Suppressing Molecular Charging, Nanochemistry, and Optical Rectification in the Tip-Enhanced Raman Geometry.

Classical versus quantum plasmons are responsible for the recorded signals in non-contact-mode versus contact-mode tip-enhanced Raman spectroscopy (TERS) and lead to distinct observables. Under otherwise identical experimental conditions, we illustrate the concept through tapping- and contact-mode TERS mapping of chemically functionalized silver nanocubes. Whereas molecular charging, chemical transformations, and optical rectification are prominent observables in contact-mode TERS, the same effects are suppressed using tapping-mode feedback. In effect, this work demonstrates that nanoscale physical and chemical processes can be accessed and/or suppressed on demand in the TERS geometry. The advantages of tapping-mode TERS are otherwise highlighted with the latter in mind.