CN109267147A - A kind of silica crucible and its method using silica crucible drawing silicon single crystal - Google Patents
A kind of silica crucible and its method using silica crucible drawing silicon single crystal Download PDFInfo
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- CN109267147A CN109267147A CN201811443842.9A CN201811443842A CN109267147A CN 109267147 A CN109267147 A CN 109267147A CN 201811443842 A CN201811443842 A CN 201811443842A CN 109267147 A CN109267147 A CN 109267147A
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- silica crucible
- coating
- crucible
- barium
- layer
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 488
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 202
- 239000013078 crystal Substances 0.000 title claims abstract description 88
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 85
- 239000010703 silicon Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 26
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 193
- 238000000576 coating method Methods 0.000 claims abstract description 95
- 239000011248 coating agent Substances 0.000 claims abstract description 93
- 210000004276 hyalin Anatomy 0.000 claims abstract description 88
- 239000002131 composite material Substances 0.000 claims abstract description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 24
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 19
- 229910052786 argon Inorganic materials 0.000 claims abstract description 12
- 239000010453 quartz Substances 0.000 claims description 44
- 229910052916 barium silicate Inorganic materials 0.000 claims description 40
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 claims description 40
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052788 barium Inorganic materials 0.000 claims description 18
- 239000006004 Quartz sand Substances 0.000 claims description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 32
- 230000007797 corrosion Effects 0.000 abstract description 32
- 230000009467 reduction Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 69
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 57
- 235000012239 silicon dioxide Nutrition 0.000 description 43
- 239000002994 raw material Substances 0.000 description 41
- 239000000463 material Substances 0.000 description 37
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 26
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 26
- 229910052906 cristobalite Inorganic materials 0.000 description 26
- 238000002425 crystallisation Methods 0.000 description 24
- 230000008025 crystallization Effects 0.000 description 24
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical group [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 23
- 229910001863 barium hydroxide Inorganic materials 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 238000000280 densification Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052571 earthenware Inorganic materials 0.000 description 10
- 229920005591 polysilicon Polymers 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000004575 stone Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002210 silicon-based material Substances 0.000 description 7
- 239000013589 supplement Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 1
- UDOGMPLCFFMHNN-UHFFFAOYSA-N [Ba].O[Si](O)(O)O Chemical group [Ba].O[Si](O)(O)O UDOGMPLCFFMHNN-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007569 slipcasting Methods 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/10—Crucibles or containers for supporting 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
- C30B15/02—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
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention provides a kind of silica crucible and its method using silica crucible drawing silicon single crystal, including bubble composite layer, hyaline layer and coating, coating includes first coating and second coating, and bubble composite layer, hyaline layer, first coating and second coating are set gradually from outside to inside；The flow for taking section to throw the stage again in pulling of crystals, putting into a certain amount of barium carbonate, while taking section to throw stage argon gas again described in controlling.The beneficial effects of the invention are as follows making silica crucible structure simple, easy to use, convenient for using when pulling of crystals, with barium carbonate coating, corrosion of the reduction silicon solution to the inner wall of silica crucible improves the service life of silica crucible.
Description
Technical field
The invention belongs to the technical fields of pulling of crystals, draw more particularly, to a kind of silica crucible and its using silica crucible
The method of silicon single crystal processed.
Background technique
Existing crystal pulling is made of with silica crucible two parts, and outside is that one layer of region with high bubble density is gas
Bubble composite layer and inside are the hyaline layers of 3-5mm, so as to improve monocrystalline crystal forming rate and quality.But since silicon is in molten condition
Down with the chemical activity of height, it can react with silica crucible, i.e. SiO2+Si → 2SiO, during this, the oxygen of generation
SiClx enters in molten silicon, so that the crystal structure in being growing changes, generate dislocation makes to influence monocrystalline Cheng Jing
It is of poor quality to obtain monocrystalline.
Summary of the invention
In view of the above problems, it is drawn the problem to be solved in the present invention is to provide a kind of silica crucible and its using silica crucible
The method of silicon single crystal is especially suitable for using during pulling of crystals, has barium silicate structure, can reduce silicon solution to quartzy earthenware
The corrosion of crucible enhances the intensity of silica crucible, reduces temperature distortion, improves its service life.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of silica crucible, including bubble are compound
Layer, hyaline layer and coating, coating include first coating and second coating, and bubble composite layer, hyaline layer, first coating are applied with second
Layer is set gradually from outside to inside.
Further, first coating is barium carbonate.
Further, second coating is barium silicate.
Further, the sum of thickness of bubble composite layer and hyaline layer is constant.
Further, the quartz sand purity of bubble composite layer is less than hyaline layer quartz sand purity.
Further, hyaline layer quartz sand purity is 99.9999%.
A method of silicon single crystal is drawn using Novel quartz crucible, takes section to throw again the stage in pulling of crystals, investment is certain
The barium carbonate of amount, while controlling the flow for taking section to throw stage argon gas again.
Further, the amount of barium carbonate is 2-5g.
Further, the flow of argon gas is 100-120slpm.
Further, it takes section to throw the stage again every time during pulling of crystals and barium carbonate is added.
The advantages and positive effects of the present invention are:
1. it is easy to use due to the adoption of the above technical scheme, so that silica crucible structure is simple, convenient for making when pulling of crystals
With with barium carbonate coating, corrosion of the reduction silicon solution to the inner wall of silica crucible improves the service life of silica crucible；
2. barium carbonate is decomposed to form barium monoxide during pulling of crystals, occur with the hyaline layer of inner wall of quartz crucible anti-
Barium silicate should be generated, which is one layer and causes small cristobalite crystallization, reduces silicon solution to inner wall of quartz crucible
Corrosion, enhances the intensity of silica crucible, reduces its temperature distortion, while improving the service life of silica crucible, and then improves
The yield of pulling of crystals；
3. adding barium carbonate, the barium silicate that supplement inner wall of quartz crucible falls off during pulling of crystals takes section to throw again
Coating reduces corrosion of the silicon solution to inner wall of quartz crucible with this, improves the service life of silica crucible, enhance silica crucible
Intensity reduces its temperature distortion, and then improves the yield of pulling of crystals, improves production efficiency.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of one embodiment of the invention.
In figure:
1, bubble composite layer 2, hyaline layer 3, coating
Specific embodiment
The present invention is further illustrated in the following with reference to the drawings and specific embodiments.
Fig. 1 shows the structural schematic diagram of one embodiment of the invention, and the structure of the present embodiment, the present embodiment has been shown in particular
It is related to a kind of silica crucible for improving charging capacity of single crystal furnace, for using when pulling of crystals, which has multilayered structure,
The small cristobalite crystallization of one layer of densification can be formed on silica crucible crucible wall, enhances crucible during pulling of crystals
Service life prevents corrosion of the silicon solution to silica crucible, improves the crystal forming rate of pulling of crystals, while enhancing silica crucible
Intensity improves the production capacity of pulling of crystals production.
A kind of silica crucible of above-mentioned raising charging capacity of single crystal furnace, including bubble composite layer 1, hyaline layer 2 and coating 3,
Bubble composite layer 1, hyaline layer 2 and coating 3 are set gradually from outside to inside, wherein and coating 3 includes first coating and second coating,
Bubble composite layer 1, hyaline layer 2, first coating and second coating are set gradually from outside to inside, it is, the silica crucible includes
Bubble composite layer 1, transparent 2, first coating and second coating four-layer structure, the four-layer structure are set gradually from outside to inside, the gas
Bubble composite layer 1 is one layer of area level with high bubble density, and it is uniform radiation by heater that setting bubble composite layer 1, which acts on,
Provided radiant heat source, the hyaline layer 2 are that have certain thickness hyaline layer, and the effect of hyaline layer 2 is to reduce to connect with solution
The bubble density in region is touched, first coating is a baric coating, and the effect of the first coating is the silicon solution pair reduced in crucible
The corrosion of crucible internal walls, second coating are the small cristobalite crystallization of one layer of densification, and the effect of second coating is reduced in crucible
Silicon solution corrosion, enhance the service life of crucible, meanwhile, which can enhance the intensity of silica crucible, extend
The service life of silica crucible.
Specifically, which is bowl structure, including superstructure and bottom structure, one end and bottom of superstructure
Portion's structure is fixedly connected, and here, superstructure is preferably integrally formed with the mode that is fixedly connected of bottom structure, stable structure,
It is unlikely to deform, convenient for using when pulling of crystals, and superstructure and substructure junction have the angle R of certain angle.Here,
Superstructure is the cylindrical structure that there is cavity in inside, and substructure is the groove structure being recessed inwardly, the cavity of superstructure
The inner space constituted with the groove of bottom structure is the space that the silica crucible contains silicon solution, and polycrystalline silicon material is placed in the stone
In English crucible, polycrystalline silicon material is heated by the heater of czochralski crystal growing furnace so that polycrystalline silicon material melt, by seeding,
Undergauge turns the drawing that the processes such as shoulder, expansion shoulder, isometrical, ending carry out silicon single crystal rod.
The superstructure is the cylindrical structure that there are cavity and upper and lower opening in inside, which includes from outside to inside
Set gradually bubble composite layer 1, hyaline layer 2, first coating and second coating, bubble composite layer 1 and hyaline layer 2 by slip casting,
The processes such as demoulding, firing are made, so as to form the bowl-shape silica crucible with bubble composite layer 1 and hyaline layer 2, bubble
Composite layer 1 and hyaline layer 2 are made by quartz sand, and the quartz sand purity of hyaline layer 2 is greater than the quartz of bubble composite layer 1
The purity of sand purity, the quartz sand of hyaline layer 2 is greater than 99.9999%, is glass sand, reduces the miscellaneous of silica crucible hyaline layer
Matter, and then the impurity that silica crucible causes entry into monocrystalline when carrying out pulling of crystals is reduced, it avoids due to silica crucible impurity mistake
Resistivity that is more and influencing monocrystalline, the hyaline layer 2 with a thickness of 3-5mm, it is preferred that the hyaline layer 2 with a thickness of 4mm, be convenient for
Reduce the bubble density with solution contact area.The sum of the thickness of the hyaline layer 2 on top and bubble composite layer 1 substantially constant is not
Become, constant dimension is kept convenient for silica crucible, convenient for being installed in pulling of crystals.
Substructure is, convenient for the installation of polycrystalline silicon material, to reduce in silica crucible bottom with the groove being recessed inwardly
The damage of wall.Substructure includes successively from outside to inside bubble composite layer 1 and hyaline layer 2, and consistent with superstructure, bubble is compound
Layer 1 is made with hyaline layer 2 by quartz sand, and the purity of the quartz sand of hyaline layer 2 is greater than the quartz sand of bubble composite layer 1
The purity of purity, the incorporation of impurity when reducing pulling of crystals, the quartz sand of hyaline layer 2 is greater than 99.9999%, so as to improve quartz
The purity of crucible.The hyaline layer 2 with a thickness of 3-7mm, preferably 5mm, can reduce in the bubble density of solution contact area,
So as to improve monocrystalline crystal forming rate.The sum of thickness of bubble composite layer 1 and hyaline layer 2 in substructure keeps substantially constant, just
In the constant dimension for keeping silica crucible.It is fixedly connected in the upper end of substructure with one end of superstructure, and lower part
Structure has the angle R of certain angle, which is located at the lower part of substructure and superstructure junction, since silica crucible exists
When carrying out pulling of crystals, when the silicon solution in silica crucible is located at the either angle R of the angle R top, answering for polycrystalline silicon raw material is carried out
It throws, the hyaline layer 2 of substructure contacts with silicon solution always, to reduce reacting for silicon solution and hyaline layer 2, reduction silicon solution pair
The corrosion of inner wall of quartz crucible enhances the intensity of silica crucible, and the wall thickness of substructure is greater than the wall thickness of superstructure, and in silicon
The angle R of liquid level of solution stops and 2 thickness of hyaline layer at the top of the angle R are greater than 1 thickness of bubble composite layer, enhance quartzy earthenware with this
The intensity of crucible, it is, 2 thickness of hyaline layer at this increases accordingly, the thickness of bubble composite layer 1 accordingly reduces, wall thickness at this
Thickness remain unchanged.
The silica crucible is mounted in czochralski crystal growing furnace, and bubble composite layer 1 has bubble, can be by the radiant heat of heater
Source homogenization, so that polycrystalline silicon raw material fusing is uniformly, improves vertical pulling convenient for providing uniform heat to polycrystalline silicon raw material in crucible
The quality of seeding when monocrystalline.Hyaline layer 2 does not have bubble, and the purity of the quartz sand of hyaline layer is greater than the pure of bubble composite layer 1
Degree, so that hyaline layer 2 can reduce the bubble density with solution contact area, so as to improve monocrystalline crystal forming rate and quality.The stone
The bubble composite layer 1 of English crucible and the material of hyaline layer 2 are quartz sand, which includes silica composition, due to silicon
It in the molten state with the chemical reaction of height, can react, react as follows: SiO2+ with the silica of hyaline layer 2
Si → 2SiO, resulting silica enter in silicon solution, so that the crystal structure in being growing changes, generate position
Mistake influences the Cheng Jing of monocrystalline, meanwhile, a large amount of pin holes are formed in hyaline layer, pin hole is more, illustrates that the impurity entered in silicon solution is got over
More, the Cheng Jingyue of monocrystalline is poor, so, first coating is set on the surface of hyaline layer 2, reduces the anti-of silicon solution and silica
It answers, first coating is formed by coating one layer of barium powder solution in hyaline layer 2 here, it is preferred that here, barium powder is hydroxide
Barium, the barium hydroxide are the barium hydroxide containing the crystallization water, which is dissolved in pure water, the barium hydroxide of saturation is formed
The baryta water of the saturation is coated in the surface of the hyaline layer 2 of silica crucible, this layer of barium hydroxide coating by aqueous solution
It can be reacted with the carbon dioxide in air after complete, form barium carbonate, so as to form first coating, reduce silicon solution to quartz
The corrosion of crucible hyaline layer.
The crucible for forming first coating is placed on single crystal growing furnace, after crucible is heated, barium carbonate resolves into barium monoxide, oxygen
The hyaline layer for changing barium and silica crucible reacts, and BaCO3+SiO2 → (high temperature) BaSiO3+CO2 ↑, due to depositing for barium silicate
So that the small cristobalite crystallization of one layer of densification is formed on silica crucible wall, to slow down silica crucible by silicon solution corrosion
Degree.So as to form second coating, i.e. second coating is barium silicate, and barium silicate is the small cristobalite crystallization of one layer of densification,
Party's quartz crystals are difficult to be permeated by silicon solution and peel off, and can be dissolved by silicon solution after peeling, can significantly improve stone
The service life of English crucible and long brilliant yield, while the intensity of silica crucible can be increased, reduce hot mastication phenomenon.
In use, with using the time increasingly longer, the barium silicate of the second coating can fall off silica crucible, at this point,
Barium carbonate is added in the crucible of heating, which is thermally decomposed into barium monoxide, barium monoxide and silicon dioxde reaction, generates silicic acid
Barium forms second coating again, the service life and long brilliant yield to supplement the barium silicate to fall off, so as to improve silica crucible.
Through the above it is recognised that the method for improving the silica crucible service life, can take section in pulling of crystals
When throwing again, it is added a certain amount of barium carbonate, supplements silica crucible inner wall surface barium silicate during pulling of crystals and fall off, with
This extend silica crucible service life, this method specifically includes the following steps:
Step 1: silica crucible is before carrying out polycrystalline silicon charge, on the inner surface of the hyaline layer 2 of the inner wall of silica crucible
The solution that the barium powder of production first coating is coated using coated tool, by coating one layer of hydroxide on the inner wall of silica crucible
Carbon dioxide reaction in the saturated solution of barium, barium hydroxide and air forms barium carbonate, i.e. first coating.Specifically, hydrogen-oxygen
It is soluble easily in water to change barium, the barium hydroxide powder containing the crystallization water is dissolved in pure water, forms barium hydroxide saturated aqueous solution, uses
The barium hydroxide saturated aqueous solution is coated on the inner surface of the hyaline layer 2 of silica crucible by the coated tools such as brush, coating machine,
One layer of barium hydroxide coating is formed on hyaline layer 2, after coating, barium hydroxide reacts with the carbon dioxide in air, shape
At barium carbonate, one layer of barium carbonate coating is formed on inner wall of quartz crucible.Barium carbonate coating can reduce silicon solution to quartzy earthenware
The corrosion of crucible hyaline layer 2 extends the service life of silica crucible.
Step 2: being packed into polycrystalline silicon raw material into the silica crucible with barium carbonate coating, and by the quartzy earthenware after charging
Crucible is mounted on czochralski crystal growing furnace, carries out pulling of crystals.Silica crucible is heated the heating of device, stone during pulling of crystals
English crucible temperature increases, the setting of bubble composite layer 1, so that the polycrystalline silicon raw material in silica crucible is heated evenly melting, quartz
Barium carbonate coating on crucible hyaline layer 2 is thermally decomposed, and barium monoxide is formed, and the hyaline layer 2 in barium monoxide and silica crucible occurs
Reaction forms barium silicate, due to the presence of barium silicate, so that forming the small cristobalite knot of one layer of densification on silica crucible wall
Crystalline substance extends the service life of silica crucible to slow down silica crucible by the degree of silicon solution corrosion.Used in silica crucible
During, the coating that barium carbonate is mixed with barium silicate is formed on the surface of hyaline layer 2, extends the use longevity of silica crucible with this
Life, meanwhile, improve the intensity of silica crucible.
Step 3: with the increase of single crystal growing furnace runing time during pulling of crystals, inner wall of quartz crucible extent of corrosion increases
Add, the barium carbonate on 2 surface of hyaline layer is completely converted into barium silicate, and with the increase for using the time, barium silicate falls off, in hyaline layer
2 surfaces form pin hole, so that silicon solution, which enters inner wall of quartz crucible by pin hole, carries out corruption to hyaline layer 2 and bubble composite layer 1
Erosion, so that the bubbles burst in silica crucible, foreign gas enters silicon solution by the pin hole on coating in bubble, molten into silicon
Impurity in liquid is more, causes the poorer at crystalloid amount of monocrystalline.So after first time during pulling of crystals takes section, into
While row polycrystalline silicon material is thrown again, barium carbonate is added in the silicon solution into silica crucible, barium carbonate is heated in silicon solution to be divided
Solution, resolves into barium monoxide, and barium monoxide reacts again with the silica at coating pin hole, barium silicate is generated, in the pin hole
Place forms cristobalite crystallization, and reduction silicon solution reacts with silica crucible, enhances the service life of silica crucible, reduces and enter silicon solution
In foreign gas, improve the crystal forming rate of pulling of silicon single crystal after multiple throw.
The detailed process of barium carbonate is added when section being taken to throw again are as follows:
Step 1, during pulling of crystals, monocrystalline length growth reach take section require after carry out ending take section, after taking section
Resistivity measurement is carried out to the monocrystalline at monocrystalline ending, measure the surplus material weight in silica crucible and carries out the calculating of resistivity,
The weight for the polysilicon that need to be thrown again and the weight of doping up alloy are calculated according to resistivity and fractional condensation meter, while calculating required carbonic acid
The weight of barium；
Step 2 carries out the weighing of barium carbonate, and load weighted barium carbonate is encapsulated in pan feeding block, expects that the material of block is polycrystalline
Silicon reduces the impurity entered in silicon solution, which includes material block body, the first plugging block and the second plugging block, in material block sheet
There is a cavity of about one connection in the centre of body, the shape of cavity with first block it is block-shaped and second block it is block-shaped adaptable,
Here, the first plugging block is identical as the shape of the second plugging block, and the first plugging block and the second plugging block are separately mounted to material block sheet
Barium carbonate is encapsulated in the cavity of material block body by the both ends of body.Specifically, material block body can be rectangular parallelepiped structure, can also
It to be square cylindrical body or other shapes, is selected according to actual needs, expects the sky among block body
The shape of chamber can be cylinder, be also possible to taper, square rectangle or other shapes, root
It is selected according to actual demand, does not do specific requirement here.The shape size of first plugging block and the second plugging block and material block sheet
The shape size of the cavity of body is adapted, and the both ends of cavity is separately mounted to convenient for the first plugging block and the second plugging block, to material
The both ends of the cavity of block body are blocked, and barium carbonate is placed in the cavity of material block body, are located at the first plugging block and second
In the space that plugging block and cavity are constituted, barium carbonate is encapsulated in material block body, multiple throwing process argon gas is avoided to take away barium carbonate,
Electrode column is caused to strike sparks, in the silicon solution after enabling barium carbonate to be melted in multiple throwing completely, in inner wall of quartz crucible surface shape
At the small cristobalite crystallization of one layer of densification, corrosion of the silicon solution to inner wall of quartz crucible is reduced.
Here, the weight of barium carbonate is 2-5g, is selected according to the size of resistivity value at monocrystalline ending, so that quartzy
Crucible in use, to the supplement of the barium silicate on inner wall of quartz crucible surface, reduces silicon solution to inner wall of quartz crucible
Corrosion, improves the intensity of silica crucible.
Polycrystalline silicon raw material is packed into multiple throwing cylinder, while the material block for being packaged with barium carbonate is also loaded onto multiple throwing cylinder by step 3
Interior, when carrying out multiple throw, the material block for being packaged with barium carbonate is put into silica crucible together with polycrystalline silicon raw material, and heated point of barium carbonate
The hyaline layer of Xie Hou, formation barium monoxide, barium monoxide and silica crucible reacts, and barium silicate is generated, in inner wall of quartz crucible shape
At the small cristobalite crystallization of one layer of densification, corrosion of the silicon solution to silica crucible is reduced, extends the use of silica crucible with this
Service life.
During pulling of crystals, a barium carbonate can be carried out with being added again into multiple barium carbonate can also be carried out
With being added again into being selected according to actual needs, extend the service life of silica crucible with this.
A kind of silica crucible coating process again, that is, secondary coating again is carried out to silica crucible, enhance silica crucible
Intensity reduces corrosion of the silicon solution to the inner wall of silica crucible, and coating process is to take section in pulling of crystals to the silica crucible again
Throwing the stage again is added barium carbonate, and barium carbonate enters after silica crucible at the angle R for being located at silica crucible, the angle R to silica crucible and
Inner wall of quartz crucible carries out coating, specifically includes the following steps:
Step 1: silica crucible is before carrying out polycrystalline silicon charge, on the inner surface of the hyaline layer 2 of the inner wall of silica crucible
The solution that the barium powder of production first coating is coated using coated tool, by coating one layer of hydroxide on the inner wall of silica crucible
Carbon dioxide reaction in the saturated solution of barium, barium hydroxide and air forms barium carbonate, i.e. first coating.Specifically, hydrogen-oxygen
It is soluble easily in water to change barium, the barium hydroxide powder containing the crystallization water is dissolved in pure water, forms barium hydroxide saturated aqueous solution, uses
The barium hydroxide saturated aqueous solution is coated on the inner surface of the hyaline layer 2 of silica crucible by the coated tools such as brush, coating machine,
One layer of barium hydroxide coating is formed on hyaline layer 2, after coating, barium hydroxide reacts with the carbon dioxide in air, shape
At barium carbonate, one layer of barium carbonate coating is formed on inner wall of quartz crucible.Barium carbonate coating can reduce silicon solution to quartzy earthenware
The corrosion of crucible hyaline layer 2 extends the service life of silica crucible.
Step 2: being packed into polycrystalline silicon raw material into the silica crucible with barium carbonate coating, and by the quartzy earthenware after charging
Crucible is mounted on czochralski crystal growing furnace, carries out pulling of crystals.Silica crucible is heated the heating of device, stone during pulling of crystals
English crucible temperature increases, the setting of bubble composite layer 1, so that the polycrystalline silicon raw material in silica crucible is heated evenly melting, quartz
Barium carbonate coating on crucible hyaline layer 2 is thermally decomposed, and barium monoxide is formed, and the hyaline layer 2 in barium monoxide and silica crucible occurs
Reaction forms barium silicate, due to the presence of barium silicate, so that forming the small cristobalite knot of one layer of densification on silica crucible wall
Crystalline substance extends the service life of silica crucible to slow down silica crucible by the degree of silicon solution corrosion.Used in silica crucible
During, the coating that barium carbonate is mixed with barium silicate is formed on the surface of hyaline layer 2, extends the use longevity of silica crucible with this
Life, meanwhile, improve the intensity of silica crucible.
Step 3: with the increase of single crystal growing furnace runing time during pulling of crystals, inner wall of quartz crucible extent of corrosion increases
Add, the barium carbonate on 2 surface of hyaline layer is completely converted into barium silicate, and with the increase for using the time, barium silicate falls off, in hyaline layer
2 surfaces form pin hole, so that silicon solution, which enters inner wall of quartz crucible by pin hole, carries out corruption to hyaline layer 2 and bubble composite layer 1
Erosion, so that the bubbles burst in silica crucible, foreign gas enters silicon solution by the pin hole on coating in bubble, molten into silicon
Impurity in liquid is more, causes the poorer at crystalloid amount of monocrystalline.So after first time during pulling of crystals takes section, into
While row polycrystalline silicon material is thrown again, barium carbonate is added in the silicon solution into silica crucible, barium carbonate is heated in silicon solution to be divided
Solution, resolves into barium monoxide, and barium monoxide reacts again with the silica at coating pin hole, barium silicate is generated, in the pin hole
Place forms cristobalite crystallization, and reduction silicon solution reacts with silica crucible, enhances the service life of silica crucible, reduces and enter silicon solution
In foreign gas, improve the crystal forming rate of pulling of silicon single crystal after multiple throw.
The detailed process of barium carbonate is added when section being taken to throw again are as follows:
Step 1, during pulling of crystals, monocrystalline length growth reach take section require after carry out ending take section, after taking section
Resistivity measurement is carried out to the monocrystalline at monocrystalline ending, measure the surplus material weight in silica crucible and carries out the calculating of resistivity,
The weight for the polysilicon that need to be thrown again and the weight of doping up alloy are calculated according to resistivity and fractional condensation meter, while calculating required carbonic acid
The weight of barium；
Step 2 carries out the weighing of barium carbonate, and load weighted barium carbonate is encapsulated in pan feeding block, expects that the material of block is polycrystalline
Silicon reduces the impurity entered in silicon solution, which includes material block body, the first plugging block and the second plugging block, in material block sheet
There is a cavity of about one connection in the centre of body, the shape of cavity with first block it is block-shaped and second block it is block-shaped adaptable,
Here, the first plugging block is identical as the shape of the second plugging block, and the first plugging block and the second plugging block are separately mounted to material block sheet
Barium carbonate is encapsulated in the cavity of material block body by the both ends of body.Specifically, material block body can be rectangular parallelepiped structure, can also
It to be square cylindrical body or other shapes, is selected according to actual needs, expects the sky among block body
The shape of chamber can be cylinder, be also possible to taper, square rectangle or other shapes, root
It is selected according to actual demand, does not do specific requirement here.The shape size of first plugging block and the second plugging block and material block sheet
The shape size of the cavity of body is adapted, and the both ends of cavity is separately mounted to convenient for the first plugging block and the second plugging block, to material
The both ends of the cavity of block body are blocked, and barium carbonate is placed in the cavity of material block body, are located at the first plugging block and second
In the space that plugging block and cavity are constituted, barium carbonate is encapsulated in material block body, multiple throwing process argon gas is avoided to take away barium carbonate,
Electrode column is caused to strike sparks, in the silicon solution after enabling barium carbonate to be melted in multiple throwing completely, in inner wall of quartz crucible surface shape
At the small cristobalite crystallization of one layer of densification, corrosion of the silicon solution to inner wall of quartz crucible is reduced.
Here, the weight of barium carbonate is 2-5g, is selected according to the size of resistivity value at monocrystalline ending, so that quartzy
Crucible in use, to the supplement of the barium silicate on inner wall of quartz crucible surface, reduces silicon solution to inner wall of quartz crucible
Corrosion, improves the intensity of silica crucible.
Polycrystalline silicon raw material is packed into multiple throwing cylinder, while the material block for being packaged with barium carbonate is also loaded onto multiple throwing cylinder by step 3
Interior, the multiple surface thrown cylinder and be located at silica crucible is convenient for polycrystalline silicon raw material and throws again, polycrystalline silicon raw material be packaged with barium carbonate
Material block be packed into it is multiple throw cylinder when, place one layer of polycrystalline silicon raw material in the multiple bottom for throwing cylinder first, place polysilicon upwards in turn
The block for being packaged with barium carbonate is added at the multiple bottom 1/3 for throwing cylinder of distance, then continues to place polycrystalline into multiple throwing cylinder for raw material
Silicon raw material, it is, the block for being packaged with barium carbonate is located at the inside of polycrystalline silicon raw material in multiple throwing cylinder, by polycrystalline silicon raw material packet
It encloses, when carrying out multiple throw, the material block for being packaged with barium carbonate is put into silica crucible together with polycrystalline silicon raw material, so that being packaged with carbon
The block of sour barium is as polycrystalline silicon raw material is at the tapered angle R for falling into silica crucible in the center of silica crucible, barium carbonate
After being thermally decomposed, barium monoxide is formed, barium monoxide reacts with the hyaline layer at the angle silica crucible R, barium silicate is generated, in quartz
The small cristobalite crystallization of one layer of densification is formed at the angle crucible R, and secondary coating again is carried out to silica crucible, reduces silicon solution to quartz
The corrosion at the angle crucible R, extends the service life of silica crucible with this.Meanwhile with add again into polycrystalline silicon raw material so that stone
Silicon solution is filled in English crucible, as barium carbonate is thermally decomposed, barium silicate is formed, in 2 table of hyaline layer of the inner wall of silica crucible
Face forms the small cristobalite crystallization of one layer of densification, reduces corrosion of the silicon solution to inner wall of quartz crucible, enhances silica crucible
Intensity improves the service life of silica crucible.
A kind of technique of novel drawing silicon single crystal carries out pulling of crystals using silica crucible with multi-layer structure, straight
When crystal-pulling takes section to throw again, a certain amount of barium carbonate is put into, while controlling the flow of argon gas when section being taken to throw again, carry out vertical pulling list
Crystalline substance, specifically includes the following steps:
Step 1: silica crucible is before carrying out polycrystalline silicon charge, on the inner surface of the hyaline layer 2 of the inner wall of silica crucible
The solution that the barium powder of production first coating is coated using coated tool, by coating one layer of hydroxide on the inner wall of silica crucible
Carbon dioxide reaction in the saturated solution of barium, barium hydroxide and air forms barium carbonate, i.e. first coating.Specifically, hydrogen-oxygen
It is soluble easily in water to change barium, the barium hydroxide powder containing the crystallization water is dissolved in pure water, forms barium hydroxide saturated aqueous solution, uses
The barium hydroxide saturated aqueous solution is coated on the inner surface of the hyaline layer 2 of silica crucible by the coated tools such as brush, coating machine,
One layer of barium hydroxide coating is formed on hyaline layer 2, after coating, barium hydroxide reacts with the carbon dioxide in air, shape
At barium carbonate, one layer of barium carbonate coating is formed on inner wall of quartz crucible.Barium carbonate coating can reduce silicon solution to quartzy earthenware
The corrosion of crucible hyaline layer 2 extends the service life of silica crucible.
Step 2: being packed into polycrystalline silicon raw material into the silica crucible with barium carbonate coating, and by the quartzy earthenware after charging
Crucible is mounted on czochralski crystal growing furnace, carries out pulling of crystals.Silica crucible is heated the heating of device, stone during pulling of crystals
English crucible temperature increases, the setting of bubble composite layer 1, so that the polycrystalline silicon raw material in silica crucible is heated evenly melting, quartz
Barium carbonate coating on crucible hyaline layer 2 is thermally decomposed, and barium monoxide is formed, and the hyaline layer 2 in barium monoxide and silica crucible occurs
Reaction forms barium silicate, due to the presence of barium silicate, so that forming the small cristobalite knot of one layer of densification on silica crucible wall
Crystalline substance extends the service life of silica crucible to slow down silica crucible by the degree of silicon solution corrosion.Used in silica crucible
During, the coating that barium carbonate is mixed with barium silicate is formed on the surface of hyaline layer 2, extends the use longevity of silica crucible with this
Life, meanwhile, improve the intensity of silica crucible.
During pulling of crystals, ending for the first time is carried out after the length growth of monocrystalline reaches and section is taken to require and takes section, is taken
After the completion of section, the resistivity at monocrystalline ending is detected, doping up alloy and barium carbonate institute are carried out according to the size of resistivity
The calculating of weight is needed, and is weighed respectively, supplement is added when carrying out pulling of crystals again.The multiple throwing of polycrystalline silicon raw material is carried out,
While progress polycrystalline silicon raw material is thrown again, the multiple throwing of barium carbonate is carried out.Polycrystalline silicon raw material is packed into multiple throwing cylinder, while will envelope
Material block equipped with barium carbonate is also loaded onto multiple throwing cylinder, and the multiple surface thrown cylinder and be located at silica crucible is convenient for polycrystalline silicon raw material
It is multiple to throw, polycrystalline silicon raw material be packaged with the material block of barium carbonate be packed into it is multiple throw cylinder when, place one layer in the multiple bottom for throwing cylinder first
Polycrystalline silicon raw material places polycrystalline silicon raw material upwards in turn, is added at the multiple bottom 1/3-1/2 for throwing cylinder of distance and is packaged with barium carbonate
Block, preferably distance is multiple throws cylinder bottom 1/3, then continues to place polycrystalline silicon raw material into multiple throwing cylinder, it is, being packaged with
The block of barium carbonate is located at the inside of polycrystalline silicon raw material in multiple throwing cylinder, is surrounded by polycrystalline silicon raw material, when carrying out multiple throw, encapsulation
There is the material block of barium carbonate to put into silica crucible together with polycrystalline silicon raw material, so that being packaged with the block of barium carbonate with polysilicon
Raw material is at the tapered angle R for falling into silica crucible in the center of silica crucible, after barium carbonate is thermally decomposed, forms oxidation
Barium, barium monoxide react with the hyaline layer at the angle silica crucible R, generate barium silicate, and one layer of cause is formed at the angle silica crucible R
Close small cristobalite crystallization, carries out secondary coating again to silica crucible, corrosion of the silicon solution to the angle silica crucible R is reduced, with this
Extend the service life of silica crucible.
During high temperature melt, the material block for being packaged with barium carbonate can immerse liquid as the polycrystalline silicon raw material of multiple throwing melts
Face, the material block for being packaged with barium carbonate melt and pass through crucible rotation, and barium carbonate can uniformly fuse into molten silicon, and heated point of barium carbonate
Solution, resolves into barium monoxide, and the silica of the hyaline layer of barium monoxide and silica crucible reacts, and barium silicate is formed, due to silicon
The presence of sour barium forms the small cristobalite crystallization of one layer of densification on the inner wall of silica crucible, enhances the intensity of silica crucible,
Corrosion of the silicon solution to inner wall of quartz crucible is reduced, the service life of silica crucible is improved.
During multiple throwing, the flow of protective gas argon gas is reduced, the flow of argon gas is 100-120slpm.Due to multiple
During throwing, part barium carbonate powder floats with argon gas at heater, due to the Sr element in barium carbonate there are 0.03%, Sr
Element burning point is 800 DEG C, and the burning of Sr element causes heater to generate electric arc, spark phenomenon occurs, influences heater and uses the longevity
Life reduces drifting for barium carbonate, improves the service life of heater so reducing the flow of argon gas during multiple throwing.
Step 3: after the polycrystalline silicon raw material in silica crucible melts, crystal pulling again is carried out, is taken when monocrystalline length is grown into
After segment length, carry out it is secondary take section, it is secondary take section to finish up after, the measurement to resistivity is carried out at monocrystalline ending, according to resistivity
Size, the selection of the dosage of doping up alloy needed for carrying out secondary multiple throwing and barium carbonate, using the secondary multiple throwing of multiple throwings cylinder progress,
Carry out polycrystalline silicon material multiple throwing while, carry out the addition of barium carbonate, repeat the above steps two the step of, carry out polysilicon
While feeding intake, one layer of barium silicate is formed on the inner wall of silica crucible, forms the small cristobalite crystallization of one layer of densification, enhancing
The intensity of silica crucible improves the service life of silica crucible.
Step 4: after secondary multiple throwing, carrying out third time crystal pulling, when the length of monocrystalline is grown into, and section is taken to require, carries out the
Section is taken three times, and after taking section to finish up three times, the measurement to resistivity is carried out at monocrystalline ending carries out three according to the size of resistivity
The selection of the dosage of doping up alloy needed for secondary multiple throwing and barium carbonate is thrown again three times using multiple throwing cylinder, is carrying out polysilicon
Material multiple throwing while, carry out the addition of barium carbonate, repeat the above steps two movement, carry out polysilicon feed intake while,
One layer of barium silicate is formed on the inner wall of silica crucible, is formed the small cristobalite crystallization of one layer of densification, is enhanced silica crucible
Intensity improves the service life of silica crucible.
Step 5: three times it is multiple throw after, carry out the 4th crystal pulling, when the length of monocrystalline is grown into, and section is taken to require, carry out the
Take section for four times, after four times take section to finish up, the measurement to resistivity is carried out at monocrystalline ending carries out four according to the size of resistivity
The selection of the dosage of doping up alloy needed for secondary multiple throwing and barium carbonate carries out four multiple throwings using multiple throwing cylinder, is carrying out polysilicon
Material multiple throwing while, carry out the addition of barium carbonate, repeat the above steps two movement, carry out polysilicon feed intake while,
One layer of barium silicate is formed on the inner wall of silica crucible, is formed the small cristobalite crystallization of one layer of densification, is enhanced silica crucible
Intensity improves the service life of silica crucible.
Continue to repeat step 5, carries out the 5th time and take section and carry out the 5th multiple throwing, successively go on, until quartzy earthenware
Until when crucible reaches service life.Using the above-mentioned novel technique that silicon single crystal is straightened, repeatedly section can be taken to throw again, it is existing
Pulling of crystals technique can at most carry out 2 multiple throw and operate, and monocrystalline inventory is thrown at 500-650 kilograms using above-mentioned new process again
Number can reach 3-4 times, or more, and monocrystalline inventory improves production capacity at 950-1200 kilograms, reduces production cost.
It needs to control in the weight that pulling of crystals takes section to be added again into barium carbonate, it, should to control the influence to silica crucible
The method for controlling barium carbonate dosage, takes section to throw the stage again for pulling of crystals, when taking section to throw again, puts into polycrystalline using multiple throwing cylinder
While silicon raw material, barium carbonate is put into, barium carbonate thermally decomposed, resolve into barium monoxide, the inner wall of barium monoxide and silica crucible
Hyaline layer reacts, and generates barium silicate, and due to the presence of barium silicate, it is small that one layer of densification is formed on inner wall of quartz crucible
Cristobalite crystallization reduces corrosion of the silicon solution to inner wall of quartz crucible, improves the service life of silica crucible.It is being added again into carbon
The dosage of barium carbonate need to be controlled when sour barium, the weight of barium carbonate more or less can all generate different influences to silica crucible, into
And the using effect of monocrystalline is influenced, it is analyzed as follows table:
It is possible thereby to know, when taking section to throw again, the dosage of barium carbonate need to be controlled, so that silica crucible, which reaches best, to be made
With effect, extend the service life of silica crucible, barium carbonate with amount control method the following steps are included:
Step 1: the area of the inner surface of silica crucible is calculated: since when taking section to throw again, barium carbonate is more with multiple throwing
Crystal silicon raw material is put into silica crucible together, the silicon dioxde reaction of the hyaline layer 2 of barium carbonate and quartz crucible inner surface, and multiple
It is covered with silica crucible after polycrystalline silicon raw material melting after throwing, so, before adding barium carbonate again, to the interior table of silica crucible
Face area is calculated, calculating process are as follows:
The area for calculating silica crucible upright side walls is calculated according to periphery product；
The surface area for calculating silica crucible bottom, is calculated according to round area；
Surface area at the angle R is calculated, is calculated according to sectorial area；
It calculates the sum of the area of silica crucible upright side walls, the surface area of bottom and area at the angle R and obtains silica crucible
Inner surface area；
Step 2: according to the density of the inner surface area of silica crucible and barium carbonate, required barium carbonate in computational theory
Weight；
Step 3: when taking section to throw again, measurement takes the surplus material in the resistivity and silica crucible of the monocrystalline of section, needed for calculating
The weight of polycrystalline silicon raw material is put into, and selects certain coefficient according to the size of resistivity, carries out the practical heavy of required barium carbonate
Amount.Here, which is 0.2-0.5, is selected according to the size of actual resistivity.The weight of actually required barium carbonate is reason
By the weight of upper barium carbonate multiplied by obtained by the coefficient.
Step 4: the barium carbonate applying electronic balance of required weight is weighed, and is encapsulated in material block, with polysilicon
Raw material is added in silica crucible when taking section to throw again together, and barium carbonate forms barium monoxide, barium monoxide and quartzy earthenware after being thermally decomposed
Hyaline layer reaction at the pin hole of crucible inner wall, generates barium silicate, forms the small cristobalite of one layer of densification in inner wall of quartz crucible
Crystallization enhances the intensity of silica crucible, reduces silica crucible temperature distortion, improves the service life of silica crucible.
The advantages and positive effects of the present invention are: due to the adoption of the above technical scheme, so that silica crucible structure letter
It is single, it is easy to use, convenient for using when pulling of crystals, there is barium carbonate coating, reduce corruption of the silicon solution to the inner wall of silica crucible
Erosion, improves the service life of silica crucible；During pulling of crystals, barium carbonate is decomposed to form barium monoxide, in silica crucible
The hyaline layer of wall, which reacts, generates barium silicate, which is one layer and causes small cristobalite crystallization, reduces silicon solution
Corrosion to inner wall of quartz crucible enhances the intensity of silica crucible, reduces its temperature distortion, while improving making for silica crucible
With the service life, and then improve the yield of pulling of crystals；During pulling of crystals takes section to throw again, barium carbonate is added, supplements stone
The barium silicate coating that English crucible internal walls fall off reduces corrosion of the silicon solution to inner wall of quartz crucible with this, improves silica crucible
Service life enhances the intensity of silica crucible, reduces its temperature distortion, and then improve the yield of pulling of crystals, improves production effect
Rate.
One embodiment of the present invention has been described in detail above, but the content is only preferable implementation of the invention
Example, should not be considered as limiting the scope of the invention.It is all according to all the changes and improvements made by the present patent application range
Deng should still be within the scope of the patent of the present invention.
Claims (10)
1. a kind of silica crucible, it is characterised in that: including bubble composite layer, hyaline layer and coating, the coating includes the first painting
Layer and second coating, the bubble composite layer, the hyaline layer, the first coating and the second coating are from outside to inside successively
Setting.
2. silica crucible according to claim 1, it is characterised in that: the first coating is barium carbonate.
3. silica crucible according to claim 1 or 2, it is characterised in that: the second coating is barium silicate.
4. silica crucible according to claim 3, it is characterised in that: the thickness of the bubble composite layer and the hyaline layer
The sum of it is constant.
5. silica crucible according to claim 4, it is characterised in that: the quartz sand purity of the bubble composite layer is less than institute
State hyaline layer quartz sand purity.
6. silica crucible according to claim 5, it is characterised in that: the hyaline layer quartz sand purity is 99.9999%.
7. a kind of method for drawing silicon single crystal using Novel quartz crucible, it is characterised in that: take section to throw the stage again in pulling of crystals,
The flow for putting into a certain amount of barium carbonate, while taking section to throw stage argon gas again described in controlling.
8. the method according to claim 7 for drawing silicon single crystal using Novel quartz crucible, it is characterised in that: the carbonic acid
The amount of barium is 2-5g.
9. the method according to claim 7 or 8 for drawing silicon single crystal using Novel quartz crucible, it is characterised in that: described
The flow of argon gas is 100-120s lpm.
10. the method according to claim 9 for drawing silicon single crystal using Novel quartz crucible, it is characterised in that: described
It is described every time during pulling of crystals to take section to throw the stage again the barium carbonate is added.
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| CN109355699A (en) * | 2018-11-29 | 2019-02-19 | 内蒙古中环光伏材料有限公司 | A kind of silica crucible and its method for improving silica crucible service life |
| CN110592663A (en) * | 2019-10-12 | 2019-12-20 | 内蒙古中环光伏材料有限公司 | Use process of quartz crucible for drawing multiple single crystals |
| CN115142121A (en) * | 2021-03-31 | 2022-10-04 | 晶科能源股份有限公司 | Method for improving crystallization rate of re-cast single crystal silicon and device for preparing single crystal silicon |
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