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.

Tip-enhanced Raman spectroscopy (TERS) has been rapidly improved over the past decade and opened up opportunities to study phonon properties of materials at the nanometer scale. In this Letter, we report on TERS of an ultrathin MoS flake on a nanostructured Au on silicon surface forming a two-dimensional (2D) crystal/plasmonic heterostructure. Au nanostructures (shaped in triangles) are prepared by nanosphere lithography, and then MoS is mechanically exfoliated on top of them. The TERS spectra acquired under resonance conditions at 638 nm excitation wavelength evidence strain changes spatially localized to regions as small as 25 nm in TERS imaging. We observe the highest Raman intensity enhancement for MoS on top of Au nanotriangles due to the strong electromagnetic confinement between the tip and a single triangle. Our results enable us to determine the local strain in MoS induced during heterostructure formation. The maximum frequency shift of E mode is determined to be (4.2 ± 0.8) cm, corresponding to 1.4% of biaxial strain induced in the MoS layer. We find that the regions of maximum local strain correspond to the regions of maximum topographic curvature as extracted from atomic force microscopy measurements. This tip-enhanced Raman spectroscopy study allows us to determine the built-in strain that arises when 2D materials interact with other nanostructures.

Two-dimensional (2D) van derWaals semiconductors have been the subject of intense research due to their low dimensionality and tunable optoelectronic properties. However, the stability of these materials in air is one of the important issues that needs to be clarified, especially for technological applications. Here the time evolution of GaSe oxidation from monolayer to bulk is investigated by Raman spectroscopy, photoluminescence emission, and x-ray photoelectron spectroscopy. The Raman spectroscopy study reveals that GaSe monolayers become oxidized almost immediately after exposure to air. However, the oxidation is a self-limiting process taking roughly 5 h to penetrate up to 3 layers of GaSe. After oxidation, GaSe single-layers decompose into amorphous Se which has a strong Raman cross section under red excitation. The present study provides a clear picture of the stability of GaSe in air and will guide future research of GaSe from single-to few-layers for the appropriate development of novel technological applications for this promising 2D material.

Two-dimensional chalcogenide semiconductors have recently emerged as a host material for quantum emitters of single photons. While several reports on defect-and strain-induced singlephoton emission from 2D chalcogenides exist, a bottom-up, lithography-free approach to producing a high density of emitters remains elusive. Further, the physical properties of quantum emission in the case of strained 2D semiconductors are far from being understood. Here, we demonstrate a bottom-up, scalable, and lithography-free approach for creating large areas of localized emitters with high density (∼150 emitters/um 2 ) in a WSe 2 monolayer. We induce strain inside the WSe 2 monolayer with high spatial density by conformally placing the WSe 2 monolayer over a uniform array of Pt nanoparticles with a size of 10 nm. Cryogenic, time-resolved, and gate-tunable luminescence measurements combined with near-field luminescence spectroscopy suggest the formation of localized states in strained regions that emit single photons with a high spatial density. Our approach of using a metal nanoparticle array to generate a high density of strained quantum emitters will be applied to scalable, tunable, and versatile quantum light sources.

We look to understand the enhancement and spatial resolution of a tip-enhanced Raman scattering (TERS) system containing a metal tip and plasmonic substrate.