Unraveling Halogen Role in Two-Step Solution Growth of Organic-Inorganic Hybrid Mixed-Halide Perovskites: Guidelines of Fabricating Single-Phase Perovskites with Predictable Stoichiometry

The challenge faced in optoelectronic applications of halide perovskites is their degradation. Minimizing material imperfections is critical to averting cascade degradation processes. Identifying causes of such imperfections is, however, hindered by mystified growth processes and is particularly urgent for mixed-halide perovskites because of inhomogeneity in growth and phase segregation under stresses. To unravel two-step solution growth of MAPbBr(x)I(3-x), we monitored the evolution of Br composition and found that the construction of perovskite lattice is contributed by iodine from PbI2 substrate and Br from MABr solution with a 1:1 ratio rather than a 2:1 ratio originally thought. Kinetic analysis based on a derived three-stage model extracted activation energies of perovskite construction and anion exchange. This model is applicable to the growth of PbI2 reacting with a mixed solution of MABr and MAI. Two guidelines of fabricating single-phase MAPbBr(x)I(3-x) with predictable stoichiometry thus developed help strategizing protocols to reproducibly fabricate mixed-halide perovskite films tailored to specific optoelectronic applications.