Irreversible accumulated SERS behavior of the molecule-linked silver and silver-doped titanium dioxide hybrid system

In recent years, surface-enhanced Raman scattering (SERS) of a molecule/metal-semiconductor hybrid system has attracted considerable interest and regarded as the synergetic contribution of the electromagnetic and chemical enhancements from the incorporation of noble metal into semiconductor nanomaterials. However, the underlying mechanism is still to be revealed in detail. Herein, we report an irreversible accumulated SERS behavior induced by near-infrared (NIR) light irradiating on a 4-mercaptobenzoic acid linked with silver and silver-doped titanium dioxide (4MBA/Ag/Ag-doped TiO₂) hybrid system. With increasing irradiation time, the SERS intensity of 4MBA shows an irreversible exponential increase, and the Raman signal of the Ag/Ag-doped TiO₂ substrate displays an exponential decrease. A microscopic understanding of the time-dependent SERS behavior is derived based on the microanalysis of the Ag/Ag-doped TiO₂ nanostructure and the molecular dynamics, which is attributed to three factors: (1) higher crystallinity of Ag/Ag-doped TiO₂ substrate; (2) photo-induced charge transfer; (3) charge-induced molecular reorientation.