Enhancement of the electrical properties of graphene grown by chemical vapor deposition via controlling the effects of polymer residue.

Residual polymer (here, poly(methyl methacrylate), PMMA) left on graphene from transfer from metals or device fabrication processes affects its electrical and thermal properties. We have found that the amount of polymer residue left after the transfer of chemical vapor deposited (CVD) graphene varies depending on the initial concentration of the polymer solution, and this residue influences the electrical performance of graphene field-effect transistors fabricated on SiO2/Si. A PMMA solution with lower concentration gave less residue after exposure to acetone, resulting in less p-type doping in graphene and higher charge carrier mobility. The electrical properties of the weakly p-doped graphene could be further enhanced by exposure to formamide with the Dirac point at nearly zero gate voltage and a more than 50% increase of the room-temperature charge carrier mobility in air. This can be attributed to electron donation to graphene by the -NH2 functional group in formamide that is absorbed in the polymer residue. This work provides a route to enhancing the electrical properties of CVD-grown graphene even when it has a thin polymer coating.

Preparation and characterization of graphene oxide paper.

Free-standing paper-like or foil-like materials are an integral part of our technological society. Their uses include protective layers, chemical filters, components of electrical batteries or supercapacitors, adhesive layers, electronic or optoelectronic components, and molecular storage. Inorganic 'paper-like' materials based on nanoscale components such as exfoliated vermiculite or mica platelets have been intensively studied and commercialized as protective coatings, high-temperature binders, dielectric barriers and gas-impermeable membranes. Carbon-based flexible graphite foils composed of stacked platelets of expanded graphite have long been used in packing and gasketing applications because of their chemical resistivity against most media, superior sealability over a wide temperature range, and impermeability to fluids. The discovery of carbon nanotubes brought about bucky paper, which displays excellent mechanical and electrical properties that make it potentially suitable for fuel cell and structural composite applications. Here we report the preparation and characterization of graphene oxide paper, a free-standing carbon-based membrane material made by flow-directed assembly of individual graphene oxide sheets. This new material outperforms many other paper-like materials in stiffness and strength. Its combination of macroscopic flexibility and stiffness is a result of a unique interlocking-tile arrangement of the nanoscale graphene oxide sheets.

Tuning the doping type and level of graphene with different gold configurations.

Au nanoparticles and films are deposited onto clean graphene surfaces to study the doping effect of different Au configurations. Micro-Raman spectra show that both the doping type and level of graphene can be tuned by fine control of the Au deposition. The morphological structures of Au on graphene are imaged by transmission electron microscopy, which indicate a size-dependent electrical characteristic: isolated Au nanoparticles produce n-type doping of graphene, while continuous Au films produce p-type doping. Accordingly, graphene field-effect transistors are fabricated, with the in situ measurements suggesting the tunable conductivity type and level by contacting with different Au configurations. For interpreting the experimental observations, the first-principles approach is used to simulate the interaction within graphene-Au systems. The results suggest that, different doping properties of Au-graphene systems are induced by the chemical interactions between graphene and the different Au configurations (isolated nanoparticle and continuous film).

Graphene-based composite materials.

Graphene sheets--one-atom-thick two-dimensional layers of sp2-bonded carbon--are predicted to have a range of unusual properties. Their thermal conductivity and mechanical stiffness may rival the remarkable in-plane values for graphite (approximately 3,000 W m(-1) K(-1) and 1,060 GPa, respectively); their fracture strength should be comparable to that of carbon nanotubes for similar types of defects; and recent studies have shown that individual graphene sheets have extraordinary electronic transport properties. One possible route to harnessing these properties for applications would be to incorporate graphene sheets in a composite material. The manufacturing of such composites requires not only that graphene sheets be produced on a sufficient scale but that they also be incorporated, and homogeneously distributed, into various matrices. Graphite, inexpensive and available in large quantity, unfortunately does not readily exfoliate to yield individual graphene sheets. Here we present a general approach for the preparation of graphene-polymer composites via complete exfoliation of graphite and molecular-level dispersion of individual, chemically modified graphene sheets within polymer hosts. A polystyrene-graphene composite formed by this route exhibits a percolation threshold of approximately 0.1 volume per cent for room-temperature electrical conductivity, the lowest reported value for any carbon-based composite except for those involving carbon nanotubes; at only 1 volume per cent, this composite has a conductivity of approximately 0.1 S m(-1), sufficient for many electrical applications. Our bottom-up chemical approach of tuning the graphene sheet properties provides a path to a broad new class of graphene-based materials and their use in a variety of applications.

Synthesis and characterization of large-area graphene and graphite films on commercial Cu-Ni alloy foils.

Controlling the thickness and uniformity during growth of multilayer graphene is an important goal. Here we report the synthesis of large-area monolayer and multilayer, particularly bilayer, graphene films on Cu-Ni alloy foils by chemical vapor deposition with methane and hydrogen gas as precursors. The dependence of the initial stages of graphene growth rate on the substrate grain orientation was observed for the first time by electron backscattered diffraction and scanning electron microscopy. The thickness and quality of the graphene and graphite films obtained on such Cu-Ni alloy foils could be controlled by varying the deposition temperature and cooling rate and were studied by optical microscopy, scanning electron microscopy, atomic force microscopy, and micro-Raman imaging spectroscopy. The optical and electrical properties of the graphene and graphite films were studied as a function of thickness.

Polymer Brushes via Controlled, Surface-Initiated Atom Transfer Radical Polymerization (ATRP) from Graphene Oxide.

A method for growing polymers directly from the surface of graphene oxide is demonstrated. The technique involves the covalent attachment of an initiator followed by the polymerization of styrene, methyl methacrylate, or butyl acrylate using atom transfer radical polymerization (ATRP). The resulting materials were characterized using a range of techniques and were found to significantly improve the solubility properties of graphene oxide. The surface-grown polymers were saponified from the surface and also characterized. Based on these results, the ATRP reactions were determined to proceed in a controlled manner and were found to leave the structure of the graphene oxide largely intact.

Colloidal suspensions of highly reduced graphene oxide in a wide variety of organic solvents.

We report that homogeneous colloidal suspensions of chemically modified graphene sheets were readily produced in a wide variety of organic solvent systems. Two different sets of solubility parameters are used to rationalize when stable colloidal suspensions of graphene oxide sheets and, separately, of reduced graphene oxide sheets in a given solvent type are possible and when they are not. As an example of the utility of such colloidal suspensions, "paperlike" materials generated by very simple filtration of the reduced graphene oxide sheets had electrical conductivity values as high as 16,000 S/m.

Transfer of large-area graphene films for high-performance transparent conductive electrodes.

Graphene, a two-dimensional monolayer of sp(2)-bonded carbon atoms, has been attracting great interest due to its unique transport properties. One of the promising applications of graphene is as a transparent conductive electrode owing to its high optical transmittance and conductivity. In this paper, we report on an improved transfer process of large-area graphene grown on Cu foils by chemical vapor deposition. The transferred graphene films have high electrical conductivity and high optical transmittance that make them suitable for transparent conductive electrode applications. The improved transfer processes will also be of great value for the fabrication of electronic devices such as field effect transistor and bilayer pseudospin field effect transistor devices.

Cracking of Polycrystalline Graphene on Copper under Tension.

Roll-to-roll manufacturing of graphene is attractive because of its compatibility with flexible substrates and its promise of high-speed production. Several prototype roll-to-roll systems have been demonstrated, which produce large-scale graphene on polymer films for transparent conducting film applications.1-4 In spite of such progress, the quality of graphene may be influenced by the tensile forces that are applied during roll-to-roll transfer. To address this issue, we conducted in situ tensile experiments on copper foil coated with graphene grown by chemical vapor deposition, which were carried out in a scanning electron microscope. Channel cracks, which were perpendicular to the loading direction, initiated over the entire graphene monolayer at applied tensile strain levels that were about twice the yield strain of the (annealed) copper. The spacing between the channel cracks decreased with increasing applied strain, and new graphene wrinkles that were parallel to the loading direction appeared. These morphological features were confirmed in more detail by atomic force microscopy. Raman spectroscopy was used to determine the strain in the graphene, which was related to the degradation of the graphene/copper interface. The experimental data allowed the fracture toughness of graphene and interfacial properties of the graphene/copper interface to be extracted based on classical channel crack and shear-lag models. This study not only deepens our understanding of the mechanical and interfacial behavior of graphene on copper but also provides guidelines for the design of roll-to-roll processes for the dry transfer of graphene.

Effects of thermally-induced changes of Cu grains on domain structure and electrical performance of CVD-grown graphene.

During the chemical vapor deposition (CVD) growth of graphene on Cu foils, evaporation of Cu and changes in the dimensions of Cu grains in directions both parallel and perpendicular to the foils are induced by thermal effects. Such changes in the Cu foil could subsequently change the shape and distribution of individual graphene domains grown on the foil surface, and thus influence the domain structure and electrical properties of the resulting graphene films. Here, a slower cooling rate is used after the CVD process, and the graphene films are found to have an improved electrical performance, which is considered to be associated with the Cu surface evaporation and grain structure changes in the Cu substrate.

Crystal structure evolution of individual graphene islands during CVD growth on copper foil.

Single-crystal percentage of graphene islands on Cu foil is associated with island sizes and shapes. In polycrystalline islands, certain grain boundary types are favored. There is no obvious relation between the number of lobes and grain orientations. An observed structure evolution and surface disorder of Cu grains can be possible factors for the formation of grain boundaries within graphene islands.

Selective surface functionalization at regions of high local curvature in graphene.

Monolayer graphene was deposited on a Si wafer substrate decorated with SiO(2) nanoparticles (NPs) and then exposed to aryl radicals that were generated in situ from their diazonium precursors. Using micro-Raman mapping, the aryl radicals were found to selectively react with the regions of graphene that covered the NPs. The enhanced chemical reactivity was attributed to the increased strain energy induced by the local mechanical deformation of the graphene.

Growth mechanism and controlled synthesis of AB-stacked bilayer graphene on Cu-Ni alloy foils.

Strongly coupled bilayer graphene (i.e., AB stacked) grows particularly well on commercial "90-10" Cu-Ni alloy foil. However, the mechanism of growth of bilayer graphene on Cu-Ni alloy foils had not been discovered. Carbon isotope labeling (sequential dosing of (12)CH(4) and (13)CH(4)) and Raman spectroscopic mapping were used to study the growth process. It was learned that the mechanism of graphene growth on Cu-Ni alloy is by precipitation at the surface from carbon dissolved in the bulk of the alloy foil that diffuses to the surface. The growth parameters were varied to investigate their effect on graphene coverage and isotopic composition. It was found that higher temperature, longer exposure time, higher rate of bulk diffusion for (12)C vs(13)C, and slower cooling rate all produced higher graphene coverage on this type of Cu-Ni alloy foil. The isotopic composition of the graphene layer(s) could also be modified by adjusting the cooling rate. In addition, large-area, AB-stacked bilayer graphene transferrable onto Si/SiO(2) substrates was controllably synthesized.

Oxidation resistance of graphene-coated Cu and Cu/Ni alloy.

The ability to protect refined metals from reactive environments is vital to many industrial and academic applications. Current solutions, however, typically introduce several negative effects, including increased thickness and changes in the metal physical properties. In this paper, we demonstrate for the first time the ability of graphene films grown by chemical vapor deposition to protect the surface of the metallic growth substrates of Cu and Cu/Ni alloy from air oxidation. In particular, graphene prevents the formation of any oxide on the protected metal surfaces, thus allowing pure metal surfaces only one atom away from reactive environments. SEM, Raman spectroscopy, and XPS studies show that the metal surface is well protected from oxidation even after heating at 200 °C in air for up to 4 h. Our work further shows that graphene provides effective resistance against hydrogen peroxide. This protection method offers significant advantages and can be used on any metal that catalyzes graphene growth.

Mechanical properties of monolayer graphene oxide.

Mechanical properties of ultrathin membranes consisting of one layer, two overlapped layers, and three overlapped layers of graphene oxide platelets were investigated by atomic force microscopy (AFM) imaging in contact mode. In order to evaluate both the elastic modulus and prestress of thin membranes, the AFM measurement was combined with the finite element method (FEM) in a new approach for evaluating the mechanics of ultrathin membranes. Monolayer graphene oxide was found to have a lower effective Young's modulus (207.6 ± 23.4 GPa when a thickness of 0.7 nm is used) as compared to the value reported for "pristine" graphene. The prestress (39.7-76.8 MPa) of the graphene oxide membranes obtained by solution-based deposition was found to be 1 order of magnitude lower than that obtained by others for mechanically cleaved graphene. The novel AFM imaging and FEM-based mapping methods presented here are of general utility for obtaining the elastic modulus and prestress of thin membranes.

Exfoliation of graphite oxide in propylene carbonate and thermal reduction of the resulting graphene oxide platelets.

Graphite oxide was exfoliated and dispersed in propylene carbonate (PC) by bath sonication. Heating the graphene oxide suspensions at 150 degrees C significantly reduced the graphene oxide platelets; paper samples comprising such reduced graphene oxide platelets had an electrical conductivity of 5230 S/m. By adding tetraethylammonium tetrafluoroborate (TEA BF(4)) to the reduced graphene oxide/PC slurry and making a two-cell ultracapacitor, specific capacitance values of about 120 F/g were obtained.

Tunable electrical conductivity of individual graphene oxide sheets reduced at "low" temperatures.

Step-by-step controllable thermal reduction of individual graphene oxide sheets, incorporated into multiterminal field effect devices, was carried out at low temperatures (125-240 degrees C) with simultaneous electrical measurements. Symmetric hysteresis-free ambipolar (electron- and hole-type) gate dependences were observed as soon as the first measurable resistance was reached. The conductivity of each of the fabricated devices depended on the level of reduction (was increased more than 10(6) times as reduction progressed), strength of the external electrical field, density of the transport current, and temperature.

Synthesis and solid-state NMR structural characterization of 13C-labeled graphite oxide.

The detailed chemical structure of graphite oxide (GO), a layered material prepared from graphite almost 150 years ago and a precursor to chemically modified graphenes, has not been previously resolved because of the pseudo-random chemical functionalization of each layer, as well as variations in exact composition. Carbon-13 (13C) solid-state nuclear magnetic resonance (SSNMR) spectra of GO for natural abundance 13C have poor signal-to-noise ratios. Approximately 100% 13C-labeled graphite was made and converted to 13C-labeled GO, and 13C SSNMR was used to reveal details of the chemical bonding network, including the chemical groups and their connections. Carbon-13-labeled graphite can be used to prepare chemically modified graphenes for 13C SSNMR analysis with enhanced sensitivity and for fundamental studies of 13C-labeled graphite and graphene.