Growth rate studies of CVD diamond in an RF plasma torch

This paper addresses the complex chemistry in the boundary later over a substrate in a chemical vapor deposition rector at atmospheric pressure. In this study, a highspeed plasma (140m/s) was created using a radio-frequency inductively coupled plasma torch for the deposition of diamond thin films. Growth rates on the order of 50 m/ h were obtained for well-faceted continuous films grown on molybdenum substrates positioned normal to the plasma flow. The highest growth rates were obtained at substrate temperatures of 1370 K and a feed gas ratio of 2.5% CH₄ in H₂. Growth rates are compared to predicted results obtained from numerical simulations, based on a one-dimensional stagnation-point flow, and are/mend to be in good agreement. Several other surface analysis techniques were used to characterize the deposited films, inchaling SEA/, Raman spectroscopy, transmission electron microscopy. Rutherfard backscattering spectroscopy, and hydrogen-forward recoil spectroscopy. Optical emission spectroscopy was used to characterize the RF plasma during the deposition process. Results from these studies form an important database for the validation and improvement of current models of the atmospheric-pressure diamond CVD environment.     

Fluid boundary layer effects in atmospheric-pressure plasma diamond film deposition

Diamond films were deposited in an atmospheric-pressure radio frequency plasma reactor. Hydrogen and methane were injected coaxially into the plasma as a high-velocity jet which impinged on the molybdenum substrate. In some cases argon was added to the reactant jet to increase its momentum, thereby reducing the boundary layer thickness. In most cases argon addition substantially, improved diamond growth. A numerical model was developed, which calculated two-dimensional reactor temperature and velocity, distributions, and the chemical kinetics in the boundary layer. The calculations indicate that under the experimental conditions argon addition reduced the thickness of the hydrogen nonequilibrium boundary layer from 3.5 to 1.0 mm. In addition, the calculations suggest that monatomic carbon may be a key diamond growth species under thermal plasma conditions.     

Control of substrate temperature during diamond deposition

A method is reported for controlling substrate temperature during chemical vapor deposition of diamond in high heat flux environments such as thermal plasmas or flames. The method is based on flowing a variable-composition argon-helium mixture through channels between the substrate and a water-cooled base. A fiberoptic pyrometer temperature reading from the back of the substrate provides feedback for active substrate temperature control. Experiments in an atmospheric-pressure RF reactor under diamond growth conditions indicated that substrate temperature could be sensitively varied by over 600 K by varying the composition of the argon-helium mixture. The effect is explained in terms of the variable thermal contact resistance at the interface between the substrate and the base.     

Diamond Deposition on Substrates with Different Geometries in a Thermal Plasma Reactor

The effects of process parameters on diamond film deposition have been considered in an atmospheric-pressure dc thermal plasma jet reactor. Two different precursor injection systems have been evaluated, counterflow and side injection. The precursor flow rate using ethanol has been found to strongly affect crystal size as well as orientation of crystal growth planes. Further, crystal size on sharp edges has been found to be up to five times larger than on planar surfaces. The effects of substrate geometry on the morphology and area of deposited diamond have been investigated as well. The results of this study show that dc thermal plasma jets can provide high diamond deposition rates, for example on wires and drills, although crystal size and film thickness show substantial variation.     

Diamond synthesis by DC thermal plasma CVD at 1 atm

Diamond crystals and films have been success full y synthesized by DC thermal plasma jet CVD at a pressure of I atrn. A novel triple torch plasma reactor has been used to generate a convergent plasma volume to entrain the participating gases. Three coalescing plasma jets produces! by this reactor direct the dissociated and ionized gaseous species onto ( 100) silicon wafer substrates where the diamond grows. In a typical 10-min run, depending on the method of .substrate preparation, either microcrystals with sizes up to 8 m or continuous films with thicknesses of 1–2 m have been obtained. X-ray diffraction, scanning electron microscopy, and Raman spectroscopy have been used for the characterization of the crystals and of the films.     

Large Scale Homogeneous Growth Mechanics of Microcrystalline Silicon Films on Rough Surface

Large scale homogenous growth of microcrystalline silicon (μc-Si:H) on cheap substrates by inductively coupled plasma (ICP) of Ar diluted SiH₄ has been studied. From XRD and Raman spectrum, we find that substrates can greatly affect the crystalline orientation, and the μc-Si:H films are comprised of small particles. Thickness detection by surface profilom-etry shows that the thin μc-Si:H films are homogenous in large scale. Distributions of both ion density and electron temperature are found to be uniform in the vicinity of substrate by means of diagnosis of Langmuir probe. Based on these experimental results, it can be proposed that rough surfaces play important roles in the crystalline network formation and Ar can affect the reaction process and improve the characteristics of μc-Si:H films. Also, ICP reactor can deposit the thin film in large scale.     

Characterization of the Converging Jet Region in a Triple Torch Plasma Reactor

Enthalpy probe measurements were taken of the converging plasma plume in a triple torch plasma reactor and related to substrate heat flux measurements. Results show excellent entrainment of process gases injected into the converging plasma plume by way of the central injection probe. At lower pressures (40 kPa), the plasma volume is equivalent to at least a 3 cm diameter, 4 cm long cylinder, with relatively uniform temperature, velocity, and substrate heat flux profiles when compared to a typical dc arc jet. Converging plasma plume size, substrate heat flux, and enthalpy profiles are also shown to be a strong function of applied system power. Substrate heat flux measurements show smaller radial gradients than enthalpy probe measurements, because of the high radial velocity component of gases above the substrate boundary layer. Enthalpy probe measurements were also conducted for diamond deposition conditions and approximate temperature and velocity profiles obtained. Problems with the uniform gas mixture assumption prohibited more accurate measurements. Reproducibility of enthalpy measurement results was shown with an average standard deviation of 11.8% for the velocity and 7.6% for the temperature measurements.     

Gold particles containing plasma-polymerized styrene as an X-ray absorber

Gold particles containing plasma-polymerized styrene film were formed simultaneously by plasma polymerization and evaporation using an inductively coupled argon gas flow type reactor. Gold was used as the evaporated metal and styrene as the monomer. The plasma etching characteristics of the film were evaluated by O₂ and CO₂ plasmas using a reactor with parallel-plate electrodes. A structure of lines and spaces of 4m width was successfully fabricated in the film on Si wafer by CO₂ plasma etching through a mask pattern of plasma-polymerized resist. A self-developed pattern was obtained through the X-ray mask with polyimide substrate by synchrotron radiation. The molecular structure and atomic composition of the film were investigated by ESCA and TEM.     

Chemical nucleation for CVD diamond growth.

A new nucleation method to form diamond by chemically pretreating silicon (111) surfaces is reported. The nucleation consists of binding covalently 2,2-divinyladamantane molecules on the silicon substrate. Then low-pressure diamond growth was performed for 2 h via microwave plasma CVD in a tubular deposition system. The resulting diamond layers presented a good cristallinity and the Raman spectra showed a single very sharp peak at 1331 cm(-1), indicating high-quality diamonds.     

Preparation and characterization of plasma-polymerized styrene thin films

Plasma-polymerized styrene (PPS) thin films (several hundred to several thousand Å thick) have been prepared under a variety of discharge conditions in a tubular reactor inductively coupled to a radio frequency (13.56 MHz) power supply. Studies have focussed on the correlation of deposited polymer structure, evidenced both at the film surface (via XPS analysis) and in the bulk polymer (via transmission FT–IR analysis) with controllable plasma parameters (coupled rf power, monomer flow rate, monomer pressure). It has been determined that the relative number of phenyl rings incorporated into the film intact is an inverse function of the power per styrene molecule ratio. Polymer deposition rate was found to be a strong function of styrene flow rate and substrate temperature. Plausible elements of the styrene plasma polymerization mechanism will be considered.     

Extending the Capabilities of the Thermodynamic Simulation of Thermochemical Processes in Inductively Coupled Plasma Discharge

The capabilities of the equilibrium thermodynamic simulation of thermochemical processes in inductively coupled plasma discharge are considered. Using a quasi-equilibrium model, the formation efficiencies of singly and doubly charged ions of 84 elements are calculated within the temperature range 4000–10000 K with a step of 500 K. The results of the calculations can be used for improving the performance characteristics of semiquantitative analysis in inductively coupled plasma mass spectrometry. The main trends in investigations on further extending the capabilities of thermodynamic simulations in inductively coupled plasma atomic emission and mass spectrometries are outlined.OAO Ekaterinburgskii zavod po obrabotke tsvetnykh metallov     

Two-temperature modeling of an arc plasma reactor

In this paper a two-temperature plasma model is established and applied to the injection of cold gases into an atmospheric-pressure, high-intensity argon arc. The required nonequilibrium plasma composition and the non-equilibrium transport properties are also calculated. The results show that the arc becomes constricted at the location of gas injection due to thermal and fluid dynamic effects of the injected cold flow. Enhanced Joule heating in the constricted arc path raises the electron as well as the heavy-particle temperatures. This temperature increase resists, via secondary effects, the penetration of the cold gas into the hot arc core which behaves more or less as a solid body as far as the injected flow is concerned. The temperature discrepancy between electrons and heavy particles is most severe at the location of cold flow injection, a finding which may have important consequences on chemical reactions in an arc plasma reactor.     

A transparent boron-nitrogen thin film formed by plasma CVD out of the discharge region

A transparent boron-nitrogen thin film of thickness 550 nm was successfully deposited out of the discharge region by rf plasma CVD. The deposition was performed with diborane (4.8 vol % in N₂) as the reactant gas and argon as the carrier gas by an inductively coupled reactor at a frequency of 13.56 MHz. The transparent films could be obtained at a low pressure of about 30 Pa, at a discharge power level of 30 W, and at room temperature without heating the substrate. The thin films obtained by rf plasma are compared with those obtained by microwave plasma. Both the refractive index and the deposition rate for the films deposited by microwave plasma are discussed according to the deposition conditions.     

Methyl Concentration Measurements During Microwave Plasma-Assisted Diamond Deposition

Absolute line-of-sight averaged measurements of methyl radical concentrationsin a microwave plasma-assisted diamond deposition reactor arepresented. The measurements are based on the use of broadband ultravioletabsorption spectroscopy to characterize the distinguishing absorptionfeature of methyl at 216 nm associated with the X(²A₂)(²A₁) electronictransition. The dependence of the line-of-sight methyl concentration andmole fractions with the percentage of methane in the feed-gas, plasma powerdensity, and position of substrate relative to the optical probe volume isstudied. The measurements suggest that the near-substrate methyl molefraction is only weakly sensitive to changes in substrate temperature andare largely influenced by the gas-phase temperature. A comparison is madebetween the measured mole fractions and recent predictions based on aone-dimensional model of this process. The measured mole fractions areconsistently greater than those predicted by about a factor of ten. Thisdiscrepancy is explained in part by the line-of-sight limitations in theexperimental facility.     

Process study of thermal plasma chemical vapor deposition of diamond,part I: Substrate material,temperature, and methane concentration

Effects of process parameters on diamond film synthesis in DC thermal plasma jet reactors are discussed including substrate material, methane concentration and substrate temperature. Diamond has been deposited on silicon, molybdenum, tungsten, tantalum, copper, nickel, titanium, and stainless steel. The adhesion of diamond film to the substrate is greatly affected by the type of substrate used. It has been found that the methane concentration strongly affects the grain size of the diamond films. Increased methane concentrations result in smaller grain sizes due to the increased number of secondary nucleations on the existing facets of diamond crystals. Substrate temperature has a strong effect on the morphology of diamond films. With increasing substrate temperature, the predominant orientation of the crystal growth planes changes from the (111) to the (100) planes. Studies of the variation of the film quality across the substrate due to the nonuniformity of thermal plasma jets indicate that microcrystalline graphite formation starts at the corners and edges of diamond crystals when the conditions become unfavorable for diamond deposition.     

Spectral diagnostics of inductively coupled RF discharge plasma

Results of UV spectral measurements in low-pressure (30–65 Pa) and atmospheric-pressure inductively coupled radiofrequency discharges at different power inputs and gas compositions typical for that of industrial processing regimes are reported. Isolated molecular bands have been observed in the spectra; by analyzing the unresolved rotational temperature of these bands, the rotational temperature of the upper emission state can be found.     

Two-dimensional model for thermal plasma chemical vapor deposition

A formulation of a global mathematical two-dimensional model for Thermal Plasma Chemical Vapor Deposition (TPCVD) is reported. Both gas-phase and surface chemical kinetics as well as ordinary and thermal diffusion are incorporated. Flow is assumed to be steady, laminar and swirlless at this stage. The results include velocity, pressure, density, temperature and chemical species distributions in the reactor, and the heat flux and the film growth characteristics at the substrate.The model has been applied to a low pressure diamond TPCVD. Two basic cases have been investigated: (1) supersonic jet regime, and (2) high speed subsonic jet regime. The results for both cases are presented and compared. In both cases, the hydrocarbon species needed for the diamond formation are assumed to be premixed in the plasma jet.The main conclusions are: (1) The low pressure high speed jets are very narrow and slow down only at the substrate through a bow shock, (2) the faster the jet, the bigger the total deposited amount of diamond but also the higher the heat flux and diamond growth rate nonuniformities.     

Nanocrystalline Diamond Thin Films Synthesis on Curved Surface

Thin films of curved surface nanocrystalline diamond (CS-NCD) are a category of important materials. However, the development of such materials is still a highly challenging task. Here we present a novel approach to synthesizing CS-NCD thin films deposited on non-spherical surfaces of molybdenum substrate using direct current plasma jet chemical vapor deposition. A special cooling system was designed and applied to ensure uniform substrate temperature. It is demonstrated from simulation and experimental results that this system is favorable for the production of thin films. The results show that the quality of CS-NCD thin films depends on the selection of optimal values of parameters including CH₄ concentration, substrate temperature, and chamber pressure. If the CH₄ concentration and/or the substrate temperature is too high or low, it results in non-diamond phase or micron-crystalline diamond thin films. Synthetic CS-NCD thin films using the proposed method have a smooth surface and uniform thickness. The average grain size and the mean surface roughness are approximately 30 and 4.3 nm respectively. Characteristics of CS-NCD thin film spectra comprised of the full width at half maximum with broad Raman peaks around 1,140 and 1,480 cm^?1, confirming the presence of the NCD phase.     

Thermal Plasma Chemical Vapor Deposition of Si-Based Ceramic Coatings from Liquid Precursors

In this paper a process based on the use of rf inductively coupled plasma is applied for the synthesis and deposition of Si-base ceramic materials (i.e., SiC, Si₃N₄, SiO₂). The starting materials are low-cost liquid disilanes. The atomization process is first investigated and the structure of the resulting coatings is characterized by means of X-ray diffraction, scanning electron microscopy as well as with transmission electron microscopy. Results of the influence of some processing parameters (i.e., chamber pressure, spray distance, substrate cooling, plasma gas nature and composition, precursor composition and atomization parameters) on the phase and microstructure of the coating is reported. Control of the microstructure (or nanostructure) as well as the phase content, namely the / ratio of the phases for SiC and Si3N4, can be achieved with such a synthesis and deposition technique.     

Comparative Study of the Decomposition of CCl4 in Cold and Thermal Plasma

Decomposition of carbon tetrachloride was studied in an inductively coupled thermal plasma reactor and in a low temperature, non-equilibrium plasma reactor, in neutral and oxidative conditions, respectively. In neutral conditions formation of solid soot, aliphatic- and cyclodienes was observed in equilibrium, and products, such as Cl₂ and C₂Cl₆ were detected in non-equilibrium plasma. Feeding of oxygen into the thermal plasma reactor depressed both soot and dienes formation and induced the formation of oxygen containing intermediates and products. GC-MS analyses of the gaseous products and the extract of the soot referred to as complex decomposition and recombination mechanism at given conditions. Presence of oxygen in the low temperature plasma reactor results in the formation of carbonyl compounds as intermediers. CO₂ and Cl₂ revealed as final products of CCl₄ decomposition in cold plasma.