Controlling Selective Doping and Energy Transfer between Transition Metal and Rare Earth Ions in Nanostructured Glassy Solids

摘要

Selective doping of optically active ions into the nanocrystalline phase(s) of glass ceramics is of interest for photoluminescence (PL) applications to control the energy transfer (ET) processes between dopants on the nanometer length scale. Here, the focus is on explaining the essential knowledge of the distribution of two groups of active ions: transition metal (Ni~(2+) and Cr~(3+)) and rare earth (Yb~(3+) and Er~(3+)) ions, which are doped into i) single-phase Ga_2O_3 and ii) dual-phase Ga_2O_3 and YF3 nanocrystals (NCs). These NCs are obtained by thermally crystallizing ternary silicate- and quinary fluorosilicatebased glasses, respectively. It is found that the two types of active ions can successfully be doped into Ga_2O_3 NCs, resulting in enhanced ET between the dopants because of the small separation distance of, e.g., <10 Å, whereas ET is significantly suppressed when Ga_2O_3 and YF_3 NCs are coprecipitated. In this case, the studied rare earth ions have a high propensity for being selectively doped in YF3 NCs. The studied transition-metal ions can always be found in Ga_2O_3 NCs irrespective of the presence of the fluoride phase. The selective doping and the ET between the two types of active ions can be controlled simultaneously on annealing. This may allow for the achievement of diverse PL properties, such as ultrabroadband near-infrared and upconversionmediated Stokes emissions.