Role of Self-Trapped Excitons in the Broadband Emission of Lead-Free Perovskite-Inspired Cu(2)AgBiI(6)

[Image: see text] The perovskite-inspired Cu(2)AgBiI(6) (CABI) absorber shows promise for low-toxicity indoor photovoltaics. However, the carrier self-trapping in this material limits its photovoltaic performance. Herein, we examine the self-trapping mechanism in CABI by analyzing the excited-state dynamics of its absorption band at 425 nm, which is responsible for the self-trapped exciton emission, using a combination of photoluminescence and ultrafast transient absorption spectroscopies. Photoexcitation in CABI rapidly generates charge carriers in the silver iodide lattice sites, which localize into the self-trapped states and luminesce. Furthermore, a Cu–Ag–I-rich phase that exhibits similar spectral responses as CABI is synthesized, and a comprehensive structural and photophysical study of this phase provides insights into the nature of the excited states of CABI. Overall, this work explains the origin of self-trapping in CABI. This understanding will play a crucial role in optimizing its optoelectronic properties. It also encourages compositional engineering as the key to suppressing self-trapping in CABI.