Czochralski process

2 Production of Czochralski silicon

High-purity, semiconductor-grade silicon (only a few
parts per million of impurities) is melted in a crucible
at 1425 degree Celsius, usually made of quartz. Dopant
impurity atoms such as boron or phosphorus can be added
Melting of
Introduction Beginning of
Crystal
Formed crystal
to the molten silicon in precise amounts to dope the silthe crystal
polysilicon,
of the seed
pulling
with a residue
growth
doping
crystal
of melted silicon
icon, thus changing it into p-type or n-type silicon, with
dierent electronic properties. A precisely oriented rodmounted seed crystal is dipped into the molten silicon.
The Czochralski process
The seed crystals rod is slowly pulled upwards and rotated simultaneously. By precisely controlling the temperature gradients, rate of pulling and speed of rotation,
The Czochralski process is a method of crystal growth
it is possible to extract a large, single-crystal, cylindrical
used to obtain single crystals of semiconductors (e.g.
ingot from the melt. Occurrence of unwanted instabilities
silicon, germanium and gallium arsenide), metals (e.g.
in the melt can be avoided by investigating and visualizpalladium, platinum, silver, gold), salts and synthetic
ing the temperature and velocity elds during the crystal
gemstones. The process is named after Polish sciengrowth process.[5] This process is normally performed in
[1]
tist Jan Czochralski, who invented the method in 1916
an inert atmosphere, such as argon, in an inert chamber,
while investigating the crystallization rates of metals.[2]
such as quartz.
He made this discovery by accident, while studying the
crystallization rate of metals when, instead of dipping his
pen into the ink, he did so in molten tin and drew a tin
3 Crystal sizes
lament, that later proved to be a single crystal.[3]
The most important application may be the growth of
large cylindrical ingots, or boules, of single crystal silicon
used in the electronics industry to make semiconductor
devices like integrated circuits. Other semiconductors,
such as gallium arsenide, can also be grown by this
method, although lower defect densities in this case can
be obtained using variants of the Bridgman-Stockbarger
technique.

Due to the eciencies of common wafer specications,

the semiconductor industry has used wafers with standardized dimensions. In the early days, the boules were
smaller, only a few inches wide. With advanced technology, high-end device manufacturers use 200 mm and 300
mm diameter wafers. The width is controlled by precise
control of the temperature, the speeds of rotation and the
speed the seed holder is withdrawn. The crystal ingots
from which these wafers are sliced can be up to 2 metres
in length, weighing several hundred kilogrammes. Larger
wafers allow improvements in manufacturing eciency,
as more chips can be fabricated on each wafer, so there
1 Application
has been a steady drive to increase silicon wafer sizes.
The next step up, 450 mm, is currently scheduled for in[6]
Monocrystalline silicon (mono-Si) grown by the troduction in 2018. Silicon wafers are typically about
Czochralski process is often referred to as monocrys- 0.20.75 mm thick, and can be polished to great attalline Czochralski silicon (Cz-Si). It is the basic ness for making integrated circuits or textured for making
material in the production of integrated circuits used solar cells.
in computers, TVs, mobile phones and all types of The process begins when the chamber is heated to apelectronic equipment and semiconductor devices.[4] proximately 1500 degrees Celsius, melting the silicon.
Monocrystalline silicon is also used in large quantities When the silicon is fully melted, a small seed crystal
by the photovoltaic industry for the production of mounted on the end of a rotating shaft is slowly lowered
conventional mono-Si solar cells. The almost perfect until it just dips below the surface of the molten silicon.
crystal structure yields the highest light-to-electricity The shaft rotates counterclockwise and the crucible roconversion eciency for silicon.
tates clockwise. The rotating rod is then drawn upwards
1

INCORPORATING IMPURITIES

Silicon crystal being grown by Czochralski process at Raytheon,

1956. The induction heating coil is visible, and the end of the
crystal just emerging from the melt. The technician is measuring
the temperature with an optical pyrometer. One of the earliest Si
plants, the crystals produced by this early apparatus were only
one inch in diameter.

and the process is called doping. This method is also used

with semiconductor materials other than silicon, such as
gallium arsenide.

4 Incorporating impurities

Crystal of Czochralski grown silicon.

very slowlyabout 25mm per hour when making a crystal of ruby[7] allowing a roughly cylindrical boule to be
formed. The boule can be from one to two metres, de- A puller rod with seed crystal for growing single-crystal silicon
by the Czochralski process.
pending on the amount of silicon in the crucible.
The electrical characteristics of the silicon are controlled When silicon is grown by the Czochralski method, the
by adding material like phosphorus or boron to the silicon melt is contained in a silica (quartz) crucible. During
before it is melted. The added material is called dopant growth, the walls of the crucible dissolve into the melt and

3
Czochralski silicon therefore contains oxygen at a typical
concentration of 1018
cm3
. Oxygen impurities can have benecial eects. Carefully chosen annealing conditions can allow the formation of oxygen precipitates. These have the eect of
trapping unwanted transition metal impurities in a process known as gettering. Additionally, oxygen impurities
can improve the mechanical strength of silicon wafers by
immobilising any dislocations which may be introduced
during device processing. It was experimentally shown in
the 1990s that the high oxygen concentration is also benecial for the radiation hardness of silicon particle detectors used in harsh radiation environment (such as CERN's
LHC/HL-LHC projects).[8][9] Therefore, radiation detectors made of Czochralski- and Magnetic Czochralskisilicon are considered to be promising candidates for
many future high-energy physics experiments.[10][11] It
has also been shown that the presence of oxygen in silicon increases impurity trapping during post-implantation
annealing processes.[12]
However, oxygen impurities can react with boron in an
illuminated environment, such as that experienced by solar cells. This results in the formation of an electrically
active boronoxygen complex that detracts from cell performance. Module output drops by approximately 3%
during the rst few hours of light exposure.[13]

IL
dV
VO VS
IL
VS
dI
dV
= kO
I
V
VS
L
O
IO
0
( )
(
)kO
IL
VS
ln
= ln 1
IO
VO
)k
(
VS O
IL = IO 1
VO
dI = kO

CS =

dIL
dVS

CS = CO kO (1 f )ko 1
f = VS /VO

5 Gallery
Crucibles used in Czochralski method
Crucible after being used

6 See also
Monocrystalline silicon
BridgmanStockbarger technique

4.1

Mathematical expression of impurity

incorporation from melt

The impurity concentration in the solid crystal that results from freezing an incremental amount of volume
can be obtained from consideration of the segregation
coecient.[14]

kO
V0
I0
C0
VL
IL
CL
VS
CS
During the growth process, volume of melt dV freezes,
and there are impurities from the melt that are removed.

dI = kO CL dV

Float-zone silicon
Laser-heated pedestal growth
Micro-pulling-down

7 References
[1] (Polish), (English), Pawe Tomaszewski, ""Jan Czochralski i jego metoda (ang.Jan Czochralski and his method),
Ocyna Wydawnicza ATUT, WrocawKcynia 2003,
ISBN 83-89247-27-5
[2] J. Czochralski (1918) Ein neues Verfahren zur Messung
der Kristallisationsgeschwindigkeit der Metalle [A new
method for the measurement of the crystallization rate of
metals], Zeitschrift fr Physikalische Chemie, 92 : 219
221.
[3] Nishinaga, Tatau (2015). Handbook of Crystal Growth:
Fundamentals (Second ed.). Amsterdam, the Netherlands: Elsevier B.V. p. 21. ISBN 978-0-444-56369-9.
[4] Czochralski Crystal Growth Method. Bbc.co.uk. 30 January 2003. Retrieved on 2011-12-06.
[5] Aleksic, Jalena; Zielke, Paul; Szymczyk, Janusz A.;
et al. (2002). Temperature and Flow Visualization in a Simulation of the Czochralski Process Using Temperature-Sensitive Liquid Crystals. Ann. N.Y.
Acad. Sci. 972: 158. Bibcode:2002NYASA.972..158A.
doi:10.1111/j.1749-6632.2002.tb04567.x.

[6] Doubts over 450mm and EUV. Electronicsweekly.com.

December 30, 2013. Retrieved on 2014-01-09.
[7] Czochralski Process. www.theimage.com. Retrieved
2016-02-25.
[8] Li, Z.; Kraner, H.W.; Verbitskaya, E.; Eremin, V.;
Ivanov, A.; Rattaggi, M.; Rancoita, P.G.; Rubinelli, F.A.;
Fonash, S.J.; et al. (1992). Investigation of the oxygenvacancy (A-center) defect complex prole in neutron irradiated high resistivity silicon junction particle detectors.
IEEE Transactions on Nuclear Science. 39 (6): 1730.
Bibcode:1992ITNS...39.1730L. doi:10.1109/23.211360.
[9] Lindstrm, G; Ahmed, M; Albergo, S; Allport, P; Anderson, D; Andricek, L; Angarano, M.M; Augelli, V; Bacchetta, N; Bartalini, P; Bates, R; Biggeri, U; Bilei, G.M;
Bisello, D; Boemi, D; Borchi, E; Botila, T; Brodbeck,
T.J; Bruzzi, M; Budzynski, T; Burger, P; Campabadal,
F; Casse, G; Catacchini, E; Chilingarov, A; Ciampolini,
P; Cindro, V; Costa, M.J; Creanza, D; Clauws, P
(2001). Radiation hard silicon detectorsdevelopments
by the RD48 (ROSE) collaboration. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment. 466 (2): 308. Bibcode:2001NIMPA.466..308L.
doi:10.1016/S0168-9002(01)00560-5.
[10] CERN RD50 Status Report 2004, CERN-LHCC-2004031 and LHCC-RD-005 and cited literature therein
[11] Harkonen, J; Tuovinen, E; Luukka, P; Tuominen, E;
Li, Z; Ivanov, A; Verbitskaya, E; Eremin, V; Pirojenko,
A; Riihimaki, I.; Virtanen, A. (2005). Particle detectors made of high-resistivity Czochralski silicon. Nuclear Instruments and Methods in Physics Research Section
A: Accelerators, Spectrometers, Detectors and Associated
Equipment. 541: 202. Bibcode:2005NIMPA.541..202H.
doi:10.1016/j.nima.2005.01.057.
[12] Custer, J. S.; Polman, A.; Van Pinxteren, H. M.
(1994). Erbium in crystal silicon: Segregation and
trapping during solid phase epitaxy of amorphous silicon. Journal of Applied Physics. 75 (6): 2809.
Bibcode:1994JAP....75.2809C. doi:10.1063/1.356173.
[13] Eikelboom, J.A., Jansen, M.J., 2000. Characterisation of
PV modules of new generations; results of tests and simulations. Report ECN-C-00-067, 18.
[14] James D. Plummer, Michael D. Deal, and Peter B. Grin,
Silicon VLSI Technology, Prentice Hall, 2000, ISBN 0-13085037-3 pp. 12627

External links
Czochralski doping process
Silicon Wafer Processing Animation on YouTube

EXTERNAL LINKS

Text and image sources, contributors, and licenses

9.1

Text

Czochralski process Source: https://en.wikipedia.org/wiki/Czochralski_process?oldid=737044717 Contributors: Bryan Derksen, Rmhermen, Maury Markowitz, Heron, Dgrant, Looxix~enwiki, Maximus Rex, Lzur, Ancheta Wis, Giftlite, Khalid hassani, Darrien, Sam Hocevar,
Discospinster, Alistair1978, Bender235, Jpgordon, Hooperbloob, Nashikawa, AnnaP, Sjschen, Bantman, Twisp, Gene Nygaard, Plattopus, Oleg Alexandrov, SeanMack, Srleer, Jaraalbe, YurikBot, The1physicist, Robchurch, Tetracube, Closedmouth, Murphyjd, Guillom,
Whobot, Oneirist, Listowy, SmackBot, Jrockley, Chendy, Kukini, Guroadrunner, Robosh, Hu12, Chetvorno, Van helsing, Myasuda, Cydebot, Krauss, Kanags, Oerjan, Headbomb, JAnDbot, Karlhahn, Mtiany71, LorenzoB, Eybot~enwiki, GoatGuy, Warut, KylieTastic,
VolkovBot, A4bot, Sabih omar, Andy Dingley, Cwkmail, Emesee, WurmWoode, Pernambuko, Mumiemonstret, Alexbot, XLinkBot, Addbot, Mr0t1633, Angrense, Lightbot, Luckas-bot, Yobot, AnomieBOT, Materialscientist, Citation bot, Jergling, Valerychani, Citation bot
4, Trappist the monk, 10987sa, AndyHe829, John of Reading, East of Borschov, GianniG46, ClueBot NG, Helpful Pixie Bot, Bibcode
Bot, D1vanloon, MSUGRA, Rfassbind, Dough34, Trackteur and Anonymous: 71

9.2

Images

File:Commons-logo.svg Source: https://upload.wikimedia.org/wikipedia/en/4/4a/Commons-logo.svg License: CC-BY-SA-3.0 Contributors: ? Original artist: ?

File:Czochralski_Process.svg Source: https://upload.wikimedia.org/wikipedia/commons/6/6e/Czochralski_Process.svg License: Public
domain Contributors: This vector image was created with Inkscape. Original artist: Twisp
File:Monokristalines_Silizium_fr_die_Waferherstellung.jpg Source:
https://upload.wikimedia.org/wikipedia/commons/2/23/
Monokristalines_Silizium_f%C3%BCr_die_Waferherstellung.jpg License: CC-BY-SA-3.0 Contributors: ? Original artist: ?
File:Silicon_grown_by_Czochralski_process_1956.jpg Source:
https://upload.wikimedia.org/wikipedia/commons/5/5a/Silicon_
grown_by_Czochralski_process_1956.jpg License: Public domain Contributors: Retrieved September 16, 2014 from <a data-xrel='nofollow' class='external text' href='http://www.americanradiohistory.com/Archive-Radio-News/50s/Radio-News-1956-05-R.
pdf'>Radio and Television News magazine, Zi-Davis Publishing Co., New York, Vol. 55, No. 5, May 1956, cover</a> on American
Radio History site Original artist: George E. Meyers
File:Silicon_seed_crystal_puller_rod.jpg Source: https://upload.wikimedia.org/wikipedia/commons/a/a3/Silicon_seed_crystal_puller_
rod.jpg License: GFDL Contributors: Own work Original artist: Warut Roonguthai
File:Snow_crystallization_in_Akureyri_2005-02-26_19-03-37.jpeg Source: https://upload.wikimedia.org/wikipedia/commons/d/d3/
Snow_crystallization_in_Akureyri_2005-02-26_19-03-37.jpeg License: Public domain Contributors: Own work Original artist: var
Arnfjr Bjarmason

9.3

Content license

Creative Commons Attribution-Share Alike 3.0