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      Highly Reproducible Epitaxial Growth of Wafer‐Scale Single‐Crystal Monolayer MoS 2 on Sapphire

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          Abstract

          2D semiconducting transition‐metal dichalcogenides (TMDs) have attracted considerable attention as channel materials for next‐generation transistors. To meet the industry needs, large‐scale production of single‐crystal monolayer TMDs in highly reproducible and energy‐efficient manner is critically significant. Herein, it is reported that the high‐reproducible, high‐efficient epitaxial growth of wafer‐scale monolayer MoS 2 single crystals on the industry‐compatible sapphire substrates, by virtue of a deliberately designed “face‐to‐face” metal‐foil‐based precursor supply route, carbon‐cloth‐filter based precursor concentration decay strategy, and the precise optimization of the chalcogenides and metal precursor ratio (i.e., S/Mo ratio). This unique growth design can concurrently guarantee the uniform release, short‐distance transport, and moderate deposition of metal precursor on a wafer‐scale substrate, affording high‐efficient and high‐reproducible growth of wafer‐scale single crystals (over two inches, six times faster than usual). Moreover, the S/Mo precursor ratio is found as a key factor for the epitaxial growth of MoS 2 single crystals with rather high crystal quality, as convinced by the relatively high electronic performances of related devices. This work demonstrates a reliable route for the batch production of wafer‐scale single‐crystal 2D materials, thus propelling their practical applications in highly integrated high‐performance nanoelectronics and optoelectronics.

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          Most cited references44

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          The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets.

          Ultrathin two-dimensional nanosheets of layered transition metal dichalcogenides (TMDs) are fundamentally and technologically intriguing. In contrast to the graphene sheet, they are chemically versatile. Mono- or few-layered TMDs - obtained either through exfoliation of bulk materials or bottom-up syntheses - are direct-gap semiconductors whose bandgap energy, as well as carrier type (n- or p-type), varies between compounds depending on their composition, structure and dimensionality. In this Review, we describe how the tunable electronic structure of TMDs makes them attractive for a variety of applications. They have been investigated as chemically active electrocatalysts for hydrogen evolution and hydrosulfurization, as well as electrically active materials in opto-electronics. Their morphologies and properties are also useful for energy storage applications such as electrodes for Li-ion batteries and supercapacitors.
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            Grains and grain boundaries in highly crystalline monolayer molybdenum disulphide

            Recent progress in large-area synthesis of monolayer molybdenum disulphide, a new two-dimensional direct-bandgap semiconductor, is paving the way for applications in atomically thin electronics. Little is known, however, about the microstructure of this material. Here we have refined chemical vapour deposition synthesis to grow highly crystalline islands of monolayer molybdenum disulphide up to 120 μm in size with optical and electrical properties comparable or superior to exfoliated samples. Using transmission electron microscopy, we correlate lattice orientation, edge morphology and crystallinity with island shape to demonstrate that triangular islands are single crystals. The crystals merge to form faceted tilt and mirror twin boundaries that are stitched together by lines of 8- and 4-membered rings. Density functional theory reveals localized mid-gap states arising from these 8-4 defects. We find that mirror twin boundaries cause strong photoluminescence quenching whereas tilt boundaries cause strong enhancement. Meanwhile, mirror twin boundaries slightly increase the measured in-plane electrical conductivity, whereas tilt boundaries slightly decrease the conductivity.
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              Large-Area Epitaxial Monolayer MoS2

              Two-dimensional semiconductors such as MoS2 are an emerging material family with wide-ranging potential applications in electronics, optoelectronics, and energy harvesting. Large-area growth methods are needed to open the way to applications. Control over lattice orientation during growth remains a challenge. This is needed to minimize or even avoid the formation of grain boundaries, detrimental to electrical, optical, and mechanical properties of MoS2 and other 2D semiconductors. Here, we report on the growth of high-quality monolayer MoS2 with control over lattice orientation. We show that the monolayer film is composed of coalescing single islands with limited numbers of lattice orientation due to an epitaxial growth mechanism. Optical absorbance spectra acquired over large areas show significant absorbance in the high-energy part of the spectrum, indicating that MoS2 could also be interesting for harvesting this region of the solar spectrum and fabrication of UV-sensitive photodetectors. Even though the interaction between the growth substrate and MoS2 is strong enough to induce lattice alignment via van der Waals interaction, we can easily transfer the grown material and fabricate devices. Local potential mapping along channels in field-effect transistors shows that the single-crystal MoS2 grains in our film are well connected, with interfaces that do not degrade the electrical conductivity. This is also confirmed by the relatively large and length-independent mobility in devices with a channel length reaching 80 μm.
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                Author and article information

                Contributors
                (View ORCID Profile)
                Journal
                Small Methods
                Small Methods
                2366-9608
                2366-9608
                July 2023
                April 10 2023
                July 2023
                : 7
                : 7
                Affiliations
                [1 ] School of Materials Science and Engineering Peking University Beijing 100871 P. R. China
                [2 ] Center for Nanochemistry Academy for Advanced Interdisciplinary Studies Peking University Beijing 100871 P. R. China
                [3 ] Electron Microscopy Laboratory, and International Center for Quantum Materials School of Physics Peking University Beijing 100871 P. R. China
                [4 ] Key Laboratory for the Physics and Chemistry of Nanodevices School of Electronics Peking University Beijing 100871 P. R. China
                Article
                10.1002/smtd.202300165
                9e565be9-3f9c-4628-9d20-833464647aae
                © 2023

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