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.

doi:10.1103/PhysRevMaterials.2.063605

Distortion modes in halide perovskites: To twist or to stretch, a matter of tolerance and lone pairs

Journal Article · Mon Jun 25 00:00:00 EDT 2018 · Physical Review Materials

DOI:https://doi.org/10.1103/PhysRevMaterials.2.063605· OSTI ID:1591769

^[1]; Bhandari, Churna ^[2]; ^[3]

Case Western Reserve Univ., Cleveland, OH (United States); Case Westrn Reserve University
Univ. of Missouri, Columbia, MO (United States)
Case Western Reserve Univ., Cleveland, OH (United States)

With first-principles calculations, we show that CsBX₃halides withB=Sn or Pb undergo octahedral rotation distortions, while for B=Ge and Si, they undergo a ferroelectric rhombohedral distortion accompanied by a rhombohedral stretching of the lattice. We demonstrate that these are mutually exclusive at their equilibrium volume although different distortions may occur as functions of lattice expansion. The choice between the two distortion modes is in part governed by the Goldschmidt tolerance factor. However, another factor explaining the difference between Sn and Pb compared with Ge and Si is the stronger lone-pair character of Ge and Si when forced to be divalent as is the case in these structures. The lone-pair chemistry is related to the off centering. While the Si-based compounds have not yet been synthesized, the Ge compounds have been established experimentally. As a final test of the importance of the tolerance factor we consider RbGeX₃, which has smaller tolerance factor than the corresponding CsGeX₃ because Rb is smaller than Cs. We find that it can lower its energy by both rotations or rhombohedral off-centering distortions but the latter lower the energy slightly more efficiently.

View Accepted Manuscript (DOE)

Research Organization:: Case Western Reserve Univ., Cleveland, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0008933

OSTI ID:: 1591769

Alternate ID(s):: OSTI ID: 1541388
OSTI ID: 1457087

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 6 Vol. 2; ISSN PRMHAR; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (34)

Morphological Control for High Performance, Solution-Processed Planar Heterojunction Perovskite Solar Cells Eperon, Giles E.; Burlakov, Victor M.; Docampo, Pablo Advanced Functional Materials, Vol. 24, Issue 1, p. 151-157 https://doi.org/10.1002/adfm.201302090	journal	September 2013
Kristallstrukturen und Phasentransformationen von Caesiumtrihalogenogermanaten(II) CsGeX3 (X = Cl, Br, I) Thiele, Gerhard; Rotter, Heinz Wilhelm; Schmidt, Klaus Dieter Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 545, Issue 2 https://doi.org/10.1002/zaac.19875450217	journal	February 1987
Die Gesetze der Krystallochemie Goldschmidt, V. M. Die Naturwissenschaften, Vol. 14, Issue 21 https://doi.org/10.1007/BF01507527	journal	May 1926
Perovskite solar cells: an emerging photovoltaic technology Park, Nam-Gyu Materials Today, Vol. 18, Issue 2 https://doi.org/10.1016/j.mattod.2014.07.007	journal	March 2015
Interplay of Octahedral Rotations and Lone Pair Ferroelectricity in CsPbF ₃ Smith, Eva H.; Benedek, Nicole A.; Fennie, Craig J. Inorganic Chemistry, Vol. 54, Issue 17 https://doi.org/10.1021/acs.inorgchem.5b01213	journal	August 2015
Interplay of Orientational Order and Electronic Structure in Methylammonium Lead Iodide: Implications for Solar Cell Operation Quarti, Claudio; Mosconi, Edoardo; De Angelis, Filippo Chemistry of Materials, Vol. 26, Issue 22 https://doi.org/10.1021/cm5032046	journal	November 2014
CsSnI₃ : Semiconductor or Metal? High Electrical Conductivity and Strong Near-Infrared Photoluminescence from a Single Material. High Hole Mobility and Phase-Transitions Chung, In; Song, Jung-Hwan; Im, Jino Journal of the American Chemical Society, Vol. 134, Issue 20, p. 8579-8587 https://doi.org/10.1021/ja301539s	journal	May 2012
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051 https://doi.org/10.1021/ja809598r	journal	May 2009
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
Organolead Halide Perovskite: New Horizons in Solar Cell Research Kim, Hui-Seon; Im, Sang Hyuk; Park, Nam-Gyu The Journal of Physical Chemistry C, Vol. 118, Issue 11, p. 5615-5625 https://doi.org/10.1021/jp409025w	journal	February 2014
Sequential deposition as a route to high-performance perovskite-sensitized solar cells Burschka, Julian; Pellet, Norman; Moon, Soo-Jin Nature, Vol. 499, Issue 7458, p. 316-319 https://doi.org/10.1038/nature12340	journal	July 2013
Efficient planar heterojunction perovskite solar cells by vapour deposition Liu, Mingzhen; Johnston, Michael B.; Snaith, Henry J. Nature, Vol. 501, Issue 7467, p. 395-398 https://doi.org/10.1038/nature12509	journal	September 2013
On the application of the tolerance factor to inorganic and hybrid halide perovskites: a revised system Travis, W.; Glover, E. N. K.; Bronstein, H. Chemical Science, Vol. 7, Issue 7 https://doi.org/10.1039/C5SC04845A	journal	January 2016
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
Low-temperature processed meso-superstructured to thin-film perovskite solar cells Ball, James M.; Lee, Michael M.; Hey, Andrew Energy & Environmental Science, Vol. 6, Issue 6 https://doi.org/10.1039/c3ee40810h	journal	January 2013
The structural diversity of AB S ₃ compounds with d ⁰ electronic configuration for the B -cation Brehm, John A.; Bennett, Joseph W.; Schoenberg, Michael Rutenberg The Journal of Chemical Physics, Vol. 140, Issue 22 https://doi.org/10.1063/1.4879659	journal	June 2014
Nonsingular Hankel functions as a new basis for electronic structure calculations Bott, E.; Methfessel, M.; Krabs, W. Journal of Mathematical Physics, Vol. 39, Issue 6 https://doi.org/10.1063/1.532437	journal	June 1998
Ab initio statistical mechanics of the ferroelectric phase transition in PbTiO 3 Waghmare, U. V.; Rabe, K. M. Physical Review B, Vol. 55, Issue 10 https://doi.org/10.1103/PhysRevB.55.6161	journal	March 1997
Lattice dynamics of BaTiO 3 , PbTiO 3 , and PbZrO 3 : A comparative first-principles study Ghosez, Ph.; Cockayne, E.; Waghmare, U. V. Physical Review B, Vol. 60, Issue 2 https://doi.org/10.1103/PhysRevB.60.836	journal	July 1999
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
Fusion of the LAPW and LMTO methods: The augmented plane wave plus muffin-tin orbital method Kotani, Takao; van Schilfgaarde, Mark Physical Review B, Vol. 81, Issue 12 https://doi.org/10.1103/PhysRevB.81.125117	journal	March 2010
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
Lattice dynamics in perovskite halides CsSn X 3 with X = I , Br , Cl Huang, Ling-yi; Lambrecht, Walter R. L. Physical Review B, Vol. 90, Issue 19 https://doi.org/10.1103/PhysRevB.90.195201	journal	November 2014
Phase stability and transformations in the halide perovskite CsSnI 3 da Silva, E. Lora; Skelton, Jonathan M.; Parker, Stephen C. Physical Review B, Vol. 91, Issue 14 https://doi.org/10.1103/PhysRevB.91.144107	journal	April 2015
Electronic band structure trends of perovskite halides: Beyond Pb and Sn to Ge and Si Huang, Ling-yi; Lambrecht, Walter R. L. Physical Review B, Vol. 93, Issue 19 https://doi.org/10.1103/PhysRevB.93.195211	journal	May 2016
Atomic structure of metal-halide perovskites from first principles: The chicken-and-egg paradox of the organic-inorganic interaction Li, Jingrui; Rinke, Patrick Physical Review B, Vol. 94, Issue 4 https://doi.org/10.1103/PhysRevB.94.045201	journal	July 2016
Competing Structural Instabilities in Cubic Perovskites Zhong, W.; Vanderbilt, David Physical Review Letters, Vol. 74, Issue 13 https://doi.org/10.1103/PhysRevLett.74.2587	journal	March 1995
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Octahedral Tilting in Perovskites. II. Structure Stabilizing Forces Woodward, P. M. Acta Crystallographica Section B Structural Science, Vol. 53, Issue 1 https://doi.org/10.1107/S0108768196012050	journal	February 1997
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
The classification of tilted octahedra in perovskites Glazer, A. M. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 28, Issue 11 https://doi.org/10.1107/S0567740872007976	journal	November 1972
Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites Lee, M. M.; Teuscher, J.; Miyasaka, T. Science, Vol. 338, Issue 6107, p. 643-647 https://doi.org/10.1126/science.1228604	journal	October 2012
Structural Phase Transitions of the Polymorphs of CsSnI₃ by Means of Rietveld Analysis of the X-Ray Diffraction Yamada, Koji; Funabiki, Shinya; Horimoto, Hiromi Chemistry Letters, Vol. 20, Issue 5, p. 801-804 https://doi.org/10.1246/cl.1991.801	journal	May 1991
Theory of displacive phase transitions in minerals Dove, Martin T. American Mineralogist, Vol. 82, Issue 3-4 https://doi.org/10.2138/am-1997-3-401	journal	April 1997

Cited By (1)

Band Gaps and Stability of CsSiX ₃ Halides Radha, Santosh K.; Lambrecht, Walter R. L. physica status solidi (a), Vol. 216, Issue 15 https://doi.org/10.1002/pssa.201800962	journal	February 2019

Similar Records

Electronic band structure trends of perovskite halides: Beyond Pb and Sn to Ge and Si

Journal Article · Mon May 23 00:00:00 EDT 2016 · Physical Review B · OSTI ID:1591890

The underappreciated lone pair in halide perovskites underpins their unusual properties

Journal Article · Sun Sep 27 00:00:00 EDT 2020 · MRS Bulletin · OSTI ID:1802379

Related Subjects

36 MATERIALS SCIENCE
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
first-principles
halide perovskite
lone-pair
phase stability

Distortion modes in halide perovskites: To twist or to stretch, a matter of tolerance and lone pairs

Citation Formats

References (34)

Cited By (1)

Similar Records

Related Subjects