Microstructure and integrity of multilayer ceramic coating with alumina top coat on silicon carbide by laser chemical vapor deposition

Thin double-layer coatings comprising an alumina top coat and mullite bond coat were deposited on SiC substrates by laser chemical vapor deposition (CVD). The effect of the presence of mullite bond coat and the phases of alumina top coat on the structural integrity against the thermal residual stress loaded by the high-temperature CVD process was examined by microstructural characterization and simulative consideration. A laminated layered structure having a dense γ-alumina top surface with a cone-like morphology are grown at a deposition temperature of 1323 K, whereas an α-alumina top layer comprising densely packed faceted grains was grown at 1473 K. The interfaces between the SiC and mullite layers were coherent owing to the formation of a thin transition layer. The γ-alumina layer formed an adhesive interface bordering the mullite layer, whereas small residual defects were formed in the α-alumina layer bordering the mullite layer. Spacings of surface cracking induced by the high-temperature deposition process in the double-layer coatings were approximately half of those in the coatings without mullite layers. As simulative results by finite element method suggested, the double-layer coatings were experimentally verified to be more tolerant to the formation of surface cracks and interfacial delamination, compared to single-layer coatings without the mullite bond layers.     

Influence of pressure on chemical vapor deposition of boron nitride from BCl3/NH3/H2 gas mixtures

Boron nitride (BN) was synthesized from BCl₃/NH₃/H₂ precursor mixtures via chemical vapor deposition, with a focus on the influence of the total partial pressure of BCl₃, NH₃, and H₂ (p_BCl3+NH3+H2) on the surface deposition rate. The surface deposition rate of BN initially increased and then decreased with increasing p_BCl3+NH3+H2, implying that the deposition process transitioned from surface reaction control to mass transfer control. BN deposition from BCl₃ and NH₃ was mainly attributable to several intermediate gaseous products containing B, N, Cl, and H, such as Cl₂BNH₂, ClB(NH₂)₂, and B(NH₂)₃. The microstructures of BN coatings deposited on SiC fibers were also analyzed. The BN coatings were uniformly and evenly deposited on the SiC fiber surfaces at low p_BCl3+NH3+H2 values, whereas excessive p_BCl3+NH3+H2 values afforded coatings containing large grains. The as-prepared BN coatings were stoichiometric but amorphous. Heat treatment substantially improved the texture and crystallinity to afford hexagonal BN.     

Structure,microstructure and disorder in low temperature chemical vapor deposited SiC coatings

Chemical vapor deposited SiC coatings were investigated at different scales by X-Ray diffraction, Raman microspectroscopy and transmission electron microscopy. They were prepared under specific conditions explaining the various (micro)structures obtained. The deposits all have a columnar morphology with a preferential orientation and a faulted cubic structure. They differ in how disorder is incorporated in the structure. Fine XRD analyses and stacking fault density assessment by TEM revealed the one-dimensionally-disordered (ODD) polytype in the < 111 > textured coatings. The frequency and spatial distribution of stacking faults vary and sometimes locally generate periodic alpha sequences. A specific type of disorder was also identified where {111} planes are arranged parallel to the growth direction within the columns. These disorders, more energetic than stacking faults, induce multiple and particularly large Raman modes. Crystal distortions, such as dislocations, are localized at the ODD domain boundaries, which are frequently interrupted as they extend during the growth.     

Influence of total pressure on the microstructures and growth mechanism of ZrC coatings prepared by chemical vapor deposition from the Zr-Br2-C3H6-H2-Ar system

Zirconium carbide (ZrC) coatings were deposited on graphite substrates by chemical vapor deposition from the Zr-Br₂-C₃H₆-H₂-Ar system. The influence of total pressure on the growth of ZrC was investigated in the range of 5–60 kPa. As the total pressure increased, the deposition rate increased evidently, and the preferential orientation of ZrC coatings changed from the (200) plane to the (220) plane. The growth mechanism changed from a mass transport reaction to a surface reaction at the total pressure of 20–40 kPa. At the total pressure below 20 kPa, the deposition was dominated by crystal growth, so the coatings were composed of well-faceted pyramidal-shaped crystals growing along the <001> direction. At the total pressure above 60 kPa, the growth of ZrC coatings was controlled by the nucleation mechanism, so the coatings were cluster-like crystals rapidly growing along the <110> direction. In addition, low pressure was conducive to the formation of near-stoichiometric ZrC without free carbon. These variations of ZrC coatings can mainly be attributed to gas supersaturation and remarkably changed transport diffusion coefficients with increasing total pressure.     

Synthesis and microstructure of the Ti3SiC2 in SiC matrix grown by chemical vapor deposition

Ti₃SiC₂ + SiC and TiC + SiC were deposited on graphite substrate at 1300–1600 °C by chemical vapor deposition with TiCl₄, SiCl₄, C₃H₈, H₂ as reactive gases. Process parameters such as temperature, pressure, concentration of C₃H₈ were varied to study their effects on the phases and microstructure of the deposited layers. The results show that binary phases of Ti₃SiC₂ + SiC are formed at temperature less than 1400 °C. For temperature above 1500 °C, TiC + SiC phases are formed. Increase of the process pressure causes the disappearance of Ti₃SiC₂ and the formation of TiC. The surface morphology of Ti₃SiC₂ shows a plate-like structure. The hardness of Ti₃SiC₂ + SiC and TiC + SiC is HV4251 and HV4612 respectively for a load of 10 g.     

Effect of the reaction atmosphere on the diameter of single-walled carbon nanotubes produced by chemical vapor deposition

The influence of the reaction atmosphere on the type of single-walled carbon nanotubes (SWNT) grown during chemical vapor deposition (CVD) was investigated. Methane decomposition was catalyzed by Fe/MgO and Fe-Mo/MgO catalysts in argon, nitrogen and their mixtures. Nitrogen influences the carbon species significantly. The aggregation of iron nanoparticles in nitrogen results in the growth of N-doped carbon nanofibers on the Fe/MgO catalyst. A limited iron nanoparticle aggregation in nitrogen occurred on a Fe-Mo/MgO catalyst, on which there was an increase in the diameter of the SWNTs as the reaction atmosphere was more enriched in nitrogen, which was characterized by Raman spectroscopy. These results provide an experimental basis for the rational selection of the reaction atmosphere, and suggest an approach to control the size of the SWNTs in a CVD method.     

Local chemical vapor deposition of carbon nanofibers from photoresist

The addition of nanofeatures to carbon microelectromechanical system (C-MEMS) structures would greatly increase surface area and enhance their performance in miniature batteries, super-capacitors, electrochemical and biological sensors. Negative photoresist posts were patterned on a Au/Ti contact layer by photolithography. After pyrolyzing the photoresist patterns to carbon patterns, graphitic nanofibers were observed near the contact layer. The incorporation of carbon nanofibers in C-MEMS structures via a simple pyrolysis of modified photoresist was investigated. Both experimental results considered to consist of a local chemical vapor deposition mechanism. The method represents a novel, elegant and inexpensive way to equip carbon microfeatures with nanostructures, in a process that could possibly be scaled up to the mass production of many electronic and biological devices.     

HfB2 coating on C/C composites prepared by chemical vapor deposition: Thermodynamics and experimental investigation

A thermodynamic calculation on the HfB₂ coating prepared by chemical vapor deposition (CVD) through HfCl₄-BCl₃-H₂-Ar system was performed, together with the relevant verification experiments. The calculation results indicated that HfB₂ coating could be obtained above 900 °C with the ratios of BCl₃/HfCl₄ and H₂/HfCl₄ higher than 1 and 12, respectively. The experimental results demonstrated that the deposition temperature, H₂ and BCl₃ flow rates had significant effects on the grain size, growth rate and phase composition of HfB₂ coatings. A dense and uniform HfB₂ coating was prepared at 1150 °C with a BCl₃/HfCl₄ ratio of 3 and a H₂/HfCl₄ ratio of 20, whose mass and linear ablation rates were 15.61 mg/s and 15.58 μm/s under oxyacetylene flame.     

Mechanism of carbon nanotube growth from camphor and camphor analogs by chemical vapor deposition

Single walled nanotubes have been synthesized by chemical vapor deposition from camphor, camphor analogs (camphorquinone, norcamphor, norbornane, camphene, fenchone), and various other precursors (menthone, 2-decanone, benzene, methane). The high temperature conditions (865 °C) and Fe/Mo alumina catalyst used in the syntheses are archetypal conditions for the production of single walled carbon nanotubes. It has been shown that the mechanism of tube growth is unlikely to depend upon the production of reactive five- and six-member rings, as has been previously suggested. The results suggest that the presence of oxygen in the precursor does not significantly improve the quality of tubes by etching amorphous carbon: it is suggested that the control of the flux of the precursor to the catalyst is more important in the production of high quality tubes. There is, however, evidence for different distributions of tube diameter being produced from different precursors.     

Fabrication of an ultra-thick-oriented 3C-SiC coating on the inner surface of a graphite tube by high-frequency induction-heated halide chemical vapor deposition

Cubic SiC (3C-SiC) is a promising material for nuclear industry applications due to its excellent properties. In this report, a highly oriented thick 3C-SiC coating with good crystallinity was prepared on the inner surface of a monolithic graphite tube via high-frequency induction-heated halide chemical vapor deposition using SiCl₄, CH₄, and H₂ as precursors. The texture coefficient (T_C(hkl)), microstructure, and deposition rate along the tube axis was studied. 3C-SiC coating with a high (111) orientation and crystallinity was obtained. Along the tube axis, T_C(111) was consistent with the temperature distribution. The surficial morphology of the 3C-SiC coating changed from pebble-like to hexangular facet and then to hemispherical. The deposition rate and coating thickness were 300 μm/h and 615 μm, respectively, which is sufficiently rapid and thick enough to obtain free-standing SiC tubes for nuclear reactors.     

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.     

Field emission properties of carbon nanotubes synthesized by capillary type atmospheric pressure plasma enhanced chemical vapor deposition at low temperature

Carbon nanotubes (CNTs) were grown using a modified atmospheric pressure plasma with NH₃(210 sccm)/N₂(100 sccm)/C₂H₂(150 sccm)/He(8 slm) at low substrate temperatures (?500 °C) and their physical and electrical characteristics were investigated as the application to field emission devices. The grown CNTs were multi-wall CNTs (at 450 °C, 15-25 layers of carbon sheets, inner diameter: 10-15 nm, outer diameter: 30-50 nm) and the increase of substrate temperature increased the CNT length and decreased the CNT diameter. The length and diameter of the CNTs grown for 8 min at 500 °C were 8 μm and 40 ± 5 nm, respectively. Also, the defects in the grown CNTs were also decreased with increasing the substrate temperature (The ratio of defect to graphite (I_D/I_G) measured by FT-Raman at 500 °C was 0.882). The turn-on electric field of the CNTs grown at 450 °C was 2.6 V/μm and the electric field at 1 mA/cm² was 3.5 V/μm.     

Micromechanical testing of carbon fibers deposited by low-pressure laser-assisted chemical vapor deposition

Carbon fibers were deposited directly from ethylene by laser-assisted chemical vapor deposition. The precursor gas pressures and the incident laser powers were varied. Micro-mechanical testing was carried out using a high-precision micro-manipulator. During three-point bend testing the fibers showed an elastic response, with no residual strain upon unloading, until fracture. The fibers’ strength and Young’s modulus are reported. A model for fiber fracture is proposed based on fiber cross-section analysis. Scanning electron microscopy was used to study the fiber cross-sections and the fiber surface morphology. The mechanical properties are related to the characteristic fiber microstructure investigated by Raman spectroscopy.     

Initiated chemical vapor deposition of polyvinylpyrrolidone-based thin films

Initiated chemical vapor deposition (iCVD) is used for the first time to deposit a non-acrylic carbon-based polymer, polyvinylpyrrolidone (PVP). PVP is known for its hydrophilicity and biocompatibility, and its thin films have found many applications in the biomedical community, one of which is as antibiofouling surfaces. From vapors of 1-vinyl-2-pyrrolidone (VP) and tert-butyl peroxide (TBPO), iCVD produces PVP thin films that are spectroscopically identical to bulk PVP without using any solvents. iCVD works by selectively fragmenting gaseous TBPO with heat to create radicals for initiation of polymerization. This selectivity ensures that the monomer VP does not disintegrate to form species that do not conform to the structure of PVP. Fourier-transform infrared (FTIR), nuclear magnetic resonance, and X-ray photoelectron spectroscopy (XPS) show full retention of the hydrophilic pyrrolidone functional group. Number-average molecular weights range between 6570 and 10,200 g/mol. The addition of ethylene glycol diacrylate (EGDA) vapor to the reaction mixture creates a cross-linked copolymer between VP and EGDA. Films with different degrees of cross-linking can be made depending on the partial pressures of the species. Methods for quantifying the relative incorporation of VP and EGDA using FTIR and XPS are introduced. The film with the lowest degree of cross-linking has a wetting angle of 11°, affirming its high hydrophilicity and iCVD's ability to retain functionality.     

Dual layer SiC coating on matrix graphite sphere prepared by pack cementation and fluidized‐bed chemical vapor deposition

A dual layer silicon carbide (SiC) coating including inner porous SiC (p‐SiC) layer and outer dense SiC (d‐SiC) layer was fabricated on the matrix graphite (MG) spheres of high‐temperature gas‐cooled reactor fuel elements by pack cementation and fluidized‐bed chemical vapor deposition process to improve the oxidation‐resistant property. Microstructure of the coating demonstrates different density and structure of the two SiC layers with no obvious boundaries between them. Weight gain curves of oxidation tests at 1773 K for 200 hours show that the coating could effectively protected the MG sphere by isolating the air infiltration with p‐SiC layer as the main functional layer and d‐SiC layer as the transition layer to improve the bond strength. Due to the transition function of p‐SiC layer, the coated spheres could understand more than 50 times thermal shocking tests from 1773 K to room temperature with no stress cracking.     

Edge defect-assisted synthesis of chemical vapor deposited bilayer molybdenum disulfide

The synthesis of two-dimensional molybdenum disulfide (MoS₂) has invoked much research interest in recent years. In this work, chemical vapor deposition (CVD) was employed to grow a novel molybdenum disulfide. The synthesis reaction was operated in an inert gas environment, with the sulfur precursor placed in the upstream zone of a double zone tube furnace, and the molybdenum trioxide (MoO₃) precursor placed in a small tube in the downstream zone. A piece of glass was used as the substrate, which was placed beside the small tube. We intentionally built a high concentration of molybdenum precursor above the substrate. The specific morphology hinged highly on the concentration of molybdenum. Abundant molybdenum atoms adsorbed on the edges of the bottom MoS₂ and formed defects, which promoted the nucleation of the top layer MoS₂ and preferentially grew from the edges. This result provides an innovative method to controllably synthesize novel bilayer molybdenum disulfide by a one-step method of chemical vapor deposition.     

Morphologies and growth mechanisms of zirconium carbide films by chemical vapor deposition

Zirconium carbide films were grown on graphite slices by chemical vapor deposition using methane, zirconium tetrachloride, and hydrogen as precursors. The growth rate of zirconium carbide films as a function of temperature was investigated. The morphologies of these films at different temperatures were also observed by scanning electron microscopy. The results indicated that the deposition of zirconium carbide was dominated by gas nucleation at temperatures below 1523 K, and by surface process at temperatures higher than 1523 K. By comparison of the deposition activation energies for zirconium carbide and deposited carbon, it was determined that the carbon deposition was the controlled process during the growing of zirconium carbide films. The effect of temperatures on the morphologies of zirconium carbide films was also discussed, based on the carbon deposition process.