Electrochemical studies on silicon deposition were performed in molten salt electrolytes. Purification of metallurgical grade silicon by electrorefining was carried out in molten Si-chloride salts at temperatures from 973 K to 1223 K. It was found that the use of a liquid alloy anode of silicon and copper was beneficial in molten CaCl2 with NaCl, CaO and dissolved Si. ICP-AES analysis results showed efficient removal of metal impurities, such as titanium, aluminum and iron, which are present in significant quantities in the feedstock. The contents of boron and phosphorus in the silicon after electrorefining were reduced from 36×10-6 and 25×10-6 to 4.6×10-6 and 2.8 ×10-6, respectively. The energy consumption of electrorefining was estimated to be about 9.3 kW?h/kg.
蔡靖罗学涛卢成浩Geir Martin HAARBERGAnnabelle LAURENTOle Edvard KONGSTEIN王淑兰
The removal of boron from metallurgical silicon in slag system of CaO-SiO2-10%CaF2 was investigated. The partition coefficient of boron （LB） between slag and silicon phase was studied under different conditions of slag basicity （CaO/SiO2 ratio）, temperature, mass ratio of slag to silicon and gas blowing. The results show that LB has a maximum value of 4.61 when the CaO/SiO2 mass ratio is around 2 at l 873 K. The logarithm of LB is linear to the reciprocal of temperatures in the range of 1 773-1 973 K. LB increases with the increase of mass ratio of slag to silicon, but it does not increase markedly when the ratio excesses 3. Gas blowing can sionificantlv increase the removal of boron, and LR increases with the increase of water vapor content.
Elimination of phosphorus vaporizing from silicon was investigated. Si-P alloy made from electronic grade silicon was used. All the samples were analyzed by GD-MS. Theory calculation determines that phosphorus evaporates from molten silicon as gas species P and P2 at a finite reduced pressure. The experimental results show that phosphorus mass fraction can be decreased from 0.046% （460ppmw） to around 0.001% （10ppmw） under the condition of temperature 1 873 K, chamber pressure 0.6-0.8 Pa, holding time 1 h. Both experimental data and calculation results agree that at high phosphorus concentration, phosphorus removal is quite dependent on high chamber pressure while it becomes independent on low chamber pressure. The reason is that phosphorus evaporates from molten silicon as gas species P2 at a relatively high phosphorus concentration, while gas species P will be dominated in its vapour at low phosphorus content.
