Electron-Volt Fluctuation of Defect Levels in Metal Halide Perovskites on a 100 ps Time Scale

Metal halide perovskites (MHPs) have gained considerable attention due to their excellent optoelectronic performance, which is often attributed to unusual defect properties. We demonstrate that midgap defect levels can exhibit very large and slow energy fluctuations associated with anharmonic acoustic motions. Therefore, care should be taken classifying MHP defects as deep or shallow, since shallow defects may become deep and vice versa. As a consequence, charges from deep levels can escape into bands, and light absorption can be extended to longer wavelengths, improving material performance. The phenomenon, demonstrated with iodine vacancy in CH₃NH₃PbI₃ using a machine learning force field, can be expected for a variety of defects and dopants in many MHPs and other soft inorganic semiconductors. Since large-scale anharmonic motions can be precursors to chemical decomposition, a known problem with MHPs, we propose that materials that are stiffer than MHPs but softer than traditional inorganic semiconductors, such as Si and TiO₂, may simultaneously exhibit excellent performance and stability.