Growth Rate of Diamond on Polycrystalline 〈110〉 Diamond Substrates from Carbon Disulfide in Hydrogen by Hot-Filament-Assisted Chemical Vapor Deposition

The growth rates for the deposition of diamond by hot-filament-assisted chemical vapor deposition using carbon disulfide (CS₂) in hydrogen and methane (CH₄) in hydrogen were investigated on polished, 〈110〉 textured, polycrystalline diamond substrates. The carbon concentration in each system was varied from 1% to 2.5%. The deposition rate increased proportionately with carbon concentration for both systems. The CH₄-H₂ system gave higher growth rates with an essentially constant difference in rate between CS₂ and CH₄. Possible explanations for this are discussed with the most likely either a catalytic effect of sulfur or sulfur-containing species on gas-phase homogeneous atomic hydrogen recombination, or the surface chemisorption of relatively less labile sulfur-containing species at the diamond surface.     

Chemical Kinetic Calculations of the Gas Phase in Filament-Assisted Chemical Vapor Deposition of Diamond

A chemical kinetic model was developed for the gas mixture in filament-assisted diamond chemical vapor deposition (CVD) systems. CH₄/H₂ mixture was studied as the starting gas mixture. The predictions of gas evolution calculated from this model were used to interpret certain published experimental observations. From the initial analysis, it was concluded that the thermodynamic state of the gas composition determined the effects of transport parameters on diamond growth. In many filament-assisted diamond CVD systems the gas composition was found to be kinetically controlled. The analysis also suggested that CH₃ is a major precursor of diamond films. When CH₄/H₂/O₂ was used as the starting gas mixture, the results indicated that the oxygen additive catalyzed the process to increase the concentrations of CH₃ and H, thereby increasing the growth rate and improving the quality of diamond films.     

Nucleation and Growth of Diamond Films on Ni-Cemented Tungsten Carbide: II, Effects of Deposition Conditions

Diamond films were deposited by hot-filament chemical vapor deposition (HFCVD) on substrates made of WC sintered with 6 wt% of Ni. The as-ground substrates were scratched with diamond powder (S samples) or scratched and wet-etched (SE samples). Diamond synthesis was carried out at substrate temperatures ranging between 600° and 1050°C, and using 1.0% or 2.0% CH₄ in H₂. The diamond nucleation density, as measured by scanning electron microscopy (SEM) and automatic image analysis (AIA), did not significantly change in the 600°-900°C temperature range, while at substrate temperatures higher than 900°C a steep decrease of the density of nuclei was observed and attributed to the thermal annealing of nucleation sites. The activation energy of the growth process was measured and found to be 21 ± 2 kcal/mol. Neither nucleation density nor growth rate were affected by an increase of CH₄ concentration in the feed gas, while a lack of crystallinity was observed at the higher methane concentration. Raman analysis showed that phase purity of the films was affected mainly by the substrate temperature: the lower the temperature, the better the film quality. The presence of Ni on the substrate surface did not induce the preferential formation of non-diamond carbon phases, as confirmed by comparing the Raman spectra obtained from both S and SE substrates. As a comparison, continuous films were deposited on scratched WC-5 wt% Co substrates under the same experimental conditions. The results indicated that the use of Ni as a binder is preferable to Co.     

Nucleation and Growth of Diamond Films on Ni-Cemented Tungsten Carbide: Effects of Substrate Pretreatments

The nucleation and growth of diamond films on Nicemented carbide is investigated. Substrates made of WC with 6 wt% of Ni were submitted to grinding, and then to different pretreatments (scratching, etching, and/or decarburization) before diamond deposition. Diamond synthesis was carried out by hot-filament chemical vapor deposition (HFCVD) using a mixture of CH₄ (1% v/v) and H₂. Depositions were performed for different lengths of time with the substrates at various temperatures. The specimens were analyzed before and after deposition by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffractometry (XRD). Raman spectra showed that the phase purity of the diamond films was not affected by the presence of nickel on the substrate surface. After wet etching pretreatments, the nucleation of diamond was enhanced, mainly at the WC grain boundaries. Continuous films were obtained on scratched and etched substrates. The decarburizing treatment led to the formation of metallic tungsten and of brittle nicke–tungsten carbide phases. These phases reacted in the early stages of diamond film formation with gaseous carbon species with a parallel process which competes with stable diamond nucleus formation. The diamond film formed after long-term deposition on these samples was not continuous.     

Fabrication and Characterization of a (100) Three-Axis-Oriented Single-Crystal (Ba0.7Sr0.3)TiO3 Thin Film Prepared by the Chemical Solution Deposition Method

Epitaxially grown single-crystal perovskite (100) three-axis-oriented (Ba_0.7Sr_0.3)TiO₃ thin films were prepared on a (100) platinum-coated (100) magnesium oxide (MgO) single-crystal substrate by the chemical solution deposition method using a solution derived from Ba(CH₃COO)₂, Sr(CH₃COO)₂, and Ti(O- i -C₃H₇)₄.
The growth of the film was found to depend on the annealing condition. A (Ba,Sr)TiO₃ thin film annealed at 1073 K was found to be a single crystal by transmission electron microscope. The single-crystal film exhibited a (100) three-axis orientation that followed the (100) orientation of the Pt substrate, as observed from an X-ray pole figure measurement and selected area electron diffraction patterns.     

Effect of Carbon Precursors on the Microstructure and Bonding State of a Boron–Carbon Compound Grown by LPCVD

Methane (CH₄) and propylene (C₃H₆) were used to fabricate a boron–carbon coating by a low-pressure chemical vapor deposition (LPCVD) technique. The effects of carbon precursors on the phase, microstructure, and bonding state of the deposits have been investigated. X-ray diffraction results show that the 2θ value of the deposit from the C₃H₆ precursor shifts to 25.78° when the coating is deposited at 1223 K, and shifts to 26.1° when deposited at 1273 K, compared with the 2θ value of the pyrocarbon (PyC) peak deposited by LPCVD, which is 25.42°, and no boron–carbon (B–C) compound peak exists. However, the phases of coating deposited from CH₄ include B₂₅C, B₁₃C₂, elemental carbon, and boron. X-ray photoelectron spectroscopy (XPS) results show that the percent contents of boron atom in the coatings from the CH₄ precursor are 61.18% and 67.78% when deposited at 1223 and 1273 K, respectively, much higher than that from the C₃H₆ precursor, 10.85% and 15.30%, respectively. Scanning electron microscopy (SEM) results show that the coatings deposited from CH₄ have a coarse crystal-like morphology; however, the coatings deposited from the C₃H₆ precursor are smooth. The formation of PyC from C₃H₆ is more facile than that from CH₄, which leads to differences in the phase, atom content, and microstructure of coatings from CH₄ and C₃H₆ precursors.     

In–Flight Carburization of Molybdenum Disilicide Powders by an Induction Plasma

In-flight carburization of MoSi₂ powders has been performed in an argon–H₂–CH₄ induction plasma. CH₄ was used as the powder carrier gas, and it reacted with MoSi₂ powders under the high-temperature conditions of the plasma. Carbon and α-SiC were the major reaction products of the in-flight carburized MoSi₂ powders. The silicon carbide formed through nucleation and subsequent growth in the liquid phase. The influence of the induction plasma power level, reactor pressure, and quantity of CH₄ on the carburization efficiency was investigated through a Box–Behnken experimental design. Under the optimal conditions achieved in this investigation, ∼8.0 wt% of carbon was incorporated into the MoSi₂ powder particles.     

Fine Patterning and Characterization of Gel Films Derived from Methyltriethoxysilane and Tetraethoxysilane

Pregrooves of 1.6 µm pitch for optical data storage have been embossed successfully by pressing a stamper against x CH₃Si(OC₂H₅)₃(100 - x )Si(OC₂H₅)₄-derived gel films (60 ≤ x ≤ 100 mol%) on glass-disk substrates of 130 mm diameter. When x is <40 mol%, the resultant films are too hard to emboss patterns uniformly. The shrinkage of the patterns is ∼4% for all the films when 60 lessthan equal to x lessthan equal to 100 mol%, even after heat treatment at 350°C, so that the nearly net negative shape of the stamper is preserved. The methyl groups in the films decompose at temperatures from 500° to 600°C.     

Effect of Addition of Silicon on the Microstructures and Bending Strength of Continuous Porous SiC–Si3N4 Composites

The microstructures and mechanical properties of continuous porous SiC–Si₃N₄ composites fabricated by multi-pass extrusion were investigated, depending on the amount of Si powder added. Si powder with different weight percentages (0%, 5%, 10%, 15%, 20%) was added to SiC powder to make raw mixture powders, with 6 wt% Y₂O₃–2 wt% Al₂O₃ as sintering additives, carbon (10–15 μm) as a pore-forming agent, ethylene vinyl acetate as a binder, and stearic acid (CH₃(CH₂)₁₆COOH) as a lubricant. In the continuous porous SiC–Si₃N₄ composites, Si₃N₄ whiskers like the hairs of nostrils were frequently observed on the wall of the pores. In this study, the morphology of Si₃N₄ whiskers was investigated with the nitridation condition and silicon addition content. In composites containing an addition of 10 wt% Si, a large number of Si₃N₄ whiskers were found at the continuous pore regions. In the sample to which 15 wt% Si powder was added, a maximum value of about 101 MPa bending strength and 57.5% relative density were obtained.     

Deposition Mechanism for Chemical Vapor Deposition of Zirconium Carbide Coatings

Zirconium carbide (ZrC) coatings were fabricated by chemical vapor deposition (CVD) using ZrCl₄, CH₄/C₃H₆, and H₂ as precursors. Both thermodynamic calculation results and the film compositions at different temperatures indicated that zirconium and carbon deposited separately during the CVD process. The ZrC deposition rates were measured for CH₄ or C₃H₆ as carbon sources at different temperatures based on coating thickness. The activation energies for ZrC deposition demonstrated that the CVD ZrC process is controlled by the carbon deposition. This is also proven by the morphologies of ZrC coatings.     

Vibrational properties of nitrogen-doped ultrananocrystalline diamond films grown by microwave plasma CVD

Ultrananocrystalline diamond (UNCD) films grown in an argon-rich Ar/CH₄/H₂ microwave plasma with nitrogen gas added in amounts of 0%–20% were studied by Raman spectroscopy with multiple excitation wavelengths in the range of 244–647 nm and by optical absorption in UV–visible. The Raman spectra have demonstrated the presence of diamond, amorphous carbon and polyacetylene in the UNCD films. Analysis of vibrational and optical properties of amorphous carbon phase proves that nitrogen stimulates the transition from amorphous carbon into an ordered graphite-like structure with narrowed optical band gap, which is supposed to be responsible for the high electrical conductivity of the N-doped UNCD.     

Growth of faceted, ballas-like and nanocrystalline diamond films deposited in CH4/H2/Ar MPCVD

The influence of Ar addition to CH₄/H₂ plasma on the crystallinity, morphology and growth rate of the diamond films deposited in MPCVD was investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. X-Ray diffraction patterns indicate that diamond films of strong (111) and weak (400) texture are produced in these samples. Faceted diamond gradually turns into ballas-like diamond with graphitic inclusions when the Ar concentration increases to above 30 vol.%, as indicated by Raman spectra. As the Ar concentration goes above 90 vol.%, nanocrystalline diamond films are formed, characterized by a 1150-cm⁻¹ peak in the Raman spectra and morphology observation. Diamond growth by CH₃ or by C₂ mechanism is proposed to interpret the change in the growth rate of diamond films with the variation of Ar content in the plasma.     

Preparation of Silicon Nitride-Titanium Nitride and Titanium-Titanium Nitride Composites from (CH3)3SiNHTiCl3-Coated Si3N4 and Ti Particles

[(Trimethylsilyl)amino]titanium trichloride, (CH₃)₃-SiNHTiClj, was isolated as a red-orange crystalline solid in 58% yield from the reaction of TiCl₄ with [(CH₃)₃Si]₂NH in 1:1 molar ratio in dichloromethane at —78°C. Pyrolysis of (CH₃)₃SiNHTiCl₃ at 600°C furnished titanium nitride. This precursor is suitable for the preparation of composites and was employed to prepare Si₃N₄-TiN and Ti-TiN powders by adding Si₃N₄ particles or titanium powders to a solution of (CH₃), SiNHTiCl₃ in dichloromethane, drying and pyrolyzing the resulting solid. This precursor also has been used as a binder to prepare Si₃N₄-TiN and Ti-TiN bodies. High-resolution transmission electron microscopic studies of the Si₃N₄-TiN composite showed that titanium nitride is concentrated on the surface of the Si₃N₄ particles.     

Surface Chemistry and Structure of Ultrafine Silicon Carbide: An FT-IR Study

Using transmission FT-IR, surface characterizations are performed on ultrafine SiC powders produced by a laser-driven method. The surface species sensitive to thermal treatments (OH, CH _{x ,}, C = O, SiH _x ) are identified on samples evacuated at various temperatures. Absorption bands attributed to overtones of the fundamental Si—C modes are also present in the IR spectra and remain unchanged after treatment. The reaction of SiC with oxygen and water vapor produces a layer of silica on the sample and gaseous CO₂; the reaction with ammonia results in a partial nitridation of the surface, with the formation of NH _x groups that apparently increase the stability of the SiC against oxidation; and reaction with hydrogen produces methane in the gas phase and causes the disappearance of the bands due to surface CH _x groups.     

Synthesis of Diamond from Carbon Disulfide in Hydrogen

The synthesis of diamond has been accomplished from carbon disulfide (CS₂) in hydrogen (H₂) using tungsten hot filament chemical vapor deposition. A continuous layer was deposited on silicon and characterized using Raman spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy. The polycrystalline film exhibited a sharp Raman peak at 1331.4 cm⁻¹ and a broad low–intensity peak at approximately 1500 cm⁻¹. X–ray diffraction analysis showed peaks corresponding to the {111}, {220}, and {311} reflections of diamond with evidence of (110) texture. Diamond growth from CS₂ in H₂ was observed to be highly faceted by scanning electron microscopy.     

Hydride Vapor Phase Epitaxy of GaN Thick Films by the Consecutive Deposition Process Using GaCl3

GaN buffer and main layers were grown by the conventional hydride vapor phase epitaxy technique using GaCl₃ consecutively. The deposited buffer layers were investigated by atomic force microscopy and X-ray analysis. To examine the behavior of the buffer layers at main layer growth temperature, heat treatment was conducted at 900°C. Based on the results of the buffer layer study, GaN thick films were grown at 1050°C. Optimum deposition conditions of buffer layer from the buffer and main layer studies generally coincided. On the φ scanning pattern, the GaN films grown on (0001) Al₂O₃ were single-crystalline. Band-edge emission dominated photoluminescence was observed at room temperature.     

Chemical Solution Deposition of (Pb1−xCax)TiO3 Thin Films with x∼0.5 as New Dielectrics for Tunable Components and Dynamic Random Access Memories

Calcium lead titanate ((Pb,Ca)TiO₃) thin films, with calcium contents of ∼50 at.%, have been prepared by chemical solution deposition (CSD). Different synthetic sol–gel methods have been used for the preparation of the precursor solutions. 1,3-propanediol, OH(CH₂)₃OH, and water, H₂O, were used as solvents. Lead (II) acetate trihydrate, Pb(OCOCH₃)₂·3H₂O, and titanium di-isopropoxide bis(acetylacetonate), Ti(OC₃H₇)₂(CH₃COCHCOCH₃)₂, were used as reagents of lead and titanium, respectively. Calcium was incorporated into the solutions as calcium acetate hydrate, Ca(OCOCH₃)₂· x H₂O, or as calcium acetylacetonate hydrate, Ca(CH₃COCHCOCH₃)₂· x H₂O. Only the use of calcium acetate led to precipitate-free solutions. Pb(II)–Ti(IV)–Ca(II) sols were obtained when calcium acetate was refluxed with the lead and titanium reagents in a diol–water solvent. These sols led to films with a homogeneous compositional profile. Solutions obtained by mixing a water solution of calcium acetate with a Pb(II)–Ti(IV) sol led to films with a heterogeneous compositional profile in which an interface between the film and the Pt bottom electrode is formed. The films derived from the Pb(II)–Ti(IV)–Ca(II) sols have values of dielectric constant at room temperature of ∼500, which, together with their low leakage currents, low dielectric losses, and tunability, make these films promising for dynamic random access memories and tunable devices.     

Modified Sol-Gel Process for the Production of Lead Titanate Films

A modified sol-gel process has been developed for the production of thin films of PbTiO₃. The new route uses the mixed ligand complex titanium diisopropoxide bis(acetylacetonate), Ti(OC₃H₇)₂(CH₃COCHCOCH₃)₂, in place of titanium tetraisopropoxide, Ti(OC₃H₇)₄. For base-catalyzed conditions, the maximum thickness of crack-free PbTiO₃ films after one high-temperature firing cycle is 1 μm. This value represents a twofold increase in thickness over that obtained using existing sol-gel routes based on Ti(OC₃H₇)₄.     

Pyrolysis of Titanium-Metal-Filled Poly(siloxane) Preceramic Polymers: Effect of Atmosphere on Pyrolysis Product Chemistry

Pyrolysis of unfilled as well as Ti-metal-filled poly(siloxane) preceramic polymers, heated at 1350^deg;C in N₂, Ar, or NH₃, was evaluated in terms of the effect of atmosphere on pyrolysis product chemistry. Pyrolysis of the unfilled poly(siloxane) in N₂ or Ar resulted in the formation of a metastable, amorphous SiO_xC_y phase with a residual turbostratic carbon phase, with the evolution of CH₄ and H₂ as the main pyrolysis products. However, pyrolysis of the unfilled poly (siloxane) in NH₃ resulted in a partial substitution of nitrogen from the atmosphere for network carbon to form a binary mixture of amorphous SiO_xC_y and SiO_xN_y phases. Pyrolysis of the Ti-filled poly(siloxane) in NH₃ resulted in the reaction of the Ti particles with the atmosphere to form nearly stoichiometric TiN. In Ar, the Ti particles react with either gaseous hydrocarbon, i.e., CH₄, or the carbon pyrolysis products of the poly(siloxane), to form slightly nonstoichiometric TiC along with a partial reduction of the SiO_xC_y matrix. Finally, in N₂, the Ti particles react with both carbon from the poly(siloxane) and nitrogen from the atmosphere to form a solid solution of TiC and TiN.     

Characterization of Photoluminescent (Y1–xEux)2O3 Thin Films Prepared by Metallorganic Chemical Vapor Deposition

The purpose of this study was to identify and correlate the microstructural and luminescence properties of europium-doped Y₂O₃ (Y_{1– x} Eu _x )₂O₃ thin films deposited by metallorganic chemical vapor deposition (MOCVD), as a function of deposition time and temperature. The influence of deposition parameters on the crystallite size and microstructural morphology were examined, as well as the influence of these parameters on the photoluminescence emission spectra. (Y_{1– x} Eu _x )₂O₃ thin films were deposited onto (111) silicon and (001) sapphire substrates by MOCVD. The films were grown by reacting yttrium and europium tris(2,2,6,6-tetramethyl–3,5-heptanedionate) precursors with an oxygen atmosphere at low pressures (5 torr (1.7 × 10³ Pa)) and low substrate temperatures (500°–700°C). The films deposited at 500°C were smooth and composed of nanocrystalline regions of cubic Y₂O₃, grown in a textured [100] or [110] orientation to the substrate surface. Films deposited at 600°C developed, with increasing deposition time, from a flat, nanocrystalline morphology into a platelike growth morphology with [111] orientation. Monoclinic (Y_{1– x} Eu _x )₂O₃ was observed in the photoluminescence emission spectra for all deposition temperatures. The increase in photoluminescence emission intensity with increasing postdeposition annealing temperature was attributed to the surface/grain boundary area-reduction effect.