Metal‐Free Halide Perovskite Single Crystals with Very Long Charge Lifetimes for Efficient X‐ray Imaging

Abstract Metal‐free halide perovskites, as a specific category of the perovskite family, have recently emerged as novel semiconductors for organic ferroelectrics and promise the wide chemical diversity of the ABX 3 perovskite structure with mechanical flexibility, light weight, and eco‐friendly processing. However, after the initial discovery 17 years ago, there has been no experimental information about their charge transport properties and only one brief mention of their optoelectronic properties. Here, growth of large single crystals of metal‐free halide perovskite DABCO‐NH 4 Br 3 (DABCO = N ‐ N ′‐diazabicyclo[2.2.2]octonium) is reported together with characterization of their instrinsic optical and electronic properties and demonstration, of metal‐free halide perovskite optoelectronics. The results reveal that the crystals have an unusually large semigap of ≈16 eV and a specific band nature with the valence band maximum and the conduction band minimum mainly dominated by the halide and DABCO 2+ , respectively. The unusually large semigap rationalizes extremely long lifetimes approaching the millisecond regime, leading to very high charge diffusion lengths (tens of μm). The crystals also exhibit high X‐ray attenuation as well as being lightweight. All these properties translate to high‐performance X‐ray imaging with sensitivity up to 173 μC Gy air −1 cm −2 . This makes metal‐free perovskites novel candidates for the next generation of optoelectronics.