Semiconducting Organic Metal Halide Complex Glasses for Efficient X‐Ray Detection

Abstract The growing demand for efficient, low‐cost, and scalable direct X‐ray detectors has prompted the exploration of materials beyond conventional inorganic semiconductors, e.g., Si, α‐Se, and Cd(Zn)Te. While organic semiconductors offer attractive features, including mechanical flexibility and low‐temperature solution processability, they often fall short in sensitivity, energy resolution, and detection limits compared to their inorganic counterparts. Here, the first demonstration of direct X‐ray detectors is reported based on a new class of materials, organic metal halide complexes (OMHCs), which are composed of metal halide species covalently bonded to organic semiconducting units. Specifically, 4‐(4‐(diphenylamino) phenyl)‐1‐(propyl)‐pyridinium zinc bromide ((TPA‐Py) 2 ZnBr 2 ) is employed in its glassy form to fabricate high‐performance direct X‐ray detectors. By applying a facile melt‐processing approach, wet‐chemistry‐synthesized (TPA‐Py) 2 ZnBr 2 single crystals can be easily transformed into air‐stable glassy samples with tunable dimensions for device integration. The resulting glassy OMHC‐based X‐ray detectors exhibit outstanding performance, including a high dark resistivity (5.37 × 10 11 Ω cm), an excellent detection sensitivity (2,020 µC Gy air −1 cm −2 ) at an electric field of 10 V mm −1 , and an ultralow detection limit of 12.44 nGy air s −1 . These results establish semiconducting OMHC glasses as a highly promising new class of materials for direct X‐ray detectors.