CN114804113B - Method for preparing high-purity SiC polycrystalline source powder by hybrid functionality silane non-initiation suspension polymerization - Google Patents
Method for preparing high-purity SiC polycrystalline source powder by hybrid functionality silane non-initiation suspension polymerization Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 15
- 230000000977 initiatory effect Effects 0.000 title claims abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 13
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 70
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 17
- 230000008025 crystallization Effects 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000197 pyrolysis Methods 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 239000000919 ceramic Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 150000001282 organosilanes Chemical class 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000007872 degassing Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000005087 graphitization Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000011109 contamination Methods 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical group [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 2
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical group [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 238000009396 hybridization Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 4
- 238000000815 Acheson method Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
- C01B32/963—Preparation from compounds containing silicon
- C01B32/977—Preparation from organic compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The preparation method of the high-purity SiC polycrystalline source powder by hybridization functionality silane non-initiation suspension polymerization relates to a preparation method of the high-purity SiC polycrystalline source powder, and aims to solve the technical problems of low purity, more byproducts, high nitrogen content and high cost of the existing preparation method of the SiC polycrystalline source powder. The method comprises the following steps: 1. preparing hybridized carbon silicon resin; 2. washing and drying resin; 3. irradiation crosslinking and primary pyrolysis carbonization are combined; 4. and (5) carrying out high-temperature reduction crystallization on the precursor ceramic. The purity of the silicon carbide polycrystalline source powder prepared by the method reaches more than 6N, and the nitrogen atom content in each gram of product is lower than 10 16 And each. Can be used in the field of high-purity silicon carbide preparation.
Description
Technical Field
The invention relates to a preparation method of high-purity silicon carbide polycrystalline source powder, belonging to the field of multifunctional inorganic materials.
Background
With the development of mobile communication networks and semiconductor industries, silicon carbide single crystals are used as important materials in the semiconductor industry, and the requirements on the performance and quality of the silicon carbide single crystals are higher and higher. Semi-insulating substrates require that silicon carbide not be too conductive, while too high a nitrogen concentration greatly increases the conductivity of silicon carbide, and the quality of the SiC polycrystalline source powder from which the silicon carbide single crystal is made is particularly important.
The purity of the SiC polycrystal source powder required for growing the SiC monocrystal is more than 6N, and three methods which can be used for preparing the SiC polycrystal material in engineering are an Acheson method (Acheson method), a CVD method and a solid-phase sintering method respectively.
According to the Acheson method, natural quartz sand and coke carbon-containing substances are used as synthetic raw materials, so that B, P and metal impurities in the raw materials inevitably enter crystal lattices of a product SiC, and a SiC material with the purity of more than 2N is difficult to prepare.
The CVD method adopts methyl chlorosilane as a raw material, prepares SiC polycrystalline powder in a reducing atmosphere, and is the method for preparing SiC polycrystalline source powder with the highest purity at present. However, the method has high requirements on materials and specifications of production equipment, and the reaction process produces more than ten byproducts, such as monomethyl trichlorosilane, dimethyl dichlorosilane, hydrogen-containing chlorosilane, trichlorosilane, silicon tetrachloride and the like, and the treatment and environmental protection investment of a large amount of chlorine-containing byproducts naturally lead to high production cost, so that the method is not suitable for large-scale industrialization.
The solid phase sintering method is a main method for preparing semi-insulating SiC single crystal materials at home and abroad at present, and the method takes high-purity carbon powder and high-purity silicon powder as starting materials, and obtains SiC polycrystalline source powder through a solid phase sintering process, so that the requirement of growing SiC single crystals can be basically met. The main problems of the method are as follows: the raw materials are high-purity materials and high-purity powder materials, so that the cost of polycrystalline SiC is increased; secondly, the raw materials are powder materials obtained by crushing bulk materials, so that impurities are necessarily introduced, and the mixed sintering of the powder is required to be subjected to unpacking, mixing, high-temperature sintering and other processes, so that the introduction of impurities, especially nitrogen element, due to the factors of high temperature, atmosphere environment and the like is unavoidable, and the quality and stability of the semi-insulating SiC single crystal are further affected.
Disclosure of Invention
The invention aims to solve the technical problems of low purity, more byproducts, high nitrogen content and high cost of the existing preparation method of SiC polycrystalline source powder, and provides a method for preparing high-purity SiC polycrystalline source powder by non-initiation suspension polymerization of hybrid functional silane.
The invention relates to a method for preparing high-purity SiC polycrystalline source powder by non-initiation suspension polymerization of hybridized functional silane, which comprises the following steps:
1. preparing hybrid carbon silicon resin:
the preparation method comprises the steps of uniformly mixing organosilane, catalytic monomer and active monomer, putting the mixture into a quartz reaction device or a reaction device with a tetrafluoroethylene lining, reacting under the conditions of heating, microwave, ultrasonic and/or ultraviolet irradiation, and obtaining hybridized carbon silicon resin through non-catalytic suspension polymerization;
2. washing and drying resin: washing the hybridized carbon silicon resin with ultrapure water until the resistivity of the outflow water reaches 18.3MΩ & cm, and ensuring that the whole washing process has no metal contamination; then conveying the hybrid carbon silicon resin into a vacuum drying chamber through a communicating vessel, and dehydrating and drying under the conditions that the temperature is 30-150 ℃ and the vacuum degree is 0.01-10000 Pa to obtain clean hybrid carbon silicon resin;
3. irradiation crosslinking combined primary pyrolytic carbonization:
putting the clean hybrid carbon silicon resin into a quartz sagger, introducing protective gas, irradiating for 5-10 hours by ultraviolet or electron, wherein the energy is 1-5 Mev, and improving the crosslinking degree; placing the crosslinked resin into a pyrolysis reactor, heating to 850-1050 ℃ and sintering for 6-24 hours to obtain an insoluble and infusible silicon carbide precursor;
or, putting the clean hybrid carbon silicon resin into a high-purity quartz sagger, introducing protective gas, and heating for 5-10 minutes by using microwaves, wherein the microwave frequency is 915MHz or 2450MHz, the microwave power is 6-60 kW, and the crosslinking degree is improved; placing the crosslinked resin into a pyrolysis reactor, heating to 850-1050 ℃ and sintering for 6-24 hours to obtain an insoluble and infusible silicon carbide precursor;
4. high-temperature reduction crystallization of precursor ceramics: the silicon carbide precursor is subjected to surface degassing treatment by high-temperature steam, and is input into a graphitization furnace, and is heated to 1650-2200 ℃ and kept under pressure of 10 under argon or hydrogen atmosphere -5 And Pa-1 atm, performing reduction crystallization for 12-36 hours to obtain the high-purity silicon carbide polycrystalline source powder.
Further, the preparation method of the hybrid carbon silicone resin in the step one comprises the following steps: firstly adding deionized water into a reaction kettle with a polytetrafluoroethylene lining, adding a catalytic monomer in a stirring state, heating to 60-75 ℃ and stirring at constant temperature for 30-50 min; then dripping organosilane and active monomer into a reaction kettle, maintaining the temperature between 60 and 75 ℃ in the dripping process, continuously stirring for 2 to 3 hours at the temperature between 60 and 75 ℃ after the dripping is finished, stopping heating, cooling to room temperature, and continuously stirring for 3 to 4 hours; and washing the resin in the kettle with deionized water, and discharging to obtain the hybrid carbon silicon resin.
Still further, the organosilane in the first step is propyl trimethoxysilane or methyl trimethoxysilane.
Still further, the catalytic monomer in the first step is aminosilane or vinylsilane.
Further, the reactive monomer in the first step is phenylsilane or diphenylsilane.
Further, the mass ratio of deionized water, catalytic monomer, organosilane and active monomer is (10-15): 1: (20-30): (10-25).
Still further, the protective gas in step four is argon.
The invention prepares the hybridized carbon silicon resin by a hybridization functionality silicane non-initiation suspension polymerization method, the hybridized carbon silicon resin is first pyrolyzed and carbonized to prepare silicon carbide precursor, the precursor is sintered at high temperature to prepare high-purity silicon carbide polycrystalline source powder, the purity of the silicon carbide polycrystalline source powder reaches more than 6N, and the nitrogen atom content in each gram of product is lower than 10 16 And each.
The method of the invention can be used in the field of high-purity silicon carbide preparation.
Drawings
FIG. 1 is a photograph of a hybrid carbon silicone obtained in step one of example 1;
FIG. 2 is a photograph of a silicon carbide precursor obtained in step three of example 1;
FIG. 3 is a report of purity analysis of high purity silicon carbide polycrystalline source powder prepared in example 1;
FIG. 4 is a report of the composition analysis of the high purity silicon carbide polycrystalline source powder prepared in example 1.
Detailed Description
The following examples are used to demonstrate the benefits of the present invention.
Example 1: the method for preparing the high-purity SiC polycrystalline source powder by the non-initiation suspension polymerization of the hybridized functional silane comprises the following steps:
1. preparation of hybrid carbon silicone resin: 282.6g of deionized water is firstly added into a reaction kettle with a polytetrafluoroethylene lining, and 20.28g of aminosilane is added under stirring; heating to 60 ℃ and stirring at constant temperature for 30min; then 493.18g of propyl trimethoxy silane and 424.91g of diphenyl dimethoxy silane are dripped into a reaction kettle, the temperature is maintained between 60 and 75 ℃ in the dripping process, stirring is continued for 2 hours at 60 to 75 ℃ after the dripping is finished, then heating is stopped, the temperature is reduced to room temperature, and stirring is continued for 3 hours; washing resin in the kettle with 2000mL of deionized water for 3 times, and discharging to obtain hybridized carbon silicon resin;
2. washing and drying resin: washing the hybridized carbon silicon resin with ultrapure water until the resistivity of the outflow water reaches 18.3MΩ & cm, and ensuring that the whole washing process has no metal contamination; then conveying the hybrid carbon silicon resin into a vacuum drying chamber through a communicating vessel, and dehydrating and drying for 12 hours at the temperature of 100 ℃ and the vacuum degree of 1000Pa to obtain clean hybrid carbon silicon resin;
3. irradiation crosslinking combined primary pyrolytic carbonization: inputting clean hybrid carbon silicon resin into a high-purity quartz sagger, simultaneously introducing protective gas argon, irradiating for 6 hours by using an electron beam of 5Mev by using an electron irradiation machine, inputting the irradiated mixture into a tube furnace, heating to 1000 ℃ and sintering for 24 hours to obtain insoluble and infusible silicon carbide precursor; siO of the high-purity quartz sagger in the step 2 The mass percent purity is 99.99 percent, and the pyrolysis yield is 72 percent in the primary pyrolysis carbonization process;
4. high-temperature reduction crystallization of precursor ceramics: and (3) carrying out surface degassing treatment on the silicon carbide precursor by high-temperature steam with the temperature of 110 ℃, then inputting the silicon carbide precursor into a graphitization furnace, heating to 2000 ℃ under the argon atmosphere, maintaining the pressure at 1000Pa, carrying out reduction crystallization, and carrying out reduction crystallization for 24 hours to obtain the high-purity silicon carbide polycrystalline source powder.
FIG. 1 is a photograph of a hybrid carbon silicone obtained in step one of example 1; the hybrid carbon silicone is white particles.
FIG. 2 is a photograph of a silicon carbide precursor obtained in step three of example 1; the silicon carbide precursor is a black powder.
The purity analysis result of the high purity silicon carbide polycrystalline source powder obtained in this example is shown in FIG. 3, and the analysis result is that the content of nitrogen atoms in each gram of the product is lower than 10 16 And each.
The analysis results of the components of the high purity silicon carbide polycrystalline source powder obtained in this example are shown in fig. 4, and it is clear from the analysis results that the purity of the high purity silicon carbide polycrystalline source powder of this example is 6N grade.
Example 2: the method for preparing the high-purity SiC polycrystalline source powder by the non-initiation suspension polymerization of the hybridized functional silane comprises the following steps:
1. preparation of hybrid carbon silicone resin: firstly, 285g of deionized water is added into a reaction kettle with a polytetrafluoroethylene lining, and 29.59g of vinyl silane is added under stirring; heating to 60 ℃ and stirring at constant temperature for 30min; then 490.42g of propyl trimethoxy silane and 422.85g of phenyl trimethoxy silane are dripped into a reaction kettle, the temperature is maintained between 60 and 75 ℃ in the dripping process, stirring is continued for 2 hours at 60 to 75 ℃ after the dripping is finished, heating is stopped, the temperature is reduced to room temperature, and stirring is continued for 3 hours; washing resin in the kettle with 2000mL of deionized water for 3 times, and discharging to obtain hybridized carbon silicon resin;
2. washing and drying resin: washing the hybridized carbon silicon resin with ultrapure water until the resistivity of the outflow water reaches 18.3MΩ & cm, and ensuring that the whole washing process has no metal contamination; then conveying the hybrid carbon silicon resin into a vacuum drying chamber through a communicating vessel, and dehydrating and drying the hybrid carbon silicon resin under the conditions of the temperature of 80 ℃ and the vacuum degree of 1000Pa to obtain clean hybrid carbon silicon resin;
3. irradiation crosslinking combined primary pyrolytic carbonization: putting the clean hybrid carbon silicon resin into a high-purity quartz sagger, simultaneously introducing argon gas for maintaining, heating for 5 minutes by microwaves, wherein the microwave frequency is 915MHz, the microwave power is 30kW, and the crosslinking degree is improved; placing the crosslinked resin into a pyrolysis reactor, heating to 950 ℃ and sintering for 20 hours to obtain an insoluble and infusible silicon carbide precursor;
4. high-temperature reduction crystallization of precursor ceramics: and (3) carrying out surface degassing treatment on the silicon carbide precursor by high-temperature steam with the temperature of 120 ℃, inputting the silicon carbide precursor into a graphitization furnace, heating to 2000 ℃ under the argon atmosphere, maintaining the pressure of 100Pa, carrying out reduction crystallization, and obtaining the high-purity silicon carbide polycrystalline source powder with the reduction crystallization time of 24 hours.
The purity of the high purity silicon carbide polycrystalline source powder of this example was grade 6N.
Example 3: the method for preparing the high-purity SiC polycrystalline source powder by the non-initiation suspension polymerization of the hybridized functional silane comprises the following steps:
1. preparation of hybrid carbon silicone resin: 352.2g of deionized water is firstly added into a reaction kettle with a polytetrafluoroethylene lining, and 29.59g of vinyl silane is added under stirring; heating to 60 ℃ and stirring at constant temperature for 30min; then 408.66g of methyltrimethoxysilane and 679.94g of phenyltrimethoxysilane are dripped into a reaction kettle, the temperature is maintained between 60 and 75 ℃ in the dripping process, stirring is continued for 2 hours at 60 to 75 ℃ after the dripping is finished, heating is stopped, the temperature is reduced to room temperature, and stirring is continued for 3 hours; washing resin in the kettle with 2000mL of deionized water for 3 times, and discharging to obtain hybridized carbon silicon resin;
3. irradiation crosslinking combined primary pyrolytic carbonization: inputting clean hybrid carbon silicon resin into a high-purity quartz sagger, simultaneously introducing protective gas argon, irradiating for 8 hours by using an electron beam of 4Mev by using an electron irradiation machine, inputting the irradiated silicon resin into a tube furnace, heating to 1050 ℃ and sintering for 20 hours to obtain insoluble and infusible silicon carbide precursor;
4. high-temperature reduction crystallization of precursor ceramics: and (3) carrying out surface degassing treatment on the silicon carbide precursor by high-temperature steam with the temperature of 130 ℃, then inputting the silicon carbide precursor into a graphitization furnace, heating to 1800 ℃ under the argon atmosphere, maintaining the pressure at 1000Pa, carrying out reduction crystallization, and obtaining the high-purity silicon carbide polycrystalline source powder with the reduction crystallization time of 36 hours.
The purity of the high purity silicon carbide polycrystalline source powder of this example was grade 6N.
Claims (5)
1. The method for preparing the high-purity SiC polycrystalline source powder by the non-initiation suspension polymerization of the hybridized functional silane is characterized by comprising the following steps of:
1. preparing hybrid carbon silicon resin: the preparation method comprises the steps of uniformly mixing organosilane, catalytic monomer and active monomer, putting the mixture into a quartz reaction device or a reaction device with a tetrafluoroethylene lining, reacting under the conditions of heating, microwave, ultrasonic and/or ultraviolet irradiation, and obtaining hybridized carbon silicon resin through non-catalytic suspension polymerization; the method comprises the following steps: firstly adding deionized water into a reaction kettle with a polytetrafluoroethylene lining, adding a catalytic monomer in a stirring state, heating to 60-75 ℃, and stirring at constant temperature for 30-50 min; then, dripping organosilane and active monomer into a reaction kettle, maintaining the temperature at 60-75 ℃ in the dripping process, continuously stirring for 2-3 hours at 60-75 ℃ after dripping, stopping heating, cooling to room temperature, and continuously stirring for 3-4 hours; washing resin in the kettle with deionized water, and discharging to obtain hybridized carbon silicon resin; wherein the organosilane is propyl trimethoxy silane or methyl trimethoxy silane; the catalytic monomer is amino silane or vinyl silane; the active monomer is phenylsilane or diphenylsilane; the mass ratio of deionized water, catalytic monomer, organosilane and active monomer is (10-15): 1: (20-30): (10-25);
2. washing and drying resin: washing the hybridized carbon silicon resin with ultrapure water until the resistivity of the outflow water reaches 18.3MΩ & cm, and ensuring that the whole washing process has no metal contamination; conveying the hybrid carbon silicon resin into a vacuum drying chamber through a communicating vessel, and dehydrating and drying under the conditions that the temperature is 30-150 ℃ and the vacuum degree is 0.01-10000 Pa to obtain clean hybrid carbon silicon resin;
3. irradiation crosslinking combined primary pyrolytic carbonization:
putting the clean hybrid carbon silicon resin into a quartz sagger, introducing protective gas, irradiating for 5-10 hours by ultraviolet or electron, wherein the energy is 1-5 Mev, and improving the crosslinking degree; placing the crosslinked resin into a pyrolysis reactor, heating to 850-1050 ℃ and sintering for 6-24 hours to obtain an insoluble and infusible silicon carbide precursor;
or, putting the clean hybrid carbon silicon resin into a high-purity quartz sagger, and simultaneously introducing protective gas to heat for 5-10 minutes by microwaves, wherein the microwave frequency is 915MHz or 2450MHz, the microwave power is 6-60 kW, so that the crosslinking degree is improved; placing the crosslinked resin into a pyrolysis reactor, heating to 850-1050 ℃ and sintering for 6-24 hours to obtain an insoluble and infusible silicon carbide precursor;
4. high-temperature reduction crystallization of precursor ceramics: the silicon carbide precursor is subjected to surface degassing treatment by high-temperature steam, and is input into a graphitization furnace, and is heated to 1650-2200 ℃ and kept under pressure of 10 under argon or hydrogen atmosphere -5 And (3) carrying out reduction crystallization for 12-36 hours under Pa-1 atm to obtain the high-purity silicon carbide polycrystalline source powder.
2. The method for preparing high-purity SiC polycrystalline source powder by non-initiation suspension polymerization of hybridized functional silane according to claim 1, wherein the protective gas in the fourth step is argon.
3. The method for preparing high-purity SiC polycrystalline source powder by non-initiation suspension polymerization of hybridized functional silane according to claim 1, wherein the temperature in the reduction crystallization in the fourth step is 1800-2000 ℃.
4. The method for preparing high-purity SiC polycrystalline source powder by non-initiation suspension polymerization of hybridized functional silane according to claim 1, wherein the pressure in the reduction crystallization in the fourth step is 100 Pa-1000 Pa.
5. The method for preparing high-purity SiC polycrystalline source powder by non-initiation suspension polymerization of hybridized functional silane according to claim 1, which is characterized in that the reduction crystallization time is 20-24 hours.
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