Ag and Si Codoped Phosphate Glasses: Plasmonic Nanocomposites with Enhanced UV Transparency

The use of silicon powder to produce plasmonic Ag nanocomposite phosphate glasses which also exhibit improved transparency in the ultraviolet (UV) is proposed. Ag₂O/Si codoped glasses were prepared in a barium-phosphate matrix by a simple melt-quench method in ambient atmosphere. The as-prepared glasses exhibit enhanced UV transparency, whereby the surface plasmon resonance of Ag nanoparticles (NPs) is manifested for the glasses with higher Ag₂O contents. ³¹P nuclear magnetic resonance spectroscopy is consistent with the formation of P–O–Si bonds, thus suggesting their possible role on the improved UV light transmission. Consequently, a model was presented accounting for the influence of silicon on the polymerization of the phosphate network concomitant with the creation of highly reactive oxygen species. Further exploiting the proposed reactive species, a real-time spectroscopic study of the plasmonic response of Ag NPs in Ag/Si codoped glass samples was carried out during an in situ thermal processing. The temperature dependence of the Ag particle precipitation was studied in the 400°C–430°C range, from which an Arrhenius-type plot allowed for estimating the activation energy of the process at 3.42 (±0.38) eV. Ultimately, the vanishing of the luminescence ascribed to Ag⁺ ions was observed in a heat-treated sample, consistent with the high reactivity acquired by the glass matrix. Silicon thus appears promising for producing UV transparent glasses for high-performance optics and for the reduction of Ag⁺ ions to produce Ag nanocomposites valuable for photonic (nanoplasmonic) applications.