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.
This study reveals that the interaction between a 2D material and its substrate can significantly modify its electronic and optical properties, and thus can be used as a means to optimize these ...properties. High-temperature （25-500℃） optical spectroscopy, which combines Raman and photoluminescence spectroscopies, is highly effective for investigating the interaction and material properties that are not accessible at the commonly used cryogenic temperature （e.g., a thermal activation process with an activation of a major fraction of the bandgap）. This study investigates a set of monolayer WS2 films, either directly grown on sapphire and SiO2 substrates by CVD or transferred onto SiO2 substrate. The coupling with the substrate is shown to depend on the substrate type, the material- substrate bonding （even for the same substrate）, and the excitation wavelength. The inherent difference in the states of strain between the as-grown and the transferred films has a significant impact on the material properties.
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.
We report that the refractive index of transition metal dichacolgenide (TMDC) monolayers, such as MoS2, WS2, and WSe2, can be substantially tuned by >60% in the imaginary part and >20% in the real ...part around exciton resonances using complementary metal–oxide–semiconductor (CMOS) compatible electrical gating. This giant tunablility is rooted in the dominance of excitonic effects in the refractive index of the monolayers and the strong susceptibility of the excitons to the influence of injected charge carriers. The tunability mainly results from the effects of injected charge carriers to broaden the spectral width of excitonic interband transitions and to facilitate the interconversion of neutral and charged excitons. The other effects of the injected charge carriers, such as renormalizing bandgap and changing exciton binding energy, only play negligible roles. We also demonstrate that the atomically thin monolayers, when combined with photonic structures, can enable the efficiencies of optical absorption (reflection) tuned from 40% (60%) to 80% (20%) due to the giant tunability of the refractive index. This work may pave the way toward the development of field-effect photonics in which the optical functionality can be controlled with CMOS circuits.
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.
MoS2 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 MoS2, 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–1 (65–75 mV/dec), 3.2 s–1 (65–85 mV/dec), and 0.1 s–1 (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 MoS2 is higher than that in low crystalline quality MoS2, which may be related with the proximity of different local crystalline structures to the vacancies.
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.
Semiconductor 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 MoS2/WS2 heterostructures consisting of monolayer MoS2 and WS2 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 2 orders of magnitude decrease of photoluminescence intensity in both epitaxial and nonepitaxial MoS2/WS2 heterostructures. Both heterostructures also show similarly improved absorption beyond the simple superimposition of the absorptions of monolayer MoS2 and WS2. Our result indicates that 2D heterostructures bear significant implications for the development of photonic devices, in particular those requesting efficient exciton separation and strong light absorption, such as solar cells, photodetectors, modulators, and photocatalysts. It also suggests that the simple stacking of dissimilar 2D materials with random orientations is a viable strategy to fabricate complex functional 2D heterostructures, which would show similar optical functionality as the counterpart with perfect epitaxy.
It is demonstrated that the luminescence efficiency of monolayers composed of MoS2, WS2, and WSe2 is significantly limited by the substrate and can be improved by orders of magnitude through ...substrate engineering. The substrate affects the efficiency mainly through doping the monolayers and facilitating defect‐assisted nonradiative exciton recombinations, while the other substrate effects including straining and dielectric screening play minor roles. The doping may come from the substrate and substrate‐borne water moisture, the latter of which is much stronger than the former for MoS2 and WS2 but negligible for WSe2. Using proper substrates such as mica or hexagonal boron nitride can substantially mitigate the doping effect. The defect‐assisted recombination depends on the interaction between the defect in the monolayer and the substrate. Suspended monolayers, in which the substrate effects are eliminated, may have efficiency up to 40% at room temperatures. The result provides useful guidance for the rational design of atomic‐scale light emission devices.
Luminescence efficiency in transition metal dichalcogenide monolayers can be improved by orders of magnitude through engineering the interaction with substrates. The luminescence efficiency of the monolayers is mainly affected through doping and facilitating nonradiative exciton recombination. Since the doping effect significantly depends on the kind of substrate, choosing the right type of substrates is a crucial step toward maximizing efficiency.
The two-dimensional (2D) nanostructure of layered chalcogenide materials (LCMs) is very interesting, but to make it a useful material platform necessiates the development of sophisticated synthetic ...control. We present the synthesis of single-crystalline SnSe2 nanoplates by a noncatalytic vapor deposition process and demonstrate that the growth is subject to strong influences from substrates. The effect of substrates is evidenced by a temperature-dependent morphological difference in the nanoplates grown on mica and silicon substrates. At a growth temperature of 280 °C, the diameter of the nanoplates grown on mica is larger than those grown on silicon by a ratio of 6.2. This ratio substantially decreases to be unity (1.04) at a higher temperature of 420 °C. Additionally, different from the nanoplates grown on silicon, which always show a well-defined hexagonal shape, the nanoplates grown on mica exhibit an irregular shape at low temperature and can gradually evolve into the hexagonal shape with increasing temperature. Our dynamics analysis suggests that the observed temperature-dependent morphological difference can be specifically correlated to the migration of SnSe2 adatoms on the surface of substrates. SnSe2 adatoms may migrate on mica more easily than on silicon substrates because of the presence of dangling bonds at the surface of silicon. The role of the facile migration on mica in the nanoplate growth may be further confirmed by a correlation between the nanoplate diameter and the distance between neighboring nanoplates. While the focus is on SnSe2, we believe that this understanding can apply to the growth of two-dimensional (2D) nanostructures of other layered chalcogenide materials (LCMs). It may pave the way for the development of a general synthetic paradigm that leverages the effect of substrates to control the growth of 2D LCM nanostructures.
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