RESUMO
Raman sensing is a powerful technique for detecting chemical signatures, especially when combined with optical enhancement techniques such as using substrates containing plasmonic nanostructures. In this work, we successfully demonstrated surface-enhanced Raman spectroscopy (SERS) of two analytes adsorbed onto gold nanosphere metasurfaces with tunable subnanometer gap widths. These metasurfaces, which push the bounds of previously studied SERS nanostructure feature sizes, were fabricated with precise control of the intersphere gap width to within 1 nm for gaps close to and below 1 nm. Analyte Raman spectra were measured for samples for a range of gap widths, and the surface-affected signal enhancement was found to increase with decreasing gap width, as expected and corroborated via electromagnetic field modeling. Interestingly, an enhancement quenching effect was observed below gaps of around 1 nm. We believe this to be one of the few studies of gap-width-dependent SERS for the subnanometer range, and the results suggest the potential of such methods as a probe of subnanometer scale effects at the interface between plasmonic nanostructures. With further study, we believe that tunable sub-nanometer gap metasurfaces could be a useful tool for the study of nonlocal and quantum enhancement-quenching effects. This could aid the development of optimized Raman-based sensors for a variety of applications.
