Enhanced Crystallization and Optimized Morphology of Perovskites Through Doping an Indium‐Based Metal–Organic Assembly: Achieving Significant Solar Cell Efficiency Enhancements

Perovskite crystallization and morphology are two essential factors to the photoelectric performances of perovskite solar cells (PSCs). A 3D metal–organic assembly [In2(phen)3Cl6]·CH3CN·2H2O (In2) is introduced for the first time into lead iodide precursor to modify the quality of a perovskite thin film through a two‐step sequential deposition method. As a result, both the lead iodide and perovskite exhibit improved crystallization and modified morphology. The optimized film presents less trap states and is thus in favor of the charge transfer as well as charge collection. Consequently, open circuit voltage (Voc) and fill factor obviously show enhancements from 0.99 to 1.04 V and from 0.66 to 0.71, respectively, yielding a significant increase in a power conversion efficiency from 15.41% to 17.15%. Meanwhile, the hydrophobic property of In2 can increase the moisture resistance of the perovskite, which offers a simple and effective method to improve the stability of PSCs. A metal–organic assembly [In2(phen)3Cl6]·CH3CN·2H2O is introduced into a precursor to modify the crystallization and morphology of PbI2 and the corresponding perovskite, thus increasing the perovskite solar cell efficiencies. This method provides a novel perspective for the development of photoelectric devices.