Size dependent solid-solid crystallization of halide perovskites

Abstract

The efficiency and stability of halide perovskite-based solar cells and light-emitting diodes directly depend on the intricate dynamics of solid-solid crystallization[1-23]. In this study, we employ a multi-scale approach using random phase approximation, density functional theory, machine learning potentials, reduced charge force fields, and both enhanced sampling biased and brute-force unbiased molecular dynamics simulations to understand the solid-solid phase transitions in cesium lead iodide perovskite. Our simulations uncover that the direct phase transition from the non-perovskite to the perovskite involves the formation of stacked-faulted and low-dimensional intermediate structures. Through extensive large-scale all-atom simulations encompassing up to 650,000 atoms, we observe that solid-solid crystallization may require the formation of a sufficiently large critical nucleus to grow into a faceted perovskite crystal. Based on simulations, we determine that utilizing (100)-faceted seeded crystallization could offer a promising path for manufacturing high-performance and stable perovskite solar cells.