WS2 Crystals Research Articles

Conversion of Layered WS2 Crystals into Mixed-Domain Electrochemical Catalysts by Plasma-Assisted Surface Reconstruction.

Electrocatalytic water splitting is crucial to generate clean hydrogen fuel, but implementation at an industrial scale remains limited due to dependence on expensive platinum (Pt)-based electrocatalysts. Here, an all-dry process to transform electrochemically inert bulk WS2 into a multidomain electrochemical catalyst that enables scalable and cost-effective implementation of the hydrogen evolution reaction (HER) in water electrolysis is reported. Direct dry transfer of WS2 flakes to a gold thin film deposited on a silicon substrate provides a general platform to produce the working electrodes for HER with tunable charge transfer resistance. By treating the mechanically exfoliated WS2 with sequential Ar-O2 plasma, mixed domains of WS2, WO3, and tungsten oxysulfide form on the surfaces of the flakes, which gives rise to a superior HER with much greater long-term stability and steady-state activity compared to Pt. Using density functional theory, ultraefficient atomic sites formed on the constituent nanodomains are identified, and the quantification of atomic-scale reactivities and resulting HER activities fully support the experimental observations.

Growth of tungsten disulfide bilayers featuring Moiré superlattices: A surface energy perspective

The bilayer (BL) transition metal dichalcogenides (TMDs), with their elevated carrier mobility and narrowed bandgap, are advantageous for future electronic applications in comparison with their monolayer (ML) counterparts. Here, we introduce a facile and efficient approach for the chemical vapor deposition synthesis of BL WS2. The method involves an acetic acid sonication treatment to modify the substrate surface morphology and the surface energy, which regulates the nucleation processes and shapes the growth mode of WS2 crystals. Further modifications to the growth conditions yield high-quality ML and BL WS2 films. A comparative study confirms the superior valley polarization and higher carrier mobility of BL WS2 compared with its ML counterpart. Additionally, a minor twist angle existed between the upper and lower layers, featuring a Moiré superlattice. This work reveals the role of surface morphology and surface energy in the growth of TMDs. Simultaneously, it offers insights into the controlled preparation of vertically stacked homo- and heterojunctions.

Defect Passivation of 2D Semiconductors by Fixating Chemisorbed Oxygen Molecules via h-BN Encapsulations.

Hexagonal boron nitride (h-BN) is a key ingredient for various 2D van der Waals heterostructure devices, but the exact role of h-BN encapsulation in relation to the internal defects of 2D semiconductors remains unclear. Here, it is reported that h-BN encapsulation greatly removes the defect-related gap states by stabilizing the chemisorbed oxygen molecules onto the defects of monolayer WS2 crystals. Electron energy loss spectroscopy (EELS) combined with theoretical analysis clearly confirms that the oxygen molecules are chemisorbed onto the defects of WS2 crystals and are fixated by h-BN encapsulation, with excluding a possibility of oxygen molecules trapped in bubbles or wrinkles formed at the interface between WS2 and h-BN. Optical spectroscopic studies show that h-BN encapsulation prevents the desorption of oxygen molecules over various excitation and ambient conditions, resulting in a greatly lowered and stabilized free electron density in monolayer WS2 crystals. This suppresses the exciton annihilation processes by two orders of magnitude compared to that of bare WS2. Furthermore, the valley polarization becomes robust against the various excitation and ambient conditions in the h-BN encapsulated WS2 crystals.

Systematic improvement of excitonic features in hydrothermally synthesized WS2 due to post-synthesis drying

WS2 nanostructures were produced by mechanically exfoliating bulk WS2 powders synthesized through a solution-based hydrothermal route using WCl6 and thioacetamide (TAA) as reactants. An unoptimized post-synthesis recipe, which constitutes the last step, is the major hindrance in achieving a reproducible and scalable production strategy of layered bulk WS2 crystals. We have reported a comprehensive study on the crystal, morphological, and luminescence properties of WS2 material which have undergone post-synthesis treatment i.e. dried at mild temperature with varied dwelling times. The as-synthesized WS2 material which used to be in distorted 1T metallic phase, due to ionic intercalation released from the organic reactants, was found to evolve crystallographically into a stable 2H semiconducting phase with increased drying temperature and dwelling time. An in-depth optical analysis of the WS2 nanostructures through PL and PLE spectroscopy revealed substantial improvement in the intensity of A and B excitonic features for the sample dried at 80 °C for 24 h, indicating a reduction in the non-radiative defect centers in the sample under the post-synthesis conditions. We believe an effective post-synthesis treatment is needed for semiconducting 2H-WS2 synthesis through the solution route to improve its crystal (i.e. structural) and optical properties for potential electronic applications.

Transition Metal Dichalcogenide WS2 Films Prepared with a Combination of Spin/Dip Coating and CVD

Recently, transition metal dichalcogenides (TMDCs) with 2D structure have attracted interest due to their many unique optical and electrical properties. The primary preparation methods for 2D materials are chemical vapor deposition (CVD), exfoliation, and other vacuum technologies. Large-scale synthesis of WS2 via solution-process is rare due to the higher temperature needed for tungsten-based precursors. Combination of spin coating or dip coating with CVD have been studied recently to make large-area 2D TMDC with good electrical properties. Here, we report a new synthetic route for large WS2 crystal that combined solution coatings and CVD process. A solution of sodium tungstate and hydrazine hydrate with sodium thiosulphate was coated on a silicon wafer via dip and spin coating. The films were then treated with CVD at various positions and temperatures to facilitate crystallization. The double coating conditions and CVD parameters were modified to obtain WS2 crystals. Triangular shaped 44 ± 4 µm WS2 crystals could be obtained with simple annealing above 900oC without gas treatment. The synthesized WS2 was found to be bulk with a triangular shape, as confirmed by Raman and AFM analyses. A PL peak of WS2 at 643 nm was observed at an early crystallization stage.

Negative-mass exciton polaritons induced by dissipative light-matter coupling in an atomically thin semiconductor

Dispersion engineering is a powerful and versatile tool that can vary the speed of light signals and induce negative-mass effects in the dynamics of particles and quasiparticles. Here, we show that dissipative coupling between bound electron-hole pairs (excitons) and photons in an optical microcavity can lead to the formation of exciton polaritons with an inverted dispersion of the lower polariton branch and hence, a negative mass. We perform direct measurements of the anomalous dispersion in atomically thin (monolayer) WS2 crystals embedded in planar microcavities and demonstrate that the propagation direction of the negative-mass polaritons is opposite to their momentum. Our study introduces the concept of non-Hermitian dispersion engineering for exciton polaritons and opens a pathway for realising new phases of quantum matter in a solid state.

Effect of organic phosphorus addition on the state of active metal species and catalytic performance of NiW/Al2O3 hydrodesulfurization catalyst

This article proposes a novel organic additive 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) for the preparation of NiW/Al2O3 efficient hydrodesulfurization (HDS) catalysts. The effects of HEDP on the nature of the tungsten and nickel species supported on the support surface after drying and calcination steps were revealed by employing ultraviolet–visible spectroscopy (UV–Vis), Raman spectroscopy, N2 adsorption–desorption and H2 temperature programmed reduction (H2-TPR). While the slab morphology and the proportion of NiWS phases were determined by X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM). Finally, dibenzothiophene (DBT) was used as a probe to evaluate the effects of HEDP modification on the catalytic performance of the prepared catalyst. The results indicate that the addition of HEDP can facilitate the formation of more polymerized tungsten oxide species and improve the availability of surface nickel atoms. The weakened interaction between active metals and support generate higher stacking numbers and shorter slab lengths among WS2 crystals on the corresponding catalyst, promote the sulfidation of both Ni and W species and enhance the proportion of NiWS phase. The catalytic evaluation results show that the HEDP-modified catalyst exhibits efficient HDS activity and higher DDS selectivity compared to the phosphoric acid-modified reference catalyst, which is attributed to a large number of accessible NiWS active sites. The present work relates the addition of organic additives with the formation of NiW species and the catalytic activity. The results highlight that the addition of HEDP is an effective strategy to improve the performance of HDS catalysts.

Ultrashort channel chemical vapor deposited bilayer WS2 field-effect transistors

Two-dimensional transition metal dichalcogenides (TMDs) are potential candidates for next generation channel materials owing to their atomically thin structure and high carrier mobility, which allow for the ultimate scaling of nanoelectronics. However, TMDs-based field-effect transistors are still far from delivering the expected performance, which is mainly attributed to their high contact resistance and low saturation velocity (vsat). In this work, we report high-performance short-channel WS2 transistors based on bandgap engineering. The bilayer WS2 channel not only shows a higher average field-effect mobility (μFE) than the monolayer channel but also exhibits excellent metal-Ohmic contact using a regular physical vapor deposition deposited Ni/Au contact, reducing the Rc value to a record low value of 0.38 kΩ · μm without any intentional doping. The bilayer WS2 device of the 80 nm channel exhibits a high on-state current of 346 μA/μm at Vds = 1 V, near-zero drain-induced barrier lowering, and a record high Ion/Ioff ratio over 109. Furthermore, a record high on-state current of 635 μA/μm at Vds = 1 V and a record high vsat of 3.8 × 106 cm/s have been achieved for a shorter 18 nm channel device, much higher than previous WS2 transistors. This work reveals the intrinsically robust nature of bilayer WS2 crystals with promising potential for integration with conventional fabrication processes.

Real-Time Diagnostics of 2D Crystal Transformations by Pulsed Laser Deposition: Controlled Synthesis of Janus WSSe Monolayers and Alloys

Energetic processing methods such as hyperthermal implantation hold special promise to achieve the precision synthesis of metastable two-dimensional (2D) materials such as Janus monolayers; however, they require precise control. Here, we report a feedback approach to reveal and control the transformation pathways in materials synthesis by pulsed laser deposition (PLD) and apply it to investigate the transformation kinetics of monolayer WS2 crystals into Janus WSSe and WSe2 by implantation of Se clusters with different maximum kinetic energies (<42 eV/Se-atom) generated by laser ablation of a Se target. Real-time Raman spectroscopy and photoluminescence are used to assess the structure, composition, and optoelectronic quality of the monolayer crystal as it is implanted with well-controlled fluxes of selenium for different kinetic energies that are regulated with in situ ICCD imaging, ion probe, and spectroscopy diagnostics. First-principles calculations, XPS, and atomic-resolution HAADF STEM imaging are used to understand the intermediate alloy compositions and their vibrational modes to identify transformation pathways. The real-time kinetics measurements reveal highly selective top-layer conversion as WS2 transforms through WS2(1-x)Se2x alloys to WSe2 and provide the means to adjust processing conditions to achieve fractional and complete Janus WSSe monolayers as metastable transition states. The general approach demonstrates a real-time feedback method to achieve Janus layers or other metastable alloys of the desired composition, and a general means to adjust the structure and quality of materials grown by PLD, addressing priority research directions for precision synthesis with real-time adaptive control.

Photoelectric properties of pristine and niobium-doped tungsten disulfide layered crystals

Tungsten disulfide (WS2) is a transition-metal dichalcogenide that is suited to next-generation electronic and optoelectronic devices. Doping is necessary for WS2 applications because it allows the inherent characteristics of WS2 to be tuned to increase its functionality. This study determines the effect of niobium (Nb) doping on the photoelectric properties of WS2 crystals. A chemical vapor transport process is used to grow pristine and Nb-doped WS2 crystals. Scanning electron microscopy images show that the WS2 specimens consist of layered crystals. The photoresponsivity of the samples increases as the incident laser power decreases. Nb-doped WS2 crystals are 92 times more photoresponsive than pristine WS2 crystals at a laser power of 2 × 10−8 W. The ratio of the normalized photocurrent for a Nb-doped sample to that for a pristine sample increases as the frequency of the illumination increases to a maximum value of 11.5 at 104 Hz. Time-dependent photocurrent measurements show that the rise and fall times for Nb-doped WS2 crystals are shorter than those for pristine WS2 crystals by at least an order of magnitude. The results of this study show that Nb doping significantly increases the optical response of WS2 crystals.

Nucleation and growth mechanism for atomic layer deposition of Al2O3 on two-dimensional WS2 monolayer

Nanoelectronics holds significant promise for two-dimensional (2D) semiconducting transition metal dichalcogenide (TMD) applications. On a polycrystalline WS2 monolayer created by metal-organic chemical vapor deposition (MOCVD) at 950 °C, we studied the nucleation, growth, and development of Al2O3 atomic layer deposition (ALD) on a SiO2/Si substrate. In this investigation, we used various complementary characterization methods, such as Raman spectroscopy, elastic recoil detection, atomic force microscopy, and time-of-flight secondary ion mass spectrometry, to understand thoroughly the intrinsic reactivity of WS2. Strong peak intensity changes at the interfaces in the Raman line scans of the SiO2/Si patterns suggest extremely crystalline WS2. After multiple ALD cycles, triangular WS2 crystals were decorated to provide a two-dimensional growth mode with a great selectivity for grain boundaries and step edges. The results of this work can be used for further exploration of the TMD monolayer structure and properties, which is essential for tailoring 2D materials for a specific application in devices.

Nonvolatile Electrical Valley Manipulation in WS2 by Ferroelectric Gating.

Valleytronics in transition metal dichalcogenides has been intensively investigated for potential applications in next-generation information storage, data processing, and signal transmission devices. Here a ferroelectric gating approach is engaged in achieving nonvolatile electrical tuning of the valley-excitonic properties of monolayer and bilayer WS2. The gating effects include carrier doping and ferroelectric coupling, which are further distinguished by comparing two geometries where the gate electrodes are in direct contact with or insulated from the WS2 crystal. The results show that the carrier doping from gate electrodes acts on WS2 through carrier screening, which only moderately alters the valley polarization. In contrast, the ferroelectric gating promotes electron-phonon interaction, introduces a strong surface polarization field, and controls the interfacial charge trapping/detrapping, causing a Stark shift in exciton energy and strongly enhancing room-temperature valley polarization. In bilayer WS2, the intralayer-interlayer exciton transition is further induced, contributing to even higher valley polarization. The ferroelectric coupling effect can still be maintained after the removal of gate voltage, showing its nonvolatile nature. The role of ferroelectricity is further verified by the anomalous temperature dependence in valley polarization. This work has revealed effective electrical control over valley excitons in semiconductors through interaction with ferroelectric materials. The reported high room-temperature valley polarization in WS2 will boost the development of valleytronics devices.

A Capillary-Force-Assisted Transfer for Monolayer Transition-Metal-Dichalcogenide Crystals with High Utilization.

The capillary-force-assisted transfer has shown application potential for constructing two-dimensional (2D) electronic and optoelectronic devices for the advantage of free of spin coating the organic compound and etching the substrate. Currently, the transfer mechanism remains obscure. The capillary adhesion mechanism and capillary invasion separation mechanism were proposed independently and rarely discussed in a comprehensive manner. What is more, the integrity and utilization remain to be improved. Here, we developed the capillary-force-assisted transfer method with high utilization and integrity. Uniformity of water transport was improved by introducing water from the sidewall of the small polydimethylsiloxane (PDMS) stamp driven by capillary force. The transfer integrity rate increased, and the location of the complete samples became predictable. The transfer utilization increased as the limited water transportation minimized the impact on the surrounding WS2. The monolayer triangle WS2 crystals from adjacent areas on the sapphire substrate were transferred one after another. Besides, local mechanical exfoliation of the continuous WS2 thin films was demonstrated, implying that the capillary adhesion is strong enough to break the strong in-plane covalent bond and overcome the van der Waals force between WS2 and sapphire substrate. Finally, the water transport model between two surfaces with different hydrophobicity combinations was derived on the basis of the Young-Laplace equation. The analysis of water transport between different interfaces reveals how capillary adhesion and capillary invasion work together to achieve capillary force transfer. This study highlights the potential of the capillary-force-assisted transfer as an efficient technique for fabricating van der Waals structures based on two-dimensional atomic crystals, especially periodic structures.

Fabrication of near-invisible solar cell with monolayer WS2

Herein, we developed a near-invisible solar cell through a precise control of the contact barrier between an indium tin oxide (ITO) electrode and a monolayer tungsten disulfide (WS2), grown by chemical vapor deposition (CVD). The contact barrier between WS2 and ITO was controlled by coating various thin metals on top of ITO (Mx/ITO) and inserting a thin layer of WO3 between Mx/ITO and the monolayer WS2, which resulted in a drastic increase in the Schottky barrier height (up to 220 meV); this could increase the efficiency of the charge carrier separation in our Schottky-type solar cell. The power conversion efficiency (PCE) of the solar cell with the optimized electrode (WO3/Mx/ITO) was more than 1000 times that of a device using a normal ITO electrode. Large-scale fabrication of the solar cell was also investigated, which revealed that a simple size expansion with large WS2 crystals and parallel long electrodes could not improve the total power (PT) obtained from the complete device even with an increase in the device area; this can be explained by the percolation theory. This problem was addressed by reducing the aspect ratio (width/channel length) of the unit device structure to a value lower than a critical threshold. By repeating the experiments on this optimized unit device with an appropriate number of series and parallel connections, PT could be increased up to 420 pW from a 1-cm2 solar cell with a very high value (79%) of average visible transmission (AVT).

Probing the long-lived photo-generated charge carriers in transition metal dichalcogenides by time-resolved microwave photoconductivity

Abstract Understanding the dissociation of excitons into long-lived free charge carriers is a crucial issue when considering the applications of transition metal dichalcogenides (excitonic semiconductors) oriented toward the use of solar energy (such as photovoltaics or photocatalysis). In our work, long-lived carriers have been observed by time-resolved microwave photoconductivity (TRMC) for the first time in both atomically thin and bulk MoS2, MoSe2, WS2, and WSe2 crystals. The lifetime of majority carriers is close to microseconds and can even reach several microseconds due to different contribution of surface and defect states, as well as surface band bending (bulk). The three components depend on the material and vary from sample to sample, therefore determining the dynamics of the TRMC signal. The rise time of TRMC signal was found to be in the range of 0.1–0.2 μs and as it depends on the studied material it can be speculated that it is related to the dissociation time of excitons captured by traps.

Interactive effect between WS2 films with different structures and space oils for improvement of tribological performance

WS2 films with different structures and space lubricating oils are combined to construct the WS2/oils composite lubricating systems. Friction and wear of the WS2/oils systems are mainly studied in vacuum. Results show that WS2/P201 systems display much lower friction coefficient (μ ≈ 0.06) than WS2/PFPE systems (μ ≈ 0.11), which is found to depend on lubricity of oils. Noteworthily, the dense WS2 film of the WS2/PFPE systems has the lowest wear rate of about 5.6 × 10−6 mm3·(N·m)−1 although friction coefficient of the system is high. This is due to good wettability of PFPE on the dense WS2 film, whose contact angle is low to 5°. Eventually, the lubricating mechanism of the WS2/oil systems are revealed via correlating interaction between oil molecules and WS2 crystals.

Growth and Optoelectronic Properties of Large-Scale Bilayer WS2 Ribbons with Unusual Shapes via Chemical Vapor Deposition

Atomically thin transition metal dichalcogenides (TMDCs) have attracted worldwide interest for their prospective potential in electronic and optoelectronic fields. However, TMDCs tend to grow into two-dimensional (2D) flakes rather than one-dimensional (1D) micro/nanoribbons due to their intrinsic layered structure. Here, large-scale bilayer WS2 ribbons with unusual shapes have been achieved through the space-confined chemical vapor deposition method via utilizing WO3 and S powders as the precursors. The microstructures and optical and electronic properties of as-grown bilayer WS2 ribbons have been systematically researched. Moreover, the possible growth mechanism of such special structures is revealed by the growth-time-dependent morphological evolution of the WS2 crystals. Our results emphasize the prospects for the successful fabrication of novel 1D TMDC structures for high-performance optoelectronic devices at nanoscale, including transistors, photocatalysts, photovoltaic cells, and spintronic devices.

A facile strategy for the growth of high-quality tungsten disulfide crystals mediated by oxygen-deficient oxide precursors.

Chemical vapor deposition (CVD) has been established as a versatile route for the large-scale synthesis of transition metal dichalcogenides, such as tungsten disulfide (WS2). Yet, the precursor composition's role on the CVD process remains largely unknown and remains to be explored. Here, we employ Pulsed Laser Deposition (PLD) in a two-stage approach to tune the oxygen content in the tungsten oxide (WO3-x) precursors and demonstrate the presence of oxygen vacancies in the oxide films leads to a more facile conversion from WO3-x to WS2. Using a joint study based on ab initio density functional theory (DFT) calculations and experimental observations, we unravel that the oxygen vacancies in WO3-x can serve as niches through which sulfur atoms enter the lattice and facilitate an efficient conversion into WS2 crystals. By solely modulating the precursor stoichiometry, the photoluminescence emission of WS2 crystals can be significantly enhanced. Atomic resolution scanning transmission electron microscopy imaging (STEM) reveals that tungsten vacancies are the dominant intrinsic defects in mono- and bilayers WS2. Moreover, bi- and multilayer WS2 crystals derived from oxides with a high V0 content exhibit dominant AA'/AB or AA(A…) stacking orientations. The atomic resolution images reveal local strain buildup in bilayer WS2 due to competing effects of complex grain boundaries. Our study provides means to tune the precursor composition to control the lateral growth of TMDs while revealing insights into the different pathways for forming grain boundaries in bilayer WS2.

Formation of nanostructured films based on MoS-=SUB=-2-=/SUB=-, WS-=SUB=-2-=/SUB=-, MoO-=SUB=-2-=/SUB=- and their heterostructures

In this work thin film coatings based on WS2, MoS2, MoO2 and their composites were synthesized, morphological and structural properties of deposited coatings were studied. Chemical vapor deposition with heated MoO3, WO3, S powder as precursors was used. Dependence of structural and morphological properties, chemical composition of deposited films on parameters of synthesis was defined. Films of vertically aligned 10 nm thick plate crystals consisting both of pure MoO2 and MoO2 covered with thin MoS2 layer were obtained. Formation of polycrystalline films of regular triangular shaped WS2 and uniform continuous 20 nm thick WS2 films with covering area of 2x2 mm has also been observed. In this work we also report about synthesis of films consisting of regular triangular shaped WS2 crystals and MoS2 irregularly shaped crystals overlapping each other. Keywords: 2D materials, transition metal dichalcogenides, heterostructures, CVD, AFM.

Dual-coupling-guided epitaxial growth of wafer-scale single-crystal WS2 monolayer on vicinal a-plane sapphire.

The growth of wafer-scale single-crystal two-dimensional transition metal dichalcogenides (TMDs) on insulating substrates is critically important for a variety of high-end applications1-4. Although the epitaxial growth of wafer-scale graphene and hexagonal boron nitride on metal surfaces has been reported5-8, these techniques are not applicable for growing TMDs on insulating substrates because of substantial differences in growth kinetics. Thus, despite great efforts9-20, the direct growth of wafer-scale single-crystal TMDs on insulating substrates is yet to be realized. Here we report the successful epitaxial growth of two-inch single-crystal WS2 monolayer films on vicinal a-plane sapphire surfaces. In-depth characterizations and theoretical calculations reveal that the epitaxy is driven by a dual-coupling-guided mechanism, where the sapphire plane-WS2 interaction leads to two preferred antiparallel orientations of the WS2 crystal, and sapphire step edge-WS2 interaction breaks the symmetry of the antiparallel orientations. These two interactions result in the unidirectional alignment of nearly all the WS2 islands. The unidirectional alignment and seamless stitching of WS2 islands are illustrated via multiscale characterization techniques; the high quality of WS2 monolayers is further evidenced by a photoluminescent circular helicity of ~55%, comparable to that of exfoliated WS2 flakes. Our findings offer the opportunity to boost the production of wafer-scale single crystals of a broad range of two-dimensional materials on insulators, paving the way to applications in integrated devices.