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Simultaneously removal of P and B from Si by Sr and Zr co-addition during Al-Si low-temperature solvent refining

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Abstract

To remove the key impurity elements, P and B, from primary Si simultaneously, Sr and Zr co-addition to Al-Si alloy systems during solvent refining has been investigated. Sr reacts with Al, Si, and P in the melt to form a P-containing Al2Si2Sr phase and Zr reacts with B to form a ZrB2 phase. In the Al-Si—Sr—Zr system, high removal fractions of P and B in the primary Si, with 84.8%—98.4% and 90.7%—96.7%, respectively, are achieved at the same time, respectively. The best removal effect is obtained in the sample with the addition of Sr-32000+Zr-3000 µg·kg−1, and the removal fractions of P and B in the purified Si reach 98.4% and 96.1%. Compared with the Sr/Zr single-addition, the removal effects of Sr and Zr co-addition on P and B do not show a significant downward trend, indicating that the nucleation and growth of the B/P-containing impurity phases are mutually independent. Finally, an evolution model is proposed to describe the nucleation and the growth stages of Sr/Zr-containing compound phases, which reveals the interaction between the impurity phases and the primary Si.

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References

  1. T. Yoshikawa and K. Morita, An evolving method for solar-grade silicon production: Solvent refining, JOM, 64(2012), No. 8, p. 946.

    Article  CAS  Google Scholar 

  2. Y.Q. Li, W. Chen, J. Lu, X.H. Lei, and L.F. Zhang, Boron removal from metallurgical-grade silicon by slag refining and gas blowing techniques: Experiments and simulations, J. Electron. Mater., 50(2021), No. 3, p. 1386.

    Article  CAS  Google Scholar 

  3. Y.S. Ren, H.P. Wang, and K. Morita, Effect of Zr addition on B-removal behaviour during solidification purification of Si with Si—Sn solvent, Vacuum, 167(2019), p. 319.

    Article  CAS  Google Scholar 

  4. S. Shi, P.T. Li, D.C. Jiang, Y. Tan, X. Li, J.X. Yang, L. Zhang, F. Wang, J.Y. Li, and H. M. Asghar, Asghar, Kinetics of evaporation under vacuum in preparation of solar-grade silicon by electron beam melting, Mater. Sci. Semicond. Process., 96(2019), p. 53.

    Article  CAS  Google Scholar 

  5. X. Gu, X.G. Yu, and D.R. Yang, Low-cost solar grade silicon purification process with Al-Si system using a powder metallurgy technique, Sep. Purif. Technol., 77(2011), No. 1, p. 33.

    Article  CAS  Google Scholar 

  6. B.Y. Ban, Y.L. Li, Q.X. Zuo, T.T. Zhang, J. Chen, and S.Y. Dai, Refining of metallurgical grade Si by solidification of Al-Si melt under electromagnetic stirring, J. Mater. Process. Technol., 222(2015), p. 142.

    Article  CAS  Google Scholar 

  7. T. Yoshikawa and K. Morita, Removal of B from Si by solidification refining with Si—Al melts, Metall. Mater. Trans. B, 36(2005), No. 6, p. 731.

    Article  Google Scholar 

  8. W.Z. Yu, Y. Xue, J. Mei, X.Z. Zhou, M.L. Xiong, and S.F. Zhang, Segregation and removal of transition metal impurities during the directional solidification refining of silicon with Al-Si solvent, J. Alloys Compd., 805(2019), p. 198.

    Article  CAS  Google Scholar 

  9. F.A. Trumbore, Solid solubilities of impurity elements in germanium and silicon, Bell Syst. Tech. J., 39(1960), No. 1, p. 205.

    Article  Google Scholar 

  10. H.X. Lai, Z.L. Sheng, J.T. Li, P.F. Xing, and X.T. Luo, Enhanced separation of phosphorus from metallurgical grade silicon by CaAl2Si2 phase reconstruction, Sep. Purif. Technol., 191(2018), p. 257.

    Article  CAS  Google Scholar 

  11. L.Q. Huang, A. Danaei, S. Thomas, P.F. Xing, J.T. Li, X.T. Luo, and M. Barati, Solvent extraction of phosphorus from Si—Cu refining system with calcium addition, Sep. Purif. Technol., 204(2018), p. 205.

    Article  CAS  Google Scholar 

  12. L. Hu, Z. Wang, X.Z. Gong, Z.C. Guo, and H. Zhang, Purification of metallurgical-grade silicon by Sn—Si refining system with calcium addition, Sep. Purif. Technol., 118(2013), p. 699.

    Article  CAS  Google Scholar 

  13. M.Y. Zhu, S.Y. Yue, G.X. Wu, K. Tang, Y.J. Xu, and J. Safarian, P removal from Si by Si—Ca—Al alloying-leaching refining: Effect of Al and the CaAl2Si2 phase, Sep. Purif. Technol., 271(2021), art. No. 118675.

  14. L.Y. Sun, Z. Wang, H. Chen, D. Wang, and G.Y. Qian, Removal of phosphorus in silicon by the formation of CaAl2Si2 phase at the solidification interface, Metall. Mater. Trans. B, 48(2017), No. 1, p. 420.

    Article  CAS  Google Scholar 

  15. S.M. Kauzlarich, C.L. Condron, J.K. Wassei, T. Ikeda, and G.J. Snyder, Structure and high-temperature thermoelectric properties of SrAl2Si2, J. Solid State Chem., 182(2009), No. 2, p. 240.

    Article  CAS  Google Scholar 

  16. J. Rakhmonov, G. Timelli, and G. Basso, Interaction of Ca, P trace elements and Sr modification in AlSi5Cu1Mg alloys, J. Therm. Anal. Calorim., 133(2018), No. 1, p. 123.

    Article  CAS  Google Scholar 

  17. Y.H. Cho, H.C. Lee, K.H. Oh, and A.K. Dahle, Effect of strontium and phosphorus on eutectic Al-Si nucleation and formation of β-Al5FeSi in hypoeutectic Al-Si foundry alloys, Metall. Mater. Trans. A, 39(2008), No. 10, p. 2435.

    Article  Google Scholar 

  18. Y. Lei, W.H. Ma, L.E. Sun, Y.N. Dai, and K. Morita, B removal by Zr addition in electromagnetic solidification refinement of Si with Si—Al melt, Metall. Mater. Trans. B, 47(2016), No. 1, p. 27.

    Article  CAS  Google Scholar 

  19. T. Yoshikawa, K. Arimura, and K. Morita, Boron removal by titanium addition in solidification refining of silicon with Si—Al melt, Metall. Mater. Trans. B, 36(2005), No. 6, p. 837.

    Article  Google Scholar 

  20. Y.S. Ren and K. Morita, Low-temperature process for the fabrication of low-boron content bulk Si from Si—Cu solution with Zr addition, ACS Sustain. Chem. Eng., 8(2020), No. 17, p. 6853.

    Article  CAS  Google Scholar 

  21. Y. Lei, W.H. Ma, J.J. Wu, K.X. Wei, G.Q. Lv, and S.T. Li, Purification of metallurgical-grade silicon using Si—Sn alloy in presence of Hf, Zr, or Ti, Mater. Sci. Semicond. Process., 88(2018), p. 97.

    Article  CAS  Google Scholar 

  22. H. Sakiani, S.H. Tabaian, and J. Chen, Effect of calcium addition on the silicon purification in the presence of low concentration of iron, J. Alloys Compd., 830(2020), art. No. 154112.

  23. H. Sakiani, S.H. Tabaian, J. Chen, J.W. Li, and B.Y. Ban, Investigating boron and phosphorus removal from silicon by Si—Ti and Si—Ti—Fe alloying systems, Sep. Purif. Technol., 250(2020), art. No. 117227.

  24. X.L. Bai, B.Y. Ban, J.W. Li, Z.Q. Fu, Z.J. Peng, C.B. Wang, and J. Chen, Effect of Ti addition on B removal during silicon refining in Al—30%Si alloy directional solidification, Sep. Purif. Technol., 174(2017), p. 345.

    Article  CAS  Google Scholar 

  25. X.L. Bai, B.Y. Ban, J.W. Li, Z.J. Peng, and J. Chen, Distribution behavior of B and P during Al-Si melt directional solidification with open-ended crucible, High Temp. Mater. Process., 37(2018), No. 3, p. 201.

    Article  CAS  Google Scholar 

  26. Y.L. Li, B.Y. Ban, J.W. Li, T.T. Zhang, X.L. Bai, J. Chen, and S.Y. Dai, Effect of cooling rate on phosphorus removal during Al-Si solvent refining, Metall. Mater. Trans. B, 46(2015), No. 2, p. 542.

    Article  CAS  Google Scholar 

  27. F. Chigondo, From metallurgical-grade to solar-grade silicon: An overview, Silicon, 10(2018), No. 3, p. 789.

    Article  CAS  Google Scholar 

  28. C. Chen, J.W. Li, X.S. Jiang, W.F. Song, J. Shi, B.Y. Ban, and J. Chen, Effect of impurity phase migration on Al—30wt.%Si solvent refining with Zr additions during directional solidification, Sep. Purif. Technol., 278(2021), art. No. 119572.

  29. V.N. Lozovskii and V.P. Popov, Temperature gradient zone melting, Prog. Cryst. Growth Charact., 6(1983), No. 1, p. 1.

    Article  CAS  Google Scholar 

  30. C. Chen, B.Y. Ban, J.F. Sun, J.W. Li, X.S. Jiang, J. Shi, and J. Chen, Mechanism of boron removal of primary Si phases and morphology evolution of impurity phases during slow cooling solidification refining of Al—30wt.%Si alloy with Zr additions, J. Alloys Compd., 860(2021), art. No. 158517.

  31. K. Kobayashi, P.H. Shingu, and R. Ozaki, Crystal growth of the primary silicon in an Al—16wt%Si alloy, J. Mater. Sci., 10(1975), No. 2, p. 290.

    Article  CAS  Google Scholar 

  32. W.Z. Yu, W.H. Ma, G.Q. Lü, Y.S. Ren, H.Y. Xue, and Y.N. Dai, Si purification by enrichment of primary Si in Al-Si melt, Trans. Nonferrous Met. Soc. China, 23(2013), No. 11, p. 3476.

    Article  CAS  Google Scholar 

  33. D. Liang, Y. Bayraktar, and H. Jones, Formation and segregation of primary silicon in Bridgman solidified Al—18.3wt% Si alloy, Acta Metall. Mater., 43(1995), No. 2, p. 579.

    Article  CAS  Google Scholar 

  34. F.W. Glaser and B. Post, System zirconium—boron, JOM, 5(1953), No. 9, p. 1117.

    Article  CAS  Google Scholar 

  35. P.J. Goodhew, J. Humphreys, and R. Beanland, Electron Microscopy and Analysis, Third edition Ed., Taylor & Francis, London and New York, 2001, p. 254.

    Google Scholar 

  36. W. Yi, J.B. Gao, Y. Tang, and L.J. Zhang, Thermodynamic descriptions of ternary Al-Si—Sr system supported by key experiments, Calphad, 68(2020), art. No. 101732.

  37. T. Yoshikawa and K. Morita, Refining of silicon during its solidification from a Si—Al melt, J. Cryst. Growth, 311(2009), No. 3, p. 776.

    Article  CAS  Google Scholar 

  38. H.M. Chen, F. Zheng, H.S. Liu, L.B. Liu, and Z.P. Jin, Thermodynamic assessment of B—Zr and Si—Zr binary systems, J. Alloys Compd., 468(2009), No. 1–2, p. 209.

    Article  CAS  Google Scholar 

  39. H. Li, L.T. Zhang, Q.F. Zeng, J.J. Wang, L.F. Cheng, H.T. Ren, and G. Kang, Crystal structure and elastic properties of ZrB compared with ZrB2: A first-principles study, Comput. Mater. Sci., 49(2010), No. 4, p. 814.

    Article  CAS  Google Scholar 

  40. G.M. Zatorska, G.S. Dmytriv, V.V. Pavlyuk, E. Bartoszak-Adamska, and M. Jaskólski, Crystal structure of the new intermetallic compound Zr2−xLix+ySi1−y (x = 0.17, y = 0.12) and its relation with the disilicide ZrSi2, J. Alloys Compd., 346(2002), No. 1–2, p. 154.

    Article  CAS  Google Scholar 

  41. W.Z. Yu, W.H. Ma, Z. Zheng, W.Y. Jiang, J. Li, and M.H. Tian, Effects of melt viscosity on enrichment and separation of primary silicon from Al-Si melt, Trans. Nonferrous Met. Soc. China, 27(2017), No. 2, p. 467.

    Article  CAS  Google Scholar 

  42. J.C. Jie, Q.C. Zou, J.L. Sun, Y.P. Lu, T.M. Wang, and T.J. Li, Separation mechanism of the primary Si phase from the hypereutectic Al-Si alloy using a rotating magnetic field during solidification, Acta Mater., 72(2014), p. 57.

    Article  CAS  Google Scholar 

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 51804294, 51874272, and 52111540265); Anhui Provincial Natural Science Foundation (No. 1808085ME121); the Key Laboratory of Photovoltaic and Energy Conservation Materials, Chinese Academy of Science (No. PECL2021QN003); Hefei Institutes of Physical Science, Chinese Academy of Sciences Director’s Fund (No. YZJJZX202018); International Clean Energy Talent Program by China Scholarship Council; Open Foundation of State Key Laboratory of Mineral Processing (No. BGRIMM-KJSKL-2022-23) and Open Foundation of State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization (No. CNMRCUKF2205).

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Correspondence to Boyuan Ban or Jian Chen.

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Chen, C., Li, J., Zuo, Q. et al. Simultaneously removal of P and B from Si by Sr and Zr co-addition during Al-Si low-temperature solvent refining. Int J Miner Metall Mater 30, 365–377 (2023). https://doi.org/10.1007/s12613-022-2504-6

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  • DOI: https://doi.org/10.1007/s12613-022-2504-6

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