Dirac fermion heating,current scaling,and direct insulator-quantum Hall transition in multilayer epitaxial graphene

We have performed magnetotransport measurements on multilayer epitaxial graphene. By increasing the driving current I through our graphene devices while keeping the bath temperature fixed, we are able to study Dirac fermion heating and current scaling in such devices. Using zero-field resistivity as a self thermometer, we are able to determine the effective Dirac fermion temperature (T_DF) at various driving currents. At zero field, it is found that T_DF ∝ I^≈1/2. Such results are consistent with electron heating in conventional two-dimensional systems in the plateau-plateau transition regime. With increasing magnetic field B, we observe an I-independent point in the measured longitudinal resistivity ρ_xx which is equivalent to the direct insulator-quantum Hall (I-QH) transition characterized by a temperature-independent point in ρ_xx. Together with recent experimental evidence for direct I-QH transition, our new data suggest that such a transition is a universal effect in graphene, albeit further studies are required to obtain a thorough understanding of such an effect.     

Tunable terahertz graphene metamaterials

Using graphene metamaterial (MM) patterns, the tunable resonant properties of graphene–SiO₂/Si (GSiO₂Si) structures deposited on flexible polymer substrates have been theoretically investigated in the terahertz regime. This study shows that the tuning mechanism of the GSiO₂Si structure mainly depends on dipolar resonance, which is different from the conventional metallic MM structure based on the LC resonance. For graphene MM structures, the resonant transmission curves can be tuned over a wide range by controlling applied electric fields. The modulation depth of transmission is about 80%. As the Fermi level of the graphene layer increases, the resonant transmission become stronger, and the resonant dips significantly shift to higher frequency.     

Frictional characteristics of exfoliated and epitaxial graphene

To determine the friction coefficient of graphene, micro-scale scratch tests are conducted on exfoliated and epitaxial graphene at ambient conditions. The experimental results show that the monolayer, bilayer, and trilayer graphene all yield friction coefficients of approximately 0.03. The friction coefficient of pristine graphene is less than that of disordered graphene, which is treated by oxygen plasma. Ramping force scratch tests are performed on graphene with various numbers of layers to determine the normal load required for the probe to penetrate graphene. A very low friction coefficient and also its high pressure resistance make graphene a promising material for antiwear coatings.     

Quantum-squeezing effects of strained multilayer graphene NEMS

Quantum squeezing can improve the ultimate measurement precision by squeezing one desired fluctuation of the two physical quantities in Heisenberg relation. We propose a scheme to obtain squeezed states through graphene nanoelectromechanical system (NEMS) taking advantage of their thin thickness in principle. Two key criteria of achieving squeezing states, zero-point displacement uncertainty and squeezing factor of strained multilayer graphene NEMS, are studied. Our research promotes the measured precision limit of graphene-based nano-transducers by reducing quantum noises through squeezed states.     

Wafer-scale homogeneity of transport properties in epitaxial graphene on SiC

Magnetotransport measurements on Hall bar devices fabricated on purely monolayer epitaxial graphene on silicon carbide (SiC/G) show a very tight spread in carrier concentration and mobility across wafer-size dimensions. In contrast, SiC/G devices containing bilayer graphene domains display variations in their electronic properties linked to the amount of bilayer content. The spread in properties among devices patterned on the same SiC/G wafer can thus be understood by considering the inhomogeneous number of layers often grown on the surface of epitaxial graphene on SiC.     

In-plane lattice thermal conductivities of multilayer graphene films

The in-plane lattice thermal conductivities of a single layer and multilayer graphene films are investigated using nonequilibrium molecular dynamics simulations. It is found the thermal conductivity of a single layer graphene is higher than that of multilayer graphene. Increasing the bonding strength between neighboring layers will reduce the in-plane thermal conductivity for multilayer graphene films. The constraints from the neighboring layer play the role of impeding phonon transport along the in-plane direction in multilayer graphene films. This observation implies the thermal conductivity of a single layer graphene will be reduced in practical applications once it is bonded on a substrate.     

Raman spectroscopy at the edges of multilayer graphene

Individual graphene layers in a multilayer graphene sample contribute their own edges. The edge of a graphene layer laid on an n layer graphene (nLG) is a building block for the edges of multilayer graphenes. We found that the D band observed from the edge of the top graphene layer laid on the nLG exhibits an identical line shape to that of disordered (n + 1)LG. Based on the spectral features of the D and 2D bands, we identified two types of alignment configurations at the edges of bilayer and trilayer graphenes, whose edges are well-aligned from their optical images.     

Iron-mediated growth of epitaxial graphene on SiC and diamond

Ordered graphene films have been fabricated on Fe-treated SiC and diamond surfaces using the catalytic conversion of sp³ to sp² carbon. In comparison with the bare SiC (0 0 0 1) surface, the graphitization temperature is reduced from over 1000 °C to 600 °C and for diamond (1 1 1), this new approach enables epitaxial graphene to be grown on this surface for the first time. For both substrates, a key development is the in situ monitoring of the entire fabrication process using real-time electron spectroscopy that provides the necessary precision for the production of films of controlled thickness. The quality of the graphene/graphite layers has been verified using angle-resolved photoelectron spectroscopy, scanning tunneling microscopy and low energy electron diffraction. Graphene is only formed on treated regions of the surface and so this offers a method for fabricating and patterning graphene structures on SiC and diamond in the solid-state at industrially realistic temperatures.     

Ultrafast modulation of optical transitions in monolayer and multilayer graphene

We study ultrafast modulations of absorption spectra for both monolayer and multilayer graphene, by performing time-resolved transmission measurements with tuning probe photon energy. While reduced absorptions by photo-excited carriers are observed in monolayer graphene irrespective of the probe energy, multilayer graphene shows increased absorption at around 0.6 eV, which is explained by the optical transitions between subband states. Intraband carrier relaxation and electron–hole recombination times are found to be as fast as 0.5 and 10 ps, respectively. Modifications of ultrafast carrier dynamics are also studied with changing temperature and excitation density.     

Field-induced recovery of massless Dirac fermions in epitaxial graphene on SiC

We report first-principles calculations of atomic and electronic structures of epitaxial single-layer graphene on Si-terminated 4H-SiC(0 0 0 1) surface under homogeneous transverse electric fields. We find that atomic positions are insensitive to applied electric fields, but the electronic band structures of the graphene layer are shifted in energy, depending strongly on the applied electric fields, while those of the buffer layer are almost unchanged. This effect finally results in field-induced closing of the energy gap at the Dirac energy point and recovery of the conic feature of the low-energy band structures of free-standing graphene, which are verified and analyzed further with a tight-binding model consisting of the single-layer and the buffer-layer graphene only. The recovery of conical dispersion of the single-layer graphene and ambipolar field-effect behavior, despite the band-gap closure under electric field, makes epitaxial single-layer graphene one of the promising alternatives to current state-of-the-art transistors for radiofrequency applications.     

Raman spectroscopy and band structure of Pd-hybridized multilayer graphene

Graphene sheets prepared through liquid exfoliation of expanded graphite were hybridized with Pd nanoparticles. The impact of these particles on the electronic and physical structure of the graphene is determined through transmission electron microscopy and Raman spectroscopy using 532 and 325 nm excitation wavelengths. Based on the changes to the Raman D and G peaks, insights are provided concerning the deposition mechanism at pristine and defective lattice sites, as well as electronic scattering. These data are compared to ab initio band structure computations. For purposes of the model, the graphene/Pd hybrid was approximated by a charged graphene sheet. The resulting structure exhibited π–π¹ expansion approaching the Γ point of the Brillouin zone which was validated by tracking the Raman D band dispersion.     

Brillouin scattering study of low-frequency bulk acoustic phonons in multilayer graphene

The low-frequency acoustic dynamics of multilayer graphene flakes, on SiO₂/Si substrate, have been studied by polarized Brillouin light scattering. Interference enhancement affords the first observation of both the in-plane longitudinal and transverse acoustic bulk modes near the Γ-point of the Brillouin zone. The experimental data yielded information on the acoustic and elastic properties of multilayer graphene. Additionally, the measured phonon dispersion is found to be in good accordance with that evaluated for graphene, based on first-principles calculations within the generalized gradient approximation. Our findings strongly suggest that the interaction between layers in multilayer graphene is weak.     

Millimeter-long multilayer graphene nanoribbons prepared by wet chemical processing

Millimeter long multilayer graphene nanoribbons were prepared by a chemical treatment of graphite oxide (GO). To our knowledge, this is the very first report to harvest ultralong graphene ribbons with length dimension >1 mm using a wet chemical process. Scanning electron microscope (SEM) images reveal the nanoribbon length larger than 1 mm and width ∼10 μm. X-ray photoelectron spectroscopy (XPS) analysis shows that oxygen-containing functional groups decreased as the extent of the chemical treatment increased. X-ray diffraction (XRD) and Raman spectroscopy studies confirmed the XPS result and unveil more graphitic sheet like structure formed as GO was reduced by more concentrated NaOH. It is found that by adjusting NaOH/GO mass ratio during the chemical treatment, we can produce >1 mm long multilayer graphene nanoribbons and achieve controllable degree of reduction to the GO material. It is expected that this technique will make ultralong graphene nanoribbons readily available for research and applications.     

Microwave absorption and radiation from large-area multilayer CVD graphene

Here we experimentally study the microwave absorption and near-field radiation behavior of monolayer and few-layer, large-area CVD graphene in the C and X bands. Artificial stacking of CVD graphene reduces the sheet resistance, as verified by non-contact microwave cavity measurements and four-probe DC resistivity. The multilayer stacked graphene exhibits increased absorption determined by the total sheet resistance. The underlying mechanism could enable us to apply nanoscale graphene sheets as optically transparent radar absorbers. Near-field radiation measurements show that our present few-layer graphene patches with sheet resistance more than 600 Ω/sq exhibit no distinctive microwave resonance and radiate less electromagnetic power with increasing layers; however, our theoretical prediction suggests that for samples to be practical as microwave antennas, doped multilayer graphene with sheet resistance less than 10 Ω/sq is required.     

Toughening of silicon nitride ceramics by addition of multilayer graphene

Silicon nitride (Si₃N₄) ceramics have superior mechanical properties allowing their broad application in many technical fields. In this work, Si₃N₄-based composites with 1–5?wt% multilayer graphene (MLG) content were fabricated by spark plasma sintering at different temperatures and holding time in order to improve the fracture resistance of the Si₃N₄ ceramic. Our investigation focused on understanding the relationships between the microstructure and mechanical properties with special attention to the intergranular phases between Si₃N₄ matrix and MLG reinforcement.We have found that nanopores developed at the Si₃N₄-MLG interface due to a reaction between carbon and the oxygen available in the topmost layer of the Si₃N₄ particles. Interface porosity has an optimum for the toughening effect. In 1?wt% MLG/Si₃N₄ composites nanopores are local, but separated at the Si₃N₄-MLG interface, which promote the MLG pull-out mechanism imparting a significant toughening effect on the composite. Beyond the optimal 1?wt% MLG content, MLG platelets agglomerate and excessive porosity are developed at the Si₃N₄-MLG interfaces, leading to weaker matrix- graphene adhesion and thus lower fracture toughness.     

SiC surface orientation and Si loss rate effects on epitaxial graphene

We have explored the properties of SiC-based epitaxial graphene grown in a cold wall UHV chamber. The effects of the SiC surface orientation and silicon loss rate were investigated by comparing the characteristics of each formed graphene. Graphene was grown by thermal decomposition on both the silicon (0001) and carbon (000-1) faces of on-axis semi-insulating 6H-SiC with a "face-down" and "face-up" orientations. The thermal gradient, in relation to the silicon flux from the surface, was towards the surface and away from the surface, respectively, in the two configurations. Raman results indicate the disorder characteristics represented by I_D/I_G down to < 0.02 in Si-face samples and < 0.05 in C-faces over the 1 cm² wafer surface grown at 1,450°C. AFM examination shows a better morphology in face-down surfaces. This study suggests that the optimum configuration slows the thermal decomposition and allows the graphene to form near the equilibrium. The Si-face-down orientation (in opposition to the temperature gradient) results in a better combination of low disorder ratio, I_D/I_G, and smooth surface morphology. Mobility of Si-face-down orientation has been measured as high as approximately 1,500 cm²/Vs at room temperature. Additionally, the field effect transistors have been fabricated on both Si-face-down and C-face-down showing an ambipolar behavior with more favorable electron conduction.     

Observation of wrinkle induced potential drops in biased chemically derived graphene thin film networks

Graphene-based electronics show much promise due to the potential high charge-carrier mobility of the material as well as its flexibility in preparation on different substrates. Recently there has been much evidence suggesting that the wrinkle structures found in pristine graphene inhibit electron transport, reducing device performance. In this study the inhibiting role of standing wrinkles within chemically derived graphene are studied quantitatively using Kelvin force microscopy. Samples were evaluated before and after annealing at 250 C to observe changes in the channel’s surface potential dependence on the state of reduction. Annealed samples were found to have inter-flake and intra-flake contribution to the potential drop and that for the latter a correlation between the potential drop magnitude and wrinkle density is found, although there is no correlation with wrinkle height. Statistical averaging across many images demonstrated that the average lower limit of wrinkle resistance in these devices is approximately 4.5 kΩ. Such high resistance demonstrate definitively that elimination of wrinkles within graphene oxide based devices is essential in order to obtain optimum performance.     

Tunable wrinkling pattern in annular graphene under circular shearing at inner edge

This work is concerned with the wrinkling phenomenon observed in an annular graphene sheet under circular shearing at its inner edge. By performing molecular mechanics simulations on the aforementioned loaded annular graphene sheet, it is observed that the unusual wrinkles formed are confined to within an annulus that hugs the perimeter of the inner radius. This confined wrinkling pattern is in contrast to the wrinkling patterns that spread throughout rectangular graphene sheets under tension or shear. The present wrinkling pattern is characterized by a wave number and wrinkle profile. The wave number at the bifurcation wrinkle is found to depend only on the inner radius of the annular graphene and it increases almost linearly with increasing inner radius. The orientation of these developed waves is found to be at a constant angle and independent from the radii ratio of annular graphene. The wrinkle profile in terms of wave amplitude and wavelength depends on the magnitude of the circular shearing. The predictable formation of wrinkles in annular graphene can be exploited for applications in nano-force sensors, tunable magnetic or electronic devices, as well as patterned stretchable electronics.     

Vertically aligned epitaxial graphene nanowalls with dominated nitrogen doping for superior supercapacitors

For graphene-based electrode materials, N doping is one of the leading approaches for enhancing the performance of supercapacitors. However, such an outstanding performance is suppressed by the agglomeration of graphene and unspecified N incorporation. Here, we demonstrate a direct growth of vertically epitaxial graphene nanowalls (GNWs) on flexible carbon cloths (CCs) via microwave plasma-enhanced chemical vapor deposition, whereby predominantly N doping was sequentially achieved by introducing in situ NH₃ plasma, to form N-doped GNWs (NGNWs). The vertically aligned three-dimensional (3D) architecture of epitaxial NGNWs and their unique selectivity to the specific N dopants make such electrodes an ideal platform, not only for enhancing the capacitive performance but also for studying the role of the CN bonding configuration in its performance. Remarkably, NGNW supercapacitors exhibit an excellent specific capacitance of 991.6 F/g (estimation based on the actively contributing component) and an apparent area-normalized capacitance of 1488.9 mF/cm², at a specific current of 14.8 A/g. This approach allows us to achieve an energy density of 275.4 Wh/kg at a power density of 14.8 kW/kg (specific current of 14.8 A/g), and a power density of 74.1 kW/kg at an energy density of 232.6 Wh/kg (specific current of 74.1 A/g) in 1 M H₂SO₄.