The underappreciated lone pair in halide perovskites underpins their unusual properties

Fabini, Douglas H.; Seshadri, Ram; Kanatzidis, Mercouri G.

doi:10.1557/mrs.2020.142

The underappreciated lone pair in halide perovskites underpins their unusual properties

Journal Article · Sun Sep 27 04:00:00 EDT 2020 · MRS Bulletin

DOI:https://doi.org/10.1557/mrs.2020.142· OSTI ID:1802379

Fabini, Douglas H. ^[1]; Seshadri, Ram ^[2]; Kanatzidis, Mercouri G. ^[3]

Max Planck Institute for Solid State Research, Heidelberg (Germany); OSTI
Univ. of California, Santa Barbara, CA (United States)
Northwestern Univ., Evanston, IL (United States)

The presence of 6s² (5s²) lone-pair electrons on the B-site Pb (Sn) in all-inorganic and hybrid halide ABX₃ perovskites distinguishes these materials from the familiar tetrahedral semiconductors traditionally employed in optoelectronics and is key to many of their appealing properties. These electrons are stereochemically active, albeit often in a hidden fashion, resulting in unusual and highly anharmonic lattice dynamics that are linked to many of the special optoelectronic properties displayed by this material class. This article describes the connections between this atypical electronic configuration and the electronic structure and lattice dynamics of these compounds. We illustrate how the lone pair leads to favorable bandwidths and band alignments, mobile holes, large ionic dielectric response, large positive thermal expansion, and even possibly defect-tolerant electronic transport. Taken together, the evidence suggests that other high-performing semiconductors may be found among compounds with lone-pair-bearing cations in high symmetry environments and a high degree of connectivity between atoms.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Santa Barbara, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012541

OSTI ID:: 1802379

Journal Information:: MRS Bulletin, Journal Name: MRS Bulletin Journal Issue: 6 Vol. 45; ISSN 0883-7694

Publisher:: Materials Research SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (84)

Local Structures around Pb(II) and Sn(II) in CH3NH3PbX3 (X = Cl, Br, I) and CH3NH3SnX3 (X = Br, I) Studied by Pb LIII-Edge and Sn K-Edge EXAFS Ishida, H.; Maeda, H.; Hirano, A. physica status solidi (a), Vol. 159, Issue 2 https://doi.org/10.1002/1521-396X(199702)159:2<277::AID-PSSA277>3.0.CO;2-C	journal	February 1997
Dielectric-Constant-Enhanced Hall Mobility in Complex Oxides Siemons, Wolter; McGuire, Michael A.; Cooper, Valentino R. Advanced Materials, Vol. 24, Issue 29 https://doi.org/10.1002/adma.201104665	journal	June 2012
Organic Cations Might Not Be Essential to the Remarkable Properties of Band Edge Carriers in Lead Halide Perovskites Zhu, Haiming; Trinh, M. Tuan; Wang, Jue Advanced Materials, Vol. 29, Issue 1 https://doi.org/10.1002/adma.201603072	journal	October 2016
What Remains Unexplained about the Properties of Halide Perovskites? Egger, David A.; Bera, Achintya; Cahen, David Advanced Materials, Vol. 30, Issue 20 https://doi.org/10.1002/adma.201800691	journal	March 2018
LOBSTER: A tool to extract chemical bonding from plane-wave based DFT: Tool to Extract Chemical Bonding Maintz, Stefan; Deringer, Volker L.; Tchougréeff, Andrei L. Journal of Computational Chemistry, Vol. 37, Issue 11 https://doi.org/10.1002/jcc.24300	journal	February 2016
The lattice parameter of highly pure silicon single crystals Becker, P.; Scyfried, P.; Siegert, H. Zeitschrift für Physik B Condensed Matter, Vol. 48, Issue 1 https://doi.org/10.1007/BF02026423	journal	August 1982
Infrared and Raman spectra of the elpasolites Cs2NaSbCl6 and Cs2NaBiCl6: Evidence for a pseudo Jahn-Teller distorted ground state Smit, W. M. A.; Dirksen, G. J.; Stufkens, D. J. Journal of Physics and Chemistry of Solids, Vol. 51, Issue 2 https://doi.org/10.1016/0022-3697(90)90092-T	journal	January 1990
Dielectric study of CH3NH3PbX3 (X = Cl, Br, I) Onoda-Yamamuro, Noriko; Matsuo, Takasuke; Suga, Hiroshi Journal of Physics and Chemistry of Solids, Vol. 53, Issue 7 https://doi.org/10.1016/0022-3697(92)90121-S	journal	July 1992
Stéréochimie des eléments comportant des paires non liées: Ge (II), As (III), Se (IV), Br (V), Sn (II), Sb (III), Te (IV), I (V), Xe (VI), Tl (I), Pb (II), et Bi (III) (oxydes, fluorures et oxyfluorures) Galy, Jean; Meunier, Georges; Andersson, Sten Journal of Solid State Chemistry, Vol. 13, Issue 1-2 https://doi.org/10.1016/0022-4596(75)90092-4	journal	February 1975
Magnetoabsorption of the lowest exciton in perovskite-type compound (CH3NH3)PbI3 Hirasawa, M.; Ishihara, T.; Goto, T. Physica B: Condensed Matter, Vol. 201 https://doi.org/10.1016/0921-4526(94)91130-4	journal	July 1994
Phase transitions in the perovskite methylammonium lead bromide, CH3ND3PbBr3 Swainson, I. P.; Hammond, R. P.; Soullière, C. Journal of Solid State Chemistry, Vol. 176, Issue 1 https://doi.org/10.1016/S0022-4596(03)00352-9	journal	November 2003
High-temperature structural evolution of caesium and rubidium triiodoplumbates Trots, D. M.; Myagkota, S. V. Journal of Physics and Chemistry of Solids, Vol. 69, Issue 10, p. 2520-2526 https://doi.org/10.1016/j.jpcs.2008.05.007	journal	October 2008
Thin-Film Preparation and Characterization of Cs ₃ Sb ₂ I ₉ : A Lead-Free Layered Perovskite Semiconductor Saparov, Bayrammurad; Hong, Feng; Sun, Jon-Paul Chemistry of Materials, Vol. 27, Issue 16 https://doi.org/10.1021/acs.chemmater.5b01989	journal	August 2015
Crystal and Electronic Structures of Complex Bismuth Iodides A ₃ Bi ₂ I ₉ ( A = K, Rb, Cs) Related to Perovskite: Aiding the Rational Design of Photovoltaics Lehner, Anna J.; Fabini, Douglas H.; Evans, Hayden A. Chemistry of Materials, Vol. 27, Issue 20 https://doi.org/10.1021/acs.chemmater.5b03147	journal	October 2015
Cs ₂ AgBiX ₆ (X = Br, Cl): New Visible Light Absorbing, Lead-Free Halide Perovskite Semiconductors McClure, Eric T.; Ball, Molly R.; Windl, Wolfgang Chemistry of Materials, Vol. 28, Issue 5 https://doi.org/10.1021/acs.chemmater.5b04231	journal	February 2016
Searching for “Defect-Tolerant” Photovoltaic Materials: Combined Theoretical and Experimental Screening Brandt, Riley E.; Poindexter, Jeremy R.; Gorai, Prashun Chemistry of Materials, Vol. 29, Issue 11 https://doi.org/10.1021/acs.chemmater.6b05496	journal	May 2017
Candidate Inorganic Photovoltaic Materials from Electronic Structure-Based Optical Absorption and Charge Transport Proxies Fabini, Douglas H.; Koerner, Mitchell; Seshadri, Ram Chemistry of Materials, Vol. 31, Issue 5 https://doi.org/10.1021/acs.chemmater.8b04542	journal	February 2019
Tetragonal Cs _1.17 In _0.81 Cl ₃ : A Charge-Ordered Indium Halide Perovskite Derivative Tan, Xiaoyan; Stephens, Peter W.; Hendrickx, Mylène Chemistry of Materials, Vol. 31, Issue 6 https://doi.org/10.1021/acs.chemmater.8b04771	journal	June 2018
Perovskites with a Twist: Strong In ¹⁺ Off-Centering in the Mixed-Valent CsInX ₃ (X = Cl, Br) McCall, Kyle M.; Friedrich, Daniel; Chica, Daniel G. Chemistry of Materials, Vol. 31, Issue 22 https://doi.org/10.1021/acs.chemmater.9b04095	journal	October 2019
Crystal Structure Evolution and Notable Thermal Expansion in Hybrid Perovskites Formamidinium Tin Iodide and Formamidinium Lead Bromide Schueller, Emily C.; Laurita, Geneva; Fabini, Douglas H. Inorganic Chemistry, Vol. 57, Issue 2 https://doi.org/10.1021/acs.inorgchem.7b02576	journal	October 2017
Critical Comparison of FAPbX ₃ and MAPbX ₃ (X = Br and Cl): How Do They Differ? Govinda, Sharada; Kore, Bhushan P.; Swain, Diptikanta The Journal of Physical Chemistry C, Vol. 122, Issue 25 https://doi.org/10.1021/acs.jpcc.8b00602	journal	December 2017
Dynamic Disorder, Band Gap Widening, and Persistent Near-IR Photoluminescence up to At Least 523 K in ASnI ₃ Perovskites (A = Cs ⁺ , CH ₃ NH ₃ ⁺ and NH ₂ –CH═NH ₂ ⁺ ) Kontos, Athanassios G.; Kaltzoglou, Andreas; Arfanis, Michalis K. The Journal of Physical Chemistry C, Vol. 122, Issue 46 https://doi.org/10.1021/acs.jpcc.8b10218	journal	November 2018
An Explanation of the Photoinduced Giant Dielectric Constant of Lead Halide Perovskite Solar Cells Almond, Darryl P.; Bowen, Chris R. The Journal of Physical Chemistry Letters, Vol. 6, Issue 9 https://doi.org/10.1021/acs.jpclett.5b00620	journal	April 2015
How Important Is the Organic Part of Lead Halide Perovskite Photovoltaic Cells? Efficient CsPbBr ₃ Cells Kulbak, Michael; Cahen, David; Hodes, Gary The Journal of Physical Chemistry Letters, Vol. 6, Issue 13 https://doi.org/10.1021/acs.jpclett.5b00968	journal	June 2015
Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons Zhu, X. -Y.; Podzorov, V. The Journal of Physical Chemistry Letters, Vol. 6, Issue 23 https://doi.org/10.1021/acs.jpclett.5b02462	journal	November 2015
Dielectric and Thermodynamic Signatures of Low-Temperature Glassy Dynamics in the Hybrid Perovskites CH ₃ NH ₃ PbI ₃ and HC(NH ₂ ) ₂ PbI ₃ Fabini, Douglas H.; Hogan, Tom; Evans, Hayden A. The Journal of Physical Chemistry Letters, Vol. 7, Issue 3 https://doi.org/10.1021/acs.jpclett.5b02821	journal	January 2016
Cesium Lead Halide Perovskites with Improved Stability for Tandem Solar Cells Beal, Rachel E.; Slotcavage, Daniel J.; Leijtens, Tomas The Journal of Physical Chemistry Letters, Vol. 7, Issue 5 https://doi.org/10.1021/acs.jpclett.6b00002	journal	February 2016
Lead-Free Halide Double Perovskites via Heterovalent Substitution of Noble Metals Volonakis, George; Filip, Marina R.; Haghighirad, Amir Abbas The Journal of Physical Chemistry Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acs.jpclett.6b00376	journal	March 2016
Cs ₂ InAgCl ₆ : A New Lead-Free Halide Double Perovskite with Direct Band Gap Volonakis, George; Haghighirad, Amir Abbas; Milot, Rebecca L. The Journal of Physical Chemistry Letters, Vol. 8, Issue 4 https://doi.org/10.1021/acs.jpclett.6b02682	journal	January 2017
Structural Instabilities Related to Highly Anharmonic Phonons in Halide Perovskites Marronnier, Arthur; Lee, Heejae; Geffroy, Bernard The Journal of Physical Chemistry Letters, Vol. 8, Issue 12 https://doi.org/10.1021/acs.jpclett.7b00807	journal	June 2017
Behavior of Methylammonium Dipoles in MAPbX ₃ (X = Br and I) Govinda, Sharada; Kore, Bhushan P.; Bokdam, Menno The Journal of Physical Chemistry Letters, Vol. 8, Issue 17 https://doi.org/10.1021/acs.jpclett.7b01740	journal	August 2017
Synthesis and Characterization of the Rare-Earth Hybrid Double Perovskites: (CH ₃ NH ₃ ) ₂ KGdCl ₆ and (CH ₃ NH ₃ ) ₂ KYCl ₆ Deng, Zeyu; Wei, Fengxia; Brivio, Federico The Journal of Physical Chemistry Letters, Vol. 8, Issue 20 https://doi.org/10.1021/acs.jpclett.7b02322	journal	September 2017
Data-Driven Systematic Search of Promising Photocatalysts for Water Splitting under Visible Light Jin, Hao; Zhang, Huijun; Li, Jianwei The Journal of Physical Chemistry Letters, Vol. 10, Issue 17 https://doi.org/10.1021/acs.jpclett.9b01977	journal	August 2019
Can Pb-Free Halide Double Perovskites Support High-Efficiency Solar Cells? Savory, Christopher N.; Walsh, Aron; Scanlon, David O. ACS Energy Letters, Vol. 1, Issue 5 https://doi.org/10.1021/acsenergylett.6b00471	journal	October 2016
Vapour-Deposited Cesium Lead Iodide Perovskites: Microsecond Charge Carrier Lifetimes and Enhanced Photovoltaic Performance Hutter, Eline M.; Sutton, Rebecca J.; Chandrashekar, Sanjana ACS Energy Letters, Vol. 2, Issue 8 https://doi.org/10.1021/acsenergylett.7b00591	journal	August 2017
Slow Electron–Hole Recombination in Lead Iodide Perovskites Does Not Require a Molecular Dipole Dastidar, Subham; Li, Siming; Smolin, Sergey Y. ACS Energy Letters, Vol. 2, Issue 10 https://doi.org/10.1021/acsenergylett.7b00606	journal	September 2017
High-Throughput Computational Assessment of Previously Synthesized Semiconductors for Photovoltaic and Photoelectrochemical Devices Kuhar, Korina; Pandey, Mohnish; Thygesen, Kristian S. ACS Energy Letters, Vol. 3, Issue 2 https://doi.org/10.1021/acsenergylett.7b01312	journal	January 2018
Cubic or Orthorhombic? Revealing the Crystal Structure of Metastable Black-Phase CsPbI ₃ by Theory and Experiment Sutton, Rebecca J.; Filip, Marina R.; Haghighirad, Amir A. ACS Energy Letters, Vol. 3, Issue 8 https://doi.org/10.1021/acsenergylett.8b00672	journal	June 2018
Study of Local Structure in Selected Organic–Inorganic Perovskites in the Pm 3̅ m Phase Worhatch, Richard J.; Kim, HyunJeong; Swainson, Ian P. Chemistry of Materials, Vol. 20, Issue 4 https://doi.org/10.1021/cm702668d	journal	February 2008
Structure and Bonding in SnWO ₄ , PbWO ₄ , and BiVO ₄ : Lone Pairs vs Inert Pairs Stoltzfus, Matthew W.; Woodward, Patrick M.; Seshadri, Ram Inorganic Chemistry, Vol. 46, Issue 10 https://doi.org/10.1021/ic061157g	journal	May 2007
Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G. Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038 https://doi.org/10.1021/ic401215x	journal	July 2013
A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovoltaic Applications Slavney, Adam H.; Hu, Te; Lindenberg, Aaron M. Journal of the American Chemical Society, Vol. 138, Issue 7 https://doi.org/10.1021/jacs.5b13294	journal	February 2016
Dynamic Stereochemical Activity of the Sn ²⁺ Lone Pair in Perovskite CsSnBr ₃ Fabini, Douglas H.; Laurita, Geneva; Bechtel, Jonathon S. Journal of the American Chemical Society, Vol. 138, Issue 36 https://doi.org/10.1021/jacs.6b06287	journal	September 2016
Intrinsic Instability of Cs ₂ In(I)M(III)X ₆ (M = Bi, Sb; X = Halogen) Double Perovskites: A Combined Density Functional Theory and Experimental Study Xiao, Zewen; Du, Ke-Zhao; Meng, Weiwei Journal of the American Chemical Society, Vol. 139, Issue 17 https://doi.org/10.1021/jacs.7b02227	journal	April 2017
Universal Dynamics of Molecular Reorientation in Hybrid Lead Iodide Perovskites Fabini, Douglas H.; Siaw, Ting Ann; Stoumpos, Constantinos C. Journal of the American Chemical Society, Vol. 139, Issue 46 https://doi.org/10.1021/jacs.7b09536	journal	November 2017
Mirrors of Bonding in Metal Halide Perovskites Goesten, Maarten G.; Hoffmann, Roald Journal of the American Chemical Society, Vol. 140, Issue 40 https://doi.org/10.1021/jacs.8b08038	journal	September 2018
Ab Initio Calculations of Band Gaps and Absolute Band Positions of Polymorphs of RbPbI ₃ and CsPbI ₃ : Implications for Main-Group Halide Perovskite Photovoltaics Brgoch, Jakoah; Lehner, Anna J.; Chabinyc, Michael The Journal of Physical Chemistry C, Vol. 118, Issue 48 https://doi.org/10.1021/jp508880y	journal	November 2014
Defect Tolerant Semiconductors for Solar Energy Conversion Zakutayev, Andriy; Caskey, Christopher M.; Fioretti, Angela N. The Journal of Physical Chemistry Letters, Vol. 5, Issue 7 https://doi.org/10.1021/jz5001787	journal	March 2014
Direct measurement of the exciton binding energy and effective masses for charge carriers in organic–inorganic tri-halide perovskites Miyata, Atsuhiko; Mitioglu, Anatolie; Plochocka, Paulina Nature Physics, Vol. 11, Issue 7 https://doi.org/10.1038/nphys3357	journal	June 2015
Inversion symmetry and bulk Rashba effect in methylammonium lead iodide perovskite single crystals Frohna, Kyle; Deshpande, Tejas; Harter, John Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04212-w	journal	May 2018
Dynamic shortening of disorder potentials in anharmonic halide perovskites Gehrmann, Christian; Egger, David A. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-11087-y	journal	July 2019
Efficient carrier transport in halide perovskites: theoretical perspectives Du, M. H. Journal of Materials Chemistry A, Vol. 2, Issue 24 https://doi.org/10.1039/C4TA01198H	journal	January 2014
Inorganic caesium lead iodide perovskite solar cells Eperon, Giles E.; Paternò, Giuseppe M.; Sutton, Rebecca J. Journal of Materials Chemistry A, Vol. 3, Issue 39 https://doi.org/10.1039/C5TA06398A	journal	January 2015
The synthesis, structure and electronic properties of a lead-free hybrid inorganic–organic double perovskite (MA) ₂ KBiCl ₆ (MA = methylammonium) Wei, Fengxia; Deng, Zeyu; Sun, Shijing Materials Horizons, Vol. 3, Issue 4 https://doi.org/10.1039/C6MH00053C	journal	January 2016
Optical phonons in methylammonium lead halide perovskites and implications for charge transport Sendner, Michael; Nayak, Pabitra K.; Egger, David A. Materials Horizons, Vol. 3, Issue 6 https://doi.org/10.1039/C6MH00275G	journal	January 2016
Searching for promising new perovskite-based photovoltaic absorbers: the importance of electronic dimensionality Xiao, Zewen; Meng, Weiwei; Wang, Jianbo Materials Horizons, Vol. 4, Issue 2 https://doi.org/10.1039/C6MH00519E	journal	January 2017
Exploring the properties of lead-free hybrid double perovskites using a combined computational-experimental approach Deng, Zeyu; Wei, Fengxia; Sun, Shijing Journal of Materials Chemistry A, Vol. 4, Issue 31 https://doi.org/10.1039/C6TA05817E	journal	January 2016
Designing indirect–direct bandgap transitions in double perovskites Tran, T. Thao; Panella, Jessica R.; Chamorro, Juan R. Materials Horizons, Vol. 4, Issue 4 https://doi.org/10.1039/C7MH00239D	journal	January 2017
Chemical tuning of dynamic cation off-centering in the cubic phases of hybrid tin and lead halide perovskites Laurita, Geneva; Fabini, Douglas H.; Stoumpos, Constantinos C. Chemical Science, Vol. 8, Issue 8 https://doi.org/10.1039/C7SC01429E	journal	January 2017
Stereochemistry of post-transition metal oxides: revision of the classical lone pair model Walsh, Aron; Payne, David J.; Egdell, Russell G. Chemical Society Reviews, Vol. 40, Issue 9 https://doi.org/10.1039/c1cs15098g	journal	January 2011
The lower oxidation states of indium Tuck, Dennis G. Chemical Society Reviews, Vol. 22, Issue 4 https://doi.org/10.1039/cs9932200269	journal	January 1993
Inorganic stereochemistry Gillespie, R. J.; Nyholm, R. S. Quarterly Reviews, Chemical Society, Vol. 11, Issue 4 https://doi.org/10.1039/qr9571100339	journal	January 1957
Potential Function for the Inversion of Ammonia Swalen, J. D.; Ibers, James A. The Journal of Chemical Physics, Vol. 36, Issue 7 https://doi.org/10.1063/1.1701290	journal	April 1962
Compilation of the Static Dielectric Constant of Inorganic Solids Young, K. F.; Frederikse, H. P. R. Journal of Physical and Chemical Reference Data, Vol. 2, Issue 2 https://doi.org/10.1063/1.3253121	journal	April 1973
Temperature dependence of the band gap of perovskite semiconductor compound CsSnI₃ Yu, Chonglong; Chen, Zhuo; J. Wang, Jian Journal of Applied Physics, Vol. 110, Issue 6, Article No. 063526 https://doi.org/10.1063/1.3638699	journal	September 2011
Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter‐wave spectroscopy Poglitsch, A.; Weber, D. The Journal of Chemical Physics, Vol. 87, Issue 11, p. 6373-6378 https://doi.org/10.1063/1.453467	journal	December 1987
Unusual defect physics in CH ₃ NH ₃ PbI ₃ perovskite solar cell absorber Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa Applied Physics Letters, Vol. 104, Issue 6 https://doi.org/10.1063/1.4864778	journal	February 2014
Electronic structure and photovoltaic application of BiI ₃ Lehner, Anna J.; Wang, Hengbin; Fabini, Douglas H. Applied Physics Letters, Vol. 107, Issue 13 https://doi.org/10.1063/1.4932129	journal	September 2015
Dielectric and ferroic properties of metal halide perovskites Wilson, Jacob N.; Frost, Jarvist M.; Wallace, Suzanne K. APL Materials, Vol. 7, Issue 1 https://doi.org/10.1063/1.5079633	journal	January 2019
Pressure-induced semiconductor-to-metal phase transition of a charge-ordered indium halide perovskite Lin, Jia; Chen, Hong; Gao, Yang Proceedings of the National Academy of Sciences, Vol. 116, Issue 47 https://doi.org/10.1073/pnas.1907576116	journal	November 2019
Effect of hydrostatic pressure on the structural phase transitions in CH ₃ NH ₃ PbX ₃ (X = Cl, Br, I) Gesi, K. Ferroelectrics, Vol. 203, Issue 1 https://doi.org/10.1080/00150199708012851	journal	November 1997
Electronic structure of the ternary chalcopyrite semiconductors CuAl S 2 , CuGa S 2 , CuIn S 2 , CuAl Se 2 , CuGa Se 2 , and CuIn Se 2 Jaffe, J. E.; Zunger, Alex Physical Review B, Vol. 28, Issue 10 https://doi.org/10.1103/PhysRevB.28.5822	journal	November 1983
Effect of pressure on the optical-absorption edges of CsGeBr 3 and CsGeCl 3 Schwarz, U.; Wagner, F.; Syassen, K. Physical Review B, Vol. 53, Issue 19 https://doi.org/10.1103/PhysRevB.53.12545	journal	May 1996
First-principles indicators of metallicity and cation off-centricity in the IV-VI rocksalt chalcogenides of divalent Ge, Sn, and Pb Waghmare, U. V.; Spaldin, N. A.; Kandpal, H. C. Physical Review B, Vol. 67, Issue 12 https://doi.org/10.1103/PhysRevB.67.125111	journal	March 2003
Enhanced Born charge and proximity to ferroelectricity in thallium halides Du, Mao-Hua; Singh, David J. Physical Review B, Vol. 81, Issue 14 https://doi.org/10.1103/PhysRevB.81.144114	journal	April 2010
Defect engineering of BaSnO 3 for high-performance transparent conducting oxide applications Scanlon, David O. Physical Review B, Vol. 87, Issue 16 https://doi.org/10.1103/PhysRevB.87.161201	journal	April 2013
Electronic band structure, phonons, and exciton binding energies of halide perovskites CsSnCl 3 , CsSnBr 3 , and CsSnI 3 Huang, Ling-yi; Lambrecht, Walter R. L. Physical Review B, Vol. 88, Issue 16 https://doi.org/10.1103/PhysRevB.88.165203	journal	October 2013
Local Polar Fluctuations in Lead Halide Perovskite Crystals Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z. Physical Review Letters, Vol. 118, Issue 13 https://doi.org/10.1103/PhysRevLett.118.136001	journal	March 2017
Distortion modes in halide perovskites: To twist or to stretch, a matter of tolerance and lone pairs Radha, Santosh Kumar; Bhandari, Churna; Lambrecht, Walter R. L. Physical Review Materials, Vol. 2, Issue 6 https://doi.org/10.1103/PhysRevMaterials.2.063605	journal	June 2018
Orientational ordering, tilting and lone-pair activity in the perovskite methylammonium tin bromide, CH₃NH₃SnBr₃ Swainson, Ian; Chi, Lisheng; Her, Jae-Hyuk Acta Crystallographica Section B Structural Science, Vol. 66, Issue 4, p. 422-429 https://doi.org/10.1107/S0108768110014734	journal	June 2010
Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites Wu, Xiaoxi; Tan, Liang Z.; Shen, Xiaozhe Science Advances, Vol. 3, Issue 7 https://doi.org/10.1126/sciadv.1602388	journal	July 2017
Colossal Positive and Negative Thermal Expansion in the Framework Material Ag3[Co(CN)6] Goodwin, A. L.; Calleja, M.; Conterio, M. J. Science, Vol. 319, Issue 5864 https://doi.org/10.1126/science.1151442	journal	February 2008
Entropically Stabilized Local Dipole Formation in Lead Chalcogenides Bozin, E. S.; Malliakas, C. D.; Souvatzis, P. Science, Vol. 330, Issue 6011 https://doi.org/10.1126/science.1192759	journal	December 2010
Identifying defect-tolerant semiconductors with high minority-carrier lifetimes: beyond hybrid lead halide perovskites Brandt, Riley E.; Stevanović, Vladan; Ginley, David S. MRS Communications, Vol. 5, Issue 2 https://doi.org/10.1557/mrc.2015.26	journal	May 2015

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