Single-crystal – oriented-crystal – and epitaxy growth processes; – Processes of growth from liquid or supercritical state – Havin growth from molten state
Reexamination Certificate
2001-01-30
2002-07-23
Kunemund, Robert (Department: 1765)
Single-crystal, oriented-crystal, and epitaxy growth processes;
Processes of growth from liquid or supercritical state
Havin growth from molten state
C117S083000, C117S084000, C117S220000, C117S221000, C117S222000, C117S223000, C117S940000, C117S900000
Reexamination Certificate
active
06423136
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to a crucible for growing large macrocrystals (or ingots) from a melt in a highly modified Stockbarger type furnace, or a comparable one in which slow growth of a solidifying macrocrystal from the melt under the influence of the earth's gravity, results in the solidified macrocrystal being supported within the walls of the crucible. It is accepted practice to refer to melt-grown isometric blanks as being “single” when the finished crystal does not exhibit flaws attributable to multiple components disregarding mosaics spread which is never less than 0.25° in the flattest cleavage and can generally be seen in the texture of thermal etch. In fact a mosaic spread of 3° is valued in pulled crystals for not showing the following flaws attributable to multiple components though their displacement may be less than 1°. However the displacement may be any angle up to 90° and still be optically homogeneous when not decorated by inclusions.
Multiple components are said to be present when they are visible as a fringe pattern, or strain pattern in an optically polished crystal. Multiplicities will fracture non-cubic crystals while mosaics will not. Mosaic spread is important for X-ray plates and gun sights. Mosaics which do not have unacceptable flaws are acceptable in a single crystal.
An ideal macrocrystal is a single crystal, but typically a macrocrystal grown is only optically monocrystalline, being formed of several crystals demarcated by boundaries within the macrocrystal. Grain boundaries within a large macrocrystal (an ingot) which are discontinuities are undesirable.
More specifically the novel crucible is useful to grow crystals of halides of an element of Group 1a and Group 2a of the Periodic Table, particularly the alkali metal fluorides and alkaline earth metal fluorides, lead fluoride and crystals of the foregoing salts which are doped with desirable metal ion dopands. High quality macrocrystals of fluorides of lithium and sodium, as well as of magnesium, calcium, barium and strontium have been produced commercially since soon after 1939 when Donald Stockbarger disclosed a method for their manufacture in U.S. Pat. No. 2,149,076 and we taught methods for purifying melts in U.S. Pat. Nos. 2,498,186 and 2,550,173. However, producing high quality macrocrystals depends upon many factors, including having the skills required to duplicate successful runs. Success depends upon anticipating the need for minute adjustments in “power hours” (rate at which power is delivered to heat the melt), among others, all of which adjustments must be made before a probe inserted in the melt shows any indication of a change in the rate of growth.
To date, a graphite crucible may be used for growing a Stockbarger macro-crystal, provided the graphite is not so porous as to allow the melt to leak through it. A crucible may have an inclined or flat bottom and either might be provided with a well for a “seed crystal” holder. If a seed is used, it is incorporated into the bottom of the macrocrystal formed.
U.S. Pat. No. 5,911,824 teaches that a particular graphite crucible could not contain a melt of thallium iodide doped sodium iodide, NaI(TI) (see col 4, lines 26-34). A NaI(Tl) crystal was successfully grown in a graphite crucible the inside surface of which is coated with graphitic pyrolitic carbon, and the crystal did not adhere to the coated surface (see col 4, lines 36-47).
However, a second crystal grown in the same crucible, adhered strongly to the crucible and could not be removed in its entirety without a remelting procedure (see col 4, lines 60-66). If the crystal was grown in a platinum crucible, the crystal adheres to the platinum. The platinum crucible must be heated to melt the surfaces of the crystal in contact with the platinum (referred to as “remelting”) before the platinum crucible may be slid off the crystal.
It is a characteristic of macrocrystals of the aforementioned fluorides of melt-grown metal or metal-like elements, that they shrink when they solidify (referred to herein as “shrinking melts”), and the first crystal grown may be readily removed because the walls of a graphite or carbon crucible are not wetted by the melt.
To be readily removed, sufficient shrinkage must occur when, and after, the melt solidifies provided also that the bond between crystal and crucible is weaker than the force needed to fracture the crystal as it cools. Since the coefficient of linear expansion of graphite is about 7.85 microinches/(inch)(° C.) measured at about 40° C., that of the salt must be greater, preferably at least 5% greater, and more preferably 10% greater. The coefficient of fluorspar is about 19.5 microinches/(inch)(° C.) measured at about 40° C., so that even in a relatively small crucible having an inside diameter in the range from about 5 cm to about 25 cm, the circumferential surface of the solidified crystal pulls away from the inner walls of the crucible, and the crystal may be lifted out of the crucible with a vacuum cup without breaking the crystal or crucible, even when the crucible is cylindrical and its sides are vertical. This may be done provided the surface tension of the melt is high enough so as to fail to substantially wet the walls of the crucible; because the melt does not wet the surface of the graphite it does not to seep into its pores. Note that the linear coefficients of expansion at melt temperature will likely be substantially different from those given above.
The effect of such shrinkage on a crystal no larger than about 7.5 cm at its greatest diameter (referred to as a 7.5 cm diameter macrocrystal) is not particularly notable even if the shrinkage is not controlled, but for larger crystals that effect is; the larger the crystal, the more detrimental are the effects of such uncontrolled shrinkage.
Using a shrinking melt to grow a Stockbarger macrocrystal typically comprises slowly moving the melt at a controlled rate from a region hotter than its solidification temperature to a region cooler than its solidification temperature, controlling the relative temperatures of the regions, and maintaining a temperature gradient in a localized zone between the regions at the boundary of the melt. The temperature gradient in the zone is sufficient to allow melt to crystallize at the cooler boundary of the localized zone. An “elevator” type furnace may be used where the crucible is raised or lowered on an elevator; or a “movable temperature gradient” furnace may be used where the furnace is moved and the crucible is stationary. The gradient between melt near the top of a crystal and the sharply localized zone is in the range from about 100° C. to about 500° C. depending upon the particular halide.
It will be evident that the temperature of the edge portion of successive layers of the melt corresponds to the solidification temperature of the melt as these edge portions reach a substantially fixed location in the path of travel of the melt and solidification begins and progresses inwardly. Preferred crystals are obtained when the zone of solidification approximates a plane. It is desirable to control the rate of heat flow through the inner portion of the melt from the hotter to the cooler region. If the rate of heat flow through the inner portion of the melt is too slow, the zone of solidification tends to be concave. Properly controlling the rate of heat flow through the inner portion of the melt allows the zone of solidification to approximate a plane.
To date, the art has addressed the problem of a macrocrystal adhering to the inner surface of the crucible by either providing a very smooth microporous graphite surface, or by coating the surface of the graphite as in the '824 patent, or by lining a mechanically stable temperature resistant material such as alundum or graphite with a thin sheet of platinum as in U.S. Pat. No. 5,997,640. In either case, the better is the separation upon solidification, the more readily the macrocrystal falls to the bottom of the crucible. In a crucible in which the porosity is s
Kunemund Robert
Lobo Alfred D.
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