Equilibrium and Kinetic Considerations in Refining of Silicon

Sammanfattning: The purity requirements for photovoltaic-grade (PV) silicon are very stringent. In PV applications, purified silicon is either doped with boron or phosphorous, so the levels of these particular elements have to be tightly controlled. An alternative process route to photovoltaic-grade silicon that has been successfully implemented on an industrial scale is a multi-step process comprising carbothermic reduction, slag refining, hydrometallurgical extraction, and finally directional solidification. There are many fundamental aspects of the process that are not fully understood and need to be defined. In the refining of silicon using slag treatment, boron dissolved in the silicon is oxidized and rejected to a liquid oxide (slag) phase. The partitioning of boron between liquid silicon and SiO2–CaO–MgO slags was examined at 1873. It was found that the distribution of boron is strongly dependent on the oxygen partial pressure and nitrogen partial pressure, as well as the slag composition. The concentration of MgO seems to have little impact on the partition ratio. The greatest partition ratios were achieved at 0.6 atm CO / 0.4 atm N2 with low silica content in the slag. Experiments were carried out to study mass transfer rates between liquid silicon and CaO–SiO2 slag using mechanical stirring at 1823 K. The evidence suggests that the reduction of calcium oxide at the interface leads to a rapid, temporary drop in the apparent interfacial tension. At low apparent interfacial tension, mechanical agitation facilitates the dispersion of metal into the slag phase, which dramatically increases the interfacial area; here it has been estimated to increase by at least one order of magnitude. As the reaction rate slows down, the apparent interfacial tension increases and the metal re-coalesces. The rates of mass transfer of both Ca and B were found to increase by agitating the melt, which shows that without forced convection, the overall kinetic rates are mass-transfer controlled. From a reactor design perspective, this is ideal since it should be simpler to achieve optimal mixing conditions with less kinetic energy input into the melt. The infiltration of silicon into graphite was found to be highly dependent on the internal structure of the graphite substrate. It was confirmed that the heating history of silicon in contact with a graphite substrate strongly influences the melting behavior, which is likely attributed to a gas-solid reaction that forms SiC below the liquidus temperature of silicon and alters the surface properties of the graphite. It was also observed that a partial pressure of CO greater than 0.05 atm in the inlet gas leads to SiC formation on the surface of the silicon and severely hinders proper melting.