PNNL

Abstract

We report tip-enhanced Raman scattering experiments in which topographic and local electric field images are recorded simultaneously. We employ a Raman-active 4,4’-dimercaptostilbene (DMS)-coated gold tip of an atomic force microscope to map the topography and image electric fields localized at nanometric (20 and 5 nm-wide) slits lithographically etched in silver. Bi-modal imaging is feasible by virtue of the recorded scanning probe position-dependent frequency-resolved optical response, which can be sub-divided into two components. The first is a 500-2250 cm-1 Raman-shifted signal, characteristic of DMS. The molecular response reports on topography through intensity contrast in the absence/presence of a plasmonic junction formed between the scanning probe and patterned silver surface. Here, we demonstrate that sub-15 nm spatial resolution is attainable using a 30 nm DMS-coated gold tip. The second response consists of two correlated sub-500 cm-1 signals arising from mirror-like reflections of (i) the incident laser, and (ii) the Raman scattered response of an underlying glass support (at 100-500 cm-1) off the gold tip. We show that both the low-wavenumber signals trace the local electric fields in the vicinity of the nanometric slits.