Layer-dependent nanoscale electrical properties of graphene studied by conductive scanning probe microscopy

The nanoscale electrical properties of single-layer graphene (SLG), bilayer graphene (BLG) and multilayer graphene (MLG) are studied by scanning capacitance microscopy (SCM) and electrostatic force microscopy (EFM). The quantum capacitance of graphene deduced from SCM results is found to increase with the layer number (n) at the sample bias of 0 V but decreases with n at -3 V. Furthermore, the quantum capacitance increases very rapidly with the gate voltage for SLG, but this increase is much slowed down when n becomes greater. On the other hand, the magnitude of the EFM phase shift with respect to the SiO₂ substrate increases with n at the sample bias of +2 V but decreases with n at -2 V. The difference in both quantum capacitance and EFM phase shift is significant between SLG and BLG but becomes much weaker between MLGs with a different n. The layer-dependent quantum capacitance behaviors of graphene could be attributed to their layer-dependent electronic structure as well as the layer-varied dependence on gate voltage, while the layer-dependent EFM phase shift is caused by not only the layer-dependent surface potential but also the layer-dependent capacitance derivation.     

Fano resonance in Raman scattering of graphene

Fano resonances and their strong doping dependence are observed in Raman scattering of single-layer graphene (SLG). As the Fermi level is varied by a back-gate bias, the Raman G band of SLG exhibits an asymmetric line shape near the charge neutrality point as a manifestation of a Fano resonance, whereas the line shape is symmetric when the graphene sample is electron or hole doped. However, the G band of bilayer graphene (BLG) does not exhibit any Fano resonance regardless of doping. The observed Fano resonance can be interpreted as interferences between the phonon and excitonic many-body spectra in SLG. The absence of a Fano resonance in the Raman G band of BLG can be explained in the same framework since excitonic interactions are not expected in BLG.     

Polarization dependence of double resonant Raman scattering band in bilayer graphene

The polarization dependence of the double resonant Raman scattering (2D) band in bilayer graphene (BLG) is studied as a function of the excitation laser energy. It has been known that the complex shape of the 2D band of BLG can be decomposed into four Lorentzian peaks with different Raman frequency shifts attributable to four individual scattering paths in the energy–momentum space. From our polarization dependence study, however, we reveal that each of the four different peaks is actually doubly degenerate in its scattering channels, i.e., two different scattering paths with similar Raman frequency shifts for each peak. We find theoretically that one of these two paths, ignored for a long time, has a small contribution to their scattering intensities but are critical in understanding their polarization dependences. Because of this, the maximum-to-minimum intensity ratios of the four peaks show a strong dependence on the excitation energy, unlike the case of single-layer graphene (SLG). Our findings thus reveal another interesting aspect of electron–phonon interactions in graphitic systems.     

A powerful tool for graphene functionalization: Benzophenone mediated UV-grafting

The surface modification of graphene is of fundamental importance when working on the fabrication of high performing polymeric nanocomposite exploiting the exciting properties of this carbon-based material. Using low cost graphene oxide as starting material, trading on its richness of –OH groups and its ability to be reduced under UV light, a facile two-step UV-based process for the reduction to graphene and the simultaneous covalent grafting of initiating moieties at its surface is here proposed. This procedure enables the subsequent photo-grafting of a great variety of monomers for graphene surface functionalization.Chemical, structural and electrical analysis of the functionalized graphene sheets demonstrated the reduction of the starting oxide and the grafting of the initiator and of the acrylic monomers used in this study. This procedure opens the route for a low cost production of grafted graphene that can be easily dispersed in organic matrices, in order to produce highly performing functional materials.     

Effects of functional groups on the mechanical and wrinkling properties of graphene sheets

The effects of the degree of functionalization, molecular structure and molecular weight of functional groups on the Young’s modulus of graphene sheets were investigated through molecular dynamics and molecular mechanics simulations. The dependence of shear modulus, strength and critical wrinkling strain of graphene sheets on the chemical functionalization was also examined. It is found that Young’s modulus depends greatly on the degree of functionalization and molecular structure of the functional groups, while the molecular weight of the functional groups plays a minor role in determining Young’s modulus. The chemical functionalization also reduces the shear modulus and critical wrinkling strain. The binding energy between the functional groups and the graphene sheets is mainly responsible for these findings.     

Covalently linked biocompatible graphene/polycaprolactone composites for tissue engineering

Two synthesis routes to graphene/polycaprolactone composites are introduced and the properties of the resulting composites compared. In the first method, mixtures are produced using solution processing of polycaprolactone and well dispersed, chemically reduced graphene oxide and in the second, an esterification reaction covalently links polycaprolactone chains to free carboxyl groups on the graphene sheets. This is achieved through the use of a stable anhydrous dimethylformamide dispersion of graphene that has been highly chemically reduced resulting in mostly peripheral ester linkages. The resulting covalently linked composites exhibit far better homogeneity and as a result, both Young’s modulus and tensile strength more than double and electrical conductivities increase by ≈ 14 orders of magnitude over the pristine polymer at less than 10% graphene content. In vitro cytotoxicity testing of the materials showed good biocompatibility resulting in promising materials for use as conducting substrates for the electrically stimulated growth of cells.     

Sonochemical synthesis and characterization of amine‐modified graphene/conducting polymer nanocomposites

The objective of this work is to modify graphene and study the effect of modification of graphene in thermal and electrical properties of graphene/polypyrrole and graphene/polyaniline nanocomposites. The amine functionalization of graphene was confirmed by Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. The nanocomposites were prepared by insitu oxidative polymerization method using ammonium persulfate as oxidant. Field emission scanning electron microscopy and high‐resolution transmission electron microscopy were used to study the morphology of the nanocomposites which indicates toward the better dispersion of modified graphene within the polymer matrices as compared to unmodified composites. The modification of graphene played an important role in the noticeable improvements in electrical conductivity of the prepared composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Functionalization of carbon nanomaterials for advanced polymer nanocomposites: A comparison study between CNT and graphene

The allotropes of carbon nanomaterials (carbon nanotubes, graphene) are the most unique and promising substances of the last decade. Due to their nanoscale diameter and high aspect ratio, a small amount of these nanomaterials can produce a dramatic improvement in the properties of their composite materials. Although carbon nanotubes (CNTs) and graphene exhibit numerous extraordinary properties, their reported commercialization is still limited due to their bundle and layer forming behavior. Functionalization of CNTs and graphene is essential for achieving their outstanding mechanical, electrical and biological functions and enhancing their dispersion in polymer matrices. A considerable portion of the recent publications on CNTs and graphene have focused on enhancing their dispersion and solubilization using covalent and non-covalent functionalization methods. This review article collectively introduces a variety of reactions (e.g. click chemistry, radical polymerization, electrochemical polymerization, dendritic polymers, block copolymers, etc.) for functionalization of CNTs and graphene and fabrication of their polymer nanocomposites. A critical comparison between CNTs and graphene has focused on the significance of different functionalization approaches on their composite properties. In particular, the mechanical, electrical, and thermal behaviors of functionalized nanomaterials as well as their importance in the preparation of advanced hybrid materials for structures, solar cells, fuel cells, supercapacitors, drug delivery, etc. have been discussed thoroughly.     

Controlled oxidative functionalization of monolayer graphene by water-vapor plasma etching

We report studies on the controlled step-by-step oxidative functionalization of monolayer graphene by chemically reactive water-vapor plasma dry etching. The use of a porous mask on top of the graphene sheets as a filter is essential to reduce the density of free radicals and weaken the sputtering effect. Micro-Raman spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy showed that the oxidation occurred in a mild and controllable way, and that a wide variety of oxygen-containing functional groups can be evenly and incrementally incorporated onto the carbon lattice. By monitoring the electrical property changes in the graphene at different levels of oxidation, we observed a transformation of the electrical conduction process from continuum percolation to variable range hopping and/or electric-field-driven tunneling, due to the progressive increase of sp³-based basal plane distortion that disrupts the transport of carriers delocalized in the sp² carbon network.     

Functionalization of surfactant wrapped graphene nanosheets with alkylazides for enhanced dispersibility

A facile and simple approach for the covalent functionalization of surfactant wrapped graphene sheets is described. The approach involves functionalization of dispersible graphene sheets with various alkylazides and 11-azidoundecanoic acid proved the best azide for enhanced dispersibility. The functionalization was confirmed by infrared spectroscopy and scanning tunneling microscopy. The free carboxylic acid groups can bind to gold nanoparticles, which were introduced as markers for the reactive sites. The interaction between gold nanoparticles and the graphene sheets was followed by UV-vis spectroscopy. The gold nanoparticle-graphene composite was characterized by transmission electron microscopy and atomic force microscopy, demonstrating the uniform distribution of gold nanoparticles all over the surface. Our results open the possibility to control the functionalization on graphene in the construction of composite nanomaterials.     

Polymer-stabilized graphene dispersions at high concentrations in organic solvents for composite production

We demonstrate a simple and effective technique for dispersing pristine (unfunctionalized) graphene at high concentrations in a wide range of organic solvents by use of a stabilizing polymer (polyvinylpyrrolidone, PVP). These polymer-stabilized graphene dispersions are shown to be highly stable and readily redispersible even after freeze-drying. This technique yields significantly higher graphene concentrations compared to prior studies. An excellent increase in the thermal conductivity of the fluid by the addition of pristine graphene is also demonstrated. These well-dispersed pristine graphene sheets were then used as a strong and conductive nano-filler for polymer composites. Graphene/PVP composites were produced by the bulk polymerization of N-vinylpyrrolidone loaded with dispersed graphene, resulting in excellent load transfer and improved mechanical and electrical properties.     

Tunable transport characteristics of p-type graphene field-effect transistors by poly(ethylene imine) overlayer

Tunable electrical transport properties of graphene field-effect transistors (GFETs) are achieved by spin-coating a poly(ethylene imine) (PEI) layer on graphene surface. The initially p-doped graphene recovers the ambipolar characteristics with the PEI overlayer. When increasing the PEI concentration in a methanol solvent, a systematic evolution of the transport properties of GFETs is observed. The carrier mobility of graphene is greatly improved by several tens of times and the hole/electron conductivity saturation is shown. The voltage of the neutrality point V_Dirac gets closer to 0 V and the plateau width around the neutrality point ΔV_Dirac becomes much smaller. It is proposed that the long-range Coulomb scattering in graphene is suppressed due to the screening effect of PEI and the performances of GFETs are consequently improved. The hysteretic behaviors of the transfer characteristic curves of GFETs are also influenced by the PEI coating. The gradual reversion of the hysteresis direction is observed when increasing the concentration of PEI, which is probably due to the two competing mechanisms between the charge trapping at the graphene/SiO₂ interface and the capacitive coupling of graphene and the PEI overlayer.     

Low percolation threshold of graphene/polymer composites prepared by solvothermal reduction of graphene oxide in the polymer solution

Graphene/polyvinylidene fluoride (PVDF) composites were prepared using in-situ solvothermal reduction of graphene oxide in the PVDF solution. The electrical conductivity of the composites was greatly improved by doping with graphene sheets. The percolation threshold of such composite was determined to be 0.31 vol.%, being much smaller than that of the composites prepared via blending reduced graphene sheets with polymer matrix. This is attributed to the large aspect ratio of the SRG sheets and their uniform dispersion in the polymer matrix. The dielectric constant of PVDF showed a marked increase from 7 to about 105 with only 0.5 vol.% loading of SRG content. Like the other conductor-insulator systems, the AC conductivity of the system also obeyed the universal dynamic response. In addition, the SRG/PVDF composite shows a much stronger nonlinear conduction behavior than carbon nanotube/nanofiber based polymer composite, owing to intense Zener tunneling between the SRG sheets. The strong electrical nonlinearity provides further support for a homogeneous dispersion of SRG sheets in the polymer matrix.     

Microwave-assisted synthesis of highly water-soluble graphene towards electrical DNA sensor

Graphene sheets have the potential for practical applications in electrochemical devices, but their development has been impeded by critical problems with aggregation of graphene sheets. Here, we demonstrated a facile and bottom-up approach for fabrication of DNA sensor device using water-soluble sulfonated reduced graphene oxide (SRGO) sheets via microwave-assisted sulfonation (MAS), showing enhanced sensitivity, reliability, and low detection limit. Key to achieving these performances is the fabrication of the SRGOs, where the MAS method enabled SRGOs to be highly dispersed in water (10 mg mL(-1)) due to the acidic sulfonated groups generated within 3 min of the functionalization reaction. The water-soluble SRGO-DNA (SRGOD) hybrids prepared by electrostatic interactions between a flat single layer of graphene sheets and DNAs are suitable for fabrication of electrical DNA sensor devices because of the unique electrical characteristics of SRGODs. The high sensing performance of SRGOD sensors was demonstrated with detection of DNA hybridization using complementary DNAs, single base mismatched DNAs, and noncomplementary DNAs, with results showing higher sensitivity and lower detection limit than those of reduced graphene oxide-based DNA sensors. Simple and easy fabrication of DNA sensor devices using SRGODs is expected to provide an effective way for electrical detection of DNA hybridization using miniature sensors without the labor-intensive labeling of the sensor and complex measurement equipment.     

Research progress of non-covalent functionalization and applications of graphene

为了扩展石墨烯的应用范围,克服石墨烯在溶液中难于溶解和难以分散等缺陷,石墨烯的表面功能化处理势在必行。而非共价键功能化由于对石墨烯结构的非破坏性可以更好地保持发挥石墨烯本身的优异性能而备受研究者的重视。本文重点综述了近年来石墨烯在非共价键功能化研究方面的进展,包括π-π相互作用、表面活性剂与石墨烯之间的疏水作用和氢键作用,并对非共价键功能化石墨烯在电极材料、电催化、场效应晶体管和透明导体方面的应用研究进行了简要的介绍。最后对石墨烯在非共价键功能化方面的发展前景进行了展望和预测。     

Furfuryl alcohol functionalized graphene nanosheets for synthesis of high carbon yield novolak composites

Graphene oxide and furfuryl alcohol modified graphene nanosheets (G‐FA) were used to prepare graphene/novolak composites. Effect of graphene compatibilization on the properties of the composites especially carbon yield value is evaluated. Both types of graphene nanosheets were dispersed uniquely in the novolak matrix as proved by X‐ray diffraction analysis. However, modification of graphene sheets by furfuryl alcohol results in more improved dispersions. Thermogravimetric analysis confirms the elevated thermal stability of the nanocomposites in comparison with the neat novolak. In addition, G‐FA containing composites have higher carbon yield values. A shift in the wave number of characteristic bonds of graphene after oxidation and modification with furfuryl alcohol, O? H, C?O, and C? O bonds, are seen in the Fourier transform infrared spectroscopy spectra. Raman results and scanning electron microscopy images show that graphene nanosheets reduced in size and wrinkled by oxidation and functionalization. Transmission electron microscopy image of the composite with 0.2 wt % of G‐FA reveals the presence of nanosheets with curvature. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40273.     

Thinning and functionalization of few-layer graphene sheets by CF4 plasma treatment

ABSTRACT: Structural changes of few-layer graphene sheets induced by CF4 plasma treatment are studied by optical microscopy and Raman spectroscopy, together with theoretical simulation. Experimental results suggest a thickness reduction of few-layer graphene sheets subjected to prolonged CF4 plasma treatment while plasma treatment with short time only leads to fluorine functionalization on the surface layer by formation of covalent bonds. Raman spectra reveal an increase in disorder by physical disruption of the graphene lattice as well as functionalization during the plasma treatment. The F/CF3 adsorption and the lattice distortion produced are proved by theoretical simulation using density functional theory, which also predicts p-type doping and Dirac cone splitting in CF4 plasma-treated graphene sheets that may have potential in future graphene-based micro/nanodevices. PACS: 81.05.ue; 73.22.Pr; 52.40.Hf.     

Enhancement of electrical and thermal conductivity of Su-8 photocrosslinked coatings containing graphene

Graphene platelets were dispersed into photocurable SU-8 resin. A strong increase of the T_g value as a function of the graphene content was observed and attributed to a mobility hindering effect on the polymeric chains caused by the graphene filler. A significant increase of electrical conductivity is achieved for composites containing functionalized graphene sheets (FGS) between 3 and 4 wt%. The thermal diffusivity of the polymer was observed to increase as a function of filler content in the nanocomposites confirming the conducting nature of the polymeric coating with incorporation of graphene.     

Nanoscale charge distribution and energy band modification in defect-patterned graphene

Defects were introduced precisely to exfoliated graphene (G) sheets on a SiO(2)/n(+) Si substrate to modulate the local energy band structure and the electron pathway using solution-phase oxidation followed by thermal reduction. The resulting nanoscale charge distribution and band gap modification were investigated by electrostatic force microscopy and spectroscopy. A transition phase with coexisting submicron-sized metallic and insulating regions in the moderately oxidized monolayer graphene were visualized and measured directly. It was determined that the delocalization of electrons/holes in a graphene "island" is confined by the surrounding defective C-O matrix, which acts as an energy barrier for mobile charge carriers. In contrast to the irreversible structural variations caused by the oxidation process, the electrical properties of graphene can be restored by annealing. The defect-patterned graphene and graphene oxide heterojunctions were further characterized by electrical transport measurement.     

Epoxy/p‐phenylenediamine functionalized graphene oxide composites and evaluation of their fracture toughness and tensile properties

In an attempt to enhance the mechanical properties of epoxy/graphene‐based composites, the interface was engineered through the functionalization of graphene oxide (GO) sheets with p‐phenylenediamine; this resulted in p‐phenylenediamine functionalized graphene oxide (GO–pPDA). The morphology and chemical structure of the GO–pPDA sheets were studied by spectroscopic methods, thermal analysis, X‐ray diffraction, and transmission electron microscopy. The characterization results show the successful covalent functionalization of GO sheets through the formation of amide bonds. In addition, p‐phenylenediamine were polymerized on graphene sheets to form crystalline nanospheres; this resulted in a GO/poly(p‐phenylenediamine) hybrid. The mechanical properties of the epoxy/GO–pPDA composite were assessed. Although the Young's modulus showed improvement, more significant improvements were observed in the strength, fracture strain, and plane‐strain fracture toughness. These improvements were attributed to the unique microstructure and strong interface between GO–pPDA and the epoxy matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43821.