Layered Transition Metal Dichalcogenides Research Articles

Carrier and thickness mediated ferromagnetism in chiral magnet Mn1/3TaS2 nanoflakes

Layered chiral magnets with broken spatial inversion symmetry (SIS) enable chiral spin textures to occur in atomically thin layers. However, most layered materials retain SIS during their crystallization. Here, we demonstrate that SIS can be broken in a layered transition metal dichalcogenide TaS2 by intercalating Mn atoms. A chiral magnetic phase in Mn1/3TaS2 has, thus, been realized. This phase enables a nonzero Dzyaloshinskii–Moriya interaction, which in turn gives rise to large topological Hall effects (THEs) below 50 K. Both the ferromagnetism and THE can be tuned at low temperatures by modulating the carrier density via a protonic gate. Measured at 20 K with Vg = −4.7 V applied to the gate and electron doping density of 1.7 × 1022 cm−3, the maximum THE was almost double that recorded with no gate voltage applied. By further reducing the sample thicknesses, both the Curie temperature Tc and the longitudinal magnetoresistance can be significantly modulated. This is consistent with the theory of critical behavior. Our work highlights the ability to control both magnetism and chiral spin textures in Mn1/3TaS2 nanoflakes. Applying this discovery may lead to a variety of practical van der Waals heterostructure devices.

Substrate Effects on Growth Dynamics of WTe2 Thin films

AbstractSynthesis of transition metal dichalcogenides (TMDCs) has been achieved through the direct conversion of metal and metal‐oxide films, demonstrating the ability to grow large area thin films with uniform thickness on a variety of substrates and direct control over the growth orientation (horizontal vs vertical) of the TMDC layers. However, the synthesized TMDC films often exhibit small grains and are more defective than their bulk counterparts. This is especially true for 2D telluride films due to the low reactivity between tellurium and transition metals such as W and Mo. In this work, the substrate interactions is examined for WTe2 converted from amorphous WOx thin films grown by atomic layer deposition, on c‐plane sapphire and SiO2 through tellurization at high temperatures. Similar to TMDC telluride MoTe2, the formation of monolayer WTe2 on sapphire is observed, but not on SiO2. However, due to decreased diffusion of W on sapphire compared to Mo, the formation of WTe2 flakes instead of continuous films is observed, providing insight into the role of the specific transition metal during the direct synthesis of TMDC telluride films.

A simple KPFM-based approach for electrostatic- free topographic measurements: the case of MoS2 on SiO2

A simple implementation of Kelvin probe force microscopy (KPFM) is reported that enables recording topographic images in the absence of any component of the electrostatic force (including the static term). Our approach is based on a close loop z-spectroscopy operated in data cube mode. Curves of the tip-sample distance as a function of time are recorded onto a 2D grid. A dedicated circuit holds the KPFM compensation bias and subsequently cut off the modulation voltage during well-defined time-windows within the spectroscopic acquisition. Topographic images are recalculated from the matrix of spectroscopic curves. This approach is applied to the case of transition metal dichalcogenides (TMD) monolayers grown by chemical vapour deposition on silicon oxide substrates. In addition, we check to what extent a proper stacking height estimation can also be performed by recording series of images for decreasing values of the bias modulation amplitude. The outputs of both approaches are shown to be fully consistent. The results exemplify how in the operating conditions of non-contact AFM under ultra-high vacuum (nc-AFM), the stacking height values can dramatically be overestimated due to variations in the tip-surface capacitive gradient, even though the KPFM controller nullifies the potential difference. We show that the number of atomic layers of a TMD can be safely assessed, only if the KPFM measurement is performed with a modulated bias amplitude reduced at its strict minimum or, even better, without any modulated bias. Last, the spectroscopic data reveal that certain kind of defects can have a counterintuitive impact on the electrostatic landscape, resulting in an apparent decrease of the measured stacking height by conventional nc-AFM/KPFM compared to other sample areas. Hence, electrostatic free z-imaging proves to be a promising tool to assess the existence of defects in atomically thin TMD layers grown on oxides.

WS2 Nanotube-Embedded SiOC Fibermat Electrodes for Sodium-Ion Batteries.

Layered transition metal dichalcogenides (TMDs) such as tungsten disulfide (WS2) are promising materials for a wide range of applications, including charge storage in batteries and supercapacitors. Nevertheless, TMD-based electrodes suffer from bottlenecks such as capacity fading at high current densities, voltage hysteresis during the conversion reaction, and polysulfide dissolution. To tame such adverse phenomena, we fabricate composites with WS2 nanotubes. Herein, we report on the superior electrochemical performance of ceramic composite fibers comprising WS2 nanotubes (WS2NTs) embedded in a chemically robust molecular polymer-derived ceramic matrix of silicon-oxycarbide (SiOC). Such a heterogeneous fiber structure was obtained via electrospinning of WS2NT/preceramic polymer solution followed by pyrolysis at elevated temperatures. The electrode capacity fading in WS2NTs was curbed by the synergistic effect between WS2NT and SiOC. As a result, the composite electrode exhibits high initial capacity of 454 mAh g-1 and the capacity retention approximately 2-3 times higher than that of the neat WS2NT electrode.

Tungsten Oxide Mediated Quasi-van der Waals Epitaxy of WS2 on Sapphire.

Conventional epitaxy plays a crucial role in current state-of-the art semiconductor technology, as it provides a path for accurate control at the atomic scale of thin films and nanostructures, to be used as the building blocks in nanoelectronics, optoelectronics, sensors, etc. Four decades ago, the terms "van der Waals" (vdW) and "quasi-vdW (Q-vdW) epitaxy" were coined to explain the oriented growth of vdW layers on 2D and 3D substrates, respectively. The major difference with conventional epitaxy is the weaker interaction between the epi-layer and the epi-substrates. Indeed, research on Q-vdW epitaxial growth of transition metal dichalcogenides (TMDCs) has been intense, with oriented growth of atomically thin semiconductors on sapphire being one of the most studied systems. Nonetheless, there are some striking and not yet understood differences in the literature regarding the orientation registry between the epi-layers and epi-substrate and the interface chemistry. Here we study the growth of WS2 via a sequential exposure of the metal and the chalcogen precursors in a metal-organic chemical vapor deposition (MOCVD) system, introducing a metal-seeding step prior to the growth. The ability to control the delivery of the precursor made it possible to study the formation of a continuous and apparently ordered WO3 mono- or few-layer at the surface of a c-plane sapphire. Such an interfacial layer is shown to strongly influence the subsequent quasi-vdW epitaxial growth of the atomically thin semiconductor layers on sapphire. Hence, here we elucidate an epitaxial growth mechanism and demonstrate the robustness of the metal-seeding approach for the oriented formation of other TMDC layers. This work may enable the rational design of vdW and quasi-vdW epitaxial growth on different material systems.

Realization of Multiple Charge-Density Waves in NbTe2 at the Monolayer Limit.

Layered transition-metal dichalcogenides down to the monolayer (ML) limit provide a fertile platform for exploring charge-density waves (CDWs). Here, we experimentally unveil the richness of the CDW phases in ML-NbTe2 for the first time. Not only the theoretically predicted 4 × 4 and 4 × 1 phases but also two unexpected and phases are realized. For such a complex CDW system, we establish an exhaustive growth phase diagram via systematic efforts in the material synthesis and scanning tunneling microscope characterization. Moreover, the energetically stable phase is the larger-scale order (), which is surprisingly in contradiction to the prior prediction (4 × 4). These findings are confirmed using two different kinetic pathways: i.e., direct growth at proper growth temperatures (T) and low-T growth followed by high-T annealing. Our results provide a comprehensive diagram of the "zoo" of CDW orders in ML-NbTe2.

PVD growth of spiral pyramid-shaped WS2 on SiO2/Si driven by screw dislocations.

Atomically thin layered transition metal dichalcogenides (TMDs), such as MoS2 and WS2, have been getting much attention recently due to their interesting electronic and optoelectronic properties. Especially, spiral TMDs provide a variety of candidates for examining the light-matter interaction resulting from the broken inversion symmetry, as well as the potential new utilization in functional optoelectronic, electromagnetic and nanoelectronics devices. To realize their potential device applications, it is desirable to achieve controlled growth of these layered nanomaterials with a tunable stacking. Here, we demonstrate the Physical Vapor Deposition (PVD) growth of spiral pyramid-shaped WS2 with ∼200 in size and the interesting optical properties via AFM and Raman spectroscopy. By controlling the precursors concentration and changing the initial nucleation rates in PVD growth, WS2 in different nanoarchitectures can be obtained. We discuss the growth mechanism for these spiral-patterned WS2 nanostructures based on the screw dislocations. This study provides a simple, scalable approach of screw dislocation-driven (SDD) growth of distinct TMD nanostructures with varying morphologies, and stacking.

Interface Engineering Modulated Valley Polarization in MoS2/hBN Heterostructure

Layered transition metal dichalcogenides (TMDs) provide a favorable research platform for the advancement of spintronics and valleytronics because of their unique spin-valley coupling effect, which is attributed to the absence of inversion symmetry coupled with the presence of time-reversal symmetry. To maneuver the valley pseudospin efficiently is of great importance for the fabrication of conceptual devices in microelectronics. Here, we propose a straightforward way to modulate valley pseudospin with interface engineering. An underlying negative correlation between the quantum yield of photoluminescence and the degree of valley polarization was discovered. Enhanced luminous intensities were observed in the MoS2/hBN heterostructure but with a low value of valley polarization, which was in stark contrast to those observed in the MoS2/SiO2 heterostructure. Based on the steady-state and time-resolved optical measurements, we reveal the correlation between exciton lifetime, luminous efficiency, and valley polarization. Our results emphasize the significance of interface engineering for tailoring valley pseudospin in two-dimensional systems and probably advance the progression of the conceptual devices based on TMDs in spintronics and valleytronics.

Variant Plateau’s law in atomically thin transition metal dichalcogenide dome networks

Since its fundamental inception from soap bubbles, Plateau’s law has sparked extensive research in equilibrated states. However, most studies primarily relied on liquids, foams or cellular structures, whereas its applicability has yet to be explored in nano-scale solid films. Here, we observed a variant Plateau’s law in networks of atomically thin domes made of solid two-dimensional (2D) transition metal dichalcogenides (TMDs). Discrete layer-dependent van der Waals (vdWs) interaction energies were experimentally and theoretically obtained for domes protruding in different TMD layers. Significant surface tension differences from layer-dependent vdWs interaction energies manifest in a variant of this fundamental law. The equivalent surface tension ranges from 2.4 to 3.6 N/m, around two orders of magnitude greater than conventional liquid films, enabling domes to sustain high gas pressure and exist in a fundamentally variant nature for several years. Our findings pave the way towards exploring variant discretised states with applications in opto-electro-mechanical devices.

Toward Perfect Surfaces of Transition Metal Dichalcogenides with Ion Bombardment and Annealing Treatment.

Layered transition metal dichalcogenides (TMDs) are two-dimensional materials exhibiting a variety of unique features with great potential for electronic and optoelectronic applications. The performance of devices fabricated with mono or few-layer TMD materials, nevertheless, is significantly affected by surface defects in the TMD materials. Recent efforts have been focused on delicate control of growth conditions to reduce the defect density, whereas the preparation of a defect-free surface remains challenging. Here, we show a counterintuitive approach to decrease surface defects on layered TMDs: a two-step process including Ar ion bombardment and subsequent annealing. With this approach, the defects, mainly Te vacancies, on the as-cleaved PtTe2 and PdTe2 surfaces were decreased by more than 99%, giving a defect density <1.0 × 1010 cm-2, which cannot be achieved solely with annealing. We also attempt to propose a mechanism behind the processes.

Defect-Engineering of 2D Dichalcogenide VSe2 to Enhance Ammonia Sensing: Acumens from DFT Calculations

Opportune sensing of ammonia (NH3) gas is industrially important for avoiding hazards. With the advent of nanostructured 2D materials, it is felt vital to miniaturize the detector architecture so as to attain more and more efficacy with simultaneous cost reduction. Adaptation of layered transition metal dichalcogenide as the host may be a potential answer to such challenges. The current study presents a theoretical in-depth analysis regarding improvement in efficient detection of NH3 using layered vanadium di-selenide (VSe2) with the introduction of point defects. The poor affinity between VSe2 and NH3 forbids the use of the former in the nano-sensing device's fabrications. The adsorption and electronic properties of VSe2 nanomaterials can be tuned with defect induction, which would modulate the sensing properties. The introduction of Se vacancy to pristine VSe2 was found to cause about an eight-fold increase (from -012 eV to -0.97 eV) in adsorption energy. A charge transfer from the N 2p orbital of NH3 to the V 3d orbital of VSe2 has been observed to cause appreciable NH3 detection by VSe2. In addition to that, the stability of the best-defected system has been confirmed through molecular dynamics simulation, and the possibility of repeated usability has been analyzed for calculating recovery time. Our theoretical results clearly indicate that Se-vacant layered VSe2 can be an efficient NH3 sensor if practically produced in the future. The presented results will thus potentially be useful for experimentalists in designing and developing VSe2-based NH3 sensors.

Tunable Superconductivity and Möbius Fermi Surfaces in an Inversion-Symmetric Twisted van der Waals Heterostructure

We theoretically study a moiré superlattice geometry consisting of mirror-symmetric twisted trilayer graphene surrounded by identical transition metal dichalcogenide layers. We show that this setup allows us to switch on or off and control the spin-orbit splitting of the Fermi surfaces via application of a perpendicular displacement field D_{0} and explore two manifestations of this control: first, we compute the evolution of superconducting pairing with D_{0}; this features a complex admixture of singlet and triplet pairing and, depending on the pairing state in the parent trilayer system, phase transitions between competing superconducting phases. Second, we reveal that, with application of D_{0}, the spin-orbit-induced spin textures exhibit vortices which lead to "Möbius fermi surfaces" in the interior of the Brillouin zone: diabatic electron trajectories, which are predicted to dominate quantum oscillation experiments, require encircling the Γ point twice, making their Möbius nature directly observable. Further, we show that the superconducting order parameter inherits the unconventional, Möbius spin textures. Our findings suggest that this system provides a promising experimental avenue for systematically studying the impact of spin-orbit coupling on the multitude of topological and correlated phases in near-magic-angle twisted trilayer graphene.

Ultra-thin grating coupler for guided exciton-polaritons in WS2 multilayers

Abstract An ultra-thin transition metal dichalcogenide (TMDC) layer can support guided exciton-polariton modes due to the strong coupling between excitons and photons. Herein, we report the guided mode resonance in an ultra-thin TMDC grating structure. Owing to the strong exciton resonances in TMDCs, a TMDC grating structure shows guided-mode resonance even at a thickness limit of ∼10 nm and is capable of realizing polaritonic dispersion in a monolithic grating structure. We investigated the polarization and thickness dependence of the optical dispersion relations of the tungsten disulfide (WS2) grating structure. In addition, we confirmed that the monolithic WS2 grating coupler can be used to couple the near-field guided exciton-polariton out into the far field. We believe that ultra-thin TMDC layers can facilitate sub-wavelength nanophotonic applications.

Precision Modification of Monolayer Transition Metal Dichalcogenides via Environmental E-Beam Patterning

Layered Transition Metal Dichalcogenides (TMDs) are an important class of materials that exhibit a wide variety of optoelectronic properties. The ability to spatially tailor their expansive property-space (e.g., conduction behavior, optical emission, surface interactions) is of special interest for applications including, but not limited to, sensing, bioelectronics, and spintronics/valleytronics. Current methods of property modulation focus on the modification of the basal surfaces and edge sites of the TMDs by the introduction of defects, functionalization with organic or inorganic moieties, alloying, heterostructure formation, and phase engineering. A majority of these methods lack the resolution for the development of next-generation nanoscale devices or are limited in the types of functionalities useful for efficient TMD property modification. In this study, we utilize electron-beam patterning on monolayer TMDs (MoSe2, WSe2 and MoS2) in the presence of a pressure-controlled atmosphere of water vapor within an environmental scanning electron microscope (ESEM). A series of parametric studies show local optical and electronic property modification depending on acceleration voltage, beam current, pressure, and electron dose. The ultimate pattern resolution achieved is 67 ± 9 nm. Raman and photoluminescence spectroscopies coupled with Kelvin Probe Force Microscopy reveal electron dose-dependent p-doping in the patterned regions, which we attribute to functionalization from the products of water vapor radiolysis (oxygen and hydroxyl groups). The modulation of the work function through patterning matches well with Density Functional Theory modeling. Finally, post-functionalization of the patterned areas with an organic fluorophore demonstrates a robust method to achieve nanoscale functionalization with high fidelity.

Tunability of the Superconductivity of NbSe2 Films Grown by Two-Step Vapor Deposition.

Layered metallic transition-metal dichalcogenides (TMDCs) are ideal platforms for exploring their fascinating electronic properties at two-dimensional limits, such as their charge density wave (CDW) and superconductivity. Therefore, developing ways to improve the crystallization quality of TMDCs is urgently needed. Here we report superconductively tunable NbSe2 grown by a two-step vapor deposition method. By optimizing the sputtering conditions, superconducting NbSe2 films were prepared from highly crystalline Nb films. The bilayer NbSe2 films showed a superconducting transition temperature that was up to 3.1 K. Similar to the salt-assisted chemical vapor deposition (CVD) method, superconducting monolayer NbSe2 crystals were also grown from a selenide precursor, and the growth strategy is suitable for many other TMDCs. Our growth method not only provides a way to improve the crystalline quality of TMDC films, but also gives new insight into the growth of monolayer TMDCs. It holds promise for exploring two-dimensional TMDCs in fundamental research and device applications.

Van der Waals Layer Transfer of 2D Materials for Monolithic 3D Electronic System Integration: Review and Outlook.

Two-dimensional materials (2DMs) have attracted a great deal of interest due to their immense potential for scientific breakthroughs and technological innovations. While some 2D transition metal dichalcogenides (TMDC) such as MoS2 and WS2 are considered as the ultimate channel materials in unltrascaled transistors as replacements for Si, there has also been increasing interest in the monolithic 3D integration of 2DMs on the Si CMOS platform or in flexible electronics as back-end-of-line transistors, memory devices/selectors, and sensors, taking advantage of 2DM properties such as a high current driving capability with low leakage current, nonvolatile switching characteristics, a large surface-to-volume ratio, and a tunable bandgap. However, the realization of both of these scenarios critically depends on the development of manufacturing-viable high-yield 2DM layers transfer from the growth substrate to the Si, since the growth of high-quality 2DM layers often requires a high-temperature growth process on template substrates. Motivated by this, extensive efforts have been made by the 2DM research community to develop various 2DM layer transfer methods, leveraging the van der Waals transfer capability of the layer-structured 2DMs. These efforts have led to a number of successful demonstrations of wafer-scale 2D TMDC layer transfer, while 2DM-enabled template growth/transfer of some functional bulk materials such as III-V, Ge, and AlN has also been demonstrated. This review surveys and compares different 2DM transfer methods developed recently, with a focus on large-area 2D TMDC film transfer along with an introduction of 2DM template-assisted van der Waals growth/transfer of non-2D thin films. We will also briefly present an outlook of our envisioned multifunctionalities in 3D integrated electronic systems enabled by monolithic 3D integration of 2DMs and III-V via van der Waals transfer and discuss possible technology options for overcoming remaining challenges.

Phonon Dominated Thermal Transport in Metallic Niobium Diselenide from First Principles Calculations.

Niobium diselenide (NbSe2) is a layered transition metal dichalcogenide material which possesses unique electrical and superconducting properties for future nanodevices. While the superconducting, electrical, and bulk thermal transport properties of NbSe2 have been widely studied, the in-plane thermal transport property of NbSe2, which is important for potential thermoelectric applications, has not been thoroughly investigated. In this report, we study the lattice in-plane thermal transport of 2D NbSe2 by solving the phonon Boltzmann transport equation with the help of the first principles calculation. The thermal conductivity obtained at room temperature is 12.3 W/mK. A detailed analysis shows that the transverse acoustic phonon dominates the lattice thermal transport, and an anomalously small portion of electron contribution to the total thermal conductivity is observed for this metallic phase. The results agree well with experimental measurements and provide detailed mode-by-mode thermal conductivity contribution from different phonon modes. This study can provide useful information for integrating NbSe2 in nanodevices where both electrical and thermal properties are critical, showing great potential for integrating monolayer NbSe2 to thermoelectric devices.

Ultrafast transient absorption measurements of photocarrier dynamics in PdSe2.

We investigate the photocarrier dynamics in bulk PdSe2, a layered transition metal dichalcogenide with a novel pentagonal structure and unique electronic and optical properties. Using femtosecond transient absorption microscopy, we study the behavior of photocarriers in mechanically exfoliated bulk PdSe2 flakes at room temperature. By employing a 400 nm ultrafast laser pulse, electron-hole pairs are generated, and their dynamics are probed using an 800 nm detection pulse. Our findings reveal that the lifetime of photocarriers in bulk PdSe2 is approximately 210 ps. Furthermore, by spatially resolving the differential reflection signal, we determine a photocarrier diffusion coefficient of about 7.3 cm2 s-1. Based on these results, we estimate a diffusion length of around 400 nm and a photocarrier mobility of approximately 300 cm2 V-1 s-1. These results shed light on the ultrafast optoelectronic properties of PdSe2, offer valuable insights into photocarriers in this emerging material, and enable design of high-performance optoelectronic devices based on PdSe2.

High temperature stability in few atomic layer MoS2 based thin film heterostructures: structural, static and dynamic magnetization properties.

Layered transition metal dichalcogenides (TMDs) have shown commendable properties for spintronic applications. From the device perspective, the structural quality of the TMD as well as its interface with the adjacent ferromagnetic (FM) layer is of paramount importance. Here, we present the spin-dynamic behaviour in the widely studied TMDs, i.e., MoS2 using Co60Fe20B20 (CoFeB), i.e., in MoS2(1-4 layers)/CoFeB(4-15 nm) heterostructures, both in the as-grown state and in the in situ annealed state (400 °C in a vacuum). Raman spectroscopy revealed systematic variation in the separation (δ) between the characteristic Raman shifts corresponding to the E2g and A1gvis-à-vis the number of layers (nL) of MoS2. The analysis of the ferromagnetic resonance (FMR) spectroscopy measurements performed on these heterostructures revealed the spin pumping from CoFeB to the MoS2 layer as evidenced by the ∼49% (∼51%) enhancement in the effective damping parameter with respect to the damping parameter of bare as-deposited (annealed) CoFeB films. This enhancement is attributed to the spin-pumping owing to the high spin-orbit coupling of monolayer MoS2. The latter is also confirmed by density functional theory calculations. By finding the effective spin mixing conductance of the MoS2/CoFeB interface, the effective spin current density in the MoS2 layer is estimated to increase from ∼0.3 to 0.7 MA m-2 with CoFeB thickness for both the as-deposited and annealed heterostructures. Furthermore, the δ vs. nL curve of the as-deposited heterostructure did not show any significant change upon annealing, which demonstrated that the spin transport and magnetic properties of these heterostructures remained unaffected even after annealing at a high temperature of 400 °C. Hence, this establishes the high thermal stability of the sputter grown MoS2/CoFeB heterostructures. Thus, this study highlights the important role of MoS2 as an efficient spin current-generating source for spin-orbit torque based magnetic memory applications, given the high-temperature stability and high-quality monolayers of MoS2 and its excellent performance with CoFeB thin films.

Enhanced electrocatalytic hydrogen evolution from nitrogen plasma-tailored MoS2 nanostructures.

Two-dimensional (2D) layered transition metal dichalcogenides such as MoS2 have been viewed as the most favorable candidates for replacing noble metals in catalyzing the hydrogen evolution reaction in water splitting owing to their earth abundance, superb chemical stability, and appropriate Gibbs free energy. However, due to its low number of catalytic sites and basal catalytic inertia, the pristine MoS2 displayed intrinsically unsatisfactory HER catalytic activity. Here, the hydrogen evolution catalytic activities of nanostructured MoS2 powder before and after plasma modification with nitrogen doping were experimentally compared, and the influence of treatment parameters on the hydrogen evolution catalytic performance of MoS2 has been studied. The feasibility of regulating hydrogen evolution catalytic activity by nitrogen doping of MoS2 was verified based on density functional theory calculations. Our work demonstrates a more convenient and faster way to develop cheap and efficient MoS2-based catalysts for electrochemical hydrogen evolution reactions. Additionally, theoretical studies reveal that N-doped MoS2 exhibits strong hybridization between Mo-d and N-p states, causing magnetism to evolve, as confirmed by experiments.