Two-dimensional (2D) semiconductors, in particular transition metal dichalcogenides (TMDCs), have attracted great interest in extending Moore’s law beyond silicon1–3. However, despite extensive efforts4–25, the growth of wafer-scale TMDC single crystals on scalable and industry-compatible substrates has not been well demonstrated. Here we demonstrate the epitaxial growth of 2 inch (~50 mm) monolayer molybdenum disulfide (MoS2) single crystals on a C-plane sapphire. We designed the miscut orientation towards the A axis (C/A) of sapphire, which is perpendicular to the standard substrates. Although the change of miscut orientation does not affect the epitaxial relationship, the resulting step edges break the degeneracy of nucleation energy for the antiparallel MoS2 domains and lead to more than a 99% unidirectional alignment. A set of microscopies, spectroscopies and electrical measurements consistently showed that the MoS2 is single crystalline and has an excellent wafer-scale uniformity. We fabricated field-effect transistors and obtained a mobility of 102.6 cm2 V−1 s−1 and a saturation current of 450 μA μm–1, which are among the highest for monolayer MoS2. A statistical analysis of 160 field-effect transistors over a centimetre scale showed a >94% device yield and a 15% variation in mobility. We further demonstrated the single-crystalline MoSe2 on C/A sapphire. Our method offers a general and scalable route to produce TMDC single crystals towards future electronics. Unidirectional alignment of MoS2 domains during epitaxial growth on C/A sapphire enables the realization of large-area MoS2 single crystals.

Epitaxial growth of wafer-scale molybdenum disulfide semiconductor single crystals on sapphire

© 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown.

Production and processing of graphene and related materials

This review discusses recent advances and future research priorities in the transition-metal dichalcogenide (TMD) field. While the community has witnessed tremendous advances through research conducted on two-dimensional (2D) TMD crystals, it is vital to seek new research opportunities beyond developed areas. To this end, in this review we focus principally on articulating areas of need in the preparation and analysis of TMD crystals encompassing dimensionalities and morphologies beyond 2D. Ultimately, the development of new synthetic methods to control key structural features of low-dimensional TMD crystals (e.g., dimensionality, morphology, and phase) will afford access to a broader range of breakthrough properties for this intriguing material class. We begin with a brief overview of the evolution of 2D TMD research, discussing both the synthetic methods that have enabled the preparation of these materials and the manifold properties they possess. We focus the bulk of our review on discussion of recent advances associated with 1D TMD crystals, which are often referred to as TMD nanoribbons, and include a discussion of recent efforts in 0D systems. We discuss synthetic strategies that have been developed to prepare such beyond 2D crystals and highlight their unique physical and chemical properties. After reviewing the host of analytical tools available for characterization of TMD materials, we identify future analytical instrumentation needs. We conclude with a discussion of the prospects of beyond 2D TMD crystals in optoelectronics, catalysis, and quantum information science.

Progress and Prospects in Transition-Metal Dichalcogenide Research Beyond 2D

Atom-thin transition metal dichalcogenides (TMDs) have emerged as fascinating materials and key structures for electrocatalysis. So far, their edges, dopant heteroatoms and defects have been intensively explored as active sites for the hydrogen evolution reaction (HER) to split water. However, grain boundaries (GBs), a key type of defects in TMDs, have been overlooked due to their low density and large structural variations. Here, we demonstrate the synthesis of wafer-size atom-thin TMD films with an ultra-high-density of GBs, up to ~1012 cm−2. We propose a climb and drive 0D/2D interaction to explain the underlying growth mechanism. The electrocatalytic activity of the nanograin film is comprehensively examined by micro-electrochemical measurements, showing an excellent hydrogen-evolution performance (onset potential: −25 mV and Tafel slope: 54 mV dec−1), thus indicating an intrinsically high activation of the TMD GBs. Transition metal dichalcogenides demonstrate fascinating capabilities for electrocatalytic H2 evolution, although the activities vary widely depending on nanomaterial sites available. Here, authors show the grain boundaries of atomically thin MoS2 to be especially active sites for H2 evolution.

/pdf/engineering-grain-boundaries-at-the-2d-limit-for-the-19fiwuw80h.pdf

Engineering grain boundaries at the 2D limit for the hydrogen evolution reaction.

Promoting the intrinsic activity and accessibility of basal plane sites in 2D layered metal dichalcogenides is desirable to optimize their catalytic performance for energy conversion and storage. Herein, a core/shell structured hybrid catalyst, which features few-layered ruthenium (Ru)-doped molybdenum disulfide (MoS2) nanosheets closely sheathing around multiwalled carbon nanotube (CNT), for highly efficient hydrogen evolution reaction (HER) is reported. With 5 at% (atomic percent) Ru substituting for Mo in MoS2, Ru-MoS2/CNT achieves the optimum HER activity, which displays a small overpotential of 50 mV at -10 mA cm-2 and a low Tafel slope of 62 mV dec-1 in 1 m KOH. Theoretical simulations reveal that Ru substituting for Mo in coordination with six S atoms is thermodynamically stable, and the in-plane S atoms neighboring Ru dopants represent new active centers for facilitating water adsorption, dissociation, and hydrogen adsorption/desorption. This work provides a multiscale structural and electronic engineering strategy for synergistically enhancing the HER activity of transition metal dichalcogenides.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.201900090

Engineering MoS2 Basal Planes for Hydrogen Evolution via Synergistic Ruthenium Doping and Nanocarbon Hybridization

Chemical vapour deposition of two-dimensional materials typically involves the conversion of vapour precursors to solid products in a vapour-solid-solid mode Here, we report the vapour-liquid-solid growth of monolayer MoS2, yielding highly crystalline ribbons with a width of few tens to thousands of nanometres This vapour-liquid-solid growth is triggered by the reaction between MoO3 and NaCl, which results in the formation of molten Na-Mo-O droplets These droplets mediate the growth of MoS2 ribbons in the 'crawling mode' when saturated with sulfur The locally well-defined orientations of the ribbons reveal the regular horizontal motion of the droplets during growth Using atomic-resolution scanning transmission electron microscopy and second harmonic generation microscopy, we show that the ribbons are grown homoepitaxially on monolayer MoS2 with predominantly 2H- or 3R-type stacking Our findings highlight the prospects for the controlled growth of atomically thin nanostructure arrays for nanoelectronic devices and the development of unique mixed-dimensional structures

Vapour–liquid–solid growth of monolayer MoS 2 nanoribbons

Chemical vapor deposition (CVD) of two-dimensional (2D) materials such as monolayer MoS2 typically involves the conversion of vapor-phase precursors to a solid product in a process that may be described as a vapor-solid-solid (VSS) mode. Here, we report the first demonstration of vapor-liquid-solid (VLS) growth of monolayer MoS2 yielding highly crystalline ribbon-shaped structures with a width of a few tens of nanometers to a few micrometers. The VLS growth mode is triggered by the reaction between molybdenum oxide and sodium chloride, which results in the formation of molten Na-Mo-O droplets. These droplets mediate the growth of MoS2 ribbons in the "crawling mode" when saturated with sulfur on a crystalline substrate. Our growth yields straight and kinked ribbons with a locally well-defined orientation, reflecting the regular horizontal motion of the liquid droplets during growth. Using atomic-resolution scanning transmission electron microscopy (STEM) and second harmonic generation (SHG) microscopy, we show that the ribbons are homoepitaxially on monolayer MoS2 surface with predominantly 2H- or 3R-type stacking. These findings pave the way to novel devices with structures of mixed dimensionalities.

Vapor-Liquid-Solid Growth of Monolayer MoS2 Nanoribbons.

Handle everyday research tasks with reliable, citation-backed results

Your personal Research Agent to handle research tasks with citation-backed results

Popular Tasks used by Researchers

How can I help with your research?

Meet SciSpace

Get more enhanced response by uploading the PDFs you want me to reference.

No relevant PDFs in your library

SciSpace is the AI research assistant for academics. Run systematic literature reviews on 280M+ papers, and write papers with cited sources. Trusted by 1M+ students, PhDs & researchers.

SciSpace | AI for Research

Analyze PDFs

Code & Manuscripts

Funding & Grants

Literature & Patents

Medical & Clinical Data

Systematic Review

Visualize & Present

Web & Data

Build a Google Scholar-like website for your research.

Build a website

Create charts and images for your research

Create a Chart

Write a paper for submission to a journal

Draft a manuscript

Patent Search

Design eye-catching scientific posters in minutes.

Scientific Poster Generation

Systematic Literature Review

One task is running at the moment. Your messages will be shown right after.

Drag and drop or click here to browse

Loved by <highlight>1 million+</highlight> researchers

Extract a list of specific topics and their sources from unstructured text

Topics

Compare and analyze relevant papers that matches with your search

Papers

Get insights from PDFs and bookmarked papers from your library

My library

Recent searches

Try searching for:

Catch AI-generated content in scholarly and non-scholarly content

{ai} Detector

Ai Writer

Get PDF Summaries, highlighted text explanations 

Chat with PDF

Effortlessly create in-text citations and bibliographies in APA and 2,500 other formats

Citation generator

Get explanations, summaries, and answers on academic papers

Ease up your research workflow with {scispace}'s cohort of exciting AI tools

Elevate your academic writing skills and convey your ideas the way you want

Paraphraser

Explore our range of reading and writing tools

Your file is being prepared and should be ready in a few minutes. If it's a large file, it might take a bit longer. You can close this window, and we'll email you the file when it's done.

You have reached a maximum limit of <strong>{limit}</strong> columns in the table. Remove at least <strong>1</strong> column to add or create another one.

Youde Shen

Author Tools

Chat about Author

Papers

Vapour–liquid–solid growth of monolayer MoS 2 nanoribbons

Vapor-Liquid-Solid Growth of Monolayer MoS2 Nanoribbons.