Crystal‐Size‐Induced Band Gap Tuning in Perovskite Films

A comprehensive picture explaining the effect of the crystal size in metal halide perovskite films on their opto‐electronic characteristics is currently lacking. We report that perovskite nanocrystallites exhibit a wider band gap due to concurrent quantum confinement and size dependent structural effects, with the latter being remarkably distinct and attributed to the perturbation from the surface of the nanocrystallites affecting the structure of their core. This phenomenon might assist in the photo‐induced charge separation within the perovskite in devices employing mesoporous layers as they restrict the size of nanocrystallites present in them. We demonstrate that the crystal size effect is widely applicable as it is ubiquitous in different compositions and deposition methods employed in the fabrication of state‐of‐the‐art perovskite solar cells. This effect is a convenient and effective way to tune the band gap of perovskites.