MAPb(Br1–xClx)3 Hybrid Perovskite Materials for Direct X-ray Detection

Abstract

The study and development in recent years of hybrid (organic–inorganic) halide perovskite materials have given them an unprecedented opportunity for direct ionizing radiation detection, given their large attenuation coefficient and sufficient charge carrier mobility lifetime product. The use of single crystals, considered as model materials, allows us to investigate their intrinsic properties. Characterizations under X-ray illumination of detector devices based on methylammonium lead tribromide (MAPbBr3) single crystals, obtained by optimized growths, show good sensitivity but high dark current density. To improve this critical parameter, while using MAPbBr3 as the base material, we employ anion engineering within the halide elements. We present here mixed halide perovskite crystals, with bromide partially replaced with chloride, obtained through optimized growths using modified inverse temperature crystallization in dimethylformamide, leading to high-quality single crystals of the general formula MAPb(Br1–xClx)3. Six chlorine contents are targeted and carefully determined experimentally via energy-dispersive X-ray analysis and X-ray powder diffraction. For each composition, several crystals are synthesized and used to prepare X-ray detection devices. Their optoelectronic properties are determined under standard X-ray medical conditions and hint at the existence of an optimal composition. MAPb(Br0.85Cl0.15)3 exhibits the best sensitivity with a value of S ≈ 3 μC mGyair–1 cm–2 for RQA5 spectral quality and the lowest dark current density with a value of Jdark ≈ 22 nA mm–2, both recorded at a 50 V mm–1 electric field. This sensitivity value doubles our own MAPbBr3 single crystal device and is higher than that of CsI(Tl)- or a-Se-based flat panels. The present work broadens the benefits and drawbacks of employing halide engineering in perovskite materials to improve the optoelectronic performance under high-energy radiation.