Scanning tunneling microscope observations of non-AB stacking of graphene on Ni films

Microscopic features of graphene segregated on Ni films prior to chemical transfer—including atomic structures of monolayers and bilayers, Moiré patterns due to non-AB stacking, as well as wrinkles and ripples caused by strain effects-have been characterized in detail by high-resolution scanning tunneling microscopy (STM). We found that the stacking geometry of the bilayer graphene usually deviates from the traditional Bernal stacking (or so-called AB stacking), resulting in the formation of a variety of Moiré patterns. The relative rotations inside the bilayer were then qualitatively deduced from the relationship between Moiré patterns and carbon lattices. Moreover, we found that typical defects such as wrinkles and ripples tend to evolve around multi-step boundaries of Ni, thus reflecting strong perturbations from substrate corrugations. These investigations of the morphology and the mechanism of formation of wrinkles and ripples are fundamental topics in graphene research. This work is expected to contribute to the exploration of electronic and transport properties of wrinkles and ripples.      

Vapour-phase graphene epitaxy at low temperatures

We report an epitaxial growth of graphene, including homo- and hetero-epitaxy on graphite and SiC substrates, at a temperature as low as ∼540 °C. This vapour-phase epitaxial growth, carried out in a remote plasma-enhanced chemical vapor deposition (RPECVD) system using methane as the carbon source, can yield large-area high-quality graphene with the desired number of layers over the entire substrate surfaces following an AB-stacking layer-by-layer growth model. We also developed a facile transfer method to transfer a typical continuous one layer epitaxial graphene with second layer graphene islands on top of the first layer with the coverage of the second layer graphene islands being 20% (1.2 layer epitaxial graphene) from a SiC substrate onto SiO₂ and measured the resistivity, carrier density and mobility. Our work provides a new strategy toward the growth of graphene and broadens its prospects of application in future electronics.      

Sequential assembly of metal-free phthalocyanine on few-layer epitaxial graphene mediated by thickness-dependent surface potential

Due to strong interactions between epitaxial graphene and SiC(0001) substrates, the overlayer charge density induced by the interface charging effect is much more attenuated than that of exfoliated graphene on SiO₂. We report herein a quantitive detection of the charge properties of few-layer graphene by surface potential measurements using electrostatic force microscopy (EFM). A minor difference in surface potential is observed to mediate a sequential assembly of metal-free phthalocyanine (H₂Pc) on monolayer, bilayer and trilayer graphenes, as demonstrated by scanning tunneling microscopy (STM). In order to understand this, we further executed density functional theory (DFT) calculations which showed higher adsorption energies for Pc on thinner graphenes. In this case, we attribute the unique growth behavior of Pc to its variable adsorption energies on few-layer graphene, and in turn the layer charge variations from the viewpoint of energy minimizations. This work is expected to provide fundamental data useful for related nanodevice fabrications.      

One-step electrochemical approach to the synthesis of Graphene/MnO2 nanowall hybrids

We have demonstrated a one-step and effective electrochemical method to synthesize graphene/MnO₂ nanowall hybrids (GMHs). Graphene oxide (GO) was electrochemically reduced to graphene (GN), accompanied by the simultaneous formation of MnO₂ with a nanowall morphology via cathodic electrochemical deposition. The morphology and structure of the GMHs were systematically characterized by scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Raman spectroscopy. The resulting GMHs combine the advantages of GN and the nanowall array morphology of MnO₂ in providing a conductive network of amorphous nanocomposite, which shows good electrochemical capacitive behavior. This simple approach should find practical applications in the large-scale production of GMHs.      

Is graphene aromatic?

We analyze the chemical bonding in graphene using a fragmental approach, the adaptive natural density partitioning method, electron sharing indices, and nucleus-independent chemical shift indices. We prove that graphene is aromatic, but its aromaticity is different from the aromaticity in benzene, coronene, or circumcoronene. Aromaticity in graphene is local with two π-electrons delocalized over every hexagon ring. We believe that the chemical bonding picture developed for graphene will be helpful for understanding chemical bonding in defects such as point defects, single-, double-, and multiple vacancies, carbon adatoms, foreign adatoms, substitutional impurities, and new materials that are derivatives of graphene.      

Synthesis of large-area, few-layer graphene on iron foil by chemical vapor deposition

We demonstrate a simple and controllable way to synthesize large-area, few-layer graphene on iron substrates by an optimized chemical vapor deposition (CVD) method using a mixture of methane and hydrogen. Based on an analysis of the Fe-C phase diagram, a suitable procedure for the successful synthesis of graphene on Fe surfaces was designed. An appropriate temperature and cooling process were found to be very important in the synthesis of highly crystalline few-layer graphene. Graphene-based field-effect transistor (FET) devices were fabricated using the resulting few-layer graphene, and showed good quality with extracted mobilities of 300–1150 cm²/(V·s).      

Triboelectricity-assisted transfer of graphene for flexible optoelectronic applications

In this work, we developed a novel triboelectricity-assisted polymer-free method for the transfer of large-area chemical vapor deposited graphene films. With the assistance of electrostatic forces from friction-generated charges, graphene sheets were successfully transferred from copper foils to flexible polymer substrates. Characterization results confirmed the presence of high quality graphene with less defects and contaminations, compared to graphene transferred by conventional poly(methyl methacrylate)-mediated processes. In addition, the graphene samples possessed outstanding electrical transport capabilities and mechanical stability, when studied as electron transfer matrixes in graphene/ZnO hybrid flexible photodetectors. Our results showed a broad application potential for this transfer method in future flexible electronics and optoelectronics.

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An exchange intercalation mechanism for the formation of a two-dimensional Si structure underneath graphene

A two-dimensional (2D) Si film can form between a graphene overlayer and a Ru(0001) substrate through an intercalation process. At the graphene/2D-Si/Ru(0001) surface, the topmost graphene layer is decoupled from the Ru substrate and becomes quasi-freestanding. The interfacial Si layers show high stability due to the protection from the graphene cover. Surface science measurements indicate that the surface Si atoms can penetrate through the graphene lattice, and density functional theory calculations suggest a Si-C exchange mechanism facilitates the penetration of Si at mild temperatures. The new mechanism may be involved for other elements on graphene, if they can bond strongly with carbon. This finding opens a new route to form 2D interfacial layers between graphene and substrates.      

Chemical versus thermal folding of graphene edges

Using molecular dynamics (MD) simulations, we have investigated the kinetics of the graphene edge folding process. The lower limit of the energy barrier is found to be ∼380 meV/? (or about 800 meV per edge atom) and ∼50 meV/? (or about 120 meV per edge atom) for folding the edges of intrinsic clean single-layer graphene (SLG) and double-layer graphene (DLG), respectively. However, the edge folding barriers can be substantially reduced by imbalanced chemical adsorption, such as of H atoms, on the two sides of graphene along the edges. Our studies indicate that thermal folding is not feasible at room temperature (RT) for clean SLG and DLG edges and is feasible at high temperature only for DLG edges, whereas chemical folding (with adsorbates) of both SLG and DLG edges can be spontaneous at RT. These findings suggest that the folded edge structures of suspended graphene observed in some experiments are possibly due to the presence of adsorbates at the edges.      

Production of graphene nanospheres by annealing of graphene oxide in solution

We report a simple method to produce graphene nanospheres (GNSs) by annealing graphene oxide (GO) solution at high-temperature with the assistance of sparks induced by the microwave absorption of graphite flakes dispersed in the solution. The GNSs were formed by rolling up of the annealed GO, and the diameters were mostly in the range 300–700 nm. The GNS exhibited a hollow sphere structure surrounded by graphene walls with a basal spacing of 0.34 nm. Raman spectroscopy and X-ray photoelectron spectroscopy of the GNSs confirmed that the GO was efficiently reduced during the fabrication process. The resulting GNSs may open up new opportunities both for fundamental research and applications, and this method may be extended to the synthesis of other nanomaterials and the fabrication of related nanostructures.      

Graphene-based conducting inks for direct inkjet printing of flexible conductive patterns and their applications in electric circuits and chemical sensors

A series of inkjet printing processes have been studied using graphene-based inks. Under optimized conditions, using water-soluble single-layered graphene oxide (GO) and few-layered graphene oxide (FGO), various high image quality patterns could be printed on diverse flexible substrates, including paper, poly(ethylene terephthalate) (PET) and polyimide (PI), with a simple and low-cost inkjet printing technique. The graphene-based patterns printed on plastic substrates demonstrated a high electrical conductivity after thermal reduction, and more importantly, they retained the same conductivity over severe bending cycles. Accordingly, flexible electric circuits and a hydrogen peroxide chemical sensor were fabricated and showed excellent performances, demonstrating the applications of this simple and practical inkjet printing technique using graphene inks. The results show that graphene materials-which can be easily produced on a large scale and possess outstanding electronic properties-have great potential for the convenient fabrication of flexible and low-cost graphene-based electronic devices, by using a simple inkjet printing technique.      

Different growth behaviors of ambient pressure chemical vapor deposition graphene on Ni(111) and Ni films: A scanning tunneling microscopy study

Graphene growth on the same metal substrate with different crystal morphologies, such as single crystalline and polycrystalline, may involve different mechanisms. We deal with this issue by preparing graphene on single crystal Ni(111) and on ∼300 nm thick Ni films on SiO₂ using an ambient pressure chemical vapor deposition (APCVD) method, and analyze the different growth behaviors for different growth parameters by atomically-resolved scanning tunneling microscopy (STM) and complementary macroscopic analysis methods. Interestingly, we obtained monolayer graphene on Ni(111), and multilayer graphene on Ni films under the same growth conditions. Based on the experimental results, it is proposed that the graphene growth on Ni(111) is strongly templated by the Ni(111) lattice due to the strong Ni-C interactions, leading to monolayer graphene growth. Multilayer graphene flakes formed on polycrystalline Ni films are usually stacked with deviations from the Bernal stacking type and show small rotations among the carbon layers. Considering the different substrate features, the inevitable grain boundaries on polycrystalline Ni films are considered to serve as the growth fronts for bilayer and even multilayer graphene.      

Ionic liquid-assisted one-step hydrothermal synthesis of TiO2-reduced graphene oxide composites

We have demonstrated a facile and efficient strategy for the fabrication of soluble reduced graphene oxide sheets (RGO) and the preparation of titanium oxide (TiO₂) nanoparticle-RGO composites using a modified one-step hydrothermal method. It was found that graphene oxide could be easily reduced under solvothermal conditions with ascorbic acid as reductant, with concomitant growth of TiO₂ particles on the RGO surface. The TiO₂-RGO composite has been thoroughly characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Microscopy techniques (scanning electron microscopy, atomic force microscopy, and transmission electron microscopy) have been employed to probe the morphological characteristics as well as to investigate the exfoliation of RGO sheets. The TiO₂-RGO composite exhibited excellent photocatalysis of hydrogen evolution.      

Sodium citrate: A universal reducing agent for reduction / decoration of graphene oxide with au nanoparticles

A facile method is proposed for the synthesis of reduced graphene oxide nanosheets (RGONS) and Au nanoparticle-reduced graphene oxide nanosheet (Au-RGONS) hybrid materials, using graphene oxide (GO) as precursor and sodium citrate as reductant and stabilizer. The resulting RGONS and Au-RGONS hybrid materials were characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, atomic force microscopy, transmission electron microscopy, and X-ray diffraction. It was found that the RGONS and Au-RGONS hybrid materials formed stable colloidal dispersions through hydrogen bonds between the residual oxygen-containing functionalities on the surface of RGONS and the hydroxyl/carboxyl groups of sodium citrate. The electrochemical responses of RGONS and Au-RGONS hybrid material-modified glassy carbon electrodes (GCE) to three kinds of biomolecules were investigated, and all of them showed a remarkable increase in electrochemical performance relative to a bare GCE.      

A facile tool for the characterization of two-dimensional materials grown by chemical vapor deposition

The metrology of two-dimensional (2D) materials such as graphene, boron nitride or molybdenum disulfide grown by chemical vapor deposition (CVD) is critical for the optimization of their synthesis. We demonstrate the use of film-induced frustrated etching (FIFE) as a facile, scalable method to reveal and quantify structural defects in continuous thin sheets. The sensitivity of the analysis technique to intentionally induced lattice defects in graphene compares favorably to the sensitivity of Raman spectroscopy. A strong correlation between the measured defectiveness and the maximum carrier mobility in graphene emphasizes the importance of the technique for growth optimization. Due to its ease and widespread availability, we anticipate that FIFE will find wide application in the characterization of CVD-synthesized 2D materials.      

Assessment of high-frequency performance limits of graphene field-effect transistors

High frequency performance limits of graphene field-effect transistors (FETs) down to a channel length of 20 nm have been examined by using self-consistent quantum simulations. The results indicate that although Klein band-to-band tunneling is significant for sub-100 nm graphene FETs, it is possible to achieve a good transconductance and ballistic on-off ratio larger than 3 even at a channel length of 20 nm. At a channel length of 20 nm, the intrinsic cut-off frequency remains at a few THz for various gate insulator thickness values, but a thin gate insulator is necessary for a good transconductance and smaller degradation of cut-off frequency in the presence of parasitic capacitance. The intrinsic cut-off frequency is close to the LC characteristic frequency set by graphene kinetic inductance (L) and quantum capacitance (C), which is about 100 GHz·μm divided by the gate length.      

One-dimensional ZnO nanostructures: Solution growth and functional properties

One-dimensional (1D) ZnO nanostructures have been studied intensively and extensively over the last decade not only for their remarkable chemical and physical properties, but also for their current and future diverse technological applications. This article gives a comprehensive overview of the progress that has been made within the context of 1D ZnO nanostructures synthesized via wet chemical methods. We will cover the synthetic methodologies and corresponding growth mechanisms, different structures, doping and alloying, position-controlled growth on substrates, and finally, their functional properties as catalysts, hydrophobic surfaces, sensors, and in nanoelectronic, optical, optoelectronic, and energy harvesting devices.      

Morphology-controlled fabrication of sulfonated graphene/polyaniline nanocomposites by liquid/liquid interfacial polymerization and investigation of their electrochemical properties

A novel morphology-controlled strategy has been developed to fabricate sulfonated graphene/polyaniline (SGEP) nanocomposites by liquid/liquid interfacial polymerization. Sulfonated graphene (SGE) sheets were synthesized and used as both a macromolecular acid dopant and substrate for the polymerization of polyaniline (PANI), affording the SGEP nanocomposites. The morphology of PANI in the nanocomposites can be controlled to be either nanorods or nanogranules by varying the synthesis conditions. The morphology of SGEP and the shape of PANI can be tuned by adding an additional dopant and varying the amount of SGE used, and this had a significant influence on the electrochemical performance of the nanocomposites as supercapacitor electrode materials. The SGEP nanocomposite with PANI nanorods exhibited a specific capacitance of 763 F/g with a capacity retention of 96% after 100 cycles and good rate properties. Composites obtained with HCl as an additional acid dopant with two different ratios of SGE to PANI showed higher specific capacitances of 793 and 931 F/g, but lower capacity retention after 100 cycles of 77% and 76%, respectively.      

Polarized light microscopy and spectroscopy of individual single-walled carbon nanotubes

Polarized light microscopy (PLM) is used to image individual single-walled carbon nanotubes (SWNTs) suspended in air across a slit opening. The imaging contrast relies on the strong optical anisotropy typical of SWNTs. We combine PLM with a tunable light source to enable hyperspectral excitation spectroscopy and nanotube chirality assignment. Comparison with fluorescence microscopy and spectroscopy confirms the assignment made with PLM. This represents a versatile new approach to imaging SWNTs and related structures.      

Perpendicularly self-oriented and shape-controlled L10-FePt nanorods directly synthesized by a temperature-modulated process

The synthesis and self-assembly of tetragonal phase-containing L1₀-Fe₅₅Pt₄₅ nanorods with high coercive field is described. The experimental procedure resulted in a tetragonal/cubic phase ratio close to 1:1 for the as-synthesized nanoparticles. Using different surfactant/solvent proportions in the process allowed control of particle morphology from nanospheres to nanowires. Monodisperse nanorods with lengths of 60 ± 5 nm and diameters of 2–3 nm were self-assembled in a perpendicular oriented array onto a substrate surface using hexadecylamine as organic spacer. Magnetic alignment and properties assigned, respectively, to the shape anisotropy and the tetragonal phase suggest that the self-assembled materials are a strong candidate to solve the problem of random magnetic alignment observed in FePt nanospheres leading to applications in ultrahigh magnetic recording (UHMR) systems capable of achieving a performance of the order of terabits/in².