Operando Characterizations of Light-Induced Junction Evolution in Perovskite Solar Cells

[Image: see text] Light-induced performance changes in metal halide perovskite solar cells (PSCs) have been studied intensively over the last decade, but little is known about the variation in microscopic optoelectronic properties of the perovskite heterojunctions in a completed device during operation. Here, we combine Kelvin probe force microscopy and transient reflection spectroscopy techniques to spatially resolve the evolution of junction properties during the operation of metal-halide PSCs and study the light-soaking effect. Our analysis showed a rise of an electric field at the hole-transport layer side, convoluted with a more reduced interfacial recombination rate at the electron-transport layer side in the PSCs with an n–i–p structure. The junction evolution is attributed to the effects of ion migration and self-poling by built-in voltage. Device performances are correlated with the changes of electrostatic potential distribution and interfacial carrier dynamics. Our results demonstrate a new route for studying the complex operation mechanism in PSCs.