Profiling the near field of a plasmonic nanoparticle with Raman-based molecular rulers

The enhanced local optical fields at the surface of illuminated metallic nanoparticles and nanostructures are of intense fundamental and technological interest. Here we report a self-consistent measurement of the spatial extent of the fringing field above a plasmonic nanoparticle surface. Bifunctional DNA-based adsorbate molecules are used as nanoscale optical rulers, providing two distinct surface enhanced Raman scattering signals that vary independently in intensity as a function of distance from the nanoparticle surface. While the measurement technique is calibrated on gold nanoshell surfaces with controlled and predictable electromagnetic nanoenvironments, this approach is broadly adaptable to a wide range of plasmonic geometries.