Synergistic Mn/Zn Bimetallic Engineering of Organic‐Inorganic Hybrid Halide Glasses for Advanced X‐Ray Scintillation

ABSTRACT Organic‐inorganic hybrid metal halide (OIMH) glass combines advantages such as low preparation temperature, high optical transparency, and abundant structural flexibility, making it a promising candidate for high‐performance X‐ray imaging. However, the recrystallization‐induced devitrification hinders its long‐term application. Therefore, developing OIMH glass with both high scintillation performance and excellent glass‐forming ability remains an important challenge. In this work, we employ a synergistic Mn/Zn bimetallic engineering strategy to enhance the scintillation performance of Mn‐based glass by increasing the Mn–Mn distance, improving X‐ray absorption ability, and promoting optical transparency. The incorporation of a dimethylamine group onto the phosphonium cation endows (BDMAP) 2 Mn x Zn 1‐x Br 4 (BDMAP = benzyl (4‐(N, N‐dimethylamino) phenyl) diphenylphosphonium) with high glass‐transition temperatures (T g >87°C). The optimized (BDMAP) 2 Mn 0.3 Zn 0.7 Br 4 transparent luminescent OIMH glass shows a high light yield (LY) of 18 315 photons/MeV, a low limit of detection (LOD) of 85.05 nGy/s, and an outstanding spatial resolution of 20 lp/mm. Notably, (BDMAP) 2 Mn 0.3 Zn 0.7 Br 4 glass shows no crystallization even after heating at 100°C for 21 weeks, demonstrating strong resistance to recrystallization. This study presents a rational design route for regulating the scintillation performance of OIMH glasses with high stability.