90th anniversary of czochralski pulling method
TRANSCRIPT
90th anniversary 90th anniversary of Czochralski methodof Czochralski method
18851885--19531953
In 2006 we celebrate the 90th 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 industrialscale. 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.
Fe2.25V0.75Al
GdCa4O(BO3)3
TheThe InstituteInstitute ofof ElectronicElectronic MaterialsMaterials TechnologyTechnology (ITME)(ITME)
UUŚŚ
••Professor Jan Czochralski was born on October 23, 1885 in KcyniaProfessor Jan Czochralski was born on October 23, 1885 in Kcynia, in , in part of Poland at that timepart of Poland at that time under the Prussian domination, as the eighth under the Prussian domination, as the eighth child of the Polish craftsmen Franciszekchild of the Polish craftsmen Franciszek Czochralski and Marta from the Czochralski and Marta from the Suchomski family. The Suchomski family. The CzochralskisCzochralskis were carpenters for many were carpenters for many generations.generations.
••Jan completed teachers' seminar in Kcynia according to the wish Jan completed teachers' seminar in Kcynia according to the wish of his of his father. He was already interested in chemistry during his schoolfather. He was already interested in chemistry during his school days. days. However, he did not accept his matriculation certificate due to However, he did not accept his matriculation certificate due to poor poor grades. grades.
••Lack of this certificate Lack of this certificate unabledunabled him him to to continuecontinue hishis education. education. ForFor some some timetime he worked in he worked in KrotoszynKrotoszyn in a drugstore.
ArmsArms ofof KcyniaKcynia
in a drugstore.
BydgoszczBydgoszcz
BerlinBerlin••AAt the end of 1904 he went to Berlin and began to work in the drut the end of 1904 he went to Berlin and began to work in the drugstore of Dr. A. gstore of Dr. A. HerbrandHerbrand in in AltglienickeAltglienicke, the districts of Berlin., the districts of Berlin.••Later he worked for a short period in the laboratory of Later he worked for a short period in the laboratory of KunheimKunheim and Co. in and Co. in NiederschNiederschöönweidenweide near Berlin and then in near Berlin and then in AllgemeineAllgemeine ElektrizitElektrizitäätsts--GesellschaftGesellschaft(AEG). The job in (AEG). The job in KabelwerkKabelwerk OberspreeOberspree and the two years spent in their research and the two years spent in their research laboratories prepared him to become head of the laboratory of stlaboratories prepared him to become head of the laboratory of steel and iron eel and iron research. This laboratory dealt with the checking the quality anresearch. This laboratory dealt with the checking the quality and purity of metals d purity of metals and alloys and was engaged in the refinement of copper. and alloys and was engaged in the refinement of copper. ••Simultaneously he attended lectures on chemistry at the Simultaneously he attended lectures on chemistry at the CharlottenburgCharlottenburgPolytechnic near Berlin. Polytechnic near Berlin. ••From 1911 to 1914 he was an assistant of From 1911 to 1914 he was an assistant of WichardWichard von von MMööllendorffllendorff with whom with whom he published his first paper devoted to the crystallography of mhe published his first paper devoted to the crystallography of metalsetals, , dislocationdislocationtheorytheory ((ZeitschriftZeitschrift des des VereinesVereines DeutcherDeutcher IngenieureIngenieure
57 (1913) 93157 (1913) 931--5, 10145, 1014--20) 20) ..
KABELWERK OBERSPREE RESEARCH KABELWERK OBERSPREE RESEARCH LABORATORIES, JAN CZOCHRALSKI (FAR LABORATORIES, JAN CZOCHRALSKI (FAR LEFT)LEFT)..
••Jan Czochralski married in 1910 Jan Czochralski married in 1910 MargueritMarguerit HaaseHaase, a pianist of Dutch origin, the, a pianist of Dutch origin, thedaughterdaughter of a rich owner of houses.of a rich owner of houses. TheyThey had three children: two had three children: two daughtersdaughters ––Leonia (1914)Leonia (1914) and Cecilia (1920,) and a son and Cecilia (1920,) and a son BorysBorys (1918).(1918).
CZOCHRALSKI'S FAMILYCZOCHRALSKI'S FAMILY
••In 1916 professor Jan In 1916 professor Jan CzochralskiCzochralski invented a method for measuring the invented a method for measuring the crystallization velocity of metals. The method was invented by acrystallization velocity of metals. The method was invented by accident and ccident and through through CzochralskiCzochralski careful observations. careful observations.
••The idea of this method is based on pulling a crystal from the mThe idea of this method is based on pulling a crystal from the melt. The grown elt. The grown during the experiment crystals as metallic wires were single cryduring the experiment crystals as metallic wires were single crystals. stals.
••The results of The results of CzochralskiCzochralski studies were published in several papers, The first studies were published in several papers, The first one was published in one was published in ZeitschriftZeitschrift ffüürr PPhysikalische hysikalische ChemieChemie 92, 219 (1918), in 92, 219 (1918), in German. German.
••This new technique allowed to obtain the good This new technique allowed to obtain the good quality single crystals of pure metals like quality single crystals of pure metals like SnSn, , PbPb, Zn. , Zn. After the II World War the After the II World War the CzochralskiCzochralski method was method was adopted by the Americans G.K. Teal and J.B. Little adopted by the Americans G.K. Teal and J.B. Little from Bell Telephone Laboratories for growing large from Bell Telephone Laboratories for growing large single crystals of semiconductors on an industrial single crystals of semiconductors on an industrial scale (Growth of germanium single crystals, Phys. scale (Growth of germanium single crystals, Phys. Rev. 78, 647 (1950) and Bull. Amer. Phys. Soc. 25, Rev. 78, 647 (1950) and Bull. Amer. Phys. Soc. 25, 16 (1950)).16 (1950)).
FranfurtFranfurt on on MeinMein••In 1917 Jan Czochralski moved to Frankfurt on In 1917 Jan Czochralski moved to Frankfurt on MeinMein and organized the Laboratory and organized the Laboratory of Metal Scienceof Metal Science..•• Several valuable scientific papers and patents were developed tSeveral valuable scientific papers and patents were developed there. Among the here. Among the patents was the highly famous patent on a tinpatents was the highly famous patent on a tin--free bearing alloy for railways, called free bearing alloy for railways, called metal B, patented in 1924 and bought by many countries all over metal B, patented in 1924 and bought by many countries all over the world, including the world, including USA, France and England. USA, France and England. ••He also pioneered investigations of the anisotropy of the hardneHe also pioneered investigations of the anisotropy of the hardness of single crystals ss of single crystals (works between 1913 and 1923), which are of great importance for(works between 1913 and 1923), which are of great importance for the plastic the plastic treatment of materials. treatment of materials. ••In 1919 In 1919 CzochralskiCzochralski was was amongamong thethe scientistsscientists whowho foundedfounded thethe German German SocietySociety for for Metal Science Metal Science andand inin 1925 1925 hehe becamebecame itsits presisentpresisent..WarsawWarsaw••When Poland regained independence he accepted in 1929 the invitaWhen Poland regained independence he accepted in 1929 the invitation of the tion of the President of Poland, President of Poland, IgnacyIgnacy MoMośścickicicki. Czochralski obtained his first honorary . Czochralski obtained his first honorary doctorate of the Faculty of Chemistry at the Warsaw doctorate of the Faculty of Chemistry at the Warsaw UniversityUniversity ofof TechnologyTechnology. It . It enabled him to take the position of a professor there. enabled him to take the position of a professor there.
TheThe CzochralskiCzochralski’’sshousehouse inin WarsawWarsaw
PROF. JAN CZOCHRALSKI, WARSAW, 1929PROF. JAN CZOCHRALSKI, WARSAW, 1929
THE POLISH PRESIDENT IGNACY MOTHE POLISH PRESIDENT IGNACY MOŚŚCICKI (FAR CICKI (FAR RIGHT) VISITING CZOCHRALSKI'S LABORATORY. RIGHT) VISITING CZOCHRALSKI'S LABORATORY. JAN CZOCHRALSKI (SECOND FROM THE LEFTJAN CZOCHRALSKI (SECOND FROM THE LEFT).).
••After the II World War due to his connections with Germans CzochAfter the II World War due to his connections with Germans Czochralski was ralski was suspected of collaboration and even arrested. The suspicion was suspected of collaboration and even arrested. The suspicion was continued to date of continued to date of his dead, but up to now there is no evidence for his collaboratihis dead, but up to now there is no evidence for his collaboration. In fact professor on. In fact professor Czochralski helped the National Army and many people during the Czochralski helped the National Army and many people during the war time. war time. Czochralski returned to Kcynia and to the chemistry and to produCzochralski returned to Kcynia and to the chemistry and to production of cosmetics ction of cosmetics and household chemicals. and household chemicals.
••He died on April 22, 1953He died on April 22, 1953 in in PoznaPoznańń due to heart disease and was buried in Kcynia. due to heart disease and was buried in Kcynia.
••Professor Jan Professor Jan CzochralskiCzochralski was outstanding metallurgist, chemist and crystallographer, was outstanding metallurgist, chemist and crystallographer, whose crystal growth method allowed dynamic development of the mwhose crystal growth method allowed dynamic development of the modern science and odern science and technology. However, after the war he was almost forgotten, esptechnology. However, after the war he was almost forgotten, especially in Poland. ecially in Poland. ••After the political changes in Poland the Tenth European CrystalAfter the political changes in Poland the Tenth European Crystallographic Meeting, lographic Meeting, organized in Wroclaw in 1986, was dedicated to Professor Jan organized in Wroclaw in 1986, was dedicated to Professor Jan CzochralskiCzochralski to to commemorate the seventieth anniversary of the discovery of the commemorate the seventieth anniversary of the discovery of the CzochralskiCzochralski method. method. ••Since its foundation in 1991, the Polish Society for Crystal GroSince its foundation in 1991, the Polish Society for Crystal Growth commemorates him wth commemorates him in the form of in the form of CzochralskiCzochralski Lecture, which is delivered as the opening lecture of every Lecture, which is delivered as the opening lecture of every Polish Crystal Growth Conference by a distinguished scientist wiPolish Crystal Growth Conference by a distinguished scientist with recognized th recognized contribution in crystal growth related fields. In 1998 this Socicontribution in crystal growth related fields. In 1998 this Society changed its name to ety changed its name to CzochralskiCzochralski Polish Society for Crystal Growth.Polish Society for Crystal Growth.
TheThe CzochralskiCzochralski’’sshousehouse inin KcyniaKcynia
„„MargowoMargowo””
Professor Professor CzochralskiCzochralski started the crystal growth of metals by immersion of a narrow started the crystal growth of metals by immersion of a narrow capillary in the crucible with melt. In capillary a small nucleucapillary in the crucible with melt. In capillary a small nucleus of crystal was formed. s of crystal was formed. Slow pullingSlow pulling outout of the melt allowed of the melt allowed to to obtain metallic obtain metallic monocrystallinemonocrystalline wires with wires with diameters of about 1 mm and lengths up to 150diameters of about 1 mm and lengths up to 150 mm. The crystal growth using the mm. The crystal growth using the CzochralskiCzochralski method is continuously improved and developed. method is continuously improved and developed.
In the Solid State Department of the In the Solid State Department of the Institute of Physics University of Institute of Physics University of Silesia modification of the Silesia modification of the CzochralskiCzochralski method from the method from the levitating melt was applied. Growing levitating melt was applied. Growing single crystals of single crystals of intermetallicsintermetallics in in crucibles degrades their purity and crucibles degrades their purity and quality due contact with quality due contact with thethe material material of of thethe crucible particularly when crucible particularly when thethesample contains high reactivity of sample contains high reactivity of rare earths. The applied rare earths. The applied cruciblelesscruciblelessmethod allows method allows to to obtain a relative obtain a relative optimal quality of single crystals of optimal quality of single crystals of rare earth rare earth intermetallicsintermetallics..
RTX RTX intermetallicsintermetallics
BergBerg--BarrettBarrett topographytopography
ZrNiAlZrNiAl
TiNiSiTiNiSi
20 40 60 80
hexagonal (Hulliger)
experimental
orthorhombic (Dwight)
2θ [deg]
Inte
nsity
[a.u
.]
0 50 100 150 200 250 3007.08
7.10
7.12
7.14
7.16
7.18
7.20
7.22
GdPdAlLa
ttice
par
amet
er a
[Å]
Temperature [K] 0 50 100 150 200 250 300
4.04
4.06
4.08
4.10
4.12 GdPdAl
Latti
ce p
aram
eter
c [Å
]
Temperature [K]
0 50 100 150 200 250
180.0
180.5
181.0
181.5
182.0
182.5
GdPdAl cal (ΘD=260K)experimental
Vol
ume
[Å3 ]
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).
0
10
20
30
0 100 200 300
Tc= 48 K
TN= 24 K
[105]
180 K
GdPdAl
Temperature (K)
Ele
ctric
al re
sist
ivity
(µΩ
m)
0
2.5
5.0
7.5
10.0
12.5
0 200 400 600 800 10000
20
40
60
80
100
1/χ = (T-θ)/C
H = 360 Oe
µeff = 7.94 µB/f.u.
C = 7.9 emuK/mole
θ = 67 K48 K
GdPdAl
Tempera ture (K)
Sus
cept
ibili
ty (e
mu/
mol
e)
Inve
rse
susc
eptib
ility
(mol
e/em
u)
2.5
5.0
7.5
10.0
0 20 40 60 80
20 K
48 K
0 100 200 300
GdPdAl [105]22 K
48 K
Temperature (K)
χ ac'
(arb
.u.)
0 10 20 30
GdPdAl Pd
Gd 5p
Gd 4fPd 4d
VB
GdPdAl
Binding energy (eV)
Inte
nsity
(arb
.u.)
0 2
Gd
10 20 30 40 50 60 70 80 90 100
O rthorhom bic s tructure - Dwight
DyP dAl e xpe rim e nta l
He xa gona l s tructure - Hullige r
2θ [de g]
Inte
nsity
(arb
. u.)
ZrNiAl
0 50 100 150 200 250 3007.15
7.16
7.17
7.18
DyPdAl Cal (ΘD=225K) Exp
Latti
ce p
aram
eter
a [Å
]
Temperature [K] 0 50 100 150 200 250 300
3.955
3.960
3.965
3.970
3.975
3.980
3.985
DyPdAl Cal (ΘD=225K) exp
Latti
ce p
aram
eter
c [Å
]
Temperature [K]
0 50 100 150 200 250 300
176.0
176.5
177.0
177.5 DyPdAl
fit (ΘD=225K)experimental
Uni
t cel
l vol
ume
[A3 ]
Temperature [K]
0.1
0.2
0.3
0.4
0.5
0.6
0 100 200
a axis
17 K25 K
DyPdAl
Temperature (K)
Res
istiv
ity (µ
Ωm
)
0 50 100 150 200 250 3007.155
7.160
7.165
7.170
7.175
7.180
7.185 HoPdAl Cal (ΘD=225K) Exp
Latti
ce p
aram
eter
a [A
]
Temperature [K] 0 50 100 150 200 250 300
3.925
3.930
3.935
3.940
3.945
3.950 HoPdAl
Cal (ΘD=225K) Exp
Latti
ce p
aram
eter
c [A
]
Temperature [K]
0 50 100 150 200 250 300
175.0
175.5
176.0 HoPdAl
Cal (ΘD=225K) Exp
Vol
ume
[A3 ]
Temperature [K]
0
0.5
1.0
1.5
2.0
0 100 200 300
110 K94 K
In
GdPdX
18 K
28 K
32 K
SnGe
Al
Ga
30 K
Si
29 K
Tempera ture (K)
Ele
ctric
al re
sist
ivity
(µΩ
m) 0.21
0.28
90 130
GdPdIn
94 K110 K
0
0.2
0.4
0.6
4.5 5.0 5.5 6.0 6.5 7.0
y=Bexp(-d)
B=83
In
GeSn
Ga
Si
Al
d
dρph
/dT(
µΩcm
/K)
CompoundCompoundX (IIIA X (IIIA groupgroup))
CrystalCrystalstructurestructureV (V (ÅÅ33))
Pd 4dPd 4dΓΓFWHM FWHM ((eVeV))
CompoundCompoundX (IVA X (IVA groupgroup))
Crystal Crystal structurestructureV (V (ÅÅ33))
Pd 4dPd 4dΓΓFWHM FWHM
((eVeV))
GdPdAl GdPdAl (143pm)(143pm) TiNiSi TiNiSi 240.4240.4
2.22.2 GdPdSi GdPdSi (118 (118 pmpm)) ββ –– GdPdSiGdPdSi455.0455.0
2.42.4
GdPdGaGdPdGa (135pm)(135pm) CoCo22SiSi240.3240.3
1.71.7 GdPdGe GdPdGe (122 (122 pmpm)) ββ –– GdPdGeGdPdGe471.6471.6
2.12.1
GdPdIn GdPdIn (167pm)(167pm) CoCo22SiSi223.0223.0
1.31.3 GdPdSn GdPdSn (140 (140 pmpm)) CoCo22SiSi264.9264.9
1.91.9
d = M·n/V
(M – molecular mass of theGdPdX compound,
n – number of molecules per unit cell volume,
V- unit cell volume)
0 10 20 30
GdPdSi
GdPdIn
Gd 5p
Pd 4d Gd 4f
Binding energy (eV)
Inte
nsity
(arb
.u.)
GdGd77TT33
Th7Fe3
Berg-Barrett topography of the Gd7Pd3 single crystal
Berg-Barrett topography of the Gd7Pd3 single crystal
Berg-Barrett topography of the Gd7Rh3 single crystal
3 0 4 0 5 0 6 0
e x pc a l
313
004
412
330
322
303
500
213
402
411
410
401
302
40031
121222
020230
111
2
211
102
00221
0
2 θ ( d e g )
Inte
nsity
(arb
.u.)
GdGd77RhRh33
3 0 4 0 5 0 6 0
e x pc a l
421
004
104
412
33032
230
350
0
213
40241
1
410
321
401
302
40031
1212
22020
2301
11230
0
211
102
00221
0
2 θ ( d e g )
Inte
nsity
(arb
.u.)
GdGd77PdPd33
0 50 100 150 200 250 300
518
519
520
521
522
523
c)Vol
ume
(Å3 )
Temperature (K)
0 50 100 150 200 250 300
6.192
6.196
6.200
6.204
6.208
6.212
b)
Latti
ce p
aram
eter
c (Å
)
0 50 100 150 200 250 300
9.82
9.83
9.84
9.85
9.86
a)
TNGd7Rh3
Latti
ce p
aram
eter
a (Å
)
exp cal (ΘD=160K)
0 50 100 150 200 250 300 350 400
538
539
540
541
542
543
c)
Vol
ume
(Å3 )
Temperature (K)
0 50 100 150 200 250 300 350 4006.260
6.265
6.270
6.275
6.280
6.285
b)
Latti
ce p
aram
eter
c (Å
)
0 50 100 150 200 250 300 350 4009.955
9.960
9.965
9.970
9.975
9.980
9.985 Tc
a)
Gd7Pd3
Latti
ce p
aram
eter
a (Å
)
exp cal (ΘD=160K)
0 10 20 30
Gd7Rh3
Gd7Pd3
Gd
Gd 5p
Gd 5d
Rh 4d
Pd 4d
Gd 4f
Binding energy (eV)
Inte
nsity
(arb
.u.)
-1 0 1 2 3 4
50
100
150
200
0 100 200 300
ρ(T)=27+0.005T2
ρ(T)=130+0.022T2
TN = 140 K
i // c
i // a
Gd7Rh3
T (K)
ρ (µ
Ωcm
)
50
100
150
200
250
0 100 200 300 400
ρ(T)=27+0.015T2
ρ(T)=60+0.022T2
T2
T=332 KGd7Pd3
i II a
i II c
T (K)
ρ (µ
Ωcm
)
-2
0
2
4
6
8
10
12
0 50 100 150 200 250 300 350
b)
Tc
Gd7Pd3∆T II a
∆T II c
T(K)
S (µ
V/K
)
-8-6-4-202468
1012
0 50 100 150 200 250 300
a)
TN
∆T II a
∆T II c Gd7Rh3
T (K)
S (µ
V/K
)
40
80
120
160
200
0 50 100 150 200
B = 8 T
140 K
B = 0 Ti // c
T (K)
ρ (µ
Ωcm
)
20
40
60
80
B = 0 T
B = 8 T
i // aGd7Rh3
ρ (µ
Ωcm
)
30
50
70
90
110
0 100 200 300
i II c
B = 0 T
B = 8T
T (K)
ρ (µ
Ωcm
)
100
150
200
250i II aGd7Pd3
B = 0 T
B = 8Tρ (µ
Ωcm
)
0
0.005
0.010
0.015
0 100 200 300 400
b)
TC=334 K
Gd7Pd3 B = 0.1 T
II a
II c
T (K)
M (µ
B/G
d)
0
0.0001
0.0002
0.0003
0 100 200 300 400
a)
ZFC
TN=140 K
II a
B = 0.5 T II c Gd7Rh3
M (µ
B/G
d)
0
20
40
60
80
0 200 400 6000
2
4χ-1=(T-355)/56.5
325 K
B = 0.03 T B II a
µeff = 8.0 µB
Gd7Pd3
Tc=332 K
Temperature (K)
Sus
cept
ibili
ty (e
mu/
mol
e)
Inve
rse
susc
eptib
ility
(mol
e/em
u)
0
0.5
1.0
1.5
0 300 600 9000
4
8
12
χ-1=(T-176)/58.4
B II aB = 0.19 T
µeff=8.2µB
Gd7Rh3TN=140 K
Sus
cept
ibili
ty (e
mu/
mol
e)
Inve
rse
susc
eptib
ility
(mol
e/em
u)
c/ac/a a/a/aaGdGd c/c/ccGdGd V/V/VVGdGd
GdPdAlGdPdAl(I)(I) 0.560.56
0.570.57
0.630.63
0.630.63
22 0.70.7 2.782.78
GdPdAlGdPdAl(II)(II) 1.961.96 0.710.71 2.752.75
GdGd77RhRh33 22..7272 1.091.09 2.652.65
GdGd77PdPd33 2.752.75 1.091.09 2.752.75
( ) ( ) ⎥⎦
⎤⎢⎣
⎡ −++=
J
JFBJeff g
gEANJJg 111µµ
ggJJ –– thethe LandeLande factorfactor
J J –– thethe totaltotal quantum quantum numbernumber
N(EN(EFF) ) –– thethe desitydesity ofof statesstates atat thethe Fermi Fermi energyenergy
A A –– thethe exchangeexchange interactioninteraction
AcknowledgmentsAcknowledgmentsAuthor thanksAuthor thanks CzochralskiCzochralski Polish Society for Crystal Growth for source Polish Society for Crystal Growth for source materials (materials (http://www.http://www.ptwkptwk.org.pl/eng/sitemap.html.org.pl/eng/sitemap.html))PawePawełł Tomaszewski Tomaszewski „„Jan Jan CzochralskiCzochralski andand his his methodmethod”” 20032003
CooperationCooperation::M. Klimczak, J. Kusz, R. TroM. Klimczak, J. Kusz, R. Troćć, A. Winiarski, , A. Winiarski,
M. M. SkuteckaSkutecka