Localized Plasmon-Stimulated Nanochemistry of Graphene Oxide on a SERS Substrate

In recent years, there has been remarkable progress in the reduction and functionalization of graphene oxide (GO) using nanoparticles and high-energy optical photons. Most of these reactions are carried out in solutions, whereas the local modification of GO on solid substrates still remains a challenge. In this work, we demonstrate the local reduction of GO and its further destruction, leading to the synthesis of polyaromatic hydrocarbons (PAHs) stimulated by localized surface plasmons (LSPs). The reduction of GO and the synthesis of PAHs have been carried out on a substrate designed for surface-enhanced Raman spectroscopy (SERS). We found that LSPs initiate the destruction of water molecules entrapped in the nanogaps between silver nanoparticles after the deposition of GO from the aqueous suspension. It was demonstrated that OH radicals, as a result of water decomposition, initiate the reduction of GO, leading to the synthesis of PAHs. The reactions have been observed in real time by using SERS. The measurement of current-voltage (I-V) characteristics through conductive atomic force microscopy (AFM), recorded in an LSP-stimulated area, have shown the increased electrical conductivity (more than ten times) compared with the conductivity of GO. The synthesis of new compounds in the LSP-stimulated area has been confirmed by the appearance of new peaks in the Raman spectra and nonlinear I-V characteristics typical for PAHs. We show that the used method allows the local modification of electrical properties of GO and controlled nanopattering of organic compounds on the surface.