MoS presents a promising low-cost catalyst for the hydrogen evolution reaction (HER), but the understanding about its active sites has remained limited. Here we present an unambiguous study of the catalytic activities of all possible reaction sites of MoS, including edge sites, sulfur vacancies, and grain boundaries. We demonstrate that, in addition to the well-known catalytically active edge sites, sulfur vacancies provide another major active site for the HER, while the catalytic activity of grain boundaries is much weaker. The intrinsic turnover frequencies (Tafel slopes) of the edge sites, sulfur vacancies, and grain boundaries are estimated to be 7.5 s (65-75 mV/dec), 3.2 s (65-85 mV/dec), and 0.1 s (120-160 mV/dec), respectively. We also demonstrate that the catalytic activity of sulfur vacancies strongly depends on the density of the vacancies and the local crystalline structure in proximity to the vacancies. Unlike edge sites, whose catalytic activity linearly depends on the length, sulfur vacancies show optimal catalytic activities when the vacancy density is in the range of 7-10%, and the number of sulfur vacancies in high crystalline quality MoS is higher than that in low crystalline quality MoS, which may be related with the proximity of different local crystalline structures to the vacancies.

The quantitative correlation of the catalytic activity with the microscopic structure of heterogeneous catalysts is a major challenge for the field of catalysis science. It requests synergistic capabilities to tailor the structure with atomic scale precision and to control the catalytic reaction to proceed through well-defined pathways. Here we leverage on the controlled growth of MoS2 atomically thin films to demonstrate that the catalytic activity of MoS2 for the hydrogen evolution reaction decreases by a factor of ∼ 4.47 for the addition of every one more layer. Similar layer dependence is also found in edge-riched MoS2 pyramid platelets. This layer-dependent electrocatalysis can be correlated to the hopping of electrons in the vertical direction of MoS2 layers over an interlayer potential barrier. Our experimental results suggest the potential barrier to be 0.119 V, consistent with theoretical calculations. Different from the conventional wisdom, which states that the number of edge sites is important, our results suggest that increasing the hopping efficiency of electrons in the vertical direction is a key for the development of high-efficiency two-dimensional material catalysts.

Single layer MoS2 is an ideal material for the emerging field of "valleytronics" in which charge carrier momentum can be finely controlled by optical excitation. This system is also known to exhibit strong many-body interactions as observed by tightly bound excitons and trions. Here we report direct measurements of valley relaxation dynamics in single layer MoS2, by using ultrafast transient absorption spectroscopy. Our results show that strong Coulomb interactions significantly impact valley population dynamics. Initial excitation by circularly polarized light creates electron-hole pairs within the K-valley. These excitons coherently couple to dark intervalley excitonic states, which facilitate fast electron valley depolarization. Hole valley relaxation is delayed up to about 10 ps due to nondegeneracy of the valence band spin states. Intervalley biexciton formation reveals the hole valley relaxation dynamics. We observe that biexcitons form with more than an order of magnitude larger binding energy compared to conventional semiconductors. These measurements provide significant insight into valley specific processes in 2D semiconductors. Hence they could be used to suggest routes to design semiconducting materials that enable control of valley polarization.

Two dimensional (2D) materials with a monolayer of atoms represent an ultimate control of material dimension in the vertical direction. Molybdenum sulfide (MoS2) monolayers, with a direct bandgap of 1.8 eV, offer an unprecedented prospect of miniaturizing semiconductor science and technology down to a truly atomic scale. Recent studies have indeed demonstrated the promise of 2D MoS2 in fields including field effect transistors, low power switches, optoelectronics, and spintronics. However, device development with 2D MoS2 has been delayed by the lack of capabilities to produce large-area, uniform, and high-quality MoS2 monolayers. Here we present a self-limiting approach that can grow high quality monolayer and few-layer MoS2 films over an area of centimeters with unprecedented uniformity and controllability. This approach is compatible with the standard fabrication process in semiconductor industry. It paves the way for the development of practical devices with 2D MoS2 and opens up new avenues for fundamental research.

The transfer of synthesized 2D MoS2 films is important for fundamental and applied research. However, it is problematic to translate the well-established transfer processes for graphene to MoS2 due to different growth mechanisms and surface properties. Here we demonstrate a surface-energy-assisted process that can perfectly transfer centimeter-scale monolayer and few-layer MoS2 films from original growth substrates onto arbitrary substrates with no observable wrinkles, cracks, and polymer residues. The unique strategies used in this process include leveraging the penetration of water between hydrophobic MoS2 films and hydrophilic growth substrates to lift off the films and dry transferring the film after the lift off. This is in stark contrast with the previous transfer process for synthesized MoS2 films, which explores the etching of the growth substrate by hot base solutions to lift off the films. Our transfer process can effectively eliminate the mechanical force caused by bubble generations, the attacks from chemical etchants, and the capillary force induced when transferring the film outside solutions as in the previous transfer process, which consists of the major causes for the previous unsatisfactory transfer. Our transfer process also benefits from using polystyrene (PS), instead of poly(methyl methacrylate) (PMMA) that was widely used previously, as the carrier polymer. PS can form more intimate interaction with MoS2 films than PMMA and is important for maintaining the integrity of the film during the transfer process. This surface-energy-assisted approach can be generally applied to the transfer of other 2D materials, such as WS2.

Ridge National Laboratory, Oak Ridge, Tennessee 37831 § These authors contribute equally. AbstractSemiconductor heterostructures provide a powerful platform to engineer the dynamics of excitons for fundamental and applied interests. However, the functionality of conventional semiconductor heterostructures is often limited by inefficient charge transfer across interfaces due to the interfacial imperfection caused by lattice mismatch. Here we demonstrate that MoS 2 /WS 2 heterostructures consisting of monolayer MoS 2 and WS 2 stacked in the vertical direction can enable equally efficient interlayer exciton relaxation regardless the epitaxy and orientation of the stacking. This is manifested by a similar two orders of magnitude decrease of

We systematically measure the dielectric function of atomically thin MoS2 films with different layer numbers and demonstrate that excitonic effects play a dominant role in the dielectric function when the films are less than 5–7 layers thick. The dielectric function shows an anomalous dependence on the layer number. It decreases with the layer number increasing when the films are less than 5–7 layers thick but turns to increase with the layer number for thicker films. We show that this is because the excitonic effect is very strong in the thin MoS2 films and its contribution to the dielectric function may dominate over the contribution of the band structure. We also extract the value of layer-dependent exciton binding energy and Bohr radius in the films by fitting the experimental results with an intuitive model. The dominance of excitonic effects is in stark contrast with what reported at conventional materials whose dielectric functions are usually dictated by band structures. The knowledge of the dielectric function may enable capabilities to engineer the light-matter interactions of atomically thin MoS2 films for the development of novel photonic devices, such as metamaterials, waveguides, light absorbers, and light emitters.

We measured the lifetime of optically created valley polarization in single layer WS 2 using transient absorption spectroscopy. The electron valley relaxation is very short (< 1ps). However the hole valley lifetime is at least two orders of magnitude longer and exhibits a temperature dependence that cannot be explained by single carrier spin/valley relaxation mechanisms. Our theoretical analysis suggests that a collective contribution of two potential processes may explain the valley relaxation in single layer WS 2 . One process involves direct scattering of excitons from K to K valleys with a spin flip-flop interaction. The other mechanism involves scattering through spin degenerate Γ valley. This second process is thermally activated with an Arrhenius behavior due to the energy barrier between Γ and K valleys.