As-grown Monolayer Research Articles

Defect-Free Nanowelding of Bilayer SnSe Nanoplates.

Nanowelding is a bottom-up technique to create custom-designed nanostructures and devices beyond the precision of lithographic methods. Here, a new technique is reported based on anisotropic lubricity at the van der Waals interface between monolayer and bilayer SnSe nanoplates and a graphene substrate to achieve precise control of the crystal orientation and the interface during the welding process. As-grown SnSe monolayer and bilayer nanoplates are commensurate with graphene's armchair direction but lack commensuration along graphene's zigzag direction, resulting in a reduced friction along that direction and a rail-like, 1D movement that permits joining nanoplates with high precision. This way, molecular beam epitaxially grown SnSe nanoplates of lateral sizes 30-100nm are manipulated by the tip of a scanning tunneling microscope at room temperature. In situ annealing is applied afterward to weld contacting nanoplates without atomic defects at the interface. This technique can be generalized to any van der Waals interfaces with anisotropic lubricity and is highly promising for the construction of complex quantum devices, such as field effect transistors, quantum interference devices, lateral tunneling junctions, and solid-state qubits.

Patterned growth of two-dimensional atomic layer semiconductors.

Transition metal dichalcogenides (TMDCs), which are representative of two-dimensional (2D) semiconductors, have attracted tremendous attention over the last two decades. TMDCs are regarded as potential candidates in modern nano- and optoelectronic applications due to their unique crystal structures and outstanding electronic and optoelectronic properties. For practical use, 2D semiconductors need to be fabricated with diverse morphologies for integration into electronic devices and to perform different functionalities. Controlled patterning synthesis with programmable geometries is therefore highly desired. We review state-of-the-art strategies for the patterned growth of atomic layer TMDCs and their heterostructures, including additive manufacturing and subtractive manufacturing for patterning single TMDC materials and the introduction of other low-dimensional nanomaterials as growth templates or hetero-atoms for element conversion in patterning TMDC heterostructures. The optoelectronic and electronic applications of the as-grown monolayer TMDC patterns are introduced. Future challenges and the prospects for the patterned growth of 2D semiconductors are discussed based on present achievements.

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.

Preliminary bond capacity exploration between monolayer graphene and cementitious composites

This study aims to explore bond capacity between monolayer graphene and cementitious composites for the first time through a pullout test. The low-pressure chemical vapor deposition method was used to synthesize monolayer graphene on the copper substrate to be embedded in the mortar made by the briquette mold. The bond capacity between them was higher than the tensile strength of the copper sheet with as-grown monolayer graphene on the surface since all specimens failed in fracture with embedment length of more than 30 mm. The monolayer graphene enhanced the copper tensile fracture stress and normalized energy during the test as the copper sheet width increased. This short communication explores a new path to quantify the bond between the monolayer graphene and the mortar to promote the understanding of the behavior of graphene-enhanced cementitious composites.

Highly Sensitive Phototransistors Based on Partially Suspended Monolayer WS2

Two-dimensional (2D) materials have attracted tremendous interests because of various advantages, such as high carrier mobility, favorable band gap, strong light-matter interaction, and flat dangling-bond-free surface. However, the photodetection performance of the pristine monolayer 2D materials is not competitive with that of their bulk counterpart due to the atomic thickness. Here, we demonstrated the direct growth of monolayer WS2 on the Si3N4 substrate by chemical vapor deposition. The porous morphology is formed at the surface of the Si3N4 substrate during the growth process, and therefore, the as-grown WS2 is partially suspended on porous Si3N4. The phototransistor based on as-grown monolayer WS2 exhibits a high responsivity of 1.58 × 105 A/W and a fast response speed of 40 ms. Because of light resonant scattering of the porous Si3N4 substrate, the absorption coefficient of monolayer WS2 is enhanced from finite element analysis. In addition, biaxial tensile strain distribution in the partially suspended WS2 induces a built-in in-plane electric field and less carrier mass from first-principles calculations. Therefore, we attributed the high performance of the phototransistor to the hybrid structure of partially suspended monolayer WS2 on the porous substrate. Our present work paves a way to achieve high-performance monolayer photodetector from substrate morphology engineering.

Perforated Carbon Nanotube Film Assisted Growth of Uniform Monolayer MoS2.

Scaling up the chemical vapor deposition (CVD) of monolayer transition metal dichalcogenides (TMDCs) is in high demand for practical applications. However, for CVD-grown TMDCs on a large scale, there are many existing factors that result in their poor uniformity. In particular, gas flow, which usually leads to inhomogeneous distributions of precursor concentrations, has yet to be well controlled. In this work, the growth of uniform monolayer MoS2 on a large scale by the delicate control of gas flows of precursors, which is realized by vertically aligning a well-designed perforated carbon nanotube (p-CNT) film face-to-face with the substrate in a horizontal tube furnace, is achieved. The p-CNT film releases gaseous Mo precursor from the solid part and allows S vapor to pass through the hollow part, resulting in uniform distributions of both gas flow rate and precursor concentrations near the substrate. Simulation results further verify that the well-designed p-CNT film guarantees a steady gas flow and a uniform spatial distribution of precursors. Consequently, the as-grown monolayer MoS2 shows quite good uniformity in geometry, density, structure, and electrical properties. This work provides a universal pathway for the synthesis of large-scale uniform monolayer TMDCs, and will advance their applications in high-performance electronic devices.

CVD growth of large-area monolayer WS2 film on sapphire through tuning substrate environment and its application for high-sensitive strain sensor

Large-area, continuous monolayer WS2 exhibits great potential for future micro-nanodevice applications due to its special electrical properties and mechanical flexibility. In this work, the front opening quartz boat is used to increase the amount of sulfur (S) vapor under the sapphire substrate, which is critical for achieving large-area films during the chemical vapor deposition processes. COMSOL simulations reveal that the front opening quartz boat will significantly introduce gas distribute under the sapphire substrate. Moreover, the gas velocity and height of substrate away from the tube bottom will also affect the substrate temperature. By carefully optimizing the gas velocity, temperature, and height of substrate away from the tube bottom, a large-scale continues monolayered WS2 film was achieved. Field-effect transistor based on the as-grown monolayer WS2 showed a mobility of 3.76 cm2V−1 s−1 and ON/OFF ratio of 106. In addition, a flexible WS2/PEN strain sensor with a gauge factor of 306 was fabricated, showing great potential for applications in wearable biosensors, health monitoring, and human–computer interaction.

Tuning photoluminescence behaviors in strained monolayer belt-like MoS2 crystals confined on TiO2(001) surface

We report on a monolayer (ML) MoS2 belt-like single crystal directly fabricated on the Rutile-TiO2(001) surface via chemical vapor deposition (CVD). We find that the photoluminescence (PL) behaviors in the ML MoS2 single crystal strongly depend on their shapes and the interface of MoS2/TiO2. Compared with the as-grown triangular ML MoS2, the PL peak position is in a blue shift and the PL intensity is increased for the as-grown ML MoS2 belt. Moreover, the PL peak position is in the blue shift by about 38 meV and the intensity is enhanced by nearly 15 times for the as-grown ML MoS2 belt crystal on TiO2 than those samples transferred onto SiO2/Si substrate. This special PL behavior can be attributed to the in-plane compressive strain that is introduced during the CVD growth of ML MoS2 belts confined by the substrate. The energy band of the strained ML MoS2 belt is changed with an up-shift in the conduction band minimum (VBM) and a down-shift in the valence band maximum (CBM), and the band gap is thus enlarged. This results in the energy band structural realignment in the interface of MoS2/TiO2, thereby weakening the charge transferring from the TiO2 substrate to MoS2 and suppressing the concentration of charged excitons to finally enhance the PL intensity of the ML MoS2 belt. The substrate-confined ML MoS2 belts provide a new route for tailoring light-matter interactions to upgrade their weak quantum yields and low light absorption, which can be utilized in optoelectronic and nanophotonic devices.

Bottom-Up-Etching-Mediated Synthesis of Large-Scale Pure Monolayer Graphene on Cyclic-Polishing-Annealed Cu(111).

Synthesis of large-scale single-crystalline graphene monolayers without multilayers involves the fabrication of proper single-crystalline substrates and the ubiquitous formation of multilayered graphene islands during chemical vapor deposition. Here, a method of cyclic electrochemical polishing combined with thermal annealing, which allows the conversion of commercial polycrystalline Cu foils to single-crystal Cu(111) with an almost 100% yield, is presented. A global "bottom-up-etching" method that is capable of fabricating large-area pure single-crystalline graphene monolayers without multilayers through selectively etching bottom multilayered graphene underneath large area as-grown graphene monolayer on Cu(111) surface is demonstrated. Terahertz time-domain spectroscopy (THz-TDS) measurement of the pure monolayer graphene film shows a high average sheet conductivity of 2.8 mS and mean carrier mobility of 6903 cm2 V-1 s-1 over a large area. Density functional theory (DFT) calculations show that the selective etching is induced by the much easier diffusion of hydrogen atoms than hydrocarbon radicals across the edges of the top graphene layer, and the simulated selective etching processes based on phase field modeling are well consistent with experimental observations. This work provides new ways toward the production of single-crystal Cu(111) and the synthesis of pure monolayer graphene with high electronic quality.

Exciton Transitions in Monolayer WS2 Activated by Swift Heavy Ion Irradiation

The emergence of monolayer transition metal dichalcogenides (TMDCs) has provided a favorable platform for exploring a broad range of novel optoelectronic device applications and quantum phenomena due to their remarkable physical and chemical characteristics. Understanding the transition and motion of excitons in TMDCs is of fundamental interest for their optoelectronic devices. Here, we demonstrate the exciton transition in monolayer WS2 that can be fine-tuned by swift heavy ion (SHI) irradiation. The dependence of trion and exciton emissions on SHI irradiation in the as-transferred and as-grown monolayer WS2 was investigated by micro photoluminescence (PL) spectra where different PL responses were monitored. The trion-to-exciton transition in the as-transferred WS2 monolayer was ascribed to SHI irradiation that resulted in charge localization and pre-existing defect annealing, whereas the exciton-to-trion transition in the as-grown WS2 monolayer was attributed to the competition of charge localization and charge transfer caused by SHI irradiation. Femtosecond transient absorption measurements were performed to study the exciton relaxation dynamics in SHI-irradiated WS2, and it was shown that defect-assisted recombination dominates the exciton relaxation process for SHI-irradiated WS2. These results open up new opportunities to manipulate and tune the optical properties of two-dimensional TMDCs, which are of special importance for the development of optoelectronic and valleytronic devices.

Probing Electronic Properties of CVD Monolayer Hexagonal Boron Nitride by an Atomic Force Microscope

Ultrathin hexagonal boron nitride (h-BN) has recently attracted a lot of attention due to its excellent properties. With the rapid development of chemical vapor deposition (CVD) technology to synthesize wafer-scale single-crystal h-BN, the properties of h-BN have been widely investigated with a variety of material characterization techniques. However, the electronic properties of monolayer h-BN have rarely been quantitatively determined due to its atomically thin thickness and high sensitivity to the surrounding environment. In this work, by the combined use of AFM (atomic force microscope) PeakForce Tunneling (PF-TUNA) mode and Kevin probe force microscopy (KPFM) model, both the electrical resistivity (529 MΩ cm) and the inherent Fermi level (∼4.95 eV) of the as-grown monolayer h-BN flakes on the copper substrate have been quantitatively analyzed. Moreover, direct visualization of the high-temperature oxidation-resistance effect of h-BN nanoflakes has been presented. Our work demonstrates a direct estimation of the electronic properties for 2D materials on the initial growth substrate without transfer, avoiding any unwanted contaminations introduced during the transfer process. The quantitative analysis by state-of-the-art atomic force microscope techniques implies that monolayer h-BN can be employed as an atomically thin and high-quality insulator for 2D electronics, as well as a high-temperature antioxidation layer for electronic device applications.

Immobilized Precursor Particle Driven Growth of Centimeter-Sized MoTe2 Monolayer.

Molybdenum ditelluride (MoTe2) has attracted ever-growing attention in recent years due to its novel characteristics in spintronics and phase-engineering, and an efficient and convenient method to achieve large-area high-quality film is an essential step toward electronic applications. However, the growth of large-area monolayer MoTe2 is challenging. Here, for the first time, we achieve the growth of a centimeter-sized monoclinic MoTe2 monolayer and manifest the mechanism of immobilized precursor particle driven growth. Microscopic characterizations reveal an obvious trend of immobilized precursor particles being consumed by the monolayer and continuing to provide a source for the growth of the monolayer. Time-of-flight secondary ion mass spectrometry verifies the attachment of hydroxide ions on the surface of the MoTe2 monolayer, thereby realizing the inhibition of crystal growth along the [001] zone axis and the continuous growth of the MoTe2 monolayer. The first-principles DFT calculations prove the mechanism of immobilized precursor particles and the absorption of hydroxide ions on the MoTe2 monolayer. The as-grown MoTe2 monolayer exhibits a surface roughness of 0.19 nm and average conductivity of 1.5 × 10-5 S/m, which prove the smoothness and uniformity of the MoTe2 monolayer. Temperature-dependent electrical measurements together with the transfer characteristic curves further demonstrate the typical semimetallic properties of monoclinic MoTe2. Our research elaborates the microscopic process of immobilized precursor particles to grow large-area MoTe2 monolayer and provides a new thinking about the growth of many other two-dimensional materials.

Large-scale MoS2(1−x)Se2x monolayers synthesized by confined-space CVD

Alloy engineering is efficient in modulating the electronic structure and physical and chemical properties of Transition metal dichalcogenides (TMDs). Here, we develop an efficient and simple confined-space CVD strategy by using a smaller quartz boat nested in a larger quartz boat for the preparation of ternary alloy MoS2(1−x)Se2x monolayers on SiO2/Si substrates with controllable composition. The effect of hydrogen ratio of the mixed carrier gas (Ar/H2) on the resultant flakes are systematically investigated. A hydrogon ratio of 15% is demonstrated to be the most appropriate to synthesize large size (more than 400 μm) single crystalline MoS2(1−x)Se2x alloy monolayers. The composition of the alloy can also be changed in a full range (2x = 0–2) by changing the weight ratio of Se and S powder. The as-grown monolayer MoS2(1−x)Se2x alloys present continuously high crystal quality in terms of Raman and PL measurements. Furthermore, to visible light (532 nm), the MoS2(1−x)Se2x based photodetectors display wonderful photoresponse with a fast response of less than 50 ms. Our work may be usedful in directing the synthesis of TMDs alloys as well as their optoelectronic applications.

Rapid Growth of Monolayer MoSe2 Films for Large-Area Electronics.

The large-scale growth of semiconducting thin films on insulating substrates enables batch fabrication of atomically thin electronic and optoelectronic devices and circuits without film transfer. Here an efficient method to achieve rapid growth of large-area monolayer MoSe2 films based on spin coating of Mo precursor and assisted by NaCl is reported. Uniform monolayer MoSe2 films up to a few inches in size are obtained within a short growth time of 5 min. The as-grown monolayer MoSe2 films are of high quality with large grain size (up to 120 μm). Arrays of field-effect transistors are fabricated from the MoSe2 films through a photolithographic process; the devices exhibit high carrier mobility of ≈27.6 cm2 V-1 s-1 and on/off ratios of ≈105. The findings provide insight into the batch production of uniform thin transition metal dichalcogenide films and promote their large-scale applications.

Monolayer MoS2 on sapphire: an azimuthal reflection high-energy electron diffraction perspective

Molybdenum disulfide (MoS2) on the c-plane sapphire has been a very popular system to study in the two-dimensional (2D) materials community. Bottom-up synthesis of monolayer (ML) MoS2 with excellent electrical properties has been achieved on sapphire by various methods, making it a very promising candidate to be used in the next generation nano-electronic devices. However, large-area ML MoS2 with comparable quality as the relatively small size exfoliated ML remains quite a challenge. To overcome this bottle neck, a comprehensive understanding of the structure of the as-grown ML material is an essential first step. Here, we report a detailed structural characterization of wafer-scale continuous epitaxial ML MoS2 grown by metalorganic chemical vapor deposition on sapphire using an azimuthal reflection high-energy electron diffraction (ARHEED) technique. With ARHEED we can map not only 2D but also 3D reciprocal space structure of the ML statistically. From the oscillation in the ARHEED intensity profile along the vertical direction of the ML, we derived a real space distance of ~3 Å at the interface of ML and sapphire. Quantitative diffraction spot broadening analyses of the 3D reciprocal space map reveals low density defects and a small angular misalignment of orientation domains in ML MoS2. Based on atomic force microscopy height distribution analysis, cross-section scanning transmission electron microscopy, and density functional theory calculations, we suggest that there exists a passivation layer between MoS2 ML and sapphire substrate. This ARHEED methodology also has been applied to ML WS2 and is expected to be applicable to other ML transition metal dichalcogenides on arbitrary crystalline or non-crystalline substrates.

Synthesis of epitaxial monolayer Janus SPtSe

Janus single-layer transition metal dichalcogenides, in which the two chalcogen layers have a different chemical nature, push chemical composition control beyond what is usually achievable with van der Waals heterostructures. Here, we report such a Janus compound, SPtSe, which is predicted to exhibit strong Rashba spin–orbit coupling. We synthetized it by conversion of a single-layer of PtSe2 on Pt(111) via sulfurization under H2S atmosphere. Our in situ and operando structural analysis with grazing incidence synchrotron X-ray diffraction reveals the process by which the Janus alloy forms. The crystalline long-range order of the as-grown PtSe2 monolayer is first lost due to thermal annealing. A subsequent recrystallization in presence of a source of sulfur yields a highly ordered SPtSe alloy, which is isostructural to the pristine PtSe2. The chemical composition is resolved, layer-by-layer, using angle-resolved X-ray photoelectron spectroscopy, demonstrating that Se-by-S substitution occurs selectively in the topmost chalcogen layer.

Large-scale monolayer molybdenum disulfide (MoS2) for mid-infrared photonics

Abstract Mid-infrared (MIR) photonics has attracted tremendous interest because of its broad applications at atmospheric windows. In this work, we report high-performance MIR photonics based on large-scale and good-quality monolayer molybdenum disulfide (MoS2). The open-aperture Z-scan measurement on the nonlinear saturable absorption features shows that the as-grown monolayer MoS2 possesses a modulation depth of 26% and a low saturable intensity of 271 kW/cm2, enabling its application as an excellent saturable absorber for the MIR pulse generation. This is further evident by the measured high effective nonlinear absorption coefficient β eff (−16 cm/MW). In addition, the two-photon absorption coefficient and the nonlinear refractive index of monolayer MoS2 are also determined by the closed-aperture Z-scan technology. As an application, we demonstrate a passively Q-switched Tm,Ho:CaLu0.1Gd0.9AlO4 (Tm,Ho:CLGA) disordered crystal laser at 2.1 μm by using the monolayer MoS2 as the saturable absorber for the first time, producing a minimum pulse width of 765 ns and a pulse repetition rate of 36 kHz. Our results demonstrate that large-scale monolayer MoS2 is a promising candidate for the MIR photonic applications.

Atomic-Scale Tuning of Graphene/Cubic SiC Schottky Junction for Stable Low-Bias Photoelectrochemical Solar-to-Fuel Conversion.

Engineering tunable graphene–semiconductor interfaces while simultaneously preserving the superior properties of graphene is critical to graphene-based devices for electronic, optoelectronic, biomedical, and photoelectrochemical applications. Here, we demonstrate this challenge can be surmounted by constructing an interesting atomic Schottky junction via epitaxial growth of high-quality and uniform graphene on cubic SiC (3C-SiC). By tailoring the graphene layers, the junction structure described herein exhibits an atomic-scale tunable Schottky junction with an inherent built-in electric field, making it a perfect prototype to systematically comprehend interfacial electronic properties and transport mechanisms. As a proof-of-concept study, the atomic-scale-tuned Schottky junction is demonstrated to promote both the separation and transport of charge carriers in a typical photoelectrochemical system for solar-to-fuel conversion under low bias. Simultaneously, the as-grown monolayer graphene with an extremely high conductivity protects the surface of 3C-SiC from photocorrosion and energetically delivers charge carriers to the loaded cocatalyst, achieving a synergetic enhancement of the catalytic stability and efficiency.

In-depth study of the chemical/electronic structures of two-dimensional molybdenum disulfide materials with sub-micrometer-resolution scanning photoelectron microscopy

The limitation of x-ray photoelectron spectroscopy (XPS) carried out with an in-lab source can be overcome by synchrotron-based scanning photoelectron microscopy (SPEM) that integrates the XPS technique with scanning microscopy, enabling the analysis of the chemical/electronic structure of a material with sub-micrometer spatial resolution. Using this analytical method, the changes in the structural properties of two-dimensional (2D) molybdenum disulfide (MoS2) materials according to the synthetic method used were studied. In addition to the monolayer form of a 2D MoS2 material (MoS2 monolayer), multilayered 2D MoS2 materials and MoS2 monolayers doped with the widely used p-type dopants, gold chloride (AuCl3) and bis(trifluoromethane)sulfonamide (TFSI), were prepared by a controlled synthetic process. Through comparative analysis of the SPEM data with those obtained by other techniques such as Raman spectroscopy, auger electron spectroscopy (AES), and atomic force microscopy (AFM), the variation in the chemical/electronic structures of MoS2 2D materials depending on the synthetic process was clarified. From SPEM data acquired from locations where AuCl3 or TFSI dopant molecules were present, all the MoS2 chemical states were confirmed to have relatively lower binding energies than those of an as-grown MoS2 monolayer. These differences are related to the effects of p-type doping on the MoS2 2D material. Separately, the increase in the MoS2 layer number is manifested in the form of brightness difference in the SPEM data. Meanwhile, all the binding energies of the MoS2 chemical states including the onset of the valence band maximum are slightly lower in the bright regions than in the dark regions, and these binding energy differences are presumably due to the change in the bandgap change based on the MoS2 layer number.

Remarkable quality improvement of as-grown monolayer MoS2 by sulfur vapor pretreatment of SiO2/Si substrates.

Monolayer MoS2 is a direct bandgap semiconductor which is believed to be one of the most promising candidates for optoelectronic devices. Chemical vapor deposition (CVD) is the most popular method to synthesize monolayer MoS2 with a large area. However, many defects are always found in monolayer MoS2 grown by CVD, such as sulfur vacancies, which severely degrade the performance of devices. This work demonstrates a concise and effective method for direct growth of high quality monolayer MoS2 by using SiO2/Si substrates pretreated with sulfur vapor. The MoS2 monolayer obtained using this method shows about 20 times PL intensity enhancement and a much narrower PL peak width than that grown on untreated substrates. Detailed characterization studies reveal that MoS2 grown on sulfur vapor pretreated SiO2/Si substrates has a much lower density of sulfur vacancies. The synthesis of monolayer MoS2 with high optical quality and low defect concentration is critical for both fundamental physics studies and potential practical device applications in the atomically thin limit.