90th anniversary of Czochralski pulling method

90th anniversary
of Czochralski method
1885-1953 1885 1953

In 2006 we celebrate the 90 th anniversary of Czochralski pulling
method.
Professor Jan Czochralski invented this method during the
investigations of the crystallization rate of metals.
In the fifties of the twentieth century his method was adopted for
growing large single crystals of semiconductors on an industrial
scale.
Moreover, a large group of applicable oxides are grown using
Czochralski method.
Also the number of single crystals of intermetallic compounds is
quickly growing thanks to this method.
The Institute of Electronic Materials Technology (ITME)
GdCa 4 O(BO 3 ) 3
UŚ
Fe 2.25 V 0.75 Al

Arms of Kcynia
•Professor Professor Jan Czochralski was born on October 23, 1885 in Kcynia, Kcynia,
in
part of Poland at that time under the Prussian domination, as the eighth
child of the Polish craftsmen Franciszek Czochralski and Marta from the
Suchomski family. The Czochralskis were carpenters for many
generations.
•Jan Jan completed teachers' seminar in Kcynia according to the wish of his
father. He was already interested in chemistry during his school days.
However, he did not accept his matriculation certificate due to poor
grades.
•Lack Lack of this certificate unabled him to continue his education. For some
time he worked in Krotoszyn in a drugstore.

Bydgoszcz

Berlin
•At t the end of 1904 he went to Berlin and began to work in the drugstore drugstore
of Dr. A.
Herbrand in Altglienicke, Altglienicke,
the districts of Berlin.
•Later Later he worked for a short period in the laboratory of Kunheim and Co. in
Niederschönweide
Niedersch nweide near Berlin and then in Allgemeine Elektrizitäts
Elektrizit ts-Gesellschaft
Gesellschaft
(AEG). The job in Kabelwerk Oberspree and the two years spent in their research
laboratories prepared him to become head of the laboratory of steel steel
and iron
research. This laboratory dealt with the checking the quality and and
purity of metals
and alloys and was engaged in the refinement of copper.
•Simultaneously Simultaneously he attended lectures on chemistry at the Charlottenburg
Polytechnic near Berlin.
•From From 1911 to 1914 he was an assistant of Wichard von Möllendorff llendorff with whom
he published his first paper devoted to the crystallography of metals metals,
, dislocation
theory (Zeitschrift Zeitschrift des Vereines Deutcher Ingenieure
57 (1913) 931-5, 931 5, 1014-20) 1014 20) .
KABELWERK OBERSPREE RESEARCH
LABORATORIES, JAN CZOCHRALSKI (FAR
LEFT).
LEFT)

•Jan Jan Czochralski married in 1910 Marguerit Haase, Haase,
a pianist of Dutch origin, the
daughter of a rich owner of houses. They had three children: two daughters –
Leonia (1914) and Cecilia (1920,) and a son Borys (1918).
CZOCHRALSKI'S FAMILY

•In In 1916 professor Jan Czochralski invented a method for measuring the
crystallization velocity of metals. The method was invented by accident accident
and
through Czochralski careful observations.
•The The idea of this method is based on pulling a crystal from the melt. melt.
The grown
during the experiment crystals as metallic wires were single crystals. crystals.
•The The results of Czochralski studies were published in several papers, The first
one was published in Zeitschrift für Physikalische
hysikalische Chemie 92, 219 (1918), in
German.
•This This new technique allowed to obtain the good
quality single crystals of pure metals like Sn, Sn,
Pb, Pb,
Zn.
After the II World War the Czochralski method was
adopted by the Americans G.K. Teal and J.B. Little
from Bell Telephone Laboratories for growing large
single crystals of semiconductors on an industrial
scale (Growth of germanium single crystals, Phys.
Rev. 78, 647 (1950) and Bull. Amer. Phys. Soc. 25,
16 (1950)).

Franfurt on Mein
•In In 1917 Jan Czochralski moved to Frankfurt on Mein and organized the Laboratory
of Metal Science. Science
• Several valuable scientific papers and patents were developed there. there.
Among the
patents was the highly famous patent on a tin-free tin free bearing alloy for railways, called
metal B, patented in 1924 and bought by many countries all over the world, including
USA, France and England.
•He He also pioneered investigations of the anisotropy of the hardness hardness
of single crystals
(works between 1913 and 1923), which are of great importance for the plastic
treatment of materials.
•In In 1919 Czochralski was among the scientists who founded the German Society for
Metal Science and in 1925 he became its presisent. presisent
Warsaw
•When When Poland regained independence he accepted in 1929 the invitation invitation
of the
President of Poland, Ignacy Mościcki Mo cicki. . Czochralski obtained his first honorary
doctorate of the Faculty of Chemistry at the Warsaw University of Technology. Technology.
It
enabled him to take the position of a professor there.
The Czochralski’s
Czochralski
house in Warsaw

PROF. JAN CZOCHRALSKI, WARSAW, 1929
THE POLISH PRESIDENT IGNACY MOŚCICKI MO CICKI (FAR
RIGHT) VISITING CZOCHRALSKI'S LABORATORY.
JAN CZOCHRALSKI (SECOND FROM THE LEFT). LEFT).

•After After the II World War due to his connections with Germans Czochralski Czochralski
was
suspected of collaboration and even arrested. The suspicion was continued to date of
his dead, but up to now there is no evidence for his collaboration. collaboration.
In fact professor
Czochralski helped the National Army and many people during the war time.
Czochralski returned to Kcynia and to the chemistry and to production production
of cosmetics
and household chemicals.
•He He died on April 22, 1953 in Poznań Pozna due to heart disease and was buried in Kcynia.
•Professor Professor Jan Czochralski was outstanding metallurgist, chemist and crystallographer,
whose crystal growth method allowed dynamic development of the modern modern
science and
technology. However, after the war he was almost forgotten, especially especially
in Poland.
•After After the political changes in Poland the Tenth European Crystallographic Crystallographic
Meeting,
organized in Wroclaw in 1986, was dedicated to Professor Jan Czochralski to
commemorate the seventieth anniversary of the discovery of the Czochralski method.
•Since Since its foundation in 1991, the Polish Society for Crystal Growth Growth
commemorates him
in the form of Czochralski Lecture, which is delivered as the opening lecture of every
Polish Crystal Growth Conference by a distinguished scientist with with
recognized
contribution in crystal growth related fields. In 1998 this Society Society
changed its name to
Czochralski Polish Society for Crystal Growth.

The Czochralski’s
Czochralski
house in Kcynia
„Margowo Margowo”

Professor Czochralski started the crystal growth of metals by immersion of a narrow
capillary in the crucible with melt. In capillary a small nucleus nucleus
of crystal was formed.
Slow pulling out of the melt allowed to obtain metallic monocrystalline wires with
diameters of about 1 mm and lengths up to 150 mm. The crystal growth using the
Czochralski method is continuously improved and developed.
In the Solid State Department of the
Institute of Physics University of
Silesia modification of the
Czochralski method from the
levitating melt was applied. Growing
single crystals of intermetallics in
crucibles degrades their purity and
quality due contact with the material
of the crucible particularly when the
sample contains high reactivity of
rare earths. The applied crucibleless
method allows to obtain a relative
optimal quality of single crystals of
rare earth intermetallics.
intermetallics

RTX intermetallics
Berg-Barrett
Berg Barrett topography
ZrNiAl
TiNiSi

Intensity [a.u.]
20 40 60 80
2θ [deg]
orthorhombic (Dwight)
experimental
hexagonal (Hulliger)

Lattice parameter a [Å]
7.22
7.20
7.18
7.16
7.14
7.12
7.10
GdPdAl
7.08
0 50 100 150 200 250 300
Temperature [K]
Volume [Å 3 ]
182.5
182.0
181.5
181.0
180.5
180.0
GdPdAl
cal (Θ D =260K)
experimental
Lattice parameter c [Å]
4.12
4.10
4.08
4.06
4.04
0 50 100 150 200 250
Temperature [K]
GdPdAl
0 50 100 150 200 250 300
Temperature [K]

The two layers of the structure of
GdPdAl (4 unit cells) at level z=0.5 (a)
and z=0 (b);
only inter-layer bonds are exhibited.
The arrows indicate the movement of
the Al-atoms and the shortening of the
bonds upon cooling (strongly
exaggerated).

Electrical resistivity (µΩm)
30
20
10
T N = 24 K
GdPdAl
T c = 48 K
[105]
180 K
0
0 100 200 300
Temperature (K)

Susceptibility (emu/mole)
12.5
10.0
7.5
5.0
2.5
48 K
θ = 67 K
C = 7.9 emuK/mole
µ eff = 7.94 µ B /f.u.
GdPdAl
H = 360 Oe
10.0
1/χ = (T-θ)/C
0
0 200 400 600 800 1000 0
0 20 40 60 80
7.5
5.0
2.5
Temperature (K)
20 K
48 K
100
80
60
40
20
Inverse susceptibility (mole/emu)

(arb.u.)
'
χ
ac
22 K
48 K
GdPdAl [105]
0 100 200 300
Temperature (K)

Intensity (arb.u.)
VB
Pd 4d
Gd 4f
GdPdAl
GdPdAl
Pd
Gd 5p
0 10 20 30
Binding energy (eV)
0 2
Gd

Intensity (arb. u.)
O rthorhom bic s tructure - Dwight
DyP dAl e xpe rim e nta l
He xa gona l s tructure - Hullige r
10 20 30 40 50 60 70 80 90 100
2θ [de g]
ZrNiAl

Lattice parameter a [Å]
7.18
7.17
7.16
DyPdAl
Cal (Θ D =225K)
Exp
7.15
0 50 100 150 200 250 300
Temperature [K]
Unit cell volume [A 3 ]
177.5
177.0
176.5
176.0
DyPdAl
fit (Θ D =225K)
experimental
Lattice parameter c [Å]
3.985
3.980
3.975
3.970
3.965
3.960
0 50 100 150 200 250 300
Temperature [K]
DyPdAl
Cal (Θ D =225K)
exp
3.955
0 50 100 150 200 250 300
Temperature [K]

Resistivity (µΩm)
0.6
0.5
0.4
0.3
0.2
DyPdAl
17 K
25 K
a axis
0.1
0 100 200
Temperature (K)

Lattice parameter a [A]
7.185
7.180
7.175
7.170
7.165
7.160
HoPdAl
Cal (Θ D =225K)
Exp
7.155
0 50 100 150 200 250 300
Temperature [K]
Volume [A 3 ]
176.0
175.5
175.0
HoPdAl
Cal (Θ D =225K)
Exp
Lattice parameter c [A]
3.950
3.945
3.940
3.935
3.930
3.925
HoPdAl
Cal (Θ D =225K)
Exp
0 50 100 150 200 250 300
Temperature [K]
0 50 100 150 200 250 300
Temperature [K]

Electrical resistivity (µΩm)
2.0
1.5
1.0
0.28
0.21
32 K
GdPdIn
94 K
110 K
90 130
GdPdX
29 K
Sn
0.5
Ge
30 K
18 K
In
0
0
28 K
94 K110
K
100 200 300
Temperature (K)
Al
Si
Ga

Compound
X (IIIA group) group
dρ ph /dT(µΩcm/K)
0.6
0.4
0.2
Al
Si
Crystal
structure
V (Å ( 3 )
GdPdAl (143pm) TiNiSi
240.4
GdPdGa (135pm) Co 2 Si
240.3
GdPdIn (167pm) Co 2 Si
223.0
Ga
Ge
Sn
y=Bexp(-d)
B=83
0
4.5 5.0 5.5 6.0 6.5 7.0
d
Pd 4d
ΓFWHM FWHM (eV eV)
In
Compound
X (IVA group) group
Crystal
structure
V (Å ( 3 )
2.2 GdPdSi (118 pm) pm β – GdPdSi
455.0
1.7 GdPdGe (122 pm) pm β – GdPdGe
471.6
1.3 GdPdSn (140 pm) pm Co 2 Si
264.9
d = M·n/V
Pd 4d
ΓFWHM FWHM
2.4
2.1
1.9
(M – molecular mass of the
GdPdX compound,
n – number of molecules per
unit cell volume,
V- unit cell volume)
(eV eV)

Intensity (arb.u.)
Pd 4d
Gd 4f
Gd 5p
GdPdSi
GdPdIn
0 10 20 30
Binding energy (eV)

Gd 7T3 Berg-Barrett topography of the Gd 7Pd 3 single crystal
Th 7 Fe 3

Berg-Barrett topography of the Gd 7Pd 3 single crystal

Berg-Barrett topography of the Gd 7Rh 3 single crystal

Intensity (arb.u.)
Intensity (arb.u.)
210
210
002
102
211
112
301
202
220
212
311
400
302
401
411
402
322
303
500
e x p
c a l
30 40 50 60
002
102
211
300
301
112
202
220
212
Gd 7Rh Rh3 2 θ (d e g )
Gd 7Pd Pd3 311
400
302
401
3 0 4 0 5 0 6 0
2 θ (d e g )
321
410
410
411
402
213
213
500
303
322
330
330
412
412
e x p
c a l
421
004
313
004
104

Lattice parameter a (Å)
Lattice parameter c (Å)
Volume (Å 3 )
9.86
9.85
9.84
9.83
9.82
6.212
6.208
6.204
6.200
6.196
6.192
523
522
521
520
519
518
Gd 7 Rh 3
T N
0 50 100 150 200 250 300
0 50 100 150 200 250 300
0 50 100 150 200 250 300
Temperature (K)
exp
cal (Θ D =160K)
b)
c)
a)
Lattice parameter a (Å)
Lattice parameter c (Å)
Volume (Å 3 )
9.985 T c
9.980
9.975
9.970
9.965
9.960
9.955
6.285
6.280
6.275
6.270
6.265
6.260
543
542
541
540
539
538
Gd 7 Pd 3
0 50 100 150 200 250 300 350 400
0 50 100 150 200 250 300 350 400
0 50 100 150 200 250 300 350 400
Temperature (K)
exp
cal (Θ D =160K)
a)
b)
c)

Intensity (arb.u.)
Gd 5d
Pd 4d
Rh 4d
Gd 7 Rh 3
Gd 7 Pd 3
Gd
Gd 4f
Gd 5p
0 10 20 30
Binding energy (eV)
-1 0 1 2 3 4

ρ (µΩcm)
200
150
100
50
Gd 7 Rh 3
T N = 140 K
ρ(T)=130+0.022T 2
ρ(T)=27+0.005T 2
i // c
i // a
0 100 200 300
T (K)
ρ (µΩcm)
250
200
150
100
50
Gd 7 Pd 3
ρ(T)=60+0.022T 2
ρ(T)=27+0.015T 2
0 100 200 300 400
T (K)
T 2
T=332 K
i II a
i II c

S (µV/K)
S (µV/K)
12
10
8
6
4
2
0
-2
-4
-6
-8
0 50 100 150 200 250 300
12
10
8
6
4
2
0
∆T II c
∆T II a
∆T II a
∆T II c
T N
T (K)
Gd 7 Pd 3
-2
0 50 100 150 200 250 300 350
T(K)
Gd 7 Rh 3
a)
b)
T c

ρ (µΩcm)
ρ (µΩcm)
80
60
40
20
200
160
120
80
Gd 7 Rh 3
i // c
i // a
B = 0 T
B = 8 T
140 K
40
0 50 100 150 200
T (K)
B = 0 T
B = 8 T
ρ (µΩcm)
ρ (µΩcm)
250
200
150
100
110
90
70
50
Gd 7 Pd 3
B = 0 T
B = 0 T
B = 8T
B = 8T
i II a
i II c
30
0 100 200 300
T (K)

M (µ B /Gd)
M (µ B /Gd)
0.0003
0.0002
0.0001
0.015
0.010
0.005
II c
II a
0
0 100 200 300 400
II a
II c
T N =140 K
Gd 7 Pd 3
B = 0.1 T
T C =334 K
0
0 100 200 300 400
T (K)
Gd Rh
7 3
B = 0.5 T
ZFC
a)
b)
Susceptibility (emu/mole)
Susceptibility (emu/mole)
1.5
1.0
0.5
0
0
80
300 600 900
Gd Pd
7 3
B = 0.03 T
B II a
0
60
40
20
T N =140 K
Gd 7 Rh 3
χ -1 =(T-176)/58.4
µ eff =8.2µ B
χ -1 =(T-355)/56.5
µ eff = 8.0 µ B
325 K
T c =332 K
0
0 200 400 600
Temperature (K)
B = 0.19 T
B II a
12
8
4
4
2
0
Inverse susceptibility (mole/emu)
Inverse susceptibility (mole/emu)

GdPdAl(I) GdPdAl(I)
0.56
c/a a/a a/ Gd
c/c c/ Gd
V/V V/ Gd
GdPdAl(II) GdPdAl(II)
0.57
1.96 0.71 2.75
Gd 7 Rh Rh3 Gd 7 Pd Pd3 µ
eff
=
g
J
µ
gJ – the Lande factor
0.63
0.63
B
J
J – the total quantum number
N(E F) ) – the desity of states at the Fermi energy
A – the exchange interaction
2 0.7 2.78
2.72 72 1.09 2.65
2.75 1.09 2.75
⎡ g −1⎤
( ) ( ) J
J + 1 ⎢1
+ AN EF
⎥
⎣
g J ⎦

Acknowledgments
Author thanks Czochralski Polish Society for Crystal Growth for source
materials (http://www.
( http://www.ptwk ptwk.org.pl/eng/sitemap.html
.org.pl/eng/sitemap.html)
Paweł Pawe Tomaszewski „Jan Jan Czochralski and his method” method 2003
Cooperation:
Cooperation
M. Klimczak, J. Kusz, R. Troć, Tro , A. Winiarski,
M. Skutecka