Transition Metal Dichalcogenides Family Research Articles

Bottom-up Synthesis of Highly Chiral 1T Molybdenum Disulfide Nanosheets.

Chirality in inorganic nanostructures has recently stimulated the attention of many researchers, both to unravel fundamental questions on the origin of chirality in inorganic and hybrid materials, as well as to introduce novel promising properties that are originated by the symmetry breaking. MoS2 is one of the most investigated among the large family of layered transition metal dichalcogenides. In particular, the metastable metallic 1T-MoS2 phase is of large interest for potential applications. However, due to thermodynamic reasons, the synthesis of 1T-MoS2 phase is quite challenging. Herein, we present the first synthesis of chiral 1T-MoS2 phase which shows remarkably high chiroptical activity with a g-factor up to 0.01. Chiral 1T-MoS2 was produced using tartaric acid as a chiral ligand to induce symmetry breaking during the material's growth under hydrothermal conditions, leading to the formation of distorted hierarchical nanosheet assemblies exhibiting chiral morphology. Thorough optimization of the synthetic conditions was carried out to maximize chiroptical activity, which is strongly related to the nanostructures' morphology. Finally, the formation mechanism of the chiral 1T-MoS2 nanosheet assemblies was investigated, focusing on the role of molecular intermediates in the growth of the nanosheets and the transfer of chirality.

Enhanced Hydrogen Evolution Reaction Activity through Bimetallic Phosphide Integration in ReS2/Re2O7 Heterostructure

AbstractDeveloping a nonprecious and sustainable electrocatalyst in clean energy generation is quite noteworthy. Transition metal chalcogenides, oxides, and phosphides have emerged as promising candidates to substitute Pt‐based catalysts. In this study, we explore the catalytic potential of ReS2, a promising member of the transition metal dichalcogenides (TMD) family, for hydrogen evolution reactions (HER). The formation of rhenium oxide during the synthesis of ReS2 and further incorporation of a bimetallic phosphide NiCuP in a sequential hydrothermal synthesis reveals an excellent HER activity, as demonstrated by photoelectrochemical and electrochemical studies. Notably, the catalyst exhibits a significantly lower overpotential of −0.10 V (corresponding to −10 mA/cm2) and achieves a high current density of approx. −271 mA/cm2 at −0.79 V versus reversible hydrogen electrode (RHE) under light irradiation. The catalyst demonstrates high stability. These findings underscore the potential of NiCuP‐integrated ReS2/Re2O7 as a highly efficient and sustainable catalyst for HER.

Janus Doping of Sulfur into Platinum Diselenide Ribbons.

2D platinum diselenide (PtSe2), a novel member of the transition metal dichalcogenides (TMDCs) family, possesses many excellent properties, including a layer-dependent bandgap, high carrier mobility, and broadband response, making it promise for applications in technologies like field-effect transistors and room-temperature photodetectors. Doping represents an effective method to modify the electrical properties of 2D TMDCs and to bestow upon them additional functions. However, to date, little research has been conducted on the successful doping of 2D PtSe2 for modification. In this study, sulfur (S) powder is utilized during the chemical vapor deposition growth process of 2D PtSe2 ribbons and successfully integrated into the PtSe2 lattice through substitutional doping. The Au substrate significantly decreases the substitution energy of Se atoms in the lower layer of PtSe2, resulting in the formation of the Janus PtSSe structure. S-doped PtSe2 ribbons demonstrate significant symmetry breaking and enhanced electrical properties, showcasing a strong nonlinear optical response and certain synaptic plasticity, further simulating some neuromorphological processes. This study not only demonstrates a viable method for controllable doping and modification of 2D PtSe2 but also establishes a platform for exploring the characteristics of Janus TMDCs.

Nanotubes and other nanostructures of VS2, WS2, and MoS2: Structural effects on the hydrogen evolution reaction

Vanadium sulfide (VS2) is a layered transition metal dichalcogenide (TMD), comparable in crystal structure to the well-known MoS2 and WS2. Theoretical predictions attribute much potential to VS2, since it is metallic-like and has an active basal plane, essential for catalytic performance. However, it is much less studied than other members of the TMD family due to the difficulties in synthesizing specific structures with controlled properties. Here we present unique structures of VS2 nanotubes and conduct a comparative study with other well-known inorganic nanotubes and nanostructures of MoS2 and WS2. We evaluate the effect of the curvature and strain, the abundance of surface defects, and the availability of surface sites in various structures by electrochemical methods. We show that MoS2 has the best intrinsic activity, which is enhanced by an extensive electrochemical surface area. The woven-like structure of the MoS2 nanotube walls provides a combined effect of strain, crystallinity, and defects. For WS2 structures, the strained surface of the nanotubes results in sites with higher intrinsic activity than the edge sites, but structures such as the nano-triangles, which provide a higher number of edge sites, exhibit competing activity. As for the VS2 structures, although theoretical calculations predict optimal active sites for the hydrogen evolution reaction (HER), they are extremely sensitive to stoichiometry variations that hamper their catalytic activity. Our findings contribute insights to the improvement and design of VS2–based nanocatalysts for the HER and shed light on the general factors that govern the activity in the unique TMD nanotubes family.

Interface engineering of tungsten disulfide by incorporating chromium nitride interfacial layer for hybrid supercapacitors

By confronting the ongoing challenges of energy storage after generation, a unique technology referred to as hybrid energy storage systems appears as a potential solution for energy storage applications. In hybrid supercapacitors, optimizing the electrode characteristics by precise interface engineering greatly improves performance, supporting the device's stability and ability to store charge. The focus of this research is on the interface engineering of tungsten disulfide from the family of transition metal dichalcogenides by the incorporation of chromium nitride interfacial layer of 100 nm on 1 cm2 substrate via magnetron sputtering. The structural characteristics of the resulting samples were acquired using SEM, XRD, Raman, and EDX. The study further employed the half-cell assembly for exploring the electrochemical performance of pure WS2 and WS2 with CrN interfacial layer. The enhanced composition of WS2/CrN was then used as a working electrode alongside activated carbon in a hybrid supercapacitor arrangement. The device reveals a specific capacity, capacitance, power and energy density of 348 C/g, 481.3 F/g, 4250 W/kg and 82.6 Wh/kg, respectively along with capacity retention of 89 % after 10,000 GCD cycles. Following this, the device's performance was evaluated using a semi-empirical approach, comparing capacitive and diffusive mechanisms from linear and quadratic models to study battery-supercapacitor hybrids.

Revealing 1T-MoS2 with 76 % purity induced by various saccharides for supercapacitor performance

The preparation of metallic phase molybdenum disulfide (1T-MoS2) through an implementable method has become a top priority in research due to its excellent electrochemical performance. In this study, 1T-MoS2 using a facile one-pot hydrothermal method is successfully synthesized by incorporating saccharides. Moreover, a comprehensive understanding of the synthesis mechanism is induced by various saccharides. Glucose, a monosaccharide, not only possesses reducibility but also plays a crucial role in preparation of sulfur vacancies. Maltose is a disaccharide that can hydrolyze into glucose and fructose, both of which exhibit reducibility. On the contrary, dextrin is difficult to break down into fructose or glucose, and faces certain challenges in promoting the formation of 1T-MoS2. Importantly, 1T-MoS2 with 76 % purity obtained in our study exhibits exceptional electrochemical performance, demonstrating a high specific capacitance of 228.4 F g−1 at 2 A g−1 and maintaining a cycling stability of 97 % after 10,000 cycles. Furthermore, an asymmetric flexible supercapacitor device is assembled by 1T-MoS2 and active carbon on carbon cloths, which shows superior flexibility, high power density, and energy density. Notably, this work not only unveils the mechanism by which saccharides influence the synthesis of 1T-MoS2 but also provides support for the preparation of other metallic members in the transition metal dichalcogenides (TMDs) family.

Nano tumbleweed-like tungsten disulfide as a viable surrogate for platinum counter electrodes in dye-sensitized solar cells

Tungsten disulfide (WS2), a notable member of the transition metal dichalcogenides family, has emerged as a promising candidate for energy storage and conversion applications. In this study, WS2 was synthesized via a hydrothermal method using sodium tungstate and thiourea as precursor materials, with hydroxylamine hydrochloride as the reducing agent and cetyl trimethyl ammonium bromide as a surfactant. The primary objective was to develop a cost-effective, easily synthesized, and scalable material capable of replacing platinum (Pt) in dye-sensitized solar cells (DSSCs), where Pt is both prohibitively expensive and scarce. Characterization of the synthesized WS2 was conducted through a range of physical analyses, including SEM, TEM, XRD, EDAX, FTIR, and Raman spectroscopy, which provided compelling evidence for the formation of a unique nano-tumbleweed-like structure of WS2. When used as a counter electrode (CE), the synthesized WS2 exhibited exceptional photocatalytic activity, resulting in a commendable power conversion efficiency (PCE) of 12.06 % when coupled with fluorine-doped tin oxide (FTO) plates coated with TiO2 as the photoanode, N719 as the dye, and Iˉ/I3ˉ as the liquid electrolyte. Additionally, the fabricated device underwent comprehensive electrical characterization, including cyclic voltammetry (CV), current-voltage (IV) measurements, electrochemical impedance spectroscopy (EIS), and Tafel analysis, revealing properties similar to those of Pt counter electrodes. Notably, WS2 demonstrated an open-circuit potential of 852 mV and a short-circuit current density of 28 mA/cm2, accompanied by a fill factor of 0.43 and a commendable lifetime of 15.92 ms.

Electronic phase transformations and energy gap variations in uniaxial and biaxial strained monolayer VS[formula omitted] TMDs: A comprehensive DFT and beyond-DFT study

In the rapidly evolving field of 2D materials, transition metal dichalcogenides (TMDs) have emerged as compelling candidates for electronic applications. This study investigates the electronic structure of the H-phase monolayer VS2 belonging to TMD family and the influence of strain on its band structure through Density Functional Theory (DFT). We employ two different pseudopotential approximations and a suite of computational methods including DFT+U, GAUPBE, G0W0, and self-GW to provide a nuanced understanding of its electronic band structure. A highlight of the study is its focus on how both uniaxial and biaxial strains, ranging from -5% to +5%, affect the electronic properties of the H-phase monolayer VS2. Our comprehensive analysis reveals that these tensile strains significantly widen the energy gap, with uniaxial strains having a more pronounced effect than their biaxial counterparts. Additionally, we identify an intriguing phase transition from a semiconducting to a metallic state under compressive strains, this transition is attributed to both symmetry breaking and bond length variation in the uniaxial case, the bond length in biaxial. These key findings not only enrich our understanding of the intricate electronic behavior of monolayer VS2 under different strains but also pave the way for the design of innovative electronic devices using strain engineering.

Study on pH dependent ON/OFF fluorescent switching behaviour of hydrothermally synthesised vanadium disulphide quantum dots (VS2-QDs)

It is fascinating to design and develop an inorganic quantum dot (QDs) which exhibit luminescence features with ion concentration, temperature, and pH sensitivity dependence. Vanadium disulphide (VS2) belongs to the family of transition metal dichalcogenides (TMDs), and is extensively studied owing to its layered characteristics features in sensing and filtrations technology, however, its fluorescence features have not been well studied so far. The current work describes a widely adopted eco-friendly hydrothermal approach for the synthesis of VS2-QDs. The average size of particles was determined to be ∼10 nm by transmission electron microscopy (TEM) and Zetasizer analysis. The synthetic approach adopted here facilitates in situ functionalization of QDs, which results in their high stability in aqueous medium and enhanced sensitivity towards their surroundings. As most of the QDs show the sensitivity towards pH, a thorough investigation of VS2 QDs for their pH dependent photoluminescence has been carried out. The VS2-QDs were discovered to exhibit a remarkable luminescence intensity that was found to be about 11 times higher in basic conditions (pH ∼ 13, QY = ∼4.80 %) as compared to that in acidic conditions (pH ∼ 1, QY = ∼1.10 %). The root cause of this ON/OFF florescence flipping may be related to the functional groups (such as −SO42−, −NH2, OH−, etc.) attached over the surface of QDs, acid etching, and protonation–deprotonation process. This paper highlights the pH dependent switching behaviour of VS2-QDs that could offer valuable information for designing a futuristic pH-based device for biomedical applications.

A comparative study on 2D materials with native high-[formula omitted] oxides for sub-10 nm transistors

Two-dimensional (2D) transition metal dichalcogenides (TMDs) with native high-κ oxides have presented a new avenue towards the development of next-generation ultra-scaled field-effect transistors (FETs). These materials have been experimentally shown to form a natively compatible oxide layer with a high dielectric constant, which can help scale down both the transistor size and the supply voltage. We present a material and device performance study into the use of several of these materials – namely HfS2, HfSe2, ZrS2, ZrSe2 – as channels in sub-10 nm FETs. All four materials exhibit isotropic transport at 10 nm channel length with ON currents over 1000 μA/μm but show anisotropic transport and degraded ON currents at 5 nm channel length. In general, the sulfide family excels in terms of subthreshold characteristics at sub-10 nm channel lengths. HfS2, in particular, surpasses all the other materials in terms of ON currents and subthreshold swing (SS), allowing it to also achieve excellent intrinsic performance. We have identified HfS2 as a superior material within this TMD family for sub-10 nm FETs.

Unveiling the orbital-selective electronic band reconstruction through the structural phase transition in TaTe2

Tantalum ditelluride (TaTe2) belongs to the family of layered transition metal dichalcogenides but exhibits a unique structural phase transition at around 170 K that accompanies the rearrangement of the Ta atomic network from a “ribbon chain” to a “butterfly-like” pattern. While multiple mechanisms including Fermi surface nesting and chemical bonding instabilities have been intensively discussed, the origin of this transition remains elusive. Here we investigate the electronic structure of single-crystalline TaTe2 with a particular focus on its modifications through the phase transition, by employing core-level and angle-resolved photoemission spectroscopy combined with first-principles calculations. Temperature-dependent core-level spectroscopy demonstrates a splitting of the Ta 4f core-level spectra through the phase transition indicative of the Ta-dominated electronic state reconstruction. Low-energy electronic state measurements further reveal an unusual kink-like band reconstruction occurring at the Brillouin zone boundary, which cannot be explained by Fermi surface nesting or band-folding effects. On the basis of the orbital-projected band calculations, this band reconstruction is mainly attributed to the modifications of specific Ta 5d states, namely, the dXY orbitals (the ones elongating along the ribbon chains) at the center Ta sites of the ribbon chains. The present results highlight the strong orbital-dependent electronic state reconstruction through the phase transition in this system and provide fundamental insights towards understanding complex electron-lattice-bond coupled phenomena. Published by the American Physical Society 2024

Room-Temperature Strong Coupling of Few-Exciton in a Monolayer WS2 with Plasmon and Dispersion Deviation.

Engineering room-temperature strong coupling of few-exciton in transition-metal dichalcogenides (TMDCs) with plasmons promises to construct compact and high-performance quantum optical devices. But it remains unimplemented due to their in-plane excitons. Here, we demonstrate the strong coupling of few-exciton within 10 in monolayer WS2 with the plasmonic mode with a large tangential component of the electric field tightly trapped around the sharp corners of an Au@Ag nanocuboid, the fewest number of excitons observed in the TMDC family so far. Furthermore, we for the first time report a significant deviation with a relative difference of up to 100.6% between the spectrum and eigenlevel splitting dispersions, which increases with decreasing coupling strength. It is also shown that the coupling strength obtained by the conventional concept of both being equal to the measured spectrum splitting is markedly overestimated. Our work enriches the understanding of strong light-matter interactions at room temperature.

Emergence of superconductivity by intercalation of alkali metals and alkaline earth metals in Janus transition-metal dichalcogenide heterostructures.

Superconductivity in two-dimensional materials has attracted considerable attention. A new material belonging to the family of Janus transition metal dichalcogenides with out-of-plane structural asymmetry has been recently found to show interesting physical and chemical properties. Using density functional theory and density functional perturbation theory, within the generalized gradient approximation with van der Waals correction, we performed a detailed investigation of the electronic structure, phonon dispersion, Eliashberg spectral function, and electron-phonon coupling of Janus MSSe bilayers (M = Mo or W) and the Janus MoSSe/WSSe heterostructure intercalated with alkali metals (Li, Na, and K) or alkaline earth metals (Mg, Ca, and Sr). We found that the Janus MoSSe bilayer, Janus WSSe bilayer, and Janus MoSSe/WSSe heterostructure transform from a direct band gap semiconductor to a metal or semimetal due to charge transfer from intercalated atoms to the Se and S planes. We showed that all compounds are dynamically stable conventional superconductors. In addition, the Janus heterostructure MoSSe/WSSe intercalated with K exhibits the highest electron-phonon coupling of about 2.12 and the highest superconducting transition temperature of about 14.77 K. Our results indicate the potential application of the Janus materials we investigated in superconductivity.

Enhanced photocatalytic performance of SnS2 under visible light irradiation: strategies and future perspectives.

Tin(II) sulfide (SnS2) has emerged as a promising candidate for visible light photocatalytic materials. As a member of the transition metal dichalcogenides (TMDs) family, SnS2 features a band gap of approximately 2.20 eV and a layered structure, rendering it suitable for visible light activation with a high specific surface area. However, the application of SnS2 as a visible light photocatalyst still requires improvement, particularly in addressing the high recombination of electrons and holes, as well as the poor selectivity inherent in its perfect crystal structure. Therefore, ongoing research focuses on strategies to enhance the photocatalytic performance of SnS2. In this comprehensive review, we analyze recent advances and promising strategies for improving the photocatalytic performance of SnS2. Various successful approaches have been reported, including controlling the reactive facets of SnS2, inducing defects in the crystal structure, manipulating morphologies, depositing noble metals, and forming heterostructures. We provide a detailed understanding of these phenomena and the preparation techniques involved, as well as future considerations for exploring new science in SnS2 photocatalysis and optimizing performance.

Vacancy-mediated inelasticity in two-dimensional vanadium-based dichalcogenides.

Amongst the two-dimensional (2D) transition metal dichalcogenide (TMDC) family, VX2 (X = S, and Se) are key members for next-generation electronic, spintronic, and energy storage applications. Structural defects may be introduced in these emerging atomically thin materials during synthesis, which can lead to both desirable and detrimental impacts on the physical and chemical properties. Owing to their brittle behaviour, defects may deteriorate the mechanical properties of 2D TMDCs drastically, causing reliability-related issues critical for long-term device-scale applications. In this context, more than 1600 classical molecular dynamics simulations were performed to obtain estimates of chirality-dependent failure stresses of 2D VX2 under technologically relevant conditions that are encountered in typical industrial and lab-scale experiments. The energy barriers associated with the fracture of defective samples were calculated using a thermal activation-based analytical model. Furthermore, the effect of various concentrations of randomly distributed defects on the mechanical reliability of VX2 samples was explored using two-parameter Weibull statistics. These monolayers were found to possess strong flaw tolerance and high Weibull modulus values, making them promising for flexible electronics and energy storage.

Fourier‐Transform Infrared Spectroscopy of MoTe2 Thin Films

Molybdenum ditelluride (MoTe2), a member of the transition metal dichalcogenide family, holds significant promise in optoelectronic applications. To harness its full potential, it is imperative to understand its fundamental optical properties, including refractive indices. Herein, measurements of the transmittance and reflectance spectra of thin MoTe2 layers are conducted featuring hexagonal and monoclinic structures across the far‐infrared (IR) and mid‐IR spectral regions. These spectra are fitted, allowing to extract the complex refractive index and optical conductance. In the semiconducting hexagonal phase, both the conductance and extinction coefficient remain negligible below 3000 cm−1 and increase at higher energies. Conversely, the monoclinic phase exhibits a conductance peak in the far‐IR region and a continuous increase from 1000 to 6000 cm−1. The findings are compared with existing theoretical and experimental results to provide further insights into MoTe2's optical behavior.

Machine learning driven prediction of lattice constants in transition metal dichalcogenides

Machine learning represents an emerging branch of artificial intelligence, centering on the enhancement of algorithms in computer programs through the utilization of data and the accumulation of research-driven knowledge. The requirement for artificial intelligence in materials science is essential due to the significant need for innovative high-performance materials on a large scale. In this report, the gradient boosting regression tree model of machine learning was applied to predict the lattice constants of cubic and trigonal MX2 systems (M=transition metal and X=chalcogen atoms). The theoretical/experimental values of the materials were compared to the predicted values to calculate the standard errors such as RMSE (root mean square error) and MAE (mean absolute error). The features used to predict lattice constants were ionic radius, lattice angles, bandgap, formation energy, total magnetic moment, density and oxidation states. The features versus contribution barplot has been drawn to reveal the contribution level of each parameter in the degree of [0,1] to obtain the predictions. This report provides a precise account of the prediction methodology for lattice parameters of the transition metal dichalcogenides family, a process that was previously not reported.

Ultrafast Fiber Laser Based on Tungsten Sulphoselenide Materials

Tungsten sulphoselenide (WSSe) alloys, belonging to the transition metal dichalcogenide family, have attracted significant interest in the area of optoelectronics because of their unique optical and electronic properties. However, there has been a dearth of sufficient research on the saturable absorption features and ultrafast lasers applications. Herein, we fabricated a WSSe-microfiber saturable absorber (SA) based on WSSe nanosheets prepared by liquid exfoliation technique. The SA provided a saturation intensity of a modulation depth of 27.95% and a nonsaturable loss of 21.34%. To investigate the potential applications of WSSe in ultrafast photonics, the prepared WSSe-microfiber was incorporated into an Er-doped fiber laser ring cavity. The results demonstrated that the WSSe-based SA successfully generated mode-locking laser pulses with a remarkably short pulse width of 231 fs. Furthermore, the output power of this ultrafast fiber laser reached an impressive value of 15.68 mW. These findings provide valuable views into the unique features of WSSe alloys in the areas of ultrafast optics and develop recipes for SA in ultrafast fiber lasers.

HfSe2: Unraveling the microscopic reason for experimental low mobility.

Monolayer HfSe2, in the family of transition metal dichalcogenides (TMDCs), is a potential thermoelectric candidate due to its low thermal conductivity. While its mobility remains low as in other 2D TMDCs is inconceivable for electronic and thermoelectric applications. Earlier theoretical attempts have failed to give justification for the orders of low experimental mobility obtained for monolayer HfSe2. We calculate the carrier mobility in the framework of the density functional perturbation theory in conjunction with the Boltzmann transport equation and correctly ascertain the experimental value. We also calculate the carrier mobility with the previously employed method, the deformation potential (DP) model, to figure out the reason for its failure. We found that it is the strong electron-optical phonon interaction that is causing the low mobility. As the DP model does not account for the optical phonons, it overestimates the relaxation time by an order of two and also underestimates the temperature dependence of mobility. A strong polar type interaction is evidenced as a manifestation of a discontinuity in the first derivative of the optical-phonons at the K and Γ points as well as a dispersive optical phonon at the K point. We also included the spin-orbit coupling which leads to an energy splitting of ∼330meV and significantly affects mobility and scattering rates.

Direct Solution Phase Synthesis and Functionalization of 2D WSe2 for Ambient Stability.

2H phase tungsten diselenide (WSe2) is a p-type 2D semiconductor from the transition metal dichalcogenides (TMDs) family with unique opto-electrical properties. Solution phase production of atomically thin WSe2is challenging due to its instability under ambient conditions. We present a highly efficient and scalable solution method for simultaneously exfoliating and functionalizingWSe2by leveraging the noncovalent interaction between mercapto-group and bulk WSe2.Single and few-layer 2H phase pure WSe2sheets of lateral size up to 5µm with minimal basal plane defects, as revealed by XPS, Raman and FTIR spectroscopy, are produced in water-ethanol mixture. Remarkably, WSe2dispersion remains stable even at high concentrations (10 mg/ml) and exhibited high colloidal stability with shelf-life exceeding a year. The findings from our study suggest that through precise manipulation of intercalation chemistry, mass production of solution processable phase-sensitive 2D materials such as WSe2can be achieved. This advancement holds great potential for facilitating their practical utilization in various real-world applications.