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.     

Solvent-free mechanochemical reduction of graphene oxide

We report a versatile and eco-friendly approach for the reduction of graphene oxide into high-quality graphene nanoplatelets by simple solid-state mechanochemical ball-milling in the presence of hydrogen. After the ball-milling process, the resultant graphene nanoplatelets show the efficient restoration of the graphitic structure completely free from any heteroatom doping (e.g., nitrogen, sulfur) and enhanced electrical conductivities up to 120 and 3400 S/m before and after an appropriate heat treatment (e.g., 900 °C for 2 h under nitrogen).     

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.     

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.     

Single step preparation of meso-porous and reduced graphene oxide by gamma-ray irradiation in gaseous phase

A facile and highly efficient route to produce simultaneously porous and reduced graphene oxide by gamma ray irradiation in hydrogen is here demonstrated. Narrowly distributed nano-scale pores (average size of ∼3 nm and surface density >44,900 pore μm⁻²) were generated across 10 μm thick graphene oxide bucky-papers at a total irradiation dose of 500 kGy. The graphene oxide sheet reduction was confirmed to occur homogeneously across the structures by Fourier transform infrared spectroscopy and Raman analysis. This one-step, catalyst-free, high penetration and through-put technique, offers great promises potential for the mass production of reduced graphene oxide from cheap graphene oxide.     

Large-area reduced graphene oxide thin film with excellent thermal conductivity and electromagnetic interference shielding effectiveness

In this work, we fabricated reduced large-area graphene oxide (rLGO) with maximum surface area of 1592 μm² through a cost-effective chemical reduction process at low temperature. The product revealed large electrical conductivity of 243 ± 12 S cm⁻¹ and thermal conductivity of 1390 ± 65 W m⁻¹ K⁻¹, values much superior to those of a conventional reduced small-area graphene oxide (with electrical conductivity of 152 ± 7.5 S cm⁻¹ and thermal conductivity of 900 ± 45 W m⁻¹ K⁻¹). The rLGO thin film also exhibited not only excellent stiffness and flexibility with Young’s modulus of 6.3 GPa and tensile strength of 77.7 MPa, but also an efficient electromagnetic interference (EMI) shielding effectiveness of ∼20 dB at 1 GHz. The excellent performance of rLGO is attributed to the fact that the larger area LGO sheets include much fewer defects that are mostly caused by the damage of graphene sp² structure around edge boundaries, resulting in large electrical conductivity. The manufacturing process of rLGO is an economical and facile approach for the large scale production of highly thermally conducting graphene thin films with efficient EMI shielding properties, greatly desirable for future portable electronic devices.     

Low-cost preparation of a conductive and catalytic graphene film from chemical reduction with AlI3

AlI₃ synthesized by I₂ and Al in ethanol was used as reductive agent to directly obtain flexible reductive graphene oxide (RGO) films with high conductivity of 5320 S/m from graphene oxide (GO) films at a low temperature of 80 °C. This reductive method has provided a low-cost and effective route for large-scale production of graphene with high catalytic activity. Structural evolution during the reduction of GO was studied by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. The RGO films served as counter electrode exhibited high electrochemical activity.     

Ultrathin perfluoropolyether coatings for silicon wafers: a XPS study

Oxidized silicon wafers were functionalized in mild conditions using alkoxysilanes containing perfluoropolyether chains: the reaction was monitored by FTIR and very thin fluorinated films were formed. After the treatment, the surface tension of the wafers decreased dramatically (from 43 mN/m for the neat wafer to 21–13 mN/m depending on the conditions of the silanization process), high repellency toward polar and apolar media was achieved. The composition of the fluorinated coatings was investigated in details by XPS spectroscopy.     

Mechanical properties of free-standing graphene oxide

The mechanical properties of free-standing graphene oxide (GO) films were investigated using nanoindentation on a dynamic contact module (DCM) system. The Young's modulus, stiffness, and ultimate strength of thin films were evaluated. Nanoindentation measurements were combined with the DCM to evaluate the mechanical properties of thin films and to predict the crack length and critical energy. Electrophoretically deposited GO film, 50 ~ 60 nm in thickness, was found to have a Young's modulus of 695 ± 53 ~ 697 ± 15 GPa. The critical energy values for 50- and 60-nm-thick films were 0.142 ~ 0.201 and 0.479 ~ 0.596 J/m², respectively. Nanoindentation combined with the DCM can thus be used to obtain the mechanical properties and critical energy of thin films.     

Graphene nanosheets based on controlled exfoliation process for enhanced lithium storage in lithium-ion battery

A facile and rapid approach was used for the fabrication of chemically derived graphene nanosheets based on the reduction of graphite oxide (GO) in tube furnace assembly at different temperatures. The morphologies, microstructures, specific surface areas and other features of GO and graphene nanosheets were characterized. Structure characterization indicates that the platelet thickness of graphene nanosheets obtained at 300 °C was 1.62 nm, which corresponds to an approximately 5 layers stacking of the monoatomic graphene nanosheets. Electrochemical performances of the as-prepared graphene nanosheets were performed, the result of which could prove the above observation that graphene nanosheets (5 layers) obtained at 300 °C actually displayed the most remarkable electrochemical performances: the first discharge and charge capacities of graphene nanosheets were as high as 2137 mAh/g and 994 mAh/g, respectively, and after 100 cycles graphene nanosheets still possessed a high capacity of 478 mAh/g.     

Effects of adding different morphological carbon nanomaterials on supercapacitive performance of sol–gel manganese oxide films

In this study, the supercapacitive performances of manganese oxide films were investigated by adding different carbon nanomaterials, including carbon nanocapsules (CNC), multiwalled carbon nanotubes (MWCNTs) and multi-layered graphene. The manganese oxide films were prepared with manganese acetate precursor by sol–gel method, and the post-treatment effects were also examined. With a heat-treatment above 300 °C, the as-prepared amorphous films transformed to a compound of Mn₃O₄ and Mn₂O₃ phases, and the smooth surface became rough as well. Cyclic voltammogram (CV) tests showed that the manganese oxide film, which was mixed with 0.05 wt% MWCNTs and annealed at 350 °C for 1 h, exhibited the optimized specific capacitance, 339.1 F/g. During 1000CV cycles, the specific capacitances of original manganese oxide film decreased gradually from 198.7 to 149.1 (75%) F/g. After same number of cycle tests, the modified films containing 0.025 wt% CNC, 0.05 wt% MWCNTs and 0.1 wt% graphene retained 201.8 (64.2%), 267.4 (78.9%) and 193.1 (57.4%) F/g respectively. The results indicates that the supercapacitive performance of manganese oxide films were significantly modified by carbon nanomaterials; in addition, the MWCNTs additive could also reduce the decay rate.     

Effect of XeF laser treatment on structure of nanocrystalline diamond films

Nanocrystalline diamond (NCD) films were deposited on Si substrates by microwave plasma-enhanced chemical vapor deposition (MPECVD) using methane/hydrogen/oxygen (30/169/0.2 sccm) as process gases. Subsequently a thin (0.33 μm) and a thick (1.01 μm) NCD films were irradiated with XeF excimer laser (λ = 351 nm) with 300 and 600 mJ cm^? 2 of energy densities in air. The NCD films became rougher after laser irradiations. Fraction of graphitic clusters decreased but oxygen content increased in the thin NCD film after laser irradiation. Opposite phenomena were observed for the thick NCD films. Effect of laser irradiation to oxygenation and graphitization of NCD films was correlated with structural properties of free surface and grain boundaries of the thin and thick NCD films.     

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.     

Preparation of pillared carbon thin films from the reduction of silylated graphite oxide by UV light irradiation and their size selective electrical response to various molecules

Silylated graphite oxide thin films were reduced by UV light irradiation using a super high pressure Hg lamp at 95 °C. The reduction of silylated graphite oxide was completed within 24 h and a new pillared carbon with an interlayer spacing of 0.81 nm was obtained. Pillared carbons with larger interlayer spacings of about 1.13 nm were also obtained from graphite oxide silylated with octyltrichlorosilane and then with 3-aminopropyltriethoxysilane for 1.5–6 h, when they were reduced by UV light irradiation and heating at 200 °C under vacuum. Selective electrical response during exposure to gaseous vinylene carbonate, acetonitrile, ozone and hydrogen molecules has been achieved by changing the pillar density in the resulting pillared carbon films.     

Junction characteristics of chemically-derived graphene/p-Si heterojunction solar cell

Experimental and theoretical investigations on the heterojunction of silicon (Si) with chemically derived graphene have been presented. The stability study of graphene oxide and reduced graphene oxide (rGO) in aqueous medium were performed by visual observation and surface charge measurement. The detailed characterization by FT-IR, UV–Vis, and Raman spectroscopy exhibited the formation of rGO with a high optical band gap of 3.6 eV. The atomic force microscopy analysis for rGO sample revealed the formation of flakes with thickness ≈ 10 nm. The rGO was spin-coated on the p-Si substrate for fabrication of a heterojunction device, with the structure of rGO/p-Si. In the fabricated device, incident light was transmitted through the thin rGO film to reach the junction interface, generating photoexciton, and thereby a photo-conversion efficiency of 0.02% was achieved. The theoretical simulation of rGO/p-Si heterojunction device using solar cell capacitance simulation 1D software showed the efficiency of 1.32%. Such large deviations in efficiency between experiment and theory have been discussed in details.     

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.     

Structural and optical studies on sol–gel derived ZnO thin films by excimer laser annealing

High-quality polycrystalline ZnO thin films were deposited onto alkali-free glasses at a temperature of 300°C in air ambience by combining sol–gel spin coating and KrF excimer laser annealing. The effects of laser irradiation energy density on the crystallization, microstructure, surface morphology, and optical transmittance of as-prepared ZnO thin films were investigated and compared to the results of thermally annealed ZnO thin films. The crystallinity level and average crystallite size of laser annealed ZnO thin films increased as laser energy density increased. The crystallinity levels and average crystallite size of excimer laser annealed (ELA) thin films were greater than those of the thermally annealed (TA) thin films. However, laser annealed thin films had abnormal grain growth when irradiation energy density was 175 mJ/cm². Experimental results indicated that the optimum irradiation energy density for excimer laser annealing of ZnO sol–gel films was 150 mJ/cm². The ELA 150 thin films had a dense microstructure, an RMS roughness value of 5.30 nm, and an optical band gap of 3.38 eV, close to the band gap of a ZnO crystal (3.4 eV).     

Anode-supported SOFCs based on Sm0.2Ce0.8O2−δ electrolyte thin-films fabricated by co-pressing using microwave combustion synthesized powders

Decreasing the electrolyte thickness is an effective approach to improve solid oxide fuel cells (SOFCs) performance for intermediate-temperature applications. Sm_0.2Ce_0.8O_2−δ (SDC) powders with low apparent density of 32±0.3 mg cm⁻³ are synthesized by microwave combustion method, and SDC electrolyte films as thin as ~10 μm are fabricated by co-pressing the powders onto a porous NiO–SDC anode substrate. Dense SDC electrolyte thin films with grain size of 300–800 nm are achieved at a low co-firing temperature of 1200 °C. Single cells based on SDC thin films show peak power densities of 0.86 W cm⁻² at 650 °C using 3 vol% humidified H₂ as fuel and ambient air as oxidant. Both the thin thickness of electrolyte films and ultra-fine grained anode structure make contributions to the improved cell performance.     

Development of a superhydrophobic polyurethane-based coating from a two-step plasma-fluoroalkyl silane treatment

A method of achieving a superhydrophobic surface based upon a highly filled polyurethane (PU) paint coating has been demonstrated through the use of a combined oxygen/argon plasma pretreatment and a fluoroalkyl silane (FAS) final treatment.The combined plasma-FAS treated PU surface has been investigated and characterised using: field emission gun secondary electron microscope (FEG-SEM); X-ray photoelectron spectroscopy (XPS); energy-dispersive X-ray spectroscopy (EDX); water contact angle analysis (WCA); atomic force microscopy (AFM), and; Fourier transform infrared spectroscopy (FTIR).It was found that the oxygen/argon plasma treatment increased both the surface roughness (R_a) and surface free energy (SFE) of the PU paint coating from approximately 60–320 nm, and, from ~52 to ~80 mN/m respectively. It was also found that the plasma process created a multiscale roughened texture through the process of differential ablation between the PU polymer and the barium sulphate solid content, which is present in the paint as an extender, and other additives. In addition, the process also imparted favourable polar groups into the PU surface from the ionised and radical oxygen species in the plasma.When the FAS coating was subsequently applied to the PU without prior plasma treatment, there was a significant increases in water contact angles. This parameter increased from approximately 60° on untreated PU to around 130° with FAS applied. In this case, the SFE decreased to ~7.5 mN/m and showed 42.0 at% fluorine present as indicated by XPS.However, subsequently applying the FAS polymer after plasma pretreatment takes advantage of the known synergistic relationship that exists between surface roughness and low surface free energy coatings. The two processes combined to create superhydrophobicity with a surface that exhibited water contact angles up to 153.1°. With this optimised process, the apparent SFE was 0.84 mN/m with a more highly fluorinated surface present. In this case 47.2 at% surface fluorine was observed by XPS.In addition to changes in SFE, plasma treatment was also observed to alter levels of surface gloss and colour. After exposure to 600 s of plasma gloss levels are shown to reduce from values of from ~50 to ~21 (GU), with small but significant corresponding increases in the lightness and yellowness of the surface.     

Improved electrical conductivity of a non-covalently dispersed graphene–carbon nanotube film by chemical p-type doping

Using a high-pressure air spray we developed a method to deposit electrically-conducting thin films consisting of non-covalently dispersed graphene and carbon nanotubes. The graphene–carbon nanotube film was immersed in a nitric acid and followed by exposure to fuming nitric acid. The acid treatment induced an increased concentration of atomic nitrogen on the graphene basal plane and carbon nanotube sidewall. This result indicates chemical p-type doping of the graphene oxide–carbon nanotube film. After the two acid treatments, the spray coated graphene oxide–carbon nanotube films on a glass substrate exhibit a low sheet resistance of 171 Ω/sq, and a high transmittance of 84% at a wavelength of 550 nm.