Influence of Solvent Coordination on Hybrid Organic–Inorganic Perovskite Formation

Solution-processed hybrid organic–inorganic perovskites (HOIPs) from organoammonium halide and lead halide precursors form efficacious active layers for photovoltaics, light-emitting diodes, and flexible electronics. Though solvent–solute coordination plays a critical role in HOIP crystallization, the influence of solvent choice on such interactions is poorly understood. We demonstrate Gutmann's donor number, DN, as a parameter that indicates the coordinating ability of the processing solvent with the Pb2+ center of the lead halide precursor. Low DN solvents interact weakly with the Pb2+ center, favoring instead complexation between Pb2+ and iodide and subsequent crystallization of perovskite. High DN solvents coordinate more strongly with the Pb2+ center, which in turn inhibits iodide coordination and stalls perovskite crystallization. Varying the concentration of high-DN additives in precursor solutions tunes the strength of lead–solvent interactions, allowing finer control over the crystallization and the resulting morphology of HOIP active layers.