Engineering 2D Material Exciton Line Shape with Graphene/h-BN Encapsulation.

Control over the optical properties of atomically thin two-dimensional (2D) layers, including those of transition metal dichalcogenides (TMDs), is needed for future optoelectronic applications. Here, the near-field coupling between TMDs and graphene/graphite is used to engineer the exciton line shape and charge state. Fano-like asymmetric spectral features are produced in WS2, MoSe2, and WSe2 van der Waals heterostructures combined with graphene, graphite, or jointly with hexagonal boron nitride (h-BN) as supporting or encapsulating layers. Furthermore, trion emission is suppressed in h-BN encapsulated WSe2/graphene with a neutral exciton red shift (44 meV) and binding energy reduction (30 meV). The response of these systems to electron beam and light probes is well-described in terms of 2D optical conductivities of the involved materials. Beyond fundamental insights into the interaction of TMD excitons with structured environments, this study opens an unexplored avenue toward shaping the spectral profile of narrow optical modes for application in nanophotonic devices.

Direct synthesis of metastable phases of 2D transition metal dichalcogenides.

The different polymorphic phases of transition metal dichalcogenides (TMDs) have attracted enormous interest in the last decade. The metastable metallic and small band gap phases of group VI TMDs displayed leading performance for electrocatalytic hydrogen evolution, high volumetric capacitance and some of them exhibit large gap quantum spin Hall (QSH) insulating behaviour. Metastable 1T(1T') phases require higher formation energy, as compared to the thermodynamically stable 2H phase, thus in standard chemical vapour deposition and vapour transport processes the materials normally grow in the 2H phases. Only destabilization of their 2H phase via external means, such as charge transfer or high electric field, allows the conversion of the crystal structure into the 1T(1T') phase. Bottom-up synthesis of materials in the 1T(1T') phases in measurable quantities would broaden their prospective applications and practical utilization. There is an emerging evidence that some of these 1T(1T') phases can be directly synthesized via bottom-up vapour- and liquid-phase methods. This review will provide an overview of the synthesis strategies which have been designed to achieve the crystal phase control in TMDs, and the chemical mechanisms that can drive the synthesis of metastable phases. We will provide a critical comparison between growth pathways in vapour- and liquid-phase synthesis techniques. Morphological and chemical characteristics of synthesized materials will be described along with their ability to act as electrocatalysts for the hydrogen evolution reaction from water. Phase stability and reversibility will be discussed and new potential applications will be introduced. This review aims at providing insights into the fundamental understanding of the favourable synthetic conditions for the stabilization of metastable TMD crystals and at stimulating future advancements in the field of large-scale synthesis of materials with crystal phase control.

Thermal Decomposition of Ternary Sodium Graphite Intercalation Compounds.

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.

Fast Exfoliation and Functionalisation of Two-Dimensional Crystalline Carbon Nitride by Framework Charging.

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.

Epitaxial graphene growth and shape dynamics on copper: phase-field modeling and experiments.

The epitaxial growth of graphene on copper foils is a complex process, influenced by thermodynamic, kinetic, and growth parameters, often leading to diverse island shapes including dendrites, squares, stars, hexagons, butterflies, and lobes. Here, we introduce a phase-field model that provides a unified description of these diverse growth morphologies and compare the model results with new experiments. Our model explicitly accounts for the anisotropies in the energies of growing graphene edges, kinetics of attachment of carbon at the edges, and the crystallinity of the underlying copper substrate (through anisotropy in surface diffusion). We show that anisotropic diffusion has a very important, counterintuitive role in the determination of the shape of islands, and we present a "phase diagram" of growth shapes as a function of growth rate for different copper facets. Our results are shown to be in excellent agreement with growth shapes observed for high symmetry facets such as (111) and (001) as well as for high-index surfaces such as (221) and (310).

3D printing of layered vanadium disulfide for water-in-salt electrolyte zinc-ion batteries.

Miniaturized aqueous zinc ion batteries are attractive energy storage devices for wearable electronics, owing to their safety and low cost. Layered vanadium disulfide (VS2) has demonstrated competitive charge storage capability for aqueous zinc ion batteries, as a result of its multivalent states and large interlayer spacing. However, VS2 electrodes are affected by quick oxide conversion, and they present predefined geometries and aspect ratios, which hinders their integration in wearables devices. Here, we demonstrate the formulation of a suitable ink for extrusion-based 3D printing (direct ink writing) based on micro flowers of layered VS2 obtained using a scalable hydrothermal process. 3D printed architectures of arbitrary design present electrochemically active, porous and micron-sized struts with tuneable mass loading. These were used as cathodes for aqueous zinc-ion battery electrodes. The 3D printed VS2 cathodes were assembled with carbon/zinc foil anodes to form full cells of zinc-ion, demonstrating a capacity of ∼1.98 mA h cm-2 with an operating voltage of 1.5 V. Upon cycling a capacity retention of around 65% was achieved after ∼100 cycles. The choice of the electrolyte (a water-in-salt electrolyte) and the design of the pre-processing of the 3D printed cathode ensured improved stability against dissolution and swift oxidation, notorious challenges for VS2 in an aqueous environment. This works paves the way towards programmable manufacturing of miniaturized aqueous batteries and the materials processing approach can be applied to different materials and battery systems to improve stability.

Ultrasensitive colorimetric detection of creatinine via its dual binding affinity for silver nanoparticles and silver ions.

Creatinine is an important biomarker for the diagnosis of chronic kidney disease (CKD). Recently, it has been reported that the concentration of salivary creatinine correlates well with the concentration of serum creatinine, which makes the former useful for the development of non-invasive and point-of-care (POC) detection for CKD diagnosis. However, there exists a technical challenge in the rapid detection of salivary creatinine at low concentrations of 3-18 µM when using the current kidney function test strips as well as the traditional methods employed in hospitals. Herein, we demonstrate a simple, sensitive colorimetric assay for the detection of creatinine with a limit-of-detection (LOD) down to the nanomolar level. Our approach utilises the dual binding affinity of creatinine for citrate-capped silver nanoparticles (Ag NPs) and Ag(i) ions, which can trigger the aggregation of Ag NPs and thus lead to the colour change of a sample. The quantitative detection of creatinine was achieved using UV-Vis spectroscopy with a LOD of 6.9 nM in artificial saliva and a linear dynamic range of 0.01-0.06 µM. This method holds promise to be further developed into a POC platform for the CKD diagnosis.

Probing the dielectric response of graphene via dual-band plasmonic nanoresonators.

In this article, we use optical transmission spectroscopy to measure the changes in the resonance features of a Au plasmonic nanoresonator array consisting of concentric ring/disc cavity elements, when graphene is introduced as an encapsulating medium. We show that by using finite element modelling to best reproduce our experimental results the dielectric response of the graphene film can be determined. We discuss the potential of such structures for chemical sensing applications.

Tuning the 1T'/2H phases in WxMo1-xSe2 nanosheets.

Controlling materials' morphology, crystal phase and chemical composition at the atomic scale has become central in materials research. Wet chemistry approaches have great potential in directing the material crystallisation process to achieve tuneable chemical compositions as well as to target specific crystal phases. Herein, we report the compositional and crystal phase tuneability achieved in the quasi-binary WxMo1-xSe2 system with chemical and crystal phase mixing down to the atomic level. A series of WxMo1-xSe2 solid solutions in the form of nanoflowers with atomically thin petals were obtained via a direct colloidal reaction by systematically varying the ratios of transition metal precursors. We investigate the effect of selenium precursor on the morphology of the WxMo1-xSe2 material and show how using elemental selenium can enable the formation of larger and distinct nanoflowers. While the synthesised materials are compositionally homogeneous, they exhibit crystal phase heterogeneity with the co-existing domains of the 1T' and 2H crystal phases, and with evidence of MoSe2 in the metastable 1T' phase. We show at single atom level of resolution, that tungsten and molybdenum can be found in both the 1T' and 2H lattices. The formation of heterophase 1T'/2H WxMo1-xSe2 electrocatalysts allowed for a considerable improvement in the activity for the acidic hydrogen evolution reaction (HER) compared to pristine, 1T'-dominated, WSe2. This work can pave the way towards engineered functional nanomaterials where properties, such as electronic and catalytic, have to be controlled at the atomic scale.

Sodium Dual-Ion Batteries with Concentrated Electrolytes.

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 NaPF6 ) and fluorine-rich carbonate-based formulation was optimized to achieve a good performance when compared with literature (based on energy and power density, calculated at coin cell and only using the active mass of active materials).

Graphene Sensor Arrays for Rapid and Accurate Detection of Pancreatic Cancer Exosomes in Patients' Blood Plasma Samples.

Biosensors based on graphene field effect transistors (GFETs) have the potential to enable the development of point-of-care diagnostic tools for early stage disease detection. However, issues with reproducibility and manufacturing yields of graphene sensors, but also with Debye screening and unwanted detection of nonspecific species, have prevented the wider clinical use of graphene technology. Here, we demonstrate that our wafer-scalable GFETs array platform enables meaningful clinical results. As a case study of high clinical relevance, we demonstrate an accurate and robust portable GFET array biosensor platform for the detection of pancreatic ductal adenocarcinoma (PDAC) in patients' plasma through specific exosomes (GPC-1 expression) within 45 min. In order to facilitate reproducible detection in blood plasma, we optimized the analytical performance of GFET biosensors via the application of an internal control channel and the development of an optimized test protocol. Based on samples from 18 PDAC patients and 8 healthy controls, the GFET biosensor arrays could accurately discriminate between the two groups while being able to detect early cancer stages including stages 1 and 2. Furthermore, we confirmed the higher expression of GPC-1 and found that the concentration in PDAC plasma was on average more than 1 order of magnitude higher than in healthy samples. We found that these characteristics of GPC-1 cancerous exosomes are responsible for an increase in the number of target exosomes on the surface of graphene, leading to an improved signal response of the GFET biosensors. This GFET biosensor platform holds great promise for the development of an accurate tool for the rapid diagnosis of pancreatic cancer.

Solution-processable organic dielectrics for graphene electronics.

We report the fabrication, at low-temperature, of solution processed graphene transistors based on carefully engineered graphene/organic dielectric interfaces. Graphene transistors based on these interfaces show improved performance and reliability when compared with traditional SiO(2) based devices. The dielectric materials investigated include Hyflon AD (Solvay), a low-k fluoropolymer, and various organic self-assembled monolayer (SAM) nanodielectrics. Both types of dielectric are solution processed and yield graphene transistors with similar operating characteristics, namely high charge carrier mobility, hysteresis free operation, negligible doping effect and improved operating stability as compared to bare SiO(2) based devices. Importantly, the use of SAM nanodielectrics enables the demonstration of low operating voltage ( < |1.5| V), solution-processable and flexible graphene transistors with tunable doping characteristics through molecular engineering of the SAM's molecular length and terminal group. The work is a significant step towards graphene microelectronics where large-volume and low-temperature processing are required.

Durable Zn-ion hybrid capacitors using 3D printed carbon composites.

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 ZnSO4, features higher ionic conductivity and lower pH compared with pristine ZnSO4, which enable uniform plating/stripping of Zn2+ ions on Zn anode, as demonstrated by in situ electrochemical and ex situ ToF-SIMs characterizations. Additionally, the multi-layered 3D Gr-C composite electrodes in ZHCs enable higher energy storage performance due to their porous architectures, high ion accessibility and dual-ion charge storage contributions. As a result, the 3D Gr-C//Zn cell unveiled a maximum capacity of 0.84 mA h cm-2 at 3 mA cm-2 with a high life cycle (78.7% at 20 mA cm-2) compared to the pristine electrolyte-based ZHCs (0.72 mA h cm-2 and 14.8%). The rapid rate measurements that we propose along with benchmarked energy density (0.87 mW h cm-2) and power density (31.7 mW cm-2) of hybrid electrolyte-based 3D Gr-C//Zn, pave the way for the development of dendrite-free and highly durable 3D energy storage devices.

Synthesis of mono- and few-layered n-type WSe2 from solid state inorganic precursors.

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 WSe2, an otherwise ambipolar material, has been mainly limited to p-doping. Here, we demonstrate the synthesis of high-quality n-type monolayered WSe2 flakes using a solid-state precursor for Se, zinc selenide. n-Type transport has been reported with prime electron mobilities of up to 10 cm2 V-1 s-1. We also demonstrate the tuneability of doping to p-type transport with hole mobilities of 50 cm2 V-1 s-1 after annealing in air. n-Doping has been attributed to the presence of Zn adatoms on the WSe2 flakes as revealed by X-ray photoelectron spectroscopy (XPS), spatially resolved time of flight secondary ion mass spectroscopy (SIMS) and angular dark-field scanning transmission electron microscopy (AD-STEM) characterization of WSe2 flakes. Monolayer WSe2 flakes exhibit a sharp photoluminescence (PL) peak at room temperature and highly uniform emission across the entire flake area, indicating a high degree of crystallinity of the material. This work provides new insight into the synthesis of TMDs with charge carrier control, to pave the way towards post-silicon electronics.

On-chip integrated graphene aptasensor with portable readout for fast and label-free COVID-19 detection in virus transport medium.

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 103 particles per mL for virus-like particles (VLPs) in clinical transport medium, outperforming the Ab-GFET biosensor counterpart. In addition, the aptasensor achieved a LOD of 160 aM for COVID-19 neutralizing antibodies in serum. The sensors were found to be highly selective, fast (sample-to-result within minutes), and stable (low device-to-device signal variation; relative standard deviations below 0.5%). A home-built portable readout electronic unit was employed for simultaneous real-time measurements of 12 GFETs per chip. Our successful demonstration of a portable GFET biosensing platform has high potential for infectious disease detection and other health-care applications.

Platinum deposition on functionalised graphene for corrosion resistant oxygen reduction electrodes.

Graphene-related materials are promising supports for electrocatalysts due to their stability and high surface area. Their innate surface chemistries can be controlled and tuned via functionalisation to improve the stability of both the carbon support and the metal catalyst. Functionalised graphenes were prepared using either aryl diazonium functionalisation or non-destructive chemical reduction, to provide groups adapted for platinum deposition. XPS and TGA-MS measurements confirmed the presence of polyethyleneglycol and sulfur-containing functional groups, and provided consistent values for the extent of the reactions. The deposited platinum nanoparticles obtained were consistently around 2 nm via reductive chemistry and around 4 nm via the diazonium route. Although these graphene-supported electrocatalysts provided a lower electrochemical surface area (ECSA), functionalised samples showed enhanced specific activity compared to a commercial platinum/carbon black system. Accelerated stress testing (AST) showed improved durability for the functionalised graphenes compared to the non-functionalised materials, attributed to edge passivation and catalyst particle anchoring.

Synthesis of emerging 2D layered magnetic materials.

van der Waals atomically thin magnetic materials have been recently discovered. They have attracted enormous attention as they present unique magnetic properties, holding potential to tailor spin-based device properties and enable next generation data storage and communication devices. To fully understand the magnetism in two-dimensions, the synthesis of 2D materials over large areas with precise thickness control has to be accomplished. Here, we review the recent advancements in the synthesis of these materials spanning from metal halides, transition metal dichalcogenides, metal phosphosulphides, to ternary metal tellurides. We initially discuss the emerging device concepts based on magnetic van der Waals materials including what has been achieved with graphene. We then review the state of the art of the synthesis of these materials and we discuss the potential routes to achieve the synthesis of wafer-scale atomically thin magnetic materials. We discuss the synthetic achievements in relation to the structural characteristics of the materials and we scrutinise the physical properties of the precursors in relation to the synthesis conditions. We highlight the challenges related to the synthesis of 2D magnets and we provide a perspective for possible advancement of available synthesis methods to respond to the need for scalable production and high materials quality.

Aqueous Inks of Pristine Graphene for 3D Printed Microsupercapacitors with High Capacitance.

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.

Effect of graphene flake size on functionalisation: quantifying reaction extent and imaging locus with single Pt atom tags.

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.

Scalable Sacrificial Templating to Increase Porosity and Platinum Utilisation in Graphene-Based Polymer Electrolyte Fuel Cell Electrodes.

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.