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,Chemistry of Materials

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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
Chemistry of Materials ( IF 7.2 ) Pub Date : 2020-01-21 , DOI: 10.1021/acs.chemmater.9b04341
Tianshuai Lyu ₁ , Pieter Dorenbos ₁

Affiliation

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 NaLu_1–xY_xGeO₄. 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 NaLu_1–xY_xGeO₄:0.01Bi³⁺ and NaLu_1–xY_xGeO₄:0.01Bi³⁺,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.

中文翻译：

ARE（Si，Ge）O ₄（A = Li，Na; RE = Y，Lu）中铋和镧系元素的真空参考结合能：旨在设计用于能量存储的电荷载流子俘获过程

为具有高电荷载流子存储能力的持久发光和存储磷光体的固态材料开发可行的设计原理仍然是一个关键的挑战。在这里，我们报告通过真空参考结合能（VRBE）图辅助能带结构工程和晶体合成优化进行这种合理设计的方法。以ARE（Si，Ge）O ₄（A = Li，Na; RE = Y，Lu）晶体系统为模型实例。首先系统地研究了掺铋和镧系元素的ARE（Si，Ge）O ₄系统的低温（10 K）光致发光激发和发射光谱，然后建立了相应的VRBE方案。在这些VRBE方案的指导下，在NaLu中探索了Bi ³⁺余辉和存储磷的性质_{1– x} Y _x GeO ₄。通过将Bi ³⁺与Bi ³⁺本身或Eu ^3+结合，Bi ³⁺似乎充当了一个深空穴陷阱中心，而Bi ³⁺和Eu ³⁺充当了一个不那么深的电子陷阱。通过调节x可以在NaLu _{1– x} Y _x GeO ₄：0.01Bi ³⁺和NaLu _{1– x} Y _x GeO ₄：0.01Bi ³⁺，0.001Eu ³⁺中实现陷阱深度可调余辉和存储。，导致进行导带工程。在NaYGeO ₄：0.01Bi ^3+中，由于Bi ²⁺释放出电子并与Bi ⁴⁺处的空穴复合，Bi ³⁺的持续发光可测量超过28 h 。发现NaYGeO ₄：0.01Bi ^3+中的载流子存储容量通过优化1200°C的合成条件在24小时内增加了约7倍。优化的NaYGeO ₄：0.001Bi ³⁺和NaYGeO ₄：0.01Bi ³⁺，0.001Eu ³⁺的热致发光（TL）强度比最先进的X射线存储荧光粉BaFBr（I）：Eu的TL高约3倍至约7倍。通过将发现和优化的NaYGeO ₄：0.01Bi ³⁺余辉磷光体与钙钛矿CsPbBr ₃和CdSe量子点相结合，证明了用于防伪应用的概念验证颜色调整。通过紫外线或X射线带电的NaYGeO ₄：0.01Bi ³⁺，0.001Eu ³⁺证明了信息存储的应用荧光粉分散在硅胶成像膜中。这项工作不仅报告了出色的存储磷光体，而且更重要的是提供了一种设计原理，可以通过结合VRBE方案指导的能带结构工程和晶体合成优化，以设计方式启动余辉和存储磷光体的更多探索。

更新日期：2020-01-22

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