The crystallization of the Bi 0.5 Nb 0.5 Te 3 O 8 (7.14 Bi 2 O 3 − 7.14Nb 2 O 5 −85.72TeO 2 ) glass composition shows numerous original spherulite-like shape or "droplets" crystalline domains through the bulk. Both SEM-EDS and microprobe measurements demonstrate that both these droplets and the glassy matrix present the same composition. The combination of information obtained from various complementary techniques, electron probe microanalysis, Raman, and SEM-EDS, then leads to the identification of the spherulites as a new Bi 0.5 Nb 0.5 Te 3 O 8 "anti-glass" phase. However, the crystallization mechanism is complex since microcracks are observed at the surface of the spherulites in some glass-ceramic materials, suggesting a confined crystal growth. Therefore, the crystallization process appears much different from a homogeneous congruent crystallization. The photoluminescence (PL) properties of the (1 wt %) Er 2 O 3 -doped Bi 0.5 Nb 0.5 Te 3 O 8 glass-ceramics were investigated during isothermal crystallization of the parent glass at 380 °C. The evolution of the PL signal ( 4 I 13/2 → 4 I 15/2 transition) enables indirect detection of the first steps of crystallization. Moreover, the PL data indicate random nucleation with respect to the location of Er 3+ ions, whereas the integrated PL intensity and lifetime values show very comparable evolution trends as a function of the crystallization rate.

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