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Nanomaterial morphology, chemical composition and 1T′/2H crystal phase tuning is achieved in colloidal WxMo1−xSe2 nanosheets synthesised by a direct colloidal reaction.

Graphene field-effect transistor (GFET) biosensors exhibit high sensitivity due to a large surface-to-volume ratio and the high sensitivity of the Fermi level to the presence of charged biomolecules near the surface. For most reported GFET biosensors, bulky external reference electrodes are used which prevent their full-scale chip integration and contribute to higher costs per test. In this study, GFET arrays with on-chip integrated liquid electrodes were employed for COVID-19 detection and functionalized with either antibody or aptamer to selectively bind the spike proteins of SARS-CoV-2. In the case of the aptamer-functionalized GFET (aptasensor, Apt-GFET), the limit-of-detection (LOD) achieved was about 10

Tuning the charge transport properties of two-dimensional transition metal dichalcogenides (TMDs) is pivotal to their future device integration in post-silicon technologies. To date, co-doping of TMDs during growth still proves to be challenging, and the synthesis of doped WSe

Na-based dual-ion batteries (DIBs) are a class of post-lithium technology with advantages including extremely fast charging, cost-effectiveness, and high natural abundance of raw materials. Operating up to high voltages (≈5.0 V), the decomposition of classic carbonate-based electrolyte formulations and the subsequent fade of capacity continues to be a major drawback in the development of these systems. Here, the performance of a Na-DIB was investigated in different commonly employed electrolyte system, and a highly concentrated (3 m NaPF

Here, the locus of functionalisation on graphene-related materials and the progress of the reaction is shown to depend strongly on the starting feedstock. Five characteristically different graphite sources were exfoliated and functionalized using a non-destructive chemical reduction method. These archetypical examples were compared via a model reaction, grafting dodecyl addends, evaluated with TGA-MS, XPS and Raman data. A general increase in grafting ratio (ranging from 1.1 wt% up to 25 wt%) and an improvement in grafting stoichiometry (C/R) were observed as flake radius decreased. Raman spectrum imaging of the functionalised natural flake graphite identified that grafting is directed towards flake edges. This behaviour was further corroborated, at atomistic resolution, by functionalising the graphene layers with bipyridine groups able to complex single platinum atoms. The distribution of these groups was then directly imaged using aberration-corrected HAADF-STEM. Platinum atoms were found to be homogeneously distributed across smaller graphenes; in contrast, a more heterogeneous distribution, with a predominance of edge grafting was observed for larger graphites. These observations show that grafting is directed towards flake edges, but not necessary at edge sites; the mechanism is attributed to the relative inaccessibility of the inner basal plane to reactive moieties, resulting in kinetically driven grafting nearer flake edges. This phenomenology may be relevant to a wide range of reactions on graphenes and other 2d materials., The flake size and morphology of the starting material strongly effect the degree and location of grafting when using reductive functionalisation.

Graphite intercalation compounds (GICs) are often used to produce exfoliated or functionalised graphene related materials (GRMs) in a specific solvent. This study explores the formation of the Na‐tetrahydrofuran (THF)‐GIC and a new ternary system based on dimethylacetamide (DMAc). Detailed comparisons of in situ temperature dependent XRD with TGA‐MS and Raman measurements reveal a series of dynamic transformations during heating. Surprisingly, the bulk of the intercalation compound is stable under ambient conditions, trapped between the graphene sheets. The heating process drives a reorganisation of the solvent and Na molecules, then an evaporation of the solvent; however, the solvent loss is arrested by restacking of the graphene layers, leading to trapped solvent bubbles. Eventually, the bubbles rupture, releasing the remaining solvent and creating expanded graphite. These trapped dopants may provide useful property enhancements, but also potentially confound measurements of grafting efficiency in liquid‐phase covalent functionalization experiments on 2D materials., Producing graphene: Graphite intercalation compounds (GICs) are often used to produce exfoliated or functionalised graphene related materials (GRMs) in a specific solvent. This study explores the formation of the Na‐tetrahydrofuran (THF)‐GIC and a new ternary system based on dimethylacetamide (DMAc).

Rechargeable Zn-ion hybrid capacitors (ZHCs) have gained considerable attention towards future energy storage applications owing to their non-flammable nature, high abundance of raw materials and remarkable energy storage performance. However, the uncontrolled growth of dendrites, interfacial corrosion of Zn anodes and limited mass loading of cathode materials, hinders their practical applicability. Herein, we demonstrate ZHCs with enhanced capacity and durability using a synergistic combination of a hybrid-ion electrolyte and a high-mass loading three-dimensionally (3D) printed graphene-carbon nanotube (Gr-C) cathode. The hybrid electrolyte composed of NaCl and ZnSO

Functionalisation of graphene with functional groups affords promising supports for electrocatalysts due to their improved durability and enhanced specific activity compared to commercial systems.

The excitonic states of transition metal dichacolgenide (TMD) monolayers are heavily influenced by their external dielectric environment based on the substrate used. In this work, various wide bandgap dielectric materials, namely hexagonal boron nitride (\textit{h}-BN) and amorphous silicon nitride (Si$_3$N$_4$), under different configurations as support or encapsulation material for WS$_2$ monolayers are investigated to disentangle the factors contributing to inhomogeneous broadening of exciton absorption lines in TMDs using electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). In addition, monolayer roughness in each configuration was determined from tilt series of electron diffraction patterns by assessing the broadening of diffraction spots by comparison with simulations. From our experiments, the main factors that play a role in linewidth broadening can be classified in increasing order of importance by: monolayer roughness, surface cleanliness, and substrate-induced charge trapping. Furthermore, because high-energy electrons are used as a probe, electron beam-induced damage on bare TMD monolayer is also revealed to be responsible for irreversible linewidth increases. \textit{h}-BN not only provides clean surfaces of TMD monolayer, and minimal charge disorder, but can also protect the TMD from irradiation damage. This work provides a better understanding of the mechanisms by which \textit{h}-BN remains, to date, the most compatible material for 2D material encapsulation, facilitating the realization of intrinsic material properties to their full potential.

The solid electrolyte interphase (SEI) is critical for lithium-ion batteries (LIBs). Understanding and control over how the SEI is formed is therefore essential to develop LIBs with improved coulombic efficiency, lifetime and capacity. Previous research has focused on how variations in electrolyte chemistry and charging conditions can manipulate the SEI, yet there remains a fundamental lack of understanding surrounding the formation mechanism of the SEI. Specifically, there is minimal research on how the electrode material itself influences the formation of the SEI. Herein, chemically equivalent yet electronically distinct mono-, bi- and multi-layered graphene are used as LIB anodes. The formation of the SEI is probed with respect to kinetics, mechanism, morphology, and composition. SEI films on monolayer graphene contain high amounts of decomposition products from the salt (LiPF6) while on multilayer graphene, the films contain a large proportion of organic products. The basal plane of SEI films contains more organic species in the side close to the electrode than close to the electrolyte because of the intrinsic charge transfer between the solvents and graphitic anodes. We demonstrate that the composition of SEI films is tunable by modifying the reduction capability of the anode relative to the electrolyte where high reduction kinetics promotes LiPF6 decomposition; low reduction kinetics leads to more solvent decomposition and sluggish phase change during SEI deposition. This work provides fundamental insights into the influence of electrode electronic structure on SEI formation, and provides future directions to improve LIBs.

Three-dimensional (3D) printing is gaining importance as a sustainable route for the fabrication of high-performance energy storage devices. It enables the streamlined manufacture of devices with programmable geometry at different length scales down to micron-sized dimensions. Miniaturized energy storage devices are fundamental components for on-chip technologies to enable energy autonomy. In this work, we demonstrate 3D printed microsupercapacitor electrodes from aqueous inks of pristine graphene without the need of high temperature processing and functional additives. With an intrinsic electrical conductivity of ∼1370 S m-1 and rationally designed architectures, the symmetric microsupercapacitors exhibit an exceptional areal capacitance of 1.57 F cm-2 at 2 mA cm-2 which is retained over 72% after repeated voltage holding tests. The areal power density (0.968 mW cm-2) and areal energy density (51.2 μWh cm-2) outperform the ones of previously reported carbon-based supercapacitors which have been either 3D or inkjet printed. Moreover, a current collector-free interdigitated microsupercapacitor combined with a gel electrolyte provides electrochemical performance approaching the one of devices with liquid-like ion transport properties. Our studies provide a sustainable and low-cost approach to fabricate efficient energy storage devices with programmable geometry.

Polymer electrolyte fuel cells hold great promise for a range of applications but require advances in durability for widespread commercial uptake. Corrosion of the carbon support is one of the main degradation pathways, hence, corrosion-resilient graphene has been widely suggested as an alternative to traditional carbon black. However, the performance of bulk graphene-based electrodes is typically lower than that of commercial carbon black due to their stacking effects. This article reports a simple, scalable and non-destructive method through which the pore structure and platinum utilisation of graphene-based membrane electrode assemblies can be significantly improved. Urea is incorporated into the catalyst ink before deposition, and is then simply removed from the catalyst layer after spraying by submerging the electrode in water. This additive hinders graphene restacking and increases porosity, resulting in a significant increase in Pt utilisation and current density. This technique does not require harsh template etching and it represents a pathway to significantly improve graphene-based electrodes by introducing hierarchical porosity using scalable liquid processes.

We demonstrate the enhanced robustness of the supercurrent through graphene-based Josephson junctions in which strong spin-orbit interactions (SOIs) are induced. We compare the persistence of a supercurrent at high out-of-plane magnetic fields between Josephson junctions with graphene on hexagonal boron-nitride and graphene on ${\mathrm{WS}}_{2}$, where strong SOIs are induced via the proximity effect. We find that in the shortest junctions both systems display signatures of induced superconductivity, characterized by a suppressed differential resistance at a low current, in magnetic fields up to 1 T. In longer junctions, however, only graphene on ${\mathrm{WS}}_{2}$ exhibits induced superconductivity features in such high magnetic fields, and they even persist up to 7 T. We argue that these robust superconducting signatures arise from quasiballistic edge states stabilized by the strong SOIs induced in graphene by ${\mathrm{WS}}_{2}$.

3D printing is a promising technique for the sustainable fabrication of energy devices with arbitrary architectures. Extrusion-based 3D printing, called Direct Ink Writing, are increasingly used for the manufacturing of batteries, supercapacitors and catalytic systems. In order to obtain me-chanically stable and functional devices, inks formulation must meet stringent criteria for printability, that are usually expressed in terms of rheological properties. Inks are rheologically complex fluids, in which the electroactive materials are mixed with additives and solvents to form an extrudable and self-standing paste. The ink formulation process plays a key role in tuning the rheology and the functional properties of the printed device. In this review, inks formulation, rheological characteristics and device performance are critically discussed, providing insights into the rheology-printability and formulation- functional properties relationships. The main strategies that have been proposed to obtain printable inks from energy materials are reviewed. The role played by the different ink components to achieve the target rheology is contextualized and the integration of different inks into an all-printed device is discussed. Finally, an outlook on the future challenges and opportunities for the DYW of energy materials is provided with the view that general formulations which do necessitate thermal post processing could widen the opportunities of this manufacturing technique enabling the use for large scale production of energy devices.

9 pags., 6 figs., 2 tabs., M. S. would like to acknowledge the President’s PhD Scholarship programme at Imperial College London for financial support. C. M. would like to acknowledge the EPSRC award EP/M022250/1, and the award of a Royal Society University Research Fellowship by the UK Royal Society. M. S. R. is supported through a studentship in the Centre for Doctoral Training on Theory and Simulation of Materials at Imperial College London funded by EPSRC Grant No. EP/L015579/1. M. N.-C. acknowledges support from the University of Birmingham (Birmingham Fellowship) and the EPSRC (grant no. EP/S018395/1). V. G. acknowledges the Spanish Ministerio de Economia y Competitividad for financial support through the grant NANOTOPO (FIS2017-91413- EXP), and also the Ministerio de Ciencia, Innovación y Universidades through the grant MELODIA (PGC2018-095777- B-C21).

We report on spin transport in WS

International audience; We report on spin transport in WS2-based 2D-magnetic tunnel junctions (2D-MTJs), unveiling a band structure spin filtering effect specific to the transition metal dichalcogenides (TMDCs) family. WS2 mono-, bi-, and trilayers are derived by a chemical vapor deposition process and further characterized by Raman spectroscopy, atomic force microscopy (AFM), and photoluminescence spec-troscopy. The WS2 layers are then integrated in complete Co/Al2O3 /WS2/Co MTJ hybrid spin-valve structures. We make use of a tunnel Co/Al2O3 spin analyzer to probe the extracted spin-polarized current from the WS2/Co interface and its evolution as a function of WS2 layer thicknesses. For monolayer WS2, our technological approach enables the extraction of the largest spin signal reported for a TMDC-based spin valve, corresponding to a spin polarization of PCo/WS2 = 12%. Interestingly, for bi-and trilayer WS2, the spin signal is reversed, which indicates a switch in the mechanism of interfacial spin extraction. With the support of ab initio calculations, we propose a model to address the experimentally measured inversion of the spin polarization based on the change in the WS2 band structure while going from monolayer (direct bandgap) to bilayer (indirect bandgap). These experiments illustrate the rich potential of the families of semiconducting 2D materials for the control of spin currents in 2D-MTJs.

Graphene is known for its high surface‐area‐to‐mass ratio. However, for graphene to be used in engineering processes such as catalytic reactors or heat exchangers, high surface‐area‐to‐volume ratio is essential. Currently, graphene is only prepared in sheet form, which limits its surface‐area‐to‐volume ratio to around 200 m2 m−3. In this study, we propose and demonstrate a technique based on chemical vapour deposition (CVD) to realise graphene on a copper‐based micro‐tubular substrate to not only substantially increase its surface‐area‐to‐volume ratio to a value over 2000 m2 m−3, but also to eliminate maldistribution of flows commonly unavoidable in flat‐sheet configurations. Our approach uses a dual‐layer micro‐tubular substrate fabricated by a phase‐inversion facilitated co‐extrusion technique. In the substrate, a thin copper outer layer is employed to enable the CVD growth of graphene, and an inner Cu‐Fe layer is adopted to provide a strong mechanical support. Our study shows that this approach is feasible to produce graphene with a very high surface‐area‐to‐volume ratio for possible practical applications in catalytic reactors or heat exchangers, though problems such as the inter‐diffusion between the two metal layers and defects in graphene need to be further addressed. To the best of our knowledge, this study is the first attempt to prepare graphene with high surface‐area‐to‐volume ratio by a CVD route.

Splitting salt water via sunlight into molecular oxygen and hydrogen for use as fuel or as an energy carrier is a clear pathway toward renewable energy. Monolayer MoS2 and WS2 are promising materials for the energetically demanding water oxidation reaction, absorbing ∼10% of incident light in the visible spectrum and possessing chemical stability and band edges more positive than the oxidation potential of water. A heterostructure of MoS2/WS2 forms a type-II heterojunction, supporting fast separation of the photogenerated charge carriers across the junction. Here, we show the role played by defects in determining the efficiency of the photon-driven oxidation process. By reducing the defects in this material system, it is possible to obtain an incident photon-to-current conversion efficiency (IPCE) of ∼1.6% and a visible-light-driven photocurrent density of 1.7 mA/cm2 for water oxidation. The efficiency is one order of magnitude higher than that of photoelectrocatalytic hydrogen reduction and water oxidation supported by liquid-phase exfoliated transition-metal dichalcogenides (TMDs). This result has been achieved with chemically vapor deposited (CVD) MoS2/WS2 heterojunctions, in the form of 100 μm large flakes assembled to form thin films. The large flakes sizes, compared to liquid-phase exfoliated materials (normally

We report a systematic study on strong enhancement of spin-orbit interaction (SOI) in graphene driven by transition-metal dichalcogenides (TMDs). Low temperature magnetotoransport measurements of graphene proximitized to different TMDs (monolayer and bulk WSe$_2$, WS$_2$ and monolayer MoS$_2$) all exhibit weak antilocalization peaks, a signature of strong SOI induced in graphene. The amplitudes of the induced SOI are different for different materials and thickness, and we find that monolayer WSe$_2$ and WS$_2$ can induce much stronger SOI than bulk ones and also monolayer MoS$_2$. The estimated spin-orbit (SO) scattering strength for the former reaches $\sim$ 10 meV whereas for the latter it is around 1 meV or less. We also discuss the symmetry and type of the induced SOI in detail, especially focusing on the identification of intrinsic and valley-Zeeman (VZ) SOI via the dominant spin relaxation mechanism. Our findings offer insight on the possible realization of the quantum spin Hall (QSH) state in graphene., 14 pages, 10 figures and 3 tables

We report valence band electronic structure evolution of graphene oxide (GO) upon its thermal reduction. Degree of oxygen functionalization was controlled by annealing temperatures, and an electronic structure evolution was monitored using real-time ultraviolet photoelectron spectroscopy. We observed a drastic increase in density of states around the Fermi level upon thermal annealing at ~600 oC. The result indicates that while there is an apparent band gap for GO prior to a thermal reduction, the gap closes after an annealing around that temperature. This trend of band gap closure was correlated with electrical, chemical, and structural properties to determine a set of GO material properties that is optimal for optoelectronics. The results revealed that annealing at a temperature of ~500 oC leads to the desired properties, demonstrated by a uniform and an order of magnitude enhanced photocurrent map of an individual GO sheet compared to as-synthesized counterpart., Comment: 9 pages, 4 figures in physica status solidi (a) 2016

Traditional synthesis methods of bulk semiconductors developed during the1970s and 1980s have recently undergone a resurgence of research interest. Physical vapour deposition (PVD), chemical vapour deposition (CVD) and metal organic chemical vapour deposition (MOCVD) have been extensively rediscovered to achieve three-atom thick metal dichalcogenides. Often defined as “graphene-analogous materials” atomically thin sulfides and selenides of group VI of transition metals have revealed a plethora of unforeseen optical, electrical and mechanical properties which make them unique candidates for future nanotechnologies, ranging from quantum electronics to large area consumer electronics. In the last few years tremendous progress has been achieved in the synthesis of high quality atomic crystals, often inspired by the consolidated synthesis methodologies of their bulk counterparts. Most interestingly, several of these methods are still used and also implemented to synthesize new compounds, expanding the range of accessible 2D materials. We review this progress and we highlight key difference in the coordination chemistry of different transition metals which are responsible for the different synthesis products.

Two-dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one-pot reductive method to produce solutions of single- and few-layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High-resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties.

Combining single-layer two-dimensional semiconducting transition metal dichalcogenides (TMDs) with graphene layer in van der Waals heterostructures offers an intriguing means of controlling the electronic properties through these heterostructures. Here, we report the electronic and structural properties of transferred single layer WS2 on epitaxial graphene using micro-Raman spectroscopy, angle-resolved photoemission spectroscopy measurements (ARPES) and Density Functional Theory (DFT) calculations. The results show good electronic properties as well as well-defined band arising from the strong splitting of the single layer WS2 valence band at K points, with a maximum splitting of 0.44 eV. By comparing our DFT results with local and hybrid functionals, we find the top valence band of the experimental heterostructure is close to the calculations for suspended single layer WS2. . Our results provide an important reference for future studies of electronic properties of WS2 and its applications in valleytronic devices., Comment: 11 pages, 3 figures + SI 7 pages 8 figures

Graphene has excellent mechanical, thermal, optical and electrical properties and this has made it a prime target for use as a filler material in the development of multifunctional polymeric composites. However, several challenges need to be overcome in order to take full advantage of the aforementioned properties of graphene. These include achieving good dispersion and interfacial properties between the graphene filler and the polymeric matrix. In the present work we report the thermal and mechanical properties of reduced graphene oxide/epoxy composites prepared via a facile, scalable and commercially-viable method. Electron micrographs of the composites demonstrate that the reduced graphene oxide (rGO) is well-dispersed throughout the composite. Although no improvements in glass transition temperature, tensile strength, and thermal stability in air of the composites were observed, good improvements in thermal conductivity (about 36%), tensile and storage moduli (more than 13%) were recorded with the addition of 2 wt% of rGO.

Catalyst degradation is one major challenge preventing the worldwide commercialization of the Proton Exchange Membrane Fuel Cells. In this study, we investigate the development of a novel hierarchical carbonaceous support for the platinum catalysts, called graphene-carbon nanotube hybrids (GCNT), and its degradation behavior during an accelerated degradation test. The carbon support is fabricated by growing graphene directly onto carbon nanotubes to form a unique all-carbon nanostructure possessing both an ultra-high density of exposed graphitic edges of graphene and a porous structure of carbon nanotubes. The GCNT-supported platinum catalyst exhibits a higher intrinsic catalytic activity than a carbon black-supported platinum catalyst, and much higher than a CNT-supported platinum catalyst. The enhanced catalytic activity of the GCNT-supported platinum catalyst is explained by the high graphitic edge density which promotes the catalytic reactions on platinum catalyst. The GCNT-supported platinum catalyst also exhibits a superior electrochemical stability over that of the carbon black-supported platinum catalyst, explained by the high crystallinity of the GCNT support. The superior stability is expressed by a lower loss in polarization performance, a smaller increase in charge transfer resistance, a lower loss in the platinum electrochemical surface area, a lower rate of carbon corrosion, and a more

Graphene oxide (GO) membranes have demonstrated great potential in liquid filtration. With the aim of real applications, GO membranes in a hollow fiber shape are of particular interest because of the high-efficiency and easy-assembly features at the module level. We report here that GO membranes on ceramic hollow fiber substrates are unstable at the dry state, mainly due to the drying-related shrinkage. And we demonstrate that these GO hollow fiber membranes can be stabilized by keeping them wet after initial controlled formation of the membranes. The GO hollow fiber membranes show higher permeation fluxes of acetone and methanol than most commercial membranes, and reject molecules larger than 300 Da, showing a great potential in the use of value-added organic solvent nanofiltration processes.

We demonstrate strong anisotropic spin-orbit interaction (SOI) in graphene induced by monolayer ${\mathrm{WS}}_{2}$. Direct comparison between graphene-monolayer ${\mathrm{WS}}_{2}$ and graphene-bulk ${\mathrm{WS}}_{2}$ systems in magnetotransport measurements reveals that monolayer transition metal dichalcogenide can induce much stronger SOI than bulk. Detailed theoretical analysis of the weak antilocalization curves gives an estimated spin-orbit energy (${E}_{\mathrm{so}}$) higher than 10 meV. The symmetry of the induced SOI is also discussed, and the dominant $z\ensuremath{\rightarrow}\ensuremath{-}z$ symmetric SOI can only explain the experimental results. Spin relaxation by the Elliot-Yafet mechanism and anomalous resistance increase with temperature close to the Dirac point indicates Kane-Mele SOI induced in graphene.

In this work, we report the colloidal synthesis of Bi2Te3 nanosheets with controlled thickness, morphology and crystallinity at temperatures as low as 20 °C. Grown at room temperature, Bi2Te3 exhibits two-dimensional morphology with thickness of 4 nm and lateral size of 200 nm. Upon increasing the temperature to 170 °C, the nanosheets demonstrate increased thickness of 16 nm and lateral dimensions of 600 nm where polycrystalline nanosheets (20 °C) are replaced by single crystal platelets (170 °C). Rapid synthesis of the material at moderately low temperatures with controllable morphology, crystallinity and consequently electrical and thermal properties can pave the way toward its large-scale production for practical applications.

The solar-assisted oxidation of water is an essential half reaction for achieving a complete cycle of water splitting. The search of efficient photoanodes that can absorb light in the visible range is of paramount importance to enable cost-effective solar energy-conversion systems. Here, we demonstrate that atomically thin layers of MoS2 and WS2 can oxidize water to O2 under incident light. Thin films of solution-processed MoS2 and WS2 nanosheets display n-type positive photocurrent densities of 0.45 mA cm–2 and O2 evolution under simulated solar irradiation. WS2 is significantly more efficient than MoS2; however, bulk heterojunctions (B-HJs) of MoS2 and WS2 nanosheets results in a 10-fold increase in incident-photon-to-current-efficiency, compared to the individual constituents. This proves that charge carrier lifetime is tailorable in atomically thin crystals by creating heterojunctions of different compositions and architectures. Our results suggest that the MoS2 and WS2 nanosheets and their B-HJ blend are interesting photocatalytic systems for water oxidation, which can be coupled with different reduction processes for solar-fuel production.

The rise of atomically thin materials has the potential to enable a paradigm shift in modern technologies by introducing multi-functional materials in the semiconductor industry. To date the growth of high quality atomically thin semiconductors (e.g. WS2) is one of the most pressing challenges to unleash the potential of these materials and the growth of mono- or bi-layers with high crystal quality is yet to see its full realization. Here, we show that the novel use of molecular precursors in the controlled synthesis of mono- and bi-layer WS2 leads to superior material quality compared to the widely used direct sulfidization of WO3-based precursors. Record high room temperature charge carrier mobility up to 52 cm2/Vs and ultra-sharp photoluminescence linewidth of just 36 meV over submillimeter areas demonstrate that the quality of this material supersedes also that of naturally occurring materials. By exploiting surface diffusion kinetics of W and S species adsorbed onto a substrate, a deterministic layer thickness control has also been achieved promoting the design of scalable synthesis routes.

The electrochemical double layer plays a fundamental role in energy storage applications. Control of the distribution of ions in the double layer at the atomistic scale offers routes to enhanced material functionality and device performance. Here we demonstrate how the addition of an element from the third row of the periodic table, phosphorus, to graphene oxide increases the measured capacitance and present density functional theory calculations that relate the enhanced charge storage to structural changes of the electrochemical double layer. Our results point to how rational design of materials at the atomistic scale can lead to improvements in their performance for energy storage.

An evanescent field microwave microscope has been developed at the National Physical Laboratory. This instrument has multiple applications and has been developed to allow traceable measurements of local complex permittivity, unlike most other microwave scanning microscopes. In this paper we describe basic operation of the microscope and show measurements on graphene samples produced at Imperial College. The microscope obtains images by raster scanning of a wire probe in ‘contact mode’. Of particular interest to the graphene community is the possibility of being able to scan over large areas (up to 4×4 mm2), and to be able to measure actual values of surface resistance without a requirement for metal contacts. As an ultrathin semimetal, a graphene layer being placed in the evanescent field of the probe is expected to behave like a lossy dielectric material, its microwave loss tangent is proportional to its conductivity. Employing a high Q dual mode re-entrant cavity as host resonator and a spherical metal probe of 180 μm diameter, we found that spatial variations of the conductivity of graphene can be clearly resolved.

Raman spectroscopic maps were used to study the local properties of graphene films as grown on corrugated copper foils, by chemical vapour deposition, and after transfer onto SiO2(300 nm)/Si substrates. Analysis of the Raman peaks show the films exhibit a striped periodic pattern of single- and bi-layer graphene. By performing simultaneous AFM–Raman line maps of the as grown film on Cu we find that the layer growth shows a strong correlation to substrate topography. As a result, compressively strained non-AB stacked bi-layer graphene forms preferentially along the ridges, whilst single-layer graphene grows inside the trenches, of the Cu foil topography. These experimental results suggest that surface mobility is not the dominating factor determining control of layer number in such growth regimes.

Two-dimensional materials are known to harbour properties very different from those of their bulk counterparts. Recent years have seen the rise of atomically thin superconductors, with a caveat that superconductivity is strongly depleted unless enhanced by specific substrates, intercalants or adatoms. Surprisingly, the role in superconductivity of electronic states originating from simple free surfaces of two-dimensional materials has remained elusive to date. Here, based on first-principles calculations, anisotropic Eliashberg theory, and angle-resolved photoemission spectroscopy (ARPES), we show that surface states in few-monolayer MgB2 make a major contribution to the superconducting gap spectrum and density of states, clearly distinct from the widely known, bulk-like σ- and π-gaps. As a proof of principle, we predict and measure the gap opening on the magnesium-based surface band up to a critical temperature as high as ~30 K for merely six monolayers thick MgB2. These findings establish free surfaces as an unavoidable ingredient in understanding and further tailoring of superconductivity in atomically thin materials.

A well-dispersed phase of exfoliated graphene oxide (GO) nanosheets was\ud initially prepared in water. This was concentrated by centrifugation and was\ud mixed with a liquid epoxy resin. The remaining water was removed by evaporation,\ud leaving a GO dispersion in epoxy resin. A stoichiometric amount of an\ud anhydride curing agent was added to this epoxy-resin mixture containing the\ud GO nanosheets, which was then cured at 90 C for 1 h followed by 160 C for\ud 2 h. A second thermal treatment step of 200 C for 30 min was then undertaken\ud to reduce further the GO in situ in the epoxy nanocomposite. An examination of\ud the morphology of such nanocomposites containing reduced graphene oxide\ud (rGO) revealed that a very good dispersion of rGO was achieved throughout the\ud epoxy polymer. Various thermal and mechanical properties of the epoxy\ud nanocomposites were measured, and the most noteworthy finding was a\ud remarkable increase in the thermal conductivity when relatively very low contents\ud of rGO were present. For example, a value of 0.25 W/mK was measured at\ud 30 C for the nanocomposite with merely 0.06 weight percentage (wt%) of rGO\ud present, which represents an increase of *40% compared with that of the\ud unmodified epoxy polymer. This value represents one of the largest increases in\ud the thermal conductivity per wt% of added rGO yet reported. These observations\ud have been attributed to the excellent dispersion of rGO achieved in these\ud nanocomposites made via this facile production method. The present results\ud show that it is now possible to tune the properties of an epoxy polymer with a\ud simple and viable method of GO addition.\ud Ad

Transient currents in atomically thin MoTe

The synthesis of wafer-scale single crystal graphene remains a challenge toward the utilization of its intrinsic properties in electronics. Until now, the large-area chemical vapor deposition of graphene has yielded a polycrystalline material, where grain boundaries are detrimental to its electrical properties. Here, we study the physicochemical mechanisms underlying the nucleation and growth kinetics of graphene on copper, providing new insights necessary for the engineering synthesis of wafer-scale single crystals. Graphene arises from the crystallization of a supersaturated fraction of carbon-adatom species, and its nucleation density is the result of competition between the mobility of the carbon-adatom species and their desorption rate. As the energetics of these phenomena varies with temperature, the nucleation activation energies can span over a wide range (1-3 eV) leading to a rational prediction of the individual nuclei size and density distribution. The growth-limiting step was found to be the attachment of carbon-adatom species to the graphene edges, which was independent of the Cu crystalline orientation.

Reduction of graphene oxide (GO) at low temperature and atmospheric pressure via plasma-assisted chemistry is demonstrated. Hydrogen gas is continuously dissociated in a microplasma to generate atomic hydrogen, which flows from the remote plasma to thin films of GO deposited on a substrate. Direct interaction with ions and other energetic species is avoided to mitigate ion-induced sputter removal or damage. The residual oxygen content and structure of the GO films after plasma treatment is systematically characterized at different temperatures and correlated to the conductivity of the films. For example, at 150 °C, we find that the plasma-reduced GO contains less than 12.5% oxygen and exhibits a sheet resistance of 4.77 × 10(4) Ω/sq, as compared with thermal reduction alone, which results in 22.9% oxygen and a sheet resistance of 2.14 × 10(6) Ω/sq. Overall, the effective removal of oxygen functional groups by atomic hydrogen enables large-scale applications of GO as flexible conductors to be realized.