Ag nanoaggregates as efficient broadband sensitizers for Tb3+ ions in silica-zirconia ion-exchanged sol-gel glasses and glass-ceramics

In this paper we report the study of down-shifting silica-zirconia glass and glass-ceramic films doped by Tb3+ ions and Ag nanoaggregates, which combine the typical spectral properties of the rare-earth-ions with the broadband sensitizing effect of the metal nanostructures. Na-Tb co-doped silica-zirconia samples were obtained by a modified sol-gel route. Dip-coating deposition followed by annealing for solvent evaporation and matrix densification were repeated several times, obtaining a homogeneous crack-free film. A final treatment at 700 °C or 1000 °C was performed to control the nanoscale structural properties of the samples, resulting respectively in a glass (G) or a glass-ceramic (GC), where tetragonal zirconia nanocrystals are surrounded by an amorphous silica matrix. Ag introduction was then achieved by ion-exchange in a molten salt bath, followed by annealing in air to control the migration and aggregation of the metal ions. The comparison of the structural, compositional and optical properties are presented for G and GC samples, providing evidence of highly efficient photoluminescence enhancement in both systems, slightly better in G than in GC samples, with a remarkable increase of the green Tb3+ PL emission at 330 nm excitation: 12 times for G and 8 times for GC samples. Furthermore, after Ag-exchange, the shape of Tb3+ excitation resembles the one of Ag ions/nanoaggregates, with a broad significant absorption in the whole UV-blue spectral region. This broadband enhanced downshifting could find potential applications in lighting devices and in PV solar cells.