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“Liquinert” Process for High-Quality Bulk Single Crystal Growth

Received: 18 January 2021    Accepted: 29 January 2021    Published: 26 February 2021
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Abstract

Bulk crystal growth technologies originate from the Czochralski (CZ) and Vertical Bridgman (VB) methods developed almost one century ago. Both methods were applied to prepare single crystals of many kind of inorganic materials, for example, semiconductors, halides and many oxides. In the VB process, molten raw materials are wetting the crucible wall easily. This phenomenon causes the sticking of grown crystals with crucibles and often leads to the cracking of the crystal and crucible. These issues prohibit us from obtaining high quality single crystals. Therefore, practical application of VB method is limited only on several materials such as CaF2 and GaAs single crystals. The issue of crucible’s wetting is present in the CZ method as well. For example, the purity of silicon single crystals is degraded from 11N raw material to 5~6N level by the oxygen and carbon contamination caused by the wetting between silicon melt and quartz crucible. These issues are yet to be solved in VB and CZ methods. Many molten materials reach the spherical shape driven by the surface tension when a residual moisture (H2O) is completely removed from the raw material, the crucible, and atmosphere. We denote this condition as the “Liquinert” state meaning “liquid being in an inert state”, non-wetting and non-reactive with the crucible at high temperature. The author has prepared many high-quality bulk crystals of mainly metallic halides and semiconductors, except oxides, by VB method when applying the “Liquinert” process. This technology is applicable to high quality bulk crystal growth of silicon as well as other inorganic materials of huge industrial interest. In this review, the “Liquinert” process, its background, methodology, examples of applications in fundamental research, and practical development are exposed. In addition, we also discuss the future of this industrial process on bulk silicon crystals for semiconductors and solar cells.

Published in American Journal of Chemical Engineering (Volume 9, Issue 1)
DOI 10.11648/j.ajche.20210901.13
Page(s) 25-33
Creative Commons

This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

Liquinert, Single Crystal Growth, Bridgman Method, Silicon, Solar Cell

References
[1] J. Czochralski: Z. Phys. Chem. 92 (1918), 219.
[2] P. W. Bridgman: Proc. Amer. Acad. Arts. Sci. 60 (1925) 305.
[3] S. Sakuragi: Proc. of Intern. Conf. on Inorganic Scintillators and their Applications, Delft University Press, (1995), 483K. Elissa, “Preparation of Shaped Scintillation Crystals under Non-Wetting Conditions” unpublished.
[4] S. Sakuragi: Kinzoku (Journal of Metal Society of Japan) 75, (2005), 771 (in Japanese).
[5] H. Grundig: Z. Phyzik, 158 (1960), 577.
[6] F. Rosenberger: Ultra-purity, Mercel Dekker, New York (1972) 3-69.
[7] K. Kobayashi and S. Sakuragi: Lecture on the Experimental Chemistry: Basic Operation 2, Maruzen, (1975), 726-746, (in Japanese).
[8] H. Kanzaki and S. Sakuragi: Journal of the Physical Society of Japan, 27, No 1. July 1969, 109-125.
[9] H. Kanzaki, S. Sakuragi and K. Sakamoto, Solid State Communication, vol. 9, 999-1022, 1971.
[10] Y. Toyozawa, Excitonic Processes in Solids, Springer-Verlag, 1986, chapter 4.
[11] Y. Toyozawa, Optical Processes in Solids, Cambridge University Press, 2003, chapter 9.
[12] Y. Fujii, S. Hoshino, S. Sakuragi, H. Kanzaki, J. W. Lynn and G. Shirane: Physical Review B, Vol. 15, No. 1, 358-368. 1977.
[13] S. Sakuragi, N. Sakai. H. Kotani, T. Miyata: Proceedings of ICALEO Volume 44, Material Processing, pp 291-297, Nov. 12-15, (1984), Boston.
[14] S. Sakuragi: Proceedings of SPIE Volume 320, Advances in Infrared Fibers II, pp 2-9, Jan. 26-28, (1982), Los Angeles.
[15] S. Sakuragi, Y. Taguchi, H. Sato, A. Kasai, H. Nanba, T. Kawai and S. Hashimoto: Proceedings of SPIE Volume 5647, 36th Annual Boulder Damage Symposium, pp 314-321.
[16] Y. Okada, S. Sakuragi, and S. Hashimoto: Japanese Journal of Applied Physics, Vol. 29, No. 11, November 1990, pp. L 1956.
[17] S. Sakuragi, S. Hashimoto and Y. Yamasaki: Proceedings of the 28th Workshop on Radiation Detectors and Their Users, KEK Proceedings 2014-11, January 2015 H/R, 16-22.
[18] N. J. Cherepy, G. Hull, A. D. Alexander, S. A. Payne, E. Loef, C. M. Wilson, K. S. Shah. U. N. Roy, A. Burger. L. A. Boatner, W. S. Choong, and W. W. Moses: Applied Physics Letters 92, 08508 (2008).
[19] T. Kawai, S. Sakuragi, and S. Hashimoto: Journal of Luminescence 176 (2016) 58-64.
[20] K. Shimazoe, A. Koyama, H. Takahashi, S. Sakuragi, & Y. Yamasaki: Nuclear Instruments and Methods in Physics Research Section A: 810, 59-62. (2016).
[21] K. Shimazoe, A. Koyama, H. Takahashi, S. Sakuragi, Y. Yamasaki: Nuclear Instruments and Methods in Physics Research Section A: 845, 503-506. (2017).
[22] S. Sakuragi: Proceedings of 19th European Photovoltaic Solar Energy Conference, Paris, France, Vol. 1, 1201-1204, 2004.
[23] S. Sakuragi, T. Shimasaki, G. Sakuragi and H. Nanba: Proceedings of 19th European Photovoltaic Solar Energy Conference, Paris, France, Vol. 1, 1197-11200, 2004.
[24] Y. Horioka, S. Sakuragi.: US Patent US 2014/0150714 A1.
[25] K. Fujiwara, Y. Horioka, and S. Sakuragi: Energy Science & Engineering 3 (2015) 419. T.
[26] Fukuda, Y. Horioka, N. Suzuki, M. Moriya, K. Tanahashi, S. Simayi, K. Shirasawa, and H. Takato, J. Crystal Growth 438 (2016), pp. 76 – 80.
[27] T. Fukuda, Y. Horioka, K. Tanahashi, S. Simayi, K. Shirasawa, and H. Takato, Oral presentation on the 63th Spring Meeting of Applies Physics of Japan, March 20, 2016: (Proceeding No. 20p-S611.
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  • APA Style

    Shiro Sakuragi. (2021). “Liquinert” Process for High-Quality Bulk Single Crystal Growth. American Journal of Chemical Engineering, 9(1), 25-33. https://doi.org/10.11648/j.ajche.20210901.13

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    ACS Style

    Shiro Sakuragi. “Liquinert” Process for High-Quality Bulk Single Crystal Growth. Am. J. Chem. Eng. 2021, 9(1), 25-33. doi: 10.11648/j.ajche.20210901.13

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    AMA Style

    Shiro Sakuragi. “Liquinert” Process for High-Quality Bulk Single Crystal Growth. Am J Chem Eng. 2021;9(1):25-33. doi: 10.11648/j.ajche.20210901.13

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  • @article{10.11648/j.ajche.20210901.13,
      author = {Shiro Sakuragi},
      title = {“Liquinert” Process for High-Quality Bulk Single Crystal Growth},
      journal = {American Journal of Chemical Engineering},
      volume = {9},
      number = {1},
      pages = {25-33},
      doi = {10.11648/j.ajche.20210901.13},
      url = {https://doi.org/10.11648/j.ajche.20210901.13},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajche.20210901.13},
      abstract = {Bulk crystal growth technologies originate from the Czochralski (CZ) and Vertical Bridgman (VB) methods developed almost one century ago. Both methods were applied to prepare single crystals of many kind of inorganic materials, for example, semiconductors, halides and many oxides. In the VB process, molten raw materials are wetting the crucible wall easily. This phenomenon causes the sticking of grown crystals with crucibles and often leads to the cracking of the crystal and crucible. These issues prohibit us from obtaining high quality single crystals. Therefore, practical application of VB method is limited only on several materials such as CaF2 and GaAs single crystals. The issue of crucible’s wetting is present in the CZ method as well. For example, the purity of silicon single crystals is degraded from 11N raw material to 5~6N level by the oxygen and carbon contamination caused by the wetting between silicon melt and quartz crucible. These issues are yet to be solved in VB and CZ methods. Many molten materials reach the spherical shape driven by the surface tension when a residual moisture (H2O) is completely removed from the raw material, the crucible, and atmosphere. We denote this condition as the “Liquinert” state meaning “liquid being in an inert state”, non-wetting and non-reactive with the crucible at high temperature. The author has prepared many high-quality bulk crystals of mainly metallic halides and semiconductors, except oxides, by VB method when applying the “Liquinert” process. This technology is applicable to high quality bulk crystal growth of silicon as well as other inorganic materials of huge industrial interest. In this review, the “Liquinert” process, its background, methodology, examples of applications in fundamental research, and practical development are exposed. In addition, we also discuss the future of this industrial process on bulk silicon crystals for semiconductors and solar cells.},
     year = {2021}
    }
    

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  • TY  - JOUR
    T1  - “Liquinert” Process for High-Quality Bulk Single Crystal Growth
    AU  - Shiro Sakuragi
    Y1  - 2021/02/26
    PY  - 2021
    N1  - https://doi.org/10.11648/j.ajche.20210901.13
    DO  - 10.11648/j.ajche.20210901.13
    T2  - American Journal of Chemical Engineering
    JF  - American Journal of Chemical Engineering
    JO  - American Journal of Chemical Engineering
    SP  - 25
    EP  - 33
    PB  - Science Publishing Group
    SN  - 2330-8613
    UR  - https://doi.org/10.11648/j.ajche.20210901.13
    AB  - Bulk crystal growth technologies originate from the Czochralski (CZ) and Vertical Bridgman (VB) methods developed almost one century ago. Both methods were applied to prepare single crystals of many kind of inorganic materials, for example, semiconductors, halides and many oxides. In the VB process, molten raw materials are wetting the crucible wall easily. This phenomenon causes the sticking of grown crystals with crucibles and often leads to the cracking of the crystal and crucible. These issues prohibit us from obtaining high quality single crystals. Therefore, practical application of VB method is limited only on several materials such as CaF2 and GaAs single crystals. The issue of crucible’s wetting is present in the CZ method as well. For example, the purity of silicon single crystals is degraded from 11N raw material to 5~6N level by the oxygen and carbon contamination caused by the wetting between silicon melt and quartz crucible. These issues are yet to be solved in VB and CZ methods. Many molten materials reach the spherical shape driven by the surface tension when a residual moisture (H2O) is completely removed from the raw material, the crucible, and atmosphere. We denote this condition as the “Liquinert” state meaning “liquid being in an inert state”, non-wetting and non-reactive with the crucible at high temperature. The author has prepared many high-quality bulk crystals of mainly metallic halides and semiconductors, except oxides, by VB method when applying the “Liquinert” process. This technology is applicable to high quality bulk crystal growth of silicon as well as other inorganic materials of huge industrial interest. In this review, the “Liquinert” process, its background, methodology, examples of applications in fundamental research, and practical development are exposed. In addition, we also discuss the future of this industrial process on bulk silicon crystals for semiconductors and solar cells.
    VL  - 9
    IS  - 1
    ER  - 

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  • Union Materials Inc., Tone-machi, Japan

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