Transition Metal Dichalcogenide Materials Research Articles

Tunable intrinsic strong light–matter coupling in transition metal dichalcogenide nanoresonators

Self-hybridizing structures based on transition metal dichalcogenides (TMDCs) are becoming promising candidates for the study of an intrinsic strong light–matter coupling because of the efficient mode overlap with much simplified geometries. However, realizing flexible tuning of intrinsic strong coupling in such TMDC-based structures is still challenging. Here, we propose a strategy for flexible tuning of the intrinsic strong light–matter coupling based on a bulk TMDC material. We report the first demonstration of the strong coupling of intrinsic excitons to whispering gallery modes (WGMs) supported by an all-TMDC nanocavity. Importantly, by simply controlling angles of incidence, a selective excitation of WGMs and an anapole can be realized, which enables a direct modulation of self-hybridized interactions from a bright WGM–exciton coupling to a dark anapole–exciton coupling. Our work is expected to provide unique opportunities for engineering a strong light–matter coupling and to open exciting avenues for highly integrated novel nanophotonic devices.

Catalytic strategies for uniform monolayer MoSe2 growth in CVD processes

To facilitate the widespread utilization of devices based on two-dimensional transition metal dichalcogenide (TMDC) materials, addressing the challenge of producing large-area and uniform monolayers is crucial. In this study, we investigated the efficacy of various catalysts in promoting the growth of monolayer MoSe2 through chemical vapor deposition (CVD) as a potential solution to improve surface coverage and uniformity while maintaining the monolayer structure. Five distinct water-soluble catalysts (sodium chloride (NaCl), zinc chloride (ZnCl2), potassium hydroxide (KOH), potassium chloride (KCl), potassium oxalate (K2C2O4)) were employed in conjunction with a glass substrate for the CVD-based growth of monolayer MoSe2. We applied these catalyst solutions as thin layers onto SiO2/Si substrates to observe their specific catalytic effects on monolayer MoSe2 formation. MoSe2 was selected as the target material due to its promising characteristics within the TMDC family, particularly its high mobility. Our findings revealed that NaCl, ZnCl2, KCl, and K2C2O4 catalysts enhanced monolayer growth in the 2H phase on SiO2/Si substrates, while the glass substrate resulted in a hybrid 1T/2H MoSe2 structure, albeit with the highest surface coverage. Furthermore, the use of a catalyst allowed us to bypass the laborious transfer step by enabling direct growth of the MoSe2 flakes on the Si/SiO2 substrate, eliminating the risk of flake damage arising from the transfer process. Among the catalyst solutions, NaCl yielded the most homogeneous MoSe2 monolayer growth with relatively high coverage.

Microwave-enhanced pyrolysis of bamboo for furfural-rich bio-oil production over WS2 catalyst

The efficient utilization of bamboo waste has attracted increasing interest as a promising solution to address the challenges associated with climate change and promote a more environmentally friendly approach to resource utilization. Herein, we demonstrated the highly selective production of furfural from bamboo through a microwave-assisted pyrolysis (MAP) process using WS2 catalysts. Firstly, the content of furfural can be precisely regulated by manipulating key process conditions such as microwave power, temperature and the mass ratio of WS2 to bamboo. Notably, compared to non-catalyzed MAP, the presence of the WS2 catalyst significantly enhanced the production of both furfural and furan components. The optimal content of furfural and furan components reached up to 66.9 area% and 75.6 area% in bio-oil under the conditions of 700 W, 400 °C and a 3:10 WS2 to bamboo ratio for 15 min. Furthermore, the liquid oil mainly consisted of C5 and C6 products (86.5 area%), indicating that MAP enhances the selectivity of small molecular products and furan compounds when coupled with the WS2 catalyst. Experimental results revealed that WS2 played bifunctional roles as a microwave absorbent and catalyst, promoting the bio-oil content and limiting the secondary pyrolysis of furan components, leading to a high selectivity of furan and a high content of furan products. This work provides valuable insights into producing furan-rich bio-oil from bamboo through MAP over transition metal dichalcogenides materials.

Realization of single MoTe2 crystal in-plane TFET by laser-induced doping technique

Significant recent progress has been achieved in the fabrication of tunnel field-effect transistors (TFETs) utilizing transition metal dichalcogenides (TMDCs) materials, particularly focusing on out-of-plane heterojunction structures. Due to the inherent limitations of doping technology for TMDCs, there have been limited investigations into the development of in-plane TFETs. In this study, we present the realization of an in-plane TFET based on a single crystal of multilayer MoTe2, utilizing a regioselective doping technique through laser irradiation. By constructing a p+/i/n++ homojunction structure, a band-to-band tunneling dominated performance with a minimum subthreshold swing value of 75 mV/dec and an on/off ratio of 105 was obtained at a low temperature. Furthermore, the “OFF” and “ON” state currents of the TFET operation were smaller than the gated diode operation in this structure, which is consistent with the tunneling mechanism.

Two-Step Conversion of Metal and Metal Oxide Precursor Films to 2D Transition Metal Dichalcogenides and Heterostructures.

The widely studied class of two-dimensional (2D) materialsknown as transition metal dichalcogenides (TMDs) are now well-poised to be employed in real-world applications ranging from electronic logic and memory devices to gas and biological sensors. Several scalable thin film synthesis techniques have demonstrated nanoscale control of TMD material thickness, morphology, structure, and chemistry and correlated these properties with high-performing, application-specific device metrics. In this review, the particularly versatile two-step conversion (2SC) method of TMD film synthesis is highlighted. The 2SC technique relies on deposition of a solid metal or metal oxide precursor material, followed by a reaction with a chalcogen vapor at an elevated temperature, converting the precursor film to a crystalline TMD. Herein, the variables at each step of the 2SC process including the impact of the precursor film material and deposition technique, the influence of gas composition and temperature during conversion, as well as other factors controlling high-quality 2D TMD synthesis are considered. The specific advantages of the 2SC approach including deposition on diverse substrates, low-temperature processing, orientation control, and heterostructure synthesis, among others, are featured. Finally, emergent opportunities that take advantage of the 2SC approach are discussed to include next-generation electronics, sensing, and optoelectronic devices, as well as catalysis for energy-related applications.

Molecular Intercalation‐Induced Two‐Phase Evolution Engineering of 1T and 2H‐MS2 (M = Mo, V, W) for Interface‐Polarization‐Enhanced Electromagnetic Absorbers

AbstractPolarization at interfaces is an important loss mechanism for electromagnetic wave (EMW) attenuation, though the motion behavior of carriers in interfaces composed of different types of conductors has yet to be investigated. Tuning the phase structure of transition metal dichalcogenides (TMDs) MS2 (M = Mo, V, W) by organics small molecule intercalation to achieve the modulation of interfacial types is an effective strategy, where 1T‐MS2 exhibits metallic properties and 2H‐MS2 has semiconducting properties. To exclude the contribution of the intrinsic properties of TMDs materials, three TMDs (MoS2, VS2, and WS2), which also possess phase transitions, are investigated. Among them, the 1T‐MS2 composite exhibits excellent EMW absorption performance under the synergistic effect of interfacial polarization and conduction loss. 1T‐MoS2/MOF‐A exhibits the best EMW absorption performance with an RLmin of −61.07 dB at a thickness of 3.0 mm and an EAB of 7.2 GHz at 2.3 mm. The effectiveness of the modulation of the interfacial polarization using 1T‐phase and 2H‐phase MS2 is demonstrated, which is important for the analysis of the carrier motion behavior during the interfacial loss.

Investigation of spectro-temporal high-order sideband generation from transition metal dichalcogenides [Invited

High-order sideband generation (HSG) in semiconductors under intense terahertz fields has been extensively studied, because it provides essential information for studying ultrafast dynamics in strong-field-dressed quantum materials. In particular, transition metal dichalcogenides (TMDCs), characterized by their unique band structures, provide an exemplary semiconductor system to explore the influence of material band structure on strong-field-induced modulation of HSG. In this work, we investigate the spectro-temporally resolved HSG from different bulk TMDC materials. Our results reveal distinct temporal HSG spectra, which can be attributed to the different absorption behaviors of these materials. Simulations based on the strong-field approximation and Floquet theory can well reproduce the experimental observations. Our work also delves into the spectro-temporal interference that emerges when neighboring harmonic orders overlap in the HSG spectrum. This work enhances our understanding of high-order sideband dynamics in strong-field-dressed semiconductors, offering insights for applications in spectrum- and phase-resolved ultrafast measurements.

Synthesis and Characterization of 2D Ternary Compound TMD Materials Ta3VSe8.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) are garnering considerable scientific interest, prompting discussion regarding their prospective applications in the fields of nanoelectronics and spintronics while also fueling groundbreaking discoveries in phenomena such as the fractional quantum anomalous Hall effect (FQAHE) and exciton dynamics. The abundance of binary compound TMDs, such as MX2 (M = Mo, W; X = S, Se, Te), has unlocked myriad avenues of exploration. However, the exploration of ternary compound TMDs remains relatively limited, with notable examples being Ta2NiS5 and Ta2NiSe5. In this study, we report the synthesis of a new 2D ternary compound TMD materials, Ta3VSe8, employing the chemical vapor transport (CVT) method. The as-grown bulk crystal is shiny and can be easily exfoliated. The crystal quality and structure are verified by X-ray diffraction (XRD), while the surface morphology, stoichiometric ratio, and uniformity are determined by scanning electron microscopy (SEM). Although the phonon property is found stable at different temperatures, magneto-resistivity evolves. These findings provide a possible approach for the realization and exploration of ternary compound TMDs.

Phase-change heterostructure with HfTe2 confinement sublayers for enhanced thermal efficiency and low-power operation through Joule heating localization

Although phase-change random-access memory (PCRAM) is a promising next-generation nonvolatile memory technology, challenges remain in terms of reducing energy consumption. This is primarily because the high thermal conductivities of phase-change materials (PCMs) promote Joule heating dissipation. Repeated phase transitions also induce long-range atomic diffusion, limiting the durability. To address these challenges, phase-change heterostructure (PCH) devices that incorporate confinement sublayers based on transition-metal dichalcogenide materials have been developed. In this study, we engineered a PCH device by integrating HfTe2, which has low thermal conductivity and excellent stability, into the PCM to realize PCRAM with enhanced thermal efficiency and structural stability. HEAT simulations were conducted to validate the superior heat confinement in the programming region of the HfTe2-based PCH device. Moreover, electrical measurements of the device demonstrated its outstanding performance, which was characterized by a low RESET current (∼1.6 mA), stable two-order ON/OFF ratio, and exceptional cycling endurance (∼2 × 107). The structural integrity of the HfTe2 confinement sublayer was confirmed using X-ray photoelectron spectroscopy and transmission electron microscopy. The material properties, including electrical conductivity, cohesive energy, and electronegativity, substantiated these findings. Collectively, these results revealed that the HfTe2-based PCH device can achieve significant improvements in performance and reliability compared with conventional PCRAM devices.

Metallic layered VSe2 saturable absorber based single- and dual-wavelength ultrafast fiber laser

Vanadium selenide (VSe2) is a special two-dimensional (2D) transition metal dichalcogenide (TMD) material with metallic properties similar to graphene, which has been proved to have saturable absorption properties and used in mode-locked fiber lasers. As an excellent saturable absorber (SA) material, VSe2 has advantage of ultrafast carrier recovery time and broadband optical response range. However, the potential application of VSe2 in the field of ultrafast photonics has not been fully developed so far. In this work, the as-prepared VSe2 nanosheets were deposited on tapered fiber by optical deposition to obtain VSe2 SA. By inserting VSe2 SA into an Er-doped fiber laser, the mode-locked pulses with a central wavelength of 1574.4 nm can be obtained. The pulse width of the laser is measured to be ∼680 fs which is narrowest in the reported VSe2 SA-based lasers. In addition, the unique dual-wavelength mode-locked pulse is also obtained by further adjusting intracavity dispersion and polarization. This kind of dual-wavelength pulse is valuable in high order harmonic generation enhancement, terahertz wave generation, dense wavelength division multiplexing, dual-frequency comb and other applications. Our results show that metallic VSe2 is of great potential value in ultrafast fiber laser.

Defects in monolayer WS2 grown via sulfurization of WSe2

The conversion of chalcogen atoms into other types of chalcogen atoms in transition metal dichalcogenides exhibits significant advantages in tuning the bandgaps and constructing lateral heterojunctions. However, despite atomic defects at the atomic scale were inevitably formed during conversion process, the construction of dislocations remains difficult. Here, we conducted in-situ sulfurization to achieve structural transformation from monolayer WSe2 to WS2 successfully. We probe these transformations at atomic scale using high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and study structural defects of sulfurized-WS2 by strain and displacement fields. We discovered that high-quality WSe2 flakes were completely sulfurized while dislocations were successfully constructed, manifesting atomic surface roughness and structural disorders. Our work provides insights into designing and optimizing customized Transition metal dichalcogenides (TMDs) materials in controlled synthesis and defect engineering.

Elucidating Local Structure and Positional Effect of Dopants in Colloidal Transition Metal Dichalcogenide Nanosheets for Catalytic Hydrogenolysis.

Tailoring nanoscale catalysts to targeted applications is a vital component in reducing the carbon footprint of industrial processes; however, understanding and controlling the nanostructure influence on catalysts is challenging. Molybdenum disulfide (MoS2), a transition metal dichalcogenide (TMD) material, is a popular example of a nonplatinum-group-metal catalyst with tunable nanoscale properties. Doping with transition metal atoms, such as cobalt, is one method of enhancing its catalytic properties. However, the location and influence of dopant atoms on catalyst behavior are poorly understood. To investigate this knowledge gap, we studied the influence of Co dopants in MoS2 nanosheets on catalytic hydrodesulfurization (HDS) through a well-controlled, ligand-directed, tunable colloidal doping approach. X-ray absorption spectroscopy and density functional theory calculations revealed the nonmonotonous relationship between dopant concentration, location, and activity in HDS. Catalyst activity peaked at 21% Co:Mo as Co saturates the edge sites and begins basal plane doping. While Co prefers to dope the edges over basal sites, basal Co atoms are demonstrably more catalytically active than edge Co. These findings provide insight into the hydrogenolysis behavior of doped TMDs and can be extended to other TMD materials.

Physics based optical modeling of iron disulfide thin films

In this work, physics based optical modeling is carried out using iron disulfide thin films deposited by using a plasma-assisted, radio frequency-powered technique. Iron disulfide is a transition metal dichalcogenide material, exhibiting a variety of unique and excellent characteristics. Various characterization techniques are employed to examine the growth rate, film thickness, and behavior of as-grown iron disulfide thin films. Furthermore, the physics based optical modeling was performed using a combination of experimental techniques and computer modeling approaches. The analyzed thin films exhibit a bandgap of around 1.16 eV. The theoretically calculated values of absorbance, transmission, and reflectance show a good match with the experimental measurements. Moreover, a physics based optical model is developed based on the experimental data and is used to calculate the external quantum efficiency and the optically generated current density of the iron disulfide films to provide insight into its use as an absorber layer.

SCAPS numerical design of MoSe2 solar cell for different buffer layers

The solar cell capacitance simulator (SCAPS-1D) has been used to simulate, design and analyze of MoSe2, an attractive transition metal dichalcogenide (TMDC) material, based heterojunction solar cells to use it as a potential alternative to conventional absorber layers used in solar cells. The work also focuses on finding optimal absorber, buffer layer thickness and impact of operating temperature on solar cell performance with a possible replacement to toxic CdS buffer layer. It has been obtained that the optimum thickness of MoSe2 absorber layer is 1 µm and buffer layer is about 0.04 µm. The efficiency obtained with CdS based buffer layer solar cell is 20.21%. Among different buffer layers such as In2S3, ZnO, ZnOS and ZnSe, the highest efficiency obtained of MoSe2 based solar cell is 20.58% with ZnO buffer layer. ZnO buffer based solar cell shows a temperature gradient of -0.355%/K compared to -0.347%/K for CdS buffer based solar cell. The findings of this work provide important guidance to fabricate high-efficiency MoSe2 thin film solar cell with non-toxic ZnO as a potential buffer layer.

Hydrogenation-induced superconductivity in monolayer

Here, we construct a new two-dimensional hydrogenated transition metal dichalcogenide material, the Janus WSH monolayer, which is created by replacing the top-layer S atoms in the 2H-WS2 monolayer with H atoms. Then we use first-principles calculations to investigate its electronic structure, phonon dispersion, and superconductivity. The results show that hydrogenation breaks the reflection symmetry, which helps orbital hybridization and to flatten the electronic bands. Thus, it leads to a high electronic density of states near the Fermi level. Additionally, the electron-phonon coupling is enhanced by the softening of phonon modes from the in-plane vibrations of W. The strong interactions between electrons and phonons result in phonon-mediated superconductivity in Janus WSH monolayer. The calculated critical temperature (T c ) is approximately 23.1 K at atmospheric pressure. This T c is about twice higher than that of existing WS2-based materials.

Mechanism of Fermi Level Pinning for Metal Contacts on Molybdenum Dichalcogenide.

The high contact resistance of transition metal dichalcogenide (TMD)-based devices is receiving considerable attention due to its limitation on electronic performance. The mechanism of Fermi level (EF) pinning, which causes the high contact resistance, is not thoroughly understood to date. In this study, the metal (Ni and Ag)/Mo-TMD surfaces and interfaces are characterized by X-ray photoelectron spectroscopy, atomic force microscopy, scanning tunneling microscopy and spectroscopy, and density functional theory systematically. Ni and Ag form covalent and van der Waals (vdW) interfaces on Mo-TMDs, respectively. Imperfections are detected on Mo-TMDs, which lead to electronic and spatial variations. Gap states appear after the adsorption of single and two metal atoms on Mo-TMDs. The combination of the interface reaction type (covalent or vdW), the imperfection variability of the TMD materials, and the gap states induced by contact metals with different weights are concluded to be the origins of EF pinning.

TMD material investigation for a low hysteresis vdW NCFET logic transistor

Boltzmann limit is inevitable in conventional MOSFETs, which prevent them to be used for low-power applications. Research in device physics can address this problem by selection of proper materials satisfying our requirements. Recently, 2D transition metal di-chalcogenide (TMD) materials are gaining interest because they help alleviate short-channel effects and DIBL problems. The TMD materials are composed by covalently bonded weak van der Waals (vdW) interaction and can be realized as hetero structures with 2D ferro-electric material CuInP2S6 at the gate stack. This paper demonstrates a vdW negative capacitance field effect transistor (NCFET) structure in TCAD and the design was validated for voltage-current Characteristics. Parametric analysis shows MoS2 with phenomenal on/off ratio, narrow hysteresis than the counterparts. Simulation shows that MoS2 vdW NCFET has a high transconductance of 2.36 µS µm−1. A steep slope of 28.54 mV dec−1 is seen in MoS2 vdW NCFET which promises the performance of logic applications at a reduced supply voltage.

Defects and Defect Engineering of Two-Dimensional Transition Metal Dichalcogenide (2D TMDC) Materials.

As layered materials, transition metal dichalcogenides (TMDCs) are promising two-dimensional (2D) materials. Interestingly, the characteristics of these materials are transformed from bulk to monolayer. The atomically thin TMDC materials can be a good alternative to group III-V and graphene because of their emerging tunable electrical, optical, and magnetic properties. Although 2D monolayers from natural TMDC materials exhibit the purest form, they have intrinsic defects that limit their application. However, the synthesis of TMDC materials using the existing fabrication tools and techniques is also not immune to defects. Additionally, it is difficult to synthesize wafer-scale TMDC materials for a multitude of factors influencing grain growth mechanisms. While defect engineering techniques may reduce the percentage of defects, the available methods have constraints for healing defects at the desired level. Thus, this holistic review of 2D TMDC materials encapsulates the fundamental structure of TMDC materials, including different types of defects, named zero-dimensional (0D), one-dimensional (1D), and two-dimensional (2D). Moreover, the existing defect engineering methods that relate to both formation of and reduction in defects have been discussed. Finally, an attempt has been made to correlate the impact of defects and the properties of these TMDC materials.

Metatungstate Chemical Vapor Deposition of WSe2: Substrate Effects, Shapes, and Morphologies

Owing to their exceptional properties, which are usually determined by the growth conditions, 2D transition metal dichalcogenides (TMDCs) offer numerous research directions for applications in the fields of spintronics, valleytronics, and optoelectronics. Here, we focus on the chemical vapor deposition (CVD) synthesis of WSe2 (tungsten diselenide) nanoclusters/nanoflakes by using a liquid precursor for tungsten (ammonium metatungstate) on Si/SiO2, fused silica, and sapphire substrates. Various WSe2 clusters with different sizes, thicknesses, and geometries were analyzed by means of optical and atomic force microscopy (AFM) and Raman spectroscopy. The observed structures were mostly WSe2 multilayers; however, monolayer formations were also found. They showed significant morphological differences, as well as wide nucleation density and size variations, possibly related to precursor/substrate surface interactions under the same CVD synthesis conditions. The largest WSe2 domains with a lateral size of up to hundreds of micrometers were observed on sapphire, probably caused by a higher growth rate of singular nucleation sites. WSe2 domains with irregular and triangular shapes were simultaneously identified on fused silica, whereas multilayered pyramidal WSe2 structures dominated in the case of Si/SiO2 substrates. The application of polarized Raman spectroscopy to precisely determine and differentiate the characteristic vibrational modes (A1g, E2g, and 2LA(M)) enabled the unambiguous identification of 2D and/or multilayered WSe2 formations with a high crystallinity level. The presented comparative analysis of samples prepared in relatively simple synthesis conditions (moderate working temperatures and ambient pressure) provides a base for further progress of the facile metatungstate CVD method and relevant opportunities for the exploration of 2D TMDC materials.

Probing Polymorphic Stacking Domains in Mechanically Exfoliated Two-Dimensional Nanosheets Using Atomic Force Microscopy and Ultralow-Frequency Raman Spectroscopy.

As one of the key features of two-dimensional (2D) layered materials, stacking order has been found to play an important role in modulating the interlayer interactions of 2D materials, potentially affecting their electronic and other properties as a consequence. In this work, ultralow-frequency (ULF) Raman spectroscopy, electrostatic force microscopy (EFM), and high-resolution atomic force microscopy (HR-AFM) were used to systematically study the effect of stacking order on the interlayer interactions as well as electrostatic screening of few-layer polymorphic molybdenum disulfide (MoS2) and molybdenum diselenide (MoSe2) nanosheets. The stacking order difference was first confirmed by measuring the ULF Raman spectrum of the nanosheets with polymorphic stacking domains. The atomic lattice arrangement revealed using HR-AFM also clearly showed a stacking order difference. In addition, EFM phase imaging clearly presented the distribution of the stacking domains in the mechanically exfoliated nanosheets, which could have arisen from electrostatic screening. The results indicate that EFM in combination with ULF Raman spectroscopy could be a simple, fast, and high-resolution method for probing the distribution of polymorphic stacking domains in 2D transition metal dichalcogenide materials. Our work might be promising for correlating the interlayer interactions of TMDC nanosheets with stacking order, a topic of great interest with regard to modulating their optoelectronic properties.