Role of Ag multimers as broadband sensitizers in Tb3+/Yb3+ co-doped glass-ceramics

Rare earth ions (RE3+) have typical photoluminescence emissions due to internal 4f orbital transitions. These emissions are narrow, with long excited state lifetimes and have the capability of spectral manipulation like wavelength shifting, down-conversion or up-conversion processes. Therefore, RE-doped materials are widely used for optical applications. However, the narrow absorption bandwidths and the small excitation cross sections for their optical transitions are major limiting factors for the full exploitation of their potentials. In this work, we show that the addition of metal nanoaggregates as broadband and efficient sensitizers can be a viable strategy to overcome these limits. Silica-zirconia (70% SiO2 - 30% ZrO2) glass-ceramic films doped by Tb3+/Yb3+ ions and an additional 5 mol.% of Na2O were prepared by sol-gel synthesis followed by a thermal annealing at 1000°C. Ag introduction was then obtained by ion-exchange in a molten salt bath and the samples were subsequently annealed in air at 380°C or 430°C to induce the migration and aggregation of the metal. The structural, compositional and optical properties of the materials were investigated, providing evidence for efficient broadband sensitization of the rare earth ions by energy transfer from Ag-dimers or multimers, which could have applications for increasing the efficiency of silicon solar cells.