Detecting stimulated Raman responses of molecules in plasmonic gap using photon induced forces.

We demonstrate the stimulated Raman nanoscopy of a small number of molecules in a plasmonic gap, excited without resonant electronic enhancement, measured using near-field photon-induced forces, eliminating the need for far-field optical detection. We imaged 30 nm diameter gold nanoparticles functionalized with a self-assembled monolayer (SAM) of 4-nitrobenzenethiol (4-NBT) molecules. The maximum number of molecules detected by the gold-coated nano-probe at the position of maximum field enhancement could be fewer than about 42 molecules. The molecules were imaged by vibrating an Atomic Force Microscope (AFM) cantilever on its second flexural eigenmode enabling the tip to be controlled much closer to the sample, thereby improving the detected signal-to-noise ratio when compared to vibrating the cantilever on its first flexural eigenmode. We also demonstrate the implementation of stimulated Raman nanoscopy measured using photon-induced force with non-collinear pump and stimulating beams which could have applications in polarization dependent Raman nanoscopy and spectroscopy and pump-probe nano-spectroscopy particularly involving infrared beam/s. We also discuss using photon induced forces as a technique to sort and select best performing metal coated tips for further use in tip-enhanced experiments.