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Title: 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:
ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Case Western Reserve Univ., Cleveland, OH (United States)
  2. 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) (SC-22)
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. doi: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. doi: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 = {2018},
month = {6}
}

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