In this study, oxyfluoride glasses with chemical composition of 45SiO2–15Al2O3–10BaO–30BaF2-xTbF3 (x = 0.2, 0.4 and 0.6 (mole ratios)) were prepared through the conventional melt-quenching method. Raman and FTIR spectra as well as molar volume calculations proved the creation of more non-bridging oxygens (NBOs) in presence of more TbF3 content. Accordingly, absorption edge in UV–Vis spectra showed a slight red-shift to longer wavelengths. The glass with 0.4 mol ratios of TbF3, exhibited the highest photoluminescence emission and its green-to-blue intensity ratio was 0.66. Therefore, this sample was chosen and heat treated at 630, 650 and 675 °C to prepare glass ceramic samples. For the sample heat treated at 650 °C, photoluminescence intensity increased and green-to-blue intensity ratio reached 0.69. Also, lifetimes of green and blue emissions increased from 3.35 ms to 3.67 ms and from 2.95 ms to 3.10 ms, respectively, when the base glass heat treated at 650 °C. Formation of BaF2 nanocrystals in glass ceramics moved the UV–Vis absorption edge to longer wavelengths significantly. Increment of the weak and dangling bonds in crystallized samples reduced Fermi energy, indirect and direct optical band gap energies from 3.792 eV to 3.301 eV, from 3.522 eV to 3.093 eV and from 4.095 eV to 3.582 eV respectively, which led to higher semiconducting behaviors.
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