A Universal Polybromide Melt Strategy for the Direct Conversion of Metals into Optoelectronic-Grade Bromide Perovskites

Abstract: Halide perovskite systems require specific metal oxidation states (M2+ or M+/M3+ pairs), limiting processing flexibility during traditional synthesis and posing stability challenges for multivalent metals like Sn, Cu, and Au. This work anchors a profound paradigm shift: a universal, single-step, organic-solvent free synthetic platform that directly converts stable elemental metal films into bromide perovskite and perovskite-related systems for a wide variety of (opto)electronic applications. The synthetic platform uses methylammonium polybromide melt (PBM) that reacts at room temperature with different elemental metals, including Pb, Sn, Au, and Cu, successfully transforming them into their respective Br-perovskite phases: MAPbBr3, MASnBr3, MA2Au2Br6, and MA2CuBr4. It is shown that the PBMs chemical activity can be tuned, and in situ X-ray diffraction captures in two cases transient intermediate phases during phase evolution. For Sn, which tends towards overoxidation to Sn4+ phase, changes in the PBMs composition coupled with a metallic Sn mediated comproportionation reaction allowed suppressing overoxidation, and formation of high quality MASnBr3 films under ambient conditions. Overall, oxidation and disproportionation potentials are found to be useful metrics for predicting M:PBM reaction outcomes. Industrially, this approach should be fully compatible with roll-to-roll infrastructure, providing a low-barrier pathway to scale next-generation optoelectronic technologies.