Tuning the Structural and Optoelectronic Properties of Cs2AgBiBr6Double-Perovskite Single Crystals through Alkali-Metal Substitution

Lead-free double perovskites have great potential as stable and nontoxic optoelectronic materials. Recently, Cs(2)AgBiBr(6)has emerged as a promising material, with suboptimal photon-to-charge carrier conversion efficiency, yet well suited for high-energy photon-detection applications. Here, the optoelectronic and structural properties of pure Cs(2)AgBiBr(6)and alkali-metal-substituted (Cs1-xYx)(2)AgBiBr6(Y: Rb+, K+, Na+;x = 0.02) single crystals are investigated. Strikingly, alkali-substitution entails a tunability to the material system in its response to X-rays and structural properties that is most strongly revealed in Rb-substituted compounds whose X-ray sensitivity outperforms other double-perovskite-based devices reported. While the fundamental nature and magnitude of the bandgap remains unchanged, the alkali-substituted materials exhibit a threefold boost in their fundamental carrier recombination lifetime at room temperature. Moreover, an enhanced electron-acoustic phonon scattering is found compared to Cs2AgBiBr6. The study thus paves the way for employing cation substitution to tune the properties of double perovskites toward a new material platform for optoelectronics.