Local Observation of Phase Segregation in Mixed-Halide Perovskite

Mixed-halide perovskites have emerged as promising materials for optoelectronics due to their tunable band gap in the entire visible region. A challenge remains, however, in the photoinduced phase segregation, narrowing the band gap of mixed-halide perovskites under illumination thus restricting applications. Here, we use a combination of spatially resolved and bulk measurements to give an in-depth insight into this important yet unclear phenomenon. We demonstrate that photoinduced phase segregation in mixed-halide perovskites selectively occurs at the grain boundaries rather than within the grain centers by using shear-force scanning probe microscopy in combination with confocal optical spectroscopy. Such difference is further evidenced by light-biased bulk Fourier-transform photocurrent spectroscopy, which shows the iodine-rich domain as a minority phase coexisting with the homogeneously mixed phase during illumination. By mapping the surface potential of mixed-halide perovskites, we evidence the higher concentration of positive space charge near the grain boundary possibly provides the initial driving force for phase segregation, while entropic mixing dominates the reverse process. Our work offers detailed insight into the microscopic processes occurring at the boundary of crystalline perovskite grains and will support the development of better passivation strategies, ultimately allowing the processing of more environmentally stable perovskite films.