Xiebo Zhou

All Chemical Vapor Deposition Synthesis and Intrinsic Bandgap Observation of MoS2/Graphene Heterostructures

A facile all-chemical vapor deposition approach is designed, which allows both sequentially grown Gr and monolayer MoS2 in the same growth process, thus allowing the direct construction of MoS2 /Gr vertical heterostructures on Au foils. A weak n-doping effect and an intrinsic bandgap of MoS2 are obtained from MoS2 /Gr/Au via scanning tunneling microscopy and spectroscopy characterization. The exciton binding energy is accurately deduced by combining photoluminescence measurements.

Grain Boundary Structures and Electronic Properties of Hexagonal Boron Nitride on Cu(111)

Grain boundaries (GBs) of hexagonal boron nitride (h-BN) grown on Cu(111) were investigated by scanning tunneling microscopy/spectroscopy (STM/STS). The first experimental evidence of the GBs composed of square-octagon pairs (4|8 GBs) was given, together with those containing pentagon-heptagon pairs (5|7 GBs). Two types of GBs were found to exhibit significantly different electronic properties, where the band gap of the 5|7 GB was dramatically decreased as compared with that of the 4|8 GB, consistent with our obtained result from density functional theory (DFT) calculations. Moreover, the present work may provide a possibility of tuning the inert electronic property of h-BN via grain boundary engineering.

Temperature-Mediated Selective Growth of MoS2/WS2 and WS2/MoS2 Vertical Stacks on Au Foils for Direct Photocatalytic Applications

A growth-temperature-mediated two-step chemical vapor deposition strategy is designed to synthesize MoS2 /WS2 and WS2 /MoS2 stacks on Au foils. Predominantly A-A stacked MoS2 /WS2 and A-B stacked WS2 /MoS2 are selectively achieved and confirmed. Relative enhancements or reductions in photocatalytic activities of MoS2 /WS2 or WS2 /MoS2 are observed under illumination, because the type-II band alignment enables directional electron flow from electrode to active site.

Nanodiode based on a multiwall CNx/carbon nanotube intramolecular junction

We prepared multiwall carbon nanotubes (MWCNTs) from the pyrolysis of ferrocene, and CN(x) nanotubes from a mixture of ferrocene and melamine. Under well chosen synthesis conditions, massive multiwall CN(x)/carbon nanotube intramolecular junctions were successfully fabricated. The individual nanotubes were used as conductance channels to obtain their transport characteristic information. Measurement results showed that the current-voltage (I-V) curve of the CN(x)/CNT junction is highly asymmetric, behaving like a diode. Moreover, the devices are very stable in ambient environment. We attribute this nonlinear property of the CN(x)/CNT junctions to their two different atomic and electronic sections.

Periodic Modulation of the Doping Level in Striped MoS2 Superstructures

Although the recently discovered monolayer transition metal dichalcogenides exhibit novel electronic and optical properties, fundamental physical issues such as the quasiparticle bandgap tunability and the substrate effects remain undefined. Herein, we present the report of a quasi-one-dimensional periodically striped superstructure for monolayer MoS2 on Au(100). The formation of the unique striped superstructure is found to be mainly modulated by the symmetry difference between MoS2 and Au(100) and their lattice mismatch. More intriguingly, we find that the monolayer MoS2 is heavily n-doped on the Au(100) facet with a bandgap of 1.3 eV, and the Fermi level is upshifted by ∼0.10 eV on the ridge (∼0.2 eV below the conduction band) in contrast to the valley regions (∼0.3 eV below the conduction band) of the striped patterns after high-temperature sample annealing process. This tunable doping effect is considered to be caused by the different defect densities over the ridge/valley regions of the superstructure. Additionally, an obvious bandgap reduction is observed in the vicinity of the domain boundary for monolayer MoS2 on Au(100). This work should therefore inspire intensive explorations of adlayer-substrate interactions, the defects, and their effects on band-structure engineering of monolayer MoS2.

Direct Chemical Vapor Deposition Growth and Band-Gap Characterization of MoS2/h-BN van der Waals Heterostructures on Au Foils

Stacked transition-metal dichalcogenides on hexagonal boron nitride (h-BN) are platforms for high-performance electronic devices. However, such vertical stacks are usually constructed by the layer-by-layer polymer-assisted transfer of mechanically exfoliated layers. This inevitably causes interfacial contamination and device performance degradation. Herein, we develop a two-step, low-pressure chemical vapor deposition synthetic strategy incorporating the direct growth of monolayer h-BN on Au foil with the subsequent growth of MoS2. In such vertical stacks, the interactions between MoS2 and Au are diminished by the intervening h-BN layer, as evidenced by the appearance of photoluminescence in MoS2. The weakened interfacial interactions facilitate the transfer of the MoS2/h-BN stacks from Au to arbitrary substrates by an electrochemical bubbling method. Scanning tunneling microscope/spectroscopy characterization shows that the central h-BN layer partially blocks the metal-induced gap states in MoS2/h-BN/Au foils. The work offers insight into the synthesis, transfer, and device performance optimization of such vertically stacked heterostructures.

Two-dimensional metallic tantalum disulfide as a hydrogen evolution catalyst

Two-dimensional metallic transition metal dichalcogenides are emerging as prototypes for uncovering fundamental physical phenomena, such as superconductivity and charge-density waves, as well as for engineering-related applications. However, the batch production of such envisioned transition metal dichalcogenides remains challenging, which has hindered the aforementioned explorations. Herein, we fabricate thickness-tunable tantalum disulfide flakes and centimetre-sized ultrathin films on an electrode material of gold foil via a facile chemical vapour deposition route. Through temperature-dependent Raman characterization, we observe the transition from nearly commensurate to commensurate charge-density wave phases with our ultrathin tantalum disulfide flakes. We have obtained high hydrogen evolution reaction efficiency with the as-grown tantalum disulfide flakes directly synthesized on gold foils comparable to traditional platinum catalysts. This work could promote further efforts for exploring new efficient catalysts in the large materials family of metallic transition metal dichalcogenides, as well as exploiting their applications towards more versatile applications.Metallic transition metal dichalcogenides are important materials for catalysis, but scalable and controllable preparation methods are scarce. Here, the authors synthesize 2H-TaS2 as centimetre-scale films of tunable thickness and show they are an efficient catalyst for hydrogen evolution.

Batch production of 6-inch uniform monolayer molybdenum disulfide catalyzed by sodium in glass

Monolayer transition metal dichalcogenides (TMDs) have become essential two-dimensional materials for their perspectives in engineering next-generation electronics. For related applications, the controlled growth of large-area uniform monolayer TMDs is crucial, while it remains challenging. Herein, we report the direct synthesis of 6-inch uniform monolayer molybdenum disulfide on the solid soda-lime glass, through a designed face-to-face metal-precursor supply route in a facile chemical vapor deposition process. We find that the highly uniform monolayer film, with the composite domains possessing an edge length larger than 400 µm, can be achieved within a quite short time of 8 min. This highly efficient growth is proven to be facilitated by sodium catalysts that are homogenously distributed in glass, according to our experimental facts and density functional theory calculations. This work provides insights into the batch production of highly uniform TMD films on the functional glass substrate with the advantages of low cost, easily transferrable, and compatible with direct applications.Growth of large-area monolayer transition metal dichalcogenides is critical for their application but remains challenging. Here Yang et al. report rapid chemical vapor deposition of 6-inch monolayer molybdenum disulfide by sufficiently uniformly supplying the precursors and catalysts.

Temperature-Triggered Sulfur Vacancy Evolution in Monolayer MoS2/Graphene Heterostructures

The existence of defects in 2D semiconductors has been predicted to generate unique physical properties and markedly influence their electronic and optoelectronic properties. In this work, it is found that the monolayer MoS2 prepared by chemical vapor deposition is nearly defect-free after annealing under ultrahigh vacuum conditions at ≈400 K, as evidenced by scanning tunneling microscopy observations. However, after thermal annealing process at ≈900 K, the existence of dominant single sulfur vacancies and relatively rare vacancy chains (2S, 3S, and 4S) is convinced in monolayer MoS2 as-grown on Au foils. Of particular significance is the revelation that the versatile vacancies can modulate the band structure of the monolayer MoS2 , leading to a decrease of the bandgap and an obvious n-doping effect. These results are confirmed by scanning tunneling spectroscopy data as well as first-principles theoretical simulations of the related morphologies and the electronic properties of the various defect types. Briefly, this work should pave a novel route for defect engineering and hence the electronic property modulation of three-atom-thin 2D layered semiconductors.

Substrate effect on the growth of monolayer dendritic MoS2 on LaAlO3 (100) and its electrocatalytic applications

In accommodating the rapid development of two-dimensional (2D) nanomaterials, chemical vapor deposition (CVD) has become a powerful tool for their batch production with desirable characteristics, such as high crystal quality, large domain size, and tunable domain shape. The crystallinity and morphology of the growth substrates usually play a crucial role in the CVD synthesis of high-quality monolayer MoS2, a kind of 2D layered material which has ignited huge interest in nanoelectronics, optoelectronics and energy harvesting, etc. Herein, by utilizing a low-pressure chemical vapor deposition (LPCVD) system, we demonstrate a regioselective synthesis of monolayer MoS2 on the corrugated single-crystal LaAlO3 (100) with twin crystal domains induced by the second-order phase transition. Unique dendritic morphologies with tunable nucleation densities were obtained in different regions of the undulated substrate, presenting a strong substrate modulation effect. Interestingly, the exposure of abundant active edge sites along with the rather high nucleation density makes the monolayer dendritic MoS2 a good electrocatalyst for hydrogen evolution reaction (HER), particularly featured by a rather high exchange current density (70.4 μA cm−2). Furthermore, uniform monolayer MoS2 films can also be obtained and transferred to arbitrary substrates. We believe that this work provides a new growth system for the controllable synthesis of 2D layered materials with unique dendritic morphologies, as well as its great application potential in energy conversion and harvesting.