Particle densities and non-equilibrium in a low-pressure argon plasma jet

Plasma diagnostic techniques have been employed to determine particle densities and temperatures in a low-pressure argon plasma jet generated by a cascade arc. These measurements allow characterization of the extent to which the plasma jet deviates from thermodynamic equilibrium and provide a basis for predicting how reactive gases will interact with the excited and ionized species in the plasma jet. It was found that the distribution of atomic states in the plasma jet is not adequately described by either local thermodynamic equilibrium (LTE) or partial local thermodynamic equilibrium (pLTE), and the jet was optically thick for 3p4s transitions across the jet radius. Excited argon neutrals outnumber ions by a large ratio, and dominate subsequent dissociation/excitation phenomena. The rate of methane destruction in the plasma jet shows that estimates for particle densities, temperature, and jet velocity are self-consistent.     

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.     

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.     

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.     

Carburizing of titanium with plasma jets under reduced pressure

The carburizing of titanium with argon-methane (0.1%) and argon-methane (0.1%)-hydrogen (2%) plasma jets at a pressure of 200 Torr was studied. The carburizing of titanium was not successful with the argon-methane plasma jet because the specimen was covered with graphitic carbon. A hard and thick TiC layer was formed by the argon-methane-hydrogen plasma jet in a short time without the deposition of graphitic carbon. Emission spectra from the plasma jets show that the addition of hydrogen increases the amount of CH radicals as well as decreases the amount of C₂ and C in the plasma jet. The decrease of C₂ and C suppresses the deposition of graphitic carbon and enhances the TiC formation.Partly presented at Gordon Research Conference on Plasma Chemistry, August 11–15, 1986, Tilton, New Hampshire.     

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.     

Influence of Gas Entry Point on Plasma Chemistry,Ion Energy and Deposited Alumina Thin Films in Filtered Cathodic Arc

The effect of gas entry point on the plasma chemistry, ion energy distributions and resulting alumina thin film growth have been investigated for a d.c. cathodic arc with an aluminum cathode operated in an oxygen/argon atmosphere. Ions of aluminum, oxygen and argon, as well as ions originating from the residual gas are investigated, and measurements for gas entry at both the cathode and close to the substrate are compared. The latter was shown to result in higher ion flux, lower levels of ionised residual gas, and lower ion energies, as compared to gas inlet at the cathode. These plasma conditions that apply when gas entry at the substrate is used result in a higher film deposition rate, less residual gas incorporation, and more stoichiometric alumina films. The results show that the choice of gas entry point is a crucial parameter in thin film growth using reactive PVD processes such as reactive cathodic arc deposition.     

Surface reactivity and energetics of CH radicals during plasma deposition of hydrogenated diamondlike carbon films

The surface reactivity of CH radicals was measured during plasma deposition of hydrogenated diamondlike carbon (DLC) films using the imaging of radicals interacting with surfaces (IRIS) method. In this technique, spatially resolved laser-induced fluorescence (LIF) is used to determine surface reactivity, R, of plasma species. The measured reactivity of CH is near unity and shows no dependence on the applied rf power (P), argon fraction, substrate temperature, or substrate bias. Kinetic translational temperatures, (T), of CH in the molecular beam were also measured. Modeling of the kinetic data yields ThetaT(CH) values of approximately 2200-2500 K and 1600-1700 K for CH4/Ar plasmas at pressures of 50 and 110 mTorr, respectively, with no clear dependence on the argon fraction (at P = 100 W). The average ThetaT(CH) does, however, change with P, (T) = approximately 2050-9050 K, over the range P = 180-20 W. These results indicate that ThetaT(CH) is associated with the electron temperature in the plasma. The rotational temperature, (R), determined from the CH rotational excitation spectrum is approximately 1450 K with no clear dependence on P or the Ar fraction in the feed. The difference between ThetaT(CH) and ThetaR(CH) can be explained by the different relaxation rates after the dissociation of CH4 by electron impact.     

Hydrogen/argon plasma jet with methane addition

Spatial distributions of plasma parameters are presented for a H₂/Ar plasma jet with addition of methane. The plasma has been generated at atmospheric pressure by a 200 A (20 kW) nontransferred do arc. Optical emission spectroscopy has been used for the measurements assuming the plasma jet to be optically thin and to have an axial symmetry. Local spectral ernissivity values have been evaluated using a routine Abel inversion procedure. Half- width and emissivity of H spectral line have been measured to determine the electron density and temperature of the plasma. The densities of excited C, CH radicals have been evaluated from the absolute emissivities of relevant molecular emission bands measured in limited spectral intervals in the visible spectrum. The emissivity ratios have been used to fund rotational and vibrational temperatures. The results supply information on methane decomposition and the behavior of molecular radicals in close-to-thermal plasma jets.     

Comparison of Laminar and Turbulent Thermal Plasma Jet Characteristics—A Modeling Study

Modeling results are presented to compare the characteristics of laminar and turbulent argon thermal plasma jets issuing into ambient air. The combined-diffusion-coefficient method and the turbulence-enhanced combined-diffusion-coefficient method are employed to treat the diffusion of ambient air into the laminar and turbulent argon plasma jects, respectively. It is shown that since only the molecular diffusion mechanism is involved in the laminar plasma jet, the mass flow rate of ambient air entrained into the laminar plasma jet is comparatively small and less dependent on the jet inlet velocity. On the other hand, since turbulent transport mechanism is dominant in the turbulent plasma jet, the entrainment rate of ambient air into the turbulent plasma jet is about one order of magnitude larger and almost directly proportional to the jet inlet velocity. As a result, the characteristics of laminar plasma jets are quite different from those of turbulent plasma jets. The length of the high-temperature region of the laminar plasma jet is much longer and increases notably with increasing jet inlet velocity or inlet temperature, while the length of the high-temperature region of the turbulent plasma jet is short and less influenced by the jet inlet velocity or inlet temperature. The predicted results are reasonably consistent with available experimental observation by using a DC arc plasma torch at arc currents 80–250 A and argon flow rates (1.8–7.0)×10⁻⁴ kg/s.     

Substrate temperature effects on film chemistry in plasma depositions of organics. II. Polymerizable precursors

The influence of substrate temperature during plasma deposition on the chemistry of the organic films formed was examined. Plasma ionization of precursor gases that are polymerizable by conventional mechanisms was studied. Film chemistry was analyzed by x-ray photoelectron spectroscopy (XPS). Monomers that polymerize by a free radical mechanism [2-hydroxyethyl methacrylate (HEMA) and hexafluorobutadiene (HFB)] form more regular polymers (i.e. with less molecular rearrangement) by plasma deposition at low substrate temperatures than monomers that polymerize by ionic mechanisms [ethylene oxide (EO) and tetrahydrofuran (THF)]. In all cases, lowering the substrate temperature during deposition produces films with elemental composition virtually identical to that of the precursor gas. Comparison of high-resolution XPS spectra of the deposited films with those for model polymers suggests that functional groups in the monomers used to generate the plasma are incorporated to a greater extent at low substrate temperatures. The effect of plasma power on the degree of precursor structure retention obtained when reduced substrate temperatures are employed was also examined. Plasma deposition of HEMA at low substrate temperatures and low plasma power produces thin films which are, by core level XPS, indistinguishable from HEMA polymerized by conventional methods. EO and THF films coated at low substrate temperatures on glass, polyethylene, or polytetrafluoroethylene varied widely in surface chemistry due to differences in film uniformity. Film quality (uniformity) is enhanced for these low reactivity precursors by pretreating substrates with an argon plasma. © 1992 John Wiley & Sons, Inc.     

ESR Study of the Plasma Polymerizations of Trimethylsilane and Methane

Electron Spin Resonance (ESR) was used to study, at the molecular level, the plasma polymerization of trimethylsilane (TMS) and methane. Direct ESR analysis of the plasma coated Al substrate required the use of a novel ESR technique. TMS plasma deposit on Al showed a single broad resonance line near g = 2.003. The signal was stable in vacuum and decayed on exposure to air, with a significant fraction persisting for days. Results show that this signal arises from silicon dangling bonds. Identical TMS signals were observed from films prepared by the DC cathodic or the AF glow discharge method but their decay rates were different. In contrast, the deposition of methane produced two distinct types of carbon-based signals depending upon the method of deposition. TMS or CH₄ films deposited by the DC cathodic method showed slow signals decay and high refractive indices value. While the use of Al as the substrate showed plasma-coating radicals, only substrate radicals were observed when PE was used as the substrate. The nature of radicals formed depends not only on the deposition method used but also on the substrate type.     

Radiofrequency Plasma Polymers Containing Ionic Phosphonate Groups: Effect of Monomer Structure and Carrier Gas on Properties and Deposition Rate

Radiofrequency (RF) plasma polymers prepared from perfluoroallylphosphonic acid (PAPA) are hydrophilic and have ionic properties. Unfortunately, deposition rates are low. The current study focuses on RF plasma polymers prepared from PAPA and pentafluoroallyldiethylphosphonate (PADP) with and without argon carrier gas. Plasma polymerized PADP films were similar in composition, structure, and properties to plasma polymerized PAPA films, but were deposited at much higher rates. The addition of argon to the PAPA discharges resulted in a decrease in mean deposition rate from 41.7 Å/min to less than 20 Å/min, while the deposition rate of plasma polymerized PADP increased significantly with the addition of argon to the discharge. PADP derived plasma polymer deposition rates ranged from 136 Å/min to 390 Å/min, depending on position in the reactor and presence or absence of argon carrier gas. PAPA-derived plasma polymers exhibited deposition rates and properties that were uniform throughout the reactor, while PADP-derived plasma polymers had maximum deposition under the upstream induction coil and linearly decreasing deposition rate with downstream distance in the reactor. Additionally, the PADP-derived plasma polymers exhibited downstream changes in atomic composition, structure, and physical properties, such as wettability and hardness. These changes were attributed to a getter effect upstream in the reactor in which ablated hydrogen species scavenge etching fluorine species in the plasma phase.     

Surface characterization of the SiOx films prepared by a remote atmospheric pressure plasma jet

The deposition rate and surface properties of SiO_x films were prepared and investigated using remote atmospheric pressure plasma (APP) jet. The APP, generated with low frequency power at 16 kHz, was fed with tetraethoxysilane (TEOS)/air gas mixture. After deposition, the SiO_x films were analyzed for chemical characteristics, elemental composition, surface morphology, and hardness. It was found that the deposition substrate temperature is the key factor to affect the deposition rate of remote APP chemical vapor deposition process. Fourier transform infrared (FTIR) spectra indicated that APP deposited SiO_x films are an inorganic feature. XPS examination revealed that the SiO_x films contained approximately 30% silicon, 58% oxygen and 12% carbon. Atomic forced microscopy (AFM) analysis results indicated a smooth surface of SiO_x films in deposition under higher substrate temperature. Also, pencil hardness tests indicated that the hardness of APP deposited SiO_x films was greatly improved with increasing substrate temperatures. Copyright © 2008 John Wiley & Sons, Ltd.     

Modeling Study on the Entrainment of Ambient Air into Subsonic Laminar and Turbulent Argon Plasma Jets

Modeling study is performed to reveal the special features of the entrainment of ambient air into subsonic laminar and turbulent argon plasma jets. Two different types of jet flows are considered, i.e., the argon plasma jet is impinging normally upon a flat substrate located in atmospheric air surroundings or is freely issuing into the ambient air. It is found that the existence of the substrate not only changes the plasma temperature, velocity and species concentration distributions in the near-substrate region, but also significantly enhances the mass flow rate of the ambient air entrained into the jet due to the additional contribution to the gas entrainment of the wall jet formed along the substrate surface. The fraction of the additional entrainment of the wall jet in the total entrained-air flow rate is especially high for the laminar impinging plasma jet and for the case with shorter substrate standoff distances. Similarly to the case of cold-gas free jets, the maximum mass flow-rate of ambient gas entrained into the turbulent impinging or free plasma jet is approximately directly proportional to the mass flow rate at the jet inlet. The maximum mass flow-rate of ambient gas entrained into the laminar impinging plasma jet slightly increases with increasing jet-inlet velocity but decreases with increasing jet-inlet temperature.     

Fast deposition of amorphous hydrogenated carbon films using a supersonically expanding arc plasma

Experiments concerning the growth rate and quality of an amorphous hydrogenated carbon film deposited in a reactor based on the supersonic expansion of an arc plasma are reported. In order to be able to calculate the deposition rate, an existing flow model has been completed with chernical reaction rate equations. The methane gas that is injected in the arc appears to be dissociated and ionized completely. The calculated deposition rates agree well with the experimental values obtained within-situ ellipsometry. The growth rates are an order of magnitude larger than those reported in the literature. Still, the film quality, expressed in terms of refractive index, optical bandgap, and hardness, is similar to those obtained by other authors.     

Probe measurements in thermal plasma jets

Measurements of composition, temperature, and velocity in atmospheric argon plasma jets are reported, using enthalpy probes. The plasma jets are generated by a commercial type plasma gun and the measurements are expected to be of particular interest for industrial applications such as plasma spraying. Emphasis has been on the central and downstream regions of the plasma flame. The entrainment of air into the jet was found to be very high, even close to the axis of the jet. Gas samples analyzed with a gas chromatograph showed demixing of the air, i.e., nitrogen is more abundant in the jet than at room temperature. The high air entrainment has a strong cooling effect on the plasma, resulting in a rapid temperature drop along the axis. The influence of the argon flow rate and of the arc current on the jet's conditions was parametrically studied. Matching of the quantities measured in the jet with the torch input confirmed the validity of the results, and the relevance of enthalpy probe diagnostics in thermal plasma jets.     

H2 plasma development of X-ray imaged patterns on plasma-polymerized resists

An X-ray imaged pattern on a plasma-polymerized film was successfully developed by H₂ plasma etching. Plasma-polymerized MMA and 6FBMA were formed by using an inductively coupled argon flow type reactor. An X-ray imaged pattern on the film was attained through a knife-cut window of a gold plate. The X-ray was generated from a Cu target at 20 kV and main wavelength 1.54 Å. The pattern development was performed using a tubular type reactor with parallel plate electrodes. The quality of plasma-polymerized resists in an X-ray lithography was evaluated by comparing it with the conventional polymer in the dry and wet process, and the minimum dose rate for a visible pattern fabrication was measured to be 4.1 J/cm² for both resists in H₂ plasma etching development.     

DC plasma polymerization of hexamethyldisiloxane

Hexamethyldisiloxane (HMDS) was polymerized onto metallic and insulating substrates in a parallel-plate DC reactor. The limits of the DC reactor with respect to pressure and power were determined for deposition of PP-HMDS films. In all conditions ranging from 5 Pa/0.3 W to 100 Pa/50 W, solid films were deposited. No powders or oily films were obtained under any condition in this operating range. The films were polymeric in nature,i.e., they were neither carbon-like nor SiO _x -like films. The structures and crosslink densities of the plasma films dependend strongly on the deposition conditions. The highest deposition rates, up to 2 μm per minute (or0.3 mg/cm² min), were obtained at high power, pressure, and flow rate conditions. An efficiency ɛ is introduced, defined as the fraction of the monomer that is retained in the form of a polymer deposited on the substrate. Efficiencies as high as 25% could be obtained in certain conditions. Pulsing the discharge power increased the conversion efficiency markedly, but the effect depended strongly on the monomer used. In addition to HMDS, plasma polymers were also deposited from pyrrole in pulsed conditions for comparison. A method is described for depositing films on insulators from a DC glow discharge using two wire meshes held at a negative potential.     

自偏压作用下纳米碳管的定向生长

以玻璃为基板材料, 在550 ℃的低温条件下利用微波等离子体化学气相沉积法合成了定向纳米碳管.结果表明, 在利用微波等离子体化学气相沉积法合成纳米碳管时, 因等离子体作用存在于基板表面的自偏压对纳米碳管的定向生长起着非常重要的作用.自偏压的作用总是使纳米碳管的生长垂直于基板表面.