稀土/过渡族离子共掺的新型发光玻璃陶瓷制备、显微结构调控与性能研究

The control and optimization of the energy transfer process between different active ions is one of the key problems to study the optical materials. Owing to the obviously distinct electronic structures of the rare earth ions (REI) and transition metal ions (TMI), it is difficult for them to simultaneously obtain excellent optical performance in the same matrix material. This project aims to prepare novel transparent glass ceramic (TGC) containing both fluoride and oxide nanocrystals by melt-quenching and subsequent heat-treatment, to realize the selectively partition of REI and TMI into the fluoride or oxide nanocrystals, and to simultaneously achieve excellent optical performance for these two active centers. The impact of the precursor glass compositions and the crystallization conditions on the crystal structure, size, distribution and crystallization fraction of these two types of precipitated nanocrystals are going to be carefully investigated. The key factors affecting the selectively partition of active ions into the specified crystal phases will be explored. The relationship between the distribution of active ions and their energy transfer will also be revealed. Based on the construction of the correlation between the preparation, microstructure and optical property of TGC, the optical performance of this novel glass ceramic will be optimized. After the accomplishment of this project, it is hoped that an experimental and theoretical basis will be provided for developing some new materials with the controlled energy transfer and designed spectral features.

不同激活离子间能量传递的控制与优化是发光材料研究的关键问题之一。作为发光中心的稀土与过渡族离子因其电子结构差异明显，难以在同一基质中同时显示优良的发光性能。本项目拟采用熔体急冷法及可控晶化处理，制备含氟化物与氧化物双纳米晶相的新型透明玻璃陶瓷，并实现共掺的稀土与过渡族离子选择性进入氟化物与氧化物晶相中，使得两种激活中心同时具有优异的发光性能。系统研究前驱玻璃组分与晶化条件对玻璃陶瓷中析出的两种纳米晶相的晶型、尺度、分布与晶化分数的影响；探明影响激活离子选择性进入特定晶相的关键因素，揭示激活离子的分布与相互间能量传递的关系；建立材料制备、显微结构与发光性能间的关联，通过进一步调控组分、结构，优化材料的发光性能。通过本项目的研究，为进一步研发具有能量传递控制特性、光谱可设计的新型发光材料奠定实验和理论基础。

采用熔体急冷法及后续热处理成功制备了系列稀土/过渡族离子（如：Eu3+/Ni2+、Tm3+/Mn2+、Pr3+/Mn2+与Er3+/Co2+等）共掺杂的、含氟化物与氧化物双纳米晶化相（如：YF3/Ga2O3、GdF3/Ga2O3、ZnAl2O4/YF3等）透明玻璃陶瓷。系统研究了氟化物与氧化物的晶化过程，实现了两类纳米晶化相在玻璃基体中的可控析出；探索了掺杂离子半径与价态、玻璃基体组分、析出晶相组成与晶型结构等对共掺杂离子分布的影响，实现了其在两类晶相中的选择性分布；受益于此，共掺杂激活离子间的能量传递由于被空间隔离而得到抑制，且由于稀土与过渡族离子均具备适合的配位晶场环境，因而获得了优异的发光性能。在此基础上，通过选择不同的稀土/过渡族离子共掺组合与氟化物/氧化物析出晶相，设计并制备了系列具有不同发光特性的透明玻璃陶瓷光功能材料：如Tm3+/Mn2+共掺杂的、含Ga2O3/YF3双纳米晶化相透明玻璃陶瓷具有多色发光性能，Co2+/Er3+共掺的、含ZnAl2O4/YF3双纳米晶化相样品同时具备饱和吸收体与激光增益介质双功能。这些研究成果对调控共掺激活离子间能量传递效应，实现材料发射光谱可工程化设计，优化发光性能具有一定指导意义。项目圆满完成，达到了预期结果。在项目实施过程中，研究成果正式发表SCI论文10篇，申请发明专利5项。