CN115724434A - Preparation method of high-purity superfine silicon powder - Google Patents
Preparation method of high-purity superfine silicon powder Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000011863 silicon-based powder Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 54
- 239000010703 silicon Substances 0.000 claims abstract description 54
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 150000003863 ammonium salts Chemical group 0.000 claims description 11
- 239000003093 cationic surfactant Substances 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000006004 Quartz sand Substances 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- JGOICJFFICGNEJ-UHFFFAOYSA-M disodium;3-[dihydroxy(oxido)silyl]propanoate Chemical compound [Na+].[Na+].O[Si](O)([O-])CCC([O-])=O JGOICJFFICGNEJ-UHFFFAOYSA-M 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- QQZJWQCLWOQDQV-UHFFFAOYSA-N 3-bromo-2-(bromomethyl)propanoic acid Chemical compound OC(=O)C(CBr)CBr QQZJWQCLWOQDQV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 239000006148 magnetic separator Substances 0.000 claims description 3
- 230000005389 magnetism Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- 238000004100 electronic packaging Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000011049 filling Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a preparation method of high-purity superfine silicon powder, belonging to the technical field of electronic packaging material preparation, wherein the silicon powder with the particle size of 13-15 mu m and the silicon powder with the particle size of 2.5-3.5 mu m are mixed according to the weight ratio of (3-4): 1, obtaining mixed silicon powder, activating the surface of the silicon powder by an acidic hydrogen peroxide oxidation system, growing a high-rigidity high-silicon cage-shaped silsesquioxane layer on the surface by taking the activated mixed silicon powder as a core, and generating silicon dioxide on the surface of the silicon powder under the condition of high-temperature heat treatment.
Description
Technical Field
The invention relates to the technical field of electronic packaging material preparation, in particular to a preparation method of high-purity superfine silicon powder.
Background
The spherical silicon micropowder is an amorphous quartz powder material with spherical particles and the main component of silicon dioxide, is white powder, and has wide development prospect due to high purity, fine particles, excellent dielectric property, low thermal expansion coefficient, high thermal conductivity and other superior properties; the spherical silicon micropowder is mainly applied to copper clad plates in large-scale integrated circuit packaging and epoxy plastic packaging material fillers, and also has application in the high and new technical fields of aviation, aerospace, coatings, catalysts, medicines, special ceramics, daily cosmetics and the like.
With the rapid development of the microelectronic industry in China, the requirements of large-scale and ultra-large-scale integrated circuits on packaging materials are higher and higher, and the requirement on the ultra-fineness and the high purity is met, and the requirement on the sphericization of particle shapes is particularly met. The spherical surface has good fluidity, the spherical surface is uniformly stirred with resin to form a film, the addition amount of the resin is small, the fluidity is best, the filling amount of the powder can reach the highest, and the weight ratio can reach 90.5%. Thus, the spheroidization means an increase in the filling rate of the fine silicon powder, and the higher the filling rate of the fine silicon powder, the smaller the thermal expansion coefficient thereof, and the lower the thermal conductivity, the closer the thermal expansion coefficient to that of single crystal silicon, and thus the better the performance of the electronic component produced therefrom. And secondly, the plastic packaging material prepared by the spheroidization has the minimum stress concentration and the highest strength, and when the stress concentration of the plastic packaging material of the angular powder is 1, the stress of the spherical powder is only 0.6, so that when the spherical powder plastic packaging material packages an integrated circuit chip, the yield is high, and mechanical damage is not easy to generate in the processes of transportation, installation and use. Thirdly, the spherical powder has small friction coefficient and small abrasion to the die, so that the service life of the die is long, and compared with angular powder, the service life of the die can be prolonged by one time.
However, the silica powder produced by the traditional process is the silica powder which is obtained by grinding the silica powder raw material and has more irregular and rhombohedral shapes, the silica powder has high viscosity and low filling rate when being used for packaging integrated circuits, the filling rate of the common silica powder is about 70 percent generally, and the produced product has defects such as flash and the like, thereby limiting the application of the silica powder in large-scale and ultra-large-scale integrated circuits.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of high-purity superfine silicon powder.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of high-purity superfine silicon powder comprises the following steps:
(1) Mixing the silicon micro powder with the particle size of 13-15 mu m and the silicon micro powder with the particle size of 2.5-3.5 mu m according to the weight ratio of (3-4): 1, mixing to obtain mixed silicon micro powder;
(2) Dispersing the mixed silicon micro powder in a hydrochloric acid solution, adding a hydrogen peroxide solution with the volume of 0.1-1% and the mass concentration of 30%, stirring at a low speed overnight, filtering out a precipitate, and washing with deionized water to be neutral to obtain first silicon micro powder;
(3) Weighing 3-aminopropyltriethoxysilane, dissolving the 3-aminopropyltriethoxysilane in absolute ethanol to obtain a solution with the concentration of 1-3wt.%, adding 1% deionized water, mixing and stirring uniformly, adding the first silicon micropowder, stirring at a low speed for reacting overnight, filtering, washing with absolute ethanol, and drying to obtain second silicon micropowder;
(4) Dispersing the second silicon micro powder in toluene or xylene, adding 3-bromo-2-bromomethyl propionic acid, introducing nitrogen for degassing, adding pentamethyl diethylenetriamine, introducing nitrogen for degassing again, stirring at room temperature for reaction for 8-12h, filtering out washing after the reaction is finished, dispersing in dimethylformamide, adding sodium azide, heating to 90-110 ℃, keeping the temperature and stirring for reaction for 24-30h, cooling to room temperature after the reaction is finished, filtering out and washing, dispersing in dimethylformamide again, adding propiolic acid under the condition of an ice water bath, adding 4-dimethylaminopyridine as a catalyst, stirring and mixing until the temperature of the system is stable, dropwise adding N, N-diisopropylcarbodiimide while stirring, stirring and reacting the reaction system under the ice water bath for 8-12h after the dropwise addition is finished, recovering to room temperature after the reaction is finished, adding aminated caged silsesquioxane, continuously stirring for reaction for 1-3h, filtering out, washing and drying to obtain third silicon micro powder;
the mass ratio of the second silica micro powder to the 3-bromo-2-bromomethylpropionic acid to the pentamethyldiethylenetriamine is 100: (3-5): (2.6-3.2); the mass ratio of the second silicon micropowder to the sodium azide, the propiolic acid, the 4-dimethylaminopyridine, the N, N-diisopropylcarbodiimide and the aminated cage-like silsesquioxane is 100: (2.6-3.6): (1-1.2): (0.1-0.14): (2.3-2.5): (8-12);
(5) And transferring the third silicon micropowder into a high-temperature furnace for high-temperature heat treatment, and cooling to room temperature to obtain the high-purity superfine silicon micropowder.
Preferably, the preparation method of the silica micropowder in the step (1) comprises the following steps:
s1, selecting SiO 2 Taking natural quartz sand with the content of 99.5-99.9% as a raw material, washing with water to remove dust and impurities on the surface, adding a hydrochloric acid solution for soaking overnight, filtering out, and washing with deionized water to be neutral;
and S2, transferring the washed quartz sand into a high-temperature furnace for melting treatment, obtaining a high-purity quartz fused mass after the temperature is reduced to room temperature, crushing the fused mass, transferring the crushed fused mass into a ball mill for ball milling, grading by an airflow classifier to obtain micro powder with the granularity of 800-2000 meshes, removing micro powder containing magnetism, metal or metal oxide by magnetic separation by a magnetic separator, and respectively obtaining silicon micro powder with the median particle size of 13-15 mu m and silicon micro powder with the median particle size of 2.5-3.5 mu m.
Preferably, the selected particle size of the natural quartz sand is 0.1-3mm.
Preferably, the melting process in step S2 is performed under the following conditions: the melting temperature is 1850 ℃, and the melting time is 12-14h.
Preferably, the ball milling medium for ball milling is a mixture of 1: (2-3): (1.5-2) alumina grinding balls with diameters of 3cm, 4cm and 5cm respectively, and performing ball milling for 25-35min.
Preferably, the treatment temperature of the high-temperature heat treatment in the step (5) is 800-1200 ℃, and the treatment time is 1-6h.
Preferably, the third fine silica powder in the step (4) further comprises the following processing steps:
dispersing the third silicon micropowder in an ethanol solution with the volume fraction of 80-95%, heating to 40-50 ℃, slowly adding a biquaternary ammonium salt cationic surfactant under stirring, continuing to keep the temperature and stir for 0.5-1h after the addition is finished, cooling to room temperature after the reaction is finished, adding carboxyethyl silanetriol sodium salt, keeping stirring and reacting for 1-2h, dropwise adding an absolute ethanol solution of ethyl orthosilicate under stirring, keeping stirring and reacting for 3-5h at a low speed after the dropwise addition is finished, filtering out precipitates after the reaction is finished, washing with absolute ethanol and deionized water in sequence, and drying;
the mass ratio of the third silicon micro powder to the biquaternary ammonium salt cationic surfactant, the sodium carboxyethyl silanetriol and the ethyl orthosilicate is 100: (1-3): (1-3): (1-5).
Preferably, the biquaternary ammonium salt cationic surfactant is a rosin-based biquaternary ammonium salt cationic surfactant.
Preferably, the processing conditions of the high-temperature heat treatment are as follows: sequentially carrying out heat treatment in the atmosphere of nitrogen and air at 800-1200 ℃ for 1-3h and 1-2h respectively.
The beneficial effects of the invention are as follows:
the preparation method is characterized in that on the basis of natural quartz micro powder, a ball milling method is combined to improve the sphericity of the silicon micro powder, and further the fluidity of the silicon micro powder is improved to reduce the influence of the doping amount of high silicon micro powder on the fluidity of a resin melt.
Furthermore, the invention utilizes the electronegativity of modified silicon dioxide, takes biquaternary ammonium salt cationic surfactant as a template, and passes through the electrostatic property and water in a solventOil amphiphilicity forms self-assembled micelles to further improve the sphericity, then carboxyethyl silanetriol sodium salt is used as a structure directing agent, tetraethoxysilane is used as a silicon source, a silicon dioxide layer is introduced on the surfaces of the micelles, and then N is added 2 And respectively calcining in the air to remove the surfactant and carbon residue to obtain the high-purity superfine silicon powder, wherein the high-purity superfine silicon powder has good grain size grading composition and sphericity, can improve the dispersibility of the high-purity superfine silicon powder in resin, reduces the influence of high doping amount on packaging viscosity, and is beneficial to further improving the filling rate.
Detailed Description
The invention is further described in connection with the following examples.
Example 1
A preparation method of high-purity superfine silicon powder comprises the following steps:
(1) Mixing silicon powder with the particle size of 13-15 mu m and silicon powder with the particle size of 2.5-3.5 mu m according to the weight ratio of 3.6:1, mixing to obtain mixed silicon micro powder;
(2) Dispersing the mixed silicon micro powder in a hydrochloric acid solution, adding a hydrogen peroxide solution with the mass concentration of 30% and the volume of 0.6% of the solution volume, stirring at a low speed overnight, filtering out a precipitate, and washing with deionized water to be neutral to obtain first silicon micro powder;
(3) Weighing 3-aminopropyltriethoxysilane, dissolving the 3-aminopropyltriethoxysilane in absolute ethanol to obtain a solution with the concentration of 1.5wt.%, adding 1% deionized water, mixing and stirring uniformly, adding the first silicon micropowder, stirring at a low speed for reacting overnight, filtering, washing with absolute ethanol, and drying to obtain a second silicon micropowder;
(4) Dispersing the second silicon micro powder in toluene or xylene, adding 3-bromo-2-bromomethyl propionic acid, introducing nitrogen for degassing, adding pentamethyl diethylenetriamine, introducing nitrogen for degassing again, stirring at room temperature for reaction for 8-12h, filtering out washing after the reaction is finished, dispersing in dimethylformamide, adding sodium azide, heating to 90-110 ℃, keeping the temperature and stirring for reaction for 24-30h, cooling to room temperature after the reaction is finished, filtering out and washing, dispersing in dimethylformamide again, adding propiolic acid under the condition of an ice water bath, adding 4-dimethylaminopyridine as a catalyst, stirring and mixing until the temperature of the system is stable, dropwise adding N, N-diisopropylcarbodiimide while stirring, stirring and reacting the reaction system under the ice water bath for 8-12h after the dropwise addition is finished, recovering to room temperature after the reaction is finished, adding aminated caged silsesquioxane, continuously stirring for reaction for 1-3h, filtering out, washing and drying to obtain third silicon micro powder;
the mass ratio of the second silica micro powder to the 3-bromo-2-bromomethylpropionic acid to the pentamethyldiethylenetriamine is 100:3.8:2.9; the mass ratio of the second silicon micropowder to the sodium azide, the propiolic acid, the 4-dimethylaminopyridine, the N, N-diisopropylcarbodiimide and the aminated cage-like silsesquioxane is (100): 3.2:1.1:0.12:2.3:10.7;
(5) Transferring the third silicon micropowder into a high-temperature furnace for high-temperature heat treatment, wherein the treatment temperature of the high-temperature heat treatment is 1000 ℃, the treatment time is 4 hours, and the high-purity superfine silicon micropowder is prepared after cooling to room temperature;
the preparation method of the silicon micropowder in the step (1) comprises the following steps:
s1, selecting SiO 2 Taking natural quartz sand with the content of 99.5-99.9% as a raw material, washing the natural quartz sand with water to remove dust and impurities on the surface, adding a hydrochloric acid solution for soaking overnight, filtering out, and washing with deionized water to be neutral;
s2, transferring the washed quartz sand into a high-temperature furnace for melting treatment, wherein the melting temperature is 1850 ℃, the melting time is 12-14 hours, obtaining a high-purity quartz fused mass after the temperature is reduced to the room temperature, transferring the fused mass into a ball mill for ball milling after crushing, and the ball milling medium is a mixture of 1:2.5:1.5 alumina grinding balls with the diameters of 3cm, 4cm and 5cm respectively, the ball milling time is 30min, the micro powder with the granularity of 800-2000 meshes is obtained after the classification of an airflow classifier, and the micro powder containing magnetism, metal or metal oxide is removed through the magnetic separation of a magnetic separator, so that the silicon micro powder with the median particle size of 13-15 mu m and the silicon micro powder with the median particle size of 2.5-3.5 mu m are respectively obtained.
Example 2
The preparation method of the high-purity superfine silicon powder is the same as the example 1, and is characterized in that: the mixed silicon micro powder is prepared from silicon micro powder with the particle size of 13-15 mu m and silicon micro powder with the particle size of 2.5-3.5 mu m according to the weight ratio of 2:1 are mixed to obtain the product.
Example 3
A preparation method of high-purity superfine silicon powder comprises the following steps:
steps (1) to (4) are the same as in example 1;
(5) Dispersing the third silicon micropowder obtained in the step (4) in an ethanol solution with the volume fraction of 90%, heating to 40-50 ℃, slowly adding the rosinyl biquaternary ammonium salt cationic surfactant under stirring, continuing to keep the temperature and stir for 0.5-1h after the addition is finished, cooling to room temperature after the reaction is finished, adding the sodium carboxyethyl silanetriol, keeping stirring and reacting for 1-2h, then dropwise adding the anhydrous ethanol solution of ethyl orthosilicate under stirring, keeping stirring and reacting at a low speed for 4h after the dropwise adding is finished, filtering out precipitates after the reaction is finished, washing with anhydrous ethanol and deionized water in sequence, and drying;
the mass ratio of the third silicon micropowder to the biquaternary ammonium salt cationic surfactant, the sodium carboxyethyl silanetriol and the ethyl orthosilicate is 100:1.4:1.3:2.8;
(6) And (4) transferring the dried product obtained in the step (5) into a high-temperature furnace, and sequentially carrying out heat treatment in the atmosphere of nitrogen and air at the heat treatment temperature of 1000 ℃ for 2 hours and 1.5 hours respectively.
Comparative example
Example 1 mixing of silica micropowder described in step (1).
The silica powder described in the comparative examples and examples 1-3 and comparative examples was used in the same formulation system for underfill performance testing with the following results:
finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A preparation method of high-purity superfine silicon powder is characterized by comprising the following steps:
(1) Mixing silicon powder with the particle size of 13-15 mu m and silicon powder with the particle size of 2.5-3.5 mu m according to the weight ratio of (3-4): 1, mixing to obtain mixed silicon micro powder;
(2) Dispersing the mixed silicon micro powder in a hydrochloric acid solution, adding a hydrogen peroxide solution with the mass concentration of 30% and the volume of 0.1-1% of the solution volume, stirring at a low speed overnight, filtering out a precipitate, and washing with deionized water to be neutral to obtain first silicon micro powder;
(3) Weighing 3-aminopropyltriethoxysilane, dissolving the 3-aminopropyltriethoxysilane in absolute ethanol to obtain a solution with the concentration of 1-3wt.%, adding 1% deionized water, mixing and stirring uniformly, adding the first silicon micropowder, stirring at a low speed for reacting overnight, filtering, washing with absolute ethanol, and drying to obtain a second silicon micropowder;
(4) Dispersing the second silicon micro powder in toluene or xylene, adding 3-bromo-2-bromomethyl propionic acid, introducing nitrogen, degassing, adding pentamethyl diethylenetriamine, introducing nitrogen, degassing, stirring at room temperature for 8-12h, filtering, washing, dispersing in dimethylformamide after reaction, adding sodium azide, heating to 90-110 ℃, keeping the temperature, stirring, reacting for 24-30h, cooling to room temperature after reaction, filtering, washing, dispersing in dimethylformamide again, adding propiolic acid under the condition of ice-water bath, adding 4-dimethylaminopyridine as a catalyst, stirring, mixing until the system temperature is stable, stirring while dropwise adding N, N-diisopropyl carbodiimide, stirring the reaction system under the ice-water bath for 8-12h after dropwise adding is completed, recovering to room temperature after reaction is completed, adding aminated cage-shaped silsesquioxane, continuously stirring, reacting for 1-3h, filtering, washing, drying, and preparing third silicon micro powder;
the mass ratio of the second silica micropowder to the 3-bromo-2-bromomethylpropionic acid to the pentamethyldiethylenetriamine is 100: (3-5): (2.6-3.2);
(5) And transferring the third silicon micropowder into a high-temperature furnace for high-temperature heat treatment, and cooling to room temperature to obtain the high-purity superfine silicon micropowder.
2. The method for preparing high-purity superfine silica powder according to claim 1, wherein the method for preparing the silica powder in the step (1) comprises the following steps:
s1, selecting SiO 2 Taking natural quartz sand with the content of 99.5-99.9% as a raw material, washing with water to remove dust and impurities on the surface, adding a hydrochloric acid solution for soaking overnight, filtering out, and washing with deionized water to be neutral;
and S2, transferring the washed quartz sand into a high-temperature furnace for melting treatment, obtaining a high-purity quartz fused mass after the temperature is reduced to room temperature, crushing the fused mass, transferring the crushed fused mass into a ball mill for ball milling, grading by an airflow classifier to obtain micro powder with the granularity of 800-2000 meshes, removing micro powder containing magnetism, metal or metal oxide by magnetic separation by a magnetic separator, and respectively obtaining silicon micro powder with the median particle size of 13-15 mu m and silicon micro powder with the median particle size of 2.5-3.5 mu m.
3. The method for preparing high-purity superfine silicon powder according to claim 2, wherein the selected particle size of the natural quartz sand is 0.1-3mm.
4. The method for preparing high-purity superfine silicon powder according to claim 2, wherein the melting treatment in step S2 is performed under the following conditions: the melting temperature is 1850 ℃, and the melting time is 12-14h.
5. The method for preparing high-purity superfine silica powder according to claim 2, wherein the ball milling medium for ball milling is a mixture of 1: (2-3): (1.5-2) alumina grinding balls with diameters of 3cm, 4cm and 5cm respectively, and performing ball milling for 25-35min.
6. The method for preparing high-purity superfine silicon powder according to claim 1, wherein the treatment temperature of the high-temperature heat treatment in the step (5) is 800-1200 ℃, and the treatment time is 1-6h.
7. The method for preparing high-purity superfine silicon powder according to claim 1, wherein the third silicon powder in the step (4) further comprises the following processing steps:
dispersing the third silicon micropowder in an ethanol solution with the volume fraction of 80-95%, heating to 40-50 ℃, slowly adding a biquaternary ammonium salt cationic surfactant under stirring, continuously keeping the temperature and stirring for 0.5-1h after the addition is finished, cooling to room temperature after the reaction is finished, adding sodium carboxyethyl silanetriol, keeping stirring and reacting for 1-2h, then dropwise adding an anhydrous ethanol solution of ethyl orthosilicate under stirring, keeping stirring and reacting at a low speed for 3-5h after the dropwise addition is finished, filtering out precipitates after the reaction is finished, washing with anhydrous ethanol and deionized water in sequence, and drying;
the mass ratio of the third silicon micropowder to the biquaternary ammonium salt cationic surfactant, the sodium carboxyethyl silanetriol and the ethyl orthosilicate is 100: (1-3): (1-3): (1-5).
8. The method according to claim 7, wherein the diquaternary ammonium salt cationic surfactant is a rosin-based diquaternary ammonium salt cationic surfactant.
9. A method for preparing high purity superfine silica powder according to claim 7, wherein the high temperature heat treatment is carried out under the following conditions: sequentially carrying out heat treatment in nitrogen and air atmosphere at 800-1200 ℃ for 1-3h and 1-2h respectively.
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| CN115521639A (en) * | 2022-09-16 | 2022-12-27 | 绩溪县黄山石英有限公司 | Superfine silica powder for latex paint |
| CN115974089B (en) * | 2023-02-17 | 2023-10-20 | 江苏海格新材料有限公司 | Production method of active silicon micropowder |
| CN117079872B (en) * | 2023-10-16 | 2024-01-26 | 南方珠江科技有限公司 | Insulated branch cable and preparation method thereof |
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| US20060239886A1 (en) * | 2005-04-22 | 2006-10-26 | Pentax Corporation | Silica aerogel coating and its production method |
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| CN111282698A (en) * | 2020-02-21 | 2020-06-16 | 江苏海格新材料有限公司 | Preparation method of electronic-grade superfine silica micropowder for copper-clad plate |
| CN113462196A (en) * | 2021-06-29 | 2021-10-01 | 江苏联瑞新材料股份有限公司 | Preparation method of narrow-distribution superfine silicon powder |
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| CN117326563B (en) * | 2023-09-28 | 2024-03-22 | 吉安豫顺新材料有限公司 | Preparation method and system of low-impurity silicon micro powder for vehicle-mounted copper-clad plate |
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