Since the early 1950’s the use of Germanium has been continuously growing as new applications are being developed. Its first commercial usage as the main material, from which the semiconductors were made, was later replaced by Silicon. The applications were then shifted to a key component in fiber optics, infrared night vision devices and space solar cells, as well as a polymerization catalyst for polyethylene terephthalate (PET). With the advance development in new technologies, the attentions have been brought back to Germanium due to its excellent semiconductor properties. New applications on the field of high efficiency solar cells, SiGe based chips, LED technologies, etc., are being developed and show a great potential. According to DERA (Deutsche Rohstoffagentur/German Mineral Resources Agency), the demand for Ge will grow considerably by 2030, pushed mostly by the increase in the fiber optics market and advanced materials sector [1]. Therefore, this paper focuses on an overview of the production chain of Germanium, especially from its concentrate up to the single crystal growth of its valuable ultra-pure metallic form to be used in high technological applications.
References
[1]
Melcher, F. and Buchholz, P. (2012) Current and Future Germanium Availability from Primary Sources. Minor Metals Conference, Cologne, 24 April 2012, 5.
[2]
Holl, R., Kling, M. and Schroll, E. (2007) Metallogenesis of Germanium—A Review. Ore Geology Reviews, 30, 145-180. https://doi.org/10.1016/j.oregeorev.2005.07.034
[3]
Jorgenson, J.D. (2006) Germanium Recycling in the United States in 2000. United States Geological Survey, Reston, Virginia.
[4]
Claeys, C. and Simoen, E. (2007) Germanium Based Technologies. Elsevier Science, Amsterdam.
[5]
Bleiwas, D.I. (2010) Byproduct Mineral Commodities Used for the Production of Photovoltaic Cells. United States Geological Survey, Reston, Virginia.
[6]
Guberman, D.E. (2017) Mineral Commodity Summaries. United States Geological Survey, Reston, Virginia.
[7]
Moreno, A.M. and Sexton, S. (1998) Non-Ferrous Metal Works of the World. Metal Bulletin Books, London.
[8]
Kelly, T. and Matos, G. (2017) U.S. Geological Survey, 2014, Germanium Statistics, Historical Statistics for Mineral and Material Commodities in the United States: U.S. Geological Survey Data Series 140. http://minerals.usgs.gov/minerals/pubs/historical-statistics
[9]
Butterman, B.W.C. and Jorgenson, J.D. (2005) Germanium. U.S. Geological Survey, Reston.
[10]
Melorose, J., Perroy, R. and Careas, S. (2014) Mineral Commodity Summaries. United States Geological Survey, Reston, Virginia.
Bracht, H. (2015) Self- and Dopant Diffusion in Silicon, Germanium, and Their Alloys. In: Kissinger, G. and Pizzini, S., Eds., Silicon, Germanium, and Their Alloys-Growth, Defects, Impurities and Nanocrystals, Taylor & Francis Group, LLC.
[13]
Singh, R., Oprysko, M. and Harame, D. (2004) Silicon Germanium: Technology, Modeling, and Design. Wiley-IEEE Press, Hoboken.
[14]
Robertz, B., Verhelle, J. and Schurmans, M. (2015) The Primary and Secondary Production of Germanium: A Life-Cycle Assessment of Different Process Alternatives, JOM, 67, 412-424. https://doi.org/10.1007/s11837-014-1267-6
[15]
Germanium, J.S.C. (2017) Zone Refining. http://eng.krasgermanium.com/processing/zone-refining
[16]
5N Plus (2017) Germanium Zone Refined Bar. http://www.5nplus.com/germanium.html
Wang, W.K., Peng, J.H. and Zhang, Z.B. (2011) Recovery Methods of Germanium. Advanced Materials Research, 295-297, 2267-2271. https://doi.org/10.4028/www.scientific.net/AMR.295-297.2267
[19]
Guggenbühl, W., Strutt, M.J.O. and Wunderlin, W. (1962) Halbleiterbauelemente. Birkhauser Basel, Basel. https://doi.org/10.1007/978-3-0348-6854-9
[20]
Weiser, K. (1958) Theoretical Calculation of Distribution Coefficients of Impurities in Germanium and Silicon, Heats of Solid Solution. Journal of Physics and Chemistry of Solids, 7, 118-126. https://doi.org/10.1016/0022-3697(58)90252-X
[21]
Pfann, W.G. (1958) Zone Melting. Wiley, Hoboken.
[22]
Cheung, N., Bertazzoli, R. and Garcia, A. (2008) Experimental Impurity Segregation and Numerical Analysis Based on Variable Solute Distribution Coefficients during Multi-Pass Zone Refining of Aluminum. Journal of Crystal Growth, 310, 1274-1280. https://doi.org/10.1016/j.jcrysgro.2008.01.007
[23]
Burton, J.A., Prim, R.C. and Slichter, W.P. (1953) The Distribution of Solute in Crystals Grown from the Melt. Part II. Experimental. Journal of Chemical Physics, 21, 1987.
[24]
Burton, J.A., Prim, R.C. and Slichter, W.P. (1953) The Distribution of Solute in Crystals Grown from the Melt. Part I: Theoretical. Journal of Chemical Physics, 21, 1987.
[25]
Tiller, W., Jackson, K., Rutter, J. and Chalmers, B. (1953) The Redistribution of Solute Atoms during the Solidification of Metals. Acta Metallurgica, 1, 428-437. https://doi.org/10.1016/0001-6160(53)90126-6
[26]
Porter, D.A. and Easterling, K.E. (1992) Solidification. In: Porter, D.A., Ed., Phase Transformations in Metals and Alloys, Chapman & Hall, London, New York, 1-56.
[27]
Chatelain, M., Albaric, M., Pelletier, D. and Botton, V. (2015) Solute Segregation in Directional Solidification: Scaling Analysis of the Solute Boundary Layer Coupled with Transient Hydrodynamic Simulations. Journal of Crystal Growth, 430, 138-147. https://doi.org/10.1016/j.jcrysgro.2015.08.013
[28]
Wilson, L.O. (1978) On Interpreting a Quantity in the Burton, Prim and Slichter Equation as a Diffusion Boundary Layer Thickness. Journal of Crystal Growth, 44, 247-250. https://doi.org/10.1016/0022-0248(78)90199-9
[29]
Nozawa, J., et al. (2013) Impurity Partitioning during Colloidal Crystallization. The Journal of Physical Chemistry B, 117, 5289-5295. https://doi.org/10.1021/jp309550y
[30]
Hubbard, G.S., Haller, E.E. and Hansen, W.L. (1977) Zone Refining High-Purity Germanium. Nuclear Science Symposium, San Francisco, 19 October 1977, 1-2.
[31]
Trumbore, F.A. (1960) Solid Solubilities of Impurity Elements in Germanium and Silicon. Bell System Technical Journal, 39, 205-303. https://doi.org/10.1002/j.1538-7305.1960.tb03928.x
[32]
Statz, H. (1963) Maximum Solid Solubility and Distribution Coefficient of Impurities in Germanium and Silicon. Journal of Physics and Chemistry of Solids, 24, 699-700. https://doi.org/10.1016/S0022-3697(63)80013-X
[33]
Trumbore, F.A., Isenberg, C.R. and Porbansky, E.M. (1958) On the Temperature-Dependence of the Distribution Coefficient: The Solid Solubilities of Tin in Silicon and Germanium. Journal of Physics and Chemistry of Solids, 9, 60-69. https://doi.org/10.1016/0022-3697(59)90091-5
[34]
Haller, E.E., Hansen, W.L., Hubbard, G.S. and Goulding, F.S. (1976) Origin and Control of the Dominant Impurities in High-Purity Germanium. IEEE Transactions on Nuclear Science, 23, 81-87. https://doi.org/10.1109/TNS.1976.4328219
[35]
Taishi, T., et al., (2010) Czochralski-Growth of Germanium Crystals Containing High Concentrations of Oxygen Impurities. Journal of Crystal Growth, 312, 2783-2787. https://doi.org/10.1016/j.jcrysgro.2010.05.045
[36]
Spim, J.A., Bernadou, M.J.S. and Garcia, A. (2000) Numerical Modeling and Optimization of Zone Refining. Journal of Alloys and Compounds, 298, 299-305. https://doi.org/10.1016/S0925-8388(99)00655-6
[37]
Rodway, G.H. and Hunt, J.D. (1989) Optimizing Zone Refining. Journal of Crystal Growth, 97, 680-688. https://doi.org/10.1016/0022-0248(89)90571-X
[38]
Prasad, D.S., Munirathnam, N.R., Rao, J.V. and Prakash, T.L. (2006) Effect of Multi-Pass, Zone Length and Translation Rate on Impurity Segregation during Zone Refining of Tellurium. Materials Letters, 60, 1875-1879. https://doi.org/10.1016/j.matlet.2005.12.041
[39]
Wang, S., Fang, H.S., Jin, Z.L., Zhao, C.J. and Zheng, L.L. (2014) Integrated Analysis and Design Optimization of Germanium Purification Process Using Zone-Refining Technique. Journal of Crystal Growth, 408, 42-48. https://doi.org/10.1016/j.jcrysgro.2014.09.019
[40]
Yang, G., et al. (2014) Investigation of Influential Factors on the Purification of Zone-Refined Germanium Ingot. Crystal Research and Technology, 49, 269-275. https://doi.org/10.1002/crat.201300418
[41]
Burger, A., Henderson, D.O., Morgan, S.H., Feng, J. and Silberman, E. (1990) Purification of Selenium by Zone Refining. Journal of Crystal Growth, 106, 34-37. https://doi.org/10.1016/0022-0248(90)90283-Q
[42]
Munirathnam, N.R., Prasad, D.S., Sudheer, C.H., Rao, J.V. and Prakash, T.L. (2005) Zone Refining of Cadmium and Related Characterization. Bulletin of Materials Science, 28, 209-212. https://doi.org/10.1007/BF02711249
[43]
Mei, P.R., Moreira, S.P., Cardoso, E., Cortes, A.D.S. and Marques, F.C. (2012) Purification of Metallurgical Silicon by Horizontal Zone Melting. Solar Energy Materials and Solar Cells, 98, 233-239. https://doi.org/10.1016/j.solmat.2011.11.014
[44]
Roussopoulos, G.S. and Rubini, P.A. (2004) A Thermal Analysis of the Horizontal Zone Refining of Indium Antimonide. Journal of Crystal Growth, 271, 333-340. https://doi.org/10.1016/j.jcrysgro.2004.07.058
[45]
Bhat, H.L. (2014) Introduction to Crystal Growth: Principles and Practice. CRC Press, Boca Raton. https://doi.org/10.1201/b17590
[46]
Kaiser, N., Croell, A., Szofran, F.R., Cobb, S.D., Dold, P. and Benz, K.W. (2001) Wetting Angle and Surface Tension of Germanium Melts on Different Substrate Materials. Journal of Crystal Growth, 231, 448-457. https://doi.org/10.1016/S0022-0248(01)01480-4
[47]
Hult, M., Belogurov, S., Caldwell, A., Janicsko, J., Kornoukhov, V. and Schonert, S. (2008) On the Underground Production of High Purity Germanium Detectors. Office for Official Publications of the European Communities, Luxembourg.
[48]
Wang, G., et al. (2012) Development of Large Size High-Purity Germanium Crystal Growth. Journal of Crystal Growth, 352, 27-30. https://doi.org/10.1016/j.jcrysgro.2012.01.018
[49]
Rudolph, P. and Nishinga, T. (2014) Handbook of Crystal Growth: Bulk Crystal Growth. Elsevier, 2, 389-397.
[50]
Wang, G., et al. (2014) Dislocation Density Control in High-Purity Germanium Crystal Growth. Journal of Crystal Growth, 393, 54-58. https://doi.org/10.1016/j.jcrysgro.2013.11.075
[51]
Roth, M., Azoulay, M., Gafni, G. and Mizrachi, M. (1990) Crystal-Melt Interface Shape of Czochralski-Grown Large Diameter Germanium Crystal. Journal of Crystal Growth, 99, 670-675. https://doi.org/10.1016/S0022-0248(08)80004-8
[52]
Vojdani, S., Dabiri, A.E. and Ashoori, H. (1974) Diameter Control of Pulled Germanium Crystals by Means of Peltier Cooling. Journal of Crystal Growth, 24-25, 374-375. https://doi.org/10.1016/0022-0248(74)90338-8
[53]
Friedrich, J., von Ammon, W. and Müller, G. (2014) Czochralski Growth of Silicon Crystals. In: Rudolph, P., Ed., Handbook of Crystal Growth: Bulk Crystal Growth, Elsevier Science, Amsterdam, 47-61.
[54]
Depuydt, B. (2001) Encyclopedia of Materials: Science and Technology. Elsevier Science, Amsterdam.
[55]
Yang, G., et al. (2012) Radial and Axial Impurity Distribution in High-Purity Germanium Crystals. Journal of Crystal Growth, 352, 43-46. https://doi.org/10.1016/j.jcrysgro.2011.12.042
[56]
Taishi, T., Ohno, Y. and Yonenaga, I. (2009) Reduction of Grown-in Dislocation Density in Ge Czochralski-Grown from the B2O3-Partially-Covered Melt. Journal of Crystal Growth, 311, 4615-4618. https://doi.org/10.1016/j.jcrysgro.2009.09.001
[57]
Taishi, T., Hashimoto, Y., Ise, H., Murao, Y., Ohsawa, T. and Yonenaga, I. (2012) Czochralski Growth Techniques of Germanium Crystals Grown from a Melt Covered Partially or Fully by Liquid B2O3. Journal of Crystal Growth, 360, 47-51. https://doi.org/10.1016/j.jcrysgro.2011.11.051
[58]
Glazov, V.M. and Shchelikov, O.D. (2000) Volume Changes during Melting and Heating of Silicon and Germanium Melts. High Temperature, 38, 429-436. https://doi.org/10.1007/BF02756000
[59]
Shingu, H., et al. (1984) Process for Producing High-Purity Aluminum. US Patent No. 4469512.
[60]
Friedrich, S., Curtolo, D.C. and Friedrich, B. (2017) Effect of Process Parameter Variation on Purity during Rotary Fractional Crystallization of Aluminum. Open Journal of Metal, 7, 25-38. https://doi.org/10.4236/ojmetal.2017.72003
