Low energy paths for octahedral tilting in inorganic halide perovskites

TL;DR

This study uses first-principles calculations to explore low energy pathways of octahedral tilting in inorganic halide perovskites, revealing dynamic disorder and specific tilt switch mechanisms that influence phase transitions.

Contribution

It identifies multiple low energy tilt paths and highlights the significance of a particular tilt switch in the phase transition dynamics of inorganic halide perovskites.

Findings

Presence of dynamic disorder in phase transitions.

Identification of a low energy tilt switch path.

Intermediate tetragonal structure explained by tilt fluctuations.

Abstract

Instabilities relating to cooperative octahedral tilting is common in materials with perovskite structures, and in particular in the sub class of halide perovskites. In this work, the energetics of octahedral tilting in the inorganic metal halide perovskites CsPbI$_3$ and CsSnI$_3$ are investigated using first-principles density functional theory calculations. Several low energy paths between symmetry equivalent variants of the stable orthorhombic (\textit{Pnma}) perovskite variant are identified and investigated. The results are in favor of the presence of dynamic disorder in the octahedral tilting phase transitions of inorganic halide perovskites. In particular, one specific type of path, corresponding to an out-of-phase "tilt switch", is found to have significantly lower energy barrier than the others, which indicates the existence of a temperature range where the dynamic fluctuations of the octahedra follow only this type of path. This could produce a time averaged structure corresponding to the intermediate tetragonal (\textit{P4/mbm}) structure observed in experiments. Deficiencies of the commonly employed simple one-dimensional "double well" potentials in describing the dynamics of the octahedra are pointed out and discussed.