Solution-Phase Halide Exchange and Targeted Annealing Kinetics in Lead Chloride Derived Hybrid Perovskites

Hybrid perovskites are a promising class of materials for a range of optoelectronic applications. Many material properties are dictated by the details of the synthetic process, yet a mechanistic understanding is lacking for the majority of these materials. We have studied the formation of methylammonium lead iodide films derived from a lead chloride precursor to understand both the casting solution chemistry and its influence on the final, largely chlorine-free, film. Using solution-phase extended X-ray absorption spectroscopy, we observe a halide exchange with the primary solution plumbate species identified as PbI_2.5Cl_0.33. The mixed halide plumbate solution species leads to formation of the crystalline intermediate phase of (CH₃NH₃)₂PbI₃Cl. Using in situ synchrotron X-ray diffraction, we show that compositional control of the casting solution can control the annealing kinetics of film formation. Our study demonstrates the importance of solution-phase chemistry and its impact on lead halide perovskite synthesis.