The nanocaps array of TiO₂/Ag bilayer with different Ag thicknesses and co-sputtering TiO₂-Ag monolayer with different TiO₂ contents were fabricated on a two-dimensional colloidal array substrate for the investigation of Surface enhanced Raman scattering (SERS) properties. For the TiO₂/Ag bilayer, when the Ag thickness increased, SERS intensity decreased. Meanwhile, a significant enhancement was observed when the sublayer Ag was 10 nm compared to the pure Ag monolayer, which was ascribed to the metal-semiconductor synergistic effect that electromagnetic mechanism (EM) provided by roughness surface and charge-transfer (CT) enhancement mechanism from TiO₂-Ag composite components. In comparison to the TiO₂/Ag bilayer, the co-sputtered TiO₂-Ag monolayer decreased the aggregation of Ag particles and led to the formation of small Ag particles, which showed that TiO₂ could effectively inhibit the aggregation and growth of Ag nanoparticles.

TiO₂/Ag bilayer films sputtered onto a 2D polystyrene (PS) bead array in a magnetron sputtering system were found to form a nanocap-shaped nanostructure composed of a TiO₂-Ag composite on each PS bead, in which the Ag nanoparticles were trapped partially or fully in the TiO₂ matrix, depending on the TiO₂ thickness. X-ray Photoelectron Spectroscopy (XPS) results showed the opposite shifts of binding energy for Ti 2p and Ag 3d, indicating the transfer of electrons from metallic Ag to TiO₂ owing to the Ag-O-TiO₂ composite formation. UV-Vis absorption spectra showed the blue shifts of the surface plasma resonance peaks, and the maximum absorption peak intensity was obtained for TiO₂ at 30 nm. The surface-enhanced Raman scattering (SERS) peak intensity first increased and then decreased when the TiO₂ thickness changed. The observations of SERS, XPS, and UV-Vis absorption spectra were explained by the dependency of the charge-transfer process on TiO₂ thickness, which was ascribed to the changing dielectric properties in the metal/semiconductor system.