First-Principles Characterization of Surface Phonons of Halide Perovskite CsPbI3 and Their Role in Stabilization

Abstract

The stability of halide perovskites has been a long-standing issue for their real-world application. Approaches to improve stability include nanostructuring, dimensionality reduction, and strain engineering, where surfaces play an important role in the formation of a stable structure. To understand the mechanism we compute the lattice dynamics of the surface of CsPbI₃ using density functional theory. We demonstrate, for the first time, that CsPbI₃ crystals exhibit surface phonons that are localized on the outermost layers of the slabs, and we perform a complete symmetry characterization including an identification of the Raman/IR active modes. These surface phonons are present in the optically active cubic phase but are absent in the optically inactive “yellow” phase. Furthermore, we show that the surface suppresses bulk instabilities by hardening soft modes of the bulk cubic phase, resulting in phase stabilization and quenching of dynamical disorder. This study is fundamental for understanding the structural behavior of halide perovskite materials with high surface area-to-volume ratios, and for guiding stabilization strategies.