单斜相(Zr,Hf)O2:Ti4+,RE3+中的离子团簇、能量传递与高灵敏光学探温研究

发光材料的温度传感研究在国际上得到广泛开展，发展灵敏性和信号可识别度高的基于非单发光中心热耦合能级的荧光强度比技术是当前的研究热点。本项目采用能量传递体关联的双发光中心荧光强度比实现探温。申请人前期研究发现了单斜相ZrO2中基于能量传递机制的Ti4+和Eu3+共存的强发射，并利用它们的荧光强度比实现了高灵敏探温；还观察到了一些与Ti4+和稀土离子(RE3+)聚集相关的发光特性。本申请拟研究Ti4+和RE3+共掺杂的单斜相(Zr,Hf)O2荧光探温材料，揭示荧光强度比及其温度特性与Zr/Hf组分，Ti4+和RE3+浓度的关系规律，优化设计出高灵敏探温材料；研究能量传递机制；探索Ti4+及Ti4+-RE3+离子团簇的存在性，等价和异价离子团簇形成和破坏的新机制；深入认识能量传递和高灵敏探温与离子团簇的相关性。本项目将为实现高灵敏荧光探温提供材料技术指导，为认识掺杂离子的空间分布特性提供新视角。

The optical thermometry of luminescent materials were investigated world widely. The current research hotspot is to develop the fluorescence intensity ratio (FIR) technology toward the high sensitivity and signal discriminability while not based upon the thermally coupled level pairs of single luminescent center. This project prepares to achieve the FIR temperature sensing on the basis of energy transfer bridged dual-emitting combination strategy. In previous studies, the applicant has observed intense luminescence from both O-Ti4+ charge transfer (CT) state and Eu3+ ions in monoclinic ZrO2 which was bridged by the novel energy transfer under ultraviolet excitation, and found that their FIR could be used for high sensitivity optical thermometry. In addition, we also observed some luminescence phenomena probably correlating with activators aggregation. Targeting the high sensitivity optical thermometry, this research proposal intends to investigate the design and optimization of Ti4+ and RE3+ co-doped monoclinic (Zr,Hf)O2 optical thermometric materials, to reveal the relationship of FIR and its temperature dependence with Zr/Hf ratio in the host and the concentration of Ti4+ and RE3+ ions. We plan to study the energy transfer mechanism between CT(O-Ti4+) and RE3+ ions. We also plan to explore the existence of Ti4+ and Ti4+-RE3+ clusters in the(Zr,Hf)O2 host lattices, and finally reveal the new mechanisms responsible for the formation and destruction of both equivalent and aliovalent ions clusters. This research is expected to provide in-depth understanding on the correlations between ion clusters and energy transfer/high sensitivity optical thermometry. It is believed that the implement of this project will provide technical guidance for the materials design towards high sensitivity fluorescence temperature sensing and give a new perspective for understanding the distribution characteristics of dopants.