Near-field chemical mapping of gold nanostructures using a functionalized scanning probe

We report on photochemical and photophysical properties produced by Surface Plasmon Resonance (SPR) on metallic nanograins by means of high resolution Functionalized Tip-Enhanced Raman Spectroscopy (F-TERS). This technique relies on a sharp gold tip functionalized with Raman-active molecules to be scanned relatively to plasmonic hot-spots on a surface. We describe the local variation of plasmon-induced Raman enhancement on the surface of nanostructures that also affects the photochemistry while the quantitative interpretation of peak intensities requires the consideration of surface topography near the tip apex. Our F-TERS maps show Raman modes of hot electron reduction of 4-nitrothiophenol (4-NTP) molecules on the tip and indicate at least partial photochemical dimerization. An apparent photo-induced reversibility of this dimerization can be conservatively explained by a local topography feature that we simulate in a finite element environment. Our experimental results reveal a spatial resolution of approximately 10 nm, corresponding to a few hundred 4-NTP molecules exposed to the near-field.