Influence of tip geometry on the spatial resolution of tip enhanced Raman mapping

In 2013, a breakthrough experiment pushed the Raman mapping of molecules via the tip-enhanced Raman scattering (TERS) technique to a sub-nanometer spatial resolution, going into the single-molecule level. This surprising result was well explained by accounting for the critical role of elastic molecule Rayleigh scattering within a plasmonic nanogap in enhancing both the localization and the intensity level of the Raman scattering signal. In this paper, we theoretically explore the influence of various geometric factors of the TERS system on the spatial resolution of Raman mapping, such as the tip curvature radius, tip conical angle, tip-substrate distance, and tip-molecule vertical distance. This investigation can help to find out the most critical geometric factor influencing the spatial resolution of TERS and march along in the right direction for further improving the performance of the TERS system.