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article
Crystal formation in Eu3+ - Doped oxyfluorophosphate glass-ceramics for luminescence thermometry
Abstract
<p>Eu<sup>3+</sup> doped-Oxyfluorophosphate glasses with a general composition 75 NaPO<sub>3</sub> - (25-x) CaO – x CaF<sub>2</sub> (with x ranging from 0 to 25 mol%) were prepared and their spectroscopic changes induced by the addition of fluorine and when applying a thermal treatment in order to grow crystals in the glasses were investigated. The addition of CaF<sub>2</sub> at the expense of CaO reduces Ω<sub>2</sub> and Ω<sub>4</sub> parameters indicating that the Eu<sup>3+</sup> ions are located in less covalent and well separated sites in oxyfluorophosphate glasses. An increase in the CaF<sub>2</sub> content at the expense of CaO also leads to an increase in the absolute thermometric sensitivity from (4.2 × 10<sup>−4</sup>) K<sup>−1</sup> to (17.6 × 10<sup>−4</sup>) K<sup>−1</sup> at 523 K while decreasing the relative thermometric sensitivity from 3.0% to 1.4%. The heat treatment leads to the precipitation of crystals, the composition of crystal phase depends on the glass composition. For the glasses with x = 0 and 10, the thermal treatment increases Ω<sub>6</sub> while reducing Ω<sub>4</sub>, as a result of an enhanced stiffness and reduced covalency of dopant's environment due to the precipitation of various crystals. As Ω<sub>2</sub> remains unchanged, the Eu<sup>3+</sup> are suspected to remain mainly in the amorphous part of the glass-ceramics in agreement with the lack of sharp peaks in the emission spectrum. For the glasses with x = 20 and 25, Ω<sub>2</sub> increases indicating a change in the site symmetry of Eu<sup>3+</sup> resulting from the dopant entering the CaF<sub>2</sub> crystalline phase. Due to the changes in the Eu<sup>3+</sup> sites in the heat treated glasses, the heat treatment of the glass increases the absolute thermal sensitivity, but reduces the relative thermal sensitivity. The oxyfluorophosphate glass-ceramic with x = 25 exhibits high absolute thermometric sensitivity compared to oxyfluorophosphate glass, but also comparatively low relative sensitivity of 0.5% K<sup>−1</sup>.</p>