WO2006068062A1 - フッ化金属単結晶体の引上げ装置および該装置を用いたフッ化金属単結晶体の製造方法 - Google Patents
フッ化金属単結晶体の引上げ装置および該装置を用いたフッ化金属単結晶体の製造方法 Download PDFInfo
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- WO2006068062A1 WO2006068062A1 PCT/JP2005/023182 JP2005023182W WO2006068062A1 WO 2006068062 A1 WO2006068062 A1 WO 2006068062A1 JP 2005023182 W JP2005023182 W JP 2005023182W WO 2006068062 A1 WO2006068062 A1 WO 2006068062A1
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- crucible
- single crystal
- metal fluoride
- pulling
- melt
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Classifications
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/02—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/10—Crucibles or containers for supporting the melt
- C30B15/12—Double crucible methods
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
Definitions
- the present invention relates to a pulling apparatus used for producing a metal fluoride single crystal used for an optical material or the like, and a method for producing a metal fluoride single crystal using the apparatus.
- Single crystals of metal fluorides such as calcium fluoride and barium fluoride have high transmittance over a wide wavelength range, low dispersion and excellent chemical stability.
- Demand is expanding as optical materials such as various devices using ultraviolet wavelength lasers, lenses for cameras, CVD devices, and window materials.
- calcium fluoride single crystals are being developed as next-generation short-wavelength light sources in the optical lithography technology.
- Expectation is expected as a projection system lens.
- the crucible lowering method is a method for growing a single crystal in a crucible by cooling the molten liquid of the single crystal production raw material in the crucible while gradually lowering the entire crucible.
- the single crystal pulling method is a method in which a seed crystal consisting of a target single crystal is brought into contact with the melt surface of the single crystal production raw material in the crucible, and then the seed crystal is gradually pulled from the heating region of the crucible. In this method, a single crystal is grown under the seed crystal by cooling.
- the scatterers are more likely to be formed in the process of crystallization of the liquid above the liquid below. There is a situation, and when a single crystal is manufactured by the single crystal pulling method, it tends to be formed more intensely than the crucible lowering method.
- the scatterers are more prominently generated when a single crystal having a large diameter than that having a small diameter is produced.
- the present inventors generally set the depth of the melt of the raw material metal fluoride in the single crystal pulling method, in which the formation of scatterers should become more intense. It has been found that the formation of the scatterer can be greatly suppressed if the crystal is pulled to a depth of 0.65 times or less the same diameter of the same month as the diameter of the crystal, and a patent application was filed earlier (Japanese Patent Application No. 2004-309430). According to this method, natural convection of the melt in the crucible that causes scatterer formation can be greatly weakened. As a result, a large-diameter metal azgrung single crystal having a small amount of the scatterer is present. The body can be manufactured efficiently.
- the growth (growth) of a single crystal in a state where the above melt is shallow can be achieved only in a state where the pulling is considerably advanced, and the obtained azgroun single crystal is located in an upper part such as a shoulder part! A considerable amount of scatterers were formed.
- the single crystal pulling apparatus is composed of an outer crucible and an inner crucible for the production of a semiconductor single crystal such as silicon doped with impurities in order to increase the uniformity of impurity concentration. It is known to use a crucible having a double structure (Patent Document 2 and Patent Document 3). However, the pulling apparatus provided with the double structure crucible described in these documents is used for single crystal growth of semiconductor materials and does not perform impurity dopants etc. In fact, the example used is not known at all.
- Patent Document 1 Pamphlet of International Publication No. 02Z077676
- Patent Document 2 Japanese Patent Application No. 61-261288
- Patent Document 3 Japanese Patent Application No. 62-87489
- the depth of the melt of the raw material metal fluoride is not affected by the diameter of the single crystal to be manufactured, the length of the straight body portion, etc. Pulling can be performed in a shallow state within a certain range, and the effect of suppressing the formation of scatterers inside the single crystal by such pulling in a shallow state of the melt can be maximized. It has been a big challenge to develop a pulling device for a metal fluoride single crystal that can be used. [0011] Further, in the production of the metal fluoride single crystal by the pulling method, when the raw material metal fluoride is used as a melt, solid impurities are often generated and float in the melt.
- the air bubbles can be observed with the naked eye under the brightness of a fluorescent lamp without using condensing illumination.
- the size of the air bubbles ranges from 100 m to several centimeters.
- the above-mentioned crystal breakage is a force that can be detected by monitoring weight changes during crystal pulling, etc. If bubbles are included, it is difficult to find during crystal pulling, and there is no component force until it is removed. This is a very big problem.
- the melt may solidify in a stalagmite shape at the crucible bottom or crucible wall.
- a sarcophagus is a big one In such a case, the single crystal that is being grown is hit against the single crystal. For this reason, it is necessary to stop the pulling of the crystal and dissolve the sarcophagus, which is also a big problem. Furthermore, like the above-mentioned crystal breakage, it is not always connected cleanly.
- Such crystal breakage, bubble inclusion, and sarcophagus are particularly noticeable when the crystal pulling is performed under reduced pressure.
- the present invention provides an apparatus for pulling a metal fluoride single crystal capable of stably growing a single crystal in a shallow state where the melt in which the formation of scatterers is highly suppressed until the end of the pulling start force is shallow. And to provide a method for producing a metal fluoride single crystal!
- the present invention provides a physic metal that suppresses the inclusion of solid impurities in the azgrung single crystal body and can also suppress partial polycrystalline silicon generated due to the solid impurities.
- An object of the present invention is to provide a single crystal pulling apparatus and a metal fluoride single crystal manufacturing method.
- the present invention provides a metal fluoride single crystal capable of stably and efficiently producing a large-sized single crystal of metal fluoride, in which the occurrence of crystal breakage, bubble inclusion, or sarcophagus during crystal growth is suppressed.
- An object of the present invention is to provide a body pulling apparatus and a method for producing a metal fluoride single crystal.
- Another object of the present invention is to provide a metal fluoride single crystal pulling apparatus and a metal fluoride single crystal production method capable of producing a single crystal having a high vacuum ultraviolet light transmittance. .
- the present inventors have conducted intensive studies in view of the above problems. As a result, it was found that the above-mentioned problems can be solved by making the crucible provided in the pulling device into a specific double crucible structure, and the present invention was completed.
- a pulling apparatus for a metal fluoride single crystal comprises a double structure crucible comprising an outer crucible and an inner crucible housed in the outer crucible in a chamber forming a single crystal growth furnace.
- the inner and outer crucibles of the outer crucible and the inner crucible in the dual structure crucible are partially in communication, and the double structure crucible can continuously change the storage depth of the inner crucible with respect to the outer crucible.
- a single crystal pulling rod which is used with a seed crystal attached to the tip, is provided directly above the inner space of the inner crucible in the chamber.
- the outer crucible can be moved up and down continuously in the chamber, and thereby the accommodation depth of the inner crucible with respect to the outer crucible can be continuously changed.
- the method for producing a metal fluoride single crystal of the present invention uses the above-described pulling apparatus, and contains a raw material metal fluoride melt in each inner space of the outer crucible and the inner crucible in the double structure crucible,
- the single crystal pulling rod After lowering the single crystal pulling rod until the seed crystal attached to the tip of the single crystal pulling rod comes into contact with the surface of the melt contained in the inner crucible, the single crystal pulling rod is gradually moved down. Pull up to grow a metal fluoride single crystal,
- the inner crucible storage depth is increased with respect to the outer crucible in accordance with the decrease in the melt contained in the inner crucible accompanying the growth of the metal fluoride single crystal. breath,
- the melt contained in the outer crucible is supplied into the inner crucible so that the amount of the melt in the inner crucible is maintained within a certain range.
- the amount of the melt in the inner crucible is not less than 3 cm in depth and the straight body diameter of the single crystal is 0. It is preferable to increase the storage depth of the inner crucible with respect to the outer crucible so that it is maintained within a range of 65 times or less.
- the single crystal to be pulled up is large, in particular, the diameter of the straight body is 150 mm or more, and the length of the straight body is 100 mm or less. Even the ultra-large one above can grow a single crystal while keeping the melt depth of the raw material metal fluoride constant.
- the pulling apparatus for a metal fluoride single crystal of the present invention is the above pulling apparatus, wherein a gap formed between the outer surface of the outer crucible and the inner surface of the inner crucible is formed by the outer surface of the outer crucible and the inner surface of the inner crucible. An annular opening that opens the space upward is formed.
- the inner crucible has the bottom end or the bottom wall of the side wall when the bottom wall is horizontal, and the inner diameter of the bottom wall of the inner crucible when the bottom wall has a downwardly convex shape. It is preferable that a communication hole for communicating the inner space of the outer crucible and the inner crucible is formed below the position where the inner diameter is 1Z4 or less! /.
- the distance between the inner wall surface of the outer crucible and the outer wall surface of the inner crucible in the opening is preferably 1Z10 to 1Z3 of the inner diameter of the outer crucible.
- the method for producing a metal fluoride single crystal of the present invention uses the above pulling apparatus,
- the molten metal fluoride material is stored in the inner space of the outer crucible and the inner crucible in the double structure crucible, and then the inner crucible is stored in the inner crucible after the accommodation depth of the inner crucible is reduced to the outer crucible.
- the inner crucible is stored deeper in the outer crucible, and the molten liquid in the outer crucible is fed into the inner crucible.
- the inner crucible when the solid impurities are floating in the molten metal fluoride at the start of the pulling, the inner crucible is once stored in the inner crucible with respect to the outer crucible, and the inner crucible is The entire amount of the single crystal raw material melt contained in the outer crucible is allowed to flow out into the outer crucible, and then the inner crucible storage depth relative to the outer crucible is deepened again, so that the raw material metal fluoride molten liquid in the outer crucible is introduced into the inner crucible. By feeding into the crucible, the solid impurities can be pulled up while being removed to the outer crucible side.
- the obtained metal fluoride azgrung single crystal can suppress the inclusion of solid impurities therein and also prevent partial polycrystallization caused by the solid impurities. Can do.
- the pulling apparatus for a metal fluoride single crystal according to the present invention is the above-described pulling apparatus, wherein the opening or a position between the inner wall surface of the outer crucible and the outer wall surface of the inner crucible below the opening. And a shielding member that shields at least a part between the inner surface of the side wall of the outer crucible and the outer surface of the side wall of the inner crucible.
- the shielding member is fixed to one of the crucibles of the inner crucible or the outer crucible, and is not fixed to the other crucible.
- the shielding member is not fixed to either the inner crucible or the outer crucible.
- the method for producing a metal fluoride single crystal of the present invention uses the above-described pulling apparatus, and contains a raw material metal fluoride melt in each inner space of the outer crucible and the inner crucible in the double structure crucible,
- the single crystal pulling rod is gradually pulled up to obtain a metal fluoride single crystal body in a state where at least a part of the upper surface of the melt contained in the outer crucible is shielded from the external force by the shielding member. It is characterized by nurturing.
- the raw material metal fluoride and the scavenger are accommodated in the gap space between the inner surface of the outer crucible and the outer surface of the inner crucible in the dual structure crucible.
- the raw material metal fluoride and the scavenger are accommodated.
- the inner wall of the outer crucible and the outer wall of the inner crucible In a state where at least part of the surface is shielded from the outside by the shielding member, the raw material metal fluoride is heated and melted,
- the single crystal pulling rod is gradually pulled up to obtain a metal fluoride single crystal body in a state where at least a part of the upper surface of the melt contained in the outer crucible is shielded from the external force by the shielding member. It is preferable to cultivate it.
- the crucible since the crucible has a double structure, it is possible to stably grow a single crystal in a shallow state where the melt in which the formation of scatterers is highly suppressed until the end of the pulling start force. It can be carried out.
- the outer crucible and the inner crucible are partially communicated with each other, and by providing an opening between the side walls, the inclusion of solid impurities inside the azgrung single crystal is suppressed. It is also possible to suppress partial polycrystallization caused by the above.
- FIG. 1 is a cross-sectional view showing an embodiment of a pulling apparatus for a metal fluoride single crystal according to the present invention.
- FIG. 2 is an enlarged cross-sectional view showing a double structure crucible of a pulling apparatus for a metal fluoride single crystal according to another embodiment of the present invention.
- FIG. 3 is a cross-sectional view illustrating a preferred position where a communication hole is arranged in an inner crucible having a bottom-convex bottom wall.
- FIG. 4 is an enlarged cross-sectional view showing a double structure crucible and a shielding member of a pulling apparatus for a metal fluoride single crystal according to still another embodiment of the present invention.
- FIG. 5 is a schematic view showing a state in which metal fluoride and a solid strength banger are put into a gap space in a double structure crucible and heated in still another embodiment of the present invention.
- the metal fluoride is not particularly limited, but specific examples thereof include calcium fluoride, magnesium fluoride, strontium fluoride, barium fluoride, lithium fluoride, fluorine.
- alkaline earth metal elements such as calcium, magnesium, strontium, norlium, and those doped with rare earth elements such as lanthanum, cerium, gadmium, ytterbium, and the like can be mentioned.
- alkaline earth metal fluorides such as calcium fluoride, magnesium fluoride, strontium fluoride, and barium fluoride, and the industrial value of the target product is also high.
- the pulling device of the present invention is a pulling device for growing (pulling up) such a single crystal of metal fluoride.
- the structure of a known pulling apparatus used for the production of a conventional metal fluoride single crystal can be used without limitation except for the crucible portion described later.
- FIG. 1 is a cross-sectional view showing an embodiment of a pulling apparatus for a metal fluoride single crystal according to the present invention
- FIG. 2 is a double view of a pulling apparatus for a metal fluoride single crystal according to another embodiment of the present invention. It is an expanded sectional view showing a structure crucible.
- an outer crucible (3) having a function as described later is provided on a cradle (3) supported by a support shaft (2) rotatable in a chamber (1).
- inner crucible (5) A dual structure crucible (6) is placed, and a raw material metal fluoride melt (7) is accommodated in each crucible.
- a heater (8) is provided around the outer crucible (4), and a heat insulating material wall (9) is provided around the heater (8).
- the heat insulating material wall (9) is also provided below the double structure crucible (6).
- the height of the upper end of the heater (8) is preferably approximately the same as the height of the upper end of the outer crucible (4), and a height slightly higher than this. Further, the heat insulating wall (9) only needs to surround the lower end force of the outer crucible (4) up to the upper end. In view of the slow cooling of the pulled single crystal, the heat insulating wall (9) surrounds the space above the outer crucible (4) where the metal fluoride single crystal (10) is pulled up. I prefer to go.
- An isolation wall (18) may be provided between the heater (8) and the outer crucible (4) for the purpose of uniformizing radiant heat from the heater (8).
- the upper end of the separating wall (18) is made higher than the upper end of the heater (8), and the upper end and the heat insulating wall (9 ),
- a lid member (19) for closing the gap between the isolation wall (18) and the heat insulating material wall (9) is preferably placed horizontally and the gap is closed.
- a rotatable single crystal pulling rod (13) with a seed crystal (11) holder (12) attached at its tip is suspended.
- the seed crystal (11) is gradually pulled up after the lower end surface comes into contact with the raw material metal fluoride melt (7) in the inner crucible (5), and a single crystal (10) grows downward. .
- the lower end of the support shaft (2) extends through the bottom wall of the chamber (1) to the outside of the chamber, and although not shown, it is a mechanism for rotating the crucible after contacting the cooler. It is connected.
- the structure other than the crucible portion is, for example, a metal fluoride described in Japanese Patent Application Laid-Open No. 2004-182587. Metal fluoride with excellent temperature distribution in the single crystal pulling region This single crystal is preferable because it can be produced satisfactorily without cracks.
- the pulling device of the present invention has a double structure (6) in which the crucible includes the outer crucible (4) and the inner crucible (5), and the double structure crucible (6) In addition, the storage depth of the inner crucible (5) relative to the outer crucible (4) can be continuously changed.
- This double structure crucible (6) has an inner crucible (5) as shown in the enlarged cross-sectional view of FIG. 2 (the pulling device of FIG. 1 is different from the internal crucible of the double structure crucible).
- a gap space formed by the inner surface of the outer crucible (4) and the inner crucible (5) (hereinafter referred to as the inner space of the outer crucible) by a method such as providing at least one communication hole (14) in the wall portion of the outer crucible. In some cases) and a part of the inner crucible (5).
- the depth of the raw material metal fluoride melt (7) accommodated in the inner crucible (5) is determined by the straight body portion of the as-grown single crystal to be pulled up.
- the depth is preferably 0.65 times or less of the diameter.
- the pulling force is applied to the outer crucible (4) from the outer crucible (4) to the inner crucible (5) so that the above-mentioned depth is maintained for as many times as possible until the end, preferably during the entire period. Replenish the melt (7).
- the depth of the crucible of the pulling apparatus used for producing a conventional metal fluoride single crystal is usually about 3 to 5 times the diameter of the straight barrel of the azgrung single crystal. If a sufficient amount of the raw material metal fluoride melt (7) is contained, the depth of the melt will be about twice as large as the diameter of the straight barrel, and even at the end of pulling up. Usually, a liquid amount exceeding 0.75 times the diameter of the straight body part remains.
- the single crystal When the single crystal is pulled in such a deep state of the melt, the influence of natural convection on the flow of the melt becomes large, which is incompatible with forced convection due to the rotation of the single crystal or the crucible. As a result, the flow becomes complicated and the temperature distribution near the growth interface of the single crystal becomes unstable. When the temperature distribution in the vicinity of the crystal growth interface is unstable, a large number of vacancies that cause scatterers are formed in the growth of the single crystal. On the other hand, as described above, the depth of the melt is 0.65 times or less the diameter of the straight barrel part of the azgrung single crystal. The shallower the natural convection that causes such vacancies, the more the number of scatterers present in the pulled single crystal can be significantly reduced.
- the scatterer is an internal defect that is visually observed as a particle that scatters and shines light when observed under condensing illumination, and the maximum diameter of the particle is Generally, it is 100 ⁇ m or less, and usually 10 to 100 ⁇ m is observed.
- the actual state is mostly vacancies, and these are generally in the shape of an octahedron or other angular shape.
- These scatterers usually have a plane almost aligned in a specific orientation of a single crystal, and when irradiated with laser light, scattered light is observed only in a specific direction determined by the incident light and the orientation of the single crystal. The From these results, it is estimated that the vacancies are negative crystals.
- the depth of the raw material metal fluoride melt (7) accommodated in the inner crucible (5) is such that the point force that exerts the effect of suppressing the formation of scatterers inside the single crystal is more pronounced. More preferably, it is not more than 0.55 times, more preferably not more than 0.50 times the diameter of the straight barrel part of the as-grown single crystal.
- the depth of the molten metal fluoride (7) is 15 cm or less, preferably 12 cm or less. Also, in the crystal pulling process, the single crystal body and the crucible, or the single crystal body and a part of the raw material solidified at the bottom of the crucible are prevented from coming into contact with each other and stored in the inner crucible (5).
- the depth of the molten metal fluoride (7) is preferably at least 0.1 times the diameter of the straight body of the azgrown single crystal, more preferably at least 3 cm.
- the storage depth of the inner crucible (5) with respect to the outer crucible (4) is continuously changed so that the depth of the melt (7) is in the above range during the pulling period, and the liquid
- the height of the single crystal pulling rod (13) may be controlled according to the change in the height of the surface. If the amount of the raw material fluoride melt (7) contained in the crucible is slightly increased at the beginning of pulling, the depth of the melt may exceed the above range. However, even in such a case, at least the straight body part, which is the most useful part for cutting out the optical member, is lifted, and the depth of the melt is kept within the above range during this period. I like it.
- the fluctuation range of the melt depth is made as small as possible from the viewpoint of further stabilizing the pulling (crystal growth) interface.
- the size of the inner crucible (5) may be determined according to the size of the metal fluoride single crystal to be produced. That is, the inner diameter of the inner crucible (5) only needs to be larger than the maximum value of the diameter of the produced metal fluoride single crystal. However, if the inner diameter of the inner crucible (5) is too large, the effect of suppressing the volatilization of the metal fluoride when a shielding member described later is provided is reduced, while the diameter of the single crystal is close to the maximum value. If it is too high, disorder of the melt (7) is likely to occur, and it may be difficult to carry out crystal pulling stably.
- the diameter of the straight body portion of the single crystal to be manufactured is the maximum value of the diameter of the single crystal.
- the depth of the inner crucible (5) exceeds the lower limit value of the preferred range of the depth of the raw material metal fluoride melt (7) contained in the inner crucible (5) described above.
- the depth is preferable. That is, it is preferable to make it deeper than 0.1 times the diameter of the straight barrel part of the as-grown single crystal to be pulled, more preferably 3 cm.
- the viewpoint power is the upper limit value of the preferred range of the depth of the molten metal fluoride (7) contained in the inner crucible (5) described above, even if the inner crucible (5) has the maximum depth ( The depth is preferably slightly greater than the diameter of the straight barrel portion of the pulled as-grown single crystal (0.65 times).
- the upper end of the inner crucible (5) has a great influence on the state of heat radiation. For this reason, it is preferable that the upper end portion is separated from the melt surface force serving as the crystal growth interface, that is, the depth of the inner crucible (5) is preferably deeper.
- the depth of the inner crucible is preferably 0.5 to 3 times the diameter of the straight barrel of the as-grown single crystal to be pulled up, more preferably 0.65 to 2 times. preferable.
- the outer crucible (4) has a diameter corresponding to the size of the single crystal to be pulled up and a depth sufficient to accommodate the molten metal fluoride (7) required for the pulling up. Things are used.
- the depth of the outer crucible (4) is preferably 1.3 to 3 times the depth of the inner crucible (5) in consideration of the smoothness of replenishment of the melt (7) into the inner crucible (5).
- the diameter of the outer crucible (4) is determined by considering the effect of removing solid impurities contained in the molten metal fluoride (7) (described later) at the opening (20) at the inner surface of the side wall of the outer crucible (4).
- the distance between the inner crucible (5) and the outer surface of the side wall of the inner crucible (5) is preferably such that the inner diameter of the outer crucible (4) is 1Z10 to 1Z3, more preferably 1Z8 to 1Z4.
- the inner surface of the side wall of the outer crucible (4) and the outer surface of the side wall of the inner crucible (5) are generally substantially perpendicular to each other at least in the range from the liquid surface of the melt (7) to the position of the opening (20). It extends in parallel.
- the inner diameter of the inner crucible (5) or the outer crucible (4) is the diameter of the largest portion of the inner diameter of the crucible, and the depth is the length to the deepest position of the upper end force of the crucible. It is.
- the shape of the bottom wall (15) surface is not particularly limited, and it is provided in the lifting device of FIG. 1 and may be a horizontal plane like the inner crucible. It may be a downwardly convex shape such as a mortar shape or an inverted frustoconical shape, such as a shape force shape or a U shape in a longitudinal section.
- the double structure crucible (6) in Fig. 2 has a bottom wall (15) surface with a V-shaped longitudinal section.
- the downward inclination angle of the bottom wall (15) surface with respect to the horizontal plane is 5%. -55 degrees is preferred. More preferably, it is 8 to 45 degrees, and particularly preferably 15 to 45 degrees.
- the horizontal plane diameter at the midpoint of the cone axis is preferably 1 Z5 or less of the inner diameter of the inner crucible (5).
- the raw material metal fluoride melt (7) contained in the inner crucible (5) refers to the depth from the melt surface to the deepest part of the bottom wall (15) surface of the inner space of the inner crucible (5).
- the communication hole (14) provided in the wall portion of the inner crucible (5) may be provided at an arbitrary position on the bottom wall (15) and the side wall (16) as occasion demands.
- a notch may be provided at the upper end of the side wall (16) of the inner crucible (5), and the inner crucibles of the outer crucible (4) and the inner crucible (5) may be communicated with each other.
- the molten liquid (7) contained in the outer crucible (4) is not contained in the inner crucible (4).
- the notch is overflowed and replenished into the inner crucible (5).
- the communication hole (14) should be provided in the wall portion as low as possible of the inner crucible (5) while being pressed. It is effective.
- the communication hole (14) is preferably provided at the lowermost end or the bottom wall of the side wall. .
- the communication hole (14) has an inner diameter of the bottom wall portion of the inner crucible (5). ) It is preferable to provide it below the position where the inner diameter is 1Z4 or less. It is more preferable to provide it below the position where it is 1Z7 or less (see FIG. 3).
- At least one communication hole is provided in the deepest portion of the inner crucible (5).
- the melt (7) cannot be smoothly replenished from the outer crucible (4) to the inner crucible (5). Since the stability of the liquid level of the melt (7) to be contained may be lowered, 0.05 to 0.8% is preferable with respect to the upper end opening area of the inner crucible (5).
- the communication hole (14) is provided with a plurality of small holes, preferably small holes having a diameter of 2 to 8 mm, in a number of 4 to: LOO, rather than as a single large diameter hole. This is preferable from the viewpoint of the stability of the molten liquid contained in the crucible (5).
- the communication holes (14) are provided as a plurality of small holes as described above, it is preferable that the holes are not unevenly distributed as much as possible, and it is particularly preferable that the central force of the inner crucible (5) is also provided symmetrically.
- the hole shape of the communication hole (14) is not particularly limited, but is usually cylindrical.
- the axial direction of the hole is usually vertical when the wall where the hole is formed is a horizontal bottom wall, and normally horizontal when the wall is a side wall. It may be slightly inclined. When the wall portion forming the hole is an inclined wall in the bottom-convex bottom wall portion, the axial direction of the hole may be an appropriate angle from the vertical direction to the horizontal direction.
- the inner crucible (5) is continuously stored in the outer crucible (4).
- either one of the outer crucible (4) and the inner crucible (5) is fixed in position relative to the chamber (1), and the other crucible is moved up and down continuously.
- a molten metal fluoride (7 When the single crystal is grown while keeping the depth of) within the above-mentioned fixed range, the pulling interface of the single crystal is lowered with time, and the heating environment from the heater (8) is subtle. May change.
- the inner crucible (5) is fixed with respect to the chamber (1), and the outer crucible (4) is placed in the chamber. It is preferable to have a structure that continuously moves up and down.
- the outer crucible (4) placed thereon can also be moved up and down by being driven, and the inner crucible (5) is further moved.
- a structure in which one end is joined to the chamber (1) or a connecting member (17) fixed to the inner member and fixed in the chamber is preferred.
- the connecting member (17) may be horizontally suspended from the side member in the chamber (1), which may also suspend the upper member in the chamber (1).
- the connecting member (17) is provided so as to have a sufficient height above the outer crucible (4) so as not to hinder the upward and downward movement of the outer crucible (4).
- the rod-like connecting member (17) is joined and fixed to the ledge member (19).
- a known mechanism is applied as the mechanism for moving the support shaft (2) up and down, and this mechanism copes with the decrease of the melt (7) contained in the inner crucible (5) with the growth of the single crystal.
- the outer crucible (4) is precisely raised so that the same amount of the melt (7) is replenished into the inner crucible (5) from the outer crucible (4).
- the production of the metal fluoride single crystal using the pulling apparatus of the present invention having the above-described structure grows the metal fluoride single crystal (10) according to the single crystal pulling method.
- the inner crucible (4) is reduced with respect to the inner crucible (5) along with the growth of the single crystal body (10) according to the decrease in the raw metal fluoride melt (7).
- the crucible (5) is stored deeper, and the amount of the molten metal fluoride (7) in the inner crucible (5) is within a certain range, preferably the inner crucible (5)
- the liquid capacity of the melt inside is stored in the outer crucible (4) so that its depth is 3 cm or more and is maintained in the range of 0.65 times or less the diameter of the straight body of the single crystal (10). It is preferable to carry out by a method of supplying the melted raw material metal fluoride (7) into the inner crucible (5).
- a large-sized metal fluoride azgroun single crystal body! ⁇ Te the number of scatterers present in whole inside of the straight body portion is 0.01 or ZCM 3 or less, preferably 0.005 or ZCM 3 or less, more preferably from 0 to 0.002 pieces ZCM 3
- the number of scatterers present in the crystal body or the entire interior of the azgrung single crystal including the shoulder portion is 0.0 3 Zcm 3 or less, preferably 0.01 Zcm 3 or less, more preferably 0 to 0 005 pieces of Zcm 3 can be obtained.
- the double-structure crucible of the lifting device to be used is connected to the outer shell by a communication port provided in the lower wall portion of the inner crucible. If the inner and outer crucibles of the crucible and the inner crucible are partly connected, before starting the pulling The following pre-operation is preferably performed at least once.
- the raw metal fluoride metal melt (7) contained in the inner crucible (5) is removed from the outer crucible (5) side. It is effective to increase the amount of spillage for each operation as much as possible, and it is preferable to drain the entire amount if possible.
- the communication hole (14) formed in the inner crucible (5) is preferably provided below the position where the inner diameter of the inner crucible (5) is 1Z4 or less, more preferably below the position where it is 1Z7 or less.
- at least one of the communication holes (14) is provided at the lower end (deepest part).
- the crucible in the apparatus for pulling a metal fluoride single crystal of the present invention has a double structure crucible (6) capable of continuously changing the storage depth of the inner crucible with respect to the outer crucible.
- the “opening” is formed between the inner surface of the side wall of the outer crucible (4) and the outer surface of the side wall of the inner crucible (5), and the outer surface of the outer crucible (4) and the inner crucible ( This means an annular open surface that opens upward the gap space formed by the inner surface of 5).
- the liquid level of the raw material metal fluoride melt (7) is usually the side wall inner surface of the outer crucible (4) below the shielding member (21) and the inner crucible (5 ) Side wall Located between the outer surface.
- the shielding member (21) extends from the outer surface of the side wall of the inner crucible (5) to the outer crucible.
- the shielding member (21) has an annular ring-like plate shape when viewed from above.
- the outer edge of the shielding member (21) is extended to the vicinity of the inner surface of the side wall of the outer crucible (4). Thereby, the metal fluoride accommodated in the inner space of the outer crucible (4) is suppressed from volatilizing from the opening (20).
- the shielding member (21) has the structure shown in Fig. 2, the outer edge of the shielding member (21) is not fixed to the inner surface of the side wall of the outer crucible (4), but the upper and lower sides of the outer crucible (or inner crucible). Keep moving. Furthermore, in order to prevent the outer edge of the shielding member (21) from rubbing against the inner surface of the side wall of the outer crucible (4) due to the vertical movement of the crucible or vibration due to various factors, the shielding member (21) It is preferable that a certain amount of gap exists between the outer edge and the inner surface of the side wall of the outer crucible (4). On the other hand, from the viewpoint of suppressing the volatilization of the metal fluoride as much as possible, it is preferable that the gap is narrow.
- the distance between the outer edge of the shielding member (21) and the inner surface of the side wall of the outer crucible (4) is preferably a force depending on the size of the outer crucible and the inner crucible, the positional accuracy of moving these crucibles up and down, and the like. .05mm More preferably, it is 0.1 mm or more, more preferably 0.5 mm or more, preferably 30 mm or less, more preferably 10 mm or less, still more preferably 5 mm or less.
- the range of the interval is preferably the same in other embodiments, for example, when the shielding member (21) is fixed to the outer crucible (4) as shown in FIG.
- the shielding member (21) is a force fixed to the outer surface of the side wall of the inner crucible (5).
- the side wall of the outer crucible (4) It can be fixed to the inner surface, or it can be fixed to the upper end of the outer crucible (4) as shown in Fig. 4-a!
- the shielding member (21) is fixed to the crucible, it is preferable to fix the shielding member (21) to the other crucible without moving the vertical force if the change in temperature environment when the crucible is moved up and down is suppressed. .
- the outer crucible (4) is raised as the single crystal is pulled up, and the molten metal fluoride (7) contained in the outer crucible (4) is added to the inner crucible (5
- the position of the liquid surface (crystal growth interface) of the melt (7) with respect to the inner crucible does not substantially change. Therefore, the change in the relative position of the shielding member (21) fixed to the inner crucible (5) with respect to the melt surface is small. Therefore, the gap formed between the shielding member (21) and the liquid surface of the melt (7) can always be kept small, and it is easy to further suppress volatilization of the metal fluoride raw material. It is easy to control the temperature change of the melt accompanying the change in volatilization amount.
- the shielding member (21) When the shielding member (21) is fixed to the crucible, a position where the gap between the molten liquid (7) and the shielding member (21) can be made as small as possible from the viewpoint that volatilization can be suppressed more efficiently. It is preferable to fix to (height). Specifically, the gap may be about 1 to 20 mm. Further, by fixing the shielding member (21) to the crucible which is not moved up and down, the gap can be kept small from the beginning to the end of the pulling of the crystal.
- the shielding member (21) is connected to the outer crucible (4) and the inner crucible as shown in Fig. 4-b.
- the crucible (5) should be suspended on the melt (7) without being fixed to the slippage.
- the shielding member (21) is dropped and used as a lid, so that the melt (7) and the shielding member (21) are separated. There is no gap between them, and the volatilization of the metal fluoride can be prevented particularly efficiently. Even in this case, it is preferable that the size of the shielding member (21) is set so that there is a certain gap without contacting the crucible to be moved up and down.
- the shielding member (21) applies to the entire area of the horizontal plane between the inner wall surface of the outer crucible (4) and the outer wall surface of the inner crucible (5).
- the ratio of the shielded area is preferably 80% or more, more preferably 90% or more, still more preferably 95% or more, and particularly preferably 98% or more.
- the inner wall surface of the outer crucible (4) and the outer wall surface of the inner crucible (5) are usually in the range up to the position of the force opening (20) at least near the position where the shielding member (21) is installed. , And extend substantially parallel to each other in the vertical direction.
- the growth of a single crystal can be performed more stably. Specifically, during crystal pulling, the crystal breaks before reaching the specified pulling length, or even though it does not break, the crystal has bubbles inside it. It is possible to effectively prevent clogging.
- volatilized metal fluoride moves and diffuses to various locations in the single crystal pulling apparatus, but condenses and solidifies when it comes into contact with a low-temperature member in the apparatus. Then, for some reason, this solidified metal fluoride is dropped, and in some cases, the solidified metal fluoride is also dropped and mixed into the melt in the crucible.
- the distance between the inner surface of the side wall of the outer crucible and the outer surface of the side wall of the inner crucible may be reduced, thereby reducing the surface area of the melt.
- the distance between the inner surface of the outer crucible side wall and the outer surface of the inner crucible side wall that is, the width of the opening is present to some extent. Therefore, if the distance between the inner surface of the side wall of the outer crucible and the outer surface of the side wall of the inner crucible is made too small, the effect of the dual structure crucible is reduced.
- the shielding member (21) as described above, the amount of the metal fluoride that volatilizes the opening (20) can be significantly reduced. Furthermore, even if there is a fallen object, the fallen object can be prevented from falling into the melt (7) from the opening (20).
- the shielding member (21) while obtaining the maximum advantage of the double structure crucible in the present invention, the adverse effects on the crystal growth due to volatilization, condensation, solidification and dropping of the metal fluoride are further achieved. Can be avoided.
- the shielding member (21) makes it easy to improve the vacuum ultraviolet light transmittance (hereinafter referred to as VUV transmittance) of the produced single crystal. This tendency is particularly noticeable when solid scavengers are used.
- the metal fluoride can be stored while being transported.It can be completely absorbed with oxides and moisture in order to adsorb it while it is being transported or to come into contact with the outside air when introducing the raw material metal fluoride into the furnace. It is difficult to start pulling the crystal in a state where the is removed. For this reason, usually, an oxygen scavenger called a scavenger is placed in the crucible together with the raw metal fluoride, and the raw metal fluoride and the scavenger are heated while evacuating under reduced pressure prior to the start of crystal pulling. A method is used in which substances are converted to volatile substances and removed.
- Various scavengers according to the type of metal fluoride to be produced are known, but usually, they are more easily bound to oxygen than the metal element constituting the metal fluoride (electronegative) A compound that is a fluoride of an element) and is more volatile than the metal fluoride to be produced.
- the metal fluoride to be manufactured is calcium fluoride
- fluoride metals such as zinc fluoride, lead fluoride, silver fluoride, copper fluoride, and fluorinated hydrocarbons such as CF and CHF Etc. are known.
- fluoride metals such as zinc fluoride, lead fluoride, silver fluoride, copper fluoride, and fluorinated hydrocarbons such as CF and CHF Etc.
- fluoride metals such as zinc fluoride, lead fluoride, silver fluoride, copper fluoride, and fluorinated hydrocarbons such as CF and CHF Etc.
- Jar is also used for refining raw metal fluoride! / Speak.
- the action mechanism of the scavenger is considered as follows. First, zinc oxide reacts with calcium hydride such as in calcium fluoride as raw material to produce zinc oxide and fluoric power. As a result, calcium oxide is removed from the system.
- the generated zinc oxide is further reduced to metallic zinc.
- the generated metallic zinc and unreacted zinc fluoride are easier to volatilize than calcium fluoride and can be removed by increasing the temperature and pressure.
- the scavenging reaction itself as described above can be surely progressed with a higher reaction rate as the temperature is higher.
- scavengers are volatile fluorides
- the higher the temperature the greater the rate of volatilization before participating in the scavenge reaction, and there was a problem in terms of substantial reaction efficiency.
- a method that can increase the usage of scavengers can also be considered. New problems arise, such as the effect of impurities in the scavenger becoming more likely.
- the shielding member (21) is provided at a position between the opening (20) or the side wall inner surface of the outer crucible (4) and the side wall outer surface of the inner crucible (5) below the opening. This reduces the volatilization of the scavenger and can increase its effectiveness even with a small amount of scavenger. it can. At the same time, the volatilization disappears even at higher temperatures.
- the raw metal fluoride (25) and the scavenger are accommodated and heated in the gap space between the inner surface of the outer crucible (4) and the inner crucible (5).
- the force balancer only volatilizes a slight gap force between the communication hole (14) and the outer edge of the shielding member (21) and the crucible wall, so that the volatilization is greatly suppressed.
- the scavenger stays in the space for a long time, and the efficiency of performing the force change reaction is increased. This is presumed to improve the VUV transmittance of the resulting metal fluoride single crystal.
- the scavenger quickly volatilizes from the opening (20), and its effect is limited. turn into. Even when a solid scavenger is not used, the provision of the shielding member (21) suppresses the volatilization of the raw metal fluoride, and the higher the temperature and the higher the metal fluoride is in the crucible. Since it is easy to maintain a vacuum for a long time, moisture adsorbed in the chamber (1), the heat insulating material (9), etc. can be removed to a high degree. Thereby, the VUV transmittance of the obtained metal fluoride single crystal can be improved.
- a metal fluoride single crystal is formed as follows. Manufacture the body. First, a metal fluoride raw material and, if necessary, a solid scavenger are heated in a space formed between the inner surface of the outer crucible and the outer surface of the inner crucible in the double structure crucible. The amount of the solid scavenger used may be appropriately set according to the purity of the raw metal fluoride, but is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the raw metal fluoride.
- the temperature is continued to rise, the temperature reaches the temperature at which the metal fluoride begins to sublime under the atmospheric pressure as described above (for example, about 1200 ° C for calcium fluoride). At this time, as shown in Fig. 5-b. If a crucible with an open top is used, a large amount of raw material metal fluoride is volatilized, so the exhaust is stopped before reaching the sublimation temperature in order to prevent contamination in the furnace. However, it is necessary to restore the pressure by introducing an inert gas such as argon.
- an inert gas such as argon.
- the volatilization (sublimation) of the raw metal fluoride can be effectively suppressed by providing the shielding member (21), it is possible to set the temperature of the above-mentioned re-pressure to a temperature higher than the sublimation start temperature It is. By maintaining a vacuum state at a temperature higher than the sublimation start temperature, moisture adsorbed on the heat insulating material or the like can be removed to a higher degree.
- the above-described double pressure may be performed after sufficiently removing moisture and oxides in the furnace in this way. It is preferable that the return pressure is performed at a temperature lower than the temperature at which the raw metal fluoride melts.
- the pressure at the time of the return pressure may be a normal pressure or a reduced pressure of about 0.5 to 70 kPa.
- the pressure at the time of returning is preferably 5 to 50 kPa, more preferably 10 to 30 kPa. is there.
- the metal fluoride single crystal may be pulled up by the method described above.
- the position (height) of the melt surface with respect to the crucible on the side not moved up and down changes.
- the shielding member (21) is preferably fixed to the crucible on the side that does not move up and down, but in this case, even when the position of the molten liquid surface becomes the highest, the liquid surface position is the shielding member. It is preferable not to be higher than (21). Further, as described above, the position of the melt surface is also a shielding member during the period of pulling up the crystal.
- the diameter of the straight body part is 100 mm or more.
- Large single crystals with a length of 40 mm or more in the moon can be stably manufactured, and the diameter of the same month 150 to 300 111111 and the length of the same month 100 to 300 mm Even a very large single crystal can be manufactured stably.
- the heater (8) a resistance heating heater is preferable.
- resistance heaters are advantageous in obtaining high-quality crystals in which the temperature distribution in the furnace tends to be steep.
- the single crystal pulling rod (13), the support shaft (2), the piercing window (22), etc. be hermetically sealed with an O-ring or a magnetic fluid seal. If leakage occurs from these parts during the melting process of the raw metal fluoride or the crystal growth process, there is a risk that the quality of the single crystal will be markedly lowered or the transparency will be lowered.
- the apparatus is usually provided with an exhaust system such as a vacuum pump, and a gas introduction / exhaust system such as a pipe connecting the exhaust system and the furnace.
- a vacuum pump for evacuating the chamber (1) a known rotary pump can be used.
- a rotary pump and an oil diffusion pump, or a combination of a rotary pump and a molecular pump is preferred.
- a load cell for measuring the crystal growth rate is installed on the single crystal pulling rod (13) or the support shaft (2), and the measured value is fed back to the heater output or the crystal pulling rate, so that a single unit of stable quality can be obtained. Crystals can be obtained.
- Members such as the double-structure crucible (6), support shaft (2), cradle (3), and shielding member (21) are usually carbon-based materials such as graphite, glassy graphite, and silicon carbide-deposited graphite. It is made of materials and refractory metals such as gold, platinum rhodium alloy and iridium. These members are particularly preferably made of a carbon-based material.
- the heater (8), the heat insulating wall (9), etc. are usually made of a carbon-based material such as graphite, vitreous graphite, or silicon carbide black ship.
- the double-structured crucible (6) is divided into an outer crucible (4) and a Z or inner crucible (5) of different sizes and shapes depending on the type and size of the metal fluoride single crystal to be produced. It is preferable to have a structure that can be replaced as appropriate.
- preferred production conditions for producing a metal fluoride single crystal using the pulling apparatus of the present invention are as follows.
- raw material metal fluoride natural minerals such as fluorite in calcium fluoride may be used, but from the viewpoint of purity, it is preferable to use a chemically synthesized product. It is also preferable to use a crushed single crystal obtained by the crucible descent method.
- Powder may be used as the raw material metal fluoride, but since the volume reduction when melted is severe, the particle size is preferably 60 ⁇ m or more, more preferably 60 to: LOOO ⁇ m. Is preferred.
- the pretreatment to remove the moisture is the power performed by heat-treating the raw material metal fluoride under reduced pressure by a vacuum pump. It is difficult to sufficiently remove the moisture inside the raw material simply by firing.
- the raw metal fluoride is preferably melted in an atmosphere containing carbon tetrafluoride, carbon trifluoride, hexafluorotechtane or the like as a gas scavenger.
- a gas scavenger carbon tetrafluoride is used. Is most preferred.
- the raw material metal fluoride subjected to such pretreatment may be grown as a single crystal by the pulling method with the molten state force as it is, but preferably it is cooled and solidified and exists on the surface thereof. Power to use solid impurities by cutting as much as possible. This is preferable from the viewpoint of reducing polycrystallization.
- the single crystal pulling device is also cleaned by heating it to a temperature higher than that for crystal growth in the presence of fluorides such as zinc fluoride and lead fluoride prior to the introduction of the raw metal fluoride. It is preferable to keep in mind.
- fluoride the same scavenger as described above may be used.
- the melting of the raw material metal fluoride is preferably performed in an inert gas atmosphere. It is preferable that the inert gas is continuously supplied into the apparatus, and the carbon dioxide produced by the reaction between the scavenger and the residual moisture is discharged outside the apparatus.
- the single crystal is pulled up at a temperature at which the temperature of the crystal growth interface of the metal fluoride becomes approximately the melting point of the metal fluoride.
- a method of controlling by the temperature at the bottom of the crucible is preferably used.
- the raw material metal fluoride is heated from the melting point to the melting point + 150 ° C at the measurement temperature of the crucible bottom, for example, if the metal fluoride is calcium fluoride, about 1420 ° C to 1570 ° C.
- the single crystal is preferably pulled at a temperature of Further, the rate of temperature increase to the temperature is preferably 50 to 500 ° C ZHr.
- an inert gas such as argon is preferable, but if necessary, crystal pulling may be performed in a fluorine-based gas atmosphere such as CF or HF.
- the seed crystal and the growing crystal are preferably rotated about the pulling axis.
- the rotation speed is preferably 5 to 30 times Z minutes.
- the crucible may be rotated in the opposite direction at the same rotation speed.
- the pulling rate of the crystal is preferably 1 to lOmmZ time.
- cooling until the single crystal body is removed from the furnace is usually performed at a temperature lowering rate of 10 ° CZ or less.
- a temperature lowering rate of about 0.5 ° CZ or less, more preferably about 0.1 to 0.3 ° CZ.
- the seed crystal used for pulling the single crystal it is preferable to use a single crystal of the same material as the metal fluoride to be grown.
- the growth surface of the seed crystal can be selected arbitrarily. Futsui When using calcium seed crystals, the ⁇ 111 ⁇ plane, ⁇ 100 ⁇ plane, ⁇ 110 ⁇ plane, and their equivalent planes should be used appropriately. Can do.
- the number of scatterers present in the entire inner part of the straight barrel portion of the azgrung single crystal and the number of scatterers present in the entire interior of the azgrown single crystal are respectively It measured by the following method.
- the double structure crucible (6) has the structure shown in FIG. 2 except that it does not have a shielding member (21). In addition, as described in Japanese Patent Application Laid-Open No. 2004-182587, it has a heat insulating material wall (9) and a ceiling plate that surrounds the space where the metal fluoride single crystal (10) is pulled up.
- a calcium fluoride single crystal was produced using the single crystal pulling apparatus having the structure shown in FIG.
- the outer crucible (4) made of high-purity graphite installed in the chamber (1) has an inner diameter of 38 cm (outer diameter of 40 cm) and a depth of 30 cm. It was.
- the inner crucible (5) accommodated in the outer crucible (4) in a state of being fixed to the lid material (19) of the chamber by the connecting member (17) has an inner diameter of 25 cm (outer diameter of 26 cm).
- the height was 14 cm.
- the bottom wall of the inner crucible (5) had a V-shaped (mortar shape) vertical cross section with an inclination angle of 15 degrees downward with respect to the horizontal plane.
- the bottom wall has a total of nine caliber forces, one at the lower end (center) and eight at regular intervals on the circumference 25 mm away from the center along the bottom wall.
- the cylindrical communication holes (14) were formed (the total opening area of these communication holes was 0.2% with respect to the upper end opening area of the inner crucible).
- the heat insulating material wall (9) was a pitch-based graphite-formed heat insulating material and had a heat dissipation capability of 9 WZm 2 'K in the thickness direction.
- the ceiling panel installed above it was made of Graphite and had a heat dissipation capacity of 5000 WZm 2 ⁇ K in the thickness direction.
- the inner crucible (5) Into the outer crucible (4) and the inner crucible (5), a total of 40 kg of raw calcium fluoride lump that has been subjected to sufficient purification and moisture removal treatment is added, and the inner crucible (5) has high purity as a scavenger. 4 g of zinc fluoride was charged and installed in the chamber 1 (1). Then, the chamber one (1) within the evacuated (5 X 10- 6 torr or less), by energizing the heater (8) to start the heating of the raw material, the temperature was raised to 250 ° C, this temperature 2 Held for hours. Thereafter, the temperature was raised again, and when the temperature reached 600 ° C, the vacuum exhaust line was shut off, high-purity argon was supplied into the chamber (1), and the internal pressure was maintained at 106.4 KPa.
- the storage depth of the inner crucible (5) in the outer crucible (4) is the depth of the raw calcium fluoride melt (7) in the inner crucible (5).
- the surface state of the melt (7) accommodated in the inner crucible (5) was observed again from the glazing window (22), but solid impurities were not confirmed this time.
- the single crystal pulling rod (13) is lowered, and the lower end surface (single crystal growth surface) of the seed crystal (11) whose crystal plane is ⁇ 111 ⁇ is used as a raw material calcium fluoride melt (7) A single crystal was started to grow.
- the seed crystal (11) was rotated 6 times at Z minutes, while the outer crucible (4) was also pulled up in the state rotated twice Z minutes in the opposite direction.
- the support shaft (2) was continuously raised so that the depth of the melt (7) in the inner crucible (5) was maintained at 6 cm.
- the temperature was lowered to room temperature.
- the number of scatterers present in the entire interior of the straight barrel portion and in the entire interior of the azgrung single crystal was measured. As a result, the number of scatterers present in the entire interior of the straight barrel was five, and the existence ratio was 0.0001 Zcm 3 . In addition, the number of scatterers present inside the entire azgrung single crystal was 21, and the existence ratio was 0.004 / cm 3 .
- the above azgrung single crystal was sliced to a thickness of 10 mm in a plane perpendicular to the growth direction, and its crystallinity was examined using an X-ray topograph. The position deviation was within 0.1 degree, and it was confirmed to be a single crystal.
- the inner crucible (5) was not used as the crucible, but only the outer crucible (4) was used. ⁇ Added the same amount of zinc.
- the capacity of the raw calcium fluoride lump in the crucible (4) is such that when melted, the melt depth is 12.2 cm (a depth of 0.76 times the diameter of the straight barrel of the azgrung single crystal). It was an amount.
- the chamber one (1) within the evacuated (5 X 10- 6 torr or less), by energizing the heater (8) to start the heating of the raw material, the temperature was raised to 250 ° C, this temperature Hold for 2 hours. After that, the temperature was raised again, and when the temperature reached 600 ° C, the vacuum exhaust line was shut off and high-purity argon was supplied into the chamber (1) to keep the internal pressure at 106.4 KPa.
- the heater output was lowered and held at 1 440 ° C for 120 minutes. At this time, when the surface state of the melt (7) accommodated in the inner crucible (5) was observed from the glazing window (22), floating of solid impurities was confirmed.
- the single crystal pulling rod (13) is lowered, and the lower end surface (single crystal growth surface) of the seed crystal (11) whose crystal plane is ⁇ 111 ⁇ is used as a raw material calcium fluoride melt (7 ) Was brought into contact with the surface of) and the growth of single crystals was started.
- the seed crystal (11) was rotated 6 times at Z minutes, while the crucible (4) was also pulled up in the opposite direction and rotated 2 times at Z minutes. After the pulling up, the temperature was lowered to room temperature.
- the amount of the raw material fluoride calcium melt (7) remaining in the crucible (4) at the end of the pulling is 7.6 cm deep (the diameter of the straight barrel of the azgrung single crystal). 0.48 times the depth).
- the number of scatterers present in the entire interior of the straight barrel portion and in the entire interior of the azgrung single crystal was measured. As a result, the number of scatterers present in total internal straight body portion was 72, their presence ratio mediation at 0.018 pieces ZCM 3 It was. The number of scatterers present in the entire interior of the azgrung single crystal was 164, and the existence ratio was 0.035 / cm 3 .
- Example 1 the amount of raw calcium fluoride lump contained in the outer crucible (4) and the inner crucible (5) was 50 kg, and the amount of high purity zinc fluoride contained in the inner crucible (5) was 2 A calcium fluoride single crystal was produced in the same manner as in Example 1 except that the amount was 5 g.
- the storage depth of the inner crucible (5) relative to the outer crucible (4) is within the inner crucible (5)!
- the depth was 12cm (0.60 times the diameter of the straight barrel diameter of azgrung single crystal).
- Example 1 the bottom surface (single crystal growth surface) of the seed crystal (11) whose crystal plane is ⁇ 100 ⁇ is brought into contact with the surface of the raw material calcium fluoride melt (7) to form a single crystal.
- a calcium fluoride single crystal was produced in the same manner as in Example 1 except that it was grown.
- the diameter of the straight body portion is 180 mm and the length of the straight body portion is 200 mm.
- 18.9 kg of calcium fluoride azgrown single crystal volume of the straight body part 5090 cm 3 , volume of the entire azgrung single crystal 5940 cm 3 ) was obtained.
- the number of scatterers present in the entire interior of the straight barrel portion and in the entire interior of the azgrung single crystal was measured. As a result, the number of scatterers present in the entire interior of the straight barrel was 4, and the existence ratio was 0.0008 Zcm 3 . In addition, the number of scatterers present in the entire interior of the azgrung single crystal was 22, and the existence ratio was 0.0035 / cm 3 .
- the chamber one (1) within the evacuated (5 X 10- 6 torr or less), by energizing the heater (8) to start the heating of the raw material, the temperature was raised to 250 ° C, this temperature 2 Held for hours. Thereafter, the temperature was raised again, and when the temperature reached 600 ° C, the evacuation line was shut off, high-purity argon was supplied into the chamber (1), and the internal pressure was maintained at 106.4 KPa.
- the support shaft (2) was lowered.
- the inner crucible (5) is stored in a shallower depth relative to the outer crucible (4), and the entire amount of the single crystal raw material melt (7) contained in the inner crucible (5) is placed in the outer crucible (5). Spilled. Thereafter, the support shaft (2) is raised again to increase the storage depth of the inner crucible (5) relative to the outer crucible (4), and the raw material barium fluoride in the outer crucible (4) is dissolved.
- the melt (7) was supplied into the inner crucible (5).
- the inner crucible (5) is stored in the outer crucible (4) at a depth of 8 cm (as-grown) in the inner crucible (5).
- the depth was 0.44 times the diameter of the straight body of the single crystal.
- the surface state of the melt (7) accommodated in the inner crucible (5) was observed again from the glazing window (22), but no solid impurities were confirmed this time.
- the single crystal pulling rod (9) is lowered, and the lower end surface (single crystal growth surface) of the seed crystal (7) whose crystal plane is ⁇ 111 ⁇ is used as the raw material barium fluoride melt (7)
- a single crystal was started to be brought into contact with the surface.
- the seed crystal (11) was rotated 6 times in Z minutes, while the outer crucible (4) was also pulled up in the opposite direction and rotated twice in Z minutes.
- the support shaft (2) was continuously raised at a speed of 0.83 mmZHr so that the depth of the melt (7) in the inner crucible (5) was maintained at 8 cm. After the pulling up, the temperature was lowered to normal temperature.
- the number of scatterers present in the entire interior of the straight barrel part and in the entire interior of the azgrown single crystal was measured for this barium fluoride azgrown single crystal. As a result, the number of scatterers present in the entire inner part of the straight body part was 5, and the existence ratio was 0.0035 Zcm 3 . The number of scatterers present in the entire interior of the azgrung single crystal was 17, and the existence ratio was 0.0044 Zcm 3 .
- a calcium fluoride single crystal is obtained by using a pulling device for producing a single crystal having the same structure as in Example 1 except that a shielding member (21) is attached to a double structure crucible (6).
- the double structure crucible (6) has an outer crucible (4) of 30cm depth and an inner diameter of 50cm, an inner crucible (5) depth of 150cm and an inner diameter of 36cm, and the crucible bottom toward the center. It was V-shaped (conical) with an inclination angle of 30 degrees downward with respect to the horizontal plane (inner angle 120 °).
- a plate-shaped shielding member (21) in the shape of a ring with a thickness of 6 mm and a gap of 1.5 mm between the inner wall of the outer crucible was attached at a position 2 cm from the upper end. .
- the inner crucible has a total of 9 pieces, one at the lower end (center) and 8 at even intervals on the circumference 25 mm away from the center along the bottom wall.
- a cylindrical communication hole (14) with an aperture force of mm was formed.
- the heat insulation wall (9) is a pitch-type graphite-formed heat insulation material with a heat dissipation capacity of 9 in the thickness direction.
- the ceiling panel installed above it was made of Graphite and had a heat dissipation capacity of 5000 WZm 2 ⁇ K in the thickness direction.
- the temperature was raised at about 50 ° C. ZHr until the temperature at the bottom of the crucible reached 250 ° C. and held at this temperature for 12 hours.
- the degree of vacuum chamber one after 24 hours was 1 X 10- 3 Pa.
- the temperature was raised again at about 50 ° C ZHr. After the temperature at the bottom of the crucible reached 1450 ° C, the temperature was further maintained for 3 hours, and then the vacuum exhaust line was shut off to remove high-purity argon. The internal pressure (furnace atmosphere pressure) was maintained at 19 kPa. After that, exhaust and gas introduction were not performed until the pulling was completed and the temperature was lowered to near room temperature. In addition, the strength of the window (22) force was confirmed. At the crucible bottom temperature of 1450 ° C, the raw material calcium fluoride was not melted.
- the heater output was increased until the temperature at the bottom of the crucible reached 1600 ° C, and the temperature was raised. After holding for 60 minutes, it was observed from the piercing window (22) provided in the upper part of the chamber, and it was confirmed that the raw material was completely melted. In this state, raise the position of the outer crucible to hook it. A portion of the molten metal raw material melt flows into the inner crucible of the inner crucible and the outer crucible (4) and the inner crucible (5) contain the calcium fluoride raw material melt (7). did.
- the heater output was lowered and held at a temperature of 1580 ° C at the bottom of the crucible for 40 minutes, and then the heater output was further lowered and held at 1540 ° C for 120 minutes.
- the support shaft (2) was lowered.
- the inner crucible (5) is stored in a shallower depth relative to the outer crucible (4), and the entire amount of the single crystal raw material melt (7) contained in the inner crucible (5) is placed in the outer crucible (4). Spilled. Thereafter, the support shaft (2) is raised again to increase the storage depth of the inner crucible (5) relative to the outer crucible (4), and the molten calcium fluoride raw material in the outer crucible (4) (7) was fed into the inner crucible (5). This operation was repeated until no solid impurities could be confirmed on the surface of the melt in the inner crucible.
- the position of the outer crucible (4) relative to the inner crucible (5) is adjusted so that the raw calcium fluoride melt (7) in the inner crucible (5) has a depth of 10 cm. It became the position.
- the lower end face (single crystal growth face) of the seed crystal (11) whose crystal face is ⁇ 111 ⁇ was brought into contact with the surface of the raw material fluoric power melt (7) to start growing the single crystal.
- the seed crystal was rotated at 8 rpm and pulled up with 4 mm ZHr. After the start of growth, the crystal growth rate was measured with a load cell installed on the pulling shaft, and this was fed back to the heater output to automatically control it to approach the preset crystal shape.
- the target crystal size under the above conditions is a single crystal having a diameter of 250 mm and a length of 150 mm of the straight body portion.
- the outer crucible (4) was gradually raised with crystal growth so that the depth of the melt (7) in the inner crucible (5) was maintained at 10 cm.
- the temperature was lowered to 300 ° C at a cooling rate of 15 ° C / Hr, and then the heater was turned off and the temperature was lowered to room temperature.
- the trouble that caused no trouble until the single crystal reached the desired size was caused four times, causing troubles such as crystal breakage and stalagmite. It was 5 times.
- the single crystal was pulled using the same single crystal pulling apparatus as in Example 5 except that the shielding member (21) was not attached to the double structure crucible (6). Note that the holding time at 250 ° C in the temperature rising process is doubled for 24 hours, and the temperature at which high-purity argon is supplied into the chamber is 600 The test was performed under the same conditions as in Example 5 except that the temperature was changed to ° C.
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- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Metallurgy (AREA)
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- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
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Priority Applications (2)
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US11/793,572 US8016942B2 (en) | 2004-12-22 | 2005-12-16 | Process for producing metal fluoride single crystal |
EP05816637A EP1849893A4 (en) | 2004-12-22 | 2005-12-16 | APPARATUS FOR PUSHING A MONOCRYSTAL OF METAL FLUORIDE AND METHOD FOR PUSHING THE SAME WITH THE APPARATUS |
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JP2004-370658 | 2004-12-22 | ||
JP2004370658 | 2004-12-22 | ||
JP2005-267398 | 2005-09-14 | ||
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PCT/JP2005/023182 WO2006068062A1 (ja) | 2004-12-22 | 2005-12-16 | フッ化金属単結晶体の引上げ装置および該装置を用いたフッ化金属単結晶体の製造方法 |
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US (1) | US8016942B2 (ja) |
EP (1) | EP1849893A4 (ja) |
TW (1) | TW200632149A (ja) |
WO (1) | WO2006068062A1 (ja) |
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JP2008239361A (ja) * | 2007-03-26 | 2008-10-09 | Tokuyama Corp | フッ化金属用加熱溶融炉に用いる断熱材の再生方法 |
JP2012012244A (ja) * | 2010-06-30 | 2012-01-19 | Tokuyama Corp | フッ化金属単結晶体の製造方法 |
JP2013193907A (ja) * | 2012-03-19 | 2013-09-30 | Kyocera Corp | 結晶成長装置、結晶成長方法および結晶成長用坩堝 |
CN113502546A (zh) * | 2021-07-06 | 2021-10-15 | 中国电子科技集团公司第十三研究所 | 一种磁场下合成及连续生长磷化物的方法 |
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JP2013193907A (ja) * | 2012-03-19 | 2013-09-30 | Kyocera Corp | 結晶成長装置、結晶成長方法および結晶成長用坩堝 |
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Also Published As
Publication number | Publication date |
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EP1849893A4 (en) | 2010-10-20 |
EP1849893A1 (en) | 2007-10-31 |
US20080000413A1 (en) | 2008-01-03 |
TW200632149A (en) | 2006-09-16 |
US8016942B2 (en) | 2011-09-13 |
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