Substitutional doping of transition metal dichalcogenides (TMDs) may provide routes to achieving tunable p-n junctions, bandgaps, chemical sensitivity, and magnetism in these materials. In this study, we demonstrate in situ doping of monolayer molybdenum disulfide (MoS2) with manganese (Mn) via vapor phase deposition techniques. Successful incorporation of Mn in MoS2 leads to modifications of the band structure as evidenced by photoluminescence and X-ray photoelectron spectroscopy, but this is heavily dependent on the choice of substrate. We show that inert substrates (i.e., graphene) permit the incorporation of several percent Mn in MoS2, while substrates with reactive surface terminations (i.e., SiO2 and sapphire) preclude Mn incorporation and merely lead to defective MoS2. The results presented here demonstrate that tailoring the substrate surface could be the most significant factor in substitutional doping of TMDs with non-TMD elements.

Bound exciton is a signature of sulfur vacancies, and thus, it can be used to investigate defects in atomically thin materials.

Large-area (~cm 2 ) films of vertical heterostructures formed by alternating graphene and transition-metal dichalcogenide (TMD) alloys are obtained by wet chemical routes followed by a thermal treatment at low temperature. In particular, we synthesized stacked graphene and WxMo1-xS2 alloy phases that were used as hydrogen evolution catalysts. We observed a Tafel slope of 38.7 mV dec -1 and 96 mV onset potential (at current density of 10 mA cm -2 ) when the heterostructure alloy was annealed at 300 o C. These results indicate that heterostructures formed by graphene and W0.4Mo0.6S2 alloys are far more efficient than WS2 and MoS2 by at least a factor of two, and they are superior than other reported TMD systems. This strategy offers a cheap and low temperature synthesis alternative able to replace Pt in the hydrogen evolution reaction (HER). Furthermore, the catalytic activity of the alloy is stable over time,i.e. the catalytic activity does not experience a significant change even after 1000 cycles. Using density functional theory calculations, we found that this enhanced hydrogen evolution in the 4 WxMo1-xS2 alloys is mainly due to the lower energy barrier created by a favorable overlap of the d-orbitals from the transition metals and the s-orbitals of H2; with the lowest energy barrier occurring for the W0.4Mo0.6S2 alloy. Thus, it is now possible to further improve the performance of the "inert" TMD basal plane via metal alloying, in addition to the previously reported strategies such as creation of point defects, vacancies and edges. The synthesis of graphene/W0.4Mo0.6S2 produced at relatively low temperatures is scalable and could be used as an effective low cost Pt-free catalyst.5

Single-and few-layered transition metal dichalcogenides, such as MoS 2 and WS 2 , are emerging two-dimensional materials exhibiting numerous and unusual physicochemical properties that could be advantageous in the fabrication of unprecedented optoelectronic devices. Here we report a novel and alternative route to synthesize triangular monocrystals of MoS 2 and Mo x W 1-x S 2 by annealing MoS 2 and MoS 2 /WO 3 precursors, respectively, in the presence of sulfur vapor. In particular, the Mo x W 1-x S 2 triangular monolayers show gradual concentration profiles of W and Mo whereby Mo concentrates in the islands' center and W is more abundant on the outskirts of the triangular monocrystals. These observations were confirmed by atomic force microscopy, and high-resolution transmission electron microscopy, as well as Raman and photoluminescence spectroscopy. The presence of tunable PL signals depending on the Mo x W 1-x S 2 stoichiometries in 2D monocrystals opens up a wide range of applications in electronics and optoelectronics.

Two-dimensional (2D) atomic crystals and van der Waals heterostructures constitute an emerging platform for developing new functional ultra-thin electronic and optoelectronic materials for novel energy-efficient devices. However, in most thin-film optical applications, there is a long-existing trade-off between the effectiveness of light-matter interactions and the thickness of semiconductor materials, especially when the materials are scaled down to atom thick dimensions. Consequently, enhancement strategies can introduce significant advances to these atomically thick materials and devices. Here we demonstrate enhanced absorption and photoluminescence generation from MoS 2 monolayers coupled with a planar nanocavity. This nanocavity consists of an alumina nanolayer spacer sandwiched between monolayer MoS 2 and an aluminum reflector, and can strongly enhance the light-matter interaction within the MoS 2 , increasing the exclusive absorption of monolayer MoS 2 to nearly 70% at a wavelength of 450 nm. The nanocavity also modifies the spontaneous emission rate, providing an additional design freedom to control the interaction between light and 2D materials.

The high field phenomena of inter-valley transfer and avalanching breakdown have long been exploited in devices based on conventional semiconductors. In this Article, we demonstrate the manifestation of these effects in atomically-thin WS2 field-effect transistors. The negative differential conductance exhibits all of the features familiar from discussions of this phenomenon in bulk semiconductors, including hysteresis in the transistor characteristics and increased noise that is indicative of travelling high-field domains. It is also found to be sensitive to thermal annealing, a result that we attribute to the influence of strain on the energy separation of the different valleys involved in hot-electron transfer. This idea is supported by the results of ensemble Monte Carlo simulations, which highlight the sensitivity of the negative differential conductance to the equilibrium populations of the different valleys. At high drain currents (>10 μA/μm) avalanching breakdown is also observed, and is attributed to trap-assisted inverse Auger scattering. This mechanism is not normally relevant in conventional semiconductors, but is possible in WS2 due to the narrow width of its energy bands. The various results presented here suggest that WS2 exhibits strong potential for use in hot-electron devices, including compact high-frequency sources and photonic detectors.

Clustered structure of social networks provides the chances of repeated exposures to carriers with similar information. It is commonly believed that the impact of repeated exposures on the spreading of information is nontrivial. Does this effect increase the probability that an individual forwards a message in social networks? If so, to what extent does this effect influence people’s decisions on whether or not to spread information? Based on a large-scale microblogging data set, which logs the message spreading processes and users’ forwarding activities, we conduct a data-driven analysis to explore the answer to the above questions. The results show that an overwhelming majority of message samples are more probable to be forwarded under repeated exposures, compared to those under only a single exposure. For those message samples that cover various topics, we observe a relatively fixed, topic-independent multiplier of the willingness of spreading when repeated exposures occur, regardless of the differences in network structure. We believe that this finding reflects average people’s intrinsic psychological gain under repeated stimuli. Hence, it makes sense that the gain is associated with personal response behavior, rather than network structure. Moreover, we find that the gain is robust against the change of message popularity. This finding supports that there exists a relatively fixed gain brought by repeated exposures. Based on the above findings, we propose a parsimonious model to predict the saturated numbers of forwarding activities of messages. Our work could contribute to better understandings of behavioral psychology and social media analytics.

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