CsI‐Antisolvent Adduct Formation in All‐Inorganic Metal Halide Perovskites

Abstract The excellent optoelectronic properties demonstrated by hybrid organic/inorganic metal halide perovskites are all predicated on precisely controlling the exact nucleation and crystallization dynamics that occur during film formation. In general, high‐performance thin films are obtained by a method commonly called solvent engineering (or antisolvent quench) processing. The solvent engineering method removes excess solvent, but importantly leaves behind solvent that forms chemical adducts with the lead‐halide precursor salts. These adduct‐based precursor phases control nucleation and the growth of the polycrystalline domains. There has not yet been a comprehensive study comparing the various antisolvents used in different perovskite compositions containing cesium. In addition, there have been no reports of solvent engineering for high efficiency in all‐inorganic perovskites such as CsPbI₃. In this work, inorganic perovskite composition CsPbI₃ is specifically targeted and unique adducts formed between CsI and precursor solvents and antisolvents are found that have not been observed for other A‐site cation salts. These CsI adducts control nucleation more so than the PbI₂–dimethyl sulfoxide (DMSO) adduct and demonstrate how the A‐site plays a significant role in crystallization. The use of methyl acetate (MeOAc) in this solvent engineering approach dictates crystallization through the formation of a CsI–MeOAc adduct and results in solar cells with a power conversion efficiency of 14.4%.