Crystallization kinetics and spectroscopic investigations on Tb3+ and Yb3+ codoped glass ceramics containing CaF2 nanocrystals

Abstract

Transparent Tb3+ and Yb3+ codoped oxyfluoride glass ceramics containing CaF2 nanocrystals were prepared by melt quenching and subsequent heat treatment. Crystallization kinetics of CaF2 nanocrystals was investigated by differential scanning calorimetric method. The average apparent activation energy Ea of the crystallization was ∼498kJ∕mol. Moreover, the value of the Avrami exponent n was 1.01. These results suggest that the crystallization mechanism of CaF2 is a diffusion controlled growth process of needles and plates of finite long dimensions. X-ray diffraction patterns and transmission electron microscopy image confirmed the CaF2 nanocrystals in the glass ceramic. Ultraviolet (UV) and visible emission spectra of the as-made glass and the glass ceramic with an excitation of a 974nm laser diode were recorded at room temperature. An intense UV emission at 381nm was observed in the glass ceramic. The origin of the enhancement of the emission at 381nm was investigated using spectroscopic technique and Judd-Ofelt analysis. The enhancement of the emission at 381nm could be attributed to the change of the ligand field of Tb3+ ions due to the incorporation of some Tb3+ and Yb3+ ions into CaF2 nanocrystals in the glass ceramic.