Additive Molecules Adsorbed on Monolayer PbI₂: Atomic Mechanism of Solvent Engineering for Perovskite Solar Cells

Solvent engineering is highly essential for the upscaling synthesis of high-quality metal halide perovskite materials for solar cells. The complexity in the colloidal containing various residual species poses great difficulty in the design of the formula of the solvent. Knowledge of the energetics of the solvent-lead iodide (PbI₂) adduct allows a quantitative evaluation of the coordination ability of the solvent. Herein, first-principles calculations are performed to explore the interaction of various organic solvents (Fa, AC, DMSO, DMF, GBL, THTO, NMP, and DPSO) with PbI₂. Our study establishes the energetics hierarchy with an order of interaction as DPSO > THTO > NMP > DMSO > DMF > GBL. Different from the common notion of forming intimate solvent-Pb bonds, our calculations reveal that DMF and GBL cannot form direct solvent-Pb²⁺ bonding. Other solvent bases, such as DMSO, THTO, NMP, and DPSO, form direct solvent-Pb bonds, which penetrate through the top iodine plane and possess much stronger adsorption than DMF and GBL. A strong solvent-PbI₂ adhesion (i.e., DPSO, NMP, and DMSO), associated with a high coordinating ability, explains low volatility, retarded precipitation of the perovskite solute, and tendency of a large grain size in the experiment. In contrast, weakly coupled solvent-PbI₂ adducts (i.e., DMF) induces a fast evaporation of the solvent, accordingly a high nucleation density and small grains of perovskites are observed. For the first time, we reveal the promoted absorption above the iodine vacancy, which implies the need for pre-treatment of PbI₂ like vacuum annealing to stabilize solvent-PbI₂ adducts. Our work establishes a quantitative evaluation of the strength of the solvent-PbI₂ adducts from the atomic scale perspective, which allows the selective engineering of the solvent for high-quality perovskite films.