Thermally activated conversion of a silicate gel to an oxyfluoride glass ceramic: Optical study using Eu3+ probe ion

Sol–gel route using metal alkoxides precursor and trifluoroacetic acid as in situ fluorination reagent has been used to prepare Eu3+-doped silicate xerogel, followed by thermal annealing to obtain oxyfluoride glass ceramic containing Eu3+-doped BaF2 nanocrystals. We have used Eu3+ as probe ion and we analyzed its characteristic features (photoluminescence, optical absorption and magnetic circular dichroism) to get information about the local environment around the ion during thermally activated evolution of the sol to xerogel and then glass ceramic. As the drying and annealing proceeds silica network is formed accompanied by precipitation of the nanofluoride crystalline phase; Eu3+ coordination changes gradually from a random and assymetric CF3COO- one (in the sol) to a symmetric one (in the BaF2 nanocrystals) given by the fluorine ions. Glass ceramization is based on a homogenous crystallization mechanism with BaF2 nucleation centres resulted from thermal decomposition of Ba-trifluoacetate at around 300 °C followed by subsequent growth into BaF2 nanocrystals above 600 °C; Eu3+-ions are incorporated during the nanocrystals growth. -- Highlights: • Glass ceramization is the result of a homogenous crystallization with BaF2 nucleation centres. • Eu3+-ions are incorporated during nanocrystals growth, above 600 °C. • Eu3+-ions are embedded dominantly in the BaF2 nanocrystals in high symmetry sites