Effect of Tm3+ codoping on Ca2Si5N8:Eu2+, Tm3+ red long-afterglow phosphor

Ca2Si5N8:Eu2+ is known to exhibit a long red afterglow when codoped with Tm3+. In this study, the effects of Tm3+ codoping on the afterglow properties of Ca2Si5N8:Eu2+ are investigated in detail using time-resolved fluorescence spectroscopy and electron spin resonance (ESR). Ca2Si5N8:Eu2+, Tm3+ shows three types of emission: broad blue emission (450 nm), blue-line emission of Tm3+ (460 and 480 nm), and red emission of Eu2+ (615 nm). The broad blue emission is related to the defect levels in the host crystal. Eu2+ and Tm3+ decay with an intrinsic time (0.8 and 80 μs, respectively), thereafter Eu2+ emits afterglows with the same slope as the defect luminescence. The afterglow decay curve from 1 to 1000 s is linear in a log–log plot. Thermoluminescence measurements show trapped levels at 0.04 and 1.4 eV for Ca2Si5N8:Eu2+, and the addition of Tm3+ increases the number of electrons trapped in levels from 0.3 to 0.8 eV. In ESR measurements, nitrogen vacancies in silicon nitride crystals can be detected by the signal intensity of Si dangling bonds. The intensity of nitrogen vacancies is decreased by codoping of Tm3+. Hyperfine signal intensity from Eu2+ nuclear magnetic moments is also decreased. These results suggest that Tm3+ is located close enough to affect the electronic configuration of nitrogen vacancies and Eu2+. Nitrogen vacancies and Tm3+–Eu2+ pairs are considered to interact with each other and energy is transferred among them, which leads to a long afterglow.