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The feasibility of silicon nitride as a regenerator matrix material for applications requiring inlet temperatures above 1000 C is examined. The present generation oxide ceramics are used as a reference to examine silicon nitride from a material characteristics, manufacturing, thermal stress and aerothermodynamic viewpoint.
Two computer codes were developed for describing flow reactors in which high purity, solar grade silicon is produced via reduction of gaseous silicon halides. The first is the CHEMPART code, an axisymmetric, marching code which treats two phase flows with models describing detailed gas-phase chemical kinetics, particle formation, and particle growth. It can be used to described flow reactors in which reactants, mix, react, and form a particulate phase. Detailed radial gas-phase composition, temperature, velocity, and particle size distribution profiles are computed. Also, deposition of heat, momentum, and mass (either particulate or vapor) on reactor walls is described. The second code is a modified version of the GENMIX boundary layer code which is used to compute rates of heat, momentum, and mass transfer to the reactor walls. This code lacks the detailed chemical kinetics and particle handling features of the CHEMPART code but has the virtue of running much more rapidly than CHEMPART, while treating the phenomena occurring in the boundary layer in more detail.
High open circuit voltage cell designs based on 0.1 Ohm cm p-type silicon were irradiated with 1 MeV electrons and their performance determined to fluences as high as 10 to the 15th power per sq cm. Of the three cell designs, radiation induced degradation was greatest in the high low emitter (HLE) cell. The diffused and ion implanted cells degraded approximately equally but less than the HLE cell. Degradation was greatest in an HLE cell exposed to X-rays before electron irradiation. The cell regions controlling both short circuit current and open circuit voltage degradation were defined in all three cell types. An increase in front surface recombination velocity accompanied time dependent degradation of an HLE cell after X-irradiation. It was speculated that this was indirectly due to a decrease in positive charge at the silicon oxide interface. Modifications aimed at reducing radiation induced degradation are proposed for all three cell types.
A miniature gas analysis system has been built based on the principles of gas chromatography (GC). The major components are fabricated in silicon using photolithography and chemical etching techniques, which allows size reductions of nearly three orders of magnitude compared to conventional laboratory instruments. The chromatography system consists of a sample injection valve and a 1.5-m-long separating capillary column, which are fabricated on a substrate silicon wafer. The output thermal conductivity detector is separately batch fabricated and integrably mounted on the substrate wafer. The theory of gas chromatography has been used to optimize the performance of the sensor so that separations of gaseous hydrocarbon mixtures are performed in less than 10 s. The system is expected to find application in the areas of portable ambient air quality monitors, implanted biological experiments, and planetary probes.
The paper presents a study to determine the fracture toughness and to characterize fracture modes of silicon as a function of the orientation of single-crystal and polycrystalline material. It is shown that bar specimens cracked by Knoop microhardness indentation and tested to fracture under four-point bending at room temperature were used to determine the fracture toughness values. It is found that the lowest fracture toughness value of single crystal silicon was 0.82 MN/m to the 3/2 in the 111 plane type orientation, although the difference in values in the 111, 110, and 100 planes was small.
Microscopic and electrical measurements were performed to explain the degradation mechanisms associated with the presence of titanium impurities in silicon. The measurements included X-ray topography, transmission electron microscopy, and deep level transient spectroscopy, before and after processing. The results indicated the presence of TiO2 precipitates, the density of which increased after phosphorus diffusion. A majority carrier trapping level was observed in the wafers before processing. It was concluded that 10% of the Ti in the N(+)/P silicon solar cells formed electrically active centers which caused degradation of the cell junction. 14% of the remaining Ti precipitated out as TiO2, forming electrically active defects, which also caused junction degradation.
The paper describes the silicon material task of the low-cost solar array project, which has the objective of establishing a silicon production capability equivalent to 500 mW per year at a price less than 10 dollars/kg (1975 dollars) in 1986. The task program is divided into four phases: technical feasibility, scale-up studies (the present phase), experimental process system development units, and implementation of large-scale production plants, and it involves the development of processes for two groups of materials, that is, semiconductor grade and solar cell grade. In addition, the effects of impurities on solar cell performance are being investigated. Attention is given to problem areas of the task program, such as environmental protection, material compatibility between the reacting chemicals and materials of construction of the equipment, and waste disposal.
Open-circuit voltages as high as 0.645 V (AM0, 25 C) have been obtained by a new process developed for low-resistivity silicon. The process utilizes high-dose phosphorus implantation followed by furnace annealing and simultaneous oxide growth. The effect of the thermally grown oxide is a reduction of surface recombination velocity; the oxide also acts as a moderately efficient antireflection (AR) coating. Boron-doped, float-zone silicon with resistivities from 0.1 to 1.0 (omega)(cm) has been processed according to this sequence; results show that the highest open-circuit voltage is obtained with 0.1(omega)(cm) starting material. The effects of Auger recombination and bandgap narrowing caused by high doping concentrations in the n(+)junction region have been investigated by implanting phosphorus over a wide range of dose levels. The effects of emitter-phosphorus concentrations tailored to optimize electric fields in the emitter have also been investigated.
The preparation and radiometric properties of silicon detectors coated with fluorescent thin films are described. The films are deposited from solutions of clear plastics, such as acrylic resins, polyvinyl toluene or polystyrene, and of organic laser dyes in a common solvent. They are optically clear, mechanically and chemically stable, yet easily applied and removed. Multiple doped films of a few microns thickness exhibit broad-band absorption from less than 250 nm to about 450 nm and narrow band emissions with peaks ranging from 380 nm to 600 nm. Internal quantum efficiencies are close to 100 percent and fluorescence decay times are in the nanosecond range. When deposited on optically denser media, a large fraction of the fluorescent emission is trapped in the substrate. Silicon photodiodes coated with multiple doped films exhibit high external quantum efficiencies and virtually flat photon response in the near UV.
It is noted that currently available reaction bonded silicon nitride (RBSN) materials are limited by relatively low strength (up to 300 MPa) and oxidation resistance, primarily due to open porosity. Attention is given to technology that was developed and used to produce an improved grade of injection molded RBSN having a density of 2.8 g/cc, with significantly decreased open porosity and a strength exceeding 350 MPa. It is shown that these results are primarily due to advances in two areas: silicon powder processing, and nitriding technique. A comparison of room temperature strength and oxidation resistance of the new material with that of state-of-the-art RBSN, showed significant improvements. It is concluded that turbine stator vanes were produced to show that this improved RBSN technology has been reduced to engineering practice.
Three high open-circuit voltage cell designs based on 0.1 ohm-cm p-type silicon were irradiated with 1 MeV electrons and their performance determined to fluences as high as 10 to the 15th/sq cm. Of the three cell designs, radiation induced degradation was greatest in the high-low emitter (HLE) cell. The diffused and ion implanted cells degraded approximately equally but less than the HLE cell. Degradation was greatest in an HLE cell exposed to X-rays before electron irradiation. The cell regions controlling both short-circuit current and open-circuit voltage degradation were defined in all three cell types. An increase in front surface recombination velocity accompanied time dependent degradation of a HLE cell after X-irradiation. It was speculated that this was indirectly due to a decrease in positive charge at the silicon-oxide interface. Modifications aimed at reducing radiation induced degradation are proposed for all three cell types.
The effect of tungsten and tungsten carbide contamination on the oxidation and cracking in air of yttria-doped silicon nitride ceramics is investigated. Silicon nitride powder containing 8 wt % Y2O3 was doped with 2 wt % W, 4 wt % W, 2 wt % WC or left undoped, and sintered in order to simulate contamination during milling, and specimens were exposed in air to 500, 750 and 1350 C for various lengths of time. Scanning electron and optical microscopy and X-ray diffraction of the specimens in the as-sintered state reveals that the addition of W or WC does not affect the phase relationships in the system, composed of alpha and beta Si3N4, melilite and an amorphous phase. Catastrophic oxidation is observed at 750 C in specimens containing 2 and 4 wt % W, accompanied by the disappearance of alpha Si3N4 and melilite from the structure. At 1350 C, the formation of a protective glassy oxide layer was observed on all specimens without catastrophic oxidation, and it is found that pre-oxidation at 1350 C also improved the oxidation resistance at 750 C of bars doped with 4 wt % W. It is suggested that tungsten contamination from WC grinding balls may be the major cause of the intermediate-temperature cracking and instability frequently observed in Si3N4-8Y2O3.
The Dow Corning approach to increasing the resistivity of solar-grade silicon from about 0.04 ohm-cm (40 ppma B) to greater than 0.1 ohm-cm (10 ppma B) involves the use of high-purity raw materials carbothermically reduced in a specially designed electric arc furnace. Final purification occurs during Czochralski crystal growth of a polycrystalline ingot. This small-scale purification technology has resulted in silicon that has been fabricated into solar cells with a maximum AM1 conversion efficiency of 13.4%.
Proposal for removing impurities from silicon ribbon and sheet could be developed into an automated production-line process. New technique which combines ion-cluster bombardment, electron-gun heating, and plasma etching, could be key step in fabricating inexpensive solar-cell arrays. Silicon sheets and ribbons treated this way could have enhanced carrier lifetimes necessary for satisfactory solar-cell performance.
Growth of continuous silicon dendritic web that is up to 5 cm wide instead on only 1.3 cm is formed by freezing of supercooled liquid silicon between two needlelike dendritic crystals. Growth takes place in a work chamber filled with argon gas. As web grows, it is drawn out of chamber through a duct and guided to a storage reel.
The reduction of the temperatures required to restore cell performance after irradiation was investigated with emphasis on the annealing characteristics of two groups of cells containing different amounts of oxygen and carbon. Examination of defect behavior in irradiated boron doped silicon leads to the tentative conclusion that further reduction in annealing temperature could be achieved by decreasing the carbon concentration and either neutralizing the divacancy and/or minimizing its formation as a result of irradiation. A significant reduction in the temperature required to remove radiation induced degradation in 0.1 ohm centimeter silicon solar cells was achieved.
Degradation of silicon and GaAs solar cells due to exposures to low energy proton and electron environments and annealing data for these cells are discussed. Degradation of silicon cells in simultaneously combined electron and low energy proton environments and previous experimental work is summarized and evaluated. The deficiencies in current solar array damage prediction techniques indicated by these data and the relevance of these deficiencies to specific missions such as intermediate altitude orbits and orbital transfer vehicles using solar electric propulsion systems are considered.
The microstructure of reaction sintered silicon nitride (RSSN) was changed over a wide range by varying the grain density, grain size of the silicon starting powder, nitriding conditions, and by introducing artificial pores. The influence of single microstructural parameters on mechanical properties like room temperature strength, creep behavior, and resistance to thermal shock was investigated. The essential factors influencing these properties were found to be total porosity, pore size distribution, and the fractions of alpha and beta Si3N4. In view of high temperature engineering applications of RSSN, potentials for optimizing the material's properties by controlled processing are discussed.