Physical and chemical characterisation of exfoliated layered nanomaterials

Liquid phase exfoliation (LPE) is a versatile and scalable production technique for two-dimensional nanomaterials, such as graphene and molybdenum disulfide (MoS2). Solution processing enables a wide range of applications, many of which are sensitive to nanosheet microscopic properties, including size, thickness and functionalisation. Yet these nanosheets remain poorly characterised with the lack of standardisation. A method to sonochemically edge functionalise MoS2 in acetone is detailed here;away of producing stable dispersions over extended periods of time (over one year) at high concentrations. By using a range of techniques, it is shown that this stabilisation is achieved through a self-limiting oxidation of MoS2 at the edges. The method results in enhanced catalytic performance for MoS2 and potentially other sulfur containing layered materials. In addition, a general method to reconstruct nanosheets size and thickness distributions based on Raman spectroscopic metrics is demonstrated with graphene and MoS2. This is essential for any research that relies on quantifying the influences of size and thickness on applications, such as mechanical reinforcement, electrical conductivity, sensing, and catalysis. A new metric for characterising layer number of MoS2 nanosheets is developed using an intensity ratio of resonant Raman modes. Raman spectroscopy is less time consuming and less dependent on sample preparation when compared to microscopic characterisation techniques that yield the same information. The method presented here is more robust than current literature metric as it does not rely on mode positions, which shift depending on factors inherent to the sample such as strain, doping, and defect density. The metric was developed for LPE nanosheets but it can also be applied to mechanically exfoliated sheets. The first proposed metric for LPE nanosheet length was developed using the main Raman modes of MoS2 for resonant spectra, showing excellent agreement with microscopic measurements. It is anticipated this combination of mapping and metric analysis can be extended to other materials, paving the way for a much-needed standardisation for industry and laboratory research applications of layered nanomaterial

Functional liquid structures by emulsification of graphene and other two-dimensional nanomaterials

Pickering emulsions stabilised with nanomaterials provide routes to a range of functional macroscopic assemblies. We demonstrate the formation and properties of water-in-oil emulsions prepared through liquid-phase exfoliation of graphene. Due to the functional nature of the stabiliser, the emulsions exhibit conductivity due to inter-particle tunnelling. We demonstrate a strain sensing application with a large gauge factor of ~40; the highest reported in a liquid. Our methodology can be applied to other two-dimensional layered materials opening up applications such as energy storage materials, and flexible and printable electronics

Localised strain and doping of 2D materials

There is a growing interest in 2D materials-based devices as the replacement for established materials, such as silicon and metal oxides in microelectronics and sensing, respectively. However, the atomically thin nature of 2D materials makes them susceptible to slight variations caused by their immediate environment, inducing doping and strain, which can vary between, and even microscopically within, devices. One of the misapprehensions for using 2D materials is the consideration of unanimous intrinsic properties over different support surfaces. The interfacial interaction, intrinsic structural disorder and external strain modulate the properties of 2D materials and govern the device performance. The understanding, measurement and control of these factors are thus one of the significant challenges for the adoption of 2D materials in industrial electronics, sensing, and polymer composites. This topical review provides a comprehensive overview of the effect of strain-induced lattice deformation and its relationship with physical and electronic properties. Using the example of graphene and MoS2 (as the prototypical 2D semiconductor), we rationalise the importance of scanning probe techniques and Raman spectroscopy to elucidate strain and doping in 2D materials. These effects can be directly and accurately characterised through Raman shifts in a non-destructive manner. A generalised model has been presented that deconvolutes the intertwined relationship between strain and doping in graphene and MoS2 that could apply to other members of the 2D materials family. The emerging field of straintronics is presented, where the controlled application of strain over 2D materials induces tuneable physical and electronic properties. These perspectives highlight practical considerations for strain engineering and related microelectromechanical applications

Surfactant-free liquid-exfoliated copper hydroxide nanocuboids for non-enzymatic electrochemical glucose detection

To facilitate printable sensing solutions particles need to be suspended and stabilised in a liquid medium. Hansen parameters were used to identify that alcohol–water blends are ideal for stabilising colloidal copper hydroxide in dispersion. The suspended material can be further separated in various size fractions with a distinct cuboid geometry which was verified using atomic force microscopy. This facilitates the development of Raman spectroscopic metrics for determining particle sizes. This aspect ratio is related to the anisotropic crystal structure of the bulk crystallites. As the size of the nanocuboids decreases electrochemical sensitivity of the material increases due to an increase in specific surface area. Electrochemical glucose sensitivity was investigated using both cyclic voltammetry and chronoamperometry. The sensitivity is noted to saturate with film thickness. The electrochemical response of 253 mA M−1 cm−2 up to 0.1 mM and 120 mA cm−2 up to 0.6 mM allow for calibration of potential devices. These results indicate suitability for use as a glucose sensor and, due to the surfactant-free, low boiling point solvent approach used to exfoliate the nanocuboids, it is an ideal candidate for printable solutions. The ease of processing will also allow this material to be integrated in composite films for improved functionality in future devices

Mid-infrared electrochromics enabled by intraband modulation in carbon nanotube networks

Tuneable infrared properties, such as transparency and emissivity, are highly desirable for a range of applications, including thermal windows and emissive cooling. Here, we demonstrate the use of carbon nanotube networks spray-deposited onto an ionic liquid-infused membrane to fabricate devices with electrochromic modulation in the mid-infrared spectrum, facilitating control of emissivity and apparent temperature. Such modulation is enabled by intraband transitions in unsorted single-walled carbon nanotube networks, allowing the use of scalable nanotube inks for printed devices. These devices are optimized by varying film thickness and sheet resistance, demonstrating the emissivity modulation (from ∼0.5 to ∼0.2). These devices and the understanding thereof open the door to selection criteria for infrared electrochromic materials based on the relationship between band structure, electrochemistry, and optothermal properties to enable the development of solution-processable large-area coatings for widespread thermal management applications

Size selection and thin-film assembly of MoS2 elucidates thousandfold conductivity enhancement in few-layer nanosheet networks

Printed electronics based on liquid-exfoliated nanosheet networks are limited by inter-nanosheet junctions and thick films which hinder field-effect gating. Here, few-layer molybdenum disulfide nanosheets are assembled by Langmuir deposition into thin films, and size selection is shown to lead to a thousandfold conductivity enhancement with potential applicability to all nanosheet networks

Ultrasensitive strain gauges enabled by graphene-stabilized silicone emulsions

Here, an approach is presented to incorporate graphene nanosheets into a silicone rubber matrix via solid stabilization of oil‐in‐water emulsions. These emulsions can be cured into discrete, graphene‐coated silicone balls or continuous, elastomeric films by controlling the degree of coalescence. The electromechanical properties of the resulting composites as a function of interdiffusion time and graphene loading level are characterized. With conductivities approaching 1 S m−1, elongation to break up to 160%, and a gauge factor of ≈20 in the low‐strain linear regime, small strains such as pulse can be accurately measured. At higher strains, the electromechanical response exhibits a robust exponential dependence, allowing accurate readout for higher strain movements such as chest motion and joint bending. The exponential gauge factor is found to be ≈20, independent of loading level and valid up to 80% strain; this consistent performance is due to the emulsion‐templated microstructure of the composites. The robust behavior may facilitate high‐strain sensing in the nonlinear regime using nanocomposites, where relative resistance change values in excess of 107 enable highly accurate bodily motion monitoring

Raman metrics for molybdenum disulfide and graphene enable statistical mapping of nanosheet populations

The growing research interest and uptake of layered nanomaterials for real-world applications require efficient, reliable, high-quality characterisation methods. Liquid-exfoliated graphene has well-established Raman spectroscopic metrics for mean size and thickness. In association with the high-resolution mapping process described here, distributions of nanosheet properties can be reconstructed. Here, we develop new, robust metrics for length and layer number of MoS₂ nanosheets, developed using resonant Raman spectroscopy, applicable to both liquid- and mechanically-exfoliated MoS₂. The use of metricised Raman mapping analysis, here demonstrated for graphene and MoS₂, facilitates the standardisation of characterisation, allowing the correlation of size- and thickness-sensitive applications’ performance with materials properties

Charge Transfer Hybrids of Graphene Oxide and the Intrinsically Microporous Polymer PIM-1

Nanohybrid materials based on nanoparticles of the intrinsically microporous polymer PIM-1 and graphene oxide (GO) are prepared from aqueous dispersions with a re-precipitation method, resulting in the surface of the GO sheets being decorated with nanoparticles of PIM-1. The significant blueshift in fluorescence signals for the GO/PIM-1 nanohybrids indicates modification of the optoelectronic properties of the PIM-1 in the presence of the GO due to their strong interactions. The stiffening in the Raman G peak of GO (by nearly 6 cm^{-1}) further indicates p-doping of the GO in the presence of PIM. Kelvin probe force microscopy (KPFM) and electrochemical reduction measurements of the nanohybrids provide direct evidence for charge transfer between the PIM-1 nanoparticles and the GO nanosheets. These observations will be of importance for future applications of GO-PIM-1 nanohybrids as substrates and promoters in catalysis and sensing