Optical Spectroscopy Investigation of the Structural and Electrical Evolution of Controllably Oxidized Graphene by a Solution Method
04 May 2012-Journal of Physical Chemistry C (American Chemical Society)-Vol. 116, Iss: 19, pp 10702-10707
TL;DR: In this paper, a precisely controlled chemical modification of exfoliated graphene on a substrate was achieved by solution-phase oxidation, which exhibited an energy band gap of 2 eV.
Abstract: A precisely controlled chemical modification of exfoliated graphene on a substrate was achieved by solution-phase oxidation. The structural and electrical evolution of graphene induced by oxygen-related defects was investigated using micro-Raman and photoluminescence spectroscopy. The sp2-hybrid carbon network in monolayer graphene was found to gradually decrease with increasing degree of oxidation. The size of the graphene quantum dots was finally reduced to about 1 nm, which exhibited an energy band gap of 2 eV. The double-layer graphene showed a symmetry breaking induced by the defects. The process of solution modification may provide a facile method to tailor the electrical properties of graphene on a chip for constructing carbon-based nanoelectronics.
Citations
More filters
TL;DR: In this article, the formation of different types of oxygen containing functional groups in GO and their influences on its structure were analyzed using X-ray diffraction (XRD), Fourier transform infra-red spectra, x-ray photoelectron spectra (XPS), zeta potential analysis and Raman spectroscopy.
1,428 citations
Cites background from "Optical Spectroscopy Investigation ..."
...[49] Wang S, Wang R, Liu X, Wang X, Zhang D, Guo Y, et al....
[...]
TL;DR: The ability to tune the selectivity of graphene through controlled generation of subnanometer pores addresses a significant challenge in the development of advanced nanoporous graphene membranes for nanofiltration, desalination, gas separation, and other applications.
Abstract: We report selective ionic transport through controlled, high-density, subnanometer diameter pores in macroscopic single-layer graphene membranes. Isolated, reactive defects were first introduced into the graphene lattice through ion bombardment and subsequently enlarged by oxidative etching into permeable pores with diameters of 0.40 ± 0.24 nm and densities exceeding 1012 cm–2, while retaining structural integrity of the graphene. Transport measurements across ion-irradiated graphene membranes subjected to in situ etching revealed that the created pores were cation-selective at short oxidation times, consistent with electrostatic repulsion from negatively charged functional groups terminating the pore edges. At longer oxidation times, the pores allowed transport of salt but prevented the transport of a larger organic molecule, indicative of steric size exclusion. The ability to tune the selectivity of graphene through controlled generation of subnanometer pores addresses a significant challenge in the dev...
706 citations
TL;DR: A well-defined graphene pattern is demonstrated by using ozone photolithography, in which the ozone-treated graphene electrodes are monolithic but separated by insulating GO regions, indicating the promising use of ozone treatment to achieve high-performance graphene-based optoelectronic devices.
Abstract: Tunable electrical and optical properties of graphene are vital to promote its use as film electrodes in a variety of devices. We developed an etching-free ozone treatment method to continuously tune the electrical resistance and optical transmittance of graphene films by simply varying the time and temperature of graphene exposure to ozone. Initially, ozone exposure dramatically decreases the electrical resistance of graphene films by p-doping, but this is followed by increases in the resistance and optical transmittance as a result of surface oxidation. The rate of resistance increase can be significantly increased by raising the treatment temperature. The ozone-oxidized graphene is not removed but is gradually transformed to graphene oxide (GO). On the basis of such effects of ozone treatment, we demonstrate a well-defined graphene pattern by using ozone photolithography, in which the ozone-treated graphene electrodes are monolithic but separated by insulating GO regions. Such a monolithic graphene pat...
94 citations
TL;DR: By combining coarse-grained molecular dynamics and newly developed accurate models of GO, the driving forces that lead to the various morphologies are resolved and computational methods to design directed synthesis routes for diverse self-assemblies and applications are provided.
Abstract: Controlling the structure of graphene and graphene oxide (GO) phases is vitally important for any of its widespread intended applications: highly ordered arrangements of nanoparticles are needed for thin-film or membrane applications of GO, dispersed nanoparticles for composite materials, and 3D porous arrangements for hydrogels. By combining coarse-grained molecular dynamics and newly developed accurate models of GO, the driving forces that lead to the various morphologies are resolved. Two hydrophilic polymers, poly(ethylene glycol) (PEG) and poly(vinyl alcohol) (PVA), are used to illustrate the thermodynamically stable morphologies of GO and relevant dispersion mechanisms. GO self-assembly can be controlled by changing the degree of oxidation, varying from fully aggregated over graphitic domains to intercalated assemblies with polymer bilayers between sheets. The long-term stability of a dispersion is extremely important for many commercial applications of GO composites. For any degree of oxidation, GO does not disperse in PVA as a thermodynamic equilibrium product, whereas in PEG dispersions are only thermodynamically stable for highly oxidized GO. These findings-validated against the extensive literature on GO systems in organic solvents-furnish quantitative explanations for the empirically unpredictable aggregation characteristics of GO and provide computational methods to design directed synthesis routes for diverse self-assemblies and applications.
81 citations
TL;DR: An electrochemical approach involving phenyl-diazonium salts is used to systematically probe electronic modification in MLG and BLG with increasing functionalization for the first time, obtaining the highest conversion values to date.
Abstract: A central question in graphene chemistry is to what extent chemical modification can control an electronically accessible band gap in monolayer and bilayer graphene (MLG and BLG). Density functional theory predicts gaps in covalently functionalized graphene as high as 2 eV, while this approach neglects the fact that lattice symmetry breaking occurs over only a prescribed radius of nanometer dimension, which we label the S-region. Therefore, high chemical conversion is central to observing this band gap in transport. We use an electrochemical approach involving phenyl-diazonium salts to systematically probe electronic modification in MLG and BLG with increasing functionalization for the first time, obtaining the highest conversion values to date. We find that both MLG and BLG retain their relatively high conductivity after functionalization even at high conversion, as mobility losses are offset by increases in carrier concentration. For MLG, we find that band gap opening as measured during transport is lin...
67 citations
References
More filters
[...]
TL;DR: Owing to its unusual electronic spectrum, graphene has led to the emergence of a new paradigm of 'relativistic' condensed-matter physics, where quantum relativistic phenomena can now be mimicked and tested in table-top experiments.
Abstract: Graphene is a rapidly rising star on the horizon of materials science and condensed-matter physics. This strictly two-dimensional material exhibits exceptionally high crystal and electronic quality, and, despite its short history, has already revealed a cornucopia of new physics and potential applications, which are briefly discussed here. Whereas one can be certain of the realness of applications only when commercial products appear, graphene no longer requires any further proof of its importance in terms of fundamental physics. Owing to its unusual electronic spectrum, graphene has led to the emergence of a new paradigm of 'relativistic' condensed-matter physics, where quantum relativistic phenomena, some of which are unobservable in high-energy physics, can now be mimicked and tested in table-top experiments. More generally, graphene represents a conceptually new class of materials that are only one atom thick, and, on this basis, offers new inroads into low-dimensional physics that has never ceased to surprise and continues to provide a fertile ground for applications.
35,293 citations
26,456 citations
TL;DR: This work shows that graphene's electronic structure is captured in its Raman spectrum that clearly evolves with the number of layers, and allows unambiguous, high-throughput, nondestructive identification of graphene layers, which is critically lacking in this emerging research area.
Abstract: Graphene is the two-dimensional building block for carbon allotropes of every other dimensionality We show that its electronic structure is captured in its Raman spectrum that clearly evolves with the number of layers The D peak second order changes in shape, width, and position for an increasing number of layers, reflecting the change in the electron bands via a double resonant Raman process The G peak slightly down-shifts This allows unambiguous, high-throughput, nondestructive identification of graphene layers, which is critically lacking in this emerging research area
13,474 citations
TL;DR: In this paper, a model and theoretical understanding of the Raman spectra in disordered and amorphous carbon is given, and the nature of the G and D vibration modes in graphite is analyzed in terms of the resonant excitation of \ensuremath{\pi} states and the long-range polarizability of the long range bonding.
Abstract: The model and theoretical understanding of the Raman spectra in disordered and amorphous carbon are given. The nature of the G and D vibration modes in graphite is analyzed in terms of the resonant excitation of \ensuremath{\pi} states and the long-range polarizability of \ensuremath{\pi} bonding. Visible Raman data on disordered, amorphous, and diamondlike carbon are classified in a three-stage model to show the factors that control the position, intensity, and widths of the G and D peaks. It is shown that the visible Raman spectra depend formally on the configuration of the ${\mathrm{sp}}^{2}$ sites in ${\mathrm{sp}}^{2}$-bonded clusters. In cases where the ${\mathrm{sp}}^{2}$ clustering is controlled by the ${\mathrm{sp}}^{3}$ fraction, such as in as-deposited tetrahedral amorphous carbon (ta-C) or hydrogenated amorphous carbon (a-C:H) films, the visible Raman parameters can be used to derive the ${\mathrm{sp}}^{3}$ fraction.
12,593 citations
TL;DR: An improved method for the preparation of graphene oxide (GO) is described, finding that excluding the NaNO(3), increasing the amount of KMnO(4), and performing the reaction in a 9:1 mixture of H(2)SO(4)/H(3)PO(4) improves the efficiency of the oxidation process.
Abstract: An improved method for the preparation of graphene oxide (GO) is described. Currently, Hummers’ method (KMnO4, NaNO3, H2SO4) is the most common method used for preparing graphene oxide. We have found that excluding the NaNO3, increasing the amount of KMnO4, and performing the reaction in a 9:1 mixture of H2SO4/H3PO4 improves the efficiency of the oxidation process. This improved method provides a greater amount of hydrophilic oxidized graphene material as compared to Hummers’ method or Hummers’ method with additional KMnO4. Moreover, even though the GO produced by our method is more oxidized than that prepared by Hummers’ method, when both are reduced in the same chamber with hydrazine, chemically converted graphene (CCG) produced from this new method is equivalent in its electrical conductivity. In contrast to Hummers’ method, the new method does not generate toxic gas and the temperature is easily controlled. This improved synthesis of GO may be important for large-scale production of GO as well as the ...
9,812 citations