稀土掺杂上转换发光玻璃陶瓷的制备及性能

Preparation and Properties of Rare Earth Doped Glass Ceramics with Upconversion Luminescence Behaviors

实验制备了一类含有SrF2∶Yb3＋,Tm3＋及SrF2∶Yb3＋,Er3＋的透明发光玻璃和玻璃陶瓷,对比研究了热处理工艺对玻璃陶瓷相组成、微观结构和光谱性能的影响规律。研究表明,玻璃陶瓷具有立方SrF2纳米晶相均匀分布于玻璃基体的复相结构,利用HRTEM可观测到SrF2纳米晶相的（111）晶面,其晶粒尺度在10~30nm之间,且该析晶相中富集有Yb3＋/Tm3＋和Yb3＋/Er3＋。基于此,玻璃陶瓷在980nm LD激光激发下的上转换发光强度较玻璃样品有较大提高。其上转换发光机制分别主要为Yb3＋-Yb3＋之间的合作上转换,Yb3＋-Tm3＋和Tm3＋-Tm3＋之间的交叉弛豫能量传递过程,以及Yb3＋-Er3＋之间的能量传递上转换。

We prepared a series of transparent luminescent glass ceramics containing SrF2： Yb3＋,Tm3＋ and SrF2： Yb3＋,Er3＋nanocrystallites,and investigated their microstructure and luminescence properties.In the glass ceramic samples,SrF2 nanocrystals were embedded uniformly in the glass matrix.Such nanocrystals sized around 10~30nm,and their（111） crystal plane could be observed through high-resolution transmission electron microscopy（HRTEM）.As Yb3＋/Tm3＋ and Yb3＋/Er3＋ in the glass ceramics could be enriched into the precipitated SrF2 nanocrystalline phase,which provide much lower phonon vibration energy than the glass matrix.As a result,the upconversion luminescence of the glass ceramics were enhanced a lot,compared with that of the glass when pumping with 980nm LD.The upconversion mechanisms are mainly due to Yb3＋-Yb3＋ cooperative upconversion,Yb3＋-Tm3＋ cross relaxations,Tm3＋-Tm3＋ cross relaxations and Yb3＋-Er3＋ energy transfer upconversion,respectively.