Enhancing the X-ray Sensitivity of Cs₂AgBiBr₆ Double Perovskite Single Crystals through Cation Engineering

Owing to their outstanding optoelectronic properties, halide perovskite (HP) materials have been employed in a wide range of applications, including solar cells, light-emitting devices, and X-ray detectors. Among them, lead-free double HPs are characterized by enhanced stability and reduced toxicity compared with lead-based alternatives. Cs₂AgBiBr₆, in particular, has emerged as a promising candidate for direct X-ray detection. The detection sensitivity, on the other hand, cannot yet compete with that of lead-containing perovskites. Developing schemes to improve X-ray detection efficiency is critical for reducing radiation exposure in medical imaging applications. Here, we investigate the potential of controlled doping and cation substitution with either lanthanides or small organic cations to improve the X-ray detection performance of Cs₂AgBiBr₆. Our findings reveal that by growing the perovskite in a slightly Bi-poor and Eu-rich environment, the X-ray sensitivity significantly increases 7-fold (from 17 to 120 μC Gy_air ^-1 cm^-2) and simultaneously improves the phototo-dark current ratio (from 2.5 to 29). Additionally, Cs-site substitution with imidazolium remarkably enhances the sensitivity over 10-fold (180 μC Gy_air ^-1 cm^-2), and ammonium enhances the phototo-dark current ratio to 37. Terahertz photoconductivity measurements reveal a positive correlation between enhanced X-ray sensitivity and improved charge transport properties (e.g., increased scattering time and, thus, carrier mobility) by doping. This study outlines straightforward strategies for boosting X-ray detection and fundamental photoconductivity in lead-free double HP, with potential implications for broader optoelectronic applications.