Air-Stable Bulk Halide Single-Crystal Scintillator Cs3Cu2I5 by Melt Growth: Intrinsic and Tl Doped with High Light Yield

Ternary metal halides with large exciton binding energy have recently gained considerable attention in the optoelectronic field due to their high photoluminescence quantum yield and large Stokes shift. Here, efficient scintillators are designed based on these advantageous properties. For the first time, bulk Cs₃Cu₂I₅ is grown using a melt method other than the intensively reported solution growth, and behaved as an intrinsic scintillator, emitting bright blue (∼450 nm) light under X-ray and γ-ray irradiation. Successful Tl doping at Cs sites tune the emission band over the entire visible range (400-700 nm) due to the synergetic effects of self-trapped excitons (STEs) and Tl centers. Notably, after doping with 1% Tl⁺, the scintillation light yield of Cs₃Cu₂I₅ increases by nearly three times to 51 000 ± 2000 ph/MeV (Cs-137, 662 keV). Cs₃Cu₂I₅:Tl shows a higher energy resolution of 4.5% at 662 keV than that of NaI:Tl and an excellent nonproportionality (<3%) in the γ-ray energy range of 60-1275 keV. A model of energy relaxation in Cs₃Cu₂I₅:Tl scintillators is proposed and discussed. In particular, it is the first Cu-based halide scintillator that has air stability, good stopping power, and the ability to grow large bulk single crystals for practical application. This work provides a strategy for tuning and broadening the spectral range of STE emitters, and bridges the lead-free halide derivatives with scintillators.