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Highly controlled deposition of exfoliated transition metal dichalcogenide (TMD) suspensions onto substrates is an important step for the creation of efficient and scalable energy, electronic, optical and sensing units. Traditional methods such as drop casting and spin coating generally result in non-uniform deposition. Some methods also require the incorporation of surfactants or initiator molecules, which contaminate the particles and require extra processing steps. Here we present a facile method for controlled and patterned deposition of films made of exfoliated TMDs over large areas. A liquid–liquid interface is achieved directly from the nanoflake suspension in dimethyl formamide, without addition of any surfactants or chemical modifiers. We demonstrate the reliable and large scale patterning of macroscopic uniform films from exfoliated TMDs, through the use of hydrophobically patterned substrates. Microcharacterisations show that the TMD nanoflakes assemble through edge-to-edge arrangement into densely-packed thin films. Additionally, heterofilms were also successfully demonstrated using the same liquid–liquid interface method, through simply mixing exfoliated MoS2 and WS2 suspensions together before film assembly. This fast approach to TMD thin film assembly provides a future platform for reliable controlled deposition and co-patterning of 2D materials on a large scale compatible with industrial standards.

There is ongoing interest in exploring new two-dimensional materials and exploiting their functionalities. Here, a top-down approach is used for developing a new morphology of ultrathin nanosheets from highly ordered bismuth sulfide crystals. The efficient chemical delamination method exfoliates the bulk powder into a suspension of corrugated ultrathin sheets, despite the fact that the Bi2S3 fundamental layers are made of atomically thin ribbons that are held together by van der Waals forces in two dimensions. Morphological analyses show that the produced corrugated sheets are as thin as 2.5 nm and can be as large as 20 μm across. Determined atomic ratios indicate that the exfoliation process introduces sulfur vacancies into the sheets, with a resulting stoichiometry of Bi2S2.6. It is hypothesized that the nanoribbons were cross-linked during the reduction process leading to corrugated sheet formation. The material is used for preparing field effect devices and was found to be highly p-doped, which is att...

Developing scalable methods of growing two dimensional molybdenum disulphide (2D MoS2) with strong optical properties, on any desired substrates, is a necessary step towards industrial uptake of this material for optical applications. In this study, Si/SiO2 substrates were functionalised using self-assembled monolayers of three different aminosilanes with various numbers of amine groups and molecular lengths as underlayers for enhancing the adherence of the molybdenum precursor. The tetrahedral [MoS4](2-) anion groups from the molybdenum precursor were bonded on these silanised Si/SiO2 substrates afterwards. The substrates were then treated with a combined thermolysis and sulphurisation step. The results showed that silanisation of the substrates using the longest chains and the largest number of amine groups provided a good foundation to grow quasi 2D MoS2 made from adjacent flakes in a mosaic formation. Microscopy and spectroscopy investigations revealed that these quasi 2D MoS2 formed using this long chain aminosilane resulted in flakes with lateral dimensions in micron and submicron ranges composed of adjoining MoS2 pieces of 20 to 60 nm in lateral dimensions, dominantly made of 3 to 5 MoS2 fundamental layers. The obtained quasi 2D MoS2 shows a high internal quantum efficiency of 2.6% associated with the quantum confinement effect and high stoichiometry of the adjoining nanoflakes that form the structure of the sheets. The synthesis technique in this study is reliable and facile and offers a procedure to form large, scalable and patternable quasi 2D MoS2 sheets on various substrates with enhanced optical properties for practical applications.

Two-dimensional (2D) tungsten disulfide (WS2) nanoflakes were synthesised and hybridised with carbon dots (CDs) using a facile two-step method of exfoliation of bulk tungsten disulphide followed by microwave irradiation of nanoflakes in a solution of citric acid. Physicochemical characterisation indicated that the hybrid consists of graphitic carbon dots with diameters of approximately 2–5 nm, attached to monolayer tungsten disulphide via electrostatic attraction forces. This synthesised hybrid material was investigated for photocatalytic applications. We found that within one hour approximately 30% more of the model organic dye was photodegraded by the hybrid material compared with the pristine 2D WS2. This enhancement was associated to the affinity of the CDs to the organic dye rather than heterojunctioning. Comparisons of the photocatalytic efficacy of this hybrid material with those of recently reported 2D transition metal dichalcogenides and their hybrids showed a significantly higher turnover frequency. Additionally, the presented microwave based synthesis method for developing hybrids of 2D WS2 and CDs, without making significant changes to the base 2D crystal structure and its surface chemistry, has not been demonstrated before. Altogether, the hybrid 2D material provides great potential for photocatalysis applications.

Substoichiometric molybdenum disulphide (MoSx) nanosheets are successfully synthesised following a novel reductive route using hydrazine salts. The resulting two dimensional crystals are found to be highly monodispersed in thickness, forming exclusively 1.9 ± 0.2 nm thick bilayers. The lateral dimensions of the nanosheets are governed by the precursor bulk particle's size. Exploring a range of hydrazine derivatives with various degrees of steric hindrance leads to the conclusion that intercalation does not occur during the process and that exfoliation is instead facilitated by the reduction of Mo centres leading to the exfoliation of substoichiometric bilayers with distorted lattices. The lattice distortion is found to be persistent across all samples with XPS analysis pointing towards a S to Mo ratio of 1.2. The resulting material features an electronic bandgap of 2.1 eV, which is wider than that of pristine monolayer MoS2 with relatively longer radiative decay time.

Sulfur-rich molybdenum sulfides are an emerging class of inorganic coordination polymers that are predominantly utilized for their superior catalytic properties. Here we investigate surface water dependent properties of sulfur-rich MoSx (x = 32/3) and its interaction with water vapor. We report that MoSx is a highly hygroscopic semiconductor, which can reversibly bind up to 0.9 H2O molecule per Mo. The presence of surface water is found to have a profound influence on the semiconductor's properties, modulating the material's photoluminescence by over 1 order of magnitude, in transition from dry to moist ambient. Furthermore, the conductivity of a MoSx-based moisture sensor is modulated in excess of 2 orders of magnitude for 30% increase in humidity. As the core application, we utilize the discovered properties of MoSx to develop an electrolyteless water splitting photocatalyst that relies entirely on the hygroscopic nature of MoSx as the water source. The catalyst is formulated as an ink that can be coated onto insulating substrates, such as glass, leading to efficient hydrogen and oxygen evolution from water vapor. The concept has the potential to be widely adopted for future solar fuel production.

Nature Communications 8: Article number: 14482; published: 17 February 2017; Updated: 22 March 2017 The original version of this Article contained a typographical error in the spelling of the author Omid Kavehei, which was incorrectly given as Omid Kevehei. This has now been corrected in both the PDF and HTML versions of the Article.

A variety of deposition methods for two-dimensional crystals have been demonstrated; however, their wafer-scale deposition remains a challenge. Here we introduce a technique for depositing and patterning of wafer-scale two-dimensional metal chalcogenide compounds by transforming the native interfacial metal oxide layer of low melting point metal precursors (group III and IV) in liquid form. In an oxygen-containing atmosphere, these metals establish an atomically thin oxide layer in a self-limiting reaction. The layer increases the wettability of the liquid metal placed on oxygen-terminated substrates, leaving the thin oxide layer behind. In the case of liquid gallium, the oxide skin attaches exclusively to a substrate and is then sulfurized via a relatively low temperature process. By controlling the surface chemistry of the substrate, we produce large area two-dimensional semiconducting GaS of unit cell thickness (∼1.5 nm). The presented deposition and patterning method offers great commercial potential for wafer-scale processes., One of the key challenges 2D materials still face is their uniform wafer-scale deposition. Here, the authors present a deposition method for post-transition metal dichalcogenides, based on transformation of an ultra-thin oxide layer on the surface of liquid elemental gallium onto an oxide-coated substrate.

A surfactant assisted technique has been used to promote the exfoliation of molybdenum disulphide (MoS2) in a water-ethanol mixture, to avoid the use of harsh organic solvents, whilst still producing sufficient concentration of MoS2 in suspension. The exfoliated flakes are converted into MoS2 quantum dots (QDs), through a hydrothermal procedure. Alternatively, when the flakes are processed with precursors for zinc sulphide (ZnS) synthesis, a simultaneous break-down and composite growth is achieved. The products are separated by centrifugation, into large ZnS spheres (200-300 nm) and small MoS2-ZnS hybrid QD materials (