In-operando control of sum-frequency generation in tip-enhanced nanocavities.

Sum-frequency generation (SFG) is a second-order nonlinear process widely used for characterizing surfaces and interfaces with monolayer sensitivity. Recently, optical field enhancement in plasmonic nanocavities has enabled SFG with continuous wave (CW) lasers from nanoscale areas of molecules, promising applications like nanoscale SFG spectroscopy and coherent upconversion for mid-infrared detection at visible frequencies. Here, we demonstrate CW SFG from individual nanoparticle-on-mirror (NPoM) cavities, which are resonant at visible frequencies and filled with a monolayer of molecules, when placed beneath a metal scanning probe tip. The tip acts as an efficient broadband antenna, focusing incident CW infrared illumination onto the nanocavity. The cascaded near-field enhancement within the NPoM nanocavity yields nonlinear optical responses across a broad range of infrared frequencies, achieving SFG enhancements of up to 14 orders of magnitude. Further, nanomechanical positioning of the tip allows for in-operando control of SFG by tuning the local field enhancement rather than the illumination intensities. The versatility of tip-enhanced nanocavities allows for SFG studies of a wide range of molecular species in the few-molecule regime without the need for complex nanofabrication. Our results also promise SFG nanoimaging with tips providing strong visible and IR field enhancement at their apex, offering a robust platform for future applications in nonlinear nanooptics.