Deciphering the Mechanism of Ultrafast Scintillation in 1D Silver Halides

The development of ultrafast scintillators is critical to the GHz X‐ray and time‐of‐flight (TOF) imaging techniques. Low‐dimensional silver‐based halides have emerged as promising candidates due to high radioluminescence efficiency and ultrafast decay time. However, the ultrafast scintillation mechanism in silver‐based halides, such as Rb2AgBr3 (RAB), remains controversial. Here, the study reveals the origin of ultrafast scintillation timing response in melt‐grown RAB bulk crystals. The RAB shows light‐yellow emission with a photoluminescence quantum yield (PLQY) of 13.9%. Under the picosecond (ps) pulse X‐ray irradiation, RAB has an ultrafast decay time of 3.2 ns that accounts for 40.5% of the total emitted light. The light yield is estimated as 3100 photons MeV−1 under 22Na irradiation. Based on the temperature‐dependent radioluminescence (RL) spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and spectrally resolved thermally‐stimulated luminescence (TSL) glow curves, it is confirmed that the bromine vacancy as the F‐center is the origin of the ultrafast scintillation component. These findings provide elaborated and fundamental insights into the ultrafast luminescent mechanisms of low‐dimensional silver‐based halides, thereby opening up new design horizons in the development of ultrafast scintillators. Rb2AgBr3 bulk crystals are synthesized with an ultrafast scintillation decay time of 3.2 ns. Excitation of F‐center in scintillation mechanism, observed here probably for the first time in halide scintillator. This work elaborates on the origin of ultrafast timing and demonstrates the feasibility of achieving ultrafast scintillation decay time based on F‐center in low‐dimensional Ag‐based halides.