Computational Screening and Discovery of Silver–Indium Halide Double Salts

Perovskite-inspired materials have emerged as promising candidates for both outdoor and indoor photovoltaic applications owing to their favorable optoelectronic properties and reduced toxicity. Here, we employ the experimentally realized AgBiI (Formula presented.) double salt as a structural prototype and replace Bi (Formula presented.) with In (Formula presented.) to design a novel lead-free halide compound, AgInI (Formula presented.). First-principles calculations predict that AgInI (Formula presented.) is both chemically and dynamically stable, exhibiting a direct bandgap of 1.72 eV, comparable to its bismuth analog. However, its predicted photovoltaic performance, evaluated using the spectroscopic limited maximum efficiency metric, is lower under both solar and LED illumination. This reduction arises primarily from symmetry-forbidden optical transitions and the absence of Bi-derived 6s (Formula presented.) lone-pair states at the valence band maximum. High-throughput screening of the Ag–In–I ternary phase space reveals several more stable and metastable compounds that fall into two structural families: tetrahedrally and octahedrally coordinated, with characteristic bandgaps near 3.0 and 2.0 eV, respectively. Despite multiple synthetic attempts, the predicted AgInI (Formula presented.) phase could not be experimentally realized, underscoring the challenges of stabilizing indium-based halide double salts. While these materials are unlikely to serve as efficient photovoltaic absorbers, their tunable bandgaps and stability make them promising candidates for charge transport and other optoelectronic applications.