Construction of an Au/g-C3N4/GO/Au Substrate by a Layer-by-layer Assembly Approach for Surface-Enhanced Raman Spectroscopy

In this work, an Au/g-C3N4/GO/Au hybrid nanofilm for surface-enhanced Raman scattering (SERS) substrate application was prepared by a facile layer-by-layer assembly technique using nanosheet-structured graphitic carbon nitride (g-C3N4), graphene oxide (GO) and 40 nm-gold nanoparticles (Au NPs). The effects of composition, assembly sequence and assembly cycles on the SERS performance were optimized to achieve the SERS-active substrate. The detection limit of Au/g-C3N4/GO/Au substrate for crystal violet and rhodamine 6 G probe molecules reached as high as 10-8 M, with good stability and uniformity. Its further application in food colorants detection (erythrosine, carmine and temptation red) had successfully met the national food safety standards and the quantitative detection for erythrosine and temptation red had also been established. Based on finite-difference time-domain element simulation and density functional theory quantum chemical calculation, the mechanism of the SERS effect of the substrate was unveiled, which is attributed to the combination of electromagnetic enhancement effect of Au nanoparticle aggregates and chemical enhancement effect of GO and g-C3N4. Notably, water droplet evaporation induced Raman enhancement was observed on the Au/g-C3N4/GO/Au substrate. This can be ascribed to the inhomogeneous evaporation of the droplet that promotes the enrichment of the probe molecules into the center of the droplet. This novel enhancement strategy provides a new idea for further improving detection sensitivity of SERS substrate materials.