Up-conversion emission tuning in triply-doped Yb~(3+)/Tm~(3+)/Er~(3+) novel fluoro-phosphate glass and glass-ceramics

摘要

New Yb~(3+), Er~（3+) and Tm~（3+） triply doped fluoro-phosphate glasses belonging to the system NaPO_3-YF_3-BaF_2-CaF_2 have been prepared by the classical melt-casting technique. Glasses containing up to 10 wt.% of rare-earth ions fluorides have been obtained and characterized by using differential scanning calorimetry (DSC), UV-visible-near-infrared spectroscopy and up-conversion emission spectroscopy under excitation with a 975 nm laser diode. Transparent and optically homogeneous glass-ceramics have been reproducibly obtained by appropriate heat treatment in view to manage the red, green and blue emissions upon 975 nm laser excitation. According to the applied thermal heat-treatment, a large enhancement of intensity of the up-conversion emission - from 10 to 160 times higher - has been achieved in the glass-ceramics compared to that of glasses, suggesting incorporation of the rare-earth ions into the crystalline phase. Furthermore, a large range of color rendering has been observed in these materials by controlling the laser excitation power and material crystallization rate. Time-resolved luminescence experiments as well as X-ray diffractometry and scanning electron microscopy techniques have been employed in order to understand and correlate the multicolor emission changes to the crystallization behavior of this material. A progressive phase transformation of the fluorite-type CaF2-based nanocrystals initially generated was observed along with increasing heat-treatment time, thus modifying the rare earth ions spectroscopic features.