Engineering topics
Publications and source records attributed to Bates, H. E..
High-purity silicon efficiently produced and transferred by continuous two-cycle reactor. New reactor operates in relatively-narrow temperature rate and uses large surfaces area to minimize heat expenditure and processing time in producing silicon by hydrogen reduction of trichlorosilane. Two cycles of reactor consists of silicon production and removal.
Delivery tube transfers molten silicon between high-temperature vessel. Transport tube is sealed to delivery vessel and receiving vessel and slanted so gravity moves molten silicon. Contamination is prevented since molten silicon only contacts quartz delivery tube.
Drop length necessary to convert molten silicon to shot reduced by proposed new process. Conversion of silicon from powder or chunks to shot often simplifies processing. Shot is more easily handled in most processing equipment. Drops of liquid silicon fall through protective cloud of argon, then through rapidly cooling bath of methanol, where they quickly turn into solid shot.
Single-crystal ribbon of silicon or other material is grown by pulling at low angle from shallow melt. By pulling crystal at small angle, technique prevents overflow problem experienced with horizontal growth. Also creates meniscus that minimizes growth defects in main portion of ribbon. Use of shallow pool prevents convection problems.
The operation of a silicon production technique was demonstrated. The essentials of the method comprise chemical vapor deposition of silicon, by hydrogen reduction of chlorosilanes, on the inside of a quartz reaction vessel having large internal surface area. The system was designed to allow successive deposition-melting cycles, with silicon removal being accomplished by discharging the molten silicon. The liquid product would be suitable for transfer to a crystal growth process, casting into solid form, or production of shots. A scaled-down prototype reactor demonstrated single pass conversion efficiency of 20 percent and deposition rates and energy consumption better than conventional Siemens reactors, via deposition rates of 365 microns/hr. and electrical consumption of 35 Kwhr/kg of silicon produced.
The low cost production of silicon by deposition of silicon from a hydrogen/chlorosilane mixture is described. Reactor design, reaction vessel support systems (physical support, power control and heaters, and temperature monitoring systems) and operation of the system are reviewed. Testing of four silicon deposition reactors is described, and test data and consequently derived data are given. An 18% conversion of trichlorosilane to silicon was achieved, but average conversion rates were lower than predicted due to incomplete removal of byproduct gases for recycling and silicon oxide/silicon polymer plugging of the gas outlet. Increasing the number of baffles inside the reaction vessel improved the conversion rate. Plans for further design and process improvements to correct the problems encountered are outlined.
A system to combine silicon formation, by hydrogen reduction of trichlorosilane, with the capability to replenish a crystal growth system is described. A variety of process parameters to allow sizing and specification of gas handling system components was estimated.
Continuous growth methodology for silicon solar cell ribbons deals with capillary effects, die effects, thermal effects and crystal shape effects. Emphasis centers on the shape of the meniscus at the ribbon edge as a factor contributing to ribbon quality with respect to defect densities. Structural and electrical characteristics of edge defined, film-fed grown silicon ribbons are elaborated. Ribbon crystal solar cells produce AMO efficiencies of 6 to 10%.
The growth and characteristics of edge defined, film fed grown (EFG) silicon ribbons are discussed. Factors involved in the growth of continuous lengths of 1 in. wide ribbons are examined. The structural and electrical characteristics of the ribbons have been studied and the results are presented. Solar cells have been fabricated using the ribbon crystals and typical AMO efficiencies of 6 to 10% have been realized.
One inch wide silicon ribbons up to 14 inches long have been produced from graphite dies. Several different techniques have been employed to improve the semiconductor purity of silicon. This has resulted in a general increase in quality although the techniques involved have not been optimized. The power factor of uncoated ribbon solar cells produced for material evaluation has increased to approximately 75% of those evaluation cells made from commercial silicon. The present limitation is believed due to low lifetime. Additional work has continued with new die materials; however, only composite dies of SiO2 and C show significant potential at this time.
Recent advances in the application of the edge-defined, film-fed growth (EFG) method to silicon ribbon are described. Ribbons up to 2 x 40 cm and 1 x 70 cm in width and length, respectively, have been grown at rates of 1 to 2.5 cm/min. The electrical properties of typical undoped ribbons are resistivity of 0.5 to 5 ohm-cm p-type, and hole mobility of 200 to 350 sq cm/V-sec. Ribbon growth speeds are consistent with the use of EFG silicon for terrestrial power.
The research which was directed toward finding an improved die material is reported. Wetting experiments were conducted with various materials to determine their compatibility with silicon. Work has also continued toward the development of quartz as a die material as new techniques have provided more optimistic results than observed in the past. As a result of the thermal modification previously described, improvements in growth stability have contributed to an increase in ribbon quality.
Hall mobility measurements on a number of single crystal silicon ribbons grown from graphite dies have shown some ribbons to have mobilities consistent with their resistivities. The behavior of other ribbons appears to be explained by the introduction of impurities of the opposite sign. Growth of a small single crystal silicon ribbon has been achieved from a beryllia dia. Residual internal stresses of the order of 7 to 18,000 psi have been determined to exist in some silicon ribbon, particularly those grown at rates in excess of 1 in./min. Growth experiments have continued toward definition of a configuration and parameters to provide a reasonable yield of single crystal ribbons. High vacuum outgassing of graphite dies and evacuation and backfilling of growth chambers have provided significant improvements in surface quality of ribbons grown from graphite dies.
Silicon ribbon growth experiments were conducted using orifices (dies) fabricated from SiC-SiO2 mixtures, fused quartz, SiC, and fine-grained, high density graphite. The best results were obtained from graphite dies. A number of different approaches was tried in modifying the thermal gradient in the dies and in holding the dies. The best results here were obtained from a 0.25-in. thick Mo disc holding a graphite die directly and fitting the die quite closely. Ribbon growths as wide as 9 mm were obtained, while the longest ribbon was 450 x 3.5 x 0.5 mm. Resistivities of ribbons grown from graphite dies have been measured over the range of 0.03 to 1.6 ohm-cm. Some thoughts and literature findings are presented regarding refractory oxide materials as potential orifices.
Thick film silicon ribbons were produced by means of the edge-defined, film-fed growth (EFG) technique. EFG is a process by which single crystals may be grown having a shape controlled by the outside dimensions of a die, the growth taking place from an extremely thin film of liquid fed by capillary action from a crucible below. The principal problem to be overcome in the application of this process to the growth of thick film silicon ribbon relates to the material, such as the shaping die. For the method to operate, this die material must be wet by the liquid silicon. To preserve semiconductor quality, the liquid silicon must not react significantly with the die material. The most promising die material for this application appears to be SiC and SiC-SiO2 admixture. In this case good wetting occurs between the molten silicon and the SiC. C is a relatively unharmful contaminant of Si and additions of quartz to SiC are found to decrease the extent of reaction.
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Thermoelectric system of Cd-Si-Ge, and tungsten diffusion bonded lead telluride
Procedure for segmenting lead telluride and silicon germanium thermoelectric elements to obtain composite elements effective over wide temperature range