Reductive Removal of Phosphorus in Silicon Using CaO-CaF2 Slag

"To develop an alternative metallurgical process for phosphorus removal in the production of solar-grade silicon (SOG-Si), slag treatment of metallurgical-grade silicon (MG-Si) was conducted, followed by acid leaching. Phosphorus-doped silicon alloy or MG-Si containing certain amounts of phosphorus and calcium was reacted at 1723 K and 1773 K with CaO--CaF2 of several compositions. Phosphorus removal from the molten silicon into the slag phase was confirmed by reduction to phosphide ions, P3-, and phosphate ions, P3-. These ions were separately determined using a wet chemical analysis method developed by ourselves. The highest phosphorus distribution ratio obtained was 2. 7 after reaction for 18 h with 17.5 mass% CaO--CaF2 slag. We then conducted acid leaching of the silicon and achieved removal of a large fraction (over 90 % ) of the phosphorus, which was much higher than that obtained by ordinary oxidizing slag treatment.IntroductionIn recent years, the production of solar cells has been increasing rapidly. Because of this, the demand for solar-grade silicon (SOG-Si) has also been growing rapidly. The development of lower-cost mass production processes is therefore needed to provide silicon feedstock. Phosphorus is one of the impurities in metallurgical-grade silicon (MG-Si). Because of its large segregation coefficient (kp = 0.35) [l ], it is difficult to remove phosphorus using a solidification refining process. Vacuum melting is considered to be a promising method for removing phosphorous from MG-Si [2], but the issues of high cost and large energy consumption have still to be resolved.Slag treatment is often used to remove impurity elements by oxidizing reactions during general oxidation refining processes. For example, phosphorus in molten steel is removed into a slag phase as phosphate ions, PO4 3-l-, by the following reaction:"