In situ optical microspectroscopy approach for the study of metal transport in dielectrics via temperature- and time-dependent plasmonics: Ag nanoparticles in SiO₂ films

This study proposes in situ optical microspectroscopy as a means for the investigation of particle growth and metal transport in nanocomposite systems based on the temperature- and time-dependent optical response of the material. The technique has been successfully employed for the real-time monitoring of the growth of Ag nanoparticles (NPs) in SiO₂ films deposited on soda-lime glass during thermal processing in nitrogen atmosphere. By fitting the surface plasmon resonance (SPR) profiles with spectra calculated by Mie theory in the quasi-static regime, the time variation in effective Ag particle size was determined and subsequently analyzed in the context of crystal growth theory. The Ag NPs were indicated to grow first through a diffusion-based process and subsequently via Ostwald ripening. The experimental determination of the activation energies associated with each one of the particle growth mechanisms was carried out based on the time evolution of the SPR of Ag NPs. Arrhenius-type analyses of a set of time-dependent isotherms allowed for estimating the activation energies at 2.3 eV for the diffusion-based growth and 2.8 eV for the ripening stage.