Reversible Halide Exchange Reaction of Organometal Trihalide Perovskite Colloidal Nanocrystals for Full-Range Band Gap Tuning

In recent years, methylammonium lead halide (MAPbX₃, where X = Cl, Br, and I) perovskites have attracted tremendous interest caused by their outstanding photovoltaic performance. Mixed halides have been frequently used as the active layer of solar cells, as a result of their superior physical properties as compared to those of traditionally used pure iodide. Herein, we report a remarkable finding of reversible halide-exchange reactions of MAPbX₃, which facilitates the synthesis of a series of mixed halide perovskites. We synthesized MAPbBr₃ plate-type nanocrystals (NCs) as a starting material by a novel solution reaction using octylamine as the capping ligand. The synthesis of MAPbBr_3–<i>x</i>Cl_<i>x</i> and MAPbBr_3–<i>x</i>I_<i>x</i> NCs was achieved by the halide exchange reaction of MAPbBr₃ with MACl and MAI, respectively, in an isopropyl alcohol solution, demonstrating full-range band gap tuning over a wide range (1.6–3 eV). Moreover, photodetectors were fabricated using these composition-tuned NCs; a strong correlation was observed between the photocurrent and photoluminescence decay time. Among the two mixed halide perovskite series, those with I-rich composition (<i>x</i> = 2), where a sole tetragonal phase exists without the incorporation of a cubic phase, exhibited the highest photoconversion efficiency. To understand the composition-dependent photoconversion efficiency, first-principles density-functional theory calculations were carried out, which predicted many plausible configurations for cubic and tetragonal phase mixed halides