Assessment of dynamic structural instabilities across 24 cubic inorganic halide perovskites
File(s)
Accepted version
Author(s)
Yang, Ruo Xi
Skelton, Jonathan M
da Silva, Estelina L
Frost, Jarvist M
Walsh, Aron
Type
Journal Article
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 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.
Date Issued
2020-01-14
Date Acceptance
2019-11-11
Citation
Journal of Chemical Physics, 2020, 152 (2), pp.024703-1-024703-9
ISSN
0021-9606
Publisher
American Institute of Physics
Start Page
024703-1
End Page
024703-9
Journal / Book Title
Journal of Chemical Physics
Volume
152
Issue
2
Copyright Statement
© 2020 Author(s). This is a pre-copy-editing, author-produced PDF of an article accepted for publication in Journal of Chemical Physics following peer review. The definitive publisher-authenticated version J. Chem. Phys. 152, 024703 (2020); https://doi.org/10.1063/1.5131575
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000539056900003&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
GROUP-THEORETICAL ANALYSIS
TOTAL-ENERGY CALCULATIONS
PHASE-TRANSITIONS
CRYSTAL-STRUCTURES
LONE-PAIR
CESIUM
TEMPERATURE
PRESSURE
CSGEBR3
CONDUCTIVITY
Publication Status
Published
Article Number
ARTN 024703
Date Publish Online
2020-01-09