U.S. patent number 3,607,115 [Application Number 04/872,042] was granted by the patent office on 1971-09-21 for crystal pulling from molten melts including solute introduction means below the seed-melt interface.
This patent grant is currently assigned to General Motors Corporation. Invention is credited to Carl E. Bleil.
United States Patent |
3,607,115 |
Bleil |
September 21, 1971 |
CRYSTAL PULLING FROM MOLTEN MELTS INCLUDING SOLUTE INTRODUCTION
MEANS BELOW THE SEED-MELT INTERFACE
Abstract
An apparatus and method are disclosed for growing crystals from
a melt of a molten solvent metal that is saturated with a solute.
Heat is withdrawn through a seed contacting the surface of the melt
to precipitate the solute onto said seed at the seed-melt
interface. The seed is pulled away from the melt at a rate
commensurate with the precipitation rates. Simultaneously, more
solute is dissolved into the melt from a solute source in the melt
beneath the growth interface while maintaining a close
source-growth interface spacing substantially constant.
Inventors: |
Bleil; Carl E. (Birmingham,
MI) |
Assignee: |
General Motors Corporation
(Detroit, MI)
|
Family
ID: |
25358710 |
Appl.
No.: |
04/872,042 |
Filed: |
October 29, 1969 |
Current U.S.
Class: |
117/212; 422/253;
164/122.1; 164/122.2; 117/936; 117/928; 23/301 |
Current CPC
Class: |
C30B
29/06 (20130101); C30B 29/08 (20130101); C30B
15/06 (20130101); Y10T 117/1048 (20150115) |
Current International
Class: |
C30B
15/06 (20060101); B01j 017/00 () |
Field of
Search: |
;23/31SP,273SP
;148/1.6 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
551,638 |
|
Jan 1958 |
|
CA |
|
555,773 |
|
Feb 1958 |
|
CA |
|
939,102 |
|
Oct 1963 |
|
GB |
|
1,011,973 |
|
Dec 1965 |
|
GB |
|
1,482,659 |
|
Apr 1967 |
|
FR |
|
848,382 |
|
Sep 1960 |
|
GB |
|
Primary Examiner: Yudkoff; Norman
Assistant Examiner: Emery; S. J.
Claims
I claim:
1. An apparatus for horizontally growing crystalline bodies which
comprises means for containing a liquid melt of a solvent metal and
a solute, means for maintaining said melt at a selected
temperature, means for holding a crystalline seed in contact with
said melt to form a seed-melt interface, means for withdrawing heat
from said melt through said seed to precipitate solute onto said
seed at said interface, solute source means for substantially
continuously introducing solute into said melt adjacent said
interface to maintain the solute concentration in said melt
substantially constant during solute precipitation onto said seed,
means for horizontally pulling said seed away from said melt at a
rate commensurate with the rate of progressive melt solidification
onto said seed means for maintaining the surface of the melt at a
substantially constant level during crystal growth, said
solute-introducing means being an immovably supported,
substantially closed container having a surface portion within the
melt under the seed-melt contact interface, said surface portion
being substantially directly below and within about one-eighth inch
below the seed-melt interface, and said surface portion having at
least one opening therein through which solute diffuses to the
seed-melt surface.
2. The apparatus for growing crystalline bodies as defined in claim
1 wherein means is provided for maintaining the surface of the melt
at a substantially constant level during crystal growth, and the
solute introducing means is an immovably supported, substantially
closed container within the melt having a surface portion under the
seed-melt contact interface, the surface portion is generally
parallel to and within about one-eighth inch below the seed-melt
interface, and the surface portion has a porous opening therein
through which solute diffuses to the seed-melt interface.
3. An apparatus for horizontally grooving a crystalline ribbonlike
body which comprises means for containing a liquid melt of a
solvent metal and a solute, means for maintaining said melt at a
selected temperature, means for maintaining said melt at a
substantially constant level, means for horizontally holding a
crystalline seed with one end in contact with said melt, means for
removing the heat of fusion from said one end of said seed to
produce progressive precipitation of said solute on said one end,
means for suppressing the net loss of the heat of fusion from the
balance of said seed contacting said melt to regulate progressive
precipitation of said solute thereon, a substantially closed solute
container means disposed within the melt container and having a
surface portion generally parallel to and within about one-eighth
inch below said melt level, a porous opening in said surface
portion through which solute passes to substantially continuously
introduce solute into said melt under said seed-melt contact
region, and means for horizontally pulling said seed away from said
melt at a rate commensurate with the rate of progressive solute
precipitation on said one end thereof to thereby produce a flat
crystalline ribbon of predetermined thickness.
4. The apparatus for horizontally growing a crystalline ribbonlike
body as defined in claim 3 wherein the surface portion of the
solute container is generally flat and includes a thin wall and the
porous opening in said flat surface portion is at least one slot
lying transverse to the direction of crystal pull.
5. The apparatus for horizontally growing a crystalline ribbonlike
body as defined in claim 3 wherein the surface portion of the
solute container is generally flat and includes a thin porous sheet
through which the solute diffuses into the melt.
6. The apparatus for horizontally growing a crystalline ribbonlike
body as defined in claim 3 wherein the surface portion of the
solute container under the seed-melt contact interface is grooved
in the direction of crystal pull to produce a ribbon of
predetermined cross section.
Description
CROSS REFERENCES TO RELATED APPLICATIONS
U.S. Ser. No. 795,561 Bleil, filed Jan. 31, 1969.
BACKGROUND OF THE INVENTION
Crystals have been grown in the past from liquid melts of the
crystalline materials. Crystals have also been grown from
supersaturated aqueous solutions of the crystalline material. U.S.
Pat. No. 3,031,275 Shockley describes a technique for growing
crystals from a melt floating on the surface of a liquid with which
the melt is immiscible. I have found a method and apparatus by
which metal and semimetal elemental and alloy crystals can be
produced using many of the desirable features of these prior
techniques, without also incurring the ancillary disadvantages of
each.
Moreover, this invention can be used to produce continuous thin
ribbon crystals. In my earlier U.S. Pat. application Ser. No.
795,561, I describe a novel technique for horizontal crystal
growing which can be used to provide elemental thin crystalline
ribbons of high purity. By modifying that technique in accordance
with this invention, a variety of advantages can result. Ribbon
growth temperature can be significantly reduced. Compound and mixed
crystal, i.e. alloy, ribbons of constant composition are readily
formed. The length of the ribbon produced is not inherently limited
by the starting volume of the melt.
SUMMARY OF THE INVENTION
It is, therefore, a principle object of this invention to provide
an improved method and apparatus for growing crystals, particularly
alloy crystals, from a saturated melt. A further object of the
invention is to provide an apparatus and method for producing thin
ribbons of alloy crystals. These and other objects of the invention
are attained by heating a solvent metal to a predetermined
temperature at which it is molten, and saturating the solvent metal
with a solute that will produce the crystal desired. A source of
additional solute is located within the melt beneath the crystal
growth interface. A close spacing is maintained between the source
and the growth interface as growth proceeds. A crystalline seed is
placed in contact with the melt above the source and heat withdrawn
through the seed to precipitate the solute onto the seed.
Concurrently, the crystalline seed is moved away from the melt at a
rate commensurate with the rate of the solute precipitation.
Simultaneously, additional solute is dissolved into the melt from
the source beneath the growth interface to maintain melt
composition substantially constant in the growth area.
BRIEF DESCRIPTION OF THE DRAWING
Other objects, features and advantages of the invention will become
more apparent from the following description of preferred examples
thereof and from the drawing, in which:
FIG. 1 shows an elevational view in partial section of a horizontal
crystal-growing apparatus that includes a solute source beneath the
growth interface;
FIG. 2 shows an enlarged isometric view of the solute source shown
in FIG. 1;
FIGS. 3, 3a and 3b show fragmentary isometric views of alternative
solute sources for the apparatus shown in FIG. 1;
FIG. 4 shows a horizontal crystal-growing apparatus with a
recirculating solute source;
FIG. 5 shows an enlarged plan view of the solute source shown in
FIG. 4; and
FIG. 6 shows a sectional view along the line 6--6 of FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As already indicated, this invention involves alloy crystals by
precipitation of a solute onto a crystalline seed from a melt
saturated with that solute. A source of solute is provided in the
melt within a predetermined distance from the growth interface,
with this spacing being maintained substantially constant during
crystal growth. Moreover, this invention also contemplates
providing a surface geometry on the solute source that will aid in
controlling the geometry of the growth interface. While this latter
concept may not be of appreciable significance for vertical crystal
growing, it is of special importance when horizontally growing
crystals in accordance with this invention. Shaping the source
surface can permit one to produce crystalline ribbons of different
surface geometries, as formed. It is in this latter connection that
this invention has particular benefits in that it can provide thin,
wide monocrystals flat on one side and of predetermined shape on
the other.
It should also be noted that this technique can be used to produce
monocrystals or polycrystalline material, as one desires. It can be
used to produce substantially elemental crystals, mixed crystals
and crystals of compounds. However, the composition of the crystals
produced will always be a function of the solid solubility of the
melt solvent in the crystal being formed. Hence, for ultimate
purity in elemental crystals this technique would not be preferred.
However, it provides a precise technique for producing elemental
crystals containing selected amounts of other substances, for
producing crystals of solute-solvent compounds of selected
composition, and the like. Since for all practical purposes this
technique produces crystals containing two or more elements I
prefer to refer to it as an alloy crystal-growing technique. The
crystal, of course, may not be a true alloy but a mixture. However,
for convenience of expression I shall refer to it as an alloy.
The actual composition of the crystal will thus depend on the
solute-solvent combination used, the temperature of the melt, etc.
Consequently, the invention has a wide applicability from the
production of elemental and compound semiconductor monocrystals to
the crystals of a variety of metals.
Further, this invention can be used for vertical crystal growing,
as will become apparent. However, the maximum benefits of the
invention are more fully realized when it is used in combination
with the horizontal crystal-growing apparatus I have described and
claimed in my earlier U.S. Pat. application Ser. No. 795,561.
Reference is now made to FIG. 1 to illustrate that preferred use.
Except for the additional provision of the solute source, the
apparatus shown in FIG. 1 is essentially the same and operated
essentially the same as described in my earlier-filed patent
application Ser. No. 795,561, which is intended to be incorporated
herein by reference. For this reason the similar aspects of
apparatus and method shall only be briefly described here.
A rectangular crucible 10 rests on a crucible support 12 within a
conventional crystal-growing enclosure (not shown) which provides a
suitable environment for crystal growth. The crucible is surrounded
by a radio frequency heater 14. The crucible is slightly overfilled
with the desired melt, so that the free surface of the melt extends
slightly above the lip 16 of crucible 10.
One end of the lower surface of a crystalline seed 18 contacts the
surface of the melt while the other end is secured to a seed holder
20 for pulling the seed horizontally away from the melt.
A melt of 95 percent indium-5 percent germanium can be used to grow
germanium crystals containing small amounts of indium at a growth
temperature of approximately 400.degree. C. A melt of 75 percent
silver-25 percent germanium can be used to produce germanium
crystals containing small amounts of silver at a growth temperature
of 700.degree. C. In such instance the seed 18 is of germanium in
which the major faces of the seed are parallel and in the (111)
plane. When horizontally pulled, the direction of pull is
<211>.
The upper surface of the end of the seed touching the melt is
contacted by a heat sink 26, which is maintained at an appropriate
temperature by means of an encircling radio frequency type heater
28. Cooling coils 30 surround the heat sink support.
A special heater 22 is recessed under the melt surface beneath the
seed adjacent crucible lip 16 over which the seed is pulled. Heater
22 lies parallel the crucible lip, and transverse to the ribbon
being formed, to supply ribbon heat lost by radiation. A
spring-loaded roller 24 in the crucible lip 16 supports the ribbon
as it is pulled over the lip. Hence, ribbon growth is restricted to
the end of the ribbon under the heat sink.
Heat sink 26 has an appendage 32 thereon for controlling
temperature and melt surface height at the end of the growing seed.
Appendage 32 has a heater therein for more precise temperature
adjustments adjacent the growth interface. A graphite bulb 34,
having a heater therein for more precise temperature adjustments
adjacent the growth interface. A graphite bulb 34, having a heater
therein is lowered into the melt at a rate commensurate with the
crystalline growth to maintain the free melt surface at a constant
height above the lip 16 of the crucible.
The solute source is a graphite or ceramic tube 36, the
construction of which is more clearly shown in FIG. 2. The source
tube 36 lies transverse to the ribbon being grown. It has a flat
surface portion 38 with a plurality of slots 39 which are
positioned beneath the growing end of the seed beneath and parallel
to the growth interface. The slots provide a permeable opening in
the source under the ribbon growth region. For best results, the
flat surface portion 38 should be maintained within about
one-eighth inch of the growth interface. Close spacing of surface
38 to the growth interface is desirable to increase the rate of
crystal growth and regulate growth interface geometry. Transport of
the solute from the source to the growth interface is diffusion
controlled. Hence, the closer the spacing of the source to the
growth interface, the faster growth can be achieved. Analogously,
the closer the source surface geometry parallel the natural growth
geometry, the easier the system is to control. The natural ribbon
growth interface in the system shown is not perfectly horizontal.
Hence, the source surface 38 is canted somewhat to be substantially
parallel to it. However, in some instances one may prefer a
different relative orientation.
There is also a concurrent indiffusion of the melt solvent into the
source through the slots 39 in the tube 36, while the source is
diffusing out. Hence, it is desirable that the volume of solute in
tube 36 be appreciable to avoid any significant solute
concentration changes during crystal growth that would adversely
affect the rate of growth or the length of the ribbon to be
produced.
Of course, for most systems the source should at least be at the
melt temperature and preferably slightly higher, to prevent the
melt and source from freezing. For this reason a source heater 40
is included in tube 36. Tube 42 extending into the source tube 36
can be used to introduce additional solute into tube 36 should it
be desired. As can be seen, tube 36 bends at a right angle to
extend up above the surface of the melt at a point removed from the
growth interface. This not only increases source volume but
provides a ready access to the tube interior.
The source opening through which the solute diffuses can be formed
in a plurality of ways, only some of which are shown. The openings
should be large enough to permit the solute to diffuse out but not
so large as to permit droplets of solute to pass through. The type,
geometry and dimensions of the source openings can thus be varied
widely, and to some extent be a function of the solute-solvent
system involved.
FIG. 2 shows a series of parallel, longitudinally oriented slots 39
in an integral flat portion of source tube 36, providing the source
openings. FIGS. 3, 3a and 3b show alternative forms of source
apertures which can be used. FIG. 3 shows a source tube 44 having a
separate flat plate 46 secured over a longitudinal opening therein.
The plate 46 has a series of parallel, longitudinally oriented
slots therein, analogous to that shown in FIG. 2.
In FIG. 3a, source tube 50 also has a flat plate 52 secured over to
a longitudinal opening therein, with a plurality of slots 54
running the length of the plate providing means for the solute to
diffuse out of the tube. However, in addition, transverse grooves
58 and 60 are provided in plate 52 to alter the rate of diffusion
of the solute out of tube 50 in those areas where the grooves
intersect. This difference in rate of diffusion will affect solute
concentration in the adjacent areas of crystal growth, which in
turn will affect the rate of growth in the related regions of the
crystal being formed. Hence, by contouring plate 52 one can contour
the lower surface of the ribbon which is being grown.
FIG. 3b shows that the source tube containing the source need not
be cylindrical but can be rectangular in cross section, as source
tube 62 shows. It also shows that a porous barrier need not be
slots but can be of any porous body, such as a sintered metal
structure 64. It might also be a screen. It should also be noted
that the porous barrier need not be flat. In fact, in some
instances it may be preferred that it be curved both radially
and/or axially.
FIG. 4 shows a ribbon growth apparatus analogous to that shown in
FIG. 1. However, the construction of the source in this embodiment
of the invention provides means for continuously circulating a
different means and adding more solute to the source. FIGS. 5 and 6
show the source in greater detail. The source is a substantially
annular closed container 68 having a flat upper surface. One
portion 72 of this flat surface has a plurality of parallel
longitudinally oriented slots therein, similar to those already
described providing a porous partition between the solvent and the
solute. It is registered beneath the growth interface in the manner
already described. A heater 74 extends down through an opening 76
into the annulus and extends around and under the porous portion
72, lying beneath the growth interface. Opening 76 is also large
enough to accommodate impeller 78 which continuously recirculates
the solute in annulus 68 to maintain its temperature and
concentration uniform throughout. The annulus is positioned within
the melt in support member 80. As the solute is consumed during
ribbon growth, or as solvent concentration in the annulus rises,
additional solute can be added by means of feeder tube 82, when
spring-biased gate 84 is opened.
The preferred temperature and rate at which crystals should be
grown will obviously be a function of the solvent system which is
employed, as well as the quality of crystal desired. Solvents for
use in growing germanium crystals include indium, gold, silver and
copper. Bismuth crystals can be grown with silver as a solvent.
Silicon crystals can be grown in gold, silver and aluminum
solvents. Antimony and tellurium crystals can be grown with gold as
a solvent. Bismuth can be used as a solvent to grow crystals of
copper, indium and mercury. Tin crystals can be grown with iron as
a solvent. Such crystals will contain varying minor amounts of the
solvent metal.
In view of the foregoing, it can be appreciated that this invention
is especially useful for horizontally pulling thin, flat
crystalline ribbons. However, it should also be acknowledged that
it can be used in the more conventional vertical Czochralski
crystal-growing technique. Crystal boules of any size suitable
cross section can be conveniently vertically pulled on a
substantially continuous basis, In such instance, the
crystal-pulling means, itself, will function as a heat sink to
conductively remove heat from the crystal. The cooler parts of the
crystal-growing apparatus will also absorb heat radiated from the
freshly grown crystal. Hence, no special heat sink need be
provided.
It is to be understood that although this invention has been
described in connection with certain specific examples thereof no
limitation is intended thereby except as defined by the appended
claims.
* * * * *