LAUSR

Laminated multilayers of perovskite films with different optical and electronic characteristics will easily realize high‐performance optoelectronic devices because it is widely demonstrated that differential distribution of film properties in the vertical direction of devices plays particularly important roles in device performance. However, the existing laminated perovskite films are hardly prepared by a solution process because there is no solvent with sufficient selectivity of solubility for different perovskite materials. Here, it is demonstrated that aniline (AN) has a largely different solubility toward the perovskite MAPbI3 and the MAPbI3 blend with an additive of hydrochloride diethylammonium chloride. By using AN as the solvent in the perovskite precursor solution, two laminated perovskite layers with different crystal size and optical and electrical characteristics are achieved. Inverted perovskite solar cells with the laminated films as active layers achieve an averaged power conversion efficiency of 20.65% originating from the high VOC 1.112 V and fill factor of 80.8%. The devices maintain 98% efficiency after 400 h under 65% RH. This work provides a very simple and feasible method for production of laminated perovskite films to achieve high‐performance perovskite solar cells.