CN116676669A - Equipment and method for purifying and treating calcium fluoride crystal growth raw material - Google Patents
Equipment and method for purifying and treating calcium fluoride crystal growth raw material Download PDFInfo
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- CN116676669A CN116676669A CN202310966536.8A CN202310966536A CN116676669A CN 116676669 A CN116676669 A CN 116676669A CN 202310966536 A CN202310966536 A CN 202310966536A CN 116676669 A CN116676669 A CN 116676669A
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- crystal growth
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- 239000002994 raw material Substances 0.000 title claims abstract description 152
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims abstract description 81
- 229910001634 calcium fluoride Inorganic materials 0.000 title claims abstract description 81
- 239000013078 crystal Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000005540 biological transmission Effects 0.000 claims abstract description 31
- 238000000746 purification Methods 0.000 claims abstract description 25
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical group F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 49
- 239000010439 graphite Substances 0.000 claims description 48
- 229910002804 graphite Inorganic materials 0.000 claims description 48
- 239000012535 impurity Substances 0.000 claims description 41
- 239000000155 melt Substances 0.000 claims description 31
- 238000002844 melting Methods 0.000 claims description 27
- 230000008018 melting Effects 0.000 claims description 27
- 239000010410 layer Substances 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000012495 reaction gas Substances 0.000 claims description 10
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 8
- 239000002344 surface layer Substances 0.000 claims description 8
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000005204 segregation Methods 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 11
- 229940123973 Oxygen scavenger Drugs 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 4
- 238000001259 photo etching Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- -1 hexafluoromethane Chemical compound 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000003071 parasitic effect Effects 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BLIQUJLAJXRXSG-UHFFFAOYSA-N 1-benzyl-3-(trifluoromethyl)pyrrolidin-1-ium-3-carboxylate Chemical compound C1C(C(=O)O)(C(F)(F)F)CCN1CC1=CC=CC=C1 BLIQUJLAJXRXSG-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 1
- 229960004065 perflutren Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/007—Mechanisms for moving either the charge or the heater
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The application relates to a purifying treatment device and a purifying treatment method for calcium fluoride crystal growth raw materials, and relates to the technical field of material purification. According to the application, the crucible is fixed in the sleeve, the heater is moved along the horizontal direction, so that the calcium fluoride raw material is melted in the horizontal area, no complex melt convection exists, solute transmission basically depends on concentration difference in the horizontal direction, the crystallization process is uniformly carried out from one side to the other side, a large number of polycrystal and defect in the crystal lump are effectively avoided, the single crystal rate is improved, and the purification effect is enhanced.
Description
Technical Field
The application relates to the technical field of material purification, in particular to a purification treatment device and method for a calcium fluoride crystal growth raw material.
Background
Calcium fluoride is an inorganic compound which is colorless crystals or white powder, is insoluble in water and slightly soluble in inorganic acid. The functions of crystal finished products produced by calcium fluoride raw materials with different purities are different, so that the calcium fluoride raw materials and products are required to be correspondingly classified according to the demands of different clients from the standpoint of comprehensive benefits. The ultraviolet-grade calcium fluoride crystal has extremely high ultraviolet transmittance, high laser damage threshold, low double refractive index and high refractive index uniformity, can be applied to 157nm and 193nm laser photoetching systems, and is a necessary material for realizing domestic replacement by photoetching at present.
Since the high purity raw materials for growing the ultraviolet-grade calcium fluoride crystal are expensive, it is most suitable to batch purify the purchased raw materials with lower purity and then put the raw materials into the ultraviolet-grade calcium fluoride for production. In the prior art, the method for purifying the calcium fluoride raw material is mainly a crucible descending method (BS method), wherein a device of the crucible descending method (BS) comprises a furnace body, a crucible, a lifting rod, a displacement sensor, a speed reducing controller, a heater and an insulating layer, the crucible slides downwards along the furnace body through the lifting rod, the displacement sensor is used for judging the descending position of the crucible, and the speed reducing controller is used for controlling the descending speed of the crucible. The method comprises the following technical processes: placing the raw materials in a closed crucible, adding deoxidizer-lead fluoride (PbF 2), and melting after high vacuum pumping; the crucible drop rate and heater power profile are then set so that the feedstock melt will begin to crystallize from the bottom of the crucible and eventually all of the feedstock melt in the crucible will crystallize as the crucible continues to move longitudinally.
However, in the purification process, the melt is crystallized at the bottom of the crucible, the crystal is directly contacted with the bottom of the crucible to easily carry out parasitic nucleation, and a large number of polycrystal and defect are generated in the crystal lump along with the downward continuous movement of the crucible, so that the single crystal rate is lower; in addition, the melt in the crucible can be in a complex convection environment, and the separated impurity ions need to be transmitted to the upper part of the melt in the anti-gravity direction, so that the influence of convection is serious. In a word, the solid-liquid interface conditions of the polycrystal are different, a large number of defects can wrap a part of impurities, and the influence of convection on solute transmission can cause inconsistent impurity removal steps everywhere, so that the purification effect of the calcium fluoride raw material is reduced.
Disclosure of Invention
The application provides a purifying treatment device and a purifying treatment method for a calcium fluoride crystal growth raw material, which are used for solving the problems of low single crystal yield and poor effect of calcium fluoride raw material purification. Meanwhile, the defects of bubbles and the like which can wrap impurities and are generated during raw material crystallization are reduced, and the purification effect of the calcium fluoride raw material is effectively improved.
In a first aspect, the application provides a purifying treatment device for calcium fluoride crystal growth raw materials, which comprises a water-cooled furnace body, a vacuum system for adjusting the atmosphere inside the furnace body and an air charging pipeline, wherein a crucible, a sleeve, a heater and an insulating layer are arranged in the furnace body, the upper end of the crucible is in an opening shape and is in clearance fit with the sleeve, the insulating layer is positioned outside the sleeve, a channel is reserved between the insulating layer and the outer wall of the sleeve, and the heater is horizontally arranged in the channel in a sliding manner.
Through adopting above-mentioned technical scheme, when purifying the calcium fluoride raw materials, the raw materials is placed in the crucible, fixes the position of crucible, makes the heater slide along the horizontal direction and heats the calcium fluoride raw materials, helps reducing the mechanical vibration of crucible department. The heater with smaller width moves along the horizontal direction, so that a small enough temperature gradient can be ensured in a relatively smaller melting zone, the melt transmission basically depends on the concentration difference in the horizontal direction, the crystallization process is not performed from bottom to top any more, but is uniformly performed from one side to the other side, the uniformity after melting to crystallization is higher, and the stability and the efficiency of purifying the calcium fluoride raw material are higher.
Further, the heater is a graphite resistance heating ring or a ceramic heating ring, the heater is wound around the circumference of the sleeve, and the ratio of the width of the heater in the horizontal direction to the length of the sleeve is (0.5-1.5): 5.
Through adopting above-mentioned technical scheme, the heater is preferably graphite resistance heating ring, and graphite resistance heating ring encircles sleeve a week and evenly distributed, can make the temperature of the position department of melting the raw materials in the crucible relatively even distribution, helps the crystal to stably precipitate.
Further, both sides of the crucible are inclined outwards, and the bottom wall of the crucible is horizontal.
Through adopting above-mentioned technical scheme, the crucible is open bevel connection structure, is favorable to filling the gas in the furnace body and gets into the raw materials middle part from the space around the raw materials, makes the air current fully enter into each position of raw materials, and gas and raw materials fully contact the reaction promptly. Various impurities volatilized in the raw materials by reaction can be carried away by the flow of the filled gas, and can not enter the raw materials again. In addition, the design of the inclined crucible opening is more favorable for taking raw materials compared with a conical cylindrical crucible.
Further, the heater horizontally slides through the transmission device, the transmission device comprises a transmission rod and driving equipment, the transmission rod is fixed on the heater, the driving equipment is located outside the furnace body, and the driving equipment drives the heater to horizontally slide through the transmission rod.
By adopting the technology, the heater can be controlled to slide along the horizontal direction outside the furnace body, so that the operation is simpler and more convenient and the efficiency is higher.
Further, a sealing ring is arranged at the joint of the transmission rod and the furnace body.
Further, the crucible and the sleeve are made of graphite, and ash content A of the graphite is less than 20ppm.
In a second aspect, the present application also provides a method for purifying a calcium fluoride crystal growth material, which uses any one of the above-described apparatuses, the method comprising:
placing raw materials into a crucible, adding an deoxidizer, vacuumizing, and sequentially filling inert gas and fluorine-containing reaction gas into a furnace body;
moving a heater to a first end of the crucible, heating raw materials in the crucible, wherein a region in the crucible corresponding to the heater is a melting region;
after the raw materials in the melting zone are melted, the heater is moved towards the second end of the crucible at a constant speed, when the heater passes, the crucible heats the raw materials in the melting zone to be in a melt shape, and when the heater passes, the raw materials in the melt shape are re-solidified into crystals, and the raw materials are flatHeng Fenning coefficient k 0 Impurities less than 1 migrate from the crystallization side to the melt side in sequence in the crucible and finally concentrate at the second end of the crucible to obtain an initial pure raw material with an impurity surface layer at one end;
removing the impurity surface layer of the primary pure raw material to obtain the high-purity raw material for calcium fluoride crystal growth.
Further, the fluorine-containing reaction gas is carbon tetrafluoride or trifluoromethane.
Further, the rate of uniform movement of the heater toward the second end of the crucible is 0.5-2.5mm/hr.
Further, the deoxidizer is zinc fluoride, and the zinc fluoride accounts for 0.02-0.07wt% of the weight of the raw material.
Zinc fluoride has a superior effect as an oxygen scavenger for calcium fluoride single crystals to lead fluoride at a transmission wavelength of not less than 157 nm.
In summary, the present application includes at least one of the following beneficial technical effects:
according to the application, the crucible is fixed in the sleeve, and the heater is moved along the horizontal direction, so that the calcium fluoride raw material is melted in the horizontal area, the section of the melting area is narrow and flat, and the raw material is heated more uniformly. The method has the advantages that no complicated melt convection exists, solute transmission basically depends on concentration difference in the horizontal direction, crystallization is not performed from bottom to top, but is uniformly performed from one side to the other side, a large number of polycrystal and defect inside a crystal lump are effectively avoided, and the monocrystal rate is improved. The uniformity of the calcium fluoride raw material after being melted to be crystallized is higher, so that the purification stability and efficiency are higher, and the purification effect is better;
the crucible is designed to be of an open structure, the fluorine-containing reaction gas and the raw materials can be fully contacted and reacted, various impurities volatilized in the raw materials during reaction can be taken away by the flow of the filled gas, and the impurities can not enter the raw materials again, so that the purity of the calcium fluoride raw materials is improved.
Drawings
FIG. 1 is a block diagram showing an apparatus for purifying a calcium fluoride crystal growth raw material in an embodiment of the present application.
Reference numerals illustrate: 1. a furnace body; 11. a sleeve; 12. a crucible; 13. a heater; 131. a graphite resistance heating ring; 132. a melting zone; 14. a transmission device; 141. a transmission rod; 142. a driving device; 15. a heat preservation layer; 16. a channel; 17. an air inlet; 171. an air inlet pipe; 172. a first tube; 173. a second pipe; 18. a valve; 2. a vacuum system.
Detailed Description
The present application will be described in further detail with reference to examples. The specific description is: the following examples were conducted under conventional conditions or conditions recommended by the manufacturer, where specific conditions were not noted; the raw materials used in the following examples were all commercially available from ordinary sources except for the specific descriptions.
The application is characterized in that:
firstly, ultraviolet-grade calcium fluoride crystals are widely used in the photoetching industry, the purity of raw materials provided by the existing domestic calcium fluoride raw material manufacturers varies from 99.9% to 99.999%, the proportion of impurity ions is also different, and imported raw materials such as Germany and Japanese crushed calcium fluoride crystals can reach 99.99999% in standard purity, but the price is extremely high. From the standpoint of comprehensive benefits, a method of directly importing the raw materials is not preferable. Especially, in the current stage, china is running on the way of domestic replacement, and the industries such as photoetching and the like also necessarily put forward demands for domestic replacement of large-size ultraviolet-grade calcium fluoride single crystal products. High purity raw materials are necessary to produce large-size, high quality, uv grade calcium fluoride single crystal products. Therefore, the commercial raw materials with lower purity are purified in batches and then put into the production of the ultraviolet-grade calcium fluoride, which is an optimal method in view of economic benefits.
Purification of low purity materials may utilize a process of melt crystallization of an impure material, which itself is a process of segregation of a solute having a solid concentration less than a liquid concentration (equilibrium segregation coefficient k) 0 Impurity ions of < 1) are continuously expelled from the crystal into the melt. The existing low-purity calcium fluoride raw material purification mode is generally that a crucible descending furnace (BS method) grows crystals, namely, the low-purity calcium fluoride raw material is placed in a closed crucible, an deoxidizer-lead fluoride (PbF 2) is added, the melting material is melted after high vacuum pumping, and the crucible descending speed and a heater power curve are set. The raw material melt will start to form a knot from the bottom of the crucibleAnd (3) crystallizing, namely, along with the continuous movement of the crucible, the melt raw material in the crucible is finally totally crystallized.
However, according to experimental results, the crystal lump produced by the method has a large number of polycrystal and defect inside, and the single crystal rate is low. In addition, the following disadvantages exist for purifying the calcium fluoride raw material: 1. the calcium fluoride raw material is in a relatively closed environment, impurities volatilized from the melt cannot be discharged to the large environment of the furnace body, and if a reaction atmosphere is used, the deoxidization effect is poor due to poor gas fluidity; 2. the calcium fluoride raw material is surrounded by a crucible, and the purity and cleanliness of the crucible material have great influence on the purification effect; 3. because the crystal is directly contacted with the crucible and is easy to parasitize and nucleate, the crystal becomes polycrystal, and the impurity removal steps are inconsistent; 4. the lead fluoride is used as an deoxidizer, and the existence of redundant +2 valent lead ions can seriously reduce the transmittance of calcium fluoride crystals at about 155nm and 205nm, so that the ultraviolet optical performance of the crystals is greatly reduced; 5. because the melt crystallization process is carried out in the vertical direction, solute segregation is inevitably greatly influenced by gravity; 6. the melt is in a complex convection environment, and the impurity ions are transferred to the upper part of the melt in the anti-gravity direction, so that the purification efficiency is definitely low.
Based on the above problems, the inventors found that there are two main reasons for the above problems, namely, the crucible is sealed, and the interior of the crucible is completely separated from the interior environment of the furnace body; 2. the crucible is movable, and the direction of movement of the crucible is longitudinal. In order to solve the above problems, the present application provides an apparatus and a method for purifying a calcium fluoride crystal growth raw material, which comprises an apparatus and a method for purifying a low purity calcium fluoride raw material, the method being realized by using an apparatus for purifying a low purity calcium fluoride raw material.
The structure of the apparatus referring to fig. 1, the apparatus includes a water-cooled furnace body 1 and a vacuum system 2 for adjusting the atmosphere inside the furnace body 1. The vacuum system 2 is pumped to vacuum by a cold pump or molecular pump, preferably a cold pump. The cold pump can be matched with the dry pump to pump the furnace body 1 to high vacuum, so that the vacuum degree reaches 5 ℃ to 10% -4 Pa or below.
The furnace body 1 is internally fixed with a sleeve 11, two ends of the sleeve 11 are in an opening shape, the sleeve 11 is internally fixed with a crucible 12, the upper end of the crucible 12 is in an opening shape, and the upper end and the lower end of the crucible 12 are in clearance fit with the inside of the sleeve 11. The volatilized impurities in the crucible 12 can escape into the sleeve 11, and then escape into the furnace body 1 along the openings at the two ends of the sleeve 11. Is beneficial to strengthening the gas circulation and the deoxidization effect. The two sides of the crucible 12 are inclined outwards, the bottom wall of the crucible 12 is horizontal, and the ratio of the width of the crucible 12 in the horizontal direction to the height of the crucible in the vertical direction is 2:1. The crucible 12 and the sleeve 11 are made of graphite, and ash A of the graphite is less than 20ppm.
The outer wall of the sleeve 11 is provided with a heater 13 in a sliding manner along the horizontal direction, the heater 13 is a graphite resistance heating ring 131 or a ceramic heating ring, and preferably, the heater 13 is a graphite resistance heating ring 131. The graphite resistance heating ring 131 is wound around the sleeve 11 circumferentially, the ratio of the width of the graphite resistance heating ring 131 in the horizontal direction to the length of the sleeve 11 in the horizontal direction is (0.5-1.5): 5, when the graphite resistance heating ring 131 passes through, the corresponding region in the crucible 12 is a melting region 132, after the graphite resistance heating ring 131 passes through, the raw material in the corresponding melting region 132 is heated, and the raw material is heated to be in a melt state.
The heater 13 slides in the furnace body 1 along the horizontal direction through a transmission device 14, the transmission device 14 comprises transmission rods 141 and driving equipment 142, the transmission rods 141 penetrate through the furnace body 1, and the number of the transmission rods 141 is 2. One end of the transmission rod 141 extending into the furnace body 1 is fixed on the graphite resistance heating ring 131, the driving device 142 is positioned outside the furnace body 1, and the driving device 142 is fixedly connected with one end of the transmission rod 141 extending out of the furnace body 1. After the driving device 142 is started, the driving device 142 drives the transmission rod 141 to slide along the horizontal direction, and the transmission rod 141 drives the graphite resistance heating ring 131 to slide outside the sleeve 11 along the horizontal direction so as to heat the raw materials in the melting zone 132 of the crucible 12.
The joint of the transmission rod 141 and the furnace body 1 is fixed with sealing gaskets, the sealing gaskets are fluororubber sealing rings, and the number of the sealing gaskets is 2. The sealing gasket is used for sealing the gap between the transmission rod 141 and the furnace body 1, so that external gas is prevented from entering the furnace body 1 and the gas in the furnace body 1 overflows to the outside.
The sleeve 11 is fixed with the heat preservation 15 outward, and the heat preservation 15 distributes in sleeve 11 circumference periphery and both sides. A channel 16 is reserved between the sleeve 11 and the heat preservation layer 15, the channel 16 is used for the graphite resistance heater 13 to slide along the horizontal direction, and the graphite resistance heater 13 is in clearance fit with the heat preservation layer 15. The heat insulating layer 15 may be made of high-purity graphite carbon felt, aluminum silicate cotton, rock mineral brocade, aluminum silicate cotton, foam bed Dan Jin, aluminum silicate cotton, glass cotton product, aluminum silicate cotton, calcium silicate heat insulating product, silicate composite felt, rock cotton, glass cotton product, etc.
The side wall of the furnace body 1 is provided with an air inlet 17, an air inlet 171 extends into the air inlet 17, one end of the air inlet 171 is fixed on the furnace body 1, one end of the air inlet 171, far away from the furnace body 1, is fixedly connected with a first pipe 172 and a second pipe 173, both the first pipe 172 and the second pipe 173 are communicated with the air inlet 171, the first pipe 172 is used for conveying inert gas, the second pipe 173 is used for conveying fluorine-containing reaction gas, and a valve 18 is arranged at the air inlet 171.
Step S1: a certain amount of low-purity calcium fluoride raw material or the calcium fluoride raw material purified by a crucible descending method (BS method) is placed in a crucible, and the raw material is abutted against the bottom wall of the crucible, which is horizontal. Oxygen scavenger accounting for 0.02 to 0.07 weight percent of the mass of the raw material is added, and preferably the oxygen scavenger accounting for 0.05 weight percent of the mass of the raw material is added, wherein the oxygen scavenger is zinc fluoride.
Zinc fluoride is used as an deoxidizer of calcium fluoride monocrystal, and the deoxidizing effect is superior to that of lead fluoride when the transmission wavelength is not less than 157 nm. Zinc fluoride has lower saturated vapor pressure than lead fluoride at high temperature, namely the content of zinc fluoride remained in the raw material is lower than that of lead fluoride under the same condition, and the comparison is particularly obvious when the Czochralski method is used for growing large-size calcium fluoride single crystals. In addition, zinc fluoride can obviously absorb the transmittance of crystal light only when the wavelength of the zinc fluoride is below 140nm, and the transmittance is obviously superior to that of lead fluoride when the wavelength of the zinc fluoride is above 140 nm.
Step S2: the inside of the furnace body is pumped to high vacuum by a cold pump, and the vacuum degree is 5 cm 10 -4 And after Pa is lower, conveying inert gas into the furnace body through a first pipe, and adjusting the air pressure in the furnace body to-60 to-40 KPa, wherein the air pressure is preferably-50 KPa. The inert gas is selected from any one of helium, neon, argon, krypton, xenon and radon, and is preferably argon.
Step S3: and delivering a fluorine-containing reaction gas to the furnace body through a second pipe, wherein the fluorine-containing reaction gas is selected from any one of carbon tetrafluoride, trifluoromethane, difluoromethane, hexafluoromethane, octafluoropropane, hydrogen fluoride, nitrogen trifluoride, sulfur hexafluoride, xenon difluoride and boron trifluoride. Preferably, the fluorine-containing reaction gas is carbon tetrafluoride, carbon tetrafluoride reacts with water molecules at a temperature ranging from 900 ℃ to 1000 ℃ to generate carbon dioxide and hydrogen fluoride, and reaction products are easily volatilized from the raw materials, so that the fluorine-containing reaction gas is preferably carbon tetrafluoride. The delivery amount of carbon tetrafluoride is quantitatively calculated based on the content of hydroxyl groups contained in the raw material placed in the crucible, in combination with a chemical reaction equation. However, the hydroxyl content of the raw material is generally not available to the raw material manufacturer. The hydroxyl content of the raw materials is a dynamic value during the storage and charging process, so that a certain number of practices are needed to obtain the proper value in actual operation. According to practice, under the precondition of unchanged large environment, 60Kg of raw materials (all new materials) are required to have the best effect of 6-7L of high-purity carbon tetrafluoride.
Step S4: starting a driving device, wherein the driving device slides the graphite resistance heating ring to the first end of the crucible along the horizontal direction through a transmission rod, and the first end of the crucible is the left end, which is marked as a 0 position, referring to fig. 1. Starting a graphite resistance heating ring, wherein the graphite resistance heating ring is molten to form a melt corresponding to the raw materials in the melting zone, and the raw materials in the area, which does not reach the graphite resistance heating ring, are solid.
The temperature at which the graphite resistance heating ring heats is the melting point of the raw material, and the melting point of the calcium fluoride is about 1400 ℃. When the graphite resistance heating ring heats the raw material, the temperature of the center of the raw material in the crucible reaches the melting point of calcium fluoride. The temperature at the heater is above the melting point of the feedstock due to loss of heat from the heater surface during transfer to the feedstock.
After the raw materials in the corresponding melting zone are completely melted, the driving device drives the graphite resistance heating ring to move at a uniform speed towards the second end of the crucible through the transmission rod, and referring to fig. 1, the second end of the crucible is the right end. The temperature of the area of the graphite resistance heating ring after passing is reduced, the raw material in the melt state starts to solidify again into crystals, and meanwhile, impurities in the crystallization raw material are gradually separated out by fractional condensation, and the impurities are uniformly transmitted from the high-concentration crystallization side to the low-concentration melting side. The uniform speed of the graphite resistance heating ring is 0.5-2.5mm/hr, preferably 1-2mm/hr.
In the process, the raw materials react with the reaction atmosphere and the deoxidizer (zinc fluoride) in sequence in the heating process so as to reduce the hydroxyl content in the raw materials.
Step S5: after the graphite resistance heating ring moves, the raw material in the melting zone of the crucible forms a concentration gradient, wherein the concentration of the melt zone on the crystallization side is high, the concentration of the melt zone on the side to be melted is low, and precipitated impurity ions can be transmitted from the crystallization side to the side to be melted in the melt, which is equivalent to natural migration of the impurity ions from the side with high concentration to the side with low concentration. And after the graphite resistance heating ring passes through the second end of the crucible, all raw materials in the crucible are completely melted and recrystallized, and impurities migrate to one end of the calcium fluoride crystal at the second end of the crucible to form an impurity surface layer, so that the primary pure raw materials are obtained. The obtained raw material with initial purity is cooled and taken out, and one side (impurity surface layer) with high impurity content is removed, so that the raw material can be used as raw material for growing ultraviolet grade calcium fluoride monocrystal for production, and the purity of the raw material purified by the method can easily reach the imported material grade (more than 99.999%).
The steps S1-S5 can be repeatedly performed on the premise of allowing cost, so as to achieve better purification effect.
Examples
Example 1
The purification treatment method of the calcium fluoride crystal growth raw material comprises the following steps:
1. placing 60kg of raw materials into a crucible, and adding 0.03kg of zinc fluoride into the raw materials;
2. the dry pump and the cold pump are used to pump the inside of the furnace body to high vacuum, and the vacuum degree reaches 5 ANG 10 -4 Stopping pumping when Pa is lower;
3. then argon is filled into the furnace through the pipe until the air pressure in the furnace body is about-50 KPa, and then 6-7L of high-purity (the purity is 99.9%) carbon tetrafluoride is conveyed into the furnace through the pipe II;
4. starting a driving device, wherein the driving device moves a graphite resistance heating ring to a first end (refer to the left end of the crucible in fig. 1) of the crucible through a transmission rod, marking the position as 0, then starting the graphite resistance heating ring, heating the crucible, wherein the self heating temperature of the graphite resistance heating ring is 1500-1600 ℃, the central temperature of raw materials in the crucible is about 1400 ℃, and the graphite resistance heating ring is molten into a melt state corresponding to the raw materials in a melting zone;
5. the driving device drives the graphite resistance heating ring to move towards the second end of the crucible (refer to the right end of the crucible in fig. 1) at a constant speed of 1.5mm/hr, the raw materials in a melt state in the melt region after passing through the graphite resistance heating ring are re-solidified into a crystalline state, meanwhile, because of solute segregation, a part of impurities are discharged from the crystal, and the discharged impurities migrate towards the area which is not reached by the graphite resistance heating ring under the driving of concentration gradient;
6. in the moving process of the graphite resistance heating ring, hydroxyl in the raw material in a heating state reacts with carbon tetrafluoride and zinc fluoride in sequence to remove the hydroxyl in the raw material;
7. after the graphite resistance heating ring passes through the second end of the crucible, finally enriching impurities in the second end of the crucible to obtain an initial pure raw material with an impurity surface layer at one end;
8. and cooling the primary pure raw material, taking out, and removing the impurity surface layer of the primary pure raw material to obtain the high-purity calcium fluoride raw material.
Examples 2 to 3
Examples 2-3 differ from example 1 in the choice and amount of oxygen scavenger, as shown in Table 1:
TABLE 1 type and amount of oxygen scavenger
| Type of oxygen scavenger | Oxygen scavenger dosage | Inner transmittance | |
| Example 1 | Zinc fluoride | 0.03kg | ≥99.8 |
| Comparative example 1 | Lead fluoride | 0.03kg | ≤99.0 |
| Example 2 | Zinc fluoride | 0.012kg | ≥99.2 |
| Example 3 | Zinc fluoride | 0.042kg | ≥99.8 |
| Comparative example 2 | Zinc fluoride | 0.005kg | ≥99.2 |
| Comparative example 3 | Zinc fluoride | 0.06kg | ≥99.8 |
In combination with table 1, the selection of the oxygen scavenger affects the ultraviolet optical properties of the single crystal grown from the purified calcium fluoride raw material, and the calcium fluoride raw materials obtained in example 1 and comparative example 1 are taken for crystal growth, and the ultraviolet transmittance of the calcium fluoride crystal grown from the two raw materials is detected by a spectrophotometer, so that the calcium fluoride crystal prepared in example 1 is obviously better in transmittance, which means that the ultraviolet optical properties are better. And lead fluoride is used as an deoxidizer, and the transmittance of calcium fluoride crystals at about 205nm and 155nm is seriously reduced by residual trace +2 valent lead ions in the raw materials, so that the ultraviolet optical performance of the calcium fluoride crystals is greatly reduced.
The zinc fluoride is used as an deoxidizer for purifying the calcium fluoride raw material, the addition amount of the deoxidizer can influence the deoxidizing effect, too little zinc fluoride can cause incomplete deoxidization, the impurity content in the purified calcium fluoride raw material is more, and the purity and ultraviolet optical performance of the calcium fluoride raw material are reduced; since an excessive amount of zinc fluoride remains in the furnace and affects the purification effect of the calcium fluoride raw material, the amount of zinc fluoride to be used is preferably 0.03kg.
Examples 4 to 5
Examples 4-5 differ from example 1 in the rate at which the graphite resistive heating ring moves, as specifically referred to in Table 2:
TABLE 2 Rate of constant movement of graphite resistance heating Ring
| Rate (mm/hr) | Crystallization Rate (%) | |
| Example 1 | 1.5 | 99.5% |
| Example 4 | 0.5 | 99.6% |
| Example 5 | 2.5 | 92.7% |
| Comparative example 4 | 0.3 | 90.5% |
| Comparative example 5 | 3.0 | 91.1% |
It was observed that the rate of movement of the graphite resistive heating rings determines the length of residence time of the melt zone at the microscopic level. Too fast, the solute is not transported, where the melt crystallizes; too slow, the timeliness is low and the cost is increased, so that the moving rate of the graphite resistance heating ring is preferably 1.5mm/hr.
Comparative example 6
Comparative example 6 purification of calcium fluoride raw material by the crucible descent method specifically comprises:
1. 60kg of raw materials are taken and placed in a closed crucible, and 0.03kg of zinc fluoride is added into the raw materials;
2. the inside of the furnace body is pumped to high vacuum by a cold pump, and the vacuum degree reaches 5 ANG 10 -4 Stopping pumping when Pa is lower;
3. heating a molten material, heating raw materials in a crucible to form a melt, setting a crucible descending speed and a heater power curve, reducing the temperature of the bottom of the crucible after the crucible descends, and separating out crystals from the bottom of the crucible, wherein impurities and volatile impurities are gradually separated out;
4. along with the longitudinal continuous movement of the crucible, the melt raw material in the crucible is finally crystallized completely to obtain the primary pure raw material;
5. and cooling the primary pure raw material, taking out, and removing impurities to obtain the purified calcium fluoride raw material.
It was examined that the single crystal ratio, time and purity of the purified calcium fluoride raw material prepared in example 1 and comparative example 6 were different, and specific reference may be made to table 3:
TABLE 3 Single Crystal Rate, time and purity of purified calcium fluoride raw Material
| Single crystal yield (%) | Time (h) | Purity (%) | |
| Example 1 | 75 | 100 | 99.9999 |
| Comparative example 6 | 55 | 120 | 99.999 |
According to the data in Table 3, the high purity calcium fluoride raw material prepared in example 1 has a much higher single crystal rate than the calcium fluoride raw material prepared in comparative example 6 under the condition of almost the same purity, and it is proved that the use of the annular heater with a smaller width to move along the horizontal direction can ensure a sufficiently small temperature gradient in a relatively smaller melting zone, solute transport is basically dependent on the concentration difference in the horizontal direction, the crystallization process advances from one side to the other side, the uniformity of the raw material after melting to crystallization is higher, the probability of parasitic nucleation is lower, and a large number of polycrystal and defect inside a crystal lump can be effectively avoided.
To sum up: according to the application, the crucible is designed to be an open bevel, the crucible is communicated with the internal environment of the furnace body, and gas in the furnace body can freely flow in the crucible and the furnace body. Simultaneously, the crucible is fixed in the furnace body, so that the graphite resistance heating ring horizontally moves to heat and melt the calcium fluoride raw material in the crucible, the melt in the crucible is uniformly crystallized from one side to the other side along the horizontal direction by adjusting the moving speed and the temperature of the graphite resistance heating ring, the concentration difference of impurity ions is formed in the melt, the precipitated impurities migrate from high concentration to low concentration, finally, the impurities are formed to be biased at one end of the raw material, and the concentration of the impurities is distributed from small to large. Avoiding the occurrence of inconsistent impurity removal steps, complex convection environment and the like, and improving the purification effect and single crystal rate of the calcium fluoride crystal.
The above embodiments are not intended to limit the scope of the present application, so: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.
Claims (10)
1. A purifying treatment device for a calcium fluoride crystal growth raw material is characterized in that: the device comprises a water-cooling furnace body, a vacuum system for adjusting the atmosphere inside the furnace body and an air charging pipeline, wherein a crucible, a sleeve, a heater and an insulating layer are arranged in the furnace body, the upper end of the crucible is in an opening shape and is in clearance fit with the sleeve, the insulating layer is positioned outside the sleeve, a channel is reserved between the insulating layer and the outer wall of the sleeve, and the heater is horizontally arranged in the channel in a sliding manner.
2. The purification treatment apparatus for calcium fluoride crystal growth raw material according to claim 1, wherein: the heater is a graphite resistance heating ring or a ceramic heating ring, the heater is wound around the circumference of the sleeve in a circle, and the ratio of the width of the heater in the horizontal direction to the length of the sleeve is (0.5-1.5): 5.
3. The purification treatment apparatus for calcium fluoride crystal growth raw material according to claim 1, wherein: the two sides of the crucible are inclined outwards, and the bottom wall of the crucible is horizontal.
4. The purification treatment apparatus for calcium fluoride crystal growth raw material according to claim 2, wherein: the heater carries out horizontal slip through transmission, transmission includes transfer line and actuating device, the transfer line is fixed in on the heater, actuating device is located outside the furnace body, actuating device passes through the transfer line drive the heater horizontal slip.
5. The purification treatment apparatus for calcium fluoride crystal growth raw material according to claim 4, wherein: and a sealing ring is arranged at the joint of the transmission rod and the furnace body.
6. The purification treatment apparatus for calcium fluoride crystal growth raw material according to any one of claims 1 to 5, wherein: the crucible and the sleeve are made of graphite, and ash content A of the graphite is less than 20ppm.
7. A purification treatment method of a calcium fluoride crystal growth raw material is characterized in that: the method using the apparatus of any one of claims 1-6, the method comprising:
placing raw materials into the crucible, adding an deoxidizer, vacuumizing, and sequentially filling inert gas and fluorine-containing reaction gas into the furnace body;
moving the heater to the first end of the crucible to heat the raw material in the crucible, wherein the area in the crucible corresponding to the heater is a melting area;
after the raw materials in the melting zone are melted, the heater is used for heatingThe crucible moves at a uniform speed towards the second end of the crucible, when the heater passes, the crucible is heated to be in a melt shape corresponding to the raw material in the melting zone, and after the heater passes, the raw material in the melt shape is re-solidified into a crystalline shape, and the equilibrium segregation coefficient k in the raw material 0 Impurities less than 1 migrate from the crystallization side to the melt side in the crucible in sequence and finally concentrate at the second end of the crucible to obtain an initial pure raw material with an impurity surface layer at one end;
and removing the impurity surface layer of the initial pure raw material to obtain the high-purity raw material for calcium fluoride crystal growth.
8. The method for purifying a calcium fluoride crystal growth raw material according to claim 7, wherein: the fluorine-containing reaction gas is carbon tetrafluoride or trifluoromethane.
9. The method for purifying a calcium fluoride crystal growth raw material according to claim 7, wherein: the rate of uniform movement of the heater toward the second end of the crucible is 0.5-2.5mm/hr.
10. The method for purifying a calcium fluoride crystal growth raw material according to claim 7, wherein: the deoxidizer is zinc fluoride, and the zinc fluoride accounts for 0.02-0.07wt% of the weight of the raw materials.
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| CN101643936A (en) * | 2008-10-16 | 2010-02-10 | 温州大学 | Horizontal growth method for lead tungstate scintillation crystal |
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