Photoluminescence emission and Raman enhancement in TERS: an experimental and analytic revisiting.

An analytic model is used to calculate the Raman and fluorescence enhancement of a molecule in between two closely spaced gold nanospheres. Instead of using the conventional approach that only the dipolar plasmonic mode is considered, we calculate the electric field enhancement in the nanometre sized gap, by taking account of the higher order modes in one gold sphere, which couples to the dipolar mode of the other sphere. The experimental confirmation is performed by gap-dependent tip-enhanced Raman spectroscopy (TERS) measurements. The photoluminescence and Raman enhancement are both observed with different growing trends as the gap width decreases. Red-shift of the background spectra is observed and implies the increasing coupling between the nanospheres. This analytic model is shown to be able to interpret the enhancement mechanisms underlying gap-dependent TERS experimental results.