Determining the Optimized Interlayer Separation Distance in Vertical Stacked 2D WS2:hBN:MoS2 Heterostructures for Exciton Energy Transfer

The 2D semiconductor monolayer transition metal dichalcogenides, WS₂ and MoS₂, are grown by chemical vapor deposition (CVD) and assembled by sequential transfer into vertical layered heterostructures (VLHs). Insulating hBN, also produced by CVD, is utilized to control the separation between WS₂ and MoS₂ by adjusting the layer number, leading to fine‐scale tuning of the interlayer interactions within the VLHs. The interlayer interactions are studied by photoluminescence (PL) spectroscopy and are demonstrated to be highly sensitive to the input excitation power. For thin hBN separators (one to two layers), the total PL emission switches from quenching to enhancement by increasing the laser power. Femtosecond broadband transient absorption measurements demonstrate that the increase in PL quantum yield results from Förster energy transfer from MoS₂ to WS₂. The PL signal is further enhanced at cryogenic temperatures due to the suppressed nonradiative decay channels. It is shown that (4 ± 1) layers of hBN are optimum for obtaining PL enhancement in the VLHs. Increasing thickness beyond this causes the enhancement factor to diminish, with the WS₂ and MoS₂ then behaving as isolated noninteracting monolayers. These results indicate how controlling the exciton generation rate influences energy transfer and plays an important role in the properties of VLHs.     

Spatial Control of Substitutional Dopants in Hexagonal Monolayer WS2: The Effect of Edge Termination

The ability to control the density and spatial distribution of substitutional dopants in semiconductors is crucial for achieving desired physicochemical properties. Substitutional doping with adjustable doping levels has been previously demonstrated in 2D transition metal dichalcogenides (TMDs); however, the spatial control of dopant distribution remains an open field. In this work, edge termination is demonstrated as an important characteristic of 2D TMD monocrystals that affects the distribution of substitutional dopants. Particularly, in chemical vapor deposition (CVD)-grown monolayer WS₂, it is found that a higher density of transition metal dopants is always incorporated in sulfur-terminated domains when compared to tungsten-terminated domains. Two representative examples demonstrate this spatial distribution control, including hexagonal iron- and vanadium-doped WS₂ monolayers. Density functional theory (DFT) calculations are further performed, indicating that the edge-dependent dopant distribution is due to a strong binding of tungsten atoms at tungsten-zigzag edges, resulting in the formation of open sites at sulfur-zigzag edges that enable preferential dopant incorporation. Based on these results, it is envisioned that edge termination in crystalline TMD monolayers can be utilized as a novel and effective knob for engineering the spatial distribution of substitutional dopants, leading to in-plane hetero-/multi-junctions that display fascinating electronic, optoelectronic, and magnetic properties.     

Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

A simple one‐pot solvothermal method is reported to synthesize VS₂ nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer‐expanded VS₂ nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm^?2, a small Tafel slope of 36 mV dec^?1, and long‐term stability of 60 h without any current fading. The performance is much better than that of the pristine VS₂ with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (?G_H) from density functional theory calculations. This work opens up a new door for developing transition‐metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.     

Atomically Sharp Dual Grain Boundaries in 2D WS2 Bilayers

It is shown that tilt grain boundaries (GBs) in bilayer 2D crystals of the transition metal dichalcogenide WS₂ can be atomically sharp, where top and bottom layer GBs are located within sub‐nanometer distances of each other. This expands the current knowledge of GBs in 2D bilayer crystals, beyond the established large overlapping GB types typically formed in chemical vapor deposition growth, to now include atomically sharp dual bilayer GBs. By using atomic‐resolution annular dark‐field scanning transmission electron microscopy (ADF‐STEM) imaging, different atomic structures in the dual GBs are distinguished considering bilayers with a 3R (AB stacking)/2H (AA′ stacking) interface as well as bilayers with 2H/2H boundaries. An in situ heating holder is used in ADF‐STEM and the GBs are stable to at least 800 °C, with negligible thermally induced reconstructions observed. Normal dislocation cores are seen in one WS₂ layer, but the second WS₂ layer has different dislocation structures not seen in freestanding monolayers, which have metal‐rich clusters to accommodate the stacking mismatch of the 2H:3R interface. These results reveal the competition between maintaining van der Waals bilayer stacking uniformity and dislocation cores required to stitch tilted bilayer GBs together.     

Electronic Doping Controlled Migration of Dislocations in Polycrystalline 2D WS2

Migration of dislocations not only determines the durability of large‐scale nanoelectronic and opto‐electronic devices based on polycrystalline 2D transition‐metal dichalcogenides (TMDCs), but also plays an important role in enhancing the performance of novel memristors. However, a fundamental question of the migration dependence on the electronic effects, which are inevitable in practical field‐effect transistors based on 2D TMDCs, and its interplay with different dislocations, remains unexplored. Here, taking WS₂ as an example, first‐principle calculations are used to show that the electronic contributions arising from defect states can greatly influence the migration barriers of dislocations. The barrier height can be reduced by as much as 50%, which is mainly attributed to the change in electronic occupation and the band energy of defect levels controlled by electronic chemical potential (Fermi level). The reduced barriers in turn lead to significantly enhanced migration, and thus the plasticity. Since defect levels from dislocations locate deep inside the bandgap, the doping‐induced tuning of barrier height can be achieved at relatively low doping concentration through either chemical doping or electrode gating. The effective electromechanical coupling in 2D TMDCs can provide new opportunities in material engineering for various potential applications.     

Charge Transfer Modulation in Vanadium-Doped WS2/Bi2O2Se Heterostructures

The field of photovoltaics is revolutionized in recent years by the development of two–dimensional (2D) type-II heterostructures. These heterostructures are made up of two different materials with different electronic properties, which allows for the capture of a broader spectrum of solar energy than traditional photovoltaic devices. In this study, the potential of vanadium (V)-doped WS₂ is investigated, hereafter labeled V-WS₂, in combination with air-stable Bi₂O₂Se for use in high-performance photovoltaic devices. Various techniques are used to confirm the charge transfer of these heterostructures, including photoluminescence (PL) and Raman spectroscopy, along with Kelvin probe force microscopy (KPFM). The results show that the PL is quenched by 40%, 95%, and 97% for WS₂/Bi₂O₂Se, 0.4 at.% V-WS₂/Bi₂O₂Se, and 2 at.% V-WS₂/Bi₂O₂Se, respectively, indicating a superior charge transfer in V-WS₂/Bi₂O₂Se compared to pristine WS₂/Bi₂O₂Se. The exciton binding energies for WS₂/Bi₂O₂Se, 0.4 at.% V-WS₂/Bi₂O₂Se and 2 at.% V-WS₂/Bi₂O₂Se heterostructures are estimated to be ≈130, 100, and 80 meV, respectively, which is much lower than that for monolayer WS₂. These findings confirm that by incorporating V-doped WS₂, charge transfer in WS₂/Bi₂O₂Se heterostructures can be tuned, providing a novel light-harvesting technique for the development of the next generation of photovoltaic devices based on V-doped transition metal dichalcogenides (TMDCs)/Bi₂O₂Se.     

Recent Progress in CVD Growth of 2D Transition Metal Dichalcogenides and Related Heterostructures

In recent years, 2D layered materials have received considerable research interest on account of their substantial material systems and unique physicochemical properties. Among them, 2D layered transition metal dichalcogenides (TMDs), a star family member, have already been explored over the last few years and have exhibited excellent performance in electronics, catalysis, and other related fields. However, to fulfill the requirement for practical application, the batch production of 2D TMDs is essential. Recently, the chemical vapor deposition (CVD) technique was considered as an elegant alternative for successfully growing 2D TMDs and their heterostructures. The latest research advances in the controllable synthesis of 2D TMDs and related heterostructures/superlattices via the CVD approach are illustrated here. The controlled growth behavior, preparation strategies, and breakthroughs on the synthesis of new 2D TMDs and their heterostructures, as well as their unique physical phenomena, are also discussed. Recent progress on the application of CVD‐grown 2D materials is revealed with particular attention to electronics/optoelectronic devices and catalysts. Finally, the challenges and future prospects are considered regarding the current development of 2D TMDs and related heterostructures.     

Potential 2D Materials with Phase Transitions: Structure,Synthesis, and Device Applications

Layered materials with phase transitions, such as charge density wave (CDW) and magnetic and dipole ordering, have potential to be exfoliated into monolayers and few‐layers and then become a large and important subfamily of two‐dimensional (2D) materials. Benefitting from enriched physical properties from the collective interactions, long‐range ordering, and related phase transitions, as well as the atomic thickness yet having nondangling bonds on the surface, 2D phase‐transition materials have vast potential for use in new‐concept and functional devices. Here, potential 2D phase‐transition materials with CDWs and magnetic and dipole ordering, including transition metal dichalcogenides, transition metal halides, metal thio/selenophosphates, chromium silicon/germanium tellurides, and more, are introduced. The structures and experimental phase‐transition properties are summarized for the bulk materials and some of the obtained monolayers. In addition, recent experimental progress on the synthesis and measurement of monolayers, such as 1T‐TaS₂, CrI₃, and Cr₂Ge₂Te₆, is reviewed.     

Visualizing the Anomalous Charge Density Wave States in Graphene/NbSe2 Heterostructures

Metallic layered transition metal dichalcogenides (TMDs) host collective many-body interactions, including the competing superconducting and charge density wave (CDW) states. Graphene is widely employed as a heteroepitaxial substrate for the growth of TMD layers and as an ohmic contact, where the graphene/TMD heterostructure is naturally formed. The presence of graphene can unpredictably influence the CDW order in 2D CDW conductors. This work reports the CDW transitions of 2H-NbSe₂ layers in graphene/NbSe₂ heterostructures. The evolution of Raman spectra demonstrates that the CDW phase transition temperatures (T_CDW) of NbSe₂ are dramatically decreased when capped by graphene. The induced anomalous short-range CDW state is confirmed by scanning tunneling microscopy measurements. The findings propose a new criterion to determine the T_CDW through monitoring the line shape of the A_1g mode. Meanwhile, the 2D band is also discovered as an indicator to observe the CDW transitions. First-principles calculations imply that interfacial electron doping suppresses the CDW states by impeding the lattice distortion of 2H-NbSe₂. The extraordinary random CDW lattice suggests deep insight into the formation mechanism of many collective electronic states and possesses great potential in modulating multifunctional devices.     

Direct Bandgap Transition in Many‐Layer MoS2 by Plasma‐Induced Layer Decoupling

We report a robust method for engineering the optoelectronic properties of many‐layer MoS₂ using low‐energy oxygen plasma treatment. Gas phase treatment of MoS₂ with oxygen radicals generated in an upstream N₂–O₂ plasma is shown to enhance the photoluminescence (PL) of many‐layer, mechanically exfoliated MoS₂ flakes by up to 20 times, without reducing the layer thickness of the material. A blueshift in the PL spectra and narrowing of linewidth are consistent with a transition of MoS₂ from indirect to direct bandgap material. Atomic force microscopy and Raman spectra reveal that the flake thickness actually increases as a result of the plasma treatment, indicating an increase in the interlayer separation in MoS₂. Ab initio calculations reveal that the increased interlayer separation is sufficient to decouple the electronic states in individual layers, leading to a transition from an indirect to direct gap semiconductor. With optimized plasma treatment parameters, we observed enhanced PL signals for 32 out of 35 many‐layer MoS₂ flakes (2–15 layers) tested, indicating that this method is robust and scalable. Monolayer MoS₂, while direct bandgap, has a small optical density, which limits its potential use in practical devices. The results presented here provide a material with the direct bandgap of monolayer MoS₂, without reducing sample thickness, and hence optical density.