In Situ TEM Monitoring of Phase-Segregation in Inorganic Mixed Halide Perovskite

Abstract

Photoinduced phase separation, which limits the available band gap energies for photovoltaic applications, was reported for a range of mixed-halide perovskites. A microscopic understanding of the phase separation mechanism is still lacking but may be beneficial to rationalize limitations as well as enable the design of phase-stable perovskite semiconductors. In this letter, electron-beam-induced phase separations and transformations were investigated in a small crystallite of CsPb(Br_0.8I_0.2)₃ by means of in situ high-resolution imaging in a transmission electron microscope. The acquired time series was evaluated using principal and independent component analysis to classify the structural change during the illumination by the electron beam. A more iodine-rich phase with the approximate composition of CsPb(Br_0.6I_0.4)₃ was found to form at the edges of the particle, while a ternary pure bromide phase of CsPbBr₃ remained at its center. These results provide an atomistic picture of in-grain phase segregation into iodide-rich phases at grain boundaries and bromide-rich phases in the interior of the grain.