Development of A Novel Dual-Layer Thick Ag Substrate for Surface-Enhanced Raman Scattering (SERS) of Self-Assembled Monolayers

Abstract

A dual-layer, thick (∼70 nm) vapor-deposited Ag substrate has been developed that gives enhancement factors on the order of 104 for surface-enhanced Raman scattering (SERS) experiments. This substrate has a total thickness of ∼70 nm but also has an outermost surface morphology that approximates that of a thin Ag island film (AgIF) substrate. This is accomplished using a dual overlayer/underlayer structure in which a thick underlayer of 45-nm Ag is vapor-deposited onto a treated glass slide. This Ag underlayer is exposed to ambient conditions under which the surface chemisorbs oxygen, leading to the thermodynamically favorable formation of an active Ag2O interface. An overlayer of 25-nm Ag is vapor-deposited on top of this structure. The first Ag/Ag2O underlayer produces an active interface that decreases the diffusion of the Ag atoms from the second vapor-deposited overlayer, thereby forming Ag particles with shapes favorable for SERS enhancement. Atomic force microscopy results show that the Ag overlayer particles have ideal shapes for SERS enhancement with morphology comparable to thin, vapor-deposited AgIFs. X-ray photoelectron spectroscopy in the O(1s) region showed the presence of multiple forms of oxygen in the Ag/Ag2O underlayer; the main forms were identified as dissolved bulk oxygen and chemisorbed oxygen. Using self-assembled monolayers (SAMs) of 1-dodecanethiol, a SERS intensity increase of ∼400% was obtained for this new overlayer/underlayer Ag substrate when compared to SAMs formed on traditional thick Ag substrates. Enhancement factors calculated from the Raman intensity of trans-1,2-bis(4-pyridyl)ethane showed a SERS enhancement of approximately 104 for this new Ag/Ag2O/Ag substrate compared with the bulk. This compares favorably with the SERS enhancements obtained using thin AgIF substrates. The Ag/Ag2O/Ag substrates showed reproducible SERS intensities (RSD = 0.45−5%). The mechanisms responsible for the overall enhancement on this new substrate are proposed to be the ideal surface morphology of the Ag overlayer particles as well as a combined enhanced electromagnetic field produced by both the Ag/Ag2O underlayer and the Ag overlayer.