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Title: Assessment of dynamic structural instabilities across 24 cubic inorganic halide perovskites

Abstract

Metal halide perovskites are promising candidates for next-generation photovoltaic and optoelectronic applications. The flexible nature of the octahedral network introduces complexity when understanding their physical behavior. It has been shown that these materials are prone to decomposition and phase competition, and the local crystal structure often deviates from the average space group symmetry. To make stable phase-pure perovskites, understanding their structure-composition relations is of central importance. We demonstrate, from lattice dynamics calculations, that the 24 inorganic perovskites ABX 3 (A = Cs, Rb; B = Ge, Sn, Pb; X = F, Cl, Br, I) exhibit instabilities in their cubic phase. These instabilities include cation displacements, octahedral tilting, and Jahn-Teller distortions. The magnitudes of the instabilities vary depending on the chemical identity and ionic radii of the composition. The tilting instabilities are energetically dominant and reduce as the tolerance factor increases, whereas cation displacements and Jahn-Teller type distortions depend on the interactions between the constituent ions. We further considered representative tetragonal, orthorhombic, and monoclinic perovskite phases to obtain phonon-stable structures for each composition. This work provides insights into the thermodynamic driving force of the instabilities and will help guide computer simulations and experimental synthesis in material screening.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]
  1. Imperial College London, London (United Kingdom). Dept. of Materials; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  2. Univ. of Manchester (United Kingdom). Dept. of Chemistry
  3. Polytechnic Univ. of Valencia (UPV) (Spain). Inst. de Diseño para la Fabricación y Producción Automatizada
  4. Imperial College London, London (United Kingdom). Dept. of Physics
  5. Imperial College London, London (United Kingdom); Yonsei Univ., Seoul (South Korea)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); Engineering and Physical Sciences Research Council (EPSRC); National Research Foundation of Korea (NRF); European Union (EU)
OSTI Identifier:
1603581
Grant/Contract Number:  
AC02-05CH11231; EP/L000202; 2018M3D1A1058536; 277757; EP/P007821/1; 785789-COMEX
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 2; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yang, Ruo Xi, Skelton, Jonathan M., da Silva, Estelina L., Frost, Jarvist M., and Walsh, Aron. Assessment of dynamic structural instabilities across 24 cubic inorganic halide perovskites. United States: N. p., 2020. Web. doi:10.1063/1.5131575.
Yang, Ruo Xi, Skelton, Jonathan M., da Silva, Estelina L., Frost, Jarvist M., & Walsh, Aron. Assessment of dynamic structural instabilities across 24 cubic inorganic halide perovskites. United States. https://doi.org/10.1063/1.5131575
Yang, Ruo Xi, Skelton, Jonathan M., da Silva, Estelina L., Frost, Jarvist M., and Walsh, Aron. Tue . "Assessment of dynamic structural instabilities across 24 cubic inorganic halide perovskites". United States. https://doi.org/10.1063/1.5131575. https://www.osti.gov/servlets/purl/1603581.
@article{osti_1603581,
title = {Assessment of dynamic structural instabilities across 24 cubic inorganic halide perovskites},
author = {Yang, Ruo Xi and Skelton, Jonathan M. and da Silva, Estelina L. and Frost, Jarvist M. and Walsh, Aron},
abstractNote = {Metal halide perovskites are promising candidates for next-generation photovoltaic and optoelectronic applications. The flexible nature of the octahedral network introduces complexity when understanding their physical behavior. It has been shown that these materials are prone to decomposition and phase competition, and the local crystal structure often deviates from the average space group symmetry. To make stable phase-pure perovskites, understanding their structure-composition relations is of central importance. We demonstrate, from lattice dynamics calculations, that the 24 inorganic perovskites ABX3 (A = Cs, Rb; B = Ge, Sn, Pb; X = F, Cl, Br, I) exhibit instabilities in their cubic phase. These instabilities include cation displacements, octahedral tilting, and Jahn-Teller distortions. The magnitudes of the instabilities vary depending on the chemical identity and ionic radii of the composition. The tilting instabilities are energetically dominant and reduce as the tolerance factor increases, whereas cation displacements and Jahn-Teller type distortions depend on the interactions between the constituent ions. We further considered representative tetragonal, orthorhombic, and monoclinic perovskite phases to obtain phonon-stable structures for each composition. This work provides insights into the thermodynamic driving force of the instabilities and will help guide computer simulations and experimental synthesis in material screening.},
doi = {10.1063/1.5131575},
url = {https://www.osti.gov/biblio/1603581}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 2,
volume = 152,
place = {United States},
year = {2020},
month = {1}
}

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