Bright Transparent Scintillators with High Fraction BaCl2: Eu2+ Nanocrystals Precipitation: An Ionic‐Covalent Hybrid Network Strategy toward Superior X‐Ray Imaging Glass‐Ceramics

Metal halide crystals are bright but hygroscopic scintillator materials that are widely used in X‐ray imaging and detectors. Precipitating them in situ in glass to form glass ceramics (GCs) scintillator offers an efficient avenue for large‐scale preparation, high spatial resolution, and excellent stability. However, precipitating a high fraction of metal halide nanocrystals in glass to maintain high light yield remains a challenge. Herein, an ionic‐covalent hybrid network strategy for constructing GCs scintillator with high crystallinity (up to ≈37%) of BaCl2: Eu2+ nanocrystals is presented. Experimental data and simulations of glass structure reveal that the Ba2+‐Cl− clustering promotes the high crystallization of BaCl2 nanocrystals. The ultralow phonon energy (≈200 cm−1) of BaCl2 nanocrystals and good Eu reduction effect enable high photoluminescence inter quantum efficiency (≈80.41%) in GC. GCs with varied crystallinity of BaCl2: Eu2+ nanocrystals demonstrate efficient radioluminescence and tunable scintillator performance. They either outperform Bi4Ge3O14 single crystal by over 132% steady‐state light yield or provide impressive X‐ray imaging resolutions of 20 lp mm−1. These findings provide a new design strategy for developing bright transparent GCs scintillators with a high fraction of metal halide nanocrystals for X‐ray high‐resolution imaging applications. An ionic‐covalent hybrid glass network is designed to fabricate transparent and stable glass ceramic scintillator with high crystallinity of BaCl2: Eu nanocrystals, which exhibits strong radioluminescence characterized by a light yield 132% of Bi4Ge3O14 single crystal. Besides, the transparent glass ceramic scintillator can be applied as X‐ray imaging application with a high spatial resolution of 20 lp mm−1.