Nanostructured Carbon Films Research Articles

Nanostructured carbon films with oriented graphitic planes

Nanostructured carbon films with oriented graphitic planes can be deposited by applying energetic carbon bombardment. The present work shows the possibility of structuring graphitic planes perpendicular to the substrate in following two distinct ways: (i) applying sufficiently large carbon energies for deposition at room temperature (E>10 keV), (ii) utilizing much lower energies for deposition at elevated substrate temperatures (T>200 °C). High resolution transmission electron microscopy is used to probe the graphitic planes. The alignment achieved at elevated temperatures does not depend on the deposition angle. The data provides insight into the mechanisms leading to the growth of oriented graphitic planes under different conditions.

Efficient Direct Electron Transfer with Enzyme on a Nanostructured Carbon Film Fabricated with a Maskless Top-Down UV/Ozone Process

We have developed a new carbon film electrode material with thornlike surface nanostructures to realize efficient direct electron transfer (DET) with enzymes, which is very important for various enzyme biosensors and for anodes or cathodes used in biofuel cells. The nanostructures were fabricated using UV/ozone treatment without a mask, and the obtained nanostructures were typically 2-3.5 nm high as confirmed by atomic force microscopy measurements. X-ray photoelectron spectroscopy and transmission electron microscopy revealed that these nanostructures could be formed by employing significantly different etching rates depending on nanometer-order differences in the local sp(3) content of the nanocarbon film, which we fabricated with the electron cyclotron resonance sputtering method. These structures could not be realized using other carbon films such as boron-doped diamond, glassy carbon, pyrolyzed polymers based on spin-coated polyimide or vacuum-deposited phthalocyanine films, or diamond-like carbon films because those carbon films have relatively homogeneous structures or micrometer-order crystalline structures. With physically adsorbed bilirubin oxidase on the nanostructured carbon surface, the DET catalytic current amplification was 30 times greater than that obtained with the original carbon film with a flat surface. This efficient DET of an enzyme could not be achieved by changing the hydrophilicity of the flat carbon surface, suggesting that DET was accelerated by the formation of nanostructures with a hydrophilic surface. Efficient DET was also observed using cytochrome c.

Improved adhesion of ultra-hard carbon films on cobalt–chromium orthopaedic implant alloy

While interfacial graphite formation and subsequent poor film adhesion is commonly reported for chemical vapor deposited hard carbon films on cobalt-based materials, we find the presence of O(2) in the feedgas mixture to be useful in achieving adhesion on a CoCrMo alloy. Nucleation studies of surface structure before formation of fully coalesced hard carbon films reveal that O(2) feedgas helps mask the catalytic effect of cobalt with carbon through early formation of chromium oxides and carbides. The chromium oxides, in particular, act as a diffusion barrier to cobalt, minimizing its migration to the surface where it would otherwise interact deleteriously with carbon to form graphite. When O(2) is not used, graphitic soot forms and films delaminate readily upon cooling to room temperature. Continuous 1μm-thick nanostructured carbon films grown with O(2) remain adhered with measured hardness of 60GPa and show stable, non-catastrophic circumferential micro-cracks near the edges of indent craters made using Rockwell indentation.

Ellipsometric study of nanostructured carbon films deposited by pulsed laser deposition

When depositing carbon films by plasma processes the resulting structure and bonding nature strongly depends on the plasma energy and background gas pressure. To produce different energy plasma, glassy carbon targets were ablated by laser pulses of different excimer lasers: KrF (248nm) and ArF (193nm). To modify plume characteristics argon atmosphere was applied. The laser plume was directed onto Si substrates, where the films were grown. To evaluate ellipsometric measurements first a combination of the Tauc-Lorentz oscillator and the Sellmeier formula (TL/S) was applied. Effective Medium Approximation models were also used to investigate film properties. Applying argon pressures above 10Pa the deposits became nanostructured as indicated by high resolution scanning electron microscopy. Above ~100 and ~20Pa films could not be deposited by KrF and ArF laser, respectively. Our ellipsometric investigations showed, that with increasing pressure the maximal refractive index of both series decreased, while the optical band gap starts with a decrease, but shows a non monotonous course. Correlation between the size of the nanostructures, bonding structure, which was followed by Raman spectroscopy and optical properties were also investigated.

Physical properties of chemical vapour deposited nanostructured carbon thin films

A simple thermal chemical vapour deposition technique is employed for the deposition of carbon films by pyrolysing the natural precursor “turpentine oil” on to the stainless steel (SS) and FTO coated quartz substrates at higher temperatures (700–1100 °C). In this work, we have studied the influence of substrate and deposition temperature on the evolution of structural and morphological properties of nanostructured carbon films. The films were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), contact angle measurements, Fourier transform infrared (FTIR) and Raman spectroscopy techniques. XRD study reveals that the films are polycrystalline exhibiting hexagonal and face-centered cubic structures on SS and FTO coated glass substrates respectively. SEM images show the porous and agglomerated surface of the films. Deposited carbon films show the hydrophobic nature. FTIR study displays C–H and O–H stretching vibration modes in the films. Raman analysis shows that, high ID/IG for FTO substrate confirms the dominance of sp 3 bonds with diamond phase and less for SS shows graphitization effect with dominant sp 2 bonds. It reveals the difference in local microstructure of carbon deposits leading to variation in contact angle and hardness, which is ascribed to difference in the packing density of carbon films, as observed also by Raman.

Structural and electrical properties of nanostructured silicon carbon films

Abstract The effect of the rf power on the structural and electrical properties of nanostructured silicon carbon films deposited by Plasma Enhanced Chemical Vapour Deposition system, using silane and methane gas mixture highly diluted in hydrogen, has been investigated. The structural and electrical properties are found to depend strongly on rf power. The increase of the rf power decreases the size of the silicon crystallites as well as the crystalline fraction and increases the carbon content in the films. The study not only indicates the correlation between crystalline fraction and the electrical conductivity but also reveals the presence of nanocrystallites in the films deposited at high rf power.

Relationship between structure and electrical resistivity in nano-structured copper-containing carbon films

Abstract The microstructure evolution of carbon/copper (C/Cu) films and its relation to the variation of film electrical resistivity has been studied. The films doped with copper in the range of 1.4–22.6 at.% Cu, were deposited by dc magnetron sputtering of composite graphite–copper target. The microstructure of films was studied by Raman spectroscopy and electron diffraction. The electrical resistivity was measured parallel and perpendicular to the substrate surface. The introducing of copper atoms into carbon matrix which consists of disordered graphite-like nano-clusters results in additional distortion of film microstructure at low copper content and some ordering of it at high copper content. At low copper concentrations the additional distortion of graphite-like clusters prevails over the input to electrical conductivity from copper atoms thus increasing the electrical resistivity of C/Cu films. At high copper concentrations the input to electrical conductivity is predominant and the film resistivity decreases.

Optical Chacterization of Plasma Enhanced Chemical Vapor Deposition of Nanocarbon Film Materials

In this paper we describe the optical emission spectroscopy studies of a plasma enhanced chemical vapor deposition of nanostructured carbon films. The nano-carbon films were deposited from a hydrogen-methane gas mixture activated by a direct current discharge. The gas discharge plasma parameters providing a stable synthesis of different carbon films have been determined. The optical emission spectra have been obtained for the discharge plasma at different pressures and gas compositions of the plasma environment. A correlation between a graphite-like structure formation and a presence of carbon dimers C 2 in the activated gas mixture has been found. A characteristic optical emission of C 2 in swan-band was analyzed to determine a spatial distribution of the carbon dimers in plasma environment.

Wettability of Ultrananocrystalline Diamond and Graphite Nanowalls Films: A Comparison with Their Single Crystal Analogs

Dramatic changes in wettability of diamond and graphite are observed when these materials are prepared in nanostructured forms--undoped and nitrogen-doped ultrananocrystalline diamond (UNCD) films, and graphite nanowalls (GNW), respectively. The nanostructured carbon films were deposited on Si by microwave plasma CVD processes. The advancing contact angle theta for water on hydrogenated undoped UNCD films increases to 106 +/- 3 degrees compared to hydrogenated single crystal diamond (theta = 92 degrees). Nitrogen doping (N2 addition to plasma) during UNCD growth makes the film more hydrophilic. The GNW films exhibited superhydrophobic behavior with theta = 144 +/- 3 degrees for water, which is higher than the contact angle of monocrystalline graphite (the basal plane) by a factor of 1.8. No chemical surface treatment is necessary to achieve such high hydrophobicity, it is accomplished solely by a specific (nanoporous, high aspect ratio) surface morphology with very low free surface energy inherent in it. The wetting behaviour of nanostructured films can be described with the Cassie-Baxter equation for heterophase nanoporous surfaces. Oxidation and hydrogenation of UNCD films make it possible to control theta over a much wider range as compared to a single crystal diamond. The influence of diamond grain size on wetting is considered taking into account the surface treatment. The corresponding variation in surface energy has been determined by the modified Young's equation.

Influence of substrate surface topography in the deposition of nanostructured diamond-like carbon films by high density plasma chemical vapor deposition

In this work, we have studied the influence of the substrate surface condition on the roughness and the structure of the nanostructured DLC films deposited by High Density Plasma Chemical Vapor Deposition. Four methods were used to modify the silicon wafers surface before starting the deposition processes of the nanostructured DLC films: micro-diamond powder dispersion, micro-graphite powder dispersion, and roughness generation by wet chemical etching and roughness generation by plasma etching. The reference wafer was only submitted to a chemical cleaning. It was possible to see that the final roughness and the sp 3 hybridization degree strongly depend on the substrate surface conditions. The surface roughness was observed by AFM and SEM and the hybridization degree of the DLC films was analyzed by Raman Spectroscopy. In these samples, the final roughness and the sp 3 hybridization quantity depend strongly on the substrate surface condition. Thus, the effects of the substrate surface on the DLC film structure were confirmed. These phenomena can be explained by the fact that the locally higher surface energy and the sharp edges may induce local defects promoting the nanostructured characteristics in the DLC films.

Investigation of electrical properties of nanostructured carbon films derived from block copolymers

Electrical properties of nanostructured carbon (ns-C) films fabricated by pyrolysis of PAN–b–PBA copolymers were investigated. Films having cylindrical morphology and pyrolyzed at 400, 500 and 600 °C were investigated. Both carbide forming (Zr, Ti) and non-carbide forming (Cu, Pt) metals spanning a wide range of electron work functions (4.1–5.5 eV) formed ohmic contacts to the ns-C films in the as-deposited state. The conductivity of the ns-C films increased roughly three orders of magnitude for every 100 °C increase in the pyrolysis temperature. Hall-effect measurements showed that the films pyrolyzed at 600 °C were n-type with a majority carrier concentration and mobility of 5.8 × 10 18 cm −3 and 0.97 cm 2/V s, respectively. Current–voltage measurements as a function of temperature ( I– V– T) were performed on films pyrolyzed at 600 °C, whereas films pyrolyzed at 400 and 500 °C were too resistive for reliable resistivity–temperature and Hall-effect measurements. The resistivity as a function of temperature was analyzed by using the reduced activation energy method and was determined to follow variable-range hopping (VRH) mechanisms at and below room temperature. The data indicates a crossover from Efros–Shklovskii VRH [J. Phys. C 8, (1975) L49] to Mott VRH [J. Non-Cryst. Solids 1, (1968) 1] at temperatures above 100 K.

Field emission characteristics of nano-structured carbon films deposited on differently pretreated Mo films

Nano-structured carbon films (NCFs) were grown on Mo layers by microwave plasma chemical vapor deposition (MPCVD) system. The Mo layers were deposited on ceramic substrates by electron beam deposition method and were pretreated by different techniques, which include ultrasonically scratching and laser-grooving technology (10 line/mm). NCFs were characterized by a field emission type scanning electron microscope (FE-SEM), Raman spectra and field emission (FE) I– V measurements. Effects of process parameters on morphologies, structures and FE properties of NCFs were examined. The experimental results show that two kinds of NCFs deposited at the same parameters employed for the MPCVD process were respectively composed of carbon nano-balls and reticular carbon nano-tubes inlayed by carbon nano-balls with dissimilar disorder structures, both NCFs showed each merits and exhibited good field emission properties, especially shown in the uniformity of FE, the uniform field emission images with areas of 4 cm 2 were obtained. Growth mechanism influenced by different pretreated method was discussed and the possible FE mechanisms of the NCFs were also investigated. Finally, the process characteristics of laser-grooving technology were analyzed, and its potential applications were predicted.

Formation of linear carbon chains during the initial stage of nanostructured carbon film growth

The initial stage of nanostructured carbon film growth is investigated by molecular dynamics simulations. The carbon film exhibits amorphous structures with linear chains and cyclic rings on the surface at low incident energies. The structural transformations from linear chains to cyclic rings and to atom networks are observed during the growth process, which is explained in terms of system stability. The atomic adsorption behavior is analyzed through the calculation of the surface potential field. The formation of linear chain structure is due to the predominance of inhomogeneous adsorption of incident atoms on the surface and preferential growth at the tip of the chain. The formation of nanostructures on the surface is argued to be the initial nucleation process of amorphous carbon films.

Correlations between switching of conductivity and optical radiation observed in thin graphite-like films

The satisfactory explanation of anomalous electromagnetics in thin graphite-like carbon films till now is absent. The most comprehensible explanation may be the high-temperature superconductivity (HTSC). The pulse widths of spasmodic switching of electrical conductivity measured in this work in the graphite-like nanostructured carbon films, produced by methods of the carbon arc (CA) and chemical vapor deposition (CVD), are 1 and 2 ns correspondingly. Such fast switching completely excludes the thermal mechanism of the process. According to HTSC logic, in the time vicinity close to jump of electroresistance, it is necessary to expect the generation of optical radiation in the infrared (IR) range. This work presents the first results on registration of IR radiation caused by the sharp change of conductivity in thin graphite-like carbon films.

Interaction of artificial carbon pyroceram mitral valve with blood plasma

The nanocrystalline material of an artificial carbon pyroceram mitral valve obtained by sintering of 15 wt.% B4C with crystals <10 nm that are uniformly distributed in 85 wt.% carbon with particles ∼10 nm has exceptionally high chemical stability in blood plasma. The electrochemical interaction resulting from contact with a possible microadditive (for example, iron) on the valve surface is experimentally modeled by polarization induced by an external current source specially to create extreme corrosion conditions. The interaction kinetics is studied at 37 °C using anodic polarization curves. Curcumin is used as an analytical reagent for spectrophotometry of boron traces in a solution. Emissive spectroscopy is used to determine iron traces in the spume-like film formed after polarization. It is established that a chemisorbed oxygen film forms when microgalvanic elements appear at 0.4 V and stable passivation of the valve surface is observed at ∼1.0 V since a low-conductive nanostructured carbon film forms. It is shown that this film results from the discharge of α-amino acids on the valve surface (amino acid residues of complex peptide chains of plasma proteins) containing heterocyclic rings. The sessile drop method shows that the valve is promptly wetted by blood plasma (wetting angle is 50 °), this also promotes the formation of a stable protective film on its surface.

Field emission properties of nano-structured carbon films with carbon needles deposited on Si using high-power-density microwave-plasma CVD method

Nano-structured carbon films (NCFs) were fabricated on Si wafer chips with hydrogen–methane gas mixture by creating high-power-density microwave (MW) plasma in a quartz tube with a low-output MW power source. Carbon sheets with many nano-protuberances were complicatedly twisted each other in the center region of the NCF while carbon needles were additionally formed in the fringe region of the NCF. These NCFs yielded field emission (FE) characteristics with the FE current density of 68 mA/cm 2 at a macroscopic electric field, E, of 10 V/μm. Since the FE currents tended to be saturated even in a medium E region, no simple Fowler–Nordheim (F–N) model was applicable. A model considering the F–N mechanism, statistic effects of FE tip structures and a space-charge-limited-current effect has been applied successfully to explain all the FE data observed for E < 10 V/μm. It turned out that E-dependent parameters such as the effective total emission area and the effective field enhancement factor should be employed to obtain sufficient quantitative agreements between the model and the experiments.

Nano-graphene structures deposited by N-IR pulsed laser ablation of graphite on Si

Thin nano-structured carbon films have been deposited in vacuum by pulsed laser ablation, from a rotating polycrystalline graphite target, on Si 〈1 0 0〉 substrates, kept at temperatures ranging from RT to 800 °C. The laser ablation was performed by a Nd:YAG laser, operating in the near IR ( λ = 1064 nm). X-ray diffraction analysis, performed at grazing incidence angle, both in-plane (ip-gid) and out-of-plane (op-gid), has shown the growth of oriented nano-sized graphene particles, characterised by high inter-planar stacking distance ( d č ∼ 0.39 nm), compared to graphite. The film structure and texturing are strongly related both to laser wavelength and substrate temperature: the low energy associated to the IR laser radiation (1.17 eV) generates activated carbon species of large dimensions that, also at low T (∼400 °C), easy evolve toward more stable sp 2 aromatic bonds, in the plume direction. Increasing temperature the nano-structure formation increases, causing a further aggregation of aromatic planes, voids formation, and a related density (by X-ray reflectivity) drop to very low values. SEM and STM show for these samples a strongly increased macroscopic roughness. The whole process, mainly at higher temperatures, is characterised by a fast kinetic mode, far from equilibrium and without any structural or spatial rearrangement.

Facile Synthesis of Nanostructured Carbon through Self‐Assembly between Block Copolymers and Carbohydrates

AbstractA simple and direct wet chemistry method is reported to simultaneously synthesize nanostructured carbon films and particles through self‐assembly of poly(styrene)‐poly(4‐vinylpyridine) (PS‐P4VP) and carbohydrate precursors (turanose, raffinose, glucose, etc.) in two fabrication processes—spin‐coating and aerosol processing. Starting with a homogeneous solution containing PS‐P4VP and carbohydrates, evaporation of solvent during either spin‐coating or an aerosol process leads to the formation of ordered mesostructured films and particles. High temperature treatment in argon atmosphere removes PS fragments, carbonizes carbohydrates and partial PVP fragments, and results in ordered nanoporous carbon films and particles. SEM, TEM, and GISAXS characterization indicates that these nanostructured carbon materials exhibit large nanopores (&gt; 20 nm), controlled 1–3 dimensional structures, and controlled surface chemistry. Nitrogen sorption isotherms and electrochemistry characterization indicates the accessibility of the carbon nanopores to both gas phase and aqueous phase. Results suggest that the nanostructured carbon films and particles can be tuned through solvent annealing, precursor concentration, and choice of block copolymers used. These carbon materials present varied practical applications for sorption and separation, sensors, electrode materials, etc.

Spectroscopic characterization of carbon chains in nanostructured tetrahedral carbon films synthesized by femtosecond pulsed laser deposition

A comparative study of carbon bonding states and Raman spectra is reported for amorphous diamondlike carbon films deposited using 120 fs and 30 ns pulsed laser ablation of graphite. The presence of sp(1) chains in femtosecond carbon films is confirmed by the appearance of a broad excitation band at 2000-2200 cm(-1) in UV-Raman spectra. Analysis of Raman spectra indicates that the concentrations of sp(1)-, sp(2)-, and sp(3)-bonded carbon are approximately 6%, approximately 43%, and approximately 51%, respectively, in carbon films prepared by femtosecond laser ablation. Using surface enhanced Raman spectroscopy, specific vibrational frequencies associated with polycumulene, polyyne, and trans-polyacetylene chains have been identified. The present study provides further insight into the composition and structure of tetrahedral carbon films containing both sp(2) clusters and sp(1) chains.

Electrical conductivity of cluster-assembled carbon/titania nanocomposite films irradiated by highly focused vacuum ultraviolet photon beams

We investigated the electrical transport properties of nanostructured carbon and carbon/titanium oxide nanocomposite films produced by supersonic cluster beam deposition and irradiated by highly focused vacuum UV photon beam. We have observed a relevant increase of the density of states at Fermi level, suggesting that the films acquire a “metallic” character. This is confirmed by the increment of the conductivity of four orders of magnitude for pure nanostructured carbon films and at least eight orders of magnitude for films containing 9at.% of titanium. A partial reversibility of the process is observed by exposing the modified films to molecular oxygen or directly to air. We demonstrate the capability of writing micrometric conductive strips (2–3μm width and 60μm length) and controlling the variation of the conductivity as a function of the titanium concentration.