Phase Segregation Dynamics in Mixed-Halide Perovskites Revealed by Plunge-Freeze Cryogenic Electron Microscopy

Abstract: Mixed-halide lead perovskites, with photoexcited charge-carrier properties suitable for high-efficiency photovoltaics, hold significant promise for high-efficiency tandem solar cells. However, phase segregation under illumination, where an iodide-rich phase forms carrier trap states, remains a barrier to applications. This study employs plunge-freeze cryogenic electron microscopy to visualize nanoscale phase segregation dynamics in CsPb(Br,I) films. By rapidly freezing the illuminated samples, we preserve transient photoexcited ion distributions for high-resolution structural and compositional analysis at the nanoscale. Cryogenic scanning transmission electron microscopy techniques (EELS, 4D-STEM) captured the dynamics of photo-induced iodine migration from grain boundaries to centers, identified the buildup of anisotropic strain, and captured the heterogeneous evolution of this process within a single grain. These findings provide new insights into microscopic phase segregation mechanisms and their dynamics, enhancing our understanding of mixed-halide perovskite photostability.