CN113417010B - High-cleanliness annealing method for polycrystalline silicon rod material - Google Patents
High-cleanliness annealing method for polycrystalline silicon rod material Download PDFInfo
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 95
- 238000000137 annealing Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000002791 soaking Methods 0.000 claims abstract description 37
- 238000005238 degreasing Methods 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000004140 cleaning Methods 0.000 claims abstract description 20
- 108010010803 Gelatin Proteins 0.000 claims abstract description 12
- 229920000159 gelatin Polymers 0.000 claims abstract description 12
- 239000008273 gelatin Substances 0.000 claims abstract description 12
- 235000019322 gelatine Nutrition 0.000 claims abstract description 12
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005530 etching Methods 0.000 claims abstract description 10
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims abstract description 9
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 229920005591 polysilicon Polymers 0.000 claims description 48
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 21
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- YYKBWYBUCFHYPR-UHFFFAOYSA-N 12-bromododecanoic acid Chemical compound OC(=O)CCCCCCCCCCCBr YYKBWYBUCFHYPR-UHFFFAOYSA-N 0.000 claims description 8
- ASIDMJNTHJYVQJ-UHFFFAOYSA-N bromo-dodecanol Chemical compound OCCCCCCCCCCCCBr ASIDMJNTHJYVQJ-UHFFFAOYSA-N 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 239000004519 grease Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 238000003754 machining Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
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Abstract
The invention discloses a high-cleanliness annealing method for a polycrystalline silicon rod material, which comprises degreasing and cleaning a polycrystalline silicon rod, soaking the polycrystalline silicon rod in pure water for the first time, acid-mixing and etching the polycrystalline silicon rod, soaking the polycrystalline silicon rod in pure water for the second time, drying the polycrystalline silicon rod in nitrogen, cleaning an annealing furnace, and annealing the polycrystalline silicon rod; the polycrystalline silicon rod material is low in surface grease content and material phase metal content, has a good machining effect, can meet a chip manufacturing process, and prepares degreasing powder in the degreasing and cleaning process of the polycrystalline silicon rod, gelatin is dissolved and added into an intermediate 6, under the action of 1-hydroxybenzotriazole, carboxyl on the intermediate 6 and amino on the surface of the gelatin undergo dehydration condensation, continue to react with an intermediate 4, and are treated by sodium chloroacetate to prepare the degreasing powder, and the degreasing powder can permeate surface active molecules into the grease, is separated from the surface of the polycrystalline silicon rod, emulsifies and disperses the grease into water, and achieves the degreasing effect.
Description
Technical Field
The invention relates to the technical field of silicon material preparation, in particular to a high-cleanliness annealing method for a polycrystalline silicon rod material.
Background
The temperature is usually above 1000 ℃, metal pollution on the surface or the body of a silicon boat under the condition can quickly diffuse and escape to the surface or the interior of a wafer to cause the failure of a chip, the silicon boat is formed by mechanically processing a polysilicon rod, the polysilicon rod is produced by a chemical vapor deposition process, the purity of the polysilicon rod produced by the process is extremely high, but in the process that the silicon rod gradually grows from a seed crystal, the material of the silicon rod has large internal stress, if the silicon rod is directly physically cut, the internal stress of the silicon rod can be directly and intensively released to cause the breakage and breakage of the material of the silicon rod, so the annealing treatment is required to be carried out on the polysilicon rod before the mechanical processing to eliminate the internal stress;
when the chip is thermally treated, the metal content on the surface of the wafer is required to be extremely low, and the metal content must be 1E10atoms/cm2In the following, therefore, silicon boats are used as carriers in direct contact, and the surface and bulk metal contamination of the silicon boats must also be at an extremely low level, so the silicon boats must have good annealing and cleaning processes to ensure the surface cleanliness;
the conventional annealing of the polysilicon rod is to place the polysilicon rod in a horizontal annealing furnace in an open environment, wherein an alumina refractory brick and an asbestos heat insulation layer are arranged in the horizontal annealing furnace, and the material phase metal content annealed by the method is high, so that the chip manufacturing process with high processing requirements cannot be met, and therefore, a set of high-cleanliness annealing technology for the polysilicon rod material needs to be developed urgently.
Disclosure of Invention
The present invention is directed to a high-cleanliness annealing method for polysilicon rod material, so as to solve the technical defects in the background art.
The purpose of the invention can be realized by the following technical scheme:
a high-cleanliness annealing method for a polycrystalline silicon rod material specifically comprises the following steps:
step S1 degreasing and cleaning the polysilicon rod: dissolving the degreased powder in boiling water, adding the polysilicon rod, boiling and degreasing for 1-1.5 h;
step S2, primary soaking of the polycrystalline silicon rod in pure water: putting the cleaned polysilicon rod into pure water, and performing primary overflow soaking at the temperature of 80-90 ℃;
step S3 mixed acid etching of polysilicon rod: putting the polycrystalline silicon rod subjected to overflow soaking into mixed acid corrosive liquid, and soaking for 3-8min at the temperature of 20-25 ℃;
step S4, carrying out secondary pure water soaking on the polycrystalline silicon rod: and putting the etched polysilicon rod into pure water, and performing secondary overflow soaking at the temperature of 80-90 ℃.
Step S5 nitrogen drying of the polysilicon rod: drying the soaked polysilicon rod in a clean room with the level of more than 1000 by using nitrogen;
step S6 annealing furnace cleaning: putting the dried silicon rod into a vertical annealing furnace, introducing purified nitrogen to replace air in the furnace, adding dichloroethylene to clean the surfaces of the furnace tube and the silicon rod, and continuously introducing purified nitrogen to replace cleaning gas dichloroethylene;
step S7 annealing of the polycrystalline silicon rod: heating to 1200 ℃, preserving heat for 3-5h, and cooling to room temperature to obtain the polysilicon rod material.
Further, the dosage mass ratio of the defatted powder and the boiling water in the step S1 is 1: 20.
further, the termination condition of the primary overflow soaking in step S2 is that the resistivity of the overflow pure water is greater than 3 Μ Ω.
Further, the mixed acid etching solution in step S3 is hydrofluoric acid: nitric acid: the volume ratio of the used acetic acid is 1:1:2 and mixing.
Further, the termination condition of the secondary overflow soaking in step S4 is that the resistivity of the overflowed pure water is greater than 15 Μ Ω.
Further, the nitrogen gas described in step S5 was purified and filtered using a 0.1 μm cartridge.
Further, the temperature rising rate in step S6 is 2 ℃/min, and the temperature lowering rate is 2 ℃/min.
Further, the defatted powder is prepared by the following steps:
step A1: heating 12-bromododecanoic acid to be molten, stirring and dropwise adding thionyl chloride under the condition that the rotating speed is 120-90 ℃ at a speed of 150r/min, heating to 80-85 ℃, carrying out reflux reaction for 3-5h to obtain an intermediate 1, adding the intermediate 1, aluminum chloride and benzene into a reaction kettle, and carrying out reflux reaction for 6-8h under the conditions that the rotating speed is 150-200r/min and the temperature is 85-90 ℃ to obtain an intermediate 2;
the reaction process is as follows:
step A2: adding the intermediate 2, potassium hydroxide and diethylene glycol into a reaction kettle, stirring and adding hydrazine hydrate under the conditions that the rotating speed is 120-80 ℃ and the temperature is 70-80 ℃, performing reflux reaction for 3-5 hours under the condition that the temperature is 120-130 ℃ to obtain an intermediate 3, adding the intermediate 3 and concentrated sulfuric acid into the reaction kettle, reacting for 3-5 hours under the condition that the temperature is 60-70 ℃, cooling to 40-50 ℃, adding deionized water, standing for layering, removing a lower water layer, adding a sodium hydroxide solution into an organic phase, adjusting the pH value to 7, and obtaining an intermediate 4;
the reaction process is as follows:
step A3: adding 12-bromo-1-dodecanol, dimethylamine, N-dimethylformamide and potassium carbonate into a reaction kettle, reacting for 2-3h at the temperature of 20-25 ℃ at the rotation speed of 150-;
the reaction process is as follows:
step A4: dissolving gelatin in deionized water, adding the intermediate 6 and 1-hydroxybenzotriazole, reacting for 3-5h at the rotation speed of 120-150r/min and the temperature of 50-60 ℃, adding the intermediate 4 and potassium carbonate, continuing to react for 3-5h, adding sodium chloroacetate, heating to the temperature of 110-120 ℃, carrying out reflux reaction for 6-8h, adjusting the pH value to 7, and distilling to remove the deionized water to obtain the degreasing powder.
The reaction process is as follows:
further, the amount of the 12-bromododecanoic acid and the thionyl chloride used in the step A1 is 1:2, the molar ratio of the intermediate 1 to the aluminum chloride to the benzene is 1:1: 5.
further, the intermediate 2, potassium hydroxide, diethylene glycol and hydrazine hydrate in the step A2 are used in a ratio of 0.15mol:0.6mol:112.5mL:30mL, and the mass fraction of sodium hydroxide is 10%.
Further, the dosage of the 12-bromo-1-dodecanol, the dimethylamine, the N, N-dimethylformamide and the potassium carbonate in the step A3 is 0.01mol:0.02mol:0.15mol:40mL, wherein the dosage ratio of the intermediate 5, oxalic acid, copper sulfate and tetrahydrofuran is 0.01mol:0.015mol:0.02mol:50 mL.
Further, the gelatin, the intermediate 6, the 1-hydroxybenzotriazole, the intermediate 4, the potassium carbonate and the sodium chloroacetate in the step A4 are used in an amount of 5:0.8:1:1.5:1.8: 0.4.
the invention has the following beneficial effects:
the high-cleanliness annealing method of the polycrystalline silicon rod material used by the invention has the advantages that the prepared polycrystalline silicon rod material has low surface grease content, low material phase metal content and good machining effect, can meet the requirements of chip manufacturing process, degreasing powder is prepared in the degreasing and cleaning process of the polycrystalline silicon rod, the degreasing powder takes 12-bromododecanoic acid as a raw material to react with thionyl chloride to prepare an intermediate 1, the intermediate 1 and benzene react under the action of aluminum chloride to prepare an intermediate 2, the intermediate 2 is further processed to prepare an intermediate 3, the intermediate 3 reacts with concentrated sulfuric acid to prepare an intermediate 4, 12-bromo-1-dodecanol reacts with dimethylamine to prepare an intermediate 5, the intermediate 5 reacts with oxalic acid to enable the alcoholic hydroxyl group on the intermediate 5 to have esterification reaction with a carboxyl group of the oxalic acid, preparing an intermediate 6, dissolving gelatin, adding the dissolved gelatin into the intermediate 6, performing dehydration condensation on carboxyl on the intermediate 6 and amino on the surface of the gelatin under the action of 1-hydroxybenzotriazole, continuously reacting with the intermediate 4, and then treating with sodium chloroacetate to prepare degreasing powder, wherein the degreasing powder can permeate surface active molecules into grease to be separated from the surface of a polycrystalline silicon rod, and the grease is emulsified and dispersed in water to achieve a degreasing effect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a high-cleanliness annealing method for a polycrystalline silicon rod material specifically comprises the following steps:
step S1 degreasing and cleaning the polysilicon rod: dissolving the degreased powder in boiling water, adding the polysilicon rod, boiling and degreasing for 1 h;
step S2, primary soaking of the polycrystalline silicon rod in pure water: putting the cleaned polycrystalline silicon rod into pure water, and performing overflow soaking at the temperature of 80 ℃ until the resistivity of the overflow pure water is greater than 3 mu omega;
step S3 mixed acid etching of polysilicon rod: putting the polycrystalline silicon rod subjected to overflow soaking into a corrosive liquid with a volume ratio of hydrofluoric acid to nitric acid to acetic acid being 1:1:2, and soaking for 3min at the temperature of 20 ℃;
step S4, carrying out secondary pure water soaking on the polycrystalline silicon rod: placing the etched polysilicon rod into pure water, and performing overflow soaking at the temperature of 80 ℃ until the resistivity of the overflow pure water is greater than 15 mu m omega;
step S5 nitrogen drying of the polysilicon rod: drying the soaked polysilicon rod in a clean room with the grade of more than 1000 by using nitrogen purified and filtered by a filter element with the diameter of 0.1 mu m;
step S6 annealing furnace cleaning: putting the dried silicon rod into a vertical annealing furnace, introducing purified nitrogen to replace air in the furnace, adding dichloroethylene to clean the surfaces of the furnace tube and the silicon rod, and continuously introducing purified nitrogen to replace cleaning gas dichloroethylene;
step S7 annealing of the polycrystalline silicon rod: under the protection of nitrogen with the heating rate of 2 ℃/min, heating to 1200 ℃, preserving heat for 3 hours, and then cooling to room temperature under the condition of cooling to 2 ℃/min to prepare the polysilicon rod material.
The degreasing powder is prepared by the following steps:
step A1: heating 12-bromododecanoic acid to be molten, stirring and dropwise adding thionyl chloride under the condition that the rotating speed is 120r/min, heating to 80 ℃, performing reflux reaction for 3 hours to obtain an intermediate 1, adding the intermediate 1, aluminum chloride and benzene into a reaction kettle, and performing reflux reaction for 6 hours under the conditions that the rotating speed is 180r/min and the temperature is 85 ℃ to obtain an intermediate 2;
step A2: adding the intermediate 2, potassium hydroxide and diethylene glycol into a reaction kettle, stirring and adding hydrazine hydrate under the conditions that the rotating speed is 120r/min and the temperature is 70 ℃, performing reflux reaction for 3 hours under the condition that the temperature is 120 ℃ to obtain an intermediate 3, adding the intermediate 3 and concentrated sulfuric acid into the reaction kettle, reacting for 3 hours under the condition that the temperature is 60 ℃, cooling to 40 ℃, adding deionized water, standing for layering, removing a lower water layer, adding a sodium hydroxide solution into an organic phase, and adjusting the pH value to be 7 to obtain an intermediate 4;
step A3: adding 12-bromo-1-dodecanol, dimethylamine, N-dimethylformamide and potassium carbonate into a reaction kettle, reacting for 2 hours at the temperature of 20 ℃ at the rotation speed of 150r/min, heating to 50 ℃, reacting for 4 hours to obtain an intermediate 5, adding the intermediate 5, oxalic acid, copper sulfate and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 5 hours at the temperature of 120 ℃ to obtain an intermediate 6;
step A4: dissolving gelatin in deionized water, adding intermediate 6 and 1-hydroxybenzotriazole, reacting for 3h at a rotation speed of 120r/min and a temperature of 50 ℃, adding intermediate 4 and potassium carbonate, continuing to react for 3h, adding sodium chloroacetate, heating to a temperature of 110 ℃, performing reflux reaction for 6h, adjusting the pH value to 7, and distilling to remove deionized water to obtain the degreasing powder.
Example 2:
a high-cleanliness annealing method for a polycrystalline silicon rod material specifically comprises the following steps:
step S1 degreasing and cleaning the polysilicon rod: dissolving the degreased powder in boiling water, adding the polysilicon rod, boiling and degreasing for 1 h;
step S2, primary soaking of the polycrystalline silicon rod in pure water: putting the cleaned polycrystalline silicon rod into pure water, and performing overflow soaking at the temperature of 80 ℃ until the resistivity of the overflow pure water is greater than 3 mu omega;
step S3 mixed acid etching of polysilicon rod: step S3 mixed acid etching of polysilicon rod: putting the polycrystalline silicon rod subjected to overflow soaking into a corrosive liquid with a volume ratio of hydrofluoric acid to nitric acid to acetic acid being 1:1:2, and soaking for 5min at the temperature of 23 ℃;
step S4, carrying out secondary pure water soaking on the polycrystalline silicon rod: placing the etched polysilicon rod into pure water, and performing overflow soaking at the temperature of 85 ℃ until the resistivity of the overflow pure water is greater than 15 mu m omega;
step S5 nitrogen drying of the polysilicon rod: drying the soaked polysilicon rod in a clean room with the grade of more than 1000 by using nitrogen purified and filtered by a filter element with the diameter of 0.1 mu m;
step S6 annealing furnace cleaning: putting the dried silicon rod into a vertical annealing furnace, introducing purified nitrogen to replace air in the furnace, adding dichloroethylene to clean the surfaces of the furnace tube and the silicon rod, and continuously introducing purified nitrogen to replace cleaning gas dichloroethylene;
step S7 annealing of the polycrystalline silicon rod: under the protection of nitrogen with the heating rate of 2 ℃/min, heating to 1200 ℃, preserving heat for 4h, and then cooling to room temperature under the condition of cooling to 2 ℃/min to prepare the polysilicon rod material.
The degreasing powder is prepared by the following steps:
step A1: heating 12-bromododecanoic acid to be molten, stirring and dropwise adding thionyl chloride under the condition that the rotating speed is 120r/min, heating to 83 ℃, performing reflux reaction for 4 hours to obtain an intermediate 1, adding the intermediate 1, aluminum chloride and benzene into a reaction kettle, and performing reflux reaction for 7 hours under the conditions that the rotating speed is 180r/min and the temperature is 88 ℃ to obtain an intermediate 2;
step A2: adding the intermediate 2, potassium hydroxide and diethylene glycol into a reaction kettle, stirring and adding hydrazine hydrate under the conditions that the rotating speed is 120r/min and the temperature is 75 ℃, performing reflux reaction for 4 hours under the condition that the temperature is 125 ℃ to obtain an intermediate 3, adding the intermediate 3 and concentrated sulfuric acid into the reaction kettle, reacting for 4 hours under the condition that the temperature is 65 ℃, cooling to 45 ℃, adding deionized water, standing for layering, removing a lower water layer, adding a sodium hydroxide solution into an organic phase, and adjusting the pH value to be 7 to obtain an intermediate 4;
step A3: adding 12-bromo-1-dodecanol, dimethylamine, N-dimethylformamide and potassium carbonate into a reaction kettle, reacting for 2.5 hours at 23 ℃ at a rotation speed of 180r/min, heating to 55 ℃, reacting for 5 hours to obtain an intermediate 5, adding the intermediate 5, oxalic acid, copper sulfate and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 6 hours at 125 ℃ to obtain an intermediate 6;
step A4: dissolving gelatin in deionized water, adding intermediate 6 and 1-hydroxybenzotriazole, reacting for 4h at a rotation speed of 120r/min and a temperature of 55 ℃, adding intermediate 4 and potassium carbonate, continuing to react for 4h, adding sodium chloroacetate, heating to a temperature of 115 ℃, performing reflux reaction for 7h, adjusting the pH value to 7, and distilling to remove deionized water to obtain the degreasing powder.
Example 3:
a high-cleanliness annealing method for a polycrystalline silicon rod material specifically comprises the following steps:
step S1 degreasing and cleaning the polysilicon rod: dissolving the degreased powder in boiling water, adding the polysilicon rod, boiling and degreasing for 1.5 h;
step S2, primary soaking of the polycrystalline silicon rod in pure water: putting the cleaned polycrystalline silicon rod into pure water, and performing overflow soaking at the temperature of 90 ℃ until the resistivity of the overflow pure water is greater than 3 mu omega;
step S3 mixed acid etching of polysilicon rod: putting the polycrystalline silicon rod subjected to overflow soaking into a corrosive liquid with a volume ratio of hydrofluoric acid to nitric acid to acetic acid being 1:1:2, and soaking for 8min at the temperature of 25 ℃;
step S4, carrying out secondary pure water soaking on the polycrystalline silicon rod: placing the etched polysilicon rod into pure water, and performing overflow soaking at the temperature of 90 ℃ until the resistivity of the overflow pure water is greater than 15 mu m omega;
step S5 nitrogen drying of the polysilicon rod: drying the soaked polysilicon rod in a clean room with the grade of more than 1000 by using nitrogen purified and filtered by a filter element with the diameter of 0.1 mu m;
step S6 annealing furnace cleaning: putting the dried silicon rod into a vertical annealing furnace, introducing purified nitrogen to replace air in the furnace, adding dichloroethylene to clean the surfaces of the furnace tube and the silicon rod, and continuously introducing purified nitrogen to replace cleaning gas dichloroethylene;
step S7 annealing of the polycrystalline silicon rod: under the protection of nitrogen with the heating rate of 2 ℃/min, heating to 1200 ℃, preserving the heat for 5 hours, and then cooling to room temperature under the condition of cooling to 2 ℃/min to prepare the polysilicon rod material.
The degreasing powder is prepared by the following steps:
step A1: heating 12-bromododecanoic acid to be molten, stirring and dropwise adding thionyl chloride under the condition that the rotating speed is 150r/min, heating to 85 ℃, performing reflux reaction for 5 hours to obtain an intermediate 1, adding the intermediate 1, aluminum chloride and benzene into a reaction kettle, and performing reflux reaction for 8 hours under the conditions that the rotating speed is 200r/min and the temperature is 90 ℃ to obtain an intermediate 2;
step A2: adding the intermediate 2, potassium hydroxide and diethylene glycol into a reaction kettle, stirring and adding hydrazine hydrate under the conditions that the rotating speed is 150r/min and the temperature is 80 ℃, performing reflux reaction for 5 hours under the condition that the temperature is 130 ℃ to obtain an intermediate 3, adding the intermediate 3 and concentrated sulfuric acid into the reaction kettle, reacting for 5 hours under the condition that the temperature is 70 ℃, cooling to 50 ℃, adding deionized water, standing for layering, removing a lower water layer, adding a sodium hydroxide solution into an organic phase, and adjusting the pH value to be 7 to obtain an intermediate 4;
step A3: adding 12-bromo-1-dodecanol, dimethylamine, N-dimethylformamide and potassium carbonate into a reaction kettle, reacting for 3 hours at 25 ℃ at the rotation speed of 200r/min, heating to 60 ℃, reacting for 6 hours to obtain an intermediate 5, adding the intermediate 5, oxalic acid, copper sulfate and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 8 hours at 130 ℃ to obtain an intermediate 6;
step A4: dissolving gelatin in deionized water, adding intermediate 6 and 1-hydroxybenzotriazole, reacting for 5h at the rotation speed of 150r/min and the temperature of 60 ℃, adding intermediate 4 and potassium carbonate, continuing to react for 5h, adding sodium chloroacetate, heating to 120 ℃, performing reflux reaction for 8h, adjusting the pH value to 7, and distilling to remove deionized water to obtain the degreasing powder.
Comparative example 1:
this comparative example compared to example 1, where the defatted flour was replaced with trisodium phosphate, the procedure was the same.
Comparative example 2:
this comparative example compared to example 1, using carbon tetrachloride instead of defatted flour, the remaining steps were the same.
Comparative example 3:
the comparative example compares with example 1 that the termination point of the primary soaking in step S2 is such that the resistivity of the pure water overflowing is more than 2 Μ Ω and less than 3 Μ Ω, and the rest steps are the same.
Comparative example 4:
the comparative example has the termination point of the secondary soaking in step S4 that the resistivity of the pure water overflowed is more than 10 mu omega and less than 15 mu omega compared with example 1, and the rest steps are the same.
Comparative example 5:
compared with the embodiment 1, the etching solution in the step S3 of the comparative example is mixed by hydrofluoric acid, nitric acid and acetic acid in a volume ratio of 3:2:1, and the rest steps are the same.
Comparative example 6
Compared with the example 1, in the comparative example, the temperature rise rate is adjusted to 5 ℃/min and the temperature drop rate is adjusted to 5 ℃/min in the step S7, and the rest steps are the same.
The polycrystalline silicon rods obtained in examples 1 to 3 and comparative examples 1 to 6 were measured for the metal content on the surface thereof in units of atoms/cm according to the standard of GB/T39145-2Meanwhile, the polysilicon rod is processed into silicon boats, the number of the silicon boats is 30, whether the silicon boats are broken or not is detected, the yield is calculated, and the result is as follows:
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Metallic iron content | 1E8 | 2E8 | 1E8 | 9E10 | 3E11 | 1E11 | 2E10 | 3E10 | 1E10 |
| Chromium metal content | 1E7 | 2E7 | 1E6 | 5E10 | 2E11 | 3E11 | 1E11 | 1E10 | 2E10 |
| Metallic nickel content | 2E6 | 2E6 | 2E6 | 1E11 | 2E11 | 2E11 | 1E10 | 1E10 | 1E10 |
| Yield of finished products | 100% | 100% | 100% | 83.3% | 76.7% | 85.4% | 82.7% | 79.3% | 91.8% |
From the above table, it is understood that the metal contents of the polysilicon rods obtained in examples 1 to 3 are all less than 1E10, and the yield of the silicon boat processed is 100%, indicating that the processing method of the present invention can remove impurities on the surface of the polysilicon rod well.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (5)
1. A high-cleanliness annealing method for a polycrystalline silicon rod material is characterized by comprising the following steps: the method specifically comprises the following steps:
step S1 degreasing and cleaning the polysilicon rod: dissolving the degreased powder in boiling water, adding the polysilicon rod, boiling and degreasing;
step S2, primary soaking of the polycrystalline silicon rod in pure water: soaking the cleaned polysilicon rod in pure water, and performing primary overflow soaking;
step S3 mixed acid etching of polysilicon rod: putting the polycrystalline silicon rod subjected to overflow soaking into mixed acid corrosive liquid for etching;
step S4, carrying out secondary pure water soaking on the polycrystalline silicon rod: soaking the cleaned polysilicon rod in pure water, and performing secondary overflow soaking;
step S5 nitrogen drying of the polysilicon rod: drying the soaked polysilicon rod in a clean room with the level of more than 1000 by using nitrogen;
step S6 annealing furnace cleaning: putting the dried silicon rod into a vertical annealing furnace, introducing purified nitrogen to replace air in the furnace, adding dichloroethylene to clean the surfaces of the furnace tube and the silicon rod, and continuously introducing purified nitrogen to replace cleaning gas dichloroethylene;
step S7 annealing of the polycrystalline silicon rod: heating to 1200 ℃, preserving heat for 3-5h, and cooling to room temperature to obtain a polycrystalline silicon rod material;
the degreasing powder is prepared by the following steps:
step A1: heating 12-bromododecanoic acid to be molten, stirring and dropwise adding thionyl chloride, carrying out reflux reaction to obtain an intermediate 1, adding the intermediate 1, aluminum chloride and benzene into a reaction kettle, and carrying out reflux reaction to obtain an intermediate 2;
the reaction process is as follows:
step A2: adding the intermediate 2, potassium hydroxide and diethylene glycol into a reaction kettle, stirring and adding hydrazine hydrate, performing reflux reaction to obtain an intermediate 3, adding the intermediate 3 and concentrated sulfuric acid into the reaction kettle, performing reaction, cooling, adding deionized water, standing for layering, removing a lower water layer, adding a sodium hydroxide solution into an organic phase, and adjusting the pH value to be 7 to obtain an intermediate 4;
the reaction process is as follows:
step A3: adding 12-bromo-1-dodecanol, dimethylamine, N-dimethylformamide and potassium carbonate into a reaction kettle, reacting, heating to react to obtain an intermediate 5, adding the intermediate 5, oxalic acid, copper sulfate and tetrahydrofuran into the reaction kettle, and performing reflux reaction to obtain an intermediate 6;
the reaction process is as follows:
step A4: dissolving gelatin in deionized water, adding an intermediate 6 and 1-hydroxybenzotriazole, reacting, adding an intermediate 4 and potassium carbonate, continuing to react, adding sodium chloroacetate, performing reflux reaction, adjusting the pH value to 7, and distilling to remove deionized water to obtain degreased powder;
the reaction process is as follows:
2. the method of claim 1, wherein the annealing process comprises: the molar ratio of the 12-bromododecanoic acid to the thionyl chloride in the step A1 is 1:2, and the molar ratio of the intermediate 1, the aluminum chloride and the benzene is 1:1: 5.
3. The method of claim 1, wherein the annealing process comprises: the using amount of the intermediate 2, the potassium hydroxide, the diethylene glycol and the hydrazine hydrate in the step A2 is 0.15mol:0.6mol:112.5mL:30mL, and the mass fraction of the sodium hydroxide is 10%.
4. The method of claim 1, wherein the annealing process comprises: the dosage ratio of the 12-bromo-1-dodecanol, the dimethylamine, the N, N-dimethylformamide and the potassium carbonate in the step A3 is 0.01mol:0.02mol:0.15mol:40mL, and the dosage ratio of the intermediate 5, the oxalic acid, the copper sulfate and the tetrahydrofuran is 0.01mol:0.015mol:0.02mol:50 mL.
5. The method of claim 1, wherein the annealing process comprises: the mass ratio of the gelatin, the intermediate 6, the 1-hydroxybenzotriazole, the intermediate 4, the potassium carbonate and the sodium chloroacetate in the step A4 is 5:0.8: 1.5:1.8: 0.4.
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