Halide Engineering in Mixed Halide Perovskite-Inspired Cu₂AgBiI₆ for Solar Cells with Enhanced Performance

Cu₂AgBiI₆ (CABI) is a promising perovskite-inspired absorber for solar cells due to its direct band gap and high absorption coefficient. However, the nonradiative recombination caused by the high extrinsic trap density limits the performance of CABI-based solar cells. In this work, we employ halide engineering by doping bromide anions (Br^–) in CABI thin films, in turn significantly improving the power conversion efficiency (PCE). By introducing Br^– in the synthetic route of CABI thin films, we identify the optimum composition as CABI-10Br (with 10% Br at the halide site). The tailored composition appears to reduce the deep trap density as shown by time-resolved photoluminescence and transient absorption spectroscopy characterizations. This leads to a dramatic increase in the lifetime of charge carriers, which therefore improves both the external quantum efficiency and the integrated short-circuit current. The photovoltaic performance shows a significant boost since the PCE under standard 1 sun illumination increases from 1.32 to 1.69% (∼30% relative enhancement). Systematic theoretical and experimental characterizations were employed to investigate the effect of Br^– incorporation on the optoelectronic properties of CABI. Our results highlight the importance of mitigating trap states in lead-free perovskite-inspired materials and that Br^– incorporation at the halide site is an effective strategy for improving the device performance.