JP5188175B2 - Silica sol and method for producing the same - Google Patents
Silica sol and method for producing the same Download PDFInfo
- Publication number
- JP5188175B2 JP5188175B2 JP2007339796A JP2007339796A JP5188175B2 JP 5188175 B2 JP5188175 B2 JP 5188175B2 JP 2007339796 A JP2007339796 A JP 2007339796A JP 2007339796 A JP2007339796 A JP 2007339796A JP 5188175 B2 JP5188175 B2 JP 5188175B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- silica sol
- silica
- range
- fine particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 211
- 239000002245 particle Substances 0.000 claims description 97
- 239000000377 silicon dioxide Substances 0.000 claims description 94
- 239000010419 fine particle Substances 0.000 claims description 79
- -1 silane compound Chemical class 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 229910000077 silane Inorganic materials 0.000 claims description 40
- 238000005498 polishing Methods 0.000 claims description 39
- 239000003960 organic solvent Substances 0.000 claims description 29
- 239000011734 sodium Substances 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 23
- 239000012046 mixed solvent Substances 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000004438 BET method Methods 0.000 claims description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims description 9
- 238000003703 image analysis method Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 6
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 59
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 46
- 239000000243 solution Substances 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 22
- 238000005259 measurement Methods 0.000 description 21
- 229910021529 ammonia Inorganic materials 0.000 description 19
- 238000006460 hydrolysis reaction Methods 0.000 description 17
- 239000000523 sample Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000003746 surface roughness Effects 0.000 description 16
- 230000007062 hydrolysis Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000000108 ultra-filtration Methods 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000008186 active pharmaceutical agent Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 101100004297 Caenorhabditis elegans bet-1 gene Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Description
本発明は、粒子の表面粗度、真球度または粒子径の変動係数などで特定される表面に疣状突起を有する球状のシリカ微粒子が溶媒に分散したシリカゾルに関するものであり、特にナトリウムおよび炭素含有量が低く、研磨材、塗料添加剤、樹脂添加剤、インク受容層の成分、化粧料の成分などへの適用が可能なものである。 The present invention relates to a silica sol in which spherical silica fine particles having ridge-like projections on the surface specified by the surface roughness, sphericity, or particle diameter variation coefficient of particles are dispersed in a solvent, particularly sodium and carbon. It has a low content and can be applied to abrasives, paint additives, resin additives, ink receiving layer components, cosmetic components, and the like.
半導体の集積回路付基板の製造においては、シリコンウェーハ上に銅などの金属で回路を形成する際に凹凸あるいは段差が生じるので、これを研磨して表面の段差がなくなるように回路の金属部分を優先的に除去することが行われている。また、シリコンウェーハ上にアルミ配線を形成し、この上に絶縁膜としてシリカ等の酸化膜を設けると配線による凹凸が生じるので、この酸化膜を研磨して平坦化することが行われている。このような基板の研磨においては、研磨後の表面は段差や凹凸がなく平坦で、さらにミクロな傷等もなく平滑であることが求められており、また研磨速度が速いことも必要である。 In the manufacture of a substrate with a semiconductor integrated circuit, irregularities or steps are formed when forming a circuit with a metal such as copper on a silicon wafer. Removal is performed preferentially. Further, when an aluminum wiring is formed on a silicon wafer and an oxide film such as silica is provided thereon as an insulating film, irregularities due to the wiring are generated. Therefore, the oxide film is polished and flattened. In the polishing of such a substrate, the surface after polishing is required to be flat with no steps or irregularities, smooth without microscopic scratches, etc., and the polishing rate must be high.
さらに、半導体材料は電気・電子製品の小型化や高性能化に伴い高集積化が進展しているが、例えばトランジスタ分離層にＮａやＫ等の不純物等が残存した場合、性能が発揮されなかったり、不具合の原因となったりすることがある。特に研磨した半導体基板や酸化膜表面にＮａが付着すると、Ｎａは拡散性が高く、酸化膜中の欠陥などに捕獲され、半導体基板に回路を形成しても絶縁不良を起こしたり、回路が短絡したりすることがあり、また誘電率が低下することがあった。このため使用条件によって、或いは使用が長期にわたった場合に前記不具合を生じることがあるので、ＮａやＫなどの不純物を殆ど含まない研磨用粒子が求められている。 In addition, semiconductor materials are becoming more highly integrated as electrical and electronic products become smaller and higher in performance. For example, when impurities such as Na and K remain in the transistor isolation layer, the performance is not exhibited. Or cause malfunctions. In particular, if Na adheres to the polished semiconductor substrate or oxide film surface, Na is highly diffusive and is trapped by defects in the oxide film, causing insulation failure even when a circuit is formed on the semiconductor substrate, or shorting the circuit. In some cases, the dielectric constant may decrease. For this reason, since the said malfunction may arise depending on use conditions or when used over a long term, the abrasive | polishing particle | grains which hardly contain impurities, such as Na and K, are calculated | required.
研磨用粒子としては、従来、シリカゾルやヒュームドシリカ、ヒュームドアルミナなどが用いられている。
ＣＭＰで使用される研磨材は、通常、シリカ、アルミナ等の金属酸化物からなる平均粒子径が２００ｎｍ程度の球状の研磨用粒子と、配線・回路用金属の研磨速度を早めるための酸化剤、有機酸等の添加剤及び純水などの溶媒から構成されているが、被研磨材の表面には下地の絶縁膜に形成した配線用の溝パターンに起因した段差（凹凸）が存在するので、主に凸部を研磨除去しながら共面まで研磨し、平坦な研磨面とすることが求められている。しかしながら、従来の球状の研磨用粒子では共面より上の部分を研磨した際に、凹部の下部にあった配線溝内の回路用金属が共面以下まで研磨される問題（ディッシング（過研磨）と呼ばれている。）があった。このようなディッシングが起きると配線の厚みが減少して配線抵抗が増加し、また、この上に形成される絶縁膜の平坦性が低下するなどの問題が生じるので、ディッシングを抑制することが求められている。
Conventionally, silica sol, fumed silica, fumed alumina, or the like is used as the abrasive particles.
The abrasive used in CMP is usually spherical abrasive particles having an average particle diameter of about 200 nm made of a metal oxide such as silica and alumina, and an oxidizer for increasing the polishing rate of the wiring / circuit metal. It is composed of additives such as organic acids and solvents such as pure water, but there are steps (unevenness) due to the groove pattern for wiring formed on the underlying insulating film on the surface of the material to be polished. It is required to polish the coplanar surface mainly while polishing and removing the convex portions to obtain a flat polished surface. However, with conventional spherical polishing particles, when polishing the part above the coplanar surface, the problem is that the circuit metal in the wiring groove at the bottom of the recess is polished to below the coplanar surface (dishing (overpolishing)) It was called.) When such dishing occurs, the thickness of the wiring decreases, the wiring resistance increases, and the flatness of the insulating film formed thereon deteriorates. Therefore, it is necessary to suppress dishing. It has been.
なお、この様な研磨剤の用途としては、アルミニウムディスク（アルミニウムまたはその基材上のメッキ層）や半導体多層配線基板のアルミニウム配線、光ディスクや磁気ディスク用ガラス基板、液晶ディスプレイ用ガラス基板、フォトマスク用ガラス基板、ガラス質材料の鏡面加工などへの適用されている。 Examples of such abrasives include aluminum disks (plated layer on aluminum or its base material), aluminum wiring of semiconductor multilayer wiring boards, glass substrates for optical disks and magnetic disks, glass substrates for liquid crystal displays, photomasks. It is applied to glass substrates for glass and mirror finishing of glassy materials.
非球状粒子を含むシリカゾルの製造方法としては、特開平１−３１７１１５号公報（特許文献１）に、画像解析法による測定粒子径（Ｄ1）と窒素ガス吸着法による測定粒子径
（Ｄ2 ）の比Ｄ1/Ｄ2が５以上であり、Ｄ1は４０〜５００ミリミクロン、そして電子顕微鏡観察による５〜４０ミリミクロンの範囲内の一様な太さで一平面内のみの伸長を有する細長い形状の非晶質コロイダルシリカ粒子が液状媒体中に分散されてなるシリカゾルの製
造方法として、（ａ）所定の活性珪酸のコロイド水溶液に水溶性のカルシウム塩またはマグネシウム塩などを含有する水溶液を、所定量添加し、混合する工程、（ｂ） 更に、ア
ルカリ金属酸化物、水溶性有機塩基又はそれらの水溶性珪酸塩をＳｉＯ2/Ｍ2Ｏ （但し、Ｍは上記アルカリ金属原子又は有機塩基の分子を表わす。）モル比として２０〜２００となるように加えて混合する工程、（ｃ）前工程によって得られた混合物を６０〜１５０℃で０．５〜４０時間加熱する工程からなる製造方法が開示されている。
As a method for producing a silica sol containing non-spherical particles, JP-A-1-317115 (Patent Document 1) discloses a measurement particle size (D 1 ) by an image analysis method and a measurement particle size (D 2 ) by a nitrogen gas adsorption method. The ratio D 1 / D 2 is 5 or more, and D 1 has a uniform thickness in the range of 5 to 40 mm by electron microscope observation and an extension in one plane only in the range of 5 to 40 mm. As a method for producing a silica sol in which amorphous colloidal silica particles having an elongated shape are dispersed in a liquid medium, (a) an aqueous solution containing a water-soluble calcium salt or magnesium salt in a predetermined colloidal aqueous solution of active silicic acid, was added a predetermined amount, the step of mixing, (b) further, alkali metal oxide, a water-soluble organic base or their water-soluble silicate SiO 2 / M 2 O (where, M is also the alkali metal atom Represents a molecule of an organic base.) From the step of adding and mixing so that the molar ratio is 20 to 200, (c) From the step of heating the mixture obtained by the previous step at 60 to 150 ° C. for 0.5 to 40 hours A manufacturing method is disclosed.
また、別のタイプの粒子として、シリカ系微粒子の表面に突起状構造を有する例として、特開平３−２５７０１０号公報（特許文献２）には、シリカ粒子表面に電子顕微鏡で観察して、０．２〜５μｍのサイズの連続的な凹凸状の突起を有し、平均粒子径が５〜１００μｍ、ＢＥＴ法比表面積が２０ｍ2／ｇ以下、且つ、細孔容積が、０．１ｍＬ／ｇ以下であるシリカ粒子に関する記載がある。
特開２００２−３３８２３２号公報（特許文献３）には、コロイダルシリカのシリカ粒子の電子線による透過投影像より求めた幾何学的平均粒子径（Ｘ１）と、シリカ粒子の表面積より算出した相当粒子径（Ｘ２）との比Ｙ（Ｘ１／Ｘ２）が１．３から２．５の範囲であり、かつその幾何学的平均粒子径が２０〜２００ｎｍの範囲であることを特徴とする二次凝集コロイダルシリカに関する発明が開示されている。より詳しくは、同二次凝集コロイダルシリカの製造方法として、単分散のコロイダルシリカにシリカ粒子の凝集剤を添加して球状の凝集二次粒子を作り、更に活性珪酸を添加して凝集粒子を一体化してなる製造方法が開示されている。
As another type of particles, as an example having a protruding structure on the surface of silica-based fine particles, Japanese Patent Application Laid-Open No. 3-257010 (Patent Document 2) shows 0 on the surface of silica particles observed with an electron microscope. .Continuous concavo-convex protrusions having a size of 2 to 5 μm, an average particle diameter of 5 to 100 μm, a BET specific surface area of 20 m 2 / g or less, and a pore volume of 0.1 mL / g or less There is a description regarding silica particles.
Japanese Patent Laid-Open No. 2002-338232 (Patent Document 3) describes an equivalent particle calculated from a geometric average particle diameter (X1) obtained from a transmission projection image of an electron beam of silica particles of colloidal silica and a surface area of the silica particles. Secondary aggregation characterized in that the ratio Y (X1 / X2) to the diameter (X2) is in the range of 1.3 to 2.5 and the geometric mean particle diameter is in the range of 20 to 200 nm. An invention relating to colloidal silica is disclosed. More specifically, as a method for producing the secondary agglomerated colloidal silica, agglomerating agent of silica particles is added to monodispersed colloidal silica to form spherical agglomerated secondary particles, and further active silicic acid is added to integrate the agglomerated particles. A manufacturing method is disclosed.
特開２００２−３８０４９号公報（特許文献４）には、母体粒子全面に、実質上球状および／または半球状の突起物を有するシリカ系微粒子であって、該突起物が化学結合により母体粒子に結着していることを特徴とするシリカ系微粒子および母体粒子全面に、実質上球状および／または半球状の突起物を有するシリカ系微粒子であって、該突起物が化学結合により母体粒子に結着してなるシリカ系微粒子について記載がある。さらに、（Ａ）特定のアルコキシシラン化合物を加水分解、縮合させてポリオルガノシロキサン粒子を生成させる工程、（Ｂ）該ポリオルガノシロキサン粒子を、表面吸着剤により表面処理する工程、および（Ｃ）上記（Ｂ）工程で表面処理されたポリオルガノシロキサン粒子全面に、該アルコキシシラン化合物を用いて突起を形成させる工程、を含むシリカ系微粒子の製造方法についても記載がある。 Japanese Patent Application Laid-Open No. 2002-38049 (Patent Document 4) discloses silica-based fine particles having substantially spherical and / or hemispherical protrusions on the entire surface of the base particles, and the protrusions are converted into base particles by chemical bonding. Silica-based fine particles having substantially spherical and / or hemispherical protrusions on the entire surface of the silica-based fine particles and base particles characterized by being bonded, and the protrusions are bonded to the base particles by chemical bonding. There is a description of the silica-based fine particles formed by wearing. Further, (A) a step of hydrolyzing and condensing a specific alkoxysilane compound to produce polyorganosiloxane particles, (B) a step of treating the polyorganosiloxane particles with a surface adsorbent, and (C) the above There is also a description of a method for producing silica-based fine particles including a step of forming protrusions on the entire surface of the polyorganosiloxane particles surface-treated in the step (B) using the alkoxysilane compound.
また、特開２００４−３５２９３号公報（特許文献５）には、母体粒子全面に、実質上球状および／または半球状の突起物を有するシリカ系粒子であって、該突起物が化学結合により母体粒子に結着しており、かつ母体粒子と突起物における１０％圧縮時の圧縮弾性率が、それぞれ異なることを特徴とするシリカ系粒子が開示されている。 Japanese Patent Application Laid-Open No. 2004-35293 (Patent Document 5) discloses silica-based particles having substantially spherical and / or hemispherical protrusions on the entire surface of the base particle, and the protrusion is chemically bonded to the base. Silica-based particles are disclosed that are bound to particles and have different compressive elastic moduli at 10% compression between the base particles and the protrusions.
特開平３−２５７０１０号公報（特許文献２）および特開２００２−３３８２３２号公報（特許文献３）の特許請求の範囲に記載されたシリカゾルについては、珪酸液を原料とするものであり、例えば、前記研磨用途に適用した場合、ナトリウムなどの不純物が電子用途に悪影響を及ぼすおそれがあった。特開２００２−３８０４９号公報（特許文献４）および特開２００４−３５２９３号公報（特許文献５）については、３官能性または２官能性のシラン化合物を原料とするものであり、シリカ微粒子が、［Ｒ-ＳｉＯ3/2］単位（Ｒは有機基）を主構成単位とするものである。
本発明は、表面に疣状突起を有する球状シリカ微粒子が溶媒に分散してなるシリカゾルであって、特に、ナトリウム、炭素などの含有割合が低レベルにある球状シリカ微粒子が溶媒に分散してなるシリカゾルを提供することにある。また、本発明は、その様なシリカゾルの製造方法を提供するものである。 The present invention is a silica sol in which spherical silica fine particles having ridge-like projections on the surface are dispersed in a solvent, and in particular, spherical silica fine particles having a low content ratio of sodium, carbon, etc. are dispersed in the solvent. It is to provide a silica sol. The present invention also provides a method for producing such a silica sol.
［１］本発明のシリカゾルは、表面に複数の疣状突起を有する球状シリカ微粒子が溶媒に分散してなるシリカゾルであって、該球状シリカ微粒子のＢＥＴ法により測定された比表面積を（ＳＡ１）とし、画像解析法により測定される該シリカ微粒子の平均粒子径（Ｄ２）から換算した比表面積を（ＳＡ２）としたときの表面粗度（ＳＡ１）／（ＳＡ２）の値が、１．９〜５．０の範囲にあり、該平均粒子径（Ｄ２）が１０〜１５０ｎｍの範囲にあり、ナトリウム含有割合が１００質量ｐｐｍ以下、炭素含有割合が０．１〜５質量％の範囲にあることを特徴とする。
［２］また、前記［１］の球状シリカ微粒子の粒子径の変動係数が３．０〜２０％の範囲にあることが好ましい。
［３］前記［１］または［２］の球状シリカ微粒子が［ＳｉＯ4/2］単位を含有するもの
であることが好ましい。
［４］本発明の前記［１］、［２］または［３］のシリカゾルの製造方法は、水溶性有機溶媒および水を含む混合溶媒の温度範囲を３０〜１５０℃に維持し、そこに、１）下記一般式（１）で表される４官能性シラン化合物の水溶性有機溶媒溶液および２）アルカリ触媒溶液とを同時に、連続的または断続的に添加し、添加終了後、更に３０〜１５０℃の温度範囲にて熟成することにより、該４官能性シラン化合物を加水分解縮合させてなるシリカゾルの製造方法において、該４官能性シラン化合物に対する水のモル比を２以上、４未満の範囲として、加水分解縮合を行うことを特徴とする。
一般式（１）：（ＲＯ）4Ｓｉ （Ｒは炭素数２〜４のアルキル基）
［５］［４］に記載のシリカゾルの製造方法は、前記［４］の４官能性シラン化合物が、テトラエトキシシランであることが好ましい。
［６］さらに、前記［１］、［２］または［３］のシリカゾルからなる研磨材を提供することができる。
［７］また、前記［６］に記載の研磨材を含有してなる研磨用組成物を提供することができる。
[1] The silica sol of the present invention is a silica sol in which spherical silica fine particles having a plurality of hook-shaped protrusions on the surface are dispersed in a solvent, and the specific surface area of the spherical silica fine particles measured by the BET method is (SA1). When the specific surface area converted from the average particle diameter (D2) of the silica fine particles measured by the image analysis method is (SA2), the value of the surface roughness (SA1) / (SA2) is 1.9 to The average particle diameter (D2) is in the range of 10 to 150 nm, the sodium content is 100 mass ppm or less, and the carbon content is in the range of 0.1 to 5 mass%. Features.
[2] The coefficient of variation of the particle diameter of the spherical silica fine particles of [1] is preferably in the range of 3.0 to 20%.
[3] It is preferable that the spherical silica fine particles of [1] or [2] contain [SiO 4/2 ] units.
[4] The method for producing a silica sol according to [1], [2] or [3] of the present invention maintains a temperature range of a mixed solvent containing a water-soluble organic solvent and water at 30 to 150 ° C., 1) A water-soluble organic solvent solution of a tetrafunctional silane compound represented by the following general formula (1) and 2) an alkali catalyst solution are added simultaneously or intermittently. In the method for producing a silica sol obtained by hydrolyzing and condensing the tetrafunctional silane compound by aging in a temperature range of ° C., the molar ratio of water to the tetrafunctional silane compound is set to a range of 2 or more and less than 4. And hydrolytic condensation.
General formula (1): (RO) 4 Si (R is an alkyl group having 2 to 4 carbon atoms)
[5] In the method for producing a silica sol according to [4], the tetrafunctional silane compound of [4] is preferably tetraethoxysilane.
[6] Furthermore, an abrasive comprising the silica sol of [1], [2] or [3] can be provided.
[7] A polishing composition comprising the abrasive according to [6] can be provided.
本発明に係る表面に疣状突起を有する球状シリカ微粒子が溶媒に分散してなるシリカゾルは、その構造に起因して、研磨材として高研磨レートを示すことが可能なものであり、特にナトリウム含有量および炭素含有量が低水準にあるため、電子用途または半導体用途の研磨材として好適なものである。また、本発明に係るシリカゾルは、その分散質である球状シリカ微粒子の有する特異な構造から、通常の球状シリカ微粒子とは異なる充填性、吸油性、電気特性、光学特性あるいは物理特性を示すことが期待される。 The silica sol obtained by dispersing spherical silica fine particles having ridge-like projections on the surface according to the present invention in a solvent is capable of exhibiting a high polishing rate as an abrasive due to its structure, and particularly contains sodium. Since the amount and the carbon content are low, it is suitable as an abrasive for electronic use or semiconductor use. In addition, the silica sol according to the present invention may exhibit different filling properties, oil absorption, electrical properties, optical properties, or physical properties from ordinary spherical silica fine particles because of the unique structure of the spherical silica fine particles that are the dispersoid. Be expected.
本発明に係るシリカゾルの分散質である球状シリカ微粒子は、以下に示す、表面粗度、真球度または粒子径の変動係数等で特定される。この球状シリカ微粒子については、表面に多数の疣状突起を有したシリカ微粒子であって、特に４官能性シランの加水分解縮合により合成されたものであり、［ＳｉＯ4/2］単位を主成分とする緻密な構造を有すること
を特徴とするものである。また、このシリカ微粒子は、原料の純度に起因して、ナトリウムまたは炭素などの不純物の含有量が低水準にあることを特徴としている。これらの特徴は、前記のシリコンウェーハの研磨を始めとする研磨用途において、優れた効果を示すも
のである。
The spherical silica fine particles that are the dispersoid of the silica sol according to the present invention are specified by the following surface roughness, sphericity, particle diameter variation coefficient, and the like. The spherical silica fine particle is a silica fine particle having a large number of ridge-like projections on the surface, which is synthesized by hydrolysis condensation of tetrafunctional silane, and has a [SiO 4/2 ] unit as a main component. It is characterized by having a dense structure. The silica fine particles are characterized in that the content of impurities such as sodium or carbon is at a low level due to the purity of the raw material. These characteristics show excellent effects in polishing applications including polishing of the silicon wafer.
本発明に係るシリカゾルについては、特にその分散質である球状シリカ微粒子の性状および組成に特徴を有するものである。以下に、本発明に係るシリカゾルについて述べる。 The silica sol according to the present invention is particularly characterized by the properties and composition of the spherical silica fine particles that are the dispersoid. Hereinafter, the silica sol according to the present invention will be described.
１．シリカゾル
［表面粗度］
本発明に係るシリカゾルの分散質である球状シリカ微粒子は、その表面に複数の疣状突起を有し、凹凸に富むものである。この様な複数の疣状突起を有する表面については表面粗度によりその範囲が規定される。本発明において表面粗度は、ＢＥＴ法により測定された比表面積（単位質量当りの表面積）の値を（ＳＡ１）とし、画像解析法により測定された平均粒子径（Ｄ２）から換算された比表面積の値を（ＳＡ２）としたとき、表面粗度＝（ＳＡ１）／（ＳＡ２）として定義される。
1. Silica sol [Surface roughness]
The spherical silica fine particles, which are the dispersoid of the silica sol according to the present invention, have a plurality of hook-shaped protrusions on the surface thereof and are rich in irregularities. The surface of such a surface having a plurality of hook-shaped protrusions is defined by the surface roughness. In the present invention, the surface roughness is the specific surface area converted from the average particle diameter (D2) measured by the image analysis method, with the value of the specific surface area (surface area per unit mass) measured by the BET method being (SA1). (SA2) is defined as surface roughness = (SA1) / (SA2).
画像解析法により測定された平均粒子径（Ｄ２）から換算された比表面積（ＳＡ２）については、透過型電子顕微鏡により、試料シリカゾルを倍率２５万倍で写真撮影して得られる写真投影図における、任意の５０個の粒子について、その最大径（ＤＬ）を測定し、その平均値を平均粒子径（Ｄ２）とした。
また、平均粒子径（Ｄ２）の値を次の式（２）に代入して、比表面積（ＳＡ２）を求めた。
About the specific surface area (SA2) converted from the average particle diameter (D2) measured by the image analysis method, in a photographic projection view obtained by photographing a sample silica sol at a magnification of 250,000 times with a transmission electron microscope, About 50 arbitrary particles, the maximum diameter (DL) was measured and the average value was made into the average particle diameter (D2).
Further, the specific surface area (SA2) was determined by substituting the value of the average particle diameter (D2) into the following formula (2).
Ｄ２＝６０００／（ρ×ＳＡ２） ・・・ （１）
ここで、Ｄ２は前記平均粒子径［ｎｍ］、ρは試料の密度［ｇ／ｃｍ3］であり、ここ
ではシリカの密度２．２を使用した。 この比表面積（ＳＡ２）の値は、平均粒子径Ｄ２を有する球状で表面が平滑なシリカ微粒子の比表面積に対応するものと言える。
D2 = 6000 / (ρ × SA2) (1)
Here, D2 is the average particle diameter [nm], ρ is the density of the sample [g / cm 3 ], and here, the density of silica 2.2 was used. The value of the specific surface area (SA2) can be said to correspond to the specific surface area of spherical silica particles having an average particle diameter D2 and a smooth surface.
他方、ＢＥＴ法は、粒子への気体（通常は窒素ガス）の吸着量から、比表面積を算定する方法であり、実際の表面状態に対応した表面積を反映したものと言える。
ここで比表面積は単位質量当りの表面積を示すから、表面粗度（ＳＡ１）／（ＳＡ２）の値については、球状粒子の場合、粒子表面に多くの疣状突起を有する程、（ＳＡ１）／（ＳＡ２）の値は大きくなる。また、粒子表面の疣状突起が少なく、平滑であるほど、（ＳＡ１）／（ＳＡ２）の値は小さくなり、その値は１に近づく傾向にある。
On the other hand, the BET method is a method of calculating the specific surface area from the amount of gas (usually nitrogen gas) adsorbed on the particles, and can be said to reflect the surface area corresponding to the actual surface state.
Here, since the specific surface area indicates the surface area per unit mass, the value of the surface roughness (SA1) / (SA2) is such that, in the case of a spherical particle, the more the surface of the particle, the more (SA1) / The value of (SA2) increases. Further, the smaller the number of wrinkle-like protrusions on the particle surface and the smoother, the smaller the value of (SA1) / (SA2) and the value tends to approach 1.
本発明において、前記シリカ微粒子の表面粗度は１．９〜５．０の範囲が好適である。表面粗度が１．９未満の場合、突起の割合が少ないかあるいは、疣状突起自体がシリカ微粒子の粒子径に比べて小さ過ぎ、球状シリカ微粒子に近くなる。表面粗度の値が５．０を超える場合は、合成が容易ではない。表面粗度のより好適な範囲としては、２．０〜４．０の範囲が推奨される。また、更に好適には、２．１〜３．７の範囲が推奨される。 In the present invention, the surface roughness of the silica fine particles is preferably in the range of 1.9 to 5.0. When the surface roughness is less than 1.9, the ratio of the protrusions is small, or the hook-shaped protrusions themselves are too small compared to the particle diameter of the silica fine particles and become close to spherical silica fine particles. When the surface roughness value exceeds 5.0, synthesis is not easy. As a more preferable range of the surface roughness, a range of 2.0 to 4.0 is recommended. More preferably, the range of 2.1 to 3.7 is recommended.
［真球度］
前記球状シリカ微粒子は、球状であることが必要であり、棒状、勾玉状、細長い形状、数珠状、卵状など、いわゆる異形粒子が含まれない。本発明において、球状とは、真球度が０．７０〜１．００の範囲にある場合を言う。ここで真球度とは、透過型電子顕微鏡により写真撮影して得られる写真投影図における任意の５０個の粒子について、 それぞれ最大径（ＤＬ）を測定し、該最大径上で、該最大径を２等分する点（中心点）を求め、該中心点を通過し、該最大径に直交する径の長さ（ＤＳ）を測定し、（ＤＬ）／（ＤＳ）の値を求め、５０個の粒子について平均値をとり、これを真球度とした。
[Sphericity]
The spherical silica fine particles are required to be spherical, and do not include so-called irregular particles such as a rod shape, a ball shape, an elongated shape, a bead shape, and an egg shape. In the present invention, the term “spherical” refers to a case where the sphericity is in the range of 0.70 to 1.00. Here, the sphericity means the maximum diameter (DL) of any 50 particles in a photographic projection obtained by photographing with a transmission electron microscope, and the maximum diameter is measured on the maximum diameter. Is obtained by obtaining a point (center point) that bisects the two points, passing through the center point, measuring the length (DS) of the diameter orthogonal to the maximum diameter, and determining the value of (DL) / (DS), An average value was taken for each particle, and this was defined as sphericity.
真球度が０．７未満の場合は、シリカ微粒子が球状とはいえず、前記の異形粒子に該当する場合が生じる。真球度の範囲については、より好適には０．８０〜１．００の範囲が
推奨される。また、更に好適には０．９０〜１．００の範囲が推奨される。
When the sphericity is less than 0.7, the silica fine particles may not be spherical and may correspond to the irregular shaped particles. About the range of sphericity, the range of 0.80-1.00 is recommended more suitably. More preferably, the range of 0.90 to 1.00 is recommended.
［平均粒子径］
前記球状シリカ微粒子の画像解析法により測定される平均粒子径（Ｄ２）については、１０〜１５０ｎｍの範囲が好適である。１０ｎｍ未満の場合は、必要な表面粗度をもった球状シリカ微粒子を調製することが容易ではない。平均粒子径（Ｄ２）が１５０ｎｍ超える場合は、原料の核微粒子の大きさにもよるが、一般に突起が平坦化する傾向が著しくなるため良好な性状の球状シリカ微粒子を得ることが容易ではない。平均粒子径の範囲については、より好適には、２０〜１００ｎｍの範囲が推奨される。また、より好適には２５〜５０ｎｍの範囲が推奨される。
[Average particle size]
About the average particle diameter (D2) measured by the image analysis method of the said spherical silica fine particle, the range of 10-150 nm is suitable. If it is less than 10 nm, it is not easy to prepare spherical silica fine particles having the required surface roughness. When the average particle diameter (D2) exceeds 150 nm, although it depends on the size of the raw material core fine particles, it is not easy to obtain spherical silica fine particles having good properties because the protrusions generally tend to be flattened. About the range of an average particle diameter, the range of 20-100 nm is more suitably recommended. More preferably, the range of 25 to 50 nm is recommended.
なお、前記球状シリカ微粒子の比表面積については、格別に限定されるものではないが、通常は１０〜１０００ｍ2／ｇの範囲が推奨される。また、好適には１００〜６００ｍ2／ｇの範囲が推奨される。 The specific surface area of the spherical silica fine particles is not particularly limited, but usually a range of 10 to 1000 m 2 / g is recommended. Moreover, the range of 100-600 m < 2 > / g is recommended suitably.
［基本構成単位および炭素含有割合］
前記球状シリカ微粒子は、後記した様に４官能性シラン化合物の加水分解縮合により調製されるものであり、基本的に［ＳｉＯ4/2］単位を含有するものである。 このため前
記球状シリカ微粒子は、加水分解縮合の進行度合にもよるが、例えば、トリエトキシシランおよび／またはジエトキシシランの加水分解縮合により得られる、［ＲＳｉＯ3/2］単
位（Ｒは有機基）および／または［Ｒ2ＳｉＯ2/2］単位（Ｒは有機基）から構成されるシリカ微粒子に比べて、炭素含有割合が低くなるため、電子または半導体関係の研磨材用途などへの適用に好適となる。
[Basic constitutional unit and carbon content]
The spherical silica fine particles are prepared by hydrolytic condensation of a tetrafunctional silane compound as described later, and basically contain [SiO 4/2 ] units. Therefore, although the spherical silica fine particles depend on the degree of progress of hydrolysis condensation, for example, [RSiO 3/2 ] units (R is an organic group) obtained by hydrolysis condensation of triethoxysilane and / or diethoxysilane. ) And / or [R 2 SiO 2/2 ] units (where R is an organic group), the carbon content is lower, which makes it suitable for use in electronic or semiconductor-related abrasives. Preferred.
前記球状シリカ微粒子中の炭素含有割合については、０．１〜５質量％の範囲が望ましい。 より好ましくは０．１〜３質量％の範囲が推奨される。また、更に好適には０．１〜１質量％の範囲が推奨される。炭素含有割合が０．１質量％未満の場合については、炭素原子の含有割合が低く望ましいものの、調製することが容易ではない。 About the carbon content rate in the said spherical silica fine particle, the range of 0.1-5 mass% is desirable. More preferably, the range of 0.1 to 3% by mass is recommended. More preferably, the range of 0.1 to 1% by mass is recommended. When the carbon content is less than 0.1% by mass, the carbon atom content is low and desirable, but it is not easy to prepare.
一方、炭素含有割合が５質量％を越える場合、アルコキシ残基の増大による、粒子強度の低下が、実用的な研磨速度を損なう程度に達する場合があり望ましくない。また、炭素により汚染されるおそれのある用途には適さなくなる。 On the other hand, when the carbon content exceeds 5% by mass, a decrease in particle strength due to an increase in alkoxy residues may reach a level that impairs a practical polishing rate. In addition, it is not suitable for applications that may be contaminated by carbon.
［Ｎａ含有割合］
前記球状シリカ微粒子については、ナトリウム（Ｎａ）についてもその含有割合が低い水準にあることが望ましい。球状シリカ微粒子中のＮａ含有割合は球状シリカ微粒子中にＮａとして１００質量ｐｐｍ以下、好ましくは５０質量ｐｐｍ以下、特に好ましくは２０質量ｐｐｍ以下であることが望ましい。Ｎａ含有割合が１００質量ｐｐｍを越えると、シリカ粒子を用いて研磨した基板にＮａが残存し、このＮａが半導体基板に形成された回路の絶縁不良を起こしたり回路が短絡したりすることがあり、絶縁用に設けた膜（絶縁膜）の誘電率が低下し金属配線にインピーダンスが増大し、応答速度の遅れ、消費電力の増大等が起きることがある。また、Ｎａイオンが移動（拡散）し、使用条件や使用が長期にわたった場合に前記不具合を生じることがある。
[Na content ratio]
About the spherical silica fine particles, it is desirable that the content ratio of sodium (Na) is at a low level. It is desirable that the Na content in the spherical silica fine particles is 100 mass ppm or less, preferably 50 mass ppm or less, particularly preferably 20 mass ppm or less as Na in the spherical silica fine particles. When the Na content exceeds 100 mass ppm, Na remains on the substrate polished with silica particles, and this Na may cause insulation failure of the circuit formed on the semiconductor substrate or the circuit may be short-circuited. In some cases, the dielectric constant of a film (insulating film) provided for insulation decreases, impedance increases in metal wiring, response speed is delayed, power consumption increases, and the like. Moreover, Na ion moves (diffuses), and the above-mentioned problem may occur when the use conditions and use are prolonged.
［粒子径の変動係数（ＣＶ値）］
本発明に係るシリカゾルの分散質である球状シリカ微粒子の表面状態については、前記表面粗度で定められるものであるが、望ましくは、粒子径の変動係数（ＣＶ値）が３．０〜２０％の範囲にあるものが推奨される。
[Variation coefficient of particle diameter (CV value)]
The surface state of the spherical silica fine particles, which are the dispersoid of the silica sol according to the present invention, is determined by the surface roughness. Preferably, the particle diameter variation coefficient (CV value) is 3.0 to 20%. Those in the range are recommended.
ここで、粒子径の変動係数（ＣＶ値）とは、粒子半径の不均一性の度合を意味する。具
体的には、電子顕微鏡による写真投影図における球状シリカ微粒子の最長径を２等分する位置を該球状シリカ微粒子の中心とし、該中心から最長径の一方の端を角度０度とし、そこから１０度づつ０度から１８０度までの半径を測定し、それらの値から半径の平均値および標準偏差を算定する。更に該標準偏差を該平均値で除すことにより、粒子径の変動係数（相対標準偏差）を求める。本出願においては、任意の５０個の粒子について、それぞれ粒子径の変動係数を求め、それらの平均値を粒子径の変動係数（ＣＶ値）とした。
粒子径の変動係数（ＣＶ値）については、好適には３．０〜２０％の範囲が好ましい。粒子径の変動係数が３．０％未満の場合は、表面の起伏が少ない球状粒子に近くなる。粒子径の変動係数が２０％を超える場合については、表面が極めて起伏に富む状態になるが、本発明に係る製造方法によって調製することは容易ではない。また、その様なシリカ微粒子は、その組成によっては、疣状突起部分の強度が低くなる場合があり、研磨材用途に適さない場合が生じかねない。粒子径の変動係数（ＣＶ値）については、好ましくは３．３〜１５％の範囲が推奨される。また、更に好ましくは、５．０〜１２％の範囲が推奨される。
Here, the variation coefficient (CV value) of the particle diameter means the degree of nonuniformity of the particle radius. Specifically, the position at which the longest diameter of the spherical silica fine particle is divided into two equal parts in a photograph projection view by an electron microscope is the center of the spherical silica fine particle, and one end of the longest diameter from the center is an angle of 0 degree. The radius from 0 degree to 180 degree is measured every 10 degrees, and the average value and the standard deviation of the radius are calculated from these values. Further, the coefficient of variation (relative standard deviation) of the particle diameter is obtained by dividing the standard deviation by the average value. In the present application, the coefficient of variation of the particle diameter was determined for each of 50 arbitrary particles, and the average value thereof was defined as the coefficient of variation of particle diameter (CV value).
The coefficient of variation (CV value) of the particle diameter is preferably in the range of 3.0 to 20%. When the variation coefficient of the particle diameter is less than 3.0%, it becomes close to a spherical particle with little surface undulation. When the variation coefficient of the particle diameter exceeds 20%, the surface becomes extremely undulating, but it is not easy to prepare by the production method according to the present invention. In addition, such silica fine particles may have a lower strength of the hook-shaped protrusions depending on the composition, and may not be suitable for use as an abrasive. The coefficient of variation (CV value) of the particle diameter is preferably in the range of 3.3 to 15%. More preferably, the range of 5.0 to 12% is recommended.
［溶媒］
前記球状シリカ微粒子が分散する分散媒としての溶媒については、水、有機溶媒、またはこれらの混合溶媒のいずれであっても使用することができる。具体的には以下の例を挙げることができる。純水、超純水、イオン交換水などの水；メタノール、エタノール、イソプロパノール、ｎ−ブタノール、メチルイソカルビノールなどのアルコール類；アセトン、２−ブタノン、エチルアミルケトン、ジアセトンアルコール、イソホロン、シクロヘキサノンなどのケトン類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドなどのアミド類；ジエチルエーテル、イソプロピルエーテル、テトラヒドロフラン、１，４−ジオキサン、３，４−ジヒドロ−２Ｈ−ピランなどのエーテル類；２−メトキシエタノール、２−エトキシエタノール、２−ブトキシエタノール、エチレングリコールジメチルエーテルなどのグリコールエーテル類；２−メトキシエチルアセテート、２−エトキシエチルアセテート、２−ブトキシエチルアセテートなどのグリコールエーテルアセテート類；酢酸メチル、酢酸エチル、酢酸イソブチル、酢酸アミル、乳酸エチル、エチレンカーボネートなどのエステル類；ベンゼン、トルエン、キシレンなどの芳香族炭化水素類；ヘキサン、ヘプタン、ｉｓｏ−オクタン、シクロヘキサンなどの脂肪族炭化水素類；塩化メチレン、１，２−ジクロルエタン、ジクロロプロパン、クロルベンゼンなどのハロゲン化炭化水素類；ジメチルスルホキシドなどのスルホキシド類；Ｎ−メチル−２−ピロリドン、Ｎ−オクチル−２−ピロリドンなどのピロリドン類などを例示することができる。また、これらの分散媒は、１種単独で使用してもよく２種以上を併用しても構わない。
[solvent]
As a solvent as a dispersion medium in which the spherical silica fine particles are dispersed, any of water, an organic solvent, or a mixed solvent thereof can be used. Specifically, the following examples can be given. Water such as pure water, ultrapure water, ion exchange water; alcohols such as methanol, ethanol, isopropanol, n-butanol, methyl isocarbinol; acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone, cyclohexanone Ketones such as N; N-dimethylformamide, amides such as N, N-dimethylacetamide; ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, and 3,4-dihydro-2H-pyran Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate Glycol ether acetates such as methyl acetate; esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethylene carbonate; aromatic hydrocarbons such as benzene, toluene, xylene; hexane, heptane, iso-octane Aliphatic hydrocarbons such as cyclohexane; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene; sulfoxides such as dimethyl sulfoxide; N-methyl-2-pyrrolidone, N-octyl Examples thereof include pyrrolidones such as -2-pyrrolidone. Moreover, these dispersion media may be used individually by 1 type, and may use 2 or more types together.
２．製造方法
本発明に係るシリカゾルの製造方法は、４官能性シラン化合物と水の量を制御しながら、水溶性有機溶媒および水の混合溶媒に、４官能性シラン化合物の水溶性有機溶媒溶液およびアルカリ触媒溶液とを同時に、連続的または断続的に添加し、熟成することを特徴とするものである。
2. Production Method A method for producing a silica sol according to the present invention includes a water-soluble organic solvent solution and an alkali solution of a tetrafunctional silane compound in a mixed solvent of a water-soluble organic solvent and water while controlling the amount of the tetrafunctional silane compound and water. The catalyst solution is characterized by being simultaneously and intermittently added and aged.
特にシリカ微粒子を得るためには、水溶性有機溶媒／水混合溶媒中、３０〜１５０℃の温度範囲にて、４官能性シラン化合物に対し、モル比で２．以上、４．０未満の量の水により加水分解縮合することが必要である。 In particular, in order to obtain silica fine particles, the molar ratio is 2. As described above, it is necessary to perform hydrolytic condensation with an amount of water less than 4.0.
これについては、この条件下においては、４官能性シラン化合物の有する４つのアルコキシ基の反応速度に違いが生じるため、加水分解縮合初期に非球状の歪んだ形状のシリカ微粒子（一次粒子）が形成され、その様な歪んだ一次粒子が二次凝集する結果、表面に疣状突起を有するシリカ微粒子が生成するものと推察される。
前記４官能性シラン化合物に対する水のモル比が２．０未満の場合は、４官能性シラン化
合物の有する４個のアルコキシ基が完全に加水分解するモル量より少なくなるため、反応が充分に進行せず、反応中に凝集または沈殿が生じ易くなる。また、４官能性シラン化合物に対する水のモル比が４．０以上の場合は、水の量が過剰であるためアルコキシ基の反応速度に、充分な差異が生じないため結果的に球状で表面の起伏に乏しいシリカ微粒子が生成し易くなる。前記４官能性シラン化合物対する水のモル比の範囲については、好適には２．０〜３．８の範囲が推奨される。更に好適には２．０〜３．６の範囲が推奨される。
Regarding this, since the reaction rate of the four alkoxy groups of the tetrafunctional silane compound varies under these conditions, non-spherical distorted silica particles (primary particles) are formed at the initial stage of hydrolysis condensation. As a result of the secondary agglomeration of such distorted primary particles, it is presumed that silica fine particles having hook-shaped projections on the surface are generated.
When the molar ratio of water to the tetrafunctional silane compound is less than 2.0, the reaction proceeds sufficiently because the four alkoxy groups of the tetrafunctional silane compound are less than the molar amount of complete hydrolysis. Otherwise, aggregation or precipitation is likely to occur during the reaction. In addition, when the molar ratio of water to the tetrafunctional silane compound is 4.0 or more, the amount of water is excessive, so that there is no sufficient difference in the reaction rate of the alkoxy group. Silica fine particles with poor undulations are easily generated. About the range of the molar ratio of the water with respect to the said tetrafunctional silane compound, the range of 2.0-3.8 is recommended suitably. The range of 2.0 to 3.6 is more preferable.
［４官能性シラン化合物］
本発明に係る製造方法で使用される４官能性シラン化合物とは、次の一般式（１）で表されるアルコキシシラン化合物を意味する。
一般式（１）：（ＲＯ）4Ｓｉ （Ｒは炭素数２〜４のアルキル基）
具体的には、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシランなどが挙げられる。炭素数５以上のアルコキシシランは、アルコキシ基の立体障害により、実用的な加水分解速度が得られない場合がある。また、テトラメトキシシランの場合は、加水分解反応の反応速度がテトラエトキシシランの場合より速く、実用的にシリカを合成するには望ましくない。実用上は、テトラエトキシシランの使用が推奨される。
[Tetrafunctional silane compound]
The tetrafunctional silane compound used in the production method according to the present invention means an alkoxysilane compound represented by the following general formula (1).
General formula (1): (RO) 4 Si (R is an alkyl group having 2 to 4 carbon atoms)
Specific examples include tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. An alkoxysilane having 5 or more carbon atoms may not have a practical hydrolysis rate due to steric hindrance of the alkoxy group. In the case of tetramethoxysilane, the reaction rate of the hydrolysis reaction is faster than that of tetraethoxysilane, which is not desirable for practically synthesizing silica. For practical use, tetraethoxysilane is recommended.
なお、本発明に係る製造方法において、通常、４官能性シラン化合物は、水溶性有機溶媒に溶解させて使用することが望ましい。水溶性有機溶媒に溶解させて使用するとにより、雰囲気中の水分の影響を低減することができる。具体的には、４官能性シラン化合物の水溶性有機溶媒溶液中の４官能性シラン化合物の濃度が、５〜９０質量％の範囲のものが好適に使用される。５質量％未満では、反応液中のシリカ濃度が低くなり、実用的とはいえない。９０質量％を超える場合は、反応条件にもよるが、反応液中のシリカ濃度が高くなりすぎて、シリカの凝集や沈殿が生じ易くなる。該４官能性シラン化合物の濃度については、好適には１０〜６０質量％の範囲が推奨される。また、更に好適には２０〜４０質量％の範囲が推奨される。 In the production method according to the present invention, it is usually desirable to use the tetrafunctional silane compound by dissolving it in a water-soluble organic solvent. When used by dissolving in a water-soluble organic solvent, the influence of moisture in the atmosphere can be reduced. Specifically, the concentration of the tetrafunctional silane compound in the water-soluble organic solvent solution of the tetrafunctional silane compound is preferably in the range of 5 to 90% by mass. If it is less than 5% by mass, the silica concentration in the reaction solution becomes low, which is not practical. When it exceeds 90% by mass, although depending on the reaction conditions, the silica concentration in the reaction solution becomes too high and silica aggregation and precipitation are likely to occur. About the density | concentration of this tetrafunctional silane compound, the range of 10-60 mass% is recommended suitably. More preferably, a range of 20 to 40% by mass is recommended.
なお、４官能性シラン化合物の水溶性有機溶媒溶液として、好適にはテトラエトキシシランのエタノール溶液の使用が推奨される。 As the water-soluble organic solvent solution of the tetrafunctional silane compound, it is recommended to use an ethanol solution of tetraethoxysilane.
［水溶性有機溶媒］
本発明に係る製造方法で使用される水溶性有機溶媒としては、前記一般式（１）で表される４官能性シラン化合物を溶解し、水溶性を示す有機溶媒が含まれる。この様な水溶性有機溶媒の例としては、エタノール、イソプロパノール、ｔ−ブタノールなどを挙げることができる。水溶性有機溶媒の選択については、使用する４官能性シラン化合物との相溶性に優れるものが好適に使用される。
[Water-soluble organic solvent]
The water-soluble organic solvent used in the production method according to the present invention includes an organic solvent that dissolves the tetrafunctional silane compound represented by the general formula (1) and exhibits water solubility. Examples of such water-soluble organic solvents include ethanol, isopropanol, and t-butanol. About selection of a water-soluble organic solvent, what is excellent in compatibility with the tetrafunctional silane compound to be used is used suitably.
［水溶性有機溶媒と水の混合溶媒］
水溶性有機溶媒と水の混合溶媒に含まれる水分量については、アルカリ触媒溶液が水分を含有しない場合は、前記４官能性シラン化合物に対する水のモル比の範囲内であることが必要となる。また、アルカリ触媒溶液が水分を含有する場合にあっては、前記混合溶媒に含まれる水分量とアルカリ触媒溶液に含まれる水分量の合計量が、前記４官能性シラン化合物に対する水のモル比の範囲内であることが必要となる。前記混合溶媒についてはこの前提を満たしたものが使用されるが、望ましくは水溶性有機溶媒の濃度が３０〜９５質量％の範囲（水分が５〜７０質量％の範囲）のものが使用される。水溶性有機溶媒の割合が３０質量％未満の場合（水分が７０質量％以上）は、４官能性シラン化合物の量や加水分解速度によるが、添加された４官能性シラン化合物と混合溶媒が混ざり難くなり、４官能性シラン化合物がゲル化する場合がある。また、水溶性有機溶媒の割合が９５質量％を超える場合（水分が５質量％未満）は、加水分解に使用する水分が過少となる場合がある
。水溶性有機溶媒と水の混合溶媒における水の割合については、好適には４０〜８０質量％の範囲が推奨される。また、更に好適には５０〜７０質量％の範囲が推奨される。
[A mixed solvent of water-soluble organic solvent and water]
The amount of water contained in the mixed solvent of the water-soluble organic solvent and water needs to be within the range of the molar ratio of water to the tetrafunctional silane compound when the alkali catalyst solution does not contain water. When the alkali catalyst solution contains water, the total amount of water contained in the mixed solvent and water contained in the alkali catalyst solution is a molar ratio of water to the tetrafunctional silane compound. It must be within range. As the mixed solvent, those satisfying this premise are used, but preferably those having a water-soluble organic solvent concentration in the range of 30 to 95% by mass (moisture in the range of 5 to 70% by mass) are used. . When the proportion of the water-soluble organic solvent is less than 30% by mass (moisture is 70% by mass or more), depending on the amount of the tetrafunctional silane compound and the hydrolysis rate, the added tetrafunctional silane compound and the mixed solvent are mixed. It becomes difficult and the tetrafunctional silane compound may be gelled. Moreover, when the ratio of the water-soluble organic solvent exceeds 95% by mass (moisture is less than 5% by mass), the water used for hydrolysis may be too small. About the ratio of the water in the mixed solvent of a water-soluble organic solvent and water, the range of 40-80 mass% is recommended suitably. More preferably, the range of 50 to 70% by mass is recommended.
［アルカリ触媒］
本発明に係る製造方法で使用されるアルカリ触媒としては、アンモニア、アミン、アルカリ金属水素化物、第４級アンモニウム化合物、アミン系カップリング剤など、塩基性を示す化合物が用いられる。なお、触媒としてアルカリ金属水素化物を用いることもできるが、前記アルコキシシランのアルコキシ基の加水分解を促進し、このため得られる粒子中に残存アルコキシ基（炭素）が減少しより硬いものとなるため、研磨速度は高いもののスクラッチが発生する場合があり、さらにナトリウム水素化物を使用した場合は、Ｎａの含有量が高くなる問題がある。
[Alkali catalyst]
As the alkali catalyst used in the production method according to the present invention, basic compounds such as ammonia, amines, alkali metal hydrides, quaternary ammonium compounds and amine coupling agents are used. Although an alkali metal hydride can be used as a catalyst, it promotes hydrolysis of the alkoxy group of the alkoxysilane, and therefore, the remaining alkoxy groups (carbon) are reduced in the resulting particles and become harder. Although the polishing rate is high, scratches may occur, and when sodium hydride is used, there is a problem that the content of Na becomes high.
アルカリ触媒の使用量については、所望の加水分解速度が得られる限り限定されるものではないが、通常は、４官能性シラン化合物１モル当たり、０． ００５〜１モルの範囲
で添加されることが好ましい。 更に好ましくは０． ０１〜０． ８モルの範囲となるように添加されていることが推奨される。なお、アルカリ触媒は、通常は水および／または水溶性有機溶媒で希釈して、アルカリ触媒溶液として使用することが好ましい。なお、この水溶性有機触媒に含まれる水分についても、加水分解に寄与するものであるので、当然に加水分解に使用される水分量に算入されるものである。
The amount of the alkali catalyst used is not limited as long as the desired hydrolysis rate can be obtained, but it is usually 0.00 per mol of the tetrafunctional silane compound. It is preferable to add in the range of 005 to 1 mol. More preferably, 0. 01-0. It is recommended that it be added in a range of 8 moles. The alkali catalyst is usually preferably diluted with water and / or a water-soluble organic solvent and used as an alkali catalyst solution. In addition, since the water contained in this water-soluble organic catalyst also contributes to hydrolysis, it is naturally included in the amount of water used for hydrolysis.
通常は、アルカリ触媒溶液におけるアルカリ触媒濃度については、０．１〜２０質量％の範囲が好ましい。０．１質量％未満では、実用的な触媒機能が得られない場合がある。また、２０質量％以上の場合、触媒機能が平衡に達する場合が多く、過剰に使用することになる場合がある。 Usually, about the alkali catalyst density | concentration in an alkali catalyst solution, the range of 0.1-20 mass% is preferable. If it is less than 0.1% by mass, a practical catalytic function may not be obtained. In addition, when the amount is 20% by mass or more, the catalyst function often reaches an equilibrium and may be used excessively.
アルカリ触媒溶液におけるアルカリ触媒濃度については、より好適には、１〜１５質量％の範囲が推奨される。更に好適には、２〜１２質量％の範囲が推奨される。
アルカリ触媒については、例えば、アンモニア水溶液、アンモニウム水溶液とエタノールの混合物などが好適に使用できる。
About the alkali catalyst density | concentration in an alkali catalyst solution, the range of 1-15 mass% is recommended more suitably. More preferably, a range of 2 to 12% by mass is recommended.
As the alkali catalyst, for example, an aqueous ammonia solution, a mixture of an aqueous ammonium solution and ethanol can be preferably used.
［製造工程］
本発明に係るシリカゾルの好適な製造方法について以下に述べるが、本発明に係るシリカゾルの製造方法は、これに限定されるものではない。前記水溶性有機溶媒と水の混合溶媒の温度範囲を３０〜１５０℃に維持し、１）４官能性シラン化合物の水溶性有機溶媒溶液および２）アルカリ触媒の水溶液とを同時に、連続的または断続的に３０分から２０時間かけて添加する。前記温度範囲については、３０℃未満では、加水分解縮合が充分に進行しないため望ましくない。混合溶媒の沸点を超える場合は、オートクレーブなどの耐圧容器を用いて行う事ができるが、１５０℃を超える場合は、非常に高い圧力がかかるため工業的でないので、望ましくない。
[Manufacturing process]
Although the suitable manufacturing method of the silica sol which concerns on this invention is described below, the manufacturing method of the silica sol which concerns on this invention is not limited to this. The temperature range of the mixed solvent of the water-soluble organic solvent and water is maintained at 30 to 150 ° C., and 1) the water-soluble organic solvent solution of the tetrafunctional silane compound and 2) the aqueous solution of the alkali catalyst are simultaneously, continuously or intermittently. For 30 minutes to 20 hours. Regarding the temperature range, if it is less than 30 ° C., hydrolysis condensation does not proceed sufficiently, which is not desirable. When it exceeds the boiling point of the mixed solvent, it can be carried out using a pressure-resistant vessel such as an autoclave. However, when it exceeds 150 ° C., it is not industrial because it is not industrial because a very high pressure is applied.
この温度範囲については好適には４０〜１００℃の範囲が推奨される。また、更に好適には、５０〜８０℃の範囲が推奨される。添加にかける前記の所要時間範囲については、好適には１〜１５時間が推奨される。また、更に好適には、２〜１０時間が推奨される。 About this temperature range, the range of 40-100 degreeC is recommended suitably. More preferably, a range of 50 to 80 ° C. is recommended. With respect to the required time range for the addition, 1 to 15 hours are preferably recommended. More preferably, 2 to 10 hours are recommended.
前記１）４官能性シラン化合物の水溶性有機溶媒溶液および２）アルカリ触媒の水溶液については、両者を同時に、連続的にまたは断続的に３０分から２０時間かけて、前記水溶性有機溶媒と水の混合溶媒に添加することが好ましい。両者の全量を一時に一括添加した場合、加水分解縮合が急激に進行するためゲル状物の発生を招き、シリカ微粒子を得ることができない。 For 1) the water-soluble organic solvent solution of the tetrafunctional silane compound and 2) the aqueous solution of the alkali catalyst, both the water-soluble organic solvent and water are used simultaneously, continuously or intermittently for 30 minutes to 20 hours. It is preferable to add to a mixed solvent. When the total amount of both is added all at once, hydrolytic condensation proceeds rapidly, resulting in the generation of a gel-like substance and silica fine particles cannot be obtained.
本発明に係る製造方法では、前記の通り、４官能性シラン化合物の反応速度の特性を利用してシリカゾルを調製するものである。例えばテトラメトキシシランを使用した場合は、その加水分解反応は、テトラエトキシシランの場合に比べて速いため、テトラエトキシシランの様にシリカゾルを形成することは容易ではない。 In the production method according to the present invention, as described above, the silica sol is prepared by utilizing the reaction rate characteristics of the tetrafunctional silane compound. For example, when tetramethoxysilane is used, it is not easy to form a silica sol like tetraethoxysilane because the hydrolysis reaction is faster than that of tetraethoxysilane.
加水分解縮合に必要な成分の添加が終了した後、所望により３０〜１５０℃にて、０．５〜１０時間の範囲で熟成することが好ましい。
例えば、未反応の４官能性シラン化合物が残存していた場合、熟成することにより、未反応の４官能性シラン化合物の反応を促進し、完結させることができる。なお、未反応の４官能性シラン化合物の残存量によっては、経時でシリカの凝集や沈殿が生じる場合がある。熟成時の前記温度範囲については好適には４０〜１００℃の範囲が推奨される。また、更に好適には、５０〜８０℃の範囲が推奨される。前記熟成時間範囲については、好適には１〜９時間が推奨される。また、更に好適には、２〜８時間が推奨される。
After completion of the addition of the components necessary for the hydrolysis and condensation, it is preferably aged at 30 to 150 ° C. for 0.5 to 10 hours if desired.
For example, when an unreacted tetrafunctional silane compound remains, the reaction of the unreacted tetrafunctional silane compound can be promoted and completed by aging. Depending on the remaining amount of the unreacted tetrafunctional silane compound, silica may aggregate or precipitate over time. A temperature range of 40 to 100 ° C. is recommended for the temperature range during aging. More preferably, a range of 50 to 80 ° C. is recommended. The aging time range is preferably 1 to 9 hours. More preferably, 2 to 8 hours are recommended.
［研磨材］
本発明に係る研磨材は、前記した研磨用シリカ粒子が分散媒に分散したものである。分散媒としては通常、水を用いるが、必要に応じてメチルアルコール、エチルアルコール、イソプロピルアルコール等のアルコール類を用いることができ、他にエーテル類、エステル類、ケトン類など水溶性の有機溶媒を用いることができる。研磨材中の研磨用シリカ粒子の濃度は１〜５０質量％、さらには３〜３０質量％の範囲にあることが好ましい。濃度が１質量％未満の場合は、基材や絶縁膜の種類によっては濃度が低すぎて研磨速度が遅く生産性が問題となることがある。シリカ粒子の濃度が５０質量％を越えると研磨材の安定性が不充分となり、研磨速度や研磨効率がさらに向上することもなく、また研磨処理のために分散液を供給する工程で乾燥物が生成して付着することがあり傷（スクラッチ）発生の原因となることがある。
[Abrasive]
The abrasive according to the present invention is obtained by dispersing the above-described abrasive silica particles in a dispersion medium. Usually, water is used as the dispersion medium, but alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol can be used as necessary. In addition, water-soluble organic solvents such as ethers, esters, and ketones can be used. Can be used. The concentration of the silica particles for polishing in the abrasive is preferably 1 to 50% by mass, more preferably 3 to 30% by mass. When the concentration is less than 1% by mass, the concentration may be too low depending on the type of the base material or the insulating film, and the polishing rate may be slow and productivity may be a problem. If the concentration of silica particles exceeds 50% by mass, the stability of the abrasive will be insufficient, the polishing rate and the polishing efficiency will not be further improved, and the dried product will be removed in the step of supplying the dispersion for polishing treatment. It may be generated and attached, which may cause scratches.
［研磨用組成物］
本発明の研磨材には、被研磨材の種類によっても異なるが、必要に応じて従来公知の過酸化水素、過酢酸、過酸化尿素などおよびこれらの混合物を添加して用いることができる。このような過酸化水素等を添加して用いると被研磨材が金属の場合には効果的に研磨速度を向上させることができる。また、必要に応じて硫酸、硝酸、リン酸、フッ酸等の酸、あるいはこれら酸のナトリウム塩、カリウム塩、アンモニウム塩およびこれらの混合物などを添加して用いることができる。この場合、複数種の材質の被研磨材を研磨する際に、特定成分の被研磨材の研磨速度を速めたり、遅くしたりすることによって、最終的に平坦な研磨面を得ることができる。その他の添加剤として、例えば、金属被研磨材表面に不動態層あるいは溶解抑制層を形成して基材の浸食を防止するためにイミダゾール、ベンゾトリアゾール、ベンゾチアゾールなどを用いることができる。また、上記不動態層を攪乱するためにクエン酸、乳酸、酢酸、シュウ酸、フタル酸、クエン酸等の有機酸あるいはこれらの有機酸塩などの錯体形成材を用いることもできる。研磨材スラリーの分散性や安定性を向上させるためにカチオン系、アニオン系、ノニオン系、両性系の界面活性剤を適宜選択して添加することができる。さらに、上記各添加剤の効果を高めるためなどに必要に応じて酸または塩基を添加して研磨材スラリーのｐＨを調節することができる。
[Polishing composition]
The abrasive of the present invention can be used by adding conventionally known hydrogen peroxide, peracetic acid, urea peroxide, or a mixture thereof, if necessary, although it varies depending on the type of material to be polished. When such hydrogen peroxide or the like is added and used, when the material to be polished is a metal, the polishing rate can be effectively improved. If necessary, an acid such as sulfuric acid, nitric acid, phosphoric acid or hydrofluoric acid, or a sodium salt, potassium salt, ammonium salt or a mixture thereof can be added. In this case, when polishing a plurality of kinds of materials to be polished, a flat polishing surface can be finally obtained by increasing or decreasing the polishing rate of the materials to be polished having a specific component. As other additives, for example, imidazole, benzotriazole, benzothiazole and the like can be used in order to form a passive layer or a dissolution suppressing layer on the surface of the metal polishing material to prevent erosion of the substrate. In order to disturb the passive layer, a complex forming material such as an organic acid such as citric acid, lactic acid, acetic acid, oxalic acid, phthalic acid, citric acid, or an organic acid salt thereof may be used. In order to improve the dispersibility and stability of the abrasive slurry, a cationic, anionic, nonionic or amphoteric surfactant can be appropriately selected and added. Furthermore, the pH of the abrasive slurry can be adjusted by adding an acid or a base as necessary in order to enhance the effect of each additive.
［好適な態様１］
表面に複数の疣状突起を有する球状シリカ微粒子が溶媒に分散してなるシリカゾルであって、該球状シリカ微粒子が、以下の１）〜５）の条件を満たすものであることを特徴とするシリカゾル。
[Preferred embodiment 1]
A silica sol in which spherical silica fine particles having a plurality of hook-shaped protrusions are dispersed in a solvent, and the spherical silica fine particles satisfy the following conditions 1) to 5): .
１）ＢＥＴ法により測定された比表面積を（ＳＡ１）とし、画像解析法により測定される該シリカ微粒子の平均粒子径（Ｄ２）から換算した比表面積を（ＳＡ２）としたときの表
面粗度（ＳＡ１）／（ＳＡ２）の値が、１．９〜５．０の範囲
２）該球状シリカ微粒子の平均粒子径（Ｄ２）が１０〜１５０ｎｍの範囲
３）該球状シリカ微粒子のナトリウム含有割合が１００質量ｐｐｍ以下
４）該球状シリカ微粒子の炭素含有割合が０．１〜５質量％の範囲
５）該球状シリカ微粒子の粒子径の変動係数が３〜２０％の範囲
［好適な態様２］ 表面に複数の疣状突起を有する球状シリカ微粒子が溶媒に分散してなるシリカゾルであって、該球状シリカ微粒子が、以下の１）〜５）の条件を満たすものであることを特徴とするシリカゾル。
１）ＢＥＴ法により測定された比表面積を（ＳＡ１）とし、画像解析法により測定される該シリカ微粒子の平均粒子径（Ｄ２）から換算した比表面積を（ＳＡ２）としたときの表面粗度（ＳＡ１）／（ＳＡ２）の値が、１．９〜５．０の範囲
２）該球状シリカ微粒子の平均粒子径（Ｄ２）が１０〜１５０ｎｍの範囲
３）該球状シリカ微粒子のナトリウム含有割合が１００質量ｐｐｍ以下
４）該球状シリカ微粒子の炭素含有割合が０．１〜５質量％の範囲
５）該球状シリカ微粒子の粒子径の変動係数が３〜２０％の範囲
６）該球状シリカ微粒子が［ＳｉＯ4/2］単位を含有するものである
1) Surface roughness when the specific surface area measured by the BET method is (SA1) and the specific surface area converted from the average particle diameter (D2) of the silica fine particles measured by the image analysis method is (SA2) ( The value of SA1) / (SA2) is in the range of 1.9 to 5.0 2) The average particle diameter (D2) of the spherical silica fine particles is in the range of 10 to 150 nm 3) The sodium content of the spherical silica fine particles is 100 Mass ppm or less 4) Range in which carbon content of spherical silica fine particles is 0.1 to 5 mass% 5) Range in which variation coefficient of particle diameter of spherical silica fine particles is 3 to 20% [Preferred embodiment 2] A silica sol obtained by dispersing spherical silica fine particles having a plurality of hook-shaped protrusions in a solvent, wherein the spherical silica fine particles satisfy the following conditions 1) to 5).
1) Surface roughness when the specific surface area measured by the BET method is (SA1) and the specific surface area converted from the average particle diameter (D2) of the silica fine particles measured by the image analysis method is (SA2) ( The value of SA1) / (SA2) is in the range of 1.9 to 5.0 2) The average particle diameter (D2) of the spherical silica fine particles is in the range of 10 to 150 nm 3) The sodium content of the spherical silica fine particles is 100 4) Range of carbon content of the spherical silica fine particles is 0.1 to 5% by mass 5) Range of variation coefficient of the particle diameter of the spherical silica fine particles is 3 to 20% 6) The spherical silica fine particles are [ Containing SiO 4/2 ] units
［好適な態様３］
エタノールおよび水を含む混合溶媒の温度範囲を３０〜１５０℃に維持し、そこに、１）テトラエトキシシランのエタノール溶液および２）アルカリ触媒の水溶液とを同時に、連続的または断続的に３０分から２０時間かけて添加し、添加終了後、更に３０〜１５０℃の温度範囲にて熟成することにより、テトラエトキシシランを加水分解縮合させてなるシリカゾルの製造方法において、テトラエトキシシランに対する水のモル比を、２以上、４未満の範囲にして、加水分解縮合を行うことを特徴とするシリカゾルの製造方法。
[Preferred Aspect 3]
The temperature range of the mixed solvent containing ethanol and water is maintained at 30 to 150 ° C., and 1) an ethanol solution of tetraethoxysilane and 2) an aqueous solution of an alkali catalyst are simultaneously or intermittently used for 30 minutes to 20 minutes. In the method for producing a silica sol obtained by hydrolyzing and condensing tetraethoxysilane by adding over time and aging in the temperature range of 30 to 150 ° C. after the addition is completed, the molar ratio of water to tetraethoxysilane is A method for producing a silica sol, wherein hydrolysis condensation is performed in a range of 2 or more and less than 4.
［実施例および比較例で用いた測定方法等］
［１］動的光散乱法による平均粒子径の測定方法
試料シリカゾルを０．５８％アンモニア水にて希釈して、シリカ濃度１質量調整し、下記粒径測定装置を用いて平均粒子径を測定した。
[Measurement methods used in Examples and Comparative Examples]
[1] Method for measuring average particle diameter by dynamic light scattering method The sample silica sol is diluted with 0.58% ammonia water, the silica concentration is adjusted to 1 mass, and the average particle diameter is measured using the following particle size measuring apparatus. did.
〔粒径測定装置〕
レーザーパーティクルアナライザー（製造元：大塚電子社、型番「レーザー粒径解析システム、ＬＰ−５１０モデルＰＡＲ−ＩＩＩ」、測定原理 動的光散乱法 測定角度90°、受光素子 光電子倍増管2インチ、測定範囲3nm〜5μm、光源 He-Neレーザー 5mW 632.8nm、温度調整範囲5〜90℃、
温度調整方式ペルチェ素子(冷却)、セラミックヒーター(加熱)、セル 10mm角 プラスチックセル、
測定対象：コロイド粒子
[Particle size measuring device]
Laser particle analyzer (Manufacturer: Otsuka Electronics Co., Ltd., model number “Laser particle size analysis system, LP-510 model PAR-III”, measurement principle Dynamic light scattering method Measurement angle 90 °, photo detector 2 inch photomultiplier tube, measurement range 3 nm ~ 5μm, light source He-Ne laser 5mW 632.8nm, temperature adjustment range 5 ~ 90 ℃,
Temperature adjustment method Peltier element (cooling), ceramic heater (heating), cell 10mm square plastic cell,
Measurement object: Colloidal particles
［２］ＢＥＴ法（窒素吸着法）による比表面積測定方法
シリカゾル５０ｍｌをＨＮＯ3でｐＨ３．５に調整し、１−プロパノール４０ｍｌを加
え、１１０℃で１６時間乾燥した試料について、乳鉢で粉砕後、マッフル炉にて５００℃、１時間焼成し、測定用試料とした。そして、比表面積測定装置（ユアサアイオニクス製、型番マルチソーブ１２）を用いて窒素吸着法（ＢＥＴ法）を用いて、窒素の吸着量から、ＢＥＴ１点法により比表面積を算出した。
[2] Specific surface area measurement method by BET method (nitrogen adsorption method) 50 ml of silica sol was adjusted to pH 3.5 with HNO 3 , 40 ml of 1-propanol was added, and the sample was dried at 110 ° C. for 16 hours. A sample for measurement was obtained by baking at 500 ° C. for 1 hour in a muffle furnace. And the specific surface area was computed by the BET 1 point method from the adsorption amount of nitrogen using the nitrogen adsorption method (BET method) using the specific surface area measuring apparatus (The product made from Yuasa Ionics, model number multisorb 12).
具体的には、試料０．５ｇを測定セルに取り、窒素３０ｖ％／ヘリウム７０ｖ％混合ガス気流中、３００℃で２０分間脱ガス処理を行い、その上で試料を上記混合ガス気流中で液体窒素温度に保ち、窒素を試料に平衡吸着させる。次に、上記混合ガスを流しながら試
料温度を徐々に室温まで上昇させ、その間に脱離した窒素の量を検出し、予め作成した検量線により、シリカゾルの比表面積を算出した。
Specifically, 0.5 g of a sample is taken in a measurement cell, degassed for 20 minutes at 300 ° C. in a mixed gas stream of nitrogen 30 v% / helium 70 v%, and then the sample is liquidized in the mixed gas stream. Keep nitrogen temperature and allow nitrogen to equilibrate to sample. Next, the sample temperature was gradually raised to room temperature while flowing the mixed gas, the amount of nitrogen desorbed during that time was detected, and the specific surface area of the silica sol was calculated using a calibration curve prepared in advance.
［３］画像解析による平均粒子径（Ｄ２）の測定方法および比表面積（ＳＡ２）の算定方法
透過型電子顕微鏡（株式会社日立製作所製、Ｈ−８００）により、試料シリカゾルを倍率２５万倍で写真撮影して得られる写真投影図における、任意の５０個の粒子について、その最大径（ＤＬ）を測定し、その平均値を平均粒子径（Ｄ２）とした。また、平均粒子径（Ｄ２）の値を次の式（２）に代入して、比表面積（ＳＡ２）を求めた。
[3] Measurement method of average particle diameter (D2) by image analysis and calculation method of specific surface area (SA2) Photograph of sample silica sol at a magnification of 250,000 using a transmission electron microscope (H-800, manufactured by Hitachi, Ltd.) The maximum diameter (DL) of any 50 particles in a photograph projection view obtained by photographing was measured, and the average value was defined as the average particle diameter (D2). Further, the specific surface area (SA2) was determined by substituting the value of the average particle diameter (D2) into the following formula (2).
Ｄ２＝６０００／（ρ×ＳＡ２） ・・・ （１）
ここで、Ｄ２は平均粒子径［ｎｍ］、ρは試料の密度［ｇ／ｃｍ3］であり、ここでは
シリカの密度２．２を使用した。
D2 = 6000 / (ρ × SA2) (1)
Here, D2 is the average particle diameter [nm], ρ is the density of the sample [g / cm 3 ], and here, the density of silica 2.2 was used.
［４］真球度の測定方法
透過型電子顕微鏡（株式会社日立製作所製、Ｈ−８００）により、試料シリカゾルを倍率２５万倍で写真撮影して得られる写真投影図における、任意の５０個の粒子について、それぞれ最大径（ＤＬ）を測定し、該最大径上で、該最大径を２等分する点（中心点）を求め、該中心点を通過し、該最大径に直交する径の長さ（ＤＳ）を測定し、（ＤＬ）／（ＤＳ）の値を求め、５０個の粒子について平均値をとり、これを真球度とした。
[4] Method for measuring sphericity Any 50 of the photographic projections obtained by photographing a sample silica sol at a magnification of 250,000 times with a transmission electron microscope (H-800, manufactured by Hitachi, Ltd.) For each particle, the maximum diameter (DL) is measured, and on the maximum diameter, a point (center point) that bisects the maximum diameter is obtained, the diameter that passes through the center point and is orthogonal to the maximum diameter The length (DS) was measured, the value of (DL) / (DS) was determined, the average value was taken for 50 particles, and this was taken as the sphericity.
［５］粒子径の変動係数の算定
透過型電子顕微鏡（株式会社日立製作所製、Ｈ−８００）により、試料シリカゾルを倍率２５万倍ないし５０万倍で写真撮影して得られる写真投影図における球状シリカ微粒子の最長径を２等分する位置を該球状シリカ微粒子の中心とし、該中心から最長径の一方の端を角度０度とし、そこから１０度づつ０度から１８０度までの半径を測定する。そして、その値から半径の平均値および標準偏差を算定する。更に該標準偏差を該平均値で除すことにより粒子径の変動係数（相対標準偏差）を求めた。この測定および算定を任意の５０個の粒子について行い、粒子径の変動係数の平均値をとり、その値を粒子径の変動係数（ＣＶ値）とした。なお、粒子径の変動係数（ＣＶ値）については、粒子径の変動係数（ＣＶ値）［％］＝（粒子径の標準偏差／粒子径の平均値）×１００として表示した。
[5] Calculation of coefficient of variation of particle diameter Spherical shape in a photographic projection obtained by photographing a sample silica sol at a magnification of 250,000 to 500,000 with a transmission electron microscope (H-800, manufactured by Hitachi, Ltd.) The position where the longest diameter of the silica fine particle is divided into two equals is the center of the spherical silica fine particle, one end of the longest diameter from the center is an angle of 0 degrees, and a radius from 0 degrees to 180 degrees is measured in 10 degrees from there. To do. And the average value and standard deviation of a radius are calculated from the value. Furthermore, the coefficient of variation (relative standard deviation) of the particle diameter was determined by dividing the standard deviation by the average value. This measurement and calculation were performed on arbitrary 50 particles, and the average value of the coefficient of variation in particle diameter was taken, and the value was taken as the coefficient of variation (CV value) in particle diameter. The particle diameter variation coefficient (CV value) was expressed as particle diameter variation coefficient (CV value) [%] = (standard deviation of particle diameter / average value of particle diameter) × 100.
［６］Ｎａの定量方法
次の手順によりナトリウムの含有量を測定した。
１）試料シリカゾル約１０ｇを白金皿に採取し、０．１ｍｇまで秤量する。
２）硝酸５ｍｌと弗化水素酸２０ｍｌを加えて、サンドバス上で加熱し、蒸発乾固する。３）液量が少なくなったら、更に弗化水素酸２０mlを加えてサンドバス上で加熱し、蒸発乾固する。
４）室温まで冷却後、硝酸２ｍｌと水を約５０ml加えて、サンドバス上で加熱溶解する。５）室温まで冷却後、フラスコ（１００ｍｌ）に入れ、水で１００ｍｌに希釈して試料溶液とする。
６）原子吸光分光光度計（株式会社日立製作所製、Z-５３００、測定モード：原子吸光、測定波長：１９０〜９００ｎｍ、シリカ試料の場合におけるＮａの検出波長は５８９．０ｎｍ)にて、試料溶液中に存在する各金属の含有量を測定した。この原子吸光分光光度計
は、フレームにより試料を原子蒸気化し、その原子蒸気層に適当な波長の光を照射し、その際の原子によって吸収された光の強さを測定し、これにより試料中の元素濃度を定量するものである。
７）試料シリカゾル１０ｇに５０％硫酸水溶液２ｍｌを加え、白金皿上にて蒸発乾固し、得られた固形物を１０００℃にて１時間焼成後、冷却して秤量する。次に、秤量した固形物を微量の５０％硫酸水溶液に溶かし、更にフッ化水素酸２０ｍｌを加えてから、白金皿
上にて蒸発乾固し、１０００℃にて１５分焼成後、冷却して秤量する。これらの重量差よりシリカ含有量を求めた。
８）上記６）と７）の結果からＳｉＯ2分に対するＮａの割合を算出した。
[6] Method for quantifying Na The sodium content was measured by the following procedure.
1) About 10 g of sample silica sol is collected in a platinum dish and weighed to 0.1 mg.
2) Add 5 ml of nitric acid and 20 ml of hydrofluoric acid, heat on a sand bath and evaporate to dryness. 3) When the amount of liquid decreases, add 20 ml of hydrofluoric acid and heat on a sand bath to evaporate to dryness.
4) After cooling to room temperature, add 2 ml of nitric acid and about 50 ml of water and dissolve by heating on a sand bath. 5) After cooling to room temperature, place in a flask (100 ml) and dilute to 100 ml with water to make the sample solution.
6) Atomic absorption spectrophotometer (manufactured by Hitachi, Ltd., Z-5300, measurement mode: atomic absorption, measurement wavelength: 190 to 900 nm, Na detection wavelength in the case of silica sample is 589.0 nm), sample solution The content of each metal present therein was measured. This atomic absorption spectrophotometer vaporizes a sample with a frame, irradiates the atomic vapor layer with light of an appropriate wavelength, and measures the intensity of light absorbed by the atoms at that time. The elemental concentration of is determined.
7) Add 2 ml of 50% sulfuric acid aqueous solution to 10 g of sample silica sol, evaporate to dryness on a platinum dish, and bake the obtained solid at 1000 ° C. for 1 hour, then cool and weigh. Next, dissolve the weighed solid in a small amount of 50% aqueous sulfuric acid, add 20 ml of hydrofluoric acid, evaporate to dryness on a platinum pan, bake at 1000 ° C. for 15 minutes, and cool. Weigh. The silica content was determined from these weight differences.
8) The ratio of Na to SiO 2 was calculated from the results of 6) and 7) above.
［７］熱酸化膜に対する研磨特性の評価方法
研磨スラリーの調製 各実施例および各比較例で得たシリカ濃度１２．６質量％のシリカゾルに、ＫＯＨを添加して、ｐＨを１０に調整した。
[7] Evaluation Method of Polishing Characteristics for Thermal Oxide Film Preparation of Polishing Slurry KOH was added to silica sol having a silica concentration of 12.6% by mass obtained in each Example and each Comparative Example, and the pH was adjusted to 10.
被研磨基板 被研磨基板として、シリコンウェーハを１０５０℃でウエット熱酸化させた熱酸化膜基板を使用した。
研磨試験 上記被研磨基板を、研磨装置（ナノファクター（株）製：ＮＦ３３０）にセットし、研磨パッド（ロデール社製「ＩＣ-１０００」）を使用し、基板荷重０．０５ＭＰａ、テーブル回転速度３０ｒｐｍで研磨用研磨スラリーを２０ｇ／分の速度で５分間供給して研磨を行った。研磨前後の膜厚を短波長エリプソメーターで測定し、研磨速度を計算した。
Substrate to be polished As the substrate to be polished, a thermal oxide film substrate obtained by wet-oxidizing a silicon wafer at 1050 ° C. was used.
Polishing test The above-mentioned substrate to be polished is set in a polishing apparatus (manufactured by Nano Factor Co., Ltd .: NF330), a polishing pad (“IC-1000” manufactured by Rodel) is used, a substrate load of 0.05 MPa, and a table rotation speed of 30 rpm. Polishing was performed by supplying a polishing slurry for polishing at a rate of 20 g / min for 5 minutes. The film thickness before and after polishing was measured with a short wavelength ellipsometer, and the polishing rate was calculated.
［８］Ｃ（炭素）の含有量測定方法
Ｃ（炭素）の含有量については、ＥＭＩＡ−３２０Ｖ（ＨＯＲＩＢＡ社製）にて測定した。
[8] Method for measuring content of C (carbon) The content of C (carbon) was measured with EMIA-320V (manufactured by HORIBA).
以下の実施例および比較例で調製したシリカゾルおよびその分散質であるシリカ微粒子に関する測定結果を表１に記した。また、以下の実施例および比較例における、４官能性シラン化合物（テトラエトキシシラン）、水、水溶性有機溶媒（エタノール）、アルカリ触媒（アンモニア溶液）などの使用量および調製条件を表２‐１および表２‐２に記した。 The measurement results regarding the silica sol prepared in the following Examples and Comparative Examples and the silica fine particles which are the dispersoids thereof are shown in Table 1. Table 2-1 shows the amounts and preparation conditions of the tetrafunctional silane compound (tetraethoxysilane), water, water-soluble organic solvent (ethanol), alkali catalyst (ammonia solution), etc. in the following Examples and Comparative Examples. And in Table 2-2.
［実施例１］
超純水２３７．３ｇにエタノール３５５．８ｇとを混合した混合溶媒を６５℃に加熱して、これにテトラエトキシシラン(多摩化学製エチルシリケート２８、ＳｉＯ2=２８．８
質量％)１１８８ｇとエタノール２２５５ｇを混合したテトラエトキシラン溶液、および
超純水１００ｇと２９．１％アンモニア水溶液４０．５ｇを混合したアンモニア希釈液とを同時に３時間かけて添加した。添加終了後、さらに６５℃で３時間熟成した。そして、限外濾過膜で固形分濃度１５質量％まで濃縮し、未反応のテトラエトキシシランを除去した。さらにロータリーエバポレーターでエタノール、アンモニアをほぼ除去し、固形分濃度１２．６質量％のシリカゾルを得た。このシリカゾルの分散質であるシリカ微粒子に関する測定結果を表１に記す。
[Example 1]
A mixed solvent obtained by mixing 237.3 g of ultrapure water and 355.8 g of ethanol was heated to 65 ° C., and tetraethoxysilane (ethyl silicate 28 manufactured by Tama Chemical, SiO 2 = 28.8) was added thereto.
(Mass%) A tetraethoxylane solution in which 1188 g and 2255 g of ethanol were mixed, and an ammonia diluted solution in which 100 g of ultrapure water and 40.5 g of 29.1% ammonia aqueous solution were mixed were added simultaneously over 3 hours. After completion of the addition, the mixture was further aged at 65 ° C. for 3 hours. And it concentrated to 15 mass% of solid content with an ultrafiltration membrane, and unreacted tetraethoxysilane was removed. Further, ethanol and ammonia were almost removed by a rotary evaporator to obtain a silica sol having a solid content concentration of 12.6% by mass. Table 1 shows the measurement results regarding silica fine particles which are the dispersoid of this silica sol.
［実施例２］
実施例１の混合溶媒に代えて、超純水１７７ｇにエタノール４１６．１ｇを添加してなる混合溶媒を使用し、さらに、実施例１のアンモニア希釈液に代えて、エタノール１６０．３ｇと２９．１％アンモニア水溶液４０．５ｇを混合したアンモニア希釈液を使用し、それ以外は、実施例１と同様にシリカゾルの調製を行った。このシリカゾルの分散質であるシリカ微粒子に関する測定結果を表１に記す。
[Example 2]
Instead of the mixed solvent of Example 1, a mixed solvent obtained by adding 416.1 g of ethanol to 177 g of ultrapure water was used. Further, instead of the ammonia dilution liquid of Example 1, 160.3 g of ethanol and 29. A silica sol was prepared in the same manner as in Example 1 except that an ammonia dilution mixed with 40.5 g of a 1% aqueous ammonia solution was used. Table 1 shows the measurement results regarding silica fine particles which are the dispersoid of this silica sol.
［実施例３］
実施例１のアンモニア希釈液に代えて、エタノール１００ｇと２９．１％アンモニア水溶液４０．５ｇを混合したアンモニア希釈液を使用し、テトラエトキシラン溶液とアンモニア希釈液の添加時間を６時間とし、それ以外は実施例１と同様にシリカゾルの調製を行った。このシリカゾルの分散質であるシリカ微粒子に関する測定結果を表１に記す。また、このシリカゾルの電子顕微鏡写真（倍率３０万倍）を図１に記す。
[Example 3]
Instead of the ammonia dilution liquid of Example 1, an ammonia dilution liquid obtained by mixing 100 g of ethanol and 40.5 g of 29.1% aqueous ammonia solution was used, and the addition time of the tetraethoxylane solution and the ammonia dilution liquid was set to 6 hours. Except for the above, silica sol was prepared in the same manner as in Example 1. Table 1 shows the measurement results regarding silica fine particles which are the dispersoid of this silica sol. An electron micrograph (magnification of 300,000 times) of this silica sol is shown in FIG.
［実施例４］
実施例１の混合溶媒に代えて、超純水１７７ｇにエタノール４１６．１ｇを添加してなる混合溶媒を使用し、実施例１のアンモニア希釈液に代えて、エタノール１００ｇと２９．１％アンモニア水溶液４０．５ｇを混合したアンモニア希釈液を使用し、テトラエトキシラン溶液とアンモニア希釈液の添加時間を１０時間とし、それ以外は実施例１と同様にシリカゾルの調製を行った。このシリカゾルの分散質であるシリカ微粒子に関する測定結果を表１に記す。
[Example 4]
Instead of the mixed solvent of Example 1, a mixed solvent obtained by adding 416.1 g of ethanol to 177 g of ultrapure water was used, and instead of the ammonia dilution liquid of Example 1, 100 g of ethanol and 29.1% aqueous ammonia solution were used. A silica sol was prepared in the same manner as in Example 1 except that an ammonia diluted solution mixed with 40.5 g was used, and the addition time of the tetraethoxylane solution and the ammonia diluted solution was 10 hours. Table 1 shows the measurement results regarding silica fine particles which are the dispersoid of this silica sol.
［実施例５］
実施例１のアンモニア希釈液に代えて、エタノール１００ｇと２９．１％アンモニア水溶液４０．５ｇを混合したアンモニア希釈液を使用し、テトラエトキシラン溶液とアンモニア希釈液の添加時間を１０時間とし、それ以外は実施例１と同様にシリカゾルの調製を行った。このシリカゾルの分散質であるシリカ微粒子に関する測定結果を表１に記す。
[Example 5]
Instead of the ammonia dilution solution of Example 1, an ammonia dilution solution obtained by mixing 100 g of ethanol and 40.5 g of 29.1% aqueous ammonia solution was used, and the addition time of the tetraethoxylane solution and the ammonia dilution solution was set to 10 hours. Except for the above, silica sol was prepared in the same manner as in Example 1. Table 1 shows the measurement results regarding silica fine particles which are the dispersoid of this silica sol.
［比較例１］
テトラエトキシシラン（多摩化学株式会社製：エチルシリケート２８、ＳｉＯ2 ＝２８質量％）５３２． ５ｇを、水−メタノール混合溶媒［水とメタノールの重量比＝２：８
］２４５０ｇに溶解させてなるテトラエトキシシラン溶液２９８２． ５ｇと、濃度０． ２５質量％のアンモニア水溶液５９６． ４ｇとを、６０℃に保持した水−メタノール混
合溶媒（純水１３９． １ｇとメタノール１６９． ９ｇからなる）に、同時に２０時間かけて添加した。なお、アンモニア／テトラエトキシシラン＝０． ０３４（モル比）だっ
た。添加終了後、さらに６５℃で、３時間熟成した。
[Comparative Example 1]
Tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: ethyl silicate 28, SiO 2 = 28 mass%) 532. 5 g of water-methanol mixed solvent [weight ratio of water to methanol = 2: 8
] A tetraethoxysilane solution 2982 dissolved in 2450 g. 5 g, concentration 0. 25% by mass aqueous ammonia solution 596. 4 g was simultaneously added to a water-methanol mixed solvent maintained at 60 ° C. (comprising 139.1 g of pure water and 169.9 g of methanol) over 20 hours. In addition, ammonia / tetraethoxysilane = 0. 034 (molar ratio). After completion of the addition, the mixture was further aged at 65 ° C. for 3 hours.
その後、限外濾過膜で未反応のテトラエトキシシラン、メタノール、アンモニアをほぼ完全に除去し、両イオン交換樹脂で精製し、ついで限外濾過膜で濃縮し、固形分濃度２０質量％のシリカゾルを得た。このシリカゾルの分散質であるシリカ微粒子に関する測定結果を表１に記す。 Thereafter, unreacted tetraethoxysilane, methanol, and ammonia are removed almost completely with an ultrafiltration membrane, purified with both ion exchange resins, and then concentrated with an ultrafiltration membrane to obtain a silica sol having a solid concentration of 20% by mass. Obtained. Table 1 shows the measurement results regarding silica fine particles which are the dispersoid of this silica sol.
［比較例２］
触媒化成工業株式会社製カタロイド（商標）ＳＩ−５０（ＢＥＴ法により測定された比表面積から換算された平均粒子径：２５ｎｍ）をシリカ濃度２０質量％に調整し、炭素含有量、Ｎａ含有量を測定し、結果を表１に示した。
[Comparative Example 2]
Cataloid (trademark) SI-50 (average particle diameter converted from the specific surface area measured by the BET method: 25 nm) manufactured by Catalyst Chemical Industry Co., Ltd. is adjusted to a silica concentration of 20% by mass, and the carbon content and Na content are adjusted. The results are shown in Table 1.
［比較例３］
超純水５９９ｇにエタノール８９９ｇとを混合した混合溶媒を６５℃に加熱して、これにテトラエトキシシラン(多摩化学製エチルシリケート２８、ＳｉＯ2=２８．８質量％)１０．００ｋｇとエタノール１８．９９ｋｇを混合したテトラエトキシラン溶液、および超純水１０．４１ｋｇと２９．１％アンモニア水溶液１６９．５ｇを混合したアンモニア希釈液とを同時に１０時間かけて添加した。 添加終了後、さらに６５℃で３時間熟成した。そして、限外濾過膜で固形分濃度１５質量％まで濃縮し未反応のテトラエトキシシランを除去した。さらに、ロータリーエバポレーターでエタノール、アンモニアをほぼ除去し固形分濃度１２．６質量％のシリカゾルを得た。このシリカゾルの分散質であるシリカ微粒子に関する測定結果を表１に記す。
[Comparative Example 3]
A mixed solvent obtained by mixing 599 g of ultrapure water and 899 g of ethanol was heated to 65 ° C., and 10.00 kg of tetraethoxysilane (Tama Chemical Ethyl silicate 28, SiO 2 = 28.8 mass%) and ethanol 18. A tetraethoxylane solution mixed with 99 kg and an ammonia diluted solution mixed with 10.41 kg of ultrapure water and 169.5 g of 29.1% aqueous ammonia solution were simultaneously added over 10 hours. After completion of the addition, the mixture was further aged at 65 ° C. for 3 hours. And it concentrated to 15 mass% of solid content with the ultrafiltration membrane, and unreacted tetraethoxysilane was removed. Further, ethanol and ammonia were almost removed by a rotary evaporator to obtain a silica sol having a solid content concentration of 12.6% by mass. Table 1 shows the measurement results regarding silica fine particles which are the dispersoid of this silica sol.
［比較例４］
超純水８５１．２ｇにメタノール５６７．７gを添加した混合溶媒を６５℃に加熱して
、これにテトラメトキシシラン(メチルシリケートＳｉＯ2=３９．６質量％)８，２９７．６ｇとメタノール２１，５８９．４ｇを混合したテトラメトキシラン溶液及び、超純水１１，２４２．１ｇと２９．１質量％アンモニア水溶液７８６．２ｇとを同時に１８時間か
けて同時に添加した。添加終了後、さらにこの温度で３時間熟成した。その後限外濾過膜で固形分濃度１５質量％まで濃縮し未反応のテトラメトキシシランを除去した。さらにロータリーエバポレーターでメタノール、アンモニアをほぼ除去し固形分濃度１２．６質量％のシリカ微粒子分散液を得た。このシリカゾルの分散質であるシリカ微粒子に関する測定結果を表１に記す。
[Comparative Example 4]
A mixed solvent in which 567.7 g of methanol was added to 851.2 g of ultrapure water was heated to 65 ° C., and 8,297.6 g of tetramethoxysilane (methyl silicate SiO 2 = 39.6 mass%) and methanol 21, A tetramethoxylane solution mixed with 589.4 g, 11,242.1 g of ultrapure water, and 786.2 g of a 29.1 mass% ammonia aqueous solution were simultaneously added over 18 hours. After completion of the addition, the mixture was further aged at this temperature for 3 hours. Thereafter, it was concentrated with an ultrafiltration membrane to a solid concentration of 15% by mass to remove unreacted tetramethoxysilane. Further, methanol and ammonia were substantially removed by a rotary evaporator to obtain a silica fine particle dispersion having a solid content concentration of 12.6% by mass. Table 1 shows the measurement results regarding silica fine particles which are the dispersoid of this silica sol.
［比較例５］
超純水２，６３２ｇに０．２８質量％アンモニア水溶液５７．８ｇと陰イオン性界面活性剤（花王株式会社製ペレックスＳＳ-Ｌ）の３．０gを混合したものをゆっくり添加し、３０分攪拌した。さらにメチルトリメトキシラン（信越化学株式会社製ＫＢＭ-１３）の
３００gを室温にて、１３．５時間かけて添加した。添加終了後、室温で、さらに３時間
熟成した。得られたゾルを限外濾過膜で固形分濃度１２質量％まで濃縮し、未反応のメチルトリメトキシシランを除去した。このシリカゾルの分散質であるシリカ微粒子に関する測定結果を表１に記す。
[Comparative Example 5]
A mixture of 2,632 g of ultrapure water and 57.8 g of 0.28 mass% aqueous ammonia solution and 3.0 g of an anionic surfactant (Perex SS-L manufactured by Kao Corporation) was slowly added and stirred for 30 minutes. did. Furthermore, 300 g of methyltrimethoxylane (KBM-13 manufactured by Shin-Etsu Chemical Co., Ltd.) was added at room temperature over 13.5 hours. After completion of the addition, the mixture was further aged at room temperature for 3 hours. The obtained sol was concentrated with an ultrafiltration membrane to a solid concentration of 12% by mass to remove unreacted methyltrimethoxysilane. Table 1 shows the measurement results regarding silica fine particles which are the dispersoid of this silica sol.
本発明のシリカゾルは、シリコンウェーハ、化合物半導体ウェーハ、磁気ディスク基板、アルミニウム基板などの電子材料の研磨加工時に用いられる研磨材または研磨用組成物として好適である。また、化粧料の原料、インク受容層の成分、樹脂組成物用の充填材、被膜形成用組成物の充填材などに好適に使用することが可能である。 The silica sol of the present invention is suitable as an abrasive or a polishing composition used in polishing electronic materials such as silicon wafers, compound semiconductor wafers, magnetic disk substrates, and aluminum substrates. Further, it can be suitably used as a raw material for cosmetics, a component of an ink receiving layer, a filler for a resin composition, a filler for a film forming composition, and the like.
Claims (6)
該球状シリカ微粒子のＢＥＴ法により測定された比表面積を（ＳＡ１）とし、画像解析法により測定される該シリカ微粒子の平均粒子径（Ｄ２）から換算した比表面積を（ＳＡ２）としたときの表面粗度（ＳＡ１）／（ＳＡ２）の値が、１．９〜５．０の範囲にあり、該平均粒子径（Ｄ２）が１０〜１５０ｎｍの範囲にあり、該球状シリカ微粒子の粒子径の変動係数が３．０〜２０％の範囲にあり、ナトリウム含有割合が１００質量ｐｐｍ以下、炭素含有割合が０．１〜５質量％の範囲にあることを特徴とするシリカゾル。 A silica sol obtained by dispersing spherical silica fine particles having a plurality of hook-shaped protrusions on a surface in a solvent,
Surface when the specific surface area of the spherical silica particles measured by the BET method is (SA1) and the specific surface area converted from the average particle diameter (D2) of the silica particles measured by the image analysis method is (SA2) The roughness (SA1) / (SA2) value is in the range of 1.9 to 5.0, the average particle size (D2) is in the range of 10 to 150 nm, and the particle size of the spherical silica fine particles varies. A silica sol having a coefficient of 3.0 to 20%, a sodium content of 100 mass ppm or less, and a carbon content of 0.1 to 5 mass%.
一般式（１）：（ＲＯ）4Ｓｉ （Ｒは炭素数２〜４のアルキル基） The temperature range of the mixed solvent containing a water-soluble organic solvent and water is maintained at 30 to 150 ° C., and 1) a water-soluble organic solvent solution of a tetrafunctional silane compound represented by the following general formula (1) and 2 ) Silica sol obtained by hydrolytic condensation of the tetrafunctional silane compound by adding the alkali catalyst solution simultaneously or intermittently, and further aging in the temperature range of 30 to 150 ° C. after completion of the addition. 3. The method for producing a silica sol according to claim 1, wherein the hydrolytic condensation is carried out with the molar ratio of water to the tetrafunctional silane compound being in the range of 2 or more and less than 4. 4.
General formula (1): (RO) 4 Si (R is an alkyl group having 2 to 4 carbon atoms)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007339796A JP5188175B2 (en) | 2007-12-28 | 2007-12-28 | Silica sol and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007339796A JP5188175B2 (en) | 2007-12-28 | 2007-12-28 | Silica sol and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009161371A JP2009161371A (en) | 2009-07-23 |
| JP5188175B2 true JP5188175B2 (en) | 2013-04-24 |
Family
ID=40964433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007339796A Active JP5188175B2 (en) | 2007-12-28 | 2007-12-28 | Silica sol and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5188175B2 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010024119A (en) * | 2008-07-24 | 2010-02-04 | Jgc Catalysts & Chemicals Ltd | Method for producing confetti-like silica sol |
| JP5615529B2 (en) * | 2009-11-16 | 2014-10-29 | 日揮触媒化成株式会社 | Inorganic oxide fine particle dispersion, polishing particle dispersion, and polishing composition |
| JP5477192B2 (en) | 2010-06-23 | 2014-04-23 | 富士ゼロックス株式会社 | Method for producing silica particles |
| JP5477193B2 (en) | 2010-06-24 | 2014-04-23 | 富士ゼロックス株式会社 | Silica particles and method for producing the same |
| JP5488255B2 (en) | 2010-06-25 | 2014-05-14 | 富士ゼロックス株式会社 | Silica particles and method for producing the same |
| JP5741005B2 (en) | 2011-01-20 | 2015-07-01 | 富士ゼロックス株式会社 | Resin particles and method for producing the same |
| JP5724401B2 (en) | 2011-01-19 | 2015-05-27 | 富士ゼロックス株式会社 | Resin particles and method for producing the same |
| JP5712824B2 (en) | 2011-07-06 | 2015-05-07 | 富士ゼロックス株式会社 | Silica particles and method for producing the same |
| JP5857525B2 (en) * | 2011-08-18 | 2016-02-10 | 富士ゼロックス株式会社 | Silica particles and method for producing the same |
| JP5831378B2 (en) | 2011-12-01 | 2015-12-09 | 富士ゼロックス株式会社 | Silica composite particles and method for producing the same |
| JP5915555B2 (en) | 2013-01-28 | 2016-05-11 | 富士ゼロックス株式会社 | Silica composite particles and method for producing the same |
| JP6603142B2 (en) * | 2015-01-20 | 2019-11-06 | 日揮触媒化成株式会社 | Silica composite fine particle dispersion, method for producing the same, and polishing slurry containing silica composite fine particle dispersion |
| JP6703437B2 (en) * | 2016-04-22 | 2020-06-03 | 日揮触媒化成株式会社 | Silica-based composite fine particle dispersion, method for producing the same, and polishing slurry containing the silica-based composite fine particle dispersion |
| SG10201904669TA (en) * | 2018-06-28 | 2020-01-30 | Kctech Co Ltd | Polishing Slurry Composition |
| KR102302664B1 (en) * | 2019-11-07 | 2021-09-14 | 한국전기연구원 | Ultra-high purity, high concentration, spherical and non-spherical colloidal silica nano-sol and fabrication method thereof for semiconductor CMP slurry |
| JP7370904B2 (en) * | 2020-03-05 | 2023-10-30 | 株式会社トッパンインフォメディア | Method for polishing interlayer insulation material of semiconductor package substrate |
| CN116768220B (en) * | 2023-07-04 | 2023-12-29 | 山东科翰硅源新材料有限公司 | Method for rapidly synthesizing high-concentration non-spherical silica sol |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3616133A1 (en) * | 1985-09-25 | 1987-11-19 | Merck Patent Gmbh | SPHERICAL SIO (DOWN ARROW) 2 (DOWN ARROW) PARTICLES |
| TW225511B (en) * | 1989-12-14 | 1994-06-21 | Nissan Chemical Ind Ltd | |
| JP4642165B2 (en) * | 1997-08-07 | 2011-03-02 | 日揮触媒化成株式会社 | Porous silica-based coating solution, coated substrate and short fibrous silica |
| JP2002038049A (en) * | 2000-07-28 | 2002-02-06 | Ube Nitto Kasei Co Ltd | Silica based fine particle and its manufacturing method |
| JP2002338232A (en) * | 2001-05-18 | 2002-11-27 | Nippon Chem Ind Co Ltd | Secondary flocculated colloidal silica, method for producing the same and abrasive composition using the same |
| JP2004315300A (en) * | 2003-04-17 | 2004-11-11 | Nippon Steel Chem Co Ltd | Silica fine particle, silica colloid in which silica fine particles are dispersed and method of manufacturing the same |
| JP5080061B2 (en) * | 2005-11-10 | 2012-11-21 | 多摩化学工業株式会社 | Method for producing neutral colloidal silica |
-
2007
- 2007-12-28 JP JP2007339796A patent/JP5188175B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009161371A (en) | 2009-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5188175B2 (en) | Silica sol and method for producing the same | |
| JP5084670B2 (en) | Silica sol and method for producing the same | |
| JP5587957B2 (en) | Konpira sugar-like sol | |
| JP5599440B2 (en) | Deformed silica sol | |
| JP5602358B2 (en) | Non-spherical silica sol, method for producing the same, and polishing composition | |
| US7753974B2 (en) | Polishing composition for semiconductor wafer, method for production thereof and polishing method | |
| JP4712556B2 (en) | Alkali-resistant vertical colloidal silica particles and method for producing the same | |
| WO2010052945A1 (en) | Aspherical silica sol, process for producing the same, and composition for polishing | |
| JP2009137791A (en) | Non-spherical combined silica sol and method for producing the same | |
| JP2009078935A (en) | "konpeito" (pointed sugar candy ball)-like composite silica sol | |
| JP2008273780A (en) | Modified silica-based sol and method for preparing the same | |
| JP4911960B2 (en) | Method for producing anisotropic silica sol | |
| JP5615529B2 (en) | Inorganic oxide fine particle dispersion, polishing particle dispersion, and polishing composition | |
| JP6868970B2 (en) | Dispersion liquid, its manufacturing method, and CMP polishing agent using it | |
| JP6207345B2 (en) | Method for producing silica particles | |
| TWI786275B (en) | Composition for chemical mechanical polishing and chemical mechanical polishing method | |
| TW202020102A (en) | Polishing composition and polishing system | |
| JP5464834B2 (en) | Polishing silica sol, polishing composition, and method for producing polishing silica sol | |
| JP6598719B2 (en) | Method for producing silica-based composite particle dispersion | |
| JP4954046B2 (en) | Method for producing ammonium-containing silica-based sol | |
| JP2009078936A (en) | Method for preparing "konpeito" (pointed sugar candy ball)-like composite silica sol | |
| JP2013227168A (en) | Colloidal silica having silica particle with unevenness on the surface, method for manufacturing the same, and polishing material using the same | |
| JP5346167B2 (en) | Particle-linked alumina-silica composite sol and method for producing the same | |
| JP7038031B2 (en) | Abrasive grain dispersion for polishing containing ceria-based composite fine particle dispersion, its manufacturing method, and ceria-based composite fine particle dispersion. | |
| JP2010024119A (en) | Method for producing confetti-like silica sol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100819 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20100819 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120316 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120424 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120625 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121225 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130122 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160201 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5188175 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |