Achieving High Operating‐Temperature Self‐powered X‐Ray Detection in Multilayered Hybrid Perovskites through Arylamine Intercalation

Abstract Polar metal halide hybrid perovskites (PHPs) that exhibit outstanding bulk photovoltaic effect (BPVE), excellent semiconductor features, and strong radiation absorption ability, have shown prominent advantages in highly sensitive direct X‐ray detection. However, it is still a challenge to explore PHPs with high BPVE temperature ranges, answering the demand of developing thermally stable passive X‐ray detection. Herein, by intercalating arylamine into lead tribromide and inducing order‐disorder phase transition, a 2D multilayered PHPs (BZA) 2 (MA)Pb 2 Br 7 ( BZPB , BZA = benzylamine, MA = methylamine) is synthesized. BZPB crystallizes in a polar space group Aea 2 at a low‐temperature phase and demonstrates a significant open‐circuit of 0.3 V deriving from BPVE under X‐ray irradiation. Meanwhile, the strong X‐ray absorption coefficient and outstanding carrier transport capability of the bilayered lead halide framework associated with the polar BPVE give BZPB excellent X‐ray detection abilities. At 0 V bias, the impressive sensitivity of BZPB is 98 µC Gy −1 cm −2 . Importantly, the introduction of the rigid BZA ring increases the energy barrier of phase transition and thus dramatically enhances the X‐ray detection operating temperature of BZPB up to 409 K without significant performance degradation. This work strongly reveals the great potential of rational design of metal halide hybrid perovskites for X‐ray detection applications.