Two orders of magnitude extra SERS enhancement on silver nanoparticle-based substrate induced by laser irradiation in nitrogen ambient.

Photo-reduction of silver oxide and light-induced Ag nanoparticle (NP) generations have been applied for Surface-enhanced Raman spectroscopy (SERS) substrate fabricated for years. In this paper, we demonstrate a general method to enhance the SERS activity of conventional Ag NPs-based SERS substrates by performing Raman scattering measurement in a nitrogen ambient after a period of laser irradiation (photoactivation). The Raman characteristic peak intensity of carbonaceous impurities adsorbed on the surfaces of Ag NPs display an additional enhancement of 93 times after photoactivation in nitrogen ambient. A 3-fold extra Raman gain enhancement is also observed in the nitrogen-protected SERS measurement of R6G molecules. The extra SERS enhancement is attributed to the sub-nanometer scale near-field coupling between the Ag NPs and the photo-generated Ag clusters in the surface oxide layer of Ag NPs. This model is verified through the finite-difference time-domain (FDTD) simulations.