Zone melting

1
Zone melting
Pfann (left) showing the first zone refining tube,
Bell Labs, 1953
Liquid moves from left to right during melting in
the float-zone crystal growth process
Silicon crystal in the beginning of the
growth process
Zone melting (or zone refining or floating zone process) is a group
of similar methods of purifying crystals, in which a narrow region of a
crystal is molten, and this molten zone is moved along the crystal. The
molten region melts impure solid at its forward edge and leaves a wake
of purer material solidified behind it as it moves through the ingot. The
impurities concentrate in the melt, and are moved to one end of the
ingot. Zone refining was developed by William Gardner Pfann in Bell
Labs as a method to prepare high purity materials for manufacturing
transistors. Its early use was on germanium for this purpose, but it can
be extended to virtually any solute-solvent system having an
appreciable concentration difference between solid and liquid phases at
equilibrium.
[1]
This process is also known as the float zone process,
particularly in semiconductor materials processing.
Process details
The principle is that the segregation coefficient k (the ratio of an
impurity in the solid phase to that in the liquid phase) is usually less
than one. Therefore, at the solid/liquid boundary, the impurity atoms
will diffuse to the liquid region. Thus, by passing a crystal boule
through a thin section of furnace very slowly, such that only a small
region of the boule is molten at any time, the impurities will be
segregated at the end of the crystal. Because of the lack of impurities in
the leftover regions which solidify, the boule can grow as a perfect
single crystal if a seed crystal is placed at the base to initiate a chosen
direction of crystal growth. When high purity is required, such as in
semiconductor industry, the impure end of the boule is cut off, and the
refining is repeated.
In zone refining, solutes are segregated at one end of the ingot in order
to purify the remainder, or to concentrate the impurities. In zone
leveling, the objective is to distribute solute evenly throughout the
purified material, which may be sought in the form of a single crystal.
For example, in the preparation of a transistor or diode semiconductor,
an ingot of germanium is first purified by zone refining. Then a small
amount of antimony is placed in the molten zone, which is passed
through the pure germanium. With the proper choice of rate of heating
and other variables, the antimony can be spread evenly through the
germanium. This technique is also used for the preparation of silicon
for use in computer chips.
Zone melting
2
Growing silicon crystal
A high-purity (99.999%=5N) tantalum single
crystal, made by the floating zone process
(cylindrical object in the center)
Heaters
A variety of heaters can be used for zone melting, with their most
important characteristic being the ability to form short molten zones
that move slowly and uniformly through the ingot. Induction coils,
ring-wound resistance heaters, or gas flames are common methods.
Another method is to pass an electric current directly through the ingot
while it is in a magnetic field, with the resulting magnetomotive force
carefully set to be just equal to the weight in order to hold the liquid
suspended. Optical heaters using high powered [Halogen
lamp|halogen] or xenon lamps are used extensively in research
facilities particularly for the production of insulators, but their use in
industry is limited by the relatively low power of the lamps, which
limits the size of crystals produced by this method. Zone melting can
be done as a batch process, or it can be done continuously, with fresh
impure material being continually added at one end and purer material
being removed from the other, with impure zone melt being removed
at whatever rate is dictated by the impurity of the feed stock.
Indirect-heating floating zone methods use an induction-heated
tungsten ring to heat the ingot radiatively, and are useful when the
ingot is of a high-resistivity semiconductor on which classical
induction heating is ineffective.
Mathematical expression of impurity concentration
When the liquid zone moves by a distance , the number of
impurities in the liquid change. Impurities are incorporated in the
melting liquid and freezing solid.
[2]
: Segregation coefficient
: Zone length
: Initial uniform impurity concentration of the rod
: Concentration of impurities in the liquid
: Number of impurities in the liquid
: Number of impurities in zone when first formed at bottom
The number of impurities in the liquid changes in accordance with the expression below during the movement
of the molten zone
Zone melting
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Applications
Solar cells
In solar cells float zone processing is particularly useful because the single crystal silicon grown has desirable
properties. The bulk charge carrier lifetime in float-zone silicon is the highest among various manufacturing
processes. Float-zone carrier lifetimes are around 1000 microseconds compared to 20-200 microseconds with
Czochralski process, and 130 microseconds with cast multi-crystalline silicon. A longer bulk lifetime increases the
efficiency of solar cells significantly.
Related processes
Zone remelting
Another related process is zone remelting, in which two solutes are distributed through a pure metal. This is
important in the manufacture of semiconductors, where two solutes of opposite conductivity type are used. For
example, in germanium, pentavalent elements of group V such as antimony and arsenic produce negative (n-type)
conduction and the trivalent elements of group III such as aluminum and boron produce positive (p-type) conduction.
By melting a portion of such an ingot and slowly refreezing it, solutes in the molten region become distributed to
form the desired n-p and p-n junctions.
References
[1] Float Zone Crystal Growth (http:/ / www. tf. uni-kiel.de/ matwis/ amat/ elmat_en/ kap_6/ advanced/ t6_1_3. html)
[2] [2] James D. Plummer, Michael D. Deal, and Peter B. Griffin, Silicon VLSI Technology, Prentice Hall, 2000, p. 129
William G. Pfann (1966) Zone Melting, 2nd edition, John Wiley & Sons.
Hermann Schildknecht (1966) Zone Melting, Verlag Chemie.
Georg Mller (1988) Crystal growth from the melt Springer-Verlag, Science 138 pages ISBN 3-540-18603-4,
ISBN 978-3-540-18603-8
Article Sources and Contributors
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Article Sources and Contributors
Zone melting Source: http://en.wikipedia.org/w/index.php?oldid=619598846 Contributors: Abune, Athaler, Beland, Bob, Bryan Derksen, Catbar, Chetvorno, Cometstyles, Dsgray, Edwtie,
Fallschirmjger, Fivemack, Gentgeen, Georgewilliamherbert, Gkb666, Hemanshu, Hooperbloob, Hu12, Jamesont, Katsina2, King of Hearts, Kitedriver, Mac, MarSch, MarsmanRom,
Materialscientist, Maximus Rex, Michael Hardy, Mrba70, Mwr0, Rbeas, Rgdboer, Rifleman 82, Schusch, ShelfSkewed, Snafflekid, Squids and Chips, Srleffler, Thacia, Woohookitty,
Yogirox234, 19 anonymous edits
Image Sources, Licenses and Contributors
Image:Zone refining Bell Labs 1954.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Zone_refining_Bell_Labs_1954.jpg License: Public Domain Contributors: Chetvorno
File:Float-zone crystal growth process svg.svg Source: http://en.wikipedia.org/w/index.php?title=File:Float-zone_crystal_growth_process_svg.svg License: Public Domain Contributors:
Float-zone_crystal_growth_process.png: Dgray derivative work: Asiela (talk)
File:Si-crystal floatingzone.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Si-crystal_floatingzone.jpg License: GNU Free Documentation License Contributors: Matthias Renner
Original uploader was Marathoni62 at de.wikipedia
File:Si-crystal floatingzone growing.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Si-crystal_floatingzone_growing.jpg License: GNU Free Documentation License Contributors:
Matthias Renner Original uploader was Marathoni62 at de.wikipedia
File:Tantalum single crystal and 1cm3 cube.jpg Source: http://en.wikipedia.org/w/index.php?title=File:Tantalum_single_crystal_and_1cm3_cube.jpg License: Free Art License Contributors:
Alchemist-hp (talk) ( www.pse-mendelejew.de)
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