Single-layer Transition Metal Dichalcogenides Research Articles

Light-Induced Polaronic Crystals in Single-Layer Transition Metal Dichalcogenides.

Light-induced ordered states can emerge in materials after irradiation with ultrafast laser pulses. However, their prediction is challenging because the inverted band occupation confounds our chemical intuition. Hence, we use a recently developed constrained density functional perturbation theory approach to systematically screen single-layer transition metal dichalcogenides (TMDs) for light-induced ordered states. We demonstrate that all examined single-layer TMDs reveal similar light-induced charge orderings. The corresponding reconstructions are periodic arrangements of polarons (polaronic crystals), characterized by triangular metal clusters and having no equivalent at equilibrium conditions. The polarons are accompanied by localized midgap states in the electronic band structure, detectable by experimental methods. We assess the selenides as the most promising candidates for potential photoexcitation experiments because they transition at low critical fluences, have low transition barriers, and maintain an open band gap under photoexcitation. Our work paves the way for innovative material design approaches targeting light-induced phases.

TEM-processed defect densities in single-layer TMDCs and their substrate-dependent signature in PL and Raman spectroscopy

The optical properties of the direct-bandgap transition metal dichalcogenides (TMDCs) MoS2 and WS2 are heavily influenced by their atomic defect structure and substrate interaction. In this work we use low-voltage chromatic and spherical aberration (CC/CS)-corrected high-resolution transmission electron microscopy to simultaneously create and image chalcogen vacancies in TMDCs. However, correlating the defect structure, produced and analyzed using transmission electron microscopy (TEM), with optical spectroscopy often presents challenges because of very different fields of view and sample platforms involved. Here we employ a reverse transfer technique to transfer electron-irradiated single-layer MoS2 and WS2 from the TEM grid to various substrates for subsequent optical examination. The dynamics of defect creation are studied in atomic resolution on a separate sample, which allows to apply the derived statistics to larger irradiated areas on the other samples. The intensity of both the defect-bound exciton peak in photoluminescence (PL) and the defect-induced LA(M) mode in Raman spectra increase with defect density. The best substrates for defect-density determination by optical spectroscopy are polystyrene for PL and SiC and Si/SiO2 for Raman spectroscopy. These investigations represent an important step towards the quantification of defects using solely optical spectroscopy, paving the way for fast, reliable, and automatable optical quality control of optoelectronic devices.

Optical Signal Investigation of Monolayer MoS2 Grown Via Glass-Assisted CVD On Patterned Surfaces

Enhancing photoluminescence (PL) in single-layer transition metal dichalcogenides has garnered significant interest, particularly for advancing high-performance 2D electronics and optoelectronics. The combination of surface engineering and contemporary growth methods has provided a platform for investigating optical signals. In this study, we present variations in PL and Raman signals of single-layer MoS2 flakes grown conformally using the glass-assisted CVD method on square-patterned surfaces with varying well depths. PL spectroscopy revealed a systematic and pronounced enhancement in intensities as the valley thickness decreased from 285 nm to 225 nm. Conversely, for the hill regions of the samples, the PL intensity initially increased with decreasing valley thickness and then decreased, despite the hill regions having a constant thickness of 300 nm. On the other hand, PL maps did not exhibit a systematic dependence of intensities on the hill-valley thickness distinction, contrary to expected results based on literature data for similar materials on flat surfaces. The origin of the intensity oscillations was attributed to possible mechanisms, including thickness-dependent interference and strain-related exciton funneling effects. Additionally, Raman measurements revealed irregular variations in intensity in hill regions, dependent on the thicknesses of the underlying SiO2 layers. Furthermore, we observed that the sizes of the flakes increased as the well depths of the underlying patterned surface decreased. This phenomenon might be attributed to alterations in the carrier gas flow pattern and varying temperature gradients between the hills and valleys. These results hold substantial potential to open new avenues for the integration of 2D transition metal dichalcogenides into on-chip electronic and optoelectronic devices.

Pump-Driven Opto-Magnetic Properties in Semiconducting Transition-Metal Dichalcogenides: An Analytical Model.

Single-layer transition-metal dichalcogenides provide an unique intrinsic entanglement between the spin/valley/orbital degrees of freedom and the polarization of scattered photons. This scenario gives rise to the well-assessed optical dichroism observed by using both steady and time-resolved probes. In this paper, we provide compact analytical modeling of the onset of a finite Faraday/Kerr optical rotation upon shining with circularly polarized light. We identify different optical features displaying optical rotation at different characteristic energies, and we describe in an analytical framework the time-dependence of their intensities as a consequence of the main spin-conserving and spin-flip processes.

Large Biaxial Compressive Strain Tuning of Neutral and Charged Excitons in Single-Layer Transition Metal Dichalcogenides.

The absorption and emission of light in single-layer transition metal dichalcogenides are governed by the formation of excitonic quasiparticles. Strain provides a powerful technique to tune the optoelectronic properties of two-dimensional materials and thus to adjust their exciton energies. The effects of large compressive strain in the optical spectrum of two-dimensional (2D) semiconductors remain rather unexplored compared to those of tensile strain, mainly due to experimental constraints. Here, we induced large, uniform, biaxial compressive strain (∼1.2%) by cooling, down to 10 K, single-layer WS2, MoS2, WSe2, and MoSe2 deposited on polycarbonate substrates. We observed a significant strain-induced modulation of neutral exciton energies, with blue shifts up to 160 meV, larger than in any previous experiments. Our results indicate a remarkably efficient transfer of compressive strain, demonstrated by gauge factor values exceeding previous results and approaching theoretical expectations. At low temperatures, we investigated the effect of compressive strain on the resonances associated with the formation of charged excitons. In WS2, a notable reduction of gauge factors for charged compared to neutral excitons suggests an increase in their binding energy, which likely results from the effects of strain added to the influence of the polymeric substrate.

Engineering Single-Layer Hollow Structure of Transition Metal Dichalcogenides with High 1T-Phase Purity for Hydrogen Evolution Reaction.

Rational design and controllable synthesis of hollow structures based on transition metal dichalcogenides (TMDs) have gained tremendous attention in the field of clean energy. However, the general synthetic strategies to fabricate single-layer hollow structures of TMDs, especially with unconventional phases (e.g., 1T or 1T'), still pose significant challenges. Herein, a scalable method is reported for the synthesis of single-layer hollow spheres (SLHS) of TMDs with high 1T-phase purity by etching bismuth (Bi) cores from pre-synthesized Bi@TMDs core-shell heterostructures including SLHS-1T-MoS2 , SLHS-1T-MoSe2 , SLHS-1T-WS2 , and SLHS-1T-WSe2 . Additionally, the etched Bi ions can be adsorbed on the single-layer TMDs shells in the form of single atoms (SAs) via the Bi─S bond. Due to the benefits of the single-layer hollow structure, high conductivity of 1T phase, and synergistic effect of Bi SAs and TMDs supports, the fabricated SLHS-1T-MoS2 exhibits superior electrocatalytic performance for hydrogen production. This work provides a way to manufacture advanced functional materials based on the single-layer hollow structures of 1T-TMDs and to expand their applications.

Ultra‐High Interfacial Thermal Conductance via Double hBN Encapsulation for Efficient Thermal Management of 2D Electronics (Small 12/2023)

Ultra-High Interfacial Thermal Conductance In article number 2205726, Baoxing Xu, Philip X.-L. Feng, Xian Zhang, and co-workers report on the ultra-high interfacial thermal conductance in encapsulated van der Waals (vdW) heterostructures with single-layer transition metal dichalcogenides MX2 (MoS2, WSe2, WS2) sandwiched between two hexagonal boron nitride (hBN) layers, through Raman spectroscopic measurements. The findings in this study reveal new thermal transport mechanisms in hBN/MX2/hBN structures and shed light on building novel flexible electronic devices.

Ultra-High Interfacial Thermal Conductance via Double hBN Encapsulation for Efficient Thermal Management of 2D Electronics.

Heat dissipation is a major limitation of high-performance electronics. This is especially important in emerging nanoelectronic devices consisting of ultra-thin layers, heterostructures, and interfaces, where enhancement in thermal transport is highly desired. Here, ultra-high interfacial thermal conductance in encapsulated van der Waals (vdW) heterostructures with single-layer transition metal dichalcogenides MX2 (MoS2 , WSe2 , WS2 ) sandwiched between two hexagonal boron nitride (hBN) layers is reported. Through Raman spectroscopic measurements of suspended and substrate-supported hBN/MX2 /hBN heterostructures with varying laser power and temperature, the out-of-plane interfacial thermal conductance in the vertical stack is calibrated. The measured interfacial thermal conductance between MX2 and hBN reaches 74 ± 25 MW m-2 K-1 , which is at least ten times higher than the interfacial thermal conductance of MX2 in non-encapsulation structures. Molecular dynamics (MD) calculations verify and explain the experimental results, suggesting a full encapsulation by hBN layers is accounting for the high interfacial conductance. This ultra-high interfacial thermal conductance is attributed to the double heat transfer pathways and the clean and tight vdW interface between two crystalline 2D materials. The findings in this study reveal new thermal transport mechanisms in hBN/MX2 /hBN structures and shed light on building novel hBN-encapsulated nanoelectronic devices with enhanced thermal management.

Two-Dimensional Transition Metal Dichalcogenide Based Biosensors: From Fundamentals to Healthcare Applications.

There has been an exponential surge in reports on two-dimensional (2D) materials ever since the discovery of graphene in 2004. Transition metal dichalcogenides (TMDs) are a class of 2D materials where weak van der Waals force binds individual covalently bonded X-M-X layers (where M is the transition metal and X is the chalcogen), making layer-controlled synthesis possible. These individual building blocks (single-layer TMDs) transition from indirect to direct band gaps and have fascinating optical and electronic properties. Layer-dependent opto-electrical properties, along with the existence of finite band gaps, make single-layer TMDs superior to the well-known graphene that paves the way for their applications in many areas. Ultra-fast response, high on/off ratio, planar structure, low operational voltage, wafer scale synthesis capabilities, high surface-to-volume ratio, and compatibility with standard fabrication processes makes TMDs ideal candidates to replace conventional semiconductors, such as silicon, etc., in the new-age electrical, electronic, and opto-electronic devices. Besides, TMDs can be potentially utilized in single molecular sensing for early detection of different biomarkers, gas sensors, photodetector, and catalytic applications. The impact of COVID-19 has given rise to an upsurge in demand for biosensors with real-time detection capabilities. TMDs as active or supporting biosensing elements exhibit potential for real-time detection of single biomarkers and, hence, show promise in the development of point-of-care healthcare devices. In this review, we provide a historical survey of 2D TMD-based biosensors for the detection of bio analytes ranging from bacteria, viruses, and whole cells to molecular biomarkers via optical, electronic, and electrochemical sensing mechanisms. Current approaches and the latest developments in the study of healthcare devices using 2D TMDs are discussed. Additionally, this review presents an overview of the challenges in the area and discusses the future perspective of 2D TMDs in the field of biosensing for healthcare devices.

Formation of oriented layered MoS2 from amorphous thin film revealed by polarized x-ray absorption spectroscopy

MoS2 is a prototypical two-dimensional van der Waals (vdW) solid, where covalently bonded S–Mo–S triplets are held together by weaker vdW forces. In this work, we have studied structural transformation from a three-dimensional amorphous phase of MoS2 into a layered vdW crystal using S L2,3 edge x-ray absorption near-edge structure (XANES) spectroscopy with in-plane and out-of-plane polarized x-ray beam. The crystallization process, which starts from an isotropic amorphous phase, is accompanied by the establishment of vdW interaction between covalently bonded layers, resulting in the anisotropic nature of the crystalline phase. We have disclosed that the preferential growth of MoS2 layers along the (200) Bragg reflection commences immediately from the amorphous phase with no intermediate crystal orientations. We have additionally identified a unique signature in the S L2,3 edge spectrum that is associated with vdW bonds and can be possibly used to determine sulfur-based single-layered and multi-layered transition metal dichalcogenides.

Single-layer and bilayer MoSTe for photocatalytic water splitting: Role of optical absorption correction and band edge distribution

Single-layer and bilayer Janus transition metal dichalcogenides (TMDCs) attain great attention for possible application in solar water splitting. The crucial issues for solar water splitting are the band edge positions and optical absorption of photocatalysts. However, for this large group of Janus TMDCs materials, their optical absorption correction by the effective unit cell volume and the charge distribution of band edges, were not investigated in most previous works. To clarify these issues, we herein studied the electronic and optical properties of typical single-layer and bilayer MoSTe using first-principles calculations. Remarkably, when corrected by the effective unit cell volume, the optical absorption of bilayer MoSTe is not enhanced when compared to that of single-layer MoSTe. On the other hand, single-layer MoSTe possesses no solar water-splitting ability for lack of suitable band edges, when the charge distribution of band edges is considered. Furthermore, favorable band edges for water splitting were achieved in bilayer MoSTe. In brief, this work emphasized the optical absorption correction by the effective unit cell volume and the charge distribution of band edges when searching for 2D photocatalysts stacking by Janus monolayers.

Janus structures of SMoSe and SVSe compositions with low enthalpy and unusual crystal chemistry

The recent synthesis of single-layer Janus-type transition metal dichalcogenides (TMDs) raises the question of the existence of other possible 2D structures with an asymmetric out-of-plane structural configuration. In the present work, a theoretical search for new Janus structures having SMoSe and SVSe compositions is performed. A detailed crystal-chemical analysis of the predicted structures is carried out, and it is shown that some of the dynamically stable structures are characterized by crystal-chemical features that are unique among TMDs, including quadruple Mo—Mo bonds and covalent S—S and Se—Se bonds. It is also shown that Mo-bearing TMDs have a tendency to form strong Mo—Mo bonds with chains or isolated dimers of molybdenum atoms, while in the case of vanadium-containing TMDs this feature is not characteristic. Two predicted crystal structures, called 1M-SVSe and 1A′-SMoSe, are especially promising for experimental synthesis and practical applications owing to their dynamical stability and rather low value of enthalpy compared with known structures. The enthalpy of 1M-SVSe is 0.22 eV per formula unit lower than that of 1T-SVSe, while the enthalpy of 1A′-SMoSe is 0.12 eV per formula unit lower than the enthalpy of 1T-SMoSe. The performed topological analysis showed that the predicted structures are unique and do not have analogues in the Inorganic Crystal Structure Database.

Probing the charged defects in single-layer WS2 at atomic level

Structural defects in two-dimensional materials offer an effective way to engineer their functionalities. In-situ local measurements to build the structure-function relationship are crucial for future device technology. Here, we present a comprehensive study of intrinsic defects in single-layer WS2 grown by chemical vapor deposition using a combination of scanning tunneling microscopy/spectroscopy, non-contact atomic force microscopy and density functional theory calculations. We probed the rarely observed positively charged defects and the intersection of adjacent charging rings at sufficiently high bias caused by subsurface defects. We also directly identified and visualized the widely observed negatively charged defects as chalcogen vacancies-related defects. The results reported here will guide future efforts of targeted defect engineering and doping of the single-layer transition metal dichalcogenides.

Disentangling Many-Body Effects in the Coherent Optical Response of 2D Semiconductors.

In single-layer (1L) transition metal dichalcogenides, the reduced Coulomb screening results in strongly bound excitons which dominate the linear and the nonlinear optical response. Despite the large number of studies, a clear understanding on how many-body and Coulomb correlation effects affect the excitonic resonances on a femtosecond time scale is still lacking. Here, we use ultrashort laser pulses to measure the transient optical response of 1L-WS2. In order to disentangle many-body effects, we perform exciton line-shape analysis, and we study its temporal dynamics as a function of the excitation photon energy and fluence. We find that resonant photoexcitation produces a blue shift of the A exciton, while for above-resonance photoexcitation the transient response at the optical bandgap is largely determined by a reduction of the exciton oscillator strength. Microscopic calculations based on excitonic Heisenberg equations of motion quantitatively reproduce the nonlinear absorption of the material and its dependence on excitation conditions.

Imaging gate-tunable Tomonaga-Luttinger liquids in 1H-MoSe2 mirror twin boundaries.

One-dimensional electron systems exhibit fundamentally different properties than higher-dimensional systems. For example, electron-electron interactions in one-dimensional electron systems have been predicted to induce Tomonaga-Luttinger liquid behaviour. Naturally occurring grain boundaries in single-layer transition metal dichalcogenides exhibit one-dimensional conducting channels that have been proposed to host Tomonaga-Luttinger liquids, but charge density wave physics has also been suggested to explain their behaviour. Clear identification of the electronic ground state of this system has been hampered by an inability to electrostatically gate such boundaries and tune their charge carrier concentration. Here we present a scanning tunnelling microscopy and spectroscopy study of gate-tunable mirror twin boundaries in single-layer 1H-MoSe2 devices. Gating enables scanning tunnelling microscopy and spectroscopy for different mirror twin boundary electron densities, thus allowing precise characterization of electron-electron interaction effects. Visualization of the resulting mirror twin boundary electronic structure allows unambiguous identification of collective density wave excitations having two velocities, in quantitative agreement with the spin-charge separation predicted by finite-length Tomonaga-Luttinger liquid theory.

Transition Metal Dichalcogenides (TMDCs) Heterostructures: Synthesis, Excitons and Photoelectric Properties.

Transition metal dichalcogenides (TMDCs) have good flexibility, light absorption, and carrier mobility, and can be used to fabricate wearable devices and photodetectors. In addition, the band gaps of these materials are adjustable, which are related to the number of stacking layers. The the material properties can be changed by vertically stacking TMDCs to form van der Waals (vdW) heterostructures. Compared with single-layer TMDC, the vdW heterostructure has better light response and more efficient photoelectric conversion. Interlayer excitons formed in vdW heterostructure have a longer exciton lifetime and unique valley selectivity compared with intralayer excitons, which promotes the research on TMDCs materials in photoelectric field, valley electronics, carrier dynamics, etc. In this paper, the methods of synthesizing heterostructures are introduced. Photoelectric properties, valley dynamics, electronic properties and related applications of TMDCs vdW heterostructures are also discussed. Heterostructures stacked with different materials, stacking modes, and twist angles all can affect the properties. Hence, it brings more creativity and research direction to the material field.

Effect of strain-induced polarization field on band structure of MoS2 nanoribbon

Single-layered transition metal dichalcogenides (TMDs) materials show intriguing device application potential due to their superior adjustability under various mechanisms. External strain can produce huge polarization fields inside two-dimensional piezoelectric semiconductor materials to modulate the relevant properties. In this paper, the strain-induced polarization field in monolayer zigzag MoS2 nanoribbon is specifically discussed. For comparison, we also study the deformation potential by means of the strain-modified bond lengths and hopping energies. The edge states and band gap indicate a distinct change due to polarization field. This work can put forward feasible perspectives for designing low-dimensional materials-based devices.

Thermal properties of single-layer MoS2-WS2 alloys enabled by machine-learned interatomic potentials.

Two-dimensional (2D) quantum materials are poised to transform conventional electronics for a wide spectrum of applications that will encompass chemical sciences. For the study of thermal transport in single-layer (1L) or multi-layer transition metal dichalcogenides (TMDs), this work explores the combination of density functional theory (DFT) and algorithmic training for the generation of a moment tensor potential (MTP) that models 1L-MoS2, 1L-WS2 and their alloys, and demonstrates a synergy of theoretical techniques that is anticipated to play an important role in the field. From a high-performance computing perspective, these yield very convenient inter-atomic (or inter-molecular in other contexts) potentials that are useful to predict the response of quantum materials to thermal perturbations, or other driving forces. We show that our trained MTP functions successfully describe vibrational properties of the systems, and their thermal conductivities. The trained potential displays consistent agreement with DFT calculations, as well as the Stillinger-Weber (SW) potential. We also find that the thermal conductivity of the 2D alloys is little affected by sulfur vacancies. This is a behavior that may aid the fine-tuning of material's thermal properties for heat management and energy storage and conversion applications.

Visualizing band structure hybridization and superlattice effects in twisted MoS2/WS2 heterobilayers

A mismatch of atomic registries between single-layer transition metal dichalcogenides (TMDs) in a two-dimensional (2D) van der Waals heterostructure produces a moiré superlattice with a periodic potential, which can be fine-tuned by introducing a twist angle between the materials. This approach is promising both for controlling the interactions between the TMDs and for engineering their electronic band structures, yet direct observation of the changes to the electronic structure introduced with varying twist angle has so far been missing. Here, we probe heterobilayers comprised of single-layer MoS2 and WS2 with twist angles ranging from 2∘ to 20∘ and determine the twist angle-dependent evolution of the electronic band structure using micro-focused angle-resolved photoemission spectroscopy. We find strong interlayer hybridization between MoS2 and WS2 electronic states at the -point of the Brillouin zone, leading to a shift of the valence band maximum in the heterostructure. Replicas of the hybridized states are observed at the center of twist angle-dependent moiré mini Brillouin zones. We confirm that these replica features arise from the inherent moiré potential by comparing our experimental observations with density functional theory calculations of the superlattice dispersion. Our direct visualization of these features underscores the potential of using twisted heterobilayer semiconductors to engineer hybrid electronic states and superlattices that alter the electronic and optical properties of 2D heterostructures for a wide range of twist angles.

Edges are more electroactive than basal planes in synthetic bulk crystals of TiS2 and TiSe2

Layered materials and derived 2D material couples such as graphite/graphene, layered and single layer pnictogens (i.e., black phosphorus and phosphorene) and transition metal dichalcogenides (TMDs) have gained a lot of attention due to their electrocatalytic properties and as potential materials for energy storage. Previous studies have shown that electrochemical reactions at graphite, MoS2 and pnictogens mainly occur at the edges and steps of crystals rather than on the basal plane. The persisting question is if this is a general trend in nature within bulk crystals of 2D materials. To come closer to the answer to this question, we studied the surface of artificially grown TiS2 and TiSe2 crystals regarding their local electrochemical activity via scanning electrochemical microscopy (SECM). Both TMDs have shown increased electrochemical activity near crystal steps/edges. For correlation, optical and topographical analysis were performed via scanning electron microscopy (SEM) and atomic force microscopy (AFM). We show that the increased electrochemical activity at edges is persistent for these layered crystalline materials, thus expanding the knowledge their properties, which is important for future application in the energy sector.