Texture and nanostructure of pyrocarbon layers deposited on planar substrates in a hot-wall reactor

Pyrocarbon layers were deposited from methane on planar substrates (pyrolytic boron nitride) at a temperature of 1100 °C and residence times of 0.1, 0.5 and 2.5 s. The depositions were performed in a hot-wall reactor with the substrates oriented parallel to the gas flow. Transmission electron microscopy was applied to study the texture and the structure of the carbon layers on a micrometer and nanometer scale. The texture is influenced by the residence time. An alteration from medium- to high-textured carbon is observed from short to long residence times. The nanostructure of high- and medium-textured pyrocarbon is characterized by domains whose sizes do not generally differ.     

Influence of pressure, temperature and surface area/volume ratio on the texture of pyrolytic carbon deposited from methane

The kinetics of carbon deposition from methane were studied over broad ranges of pressures, temperatures and reciprocal surface area/volume ratios. Based on these results, it was possible to distinguish between a growth and a nucleation mechanism of carbon deposition and to select conditions for the preparation of well-defined samples for texture analysis by transmission electron microscopy and selected area electron diffraction. Maximal texture degrees were obtained at medium or high values of the above parameters, but never at low values, at which carbon formation is based on the growth mechanism and dominated by small linear hydrocarbons. High-textured carbon resulting from the growth mechanism is concluded to be formed from a gas phase with an optimum ratio of aromatic to small linear hydrocarbons, which supports the earlier proposed particle-filler model of carbon formation. High-textured carbon may also be formed from a gas phase dominated by polycyclic aromatic hydrocarbons (nucleation mechanism) provided that the residence time is sufficiently long that fully condensed, planar polycyclic aromatic hydrocarbons can be formed in the gas phase.     

Structural analysis of pyrolytic carbon deposits on a planar cordierite substrate

Pyrolytic carbon deposits were produced by chemical vapor deposition on a planar substrate of cordierite using methane as a source gas. The structure of the deposits was characterized by light microscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) combined with electron-energy-loss spectroscopy (EELS). The surface morphology is characterized by a cell structure induced by grains elongated perpendicular to the substrate surface. Energetic shift and intensity fluctuation of plasmon peaks in EELS spectra taken from cell and interface regions between the cells correlate with an alteration of the SEM image contrast observed on freshly fractured surfaces. This correlation suggests the presence of a mixture of two materials exhibiting different crystallization degrees. The material located at the interface is more amorphous-like in comparison to the graphite-like material located within cells.     

Deposition rates during the early stages of pyrolytic carbon deposition in a hot-wall reactor and the development of texture

Pyrolytic carbon layers were deposited from methane/oxygen/argon mixtures on planar substrates (silicon wafers) at a total pressure of 100 kPa, a maximum gas residence time of 2 s and a temperature of 1100 °C. The depositions were performed in a hot-wall reactor with the substrate oriented parallel to the gas flow. Particular attention was paid to factors that influence the reproducibility of the deposited layers. Scanning and transmission electron microscopy were applied to study the thickness profiles and the texture of the carbon layers. The surface topography was investigated by atomic force microscopy. For pyrolytic carbon deposited without oxygen, an alteration from medium- to high-textured carbon is observed with increasing residence time. Islands are observed on the surface of the layer whose size increases with the texture. For pyrolytic carbon deposited with 3% oxygen, lower deposition rates were obtained and a strong modification of the texture is found compared to gas mixtures without oxygen.     

Consideration of reaction mechanisms leading to pyrolytic carbon of different textures

A distinction between a growth and a nucleation mechanism is not sufficient to draw direct conclusions in relation to the texture of pyrolytic carbon. This is determined by the carbon formation mechanisms, which are analogous or at least similar to the mechanisms of aromatic growth. The latter mechanisms are reviewed in the first part of the paper with special consideration of structural chemical aspects. The relevance of the individual mechanisms is analyzed in the second part based on experimentally determined reaction products. Most important mechanisms are aryl-aryl combination, intramolecular dehydrocyclization and ethine addition reactions. The influence of mechanisms concerning an inhibition of the formation of five-membered rings and a transformation of five- into six-membered rings is difficult to estimate. The results indicate that a high textured carbon is formed from a gas phase exhibiting an optimum ratio of aromatic to small linear hydrocarbons (ethine). This model is called the particle-filler model (aromatic hydrocarbons: molecular particles; ethine: molecular filler).     

Liquid reagent CVD of carbon. I. Processing and microstructure

The processing and microstructure of carbon coatings deposited using liquid reagent CVD were studied. High density pyrolytic carbon coatings were successfully deposited on graphite and molybdenum substrates from benzene and cyclohexane precursors. Very high deposition rates were obtained. Examination via transmission electron microscopy showed that the deposits were of the desired turbostratic nodular structure with low texture.     

Textures of pyrolytic carbon formed in the chemical vapor infiltration of capillaries

Capillaries, 1.1 mm in diameter and 17.0 or 32.5 mm in length, were infiltrated at a temperature of 1100 °C and methane pressures from 5 to 30 kPa. Layer thickness and carbon texture were determined at cross-sections of 2, 16 and 32 mm from the open end of the capillaries using polarized light microscopy. Average deposition rates, determined from layer thickness and infiltration time, as a function of methane pressure indicate a rate increase up to a saturation adsorption at pressures between 10 and 15 kPa (range 1) and a strong rate increase above these pressures (range 2). This result implies carbon formations based on the growth mechanism in range 1 and the nucleation mechanism in range 2. The carbon texture shows a maximum in range 1 and a minimum in the transition from range 1 to range 2 followed by a clear increase in range 2. The maximum in range 1 corresponds to the particle-filler model describing formation of various textures of carbon by the ratio of aromatic species to C₂ species. Increasing texture degrees in range 2 suggest that the nucleation mechanism may lead to high textured carbon provided that the residence time for intramolecular rearrangments of polycyclic aromatic hydrocarbons is sufficient.     

Synthesis of vertically aligned carbon nanotubes on metal deposited quartz plates

Without plasma aid, we have successfully synthesized vertically aligned carbon nanotubes (CNTs) on iron-, cobalt- or nickel-deposited quartz plates by chemical vapor deposition with ethylenediamine as a precursor. The amine serves as both etching reagent for the formation of metal nanoparticles and carbon source for the growth of aligned carbon nanotubes. The carbon nanotubes were vertically aligned in high density on a large area of the plain silica substrates. The density and diameter of CNTs is determined by the thickness of the deposited metal film and the length of the tubes can be controlled by varying the reaction time. High-resolution transmission electron microscopy analysis reveals that the synthesized CNTs are multiwalled with a bamboo-like structure. Energy dispersive X-ray spectra demonstrate that the CNTs are formed as tip growths. Raman spectrum provides definite evidence that the prepared CNTs are multiwalled graphitic structure.     

Synthesis and characteristics of iron nanoparticles in a carbon matrix along with the catalytic graphitization of amorphous carbon

Iron nanoparticles in a carbon matrix were synthesized by in situ pyrolysis of maleic anhydride and ferrocene, using different molecular weight percentages. The characterization and magnetic properties of the carbon-iron system were investigated systematically. Transmission electron microscope (TEM) images showed that the as-prepared samples consist of nanometric dark grains (iron-rich phase) embedded in a light matrix (carbon-rich phase). X-ray diffraction and TEM selected area diffraction revealed catalytic graphitization and iron phases present in the sample. The carbon-metal system shows a finite hysteresis loop even at room temperature indicating its ferromagnetic nature. The saturation magnetization equals the bulk iron carbide value at low temperature. The coercive force exhibits 1/d dependence at low temperature having a maximum H_C of 2 kOe for the lowest iron concentration sample.     

Chemical vapor deposition of pyrolytic carbon on carbon nanotubes: Part 1. Synthesis and morphology

The chemical vapor deposition of the pyrocarbon from a CH₄+H₂ mixture is investigated using nanofilamentous substrates. The process consists of growing carbon nanotubes via a catalytic process, which then are thickened by pyrolytic carbon deposition to reach diameters in the nanometer to micrometer range. A key characteristic of the experimental reactor used was the long length of its isothermal zone, preceded (and followed) by a low thermal gradient zone. This allowed us to investigate the role of the variation of the local gas phase composition, which depends on the post-cracking secondary reactions, and on the quantity and quality of the deposited carbon. The ‘time of flight’ of the reactive species was found to be a leading parameter in the pyrolytic carbon deposition process. Various nanometric and micrometric morphologies, several of which are new, were synthesised and found constituted with an association of different sub-morphologies. The various morphologies, that can be sorted following a factor of morphological complexity, were investigated by scanning electron microscopy.     

Kinetics of surface reactions in carbon deposition from light hydrocarbons

Carbon deposition from ethene, ethine and propene as a function of pressure was studied at various temperatures and two different surface area/volume ratios. Deposition rates as a function of pressure of all hydrocarbons indicate Langmuir-Hinshelwood kinetics which suggests that the deposition process is controlled by the heterogeneous surface reactions (growth mechanism). These kinetics are favored at decreasing reactivity (C₃H₆>C₂H₂>C₂H₄), decreasing temperature and residence time as well as increasing surface area/volume ratio. A linear rate increase at high pressures suggests that carbon is additionally or preferentially deposited by aromatic condensation reactions between polycyclic aromatic hydrocarbons large enough to be physisorbed or condensed on the substrate surface (nucleation mechanism). The results completely agree with earlier results obtained with methane.     

Nanostructures of pyrolytic carbon from a polyacetylene thin film

Pyrolysis of a polyacetylene thin film has been performed in order to carbonize at temperatures of 500 to 1000 °C in vacuum. A trans-polyacetylene thin film was synthesized using a Ziegler-Natta catalyst. A black char below 20% in weight of the original PA film remained after pyrolysis. Structural properties and morphology of the black chars were investigated using Raman scattering spectrum, X-ray diffraction measurements, and scanning and transmission electron microscopy. Dehydrogenation and carbonization of the PA film were almost finished at a pyrolysis temperature of 800 °C. However, hollow spherical or elliptical nano-particles of tens of nanometers in size, which are composed of graphite structure, were included in the black chars obtained at all pyrolysis temperatures in this work. The formation mechanism of a graphite crystal in nanometer size from a PA crystal was discussed.     

Chemistry and kinetics of chemical vapor deposition of pyrocarbon: VI. influence of temperature using methane as a carbon source

The chemical vapor deposition of carbon from methane was investigated at an ambient pressure of about 100 kPa, a methane partial pressure of 10 kPa and temperatures ranging from 1050–1125°C. Carbon deposition rates and compositions of the gas phase as a function of residence time have been determined using a substrate with a surface area/reactor volume ratio of 40 cm⁻¹. Increasing temperatures lead to strongly increasing deposition rates, decreasing partial pressures of ethane and increasing partial pressures of ethene, ethine and benzene. The overall activation energy of carbon deposition, determined from the initial deposition rates at a residence time versus zero amounts to 446 kJ/mol as compared to 431.5, 448 and 452.5 kJ/mol reported in earlier papers. Two possible rate-limiting steps are discussed, namely dissociation of methane, which is favored in the earlier papers, and dissociation of carbon–hydrogen surface complexes.     

Influence of the surface area/volume ratio on the chemistry of carbon deposition from methane

The chemistry of carbon deposition from methane as a function of methane pressure was studied at a temperature of 1100 °C and surface area/volume ratios of 0.8 and 3.2 mm⁻¹ by analysis of both gaseous and condensing, i.e. aromatic reaction products. Conversion of methane as well as the yields of the hydrocarbons formed increase with increasing pressure. The surface area/volume ratio has a significant influence on the formation of aromatic hydrocarbons showing much higher yields at the lower ratio. This result, expected from preceding studies of deposition rates, confirms that a change of this ratio leads to a change of the deposition chemistry of carbon.     

Pyrocarbons

A review of literature on various kinds of pyrocarbons is given. Their characterization by optical microscopy, TEM imaging (transmission electron microscopy) and diffraction techniques is discussed. Various models are also described critically, as well as the possible mechanisms of deposition.