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Er3+ doped phosphate glasses with the composition 75NaPO3-25CaF2 (mol%) were prepared at different melting temperatures to demonstrate the importance to quantify the fluorine content when preparing oxyfluoride glasses. Indeed, increasing the melting temperature from 900 to 1000 °C leads to a small reduction in the fluorine content from 9.4 at % to 8.8 at % as quantified using EPMA. Whereas this loss of fluorine can be suspected from small changes in the thermal properties of the glass, it increases significantly the glass crystallization tendency in this glass system. This means that a heat treatment of the as-prepared glass should be performed when evaporation of fluorine during the glass melting is suspected. Sample preparation for the characterization of the spectroscopic properties of the glasses is discussed here as well; bulk glasses should be used when measuring the spectroscopic properties of oxyfluoride glasses, which are known to be hygroscopic. It is shown, in this work, that a heat treatment of the glass within the investigated glass system leads to transparent glass-ceramics with volume precipitation of Er3+ doped CaF2 crystals with strong upconversion.

Persistent luminescence (PeL) was obtained from glasses with the composition (75NaPO3-25CaF2) (in mol%) by adding PeL microparticles SrAl2O4:Eu2+,Dy3+ in the melts using the direct doping method. The glasses exhibit a strong PeL although they crystallize upon quenching. The crystallization was related to the poor thermal stability of the glass, and also to the extensive loss of fluorine during the glass preparation. The use of quartz crucibles and the long process time used to prepare glasses using the direct doping method are responsible for the fluorine losses.

Glasses with the composition (75 NaPO3-(25-x) CaO-xCaF2) (in mol %) were prepared with 0.15 mol% of Er2O3. The effect of the glass composition and of heat treatment on the spectroscopic properties of the newly developed glasses is reported. With the progressive replacement of CaO by CaF2, the Er3+:4I13/2 lifetime and the intensity of the upconversion emission increase whereas the intensity of the emission at 1.5 μm decreases due to the decrease in the phonon energy in the as-prepared glasses. The glasses were heat treated at 20 °C above their respective glass transition temperature for 17 h to form nuclei and then at their crystallization temperature from 15min to 1 h to grow the nuclei into crystals. The heat treatment leads to the precipitation of crystalline phases, the composition of which depends upon the glass composition. As the Er3+:4I13/2 lifetime increases and the intensity of the upconversion increases for the glass with x = 0 after heat treatment, the Er3+ ions are expected to be incorporated into the phosphate-based crystals. However, as the shape of the emission band at 1.5 μm remains unchanged and the intensity of the upconversion decreases significantly after heat treatment of the glasses with x > 10, the crystals found in the glass-ceramics with x > 10 are thought to free of Er3+ ions. Although Er3+ ions entered in the CaF2 crystals precipitating in aluminosilicate glass, the Er3+ ions are believed to remain in the amorphous phosphate part of the glass-ceramic containing CaF2 crystals.