Transition Metal Dichalcogenide Films Research Articles

Van der Waals growth of monolayer transition metal dichalcogenide superconductors on ultra-flat graphene

Abstract Two-dimensional (2D) superconductors have desirable physical properties and a wide range of potential applications. However, many 2D superconducting materials have poor structural integrity and performance at thicknesses down to monolayer. Therefore, they are still hardly exploited in large-scale practical applications. In this study, we demonstrate a growth strategy based on the two-step vapor deposition process and van der Waals (vdW) ultra-flat graphene as a buffer layer, and thereafter realize the wafer-scale monolayer transition metal dichalcogenide (TMD) films, especially for 2D TMD superconductors. By comparing different non-vdW and vdW growth substrates, we demonstrate that ultra-flat graphene films provide an atomically smooth surface and effectively isolates oxygen-dangling bonds, and finally promote the superconducting behaviours of monolayer NbSe2 and TaS2 films. This growth strategy could also be extended to other wafer-scale TMD films and be of both fundamental and technological significance in the development of wafer-scale monolayer TMD-based devices.

Phase-Selective Synthesis of Rhombohedral WS2 Multilayers by Confined-Space Hybrid Metal-Organic Chemical Vapor Deposition.

Rhombohedral polytype transition metal dichalcogenide (TMDC) multilayers exhibit non-centrosymmetric interlayer stacking, which yields intriguing properties such as ferroelectricity, a large second-order susceptibility coefficient χ(2), giant valley coherence, and a bulk photovoltaic effect. These properties have spurred significant interest in developing phase-selective growth methods for multilayer rhombohedral TMDC films. Here, we report a confined-space, hybrid metal-organic chemical vapor deposition method that preferentially grows 3R-WS2 multilayer films with thickness up to 130 nm. We confirm the 3R stacking structure via polarization-resolved second-harmonic generation characterization and the 3-fold symmetry revealed by anisotropic H2O2 etching. The multilayer 3R WS2 shows a dendritic morphology, which is indicative of diffusion-limited growth. Multilayer regions with large, stepped terraces enable layer-resolved evaluation of the optical properties of 3R-WS2 via Raman, photoluminescence, and differential reflectance spectroscopy. These measurements confirm the interfacial quality and suggest ferroelectric modification of the exciton energies.

Toward Mass Production of Transition Metal Dichalcogenide Solar Cells: Scalable Growth of Photovoltaic-Grade Multilayer WSe2 by Tungsten Selenization.

Semiconducting transition metal dichalcogenides (TMDs) are promising for high-specific-power photovoltaics due to their desirable band gaps, high absorption coefficients, and ideally dangling-bond-free surfaces. Despite their potential, the majority of TMD solar cells to date are fabricated in a nonscalable fashion, with exfoliated materials, due to the lack of high-quality, large-area, multilayer TMDs. Here, we present the scalable, thickness-tunable synthesis of multilayer WSe2 films by selenizing prepatterned tungsten with either solid-source selenium at 900 °C or H2Se precursors at 650 °C. Both methods yield photovoltaic-grade, wafer-scale WSe2 films with a layered van der Waals structure and superior characteristics, including charge carrier lifetimes up to 144 ns, over 14× higher than those of any other large-area TMD films previously demonstrated. Simulations show that such carrier lifetimes correspond to ∼22% power conversion efficiency and ∼64 W g-1 specific power in a packaged solar cell, or ∼3 W g-1 in a fully packaged solar module. The results of this study could facilitate the mass production of high-efficiency multilayer WSe2 solar cells at low cost.

Large-Area Epitaxial Growth of Transition Metal Dichalcogenides.

Over the past decade, research on atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDs) has expanded rapidly due to their unique properties such as high carrier mobility, significant excitonic effects, and strong spin-orbit couplings. Considerable attention from both scientific and industrial communities has fully fueled the exploration of TMDs toward practical applications. Proposed scenarios, such as ultrascaled transistors, on-chip photonics, flexible optoelectronics, and efficient electrocatalysis, critically depend on the scalable production of large-area TMD films. Correspondingly, substantial efforts have been devoted to refining the synthesizing methodology of 2D TMDs, which brought the field to a stage that necessitates a comprehensive summary. In this Review, we give a systematic overview of the basic designs and significant advancements in large-area epitaxial growth of TMDs. We first sketch out their fundamental structures and diverse properties. Subsequent discussion encompasses the state-of-the-art wafer-scale production designs, single-crystal epitaxial strategies, and techniques for structure modification and postprocessing. Additionally, we highlight the future directions for application-driven material fabrication and persistent challenges, aiming to inspire ongoing exploration along a revolution in the modern semiconductor industry.

Evolution of transition metal dichalcogenide film properties during chemical vapor deposition: from monolayer islands to nanowalls

Unique properties possessed by transition metal dichalcogenides (TMDs) attract much attention in terms of investigation of their formation and dependence of their characteristics on the production process parameters. Here, we investigate the formation of TMD films during chemical vapor deposition (CVD) in a mixture of thermally activated gaseous H2S and vaporized transition metals. Our observations of changes in morphology, Raman spectra, and photoluminescence (PL) properties in combination with in situ measurements of the electrical conductivity of the deposits formed at various precursor concentrations and CVD durations are evidence of existence of particular stages in the TMD material formation. Gradual transformation of PL spectra from trion to exciton type is detected for different stages of the material formation. The obtained results and proposed methods provide tailoring of TMD film characteristics necessary for particular applications like photodetectors, photocatalysts, and gas sensors.

A High‐Speed Image Sensor Based on Large‐Area MoTe2/Si Photodiode Arrays

AbstractThe market demand for optoelectronic devices is increasing, leading to a need for low‐cost, high‐performance image sensors that can operate effectively in challenging environments such as darkness and fog. The emerging 2D transition metal dichalcogenides (TMDs) have garnered significant interest due to their exceptional optoelectronic properties and compatibility with silicon (Si) complementary metal oxide semiconductor (CMOS) technology. However, the large‐scale synthesis of TMD films and uniform preparation of photodiode arrays remain challenging. This paper reports a synthesis method for heteroepitaxial growth of 2H‐ molybdeum diyelluride (MoTe2) semiconducting films on 3D wafer‐level Si substrates. Using this method, arrays of 2H‐MoTe2/Si heterojunction photodiodes are prepared that demonstrate excellent uniformity and 100% device yield. The photodiodes exhibit satisfactory optoelectronic properties, including a small dark current maintained within a range of 1–3 nA and a maximum responsivity of 521.1 mAW−1 under near‐infrared light at 800 nm, with rise and fall times of less than 4 ms. To demonstrate the image‐sensing capabilities of the photodiode array under visible and near‐infrared (NIR) light illumination, a complete imaging system is designed.The MoTe2/Si photodiode arrays examined in this study offer a practical solution for integrating Si‐based readout circuits and photodetector arrays on a single chip.

Cryogenic nonlinear microscopy of high-Q metasurfaces coupled with transition metal dichalcogenide monolayers.

Monolayers of transition metal dichalcogenides (TMDCs) demonstrate plenty of unique properties due to the band structure. Symmetry breaking brings second-order susceptibility to meaningful values resulting in the enhancement of corresponding nonlinear effects. Cooling the TMDC films to cryogenic temperatures leads to the emergence of two distinct photoluminescence peaks caused by the exciton and trion formation. These intrinsic excitations are known to enhance second harmonic generation. The nonlinear signal can be greatly increased if these material resonances are boosted by high-quality factor geometric resonance of all-dielectric metasurfaces. Here, we experimentally observe optical second harmonic generation caused by excitons of 2D semiconductor MoSe2 at room and cryogenic temperatures enhanced by spectrally overlapped high-Q resonance of TiO2 nanodisks metasurface. The enhancement reaches two orders of magnitude compared to the case when the resonances are not spectrally overlapped.

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.

Low-Temperature Synthesis of WSe2 by the Selenization Process under Ultrahigh Vacuum for BEOL Compatible Reconfigurable Neurons.

Low-temperature large-area growth of two-dimensional (2D) transition-metal dichalcogenides (TMDs) is critical for their integration with silicon chips. Especially, if the growth temperatures can be lowered below the back-end-of-line (BEOL) processing temperatures, the Si transistors can interface with 2D devices (in the back end) to enable high-density heterogeneous circuits. Such configurations are particularly useful for neuromorphic computing applications where a dense network of neurons interacts to compute the output. In this work, we present low-temperature synthesis (400 °C) of 2D tungsten diselenide (WSe2) via the selenization of the W film under ultrahigh vacuum (UHV) conditions. This simple yet effective process yields large-area, homogeneous films of 2D TMDs, as confirmed by several characterization techniques, including reflection high-energy electron diffraction, atomic force microscopy, transmission electron microscopy, and different spectroscopy methods. Memristors fabricated using the grown WSe2 film are leveraged to realize a novel compact neuron circuit that can be reconfigured to enable homeostasis.

Dual-Limit Growth of Large-Area Monolayer Transition Metal Dichalcogenides.

The large-scale growth of monolayer transition metal dichalcogenide (TMDC) films is a determinant for the implementation of two-dimensional materials in industrial applications. However, the simultaneous realization of uniform monolayer thickness and large-area coverage is still a challenge, because it requires precise control of reaction kinetics in both space and time dimensions. Herein, we achieve a variety of large-area monolayer TMDCs films by a dual-limit growth (DLG) that is realized through nanoporous carbon nanotube (CNT) films. In the DLG, a precursor-loaded CNT film placed face-to-face with a substrate provides a space-limited environment facilitating the monolayer growth, while the byproducts formed in the CNT film timely limits the supply of precursors released from nanopores of the CNT film, inhibiting the growth of multilayer TMDCs on the substrate. Consequently, large-area monolayer TMDC films are grown in a wide range of reaction times and show good homogeneity in thickness, optical properties, and device performance over the entire substrate. The DLG strategy is widely applicable for the growth of a variety of TMDC films including WSe2, MoS2, MoSe2, WS2, and ReS2. Our work provides a universal strategy to attain large-area monolayer TMDC films that can be used in practical applications of integrated circuits.

Independent enhancement of the in-plane Seebeck effect in 2D PtSe2/PtSe2 homostructures via a facile interface tuning method

Atomically thin two-dimensional (2D) transition-metal dichalcogenide (TMDC) films have emerged as promising semiconducting materials for use in thermoelectric (TE) applications. However, the utilization of such materials remains challenging owing to the relatively high intrinsic resistance as the size of the TMDC thin films increases to the centimeter scale. These 2D TMDC films can also form vertically stacked homo- or heterostructures at large interfaces with other 2D TMDC films, resulting in unique TE properties at room temperature. This article reports on the in-plane TE properties when the interfaces formed within a PtSe2/PtSe2 (3 nm/3 nm) homostructure are modulated as a function of O2 plasma treatment time. The results show enhanced Seebeck coefficients compared with that of the single-layer PtSe2 with the same thickness. The independent enhancement in the Seebeck coefficient while keeping the electrical conductivity leads to a substantial increase in the power factor. Such extra Seebeck voltage in 2D PtSe2/PtSe2 homostructures is mainly as a result of momentum exchange by charge carriers caused by the temperature gradient in the vertical direction, which occurs in-plane Seebeck coefficient measurements, at the interface between the PtSe2 layers in the in-plane temperature gradient along the samples. These results resemble the characteristics of the phonon drag effect at low temperatures, which can independently increase the Seebeck coefficient at room temperature.

Large-area single-crystal TMD growth modulated by sapphire substrates.

Transition metal dichalcogenides (TMDs) have recently attracted extensive attention due to their unique physical and chemical properties; however, the preparation of large-area TMD single crystals is still a great challenge. Chemical vapor deposition (CVD) is an effective method to synthesize large-area and high-quality TMD films, in which sapphires as suitable substrates play a crucial role in anchoring the source material, promoting nucleation and modulating epitaxial growth. In this review, we provide an insightful overview of different epitaxial mechanisms and growth behaviors associated with the atomic structure of sapphire surfaces and the growth parameters. First, we summarize three epitaxial growth mechanisms of TMDs on sapphire substrates, namely, van der Waals epitaxy, step-guided epitaxy, and dual-coupling-guided epitaxy. Second, we introduce the effects of polishing, cutting, and annealing processing of the sapphire surface on the TMD growth. Finally, we discuss the influence of other growth parameters, such as temperature, pressure, carrier gas, and substrate position, on the growth kinetics of TMDs. This review might provide deep insights into the controllable growth of large-area single-crystal TMDs on sapphires, which will propel their practical applications in high-performance nanoelectronics and optoelectronics.

Electrodeposition of Transition Metal Dichalcogenide Thin- Films from Non-Aqueous Solvents

Transition metal dichalcogenides (TMDCs) are an interesting group of 2D materials characterised with a layered structure analogous to graphene and they possess unique electronic and optical properties, especially when in the few- and mono-layer form. Developing scalable techniques for depositing TMDCs is a major challenge which needs to be overcome to fabricate functional devices with these materials. Electrodeposition is an industrially relevant technique that has some key advantages over other conventional deposition methods. It is a low cost and easily scalable technique and could be used for obtaining complex nanoscale features and for depositing over topologically demanding surfaces. Even though the electrodeposition of MoS2 has been achieved both in aqueous and non-aqueous electrolytes, not much progress has been made in the deposition of other TMDC materials. Tungsten based TMDCs such as WS2 and WSe2 are shown to be very promising materials in different applications, however electrodepositing them remains extremely challenging. One of the major obstacles here is developing electrochemically active precursors which are compatible with the electrolyte system and able to deliver both the tungsten and chalcogens to the electrolyte. Controlling and optimizing the deposition process to obtain few- and mono-layer TMDCs is another challenge. In addition, the choice of substrates for deposition is very important, especially for direct growth of ultra-thin TMDCs. Electrodeposition, being a bottom-up deposition method, would benefit from an atomically thin and smooth substrate such as graphene for depositing few- and mono-layer TMDCs.Here we present non-aqueous electroplating as a scalable alternative technique for tungsten-based TMDC deposition, with WS2 and WSe2 as examples. Tailored single source precursors were developed to use in non-aqueous electrolytes. WS2 was electrodeposited from dichloromethane (CH2Cl2) using the [NEt4]2[WS2Cl4] precursor. WSe2 was then electrodeposited from acetonitrile (CH3CN) electrolyte using [WSeCl4] as the precursor. Electrochemical quartz crystal microbalance (EQCM) studies were performed to optimize the deposition process and to probe the mechanism of precursor electrochemistry. Electrochemical deposition parameters were then carefully adjusted to obtain few- and mono-layer TMDCs. Patterned graphene electrodes were used as an atomically thin and smooth platform for the deposition of few- and mono-layer WS2. Few-layer TMDC films obtained on graphene were found to be much smoother than films deposited on other standard substrates such as titanium nitride (TiN) or Pt. These TMDC/graphene structures gave interesting 2D heterostructures which are technologically important for different applications.This work was funded by EPSRC grant references EP/V062689/1, EP/V062387/1 and EP/P025137/1

Efficiency limit of transition metal dichalcogenide solar cells

Ultrathin transition metal dichalcogenide (TMD) films show great promise as absorber materials in high-specific-power (i.e., high-power-per-weight) solar cells, due to their high optical absorption, desirable band gaps, and self-passivated surfaces. However, the ultimate performance limits of TMD solar cells remain unknown today. Here, we establish the efficiency limits of multilayer (≥5 nm-thick) MoS2, MoSe2, WS2, and WSe2 solar cells under AM 1.5 G illumination as a function of TMD film thickness and material quality. We use an extended version of the detailed balance method which includes Auger and defect-assisted Shockley-Read-Hall recombination mechanisms in addition to radiative losses, calculated from measured optical absorption spectra. We demonstrate that single-junction solar cells with TMD films as thin as 50 nm could in practice achieve up to 25% power conversion efficiency with the currently available material quality, making them an excellent choice for high-specific-power photovoltaics.

Characterization of 2D Transition Metal Dichalcogenides Through Anisotropic Exciton Behaviors.

This study reports the first attempt to characterize the quality, defects, and strain of as-grown monolayer transition metal dichalcogenide (TMDC)-based 2D materials through exciton anisotropy. A standard ellipsometric parameter (Ψ) to observe anisotropic exciton behavior in monolayer 2D materials is used. According to the strong exciton effect from phonon-electron coupling processes, the change in the exciton in the Van Hove singularity is sensitive to lattice distortions such as defects and strain. In comparison with Raman spectroscopy, the variations in exciton anisotropy in Ψ are more sensitive for detecting slight changes in the quality and strain of monolayer TMDC films. Moreover, the optical power requirement for TMDC characterization through exciton anisotropy in Ψ is ≈10-5mWcm-2, which is significantly less than that of Raman spectroscopy (≈106mWcm-2). The standard deviation of the signals varies with strain (defects) in Raman spectra and exciton anisotropies in Ψ are 0.700 (0.795) and 0.033 (0.073), indicating that exciton anisotropy is more sensitive to slight changes in the quality of monolayer TMDC films.

Selective Control of Phases and Electronic Structures of Monolayer TaTe2.

Transition metal dichalcogenide (TMDC) films exhibit rich phases and superstructures, which can be controlled by the growth conditions as well as post-growth annealing treatment. Here, the selective growth of monolayer TaTe2 films with different phases as well as superstructures using molecular beam epitaxy (MBE) is reported. Monolayer 1H-TaTe2 and 1T-TaTe2 films can be selectively controlled by varying the growth temperature, and their different electronic structures are revealed through the combination of angle-resolved photoemission spectroscopy measurements (ARPES) and first-principles calculations. Moreover, post-growth annealing of the 1H-TaTe2 film further leads to a transition from a superstructure to a new 2 × 2 superstructure, where two gaps are observed in the electronic structure and persist up to room temperature. First-principles calculations reveal the role of the phonon instability in the formation of superstructures and the effect of local atomic distortions on the modified electronic structures. This work demonstrates the manipulation of the rich phases and superstructures of monolayer TaTe2 films by controlling the growth kinetics and post-growthannealing.

The Role of Carbon in Metal-Organic Chemical Vapor Deposition-Grown MoS2 Films.

Acquiring homogeneous and reproducible wafer-scale transition metal dichalcogenide (TMDC) films is crucial for modern electronics. Metal-organic chemical vapor deposition (MOCVD) offers a promising approach for scalable production and large-area integration. However, during MOCVD synthesis, extraneous carbon incorporation due to organosulfur precursor pyrolysis is a persistent concern, and the role of unintentional carbon incorporation remains elusive. Here, we report the large-scale synthesis of molybdenum disulfide (MoS2) thin films, accompanied by the formation of amorphous carbon layers. Using Raman, photoluminescence (PL) spectroscopy, and transmission electron microscopy (TEM), we confirm how polycrystalline MoS2 combines with extraneous amorphous carbon layers. Furthermore, by fabricating field-effect transistors (FETs) using the carbon-incorporated MoS2 films, we find that traditional n-type MoS2 can transform into p-type semiconductors owing to the incorporation of carbon, a rare occurrence among TMDC materials. This unexpected behavior expands our understanding of TMDC properties and opens up new avenues for exploring novel device applications.

Probing Carrier Dynamics in Large-Scale MBE-Grown PtSe2 Films by Terahertz Spectroscopy.

Atomically thin platinum diselenide (PtSe2) films are promising for applications in the fields of electronics, spintronics, and photodetectors owing to their tunable electronic structure and high carrier mobility. Using terahertz (THz) spectroscopy techniques, we investigated the layer-dependent semiconducting-to-metallic phase transition and associated intrinsic carrier dynamics in large-scale PtSe2 films grown by molecular beam epitaxy. The uniformity of large-scale PtSe2 films was characterized by spatially and frequency-resolved THz-based sheet conductivity mapping. Furthermore, we use an optical-pump-THz-probe technique to study the transport dynamics of photoexcited carriers and explore light-induced intergrain carrier transport in PtSe2 films. We demonstrate large-scale THz-based mapping of the electrical properties of transition metal dichalcogenide films and show that the two noncontact THz-based approaches provide insight in the spatial and temporal properties of PtSe2 films.

Temperature-Dependent Structural and Electrical Properties of Metal-Organic CVD MoS2 Films.

Metal-Organic CVD method (MOCVD) allows for deposition of ultrathin 2D transition metal dichalcogenides (TMD) films of electronic quality onto wafer-scale substrates. In this work, the effect of temperature on structure, chemical states, and electronic qualities of the MOCVD MoS2 films were investigated. The results demonstrate that the temperature increase in the range of 650 °C to 950 °C results in non-monotonic average crystallite size variation. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and Raman spectroscopy investigation has established the film crystal structure improvement with temperature increase in this range. At the same time, X-Ray photoelectron spectroscopy (XPS) method allowed to reveal non-stoichiometric phase fraction increase, corresponding to increased sulfur vacancies (VS) concentration from approximately 0.9 at.% to 3.6 at.%. Established dependency between the crystallite domains size and VS concentration suggests that these vacancies are form predominantly at the grain boundaries. The results suggest that an increased Vs concentration and enhanced charge carriers scattering at the grains' boundaries should be the primary reasons of films' resistivity increase from 4 kΩ·cm to 39 kΩ·cm.

Electroluminescence from Megasonically Solution-Processed MoS2 Nanosheet Films.

Due to their superior optoelectronic properties, monolayer two-dimensional (2D) transition metal dichalcogenides (TMDs) have attracted significant attention for electroluminescent devices. However, challenges in isolating optoelectronically active TMD monolayers using scalable liquid phase exfoliation have precluded electroluminescence in large-area, solution-processed TMD films. Here, we overcome these limitations and demonstrate electroluminescence from molybdenum disulfide (MoS2) nanosheet films by employing a monolayer-rich MoS2 ink produced by electrochemical intercalation and megasonic exfoliation. Characteristic monolayer MoS2 photoluminescence and electroluminescence spectral peaks at 1.88-1.90 eV are observed in megasonicated MoS2 films, with the emission intensity increasing with film thickness over the range 10-70 nm. Furthermore, employing a vertical light-emitting capacitor architecture enables uniform electroluminescence in large-area devices. These results indicate that megasonically exfoliated MoS2 monolayers retain their direct bandgap character in electrically percolating thin films even following multistep solution processing. Overall, this work establishes megasonicated MoS2 inks as an additive manufacturing platform for flexible, patterned, and miniaturized light sources that can likely be expanded to other TMD semiconductors.