Charge-Carrier Mobility and Localization in Semiconducting CuAgBiI for Photovoltaic Applications.

Lead-free silver-bismuth semiconductors have become increasingly popular materials for optoelectronic applications, building upon the success of lead halide perovskites. In these materials, charge-lattice couplings fundamentally determine charge transport, critically affecting device performance. In this study, we investigate the optoelectronic properties of the recently discovered lead-free semiconductor CuAgBiI using temperature-dependent photoluminescence, absorption, and optical-pump terahertz-probe spectroscopy. We report ultrafast charge-carrier localization effects, evident from sharp THz photoconductivity decays occurring within a few picoseconds after excitation and a rise in intensity with decreasing temperature of long-lived, highly Stokes-shifted photoluminescence. We conclude that charge carriers in CuAgBiI are subject to strong charge-lattice coupling. However, such small polarons still exhibit mobilities in excess of 1 cm V s at room temperature because of low energetic barriers to formation and transport. Together with a low exciton binding energy of ∼29 meV and a direct band gap near 2.1 eV, these findings highlight CuAgBiI as an attractive lead-free material for photovoltaic applications.