title: From single to multiple Ag-layer modification of Au nanocavity substrates: a tunable probe of the chemical surface-enhanced Raman scattering mechanism.
abstract: We present experimental and computational results that enlighten the mechanisms underlying the chemical contribution to surface-enhanced Raman scattering (SERS). Gold void metallic arrays electrochemically covered either by a Ag monolayer or 10-100 Ag layers were modified with a self-assembled monolayer of 4-mercaptopyridine as a molecular Raman probe displaying a rich and unexpected Raman response. A resonant increase of the Raman intensity in the red part of the spectrum is observed that cannot be related to plasmon excitations of the cavity-array. Notably, we find an additional 10-20 time increase of the SERS amplification upon deposition of a single Ag layer on the Au substrate, which is, however, almost quenched upon deposition of 10 atomic layers. Further deposition of 100 atomic Ag layers results in a new increase of the SERS signal, consistent with the improved plasmonic efficiency of Ag bulk-like structures. The SERS response as a function of the Ag layer thickness is analyzed in terms of ab initio calculations and a microscopic model for the SERS chemical mechanism based on a resonant charge transfer process between the molecular HOMO state and the Fermi level in the metal surface. We find that a rearrangement of the electronic charge density related to the presence of the Ag monolayer in the Au/Ag/molecule complex causes an increase in the distance between the HOMO center of charge and the metallic image plane that is responsible for the variation of Raman enhancement between the studied substrates. Our results provide a general platform for studying the chemical contribution to SERS, and for enhancing the Raman efficiency of tailored Au-SERS templates through electrochemical modification with Ag films.
authors.affiliation: Centro Atómico Bariloche, Instituto Balseiro, Comisión Nacional de Energía Atómica, 8400 S. C. de Bariloche, Río Negro, Argentina. tognalli@cab.cnea.gov.ar
authors.forename: Nicolás G
authors.initials: NG
authors.lastname: Tognalli
authors.forename: Emiliano
authors.initials: E
authors.lastname: Cortés
authors.forename: Alexander D
authors.initials: AD
authors.lastname: Hernández-Nieves
authors.forename: Pilar
authors.initials: P
authors.lastname: Carro
authors.forename: Gonzalo
authors.initials: G
authors.lastname: Usaj
authors.forename: Carlos A
authors.initials: CA
authors.lastname: Balseiro
authors.forename: María E
authors.initials: ME
authors.lastname: Vela
authors.forename: Roberto C
authors.initials: RC
authors.lastname: Salvarezza
authors.forename: Alejandro
authors.initials: A
authors.lastname: Fainstein