CN116042180A - Preparation process of nano silicon cerium powder for polishing semiconductor monocrystalline silicon wafer - Google Patents
Preparation process of nano silicon cerium powder for polishing semiconductor monocrystalline silicon wafer Download PDFInfo
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- CN116042180A CN116042180A CN202310315057.XA CN202310315057A CN116042180A CN 116042180 A CN116042180 A CN 116042180A CN 202310315057 A CN202310315057 A CN 202310315057A CN 116042180 A CN116042180 A CN 116042180A
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- 238000005498 polishing Methods 0.000 title claims abstract description 59
- 239000000843 powder Substances 0.000 title claims abstract description 39
- RBZGEUJLKTVORU-UHFFFAOYSA-N 12014-84-5 Chemical compound [Ce]#[Si] RBZGEUJLKTVORU-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000004065 semiconductor Substances 0.000 title claims abstract description 25
- 229910021421 monocrystalline silicon Inorganic materials 0.000 title claims abstract description 23
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 57
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 45
- 239000002244 precipitate Substances 0.000 claims abstract description 36
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 150000000703 Cerium Chemical class 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 14
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 229960001759 cerium oxalate Drugs 0.000 claims description 3
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical group [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 3
- 238000007602 hot air drying Methods 0.000 claims description 3
- 238000007603 infrared drying Methods 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000003916 acid precipitation Methods 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- -1 laser mirrors Substances 0.000 description 5
- 239000011246 composite particle Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000087 laser glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Classifications
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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
- C09K3/1436—Composite particles, e.g. coated particles
-
- 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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Silicon Compounds (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention provides a preparation process of nano silicon cerium powder for polishing a semiconductor monocrystalline silicon wafer, which comprises the following steps: s1, preparing a sodium silicate solution; s2, preparing an acid solution; s3, dropwise adding the S2 solution into the S1 to generate silicic acid precipitation; s4, filtering and washing the precipitate to prepare silicic acid suspension; s5, dissolving cerium salt in S4; s6, alkaline dissolution is dripped into the solution S5 to form coprecipitation of silicic acid and cerium hydroxide; and S7, filtering, drying and calcining the precipitate of the step S6 to obtain the required nano-silicon-cerium composite powder. The composite powder is prepared into polishing solution, and under the same concentration, the polishing efficiency is higher than that of silica sol for imported polishing, and meanwhile, the problems of silica sol crystallization precipitation, difficult cleaning and the like are solved.
Description
Technical Field
The invention relates to the technical field of surface polishing treatment of semiconductor monocrystalline silicon wafers, in particular to a preparation process of nano silicon cerium powder for polishing semiconductor monocrystalline silicon wafers.
Background
Chemical mechanical polishing is a technique for planarizing a surface of a workpiece by chemical and mechanical action of a polishing liquid, which can be used for ultra-smooth planarization of surfaces including laser glass, laser mirrors, semiconductor wafers, and semiconductor processes. Polishing solutions for use in superfinishing or polishing the surface of a substrate are well known in the art and generally include abrasives and dispersants in aqueous solutions, etchants, and the like. The abrasives recognized in the art include cerium oxide, silicon oxide, aluminum oxide, zirconium oxide, iron oxide, chromium oxide, and the like. The polishing solution using the rare earth polishing powder and the silicon oxide polishing powder as abrasive has the advantages of high polishing speed and high precision. In recent years, with rapid development of optics and semiconductors, laser glass, optical elements, semiconductors, and the like have increasingly demanded polishing powders, and polishing accuracy has been demanded more and more.
For this reason, the prior art has studied various methods for improving the polishing efficiency and uniformity of conventional polishing solutions while minimizing defects of the polished surface and damage to the underlying structure. For example, US5264010a discloses a polishing liquid comprising cerium oxide, fumed silica and precipitated silica, which can significantly improve polishing efficiency. CN101671538A discloses a method for synthesizing silicon/cerium composite particles by adopting a hydrothermal method with silica sol and cerium nitrate. CN104745146 discloses a method for preparing silicon/cerium composite particles by coprecipitation of silica sol and cerium salts such as cerium nitrate.
However, the polishing solution prepared by the prior silicon-cerium composite abrasive has a great gap between polishing efficiency and accuracy and imported silica sol, and the silicon-cerium composite abrasive for further improving polishing efficiency and processing accuracy in the monocrystalline silicon wafer polishing process still needs to be researched, and meanwhile, the problem that the silica sol is easy to crystallize and separate out to cause scratches in polishing is solved.
Disclosure of Invention
The invention aims to provide a preparation process of nano silicon cerium powder for polishing a semiconductor monocrystalline silicon wafer, aiming at the problem of nano silicon cerium composite powder in the prior art.
For this purpose, the above object of the present invention is achieved by the following technical solutions:
a preparation process of nano silicon cerium powder for polishing a semiconductor monocrystalline silicon wafer comprises the following steps:
s1, dissolving sodium silicate in pure water to prepare sodium silicate solution;
s2, preparing an acid solution, wherein the concentration of the acid solution is 0.1-35%;
s3, dropwise adding the acid solution obtained in the step S2 into the solution S1 under stirring, and reacting to generate silicic acid precipitate;
s4, filtering the precipitate obtained in the step S3, washing with water to obtain silicic acid, and preparing the silicic acid and pure water into suspension;
s5, dissolving cerium salt in the silicic acid suspension generated in the step S4, and then adding a surfactant;
s6, dropwise adding an alkaline solution into the solution generated in the step S5 to form coprecipitation of silicic acid and cerium hydroxide;
and S7, filtering, drying and calcining the precipitate generated in the step S6 to obtain the silicon-cerium composite powder.
The invention can also adopt or combine the following technical proposal when adopting the technical proposal:
as a preferable technical scheme of the invention: the concentration of sodium silicate in the step S1 is 1-40%.
As a preferable technical scheme of the invention: in step S2, the acid solution is an inorganic acid, such as sulfuric acid, nitric acid, and hydrochloric acid; or the acid solution is organic acid such as oxalic acid and citric acid; or the acid solution is carbonic acid generated by introducing carbon dioxide gas. The concentration of the acid solution is 0.1-35%.
As a preferable technical scheme of the invention: and in the step S5, cerium salt in the cerium salt is selected from cerium carbonate, cerium acetate, cerium oxalate, cerium nitrate or cerium chloride. The concentration of the cerium salt is 1-20%.
As a preferable technical scheme of the invention: the surfactant in the step S5 is one or more of cetyl trimethyl ammonium bromide, polyethylene glycol, stearic acid, sodium polyacrylate, ammonium polyacrylate and quaternary ammonium compound.
As a preferable technical scheme of the invention: in the step S6, the alkaline solution is selected from ammonia water, urea, sodium carbonate, sodium bicarbonate or ammonium bicarbonate.
As a preferable technical scheme of the invention: the drying mode in the step S7 is selected from hot air drying, infrared drying, microwave drying or spray drying; the calcining equipment is a muffle furnace, a shuttle furnace, a trolley furnace, a lifting furnace, a push plate furnace or a roller furnace; the calcination temperature is 400-1100 ℃.
According to the preparation process of the nano silicon cerium powder for polishing the semiconductor monocrystalline silicon wafer, sodium silicate is hydrolyzed to obtain silicic acid precipitate, the silicic acid precipitate is mixed with cerium nitrate solution, ammonia water is used as a precipitating agent to obtain composite particles of cerium hydroxide coated silicic acid, the composite particles are filtered, dried and calcined to obtain nano silicon/cerium composite powder; the preparation method of the nano silicon cerium composite powder is simple and stable, has few procedures, low requirements on equipment, few raw material types, and low production cost, and generates tail gas which is easy to absorb and treat, and is nontoxic and pollution-free; in addition, the silicon-cerium composite powder produced by adding a certain amount of surfactant is spherical, has high purity, does not agglomerate, has narrow particle size distribution and is easy to disperse; the silicon-cerium composite powder is applied to the field of polishing of semiconductor monocrystalline silicon wafers, has higher polishing efficiency than imported coarse polished silica sol under the same concentration, does not have the problems of crystallization precipitation of the silica sol, difficult cleaning after polishing and the like, and has wide application prospects in the fields of polishing of semiconductor monocrystalline silicon wafers and the like.
Drawings
FIG. 1 is a photograph of a first electron microscope of nano-silicon cerium powder for polishing a semiconductor monocrystalline silicon wafer;
fig. 2 is a second electron microscope photograph of nano-silicon cerium in the preparation process of nano-silicon cerium powder for polishing a semiconductor monocrystalline silicon wafer.
Detailed Description
The invention will be described in further detail with reference to the drawings and specific embodiments.
The invention relates to a preparation process of nano silicon cerium powder for polishing a semiconductor monocrystalline silicon wafer, which comprises the following steps:
s1, preparing a sodium silicate solution: dissolving sodium silicate with certain mass in pure water;
s2, preparing an acid solution with a certain concentration;
s3, dripping the acid solution obtained in the step S2 into the solution S1 at a certain speed under the stirring state, and reacting to generate silicic acid precipitate;
s4, filtering the precipitate obtained in the step S3, washing the precipitate with water to obtain silicic acid, and preparing the silicic acid and pure water into suspension with a certain concentration;
s5, dissolving a certain amount of cerium salt in the suspension of the silicic acid of S4, and adding a certain amount of surfactant;
s6, dropwise adding an alkaline solution into the solution S5 to form coprecipitation of silicic acid and cerium hydroxide;
and S7, filtering, drying and calcining the precipitate generated in the step S6 to obtain the silicon-cerium composite powder.
Further, the concentration of sodium silicate in the step S1 is 1-40%.
Further, the acid solution in the step S2 is inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid, etc., organic acid such as oxalic acid, citric acid, etc., or carbon dioxide gas is introduced to generate carbonic acid; the concentration of the acid solution is 0.1-35%.
Further, in step S5, the cerium salt is cerium carbonate, cerium acetate, cerium oxalate, cerium nitrate, cerium chloride, or the like. The concentration of the cerium salt is 1-20%.
Further, the surfactant in step S5 is one or more of cetyltrimethylammonium bromide, polyethylene glycol, stearic acid, sodium polyacrylate, ammonium polyacrylate and quaternary ammonium compound.
Further, in step S6, the alkaline solution is ammonia water, urea, sodium carbonate, or sodium bicarbonate.
Further, in step S7, the drying mode is hot air drying, infrared drying, microwave drying, spray drying, etc.; the calcining equipment is a muffle furnace, a shuttle furnace, a trolley furnace, a lifting furnace, a push plate furnace, a roller furnace and the like; the calcination temperature is 400-1100 ℃.
The invention relates to a preparation process of nano silicon cerium powder for polishing a semiconductor monocrystalline silicon wafer, which is characterized in that the composite powder is prepared into polishing solution, and under the same concentration, the polishing efficiency is higher than that of silica sol for import polishing, and meanwhile, the problems of crystallization precipitation of the silica sol, difficult cleaning and the like are solved.
Example 1
Taking 28g of sodium silicate solution and 72 g of pure water, preparing hydrochloric acid with the concentration of 35%, adding the hydrochloric acid solution into the sodium silicate solution at the flow rate of 10ml/min, stirring while adding acid, and separating out the white precipitate by adopting a centrifuge when the pH value of the solution is 5-6 and the reaction is finished. The obtained precipitated silicic acid was stirred and mixed with 90 g of pure water to form a dispersed suspension. 15 g of cerium nitrate solution was added to the silicic acid suspension, and 0.1 g of ammonium polyacrylate was added thereto, followed by sufficiently stirring for dissolution. 40% ammonia water was diluted to a concentration of 10%, and an ammonia water solution was added to the cerium salt-containing silicic acid suspension at a concentration of 5ml/min, and when the pH was raised to about 9, the reaction was completed, and silicic acid and cerium hydroxide were precipitated. The precipitate was separated from the water using a centrifuge and the precipitate was dried. And crushing the dried precipitate, calcining, heating to 800 ℃ at a temperature of 5 ℃ per minute, preserving heat for one hour, and cooling to room temperature along with a furnace to obtain 10-20 nm silicon-cerium composite powder. Fig. 1 and 2 are electron micrographs of this example.
Example 2
10g of sodium silicate solution is taken to 90 g of pure water, 10% concentration citric acid is prepared, the citric acid solution is introduced into the sodium silicate solution at a flow rate of 1L/min, the solution is stirred while acid is added, until white precipitate is fully separated out, when the pH value of the solution is 5-6, the reaction is finished, and a centrifuge is used for separating the precipitate silicic acid from water. The obtained precipitated silicic acid was stirred and mixed with 90 g of pure water to form a dispersed suspension. 7 g of cerium nitrate solution was added to the silicic acid suspension, and 0.1 g of ammonium polyacrylate was added thereto, followed by sufficiently stirring for dissolution. 40% ammonia water was diluted to a concentration of 10%, and an ammonia water solution was added to the cerium salt-containing silicic acid suspension at a concentration of 5ml/min, and when the pH was raised to about 9, the reaction was completed, and silicic acid and cerium hydroxide were precipitated. The precipitate was separated from the water using a centrifuge and the precipitate was dried. And crushing the dried precipitate, calcining, heating to 800 ℃ at a temperature of 5 ℃ per minute, preserving heat for one hour, and cooling to room temperature along with a furnace to obtain 10-20 nm silicon-cerium composite powder.
Example 3
2g of sodium silicate solution is taken and 98 g of pure water is added, carbon dioxide gas is added into the sodium silicate solution at a flow rate of 1L/min, the mixture is stirred while the carbon dioxide gas is added, until white precipitate is fully separated out, and when the pH value of the solution is 5-6, the reaction is finished, and a centrifuge is used for separating the precipitated silicic acid from water. The obtained precipitated silicic acid was stirred and mixed with 90 g of pure water to form a dispersed suspension. 1 g of cerium chloride solution was added to the silicic acid suspension, and 0.1 g of polyethylene glycol 2000 was added thereto, followed by stirring and dissolution. Sodium carbonate is used to prepare 10% concentration, and sodium carbonate solution is added into the silicic acid suspension containing cerium salt at a concentration of 5ml/min, when the pH value is raised to about 9, the reaction is complete, and silicic acid and cerium hydroxide are precipitated. The precipitate was separated from the water using a centrifuge and the precipitate was dried. And crushing the dried precipitate, calcining, heating to 850 ℃ at a temperature of 10 ℃ per minute, preserving heat for two hours, and cooling to room temperature along with a furnace to obtain the 50-60 nanometer silicon-cerium composite powder.
Example 4
Taking 40g of sodium silicate solution and 60 g of pure water, preparing nitric acid with the concentration of 10%, adding the nitric acid solution into the sodium silicate solution at the flow rate of 5ml/min, stirring while adding acid, and separating out the white precipitate by adopting a centrifuge when the pH value of the solution is 5-6 and the reaction is finished. The obtained precipitated silicic acid was stirred and mixed with 80 g of pure water to form a dispersed suspension. 30 g of cerium nitrate solution is added into the suspension of silicic acid, and 0.2 g of quaternary ammonium salt dispersing agent is added, and the mixture is fully stirred and dissolved. Preparing urea into 10% concentration, adding urea solution into the cerium salt-containing silicic acid suspension at a concentration of 1ml/min, adding urea solution into the suspension to obtain 100ml, slowly decomposing urea in the suspension, reacting with cerium ions to generate cerium hydroxide, reacting for 8 hours, and precipitating silicic acid and cerium hydroxide until the reaction is complete. The precipitate was separated from the water using a centrifuge and the precipitate was dried. And crushing the dried precipitate, calcining, heating to 800 ℃ at a temperature of 5 ℃ per minute, preserving heat for one hour, and cooling to room temperature along with a furnace to obtain the 20-30 nanometer silicon-cerium composite powder.
Example 5
Taking 20g of sodium silicate solution and 80 g of pure water, preparing 10% concentration citric acid, introducing the citric acid solution into the sodium silicate solution at a flow rate of 1L/min, adding acid while stirring, and separating out white precipitate completely, when the pH value of the solution is 5-6, and separating the precipitate silicic acid from water by adopting a centrifuge. The obtained precipitated silicic acid was stirred and mixed with 90 g of pure water to form a dispersed suspension. 10g of cerium nitrate solution was added to the silicic acid suspension, and 0.1 g of ammonium polyacrylate was added thereto, followed by sufficiently stirring for dissolution. Preparing ammonium bicarbonate with the concentration of 10%, adding the ammonium bicarbonate into the cerium salt-containing silicic acid suspension at the concentration of 5ml/min, and completely reacting when the pH value is raised to about 9, and precipitating silicic acid and cerium hydroxide. The precipitate was separated from the water using a centrifuge and the precipitate was dried. And crushing the dried precipitate, calcining, heating to a temperature of 850 ℃ at a temperature of 15 ℃ per minute, preserving heat for one hour, and cooling to room temperature along with a furnace to obtain the 70-80 nanometer silicon-cerium composite powder.
Polishing test: 1. mixing the nano silicon-cerium composite powder prepared in the example 1 with a proper amount of deionized water under stirring to obtain a polishing solution with the mass fraction of 30%, mixing the nano silicon-cerium composite powder prepared in the example 2 with a proper amount of deionized water under stirring to obtain a polishing solution with the mass fraction of 2%, and mixing the imported silica sol (containing 40% of silica abrasive particles with the particle size of 50 nanometers) with a proper amount of deionized water under stirring to obtain a polishing solution with the mass fraction of 2%.
The five polishing solutions were used for polishing test of 6-inch monocrystalline silicon wafers, respectively, using a herud 9B polisher, in combination with a sub 600 polishing pad, and polishing conditions and respective polishing test results are shown in table 1.
Table 1: polishing efficiency and roughness comparison
| Polishing liquid | Concentration of | Pressure kg/cm 2 | Rotational speed r/min | Polishing efficiency nm/min | Roughness nm |
| Example one | 2% | 0.45 | 20 | 250 | 0.691 |
| Example two | 2% | 0.45 | 20 | 220 | 0.653 |
| Inlet silica sol | 2% | 0.45 | 20 | 209 | 0.672 |
The above detailed description is intended to illustrate the present invention by way of example only and not to limit the invention to the particular embodiments disclosed, but to limit the invention to the precise embodiments disclosed, and any modifications, equivalents, improvements, etc. that fall within the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation process of nano silicon cerium powder for polishing a semiconductor monocrystalline silicon wafer comprises the following steps:
s1, dissolving sodium silicate in pure water to prepare sodium silicate solution;
s2, preparing an acid solution, wherein the concentration of the acid solution is 0.1-35%;
s3, dropwise adding the acid solution obtained in the step S2 into the solution S1 under stirring, and reacting to generate silicic acid precipitate;
s4, filtering the silicic acid precipitate obtained in the step S3, washing with water to obtain silicic acid, and preparing the silicic acid and pure water into suspension;
s5, dissolving cerium salt in the silicic acid suspension generated in the step S4, and adding a surfactant, wherein the concentration of the cerium salt is 1-20%;
s6, dropwise adding an alkaline solution into the solution generated in the step S5 to form coprecipitation of silicic acid and cerium hydroxide;
and S7, filtering, drying and calcining the precipitate generated in the step S6 to obtain the silicon-cerium composite powder.
2. The process for preparing nano-silicon cerium powder for polishing a semiconductor single crystal silicon wafer according to claim 1, wherein: the concentration of sodium silicate in the step S1 is 1-40%.
3. The process for preparing nano-silicon cerium powder for polishing a semiconductor single crystal silicon wafer according to claim 1, wherein: in step S2, the acid solution is an inorganic acid, such as sulfuric acid, nitric acid, and hydrochloric acid; or the acid solution is organic acid such as oxalic acid and citric acid; or the acid solution is carbonic acid generated by introducing carbon dioxide gas.
4. The process for preparing nano-silicon cerium powder for polishing a semiconductor single crystal silicon wafer according to claim 1, wherein: and in the step S5, cerium salt in the cerium salt is selected from cerium carbonate, cerium acetate, cerium oxalate, cerium nitrate or cerium chloride.
5. The process for preparing nano-silicon cerium powder for polishing a semiconductor single crystal silicon wafer according to claim 1, wherein: the surfactant in the step S5 is one or more of cetyl trimethyl ammonium bromide, polyethylene glycol, stearic acid, sodium polyacrylate, ammonium polyacrylate and quaternary ammonium compound.
6. The process for preparing nano-silicon cerium powder for polishing a semiconductor single crystal silicon wafer according to claim 1, wherein: in the step S6, the alkaline solution is selected from ammonia water, urea, sodium carbonate, sodium bicarbonate or ammonium bicarbonate.
7. The process for preparing nano-silicon cerium powder for polishing a semiconductor single crystal silicon wafer according to claim 1, wherein: the drying mode in the step S7 is selected from hot air drying, infrared drying, microwave drying or spray drying; the calcining equipment is a muffle furnace, a shuttle furnace, a trolley furnace, a lifting furnace, a push plate furnace or a roller furnace; the calcination temperature is 400-1100 ℃.
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