Local Rearrangement of the Iodide Defect Structure Determines the Phase Segregation Effect in Mixed-Halide Perovskites

Mixed-halide perovskites represent a particularly relevant case within the family of lead-halide perovskites. Beyond their technological relevance for a variety of optoelectronic devices, photoinduced structural changes characteristic of this type of material lead to extreme photophysical changes that are currently the subject of intense debate. Herein we show that the conspicuous photoinduced phase segregation characteristic of these materials is primarily the result of the local and metastable rearrangement of the iodide sublattice. A local photophysical study comprising spectrally resolved laser scanning confocal microscopy is employed to find a correlation between the defect density and the dynamics of photoinduced changes, which extend far from the illuminated region. We observe that iodide-rich regions evolve much faster from highly defective regions. Also, by altering the material composition, we find evidence for the interplay between the iodide-related defect distribution and the intra- and interdomain migration dynamics giving rise to the complexity of this process.