In monolayer transition metal dichalcogenides, quantum emitters are associated with localized strain that can be deterministically applied to create designer nano-arrays of single photon sources. Despite an overwhelming empirical correlation with local strain, the nanoscale interplay between strain, excitons, defects and local crystalline structure that gives rise to these quantum emitters is poorly understood. Here, we combine room-temperature nano-optical imaging and spectroscopy of excitons in nanobubbles of localized strain in monolayer WSe2 with atomistic structural models to elucidate how strain induces nanoscale confinement potentials that give rise to highly localized exciton states in 2D semiconductors. Nano-optical imaging of nanobubbles in low-defect monolayers reveal localized excitons on length scales of ~10 nm at multiple sites along the periphery of individual nanobubbles, which is in stark contrast to predictions of continuum models of strain. These results agree with theoretical confinement potentials that are atomistically derived from measured topographies of existing nanobubbles. Our results provide one-of-a-kind experimental and theoretical insight of how strain-induced confinement-without crystalline defects-can efficiently localize excitons on length scales commensurate with exciton size, providing key nanoscale structure-property information for quantum emitter phenomena in monolayer WSe2.The intense light-matter interactions of two-dimensional (2D) monolayer transition metal dichalcogenides (1L-TMDs) are mediated by a diverse suite of excitonic phenomena that present a wealth of opportunities for novel optoelectronic functionalities in areas spanning from high- *

Gold-mediated exfoliation of MoS 2 has recently attracted considerable interest. The strong interaction between MoS 2 and Au facilitates preferential production of centimeter-sized monolayer MoS 2 with near-unity yield and provides a heterostructure system noteworthy from a fundamental standpoint. However, little is known about the detailed nature of the MoS 2 –Au interaction and its evolution with the MoS 2 thickness. Here, we identify the specific vibrational and binding energy fingerprints of this interaction using Raman and X-ray photoelectron spectroscopy, which indicate substantial strain and charge doping in monolayer MoS 2 . Tip-enhanced Raman spectroscopy reveals heterogeneity of the MoS 2 –Au interaction at the nanoscale, reflecting the spatial nonconformity between the two materials. Micro-Raman spectroscopy shows that this interaction is strongly affected by the roughness and cleanliness of the underlying Au. Our results elucidate the nature of the MoS 2 –Au interaction and guide strain and charge doping engineering of MoS 2 .

The important role of water in growth of monolayer transition metal dichalcogenides Interest in transition metal dichalcogenides (TMDs) has been renewed by the discovery of emergent properties when reduced to single, two-dimensional (2D) layers. The transition to direct band gap [1,2], emerging charge density waves [3,4], high mobility [5][6][7], and valley polarization [8][9][10] are some of the many exciting properties that have been reported in the TMD literature recently. A major bottleneck to this research is the lack of reproducible and large scale synthetic methods for high quality, consistent monolayer TMD samples. The dominant growth method is the vaporization and subsequent chalcogenization of solid metal oxides in the presence of gaseous chalcogen precursors. This process is commonly referred to as chemical vapor deposition (CVD) or powder vaporization [11][12][13][14]. Due to its simplicity, CVD is extensively used by the TMD community to produce high quality, micron-sized single crystals [11][12][13][15][16][17][18][19]. Understanding the vaporization chemistry of solid transition metal precursors and vapor transport of volatilized precursors, particularly with respect to the influence of water vapor, is critical. Humidity, i.e. water content of the reaction environment, is an important parameter in the gas phase synthesis of inorganic materials, and while it is typically thought of as a contaminant, water is also an effective transport agent [20][21][22][23]. In this communication, we describe the synthesis of luminescent monolayer TMD islands by introducing water vapor as a simple means of controlling the volatilization and transport of the metal oxide precursor. Our experiments demonstrate a direct correlation between gas phase water content and the morphology of the resulting films. In particular, explicit control of the in situ water vapor concentration allows us to switch between two modes of growth: one in an effectively dry environment, in which the transition metal oxide source is converted directly to TMD material through a solid state reaction with the chalcogen source, and another in which the transition metal oxide undergoes vapor transport followed by reaction with the chalcogen source. We show that a small amount of water enhances the volatilization, and hence vapor transport, of the oxides of tungsten and molybdenum at the elevated temperatures (500-800 °C) used in the conversion or growth of their TMD counterparts. We attribute this effect to the enhanced vaporization of WO 3 and MoO 3 in the presence of water, first demonstrated in the 1930s and Our results show a direct correlation between gas phase water content and the morphology of TMD films. In particular, we show that the presence of water enhances volatilization, and therefore the vapor transport of tungsten and molybdenum oxide. Surprisingly, we find that water not only plays an important role in volatilization but is also compatible with TMD growth. In fact, carefully controlled humidity can consistently produce high qual...

We demonstrate fast (0.25 s/pixel) nanoscale chemical imaging in aqueous solution via tipenhanced Raman scattering (TERS), with sub-15 nm spatial resolution. The substrate consists of 4-mercaptobenzonitrile-functionalized monocrystalline gold triangular platelets immersed in H2O, which we map using a gold-coated AFM probe illuminated using a 633 nm laser source. We find that the recorded TERS images trace the enhanced local optical fields that are sustained towards the edges and corners of the triangles. In effect, we directly map local optical fields of a plasmonic substrate in aqueous solution through molecular TERS. Overall, our described platform and approach may generally be used for chemical and biological imaging, and potentially, to follow chemical transformations at solid-liquid interfaces through TERS.

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 ID/IG 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.

Understanding growth, grain boundaries (GBs), and defects of emerging two-dimensional (2D) materials is key to enabling their future applications. For quick, nondestructive metrology, many studies rely on confocal Raman spectroscopy, the spatial resolution of which is constrained by the diffraction limit (∼0.5 μm). Here we use tip-enhanced Raman spectroscopy (TERS) for the first time on synthetic MoSe2 monolayers, combining it with other scanning probe microscopy (SPM) techniques, all with sub-20 nm spatial resolution. We uncover strong nanoscale heterogeneities in the Raman spectra of MoSe2 transferred to gold substrates [one near 240 cm–1 (A1′), and others near 287 cm–1 (E′), 340 cm–1, and 995 cm–1], which are not observable with common confocal techniques and appear to imply the presence of nanoscale domains of MoO3. We also observe strong tip-enhanced photoluminescence (TEPL), with a signal nearly an order of magnitude greater than the far-field PL. Combining TERS with other SPM techniques, we find that GBs can cut into larger domains of MoSe2, and that carrier densities are higher at GBs than away from them.

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.

Supramolecular ordering of organic semiconductors is the key factor defining their electrical characteristics. Yet, it is extremely difficult to control, particularly at the interface with metal and dielectric surfaces in semiconducting devices. We have explored the growth of n-type semiconducting films based on hydrogen-bonded monoalkylnaphthalenediimide (NDI-R) from solution and through vapor deposition on both conductive and insulating surfaces. We combined scanning tunneling and atomic force microscopies with X-ray diffraction analysis to characterize, at the submolecular level, the evolution of the NDI-R molecular packing in going from monolayers to thin films. On a conducting (graphite) surface, the first monolayer of NDI-R molecules adsorbs in a flat-lying (face-on) geometry, whereas in subsequent layers the molecules pack edge-on in islands (Stranski− Krastanov-like growth). On SiO 2 , the NDI-R molecules form into islands comprising edge-on packed molecules (Volmer−Weber mode). Under all the explored conditions, self-complementary H bonding of the imide groups dictates the molecular assembly. The measured electron mobility of the resulting films is similar to that of dialkylated NDI molecules without H bonding. The work emphasizes the importance of H bonding interactions for controlling the ordering of organic semiconductors, and demonstrates a connection between on-surface self-assembly and the structural parameters of thin films used in electronic devices.