CN103046034A - Method for matrix strengthening and surface coating of graphite guide cylinder for czochralski silicon single crystal - Google Patents
Method for matrix strengthening and surface coating of graphite guide cylinder for czochralski silicon single crystal Download PDFInfo
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- CN103046034A CN103046034A CN2013100078798A CN201310007879A CN103046034A CN 103046034 A CN103046034 A CN 103046034A CN 2013100078798 A CN2013100078798 A CN 2013100078798A CN 201310007879 A CN201310007879 A CN 201310007879A CN 103046034 A CN103046034 A CN 103046034A
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Abstract
The invention discloses a method for matrix strengthening and surface coating of a graphite guide cylinder for a czochralski silicon single crystal. The method comprises the following steps that (1) surface pretreatment is conducted; (2) hydrocarbon gas is adopted for chemical vapor deposition, and a matrix is strengthened; (3) silicon carbide powder, silicon powder and a solvent are mixed at a mass ratio of 1:(3-5):(6-8) and stirred uniformly; slurry is obtained; the surface of the graphite guide cylinder is uniformly coated with the slurry about 30-50 micrometers thick, and then the graphite guide cylinder is put into a curing furnace for baking treatment; (4) the graphite guide cylinder is placed in a high temperature furnace for in-situ reaction; an SiC outer layer is prepared; and (5) the graphite guide cylinder is placed in a chemical vapor deposition furnace, and the hydrocarbon gas is adopted for the chemical vapor deposition. With the method, the strength of the graphite guide cylinder can be effectively improved in a high temperature use process, and the problems that the existing graphite guide cylinder has external surface oxidization, overall cracking, chipping, and the like after short-term use can be effectively solved.
Description
Technical field
The present invention relates to a kind of czochralski silicon monocrystal method of graphite guide shell matrix strengthening and top coat.
Background technology
Guide shell is accessory indispensable in the monocrystalline silicon growing furnace, adopts high-purity isostatic pressing formed graphite to make more.Graphite guide shell urceolus is placed in directly over the crucible, easily produces under silicon steam and oxidizing gas effect and corrodes and cracking.The consumption of graphite guide shell has certain ratio in the total cost of monocrystalline silicon growing, the unexpected damage of guide shell can cause crucible, well heater to damage, even causes whole thermal field to damage.Therefore, the antioxidant property of raising graphite guide shell is most important for the cost control of monocrystalline silicon growing.
CN1414330A discloses a kind of graphite crucible having high temperature carbon resisting coating layer on April 30th, 2003, is mainly used in the founding of u-ni alloy high temperature, owing to contain metallic element in this coating, is not suitable for the coating processing requirements of accessory in the monocrystal growing furnace.
CN1554802A discloses a kind of method for preparing used by nuclear reactor graphite surface oxidation resistant coating material silicon carbide on December 15th, 2004, the method is controlled the cracking Polycarbosilane by changing cracking temperature and cracking atmosphere carbon/silicon recently prepares coat of silicon carbide, raw materials used Polycarbosilane is expensive, production cost is high, does not utilize and applies.
CN102373417 discloses a kind of method for preparing the SiC coating on the graphite material surface on March 14th, 2012, the method adopts the ultra-high vacuum multifunctional magnetic-controlled sputtering coating equipment, selecting purity is that 99.9% silica flour prepares the Si target, volume fraction is that 99.99% high-purity argon gas is sputter gas, in graphite material surface preparation Si coating, then obtain anti-oxidant SiC coating through vacuum heat treatment through rf magnetron sputtering.It is high to the performance requriements of equipment to prepare the SiC coating with the method, and technical process is longer, and production cost is higher, and is relatively poor to heavy parts adaptability.
At present, existing graphite guide shell ubiquity short-term is prone to the outside surface oxidation after using, and whole cracking falls the phenomenons such as piece, thereby makes troubles to production, affects Business Economic Benefit.
Summary of the invention
Technical problem to be solved by this invention is, provide a kind of graphite guide shell that makes after short-term is used, not to be prone to the outside surface oxidation, whole cracking, fall the czochralski silicon monocrystal of the phenomenon such as piece with the method for graphite guide shell matrix strengthening and top coat, the method suitability is strong, technical process is simple, and production cost is low.
The technical scheme that the present invention solves its technical problem employing is: a kind of czochralski silicon monocrystal method of graphite guide shell matrix strengthening and top coat may further comprise the steps:
(1) to the surface of graphite guide shell polish, cleaning and drying treatment;
(2) the graphite guide shell after step (1) is processed is placed in the chemical vapor deposition stove, adopt hydrocarbon gas to carry out chemical vapour deposition, depositing temperature is 900～1200 ℃, depositing time 50～100 hours, the hydrocarbon gas flow is 30～50L/min, and nitrogen flow is 15～30L/min;
(3) in quality proportioning carborundum powder: silica flour: solvent=1:(3～5): the ratio of (6～8) is mixed each raw material, stirs, and gets slurry; Adopt spread coating or spraying method that the graphite guide shell that the gained slurry evenly is coated on after step (2) is processed is surperficial, coating thickness 30～50 μ m, then insert and carry out baking processing in the curing oven, be warming up to 160～200 ℃, afterheat baking 1～2 hour with the temperature rise rate of 60 ± 2 ℃/h;
(4) place High Temperature Furnaces Heating Apparatus to carry out reaction in－situ the graphite guide shell after step (3) is processed, temperature of reaction is 1850～2300 ℃, adopts nitrogen or argon shield, and insulation reaction 2～6 hours makes the SiC skin;
(5) the graphite guide shell after step (4) is processed is placed in the chemical vapor deposition stove, adopt hydrocarbon gas to carry out chemical vapour deposition, depositing temperature is 900～1200 ℃, and depositing time is 10～20 hours, the hydrocarbon gas flow is 20～40L/min, and nitrogen flow is 10～20L/min.
Further, in the step (3), described carborundum powder is α-SiC, and granularity is 400～1200 orders; Described silicon particle size is 400～800 orders; Described solvent is silicon sol, alcohol or Diethylene Glycol.
Further, in step (2) and the step (5), the hydrocarbon gas of chemical vapour deposition is methane, propane or propylene.
Studies show that the pyrocarbon coating on graphite material surface and coat of silicon carbide have good antioxidant property in graphite guide shell working temperature interval, is the most important and effective anti-oxidation barrier of graphite matrix.In order to improve the conjugation of sealer and graphite matrix, make the antioxidant defense layer have excellent thermal shock resistance, the bonding interface of coating and graphite matrix can be consisted of the function-graded material surface of thermal stresses mitigation type.Function-graded material is the material that a kind of performance changes in gradient, and its special construction and conjugation make it have excellent thermal shock resistance, and the SiC sealer is a kind of typical thermal stresses mitigation type function-graded material.
The present invention carries out pre-treatment to graphite guide shell surface first, then with the chemical Vapor deposition process RESEARCH OF PYROCARBON graphite guide shell matrix is strengthened, and makes the SiC cementation zone by reaction in－situ again; For preventing corrosive gases to the erosion of skin-material, adopt chemical Vapor deposition process that the SiC skin is carried out densification, prepare the outer field compound coating of RESEARCH OF PYROCARBON internal layer and SiC.Prepared compound coating is anti-oxidant, resistance to corrosion is strong, can strengthen body material, improves hardness and the compactness on surface, prolongs the work-ing life of product, improves the working reliability of product.
The present invention can stop the intrusion of silicon steam and oxidizing gas, can effectively improve the intensity of graphite guide shell in the applied at elevated temperature process, can effectively solve existing graphite guide shell and the outside surface oxidation occur after short-term is used, the whole cracking fallen the problem of the phenomenons such as piece; The unsetting silicon of surface attachment is very easily cleaning also, and during cleaning, the surface is complete, unlikely damage.
In addition, the present invention adopts spraying or brushes, and silicon source distribution is controlled, and surface hardness is high, and coating and body material consist of gradient material, and thermal insulation is good, and good thermal shock is without decrepitation.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
Present embodiment may further comprise the steps:
(1) to the surface of graphite guide shell polish, cleaning and drying treatment;
(2) will be after step (1) be processed the graphite guide shell place in the chemical vapor deposition stove, adopt hydrocarbon gas propane to carry out chemical vapour deposition, depositing temperature is 1000 ℃, and the propane flow is 45L/min, nitrogen flow is 20L/min, and depositing time is 60 hours;
(3) in quality proportioning carborundum powder: the ratio of silica flour: solvent=1:3:7 is mixed each raw material, stirs, and gets slurry; Adopt spraying method that the gained slurry evenly is coated on graphite guide shell surface after step (2) is processed, then coating thickness 40 μ m insert and carry out baking processing in the curing oven, are warming up to 180 ℃, afterheat baking 1.5 hours with the temperature rise rate of 60 ± 1 ℃/h;
Described carborundum powder is α-SiC, and granularity is 1200 orders; Described silicon particle size is 400 orders; Described solvent is silicon sol;
(4) place High Temperature Furnaces Heating Apparatus to carry out reaction in－situ the graphite guide shell after step (3) is processed, temperature of reaction is 1860 ℃, adopts nitrogen protection, and insulation reaction 3 hours makes the SiC skin;
(5) the graphite guide shell after step (4) is processed is placed in the chemical vapor deposition stove, adopt hydrocarbon gas propane to carry out chemical vapour deposition, depositing temperature is 1000 ℃, and depositing time is 20 hours, the propane flow is 25L/min, and nitrogen flow is 15L/min.
The graphite guide shell of present embodiment preparation uses in 24 cun monocrystalline silicon growing furnace, and use temperature is 1500 ℃, uses 1500 hours, and top coat is without cracking, powder falling phenomenon; The outside dirt settling of guide shell only needs slightly wiping just can remove.
Embodiment 2
Present embodiment may further comprise the steps:
(1) to the surface of graphite guide shell polish, cleaning and drying treatment;
(2) will be after step (1) be processed the graphite guide shell place in the chemical vapor deposition stove, adopt hydrocarbon gas methane to carry out chemical vapour deposition, depositing temperature is 1000 ℃, and methane flow is 36L/min, nitrogen flow is 20L/min, and depositing time is 50 hours;
(3) with carborundum powder, silica flour and solvent in quality proportioning carborundum powder: the ratio of silica flour: solvent=1:4:8 is mixed, and stirs, and gets slurry; Adopt spread coating that the gained slurry evenly is coated on graphite guide shell surface after step (2) is processed, then coating thickness 35-45 μ m inserts and carries out baking processing in the curing oven, is warming up to 170 ℃, afterheat baking 2 hours with the temperature rise rate of 60 ± 1 ℃/h;
Described carborundum powder is α-SiC, and granularity is 1200 orders; Described silicon particle size is 400 orders; Described solvent is alcohol;
(4) place High Temperature Furnaces Heating Apparatus to carry out reaction in－situ the graphite guide shell after step (3) is processed, temperature of reaction is 2000 ℃, adopts argon shield, and insulation reaction 3 hours makes the SiC skin;
(5) the graphite guide shell after step (4) is processed is placed in the chemical vapor deposition stove, adopt hydrocarbon gas methane to carry out chemical vapour deposition, depositing temperature is 1000 ℃, and depositing time is 20 hours, methane flow is 30L/min, and nitrogen flow is 15L/min.
The graphite guide shell of present embodiment preparation uses in 24 cun monocrystalline silicon growing furnace, and use temperature is 1500 ℃, uses 1550 hours, and top coat is without cracking, powder falling phenomenon; The outside dirt settling of guide shell only needs slightly wiping just can remove.
Embodiment 3
Present embodiment may further comprise the steps:
(1) to the surface of graphite guide shell polish, cleaning and drying treatment;
(2) will be after step (1) be processed the graphite guide shell place in the chemical vapor deposition stove, adopt the hydrocarbon gas propylene to carry out chemical vapour deposition, depositing temperature is 1000 ℃, and the propylene flow is 50L/min, nitrogen flow is 28L/min, and depositing time is 80 hours;
(3) with carborundum powder, silica flour and solvent in quality proportioning carborundum powder: the ratio of silica flour: solvent=1:4:7 is mixed, and stirs, and gets slurry; Adopt spread coating that the gained slurry evenly is coated on graphite guide shell surface after step (2) is processed, then coating thickness 35 μ m insert and carry out baking processing in the curing oven, are warming up to 170 ℃, afterheat baking 2 hours with the temperature rise rate of 60 ± 1 ℃/h;
Described carborundum powder is α-SiC, and granularity is 1200 orders; Described silicon particle size is 400 orders; Described solvent is Diethylene Glycol;
(4) place High Temperature Furnaces Heating Apparatus to carry out reaction in－situ the graphite guide shell after step (3) is processed, temperature of reaction is 2200 ℃, adopts nitrogen protection, and insulation reaction 2 hours makes the SiC skin;
(5) the graphite guide shell after step (4) is processed is placed in the chemical vapor deposition stove, adopt the hydrocarbon gas propylene to carry out chemical vapour deposition, depositing temperature is 1000 ℃, and depositing time is 20 hours, the propylene flow is 40L/min, and nitrogen flow is 18L/min.
The graphite guide shell of present embodiment preparation uses in 24 cun monocrystalline silicon growing furnace, and use temperature is 1500 ℃, uses 1570 hours, and top coat is without cracking, powder falling phenomenon; The outside dirt settling of guide shell only needs slightly wiping just can remove.
Claims (3)
1. a czochralski silicon monocrystal is characterized in that with the method for graphite guide shell matrix strengthening and top coat, may further comprise the steps:
(1) to the surface of graphite guide shell polish, cleaning and drying treatment;
(2) the graphite guide shell after step (1) is processed is placed in the chemical vapor deposition stove, adopt hydrocarbon gas to carry out chemical vapour deposition, depositing temperature is 900～1200 ℃, depositing time 50～100 hours, the hydrocarbon gas flow is 30～50L/min, and nitrogen flow is 15～30L/min;
(3) in quality proportioning carborundum powder: silica flour: solvent=1:(3～5): the ratio of (6～8) is mixed each raw material, stirs, and gets slurry; Adopt spread coating or spraying method that the graphite guide shell that the gained slurry evenly is coated on after step (2) is processed is surperficial, coating thickness 30～50 μ m, then insert and carry out baking processing in the curing oven, be warming up to 160～200 ℃, afterheat baking 1～2 hour with the temperature rise rate of 60 ± 2 ℃/h;
(4) place High Temperature Furnaces Heating Apparatus to carry out reaction in－situ the graphite guide shell after step (3) is processed, temperature of reaction is 1850～2300 ℃, adopts nitrogen or argon shield, and insulation reaction 2～6 hours makes the SiC skin;
(5) the graphite guide shell after step (4) is processed is placed in the chemical vapor deposition stove, adopt hydrocarbon gas to carry out chemical vapour deposition, depositing temperature is 900～1200 ℃, and depositing time is 10～20 hours, the hydrocarbon gas flow is 20～40L/min, and nitrogen flow is 10～20L/min.
2. czochralski silicon monocrystal according to claim 1 is characterized in that with the method for graphite guide shell matrix strengthening and top coat in the step (3), described carborundum powder is α-SiC, and granularity is 400～1200 orders; Described silicon particle size is 400～800 orders; Described solvent is silicon sol, alcohol or Diethylene Glycol.
3. czochralski silicon monocrystal according to claim 1 and 2 is characterized in that with the method for graphite guide shell matrix strengthening and top coat in step (2) and the step (5), the hydrocarbon gas of chemical vapour deposition is methane, propane or propylene.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410560A (en) * | 2020-04-02 | 2020-07-14 | 江苏嘉明碳素新材料有限公司 | Preparation method of silicified graphite with high-density SiC coating |
| CN111763096A (en) * | 2020-07-29 | 2020-10-13 | 上海骐杰碳素材料有限公司 | Carbon-based material for heat preservation device |
| CN112624782A (en) * | 2020-12-11 | 2021-04-09 | 包头美科硅能源有限公司 | Application method of crucible edge coating |
| CN115448752A (en) * | 2022-09-26 | 2022-12-09 | 攀钢集团研究院有限公司 | Method for prolonging service life of graphite crucible for vanadium-nitrogen alloy |
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| JPS5841782A (en) * | 1981-09-07 | 1983-03-11 | 品川白煉瓦株式会社 | Oxidation prevention for graphite-containing refractories |
| US4535035A (en) * | 1984-01-17 | 1985-08-13 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Oxidation resistant slurry coating for carbon-based materials |
| CN101565328A (en) * | 2009-05-26 | 2009-10-28 | 西北工业大学 | Method for preparing carbon/carbon composite material antioxidation coating layer |
| CN102277560A (en) * | 2011-08-23 | 2011-12-14 | 南京理工大学 | Method for improving oxidation resistance of graphite electrode by obtaining SiC/C gradient surface coating through chemical vapor deposition |
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2013
- 2013-01-10 CN CN201310007879.8A patent/CN103046034B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5841782A (en) * | 1981-09-07 | 1983-03-11 | 品川白煉瓦株式会社 | Oxidation prevention for graphite-containing refractories |
| US4535035A (en) * | 1984-01-17 | 1985-08-13 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Oxidation resistant slurry coating for carbon-based materials |
| CN101565328A (en) * | 2009-05-26 | 2009-10-28 | 西北工业大学 | Method for preparing carbon/carbon composite material antioxidation coating layer |
| CN102277560A (en) * | 2011-08-23 | 2011-12-14 | 南京理工大学 | Method for improving oxidation resistance of graphite electrode by obtaining SiC/C gradient surface coating through chemical vapor deposition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410560A (en) * | 2020-04-02 | 2020-07-14 | 江苏嘉明碳素新材料有限公司 | Preparation method of silicified graphite with high-density SiC coating |
| CN111763096A (en) * | 2020-07-29 | 2020-10-13 | 上海骐杰碳素材料有限公司 | Carbon-based material for heat preservation device |
| CN112624782A (en) * | 2020-12-11 | 2021-04-09 | 包头美科硅能源有限公司 | Application method of crucible edge coating |
| CN115448752A (en) * | 2022-09-26 | 2022-12-09 | 攀钢集团研究院有限公司 | Method for prolonging service life of graphite crucible for vanadium-nitrogen alloy |
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