Surface defects have been a key constraint for perovskite photovoltaics. Herein, 1,3‐dimethyl‐3‐imidazolium hexafluorophosphate (DMIMPF6) ionic liquid (IL) is adopted to passivate the surface of a formamidinium‐cesium lead iodide perovskite (Cs0.08FA0.92PbI3) and also reduce the energy barrier between the perovskite and hole transport layer. Theoretical simulations and experimental results demonstrate that Pb‐cluster and Pb‐I antisite defects can be effectively passivated by [DMIM]+ bonding with the Pb2+ ion on the perovskite surface, leading to significantly suppressed non‐radiative recombination. As a result, the solar cell efficiency was increased to 23.25 % from 21.09 %. Meanwhile, the DMIMPF6‐treated perovskite device demonstrated long‐term stability because the hydrophobic DMIMPF6 layer blocked moisture permeation.

Inorganic cesium lead halide perovskite solar cells (PSCs) have received enormous attention due to their excellent stability compared with that of their organic–inorganic counterparts. However, the lack of optimization strategies leads the inorganic PSCs to suffer from low efficiency arising from significant recombination. To overcome this dilemma, a surface modification of the electron transport layer (ETL)/perovskite interface is undertaken by using SmBr3 to improve the crystallization and morphology of the perovskite layer for enhanced ETL/perovskite interface interaction. Encouragingly, a gradient energy band is created at the interface with an outstanding hole blocking effect. As a result, both the charge recombination occurring at the interface and the nonradiative recombination inside the perovskite are suppressed, and, simultaneously, the charge extraction is improved successfully. Therefore, the power conversion efficiency of the CsPbIBr2 PSCs is increased to as high as 10.88% under one sun illumination, which is 30% higher than its counterparts without the modification. It is logically inferred that this valuable optimization strategy can be extended to other analogous structures and materials.