Milestones:Czochralski

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Title

Czochralski Method of Crystal Growth, 1916

Citation

In 1916, Jan Czochralski invented a method of crystal growth used to obtain single crystals of semiconductors, metals, salts and synthetic gemstones during his work at AEG in Berlin, Germany. He developed the process further at the Warsaw University of Technology, Poland. The Czochralski process enabled development of electronic semiconductor devices and modern electronics.

Street address(es) and GPS coordinates of the Milestone Plaque Sites

1) Pl. Politechniki 1, 00-665 Warszawa (Warsaw), Poland; GPS - 52.220527 (latitude), 21.010357 (longitude)and2) Hochschule für Technik und Wirtschaft Berlin, Treskowallee 8, 10318 Berlin, Germany GPS (latitude, longitude) 52.493235, 13.525455and3) Main Square (in the center), Kcynia (small city with some 4500 inhibitants), Poland (the plaque will be in Polish language only), 1) Pl. Politechniki 1, 00-665 Warszawa (Warsaw), Poland; GPS - 52.220527 (latitude), 21.010357 (longitude)

and

2) Hochschule für Technik und Wirtschaft Berlin, Treskowallee 8, 10318 Berlin, Germany GPS (latitude, longitude) 52.493235, 13.525455

and

3) Main Square (in the center), Kcynia (small city with some 4500 inhibitants), Poland (the plaque will be in Polish language only)

Details of the physical location of the plaque

1) The plaque will be placed at the Main Hall, Warsaw University of Technology, Warsaw, Poland; 2) The plaque will be placed at the building close to the lab at Hochschule für Technik und Wirtschaft Berlin, Germany 3) The plaque will placed on large stone located close to the Jan Chochralski monument, Main Square (in the center of the city), Kcynia, Poland

How the intended plaque site is protected/secured

The plaque site is publicly accessible at one of the largest university of technology in Poland (Warsaw University of Technology) with high concentration of academics and students. There is also open access for the public free entrance. The plaque site is publicly accessible at the University of Applied Sciences for Engineering and Economics. There is also open access for the public free entrance. The plaque site at Kcynia city is publicly accessible.

Historical significance of the work

Monocrystalline silicon (mono-Si) grown by the Czochralski process is often referred to as monocrystalline Czochralski silicon (Cz-Si). It is the basic material in the production of integrated circuits used in all types of modern electronic equipment and semiconductor devices, e.g., computers, TVs, mobile phones etc. Monocrystalline silicon is also used in large quantities by the photovoltaic industry for the production of conventional mono-Si solar cells. The almost perfect crystal structure yields the highest light-to-electricity conversion efficiency for silicon. The method of monocristalline silicon growth for large scale industry application started some 30 year later after the method was invented. A year before leaving AEG company in Berlin, in 1916, J.Czochralski wrote a paper on the crystal growth method, later named the “Czochralski method”. The paper was received by the editorial board on August 19, 1916 and was published in 1918, with a two year delay [J. Czochralski, ”Ein neues Verfahren zur Messung des Kristallisationsgeschwindigkeit der Metalle”, Z.Phys. Chem. 92, 219 (1918)]. In the scientific literature, the year 1916 was adopted as the date of elaboration of the method. The idea of Czochralski method is based on pulling a crystal from the melt against gravity forces. This feature contitutes an important difference in respect to other known crystal growth methods. Czochralski has grown single crystals of tin, zinc and lead by this simple method and investigated their rate of crystallization. The paper provided a description of a device, which contained a silk thread with a holder and was completed with a glass rod. A part of the glass immersed in the molten metal was covered with a metal layer, and then the growth was continued. The obtained wires were of about 1 mm diameter and had up to 150 cm in length. The Czochralski method was improved and cited by some authors from the very beginning. For example, in 1918 Wartenberg used a seed zinc wire to grow the crystals of zinc. Later, in 1922, Gompez called this method for the first time the Czochralski method. Later, works describing the method were written by Mark et al. in 1923, by Sachs in 1925 and by others. After invention of germanium-based transistor in 1947, Gordon K. Teal from Bell Laboratory used the Czochralski method to obtain germanium single crystals. The first single crystal of germanium was obtained in 1948 and the results were presented at the Oak Ridge Meeting of the American Physical Society in 1950, and were reported in G.K. Teal, Phys. Rev. 78, 647 (1950). One of the sentences confirms the used method: “germanium single crystals of a variety of shapes, sizes and electrical properties have been produced by means of a pulling technique distinguished from that of Czochralski and others in improvement”. It should be noted that the Czochralski method of crystal growth is continuously improved and developed with regard to the technical level of process automation and including thermodynamic considerations of growth processes even today. It permits to prepare a high quality bulk single crystals, among them silicon, as well as a multitude of oxides, fluorides, metals and alloys, multi-component compounds and solid solutions. Now, the main advantages of the Czochralski method are growing single crystals in defined crystallographic orientations with different sizes, shapes, which are mainly limited by a design of crystal puller.

Features that set this work apart from similar achievements

The Bridgman method is a popular way of producing certain semiconductor crystals such as gallium arsenide, for which the Czochralski process is the most difficult. The process can reliably produce single crystal ingots, but does not necessarily result in uniform properties through the crystal. Bridgman–Stockbarger technique is named after Harvard physicist Percy Williams Bridgman (1882-1961) and MIT physicist Donald C. Stockbarger (1895–1952). The technique includes two similar but distinct methods primarily used for growing boules (single crystal ingots), but which can be used for solidifying polycrystalline ingots as well. The methods involve heating polycrystalline material above its melting point and slowly cooling it from one end of its container, where a seed crystal is located. A single crystal of the same crystallographic orientation as the seed material is grown on the seed and is progressively formed along the length of the container. The process can be carried out in a horizontal or vertical orientation, and usually involves a rotating crucible/ampoule to stir the melt. The uncontrolled gradient produced at the exit of the furnace; the Stockbarger technique introduces a baffle, or shelf, separating two coupled furnaces with temperatures above and below the freezing point. Stockbarger's modification of the Bridgman technique allows for better control over the temperature gradient at the melt/crystal interface

Significant references

The full texts of the following references have been submitted to the IEEE History Center staff.

Jurgen Evers,* Peter Klufers, Rudolf Staudigl,* and Peter Stallhofer – “Czochralski's Creative Mistake: A Milestone on the Way to the Gigabit Era”, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ange.200300587 Angew. Chem. 2003, 115, 5862–5877 2. J. Harkonen, E. Tuovinen, P. Luukka, E. Tuominen, at el. –“ Particle detectors made of high-resistivity Czochralski silicon”, Nuclear Instruments and Methods in Physics Research A 541 (2005) 202–207 3. Jing-lan Chen, Shu-xia Gao, Wen-hong Wang, Ming Zhang, at el. –“ Single crystals of Tb0.3Dy0.7Fe2 grown by Czochralski method with cold crucible”, Journal of Crystal Growth 236 (2002) 305–310 4. Magdalena Wencka, MirthaPillaca, PeterGille –“ Single crystal growth of Ga3Ni2 by the Czochralski method”, Journal of Crystal Growth 449 (2016) 114–118 5. Czochralski process – Wikipedia

Supporting materials

1. Jurgen Evers,* Peter Klufers, Rudolf Staudigl,* and Peter Stallhofer – “Czochralski's Creative Mistake: A Milestone on the Way to the Gigabit Era”, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ange.200300587 Angew. Chem. 2003, 115, 5862–5877
2. J. Harkonen, E. Tuovinen, P. Luukka, E. Tuominen, at el. –“ Particle detectors made of high-resistivity Czochralski silicon”, Nuclear Instruments and Methods in Physics Research A 541 (2005) 202–207
3. Jing-lan Chen, Shu-xia Gao, Wen-hong Wang, Ming Zhang, at el. –“ Single crystals of Tb0.3Dy0.7Fe2 grown by Czochralski method with cold crucible”, Journal of Crystal Growth 236 (2002) 305–310
4. Magdalena Wencka, MirthaPillaca, PeterGille –“ Single crystal growth of Ga3Ni2 by the Czochralski method”, Journal of Crystal Growth 449 (2016) 114–118
5. Czochralski process – Wikipedia

Additional reading Tomaszewski, Pawel E., Jan Czochralski Restored, 2012, Officyna Wydawnicza ATUT, Wroclaw