CN112209391A - Preparation method of flower-shaped silicon dioxide abrasive particles - Google Patents
Preparation method of flower-shaped silicon dioxide abrasive particles Download PDFInfo
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- CN112209391A CN112209391A CN202011134849.XA CN202011134849A CN112209391A CN 112209391 A CN112209391 A CN 112209391A CN 202011134849 A CN202011134849 A CN 202011134849A CN 112209391 A CN112209391 A CN 112209391A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 69
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 66
- 239000002245 particle Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 77
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 46
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 22
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 19
- 230000008020 evaporation Effects 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000001509 sodium citrate Substances 0.000 claims description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000006061 abrasive grain Substances 0.000 claims description 12
- 235000019353 potassium silicate Nutrition 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- 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 8
- 239000003729 cation exchange resin Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000005498 polishing Methods 0.000 abstract description 58
- 229910052594 sapphire Inorganic materials 0.000 abstract description 30
- 239000010980 sapphire Substances 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 13
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 230000003746 surface roughness Effects 0.000 abstract description 4
- 230000001788 irregular Effects 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 230000000694 effects Effects 0.000 description 16
- 239000007787 solid Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 5
- 239000004530 micro-emulsion Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910020489 SiO3 Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a preparation method and application of flower-shaped silicon dioxide nano abrasive particles. The flower-shaped silicon dioxide nano abrasive particles are silicon dioxide nano particles with extremely irregular shapes, and the preparation method comprises the steps of utilizing tetraethyl orthosilicate to prepare flower-shaped seed crystals on the surfaces of small water drops in a water-in-oil system through irregular hydrolysis, condensation and fracture, and obtaining the flower-shaped silicon dioxide nano abrasive particles through asymmetry of the seed crystals in an oil-in-water system during silicic acid condensation growth. Compared with the conventional spherical silicon dioxide abrasive particles, the material removal rate of the flower-shaped silicon dioxide nano abrasive particles on the sapphire wafer is improved by 117%, and the surface roughness after polishing can be effectively reduced.
Description
Technical Field
The invention relates to nanometer abrasive particles with irregular shapes and a preparation method thereof. In particular to a flower-shaped silicon dioxide abrasive grain which is used in the polishing process of a sapphire wafer and belongs to the technical field of surface polishing processing.
Background
Sapphire, alpha-Al in single crystal form2O3Has high strength, high hardness, high temperature resistance, corrosion resistance and abrasion resistanceThe material has a series of excellent physical and chemical properties such as good wiping and light transmitting properties, good electrical insulation properties and the like, and is widely applied to infrared military devices, satellite space technology, window materials of consumer electronics, high-precision optical instruments and meters, Light Emitting Diodes (LEDs) and substrate materials of superconducting nanostructures. In recent years, with the further increase of the demands of consumer electronics industry, national defense industry materials and civil window, the market demand for sapphire materials keeps growing rapidly, which puts higher demands on the processing quality of sapphire wafers, and the material removal rate of the sapphire wafers is improved to the maximum extent while the surface defects such as micro-protrusions and micro-scratches on the surfaces of the sapphire wafers are removed.
Currently, chemical mechanical polishing technology is commonly used to polish the surface of sapphire wafers. The polishing solution is the most main consumable material for chemical mechanical polishing, the inorganic nano abrasive particles are one of the important components in the polishing solution, and the silicon oxide nano particles are the abrasive particles which are most widely applied to polishing of sapphire wafers due to moderate hardness, excellent dispersibility and stability of the silicon oxide nano particles. Most of the silica abrasive particles in the conventional industry are spherical nano particles, but the polishing efficiency is low, and the increasing industrial requirements cannot be met.
Disclosure of Invention
The invention aims to solve the problem of low polishing rate of the existing spherical silicon oxide abrasive particles and provides a preparation method of flower-shaped silicon dioxide nano abrasive particles.
In order to achieve the above object, the present invention adopts the following technical scheme that a method for preparing flower-shaped silica abrasive particles comprises the following steps:
s01: adding polyvinylpyrrolidone into n-amyl alcohol, stirring until the polyvinylpyrrolidone is completely dissolved, adding absolute ethyl alcohol and a sodium citrate solution, stirring until the solution becomes turbid, adding ammonia water, stirring, heating the mixed solution, then slowly dropwise adding tetraethyl orthosilicate, continuously stirring, continuously reacting for 2 hours at a constant temperature of 70 ℃, sealing and cooling for 24 hours to obtain flower-shaped silicon dioxide seed crystals;
s02: passing the water glass solution through a cation exchange resin pretreated with HCl to obtain an active silicic acid solution;
s03: adding deionized water into the flower-shaped silicon dioxide seed crystal, stirring until the mixed solution is milky, heating, dropwise adding the active silicic acid solution and the NaOH solution, keeping the dropwise adding speed consistent with the water evaporation speed, wherein the pH of the mixed solution is regulated by the NaOH solution to be kept between 9 and 11, and performing oil-water separation in the process of dropwise adding the active silicic acid solution and the NaOH solution; after the silicic acid is added, continuously stirring and cooling to room temperature to obtain the flower-shaped silicon oxide abrasive particles.
Further, the ammonia water in the step S01 is 25 wt.% ammonia water; the sodium citrate solution was 0.36M sodium citrate solution.
Further, in the step S01, the mass ratio of the polyvinylpyrrolidone, the n-amyl alcohol, the absolute ethyl alcohol, the sodium citrate solution, the ammonia water, the TEOS, and the like is: 6-10: 122 to 244: 20: 10: 4-9: 5 to 10.
Further, 8 wt.% of water glass in the step S02 is converted into 2-3 wt.% of active silicic acid through cationic resin.
Further, in the step S03, the mass ratio of the flower-shaped silicon dioxide seed crystal, the deionized water, and the active silicic acid is: 300: 600-1000: 1600.
further, the pH is maintained at 10 in the step S03.
The invention has the following beneficial effects: (1) the flower-shaped silicon oxide is prepared by adopting a water-in-oil-in-water binary system microemulsion template method. The flower-shaped silicon oxide abrasive particles are prepared by the hydrolysis, condensation and fracture of TEOS in small droplets in a water-in-oil system and the asymmetry of silicic acid in an oil-in-water system during condensation and growth.
(2) The polishing solution of the flower-shaped silicon dioxide nano abrasive particles is applied to the chemical mechanical polishing of sapphire wafers, can effectively reduce the surface roughness of sapphire, and improves the polishing rate of the flower-shaped silicon dioxide nano abrasive particles by 117 percent compared with the conventional industrial spherical silicon oxide abrasive particles.
(3) Compared with the conventional industrial spherical silicon oxide abrasive grain, the flower-shaped silicon dioxide nano abrasive grain has more effective contact sites with a sapphire wafer, and the synergistic effect of the mechanical grinding effect and the solid-phase chemical reaction is optimal, so that the aim of efficient processing is fulfilled.
Drawings
FIG. 1 is a diagram showing a synthesis apparatus for performing a reaction and oil-water separation in step S03 according to the present invention;
FIG. 2 is a SEM image of the flower-shaped silica nano-abrasive grains in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings.
The invention provides a preparation method of flower-shaped silicon dioxide abrasive particles, which comprises the following steps:
s01: adding polyvinylpyrrolidone (PVP) into n-amyl alcohol, stirring until the polyvinylpyrrolidone is completely dissolved, adding absolute ethyl alcohol and 0.36M sodium citrate solution, stirring until the solution becomes turbid, adding 25 wt.% of ammonia water, stirring, heating the mixed solution, slowly dropwise adding tetraethyl orthosilicate (TEOS), continuously stirring, continuously reacting for 2 hours at constant temperature of 70 ℃, sealing and cooling for 24 hours to obtain flower-shaped silicon dioxide crystal seeds; the PVP, n-amyl alcohol, absolute ethyl alcohol, a 0.36M sodium citrate solution, 25 wt.% ammonia water and TEOS are mixed according to the mass ratio: 6-10: 122 to 244: 20: 10: 4-9: 5 to 10.
S02: passing 8 wt.% of a water glass solution through a cation exchange resin pretreated with HCl to obtain a silicic acid solution with activity of 2-3 wt.%;
s03: and adding deionized water into the flower-shaped silicon dioxide seed crystal, stirring until the mixed solution is milky, heating, dropwise adding the active silicic acid solution prepared in the step S02 and a NaOH solution, and keeping the dropwise adding speed consistent with the water evaporation speed, wherein the pH of the mixed solution is adjusted to be 9-11 by the NaOH solution, and preferably about 10. Performing oil-water separation in the process of dropwise adding the active silicic acid solution and the NaOH solution; continuously stirring and cooling to room temperature after the silicic acid is added dropwise to obtain flower-shaped silicon oxide abrasive grains; wherein. The mass ratio of the flower-shaped silicon dioxide seed crystal to the deionized water to the active silicic acid is as follows: 300: 600-1000: 1600.
the application of the flower-shaped silicon dioxide nano abrasive particles provided by the invention is characterized in that the flower-shaped silicon dioxide nano abrasive particles are adopted to prepare the polishing solution, the polishing solution is applied to polishing of sapphire wafers, the polishing rate can be obviously improved, the polishing precision of spherical silica sol abrasive particles is kept, and the polishing effect of high efficiency and high precision is achieved.
The preparation process according to the invention is further illustrated below with reference to the examples:
example 1
The embodiment provides a preparation method of flower-shaped silica nano abrasive particles, which is used for preparing the flower-shaped silica nano abrasive particles by a two-system microemulsion template method and comprises the following steps:
(1) adding 6g of PVP into a three-neck flask filled with 300ml of n-amyl alcohol, stirring until the PVP is completely dissolved, adding 25ml of absolute ethyl alcohol and 10ml of 0.36M sodium citrate solution, stirring until the solution becomes turbid, adding 5ml of 25 wt.% ammonia water, stirring, heating the mixed solution to 70 ℃, then slowly dropwise adding 5ml of tetraethyl orthosilicate (TEOS), continuously stirring after dropwise adding, continuously reacting at the constant temperature of 70 ℃ for 2 hours, then pouring into a beaker, sealing and cooling overnight to obtain the flower-shaped silicon dioxide seed crystal.
(2) Adding a certain amount of 8 wt.% water glass (Na)2SiO3) The solution was passed through a cation exchange resin pretreated with HCl to obtain a fresh 2 wt.% active silicic acid solution.
(3) Adding 1000ml of deionized water into the seed crystal prepared in the step (1), stirring until the mixed solution is milky, heating to boil, dropwise adding 1600ml of 2.3 wt.% of fresh silicic acid and 3 wt.% of NaOH solution at a constant speed, keeping the water evaporation speed consistent with the water evaporation speed at the dropwise adding speed, wherein the pH is kept at about 10, and carrying out oil-water separation by using the device shown in the figure 1 during the dropwise adding process. After the silicic acid is added, continuously stirring and cooling to room temperature to obtain the flower-shaped silicon oxide abrasive particles.
In this example, a flower-like silica polishing solution with a solid mass fraction of flower-like silica abrasive grains of 6.0 wt.% was finally obtained.
The polishing effect of the polishing liquid of this example on a sapphire wafer is shown in Table 1.
Example 2
The embodiment provides a preparation method of flower-shaped silica nano abrasive particles, which is used for preparing the flower-shaped silica nano abrasive particles by a two-system microemulsion template method and comprises the following steps:
(1) adding 7g of PVP into a three-neck flask filled with 300ml of n-amyl alcohol, stirring until the PVP is completely dissolved, adding 25ml of absolute ethyl alcohol and 10ml of 0.36M sodium citrate solution, stirring until the solution becomes turbid, adding 6.75ml of 25 wt.% ammonia water, stirring, heating the mixed solution to 70 ℃, then slowly dropwise adding 6ml of tetraethyl orthosilicate (TEOS), continuously stirring after dropwise adding, continuously reacting for 2 hours at the constant temperature of 70 ℃, then pouring into a beaker, sealing and cooling overnight to obtain the flower-shaped silicon dioxide seed crystal.
(2) Passing an 8 wt.% water glass solution through a cation exchange resin pretreated with HCl to obtain a silicic acid solution of activity 3 wt.%; .
(3) Adding 900ml of deionized water into the seed crystal prepared in the step (1), stirring until the mixed solution is milky, heating to boil, dropwise adding 1600ml of 2.3 wt.% of fresh silicic acid and 3 wt.% of NaOH solution at a constant speed, keeping the water evaporation speed consistent with the water evaporation speed at the dropwise adding speed, wherein the pH is kept at about 10, and carrying out oil-water separation by using the device shown in the figure 1 during the dropwise adding process. After the silicic acid is added, continuously stirring and cooling to room temperature to obtain the flower-shaped silicon oxide abrasive particles.
In this example, a flower-like silica polishing solution with a solid mass fraction of flower-like silica abrasive grains of 6.3 wt.% was finally obtained.
The polishing effect of the polishing liquid of this example on a sapphire wafer is shown in Table 1.
Example 3
The embodiment provides a preparation method of flower-shaped silica nano abrasive particles, which is used for preparing the flower-shaped silica nano abrasive particles by a two-system microemulsion template method and comprises the following steps:
(1) adding 8g of PVP into a three-neck flask filled with 300ml of n-amyl alcohol, stirring until the PVP is completely dissolved, adding 25ml of absolute ethyl alcohol and 10ml of 0.36M sodium citrate solution, stirring until the solution becomes turbid, adding 6.75ml of 25 wt.% ammonia water, stirring, heating the mixed solution to 70 ℃, then slowly dropwise adding 9ml of tetraethyl orthosilicate (TEOS), continuously stirring after dropwise adding, continuously reacting for 2 hours at the constant temperature of 70 ℃, then pouring into a beaker, sealing and cooling overnight to obtain the flower-shaped silicon dioxide seed crystal.
(2) Passing an 8 wt.% water glass solution through a cation exchange resin pretreated with HCl to obtain a silicic acid solution with an activity of 2.3 wt.%;
(3) adding 700ml of deionized water into the seed crystal prepared in the step (1), stirring until the mixed solution is milky, heating to boil, dropwise adding 1600ml of 2.3 wt.% of fresh silicic acid and 3 wt.% of NaOH solution at a constant speed, keeping the water evaporation speed consistent with the water evaporation speed at the dropwise adding speed, wherein the pH is kept at about 10, and carrying out oil-water separation by using the device shown in the figure 1 during the dropwise adding process. After the silicic acid is added, continuously stirring and cooling to room temperature to obtain the flower-shaped silicon oxide abrasive particles.
In this example, a flower-like silica polishing solution with a solid mass fraction of flower-like silica abrasive grains of 6.8 wt.% was finally obtained.
The polishing effect of the polishing liquid of this example on a sapphire wafer is shown in Table 1.
Example 4
The embodiment provides a preparation method of flower-shaped silica nano abrasive particles, which is used for preparing the flower-shaped silica nano abrasive particles by a two-system microemulsion template method and comprises the following steps:
(1) adding 10g of PVP into a three-neck flask filled with 300ml of n-amyl alcohol, stirring until the PVP is completely dissolved, adding 25ml of absolute ethyl alcohol and 10ml of 0.18M sodium citrate solution, stirring until the solution becomes turbid, adding 6.75ml of 25 wt.% ammonia water, stirring, heating the mixed solution to 70 ℃, then slowly dropwise adding 10ml of tetraethyl orthosilicate (TEOS), continuously stirring after dropwise adding, continuously reacting for 2 hours at the constant temperature of 70 ℃, then pouring into a beaker, sealing and cooling overnight to obtain the flower-shaped silicon dioxide seed crystal.
(2) Passing an 8 wt.% water glass solution through a cation exchange resin pretreated with HCl to obtain a silicic acid solution with an activity of 2.3 wt.%;
(3) adding 600ml of deionized water into the seed crystal prepared in the step (1), stirring until the mixed solution is milky, heating to boil, dropwise adding 1600ml of 2.3 wt.% of fresh silicic acid and 3 wt.% of NaOH solution at a constant speed, keeping the water evaporation speed consistent with the water evaporation speed at the dropwise adding speed, wherein the pH is kept at about 10, and carrying out oil-water separation by using the device shown in the figure 1 during the dropwise adding process. After the silicic acid is added, continuously stirring and cooling to room temperature to obtain the flower-shaped silicon oxide abrasive particles.
In this example, a flower-like silica polishing solution with a solid mass fraction of flower-like silica abrasive grains of 7.1 wt.% was finally obtained.
The polishing effect of the polishing liquid of this example on a sapphire wafer is shown in Table 1.
Comparative example 1
In a comparative example, a method of making spherical silica abrasive particles includes the steps of:
(1) adding a certain amount of 8 wt.% water glass (Na)2SiO3) The solution was passed through a cation exchange resin pretreated with HCl to obtain a freshly prepared 2.3 wt.% active silicic acid solution.
(2) 300ml of conventional industrial seed crystals were taken, diluted with 1000ml of deionized water, stirred and heated to boiling, and 1600ml of a 2.3 wt.% solution of fresh silicic acid and 3 wt.% of NaOH were added dropwise thereto at a constant rate, maintaining the rate of evaporation of water at the rate of dropwise addition consistent with the rate of evaporation of water, wherein the pH was maintained at around 10. After the silicic acid is added dropwise, continuously stirring and cooling to room temperature to obtain the spherical silicon oxide abrasive particles.
In this comparative example, a silica sol having a solid mass fraction of spherical silica abrasive particles of 6.0 wt.% was finally obtained.
The polishing effect of the polishing solution of this comparative example on sapphire wafers is shown in Table 1.
Comparative example 2
In a comparative example, a method of making spherical silica abrasive particles includes the steps of:
(1) the procedure was the same as in comparative example 1
(2) 300ml of conventional industrial seed crystals were taken, diluted with 900ml of deionized water, stirred and heated to boiling, and 1600ml of a 2.3 wt.% solution of fresh silicic acid and 3 wt.% NaOH were added dropwise thereto at a constant rate, maintaining the rate of evaporation of water at the rate of dropwise addition consistent with the rate of evaporation of water, wherein the pH was maintained at around 10. After the silicic acid is added dropwise, continuously stirring and cooling to room temperature to obtain the spherical silicon oxide abrasive particles.
In this comparative example, a silica sol having a solid mass fraction of spherical silica abrasive particles of 6.3 wt.% was finally obtained.
The polishing effect of the polishing solution of this comparative example on sapphire wafers is shown in Table 1.
Comparative example 3
In a comparative example, a method of making spherical silica abrasive particles includes the steps of:
(1) the procedure was the same as in comparative example 1
(2) 300ml of conventional industrial seed crystals were taken, diluted with 700ml of deionized water, stirred and heated to boiling, and 1600ml of a 2.3 wt.% solution of fresh silicic acid and 3 wt.% of NaOH were added dropwise thereto at a constant rate, maintaining the rate of evaporation of water at the rate of dropwise addition consistent with the rate of evaporation of water, wherein the pH was maintained at around 10. After the silicic acid is added dropwise, continuously stirring and cooling to room temperature to obtain the spherical silicon oxide abrasive particles.
In this comparative example, a silica sol having a solid mass fraction of spherical silica abrasive particles of 6.8 wt.% was finally obtained.
The polishing effect of the polishing solution of this comparative example on sapphire wafers is shown in Table 1.
Comparative example 4
In a comparative example, a method of making spherical silica abrasive particles includes the steps of:
(1) the procedure was the same as in comparative example 1
(2) 300ml of conventional industrial seed crystals were taken, diluted with 600ml of deionized water, stirred and heated to boiling, and 1600ml of a 2.3 wt.% solution of fresh silicic acid and 3 wt.% NaOH were added dropwise thereto at a constant rate, maintaining the rate of evaporation of water at the rate of dropwise addition consistent with the rate of evaporation of water, wherein the pH was maintained at around 10. After the silicic acid is added dropwise, continuously stirring and cooling to room temperature to obtain the spherical silicon oxide abrasive particles.
In this comparative example, a silica sol having a solid mass fraction of spherical silica abrasive particles of 7.1 wt.% was finally obtained.
The polishing effect of the polishing solution of this comparative example on sapphire wafers is shown in Table 1.
The polishing test was performed on the sapphire wafers under certain polishing conditions using the polishing liquids of examples 1 to 4 and comparative examples 1 to 4 described above.
The polishing conditions for the polishing test were as follows:
polishing machine: UNIPOL-1502 single side polisher;
workpiece: a sapphire (0001) plane having a diameter of 50.8 mm;
polishing the pad: a polyurethane polishing pad;
polishing pressure: 6 kg;
rotating speed of a lower disc: 70 rpm;
polishing time: 2 h;
after polishing, the sapphire wafer is washed and dried according to the sequence of the cleaning solution, the deionized water and the ethanol, the mass of the sapphire wafer before and after polishing is weighed by a precision analytical balance, and the material removal rate MRR is calculated. Further, the surface roughness Ra before and after the sapphire polishing was measured by an Ambios Xi-100 surface profiler with a resolution of
The depth of focus was 3.0. mu.m, the working distance was 7.4mm, and the measurement area was 500. mu. m.times.500. mu.m.
The polishing effects of the polishing solutions of the respective examples on sapphire wafers are shown in Table 1. As can be seen from Table 1, the removal rates of the materials of examples 1 to 4 are significantly increased as compared with the polishing solutions of spherical silica abrasive particles having the same solid content in the comparative examples, and the rate of increase of the removal rate of the material is high as the solid content is increased. The surface roughness of all examples is not much different from that of the comparative examples. Wherein the material removal rate of the flower-shaped silica abrasive particles of example 2 was increased by 117% compared to the spherical silica abrasive particles.
TABLE 1 polishing Effect of the silicon oxide abrasive grains of examples of the present invention and comparative examples on sapphire wafers
In conclusion, compared with the conventional industrial spherical silica abrasive particles, the flower-shaped silica nano abrasive particles provided by the invention are used for polishing the sapphire wafer, can remarkably improve the material removal rate, and can keep the surface precision of the spherical silica sol abrasive particles after polishing the sapphire wafer. Compared with the single-point contact during polishing of the conventional spherical silicon oxide abrasive particles, the flower-shaped silicon oxide nano abrasive particles have more effective contact sites, so that the aim of removing more silicon oxide nano abrasive particles is fulfilled.
The above description is only a preferred embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, so that all equivalent structural changes made by using the contents of the specification and the drawings of the present invention should be included in the scope of the appended claims.
Claims (6)
1. A method for preparing flower-shaped silicon dioxide abrasive particles is characterized by comprising the following steps:
s01: adding polyvinylpyrrolidone into n-amyl alcohol, stirring until the polyvinylpyrrolidone is completely dissolved, adding absolute ethyl alcohol and a sodium citrate solution, stirring until the solution becomes turbid, adding ammonia water, stirring, heating the mixed solution, then slowly dropwise adding tetraethyl orthosilicate, continuously stirring, continuously reacting for 2 hours at a constant temperature of 70 ℃, sealing and cooling for 24 hours to obtain flower-shaped silicon dioxide seed crystals;
s02: passing the water glass solution through a cation exchange resin pretreated with HCl to obtain an active silicic acid solution;
s03: adding deionized water into the flower-shaped silicon dioxide seed crystal, stirring until the mixed solution is milky, heating, dropwise adding the active silicic acid solution and the NaOH solution, keeping the dropwise adding speed consistent with the water evaporation speed, wherein the pH of the mixed solution is regulated by the NaOH solution to be kept at 9-11, and performing oil-water separation in the process of dropwise adding the active silicic acid solution and the NaOH solution; after the silicic acid is added, continuously stirring and cooling to room temperature to obtain the flower-shaped silicon oxide abrasive particles.
2. The method of manufacturing a flower-shaped silica abrasive grain according to claim 1, wherein the ammonia water used in step S01 is 25 wt.% ammonia water; the sodium citrate solution was 0.36M sodium citrate solution.
3. The method for preparing the flower-shaped silica abrasive particles according to claim 1, wherein the mass ratio of the polyvinylpyrrolidone, the n-amyl alcohol, the absolute ethyl alcohol, the sodium citrate solution, the ammonia water, the TEOS and the like in the step S01 is as follows: 6-10: 122 to 244: 20: 10: 4-9: 5 to 10.
4. The method of claim 1, wherein 8 wt.% of the water glass is converted into 2 to 3 wt.% of the active silicic acid by the cationic resin in step S02.
5. The method for preparing the flower-shaped silica abrasive particles according to claim 1, wherein the mass ratio of the flower-shaped silica seed crystal, the deionized water and the active silicic acid in the step S03 is as follows: 300: 600-1000: 1600.
6. the method of manufacturing a flower-shaped silica abrasive grain according to claim 1, wherein the pH is maintained at 10 in step S03.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114525108A (en) * | 2022-02-18 | 2022-05-24 | 太仓硅源纳米材料有限公司 | Silica sol active abrasive particles for chemical mechanical polishing and preparation method thereof |
| CN115893427A (en) * | 2022-12-07 | 2023-04-04 | 北京航天赛德科技发展有限公司 | Silicon oxide material with rod-like structure and synthesis method and application thereof |
-
2020
- 2020-10-21 CN CN202011134849.XA patent/CN112209391A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| LEI XU ET AL: "Preparation of flower-shaped silica abrasives by double system template method and its effect on polishing performance of sapphire wafers" * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114525108A (en) * | 2022-02-18 | 2022-05-24 | 太仓硅源纳米材料有限公司 | Silica sol active abrasive particles for chemical mechanical polishing and preparation method thereof |
| CN115893427A (en) * | 2022-12-07 | 2023-04-04 | 北京航天赛德科技发展有限公司 | Silicon oxide material with rod-like structure and synthesis method and application thereof |
| CN115893427B (en) * | 2022-12-07 | 2023-12-29 | 北京航天赛德科技发展有限公司 | Silicon oxide material with rod-shaped structure and synthesis method and application thereof |
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Application publication date: 20210112 |