CN115611287B - Preparation method of ultra-high purity silica sol with adjustable association degree, ultra-high purity silica sol and application of ultra-high purity silica sol - Google Patents
Preparation method of ultra-high purity silica sol with adjustable association degree, ultra-high purity silica sol and application of ultra-high purity silica sol Download PDFInfo
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000011164 primary particle Substances 0.000 claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000003960 organic solvent Substances 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 44
- 239000012498 ultrapure water Substances 0.000 claims description 31
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 30
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- -1 alkoxy silane Chemical compound 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 238000000108 ultra-filtration Methods 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 5
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- NQOFYFRKWDXGJP-UHFFFAOYSA-N 1,1,2-trimethylguanidine Chemical compound CN=C(N)N(C)C NQOFYFRKWDXGJP-UHFFFAOYSA-N 0.000 claims description 3
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 abstract description 11
- 241001089723 Metaphycus omega Species 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011163 secondary particle Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000002572 peristaltic effect Effects 0.000 description 10
- 230000003321 amplification Effects 0.000 description 8
- 238000003199 nucleic acid amplification method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000003082 abrasive agent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000017060 Arachis glabrata Nutrition 0.000 description 3
- 241001553178 Arachis glabrata Species 0.000 description 3
- 235000010777 Arachis hypogaea Nutrition 0.000 description 3
- 235000018262 Arachis monticola Nutrition 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000020232 peanut Nutrition 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000012431 wafers Nutrition 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
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
Abstract
The invention discloses a preparation method of ultra-high purity silica sol with adjustable association degree, ultra-high purity silica sol and application thereof, wherein the relative dielectric constant of a system is adjusted and controlled through the proportion and the proportion of different solvents, and then the ultra-high purity silica sol with the mass fraction of more than 20%, the primary particle size of 30-150nm and the association degree of 1.2-2.7 is obtained through a series of steps of sol gel, concentration, water replacement, filtration and the like. The invention solves the problems of difficult control of association degree and complex process in the traditional alkoxide method, and has better stability among batches.
Description
Technical Field
The invention belongs to the field of nano material preparation, and in particular relates to a method for preparing ultra-high purity silica sol by an alkoxide method with adjustable association degree, a product and application of the product in the field of semiconductor CMP polishing.
Background
Silica sol is a colloidal substance obtained by dispersing silica particles in water or other solvents, and is widely used in the industries of papermaking, catalysts, casting, paints, and the like. In recent years, high purity silica sols are widely used in the Chemical Mechanical Polishing (CMP) step of silicon wafers and semiconductor devices.
In the manufacturing process of semiconductor devices, hundreds of CMP steps are involved, and the requirements of different CMP processes on abrasive materials are different, including purity, particle size, morphology, etc. For purity, the alkoxide method is a relatively mature process for producing ultra-high purity silica sol at present, and the purity of the silica sol prepared by the alkoxide method is directly related to the purity of raw materials.
With respect to particle size, in rough polishing of CMP, a higher removal rate is required, and thus large-particle abrasives are more favored, whereas in fine polishing, surface flatness is more favored, and small-particle abrasives are favored. For morphology, the particle morphology of the silica sol prepared by the alkoxide method can be divided into spheres and non-spheres, wherein the non-spheres can be divided into peanut type and abnormal type according to different association degrees, and the association degree refers to the ratio of the secondary particle diameter to the primary particle diameter of the particles. When the association degree is less than 1.7, the particles are spherical; when the association degree is between 1.7 and 2.3, the particles are associated in pairs to form peanut type particles; when the association degree is more than 2.3, the particles are abnormal. Peanut-shaped and special-shaped abrasive materials can obviously improve polishing rate. The particle size and association degree of the silica sol are controlled by controlling the concentration of the reactants, the concentration of the catalyst, the adding speed of the reactants and the like in a combined manner, but the particle size and association degree of the silica sol are greatly influenced by the control of the factors, and when the particle size of the prepared silica sol is gradually increased, the prepared silica sol is more biased to be spherical, and the association degree is smaller than 1.7.
CN101495409A is prepared by mixing TMOS and methanol at a volume ratio of 3:1 as raw material solutions, mixing methanol, water and ammonia water as reaction solvents, wherein the concentrations of water and ammonia water in the reaction solvents are 15wt% and 1wt%, respectively, dropwise adding 1 volume of the raw material solution into 9 volumes of the reaction solvents at 20 ℃, and obtaining peanut-shaped silica sol with a primary particle size of 32.1nm, a secondary particle size of 74.8nm and a degree of association of 2.33 after the reaction. The JPA2011201719 and the JPA2013082584 are prepared into acidic or neutral seed solution through a particle growth method, and then the concentration, the addition speed and the like of the seed solution are controlled through adding the seed solution and the alkali catalyst to prepare the special-shaped silica sol.
Therefore, the peanut-shaped silica sol is prepared by strictly controlling the concentration of reactants and catalysts in a reaction system and the adding speed of reaction raw materials under different conditions in the prior art, but the parameters of the whole process are difficult to control, the repeatability is poor, obvious amplification effects exist, and the particle size and the association degree can be influenced by each parameter, so that the large-particle-size peanut-shaped silica sol is difficult to prepare by the traditional alkoxide method. The preparation of the special-shaped silica sol is to synthesize the silica sol by a two-step method, the influence factors are more in the synthesis process, the production process is complex, and in the industrial production, the mass transfer and the heat transfer are difficult in the reaction process, obvious amplification effects exist, so that the stability among batches is difficult to control.
Thus, there remains a need for a simple and easy method for preparing a desired silica sol of a certain degree of association by adjusting or monitoring a certain parameter.
Disclosure of Invention
Aiming at the problems, the invention creatively provides a preparation method of the ultra-high purity silica sol with adjustable association degree, which comprises the steps of uniformly mixing an organic solvent, ultrapure water and a base catalyst according to a certain proportion, and adjusting and controlling the dielectric constant of a reaction system instead of the concentration of a reactant and the adding speed of the reactant, so that the silica sol with different association degrees can be controllably prepared under different particle sizes, the amplification effect is smaller, the batch-to-batch stability of the particle morphology is better, and the process is relatively simple for producing the special-shaped silica sol.
It is another object of the present invention to provide such an ultra-high purity silica sol product.
It is a further object of the present invention to provide the use of such ultra-high purity silica sols in CMP.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the preparation method of the ultra-high purity silica sol with adjustable association degree comprises the following steps:
1) And (3) preparing a solution A: uniformly mixing an organic solvent, ultrapure water and a base catalyst in a certain proportion, and adjusting the types and the dosage of the organic solvent to ensure that the relative dielectric constant of A liquid is between 39 and 52, and the association degree of the prepared silica sol is between 1.2 and 2.7; wherein,
adjusting the relative dielectric constant of the solution A to be more than 50, wherein the association degree of the prepared silica sol is less than 1.7, and the silica sol is spherical;
the relative dielectric constant of the solution A is regulated to be between 43 and 50, the association degree of the prepared silica sol is correspondingly between 1.7 and 2.3, and the silica sol is peanut-shaped;
adjusting the relative dielectric constant of the solution A to be less than 43, wherein the association degree of the prepared silica sol is more than 2.3, and the silica sol is special-shaped;
2) And (3) preparing a solution B: uniformly mixing an organic solvent and alkoxy silane;
3) Initial silica sol preparation: adding the solution B into the solution A at a certain temperature, and stirring and reacting to obtain initial silica sol;
4) Concentrating: concentrating the initial silica sol to a mass fraction of 10-20% by vacuum heating concentration;
5) Solvent replacement: replacing the organic solvent in the concentrated silica sol with ultrapure water, and concentrating to more than 20% by mass;
6) And (3) filtering: and filtering the concentrated silica sol to remove large particles to obtain the ultra-high purity silica sol.
Wherein the organic solvent in the step 1) and the step 2) is one or more of methanol, ethanol, propanol, isopropanol, acetonitrile, acetone, methyl ethyl ketone, diethyl ether, ethyl propyl ether and the like; preferably, the organic solvent in the liquid B is the same as the organic solvent in the liquid a.
Wherein the resistivity of the ultrapure water in the step 1) is not less than 10 M.OMEGA.cm, preferably not less than 18.2 M.OMEGA.cm.
Wherein, the alkali catalyst in the step 1) is at least any one of alkali metal hydroxide, ammonia water, organic amine or guanidine compound; preferably, the alkali metal hydroxide is selected from at least any one of potassium hydroxide, sodium hydroxide and lithium hydroxide, the organic amine is selected from at least any one of ethylenediamine, triethanolamine and tetramethyl ammonium hydroxide, and the guanidine compound is selected from at least any one of tetramethyl guanidine, trimethyl guanidine and guanidine carbonate; more preferably, the base catalyst is selected from ammonia, ethylenediamine or tetramethylammonium hydroxide.
Wherein, the mass fraction of the organic solvent in the A solution in the step 1) is 20% -80%, the mass fraction of the ultrapure water is 19% -79%, and the mass fraction of the base catalyst is 0.5% -1.5%.
Wherein, the alkoxy silane in the step 2) is one or more of tetramethoxy silane, tetraethoxy silane and tetrapropoxy silane, and is preferably tetramethoxy silane.
Wherein the volume ratio of the organic solvent to the alkoxy silane in the step 2) is 1:4-4:1, and the molar ratio of the alkoxy silane to the water in the step 1) is less than 1; preferably, the volume ratio of the organic solvent to the alkoxysilane is 1:3-1:1, wherein the molar ratio of the alkoxy silane to water is less than 1:4.
Wherein, the initial silica sol in the step 3) is prepared, and the reaction temperature is between 5 ℃ and 50 ℃, preferably between 5 ℃ and 30 ℃; the dripping time of the solution B to the solution A is 0.1min-40min, preferably 0.1min-20min, the stirring speed is 200r/min-1000r/min, and the reaction time is 0.5h-3h.
Wherein, the solvent replacement in the step 5) adopts the heating and the ultra-pure water supplementing, the solvent in the water is removed by evaporation, or adopts the ultra-filtration mode, and the ultra-pure water supplementing and the concentration are carried out until the solvent content in the silica sol is removed to be below 200ppm, preferably below 100 ppm; more preferably, the concentration in the step 5) adopts vacuum heating concentration or ultrafiltration membrane concentration, and the mass fraction of the silica sol is concentrated to more than 20%.
Wherein, the filtering in the step 6) adopts a filter element made of PFA material, and adopts two-stage or three-stage filtering, and the filtering precision is 0.2 μm-5 μm.
On the other hand, the ultra-high purity silica sol prepared by the method has the morphology of sphere, peanut or special shape, the primary particle size is between 30 and 150nm, the association degree is between 1.2 and 2.7, and the total content of metal ions is less than 1ppm.
In a further aspect, the ultra-high purity silica sol as described above is used in Chemical Mechanical Polishing (CMP).
Compared with the prior art, the invention has the following beneficial effects:
1) The invention creatively proposes to adjust the relative dielectric constant of a reaction system by changing the types and the proportion of the organic solvent in the alkoxide method instead of changing the concentration and the dropping speed of reactants, so that the association degree of the silica sol correspondingly prepared between 39 and 52 can be 1.2 to 2.7 under different particle sizes, and the spherical, peanut-shaped or special-shaped silica sol can be stably prepared within the range of 30 to 150nm of primary particle size.
2) Compared with the traditional alkoxide method, the method can realize batch-to-batch stability through fine control of process conditions, and the method only regulates and controls the relative dielectric constant of the system on the premise of controlling certain target particle size without monitoring the concentration and the dropping speed of various raw materials, so that the operation is simpler, the method is suitable for industrial mass production, and the batch-to-batch stability is easier to control.
Drawings
FIG. 1 is a graph showing the association degree with the relative dielectric constant of the silica sol prepared according to the present invention.
Fig. 2 is a TEM image of silica sol particles prepared in a solvent system of different dielectric constants according to an embodiment of the present invention.
Detailed Description
In order to better understand the technical solution of the present invention, the following further illustrates the preparation method of the present invention by way of more specific examples, without any limitation.
The preparation method of the ultra-high purity silica sol with adjustable association degree comprises the following steps:
1) And (3) preparing a solution A: uniformly mixing an organic solvent, ultrapure water and a base catalyst in a certain proportion, and adjusting the type and the dosage of the organic solvent to ensure that the relative dielectric constant of A liquid is between 39 and 52, wherein the association degree of the prepared silica sol is between 1.2 and 2.7; wherein,
adjusting the relative dielectric constant of the solution A to be more than 50, wherein the association degree of the prepared silica sol is less than 1.7, and the silica sol is spherical;
the relative dielectric constant of the solution A is regulated to be between 43 and 50, the association degree of the prepared silica sol is correspondingly between 1.7 and 2.3, and the silica sol is peanut-shaped;
adjusting the relative dielectric constant of the solution A to be less than 43, wherein the association degree of the prepared silica sol is more than 2.3, and the silica sol is special-shaped;
2) And (3) preparing a solution B: uniformly mixing an organic solvent and alkoxy silane;
3) Initial silica sol preparation: adding the solution B into the solution A at a specific speed at a specific temperature, and stirring and reacting for a period of time to obtain initial silica sol;
4) Concentrating: concentrating the initial silica sol to obtain a concentrated silica sol with the mass fraction of 10-20%;
5) Solvent replacement: replacing methanol in the concentrated silica sol with ultrapure water, concentrating until the mass fraction is 20% or more;
6) And (3) filtering: and filtering the concentrated silica sol to remove large particles, thus obtaining the high-purity silica sol product.
The organic solvent in the step 1) is any one or more of methanol, ethanol, propanol, isopropanol, acetonitrile, acetone, methyl ethyl ketone, diethyl ether, ethyl propyl ether and the like, and preferably methanol. The ultrapure water is deionized water having a resistivity of 10 M.OMEGA.cm or more, and is prepared by using a mil-q direct water purifier, for example, and includes, but is not limited to, deionized water having a resistivity of 10 M.OMEGA.cm, 11 M.OMEGA.cm, 12 M.OMEGA.cm, 13 M.OMEGA.cm, 14 M.OMEGA.cm, 15 M.OMEGA.cm, 16 M.OMEGA.cm, 17 M.OMEGA.cm, 18 M.OMEGA.cm, 19 M.OMEGA.cm, 20 M.OMEGA.cm, and preferably having a resistivity of 18.2 M.OMEGA.cm or more. The base catalyst is alkali metal hydroxide such as potassium hydroxide and sodium hydroxide, ammonia water or organic amine such as ethylenediamine, triethanolamine and tetramethyl ammonium hydroxide, or guanidine compound such as: one or more of tetramethyl guanidine, trimethyl guanidine and guanidine carbonate, preferably ammonia water, ethylenediamine and tetramethyl ammonium hydroxide.
The contents of the three substances in the solution A are as follows: the mass fraction of the organic solvent is 20% -80%, the mass fraction of the ultrapure water is 19% -79%, and the mass fraction of the alkali catalyst is 0.5-1.5%. The dielectric constant of the system is regulated and controlled by regulating and controlling the proportion and the proportion of different solvents, so that the dielectric constant of the A liquid is more than 50, the association degree of the prepared silica sol is less than 1.7, and the silica sol is spherical; the relative dielectric constant of the solution A is between 43 and 50, the association degree of the prepared silica sol is between 1.7 and 2.3, and the silica sol is peanut-shaped; the relative dielectric constant of the solution A is smaller than 43, and the association degree of the prepared silica sol is larger than 2.3, and the silica sol is shaped.
The organic solvent in the step 2) is one or more of methanol, ethanol, propanol, isopropanol, acetonitrile, acetone, methyl ethyl ketone, diethyl ether, ethyl propyl ether and the like, and preferably, the type and the proportion of the organic solvent in the liquid B are the same as those in the liquid A. The alkoxysilane is one or more of tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane, preferably tetramethoxysilane. Wherein the volume ratio of the organic solvent to the alkoxysilane is 1:4-4:1, the molar ratio of the alkoxysilane to the water is less than 1, preferably the volume ratio of the organic solvent to the alkoxysilane is 1:3-1:1, the molar ratio of alkoxysilane to water is less than 1:4 and greater than 1:170.
the initial silica sol preparation in said step 3), for example, is carried out at a reaction temperature of between 5 and 50 ℃, including, for example, but not limited to, 5 ℃,10 ℃,15 ℃,20 ℃, 25 ℃, 30 ℃, 35 ℃,40 ℃, 45 ℃, 50 ℃, preferably 5 to 30 ℃. Adding the solution B into the solution A at the temperature, wherein the dripping time of the solution B into the solution A is 0.1min-10min, such as 0.1min, 0.5min, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, preferably 0.1min-20min; stirring speeds of 200r/min to 1000r/min, including for example but not limited to 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, preferably 600r/min; the reaction time is 0.5h-3h, including for example but not limited to 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, preferably 2h, by which step the initial silica sol is prepared.
Concentrating in the step 4) by vacuum heating to concentrate the initial silica sol into a concentrated silica sol with the mass fraction of 10-20%. The vacuum heating concentration mode can refer to the prior art, and is well known to those skilled in the art.
The solvent replacement in the step 5) is carried out by replenishing ultrapure water while heating, and evaporating the solvent in the water, so that the organic solvent in the concentrated silica sol is replaced by the ultrapure water; or concentrating while supplementing ultrapure water by ultrafiltration, the final purpose of which is to remove the solvent content in the silica sol to below 200ppm, preferably below 100ppm, regardless of the concentration mode used. When the solvent is replaced until the solvent content is 200ppm or less than 100ppm, the mass fraction of the silica sol is concentrated to more than 20% by adopting a vacuum heating concentration or ultrafiltration membrane concentration mode. The vacuum heating concentration can refer to scraping plate evaporation, forced circulation evaporation or rectification which are common in industry, and the ultrafiltration membrane concentration can refer to an ultrafiltration membrane concentration device which is common in industry.
And 6) filtering the concentrated silica sol to remove large particles to obtain the peanut-shaped ultra-high purity silica sol, wherein a filter element made of PFA material is adopted for filtering, two-stage or three-stage filtering is adopted for filtering, the filtering precision is 0.2-5 mu m, the ultra-high purity silica sol is obtained after filtering, the morphology of the silica sol particles is spherical, peanut-shaped or special-shaped, the association degree is between 1.2 and 2.7, and the total content of metal ions is less than 1ppm.
The preparation process of the present invention is further illustrated by the following more specific examples, without any limitation.
The main raw materials used in the following examples and comparative examples are as follows:
| raw materials | Manufacturer' s | Specification of specification |
| Deionized water | Self-made by adopting mil-q direct water purifier | 18.2MΩ.cm |
| Ammonia water | SUZHOU CRYSTAL CLEAR CHEMICAL Co.,Ltd. | UP level |
| Methanol | SUZHOU CRYSTAL CLEAR CHEMICAL Co.,Ltd. | UP level |
| Ethanol | SUZHOU CRYSTAL CLEAR CHEMICAL Co.,Ltd. | UP level |
| Isopropyl alcohol | SUZHOU CRYSTAL CLEAR CHEMICAL Co.,Ltd. | UP level |
| Acetone (acetone) | Nanjing chemical reagent | Electronic grade |
| Methyl ethyl ketone | SUZHOU CRYSTAL CLEAR CHEMICAL Co.,Ltd. | UP level |
| Ethyl propyl ether | Alatine | UP level |
| Tetramethoxysilane | Nantongsojier | 99.5％ |
The detection method comprises the following steps:
the solid content test method refers to HGT 2521-2008 industrial silica sol.
The secondary particle size of the silica sol colloidal particles is measured by a Markov particle sizer Zetasizer Nano ZS, and the primary particle size is measured by a BET specific surface area measurement method to obtain a specific surface area S bet Primary particle size of 2727/S bet . The degree of association is the ratio of the secondary particle size to the primary particle size.
The apparent morphology of the silica sol was characterized by TEM.
The concentration of metal ions was tested using Agilent 7900 ICP-MS.
The relative permittivity of the organic solvent was measured by the following method: the QS18A universal bridge is adopted, and the capacitance C when the medium is filled is measured by the universal bridge 1 Then measuring the size of the plate capacitor, and calculating the vacuum capacitance C 2 ，C 2 ＝ε 0 * S/d, where ε 0 Is the dielectric constant under vacuum, S is the area of the opposite polar plate, d is the distance between the two polar plates, the dielectric constant of the medium is epsilon r ＝C 1 /C 2 . The relative permittivity of the solvent A was measured in the present invention.
The main process conditions of table 1 are followed for each example and comparative example:
example 1
117.75g of methanol, 70.55g of water and 7.61g of ammonia water are mixed and stirred uniformly to obtain solution A, 15ml of methanol and 5ml of Tetramethoxysilane (TMOS) are mixed uniformly to obtain solution B, the solution B is added into the solution A by a peristaltic pump, and the addition is completed after 10 s. Reacting for 3h at 20 ℃ and 300r/min to obtain the initial silica sol. Then, the silica sol was concentrated to about 20% by heating under reduced pressure at 10Kpa and 100 ℃. Then adding ultrapure water and evaporating until the content of organic matters in the silica sol is reduced to below 100 ppm. At this time, an ultra-high purity silica sol having a mass concentration of 20%, a primary particle diameter of 100nm, a secondary particle diameter of 120nm, a degree of association of 1.2 and a total metal ion content of less than 1ppm was obtained.
Example 2
117.75g of ethyl propyl ether, 70.55g of water and 7.61g of ammonia water are mixed and stirred uniformly to obtain a solution A, 15ml of ethyl propyl ether and 5ml of Tetramethoxysilane (TMOS) are mixed uniformly to obtain a solution B, the solution B is added into the solution A by a peristaltic pump, and the addition is completed after 10 seconds. Reacting for 3h at 20 ℃ and 300r/min to obtain the initial silica sol. Then, the silica sol was concentrated to about 20% by heating under reduced pressure at 10Kpa and 100 ℃. Then adding ultrapure water and evaporating until the content of organic matters in the silica sol is reduced to below 100 ppm. At this time, an ultra-high purity silica sol having a mass concentration of 20%, a primary particle diameter of 100nm, a secondary particle diameter of 243nm, a degree of association of 2.43 and a total metal ion content of less than 1ppm was obtained.
Example 3
41.18g of methanol, 76.57g of ethyl propyl ether, 70.55g of water and 7.61g of ammonia water are mixed and stirred uniformly to obtain solution A, 15ml of organic solvent (the mixture with the same proportion of the organic solvent in the solution A) and 5ml of Tetramethoxysilane (TMOS) are mixed uniformly to obtain solution B, the solution B is added into the solution A by a peristaltic pump, and the addition is completed after 10 s. Reacting for 3h at 20 ℃ and 300r/min to obtain the initial silica sol. Then, the silica sol was concentrated to about 20% by heating under reduced pressure at 10Kpa and 100 ℃. Then adding ultrapure water, evaporating until the content of organic matters in the silica sol is reduced to below 100ppm, and then adopting filter cores of 5 mu m and 0.3 mu m for secondary filtration respectively to filter out large particles. At this time, an ultra-high purity silica sol having a mass concentration of 20%, a primary particle diameter of 98nm, a secondary particle diameter of 208nm, a degree of association of 2.2 and a total metal ion content of less than 1ppm was obtained.
Example 4
100g of methanol, 17.75g of ethyl propyl ether, 70.55g of water and 7.61g of ammonia water are mixed and stirred uniformly to obtain solution A, 15ml of organic solvent (the mixture with the same proportion of the organic solvent in the solution A) and 5ml of Tetramethoxysilane (TMOS) are mixed uniformly to obtain solution B, the solution B is added into the solution A by a peristaltic pump, and the addition is completed after 10 s. Reacting for 3h at 20 ℃ and 300r/min to obtain the initial silica sol. Then, the silica sol was concentrated to about 20% by heating under reduced pressure at 10Kpa and 100 ℃. Then adding ultrapure water and evaporating until the content of organic matters in the silica sol is reduced to below 100 ppm. At this time, an ultra-high purity silica sol having a mass concentration of 20%, a primary particle diameter of 100nm, a secondary particle diameter of 165nm, a degree of association of 1.65 and a total metal ion content of less than 1ppm was obtained.
Example 5
17.75g of methanol, 100g of ethyl propyl ether, 70.55g of water and 7.61g of ammonia water are mixed and stirred uniformly to obtain solution A, 15ml of organic solvent (the mixture with the same proportion of the organic solvent in the solution A) and 5ml of Tetramethoxysilane (TMOS) are mixed uniformly to obtain solution B, the solution B is added into the solution A by a peristaltic pump, and the addition is completed after 10 s. Reacting for 3h at 20 ℃ and 300r/min to obtain the initial silica sol. Then, the silica sol was concentrated to about 20% by heating under reduced pressure at 10Kpa and 100 ℃. Then adding ultrapure water and evaporating until the content of organic matters in the silica sol is reduced to below 100 ppm. At this time, an ultra-high purity silica sol having a mass concentration of 20%, a primary particle diameter of 100nm, a secondary particle diameter of 226nm, a degree of association of 2.26 and a total metal ion content of less than 1ppm was obtained.
Example 6
17.75g of methanol, 100g of ethyl propyl ether, 74.24g of water and 3.92g of ammonia water are mixed and stirred uniformly to obtain solution A, 5ml of organic solvent (the mixture with the same proportion of the organic solvent in the solution A) and 15ml of Tetramethoxysilane (TMOS) are mixed uniformly to obtain solution B, the solution B is added into the solution A by a peristaltic pump, and the addition is completed after 20 minutes. The reaction is carried out for 0.5h at 45 ℃ and 900r/min, and the initial silica sol is obtained. Then, the silica sol was concentrated to about 20% by heating under reduced pressure at 10Kpa and 100 ℃. Then adding ultrapure water, evaporating until the content of organic matters in the silica sol is reduced to below 100ppm, and then adopting filter cores of 5 mu m and 0.2 mu m for secondary filtration respectively to filter out large particles. At this time, an ultra-high purity silica sol having a mass concentration of 20%, a primary particle diameter of 30nm, a secondary particle diameter of 67nm, a degree of association of 2.23 and a total metal ion content of less than 1ppm was obtained.
Example 7
17.75g of methanol, 100g of ethyl propyl ether, 66.41g of water and 11.75g of ammonia water are mixed and stirred uniformly to obtain solution A, 5ml of organic solvent (the mixture with the same proportion of the organic solvent in the solution A) and 15ml of Tetramethoxysilane (TMOS) are mixed uniformly to obtain solution B, the solution B is added into the solution A by a peristaltic pump, and the addition is completed after 40 minutes. The reaction is carried out for 0.5h at 45 ℃ and 900r/min, and the initial silica sol is obtained. Then, the silica sol was concentrated to about 20% by heating under reduced pressure at 10Kpa and 100 ℃. Then adding ultrapure water, evaporating until the content of organic matters in the silica sol is reduced to below 100ppm, and then adopting filter cores of 5 mu m and 0.2 mu m for secondary filtration respectively to filter out large particles. At this time, an ultra-high purity silica sol having a mass concentration of 20%, a primary particle diameter of 50nm, a secondary particle diameter of 112.5nm, a degree of association of 2.25 and a total metal ion content of less than 1ppm was obtained.
Example 8
The amplification effect was verified by amplifying example 6 by 100-fold and 1000-fold, and the amplification experiment was repeated three times by 100-fold, and the particle size and association degree of the obtained silica sol are shown in table 1, respectively.
Comparative example 1
173.77g of methanol, 26.07g of water and 1.74g of ammonia water are mixed and stirred uniformly to obtain solution A, 17ml of tetramethoxysilane and 5.67ml of methanol are mixed uniformly to obtain solution B, the solution B is added into the solution A by a peristaltic pump, and the addition is completed after 20 minutes. Reacting for 3h at 20 ℃ and 300r/min to obtain the initial silica sol. Then, the silica sol was concentrated to about 20% by heating under reduced pressure at 10Kpa and 100 ℃. Then adding ultrapure water, evaporating until the content of organic matters in the silica sol is reduced to below 100ppm, and then adopting filter cores of 5 mu m and 0.3 mu m for secondary filtration respectively to filter out large particles. At this time, an ultra-high purity silica sol having a mass concentration of 20%, a primary particle diameter of 35nm, a secondary particle diameter of 56nm, a degree of association of 1.6 and a total metal ion content of less than 1ppm was obtained.
Comparative example 2
173.77g of methanol, 23.89g of water and 3.92g of ammonia water are mixed and stirred uniformly to obtain solution A, 17ml of tetramethoxysilane and 5.67ml of methanol are mixed uniformly to obtain solution B, and the solution B is added into the solution A by a peristaltic pump for 15 min. Reacting for 3h at 15 ℃ and 700r/min to obtain the initial silica sol. Then, the silica sol was concentrated to about 20% by heating under reduced pressure at 10Kpa and 100 ℃. Then adding ultrapure water, evaporating until the content of organic matters in the silica sol is reduced to below 100ppm, and then adopting filter cores of 5 mu m and 0.3 mu m for secondary filtration respectively to filter out large particles. At this time, an ultra-high purity silica sol having a mass concentration of 20%, a primary particle diameter of 50nm, a secondary particle diameter of 70nm, a degree of association of 1.4 and a total metal ion content of less than 1ppm was obtained.
Comparative example 3
173.77g of methanol, 20.64g of water and 7.17g of ammonia water are mixed and stirred uniformly to obtain solution A, 17ml of tetramethoxysilane and 5.67ml of methanol are mixed uniformly to obtain solution B, the solution B is added into the solution A by a peristaltic pump, and the addition is completed after 10 minutes. Reacting for 3 hours at 10 ℃ and 700r/min to obtain the initial silica sol. Then, the silica sol was concentrated to about 20% by heating under reduced pressure at 10Kpa and 100 ℃. Then adding ultrapure water, evaporating until the content of organic matters in the silica sol is reduced to below 100ppm, and then adopting filter cores of 5 mu m and 0.3 mu m for secondary filtration respectively to filter out large particles. At this time, an ultra-high purity silica sol having a mass concentration of 20%, a primary particle diameter of 100nm, a secondary particle diameter of 120nm, a degree of association of 1.2 and a total metal ion content of less than 1ppm was obtained.
Comparative example 4
Comparative example 2 was amplified by 100-fold and 1000-fold in the same ratio, the amplification effect was verified, and the 100-fold amplification experiment was repeated three times, and the particle size and association degree of the obtained silica sol were shown in table 1, respectively.
Table 1 amounts and ratios of solvents in examples and comparative examples
In examples 1 to 5, the other reaction conditions were controlled to be unchanged, and only the amount and the ratio of the organic solvent in the solution a were changed, but the amount of the reactant water was not changed, and the relative dielectric constant of the solution a was controlled, so that spherical, peanut-shaped or abnormal-shaped silica sols, as shown in fig. 2, corresponding to the spherical, abnormal-shaped and peanut-shaped silica sols, respectively, could be prepared. As can be seen from fig. 1, the degree of association gradually decreases as the relative dielectric constant of the liquid a increases. As the proportion and the quantity of the organic solvent in the A are only changed, and the conditions such as water quantity, catalyst quantity, TMOS quantity and the like are not changed, the particle sizes of the prepared colloidal particles are nearly consistent. In comparative examples 1 to 3, the degree of association of the silica sol prepared by the conventional alkoxide method was also affected by the amount of water, the amount of ammonia water, the temperature, the rate of TMOS addition, etc., and although the relative dielectric constant was also between 39 and 52, when the particle size was controlled by other factors such as the amount of water, etc., the degree of association gradually decreased as the particle size gradually increased, and the prepared particles were more spherical, again proving that it was more difficult to prepare silica sols having a large particle size and a high degree of association by the conventional alkoxide method. In the comparative example, although the relative dielectric constant was adjusted by adjusting the amounts of methanol and water, the change in the amount of water also had an effect on the degree of association. In the embodiments 6 and 7, the amount of water in the solution A is fixed, and the dielectric constant is regulated by other organic solvents, so that the association degree can be well regulated, and the particle size of the prepared nano particles can be regulated, thereby preparing spherical, peanut-shaped or irregularly-shaped silica sol with different particle sizes.
The conventional alkoxide method is used for regulating the association degree by regulating the amount of the catalyst, the amount of water, the temperature, the addition speed of TMOS and the like, and is often influenced by mass transfer and heat transfer, in repeated experiments of comparative example 2, comparative example 4-1 and comparative example 4-2, the experimental repeatability is poor, and in amplified production, for example, comparative examples 4-3 and 4-4 are relatively good and the amplification effect is relatively small due to slower heat transfer and heat transfer.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (17)
1. The preparation method of the ultra-high purity silica sol with adjustable association degree is characterized by comprising the following steps of:
1) And (3) preparing a solution A: uniformly mixing an organic solvent, ultrapure water and a base catalyst in a certain proportion, and adjusting the type and the dosage of the organic solvent to ensure that the relative dielectric constant of the A liquid is between 39 and 52, wherein the association degree of the prepared silica sol is between 1.2 and 2.7; wherein,
adjusting the relative dielectric constant of the solution A to be more than 50, wherein the association degree of the prepared silica sol is less than 1.7, and the silica sol is spherical;
the relative dielectric constant of the solution A is regulated to be between 43 and 50, the association degree of the prepared silica sol is correspondingly between 1.7 and 2.3, and the silica sol is peanut-shaped;
adjusting the relative dielectric constant of the solution A to be less than 43, wherein the association degree of the prepared silica sol is more than 2.3, and the silica sol is special-shaped;
2) And (3) preparing a solution B: uniformly mixing an organic solvent and alkoxy silane; the volume ratio of the organic solvent to the alkoxy silane is 1:4-4:1;
3) Initial silica sol preparation: adding the solution B into the solution A at the temperature of 5-50 ℃, and stirring and reacting to obtain initial silica sol;
4) Concentrating: concentrating the initial silica sol to a mass fraction of 10-20%;
5) Solvent replacement: replacing the organic solvent in the concentrated silica sol with ultrapure water, and concentrating to more than 20% by mass;
6) And (3) filtering: filtering the concentrated silica sol to remove large particles to obtain the ultra-high purity silica sol;
the organic solvent in the step 1) and the step 2) is one or more of methanol, ethanol, propanol, isopropanol, acetonitrile, acetone, methyl ethyl ketone, diethyl ether and ethyl propyl ether; the organic solvent in the solution B is the same as the organic solvent in the solution A;
the mass fraction of the organic solvent in the solution A in the step 1) is 20-80%, the mass fraction of the ultrapure water is 19-79%, and the mass fraction of the base catalyst is 0.5-1.5%;
the molar ratio of the alkoxysilane in step 2) to the water in step 1) is less than 1;
the initial silica sol in the step 3) is prepared, the dripping time of the solution B to the solution A is 0.1-40 min, and the stirring speed is 200-1000 r/min.
2. The method for preparing ultra-high purity silica sol with controllable degree of association according to claim 1, wherein the resistivity of the ultra-pure water in step 1) is not less than 10mΩ·cm.
3. The method for preparing ultra-high purity silica sol with controllable degree of association according to claim 2, wherein the resistivity of the ultra-high purity water is not less than 18.2M Ω -cm.
4. The method for preparing ultra-high purity silica sol with controllable degree of association according to claim 1, wherein the base catalyst in step 1) is at least one selected from alkali metal hydroxide, ammonia, organic amine and guanidine compound.
5. The method for preparing ultra-high purity silica sol with controllable association degree according to claim 4, wherein the alkali metal hydroxide is at least one selected from potassium hydroxide, sodium hydroxide and lithium hydroxide, the organic amine is at least one selected from ethylenediamine, triethanolamine and tetramethylammonium hydroxide, and the guanidine compound is at least one selected from tetramethylguanidine, trimethylguanidine and guanidine carbonate.
6. The method for preparing ultra-high purity silica sol with controllable degree of association according to claim 4, wherein the base catalyst is selected from ammonia water, ethylenediamine or tetramethylammonium hydroxide.
7. The method for preparing ultra-high purity silica sol with adjustable association degree according to claim 1, wherein the alkoxysilane in the step 2) is one or more of tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane.
8. The method for preparing ultra-high purity silica sol with adjustable association degree according to claim 7, wherein the alkoxysilane is tetramethoxysilane.
9. The method for preparing the ultra-high purity silica sol with adjustable association degree according to claim 1, wherein the volume ratio of the organic solvent to the alkoxysilane is 1:3-1:1, wherein the molar ratio of the alkoxy silane to water is less than 1:4.
10. The method for preparing ultra-high purity silica sol with adjustable association degree according to claim 1, wherein the initial silica sol in the step 3) is prepared, the dropwise adding time of the solution B to the solution A is 0.1min-20min, and the reaction time is 0.5h-3h.
11. The method for preparing ultra-high purity silica sol with controllable degree of association according to claim 1, wherein the initial silica sol in step 3) is prepared at a reaction temperature of 5-30 ℃.
12. The method for preparing ultra-high purity silica sol with adjustable association degree according to claim 1, wherein the solvent replacement in step 5) is performed by adding ultrapure water while heating, evaporating the solvent in the water, or concentrating while adding ultrapure water by ultrafiltration until the solvent content in the silica sol is reduced to 200ppm or less.
13. The method for preparing ultra-high purity silica sol with controllable degree of association according to claim 12, wherein the solvent content in the silica sol is reduced to 100ppm or less.
14. The method for preparing ultra-high purity silica sol with adjustable association degree according to claim 13, wherein the concentration in the step 5) is performed by vacuum heating concentration or ultrafiltration membrane concentration, and the mass fraction of the silica sol is concentrated to more than 20%.
15. The method for preparing ultra-pure silica sol with adjustable association degree according to claim 1, wherein the filtering in the step 6) is performed by a filter element made of PFA material, and the filtering precision is 0.2 μm-5 μm by two-stage or three-stage filtering.
16. The ultra-high purity silica sol obtained by the preparation method of any one of claims 1 to 15, wherein the morphology of the silica sol particles is spherical, peanut-shaped or irregularly-shaped, the primary particle size is between 30 and 150nm, the association degree is between 1.2 and 2.7, and the total content of metal ions is less than 1ppm.
17. Use of the ultra-high purity silica sol of claim 16 in chemical mechanical polishing.
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