CN115893427B - Silicon oxide material with rod-shaped structure and synthesis method and application thereof - Google Patents
Silicon oxide material with rod-shaped structure and synthesis method and application thereof Download PDFInfo
- Publication number
- CN115893427B CN115893427B CN202211566432.XA CN202211566432A CN115893427B CN 115893427 B CN115893427 B CN 115893427B CN 202211566432 A CN202211566432 A CN 202211566432A CN 115893427 B CN115893427 B CN 115893427B
- Authority
- CN
- China
- Prior art keywords
- silicon oxide
- silicic acid
- oxide material
- rod
- triethanolamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 75
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 73
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 80
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000002245 particle Substances 0.000 claims abstract description 63
- 239000013078 crystal Substances 0.000 claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 29
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 238000005498 polishing Methods 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 239000004065 semiconductor Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 5
- 230000006911 nucleation Effects 0.000 claims abstract description 4
- 238000010899 nucleation Methods 0.000 claims abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 20
- -1 polyoxyethylene Polymers 0.000 claims description 18
- 239000004115 Sodium Silicate Substances 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 230000001276 controlling effect Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910001415 sodium ion Inorganic materials 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910001431 copper ion Inorganic materials 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003957 anion exchange resin Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000009616 inductively coupled plasma Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003729 cation exchange resin Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention discloses a silicon oxide material with a rod-shaped structure, and a synthesis method and application thereof, wherein the silicon oxide material comprises the following components: step 1, preparing silicic acid; step 2: preparing seed crystal; adding pure water, alcohol and triethanolamine (or ammonia water) into the silicic acid prepared in the step 1; the alcohol is a polymerization inhibitor, the triethanolamine or ammonia water is a pH value regulator, under the combined action of silicic acid, an alcohol polymerization inhibitor and triethanolamine (or ammonia water), the normal polycondensation nucleation process of silicic acid is interfered, and the prepared seed crystal is in a chain shape; step 3: the chain seed crystal is used to prepare base liquid, the constant liquid level evaporation method is adopted to further synthesize and grow up, particles which break into rod-shaped structures occur in weaker places in the chain seed crystal, the particles further grow up, the silicon oxide material with the rod-shaped structures is obtained, the polishing efficiency of a semiconductor can be improved, the whole synthesis process is simple, and the prepared silicon oxide material has low metal ion content and good stability.
Description
Technical Field
The invention relates to the technical field of synthesis of silicon oxide materials, in particular to a silicon oxide material with a rod-shaped structure, and a synthesis method and application thereof.
Background
The silicon oxide material is a colloidal solution of nano-scale silicon dioxide particles dispersed in water, the concentration is generally 10% -40%, the particle size range is generally 5-150 nm, the appearance of the particles can be seen to be spherical under a scanning electron microscope, and the silicon oxide material has good stability under the condition of acidity or alkalinity, so that the silicon oxide material can be used as polishing and grinding slurry, is widely applied to chemical mechanical polishing technology and has irreplaceable positions.
The silicon oxide materials with a rod-shaped structure are disclosed in the published literature, the polishing efficiency can be improved, the silicon oxide materials with irregular morphology or potato shape can be prepared by adding inorganic salt in the patent CN103408027A and the patent CN101402829A, but the silicon oxide materials prepared by the method have higher content of metal ion impurities and cannot be used for semiconductor polishing application with higher requirements on metal ions. Patents CN101626979 and CN104556059a respectively disclose that the slender or non-spherical silicon oxide material is prepared by high-temperature pressurization, but the preparation process is complex and the cost is high.
In general, the metal ion content of the silicon oxide material prepared by the ion exchange method is always 0.1-0.3 percent, and the requirements on polishing processing are also higher and higher along with the continuous decrease of the characteristic line width of the semiconductor. The metal ions in the silicon oxide material are concentrated on the surface of the polishing material in the polishing process, so that the metal ions are polluted, and the content of the metal ions in the silicon oxide material should be reduced as much as possible.
Disclosure of Invention
The invention aims to solve the technical problem of providing a silicon oxide material with a rod-shaped structure, and a synthesis method and application thereof, so that the prepared silicon oxide material is rod-shaped, the semiconductor polishing efficiency can be improved, the synthesis process is simple, the metal ion content is low, and the stability is good.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for synthesizing a silicon oxide material having a rod-like structure, comprising:
step 1, preparing silicic acid;
step 2: preparing seed crystal; adding pure water, alcohol and triethanolamine into the silicic acid prepared in the step 1; or adding pure water, alcohol and ammonia water into the silicic acid prepared in the step 1; the alcohol is a polymerization inhibitor, the triethanolamine or ammonia water is a pH value regulator, and under the combined action of silicic acid, an alcohol polymerization inhibitor and the triethanolamine or ammonia water, the normal polycondensation nucleation process of the silicic acid is interfered, and the prepared seed crystal is in a chain shape;
step 3: preparing a base solution by using chain seed crystals, further synthesizing and growing by adopting a constant liquid level evaporation method, and breaking the weaker part of the chain seed crystals into particles with a rod-shaped structure, wherein the particles further grow to obtain the silicon oxide material with the rod-shaped structure.
As a further improvement of the present invention, the step 1 of preparing silicic acid comprises: diluting commercial sodium silicate solution to 2-6% by mass, then passing the diluted sodium silicate solution through cation resin to obtain silicic acid, adding complexing agent accounting for 0.1-1% by mass of the diluted sodium silicate solution into the silicic acid, standing for 1-10 hours, then passing through anion exchange resin to obtain silicic acid, adding dispersing agent accounting for 0.01-0.1% by mass of the diluted sodium silicate solution into the silicic acid, regulating pH value to be less than 1.5 by strong acid, and then passing through cation exchange resin after standing for 1-10 hours to obtain silicic acid with good stability, wherein the viscosity is 2-5Pa.s, and the pH is 2.0-3.5.
Preferably, in the step 1: the complexing agent is one or more of EDTA and citric acid; and/or the strong acid is one or more of hydrochloric acid, sulfuric acid and nitric acid; and/or the dispersing agent is one or more of polyoxyethylene and polyethylene glycol.
Further, the step 2 of preparing the seed crystal includes: adding the silicic acid prepared in the step 1 into a reaction kettle, adding pure water and alcohol under stirring, regulating the pH value to 8.0-11.0 by using triethanolamine or ammonia water with the concentration of 5-15%, heating to boil, adopting constant liquid level evaporation synthesis, maintaining the liquid level balance by adding the silicic acid in the synthesis process, controlling the pH value to 8.0-11.0 by adding the triethanolamine or ammonia water, synthesizing for 5-20 hours, cooling to room temperature after finishing, preparing seed crystals, and obtaining the particles in a chain shape under a scanning electron microscope.
Preferably, in the step 2: the alcohol is one or more of glycerol and ethylene glycol.
Further, the step 3 of preparing the silicon oxide material comprises the steps of adding the seed crystal prepared in the step 2 and pure water as base solution into a reaction kettle, heating to boiling under a stirring state, adopting constant liquid level evaporation synthesis, maintaining the liquid level balance in the synthesis process by adding silicic acid, controlling the pH value to be 8.0-11.0 by adding triethanolamine or ammonia water, and cooling to room temperature after the synthesis is finished for 10-50 hours, thereby obtaining the silicon oxide material, wherein the particles are in a rod shape when seen under a scanning electron microscope.
Further, the silicon oxide material prepared in the step 3 has the content of 10-40%, the particle size measured by a Markov laser particle size analyzer is 10-150nm, the appearance of particles is a rod-shaped structure under a scanning electron microscope, the association degree of the particles is 2.0-4.0, the number of the rod-shaped particles is more than 80%, the content of sodium ions measured by an inductively coupled plasma mass spectrometer is less than 40ppm, the content of aluminum ions is less than 30ppm, the content of iron ions is less than 10ppm, and the content of copper ions is less than 0.2ppm.
The invention also provides a silicon oxide material with a rod-shaped structure, which is synthesized by adopting the synthesis method.
The invention also provides an application of the silicon oxide material with the rod-shaped structure in semiconductor polishing.
The reaction principle of the invention is as follows: diluting commercial sodium silicate into 2-6% content, obtaining silicic acid with low metal ion content and good stability by cation resin and anion resin and auxiliary agent, then synthesizing, adding alcohol and triethanolamine (or ammonia water) in the process of synthesizing seed crystal, wherein the alcohol is polymerization inhibitor for preventing the silicic acid from being condensed into particles, and the triethanolamine or ammonia water is pH value regulator, and under the combined action of silicic acid, alcohol and triethanolamine (or ammonia water), the normal polycondensation nucleation process of silicic acid is interfered, so that the synthesized seed crystal is in chain shape. Preparing a base solution by using chain seed crystals, further synthesizing and growing by adopting a constant liquid level evaporation method, and further growing the particles by breaking the weaker parts of the chain seed crystals into particles with a rod-shaped structure due to no addition of polymerization inhibitor, thereby obtaining the silicon oxide material with the rod-shaped structure with a certain particle size.
By adopting the technical scheme, the invention has at least the following advantages:
the invention synthesizes chain crystal seeds by using silicic acid, alcohols and triethanolamine (or ammonia water), further synthesizes and grows the chain crystal seeds to obtain a rod-shaped silicon oxide material with a certain particle size, the content of metal ions is not introduced in the whole synthesis process, the prepared silicon oxide material is 10-40%, the particle size measured by a Markov laser particle size meter is 10-150nm, the appearance of the particles is in a rod-shaped structure under a scanning electron microscope, the association degree of the particles is 2.0-4.0, the number of the rod-shaped particles is more than 80%, the content of sodium ions measured by an inductively coupled plasma mass spectrometer is less than 40ppm, the content of aluminum ions is less than 30ppm, the content of iron ions is less than 10ppm, the content of copper ions is less than 0.2ppm, the synthesis process is simple, the content of metal ions of the silicon oxide material is low, and the stability is good.
Drawings
The foregoing is merely an overview of the present invention, and the present invention is further described in detail below with reference to the accompanying drawings and detailed description.
FIG. 1 shows a chain-like structure seed particle as seen under a scanning electron microscope, wherein (a) is example 1 and (b) is example 2;
FIG. 2 shows a silicon oxide material having a rod-like structure as seen under a scanning electron microscope, wherein (a) is example 1 and (b) is example 2;
FIG. 3 is a view of a scanning electron microscope showing seed particles of spherical structure, wherein (a) is comparative example 1 and (b) is comparative example 2;
fig. 4 is a view of a silicon oxide material of a spherical structure as seen under a scanning electron microscope, wherein (a) is comparative example 1 and (b) is comparative example 2.
Detailed Description
The present invention will be further described with reference to examples, but the present invention is not limited to the following examples, and any products which are the same as or similar to the present invention and are obtained in the light of the present invention are within the scope of protection (note: the content of each substance in each of the following examples is mass percent).
Example 1:
step 1: and (3) preparing silicic acid. Diluting commercial sodium silicate solution to a content of 4.0%, taking 7Kg of the solution (diluted sodium silicate solution) and passing through a cationic resin to prepare silicic acid, adding 7g of EDTA into the silicic acid, standing for 1 hour, passing through an anion exchange resin to obtain silicic acid, adding 0.14g of polyoxyethylene into the silicic acid, regulating pH to 1.41 by hydrochloric acid, standing for 1 hour, and passing through the cationic resin to obtain silicic acid with good stability, wherein the viscosity of the silicic acid is 3.2Pa.s, and the pH value is 2.7.
Step 2: preparing seed crystal, adding 120g silicic acid, 480g pure water and 6g glycerol into a three-neck flask with 1L, adding triethanolamine with the concentration of 10% under stirring to adjust the pH value to 8.8, turning on a heating switch, adopting constant liquid level evaporation synthesis, maintaining the liquid level balance in the synthesis process by adding silicic acid, controlling the pH value to 8.0-11.0 by adding triethanolamine, synthesizing for 15 hours, cooling to room temperature after finishing, and obtaining a chain-shaped silicon oxide material, namely seed crystal, the content of which is 12.5%, measuring the particle diameter of 10nm by a Markov laser particle size analyzer, and viewing the appearance of the particles to be a chain-shaped structure under a scanning electron microscope, as shown in (a) of fig. 1.
Step 3: adding 96g of seed crystal and 504g of pure water into a 1L three-neck flask, turning on a stirring and heating switch, adopting constant liquid level evaporation synthesis, maintaining liquid level balance in the synthesis process by adding silicic acid, controlling the pH value to be 8.0-11.0 by adding triethanolamine, synthesizing for 26 hours, cooling to room temperature after finishing to obtain a silicon oxide material, wherein the content of the silicon oxide material is 21.4%, the particle size of the silicon oxide material is 37nm as measured by a Markov laser particle size meter, the content of sodium ion is 21ppm, the content of aluminum ion is 26ppm, the content of iron ion is 7ppm, the content of copper ion is 0.08ppm as measured by an inductively coupled plasma mass spectrometer, and the appearance of particles is in a rod-shaped structure as shown in a scanning electron microscope, and the association degree of the particles is 2.0-4.0 and the number of the rod-shaped particles is more than 80%.
Example 2:
step 1: and (3) preparing silicic acid. Diluting commercial sodium silicate solution to the content of 4.0%, taking 15Kg, passing through cation resin to prepare silicic acid, adding 3g of citric acid into the silicic acid, standing for 5 hours, then passing through anion exchange resin to obtain silicic acid, adding 0.45g of polyethylene glycol into the silicic acid, adjusting pH to 1.33 by sulfuric acid, standing for 4 hours, and then passing through cation exchange resin to obtain silicic acid with good stability, wherein the viscosity of the silicic acid is 2.8Pa.s, and the pH is 2.5.
Step 2: preparing seed crystal, adding 300g silicic acid, 1200g pure water and 15g ethylene glycol into a 2L three-neck flask, adding 15% ammonia water to adjust pH=10.3 under stirring, turning on a heating switch, adopting constant liquid level evaporation synthesis, maintaining liquid level balance in the synthesis process by adding silicic acid, controlling pH value to 8.0-11.0 by adding ammonia water, synthesizing for 13 hours, cooling to room temperature after finishing, and obtaining chain-shaped silicon oxide material, namely seed crystal, the content of which is 12.1%, the particle size of which is 12nm, and observing the appearance of particles to be a chain-shaped structure under a scanning electron microscope, as shown in fig. 1 (b). Since the same kind of auxiliary agents are adopted in the examples 1 and 2, the obtained granules have the same appearance, which shows that the same kind of auxiliary agents can be prepared.
Step 3: 248g of seed crystal and 1252g of pure water are added into a 2L three-neck flask, a stirring and heating switch is turned on, constant liquid level evaporation synthesis is adopted, liquid level balance is maintained in the synthesis process by adding silicic acid, the pH value is controlled to be 8.0-11.0 by adding ammonia water, the synthesis time is 31 hours, and the silicon oxide material is cooled to room temperature after the completion, so that the silicon oxide material is prepared, the content of the silicon oxide material is 24.4%, the particle size of the silicon oxide material is 28nm as measured by a Markov laser particle size meter, the content of sodium ion is 27ppm, the content of aluminum ion is 25ppm, the content of iron ion is 8ppm, the content of copper ion is 0.1ppm as measured by an inductively coupled plasma mass spectrometer, the appearance of particles is in a rod-shaped structure as shown in a scanning electron microscope, the association degree of the particles is 2.0-4.0, and the number of the rod-shaped particles is more than 80%. As above, since the same kind of auxiliary agents are adopted in examples 1 and 2, the obtained granules have the same appearance, which indicates that the same kind of auxiliary agents can be prepared.
Comparative example 1:
step 1: and (3) preparing silicic acid. Diluting commercial sodium silicate solution to the content of 4.0%, taking 7Kg, then passing through cation resin to prepare silicic acid, adding 7g of EDTA into the silicic acid, standing for 1 hour, then passing through anion exchange resin to obtain silicic acid, adding 0.14g of polyoxyethylene into the silicic acid, regulating the pH value to be 1.41 by hydrochloric acid, standing for 1 hour, then passing through cation exchange resin to obtain silicic acid with good stability, wherein the viscosity of the silicic acid is 3.1Pa.s, and the pH value is 2.7.
Step 2: preparing seed crystal, adding 120g silicic acid and 480g pure water into a 1L three-neck flask, adding triethanolamine with the concentration of 10% under stirring to regulate pH to 8.8, turning on a heating switch, adopting constant liquid level evaporation synthesis, maintaining liquid level balance in the synthesis process by adding silicic acid, controlling pH value to 8.0-11.0 by adding triethanolamine, synthesizing for 15 hours, cooling to room temperature after finishing, and obtaining silicon oxide material, namely seed crystal, the content of which is 13.0%, measuring the particle size of 11nm by a Markov laser particle size meter, and observing the appearance of the particles to be spherical under a scanning electron microscope, as shown in fig. 3 (a).
Step 3: adding 96g of seed crystal and 504g of pure water into a 1L three-neck flask, turning on a stirring and heating switch, adopting constant liquid level evaporation synthesis, maintaining liquid level balance in the synthesis process by adding silicic acid, controlling the pH value to be 8.0-11.0 by adding organic weak base, and cooling to room temperature after the synthesis time is 26 hours, so as to obtain a silicon oxide material, wherein the content of the silicon oxide material is 23.5%, the particle size of the silicon oxide material is 40nm as measured by a Markov laser particle size meter, the content of sodium ion is 23ppm, the content of aluminum ion is 25ppm, the content of iron ion is 7ppm, the content of copper ion is 0.07ppm, and the appearance of the particle is spherical as shown in a scanning electron microscope, as shown in fig. 4 (a).
As is clear from the comparison between comparative example 1 and example 1, the addition of alcohol is critical to the overall synthesis process, and the absence of alcohol does not allow the production of chain-like seeds and thus rod-like silica materials.
Comparative example 2:
step 1: and (3) preparing silicic acid. Diluting commercial sodium silicate solution to the content of 4.0%, taking 15Kg, passing through cation resin to prepare silicic acid, adding 3g of citric acid into the silicic acid, standing for 5 hours, then passing through anion exchange resin to obtain silicic acid, adding 0.45g of polyethylene glycol into the silicic acid, adjusting pH to 1.33 by sulfuric acid, standing for 4 hours, then passing through cation exchange resin to obtain silicic acid with good stability, wherein the viscosity of the silicic acid is 2.7Pa.s, and the pH is 2.5.
Step 2: seed crystal is prepared, 300g of silicic acid, 1200g of pure water and 15g of ethylene glycol are added into a 2L three-neck flask, sodium hydroxide with the concentration of 5% is added under stirring to adjust the pH value to be 10.3, a heating switch is turned on, constant liquid level evaporation synthesis is adopted, the liquid level balance is maintained in the synthesis process through adding the silicic acid, the pH value is controlled to be 8.0-11.0 through adding the sodium hydroxide, the synthesis time is 13 hours, the mixture is cooled to room temperature after the end, the silicon oxide material, namely the seed crystal, the content of which is 12.3%, the particle size of which is measured by a Markov laser particle size meter is 12nm, and the appearance of particles is spherical under a scanning electron microscope, as shown in fig. 3 (b).
Step 3: 248g seed crystal and 1252g pure water are added into a 2L three-neck flask, a stirring and heating switch is turned on, constant liquid level evaporation synthesis is adopted, liquid level balance is maintained in the synthesis process through adding silicic acid, the pH value is controlled to be 8.0-11.0 through adding sodium hydroxide, the synthesis time is 35 hours, and after the synthesis is finished, the silicon oxide material is cooled to room temperature, so that the silicon oxide material is prepared, the content of the silicon oxide material is 21.9%, the particle size of the silicon oxide material is 38nm as measured by a Markov laser particle size meter, the sodium ion content of the silicon oxide material is 2590ppm, the sodium ion content of the silicon oxide material is 6000ppm as measured by an inductively coupled plasma mass spectrometer, the aluminum ion content of the silicon oxide material is 26ppm, the iron ion content of the silicon oxide material is 16ppm, the copper ion content of the silicon oxide material is 1.5ppm, and the appearance of the silicon oxide particle is spherical as shown in a scanning electron microscope, and the silicon oxide material is shown in fig. 4 (b).
As is clear from comparison of comparative example 2 with example 2, the use of ammonia water as an inorganic strong base makes it impossible to obtain a seed crystal in a chain form under the same conditions, and further makes it impossible to obtain a rod-shaped silica material. Therefore, chain crystal seeds can be prepared only under the combined action of silicic acid, alcohol and inorganic weak base, and then the silicon oxide material with a rod-shaped structure is prepared.
In summary, the present invention can synthesize chain seed crystals by using silicic acid, alcohols and triethanolamine (or ammonia water), and further synthesize rod-shaped silicon oxide materials having a certain particle size by the chain seed crystals.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the invention in any way, and some simple modifications, equivalent variations or modifications can be made by those skilled in the art using the teachings disclosed herein, which fall within the scope of the present invention.
Claims (9)
1. A method for synthesizing a silicon oxide material having a rod-like structure, comprising:
step 1, preparing silicic acid;
step 2: preparing seed crystal; adding pure water, alcohol and triethanolamine into the silicic acid prepared in the step 1; or adding pure water, alcohol and ammonia water into the silicic acid prepared in the step 1; the alcohol is a polymerization inhibitor, the triethanolamine or ammonia water is a pH value regulator, and under the combined action of silicic acid, an alcohol polymerization inhibitor and the triethanolamine or ammonia water, the normal polycondensation nucleation process of the silicic acid is interfered, and the prepared seed crystal is in a chain shape;
step 3: preparing a base solution by using chain seed crystals, further synthesizing and growing by adopting a constant liquid level evaporation method, and breaking the weaker part of the chain seed crystals into particles with a rod-shaped structure, wherein the particles further grow to obtain the silicon oxide material with the rod-shaped structure.
2. The method for synthesizing a silicon oxide material having a rod-like structure according to claim 1, wherein the step 1 of preparing silicic acid comprises:
diluting commercial sodium silicate solution to 2-6% by mass, then passing the diluted sodium silicate solution through cation resin to obtain silicic acid, adding complexing agent accounting for 0.1-1% by mass of the diluted sodium silicate solution into the silicic acid, standing for 1-10 hours, then passing through anion exchange resin to obtain silicic acid, adding dispersing agent accounting for 0.01-0.1% by mass of the diluted sodium silicate solution into the silicic acid, regulating pH value to be less than 1.5 by strong acid, standing for 1-10 hours, and then passing through cation exchange resin to obtain silicic acid with good stability, wherein the viscosity is 2-5Pa.s, and the pH is 2.0-3.5.
3. The method for synthesizing a silicon oxide material having a rod-like structure according to claim 2, wherein in the step 1:
the complexing agent is one or more of EDTA and citric acid;
and/or the strong acid is one or more of hydrochloric acid, sulfuric acid and nitric acid;
and/or the dispersing agent is one or more of polyoxyethylene and polyethylene glycol.
4. A method for synthesizing a silicon oxide material having a rod-like structure according to any one of claims 1 to 3, wherein the step 2 of preparing a seed crystal comprises:
adding the silicic acid prepared in the step 1 into a reaction kettle, adding pure water and alcohol under stirring, regulating the pH value to 8.0-11.0 by using triethanolamine or ammonia water with the concentration of 5-15%, heating to boil, adopting constant liquid level evaporation synthesis, maintaining the liquid level balance by adding the silicic acid in the synthesis process, controlling the pH value to 8.0-11.0 by adding the triethanolamine or ammonia water, synthesizing for 5-20 hours, cooling to room temperature after finishing, preparing seed crystals, and obtaining the particles in a chain shape under a scanning electron microscope.
5. The method for synthesizing a silicon oxide material having a rod-like structure according to claim 4, wherein in the step 2:
the alcohol is one or more of glycerol and ethylene glycol.
6. A method for synthesizing a silicon oxide material having a rod-like structure according to any one of claims 1 to 3, wherein the step 3 of preparing a silicon oxide material comprises:
adding the seed crystal and pure water prepared in the step 2 into a reaction kettle as base solution, heating to boiling under stirring, adopting constant liquid level evaporation synthesis, maintaining liquid level balance in the synthesis process by adding silicic acid, controlling the pH value to be 8.0-11.0 by adding triethanolamine or ammonia water, synthesizing for 10-50 hours, cooling to room temperature after finishing, and obtaining the silicon oxide material, wherein the particles are in a rod shape under a scanning electron microscope.
7. The method for synthesizing a silicon oxide material having a rod-like structure according to any one of claims 1 to 3, wherein the silicon oxide material prepared in the step 3 has a content of 10 to 40%, a particle diameter of 10 to 150nm as measured by a malvern laser particle sizer, a rod-like structure is shown by a particle appearance under a scanning electron microscope, a particle association degree is between 2.0 and 4.0, the number of rod-like particles is more than 80%, a sodium ion content of less than 40ppm, an aluminum ion content of less than 30ppm, an iron ion content of less than 10ppm, and a copper ion content of less than 0.2ppm as measured by an inductively coupled plasma mass spectrometer.
8. A silicon oxide material having a rod-like structure, characterized by being synthesized by the synthesis method according to any one of claims 1 to 7.
9. Use of the silicon oxide material having a rod-like structure as defined in claim 8 in semiconductor polishing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211566432.XA CN115893427B (en) | 2022-12-07 | 2022-12-07 | Silicon oxide material with rod-shaped structure and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211566432.XA CN115893427B (en) | 2022-12-07 | 2022-12-07 | Silicon oxide material with rod-shaped structure and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115893427A CN115893427A (en) | 2023-04-04 |
| CN115893427B true CN115893427B (en) | 2023-12-29 |
Family
ID=86479333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211566432.XA Active CN115893427B (en) | 2022-12-07 | 2022-12-07 | Silicon oxide material with rod-shaped structure and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115893427B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5221497A (en) * | 1988-03-16 | 1993-06-22 | Nissan Chemical Industries, Ltd. | Elongated-shaped silica sol and method for preparing the same |
| JP2003128413A (en) * | 2001-10-19 | 2003-05-08 | Catalysts & Chem Ind Co Ltd | Method for producing silica sol |
| JP2006213541A (en) * | 2005-02-02 | 2006-08-17 | Catalysts & Chem Ind Co Ltd | Method for producing high purity aqueous silica sol |
| CN103803560A (en) * | 2014-01-23 | 2014-05-21 | 齐鲁工业大学 | Curved rod mesoporous SiO2 and preparation method thereof |
| CN104495857A (en) * | 2014-12-10 | 2015-04-08 | 深圳市力合材料有限公司 | Method for rapidly preparing large-particle-size silica sol |
| CN104925819A (en) * | 2015-06-21 | 2015-09-23 | 天津市职业大学 | Method for manufacturing rod-shaped nanometer silicon dioxide hydrosol and application thereof |
| CN106629746A (en) * | 2017-01-22 | 2017-05-10 | 东北师范大学 | Preparation method of rodlike silicon dioxide nano-materials |
| CN110980745A (en) * | 2019-10-30 | 2020-04-10 | 航天特种材料及工艺技术研究所 | Silica sol and preparation method thereof |
| CN112209391A (en) * | 2020-10-21 | 2021-01-12 | 上海胶束化工有限公司 | Preparation method of flower-shaped silicon dioxide abrasive particles |
| CN112499634A (en) * | 2020-12-23 | 2021-03-16 | 临沂市科翰硅制品有限公司 | Preparation method of silica sol |
| CN114477190A (en) * | 2021-12-23 | 2022-05-13 | 山东金亿达新材料有限公司 | Preparation method and application of silica sol for chemical polishing |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044786B (en) * | 2016-06-01 | 2019-05-07 | 上海新安纳电子科技有限公司 | Big partial size silica solution of polydispersion and preparation method thereof |
| JP7021194B2 (en) * | 2017-03-31 | 2022-02-16 | 日揮触媒化成株式会社 | Method for manufacturing silica particle dispersion |
| TWI777011B (en) * | 2017-12-27 | 2022-09-11 | 日商日揮觸媒化成股份有限公司 | Method for producing chain particle dispersion liquid for abrasives |
-
2022
- 2022-12-07 CN CN202211566432.XA patent/CN115893427B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5221497A (en) * | 1988-03-16 | 1993-06-22 | Nissan Chemical Industries, Ltd. | Elongated-shaped silica sol and method for preparing the same |
| JP2003128413A (en) * | 2001-10-19 | 2003-05-08 | Catalysts & Chem Ind Co Ltd | Method for producing silica sol |
| JP2006213541A (en) * | 2005-02-02 | 2006-08-17 | Catalysts & Chem Ind Co Ltd | Method for producing high purity aqueous silica sol |
| CN103803560A (en) * | 2014-01-23 | 2014-05-21 | 齐鲁工业大学 | Curved rod mesoporous SiO2 and preparation method thereof |
| CN104495857A (en) * | 2014-12-10 | 2015-04-08 | 深圳市力合材料有限公司 | Method for rapidly preparing large-particle-size silica sol |
| CN104925819A (en) * | 2015-06-21 | 2015-09-23 | 天津市职业大学 | Method for manufacturing rod-shaped nanometer silicon dioxide hydrosol and application thereof |
| CN106629746A (en) * | 2017-01-22 | 2017-05-10 | 东北师范大学 | Preparation method of rodlike silicon dioxide nano-materials |
| CN110980745A (en) * | 2019-10-30 | 2020-04-10 | 航天特种材料及工艺技术研究所 | Silica sol and preparation method thereof |
| CN112209391A (en) * | 2020-10-21 | 2021-01-12 | 上海胶束化工有限公司 | Preparation method of flower-shaped silicon dioxide abrasive particles |
| CN112499634A (en) * | 2020-12-23 | 2021-03-16 | 临沂市科翰硅制品有限公司 | Preparation method of silica sol |
| CN114477190A (en) * | 2021-12-23 | 2022-05-13 | 山东金亿达新材料有限公司 | Preparation method and application of silica sol for chemical polishing |
Non-Patent Citations (2)
| Title |
|---|
| Synthesis, functionalization, and applications of morphologycontrollable silica-based nanostructures: A review;Bin Sun，et al.;《Progress in Solid State Chemistry》;全文 * |
| 一种非球形纳米二氧化硅颗粒制备新方法;孔慧;刘卫丽;宋志棠;;材料导报(10);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115893427A (en) | 2023-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5602358B2 (en) | Non-spherical silica sol, method for producing the same, and polishing composition | |
| JP5587957B2 (en) | Konpira sugar-like sol | |
| US5116535A (en) | Aqueous colloidal dispersion of fumed silica without a stabilizer | |
| TWI493612B (en) | Polishing composition | |
| US20110045745A1 (en) | Doped Ceria Abrasives with Controlled Morphology and Preparation Thereof | |
| KR101805238B1 (en) | Polishing composition | |
| KR101427418B1 (en) | Polishing composition and polishing process | |
| JP7213234B2 (en) | Silica particle dispersion, polishing composition, and method for producing silica particle dispersion | |
| JP2013032276A (en) | Deformed silica sol | |
| KR20050107395A (en) | Alkali-resistant cocoon-shaped colloidal silica particle and process for producing the same | |
| TWI440601B (en) | Silica sols with controlled minimum particle size and preparation thereof | |
| TWI761629B (en) | Dispersion of silica particles and method for producing the same | |
| JP4549878B2 (en) | Method for producing high-purity aqueous silica sol | |
| JP6207345B2 (en) | Method for producing silica particles | |
| US10190023B2 (en) | Silica-based polishing particle and abrasive | |
| CN115893427B (en) | Silicon oxide material with rod-shaped structure and synthesis method and application thereof | |
| JP2009126741A (en) | Non-spherical alumina-silica composite sol, method for producing the same and composition for polishing | |
| CN110980745B (en) | Silica sol and preparation method thereof | |
| US20030113251A1 (en) | Method for preparing shape-changed nanosize colloidal silica | |
| JP2003176123A (en) | Silica dispersion liquid | |
| JP3362793B2 (en) | Method for producing silica sol | |
| JP2010024119A (en) | Method for producing confetti-like silica sol | |
| JP5421006B2 (en) | Particle-linked silica sol and method for producing the same | |
| KR20210130145A (en) | Silica particles and their manufacturing method, silica sol, polishing composition, polishing method, semiconductor wafer manufacturing method, and semiconductor device manufacturing method | |
| EP1422277A1 (en) | High concentration silica slurry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |