Distortion modes in halide perovskites: To twist or to stretch, a matter of tolerance and lone pairs
Abstract
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.
- Authors:
-
[1];
[1]
- Case Western Reserve Univ., Cleveland, OH (United States)
- Univ. of Missouri, Columbia, MO (United States)
- Publication Date:
- Research Org.:
- Case Western Reserve Univ., Cleveland, OH (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1591769
- Alternate Identifier(s):
- OSTI ID: 1457087
- Grant/Contract Number:
- SC0008933
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review Materials
- Additional Journal Information:
- Journal Volume: 2; Journal Issue: 6; Journal ID: ISSN 2475-9953
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; halide perovskite; phase stability; first-principles; lone-pair
Citation Formats
Radha, Santosh Kumar, Bhandari, Churna, and Lambrecht, Walter R. L. Distortion modes in halide perovskites: To twist or to stretch, a matter of tolerance and lone pairs. United States: N. p., 2018.
Web. doi:10.1103/PhysRevMaterials.2.063605.
Radha, Santosh Kumar, Bhandari, Churna, & Lambrecht, Walter R. L. Distortion modes in halide perovskites: To twist or to stretch, a matter of tolerance and lone pairs. United States. https://doi.org/10.1103/PhysRevMaterials.2.063605
Radha, Santosh Kumar, Bhandari, Churna, and Lambrecht, Walter R. L. Mon .
"Distortion modes in halide perovskites: To twist or to stretch, a matter of tolerance and lone pairs". United States. https://doi.org/10.1103/PhysRevMaterials.2.063605. https://www.osti.gov/servlets/purl/1591769.
@article{osti_1591769,
title = {Distortion modes in halide perovskites: To twist or to stretch, a matter of tolerance and lone pairs},
author = {Radha, Santosh Kumar and Bhandari, Churna and Lambrecht, Walter R. L.},
abstractNote = {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.},
doi = {10.1103/PhysRevMaterials.2.063605},
journal = {Physical Review Materials},
number = 6,
volume = 2,
place = {United States},
year = {Mon Jun 25 00:00:00 EDT 2018},
month = {Mon Jun 25 00:00:00 EDT 2018}
}
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Works referencing / citing this record:
Band Gaps and Stability of CsSiX 3 Halides
journal, February 2019
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