LAUSR

Doping of all‐inorganic lead halide perovskites to enhance their photovoltaic performance and stability has been reported to be effective. Up to now most studies have focused on the doping of elements in to the perovskite lattice. However, most of them cannot be doped into the perovskite lattice and the roles of these dopants are still controversial. Herein,the authors introduce CdI2 as an additive into CsPbI3−xBrx and use it as active layer to fabricate high‐performance inorganic perovskite solar cells (PSCs). Cd with a smaller radius than Pb can partially substitute Pb in the perovskite lattice by up to 2 mol%. Meanwhile, the remaining Cd stays on the surface and grain boundaries (GB) of the perovskite film in the form of Cs2CdI4−xBr−x, which is found to reduce non‐radiative recombination. These effects result in prolonged charge carrier lifetime, suppressed defect formation, decreased GBs, and an upward shift of energybands in the Cd‐containing film. A champion efficiency of 20.8% is achieved for Cd‐incorporated PSCs, together with improved device ambient stability. This work highlights the importance of simultaneous lattice engineering, defectcontrol and atomic‐level characterization in achieving high‐performance inorganic PSCs with well‐defined structure‐property relationships.