Passivation Threshold for the Oxidation of Liquid Silicon and Thermodynamic Non-equilibrium in the Gas Phase

The present study focuses on a specific step of the metallurgical path of purification to provide solar-grade silicon: the removal of boron through the injection of H2O(g)-H2(g)-Ar(g) (cold gas process). A progressive increase of the oxidant H2O(g) concentration at injection increases the speed of the process until a silica layer appears at the surface of the liquid silicon to be purified. It then stops the purification. During the process, silica aerosols may form in the gas boundary layer. This modifies the flows of oxidants and the gas concentrations at the liquid silicon surface. Using a monodimensional model, this article shows that a hypothesis of thermodynamic equilibrium of silica aerosols with the gas phase in the boundary layer has to be dropped in order to explain the appearance of a silica passivating layer. The passivation threshold is defined as the limit concentration of the oxidant at the injection below which there is no silica on the liquid silicon surface and beyond which silica particles appear on the liquid silicon surface. Three experiments of estimation of the passivation threshold with the injection of water vapor are used to confirm an empirical criterion for the prediction of the appearance of the silica layer. Two other sets of experiments with the injection of Ar-O2 are also being studied where the kinetics of the formation of silica aerosols seems to be slower than when water vapor is used. An optimization of the speed of boron removal under the assumption of a maximal concentration of water vapor before the appearance of a passivating silica layer would require an increase of the liquid silicon surface temperature from the fusion temperature of silicon.