U.S. patent number 3,796,552 [Application Number 05/215,229] was granted by the patent office on 1974-03-12 for crucible.
This patent grant is currently assigned to Hughes Aircraft Company. Invention is credited to Donald M. Cripe, Morton Robinson.
United States Patent |
3,796,552 |
Robinson , et al. |
March 12, 1974 |
CRUCIBLE
Abstract
The crucible is formed of compacted graphite or vitreous carbon
and has an interior tapered toward its nucleation point. Single and
multiport types are described for growing one or more crystals
similtaneously. The crucible is useful for growing laser quality
crystals of alkaline earth and rare earth fluorides, including
mixed rare earth fluorides and mixed rare earth-alkaline earth
fluorides which are free from oxides and oxyfluorides.
Inventors: |
Robinson; Morton (Granada
Hills, CA), Cripe; Donald M. (Santa Monica, CA) |
Assignee: |
Hughes Aircraft Company (Culver
City, CA)
|
Family
ID: |
26909841 |
Appl.
No.: |
05/215,229 |
Filed: |
January 3, 1972 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
627355 |
Mar 31, 1967 |
3649552 |
Mar 14, 1972 |
|
|
Current U.S.
Class: |
117/223; 422/547;
164/122.2; 432/263; 117/940; 117/900; 266/275; 423/489 |
Current CPC
Class: |
C30B
29/12 (20130101); C01F 17/271 (20200101); C30B
11/002 (20130101); C01F 17/13 (20200101); C01F
17/206 (20200101); C30B 11/00 (20130101); H01S
3/16 (20130101); C01F 17/265 (20200101); C01F
17/36 (20200101); Y10S 117/90 (20130101); Y10S
117/906 (20130101); Y10T 117/1092 (20150115) |
Current International
Class: |
C30B
11/00 (20060101); C01F 17/00 (20060101); H01S
3/16 (20060101); B01l 003/04 () |
Field of
Search: |
;23/277R,273R,31SP,273SP,292 ;148/15,16 ;164/60 ;432/263
;266/34V,39 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Fisher, "Modern Laboratory Appliances" Catalog No. 63 (1962), pp.
170 & 189..
|
Primary Examiner: Tayman, Jr.; James H.
Attorney, Agent or Firm: Haskell; James K. Sternfels; Lewis
B. MacAllister; W. H.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This is a division of application Ser. No. 627,355, filed March 31,
1967, now U.S. Pat. No. 3,649,552 patented March 14, 1972.
Claims
1. A crucible for growing crystals from starting materials
comprising an elongate tube for receiving the starting materials
and having:
internal bore means bounded at both ends by means defining
openings, said opening means at a first of said ends being larger
in dimension than the opening means at a second of said ends to
provide said bore means with a taper decreasing from said first end
to said second end; and
a closed tapered pointed end at and terminating said second end of
said
2. A crucible as in claim 1 further including an entry portion
provided with opening means of greater dimension than that of said
bore means at said first end and a connecting portion secured
between said entry portion and said tube at said first end, said
connecting portion having a tapered bore diminishing in dimension
from the entry portion bore to the first
3. A crucible as in claim 1 wherein said tube is constructed of
compacted
4. A multiport crucible for simultaneously processing several
cyrstals including a plurality of elongate tubes for each of the
several crystals, each said tube having internal bore means bounded
by first and second open portions, and a closed pointed end
terminating said second open portion, said bore means of each said
tube being of greater dimension at said first open portion than at
said second open portion to form a taper in said bore means, and
means securing said tubes together at said first open portions.
5. A crucible as in claim 4 further including an entry section
having a plurality of entry ports, each of said ports having a
dimension greater than that of each of said first open portions,
and passage means connected
6. A crucible as in claim 5 further including a plurality of fins
secured
7. A crucible as in claim 6 formed from compacted graphite.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a crucible for growing crystals.
It is specifically useful in the preparation of optically pure
crystals of alkaline earth and rare earth fluorides, including
mixed rare earth fluorides and mixed rare earth-alkaline earth
fluorides of laser quality free from oxides and oxyfluorides.
Laser devices require the use of crystals which are of ultra-high
optical purity since even minute impurities cause internal scatter
and opaqueness in the crystal, thereby preventing the desired light
amplification. In recent years, interest has centered on crystals
doped with rare earths since the rare earths possess qualities
which are well-suited for laser studies. However, optical-grade
fluoride single crystals, especially rare earth fluoride single
crystal hosts doped with rare earth ions, have been particularly
difficult to grow by prior art methods (see, for example, J.
Czochralski, Z. Physik Chem., Vol. 92, p. 219 (1918); D. C.
Stockbarger, Journal of the Optical Society of America, Vol. 39, p.
731 (1949); H. Guggenheim, Journal of Applied Physics, Vol. 34, No.
8, pp. 2482 - 2485, August, 1963).
PRIOR ART
Methods of growing crystals have been limited in that only one
crystal at a time could be grown. Because the growth of high
quality crystals is markedly dependent upon temperature and
uniformity of temperature within the crystal, the time for growing
a single crystal encompassed a period of time which can easily
extend from a few days to as much as a few weeks. Consequently, it
has not been previously possible to obtain a large quantity
production of crystals in the absence of a large number of furnaces
in which the crystals may be grown. It is obvious, therefore, that
the growth of a large number of crystals required a correspondingly
large investment in process equipment.
Furthermore, the crucibles used in prior processes to form such
crystals as laser crystals were formed for platinum or platinum
lined with carbon. When a platinum crucible is used, the formed
crystal adheres to the platinum which requires that the crucible be
torn away from the crystal so that the crystal may be obtained.
Thus, such a crucible becomes unusable for further growth. When
carbon is used as a liner for a platinum crucible and is exposed to
such corrosive gasses as hydrogen fluoride, a reaction occurs at
elevated temperatures to cause a diffusion of the carbon through
the platinum. The platinum becomes brittle although the fluoride
crystal is not contaminated; however, the lifetime of the platinum
with its carbon liner is shortened. Furthermore, many prior
processes utilized a closed crucible in which the crystal material
and ambient atmosphere are contained so that, if the ambient
atmosphere included hydrogen fluoride, noxious fumes would not
escape therefrom. However, when the crystal was formed, the
crucible had to be destroyed in order to remove the crystal.
SUMMARY OF THE INVENTION
The present invention overcomes these and other problems also by
providing a very simple process means wherein a multiplicity of
quality crystals may be formed at the same time.
In the growth of a crystal, a starting material may be loaded into
a crucible which is formed with an open end. The crucible with the
staring material therein is attached to a lowering rod in a crystal
growth furnace and the temperature of the furnace is slowly raised
in a desired atmosphere above the melting point of the material to
produce melt.
The crucible is so constructed as to aid contact of the atmosphere
with the melt, if needed. The crucible is then lowered at a rate
commensurate with the growth rate of the crystal. At the end of the
growth travel region, crystal annealing usually takes place. The
time required for satisfactory annealing depends on the crystal
material and the crucible material as well as the length and
diameter of the crystal. The crystal is slowly cooled to a
specified temperature, and the furnace is cooled to room
temperature over a suitable period of time.
Preferably, when used to grow the fluoride crystals, the crucibles
are made from graphite since neither a fluoride melt nor hydrogen
fluoride atmosphere affects it. Other advantages of graphite are
that the fluorides do not wet the graphite thus facilitating
removal of the crystal from the crucible and that the graphite is
of sufficient mechanical stability so that no fine graphite
materials are transferred as impurities to the crystal. The
crucibles are formed with one or more ports so that one or more
crystals may be grown singly or simultaneously. Each port is closed
at its bottom end and open at its upper end. The diameter of each
port is greatest at its open end and decreases toward its closed
end where it terminates at a point to facilitate nucleation of a
single crystal. The decreasing diameter, in conjunction with the
non-wetting characteristic of graphite, permits easy removal of the
crystal grown. The decreasing diameter also acts as a funnel to
increase contact of hydrogen fluoride with the melt. It is to be
understood, however, that the graphite crucibles will facilitate
removal of crystals regardless of the particular method of halide
crystal growth employed.
Any suitable furnace may be used for crystal growth.
Other aims and objects, as well as a more complete understanding of
the present invention will appear from the following explanation of
exemplary embodiments and the accompanying drawings thereof, in
which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view, partly in section, of a single
port crucible for growing a single crystal;
FIG. 2 is a side elevational view of a multiport crucible for
growing simultaneously several crystals;
FIG. 3 is a top view, taken along lines 3--3 of FIG. 2, of the
multiport crucible;
FIG. 4 is a sectional view, taken along lines 4--4 of FIG. 2, of
the multiport crucible;
FIG. 5 is a sectional view, taken along lines 5--5 of FIG. 2, of
the multiport crystal;
FIG. 6 is a bottom view, taken along lines 6--6 of FIG. 2, of the
multiport crucible;
FIG. 7 is a side elevational view of a second multiport crucible
for growing several crystals simultaneously; and
FIG. 8 is a view, taken along lines 8--8 of FIG. 7, of the second
embodiment of the multiport crucible.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
One use of the present invention is more fully described in the
above-noted U.S. Pat. No. 3,649,552.
The crucibles are formed entirely for vitreous carbon or a
compacted graphite since neither the corrosive nature of a fluoride
melt nor a hydrogen fluoride atmosphere affects the graphite. In
addition, the fluorides do not wet the graphite, thus making the
removal of the product quite easy. Furthermore, carbon has a
melting point which is at least twice that of any of the crystals
made by the inventive method and is insoluble therein. The graphite
crucibles additionally have good thermal characteristics such that
the heat of the furnace may be applied uniformly throughout the
crystals during their growth. The graphite crucibles are relatively
inexpensive, are easily machinable, and tend to resist shock. It is
in part for these reasons that it is possible to form multiport
crucibles so that several crystals may be grown simultaneously.
A single port crucible 110 is depicted in FIG. 1 and comprises a
tubular portion 112, an entry portion 114, and an intermediate
portion 116. Tubular portion 112 terminates in a point 118 for
closure thereof. The crucible is provided with a bore 120 which
varies according to the particular portion to form inner walls 122,
124 and 126, respectively, of tubular portion 112, entry portion
114 and intermediate portion 116. Inner wall 112 of portion 112 is
provided with a diameter at its upper end 128 which is greater than
the diameter at its lower end 130. Thus, inner wall 122 tapers from
its upper end to its lower end. Inner wall 132 of point 118
converges to a point from lower end 130 of portion 122 to serve as
a nucleation point by which growth of a single crystal may be
accomplished. Inner wall 124 of portion 114 is cylindrical and is
provided with a diameter which is relatively larger than the
diameter of walls 126 and 122. Inner wall 126 of portion 116
converges from inner wall 124 to the upper end 128 of inner wall
122 thus providing a gentle taper of bore 120.
Referring now to FIGS. 1-6, a multiport crucible 132 comprises a
solid upper section 134, having an entry portion 136 and an
intermediate portion 138, and a lower section 140 having tubular
portions 142 and fins 144. Entry portion 136 is provided with an
outer diameter which is greater than that of lower section 140 and
intermediate portion 138 has an outer diameter which tapers from
that of portion 136 to that of section 140. A tapped and internally
threaded connecting means 146 is centrally disposed within entry
portion 136 and crucible 132 and forms an opening in upper face 148
of portion 136. An externally threaded rod is adapted to threadedly
engage crucible 132 within connecting means 146 to enable the
positioning and movement of the multiport crucible within a crystal
growing furnace.
As depicted in FIGS. 2-6, crucible 132 is adapted to permit
simultaneous growth of six crystals in six individual components
150 of crucible 132. The internal construction of each component
150 is similar to that as illustrated with respect to FIG. 1 in
such a manner that each tubular portion 142 is provided with an
inner wall 152 which tapers from its upper end toward its lower
end, entry portion 136 is provided with an inner cylindrical wall
154 and intermediate portion 138 is provided with a tapered inner
wall 156 which joins inner wall 154 with the upper end of inner
wall 152. The lower end of inner wall 152 converges to a nucleation
point 158 within a point 160 of tubular portion 142.
Fins 144 extend downwardly from intermediate portion 138 and are
formed with curved suraces 162, as best seen in FIGS. 5 and 6,
which are spaced from but concentric with tubular portion 142. Fins
144 are used to add support to crucible 132, to protect points 160
of tubular portions 142, and to prevent dissipation of heat from
the tubular portions so that the growth and the stability of the
crystals will be enhanced. A circular output 164, concentric with
the axis of crucible 132, is placed interior to tubular portions
142 and fins 144 to permit even distribution of heat to the
crystals during the time of their formation.
A third embodiment (see FIGS. 7 and 8) comprises a multiport
crucible 170 including four tubular components 172 having pointed
extremities 174 at one end thereof and entry portions 176 at the
other extremity thereof. Components 172 are joined at their upper
ends by a web 178 (see FIG. 8) and a threaded nipple 180 extends
from web 178 for engagement with a rod. The inner walls 182 of each
of the tubular components 172 are similar to inner wall 122 of
tubular portion 112, as depicted in FIG. 1.
In all cases, those inner walls which are in contact with the
crystal are tapered in order to facilitate removal of the crystal
after having been grown without necessitating the destruction of
the crucible.
Although the invention has been described with reference to
particular embodiments thereof, it should be realized that various
changes and modifications may be made therein without departing
from the spirit and scope of the invention.
* * * * *