Photo-oxidative Crack Propagation in Transition Metal Dichalcogenides.

Monolayered transition-metal dichalcogenides (TMDs) are easily exposed to air, and their crystal quality can often be degraded via oxidation, leading to poor electronic and optical device performance. The degradation becomes more severe in the presence of defects, grain boundaries, and residues. Here, we report crack propagation in pristine TMD monolayers grown by chemical vapor deposition under ambient conditions and light illumination. Under a high relative humidity (RH) of ∼60% and white light illumination, the cracks appear randomly. Photo-oxidative cracks gradually propagated along the grain boundaries of the TMD monolayers. In contrast, under low RH conditions of ∼2%, cracks were scarcely observed. Crack propagation is predominantly attributed to the accumulation of water underneath the TMD monolayers, which is preferentially absorbed by hygroscopic alkali metal-based precursor residues. Crack propagation is further accelerated by the cyclic process of photo-oxidation in a basic medium, leading to localized tensile strain. We also found that such crack propagation is prevented after the removal of alkali metals via the transfer of the sample to other substrates.

Sequential Growth of Vertical Transition-Metal Dichalcogenide Heterostructures on Rollable Aluminum Foil.

Vertical van der Waals heterostructures (vdWhs), which are made by layer-by-layer stacking of two-dimensional (2D) materials, offer great opportunities for the development of extraordinary physics and devices such as topological superconductivity, robust quantum Hall phenomenon, electron-hole pair condensation, Coulomb drag, and tunneling devices. However, the size of vdWhs is still limited to the order of a few micrometers, which restricts the large-scale roll-to-roll processes for industrial applications. Herein, we report the sequential growth of a 14 in. vertical vdWhs on a rollable Al foil via chemical vapor deposition. By supplying chalcogen precursors to liquid transition-metal precursor-coated Al foils, we grew a wide range of individual 2D transition-metal dichalcogenide (TMD) films, including MoS2, VS2, ReS2, WS2, SnS2, WSe2, and vanadium-doped MoS2. Additionally, by repeating the growth process, we successfully achieved the layer-by-layer growth of ReS2/MoS2 and SnS2/ReS2/MoS2 vdWhs. The chemically inert Al native oxide layer inhibits the diffusion of chalcogen and metal atoms into Al foils, allowing for the growth of diverse TMDs and their vdWhs. The conductive Al substrate enables the effective use of vdWhs/Al as a hydrogen evolution reaction electrocatalyst with a transfer-free process. This work provides a robust route for the commercialization of 2D TMDs and their vdWhs at a low cost.

Substitutional Vanadium Sulfide Nanodispersed in MoS2 Film for Pt-Scalable Catalyst.

Among transition metal dichalcogenides (TMdCs) as alternatives for Pt-based catalysts, metallic-TMdCs catalysts have highly reactive basal-plane but are unstable. Meanwhile, chemically stable semiconducting-TMdCs show limiting catalytic activity due to their inactive basal-plane. Here, metallic vanadium sulfide (VSn ) nanodispersed in a semiconducting MoS2 film (V-MoS2 ) is proposed as an efficient catalyst. During synthesis, vanadium atoms are substituted into hexagonal monolayer MoS2 to form randomly distributed VSn units. The V-MoS2 film on a Cu electrode exhibits Pt-scalable catalytic performance; current density of 1000 mA cm-2 at 0.6 V and overpotential of -0.08 V at a current density of 10 mA cm-2 with excellent cycle stability for hydrogen-evolution-reaction (HER). The high intrinsic HER performance of V-MoS2 is explained by the efficient electron transfer from the Cu electrode to chalcogen vacancies near vanadium sites with optimal Gibbs free energy (-0.02 eV). This study provides insight into ways to engineer TMdCs at the atomic-level to boost intrinsic catalytic activity for hydrogen evolution.

Epitaxial Single-Crystal Growth of Transition Metal Dichalcogenide Monolayers via the Atomic Sawtooth Au Surface.

Growth of 2D van der Waals layered single-crystal (SC) films is highly desired not only to manifest the intrinsic physical and chemical properties of materials, but also to enable the development of unprecedented devices for industrial applications. While wafer-scale SC hexagonal boron nitride film has been successfully grown, an ideal growth platform for diatomic transition metal dichalcogenide (TMdC) films has not been established to date. Here, the SC growth of TMdC monolayers on a centimeter scale via the atomic sawtooth gold surface as a universal growth template is reported. The atomic tooth-gullet surface is constructed by the one-step solidification of liquid gold, evidenced by transmission electron microscopy. The anisotropic adsorption energy of the TMdC cluster, confirmed by density-functional calculations, prevails at the periodic atomic-step edge to yield unidirectional epitaxial growth of triangular TMdC grains, eventually forming the SC film, regardless of the Miller indices. Growth using the atomic sawtooth gold surface as a universal growth template is demonstrated for several TMdC monolayer films, including WS2 , WSe2 , MoS2 , the MoSe2 /WSe2 heterostructure, and W1- x Mox S2 alloys. This strategy provides a general avenue for the SC growth of diatomic van der Waals heterostructures on a wafer scale, to further facilitate the applications of TMdCs in post-silicon technology.

Wafer-Scale van der Waals Heterostructures with Ultraclean Interfaces via the Aid of Viscoelastic Polymer.

Two-dimensional (2D) van der Waals (vdW) heterostructures exhibit novel physical and chemical properties, allowing the development of unprecedented electronic, optical, and electrochemical devices. However, the construction of wafer-scale vdW heterostructures for practical applications is still limited due to the lack of well-established growth and transfer techniques. Herein, we report a method for the fabrication of wafer-scale 2D vdW heterostructures with an ultraclean interface between layers via the aid of a freestanding viscoelastic polymer support layer (VEPSL). The low glass transition temperature ( Tg) and viscoelastic nature of the VEPSL ensure absolute conformal contact between 2D layers, enabling the easy pick-up of layers and attaching to other 2D layers. This eventually leads to the construction of random sequence 2D vdW heterostructures such as molybdenum disulfide/tungsten disulfide/molybdenum diselenide/tungsten diselenide/hexagonal boron nitride. Furthermore, the VEPSL allows the conformal transfer of 2D vdW heterostructures onto arbitrary substrates, irrespective of surface roughness. To demonstrate the significance of the ultraclean interface, the fabricated molybdenum disulfide/graphene heterostructure employed as an electrocatalyst yielded excellent results of 73.1 mV·dec-1 for the Tafel slope and 0.12 kΩ of charge transfer resistance, which are almost twice as low as that of the impurity-trapped heterostructure.

Wafer-scale single-crystal hexagonal boron nitride film via self-collimated grain formation.

Although polycrystalline hexagonal boron nitride (PC-hBN) has been realized, defects and grain boundaries still cause charge scatterings and trap sites, impeding high-performance electronics. Here, we report a method of synthesizing wafer-scale single-crystalline hBN (SC-hBN) monolayer films by chemical vapor deposition. The limited solubility of boron (B) and nitrogen (N) atoms in liquid gold promotes high diffusion of adatoms on the surface of liquid at high temperature to provoke the circular hBN grains. These further evolve into closely packed unimodal grains by means of self-collimation of B and N edges inherited by electrostatic interaction between grains, eventually forming an SC-hBN film on a wafer scale. This SC-hBN film also allows for the synthesis of wafer-scale graphene/hBN heterostructure and single-crystalline tungsten disulfide.

Synthesis of Large-Area Tungsten Disulfide Films on Pre-Reduced Tungsten Suboxide Substrates.

We report a facile method for the synthesis of large-area tungsten disulfide (WS2) films by means of chemical vapor deposition (CVD). To promote WS2 film growth, the precursor solution, which includes pre-reduced tungsten suboxides, is prepared by using hydrazine as the strong reducing agent and spin-coated onto the growth substrate. Growth is then carried out in a CVD chamber vaporized with dimethyl disulfide as the sulfur precursor. Although only WS2 flakes are grown with unreduced tungsten precursors under a hydrogen atmosphere, WS2 films are readily attained on pre-reduced tungsten suboxide substrates without the need for further reduction by hydrogen, which is noted to induce discontinuity of the grown film. The result presents the coverage of WS2 to be proportional to the amount of reduced tungsten suboxides, which is revealed by X-ray photoelectron spectroscopy. Furthermore, it is found that the multilayer WS2 flakes grow along the grain boundary, which allows the analysis of the grain size of WS2 films by optical microscopy images only. WS2 field effect transistors are fabricated by conventional photolithography and show an average electron mobility of 0.4 cm2 V-1 s-1 and a high on/off ratio of 106 at room temperature.

A Novel and Facile Route to Synthesize Atomic-Layered MoS2 Film for Large-Area Electronics.

High-quality and large-area molybdenum disulfide (MoS2 ) thin film is highly desirable for applications in large-area electronics. However, there remains a challenge in attaining MoS2 film of reasonable crystallinity due to the absence of appropriate choice and control of precursors, as well as choice of suitable growth substrates. Herein, a novel and facile route is reported for synthesizing few-layered MoS2 film with new precursors via chemical vapor deposition. Prior to growth, an aqueous solution of sodium molybdate as the molybdenum precursor is spun onto the growth substrate and dimethyl disulfide as the liquid sulfur precursor is supplied with a bubbling system during growth. To supplement the limiting effect of Mo (sodium molybdate), a supplementary Mo is supplied by dissolving molybdenum hexacarbonyl (Mo(CO)6 ) in the liquid sulfur precursor delivered by the bubbler. By precisely controlling the amounts of precursors and hydrogen flow, full coverage of MoS2 film is readily achievable in 20 min. Large-area MoS2 field effect transistors (FETs) fabricated with a conventional photolithography have a carrier mobility as high as 18.9 cm2 V-1 s-1 , which is the highest reported for bottom-gated MoS2 -FETs fabricated via photolithography with an on/off ratio of ≈105 at room temperature.