Multimodal Tip-Enhanced Nonlinear Optical Nanoimaging of Plasmonic Silver Nanocubes

Optical field localization at plasmonic tip-sample nanojunctions has enabled high-spatial-resolution chemical analysis through tip-enhanced linear optical spectroscopies, including Raman scattering and photoluminescence. Here, we illustrate that nonlinear optical processes, including parametric four-wave mixing (4WM), second-harmonic/sum-frequency generation (SHG and SFG), and two-photon photoluminescence (TPPL), can be enhanced at plasmonic junctions and spatiospectrally resolved simultaneously with few-nm spatial resolution under ambient conditions. Through a detailed analysis of our spectral nanoimages, we find that the efficiencies of the local nonlinear signals are determined by sharp tip-sample junction resonances that vary over the few-nanometer length scale. Namely, plasmon resonances centered at or around the different nonlinear signals are tracked through TPPL, and they are found to selectively enhance nonlinear signals with closely matched optical resonances.