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Sample records for a-site substituted perovskite

  1. 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.

  2. 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).

  3. Orientational Glass Formation in Substituted Hybrid Perovskites

    DOE PAGES

    Mozur, Eve M.; Maughan, Annalise E.; Cheng, Yongqiang; ...

    2017-11-07

    Hybrid organic-inorganic perovskites have gained notoriety in the photovoltaic community for their composition-tunable band gaps and long-lived electronic excited states, which are known to be related to the crystalline phase. While indirect evidence suggests that coupling between polar organic cations affects the phase behavior, it remains unclear how the coupling manifests in hybrid perovskites such as methylammonium lead halides (CH 3NH 3PbX 3). Here, we present crystallographic and spectroscopic data for the series (CH 3NH 3) 1-xCs xPbBr 3. CH 3NH 3PbBr 3 behaves as a plastic crystal in the high temperature cubic phase, and substitution of CH 3NH 3more » + with Cs + leads to the formation of an orientational glass. While the organic molecule exhibits slow, glassy reorientational dynamics, the inorganic framework continues to undergo crystallographic phase transitions. These crystallographic transitions occur in the absence of thermodynamic signatures in the specific heat, which suggests that the phase transitions result from underlying instabilities intrinsic to the inorganic lattice. However, these transitions are not decoupled from the reorientations of the organic molecule, as indicated by inelastic and quasielastic neutron scattering. Observation of a reentrant phase transition in (CH 3NH 3) 0.8Cs 0.2PbBr 3 permits the resolution of these complex behaviors within the context of strain mediated interactions. Lastly, together, these results provide critical insight into the coupled phase behavior and dynamics in hybrid perovskites.« less

  4. Stabilized wide bandgap perovskite solar cells by tin substitution

    DOE PAGES

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

    2016-11-16

    Wide bandgap MAPb(I 1-yBr y) 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 MAPb 0.75Sn 0.25(I 1-yBr y) 3 perovskite solar cells show stable photovoltaic performance under continuous illumination. Among these cells, the one based on MAPb 0.75Sn 0.25(I 0.4Br 0.6) 3 perovskite shows the highest efficiency of 12.59%more » 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 MAPb 0.75Sn 0.25(I 1-yBr y) 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

  5. 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.

  6. 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 MAPbX 3 (MA = methylammonium, X = Br or Cl) to achieve a tunable densitymore » of states within the parent gap. Computational screening identified both Fe- and Co-substituted MAPbBr 3 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

  7. Substitutional Growth of Methylammonium Lead Iodide Perovskites in Alcohols

    DOE PAGES

    Acik, Muge; Alam, Todd M.; Guo, Fangmin; ...

    2017-09-29

    Methylammonium lead iodide (MAPbI 3) perovskites are organic–inorganic semiconductors with long carrier diffusion lengths serving as the light-harvesting component in optoelectronics. Through a substitutional growth of MAPbI 3 catalyzed by polar protic alcohols, evidence is shown in this paper for their substrate- and annealing-free production and use of toxic solvents and high temperature is prevented. The resulting variable-sized crystals (≈100 nm–10 µm) are found to be tetragonally single-phased in alcohols and precipitated as powders that are metallic-lead-free. A comparatively low MAPbI 3 yield in toluene supports the role of alcohol polarity and the type of solvent (protic vs aprotic). Themore » theoretical calculations suggest that overall Gibbs free energy in alcohols is lowered due to their catalytic impact. Based on this alcohol-catalyzed approach, MAPbI 3 is obtained, which is chemically stable in air up to ≈1.5 months and thermally stable (≤300 °C). Finally, this method is amendable to large-scale manufacturing and ultimately can lead to energy-efficient, low-cost, and stable devices.« less

  8. (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.

  9. Enhancement in magnetocaloric properties of ErCrO3 via A-site Gd substitution

    NASA Astrophysics Data System (ADS)

    Shi, Jianhang; Yin, Shiqi; Seehra, Mohindar S.; Jain, Menka

    2018-05-01

    Rare earth chromites (RCrO3) continue to be of considerable interest due to their intriguing physical properties such as spin-reorientation, multiferroicity, and magnetocaloric effect. In this paper, we compare the structural, magnetic, and magnetocaloric properties of bulk ErCrO3 with those of bulk Er0.33Gd0.67CrO3, the latter obtained by Gd substitution at the A-site (Er-site) and report substantial enhancement in the magnetocaloric response by Gd substitution. The samples prepared by the citrate route were structurally characterized at room temperature using x-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy. The XRD measurements refined by Rietveld analysis indicate that both samples crystallized in the orthorhombically distorted perovskite structure with Pbnm space group. Magnetic measurements on both samples were carried out between 5 K and 300 K in magnetic fields up to 7 T and show that TNC r (where Cr3+ orders) for Er0.33Gd0.67CrO3 is enhanced to 155 K vs. 133 K for ErCrO3 with analogous changes in the other magnetic parameters. Isothermal magnetization M vs. H data at different temperatures were used to determine changes in the magnetic entropy ( -ΔS ) and relative cooling power (RCP) for the two samples showing considerable improvement with Gd substitution in bulk ErCrO3. The maximum value of -ΔS for Er0.33Gd0.67CrO3 is 27.6 J kg-1 K-1 at 5 K and 7 T with a RCP of 531.1 J kg-1, in comparison to maximum -ΔS = 10.7 J kg-1 K-1 at 15 K with an RCP of 416.4 J kg-1 for ErCrO3 at 7 T.

  10. A-site Ordered Chromium Perovskites, ACu3Cr4O12 with A = Trivalent Ions

    NASA Astrophysics Data System (ADS)

    Sugiyama, Jun; Nozaki, Hiroshi; Umegaki, Izumi; Higemoto, Wataru; Isobe, Masahiko; Takagi, Hidenori; Sakurai, Hiroya; Ansaldo, Eduardo J.; Brewer, Jess H.; Sassa, Yasmine; Forslund, Ola Kenji; Månsson, Martin

    The magnetic ground state of the A-site ordered chromium perovskites, ACu3Cr4O12 with A = Y, La, Eu, and Lu has been investigated with μ+SR using powder samples prepared by a high-pressure technique. Weak transverse field measurements revealed that the four compounds enter into a magnetic phase below 230-260 K. Moreover, the transition temperature (TN) was found to decrease with increasing the size of A3+ ions. Zero field measurements indicated the formation of static antiferromagnetic (AF) order in ACu3Cr4O12 below TN. Furthermore, since the internal magnetic field in the AF phase is independent of A, the role of 4f electrons on the AF state is very limited and/or eventually absence in ACu3Cr4O12.

  11. A DFT+U study of A-site and B-site substitution in BaFeO3-δ.

    PubMed

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

    2015-09-28

    BaFeO3-δ (BFO)-based perovskites have emerged as cheap and effective oxygen electrocatalysts for oxygen reduction reaction at high temperatures. The BFO cubic phase facilitates a high oxygen deficiency and is commonly stabilised by partial substitution. Understanding the electronic mechanisms of substitution and oxygen deficiency is key to rational material design, and can be realised through DFT analysis. In this work an in-depth first principle DFT+U study is undertaken to determine site distinctive characteristics for 12.5%, Y, La and Ce substitutions in BFO. In particular, it is shown that B-site doped structures exhibit a lower energy cost for oxygen vacancy formation relative to A site doping and pristine BFO. This is attributed to the stabilisation of holes in the oxygen sub-lattice and increased covalency of the Fe-O bonds of the FeO6 octahedra in B-site-substituted BFO. Charge analysis shows that A-site substitution amounts to donor doping and consequently impedes the accommodation of other donors (i.e. oxygen vacancies). However, A-site substitution may also exhibit a higher electronic conductivity due to less lattice distortion for oxygen deficiency compared to B-site doped structures. Furthermore, analysis of the local structural effects provides physical insight into stoichiometric expansions observed for this material.

  12. A-Site Cation Substitutions in Strained Y-Doped BaZrO 3 Multilayer Films Leading to Fast Proton Transport Pathways

    SciTech Connect

    Aruta, Carmela; Han, Chu; Zhou, Si

    Proton-conducting perovskite oxides form a class of solid electrolytes for novel electrochemical devices operating at moderate temperatures. Here, we use hard X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and density functional theory calculations to investigate the structure and elucidate the origin of the fast proton transport properties of strained ultrathin films of Y-doped BaZrO 3 grown by pulsed lased deposition on NdGaO 3. Our study shows that our BaZr 0.8Y 0.2O 3 films incorporate a significant amount of Y dopants, and to a lesser extent also Zr ions, substituting for Ba 2+, and that these substitutional defects agglomerate forming columnarmore » regions crossing vertically from the surface to the interface the entire film. In conclusion, our calculations also show that, in regions rich in Y substitutions for both Zr and Ba, the proton transfer process involves nearly zero-energy barriers, indicating that A-site cation substitutions by Y lead to fast transport pathways and hence are responsible for the previously observed enhanced values of the proton conductivity of these perovskite oxide films.« less

  13. 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.

  14. 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

  15. 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 Li 7La 3Z r2-xA xO 12 (LLZO, A = Ta, Ti) garnets, and chromium-substituted La (2/3)-xLi 3xTi 1-yCr yO 3 (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 phasemore » with minor impurity phases for Cr-LLTO. Ionic conductivity for Ti-LLZO (Li 7La 3Zr 1.4Ti 0.6O 12), Ta-LLZO (Li 6.03La 3Zr 1.533Ta 0.46O 12), and Cr-LLTO (La (2/3)-xLi 3xTi 0.9Cr 0.1O 3) 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 (Ti 0.6-LLZO), 0.54 eV (Ta 0.5-LLZO), and 0.20 eV (Cr 0.1-LLTO).« less

  16. 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.

  17. Enhanced magnetism of perovskite oxides, Sr(Sn,Fe)O3- δ , by substitution of nonmagnetic Ca and Ti ions

    NASA Astrophysics Data System (ADS)

    Nomura, Kiyoshi; Suzuki, Shigeyo; Mizunuma, Tomoya; Koike, Yuya; Okazawa, Atsushi

    2017-11-01

    Magnetic properties of perovskite oxides, SrSn1- x Fe x O3- δ ( x ≤ 0.15), substituted with nonmagnetic Ca and Ti ions were studied. XRD patterns showed the orthorhombic structure (close to tetragonal) of (Sr1- y Ca y )(Sn1- x Fe x )O3- δ and Sr(Sn1- x- y Fe x Ti y )O3- δ . The cell volumes decreased with the increase of Ca and Ti doping rates. Although Ti-substituted Sr(Sn, Fe)O3- δ showed small saturation magnetizations as compared with non-Ti substituted one, the magnetization increased a little with Ti doping rates up to 15%. On the other hand, all Ca-substituted Sr(Sn, Fe)O3- δ showed larger saturation magnetization than non-Ca substituted one. Two doublets of Fe3+ and a doublet of Fe4+ were observed in Mössbauer spectra of Ca-substituted Sr(Sn, Fe)O3- δ with weak ferromagnetism, and two sextets of high spin Fe3+ were additionally observed in Mössbauer spectra of Ca-doped Sr(Sn, Fe)O3- δ with relatively strong ferromagnetism. When Sr(Sn, Fe)O3- δ were further codoped with Ca and Ti ions, they showed the stable and enhanced ferromagnetic properties. It is considered that magnetic polarons among high spin Fe3+ species are overlapped by shrinking or deforming the crystal structure of perovskite oxides. That is the magnetism induced by a chemical pressure of perovskite oxides.

  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

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

  19. Spin-state responses to light impurity substitution in low-spin perovskite LaCoO3

    NASA Astrophysics Data System (ADS)

    Tomiyasu, Keisuke; Kubota, Yuuki; Shimomura, Saya; Onodera, Mitsugi; Koyama, Syun-Ichi; Nojima, Tsutomu; Ishihara, Sumio; Nakao, Hironori; Murakami, Youichi

    2013-06-01

    We studied the spin-state responses to light impurity substitution in low-spin perovskite LaCoO3 (Co3+: d6) through magnetization, x-ray fluorescence, and electrical resistivity measurements of single-crystal LaCo0.99M0.01O3 (M = Cr, Mn, Fe, Ni). In the magnetization curves measured at 1.8 K, a change in the spin-state was not observed for Cr, Mn, or Fe substitution but was observed for Ni substitution. Strong magnetic anisotropy was also found in the Ni-substituted sample. The fluorescence measurements revealed that the valences were roughly estimated to be Cr3+, Mn(4-δ)+, Fe(3+δ')+, and Ni3+. From the observed chemical trends, we propose that the chemical potential is a key factor in inducing the change of the low-spin state. By expanding a model of the ferromagnetic spin-state heptamer generated by hole doping [Podlesnyak , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.101.247603 101, 247603 (2008)], the emergence of highly anisotropic spin-state molecular ferromagnets induced by low-spin Ni3+ with Jahn-Teller activity is suggested. We also discuss applicability of the present results to other materials with Fe (d6).

  20. Magnetic, thermodynamic and optical properties of Sb-substituted Ba2PrBiO6 double perovskite oxides

    NASA Astrophysics Data System (ADS)

    Onodera, K.; Kogawa, T.; Matsukawa, M.; Taniguchi, H.; Nishidate, K.; Matsushita, A.; Shimoda, M.

    2018-03-01

    We demonstrated crystal structures, magnetic, thermodynamic and optical properties of the B-site substituted perovskite oxides Ba2Pr(Bi1 ‑ x,Sbx ) O6 (x=0, 0.1 and 0.2). Polycrystalline samples of Sb-substituted Ba2PrBiO6 were prepared with the conventional solid-state reaction technique. The X-ray diffraction data revealed that the polycrystalline samples are an almost single phase with a monoclinic structure (C2 /m). Substitution of smaller Sb ion at Bi site causes a monotonic decrease in both the lattice parameters and volume. Magnetization measurements at high temperatures above 200 K show that the effective magnetic moment is estimated to be around 3.15 µB , which is close to that for Pr3+ion. The X-ray photoemission spectroscopy analysis revealed that a prominent peak of Pr3+ is dominant with a smaller shoulder structure of Pr4+. A Schottky-like anomaly observed in the low-temperature specific heat measurement is explained by low-lying splitting of Pr ions under the crystal field effect. Optical spectra were measured using a diffuse-reflectance method. The band gaps were estimated from the optical data to be 0.977 eV and 1.073 eV, at x = 0 and 0.2, respectively. The effect of band gap opening due to Sb substitution is examined by using the density functional theory.

  1. Characterization of ordering in A-site deficient perovskite Ca 1–xLa 2x/3TiO 3 using STEM/EELS

    DOE PAGES

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

    2016-09-15

    The vacancy ordering behavior of an A-site deficient perovskite system, Ca 1–xLa 2x/3TiO 3, was studied using atomic resolution scanning transmission electron microscopy (STEM) in conjunction with electron energy-loss spectroscopy (EELS), with the aim of determining the role of A-site composition changes. At low La content (x = 0.2), adopting Pbnm symmetry, there was no indication of long-range ordering. Domains, with clear boundaries, were observed in bright-field (BF) imaging, but were not immediately visible in the corresponding high-angle annular dark-field (HAADF) image. These boundaries, with the aid of displacement maps from A-site cations in the HAADF signal, are shown tomore » be tilt boundaries. At the La-rich end of the composition (x = 0.9), adopting Cmmm symmetry, long-range ordering of vacancies and La 3+ ions was observed, with alternating La-rich and La-poor layers on (001)p planes, creating a double perovskite lattice along the c axis. These highly ordered domains can be found isolated within a random distribution of vacancies/La 3+, or within a large population, encompassing a large volume. In regions with a high number density of double perovskite domains, these highly ordered domains were separated by twin boundaries, with 90° or 180° lattice rotations across boundaries. In conclusion, the occurrence and characteristics of these ordered structures are discussed and compared with similar perovskite systems.« less

  2. 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. 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.

  4. 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

  5. A -Site Ordered Double Perovskite CaMnTi 2 O 6 as a Multifunctional Piezoelectric and Ferroelectric–Photovoltaic Material

    SciTech Connect

    Gou, Gaoyang; Charles, Nenian; Shi, Jing

    2017-09-11

    The double perovskite CaMnTi2O6, is a rare A site ordered perovskite oxide that exhibits a sizable ferroelectric polarization and relatively high Curie temperature. Using first-principles calculations combined with detailed symmetry analyses, we identify the origin of the ferroelectricity in CaMnTi2O6. We further explore the material properties of CaMnTi2O6, including its ferroelectric polarization, dielectric and piezoelectric responses, magnetic order, electronic structure, and optical absorption coefficient. It is found that CaMnTi2O6 exhibits room-temperature-stable ferroelectricity and moderate piezoelectric responses. Moreover, CaMnTi2O6 is predicted to have a semiconducting energy band gap similar to that of BiFeO3, and its band gap can further be tuned-viamore » distortions of the planar Mn-O bond lengths. CaMnTi2O6 exemplifies a new class of single-phase semiconducting ferroelectric perovskites for potential applications in ferroelectric photovoltaic solar cells.« less

  6. Resonance Raman and excitation energy dependent charge transfer mechanism in halide-substituted hybrid perovskite solar cells.

    PubMed

    Park, Byung-wook; Jain, Sagar M; Zhang, Xiaoliang; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

    2015-02-24

    Organo-metal halide perovskites (OMHPs) are materials with attractive properties for optoelectronics. They made a recent introduction in the photovoltaics world by methylammonium (MA) lead triiodide and show remarkably improved charge separation capabilities when chloride and bromide are added. Here we show how halide substitution in OMHPs with the nominal composition CH3NH3PbI2X, where X is I, Br, or Cl, influences the morphology, charge quantum yield, and local interaction with the organic MA cation. X-ray diffraction and photoluminescence data demonstrate that halide substitution affects the local structure in the OMHPs with separate MAPbI3 and MAPbCl3 phases. Raman spectroscopies as well as theoretical vibration calculations reveal that this at the same time delocalizes the charge to the MA cation, which can liberate the vibrational movement of the MA cation, leading to a more adaptive organic phase. The resonance Raman effect together with quantum chemical calculations is utilized to analyze the change in charge transfer mechanism upon electronic excitation and gives important clues for the mechanism of the much improved photovoltage and photocurrent also seen in the solar cell performance for the materials when chloride compounds are included in the preparation.

  7. Bromine substitution improves excited-state dynamics in mesoporous mixed halide perovskite films

    SciTech Connect

    Talbert, Eric M.; Zarick, Holly F.; Boulesbaa, Abdelaziz

    Here in this study, ultrafast transient absorption spectroscopy (TAS) is utilized to examine the excited-state dynamics in methylammonium lead iodide/bromide (MAPb(I 1-xBrx)3) perovskites as a function of bromide content. TAS spectral behavior reveals characteristic lifetimes for thermalization, recombination, and charge carrier injection of MAPb(I 1-xBr x) 3 from x = 0 to 0.3 infiltrated in mesoporous titania films. Carrier recombination and charge injection lifetimes demonstrated a discernable increase with Br content likely because high carrier populations are supported by the higher density of vacant electronic states in mixed-halide perovskites due to the increased capacity of the conduction band. However, wemore » observe for the first time that carrier thermalization lifetimes significantly decrease with increasing Br. This suggests that the shift in crystal structure from tetragonal towards pseudocubic accelerates carrier cooling, resulting in the relief of the hot phonon bottleneck. Furthermore, the stabilized MAPb(I 1-xBrx) 3 samples exhibit a lower Burstein–Moss shift of 0.07–0.08 eV compared to pure MAPbI 3 (0.12 eV). Our results provide evidence that Br inclusion contributes to a broadening of the parabolic conduction band and to improvement in electron–phonon coupling and phonon propagation in the lattice.« less

  8. Bromine substitution improves excited-state dynamics in mesoporous mixed halide perovskite films.

    PubMed

    Talbert, Eric M; Zarick, Holly F; Boulesbaa, Abdelaziz; Soetan, Naiya; Puretzky, Alexander A; Geohegan, David B; Bardhan, Rizia

    2017-08-24

    In this study, ultrafast transient absorption spectroscopy (TAS) is utilized to examine the excited-state dynamics in methylammonium lead iodide/bromide (MAPb(I 1-x Br x ) 3 ) perovskites as a function of bromide content. TAS spectral behavior reveals characteristic lifetimes for thermalization, recombination, and charge carrier injection of MAPb(I 1-x Br x ) 3 from x = 0 to 0.3 infiltrated in mesoporous titania films. Carrier recombination and charge injection lifetimes demonstrated a discernable increase with Br content likely because high carrier populations are supported by the higher density of vacant electronic states in mixed-halide perovskites due to the increased capacity of the conduction band. However, we observe for the first time that carrier thermalization lifetimes significantly decrease with increasing Br. This suggests that the shift in crystal structure from tetragonal towards pseudocubic accelerates carrier cooling, resulting in the relief of the hot phonon bottleneck. Furthermore, the stabilized MAPb(I 1-x Br x ) 3 samples exhibit a lower Burstein-Moss shift of 0.07-0.08 eV compared to pure MAPbI 3 (0.12 eV). Our results provide evidence that Br inclusion contributes to a broadening of the parabolic conduction band and to improvement in electron-phonon coupling and phonon propagation in the lattice.

  9. Enhanced performance in perovskite solar cells via bromide ion substitution and ethanol treatment

    NASA Astrophysics Data System (ADS)

    Feng, Bingjie; Duan, Jinxia; Tao, Li; Zhang, Jun; Wang, Hao

    2018-02-01

    Mixed lead halide (Pb(I1-xBrx)2) as the seed layer was employed to prepare mixed lead-halide perovskite (MAPbI3-2xBr2x, MA = CH3NH3) films through two-step sequential deposition method. Ethanol treatment process was also introduced for the control of morphology and microstructure of Pb(I1-xBrx)2 films. The ethanol treatment accelerates the crystallization of Pb(I1-xBrx)2 and the resulted Pb(I1-xBrx)2 films exhibit a porous structure which facilitates more complete conversion of PbI2 at the same time. As a result, high purity and highly crystallized MAPbI3-2xBr2x films are obtained. The photovoltaic performance of assembled perovskite solar cells based on MAPbI3-2xBr2x films are improved upon ethanol treatment and a champion power conversion efficiency (PCE) of 15.53% is obtained with x = 0.2. After exposed in air condition for 14 days, a 86% of initial PCE remains in the champion device.

  10. Bromine substitution improves excited-state dynamics in mesoporous mixed halide perovskite films

    DOE PAGES

    Talbert, Eric M.; Zarick, Holly F.; Boulesbaa, Abdelaziz; ...

    2017-08-02

    Here in this study, ultrafast transient absorption spectroscopy (TAS) is utilized to examine the excited-state dynamics in methylammonium lead iodide/bromide (MAPb(I 1-xBrx)3) perovskites as a function of bromide content. TAS spectral behavior reveals characteristic lifetimes for thermalization, recombination, and charge carrier injection of MAPb(I 1-xBr x) 3 from x = 0 to 0.3 infiltrated in mesoporous titania films. Carrier recombination and charge injection lifetimes demonstrated a discernable increase with Br content likely because high carrier populations are supported by the higher density of vacant electronic states in mixed-halide perovskites due to the increased capacity of the conduction band. However, wemore » observe for the first time that carrier thermalization lifetimes significantly decrease with increasing Br. This suggests that the shift in crystal structure from tetragonal towards pseudocubic accelerates carrier cooling, resulting in the relief of the hot phonon bottleneck. Furthermore, the stabilized MAPb(I 1-xBrx) 3 samples exhibit a lower Burstein–Moss shift of 0.07–0.08 eV compared to pure MAPbI 3 (0.12 eV). Our results provide evidence that Br inclusion contributes to a broadening of the parabolic conduction band and to improvement in electron–phonon coupling and phonon propagation in the lattice.« less

  11. Structural and magnetic behavior of (Ni, Cu) substituted Nd0.67Sr0.33MnO3 perovskite compounds

    NASA Astrophysics Data System (ADS)

    Arun, B.; Sudakshina, B.; Akshay, V. R.; Chandrasekhar, K. Devi; Yang, H. D.; Vasundhara, M.

    2018-05-01

    Structural and magnetic phase transition of Ni and Cu substituted Nd0.67Sr0.33MnO3 perovskite compounds have been investigated. The Rietveld refinement of X-ray powder diffraction patterns confirms that both compounds have crystallized into an orthorhombic structure with Pbnm space group same as that of Nd0.67Sr0.33MnO3 compound. X-ray absorption spectra studies completely ruled out the possibility of existence of any impurities. Both compounds do not obey the Curie-Weiss law indicates the presence of some ferromagnetic clusters within the paramagnetic matrix. Ni substituted compound shows a lower value of TC and Cu substituted compound shows a higher value of TC than that of the parent. Non-saturating tendency of magnetization is more prominently seen in the case of Cu substituted compound, indicating an increase in the AFM component.

  12. 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.

  13. Effects of Mn substitution on the thermoelectric properties of the electron-doped perovskite Sr1-xLaxTiO3

    NASA Astrophysics Data System (ADS)

    Okuda, T.; Hata, H.; Eto, T.; Nishina, K.; Kuwahara, H.; Nakamura, M.; Kajimoto, R.

    2014-12-01

    We have tried to improve the n-type thermoelectric properties of the electron- doped Perovskite Sr1-xLaxTiO3 by a Mn substitution. The 1 ~ 2 % Mn substitution enhances the Seebeck coefficient (S) and reduces the thermal conductivity (κ) by about 50 % at room temperature (RT) without largely increasing the resistivity for the 5 % electron-doped SrTiO3. Consequently, the power factor at RT keeps a large value comparable to that of Bi2Te3 and the dimensionless figure-of-merits at RT increases twofold by the slight Mn substitution. Such a large reduction of κ at RT is perhaps due to the effect of Jahn-Teller active Mn3+ ions, around which dynamical local lattice distortion may occur.

  14. Thermoelectric properties of p-type perovskite compounds LaCoO3 systems containing the A-site vacancy

    NASA Astrophysics Data System (ADS)

    Anzai, Mayuka; Kawakami, Hiroshi; Saito, Miwa; Yamamura, Hiroshi

    2011-05-01

    Thermoelectric properties of Sr-doped LaCoO3 system which includes both La1-xSrxCoO3 and La0.95-xSrxsquare0.05CoO3 containing the A-site vacancy were prepared by solid state reaction. The crystal phases of the samples were investigated by X-ray diffraction method. The electrical conductivity, Seebeck coefficient, and thermal conductivity were investigated, focusing the effect of A-site vacancy. Doping of Sr to LaCoO3 improved the electrical conductivity but decreased the seebeck coefficient and increased the thermal conductivity. A-site vacancy of La0.95-xSrxsquare0.05CoO3 system, in comparison with La1-xSrxCoO3 system, increased electrical conductivity, and decreased lattice thermal conductivity. As a result, it was found that the thermoelectric properties of La0.95-xSrxsquare0.05CoO3 containing the A-site vacancy showed the higher values than those of La1-xSrxCoO3. The introduction of A-site vacancy was effective on the improvement of thermoelectric property.

  15. The effect of A-site substitution on the structure and magnetism of Sr2-xPrxFeCoO6 (x = 0, 1, 2)

    NASA Astrophysics Data System (ADS)

    Haripriya, G. R.; Chakraborty, Debamitra; Pradheesh, R.; Sankaranarayanan, V.; Sethupathi, K.

    2018-05-01

    The paper presents the variation of structure and magnetism observed with the A-site composition of the double perovskite oxide Sr2-xPrxFeCoO6 (x = 0, 1, 2). The lattice symmetry was found to be lowered from tetragonal (x = 0) to orthorhombic (x = 2). With a ratio 1:1 of Sr and Pr, a highly asymmetric monoclinic structure is observed. The magnetic behavior of the middle member (x = 1) shows resemblance with that of Sr2FeCoO6, indicating the effect of Sr in the dilution of rare earth magnetism.

  16. Investigation by Monte Carlo simulation of substitution doping in the Double Perovskite Sr2CrRe1-xWxO6

    NASA Astrophysics Data System (ADS)

    El Rhazouani, O.; Benyoussef, A.

    2018-01-01

    Re-substitution doping by W has been investigated in the Double Perovskite (DP) Sr2CrRe1-xWxO6 for x ranging from 10 to 90% by using a Monte Carlo Simulation (MCS) in the framework of Ising model. Exchange couplings used in the simulation have been approximated in previous work for experimental Curie temperatures (TC). Doping effect on: partial and total magnetization, magnetic susceptibility, internal energy, specific heat, and Curie temperature has been studied. A sharp drop of partial magnetizations at 40% of W-concentration has been noticed at the magnetic transition. Apparition of a non-monotonic behavior of the total magnetization at 20% of W-concentration. Effect of doping on the stability of the compound has been emphasized. A quasilinear decrease of TC has been observed by increasing the concentration percentage of substitution doping by W.

  17. Interplay of 3 d - and 5 d -sublattice magnetism in the double perovskite substitution series La2Zn1 -xCoxIrO6

    NASA Astrophysics Data System (ADS)

    Vogl, M.; Corredor, L. T.; Dey, T.; Morrow, R.; Scaravaggi, F.; Wolter, A. U. B.; Aswartham, S.; Wurmehl, S.; Büchner, B.

    2018-01-01

    We report on the interplay of 3 d - and 5 d -sublattice magnetism in polycrystalline samples of the double perovskite substitution series La2Zn1 -xCoxIrO6 . Powder x-ray diffraction reveals no major structural changes within the series. In magnetization measurements, a gradual shift of the transition temperature from TN ≈91 K for the Co parent compound to TN ≈8.7 K for the Zn parent compound is observed. The data on the Zn-rich members of the substitution series indicate that this is accompanied by changing roles of the 3 d sublattice of Co2 + and the strongly spin-orbit coupled 5 d -sublattice of Ir4 + with its jeff=1 /2 ground state, as a function of the Co/Zn ratio. Temperature-dependent specific-heat studies revealed a reduced magnetic entropy, pointing towards a large spin-orbit coupling and orbital contribution in the system.

  18. A Family of A-Site Cation-Deficient Double-Perovskite-Related Iridates: Ln9Sr2Ir4O24 (Ln = La, Pr, Nd, Sm).

    PubMed

    Ferreira, Timothy; Smith, Mark D; Zur Loye, Hans-Conrad

    2018-06-21

    The compositions of the general formula Ln 11- x Sr x Ir 4 O 24 (Ln = La, Pr, Nd, Sm; 1.37 ≥ x ≥ 2) belonging to a family of A-site cation-deficient double-perovskite-related oxide iridates were grown as highly faceted single crystals from a molten strontium chloride flux. Their structures were determined by single-crystal X-ray diffraction. On the basis of the single-crystal results, additional compositions, Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm), were prepared as polycrystalline powders via solid-state reactions and structurally characterized by Rietveld refinement. The compositions Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm) contain Ir(V) and Ir(IV) in a 1:3 ratio with an average iridium oxidation state of 4.25. The single-crystal compositions La 9.15 Sr 1.85 Ir 4 O 24 and Pr 9.63 Sr 1.37 Ir 4 O 24 contain relatively less Ir(V), with the average iridium oxidation states being 4.21 and 4.09, respectively. The magnetic properties of Ln 9 Sr 2 Ir 4 O 24 (Ln = La, Pr, Nd, Sm) were measured, and complex magnetic behavior was observed in all cases at temperatures below 30 K.

  19. 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 AMX 3, 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 MX 6 octahedra or by simply contracting the lattice isotropically. The former effect tendsmore » 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. 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

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

    SciTech Connect

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

    Tin and lead iodide perovskite semiconductors of the composition AMX 3, 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 MX 6 octahedra or by simply contracting the lattice isotropically. The former effect tendsmore » 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. 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

  1. 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 AMX 3 , 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 MX 6 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.

  2. 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.

  3. Time-Dependent Mechanical Response of APbX 3 (A = Cs, CH 3NH 3; 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 ABX 3, 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. Themore » magnitudes 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

  4. 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)-4 H -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 PC 71 BM, 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 .

  5. 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

    2017-10-09

    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.

  6. 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

  7. Spin State Control of the Perovskite Rh/Co Oxides

    PubMed Central

    Terasaki, Ichiro; Shibasaki, Soichiro; Yoshida, Shin; Kobayashi, Wataru

    2010-01-01

    We show why and how the spin state of transition-metal ions affects the thermoelectric properties of transition-metal oxides by investigating two perovskite-related oxides. In the A-site ordered cobalt oxide Sr3YCo4O10.5, partial substitution of Ca for Sr acts as chemical pressure, which compresses the unit cell volume to drive the spin state crossover, and concomitantly changes the magnetization and thermopower. In the perovskite rhodium oxide LaRhO3, partial substitution of Sr for La acts as hole-doping, and the resistivity and thermopower decrease systematically with the Sr concentration. The thermopower remains large values at high temperatures (>150 μV/K at 800 K), which makes a remarkable contrast to La1−xSrxCoO3. We associate this with the stability of the low spin state of the Rh3+ ions.

  8. 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.

  9. Charge disproportionation of mixed-valent Cr triggered by Bi lone-pair effect in the A -site-ordered perovskite BiC u3C r4O12

    NASA Astrophysics Data System (ADS)

    Etter, Martin; Isobe, Masahiko; Sakurai, Hiroya; Yaresko, Alexander; Dinnebier, Robert E.; Takagi, Hidenori

    2018-05-01

    A new A -site-ordered perovskite BiC u3C r4O12 is synthesized under a high pressure of 7.7 GPa. A phase transition from a paramagnetic metal to a ferrimagnetic metal is observed at Tc=190 K accompanied with a structural change from cubic to monoclinic. Structural analysis of the low-temperature monoclinic phase reveals that this transition represents a charge disproportionation of C r3.75 + into C r4 + and C r3.5 + . We argue that the asymmetric displacement of Bi caused by a lone-pair effect triggers the formation of a dimeric Cr4+2O5 unit and leads to an ordering of C r4 + and C r3.5 + below the transition.

  10. 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.

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

    PubMed

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

    2017-11-20

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

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

    PubMed

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

    2018-04-11

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

  13. 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.

  14. 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

    2017-05-04

    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. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Study of A-site doping of SrBi4Ti4O15 Bi-layered compounds using micro-Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Hao, H.; Liu, H. X.; Cao, M. H.; Min, X. M.; Ouyang, S. X.

    2006-10-01

    The temperature-dependent Raman spectra of Mg- and La-doped SrBi4Ti4O15 (SBT) were studied in the range 40 590 °C. A quantum chemistry calculation was employed to estimate these two substitution states. It was found that A-site doping in this study not only caused multiplicative substitution states, but also the Raman spectra changed with the substitution amount. In a La-doped perovskite-like layer, La would occupy the Bi site when x>0.10 and the 314 and 550 cm-1 modes related to the rotating and tilting of the TiO6 octahedron firstly became wide and then became sharp. With the increase of the substitution amount, both substitution states of Mg-doped SBT lead to the widening of 270 and 520 cm-1 peaks.

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

    NASA Astrophysics Data System (ADS)

    Choquette, Amber K.

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

    The electronic structure of RbTiOPO4 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 KTiOPO4, RbTiOPO4, K0.535R0.465TiOPO4 and TlTiOPO4 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.

  18. 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.

  19. Octahedral tilting instabilities in inorganic halide perovskites

    NASA Astrophysics Data System (ADS)

    Bechtel, Jonathon S.; Van der Ven, Anton

    2018-02-01

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

  20. Exploring the Effects of the Pb2+ 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 MAPbI 3 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 MAPb 1-x Hg x I 3 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.

  1. 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.

  2. Large effects of A-site average cation size on the properties of the double perovskites Ba2-xSrxMnReO6:  A d5-d1 system

    NASA Astrophysics Data System (ADS)

    Popov, Guerman; Greenblatt, Martha; Croft, Mark

    2003-01-01

    Ba2-xSrxMnReO6 (x=0, 0.5, 1, 2) phases with a double-perovskite structure were prepared by solid-state techniques in evacuated sealed silica tubes. Mn2+ and Re6+ are virtually completely ordered on the B sites. The compounds are ferrimagnetic below 120 K. The maximum saturation moment was obtained for a compound with x=0.5 whose tolerance factor is closest to 1. The whole series of compounds, 0.0⩽x⩽2.0, exhibits semiconducting behavior with variable-range hopping type of conduction. Sr2MnReO6 has an unusually high coercive field (2.6 T at 5 K) and two transitions in the M-H loop. Ba2MnReO6 shows large positive magnetoresistance (14% at 80 K, 5 T) below 140 K, while the other compositions studied exhibit negative magnetoresistance in the temperature range measured.

  3. Light-Independent Ionic Transport in Inorganic Perovskite and Ultrastable Cs-Based Perovskite Solar Cells.

    PubMed

    Zhou, Wenke; Zhao, Yicheng; Zhou, Xu; Fu, Rui; Li, Qi; Zhao, Yao; Liu, Kaihui; Yu, Dapeng; Zhao, Qing

    2017-09-07

    Due to light-induced effects in CH 3 NH 3 -based perovskites, such as ion migration, defects formation, and halide segregation, the degradation of CH 3 NH 3 -based perovskite solar cells under maximum power point is generally implicated. Here we demonstrated that the effect of light-enhanced ion migration in CH 3 NH 3 PbI 3 can be eliminated by inorganic Cs substitution, leading to an ultrastable perovskite solar cell. Quantitatively, the ion migration barrier for CH 3 NH 3 PbI 3 is 0.62 eV under dark conditions, larger than that of CsPbI 2 Br (0.45 eV); however, it reduces to 0.07 eV for CH 3 NH 3 PbI 3 under illumination, smaller than that for CsPbI 2 Br (0.43 eV). Meanwhile, photoinduced halide segregation is also suppressed in Cs-based perovskites. Cs-based perovskite solar cells retained >99% of the initial efficiency (10.3%) after 1500 h of maximum power point tracking under AM1.5G illumination, while CH 3 NH 3 PbI 3 solar cells degraded severely after 50 h of operation. Our work reveals an uncovered mechanism for stability improvement by inorganic cation substitution in perovskite-based optoelectronic devices.

  4. 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.

  5. Perovskite-Perovskite Homojunctions via Compositional Doping.

    PubMed

    Dänekamp, Benedikt; Müller, Christian; Sendner, Michael; Boix, Pablo P; Sessolo, Michele; Lovrincic, Robert; Bolink, Henk J

    2018-05-11

    One of the most important properties of semiconductors is the possibility of controlling their electronic behavior via intentional doping. Despite the unprecedented progress in the understanding of hybrid metal halide perovskites, extrinsic doping of perovskite remains nearly unexplored and perovskite-perovskite homojunctions have not been reported. Here we present a perovskite-perovskite homojunction obtained by vacuum deposition of stoichiometrically tuned methylammonium lead iodide (MAPI) films. Doping is realized by adjusting the relative deposition rates of MAI and PbI 2 , obtaining p-type (MAI excess) and n-type (MAI defect) MAPI. The successful stoichiometry change in the thin films is confirmed by infrared spectroscopy, which allows us to determine the MA content in the films. We analyzed the resulting thin-film junction by cross-sectional scanning Kelvin probe microscopy (SKPM) and found a contact potential difference (CPD) of 250 mV between the two differently doped perovskite layers. Planar diodes built with the perovskite-perovskite homojunction show the feasibility of our approach for implementation in devices.

  6. Computational mineral physics and the physical properties of perovskite.

    PubMed

    Brodholt, John P; Oganov, A R; Price, G D

    2002-11-15

    The inherent uncertainties in modern first-principles calculations are reviewed using geophysically relevant examples. The elastic constants of perovskite at lower-mantle temperatures and pressures are calculated using ab initio molecular dynamics. These are used in conjunction with seismic tomographic models to estimate that the lateral temperature contrasts in the Earth's lower mantle are 800 K at a depth of 1000 km, and 1500 K at a depth of 2000 km. The effect of Al(3+) on the compressibility of MgSiO(3) perovskite is calculated using three different pseudopotentials. The results confirm earlier work and show that the compressibility of perovskites with Al(3+) substituted for both Si(4+) and Mg(2+) is very similar to the compressibility of Al(3+)-free perovskite. Even when 100% of the Si(4+) and Mg(2+) ions are replaced with Al(3+), the bulk modulus is only 7% less than that for Al(3+)-free perovskite. In contrast, perovskites where Al(3+) substitutes for Si(4+) only and that are charge balanced by oxygen vacancies do show higher compressibilities. When corrected to similar concentrations of Al(3+), the calculated compressibilities of the oxygen-vacancy-rich perovskites are in agreement with experimental results.

  7. 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.

  8. Hybrid Perovskite/Perovskite Heterojunction Solar Cells.

    PubMed

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

    2016-06-28

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

  9. Effect of La3+ substitution with Gd3+ on the resistive switching properties of La0.7Sr0.3MnO3 thin films

    NASA Astrophysics Data System (ADS)

    Lee, Hong-Sub; Park, Chang-Sun; Park, Hyung-Ho

    2014-05-01

    This study demonstrated that the resistive switching voltage of perovskite manganite material could be controlled by A-site cation substitution in "A" MnO3 perovskite manganite structure. A partial substitution of La3+ in La0.7Sr0.3MnO3 with smaller cation Gd3+ induced A-site vacancy of the largest Sr2+ cation with surface segregation of SrOy due to ionic size mismatch, and the induced vacancies reduced migration energy barrier. The operating voltage decreased from 3.5 V to 2.5 V due to a favorable condition for electrochemical migration and redox of oxygen ions. Moreover, surface-segregated SrOy was enhanced with Gd-substitution and the SrOy reduced Schottky-like barrier height and resistive switching ratio from the potential drop and screening effect. The relationship between A-site vacancy generation resulting in surface segregation of SrOy and resistive switching behavior was also investigated by energy resolved x-ray photoelectron spectroscopy, O 1s near edge x-ray absorption spectroscopy, and current voltage measurement.

  10. 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.

  11. 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

  12. Perovskite-type catalytic materials for environmental applications.

    PubMed

    Labhasetwar, Nitin; Saravanan, Govindachetty; Kumar Megarajan, Suresh; 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, N 2 O 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.

  13. Dynamic Optoelectronic Properties in Perovskite Oxide Thin Films Measured with Ultrafast Transient Absorption & Reflectance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Smolin, Sergey Y.

    -dependent, variable-angle spectroscopic ellipsometry and time-resolved ultrafast optical spectroscopy on a type I heterostructure, we clarify thermal and electronic contributions to spectral transients in LaFeO3. Upon comparison to thermally-derived static spectra of LaFeO3, we find that thermal contributions dominate the transient absorption and reflectance spectra above the band gap. A transient photoinduced absorption feature below the band gap at 1.9 eV is not reproduced in the thermally derived spectra and has significantly longer decay kinetics from the thermallyinduced features; therefore, this long lived photoinduced absorption is likely derived, at least partially, from photoexcited carriers with lifetimes much longer than 3 nanoseconds. LaFeO3 has a wide band gap of 2.4 eV but its absorption can be decreased with chemical substitution of Sr for Fe to make it more suitable for various applications. This type of A-site substitution is a common route to change static optical absorption in perovskite oxides, but there are no systematic studies looking at how A-site substitution changes dynamic optoelectronic properties. To understand the relationship between composition and static and dynamic optical properties we worked with the model system of La1-xSrxFeO 3-delta epitaxial films grown on LSAT, 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 with broadband visible (1.6 eV to 4 eV) and near-infrared (0.9 eV to 1.5 eV) probes. The sign of the reflectance

  14. Sugar Substitutes

    MedlinePlus

    ... Substitutes Share Print Sugar substitutes are chemical or plant-based substances used to sweeten or enhance the ... made with saccharin. Stevia sweeteners Stevia is a plant-based sugar substitute that has no calories. The ...

  15. 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.

  16. 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

  17. 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.

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

    SciTech Connect

    Khaliq, Jibran; Chen, Kan; Li, Chunchun

    2015-02-21

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

  19. Advancement on Lead-Free Organic-Inorganic Halide Perovskite Solar Cells: A Review.

    PubMed

    Sani, Faruk; Shafie, Suhaidi; Lim, Hong Ngee; Musa, Abubakar Ohinoyi

    2018-06-14

    Remarkable attention has been committed to the recently discovered cost effective and solution processable lead-free organic-inorganic halide perovskite solar cells. Recent studies have reported that, within five years, the reported efficiency has reached 9.0%, which makes them an extremely promising and fast developing candidate to compete with conventional lead-based perovskite solar cells. The major challenge associated with the conventional perovskite solar cells is the toxic nature of lead (Pb) used in the active layer of perovskite material. If lead continues to be used in fabricating solar cells, negative health impacts will result in the environment due to the toxicity of lead. Alternatively, lead free perovskite solar cells could give a safe way by substituting low-cost, abundant and non toxic material. This review focuses on formability of lead-free organic-inorganic halide perovskite, alternative metal cations candidates to replace lead (Pb), and possible substitutions of organic cations, as well as halide anions in the lead-free organic-inorganic halide perovskite architecture. Furthermore, the review gives highlights on the impact of organic cations, metal cations and inorganic anions on stability and the overall performance of lead free perovskite solar cells.

  20. Perovskites keep on giving

    NASA Astrophysics Data System (ADS)

    2018-05-01

    Whether you like exploring the mysteries of light-matter interactions, playing with a versatile chemical platform, or developing the most efficient devices, metal halide perovskites could be the materials for you.

  1. 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.

  2. Entropy in halide perovskites

    NASA Astrophysics Data System (ADS)

    Katan, Claudine; Mohite, Aditya D.; Even, Jacky

    2018-05-01

    Claudine Katan, Aditya D. Mohite and Jacky Even discuss the possible impact of various entropy contributions (stochastic structural fluctuations, anharmonicity and lattice softness) on the optoelectronic properties of halide perovskite materials and devices.

  3. Role of A-site Ca and B-site Zr substitution in BaTiO3 lead-free compounds: Combined experimental and first principles density functional theoretical studies

    NASA Astrophysics Data System (ADS)

    Keswani, Bhavna C.; Saraf, Deepashri; Patil, S. I.; Kshirsagar, Anjali; James, A. R.; Kolekar, Y. D.; Ramana, C. V.

    2018-05-01

    We report on the combined experimental and theoretical simulation results of lead-free ferroelectrics, Ba(1-x)CaxTiO3 (x = 0.0-0.3) and BaTi(1-y)ZryO3 (y = 0.0-0.2), synthesized by standard solid state reaction method. First principles density functional calculations are used to investigate the electronic structure, dynamical charges, and spontaneous polarization of these compounds. In addition, the structural, ferroelectric, piezoelectric, and dielectric properties are studied using extensive experiments. The X-ray diffraction and temperature dependent Raman spectroscopy studies indicate that the calcium (Ca) substituted compositions exhibit a single phase crystal structure, while zirconium (Zr) substituted compositions are biphasic. The scanning electron micrographs reveal the uniform and highly dense microstructure. The presence of polarization-electric field and strain-electric field hysteresis loops confirms the ferroelectric and piezoelectric nature of all the compositions. Our results demonstrate higher values for polarization, percentage strain, piezoelectric coefficients, and electrostrictive coefficient compared to those existing in the literature. For smaller substitutions of Ca and Zr in BaTiO3, a direct piezoelectric coefficient (d33) is enhanced, while the highest d33 value (˜300 pC/N) is observed for BaTi0.96Zr0.04O3 due to the biphasic ferroelectric behavior. Calculation of Born effective charges indicates that doping with Ca or Zr increases the dynamical charges on Ti as well as on O and decreases the dynamical charge on Ba. An increase in the dynamical charges on Ti and O is ascribed to the increase in covalency of Ti-O bond that reduces the polarizability of the crystal. A broader range of temperatures is demonstrated to realize the stable phase in the Ca substituted compounds. The results indicate enhancement in the temperature range of applicability of these compounds for device applications. The combined theoretical and experimental study is

  4. What makes the difference in perovskite titanates?

    NASA Astrophysics Data System (ADS)

    Bussmann-Holder, Annette; Roleder, Krystian; Ko, Jae-Hyeon

    2018-06-01

    We have investigated in detail the lattice dynamics of five different perovskite titanates ATiO3 (A = Ca, Sr, Ba, Pb, Eu) where the A sites are occupied by +2 ions. In spite of the largely ionic character of these ions, the properties of these compounds differ substantially. They range from order/disorder like, to displacive ferroelectric, quantum paraelectric, and antiferromagnetic. All compounds crystallize in the cubic structure at high temperature and undergo structural phase transitions to tetragonal symmetry, partly followed by further transitions to lower symmetries. Since the TiO6 moiety is the essential electronic and structural unit, the question arises, what makes the significant difference between them. It is shown that the lattice dynamics of these compounds are very different, and that mode-mode coupling effects give rise to many distinct properties. In addition, the oxygen ion nonlinear polarizability plays a key role since it dominates the anharmonicity of these perovskites and determines the structural instability.

  5. Perovskite photonic sources

    NASA Astrophysics Data System (ADS)

    Sutherland, Brandon R.; Sargent, Edward H.

    2016-05-01

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

  6. Electrical and magnetic properties of La0.67Ba0.33Mn1- x (Me) x O3 perovskite manganites: case of manganese substituted by trivalent (Me = Cr) and tetravalent (Me = Ti) elements

    NASA Astrophysics Data System (ADS)

    Oumezzine, Marwène; Peña, Octavio; Kallel, Sami; Kallel, Nabil; Guizouarn, Thierry; Gouttefangeas, Francis; Oumezzine, Mohamed

    2014-03-01

    The effects of non-magnetic Ti4+ substitution on the structural, electrical and magnetic properties of La0.67Ba0.33Mn1- x Ti x O3 (0≤ x≤0.1) are investigated and compared to those existing in La0.67Ba0.33Mn1- x Cr x O3 (magnetic Cr3+). The structural refinement by the Rietveld method revealed that Ti-doped samples crystallize in the cubic lattice with space group , while samples with Cr crystallize in the hexagonal setting of the rhombohedral space group for identical contents of dopant. The most relevant structural features are an increase of the lattice parameters, of the cell volume and of the inter-ionic distances with increasing Ti doping level. Both series of samples show a decrease of the paramagnetic-ferromagnetic transition temperature when the amount of chromium or titanium increases. Transport measurements show that when increasing the metal doping, the resistivity increases whereas the metallic behavior of the parent compound La0.67Ba0.33MnO3 is destroyed. For a substitution higher than 5 at.% of Ti and 10 at.% of Cr, the samples exhibit a semiconducting behavior in the whole range of temperature, for which the electronic transport can be explained by variable range hopping and/or small polaron hopping models.

  7. Cu-In Halide Perovskite Solar Absorbers.

    PubMed

    Zhao, Xin-Gang; Yang, Dongwen; Sun, Yuanhui; Li, Tianshu; Zhang, Lijun; Yu, Liping; Zunger, Alex

    2017-05-17

    The long-term chemical instability and the presence of toxic Pb in otherwise stellar solar absorber APbX 3 made of organic molecules on the A site and halogens for X have hindered their large-scale commercialization. Previously explored ways to achieve Pb-free halide perovskites involved replacing Pb 2+ with other similar M 2+ cations in ns 2 electron configuration, e.g., Sn 2+ or by Bi 3+ (plus Ag + ), but unfortunately this showed either poor stability (M = Sn) or weakly absorbing oversized indirect gaps (M = Bi), prompting concerns that perhaps stability and good optoelectronic properties might be contraindicated. Herein, we exploit the electronic structure underpinning of classic Cu[In,Ga]Se 2 (CIGS) chalcopyrite solar absorbers to design Pb-free halide perovskites by transmuting 2Pb to the pair [B IB + C III ] such as [Cu + Ga] or [Ag + In] and combinations thereof. The resulting group of double perovskites with formula A 2 BCX 6 (A = K, Rb, Cs; B = Cu, Ag; C = Ga, In; X = Cl, Br, I) benefits from the ionic, yet narrow-gap character of halide perovskites, and at the same time borrows the advantage of the strong Cu(d)/Se(p) → Ga/In(s/p) valence-to-conduction-band absorption spectra known from CIGS. This constitutes a new group of CuIn-based Halide Perovskite (CIHP). Our first-principles calculations guided by such design principles indicate that the CIHPs class has members with clear thermodynamic stability, showing direct band gaps, and manifesting a wide-range of tunable gap values (from zero to about 2.5 eV) and combination of light electron and heavy-light hole effective masses. Materials screening of candidate CIHPs then identifies the best-of-class Rb 2 [CuIn]Cl 6 , Rb 2 [AgIn]Br 6 , and Cs 2 [AgIn]Br 6 , having direct band gaps of 1.36, 1.46, and 1.50 eV, and theoretical spectroscopic limited maximal efficiency comparable to chalcopyrites and CH 3 NH 3 PbI 3 . Our finding offers a new routine for designing new-type Pb-free halide perovskite solar

  8. 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.

  9. 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

  10. Effect of aluminium on the compressibility of silicate perovskite

    NASA Astrophysics Data System (ADS)

    Daniel, Isabelle; Bass, Jay D.; Fiquet, Guillaume; Cardon, Hervé; Zhang, Jianzhong; Hanfland, Michael

    2004-08-01

    Volume measurements for aluminous MgSiO3 perovskite containing 5 mol% Al2O3 were carried out up to pressures of 40 GPa at ambient temperature, using monochromatic synchrotron X-ray diffraction. A least-squares refinement of the data to the Birch-Murnaghan equation of state yields the following parameters V0 = 163.234(8) Å3, KT0 = 251.5(13) GPa, K'0 = 4. Within uncertainties, the presence of 5 mol% Al2O3 in MgSiO3 perovskite induces a decrease of the bulk modulus in the range of 0% to 1.8%. Thus, KT of perovskite is affected little if at all by the presence of Al3+. This result is in excellent agreement with the values deduced from sound velocity measurements on the same sample [Jackson et al., 2004]. We discuss the possible origin of discrepancies among the different bulk moduli reported to date for aluminous perovskite. In light of recent calculations, our results are consistent with aluminium being dissolved in MgSiO3 perovskite through a coupled substitution mechanism involving the replacement of both Mg2+ and Si4+ in the dodecahedral and octahedral sites by 2 Al3+. Moreover, any slight reduction in the bulk modulus of MgSiO3 perovskite induced by the dissolution of 5 mol% Al2O3, indicates that the relative proportions of the minerals characteristic of the lower mantle, as inferred from seismological models, should not be significantly altered by the introduction of Al in the system.

  11. 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.

  12. Blood substitutes.

    PubMed Central

    Kostrzewska, E.

    1976-01-01

    With the development of modern methods of surgery, anaesthesia, and pre- and postoperative care the requirement for blood substitutes is continuously increasing. We present a review of the different blood substitutes which are already in clinical use or in an advanced stage of experimental investigation for possible practical administration. Our own clinical experience with dextrans and experimental studies on stroma-free haemoglobin and hydroxyethyl starch solutions are described. PMID:57736

  13. 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

  14. Tailoring perovskite compounds for broadband light absorption

    NASA Astrophysics Data System (ADS)

    Lu, Hengchang; Guo, Xiaowei; Yang, Cheng; Li, Shaorong

    2018-01-01

    Perovskite solar cells have experienced an outstanding advance in power conversion efficiency (PCE) by optimizing the perovskite layer morphology, composition, interfaces, and charge collection efficiency. To enhance PCE, the mixed perovskites were proposed in recent years. In this study, optoelectronic performance of pure perovskites and mixed ones were investigated. It was demonstrated that the mixed perovskites exhibit superior to the pure ones. The mixed material can absorb broadband light absorption and result in increased short circuit current density and power conversion efficiency.

  15. Curtailing Perovskite Processing Limitations via Lamination at the Perovskite/Perovskite Interface

    SciTech Connect

    Van Hest, Marinus F; Moore, David; Klein, Talysa

    Standard layer-by-layer solution processing methods constrain lead-halide perovskite device architectures. The layer below the perovskite must be robust to the strong organic solvents used to form the perovskite while the layer above has a limited thermal budget and must be processed in nonpolar solvents to prevent perovskite degradation. To circumvent these limitations, we developed a procedure where two transparent conductive oxide/transport material/perovskite half stacks are independently fabricated and then laminated together at the perovskite/perovskite interface. Using ultraviolet-visible absorption spectroscopy, external quantum efficiency, X-ray diffraction, and time-resolved photoluminesence spectroscopy, we show that this procedure improves photovoltaic properties of the perovskite layer.more » Applying this procedure, semitransparent devices employing two high-temperature oxide transport layers were fabricated, which realized an average efficiency of 9.6% (maximum: 10.6%) despite series resistance limitations from the substrate design. Overall, the developed lamination procedure curtails processing constraints, enables new device designs, and affords new opportunities for optimization.« less

  16. 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

  17. Glory of piezoelectric perovskites.

    PubMed

    Uchino, Kenji

    2015-08-01

    This article reviews the history of piezoelectric perovskites and forecasts future development trends, including Uchino's discoveries such as the Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 electrostrictor, Pb(Zn 1/3 Nb 2/3 )O 3 -PbTiO 3 single crystal, (Pb, La)(Zr, Ti)O 3 photostriction, and Pb(Zr, Ti)O 3 -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.

  18. 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

  19. 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 AMX 3 (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, APbX 3 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.

  20. Colossal change in thermopower with temperature-driven p-n-type conduction switching in La x Sr2-x TiFeO6 double perovskites

    NASA Astrophysics Data System (ADS)

    Roy, Pinku; Maiti, Tanmoy

    2018-02-01

    Double perovskite materials have been studied in detail by many researchers, as their magnetic and electronic properties can be controlled by the substitution of alkaline earth metals or lanthanides in the A site and transition metals in the B site. Here we report the temperature-driven, p-n-type conduction switching assisted, large change in thermopower in La3+-doped Sr2TiFeO6-based double perovskites. Stoichiometric compositions of La x Sr2-x TiFeO6 (LSTF) with 0  ⩽  x  ⩽  0.25 were synthesized by the solid-state reaction method. Rietveld refinement of room-temperature XRD data confirmed a single-phase solid solution with cubic crystal structure and Pm\\bar{3}m space group. From temperature-dependent electrical conductivity and Seebeck coefficient (S) studies it is evident that all the compositions underwent an intermediate semiconductor-to-metal transition before the semiconductor phase reappeared at higher temperature. In the process of semiconductor-metal-semiconductor transition, LSTF compositions demonstrated temperature-driven p-n-type conduction switching behavior. The electronic restructuring which occurs due to the intermediate metallic phase between semiconductor phases leads to the colossal change in S for LSTF oxides. The maximum drop in thermopower (ΔS ~ 2516 µV K-1) was observed for LSTF with x  =  0.1 composition. Owing to their enormous change in thermopower of the order of millivolts per kelvin, integrated with p-n-type resistance switching, these double perovskites can be used for various high-temperature multifunctional device applications such as diodes, sensors, switches, thermistors, thyristors, thermal runaway monitors etc. Furthermore, the conduction mechanisms of these oxides were explained by the small polaron hopping model.

  1. 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

    2016-09-28

    Owing to its ideal semiconducting band gap and good carrier transport properties, the fully inorganic perovskite CsSnI 3 has been proposed as a visible-light absorber for photovoltaic (PV) applications. However, compared to the organic inorganic lead halide perovskite CH 3NH 3PbI 3, CsSnI 3 solar cells display very low energy conversion efficiency. In this work, we propose a potential route to improve the PV properties of CsSnI 3. Using first-principles calculations, we examine the crystal structures and electronic properties of CsSnI 3, including its structural polymorphs. Next, we purposefully order Cs and Rb cations on the A site to createmore » the double perovskite (CsRb)Sn 2I 6. We find that a stable ferroelectric polarization arises from the nontrivial coupling between polar displacements and octahedral rotations of the SnI 6 network. These ferroelectric double perovskites are predicted to have energy band gaps and carrier effective masses similar to those of CsSnI 3. More importantly, unlike nonpolar CsSnI 3, the electric polarization present in ferroelectric (CsRb)Sn 2I 6 can effectively separate the photoexcited carriers, leading to novel ferroelectric PV materials with,potentially enhanced energy conversion efficiency.« less

  2. Enhancement of redox- and phase-stability of thermoelectric CaMnO3-δ by substitution

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    Redox Reactivity and structural phase transitions have a major impact on transport and me-chemical properties of thermoelectric CaMnO3-δ. In this study series of Ca1-xAxMn1-yByO3-δ (0≤x,y≤0.8) compounds, each with A-site (Dy3+, Yb3+) or B-site (Nb5+, Ta5+ and Mo6+, W6+) 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.

  3. Perovskites in catalysis and electrocatalysis.

    PubMed

    Hwang, Jonathan; Rao, Reshma R; Giordano, Livia; Katayama, Yu; Yu, Yang; Shao-Horn, Yang

    2017-11-10

    Catalysts for chemical and electrochemical reactions underpin many aspects of modern technology and industry, from energy storage and conversion to toxic emissions abatement to chemical and materials synthesis. This role necessitates the design of highly active, stable, yet earth-abundant heterogeneous catalysts. In this Review, we present the perovskite oxide family as a basis for developing such catalysts for (electro)chemical conversions spanning carbon, nitrogen, and oxygen chemistries. A framework for rationalizing activity trends and guiding perovskite oxide catalyst design is described, followed by illustrations of how a robust understanding of perovskite electronic structure provides fundamental insights into activity, stability, and mechanism in oxygen electrocatalysis. We conclude by outlining how these insights open experimental and computational opportunities to expand the compositional and chemical reaction space for next-generation perovskite catalysts. Copyright © 2017, American Association for the Advancement of Science.

  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. Perovskites in catalysis and electrocatalysis

    NASA Astrophysics Data System (ADS)

    Hwang, Jonathan; Rao, Reshma R.; Giordano, Livia; Katayama, Yu; Yu, Yang; Shao-Horn, Yang

    2017-11-01

    Catalysts for chemical and electrochemical reactions underpin many aspects of modern technology and industry, from energy storage and conversion to toxic emissions abatement to chemical and materials synthesis. This role necessitates the design of highly active, stable, yet earth-abundant heterogeneous catalysts. In this Review, we present the perovskite oxide family as a basis for developing such catalysts for (electro)chemical conversions spanning carbon, nitrogen, and oxygen chemistries. A framework for rationalizing activity trends and guiding perovskite oxide catalyst design is described, followed by illustrations of how a robust understanding of perovskite electronic structure provides fundamental insights into activity, stability, and mechanism in oxygen electrocatalysis. We conclude by outlining how these insights open experimental and computational opportunities to expand the compositional and chemical reaction space for next-generation perovskite catalysts.

  6. 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.

  7. Perovskite Solar Cells | Photovoltaic Research | NREL

    Science.gov Websites

    & Devices pages: High-Efficiency Crystalline PV Polycrystalline Thin-Film PV Perovskite and Organic -Defect Hybrid Organic/Inorganic Perovskite Films as PV Absorbers. (FY 2015FY 2016). In collaboration with organic metal halide perovskite (see article). Ultrahigh-Efficiency and Low-Cost Polycrystalline Halide

  8. Perovskite and Organic Photovoltaics | Photovoltaic Research | NREL

    Science.gov Websites

    Perovskite and Organic Photovoltaics Perovskite and Organic Photovoltaics Scientist holds several solar cells; 2) electronic energy level alignment at the carbon nanotube/organic metal halide perovskite Hest in the PDIL in the S and TF at NREL. Organic Photovoltaics (OPV) We develop and apply new absorber

  9. 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.

  10. 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.

  11. Pure white-light emitting ultrasmall organic-inorganic hybrid perovskite nanoclusters.

    PubMed

    Teunis, Meghan B; Lawrence, Katie N; Dutta, Poulami; Siegel, Amanda P; Sardar, Rajesh

    2016-10-14

    Organic-inorganic hybrid perovskites, direct band-gap semiconductors, have shown tremendous promise for optoelectronic device fabrication. We report the first colloidal synthetic approach to prepare ultrasmall (∼1.5 nm diameter), white-light emitting, organic-inorganic hybrid perovskite nanoclusters. The nearly pure white-light emitting ultrasmall nanoclusters were obtained by selectively manipulating the surface chemistry (passivating ligands and surface trap-states) and controlled substitution of halide ions. The nanoclusters displayed a combination of band-edge and broadband photoluminescence properties, covering a major part of the visible region of the solar spectrum with unprecedentedly large quantum yields of ∼12% and photoluminescence lifetime of ∼20 ns. The intrinsic white-light emission of perovskite nanoclusters makes them ideal and low cost hybrid nanomaterials for solid-state lighting applications.

  12. Calcium doped MAPbI3 with better energy state alignment in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Lu, Chaojie; Zhang, Jing; Hou, Dagang; Gan, Xinlei; Sun, Hongrui; Zeng, Zhaobing; Chen, Renjie; Tian, Hui; Xiong, Qi; Zhang, Ying; Li, Yuanyuan; Zhu, Yuejin

    2018-05-01

    The organic-inorganic perovskite material with better energy alignment in the solar cell device will have a profound impact on the solar cell performance. It is valuable to tune the energy states by element substitution and doping in perovskites. Here, we present that Ca2+ is incorporated into CH3NH3PbI3, which up-shifts the valence band maximum and the conduction band minimum, leading to a difference between the bandgap and the Fermi level in the device. Consequently, Ca2+ incorporation results in an enhancement of the photovoltage and photocurrent, achieving a summit efficiency of 18.3% under standard 1 sun (AM 1.5). This work reveals the doped perovskite to improve the solar cell performance by tuning the energy state.

  13. Graded bandgap perovskite solar cells.

    PubMed

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

    2017-05-01

    Organic-inorganic halide perovskite materials have emerged as attractive alternatives to conventional solar cell building blocks. Their high light absorption coefficients and long diffusion lengths suggest high power conversion efficiencies, and indeed perovskite-based single bandgap and tandem solar cell designs have yielded impressive performances. One approach to further enhance solar spectrum utilization is the graded bandgap, but this has not been previously achieved for perovskites. In this study, we demonstrate graded bandgap perovskite solar cells with steady-state conversion efficiencies averaging 18.4%, with a best of 21.7%, all without reflective coatings. An analysis of the experimental data yields high fill factors of ∼75% and high short-circuit current densities up to 42.1 mA cm -2 . The cells are based on an architecture of two perovskite layers (CH 3 NH 3 SnI 3 and CH 3 NH 3 PbI 3-x Br x ), incorporating GaN, monolayer hexagonal boron nitride, and graphene aerogel.

  14. White perovskite based lighting devices.

    PubMed

    Bidikoudi, M; Fresta, E; Costa, R D

    2018-06-28

    Hybrid organic-inorganic and all-inorganic metal halide perovskites have been one of the most intensively studied materials during the last few years. In particular, research focusing on understanding how to tune the photoluminescence features and to apply perovskites to optoelectronic applications has led to a myriad of new materials featuring high photoluminescence quantum yields covering the whole visible range, as well as devices with remarkable performances. Having already established their successful incorporation in highly efficient solar cells, the next step is to tackle the challenges in solid-state lighting (SSL) devices. Here, the most prominent is the preparation of white-emitting devices. Herein, we have provided a comprehensive view of the route towards perovskite white lighting devices, including thin film light-emitting diodes (PeLEDs) and hybrid LEDs (HLEDs), using perovskite based color down-converting coatings. While synthesis and photoluminescence features are briefly discussed, we focus on highlighting the major achievements and limitations in white devices. Overall, we expect that this review will provide the reader a general overview of the current state of perovskite white SSL, paving the way towards new breakthroughs in the near future.

  15. Crystal structure and thermoelectric properties of Sr-Mo substituted CaMnO3: a combined experimental and computational study.

    PubMed

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

    2015-12-21

    A combination of experimental and computational techniques has been employed to study doping effects in perovskite CaMnO 3 . High quality Sr-Mo co-substituted CaMnO 3 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 CaMnO 3 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 Mn 3+ in the Mn 4+ 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. Ca 0.7 Sr 0.3 Mn 0.96 Mo 0.04 O 3 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

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

  17. Hybrid Organic-Inorganic Perovskite Photodetectors.

    PubMed

    Tian, Wei; Zhou, Huanping; Li, Liang

    2017-11-01

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

  18. High Photoluminescence Quantum Yields in Organic Semiconductor-Perovskite Composite Thin Films.

    PubMed

    Longo, Giulia; La-Placa, Maria-Grazia; Sessolo, Michele; Bolink, Henk J

    2017-10-09

    One of the obstacles towards efficient radiative recombination in hybrid perovskites is a low exciton binding energy, typically in the orders of tens of meV. It has been shown that the use of electron-donor additives can lead to a substantial reduction of the non-radiative recombination in perovskite films. Herein, the approach using small molecules with semiconducting properties, which are candidates to be implemented in future optoelectronic devices, is presented. In particular, highly luminescent perovskite-organic semiconductor composite thin films have been developed, which can be processed from solution in a simple coating step. By tuning the relative concentration of methylammonium lead bromide (MAPbBr 3 ) and 9,9spirobifluoren-2-yl-diphenyl-phosphine oxide (SPPO1), it is possible to achieve photoluminescent quantum yields (PLQYs) as high as 85 %. This is attributed to the dual functions of SPPO1 that limit the grain growth while passivating the perovskite surface. The electroluminescence of these materials was investigated by fabricating multilayer LEDs, where charge injection and transport was found to be severely hindered for the perovskite/SPPO1 material. This was alleviated by partially substituting SPPO1 with a hole-transporting material, 1,3-bis(N-carbazolyl)benzene (mCP), leading to bright electroluminescence. The potential of combining perovskite and organic semiconductors to prepare materials with improved properties opens new avenues for the preparation of simple lightemitting devices using perovskites as the emitter. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Oxygen-induced defects at the lead halide perovskite/graphene oxide interfaces

    DOE PAGES

    Acik, Muge; Park, In Kee; Koritala, Rachel E.; ...

    2017-12-21

    Here, graphene oxide or its reduced derivative (GO/RGO) replace metal oxides in perovskite photovoltaics to achieve energy band alignment for minimization of the energy barriers at the film interfaces allowing efficient charge transport, and eliminate stability issues. However, the power conversion efficiencies fall in a wide range (~0.6–18%). Therefore, the perovskite growth and nucleation on GO/RGO require fundamental understanding to improve device function for controlled fabrication, which remain a major challenge. We analyze the surface morphology and crystallization of the lead halide perovskites (MAPbX 3) at 20–300 °C on GO using X-ray diffraction and photoelectron spectroscopy. To determine defect mechanismsmore » and their composition, we perform in situ transmission infrared and micro Raman spectroscopy, and the cross-sectional scanning microscopy that captures interfacial imperfections with the oxygen defects. We demonstrate the oxygen-induced defects at the MAPbX 3/GO interfaces that initiate at room temperature, and occur through the nucleophilic substitution reactions. Unexpectedly, structural defects nucleate in GO forming chemically reduced GO, and modify the surface morphology that yield a poor perovskite growth. Our theoretical studies also reveal that energetically favorable, exothermic reactions between the halides of the perovskite precursors and the oxygen groups of GO generate acidic reaction by-products ( i.e. HX), that confirm the formation of oxygen-induced defects.« less

  20. Oxygen-induced defects at the lead halide perovskite/graphene oxide interfaces

    SciTech Connect

    Acik, Muge; Park, In Kee; Koritala, Rachel E.

    Here, graphene oxide or its reduced derivative (GO/RGO) replace metal oxides in perovskite photovoltaics to achieve energy band alignment for minimization of the energy barriers at the film interfaces allowing efficient charge transport, and eliminate stability issues. However, the power conversion efficiencies fall in a wide range (~0.6–18%). Therefore, the perovskite growth and nucleation on GO/RGO require fundamental understanding to improve device function for controlled fabrication, which remain a major challenge. We analyze the surface morphology and crystallization of the lead halide perovskites (MAPbX 3) at 20–300 °C on GO using X-ray diffraction and photoelectron spectroscopy. To determine defect mechanismsmore » and their composition, we perform in situ transmission infrared and micro Raman spectroscopy, and the cross-sectional scanning microscopy that captures interfacial imperfections with the oxygen defects. We demonstrate the oxygen-induced defects at the MAPbX 3/GO interfaces that initiate at room temperature, and occur through the nucleophilic substitution reactions. Unexpectedly, structural defects nucleate in GO forming chemically reduced GO, and modify the surface morphology that yield a poor perovskite growth. Our theoretical studies also reveal that energetically favorable, exothermic reactions between the halides of the perovskite precursors and the oxygen groups of GO generate acidic reaction by-products ( i.e. HX), that confirm the formation of oxygen-induced defects.« less

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  2. Lead-free Halide Perovskites via Functionality-directed Materials Screening

    NASA Astrophysics Data System (ADS)

    Zhang, Lijun; Yang, Dongwen; Lv, Jian; Zhao, Xingang; Yang, Ji-Hui; Yu, Liping; Wei, Su-Huai; Zunger, Alex

    Hybrid organic-inorganic halide perovskites with the prototype material of CH3NH3PbI3 have recently attracted much interest as low-cost and high-performance photovoltaic absorbers but one would like to improve their stability and get rid of toxic Pb. We used photovoltaic-functionality-directed materials screening approach to rationally design via first-principles DFT calculations Pb-free halide perovskites. Screening criteria involve thermodynamic and crystallographic stability, as well as solar band gaps, light carrier effective masses, exciton binding, etc. We considered both single atomic substitutions in AMX3 normal perovskites (altering chemical constituents of A, M and X individually) as well as double substitution of 2M into B+C in A2BCX6 double-perovskites. Chemical trends in phase stabilities and optoelectronic properties are discussed with some promising cases exhibiting solar cell efficiencies comparable to that of CH3NH3PbI3. L.Z. founded by Recruitment Program of Global Youth Experts and National Key Research and Development Program of China, and A.Z. by DOE EERE Sun Shot of USA.

  3. Exploration of Near-Infrared-Emissive Colloidal Multinary Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform.

    PubMed

    Lignos, Ioannis; Morad, Viktoriia; Shynkarenko, Yevhen; Bernasconi, Caterina; Maceiczyk, Richard M; Protesescu, Loredana; Bertolotti, Federica; Kumar, Sudhir; Ochsenbein, Stefan T; Masciocchi, Norberto; Guagliardi, Antonietta; Shih, Chih-Jen; Bodnarchuk, Maryna I; deMello, Andrew J; Kovalenko, Maksym V

    2018-05-22

    Hybrid organic-inorganic and fully inorganic lead halide perovskite nanocrystals (NCs) have recently emerged as versatile solution-processable light-emitting and light-harvesting optoelectronic materials. A particularly difficult challenge lies in warranting the practical utility of such semiconductor NCs in the red and infrared spectral regions. In this context, all three archetypal A-site monocationic perovskites-CH 3 NH 3 PbI 3 , CH(NH 2 ) 2 PbI 3 , and CsPbI 3 -suffer from either chemical or thermodynamic instabilities in their bulk form. A promising approach toward the mitigation of these challenges lies in the formation of multinary compositions (mixed cation and mixed anion). In the case of multinary colloidal NCs, such as quinary Cs x FA 1- x Pb(Br 1- y I y ) 3 NCs, the outcome of the synthesis is defined by a complex interplay between the bulk thermodynamics of the solid solutions, crystal surface energies, energetics, dynamics of capping ligands, and the multiple effects of the reagents in solution. Accordingly, the rational synthesis of such NCs is a formidable challenge. Herein, we show that droplet-based microfluidics can successfully tackle this problem and synthesize Cs x FA 1- x PbI 3 and Cs x FA 1- x Pb(Br 1- y I y ) 3 NCs in both a time- and cost-efficient manner. Rapid in situ photoluminescence and absorption measurements allow for thorough parametric screening, thereby permitting precise optical engineering of these NCs. In this showcase study, we fine-tune the photoluminescence maxima of such multinary NCs between 700 and 800 nm, minimize their emission line widths (to below 40 nm), and maximize their photoluminescence quantum efficiencies (up to 89%) and phase/chemical stabilities. Detailed structural analysis revealed that the Cs x FA 1- x Pb(Br 1- y I y ) 3 NCs adopt a cubic perovskite structure of FAPbI 3 , with iodide anions partially substituted by bromide ions. Most importantly, we demonstrate the excellent transference of reaction

  4. “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., E-mail: michael.hayward@chem.ox.ac.uk

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

  5. 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.

  6. Monolithic Perovskite Silicon Tandem Solar Cells with Advanced Optics

    SciTech Connect

    Goldschmidt, Jan C.; Bett, Alexander J.; Bivour, 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.

  7. Cation ordering and effect of biaxial strain in double perovskite CsRbCaZnCl 6

    DOE PAGES

    Pilania, G.; Uberuaga, B. P.

    2015-03-19

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

  8. Thermochromic halide perovskite solar cells.

    PubMed

    Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A; Xie, Chenlu; Cui, Fan; Alivisatos, A Paul; Limmer, David T; Yang, Peidong

    2018-03-01

    Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

  9. Thermochromic halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Lin, Jia; Lai, Minliang; Dou, Letian; Kley, Christopher S.; Chen, Hong; Peng, Fei; Sun, Junliang; Lu, Dylan; Hawks, Steven A.; Xie, Chenlu; Cui, Fan; Alivisatos, A. Paul; Limmer, David T.; Yang, Peidong

    2018-03-01

    Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.

  10. 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.

  11. 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.

  12. Biexciton Auger Recombination Differs in Hybrid and Inorganic Halide Perovskite Quantum Dots.

    PubMed

    Eperon, Giles E; Jedlicka, Erin; Ginger, David S

    2018-01-04

    We use time-resolved photoluminescence measurements to determine the biexciton Auger recombination rate in both hybrid organic-inorganic and fully inorganic halide perovskite nanocrystals as a function of nanocrystal volume. We find that the volume scaling of the biexciton Auger rate in the hybrid perovskites, containing a polar organic A-site cation, is significantly shallower than in the fully inorganic Cs-based nanocrystals. As the nanocrystals become smaller, the Auger rate in the hybrid nanocrystals increases even less than expected, compared to the fully inorganic nanocrystals, which already show a shallower volume dependence than other material systems such as chalcogenide quantum dots. This finding suggests there may be differences in the strength of Coulombic interactions between the fully inorganic and hybrid perovskites, which may prove to be crucial in selecting materials to obtain the highest performing devices in the future, and hints that there could be something "special" about the hybrid materials.

  13. 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

  14. 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.

  15. Highly efficient and stable inverted perovskite solar cell employing PEDOT:GO composite layer as a hole transport layer.

    PubMed

    Yu, Jae Choul; Hong, Ji A; Jung, Eui Dae; Kim, Da Bin; Baek, Soo-Min; Lee, Sukbin; Cho, Shinuk; Park, Sung Soo; Choi, Kyoung Jin; Song, Myoung Hoon

    2018-01-18

    The beneficial use of a hole transport layer (HTL) as a substitution for poly(3,4-ethlyenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) is regarded as one of the most important approaches for improving the stability and efficiency of inverted perovskite solar cells. Here, we demonstrate highly efficient and stable inverted perovskite solar cells by applying a GO-doped PEDOT:PSS (PEDOT:GO) film as an HTL. The high performance of this solar cell stems from the excellent optical and electrical properties of the PEDOT:GO film, including a higher electrical conductivity, a higher work function related to the reduced contact barrier between the perovskite layer and the PEDOT:GO layer, enhanced crystallinity of the perovskite crystal, and suppressed leakage current. Moreover, the device with the PEDOT:GO layer showed excellent long-term stability in ambient air conditions. Thus, the enhancement in the efficiency and the excellent stability of inverted perovskite solar cells are promising for the eventual commercialization of perovskite optoelectronic devices.

  16. 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

  17. Simple, heart-smart substitutions

    MedlinePlus

    Coronary artery disease - heart smart substitutions; Atherosclerosis - heart smart substitutions; Cholesterol - heart smart substitutions; Coronary heart disease - heart smart substitutions; Healthy diet - heart ...

  18. Vapor Grown Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Abdussamad Abbas, Hisham

    Perovskite solar cells has been the fastest growing solar cell material till date with verified efficiencies of over 22%. Most groups in the world focuses their research on solution based devices that has residual solvent in the material bulk. This work focuses extensively on the fabrication and properties of vapor based perovskite devices that is devoid of solvents. The initial part of my work focuses on the detailed fabrication of high efficiency consistent sequential vapor NIP devices made using P3HT as P-type Type II heterojunction. The sequential vapor devices experiences device anomalies like voltage evolution and IV hysteresis owing to charge trapping in TiO2. Hence, sequential PIN devices were fabricated using doped Type-II heterojunctions that had no device anomalies. The sequential PIN devices has processing restriction, as organic Type-II heterojunction materials cannot withstand high processing temperature, hence limiting device efficiency. Thereby bringing the need of co-evaporation for fabricating high efficiency consistent PIN devices, the approach has no-restriction on substrates and offers stoichiometric control. A comprehensive description of the fabrication, Co-evaporator setup and how to build it is described. The results of Co-evaporated devices clearly show that grain size, stoichiometry and doped transport layers are all critical for eliminating device anomalies and in fabricating high efficiency devices. Finally, Formamidinium based perovskite were fabricated using sequential approach. A thermal degradation study was conducted on Methyl Ammonium Vs. Formamidinium based perovskite films, Formamidinium based perovskites were found to be more stable. Lastly, inorganic films such as CdS and Nickel oxide were developed in this work.

  19. Recent advances of flexible hybrid perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Shin, Dong Hee; Heo, Jin Hyuck; Im, Sang Hyuk

    2017-11-01

    Recently, hybrid perovskite solar cells have attracted great interest because they can be fabricated to low cost, flexible, and highly efficient solar cells. Here, we introduced recent advances of flexible hybrid perovskite solar cells. We introduced research background of flexible perovskite solar cells in introduction part. Then we composed the main body to i) structure and properties of hybrid perovskite solar cells, ii) why flexible hybrid perovskite solar cells are important?, iii) transparent conducting oxide (TCO) based flexible hybrid perovskite solar cells, and iv) TCO-free transparent conducting electrode (TCE) based flexible hybrid perovskite solar cells. Finally, we summarized research outlook of flexible hybrid perovskite solar cells.

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

    SciTech Connect

    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 hasmore » 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 0.8« less

  1. 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.

  2. Perovskite in Earth’s deep interior

    NASA Astrophysics Data System (ADS)

    Hirose, Kei; Sinmyo, Ryosuke; Hernlund, John

    2017-11-01

    Silicate perovskite-type phases are the most abundant constituent inside our planet and are the predominant minerals in Earth’s lower mantle more than 660 kilometers below the surface. Magnesium-rich perovskite is a major lower mantle phase and undergoes a phase transition to post-perovskite near the bottom of the mantle. Calcium-rich perovskite is proportionally minor but may host numerous trace elements that record chemical differentiation events. The properties of mantle perovskites are the key to understanding the dynamic evolution of Earth, as they strongly influence the transport properties of lower mantle rocks. Perovskites are expected to be an important constituent of rocky planets larger than Mars and thus play a major role in modulating the evolution of terrestrial planets throughout the universe.

  3. Two-Dimensional Lead Halide Perovskites Templated by a Conjugated Asymmetric Diammonium.

    PubMed

    Hautzinger, Matthew P; Dai, Jun; Ji, Yujin; Fu, Yongping; Chen, Jie; Guzei, Ilia A; Wright, John C; Li, Youyong; Jin, Song

    2017-12-18

    We report novel two-dimensional lead halide perovskite structures templated by a unique conjugated aromatic dication, N,N-dimethylphenylene-p-diammonium (DPDA). The asymmetrically substituted primary and tertiary ammoniums in DPDA facilitate the formation of two-dimensional network (2DN) perovskite structures incorporating a conjugated dication between the PbX 4 2- (X = Br, I) layers. These 2DN structures of (DPDA)PbI 4 and (DPDA)PbBr 4 were characterized by single-crystal X-ray diffraction, showing uniquely low distortions in the Pb-X-Pb bond angle for 2D perovskites. The Pb-I-Pb bond angle is very close to ideal (180°) for a 2DN lead iodide perovskite, which can be attributed to the ability of the rigid diammonium DPDA to insert into the PbX 6 2- octahedral pockets. Optical characterization of (DPDA)PbI 4 shows an excitonic absorption peak at 2.29 eV (541 nm), which is red-shifted in comparison to similar 2DN lead iodide structures. Temperature-dependent photoluminescence of both compounds reveals both a self-trapped exciton and free exciton emission feature. The reduced exciton absorption energy and emission properties are attributed to the dication-induced structural order of the inorganic PbX 4 2- layers. DFT calculation results suggest mixing of the conjugated organic orbital component in the valence band of these 2DN perovskites. These results demonstrate a rational new strategy to incorporate conjugated organic dications into hybrid perovskites and will spur spectroscopic investigations of these compounds as well as optoelectronic applications.

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

    SciTech Connect

    Subhashini, P., E-mail: subhashinisvu@gmail.com; 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 crystalmore » 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.« less

  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. 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

  7. 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.

  8. 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 Cs 3 Sb 2 Br 9 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 (Cs 3 Sb 2 X 9 ) 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.

  9. Inhomogeneous degradation in metal halide perovskites

    NASA Astrophysics Data System (ADS)

    Yang, Rong; Zhang, Li; Cao, Yu; Miao, Yanfeng; Ke, You; Wei, Yingqiang; Guo, Qiang; Wang, Ying; Rong, Zhaohua; Wang, Nana; Li, Renzhi; Wang, Jianpu; Huang, Wei; Gao, Feng

    2017-08-01

    Although the rapid development of organic-inorganic metal halide perovskite solar cells has led to certified power conversion efficiencies of above 20%, their poor stability remains a major challenge, preventing their practical commercialization. In this paper, we investigate the intrinsic origin of the poor stability in perovskite solar cells by using a confocal fluorescence microscope. We find that the degradation of perovskite films starts from grain boundaries and gradually extend to the center of the grains. Firmly based on our findings, we further demonstrate that the device stability can be significantly enhanced by increasing the grain size of perovskite crystals. Our results have important implications to further enhance the stability of optoelectronic devices based on metal halide perovskites.

  10. 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.

  11. Defect Genome of Cubic Perovskites for Fuel Cell Applications

    SciTech Connect

    Balachandran, Janakiraman; Lin, Lianshan; Anchell, Jonathan S.

    Heterogeneities such as point defects, inherent to material systems, can profoundly influence material functionalities critical for numerous energy applications. This influence in principle can be identified and quantified through development of large defect data sets which we call the defect genome, employing high-throughput ab initio calculations. However, high-throughput screening of material models with point defects dramatically increases the computational complexity and chemical search space, creating major impediments toward developing a defect genome. In this paper, we overcome these impediments by employing computationally tractable ab initio models driven by highly scalable workflows, to study formation and interaction of various point defectsmore » (e.g., O vacancies, H interstitials, and Y substitutional dopant), in over 80 cubic perovskites, for potential proton-conducting ceramic fuel cell (PCFC) applications. The resulting defect data sets identify several promising perovskite compounds that can exhibit high proton conductivity. Furthermore, the data sets also enable us to identify and explain, insightful and novel correlations among defect energies, material identities, and defect-induced local structural distortions. Finally, such defect data sets and resultant correlations are necessary to build statistical machine learning models, which are required to accelerate discovery of new materials.« less

  12. Defect Genome of Cubic Perovskites for Fuel Cell Applications

    DOE PAGES

    Balachandran, Janakiraman; Lin, Lianshan; Anchell, Jonathan S.; ...

    2017-10-10

    Heterogeneities such as point defects, inherent to material systems, can profoundly influence material functionalities critical for numerous energy applications. This influence in principle can be identified and quantified through development of large defect data sets which we call the defect genome, employing high-throughput ab initio calculations. However, high-throughput screening of material models with point defects dramatically increases the computational complexity and chemical search space, creating major impediments toward developing a defect genome. In this paper, we overcome these impediments by employing computationally tractable ab initio models driven by highly scalable workflows, to study formation and interaction of various point defectsmore » (e.g., O vacancies, H interstitials, and Y substitutional dopant), in over 80 cubic perovskites, for potential proton-conducting ceramic fuel cell (PCFC) applications. The resulting defect data sets identify several promising perovskite compounds that can exhibit high proton conductivity. Furthermore, the data sets also enable us to identify and explain, insightful and novel correlations among defect energies, material identities, and defect-induced local structural distortions. Finally, such defect data sets and resultant correlations are necessary to build statistical machine learning models, which are required to accelerate discovery of new materials.« less

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  14. 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)

  15. Static and dynamic optical properties of La 1-xSr xFeO 3-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 La 1-xSr xFeO 3-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 1.25more » 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.« less

  16. Strained hybrid perovskite thin films and their impact on the intrinsic stability of perovskite solar cells

    PubMed Central

    Zhao, Jingjing; Deng, Yehao; Wei, Haotong; Zheng, Xiaopeng; Yu, Zhenhua; Shao, Yuchuan; Shield, Jeffrey E.; Huang, Jinsong

    2017-01-01

    Organic-inorganic hybrid perovskite (OIHP) solar cells have achieved comparable efficiencies to those of commercial solar cells, although their instability hinders their commercialization. Although encapsulation techniques have been developed to protect OIHP solar cells from external stimuli such as moisture, oxygen, and ultraviolet light, understanding of the origin of the intrinsic instability of perovskite films is needed to improve their stability. We show that the OIHP films fabricated by existing methods are strained and that strain is caused by mismatched thermal expansion of perovskite films and substrates during the thermal annealing process. The polycrystalline films have compressive strain in the out-of-plane direction and in-plane tensile strain. The strain accelerates degradation of perovskite films under illumination, which can be explained by increased ion migration in strained OIHP films. This study points out an avenue to enhance the intrinsic stability of perovskite films and solar cells by reducing residual strain in perovskite films. PMID:29159287

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

    PubMed

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

    2018-01-10

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

  18. Recent patents on perovskite ferroelectric nanostructures.

    PubMed

    Zhu, Xinhua

    2009-01-01

    Ferroelectric oxide materials with a perovskite structure have promising applications in electronic devices such as random access memories, sensors, actuators, infrared detectors, and so on. Recent advances in science and technology of ferroelectrics have resulted in the feature sizes of ferroelectric-based electronic devices entering into nanoscale dimensions. At nanoscale perovskite ferroelectric materials exhibit a pronounced size effect manifesting itself in a significant deviation of the properties of low-dimensional structures from the bulk and film counterparts. One-dimensional perovskite ferroelectric nanotube/nanowire systems, offer fundamental scientific opportunities for investigating the intrinsic size effects in ferroelectrics. In the past several years, much progress has been made both in fabrication and physical property testing of perovskite ferroelectric nanostructures. In the first part of this paper, the recent patents and literatures for fabricating ferroelectric nanowires, nanorods, nanotubes, and nanorings with promising features, are reviewed. The second part deals with the recent advances on the physical property testing of perovskite ferroelectric nanostructures. The third part summarizes the recently patents and literatures about the microstructural characterizations of perovskite ferroelectric nanostructures, to improve their crystalline quality, morphology and uniformity. Finally, we conclude this review with personal perspectives towards the potential future developments of perovskite ferroelectric nanostructures.

  19. 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 +, Pb 2+, 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 TiO 2/perovskite/spiro-OMeTAD-based PSC, Li +-ion migration from spiro-OMeTAD to the perovskite and TiO 2 layer is illustrated by time-of-flight secondary-ion mass spectrometry. The movementmore » of Li + ions in PSCs plays an important role in modulating the solar cell performance, tuning TiO 2 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

  20. Room-temperature ferromagnetism in Fe-based perovskite solid solution in lead-free ferroelectric Bi0.5Na0.5TiO3 materials

    NASA Astrophysics Data System (ADS)

    Hung, Nguyen The; Bac, Luong Huu; Trung, Nguyen Ngoc; Hoang, Nguyen The; Van Vinh, Pham; Dung, Dang Duc

    2018-04-01

    The integration of ferromagnetism in lead-free ferroelectric materials is important to fabricate smart materials for electronic devices. In this work, (1 - x)Bi0.5Na0.5TiO3 + xMgFeO3-δ materials (x = 0-9 mol%) were prepared through sol-gel method. X-ray diffraction characterization indicated that MgFeO3-δ materials existed as a well solid solution in lead-free ferroelectric Bi0.5Na0.5TiO3 materials. The rhombohedral structure of Bi0.5Na0.5TiO3 materials was distorted due to the random distribution of Mg and Fe cations into the host lattice. The reduced optical band gap and the induced room-temperature ferromagnetism were due to the spin splitting of transition metal substitution at the B-site of perovskite Bi0.5Na0.5TiO3 and the modification by A-site co-substitution. This work elucidates the role of secondary phase as solid solution in Bi0.5Na0.5TiO3 material for development of lead-free multiferroelectric materials.

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

    DOE PAGES

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

    2016-05-25

    In this study, we demonstrate the large grained perovskite solar cells prepared from precursor solution comprising single-crystal perovskite powders for the first time. Here, the resultant large grained perovskite thin film possesses negligible physical (structural) gap between each large grain and are highly crystalline as evidenced by its fan-shaped birefringence observed under polarized light, which is very different to the thin film prepared from the typical precursor route (MAI + PbI 2).

  2. Principles of Chemical Bonding and Band Gap Engineering in Hybrid Organic-Inorganic Halide Perovskites.

    PubMed

    Walsh, Aron

    2015-03-19

    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, CH 3 NH 3 PbI 3 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.

  3. Lead-Free, Two-Dimensional Mixed Germanium and Tin Perovskites.

    PubMed

    Cheng, Pengfei; Wu, Tao; Liu, Junxue; Deng, Wei-Qiao; Han, Keli

    2018-05-17

    Hybrid two-dimensional (2D) organic-inorganic perovskites continue to draw increased attention in view of their outstanding performance in optoelectronic devices such as solar cells and light-emitting devices. Herein, for the first time, we report the synthesis and characterization of lead-free, 2D mixed Ge-Sn halide perovskites, (PEA) 2 Ge 1- x Sn x I 4 (where PEA = C 6 H 5 CH 2 CH 2 NH 3 + ), and demonstrate that the bandgaps decrease linearly with increasing Sn content. Most importantly, among them, (PEA) 2 Ge 0.5 Sn 0.5 I 4 possesses the smallest bandgap of 1.95 eV. Density functional theory calculations confirm that Sn substitution induces a smaller bandgap and more dispersed band structure, which are desirable characteristics of light-absorbing materials. In addition, conductivity and stability of (PEA) 2 Ge 0.5 Sn 0.5 I 4 have also been assessed.

  4. Perovskites: transforming photovoltaics, a mini-review

    DOE PAGES

    Chilvery, Ashwith Kumar; Batra, Ashok K.; Yang, Bin; ...

    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.

  5. 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, electronmore » 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

  6. Hybrid Lead Halide Layered Perovskites with Silsesquioxane Interlayers.

    PubMed

    Kataoka, Sho; Kaburagi, Wako; Mochizuki, Hiroyuki; Kamimura, Yoshihiro; Sato, Kazuhiko; Endo, Akira

    2018-01-01

    Hybrid organic-lead halide perovskites exhibit remarkable properties as semiconductors and light absorbers. Here, we report the formation of silsesquioxane-lead halide hybrid layered perovskites. We prepared silsesquioxane with a cubic cage-like structure and fabricated hybrid silsesquioxane-lead halide layered perovskites in a self-assembled manner. It is demonstrated that the silsesquioxane maintain their cage-like structure between lead halide perovskite layers. The silsesquioxane-lead halide perovskites also show excitonic absorption and emission in the visible light region similar to typical lead halide layered perovskites.

  7. 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. 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.

  9. Mixed-Halide Perovskites with Stabilized Bandgaps.

    PubMed

    Xiao, Zhengguo; Zhao, Lianfeng; Tran, Nhu L; Lin, Yunhui Lisa; Silver, Scott H; Kerner, Ross A; Yao, Nan; Kahn, Antoine; Scholes, Gregory D; Rand, Barry P

    2017-11-08

    One merit of organic-inorganic hybrid perovskites is their tunable bandgap by adjusting the halide stoichiometry, an aspect critical to their application in tandem solar cells, wavelength-tunable light emitting diodes (LEDs), and lasers. However, the phase separation of mixed-halide perovskites caused by light or applied bias results in undesirable recombination at iodide-rich domains, meaning open-circuit voltage (V OC ) pinning in solar cells and infrared emission in LEDs. Here, we report an approach to suppress halide redistribution by self-assembled long-chain organic ammonium capping layers at nanometer-sized grain surfaces. Using the stable mixed-halide perovskite films, we are able to fabricate efficient and wavelength-tunable perovskite LEDs from infrared to green with high external quantum efficiencies of up to 5%, as well as linearly tuned V OC from 1.05 to 1.45 V in solar cells.

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

    PubMed

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

    2018-02-06

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

  11. 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.

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

    PubMed

    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

    2016-10-21

    The perovskite SrIrO_{3} 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 Sn^{4+} for Ir^{4+} in the SrIr_{1-x}Sn_{x}O_{3} perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic (AF) phase at T_{N}≥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 T_{N} 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 T_{N}. 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 T_{N} in the same way as proposed by Slater.

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

    NASA Astrophysics Data System (ADS)

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

    2018-05-01

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

  14. Constructing Efficient and Stable Perovskite Solar Cells via Interconnecting Perovskite Grains.

    PubMed

    Hou, Xian; Huang, Sumei; Ou-Yang, Wei; Pan, Likun; Sun, Zhuo; Chen, Xiaohong

    2017-10-11

    A high-quality perovskite film with interconnected perovskite grains was obtained by incorporating terephthalic acid (TPA) additive into the perovskite precursor solution. The presence of TPA changed the crystallization kinetics of the perovskite film and promoted lateral growth of grains in the vicinity of crystal boundaries. As a result, sheet-shaped perovskite was formed and covered onto the bottom grains, which made some adjacent grains partly merge together to form grains-interconnected perovskite film. Perovskite solar cells (PSCs) with TPA additive exhibited a power conversion efficiency (PCE) of 18.51% with less hysteresis, which is obviously higher than that of pristine cells (15.53%). PSCs without and with TPA additive retain 18 and 51% of the initial PCE value, respectively, aging for 35 days exposed to relative humidity 30% in air without encapsulation. Furthermore, MAPbI 3 film with TPA additive shows superior thermal stability to the pristine one under 100 °C baking. The results indicate that the presence of TPA in perovskite film can greatly improve the performance of PSCs as well as their moisture resistance and thermal stability.

  15. Thermoelasticity of (Mg,Fe)SiO3 perovskite

    NASA Astrophysics Data System (ADS)

    Shukla, Gaurav; Wu, Zhongqing; Hsu, Han; Cococcioni, Matteo; Wentzcovitch, Renata

    2015-03-01

    We present LDA+U calculations of high temperature elastic properties of (Mg(1 - x)Fex2+)SiO3 bridgemanite (0 <= x <= 0 . 125), the most abundant constituent of Earth's lower mantle. Calculations of aggregate elastic moduli and acoustic velocities for the Mg-end member (x=0) are in excellent agreement with the latest high pressure and high temperature experimental measurements. In the iron bearing system, we particularly focus on the change in thermoelastic parameters across the state change that occurs in ferrous iron above ~30 GPa, often attributed to a high-spin (HS) to intermediate spin (IS) crossover but explained by calculations as a lateral displacement of substitutional iron in the perovskite cage. We show that the measured effect on the equation of state of this change in the state of iron can be explained by the lateral displacement of substitutional iron, not by the HS to IS crossover. Calculated elastic properties of (Mg0.875 Fe0.125 2 +)SiO3 along an adiabatic mantle geotherm, somewhat overestimate longitudinal velocities but produce densities and shear velocities consistent with Preliminary Reference Earth Model data throughout most of the lower mantle. Research supported by NSF/EAR and NSF/CAREER.

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

    PubMed

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

    2018-04-05

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

  17. 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

  18. 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.

  19. 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-C 60 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.

  20. 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, (Sr 1-xLa x)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.

  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. No Substitute for Quality.

    ERIC Educational Resources Information Center

    Russo, Alexander

    2001-01-01

    School leaders are trying pay incentives, consortia, and temp firms to assuage their need for qualified substitute teachers. Five coping strategies include making the job more attractive, increasing the candidate pool, hiring some permanent subs, using automated calling systems, and examining systemic issues. Substitutes are unionizing in some…

  3. Managing Substitute Teaching.

    ERIC Educational Resources Information Center

    Jones, Kevin R.

    1999-01-01

    This news brief presents information on managing substitute teaching. The information is based on issues discussed at a summit meeting which included public school administrators and personnel directors from around the nation. The main topics of concern focused around four core components related to the management of substitute teaching:…

  4. Making and Breaking of Lead Halide Perovskites

    DOE PAGES

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

    2016-01-20

    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 rapidmore » 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

  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. Water electrolysis on La 1-xSr xCoO 3-δ perovskite electrocatalysts

    SciTech Connect

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

    2016-03-23

    Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr 2+ substitution into La 1-xSr xCoO 3-δ. We attempt tomore » rationalize the high activities of La 1-xSr xCoO 3-δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO 2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.« less

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

    NASA Astrophysics Data System (ADS)

    Mitzi, David

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

  8. Water electrolysis on La 1-xSr xCoO 3-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 Sr 2+ substitution into La 1–xSr xCoO 3–δ. We attemptmore » to rationalize the high activities of La 1–xSr xCoO 3–δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO 2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.« less

  9. 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 TiO 2 /perovskite interface was also obtained which in turn allow us to achieve a higher V oc value.

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  11. 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

  12. Hybrid Perovskites: Prospects for Concentrator Solar Cells.

    PubMed

    Lin, Qianqian; Wang, Zhiping; Snaith, Henry J; Johnston, Michael B; Herz, Laura M

    2018-04-01

    Perovskite solar cells have shown a meteoric rise of power conversion efficiency and a steady pace of improvements in their stability of operation. Such rapid progress has triggered research into approaches that can boost efficiencies beyond the Shockley-Queisser limit stipulated for a single-junction cell under normal solar illumination conditions. The tandem solar cell architecture is one concept here that has recently been successfully implemented. However, the approach of solar concentration has not been sufficiently explored so far for perovskite photovoltaics, despite its frequent use in the area of inorganic semiconductor solar cells. Here, the prospects of hybrid perovskites are assessed for use in concentrator solar cells. Solar cell performance parameters are theoretically predicted as a function of solar concentration levels, based on representative assumptions of charge-carrier recombination and extraction rates in the device. It is demonstrated that perovskite solar cells can fundamentally exhibit appreciably higher energy-conversion efficiencies under solar concentration, where they are able to exceed the Shockley-Queisser limit and exhibit strongly elevated open-circuit voltages. It is therefore concluded that sufficient material and device stability under increased illumination levels will be the only significant challenge to perovskite concentrator solar cell applications.

  13. Molecular behavior of zero-dimensional perovskites

    PubMed Central

    Yin, Jun; Maity, Partha; De Bastiani, Michele; Dursun, Ibrahim; Bakr, Osman M.; Brédas, Jean-Luc; Mohammed, Omar F.

    2017-01-01

    Low-dimensional perovskites offer a rare opportunity to investigate lattice dynamics and charge carrier behavior in bulk quantum-confined solids, in addition to them being the leading materials in optoelectronic applications. In particular, zero-dimensional (0D) inorganic perovskites of the Cs4PbX6 (X = Cl, Br, or I) kind have crystal structures with isolated lead halide octahedra [PbX6]4− surrounded by Cs+ cations, allowing the 0D crystals to exhibit the intrinsic properties of an individual octahedron. Using both experimental and theoretical approaches, we studied the electronic and optical properties of the prototypical 0D perovskite Cs4PbBr6. Our results underline that this 0D perovskite behaves akin to a molecule, demonstrating low electrical conductivity and mobility as well as large polaron binding energy. Density functional theory calculations and transient absorption measurements of Cs4PbBr6 perovskite films reveal the polaron band absorption and strong polaron localization features of the material. A short polaron lifetime of ~2 ps is observed in femtosecond transient absorption experiments, which can be attributed to the fast lattice relaxation of the octahedra and the weak interactions among them. PMID:29250600

  14. 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.

  15. Hybrid Perovskites: Prospects for Concentrator Solar Cells

    PubMed Central

    Lin, Qianqian; Wang, Zhiping; Snaith, Henry J.; Johnston, Michael B.

    2018-01-01

    Abstract Perovskite solar cells have shown a meteoric rise of power conversion efficiency and a steady pace of improvements in their stability of operation. Such rapid progress has triggered research into approaches that can boost efficiencies beyond the Shockley–Queisser limit stipulated for a single‐junction cell under normal solar illumination conditions. The tandem solar cell architecture is one concept here that has recently been successfully implemented. However, the approach of solar concentration has not been sufficiently explored so far for perovskite photovoltaics, despite its frequent use in the area of inorganic semiconductor solar cells. Here, the prospects of hybrid perovskites are assessed for use in concentrator solar cells. Solar cell performance parameters are theoretically predicted as a function of solar concentration levels, based on representative assumptions of charge‐carrier recombination and extraction rates in the device. It is demonstrated that perovskite solar cells can fundamentally exhibit appreciably higher energy‐conversion efficiencies under solar concentration, where they are able to exceed the Shockley–Queisser limit and exhibit strongly elevated open‐circuit voltages. It is therefore concluded that sufficient material and device stability under increased illumination levels will be the only significant challenge to perovskite concentrator solar cell applications. PMID:29721426

  16. 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 to...

  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 to...

  18. 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 to...

  19. 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 to...

  20. 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.

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

    DOE PAGES

    Fu, Yongping; Zhu, Haiming; Schrader, Alex W.; ...

    2016-01-04

    The excellent intrinsic optoelectronic properties of methylammonium lead halide perovskites (MAPbX 3, 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 (FAPbX 3) that feature red-shifted emission and better thermal stability compared to MAPbX 3. We demonstrate optically pumped room-temperature near-infrared (~820 nm) and green lasing (~560more » nm) from FAPbI 3 (and MABr-stabilized FAPbI 3) and FAPbBr 3 nanowires with low lasing thresholds of several microjoules per square centimeter and high quality factors of about 1500–2300. More remarkably, the FAPbI 3 and MABr-stabilized FAPbI 3 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 MAPbI 3 (~10 7 laser shots). We further demonstrate tunable nanowire lasers in wider wavelength region from FA-based lead halide perovskite alloys (FA,MA)PbI 3 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.« less

  2. Rubidium as an Alternative Cation for Efficient Perovskite Light-Emitting Diodes.

    PubMed

    Kanwat, Anil; Moyen, Eric; Cho, Sinyoung; Jang, Jin

    2018-05-16

    Incorporation of rubidium (Rb) into mixed lead halide perovskites has recently achieved record power conversion efficiency and excellent stability in perovskite solar cells. Inspired by these tremendous advances in photovoltaics, this study demonstrates the impact of Rb incorporation into MAPbBr 3 -based light emitters. Rb partially substitutes MA (methyl ammonium), resulting in a mixed cation perovskite with the formula MA (1- x) Rb x PbBr 3 . Pure MAPbBr 3 crystallizes into a polycrystalline layer with highly defective sub-micrometer grains. However, the addition of a small amount of Rb forms MA (1- x) Rb x PbBr 3 nanocrystals (10 nm) embedded in an amorphous matrix of MA/Rb Br. These nanocrystals grow into defect-free sub-micrometer-sized crystallites with further addition of Rb, resulting in a 3-fold increase in exciton lifetime when the molar ratio of MABr/RbBr is 1:1. A thin film fabricated with a 1:1 molar ratio of MABr/RbBr showed the best electroluminescent properties with a current efficiency (CE) of 9.45 cd/A and a luminance of 7694 cd/m 2 . These values of CE and luminance are, respectively, 19 and 10 times larger than those achieved by pure MAPbBr 3 devices (0.5 cd/A and 790 cd/m 2 ). We believe this work provides important information on the future compositional optimization of Rb + -based mixed cation perovskites for obtaining high-performance light-emitting diodes.

  3. 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.

  4. Autothermal reforming catalyst having perovskite structure

    DOEpatents

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

    2009-03-24

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

  5. Aqueous-Containing Precursor Solutions for Efficient Perovskite Solar Cells.

    PubMed

    Liu, Dianyi; Traverse, Christopher J; Chen, Pei; Elinski, Mark; Yang, Chenchen; Wang, Lili; Young, Margaret; Lunt, Richard R

    2018-01-01

    Perovskite semiconductors have emerged as competitive candidates for photovoltaic applications due to their exceptional optoelectronic properties. However, the impact of moisture instability on perovskite films is still a key challenge for perovskite devices. While substantial effort is focused on preventing moisture interaction during the fabrication process, it is demonstrated that low moisture sensitivity, enhanced crystallization, and high performance can actually be achieved by exposure to high water content (up to 25 vol%) during fabrication with an aqueous-containing perovskite precursor. The perovskite solar cells fabricated by this aqueous method show good reproducibility of high efficiency with average power conversion efficiency (PCE) of 18.7% and champion PCE of 20.1% under solar simulation. This study shows that water-perovskite interactions do not necessarily negatively impact the perovskite film preparation process even at the highest efficiencies and that exposure to high contents of water can actually enable humidity tolerance during fabrication in air.

  6. 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 -OCH 3 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.

  7. Synthesis of substituted pyrazines

    DOEpatents

    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##

  8. Feature issue introduction: halide perovskites for optoelectronics.

    PubMed

    White, Thomas P; Deleporte, Emmanuelle; Sum, Tze-Chien

    2018-01-22

    This joint Optics Express and Optical Materials Express feature issue presents a collection of nine papers on the topic of halide perovskites for optoelectronics. Perovskite materials have attracted significant attention over the past four years, initially for their outstanding performance in thin film solar cells, but more recently for applications in light-emitting devices (LEDs and lasers), photodetectors and nonlinear optics. At the same time, there is still much more to learn about the fundamental properties of these materials, and how these depend on composition, processing, and exposure to the environment. This feature issue provides a snapshot of some of the latest research in this rapidly-evolving multidisciplinary field.

  9. Novel catalytic properties of quadruple perovskites

    PubMed Central

    Yamada, Ikuya

    2017-01-01

    ABSTRACT Quadruple perovskite oxides AA′3 B 4O12 demonstrate a rich variety of structural and electronic properties. A large number of constituent elements for A/A′/B-site cations can be introduced using the ultra-high-pressure synthesis method. Development of novel functional materials consisting of earth-abundant elements plays a crucial role in current materials science. In this paper, functional properties, especially oxygen reaction catalysis, for quadruple perovskite oxides CaCu3Fe4O12 and AMn7O12 (A = Ca, La) composed of earth-abundant elements are reviewed. PMID:28970864

  10. 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

  11. Perovskite Solar Cells—Towards Commercialization

    DOE PAGES

    Ono, Luis K.; Park, Nam-Gyu; Zhu, Kai; ...

    2017-07-13

    The Symposium ES1, Perovskite Solar Cells - Towards Commercialization, held at the 2017 Materials Research Society (MRS) Spring Meeting in Phoenix, Arizona (April 17-21, 2017) received ~200 abstracts. The 23 invited talks and 72 contributed oral presentations as well as 3 poster presentation sessions were organized into 13 principal themes according to the contents of the received abstracts. This Energy Focus article provides a concise summary of the opinions from the scientists and engineers who participated in this symposium regarding the recent progresses, challenges, and future directions for perovskite solar cells as well as other optoelectronic devices.

  12. 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

  13. Enhanced planar perovskite solar cell efficiency and stability using a perovskite/PCBM heterojunction formed in one step.

    PubMed

    Zhou, Long; Chang, Jingjing; Liu, Ziye; Sun, Xu; Lin, Zhenhua; Chen, Dazheng; Zhang, Chunfu; Zhang, Jincheng; Hao, Yue

    2018-02-08

    Perovskite/PCBM heterojunctions are efficient for fabricating perovskite solar cells with high performance and long-term stability. In this study, an efficient perovskite/PCBM heterojunction was formed via conventional sequential deposition and one-step formation processes. Compared with conventional deposition, the one-step process was more facile, and produced a perovskite thin film of substantially improved quality due to fullerene passivation. Moreover, the resulting perovskite/PCBM heterojunction exhibited more efficient carrier transfer and extraction, and reduced carrier recombination. The perovskite solar cell device based on one-step perovskite/PCBM heterojunction formation exhibited a higher maximum PCE of 17.8% compared with that from the conventional method (13.7%). The device also showed exceptional stability, retaining 83% of initial PCE after 60 days of storage under ambient conditions.

  14. Origins of n -type doping difficulties in perovskite stannates

    NASA Astrophysics Data System (ADS)

    Weston, L.; Bjaalie, L.; Krishnaswamy, K.; Van de Walle, C. G.

    2018-02-01

    The perovskite stannates (A SnO3 ; A = Ba, Sr, Ca) are promising for oxide electronics, but control of n -type doping has proved challenging. Using first-principles hybrid density functional calculations, we investigate La dopants and explore the formation of compensating acceptor defects. We find that La on the A site always behaves as a shallow donor, but incorporation of La on the Sn site can lead to self-compensation. At low La concentrations and in O-poor conditions, oxygen vacancies form in BaSnO3. A -site cation vacancies are found to be dominant among the native compensating centers. Compared to BaSnO3, charge compensation is a larger problem for the wider-band-gap stannates, SrSnO3 and CaSnO3, a trend we can explain based on conduction-band alignments. The formation of compensating acceptor defects can be inhibited by choosing oxygen-poor (cation-rich) growth or annealing conditions, thus providing a pathway for improved n -type doping.

  15. Structural and magnetic properties of SrMn1-xRuxO3 perovskites

    NASA Astrophysics Data System (ADS)

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

    2007-03-01

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

  16. 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 (CsPbX 3; 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 CsPbI 3 with Cl – or Br – causes a significant blue-shift in absorption and photoluminescence, whereas reacting I – with CsPbBr 3 causesmore » 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.« less

  17. 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; Department of Physics, Faculty Science, University Putra of Malaysia; Shaari, Abdul Halim

    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 andmore » 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.« less

  18. 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.

  19. Amine treatment induced perovskite nanowire network in perovskite solar cells: efficient surface passivation and carrier transport

    NASA Astrophysics Data System (ADS)

    Xiao, Ke; Cui, Can; Wang, Peng; Lin, Ping; Qiang, Yaping; Xu, Lingbo; Xie, Jiangsheng; Yang, Zhengrui; Zhu, Xiaodong; Yu, Xuegong; Yang, Deren

    2018-02-01

    In the fabrication of high efficiency organic-inorganic metal halide perovskite solar cells (PSCs), an additional interface modifier is usually applied for enhancing the interface passivation and carrier transport. In this paper, we develop an innovative method with in-situ growth of one-dimensional perovskite nanowire (1D PNW) network triggered by Lewis amine over the perovskite films. To our knowledge, this is the first time to fabricate PSCs with shape-controlled perovskite surface morphology, which improved power conversion efficiency (PCE) from 14.32% to 16.66% with negligible hysteresis. The amine molecule can passivate the trap states on the polycrystalline perovskite surface to reduce trap-state density. Meanwhile, as a fast channel, the 1D PNWs would promote carrier transport from the bulk perovskite film to the electron transport layer. The PSCs with 1D PNW modification not only exhibit excellent photovoltaic performances, but also show good stability with only 4% PCE loss within 30 days in the ambient air without encapsulation. Our results strongly suggest that in-situ grown 1D PNW network provides a feasible and effective strategy for nanostructured optoelectronic devices such as PSCs to achieve superior performances.

  20. Linking local structure and properties in perovskites containing equal concentrations of manganese and ruthenium

    SciTech Connect

    King, Graham; Ricciardo, Rebecca A.; Soliz, Jennifer R.

    The local structures of six perovskite compounds containing equal amounts of manganese and ruthenium on the B-site have been investigated by neutron and x-ray pair distribution function analysis. The compounds SrMn{sub 0.5}Ru{sub 0.5}O{sub 3}, Sr{sub 0.5}Ca{sub 0.5}Mn{sub 0.5}Ru{sub 0.5}O{sub 3}, and CaMn{sub 0.5}Ru{sub 0.5}O{sub 3} were studied to investigate the effects of pure chemical pressure on the local structure and valency ratio between Mn{sup 3+}/Ru{sup 5+} and Mn{sup 4+}/Ru{sup 4+}. Reverse Monte Carlo simulations confirm that there is a shift in the B-site cation charge distribution from nearly equal amounts of Mn{sup 3+}, Ru{sup 5+}, Mn{sup 4+}, and Ru{sup 4+}more » for SrMn{sub 0.5}Ru{sub 0.5}O{sub 3} to primarily Mn{sup 4+} and Ru{sup 4+} for CaMn{sub 0.5}Ru{sub 0.5}O{sub 3}. The compounds Ba{sub 0.5}La{sub 0.5}Mn{sub 0.5}Ru{sub 0.5}O{sub 3}, Ca{sub 0.5}La{sub 0.5}Mn{sub 0.5}Ru{sub 0.5}O{sub 3}, and Sr{sub 0.5}Ca{sub 0.25}La{sub 0.25}Mn{sub 0.5}Ru{sub 0.5}O{sub 3} were also investigated to study the effects of changing the charge of the A-site cation. Although substitution of La{sup 3+} for a divalent alkaline earth ion increases the Mn{sup 3+} content, this series of compounds also shows a relative increase in the concentration of Mn{sup 4+} as the average size of the A-site cation is decreased. In all compounds the octahedra containing Mn{sup 3+} are found to be Jahn-Teller distorted regardless of whether or not long-range orbital ordering is observed, while the Ru-centered octahedra are symmetric. No evidence for short-range cation ordering at either the A- or B-sites was found for any of the compositions. This study also reports that locally the A-site cations lie closer to the Mn ions than to the Ru ions and this asymmetry appears to be correlated to the degree of octahedral tilting.« less

  1. Influence of Rb/Cs Cation-Exchange on Inorganic Sn Halide Perovskites: From Chemical Structure to Physical Properties.

    PubMed

    Jung, Young-Kwang; Lee, Ji-Hwan; Walsh, Aron; Soon, Aloysius

    2017-04-11

    CsSnI 3 is a potential lead-free inorganic perovskite for solar energy applications due to its nontoxicity and attractive optoelectronic properties. Despite these advantages, photovoltaic cells using CsSnI 3 have not been successful to date, in part due to low stability. We demonstrate how gradual substitution of Rb for Cs influences the structural, thermodynamic, and electronic properties on the basis of first-principles density functional theory calculations. By examining the effect of the Rb:Cs ratio, we reveal a correlation between octahedral distortion and band gap, including spin-orbit coupling. We further highlight the cation-induced variation of the ionization potential (work function) and the importance of surface termination for tin-based halide perovskites for engineering high-performance solar cells.

  2. 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.

  3. 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

  4. The substitutability of reinforcers.

    PubMed

    Green, Leonard; Freed, Debra E

    1993-07-01

    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.

  5. 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.

  6. Improved perovskite phototransistor prepared using multi-step annealing method

    NASA Astrophysics Data System (ADS)

    Cao, Mingxuan; Zhang, Yating; Yu, Yu; Yao, Jianquan

    2018-02-01

    Organic-inorganic hybrid perovskites with good intrinsic physical properties have received substantial interest for solar cell and optoelectronic applications. However, perovskite film always suffers from a low carrier mobility due to its structural imperfection including sharp grain boundaries and pinholes, restricting their device performance and application potential. Here we demonstrate a straightforward strategy based on multi-step annealing process to improve the performance of perovskite photodetector. Annealing temperature and duration greatly affects the surface morphology and optoelectrical properties of perovskites which determines the device property of phototransistor. The perovskite films treated with multi-step annealing method tend to form highly uniform, well-crystallized and high surface coverage perovskite film, which exhibit stronger ultraviolet-visible absorption and photoluminescence spectrum compare to the perovskites prepared by conventional one-step annealing process. The field-effect mobilities of perovskite photodetector treated by one-step direct annealing method shows mobility as 0.121 (0.062) cm2V-1s-1 for holes (electrons), which increases to 1.01 (0.54) cm2V-1s-1 for that treated with muti-step slow annealing method. Moreover, the perovskite phototransistors exhibit a fast photoresponse speed of 78 μs. In general, this work focuses on the influence of annealing methods on perovskite phototransistor, instead of obtains best parameters of it. These findings prove that Multi-step annealing methods is feasible to prepared high performance based photodetector.

  7. Highly Efficient Spectrally Stable Red Perovskite Light-Emitting Diodes.

    PubMed

    Tian, Yu; Zhou, Chenkun; Worku, Michael; Wang, Xi; Ling, Yichuan; Gao, Hanwei; Zhou, Yan; Miao, Yu; Guan, Jingjiao; Ma, Biwu

    2018-05-01

    Perovskite light-emitting diodes (LEDs) have recently attracted great research interest for their narrow emissions and solution processability. Remarkable progress has been achieved in green perovskite LEDs in recent years, but not blue or red ones. Here, highly efficient and spectrally stable red perovskite LEDs with quasi-2D perovskite/poly(ethylene oxide) (PEO) composite thin films as the light-emitting layer are reported. By controlling the molar ratios of organic salt (benzylammonium iodide) to inorganic salts (cesium iodide and lead iodide), luminescent quasi-2D perovskite thin films are obtained with tunable emission colors from red to deep red. The perovskite/polymer composite approach enables quasi-2D perovskite/PEO composite thin films to possess much higher photoluminescence quantum efficiencies and smoothness than their neat quasi-2D perovskite counterparts. Electrically driven LEDs with emissions peaked at 638, 664, 680, and 690 nm have been fabricated to exhibit high brightness and external quantum efficiencies (EQEs). For instance, the perovskite LED with an emission peaked at 680 nm exhibits a brightness of 1392 cd m -2 and an EQE of 6.23%. Moreover, exceptional electroluminescence spectral stability under continuous device operation has been achieved for these red perovskite LEDs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. 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)

    Bilodeau, Steven (Inventor); Baum, Thomas H. (Inventor); Roeder, Jeffrey F. (Inventor); Chen, Ing-Shin (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.

  9. Effect of Rubidium Incorporation on the Structural, Electrical, and Photovoltaic Properties of Methylammonium Lead Iodide-Based Perovskite Solar Cells

    SciTech Connect

    Park, Ik Jae; Seo, Seongrok; Park, Min Ah

    We report the electrical properties of rubidium-incorporated methylammonium lead iodide ((Rb xMA 1-x)PbI 3) films and the photovoltaic performance of (Rb xMA 1-x)PbI 3 film-based p-i-n-type perovskite solar cells (PSCs). The incorporation of a small amount of Rb + (x = 0.05) increases both the open circuit voltage (V oc) and the short circuit photocurrent density (J sc) of the PSCs, leading to an improved power conversion efficiency (PCE). However, a high fraction of Rb + incorporation (x = 0.1 and 0.2) decreases the J sc and thus the PCE, which is attributed to the phase segregation of the singlemore » tetragonal perovskite phase to a MA-rich tetragonal perovskite phase and a RbPbI 3 orthorhombic phase at high Rb fractions. Conductive atomic force microscopic and admittance spectroscopic analyses reveal that the single-phase (Rb 0.05MA 0.95)PbI 3 film has a high electrical conductivity because of a reduced deep-level trap density. We also found that Rb substitution enhances the diode characteristics of the PSC, as evidenced by the reduced reverse saturation current (J 0). The optimized (Rb xMA 1-x)PbI 3 PSCs exhibited a PCE of 18.8% with negligible hysteresis in the photocurrent-voltage curve. The results from this work enhance the understanding of the effect of Rb incorporation into organic-inorganic hybrid halide perovskites and enable the exploration of Rb-incorporated mixed perovskites for various applications, such as solar cells, photodetectors, and light-emitting diodes.« less

  10. Effect of Rubidium Incorporation on the Structural, Electrical, and Photovoltaic Properties of Methylammonium Lead Iodide-Based Perovskite Solar Cells

    DOE PAGES

    Park, Ik Jae; Seo, Seongrok; Park, Min Ah; ...

    2017-11-10

    We report the electrical properties of rubidium-incorporated methylammonium lead iodide ((Rb xMA 1-x)PbI 3) films and the photovoltaic performance of (Rb xMA 1-x)PbI 3 film-based p-i-n-type perovskite solar cells (PSCs). The incorporation of a small amount of Rb + (x = 0.05) increases both the open circuit voltage (V oc) and the short circuit photocurrent density (J sc) of the PSCs, leading to an improved power conversion efficiency (PCE). However, a high fraction of Rb + incorporation (x = 0.1 and 0.2) decreases the J sc and thus the PCE, which is attributed to the phase segregation of the singlemore » tetragonal perovskite phase to a MA-rich tetragonal perovskite phase and a RbPbI 3 orthorhombic phase at high Rb fractions. Conductive atomic force microscopic and admittance spectroscopic analyses reveal that the single-phase (Rb 0.05MA 0.95)PbI 3 film has a high electrical conductivity because of a reduced deep-level trap density. We also found that Rb substitution enhances the diode characteristics of the PSC, as evidenced by the reduced reverse saturation current (J 0). The optimized (Rb xMA 1-x)PbI 3 PSCs exhibited a PCE of 18.8% with negligible hysteresis in the photocurrent-voltage curve. The results from this work enhance the understanding of the effect of Rb incorporation into organic-inorganic hybrid halide perovskites and enable the exploration of Rb-incorporated mixed perovskites for various applications, such as solar cells, photodetectors, and light-emitting diodes.« less

  11. Effect of Rubidium Incorporation on the Structural, Electrical, and Photovoltaic Properties of Methylammonium Lead Iodide-Based Perovskite Solar Cells.

    PubMed

    Park, Ik Jae; Seo, Seongrok; Park, Min Ah; Lee, Sangwook; Kim, Dong Hoe; Zhu, Kai; Shin, Hyunjung; Kim, Jin Young

    2017-12-06

    We report the electrical properties of rubidium-incorporated methylammonium lead iodide ((Rb x MA 1-x )PbI 3 ) films and the photovoltaic performance of (Rb x MA 1-x )PbI 3 film-based p-i-n-type perovskite solar cells (PSCs). The incorporation of a small amount of Rb + (x = 0.05) increases both the open circuit voltage (V oc ) and the short circuit photocurrent density (J sc ) of the PSCs, leading to an improved power conversion efficiency (PCE). However, a high fraction of Rb + incorporation (x = 0.1 and 0.2) decreases the J sc and thus the PCE, which is attributed to the phase segregation of the single tetragonal perovskite phase to a MA-rich tetragonal perovskite phase and a RbPbI 3 orthorhombic phase at high Rb fractions. Conductive atomic force microscopic and admittance spectroscopic analyses reveal that the single-phase (Rb 0.05 MA 0.95 )PbI 3 film has a high electrical conductivity because of a reduced deep-level trap density. We also found that Rb substitution enhances the diode characteristics of the PSC, as evidenced by the reduced reverse saturation current (J 0 ). The optimized (Rb x MA 1-x )PbI 3 PSCs exhibited a PCE of 18.8% with negligible hysteresis in the photocurrent-voltage curve. The results from this work enhance the understanding of the effect of Rb incorporation into organic-inorganic hybrid halide perovskites and enable the exploration of Rb-incorporated mixed perovskites for various applications, such as solar cells, photodetectors, and light-emitting diodes.

  12. Scalable fabrication of perovskite solar cells

    DOE PAGES

    Li, Zhen; Klein, Talysa R.; Kim, Dong Hoe; ...

    2018-03-27

    Perovskite materials use earth-abundant elements, have low formation energies for deposition and are compatible with roll-to-roll and other high-volume manufacturing techniques. These features make perovskite solar cells (PSCs) suitable for terawatt-scale energy production with low production costs and low capital expenditure. Demonstrations of performance comparable to that of other thin-film photovoltaics (PVs) and improvements in laboratory-scale cell stability have recently made scale up of this PV technology an intense area of research focus. Here, we review recent progress and challenges in scaling up PSCs and related efforts to enable the terawatt-scale manufacturing and deployment of this PV technology. We discussmore » common device and module architectures, scalable deposition methods and progress in the scalable deposition of perovskite and charge-transport layers. We also provide an overview of device and module stability, module-level characterization techniques and techno-economic analyses of perovskite PV modules.« less

  13. Perovskite Patent Portfolio | Photovoltaic Research | NREL

    Science.gov Websites

    deposition of high-quality perovskite films. These techniques have been published in multiple peer-reviewed substrates that are suitable for high-throughput manufacturing and that can maximize the yield of the % to 3% increase in conversion efficiency when compared to a MAPbI3 film prepared with a standard

  14. [Delegation yes, substitution no!].

    PubMed

    Schroeder, A

    2014-08-01

    The aging of society leads on the one hand to increasing case numbers and on the other hand to a reduction in the number of physicians available for patient treatment. The delegation and substitution of medical duties as a tried and tested method is increasingly being recommended in order to compensate for the lack of physicians. The Berufsverband der Deutschen Urologen (BDU, Professional Association of German Urologists) supports the guiding principle of the Bundesärztekammer (Federal Medical Council) of "delegation yes, substitution no" and rejects a substitution of medical duties by non-medical academic health personnel. Against the background of the demographic changes, the increasing need for treatment and the current deficiency of junior physicians, a more extensive inclusion of well-qualified and experienced non-medical personnel by the delegation of medically responsible duties (medical scope of practice) can be an appropriate measure to maintain a good medical service in practices, hospitals and nursing homes.

  15. 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

  16. B-Site Metal Cation Exchange in Halide Perovskites

    DOE PAGES

    Eperon, Giles E.; Ginger, David S.

    2017-05-02

    Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation ofmore » the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.« less

  17. B-Site Metal Cation Exchange in Halide Perovskites

    SciTech Connect

    Eperon, Giles E.; Ginger, David S.

    Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation ofmore » the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.« less

  18. 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

  19. 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.

  20. 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 40 CFR 721.10126 - Alkyl amino substituted triazine amino substituted benezenesulfonic acid reaction product with...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo substituted phenyl azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo...

  2. 40 CFR 721.10126 - Alkyl amino substituted triazine amino substituted benezenesulfonic acid reaction product with...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo substituted phenyl azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo...

  3. 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.…

  4. 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…

  5. Perovskite Solar Cell Stability Workshop: Quick Look Report

    DTIC Science & Technology

    2016-08-12

    Commercialization of Perovskite PV – Markets, Concerns, Opportunities” by Dirk Weiss, First Solar , USA j. “Expectations for PV Product Testing Today” by Sarah...Perovskite Solar Cell Stability Workshop Quick-Look Report Held by the Office of Naval Research at University...Workshop Summary, 11-12 Aug 2016 4. TITLE AND SUBTITLE Perovskite Solar Cell Stability Workshop: Quick-Look Report 5. FUNDING NUMBERS 6. AUTHOR(S

  6. Electron localization and magnetism in SrRuO3 with non-magnetic cation substitution

    NASA Astrophysics Data System (ADS)

    Tong, W.; Huang, F.-Q.; Chen, I.-W.

    2011-03-01

    The destruction of the ferromagnetism of alloyed SrRuO3 can be caused by electron localization at the substitution sites. Among all the non-magnetic cations that enter the B site, Zr4 + is the least disruptive to conductivity and ferromagnetism. This is because Zr4 + does not cause any charge disorder, and its empty d electron states which are poorly matched in energy with the Ru t2g4 states cause the least resonance scattering of Ru's d electrons. Conducting Sr(Ru, Zr)O3 may be used as an electrode for perovskite-based thin film devices, while its insulating counterpart provides unprecedented magnetoresistance, seldom seen in other non-manganite and non-cobaltite perovskites.

  7. Impact of Ultrathin C60 on Perovskite Photovoltaic Devices.

    PubMed

    Liu, Dianyi; Wang, Qiong; Traverse, Christopher J; Yang, Chenchen; Young, Margaret; Kuttipillai, Padmanaban S; Lunt, Sophia Y; Hamann, Thomas W; Lunt, Richard R

    2018-01-23

    Halide perovskite solar cells have seen dramatic progress in performance over the past several years. Certified efficiencies of inverted structure (p-i-n) devices have now exceeded 20%. In these p-i-n devices, fullerene compounds are the most popular electron-transfer materials. However, the full function of fullerenes in perovskite solar cells is still under investigation, and the mechanism of photocurrent hysteresis suppression by fullerene remains unclear. In previous reports, thick fullerene layers (>20 nm) were necessary to fully cover the perovskite film surface to make good contact with perovskite film and avoid large leakage currents. In addition, the solution-processed fullerene layer has been broadly thought to infiltrate into the perovskite film to passivate traps on grain boundary surfaces, causing suppressed photocurrent hysteresis. In this work, we demonstrate an efficient perovskite photovoltaic device with only 1 nm C 60 deposited by vapor deposition as the electron-selective material. Utilizing a combination of fluorescence microscopy and impedance spectroscopy, we show that the ultrathin C 60 predominately acts to extract electrons from the perovskite film while concomitantly suppressing the photocurrent hysteresis by reducing space charge accumulation at the interface. This work ultimately helps to clarify the dominant role of fullerenes in perovskite solar cells while simplifying perovskite solar cell design to reduce manufacturing costs.

  8. Development of Perovskite-Type Materials for Thermoelectric Application.

    PubMed

    Wu, Tingjun; Gao, Peng

    2018-06-12

    Oxide perovskite materials have a long history of being investigated for thermoelectric applications. Compared to the state-of-the-art tin and lead chalcogenides, these perovskite compounds have advantages of low toxicity, eco-friendliness, and high elemental abundance. However, because of low electrical conductivity and high thermal conductivity, the total thermoelectric performance of oxide perovskites is relatively poor. Variety of methods were used to enhance the TE properties of oxide perovskite materials, such as doping, inducing oxygen vacancy, embedding crystal imperfection, and so on. Recently, hybrid perovskite materials started to draw attention for thermoelectric application. Due to the low thermal conductivity and high Seebeck coefficient feature of hybrid perovskites materials, they can be promising thermoelectric materials and hold the potential for the application of wearable energy generators and cooling devices. This mini-review will build a bridge between oxide perovskites and burgeoning hybrid halide perovskites in the research of thermoelectric properties with an aim to further enhance the relevant performance of perovskite-type materials.

  9. 2D Ruddlesden-Popper Perovskites for Optoelectronics.

    PubMed

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

    2018-01-01

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

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

    DOE PAGES

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

    2016-10-20

    The perovskite SrIrO 3 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 Sn 4+ for Ir 4+ in the SrIr 1–xSn xO 3 perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic (AF) phase at T N ≥ 225 K. The continuous change of the cell volume as detected by x-ray diffractionmore » and the λ-shape transition of the specific heat on cooling through T N 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 T N. 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 T N in the same way as proposed by Slater.« less

  11. In situ nucleophilic substitutional growth of methylammonium lead iodide polycrystals.

    SciTech Connect

    Acik, Muge; Alam, Todd M.; Guo, Fangmin

    2017-01-01

    Methylammonium lead iodide (MAPbIx) perovskites are organic-inorganic semiconductors that serve as the light-harvesting component of the photovoltaics, and are desirable with their long diffusion length yielding power conversion efficiencies of ≥22%. Conventional techniques grow perovskites by spin coating precursors on an oxide or a polymer substrate followed by annealing, however, use of high boiling point solvents and high temperatures hinder device stability and performance. Through a one-step, acid-catalyzed nucleophilic-substitutional crystal growth in polar protic solvents, we show evidence for the substrate- and annealing- free production of MAPbIx polycrystals that are metallic-lead-free with negligibly small amount of PbI2 precipitation (<10%). Onmore » the basis of this chemical composition, we have devised an in situ growth of highly air (upto ~1.5 months) and thermally-stable (≤300°C), tetragonal-phased, variable-sized polycrystals (~100 nm-10 μm) amendable for large-area deposition, and ultimately, large-scale manufacturing. This method is encouraging for stable optoelectronic devices, and leads to energy-efficient and low-cost processing.« less

  12. 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

  13. Ceramic Single Phase High-Level Nuclear Waste Forms: Hollandite, Perovskite, and Pyrochlore

    NASA Astrophysics Data System (ADS)

    Vetter, M.; Wang, J.

    2017-12-01

    The lack of viable options for the safe, reliable, and long-term storage of nuclear waste is one of the primary roadblocks of nuclear energy's sustainable future. The method being researched is the incorporation and immobilization of harmful radionuclides (Cs, Sr, Actinides, and Lanthanides) into the structure of glasses and ceramics. Borosilicate glasses are the main waste form that is accepted and used by today's nuclear industry, but they aren't the most efficient in terms of waste loading, and durability is still not fully understood. Synroc-phase ceramics (i.e. hollandite, perovskite, pyrochlore, zirconolite) have many attractive qualities that glass waste forms do not: high waste loading, moderate thermal expansion and conductivity, high chemical durability, and high radiation stability. The only downside to ceramics is that they are more complex to process than glass. New compositions can be discovered by using an Artificial Neural Network (ANN) to have more options to optimize the composition, loading for performance by analyzing the non-linear relationships between ionic radii, electronegativity, channel size, and a mineral's ability to incorporate radionuclides into its structure. Cesium can be incorporated into hollandite's A-site, while pyrochlore and perovskite can incorporate actinides and lanthanides into their A-site. The ANN is used to predict new compositions based on hollandite's channel size, as well as the A-O bond distances of pyrochlore and perovskite, and determine which ions can be incorporated. These new compositions will provide more options for more experiments to potentially improve chemical and thermodynamic properties, as well as increased waste loading capabilities.

  14. Enhancement of thermoelectric performance in strontium titanate by praseodymium substitution

    NASA Astrophysics Data System (ADS)

    Kovalevsky, A. V.; Yaremchenko, A. A.; Populoh, S.; Weidenkaff, A.; Frade, J. R.

    2013-02-01

    In order to identify the effects of Pr additions on thermoelectric properties of strontium titanate, crystal structure, electrical and thermal conductivity, and Seebeck coefficient of Sr1-xPrxTiO3 (x = 0.02-0.30) materials were studied at 400 < T < 1180 K under highly reducing atmosphere. The mechanism of electronic transport was found to be similar up to 10% of praseodymium content, where generation of the charge carriers upon substitution resulted in significant increase of the electrical conductivity, moderate decrease in Seebeck coefficient, and general improvement of the power factor. Formation of point defects in the course of substitution led to suppression of the lattice thermal conductivity, whilst the contribution from electronic component was increasing with carrier concentration. Possible formation of layered structures and growing distortion of the perovskite lattice resulted in relatively low thermoelectric performance for Sr0.80Pr0.20TiO3 and Sr0.70Pr0.30TiO3. The maximum dimensionless figure of merit was observed for Sr0.90Pr0.10TiO3 and amounted to ˜0.23 at 670 K and ˜0.34 at 1170 K, close to the values, obtained in similar conditions for the best bulk thermoelectrics, based on rare-earth substituted SrTiO3.

  15. Mechanical behavior and electrical conductivity of La1-xCaxCoO3 (x = 0, 0.2, 0.4, 0.55) perovskites

    SciTech Connect

    Pathak, Siddhartha; Steinmetz, David; Kuebler, Jakob

    2010-01-01

    This paper compares the important mechanical properties and the electrical conductivities from room temperature to 800oC of four LaCoO3 based cobaltite compositions with 0, 20, 40 and 55% Ca2+ ions substituted on the A site of the perovskite structure respectively. Ca2+ doped lanthanum cobaltite materials are strong candidates for use as cathodes in lower temperature solid oxide fuel cells operating at or below 800oC. Among these four cobaltite compositions, two (LaCoO3 and La0.8Ca0.2CoO3) were found to be phase pure materials, whereas the remaining two compositions (La0.6Ca0.4CoO3 and La0.45Ca0.55CoO3) contained precipitation of secondary phases such as CaO and Co3O4. The mechanicalmore » properties of the four compositions, in terms of Young s modulus, four-point bending strength and fracture toughness measurements, were measured at both room temperature and 800oC. At room temperature, doping with Ca2+ was found to substantially increase the mechanical properties of the cobaltites, whereas at 800oC the pure LaCoO3 composition exhibited higher modulus and strength values than La0.8Ca0.2CoO3. All of the four compositions exhibited ferroelastic behavior, as shown by the hysteresis loops generated during uniaxial load-unload compression tests. Electrical conductivity measurements showed the La0.8Ca0.2CoO3 composition to have the highest conductivity among the four compositions.« less

  16. X-ray absorption spectroscopy and neutron diffraction study of the perovskite-type rare-earth cobaltites

    NASA Astrophysics Data System (ADS)

    Sikolenko, V.; Efimova, E.; Franz, A.; Ritter, C.; Troyanchuk, I. O.; Karpinsky, D.; Zubavichus, Y.; Veligzhanin, A.; Tiutiunnikov, S. I.; Sazonov, A.; Efimov, V.

    2018-05-01

    Correlations between local and long-range structure distortions in the perovskite-type RE1-xSrxCoO3-δ (RE = La, Pr, Nd; x = 0.0 and 0.5) compounds have been studied at room temperature by extended X-ray absorption fine structure (EXAFS) at the Co K-edge and high-resolution neutron powder diffraction (NPD). The use of two complementary experimental techniques allowed us to explore the influence of the type of rare-earth element and strontium substitution on unusual behavior of static and dynamic features of both the Co-O bond lengths.

  17. 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.

  18. 4d Electronic structure analysis of ruthenium in the perovskite oxides by Ru K- and L-edge XAS.

    PubMed

    Kim, J Y; Hwang, S H; Kim, S J; Demazeau, G; Choy, J H; Shimada, H

    2001-03-01

    The 4d electronic structure of ruthenium in the perovskite oxides, La2MRuIVO6 (M = Zn, Mg, and Li) and Ba2YRuVO6, has been investigated by the Ru K-and L-edge XANES and EXAFS analyses. Such X-ray absorption spectroscopic results clarify that the RuIV (d4) and RuV (d3) ions are stabilized in nearly regular Oh site. Comparing the Ru L-edge XANES spectra of perovskites containing isovalent ruthenium, it has been found that the t2g state is mainly influenced by A site cation, whereas the eg is mainly affected by neighboring B site cation. The experimental EXAFS spectra in the range of R < or = approximately 4.5 A are well reproduced by ab-initio calculation based on crystallographic data, which supports the long-range structure presented by Rietveld refinement.

  19. 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

  20. Epitaxial Electrodeposition of Methylammonium Lead Iodide Perovskites

    DOE PAGES

    Koza, Jakub A.; Hill, James C.; Demster, Ashley C.; ...

    2015-12-16

    Here, an electrochemical/chemical route is introduced to deposit both textured and epitaxial films of methylammonium lead iodide (MAPbI 3) perovskites. The perovskite films are produced by chemical conversion of lead dioxide films that have been electrodeposited as either textured or epitaxial films onto [111]-textured Au and [100] and [111] single-crystal Au substrates. The epitaxial relationships for the MAPbI 3 films are MAPbI 3(001)[010]∥PbO 2(100)<001> and MAPbI 3(110)[111]∥PbO 2(100)<001> regardless of the Au substrate orientation, because the in-plane order of the converted film is controlled by the epitaxial PbO 2 precursor film. The textured and epitaxial MAPbI 3 films both havemore » trap densities lower than and photoluminescence intensities higher than those of polycrystalline films produced by spin coating.« less

  1. 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.

  2. 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,more » and material properties is discussed. Various chemical synthesis and processing methods for superior device performance in solar cells and optoelectronic devices are reviewed.« less

  3. Synthesis of solid solutions of perovskites

    SciTech Connect

    Dambekalne, M.Y.; Antonova, M.K.; Perro, I.T.

    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 theoreticalmore » value and showing zero apparent porosity and water absorption.« less

  4. 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

  5. Synthesis of a polar ordered oxynitride perovskite

    SciTech Connect

    Vadapoo, Rajasekarakumar; Ahart, Muhtar; Somayazulu, Maddury

    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)] 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 O 2 N stood out with huge predicted polarization and nonlinear optic coefficients. In this study, we demonstrate the synthesis of perovskite-structured YSi O 2 N by using a combination of a diamond-anvil cell and inmore » 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.« less

  6. [Generic drug substitution].

    PubMed

    Tamir, Orly; Halkin, Hillel; Shemer, Joshua

    2006-09-01

    The rapidly rising health care expenditures, attributed mainly to the high cost of prescription drugs, have led governments around the world to look to generics as a means of containing costs in the pharmaceutical market. Generic drugs provide a less expensive alternative to brand name drugs due to the elimination of the need to perform lengthy and costly clinical trials, as required for innovative drugs. Essentially, generic substitution of drugs may be performed only after showing unequivocally that the generic formulation is identical in its active ingredients, strength, and route of administration as its innovative counterpart, and that they are bioequivalent to each other. Although the two are in essence the same, generic substitution is occasionally a controversial matter.

  7. Acid–base catalysis over perovskites: a review

    SciTech Connect

    Polo-Garzon, Felipe; Wu, Zili

    We present that perovskite catalysts have been extensively studied for reduction–oxidation (redox) reactions; however, their acid–base catalytic properties are still under-explored. This review collects work aiming to study the acid–base catalytic properties of perovskites. Reports regarding combined acid–base/redox catalysis over perovskites lie beyond the scope of the present review. For the characterization of acid–base properties, researchers have studied the interaction of probe molecules with perovskite surfaces by means of multiple techniques that provide information about the density, strength and type of adsorption sites. The top-surface composition of perovskites, which relates to the abundance of the acid–base sites, has been studiedmore » by means of low energy ion scattering (LEIS), and, the less surface sensitive, conventional X-ray photoelectron spectroscopy (XPS). Probe reactions, with the conversion of 2-propanol as the common choice, have also been employed for characterizing the acid–base catalytic properties of perovskites. The complex nature of perovskite surfaces, which explains the still absent fundamental relations between the structure of the catalyst and reaction rates/selectivity, encounters a great challenge due to the surface reconstruction of these materials. In this review, we devote a special section to highlight recent publications that report the impact of surface reconstruction and particle shape on acid–base catalysis over perovskites. In addition, we review promising catalytic performances of perovskite catalysts for other reactions of interest. Challenges in acid–base catalysis over perovskites focus on the development of time-resolved monolayer-sensitive characterization of surfaces under operando conditions and the discernment of combined acid–base/redox reaction mechanisms. Finally, opportunities lay on tuning the acid–base characteristics of perovskites with computation-based catalytic descriptors to

  8. Acid–base catalysis over perovskites: a review

    DOE PAGES

    Polo-Garzon, Felipe; Wu, Zili

    2018-01-15

    We present that perovskite catalysts have been extensively studied for reduction–oxidation (redox) reactions; however, their acid–base catalytic properties are still under-explored. This review collects work aiming to study the acid–base catalytic properties of perovskites. Reports regarding combined acid–base/redox catalysis over perovskites lie beyond the scope of the present review. For the characterization of acid–base properties, researchers have studied the interaction of probe molecules with perovskite surfaces by means of multiple techniques that provide information about the density, strength and type of adsorption sites. The top-surface composition of perovskites, which relates to the abundance of the acid–base sites, has been studiedmore » by means of low energy ion scattering (LEIS), and, the less surface sensitive, conventional X-ray photoelectron spectroscopy (XPS). Probe reactions, with the conversion of 2-propanol as the common choice, have also been employed for characterizing the acid–base catalytic properties of perovskites. The complex nature of perovskite surfaces, which explains the still absent fundamental relations between the structure of the catalyst and reaction rates/selectivity, encounters a great challenge due to the surface reconstruction of these materials. In this review, we devote a special section to highlight recent publications that report the impact of surface reconstruction and particle shape on acid–base catalysis over perovskites. In addition, we review promising catalytic performances of perovskite catalysts for other reactions of interest. Challenges in acid–base catalysis over perovskites focus on the development of time-resolved monolayer-sensitive characterization of surfaces under operando conditions and the discernment of combined acid–base/redox reaction mechanisms. Finally, opportunities lay on tuning the acid–base characteristics of perovskites with computation-based catalytic descriptors to

  9. Quasiparticle Interference on Cubic Perovskite Oxide Surfaces.

    PubMed

    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

    2017-08-25

    We report the observation of coherent surface states on cubic perovskite oxide SrVO_{3}(001) thin films through spectroscopic-imaging scanning tunneling microscopy. A direct link between the observed quasiparticle interference patterns and the formation of a d_{xy}-derived surface state is supported by first-principles calculations. We show that the apical oxygens on the topmost VO_{2} plane play a critical role in controlling the coherent surface state via modulating orbital state.

  10. Magnetic field effects in hybrid perovskite devices

    NASA Astrophysics Data System (ADS)

    Zhang, C.; Sun, D.; Sheng, C.-X.; Zhai, Y. X.; Mielczarek, K.; Zakhidov, A.; Vardeny, Z. V.

    2015-05-01

    Magnetic field effects have been a successful tool for studying carrier dynamics in organic semiconductors as the weak spin-orbit coupling in these materials gives rise to long spin relaxation times. As the spin-orbit coupling is strong in organic-inorganic hybrid perovskites, which are promising materials for photovoltaic and light-emitting applications, magnetic field effects are expected to be negligible in these optoelectronic devices. We measured significant magneto-photocurrent, magneto-electroluminescence and magneto-photoluminescence responses in hybrid perovskite devices and thin films, where the amplitude and shape are correlated to each other through the electron-hole lifetime, which depends on the perovskite film morphology. We attribute these responses to magnetic-field-induced spin-mixing of the photogenerated electron-hole pairs with different g-factors--the Δg model. We validate this model by measuring large Δg (~ 0.65) using field-induced circularly polarized photoluminescence, and electron-hole pair lifetime using picosecond pump-probe spectroscopy.

  11. 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 ABX 3 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 reviewedmore » with an eye toward their potential application in emerging optoelectronic technologies. Significant attention is given to the prototypical compound methylammonium lead iodide (CH 3NH 3PbI 3) 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

  12. Light-trapping in perovskite solar cells

    SciTech Connect

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

    We numerically demonstrate enhanced light harvesting efficiency in both CH 3NH 3PbI 3 and CH(NH 2) 2PbI 3-based perovskite solar cells using inverted verticalcone photonic-crystal nanostructures. For CH 3NH 3PbI 3 perovskite solar cells, the maximum achievable photocurrent density (MAPD) reaches 25.1 mA/cm 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 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 60more » degree for both S- and P- polarizations. For the corresponding CH(NH 2) 2PbI 3 based perovskite solar cell, with absorption range of 300 nm to 850 nm, we find a MAPD of 29.1 mA/cm 2, corresponding to 95.4% of the total available photocurrent. Furthermore, the projected power conversion efficiency of the CH(NH 2) 2PbI 3 based photonic crystal solar cell is 23.4%, well above the current world record efficiency of 20.1%.« less

  13. 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 CH 3NH 3PbI 3 and CH(NH 2) 2PbI 3-based perovskite solar cells using inverted verticalcone photonic-crystal nanostructures. For CH 3NH 3PbI 3 perovskite solar cells, the maximum achievable photocurrent density (MAPD) reaches 25.1 mA/cm 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 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 60more » degree for both S- and P- polarizations. For the corresponding CH(NH 2) 2PbI 3 based perovskite solar cell, with absorption range of 300 nm to 850 nm, we find a MAPD of 29.1 mA/cm 2, corresponding to 95.4% of the total available photocurrent. Furthermore, the projected power conversion efficiency of the CH(NH 2) 2PbI 3 based photonic crystal solar cell is 23.4%, well above the current world record efficiency of 20.1%.« less

  14. 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.

  15. 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

  16. Effect of lone-electron-pair cations on the orientation of crystallographic shear planes in anion-deficient perovskites.

    PubMed

    Batuk, Dmitry; Batuk, Maria; Abakumov, Artem M; Tsirlin, Alexander A; McCammon, Catherine; Dubrovinsky, Leonid; Hadermann, Joke

    2013-09-03

    Factors affecting the structure and orientation of the crystallographic shear (CS) planes in anion-deficient perovskites were investigated using the (Pb(1-z)Sr(z))(1-x)Fe(1+x)O(3-y) perovskites as a model system. The isovalent substitution of Sr(2+) for Pb(2+) highlights the influence of the A cation electronic structure because these cations exhibit very close ionic radii. Two compositional ranges have been identified in the system: 0.05 ≤ z ≤ 0.2, where the CS plane orientation gradually varies but stays close to (203)p, and 0.3 ≤ z ≤ 0.45 with (101)p CS planes. The incommensurately modulated structure of Pb0.792Sr0.168Fe1.040O2.529 was refined from neutron powder diffraction data using the (3 + 1)D approach (space group X2/m(α0γ), X = (1/2, 1/2, 1/2, 1/2), a = 3.9512(1) Å, b = 3.9483(1) Å, c = 3.9165(1) Å, β = 93.268(2)°, q = 0.0879(1)a* + 0.1276(1)c*, RF = 0.023, RP = 0.029, and T = 900 K). A comparison of the compounds with different CS planes indicates that the orientation of the CS planes is governed mainly by the stereochemical activity of the lone-electron-pair cations inside the perovskite blocks.

  17. NREL Technique Leads to Improved Perovskite Solar Cells | News | NREL

    Science.gov Websites

    ), devised a method to improve perovskite solar cells, making them more efficient and reliable with higher according to the skills of the researchers making perovskites at different laboratories, to somewhere cell. The scientists from NREL and SJTU came up with a better method, using what's called the Ostwald

  18. Perovskite Technology is Scalable, But Questions Remain about the Best

    Science.gov Websites

    Methods | News | NREL Perovskite Technology is Scalable, But Questions Remain about the Best Methods News Release: Perovskite Technology is Scalable, But Questions Remain about the Best Methods NREL be used on a larger surface. The NREL researchers examined potential scalable deposition methods

  19. NREL Scientists Demonstrate Remarkable Stability in Perovskite Solar Cells

    Science.gov Websites

    environmentally stable, high-efficiency perovskite solar cell, bringing the emerging technology a step closer to needed to make the devices durable enough for long-term use. NREL's unencapsulated solar cell-a cell used Unencapsulated Perovskite Solar Cells for >1000 Hours of Operational Stability." "A solar cell in

  20. Impact of Interfacial Layers in Perovskite Solar Cells.

    PubMed

    Cho, An-Na; Park, Nam-Gyu

    2017-10-09

    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.

  1. 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.

  2. Economic aspects of drug substitution

    PubMed Central

    Salehi, Hossein; Schweitzer, Stuart O.

    1985-01-01

    One of the major directions of health policy is the attempt to contain expenditures on pharmaceuticals by encouraging substitution of generic for brand name drug products. Yet, a major marketing survey of prescribing and dispensing patterns in California in 1977 found relatively little drug substitution occurring, and in fact substitution of more expensive products occurred more frequently than did substitution of less expensive products. This article tests alternative models of pharmacy dispensing behavior to better explain substitution patterns and it estimates price functions to measure the extent to which cost savings on generic products are passed on to consumers. PMID:10311162

  3. 40 CFR 721.981 - Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.981 Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex. (a) Chemical substance and significant new...

  4. 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.

  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. Perovskite-fullerene hybrid materials suppress hysteresis in planar diodes

    NASA Astrophysics Data System (ADS)

    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.

    2015-05-01

    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.

  7. 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

  8. Planar-integrated single-crystalline perovskite photodetectors

    PubMed Central

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

    2015-01-01

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

  9. 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.

  10. 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.

  11. Reconditioning perovskite films in vapor environments through repeated cation doping

    NASA Astrophysics Data System (ADS)

    Boonthum, Chirapa; Pinsuwan, Kusuma; Ponchai, Jitprabhat; Srikhirin, Toemsak; Kanjanaboos, Pongsakorn

    2018-06-01

    Perovskites have attracted considerable attention for application as high-efficiency photovoltaic devices owing to their low-cost and low-temperature fabrication. A good surface and high crystallinity are necessary for high-performance devices. We examine the negative effects of chemical ambiences on the perovskite crystal formation and morphology. The repeated cation doping (RCD) technique was developed to remedy these issues by gradually dropping methylammonium ions on top of about-to-form perovskite surfaces to cause recrystallization. RCD promotes pinhole-free, compact, and polygonal-like surfaces under various vapor conditions. Furthermore, it enhances the electronic properties and crystallization. The benefits of RCD extend beyond perovskites under vapor ambiences, as it can improve regular and wasted perovskites.

  12. Synthesis and applications of nanoporous perovskite metal oxides

    PubMed Central

    Huang, Xiubing; Zhao, Guixia

    2018-01-01

    Perovskite-type metal oxides have been widely investigated and applied in various fields in the past several decades due to their extraordinary variability of compositions and structures with targeted physical and chemical properties (e.g., redox behaviour, oxygen mobility, electronic and ionic conductivity). Recently, nanoporous perovskite metal oxides have attracted extensive attention because of their special morphology and properties, as well as superior performance. This minireview aims at summarizing and reviewing the different synthesis methods of nanoporous perovskite metal oxides and their various applications comprehensively. The correlations between the nanoporous structures and the specific performance of perovskite oxides are summarized and highlighted. The future research directions of nanoporous perovskite metal oxides are also prospected. PMID:29862001

  13. Double perovskites overtaking the single perovskites: A set of new solar harvesting materials with much higher stability and efficiency

    NASA Astrophysics Data System (ADS)

    Kangsabanik, Jiban; Sugathan, Vipinraj; Yadav, Anuradha; Yella, Aswani; Alam, Aftab

    2018-05-01

    Solar energy plays an important role in substituting the ever declining source of fossil fuel energy. Finding novel materials for solar cell applications is an integral part of photovoltaic research. Hybrid lead halide perovskites are one of, if not the most, well sought material in the photovoltaic research community. Its unique intrinsic properties, flexible synthesis techniques, and device fabrication architecture made the community highly buoyant over the past few years. Yet, there are two fundamental issues that still remain a concern, i.e., the stability in external environment and the toxicity due to Pb. This led to a search for alternative materials. More recently, double perovskite [A2B B'X6 (X =Cl, Br, I)] materials have emerged as a promising choice. Few experimental synthesis and high throughput computational studies have been carried out to check for promising candidates of this class. The main outcome from these studies, however, can essentially be summarized into two categories: (i) either they have an indirect band gap or (ii) a direct but large optical band gap, which is not suitable for solar devices. Here we propose a large set of stable double perovskite materials, Cs2B B 'X6 (X =Cl, Br, I), which show indirect to direct band gap transition via small Pb+2 doping at both B and B'sites. This is done by careful band (orbital) engineering using first-principles calculations. This kind of doping has helped to change the topology of the band structure, triggering an indirect to direct transition that is optically allowed. It also reduces the band gap significantly, bringing it well into the visible region. We also simulated the optical absorption spectra of these systems and found a comparable/higher absorption coefficient and solar efficiency with respect to the state of the art photovoltaic absorber material CH3NH3PbI3 . A number of materials Cs2(B0.75Pb0.25) (B0.75'Pb0.25) X6 (for various combinations of B ,B ', and X ) are found to be promising

  14. Methodologies in Creating Skin Substitutes

    PubMed Central

    Nicholas, Mathew N; Jeschke, Marc G; Amini-Nik, Saeid

    2016-01-01

    The creation of skin substitutes has significantly decreased morbidity and mortality of skin wounds. Although there are still a number of disadvantages of currently available skin substitutes, there has been a significant decline in research advances over the past several years in improving these skin substitutes. Clinically most skin substitutes used are acellular and do not use growth factors to assist wound healing, key areas of potential in this field of research. This article discusses the five necessary attributes of an ideal skin substitute. It comprehensively discusses the three major basic components of currently available skin substitutes: scaffold materials, growth factors, and cells, comparing and contrasting what has been used so far. It then examines a variety of techniques in how to incorporate these basic components together to act as a guide for further research in the field to create cellular skin substitutes with clinically better results. PMID:27154041

  15. 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

  16. 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.

  17. First-principles thermodynamics study of phase stability in inorganic halide perovskite solid solutions

    NASA Astrophysics Data System (ADS)

    Bechtel, Jonathon S.; Van der Ven, Anton

    2018-04-01

    Halide substitution gives rise to a tunable band gap as a function of composition in halide perovskite materials. However, photoinduced phase segregation, observed at room temperature in mixed halide A Pb (IxBr1-x) 3 systems, limits open circuit voltages and decreases photovoltaic device efficiencies. We investigate equilibrium phase stability of orthorhombic P n m a γ -phase CsM (XxY1-x) 3 perovskites where M is Pb or Sn, and X and Y are Br, Cl, or I. Finite-temperature phase diagrams are constructed using a cluster expansion effective Hamiltonian parameterized from first-principles density-functional-theory calculations. Solid solution phases for CsM (IxBr1-x) 3 and CsM (BrxCl1-x) 3 are predicted to be stable well below room temperature while CsM (IxCl1-x) 3 systems have miscibility gaps that extend above 400 K. The height of the miscibility gap correlates with the difference in volume between end members. Also layered ground states are found on the convex hull at x =2 /3 for CsSnBr2Cl ,CsPbI2Br , and CsPbBrCl2. The impact of these ground states on the finite temperature phase diagram is discussed in the context of the experimentally observed photoinduced phase segregation.

  18. Trifluoromethyl-substituted polymers

    NASA Technical Reports Server (NTRS)

    1993-01-01

    Current work sponsored by the grant at Southwest Texas State University is directed toward the synthesis and characterization of: (1) N-alkylated polyamides derived from o-fluorinated diacids; (2) highly fluorinated polyethers; (3) polyesters derived from 2-hydroxy-2-propyl substituted arenes and/or 2,5-difluoroterephthalic acid; and (4) silicon-containing fluoropolymers. Work during the period from 1 July to 31 Dec. 1993 focused primarily on items 3 and 4 and on the development of a phosphorus containing modification of '12F-PEK.'

  19. Soluble Ethylmercapto Substituted Polythiophenes

    DTIC Science & Technology

    1988-09-27

    r - * aS 7 C- CgSnrmnue on reverse if necessary ari a envtiy OY aOCK numnoer) Polymners o -vmrat and 3’.4-bis(ethyirrercapto’ thiophenes have been...svrnthesized and Cn’ara’cserized. These polymers are soluble in com mon organic soivents such as mehlen c0oie cirrr and T1{F. Su-ucsjr...icharacserizanion using FT-ER and NMNR specuaoscopy show that these polymners have a * ve~~Jer~ed( tnlimercamto substituted 1.5-(thienylene) ocjivmeric structure

  20. Hexavalent Chromium Substitution Projects

    DTIC Science & Technology

    2011-05-12

    Hexavalent Chromium Substitution Projects Date (12 May 2011) Gene McKinley ASC/WNV (937) 255-3596 Gene.McKinley@wpafb.af.mil Aeronautical Systems...valid OMB control number. 1. REPORT DATE 12 MAY 2011 2. REPORT TYPE 3. DATES COVERED 00-00-2011 to 00-00-2011 4. TITLE AND SUBTITLE Hexavalent ...A-10) – AETC (T-6, T-38 and T1A) • Both Cr Primers & Non-Cr primers as well as Cr Surface Treatment – F-22 8 Non- Chrome Tie-coat & touch-up

  1. Density functional calculations of carbon substituting for Zr in barium zirconate

    NASA Astrophysics Data System (ADS)

    Al-Hadidi, Meaad; Goss, J. P.; Al-Ani, Oras A.; Briddon, P. R.; Rayson, M. J.

    2017-06-01

    Oxide perovskites such as BaZrO3 possess many significant properties which render them useful in many technological and scientific applications such as sensors, optoelectronics, laser frequency doubling and high capacity memory cells. Several methods are used to grow BaZrO3 crystal, and organic species that may be present during growth lead to carbon contamination. We have investigated, using density-functional theory, the role of carbon impurities on the structural, electrical and electronic properties of carbon substituting of Zr in cubic barium zirconate. The local vibrational modes of the defect centre has been calculated and we suggest it is a feasible route to experimental identification

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

    NASA Astrophysics Data System (ADS)

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

    2018-05-01

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

  3. First principles study on mixed orthorhombic perovskite CH3NH3 Pb(I1-xBrx) 3

    NASA Astrophysics Data System (ADS)

    Fang, Zhou; Yi, Zhijun

    2017-11-01

    Chemically tuned inorganic-organic hybrid halide perovskites based on iodine and bromine halide anions have been studied using first-principles calculations. Firstly, our results show that the volume of CH3NH3 Pb(I1-xBrx) 3 decreases linearly with the concentration of Br ions, and the band gap can be tuned from 1.9 eV to 2.3 eV by substituting I with Br, resulting in the shift of absorption onset from 650 nm (1.9 eV) to 540 nm (2.3 eV). Secondly, our calculations show that the color of crystal can be tuned from wine to yellow by substituting I with Br.

  4. Characterization of mixed-conducting barium cerate-based perovskites for potential fuel cell applications

    NASA Astrophysics Data System (ADS)

    Mukundan, R.

    levels (≥40 mole%) due to an enhancement of the electronic conductivity. The Ba(Prsb{0.8}Gdsb{0.2})Osb{2.9} sample was found to have the best mixed-conducting properties of all the perovskites evaluated, sigmasb{T}=0.75 S/cm in air at 800sp°C, tsb{H+}=0.15 in a wet argon//dry argon gradient, and tsb{0.2-}≈ 0.05 in a dry air//dry argon gradient. The cathodic overpotentials of the mixed-conducting Pr-doped barium cerates were low, and decreased with increasing ionic and electronic conductivity of the electrode. The lowest overpotential was obtained for the Ba(Prsb{0.8}Gdsb{0.2})Osb{2.9}, cathode, and at low current densities was comparable to that of an optimized porous Pt-electrode. While the substitution of Nb and Ta for Ce lead to an enhancement in the electronic conductivity under reducing conditions associated with the increased reduction of Cesp{4+} to Cesp{3+}, the ionic-conductivity of these perovskites was low. There was no evidence for any protonic conductivity in the 15 mole% Nb and Ta substituted barium cerates. Moreover the anodic overpotential and the anode resistance of these perovskites on a Ba(Cesb{0.8}Gdsb{0.2})Osb{2.9} electrolyte were both high.

  5. Band gap and mobility of epitaxial perovskite BaSn1 -xHfxO3 thin films

    NASA Astrophysics Data System (ADS)

    Shin, Juyeon; Lim, Jinyoung; Ha, Taewoo; Kim, Young Mo; Park, Chulkwon; Yu, Jaejun; Kim, Jae Hoon; Char, Kookrin

    2018-02-01

    A wide band-gap perovskite oxide BaSn O3 is attracting much attention due to its high electron mobility and oxygen stability. On the other hand, BaHf O3 was recently reported to be an effective high-k gate oxide. Here, we investigate the band gap and mobility of solid solutions of BaS n1 -xH fxO3 (x =0 -1 ) (BSHO) as a basis to build advanced perovskite oxide heterostructures. All the films were epitaxially grown on MgO substrates using pulsed laser deposition. Density functional theory calculations confirmed that Hf substitution does not create midgap states while increasing the band gap. From x-ray diffraction and optical transmittance measurements, the lattice constants and the band-gap values are significantly modified by Hf substitution. We also measured the transport properties of n -type La-doped BSHO films [(Ba ,La ) (Sn ,Hf ) O3 ] , investigating the feasibility of modulation doping in the BaSn O3/BSHO heterostructures. The Hall measurement data revealed that, as the Hf content increases, the activation rate of the La dopant decreases and the scattering rate of the electrons sharply increases. These properties of BSHO films may be useful for applications in various heterostructures based on the BaSn O3 system.

  6. 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.

  7. 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

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

    SciTech Connect

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin

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

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

    PubMed

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

    2016-08-01

    Organic-inorganic hybrid perovskites have cemented their position as an exceptional class of optoelectronic materials thanks to record photovoltaic efficiencies of 22.1%, as well as promising demonstrations of light-emitting diodes, lasers, and light-emitting transistors. Perovskite materials with photoluminescence quantum yields close to 100% and perovskite light-emitting diodes with external quantum efficiencies of 8% and current efficiencies of 43 cd A(-1) have been achieved. Although perovskite light-emitting devices are yet to become industrially relevant, in merely two years these devices have achieved the brightness and efficiencies that organic light-emitting diodes accomplished in two decades. Further advances will rely decisively on the multitude of compositional, structural variants that enable the formation of lower-dimensionality layered and three-dimensional perovskites, nanostructures, charge-transport materials, and device processing with architectural innovations. Here, the rapid advancements in perovskite light-emitting devices and lasers are reviewed. The key challenges in materials development, device fabrication, operational stability are addressed, and an outlook is presented that will address market viability of perovskite light-emitting devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Random lasing actions in self-assembled perovskite nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Shuai; Sun, Wenzhao; Li, Jiankai; Gu, Zhiyuan; Wang, Kaiyang; Xiao, Shumin; Song, Qinghai

    2016-05-01

    Solution-based perovskite nanoparticles have been intensively studied in the past few years due to their applications in both photovoltaic and optoelectronic devices. Here, based on the common ground between solution-based perovskite and random lasers, we have studied the mirrorless lasing actions in self-assembled perovskite nanoparticles. After synthesis from a solution, discrete lasing peaks have been observed from optically pumped perovskites without any well-defined cavity boundaries. We have demonstrated that the origin of the random lasing emissions is the scattering between the nanostructures in the perovskite microplates. The obtained quality (Q) factors and thresholds of random lasers are around 500 and 60 μJ/cm2, respectively. Both values are comparable to the conventional perovskite microdisk lasers with polygon-shaped cavity boundaries. From the corresponding studies on laser spectra and fluorescence microscope images, the lasing actions are considered random lasers that are generated by strong multiple scattering in random gain media. In additional to conventional single-photon excitation, due to the strong nonlinear effects of perovskites, two-photon pumped random lasers have also been demonstrated for the first time. We believe this research will find its potential applications in low-cost coherent light sources and biomedical detection.

  11. Perovskite/Carbon Composites: Applications in Oxygen Electrocatalysis.

    PubMed

    Zhu, Yinlong; Zhou, Wei; Shao, Zongping

    2017-03-01

    Oxygen electrocatalysis, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), plays an extremely important role in oxygen-based renewable-energy technologies such as rechargeable metal-air batteries, regenerative fuel cells and water splitting. Perovskite oxides have recently attracted increasing interest and hold great promise as efficient ORR and OER catalysts to replace noble-metal-based catalysts, owing to their high intrinsic catalytic activity, abundant variety, low cost, and rich resources. The introduction of perovskite-carbon interfaces by forming perovskite/carbon composites may bring a synergistic effect between the two phases, thus benefiting the oxygen electrocatalysis. This review provides a comprehensive overview of recent advances in perovskite/carbon composites for oxygen electrocatalysis in alkaline media, aiming to provide insights into the key parameters that influence the ORR/OER performance of the composites, including the physical/chemical properties and morphologies of the perovskites, the multiple roles of carbon, the synthetic method and the synergistic effect. A special emphasis is placed on the origin of the synergistic effect associated with the interfacial interaction between the perovskite and the carbon phases for enhanced ORR/OER performance. Finally, the existing challenges and the future directions for the synthesis and development of more efficient oxygen catalysts based on perovskite/carbon composites are proposed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    DOE PAGES

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; ...

    2016-03-01

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

  13. Improving the photovoltaic performance of perovskite solar cells with acetate

    PubMed Central

    Zhao, Qian; Li, G. R.; Song, Jian; Zhao, Yulong; Qiang, Yinghuai; Gao, X. P.

    2016-01-01

    In an all-solid-state perovskite solar cell, methylammonium lead halide film is in charge of generating photo-excited electrons, thus its quality can directly influence the final photovoltaic performance of the solar cell. This paper accentuates a very simple chemical approach to improving the quality of a perovskite film with a suitable amount of acetic acid. With introduction of acetate ions, a homogeneous, continual and hole-free perovskite film comprised of high-crystallinity grains is obtained. UV-visible spectra, steady-state and time-resolved photoluminescence (PL) spectra reveal that the obtained perovskite film under the optimized conditions shows a higher light absorption, more efficient electron transport, and faster electron extraction to the adjoining electron transport layer. The features result in the optimized perovskite film can provide an improved short-circuit current. The corresponding solar cells with a planar configuration achieves an improved power conversion efficiency of 13.80%, and the highest power conversion efficiency in the photovoltaic measurements is up to 14.71%. The results not only provide a simple approach to optimizing perovskite films but also present a novel angle of view on fabricating high-performance perovskite solar cells. PMID:27934924

  14. Improving the photovoltaic performance of perovskite solar cells with acetate.

    PubMed

    Zhao, Qian; Li, G R; Song, Jian; Zhao, Yulong; Qiang, Yinghuai; Gao, X P

    2016-12-09

    In an all-solid-state perovskite solar cell, methylammonium lead halide film is in charge of generating photo-excited electrons, thus its quality can directly influence the final photovoltaic performance of the solar cell. This paper accentuates a very simple chemical approach to improving the quality of a perovskite film with a suitable amount of acetic acid. With introduction of acetate ions, a homogeneous, continual and hole-free perovskite film comprised of high-crystallinity grains is obtained. UV-visible spectra, steady-state and time-resolved photoluminescence (PL) spectra reveal that the obtained perovskite film under the optimized conditions shows a higher light absorption, more efficient electron transport, and faster electron extraction to the adjoining electron transport layer. The features result in the optimized perovskite film can provide an improved short-circuit current. The corresponding solar cells with a planar configuration achieves an improved power conversion efficiency of 13.80%, and the highest power conversion efficiency in the photovoltaic measurements is up to 14.71%. The results not only provide a simple approach to optimizing perovskite films but also present a novel angle of view on fabricating high-performance perovskite solar cells.

  15. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    SciTech Connect

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou

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

  16. Electronic doping of transition metal oxide perovskites

    SciTech Connect

    Cammarata, Antonio, E-mail: cammaant@fel.cvut.cz; Rondinelli, James M.

    2016-05-23

    CaFeO{sub 3} is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO{sub 3}. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

  17. Explicit Substitutions and All That

    NASA Technical Reports Server (NTRS)

    Ayala-Rincon, Mauricio; Munoz, Cesar; Busnell, Dennis M. (Technical Monitor)

    2000-01-01

    Explicit substitution calculi are extensions of the Lambda-calculus where the substitution mechanism is internalized into the theory. This feature makes them suitable for implementation and theoretical study of logic-based tools such as strongly typed programming languages and proof assistant systems. In this paper we explore new developments on two of the most successful styles of explicit substitution calculi: the lambda(sigma)- and lambda(s(e))-calculi.

  18. Explicit Substitutions and All That

    NASA Technical Reports Server (NTRS)

    Ayala-Rincon, Mauricio; Munoz, Cesar

    2000-01-01

    Explicit substitution calculi are extensions of the lambda-calculus where the substitution mechanism is internalized into the theory. This feature makes them suitable for implementation and theoretical study of logic-based tools such as strongly typed programming languages and proof assistant systems. In this paper we explore new developments on two of the most successful styles of explicit substitution calculi: the lambda sigma- and lambda S(e)-calculi.

  19. Why does trigonometric substitution work?

    NASA Astrophysics Data System (ADS)

    Cunningham, Daniel W.

    2018-05-01

    Modern calculus textbooks carefully illustrate how to perform integration by trigonometric substitution. Unfortunately, most of these books do not adequately justify this powerful technique of integration. In this article, we present an accessible proof that establishes the validity of integration by trigonometric substitution. The proof offers calculus instructors a simple argument that can be used to show their students that trigonometric substitution is a valid technique of integration.

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

    NASA Astrophysics Data System (ADS)

    Kang, Sung Gu

    2018-06-01

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

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

    NASA Astrophysics Data System (ADS)

    Colomer, M. T.; Kilner, J. A.

    2015-08-01

    This work reports the effect of two different sintering times, 6 and 48 h on the structural, microstructural, and chemical features of Ni-doped La0.90Sr0.10GaO3.00-δ. Independently of the sintering time, La0.90Sr0.10Ga1-xNixO3.00-δ (where x=0.10, and 0.20 (mol)) presents a rhombohedral symmetry with a lattice volume that decreases when NiO dopant increases. Besides the perovskite, LaSrGa3.00O7.00 (nominal composition) is present as second phase in all cases. When the samples are doped with NiO, the peaks of this second phase are shifted with respect to the peaks of the pure phase. These shifts suggest that this second phase could admit some Ni ions in its structure. According to the XRD patterns, the amount of the latter phase is larger when sintering time is increased. Electron probe microanalysis (EPMA) indicated that the matrix of the samples sintered for 6 h is constituted by a perovskite with an experimental composition very close to the nominal one. However, when the samples are sintered for 48 h the matrix of each sample is constituted by two perovskites; both with compositional deviations with respect to their nominal one. In particular, a significant Sr depletion compensated by a La increment in the A site is observed. Those compositional deviations could be mainly due to the diffusion of the cations in the bulk and/or from the bulk to the surface of the samples. That diffusion can favour the formation, not only, of a second perovskite with a different composition in relation with the first one formed, but also, the formation of second phases. In addition, a very slight broadening of Bragg peaks of the perovskites sintered for 48 h is observed by XRD and can be related to the presence of two different perovskites in each sample according to EPMA results. By BSEM and EPMA analyses La4.00Ga2.00O9.00 (nominal composition) is also observed as second phase when samples are treated for 48 h.

  2. Thermoelectric Properties of the Ca1- x R x MnO3 Perovskite System (R: Pr, Nd, Sm) for High-Temperature Applications

    NASA Astrophysics Data System (ADS)

    Choi, Soon-Mok; Lim, Chang-Hyun; Seo, Won-Seon

    2011-05-01

    Perovskite oxides have attracted considerable attention in the area of thermoelectrics owing to the advantages of their isotropic crystal structure and straightforward control of their electrical properties. Among the many perovskites, different types of polycrystalline Ca1- x R x MnO3 (R: Pr, Nd, Sm) were prepared by solid-state reaction in this study. Three different rare-earth dopants were substituted at the Ca-ion site at various amounts. Considering phase stability, rare-earth ions with nearly the same ionic radius as Ca2+ were selected. To assess thermoelectric performance, the electrical conductivity, Seebeck coefficient, and power factor were measured, and phase analysis was conducted. The effects of ionic radius variation on single phase formation and the effect of doping amount on carrier concentration are discussed.

  3. Topochemical synthesis of cation ordered double perovskite oxynitrides.

    PubMed

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

    2017-04-19

    Topochemical nitridation in ammonia at moderate temperatures of cation ordered Sr 2 FeWO 6 produces new antiferromagnetic double perovskite oxynitrides Sr 2 FeWO 6-x N x with 0 < x ≤ 1. Nitrogen introduction induces the oxidation of Fe 2+ to Fe 3+ and decreases T N from 38 K (x = 0) to 13 K for Sr 2 FeWO 5 N which represents the first example of a double perovskite oxynitride with both high cationic order and nitrogen content. This synthetic approach can be extended to other cation combinations expanding the possibility of new materials in the large group of double perovskites.

  4. High-pressure synthesis of the cubic perovskite BaRuO3 and evolution of ferromagnetism in ARuO3 (A = Ca, Sr, Ba) ruthenates.

    PubMed

    Jin, C-Q; Zhou, J-S; Goodenough, J B; Liu, Q Q; Zhao, J G; Yang, L X; Yu, Y; Yu, R C; Katsura, T; Shatskiy, A; Ito, E

    2008-05-20

    The cubic perovskite BaRuO(3) has been synthesized under 18 GPa at 1,000 degrees C. Rietveld refinement indicates that the new compound has a stretched Ru-O bond. The cubic perovskite BaRuO(3) remains metallic to 4 K and exhibits a ferromagnetic transition at T(c) = 60 K, which is significantly lower than the T(c) approximately = 160 K for SrRuO(3). The availability of cubic perovskite BaRuO(3) not only makes it possible to map out the evolution of magnetism in the whole series of ARuO(3) (A = Ca, Sr, Ba) as a function of the ionic size of the A-site r(A,) but also completes the polytypes of BaRuO(3). Extension of the plot of T(c) versus r(A) in perovskites ARuO(3) (A = Ca, Sr, Ba) shows that T(c) does not increase as the cubic structure is approached, but has a maximum for orthorhombic SrRuO(3). Suppressing T(c) by Ca and Ba doping in SrRuO(3) is distinguished by sharply different magnetic susceptibilities chi(T) of the paramagnetic phase. This distinction has been interpreted in the context of a Griffiths' phase on the (Ca Sr)RuO(3) side and bandwidth broadening on the (Sr,Ba)RuO(3) side.

  5. High-pressure synthesis of the cubic perovskite BaRuO3 and evolution of ferromagnetism in ARuO3 (A = Ca, Sr, Ba) ruthenates

    PubMed Central

    Jin, C.-Q.; Zhou, J.-S.; Goodenough, J. B.; Liu, Q. Q.; Zhao, J. G.; Yang, L. X.; Yu, Y.; Yu, R. C.; Katsura, T.; Shatskiy, A.; Ito, E.

    2008-01-01

    The cubic perovskite BaRuO3 has been synthesized under 18 GPa at 1,000°C. Rietveld refinement indicates that the new compound has a stretched Ru–O bond. The cubic perovskite BaRuO3 remains metallic to 4 K and exhibits a ferromagnetic transition at Tc = 60 K, which is significantly lower than the Tc ≈ 160 K for SrRuO3. The availability of cubic perovskite BaRuO3 not only makes it possible to map out the evolution of magnetism in the whole series of ARuO3 (A = Ca, Sr, Ba) as a function of the ionic size of the A-site rA, but also completes the polytypes of BaRuO3. Extension of the plot of Tc versus rA in perovskites ARuO3 (A = Ca, Sr, Ba) shows that Tc does not increase as the cubic structure is approached, but has a maximum for orthorhombic SrRuO3. Suppressing Tc by Ca and Ba doping in SrRuO3 is distinguished by sharply different magnetic susceptibilities χ(T) of the paramagnetic phase. This distinction has been interpreted in the context of a Griffiths' phase on the (Ca Sr)RuO3 side and bandwidth broadening on the (Sr,Ba)RuO3 side. PMID:18480262

  6. Microscopic origin of entropy-driven polymorphism in hybrid organic-inorganic perovskite materials

    NASA Astrophysics Data System (ADS)

    Butler, Keith T.; Svane, Katrine; Kieslich, Gregor; Cheetham, Anthony K.; Walsh, Aron

    2016-11-01

    Entropy is a critical, but often overlooked, factor in determining the relative stabilities of crystal phases. The importance of entropy is most pronounced in softer materials, where small changes in free energy can drive phase transitions, which has recently been demonstrated in the case of organic-inorganic hybrid-formate perovskites. In this Rapid Communication we demonstrate the interplay between composition and crystal structure that is responsible for the particularly pronounced role of entropy in determining polymorphism in hybrid organic-inorganic materials. Using ab initio based lattice dynamics, we probe the origins and effects of vibrational entropy of four archetype perovskite (A B X3 ) structures. We consider an inorganic material (SrTiO3), an A -site hybrid-halide material (CH3NH3) PbI3 , a X -site hybrid material KSr (BH4)3 , and a mixed A - and X -site hybrid-formate material (N2H5) Zn (HCO2)3 , comparing the differences in entropy between two common polymorphs. The results demonstrate the importance of low-frequency intermolecular modes in determining the phase stability in these materials. The understanding gained allows us to propose a general principle for the relative stability of different polymorphs of hybrid materials as temperature is increased.

  7. Improving the Stability of Metal Halide Perovskite Materials and Light-Emitting Diodes.

    PubMed

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

    2018-01-25

    Metal halide perovskites (MHPs) have numerous advantages as light emitters such as high photoluminescence quantum efficiency with a direct bandgap, very narrow emission linewidth, high charge-carrier mobility, low energetic disorder, solution processability, simple color tuning, and low material cost. Based on these advantages, MHPs have recently shown unprecedented radical progress (maximum current efficiency from 0.3 to 42.9 cd A -1 ) in the field of light-emitting diodes. However, perovskite light-emitting diodes (PeLEDs) suffer from intrinsic instability of MHP materials and instability arising from the operation of the PeLEDs. Recently, many researchers have devoted efforts to overcome these instabilities. Here, the origins of the instability in PeLEDs are reviewed by categorizing it into two types: instability of (i) the MHP materials and (ii) the constituent layers and interfaces in PeLED devices. Then, the strategies to improve the stability of MHP materials and PeLEDs are critically reviewed, such as A-site cation engineering, Ruddlesden-Popper phase, suppression of ion migration with additives and blocking layers, fabrication of uniform bulk polycrystalline MHP layers, and fabrication of stable MHP nanoparticles. Based on this review of recent advances, future research directions and an outlook of PeLEDs for display applications are suggested. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Composition-Graded Cesium Lead Halide Perovskite Nanowires with Tunable Dual-Color Lasing Performance.

    PubMed

    Huang, Ling; Gao, Qinggang; Sun, Ling-Dong; Dong, Hao; Shi, Shuo; Cai, Tong; Liao, Qing; Yan, Chun-Hua

    2018-05-21

    Cesium lead halide (CsPbX 3 ) perovskite has emerged as a promising low-threshold multicolor laser material; however, realizing wavelength-tunable lasing output from a single CsPbX 3 nanostructure is still constrained by integrating different composition. Here, the direct synthesis of composition-graded CsPbBr x I 3- x nanowires (NWs) is reported through vapor-phase epitaxial growth on mica. The graded composition along the NW, with an increased Br/I from the center to the ends, comes from desynchronized deposition of cesium lead halides and temperature-controlled anion-exchange reaction. The graded composition results in varied bandgaps along the NW, which induce a blueshifted emission from the center to the ends. As an efficient gain media, the nanowire exerts position-dependent lasing performance, with a different color at the ends and center respectively above the threshold. Meanwhile, dual-color lasing with a wavelength separation of 35 nm is activated simultaneously at a site with an intermediate composition. This position-dependent dual-color lasing from a single nanowire makes these metal halide perovskites promising for applications in nanoscale optical devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Magnetic Field Effects in Hybrid Perovskite Devices

    NASA Astrophysics Data System (ADS)

    Zhang, C.; Sun, D.; Sheng, C.-X.; Zhai, Y.; Mielczarek, K.; Zakhidov, A.; Vardeny, Z. V.

    2015-03-01

    Solar cells based on the organic-inorganic perovskites (CH3NH3PbX3, X =halogen) have reached a remarkable power conversion efficiency approaching 20%, which calls for research studies of the photophysics behind this high device performance. We measured significant magneto-photocurrent (MPC) response in CH3NH3PbI3-xClx photovoltaic cells, in the form of Lorentzian up to field B = 1T. We attribute the MPC(B) response to spin mixing of loosely-bound photogenerated e-h pairs having different g-factor (dubbed `` Δg mechanism''). We verified this mechanism by measuring Δg directly, using the field induced circularly polarized photoluminescence emission at low temperature, along with the photocarriers' lifetime measured by picosecond pump-probe spectroscopy. We conclude that MPC of spin 1/2 e-h pairs provides a promising method for investigating the spin-related properties of photoexcitations in the novel hybrid perovskites.

  10. All-Inorganic Perovskite Solar Cells.

    PubMed

    Liang, Jia; Wang, Caixing; Wang, Yanrong; Xu, Zhaoran; Lu, Zhipeng; Ma, Yue; Zhu, Hongfei; Hu, Yi; Xiao, Chengcan; Yi, Xu; Zhu, Guoyin; Lv, Hongling; Ma, Lianbo; Chen, Tao; Tie, Zuoxiu; Jin, Zhong; Liu, Jie

    2016-12-14

    The research field on perovskite solar cells (PSCs) is seeing frequent record breaking in the power conversion efficiency (PCE). However, organic-inorganic hybrid halide perovskites and organic additives in common hole-transport materials (HTMs) exhibit poor stability against moisture and heat. Here we report the successful fabrication of all-inorganic PSCs without any labile or expensive organic components. The entire fabrication process can be operated in ambient environment without humidity control (e.g., a glovebox). Even without encapsulation, the all-inorganic PSCs present no performance degradation in humid air (90-95% relative humidity, 25 °C) for over 3 months (2640 h) and can endure extreme temperatures (100 and -22 °C). Moreover, by elimination of expensive HTMs and noble-metal electrodes, the cost was significantly reduced. The highest PCE of the first-generation all-inorganic PSCs reached 6.7%. This study opens the door for next-generation PSCs with long-term stability under harsh conditions, making practical application of PSCs a real possibility.

  11. Mesoscopic Perovskite Light-Emitting Diodes.

    PubMed

    Palma, Alessandro Lorenzo; Cinà, Lucio; Busby, Yan; Marsella, Andrea; Agresti, Antonio; Pescetelli, Sara; Pireaux, Jean-Jacques; Di Carlo, Aldo

    2016-10-03

    Solution-processed hybrid bromide perovskite light-emitting-diodes (PLEDs) represent an attractive alternative technology that would allow overcoming the well-known severe efficiency drop in the green spectrum related to conventional LEDs technologies. In this work, we report on the development and characterization of PLEDs fabricated using, for the first time, a mesostructured layout. Stability of PLEDs is a critical issue; remarkably, mesostructured PLEDs devices tested in ambient conditions and without encapsulation showed a lifetime well-above what previously reported with a planar heterojunction layout. Moreover, mesostructured PLEDs measured under full operative conditions showed a remarkably narrow emission spectrum, even lower than what is typically obtained by nitride- or phosphide-based green LEDs. A dynamic analysis has shown fast rise and fall times, demonstrating the suitability of PLEDs for display applications. Combined electrical and advanced structural analyses (Raman, XPS depth profiling, and ToF-SIMS 3D analysis) have been performed to elucidate the degradation mechanism, the results of which are mainly related to the degradation of the hole-transporting material (HTM) and to the perovskite-HTM interface.

  12. Finding New Perovskite Halides via Machine learning

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-01

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning) via building a support vector machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  13. Perovskite oxides: Oxygen electrocatalysis and bulk structure

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

  14. Finding new perovskite halides via machine learning

    SciTech Connect

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach toward rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning, henceforth referred to as ML) via building a support vectormore » machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX 3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br, or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 185 experimentally known ABX 3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor, and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. As a result, the trained and validated models then predict, with a high degree of confidence, several novel ABX 3 compositions with perovskite crystal structure.« less

  15. Finding new perovskite halides via machine learning

    DOE PAGES

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; ...

    2016-04-26

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach toward rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning, henceforth referred to as ML) via building a support vectormore » machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX 3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br, or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 185 experimentally known ABX 3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor, and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. As a result, the trained and validated models then predict, with a high degree of confidence, several novel ABX 3 compositions with perovskite crystal structure.« less

  16. 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)

    Bilodeau, Steven (Inventor); Baum, Thomas H. (Inventor); Roeder, Jeffrey F. (Inventor); Chen, Ing-Shin (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.

  17. Substitution in recreation choice behavior

    Treesearch

    George L. Peterson; Daniel J. Stynes; Donald H. Rosenthal; John F. Dwyer

    1985-01-01

    This review discusses concepts and theories of substitution in recreation choice. It brings together the literature of recreation research, psychology, geography, economics, and transportation. Parallel and complementary developments need integration into an improved theory of substitution. Recreation decision behavior is characterized as a nested or sequential choice...

  18. Why Does Trigonometric Substitution Work?

    ERIC Educational Resources Information Center

    Cunningham, Daniel W.

    2018-01-01

    Modern calculus textbooks carefully illustrate how to perform integration by trigonometric substitution. Unfortunately, most of these books do not adequately justify this powerful technique of integration. In this article, we present an accessible proof that establishes the validity of integration by trigonometric substitution. The proof offers…

  19. Generic substitution of antiepileptic drugs.

    PubMed

    Sander, Josemir W; Ryvlin, Philippe; Stefan, Hermann; Booth, Daniel R; Bauer, Jürgen

    2010-12-01

    Substitution of antiepileptic drugs with generic formulations may affect individual people, as well as healthcare systems. Analyses of large medical claims databases suggest that generic substitution of antiepileptic drugs is associated with increased morbidity and greater use of healthcare resources. While a single brand-to-generic switch may be associated with a slight increase in overall medical costs, multiple switches may be associated with higher costs, perhaps because different generic agents are not required to be bioequivalent to each other. Generic substitution also affects the individual: along with the possible increased risk of seizures or adverse events, inconsistency of supply may make the medication appear unfamiliar, thus discouraging adherence. Importantly, substitution is often carried out at the dispensing level, without the knowledge or consent of physicians and affected individuals. Therefore, regulatory and professional bodies advocate that substitution should not be carried out without specific counseling of the individual by healthcare professionals on the details and implications of the change.

  20. Unraveling luminescence mechanisms in zero-dimensional halide perovskites

    DOE PAGES

    Han, Dan; Shi, Hongliang; Ming, Wenmei; ...

    2018-01-01

    Zero-dimensional (0D) halides perovskites, in which anionic metal-halide octahedra (MX 6 ) 4− are separated by organic or inorganic countercations, have recently shown promise as excellent luminescent materials.

  1. Working Mechanism for Flexible Perovskite Solar Cells with Simplified Architecture.

    PubMed

    Xu, Xiaobao; Chen, Qi; Hong, Ziruo; Zhou, Huanping; Liu, Zonghao; Chang, Wei-Hsuan; Sun, Pengyu; Chen, Huajun; De Marco, Nicholas; Wang, Mingkui; Yang, Yang

    2015-10-14

    In this communication, we report an efficient and flexible perovskite solar cell based on formamidinium lead trihalide (FAPbI3) with simplified configuration. The device achieved a champion efficiency of 12.70%, utilizing direct contact between metallic indium tin oxide (ITO) electrode and perovskite absorber. The underlying working mechanism is proposed subsequently, via a systematic investigation focusing on the heterojunction within this device. A significant charge storage has been observed in the perovskite, which is believed to generate photovoltage and serves as the driving force for charge transferring from the absorber to ITO electrode as well. More importantly, this simplified device structure on flexible substrates suggests its compatibility for scale-up fabrication, which paves the way for commercialization of perovskite photovoltaic technology.

  2. Recent progress in efficient hybrid lead halide perovskite solar cells

    PubMed Central

    Cui, Jin; Yuan, Huailiang; Li, Junpeng; Xu, Xiaobao; Shen, Yan; Lin, Hong; Wang, Mingkui

    2015-01-01

    The efficiency of perovskite solar cells (PSCs) has been improved from 9.7 to 19.3%, with the highest value of 20.1% achieved in 2014. Such a high photovoltaic performance can be attributed to optically high absorption characteristics and balanced charge transport properties with long diffusion lengths of the hybrid lead halide perovskite materials. In this review, some fundamental details of hybrid lead iodide perovskite materials, various fabrication techniques and device structures are described, aiming for a better understanding of these materials and thus highly efficient PSC devices. In addition, some advantages and open issues are discussed here to outline the prospects and challenges of using perovskites in commercial photovoltaic devices. PMID:27877815

  3. Unraveling luminescence mechanisms in zero-dimensional halide perovskites

    DOE PAGES

    Han, Dan; Shi, Hongliang; Ming, Wenmei; ...

    2018-05-18

    Here, zero-dimensional (0D) halides perovskites, in which anionic metal-halide octahedra (MX 6) 4– are separated by organic or inorganic countercations, have recently shown promise as excellent luminescent materials.

  4. Laser Direct Write Synthesis of Lead Halide Perovskites

    SciTech Connect

    Chou, Stanley S.; Swartzentruber, Brian S.; Janish, Matthew T.

    Lead halide perovskites are increasingly considered for applications beyond photovoltaics, for example, light emission and detection, where an ability to pattern and prototype microscale geometries can facilitate the incorporation of this class of materials into devices. In this study, we demonstrate laser direct write of lead halide perovskites, a remarkably simple procedure that takes advantage of the inverse dependence between perovskite solubility and temperature by using a laser to induce localized heating of an absorbing substrate. We also demonstrate arbitrary pattern formation of crystalline CH 3NH 3PbBr 3 on a range of substrates and fabricate and characterize a microscale photodetectormore » using this approach. This direct write methodology provides a path forward for the prototyping and production of perovskite-based devices.« less

  5. NREL Research Pinpoints Promise of Polycrystalline Perovskites | News |

    Science.gov Websites

    Beard, David Moore and Elisa Miller are co-authors of a new paper in Nature Energy about perovskites , Yong Yan, Elisa M. Miller, and Kai Zhu. Beard said the research determined surface recombination

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

    ERIC Educational Resources Information Center

    Francisco, E.; And Others

    1988-01-01

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

  7. Present status and future prospects of perovskite photovoltaics

    NASA Astrophysics Data System (ADS)

    Snaith, Henry J.

    2018-05-01

    Solar cells based on metal halide perovskites continue to approach their theoretical performance limits thanks to worldwide research efforts. Mastering the materials properties and addressing stability may allow this technology to bring profound transformations to the electric power generation industry.

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

    DOE PAGES

    Zhu, Huiyuan; Zhang, Pengfei; Dai, Sheng

    2015-09-21

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

  9. Laser Direct Write Synthesis of Lead Halide Perovskites

    DOE PAGES

    Chou, Stanley S.; Swartzentruber, Brian S.; Janish, Matthew T.; ...

    2016-09-05

    Lead halide perovskites are increasingly considered for applications beyond photovoltaics, for example, light emission and detection, where an ability to pattern and prototype microscale geometries can facilitate the incorporation of this class of materials into devices. In this study, we demonstrate laser direct write of lead halide perovskites, a remarkably simple procedure that takes advantage of the inverse dependence between perovskite solubility and temperature by using a laser to induce localized heating of an absorbing substrate. We also demonstrate arbitrary pattern formation of crystalline CH 3NH 3PbBr 3 on a range of substrates and fabricate and characterize a microscale photodetectormore » using this approach. This direct write methodology provides a path forward for the prototyping and production of perovskite-based devices.« less

  10. Unraveling luminescence mechanisms in zero-dimensional halide perovskites

    SciTech Connect

    Han, Dan; Shi, Hongliang; Ming, Wenmei

    Zero-dimensional (0D) halides perovskites, in which anionic metal-halide octahedra (MX 6 ) 4− are separated by organic or inorganic countercations, have recently shown promise as excellent luminescent materials.

  11. Radiative efficiency of lead iodide based perovskite solar cells

    PubMed Central

    Tvingstedt, Kristofer; Malinkiewicz, Olga; Baumann, Andreas; Deibel, Carsten; Snaith, Henry J.; Dyakonov, Vladimir; Bolink, Henk J.

    2014-01-01

    The maximum efficiency of any solar cell can be evaluated in terms of its corresponding ability to emit light. We herein determine the important figure of merit of radiative efficiency for Methylammonium Lead Iodide perovskite solar cells and, to put in context, relate it to an organic photovoltaic (OPV) model device. We evaluate the reciprocity relation between electroluminescence and photovoltaic quantum efficiency and conclude that the emission from the perovskite devices is dominated by a sharp band-to-band transition that has a radiative efficiency much higher than that of an average OPV device. As a consequence, the perovskite have the benefit of retaining an open circuit voltage ~0.14 V closer to its radiative limit than the OPV cell. Additionally, and in contrast to OPVs, we show that the photoluminescence of the perovskite solar cell is substantially quenched under short circuit conditions in accordance with how an ideal photovoltaic cell should operate. PMID:25317958

  12. Perovskite as light harvester: a game changer in photovoltaics.

    PubMed

    Kazim, Samrana; Nazeeruddin, Mohammad Khaja; Grätzel, Michael; Ahmad, Shahzada

    2014-03-10

    It is not often that the scientific community is blessed with a material, which brings enormous hopes and receives special attention. When it does, it expands at a rapid pace and its every dimension creates curiosity. One such material is perovskite, which has triggered the development of new device architectures in energy conversion. Perovskites are of great interest in photovoltaic devices due to their panchromatic light absorption and ambipolar behavior. Power conversion efficiencies have been doubled in less than a year and over 15% is being now measured in labs. Every digit increment in efficiency is being celebrated widely in the scientific community and is being discussed in industry. Here we provide a summary on the use of perovskite for inexpensive solar cells fabrication. It will not be unrealistic to speculate that one day perovskite-based solar cells can match the capability and capacity of existing technologies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Hole-Transport Materials for Perovskite Solar Cells.

    PubMed

    Calió, Laura; Kazim, Samrana; Grätzel, Michael; Ahmad, Shahzada

    2016-11-14

    The pressure to move towards renewable energy has inspired researchers to look for ideas in photovoltaics that may lead to a major breakthrough. Recently the use of perovskites as a light harvester has lead to stunning progress. The power conversion efficiency of perovskite solar cells is now approaching parity (>22 %) with that of the established technology which took decades to reach this level of performance. The use of a hole transport material (HTM) remains indispensable in perovskite solar cells. Perovskites can conduct holes, but they are present at low levels, and for efficient charge extraction a HTM layer is a prerequisite. Herein we provide an overview of the diverse types of HTM available, from organic to inorganic, in the hope of encouraging further research and the optimization of these materials. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Red cell substitutes.

    PubMed

    Winslow, Robert M

    2007-01-01

    Oxygen-carrying plasma expanders (blood substitutes) have been sought for over a century. Development of current products is a result of evolution in the understanding of proteins in general, of hemoglobin in particular, and of how cell-free hemoglobin interacts with the control of local blood flow to ensure adequate tissue oxygenation. Hemoglobin-based products are considered in four "generations" corresponding to major improvements. First-generation products consisted of hemoglobin, freed of red cell membranes (stroma-free hemoglobin [SFH]), which was renal toxic and vasoactive. Second-generation products were polymerized with aldehyde reagents to reduce or eliminate the renal toxicity, but the products were heterogeneous and still vasoactive. Third-generation products employed more specific intramolecular crosslinking to eliminate polymerization and promote homogeneity, but they also remained vasoactive. Fourth-generation products are based on a new understanding of the way in which microvascular blood flow is controlled and the influence of O(2) delivery to vascular walls. After more than a century of research, one of these new solutions should find use as an alternative to red cells for transfusion in certain clinical settings.

  15. Maximizing and stabilizing luminescence from halide perovskites with potassium passivation

    NASA Astrophysics Data System (ADS)

    Abdi-Jalebi, Mojtaba; Andaji-Garmaroudi, Zahra; Cacovich, Stefania; Stavrakas, Camille; Philippe, Bertrand; Richter, Johannes M.; Alsari, Mejd; Booker, Edward P.; Hutter, Eline M.; Pearson, Andrew J.; Lilliu, Samuele; Savenije, Tom J.; Rensmo, Håkan; Divitini, Giorgio; Ducati, Caterina; Friend, Richard H.; Stranks, Samuel D.

    2018-03-01

    Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield—a quantity that must be maximized to obtain high efficiency—remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can

  16. Maximizing and stabilizing luminescence from halide perovskites with potassium passivation.

    PubMed

    Abdi-Jalebi, Mojtaba; Andaji-Garmaroudi, Zahra; Cacovich, Stefania; Stavrakas, Camille; Philippe, Bertrand; Richter, Johannes M; Alsari, Mejd; Booker, Edward P; Hutter, Eline M; Pearson, Andrew J; Lilliu, Samuele; Savenije, Tom J; Rensmo, Håkan; Divitini, Giorgio; Ducati, Caterina; Friend, Richard H; Stranks, Samuel D

    2018-03-21

    Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield-a quantity that must be maximized to obtain high efficiency-remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can approach

  17. Application of carbon nanotubes in perovskite solar cells: A review

    NASA Astrophysics Data System (ADS)

    Oo, Thet Tin; Debnath, Sujan

    2017-11-01

    Solar power, as alternative renewable energy source, has gained momentum in global energy generation in recent time. Solar photovoltaics (PV) systems now fulfill a significant portion of electricity demand and the capacity of solar PV capacity is growing every year. PV cells efficiency has improved significantly following decades of research, evolving into third generations of PV cells. These third generation PV cells are set out to provide low-cost and efficient PV systems, further improving the commercial competitiveness of solar energy generation. Among these latest generations of PV cells, perovskite solar cells have gained attraction due to the simple manufacturing process and the immense growth in PV efficiency in a short period of research and development. Despite these advantages, perovskite solar cells are known for the weak stability and decomposition in exposure to humidity and high temperature, hindering the possibility of commercialization. This paper will discuss the role of carbon nanotubes (CNTs) in improving the efficiency and stability of perovskite solar cells, in various components such as perovskite layer and hole transport layer, as well as the application of CNTs in unique aspects. These includes the use of CNTs fiber in making the perovskite solar cells flexible, as well as simplification of perovskite PV production by using CNT flash evaporation printing process. Despite these advances, challenges remain in incorporation CNTs into perovskite such as lower conversion efficiency compared to rare earth metals and improvements need to be made. Thus, the paper will be also highlighting the CNTs materials suggested for further research and improvement of perovskite solar cells.

  18. 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    PubMed

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

    2016-11-30

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

  20. How Do Substitute Teachers Substitute? An Empirical Study of Substitute-Teacher Labor Supply

    ERIC Educational Resources Information Center

    Gershenson, Seth

    2012-01-01

    This paper examines the daily labor supply of a potentially important, but often overlooked, source of instruction in U.S. public schools: substitute teachers. I estimate a sequential binary-choice model of substitute teachers' job-offer acceptance decisions using data on job offers made by a randomized automated calling system. Importantly, this…

  1. Perovskite classification: An Excel spreadsheet to determine and depict end-member proportions for the perovskite- and vapnikite-subgroups of the perovskite supergroup

    NASA Astrophysics Data System (ADS)

    Locock, Andrew J.; Mitchell, Roger H.

    2018-04-01

    Perovskite mineral oxides commonly exhibit extensive solid-solution, and are therefore classified on the basis of the proportions of their ideal end-members. A uniform sequence of calculation of the end-members is required if comparisons are to be made between different sets of analytical data. A Microsoft Excel spreadsheet has been programmed to assist with the classification and depiction of the minerals of the perovskite- and vapnikite-subgroups following the 2017 nomenclature of the perovskite supergroup recommended by the International Mineralogical Association (IMA). Compositional data for up to 36 elements are input into the spreadsheet as oxides in weight percent. For each analysis, the output includes the formula, the normalized proportions of 15 end-members, and the percentage of cations which cannot be assigned to those end-members. The data are automatically plotted onto the ternary and quaternary diagrams recommended by the IMA for depiction of perovskite compositions. Up to 200 analyses can be entered into the spreadsheet, which is accompanied by data calculated for 140 perovskite compositions compiled from the literature.

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

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

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

  3. Fabrication of Semiconducting Methylammonium Lead Halide Perovskite Particles by Spray Technology

    NASA Astrophysics Data System (ADS)

    Ahmadian-Yazdi, Mohammad-Reza; Eslamian, Morteza

    2018-01-01

    In this "nano idea" paper, three concepts for the preparation of methylammonium lead halide perovskite particles are proposed, discussed, and tested. The first idea is based on the wet chemistry preparation of the perovskite particles, through the addition of the perovskite precursor solution to an anti-solvent to facilitate the precipitation of the perovskite particles in the solution. The second idea is based on the milling of a blend of the perovskite precursors in the dry form, in order to allow for the conversion of the precursors to the perovskite particles. The third idea is based on the atomization of the perovskite solution by a spray nozzle, introducing the spray droplets into a hot wall reactor, so as to prepare perovskite particles, using the droplet-to-particle spray approach (spray pyrolysis). Preliminary results show that the spray technology is the most successful method for the preparation of impurity-free perovskite particles and perovskite paste to deposit perovskite thin films. As a proof of concept, a perovskite solar cell with the paste prepared by the sprayed perovskite powder was successfully fabricated.

  4. Fabrication of Semiconducting Methylammonium Lead Halide Perovskite Particles by Spray Technology.

    PubMed

    Ahmadian-Yazdi, Mohammad-Reza; Eslamian, Morteza

    2018-01-10

    In this "nano idea" paper, three concepts for the preparation of methylammonium lead halide perovskite particles are proposed, discussed, and tested. The first idea is based on the wet chemistry preparation of the perovskite particles, through the addition of the perovskite precursor solution to an anti-solvent to facilitate the precipitation of the perovskite particles in the solution. The second idea is based on the milling of a blend of the perovskite precursors in the dry form, in order to allow for the conversion of the precursors to the perovskite particles. The third idea is based on the atomization of the perovskite solution by a spray nozzle, introducing the spray droplets into a hot wall reactor, so as to prepare perovskite particles, using the droplet-to-particle spray approach (spray pyrolysis). Preliminary results show that the spray technology is the most successful method for the preparation of impurity-free perovskite particles and perovskite paste to deposit perovskite thin films. As a proof of concept, a perovskite solar cell with the paste prepared by the sprayed perovskite powder was successfully fabricated.

  5. Structural investigations and the effect of strain on lead based double perovskites

    NASA Astrophysics Data System (ADS)

    Abbett, Brian; Fennie, Craig J.

    2014-03-01

    The A2 BB' O6 double perovskite structure, in which the B and B' ions are ordered (typically in a rocksalt configuration), provides a versatile platform to realize new properties such as multiferroicity. In particular, compounds with a lone-pair cation on the A-site, such as A=Pb2+, and magnetic B=Co, Mn, and diamagnetic B'= Te, Mo, W, Re, cations have been investigated experimentally, but as of yet none have been found to display ferroelectricity, although several are known to be antiferroelectric. Here we present a first-principles study of the structural and dielectric properties of this family of compounds. We resolve any conflicting reports in the literature as to the ground state structure of compounds and predict the ground state structure when no structural data is available. Additionally, we investigate the effect of epitaxial strain on the structural and magnetic properties.

  6. Mechanical tunability via hydrogen bonding in metal-organic frameworks with the perovskite architecture.

    PubMed

    Li, Wei; Thirumurugan, A; Barton, Phillip T; Lin, Zheshuai; Henke, Sebastian; Yeung, Hamish H-M; Wharmby, Michael T; Bithell, Erica G; Howard, Christopher J; Cheetham, Anthony K

    2014-06-04

    Two analogous metal-organic frameworks (MOFs) with the perovskite architecture, [C(NH2)3][Mn(HCOO)3] (1) and [(CH2)3NH2][Mn(HCOO)3] (2), exhibit significantly different mechanical properties. The marked difference is attributed to their distinct modes of hydrogen bonding between the A-site amine cation and the anionic framework. The stronger cross-linking hydrogen bonding in 1 gives rise to Young's moduli and hardnesses that are up to twice those in 2, while the thermal expansion is substantially smaller. This study presents clear evidence that the mechanical properties of MOF materials can be substantially tuned via hydrogen-bonding interactions.

  7. High Performance Tandem Perovskite/Polymer Solar Cells

    NASA Astrophysics Data System (ADS)

    Liu, Yao; Bag, Monojit; Page, Zachariah; Renna, Lawrence; Kim, Paul; Choi, Jaewon; Emrick, Todd; Venkataraman, D.; Russell, Thomas

    Combining perovskites with other inorganic materials, such as copper indium gallium diselenide (CIGS) or silicon, is enabling significant improvement in solar cell device performance. Here, we demonstrate a highly efficient hybrid tandem solar cell fabricated through a facile solution deposition approach to give a perovskite front sub-cell and a polymer:fullerene blend back sub-cell. This methodology eliminates the adverse effects of thermal annealing during perovskite fabrication on polymer solar cells. The record tandem solar cell efficiency of 15.96% is 40% greater than the corresponding perovskite-based single junction device and 65% greater than the polymer-based single junction device, while mitigating deleterious hysteresis effects often associated with perovskite solar cells. The hybrid tandem devices demonstrate the synergistic effects arising from the combination of perovskite and polymer-based materials for solar cells. This work was supported by the Department of Energy-supported Energy Frontier Research Center at the University of Massachusetts (DE-SC0001087). The authors acknowledge the W.M. Keck Electron Microscopy.

  8. Two-Photon Absorption in Organometallic Bromide Perovskites.

    PubMed

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

    2015-09-22

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

  9. Confining metal-halide perovskites in nanoporous thin films

    PubMed Central

    Demchyshyn, Stepan; Roemer, Janina Melanie; Groiß, Heiko; Heilbrunner, Herwig; Ulbricht, Christoph; Apaydin, Dogukan; Böhm, Anton; Rütt, Uta; Bertram, Florian; Hesser, Günter; Scharber, Markus Clark; Sariciftci, Niyazi Serdar; Nickel, Bert; Bauer, Siegfried; Głowacki, Eric Daniel; Kaltenbrunner, Martin

    2017-01-01

    Controlling the size and shape of semiconducting nanocrystals advances nanoelectronics and photonics. Quantum-confined, inexpensive, solution-derived metal halide perovskites offer narrowband, color-pure emitters as integral parts of next-generation displays and optoelectronic devices. We use nanoporous silicon and alumina thin films as templates for the growth of perovskite nanocrystallites directly within device-relevant architectures without the use of colloidal stabilization. We find significantly blue-shifted photoluminescence emission by reducing the pore size; normally infrared-emitting materials become visibly red, and green-emitting materials become cyan and blue. Confining perovskite nanocrystals within porous oxide thin films drastically increases photoluminescence stability because the templates auspiciously serve as encapsulation. We quantify the template-induced size of the perovskite crystals in nanoporous silicon with microfocus high-energy x-ray depth profiling in transmission geometry, verifying the growth of perovskite nanocrystals throughout the entire thickness of the nanoporous films. Low-voltage electroluminescent diodes with narrow, blue-shifted emission fabricated from nanocrystalline perovskites grown in embedded nanoporous alumina thin films substantiate our general concept for next-generation photonic devices. PMID:28798959

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

    NASA Astrophysics Data System (ADS)

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

    2018-06-01

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

  11. Controlled Homoepitaxial Growth of Hybrid Perovskites.

    PubMed

    Lei, Yusheng; Chen, Yimu; Gu, Yue; Wang, Chunfeng; Huang, Zhenlong; Qian, Haoliang; Nie, Jiuyuan; Hollett, Geoff; Choi, Woojin; Yu, Yugang; Kim, NamHeon; Wang, Chonghe; Zhang, Tianjiao; Hu, Hongjie; Zhang, Yunxi; Li, Xiaoshi; Li, Yang; Shi, Wanjun; Liu, Zhaowei; Sailor, Michael J; Dong, Lin; Lo, Yu-Hwa; Luo, Jian; Xu, Sheng

    2018-05-01

    Organic-inorganic hybrid perovskites have demonstrated tremendous potential for the next-generation electronic and optoelectronic devices due to their remarkable carrier dynamics. Current studies are focusing on polycrystals, since controlled growth of device compatible single crystals is extremely challenging. Here, the first chemical epitaxial growth of single crystal CH 3 NH 3 PbBr 3 with controlled locations, morphologies, and orientations, using combined strategies of advanced microfabrication, homoepitaxy, and low temperature solution method is reported. The growth is found to follow a layer-by-layer model. A light emitting diode array, with each CH 3 NH 3 PbBr 3 crystal as a single pixel, with enhanced quantum efficiencies than its polycrystalline counterparts is demonstrated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Ion-Migration Inhibition by the Cation-π Interaction in Perovskite Materials for Efficient and Stable Perovskite Solar Cells.

    PubMed

    Wei, Dong; Ma, Fusheng; Wang, Rui; Dou, Shangyi; Cui, Peng; Huang, Hao; Ji, Jun; Jia, Endong; Jia, Xiaojie; Sajid, Sajid; Elseman, Ahmed Mourtada; Chu, Lihua; Li, Yingfeng; Jiang, Bing; Qiao, Juan; Yuan, Yongbo; Li, Meicheng

    2018-06-25

    Migration of ions can lead to photoinduced phase separation, degradation, and current-voltage hysteresis in perovskite solar cells (PSCs), and has become a serious drawback for the organic-inorganic hybrid perovskite materials (OIPs). Here, the inhibition of ion migration is realized by the supramolecular cation-π interaction between aromatic rubrene and organic cations in OIPs. The energy of the cation-π interaction between rubrene and perovskite is found to be as strong as 1.5 eV, which is enough to immobilize the organic cations in OIPs; this will thus will lead to the obvious reduction of defects in perovskite films and outstanding stability in devices. By employing the cation-immobilized OIPs to fabricate perovskite solar cells (PSCs), a champion efficiency of 20.86% and certified efficiency of 20.80% with negligible hysteresis are acquired. In addition, the long-term stability of cation-immobilized PSCs is improved definitely (98% of the initial efficiency after 720 h operation), which is assigned to the inhibition of ionic diffusions in cation-immobilized OIPs. This cation-π interaction between cations and the supramolecular π system enhances the stability and the performance of PSCs efficiently and would be a potential universal approach to get the more stable perovskite devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Selective dissolution of halide perovskites as a step towards recycling solar cells

    PubMed Central

    Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee; Park, So Yeon; Li, Zhen; Zhu, Kai; Jung, Hyun Suk

    2016-01-01

    Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Herein, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easily decomposed in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb2+ cations. After 10 cycles of recycling, a mesoporous TiO2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells. PMID:27211006

  14. Selective dissolution of halide perovskites as a step towards recycling solar cells

    NASA Astrophysics Data System (ADS)

    Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee; Park, So Yeon; Li, Zhen; Zhu, Kai; Jung, Hyun Suk

    2016-05-01

    Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Herein, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easily decomposed in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb2+ cations. After 10 cycles of recycling, a mesoporous TiO2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells.

  15. High annealing temperature induced rapid grain coarsening for efficient perovskite solar cells.

    PubMed

    Cao, Xiaobing; Zhi, Lili; Jia, Yi; Li, Yahui; Cui, Xian; Zhao, Ke; Ci, Lijie; Ding, Kongxian; Wei, Jinquan

    2018-08-15

    Thermal annealing plays multiple roles in fabricating high quality perovskite films. Generally, it might result in large perovskite grains by elevating annealing temperature, but might also lead to decomposition of perovskite. Here, we study the effects of annealing temperature on the coarsening of perovskite grains in a temperature range from 100 to 250 °C, and find that the coarsening rate of the perovskite grain increase significantly with the annealing temperature. Compared with the perovskite films annealed at 100 °C, high quality perovskite films with large columnar grains are obtained by annealing perovskite precursor films at 250 °C for only 10 s. As a result, the power conversion efficiency of best solar cell increased from 12.35% to 16.35% due to its low recombination rate and high efficient charge transportation in solar cells. Copyright © 2018. Published by Elsevier Inc.

  16. Selective dissolution of halide perovskites as a step towards recycling solar cells.

    PubMed

    Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee; Park, So Yeon; Li, Zhen; Zhu, Kai; Jung, Hyun Suk

    2016-05-23

    Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Herein, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easily decomposed in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb(2+) cations. After 10 cycles of recycling, a mesoporous TiO2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells.

  17. Strain effects on oxygen migration in perovskites.

    PubMed

    Mayeshiba, Tam; Morgan, Dane

    2015-01-28

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

  18. Planar Heterojunction Perovskite Solar Cells Incorporating Metal-Organic Framework Nanocrystals.

    PubMed

    Chang, Ting-Hsiang; Kung, Chung-Wei; Chen, Hsin-Wei; Huang, Tzu-Yen; Kao, Sheng-Yuan; Lu, Hsin-Che; Lee, Min-Han; Boopathi, Karunakara Moorthy; Chu, Chih-Wei; Ho, Kuo-Chuan

    2015-11-25

    Zr-based porphyrin metal-organic framework (MOF-525) nanocrystals with a crystal size of about 140 nm are synthesized and incorporated into perovskite solar cells. The morphology and crystallinity of the perovskite thin film are enhanced since the micropores of MOF-525 allow the crystallization of perovskite to occur inside; this observation results in a higher cell efficiency of the obtained MOF/perovskite solar cell. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. DESIGNING ENVIRONMENTALLY BENIGN SOLVENT SUBSTITUTES

    EPA Science Inventory

    Since the signing of 1987 Montreal Protocol, reducing and eliminating the use of harmful solvents has become an internationally imminent environmental protection mission. Solvent substitution is an effective way to achieve this goal. The Program for Assisting the Replacement of...

  20. Business as a Site of Language Contact.

    ERIC Educational Resources Information Center

    Harris, Sandra; Bargiela-Chiappini, Francesca

    2003-01-01

    Discusses the field of language for business. Argues for redressing the balance of research into business as a site of language contact in favor of less well-represented languages and cultures through indigenous discourse studies, and notes the increasing frequency and importance of work involving Asian languages. (Author/VWL)

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

    PubMed

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

    2016-06-25

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

  2. Exploration of organic-inorganic hybrid perovskites for surface-enhanced infrared spectroscopy of small molecules.

    PubMed

    Chen, Jia; Mo, Zhi-Hong; Yang, Xiao; Zhou, Hai-Ling; Gao, Qin

    2017-06-22

    The organic-inorganic hybrid perovskites efficiently enhance the infrared absorption of small molecules. It is suggested that the quantum wells of perovskites enable the electrons of the perovskites to be excited by light in the infrared region. The exploration has opened a new path for chemical sensing through infrared spectroscopy.

  3. Overcoming the Photovoltage Plateau in Large Bandgap Perovskite Photovoltaics.

    PubMed

    Rajagopal, Adharsh; Stoddard, Ryan J; Jo, Sae Byeok; Hillhouse, Hugh W; Jen, Alex K-Y

    2018-05-09

    Development of large bandgap (1.80-1.85 eV E g ) perovskite is crucial for perovskite-perovskite tandem solar cells. However, the performance of 1.80-1.85 eV E g perovskite solar cells (PVKSCs) are significantly lagging their counterparts in the 1.60-1.75 eV E g range. This is because the photovoltage ( V oc ) does not proportionally increase with E g due to lower optoelectronic quality of conventional (MA,FA,Cs)Pb(I,Br) 3 and results in a photovoltage plateau ( V oc limited to 80% of the theoretical limit for ∼1.8 eV E g ). Here, we incorporate phenylethylammonium (PEA) in a mixed-halide perovskite composition to solve the inherent material-level challenges in 1.80-1.85 eV E g perovskites. The amount of PEA incorporation governs the topography and optoelectronic properties of resultant films. Detailed structural and spectroscopic characterization reveal the characteristic trends in crystalline size, orientation, and charge carrier recombination dynamics and rationalize the origin of improved material quality with higher luminescence. With careful interface optimization, the improved material characteristics were translated to devices and V oc values of 1.30-1.35 V were achieved, which correspond to 85-87% of the theoretical limit. Using an optimal amount of PEA incorporation to balance the increase in V oc and the decrease in charge collection, a highest power conversion efficiency of 12.2% was realized. Our results clearly overcome the photovoltage plateau in the 1.80-1.85 eV E g range and represent the highest V oc achieved for mixed-halide PVKSCs. This study provides widely translatable insights, an important breakthrough, and a promising platform for next-generation perovskite tandems.

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

    SciTech Connect

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

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

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

    DOE PAGES

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

    2017-09-05

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

  6. Employing Lead Thiocyanate Additive to Reduce the Hysteresis and Boost the Fill Factor of Planar Perovskite Solar Cells

    SciTech Connect

    Ke, Weijun; Xiao, Chuanxiao; Wang, Changlei

    2016-05-04

    Lead thiocyanate in the perovskite precursor can increase the grain size of a perovskite thin film and reduce the conductivity of the grain boundaries, leading to perovskite solar cells with reduced hysteresis and enhanced fill factor. A planar perovskite solar cell with grain boundary and interface passivation achieves a steady-state efficiency of 18.42%.

  7. High Br- Content CsPb(Cl yBr1- y)3 Perovskite Nanocrystals with Strong Mn2+ Emission through Diverse Cation/Anion Exchange Engineering.

    PubMed

    Li, Fei; Xia, Zhiguo; Pan, Caofeng; Gong, Yue; Gu, Lin; Liu, Quanlin; Zhang, Jin Z

    2018-04-11

    The unification of tunable band edge (BE) emission and strong Mn 2+ doping luminescence in all-inorganic cesium lead halide perovskite nanocrystals (NCs) CsPbX 3 (X = Cl and Br) is of fundamental importance in fine tuning their optical properties. Herein, we demonstrate that benefiting from the differentiation of the cation/anion exchange rate, ZnBr 2 and preformed CsPb 1- x Cl 3 : xMn 2+ NCs can be used to obtain high Br - content Cs(Pb 1- x- z Zn z )(Cl y Br 1- y ) 3 : xMn 2+ perovskite NCs with strong Mn 2+ emission, and the Mn 2+ substitution ratio can reach about 22%. More specifically, the fast anion exchange could be realized by the soluble halide precursors, leading to anion exchange within a few seconds as observed from the strong BE emission evolution, whereas the cation exchange instead generally required at least a few hours; moreover, their exchange mechanism and dynamics process have been evaluated. The Mn 2+ emission intensity could be further varied by controlling the replacement of Mn 2+ by Zn 2+ with prolonged ion exchange reaction time. White light emission of the doped perovskite NCs via this cation/anion synergistic exchange strategy has been realized, which was also successfully demonstrated in a prototype white light-emitting diode (LED) device based on a commercially available 365 nm LED chip.

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

    PubMed Central

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

    2016-01-01

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

  9. Electronic and optical properties of MAPbX3 perovskites (X = I, Br, Cl): a unified DFT and GW theoretical analysis.

    PubMed

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

    2016-10-05

    Materials engineering is a key for the enhancement of photovoltaics technology. This is particularly true for the novel class of perovskite solar cells. Accurate theoretical modelling can help establish general trends of behavior when addressing structural changes. Here, we consider the effects due to halide substitution in organohalide CH 3 NH 3 PbX 3 perovskites exploring the halide series with X = Cl, Br, I. For this task, we use accurate DFT and GW methods including spin-orbit coupling. We find the expected band gap increase when moving from X = I to Cl, in line with the experimental data. Most notably, the calculated absorption coefficients for I, Br and Cl are nicely reproducing the behavior reported experimentally. A common feature of all the simulated band structures is a significant Rashba effect. This is similar for MAPbI 3 and MAPbBr 3 while MAPbCl 3 shows in general a reduced Rashba interaction coefficient. Finally, a monotonic increase of the exciton reduced masses is calculated when moving from I to Br to Cl, in line with the stronger excitonic character of the lighter perovskite halides.

  10. MgSiO3-FeSiO3-Al2O3 in the Earth's lower mantle: Perovskite and garnet at 1200 km depth

    NASA Technical Reports Server (NTRS)

    O'Neill, Bridget; Jeanloz, Raymond

    1994-01-01

    Natural pyroxene and garnet starting material are used to study the effects of joint Fe and Al substitution into MgSiO3 perovskite at approxmiately 50 GPa. Garnet is found to coexist with perovskite in samples containing both Fe and Al to pressures occurring deep into the lower mantel (approximately 1200 km depth). The volume of the perovskite unit cell is V(sub o(Angstrom(exp 3)) = 162.59 + 5.95x(sub FeSiO3) + 10.80x(sub Al2O3) with aluminum causing a significant increase in the distortion from the ideal cubic cell. On the basis of a proposed extension of the MgSiO3-Al2O3 high-pressure phase diagram toward FeSiO3, Fe is shown to partition preferentially into the garnet phase. The stability of garnet deep into the lower mantel may hinder the penetration of subducted slabs below the transition zone.

  11. A Long-Term View on Perovskite Optoelectronics.

    PubMed

    Docampo, Pablo; Bein, Thomas

    2016-02-16

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

  12. Effect of Element Substitution at V site on Thermoelectric Properties of Aurivillius Phase Bi2VO5.5

    NASA Astrophysics Data System (ADS)

    Kohri, Hitoshi; Yagasaki, Takayoshi

    2016-10-01

    Thermoelectric oxides are suitable at the high temperature range because of chemical stability. Aurivillius compounds are bismuth layered oxides, and known as oxygen ion conductors. The Aurivillius compounds consist of Perovskite layers and Bi-O layers. It is expected that nano-layered structure shows high Seebeck coefficients due to the quantum confinement of carriers in Perovskite layers. It was reported that the Seebeck coefficient of hot pressed specimens for Aurivillius phase Bi2VO5.5 was a high value of -28.3 mVK-1 at 1010 K, and the electrical resistivity of one was also a high value of 0.033 Ωm at 1010 K. In this paper, the effect of element substitution at the V site on thermoelectric properties of Aurivillius phase Bi2VO5.5 was investigated. Bi2V1- x M x O5.5 (M = Cr, Mo, W x = 0, 0.05, 0.1, 0.2) were prepared by solid-state reaction. The electrical resistivity of Cr-substituted specimens were indicated at larger values than the ones for unsubstituted specimens over the measurement temperature range. The resistivity above 800 K was reduced by substitution of W or Mo. W as a substituted element was effective for reducing the thermal conductivity of Bi2VO5.5. The maximum value of the dimensionless figure of merit ZT was 0.05 at 799 K for Bi2V0.8Mo0.2O5.5 and at 902 K for Bi2V0.8W0.1O5.5. The maximum ZT of an unsubstituted sample was 0.02 at 993 K. From these results, it was found that tungsten or molybdenum substitution was effective to improve ZT for Aurivillius phase Bi2VO5.5.

  13. Exciton Dynamics of 2D Hybrid Perovskite Nanocrystal

    NASA Astrophysics Data System (ADS)

    Guo, Rui; Zhu, Zhuan; Boulesbaa, Abdelaziz; Venkatesan, Swaminathan; Xiao, Kai; Bao, Jiming; Yao, Yan; Li, Wenzhi

    Organic-inorganic hybrid perovskites have emerged as promising materials for applications in photovoltaic and optoelectronic devices. Among the perovskites, two dimensional (2D) perovskites are of great interests due to their remarkable optical and electrical properties as well as the flexibility of material selection for the organic and inorganic moieties. In this study, we demonstrate the solution-phase growth of large square-shaped single-crystalline 2D hybrid perovskites of (C6H5C2H4 NH3) 2 PbBr4 with a few unit cells thickness. Compared to the bulk crystal, a band gap shift and new photoluminescence (PL) peak are observed from the hybrid perovskite sheets. Color of the 2D crystals can be tuned by adjusting the sheet thickness. Pump-probe spectroscopy is used to investigate the exciton dynamics and exhibits a biexponential decay with an amplitude-weighted lifetime of 16.7 ps. Such high-quality (C6H5C2H4 NH3) 2 PbBr4 sheets are expected to have high PL quantum efficiency which can be adopted for light-emitting devices. National Science Foundation (Grant No. CMMI-1334417 and DMR-1506640).

  14. A Direct Bandgap Copper-Antimony Halide Perovskite.

    PubMed

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

    2017-07-12

    Since the establishment of perovskite solar cells (PSCs), there has been an intense search for alternative materials to replace lead and improve their stability toward moisture and light. As single-metal perovskite structures have yielded unsatisfactory performances, an alternative is the use of double perovskites that incorporate a combination of metals. To this day, only a handful of these compounds have been synthesized, but most of them have indirect bandgaps and/or do not have bandgaps energies well-suited for photovoltaic applications. Here we report the synthesis and characterization of a unique mixed metal ⟨111⟩-oriented layered perovskite, Cs 4 CuSb 2 Cl 12 (1), that incorporates Cu 2+ and Sb 3+ into layers that are three octahedra thick (n = 3). In addition to being made of abundant and nontoxic elements, we show that this material behaves as a semiconductor with a direct bandgap of 1.0 eV and its conductivity is 1 order of magnitude greater than that of MAPbI 3 (MA = methylammonium). Furthermore, 1 has high photo- and thermal-stability and is tolerant to humidity. We conclude that 1 is a promising material for photovoltaic applications and represents a new type of layered perovskite structure that incorporates metals in 2+ and 3+ oxidation states, thus significantly widening the possible combinations of metals to replace lead in PSCs.

  15. Temperature Gradient-Induced Instability of Perovskite via Ion Transport.

    PubMed

    Wang, Xinwei; Liu, Hong; Zhou, Feng; Dahan, Jeremy; Wang, Xin; Li, Zhengping; Shen, Wenzhong

    2018-01-10

    Perovskite has been known as a promising novel material for photovoltaics and other fields because of its excellent opto-electric properties and convenient fabrication. However, its stability has been a widely known haunting factor that has severely deteriorated its application in reality. In this work, it has been discovered for the first time that perovskite can become significantly chemically unstable with the existence of a temperature gradient in the system, even at temperature far below its thermal decomposition condition. A study of the detailed mechanism has revealed that the existence of a temperature gradient could induce a mass transport process of extrinsic ionic species into the perovskite layer, which enhances its decomposition process. Moreover, this instability could be effectively suppressed with a reduced temperature gradient by simple structural modification of the device. Further experiments have proved the existence of this phenomenon in different perovskites with various mainstream substrates, indicating the universality of this phenomenon in many previous studies and future research. Hopefully, this work may bring deeper understanding of its formation mechanisms and facilitate the general development of perovskite toward its real application.

  16. Electron–phonon coupling in hybrid lead halide perovskites

    PubMed Central

    Wright, Adam D.; Verdi, Carla; Milot, Rebecca L.; Eperon, Giles E.; Pérez-Osorio, Miguel A.; Snaith, Henry J.; Giustino, Feliciano; Johnston, Michael B.; Herz, Laura M.

    2016-01-01

    Phonon scattering limits charge-carrier mobilities and governs emission line broadening in hybrid metal halide perovskites. Establishing how charge carriers interact with phonons in these materials is therefore essential for the development of high-efficiency perovskite photovoltaics and low-cost lasers. Here we investigate the temperature dependence of emission line broadening in the four commonly studied formamidinium and methylammonium perovskites, HC(NH2)2PbI3, HC(NH2)2PbBr3, CH3NH3PbI3 and CH3NH3PbBr3, and discover that scattering from longitudinal optical phonons via the Fröhlich interaction is the dominant source of electron–phonon coupling near room temperature, with scattering off acoustic phonons negligible. We determine energies for the interacting longitudinal optical phonon modes to be 11.5 and 15.3 meV, and Fröhlich coupling constants of ∼40 and 60 meV for the lead iodide and bromide perovskites, respectively. Our findings correlate well with first-principles calculations based on many-body perturbation theory, which underlines the suitability of an electronic band-structure picture for describing charge carriers in hybrid perovskites. PMID:27225329

  17. Decreasing the electronic confinement in layered perovskites through intercalation.

    PubMed

    Smith, Matthew D; Pedesseau, Laurent; Kepenekian, Mikaël; Smith, Ian C; Katan, Claudine; Even, Jacky; Karunadasa, Hemamala I

    2017-03-01

    We show that post-synthetic small-molecule intercalation can significantly reduce the electronic confinement of 2D hybrid perovskites. Using a combined experimental and theoretical approach, we explain structural, optical, and electronic effects of intercalating highly polarizable molecules in layered perovskites designed to stabilize the intercalants. Polarizable molecules in the organic layers substantially alter the optical and electronic properties of the inorganic layers. By calculating the spatially resolved dielectric profiles of the organic and inorganic layers within the hybrid structure, we show that the intercalants afford organic layers that are more polarizable than the inorganic layers. This strategy reduces the confinement of excitons generated in the inorganic layers and affords the lowest exciton binding energy for an n = 1 perovskite of which we are aware. We also demonstrate a method for computationally evaluating the exciton's binding energy by solving the Bethe-Salpeter equation for the exciton, which includes an ab initio determination of the material's dielectric profile across organic and inorganic layers. This new semi-empirical method goes beyond the imprecise phenomenological approximation of abrupt dielectric-constant changes at the organic-inorganic interfaces. This work shows that incorporation of polarizable molecules in the organic layers, through intercalation or covalent attachment, is a viable strategy for tuning 2D perovskites towards mimicking the reduced electronic confinement and isotropic light absorption of 3D perovskites while maintaining the greater synthetic tunability of the layered architecture.

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

    NASA Astrophysics Data System (ADS)

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

    2017-10-01

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

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

    PubMed

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

    2017-12-01

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

  20. X-ray Scintillation in Lead Halide Perovskite Crystals

    PubMed Central

    Birowosuto, M. D.; Cortecchia, D.; Drozdowski, W.; Brylew, K.; Lachmanski, W.; Bruno, A.; Soci, C.

    2016-01-01

    Current technologies for X-ray detection rely on scintillation from expensive inorganic crystals grown at high-temperature, which so far has hindered the development of large-area scintillator arrays. Thanks to the presence of heavy atoms, solution-grown hybrid lead halide perovskite single crystals exhibit short X-ray absorption length and excellent detection efficiency. Here we compare X-ray scintillator characteristics of three-dimensional (3D) MAPbI3 and MAPbBr3 and two-dimensional (2D) (EDBE)PbCl4 hybrid perovskite crystals. X-ray excited thermoluminescence measurements indicate the absence of deep traps and a very small density of shallow trap states, which lessens after-glow effects. All perovskite single crystals exhibit high X-ray excited luminescence yields of >120,000 photons/MeV at low temperature. Although thermal quenching is significant at room temperature, the large exciton binding energy of 2D (EDBE)PbCl4 significantly reduces thermal effects compared to 3D perovskites, and moderate light yield of 9,000 photons/MeV can be achieved even at room temperature. This highlights the potential of 2D metal halide perovskites for large-area and low-cost scintillator devices for medical, security and scientific applications. PMID:27849019

  1. 14 CFR 1260.55 - Reports substitution.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... AGREEMENTS General Special Conditions § 1260.55 Reports substitution. Reports Substitution October 2000 Technical Reports may be substituted for the required Performance Reports. The title page of such reports... 14 Aeronautics and Space 5 2013-01-01 2013-01-01 false Reports substitution. 1260.55 Section 1260...

  2. 14 CFR 1260.55 - Reports substitution.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... AGREEMENTS General Special Conditions § 1260.55 Reports substitution. Reports Substitution October 2000 Technical Reports may be substituted for the required Performance Reports. The title page of such reports... 14 Aeronautics and Space 5 2010-01-01 2010-01-01 false Reports substitution. 1260.55 Section 1260...

  3. 14 CFR 1260.55 - Reports substitution.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... AGREEMENTS General Special Conditions § 1260.55 Reports substitution. Reports Substitution October 2000 Technical Reports may be substituted for the required Performance Reports. The title page of such reports... 14 Aeronautics and Space 5 2011-01-01 2010-01-01 true Reports substitution. 1260.55 Section 1260...

  4. 14 CFR 1260.55 - Reports substitution.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... AGREEMENTS General Special Conditions § 1260.55 Reports substitution. Reports Substitution October 2000 Technical Reports may be substituted for the required Performance Reports. The title page of such reports... 14 Aeronautics and Space 5 2012-01-01 2012-01-01 false Reports substitution. 1260.55 Section 1260...

  5. Size-Dependent Photon Emission from Organometal Halide Perovskite Nanocrystals Embedded in an Organic Matrix

    PubMed Central

    2015-01-01

    In recent years, organometal halide perovskite materials have attracted significant research interest in the field of optoelectronics. Here, we introduce a simple and low-temperature route for the formation of self-assembled perovskite nanocrystals in a solid organic matrix. We demonstrate that the size and photoluminescence peak of the perovskite nanocrystals can be tuned by varying the concentration of perovskite in the matrix material. The physical origin of the blue shift of the perovskite nanocrystals’ emission compared to its bulk phase is also discussed. PMID:25949773

  6. Role of organic and inorganic cations on thermal behavior of lead iodide perovskites

    NASA Astrophysics Data System (ADS)

    Singh, Rajan Kumar; Dash, Saumya R.; Kumar, Ranveer; Jain, Neha; Singh, Jai

    2018-04-01

    Recently, organic-inorganic perovskite materials have attracted much attention due to their enormous potential for use in future of new sustainable energy sources. However, fabrication of environmental friendly perovskite and achieving better stability is a major concern towards the commercialization. Here we study the role of cations in the perovskite powder and their influence upon thermodynamic stability. In this study we find, inorganic (cesium, Cs+) cation is shown to be more efficient in the thermal stabilization of the perovskite material than organic (methylamine, CH3NH2+) cation. This study reviles that stability of perovskite can be improved by incorporation of inorganic cation.

  7. Bandgap Engineering of Lead-Free Double Perovskite Cs2 AgBiBr6 through Trivalent Metal Alloying.

    PubMed

    Du, Ke-Zhao; Meng, Weiwei; Wang, Xiaoming; Yan, Yanfa; Mitzi, David B

    2017-07-03

    The double perovskite family, A 2 M I M III X 6 , is a promising route to overcome the lead toxicity issue confronting the current photovoltaic (PV) standout, CH 3 NH 3 PbI 3 . Given the generally large indirect band gap within most known double perovskites, band-gap engineering provides an important approach for targeting outstanding PV performance within this family. Using Cs 2 AgBiBr 6 as host, band-gap engineering through alloying of In III /Sb III has been demonstrated in the current work. Cs 2 Ag(Bi 1-x M x )Br 6 (M=In, Sb) accommodates up to 75 % In III with increased band gap, and up to 37.5 % Sb III with reduced band gap; that is, enabling ca. 0.41 eV band gap modulation through introduction of the two metals, with smallest value of 1.86 eV for Cs 2 Ag(Bi 0.625 Sb 0.375 )Br 6 . Band structure calculations indicate that opposite band gap shift directions associated with Sb/In substitution arise from different atomic configurations for these atoms. Associated photoluminescence and environmental stability of the three-metal systems are also assessed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Potential application of CuSbS2 as the hole transport material in perovskite solar cell: A simulation study

    NASA Astrophysics Data System (ADS)

    Teimouri, R.; Mohammadpour, R.

    2018-06-01

    CH3 NH3 PbI3 (MAPbI3) thin film solar cells, which are reported at laboratory efficiency scale of nearly 22%, are the subject of much attention by energy researchers due to their low cost buildup, acceptable efficiency, high absorption coefficient and diffusion length. The main purpose of this research is to simulate the structure of thin film perovskite solar cells through numerical simulation of SCAPS based on the empirical data for different hole transport layers. After simulating the initial structure of FTO/TiO2/CH3NH3PbI3/Spiro-OMeTAD solar cell, the hole transport layer Spiro-OMeTAD thickness was optimized on a small scale using modeling. The researchers also sought to reduce the amount of this material and the cost of construction. Ultimately, an optimum thickness of 140 nm was obtained for this cell with efficiency of 22.88%. The effect of employing alternative inorganic hole transport layer was investigated as a substitute for Spiro-OMeTAD; Copper antimony sulphide (CuSbS2) was selected due to abundant and available material and high open circuit voltage of about 988 mV. Thickness variations were also performed on a MAPbI3/CuSbS2 solar cell. Finally, It has obtained that perovskite solar cell with 120 nm-thick of CuSbS2 has 23.14% conversion efficiency with acceptable VOC and JSC values.

  9. Quantum mechanical studies of complex ferroelectric perovskites

    NASA Astrophysics Data System (ADS)

    Ramer, Nicholas John

    In many electronic device applications, there is a need to interconvert electrical energy and other types of energy. Ferroelectric materials, which possess a voltage-dependent polarization, can enable this energy conversion process. Because of the broad interest in ferroelectric materials for these devices, there is a critical research effort, both experimental and theoretical, to understand these materials and aid in the development of materials with improved properties. This thesis presents detailed quantum mechanical investigations of the behavior of a complex ferroelectric perovskite under applied stress. In particular, we have chosen to study the solid solution PbZr1-xTix O3 (PZT). Since the study of ferroelectricity involves understanding both its structural and electronic signatures in materials, it has necessitated the development of a novel theoretical technique which improves the accuracy of the pseudopotentials used in our density functional theory calculations as well as a new method for constructing three-dimensional atomistic responses to small amounts of external stress. To examine the material's behavior under larger amounts of stress, we have studied the behavior of a composition of PZT lying near a structural phase boundary. On either side of the phase boundary, the material is characterized by a different polarization direction and may easily be switched between phases by applying external stress. In addition to stress-induced phase transitions, most ferroelectric materials also have composition dependent phase boundaries. Since different compositions of PZT would require increased computational effort, we have formulated an improved virtual crystal approach that makes tractable the study of the entire composition range. Using this method, we have been able to show for the first time via first-principles calculations, a composition dependent phase transition in a ferroelectric material. This thesis has accomplished three important goals: new

  10. Structural and thermoelectric properties of n-type Sr1- x Ti x MnO3- δ perovskite system

    NASA Astrophysics Data System (ADS)

    Kim, C. M.; Seo, J. W.; Choi, S.-M.; Seo, W.-S.; Lee, S.; Lim, Y. S.; Park, K.

    2015-03-01

    A series of Sr1- x Ti x MnO3- δ (0.05 ≤ x ≤ 0.3) was fabricated by the solid-state reaction method. We studied the structural and thermoelectric properties of Sr1- x Ti x MnO3- δ , with respect to the partial substitution of Ti4+ for Sr2+. The sintered Sr1- x Ti x MnO3- δ crystallized in the hexagonal perovskite-type structure with a space group of P6 3 / mmc. For x ≤ 0.1, the partial substitution of Ti4+ for Sr2+ led to increases in the electrical conductivity and the absolute value of the Seebeck coefficient, thus enhancing the power factor. The highest power factor (2.5 × 10-5 Wm-1K-2) was obtained for Sr0.9Ti0.1MnO3- δ at 800°C. The partial substitution of Ti4+ for Sr2+ in SrMnO3- δ led to a significant improvement in the thermoelectric properties. [Figure not available: see fulltext.

  11. Efficient semitransparent perovskite solar cells for 23.0%-efficiency perovskite/silicon four-terminal tandem cells

    SciTech Connect

    Chen, Bo; Bai, Yang; Yu, Zhengshan

    Here, we have investigated semi-transparent perovskite solar cells and infrared enhanced silicon heterojunction cells for high-efficiency tandem devices. A semi-transparent metal electrode with good electrical conductivity and optical transparency has been fabricated by thermal evaporation of 7 nm of Au onto a 1-nm-thick Cu seed layer. For this electrode to reach its full potential, MAPbI3 thin films were formed by a modified one-step spin-coating method, resulting in a smooth layer that allowed the subsequent metal thin film to remain continuous. The fabricated semi-transparent perovskite solar cells demonstrated 16.5% efficiency under one-sun illumination, and were coupled with infrared-enhanced silicon heterojunction cellsmore » tuned specifically for perovskite/Si tandem devices. A double-layer antireflection coating at the front side and MgF2 reflector at rear side of the silicon heterojunction cells reduced parasitic absorption of near-infrared light, leading to 6.5% efficiency after filtering with a perovskite device and 23.0% summed efficiency for the perovskite/Si tandem device.« less

  12. Efficient semitransparent perovskite solar cells for 23.0%-efficiency perovskite/silicon four-terminal tandem cells

    DOE PAGES

    Chen, Bo; Bai, Yang; Yu, Zhengshan; ...

    2016-07-19

    Here, we have investigated semi-transparent perovskite solar cells and infrared enhanced silicon heterojunction cells for high-efficiency tandem devices. A semi-transparent metal electrode with good electrical conductivity and optical transparency has been fabricated by thermal evaporation of 7 nm of Au onto a 1-nm-thick Cu seed layer. For this electrode to reach its full potential, MAPbI3 thin films were formed by a modified one-step spin-coating method, resulting in a smooth layer that allowed the subsequent metal thin film to remain continuous. The fabricated semi-transparent perovskite solar cells demonstrated 16.5% efficiency under one-sun illumination, and were coupled with infrared-enhanced silicon heterojunction cellsmore » tuned specifically for perovskite/Si tandem devices. A double-layer antireflection coating at the front side and MgF2 reflector at rear side of the silicon heterojunction cells reduced parasitic absorption of near-infrared light, leading to 6.5% efficiency after filtering with a perovskite device and 23.0% summed efficiency for the perovskite/Si tandem device.« less

  13. Paintable Carbon-Based Perovskite Solar Cells with Engineered Perovskite/Carbon Interface Using Carbon Nanotubes Dripping Method.

    PubMed

    Ryu, Jaehoon; Lee, Kisu; Yun, Juyoung; Yu, Haejun; Lee, Jungsup; Jang, Jyongsik

    2017-10-01

    Paintable carbon electrode-based perovskite solar cells (PSCs) are of particular interest due to their material and fabrication process costs, as well as their moisture stability. However, printing the carbon paste on the perovskite layer limits the quality of the interface between the perovskite layer and carbon electrode. Herein, an attempt to enhance the performance of the paintable carbon-based PSCs is made using a modified solvent dripping method that involves dripping of the carbon nanotubes (CNTs), which is dispersed in chlorobenzene solution. This method allows CNTs to penetrate into both the perovskite film and carbon electrode, facilitating fast hole transport between the two layers. Furthermore, this method is results in increased open circuit voltage (V oc ) and fill factor (FF), providing better contact at the perovskite/carbon interfaces. The best devices made with CNT dripping show 13.57% power conversion efficiency and hysteresis-free performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Symmetry mismatch-driven perpendicular magnetic anisotropy for perovskite/brownmillerite heterostructures.

    PubMed

    Zhang, Jing; Zhong, Zhicheng; Guan, Xiangxiang; Shen, Xi; Zhang, Jine; Han, Furong; Zhang, Hui; Zhang, Hongrui; Yan, Xi; Zhang, Qinghua; Gu, Lin; Hu, Fengxia; Yu, Richeng; Shen, Baogen; Sun, Jirong

    2018-05-15

    Grouping different transition metal oxides together by interface engineering is an important route toward emergent phenomenon. While most of the previous works focused on the interface effects in perovskite/perovskite heterostructures, here we reported on a symmetry mismatch-driven spin reorientation toward perpendicular magnetic anisotropy in perovskite/brownmillerite heterostructures, which is scarcely seen in tensile perovskite/perovskite heterostructures. We show that alternately stacking perovskite La 2/3 Sr 1/3 MnO 3 and brownmillerite LaCoO 2.5 causes a strong interface reconstruction due to symmetry discontinuity at interface: neighboring MnO 6 octahedra and CoO 4 tetrahedra at the perovskite/brownmillerite interface cooperatively relax in a manner that is unavailable for perovskite/perovskite interface, leading to distinct orbital reconstructions and thus the perpendicular magnetic anisotropy. Moreover, the perpendicular magnetic anisotropy is robust, with an anisotropy constant two orders of magnitude greater than the in-plane anisotropy of the perovskite/perovskite interface. The present work demonstrates the great potential of symmetry engineering in designing artificial materials on demand.

  15. Fast Postmoisture Treatment of Luminescent Perovskite Films for Efficient Light-Emitting Diodes.

    PubMed

    Wang, Haoran; Li, Xiaomin; Yuan, Mingjian; Yang, Xuyong

    2018-04-01

    Despite the recent advances in the performance of perovskite light-emitting diodes (PeLEDs), the effects of water on the perovskite emissive layer and its electroluminescence are still unclear, even though it has been previously demonstrated that moisture has a significant impact on the quality of perovskite films in the fabrication process of perovskite solar cells and is a prerequisite for obtaining high-performance PeLEDs. Here, the effects of postmoisture on the luminescent CH 3 NH 3 PbBr 3 (MAPbBr 3 ) perovskite films are systematically investigated. It is found that postmoisture treatment can efficiently control the morphology and growth of perovskite films and only a fast moisture exposure at a 60% high relative humidity results in significantly improved crystallinity, carrier lifetime, and photoluminescence quantum yield of perovskite films. With the optimized moisture-treated perovskite films, a high-performance PeLED is fabricated, exhibiting a maximum current efficiency of 20.4 cd A -1 , which is an almost 20-fold enhancement when compared with perovskite films without moisture treatment. The results provide valuable insights into the moisture-assisted growth of luminescent perovskite films and will aid in the development of high-performance perovskite light-emitting devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Interfacial Engineering of Perovskite Solar Cells by Employing a Hydrophobic Copper Phthalocyanine Derivative as Hole-Transporting Material with Improved Performance and Stability.

    PubMed

    Jiang, Xiaoqing; Yu, Ze; Lai, Jianbo; Zhang, Yuchen; Hu, Maowei; Lei, Ning; Wang, Dongping; Yang, Xichuan; Sun, Licheng

    2017-04-22

    In high-performance perovskite solar cells (PSCs), hole-transporting materials (HTMs) play an important role in extracting and transporting the photo-generated holes from the perovskite absorber to the cathode, thus reducing unwanted recombination losses and enhancing the photovoltaic performance. Herein, solution-processable tetra-4-(bis(4-tert-butylphenyl)amino)phenoxy-substituted copper phthalocyanine (CuPc-OTPAtBu) was synthesized and explored as a HTM in PSCs. The optical, electrochemical, and thermal properties were fully characterized for this organic metal complex. The photovoltaic performance of PSCs employing this CuPc derivative as a HTM was further investigated, in combination with a mixed-ion perovskite as a light absorber and a low-cost vacuum-free carbon as cathode. The optimized devices [doped with 6 % (w/w) tetrafluoro-tetracyano-quinodimethane (F4TCNQ)] showed a decent power conversion efficiency of 15.0 %, with an open-circuit voltage of 1.01 V, a short-circuit current density of 21.9 mA cm -2 , and a fill factor of 0.68. Notably, the PSC devices studied also exhibited excellent long-term durability under ambient condition for 720 h, mainly owing to the introduction of the hydrophobic HTM interlayer, which prevents moisture penetration into the perovskite film. The present work emphasizes that solution-processable CuPc holds a great promise as a class of alternative HTMs that can be further explored for efficient and stable PSCs in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Atomically thin two-dimensional organic-inorganic hybrid perovskites.

    PubMed

    Dou, Letian; Wong, Andrew B; Yu, Yi; Lai, Minliang; Kornienko, Nikolay; Eaton, Samuel W; Fu, Anthony; Bischak, Connor G; Ma, Jie; Ding, Tina; Ginsberg, Naomi S; Wang, Lin-Wang; Alivisatos, A Paul; Yang, Peidong

    2015-09-25

    Organic-inorganic hybrid perovskites, which have proved to be promising semiconductor materials for photovoltaic applications, have been made into atomically thin two-dimensional (2D) sheets. We report the solution-phase growth of single- and few-unit-cell-thick single-crystalline 2D hybrid perovskites of (C4H9NH3)2PbBr4 with well-defined square shape and large size. In contrast to other 2D materials, the hybrid perovskite sheets exhibit an unusual structural relaxation, and this structural change leads to a band gap shift as compared to the bulk crystal. The high-quality 2D crystals exhibit efficient photoluminescence, and color tuning could be achieved by changing sheet thickness as well as composition via the synthesis of related materials. Copyright © 2015, American Association for the Advancement of Science.

  18. Atomically thin two-dimensional organic-inorganic hybrid perovskites

    NASA Astrophysics Data System (ADS)

    Dou, Letian; Wong, Andrew B.; Yu, Yi; Lai, Minliang; Kornienko, Nikolay; Eaton, Samuel W.; Fu, Anthony; Bischak, Connor G.; Ma, Jie; Ding, Tina; Ginsberg, Naomi S.; Wang, Lin-Wang; Alivisatos, A. Paul; Yang, Peidong

    2015-09-01

    Organic-inorganic hybrid perovskites, which have proved to be promising semiconductor materials for photovoltaic applications, have been made into atomically thin two-dimensional (2D) sheets. We report the solution-phase growth of single- and few-unit-cell-thick single-crystalline 2D hybrid perovskites of (C4H9NH3)2PbBr4 with well-defined square shape and large size. In contrast to other 2D materials, the hybrid perovskite sheets exhibit an unusual structural relaxation, and this structural change leads to a band gap shift as compared to the bulk crystal. The high-quality 2D crystals exhibit efficient photoluminescence, and color tuning could be achieved by changing sheet thickness as well as composition via the synthesis of related materials.

  19. Solution-Phase Synthesis of Cesium Lead Halide Perovskite Nanowires.

    PubMed

    Zhang, Dandan; Eaton, Samuel W; Yu, Yi; Dou, Letian; Yang, Peidong

    2015-07-29

    Halide perovskites have attracted much attention over the past 5 years as a promising class of materials for optoelectronic applications. However, compared to hybrid organic-inorganic perovskites, the study of their pure inorganic counterparts, like cesium lead halides (CsPbX3), lags far behind. Here, a catalyst-free, solution-phase synthesis of CsPbX3 nanowires (NWs) is reported. These NWs are single-crystalline, with uniform growth direction, and crystallize in the orthorhombic phase. Both CsPbBr3 and CsPbI3 are photoluminescence active, with composition-dependent temperature and self-trapping behavior. These NWs with a well-defined morphology could serve as an ideal platform for the investigation of fundamental properties and the development of future applications in nanoscale optoelectronic devices based on all-inorganic perovskites.

  20. A polymer scaffold for self-healing perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Zhao, Yicheng; Wei, Jing; Li, Heng; Yan, Yin; Zhou, Wenke; Yu, Dapeng; Zhao, Qing

    2016-01-01

    Advancing of the lead halide perovskite solar cells towards photovoltaic market demands large-scale devices of high-power conversion efficiency, high reproducibility and stability via low-cost fabrication technology, and in particular resistance to humid environment for long-time operation. Here we achieve uniform perovskite film based on a novel polymer-scaffold architecture via a mild-temperature process. These solar cells exhibit efficiency of up to ~16% with small variation. The unencapsulated devices retain high output for up to 300 h in highly humid environment (70% relative humidity). Moreover, they show strong humidity resistant and self-healing behaviour, recovering rapidly after removing from water vapour. Not only the film can self-heal in this case, but the corresponding devices can present power conversion efficiency recovery after the water vapour is removed. Our work demonstrates the value of cheap, long chain and hygroscopic polymer scaffold in perovskite solar cells towards commercialization.

  1. Local Polar Fluctuations in Lead Halide Perovskite Crystals

    SciTech Connect

    Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.

    2017-03-01

    Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH3NH3PbBr3) and all-inorganic (CsPbBr3) leadhalide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-tohead Cs motion coupledmore » to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr3.« less

  2. Lasing from lead halide perovskite semiconductor microcavity system.

    PubMed

    Wang, Jun; Da, Peimei; Zhang, Zhe; Luo, Song; Liao, Liming; Sun, Zeyuan; Shen, Xuechu; Wu, Shiwei; Zheng, Gengfeng; Chen, Zhanghai

    2018-06-07

    Organic-inorganic halide perovskite semiconductors are ideal gain media for fabricating laser and photonic devices due to high absorption, photoluminescence (PL) efficiency and low nonradiative recombination losses. Herein, organic-inorganic halide perovskite CH3NH3PbI3 is embedded in the Fabry-Perot (FP) microcavity, and a wavelength-tunable excitonic lasing with a threshold of 12.9 μJ cm-2 and the spectral coherence of 0.76 nm are realized. The lasing threshold decreases and the spectral coherence enhances as the temperature decreases; these results are ascribed to the suppression of exciton irradiative recombination caused by thermal fluctuation. Moreover, both lasing and light emission below threshold from the perovskite microcavity (PM) system demonstrate a redshift with the decreasing temperature. These results provide a feasible platform based on the PM system for the study of light-matter interaction for quantum optics and the development of optoelectronic devices such as polariton lasers.

  3. Intrinsic white-light emission from layered hybrid perovskites.

    PubMed

    Dohner, Emma R; Jaffe, Adam; Bradshaw, Liam R; Karunadasa, Hemamala I

    2014-09-24

    We report on the second family of layered perovskite white-light emitters with improved photoluminescence quantum efficiencies (PLQEs). Upon near-ultraviolet excitation, two new Pb-Cl and Pb-Br perovskites emit broadband "cold" and "warm" white light, respectively, with high color rendition. Emission from large, single crystals indicates an origin from the bulk material and not surface defect sites. The Pb-Br perovskite has a PLQE of 9%, which is undiminished after 3 months of continuous irradiation. Our mechanistic studies indicate that the emission has contributions from strong electron-phonon coupling in a deformable lattice and from a distribution of intrinsic trap states. These hybrids provide a tunable platform for combining the facile processability of organic materials with the structural definition of crystalline, inorganic solids.

  4. Exciton localization in solution-processed organolead trihalide perovskites

    PubMed Central

    He, Haiping; Yu, Qianqian; Li, Hui; Li, Jing; Si, Junjie; Jin, Yizheng; Wang, Nana; Wang, Jianpu; He, Jingwen; Wang, Xinke; Zhang, Yan; Ye, Zhizhen

    2016-01-01

    Organolead trihalide perovskites have attracted great attention due to the stunning advances in both photovoltaic and light-emitting devices. However, the photophysical properties, especially the recombination dynamics of photogenerated carriers, of this class of materials are controversial. Here we report that under an excitation level close to the working regime of solar cells, the recombination of photogenerated carriers in solution-processed methylammonium–lead–halide films is dominated by excitons weakly localized in band tail states. This scenario is evidenced by experiments of spectral-dependent luminescence decay, excitation density-dependent luminescence and frequency-dependent terahertz photoconductivity. The exciton localization effect is found to be general for several solution-processed hybrid perovskite films prepared by different methods. Our results provide insights into the charge transport and recombination mechanism in perovskite films and help to unravel their potential for high-performance optoelectronic devices. PMID:26996605

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

    PubMed

    Saparov, Bayrammurad; Mitzi, David B

    2016-04-13

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

  6. Chemical Stabilization of Perovskite Solar Cells with Functional Fulleropyrrolidines

    PubMed Central

    2017-01-01

    While perovskite solar cells have invigorated the photovoltaic research community due to their excellent power conversion efficiencies (PCEs), these devices notably suffer from poor stability. To address this crucial issue, a solution-processable organic chemical inhibition layer (OCIL) was integrated into perovskite solar cells, resulting in improved device stability and a maximum PCE of 16.3%. Photoenhanced self-doping of the fulleropyrrolidine mixture in the interlayers afforded devices that were advantageously insensitive to OCIL thickness, ranging from 4 to 190 nm. X-ray photoelectron spectroscopy (XPS) indicated that the fulleropyrrolidine mixture improved device stability by stabilizing the metal electrode and trapping ionic defects (i.e., I–) that originate from the perovskite active layer. Moreover, degraded devices were rejuvenated by repeatedly peeling away and replacing the OCIL/Ag electrode, and this repeel and replace process resulted in further improvement to device stability with minimal variation of device efficiency. PMID:29532021

  7. Chemical Stabilization of Perovskite Solar Cells with Functional Fulleropyrrolidines.

    PubMed

    Liu, Yao; Page, Zachariah A; Zhou, Dongming; Duzhko, Volodimyr V; Kittilstved, Kevin R; Emrick, Todd; Russell, Thomas P

    2018-02-28

    While perovskite solar cells have invigorated the photovoltaic research community due to their excellent power conversion efficiencies (PCEs), these devices notably suffer from poor stability. To address this crucial issue, a solution-processable organic chemical inhibition layer (OCIL) was integrated into perovskite solar cells, resulting in improved device stability and a maximum PCE of 16.3%. Photoenhanced self-doping of the fulleropyrrolidine mixture in the interlayers afforded devices that were advantageously insensitive to OCIL thickness, ranging from 4 to 190 nm. X-ray photoelectron spectroscopy (XPS) indicated that the fulleropyrrolidine mixture improved device stability by stabilizing the metal electrode and trapping ionic defects (i.e., I - ) that originate from the perovskite active layer. Moreover, degraded devices were rejuvenated by repeatedly peeling away and replacing the OCIL/Ag electrode, and this repeel and replace process resulted in further improvement to device stability with minimal variation of device efficiency.

  8. A polymer scaffold for self-healing perovskite solar cells

    PubMed Central

    Zhao, Yicheng; Wei, Jing; Li, Heng; Yan, Yin; Zhou, Wenke; Yu, Dapeng; Zhao, Qing

    2016-01-01

    Advancing of the lead halide perovskite solar cells towards photovoltaic market demands large-scale devices of high-power conversion efficiency, high reproducibility and stability via low-cost fabrication technology, and in particular resistance to humid environment for long-time operation. Here we achieve uniform perovskite film based on a novel polymer-scaffold architecture via a mild-temperature process. These solar cells exhibit efficiency of up to ∼16% with small variation. The unencapsulated devices retain high output for up to 300 h in highly humid environment (70% relative humidity). Moreover, they show strong humidity resistant and self-healing behaviour, recovering rapidly after removing from water vapour. Not only the film can self-heal in this case, but the corresponding devices can present power conversion efficiency recovery after the water vapour is removed. Our work demonstrates the value of cheap, long chain and hygroscopic polymer scaffold in perovskite solar cells towards commercialization. PMID:26732479

  9. A polymer scaffold for self-healing perovskite solar cells.

    PubMed

    Zhao, Yicheng; Wei, Jing; Li, Heng; Yan, Yin; Zhou, Wenke; Yu, Dapeng; Zhao, Qing

    2016-01-06

    Advancing of the lead halide perovskite solar cells towards photovoltaic market demands large-scale devices of high-power conversion efficiency, high reproducibility and stability via low-cost fabrication technology, and in particular resistance to humid environment for long-time operation. Here we achieve uniform perovskite film based on a novel polymer-scaffold architecture via a mild-temperature process. These solar cells exhibit efficiency of up to ∼ 16% with small variation. The unencapsulated devices retain high output for up to 300 h in highly humid environment (70% relative humidity). Moreover, they show strong humidity resistant and self-healing behaviour, recovering rapidly after removing from water vapour. Not only the film can self-heal in this case, but the corresponding devices can present power conversion efficiency recovery after the water vapour is removed. Our work demonstrates the value of cheap, long chain and hygroscopic polymer scaffold in perovskite solar cells towards commercialization.

  10. Los Alamos Discovers Super Efficient Solar Using Perovskite Crystals

    ScienceCinema

    Mohite, Aditya; Nie, Wanyi

    2018-05-11

    State-of-the-art photovoltaics using high-purity, large-area, wafer-scale single-crystalline semiconductors grown by sophisticated, high temperature crystal-growth processes offer promising routes for developing low-cost, solar-based clean global energy solutions for the future. Solar cells composed of the recently discovered material organic-inorganic perovskites offer the efficiency of silicon, yet suffer from a variety of deficiencies limiting the commercial viability of perovskite photovoltaic technology. In research to appear in Science, Los Alamos National Laboratory researchers reveal a new solution-based hot-casting technique that eliminates these limitations, one that allows for the growth of high-quality, large-area, millimeter-scale perovskite crystals and demonstrates that highly efficient and reproducible solar cells with reduced trap assisted recombination can be realized.

  11. Local polar fluctuations in lead halide perovskite crystals

    DOE PAGES

    Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; ...

    2017-03-28

    Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH 3NH 3PbBr 3) and all-inorganic (CsPbBr 3) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. Furthermore, MD simulations indicatemore » that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr 3.« less

  12. Specific features of nonvalent interactions in orthorhombic perovskites

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  13. Research progress on organic-inorganic halide perovskite materials and solar cells

    NASA Astrophysics Data System (ADS)

    Ono, Luis K.; Qi, Yabing

    2018-03-01

    Owing to the intensive research efforts across the world since 2009, perovskite solar cell power conversion efficiencies (PCEs) are now comparable or even better than several other photovoltaic (PV) technologies. In this topical review article, we review recent progress in the field of organic-inorganic halide perovskite materials and solar cells. We associate these achievements with the fundamental knowledge gained in the perovskite research. The major recent advances in the fundamental perovskite material and solar cell research are highlighted, including the current efforts in visualizing the dynamical processes (in operando) taking place within a perovskite solar cell under operating conditions. We also discuss the existing technological challenges. Based on a survey of recently published works, we point out that to move the perovskite PV technology forward towards the next step of commercialization, what perovskite PV technology need the most in the coming next few years is not only further PCE enhancements, but also up-scaling, stability, and lead-toxicity.

  14. Suppressed decomposition of organometal halide perovskites by impermeable electron-extraction layers in inverted solar cells

    PubMed Central

    Brinkmann, K.O.; Zhao, J.; Pourdavoud, N.; Becker, T.; Hu, T.; Olthof, S.; Meerholz, K.; Hoffmann, L.; Gahlmann, T.; Heiderhoff, R.; Oszajca, M. F.; Luechinger, N. A.; Rogalla, D.; Chen, Y.; Cheng, B.; Riedl, T

    2017-01-01

    The area of thin-film photovoltaics has been overwhelmed by organometal halide perovskites. Unfortunately, serious stability concerns arise with perovskite solar cells. For example, methyl-ammonium lead iodide is known to decompose in the presence of water and, more severely, even under inert conditions at elevated temperatures. Here, we demonstrate inverted perovskite solar cells, in which the decomposition of the perovskite is significantly mitigated even at elevated temperatures. Specifically, we introduce a bilayered electron-extraction interlayer consisting of aluminium-doped zinc oxide and tin oxide. We evidence tin oxide grown by atomic layer deposition does form an outstandingly dense gas permeation barrier that effectively hinders the ingress of moisture towards the perovskite and—more importantly—it prevents the egress of decomposition products of the perovskite. Thereby, the overall decomposition of the perovskite is significantly suppressed, leading to an outstanding device stability. PMID:28067308

  15. Ultrasmooth Perovskite Film via Mixed Anti-Solvent Strategy with Improved Efficiency.

    PubMed

    Yu, Yu; Yang, Songwang; Lei, Lei; Cao, Qipeng; Shao, Jun; Zhang, Sheng; Liu, Yan

    2017-02-01

    Most antisolvents employed in previous research were miscible with perovskite precursor solution. They always led to fast formation of perovskite even if the intermediate stage existed, which was not beneficial to obtain high quality perovskite films and made the formation process less controllable. In this work, a novel ethyl ether/n-hexane mixed antisolvent (MAS) was used to achieve high nucleation density and slow down the formation process of perovskite, producing films with improved orientation of grains and ultrasmooth surfaces. These high quality films exhibited efficient charge transport at the interface of perovskite/hole transport material and perovskite solar cells based on these films showed greatly improved performance with the best power conversion efficiency of 17.08%. This work also proposed a selection principle of MAS and showed that solvent engineering by designing the mixed antisolvent system can lead to the fabrication of high-performance perovskite solar cells.

  16. Pin-Hole Free Perovskite Film for Solar Cells Application Prepared by Controlled Two-Step Spin-Coating Method

    NASA Astrophysics Data System (ADS)

    Bahtiar, A.; Rahmanita, S.; Inayatie, Y. D.

    2017-05-01

    Morphology of perovskite film is a key important for achieving high performance perovskite solar cells. Perovskite films are commonly prepared by two-step spin-coating method. However, pin-holes are frequently formed in perovskite films due to incomplete conversion of lead-iodide (PbI2) into perovskite CH3NH3PbI3. Pin-holes in perovskite film cause large hysteresis in current-voltage curve of solar cells due to large series resistance between perovskite layer-hole transport material. Moreover, crystal structure and grain size of perovskite crystal are also other important parameters for achieving high performance solar cells, which are significantly affected by preparation of perovskite film. We studied the effect of preparation of perovskite film using controlled spin-coating parameters on crystal structure and morphological properties of perovskite film. We used two-step spin-coating method for preparation of perovskite film with varied spinning speed, spinning time and temperature of spin-coating process to control growth of perovskite crystal aimed to produce high quality perovskite crystal with pin-hole free and large grain size. All experiment was performed in air with high humidity (larger than 80%). The best crystal structure, pin-hole free with large grain crystal size of perovskite film was obtained from film prepared at room temperature with spinning speed 1000 rpm for 20 seconds and annealed at 100°C for 300 seconds.

  17. Rational design of dipolar chromophore as an efficient dopant-free hole-transporting material for perovskite solar cells

    DOE PAGES

    Li, Zhong’an; Zhu, Zonglong; Chueh, Chu -Chen; ...

    2016-08-23

    In this paper, an electron donor-acceptor (D-A) substituted dipolar chromophore ( BTPA-TCNE) is developed to serve as an efficient dopant-free hole-transporting material (HTM) for perovskite solar cells (PVSCs). BTPA-TCNE is synthesized via a simple reaction between a triphenylamine-based Michler’s base and tetracyanoethylene. This chromophore possesses a zwitterionic resonance structure in the ground state, as evidenced by X-ray crystallography and transient absorption spectroscopies. Moreover, BTPA-TCNE shows an antiparallel molecular packing (i.e., centrosymmetric dimers) in its crystalline state, which cancels out its overall molecular dipole moment to facilitate charge transport. Finally, BTPA-TCNE can be employed as an effective dopant-free HTM to realizemore » an efficient (PCE ≈ 17.0%) PVSC in the conventional n-i-p configuration, outperforming the control device with doped spiro-OMeTAD HTM.« less

  18. First-principles study on ferromagnetism in double perovskite Sr2AlTaO6 doped with Cu or Zn at B sites

    NASA Astrophysics Data System (ADS)

    Li, Y. D.; Wang, C. C.; Guo, Y. M.; Yu, Y.; Lu, Q. L.; Huang, S. G.; Li, Q. J.; Wang, H.; Cheng, R. L.; Liu, C. S.

    2018-05-01

    The possibilities of ferromagnetism induced by nonmagnetic dopants (Cu, Zn) in double perovskite Sr2AlTaO6 at B sites are investigated by density functional theory. Calculations reveal that substitutions at Ta-site tend to form high spin electronic configurations and could induce ferromagnetism which can be attributed to the hole-mediated p- d hybridization between Cu (or Zn) eg states and the neighboring O 2p states. The dopants preferably substitute at Al-site and adopt low spin electronic structures. Due to the smaller hole concentration and weaker covalent intensity, Sr2AlTaO6 with dopants at Al-site exhibits p-type metallic semiconductors without spin polarization.

  19. 40 CFR 721.2577 - Copper complex of (substituted sulfonaphthyl azo substituted phenyl) disulfonaphthyl azo, amine...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Copper complex of (substituted... Copper complex of (substituted sulfonaphthyl azo substituted phenyl) disulfonaphthyl azo, amine salt... substances identified generically as copper complex of (substituted sulfonaphthyl azo substituted phenyl...

  20. Bifacial Perovskite Solar Cells Featuring Semitransparent Electrodes.

    PubMed

    Hanmandlu, Chintam; Chen, Chien-Yu; Boopathi, Karunakara Moorthy; Lin, Hao-Wu; Lai, Chao-Sung; Chu, Chih-Wei

    2017-09-27

    Inorganic-organic hybrid perovskite solar cells (PSCs) are promising devices for providing future clean energy because of their low cost, ease of fabrication, and high efficiencies, similar to those of silicon solar cells. These materials have been investigated for their potential use in bifacial PSCs, which can absorb light from both sides of the electrodes. Here, we fabricated bifacial PSCs featuring transparent BCP/Ag/MoO 3 rear electrodes, which we formed through low-temperature processing using thermal evaporation methods. We employed a comprehensive optical distribution program to calculate the distributions of the optical field intensities with constant thicknesses of the absorbing layer in the top electrode configuration. The best PSC having a transparent BCP/Ag/MoO 3 electrode achieved PCEs of 13.49% and 9.61% when illuminated from the sides of the indium tin oxide and BCP/Ag/MoO 3 electrodes, respectively. We observed significant power enhancement when operating this PSC using mirror reflectors and bifacial light illumination from both sides of the electrodes.

  1. Excitonic Effects in Methylammonium Lead Halide Perovskites.

    PubMed

    Chen, Xihan; Lu, Haipeng; Yang, Ye; Beard, Matthew C

    2018-05-17

    The exciton binding energy in methylammonium lead iodide (MAPbI 3 ) is about 10 meV, around 1/3 of the available thermal energy ( k B T ∼ 26 meV) at room temperature. Thus, exciton populations are not stable at room temperature at moderate photoexcited carrier densities. However, excitonic resonances dominate the absorption onset. Furthermore, these resonances determine the transient absorbance and transient reflectance spectra. The exciton binding energy is a reflection of the Coulomb interaction energy between photoexcited electrons and holes. As such, it serves as a marker for the strength of electron/hole interactions and impacts a variety of phenomena, such as, absorption, radiative recombination, and Auger recombination. In this Perspective, we discuss the role of excitons and excitonic resonances in the optical properties of lead-halide perovskite semiconductors. Finally, we discuss how the strong light-matter interactions induce an optical stark effect splitting the doubly spin degenerate ground exciton states and are easily observed at room temperature.

  2. A hybrid organic-inorganic perovskite dataset

    NASA Astrophysics Data System (ADS)

    Kim, Chiho; Huan, Tran Doan; Krishnan, Sridevi; Ramprasad, Rampi

    2017-05-01

    Hybrid organic-inorganic perovskites (HOIPs) have been attracting a great deal of attention due to their versatility of electronic properties and fabrication methods. We prepare a dataset of 1,346 HOIPs, which features 16 organic cations, 3 group-IV cations and 4 halide anions. Using a combination of an atomic structure search method and density functional theory calculations, the optimized structures, the bandgap, the dielectric constant, and the relative energies of the HOIPs are uniformly prepared and validated by comparing with relevant experimental and/or theoretical data. We make the dataset available at Dryad Digital Repository, NoMaD Repository, and Khazana Repository (http://khazana.uconn.edu/), hoping that it could be useful for future data-mining efforts that can explore possible structure-property relationships and phenomenological models. Progressive extension of the dataset is expected as new organic cations become appropriate within the HOIP framework, and as additional properties are calculated for the new compounds found.

  3. Large Thermal Motion in Halide Perovskites

    DOE PAGES

    Tyson, T. A.; Gao, W.; Chen, Y. -S.; ...

    2017-08-24

    Solar cells based on hybrid perovskites have shown high efficiency while possessing simple processing methods. To gain a fundamental understanding of their properties on an atomic level, we investigate single crystals of CH 3NH 3PbI 3 with a narrow transition (~5 K) near 327 K. Temperature dependent structural measurements reveal a persistent tetragonal structure with smooth changes in the atomic displacement parameters (ADPs) on crossing T*. We show that the ADPs for I ions yield extended flat regions in the potential wells consistent with the measured large thermal expansion parameter. Molecular dynamics simulations reveal that this material exhibits significant asymmetriesmore » in the Pb-I pair distribution functions. We also show that the intrinsically enhanced freedom of motion of the iodine atoms enables large deformations. This flexibility (softness) of the atomic structure results in highly localized atomic relaxation about defects and hence accounts for both the high carrier mobility as well as the structural instability.« less

  4. Topological Oxide Insulator in Cubic Perovskite Structure

    PubMed Central

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

    2013-01-01

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

  5. Overcoming the Photovoltage Plateau in Large Bandgap Perovskite Photovoltaics

    DOE PAGES

    Rajagopal, Adharsh; Stoddard, Ryan J.; Jo, Sae Byeok; ...

    2018-05-07

    Development of large bandgap (1.80−1.85 eV Eg) perovskite is crucial for perovskite−perovskite tandem solar cells. However, the performance of 1.80−1.85 eV Eg perovskite solar cells (PVKSCs) are significantly lagging their counterparts in the 1.60−1.75 eV Eg range. This is because the photovoltage (Voc) does not proportionally increase with Eg due to lower optoelectronic quality of conventional (MA,FA,Cs)Pb(I,Br)3 and results in a photovoltage plateau (Voc limited to 80% of the theoretical limit for ∼1.8 eV Eg). Here, we incorporate phenyl- ethylammonium (PEA) in a mixed-halide perovskite composition to solve the inherent material-level challenges in 1.80−1.85 eV Eg perovskites. The amount ofmore » PEA incorporation governs the topography and optoelectronic properties of resultant films. Detailed structural and spectroscopic characterization reveal the characteristic trends in crystalline size, orientation, and charge carrier recombination dynamics and rationalize the origin of improved material quality with higher luminescence. With careful interface optimization, the improved material characteristics were translated to devices and Voc values of 1.30−1.35 V were achieved, which correspond to 85−87% of the theoretical limit. Using an optimal amount of PEA incorporation to balance the increase in Voc and the decrease in charge collection, a highest power conversion efficiency of 12.2% was realized. Our results clearly overcome the photovoltage plateau in the 1.80−1.85 eV Eg range and represent the highest Voc achieved for mixed-halide PVKSCs. This study provides widely translatable insights, an important breakthrough, and a promising platform for next- generation perovskite tandems.« less

  6. Overcoming the Photovoltage Plateau in Large Bandgap Perovskite Photovoltaics

    SciTech Connect

    Rajagopal, Adharsh; Stoddard, Ryan J.; Jo, Sae Byeok

    Development of large bandgap (1.80−1.85 eV Eg) perovskite is crucial for perovskite−perovskite tandem solar cells. However, the performance of 1.80−1.85 eV Eg perovskite solar cells (PVKSCs) are significantly lagging their counterparts in the 1.60−1.75 eV Eg range. This is because the photovoltage (Voc) does not proportionally increase with Eg due to lower optoelectronic quality of conventional (MA,FA,Cs)Pb(I,Br)3 and results in a photovoltage plateau (Voc limited to 80% of the theoretical limit for ∼1.8 eV Eg). Here, we incorporate phenyl- ethylammonium (PEA) in a mixed-halide perovskite composition to solve the inherent material-level challenges in 1.80−1.85 eV Eg perovskites. The amount ofmore » PEA incorporation governs the topography and optoelectronic properties of resultant films. Detailed structural and spectroscopic characterization reveal the characteristic trends in crystalline size, orientation, and charge carrier recombination dynamics and rationalize the origin of improved material quality with higher luminescence. With careful interface optimization, the improved material characteristics were translated to devices and Voc values of 1.30−1.35 V were achieved, which correspond to 85−87% of the theoretical limit. Using an optimal amount of PEA incorporation to balance the increase in Voc and the decrease in charge collection, a highest power conversion efficiency of 12.2% was realized. Our results clearly overcome the photovoltage plateau in the 1.80−1.85 eV Eg range and represent the highest Voc achieved for mixed-halide PVKSCs. This study provides widely translatable insights, an important breakthrough, and a promising platform for next- generation perovskite tandems.« less

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

    SciTech Connect

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

    2015-05-15

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

  8. Substituted decision making: elder guardianship.

    PubMed

    Leatherman, Martha E; Goethe, Katherine E

    2009-11-01

    The goal of this column is to help experienced clinicians navigate the judicial system when they are confronted with requests for capacity evaluations that involve guardianship (conservatorship). The interface between the growing elderly medical population and increasing requests for substituted decision making is becoming more complex. This column will help practicing psychiatrists understand the medical, legal, and societal factors involved in adult guardianship. Such understanding is necessary in order to effectively perform guardianship evaluations and adequately inform courts, patients, and families about the psychiatric diagnoses central to substituted decision making.

  9. Ultrafast time-resolved spectroscopy of lead halide perovskite films

    NASA Astrophysics Data System (ADS)

    Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

    2015-09-01

    Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

  10. Methods for producing single crystal mixed halide perovskites

    DOEpatents

    Zhu, Kai; Zhao, Yixin

    2017-07-11

    An aspect of the present invention is a method that includes contacting a metal halide and a first alkylammonium halide in a solvent to form a solution and maintaining the solution at a first temperature, resulting in the formation of at least one alkylammonium halide perovskite crystal, where the metal halide includes a first halogen and a metal, the first alkylammonium halide includes the first halogen, the at least one alkylammonium halide perovskite crystal includes the metal and the first halogen, and the first temperature is above about 21.degree. C.

  11. Perovskite Solar Cells and Devices at EPFL Valais Wallis.

    PubMed

    Nazeeruddin, Mohammad Khaja

    2016-09-22

    Stability required! Perovskite solar cells have emerged as one of the most exciting fields of research, owing to their impressive rise in power conversion efficiency surpassing 22% in six short years of research. Current research is focused on ways to improve stability of perovskite-based devices, a key characteristic required to bring this technology from the lab into the market. In this Editorial, guest editor Prof. Mohammad Khaja Nazeeruddin describes the context of this Special Issue, and summarizes the work being performed in his research group toward this low-cost near-future photovoltaic technology. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Substitution determination of Fmoc‐substituted resins at different wavelengths

    PubMed Central

    Kley, Markus; Bächle, Dirk; Loidl, Günther; Meier, Thomas; Samson, Daniel

    2017-01-01

    In solid‐phase peptide synthesis, the nominal batch size is calculated using the starting resin substitution and the mass of the starting resin. The starting resin substitution constitutes the basis for the calculation of a whole set of important process parameters, such as the number of amino acid derivative equivalents. For Fmoc‐substituted resins, substitution determination is often performed by suspending the Fmoc‐protected starting resin in 20% (v/v) piperidine in DMF to generate the dibenzofulvene–piperidine adduct that is quantified by ultraviolet–visible spectroscopy. The spectrometric measurement is performed at the maximum absorption wavelength of the dibenzofulvene–piperidine adduct, that is, at 301.0 nm. The recorded absorption value, the resin weight and the volume are entered into an equation derived from Lambert–Beer's law, together with the substance‐specific molar absorption coefficient at 301.0 nm, in order to calculate the nominal substitution. To our knowledge, molar absorption coefficients between 7100 l mol−1 cm−1 and 8100 l mol−1 cm−1 have been reported for the dibenzofulvene–piperidine adduct at 301.0 nm. Depending on the applied value, the nominal batch size may differ up to 14%. In this publication, a determination of the molar absorption coefficients at 301.0 and 289.8 nm is reported. Furthermore, proof is given that by measuring the absorption at 289.8 nm the impact of wavelength accuracy is reduced. © 2017 The Authors Journal of Peptide Science published by European Peptide Society and John Wiley & Sons Ltd. PMID:28635051

  13. Substitution determination of Fmoc-substituted resins at different wavelengths.

    PubMed

    Eissler, Stefan; Kley, Markus; Bächle, Dirk; Loidl, Günther; Meier, Thomas; Samson, Daniel

    2017-10-01

    In solid-phase peptide synthesis, the nominal batch size is calculated using the starting resin substitution and the mass of the starting resin. The starting resin substitution constitutes the basis for the calculation of a whole set of important process parameters, such as the number of amino acid derivative equivalents. For Fmoc-substituted resins, substitution determination is often performed by suspending the Fmoc-protected starting resin in 20% (v/v) piperidine in DMF to generate the dibenzofulvene-piperidine adduct that is quantified by ultraviolet-visible spectroscopy. The spectrometric measurement is performed at the maximum absorption wavelength of the dibenzofulvene-piperidine adduct, that is, at 301.0 nm. The recorded absorption value, the resin weight and the volume are entered into an equation derived from Lambert-Beer's law, together with the substance-specific molar absorption coefficient at 301.0 nm, in order to calculate the nominal substitution. To our knowledge, molar absorption coefficients between 7100 l mol -1  cm -1 and 8100 l mol -1  cm -1 have been reported for the dibenzofulvene-piperidine adduct at 301.0 nm. Depending on the applied value, the nominal batch size may differ up to 14%. In this publication, a determination of the molar absorption coefficients at 301.0 and 289.8 nm is reported. Furthermore, proof is given that by measuring the absorption at 289.8 nm the impact of wavelength accuracy is reduced. © 2017 The Authors Journal of Peptide Science published by European Peptide Society and John Wiley & Sons Ltd. © 2017 The Authors Journal of Peptide Science published by European Peptide Society and John Wiley & Sons Ltd.

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

    SciTech Connect

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

    2017-01-15

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

  15. Magnetism and the spin state in cubic perovskite CaCo O 3 synthesized under high pressure

    SciTech Connect

    Xia, Hailiang; Dai, Jianhong; Xu, Yuanji

    Cubic SrCo O 3 with an intermediate spin state can only be stabilized by high pressure and high temperature (HPHT) treatment. It is metallic and ferromagnetic with the highest Curie temperature of the transition-metal perovskites. The chemical substitution by Ca on Sr sites would normally lower crystal symmetry from cubic to orthorhombic as seen in the perovskite family of Ca M O 3 ( M = M 4 + of transition metals, G e 4 + , S n 4 + , and Z r 4 +) at room temperature. This structural change narrows the bandwidth, so as to furthermore » enhance the Curie temperature as the crossover to the localized electronic state is approached. Here, we report a successful synthesis of the perovskite CaCo O 3 with a HPHT treatment. Surprisingly, CaCo O 3 crystallizes in a simple cubic structure that remains stable down to 20 K, the lowest temperature in the structural study. The new perovskite has been thoroughly characterized by a suite of measurements including transport, magnetization, specific heat, thermal conductivity, and thermoelectric power. Furthermore, metallic CaCo O 3 undergoes two successive magnetic transitions at 86 K and 54 K as temperature decreases. The magnetization at 5 K is compatible with the intermediate spin state t 4 e 1 of C o 4 + at the octahedral site. The thermal expansion of the Co-O bond length indicates that the population of high spin state t 3 e 2 increases for T > 100 K . The shortest Co-O bond length in cubic CaCo O 3 is responsible for delocalizing electrons in the π * -band and itinerant-electron ferromagnetism at T < 54 K . In our comprehensive comparison between SrCo O 3 and CaCo O 3 and the justification of their physical properties by first-principles calculation were made in this report. Partially filled π * and σ * bands would make CaCo O 3 suitable to study the Hund's coupling effect in a metal.« less

  16. Magnetism and the spin state in cubic perovskite CaCo O 3 synthesized under high pressure

    DOE PAGES

    Xia, Hailiang; Dai, Jianhong; Xu, Yuanji; ...

    2017-07-17

    Cubic SrCo O 3 with an intermediate spin state can only be stabilized by high pressure and high temperature (HPHT) treatment. It is metallic and ferromagnetic with the highest Curie temperature of the transition-metal perovskites. The chemical substitution by Ca on Sr sites would normally lower crystal symmetry from cubic to orthorhombic as seen in the perovskite family of Ca M O 3 ( M = M 4 + of transition metals, G e 4 + , S n 4 + , and Z r 4 +) at room temperature. This structural change narrows the bandwidth, so as to furthermore » enhance the Curie temperature as the crossover to the localized electronic state is approached. Here, we report a successful synthesis of the perovskite CaCo O 3 with a HPHT treatment. Surprisingly, CaCo O 3 crystallizes in a simple cubic structure that remains stable down to 20 K, the lowest temperature in the structural study. The new perovskite has been thoroughly characterized by a suite of measurements including transport, magnetization, specific heat, thermal conductivity, and thermoelectric power. Furthermore, metallic CaCo O 3 undergoes two successive magnetic transitions at 86 K and 54 K as temperature decreases. The magnetization at 5 K is compatible with the intermediate spin state t 4 e 1 of C o 4 + at the octahedral site. The thermal expansion of the Co-O bond length indicates that the population of high spin state t 3 e 2 increases for T > 100 K . The shortest Co-O bond length in cubic CaCo O 3 is responsible for delocalizing electrons in the π * -band and itinerant-electron ferromagnetism at T < 54 K . In our comprehensive comparison between SrCo O 3 and CaCo O 3 and the justification of their physical properties by first-principles calculation were made in this report. Partially filled π * and σ * bands would make CaCo O 3 suitable to study the Hund's coupling effect in a metal.« less

  17. Magnetism and the spin state in cubic perovskite CaCo O3 synthesized under high pressure

    NASA Astrophysics Data System (ADS)

    Xia, Hailiang; Dai, Jianhong; Xu, Yuanji; Yin, Yunyu; Wang, Xiao; Liu, Zhehong; Liu, Min; McGuire, Michael A.; Li, Xiang; Li, Zongyao; Jin, Changqing; Yang, Yifeng; Zhou, Jianshi; Long, Youwen

    2017-07-01

    Cubic SrCo O3 with an intermediate spin state can only be stabilized by high pressure and high temperature (HPHT) treatment. It is metallic and ferromagnetic with the highest Curie temperature of the transition-metal perovskites. The chemical substitution by Ca on Sr sites would normally lower crystal symmetry from cubic to orthorhombic as seen in the perovskite family of Ca M O3 (M =M4 + of transition metals, G e4 + , S n4 + , and Z r4 + ) at room temperature. This structural change narrows the bandwidth, so as to further enhance the Curie temperature as the crossover to the localized electronic state is approached. We report a successful synthesis of the perovskite CaCo O3 with a HPHT treatment. Surprisingly, CaCo O3 crystallizes in a simple cubic structure that remains stable down to 20 K, the lowest temperature in the structural study. The new perovskite has been thoroughly characterized by a suite of measurements including transport, magnetization, specific heat, thermal conductivity, and thermoelectric power. Metallic CaCo O3 undergoes two successive magnetic transitions at 86 K and 54 K as temperature decreases. The magnetization at 5 K is compatible with the intermediate spin state t4e1 of C o4 + at the octahedral site. The thermal expansion of the Co-O bond length indicates that the population of high spin state t3e2 increases for T >100 K . The shortest Co-O bond length in cubic CaCo O3 is responsible for delocalizing electrons in the π*-band and itinerant-electron ferromagnetism at T <54 K . A comprehensive comparison between SrCo O3 and CaCo O3 and the justification of their physical properties by first-principles calculation have also been made in this report. Partially filled π* and σ* bands would make CaCo O3 suitable to study the Hund's coupling effect in a metal.

  18. Structure, magnetism and electronic properties in 3d-5d based double perovskite ({Sr_{1-x}} Y x )2FeIrO6

    NASA Astrophysics Data System (ADS)

    Kharkwal, K. C.; Pramanik, A. K.

    2017-12-01

    The 3d-5d based double perovskites are of current interest as they provide model systems to study the interplay between electronic correlation (U) and spin-orbit coupling (SOC). Here, we report detailed structural, magnetic and transport properties of doped double perovskite material (Sr1-x Y x )2FeIrO6 with x ≤slant 0.2 . With substitution of Y, the system retains its original crystal structure but structural parameters change with x in nonmonotonic fashion. The magnetization data for Sr2FeIrO6 show antiferromagnetic type magnetic transition around 45 K however, a close inspection of the data indicates a weak magnetic phase transition around 120 K. No change of structural symmetry has been observed down to low temperature, although the lattice parameters show sudden changes around the magnetic transitions. Sr2FeIrO6 shows an insulating behavior over the whole temperature range, which nevertheless does not change with Y substitution. The nature of charge conduction is found to follow thermally activated Mott’s variable range hopping and power law behavior for parent and doped samples, respectively. Interestingly, evolution of structural, magnetic and transport behavior in (Sr1-x Y x )2FeIrO6 is observed to reverse with x > 0.1 , which is believed to arise due to a change in the transition metal ionic state.

  19. Structure, magnetism and electronic properties in 3d-5d based double perovskite ([Formula: see text]Y x )2FeIrO6.

    PubMed

    Kharkwal, K C; Pramanik, A K

    2017-11-13

    The 3d-5d based double perovskites are of current interest as they provide model systems to study the interplay between electronic correlation (U) and spin-orbit coupling (SOC). Here, we report detailed structural, magnetic and transport properties of doped double perovskite material ([Formula: see text]Y x ) 2 FeIrO 6 with [Formula: see text]. With substitution of Y, the system retains its original crystal structure but structural parameters change with x in nonmonotonic fashion. The magnetization data for Sr 2 FeIrO 6 show antiferromagnetic type magnetic transition around 45 K; however, a close inspection of the data indicates a weak magnetic phase transition around 120 K. No change of structural symmetry has been observed down to low temperature, although the lattice parameters show sudden changes around the magnetic transitions. Sr 2 FeIrO 6 shows an insulating behavior over the whole temperature range, which nevertheless does not change with Y substitution. The nature of charge conduction is found to follow thermally activated Mott's variable range hopping and power law behavior for parent and doped samples, respectively. Interestingly, evolution of structural, magnetic and transport behavior in ([Formula: see text]Y x ) 2 FeIrO 6 is observed to reverse with [Formula: see text], which is believed to arise due to a change in the transition metal ionic state.

  20. Potential for structural lumber substitutes

    Treesearch

    Theodore L. Laufenberg

    1985-01-01

    The potential for substitution of structural wood composites into solid-sawn lumber markets is presented from the technological viewpoint. Technological limitations of existing composite processes and products are reviewed in the context of the present laminated veneer lumber (LVL), flakeboard, and fiber/ paper industries. The limits of mechanical property potential...

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

    NASA Technical Reports Server (NTRS)

    Li, Xiaoyuan; Jeanloz, Raymond

    1987-01-01

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

  2. Polymorphic Transitions in Cerium-Substituted Zirconolite (CaZrTi 2O 7)

    DOE PAGES

    Clark, Braeden M.; Sundaram, S. K.; Misture, Scott T.

    2017-07-19

    Compounds with the formulae CaZr 1–xCe xTi 2O 7 with x = 0.1–0.5 were synthesized by solid state reaction. Cerium was used as a surrogate for actinide elements. A transition from the 2M polymorph to the 4M polymorph (expanded unit cell due to cation ordering) in zirconolite was observed with increasing cerium content. The presence of both tri- and tetravalent Ce, contrary to formulation, was confirmed using X-ray absorption near edge spectroscopy, suggesting substitution on both Ca and Zr sites. Sintering was carried out via spark plasma sintering, during which the perovskite phase (Ca 0.4Ce 0.4TiO 3) was stabilized duemore » to the reducing conditions of this technique. Scanning electron microscopy and energy dispersive spectrometry revealed that the 2M polymorph was dilute in Ce content in comparison to the 4M-zirconolite. High temperature X-ray diffraction was used to detail the kinetics of perovskite to zirconolite transition. It was found that CaCeTi 2O 7 (cubic pyrochlore) formed as an intermediate phase during the transition. Lastly, our results show that a transition from 2M- to 4M-zirconolite occurs with increasing Ce content and can be controlled by adjusting the P O2 and the heat treatment temperature.« less

  3. Polymorphic Transitions in Cerium-Substituted Zirconolite (CaZrTi 2O 7)

    SciTech Connect

    Clark, Braeden M.; Sundaram, S. K.; Misture, Scott T.

    Compounds with the formulae CaZr 1–xCe xTi 2O 7 with x = 0.1–0.5 were synthesized by solid state reaction. Cerium was used as a surrogate for actinide elements. A transition from the 2M polymorph to the 4M polymorph (expanded unit cell due to cation ordering) in zirconolite was observed with increasing cerium content. The presence of both tri- and tetravalent Ce, contrary to formulation, was confirmed using X-ray absorption near edge spectroscopy, suggesting substitution on both Ca and Zr sites. Sintering was carried out via spark plasma sintering, during which the perovskite phase (Ca 0.4Ce 0.4TiO 3) was stabilized duemore » to the reducing conditions of this technique. Scanning electron microscopy and energy dispersive spectrometry revealed that the 2M polymorph was dilute in Ce content in comparison to the 4M-zirconolite. High temperature X-ray diffraction was used to detail the kinetics of perovskite to zirconolite transition. It was found that CaCeTi 2O 7 (cubic pyrochlore) formed as an intermediate phase during the transition. Lastly, our results show that a transition from 2M- to 4M-zirconolite occurs with increasing Ce content and can be controlled by adjusting the P O2 and the heat treatment temperature.« less

  4. The Influence of Fe Substitution in Lanthanum Calcium Cobalt Oxide on the Oxygen Evolution Reaction in Alkaline Media

    DOE PAGES

    Abreu-Sepulveda, Maria A.; Dhital, Chetan; Huq, Ashfia; ...

    2016-07-30

    The effect due to systematic substitution of cobalt by iron in La 0.6Ca 0.4Co 1-xFe xO 3 towards the oxygen evolution reaction(OER) in alkaline media has been investigated. We synthesized these compounds by a facile glycine-nitrate synthesis and the phase formation was confirmed by X-ray diffraction and Neutron Diffraction elemental analysis. The apparent OER activity was evaluated by quasi steady state current measurements in alkaline media using a traditional three-electrode cell. X-ray photoelectron spectroscopy shows iron substitution causes an increase in the surface concentration of various cobalt oxidation states. Tafel slope in the vicinity of 60 mV/decade and electrochemical reactionmore » order towards OH- near unity were achieved for the unsubstituted La 0.6Ca 0.4CoO 3. Moreover, a decrease in the Tafel slope to 49 mV/decade was observed when iron is substituted in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction, however the relationship of specific current density with Fe fraction is not linear. High Fe substitutions, La 0.6Ca 0.4Co 0.2Fe 0.8O 3 and La 0.6Ca 0.4Co 0.1Fe 0.9O 3 showed higher area specific activity towards OER than La 0.6Ca 0.4CoO 3 or La 0.6Ca 0.4FeO 3. Finally, we believe iron inclusion in the cobalt sites of the perovskite helps decrease the electron transfer barrier and facilitates the formation of cobalt-hydroxide at the surface. Possible OER mechanisms based on the observed kinetic parameters will be discussed.« less

  5. 40 CFR Appendix B to Subpart G of... - Substitutes Subject to Use Restrictions and Unacceptable Substitutes

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Use Conditions Substitutes Application Substitute Decision Conditions Comments Electronics Cleaning w.... Electronics cleaning w/CFC-113 Dibromomethane Unacceptable High ODP; other alternatives exist. Electronics...

  6. Enhancement of photoresponse property of perovskite solar cell by aluminium chloride (AlCl3)

    NASA Astrophysics Data System (ADS)

    Ghosh, S. S.; Sil, A.

    2018-05-01

    The fabrication of a three layer solar cell device is a new area of research. The formation of perovskite phase is evident from x-ray diffraction and its particle size is observed by microstructural analysis. A thin layer of gold coating over the device increases the surface conductivity. Direct contact between a SnCl2 or AlCl3 based perovskite with the gold coating increases the durability of the film but decreases the hole transport properties due to absence of an organic hole transport material. The absorbance spectroscopy analysis gives characteristic peaks showing the evidence of ITO, TiO2 (rutile) and Sn2+ complexes present in the Sn-perovskite film or Al3+ complexes present within the Al-perovskite cell. The desired absorbance near 550 nm due to Al3+ complexes causes a much higher flow of current on illumination and thus is also evidenced by the presence of comparatively high intensity PL spectra in the Al-perovskite system which occurred due to free exciton formation near band edge excitation. The fill factor of the devices is estimated as ∼0.83 and ∼0.65 for Sn-perovskite and Al-perovskite devices respectively. The PCE values of Sn-perovskite and Al-perovskite devices are calculated 0.39% and 0.96% respectively, which establish Al-perovskite film as a useful component for future solar cell device manufacturing.

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

    PubMed

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

    2017-10-09

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

  8. Fabrication of single phase 2D homologous perovskite microplates by mechanical exfoliation

    NASA Astrophysics Data System (ADS)

    Li, Junze; Wang, Jun; Zhang, Yingjun; Wang, Haizhen; Lin, Gaoming; Xiong, Xuan; Zhou, Weihang; Luo, Hongmei; Li, Dehui

    2018-04-01

    The two-dimensional (2D) Ruddlesden-Popper type perovskites have attracted intensive interest for their great environmental stability and various potential optoelectronic applications. Fundamental understanding of the photophysical and electronic properties of the 2D perovskites with pure single phase is essential for improving the performance of the optoelectronic devices and designing devices with new architectures. Investigating the optical and electronic properties of these materials with pure single phase is required to obtain pure single phase 2D perovskites. Here, we report on an alternative approach to fabricate (C4H9NH3)2(CH3NH3) n-1Pb n I3n+1 microplates with pure single n-number perovskite phase for n  >  2 by mechanical exfoliation. Micro-photoluminescence and absorption spectroscopy studies reveal that the as-synthesized 2D perovskite plates for n  >  2 are comprised by dominant n-number phase and small inclusions of hybrid perovskite phases with different n values, which is supported by excitation power dependent photoluminescence. By mechanical exfoliation method, 2D perovskite microplates with the thickness of around 20 nm are obtained, which surprisingly have single n-number perovskite phase for n  =  2-5. In addition, we have demonstrated that the exfoliated 2D perovskite microplates can be integrated with other 2D layered materials such as boron nitride, and are able to be transferred to prefabricated electrodes for photodetections. Our studies not only provide a strategy to prepare 2D perovskites with a single n-number perovskite phase allowing us to extract the basic optical and electronic parameters of pure phase perovskites, but also demonstrate the possibility to integrate the 2D perovskites with other 2D layered materials to extend the device’s functionalities.

  9. Low-cost electrodes for stable perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Bastos, João P.; Manghooli, Sara; Jaysankar, Manoj; Tait, Jeffrey G.; Qiu, Weiming; Gehlhaar, Robert; De Volder, Michael; Uytterhoeven, Griet; Poortmans, Jef; Paetzold, Ulrich W.

    2017-06-01

    Cost-effective production of perovskite solar cells on an industrial scale requires the utilization of exclusively inexpensive materials. However, to date, highly efficient and stable perovskite solar cells rely on expensive gold electrodes since other metal electrodes are known to cause degradation of the devices. Finding a low-cost electrode that can replace gold and ensure both efficiency and long-term stability is essential for the success of the perovskite-based solar cell technology. In this work, we systematically compare three types of electrode materials: multi-walled carbon nanotubes (MWCNTs), alternative metals (silver, aluminum, and copper), and transparent oxides [indium tin oxide (ITO)] in terms of efficiency, stability, and cost. We show that multi-walled carbon nanotubes are the only electrode that is both more cost-effective and stable than gold. Devices with multi-walled carbon nanotube electrodes present remarkable shelf-life stability, with no decrease in the efficiency even after 180 h of storage in 77% relative humidity (RH). Furthermore, we demonstrate the potential of devices with multi-walled carbon nanotube electrodes to achieve high efficiencies. These developments are an important step forward to mass produce perovskite photovoltaics in a commercially viable way.

  10. Perovskite Solar Cells for High-Efficiency Tandems

    SciTech Connect

    McGehee, Michael; Buonassisi, Tonio

    The first monolithic perovskite/silicon tandem was made with a diffused silicon p-n junction, a tunnel junction made of n ++ hydrogenated amorphous silicon, a titania electron transport layer, a methylammonium lead iodide absorber, and a Spiro-OMeTAD hole transport layer (HTL). The power conversion efficiency (PCE) was only 13.7% due to excessive parasitic absorption of light in the HTL, limiting the matched current density to 11.5 mA/cm 2. Werner et al. 15 raised the PCE to a record 21.2% by switching to a silicon heterojunction bottom cell and carefully tuning layer thicknesses to achieve lower optical loss and a higher currentmore » density of 15.9 mA/cm 2. It is clear from these reports that minimizing parasitic absorption in the window layers is crucial to achieving higher current densities and efficiencies in monolithic tandems. To this end, the window layers through which light first passes before entering the perovskite and silicon absorber materials must be highly transparent. The front electrode must also be conductive to carry current laterally across the top of the device. Indium tin oxide (ITO) is widely utilized as a transparent electrode in optoelectronic devices such as flat-panel displays, smart windows, organic light-emitting diodes, and solar cells due to its high conductivity and broadband transparency. ITO is typically deposited through magnetron sputtering; however, the high kinetic energy of sputtered particles can damage underlying layers. In perovskite solar cells, a sputter buffer layer is required to protect the perovskite and organic carrier extraction layers from damage during sputter deposition. The ideal buffer layer should also be energetically well aligned so as to act as a carrier-selective contact, have a wide bandgap to enable high optical transmission, and have no reaction with the halides in the perovskite. Additionally, this buffer layer should act as a diffusion barrier layer to prevent both organic cation evolution and

  11. Oxide perovskite crystals for HTSC film substrates microwave applications

    NASA Technical Reports Server (NTRS)

    Bhalla, A. S.; Guo, Ruyan

    1995-01-01

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

  12. Thermodynamic origin of instability in hybrid halide perovskites

    PubMed Central

    Tenuta, E.; Zheng, C.; Rubel, O.

    2016-01-01

    Degradation of hybrid halide perovskites under the influence of environmental factors impairs future prospects of using these materials as absorbers in solar cells. First principle calculations can be used as a guideline in search of new materials, provided we can rely on their predictive capabilities. We show that the instability of perovskites can be captured using ab initio total energy calculations for reactants and products augmented with additional thermodynamic data to account for finite temperature effects. Calculations suggest that the instability of CH3NH3PbI3 in moist environment is linked to the aqueous solubility of the CH3NH3I salt, thus making other perovskite materials with soluble decomposition products prone to degradation. Properties of NH3OHPbI3, NH3NH2PbI3, PH4PbI3, SbH4PbI3, CsPbBr3, and a new hypothetical SF3PbI3 perovskite are studied in the search for alternative solar cell absorber materials with enhanced chemical stability. PMID:27883032

  13. Nanoscale Confinement Leads to New All-inorganic Perovskite with

    Science.gov Websites

    research into perovskites has centered on a hybrid organic-inorganic structure. Since research into climbed steadily and now shows greater than 22 percent power conversion efficiency. However, the organic unstable organic component and open the door to high-efficiency quantum dot optoelectronics that can be

  14. How Strong Is the Hydrogen Bond in Hybrid Perovskites?

    PubMed Central

    2017-01-01

    Hybrid organic–inorganic perovskites represent a special class of metal–organic framework where a molecular cation is encased in an anionic cage. The molecule–cage interaction influences phase stability, phase transformations, and the molecular dynamics. We examine the hydrogen bonding in four AmBX3 formate perovskites: [Am]Zn(HCOO)3, with Am+ = hydrazinium (NH2NH3+), guanidinium (C(NH2)3+), dimethylammonium (CH3)2NH2+, and azetidinium (CH2)3NH2+. We develop a scheme to quantify the strength of hydrogen bonding in these systems from first-principles, which separates the electrostatic interactions between the amine (Am+) and the BX3– cage. The hydrogen-bonding strengths of formate perovskites range from 0.36 to 1.40 eV/cation (8–32 kcalmol–1). Complementary solid-state nuclear magnetic resonance spectroscopy confirms that strong hydrogen bonding hinders cation mobility. Application of the procedure to hybrid lead halide perovskites (X = Cl, Br, I, Am+ = CH3NH3+, CH(NH2)2+) shows that these compounds have significantly weaker hydrogen-bonding energies of 0.09 to 0.27 eV/cation (2–6 kcalmol–1), correlating with lower order–disorder transition temperatures. PMID:29216715

  15. Perovskite-Fullerene Hybrid Materials Eliminate Hysteresis In Planar Diodes

    DOE PAGES

    Xu, Jixian; Buin, Andrei; Ip, Alexander H.; ...

    2015-03-31

    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 solarmore » 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.« less

  16. Synthesis of Cesium Lead Halide Perovskite Quantum Dots

    ERIC Educational Resources Information Center

    Shekhirev, Mikhail; Goza, John; Teeter, Jacob D.; Lipatov, Alexey; Sinitskii, Alexander

    2017-01-01

    Synthesis of quantum dots is a valuable experiment for demonstration and discussion of quantum phenomena in undergraduate chemistry curricula. Recently, a new class of all-inorganic perovskite quantum dots (QDs) with a formula of CsPbX[subscript 3] (X = Cl, Br, I) was presented and attracted tremendous attention. Here we adapt the synthesis of…

  17. Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects

    DOE PAGES

    Liu, Yuanyue; Xiao, Hai; Goddard, William A.

    2016-04-21

    Two-dimensional (2D) halide perovskites are emerging as promising candidates for nanoelectronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g., transition metal dichalcogenides MX 2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gapmore » states. Here, we show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX 2. The donors tend to have high formation energies and the harmful defects are difficult to form at a low halide chemical potential. Thus, we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them.« less

  18. Excitations Partition into Two Distinct Populations in Bulk Perovskites

    SciTech Connect

    Wang, Lili; Brawand, Nicholas P.; Vörös, Márton

    2018-01-09

    Organolead halide perovskites convert optical excitations to charge carriers with remarkable efficiency in optoelectronic devices. Previous research predominantly documents dynamics in perovskite thin films; however, extensive disorder in this platform may obscure the observed carrier dynamics. Here, carrier dynamics in perovskite single-domain single crystals is examined by performing transient absorption spectroscopy in a transmissive geometry. Two distinct sets of carrier populations that coexist at the same radiation fluence, but display different decay dynamics, are observed: one dominated by second-order recombination and the other by third-order recombination. Based on ab initio simulations, this observation is found to be most consistent withmore » the hypothesis that free carriers and localized carriers coexist due to polaron formation. The calculations suggest that polarons will form in both CH3NH3PbBr3 and CH3NH3PbI3 crystals, but that they are more pronounced in CH3NH3PbBr3. Single-crystal CH3NH3PbBr3 could represent the key to understanding the impact of polarons on the transport properties of perovskite optoelectronic devices.« less

  19. Multifunctional MgO Layer in Perovskite Solar Cells.

    PubMed

    Guo, Xudong; Dong, Haopeng; Li, Wenzhe; Li, Nan; Wang, Liduo

    2015-06-08

    A multifunctional magnesium oxide (MgO) layer was successfully introduced into perovskite solar cells (PSCs) to enhance their performance. MgO was coated onto the surface of mesoporous TiO(2) by the decomposition of magnesium acetate and, therefore, could block contact between the perovskite and TiO(2). X-ray photoelectron spectroscopy and infrared spectroscopy showed that the amount of H(2)O/hydroxyl absorbed on the TiO(2) decreased after MgO modification. The UV/Vis absorption spectra of the perovskite with MgO modification revealed an enhanced photoelectric performance compared with that of unmodified perovskite after UV illumination. In addition to the photocurrent, the photovoltage and fill factor also showed an enhancement after modification, which resulted in an increase in the overall efficiency of the cell from 9.6 to 13.9 %. Electrochemical impedance spectroscopy (EIS) confirmed that MgO acts as an insulating layer to reduce charge recombination. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Field-emission from quantum-dot-in-perovskite solids

    PubMed Central

    García de Arquer, F. Pelayo; Gong, Xiwen; Sabatini, Randy P.; Liu, Min; Kim, Gi-Hwan; Sutherland, Brandon R.; Voznyy, Oleksandr; Xu, Jixian; Pang, Yuangjie; Hoogland, Sjoerd; Sinton, David; Sargent, Edward

    2017-01-01

    Quantum dot and well architectures are attractive for infrared optoelectronics, and have led to the realization of compelling light sensors. However, they require well-defined passivated interfaces and rapid charge transport, and this has restricted their efficient implementation to costly vacuum-epitaxially grown semiconductors. Here we report solution-processed, sensitive infrared field-emission photodetectors. Using quantum-dots-in-perovskite, we demonstrate the extraction of photocarriers via field emission, followed by the recirculation of photogenerated carriers. We use in operando ultrafast transient spectroscopy to sense bias-dependent photoemission and recapture in field-emission devices. The resultant photodiodes exploit the superior electronic transport properties of organometal halide perovskites, the quantum-size-tuned absorption of the colloidal quantum dots and their matched interface. These field-emission quantum-dot-in-perovskite photodiodes extend the perovskite response into the short-wavelength infrared and achieve measured specific detectivities that exceed 1012 Jones. The results pave the way towards novel functional photonic devices with applications in photovoltaics and light emission. PMID:28337981

  1. Comprehensive design of omnidirectional high-performance perovskite solar cells

    PubMed Central

    Zhang, Yutao; Xuan, Yimin

    2016-01-01

    The comprehensive design approach is established with coupled optical-electrical simulation for perovskite-based solar cell, which emerged as one of the most promising competitors to silicon solar cell for its low-cost fabrication and high PCE. The selection of structured surface, effect of geometry parameters, incident angle-dependence and polarization-sensitivity are considered in the simulation. The optical modeling is performed via the finite-difference time-domain method whilst the electrical properties are obtained by solving the coupled nonlinear equations of Poisson, continuity, and drift-diffusion equations. The optical and electrical performances of five different structured surfaces are compared to select a best structured surface for perovskite solar cell. The effects of the geometry parameters on the optical and electrical properties of the perovskite cell are analyzed. The results indicate that the light harvesting is obviously enhanced by the structured surface. The electrical performance can be remarkably improved due to the enhanced light harvesting of the designed best structured surface. The angle-dependence for s- and p-polarizations is investigated. The structured surface exhibits omnidirectional behavior and favorable polarization-insensitive feature within a wide incident angle range. Such a comprehensive design approach can highlight the potential of perovskite cell for power conversion in the full daylight. PMID:27405419

  2. Comprehensive design of omnidirectional high-performance perovskite solar cells.

    PubMed

    Zhang, Yutao; Xuan, Yimin

    2016-07-13

    The comprehensive design approach is established with coupled optical-electrical simulation for perovskite-based solar cell, which emerged as one of the most promising competitors to silicon solar cell for its low-cost fabrication and high PCE. The selection of structured surface, effect of geometry parameters, incident angle-dependence and polarization-sensitivity are considered in the simulation. The optical modeling is performed via the finite-difference time-domain method whilst the electrical properties are obtained by solving the coupled nonlinear equations of Poisson, continuity, and drift-diffusion equations. The optical and electrical performances of five different structured surfaces are compared to select a best structured surface for perovskite solar cell. The effects of the geometry parameters on the optical and electrical properties of the perovskite cell are analyzed. The results indicate that the light harvesting is obviously enhanced by the structured surface. The electrical performance can be remarkably improved due to the enhanced light harvesting of the designed best structured surface. The angle-dependence for s- and p-polarizations is investigated. The structured surface exhibits omnidirectional behavior and favorable polarization-insensitive feature within a wide incident angle range. Such a comprehensive design approach can highlight the potential of perovskite cell for power conversion in the full daylight.

  3. Controlling octahedral rotations in a perovskite via strain doping

    DOE PAGES

    Herklotz, Andreas; Biegalski, Michael D.; Lee, Ho Nyung; ...

    2016-05-24

    The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film canmore » be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO 3 films coherently grown on SrTiO 3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. Lastly, these results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials.« less

  4. Oxygen Vacancy Linear Clustering in a Perovskite Oxide

    DOE PAGES

    Eom, Kitae; Choi, Euiyoung; Choi, Minsu; ...

    2017-07-14

    Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. We report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO 3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti 2+ valence state or corresponding Ti 3d 2 electronic configuration along with divacancymore » cluster model analysis and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO 3 was verified by further X-ray diffuse scattering analysis. And because SrTiO 3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.« less

  5. Oxygen Vacancy Linear Clustering in a Perovskite Oxide

    SciTech Connect

    Eom, Kitae; Choi, Euiyoung; Choi, Minsu

    Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. We report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO 3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti 2+ valence state or corresponding Ti 3d 2 electronic configuration along with divacancymore » cluster model analysis and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO 3 was verified by further X-ray diffuse scattering analysis. And because SrTiO 3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.« less

  6. Electronic spin state of Fe,Al-containing MgSiO3 perovskite at lower mantle conditions

    NASA Astrophysics Data System (ADS)

    Kupenko, I.; McCammon, C.; Sinmyo, R.; Prescher, C.; Chumakov, A. I.; Kantor, A.; Rüffer, R.; Dubrovinsky, L.

    2014-02-01

    We have investigated silicate perovskite with composition Mg0.83Fe0.21Al0.06Si0.91O3 relevant for the lower mantle at pressures up to 81 GPa and temperatures up to 2000 K using conventional Mössbauer spectroscopy and synchrotron Nuclear Forward Scattering (NFS) combined with double-sided laser heating in a diamond anvil cell. Room temperature Mössbauer and NFS spectra at low pressure are dominated by high-spin Fe2 +, with minor amounts of Fe3 + and a component assigned to a metastable position of high-spin Fe2 + in the A-site predicted by computational studies. NFS data show a sharp transition (< 20 GPa) from high-spin Fe2 + to a new component with extremely high quadrupole splitting, similar to previous studies. Mössbauer data show the same transition, but over a broader pressure range likely due to the higher pressure gradient. The new Fe2 + component is assigned to intermediate-spin Fe2 +, consistent with previous X-ray emission studies. NFS data at high temperatures and high pressures comparable to those in the lower mantle are consistent with the presence of Fe2 + only in the intermediate-spin state and Fe3 + only in the high-spin state. Our results are therefore consistent with the occurrence of spin crossover only in Fe2 + in Fe-, Al-containing perovskite within the lower mantle.

  7. Architecture of the Interface between the Perovskite and Hole-Transport Layers in Perovskite Solar Cells.

    PubMed

    Moriya, Masahiro; Hirotani, Daisuke; Ohta, Tsuyoshi; Ogomi, Yuhei; Shen, Qing; Ripolles, Teresa S; Yoshino, Kenji; Toyoda, Taro; Minemoto, Takashi; Hayase, Shuzi

    2016-09-22

    The interface between the perovskite (PVK, CH 3 NH 3 PbI 3 ) and hole-transport layers in perovskite solar cells is discussed. The device architecture studied is as follows: F-doped tin oxide (FTO)-coated glass/compact TiO 2 /mesoporous TiO 2 /PVK/2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (Spiro-MeOTAD)/Au. After a thin layer of 4,4,4-trifluorobutylammonium iodide (TFBA) was inserted at the interface between PVK and Spiro-MeOTAD, the photovoltaic efficiency increased from 11.6-14.5 % to 15.1-17.6 %. TFBA (10 ppm) was added in the PVK solution before coating. Owing to the low surface tension of TFBA, TFBA rose to the surface of the PVK layer spontaneously during spin-coating to make a thin organic layer. The PVK grain boundaries also seemed to be passivated with the addition of TFBA. However, large differences in Urbach energies and valence band energy level were not observed for the PVK layer with and without the addition of TFBA. The charge recombination time constant between the PVK and the Spiro-MeOTAD became slower (from 8.4 to 280 μsec) after 10 ppm of TFBA was added in the PVK. The experimental results using TFBA conclude that insertion of a very thin layer at the interface between PVK and Spiro-MeOTAD is effective for suppressing charge recombination and increasing photovoltaic performances. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Characterization of perovskite layer on various nanostructured silicon wafer

    NASA Astrophysics Data System (ADS)

    Rostan, Nur Fairuz Mohd; Sepeai, Suhaila; Ramli, Noor Fadhilah; Azhari, Ayu Wazira; Ludin, Norasikin Ahmad; Teridi, Mohd Asri Mat; Ibrahim, Mohd Adib; Zaidi, Saleem H.

    2017-05-01

    Crystalline silicon (c-Si) solar cell dominates 90% of photovoltaic (PV) market. The c-Si is the most mature of all PV technologies and expected to remain leading the PV technology by 2050. The attractive characters of Si solar cell are stability, long lasting and higher lifetime. Presently, the efficiency of c-Si solar cell is still stuck at 25% for one and half decades. Tandem approach is one of the attempts to improve the Si solar cell efficiency with higher bandgap layer is stacked on top of Si bottom cell. Perovskite offers a big potential to be inserted into a tandem solar cell. Perovskite with bandgap of 1.6 to 1.9 eV will be able to absorb high energy photons, meanwhile c-Si with bandgap of 1.124 eV will absorb low energy photons. The high carrier mobility, high carrier lifetime, highly compatible with both solution and evaporation techniques makes perovskite an eligible candidate for perovskite-Si tandem configuration. The solution of methyl ammonium lead iodide (MAPbI3) was prepared by single step precursor process. The perovskite layer was deposited on different c-Si surface structure, namely planar, textured and Si nanowires (SiNWs) by using spin-coating technique at different rotation speeds. The nanostructure of Si surface was textured using alkaline based wet chemical etching process and SiNW was grown using metal assisted etching technique. The detailed surface morphology and absorbance of perovskite were studied in this paper. The results show that the thicknesses of MAPbI3 were reduced with the increasing of rotation speed. In addition, the perovskite layer deposited on the nanostructured Si wafer became rougher as the etching time and rotation speed increased. The average surface roughness increased from ˜24 nm to ˜38 nm for etching time range between 5-60 min at constant low rotation speed (2000 rpm) for SiNWs Si wafer.

  9. Optical Properties of Nitrogen-Substituted Strontium Titanate Thin Films Prepared by Pulsed Laser Deposition

    PubMed Central

    Marozau, Ivan; Shkabko, Andrey; Döbeli, Max; Lippert, Thomas; Logvinovich, Dimitri; Mallepell, Marc; Schneider, Christof W.; Weidenkaff, Anke; Wokaun, Alexander

    2009-01-01

    Perovskite-type N‑substituted SrTiO3 thin films with a preferential (001) orientation were grown by pulsed laser deposition on (001)-oriented MgO and LaAlO3 substrates. Application of N2 or ammonia using a synchronized reactive gas pulse produces SrTiO3-x:Nx films with a nitrogen content of up to 4.1 at.% if prepared with the NH3 gas pulse at a substrate temperature of 720 °C. Incorporating nitrogen in SrTiO3 results in an optical absorption at 370‑460 nm associated with localized N(2p) orbitals. The estimated energy of these levels is ≈2.7 eV below the conduction band. In addition, the optical absorption increases gradually with increasing nitrogen content.

  10. Dilution-Induced Formation of Hybrid Perovskite Nanoplatelets.

    PubMed

    Tong, Yu; Ehrat, Florian; Vanderlinden, Willem; Cardenas-Daw, Carlos; Stolarczyk, Jacek K; Polavarapu, Lakshminarayana; Urban, Alexander S

    2016-12-27

    Perovskite nanocrystals (NCs) are an important extension to the fascinating field of hybrid halide perovskites. Showing significantly enhanced photoluminescence (PL) efficiency and emission wavelengths tunable through halide content and size, they hold great promise for light-emitting applications. Despite the rapid advancement in this field, the physical nature and size-dependent excitonic properties have not been well investigated due to the challenges associated with their preparation. Herein we report the spontaneous formation of highly luminescent, quasi-2D organic-inorganic hybrid perovskite nanoplatelets (NPls) upon dilution of a dispersion of bulk-like NCs. The fragmentation of the large NCs is attributed to osmotic swelling induced by the added solvent. An excess of organic ligands in the solvent quickly passivates the newly formed surfaces, stabilizing the NPls in the process. The thickness of the NPls can be controlled both by the dilution level and by the ligand concentration. Such colloidal NPls and their thin films were found to be extremely stable under continuous UV light irradiation. Full tunability of the NPl emission wavelength is achieved by varying the halide ion used (bromide, iodide). Additionally, time-resolved PL measurements reveal an increasing radiative decay rate with decreasing thickness of the NPls, likely due to an increasing exciton binding energy. Similarly, measurements on iodide-containing NPls show a transformation from biexponential to monoexponential PL decay with decreasing thickness, likely due to an increasing fraction of excitonic recombination. This interesting phenomenon of change in fluorescence upon dilution is a result of the intricate nature of the perovskite material itself and is uncommon in inorganic materials. Our findings enable the synthesis of halide perovskite NCs with high quantum efficiency and good stability as well as a tuning of both their optical and morphological properties.

  11. Hybrid Dion-Jacobson 2D Lead Iodide Perovskites.

    PubMed

    Mao, Lingling; Ke, Weijun; Pedesseau, Laurent; Wu, Yilei; Katan, Claudine; Even, Jacky; Wasielewski, Michael R; Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2018-03-14

    The three-dimensional hybrid organic-inorganic perovskites have shown huge potential for use in solar cells and other optoelectronic devices. Although these materials are under intense investigation, derivative materials with lower dimensionality are emerging, offering higher tunability of physical properties and new capabilities. Here, we present two new series of hybrid two-dimensional (2D) perovskites that adopt the Dion-Jacobson (DJ) structure type, which are the first complete homologous series reported in halide perovskite chemistry. Lead iodide DJ perovskites adopt a general formula A'A n-1 Pb n I 3 n+1 (A' = 3-(aminomethyl)piperidinium (3AMP) or 4-(aminomethyl)piperidinium (4AMP), A = methylammonium (MA)). These materials have layered structures where the stacking of inorganic layers is unique as they lay exactly on top of another. With a slightly different position of the functional group in the templating cation 3AMP and 4AMP, the as-formed DJ perovskites show different optical properties, with the 3AMP series having smaller band gaps than the 4AMP series. Analysis on the crystal structures and density functional theory (DFT) calculations suggest that the origin of the systematic band gap shift is the strong but indirect influence of the organic cation on the inorganic framework. Fabrication of photovoltaic devices utilizing these materials as light absorbers reveals that (3AMP)(MA) 3 Pb 4 I 13 has the best power conversion efficiency (PCE) of 7.32%, which is much higher than that of the corresponding (4AMP)(MA) 3 Pb 4 I 13 .

  12. Modeling organohalide perovskites for photovoltaic applications: From materials to interfaces

    NASA Astrophysics Data System (ADS)

    de Angelis, Filippo

    2015-03-01

    The field of hybrid/organic photovoltaics has been revolutionized in 2012 by the first reports of solid-state solar cells based on organohalide perovskites, now topping at 20% efficiency. First-principles modeling has been widely applied to the dye-sensitized solar cells field, and more recently to perovskite-based solar cells. The computational design and screening of new materials has played a major role in advancing the DSCs field. Suitable modeling strategies may also offer a view of the crucial heterointerfaces ruling the device operational mechanism. I will illustrate how simulation tools can be employed in the emerging field of perovskite solar cells. The performance of the proposed simulation toolbox along with the fundamental modeling strategies are presented using selected examples of relevant materials and interfaces. The main issue with hybrid perovskite modeling is to be able to accurately describe their structural, electronic and optical features. These materials show a degree of short range disorder, due to the presence of mobile organic cations embedded within the inorganic matrix, requiring to average their properties over a molecular dynamics trajectory. Due to the presence of heavy atoms (e.g. Sn and Pb) their electronic structure must take into account spin-orbit coupling (SOC) in an effective way, possibly including GW corrections. The proposed SOC-GW method constitutes the basis for tuning the materials electronic and optical properties, rationalizing experimental trends. Modeling charge generation in perovskite-sensitized TiO2 interfaces is then approached based on a SOC-DFT scheme, describing alignment of energy levels in a qualitatively correct fashion. The role of interfacial chemistry on the device performance is finally discussed. The research leading to these results has received funding from the European Union Seventh Framework Programme [FP7/2007 2013] under Grant Agreement No. 604032 of the MESO project.

  13. CH3NH3I post-treatment improves the performance of perovskite solar cells via eliminating the impure phases

    NASA Astrophysics Data System (ADS)

    Liang, Jingjing; Liang, Chunjun; Zhang, Huimin; Sun, Mengjie; Liu, Hong; Ji, Chao; Zhang, Xuewen; Li, Dan; He, Zhiqun

    Organic-inorganic halide perovskites are currently generating extensive interest for applications in solar cells. The perovskite morphology and composition have significant roles in solar cells. Impure phases, which will influence the performance of solar cells, are inevitably present in the film of perovskite. We found that another MAI deposition on the previous perovskite could ameliorate the film. The post-deposited MAI participates in the reconstruction of the perovskite, leading to reduced amount of impure phase, increased grain size, increased absorption and significantly improved power conversion efficiency. The results demonstrate a treatment approach to fabricate efficient planar heterojunction perovskite solar cells.

  14. Pseudohalide (SCN(-))-Doped MAPbI3 Perovskites: A Few Surprises.

    PubMed

    Halder, Ansuman; Chulliyil, Ramya; Subbiah, Anand S; Khan, Tuhin; Chattoraj, Shyamtanu; Chowdhury, Arindam; Sarkar, Shaibal K

    2015-09-03

    Pseudohalide thiocyanate anion (SCN(-)) has been used as a dopant in a methylammonium lead tri-iodide (MAPbI3) framework, aiming for its use as an absorber layer for photovoltaic applications. The substitution of SCN(-) pseudohalide anion, as verified using Fourier transform infrared (FT-IR) spectroscopy, results in a comprehensive effect on the optical properties of the original material. Photoluminescence measurements at room temperature reveal a significant enhancement in the emission quantum yield of MAPbI3-x(SCN)x as compared to MAPbI3, suggestive of suppression of nonradiative channels. This increased intensity is attributed to a highly edge specific emission from MAPbI3-x(SCN)x microcrystals as revealed by photoluminescence microscopy. Fluoresence lifetime imaging measurements further established contrasting carrier recombination dynamics for grain boundaries and the bulk of the doped material. Spatially resolved emission spectroscopy on individual microcrystals of MAPbI3-x(SCN)x reveals that the optical bandgap and density of states at various (local) nanodomains are also nonuniform. Surprisingly, several (local) emissive regions within MAPbI3-x(SCN)x microcrystals are found to be optically unstable under photoirradiation, and display unambiguous temporal intermittency in emission (blinking), which is extremely unusual and intriguing. We find diverse blinking behaviors for the undoped MAPbI3 crystals as well, which leads us to speculate that blinking may be a common phenomenon for most hybrid perovskite materials.

  15. Cation distribution, magnetic properties and cubic-perovskite phase transition in bismuth-doped nickel ferrite

    NASA Astrophysics Data System (ADS)

    Gore, Shyam K.; Jadhav, Santosh S.; Tumberphale, Umakant B.; Shaikh, Shoyeb M.; Naushad, Mu; Mane, Rajaram S.

    2017-12-01

    The phase transition of bismuth-substituted nickel ferrite, synthesized by using a simple sol-gel autocombustion method, from cubic to perovskite is confirmed from the X-ray diffraction spectrums. The changes in isomer shift, hyperfine field and cation distribution are obtained from the Mossbauer spectroscopy analysis. The cation distribution demonstrates Ni2+ cations occupy tetrahedral sites, while Fe3+ and Bi3+ occupy both tetrahedral as well as octahedral sites. For higher concentrations of bismuth, saturation magnetization is increased whereas, coercivity is decreased which is related to phase change. The variations of dielectric constant, tangent loss and conductivity (ac) with frequency (10 Hz-5 MHz) have been explored with Bi3+-doping i.e. 'x'. According to Maxwell-Wagener model, there is an involvement of electron hopping kinetics as both dielectric constant and tangent loss are decreased with increasing frequency. Increase of conductivity with frequency (measured at room temperature, 27 °C) is attributed to increase of number of carriers and mobility.

  16. Exciton-to-Dopant Energy Transfer in Mn-Doped Cesium Lead Halide Perovskite Nanocrystals.

    PubMed

    Parobek, David; Roman, Benjamin J; Dong, Yitong; Jin, Ho; Lee, Elbert; Sheldon, Matthew; Son, Dong Hee

    2016-12-14

    We report the one-pot synthesis of colloidal Mn-doped cesium lead halide (CsPbX 3 ) perovskite nanocrystals and efficient intraparticle energy transfer between the exciton and dopant ions resulting in intense sensitized Mn luminescence. Mn-doped CsPbCl 3 and CsPb(Cl/Br) 3 nanocrystals maintained the same lattice structure and crystallinity as their undoped counterparts with nearly identical lattice parameters at ∼0.2% doping concentrations and no signature of phase separation. The strong sensitized luminescence from d-d transition of Mn 2+ ions upon band-edge excitation of the CsPbX 3 host is indicative of sufficiently strong exchange coupling between the charge carriers of the host and dopant d electrons mediating the energy transfer, essential for obtaining unique properties of magnetically doped quantum dots. Highly homogeneous spectral characteristics of Mn luminescence from an ensemble of Mn-doped CsPbX 3 nanocrystals and well-defined electron paramagnetic resonance spectra of Mn 2+ in host CsPbX 3 nanocrystal lattices suggest relatively uniform doping sites, likely from substitutional doping at Pb 2+ . These observations indicate that CsPbX 3 nanocrystals, possessing many superior optical and electronic characteristics, can be utilized as a new platform for magnetically doped quantum dots expanding the range of optical, electronic, and magnetic functionality.

  17. Electronic Structure Approach to Tunable Electronic Properties of Hybrid Organic-Inorganic Perovskites

    NASA Astrophysics Data System (ADS)

    Liu, Garnett; Huhn, William; Mitzi, David B.; Kanai, Yosuke; Blum, Volker

    We present a study of the electronic structure of layered hybrid organic-inorganic perovskite (HOIP) materials using all-electron density-functional theory. Varying the nature of the organic and inorganic layers should enable systematically fine-tuning the carrier properties of each component. Using the HSE06 hybrid density functional including spin-orbit coupling (SOC), we validate the principle of tuning subsystem-specific parts of the electron band structures and densities of states in CH3NH3PbX3 (X=Cl, Br, I) compared to a modified organic component in layered (C6H5C2H4NH3) 2PbX4 (X=Cl, Br, I) and C20H22S4N2PbX4 (X=Cl, Br, I). We show that tunable shifts of electronic levels indeed arise by varying Cl, Br, I as the inorganic components, and CH3NH3+ , C6H5C2H4NH3+ , C20H22S4N22 + as the organic components. SOC is found to play an important role in splitting the conduction bands of the HOIP compounds investigated here. The frontier orbitals of the halide shift, increasing the gap, when Cl is substituted for Br and I.

  18. Hollow Fibers Networked with Perovskite Nanoparticles for H2 Production from Heavy Oil

    NASA Astrophysics Data System (ADS)

    Jeon, Yukwon; Park, Dae-Hwan; Park, Joo-Il; Yoon, Seong-Ho; Mochida, Isao; Choy, Jin-Ho; Shul, Yong-Gun

    2013-10-01

    Design of catalytic materials has been highlighted to build ultraclean use of heavy oil including liquid-to-gas technology to directly convert heavy hydrocarbons into H2-rich gas fuels. If the H2 is produced from such heavy oil through high-active and durable catalysts in reforming process that is being constructed in hydrogen infrastructure, it will be addressed into renewable energy systems. Herein, the three different hollow fiber catalysts networked with perovskite nanoparticles, LaCr0.8Ru0.2O3, LaCr0.8Ru0.1Ni0.1O3, and LaCr0.8Ni0.2O3 were prepared by using activated carbon fiber as a sacrificial template for H2 production from heavy gas oil reforming. The most important findings were arrived at: (i) catalysts had hollow fibrous architectures with well-crystallized structures, (ii) hollow fibers had a high specific surface area with a particle size of ~50 nm, and (iii) the Ru substituted ones showed high efficiency for H2 production with substantial durability under high concentrations of S, N, and aromatic compounds.

  19. Hollow fibers networked with perovskite nanoparticles for H2 production from heavy oil.

    PubMed

    Jeon, Yukwon; Park, Dae-Hwan; Park, Joo-Il; Yoon, Seong-Ho; Mochida, Isao; Choy, Jin-Ho; Shul, Yong-Gun

    2013-10-09

    Design of catalytic materials has been highlighted to build ultraclean use of heavy oil including liquid-to-gas technology to directly convert heavy hydrocarbons into H2-rich gas fuels. If the H2 is produced from such heavy oil through high-active and durable catalysts in reforming process that is being constructed in hydrogen infrastructure, it will be addressed into renewable energy systems. Herein, the three different hollow fiber catalysts networked with perovskite nanoparticles, LaCr(0.8)Ru(0.2)O3, LaCr(0.8)Ru(0.1)Ni(0.1)O3, and LaCr(0.8)Ni(0.2)O3 were prepared by using activated carbon fiber as a sacrificial template for H2 production from heavy gas oil reforming. The most important findings were arrived at: (i) catalysts had hollow fibrous architectures with well-crystallized structures, (ii) hollow fibers had a high specific surface area with a particle size of ≈50 nm, and (iii) the Ru substituted ones showed high efficiency for H2 production with substantial durability under high concentrations of S, N, and aromatic compounds.

  20. Hollow Fibers Networked with Perovskite Nanoparticles for H2 Production from Heavy Oil

    PubMed Central

    Jeon, Yukwon; Park, Dae-Hwan; Park, Joo-Il; Yoon, Seong-Ho; Mochida, Isao; Choy, Jin-Ho; Shul, Yong-Gun

    2013-01-01

    Design of catalytic materials has been highlighted to build ultraclean use of heavy oil including liquid-to-gas technology to directly convert heavy hydrocarbons into H2–rich gas fuels. If the H2 is produced from such heavy oil through high-active and durable catalysts in reforming process that is being constructed in hydrogen infrastructure, it will be addressed into renewable energy systems. Herein, the three different hollow fiber catalysts networked with perovskite nanoparticles, LaCr0.8Ru0.2O3, LaCr0.8Ru0.1Ni0.1O3, and LaCr0.8Ni0.2O3 were prepared by using activated carbon fiber as a sacrificial template for H2 production from heavy gas oil reforming. The most important findings were arrived at: (i) catalysts had hollow fibrous architectures with well-crystallized structures, (ii) hollow fibers had a high specific surface area with a particle size of ≈50 nm, and (iii) the Ru substituted ones showed high efficiency for H2 production with substantial durability under high concentrations of S, N, and aromatic compounds. PMID:24104596