Visualising the distribution of structural defects and functional groups present on the surface of two-dimensional (2D) materials such as graphene oxide challenges the sensitivity and spatial resolution of the most advanced analytical techniques. Here we demonstrate mapping of functional groups on a carboxyl-modified graphene oxide (GO–COOH) surface with a spatial resolution of ≈10 nm using tip-enhanced Raman spectroscopy (TERS). Furthermore, we extend the capability of TERS by measuring local electronic properties in situ, in addition to the surface topography and chemical composition. Our results reveal that the Fermi level at the GO–COOH surface decreases as the I_D/I_G ratio increases, correlating the local defect density with the Fermi level at nanometre length-scales. The in situ multi-parameter microscopy demonstrated in this work significantly improves the accuracy of nanoscale surface characterisation, eliminates measurement artefacts, and opens up the possibilities for characterising optoelectronic devices based on 2D materials under operational conditions.

Two-dimensional transition metal dichalcogenides are gaining increasing interest due to their promising optical properties. In particular, molybdenum disulfide (MoS₂) which displays a band-gap change from indirect at 1.29 eV for bulk materials to direct at 1.8 eV for the material monolayer. This particular effect can lead to a strong light interaction which can pave the way for a new approach to the next generation of visible light emitting devices. In this work we show the nanoscale variation of light emission properties by tip-enhanced photoluminescence microscopy and spectroscopy in the MoS₂ monolayer, grown by chemical vapour deposition. The variations of the light emission properties are due to different effects depending on the shape of the MoS₂ single layer, for instance, a different concentration of point defect in an irregularly shaped flake and the presence of a nanoscale terrace in a triangular monolayer. Simultaneously, atomic force microscopy reveals indeed the presence of a nanometric terrace, composed of an additional layer of MoS₂, and tip-enhanced PL intensity imaging shows a localized intensity decrease.

Tip-enhanced Raman spectroscopy reveals structural and chemical modification of patterned graphene nanoribbons fabricated using electron beam lithography.

This work demonstrates the enhancement in plasmonic sensing efficacy resulting from spatially-localized functionalization on nanostructured surfaces, whereby probe molecules are concentrated in areas of high field concentration. Comparison between SERS measurements on nanostructured surfaces (arrays of nanodisks 110 and 220 nm in diameter) with homogeneous and spatially-localized functionalization with thiophenol demonstrates that the Raman signal originates mainly from areas with high field concentration. TERS measurements with 10 nm spatial resolution confirm the field distribution profiles predicted by the numerical modeling. Though this enhancement in plasmonic sensing efficacy is demonstrated with SERS, results apply equally well to any type of optical/plasmonic sensing on functionalized surfaces with nanostructuring.

Le TERS pour tip enhanced raman scattering, est une technique de pointe (dans tous les sens du terme) basée sur l’amplification du signal Raman relative à la résonance de plasmons de surface. Cette technique non-destructive, qui ne nécessite pas de marquage particulier, permet de caractériser un échantillon à l’échelle nanométrique. Le TERS s’impose aujourd’hui pour sonder les propriétés physico-chimiques des nanomatériaux et participer ainsi au développement de nouvelles applications dans le domaine des nanotechnologies.