Graphene oxide and shape-controlled silver nanoparticle hybrids for ultrasensitive single-particle surface-enhanced Raman scattering (SERS) sensing.

Graphene oxide (GO) is an emerging material for surface-enhanced Raman scattering (SERS) due to its strong chemical enhancement. Studying the SERS performance of plasmonic nanoparticle/GO hybrid materials at the single particle level is crucial for direct probing of the chemical effect of GO on plasmonic nanoparticles. In this work, we integrate GO and shape-controlled Ag nanoparticles to create hybrid nanomaterials, and the chemical enhancement arising from GO is investigated using single-particle SERS measurements. Ag nanoparticle@GO hybrid nanostructures are prepared by assembling Ag nanoparticles, including spheres, cubes and octahedra with GO sheets. The SERS behaviors of the hybrid nanostructures are characterized, and 2-3 times enhanced SERS intensities are detected from the Ag nanoparticle@GO hybrid nanostructures as compared to pure Ag nanoparticles. Furthermore, we probe the mechanism of SERS enhancement in the hybrid nanostructures by changing the surface coverage of GO on Ag octahedra, by using reduced GO in place of GO as well as by using probe molecules of different electronegativities. This hybrid system is an excellent candidate for single-particle SERS sensors. Sub-nanomolar levels of aromatic molecules are detected using a single Ag/GO hybrid nanomaterial. This as-prepared GO and shape-controlled Ag nanoparticle hybrid is capable of serving as a high performance SERS platform, providing new opportunities for efficient chemical and biological sensing applications.