Giant gap-plasmon tip-enhanced Raman scattering of MoS monolayers on Au nanocluster arrays.

In this article, we present the results of a gap-plasmon tip-enhanced Raman scattering study of MoS monolayers deposited on a periodic array of Au nanostructures on a silicon substrate forming a two dimensional (2D) crystal/plasmonic heterostructure. We observe a giant Raman enhancement of the phonon modes in the MoS monolayer located in the plasmonic gap between the Au tip apex and Au nanoclusters. Tip-enhanced Raman mapping allows us to determine the gap-plasmon field distribution responsible for the formation of hot spots. These hot spots provide an unprecedented giant Raman enhancement of 5.6 × 10 and a spatial resolution as small as 2.3 nm under ambient conditions. Moreover, due to strong hot electron doping in the order of 1.8 × 10 cm, we observe a structural change of MoS from the 2H to the 1T phase. Owing to the very good spatial resolution, we are able to spatially resolve those doping sites. To the best of our knowledge, this is the first time reporting of such a phenomenon with nm spatial resolution. Our results will open the perspectives of optical diagnostics with nanometer resolution for many other 2D materials.