Bulk Transition Metal Dichalcogenides Research Articles

Role of chalcogen vacancies and hydrogen in the optical and electrical properties of bulk transition-metal dichalcogenides

Like in any other semiconductor, point defects in transition-metal dichalcogenides (TMDs) are expected to strongly impact their electronic and optical properties. However, identifying defects in these layered two-dimensional materials has been quite challenging with controversial conclusions despite the extensive literature in the past decade. Using first-principles calculations, we revisit the role of chalcogen vacancies and hydrogen impurity in bulk TMDs, reporting formation energies and thermodynamic and optical transition levels. We show that the S vacancy can explain recently observed cathodoluminescence spectra of MoS2 flakes and predict similar optical levels in the other TMDs. In the case of the H impurity, we find it more stable sitting on an interstitial site in the Mo plane, acting as a shallow donor, and possibly explaining the often observed n-type conductivity in some TMDs. We also predict the frequencies of the local vibration modes for the H impurity, aiding its identification through Raman or infrared spectroscopy.

Plasmon-assisted boosting of strong self-hybrid exciton–anapole coupling in bulk transition metal dichalcogenides nanoresonators

Intrinsic strong coupling between excitons and anapole mode in self-hybridizing transition metal dichalcogenide (TMD) nanostructures has recently attracted much attention for their capability of improving exciton–anapole interactions as a consequence of the nonradiative feature of anapole mode and the excellent mode overlap in the self-hybridizing geometry. Here, we propose a strategy for further enhancing exciton–anapole coupling. By embedding Au dimers as plasmonic components in slotted bulk WS2 nanodisks, a plasmon-induced electric field strength enhancement over nearly 140 times is achieved compared to that of the bulk WS2 nanodisk, boosting the strong exciton–anapole hybridization with greatly enhanced Rabi splitting up to 532 meV. Importantly, we demonstrate not only the effect of the plasmon mode on the initial Rabi phase of the anapole mode but also the great reduction of the ultrafast energy transfer time by the constructed full-quantum model. The plasmon-assisted hybrid system proposed in this paper provides a promising approach for enhancing strong light–matter interactions and may pave the way for the development of high-performance TMD-based photonic devices.

Monolayer-like Exciton Recombination Dynamics of Multilayer MoSe2 Observed by Pump-Probe Microscopy.

Transition metal dichalcogenides (TMDCs) have garnered considerable interest over the past decade as a class of semiconducting layered materials. Most studies on the carrier dynamics in these materials have focused on the monolayer due to its direct bandgap, strong photoluminescence, and strongly bound excitons. However, a comparative understanding of the carrier dynamics in multilayer (e.g., >10 layers) flakes is still absent. Recent computational studies have suggested that excitons in bulk TMDCs are confined to individual layers, leading to room-temperature stable exciton populations. Using this new context, we explore the carrier dynamics in MoSe2 flakes that are between ∼16 and ∼125 layers thick. We assign the kinetics to exciton-exciton annihilation (EEA) and Shockley-Read-Hall recombination of free carriers. Interestingly, the average observed EEA rate constant (0.003 cm2/s) is nearly independent of flake thickness and 2 orders of magnitude smaller than that of an unencapsulated monolayer (0.33 cm2/s) but very similar to values observed in encapsulated monolayers. Thus, we posit that strong intralayer interactions minimize the effect of layer thickness on recombination dynamics, causing the multilayer to behave like the monolayer and exhibit an apparent EEA rate intrinsic to MoSe2.

The origin of the band-splitting and the spin polarization in bulk 2H-WSe2

Recently, band-splitting associated with spin polarization at K- and K′-points of the Brillouin zone has been found in centrosymmetric transition metal dichalcogenide materials. This discovery offers a possibility on centrosymmetric crystals for potential valleytronic applications. However, the origin of the band-splitting and the spin polarization in multilayer and bulk transition metal dichalcogenides remains unclear as the interlayer coupling should play a role when compared with that in monolayers. Here, by performing spin- and angle-resolved photoemission spectroscopy in bulk 2H-WSe2 at variable temperatures, we have quantitatively established contributions of the intralayer spin–orbit coupling and interlayer coupling. While the strength of the intralayer spin–orbit coupling is determined to be 450 meV, independent of the temperature, the strength of the interlayer coupling is found to increase from 68 to 172 meV as the temperature decreases from 300 to 80 K. This is also accompanied by an increase in the total band-splitting and a decrease in the spin polarization. This work reveals the micro-mechanism of spin and interlayer interaction in centrosymmetric materials, which provides a basis for the development of next-generation energy-efficient valleytronic devices.

Strong light-matter interactions of exciton in bulk WS2 and a toroidal dipole resonance.

Exciton-polaritonic states are generated by strong interactions between photons and excitons in nanocavities. Bulk transition metal dichalcogenides (TMDCs) host excitons with a large binding energy at room temperature, and thus are regarded as an ideal platform for realizing exciton-polaritons. In this work, we investigate the strong coupling properties between high-Q toroidal dipole (TD) resonance and bulk WS2 excitons in a hybrid metasurface, consisting of Si3N4 nanodisk arrays with embedded WS2. Multipole decomposition and near-field distribution confirm that Si3N4 nanodisk arrays support strong TD resonance. The TD resonance wavelength is easily tuned to overlap with the bulk WS2 exciton wavelength, and strong coupling is observed when the bulk WS2 is integrated with the hollow nanodisk and the oscillator strength of the WS2 material is adjusted to be greater than 0.6. The Rabi splitting of the hybrid device is up to 65 meV. In addition, strong coupling is confirmed by the anticrossing of fluorescence enhancement in the hybrid Si3N4-WS2 metastructure. Our findings are expected to be of importance for both fundamental research in TMDC-based light-matter interactions and practical applications in the design of high-performance exciton-polariton devices.

Strong coupling between excitons and quasibound states in the continuum in bulk transition metal dichalcogenides

We investigate the strong coupling between the excitons and quasi-bound states in the continuum (BIC) resonance in a bulk WS$_2$ metasurface. Here we employ the bulk WS$_2$ to construct an ultrathin nanodisk metasurface, supporting the symmetry-protected magnetic dipole (MD) quasi-BIC resonance, which can self-hybridize with the excitons and lead to a strong light-matter interaction enhancement within the structure without the necessity for an external cavity. This strong coupling can be charactered by the considerable Rabi splitting of 159 meV and the clearly anti-crossing behavior appeared in the absorption spectrum. Furthermore, we analyze such light-matter coupling by constructing a Hamiltonian model including the surplus excitons, and tune the interaction from weak coupling to strong coupling regimes via the tunability radiation loss of the quasi-BIC resonance. Our results have great potential for manipulating the exciton-polaritons at room temperature, and provide a promising prospect for photonic devices that exploit strong coupling in applications.

Patterned Growth of Transition Metal Dichalcogenide Monolayers and Multilayers for Electronic and Optoelectronic Device Applications.

A simple, large area, and cost-effective soft lithographic method is presented for the patterned growth of high-quality 2D transition metal dichalcogenides (TMDs). Initially, a liquid precursor (Na2 MoO4 in an aqueous solution) is patterned on the growth substrate using the micromolding in capillaries technique. Subsequently, a chemical vapor deposition step is employed to convert the precursor patterns to monolayer, few layers, or bulk TMDs, depending on the precursor concentration. The grown patterns are characterized using optical microscopy, atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and photoluminescence spectroscopy to reveal their morphological, chemical, and optical characteristics. Additionally, electronic and optoelectronic devices are realized using the patterned TMDs and tested for their applicability in field effect transistors and photodetectors. The photodetectors made of MoS2 line patterns show a very high responsivity of 7674 A W-1 and external quantum efficiency of 1.49 × 106 %. Furthermore, the multiple grain boundaries present in patterned TMDs enable the fabrication of memtransistor devices. The patterning technique presented here may be applied to many other TMDs and related heterostructures, potentially advancing the fabrication of TMDs-based device arrays.

Anisotropic slot waveguides with bulk transition metal dichalcogenides for crosstalk reduction and high-efficiency mode conversion.

Conventional slot waveguides (CSWs) consisting of an isotropic low-index material sandwiched by two high-index silicon wires have been extensively used in functional photonic devices, including chemical sensing, optical modulating, and all-optical signal processing, due to its significantly enhanced electric field perpendicular to the interfaces in the slot layer. However, there are two drawbacks to be improved if the CSWs are used for signal transmission in photonic integrated circuits, including the crosstalk between waveguides and direct butting mode conversion efficiency (MCE) to a silicon (Si)-strip waveguide. In this study, we propose an anisotropic SW with bulk transition metal dichalcogenide (ASWTMD) to relieve the two shortcomings by replacing the isotropic low-index slot layer with a bulk molybdenum disulfide layer having a high refractive index and giant optical anisotropy. We demonstrated the crosstalk reduction (CR) of the proposed ASWTMD by analyzing the mode profile, power confinement, and coupling strength. We also investigated the MCE by examining the mode overlap ratio and power evolution. The proposed ASWTMD shows significant CR and superior MCE for the transverse electric and transverse magnetic modes compared to those of a CSW with a SiO2-slot layer. The present design paves the possible extensibility to other transition metal dichalcogenides (TMDs) for designing state-of-the-art TMD-based photonic devices exploiting their extraordinary optical properties.

Nonlinear Exciton‐Mie Coupling in Transition Metal Dichalcogenide Nanoresonators

AbstractThanks to a high refractive index, giant optical anisotropy, and pronounced excitonic response, bulk transition metal dichalcogenides (TMDCs) have recently been discovered to be an ideal foundation for post‐silicon photonics. The inversion symmetry of bulk TMDCs, on the other hand, prevents their use in nonlinear‐optical processes such as second‐harmonic generation (SHG). To overcome this obstacle and broaden the application scope of TMDCs, MoS2 nanodisks are engineered to couple Mie resonances with C‐excitons. As a result, their alliance produces 23‐fold enhancement of SHG intensity with respect to the resonant SHG from a high‐quality exfoliated MoS2 monolayer under C‐exciton excitation. Furthermore, SHG demonstrates a strongly anisotropic response typical of a MoS2 monolayer due to the single‐crystal structure of the fabricated nanodisks, providing a polarization degree of freedom to manipulate SHG. Hence, these results significantly improve the potential of bulk TMDCs enabling an avenue for next‐generation nonlinear photonics.

A biodegradable polymer-assisted efficient and universal exfoliation route to a stable few layer dispersion of transition metal dichalcogenides

Quasi two-dimensional transition metal dichalcogenides (2D-TMDs) with 1–5 layers have been obtained by developing an effective and highly efficient bio-based polymer-solvent system by mild ultrasonication. The hydroxypropyl cellulose (HPC)/1-Butanol (BuOH) system was determined to be an universal polymer-solvent system to effectively exfoliate the bulk transition metal dichalcogenides (TMDs) MoS2, TiS2, WS2, NbS2 and MoSe2. The above process is significant as it is a room temperature liquid phase exfoliation method that leads to a stable dispersion of a few layer 2D-TMD having significant proportion (>50%) of exfoliated material which remains stable in suspension for several months.

Evidence for the Fulde\u2013Ferrell\u2013Larkin\u2013Ovchinnikov state in bulk NbS2

We present measurements of the magnetic torque, specific heat and thermal expansion of the bulk transition metal dichalcogenide (TMD) superconductor NbS2 in high magnetic fields, with its layer structure aligned strictly parallel to the field using a piezo rotary positioner. The upper critical field of superconducting TMDs in the 2D form is known to be dramatically enhanced by a special form of Ising spin orbit coupling. This Ising superconductivity is very robust to the Pauli paramagnetic effect and can therefore exist beyond the Pauli limit for superconductivity. We find that superconductivity beyond the Pauli limit still exists in bulk single crystals of NbS2 for a precisely parallel field alignment. However, the comparison of our upper critical field transition line with numerical simulations rather points to the development of a Fulde-Ferrell-Larkin-Ovchinnikov state above the Pauli limit as a cause. This is also consistent with the observation of a magnetic field driven phase transition in the thermodynamic quantities within the superconducting state near the Pauli limit.

Spontaneous interlayer compression in commensurately stacked van der Waals heterostructures

Interest in layered two dimensional materials, particularly stacked heterostructures of transition metal dichalcogenides, has led to the need for a better understanding of the structural and electronic changes induced by stacking. Here, we investigate the effects of idealized heterostructuring, with periodic commensurate stacking, on the structural, electronic, and vibrational properties, when compared to the counterpart bulk transition metal dichalcogenide. We find that in heterostructures with dissimilar chalcogen species there is a strong compression of the inter-layer spacing, compared to the bulk compounds. This compression of the heterostructure is caused by an increase in the strength of the induced polarization interaction between the layers, but not a full charge transfer. We argue that this effect is real, not due to the imposed commensurability, and should be observable in heterostructures combining different chalcogens. Interestingly, we find that incommensurate stacking of Ti-based dichalcogenides leads to the stabilization of the charge density wave phonon mode, which is unstable in the 1T phase at low temperature. Mixed Ti- and Zr-heterostructures are still unstable, but with a charge density wave or a ferroelectric instability.

Theoretical study of structural and electronic properties of 2H -phase transition metal dichalcogenides

Computational physics and chemistry are called to play a very important role in the development of new technologies based on two-dimensional (2D) materials, reducing drastically the number of trial and error experiments needed to obtain meaningful advances in the field. Here, we present a thorough theoretical study of the structural and electronic properties of the single-layer, double-layer, and bulk transition metal dichalcogenides ${\mathrm{MoS}}_{2}$, ${\mathrm{MoSe}}_{2}$, ${\mathrm{MoTe}}_{2}$, ${\mathrm{WS}}_{2}$, ${\mathrm{WSe}}_{2}$, and ${\mathrm{WTe}}_{2}$ in the $2H$ phase, for which only partial experimental information is available. We show that the properties of these systems depend strongly on the density functional theory approach used in the calculations and that inclusion of weak dispersion forces is mandatory for a correct reproduction of the existing experimental data. By using the most accurate functionals, we predict interlayer separations, direct and indirect band gaps, and spin-orbit splittings in those systems for which there is no experimental information available. We also discuss the variation of these properties with the specific chalcogen and transition metal atom.

Symmetry and control of spin-scattering processes in two-dimensional transition metal dichalcogenides

Transition metal dichalcogenides (TMDs) combine interesting optical and spintronic properties in an atomically thin material, where the light polarization can be used to control the spin and valley degrees of freedom for the development of novel optospintronic devices. These promising properties emerge due to their large spin-orbit coupling in combination with their crystal symmetries. Here, we provide simple symmetry arguments in a group-theory approach to unveil the symmetry-allowed spin-scattering mechanisms, and indicate how one can use these concepts towards an external control of the spin lifetime. We perform this analysis for both monolayer (inversion asymmetric) and bilayer (inversion symmetric) crystals, indicating the different mechanisms that play a role in these systems. We show that in monolayer TMDs, electrons and holes transform fundamentally differently----leading to distinct spin-scattering processes. We find that one of the electronic states in the conduction band is partially protected by time-reversal symmetry, indicating a longer spin lifetime for that state. In bilayer and bulk TMDs, a hidden spin polarization can exist within each layer despite the presence of global inversion symmetry. We show that this feature enables control of the interlayer spin-flipping scattering processes via an out-of-plane electric field, providing a mechanism for electrical control of the spin lifetime.

All van der Waals Integrated Nanophotonics with Bulk Transition Metal Dichalcogenides

Integrated optics is at the heart of a wide range of systems from remote sensing and communications to computing and quantum information processing. Demand for smaller and more energy efficient structures stimulates search for more advanced material platforms. Here, we propose a concept of an all van der Waals photonics, where we show that electronically bulk transition metal dichalcogenide (TMDC) semiconductors are well fitted for the design of key optical components for nanoscale and integrated photonics. Specifically, we demonstrate theoretically that owing to low optical loss and high refractive index across near-infrared and telecom frequency bands, components made of bulk TMDCs can potentially outperform counterparts made of conventional 3D semiconductors, such as Si and III/Vs. We discuss several key quantum and classical optical components and show that bulk TMDCs may pave the way to smaller footprint devices, more energy efficient electro-optical modulators, and stronger quantum light-materials interaction. Enhanced optical performance, ease of integration, and a wide selection of materials suggest that bulk TMDCs may complement and, potentially, replace existing integrated photonics systems.

Thickness dependence of work function, ionization energy, and electron affinity of Mo and W dichalcogenides from DFT and GW calculations

Transition-metal dichalcogenides (TMDs) are promising for two-dimensional (2D) semiconducting devices and novel phenomena. For 2D applications, their work function, ionization energy, and electron affinity are required as a function of thickness, but research on this is yet to cover the full family of compounds. Here, we present the work function, ionization energy, and electron affinity of few-layer and bulk MX2 (M = Mo, W and X = S, Se, Te) in 2H phase obtained accurately by the density functional theory and GW calculations. For each compound, we consider one-, two-, three-, four-layer, and bulk geometry. In GW calculations, accurate results are obtained by nonuniform q sampling for two-dimensional geometry. From band energies including the GW self-energy correction, we estimate the work function, band gap, ionization energy, and electron affinity as functions of the number of layers. We compare our results with available theoretical and experimental reports, and we discuss types of band alignments in in-plane and out-of-plane junctions of these few-layer and bulk TMDs.

Broadband optical properties of monolayer and bulk MoS2

Layered semiconductors such as transition metal dichalcogenides (TMDs) offer endless possibilities for designing modern photonic and optoelectronic components. However, their optical engineering is still a challenging task owing to multiple obstacles, including the absence of a rapid, contactless, and the reliable method to obtain their dielectric function as well as to evaluate in situ the changes in optical constants and exciton binding energies. Here, we present an advanced approach based on ellipsometry measurements for retrieval of dielectric functions and the excitonic properties of both monolayer and bulk TMDs. Using this method, we conduct a detailed study of monolayer MoS2 and its bulk crystal in the broad spectral range (290–3300 nm). In the near- and mid-infrared ranges, both configurations appear to have no optical absorption and possess an extremely high dielectric permittivity making them favorable for lossless subwavelength photonics. In addition, the proposed approach opens a possibility to observe a previously unreported peak in the dielectric function of monolayer MoS2 induced by the use of perylene-3,4,9,10-tetracarboxylic acid tetrapotassium salt (PTAS) seeding promoters for MoS2 synthesis and thus enables its applications in chemical and biological sensing. Therefore, this technique as a whole offers a state-of-the-art metrological tool for next-generation TMD-based devices.

Thickness dependence of solar cell efficiency in transition metal dichalcogenides MX2 (M: Mo, W; X: S, Se, Te)

Bulk transition metal dichalcogenides are indirect gap semiconductors with optical gaps in the range of 0.7–1.6 eV, which makes them suitable for solar cell applications. In this work, we study the electronic structure, optical properties, and the thickness dependence of the solar cell efficiencies of MX2 (M: Mo, W; X: S, Se, Te) with density functional theory and GW + BSE. Through this analysis, we find a change in solar cell efficiency trends at slab thicknesses of 3 μm. For thin films solar cells (thicknesses smaller than 3 μm), the tellurides present the highest efficiencies (about 20% for a 100 nm thick slab). In contrast, for thicknesses greater than 3 μm, our results indicate that a maximum solar cell efficiency can be achieved in WS2. For instance, a 100 μm slab of WS2 presents a solar cell efficiency of 36.3%, making this material a promising candidate for solar cell applications.

Gate-controlled spin relaxation in bulk WSe2 flakes

We have studied the spin relaxation dynamics in both n- and p-type layered bulk WSe2 under a perpendicular electric field by employing time-resolved Kerr rotation and helicity-resolved transient reflection measurements. The experimental results reveal the efficient tuning of spin relaxation time from 3 ps to 46 ps by the external electric field at 10 K. The dependence of spin relaxation time on the external electric field is understood based on active interlayer hopping. These studies demonstrate the gate-tunable spin polarization and relaxation in bulk transition metal dichalcogenides (TMDCs), which are fundamentally important for understanding spin dynamics and the practical design of spintronic devices based on bulk TMDCs.

Electronic Structure Mosaicity of Monolayer Transition Metal Dichalcogenides by Spontaneous Pattern Formation of Donor Molecules.

Modulating the electronic structure of semiconducting materials is critical to developing high-performance electronic and optical devices. Transition metal dichalcogenides (TMDCs) are atomically thin semiconducting materials. However, before they can be used successfully in electronic and optical devices, modulation of their carrier concentration at the nanometer scale must be achieved. Molecular doping has been successful in modulating the carrier concentration; however, the scientific approach for selective and local carrier doping at the nanometer scale is still missing. Here, we demonstrate a proof-of-concept of modulating the carrier concentration of TMDCs laterally on a scale of around 100 nm using spontaneous pattern formation of an ultrathin film consisting of molecular electron dopants. When the water made contact with the molecular film (∼10 nm), a spontaneous pattern formation was observed on both the monolayer and bulk TMDCs. We revealed that the pattern-formation dynamics and nanoscopic flow rate of the molecules were highly dependent on the thickness of the TMDCs, since the band gap varies based on the number of layers. Analyses of topographic images of the molecular patterns and photoluminescence spectra of the TMDCs indicated that the spontaneously patterned molecular films induced a local carrier doping. Our results demonstrate a spontaneous formation of a mosaic electronic structure. This work is useful for making tiny-scale electronic junctions on TMDCs and semiconducting materials to make numerous p/n junctions simultaneously for optoelectronic devices.