The reduction processes of Eu3+ ions in aluminoborosilicate glasses were studied using both high-temperature melting in air and β-irradiation by time-resolved luminescence and electron paramagnetic resonance spectroscopies. The Eu2+ ions produced during the synthesis are characterized by the UV excited broadband luminescence in the blue region due to the 4f65d1–4f7 transition. This band revealed the presence more than one Eu2+ site participating in the emission with different crystalline fields and with different covalency of surrounding ligands. In irradiated glasses, the observed redshift of the Eu2+ emission band is related to the different relative proportion between Eu2+ sites.
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