Group VI Transition Metal Dichalcogenides Research Articles

Revealing hidden spin polarization in centrosymmetric van der Waals materials on ultrafast timescales

One of the key challenges for spintronic and quantum technologies is to achieve active control of the spin angular momentum of electrons in nanoscale materials on ultrafast, femtosecond timescales. While conventional ferromagnetic materials and materials supporting spin texture suffer both from conceptional limitations in miniaturization and inefficiency of optical and electronic manipulation, non-magnetic centrosymmetric layered materials with hidden spin polarization may offer an alternative pathway to manipulate the spin degree of freedom by external stimuli. Here we demonstrate an approach for generating transient spin polarization on a femtosecond timescale in the otherwise spin-unpolarized band structure of the centrosymmetric 2H-stacked group VI transition metal dichalcogenide WSe2. Using ultrafast optical excitation of a fullerene layer grown on top of WSe2, we trigger an ultrafast interlayer electron transfer from the fullerene layer into the WSe2 crystal. The resulting transient charging of the C60/WSe2 interface leads to a substantial interfacial electric field that by means of spin-layer-valley locking ultimately creates ultrafast spin polarization without the need of an external magnetic field. Our findings open a novel pathway for true optical engineering of spin functionalities such as the sub-picosecond generation and manipulation of ultrafast spin currents in 2D heterostructures.

The coexistence and competition of charge-density wave and superconductivity in the electron-doped H- MX2 (M = Mo, W and X=S, Se)

In the group VI transition metal dichalcogenides (TMDs), an insulator family with two-dimensional structure, MoS2 has recently demonstrated to be involved in charge-density wave (CDW) and superconductivity (SC). Nevertheless, there is a lack of a cohesive theoretical framework and fragmentation in the existing theoretical models of the relationship between CDW and SC for this system. Base on first-principles calculations, the effects of electron doping on the electronic properties, electron-phonon interaction and SC are investigated comprehensively for monolayer H- MX2 (M = Mo, W and X = S, Se) here. We confirmed that two CDW phases, 23×23 and 2 × 2, are originated from Fermi surface nesting (FSN) and electron-phonon coupling (EPC), respectively. A complicated phase diagram of doping concentration dependencies of CDW and SC critical temperatures (TC) is created, by SC coexisting with 23×23 CDW phase while competing with 2 × 2 CDW phase. The physical mechanisms of such coexistence and competition are also explained here. Our results extend the theoretical investigation by providing a comprehensive and in-depth analysis of CDW and SC in the group VI TMDs, and open up an alternative path for the exploration and regulation of collective phases of two-dimensional materials.

Spin-Polarized Charge Separation at Two-Dimensional Semiconductor/Molecule Interfaces.

Spin-polarized electrons can improve the efficiency and selectivity of photo- and electro-catalytic reactions, as demonstrated in the past with magnetic or magnetized catalysts. Here, we present a scheme in which spin-polarized charge separation occurs at the interfaces of nonmagnetic semiconductors and molecular films in the absence of a magnetic field. We take advantage of the spin-valley-locked band structure and valley-dependent optical selection rule in group VI transition metal dichalcogenide (TMDC) monolayers to generate spin-polarized electron-hole pairs. Photoinduced electron transfer from WS2 to fullerene (C60) and hole transfer from MoSe2 to phthalocyanine (H2Pc) are found to result in spin polarization lifetimes that are 1 order of magnitude longer than those in the TMDC monolayers alone. Our findings connect valleytronic properties of TMDC monolayers to spin-polarized interfacial charge transfer and suggest a viable route toward spin-selective photocatalysis.

Investigating the impact of growth temperature on the direct integration of pure phase 2H-MoTe2 with Si(1 1 1) using molecular beam epitaxy

Group-VI transition metal dichalcogenides (TMDCs) have garnered significant attention due to their novel properties in the two-dimensional realm. Among these TMDCs, MoTe2 is a particularly intriguing material with a small difference between Gibbs free energies of its semiconducting and semimetallic phases, rendering it suitable for a wide array of applications. In this study, we report the molecular beam epitaxy (MBE) growth of 2H-MoTe2 directly on a silicon (111) substrate, which holds great significance due to its compatibility with the existing integrated circuit industry. By employing a growth strategy involving a Te-rich silicon surface, we achieved the growth of high-quality, phase-pure 2H-MoTe2 films. The effect of growth temperature on the film quality was investigated, revealing that the growth at 450 °C led to highly crystalline and layered growth. The thickness, roughness and stoichiometry of the grown films were characterized using spectroscopic ellipsometry, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). Raman spectroscopy confirmed the presence of the desired 2H-phase for the grown films. The direct integration of MoTe2 with silicon opens up exciting possibilities for its utilization in nanoelectronics and optoelectronics devices.

Anisotropic Interlayer Force Field for Group-VI Transition Metal Dichalcogenides.

An anisotropic interlayer force field that describes the interlayer interactions in homogeneous and heterogeneous interfaces of group-VI transition metal dichalcogenides (MX2, where M = Mo, W, and X = S, Se) is presented. The force field is benchmarked against density functional theory calculations for bilayer systems within the Heyd-Scuseria-Ernzerhof hybrid density functional approximation, augmented by a nonlocal many-body dispersion treatment of long-range correlation. The parametrization yields good agreement with the reference calculations of binding energy curves and sliding potential energy surfaces. It is found to be transferable to transition metal dichalcogenide (TMD) junctions outside of the training set that contain the same atom types. Calculated bulk moduli agree with most previous dispersion-corrected density functional theory predictions, which underestimate the available experimental values. Calculated phonon spectra of the various junctions under consideration demonstrate the importance of appropriately treating the anisotropic nature of the layered interfaces. Considering our previous parametrization for MoS2, the anisotropic interlayer potential enables accurate and efficient large-scale simulations of the dynamical, tribological, and thermal transport properties of a large set of homogeneous and heterogeneous TMD interfaces.

Classification and Simulation of Structural Phase Transformation-Induced Interfacial Defects in Group VI Transition-Metal Dichalcogenide Monolayers.

Polymorphic 2D materials have recently emerged as promising candidates for use in nanoelectronic devices by way of their ability to undergo structural phase transformations induced by external fields. Under cyclic transformations, however, induced interfacial defects may proliferate and compromise the system properties. Herein, we first employ geometric analysis to classify such defects generated during the 2H ↔ 1T and 2H ↔ 1T' transformations in group VI transition-metal dichalcogenide monolayers. Then, simulations of a mesoscale model with atomistic spatial resolution are conducted to assess the proliferation of such defects during cyclic 2H ↔ 1T transformations. It is shown that defect densities reach a steady state, with the 2H phase remaining more pristine than the 1T and 1T' states. We expect that the effects of these defects on the device performance are application-dependent and will require further inquiry.

Solution-Phase Synthesis of Vanadium Intercalated 1T′-WS2 with Tunable Electronic Properties

Metal ion intercalation into Group VI transition metal dichalcogenides enables control over their carrier transport properties. In this work, we demonstrate a low-temperature, solution-phase synthetic method to intercalate cationic vanadium complexes into bulk WS2. Vanadium intercalation expands the interlayer spacing from 6.2 to 14.2 Å and stabilizes the 1T' phase of WS2. Kelvin-probe force microscopy measurements indicate that vanadium binding in the van der Waals gap causes an increase in the Fermi level of 1T'-WS2 by 80 meV due to hybridization of vanadium 3d orbitals with the conduction band of the TMD. As a result, the carrier type switches from p-type to n-type, and carrier mobility increases by an order of magnitude relative to the Li-intercalated precursor. Both the conductivity and thermal activation barrier for carrier transport are readily tuned by varying the concentration of VCl3 during the cation-exchange reaction.

Layered Semiconductor Cr0.32Ga0.68Te2.33 with Concurrent Broken Inversion Symmetry and Ferromagnetism: A Bulk Ferrovalley Material Candidate.

The valleytronic state found in group-VI transition-metal dichalcogenides such as MoS2 has attracted immense interest since its valley degree of freedom could be used as an information carrier. However, valleytronic applications require spontaneous valley polarization. Such an electronic state is predicted to be accessible in a new ferroic family of materials, i.e., ferrovalley materials, which features the coexistence of spontaneous spin and valley polarization. Although many atomic monolayer materials with hexagonal lattices have been predicted to be ferrovalley materials, no bulk ferrovalley material candidates have been reported or proposed. Here, we show that a new non-centrosymmetric van der Waals (vdW) semiconductor Cr0.32Ga0.68Te2.33, with intrinsic ferromagnetism, is a possible candidate for bulk ferrovalley material. This material exhibits several remarkable characteristics: (i) it forms a natural heterostructure between vdW gaps, a quasi-two-dimensional (2D) semiconducting Te layer with a honeycomb lattice stacked on the 2D ferromagnetic slab comprised of the (Cr, Ga)-Te layers, and (ii) the 2D Te honeycomb lattice yields a valley-like electronic structure near the Fermi level, which, in combination with inversion symmetry breaking, ferromagnetism, and strong spin-orbit coupling contributed by heavy Te element, creates a possible bulk spin-valley locked electronic state with valley polarization as suggested by our DFT calculations. Further, this material can also be easily exfoliated to 2D atomically thin layers. Therefore, this material offers a unique platform to explore the physics of valleytronic states with spontaneous spin and valley polarization in both bulk and 2D atomic crystals.

Switching of K-Q intervalley trions fine structure and their dynamics in n-doped monolayer WS<sub>2</sub>

Monolayer group VI transition metal dichalcogenides (TMDs) have recently emerged as promising candidates for photonic and opto-valleytronic applications. The optoelectronic properties of these atomically-thin semiconducting crystals are strongly governed by the tightly bound electron-hole pairs such as excitons and trions (charged excitons). The anomalous spin and valley configurations at the conduction band edges in monolayer WS₂ give rise to even more fascinating valley many-body complexes. Here we find that the indirect Q valley in the first Brillouin zone of monolayer WS₂plays a critical role in the formation of a new excitonic state, which has not been well studied. By employing a high-quality h-BN encapsulated WS₂ field-effect transistor, we are able to switch the electron concentration within K-Q valleys at conduction band edges. Consequently, a distinct emission feature could be excited at the high electron doping region. Such feature has a competing population with the K valley trion, and experiences nonlinear power-law response and lifetime dynamics under doping. Our findings open up a new avenue for the study of valley many-body physics and quantum optics in semiconducting 2D materials, as well as provide a promising way of valley manipulation for next-generation entangled photonic devices.

Magnetic ground states of honeycomb lattice Wigner crystals

Lattice Wigner crystal states stabilized by long-range Coulomb interactions have recently been realized in two-dimensional moiré materials. We employ large-scale unrestricted Hartree-Fock techniques to unveil the magnetic phase diagrams of honeycomb lattice Wigner crystals. For the three lattice filling factors with the largest charge gaps, n=2/3,1/2,1/3, the magnetic phase diagrams contain multiple phases, including ones with non-collinear and non-coplanar spin arrangements. We discuss magnetization evolution with external magnetic field, which has potential as an experimental signature of exotic spin states. Our theoretical results could potentially be validated in moiré materials formed from group VI transition metal dichalcogenide twisted homobilayers.

An electronic nose based on 2D group VI transition metal dichalcogenides/organic compounds sensor array

Rapid volatile organic compounds (VOCs) detection is a hot topic today; in this framework nanomaterials and their tailorable chemistry offer a plethora of compelling opportunities. In this work, Group VI transition metal dichalcogenides (TMDs, i.e., MoS2, WSe2, MoSe2, and WSe2) were functionalized with organic compounds (ellagic acid, tannic acid, catechin, and sodium cholate) able to assist their sonochemical exfoliation in water. The 16 resulting water-dispersed 2D hybrid inorganic/organic TMDs resulted in a few-layer nanoflakes conformation and were used to modify quartz crystal microbalances (QCMs) to equip an e-nose for VOCs determination. The ability of the sensors for the detection of VOCs was assessed on alcohols, terpenes, esters, and aldehydes; the responses were significatively different, confirming the synergic effect of TMD and the organic compound in the interaction with VOCs. The 16 sensors exhibited quantitative responses for VOCs (R2≥0.978) with fast signals recovery (<100 s) and repeatable (RSD ≤9.3%, n = 5), reproducible (RSD ≤12.8%, n = 3) and stable (RSD ≤14.6%, 3 months) signals. As proof of applicability, in an e-nose format, banana aroma evolution during post-harvest ripening was successfully monitored using the 2D TMDs-based sensors array. These data demonstrate that TMDs exfoliated in water with different organic compounds are sustainable functional nanomaterials, able to offer new opportunities in nano-bioelectronic applications.

Phenolic compounds as redox-active exfoliation agents for group VI transition metal dichalcogenides

Simple, cheap, and green exfoliation methods for the mass production of two-dimensional (2D) nanomaterials are still required for their widespread adoption. In this context, this work presents a systematic study regarding the exfoliation of group VI transition metal dichalcogenides (TMDs) using 14 different food-derived phenolic compounds of different structural complexity. Phenolic compounds have demonstrated to successfully assist the liquid phase exfoliation conferring unique redox functionalities to the TMDs nanosheets. The most performant exfoliating agents have been carefully optimized and demonstrated to produce stable 2D nanoflakes dispersions with peculiar electrochemical properties. This work proves how properly selected natural stabilizing agents allow an effective TMDs exfoliation, giving rise to hybrid organic/inorganic nanomaterials with functional electrochemical and additional catalytic features. The reported approach opens new paths for the green production of exfoliated 2D functional nanomaterials for sensing, biosensing, and energy applications.

Phase transition of Al2O3-encapsulated MoTe2 via rapid thermal annealing

Among group VI transition metal dichalcogenides, MoTe2 is predicted to have the smallest energy offset between semiconducting 2H and semimetallic 1T′ states. This makes it an attractive phase change material for both electronic and optoelectronic applications. Here, we report fast, nondestructive, and full phase change in Al2O3-encapsulated 2H-MoTe2 thin films to 1T′-MoTe2 using rapid thermal annealing at 900 °C. Phase change was confirmed using Raman spectroscopy after a short annealing duration of 10 s in both vacuum and nitrogen ambient. No thickness dependence of the transition temperatures was observed for flake thickness ranging from 1.5 to 8 nm. These results represent a major step forward in understanding the structural phase transition properties of MoTe2 thin films using external heating and underline the importance of surface encapsulation for avoiding thin film degradation.

The Role of Additives in Suppressing the Degradation of Liquid-Exfoliated WS2 Monolayers.

Group VI transition metal dichalcogenides (TMDs) are considered to be chemically widely inert, but recent reports point toward an oxidation of monolayered sheets in ambient conditions, due to defects. To date, the degradation of monolayered TMDs is only studied on individual, substrate-supported nanosheets with varying defect type and concentration, strain, and in an inhomogeneous environment. Here, degradation kinetics of WS2 nanosheet ensembles in the liquid phase are investigated through photoluminescence measurements, which selectively probe the monolayers. Monolayer-enriched WS2 dispersions are produced with varying lateral sizes in the two common surfactant stabilizers sodium cholate (SC) and sodium dodecyl sulfate (SDS). Well-defined degradation kinetics are observed, which enable the determination of activation energies of the degradation and decouple photoinduced and thermal degradation. The thermal degradation is slower than the photoinduced degradation and requires higher activation energy. Using SC as surfactant, it is sufficiently suppressed. The photoinduced degradation can be widely prevented through chemical passivation achieved through the addition of cysteine which, on the one hand, coordinates to defects on the nanosheets and, on the other hand, stabilizes oxides on the surface, which shield the nanosheets from further degradation.

Defect-Enabled Phase Programming of Transition Metal Dichalcogenide Monolayers.

The ability to tune the local electronic transport properties of group VI transition metal dichalcogenide (TMD) monolayers by strain-induced structural phase transformations ("phase programming") has stimulated much interest in the potential applications of such layers as ultrathin programmable and dynamically switchable nanoelectronics components. In this manuscript, we propose a new approach toward controlling TMD monolayer phases by employing macroscopic in-plane strains to amplify heterogeneous strains arising from tailored, spatially extended defects within the monolayer. The efficacy of our proposed approach is demonstrated via numerical simulations of emerging domains localized around arrays of holes, grain boundaries, and compositional heterointerfaces. Quantitative relations between the macroscopic strains required, spatial resolution of domain patterns, and defect configurations are developed. In particular, the introduction of arrays of holes is identified as the most feasible phase programming route.

Revisiting Intercalation‐Induced Phase Transitions in 2D Group VI Transition Metal Dichalcogenides

Intercalation of alkali metals is widely studied to introduce a structural phase transition from 2H to 1T′ in 2D group VI transition metal dichalcogenides (TMDCs). This highly efficient phase transition method has enabled an access to a library of phases with novel physical and chemical properties attractive for functional devices and electrochemical catalysis. However, despite numerous studies that have predicted that charge doping mainly contributes to the structural phase transition in the intercalation process, a mechanistic understanding of the phase transition at the atomic level has not been fully revealed. Furthermore, the coupled effects of strain and other intrinsic or extrinsic factors on the intercalation‐induced phase transition have not been quantitatively determined. Herein, the progress of the intercalation‐induced phase transition is briefly overviewed and the knowledge gaps in the current understanding of phase transition and intercalation in 2D TMDCs are highlighted. To fully gain the microscopic picture of the intercalation‐induced phase transition, in situ multimodal probes to monitor the real‐time structure−property relationship during intercalation are suggested. The proposed research directions further direct material scientists to efficiently engineer phase transition pathways in 2D materials to explore novel functional phases.

Γ valley transition metal dichalcogenide moiré bands

The valence band maxima of most group VI transition metal dichalcogenide thin films remain at the Γ point all of the way from bulk to bilayer. In this paper, we develop a continuum theory of the moiré minibands that are formed in the valence bands of Γ-valley homobilayers by a small relative twist. Our effective theory is benchmarked against large-scale ab initio electronic structure calculations that account for lattice relaxation. As a consequence of an emergent [Formula: see text] symmetry, we find that low-energy Γ-valley moiré holes differ qualitatively from their K-valley counterparts addressed previously; in energetic order, the first three bands realize 1) a single-orbital model on a honeycomb lattice, 2) a two-orbital model on a honeycomb lattice, and 3) a single-orbital model on a kagome lattice.

Controllable Thin-Film Approaches for Doping and Alloying Transition Metal Dichalcogenides Monolayers.

Two‐dimensional (2D) transition metal dichalcogenides (TMDs) exhibit exciting properties and versatile material chemistry that are promising for device miniaturization, energy, quantum information science, and optoelectronics. Their outstanding structural stability permits the introduction of various foreign dopants that can modulate their optical and electronic properties and induce phase transitions, thereby adding new functionalities such as magnetism, ferroelectricity, and quantum states. To accelerate their technological readiness, it is essential to develop controllable synthesis and processing techniques to precisely engineer the compositions and phases of 2D TMDs. While most reviews emphasize properties and applications of doped TMDs, here, recent progress on thin‐film synthesis and processing techniques that show excellent controllability for substitutional doping of 2D TMDs are reported. These techniques are categorized into bottom–up methods that grow doped samples on substrates directly and top–down methods that use energetic sources to implant dopants into existing 2D crystals. The doped and alloyed variants from Group VI TMDs will be at the center of technical discussions, as they are expected to play essential roles in next‐generation optoelectronic applications. Theoretical backgrounds based on first principles calculations will precede the technical discussions to help the reader understand each element's likelihood of substitutional doping and the expected impact on the material properties.

Solution-based “bottom-up” synthesis of group VI transition metal dichalcogenides and their applications

“Bottom-up’’ synthetic methods have the potential to produce high quality TMD nanostructures with controllable properties such as size, phase, morphology, and at low-cost.

Disorder engineering in transition metal dichalcogenides toward efficient high current density reduction electrocatalysts

In this perspective, we highlight the importance of nanoscale disorder and mesoscale morphology to enhance the activity and tune the selectivity of group VI transition metal dichalcogenide electrocatalysts toward two paramount reductions reactions as H2 evolution reaction and CO2 reduction. The strategy we propose takes advantage of the metastable nanoscale atomic arrangement of highly disordered and amorphous materials, to overcome the limits of the typical transition metal dichalcogenide crystalline catalysts. For the H2 evolution reaction, going beyond the creation of point defects in crystalline structures in favor of fully amorphous organizations not only increases the per-site activity and active surface area but also improves the conductivity and the reaction kinetics. In addition, the incorporation of nanoscale disorder promotes the formation of complex products in CO2 reduction through reaction pathways inaccessible on other sites. On the other hand, the mesoscale architecture of the catalyst controls mass transport in both the liquid and gas phase, as well as determines the real-world performance of catalysts. We suggest that by exploiting disordered nanoscale organization and controlled mesoscale features, the performances can be drastically improved to reach the state-of-art metallic electrocatalysts.