Synthesis of the Elusive Bulk Iodide Double-Perovskite Semiconductor, Cs2AgBiI6: Microcrystals and Photoconductive Films

Three-dimensional (3D) iodide double-perovskite (elpasolite) semiconductors have attracted interest as potential lead-free metal-halide absorber layers for solar applications. Although studied extensively by computational methods, they have remained largely inaccessible synthetically, consistent with their predicted thermodynamic instability. Here, we report the first synthesis of bulk Cs2AgBiI6, demonstrating both microcrystalline and thin-film forms. Microcrystalline powders of Cs2AgBiI6 were prepared via anion exchange from phase-pure Cs2AgBiBr6 microcrystals. The resulting iodide elpasolite shows broad absorption throughout the visible with a 1.70 ± 0.05 eV optical bandgap and near-infrared photoluminescence centered at 1.03 eV. We identify the elimination of trace moisture in bulk Cs2AgBiBr6 as the critical factor enabling complete halide exchange and isolation of bulk Cs2AgBiI6 with phase purity. In inert atmosphere, microcrystalline Cs2AgBiI6 shows no decomposition when stored for months at room temperature or heated to ∼70 °C, and it appears equally stable in dry air. Building upon these insights, we then demonstrate the preparation of phase-pure Cs2AgBiI6 films by flash thermal evaporation of Cs2AgBiBr6 followed by anion exchange. Photoconductivity measurements on such Cs2AgBiI6 films demonstrate photocarrier generation and transport, marking the first optoelectronic measurement on this elusive 3D iodide double perovskite.