Defect Passivation and Crystallization Regulation for Efficient and Stable Formamidinium Lead Iodide Solar Cells with Multifunctional Amidino Additive

Abstract Amidino‐based additives show great potential in high‐performance perovskite solar cells (PSCs). However, the role of different functional groups in amidino‐based additives have not been well elucidated. Herein, two multifunctional amidino additives 4‐amidinobenzoic acid hydrochloride (ABAc) and 4‐amidinobenzamide hydrochloride (ABAm) are employed to improve the film quality of formamidinium lead iodide (FAPbI 3 ) perovskites. Compared with ABAc, the amide group imparts ABAm with larger dipole moment and thus stronger interactions with the perovskite components, i.e., the hydrogen bonds between N…H and I − anion and coordination bonds between C = O and Pb 2+ cation. It strengthens the passivation effect of iodine vacancy defect and slows down the crystallization process of α‐FAPbI 3 , resulting in the significantly reduced non‐radiative recombination, long carrier lifetime of 1.7 µs, uniformly large crystalline grains, and enhances hydrophobicity. Profiting from the improved film quality, the ABAm‐treated PSC achieves a high efficiency of 24.60%, and maintains 93% of the initial efficiency after storage in ambient environment for 1200 hours. This work provides new insights for rational design of multifunctional additives regarding of defect passivation and crystallization control toward highly efficient and stable PSCs.