We report the effect of thermal annealing on structure, composition, optical transmittance and thickness of a novel fluorozirconate glass (ZLANI) containing Zr, La, Al, Na and In fluorides. In this work, pulsed laser deposition was used to grow thin films of ZLANI, and thermal annealing at different temperatures was performed on the films. Annealing did not change the composition, but a clear structural evolution of the ZLANI glass was observed by transmission electron microscopy (TEM), showing that we can control microstructure independent of composition. An increase in transmittance after the film was subject to a 100 °C thermal anneal was ascribed to the removal of defects and structural relaxation in the amorphous state. Following an anneal of 200 °C, the transmittance decreases due to heterogeneous formation of crystalline nuclei and changes in the local bonding. After the final annealing at 300 °C, a wider-scale crystallization occurred, with some major crystal phases formed as Zr₂F₈(H₂O)₆ and ZrO₂, which alters the shape of the transmittance curve. The crystalline content of the crystal phases that form in the annealed films was quantified using hollow cone dark field TEM imaging. The 100 °C or 200 °C annealing decreases the film thickness by inducing structural relaxation and densification of the amorphous films, while the thickness increase of the 300 °C annealed film resulted from the formed large crystals. These results provide insights for the design of multilayer nanocomposites with a ZLANI glass matrix, which have potential applications as up-/down-conversion luminescent materials and X-ray storage phosphors.

我们报告了热退火对包含Zr，La，Al，Na和In氟化物的新型氟锆酸盐玻璃（ZLANI）的结构，组成，透光率和厚度的影响。在这项工作中，使用脉冲激光沉积来生长ZLANI薄膜，并对薄膜进行不同温度的热退火。退火没有改变组成，但是通过透射电子显微镜（TEM）观察到ZLANI玻璃的明显结构演变，表明我们可以独立于组成来控制微观结构。对该膜进行100°C热退火后，透射率的增加归因于缺陷的去除和非晶态结构的松弛。在200°C退火后，透射率由于晶核的不均匀形成和局部键的变化而降低。在300°C下最终退火后，发生了更大规模的结晶，形成了一些主要的晶体相，如Zr。₂ F ₈（H ₂ O）₆和ZrO ₂，改变了透射率曲线的形状。使用空心锥暗场TEM成像定量分析在退火膜中形成的晶相的晶体含量。100°C或200°C退火通过引起非晶态膜的结构弛豫和致密化来减小膜厚，而300°C退火膜的厚度增大是由形成的大晶体引起的。这些结果为具有ZLANI玻璃基质的多层纳米复合材料的设计提供了见识，这些复合材料具有上/下转换发光材料和X射线存储荧光粉的潜在应用。