JAN CZOCHRALSKI ACHIEVEMENTS Anna Paj¹czkowska

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1 Warsaw International Forum on Science and Technology of Crystal Growth March , Sendai, Japan JAN CZOCHRALSKI ACHIEVEMENTS Anna Paj¹czkowska Kcynia

2 Father of the Czochralski method There are many scientists in the field of physics, chemistry and in general meaning material science whose name are well known all over the world. One of them is Jan Czochralski who has permanent position as a father of crystal growth method named the Czochralski method; CZ-method Jan Czochralski about 22 years old

3 1. Introduction C O N T E N T: 2. Jan Czochralski s life and family Education 4. Employment 5. Publications 6. Crystal growth method the Czochralski method the Czochralski method in the literature the Czochralski method in the Czochralski papers 7. Prof. J. Czochralski as a metallurgist Investigated materials Metods of investigation 8. Conclusions

4 His life and family: Prof. Dr Jan Czochralski was born on October 23, 1885 in Kcynia (small town situated in the central part of Poland near Toruñ Copernicus town ). Jan Czochralski was born as the eight child of the Polish craftsmen Franciszek Czochralski and Marta from the Suchomski family. The Czochralskis were carpenters for many generations. Jan Czochralski married in 1910 Marguerits Haase, a pianist of Dutch origin, the dauther of a rich owner of tenement houses. He died on April 22, 1953 in Poznan (heart disease) and was buried in Kcynia. Jan and Marta Czochralski had three children: two dauthers Leonia (1914) and Cecilia (1920,) and a son Borys (1918). All children died. At the present time his nephew prof. Jan Czochralski works at Warsaw University as a teacher of German language.

5 He was born in 1885 in Kcynia. INSTYTUT TECHNOLOGII MATERIA ÓW ELEKTRONICZNYCH E D U C A T I O N: Exercise school, 6-years at Teachers Seminar in Kcynia. Then he completed Teachers Seminar (his matriculation certificate was not found). In 1904 he moved to Berlin and started to work. Simultaneously he attended lectures on chemistry faculty in Charlottenburg Polytechnic in Berlin. In about 1910 he obtained the degree of chemist-engineer (the diplom was not found). From 1911 to 1914 he was an assistant of Wichard von Moellendorff. His first publication was devoted to metal crystallography, dislocation theory (Technologische Schluesse aus Kristallographie der Metalle Technological conclusions from metal crystallography) Z.d.V.d.Ing. 57(1913)931 and 1014.

6 In Germany: INSTYTUT TECHNOLOGII MATERIA ÓW ELEKTRONICZNYCH E M P L O Y M E N T 1904 he worked in pharmacy and drugstore of Dr A. Herbrand in Berlin Central Lab. of Kunheim&Co. in Niederschoenweide (near Berlin) 1907 Allgemeinen Elecrizitaets-Gesellschaft (AEG), Kabelwerk Oberspree in Oberschoenweide and Haelsenbau he was an assistant of Wichard von Moellendorff - first paper from 1916 he was the Head of Laboratory of Steel and Iron Research. He investigated purity and quality of metals and worked on copper refinement. The main task of Czochralski was the introduction of aluminium to electrical engeeneringproduction of aluminium products, alloys, standarizaton of metallographic studies he moved to Frankfurt on Mein, organized the Laboratory of metals Science of the Metall Gesselschaft A.G. metal B, patented in Pioneer investigations of anisotropy of hardness of single crystals ( )-important works for plastic treatment of materials.

7 In Poland: He did not accept the offer given by H. Ford to work in USA - he accepted the proposal given by the Polish President I. Moœcicki and in 1929 he came back to Poland 1929 the honorary doctorate given by Warsaw University of Technology (WUT) 1930 the title and position of professor in the Faculty of Chemistry of Warsaw University of Technology where he organized his laboratory: Department of Metallurgy and Metals Science at Warsaw University of Technology and then Institute of Metallurgy and Metal Science. He also founded Metallurgical Section in the Chemical Research Institute. He continued the studies of the rate of crystallization of metals, elastic properties, corrosion of metals and alloys 1939 II World War all laboratories in Warsaw were closed by German occupants In 1940 his laboratory was opened and then some others at the WUT In 1945 he moved to Kcynia and opened the firm BION produced chemicals for drugstore He died in 1953

8 Czochralski publications (about 250) in : German journals: Z. d. V. d. Ing. Zeitschrift des Vereins deutscher Ingeneurie Z. Met. Zeitschrift für Metallkunde Z. anorg. allg. Chem. Zeitschrift für anorganische und allgemeine Chemie Z. angew. Chemie Zeitschrift für angewande Chemie Giess. Ztg. Giesserei Zeitung (organ des Gesamtverbandes Deutscher Metallgiessereien) Polish journals: Wiad. Inst. Met. Met. Wiadomoœci Instytutu Metalurgii i Metaloznawstwa Przem. Chem. - Przemys³ Chemiczny Przem. Mech. - Przegl¹d Mechaniczny Patents Books in Polish and German languages Conferences and visits European countries and USA Very rich citation, works from 1880, used languages: German, Polish, French Societies: Deutsche Gesellschaft für Metallkunde 1924, v-president and President 1926 Polish Chemical Society 1929 Society of Polish Mechanic Engineers honour member

9 the Czochralski method in the Czochralski papers: The results of the study of the rate of crystallization of tin, zinc and lead were published in Z.phys.Chem. 92 (1918) , Ein neues Verfahren zur Messung des Kristallisationsgeschwindigkeit der Metalle The paper was received by the editorial board on August 19, He found that the crystallization wire was single crystal of diam. about 1 mm and lengths up to 150 cm. The paper reported the description of a lifter and its junction with wire. The maximum rate of pulling of a crystal was recognized as the proper characteristics of the crystallizing material In the Polish journal: J. Czochralski, W. Garlicka, (Crystallization rate of sodium and the relations between atomic heat of solidification and crystallization rate) Wiad. Inst. Met. Met. 3 (1936) citated his method as the Czochralski method with reference to the paper 1918 Statement: the rate of crystallization is the best at the certain supercooling at the crystal-melt interface. The atomic, molecular Kossel s theory is discussed paper is citated in: Quantentheorie u. Chemie, J. Czochralski, J. Miko³ajczyk, as above, (1936) crystallization of Al % (rate of crystalization - dendritic and single crystal growth; rate mm/min -microscopic).

10 Historical outline of the Czochralski method -CZ-method (from the paper: J. Czochralski, 'Ein neues Verfahren zur Messung des Kristallisationsgeschwindigkeit der Metalle ' Z. phys. Chem. 92 (1918) ). The paper was received by the editorial board on August 19, Crystallization of tin, zinc and lead were performed. He found that the crystallization wire was single crystal of diam. about 1mm and lengths up to 150cm. The paper reported the description of a lifter and its junction with wire and the maximum rate of pulling of a crystal was recognized as the proper characteristics of the crystallizing material.

11 the Czochralski method in the Czochralski papers: The results of the study of the rate of crystallization of tin, zinc and lead were published in Z.phys.Chem. 92 (1918) , Ein neues Verfahren zur Messung des Kristallisationsgeschwindigkeit der Metalle The paper was received by the editorial board on August 19, He found that the crystallization wire was single crystal of diam. about 1 mm and lengths up to 150 cm. The paper reported the description of a lifter and its junction with wire. The maximum rate of pulling of a crystal was recognized as the proper characteristics of the crystallizing material In the Polish journal: J. Czochralski, W. Garlicka, (Crystallization rate of sodium and the relations between atomic heat of solidification and crystallization rate) Wiad. Inst. Met. Met. 3 (1936) citated his method as the Czochralski method with reference to the paper 1918 Statement: the rate of crystallization is the best at the certain supercooling at the crystal-melt interface. The atomic, molecular Kossel s theory is discussed paper is citated in: Quantentheorie u. Chemie, J. Czochralski, J. Miko³ajczyk, as above, (1936) crystallization of Al % (rate of crystalization - dendritic and single crystal growth; rate mm/min -microscopic).

12 Crystallization rate of sodium and the relations between atomic heat of solidification and crystallization rate (J. Czochralski, W Garlicka, Wiad. Inst. Met. Met. 3 (1936) 39 41, in Polish) The method as the Czochralski method with reference to the paper is citated. Relations-rate of crystallization and atomic heat of crystallization, from 50 cal/g-ag to 61.8 kcal/g-p. Reciprocal relation of crystallization rate and atomic heat of solidification (equilibrium temperature between liquid and crystal). Most heat is transported by crystal A-mixer; B-junction; D-crank handle; E, R-transmission wheels; G-record player mechanism; K-ksylen; M-motor; S-scale; T 1, T 2, T 3 -thermometers; W-paraphine bath; Z-needle (seed)

13 the Czochralski method in the published papers: H. von Wartenberg (Verhandlung der Deutsche Phys. Gesellschaft 20(1918)113, Über elastische Nachwirkung bei Metallen ) used seeds (zinc wire) to grow the crystals of zinc. E.v.Gomperz (Z. Phys.8(1922)184, Untersuchungen an Einkristalldrähten ) called for the first time this method Czochralski s name then Linder (E.G.Linder, Phys. Rev. 26(1925)486, Thermo-electric effect in single crystal zinc wires ) used first time the English name the Czochralski method. Later works dealing with the method are given by Mark et al. (H. Mark, M.Polanyi and E. Schmidt, Z. Phys. 12(1923)58, Vorgänge bei der Dehnung von Zinkkristallen ), Sachs (G. Sachs, Z. Met. 17(1925)238, Die Herstellung von Metallkristallen ) and also Schmidt and Boas (E. Schmidt and W. Boas, Kristallplastizität, J. Springer, Berlin, 1935, Plasticity of crystals, Hughes, London, 1950). After the Second World War, during the time of transistor discovery, scientists at the Bell Lab. in Murray Hill (Gordon K. Teal et al.) extended the Czochralski method to the growth of non-metallic materials starting with germanium and then silicon. It seems that after publication of Buckley s book Crystal Growth in 1951 the name of Czochralski was widely spread and was definitively connected with the method of crystal pulling. Today the Czochralski method is used to grow other semiconductors, oxides, fluorides and a number of binary and multicomponents compounds. All the time the method is improved and developed.

14 Metals and their alloys INSTYTUT TECHNOLOGII MATERIA ÓW ELEKTRONICZNYCH M A T E R I A L S: Aluminium to electrotechnology in ~ 1907 only four countries produced Al products investigation of aluminium and their alloys (recrystallization, alloys with several metals), aluminium alloy-silumin, eutectic alloy of 87% Al + 13% Si high mechanical strength, light discovered by A. Pacz a in 1920 and investigated by J.Czoch. Z. Met.13(1921) 507; enriched by several metal dopants weak effects, Na, Li (1937) the best. investigation of rotguss - bronze of tin-zinc, doped with Pb, Sb, As, Bi (Z. Met. (1920) bearing alloy not containing tin, metal - B (Bahn - metal) with small amounts of Li, Na, Ca and Al (applications in railway and industry), patent in 1924 (after 12 years of investigations) old bearing alloy Pb + (13%, 50%, 86%) Sn new metal B Pb %Ca, 0.58% Na, 0.04 Li and % Al - high mechanical properties (hardness, bending stregth, high Tm) (metal Satco (USA) 98% Pb, 0.04% Li, 0.04% K, 0.075% Mg, 0.05% Al, 0.25% Hg, 1% Sn)

15 Materials investigations: studies on the rate of crystallization of metals resulted in the Czochralski method of growing single crystals which has become widely applied till now studies on the recrystallization of metals resulted in recrystallization diagrams used commonly for description of the properties of materials change of heat effects after recrystallization in time - calorimetric investigations (heat effects decrease to zero after few days) for the measurements of self - improvement of materials, among others, the method of analysis of heating curves has been developed studies of corrosion of different materials stimulated the development of homogeneous and controlled conditions of measurements reagents: wet ammonia, HgCl 2 and HgO, vapour of H 2 O+3%NaCl (Al high pure and techn.), investigations loss of mass and vol % of evaporated H 2 mechanical properties: elasticity, expansions, degree of squeeze, fissility, bending strength plastic deformations of single crystals, slip plane, slip band dislocation motion on crystall. planes metallographic investigations required the developing of new methods of etching which inter alia resulted in Czochralski reagents for the etching of gold Czochralski solutions: Gold etching - new solution better than aqua regia: HCl or 4p.HCl + 1p.H 2 O with anhydride chromic acid (CrO 3 )

16 Materials investigations: studies on the rate of crystallization of metals resulted in the Czochralski method of growing single crystals which has become widely applied till now studies on the recrystallization of metals resulted in recrystallization diagrams used commonly for description of the properties of materials change of heat effects after recrystallization in time - calorimetric investigations (heat effects decrease to zero after few days) for the measurements of self - improvement of materials, among others, the method of analysis of heating curves has been developed studies of corrosion of different materials stimulated the development of homogeneous and controlled conditions of measurements reagents: wet ammonia, HgCl 2 and HgO, vapour of H 2 O+3%NaCl (Al high pure and techn.), investigations loss of mass and vol % of evaporated H 2 mechanical properties: elasticity, expansions, degree of squeeze, fissility, bending strength plastic deformations of single crystals, slip plane, slip band dislocation motion on crystall. planes metallographic investigations required the developing of new methods of etching which inter alia resulted in Czochralski reagents for the etching of gold Czochralski solutions: Gold etching - new solution better than aqua regia: HCl or 4p.HCl + 1p.H 2 O with anhydride chromic acid (CrO 3 )

17 Diagram of calcium recrystalliztion (J. Czochralski, W. elewska, Wiad. Inst. Met. Met. 5 (1938) 1) Degree of deformation is a change of sample height, before and after annealing in different temperatures and cooled to room temperature. Recrystallization takes place after deformation of metals and during their return to an equilibrium state. Etching and polishing solutions to investigate size of grains. Experimental diagram is disordered by some thermochemical properties of metals as: phase transformations-non continuity. On the axis: size of grains, temperature in C and degree of deformation in %.

18 Orientation and etching of crystals (Tammann, Bridgman) J. Czochralski, J. Skowroñska, Przem. Chem. 3 (1937) 65 Spherical surface of AI, cubic face (etching sol % H 2 F 2 ) Twins on (1010) plane of Zn crystal ( etching sol. - conc. HCI)

19 Orientation and etching of crystals (Tammann, Bridgman) (J. Czochralski, J. Skowronska, Przem. Chem. 3 (1937) 65) Spherical surface of Zn crystal, hexagonal symmetry Triangular figures of (0001) plane of Zn (etching sol. - HCI + H 2 O)

20 Lattice dynamics at plastic deformations (J. Czochralski Z.Met. 15 (1923) 60 and 126) Formation of translation P-press Distorted lattice -displaced atoms

21 Metallographic investigations: Metallografic microscopy INSTYTUT TECHNOLOGII MATERIA ÓW ELEKTRONICZNYCH Methods of investigations: the method of quantitative determination of nonmetallic precipitates in iron and steel (microscopic observations and analysis of electrical resistivity of precipitates and the matrix) was born out of studies of the quality of materials Radiomicroscopy detection of electromagnetic waves an attemp to detect nonmetallic precipitates using a specially constructed radiomicroscope (investigation of the static and dynamic characteristic, the contact of the needle with the metal under study) (Z. anorg. allg. Chem. 144 (1925) ). Alloy of Al-Si is investigated as a detector in a radio circut and is placed under a microscope, and a needle connected to the earth through a pair of ear-phones is brought into contact with different parts of the surface of the alloy. There are areas where the detector action was very poor. J.Czoch. explained that the alloy was not homogeneous and Si crystal were separated from melt and were very pure and detector power was lost. Resistivity measurements, J. Czochralski, W. Garlicka, Wiad. Inst. Met. Met. 3 (1936) 39 Changes of resistivity of nonmetalic particles in alloys. Batery 4V, potentiometr, needle of gramophone, sample, miliampermeter (60 ma starting current), compared with conductivity measurements and micrography. Goniometr one circle, acc. 1 0 Œwiêtos³awski microcalorimeter heat effects

22 Radio technic in the service of metallography (detection of electromagnetic waves) J. Czochralski, Z. anorg. allgem. Chem. 144(1925)263 J. Czochralski,W. Sznuk, Wiad. Inst. Met. Met. 3(1936)5 A sample of alloy (Al-Si), (Fe-silicate, steel) is connected in the circuit and placed under a microscope, and a needle connected to earth through a pair of ear-phones is brought into contact with different parts of the surface of the alloy. That the alloy is not homogeneous is evidenced by the fact that there are areas where the detector action is very poor. J.C. believes that the poor Si has separated from the melt and that the areas of poor detector action are due to these crystals of pure Si. The cause of the poor detector action of these crystals may be: (1) a new modification of Si is present; (2) the Si is very pure, because of recrystallization and has lost its detector power as a result of loss its impurities. MT-microscope table, N-metal needle (copper, steel) D-investigated plate of metal, A-antene, E-earth, L-induction coil, T-ear-phone

23 Investigations of metal/alloys crystallinity, grain orientations (J. Czochralski Z.anorg.allg.Chem. 144 (1925) 131) optical methods, polished, etched samples, reflection light at different angles, goniometer Scheme of aparatus for optical measurements A-projection lamp, B' and B"-shutters, L ' and L "-lenses, K-crystal, W-angle measurement (not goniometr) Scheme of crystal with different oriented planes, grains A, B, C -regions of various orientation, reflected light

24 International Forum on Science and Technology of Crystal Growth March , Sendai, Japan Conclusions: Professor dr Jan Czochralski was a metallurgist and he investigated various processes of metal solidifications, crystallization and properties of crystals structural, mechanical, thermochemical His achievements were outstanding and marked out new roads in science and technology Professor dr Jan Czochralski remains in our memory as a great scientist, inventor, well-known in material science, electronics and crystallography the father of crystal growth method the Czochralski method CZ method Professor dr Jan Czochralski signature (named badgerdog ) as the Head of Research Institute of Chemical Metallurgy at the Technical University in Warsaw, from the document Nov. 11, 1936.

25 Kcynia INSTYTUT TECHNOLOGII MATERIA ÓW ELEKTRONICZNYCH Warsaw POLAND

26 Events devoted to Jan Czochralski memory Papers in Polish and international journals - dr P. Tomaszewski Meetings internationals, two visits of foreign scientists in Kcynia Workshop 2000 (ITME, Warsaw) the first visit VI Polish Conference on Crystal Growth, May, 2001 in Poznañ - the second visit Medals * Founded by the 1 st Asian Conference on Crystal Growth and Crystal Technology (CGCT-1), Aug.-Sept., 2000, in Sendai Two Awards-Jan Czochralski medal Award for Crystal Growth - Dr. Tomoki Inada Award for Crystal Technology Prof. Shuji Nakamura Foundation of Materials Science Development * Gold Medal of Jan Czochralski dr Paul Siffert, Nov., 2000, in Cracow, MRS Meeting in Central and Eastern Europe * Gold Medal of Jan Czochralski- Prof. Kazimierz J. Flaga, June 2001, Strasbourg, E-MRS Spring Meeting

27 th anniversary of Jan Czochralski death

28 45th anniversary of Jan Czochralski death

29 INSTYTUT TECHNOLOGII MATERIA ÓW ELEKTRONICZNYCH