Spontaneous octahedral tilting in the cubic inorganic cesium halide perovskites CsSnX3 and CsPbX3 (X = F, Cl, Br, I)

Ruo Xi Yang, Jonathan M. Skelton, E. Lora Da Silva, Jarvist M. Frost, Aron Walsh

Research output: Contribution to journalArticlepeer-review

151 Citations (Scopus)


The local crystal structures of many perovskite-structured materials deviate from the average space-group symmetry. We demonstrate, from lattice-dynamics calculations based on quantum chemical force constants, that all of the cesium-lead and cesium-tin halide perovskites exhibit vibrational instabilities associated with octahedral titling in their high-temperature cubic phase. Anharmonic double-well potentials are found for zone-boundary phonon modes in all compounds with barriers ranging from 108 to 512 meV. The well depth is correlated with the tolerance factor and the chemistry of the composition, but is not proportional to the imaginary harmonic phonon frequency. We provide quantitative insights into the thermodynamic driving forces and distinguish between dynamic and static disorder based on the potential-energy landscape. A positive band gap deformation (spectral blue shift) accompanies the structural distortion, with implications for understanding the performance of these materials in applications areas including solar cells and light-emitting diodes.

Original languageEnglish
Pages (from-to)4720-4726
Number of pages7
JournalJournal of Physical Chemistry Letters
Issue number19
Publication statusPublished - 2017 Oct 5

Bibliographical note

Funding Information:
The research has been funded by the European Research Council (project 27757) and the EPSRC (grant nos. EP/ K016288/1 and EP/K004956/1). Via our membership in the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk).

Publisher Copyright:
© 2017 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Physical and Theoretical Chemistry


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