Tip-enhanced Raman spectroscopy (TERS) with sub-nanometer spatial resolution has been recently demonstrated experimentally. However, the physical mechanism underlying is still under discussion. Here, we theoretically investigate the electric field gr
adient of a coupled tip-substrate system. Our calculations suggest that the ultra-high spatial resolution of TERS can be partially attributed to the electric field gradient effect owning to its tighter spatial confinement and sensitivity to the infrared (IR)-active of molecules.
We employ tip-enhanced infrared near-field microscopy to study the plasmonic properties of epitaxial quasi-free-standing monolayer graphene on silicon carbide. The near-field images reveal propagating graphene plasmons, as well as a strong plasmon re
flection at gaps in the graphene layer, which appear at the steps between the SiC terraces. When the step height is around 1.5 nm, which is two orders of magnitude smaller than the plasmon wavelength, the reflection signal reaches 20% of its value at graphene edges, and it approaches 50% for step heights as small as 5 nm. This intriguing observation is corroborated by numerical simulations, and explained by the accumulation of a line charge at the graphene termination. The associated electromagnetic fields at the graphene termination decay within a few nanometers, thus preventing efficient plasmon transmission across nanoscale gaps. Our work suggests that plasmon propagation in graphene-based circuits can be tailored using extremely compact nanostructures, such as ultra-narrow gaps. It also demonstrates that tip-enhanced near-field microscopy is a powerful contactless tool to examine nanoscale defects in graphene.
