Formation of high-quality quasi-free-standing bilayer graphene on SiC(0 0 0 1) by oxygen intercalation upon annealing in air

We report on the conversion of epitaxial monolayer graphene on SiC(0 0 0 1) into decoupled bilayer graphene by performing an annealing step in air. We prove by Raman scattering and photoemission experiments that it has structural and electronic properties that characterize its quasi-free-standing nature. The (6√3 × 6√3)R30° buffer layer underneath the monolayer graphene loses its covalent bonding to the substrate and is converted into a graphene layer due to the oxidation of the SiC surface. The oxygen reacts with the SiC surface without inducing defects in the topmost carbon layers. The high-quality bilayer graphene obtained after air annealing is p-doped and homogeneous over a large area.     

Grand canonical Monte Carlo simulations of nitrogen adsorption on graphene materials with varying layer number

Fabrication of monolayer graphene is a challenge and many processes yield few-layer or multi-layer graphene materials instead. The layer number is an important property of those materials and a quality control variable in graphene manufacture. We demonstrated that N₂ adsorption on graphene materials was used to distinguish its layer number. We performed grand canonical Monte Carlo simulation of N₂ adsorption on graphene materials with 1–10 layers to indicate the possibility of distinction of layer number by evaluating the dependence of N₂ adsorption characteristics on the layer number of graphene materials as well as the adsorption mechanism. The threshold relative pressures of monolayer adsorption of N₂ on monolayer and two-layer graphene were 1 × 10⁻³ and 2 × 10⁻⁴, respectively, while those of the others were 1 × 10⁻⁴. In contrast, the threshold pressures of second layer adsorption of N₂ were similar to each other. The difference of threshold pressures is attributed to stabilized energies induced by interactions with graphene materials. Therefore, the layer number of graphene materials could be evaluated from the threshold pressures of adsorption, providing a guide to aid fabrication of graphene materials.     

Low temperature growth of complete monolayer graphene films on Ni-doped copper and gold catalysts by a self-limiting surface reaction

We report on the fabrication of completely uniform monolayer graphene on a metal thin film over a 150 mm Si substrate at a low temperature of 600 °C by inductively coupled plasma-enhanced chemical vapor deposition (ICPCVD). Through novel use of bimetallic catalyst such as CuNi and AuNi alloys we were able to control catalytic reaction at the metal surface and grow complete monolayer graphene with a Ni content less than 20 at.%. We also found that the 2D/G intensity ratio in the Raman spectra was almost invariant with growth time and the C 1s peak in the XPS spectra was observed only at the metal surface. This implies that monolayer graphene was possibly grown on these Ni-doped copper and gold catalysts by a self-limiting surface reaction under our CVD condition. From DFT calculations, it was shown that the catalytic activity of normally inactive Cu and Au could be enhanced through the addition of Ni atoms at surface sites, providing graphene growth at lower temperatures than pure Cu or Au. The carrier mobility of graphene films grown on these CuNi and AuNi alloy catalyst was measured to be over 9000 cm² V⁻¹ s⁻¹ at room temperature, which is comparable to that of CVD graphene film grown on Cu foil. Therefore, we suggest an efficient way in growing a complete monolayer graphene on thin films at low temperatures, which could be a key issue in the application of graphene devices.     

High quality graphene sheets from graphene oxide by hot-pressing

We report a simple and effective route to convert graphene oxide sheets to good quality graphene sheets using hot pressing. The reduced graphene oxide sheets obtained from graphene oxide by low temperature thermal exfoliation are annealed at 1500 °C and 40 MPa uniaxial pressures for 5 min in vacuum. No appreciable oxygen content was observed from X-ray photoelectron spectroscopy and no D peak was detected in the Raman spectrum. The graphene sheets produced had a much higher electron mobility (1000 cm² V⁻¹ S⁻¹) than other chemically modified graphenes.     

On the intercalation of CO molecules in ultra-high vacuum conditions underneath graphene epitaxially grown on metal substrates

We have studied the interaction of CO with epitaxial graphene on Pt(1 1 1) and Ru(0 0 0 1) by means of high-resolution electron energy loss spectroscopy measurements. Our experiments unambiguously demonstrate that in ultra-high vacuum conditions CO does not intercalate underneath the graphene monolayer supported on Pt(1 1 1) and Ru(0 0 0 1). For submonolayer coverages of graphene on Pt(1 1 1), CO adsorption occurs only in Pt on-top sites while bridge sites, usually populated on the clean Pt(1 1 1) surface, are inhibited. Instead, we find that epitaxial graphene is rather reactive toward water molecules.     

Interaction between graphene and copper substrate: The role of lattice orientation

We present a comprehensive study of graphene grown by chemical vapor deposition on copper single crystals with exposed (1 0 0), (1 1 0) and (1 1 1) faces. Direct examination of the as-grown graphene by Raman spectroscopy using a range of visible excitation energies and microRaman mapping shows distinct strain and doping levels for individual Cu surfaces. Comparison of results from Raman mapping with X-ray diffraction techniques and atomic force microscopy shows it is neither the crystal quality nor the surface topography responsible for the specific strain and doping values, but it is the Cu lattice orientation itself. We also report an exceptionally narrow Raman 2D band width caused by the interaction between graphene and metallic substrate. The appearance of this extremely narrow 2D band with full-width-at-half maximum (FWHM) as low as 16 cm⁻¹ is correlated with flat and undoped regions on the Cu(1 0 0) and (1 1 0) surfaces. The generally compressed (∼0.3% of strain) and n-doped (Fermi level shift of ∼250 meV) graphene on Cu(1 1 1) shows the 2D band FWHM minimum of ∼20 cm⁻¹. In contrast, graphene grown on Cu foil under the same conditions reflects the heterogeneity of the polycrystalline surface and its 2D band is accordingly broader with FWHM >24 cm⁻¹.     

A theoretical analysis of the surface dependent binding,peeling and folding of graphene on single crystal copper

The binding, peeling and folding behavior of graphene on different surfaces of single crystal copper were examined theoretically. We show that the binding energy is the highest on the Cu(1 1 1), and follows the order of Cu(1 1 1) > (1 0 0) > (1 1 0) > (1 1 2). Conventional theory is capable of capturing the dynamic process of graphene peeling seen from molecular dynamics simulations. We show that the number of graphene layers on Cu surfaces could be distinguished by performing simple peeling tests. Further investigation of the folding/unfolding of graphene on Cu surfaces shows that Cu(1 1 1) favors the growth of monolayer graphene. These observations on the interaction between graphene with single crystal Cu surfaces might provide guidelines for improving graphene fabrication.     

Non-metal catalytic synthesis of graphene from a polythiophene monolayer on silicon dioxide

Direct synthesis of graphene without metal catalysts on a dielectric substrate is a major goal in graphene-based electronics and is an increasingly popular nanotechnology alternative to metal oxide semiconductor technology. However, current methods for the synthesis of these graphenes have many limitations, including the use of metal catalyst. Herein, we report a facile approach to the direct synthesis of graphene sheets based on the self-assembled monolayers (SAMs) technique. The new method for metal catalyst-free direct synthesis of a graphene sheet is through a solution-processable, inexpensive, easy, and reproducible cross-linked polythiophene self-assembled monolayer (SAM) that is formed via the [4 + 2] π cycloaddition reaction of π-electron conjugated thiophene layer self-assembled on the dielectric silicon dioxide substrate. The bifunctional molecules were carefully designed to create an SAM via silanization of alkoxy silane groups on the SiO₂ substrate, and at the other end, a thin cross-linked polythiophene layer via a [4 + 2] π-electron cycloaddition reaction of π-electron conjugated thiophene SAM. By heating the cross-linked polythiophene SAM up to 1000 °C under a high vacuum, single-layered or few-layered graphene sheets were successfully prepared on the dielectric silicon oxide substrate.     

Lap joining of graphene flakes by current-assisted CO2 laser irradiation

A novel approach utilizing current-assisted CO₂ laser irradiation was used to join two monolayer graphene flakes. Two partially overlapped graphene flakes were irradiated with a continuous wave CO₂ laser, together with a current at a constant voltage of 30 V. Raman spectrometer and transmission electron microscope (TEM) analyses showed the joining signal at a laser power density of 8 W/cm² with an irradiation time of 30 s and a current of 25 mA (30 V) for 5 min. The joining mechanism of graphene flakes was also investigated. We provide a novel route to realize large-area graphene joint for potential applications.     

Porous structures in stacked,crumpled and pillared graphene-based 3D materials

Graphene, an atomically thin material with the theoretical surface area of 2600 m² g⁻¹, has great potential in the fields of catalysis, separation, and gas storage if properly assembled into functional 3D materials at large scale. In ideal non-interacting ensembles of non-porous multilayer graphene plates, the surface area can be adequately estimated using the simple geometric law ∼2600 m² g⁻¹/N, where N is the number of graphene sheets per plate. Some processing operations, however, lead to secondary plate–plate stacking, folding, crumpling or pillaring, which give rise to more complex structures. Here we show that bulk samples of multilayer graphene plates stack in an irregular fashion that preserves the 2600/N surface area and creates regular slot-like pores with sizes that are multiples of the unit plate thickness. In contrast, graphene oxide deposits into films with massive area loss (2600–40 m² g⁻¹) due to nearly perfect alignment and stacking during the drying process. Pillaring graphene oxide sheets by co-deposition of colloidal-phase particle-based spacers has the potential to partially restore the large monolayer surface. Surface areas as high as 1000 m² g⁻¹ are demonstrated here through colloidal-phase deposition of graphene oxide with water-dispersible aryl-sulfonated ultrafine carbon black as a pillaring agent.     

Periodically rippled graphene on Ru(0 0 0 1): A template for site-selective adsorption of hydrogen dimers via water splitting and hydrogen-spillover at room temperature

The interaction of water with periodically rippled graphene deposited on Ru(0 0 0 1) and nearly-flat graphene/Pt(1 1 1) has been investigated by using high-resolution electron energy loss spectroscopy. Graphene samples were exposed to ambient air humidity as well as to water molecules under controlled conditions in vacuum. In both cases, loss measurements show that water molecules dosed at room temperature dissociate giving rise to C–H bonds. We suggest that water molecules intercalate under graphene and are split by the underlying metal catalyst. On the lattice-mismatched graphene/Ru(0 0 0 1) interface, the corrugation of the graphene overlayer induces site selectivity for H adsorption in ortho and para dimers. On the other hand, no dimer formation occurs for the nearly-flat, multidomain graphene/Pt(1 1 1) interface.     

Surface modification of poly-l-lactic acid fibrous scaffolds by a molecular-designed multi-walled carbon nanotube multilayer for enhancing cell interactions

We presented a molecular-designed multi-walled carbon nanotube (MWCNT) layer-by-layer (LbL) multilayer on poly-l-lactic acid (PLLA) electrospun fibers for engineering cell/CNT interfaces. A stable, positively charged monolayer was created on the fiber surface by the aminolysis reaction of poly(ethylene imine) (PEI) with PLLA, followed by alternate deposition in negatively charged MWCNT and positively charged chitosan (CS). Thermogravimetric analysis indicated a sustained growth of the MWCNT during the self-assembly process. The interactions between MWCNT and polycation crucially affected the specific structure and properties of the MWCNT multilayer. MWCNT/PEI electrostatic interactions reduced the gap between MWCNTs and improved the π → π¹ transitions. However, the CS chains tended to be more serpentine than the chains of PEI molecules, which might have hindered the π → π¹ transitions. On the other hand, the electrostatic interactions might have enhanced the disorder grade of the MWCNT structure, as indicated by Raman analysis. The scaffolds maintained their fibrous and porous structure after MWCNT multilayer modification and supported fibroblast growth. The MWCNT multilayer induced cell migration toward the interior of the scaffolds. Therefore, we created a simple yet efficient method of building a CNT multilayer on three-dimensional (3D) fibrous scaffolds for enhancing cell-matrix interactions.     

Extraordinary toughening enhancement and flexural strength in Si3N4 composites using graphene sheets

Two types of Si₃N₄ composites containing graphene nanostructures using two different graphene sources, pristine graphene nanoplatelets and graphene oxide layers were produced by Spark Plasma Sintering. The maximum toughness of 10.4 MPa m^1/2, measured by flexure testing of pre-cracked bars, was achieved for a composite (∼60β/40α-Si₃N₄, ∼300 nm grain size) with 4 vol.% of reduced graphene oxide, indicating a toughening enhancement of 135% when compared to a similar Si₃N₄. This was also accompanied by a 10% increase in flexure strength (1040 MPa). For the composites with thicker graphene nanoplateletes only a 40% of toughness increase (6.6 MPa m^1/2) without strength improvement was observed for the same filler content. The large difference in the maximum toughness values accomplished for both types of composites was attributed to variations in the graphene/Si₃N₄ interface characteristics and the extent of monolayer graphene exfoliation.     

Thermal chemical vapor deposition grown graphene heat spreader for thermal management of hot spots

Graphene of different layer numbers was fabricated using thermal chemical vapor deposition (TCVD), and it was demonstrated as a heat spreader in electronic packaging. Platinum thermal evaluation chips were used to evaluate the thermal performance of the graphene heat spreaders. The temperature of a hot spot driven at a heat flux of up to 430 W cm⁻² was decreased from 121 °C to 108 °C (ΔT ≈ 13 °C) with the insertion of the monolayer graphene heat spreader, compared with the multilayer (n = 6–10) ones’ temperature drop of ∼8 °C. Various parameters affecting the thermal performance of graphene heat spreaders were discussed, e.g. layer numbers of graphene, phonon scattering, thermal boundary resistance. We demonstrate the potentials of using a complementary metal oxide semiconductor compatible TCVD process to utilize graphene as a heat spreader for heat dissipation purposes.     

Direct formation of graphene layers on diamond by high-temperature annealing with a Cu catalyst

The formation of high-quality graphene layers on diamond was achieved based on a high-temperature annealing method using a Cu catalyst. Typical features of monolayer graphene were observed in the Raman spectra of layers formed by annealing of Cu/diamond heterostructures at 950 °C for 90 min. The coverage ratio of these graphene layers on diamond was estimated to be on the order of 85% by Raman mapping of the 2D peak. The sheet hole concentration and mobility values of the layers were estimated to be ~ 10¹³ cm^− 2 and ~ 670 cm²/Vs, respectively. These values are comparable to those previously observed for high-quality graphene layers on SiC.     

Effect of hydrogenation on graphene thermal transport

We studied thermal conductivity of the three most stable hydrogenated graphene (graphane) conformers by means of non-equilibrium molecular dynamics. We estimated thermal conductivity for pristine graphene with sample length 2.1 (2.4) μm as large as κ = 745.4 ± 0.3 and 819.1 ± 0.3 W m⁻¹ K⁻¹ in the armchair and zigzag directions, respectively, in very good agreement with previous theoretical results based on the Boltzmann transport equation. In the case of the three graphane isomers we observed a dramatic κ reduction by at least one order of magnitude with respect to pristine graphene. We elucidated this reduction in terms of different phonon density of states and mean-free path distribution between graphene and graphane. The deterioration of thermal transport upon hydrogenation in graphene, could be proposed as a way to tune thermal transport in graphene for phononic applications such as thermal diodes.     

Self-limited growth of large-area monolayer graphene films by low pressure chemical vapor deposition for graphene-based field effect transistors

During the last decade, fabrication of high-quality graphene films by chemical vapor deposition (CVD) for nanoelectronics and optoelectronic applications has attracted increasing attention. However, processing of large-area monolayer and defect-free graphene films is still challenging. In this work, we have studied the effect of processing conditions on the self-limited growth of graphene monolayers on copper foils during low pressure CVD both experimentally and theoretically based on thermokinetics and kinetics of Langmuir adsorption. The effect of copper pre-treatment, growth time, and carbon potential of the atmosphere (indicated by the methane-to-hydrogen gas ratio, r) on the quality of graphene nanosheets (number of layers, surface roughness and the lateral size) were studied. Microscopic studies show that careful pre-treatment of the copper foil by electropolishing provides a suitable condition for the self-limited growth of graphene with minimum surface roughness and defects. Raman spectroscopy and atomic force microscopy determine that the number of graphene sheets decreases with increasing the carbon potential while smother surfaces are attained. Large-area monolayer graphene films are obtained at relatively high carbon potential (r=1) and controlled growth time (10 min) at 1000 °C. Measurement of the electrical response of the prepared monolayer graphene films on SiO₂ (300 nm)/Si substrates in a field effect transistor (FET) device shows a high mobility of 2780 cm² V⁻¹ s⁻¹. Interestingly, the device exhibits p-type semiconducting behavior with the Dirac point at a gate voltage of 25 V. The finding show a great promise for graphene-based FET devices for future nanoelectronics.     

Influence of the electrochemical reduction process on the performance of graphene-based capacitors

Electrochemically reduced graphene was used as the key element in the preparation of electric double-layer capacitors where the thickness of the electrode was only a few hundred nano-meters. The resultant electrodes showed different specific capacitances after pre-reduction with scanning potential windows of −1.0 to 1.6 V, −1.5 to 0 V and −1.0 to 1.0 V. Also, a specific capacitance of 246 F/g was obtained as the graphene oxide electrode was reduced with an applied potential of −1.0 to 1.0 V for 4000 s. The influence of the residual oxygen functional groups and sp² domains in electrochemically reduced graphene were investigated for capacitance performance.     

Customized casting of unstacked graphene with high surface area (>1300 m2 g−1) and its application in oxygen reduction reaction

Introducing graphene protuberances covalently bonded with the graphene sheets is a straightforward strategy to avoid the stacking of graphene layers. The as-obtained unstacked double-layer templated graphene (DTG) is expected to fully demonstrate intrinsic properties of graphene assemblies if its detailed structure and component can be well controlled. Herein, both the lateral size and graphene protuberance size and areal density of DTG were well modulated through adjusting the template morphology and casting procedures. The lateral size of the as-obtained DTG was ranging from 0.4 to 2 μm. They exhibited a very high specific surface area ranging from 1336 to 1579 m² g⁻¹ and tailorable graphene protuberances with areal density from 5.3 × 10¹⁴ to 7.8 × 10¹⁴ m⁻². DTG flakes with more hydrophilic surface and well tunable reactivity were obtained by introducing nitrogen into DTG through in-situ deposition. The as-synthesized N-doped DTG afforded significantly improved reactivity on oxygen reduction reaction (nearly 50 mV positively shifted onset potential compared with that of pristine DTG and a current preservation of 92.8% after 16,000 s test).     

Towards the perfect graphene membrane? – Improvement and limits during formation of high quality graphene grown on Cu-foils

We investigated the structure and crystalline quality of monolayer graphene grown by hydrogen and methane chemical vapor deposition (CVD) on polycrystalline Cu foils. Our data show that the high temperature hydrogen pretreatment of the Cu foil has to be performed at a sufficiently high H₂ pressure in order to avoid graphene (g) formation already during the pretreatment, which limits the achievable domain size during subsequent growth in the CH₄/H₂ mixture. Methane–hydrogen CVD sustains g growth but induces the faceting of the Cu substrate. Characterization by low energy electron microscopy evidenced a staircase Cu substrate morphology of alternating (4 1 0) and (1 0 0) planes interrupted by (n 1 1) type facets. The g flakes cover the staircase shaped support as a coherent layer. The polycrystalline film mostly contains rotational domains that are preferentially, but not strictly, aligned with respect to the stepped support surface. The substrate induced corrugated morphology occurs also underneath large single crystalline flakes and is transferred to suspended membranes, produced by etching the Cu underneath the graphene. Thus, membranes manufactured from g-Cu are non flat. This explains their reported softened elastic response and the formation of so called nanorippled graphene after transfer from the Cu support which deteriorates its electrical conductivity.