MnO3 perovskites synthesized by sol-gel method: the effect of potassium substitution on the magnetic and electrical properties

    NASA Astrophysics Data System (ADS)

    Zaidi, Asma; Alharbi, T.; Dhahri, J.; Alzobaidi, S.; Zaidi, M. A.; Hlil, E. K.

    2017-01-01

    The influence of the potassium substitution for Pb ions in the mixed valence perovskites La0.67Pb0.33- x K x MnO3 (0 ≤ x ≤ 0.15) was investigated by X-ray diffraction, magnetic and electric transport measurements. All the compositions were synthesized using the sol-gel technique. X-ray diffraction and structure refinement showed that they crystallize in the rhombohedral structure with R{bar{3}}c space group. Upon K doping on Pb sites, the lattice parameters, unit cell volume, and the Mn-O-Mn bond angle were reduced. All the samples exhibited a ferromagnetic-paramagnetic transition and metallic-semiconductor one with increasing temperature. The analysis of the electrical resistivity data concluded that the metallic (ferromagnetic) part of the resistivity (below T M-Sc) can be explained by the following equation ρ( T) = ρ 0 + ρ 2 T 2 + ρ 4.5 T 4.5, signifying the importance of the domain boundary/grain, combination of electron-magnon, electron-electron and electron-phonon scattering processes. At higher-temperature ( T > T M-Sc) paramagnetic semiconducting regime, the adiabatic small polarons hopping mechanism (ASPH) was found to fit well.

  6. Dopant-site occupancies and superconducting properties of the Fe-substituted La 2.5Nd 0.5CaBa 3(Cu 1-xFe x) 7O z perovskite

    NASA Astrophysics Data System (ADS)

    Kundaliya, Darshan C.; Vij, Reeta; Kuberkar, D. G.; Kulkarni, R. G.

    2000-12-01

    The structural and superconducting properties of single-phase Fe-substituted La 2.5Nd 0.5CaBa 3(Cu 1-xFe x) 7O z (LNCBCuFe) with 0.0⩽ x⩽0.06 compounds having triple-perovskite structure are investigated using X-ray diffraction, a.c. susceptibility, d.c. magnetization, oxygen content and Mössbauer effect measurements. Mössbauer spectral analysis of x=0.03 sample displays unusual Fe-dopant site occupancies and the Cu(2) plane to Cu(1) chain site ratio in the LNCBCuFe are quite different from those of the usual Fe-doped YBa 2Cu 3O 7-δ. Specifically, we observe substantial occupation of a new chain-associated quasi-octahedral site, E, at 300 K which transforms into the well-known distorted tetrahedron chain site, A, on lowering the temperature to 78 K. The observed reduction of Tc with increasing x in LNCBCuFe supports the view that the hole filling mechanism contributes predominantly to the suppression of superconductivity by Fe.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Exploring the Effects of the Pb(2+) Substitution in MAPbI3 on the Photovoltaic Performance of the Hybrid Perovskite Solar Cells.

    PubMed

    Frolova, Lyubov A; Anokhin, Denis V; Gerasimov, Kirill L; Dremova, Nadezhda N; Troshin, Pavel A

    2016-11-03

    Here we report a systematic study of the Pb(2+) substitution in the hybrid iodoplumbate MAPbI3 with a series of elements affecting optoelectronic, structural, and morphological properties of the system. It has been shown that even partial replacement of lead with Cd(2+), Zn(2+), Fe(2+), Ni(2+), Co(2+), In(3+), Bi(3+), Sn(4+), and Ti(4+) results in a significant deterioration of the photovoltaic characteristics. On the contrary, Hg-containing hybrid MAPb1-xHgxI3 salts demonstrated a considerably improved solar cell performance at optimal mercury loading. This result opens up additional dimension in the compositional engineering of the complex lead halides for designing novel photoactive materials with advanced optoelectronic and photovoltaic properties.

  13. Investigation of cation (Sn2+) and anion (N3-) substitution in favor of visible light photocatalytic activity in the layered perovskite K2La2Ti3O10.

    PubMed

    Kumar, Vinod; Govind; Uma, S

    2011-05-15

    Noticeable lowering of the energy gaps have been achieved for the layered perovskite K(2)La(2)Ti(3)O(10) as a result of the attempts made to incorporate Sn(2+) and N(3-) ions. Incorporation of Sn(2+) ions was carried out by the ion-exchange reaction of K(2)La(2)Ti(3)O(10) with aqueous tin(II) chloride solution. Nitrogen incorporation was attempted by the solid state reaction of the parent oxide with urea around 400 °C in air. The resultant oxides have been characterized by power X-ray diffraction, UV-visible diffuse reflectance spectroscopy, and Fourier transform infrared spectroscopy. Room temperature ion-exchange was sufficient to introduce Sn(2+) ions with the resulting product of composition (Sn(0.45)K(0.2)H(0.9))La(2)Ti(3)O(10) · H(2)O. Visible light absorption was observed with the absorption edge red shift of ∼ 100 nm from that of the parent K(2)La(2)Ti(3)O(10). The lowering of the band gap was as expected by the contribution of Sn 5s orbitals to the O 2p orbitals in the formation of the valence band. Nitridation using urea resulted not only in nitrogen doping but with the additional sensitization by the presence of carbon nitride (CN) polymers, which again resulted in visible light absorption. The product oxides obtained as a result of cation and anion intended substitutional studies have been found to be useful for the visible light photocatalytic decomposition of organic dyes such as rhodamine B. Copyright © 2011 Elsevier B.V. All rights reserved.

  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. High-Efficiency Perovskite Solar Cells Based on New TPE Compounds as Hole Transport Materials: The Role of 2,7- and 3,6-Substituted Carbazole Derivatives.

    PubMed

    Zhu, Linna; Shan, Yahan; Wang, Rui; Liu, Debei; Zhong, Cheng; Song, Qunliang; Wu, Fei

    2017-03-28

    In this work, four tetraphenylethylene (TPE)-centered hole transport materials (HTMs), with 2,7- or 3,6-substituted carbazole derivatives as periphery groups are deliberately synthesized and characterized. Their photophysical properties, energy levels, and photovoltaic performances are systematically investigated, and their performances as HTMs are discussed with respect to the different substituent positions on the carbazole moiety. It is interesting to find that the TPE-based HTMs with 2,7-carbazole substituents rival the 3,6-carbazole substituents in hole mobility and hole extraction ability. A high power conversion efficiency of up to 16.74 % is achieved for the devices based on the 2,7-carbazole periphery arms, which is even higher than the one of the "star" HTM Spiro-OMeTAD (2,2-7,7-tetrakis(N,N'-diparamethoxy-phenylamine 9,9'-spirobifluorene) under the same conditions. As far as we know, this is the highest efficiency achieved in tetraphenylethylene derivatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. The effect of partial substitution of Ni by Mg on the structural, magnetic and spectroscopic properties of the double perovskite Sr2NiTeO6.

    PubMed

    Orayech, B; Ortega-San-Martín, L; Urcelay-Olabarria, I; Lezama, L; Rojo, T; Arriortua, María I; Igartua, J M

    2016-09-28

    In this report, the structural, magnetic and spectroscopic properties of the freeze-drying synthesized Sr2Ni1-xMgxTeO6 (x = 0.0, 0.1, 0.2, 0.3 and 0.5) oxides are analyzed by means of X-ray powder diffraction (XRPD) and neutron powder diffraction (NPD), electron paramagnetic resonance, diffuse reflectance and magnetic susceptibility. The XRPD and NPD data analysis using the mode-crystallography approach have revealed that at room temperature (RT), all the compositions are monoclinically distorted with the space group I2/m. The high and low temperature analyses have shown that these materials suffer a series of three structural phase transitions. The EPR results have shown that the spectra of all the compositions are centred at g≈ 2.28, indicating a slightly distorted octahedral environment of Ni(2+), which is in agreement with the crystal structure analysis. The increase of the Mg(2+) content in Sr2Ni1-xMgxTeO6, provokes a decrease of the dipolar interaction effects and thus, the resonance becomes narrower. This resonance does not completely disappear which leads to the idea that the long-range magnetic order is not completely established when x≥ 0.3. The substitution of the Ni(2+) (S = 1) ions by Mg(2+) (S = 0) ions, also induces a weakening of the antiferromagnetic interactions, which is reflected in the diminishing of the absolute value of θ and the Néel temperature TN. The magnetic structure determination revealed the existence of an antiferromagnetic coupling for x- and z-spin components of the nickel atoms.

  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. 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

  19. Dielectric properties and substitution preference of yttrium doped barium zirconium titanate ceramics

    NASA Astrophysics Data System (ADS)

    Shan, D.; Qu, Y. F.; Song, J. J.

    2007-01-01

    The dielectric properties of Ba(Zr 0.25Ti 0.75)O 3+ xY 2O 3 ceramics are investigated. We believe that, integrating with the lattice parameters, there is an alternation of substitution preference of yttrium ions for the host cations in perovskite lattice that is responsible for the Curie point. The Tc rises with the increase of Y 3+ doping when the doping content is less than 0.05 at%, owing to the replacement of Y 3+ ions for Ba 2+ ions at the A-site; when the Y 3+ content is more than 0.05 at%, Y 3+ ions tend to occupy the B-site in perovskite lattice, causing a drop of Tc. Owing to the modifications of Y 3+ doping, the loss tangent of BZT ceramics is depressed remarkably, making it a superior candidate to replace widely used lead-contained ceramics.

  20. Superior stability for perovskite solar cells with 20% efficiency using vacuum co-evaporation.

    PubMed

    Zhu, Xuejie; Yang, Dong; Yang, Ruixia; Yang, Bin; Yang, Zhou; Ren, Xiaodong; Zhang, Jian; Niu, Jinzhi; Feng, Jiangshan; Liu, Shengzhong Frank

    2017-08-31

    Chemical composition and film quality are two key figures of merit for large-area high-efficiency perovskite solar cells. To date, all studies on mixed perovskites have used solution-processing, which results in imperfect surface coverage and pin-holes generated during solvent evaporation, execrably influencing the stability and efficiency of perovskite solar cells. Herein, we report our development using a vacuum co-evaporation deposition method to fabricate pin-hole-free cesium (Cs)-substituted perovskite films with complete surface coverage. Apart from the simplified procedure, the present method also promises tunable band gap, reduced trap-state density and longer carrier lifetime, leading to solar cell efficiency as high as 20.13%, which is among the highest reported for planar perovskite solar cells. The splendid performance is attributed to superior merits of the Cs-substituted perovskite film including tunable band gap, reduced trap-state density and longer carrier lifetime. Moreover, the Cs-substituted perovskite device without encapsulation exhibits significantly higher stability in ambient air compared with the single-component counterpart. When the Cs-substituted perovskite solar cells are stored in dark for one year, the PCE remains at 19.25%, degrading only 4.37% of the initial efficiency. The excellent stability originates from reduced lattice constant and relaxed strain in perovskite lattice by incorporating Cs cations into the crystal lattice, as demonstrated by the positive peak shifts and reduced peak width in X-ray diffraction analysis.

  1. Self-Assembled PbSe Nanowire:Perovskite Hybrids.

    PubMed

    Yang, Zhenyu; Yassitepe, Emre; Voznyy, Oleksandr; Janmohamed, Alyf; Lan, Xinzheng; Levina, Larissa; Comin, Riccardo; Sargent, Edward H

    2015-12-02

    Inorganic semiconductor nanowires are of interest in nano- and microscale photonic and electronic applications. Here we report the formation of PbSe nanowires based on directional quantum dot alignment and fusion regulated by hybrid organic-inorganic perovskite surface ligands. All material synthesis is carried out at mild temperatures. Passivation of PbSe quantum dots was achieved via a new perovskite ligand exchange. Subsequent in situ ammonium/amine substitution by butylamine enables quantum dots to be capped by butylammonium lead iodide, and this further drives the formation of a PbSe nanowire superlattice in a two-dimensional (2D) perovskite matrix. The average spacing between two adjacent nanowires agrees well with the thickness of single atomic layer of 2D perovskite, consistent with the formation of a new self-assembled semiconductor nanowire:perovskite heterocrystal hybrid.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. An efficient copper phthalocyanine additive of perovskite precursor for improving the photovoltaic performance of planar perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Wu, Shufang; Liu, Qingwei; Zheng, Ya; Li, Renjie; Peng, Tianyou

    2017-08-01

    Solution processable planar heterojunction perovskite solar cell has drawn much attention as a promising low-cost photovoltaic device, and much effort has been made to improve its power conversion efficiency by choosing appropriate additives for the perovskite precursor solution. Different to those additives reported, a soluble and thermal stable tert-butyl substituted copper phthalocyanine (CuPc(tBu)4) as additive is first introduced into the perovskite precursor solution of a planar perovskite solar cell that is fabricated via the one-step solution process. It is found that the pristine device without CuPc(tBu)4 additive exhibits a power conversion efficiency of 15.3%, while an extremely low concentration (4.4 × 10-3 mM) of CuPc(tBu)4 in the precursor solution leads to the corresponding device achieving an enhanced power conversion efficiency of 17.3%. CuPc(tBu)4 as an additive can improve the quality of perovskite layer with higher crystallinity and surface coverage, then resulting in enhanced light absorption and reduced charge recombination, and thus the better power conversion efficiency. The finding presented here provides a new choice for improving the quality of perovskite layer and the photovoltaic performance of the planar heterojunction perovskite solar cells.

  8. 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

  9. Perovskite-type catalytic materials for environmental applications

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  10. Perovskite-type catalytic materials for environmental applications

    PubMed Central

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

    2015-01-01

    Perovskites are mixed-metal oxides that are attracting much scientific and application interest owing to their low price, adaptability, and thermal stability, which often depend on bulk and surface characteristics. These materials have been extensively explored for their catalytic, electrical, magnetic, and optical properties. They are promising candidates for the photocatalytic splitting of water and have also been extensively studied for environmental catalysis applications. Oxygen and cation non-stoichiometry can be tailored in a large number of perovskite compositions to achieve the desired catalytic activity, including multifunctional catalytic properties. Despite the extensive uses, the commercial success for this class of perovskite-based catalytic materials has not been achieved for vehicle exhaust emission control or for many other environmental applications. With recent advances in synthesis techniques, including the preparation of supported perovskites, and increasing understanding of promoted substitute perovskite-type materials, there is a growing interest in applied studies of perovskite-type catalytic materials. We have studied a number of perovskites based on Co, Mn, Ru, and Fe and their substituted compositions for their catalytic activity in terms of diesel soot oxidation, three-way catalysis, N2O decomposition, low-temperature CO oxidation, oxidation of volatile organic compounds, etc. The enhanced catalytic activity of these materials is attributed mainly to their altered redox properties, the promotional effect of co-ions, and the increased exposure of catalytically active transition metals in certain preparations. The recent lowering of sulfur content in fuel and concerns over the cost and availability of precious metals are responsible for renewed interest in perovskite-type catalysts for environmental applications. PMID:27877813

  11. 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.

  12. 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.

  13. 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.

  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 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.

  15. 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

  16. 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.

  17. Perovskite-related oxynitrides in photocatalysis.

    PubMed

    Pokrant, Simone; Maegli, Alexandra E; Chiarello, Gian Luca; Weidenkaff, Anke

    2013-01-01

    Over the last decades photocatalytic water splitting has become of increasing importance for fundamental and applied research, since the direct conversion of sunlight into chemical energy via the production of H2 has the potential to contribute to the world's energy needs without CO2 generation. One of the unsolved challenges consists of finding a highly efficient photocatalyst that is cheap, environmentally friendly, contains exclusively abundant elements, is (photo)chemically stable and absorbs visible light. Photocatalytic efficiency is closely connected to both structural properties like crystallinity, particle size and surface area and to electronic properties like the band gap and the quantum efficiency. Hence extensive control over a large parameter field is necessary to design a good photocatalyst. A material class where the structure-composition-property relations and the influence of substitution effects are well studied is the perovskite-type family of compounds. The perovskite-related oxynitrides belong to this very flexible compound family where many of the necessary characteristics for a photocatalyst are already given and some of the intrinsic properties like the band gap can be tuned within the same crystal structure by substitution. In this work we present materials' design concepts to improve the photocatalytic efficiency of a perovskite-type catalyst and describe their effects on the photocatalytic activity.

  18. 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.

  19. Probing the electronic structures of ternary perovskite and pyrochlore oxides containing Sn(4+) or Sb(5+).

    PubMed

    Mizoguchi, Hiroshi; Eng, Hank W; Woodward, Patrick M

    2004-03-08

    Experimental and computational studies were performed to understand the electronic structure of ternary perovskites (ASnO(3), A = Ca, Sr, Ba, Cd), pyrochlores (RE(2)Sn(2)O(7), RE = Y, La, Lu; Cd(2)Sb(2)O(7)), and defect pyrochlore oxides (Ag(2)Sb(2)O(6)) containing the main group ions Sn(4+) and Sb(5+). In all compounds, the lowest energy states in the conduction band arise primarily from the antibonding Sn/Sb 5s-O 2p interaction. In the alkaline-earth stannate perovskites (BaSnO(3), SrSnO(3), and CaSnO(3)) the conduction bandwidth decreases strongly in response to the octahedral tilting distortion triggered by the decreasing size of the alkaline-earth cation. This in turn leads to a corresponding increase in the band gap from 3.1 eV in BaSnO(3) to 4.4 eV in CaSnO(3). The band gap of CdSnO(3) is relatively small (3.0 eV) considering the large octahedral tilting distortion. The origin of this apparent anomaly is the mixing between the empty Cd 5s orbitals and the antibonding Sn 5s-O 2p states. This mixing leads to a widening of the conduction band and a corresponding decrease in the band gap. The participation of the normally inert A-site cation in the electronic structure near the Fermi level can be considered an inductive effect, as it utilizes substitution on the A-site to directly modify the electronic structure of the SnO(3)(2)(-) framework. While the pyrochlore structure is more complicated, the energy level and width of the lowest energy conduction band can be analyzed in a manner similar to that utilized on the perovskite structure. The Sn-O-Sn and Sb-O-Sb bonds are highly distorted from linear geometry in pyrochlore, leading to a relatively narrow conduction band and a wide band gap. In Cd(2)Sb(2)O(7) and Ag(2)Sb(2)O(6) the Cd(2+) and Ag(+) ions exhibit a strong inductive effect that widens the conduction band and lowers the band gap significantly, very similar to the effect observed in the perovskite form of CdSnO(3).

  20. 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.

  1. Oxidation Reactions of Ethane over Ba-Ce-O Based Perovskites

    SciTech Connect

    Miller, James E.; Sault, Allen G.; Trudell, Daniel E.; Nenoff, Tina M.; Thoma, Steven G.; Jackson, Nancy B.

    1999-08-18

    Ethane oxidation reactions were studied over pure and Ca-, Mg-, Sr-, La-, Nd-, and Y-substituted BaCeO{sub 3} perovskites under oxygen limited conditions. Several of the materials, notably the Ca- and Y-substituted materials, show activity for complete oxidation of the hydrocarbon to CO{sub 2} at temperatures below 650 C. At higher temperatures, the oxidative dehydrogenation (ODH) to ethylene becomes significant. Conversions and ethylene yields are enhanced by the perovskites above the thermal reaction in our system in some cases. The perovskite structure is not retained in the high temperature reaction environment. Rather, a mixture of carbonates and oxides is formed. Loss of the perovskite structure correlates with a loss of activity and selectivity to ethylene.

  2. Theoretical insights into multibandgap hybrid perovskites for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Even, Jacky; Sapori, Daniel; Pedesseau, Laurent; Rolland, Alain; Kepenekian, Mikael; Robles, Roberto; Wang, Shijian; Huang, Yong; Beck, Alexandre; Durand, Olivier; Katan, C.

    2015-09-01

    This paper reviews some of the recent theoretical investigations on the Rashba Dresselhaus spin effects and dielectric properties of CH3NH3PbI3 hybrid perovskites and CsPbI3 all-inorganic perovskites using Density functional theory. The spin vectors rotate in the non-centrosymmetric P4mm tetragonal phase, respectively clockwise and counterclockwise, in a manner that is characteristic of a pure Rashba effect. The high frequency dielectric constants ɛ∞ of MAPbI3 and CsPbI3 are similar as anticipated, since large differences are only expected at very low frequency where additional contributions from molecular reorientations show off for the hybrid compounds. A first simulation of a perovskite on silicon tandem cell, including a tunnel junction, is also investigated. Effect of halogen substitution (I/Br) is inspected, revealing limitations for short-circuit current and open-circuit voltage electrical characteristics.

  3. 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.

  4. 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.

  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. Optical analysis of CH3NH3Sn x Pb1-x I3 absorbers: a roadmap for perovskite-on-perovskite tandem solar cells.

    PubMed

    Anaya, Miguel; Correa-Baena, Juan P; Lozano, Gabriel; Saliba, Michael; Anguita, Pablo; Roose, Bart; Abate, Antonio; Steiner, Ullrich; Grätzel, Michael; Calvo, Mauricio E; Hagfeldt, Anders; Míguez, Hernán

    2016-08-07

    Organic-inorganic perovskite structures in which lead is substituted by tin are exceptional candidates for broadband light absorption. Herein we present a thorough analysis of the optical properties of CH3NH3Sn x Pb1-x I3 films, providing the field with definitive insights about the possibilities of these materials for perovskite solar cells of superior efficiency. We report a user's guide based on the first set of optical constants obtained for a series of tin/lead perovskite films, which was only possible to measure due to the preparation of optical quality thin layers. According to the Shockley-Queisser theory, CH3NH3Sn x Pb1-x I3 compounds promise a substantial enhancement of both short circuit photocurrent and power conversion efficiency in single junction solar cells. Moreover, we propose a novel tandem architecture design in which both top and bottom cells are made of perovskite absorbers. Our calculations indicate that such perovskite-on-perovskite tandem devices could reach efficiencies over 35%. Our analysis serves to establish the first roadmap for this type of cells based on actual optical characterization data. We foresee that this study will encourage the research on novel near-infrared perovskite materials for photovoltaic applications, which may have implications in the rapidly emerging field of tandem devices.

  7. The lanthanum gallate-based mixed conducting perovskite ceramics

    NASA Astrophysics Data System (ADS)

    Politova, E. D.; Stefanovich, S. Yu.; Aleksandrovskii, V. V.; Kaleva, G. M.; Mosunov, A. V.; Avetisov, A. K.; Sung, J. S.; Choo, K. Y.; Kim, T. H.

    2005-01-01

    The structure, microstructure, dielectric, and transport properties of the anion deficient perovskite solid solutions (La,Sr)(Ga,Mg,M)O3- with M=Fe, Ni have been studied. Substitution of iron and nickel for gallium up to about 20 and 40 at.% respectively, leads to the perovskite lattice contraction due to the cation substitutions by the transition elements. The transition from pure ionic to mixed ionic-electronic conductivity was observed for both the systems studied. Both the enhancement of total conductivity and increasing in the thermal expansion coefficient values has been proved to correlate with the increasing amount of weakly bounded oxygen species in the Fe or Ni-doped ceramics. The oxygen ionic conductivity has been estimated from the kinetic experiments using the dc-conductivity and dilatometry methods under the condition of the stepwise change of the atmosphere from nitrogen to oxygen.

  8. The effect of minor elements on H incorporation in MgSiO3 perovskite

    NASA Astrophysics Data System (ADS)

    Watson, H. C.; Fei, Y.; Hauri, E.; Reid, F.; Jacobsen, S. D.

    2006-12-01

    It has been predicted that silicate perovskite in the lower mantle may be a significant reservoir for hydrogen in the Earth's interior, although quantitative analysis of the hydrogen storage capacity has remained elusive. This is primarily due to difficulties in interpreting FTIR spectra of perovskite samples at room pressure [eg. Murakami et al. 2002, Science 295, 1885-1887, Bolfan-Casanova et al. 2003, Geophys. Res. Lett. 30, 1905, Litasov et al. 2003, EPSL 211, 189-203]. The mechanism by which H is thought to be incorporated into perovskite is through substitution of minor trivalent elements such as Al and Fe. This may open oxygen vacancies that are in turn, filled with OH groups for charge balance , although coupled substitution (e.g. 2Al3+ ----> Si^{4+}+Mg2+) is also a possibility [Navrotsky 1999, Science 284 5421, 1788 - 1789]. We have synthesized Al-bearing, and Al-Fe bearing perovskite samples under hydrous conditions in a multi-anvil apparatus at pressures ranging from 23-26 GPa and 1800°C and 1200°C. The starting materials consisted of either oxide powders with brucite as the source of H2O, or pre-synthesized Al, Fe bearing hydrous enstatite. The resulting perovskite crystals range in size from <20 microns to >100 microns in size. Their major element chemistry has been characterized by electron microprobe, and the H content of samples has been measured by secondary ion mass spectrometry using a 6f Cameca ion microprobe and is substantial (>1000ppm in some samples). Preliminary FTIR measurements support the idea that the H measured is structurally bound in the perovskite crystal. We find a linear correlation between Al and H content in the perovskite, and discussion follows on the substitution mechanisms for minor elements and H into perovskite at conditions relevant to the uppermost lower mantle.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. High stability of electro-transport and magnetism against the A-site cation disorder in SrRuO3

    NASA Astrophysics Data System (ADS)

    Wang, Y. L.; Liu, M. F.; Liu, R.; Xie, Y. L.; Li, X.; Yan, Z. B.; Liu, J.-M.

    2016-06-01

    It is known that the electro-transport and magnetism of perovskite alkaline-earth ruthenate oxides are sensitive to the lattice distortion associated with the A-site cation size. Orthorhombic CaRuO3 and cubic BaRuO3 exhibit distinctly different electro-transport and magnetic properties from orthorhombic SrRuO3. It has been suggested that SrRuO3 can be robust against some intrinsic/external perturbations but fragile against some others in terms of electro-transport and magnetism, and it is our motivation to explore such stability against the local site cation disorder. In this work, we prepare a set of SrRuO3-based samples with identical averaged A-site size but different A-site cation disorder (size mismatch) by Ca and Ba co-substitution of Sr. It is revealed that the electro-transport and magnetism of SrRuO3 demonstrate relatively high stability against this A-site cation disorder, characterized by the relatively invariable electrical and magnetic properties in comparison with those of SrRuO3 itself. A simple electro-transport network model is proposed to explain quantitatively the measured behaviors. The present work suggests that SrRuO3 as an itinerant electron ferromagnetic metal possesses relatively high robustness against local lattice distortion and cation occupation disorder.

  15. High stability of electro-transport and magnetism against the A-site cation disorder in SrRuO3.

    PubMed

    Wang, Y L; Liu, M F; Liu, R; Xie, Y L; Li, X; Yan, Z B; Liu, J-M

    2016-06-14

    It is known that the electro-transport and magnetism of perovskite alkaline-earth ruthenate oxides are sensitive to the lattice distortion associated with the A-site cation size. Orthorhombic CaRuO3 and cubic BaRuO3 exhibit distinctly different electro-transport and magnetic properties from orthorhombic SrRuO3. It has been suggested that SrRuO3 can be robust against some intrinsic/external perturbations but fragile against some others in terms of electro-transport and magnetism, and it is our motivation to explore such stability against the local site cation disorder. In this work, we prepare a set of SrRuO3-based samples with identical averaged A-site size but different A-site cation disorder (size mismatch) by Ca and Ba co-substitution of Sr. It is revealed that the electro-transport and magnetism of SrRuO3 demonstrate relatively high stability against this A-site cation disorder, characterized by the relatively invariable electrical and magnetic properties in comparison with those of SrRuO3 itself. A simple electro-transport network model is proposed to explain quantitatively the measured behaviors. The present work suggests that SrRuO3 as an itinerant electron ferromagnetic metal possesses relatively high robustness against local lattice distortion and cation occupation disorder.

  16. High stability of electro-transport and magnetism against the A-site cation disorder in SrRuO3

    PubMed Central

    Wang, Y. L.; Liu, M. F.; Liu, R.; Xie, Y. L.; Li, X.; Yan, Z. B.; Liu, J.-M.

    2016-01-01

    It is known that the electro-transport and magnetism of perovskite alkaline-earth ruthenate oxides are sensitive to the lattice distortion associated with the A-site cation size. Orthorhombic CaRuO3 and cubic BaRuO3 exhibit distinctly different electro-transport and magnetic properties from orthorhombic SrRuO3. It has been suggested that SrRuO3 can be robust against some intrinsic/external perturbations but fragile against some others in terms of electro-transport and magnetism, and it is our motivation to explore such stability against the local site cation disorder. In this work, we prepare a set of SrRuO3-based samples with identical averaged A-site size but different A-site cation disorder (size mismatch) by Ca and Ba co-substitution of Sr. It is revealed that the electro-transport and magnetism of SrRuO3 demonstrate relatively high stability against this A-site cation disorder, characterized by the relatively invariable electrical and magnetic properties in comparison with those of SrRuO3 itself. A simple electro-transport network model is proposed to explain quantitatively the measured behaviors. The present work suggests that SrRuO3 as an itinerant electron ferromagnetic metal possesses relatively high robustness against local lattice distortion and cation occupation disorder. PMID:27297396

  17. 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

  18. Influence of the mixed organic cation ratio in lead iodide based perovskite on the performance of solar cells.

    PubMed

    Salado, Manuel; Calio, Laura; Berger, Rüdiger; Kazim, Samrana; Ahmad, Shahzada

    2016-10-05

    Lead halide based perovskite solar cells are presently the flagship among the third generation solution-processed photovoltaic technologies. The organic cation part in the perovskite plays an important role in terms of crystal structure tuning from tetragonal to trigonal or pseudocubic or vice versa depending on the organic cations used, while it also displays different microstructure. In this paper, we demonstrate the influence of the organic cation part with respect to optical properties, hysteresis behavior, and stability. This study offers a clear understanding of the perovskite properties and how they can be modulated by compositional engineering. With a rational choice, light harvesting abilities and hysteresis behavior can be controlled in these systems. The substitution of formamidinium cation by methylammonium cation allows achieving low temperature annealing and inducing stability in perovskites together with enhanced photovoltaic properties. By the use of in-situ scanning force microscopy experiments the conversion of precursors to perovskite at a particular temperature can be visualized.

  19. 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.

  20. Substitute Solutions.

    ERIC Educational Resources Information Center

    Jones, Kevin R.; Hawkins, Amber

    2000-01-01

    In summer 1999, a group of Park City, Utah, school administrators, personnel directors, human-resource specialists, and substitute teacher coordinators brainstormed on improving the recruitment, training, and retention of substitute teachers. Providing effective preservice and on-the-job training and professional recognition are key suggestions.…

  1. [Bone substitutes].

    PubMed

    Jordana, Fabienne; Le Visage, Catherine; Weiss, Pierre

    2017-01-01

    Bone substitutes, used to fill a defect after a surgery or a trauma, provide a mechanical support and might induce bone healing. They constitute an alternative to autogenous bone grafts, the 'gold standard' which remains the reference despite its risk of postoperative complications. The clinician choice of a bone substitute is based on the required bone volume, the handling (injectability, malleability) and mechanical properties (setting time, viscosity, resorbability among others) of the material. Bone substitutes are commonly used in orthopedic surgery, neurosurgery, stomatology and dental applications. Their use increases steadily, with the recent clinical development of injectable forms. In addition, novel technologies by subtractive or additive techniques allow today the production of controlled architecture materials. Here, we present a bone substitutes classification according to their origin (natural or synthetic) and chemical composition, and the most common use of these substitutes. © 2017 médecine/sciences – Inserm.

  2. Skin Substitutes

    PubMed Central

    Howe, Nicole; Cohen, George

    2014-01-01

    In a relatively short timespan, a wealth of new skin substitutes made of synthetic and biologically derived materials have arisen for the purpose of wound healing of various etiologies. This review article focuses on providing an overview of skin substitutes including their indications, contraindications, benefits, and limitations. The result of this overview was an appreciation of the vast array of options available for clinicians, many of which did not exist a short time ago. Yet, despite the rapid expansion this field has undergone, no ideal skin substitute is currently available. More research in the field of skin substitutes and wound healing is required not only for the development of new products made of increasingly complex biomolecular material, but also to compare the existing skin substitutes. PMID:25371771

  3. 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.

  4. 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.

  5. Systematic Thermodynamics of Layered Perovskites: Ruddlesden-Popper Phases.

    PubMed

    Glasser, Leslie

    2017-08-07

    Perovskite, CaTiO3, is the prototype of an extensive group of materials. They are capable of considerable chemical modification, with the further capability of undergoing structural modification by the intercalation of thin sheets of intrusive materials (both inorganic and organic) between the cubic perovskite layers, to form a range of "layered" perovskites. These changes bring about alterations in their electronic, structural, and other properties, permitting some "tuning" toward specific ends. This paper collects the limited known thermodynamic data for layered perovskites of various chemical compositions and demonstrates by example that the thermodynamic layer values are substantially additive. This additivity may be exploited by summing properties of the constituent oxides, by adding differences between adjacent compositions within a series, or even by substitution of oxides for one another, thus permitting prediction beyond the known range of compositions. Strict additivity implies full reversibility so that the additive product may be unstable and may undergo structural changes, producing materials with new and potentially useful properties such as ferroelectricity, polarity, giant magnetoresistance, and superconductivity.

  6. Hybrid halide perovskite solar cell precursors: colloidal chemistry and coordination engineering behind device processing for high efficiency.

    PubMed

    Yan, Keyou; Long, Mingzhu; Zhang, Tiankai; Wei, Zhanhua; Chen, Haining; Yang, Shihe; Xu, Jianbin

    2015-04-08

    The precursor of solution-processed perovskite thin films is one of the most central components for high-efficiency perovskite solar cells. We first present the crucial colloidal chemistry visualization of the perovskite precursor solution based on analytical spectra and reveal that perovskite precursor solutions for solar cells are generally colloidal dispersions in a mother solution, with a colloidal size up to the mesoscale, rather than real solutions. The colloid is made of a soft coordination complex in the form of a lead polyhalide framework between organic and inorganic components and can be structurally tuned by the coordination degree, thereby primarily determining the basic film coverage and morphology of deposited thin films. By utilizing coordination engineering, particularly through employing additional methylammonium halide over the stoichiometric ratio for tuning the coordination degree and mode in the initial colloidal solution, along with a thermal leaching for the selective release of excess methylammonium halides, we achieved full and even coverage, the preferential orientation, and high purity of planar perovskite thin films. We have also identified that excess organic component can reduce the colloidal size of and tune the morphology of the coordination framework in relation to final perovskite grains and partial chlorine substitution can accelerate the crystalline nucleation process of perovskite. This work demonstrates the important fundamental chemistry of perovskite precursors and provides genuine guidelines for accurately controlling the high quality of hybrid perovskite thin films without any impurity, thereby delivering efficient planar perovskite solar cells with a power conversion efficiency as high as 17% without distinct hysteresis owing to the high quality of perovskite thin films.

  7. 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.

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

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

    PubMed

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

    2012-01-01

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

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

    SciTech Connect

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

    2010-01-01

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

  3. 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.

  4. Advances in Perovskite Solar Cells

    PubMed Central

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

    2016-01-01

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

  5. 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.

  6. 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.

  7. Hydrogen Incorporation in Aluminous MgSiO3-Perovskite

    NASA Astrophysics Data System (ADS)

    Smyth, J. R.; Jacobsen, S. D.; Huss, G. R.; Miyajima, N.; Pamato, M. G.

    2013-12-01

    We have synthesized hydrous, aluminum-bearing MgSiO3 perovskite samples at 25GPa and various temperatures from 1600 to 2200C in a multi-anvil press and have characterized the samples by single-crystal X-ray diffraction, Raman spectroscopy, electron microprobe (EPMA), transmission electron microscopy (TEM), and secondary ion mass spectroscopy (SIMS). Perovskite crystals range up to 100 micrometers in size and contain 1 - 2.5% by weight Al2O3. SIMS analyses with a probe spot of approximately 10 micron square indicate up to several thousand ppm by weight H2O which corresponds to one H per Al atom in the structure. Microprobe chemical analysis and crystal structure refinement from single crystal X-ray data indicates that Al substitutes in the Si site, but not in the Mg site. However, Raman spectroscopy indicates the presence of micro-inclusions of brucite, super-hydrous phase B (SHyB), magnesite, and stishovite in most samples. Some of the perovskite crystals in the samples synthesized at temperatures above 2100 C exhibit rounded inclusions that are interpreted to be melt that quenched to perovskite plus brucite, phase D, and/or stishovite. Nearly all spectra show O-H stretching bands that are associated with brucite and/or Shy-B. None of the samples show a Raman peak in the O-H stretching region (3000 to 3700 cm-1) that correlates in intensity with perovskite Raman lattice modes. Our provisional interpretation is that the MgSiO3-perovskite structure incorporates very little H2O (<100 ppmw) and that most of the H in the samples is contained in brucite, phase D, superhydrous phase B (SHyB) or aluminous stishovite. This implies that the magnesium silicate perovskite phase in the lower mantle is unlikely to be a significant host for H in the lower mantle. However, phase D may be stabilized to higher temperatures by incorporation of Al and is extremely hydrous so that two modal percent of phase D may allow the lower mantle to contain several thousand ppmw H2O. Such a small

  8. Observation of Enhanced Hole Extraction in Br Concentration Gradient Perovskite Materials.

    PubMed

    Kim, Min-Cheol; Kim, Byeong Jo; Son, Dae-Yong; Park, Nam-Gyu; Jung, Hyun Suk; Choi, Mansoo

    2016-09-14

    Enhancing hole extraction inside the perovskite layer is the key factor for boosting photovoltaic performance. Realization of halide concentration gradient perovskite materials has been expected to exhibit rapid hole extraction due to the precise bandgap tuning. Moreover, a formation of Br-rich region on the tri-iodide perovskite layer is expected to enhance moisture stability without a loss of current density. However, conventional synthetic techniques of perovskite materials such as the solution process have not achieved the realization of halide concentration gradient perovskite materials. In this report, we demonstrate the fabrication of Br concentration gradient mixed halide perovskite materials using a novel and facile halide conversion method based on vaporized hydrobromic acid. Accelerated hole extraction and enhanced lifetime due to Br gradient was verified by observing photoluminescence properties. Through the combination of secondary ion mass spectroscopy and transmission electron microscopy with energy-dispersive X-ray spectroscopy analysis, the diffusion behavior of Br ions in perovskite materials was investigated. The Br-gradient was found to be eventually converted into a homogeneous mixed halide layer after undergoing an intermixing process. Br-substituted perovskite solar cells exhibited a power conversion efficiency of 18.94% due to an increase in open circuit voltage from 1.08 to 1.11 V and an advance in fill-factor from 0.71 to 0.74. Long-term stability was also dramatically enhanced after the conversion process, i.e., the power conversion efficiency of the post-treated device has remained over 97% of the initial value under high humid conditions (40-90%) without any encapsulation for 4 weeks.

  9. 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.

  10. Structural And Electrical Properties oF (La0.5-xPrxBa0.5)(Mn0.5Ti0.5)O3 Perovskite

    NASA Astrophysics Data System (ADS)

    Alias, Nor Hayati; Shaari, Abdul Halim; Wan Yusoff, Wan Mohd Daud; Mahmood, Che Seman

    2010-01-01

    A single phase monoclinic new perovskite based titano-manganite (La0.5-xPrxBa0.5)(Mn0.5Ti0.5)O3 has been successfully prepared by ceramic solid-state technique at sintering temperature of 1300° C. The concentration of Pr (Praseodymium), x, in molar proportion in A site has been varied as x = 0, 0.02 and 0.2. Analysis has been carried out to determine the electrical properties of the synthesized material at frequency ranging from 5 Hz to 1 MHz; and at temperature range between 25° C to 200° C. It is found that Pr addition promoted liquid phase sintering diffusion, porosity and agglomeration formation at 1300° C. Dual relaxation is observed in unsubstituted Pr sample x = 0 and high Pr substituted sample x = 0.2. This phenomenon was a combinational contribution from a quasi dc (QDC) or low frequency dispersion (LFD), two cole-cole relaxational responses and a resistor. While low concentrated Pr substituted sampled x = 0.02 shows a combinational contribution from a quasi dc (QDC) or low frequency dispersion (LFD), single cole-cole relaxational response and a resistor at room temperature. Pr substitution at x = 0 (max 12000) and x = 0.2 (max 16000) showed high dielectric values compared to low substituted sample x = 0.02. Variation of dielectric loss tangent (tan δ) are observed for all samples at temperature ranged studied.

  11. Solvent substitution

    SciTech Connect

    Not Available

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. The Role of Pb in Piezoelectrics and Possible Substitutions for It

    SciTech Connect

    Singh, David J; Ghita, M.; Halilov, S. V.; Fornari, M.

    2005-01-01

    The interplay between the various patterns of structural instability that are related to the electromechanical coupling in ferroelectric perovskites is discussed using results of density functional based first principles calculations. We focus on two main issues: (1) the competition between tetragonal and rhombohedral ferroelectric states in A-site driven (tolerance factor, t<1) perovskites, and (2) the competition of ferroelectricity and antiferroelectric octahedral rotation. The role of Pb is reviewed in terms of cross gap hybridization of Pb 6p states with O 2p orbitals, and an alternate mechanism for reducing the tendency towards tilt instabilities in low tolerance factor perovskites based on frustration is discussed.

  19. Giant magnetoresistance of manganese oxides with a layered perovskite structure

    NASA Astrophysics Data System (ADS)

    Moritomo, Y.; Asamitsu, A.; Kuwahara, H.; Tokura, Y.

    1996-03-01

    MANGANESE oxides with the cubic perovskite structure (typified by LaMnO3) have stimulated considerable interest because of their magnetoresistive properties1-9 they exhibit extremely large changes in electrical resistance in response to applied magnetic fields, a property that is of technological relevance for the development of magnetic memory and switching devices. But for such applications to be viable, great improvements will be needed in both the sensitivity and temperature dependence of the magnetoresistive response. One approach under consideration for optimizing these properties is chemical substitution10. Here we demonstrate an alternative strategy, in which we synthesize layered variants of the cubic perovskite parent compounds that have a controlled number of MnO2 sheets per unit cell. This strategy is structurally analogous to that employed for the systematic exploration of the high-transition-temperature copper oxide superconductors11. We find that the magneto-resistive properties of these materials depend sensitively on the dimensionality of the manganese oxide lattice. Although the properties of our materials are still far from optimal, further exploration of this series of layered perovskites may prove fruitful.

  20. Carbon Nanotube Charge Collectors in Doped Hybrid Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Olds, Zane; Haroldson, Ross; Mielczarek, Kamil; Zakhidov, Anvar

    2015-03-01

    Hybrid organo-metallic solar cells based on perovskite crystals have had steadily improved power conversion efficiencies over the past two years, and within this period have achieved efficiencies over 19%. We show that additions of Metal-Halide dopants, such as Cobalt (II) Iodide or Indium and Bismuth materials, can cause substitutional doping at the Lead atom. This may result in structural distortions (as in isovalent Co-doping) within the lattice causing change in the spatial distribution of charge carriers. We show that Co-doping results in an increased open circuit voltage upon light soaking due to possible higher charge accumulation. We also have investigated effects of p-doping the hole transport layer. We also incorporate composite sheets of MW carbon nanotubes and silver nanowires as charge collectors. These sheets provide a transparent and flexible electrode with lower sheet resistance due to integration of Ag nanowires. This has an effect on the work function of the sheet, making it more versatile as an electrode for use in a variety of device structures. This allows us a semi-transparent perovskite device, where incident light can be absorbed from either side of the device. This is beneficial towards achieving multi-junction perovskite solar cells. Undergraduate Research Assistant

  1. First principles study of 2D layered organohalide tin perovskites

    NASA Astrophysics Data System (ADS)

    Fraccarollo, Alberto; Canti, Lorenzo; Marchese, Leonardo; Cossi, Maurizio

    2017-06-01

    This article describes the structure and the electronic properties of a series of layered perovskites of a general formula (A+)2(SnX4)-2 where X = I, Br and A+ is an organic cation, either formamidinium, 1-methylimidazolium, or phenylethylammonium. For each system, two conformations are considered, with eclipsed or staggered stacking of the adjacent inorganic layers. Geometry optimizations are performed at the density functional theory level with generalized gradient approximation (GGA) functional and semiempirical correction for dispersion energies; band profiles and bandgaps are computed including both spin orbit coupling (SOC) and correlation (GW) effects through an additive scheme. The theoretical procedures are validated by reproducing the experimental data of a well known 3D tin iodide perovskite. The results, combined with the calculations previously reported on PbI4 analogues, allow us to discuss the effect of cation, metal, and halide substitution in these systems and in particular to explore the possibility of changing the electronic bandgap as required by different applications. The balance of SOC and GW effects depends on the chemical nature of the studied perovskites and strongly influences the value of the simulated bandgap.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  7. 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.

  8. Fluorine Functionalized Graphene Nano Platelets for Highly Stable Inverted Perovskite Solar Cells.

    PubMed

    Kim, Gi-Hwan; Jang, Hyungsu; Yoon, Yung Jin; Jeong, Jaeki; Park, Song Yi; Walker, Bright; Jeon, In-Yup; Jo, Yimhyun; Yoon, Hyun; Kim, Minjin; Baek, Jong-Beom; Kim, Dong Suk; Kim, Jin Young

    2017-09-14

    Edged-selectively fluorine (F) functionalized graphene nanoplatelets (EFGnPs-F) with a p-i-n structure of perovskite solar cells achieved 82% stability relative to initial performance over 30 days of air exposure without encapsulation. The enhanced stability stems from F-substitution on EFGnPs; fluorocarbons such as polytetrafluoroethylene are well-known for their superhydrophobic properties and being impervious to chemical degradation. These hydrophobic moieties tightly protect perovskite layers from air degradation. To directly compare the effect of similar hydrophilic graphene layers, edge-selectively hydrogen functionalized graphene nanoplatelet (EFGnPs-H) treated devices were tested under the same conditions. Like the pristine MAPbI3 perovskite devices, EFGnPs-H treated devices were completely degraded after 10 days. The hydrophobic properties of EFGnPs-F were characterized by contact angle measurement. The test results showed great water repellency compared to pristine perovskite films or EFGnPs-H coated films. This resulted in highly air-stable p-i-n perovskite solar cells.

  9. Spatially separated charge densities of electrons and holes in organic-inorganic halide perovskites

    SciTech Connect

    Li, Dan; Liang, Chunjun E-mail: zhqhe@bjtu.edu.cn; Zhang, Huimin; You, Fangtian; He, Zhiqun E-mail: zhqhe@bjtu.edu.cn; Zhang, Chunxiu

    2015-02-21

    Solution-processable methylammonium lead trihalide perovskites exhibit remarkable high-absorption and low-loss properties for solar energy conversion. Calculation from density functional theory indicates the presence of non-equivalent halogen atoms in the unit cell because of the specific orientation of the organic cation. Considering the 〈100〉 orientation as an example, I{sub 1}, one of the halogen atoms, differs from the other iodine atoms (I{sub 2} and I{sub 3}) in terms of its interaction with the organic cation. The valance-band-maximum (VBM) and conduction-band-minimum (CBM) states are derived mainly from 5p orbital of I{sub 1} atom and 6p orbital of Pb atom, respectively. The spatially separated charge densities of the electrons and holes justify the low recombination rate of the pure iodide perovskite. Chlorine substitution further strengthens the unique position of the I{sub 1} atom, leading to more localized charge density around the I{sub 1} atom and less charge density around the other atoms at the VBM state. The less overlap of charge densities between the VBM and CBM states explains the relatively lower carrier recombination rate of the iodine-chlorine mixed perovskite. Chlorine substitution significantly reduces the effective mass at a direction perpendicular to the Pb-Cl bond and organic axis, enhancing the carrier transport property of the mixed perovskite in this direction.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. Hybrid perovskite resulting from the solid-state reaction between the organic cations and perovskite layers of alpha1-(Br-(CH(2))(2)-NH(3))(2)PbI(4).

    PubMed

    Sourisseau, Sebastien; Louvain, Nicolas; Bi, Wenhua; Mercier, Nicolas; Rondeau, David; Buzaré, Jean-Yves; Legein, Christophe

    2007-07-23

    The alpha1-(Br-(CH(2))(2)-NH(3))(2)PbI(4) hybrid perovskite undergoes a solid-state transformation, that is, the reaction between the organic cations and the perovskite layers to give the new hybrid perovskite (Br-(CH(2))(2)-NH(3))(2-x)(I-(CH(2))(2)-NH(3))(x)PbBr(x)I(4-x), based on mixed halide inorganic layers. This transformation has been followed by a conventional powder X-ray diffraction system equipped with a super speed detector, and both solid-state (13)C NMR and ESI/MS measurements have been adopted in the estimation of the rate of halide substitution. The first reaction step leads to the special composition of x approximately 1 (A phase), while the complete substitution is not achieved even at elevated temperature (x(max) approximately 1.85 (B phase)). This unprecedented solid-state reaction between organic and inorganic components of a hybrid perovskite can be considered as a completely new strategy to achieve interesting hybrid perovskites.

  17. 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.

  18. 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.

  19. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, K.D.

    1991-06-25

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

  20. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, Kenneth D.

    1991-01-01

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

  1. 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.

  2. “Ba{sub 6}Nb{sub 4}RuO{sub 18}” and “LaBa{sub 4}Nb{sub 3}RuO{sub 15}” – The structural consequences of substituting paramagnetic cations into A{sub n}B{sub n−1}O{sub 3n} cation-deficient perovskite oxides

    SciTech Connect

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

    2016-06-15

    The B-cation deficient perovskite phases Ba{sub 6}Nb{sub 4}RuO{sub 18} and LaBa{sub 4}Nb{sub 3}RuO{sub 15} were prepared by ceramic synthesis. Neutron powder diffraction analysis indicates that rather than the 6-layer and 5-layer cation-deficient perovskite structures expected for these phases (by analogy to the known structures of Ba{sub 6}Nb{sub 4}TiO{sub 18} and LaBa{sub 4}Nb{sub 3}TiO{sub 15}) they adopt 5-layer and 4-layer B-cation deficient perovskite structures respectively, and are better described as Ba{sub 5}Nb{sub 3.33}Ru{sub 0.81}O{sub 15} and Ba{sub 3.16}La{sub 0.84}Nb{sub 2.36}Ru{sub 0.72}O{sub 12}. The factors that lead to the compositionally analogous Nb/Ru and Nb/Ti phases adopting different structures are discussed on the basis of the difference between d{sup 0} and non-d{sup 0} transition metal cations. - Graphical abstract: The ruthenium-containing B-cation deficient perovskite phases, Ba{sub 5}Nb{sub 3.33}Ru{sub 0.81}O{sub 15} and Ba{sub 3.16}La{sub 0.84}Nb{sub 2.36}Ru{sub 0.72}O{sub 12}, adopt 5-layer and 4-layer structures respectively, rather than the 6-layer and 5-layer cation-deficient structures adopted by the analogous titanium-containing phases Ba{sub 6}Nb{sub 4}TiO{sub 18} and LaBa{sub 4}Nb{sub 3}TiO{sub 15}. Display Omitted - Highlights: • B-cation deficient perovskite containing paramagnetic cations. • B-cation deficient structure determined by neutron powder diffraction. • Low ‘solubility’ of BaRuO{sub 3} in Ba{sub 5}Nb{sub 4}O{sub 15} leads to novel structure.

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

    PubMed Central

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

    2016-01-01

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

  4. Assessing the toxicity of Pb- and Sn-based perovskite solar cells in model organism Danio rerio

    NASA Astrophysics Data System (ADS)

    Babayigit, Aslihan; Duy Thanh, Dinh; Ethirajan, Anitha; Manca, Jean; Muller, Marc; Boyen, Hans-Gerd; Conings, Bert

    2016-01-01

    Intensive development of organometal halide perovskite solar cells has lead to a dramatic surge in power conversion efficiency up to 20%. Unfortunately, the most efficient perovskite solar cells all contain lead (Pb), which is an unsettling flaw that leads to severe environmental concerns and is therefore a stumbling block envisioning their large-scale application. Aiming for the retention of favorable electro-optical properties, tin (Sn) has been considered the most likely substitute. Preliminary studies have however shown that Sn-based perovskites are highly unstable and, moreover, Sn is also enlisted as a harmful chemical, with similar concerns regarding environment and health. To bring more clarity into the appropriateness of both metals in perovskite solar cells, we provide a case study with systematic comparison regarding the environmental impact of Pb- and Sn-based perovskites, using zebrafish (Danio Rerio) as model organism. Uncovering an unexpected route of intoxication in the form of acidification, it is shown that Sn based perovskite may not be the ideal Pb surrogate.

  5. Assessing the toxicity of Pb- and Sn-based perovskite solar cells in model organism Danio rerio

    PubMed Central

    Babayigit, Aslihan; Duy Thanh, Dinh; Ethirajan, Anitha; Manca, Jean; Muller, Marc; Boyen, Hans-Gerd; Conings, Bert

    2016-01-01

    Intensive development of organometal halide perovskite solar cells has lead to a dramatic surge in power conversion efficiency up to 20%. Unfortunately, the most efficient perovskite solar cells all contain lead (Pb), which is an unsettling flaw that leads to severe environmental concerns and is therefore a stumbling block envisioning their large-scale application. Aiming for the retention of favorable electro-optical properties, tin (Sn) has been considered the most likely substitute. Preliminary studies have however shown that Sn-based perovskites are highly unstable and, moreover, Sn is also enlisted as a harmful chemical, with similar concerns regarding environment and health. To bring more clarity into the appropriateness of both metals in perovskite solar cells, we provide a case study with systematic comparison regarding the environmental impact of Pb- and Sn-based perovskites, using zebrafish (Danio Rerio) as model organism. Uncovering an unexpected route of intoxication in the form of acidification, it is shown that Sn based perovskite may not be the ideal Pb surrogate. PMID:26759068

  6. Assessing the toxicity of Pb- and Sn-based perovskite solar cells in model organism Danio rerio.

    PubMed

    Babayigit, Aslihan; Duy Thanh, Dinh; Ethirajan, Anitha; Manca, Jean; Muller, Marc; Boyen, Hans-Gerd; Conings, Bert

    2016-01-13

    Intensive development of organometal halide perovskite solar cells has lead to a dramatic surge in power conversion efficiency up to 20%. Unfortunately, the most efficient perovskite solar cells all contain lead (Pb), which is an unsettling flaw that leads to severe environmental concerns and is therefore a stumbling block envisioning their large-scale application. Aiming for the retention of favorable electro-optical properties, tin (Sn) has been considered the most likely substitute. Preliminary studies have however shown that Sn-based perovskites are highly unstable and, moreover, Sn is also enlisted as a harmful chemical, with similar concerns regarding environment and health. To bring more clarity into the appropriateness of both metals in perovskite solar cells, we provide a case study with systematic comparison regarding the environmental impact of Pb- and Sn-based perovskites, using zebrafish (Danio Rerio) as model organism. Uncovering an unexpected route of intoxication in the form of acidification, it is shown that Sn based perovskite may not be the ideal Pb surrogate.

  7. Charge carrier mobility in hybrid halide perovskites

    PubMed Central

    Motta, Carlo; El-Mellouhi, Fedwa; Sanvito, Stefano

    2015-01-01

    The charge transport properties of hybrid halide perovskites are investigated with a combination of density functional theory including van der Waals interaction and the Boltzmann theory for diffusive transport in the relaxation time approximation. We find the mobility of electrons to be in the range 5–10 cm2V−1s−1 and that for holes within 1–5 cm2V−1s−1, where the variations depend on the crystal structure investigated and the level of doping. Such results, in good agreement with recent experiments, set the relaxation time to about 1 ps, which is the time-scale for the molecular rotation at room temperature. For the room temperature tetragonal phase we explore two possible orientations of the organic cations and find that the mobility has a significant asymmetry depending on the direction of the current with respect to the molecular axis. This is due mostly to the way the PbI3 octahedral symmetry is broken. Interestingly we find that substituting I with Cl has minor effects on the mobilities. Our analysis suggests that the carrier mobility is probably not a key factor in determining the high solar-harvesting efficiency of this class of materials. PMID:26235910

  8. Charge carrier mobility in hybrid halide perovskites.

    PubMed

    Motta, Carlo; El-Mellouhi, Fedwa; Sanvito, Stefano

    2015-08-03

    The charge transport properties of hybrid halide perovskites are investigated with a combination of density functional theory including van der Waals interaction and the Boltzmann theory for diffusive transport in the relaxation time approximation. We find the mobility of electrons to be in the range 5-10 cm(2)V(-1)s(-1) and that for holes within 1-5 cm(2)V(-1)s(-1), where the variations depend on the crystal structure investigated and the level of doping. Such results, in good agreement with recent experiments, set the relaxation time to about 1 ps, which is the time-scale for the molecular rotation at room temperature. For the room temperature tetragonal phase we explore two possible orientations of the organic cations and find that the mobility has a significant asymmetry depending on the direction of the current with respect to the molecular axis. This is due mostly to the way the PbI3 octahedral symmetry is broken. Interestingly we find that substituting I with Cl has minor effects on the mobilities. Our analysis suggests that the carrier mobility is probably not a key factor in determining the high solar-harvesting efficiency of this class of materials.

  9. 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.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  12. Catalytic combustion of benzene over nanosized LaMnO3 perovskite oxides.

    PubMed

    Jung, Won Young; Lim, Kwon Taek; Lee, Gun Dae; Lee, Man Sig; Hong, Seong-Soo

    2013-09-01

    In this study, LaMnO3 perovskite type oxides were successfully prepared using the malic acid method. The oxides were characterized by TG/DTA, XRD, XPS, TEM and H2-TPR and their catalytic activities for the combustion of benzene were determined. Almost all of the catalysts showed perovskite crystalline phase and had a particle size of 15-60 nm. The LaMnO3 catalysts prepared with more than 1.0 mol of malic acid showed the highest activity and the conversion reached almost 100% at 310 degrees C. The catalysts were modified to enhance the activity by substituting the metal at the A or B site of the perovskite oxides. In the LaMnO3-type catalyst, the partial substitution of Sr into site A enhanced the catalytic activity during benzene combustion. In addition, the partial substitution of Co into site B also increased the catalytic activity and the catalytic activity was in the following order: Co > Cu > Fe in the LaMn1_xBxO3(B = Co, Fe, Cu) type catalysts.

  13. 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

  14. Research Update: Hybrid organic-inorganic perovskite (HOIP) thin films and solar cells by vapor phase reaction

    NASA Astrophysics Data System (ADS)

    Shen, Po-Shen; Chiang, Yu-Hsien; Li, Ming-Hsien; Guo, Tzung-Fang; Chen, Peter

    2016-09-01

    With the rapid progress in deposition techniques for hybrid organic-inorganic perovskite (HOIP) thin films, this new class of photovoltaic (PV) technology has achieved material quality and power conversion efficiency comparable to those established technologies. Among the various techniques for HOIP thin films preparation, vapor based deposition technique is considered as a promising alternative process to substitute solution spin-coating method for large-area or scale-up preparation. This technique provides some unique benefits for high-quality perovskite crystallization, which are discussed in this research update.

  15. 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).

  16. 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

  17. 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

  18. Structural studies on the substitution of Ag, Na doped LCSMO CMR manganites

    NASA Astrophysics Data System (ADS)

    Subhashini, P.; Munirathinam, B.; Krishnaiah, M.; Venkatesh, R.; Venkateswarlu, D.; Ganesan, V.

    2016-05-01

    Synthesis and characterization of colossal magnetoresistance (CMR) materials has been a subject of scientific research due to the unique transport, magnetotransport, and magnetic properties. The single phase polycrystalline La0.7Ca0.1Sr0.1M0.1MnO3 (LCSMO) (M=Ag and Na) samples prepared using nitrate route method. The structural properties are studied at different dopants by X-ray diffraction. The surface morphology and elemental analysis of both samples were carried out by scanning electron microscopy (SEM) and energy dispersive X-ray technique (EDAX) respectively. The structural analysis shows that the LCSMO is crystallized in an orthorhombic perovskite structure belonging to Pnma space group. The crystal size of the sample is calculated using Scherrer formula. The SEM images show that the polycrystalline grains are observed to be near spherical shape and uniform in size. EDAX spectra taken from the surface of the synthesized powders show a nominal composition near the desired one for M=Na sample where as some vacancies are present in the A-site in the case of Ag substitution as will be discussed in this paper.

  19. Structural studies on the substitution of Ag, Na doped LCSMO CMR manganites

    SciTech Connect

    Subhashini, P. Krishnaiah, M.; Munirathinam, B.

    2016-05-06

    Synthesis and characterization of colossal magnetoresistance (CMR) materials has been a subject of scientific research due to the unique transport, magnetotransport, and magnetic properties. The single phase polycrystalline La{sub 0.7}Ca{sub 0.1}Sr{sub 0.1}M{sub 0.1}MnO{sub 3} (LCSMO) (M=Ag and Na) samples prepared using nitrate route method. The structural properties are studied at different dopants by X-ray diffraction. The surface morphology and elemental analysis of both samples were carried out by scanning electron microscopy (SEM) and energy dispersive X-ray technique (EDAX) respectively. The structural analysis shows that the LCSMO is crystallized in an orthorhombic perovskite structure belonging to Pnma space group. The crystal size of the sample is calculated using Scherrer formula. The SEM images show that the polycrystalline grains are observed to be near spherical shape and uniform in size. EDAX spectra taken from the surface of the synthesized powders show a nominal composition near the desired one for M=Na sample where as some vacancies are present in the A-site in the case of Ag substitution as will be discussed in this paper.

  20. General trends for the effect of ionic substitution on the band gap of MAPbX3

    NASA Astrophysics Data System (ADS)

    Qiu, Dechun; Huang, Fuqiang; Li, Shenggang; Mi, Qixi

    2017-09-01

    Perovskites are diverse materials to explore for advanced functional applications, but experimental or computational characterization of individual perovskite compositions is inefficient considering nearly endless possible combinations of the constituent ions. We analyze the band edges of a semiconducting perovskite by constructing electronic wavefunctions based on orbital symmetries, and then extract such information as electron wavevectors, band-edge transition, and chemical bonding. Using MAPbX3 (MA = methylammonium; X = Br, I), CsCdBr3, CsCaBr3, and TMASn(N3)3 (TMA = tetramethylammonium) as prototypical perovskites, we propose a set of trends on whether ionic substitution changes MAPbX3 from a direct band gap to an indirect one. Compositions containing an s2 metal cation and a (pseudo)halide are found to exhibit a direct band gap as MAPbX3 does. The broad applicability of these trends, verified by an extensive range of perovskite compositions, indicates that pseudohalide perovskites should be explored for novel functional materials, and that substitution of Pb2+ in MAPbI3 by non-s2 metal cations will probably deteriorate the optoelectronic properties of MAPbI3.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Crystal structure and thermoelectric properties of Sr–Mo substituted CaMnO3: a combined experimental and computational study† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5tc02318a

    PubMed Central

    Srivastava, D.; Azough, F.; Combe, E.; Funahashi, R.; Kepaptsoglou, D. M.; Ramasse, Q. M.; Molinari, M.; Yeandel, S. R.; Baran, J. D.

    2015-01-01

    A combination of experimental and computational techniques has been employed to study doping effects in perovskite CaMnO3. High quality Sr–Mo co-substituted CaMnO3 ceramics were prepared by the conventional mixed oxide route. Crystallographic data from X-ray and electron diffraction showed an orthorhombic to tetragonal symmetry change on increasing the Sr content, suggesting that Sr widens the transition temperature in CaMnO3 preventing phase transformation-cracking on cooling after sintering, enabling the fabrication of high density ceramics. Atomically resolved imaging and analysis showed a random distribution of Sr in the A-site of the perovskite structure and revealed a boundary structure of 90° rotational twin boundaries across {101}orthorhombic; the latter are predominant phonon scattering sources to lower the thermal conductivity as suggested by molecular dynamics calculations. The effect of doping on the thermoelectric properties was evaluated. Increasing Sr substitution reduces the Seebeck coefficient but the power factor remains high due to improved densification by Sr substitution. Mo doping generates additional charge carriers due to the presence of Mn3+ in the Mn4+ matrix, reducing electrical resistivity. The major impact of Sr on thermoelectric behaviour is the reduction of the thermal conductivity as shown experimentally and by modelling. Strontium containing ceramics showed thermoelectric figure of merit (ZT) values higher than 0.1 at temperatures above 850 K. Ca0.7Sr0.3Mn0.96Mo0.04O3 ceramics exhibit enhanced properties with S 1000K = –180 μV K–1, ρ 1000K = 5 × 10–5 Ωm, k 1000K = 1.8 W m–1 K–1 and ZT ≈ 0.11 at 1000 K. PMID:28496979

  6. Stabilization of the Perovskite Phase of Formamidinium Lead Triiodide by Methylammonium, Cs, and/or Rb Doping.

    PubMed

    Syzgantseva, Olga A; Saliba, Michael; Grätzel, Michael; Rothlisberger, Ursula

    2017-03-16

    In this work we perform a computational study comparing the influence of monovalent cation substitution by methylammonium (MA(+)), cesium (Cs(+)), and rubidium (Rb(+)) on the properties of formamidinium lead triiodide (FAPbI3)-based perovskites. The relative stability of the desired, photoactive perovskite α phase ("black phase") and the nonphotoactive, nonperovskite δ phase ("yellow phase") is studied as a function of dopant nature, concentration and temperature. Cs(+) and Rb(+) are shown to be more efficient in the stabilization of the perovskite α phase than MA(+). Furthermore, varying the dopant concentration allows changing the relative stability at different temperatures, in particular stabilizing the α phase already at 200 K. Upon Cs(+) or Rb(+) doping, the corresponding onset of the optical spectrum is blue-shifted by 0.1-0.2 eV with respect to pure FAPbI3.

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

    PubMed Central

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

    2016-01-01

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

  8. Catalytic Oxidation of Benzene Over LaCoO3 Perovskite-Type Oxides Prepared Using Microwave Process.

    PubMed

    Jung, Won Young; Song, Young In; Lim, Kwon Taek; Lee, Gun Dae; Lee, Man Sig; Hong, Seong-Soo

    2015-01-01

    LaCoO3 perovskite type oxides were successfully prepared using microwave-assisted method, characterized by TG/DTA, XRD, XPS and H2-TPR and their catalytic activities for combustion of benzene were determined. Almost of catalyst showed perovskite crystalline phase and 13-84 nm particle size. LaCoO3 catalysts prepared by microwave-assisted method showed the highest activity and the conversion reached almost 100% at 360 degrees C. In the LaCoO3-type catalyst, the partial substitution of Sr into site A enhanced the catalytic activity on the combustion of benzene. The higher amount of the chemisorbed oxygen was, the better the performance of the combustion catalyst. The catalytic activity of perovskite-type oxides showed a good relationship with the results of H2-TPR and XPS measurement.

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

    PubMed

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

    2016-06-09

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  11. Static and dynamic optical properties of La1-xSrxFeO3-δ: The effects of A-site and oxygen stoichiometry

    DOE PAGES

    Sergey Y. Smolin; Sfeir, Matthew Y.; Scafetta, Mark D.; ...

    2015-12-09

    Perovskite oxides are a promising material class for photovoltaic and photocatalytic applications due to their visible band gaps, nanosecond recombination lifetimes, and great chemical diversity. However, there is limited understanding of the link between composition and static and dynamic optical properties, despite the critical role these properties play in the design of light-harvesting devices. To clarify these relationships, we systemically studied the optoelectronic properties in La1-xSrxFeO3-δ epitaxial films, uncovering the effects of A-site cation substitution and oxygen stoichiometry. Variable-angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and amore » red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy, revealing similar nanosecond photoexcited carrier lifetimes for oxygen deficient and stoichiometric films with the same nominal Fe valence. Furthermore, these results demonstrate that while the static optical absorption is strongly dependent on nominal Fe valence tuned through cation or anion stoichiometry, oxygen vacancies do not appear to play a significantly detrimental role in the recombination kinetics.« less

  12. 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.

  13. 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.

  14. 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.).

  15. 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.

  16. Perovskite Superlattices as Tunable Microwave Devices

    NASA Technical Reports Server (NTRS)

    Christen, H. M.; Harshavardhan, K. S.

    2003-01-01

    Experiments have shown that superlattices that comprise alternating epitaxial layers of dissimilar paraelectric perovskites can exhibit large changes in permittivity with the application of electric fields. The superlattices are potentially useful as electrically tunable dielectric components of such microwave devices as filters and phase shifters. The present superlattice approach differs fundamentally from the prior use of homogeneous, isotropic mixtures of base materials and dopants. A superlattice can comprise layers of two or more perovskites in any suitable sequence (e.g., ABAB..., ABCDABCD..., ABACABACA...). Even though a single layer of one of the perovskites by itself is not tunable, the compositions and sequence of the layers can be chosen so that (1) the superlattice exhibits low microwave loss and (2) the interfacial interaction between at least two of the perovskites in the superlattice renders either the entire superlattice or else at least one of the perovskites tunable.

  17. 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.

  18. 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.

  19. Optimization of spray coating for the fabrication of sequentially deposited planar perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Habibi, Mehran; Ahmadian-Yazdi, Mohammad-Reza; Eslamian, Morteza

    2017-04-01

    We use facile coating techniques including spray coating and drop casting to fabricate methylammonium lead iodide perovskite solar cells through a two-step sequential deposition approach. In the first step, for the deposition of the lead iodide, spray coating substitutes for the commonly used lab-scale spin coating, while the operating parameters of the former process are optimized to achieve a fully covered and uniform film of lead iodide. In the second step, to deposit methylammonium iodide atop the lead iodide layer to form methylammonium lead iodide perovskite, dip-coating process is replaced by the touch-free drop casting and scalable pulsed-spray coating. It is found that the performance of the perovskite films and devices made by pulsed-spray coating and drop casting is similar to those prepared by dip coating, while the large-scale production capabilities of such methods beside the low material consumptions of drop casting prove their potential to replace dip coating in large-scale manufacturing of perovskite solar cells. The champion devices fabricated by spray-drop and spin-drop techniques demonstrated power conversion efficiencies of 6.92% and 9.48%, respectively. It is expected that device fabrication in a low-humidity environment using the optimized parameters and optimization of other layers will result in higher efficiencies.

  20. Thermoelasticity of Al- and Fe-bearing MgSiO3 Post-perovskite

    NASA Astrophysics Data System (ADS)

    Shukla, G.; Sarkar, K.; Wentzcovitch, R. M.

    2016-12-01

    We present ab initio (LDA + Usc) calculations of high-temperature and high-pressure elastic properties of pure, iron- (ferrous, Fe2+; and ferric, Fe3+ ), and aluminum-bearing MgSiO3 post-perovskite, possibly the dominant phase in the deep lower mantle and the D" region of the Earth. Thermal effects are addressed within the quasi-harmonic approximation by combining vibrational density of states (VDOS) and static elastic constants. Aggregate elastic moduli and sound velocities for the Mg-end member are successfully compared with limited experimental data available. Effects of iron (Fe) and aluminum (Al) substitutions on elastic properties and their pressure and temperature dependence have been thoroughly investigated. At the observed perovskite to post-perovskite transition (P = 125 GPa and T = 2500 K), compressional and shear velocities increase by 0-1% and 1.5-3.75%, respectively. This observation is consistent with seismic observations of the D" region, which suggests that our robust estimates of elastic properties of the post-perovskite phase will be very helpful to understand lateral velocity variations in the deep lower mantle region and constrain its composition and thermal structure.

  1. High Quantum Yield Blue Emission from Lead-Free Inorganic Antimony Halide Perovskite Colloidal Quantum Dots.

    PubMed

    Zhang, Jian; Yang, Ying; Deng, Hui; Farooq, Umar; Yang, Xiaokun; Khan, Jahangeer; Tang, Jiang; Song, Haisheng

    2017-09-26

    Colloidal quantum dots (QDs) of lead halide perovskite have recently received great attention owing to their remarkable performances in optoelectronic applications. However, their wide applications are hindered from toxic lead element, which is not environment- and consumer-friendly. Herein, we utilized heterovalent substitution of divalent lead (Pb(2+)) with trivalent antimony (Sb(3+)) to synthesize stable and brightly luminescent Cs3Sb2Br9 QDs. The lead-free, full-inorganic QDs were fabricated by a modified ligand-assisted reprecipitation strategy. A photoluminescence quantum yield (PLQY) was determined to be 46% at 410 nm, which was superior to that of other reported halide perovskite QDs. The PL enhancement mechanism was unraveled by surface composition derived quantum-well band structure and their large exciton binding energy. The Br-rich surface and the observed 530 meV exciton binding energy were proposed to guarantee the efficient radiative recombination. In addition, we can also tune the inorganic perovskite QD (Cs3Sb2X9) emission wavelength from 370 to 560 nm via anion exchange reactions. The developed full-inorganic lead-free Sb-perovskite QDs with high PLQY and stable emission promise great potential for efficient emission candidates.

  2. 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..

  3. Electron-doping through La{sup III}-for-Sr{sup II} substitution in (Sr{sub 1-} {sub x} La {sub x} ){sub 2}FeTaO{sub 6}: Effects on the valences and ordering of the B-site cations, Fe and Ta

    SciTech Connect

    Rautama, E.-L.; Chan, T.S.; Liu, R.S.; Chen, J.M.; Yamauchi, H.; Karppinen, M. . E-mail: karppinen@msl.titech.ac.jp

    2006-01-15

    We have employed aliovalent A-site cation substitution, La{sup III}-for-Sr{sup II}, to dope the Sr(Fe{sub 0.5}Ta{sub 0.5})O{sub 3} perovskite oxide with electrons. Essentially single-phase samples of (Sr{sub 1-} {sub x} La {sub x} )(Fe{sub 0.5}Ta{sub 0.5})O{sub 3} were successfully synthesized up to x{approx}0.3 in a vacuum furnace at 1400 deg. C. The samples were found to crystallize (rather than with orthorhombic symmetry) in monoclinic space group P2{sub 1}/n that accounts for the partial ordering of the B-site cations, Fe and Ta. With increasing La-substitution level, x, the degree of Fe/Ta order was found to increase such that the La-richest compositions are best described by the B-site ordered double-perovskite formula (Sr,La){sub 2}FeTaO{sub 6}. From Fe L {sub 3} and Ta L {sub 3} XANES spectra it was revealed that upon electron doping the two B-site cations, Fe{sup III} and Ta{sup V}, are both prone to reduction. Magnetic susceptibility measurements showed spin-glass type behaviour for all the samples with a transition temperature slightly increasing with increasing x. -- Graphical abstract: Valence states of Fe and Ta are controlled in the partially ordered perovskite oxide (Sr,La){sub 2}FeTaO{sub 6}, through aliovalent La{sup III}-for-Sr{sup II} substitu0010ti.

  4. Optical analysis of CH3NH3SnxPb1–xI3 absorbers: a roadmap for perovskite-on-perovskite tandem solar cells† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ta04840d Click here for additional data file.

    PubMed Central

    Anaya, Miguel; Lozano, Gabriel; Saliba, Michael; Anguita, Pablo; Roose, Bart; Abate, Antonio; Steiner, Ullrich; Grätzel, Michael; Calvo, Mauricio E.; Hagfeldt, Anders

    2016-01-01

    Organic–inorganic perovskite structures in which lead is substituted by tin are exceptional candidates for broadband light absorption. Herein we present a thorough analysis of the optical properties of CH3NH3SnxPb1–xI3 films, providing the field with definitive insights about the possibilities of these materials for perovskite solar cells of superior efficiency. We report a user's guide based on the first set of optical constants obtained for a series of tin/lead perovskite films, which was only possible to measure due to the preparation of optical quality thin layers. According to the Shockley–Queisser theory, CH3NH3SnxPb1–xI3 compounds promise a substantial enhancement of both short circuit photocurrent and power conversion efficiency in single junction solar cells. Moreover, we propose a novel tandem architecture design in which both top and bottom cells are made of perovskite absorbers. Our calculations indicate that such perovskite-on-perovskite tandem devices could reach efficiencies over 35%. Our analysis serves to establish the first roadmap for this type of cells based on actual optical characterization data. We foresee that this study will encourage the research on novel near-infrared perovskite materials for photovoltaic applications, which may have implications in the rapidly emerging field of tandem devices. PMID:27774148

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  6. 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

  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. 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.

  13. Covalently Functionalized SWCNTs as Tailored p-Type Dopants for Perovskite Solar Cells.

    PubMed

    Miletić, Tanja; Pavoni, Eleonora; Trifiletti, Vanira; Rizzo, Aurora; Listorti, Andrea; Colella, Silvia; Armaroli, Nicola; Bonifazi, Davide

    2016-10-04

    The covalent functionalization of (7,6)-enriched single-walled carbon nanotubes (SWCNTs) with oligophenylenevinylene (OPV) moieties terminating with a dimethylamino group is proposed as an efficient way to enhance the affinity of CNTs with spiro-MeOTAD in perovskite-based solar cells. The evidence of SWCNTs functionalization and the degree of OPV substitution on SWCNTs are established from TGA, XPS, TEM, and Raman techniques. Our tailored doping materials afford photovoltaic performances in line with conventional Li-doped spiro-MeOTAD, showing at the same time a significantly improved chemical stability of the perovskite component over time. Furthermore, the comparison of the photovoltaic performances with those obtained with nonfunctionalized SWCNTs suggest that the presence of the organic appends ensures highly reproducible PV performances. These results demonstrate the suitability of this functionalized SWCNT material as a valid doping agent for spiro-MeOTAD, representing a viable alternative to the conventional Li salt.

  14. 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.

  15. Geometrical Spin Frustration of Unusually High Valence Fe(5+) in the Double Perovskite La2LiFeO6.

    PubMed

    Xiong, Peng; Seki, Hayato; Guo, Haichuan; Hosaka, Yoshiteru; Saito, Takashi; Mizumaki, Masaichiro; Shimakawa, Yuichi

    2016-06-20

    A double perovskite-structure oxide La2LiFeO6 with unusually high-valence Fe(5+) was synthesized using a high-pressure technique. The Li(+) and Fe(5+) ions at the B site in the rhombohedral R3̅ perovskite structure are ordered in a rock salt manner, and the resultant tetrahedral network of Fe(5+) gives geometrical spin frustration, which is consistent with a large frustration index f (|θ|/TN) ≈ 10. Mg(2+) substitution for Li(+) produces Fe(4+) from some Fe(5+) and changes the magnetic properties. The Weiss temperature is increased from -119 to 21 K by the substitution of only 1%, significantly decreasing the frustration index. The geometrical frustration of the Fe(5+) spin sublattice cannot be tolerant for even a very small amount of Fe(4+) disturbance.

  16. 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

  17. 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.

  18. Dense Membranes for Anode Supported all Perovskite IT-SOFCs

    SciTech Connect

    Rambabu Bobba

    2006-09-14

    During this first year of the project, a post doctoral fellow (Dr. Hrudananda Jena), and two graduate students (Mr. Vinay B. V. Sivareddy, Aswin Somuru), were supported through this project funds. Also, partial support was provided to three undergraduate students (Jonthan Dooley, India Snowden, Jeremy Gilmore) majoring in Chemistry, Physics, and Engineering disciplines. Various wet chemical methods of synthesis have been attempted to prepare perovskite oxide powders with a hope to improve and engineer its properties to meet the requirements of Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFCs) components. Various compounds were synthesized, characterized by XRD, TEM, SEM, XPS, electron microprobe and their electrical transport properties were measured by EIS at elevated temperatures and compared. Sonochemical technique (power of ultra sonic probe 750 watt) combined with hydrothermal treatment of precursors for the preparation of calcium hydroxy apatites (Ca-HAp) was used for the first time. Ca-HAp was substituted with Sr and Mg (50% replacement of Ca in Ca-HAp) to study the effect of substitution on Ca-HAp. Calcium hydroxy apatite is a bioceramic and has potential applications as artificial bone, enamel materials. In this study we tried to investigate its use as proton conductors in PC-SOFC. The properties like electrical conductivity, crystal structure, compositions of CaHAp were studied and compared with the natural bone material. The comparison found to be excellent indicating the efficiency of the preparation techniques. The typical value of conductivity measured is 0.091 x 10{sup -6} Scm{sup -1} at 25 C and 19.26 x 10{sup -6} Scm{sup -1} at 850 C with an applied frequency of 100 kHz. The conductivity increases on increasing frequency and temperature and reaches 0.05mS/cm at 500 C. The crystal structure and phase stability of perovskites as well as apatites were investigated with respect to substitution of various iso-valent and alivalent ions to

  19. Nucleophilic Aromatic Substitution.

    ERIC Educational Resources Information Center

    Avila, Walter B.; And Others

    1990-01-01

    Described is a microscale organic chemistry experiment which demonstrates one feasible route in preparing ortho-substituted benzoic acids and provides an example of nucleophilic aromatic substitution chemistry. Experimental procedures and instructor notes for this activity are provided. (CW)

  20. Nucleophilic Aromatic Substitution.

    ERIC Educational Resources Information Center

    Avila, Walter B.; And Others

    1990-01-01

    Described is a microscale organic chemistry experiment which demonstrates one feasible route in preparing ortho-substituted benzoic acids and provides an example of nucleophilic aromatic substitution chemistry. Experimental procedures and instructor notes for this activity are provided. (CW)

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. Structure engineering of hole-conductor free perovskite-based solar cells with low-temperature-processed commercial carbon paste as cathode.

    PubMed

    Zhang, Fuguo; Yang, Xichuan; Wang, Haoxin; Cheng, Ming; Zhao, Jianghua; Sun, Licheng

    2014-09-24

    Low-temperature-processed (100 °C) carbon paste was developed as counter electrode material in hole-conductor free perovskite/TiO2 heterojunction solar cells to substitute noble metallic materials. Under optimized conditions, an impressive PCE value of 8.31% has been achieved with this carbon counter electrode fabricated by doctor-blading technique. Electrochemical impedance spectroscopy demonstrates good charge transport characteristics of low-temperature-processed carbon counter electrode. Moreover, this carbon counter electrode-based perovskite solar cell exhibits good stability over 800 h.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. Slater insulator in iridate perovskites with strong spin-orbit coupling

    DOE PAGES

    Cui, Q.; Cheng, J. -G.; Fan, W.; ...

    2016-10-20

    The perovskite SrIrO3 is an exotic narrow-band metal owing to a confluence of the strengths of the spin-orbit coupling (SOC) and the electron-electron correlations. It has been proposed that topological and magnetic insulating phases can be achieved by tuning the SOC, Hubbard interactions, and/or lattice symmetry. Here, we report that the substitution of nonmagnetic, isovalent Sn4+ for Ir4+ in the SrIr1–xSnxO3 perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic (AF) phase at TN ≥ 225 K. The continuous change of the cell volume as detected by x-ray diffraction and the λ-shape transition of the specificmore » heat on cooling through TN demonstrate that the metal-insulator transition is of second order. Neutron powder diffraction results indicate that the Sn substitution enlarges an octahedral-site distortion that reduces the SOC relative to the spin-spin exchange interaction and results in the type-G AF spin ordering below TN. Measurement of high-temperature magnetic susceptibility shows the evolution of magnetic coupling in the paramagnetic phase typical of weak itinerant-electron magnetism in the Sn-substituted samples. Furthermore, a reduced structural symmetry in the magnetically ordered phase leads to an electron gap opening at the Brillouin zone boundary below TN in the same way as proposed by Slater.« less

  17. Slater Insulator in Iridate Perovskites with Strong Spin-Orbit Coupling

    NASA Astrophysics Data System (ADS)

    Cui, Q.; Cheng, J.-G.; Fan, W.; Taylor, A. E.; Calder, S.; McGuire, M. A.; Yan, J.-Q.; Meyers, D.; Li, X.; Cai, Y. Q.; Jiao, Y. Y.; Choi, Y.; Haskel, D.; Gotou, H.; Uwatoko, Y.; Chakhalian, J.; Christianson, A. D.; Yunoki, S.; Goodenough, J. B.; Zhou, J.-S.

    2016-10-01

    The perovskite SrIrO3 is an exotic narrow-band metal owing to a confluence of the strengths of the spin-orbit coupling (SOC) and the electron-electron correlations. It has been proposed that topological and magnetic insulating phases can be achieved by tuning the SOC, Hubbard interactions, and/or lattice symmetry. Here, we report that the substitution of nonmagnetic, isovalent Sn4 + for Ir4 + in the SrIr1 -xSnxO3 perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic (AF) phase at TN≥225 K . The continuous change of the cell volume as detected by x-ray diffraction and the λ -shape transition of the specific heat on cooling through TN demonstrate that the metal-insulator transition is of second order. Neutron powder diffraction results indicate that the Sn substitution enlarges an octahedral-site distortion that reduces the SOC relative to the spin-spin exchange interaction and results in the type-G AF spin ordering below TN . Measurement of high-temperature magnetic susceptibility shows the evolution of magnetic coupling in the paramagnetic phase typical of weak itinerant-electron magnetism in the Sn-substituted samples. A reduced structural symmetry in the magnetically ordered phase leads to an electron gap opening at the Brillouin zone boundary below TN in the same way as proposed by Slater.

  18. 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

  19. 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.

  20. Enhancement of redox- and phase-stability of thermoelectric CaMnO{sub 3−δ} by substitution

    SciTech Connect

    Thiel, Philipp; Populoh, Sascha; Yoon, Songhak; Weidenkaff, Anke

    2015-09-15

    Redox Reactivity and structural phase transitions have a major impact on transport and me-chemical properties of thermoelectric CaMnO{sub 3−δ}. In this study series of Ca{sub 1−x}A{sub x}Mn{sub 1−y}B{sub y}O{sub 3−δ} (0≤x,y≤0.8) compounds, each with A-site (Dy{sup 3+}, Yb{sup 3+}) or B-site (Nb{sup 5+}, Ta{sup 5+} and Mo{sup 6+}, W{sup 6+}) substitution, were synthesized and crystallographically analyzed. It was found that the high-temperature oxygen content is widely independent from the substituent. Subsequently, with increasing temperature the differences in the Seebeck coefficient vanish above 1200 K. With increasing substitution the orthorhombic distortion of the perovskite-like phase increases. The orthorhombic distortion and the upper temperature limit of the stability of the orthorhombic crystal structure show an almost linear dependency. Accordingly, the mechanical stability of all-oxides thermoelectric converters at temperatures exceeding 1000 K will be increased employing materials with high substitution level and substituents inducing a high orthorhombic distortion. - Graphical abstract: Thermoelectric n-type CaMn{sub 0.98}W{sub 0.02}O{sub 3−δ}—Transport properties and expansion coefficient of: Oxygen loss (green region) and upper stability limit of the orthorhombic phase (yellow region) strongly affect the transport properties. Both features also cause lattice expansion, which leads to cracking of thermoelectric all-oxide converters. We report how the upper limit for application can be shifted to even higher temperatures. - Highlights: • Level of Mn{sup 3+} at RT determines reduction behavior of Ca{sub 1−x}A{sub x}Mn{sub 1−y}B{sub y}O{sub 3−δ} at HT. • Differences in Seebeck coefficient vanish at T>1200 K independent from substitution. • Substitution increases orthorhombicity of Ca{sub 1−x}A{sub x}Mn{sub 1−y}B{sub y}O{sub 3−δ}. • Linear dependence of orthorhombicity and phase stability. • Design guidelines for

  1. 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.

  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. Spin state of ferric iron in MgSiO{sub 3} perovskite and its effect on elastic properties.

    SciTech Connect

    Catalli, K.; Shim, S. H.; Prakapenka, V. B.; Zhao, J.; Sturhahn, W.; Chow, P.; Xiao, Y.; Liu, H.; Cynn, H.; Evans, W. J.; Massachusetts Inst. of Tech.

    2010-01-15

    Recent studies have indicated that a significant amount of iron in MgSiO{sub 3} perovskite (Pv) is Fe{sup 3+} (Fe{sup 3+}/{Sigma}Fe = 10-60%) due to crystal chemistry effects at high pressure (P) and that Fe{sup 3+} is more likely than Fe{sup 2+} to undergo a high-spin (HS) to low-spin (LS) transition in Pv in the mantle. We have measured synchrotron Moessbauer spectroscopy (SMS), X-ray emission spectroscopy (XES), and X-ray diffraction (XRD) of Pv with all iron in Fe{sup 3+} in the laser-heated diamond-anvil cell to over 100 GPa. Fe{sup 3+} increases the anisotropy of the Pv unit cell, whereas Fe{sup 2+} decreases it. In Pv synthesized above 50 GPa, Fe{sup 3+} enters into both the dodecahedral (A) and octahedral (B) sites approximately equally, suggesting charge coupled substitution. Combining SMS and XES, we found that the LS population in the B site gradually increases with pressure up to 50-60 GPa where all Fe{sup 3+} in the B site becomes LS, while Fe{sup 3+} in the A site remains HS to at least 136 GPa. Fe{sup 3+} makes Pv more compressible than Mg-endmember below 50 GPa because of the gradual spin transition in the B site together with lattice compression. The completion of the spin transition at 50-60 GPa increases bulk modulus with no associated change in density. This elasticity change can be a useful seismic probe for investigating compositional heterogeneities associated with Fe{sup 3+}.

  4. First principles investigation of substituted strontium hexaferrite

    NASA Astrophysics Data System (ADS)

    Dixit, Vivek

    This dissertation investigates how the magnetic properties of strontium hexaferrite change upon the substitution of foreign atoms at the Fe sites. Strontium hexaferrite, SrFe12O19, is a commonly used hard magnetic material and is produced in large quantities (around 500,000 tons per year). For different applications of strontium hexaferrite, its magnetic properties can be tuned by a proper substitution of the foreign atoms. Experimental screening for a proper substitution is a cost-intensive and time-consuming process, whereas computationally it can be done more efficiently. We used the 'density functional theory' a first principles based method to study substituted strontium hexaferrite. The site occupancies of the substituted atoms were estimated by calculating the substitution energies of different configurations. The formation probabilities of configurations were used to calculate the magnetic properties of substituted strontium hexaferrite. In the first study, Al-substituted strontium hexaferrite, SrFe12-x AlxO19 with x=0.5 and x=1.0 were investigated. It was found that at the annealing temperature the non-magnetic Al +3 ions preferentially replace Fe+3 ions from the 12 k and 2a sites. We found that the magnetization decreases and the magnetic anisotropy field increases as the fraction, x of the Al atoms increases. In the second study, SrFe12-xGaxO19 and SrFe12-xInxO19 with x=0.5 and x=1.0 were investigated. In the case of SrFe12-xGaxO19, the sites where Ga+3 ions prefer to enter are: 12 k, 2a, and 4f1. For SrFe12-xInxO19, In+3 ions most likely to occupy the 12k, 4f1 , and 4f2 sites. In both cases the magnetization was found to decrease slightly as the fraction of substituted atom increases. The magnetic anisotropy field increased for SrFe12-xGaxO 19, and decreased for SrFe12-xInxO19 as the concentration of substituted atoms increased. In the third study, 23 elements (M) were screened for their possible substitution in strontium hexaferrite, SrFe12-xMxO 19

  5. 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

  6. Fermi arcs vs. fermi pockets in electron-doped perovskite iridates

    SciTech Connect

    He, Junfeng; Hafiz, H.; Mion, Thomas R.; Hogan, T.; Dhital, C.; Chen, X.; Lin, Qisen; Hashimoto, M.; Lu, D. H.; Zhang, Y.; Markiewicz, R. S.; Bansil, A.; Wilson, S. D.; He, Rui -Hua

    2015-02-23

    We report on an angle resolved photoemission (ARPES) study of bulk electron-doped perovskite iridate, (Sr1-xLax)₃Ir₂O₇. Fermi surface pockets are observed with a total electron count in keeping with that expected from La substitution. Depending on the energy and polarization of the incident photons, these pockets show up in the form of disconnected “Fermi arcs”, reminiscent of those reported recently in surface electron-doped Sr₂IrO₄. Our observed spectral variation is consistent with the coexistence of an electronic supermodulation with structural distortion in the system.

  7. Density functional simulation of carbon at the titanium site in perovskite barium titanate

    NASA Astrophysics Data System (ADS)

    AL-Hadidi, Meaad S.; Goss, J. P.; Briddon, P. R.; Al-Hamadany, Raied A.; Ahmed, Mariam E.; Rayson, M. J.

    2015-04-01

    The perovskite family includes many titanates which have been used in various applications. BaTiO3 is interesting due to its room-temperature ferroelectric properties and relative low toxicity. Organic precursors present during growth make carbon a potentially key impurity, which would subsequently impact upon the BaTiO3 properties. This paper presents a density function study of the structural and electronic properties of carbon substituting for Ti in rhombohedral BaTiO3. The local vibrational modes of the defect centre has been calculated and suggested as a possible route to experimental identification.

  8. Fermi arcs vs. fermi pockets in electron-doped perovskite iridates

    DOE PAGES

    He, Junfeng; Hafiz, H.; Mion, Thomas R.; ...

    2015-02-23

    We report on an angle resolved photoemission (ARPES) study of bulk electron-doped perovskite iridate, (Sr1-xLax)₃Ir₂O₇. Fermi surface pockets are observed with a total electron count in keeping with that expected from La substitution. Depending on the energy and polarization of the incident photons, these pockets show up in the form of disconnected “Fermi arcs”, reminiscent of those reported recently in surface electron-doped Sr₂IrO₄. Our observed spectral variation is consistent with the coexistence of an electronic supermodulation with structural distortion in the system.

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. A new family of barium-doped Sr2Fe1.5Mo0.5O6-δ perovskites for application in intermediate temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Dai, Ningning; Wang, Zhenhua; Jiang, Taizhi; Feng, Jie; Sun, Wang; Qiao, Jinshuo; Rooney, David; Sun, Kening

    2014-12-01

    Sr2-xBaxFe1.5Mo0.5O6-δ (x = 0, 0.2, 0.4, 0.6, 0.8, 1) perovskite materials have been prepared as potential cathodes for intermediate temperature solid oxide fuel cells (IT-SOFCs) via a sol-gel combustion method. X-ray diffraction (XRD) confirms that the expansion of the unit cell derived from the substitution of the large radius Ba atom, with the impurity phase structure only being detected when x = 0.8 and 1. Concurrently, thermal expansion coefficients (TECs) increase with increasing Ba doping. X-ray photoelectron spectrometry (XPS) measurements show that A-site doped Ba in the perovskite has an insignificant impact on the existence and ratio of Fe2+/Fe3+ and Mo6+/Mo5+ species within the Sr2-xBaxFe1.5Mo0.5O6-δ (x = 0.2, 0.4, 0.6) (SBFM) samples. Compared with Sr2Fe1.5Mo0.5O6-δ, the SBFM cathodes exhibited better electrochemical performance, which has been confirmed by the electrochemical impedance spectra (EIS). In particular, Sr1.8Ba0.2Fe1.5Mo0.5O6-δ (SB0.2FM) shows the lowest interface polarization (Rp). Furthermore the peak power densities of single cells based on the SB0.2FM cathode are 0.87 and 1.30 W cm-2 at 700 and 750 °C, respectively. All these results suggest that SBFM materials are promising cathodes for IT-SOFCs.

  14. 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.

  15. 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.

  16. Water electrolysis on La1-xSrxCoO3-δ perovskite electrocatalysts

    DOE PAGES

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; ...

    2016-03-23

    Here, perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr2+ substitution into La1–xSrxCoO3–δ. We attempt to rationalize the highmore » activities of La1–xSrxCoO3–δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.« less

  17. Water electrolysis on La1-xSrxCoO3-δ perovskite electrocatalysts

    NASA Astrophysics Data System (ADS)

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; Hardin, William G.; Dai, Sheng; Kolpak, Alexie M.; Johnston, Keith P.; Stevenson, Keith J.

    2016-03-01

    Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B-O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co-O bond and the concentration of oxygen vacancies are controlled through Sr2+ substitution into La1-xSrxCoO3-δ. We attempt to rationalize the high activities of La1-xSrxCoO3-δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.

  18. Water electrolysis on La(1-x)Sr(x)CoO(3-δ) perovskite electrocatalysts.

    PubMed

    Mefford, J Tyler; Rong, Xi; Abakumov, Artem M; Hardin, William G; Dai, Sheng; Kolpak, Alexie M; Johnston, Keith P; Stevenson, Keith J

    2016-03-23

    Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B-O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co-O bond and the concentration of oxygen vacancies are controlled through Sr(2+) substitution into La(1-x)Sr(x)CoO(3-δ) . We attempt to rationalize the high activities of La(1-x)Sr(x)CoO(3-δ) through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.

  19. Identifying the charge generation dynamics in Cs(+)-based triple cation mixed perovskite solar cells.

    PubMed

    Salado, Manuel; Kokal, Ramesh K; Calio, Laura; Kazim, Samrana; Deepa, Melepurath; Ahmad, Shahzada

    2017-08-30

    Triple cation based perovskite solar cells offer enhanced moisture tolerance and stability compared to mixed perovskites. Slight substitution of methyl ammonium or formamidinium cation by cesium (Cs(+)), was also reported to eliminate halide segregation due to its smaller size. To elucidate the device kinetics and understand the role of the Cs, we undertook different modes of scanning probe microscopy and electrochemical impedance spectroscopy (EIS) experiments. Kelvin probe force microscopy revealed that the incorporation of the Cs cation increases the contact potential difference (CPD), this CPD further increases when Spiro-OMeTAD is used as a hole transport material. The current at the nanoscale level shows improvement with Cs inclusion and further enhancement by the Spiro-OMeTAD deposition, studied under light illumination, which supports the high photocurrent density obtained from the cells. EIS demonstrates that in a triple cation environment, reduced carrier recombination at the TiO2/perovskite interface was also obtained which in turn allow us to achieve a higher Voc value.

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

    SciTech Connect

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

    2015-10-15

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

  1. Ag-Incorporated Organic-Inorganic Perovskite Films and Planar Heterojunction Solar Cells.

    PubMed

    Chen, Qi; Chen, Lei; Ye, Fengye; Zhao, Ting; Tang, Feng; Rajagopal, Adharsh; Jiang, Zheng; Jiang, Shenlong; Jen, Alex K-Y; Xie, Yi; Cai, Jinhua; Chen, Liwei

    2017-04-06

    Controlled doping for adjustable material polarity and charge carrier concentration is the basis of semiconductor materials and devices, and it is much more difficult to achieve in ionic semiconductors (e.g., ZnO and GaN) than in covalent semiconductors (e.g., Si and Ge), due to the high intrinsic defect density in ionic semiconductors. The organic-inorganic perovskite material, which is frenetically being researched for applications in solar cells and beyond, is also an ionic semiconductor. Here we present the Ag-incorporated organic-inorganic perovskite films and planar heterojunction solar cells. Partial substitution of Pb(2+) by Ag(+) leads to improved film morphology, crystallinity, and carrier dynamics as well as shifted Fermi level and reduced electron concentration. Consequently, in planar heterojunction photovoltaic devices with inverted stacking structure, Ag incorporation results in an enhancement of the power conversion efficiency from 16.0% to 18.4% in MAPbI3 based devices and from 11.2% to 15.4% in MAPbI3-xClx based devices. Our work implies that Ag incorporation is a feasible route to adjust carrier concentrations in solution-processed perovskite materials in spite of the high concentration of intrinsic defects.

  2. 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

  3. Hole-Transporting Materials with a Two-Dimensionally Expanded π-System around an Azulene Core for Efficient Perovskite Solar Cells.

    PubMed

    Nishimura, Hidetaka; Ishida, Naoki; Shimazaki, Ai; Wakamiya, Atsushi; Saeki, Akinori; Scott, Lawrence T; Murata, Yasujiro

    2015-12-23

    Two-dimensionally expanded π-systems, consisting of partially oxygen-bridged triarylamine skeletons that are connected to an azulene (1-3) or biphenyl core (4), were synthesized and characterized. When tetra-substituted azulene 1 was used as a hole-transporting material (HTM) in perovskite solar cells, the observed performance (power conversion efficiency = 16.5%) was found to be superior to that of the current HTM standard Spiro-OMeTAD. A comparison of the hole mobility, the ability to control the HOMO and LUMO levels, and the hole-collection efficiency at the perovskite/HTM interface in 1 with reference compounds (2-4 and Spiro-OMeTAD) led to the elucidation of key factors required for HTMs to act efficiently in perovskite solar cells.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Colloidal Organolead Halide Perovskite with a High Mn Solubility Limit: A Step Toward Pb-Free Luminescent Quantum Dots.

    PubMed

    Arunkumar, Paulraj; Gil, Kyeong Hun; Won, Seob; Unithrattil, Sanjith; Kim, Yoon Hwa; Kim, Ha Jun; Im, Won Bin

    2017-09-07

    Organolead halide perovskites have emerged as a promising optoelectronic material for lighting due to its high quantum yield, color-tunable, and narrow emission. Despite their unique properties, toxicity has intensified the search for ecofriendly alternatives through partial or complete replacement of lead. Herein, we report a room-temperature synthesized Mn(2+)-substituted 3D-organolead perovskite displacing ∼90% of lead, simultaneously retaining its unique excitonic emission, with an additional orange emission of Mn(2+) via energy transfer. A high Mn solubility limit of 90% was attained for the first time in lead halide perovskites, facilitated by the flexible organic cation (CH3NH3)(+) network, preserving the perovskite structure. The emission intensities of the exciton and Mn were influenced by the halide identity that regulates the energy transfer to Mn. Homogeneous emission and electron spin resonance characteristics of Mn(2+) indicate a uniform distribution of Mn. These results suggest that low-toxicity 3D-CH3NH3Pb1-xMnxBr3-(2x+1)Cl2x+1 nanocrystals may be exploited as magnetically doped quantum dots with unique optoelectronic properties.

  10. 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.

  11. Mineral physics of the perovskite to post-perovskite transition in CaIrO3 - seismological implications for the lower mantle

    NASA Astrophysics Data System (ADS)

    Tronnes, R. G.; Stolen, S.; Boffa-Ballaran, T.; Frost, D. J.; Balic-Zunic, T.; Olsen, L. A.

    2007-12-01

    In the system CaIrO3 the perovskite (pv, Pbnm) to post-perovskite (ppv, Cmcm) phase transition is accessible at 1-5 GPa and 1450-1610 C. Both of the CaIrO3-phases are quenchable to ambient conditions, making the system suitable for studies of crystallographic, crystal chemical and mineral physical properties that may provide important guidelines to the behaviour of MgSiO3-based compositions of the lower mantle. Combined results from experimental phase relations, experimental pV-EoS [1], thermal expansivity and density functional theory (DFT) modeling [2] provide insights into the seismologic and geodynamic features of the pv-ppv-transition in the lowermost mantle. Experimental phase relations in the 1-5 GPa range and DFT modeling give Clapeyron slopes for the pv-ppv-transition of 24.5 and 19 MPa/K, respectively, which is about twice the published dp/dT-slopes of the MgSiO3-system. The compressibility of the CaIrO3-crystal structures derived from pv-EoS experiments and DFT-modelling are very similar. In ppv the b-axis compressibility is about twice that of the other two axes. In pv the a- and c-axis compressibilities exceed that of the b-axis by factors of 3 and 2, respectively. The bulk modulus change of the pv to ppv transition is negative, whereas the DFT-derived shear moduli of the two phases give a positive delta-G of the same transition. These results are consistent with DFT-modelling of the MgSiO3-system and with seismological data [3,4]. The apparent suitability of the CaIrO3-component as a low-pressure analogue for the lower mantle MgSiO3-component in terms of crystallographic and mineral physics properties has encouraged an investigation of the incorporation of trivalent cations. By studying the incorporation of a small selection of ions with variable radii in CaIrO3-based pv and ppv, we are searching for systematic relations between various trivalent cation proportions, substitution mechanisms and elasticity parameters. [1] T Boffa-Ballaran, RG Tronnes, D

  12. Static and dynamic optical properties of La1-xSrxFeO3-δ: The effects of A-site and oxygen stoichiometry

    SciTech Connect

    Sergey Y. Smolin; Sfeir, Matthew Y.; Scafetta, Mark D.; Choquette, Amber K.; Baxter, Jason B.; May, Steven J.

    2015-12-09

    Perovskite oxides are a promising material class for photovoltaic and photocatalytic applications due to their visible band gaps, nanosecond recombination lifetimes, and great chemical diversity. However, there is limited understanding of the link between composition and static and dynamic optical properties, despite the critical role these properties play in the design of light-harvesting devices. To clarify these relationships, we systemically studied the optoelectronic properties in La1-xSrxFeO3-δ epitaxial films, uncovering the effects of A-site cation substitution and oxygen stoichiometry. Variable-angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and a red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy, revealing similar nanosecond photoexcited carrier lifetimes for oxygen deficient and stoichiometric films with the same nominal Fe valence. Furthermore, these results demonstrate that while the static optical absorption is strongly dependent on nominal Fe valence tuned through cation or anion stoichiometry, oxygen vacancies do not appear to play a significantly detrimental role in the recombination kinetics.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Nanowire Lasers of Formamidinium Lead Halide Perovskites and Their Stabilized Alloys with Improved Stability.

    PubMed

    Fu, Yongping; Zhu, Haiming; Schrader, Alex W; Liang, Dong; Ding, Qi; Joshi, Prakriti; Hwang, Leekyoung; Zhu, X-Y; Jin, Song

    2016-02-10

    The excellent intrinsic optoelectronic properties of methylammonium lead halide perovskites (MAPbX3, X = Br, I), such as high photoluminescence quantum efficiency, long carrier lifetime, and high gain coupled with the facile solution growth of nanowires make them promising new materials for ultralow-threshold nanowire lasers. However, their photo and thermal stabilities need to be improved for practical applications. Herein, we report a low-temperature solution growth of single crystal nanowires of formamidinium lead halide perovskites (FAPbX3) that feature red-shifted emission and better thermal stability compared to MAPbX3. We demonstrate optically pumped room-temperature near-infrared (∼820 nm) and green lasing (∼560 nm) from FAPbI3 (and MABr-stabilized FAPbI3) and FAPbBr3 nanowires with low lasing thresholds of several microjoules per square centimeter and high quality factors of about 1500-2300. More remarkably, the FAPbI3 and MABr-stabilized FAPbI3 nanowires display durable room-temperature lasing under ∼10(8) shots of sustained illumination of 402 nm pulsed laser excitation (150 fs, 250 kHz), substantially exceeding the stability of MAPbI3 (∼10(7) laser shots). We further demonstrate tunable nanowire lasers in wider wavelength region from FA-based lead halide perovskite alloys (FA,MA)PbI3 and (FA,MA)Pb(I,Br)3 through cation and anion substitutions. The results suggest that formamidinium lead halide perovskite nanostructures could be more promising and stable materials for the development of light-emitting diodes and continuous-wave lasers.

  6. 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.

  7. A Hand to Substitutes

    ERIC Educational Resources Information Center

    Javernick, Ellen

    2005-01-01

    In the days before computers, passing on information to substitutes was difficult. Now teachers can individualize their lesson plans to guarantee that substitute teachers and the students will both have a good day. This article provides some plan-ahead procedures that have worked for the author.

  8. Working with Substitute Teachers.

    ERIC Educational Resources Information Center

    Wilson, Karen

    1999-01-01

    Resolving the perennial problem of substitute teachers' high turnover and low availability is feasible, if principals welcome, orient, and assign them properly. Regular teachers should prepare a folder containing class lists, daily schedules, seating charts, expectations of students, and meaningful lesson plans. Substitutes should be treated as…

  9. Florida's Substitute Teachers.

    ERIC Educational Resources Information Center

    Odutola, Adeniji A.; Etemadi, Judy N.

    2002-01-01

    Describes the statutory duties of the Florida Education Standards Commission, highlighting a study of the working conditions of Florida's substitute teachers. Researchers collected data on school board policies regarding substitutes' educational levels required, initial training and staff development opportunities required, salary schedules, and…

  10. Prediction of novel perovskite-type oxyhydride KTi(O2H) with two-dimensional electronic states

    NASA Astrophysics Data System (ADS)

    Sato, Nobuya; Tsuneyuki, Shinji

    2015-03-01

    Perovskite-type oxides AB O3 have been widely studied for its dielectricity. The properties of these materials significantly change by substituting A or B cations, while compositions of A and B cations are limited to (A2+, B4+) and (A3+, B3+) for charge neutrality. Recently, it has been demonstrated that oxygen anions in BaTiO3 can be partially substituted with hydride ions (H-), suggesting that more varieties of compositions might be realized (e.g., (A+, B4+)) combined with oxygen substitution. In this work, using first-principles calculations, we investigate an unsynthesized model composition with the oxygen substitution, KTi(O2H). This compound is expected to crystalize into the perovskite-type structure from its tolerance factor. We confirm its stability with the crystal structure optimization and calculation of its formation energy for possible reactions. The material is insulating with large electronic polarization and has two-dimensional low-energy electronic states within Ti-O-H planes. For its unconventional composition and the peculiar two-dimensional property, this material may realize novel electronic properties. N. S. was supported by Japan Society for the Promotion of Science through Program for Leading Graduate Schools (MERIT).

  11. How to regulate energy levels and hole mobility of spiro-type hole transport materials in perovskite solar cells.

    PubMed

    Chi, Wei-Jie; Sun, Ping-Ping; Li, Ze-Sheng

    2016-10-21

    Methoxyaniline-based organic small molecules with three-dimensional structure have been proven as the most promising hole conductor for state-of-the-art perovskite devices. A fundamental understanding of the electronic properties and hole transport behavior of spiro-CPDT analogues, which is dependent on the number and position of the -OCH3 groups, is significant for their potential applications as hole transport materials of perovskite solar cells. Our results from density functional theory calculations indicate that meta-substitution is more beneficial to reduce the highest occupied molecular orbital (HOMO) levels of molecules compared with ortho- and para-substitution. Furthermore, the hole mobility can be improved by ortho-substitution or mixed ortho- and para-substitution. Most interestingly, it is found that the improvement in hole mobility is at the expense of raising the HOMO level of spiro-CPDT analogues. These results can be useful in the process of designing and synthesizing excellent hole transport materials with suitable HOMO levels and high hole mobility.

  12. 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

  13. High-pressure Raman spectroscopy of perovskite oxynitride SrTaO2N

    NASA Astrophysics Data System (ADS)

    Son, Y.-G.; Jeong, I.-K.

    2016-09-01

    Perovskite oxynitrides exhibit emergent physical properties driven by a substitution of nitrogen for oxygen. The nitrogen substitution distorts the octahedra and induces octahedral tilting which are responsible for a relaxor-like temperature-insensitive dielectric response. To study the local structural evolution of oxynitride SrTaO2N under pressure, we performed in-situ high-pressure Raman spectroscopy measurements with a diamond anvil cell up to a pressure of P = 19 GPa. We find that forbidden modes were active, indicating a lowering of local symmetry from non-polar I4/mcm due to the octahedral distortion. Under pressure, a mode associated with TaO4N2 exhibits a negative wavenumber shift and merges with a nearby mode at a pressure of P ≃ 4.2 GPa. This result indicates a suppression of octahedral tilting under pressure.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. Possible ferrimagnetism and ferroelectricity of half-substituted rare-earth titanate: A first-principles study on Y0.5La0.5TiO3

    NASA Astrophysics Data System (ADS)

    An, Ming; Zhang, Hui-Min; Weng, Ya-Kui; Zhang, Yang; Dong, Shuai

    2016-04-01

    Titanates with the perovskite structure, including ferroelectrics (e.g., BaTiO3) and ferromagnetic ones (e.g., YTiO3), are important functional materials. Recent theoretical studies predicted multiferroic states in strained EuTiO3 and titanate superlattices, the former of which has already been experimental confirmed. Here, a first-principles calculation is performed to investigate the structural, magnetic, and electronic properties of Y half-substituted LaTiO3. Our results reveal that the magnetism of Y0.5La0.5TiO3 sensitively depends on its structural details because of the inherent phase competition. The lowest energy state is the ferromagnetic state, resulting in 0.25 μ B /Ti. Furthermore, some configurations of Y0.5La0.5TiO3 exhibit hybrid improper polarizations, which can be significantly affected by magnetism, resulting in the multiferroic properties. Because of the quenching disorder of substitution, the real Y0.5La0.5TiO3 material with random A-site ions may exhibit interesting relaxor behaviors.

  20. 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.

  1. 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

  2. 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.

  3. Sustainability and substitutability.

    PubMed

    Fenichel, Eli P; Zhao, Jinhua

    2015-02-01

    Developing a quantitative science of sustainability requires bridging mathematical concepts from fields contributing to sustainability science. The concept of substitutability is central to sustainability but is defined differently by different fields. Specifically, economics tends to define substitutability as a marginal concept while fields such as ecology tend to focus on limiting behaviors. We explain how to reconcile these different views. We develop a model where investments can be made in knowledge to increase the elasticity of substitution. We explore the set of sustainable and optimal trajectories for natural capital extraction and built and knowledge capital accumulation. Investments in substitutability through knowledge stock accumulation affect the value of natural capital. Results suggest that investing in the knowledge stock, which can enhance substitutability, is critical to desirable sustainable outcomes. This result is robust even when natural capital is not managed optimally. This leads us to conclude that investments in the knowledge stock are of first order importance for sustainability.

  4. 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}.

  5. 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.

  6. 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.

  7. 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.

  8. Structural And Electrical Properties oF (La{sub 0.5-x}Pr{sub x}Ba{sub 0.5})(Mn{sub 0.5}Ti{sub 0.5})O{sub 3} Perovskite

    SciTech Connect

    Alias, Nor Hayati; Shaari, Abdul Halim; Wan Yusoff, Wan Mohd Daud; Mahmood, Che Seman

    2010-01-05

    A single phase monoclinic new perovskite based titano-manganite (La{sub 0.5-x}Pr{sub x}Ba{sub 0.5})(Mn{sub 0.5}Ti{sub 0.5})O{sub 3} has been successfully prepared by ceramic solid-state technique at sintering temperature of 1300 deg. C. The concentration of Pr (Praseodymium), x, in molar proportion in A site has been varied as x = 0, 0.02 and 0.2. Analysis has been carried out to determine the electrical properties of the synthesized material at frequency ranging from 5 Hz to 1 MHz; and at temperature range between 25 deg. C to 200 deg. C. It is found that Pr addition promoted liquid phase sintering diffusion, porosity and agglomeration formation at 1300 deg. C. Dual relaxation is observed in unsubstituted Pr sample x = 0 and high Pr substituted sample x = 0.2. This phenomenon was a combinational contribution from a quasi dc (QDC) or low frequency dispersion (LFD), two cole-cole relaxational responses and a resistor. While low concentrated Pr substituted sampled x = 0.02 shows a combinational contribution from a quasi dc (QDC) or low frequency dispersion (LFD), single cole-cole relaxational response and a resistor at room temperature. Pr substitution at x = 0(max 12000) and x = 0.2(max 16000) showed high dielectric values compared to low substituted sample x = 0.02. Variation of dielectric loss tangent (tan delta) are observed for all samples at temperature ranged studied.

  9. Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution

    DOE PAGES

    Doane, Tennyson L.; Ryan, Kayla L.; Pathade, Laxmikant; ...

    2016-05-05

    The ability of cesium lead halide (CsPbX3; X = Cl–, Br–, I–) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. Also, the exchange of CsPbI3 with Cl– or Br– causes a significant blue-shift in absorption and photoluminescence, whereas reacting I– with CsPbBr3 causes a red-shift of similar magnitudes. With the high localmore » halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. Finally, the merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites.« less

  10. Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution.

    PubMed

    Doane, Tennyson L; Ryan, Kayla L; Pathade, Laxmikant; Cruz, Kevin J; Zang, Huidong; Cotlet, Mircea; Maye, Mathew M

    2016-06-28

    The ability of cesium lead halide (CsPbX3; X = Cl(-), Br(-), I(-)) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. The exchange of CsPbI3 with Cl(-) or Br(-) causes a significant blue-shift in absorption and photoluminescence, whereas reacting I(-) with CsPbBr3 causes a red-shift of similar magnitudes. With the high local halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. The merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites.

  11. 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.

  12. Thermoelectric and structural correlations in (S r1 -x -yC axN dy) Ti O3 perovskites

    NASA Astrophysics Data System (ADS)

    Somaily, H.; Kolesnik, S.; Dabrowski, B.; Chmaissem, O.

    2017-08-01

    Structural and thermoelectric properties are reported for a specially designed class of A -site substituted perovskite titanates, (S r1 -x -yC axN dy) Ti O3 . Two series synthesized with various A -site Sr-rich or Ca-rich (Sr-poor) concentrations were investigated using high-resolution neutron powder diffraction as a function of temperature and Nd doping. Each series was designed to have a nominally constant tolerance factor at room temperature. We determine the room temperature structures as tetragonal I 4 /m c m and orthorhombic P b n m for the Sr-rich and Ca-rich series, respectively. Three low-temperature orthorhombic structures, P b n m , I b m m , and P b c m were also observed for the Sr-rich series, whereas the symmetry of the Ca-rich series remains unchanged throughout the full measured temperature range. Thermoelectric properties of (S r1 -x -yC axN dy) Ti O3 were investigated and correlated with the structural variables. We succeeded in achieving a relatively high figure of merit Z T =0.07 at ˜400 K in the Sr-rich S r0.76C a0.16N d0.08Ti O3 composition which is comparable to that of the best n -type TE SrT i0.80N b0.20O3 oxide material reported to date. For a fixed tolerance factor, the Nd doping enhances the carrier density and effective mass at the expense of the Seebeck coefficient. Thermal conductivity greatly reduces upon Nd doping in the Ca-rich series. With an enhanced Seebeck coefficient at elevated temperatures and reduced thermal conductivity, we predict that S r0.76C a0.16N d0.08Ti O3 and similar compositions have the potential to become some of the best materials in their class of thermoelectric oxides.

  13. 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.

  14. 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.

  15. A mechanical spectrum study of double perovskite Y 1- xCa xBaCuFeO 5+δ

    NASA Astrophysics Data System (ADS)

    Ying, X. N.; Xu, Z. C.

    2008-05-01

    The mechanical spectrum of double perovskite Y BaCuFeO 5+δ was measured using the vibrating reed method from 100 K to room temperature at kilohertz frequency. A sharp internal friction peak around 203 K and a broad one around 260 K were observed in Y BaCuFeO 5+δ. A deviation of the temperature dependent reduced modulus from linear behavior above 203 K is observed which is concurrent with the sharp internal friction peak. This suggests a phase transition mechanism of the sharp internal friction peak. The intensities of the two internal friction peaks were both depressed upon partial Ca substitution of Y. By comparison of the mechanical spectrum with the bilayer superconductor Y Ba 2Cu 3O 7+δ, one kind of transition in double perovskite oxide is proposed for the sharp internal friction peak.

  16. 40 CFR 721.981 - Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... naphthalenyl-substituted azonaphthol chromium complex. 721.981 Section 721.981 Protection of Environment...-substituted naphthalenyl-substituted azonaphthol chromium complex. (a) Chemical substance and significant new... naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex (PMN P-93-1631) is subject...

  17. 40 CFR 721.981 - Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... naphthalenyl-substituted azonaphthol chromium complex. 721.981 Section 721.981 Protection of Environment...-substituted naphthalenyl-substituted azonaphthol chromium complex. (a) Chemical substance and significant new... naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex (PMN P-93-1631) is subject...

  18. 40 CFR 721.981 - Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... naphthalenyl-substituted azonaphthol chromium complex. 721.981 Section 721.981 Protection of Environment...-substituted naphthalenyl-substituted azonaphthol chromium complex. (a) Chemical substance and significant new... naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex (PMN P-93-1631) is subject...

  19. 40 CFR 721.981 - Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... naphthalenyl-substituted azonaphthol chromium complex. 721.981 Section 721.981 Protection of Environment...-substituted naphthalenyl-substituted azonaphthol chromium complex. (a) Chemical substance and significant new... naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex (PMN P-93-1631) is subject...

  20. 40 CFR 721.981 - Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... naphthalenyl-substituted azonaphthol chromium complex. 721.981 Section 721.981 Protection of Environment...-substituted naphthalenyl-substituted azonaphthol chromium complex. (a) Chemical substance and significant new... naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex (PMN P-93-1631) is subject...

  1. 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.

  2. 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.

  3. Sugar substitutes during pregnancy

    PubMed Central

    Pope, Eliza; Koren, Gideon; Bozzo, Pina

    2014-01-01

    Abstract Question I have a pregnant patient who regularly consumes sugar substitutes and she asked me if continuing their use would affect her pregnancy or child. What should I tell her, and are there certain options that are better for use during pregnancy? Answer Although more research is required to fully determine the effects of in utero exposure to sugar substitutes, the available data do not suggest adverse effects in pregnancy. However, it is recommended that sugar substitutes be consumed in moderate amounts, adhering to the acceptable daily intake standards set by regulatory agencies. PMID:25392440

  4. Sugar substitutes during pregnancy.

    PubMed

    Pope, Eliza; Koren, Gideon; Bozzo, Pina

    2014-11-01

    I have a pregnant patient who regularly consumes sugar substitutes and she asked me if continuing their use would affect her pregnancy or child. What should I tell her, and are there certain options that are better for use during pregnancy? Although more research is required to fully determine the effects of in utero exposure to sugar substitutes, the available data do not suggest adverse effects in pregnancy. However, it is recommended that sugar substitutes be consumed in moderate amounts, adhering to the acceptable daily intake standards set by regulatory agencies. Copyright© the College of Family Physicians of Canada.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Chemical and electronic characterization of cobalt in Lanthanumperovskites. Effects of Strontium substitution

    SciTech Connect

    Hueso, Jose L.; Holgado, Juan P.; Pereniguez, Rosa; Mun, Simon; Salmeron, Miquel; Caballero, Alfonso

    2009-02-06

    Two different cobaltites, LaCoO{sub 3} and La{sub 0.5}Sr{sub 0.5}CoO{sub 3-{delta}}, have been prepared and characterized by means of high energy Co K-edge and low energy O K-edge X-ray absorption spectroscopy (XAS). The partial substitution of La(III) by Sr(II) species induces important changes in the reactivity and electronic state of the perovskite, while little or no changes can be detected in the formal oxidation state of cobalt atoms. The presence of strontium cations induces two main effects in the chemical and electronic behavior of the perovskite. The charge balance with Sr(II) species is reached by the formation of oxygen vacancies throughout the network, which increases the reactivity of the perovskite, now more reducible than the original LaCoO{sub 3} perovskite. O K-edge XAS experiments indicate that the Sr(II) species cause d electrons of cobalt cations to change from low to high spin configuration. Our data allow us to propose that this change in spin multiplicity is induced by the bigger size of Sr(II) cations, which aligns the Co-O-Co atoms, and favors the overlapping of {pi}-symmetry cobalt and oxygen orbitals, reducing the splitting energy of e{sub g} and t{sub 2g} levels.

  10. 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

  11. Synthesis of substituted pyrazines

    SciTech Connect

    Pagoria, Philip F.; Zhang, Mao Xi

    2016-10-04

    A method for synthesizing a pyrazine-containing material according to one embodiment includes contacting an iminodiacetonitrile derivative with a base and a reagent selected from a group consisting of hydroxylamine, a hydroxylamine salt, an aliphatic primary amine, a secondary amine, an aryl-substituted alkylamine a heteroaryl-substituted alkyl amine, an alcohol, an alkanolamine and an aryl alcoholamine. Additional methods and several reaction products are presented. ##STR00001##

  12. Ab initio modeling of 2D layered organohalide lead perovskites

    NASA Astrophysics Data System (ADS)

    Fraccarollo, Alberto; Cantatore, Valentina; Boschetto, Gabriele; Marchese, Leonardo; Cossi, Maurizio

    2016-04-01

    A number of 2D layered perovskites A2PbI4 and BPbI4, with A and B mono- and divalent ammonium and imidazolium cations, have been modeled with different theoretical methods. The periodic structures have been optimized (both in monoclinic and in triclinic systems, corresponding to eclipsed and staggered arrangements of the inorganic layers) at the DFT level, with hybrid functionals, Gaussian-type orbitals and dispersion energy corrections. With the same methods, the various contributions to the solid stabilization energy have been discussed, separating electrostatic and dispersion energies, organic-organic intralayer interactions and H-bonding effects, when applicable. Then the electronic band gaps have been computed with plane waves, at the DFT level with scalar and full relativistic potentials, and including the correlation energy through the GW approximation. Spin orbit coupling and GW effects have been combined in an additive scheme, validated by comparing the computed gap with well known experimental and theoretical results for a model system. Finally, various contributions to the computed band gaps have been discussed on some of the studied systems, by varying some geometrical parameters and by substituting one cation in another's place.

  13. Substitution of anticonvulsant drugs

    PubMed Central

    Steinhoff, Bernhard J; Runge, Uwe; Witte, Otto W; Stefan, Hermann; Hufnagel, Andreas; Mayer, Thomas; Krämer, Günter

    2009-01-01

    Changing from branded drugs to generic alternatives, or between different generic formulations, is common practice aiming at reducing health care costs. It has been suggested that antiepileptic drugs (AEDs) should be exempt from substitution because of the potential negative consequences of adverse events and breakthrough seizures. Controlled data are lacking on the risk of substitution. However, retrospective data from large medical claims databases suggest that switching might be associated with increased use of AED and non-AED medications, and health care resources (including hospitalization). In addition, some anecdotal evidence from patients and health care providers’ surveys suggest a potentially negative impact of substitution. Well-controlled data are needed to assess the real risk associated with substitution, allowing health care professionals involved in the care of patients with epilepsy to make informed decisions. This paper reviews currently available literature, based on which the authors suggest that the decision to substitute should be made on an individual basis by the physician and an informed patient. Unendorsed or undisclosed substitution at the pharmacy level should be discouraged. PMID:19707254

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

    PubMed

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

    2016-04-11

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

  15. Applications of cesium in the perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Ye, Fengjun; Yang, Wenqiang; Luo, Deying; Zhu, Rui; Gong, Qihuang

    2017-01-01

    Perovskite solar cells have experienced an unprecedented rapid development in the power conversion efficiency (PCE) during the past 7 years, and the record PCE has been already comparable to the traditional polycrystalline silicon solar cells. Presently, it is more urgent to address the challenge on device stability for the future commercial application. Recently, the inorganic cesium lead halide perovskite has been intensively studied as one of the alternative candidates to improve device stability through controlling the phase transition. The cesium (Cs)-doped perovskites show more superior stability comparing with organic methylammonium (MA) lead halide perovskite or formamidinium (FA) lead halide perovskite. Here, recent progress of the inorganic cesium application in organic–inorganic perovskite solar cells (PSCs) is highlighted from the viewpoints of the device efficiency and the device stability. Project supported by the 973 Program of China (No. 2015CB932203), the National Natural Science Foundation of China (Nos. 61377025, 91433203), and the Young 1000 Talents Global Recruitment Program of China.

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

    SciTech Connect

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

    2014-04-14

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

  17. Recent progress in stability of perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Qin, Xiaojun; Zhao, Zhiguo; Wang, Yidan; Wu, Junbo; Jiang, Qi; You, Jingbi

    2017-01-01

    Perovskite solar cells have attracted significant attention in just the past few years in solar cell research fields, where the power conversion efficiency was beyond 22.1%. Now, the most important challenge for perovskite solar cells in practical applications is the stability issue. In this mini-review, we will summarize the degradation mechanism of perovskite solar cells, including the perovskite material itself and also the interfaces. While we also provide our opinion on improving the stability of perovskite solar cells. Project supported by China Huaneng Group Project High Performance Perovskite Solar Cells (No. TW-15-HJK01), the National Key Research and Development Program of China (No. 2016YFB0700700), the National 1000 Young Talent Awards, and the National Natural Science Foundation of China (No. 61574133).

  18. Graphene petals as potential electrode for perovskite based solar cells

    NASA Astrophysics Data System (ADS)

    Singh, Shivi

    The recent discovery of perovskites absorbers for high efficiency solar cells has sparked interest of the solar cell community. In the present study formation and growth of perovskite (both single and mixed halide) is analyzed and a procedure is developed to increase reproducibility of these layers. Graphene nano-petals are also studied as a potential electrode for perovskite solar cells, to assist in growth of better quality perovskite layers. X-ray diffraction, scanning electron microscopy and UV-vis spectroscopy are used to study the effect of different parameters on morphological features of perovskite. Different solar cell geometries are also tested, and a working geometry for single stack perovskite solar cell is proposed which uses graphene nano-petals as an electrode.

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

    PubMed

    Chen, Kun; Tüysüz, Harun

    2015-11-09

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

  20. Photoluminescence behavior of nanoimprinted halide perovskite at low temperatures

    NASA Astrophysics Data System (ADS)

    Sadrieva, Zarina F.; Kapitonov, Yu.; Balachandran, B.; Gu, Q.; Hu, W.; Makarov, Sergey V.; Bogdanov, Andrey A.

    2017-09-01

    Perovskite materials and bound state in the continuum are hot topics now. Development of these fields will lead to inventing advanced photonic devices. Here we report theoretical and experimental results for a high-Q cavity based on nanoimprinted perovskite film. We reveal that bound state in the continuum transformed into a resonant state due to leakage into substrate leads to significant enhancement of the photoluminescence signal of the perovskite cavity.

  1. Photovoltaic Performance of Perovskite Solar Cells with Different Grain Sizes.

    PubMed

    Kim, Hyung Do; Ohkita, Hideo; Benten, Hiroaki; Ito, Shinzaburo

    2016-02-03

    Perovskite solar cells exhibit improved photovoltaic parameters with increasing perovskite grain size. The larger photocurrent is due to the enhanced absorption efficiency for thicker perovskite layers. The larger open-circuit voltage (VOC ) is ascribed to the reduced trap-assisted recombination for the larger grains. As a result, the power conversion efficiency exceeds 19% at best. Further improvement in VOC would be possible if the trap density were reduced.

  2. Effect of A-site Non-stoichiometry on LSCF Cathodes

    SciTech Connect

    Templeton, Jared W.; Lu, Zigui; Stevenson, Jeffry W.; Hardy, John S.

    2011-09-01

    LSCF Cathodes were explored when effected with A-site non-stoichiometry. At 700-800 C, the operating temperatures of intermediate temperature (IT-) SOFCs have enabled the use of stainless steels in the SOFC framework and current collectors, allowing significant reductions in cost. However, the lower operating temperatures of IT-SOFC's also result in significant decreases in power densities of cells with LSM cathodes due to their high activation energies. LSCF is a mixed ionic electronic conducting perovskite that exhibits higher performance than LSM/YSZ composites and shows potential as a replacement cathode. This study investigates the effect of A-site stoichiometry on the performance of LSCF cathodes. Cell tests showed that A-site and Sr-deficient LSCF cathodes consistently outperformed stoichiometric LSCF cathodes, exhibiting up to 10% higher cell power densities. It was also observed that all stoichiometric, A-site, and Sr-deficient LSCF cathodes degraded over time at similar rates. Contributions of ohmic and electrode polarization losses to cell degradation rates were similar regardless of cathode composition.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  4. Post-perovskite Transition in Anti-structure

    NASA Astrophysics Data System (ADS)

    Wang, Bosen; Ohgushi, Kenya

    2016-11-01

    The discovery of the post-perovskite transition, which is the structural transition from the perovskite to post-perovskite structure in MgSiO3 under pressure, has aroused great interests in geosciences. Despite of previous extensive studies, key factors of the post-perovsktie transition are still under hot debate primarily due to the big difficulty in performing systematic experiments under extreme conditions. Hence, search for new materials showing the post-perovskite transition under ambient pressure has been highly expected. We here report a new-type of materials Cr3AX (A = Ga, Ge; X = C, N), which exhibits the post-perovskite transition as a function of “chemical pressure” at ambient physical pressure. The detailed structural analysis indicates that the tolerance factor, which is the measure of the ionic radius mismatch, plays the key role in the post-perovskite transition. Moreover, we found a tetragonal perovskite structure with loss of inversion symmetry between the cubic perovskite and orthorhombic post-perovskite structures. This finding stimulates a search for a ferroelectric state in MgSiO3.

  5. Post-perovskite Transition in Anti-structure.

    PubMed

    Wang, Bosen; Ohgushi, Kenya

    2016-11-30

    The discovery of the post-perovskite transition, which is the structural transition from the perovskite to post-perovskite structure in MgSiO3 under pressure, has aroused great interests in geosciences. Despite of previous extensive studies, key factors of the post-perovsktie transition are still under hot debate primarily due to the big difficulty in performing systematic experiments under extreme conditions. Hence, search for new materials showing the post-perovskite transition under ambient pressure has been highly expected. We here report a new-type of materials Cr3AX (A = Ga, Ge; X = C, N), which exhibits the post-perovskite transition as a function of "chemical pressure" at ambient physical pressure. The detailed structural analysis indicates that the tolerance factor, which is the measure of the ionic radius mismatch, plays the key role in the post-perovskite transition. Moreover, we found a tetragonal perovskite structure with loss of inversion symmetry between the cubic perovskite and orthorhombic post-perovskite structures. This finding stimulates a search for a ferroelectric state in MgSiO3.

  6. Post-perovskite Transition in Anti-structure

    PubMed Central

    Wang, Bosen; Ohgushi, Kenya

    2016-01-01

    The discovery of the post-perovskite transition, which is the structural transition from the perovskite to post-perovskite structure in MgSiO3 under pressure, has aroused great interests in geosciences. Despite of previous extensive studies, key factors of the post-perovsktie transition are still under hot debate primarily due to the big difficulty in performing systematic experiments under extreme conditions. Hence, search for new materials showing the post-perovskite transition under ambient pressure has been highly expected. We here report a new-type of materials Cr3AX (A = Ga, Ge; X = C, N), which exhibits the post-perovskite transition as a function of “chemical pressure” at ambient physical pressure. The detailed structural analysis indicates that the tolerance factor, which is the measure of the ionic radius mismatch, plays the key role in the post-perovskite transition. Moreover, we found a tetragonal perovskite structure with loss of inversion symmetry between the cubic perovskite and orthorhombic post-perovskite structures. This finding stimulates a search for a ferroelectric state in MgSiO3. PMID:27901099

  7. Perovskite solar cells: Shedding light on film crystallization

    NASA Astrophysics Data System (ADS)

    Bakr, Osman M.; Mohammed, Omar F.

    2017-06-01

    A study on the formation of methylammonium lead iodide perovskite films reveals that light illumination influences the crystallization kinetics, therefore affecting the final photovoltaic performance of these materials.

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

    PubMed

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

    2014-03-27

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

  9. 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.

  10. Organohalide Perovskites for Solar Energy Conversion.

    PubMed

    Lin, Qianqian; Armin, Ardalan; Burn, Paul L; Meredith, Paul

    2016-03-15

    Lead-based organohalide perovskites have recently emerged as arguably the most promising of all next generation thin film solar cell technologies. Power conversion efficiencies have reached 20% in less than 5 years, and their application to other optoelectronic device platforms such as photodetectors and light emitting diodes is being increasingly reported. Organohalide perovskites can be solution processed or evaporated at low temperatures to form simple thin film photojunctions, thus delivering the potential for the holy grail of high efficiency, low embedded energy, and low cost photovoltaics. The initial device-driven "perovskite fever" has more recently given way to efforts to better understand how these materials work in solar cells, and deeper elucidation of their structure-property relationships. In this Account, we focus on this element of organohalide perovskite chemistry and physics in particular examining critical electro-optical, morphological, and architectural phenomena. We first examine basic crystal and chemical structure, and how this impacts important solar-cell related properties such as the optical gap. We then turn to deeper electronic phenomena such as carrier mobilities, trap densities, and recombination dynamics, as well as examining ionic and dielectric properties and how these two types of physics impact each other. The issue of whether organohalide perovskites are predominantly nonexcitonic at room temperature is currently a matter of some debate, and we summarize the evidence for what appears to be the emerging field consensus: an exciton binding energy of order 10 meV. Having discussed the important basic chemistry and physics we turn to more device-related considerations including processing, morphology, architecture, thin film electro-optics and interfacial energetics. These phenomena directly impact solar cell performance parameters such as open circuit voltage, short circuit current density, internal and external quantum efficiency

  11. Slater insulator in iridate perovskites with strong spin-orbit coupling

    SciTech Connect

    Cui, Q.; Cheng, J. -G.; Fan, W.; Taylor, Alice E.; Calder, Stuart A.; McGuire, Michael A.; Yan, Jia -Qiang; Meyers, D.; Li, X.; Cai, Y. Q.; Jiao, Y. Y.; Choi, Y.; Haskel, Daniel; Gotou, H.; Uwatoko, Yoshiya; Chakhalian, J.; Christianson, Andrew D.; Yunoki, S.; Goodenough, J. B.; Zhou, J. -S.

    2016-10-20

    The perovskite SrIrO3 is an exotic narrow-band metal owing to a confluence of the strengths of the spin-orbit coupling (SOC) and the electron-electron correlations. It has been proposed that topological and magnetic insulating phases can be achieved by tuning the SOC, Hubbard interactions, and/or lattice symmetry. Here, we report that the substitution of nonmagnetic, isovalent Sn4+ for Ir4+ in the SrIr1–xSnxO3 perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic (AF) phase at TN ≥ 225 K. The continuous change of the cell volume as detected by x-ray diffraction and the λ-shape transition of the specific heat on cooling through TN demonstrate that the metal-insulator transition is of second order. Neutron powder diffraction results indicate that the Sn substitution enlarges an octahedral-site distortion that reduces the SOC relative to the spin-spin exchange interaction and results in the type-G AF spin ordering below TN. Measurement of high-temperature magnetic susceptibility shows the evolution of magnetic coupling in the paramagnetic phase typical of weak itinerant-electron magnetism in the Sn-substituted samples. Furthermore, a reduced structural symmetry in the magnetically ordered phase leads to an electron gap opening at the Brillouin zone boundary below TN in the same way as proposed by Slater.

  12. Slater Insulator in Iridate Perovskites with Strong Spin-Orbit Coupling

    SciTech Connect

    Cui, Q.; Cheng, J. -G.; Fan, W.; Taylor, A. E.; Calder, S.; McGuire, M. A.; Yan, J. -Q.; Meyers, D.; Li, X.; Cai, Y. Q.; Jiao, Y. Y.; Choi, Y.; Haskel, D.; Gotou, H.; Uwatoko, Y.; Chakhalian, J.; Christianson, A. D.; Yunoki, S.; Goodenough, J. B.; Zhou, J. -S.

    2016-10-20

    The perovskite (Pv) SrIrO3 is an exotic narrow-band metal owing to a confluence of the strengths of the spin-orbit coupling (SOC) and the electron-electron correlations. It has been proposed that topological and magnetic insulating phases can be achieved by tuning the SOC, Hubbard interactions, and/or lattice symmetry. Here, we report that the substitution of nonmagnetic, isovalent Sn4+ for Ir4+ in the SrIr1-xSnxO3 perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic phase at TN ≥ 225 K. The continuous change of the cell volume as detected by X-ray diffraction and the l-shape transition of the specific heat on cooling through TN demonstrate that the metal-insulator transition is of second-order. Neutron powder diffraction results indicate that the Sn substitution enlarges an octahedral-site distortion that reduces the SOC relative to the spin-spin exchange interaction and results in the type-G AF spin ordering below TN. Measurement of high-temperature magnetic susceptibility shows the evolution of magnetic coupling in the paramagnetic phase typical of weak itinerant-electron magnetism in the Sn-substituted samples. A reduced structural symmetry in the magnetically ordered phase leads to an electron gap opening at the Brillouin zone boundary below TN in the same way as proposed by Slater.

  13. The substitutability of reinforcers

    PubMed Central

    Green, Leonard; Freed, Debra E.

    1993-01-01

    Substitutability is a construct borrowed from microeconomics that describes a continuum of possible interactions among the reinforcers in a given situation. Highly substitutable reinforcers, which occupy one end of the continuum, are readily traded for each other due to their functional similarity. Complementary reinforcers, at the other end of the continuum, tend to be consumed jointly in fairly rigid proportion, and therefore cannot be traded for one another except to achieve that proportion. At the center of the continuum are reinforcers that are independent with respect to each other; consumption of one has no influence on consumption of another. Psychological research and analyses in terms of substitutability employ standard operant conditioning paradigms in which humans and nonhumans choose between alternative reinforcers. The range of reinforcer interactions found in these studies is more readily accommodated and predicted when behavior-analytic models of choice consider issues of substitutability. New insights are gained into such areas as eating and drinking, electrical brain stimulation, temporal separation of choice alternatives, behavior therapy, drug use, and addictions. Moreover, the generalized matching law (Baum, 1974) gains greater explanatory power and comprehensiveness when measures of substitutability are included. PMID:16812696

  14. 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.

  15. Synthesis of the novel perovskite-type oxyfluoride PbScO 2F under high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Katsumata, Tetsuhiro; Nakashima, Mamoru; Umemoto, Hiroshi; Inaguma, Yoshiyuki

    2008-10-01

    We synthesized a novel perovskite-type oxyfluoride, PbScO 2F, and investigated its crystal structure, thermal stability and dielectric properties. PbScO 2F has a cubic perovskite-type structure with Pb ions displaced from the ideal A-site positions along the <110> direction. By thermal gravity and differential thermal analyses, we found that this compound is stable up to 963 K (690 °C) under ambient atmosphere. The dielectric permittivity of PbScO 2F is approximately 80, at room temperature, which is almost the same as KTiO 2F and smaller than that of PbFeO 2F. Furthermore, an anomaly in the dielectric permittivity was observed in the vicinity of 100 K that seems to be related to the displacement of the Pb ions.

  16. New antiferromagnetic perovskite CaCo3V4O12 prepared at high-pressure and high-temperature conditions.

    PubMed

    Ovsyannikov, Sergey V; Zainulin, Yury G; Kadyrova, Nadezda I; Tyutyunnik, Alexander P; Semenova, Anna S; Kasinathan, Deepa; Tsirlin, Alexander A; Miyajima, Nobuyoshi; Karkin, Alexander E

    2013-10-21

    A new perovskite, CaCo(2+)3V(4+)4O12, has been synthesized at high-pressure and high-temperature (HP-HT) conditions. The properties of this perovskite were examined by a range of techniques. CaCo3V4O12 was found to adopt a double-perovskite cubic lattice [a = 7.3428(6) Å] with Im3 symmetry. We have established that this new perovskite is stable at ambient conditions, and its oxidation and/or decomposition at ambient pressure begins above 500 °C. It undergoes an abrupt antiferromagnetic transition around 98 K. Electrical resistivity data suggest semimetallic conductivity in the temperature range of 1.6-370 K. We have established that the Co(2+) ions in CaCo3V4O12 are in the high-spin state with a sizable orbital moment, even though their square-planar oxygen coordination could be more suitable for the low-spin state, which is prone to Jahn-Teller distortion. Electrical resistivity curves also exhibit a distinct steplike feature around 100 K. CaCo3V4O12 is a first example of perovskite in which the sites A' are fully occupied by Co(2+) ions, and hence its synthesis opens the door to a new class of double perovskites, ACo3B4O12, that may be derived by chemical substitution of the A sublattice by lanthanides, sodium, strontium, and bismuth and by other elements and/or of the B sublattice by some other transition metals.

  17. Aryl substitution of pentacenes

    PubMed Central

    Waterloo, Andreas R; Sale, Anna-Chiara; Lehnherr, Dan; Hampel, Frank

    2014-01-01

    Summary A series of 11 new pentacene derivatives has been synthesized, with unsymmetrical substitution based on a trialkylsilylethynyl group at the 6-position and various aryl groups appended to the 13-position. The electronic and physical properties of the new pentacene chromophores have been analyzed by UV–vis spectroscopy (solution and thin films), thermoanalytical methods (DSC and TGA), cyclic voltammetry, as well as X-ray crystallography (for 8 derivatives). X-ray crystallography has been specifically used to study the influence of unsymmetrical substitution on the solid-state packing of the pentacene derivatives. The obtained results add to our ability to better predict substitution patterns that might be helpful for designing new semiconductors for use in solid-state devices. PMID:25161729

  18. Perovskite Materials: Solar Cell and Optoelectronic Applications

    SciTech Connect

    Yang, Bin; Geohegan, David B; Xiao, Kai

    2017-01-01

    Hybrid organometallic trihalide perovskites are promising candidates in the applications for next-generation, high-performance, low-cost optoelectronic devices, including photovoltaics, light emitting diodes, and photodetectors. Particularly, the solar cells based on this type of materials have reached 22% lab scale power conversion efficiency in only about seven years, comparable to the other thin film photovoltaic technologies. Hybrid perovskite materials not only exhibit superior optoelectronic properties, but also show many interesting physical properties such as ion migration and defect physics, which may allow the exploration of more device functionalities. In this article, the fundamental understanding of the interrelationships between crystal structure, electronic structure, and material properties is discussed. Various chemical synthesis and processing methods for superior device performance in solar cells and optoelectronic devices are reviewed.

  19. Machine learning bandgaps of double perovskites

    DOE PAGES

    Pilania, G.; Mannodi-Kanakkithodi, A.; Uberuaga, B. P.; ...

    2016-01-19

    The ability to make rapid and accurate predictions on bandgaps of 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 of double perovskites. After evaluating a set of more than 1.2 million features, we identify lowest occupied Kohn-Sham levels and elemental electronegativities of the constituent atomic species as the mostmore » crucial and relevant predictors. As a result, the developed models are validated and tested using the best practices of data science and further analyzed to rationalize their prediction performance.« less

  20. 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.

  1. Machine learning bandgaps of double perovskites

    PubMed Central

    Pilania, G.; Mannodi-Kanakkithodi, A.; Uberuaga, B. P.; Ramprasad, R.; Gubernatis, J. E.; Lookman, T.

    2016-01-01

    The ability to make rapid and accurate predictions on bandgaps of 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 of double perovskites. After evaluating a set of more than 1.2 million features, we identify lowest occupied Kohn-Sham levels and elemental electronegativities 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 and further analyzed to rationalize their prediction performance. PMID:26783247

  2. Machine learning bandgaps of double perovskites

    SciTech Connect

    Pilania, G.; Mannodi-Kanakkithodi, A.; Uberuaga, B. P.; Ramprasad, R.; Gubernatis, J. E.; Lookman, T.

    2016-01-19

    The ability to make rapid and accurate predictions on bandgaps of 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 of double perovskites. After evaluating a set of more than 1.2 million features, we identify lowest occupied Kohn-Sham levels and elemental electronegativities of the constituent atomic species as the most crucial and relevant predictors. As a result, the developed models are validated and tested using the best practices of data science and further analyzed to rationalize their prediction performance.

  3. Machine learning bandgaps of double perovskites

    NASA Astrophysics Data System (ADS)

    Pilania, G.; Mannodi-Kanakkithodi, A.; Uberuaga, B. P.; Ramprasad, R.; Gubernatis, J. E.; Lookman, T.

    2016-01-01

    The ability to make rapid and accurate predictions on bandgaps of 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 of double perovskites. After evaluating a set of more than 1.2 million features, we identify lowest occupied Kohn-Sham levels and elemental electronegativities 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 and further analyzed to rationalize their prediction performance.

  4. Machine learning bandgaps of double perovskites.

    PubMed

    Pilania, G; Mannodi-Kanakkithodi, A; Uberuaga, B P; Ramprasad, R; Gubernatis, J E; Lookman, T

    2016-01-19

    The ability to make rapid and accurate predictions on bandgaps of 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 of double perovskites. After evaluating a set of more than 1.2 million features, we identify lowest occupied Kohn-Sham levels and elemental electronegativities 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 and further analyzed to rationalize their prediction performance.

  5. Organic Charge Carriers for Perovskite Solar Cells.

    PubMed

    Völker, Sebastian F; Collavini, Silvia; Delgado, Juan Luis

    2015-09-21

    The photovoltaic field is currently experiencing the "perovskite revolution". These materials have been known for decades, but only recently have they been applied in solid-state solar cells to obtain outstanding power conversion efficiencies. Given that the variety of perovskites used so far is limited, a lot of attention has been devoted to the development of suitable organic charge-transport materials to improve device performance. In this article, we will focus on the most promising materials able to transport electrons or holes from a structural point of view. Thereby, we focus on organic materials owing to their ease of preparation and manipulation, and this is nicely combined with the potential tuning of their properties through chemical synthesis.

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

    NASA Astrophysics Data System (ADS)

    Shirahata, Yasuhiro; Oku, Takeo

    2017-01-01

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

  7. Evaluation of recipes for obtaining single terminated perovskite oxide substrates

    NASA Astrophysics Data System (ADS)

    Gunnarsson, R.; Kalabukhov, A. S.; Winkler, D.

    2009-01-01

    We have re-assessed different methods to obtain single terminated perovskite oxide substrate surfaces of SrTiO3, LaAlO3 and NdGaO3. The surfaces have been probed by a combination of atomic and lateral force microscopy, X-ray photoelectron spectroscopy and reflection high-energy electron diffraction. (0 0 1)SrTiO3 surfaces were prepared with HF or plasma etching and annealing, (0 0 1)LaAlO3 surfaces were prepared with or without HCl etching and a consecutive annealing at 750-1100 °C, and (1 1 0)NdGaO3 surfaces were only annealed. Two of the recipes have previously been suggested to result in A-site terminated surfaces. However, except for the case of high-temperature annealed LaAlO3 where we observe a double-terminated surface, our data suggest that the single terminated surfaces obtained by these methods were of B-site type.

  8. Photoluminescence of A- and B-site Eu3+-substituted (SrxBa1-x)2CaWyMo1-yO6 phosphors

    NASA Astrophysics Data System (ADS)

    Sletnes, M.; Lindgren, M.; Valmalette, J. C.; Wagner, N. P.; Grande, T.; Einarsrud, M.-A.

    2016-05-01

    The photoluminescence of two series of A- and B-site Eu3+ substituted (SrxBa1-x)2CaWyMo1-yO6 double perovskite phosphor materials, (SrxBa1-x)1.96Eu0.02K0.02CaWyMo1-yO6 and (SrxBa1-x)2Ca0.96Eu0.02Li0.02WyMo1-yO6 (x and y=0, 0.25, 0.50, 0.75, and 1), were studied systematically as a function of stoichiometry and crystal structure. The Eu3+ lattice sites controlled by co-doping with either K or Li were confirmed by Raman spectroscopy. The variation in integrated emission intensity and emission colour over the experimental matrix was examined using statistical tools, and the observed trends were rationalized based on the physical and electronic structure of the phosphors. Phosphors with Eu on B-site with maximum Sr content had remarkably higher emission intensities than all other materials, but the emission was more orange than red due to domination of the 5D0-7F1 (595 nm) transition of Eu3+. The relative intensities of the 5D0-7F2 (615 nm) and 5D0-7F1 transitions of Eu3+, and thus the red-shift of the emission, decreased linearly with increasing Sr content in the A-site Eu-substituted phosphors, and reached a maximum for Sr1.96Eu0.02K0.02CaW0.25Mo0.75O6. A maximum external quantum efficiency of 17% was obtained for the phosphor Sr2Ca0.7Eu0.15Li0.15W0.5Mo0.5O6 with Eu on B-site.

  9. Quasiparticle Interference on Cubic Perovskite Oxide Surfaces

    NASA Astrophysics Data System (ADS)

    Okada, Yoshinori; Shiau, Shiue-Yuan; Chang, Tay-Rong; Chang, Guoqing; Kobayashi, Masaki; Shimizu, Ryota; Jeng, Horng-Tay; Shiraki, Susumu; Kumigashira, Hiroshi; Bansil, Arun; Lin, Hsin; Hitosugi, Taro

    2017-08-01

    We report the observation of coherent surface states on cubic perovskite oxide SrVO3(001 ) thin films through spectroscopic-imaging scanning tunneling microscopy. A direct link between the observed quasiparticle interference patterns and the formation of a dx y -derived surface state is supported by first-principles calculations. We show that the apical oxygens on the topmost VO2 plane play a critical role in controlling the coherent surface state via modulating orbital state.

  10. The photophysics of perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Sum, Tze Chien

    2014-09-01

    Solution-processed hybrid organic-inorganic perovskite solar cells, a newcomer to the photovoltaic arena, have taken the field by storm with their extraordinary power conversion efficiencies exceeding 17%. In this paper, the photophysics and the latest findings on the carrier dynamics and charge transfer mechanisms in this new class of photovoltaic material will be examined and distilled. Some open photophysics questions will also be discussed.

  11. Surface-Driven Magnetotransport in Perovskite Nanocrystals.

    PubMed

    Thi N'Goc, Ha Le; Mouafo, Louis Donald Notemgnou; Etrillard, Céline; Torres-Pardo, Almudena; Dayen, Jean-François; Rano, Simon; Rousse, Gwenaëlle; Laberty-Robert, Christel; Calbet, Jose Gonzales; Drillon, Marc; Sanchez, Clément; Doudin, Bernard; Portehault, David

    2017-03-01

    Unique insights into magnetotransport in 20 nm ligand-free La0.67 Sr0.33 MnO3 perovskite nanocrystals of nearly perfect crystalline quality reveal a chemically altered 0.8 nm thick surface layer that triggers exceptionally large magnetoresistance at low temperature, independently of the spin polarization of the ferromagnetic core. This discovery shows how the nanoscale impacts magnetotransport in a material widely spread as electrode in hybrid spintronic devices.

  12. Crystal structure and optical property of complex perovskite oxynitrides ALi0.2Nb0.8O2.8N0.2, ANa0.2Nb0.8O2.8N0.2, and AMg0.2Nb0.8O2.6N0.4 (A = Sr, Ba)

    NASA Astrophysics Data System (ADS)

    Moon, Keon Ho; Avdeev, Maxim; Kim, Young-Il

    2017-10-01

    Oxynitride type complex perovskites AM0.2Nb0.8O3-xNx (A = Sr, Ba; M = Li, Na, Mg) were newly synthesized by the solid state diffusion of Li+, Na+, or Mg2+ into the layered oxide, A5Nb4O15, with concurrent O/N substitution. Neutron and synchrotron X-ray Rietveld refinement showed that SrLi0.2Nb0.8O2.8N0.2, SrNa0.2Nb0.8O2.8N0.2, and SrMg0.2Nb0.8O2.6N0.4 had body-centered tetragonal symmetry (I4/mcm), while those with A = Ba had simple cubic symmetry (Pm 3 ̅ m). In the tetragonal Sr-compounds, the nitrogen atoms were localized on the c-axial 4a site. However, the octahedral cations, M/Nb (M = Li, Na, Mg) were distributed randomly in all six compounds. The lattice volume of AM0.2Nb0.8O3-xNx was dependent on various factors including the type of A and the electronegativity of M. Compared to the simple perovskites, ANbO2N (A = Sr, Ba), AM0.2Nb0.8O3-xNx had wider band gaps (1.76-2.15 eV for A = Sr and 1.65-2.10 eV for A = Ba), but significantly lower sub-gap absorption.

  13. Light-trapping in perovskite solar cells

    SciTech Connect

    Du, Qing Guo; Shen, Guansheng; John, Sajeev

    2016-06-15

    We numerically demonstrate enhanced light harvesting efficiency in both CH{sub 3}NH{sub 3}PbI{sub 3} and CH(NH{sub 2}){sub 2}PbI{sub 3}-based perovskite solar cells using inverted vertical-cone photonic-crystal nanostructures. For CH{sub 3}NH{sub 3}PbI{sub 3} perovskite solar cells, the maximum achievable photocurrent density (MAPD) reaches 25.1 mA/cm{sup 2}, corresponding to 92% of the total available photocurrent in the absorption range of 300 nm to 800 nm. Our cell shows 6% absorption enhancement compared to the Lambertian limit (23.7 mA/cm{sup 2}) and has a projected power conversion efficiency of 12.9%. Excellent solar absorption is numerically demonstrated over a broad angular range from 0 to 60 degree for both S- and P- polarizations. For the corresponding CH(NH{sub 2}){sub 2}PbI{sub 3} based perovskite solar cell, with absorption range of 300 nm to 850 nm, we find a MAPD of 29.1 mA/cm{sup 2}, corresponding to 95.4% of the total available photocurrent. The projected power conversion efficiency of the CH(NH{sub 2}){sub 2}PbI{sub 3} based photonic crystal solar cell is 23.4%, well above the current world record efficiency of 20.1%.

  14. Intriguing Optoelectronic Properties of Metal Halide Perovskites.

    PubMed

    Manser, Joseph S; Christians, Jeffrey A; Kamat, Prashant V

    2016-11-09

    A new chapter in the long and distinguished history of perovskites is being written with the breakthrough success of metal halide perovskites (MHPs) as solution-processed photovoltaic (PV) absorbers. The current surge in MHP research has largely arisen out of their rapid progress in PV devices; however, these materials are potentially suitable for a diverse array of optoelectronic applications. Like oxide perovskites, MHPs have ABX3 stoichiometry, where A and B are cations and X is a halide anion. Here, the underlying physical and photophysical properties of inorganic (A = inorganic) and hybrid organic-inorganic (A = organic) MHPs are reviewed with an eye toward their potential application in emerging optoelectronic technologies. Significant attention is given to the prototypical compound methylammonium lead iodide (CH3NH3PbI3) due to the preponderance of experimental and theoretical studies surrounding this material. We also discuss other salient MHP systems, including 2-dimensional compounds, where relevant. More specifically, this review is a critical account of the interrelation between MHP electronic structure, absorption, emission, carrier dynamics and transport, and other relevant photophysical processes that have propelled these materials to the forefront of modern optoelectronics research.

  15. Large polarons in lead halide perovskites

    PubMed Central

    Miyata, Kiyoshi; Meggiolaro, Daniele; Trinh, M. Tuan; Joshi, Prakriti P.; Mosconi, Edoardo; Jones, Skyler C.; De Angelis, Filippo; Zhu, X.-Y.

    2017-01-01

    Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3− frameworks, irrespective of the cation type. The difference lies in the polaron formation time, which, in CH3NH3PbBr3 (0.3 ps), is less than half of that in CsPbBr3 (0.7 ps). First-principles calculations confirm large polaron formation, identify the Pb-Br-Pb deformation modes as responsible, and explain quantitatively the rate difference between CH3NH3PbBr3 and CsPbBr3. The findings reveal the general advantage of the soft [PbX3]− sublattice in charge carrier protection and suggest that there is likely no mechanistic limitations in using all-inorganic or mixed-cation lead halide perovskites to overcome instability problems and to tune the balance between charge carrier protection and mobility. PMID:28819647

  16. Light-trapping in perovskite solar cells

    DOE PAGES

    Du, Qing Guo; Shen, Guansheng; John, Sajeev

    2016-06-01

    We numerically demonstrate enhanced light harvesting efficiency in both CH3NH3PbI3 and CH(NH2)2PbI3-based perovskite solar cells using inverted verticalcone photonic-crystal nanostructures. For CH3NH3PbI3 perovskite solar cells, the maximum achievable photocurrent density (MAPD) reaches 25.1 mA/cm2, corresponding to 92% of the total available photocurrent in the absorption range of 300 nm to 800 nm. Our cell shows 6% absorption enhancement compared to the Lambertian limit (23.7 mA/cm2) and has a projected power conversion efficiency of 12.9%. Excellent solar absorption is numerically demonstrated over a broad angular range from 0 to 60 degree for both S- and P- polarizations. For the corresponding CH(NH2)2PbI3more » based perovskite solar cell, with absorption range of 300 nm to 850 nm, we find a MAPD of 29.1 mA/cm2, corresponding to 95.4% of the total available photocurrent. Furthermore, the projected power conversion efficiency of the CH(NH2)2PbI3 based photonic crystal solar cell is 23.4%, well above the current world record efficiency of 20.1%.« less

  17. Resistance switching memory in perovskite oxides

    SciTech Connect

    Yan, Z.B. Liu, J.-M.

    2015-07-15

    The resistance switching behavior has recently attracted great attentions for its application as resistive random access memories (RRAMs) due to a variety of advantages such as simple structure, high-density, high-speed and low-power. As a leading storage media, the transition metal perovskite oxide owns the strong correlation of electrons and the stable crystal structure, which brings out multifunctionality such as ferroelectric, multiferroic, superconductor, and colossal magnetoresistance/electroresistance effect, etc. The existence of rich electronic phases, metal–insulator transition and the nonstoichiometric oxygen in perovskite oxide provides good platforms to insight into the resistive switching mechanisms. In this review, we first introduce the general characteristics of the resistance switching effects, the operation methods and the storage media. Then, the experimental evidences of conductive filaments, the transport and switching mechanisms, and the memory performances and enhancing methods of perovskite oxide based filamentary RRAM cells have been summarized and discussed. Subsequently, the switching mechanisms and the performances of the uniform RRAM cells associating with the carrier trapping/detrapping and the ferroelectric polarization switching have been discussed. Finally, the advices and outlook for further investigating the resistance switching and enhancing the memory performances are given.

  18. Intriguing optoelectronic properties of metal halide perovskites

    DOE PAGES

    Manser, Joseph S.; Christians, Jeffrey A.; Kamat, Prashant V.

    2016-06-21

    Here, a new chapter in the long and distinguished history of perovskites is being written with the breakthrough success of metal halide perovskites (MHPs) as solution-processed photovoltaic (PV) absorbers. The current surge in MHP research has largely arisen out of their rapid progress in PV devices; however, these materials are potentially suitable for a diverse array of optoelectronic applications. Like oxide perovskites, MHPs have ABX3 stoichiometry, where A and B are cations and X is a halide anion. Here, the underlying physical and photophysical properties of inorganic (A = inorganic) and hybrid organic-inorganic (A = organic) MHPs are reviewed withmore » an eye toward their potential application in emerging optoelectronic technologies. Significant attention is given to the prototypical compound methylammonium lead iodide (CH3NH3PbI3) due to the preponderance of experimental and theoretical studies surrounding this material. We also discuss other salient MHP systems, including 2- dimensional compounds, where relevant. More specifically, this review is a critical account of the interrelation between MHP electronic structure, absorption, emission, carrier dynamics and transport, and other relevant photophysical processes that have propelled these materials to the forefront of modern optoelectronics research.« less

  19. Defect Tolerance in Methylammonium Lead Triiodide Perovskite

    SciTech Connect

    Steirer, K. Xerxes; Schulz, Philip; Teeter, Glenn; Stevanovic, Vladan; Yang, Mengjin; Zhu, Kai; Berry, Joseph J.

    2016-08-12

    Photovoltaic applications of perovskite semiconductor material systems have generated considerable interest in part because of predictions that primary defect energy levels reside outside the bandgap. We present experimental evidence that this enabling material property is present in the halide-lead perovskite, CH3NH3PbI3 (MAPbI3), consistent with theoretical predictions. By performing X-ray photoemission spectroscopy, we induce and track dynamic chemical and electronic transformations in the perovskite. These data show compositional changes that begin immediately with exposure to X-ray irradiation, whereas the predominant electronic structure of the thin film on compact TiO2 appears tolerant to the formation of compensating defect pairs of VI and VMA and for a large range of I/Pb ratios. Changing film composition is correlated with a shift of the valence-band maximum only as the halide-lead ratio drops below 2.5. This delay is attributed to the invariance of MAPbI3 electronic structure to distributed defects that can significantly transform the electronic density of states only when in high concentrations.

  20. Light-trapping in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Du, Qing Guo; Shen, Guansheng; John, Sajeev

    2016-06-01

    We numerically demonstrate enhanced light harvesting efficiency in both CH3NH3PbI3 and CH(NH2)2PbI3-based perovskite solar cells using inverted vertical-cone photonic-crystal nanostructures. For CH3NH3PbI3 perovskite solar cells, the maximum achievable photocurrent density (MAPD) reaches 25.1 mA/cm2, corresponding to 92% of the total available photocurrent in the absorption range of 300 nm to 800 nm. Our cell shows 6% absorption enhancement compared to the Lambertian limit (23.7 mA/cm2) and has a projected power conversion efficiency of 12.9%. Excellent solar absorption is numerically demonstrated over a broad angular range from 0 to 60 degree for both S- and P- polarizations. For the corresponding CH(NH2)2PbI3 based perovskite solar cell, with absorption range of 300 nm to 850 nm, we find a MAPD of 29.1 mA/cm2, corresponding to 95.4% of the total available photocurrent. The projected power conversion efficiency of the CH(NH2)2PbI3 based photonic crystal solar cell is 23.4%, well above the current world record efficiency of 20.1%.

  1. Metal halide perovskite nanomaterials: synthesis and applications.

    PubMed

    Ha, Son-Tung; Su, Rui; Xing, Jun; Zhang, Qing; Xiong, Qihua

    2017-04-01

    Nanomaterials refer to those with at least one dimension being at the nanoscale (i.e. <100 nm) such as quantum dots, nanowires, and nanoplatelets. These types of materials normally exhibit optical and electrical properties distinct from their bulk counterparts due to quantum confinement or strong anisotropy. In this perspective, we will focus on a particular material family: metal halide perovskites, which have received tremendous interest recently in photovoltaics and diverse photonic and optoelectronic applications. The different synthesis approaches and growth mechanisms will be discussed along with their novel characteristics and applications. Taking perovskite quantum dots as an example, the quantum confinement effect and high external quantum efficiency are among these novel properties and their excellent performance in applications, such as single photon emitters and LEDs, will be discussed. Understanding the mechanism behind the formation of these nanomaterial forms of perovskite will help researchers to come up with effective strategies to combat the emerging challenges of this family of materials, such as stability under ambient conditions and toxicity, towards next generation applications in photovoltaics and optoelectronics.

  2. 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.

  3. Equation of State of Lower Mantle (Al,Fe)-MgSiO3 Perovskite

    NASA Astrophysics Data System (ADS)

    Prewitt, C. T.; Andrault, D.; Bolfan-Casanova, N.; Guignot, N.

    2001-12-01

    The compression behavior of various (Al,Fe)-MgSiO3 perovskites was investigated by powder X-ray diffraction up to 70 GPa on the ID30 beamline of ESRF (Grenoble). We used diamond anvil cell coupled with CO2 laser-heating, a most powerful technique to relax stresses and perform reliable equation of state up to typical lower mantle pressures. In contrast to Fe which essentially increases the room pressure unit cell volume [1], the effect of Al is to increase the bulk modulus of silicate perovskite. This result contrast with previous determinations performed at pressures below 10 GPa on samples synthesized in the multi-anvil press [2, 3]. Such a difference can be explained by a change in the substitution mechanism of Al in MgSiO3 with increasing pressure and temperature, in agreement with recent ab-initio calculations [4]. Our results confirm that the Earth's lower mantle (Mg+Fe)/Si ratio is greater than unity, because of the high stiffness of silicate perovskite. 1- H.K. Mao, R.J. Hemley, Y. Fei, J.F. Shu, L.C. Chen, A.P. Jephcoat, Y. Wu and W.A. Basset, Journal of Geophysical Research 96(B5), 8069-8079, 1991. 2- A. Kubo, T. Yagi, S. Ono and M. Akaogi, in: Proceeding of the Japan Academy 76, pp. 103-107, 2000. 3- J. Zhang and D.J. Weidner, Science 284, 782-784, 1999. 4- J.P. Brodholt, Nature 407, 620-622, 2000.

  4. Performing Substitute Teaching

    ERIC Educational Resources Information Center

    Bletzer, Keith V.

    2010-01-01

    Formal education is both a right and an obligation bestowed on young people in most all nations of the world. Teachers (adults) and students (youth) form a co-present dyadic contract that must be maintained within the classroom. Substitute teachers fill a role in sustaining the integrity of this teacher-student link, whenever teachers are absent.…

  5. The Age of Substitutability

    ERIC Educational Resources Information Center

    Goeller, H. E.; Weinberg, Alvin M.

    1976-01-01

    Dwindling mineral resources might cause a shift from nonrenewable resources to renewable resources and inexhaustible elements such as iron and aluminum. Alternative energy sources such as breeder, fusion, solar, and geothermal power must be developed for production and recycling of materials. Substitution and, hence, living standards ultimately…

  6. No cheap substitutes.

    PubMed

    Griffiths, Peter

    2016-06-15

    The Nuffield Trust report on reshaping the healthcare workforce was published last month. Its conclusions were widely reported as a recommendation to 'train up' nurses as a solution to junior doctor shortages, with support workers, in turn, substituting for registered nurses.

  7. The Age of Substitutability

    ERIC Educational Resources Information Center

    Goeller, H. E.; Weinberg, Alvin M.

    1976-01-01

    Dwindling mineral resources might cause a shift from nonrenewable resources to renewable resources and inexhaustible elements such as iron and aluminum. Alternative energy sources such as breeder, fusion, solar, and geothermal power must be developed for production and recycling of materials. Substitution and, hence, living standards ultimately…

  8. Performing Substitute Teaching

    ERIC Educational Resources Information Center

    Bletzer, Keith V.

    2010-01-01

    Formal education is both a right and an obligation bestowed on young people in most all nations of the world. Teachers (adults) and students (youth) form a co-present dyadic contract that must be maintained within the classroom. Substitute teachers fill a role in sustaining the integrity of this teacher-student link, whenever teachers are absent.…

  9. Screening Substitute Teachers.

    ERIC Educational Resources Information Center

    Kakkuri, Mark

    2000-01-01

    The screening process a school district uses in hiring substitute teachers is critical to striking a balance between required qualifications and immediate need. Typically, screening involves at least one of the following: pre-screening, paper and pencil screening, interviews, and background checks, each of which is used to different degrees…

  10. Organizing Substitute Teachers.

    ERIC Educational Resources Information Center

    Vail, Kathleen

    2000-01-01

    Many substitute teachers are underpaid, undertrained, and "invisible" employees lacking health benefits and respect from regular colleagues. Grass-roots organizing efforts have improved working conditions for subs in two Florida and California districts. Districts' improvement initiatives should be guided by concerns for student…

  11. Thermodynamics of mixing in MgSiO 3-Al 2O 3 perovskite and ilmenite from ab initio calculations

    NASA Astrophysics Data System (ADS)

    Jung, D. Y.; Vinograd, V. L.; Fabrichnaya, O. B.; Oganov, A. R.; Schmidt, M. W.; Winkler, B.

    2010-07-01

    The thermodynamic mixing functions of MgSiO 3-Al 2O 3 solid solutions in perovskite and ilmenite structures were modeled based on the results of ab initio calculations applied to a set of supercell structures containing 64 and 48 exchangeable sites, respectively. The sampled structures were constructed from the supercells of the end-members MgSiO 3 perovskite and Al 2O 3 corundum by inserting double AlAl and MgSi defects, respectively, at all possible distances. From these calculations the pairwise effective interactions were derived and used to calculate enthalpy differences between successive configurations produced in Monte Carlo simulation runs. The temperature dependent enthalpies of mixing of the solid solutions were evaluated as averages over the Monte Carlo runs while the free energies of mixing were calculated with the method of thermodynamic integration. The phase equilibria of perovskite, ilmenite and garnet in the Mg-Si-Al-O system were calculated using the computed models of mixing and the standard thermodynamic properties of the end-members from the data base of Fabrichnaya (1999). The obtained activity-composition models are in good agreement with available experimental constraints, thereby showing that the thermodynamic effects of mixing in silicate solid solutions with coupled substitutions can be reliably predicted based on ab initio calculated total energies of a small set of supercell structures.

  12. Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts

    PubMed Central

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; Hardin, William G.; Dai, Sheng; Kolpak, Alexie M.; Johnston, Keith P.; Stevenson, Keith J.

    2016-01-01

    Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr2+ substitution into La1−xSrxCoO3−δ. We attempt to rationalize the high activities of La1−xSrxCoO3−δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis. PMID:27006166

  13. Bifunctional alkyl chain barriers for efficient perovskite solar cells.

    PubMed

    Zhang, Jing; Hu, Zhelu; Huang, Like; Yue, Guoqiang; Liu, Jinwang; Lu, Xingwei; Hu, Ziyang; Shang, Minghui; Han, Liyuan; Zhu, Yuejin

    2015-04-25

    Perovskite solar cells as a hot research topic show the necessity of controlling the interface. In this work, an insulating alkyl chain layer is self-assembled at the perovskite/hole transport material interface, which successfully exhibits a dual function: blocking electron recombination and resisting moisture at the same time. Improved solar energy conversion efficiency and stability of the device are both achieved.

  14. Morphological Optimization of Perovskite Thin Films via Dynamic Zone Annealing

    NASA Astrophysics Data System (ADS)

    Sun, Yan; Wang, Kai; Gong, Xiong; Karim, Alamgir

    2015-03-01

    Organolead Halide Perovskites have been proved to be excellent candidates for application in low-cost high-efficient solar cells owing to their superior desired optical and electrical properties, as well as compatibility with low-temperature solution-processed manufacturing. However, most perovskites applications in photovoltaics require high quality perovskite films. Although tremendous works on tuning perovskite film morphology have been reported previously, it is still a challenge to realize high quality perovskite film with controllable film uniformity and surface coverage, neither the mechanisms in the formation of perovskite. To address the issues above, here we demonstrate the effect of Dynamic Zone Annealing (DZA) on perovskite morphologies, which is proved as an efficient method to control the structure and morphology in crystalline polymer and block copolymers. Via applying the DZA method, the mechanism in perovskite film formation is studied. Furthermore, by optimizing DZA parameter such as maximum temperature, temperature gradient and zone velocity to control dendritic morphology and the grain growth, enhanced device performance was realized eventually. Equal contribution.

  15. Enhanced Charge Collection with Passivation Layers in Perovskite Solar Cells.

    PubMed

    Lee, Yong Hui; Luo, Jingshan; Son, Min-Kyu; Gao, Peng; Cho, Kyung Taek; Seo, Jiyoun; Zakeeruddin, Shaik M; Grätzel, Michael; Nazeeruddin, Mohammad Khaja

    2016-05-01

    The Al2 O3 passivation layer is beneficial for mesoporous TiO2 -based perovskite solar cells when it is deposited selectively on the compact TiO2 surface. Such a passivation layer suppressing surface recombination can be formed by thermal decomposition of the perovskite layer during post-annealing.

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

    PubMed

    Aharon, Sigalit; Etgar, Lioz

    2016-05-11

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

  17. Impact of Interfacial Layers in Perovskite Solar Cells.

    PubMed

    Cho, An-Na; Park, Nam-Gyu

    2017-07-23

    Perovskite solar cells (PCSs) are composed of organic-inorganic lead halide perovskite as the light harvester. Since the first report on a long-term-durable, 9.7 % efficient, solid-state perovskite solar cell, organic-inorganic halide perovskites have received considerable attention because of their excellent optoelectronic properties. As a result, a power conversion efficiency (PCE) exceeding 22 % was certified. Controlling the grain size, grain boundary, morphology, and defects of the perovskite layer is important for achieving high efficiency. In addition, interfacial engineering is equally or more important to further improve the PCE through better charge collection and a reduction in charge recombination. In this Review, the type of interfacial layers and their impact on photovoltaic performance are investigated for both the normal and the inverted cell architectures. Four different interfaces of fluorine-doped tin oxide (FTO)/electron-transport layer (ETL), ETL/perovskite, perovskite/hole-transport layer (HTL), and HTL/metal are classified, and their roles are investigated. The effects of interfacial engineering with organic or inorganic materials on photovoltaic performance are described in detail. Grain-boundary engineering is also included because it is related to interfacial engineering and the grain boundary in the perovskite layer plays an important role in charge conduction, recombination, and chargecarrier life time. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Miscellaneous Lasing Actions in Organo-Lead Halide Perovskite Films.

    PubMed

    Duan, Zonghui; Wang, Shuai; Yi, Ningbo; Gu, Zhiyuan; Gao, Yisheng; Song, Qinghai; Xiao, Shumin

    2017-06-21

    Lasing actions in organo-lead halide perovskite films have been heavily studied in the past few years. However, due to the disordered nature of synthesized perovskite films, the lasing actions are usually understood as random lasers that are formed by multiple scattering. Herein, we demonstrate the miscellaneous lasing actions in organo-lead halide perovskite films. In addition to the random lasers, we show that a single or a few perovskite microparticles can generate laser emissions with their internal resonances instead of multiple scattering among them. We experimentally observed and numerically confirmed whispering gallery (WG)-like microlasers in polygon shaped and other deformed microparticles. Meanwhile, owing to the nature of total internal reflection and the novel shape of the nanoparticle, the size of the perovskite WG laser can be significantly decreased to a few hundred nanometers. Thus, wavelength-scale lead halide perovskite lasers were realized for the first time. All of these laser behaviors are complementary to typical random lasers in perovskite film and will help the understanding of lasing actions in complex lead halide perovskite systems.

  19. 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.

  20. Solution Chemistry Engineering toward High-Efficiency Perovskite Solar Cells.

    PubMed

    Zhao, Yixin; Zhu, Kai

    2014-12-04

    Organic and inorganic hybrid perovskites (e.g., CH3NH3PbI3) have emerged as a revolutionary class of light-absorbing semiconductors that has demonstrated a rapid increase in efficiency within a few years of active research. Controlling perovskite morphology and composition has been found critical to developing high-performance perovskite solar cells. The recent development of solution chemistry engineering has led to fabrication of greater than 15-17%-efficiency solar cells by multiple groups, with the highest certified 17.9% efficiency that has significantly surpassed the best-reported perovskite solar cell by vapor-phase growth. In this Perspective, we review recent progress on solution chemistry engineering processes and various control parameters that are critical to the success of solution growth of high-quality perovskite films. We discuss the importance of understanding the impact of solution-processing parameters and perovskite film architectures on the fundamental charge carrier dynamics in perovskite solar cells. The cost and stability issues of perovskite solar cells will also be discussed.

  1. Substitution effects on bismuth based multifunctional materials

    NASA Astrophysics Data System (ADS)

    Krezhov, Kiril; Kovachev, Stefan; Svab, Erzsebet

    Described are our targeted experiments to improve understanding of some key aspects of the mechanisms contributing to intrinsic effects such as the magnetoelectric coupling in oxides. The magnetoelectric materials have long been of interest because of useful combinations of electrical, magnetic, optical and catalytic properties. Particularly spectacular are the manganites(M=Mn) for which apart from the strong magnetoresistance (MR) effect another striking feature is the occurrence of charge and orbital ordering (CO-OO) effects connected with the specific orbital orientation and the spatial arrangement of the eg orbitals. The MR and CO-OO effects are a manifestation of the strong interplay between the orbital, charge, and spin degrees of freedom in these systems and in some cases gives rise to multiferroicity. In this regard, some of our research is on new ABO3, AB2O5 and double perovskites A2BB'O6 containing p elements with lone pair electrons such as Bi3+. Bismuth creates irregular oxygen coordination environment and to stabilize its valence state often requires the use of high pressure or specific soft chemistry. Studied are the effects of cationic substitution on the structural parameters of the perovskites (Bi1-yRy)1-xAxMnO3 (R = rare earth; A= Ca2+, Sr2+; x,y=0.5), BiFexMn2-xO5, La1-xBiXMn2O5 etc. Ab-initio density functional theory calculations were performed to study the structure, magnetic and optical properties of multiferroic BiFeO3, also modified with La3+ and Mn3+. Synthesized and characterized is a new bismuth oxide - multiferroic BiFe2O5-δ A number of studies continue to address this class of materials and related-type materials such as cobaltites, chromites and ferrites, much of the work being driven by the potential applications as electrode materials in solid oxide fuel cells, exhaust gas sensors, membranes for separation processes or as catalysts but lately new functionalities emerge and are in the focus for use in electronics and information

  2. Highly efficient light management for perovskite solar cells.

    PubMed

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

    2016-01-06

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

  3. Highly efficient light management for perovskite solar cells

    PubMed Central

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

    2016-01-01

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

  4. Perovskite-fullerene hybrid materials suppress hysteresis in planar diodes.

    PubMed

    Xu, Jixian; Buin, Andrei; Ip, Alexander H; Li, Wei; Voznyy, Oleksandr; Comin, Riccardo; Yuan, Mingjian; Jeon, Seokmin; Ning, Zhijun; McDowell, Jeffrey J; Kanjanaboos, Pongsakorn; Sun, Jon-Paul; Lan, Xinzheng; Quan, Li Na; Kim, Dong Ha; Hill, Ian G; Maksymovych, Peter; Sargent, Edward H

    2015-05-08

    Solution-processed planar perovskite devices are highly desirable in a wide variety of optoelectronic applications; however, they are prone to hysteresis and current instabilities. Here we report the first perovskite-PCBM hybrid solid with significantly reduced hysteresis and recombination loss achieved in a single step. This new material displays an efficient electrically coupled microstructure: PCBM is homogeneously distributed throughout the film at perovskite grain boundaries. The PCBM passivates the key PbI3(-) antisite defects during the perovskite self-assembly, as revealed by theory and experiment. Photoluminescence transient spectroscopy proves that the PCBM phase promotes electron extraction. We showcase this mixed material in planar solar cells that feature low hysteresis and enhanced photovoltage. Using conductive AFM studies, we reveal the memristive properties of perovskite films. We close by positing that PCBM, by tying up both halide-rich antisites and unincorporated halides, reduces electric field-induced anion migration that may give rise to hysteresis and unstable diode behaviour.

  5. 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.

  6. Nano-structured electron transporting materials for perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Liu, Hefei; Huang, Ziru; Wei, Shiyuan; Zheng, Lingling; Xiao, Lixin; Gong, Qihuang

    2016-03-01

    Organic-inorganic hybrid perovskite solar cells have been developing rapidly in the past several years, and their power conversion efficiency has reached over 20%, nearing that of polycrystalline silicon solar cells. Because the diffusion length of the hole in perovskites is longer than that of the electron, the performance of the device can be improved by using an electron transporting layer, e.g., TiO2, ZnO and TiO2/Al2O3. Nano-structured electron transporting materials facilitate not only electron collection but also morphology control of the perovskites. The properties, morphology and preparation methods of perovskites are reviewed in the present article. A comprehensive understanding of the relationship between the structure and property will benefit the precise control of the electron transporting process and thus further improve the performance of perovskite solar cells.

  7. Nano-structured electron transporting materials for perovskite solar cells.

    PubMed

    Liu, Hefei; Huang, Ziru; Wei, Shiyuan; Zheng, Lingling; Xiao, Lixin; Gong, Qihuang

    2016-03-28

    Organic-inorganic hybrid perovskite solar cells have been developing rapidly in the past several years, and their power conversion efficiency has reached over 20%, nearing that of polycrystalline silicon solar cells. Because the diffusion length of the hole in perovskites is longer than that of the electron, the performance of the device can be improved by using an electron transporting layer, e.g., TiO2, ZnO and TiO2/Al2O3. Nano-structured electron transporting materials facilitate not only electron collection but also morphology control of the perovskites. The properties, morphology and preparation methods of perovskites are reviewed in the present article. A comprehensive understanding of the relationship between the structure and property will benefit the precise control of the electron transporting process and thus further improve the performance of perovskite solar cells.

  8. Highly efficient light management for perovskite solar cells

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  9. Recent progress and challenges of organometal halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Yang, Liyan; Barrows, Alexander T.; Lidzey, David G.; Wang, Tao

    2016-02-01

    We review recent progress in the development of organometal halide perovskite solar cells. We discuss different compounds used to construct perovskite photoactive layers, as well as the optoelectronic properties of this system. The factors that affect the morphology of the perovskite active layer are explored, e.g. material composition, film deposition methods, casting solvent and various post-treatments. Different strategies are reviewed that have recently emerged to prepare high performing perovskite films, creating polycrystalline films having either large or small grain size. Devices that are constructed using meso-superstructured and planar architectures are summarized and the impact of the fabrication process on operational efficiency is discussed. Finally, important research challenges (hysteresis, thermal and moisture instability, mechanical flexibility, as well as the development of lead-free materials) in the development of perovskite solar cells are outlined and their potential solutions are discussed.

  10. Planar-integrated single-crystalline perovskite photodetectors

    PubMed Central

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

    2015-01-01

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

  11. Integrating perovskite solar cells into a flexible fiber.

    PubMed

    Qiu, Longbin; Deng, Jue; Lu, Xin; Yang, Zhibin; Peng, Huisheng

    2014-09-22

    Perovskite solar cells have triggered a rapid development of new photovoltaic devices because of high energy conversion efficiencies and their all-solid-state structures. To this end, they are particularly useful for various wearable and portable electronic devices. Perovskite solar cells with a flexible fiber structure were now prepared for the first time by continuously winding an aligned multiwalled carbon nanotube sheet electrode onto a fiber electrode; photoactive perovskite materials were incorporated in between them through a solution process. The fiber-shaped perovskite solar cell exhibits an energy conversion efficiency of 3.3%, which remained stable on bending. The perovskite solar cell fibers may be woven into electronic textiles for large-scale application by well-developed textile technologies.

  12. Recent progress and challenges of organometal halide perovskite solar cells.

    PubMed

    Yang, Liyan; Barrows, Alexander T; Lidzey, David G; Wang, Tao

    2016-02-01

    We review recent progress in the development of organometal halide perovskite solar cells. We discuss different compounds used to construct perovskite photoactive layers, as well as the optoelectronic properties of this system. The factors that affect the morphology of the perovskite active layer are explored, e.g. material composition, film deposition methods, casting solvent and various post-treatments. Different strategies are reviewed that have recently emerged to prepare high performing perovskite films, creating polycrystalline films having either large or small grain size. Devices that are constructed using meso-superstructured and planar architectures are summarized and the impact of the fabrication process on operational efficiency is discussed. Finally, important research challenges (hysteresis, thermal and moisture instability, mechanical flexibility, as well as the development of lead-free materials) in the development of perovskite solar cells are outlined and their potential solutions are discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

  14. Binary halide, ternary perovskite-like, and perovskite-derivative nanostructures: hot injection synthesis and optical and photocatalytic properties.

    PubMed

    Lim, Suh-Ciuan; Lin, Hsuan-Peng; Tsai, Wei-Lun; Lin, Hao-Wu; Hsu, Yao-Tsung; Tuan, Hsing-Yu

    2017-03-17

    A variety of crystalline colloid binary halide, ternary perovskite-like and ternary perovskite-derivative nanostructures with well-defined morphologies were synthesized, thus expanding materials chemistry to the new category of nanomaterials. The optical and photocatalytic properties of ternary nanostructures were investigated.

  15. Tunable Negative Thermal Expansion in Layered Perovskites from Quasi-Two-Dimensional Vibrations

    NASA Astrophysics Data System (ADS)

    Huang, Liang-Feng; Lu, Xue-Zeng; Rondinelli, James M.

    2016-09-01

    We identify a quasi-two-dimensional (quasi-2D) phonon mode in the layered-perovskite Ca3Ti2O7, which exhibits an acoustic branch with quadratic dispersion. Using first-principles methods, we show this mode exhibits atomic displacements perpendicular to the layered [CaTiO3]2 blocks comprising the structure and a negative Grüneisen parameter. Owing to these quasi-2D structural and dynamical features, we find that the mode can be utilized to realize unusual membrane effects, including a tunable negative thermal expansion (NTE) and a rare pressure-independent thermal softening of the bulk modulus. Detailed microscopic analysis shows that the NTE relies on strong intralayer Ti—O covalent bonding and weaker interlayer interactions, which is in contrast to conventional NTE mechanisms for perovskites, such as rigid-unit modes, structural transitions, and electronic or magnetic ordering. The general application of the quasi-2D lattice dynamics opens exciting avenues for the control of lattice dynamical and thermodynamic responses of other complex layered compounds through rational chemical substitution, as we show in A3Zr2O7 (A =Ca , Sr), and by heterostructuring.

  16. Tunable Negative Thermal Expansion in Layered Perovskites from Quasi-Two-Dimensional Vibrations.

    PubMed

    Huang, Liang-Feng; Lu, Xue-Zeng; Rondinelli, James M

    2016-09-09

    We identify a quasi-two-dimensional (quasi-2D) phonon mode in the layered-perovskite Ca_{3}Ti_{2}O_{7}, which exhibits an acoustic branch with quadratic dispersion. Using first-principles methods, we show this mode exhibits atomic displacements perpendicular to the layered [CaTiO_{3}]_{2} blocks comprising the structure and a negative Grüneisen parameter. Owing to these quasi-2D structural and dynamical features, we find that the mode can be utilized to realize unusual membrane effects, including a tunable negative thermal expansion (NTE) and a rare pressure-independent thermal softening of the bulk modulus. Detailed microscopic analysis shows that the NTE relies on strong intralayer Ti-O covalent bonding and weaker interlayer interactions, which is in contrast to conventional NTE mechanisms for perovskites, such as rigid-unit modes, structural transitions, and electronic or magnetic ordering. The general application of the quasi-2D lattice dynamics opens exciting avenues for the control of lattice dynamical and thermodynamic responses of other complex layered compounds through rational chemical substitution, as we show in A_{3}Zr_{2}O_{7} (A=Ca, Sr), and by heterostructuring.

  17. Ab initio study of the polarization dependence of the optoelectronic properties of hybrid halide perovskites

    NASA Astrophysics Data System (ADS)

    Leppert, Linn; Reyes-Lillo, Sebastian E.; Neaton, Jeffrey B.; Neaton Team

    With efficiencies as high as 20%, hybrid organic-inorganic halide perovskites have garnered much of the photovoltaic community's attention. In light of recent experimental results, we investigate the coupling mechanism between polarization and optoelectronic properties of methylammonium (MA) lead iodide, (CH3NH3)PbI3, and related halide perovskites. In particular, we study the conditions that promote a combined effect of strong spin-orbit coupling and inversion symmetry breaking and that lead to a sizable Rashba/Dresselhaus effect. Using density functional theory calculations, we elucidate the emergence of Rashba/Dresselhaus splitting associated with local distortions and long-range coherent alignment of MA moieties in the material. We examine the extent to which the magnitude of the splitting, as well as other important electronic and optical properties, can be altered by increasing the macroscopic polarization. This opens avenues for manipulation of optoelectronic properties by an external electric field and/or chemical substitution of the MA molecule.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  19. Principles of Chemical Bonding and Band Gap Engineering in Hybrid Organic–Inorganic Halide Perovskites

    PubMed Central

    2015-01-01

    The performance of solar cells based on hybrid halide perovskites has seen an unparalleled rate of progress, while our understanding of the underlying physical chemistry of these materials trails behind. Superficially, CH3NH3PbI3 is similar to other thin-film photovoltaic materials: a semiconductor with an optical band gap in the optimal region of the electromagnetic spectrum. Microscopically, the material is more unconventional. Progress in our understanding of the local and long-range chemical bonding of hybrid perovskites is discussed here, drawing from a series of computational studies involving electronic structure, molecular dynamics, and Monte Carlo simulation techniques. The orientational freedom of the dipolar methylammonium ion gives rise to temperature-dependent dielectric screening and the possibility for the formation of polar (ferroelectric) domains. The ability to independently substitute on the A, B, and X lattice sites provides the means to tune the optoelectronic properties. Finally, ten critical challenges and opportunities for physical chemists are highlighted. PMID:25838846

  20. Weakening of Calcium Iridate During its Transformation from Perovskite to Post-Perovskite

    SciTech Connect

    Hunt, S.; Weidner, D; Li, L; Wang, L; Walte, N; Brodholt, J; Dobson, D

    2009-01-01

    The lowermost part of the Earth's mantle - the {approx}200-km-thick D{double_prime} layer - shows anomalous seismic properties, and is rheologically distinct from the rest of the lower mantle. The difference is thought to result from a phase transition from silicate perovskite to silicate post-perovskite. However, the rheology of the latter phase remains to be documented owing to experimental difficulties in reproducing pressures equivalent to those in the lowermost mantle. Here we address this problem by conducting laboratory experiments that use calcium iridate, which has been shown to be an appropriate low-pressure analogue. We find that the post-perovskite phase of this analogue is approximately five times weaker than its perovskite phase, and that it further weakens by a factor of two during the phase transformation; these are minimum estimates. If, as is likely, a similar weakening occurs in lower-mantle magnesium - silicate compositions, this could provide an explanation for the behaviour of the lowermost mantle as inferred from geophysical data.

  1. Enhanced Microwave Absorption Properties by Tuning Cation Deficiency of Perovskite Oxides of Two-Dimensional LaFeO3/C Composite in X-Band.

    PubMed

    Liu, Xiang; Wang, Lai-Sen; Ma, Yating; Zheng, Hongfei; Lin, Liang; Zhang, Qinfu; Chen, Yuanzhi; Qiu, Yulong; Peng, Dong-Liang

    2017-03-01

    Development of microwave absorption materials with tunable thickness and bandwidth is particularly urgent for practical applications but remains a great challenge. Here, two-dimensional nanocomposites consisting of perovskite oxides (LaFeO3) and amorphous carbon were successfully obtained through a one pot with heating treatment using sodium chloride as a hard template. The tunable absorption properties were realized by introducing A-site cation deficiency in LaFeO3 perovskite. Among the A-site cation-deficient perovskites, La0.62FeO3/C (L0.62FOC) has the best microwave absorption properties in which the maximum absorption is -26.6 dB at 9.8 GHz with a thickness of 2.94 mm and the bandwidth range almost covers all X-band. The main reason affecting the microwave absorption performance was derived from the A-site cation deficiency which induced more dipoles polarization loss. This work proposes a promising method to tune the microwave absorption performance via introducing deficiency in a crystal lattice.

  2. Hydrothermal Synthesis of a New Double Perovskite-Type Bismuthate, (Ba0.75K0.14H0.11)BiO3·nH2O

    NASA Astrophysics Data System (ADS)

    Jiang, Hong; Kumada, Nobuhiro; Yonesaki, Yoshinori; Takei, Takahiro; Kinomura, Nobukazu; Yashima, Masatomo; Azuma, Masaki; Oka, Kengo; Shimakawa, Yuichi

    2009-01-01

    A new double perovskite-type bismuthate, (Ba0.75K0.14H0.11)BiO3·nH2O was prepared by low-temperature hydrothermal reaction. This compound had the double perovskite-type structure with a cubic cell of a = 0.85444(3) nm, in which the A site was occupied by Ba atoms, K atoms, and water molecules, and Bi atoms occupied one crystallographic site. This compound exhibited superconductive diamagnetism with an onset temperature of about 8 K.

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

    NASA Astrophysics Data System (ADS)

    Pashchenko, A. V.; Pashchenko, V. P.; Prokopenko, V. K.; Turchenko, V. A.; Revenko, Yu. F.; Mazur, A. S.; Sycheva, V. Ya.; Liedienov, N. A.; Pitsyuga, V. G.; Levchenko, G. G.

    2017-01-01

    The structure, the structure imperfection, and the magnetoresistance, magnetotransport, and microstructure properties of rare-earth perovskite La0.3Ln0.3Sr0.3Mn1.1O3-δ manganites are studied by X-ray diffraction, thermogravimetry, electrical resistivity measurement, magnetic, 55Mn NMR, magnetoresistance measurement, and scanning electron microscopy. It is found that the structure imperfection increases, and the symmetry of a rhombohedrally distorted R3̅ c perovskite structure changes into its pseudocubic type during isovalent substitution for Ln = La3+, Pr3+, Nd3+, Sm3+, or Eu3+ when the ionic radius of an A cation decreases. Defect molar formulas are determined for a real perovskite structure, which contains anion and cation vacancies. The decrease in the temperatures of the metal-semiconductor ( T ms) and ferromagnet-paramagnet ( T C) phase transitions and the increase in electrical resistivity ρ and activation energy E a with increasing serial number of Ln are caused by an increase in the concentration of vacancy point defects, which weaken the double exchange 3 d 4(Mn3+)-2 p 6(O2-)-3 d 3(Mn4+)- V ( a)-3 d 4(Mn3+). The crystal structure of the compositions with Ln = La contains nanostructured planar clusters, which induce an anomalous magnetic hysteresis at T = 77 K. Broad and asymmetric 55Mn NMR spectra support the high-frequency electronic double exchange Mn3+(3 d 4) ↔ O2-(2 p 6) ↔ Mn4+(3 d 3) and indicate a heterogeneous surrounding of manganese by other ions and vacancies. A correlation is revealed between the tunneling magnetoresistance effect and the crystallite size. A composition-structure imperfection-property experimental phase diagram is plotted. This diagram supports the conclusion about a strong influence of structure imperfection on the formation of the magnetic, magnetotransport, and magnetoresistance properties of rare-earth perovskite manganites.

  4. Structure - property relations in lead tungstate based perovskite relaxor ferroelectrics

    NASA Astrophysics Data System (ADS)

    Juhas, Pavol

    The structure and dielectric properties of (1 - x)Pb(Sc 2/3W1/3)O3-(x)PbTiO3 (PSW-PT), (1 - x)Pb(Sc2/3W1/3)O 3-(x)PbZrO3 (PSW-PZ) and (1 - x)Pb(Sc1/2W1/4Ti1/4)O3-( x)Pb(Sc1/2Nb1/2)O3 (PSWT-PSN) ceramics have been investigated over a full substitution range. All compositions with x < 0.5 adopt a cubic perovskite structure; however, for x ≤ 0.25 the periodicity of the lattice is doubled due to a 1:1 ordered distribution of the B-site cations. The structural order in PSW can be described by a "random site model" with one cation site occupied by Sc3+ and the other by a random distribution of the remaining ions ( Sc3+1/3W6+2/3 ). This ordering is destabilized in solid solutions of PSW with PbZrO 3, but highly stabilized by PbTiO3, with a degree of order in excess of 95% for x ≤ 0.25 in (1 - x )PSW-(x)PT. The distinct effects of Zr and Ti on the B-site order are accompanied by remarkably different alterations in the dielectric response of the two solid solutions. Both systems are relaxor ferroelectrics, and for the substitution of PZ the temperature of permittivity maximum Tepsilon,max increases with x. However, Tepsilon,max decreases for additions of Ti up to x ≈ 0.25, even though PT has a much higher Curie temperature ( TC = 763 K) than PZ (503 K). Variations of T epsilon,max in the PSW-PT system could be also induced by altering the degree of order of a given composition; changes as high as 50°C were observed for x = 0.25. Strong effects of order were also observed in (0.25)PSWT-(0.75)PSN, where the introduction of partial order induced a relaxor to ferroelectric transition. To understand the relations between the atomic structure and dielectric properties, the effects of PT and PZ on the structure and ordering of PSW were studied using synchrotron x-ray and neutron diffraction. Rietveld refinement was carried out on the PSW-PT and PSW-PZ systems to determine their average long-range crystallographic structure, along with Pair Distribution Function (PDF

  5. Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites.

    PubMed

    Nagabhushana, G P; Shivaramaiah, Radha; Navrotsky, Alexandra

    2016-07-12

    Hybrid perovskites, especially methylammonium lead iodide (MAPbI3), exhibit excellent solar power conversion efficiencies. However, their application is plagued by poor chemical and structural stability. Using direct calorimetric measurement of heats of formation, MAPbI3 is shown to be thermodynamically unstable with respect to decomposition to lead iodide and methylammonium iodide, even in the absence of ambient air or light or heat-induced defects, thus limiting its long-term use in devices. The formation enthalpy from binary halide components becomes less favorable in the order MAPbCl3, MAPbBr3, MAPbI3, with only the chloride having a negative heat of formation. Optimizing the geometric match of constituents as measured by the Goldschmidt tolerance factor provides a potentially quantifiable thermodynamic guide for seeking chemical substitutions to enhance stability.

  6. Effect of chemical doping on the visible emission in Cu ions doped perovskite zirconates

    NASA Astrophysics Data System (ADS)

    Lee, D. J.; Lee, Y. S.

    2016-08-01

    We investigated the effect of the chemical doping on the visible emission of the Cu-ion-doped perovskite zirconates. We synthesized the Cu-ion-doped Sr1- x Ca x ZrO3 (SCZO:Cu) compounds ( x = 0 - 1), where the structural distortion and the chemical disorder were tuned due to the ionic size difference between Sr2+ and Ca2+. The nominal doping concentration of Cu ion was chosen to be 1%. We found that the visible emission in SCZO:Cu was suppressed dramatically with the substitution of Ca2+ for Sr2+ ( x > 0). The violet emission was more susceptible to the structural distortion than the orange and the green emissions. These experimental findings were discussed in relation to the electronic properties of SCZO:Cu.

  7. Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites

    PubMed Central

    Nagabhushana, G. P.; Shivaramaiah, Radha; Navrotsky, Alexandra

    2016-01-01

    Hybrid perovskites, especially methylammonium lead iodide (MAPbI3), exhibit excellent solar power conversion efficiencies. However, their application is plagued by poor chemical and structural stability. Using direct calorimetric measurement of heats of formation, MAPbI3 is shown to be thermodynamically unstable with respect to decomposition to lead iodide and methylammonium iodide, even in the absence of ambient air or light or heat-induced defects, thus limiting its long-term use in devices. The formation enthalpy from binary halide components becomes less favorable in the order MAPbCl3, MAPbBr3, MAPbI3, with only the chloride having a negative heat of formation. Optimizing the geometric match of constituents as measured by the Goldschmidt tolerance factor provides a potentially quantifiable thermodynamic guide for seeking chemical substitutions to enhance stability. PMID:27357677

  8. First-principles study of ionic oxygen mobility of Sr-containing LaAlO(3) perovskite.

    PubMed

    Hernández, Norge Cruz; Fernández Sanz, Javier; Alvarez, Luis Javier

    2009-07-29

    The fundamental phenomena underlying the electrical conduction properties of Sr-containing LaAlO(3) perovskites are studied through DFT simulations. The most energetically favourable substitution sites for Sr in the LaAlO(3) lattice and the energetic barriers for oxygen diffusion were calculated. Ab initio molecular dynamics was used to investigate the onset of oxygen transport. Experimental characterization of this material has suggested the existence of undercoordinated Al atoms upon substitution of La with Sr. Our results confirm the existence of four-  (Al(IV)) and fivefold (Al(V))-coordinated Al at the expense of the amount of sixfold-coordinated ones (Al(VI)), and explain the appearance of a small peak at 66 ppm in the (27)Al NMR spectrum.

  9. Sensory Substitution for Wounded Servicemembers

    DTIC Science & Technology

    2009-10-28

    traumatic brain injury (TBI) and two civilians, all with partial visual impairment , evaluated the vision sensory substitution systems. The servicemember...Mobility Augmentation; Wounded Service Members; Human-Centered Computing; Vision Augmentation, Vision , Balance and Hearing; Sensory Substitution-enabled...mitigation of vision sensory and mobility losses. 2) Improved the usefulness of available sensory substitution technologies for injured military

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

    SciTech Connect

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

    2016-06-13

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (V $••\\atop{o}$) enriched at the surface. Here we show that reducing the surface V $••\\atop{o}$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $••\\atop{o}$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a `volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.

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

    PubMed

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

    2016-09-01

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.

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

    DOE PAGES

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; ...

    2016-06-13

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO 3 ) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H 2 O and CO 2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, Sr La ') by the positively charged oxygen vacancies (Vmore » $$••\\atop{o}$$) enriched at the surface. Here we show that reducing the surface V $$••\\atop{o}$$ concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O 2 molecules. We take La 0.8 Sr 0.2 CoO 3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of V $$••\\atop{o}$$ and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.« less

  14. 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)

    2001-01-01

    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.

  15. Approaching compositional limits of perovskite - type oxides and oxynitrides by synthesis of Mg0.25Ca0.65Y0.1Ti(O,N)3, Ca1-xYxZr(O,N)3 (0.1 ≤ x ≤ 0.4), and Sr1-xLaxZr(O,N)3 (0.1 ≤ x ≤ 0.4)

    NASA Astrophysics Data System (ADS)

    Widenmeyer, Marc; Peng, Chen; Baki, Aykut; Xie, Wenjie; Niewa, Rainer; Weidenkaff, Anke

    2016-04-01

    Partial substitution of cations and anions in perovskite-type materials is a powerful way to tune the desired properties. The systematic variation of the cations size, the partial exchange of O2- for N3- and their effect on the size of the optical band gap and the thermal stability was investigated here. The anionic substitution resulted in the formation of the orthorhombic perovskite-type oxynitrides Mg0.25Ca0.65Y0.1Ti(O,N)3, Ca1-xYxZr(O,N)3, and Sr1-xLaxZr(O,N)3. A two-step synthesis protocol was applied: i) (nano-crystalline) oxide precursors were synthesized by a Pechini method followed by ii) ammonolysis in flowing NH3 at T = 773 K (Ti) and T = 1273 K (Zr), respectively. High-temperature synthesis of such oxide precursors by solid-state reaction generally resulted in phase separation of the different A-site cations. Changes of the crystal structures were investigated by Rietveld refinements of the powder XRD data, thermal stability by DSC/TG measurements in oxygen atmosphere, oxygen and nitrogen contents by O/N analysis using hot gas extraction technique, and optical band gaps by photoluminescence spectroscopy. By moving from Mg0.25Ca0.65Y0.1Ti(O,N)3 via Ca1-xYxZr(O,N)3 to Sr1-xLaxZr(O,N)3, the degree of tilting of the octahedral network is reduced, as observed by an increase in the B-X-B angles caused by the simultaneously increasing effective ionic radius of the A-site cation(s). In general, increasing substitution levels on the A-site (Y3+ and La3+) are accompanied by an enhanced replacement of O2- by N3-. In all three systems, this anionic substitution resulted in a reduction of the optical band gap by approximately 1 eV (Ti) and up to 2.1 eV (Zr) compared to the respective oxides. For Mg0.25Ca0.65Y0.1Ti(O,N)3 an optical band gap of 2.2 eV was observed, appropriate for a solar water splitting photocatalyst. The Zr-based oxynitrides required a by a factor of 2 higher nitrogen contents to significantly reduce the optical band gap and the measured values of 2

  16. Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution

    SciTech Connect

    Doane, Tennyson L.; Ryan, Kayla L.; Pathade, Laxmikant; Cruz, Kevin J.; Zang, Huidong; Cotlet, Mircea; Maye, Mathew M.

    2016-05-05

    The ability of cesium lead halide (CsPbX3; X = Cl, Br, I) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. Also, the exchange of CsPbI3 with Cl or Br causes a significant blue-shift in absorption and photoluminescence, whereas reacting I with CsPbBr3 causes a red-shift of similar magnitudes. With the high local halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. Finally, the merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites.

  17. Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution

    SciTech Connect

    Doane, Tennyson L.; Ryan, Kayla L.; Pathade, Laxmikant; Cruz, Kevin J.; Zang, Huidong; Cotlet, Mircea; Maye, Mathew M.

    2016-05-05

    The ability of cesium lead halide (CsPbX3; X = Cl, Br, I) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. Also, the exchange of CsPbI3 with Cl or Br causes a significant blue-shift in absorption and photoluminescence, whereas reacting I with CsPbBr3 causes a red-shift of similar magnitudes. With the high local halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. Finally, the merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites.

  18. Ferroelectricity in d0 double perovskite fluoroscandates

    NASA Astrophysics Data System (ADS)

    Charles, Nenian; Rondinelli, James M.

    2015-08-01

    Ferroelectricity in strain-free and strained double perovskite fluorides, Na3ScF6 and K2NaScF6 , is investigated using first-principles density functional theory. Although the experimental room temperature crystal structures of these fluoroscandates are centrosymmetric, i.e., Na3ScF6 (P 21/n ) and K2NaScF6 (F m 3 ¯m ), lattice dynamical calculations reveal that soft polar instabilities exist in each prototypical cubic phase and that the modes harden as the tolerance factor approaches unity. Thus the double fluoroperovskites bear some similarities to A B O3 perovskite oxides; however, in contrast, these fluorides exhibit large acentric displacements of alkali metal cations (Na, K) rather than polar displacements of the transition metal cations. Biaxial strain investigations of the centrosymmetric and polar Na3ScF6 and K2NaScF6 phases reveal that the paraelectric structures are favored under compressive strain, whereas polar structures with in-plane electric polarizations (˜5 -18 μ C cm-2 ) are realized at sufficiently large tensile strains. The electric polarization and stability of the polar structures for both chemistries are found to be further enhanced and stabilized by a coexisting single octahedral tilt system. Our results suggest that polar double perovskite fluorides may be realized by suppression of octahedral rotations about more than one Cartesian axis; structures exhibiting in- or out-of-phase octahedral rotations about the c axis are more susceptible to polar symmetries.

  19. Structural characterization of a new acentric Ruddlesden-Popper layered perovskite compound: LiHSrTa2O7.

    PubMed

    Galven, Cyrille; Fourquet, Jean-Louis; Suard, Emmanuelle; Crosnier-Lopez, Marie-Pierre; Le Berre, Françoise

    2010-04-07

    A new n = 2 member acentric Ruddlesden-Popper layered perovskite LiHSrTa(2)O(7) (LiDSrTa(2)O(7)) has been synthesized and structurally characterized from Rietveld treatment of its powder X-ray and high-resolution neutron diffraction data. It can be synthesized by a partial Li(+)/H(+) exchange from the mother phase Li(2)SrTa(2)O(7) either in solid state by NH(4)Cl or in dilute HNO(3) by controlling the amount of H(+). This compound crystallizes in the orthorhombic acentric space group Ama2 (no. 40) with lattice constants a = radical2a(p) approximately 5.5522(1) A, b = radical2a(p) approximately 5.5248(1) A and c approximately 18.7745(4) A. Classically, Ta(5+) ions occupy the octahedral sites of the kinked perovskite blocks and Sr(2+) ions completely fill the perovskite cages while Li(+) and D(+) ions are found in the interlayer spacing. Efficient positive second harmonic generation response, performed at room temperature on a polycrystalline sample, shows unambiguously the acentric character of this new phase. Interestingly, the choice of the acentric Ama2 space group to describe the structure is revealed only by high-resolution neutron diffraction data: in the interlayer spacing, Li(+) and D(+) cations are unequally distributed on different sites (two 4a sites for Li(+) and two 4b sites for D(+) ions).

  20. 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.