Layered Dichalcogenides Research Articles

Fractional quantum Hall phases in high-mobility n-type molybdenum disulfide transistors

AbstractTransistors based on semiconducting transition metal dichalcogenides can, in theory, offer high carrier mobilities, strong spin–orbit coupling and inherently strong electronic interactions at the quantum ground states. This makes them well suited for use in nanoelectronics at low temperatures. However, creating robust ohmic contacts to transition metal dichalcogenide layers at cryogenic temperatures is difficult. As a result, it is not possible to reach the quantum limit at which the Fermi level is close to the band edge and thus probe electron correlations in the fractionally filled Landau-level regime. Here we show that ohmic contacts to n-type molybdenum disulfide can be created over a temperature range from millikelvins to 300 K using a window-contacted technique. We observe field-effect mobilities of over 100,000 cm2 V−1 s−1 and quantum mobilities of over 3,000 cm2 V−1 s−1 in the conduction band at low temperatures. We also report evidence for fractional quantum Hall states at filling fractions of 4/5 and 2/5 in the lowest Landau levels of bilayer molybdenum disulfide.

Theory of Linear-Circular Dichroism in Monoatomic Layers of Transition Metal Dichalcogenides Taking into Account the Rabi Effect

We have developed a theory of dimensional quantization for nanostructures, both one-dimensional and zero-dimensional, constructed from monoatomic layers of transition metal dichalcogenides (TMDCs). This theory has enabled us to derive expressions for the energy spectra of charge carriers in both even and odd states (relative to coordinate inversion), as these states occur within quantum-confined lines and points of the TMDC monoatomic layers, dependent on their geometric dimensions. Our numerical analysis provides a detailed exploration of the quantum-confined energy states of electrons within these nanostructures, offering insights into their potential applications in advanced nanoelectronic devices. This work not only advances our understanding of the energy characteristics of TMDC monoatomic layers but also contributes to the broader field of material science by exploring the effects of dimensional quantization on electronic properties.

Homo-Site Nucleation Growth of Twisted Bilayer MoS2 with Commensurate Angles.

Moiré superlattices, composed of two layers of transition metal dichalcogenides with a relative twist angle, provide a novel platform for exploring the correlated electronic phases and excitonic physics. Here, a gas-flow perturbation chemical vapor deposition (CVD) approach is demonstrated to directly grow MoS2 bilayer with versatile twist angles. It is found that the formation of twisted bilayer MoS2 homostructures sensitively depends on the gas-flow perturbation modes, correspondingly featuring the nucleation sites of the second layer at the same (homo-site) as or at the different (hetero-site) from that of the first layer. The commensurate twist angle of ≈22° in homo-site nucleation strategy accounts for ≈16% among the broad range of twist angles due to its low formation energy, which is in consistence with the theoretical calculation. More importantly, moiré interlayer excitons with the enhanced photoluminescence (PL) intensity and the prolonged lifetime are evidenced in the twisted bilayer MoS2 with a commensurate angle of 22°, which is owing to the reason that the strong moiré potential facilitates the interlayer excitons to be trapped in the moiré superlattices. The work provides a feasible route to controllably built twisted MoS2 homostructures with strong moiré potential to investigate the correlated physics in twistronics systems.

Optical control of berry curvature in gated WSe2 bilayers

Abstract Unlike single layers of 2H transition metal dichalcogenides (TMDCs), bilayers of 2H TMDCs maintain inversion and time reversal (TR) symmetries, resulting in a vanishing Berry curvature ( Ω ( k ) ∼ 0 ) that inhibits various potential transport phenomena. A nonzero Berry curvature ( Ω ( k ) ≠ 0 ) is imperative for the occurrence of several unconventional transport phenomena, including the anomalous Hall effect and the anomalous Nernst effect. To overcome this limitation, we break these symmetries in bilayer TMDCs using electrostatic gating and circularly polarized light as external means. For non-gated WSe2 bilayers, circularly polarized light breaks TR symmetry, creating a finite Berry curvature signal in both conduction and valence bands, controllable by light intensity and its polarity. In gated WSe2 bilayers, where inversion symmetry is also broken, we observe a sign reversal in Berry curvature within the conduction bands, the extent of which depends on the relative strengths of the electric gating and light intensity. Overall, under finite bias and light intensity, the 2H bilayers of WSe2 exhibits finite spin Hall, valley Hall, and anomalous Hall conductivities, which depend on the strengths of the applied perturbations.

High Mobility Transistors and Flexible Optical Synapses Enabled by Wafer-Scale Chemical Transformation of Pt-Based 2D Layers.

Electronic devices employing two-dimensional (2D) van der Waals (vdW) transition-metal dichalcogenide (TMD) layers as semiconducting channels often exhibit limited performance (e.g., low carrier mobility), in part, due to their high contact resistances caused by interfacing non-vdW three-dimensional (3D) metal electrodes. Herein, we report that this intrinsic contact issue can be efficiently mitigated by forming the 2D/2D in-plane junctions of 2D semiconductor channels seamlessly interfaced with 2D metal electrodes. For this, we demonstrated the selectively patterned conversion of semiconducting 2D PtSe2 (channels) to metallic 2D PtTe2 (electrodes) layers by employing a wafer-scale low-temperature chemical vapor deposition (CVD) process. We investigated a variety of field-effect transistors (FETs) employing wafer-scale CVD-2D PtSe2/2D PtTe2 heterolayers and identified that silicon dioxide (SiO2) top-gated FETs exhibited an extremely high hole mobility of ∼120 cm2 V-1 s-1 at room temperature, significantly surpassing performances with previous wafer-scale 2D PtSe2-based FETs. The low-temperature nature of the CVD method further allowed for the direct fabrication of wafer-scale arrays of 2D PtSe2/2D PtTe2 heterolayers on polyamide (PI) substrates, which intrinsically displayed optical pulse-induced artificial synaptic behaviors. This study is believed to vastly broaden the applicability of 2D TMD layers for next-generation, high-performance electronic devices with unconventional functionalities.

Cycle-to-cycle switching endurance variability in vertically aligned nanocrystalline molybdenum disulfide: computational insights

We propose a model to depict abrupt transient changes in the endurance test results of a resistive switching device comprising vertically oriented layers of nanocrystalline transition metal dichalcogenide layers with respect to the substrate. We aim to relate and understand the so-called resistance drift occurring in the endurance test results with our model, which is further tested using density functional theory simulations. We conclude that the relationship between resistance drift and skin effect is dominated by alternating electric current resistance and surface resistance. These results are crucial for understanding the resistance drift occurring in several resistive switching devices operating based on defects and ions.

Integration of layered group IV selenides: From SnSe–SnSe2-xSx core-shell crystals to complex (SnSe–SnSe2-xSx)-GeSe van der waals heterostructures

The layered semiconductor tin selenide (SnSe) has received extensive interest due to its promising thermoelectric and ferroelectric properties. Integrating SnSe with other layered crystals in heterostructures can enable the modification of charge- and thermal transport, electrical polarization, and other properties such as chemical stability, optoelectronics, and photonics. Here, we demonstrate the vapor transport synthesis of single-crystalline SnSe monochalcogenide flakes that are spontaneously encapsulated in a thin layered SnSe2-xSx dichalcogenide shell. In a second growth step, such SnSe–SnSe2-xSx heterostructures are integrated with the monochalcogenide GeSe, which is laterally stitched to the SnSe side facets while preserving the dichalcogenide shell across the basal facets. This architecture is confirmed by optical microscopy, electron microscopy and diffraction, energy dispersive X-ray and Raman spectroscopies, as well as cathodoluminescence spectroscopy. The results extend our capabilities for materials integration by forming complex heterostructures with both vertical van der Waals interfaces and covalent lateral interfaces between layered semiconductors.

Direct Assessment of Defective Regions in Monolayer MoS2 Field-Effect Transistors through In Situ Scanning Probe Microscopy Measurements.

Implementing two-dimensional materials in field-effect transistors (FETs) offers the opportunity to continue the scaling trend in the complementary metal-oxide-semiconductor technology roadmap. Presently, the search for electrically active defects, in terms of both their density of energy states and their spatial distribution, has turned out to be of paramount importance in synthetic transition metal dichalcogenides layers, as they are suspected of severely inhibiting these devices from achieving their highest performance. Although advanced microscopy tools have allowed the direct detection of physical defects such as grain boundaries and point defects, their implementation at the device scale to assess the active defect distribution and their impact on field-induced channel charge modulation and current transport is strictly restrained. Therefore, it becomes critical to directly probe the gate modulation effect on the carrier population at the nanoscale of an FET channel, with the objective to establish a direct correlation with the device characteristics. Here, we have investigated the active channel in a monolayer MoS2 FET through in situ scanning probe microscopy, namely, Kelvin probe force microscopy and scanning capacitance microscopy, to directly identify active defect sites and to improve our understanding of the contribution of grain boundaries, bilayer islands, and defective grain domains to channel conductance.

Pressure-induced metallization and enhanced photoelectric activity in layered tin disulfide

Two-dimensional layered metal dichalcogenides have given rise to considerable interest in electronics and optoelectronics fields because of their excellent physical and chemical properties and promising applications. Tin disulfide (SnS2) is an important member of them due to its environment-friendly and resource-rich characteristics. Here, a series of in situ electrical transport experiments and photocurrent measurements under high pressure have been performed to investigate the electrical and opto-electrical properties of 4H-SnS2. With increasing pressure, the electrical resistivity of 4H-SnS2 decrease significantly, leading to a transition from semiconducting to metallic state above 58.6 GPa. The increase in pressure results in a substantial enhancement in photoelectric activity, indicating the extensive potential of utilizing pressure as a trigger for in situ optoelectronic applications. Combined with our previous results of x-ray diffraction and optical absorption at high pressure, pressure-induced structural distortion, bandgap narrowing, metallization, and enhancement of photoelectric activity of 4H-SnS2 are tunable and reversible, which are of great significance for both fundamental research and device design.

Synthesis of NbSe2/Bilayer Nb‐Doped WSe2 Heterostructure from Exfoliated WSe2 Flakes

Forming heterostructures of 2D metals and semiconductors using chemical vapor deposition (CVD) has significant potential to effectively reduce contact resistance in electronic devices. However, semiconducting transition metal dichalcogenide (TMD) layers in metal–semiconductor heterostructures are currently restricted to monolayers despite the superior mobility and density of states in bilayer TMDs. Herein, NbSe2/bilayer Nb‐doped WSe2 metal/semiconductor heterostructure from exfoliated WSe2 flakes are synthesized first. The exfoliated WSe2 bulk crystals on an Nb‐coated substrate are heated to 950 °C under a flow of selenium vapor, and then the NbSe2/bilayer Nb‐doped WSe2 heterostructures are formed. Statistics on the number of Nb‐doped WSe2 layers grown on a 1 cm × 1 cm CVD substrate shows that 65% of the Nb‐doped WSe2 layers are grown as bilayers. X‐ray photoelectron spectroscopy, optical microscopy, and transmission electron microscopy clearly clarify the number of Nb‐doped WSe2 layers and heterostructure of NbSe2/bilayer Nb‐doped WSe2. Electrical measurements using Cr contacts show that bilayer Nb‐doped WSe2 displays 7‐ and 10‐times higher mobility and on/off ratio than monolayer Nb‐doped WSe2. The mobility and on/off ratio are further doubled in NbSe2/bilayer Nb‐doped WSe2 contact compared to Cr/bilayer Nb‐doped WSe2 contact, attributed to a clean interface in vertical stack heterostructure, enhancing electrical performance.

The impact of hBN layers on guided exciton–polariton modes in WS2 multilayers

Abstract Guided exciton–polariton modes naturally exist in bare transition metal dichalcogenide (TMDC) layers due to self-hybridization between excitons and photons. However, these guided polariton modes exhibit a limited propagation distance owing to the substantial exciton absorption within the material. Here, we investigated the impact of hexagonal boron nitride (hBN) layers on guided exciton–polariton modes in WS2 multilayers. By integrating hBN layers, we demonstrate a notable enhancement in the quality of guided exciton–polariton modes. The hBN layers can reduce substrate surface roughness and provide surface protection for the WS2 layer, mitigating inhomogeneous broadening of the exciton resonance. Consequently, we experimentally observed that the propagation distance of polariton modes substantially increased with hBN layers. Additionally, the polariton spectrum broadened due to efficient exciton relaxation to the polariton states at lower energies. Comparison with simulation data emphasizes that the observed improvements are primarily attributed to enhanced exciton quality. The promising outcomes with hBN encapsulation suggest its potential to overcome strong excitonic losses of the guided exciton polariton in implementing nanophotonic devices. Furthermore, this approach provides a new avenue for exploring the novel physics of guided exciton–polariton modes and their potential applications in polariton-based all-optical integrated circuits.

Modulating mediation medium for few layered dichalcogenides enhances inhibition of common pathogens

Illustration of inhibition of pathogens by few layered dichalcogenides.

Reversible Transition of Semiconducting PtSe2 and Metallic PtTe2 for Scalable All-2D Edge-Contacted FETs.

Two-dimensional (2D) transition metal dichalcogenide (TMD) layers are highly promising as field-effect transistor (FET) channels in the atomic-scale limit. However, accomplishing this superiority in scaled-up FETs remains challenging due to their van der Waals (vdW) bonding nature with respect to conventional metal electrodes. Herein, we report a scalable approach to fabricate centimeter-scale all-2D FET arrays of platinum diselenide (PtSe2) with in-plane platinum ditelluride (PtTe2) edge contacts, mitigating the aforementioned challenges. We realized a reversible transition between semiconducting PtSe2 and metallic PtTe2 via a low-temperature anion exchange reaction compatible with the back-end-of-line (BEOL) processes. All-2D PtSe2 FETs seamlessly edge-contacted with transited metallic PtTe2 exhibited significant performance improvements compared to those with surface-contacted gold electrodes, e.g., an increase of carrier mobility and on/off ratio by over an order of magnitude, achieving a maximum hole mobility of ∼50.30 cm2 V-1 s-1 at room temperature. This study opens up new opportunities toward atomically thin 2D-TMD-based circuitries with extraordinary functionalities.

Manipulation of fractionalized charge in the metastable topologically entangled state of a doped Wigner crystal

Metastability of many-body quantum states is rare and still poorly understood. An exceptional example is the low-temperature metallic state of the layered dichalcogenide 1T-TaS2 in which electronic order is frozen after external excitation. Here we visualize the microscopic dynamics of injected charges in the metastable state using a multiple-tip scanning tunnelling microscope. We observe non-thermal formation of a metastable network of dislocations interconnected by domain walls, that leads to macroscopic robustness of the state to external thermal perturbations, such as small applied currents. With higher currents, we observe annihilation of dislocations following topological rules, accompanied with a change of macroscopic electrical resistance. Modelling carrier injection into a Wigner crystal reveals the origin of formation of fractionalized, topologically entangled networks, which defines the spatial fabric through which single particle excitations propagate. The possibility of manipulating topological entanglement of such networks suggests the way forward in the search for elusive metastable states in quantum many body systems.

Vitality of Intralayer Vibration in hBN for Effective Long-Range Interlayer Hole Transfer across High Barriers in MoSe2/hBN/WSe2 Heterostructures.

Introducing the two-dimensional (2D) hexagonal boron nitride (hBN) between 2D transition metal dichalcogenide (TMD) layers promises convenient manipulation of the interlayer exciton (IX) and interlayer charge transfer in TMD/hBN/TMD heterostructures, while the role of inserted hBN layers during IX formation is controversial. Employing ab initio nonadiabatic molecular dynamics (NAMD) simulations and the electron-phonon coupling model, we systematically investigate interlayer hole transfer in MoSe2/WSe2 bilayers intercalated by hBN layers with various thicknesses. The conventional direct hole transfer from MoSe2 to WSe2 is decelerated by 2-3 orders of magnitude after the hBN insertion. Meanwhile, a novel channel intermediated by a deeper hole of WSe2 becomes dominant, where the intralayer shear mode of hBN plays a crucial role by reducing the energy barriers for this new channel. The unique role of hBN layers is revealed for the first time, enriching the knowledge of the underlying microscopic mechanisms and providing instructive guidance to practical van der Waals optoelectronic devices.

Hydrogen Transport Between Layers of Transition Metal‐Dichalcogenides

AbstractHydrogen is a crucial source of green energy and is extensively studied for its potential usage in fuel cells. The advent of 2D crystals (2DCs) has taken hydrogen research to new heights, enabling it to tunnel through layers of 2DCs or be transported within voids between the layers, as demonstrated in recent experiments by Geim's group. In this study, it investigates how the composition and stacking of transition‐metal dichalcogenide (TMDC) layers influence the transport and self‐diffusion coefficients (D) of hydrogen atoms using well‐tempered metadynamics (WTMetaD) simulations. The findings show that modifying either the transition metal or the chalcogen atoms significantly affects the free energy barriers (ΔF) and, consequently, the self‐diffusion of hydrogen atoms between the 2DC layers. In the polytype (2H stacking), MoSe2 exhibits the lowest ΔF, while WS2 has the highest, resulting in the largest D for the former system. Additionally, hydrogen atoms inside the (or 3R) polytype encounter more than twice lower energy barriers and, thus, much higher diffusivity compared to those within the most stable stacking. These findings are particularly significant when investigating twisted layers or homo‐ or heterostructures, as different stacking areas may dominate over others, potentially leading to directional transport and interesting materials for ion or atom sieving.

Electronic band structure and thermoelectric properties of ternary SnSxSe2−x (x = 0,1,2)

In this work, we present a thorough investigation of the electronic structure of layered metal dichalcogenides ternary SnSxSe2−x, where x = 0, 1, and 2. The calculations have been performed by the density functional theory (DFT), density functional perturbation theory (DFPT), and Boltzmann transport theory. It has been found that adding Sulfur to the structure leads to an increase in i) direct and indirect band gaps, ii) the Seebeck coefficient iii) the acoustic and optical branches iv) the power factor v) the lattice thermal conductivity. The thermoelectric properties are studied from the first principle for the whole series of compositions at the highest achievable n- and p-doping levels.

Impact of Carbon Impurities on Air Stability of MOCVD 2D-MoS2

Metal–organic chemical vapor deposition (MOCVD) is a key method for scalable synthesis of two-dimensional transition metal dichalcogenide (2D-TMDC) layers. However, it faces several challenges, such as the unintentional co-deposition of carbon impurities resulting from the pyrolysis of metal–organic precursors. This study investigates the chemical features of carbon and its impact on the photoluminescence property and air stability of 2D-MoS2. Using X-ray photoemission spectroscopy (XPS), it was found that the carbon impurities show characteristics similar to those of sp2-bonded graphitic carbon. Upon prolonged (20–40 weeks) exposure to the atmosphere, the incorporated carbon appears to react with 2D-MoS2, forming a MoS2−xCx solid solution. At the same time, a gradual decrease in the S/Mo ratio implies the formation of sulfur vacancies was also observed. These two processes lead to crystal degradation over time, as evidenced by the gradual quenching of the Raman and photoluminescence (PL) peaks. More detailed PL analyses suggest a charge transfer mechanism between sp2-carbon/2D-MoS2 and 2D-MoS2/air-adsorbates, which, in the short term, could alter PL emissions and appear to further intensify the degradation of 2D-MoS2 in the long-term. The findings highlight the strong impact of unintentionally co-deposited carbon on the optical properties and air stability of MOCVD 2D-MoS2 layers.

Impacts of dielectric screening on the luminescence of monolayer WSe2

Single layers of transition metal dichalcogenides (TMDCs), such as WSe2 have gathered increasing attention due to their intense electron–hole interactions, being considered promising candidates for developing novel optical applications. Within the few-layer regime, these systems become highly sensitive to the surrounding environment, enabling the possibility of using a proper substrate to tune desired aspects of these atomically-thin semiconductors. In this scenario, the dielectric environment provided by the substrates exerts significant influence on electronic and optical properties of these layered materials, affecting the electronic band-gap and the exciton binding energy. However, the corresponding effect on the luminescence of TMDCs is still under discussion. To elucidate these impacts, we used a broad set of materials as substrates for single-layers of WSe2, enabling the observation of these effects over a wide range of electrical permittivities. Our results demonstrate that an increasing permittivity induces a systematic red-shift of the optical band-gap of WSe2, intrinsically related to a considerable reduction of the luminescence intensity. Moreover, we annealed the samples to ensure a tight coupling between WSe2 and its substrates, reducing the effect of undesired adsorbates trapped in the interface. Ultimately, our findings reveal how critical the annealing temperature can be, indicating that above a certain threshold, the heating treatment can induce adverse impacts on the luminescence. Furthermore, our conclusions highlight the influence the dielectric properties of the substrate have on the luminescence of WSe2, showing that a low electrical permittivity favours preserving the native properties of the adjacent monolayer.

Achieving near-perfect light absorption in atomically thin transition metal dichalcogenides through band nesting

Near-perfect light absorbers (NPLAs), with absorbance, {{{{{{{mathcal{A}}}}}}}}, of at least 99%, have a wide range of applications ranging from energy and sensing devices to stealth technologies and secure communications. Previous work on NPLAs has mainly relied upon plasmonic structures or patterned metasurfaces, which require complex nanolithography, limiting their practical applications, particularly for large-area platforms. Here, we use the exceptional band nesting effect in TMDs, combined with a Salisbury screen geometry, to demonstrate NPLAs using only two or three uniform atomic layers of transition metal dichalcogenides (TMDs). The key innovation in our design, verified using theoretical calculations, is to stack monolayer TMDs in such a way as to minimize their interlayer coupling, thus preserving their strong band nesting properties. We experimentally demonstrate two feasible routes to controlling the interlayer coupling: twisted TMD bi-layers and TMD/buffer layer/TMD tri-layer heterostructures. Using these approaches, we demonstrate room-temperature values of {{{{{{{mathcal{A}}}}}}}}=95% at λ=2.8 eV with theoretically predicted values as high as 99%. Moreover, the chemical variety of TMDs allows us to design NPLAs covering the entire visible range, paving the way for efficient atomically-thin optoelectronics.