We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a ‘hands-on’ approach, providing practical details and procedures as derived from literature as well as from the authors’ experience, in order to enable the reader to reproduce the results. Section is devoted to ‘bottom up’ approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section covers ‘top down’ techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers’ and modified Hummers’ methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by ...

Electrically conductive composites comprising polymers and graphene are extremely versatile and have a wide range of potential applications. The conductivity of these composites depends on the choice of polymer matrix, the type of graphene filler, the processing methodology, and any post-production treatments. In this review, we discuss the progress in graphene–polymer composites for electrical applications. Graphene filler types are reviewed, the progress in modelling these composites is outlined, the current optimal composites are presented, and the example of strain sensors is used to demonstrate their application.

We present a novel approach for detecting and visualizing graphene oxide (GO) with high contrast on different substrates, including glass, quartz, and silicon. Visualization of GO sheets is accomplished through quenching the fluorescence of a thiophene dye, giving high optical contrast without the need to use interference methods. A comparison of fluorescence, AFM, and XRD measurements confirmed that even a single GO sheet can completely quench the fluorescence and thus be quickly visualized.

The tuning of the molecular material work-function via strong coupling with vacuum electromagnetic fields is demonstrated. Kelvin probe microscopy extracts the surface potential (SP) changes of a photochromic molecular film on plasmonic hole arrays and inside Fabry-Perot cavities. Modulating the optical cavity resonance or the photochromic film effectively tunes the work-function, suggesting a new tool for tailoring material properties.

In microelectronics and biology, many fundamental processes involve the exchange of charges between small objects, such as nanocrystals in photovoltaic blends or individual proteins in photosynthetic reactions. Because these nanoscale electronic processes strongly depend on the structure of the electroactive assemblies, a detailed understanding of these phenomena requires unraveling the relationship between the structure of the nano-object and its electronic function. Because of the fragility of the structures involved and the dynamic variance of the electric potential of each nanostructure during the charge generation and transport processes, understanding this structure-function relationship represents a great challenge. This Account discusses how our group and others have exploited scanning probe microscopy based approaches beyond imaging, particularly Kelvin probe force microscopy (KPFM), to map the potential of different nanostructures with a spatial and voltage resolution of a few nanometers and millivolts, respectively. We describe in detail how these techniques can provide researchers several types of chemical information. First, KPFM allows researchers to visualize the photogeneration and splitting of several unitary charges between well-defined nano-objects having complementary electron-acceptor and -donor properties. In addition, this method maps charge injection and transport in thin layers of polycrystalline materials. Finally, KPFM can monitor the activity of immobilized chemical components of natural photosynthetic systems. In particular, researchers can use KPFM to measure the electric potential without physical contact between the tip and the nanostructure studied. These measurements exploit long-range electrostatic interactions between the scanning probe and the sample, which scale with the square of the probe-sample distance, d. While allowing minimal perturbation, these long-range interactions limit the resolution attainable in the measurement of potentials. Although the spatial resolution of KPFM is on the nanometer scale, it is inferior to that of other related techniques such as atomic force or scanning tunneling microscopy, which are based on short-range interactions scaling as d(-7) or e(-d), respectively. To overcome this problem, we have recently devised deconvolution procedures that allow us to quantify the electric potential of a nano-object removing the artifacts due to its nanometric size.

Blends of reduced graphene oxide (RGO) and poly(3-hexylthiophene) (P3HT) are used as the active layer of field-effect transistors (FETs). By using sequential deposition of the two components, the density of RGO sheets can be tuned linearly, thereby modulating their contribution to the charge transport in the transistors, and the onset of charge percolation. The surface potential of RGO, P3HT and source-drain contacts is measured on the nanometric scale with Kelvin Probe Force Microscopy (KPFM), and correlated with the macroscopic performance of the FETs. KPFM is also used to monitor the potential decay along the channel in the working FETs.

We describe a fast and versatile method to functionalize high-quality graphene with organic molecules by exploiting the synergistic effect of supramolecular and covalent chemistry. With this goal, we designed and synthesized molecules comprising a long aliphatic chain and an aryl diazonium salt. Thanks to the long chain, these molecules physisorb from solution onto CVD graphene or bulk graphite, self-assembling in an ordered monolayer. The sample is successively transferred into an aqueous electrolyte, to block any reorganization or desorption of the monolayer. An electrochemical impulse is used to transform the diazonium group into a radical capable of grafting covalently to the substrate and transforming the physisorption into a covalent chemisorption. During covalent grafting in water, the molecules retain the ordered packing formed upon self-assembly. Our two-step approach is characterized by the independent control over the processes of immobilization of molecules on the substrate and their covalent tethering, enabling fast (t < 10 s) covalent functionalization of graphene. This strategy is highly versatile and works with many carbon-based materials including graphene deposited on silicon, plastic, and quartz as well as highly oriented pyrolytic graphite.

A simple, fast and general protocol for quantitative analysis of X-ray photoelectron spectroscopy (XPS) data provides accurate estimations of chemical species in graphene and related materials (GRMs). XPS data are commonly used to estimate the quality of and defects in graphene and graphene oxide (GO), by comparing carbon and oxygen 1s XPS peaks, obtaining an O/C ratio. This approach, however, cannot be used in the presence of extraneous oxygen contamination. The protocol, based on quantitative line-shape analysis of C 1s signals, uses asymmetric pseudo-Voigt line-shapes (APV), in contrast to Gaussian-based approaches conventionally used in fitting XPS spectra, thus allowing better accuracy in quantifying C 1s contributions from graphitic carbon (sp 2), defects (sp 3 carbon), carbons bonded to hydroxyl and epoxy groups, and from carbonyl and carboxyl groups. The APV protocol was evaluated on GRMs with O/C ratios ranging from 0.02 to 0.30 with film thicknesses from monolayers to bulk-like (>30nm) layers and also applied to previously published data, showing better results compared to those from conventional XPS fitting protocols. Based uniquely on C 1s data, the APV protocol can quantify O/C ratio and the presence of specific functional groups in GRMs even on SiOx, substrates, or in samples containing water.