Quantum mechanical limit to plasmonic enhancement as observed by surface-enhanced Raman scattering.

Plasmonic nanostructures enable light to be concentrated into nanoscale 'hotspots', wherein the intensity of light can be enhanced by orders of magnitude. This plasmonic enhancement significantly boosts the efficiency of nanoscale light-matter interactions, enabling unique linear and nonlinear optical applications. Large enhancements are often observed within narrow gaps or at sharp tips, as predicted by the classical electromagnetic theory. Only recently has it become appreciated that quantum mechanical effects could emerge as the feature size approaches atomic length-scale. Here we experimentally demonstrate, through observations of surface-enhanced Raman scattering, that the emergence of electron tunnelling at optical frequencies limits the maximum achievable plasmonic enhancement. Such quantum mechanical effects are revealed for metallic nanostructures with gap-widths in the single-digit angstrom range by correlating each structure with its optical properties. This work furthers our understanding of quantum mechanical effects in plasmonic systems and could enable future applications of quantum plasmonics.