Structural and optical properties in Tm3+/Tm3+-Yb3+ doped NaLuF4 glass-ceramics

Transparent NaLuF4 glass-ceramics (GCs) doped with Tm3+ and Tm3+/Yb3+ have been prepared by melting-quenching followed by thermal treatment at temperatures near the glass transition temperature. The crystallization process has been studied using X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). NaLuF4 nanocrystals (NCs) ranging 9-30 nm in size are the only crystalline phase, the crystal size increasing with the dopant concentration. Energy dispersive X-ray (EDX) measurements confirm the Tm3+ and Yb3+ incorporation in the NCs. Optical characterization included the analysis of up-conversion (UC) as well as the Near-infrared (NIR) luminescence. NIR emission spectra of Tm3+ and Yb3+ in co-doped samples confirmed an efficient energy transfer between both ions. No UC emissions are observed in Tm3+ single-doped glass and GCs. Yb3+ incorporation favors the Tm3+-Tm3+ UC processes resulting in Tm3+ blue, yellowish-red and NIR UC emissions after excitation at 975 nm. Blue UC emission is also observed in the codoped samples after Tm3+ excitation at 791 nm. These effects were more evident for the GCs compared to the base glasses, confirming the RE ions incorporation in the NCs. As a result, these GCs can be used to tune the UC emission from NIR to blue by selective excitation.