Nanoscopic cross-grain cation homogenization in perovskite solar cells

Multiscale cation inhomogeneity has been a major hurdle in state-of-the-art formamidinium-caesium (FA-Cs) mixed-cation perovskites for achieving perovskite solar cells with optimal power conversion efficiencies and durability. Although the field has attempted to homogenize the overall distributions of FA-Cs in perovskite films from both plan and cross-sectional views, our understanding of grain-to-grain cation inhomogeneity and ability to tailor it-that is, spatially resolving the FA-Cs compositional difference between individual grains down to the nanoscale-are lacking. Here we reveal that as fundamental building blocks of a perovskite film, individual grains exhibit cationic compositions deviating from the prescribed ideal composition, severely limiting the interfacial optoelectronic properties and perovskite layer durability. This performance-limiting nanoscopic factor is linked to thermodynamic-driven morphological grooving, leading to a segmented surface landscape. At the grain triple junctions, grooves form nanoscale groove traps that hinder the mixing of solid-state cations across grains and thus retard inter-grain FA-Cs mixing. By rationally modulating the heterointerfacial energies, we reduced the depth of these nanoscale groove traps by a factor of three, significantly improving cation homogeneity. Perovskite solar cells with shallower nanoscale groove traps demonstrate enhanced power conversion efficiencies (25.62%) and improved stability under various standardized international protocols. Our work highlights the significance of resolving surface nano-morphologies for homogeneous properties of perovskites.