Cecilia Mattevi

Structural evolution during the reduction of chemically derived graphene oxide

The excellent electrical, optical and mechanical properties of graphene have driven the search to find methods for its large-scale production, but established procedures (such as mechanical exfoliation or chemical vapour deposition) are not ideal for the manufacture of processable graphene sheets. An alternative method is the reduction of graphene oxide, a material that shares the same atomically thin structural framework as graphene, but bears oxygen-containing functional groups. Here we use molecular dynamics simulations to study the atomistic structure of progressively reduced graphene oxide. The chemical changes of oxygen-containing functional groups on the annealing of graphene oxide are elucidated and the simulations reveal the formation of highly stable carbonyl and ether groups that hinder its complete reduction to graphene. The calculations are supported by infrared and X-ray photoelectron spectroscopy measurements. Finally, more effective reduction treatments to improve the reduction of graphene oxide are proposed.

A review of chemical vapour deposition of graphene on copper

The discovery of uniform deposition of high-quality single layered graphene on copper has generated significant interest. That interest has been translated into rapid progress in terms of large area deposition of thin films via transfer onto plastic and glass substrates. The opto-electronic properties of the graphene thin films reveal that they are of very high quality with transmittance and conductance values of >90% and 30Ω/sq, both are comparable to the current state-of-the-art indium tin oxide transparent conductor. In this Feature Article, we provide a detailed and up to date description of the literature on the subject as well as highlighting challenges that must be overcome for the utilization of graphene deposited on copper substrates by chemical vapour deposition.

Atomic and Electronic Structure of Graphene-Oxide

We elucidate the atomic and electronic structure of graphene oxide (GO) using annular dark field imaging of single and multilayer sheets and electron energy loss spectroscopy for measuring the fine structure of C and O K-edges in a scanning transmission electron microscope. Partial density of states and electronic plasma excitations are also measured for these GO sheets showing unusual pi* + sigma* excitation at 19 eV. The results of this detailed analysis reveal that the GO is rough with an average surface roughness of 0.6 nm and the structure is predominantly amorphous due to distortions from sp3 C-O bonds. Around 40% sp3 bonding was found to be present in these sheets with measured O/C ratio of 1:5. These sp2 to sp3 bond modifications due to oxidation are also supported by ab initio calculations

Unusual infrared-absorption mechanism in thermally reduced graphene oxide

Infrared absorption of atomic and molecular vibrations in solids can be affected by electronic contributions through non-adiabatic interactions, such as the Fano effect. Typically, the infrared-absorption lineshapes are modified, or infrared-forbidden modes are detectable as a modulation of the electronic absorption. In contrast to such known phenomena, we report here the observation of a giant-infrared-absorption band in reduced graphene oxide, arising from the coupling of electronic states to the asymmetric stretch mode of a yet-unreported structure, consisting of oxygen atoms aggregated at the edges of defects. Free electrons are induced by the displacement of the oxygen atoms, leading to a strong infrared absorption that is in phase with the phonon mode. This new phenomenon is only possible when all other oxygen-containing chemical species, including hydroxyl, carboxyl, epoxide and ketonic functional groups, are removed from the region adjacent to the edges, that is, clean graphene patches are present.

Activation energy paths for graphene nucleation and growth on Cu.

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.

Highly Uniform 300 mm Wafer-Scale Deposition of Single and Multilayered Chemically Derived Graphene Thin Films

The deposition of atomically thin highly uniform chemically derived graphene (CDG) films on 300 mm SiO(2)/Si wafers is reported. We demonstrate that the very thin films can be lifted off to form uniform membranes that can be free-standing or transferred onto any substrate. Detailed maps of thickness using Raman spectroscopy and atomic force microscopy height profiles reveal that the film thickness is very uniform and highly controllable, ranging from 1-2 layers up to 30 layers. After reduction using a variety of methods, the CDG films are transparent and electrically active with FET devices yielding high mobilities of approximately 15 cm(2)/(V s) and sheet resistance of approximately 1 kOmega/sq at approximately 70% transparency.

Mesoscale assembly of chemically modified graphene into complex cellular networks

The widespread technological introduction of graphene beyond electronics rests on our ability to assemble this two-dimensional building block into three-dimensional structures for practical devices. To achieve this goal we need fabrication approaches that are able to provide an accurate control of chemistry and architecture from nano to macroscopic levels. Here, we describe a versatile technique to build ultralight (density ≥1 mg cm−3) cellular networks based on the use of soft templates and the controlled segregation of chemically modified graphene to liquid interfaces. These novel structures can be tuned for excellent conductivity; versatile mechanical response (elastic-brittle to elastomeric, reversible deformation, high energy absorption) and organic absorption capabilities (above 600 g per gram of material). The approach can be used to uncover the basic principles that will guide the design of practical devices that by combining unique mechanical and functional performance will generate new technological opportunities.

Plasma-Assisted Reduction of Graphene Oxide at Low Temperature and Atmospheric Pressure for Flexible Conductor Applications.

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.

Partially oxidized graphene as a precursor to graphene

Solution exfoliation of graphite holds promise for large-scale bulk synthesis of graphene. Non-covalent exfoliation is attractive because the electronic structure of graphene is preserved but the yield is low and the lateral dimensions of the sheets are small. Chemical exfoliation via formation of graphite oxide is a highly versatile and scalable route but the covalent functionalization of graphene with oxygen significantly alters the properties. Here, we report a new method for large-scale facile synthesis of micron-sized partially oxidized graphene (POG) sheets with dramatically improved electronic properties compared to other solution-phase exfoliated graphene. Due to low initial oxygen content (∼12%), POG requires only mild annealing (<300 °C) to achieve a sheet resistance of 28 kΩ sq−1 at the neutrality point, only a factor of ∼4 larger than the intrinsic sheet resistance of pristine graphene (∼6 kΩ sq−1) and substantially lower than graphene exfoliated by other methods. Such a partial oxidation approach opens up new promising routes to solution based high-performance, low temperature, transparent and conducting graphene-based flexible electronics.

Amorphous Molybdenum Sulfide on Graphene–Carbon Nanotube Hybrids as Highly Active Hydrogen Evolution Reaction Catalysts

In this study, we report on the deposition of amorphous molybdenum sulfide (MoSx, with x ≈ 3) on a high specific surface area conductive support of Graphene-Carbon Nanotube hybrids (GCNT) as the Hydrogen Evolution Reaction (HER) catalysts. We found that the high surface area GCNT electrode could support the deposition of MoSx at much higher loadings compared with simple porous carbon paper or flat graphite paper. The morphological study showed that MoSx was successfully deposited on and was in good contact with the GCNT support. Other physical characterization techniques suggested the amorphous nature of the deposited MoSx. With a typical catalyst loading of 3 mg cm(-2), an overpotential of 141 mV was required to obtain a current density of 10 mA cm(-2). A Tafel slope of 41 mV decade(-1) was demonstrated. Both measures placed the MoSx-deposited GCNT electrode among the best performing molybdenum sulfide-based HER catalysts reported to date. The electrode showed a good stability with only a 25 mV increase in overpotential required for a current density of 10 mA cm(-2), after undergoing 500 potential sweeps with vigorous bubbling present. The current density obtained at -0.5 V vs SHE (Standard Hydrogen Electrode potential) decreased less than 10% after the stability test. The deposition of MoSx on high specific surface area conductive electrodes demonstrated to be an efficient method to maximize the catalytic performance toward HER.