Monolayer MoS2 Crystals Research Articles

Large-Scale Direct Growth of Monolayer MoS2 on Patterned Graphene for van der Waals Ultrafast Photoactive Circuits.

Two-dimensional (2D) van der Waals heterostructures combine the distinct properties of individual 2D materials, resulting in metamaterials, ideal for emergent electronic, optoelectronic, and spintronic phenomena. A significant challenge in harnessing these properties for future hybrid circuits is their large-scale realization and integration into graphene interconnects. In this work, we demonstrate the direct growth of molybdenum disulfide (MoS2) crystals on patterned graphene channels. By enhancing control over vapor transport through a confined space chemical vapor deposition growth technique, we achieve the preferential deposition of monolayer MoS2 crystals on monolayer graphene. Atomic resolution scanning transmission electron microscopy reveals the high structural integrity of the heterostructures. Through in-depth spectroscopic characterization, we unveil charge transfer in Graphene/MoS2, with MoS2 introducing p-type doping to graphene, as confirmed by our electrical measurements. Photoconductivity characterization shows that photoactive regions can be locally created in graphene channels covered by MoS2 layers. Time-resolved ultrafast transient absorption (TA) spectroscopy reveals accelerated charge decay kinetics in Graphene/MoS2 heterostructures compared to standalone MoS2 and upconversion for below band gap excitation conditions. Our proof-of-concept results pave the way for the direct growth of van der Waals heterostructure circuits with significant implications for ultrafast photoactive nanoelectronics and optospintronic applications.

Molten glass-mediated conditional CVD growth of MoS2 monolayers and effect of surface treatment on their optical properties

In the rapidly developing field of optoelectronics, the utilization of transition-metal dichalcogenides with adjustable band gaps holds great promise. MoS2, in particular, has garnered considerable attention owing to its versatility. However, a persistent challenge is to establish a simple, reliable and scalable method for large-scale synthesis of continuous monolayer films. In this study, we report the growth of continuous large-area monolayer MoS2 films using a glass-assisted chemical vapor deposition (CVD) process. High-quality monolayer films were achieved by precisely controlling carrier gas flow and sulfur vaporization with a customized CVD system. Additionally, we explored the impact of chemical treatment using lithium bistrifluoromethylsulfonylamine (Li-TFSI) salt on the optical properties of monolayer MoS2 crystals. To investigate the evolution of excitonic characteristics, we conditionally grew monolayer MoS2 flakes by controlling sulfur evaporation. We reported two scenarios on MoS2 films and flakes based on substrate-related strain and defect density. Our findings revealed that high-quality monolayer MoS2 films exhibited lower treatment efficiency due to substrate-induced surface strain. whereas defective monolayer MoS2 flakes demonstrated a higher treatment sensitivity due to the p-doping effect. The Li-TFSI-induced changes in exciton density were elucidated through photoluminescence, Raman, and x-ray photoelectron spectroscopy results. Furthermore, we demonstrated treatment-related healing in flakes under variable laser excitation power. The advancements highlighted in our study carry significant implications for the scalable fabrication of diverse optoelectronic devices, potentially paving the way for widespread real-world applications.

In Situ Imaging of Two-Dimensional Crystal Growth Using a Heat-Resistant Optical Microscope.

Revealing low-dimensional material growth dynamics is critical for crystal growth engineering. However, in a practical high-temperature growth system, the crystal growth process is a black box because of the lack of heat-resistant imaging tools. Here, we develop a heat-resistant optical microscope and embed it in a chemical vapor deposition (CVD) system to investigate two-dimensional (2D) crystal growth dynamics. This in situ optical imaging CVD system can tolerate temperatures of ≤900 °C with a spatial resolution of ∼1 μm. The growth of monolayer MoS2 crystals was studied as a model for 2D crystal growth. The nucleation and growth process have been imaged. Model analysis and simulation have revealed the growth rate, diffusion coefficient, and spatial distribution of the precursor. More importantly, a new vertex-kink-ledge model has been suggested for monolayer crystal growth. This work provides a new technique for in situ microscopic imaging at high temperatures and fundamental insight into 2D crystal growth.

Toward Controlled Synthesis of 2D Crystals by CVD: Learning from the Real-Time Crystal Morphology Evolutions.

The rich morphology of 2D materials grown through chemical vapor deposition (CVD), is a distinctive feature. However, understanding the complex growth of 2D crystals under practical CVD conditions remains a challenge due to various intertwined factors. Real-time monitoring is crucial to providing essential data and enabling the use of advanced tools like machine learning for unraveling these complexities. In this study, we present a custom-built miniaturized CVD system capable of observing and recording 2D MoS2 crystal growth in real time. Image processing converts the real-time footage into digital data, and machine learning algorithms (ML) unveil the significant factors influencing growth. The machine learning model successfully predicts CVD growth parameters for synthesizing ultralarge monolayer MoS2 crystals. It also demonstrates the potential to reverse engineer CVD growth parameters by analyzing the as-grown 2D crystal morphology. This interdisciplinary approach can be integrated to enhance our understanding of controlled 2D crystal synthesis through CVD.

Probing Sulfur Vacancies in CVD-Grown Monolayer MoS2 on SiO2/Si in the Temperature Range 750–900°C

This work reports morphologically alike, high-quality monolayer MoS2 flakes with a similar strain at various growth temperatures (750–900°C) achieved by adjusting sulfur temperature. The growth dynamics of MoS2 are correlated with changes in the photoluminescence (PL) and Raman peak positions. Monolayer MoS2 crystals are synthesized at different growth temperatures from 750°C to 900°C using chemical vapor deposition (CVD). We examined the structural quality and aimed to extract the recombination mechanisms in MoS2 using low-temperature, variable, and low-laser-intensity PL measurements. Our studies of the defect-associated bound exciton emission are well correlated with the blueshift in the A1g mode of Raman spectra, blueshift in PL spectra, and x-ray photoelectron spectroscopy results for crystal grown at 900°C. Our research findings not only shed light on a thorough, non-intrusive method for modifying growth parameters to enhance optical performance, but they also suggest a way to modify the optical characteristics of MoS2 while maintaining the morphology.

Effects of forming gas annealing on the doping of monolayer MoS2 crystals

Here we report the effects of forming gas (5% H2 in N2) annealing on the doping behavior of mechanically-exfoliated, natural n-type MoS2 monolayers. Although the fabricated MoS2 transistors exhibited an enhanced device performance because of the reduced contact resistance after annealing at 200 °C for 2 h, the corresponding Raman and photoluminescence spectra suggested that the forming gas annealing suppressed the n-type doping behavior of MoS2. X-ray photoelectron spectroscopy and Kelvin probe force microscopy measurements consistently suggested a downward movement of the Fermi level of the MoS2 monolayers after the forming gas annealing. These results demonstrate the importance of optimizing the process conditions during the forming gas annealing for the fabrication of MoS2 transistors and devices based on transition metal dichalcogenides.

Chemical Vapor Deposition of Uniform and Large-Domain Molybdenum Disulfide Crystals on Glass/Al2O3 Substrates.

Two-dimensional molybdenum disulfide (MoS2) has attracted significant attention for next-generation electronics, flexible devices, and optical applications. Chemical vapor deposition is the most promising route for the production of large-scale, high-quality MoS2 films. Recently, the chemical vapor deposition of MoS2 films on soda-lime glass has attracted great attention due to its low cost, fast growth, and large domain size. Typically, a piece of Mo foil or graphite needs to be used as a buffer layer between the glass substrates and the CVD system to prevent the glass substrates from being fragmented. In this study, a novel method was developed for synthesizing MoS2 on glass substrates. Inert Al2O3 was used as the buffer layer and high-quality, uniform, triangular monolayer MoS2 crystals with domain sizes larger than 400 μm were obtained. To demonstrate the advantages of glass/Al2O3 substrates, a direct comparison of CVD MoS2 on glass/Mo and glass/Al2O3 substrates was performed. When Mo foil was used as the buffer layer, serried small bilayer islands and bright core centers could be observed on the MoS2 domains at the center and edges of glass substrates. As a control, uniform MoS2 crystals were obtained when Al2O3 was used as the buffer layer, both at the center and the edge of glass substrates. Raman and PL spectra were further characterized to show the merit of glass/Al2O3 substrates. In addition, the thickness of MoS2 domains was confirmed by an atomic force microscope and the uniformity of MoS2 domains was verified by Raman mapping. This work provides a novel method for CVD MoS2 growth on soda-lime glass and is helpful in realizing commercial applications of MoS2.

Decreased n-type behavior of monolayer MoS2 crystals annealed in sulfur atmosphere

Herein, we report decreased n-type behavior of mechanically exfoliated monolayer MoS2 crystals via annealing in sulfur atmosphere. The Raman, photoluminescence, and X-ray photoelectron spectroscopy (XPS) measurements consistently suggested decreased n-type behavior of the monolayer MoS2 crystals after an hour of thermal annealing at 200 °C in sulfur atmosphere. Such decreased n-type behavior could be attributed to the reduced concentration of sulfur vacancies after the annealing, suggested by the analysis of XPS spectra. Furthermore, after the annealing in sulfur atmosphere, the monolayer MoS2 transistors exhibited positively shifted threshold voltages and reduced on-currents, confirming decreased n-type conduction. These results demonstrate that the reduction of the concentration of sulfur vacancies decreases n-type behavior in monolayer MoS2, providing valuable information on understanding the effect of sulfur vacancies on the performance of monolayer MoS2 devices.

Strain-Induced Growth of Twisted Bilayers during the Coalescence of Monolayer MoS2 Crystals

Tailoring the grain boundaries (GBs) and twist angles between two-dimensional (2D) crystals are two crucial synthetic challenges to deterministically enable envisioned applications such as moiré excitons, emerging magnetism, or single-photon emission. Here, we reveal how twisted 2D bilayers can be synthesized from the collision and coalescence of two growing monolayer MoS2 crystals during chemical vapor deposition. The twisted bilayer (TB) moiré angles are found to preserve the misorientation angle (θ) of the colliding crystals. The shapes of the TB regions are rationalized by a kink propagation model that predicts the GB formed by the coalescing crystals. Optical spectroscopy measurements reveal a θ-dependent long-range strain in crystals with stitched grain boundaries and a sharp (θ > 20°) threshold for the appearance of TBs, which relieves this strain. Reactive molecular dynamics simulations explain this strain from the continued growth of the crystals during coalescence due to the insertion of atoms at unsaturated defects along the GB, a process that self-terminates when the defects become saturated. The simulations also reproduce atomic-resolution electron microscopy observations of faceting along the GB, which is shown to arise from the growth-induced long-range strain. These facets align with the axes of the colliding crystals to provide favorable nucleation sites for second-layer growth of a TB with twist angles that preserve the misorientation angle θ. This interplay between strain generation and aligned nucleation provides a synthetic pathway for the growth of TBs with deterministic angles.

Gamma Radiation-Induced Oxidation, Doping, and Etching of Two-Dimensional MoS2 Crystals.

Two-dimensional (2D) MoS2 is a promising material for future electronic and optoelectronic applications. 2D MoS2 devices have been shown to perform reliably under irradiation conditions relevant for a low Earth orbit. However, a systematic investigation of the stability of 2D MoS2 crystals under high-dose gamma irradiation is still missing. In this work, absorbed doses of up to 1000 kGy are administered to 2D MoS2. Radiation damage is monitored via optical microscopy and Raman, photoluminescence, and X-ray photoelectron spectroscopy techniques. After irradiation with 500 kGy dose, p-doping of the monolayer MoS2 is observed and attributed to the adsorption of O2 onto created vacancies. Extensive oxidation of the MoS2 crystal is attributed to reactions involving the products of adsorbate radiolysis. Edge-selective radiolytic etching of the uppermost layer in 2D MoS2 is attributed to the high reactivity of active edge sites. After irradiation with 1000 kGy, the monolayer MoS2 crystals appear to be completely etched. This holistic study reveals the previously unreported effects of high-dose gamma irradiation on the physical and chemical properties of 2D MoS2. Consequently, it demonstrates that radiation shielding, adsorbate concentrations, and required device lifetimes must be carefully considered, if devices incorporating 2D MoS2 are intended for use in high-dose radiation environments.

Ionic liquid gel gate tunable p-Si/MoS2 heterojunction p-n diode

Monolayer MoS2 crystals investigated in this work were grown via chemical vapor deposition on Si/SiO2 substrates. Using a wet KOH etch, these crystals were transferred onto the edge of a freshly cleaved p-Si/SiO2 wafer where they formed mechanically robust heterojunctions at the p-Si/MoS2 interface. Electrical characterization of the device across the junction yielded an asymmetric I–V response similar to that of a p-n diode. The I–V response was electrostatically tunable via an ionic liquid gel gate. This is the first report demonstrating reversible gate control of the p-Si/MoS2 diode current by several orders of magnitude while lowering its turn-on voltage. Fermi energy level shifts within the MoS2 bandgap by the gate was believed to be responsible for the observed effects. The ease of fabrication, low operating voltages (<±2 V), and moderately high throughput currents (∼1 µA) are attractive features of this diode, especially for use in sensors and power saving electronics.

The Intricate Love Affairs between MoS2 and Metallic Substrates

AbstractMechanical exfoliation yields high‐quality 2D materials but is challenging to scale up due to the small lateral size and low yield of the exfoliated crystals. Gold‐mediated exfoliation of macroscale monolayer MoS2 and related crystals addresses this problem. However, it remains unclear whether this method can be extended to other metals. Herein, mechanical exfoliation of MoS2 on a range of metallic substrates is studied. It is found that Au outperforms all the other metals in their ability to exfoliate macroscale monolayer MoS2. This is rationalized by gold's ability to resist oxidation, which is compromised on other metals and leads to a weakened binding with MoS2. An anomalously high monolayer yield found for Ag suggests that the large interfacial strain in the metal–MoS2 heterostructures measured by Raman spectroscopy also is a critical factor facilitating the exfoliation, while the relative differences in the metal–MoS2 binding play only a minor role. These results provide a new incentive for investigations of 2D material‐substrate combinations applicable where high‐quality 2D crystals of macroscopic dimensions are of importance.

Scalable Functionalization of Optical Fibers Using Atomically Thin Semiconductors.

Atomically thin transition metal dichalcogenides are highly promising for integrated optoelectronic and photonic systems due to their exciton-driven linear and nonlinear interactions with light. Integrating them into optical fibers yields novel opportunities in optical communication, remote sensing, and all-fiber optoelectronics. However, the scalable and reproducible deposition of high-quality monolayers on optical fibers is a challenge. Here, the chemical vapor deposition of monolayer MoS2 and WS2 crystals on the core of microstructured exposed-core optical fibers and their interaction with the fibers' guided modes are reported. Two distinct application possibilities of 2D-functionalized waveguides to exemplify their potential are demonstrated. First, the excitonic 2D material photoluminescence is simultaneously excited and collected with the fiber modes, opening a novel route to remote sensing. Then it is shown that third-harmonic generation is modified by the highly localized nonlinear polarization of the monolayers, yielding a new avenue to tailor nonlinear optical processes in fibers. It is anticipated that the results may lead to significant advances in optical-fiber-based technologies.

Simultaneous Identification of Low and High Atomic Number Atoms in Monolayer 2D Materials Using 4D Scanning Transmission Electron Microscopy

Simultaneous imaging of individual low and high atomic number atoms using annular dark field scanning transmission electron microscopy (ADF-STEM) is often challenging due to substantial differences in their scattering cross sections. This often leads to contrast from only the high atomic number species when imaged using ADF-STEM such as the Mo and 2S sites in monolayer MoS2 crystals, without detection of lighter atoms such as C, O, or N. Here, we show that by capturing an array of convergent beam electron diffraction patterns using a 2D pixelated electron detector (2D-PED) in a 4D STEM geometry enables identification of individual low and high atomic number atoms in 2D materials by multicomponent imaging. We have used ptychographic phase reconstructions, combined with angular dependent ADF-STEM reconstructions, to image light elements at lateral (nanopores) and vertical interfaces (surface dopants) within 2D monolayer MoS2. Differential phase contrast imaging (Div(DPC)) using quadrant segmentation of the 2D pixelated direct electron detector data not only qualitatively matches the ptychographic phase reconstructions in both resolution and contrast but also offers the additional potential for real time display. Using 4D-STEM, we have identified surface adatoms on MoS2 monolayers and have separated atomic columns with similar total atomic number into their relative combinations of low and high atomic number elements. These results demonstrate the rich information present in the data obtained during 4D-STEM imaging of ultrathin 2D materials and the ability of this approach to extract unique insights beyond conventional imaging.

Employing a Bifunctional Molybdate Precursor To Grow the Highly Crystalline MoS2 for High-Performance Field-Effect Transistors.

Growth of the large-sized and high-quality MoS2 single crystals for high-performance low-power electronic applications is an important step to pursue. Despite the significant improvement made in minimizing extrinsic MoS2 contact resistance based on interfacial engineering of the devices, the electron mobility of field-effect transistors (FETs) made of a synthetic monolayer MoS2 is yet far below the expected theoretical values, implying that the MoS2 crystal quality needs to be further improved. Here, we demonstrate the high-performance two-terminal MoS2 FETs with room-temperature electron mobility up to ∼90 cm2 V-1 s-1 based on the sulfurization growth of the bifunctional precursor, sodium molybdate dihydrate. This unique transition-metal precursor, serving as both the crystalline Mo source and seed promotor (sodium), could facilitate the lateral growth of the highly crystalline monolayer MoS2 crystals (edge length up to ∼260 μm). Substrate surface treatment with oxygen plasma prior to the deposition of the Mo precursor is fundamental to increase the wettability between the Mo source and the substrate, promoting the thinning and coalescence of the source clusters during the growth of large-sized MoS2 single crystals. The control of growth temperature is also an essential step to grow a strictly monolayer MoS2 crystal. A proof-of-concept for thermoelectric device integration utilizing monolayer MoS2 sheds light on its potential in low-voltage and self-powered electronics.

Elucidation of the growth mechanism of MoS2 during the CVD process

ABSTRACTChemical vapor deposition (CVD) growth of two-dimensional molybdenum disulfide (MoS2) using molybdenum trioxide (MoO3) and sulfur (S) powder often results in intermediate molybdenum oxy-sulfide (MoOS2) species along with MoS2 due to a lack of control over the vapor pressure required for the clean growth. Much effort has been devoted in understanding and controlling of these intermediate MoOS2 specifies. Here, we show that with a second step sulfurization at moderate temperatures, these MoOS2 crystals can be transformed to monolayer MoS2 crystals. Scanning electron microscopy, Raman and photoluminescence spectroscopy and atomic force microscopy characterization carried out before and after re-sulfurization confirm the monolayer MoS2 growth via this route. This study shows that MoOS2 formed at the intermediate state can be successfully recycled to MoS2.

Self-Limiting Growth of High-Quality 2D Monolayer MoS2 by Direct Sulfurization Using Precursor-Soluble Substrates for Advanced Field-Effect Transistors and Photodetectors

Monolayer transition metal dichalcogenides (TMDs) have demonstrated great potential in next-generation electronics due to their unique optical and electronic properties. However, it remains challenging to produce uniform high-quality TMDs over a large scale. The direct sulfurization method holds great promise in achieving large-scale synthesis, but the obtained materials suffer from small grain size and multilayer regions. Herein, low-cost glass substrate is used to achieve facile growth of large-area uniform and large-size monolayer MoS2 crystals via a modified direct sulfurization method. We find that the ability of glass to incorporate predeposited precursors into its molten state is the key to the production of high-quality monolayer MoS2 crystals. The monolayer MoS2 crystals possess the largest average crystal size (∼100 μm) for MoS2 grown by the direct sulfurization method, with large-area uniformity, which is only limited by the size of the substrate. A combination of low-cost, uniformity, scalability, simplicity, and high quality is achieved in our method which showed great promise for the development of wafer scale electronic devices based on 2D materials. Our work also provides a new look at the role substrates could play in the synthesis and the possibilities of using other glass or liquid substrates for the growth of high-quality 2D materials.

Epitaxial Growth of Monolayer MoS2 on SrTiO3 Single Crystal Substrates for Applications in Nanoelectronics

Monolayer molybdenum disulfide (MoS2) crystals grown on amorphous substrates such as SiO2 are randomly oriented. However, when MoS2 is grown on crystalline substrates, the crystal shapes and orientations are also influenced by their epitaxial interaction with the substrate. In this paper, we present the results from chemical vapor deposition growth of MoS2 on three different terminations of single crystal strontium titanate (SrTiO3) substrates. On SrTiO3(111), the monolayer MoS2 crystals form equilateral triangles with two main orientations, in which they align their ⟨2110⟩-type directions (i.e., the sulfur-terminated edge directions) with the ⟨110⟩-type directions on SrTiO3. This arrangement allows near-perfect coincidence epitaxy between seven MoS2 unit cells and four SrTiO3 unit cells. On SrTiO3(110), the MoS2 crystals tend to align their edges with both the ⟨110⟩ and ⟨112⟩ directions on SrTiO3 because these both provide favorable coincidence lattice registry. This distorts the crystal shapes and...

Degradation behaviors and mechanisms of MoS2 crystals relevant to bioabsorbable electronics

Monolayer molybdenum disulfide (MoS2) exhibits unique semiconducting and bioresorption properties, giving this material enormous potential for electronic/biomedical applications, such as bioabsorbable electronics. In this regard, understanding the degradation performance of monolayer MoS2 in biofluids allows modulation of the properties and lifetime of related bioabsorbable devices and systems. Herein, the degradation behaviors and mechanisms of monolayer MoS2 crystals with different misorientation angles are explored. High-angle grain boundaries (HAGBs) biodegrade faster than low-angle grain boundaries (LAGBs), exhibiting degraded edges with wedge and zigzag shapes, respectively. Triangular pits that formed in the degraded grains have orientations opposite to those of the parent crystals, and these pits grow into larger pits laterally. These behaviors indicate that the degradation is induced and propagated based on intrinsic defects, such as grain boundaries and point defects, because of their high chemical reactivity due to lattice breakage and the formation of dangling bonds. High densities of dislocations and point defects lead to high chemical reactivity and faster degradation. The structural cause of MoS2 degradation is studied, and a feasible approach to study changes in the properties and lifetime of MoS2 by controlling the defect type and density is presented. The results can thus be used to promote the widespread use of two-dimensional materials in bioabsorption applications.

Synthesis mechanism of MoS2 layered crystals by chemical vapor deposition using MoO3 and sulfur powders

Monolayer MoS2 layered crystals have attracted significant attention owing to their potential applicability in emerging devices, and chemical vapor deposition (CVD) is the best method so far to obtain monolayer MoS2 single crystals. Although many studies have been published on MoS2 monolayer crystals grown by CVD, there is a lack of understanding of its synthesis pathway. Therefore, in this paper, we studied the mechanism of the synthesis pathway when monolayer MoS2 crystals are synthesized by conventional CVD using MoO3 and sulfur powders. It was found that solid MoO2 produced by the reduction of MoO3 by sulfur plays a very important role in the synthesis of MoS2 layered crystals as an intermediate phase.