| Summary: | The demand for modern materials, especially glasses, used in different applications, such as radiation sensors and spectral converters, requires a detailed study of their properties. The incorporation of fluoride compounds in borate glasses and their crystallization at the nanometric scale allows the properties of these materials to be further enhanced. Although many works showed improvements in some of these properties, some critical aspects, such as the crystallization mechanism and the role of the fluorine phase, need more investigation. We worked with xNaF (100 − x)BaO·2B<sub>2</sub>O<sub>3</sub> glasses with x = 0, 5, 10, 15, 20, 25, 30, and 35% (in mol) to increase the knowledge in this field. The structural modifications and the thermally stimulated luminescence of the glasses were studied, and their crystallization was analyzed by thermal analysis and X-ray diffraction. A continuous trap distribution was found, which was responsible for its very good luminescent signal, especially in glasses with 20% NaF. By selecting a suitable amount of NaF, it is possible to obtain nanocrystals of BaF<sub>2</sub>. These promising results we reached show the applicability of these materials.
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