Zero-Dimensional Lead-Free FA₃Bi₂I₉ Single Crystals for High-Performance X-ray Detection

Direct X-ray detectors based on metal halide perovskites and their derivatives exhibit high sensitivity and low limit of detection (LoD). Compared with three-dimensional (3D) hybrid lead halide perovskites, low-dimensional A₃Bi₂I₉ perovskite derivatives (A = Cs, Rb, NH₄, CH₃NH₃(MA)) present better stability, greater environmental friendliness, and comparable X-ray detection performance. Here, we report FA₃Bi₂I₉ (FA= CH(NH₂)₂) single crystals (SCs) as a new member of the A₃Bi₂I₉ series for X-ray detection, which were prepared by the nucleation-controlled secondary solution constant temperature evaporation (SSCE) method. Centimeter-sized FA₃Bi₂I₉ SCs show a full width at half-maximum (fwhm) of 0.0096°, which is superior to that of recently reported Cs₃Bi₂I₉ (0.058°) and MA₃Bi₂I₉ SCs (0.024°) obtained by inverse temperature crystallization (ITC). The as-grown FA₃Bi₂I₉ SC shows a large resistivity of 7.8 × 10¹⁰ Ω cm and a high ion migration activation energy (E_a) of 0.56 eV, which can guarantee a low noise level and good operational stability under a large external bias. The FA₃Bi₂I₉ SC detector exhibits a LoD of 0.2 μGy_air s^-1, a sensitivity of 598.1 μC Gy_air ^-1 cm ^-2, and an X-ray detection efficiency of 33.5%, which are much better than those of the commercialized amorphous selenium detector. Results presented here will provide a new lead-free perovskite-type material to achieve green, sensitive, and stable X-ray detectors.