Near-Field Spectral Response of Optically Excited Scanning Tunneling Microscope Junctions Probed by Single-Molecule Action Spectroscopy

[Image: see text] The near-field spectral response of metallic nanocavities is a key characteristic in plasmon-assisted photophysical and photochemical processes. Here, we show that the near-field spectral response of an optically excited plasmonic scanning tunneling microscope (STM) junction can be probed by single-molecule reactions that serve as a nanoscale sensor detecting the local field intensity. Near-field action spectroscopy for the cis ↔ cis tautomerization of porphycene on a Cu(110) surface reveals that the field enhancement in the STM junction largely depends on microscopic structures not only on the tip apex, but also on its shaft. Using nanofabrication of Au tips with focused ion beam, we show that the spectral response is strongly modulated through the interference between the localized surface plasmon in the junction and propagating surface plasmon polariton generated on the shaft. Furthermore, it is demonstrated that the near-field spectral response can be manipulated by precisely shaping the tip shaft.