Technical-grade silicon is purified to produce silicon having less than 1 ppm of electrically effective impurities therein, particularly boron and phosphorus, by treating molten technical silicon with a hydrogen containing gas in the presence of water so as to remove such impurities from the molten silicon.
Relatively pure Si (having less than about 1 ppm of detrimental impurities therein) is obtained from ordinary quartz sand by uniformly admixing such sand with suitable glass-forming materials, such as boron oxide and alkali-metal carbonates or oxides, melting such admixture to form a glass, annealing the glass so as to obtain a phase separation comprised of an SiO.sub.2 -- rich phase and an impurity-rich phase, extracting the impurity-rich phase via strong acid, such as nitric acid, washing and drying the remaining glass and reducing such glass with carbon-containing compounds, such as graphite, sucrose, starch, etc., in an electric arc. The so-obtained relatively pure silicon is suitable for fabrication into semiconductor components, such as solar cells.
Highly pure silicon is produced by refining impure silicon to remove deleterious impurities by contacting a melt of the impure silicon with a reacitve gas which comprises a gaseous halogen compound mixed with steam, hydrogen or a stem/hydrogen mixture.
An object of the present invention is to provide a process and apparatus for the continuous flow production of polycrystalline silicon from metallic silicon or silicon oxide as a raw material and also for the manufacture of a wafer by using it, which process and apparatus permit the mass production at a low cost. The above object can be attained by the manufacture of polycrystalline silicon and a silicon wafer for a solar cell by the following steps: (A) smelting metallic silicon under reduced pressure, carrying out solidification for the removal of the impurity components from the melt, thereby obtaining a first ingot, (B) removing the impurity concentrated portion from the ingot by cutting, (C) re-melting the remaining portion, removing boron and carbon from the melt by oxidizing under an oxidizing atmosphere, and blowing a mixed gas of argon and water to carry out deoxidization, (D) casting the deoxidized melt into a mold, and carried out directional solidification to obtain a second ingot, and (E) removing the impurity concentrated portion of the ingot obtained by directional solidification by cutting.
In the production of silicon articles at an elevated temperature, a stream comprising a controlled mixture of an oxygen-containing first gas and a second gas is admitted to the processing chamber. The first gas is one which partially dissociates under the conditions in the chamber to form both oxygen and the second gas. The second gas is one which is not harmful to silicon at the conditions in the chamber. Substantially equilibrium conditions are established in the chamber so that the dissociation of the first gas to oxygen occurs reversibly. The partial pressure of oxygen (P.sub.O.sbsb.2) is sensed in the chamber during processing of the article. In response to the P.sub.O.sbsb.2 level, the ratio of the rates of flow of the oxygen-containing gas and the second gas is adjusted so as to maintain the P.sub.O.sbsb.2 at a level less than about 10.sup.-6 atmosphere, and usually no greater than about 10.sup.-10 atmosphere, at which the density of oxygen-related defects in the processed silicon article is acceptably low. Oxygen-related defects in the silicon are thereby reduced. If graphite structures are present in the hot zone of the processing chamber, they are preferably coated with an impervious coating which will stand the high temperature and will prevent the gas stream from coming into contact with the hot graphite. Carbon-related defects in the silicon are thereby also reduced.
