Suppression of Ionic and Electronic Conductivity by Multilayer Heterojunctions Passivation Toward Sensitive and Stable Perovskite X‐Ray Detectors

Abstract Organic‐inorganic hybrid perovskites are promising candidates for direct X‐ray detection and imaging. The relatively high dark current in perovskite single crystals (SCs) is a major limiting factor hindering the pursuit of performance and stability enhancement. In this study, the contribution of dark current is disentangled from electronic (σ_e) and ionic conductivity (σ_i) and shows that the high σ_i dominates the dark current of MAPbBr₃ SCs. A multilayer heterojunctions passivation strategy is developed that suppresses not only the σ_i by two orders of magnitude but also σ_e by a factor of 1.6. The multilayer heterojunctions passivate the halide vacancy defects and increase the electron and hole injection barrier by inducing surface p‐type doping of MAPbBr₃. This enables the MAPbBr₃ SC X‐ray detectors to obtain a high sensitivity of 19 370 µC Gy_air⁻¹ cm⁻² under a high electric field of 100 V cm⁻¹, a record high sensitivity for bromine self‐powered devices, and a low detection limit of 42.3 nGy_air s⁻¹. The unencapsulated detectors demonstrate a stable baseline after storage for 210 days and outstanding operational stability upon irradiation with an accumulated dose of up to 1944 mGy_air.