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.     

Formation of qualified epitaxial graphene on Si substrates using two-step heteroexpitaxy of C-terminated 3C-SiC(-1-1-1) on Si(110)

Formation of epitaxial graphene (EG) on 3C–SiC films heteroepitaxially grown on Si substrates, otherwise known as graphene-on-silicon (GOS) technology, has a high potential in future nanocarbon-based electronics. The EG's quality in GOS however remains mediocre due mostly to the high density of crystal defects in the 3C–SiC/Si films caused by the large (~ 20%) lattice-mismatch between Si and 3C–SiC crystals. Resultant Si out-diffusion along the planar defects during the high-temperature (~ 1525 K) graphitization annealing can also account for the degradation. Here we propose a two-step growth technique that consists of seeding of rotated 3C-SiC(-1-1-1) crystallites on the Si(110) substrate, conducted in the high-temperature-low-pressure regime, followed by a rapid growth of SiC films in the low-temperature-high-pressure regime. We succeeded in forming an almost lattice-relaxed 3C-SiC(-1-1-1) film on Si(110), having a sufficient thickness (~ 200 nm) that we believe is able to suppress the Si out-diffusion during graphitization. A graphitization annealing applied to this epi-film yields an EG, whose domain size is increased by 60% as compared to that of conventional GOS films.     

Evolution of epitaxial graphene layers on 3C SiC/Si (1 1 1) as a function of annealing temperature in UHV

The growth of graphene on SiC/Si substrates is an appealing alternative to the growth on bulk SiC for cost reduction and to better integrate the material with Si based electronic devices. In this paper, we present a thorough in situ study of the growth of epitaxial graphene on 3C SiC (1 1 1)/Si (1 1 1) substrates via high temperature annealing (ranging from 1125 to 1375 °C) in ultra high vacuum (UHV). The quality and number of graphene layers have been investigated by using X-ray Photoelectron Spectroscopy (XPS), while the surface characterization have been studied by Scanning Tunnelling Microscopy (STM). Ex-situ Raman spectroscopy measurements confirm our findings, which demonstrate the exponential dependence of the number of graphene layers on the annealing temperature.     

Growth of large area monolayer graphene on 3C-SiC and a comparison with other SiC polytypes

Epitaxial graphene growth was performed on the Si-terminated face of 4H-, 6H-, and 3C-SiC substrates by silicon sublimation from SiC in argon atmosphere at a temperature of 2000 °C. Graphene surface morphology, thickness and band structure have been assessed by using atomic force microscopy, low-energy electron microscopy, and angle-resolved photoemission spectroscopy, respectively. Differences in the morphology of the graphene layers on different SiC polytypes is related mainly to the minimization of the terrace surface energy during the step bunching process. The uniformity of silicon sublimation is a decisive factor for obtaining large area homogenous graphene. It is also shown that a lower substrate surface roughness results in more uniform step bunching with a lower distribution of step heights and consequently better quality of the grown graphene. Large homogeneous areas of graphene monolayers (over 50 × 50 μm²) have been grown on 3C-SiC (1 1 1) substrates. The comparison with the other polytypes suggests a similarity in the surface behaviour of 3C- and 6H-SiC.     

A simple method to synthesize graphene at 633 K by dechlorination of hexachlorobenzene on Cu foils

A modified chemical vapor deposition method to synthesize graphene at 360 °C is described. Hexachlorobenzene (HCB) was used as carbon source, and copper foils were used as not only the substrates for graphene deposition but also the catalyst to HCB dechlorination. The possible growth mechanism was investigated using X-ray photoelectron spectroscopy. Enhancement of HCB dechlorination by copper played a key role in synthesis of graphene at such a low temperature.     

The role of SiC as a diffusion barrier in the formation of graphene on Si(111)

In this paper, we investigate the role of SiC as a diffusion barrier for Si in the formation of graphene on Si(111) via direct deposition of solid-state carbon atoms in ultra-high vacuum. Therefore, various thicknesses of the SiC layer preformed on the Si substrates were produced in order to evaluate its influence on the quality of graphene formation at different substrate temperatures from 900 °C to 1100 °C. At a given temperature of 1100 °C, we found that a thicker SiC layer can suppress silicon-out diffusion from the substrate and improve the structural quality of the graphene layer. The samples were analyzed by low energy electron diffraction, Auger electron spectroscopy, X-ray photoemission spectroscopy, Raman spectroscopy, and scanning tunneling microscopy.     

Quasi-free-standing monolayer and bilayer graphene growth on homoepitaxial on-axis 4H-SiC(0 0 0 1) layers

Quasi-free-standing monolayer and bilayer graphene is grown on homoepitaxial layers of 4H-SiC. The SiC epilayers themselves are grown on the Si-face of nominally on-axis semi-insulating substrates using a conventional SiC hot-wall chemical vapor deposition reactor. The epilayers were confirmed to consist entirely of the 4H polytype by low temperature photoluminescence. The doping of the SiC epilayers may be modified allowing for graphene to be grown on a conducing substrate. Graphene growth was performed via thermal decomposition of the surface of the SiC epilayers under Si background pressure in order to achieve control on thickness uniformity over large area. Monolayer and bilayer samples were prepared through the conversion of a carbon buffer layer and monolayer graphene respectively using hydrogen intercalation process. Micro-Raman and reflectance mappings confirmed predominantly quasi-free-standing monolayer and bilayer graphene on samples grown under optimized growth conditions. Measurements of the Hall properties of Van der Pauw structures fabricated on these layers show high charge carrier mobility (>2000 cm²/Vs) and low carrier density (<0.9 × 10¹³ cm⁻²) in quasi-free-standing bilayer samples relative to monolayer samples. Also, bilayers on homoepitaxial layers are found to be superior in quality compared to bilayers grown directly on SI substrates.     

Microstructure and growth mechanism of multi-layer graphene standing on polycrystalline SiC microspheres

Multi-layer graphene standing on polycrystalline SiC microspheres was prepared by pyrolyzing liquid polysilacarbosilane. The lateral dimension of the multi-layer graphene is ∼100 nm and the average diameter of the microspheres is ∼0.9 μm. The growth of the multi-layer graphene is proposed to be initiated by phase separation of the microspheres, and facilitated with both crystallization inside and chemical vapor deposition outside. This method offers an alternative way to prepare multi-layer graphene on SiC without the need for 4H– or 6H–SiC crystals.     

Erosive wear resistance of NCD coatings produced by pulsed microwave discharges

Erosion tests on nanocrystalline diamond (NCD) films are relevant not only for the evaluation of the erosive wear resistance, anticipating applications where coated materials are exposed to particle impacts, but also as a way to evaluate their adhesion to the substrates. NCD films were grown on Si₃N₄ ceramic by microwave plasma assisted deposition in continuous (CW) and pulsed (PW-50 Hz and PW-500 Hz) discharge modes in argon-rich gas mixture. The films grown in PW modes presented lower crystallite size and lower surface roughness than those grown in CW one, while the use of CF₄ plasma pre-treatment of the substrate lead to further film homogeneity. The erosive wear resistance of NCD was evaluated by solid particle impact using SiC (45–250 μm size) as erodent material, with selected parameters accordingly to Hertzian stress field calculations. Film weight loss was undetectable until delamination took place. When tested with 150 μm SiC particles, the CF₄ plasma pre-treated substrates yield a three-fold increase (15 min) in delamination time comparing to untreated specimens, while samples coated under PW-50 Hz conditions presented a six times lower erosion rate compared to CW ones. It is believed that the improved nucleation behaviour by the use of PW mode and its higher homogeneity on the CF₄ plasma pre-treated samples decrease the flaw population on the diamond/substrate interface, leading to improved adhesion levels.     

Low temperature elastic properties of chemically reduced and CVD-grown graphene thin films

We have measured internal friction and shear modulus of both reduced graphene oxide and chemical-vapor deposited graphene films measuring as thin as 5 nm. Graphene oxide films were deposited from solutions by spin-coating, and graphene films were synthesized by chemical-vapor deposition (CVD) on Ni thin films. In both cases, these films were transferred from their host substrate into a water bath, then re-deposited onto to a high-Q single crystal silicon mechanical double-paddle oscillator. A minimal thickness dependence of both internal friction and shear modulus was found within the experimental uncertainty for reduced graphene oxide films varying thickness from 5 to 90 nm. The internal friction of all films exhibits a temperature independent plateau below 10 K. The values of the plateaus are similar for both the reduced graphene oxide films and CVD graphene films, and they are as high as the universal “glassy range” where the tunneling states dominated internal friction of amorphous solids lies. This result shows that from a mechanical loss point of view, both graphene oxide and CVD graphene films have high and similar level of disorder. Raman measurements performed on the same samples show higher structure order in CVD graphene films than in graphene oxide films. Our results suggest that internal friction probes different sources of disorder from those by Raman, and the disorder is not directly related to the existence of C–O binding in the graphene oxide films. The shear modulus averages 53 GPa after subtracting Young's modulus component from the vibration mode used in experiments.     

Monolayer graphene as ultimate chemical passivation layer for arbitrarily shaped metal surfaces

Monolayer graphene was grown on polycrystalline Ru thin films on patterned fused silica. The Ru films grow with columnar structure with strongly aligned grains exposing flat (0 0 0 1) surface facets within the 3D geometric patterns and on the adjacent planar silica surface. The monolayer graphene was found to completely and uniformly cover the Ru films on the complex engineered substrates. In addition, we demonstrate that the single atomic layer graphene protects the underlying metal surface against reaction with ambient gases of particular importance for applications such as concave focusing mirrors, non-planar microelectrode arrays, etc.     

Exceptional micromachining performance of silicon carbide ceramics by adding graphene nanoplatelets

The electrical discharge machining (EDM) performance of silicon carbide (SiC) ceramics containing graphene nanoplatelets (GNPs) is investigated for the first time. Under fine machining conditions, the material removal rate (MRR) dramatically increases up to 186% when 20 vol.% of GNPs are added to SiC ceramics, leading to reductions on the electrode wear rate of 132%. The EDMed nanocomposites exhibit surface roughness ≤ 0.8 μm. This outstanding EDM response of the graphene nanocomposites as compared to monolithic SiC is explained by their enhanced transport properties, establishing a direct dependence of MRR with the electrical conductivity. EDM performance of the nanocomposites also depends on the testing direction for materials with low GNPs connectivity (≤ 10 vol.%). Melting/evaporation are the main removal mechanisms, thermal spalling also operating for low thermal conducting materials. The employ of EDM on SiC/graphene nanocomposites allows machining microparts with a fine dimensional precision, opening new opportunities for SiC-based microcomponents.     

Influence of SiC particle addition on the nucleation density and adhesion strength of MPCVD diamond coatings on Si3N4 substrates

It is generally accepted that SiC layers are often involved in the adhesion efficiency of chemical vapour deposition (CVD) diamond films on Si-containing substrates. Si₃N₄–SiC composite substrates with different amounts of SiC particles (0–50 wt%) were then used for diamond deposition. Samples were produced by pressureless sintering (1750°C, N₂ atmosphere, 2–4 h). The diamond films were grown on a commercial MPCVD reactor using H₂/CH₄ mixtures. Despite there being no special substrate pre-treatment, the films were densely nucleated when SiC was added (N_d≈1×10¹⁰ cm⁻²) with primary nanosized (∼100 nm) particles, followed by a less dense (N_d≈1×10⁶ cm⁻²) secondary nucleation. Indentation experiments with a Brale tip of up to 588 N applied load corroborated the benefit of SiC inclusion for a strong adhesion. The low thermal expansion coefficient mismatch between Si₃N₄ and diamond resulted in very low compressive stresses in the film, as proved by micro-Raman spectroscopy.     

Graphene layers produced from carbon nanotubes by friction

Graphene layers have been produced from multi-walled carbon nanotube (MWCNT) bulk materials by friction when polished on ground-glass, offering a novel and effective method to produce graphene layers, which, more importantly, could be transferred to other substrates by rubbing. Field emission scanning electron microscopy, Raman spectroscopy, atomic force microscopy, transmission electron microscopy and selected area electron diffraction confirmed the formation of graphene layers. They were thought to be peeled away from the MWCNT walls due to friction. The reflection spectra showed that absorption of as-produced graphene layers decreased with wavelength in the range of 250–400 nm, compared to the MWCNT bulk material having strong absorption at 350 nm. Nanoscratch test was used to determine the mechanical properties of graphene films, suggesting the tolerance of as-produced graphene film to flaws introduced by scratch.     

Tuning doping and strain in graphene by microwave-induced annealing

We propose microwave-induced annealing as a rapid, simple, and effective method of controlling surface doping and strain in graphene. Raman spectroscopy was used to confirm that heavy and uniform p-type (1.2 × 10¹³ cm⁻²) doping can be achieved within only 5 min without unintended defects by placing graphene onto a substrate with a sufficiently high dielectric constant and exposing graphene and its substrate to microwave irradiation. Further, we showed that ripples are formed in suspended graphene when it is exposed to microwave irradiation. Silicon has a sufficiently high dielectric constant (11.9) and graphene is commonly deposited on silicon-based substrates, so our proposed microwave-induced annealing technique can be used for the rapid manipulation of the properties of graphene at low cost.     

Direct reduction of graphene oxide films into highly conductive and flexible graphene films by hydrohalic acids

We report a simple but highly-effective hydrohalic acid reducing method to reduce graphene oxide (GO) films into highly conductive graphene films without destroying their integrity and flexibility at low temperature based on the nucleophilic substitution reaction. GO films reduced for 1 h at 100 °C in 55% hydroiodic (HI) acid have an electrical conductivity as high as 298 S/cm and a C/O ratio above 12, both of which are much higher than films reduced by other chemical methods. The reduction maintains good integrity and flexibility, and even improves the strength and ductility, of the original GO films. Based on this reducing method, a flexible graphene-based transparent conductive film with a sheet resistance of 1.6 kΩ/sq and 85% transparency was obtained, further verifying the advantage of HI acid reduction.     

A simple method to synthesize continuous large area nitrogen-doped graphene

Large area nitrogen (N)-doped graphene films were grown on copper foil by chemical vapor deposition. The as-grown films consisted of a single atomic layer that was continuous across the copper surface steps and grain boundaries, and could be easily transferred to a variety of substrates. N-doping was confirmed by X-ray photoelectron spectroscopy, Raman spectroscopy, and elemental mapping. N atoms were suggested to mainly form a “pyrrolic” nitrogen structure, and the doping level of N reached up to 3.4 at.%. The N-doped graphene exhibited an n-type behavior, and nitrogen doping would open a band gap in the graphene. This study presents use of a new liquid precursor to obtain large area, continuous and mostly single atom layer N-doped graphene films.     

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.     

Photo-thermal chemical vapor deposition of graphene on copper

We demonstrate the synthesis of single-layer graphene films on copper by photo-thermal chemical vapor deposition (PTCVD) realized using a rapid thermal processing system typically used in CMOS processing. Influence of the temperature on the low-pressure (10 mbar) graphene synthesis using methane precursor was characterized by analyzing the crystalline quality, thickness and electronic properties of the films. Using a growth time of only 60 s, for graphene fabricated at 950 °C the sheet resistance and mobility show equivalent quality compared to thermal CVD graphene. Moreover, μ-Raman mapping reveals very low defect density and high 2D to G band ratio similar to the fingerprint of exfoliated single-layer graphene. The synthesis process was found to exhibit a threshold at around 900 °C at which (and below) the single-layer graphene film does not contain adlayer flakes typically observed in high temperature CVD graphene on copper. Our study shows that PTCVD can be used for the high throughput fabrication of high-quality single-layer graphene on copper and is therefore a promising method while pursuing cost-effective graphene fabrication.     

Silicon carbide films from polycarbosilane and their usage as buffer layers for diamond deposition

Thin films of polycarbosilane (PCS) were coated on a Si (100) wafer and converted to silicon carbide (SiC) by pyrolyzing them between 800 and 1150 °C. Granular SiC films were derived between 900 and 1100 °C whereas smooth SiC films were developed at 800 and 1150 °C. Enhancement of diamond nucleation was exhibited on the Si (100) wafer with the smooth SiC layer generated at 1150 °C, and a nucleation density of 2 × 10¹¹ cm^− 2 was obtained. Nucleation density reduced to 3 × 10¹⁰ cm^− 2 when a bias voltage of − 100 V was applied on the SiC-coated Si substrate. A uniform diamond film with random orientations was deposited to the PCS-derived SiC layer. Selective growth of diamond film on top of the SiC buffer layer was demonstrated.