Visualizing Electric Fields at Au(111) Step Edges via Tip-Enhanced Raman Scattering

Tip-enhanced Raman scattering (TERS) can be used to image plasmon-enhanced local electric fields on the nanoscale. This is illustrated through ambient TERS measurements recorded using silver atomic force microscope tips coated with 4-mercaptobenzonitrile molecules and used to image step edges on an Au(111) surface. The observed two-dimensional TERS images uniquely map electric fields localized at Au(111) step edges following 671 nm excitation. We establish that our measurements are not only sensitive to spatial variations in the enhanced electric fields but also to their vector components. We also experimentally demonstrate that (i) few nanometer precision is attainable in TERS nanoscopy using corrugated tips with nominal radii on the order of 100-200 nm, and (ii) TERS signals do not necessarily exhibit the expected E⁴ dependence. Overall, we illustrate the concept of electric field imaging via TERS and establish the connections between our observations and conventional TERS chemical imaging measurements.