Composition–Structure–Property Correlations in Rare-Earth-Doped Heavy Metal Oxyfluoride Glasses

Structure–property correlations in oxyfluoride glasses have been explored in a series of lead fluoroborate and lead fluorogermanate glasses with nominal compositions (50 – x – y – z)B2O3–40PbO–y(Al2O3)–(10 + x)PbF2–zREF3 and (50 – x – y)GeO2–40PbO–y(Al2O3)–(10 + x)PbF2–zREF3 (x, y = 0, 10, 0 ≤ z ≤ 0.5, RE = Eu, Yb). Starting from glasses with a fixed PbF2 content of 10 mol %, we explore the effects of (1) increasing PbF2 content to 20 mol % and (2) incorporating the intermediate oxide Al2O3 at the expense of GeO2 or B2O3. The emission characteristics studied on Eu-doped glasses are rationalized on the basis of structural information obtained by Raman, nuclear magnetic resonance (NMR), and pulsed electron paramagnetic resonance (EPR) spectroscopies on Yb-doped samples. In the Ge-oxyfluoride glasses, increasing PbF2 content results in enhanced excited-state lifetimes of the rare-earth ions, and for this system, Eu3+ emission profiles, NMR, and EPR results suggest an increased average number of fluoride ions...

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