CN116731674A - Nanometer abrasive particles, preparation method thereof and application thereof in chemical mechanical polishing - Google Patents
Nanometer abrasive particles, preparation method thereof and application thereof in chemical mechanical polishing Download PDFInfo
- Publication number
- CN116731674A CN116731674A CN202310526232.XA CN202310526232A CN116731674A CN 116731674 A CN116731674 A CN 116731674A CN 202310526232 A CN202310526232 A CN 202310526232A CN 116731674 A CN116731674 A CN 116731674A
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- Prior art keywords
- acid
- solution
- abrasive particles
- nano
- particles
- Prior art date
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- 239000002245 particle Substances 0.000 title claims abstract description 131
- 238000005498 polishing Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000002105 nanoparticle Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 136
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 46
- 239000002253 acid Substances 0.000 claims description 38
- 238000005530 etching Methods 0.000 claims description 26
- 239000003093 cationic surfactant Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000003929 acidic solution Substances 0.000 claims description 15
- 239000012798 spherical particle Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 claims description 8
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- 125000003636 chemical group Chemical group 0.000 claims description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 239000003223 protective agent Substances 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229940013688 formic acid Drugs 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011368 organic material Substances 0.000 claims description 4
- 229940116315 oxalic acid Drugs 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- OQZAQBGJENJMHT-UHFFFAOYSA-N 1,3-dibromo-5-methoxybenzene Chemical compound COC1=CC(Br)=CC(Br)=C1 OQZAQBGJENJMHT-UHFFFAOYSA-N 0.000 claims description 3
- HSNJERRVXUNQLS-UHFFFAOYSA-N 1-(4-tert-butylphenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(C(C)(C)C)C=C1 HSNJERRVXUNQLS-UHFFFAOYSA-N 0.000 claims description 3
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 3
- JMHWNJGXUIJPKG-UHFFFAOYSA-N CC(=O)O[SiH](CC=C)OC(C)=O Chemical compound CC(=O)O[SiH](CC=C)OC(C)=O JMHWNJGXUIJPKG-UHFFFAOYSA-N 0.000 claims description 3
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- FQEKAFQSVPLXON-UHFFFAOYSA-N butyl(trichloro)silane Chemical compound CCCC[Si](Cl)(Cl)Cl FQEKAFQSVPLXON-UHFFFAOYSA-N 0.000 claims description 3
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 3
- 229940005991 chloric acid Drugs 0.000 claims description 3
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 claims description 3
- MLGFKQNIGKTEEV-UHFFFAOYSA-M diethyl(dimethyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CC MLGFKQNIGKTEEV-UHFFFAOYSA-M 0.000 claims description 3
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 claims description 3
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 3
- ZHKRBCQSLSTSAO-UHFFFAOYSA-N dodecyl(trimethyl)silane Chemical compound CCCCCCCCCCCC[Si](C)(C)C ZHKRBCQSLSTSAO-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 3
- CJCLDCFGJRZTSP-UHFFFAOYSA-N ethenyl-tri(propan-2-yl)silane Chemical compound CC(C)[Si](C=C)(C(C)C)C(C)C CJCLDCFGJRZTSP-UHFFFAOYSA-N 0.000 claims description 3
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229940071870 hydroiodic acid Drugs 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- -1 polypropylene carbonate Polymers 0.000 claims description 3
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- ODTSDWCGLRVBHJ-UHFFFAOYSA-M tetrahexylazanium;chloride Chemical compound [Cl-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC ODTSDWCGLRVBHJ-UHFFFAOYSA-M 0.000 claims description 3
- SXAWRMKQZKPHNJ-UHFFFAOYSA-M tetrapentylazanium;chloride Chemical compound [Cl-].CCCCC[N+](CCCCC)(CCCCC)CCCCC SXAWRMKQZKPHNJ-UHFFFAOYSA-M 0.000 claims description 3
- JVOPCCBEQRRLOJ-UHFFFAOYSA-M tetrapentylazanium;hydroxide Chemical compound [OH-].CCCCC[N+](CCCCC)(CCCCC)CCCCC JVOPCCBEQRRLOJ-UHFFFAOYSA-M 0.000 claims description 3
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 claims description 3
- GBXOGFTVYQSOID-UHFFFAOYSA-N trichloro(2-methylpropyl)silane Chemical compound CC(C)C[Si](Cl)(Cl)Cl GBXOGFTVYQSOID-UHFFFAOYSA-N 0.000 claims description 3
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 3
- LFXJGGDONSCPOF-UHFFFAOYSA-N trichloro(hexyl)silane Chemical compound CCCCCC[Si](Cl)(Cl)Cl LFXJGGDONSCPOF-UHFFFAOYSA-N 0.000 claims description 3
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 3
- 229960004319 trichloroacetic acid Drugs 0.000 claims description 3
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 claims description 3
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical compound CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 3
- NRWCNEBHECBWRJ-UHFFFAOYSA-M trimethyl(propyl)azanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)C NRWCNEBHECBWRJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 3
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- SIQRHSDBXPLBMI-UHFFFAOYSA-N pyridin-2-ylsilane Chemical compound [SiH3]C1=CC=CC=N1 SIQRHSDBXPLBMI-UHFFFAOYSA-N 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 61
- 239000005543 nano-size silicon particle Substances 0.000 abstract description 57
- 239000011148 porous material Substances 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 5
- 238000007517 polishing process Methods 0.000 abstract description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 15
- 229910000077 silane Inorganic materials 0.000 description 15
- 150000001768 cations Chemical class 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000002077 nanosphere Substances 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LLYCMZGLHLKPPU-UHFFFAOYSA-N perbromic acid Chemical compound OBr(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-N 0.000 description 1
- VSRVYCZMSNZEPA-UHFFFAOYSA-N pyridine silane Chemical compound [SiH4].C1=CC=NC=C1 VSRVYCZMSNZEPA-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
Abstract
The application discloses nano abrasive particles, a preparation method thereof and application thereof in chemical mechanical polishing, and belongs to the field of chemical mechanical planarization. A nano abrasive particle, wherein the surface of the nano abrasive particle is distributed with a meteorite structure. Because the particles with the meteorite structures have a certain angle between the external tangent and the internal tangent, the sharp angle can further improve the mechanical action of polishing in the polishing process; in addition, compared with the original particles or particles with other morphologies, the nano particles with the meteorite structure have larger specific surface area and pore volume, and the contact area between the particles and the polished species can be realized by a method of modifying the surface properties, so that the polishing rate is improved; in addition, the nano silicon oxide particles based on the meteorite structure have a relatively large number of pore structures, so that the toughness of the particles can be improved, the hardness of the particles can be reduced, and the scratch problem caused by polishing the particles can be reduced.
Description
Technical Field
The application relates to nano abrasive particles, a preparation method thereof and application thereof in chemical mechanical polishing, and belongs to the field of chemical mechanical planarization.
Background
In the prior art, in order to increase the high removal rate of polished abrasive and reduce scratches on products (e.g., chips), nano-silica is modified so as to be connected to each other by reacting with a silane coupling agent to form non-spherical clusters.
Disclosure of Invention
According to a first aspect of the present application, there is provided a nano abrasive particle. The nano abrasive particles have a meteorite structure, and a certain angle exists between an external tangent line and an internal tangent line of the particles with the meteorite structure, so that the sharp angle can further improve the mechanical action of polishing in the polishing process; in addition, compared with the original particles or particles with other morphologies, the nano particles with the meteorite structure have larger specific surface area and pore volume, and the contact area between the particles and the polished species can be realized by a method of modifying the surface properties, so that the polishing rate is improved; in addition, the nano silicon oxide particles based on the meteorite structure have a relatively large number of pore structures, so that the toughness of the particles can be improved, the hardness of the particles can be reduced, and the scratch problem caused by polishing the particles can be reduced.
A nano abrasive particle, wherein the surface of the nano abrasive particle is distributed with a meteorite structure.
Optionally, a pointed structure is formed between the merle surface of the merle structure and the nanoparticle surface.
Optionally, the pointed structures are formed by external and internal tangents to the nano abrasive particles.
Optionally, the merle face of the merle structure is directionally grafted with a chemical group.
Chemical groups include positive and negative charges/oxidizing groups, which are released during CMP to increase polishing efficiency.
Optionally, the number of merle structures n >1;
the maximum distance L <150nm of the merle surface of the merle structure.
Optionally, the angle of the pointed structure is θ, where θ is 5+.ltoreq.170 °.
Alternatively, θ is independently selected from any value or range value between any two of 5 °, 10 °, 15 °, 20 °, 25 °, 30 °, 35 °, 40 °, 45 °,50 °, 55 °, 60 °, 65 °, 70 °, 75 °, 80 °, 85 °, 90 °, 95 °, 100 °, 110 °, 120 °, 130 °, 140 °, 150 °, 160 °, 170 °.
Optionally, the nano abrasive particles are at least one selected from inorganic materials, organic materials, and composite materials.
Optionally, the inorganic material is at least one selected from the group consisting of silica, alumina, ceria, and zirconia.
Optionally, the organic material is selected from at least one of polystyrene, polyacrylate, polypropylene carbonate.
Optionally, the nano abrasive particles are spherical particles or non-spherical particles.
Preferably spherical silica, but may also be peanut-shaped or otherwise non-spherical in shape.
The particle diameter of the spherical nano silicon oxide particles is 5-150 nm, preferably 10-100 nm.
Optionally, the non-spherical particles comprise a linker consisting of 2 to 5 of the nano abrasive particles.
Optionally, the dimension of the linker is 5-200 nm.
The secondary particle size of the nano particles is 5-200 nm, and the morphology of the nano particles can be spherical particles or connector non-spherical particles of 2-5 nano particles or non-spherical nano particles with other morphologies; the particles with the meteorite structure are used as the abrasive of the polishing solution of the chemical mechanical planarization process, have high removal rate and have less scratches on products (such as chips).
Optionally, the diameter of the spherical particle is D, the width of the merle structure is a, and the depth of the merle structure is h, then:
a/D=0.01~0.5,h/D=0.01~0.5。
alternatively, a/D is independently selected from any value or range of values between any two of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30, 035, 0.40, 0.45, 0.50.
Alternatively, h/D is independently selected from any value or range of values between any two of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30, 035, 0.40, 0.45, 0.50.
Optionally, the particle size of the spherical particles is 5-150 nm.
Alternatively, the spherical particles have a particle size independently selected from any value or range between any two of 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm.
According to a second aspect of the present application, there is provided a method of preparing nano abrasive particles. According to the method, after spherical nano silicon oxide particles act with a protective agent, selective etching is performed on the surface of the nano silicon oxide, and non-spherical silicon dioxide particles are generated by utilizing the etching speed difference of different positions. Namely, the distribution of different sites on the surface of the nano silicon oxide can be realized by regulating the proportion of the two, and the silicon oxide of the covered site is protected by the silane coupling agent and the cationic surfactant due to the difference in corrosion resistance between the covered site and the uncovered site, so that the silicon oxide is not easy to corrode. Therefore, the preparation of the meteorite structure on the surface of the nano silicon oxide is realized by the principle. The protective agent can be a silane coupling agent or a cationic surfactant, the silane coupling agent is connected with the nano silicon oxide particles through a silicon oxygen bond formed by reaction, and the cationic surfactant is adsorbed on the surfaces of the nano silicon oxide particles through electrostatic action. The acid etching method is to generate SiF 4 The gas can be well separated from the solution. Alkaline etching is deposited with a change in pH, thereby causing the etched species to change morphology.In addition, since the cation is realized by adsorption in such a manner that it is physically electrostatically attracted, it may not be finer than the structure obtained by the silane coupling agent at the time of etching.
The preparation method of the nano abrasive particles comprises the following steps:
s1, reacting a mixed solution containing nano particles and a protective agent to obtain surface modified nano abrasive particles;
and S2, etching the surface-modified nano abrasive particles to obtain the nano abrasive particles.
Optionally, the nanoparticles in step S1 are of a material consistent with the nano abrasive particles.
Optionally, the protecting agent is at least one selected from silane coupling agents and cationic surfactants.
Optionally, the silane coupling agent is selected from at least one of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, β (3, 4) epoxycyclohexylethyltrimethoxysilane, 1,2 bis-trimethoxysilylethane, methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, 3 aminopropyltrimethoxysilane, 3 aminopropyltriethoxysilane, N-aminoethyl- γ -aminopropyltrimethoxysilane, 3 mercaptopropyltrimethoxysilane, 3 mercaptopropyltriethoxysilane, methylvinyldiethoxysilane, 3 chloropropyltrimethoxysilane, hexamethyldisilazane, hexamethyldisiloxane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, pyridine silane, N-butyltrichlorosilane, isobutyltrichlorosilane, hexyltrichlorosilane, vinyltrichlorosilane, vinyltriisopropylsilane, diphenyldimethoxysilane, dodecyltrimethylsilane.
Optionally, the cationic surfactant is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, methyltriethylammonium hydroxide, diethyldimethylammonium hydroxide, triethylmethylammonium hydroxide, benzyltrimethylammonium hydroxide, tributylmethylammonium hydroxide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrapentylammonium chloride, tetrahexylammonium chloride, methyltriethylammonium chloride, diethyldimethylammonium chloride, triethylmethylammonium chloride, benzyltrimethylammonium chloride, tripropylmethylammonium chloride, methyltributylammonium chloride, dioctyldimethylammonium chloride, didecyldimethylammonium chloride, and cetylamido propyltrimethylammonium chloride.
Optionally, the method comprises the following steps:
s1, reacting a mixture containing a nanoparticle solution and a silane coupling agent solution to obtain surface-modified nano abrasive particles; or alternatively, the first and second heat exchangers may be,
reacting II the mixture containing the nanoparticle solution and the cationic surfactant solution to obtain surface-modified nano abrasive particles;
s2, etching the surface-modified nano abrasive particles to obtain the nano abrasive particles;
optionally, in step S1, the volume ratio of the nanoparticle solution to the silane coupling agent solution is 0.01 to 0.4.
Alternatively, the volume ratio of the nanoparticle solution to the silane coupling agent solution is independently selected from any of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, or a range value between any two.
Optionally, in step S1, the volume ratio of the nanoparticle solution to the cationic surfactant solution is 0.01 to 0.6.
Optionally, the volume ratio of the nanoparticle solution to the cationic surfactant solution is independently selected from the values of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.55, 0.57, 0.59, 0.55, or any two of the values.
Optionally, in step S1, the silane coupling agent solution is a silane coupling agent, water and alcohol according to a molar ratio of 1: (0-700): (0-20), wherein the molar ratio is not in the range of 0.
Optionally, in step S1, the silane coupling agent solution is a silane coupling agent, water and alcohol according to a molar ratio of 1: (100-600): (5-15).
Optionally, in step S1, the silane coupling agent solution is a silane coupling agent, water and alcohol according to a molar ratio of 1: (200-400): (7-12).
Optionally, the nanoparticle solution has a pH of 7 to 11.
Optionally, the pH value of the silane coupling agent solution is 1-4.
Alternatively, in step S1, the conditions for reaction I are as follows:
the temperature is 20-80 ℃;
the time is 0.5-3 h.
Alternatively, in step S1, the conditions for reaction ii are as follows:
the temperature is 20-50 ℃;
the time is 1-3 h.
Optionally, in step S2, the etching includes alkaline etching and acidic etching.
Optionally, the alkaline etching comprises the steps of:
and (3) regulating the pH value of the surface-modified nano abrasive particles to 10.5-14 by using an alkaline solution D, reacting for 5-24 hours at the temperature of 85-120 ℃, and regulating the pH value to 7-10.5 by using an acidic solution E to obtain the nano abrasive particles.
Optionally, the alkaline solution D is at least one selected from sodium hydroxide solution, potassium hydroxide solution and sodium bicarbonate solution.
In the step of adjusting the pH of the silane modified nano silicon oxide solution B to between 10.5 and 14 by using an alkaline solution D, the pH range is preferably 11 to 12.5; in the step of reacting for 5-24 hours at 85-120 ℃, the reaction temperature is preferably 85-95 ℃ and the reaction time is preferably 5-11 hours; or in the step of adjusting the pH of the nano-silica solution C with the cations attached to the surface to between 10.5 and 14 with an alkaline solution D, the pH is preferably in the range of 11 to 12.5; in the step of reacting for 5-24 hours at 85-120 ℃, the reaction temperature is preferably 85-95 ℃ and the reaction time is preferably 5-11 hours.
In the step of adjusting the pH to 7 to 10.5 with the acidic solution E, the pH is preferably in the range of 7 to 8.5.
Optionally, the acidic solution E is at least one selected from inorganic acids and organic acids.
Optionally, the inorganic acid is at least one selected from hydrochloric acid, nitric acid, boric acid, acetic acid and sulfuric acid.
Optionally, the organic acid is at least one selected from formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, 2, 3-dihydroxysuccinic acid and 2-hydroxysuccinic acid.
Optionally, the acid etching comprises the steps of:
and (3) reacting the mixture containing the surface modified nano abrasive particles and the acid solution D to obtain the nano abrasive particles.
Optionally, the molar ratio of the surface-modified nano abrasive particles to the acidic solution D is 1: (0.001-1);
the above molar ratios are calculated as silicon and fluorine, respectively.
Alternatively, the molar ratio of the surface-modified nano-abrasive particles to the acidic solution D is independently selected from 1:0.001, 1:0.002, 1:0.003, 1:0.004, 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.010, 1:0.015, 1:0.020, 1:0.025, 1:0.030, 1:0.035, 1:0.040, 1:0.045, 1:0.050, 1:0.060, 1:0.070, 1:0.080, 1:0.090, 1:0.100, 1:0.200, 1:0.300, 1:0.400, 1:0.500, 1:0.600, 1:0.700, 1:0.800, 1:0.900, 1: any value in 1.000 or a range value between any two.
Mixing a silane modified nano silicon oxide solution B with an acid solution D, wherein the dosage ratio of the silane modified nano silicon oxide solution B to the acid solution D is 1 calculated by the mole ratio of silicon to fluorine: (0.001-1), reacting for 5-24 hours at the temperature of 40-120 ℃ to obtain non-spherical nano silicon oxide particle solution; or mixing the nano silicon oxide solution C with the surface attached with cations with the acid solution D, wherein the dosage ratio of the nano silicon oxide solution C to the acid solution D is 1 calculated by the mole ratio of silicon to fluorine: (0.001-1), and reacting for 5-24 hours at the temperature of 40-120 ℃ to obtain non-spherical nano silicon oxide particle solution.
In the step of mixing the silane modified nano silicon oxide solution B and the acid solution D, the dosage ratio of the silane modified nano silicon oxide solution B to the acid solution D is preferably 1: (0.001-0.3); in the step of reacting for 5-24 hours at 40-120 ℃, the reaction temperature is preferably 40-95 ℃ and the reaction time is preferably 5-11 hours; in the step of mixing the nano silicon oxide solution C with the cations attached to the surface and the acid solution D, the dosage ratio of the nano silicon oxide solution C to the acid solution D is preferably 1: (0.001-0.3); in the step of reacting for 5-24 hours at 40-120 ℃, the reaction temperature is preferably 40-95 ℃ and the reaction time is preferably 5-11 hours.
Alternatively, the conditions for reaction III are as follows:
the temperature is 40-120 ℃;
the time is 5-24 hours.
Optionally, the acid solution D is prepared from a fluoride solution E and a strong acid solution F according to a molar ratio of 1: (0.01-20).
Optionally, the fluoride solution E is at least one selected from hydrofluoric acid, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride, tetrabutylammonium fluoride.
Optionally, the strong acid solution F is selected from at least one of organic acid and inorganic acid.
Optionally, the organic acid is at least one selected from trifluoroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, oxalic acid and formic acid.
Optionally, the inorganic acid is selected from at least one of sulfuric acid, nitric acid, perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrobromic acid, metaperiodic acid, chloric acid, hydrobromic acid, metaphosphoric acid, permanganic acid, hydroboric acid, and fluorosulfonic acid.
According to a third aspect of the present application there is provided the use of nano abrasive particles.
The nano abrasive particles and/or the nano abrasive particles obtained by the preparation method are applied to chemical mechanical polishing.
The application has the beneficial effects that:
1) According to the nano abrasive particles provided by the application, as the particles with the meteorite structures have a certain angle between the external tangent and the internal tangent, the sharp angle can further improve the mechanical action of polishing in the polishing process; in addition, compared with the original particles or particles with other morphologies, the nano particles with the meteorite structure have larger specific surface area and pore volume, and the contact area between the particles and the polished species can be realized by a method of modifying the surface properties, so that the polishing rate is improved; in addition, the nano silicon oxide particles based on the meteorite structure have a relatively large number of pore structures, so that the toughness of the particles can be improved, the hardness of the particles can be reduced, and the scratch problem caused by polishing the particles can be reduced.
2) According to the preparation method of the nano abrasive particles, provided by the application, the silane coupling agent or the combination between the cationic surfactant and the nano silicon oxide is adopted, the distribution of different sites on the surface of the nano silicon oxide can be realized by regulating and controlling the proportion of the silane coupling agent or the cationic surfactant and the nano silicon oxide, and the silicon oxide at the covered site is protected by the silane coupling agent and the cationic surfactant and is not easy to corrode due to the different corrosion resistance properties between the covered site and the uncovered site. Therefore, the preparation of the meteorite structure on the surface of the nano silicon oxide is realized.
Drawings
FIG. 1 is a schematic representation of the nano-abrasive particles of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials in the examples of the present application were purchased commercially.
Unless otherwise indicated, conventional testing methods or instrumental recommended testing methods are employed.
According to one embodiment of the present application, a nano abrasive particle is provided. The surface of the nanoparticle is distributed with different sizes and numbers of merles.
According to one embodiment of the application, the merle is uniformly distributed on the surface of the silica particle, wherein the number n of merles is >1, the maximum distance of the merle surface is <150nm, and the angle between the merle and the tangent line near the particle surface is 5 DEG theta < 170 deg.
According to one embodiment of the application, the nanoparticles are spherical silica or peanut-shaped or other non-spherical. In order to increase the removal rate and reduce scratches on the product (e.g., chip), spherical silicon oxide is preferred. The particle diameter of the spherical nano silicon oxide particles is 5-150 nm, preferably 10-100 nm.
According to one embodiment of the application, when the nanoparticle is spherical silica, the width of the merle structure is a, the depth of the merle structure is h, and the diameter of the spherical nanoparticle is D, wherein a/d=0.01 to 0.5, and h/d=0.01 to 0.5.
According to one embodiment of the application, a sharp corner is defined between the merle face of the merle structure and the nanoparticle surface. The sharp corners are defined as edges.
The meteorite is deeper, so that a sharp angle structure can be formed between the meteorite surface and the surface of the nano particle, and the polishing efficiency can be improved. This is due to the presence of the outer tangent and the inner tangent of the particles with the crater structure at an angle that further enhances the mechanical action of the polish during the polishing process.
According to one embodiment of the application, the specific surface area of the nanospheres of the merle structure is much greater than that of the smooth nanospheres.
According to one embodiment of the application, the meteorite surface may be oriented to graft chemical groups. The chemical groups include positive and negative charges and/or oxidizing groups. The larger specific surface area of the nanospheres of the merle structure can achieve the contact area of the particles and the species after polishing. And chemical groups can be slowly released during CMP (chemical mechanical polishing) to improve polishing efficiency.
According to one embodiment of the application, the secondary particle size of the nanoparticle is 5-200 nm, and the nanoparticle morphology may be spherical particles or linker non-spherical particles of 2-5 nanoparticles or non-spherical nanoparticles of other morphologies.
According to one embodiment of the present application, the nano abrasive particles are selected from at least one of silica, alumina, ceria, zirconia.
According to one embodiment of the present application, the nano abrasive particles are selected from at least one of polystyrene, polyacrylate, polypropylene carbonate.
The nano silicon oxide particles with the meteorite structure have a relatively large number of pore structures, so that the toughness of the particles can be improved, the hardness of the particles can be reduced, and the scratch problem caused by polishing the particles can be reduced.
According to an embodiment of the present application, there is provided a method of preparing nano abrasive particles:
s1, reacting a mixture of nano particles and a silane coupling agent solution to obtain silane modified nano silicon oxide;
s2, adjusting the pH value of the silane modified nano silicon oxide solution B to be between 10.5 and 14 by using an alkaline solution D, reacting for 5 to 24 hours at the temperature of between 85 and 120 ℃, and then adjusting the pH value of the solution to be between 7 and 10.5 by using an acidic solution E to obtain the non-spherical nano silicon oxide particle solution.
Alkaline etching is also deposited with a change in pH, thereby causing the etched species to change morphology. In the actual operation process, the selection can be performed according to the requirements.
According to one embodiment of the present application, in step S1, the silane coupling agent solution is a solution of a silane coupling agent, water and alcohol in a molar ratio of 1: (0-700): (0-20), wherein the molar ratio is not in the range of 0.
According to one embodiment of the present application, in step S1, the silane coupling agent solution is a solution of a silane coupling agent, water and alcohol in a molar ratio of 1: (100-600): (5-15).
According to one embodiment of the present application, in step S1, the silane coupling agent solution is a solution of a silane coupling agent, water and alcohol in a molar ratio of 1: (200-400): (7-12).
According to one embodiment of the present application, in the step S2, the pH of the silane-modified nano-silica solution B is adjusted to between 10.5 and 14 with an alkaline solution D, preferably in the range of 11 to 12.5; in the step of reacting for 5 to 24 hours at the temperature of 85 to 120 ℃, the reaction temperature is preferably 85 to 95 ℃ and the reaction time is preferably 5 to 11 hours.
According to one embodiment of the present application, there is provided a method of preparing nano abrasive particles,
s1, reacting a mixture of nano particles and a silane coupling agent solution to obtain silane modified nano silicon oxide;
s2, mixing a silane modified nano silicon oxide solution B with an acid solution D, wherein the dosage ratio of the silane modified nano silicon oxide solution B to the acid solution D is 1 calculated by the mole ratio of silicon to fluorine: (0.001-1), and reacting for 5-24 hours at the temperature of 40-120 ℃ to obtain non-spherical nano silicon oxide particle solution.
The acid etching method is to generate SiF 4 Gas, siF 4 The gas can be well separated from the solution. Therefore, the practical operation is facilitated.
According to one embodiment of the present application, in step S1, the silane coupling agent solution is a solution of a silane coupling agent, water and alcohol in a molar ratio of 1: (0-700): (0-20), wherein the molar ratio is not in the range of 0.
According to one embodiment of the present application, in step S1, the silane coupling agent solution is a solution of a silane coupling agent, water and alcohol in a molar ratio of 1: (100-600): (5-15).
According to one embodiment of the present application, in step S1, the silane coupling agent solution is a solution of a silane coupling agent, water and alcohol in a molar ratio of 1: (200-400): (7-12).
According to an embodiment of the present application, in the step S2, in the step of mixing the silane modified nano silicon oxide solution B with the acidic solution D, the ratio of the amounts of the two is preferably 1, calculated as the molar ratio of silicon to fluorine: (0.001-0.3); in the step of reacting for 5-24 hours at 40-120 ℃, the reaction temperature is preferably 40-95 ℃ and the reaction time is preferably 5-11 hours.
According to one embodiment of the present application, there is provided a method of preparing nano abrasive particles,
s1, reacting a mixture of nano particles and a cationic surfactant solution II to obtain surface modified nano abrasive particles;
s2, adjusting the pH value of the nano silicon oxide solution C with the cations attached to the surface to be between 10.5 and 14 by using an alkaline solution D, reacting for 5 to 24 hours at the temperature of between 85 and 120 ℃, and then adjusting the pH value of the nano silicon oxide solution C to be between 7 and 10.5 by using an acidic solution E to obtain a non-spherical nano silicon oxide particle solution.
The cations are adsorbed in such a way that they are physically electrostatically attracted, so that they may not be as fine as the structures obtained with the silane coupling agent at the time of etching.
According to an embodiment of the present application, in S2, in the step of adjusting the pH of the surface-cation-attached nano-silica solution C to between 10.5 and 14 with the alkaline solution D, the pH is preferably in the range of 11 to 12.5; in the step of reacting for 5-24 hours at 85-120 ℃, the reaction temperature is preferably 85-95 ℃ and the reaction time is preferably 5-11 hours.
According to one embodiment of the present application, there is provided a method of preparing nano abrasive particles,
s1, reacting a mixture of nano particles and a cationic surfactant solution II to obtain surface modified nano abrasive particles;
s2, mixing the nano silicon oxide solution C with the surface attached with cations with the acid solution D, wherein the dosage ratio of the nano silicon oxide solution C to the acid solution D is 1 calculated by the mole ratio of silicon to fluorine: (0.001-1), and reacting for 5-24 hours at the temperature of 40-120 ℃ to obtain non-spherical nano silicon oxide particle solution.
According to an embodiment of the present application, in the step S2, in the step of mixing the nano silicon oxide solution C with the surface attached with the cation with the acidic solution D, the ratio of the amount of the nano silicon oxide solution C to the acidic solution D is preferably 1: (0.001-0.3); in the step of reacting for 5-24 hours at 40-120 ℃, the reaction temperature is preferably 40-95 ℃ and the reaction time is preferably 5-11 hours.
According to one embodiment of the present application, the silane coupling agent is selected from at least one of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, β (3, 4) epoxycyclohexylethyltrimethoxysilane, 1,2 bis-trimethoxysilylethane, methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, 3 aminopropyltrimethoxysilane, 3 aminopropyltriethoxysilane, N-aminoethylγaminopropyltrimethoxysilane, 3 mercaptopropyltrimethoxysilane, 3 mercaptopropyltriethoxysilane, methylvinyldiethoxysilane, 3 chloropropyltrimethoxysilane, hexamethyldisilazane, hexamethyldisiloxane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, pyridinylsilane, N-butyltrichlorosilane, isobutyltrichlorosilane, hexyltrichlorosilane, vinyltrichlorosilane, vinyltriisopropylsilane, diphenyldimethoxysilane, dodecyltrimethylsilane.
According to one embodiment of the present application, the cationic surfactant is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, methyltriethylammonium hydroxide, diethyldimethylammonium hydroxide, triethylmethylammonium hydroxide, benzyltrimethylammonium hydroxide, tributylmethylammonium hydroxide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrapentylammonium chloride, tetrahexylammonium chloride, methyltriethylammonium chloride, diethyldimethylammonium chloride, triethylmethylammonium chloride, benzyltrimethylammonium chloride, tripropylmethylammonium chloride, methyltributylammonium chloride, dioctyldimethylammonium chloride, didecyldimethylammonium chloride, and hexadecylamido propyltrimethylammonium chloride.
According to one embodiment of the application, in step S1, the conditions of reaction I are as follows:
the temperature is 20-80 ℃;
the time is 0.5-3 h.
According to one embodiment of the application, in step S1, the conditions for reaction ii are as follows:
the temperature is 20-50 ℃;
the time is 1-3 h.
According to one embodiment of the present application, the acidic solution E is at least one selected from the group consisting of inorganic acids and organic acids.
According to an embodiment of the present application, the inorganic acid is at least one selected from the group consisting of hydrochloric acid, nitric acid, boric acid, acetic acid, and sulfuric acid.
According to one embodiment of the application, the organic acid is selected from at least one of formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, 2, 3-dihydroxysuccinic acid, 2-hydroxysuccinic acid.
According to one embodiment of the application, the acid solution D is prepared from a fluoride solution E and a strong acid solution F according to a molar ratio of 1: (0.01-20).
According to an embodiment of the present application, the fluoride solution E is at least one selected from hydrofluoric acid, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride, tetrabutylammonium fluoride.
According to one embodiment of the present application, the strong acid solution F is at least one selected from the group consisting of organic acids and inorganic acids.
According to one embodiment of the present application, the organic acid is at least one selected from trifluoroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, oxalic acid, formic acid.
According to one embodiment of the present application, the inorganic acid is at least one selected from sulfuric acid, nitric acid, perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, perbromic acid, metaperiodic acid, chloric acid, bromic acid, metaphosphoric acid, permanganic acid, hydroboric acid, fluorosulfonic acid.
Example 1
(1) Preparation of nano silicon oxide solution
And obtaining the nano silicon oxide solution according to a conventional hydrolysis precipitation method.
(2) Preparation of silane coupling agent hydrolysis solution
Methyltrimethoxysilane in molar ratio: water: ethanol=1: 10:1, preparing a silane coupling agent hydrolysis solution.
(3) Preparation of silane modified nano silicon oxide solution
Weighing 100ml of the nano silicon oxide solution (the concentration is 10 wt.%), regulating the pH to 8, weighing 30ml of the silane coupling agent hydrolysis solution, regulating the pH to 2, mixing and stirring for 1h at 30 ℃ to obtain the silane modified nano silicon oxide solution.
(4) Alkaline etching of nano abrasive particles
Adjusting the pH value of the silane modified nano silicon oxide solution to 11 by using a sodium hydroxide solution, and reacting for 10 hours at 100 ℃; and then adjusting the pH value to 8 by using hydrochloric acid solution to obtain the nano abrasive particles.
Example 2
(1) Preparation of nano silicon oxide solution
And obtaining the nano silicon oxide solution according to a conventional hydrolysis precipitation method.
(2) Preparation of cationic surfactant solutions
Methyl tributyl ammonium chloride solution was prepared at a concentration of 10wt.%.
(3) Preparation of cationic modified nano silicon oxide solution
And uniformly mixing 100ml of the nano silicon oxide solution and 10ml of the methyltributylammonium chloride solution to obtain the cationic modified nano silicon oxide solution.
(4) Alkaline etching of nano abrasive particles
Adjusting the pH value of the cation modified nano silicon oxide solution to 11 by using a sodium hydroxide solution, and reacting for 10 hours at 100 ℃; and then adjusting the pH value to 8 by using hydrochloric acid solution to obtain the nano abrasive particles.
Example 3
(1) As in example 1.
(2) As in example 1.
(3) As in example 1.
(4) Acid etching of nano abrasive particles
Hydrofluoric acid and trifluoroacetic acid are mixed according to the following ratio of 1:1 into an acid solution D;
silane modified nano silicon oxide solution and acid solution D are prepared according to the following steps of 1:0.2 (in terms of the molar ratio of silicon to fluorine) and reacting at 50 ℃ for 10 hours to obtain the nano abrasive particles.
Example 4
(1) As in example 2.
(2) As in example 2.
(3) As in example 2.
(4) Acid etching of nano abrasive particles
Hydrofluoric acid and trifluoroacetic acid are mixed according to the following ratio of 1:1 into an acid solution D;
cation modified nano silicon oxide solution and acid solution D are mixed according to the following ratio of 1:0.2 (in terms of the molar ratio of silicon to fluorine) and reacting at 50 ℃ for 10 hours to obtain the nano abrasive particles.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (10)
1. The nano abrasive particles are characterized in that the surfaces of the nano abrasive particles are distributed with meteorite structures.
2. The nano-abrasive particles of claim 1 wherein a pointed structure is formed between the merle surface of the merle structure and the surface of the nano-particles;
preferably, the sharp corner structure is formed by an external tangent line and an internal tangent line of the nano abrasive particles;
preferably, the merle face of the merle structure is directionally grafted with a chemical group.
3. The nano-abrasive particle of claim 1 wherein the number of merle structures n >1;
the maximum distance L <150nm of the meteorite surface of the meteorite structure;
preferably, the angle of the sharp-angled structure is theta, wherein theta is more than or equal to 5 degrees and less than or equal to 170 degrees.
4. The nano abrasive particles according to claim 1, wherein the nano abrasive particles are at least one selected from inorganic materials, organic materials, composite materials;
preferably, the inorganic material is at least one selected from the group consisting of silica, alumina, ceria, and zirconia;
preferably, the organic material is selected from at least one of polystyrene, polyacrylate, polypropylene carbonate.
5. The nano-abrasive particles according to claim 1, wherein the nano-abrasive particles are spherical particles or non-spherical particles;
preferably, the non-spherical particles comprise a linker consisting of 2 to 5 of the nano abrasive particles;
preferably, the dimension of the connector is 5-200 nm;
preferably, the diameter of the spherical particle is D, the width of the merle structure is a, and the depth of the merle structure is h, then:
a/D=0.01~0.5,h/D=0.01~0.5;
preferably, the spherical particles have a particle size of 5 to 150nm.
6. The method for producing nano abrasive particles according to any one of claims 1 to 5, comprising the steps of:
s1, reacting a mixed solution containing nano particles and a protective agent to obtain surface modified nano abrasive particles;
and S2, etching the surface-modified nano abrasive particles to obtain the nano abrasive particles.
7. The method of claim 5, wherein the nanoparticles in step S1 are of the same material as the nano-abrasive particles;
preferably, the protective agent is at least one selected from silane coupling agents and cationic surfactants;
preferably, the silane coupling agent is at least one selected from methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, β (3, 4) epoxycyclohexylethyltrimethoxysilane, 1,2 bis-trimethoxysilylethane, methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, 3 aminopropyltrimethoxysilane, 3 aminopropyltriethoxysilane, N-aminoethyl gamma aminopropyltrimethoxysilane, 3 mercaptopropyltrimethoxysilane, 3 mercaptopropyltriethoxysilane, methylvinyldiethoxysilane, 3 chloropropyltrimethoxysilane, hexamethyldisilazane, hexamethyldisiloxane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, pyridinylsilane, N-butyltrichlorosilane, isobutyltrichlorosilane, hexyltrichlorosilane, vinyltrichlorosilane, vinyltriisopropylsilane, diphenyldimethoxysilane, dodecyltrimethylsilane;
preferably, the cationic surfactant is selected from at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, methyltriethylammonium hydroxide, diethyldimethylammonium hydroxide, triethylmethylammonium hydroxide, benzyltrimethylammonium hydroxide, tributylmethylammonium hydroxide, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrapentylammonium chloride, tetrahexylammonium chloride, methyltriethylammonium chloride, diethyldimethylammonium chloride, triethylmethylammonium chloride, benzyltrimethylammonium chloride, tripropylmethylammonium chloride, methyltributylammonium chloride, dioctyldimethylammonium chloride, didecyldimethylammonium chloride, and cetylamido propyltrimethylammonium chloride.
8. The method of manufacturing according to claim 6, comprising the steps of:
s1, reacting a mixture containing a nanoparticle solution and a silane coupling agent solution to obtain surface-modified nano abrasive particles; or alternatively, the first and second heat exchangers may be,
reacting II the mixture containing the nanoparticle solution and the cationic surfactant solution to obtain surface-modified nano abrasive particles;
s2, etching the surface-modified nano abrasive particles to obtain the nano abrasive particles;
preferably, in the step S1, the volume ratio of the nanoparticle solution to the silane coupling agent solution is 0.01 to 0.4;
preferably, in step S1, the volume ratio of the nanoparticle solution to the cationic surfactant solution is 0.01 to 0.6;
preferably, in step S1, the silane coupling agent solution is a silane coupling agent, water and alcohol according to a molar ratio of 1: (0-700): (0-20), wherein the molar ratio is not in the range of 0;
preferably, the pH value of the nanoparticle solution is 7-11;
preferably, the pH value of the silane coupling agent solution is 1-4;
preferably, in step S1, the conditions of reaction i are as follows:
the temperature is 20-80 ℃;
the time is 0.5-3 h;
preferably, in step S1, the conditions for reaction ii are as follows:
the temperature is 20-50 ℃;
the time is 1-3 h.
9. The method according to claim 6, wherein in step S2, the etching includes alkaline etching and acidic etching;
preferably, the alkaline etching comprises the steps of:
the pH value of the surface modified nano abrasive particles is adjusted to 10.5-14 by using an alkaline solution D, and after the surface modified nano abrasive particles react for 5-24 hours at the temperature of 85-120 ℃, the pH value of the surface modified nano abrasive particles is adjusted to 7-10.5 by using an acidic solution E, so that the nano abrasive particles are obtained;
preferably, the alkaline solution D is at least one selected from sodium hydroxide solution, potassium hydroxide solution and sodium bicarbonate solution;
preferably, the acidic solution E is at least one selected from inorganic acid and organic acid;
preferably, the inorganic acid is at least one selected from hydrochloric acid, nitric acid, boric acid, acetic acid and sulfuric acid;
preferably, the organic acid is selected from at least one of formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, 2, 3-dihydroxysuccinic acid and 2-hydroxysuccinic acid;
preferably, the acid etching comprises the steps of:
reacting III a mixture containing the surface-modified nano abrasive particles and an acidic solution D to obtain the nano abrasive particles;
preferably, the molar ratio of the surface-modified nano abrasive particles to the acidic solution D is 1: (0.001-1);
the above molar ratios are calculated as silicon and fluorine, respectively;
preferably, the conditions for reaction III are as follows:
the temperature is 40-120 ℃;
the time is 5-24 hours;
preferably, the acid solution D is prepared from a fluoride solution E and a strong acid solution F according to a molar ratio of 1: (0.01-20);
preferably, the fluoride solution E is at least one selected from hydrofluoric acid, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride, tetrabutylammonium fluoride;
preferably, the strong acid solution F is selected from at least one of organic acid and inorganic acid;
preferably, the organic acid is at least one selected from trifluoroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, oxalic acid and formic acid;
preferably, the inorganic acid is at least one selected from sulfuric acid, nitric acid, perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrobromic acid, metaperiodic acid, chloric acid, hydrobromic acid, metaphosphoric acid, permanganic acid, hydroboric acid, and fluorosulfonic acid.
10. Use of the nano abrasive particles according to any one of claims 1 to 5 and/or the nano abrasive particles obtained by the preparation method according to any one of claims 6 to 9 in chemical mechanical polishing.
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