Two-dimensional Transition Metal Dichalcogenides Research Articles

Liquid Nitrogen Exfoliation and Nanodispersion of WS2 for Thermocatalysts.

The efficient and clean exfoliation of single and/or few-layer nanosheets of WS2, a two-dimensional transition metal dichalcogenides, remains a significant challenge. In this study, a simple exfoliation method was proposed to produce ultrathin WS2 nanosheets by combining the liquid nitrogen exfoliation and nanodispersion techniques. This approach efficiently exfoliated WS2 into several layers of nanosheets via rapid temperature changes and mechanical stress without inducing defects or contamination. After five cycles of heating/liquid nitrogen and nanodispersion, the resulting WS2 nanosheets (WS2-5N ND) were confirmed to have been successfully exfoliated into 1-4 layers. When applied as a promoter in a thermocatalyst for the selective catalytic reduction of NOX using NH3, 2V3WS2/Ti (WS2-5N ND) exhibited excellent NOX conversion and N2 selectivity, along with excellent durability even in the presence of SO2. This result was greater than 2V3WS2/Ti (WS2-5N) subjected to only liquid nitrogen exfoliation, proving the importance of the simultaneous action of both methods. This method is expected to be an important contribution to ongoing research on high-performance WS2-based catalysts, thereby opening up potential opportunities for a wide range of applications.

Broadband self-powered MoS2/PdSe2/WSe2 PSN heterojunction photodetector for high-performance optical imaging and communication

Two-dimensional (2D) semi-metal transition metal dichalcogenides (TMDs) have drawn significant attention for their distinctive physical properties. However, the inherent high dark current of these materials and the single structure of detectors hinder the further development of photodetectors with high performance. Here, we construct a PSN (p-type semiconductor/semi-metal/n-type semiconductor) architecture by sandwiching 2D semi-metal between two semiconductor layers. In this architecture, the top and bottom layers generate an internal built-in electric field, while the middle layer serves as an absorption layer for low-energy photons and facilitates the dissociation of photo-generated carriers. As a result, the heterojunction device demonstrates a wide spectrum optical response from visible to infrared light (405 nm to 1550 nm) without requiring an external voltage. Working in self-powered mode at room temperature, the device achieves a responsivity of 0.56 A/W, a detectivity of 5.63 × 1011 Jones, and a rapid response speed of 190/74 µs. Additionally, the device shows potential for applications in fast optical communication and multi-wavelength optical imaging. This work presents a novel approach for developing a new type of broadband, self-powered, high-performance miniaturized semi-metal-based photodetector.

Understanding Iron-Doping Modulating Domain Orientation and Improving the Device Performance of Monolayer Molybdenum Disulfide.

Domain orientation modulation and controlled doping of two-dimensional (2D) transition-metal dichalcogenides (TMDCs) are two pivotal tasks for synthesizing wafer-scale single crystals and boosting device performances. However, realizing two such targets and uncovering internal physical mechanisms remain daunting challenges. We develop an accurate Fe doping strategy, which enables domain orientation control and electron mobility improvement of monolayer MoS2. By tuning of the Fe dopant dosages, parallel steps with different heights are formed, which induce edge-nucleation of unidirectionally aligned monolayer MoS2. In parallel, Fe doping induces the down shift of the conduction band minimum of monolayer MoS2 and matches well with the work function of an electrode, which reduces Schottky barrier height and delivers ultralow contact resistance (561 Ω μm) and excellent electron mobility (37.5 cm2 V-1 s-1). The modulation mechanism is clarified by combining theory calculations and electronic structure characterizations. This work hereby provides a new paradigm for synthesizing wafer-scale 2D TMDC single crystals and constructing high-performance devices.

Prediction of a novel two-dimensional superatomic Cd6S2 monolayer for photocatalytic water splitting.

Two-dimensional transition metal dichalcogenides possess a significant specific surface area, adjustable bandgaps, and excellent optical absorption properties, rendering them highly conducive to photocatalytic applications. Herein, a MoS2-like 2D superatomic Cd6S2 monolayer is predicted, wherein the octahedral Cd6 superatom unit connects with S atoms via six vertices. Chemical bonding analysis reveals that the remarkable dynamic, thermal, and mechanical stability of the Cd6S2 monolayer results from the covalent Cd-S bonds and the 6-center 8-electron (6c-8e) delocalized bond within the Cd6 core, which ensures the chemical octet rule for both the S atom and the Cd6 superatom. Demonstrating notable optical absorption coefficients and a strain-tuned energy band structure, the Cd6S2 monolayer emerges as a viable candidate for catalyzing the solar-powered splitting of water. This work offers an alternative avenue to modify or improve the properties of 2D materials for photocatalytic applications through superatomic assembly.

Transition Metal Dichalcogenides in Electrocatalytic Water Splitting

Two-dimensional transition metal dichalcogenides (TMDs), also known as MX2, have attracted considerable attention due to their structure analogous to graphene and unique properties. With superior electronic characteristics, tunable bandgaps, and an ultra-thin two-dimensional structure, they are positioned as significant contenders in advancing electrocatalytic technologies. This article provides a comprehensive review of the research progress of two-dimensional TMDs in the field of electrocatalytic water splitting. Based on their fundamental properties and the principles of electrocatalysis, strategies to enhance their electrocatalytic performance through layer control, doping, and interface engineering are discussed in detail. Specifically, this review delves into the basic structure, properties, reaction mechanisms, and measures to improve the catalytic performance of TMDs in electrocatalytic water splitting, including the creation of more active sites, doping, phase engineering, and the construction of heterojunctions. Research in these areas can provide a deeper understanding and guidance for the application of TMDs in the field of electrocatalytic water splitting, thereby promoting the development of related technologies and contributing to the solution of energy and environmental problems. TMDs hold great potential in electrocatalytic water splitting, and future research needs to further explore their catalytic mechanisms, develop new TMD materials, and optimize the performance of catalysts to achieve more efficient and sustainable energy conversion. Additionally, it is crucial to investigate the stability and durability of TMD catalysts during long-term reactions and to develop strategies to improve their longevity. Interdisciplinary cooperation will also bring new opportunities for TMD research, integrating the advantages of different fields to achieve the transition from basic research to practical application.

An in-depth study of the synthesis of ReSe2 for anisotropic Raman characteristics

Abstract Two-dimensional transition metal dichalcogenides (TMDs) have received more interest for their potential role in future electronic and optoelectronic applications. Unlike other TMDs, Rhenium diselenide (ReSe2) stands out for its distinctive anisotropic growth characteristics. These unique features arise from its low lattice symmetry and interlayer decoupling, this has sparked significant interest among researchers. Previous research has indicated the presence of various growth patterns, including dendritic formations and structures resembling flowers. In this study, we effectively produced ReSe2 using the ‘Tilting Boat’ method to achieve growth on a 21 μm scale. Through precise manipulation of the growth conditions, we successfully attained flakes of 21 μm scale in comparison to prior findings. Moreover, we successfully produced a variety of shapes, including triangles, diamonds, and hexagons, on 1 × 1 cm2 Si/SiO2 substrates. Furthermore, we achieved the successful production of a continuous ReSe2 film on a 1 × 3 cm2 Al2O3 substrate. We verified the distinct anisotropic properties of ReSe2 via Raman Spectroscopy. Furthermore, we acquired three-dimensional visual representations of ReSe2 flakes and continuous films via SEM measurements. By employing EDS data and analysing x-ray photoelectron spectroscopy spectra, we have established a compositional ratio of 1:2 for Re and Se, which aligns with the MX2 structure. This confirmation indicates the successful synthesis of high-quality ReSe2 flakes.

Long-Lived Topological Flatband Excitons in Semiconductor Moiré Heterostructures: A Bosonic Kane-Mele Model Platform.

Moiré superlattices based on two-dimensional transition metal dichalcogenides (TMDs) have emerged as a highly versatile and fruitful platform for exploring correlated topological electronic phases. One of the most remarkable examples is the recently discovered fractional quantum anomalous Hall effect (FQAHE) under zero magnetic field. Here, we propose a minimal structure that hosts long-lived excitons-a ubiquitous bosonic excitation in TMD semiconductors-with narrow topological bosonic bands. The nontrivial exciton topology originates from hybridization of moiré interlayer excitons and is tunable by controlling twist angle and electric field. At small twist angle, the lowest exciton bands are isolated from higher energy bands and provide a solid-state realization of the bosonic Kane-Mele model with topological flatbands, which could potentially support the bosonic version of FQAHE.

Diverse Excitonic Phenomena in Asymmetric Trilayer Transition Metal Dichalcogenide Heterostructures.

Interlayer excitons formed in two-dimensional transition metal dichalcogenide (TMD) heterostructures can be easily tuned due to the large spatial separation. In this work, we discuss the electronic and excitonic optical properties of trilayer heterostructures MoS2/MoSSe/WSe2 and MoS2/MoSSe/MoSe2 using state-of-the-art GW+BSE calculations. In both trilayer geometries, we discover a variety of exciton states, including interlayer excitons, every-other-layer excitons, and their hybridized states, h-IX. Importantly, the h-IXs are optically bright through hybridizing with the intralayer excitons, and the radiative lifetimes of h-IXs range from subnanoseconds to tens of microseconds at 77 K, depending on their compositions. We also reveal that the diversity of the low-lying IXs in MoS2/MoSSe/MoSe2 is higher than that of MoS2/MoSSe/WSe2, because more energy levels participate in transitions in MoS2/MoSSe/MoSe2. Our findings demonstrate that the appropriate energy alignment via manipulating the Janus layer is crucial for realizing rich excitonic states in trilayer TMD heterostructures.

Gamma rays impact on 2D-MoS2 in water solution.

Two-dimensional transition metal dichalcogenides, particularly MoS2, are interesting materials for many applications in aerospace research, radiation therapy and bioscience more in general. Since in many of these applications MoS2-based nanomaterials can be placed in an aqueous environment while exposed to ionizing radiation, both experimental and theoretical studies of their behaviour under these conditions is particularly interesting. Here, we study the effects of tiny imparted doses of 511keV photons to MoS2 nanoflakes in water solution. To the best of our knowledge, this is the first study in which ionizing radiation on 2D-MoS2 occurs in water. Interestingly, we find that, in addition to the direct interaction between high-energy photons and nanoflakes, reactive chemical species, generated by γ-photons induced radiolysis of water, come into play a relevant role. A radiation transport Monte Carlo simulation allowed determining the elements driving the morphological and spectroscopical changes of 2D-MoS2, experimentally monitored by SEM microscopy, DLS, Raman and UV-vis spectroscopy, AFM, and X-ray photoelectron techniques. Our study demonstrates that radiolysis products affect the Molybdenum oxidation state, which is massively changed from the stable + 4 and + 6 states into the rarer and more unstable + 5. These findings will be relevant for radiation-based therapies and diagnostics in patients that are assuming drugs or contrast agents containing 2D-MoS2 and for aerospace biomedical applications of 2DMs investigating their actions into living organisms on space station or satellites.

Atomic Nb-doping of WS2 for high-performance synaptic transistors in neuromorphic computing

Owing to the controllable growth and large-area synthesis for high-density integration, interest in employing atomically thin two-dimensional (2D) transition-metal dichalcogenides (TMDCs) for synaptic transistors is increasing. In particular, substitutional doping of 2D materials allows flexible modulation of material physical properties, facilitating precise control in defect engineering for eventual synaptic plasticity. In this study, to increase the switch ratio of synaptic transistors, we selectively performed experiments on WS2 and introduced niobium (Nb) atoms to serve as the channel material. The Nb atoms were substitutionally doped at the W sites, forming a uniform distribution across the entire flakes. The synaptic transistor devices exhibited an improved switch ratio of 103, 100 times larger than that of devices prepared with undoped WS2. The Nb atoms in WS2 play crucial roles in trapping and detrapping electrons. The modulation of channel conductivity achieved through the gate effectively simulates synaptic potentiation, inhibition, and repetitive learning processes. The Nb-WS2 synaptic transistor achieves 92.30% recognition accuracy on the Modified National Institute of Standards and Technology (MNIST) handwritten digit dataset after 125 training iterations. This study’s contribution extends to a pragmatic and accessible atomic doping methodology, elucidating the strategies underlying doping techniques for channel materials in synaptic transistors.

Janus Monolayer of 1T-TaSSe: A Computational Study.

Materials exhibiting charge density waves are attracting increasing attention owing to their complex physics and potential for applications. In this paper, we present a computational, first principles-based study of the Janus monolayer of 1T-TaSSe transition metal dichalcogenide. We extensively compare the results with those obtained for parent compounds, TaS2 and TaSe2 monolayers, with confirmed presence of 13×13 charge density waves. The structural and electronic properties of the normal (undistorted) phase and distorted phase with 13×13 periodic lattice distortion are discussed. In particular, for a normal phase, the emergence of dipolar moment due to symmetry breaking is demonstrated, and its sensitivity to an external electric field perpendicular to the monolayer is investigated. Moreover, the appearance of imaginary energy phonon modes suggesting structural instability is shown. For the distorted phase, we predict the presence of a flat, weakly dispersive band related to the appearance of charge density waves, similar to the one observed in parent compounds. The results suggest a novel platform for studying charge density waves in two-dimensional transition metal dichalcogenides.

Engineering Two-dimensional tungsten-doped molybdenum selenide transformed conformational nanoarchitectonics: Trimodal therapeutic nanoagents for enhanced synergistic Photothermal/Chemodynamic/Chemotherapy of breast carcinoma

Two-dimensional transition metal dichalcogenides (TMDCs) exhibit promising photothermal therapy (PTT) and chemodynamic therapy (CDT) for anti-tumour treatment. Herein, we proposed an engineering strategy to regulate the lattice structure of tungsten-doped molybdenum selenide (MoxW1−xSe2) transformed conformational nanoarchitectonics using a microwave-assisted solvothermal method for enhancing peroxidase (POD)-like catalytic performance by adjusting the ratio of molybdenum (Mo) and tungsten (W). Furthermore, the optimised Mo0.8W0.2Se2 nanoflakes surface was modified with chitosan (CHI) for improved biocompatibility and nanocatalytic efficacy, then the obtained CHI-Mo0.8W0.2Se2 subsequently loaded the chemotherapeutic drug mitoxantrone (MTO) for enhanced 4 T1 cells killing ability, shortly denoted as CHI-Mo0.8W0.2Se2-MTO for PTT-augmented CDT and chemotherapy (CT). A series of performance validations successfully showed that electrons tend to transfer from W to Mo in CHI-Mo0.8W0.2Se2, which resulted in superior POD-like activity (Km = 0.038 mM) of CHI-Mo0.8W0.2Se2 compared with that of horseradish peroxidase. Furthermore, CHI-Mo0.8W0.2Se2-MTO with excellent photothermal conversion efficiency (PCE=63.2 %) in the near-infrared (NIR) region could further promote endogenous •OH generation and MTO controlled release within solid tumours. In vivo studies confirmed the successful achievement of synergistic therapeutic effects (tumour inhibition rate of over 90 %) with minimised side effects. Versatile therapeutic nanoagents hold great potential for personalised therapy of breast cancer and will find their way to the pharmaceutical field.

High-Performance p-Type Quasi-Ohmic of WSe2 Transistors Using Vanadium-Doped WSe2 as Intermediate Layer Contact.

Two-dimensional (2D) transition-metal dichalcogenides (TMDCs), such as tungsten diselenide (WSe2), hold immense potential for applications in electronic and optoelectronic devices. However, a significant Schottky barrier height (SBH) at the metal-semiconductor (MS) interface reduces the electronic device performance. Here, we present a unique 2D/2D contact method for minimizing contact resistance and reducing the SBH. This approach utilizes vanadium-doped WSe2 (V-WSe2) as the drain and source contacts. The fabricated transistor exhibited a stable operation with p-type quasi-ohmic contact and a high on/off current ratio surpassing 108 at room temperature, reaching 1011 at 10 K. The device achieved an on-current of 68.87 μA, a high mobility of 103.80 cm2 V-1 s-1, a low contact resistance of 0.92 kΩ, and remarkably low SBH values of 1.51 meV for holes at VGS = -120 V with fixed VDS = 1 V. Furthermore, a Schottky photodiode has been fabricated, utilizing V-WSe2 and Cr as the asymmetric contact platform, showing a responsivity of 116 mA W1-. The findings of this study suggest a simple and efficient method for improving the performance of TMDC-based transistors.

Defect-engineered monolayer MoS2 with enhanced memristive and synaptic functionality for neuromorphic computing

Two-dimensional transition metal dichalcogenides (TMDs)-based memristors are promising candidates for realizing artificial synapses in next-generation computing. However, practical implementation faces several challenges, such as high non-linearity and asymmetry in synaptic weight updates, limited dynamic range, and cycle-to-cycle variability. Here, utilizing optimal-power argon plasma treatment, we significantly enhance the performance matrix of memristors fabricated from monolayer MoS2. Our approach not only improves linearity and symmetry in synaptic weight updates but also increases the number of available synaptic weight updates and enhances Spike-Time Dependent Plasticity. Notably, it broadens the switching ratio by two orders, minimizes cycle-to-cycle variability, reduces non-linear factors, and achieves an energy consumption of ~30 fJ per synaptic event. Implementation of these enhancements is demonstrated through Artificial Neural Network simulations, yielding a learning accuracy of ~97% on the MNIST hand-written digits dataset. Our findings underscore the significance of defect engineering as a powerful tool in advancing the synaptic functionality of memristors.

Enhancing reliability in oxide-based memristors using two-dimensional transition metal dichalcogenides

Oxide-based memristor is an attractive candidate for future nonvolatile resistive random access memory (RRAM) devices. However, it suffers from insufficient reliability, owing to the randomness of the conductive filaments, hindering the practical use of the memristor for future RRAM applications. Here, we propose harnessing the two-dimensional (2D) transition metal dichalcogenides (TMDs) on oxide memristor to achieve high device reliability by controlling oxygen vacancy-based filaments near the TMDs/oxide interface. By forming the Pt/WSe2/HfxZr1-xO2 (HZO)/TiN structure, the fabricated memristor exhibits high reliability with good cyclic endurance (over 2,000 cycles), retention (104 s), and low cycle-to-cycle variability. Surface chemical analysis reveals the abundant oxygen vacancies induced by forming WSe2/HZO interface are the source of filamentary switching. By incorporating 2D materials and oxides, the practical application of memristor to future information processing devices can be boosted by the enhanced device reliability.

Compositionally Graded MoS2xTe2(1-x)/MoS2 van der Waals Heterostructures for Ultrathin Photovoltaic Applications.

van der Waals heterojunctions utilizing two-dimensional (2D) transition-metal dichalcogenide (TMD) materials have emerged as focal points in the field of optoelectronic devices, encompassing applications in light-emitting devices, photodetectors, solar cells, and beyond. In this study, we transferred few-atomic-layer films of compositionally graded ternary MoS2xTe2(1-x) alloys onto metal-organic chemical vapor deposition-grown molybdenum disulfide (MoS2) as p- and n-type structures, leading to the creation of a van der Waals vertical heterostructure. The characteristics of the fabricated MoS2xTe2(1-x)/MoS2 vertical-stacked heterojunction were investigated considering the influence of tellurium (Te) incorporation. The systematic variation of parameter x (i.e., 0.8, 0.6, 0.5, 0.3, and 0) allowed for an exploration of the impact of Te incorporation on the photovoltaic performance of these heterojunctions. As a result, the power conversion efficiency was enhanced by approximately 6 orders of magnitude with increasing Te concentration; notably, photoresponsivities as high as ∼6.4 A/W were achieved. These findings emphasize the potential for enhancing ultrathin solar energy conversion in heterojunctions based on 2D TMDs.

Towards the scalable synthesis of two-dimensional heterostructures and superlattices beyond exfoliation and restacking.

Two-dimensional transition metal dichalcogenides, which feature atomically thin geometry and dangling-bond-free surfaces, have attracted intense interest for diverse technology applications, including ultra-miniaturized transistors towards the subnanometre scale. A straightforward exfoliation-and-restacking approach has been widely used for nearly arbitrary assembly of diverse two-dimensional (2D) heterostructures, superlattices and moiré superlattices, providing a versatile materials platform for fundamental investigations of exotic physical phenomena and proof-of-concept device demonstrations. While this approach has contributed importantly to the recent flourishing of 2D materials research, it is clearly unsuitable for practical technologies. Capturing the full potential of 2D transition metal dichalcogenides requires robust and scalable synthesis of these atomically thin materials and their heterostructures with designable spatial modulation of chemical compositions and electronic structures. The extreme aspect ratio, lack of intrinsic substrate and highly delicate nature of the atomically thin crystals present fundamental difficulties in material synthesis. Here we summarize the key challenges, highlight current advances and outline opportunities in the scalable synthesis of transition metal dichalcogenide-based heterostructures, superlattices and moiré superlattices.

2D TMDC aging: a case study of monolayer WS2 and mitigation strategies.

Due to their unique properties, two-dimensional transition metal dichalcogenides (2D TMDCs) are considered for diverse applications in microelectronics, sensing, catalysis, to name a few. A common challenge in 2D TMDC research is the film's inherent instability i.e., spontaneous oxidation upon ambient exposure. The present study systematically explores the effect aging on the film composition and photoluminescent properties of monolayer WS2, synthetically grown by metal-organic chemical vapor deposition. The aging rate is investigated for different oxygen (i.e., O2 gas concentration and humidity) and light-controlled environments. Simple mitigation strategies that do not involve capping the 2D TMDC layer are discussed, and their effectiveness demonstrated by benchmarking the evolution in photoluminescence response against ambient exposed monolayer WS2. These results highlight the need to store 2D TMDCs in controlled environments to preserve the film quality and how future studies can account for the aging effect.

Enhanced Carrier Transport Performance of Monolayer Hafnium Disulphide by Strain Engineering.

For semiconducting two-dimensional transition metal dichalcogenides (TMDs), the carrier transport properties of the material are affected by strain engineering. In this study, we investigate the carrier mobility of monolayer hafnium disulphide (HfS2) under different biaxial strains by first-principles calculations combined with the Kubo-Greenwood mobility approach and the compact band model. The decrease/increase in the effective mass of the conduction band (CB) of monolayer HfS2 caused by biaxial tensile/compressive strain is the major reason for the enhancement/degradation of its electron mobility. The lower hole effective mass of the valence bands (VB) in monolayer HfS2 under biaxial compressive strain improves its hole transport performance compared to that under biaxial tensile strain. In summary, biaxial compressive strain causes a decrease in both the effective mass and phonon scattering rate of monolayer HfS2, resulting in an increase in its carrier mobility. Under the biaxial compressive strain reaches 4%, the electron mobility enhancement ratio of the CB of monolayer HfS2 is ~90%. For the VB of monolayer HfS2, the maximum hole mobility enhancement ratio appears to be ~13% at a biaxial compressive strain of 4%. Our results indicate that the carrier transport performance of monolayer HfS2 can be greatly improved by strain engineering.

Engineered Two-Dimensional Transition Metal Dichalcogenides for Energy Conversion and Storage.

Designing efficient and cost-effective materials is pivotal to solving the key scientific and technological challenges at the interface of energy, environment, and sustainability for achieving NetZero. Two-dimensional transition metal dichalcogenides (2D TMDs) represent a unique class of materials that have catered to a myriad of energy conversion and storage (ECS) applications. Their uniqueness arises from their ultra-thin nature, high fractions of atoms residing on surfaces, rich chemical compositions featuring diverse metals and chalcogens, and remarkable tunability across multiple length scales. Specifically, the rich electronic/electrical, optical, and thermal properties of 2D TMDs have been widely exploited for electrochemical energy conversion (e.g., electrocatalytic water splitting), and storage (e.g., anodes in alkali ion batteries and supercapacitors), photocatalysis, photovoltaic devices, and thermoelectric applications. Furthermore, their properties and performances can be greatly boosted by judicious structural and chemical tuning through phase, size, composition, defect, dopant, topological, and heterostructure engineering. The challenge, however, is to design and control such engineering levers, optimally and specifically, to maximize performance outcomes for targeted applications. In this review we discuss, highlight, and provide insights on the significant advancements and ongoing research directions in the design and engineering approaches of 2D TMDs for improving their performance and potential in ECS applications.