Poling-assisted bleaching of soda-lime float glasses containing silver nanoparticles with a decreasing filling factor across the depth

Abstract

The recently discovered poling-assisted bleaching of glass with embedded silver nanoparticles has renewed the interest in thermal poling as a simple, reliable, and low-cost technique for controlling locally the surface-plasmon-resonant optical properties of metal-doped nanocomposite glasses. In the present study, the emphasis is put on the influence of the volume filling factor of metallic clusters on poling-assisted bleaching. Soda-lime silicate glass samples containing spherical silver nanoparticles with a decreasing filling factor across the depth were subject to thermal poling experiments with various poling temperatures, voltages, and times. Optical extinction spectra were measured from ultraviolet to near-infrared ranges and the surface-plasmon-resonant extinction due to silver nanoparticles (around 410nm) was modeled by the Maxwell Garnett [Philos. Trans. R. Soc. London, Ser. A 203, 385 (1904); 205, 237 (1906)] effective medium theory which was adapted in order to take into account the filling factor depth profile. A method was proposed for the retrieval of the filling factor depth profile from optical extinction spectra recorded in fresh and chemically etched samples. A stretched exponential depth profile turned out to be necessary in order to model samples having a high filling factor near the surface. Based on the fact that the electric-field-assisted dissolution of embedded metallic nanoparticles proceeded progressively from the top surface, a bleaching front was defined that moved forward in depth as time elapsed. The position of the bleaching front was determined after each poling experiment by fitting the measured extinction spectrum to the theoretical one. In samples with higher peak value and steeper gradient of the filling factor, the bleaching front reached more rapidly a steady-state depth as poling time increased. Also it increased less strongly with increasing poling voltage. These results were in agreement with the physics of the dissolution process. Finally, clear evidence of injection of hydrogenated ionic species from the atmosphere into the sample during poling was obtained from the growth of the infrared extinction peak associated with OH radicals.