A. C. Ferrari

Raman Spectrum of Graphene and Graphene Layers

Graphene is the two-dimensional (2d) building block for carbon allotropes of every other dimensionality. It can be stacked into 3d graphite, rolled into 1d nanotubes, or wrapped into 0d fullerenes. Its recent discovery in free state has finally provided the possibility to study experimentally its electronic and phonon properties. Here we show that graphenes electronic structure is uniquely captured in its Raman spectrum that clearly evolves with increasing number of layers. Raman fingerprints for single-, bi- and few-layer graphene reflect changes in the electronic structure and electron-phonon interactions and allow unambiguous, high-throughput, non-destructive identification of graphene layers, which is critically lacking in this emerging research area.

Graphene photonics and optoelectronics

The richness of optical and electronic properties of graphene attracts enormous interest. Graphene has high mobility and optical transparency, in addition to flexibility, robustness and environmental stability. So far, the main focus has been on fundamental physics and electronic devices. However, we believe its true potential lies in photonics and optoelectronics, where the combination of its unique optical and electronic properties can be fully exploited, even in the absence of a bandgap, and the linear dispersion of the Dirac electrons enables ultrawideband tunability. The rise of graphene in photonics and optoelectronics is shown by several recent results, ranging from solar cells and light-emitting devices to touch screens, photodetectors and ultrafast lasers. Here we review the state-of-the-art in this emerging field.

High-yield production of graphene by liquid-phase exfoliation of graphite

Fully exploiting the properties of graphene will require a method for the mass production of this remarkable material. Two main routes are possible: large-scale growth or large-scale exfoliation. Here, we demonstrate graphene dispersions with concentrations up to approximately 0.01 mg ml(-1), produced by dispersion and exfoliation of graphite in organic solvents such as N-methyl-pyrrolidone. This is possible because the energy required to exfoliate graphene is balanced by the solvent-graphene interaction for solvents whose surface energies match that of graphene. We confirm the presence of individual graphene sheets by Raman spectroscopy, transmission electron microscopy and electron diffraction. Our method results in a monolayer yield of approximately 1 wt%, which could potentially be improved to 7-12 wt% with further processing. The absence of defects or oxides is confirmed by X-ray photoelectron, infrared and Raman spectroscopies. We are able to produce semi-transparent conducting films and conducting composites. Solution processing of graphene opens up a range of potential large-area applications, from device and sensor fabrication to liquid-phase chemistry.

Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane

Although graphite is known as one of the most chemically inert materials, we have found that graphene, a single atomic plane of graphite, can react with atomic hydrogen, which transforms this highly conductive zero-overlap semimetal into an insulator. Transmission electron microscopy reveals that the obtained graphene derivative (graphane) is crystalline and retains the hexagonal lattice, but its period becomes markedly shorter than that of graphene. The reaction with hydrogen is reversible, so that the original metallic state, the lattice spacing, and even the quantum Hall effect can be restored by annealing. Our work illustrates the concept of graphene as a robust atomic-scale scaffold on the basis of which new two-dimensional crystals with designed electronic and other properties can be created by attaching other atoms and molecules.

Raman spectroscopy as a versatile tool for studying the properties of graphene

Raman spectroscopy is an integral part of graphene research. It is used to determine the number and orientation of layers, the quality and types of edge, and the effects of perturbations, such as electric and magnetic fields, strain, doping, disorder and functional groups. This, in turn, provides insight into all sp(2)-bonded carbon allotropes, because graphene is their fundamental building block. Here we review the state of the art, future directions and open questions in Raman spectroscopy of graphene. We describe essential physical processes whose importance has only recently been recognized, such as the various types of resonance at play, and the role of quantum interference. We update all basic concepts and notations, and propose a terminology that is able to describe any result in literature. We finally highlight the potential of Raman spectroscopy for layered materials other than graphene.

Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor

We demonstrate electrochemical top gating of graphene by using a solid polymer electrolyte. This allows to reach much higher electron and hole doping than standard back gating. In-situ Raman measurements monitor the doping. The G peak stiffens and sharpens for both electron and hole doping, while the 2D peak shows a different response to holes and electrons. Its position increases for hole doping, while it softens for high electron doping. The variation of G peak position is a signature of the non-adiabatic Kohn anomaly at

Quantifying Defects in Graphene via Raman Spectroscopy at Different Excitation Energies

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Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage

. On the other hand, for visible excitation, the variation of the 2D peak position is ruled by charge transfer. The intensity ratio of G and 2D peaks shows a strong dependence on doping, making it a sensitive parameter to monitor charges.The recent discovery of graphene has led to many advances in two-dimensional physics and devices. The graphene devices fabricated so far have relied on SiO(2) back gating. Electrochemical top gating is widely used for polymer transistors, and has also been successfully applied to carbon nanotubes. Here we demonstrate a top-gated graphene transistor that is able to reach doping levels of up to 5x1013 cm-2, which is much higher than those previously reported. Such high doping levels are possible because the nanometre-thick Debye layer in the solid polymer electrolyte gate provides a much higher gate capacitance than the commonly used SiO(2) back gate, which is usually about 300 nm thick. In situ Raman measurements monitor the doping. The G peak stiffens and sharpens for both electron and hole doping, but the 2D peak shows a different response to holes and electrons. The ratio of the intensities of the G and 2D peaks shows a strong dependence on doping, making it a sensitive parameter to monitor the doping.

Raman spectroscopy of amorphous, nanostructured, diamond–like carbon, and nanodiamond

We present a Raman study of Ar(+)-bombarded graphene samples with increasing ion doses. This allows us to have a controlled, increasing, amount of defects. We find that the ratio between the D and G peak intensities, for a given defect density, strongly depends on the laser excitation energy. We quantify this effect and present a simple equation for the determination of the point defect density in graphene via Raman spectroscopy for any visible excitation energy. We note that, for all excitations, the D to G intensity ratio reaches a maximum for an interdefect distance ∼3 nm. Thus, a given ratio could correspond to two different defect densities, above or below the maximum. The analysis of the G peak width and its dispersion with excitation energy solves this ambiguity.

Graphene mode-locked ultrafast laser.

Background The integration of graphene in photovoltaic modules, fuel cells, batteries, supercapacitors, and devices for hydrogen generation offers opportunities to tackle challenges driven by the increasing global energy demand. Graphene’s two-dimensional (2D) nature leads to a theoretical surface-to-mass ratio of ~2600 m2/g, which combined with its high electrical conductivity and flexibility, gives it the potential to store electric charge, ions, or hydrogen. Other 2D crystals, such as transition metal chalcogenides (TMDs) and transition metal oxides, are also promising and are now gaining increasing attention for energy applications. The advantage of using such 2D crystals is linked to the possibility of creating and designing layered artificial structures with “on-demand” properties by means of spin-on processes, or layer-by-layer assembly. This approach exploits the availability of materials with metallic, semiconducting, and insulating properties. Advances The success of graphene and related materials (GRMs) for energy applications crucially depends on the development and optimization of production methods. High-volume liquid-phase exfoliation is being developed for a wide variety of layered materials. This technique is being optimized to control the flake size and to increase the edge-to-surface ratio, which is crucial for optimizing electrode performance in fuel cells and batteries. Micro- or nanocrystal or flake edge control can also be achieved through chemical synthesis. This is an ideal route for functionalization, in order to improve storage capacity. Large-area growth via chemical vapor deposition (CVD) has been demonstrated, producing material with high structural and electronic quality for the preparation of transparent conducting electrodes for displays and touch-screens, and is being evaluated for photovoltaic applications. CVD growth of other multicomponent layered materials is less mature and needs further development. Although many transfer techniques have been developed successfully, further improvement of high-volume manufacturing and transfer processes for multilayered heterostructures is needed. In this context, layer-by-layer assembly may enable the realization of devices with on-demand properties for targeted applications, such as photovoltaic devices in which photon absorption in TMDs is combined with charge transport in graphene. Outlook Substantial progress has been made on the preparation of GRMs at the laboratory level. However, cost-effective production of GRMs on an industrial scale is needed to create the future energy value chain. Applications that could benefit the most from GRMs include flexible electronics, batteries with efficient anodes and cathodes, supercapacitors with high energy density, and solar cells. The realization of GRMs with specific transport and insulating properties on demand is an important goal. Additional energy applications of GRMs comprise water splitting and hydrogen production. As an example, the edges of MoS2 single layers can oxidize fuels—such as hydrogen, methanol, and ethanol—in fuel cells, and GRM membranes can be used in fuel cells to improve proton exchange. Functionalized graphene can be exploited for water splitting and hydrogen production. Flexible and wearable devices and membranes incorporating GRMs can also generate electricity from motion, as well as from water and gas flows. Tailored GRMs for energy applications. The ability to produce GRMs with desired specific properties paves the way to their integration in a variety of energy devices. Solution processing and chemical vapor deposition are the ideal means to produce thin films that can be used as electrodes in energy devices (such as solar panels, batteries, fuel cells, or in hydrogen storage). Chemical synthesis is an attractive route to produce “active” elements in solar cell or thermoelectric devices. Graphene and related two-dimensional crystals and hybrid systems showcase several key properties that can address emerging energy needs, in particular for the ever growing market of portable and wearable energy conversion and storage devices. Graphene’s flexibility, large surface area, and chemical stability, combined with its excellent electrical and thermal conductivity, make it promising as a catalyst in fuel and dye-sensitized solar cells. Chemically functionalized graphene can also improve storage and diffusion of ionic species and electric charge in batteries and supercapacitors. Two-dimensional crystals provide optoelectronic and photocatalytic properties complementing those of graphene, enabling the realization of ultrathin-film photovoltaic devices or systems for hydrogen production. Here, we review the use of graphene and related materials for energy conversion and storage, outlining the roadmap for future applications. Layered materials power the cause Methods for storing and converting energy, including fuel cells, solar cells, and water splitting, often benefit from having materials with a large surface area. When combined with a high surface reactivity, high conductivity, or useful optical properties, two-dimensional layered materials become of notable interest for a range of applications. Bonaccorso et al. review the progress that has been made using graphene and other layered or two-dimensional materials at laboratory scales and the challenges in producing these materials in industrially relevant quantities. Science, this issue 10.1126/science.1246501