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A current listing of IR observations of circumstellar molecules is presented. These observations were performed using Fabry-Perot, Fourier transform, and laser heterodyne spectroscopy. The most abundant species were CO, SiO, and HCN, while trace species included NH3, CH4, SiH4, and CS. Among the undetected species were H2, HCl, and CH2.
The kinetics of low pressure CVD growth of SiO2 from SiH4 and O2 has been investigated for the case of an indirect (remote) plasma process. Homogeneous (gas phase) and heterogeneous operating ranges have been experimentally identified. The process was shown to be consistent within the heterogeneous surface-reaction dominated range of operation. A kinetic rate equation is given for growth at 14 W RF power input and 400 mtorr total pressure on both InP and Si substrates. The process exhibits an activation energy of 8.4 + or - 0.6 kcal/mol.
Coherent anti-Stokes Raman spectroscopy (CARS) and mass spectrometry (MS) have been applied to in situ process diagnostics of a silane plasma for device-quality a-Si:H film deposition. Silane depletion was directly measured by CARS and is linearly dependent on RF power in the region of 4-12 W with a slope of 0.5 percent/mW-sq cm. The depletion is also dependent on SiH4 flow rate starting with a 50 percent depletion at a low flow rate of 5.6 sccm and asymptotically approaching an 8 percent depletion at a flow rate of 80 sccm. The mass spectral line signal intensity of disilane increases with RF power and shows an apparent transition at 6 W. Disilane formation in silane plasma, film deposition rate, and silane depletion ratio as a function of the RF power indicate that the film growth mechanism in the low-power region of 3.5-6.5 W is substantially different from that in the high-power region of 6.5-12 W.
This paper reports on an in situ silicon deposition process diagnostics, using CARS performed at state-of-the-art a-Si:H film deposition conditions in a reactor designed for a-Si:H solar cell fabrication. The diagnostics procedure measures the silane depletion in an RF plasma as a function of the silane flow rate (where the relationship is linear between 50-percent depletion, at a flow rate of 5.6 sccm, and about 8-percent depletion, at 80 sccm) and the RF power (where the silane depletion is linearly dependent on the RF power in the region of 4 to 12 W). The linear RF power dependence of the silane depletion is considered to be consistent with the mechanism of silane decomposition primarily by electron impact dissociations, while the flow rate dependence is interpreted in terms of the residence time of the SiH4 molecules in the glow discharge region, where an increase of the residence time at a low flow rate results in a high depletion ratio.
This paper reports preliminary measurements of the oxygen isotopic fractionation that occurs during the condensation of refractory metal oxide smokes. Fractionation occurred at temperatures in excess of 500 K during and/or subsequent to reaction of SiH4, Fe(CO)5, Al(CH3)3, and O2 in a H2 carrier gas. Observed isotopic fractionation was as high as -15 per mil/amu. The magnitude of the isotopic fractionation suggests that the process is kinetically controlled since the effect is greatly in excess of that expected for equilibrium isotopic exchange.
A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamic maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of Region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicon carbide is the single stable solid phase in Region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4, and SiH. Analysis of the kinetics of reaction for Region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to Regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.
It is demonstrated that the steady-state and kinetic characteristics of ECR (electron cyclotron resonance) and RF glow discharge plasmas can be readily monitored by OES (optical emission spectroscopy) in real time during a-Si:H and a-SiC:H film depositions using an OMA detection system. The ECR and RF glow discharge plasmas used for a-Si:H and a-SiC:H film depositions were studied by monitoring the emission of SiH(asterisk), H(asterisk), H(asterisk)2, and CH(asterisk) excited states. The OES of the ECR plasma shows a strong emission at 434 nm from H(asterisk), which is not detectable in the glow discharge plasma. Steady-state OES studies have established preliminary correlations between SiH(asterisk) and CH(asterisk) emission intensities and the film deposition rate. Transient OES spectra of SiH4 and CH4 plasmas have shown different kinetics in SiH(asterisk) and CH(asterisk) emission intensities. Transient studies of the SiH(asterisk) emission intensity have indicated that additional mechanisms for producing the SiH(asterisk) species become evident in hydrogen-diluted silane plasmas.
Experimental techniques for studying the processes which occur during the life cycle of a refractory grain are reviewed. Consideration is given to the construction of a differentially-pumped beam-mass spectrometer which is expected to determine the relative stability of small clusters in the Fe-Mg-Si-O and Ca-Ti-Al-O systems as a function of temperature and pressure. Also, a smoke generator has been constructed to produce gram quantities of amorphous grains for use in thermal annealing and hydrous alteration studies of smokes containing Fe-Mg-Al-Ti-Ca-Si-O and Cl. Topics of the studies include the properties of grains produced in a flow condensation apparatus, the sorption efficiency of Si2O3 smokes for AR gas, the processing of ices containing refractory precursors such as SiH4 or Fe(CO)5 plus water, and the residue from 1 MeV bombardment and warming of an amorphous Fe-SiO smoke.
The nitriding kinetics of Si and Si plus SiC powder mixtures were studied to simulate the fabrication of RBSN-SiC ceramic matrix composites. Very clean, assynthesized, and solvent-exposed powders were studied; C-rich and Si-rich SiC 0.04-0.05 micron diameter powders were mixed in varying concentrations with SiH4-derived 0.2-0.3 micron diameter Si powder. Complete nitridation is achieved with C-rich SiC powders in 140 min at 1250 C, and in the centers of Si-rich SiC powders in 15 min. The effects on the incubation periods, fast reaction periods, and slow reaction periods that characterize these nitriding processes were studied to explain unusual reverse reaction gradients and other effects of contamination.
A comparative study is made to identify the most advantageous fuel/oxidizer combinations which could be supplied to spacecraft from in situ resources or from the most economical earth-transported storable fuels. The performance of the unconventional fuel/oxidizer combinations in question are computed for a wide range of pressures, expansion ratios and initial temperatures. The propellants discussed are, (1) for LEO: H2 + O2, NH3 + N2O4; (2) for the moon: CH4 + O2, SiH4 + O2, H2 + Al + O2, butyl rubber + O2, silicone + O2, and polystyrene + O2; and (3) for Mars: CO + O2, CO + H2O2, CO + N2O4, C2H5OH + O2, and CH3OH + O2.
Studies of the properties of refractory metal oxide smokes condensed from a gas containing various combinations of SiH4, Fe(CO)5, Al(CH3)3, TiCl4, O2 and N2O in a hydrogen carrier stream at 500 K greater than T greater than 1500 K were performed. Ultraviolet, visible and infrared spectra of pure, amorphous SiO(x), FeO(x), AlO(x) and TiO(x) smokes are discussed, as well as the spectra of various co-condensed amorphous oxides, such as FE(x)SiO(y) or Fe(x)AlO(y). Preliminary studies of the changes induced in the infrared spectra of iron-containing oxide smokes by vacuum thermal annealing suggest that such materials become increasingly opaque in the near infrared with increased processing: hydration may have the opposite effect. More work on the processing of these materials is required to confirm such a trend: this work is currently in progress. Preliminary studies of the ultraviolet spectra of amorphous Si2O3 and MgSiO(x) smokes revealed no interesting features in the region from 200 to 300 nm. Studies of the ultraviolet spectra of both amorphous, hydrated and annealed SiO(x), TiO(x), AlO(x) and FeO(x) smokes are currently in progress. Finally, data on the oxygen isotopic composition of the smokes produced in the experiments are presented, which indicate that the oxygen becomes isotopically fractionated during grain condensation. Oxygen in the grains is as much as 3 percent per amu lighter than the oxygen in the original gas stream. The authors are currently conducting experiments to understand the mechanism by which fractionation occurs.
A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamics maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicone carbide is the single stable solid phase in region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4 and SiH. Analyses of the kinetics of reaction for region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.
Amorphous and microcrystalline silicon carbon films (a-SiC:H, micro-c-SiC:H) have been deposited using SiH4, CH4 and H2 mixed gas ECR (electron cyclotron resonance) plasmas. The optical bandgap of a-SiC:H films is not dependent on the hydrogen dilution in the ECR plasma. The deposition rate of a-SiC:H films is found to be strongly dependent on the ECR magnetic field and the hydrogen dilution. The hydrogen dilution effect on the deposition rate indicates that the etching in ECR hydrogen plasmas plays an important role in the deposition of a-SiC:H films. The optical constants n and k of ECR-deposited a-SiC:H films in the wavelength region of 0.4 to 1.0 micron are determined to be 2.03-1.90 and 0.04-0.00, respectively. The microstructures of ECR-deposited micro-c-SiC:H films are shown by X-ray diffraction and SEM (scanning electron microscopy) to be composed of 1000-A alpha-SiC microcrystallites and amorphous network structures.
Structural fibers are currently being considered as reinforcements for intermetallic and ceramic materials. Some of these fibers, however, are easily degraded in a high temperature oxidative environment. Therefore, coatings are needed to protect the fibers from environmental attack. Silicon carbide (SiC) was chemically vapor deposited (CVD) on Textron's SCS6 fibers. Fiber temperatures ranging from 1350 to 1500 C were studied. Silane (SiH4) and propane (C2H8) were used for the source gases and different concentrations of these source gases were studied. Deposition rates were determined for each group of fibers at different temperatures. Less variation in deposition rates were observed for the dilute source gas experiments than the concentrated source gas experiments. A careful analysis was performed on the stoichiometry of the CVD SiC coating using electron microprobe. Microstructures for the different conditions were compared. At 1350 C, the microstructures were similar; however, at higher temperatures, the microstructure for the more concentrated source gas group were porous and columnar in comparison to the cross sections taken from the same area for the dilute source gas group.
Cross-sections and appearance potentials for the production of various negative ion species by electron impact on SiH4 have been measured. They are compared with two previous measurements which widely differ with each other. Hess' law has been applied to predict the various possible channels of dissociation.
Device-quality a-Si:H and a-SiC:H films have been deposited using electron cyclotron resonance (ECR) microwave plasmas of SiH4, CH4, and H2 mixtures. Typical material properties of ECR-deposited, photosensitive a-Si:H films are: (1) high photosensitivity up to 2 x 106 with a photoconductivity of 10 exp -5 to 10 exp -4/(Ohm-cm), (2) a Tauc gap of 1.75 to 1.85 eV, (3) an Urbach slope of 50-60 meV determined by the constant photocurrent method, and (4) an integrated defect density of 1-2 x 10 exp 16/cu cm determined by junction capacitance measurements. Highly conductive, p-type a-SiC:H films have been produced by ECR plasmas with a conductivity of 0.2/(Ohm-cm).
Structural fibers are currently being considered as reinforcements for intermetallic and ceramic materials. Some of these fibers, however, are easily degraded in a high temperature oxidative environment. Therefore, coatings are needed to protect the fibers from environmental attack. Silicon carbide (SiC) was chemically vapor deposited (CVD) on Textron's SCS6 fibers. Fiber temperatures ranging from 1350 to 1500 C were studied. Silane (SiH4) and propane (C2H8) were used for the source gases and different concentrations of these source gases were studied. Deposition rates were determined for each group of fibers at different temperatures. Less variation in deposition rates were observed for the dilute source gas experiments than the concentrated source gas experiments. A careful analysis was performed on the stoichiometry of the CVD SiC coating using electron microprobe. Microstructures for the different conditions were compared. At 1350 C, the microstructures were similar; however, at higher temperatures, the microstructure for the more concentrated source gas group were porous and columnar in comparison to the cross sections taken from the same area for the dilute source gas group.
The paper reports electron cyclotron resonance (ECR) deposition of a-Si:H and a-SiC:H thin films using SiH4, CH4, and hydrogen mixed gas plasmas. The ECR deposition conditions were investigated in the pressure region of 0.1 to 100 mtorr, and the film properties were characterized by light and dark conductivity measurements, XRD, Raman spectroscopy, optical transmission, and IR spectroscopy. In addition, the hydrogen dilution effect on ECR-deposited a-SiC:H was investigated.