Stability Trend of Tilted Perovskites

TL;DR

This study uses first-principles calculations to analyze the stability of tilted phases in halide perovskites, revealing linear correlations with tolerance factor and atomic packing fraction, and extending stability descriptors to tilted phases.

Contribution

It introduces a comprehensive first-principles analysis of octahedral tilting in halide perovskites and validates the stability descriptor (t+μ)η for tilted phases.

Findings

Stabilization energies correlate linearly with tolerance factor t.

Tilt energies are linearly correlated with atomic packing fraction change ({Δ}η).

The stability descriptor (t+μ)η effectively predicts stability of tilted perovskites.

Abstract

Halide perovskites, with prototype cubic phase ABX3, undergo various phase transitions accompanied by rigid rotations of corner-sharing BX6 octahedra. Using first-principles density functional theory calculations, we have performed a comprehensive investigation of all the possible octahedral tilting in eighteen halide perovskites ABX3 (A = Cs, Rb, K; B= Pb, Sn; X= I, Br, Cl) and found that the stabilization energies i.e. energy differences between cubic and the most stable tilted phases, are linearly correlated with tolerance factor t. Moreover, the tilt energies i.e. energy differences between cubic and various tilted phases, are linearly correlated with the change of atomic packing fractions ({\Delta}{\eta}), confirming the importance of atomic packing fraction as part of stability descriptor (t+{\mu}){\eta}, proposed in our previous work [JACS 139, 14905 (2017)]. We further demonstrate that (t+{\mu}){\eta}remains the best stability descriptor for tilted perovskites among descriptor candidates of {\eta}, {\mu}, t, and t+{\mu},extending previously proposed stability trend from cubic phases to tilted phases in general perovskites.