Distribution of impurity elements in slag–silicon equilibria for oxidative refining of metallurgical silicon for solar cell applications

The possibility of refining metallurgical grade silicon to a high-purity product for solar cell applications by the slagging of impurity elements was investigated. Distribution coefficients were determined for B, Ca, Mg, Fe, K and P between magnesia or alumina saturated Al2O3–CaO–MgO–SiO2 and Al2O3–BaO–SiO2 slags and silicon at 1500 °C. The partitioning of the impurity elements between molten silicon and slag was examined in terms of basicity and oxygen potential of the slag, with particular focus on the behaviour of boron and phosphorus. The experimental results showed that both of these aspects of slag chemistry have a significant influence on the distribution coefficient of B and P. Increasing the oxygen potential by additions of silica was found to increase the distribution coefficients for both B and P. Increasing the basicity of the slag was not always effective in achieving high removal of these elements from silicon as excess amounts of basic oxides lower the activity of silica and consequently the oxygen potential. The extent of this effect is such that increasing basicity can lead to a decrease in distribution coefficient. Increasing lime in the slag increased distribution coefficients for B and P, but this counterbalancing effect was such that distributions were the lowest in barium-containing slags, despite barium oxide being the most basic of the fluxes used in this study. The highest removal efficiencies achieved were of the order of 80% and 90% for B and P, respectively. It was demonstrated that for the removal of B and P from metallurgical-grade silicon to solar-grade levels, a slag mass about 5 times the mass of silicon would be required.