Vacuum-Referred Binding Energies of Bismuth and Lanthanide Levels in ARE(Si,Ge)O4 (A = Li, Na; RE = Y, Lu): Toward Designing Charge-Carrier-Trapping Processes for Energy Storage

Developing a feasible design principle for solid-state materials for persistent luminescence and storage phosphors with high charge carrier storage capacity remains a crucial challenge. Here we report a methodology for such rational design via vacuum referred binding energy (VRBE) diagram aided band structure engineering and crystal synthesis optimization. The ARE(Si,Ge)O4 (A = Li, Na; RE = Y, Lu) crystal system was selected as a model example. Low-temperature (10 K) photoluminescence excitation and emission spectra of bismuth- and lanthanide-doped ARE(Si,Ge)O4 system were first systematically studied, and the corresponding VRBE schemes were then established. Guided by these VRBE schemes, Bi3+ afterglow and storage phosphor properties were explored in NaLu1?xYxGeO4. By combining Bi3+ with Bi3+ itself or Eu3+, Bi3+ appears to act as a deep hole-trapping center, while Bi3+ and Eu3+ act as less-deep electron traps. Trap depth tunable afterglow and storage were realized in NaLu1?xYxGeO4:0.01Bi3+ and NaLu1?xYxGeO4:0.01Bi3+,0.001Eu3+ by adjusting x, leading to conduction band engineering. More than 28 h of persistent luminescence of Bi3+ was measurable in NaYGeO4:0.01Bi3+ due to electron release from Bi2+ and recombination with a hole at Bi4+. The charge carrier storage capacity in NaYGeO4:0.01Bi3+ was discovered to increase ?7 times via optimizing synthesis condition at 1200 ?C during 24 h. The thermoluminescence (TL) intensity of the optimized NaYGeO4:0.001Bi3+ and NaYGeO4:0.01Bi3+,0.001Eu3+ is ?3, and ?7 times higher than the TL of the state-of-the-art X-ray storage phosphor BaFBr(I):Eu. Proof-of-concept color tuning for anti-counterfeiting application was demonstrated by combining the discovered and optimized NaYGeO4:0.01Bi3+ afterglow phosphor with perovskite CsPbBr3 and CdSe quantum dots. Information storage application was demonstrated by UV-light- or X-ray-charged NaYGeO4:0.01Bi3+,0.001Eu3+ phosphor dispersed in a silicone gel imaging film. This work not only reports excellent storage phosphors but more importantly provides a design principle that can initiate more exploration of afterglow and storage phosphors in a designed way through combining VRBE-scheme-guided band structure engineering and crystal synthesis optimization.