Thermodynamic Study for the Removal of Phosphorus from Molten Silicon

"The production of solar cells is increasing dramatically and the shortage of polycrystalline silicon for these cells has become a serious problem, making development of a low-cost production process for solar grade silicon essential. An electron beam melting technique is known to be effective for the removal of phosphorus from molten silicon. Although the phosphorus is removed by preferential evaporation in this process, the rate of removal is not sufficient, and its improvement requires thermodynamic information on phosphorus in the molten silicon. In this research, the vapor pressure of phosphorus in equilibrium with a siliconphosphorus alloy was measured by double Knudsen cell mass spectrometry with a system blowing gas into the Knudsen cell. The activity of phosphorus in silicon, the Gibbs energy change of the dissolution of phosphorus in silicon, and other factors were estimated from the results. Using these data, we provided guidelines on how this process can be improved.IntroductionSolar energy is in great demand since it is inexhaustible and cleaner than that from conventional energy resources. Silicon is the material most widely used to convert solar energy into electricity. Figure 1 shows the recent production of solar cells. High purity silicon for solar cells, namely solar grade silicon (SOG-Si), has been commercially supplied mainly from off-grade high purity silicon in the semiconductor industry. However, production of solar cells has increased rapidly in recent years, and the shortage of SOG-Si has become a serious problem, so that a new processes which can produce SOG-Si economically are required.Directional solidification was applied to remove transition metal elements such as Fe or Ti by segregating them from the remaining melt. However, such solidification is useless for phosphorus because the segregation coefficient of phosphorus is nearly unity. Numerous approaches have been made in an attempt to produce a resource of low cost SOG-Si from metallurgical-grade silicon (MG-Si). [1,2]"