JP6829007B2 - A polishing slurry containing a silica-based composite fine particle dispersion, a method for producing the same, and a silica-based composite fine particle dispersion. - Google Patents
A polishing slurry containing a silica-based composite fine particle dispersion, a method for producing the same, and a silica-based composite fine particle dispersion. Download PDFInfo
- Publication number
- JP6829007B2 JP6829007B2 JP2016099926A JP2016099926A JP6829007B2 JP 6829007 B2 JP6829007 B2 JP 6829007B2 JP 2016099926 A JP2016099926 A JP 2016099926A JP 2016099926 A JP2016099926 A JP 2016099926A JP 6829007 B2 JP6829007 B2 JP 6829007B2
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- JP
- Japan
- Prior art keywords
- silica
- particles
- composite fine
- based composite
- particle dispersion
- 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.)
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 626
- 239000000377 silicon dioxide Substances 0.000 title claims description 300
- 239000010419 fine particle Substances 0.000 title claims description 277
- 239000006185 dispersion Substances 0.000 title claims description 201
- 239000002131 composite material Substances 0.000 title claims description 179
- 238000005498 polishing Methods 0.000 title claims description 138
- 238000004519 manufacturing process Methods 0.000 title claims description 43
- 239000002002 slurry Substances 0.000 title claims description 38
- 239000002245 particle Substances 0.000 claims description 296
- 239000007788 liquid Substances 0.000 claims description 77
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 64
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 56
- 239000000758 substrate Substances 0.000 claims description 42
- 238000004448 titration Methods 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 37
- 239000006228 supernatant Substances 0.000 claims description 33
- 229910052684 Cerium Inorganic materials 0.000 claims description 28
- 239000012535 impurity Substances 0.000 claims description 28
- 239000000084 colloidal system Substances 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 27
- 238000011282 treatment Methods 0.000 claims description 25
- 125000002091 cationic group Chemical group 0.000 claims description 24
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000004065 semiconductor Substances 0.000 claims description 23
- 239000011164 primary particle Substances 0.000 claims description 20
- 238000005259 measurement Methods 0.000 claims description 16
- 230000001133 acceleration Effects 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 238000002441 X-ray diffraction Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 229910052776 Thorium Inorganic materials 0.000 claims description 11
- 229910052770 Uranium Inorganic materials 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 230000005540 biological transmission Effects 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 47
- -1 lanthanium Chemical compound 0.000 description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 239000007787 solid Substances 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 229910004298 SiO 2 Inorganic materials 0.000 description 22
- 239000000047 product Substances 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 19
- 229910000420 cerium oxide Inorganic materials 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 125000004429 atom Chemical group 0.000 description 16
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 16
- 235000012239 silicon dioxide Nutrition 0.000 description 15
- 238000005119 centrifugation Methods 0.000 description 14
- 239000004094 surface-active agent Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000003917 TEM image Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 239000002202 Polyethylene glycol Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 10
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 150000002433 hydrophilic molecules Chemical class 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 235000011054 acetic acid Nutrition 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000003703 image analysis method Methods 0.000 description 7
- 238000009616 inductively coupled plasma Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000000108 ultra-filtration Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000005215 alkyl ethers Chemical class 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000002296 dynamic light scattering Methods 0.000 description 6
- 150000002391 heterocyclic compounds Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000006061 abrasive grain Substances 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000011246 composite particle Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- 239000006174 pH buffer Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 239000011882 ultra-fine particle Substances 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003082 abrasive agent Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 238000000790 scattering method Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 150000003871 sulfonates Chemical class 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
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- 239000010452 phosphate Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 238000003918 potentiometric titration Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- FALCMQXTWHPRIH-UHFFFAOYSA-N 2,3-dichloroprop-1-ene Chemical compound ClCC(Cl)=C FALCMQXTWHPRIH-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
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- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 2
- 102220470957 Amiloride-sensitive sodium channel subunit delta_R21A_mutation Human genes 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
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Description
本発明は、半導体デバイス製造に使用される研磨剤として好適なシリカ系複合微粒子分散液に関し、特に基板上に形成された被研磨膜を、化学機械的研磨（ケミカルメカニカルポリッシング、ＣＭＰ）で平坦化するためのシリカ系複合微粒子分散液、その製造方法及びシリカ系複合微粒子分散液を含む研磨用スラリーに関する。 The present invention relates to a silica-based composite fine particle dispersion suitable as an abrasive used in semiconductor device manufacturing, and particularly flattens a film to be polished formed on a substrate by chemical mechanical polishing (CMP). The present invention relates to a silica-based composite fine particle dispersion, a method for producing the same, and a polishing slurry containing the silica-based composite fine particle dispersion.
半導体基板、配線基板などの半導体デバイスなどは、高密度化・微細化することで高性能化を実現している。この半導体の製造工程においては、いわゆるケミカルメカニカルポリッシング（ＣＭＰ）が適用されており、具体的にはシャロートレンチ素子分離、層間絶縁膜の平坦化、コンタクトプラグやＣｕダマシン配線の形成などに必須の技術となっている。 Semiconductor devices such as semiconductor substrates and wiring boards have achieved high performance by increasing the density and miniaturization. So-called chemical mechanical polishing (CMP) is applied in the manufacturing process of this semiconductor. Specifically, it is an essential technology for separating shallow trench elements, flattening an interlayer insulating film, and forming contact plugs and Cu damascene wiring. It has become.
一般にＣＭＰ用研磨剤は、砥粒とケミカル成分とからなり、ケミカル成分は対象被膜を酸化や腐食などさせることにより研磨を促進させる役割を担う。一方で砥粒は機械的作用により研磨する役割を持ち、コロイダルシリカやヒュームドシリカ、セリア粒子が砥粒として使われる。特にセリア粒子は酸化ケイ素膜に対して特異的に高い研磨速度を示すことから、シャロートレンチ素子分離工程での研磨に適用されている。
シャロートレンチ素子分離工程では、酸化ケイ素膜の研磨だけではなく、窒化ケイ素膜の研磨も行われる。素子分離を容易にするためには、酸化ケイ素膜の研磨速度が高く、窒化ケイ素膜の研磨速度が低い事が望ましく、この研磨速度比（選択比）も重要である。
Generally, an abrasive for CMP is composed of abrasive grains and a chemical component, and the chemical component plays a role of promoting polishing by oxidizing or corroding the target film. On the other hand, abrasive grains have a role of polishing by mechanical action, and colloidal silica, fumed silica, and ceria particles are used as abrasive grains. In particular, ceria particles show a specifically high polishing rate with respect to the silicon oxide film, and are therefore applied to polishing in the shallow trench element separation step.
In the shallow trench element separation step, not only the silicon oxide film is polished, but also the silicon nitride film is polished. In order to facilitate element separation, it is desirable that the polishing rate of the silicon oxide film is high and the polishing rate of the silicon nitride film is low, and this polishing rate ratio (selection ratio) is also important.
従来、このような部材の研磨方法として、比較的粗い１次研磨処理を行った後、精密な２次研磨処理を行うことにより、平滑な表面あるいはスクラッチなどの傷が少ない極めて高精度の表面を得る方法が行われている。
このような仕上げ研磨としての２次研磨に用いる研磨剤に関して、従来、例えば次のような方法等が提案されている。
Conventionally, as a polishing method for such a member, a relatively rough primary polishing process is then performed, and then a precise secondary polishing process is performed to obtain a smooth surface or an extremely high-precision surface with few scratches. The way to get it is done.
Conventionally, for example, the following methods have been proposed with respect to the polishing agent used for the secondary polishing as such finish polishing.
例えば、特許文献１には、硝酸第一セリウムの水溶液と塩基とを、ｐＨが５〜１０となる量比で攪拌混合し、続いて７０〜１００℃に急速加熱し、その温度で熟成することを特徴とする酸化セリウム単結晶からなる酸化セリウム超微粒子（平均粒子径１０〜８０ｎｍ）の製造方法が記載されており、更にこの製造方法によれば、粒子径の均一性が高く、かつ粒子形状の均一性も高い酸化セリウム超微粒子を提供できると記載されている。 For example, in Patent Document 1, an aqueous solution of first cerium nitrate and a base are stirred and mixed at an amount ratio of 5 to 10 and then rapidly heated to 70 to 100 ° C. and aged at that temperature. A method for producing ultrafine particles of cerium oxide (average particle size of 10 to 80 nm) composed of a cerium oxide single crystal is described, and further, according to this production method, the particle size is highly uniform and the particle shape is high. It is stated that cerium oxide ultrafine particles having high uniformity can be provided.
また、非特許文献１は、特許文献１に記載の酸化セリウム超微粒子の製造方法と類似した製造工程を含むセリアコートシリカの製造方法を開示している。このセリアコートシリカの製造方法は、特許文献１に記載の製造方法に含まれるような焼成―分散の工程を有さないものである。 In addition, Non-Patent Document 1 discloses a method for producing ceria-coated silica, which comprises a production process similar to the method for producing cerium oxide ultrafine particles described in Patent Document 1. This method for producing ceria-coated silica does not include a firing-dispersion step as included in the production method described in Patent Document 1.
さらに、特許文献２には、非晶質のシリカ粒子Ａの表面に、ジルコニウム、チタニウム、鉄、マンガン、亜鉛、セリウム、イットリウム、カルシウム、マグネシウム、フッ素、ランタニウム、ストロンチウムより選ばれた１種以上の元素を含む結晶質の酸化物層Ｂを有することを特徴とするシリカ系複合粒子が記載されている。また、好ましい態様として、非晶質のシリカ粒子Ａの表面に、アルミニウム等の元素を含む非晶質の酸化物層であって、非晶質のシリカ層とは異なる非晶質の酸化物層Ｃを有し、さらに、その上にジルコニウム、チタニウム、鉄、マンガン、亜鉛、セリウム、イットリウム、カルシウム、マグネシウム、フッ素、ランタニウム、ストロンチウムより選ばれた１種以上の元素を含む結晶質の酸化物層Ｂを有することを特徴とするシリカ系複合粒子が記載されている。そして、このようなシリカ系複合粒子は、非晶質のシリカ粒子Ａの表面に、結晶質の酸化物層Ｂを有するために、研磨速度を向上させることができ、かつ、シリカ粒子に前処理をすることにより、焼成時に粒子同士の焼結が抑制され研磨スラリー中での分散性を向上させることができ、さらに、酸化セリウムを含まない、あるいは酸化セリウムの使用量を大幅に低減することができるので、安価であって研磨性能の高い研磨材を提供することができると記載されている。また、シリカ系粒子Ａと酸化物層Ｂの間にさらに非晶質の酸化物層Ｃを有するものは、粒子の焼結抑制効果と研磨速度を向上させる効果に特に優れると記載されている。 Further, in Patent Document 2, one or more kinds selected from zirconium, titanium, iron, manganese, zinc, cerium, yttrium, calcium, magnesium, fluorine, lanthanium, and strontium are provided on the surface of amorphous silica particles A. Described are silica-based composite particles characterized by having a crystalline oxide layer B containing an element. Further, as a preferred embodiment, an amorphous oxide layer containing an element such as aluminum on the surface of the amorphous silica particles A, which is different from the amorphous silica layer. A crystalline oxide layer having C and further containing one or more elements selected from zirconium, titanium, iron, manganese, zinc, cerium, ittrium, calcium, magnesium, fluorine, lanthanum, and strontium. Silica-based composite particles characterized by having B are described. Since such a silica-based composite particle has a crystalline oxide layer B on the surface of the amorphous silica particle A, the polishing speed can be improved and the silica particles are pretreated. By doing so, sintering of particles can be suppressed during firing and dispersibility in the abrasive slurry can be improved, and cerium oxide is not contained or the amount of cerium oxide used can be significantly reduced. It is stated that it is possible to provide an abrasive material that is inexpensive and has high polishing performance. Further, it is described that those having an amorphous oxide layer C between the silica-based particles A and the oxide layer B are particularly excellent in the effect of suppressing the sintering of the particles and the effect of improving the polishing rate.
しかしながら、特許文献１に記載の酸化セリウム超微粒子について、本発明者が実際に製造して検討したところ、研磨速度が低く、さらに、研磨基材の表面に欠陥（面精度の悪化、スクラッチ増加、研磨基材表面への研磨材の残留）を生じやすいことが判明した。
これは、焼成工程を含むセリア粒子の製造方法（焼成によりセリア粒子の結晶化度が高まる）に比べて、特許文献１に記載の酸化セリウム超微粒子の製法は、焼成工程を含まず、液相（硝酸第一セリウムを含む水溶液）から酸化セリウム粒子を結晶化させるだけなので、生成する酸化セリウム粒子の結晶化度が相対的に低く、また、焼成処理を経ないため酸化セリウムが母粒子と固着せず、酸化セリウムが研磨基材の表面に残留することが主要因であると、本発明者は推定している。
However, when the present inventor actually produced and examined the cerium oxide ultrafine particles described in Patent Document 1, the polishing rate was low, and further, defects on the surface of the polishing base material (deterioration of surface accuracy, increase in scratches, etc.) It was found that (residue of abrasive material on the surface of the polishing base material) is likely to occur.
This is because the method for producing cerium oxide ultrafine particles described in Patent Document 1 does not include a firing step and is a liquid phase, as compared with a method for producing ceria particles including a firing step (the degree of crystallization of ceria particles is increased by firing). Since the cerium oxide particles are only crystallized from (an aqueous solution containing primary cerium nitrate), the degree of crystallization of the produced cerium oxide particles is relatively low, and since the cerium oxide particles are not subjected to a firing treatment, the cerium oxide is solidified with the mother particles. The present inventor presumes that the main factor is that cerium oxide remains on the surface of the abrasive substrate without being attached.
また、非特許文献１に記載のセリアコートシリカは焼成していないため、現実の研磨速度は低いと考えられ、また、研磨基材の表面への粒子の残留も懸念される。 Further, since the ceria-coated silica described in Non-Patent Document 1 is not calcined, it is considered that the actual polishing rate is low, and there is a concern that particles may remain on the surface of the polishing substrate.
さらに、特許文献２に記載の酸化物層Ｃを有する態様のシリカ系複合粒子を用いて研磨すると、アルミニウム等の不純物が半導体デバイスの表面に残留し、半導体デバイスへ悪影響を及ぼすこともあることを、本発明者は見出した。 Further, when the silica-based composite particles having the oxide layer C described in Patent Document 2 are used for polishing, impurities such as aluminum may remain on the surface of the semiconductor device and adversely affect the semiconductor device. , The inventor has found.
本発明は上記のような課題を解決することを目的とする。すなわち、本発明は、シリカ膜、Ｓｉウェハや難加工材であっても高速で研磨することができ、同時に高面精度（低スクラッチ等）を達成でき、半導体基板、配線基板などの半導体デバイスの表面の研磨に好ましく用いることができるシリカ系複合微粒子分散液、その製造方法及びシリカ系複合微粒子分散液を含む研磨用スラリーを提供することを目的とする。 An object of the present invention is to solve the above problems. That is, the present invention can polish a silica film, a Si wafer, or a difficult-to-process material at high speed, and at the same time, can achieve high surface accuracy (low scratch, etc.), and can be used for semiconductor devices such as semiconductor substrates and wiring substrates. It is an object of the present invention to provide a silica-based composite fine particle dispersion that can be preferably used for surface polishing, a method for producing the same, and a polishing slurry containing the silica-based composite fine particle dispersion.
本発明者は上記課題を解決するため鋭意検討し、本発明を完成させた。
本発明は以下の（１）〜（１１）である。
（１）非晶質シリカを主成分とする母粒子の表面上に結晶性セリアを主成分とする子粒子を有し、下記［１］から[４]の特徴を備える平均粒子径５０〜３５０ｎｍのシリカ系複合微粒子を含む、シリカ系複合微粒子分散液。
［１］前記シリカ系複合微粒子は、シリカとセリアとの質量比が１００：１１〜３１６であること。
［２］前記シリカ系複合微粒子は、Ｘ線回折に供すると、セリアの結晶相のみが検出されること。
［３］前記シリカ系複合微粒子に含まれる、一次粒子が直接的または間接的に２個または３個連結した結合粒子の重量割合が６０％以上であること。
（２）前記シリカ系複合微粒子に含まれる不純物の含有割合が、次の（ａ）及び（ｂ）のとおりであることを特徴とする上記（１）に記載のシリカ系複合微粒子分散液。
（ａ）Ｎａ、Ａｇ、Ａｌ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｋ、Ｍｇ、Ｎｉ、Ｔｉ、Ｚｎ及びＺｒの含有率が、それぞれ１００ｐｐｍ以下。
（ｂ）Ｕ、Ｔｈ、Ｃｌ、ＮＯ3、ＳＯ4及びＦの含有率が、それぞれ５ｐｐｍ以下。
（３）さらに、前記子粒子の表面にシリカ被膜を有していることを特徴とする、上記（１）又は（２）に記載のシリカ系複合微粒子分散液。
（４）ｐＨ値が３〜８の範囲である場合の滴定前の流動電位がマイナスの電位であることを特徴とする、上記（１）〜（３）の何れかに記載のシリカ系複合微粒子分散液。
（５）前記シリカ系複合微粒子について、透過型電子顕微鏡を用いて観察できる前記シリカ被膜の部分に電子ビームを選択的に当てたＥＤＳ測定によって求める、Ｃｅ原子数％に対するＳｉ原子数％の比（Ｓｉ原子数％／Ｃｅ原子数％）が０．９以上であることを特徴とする上記（１）〜（４）の何れかに記載のシリカ系複合微粒子分散液。
（６）カチオンコロイド滴定を行った場合に、下記式（１）で表される流動電位変化量（ΔＰＣＤ）と、クニックにおけるカチオンコロイド滴定液の添加量（Ｖ）との比（ΔＰＣＤ／Ｖ）が−１１０．０〜−１５．０となる流動電位曲線が得られる、請求項１〜５のいずれかに記載のシリカ系複合微粒子分散液。
ΔＰＣＤ／Ｖ＝（Ｉ−Ｃ）／Ｖ・・・式（１）
Ｃ：前記クニックにおける流動電位（ｍＶ）
Ｉ：前記流動電位曲線の開始点における流動電位（ｍＶ）
Ｖ：前記クニックにおける前記カチオンコロイド滴定液の添加量（ｍｌ）
（７）上記（１）〜（６）の何れかに記載のシリカ系複合微粒子分散液を含む研磨用スラリー。
（８）シリカ膜が形成された半導体基板の平坦化用研磨スラリーであることを特徴とする上記（７）記載の研磨用スラリー。
（９）下記の工程１〜工程４を含むことを特徴とするシリカ系複合微粒子分散液の製造方法。
工程１：シリカ微粒子が溶媒に分散してなるシリカ微粒子分散液を撹拌し、温度を５〜９８℃、ｐＨを範囲７．０〜９．０に維持しながら、ここへセリウムの金属塩を連続的又は断続的に添加し、前駆体粒子を含む前駆体粒子分散液を得る工程。
工程２：前記前駆体粒子分散液を乾燥させ、４００〜１,２００℃で焼成し、得られた焼成体に、次の（ｉ）又は（ｉｉ）の処理をして焼成体解砕分散液を得る工程。
（ｉ）乾式で解砕・粉砕処理し、溶媒を加えて溶媒分散処理する。
（ｉｉ）溶媒を加えて、湿式で解砕・粉砕処理する。
工程３：前記焼成体解砕分散液を、相対遠心加速度３００Ｇ以上にて遠心分離処理を行い、続いて沈降成分を除去することにより上澄液を得る工程。
工程４：前記上澄液を、相対遠心加速度３００Ｇ以上にて遠心分離処理を行い、続いて沈降成分を回収し、シリカ系複合微粒子分散液を得る工程。
（１０）前記シリカ微粒子に含まれる不純物の含有割合が、次の（ａ）及び（ｂ）のとおりであることを特徴とする上記（９）記載のシリカ系複合微粒子分散液の製造方法。
（ａ）Ｎａ、Ａｇ、Ａｌ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｋ、Ｍｇ、Ｎｉ、Ｔｉ、Ｚｎ及びＺｒの含有率が、それぞれ１００ｐｐｍ以下。
（ｂ）Ｕ、Ｔｈ、Ｃｌ、ＮＯ3、ＳＯ4及びＦの含有率が、それぞれ５ｐｐｍ以下。
（１１）前記工程２の（ｉｉ）が、溶媒を加えて、ｐＨ９．０〜１０．６の範囲にて、湿式で解砕・粉砕処理する処理である、上記（９）又は（１０）に記載のシリカ系複合微粒子分散液の製造方法。
The present inventor has made diligent studies to solve the above problems and completed the present invention.
The present invention is the following (1) to (11).
(1) An average particle diameter of 50 to 350 nm, which has child particles containing crystalline ceria as a main component on the surface of a mother particle containing amorphous silica as a main component and has the following characteristics [1] to [4]. A silica-based composite fine particle dispersion containing the silica-based composite fine particles.
[1] The silica-based composite fine particles have a mass ratio of silica to ceria of 100: 11-316.
[2] When the silica-based composite fine particles are subjected to X-ray diffraction, only the crystal phase of ceria is detected.
[3] The weight ratio of the bonded particles contained in the silica-based composite fine particles in which two or three primary particles are directly or indirectly linked is 60% or more.
(2) The silica-based composite fine particle dispersion liquid according to (1) above, wherein the content ratio of impurities contained in the silica-based composite fine particles is as follows (a) and (b).
(A) The contents of Na, Ag, Al, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn and Zr are 100 ppm or less, respectively.
(B) The contents of U, Th, Cl, NO 3 , SO 4 and F are 5 ppm or less, respectively.
(3) The silica-based composite fine particle dispersion liquid according to (1) or (2) above, which further has a silica film on the surface of the child particles.
(4) The silica-based composite fine particles according to any one of (1) to (3) above, wherein the flow potential before titration is a negative potential when the pH value is in the range of 3 to 8. Dispersion solution.
(5) The ratio of the number of Si atoms to the Ce atom number% determined by EDS measurement in which the silica-based composite fine particles are selectively applied with an electron beam to the silica coating portion that can be observed using a transmission electron microscope (5). The silica-based composite fine particle dispersion according to any one of (1) to (4) above, wherein (Si atom number% / Ce atom number%) is 0.9 or more.
(6) When cationic colloid titration is performed, the ratio (ΔPCD / V) of the flow potential change amount (ΔPCD) represented by the following formula (1) to the addition amount (V) of the cationic colloid titration solution in the knick. The silica-based composite fine particle dispersion according to any one of claims 1 to 5, wherein a flow potential curve having a value of -110.0 to -15.0 can be obtained.
ΔPCD / V = (IC) / V ... Equation (1)
C: Flow potential (mV) in the knick
I: Flow potential (mV) at the start point of the flow potential curve
V: Addition amount (ml) of the cationic colloid titration solution in the knick
(7) A polishing slurry containing the silica-based composite fine particle dispersion according to any one of (1) to (6) above.
(8) The polishing slurry according to (7) above, which is a polishing slurry for flattening a semiconductor substrate on which a silica film is formed.
(9) A method for producing a silica-based composite fine particle dispersion, which comprises the following steps 1 to 4.
Step 1: The silica fine particle dispersion liquid in which the silica fine particles are dispersed in the solvent is stirred, and the metal salt of cerium is continuously added thereto while maintaining the temperature at 5 to 98 ° C. and the pH in the range of 7.0 to 9.0. A step of obtaining a precursor particle dispersion liquid containing precursor particles by adding the particles intermittently or intermittently.
Step 2: The precursor particle dispersion is dried and fired at 400 to 1,200 ° C., and the obtained fired body is subjected to the following treatment (i) or (ii) to crush and disperse the fired body. The process of obtaining.
(I) It is crushed and pulverized by a dry method, and a solvent is added to disperse the solvent.
(Ii) A solvent is added, and the mixture is crushed and pulverized in a wet manner.
Step 3: A step of centrifuging the fired body crushed dispersion at a relative centrifugal acceleration of 300 G or more, and subsequently removing a sedimentation component to obtain a supernatant.
Step 4: A step of centrifuging the supernatant at a relative centrifugal acceleration of 300 G or more, and then recovering the sedimented components to obtain a silica-based composite fine particle dispersion.
(10) The method for producing a silica-based composite fine particle dispersion liquid according to (9) above, wherein the content ratio of impurities contained in the silica fine particles is as described in (a) and (b) below.
(A) The contents of Na, Ag, Al, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn and Zr are 100 ppm or less, respectively.
(B) The contents of U, Th, Cl, NO 3 , SO 4 and F are 5 ppm or less, respectively.
(11) The above-mentioned (9) or (10), wherein (ii) of the step 2 is a process of adding a solvent and performing a wet crushing / crushing treatment in a pH range of 9.0 to 10.6. The method for producing a silica-based composite fine particle dispersion liquid.
本発明によれば、シリカ膜、Ｓｉウェハや難加工材であっても高速で研磨することができ、同時に高面精度（低スクラッチ等）を達成でき、半導体基板、配線基板などの半導体デバイスの表面の研磨に好ましく用いることができるシリカ系複合微粒子分散液、その製造方法及びシリカ系複合微粒子分散液を含む研磨用スラリーを提供することができる。
本発明のシリカ系複合微粒子分散液は、半導体デバイス表面の平坦化に有効であり、特にはシリカ絶縁膜が形成された基板の研磨に好適である。
According to the present invention, even silica films, Si wafers and difficult-to-process materials can be polished at high speed, and at the same time, high surface accuracy (low scratches, etc.) can be achieved, and semiconductor devices such as semiconductor substrates and wiring substrates can be polished. It is possible to provide a silica-based composite fine particle dispersion that can be preferably used for surface polishing, a method for producing the same, and a polishing slurry containing the silica-based composite fine particle dispersion.
The silica-based composite fine particle dispersion liquid of the present invention is effective for flattening the surface of a semiconductor device, and is particularly suitable for polishing a substrate on which a silica insulating film is formed.
本発明について説明する。
本発明は、非晶質シリカを主成分とする母粒子（「母粒子」のことを以下では「シリカ微粒子」ともいう）の表面上に結晶性セリアを主成分とする子粒子を有し、下記［１］から［３］の特徴を備える平均粒子径５０〜３５０ｎｍのシリカ系複合微粒子を含む、シリカ系複合微粒子分散液である。
［１］前記シリカ系複合微粒子は、シリカとセリアとの質量比が１００：１１〜３１６であること。
［２］前記シリカ系複合微粒子は、Ｘ線回折に供すると、セリアの結晶相のみが検出されること。
［３］前記シリカ系複合微粒子に含まれる、一次粒子が直接的または間接的に２個または３個連結した結合粒子の重量割合が６０％以上であること。
このようなシリカ系複合微粒子分散液を、以下では「本発明の分散液」ともいう。
また、本発明の分散液が含むシリカ系複合微粒子を、以下では「本発明の複合微粒子」ともいう。
The present invention will be described.
The present invention has child particles containing crystalline ceria as a main component on the surface of a mother particle containing amorphous silica as a main component (the "mother particle" is also referred to as "silica fine particles" below). It is a silica-based composite fine particle dispersion liquid containing silica-based composite fine particles having an average particle diameter of 50 to 350 nm having the following characteristics [1] to [3].
[1] The silica-based composite fine particles have a mass ratio of silica to ceria of 100: 11-316.
[2] When the silica-based composite fine particles are subjected to X-ray diffraction, only the crystal phase of ceria is detected.
[3] The weight ratio of the bonded particles contained in the silica-based composite fine particles in which two or three primary particles are directly or indirectly linked is 60% or more.
Such a silica-based composite fine particle dispersion is also hereinafter referred to as "dispersion of the present invention".
Further, the silica-based composite fine particles contained in the dispersion liquid of the present invention are also hereinafter referred to as "composite fine particles of the present invention".
また、本発明は、下記の工程１〜工程４を含むことを特徴とするシリカ系複合微粒子分散液の製造方法である。
工程１：シリカ微粒子が溶媒に分散してなるシリカ微粒子分散液を撹拌し、温度を５〜９８℃、ｐＨを範囲７．０〜９．０に維持しながら、ここへセリウムの金属塩を連続的又は断続的に添加し、前駆体粒子を含む前駆体粒子分散液を得る工程。
工程２：前記前駆体粒子分散液を乾燥させ、４００〜１,２００℃で焼成し、得られた焼成体に、次の（ｉ）又は（ｉｉ）の処理をして焼成体解砕分散液を得る工程。
（ｉ）乾式で解砕・粉砕処理し、溶媒を加えて溶媒分散処理する。
（ｉｉ）溶媒を加えて、湿式で解砕・粉砕処理する。
工程３：前記焼成体解砕分散液を、相対遠心加速度３００Ｇ以上にて遠心分離処理を行い、続いて沈降成分を除去することによりシリカ系複合微粒子分散液を得る工程。
工程４：前記上澄液を、相対遠心加速度３００Ｇ以上にて遠心分離処理を行い、続いて沈降成分を回収し、シリカ系複合微粒子分散液を得る工程。
なお、相対遠心加速度とは、地球の重力加速度を１Ｇとして、その比で表したものである。
このようなシリカ系複合微粒子分散液の製造方法を、以下では「本発明の製造方法」ともいう。
Further, the present invention is a method for producing a silica-based composite fine particle dispersion, which comprises the following steps 1 to 4.
Step 1: The silica fine particle dispersion liquid in which the silica fine particles are dispersed in the solvent is stirred, and the metal salt of cerium is continuously added thereto while maintaining the temperature at 5 to 98 ° C. and the pH in the range of 7.0 to 9.0. A step of obtaining a precursor particle dispersion liquid containing precursor particles by adding the particles intermittently or intermittently.
Step 2: The precursor particle dispersion is dried and fired at 400 to 1,200 ° C., and the obtained fired body is subjected to the following treatment (i) or (ii) to crush and disperse the fired body. The process of obtaining.
(I) It is crushed and pulverized by a dry method, and a solvent is added to disperse the solvent.
(Ii) A solvent is added, and the mixture is crushed and pulverized in a wet manner.
Step 3: A step of centrifuging the fired body crushed dispersion at a relative centrifugal acceleration of 300 G or more, and subsequently removing a sedimentation component to obtain a silica-based composite fine particle dispersion.
Step 4: A step of centrifuging the supernatant at a relative centrifugal acceleration of 300 G or more, and then recovering the sedimented components to obtain a silica-based composite fine particle dispersion.
The relative centrifugal acceleration is expressed by the ratio of the gravitational acceleration of the earth as 1G.
The method for producing such a silica-based composite fine particle dispersion is also referred to as "the production method of the present invention" below.
本発明の分散液は、本発明の製造方法によって製造することが好ましい。 The dispersion of the present invention is preferably produced by the production method of the present invention.
以下において、単に「本発明」と記した場合、本発明の分散液、本発明の複合微粒子及び本発明の製造方法のいずれをも意味するものとする。 In the following, when the term "invention" is simply used, it means any of the dispersion liquid of the present invention, the composite fine particles of the present invention, and the production method of the present invention.
本発明の複合微粒子について説明する。 The composite fine particles of the present invention will be described.
＜母粒子＞
本発明の複合微粒子において、母粒子は非晶質シリカを主成分とする。
<Mother particle>
In the composite fine particles of the present invention, the mother particles contain amorphous silica as a main component.
本発明における母粒子に含まれるシリカが非晶質であることは、例えば、次の方法で確認することができる。母粒子（シリカ微粒子）を含む分散液（シリカ微粒子分散液）を乾燥させた後、乳鉢を用いて粉砕し、例えば、従来公知のＸ線回折装置（例えば、理学電気株式会社製、ＲＩＮＴ１４００）によってＸ線回折パターンを得ると、Ｃｒｉｓｔｏｂａｌｉｔｅのような結晶性シリカのピークは現れない。このことから、母粒子（シリカ微粒子）に含まれるシリカは非晶質であることを確認できる。 It can be confirmed, for example, that the silica contained in the mother particles in the present invention is amorphous by the following method. A dispersion containing mother particles (silica fine particles) (silica fine particle dispersion) is dried and then pulverized using a dairy pot, and for example, by a conventionally known X-ray diffractometer (for example, RINT1400 manufactured by Rigaku Denki Co., Ltd.). When the X-ray diffraction pattern is obtained, the peak of crystalline silica such as Cristobalite does not appear. From this, it can be confirmed that the silica contained in the mother particles (silica fine particles) is amorphous.
また「主成分」とは、含有率が９０質量％以上であることを意味する。すなわち、母粒子において、非晶質シリカの含有率は９０質量％以上である。この含有率は９５質量％以上であることが好ましく、９８質量％以上であることがより好ましく、９９．５質量％以上であることがより好ましい。
以下に示す本発明の説明において「主成分」の文言は、このような意味で用いるものとする。
Further, the "main component" means that the content is 90% by mass or more. That is, the content of amorphous silica in the mother particles is 90% by mass or more. This content is preferably 95% by mass or more, more preferably 98% by mass or more, and further preferably 99.5% by mass or more.
In the description of the present invention shown below, the wording of "principal component" shall be used in this sense.
母粒子は非晶質シリカを主成分とし、その他のもの、例えば、結晶性シリカや不純物元素を含んでもよい。
例えば、前記母粒子（シリカ微粒子）において、Ｎａ、Ａｇ、Ａｌ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｋ、Ｍｇ、Ｎｉ、Ｔｉ、Ｚｎ及びＺｒの各元素（以下、「特定不純物群１」と称する場合がある）の含有率が、それぞれ１００ｐｐｍ以下であることが好ましい。さらに９０ｐｐｍ以下であることが好ましい。また、前記母粒子（シリカ微粒子）におけるＵ、Ｔｈ、Ｃｌ、ＮＯ3、ＳＯ4及びＦの各元素（以下、「特定不純物群２」と称する場合がある）の含有率は、それぞれ５ｐｐｍ以下であることが好ましい。
一般に水硝子を原料として調製したシリカ微粒子は、原料水硝子に由来する前記特定不純物群１と前記特定不純物群２を合計で数千ｐｐｍ程度含有する。
このようなシリカ微粒子が溶媒に分散してなるシリカ微粒子分散液の場合、イオン交換処理を行って前記特定不純物群１と前記特定不純物群２の含有率を下げることは可能であるが、その場合でも前記特定不純物群１と前記特定不純物群２が合計で数ｐｐｍから数百ｐｐｍ残留する。そのため水硝子を原料としたシリカ粒子を用いる場合は、酸処理等で不純物低減させることも行われている。
これに対し、アルコキシシランを原料として合成したシリカ微粒子が溶媒に分散してなるシリカ微粒子分散液の場合、通常、前記特定不純物群１及び前記特定不純物群２における各元素と各陰イオンの含有率は、それぞれ２０ｐｐｍ以下である。
なお、本発明において、母粒子（シリカ微粒子）におけるＮａ、Ａｇ、Ａｌ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｋ、Ｍｇ、Ｎｉ、Ｔｉ、Ｚｎ、Ｚｒ、Ｕ、Ｔｈ、Ｃｌ、ＮＯ3、ＳＯ4及びＦの各々の含有率は、それぞれ次の方法を用いて測定して求めた値とする。
・Ｎａ及びＫ：原子吸光分光分析
・Ａｇ、Ａｌ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｍｇ、Ｎｉ、Ｔｉ、Ｚｎ、Ｚｒ、Ｕ及びＴｈ：ＩＣＰ（誘導結合プラズマ発光分光分析）
・Ｃｌ：電位差滴定法
・ＮＯ3、ＳＯ4及びＦ：イオンクロマトグラフ
The mother particle contains amorphous silica as a main component, and may contain other substances such as crystalline silica and impurity elements.
For example, in the mother particles (silica fine particles), each element of Na, Ag, Al, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn and Zr (hereinafter referred to as "specific impurity group 1"). The content of (in some cases) is preferably 100 ppm or less. Further, it is preferably 90 ppm or less. Further, the content of each element of U, Th, Cl, NO 3 , SO 4 and F (hereinafter, may be referred to as “specific impurity group 2”) in the mother particles (silica fine particles) is 5 ppm or less. It is preferable to have.
Generally, silica fine particles prepared using water glass as a raw material contain a total of about several thousand ppm of the specific impurity group 1 and the specific impurity group 2 derived from the raw water glass.
In the case of a silica fine particle dispersion liquid in which such silica fine particles are dispersed in a solvent, it is possible to reduce the content of the specific impurity group 1 and the specific impurity group 2 by performing an ion exchange treatment, but in that case, However, the specific impurity group 1 and the specific impurity group 2 remain in a total of several ppm to several hundred ppm. Therefore, when silica particles made from water glass are used, impurities are reduced by acid treatment or the like.
On the other hand, in the case of a silica fine particle dispersion in which silica fine particles synthesized from alkoxysilane as a raw material are dispersed in a solvent, the content of each element and each anion in the specific impurity group 1 and the specific impurity group 2 is usually obtained. Is 20 ppm or less, respectively.
In the present invention, Na, Ag, Al, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn, Zr, U, Th, Cl, NO 3 , SO 4 in the mother particles (silica fine particles) Each of the contents of and F shall be a value obtained by measuring using the following method.
-Na and K: Atomic absorption spectroscopic analysis-Ag, Al, Ca, Cr, Cu, Fe, Mg, Ni, Ti, Zn, Zr, U and Th: ICP (inductively coupled plasma emission spectroscopic analysis)
・ Cl: Potentiometric titration ・ NO 3 , SO 4 and F: Ion chromatograph
後述のとおり本発明におけるシリカ系複合微粒子の平均粒子径は５０〜３５０ｎｍの範囲にあるので、その母粒子の平均粒子径は必然的に３５０ｎｍより小さい値となる。なお、本願において母粒子の平均粒子径は、後述する本発明の製造方法が含む工程１で使用するシリカ微粒子分散液に含まれるシリカ微粒子の平均粒子径と同じとする。この母粒子の平均粒子径が３０〜２００ｎｍの範囲であるシリカ系複合微粒子が好適に使用される。
母粒子の平均粒子径が上記のような範囲にあると、本発明の分散液を研磨剤として用いた場合にスクラッチが少なくなる。母粒子の平均粒子径が小さすぎると研磨レートが不足する。平均粒子径が大きすぎると、かえって研磨レートが低下する。また、基板の面精度が悪化する傾向がある。
As will be described later, since the average particle size of the silica-based composite fine particles in the present invention is in the range of 50 to 350 nm, the average particle size of the mother particles is inevitably smaller than 350 nm. In the present application, the average particle size of the mother particles is the same as the average particle size of the silica fine particles contained in the silica fine particle dispersion used in step 1 included in the production method of the present invention described later. Silica-based composite fine particles having an average particle size of the mother particles in the range of 30 to 200 nm are preferably used.
When the average particle size of the mother particles is in the above range, scratches are reduced when the dispersion of the present invention is used as an abrasive. If the average particle size of the mother particles is too small, the polishing rate will be insufficient. If the average particle size is too large, the polishing rate will decrease. In addition, the surface accuracy of the substrate tends to deteriorate.
本発明における母粒子（シリカ微粒子）の平均粒子径は、動的光散乱法又はレーザー回折散乱法で測定された値を意味する。具体的には、次の方法で測定して得た値を意味するものとする。シリカ微粒子を水等に分散させ、シリカ微粒子分散液を得た後、このシリカ微粒子分散液を、公知の動的光散乱法による粒子径測定装置（例えば、日機装株式会社製マイクロトラックＵＰＡ装置や、大塚電子社製ＰＡＲ−ＩＩＩ）あるいはレーザー回折散乱法による測定装置（例えば、ＨＯＲＩＢＡ社製ＬＡ―９５０）を用いて測定する。
なお、測定装置は各工程の目的や想定される粒子径や粒度分布に応じて使い分けられる。具体的には約１００ｎｍ以下で粒度の揃った原料の単分散シリカ微粒子はＰＡＲ−ＩＩＩを用い、１００ｎｍ以上とサイズが大きな単分散の原料シリカ微粒子はＬＡ−９５０で測定し、解砕によりミクロンメーターからナノメーターまで粒子径が幅広く変化する解砕工程では、マイクロトラックＵＰＡやＬＡ−９５０を用いることが好ましい。
The average particle size of the mother particles (silica fine particles) in the present invention means a value measured by a dynamic light scattering method or a laser diffraction scattering method. Specifically, it shall mean the value obtained by measuring by the following method. After the silica fine particles are dispersed in water or the like to obtain a silica fine particle dispersion liquid, the silica fine particle dispersion liquid is used in a known particle size measuring device by a dynamic light scattering method (for example, a Microtrac UPA device manufactured by Nikkiso Co., Ltd.). Measurement is performed using a measuring device (for example, LA-950 manufactured by HORIBA) or a measuring device by a laser diffraction scattering method (PAR-III manufactured by Otsuka Electronics Co., Ltd.).
The measuring device is used properly according to the purpose of each process and the assumed particle size and particle size distribution. Specifically, PAR-III is used for the monodisperse silica fine particles of the raw material having a uniform particle size of about 100 nm or less, and LA-950 is used for the monodisperse raw material silica fine particles having a large size of 100 nm or more, and micrometered by crushing. It is preferable to use Microtrack UPA or LA-950 in the crushing step in which the particle size varies widely from to nanometer.
母粒子（シリカ微粒子）の形状は特に限定されず、例えば、球状、俵状、短繊維状、四面体状（三角錐型）、六面体状、八面体状、板状、不定形の他に表面に疣状突起を有するものや、金平糖状のものであってもよく、また、多孔質状のものであってもよいが、球状のものが好ましい。球状とは、単一粒子の母粒子の短径／長径比が０．８以下の粒子個数比が１０％以下のものである。母粒子は、短径／長径比が０．８以下の粒子個数比が５％以下のものであることがより好ましく、０％のものであることがさらに好ましい。
短径／長径比は、後述する本発明の複合微粒子の短径／長径比の測定方法（画像解析法）と同様の方法で測定する。
The shape of the matrix particles (silica fine particles) is not particularly limited, and is, for example, spherical, bale-shaped, short-fibrous, tetrahedral-shaped (trigonal pyramidal), hexahedral, octahedral, plate-shaped, amorphous, and surface. It may have a scab-like protrusion, a golden flat sugar-like one, or a porous one, but a spherical one is preferable. The spherical shape means that the minor / major particle ratio of the mother particles of a single particle is 0.8 or less and the particle number ratio is 10% or less. The mother particles have a minor axis / major axis ratio of 0.8 or less and a particle number ratio of 5% or less, more preferably 0% or less.
The minor axis / major axis ratio is measured by the same method as the method for measuring the minor axis / major axis ratio (image analysis method) of the composite fine particles of the present invention described later.
＜子粒子＞
本発明の複合微粒子は、上記のような母粒子の表面上に子粒子を有する。ここで、母粒子の表面に子粒子が結合していることが好ましい。また、例えば、シリカ被膜が全体を被覆している子粒子が、シリカ被膜を介して母粒子に結合していてもよい。このような態様であっても、母粒子の表面上に子粒子が存在する態様であり、本発明の技術的範囲に含まれる。
<Child particles>
The composite fine particles of the present invention have child particles on the surface of the mother particles as described above. Here, it is preferable that the child particles are bonded to the surface of the mother particles. Further, for example, the child particles whose entire surface is covered with the silica film may be bonded to the mother particles via the silica film. Even in such an embodiment, the child particles are present on the surface of the mother particle, which is included in the technical scope of the present invention.
本発明の複合微粒子において、子粒子は結晶性セリアを主成分とする。 In the composite fine particles of the present invention, the child particles contain crystalline ceria as a main component.
前記子粒子が結晶性セリアであることは、例えば、本発明の分散液を、乾燥させたのち乳鉢を用いて粉砕し、例えば従来公知のＸ線回折装置（例えば、理学電気株式会社製、ＲＩＮＴ１４００）によって得たＸ線回折パターンにおいて、セリアの結晶相のみが検出されることから確認できる。なお、セリアの結晶相としては、Ｃｅｒｉａｎｉｔｅ等が挙げられる。 The fact that the child particles are crystalline ceria means that, for example, the dispersion liquid of the present invention is dried and then pulverized using a mortar, and for example, a conventionally known X-ray diffractometer (for example, RINT1400 manufactured by Rigaku Denki Co., Ltd.) ), Only the crystal phase of ceria is detected in the X-ray diffraction pattern. Examples of the crystal phase of ceria include Cerianate and the like.
子粒子は結晶性セリア（結晶性Ｃｅ酸化物）を主成分とし、その他のもの、例えばセリウム以外の元素を含んでもよい。
ただし、上記のように、本発明の複合微粒子をＸ線回折に供するとセリアの結晶相のみが検出される。すなわち、セリア以外の結晶相を含んでいたとしても、その含有率は少ないため、Ｘ線回折による検出範囲外となる。
なお、「主成分」の定義は前述の通りである。
The child particles are mainly composed of crystalline ceria (crystalline Ce oxide), and may contain other elements such as elements other than cerium.
However, as described above, when the composite fine particles of the present invention are subjected to X-ray diffraction, only the crystal phase of ceria is detected. That is, even if a crystal phase other than ceria is contained, its content is small, so that it is out of the detection range by X-ray diffraction.
The definition of "principal component" is as described above.
前記子粒子は、結晶性セリアであれば、好適に使用することができる。このような結晶性セリアとして、例えば、本発明の複合微粒子をＸ線回折に供して測定される、結晶性セリアの（１１１）面（２θ＝２８度近傍）の結晶子径は１０〜２５ｎｍの範囲のものが好ましい。 As long as the child particles are crystalline ceria, they can be preferably used. As such crystalline ceria, for example, the crystallite diameter of the (111) plane (near 2θ = 28 degrees) of the crystalline ceria measured by subjecting the composite fine particles of the present invention to X-ray diffraction is 10 to 25 nm. Those in the range are preferable.
なお、結晶性セリアの（１１１）面（２θ＝２８度近傍）の結晶子径は、次に説明する方法によって得られる値を意味するものとする。
初めに、本発明の複合微粒子を、乳鉢を用いて粉砕し、例えば従来公知のＸ線回折装置（例えば、理学電気(株)製、ＲＩＮＴ１４００）によってＸ線回折パターンを得る。そして、得られたＸ線回折パターンにおける２θ＝２８度近傍の（１１１）面のピークの半価幅を測定し、下記のＳｃｈｅｒｒｅｒの式により、結晶子径を求めることができる。
Ｄ＝Ｋλ／βｃｏｓθ
Ｄ：結晶子径（オングストローム）
Ｋ：Ｓｃｈｅｒｒｅｒ定数
λ：Ｘ線波長（１．７８８９オングストローム、Ｃｕランプ）
β：半価幅（ｒａｄ）
θ：反射角
The crystallite diameter of the (111) plane (near 2θ = 28 degrees) of the crystalline ceria means a value obtained by the method described below.
First, the composite fine particles of the present invention are pulverized using a mortar, and an X-ray diffraction pattern is obtained by, for example, a conventionally known X-ray diffractometer (for example, RINT1400 manufactured by Rigaku Denki Co., Ltd.). Then, the half-value width of the peak of the (111) plane near 2θ = 28 degrees in the obtained X-ray diffraction pattern is measured, and the crystallite diameter can be obtained by the following Scherrer equation.
D = Kλ / βcosθ
D: Crystallite diameter (Angstrom)
K: Scherrer constant λ: X-ray wavelength (1.7889 angstrom, Cu lamp)
β: Half price range (rad)
θ: Reflection angle
子粒子の大きさは、母粒子より小さく、平均粒子径１１〜２６ｎｍであることが好ましく、１２〜２３ｎｍであることがより好ましい。子粒子の大きさは、透過型電子顕微鏡を用いて３０万倍に拡大した写真投影図において、任意の５０個の子粒子について平均粒子径を測定し、これらを単純平均して得た値を意味する。 The size of the child particles is smaller than that of the mother particles, and the average particle diameter is preferably 11 to 26 nm, more preferably 12 to 23 nm. The size of the child particles is obtained by measuring the average particle size of any 50 child particles in a photographic projection drawing magnified 300,000 times using a transmission electron microscope and simply averaging these. means.
＜シリカ被膜＞
本発明の複合微粒子は、前記母粒子の表面上に前記子粒子を有し、さらにその子粒子の表面にシリカ被膜を有していることが好ましい。ここで、前記母粒子の表面に前記子粒子が結合しており、さらにそれらを覆うシリカ被膜を有していることがより好ましい。すなわち、前記母粒子の表面に前記子粒子が結合してなる複合粒子の一部又は全体をシリカ被膜が覆っていることがより好ましい。よって、本発明の複合微粒子の最表面にはシリカ被膜が存在していることがより好ましい。
また、母粒子（一次粒子）と別の１個または２個の母粒子（一次粒子）とが子粒子およびシリカ被膜を介して間接的に連結して結合粒子を構成していてもよい。
さらに、母粒子（一次粒子）と別の１個または２個の母粒子（一次粒子）とが直接に結合しており（すなわち直接的に連結しており）、それらの全部または一部を覆うように子粒子およびシリカ被膜が付いている結合粒子を構成していてもよい。
<Silica coating>
It is preferable that the composite fine particles of the present invention have the child particles on the surface of the mother particles and further have a silica film on the surface of the child particles. Here, it is more preferable that the child particles are bonded to the surface of the mother particles and further have a silica film covering them. That is, it is more preferable that a silica film covers a part or the whole of the composite particles formed by binding the child particles to the surface of the mother particles. Therefore, it is more preferable that a silica film is present on the outermost surface of the composite fine particles of the present invention.
Further, the mother particle (primary particle) and another one or two mother particles (primary particle) may be indirectly connected via the child particle and the silica film to form a bonded particle.
In addition, the mother particle (primary particle) and another one or two mother particles (primary particle) are directly bonded (ie, directly linked) and cover all or part of them. As described above, child particles and bonded particles having a silica coating may be formed.
本発明の複合微粒子が子粒子の表面にシリカ被膜を有している場合、透過型電子顕微鏡を用いて観察して得られる像（ＴＥＭ像）では、母粒子の表面に子粒子の像が濃く現れるが、その子粒子の外側、すなわち、本発明の複合微粒子の表面側には、相対的に薄い像として、シリカ被膜が現れる。また、子粒子（セリア微粒子）が母粒子（シリカ微粒子）と結合している態様であることが好ましく、シリカ被膜が全体または一部を被覆している子粒子が、シリカ被膜を介して母粒子に結合していてもよい。
また、本発明の複合微粒子が子粒子の表面にシリカ被膜を有している場合、本発明の複合微粒子をＥＤＳ分析に供し、元素分布を得ると、粒子の表面側にＣｅ濃度が高い部分が現れるが、さらにその外側にＳｉ濃度が高い部分が現れる。
また、上記のように透過型電子顕微鏡によって特定した前記シリカ被膜の部分に電子ビームを選択的に当てたＥＤＳ測定を行って当該部分のＳｉ原子数％及びＣｅ原子数％を求めると、Ｓｉ原子数％が非常に高いことを確認することができる。具体的には、Ｃｅ原子数％に対するＳｉ原子数％の比（Ｓｉ原子数％／Ｃｅ原子数％）が０．９以上となることが好ましい。
When the composite fine particles of the present invention have a silica film on the surface of the child particles, the image of the child particles is dark on the surface of the mother particles in the image (TEM image) obtained by observing with a transmission electron microscope. Although it appears, a silica film appears as a relatively thin image on the outside of the child particles, that is, on the surface side of the composite fine particles of the present invention. Further, it is preferable that the child particles (ceria fine particles) are bonded to the mother particles (silica fine particles), and the child particles whose silica film covers the whole or a part of the child particles are the mother particles via the silica film. May be combined with.
Further, when the composite fine particles of the present invention have a silica film on the surface of the child particles, when the composite fine particles of the present invention are subjected to EDS analysis and the element distribution is obtained, a portion having a high Ce concentration is found on the surface side of the particles. Although it appears, a portion having a high Si concentration appears on the outside.
Further, when EDS measurement in which an electron beam is selectively applied to the portion of the silica coating identified by the transmission electron microscope as described above to obtain the Si atom number% and the Ce atom number% of the portion, the Si atom is obtained. It can be confirmed that a few percent is very high. Specifically, the ratio of the number of Si atoms to the number of Ce atoms (Si atom number% / Ce atom number%) is preferably 0.9 or more.
このようなシリカ被膜は、子粒子（セリア結晶粒子）と母粒子（シリカ微粒子）の結合（力）を助長すると考えられる。よって、例えば、本発明の分散液を得る工程で、焼成して得られたシリカ系複合微粒子について湿式による解砕・粉砕を行うことで、シリカ系複合微粒子分散液が得られるが、シリカ被膜により、子粒子（セリア結晶粒子）が母粒子（シリカ微粒子）から外れる事を防ぐ効果があるものと考えられる。この場合、局部的な子粒子の脱落は問題なく、また、子粒子の表面の全てがシリカ被膜で覆われていなくても良い。子粒子が解砕・粉砕工程で母粒子から外れない程度の強固さがあれば良い。
このような構造を備えると、本発明の分散液を研磨剤として用いた場合、研磨速度が高く、面精度やスクラッチの悪化が少ないと考えられる。また、結晶化しているため粒子表面の−ＯＨ基が少なく、研磨基板表面の−ＯＨ基との相互作用が少ないため研磨基板表面への付着が少ないと考えられる。
例えば、被研磨基材がシリカ系材料の場合、被研磨基材表面にもシラノール基（ＳｉＯＨ）が存在するが、研磨粒子（シリカ）の表面にもＳｉＯＨが存在すると、両シラノール基が反応して研磨粒子が被研磨基材表面へ残留する場合があると考えられる。また遊離セリアは正の電荷をもつため基板へ付着しやすい。本発明の複合微粒子が子粒子の表面にシリカ被膜を有している場合、セリア粒子表面へのシリカ被覆はセリア粒子に負の電荷を付与するため、基板への付着を低減化する効果もある。
また、セリアはシリカや研磨基板、研磨パッドとは電位が異なり、ｐＨはアルカリ性から中性付近でマイナスのゼータ電位が減少して行き、弱酸性領域では逆のプラスの電位を持つ。そのため電位の大きさの違いや極性の違いなどで研磨基材や研磨パッドに付着し、研磨基材や研磨パッドに残り易い。一方、本発明の複合微粒子が子粒子の表面にシリカ被膜を有している場合、本発明のシリカ系複合微粒子は、子粒子であるセリアがシリカ被膜でその少なくとも一部が覆われているため、ｐＨがアルカリ性から酸性までマイナスの電位を維持するため、研磨基材や研磨パッドへの砥粒残りが起きにくい。
It is considered that such a silica film promotes the bond (force) between the child particles (ceria crystal particles) and the mother particles (silica fine particles). Therefore, for example, in the step of obtaining the dispersion liquid of the present invention, the silica-based composite fine particles obtained by firing are crushed and pulverized by a wet method to obtain a silica-based composite fine particle dispersion liquid. , It is considered that there is an effect of preventing the child particles (ceria crystal particles) from coming off from the mother particles (silica fine particles). In this case, there is no problem in local dropout of the child particles, and the entire surface of the child particles does not have to be covered with the silica film. It suffices if the child particles are strong enough not to be separated from the mother particles in the crushing / crushing process.
With such a structure, when the dispersion liquid of the present invention is used as an abrasive, it is considered that the polishing speed is high and the surface accuracy and scratches are less deteriorated. Further, since it is crystallized, there are few -OH groups on the particle surface, and it is considered that there is little interaction with the -OH groups on the surface of the polished substrate, so that the adhesion to the surface of the polished substrate is small.
For example, when the base material to be polished is a silica-based material, silanol groups (SiOH) are also present on the surface of the base material to be polished, but when SiOH is also present on the surface of the polishing particles (silica), both silanol groups react. It is considered that the abrasive particles may remain on the surface of the substrate to be polished. In addition, free ceria has a positive charge and easily adheres to the substrate. When the composite fine particles of the present invention have a silica film on the surface of the child particles, the silica coating on the surface of the ceria particles imparts a negative charge to the ceria particles, so that there is also an effect of reducing adhesion to the substrate. ..
In addition, ceria has a different potential from silica, a polishing substrate, and a polishing pad, and the pH has a negative zeta potential that decreases from alkaline to near neutral, and has the opposite positive potential in a weakly acidic region. Therefore, it easily adheres to the polishing base material or the polishing pad due to the difference in the magnitude of the potential or the difference in the polarity, and easily remains on the polishing base material or the polishing pad. On the other hand, when the composite fine particles of the present invention have a silica film on the surface of the child particles, the silica-based composite fine particles of the present invention have ceria, which is a child particle, covered with a silica film at least a part thereof. Since the pH maintains a negative potential from alkaline to acidic, it is unlikely that abrasive particles will remain on the polishing substrate or polishing pad.
本発明の複合微粒子が子粒子の表面にシリカ被膜を有している場合、シリカ被膜の厚さは、ＴＥＭ像やＳＥＭ像から母粒子上のセリアの子粒子のシリカ被膜による被覆具合で概ね求められる。つまり、上記のように、ＴＥＭ像では、母粒子の表面に粒子径が約２０ｎｍ前後の子粒子の像が濃く現れ、その子粒子の外側に相対的に薄い像としてシリカ被膜が現れるので、子粒子の大きさと対比する事で、シリカ被膜の厚さを概ね求めることができる。この厚さは、ＳＥＭ像から子粒子が凹凸としてハッキリ確認できて、ＴＥＭ像からシリカ系複合微粒子の輪郭に凹凸が見られるのならば、シリカ被膜の厚さは２０ｎｍをはるかに下回る事が考えられる。一方、ＳＥＭ像から子粒子の凹凸がはっきりせずに、ＴＥＭ像からもシリカ系複合微粒子の輪郭に凹凸が見られないなら、シリカ被膜の厚さは約２０ｎｍ前後であると考えられる。 When the composite fine particles of the present invention have a silica film on the surface of the child particles, the thickness of the silica film can be roughly determined from the TEM image or SEM image by the degree of coating of the child particles of ceria on the mother particle with the silica film. Be done. That is, as described above, in the TEM image, the image of the child particles having a particle diameter of about 20 nm appears darkly on the surface of the mother particles, and the silica film appears as a relatively thin image on the outside of the child particles. The thickness of the silica film can be roughly determined by comparing with the size of. If the child particles can be clearly confirmed as unevenness from the SEM image and the contour of the silica-based composite fine particles is uneven from the TEM image, it is considered that the thickness of the silica film is far less than 20 nm. Be done. On the other hand, if the unevenness of the child particles is not clear from the SEM image and the unevenness is not seen in the contour of the silica-based composite fine particles from the TEM image, the thickness of the silica film is considered to be about 20 nm.
なお、本発明の複合微粒子が子粒子の表面にシリカ被膜を有している場合、上記のように最外層（母粒子側とは反対側の層）のシリカ被膜は、子粒子（セリア微粒子）の全体を完全に覆っていなくてもよい。すなわち、本発明の複合微粒子が子粒子の表面にシリカ被膜を有している場合、本発明の複合微粒子の最表面にはシリカ被膜が存在しているが、シリカ被膜が存在していない部分があってもよい。また、シリカ系複合微粒子の母粒子が露出する部分が存在しても構わない。 When the composite fine particles of the present invention have a silica film on the surface of the child particles, the silica film on the outermost layer (the layer opposite to the mother particle side) is the child particles (ceria fine particles) as described above. It does not have to completely cover the whole. That is, when the composite fine particles of the present invention have a silica film on the surface of the child particles, the silica film is present on the outermost surface of the composite fine particles of the present invention, but the portion where the silica film is not present is present. There may be. Further, there may be a portion where the mother particles of the silica-based composite fine particles are exposed.
＜本発明の複合微粒子＞
本発明の複合微粒子は、上記のように、母粒子の表面に、上記のような子粒子を有している。
<Composite fine particles of the present invention>
As described above, the composite fine particles of the present invention have child particles as described above on the surface of the mother particles.
本発明の複合微粒子において、シリカとセリアとの質量比は１００：１１〜３１６であり、１００：３０〜２３０であることが好ましく、１００：３０〜１５０であることがより好ましく、１００：６０〜１２０であることがさらに好ましい。シリカとセリアとの質量比は、概ね、母粒子と子粒子との質量比と同程度と考えられる。母粒子に対する子粒子の量が少なすぎると、母粒子同士が結合し、粗大粒子が発生する場合がある。この場合に本発明の分散液を含む研磨剤（研磨スラリー）は、研磨基材の表面に欠陥（スクラッチの増加などの面精度の低下）を発生させる可能性がある。また、シリカに対するセリアの量が多すぎても、コスト的に高価になるばかりでなく、資源リスクが増大する。さらに、粒子同士の融着が進む。その結果、基板表面の粗度が上昇（表面粗さＲａの悪化）したり、スクラッチが増加する、更に遊離したセリアが基板に残留する、研磨装置の廃液配管等への付着といったトラブルを起こす原因ともなりやすい。
なお、前記質量比を算定する場合の対象となるシリカとは、次の（Ｉ）と(ＩＩ)の両方を含むものである。
（Ｉ）母粒子を構成するシリカ成分
（ＩＩ）母粒子に子粒子（セリア成分）が結合してなる複合微粒子を、覆ってなるシリカ被膜に含まれるシリカ成分
In the composite fine particles of the present invention, the mass ratio of silica to ceria is 100: 11-316, preferably 100: 30 to 230, more preferably 100: 30 to 150, and 100: 60 to 100. It is more preferably 120. The mass ratio of silica and ceria is considered to be approximately the same as the mass ratio of mother particles and child particles. If the amount of child particles relative to the mother particle is too small, the mother particles may bond to each other to generate coarse particles. In this case, the polishing agent (polishing slurry) containing the dispersion liquid of the present invention may cause defects (decrease in surface accuracy such as increase in scratches) on the surface of the polishing base material. Moreover, if the amount of ceria relative to silica is too large, not only the cost becomes high, but also the resource risk increases. Further, the fusion of particles progresses. As a result, the roughness of the substrate surface increases (the surface roughness Ra deteriorates), scratches increase, free ceria remains on the substrate, and the polishing device adheres to the waste liquid piping, etc. Easy to get along with.
The silica to be used when calculating the mass ratio includes both the following (I) and (II).
(I) Silica component constituting the mother particle (II) Silica component contained in the silica film covering the composite fine particles formed by binding the child particles (ceria component) to the mother particle.
本発明の複合微粒子におけるシリカ（ＳｉＯ2）とセリア（ＣｅＯ2）の含有率（質量％）は、まず本発明の複合微粒子の分散液（本発明の分散液）の固形分濃度を、１０００℃灼熱減量を行って秤量により求める。
次に、所定量の本発明の複合微粒子に含まれるセリウム（Ｃｅ）の含有率（質量％）をＩＣＰプラズマ発光分析により求め、ＣｅＯ2質量％に換算する。そして、本発明の複合微粒子を構成するＣｅＯ2以外の成分はＳｉＯ2であるとして、ＳｉＯ2質量％を算出することができる。
なお、本発明の製造方法においては、シリカとセリアの質量比は、本発明の分散液を調製する際に投入したシリカ源物質とセリア源物質との使用量から算定することもできる。これは、セリアやシリカが溶解し除去されるプロセスとなっていない場合に適用でき、そのような場合はセリアやシリカの使用量と分析値が良い一致を示す。
The content (% by mass) of silica (SiO 2 ) and ceria (CeO 2 ) in the composite fine particles of the present invention is determined by first determining the solid content concentration of the dispersion liquid (dispersion liquid of the present invention) of the composite fine particles of the present invention at 1000 ° C. Calculate by weighing after burning weight loss.
Next, the content (mass%) of cerium (Ce) contained in a predetermined amount of the composite fine particles of the present invention is determined by ICP plasma emission analysis and converted into CeO 2 % by mass. Then, it is possible to calculate SiO 2 mass%, assuming that the component other than CeO 2 constituting the composite fine particles of the present invention is SiO 2 .
In the production method of the present invention, the mass ratio of silica and ceria can also be calculated from the amount of the silica source substance and the ceria source substance used when preparing the dispersion of the present invention. This can be applied when the process is not such that ceria or silica is dissolved and removed, in which case the amount of ceria or silica used and the analytical value are in good agreement.
本発明の複合微粒子はシリカ微粒子（母粒子）の表面に粒子状の結晶性セリア（子粒子）が焼結等して結合したもの等であるので、凹凸の表面形状を有している。
すなわち、母粒子と子粒子との少なくとも一方（好ましくは双方）が、それらの接点において、焼結結合し、強固に結合していることが好ましい。ただし、シリカ被膜の覆われた子粒子が、そのシリカ被膜を介して母粒子と結合している場合もある。
Since the composite fine particles of the present invention are formed by sintering and bonding particulate crystalline ceria (child particles) on the surface of silica fine particles (mother particles), they have an uneven surface shape.
That is, it is preferable that at least one (preferably both) of the mother particle and the child particle is sintered and bonded at their contact point and is firmly bonded. However, there are cases where the child particles covered with the silica film are bonded to the mother particles via the silica film.
本発明の複合微粒子の形状は、格別に制限されるものではないが、実用上は、粒子連結型であってもよい。粒子連結型とは、２個以上の母粒子同士が各々一部において結合しているものを意味する。母粒子同士は少なくとも一方（好ましくは双方）がそれらの接点において溶着し、好ましくは双方が固着することで強固に結合しているものと考えられる。ここで、母粒子同士が結合した後に、その表面に子粒子が結合した場合の他、母粒子の表面に子粒子が結合した後、他のものに結合した場合であっても、粒子連結型とする。
連結型であると基板との接触面積を多くとることができるため、研磨エネルギーを効率良く基板へ伝えることができる。そのため、研磨速度が高い。また、粒子当たりの研磨圧力が単粒子よりも低くなるためスクラッチも少ない。
The shape of the composite fine particles of the present invention is not particularly limited, but in practice, it may be a particle-connected type. The particle-connected type means that two or more mother particles are partially bonded to each other. It is considered that at least one (preferably both) of the mother particles is welded at their contact points, and preferably both are firmly bonded to each other. Here, in addition to the case where the child particles are bonded to the surface of the mother particles after they are bonded to each other, the particle-connected type is also used even when the child particles are bonded to the surface of the mother particles and then bonded to another particle. And.
Since the contact area with the substrate can be increased in the connected type, the polishing energy can be efficiently transmitted to the substrate. Therefore, the polishing speed is high. In addition, since the polishing pressure per particle is lower than that of a single particle, there are few scratches.
本発明の複合微粒子において、前記シリカ系複合微粒子に含まれる、一次粒子が直接的または間接的に２個または３個連結した結合粒子の重量割合が６０％以上である。
ここで、本発明の複合微粒子の構成要素である各粒子の主な態様として、以下の（ア）〜（エ）が挙げられる。
（ア）母粒子に子粒子が付いてなる本発明の複合微粒子（１個）。
（イ）母粒子に子粒子が付いており、さらにシリカ被膜を付いている、本発明の複合微粒子（１個）。
（ウ）母粒子に子粒子が付いてなる１個の一次粒子と、別の１個または２個の同様の一次粒子とが直接的に結合し、それらの全部または一部を覆うようにシリカ被膜が付いて構成されている結合粒子。
（エ）母粒子に子粒子が付いてなる１個の一次粒子と、別の１個または２個の同様の一次粒子とが、シリカ被膜を介して間接的に結合している結合粒子。
In the composite fine particles of the present invention, the weight ratio of the bonded particles contained in the silica-based composite fine particles in which two or three primary particles are directly or indirectly linked is 60% or more.
Here, the following (a) to (d) can be mentioned as the main aspects of each particle which is a component of the composite fine particles of the present invention.
(A) The composite fine particles (1 piece) of the present invention in which child particles are attached to mother particles.
(A) The composite fine particles (1 piece) of the present invention having child particles attached to the mother particles and further having a silica film.
(C) Silica so that one primary particle in which a child particle is attached to a mother particle and another one or two similar primary particles are directly bonded to each other and cover all or a part of them. Bonded particles that are composed of a coating.
(D) Bonded particles in which one primary particle in which a child particle is attached to a mother particle and another one or two similar primary particles are indirectly bonded via a silica film.
本発明の複合微粒子では、上記の（ウ）または（エ）に該当する、一次粒子が直接的または間接的に２個または３個連結した結合粒子の重量割合が６０％以上である。この場合、本発明の複合微粒子は三次元的構造を備える粒子の含有率が低くなるので、研磨剤としても用いた場合にスクラッチ生成をより抑制できる点で好ましい。なお、ここで一次粒子が３個連結している場合は、これらの３個が直鎖状に連結している場合と、これらの３個が環状に結合している場合とがある。 In the composite fine particles of the present invention, the weight ratio of the bonded particles corresponding to the above (c) or (d), in which two or three primary particles are directly or indirectly linked, is 60% or more. In this case, the composite fine particles of the present invention have a low content of particles having a three-dimensional structure, and are preferable in that scratch formation can be further suppressed when used as an abrasive. Here, when three primary particles are connected, there are cases where these three particles are linearly connected and cases where these three particles are connected in a ring shape.
前記シリカ系複合微粒子に含まれる、前記結合粒子の重量割合は、画像解析法によって粒子個数割合を測定して得た後、これを重量割合に換算して得た値を意味するものとする。
具体的には、十分に希釈し分散させた複合微粒子分散液を、乾燥させ、本発明の複合微粒子試料を準備し、透過型電子顕微鏡により、倍率２５万倍（ないしは５０万倍）で写真撮影して写真投影図を得て、視認される任意の独立した粒子５０個について、それぞれの粒子個数を測定し、その結果から粒子個数割合を求めた後、重量割合に換算して、前記結合粒子の割合を求めるものとする。なお、重量割合換算値の求め方は、粒子個数毎に以下に記す式にて重量を求め、すべての粒子個数の総重量に対して百分率で求めた。
式：（複合微粒子の平均粒子径÷２）3×複合微粒子の真比重×粒子個数
なお、電子顕微鏡写真では、試料の乾燥処理時に粒子が寄り集まり凝集して見える可能性もあるため、本測定方法の妥当性を確認した。
まず後に記載する合成例の焼成体解砕分散液について粒度分布測定装置（例えばＣＰＳ社製Ｄｉｓｃ Ｃｅｔｒｉｆｕｇｅ ＤＣ１８０００）で粒度分布を測定した。粒度分布測定装置では複数のピークが確認されたが、粒子径が一番小さいピークのピークトップを１個体の粒子径（Ｄ１）であるとし、以降のピークをＤ２、Ｄ３、Ｄ４とした。次にこの１個体粒子の２倍の体積に等しい球の粒子径を２個体とし、Ｄ２'を算出した。また３倍、４倍に等しい球の体積を同様にＤ３'、Ｄ４'として求めた。その結果、Ｄ２とＤ２'、Ｄ３とＤ３'、Ｄ４とＤ４'は良い一致を示した。このことから、粒度分布測定装置で１〜４個玉の測定は妥当であると考えた。そしてこの粒度分布測定結果をピーク分離して、１〜４個体の重量割合を算出した。
次に電子顕微鏡写真から、１〜４個体の粒子個数を測定し、これを重量割合に換算し、粒度分布測定装置の重量割合と比較した。その結果、両者は良い一致を示したことから、電子顕微鏡の画像解析法は妥当であると判断した。
なお、本願においては、他の粒子と連結していない単独の一次粒子を「１個玉」、一次粒子が直接的または間接的に２個連結した粒子を「２個玉」、一次粒子が直接的または間接的に３個連結した粒子を「３個玉」、一次粒子が直接的または間接的に４個連結した粒子を「４個玉」とも称する。
The weight ratio of the bonded particles contained in the silica-based composite fine particles means a value obtained by measuring the number of particles ratio by an image analysis method and then converting it into a weight ratio.
Specifically, a sufficiently diluted and dispersed composite fine particle dispersion is dried, a composite fine particle sample of the present invention is prepared, and a photograph is taken with a transmission electron microscope at a magnification of 250,000 times (or 500,000 times). Then, a photographic projection was obtained, the number of each of 50 independent particles to be visually recognized was measured, the particle number ratio was obtained from the result, and then converted into a weight ratio to obtain the bonded particles. The ratio of The weight ratio conversion value was calculated for each number of particles by the formula described below, and was calculated as a percentage of the total weight of all the number of particles.
Formula: (Average particle size of composite fine particles ÷ 2) 3 × True specific gravity of composite fine particles × Number of particles In the electron micrograph, the particles may gather together and appear to be aggregated during the drying process of the sample. The validity of the method was confirmed.
First, the particle size distribution of the calcined body crushed dispersion of the synthetic example described later was measured with a particle size distribution measuring device (for example, Disc Cetrifuge DC18000 manufactured by CPS). Although a plurality of peaks were confirmed in the particle size distribution measuring device, the peak top of the peak having the smallest particle diameter was defined as the particle diameter (D1) of one individual, and the subsequent peaks were designated as D2, D3, and D4. Next, D2'was calculated by setting the particle diameter of the sphere, which is equal to twice the volume of this one individual particle, to two individuals. Further, the volumes of spheres equal to 3 times and 4 times were similarly obtained as D3'and D4'. As a result, D2 and D2', D3 and D3', and D4 and D4' showed good agreement. From this, it was considered that the measurement of 1 to 4 balls with the particle size distribution measuring device was appropriate. Then, the particle size distribution measurement results were peak-separated to calculate the weight ratio of 1 to 4 individuals.
Next, the number of particles of 1 to 4 individuals was measured from the electron micrograph, converted into a weight ratio, and compared with the weight ratio of the particle size distribution measuring device. As a result, both showed good agreement, and it was judged that the electron microscope image analysis method was appropriate.
In the present application, a single primary particle that is not connected to other particles is a "single ball", a particle in which two primary particles are directly or indirectly connected is a "double ball", and the primary particle is directly. A particle in which three particles are directly or indirectly connected is also referred to as a "three-ball", and a particle in which four primary particles are directly or indirectly connected is also referred to as a "four-ball".
本発明の複合微粒子は、比表面積が４〜１００ｍ2／ｇであることが好ましく、３０〜６０ｍ2／ｇであることがより好ましい。 The composite fine particles of the present invention preferably have a specific surface area of 4 to 100 m 2 / g, more preferably 30 to 60 m 2 / g.
ここで、比表面積（ＢＥＴ比表面積）の測定方法について説明する。
まず、乾燥させた試料（０．２ｇ）を測定セルに入れ、窒素ガス気流中、２５０℃で４０分間脱ガス処理を行い、その上で試料を窒素３０体積％とヘリウム７０体積％の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の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、試料の比表面積を測定する。
このようなＢＥＴ比表面積測定法（窒素吸着法）は、例えば従来公知の表面積測定装置を用いて行うことができる。
本発明において比表面積は、特に断りがない限り、このような方法で測定して得た値を意味するものとする。
Here, a method for measuring the specific surface area (BET specific surface area) will be described.
First, a dried sample (0.2 g) is placed in a measurement cell, degassed at 250 ° C. for 40 minutes in a nitrogen gas stream, and then the sample is mixed with 30% by volume of nitrogen and 70% by volume of helium. Keep the liquid nitrogen temperature in the air stream and allow nitrogen to equilibrate and adsorb to the sample. Next, the temperature of the sample is gradually raised to room temperature while flowing the mixed gas, the amount of nitrogen desorbed during that period is detected, and the specific surface area of the sample is measured by a calibration curve prepared in advance.
Such a BET specific surface area measurement method (nitrogen adsorption method) can be performed using, for example, a conventionally known surface area measuring device.
In the present invention, the specific surface area means a value obtained by measuring by such a method unless otherwise specified.
本発明の複合微粒子の平均粒子径は５０〜３５０ｎｍであることが好ましく、１７０〜２６０ｎｍであることがより好ましい。本発明の複合微粒子の平均粒子径が５０〜３５０ｎｍの範囲にある場合、研磨材として適用した際に研磨速度が高くなり好ましい。
本発明の複合微粒子の平均粒子径は、動的光散乱法又はレーザー回折散乱法で測定された値を意味する。具体的には、次の方法で測定して得た値を意味するものとする。本発明の複合微粒子を水に分散させ、この複合微粒子分散液を、公知の動的光散乱法による粒子径測定装置（例えば、日機装株式会社製マイクロトラックＵＰＡ装置や、大塚電子社製ＰＡＲ−ＩＩＩ）あるいはレーザー回折散乱法による測定装置（例えば、ＨＯＲＩＢＡ社製ＬＡ―９５０）を用いて測定する。
The average particle size of the composite fine particles of the present invention is preferably 50 to 350 nm, more preferably 170 to 260 nm. When the average particle size of the composite fine particles of the present invention is in the range of 50 to 350 nm, the polishing rate becomes high when applied as an abrasive, which is preferable.
The average particle size of the composite fine particles of the present invention means a value measured by a dynamic light scattering method or a laser diffraction scattering method. Specifically, it shall mean the value obtained by measuring by the following method. The composite fine particles of the present invention are dispersed in water, and the composite fine particle dispersion is used in a known particle size measuring device by a dynamic light scattering method (for example, a Microtrack UPA device manufactured by Nikkiso Co., Ltd. or PAR-III manufactured by Otsuka Electronics Co., Ltd.). ) Or a measuring device by a laser diffraction scattering method (for example, LA-950 manufactured by HORIBA).
本発明の複合微粒子において、前記特定不純物群１の各元素の含有率は、それぞれ１００ｐｐｍ以下であることが好ましい。さらに５０ｐｐｍ以下であることが好ましく、４５ｐｐｍ以下であることがより好ましい。また、本発明の複合微粒子における前記特定不純物群２の各元素の含有率は、それぞれ５ｐｐｍ以下であることが好ましい。本発明の複合微粒子における特定不純物群１及び前記特定不純物群２それぞれの元素の含有率を低減させる方法については、母粒子（シリカ微粒子）について述べた方法が適用できる。
なお、本発明の複合微粒子における前記特定不純物群１と前記特定不純物群２の各々の元素の含有率は、ＩＣＰ（誘導結合プラズマ発光分光分析装置）を用いて測定して求める値とする。
In the composite fine particles of the present invention, the content of each element in the specific impurity group 1 is preferably 100 ppm or less. Further, it is preferably 50 ppm or less, and more preferably 45 ppm or less. Further, the content of each element of the specific impurity group 2 in the composite fine particles of the present invention is preferably 5 ppm or less. As a method for reducing the content of each element of the specific impurity group 1 and the specific impurity group 2 in the composite fine particles of the present invention, the method described for the mother particles (silica fine particles) can be applied.
The content of each element of the specific impurity group 1 and the specific impurity group 2 in the composite fine particles of the present invention is a value obtained by measuring using an ICP (inductively coupled plasma emission spectroscopic analyzer).
本発明の複合微粒子は、前記特定不純物群１の各元素含有率がそれぞれ１００ｐｐｍ以下であり、前記特定不純物群２の各元素含有率がそれぞれ５ｐｐｍ以下であることを特徴とする複合酸化物微粒子分散液である場合と、必ずしもこの条件を満たさない複合酸化物微粒子である場合がある。このうち、前者は、高純度な研磨剤の適用が求められる用途、例えば、半導体基板、配線基板などの半導体デバイスなどの研磨用途において研磨剤として好適に使用することができる。また、後者は、高純度な研磨剤の適用が求められない用途、例えば、ガラス研磨などに適用される。（前者は、高純度な研磨剤の適用が求められない用途にも当然に適用可能である。） The composite fine particles of the present invention are characterized in that each element content of the specific impurity group 1 is 100 ppm or less and each element content of the specific impurity group 2 is 5 ppm or less. It may be a liquid or a composite oxide fine particle that does not necessarily satisfy this condition. Of these, the former can be suitably used as an abrasive in applications where the application of a high-purity abrasive is required, for example, in applications such as semiconductor devices such as semiconductor substrates and wiring substrates. Further, the latter is applied to applications where the application of a high-purity abrasive is not required, for example, glass polishing. (The former is naturally applicable to applications that do not require the application of high-purity abrasives.)
＜本発明の分散液＞
本発明の分散液について説明する。
本発明の分散液は、上記のような本発明の複合微粒子が分散溶媒に分散しているものである。
<Dispersion of the present invention>
The dispersion liquid of the present invention will be described.
The dispersion liquid of the present invention is one in which the composite fine particles of the present invention as described above are dispersed in a dispersion solvent.
本発明の分散液は分散溶媒として、水及び／又は有機溶媒を含む。この分散溶媒として、例えば純水、超純水、イオン交換水のような水を用いることが好ましい。さらに、本発明の分散液は、添加剤として、研磨促進剤、界面活性剤、ｐＨ調整剤及びｐＨ緩衝剤からなる群より選ばれる１種以上を含んでいてもよい。 The dispersion liquid of the present invention contains water and / or an organic solvent as the dispersion solvent. As the dispersion solvent, it is preferable to use water such as pure water, ultrapure water, or ion-exchanged water. Further, the dispersion liquid of the present invention may contain, as an additive, one or more selected from the group consisting of a polishing accelerator, a surfactant, a pH adjuster and a pH buffer.
また、本発明の分散液を備える分散溶媒として、例えばメタノール、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、イソオクタン、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の有機溶媒を用いることができる。これらを水と混合して用いてもよい。 Further, as the dispersion solvent containing the dispersion liquid of the present invention, alcohols such as methanol, ethanol, isopropanol, n-butanol, methyl isocarbinol and the like; acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone and cyclohexanone. Ketones such as; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H-pyran Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether; glycol ether acetates such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate; acetic acid Ethers such as methyl, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethylene carbonate; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, isooctane and cyclohexane; chloride Halogenized hydrocarbons such as methylene, 1,2-dichloroethane, dichloropropane, chlorobenzene; sulfoxides such as dimethylsulfoxide; organics such as pyrrolidones such as N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone A solvent can be used. These may be mixed with water and used.
本発明の分散液に含まれる固形分濃度は０．３〜５０質量％の範囲にあることが好ましい。 The solid content concentration contained in the dispersion liquid of the present invention is preferably in the range of 0.3 to 50% by mass.
本発明の分散液は、カチオンコロイド滴定を行った場合に、下記式（１）で表される流動電位変化量（ΔＰＣＤ）と、クニックにおけるカチオンコロイド滴定液の添加量（Ｖ）との比（ΔＰＣＤ／Ｖ）が―１１０．０〜―１５．０となる流動電位曲線が得られるものであることが好ましい。
ΔＰＣＤ／Ｖ＝（Ｉ−Ｃ）／Ｖ・・・式（１）
Ｃ：前記クニックにおける流動電位（ｍＶ）
Ｉ：前記流動電位曲線の開始点における流動電位（ｍＶ）
Ｖ：前記クニックにおける前記カチオンコロイド滴定液の添加量（ｍｌ）
In the dispersion of the present invention, when cationic colloid titration is performed, the ratio of the amount of change in flow potential (ΔPCD) represented by the following formula (1) to the amount (V) of the cationic colloid titrator added in the knick (V). It is preferable that a flow potential curve having ΔPCD / V) of -110.0 to -15.0 can be obtained.
ΔPCD / V = (IC) / V ... Equation (1)
C: Flow potential (mV) in the knick
I: Flow potential (mV) at the start point of the flow potential curve
V: Addition amount (ml) of the cationic colloid titration solution in the knick
ここで、カチオンコロイド滴定は、固形分濃度を１質量％に調整した本発明の分散液８０ｇにカチオンコロイド滴定液を添加することで行う。カチオンコロイド滴定液として、０．００１Ｎポリ塩化ジアリルジメチルアンモニウム溶液を用いる。 Here, the cationic colloid titration is performed by adding the cationic colloid titration solution to 80 g of the dispersion liquid of the present invention in which the solid content concentration is adjusted to 1% by mass. A 0.001N polychlorinated diallyldimethylammonium chloride solution is used as the cationic colloid titration solution.
このカチオンコロイド滴定によって得られる流動電位曲線とは、カチオン滴定液の添加量（ｍｌ）をＸ軸、本発明の分散液の流動電位（ｍＶ）をＹ軸に取ったグラフである。
また、クニックとは、カチオンコロイド滴定によって得られる流動電位曲線において急激に流動電位が変化する点（変曲点）である。そして点Ａにおける流動電位をＣ（ｍＶ）とし、点Ａにおけるカチオンコロイド滴定液の添加量をＶ（ｍｌ）とする。
流動電位曲線の開始点とは、滴定前の本発明の分散液における流動電位である。具体的には、カチオンコロイド滴定液の添加量が０である点を開始点とする。この点における流動電位をＩ（ｍＶ）とする。
The flow potential curve obtained by this cation colloid titration is a graph in which the addition amount (ml) of the cation titration solution is on the X-axis and the flow potential (mV) of the dispersion liquid of the present invention is on the Y-axis.
The knick is a point (inflection point) where the flow potential changes rapidly in the flow potential curve obtained by cation colloid titration. Then, the flow potential at the point A is C (mV), and the amount of the cationic colloid titrant added at the point A is V (ml).
The starting point of the flow potential curve is the flow potential in the dispersion of the present invention before titration. Specifically, the starting point is the point where the amount of the cationic colloid titration solution added is 0. Let the flow potential at this point be I (mV).
上記のΔＰＣＤ／Ｖの値が−１１０．０〜−１５．０であると、本発明の分散液を研磨剤として用いた場合、研磨剤の研磨速度がより向上する。このΔＰＣＤ／Ｖは、本発明の複合微粒子表面におけるシリカ被膜の被覆具合及び／又は複合微粒子の表面における子粒子の露出具合あるいは脱離しやすいシリカの存在を反映していると考えられる。ΔＰＣＤ／Ｖの値が上記範囲内であると、湿式による解砕・粉砕時において子粒子は脱離する事が少なく、研磨速度も高いと本発明者は推定している。逆にΔＰＣＤ／Ｖの値が−１１０．０よりもその絶対値が大きい場合は、複合微粒子表面がシリカ被膜で全面覆われているため解砕・粉砕工程にて子粒子脱落は起き難いが研磨時にシリカが脱離しがたく研磨速度が低下する。一方、−１５．０よりもその絶対値が小さい場合は脱落が起きやすいと考えられる。上記範囲内であると、研磨時において子粒子表面が適度に露出して子粒子の脱落が少なく、研磨速度がより向上すると本発明者は推定している。ΔＰＣＤ／Ｖは、−１００．０〜−１５．０であることがより好ましく、−１００．０〜−２０．０であることがさらに好ましい。 When the above value of ΔPCD / V is -110.0 to -15.0, the polishing speed of the abrasive is further improved when the dispersion of the present invention is used as the abrasive. It is considered that this ΔPCD / V reflects the coating condition of the silica film on the surface of the composite fine particles of the present invention and / or the exposure condition of the child particles on the surface of the composite fine particles or the presence of silica which is easily detached. The present inventor presumes that when the value of ΔPCD / V is within the above range, the child particles are less likely to be desorbed during crushing and crushing by a wet method, and the polishing rate is high. On the contrary, when the absolute value of ΔPCD / V is larger than -110.0, the surface of the composite fine particles is entirely covered with a silica film, so that child particles are unlikely to fall off in the crushing / crushing process, but polishing. Sometimes silica is hard to remove and the polishing speed is reduced. On the other hand, if the absolute value is smaller than -15.0, it is considered that dropout is likely to occur. Within the above range, the present inventor presumes that the surface of the child particles is appropriately exposed during polishing, the child particles are less likely to fall off, and the polishing speed is further improved. ΔPCD / V is more preferably -100.0 to -15.0, and even more preferably -100.0 to -20.0.
本発明の分散液は、そのｐＨ値を３〜８の範囲とした場合に、カチオンコロイド滴定を始める前、すなわち、滴定量がゼロである場合の流動電位がマイナスの電位となるものであることが好ましい。これは、この流動電位がマイナスの電位を維持する場合、同じくマイナスの表面電位を示す研磨基材への砥粒（シリカ系複合微粒子）の残留が生じ難いからである。 The dispersion liquid of the present invention has a negative potential when the pH value is in the range of 3 to 8, and the flow potential before starting the cationic colloid titration, that is, when the titration amount is zero. Is preferable. This is because when the flow potential maintains a negative potential, it is difficult for abrasive grains (silica-based composite fine particles) to remain on the polishing substrate, which also exhibits a negative surface potential.
本発明の分散液の製造方法は特に限定されないが、次に説明する本発明の製造方法によって製造することが好ましい。 The method for producing the dispersion liquid of the present invention is not particularly limited, but it is preferably produced by the production method of the present invention described below.
＜本発明の製造方法＞
本発明の製造方法について説明する。
本発明の製造方法は以下に説明する工程１〜工程４を備える。
<Manufacturing method of the present invention>
The production method of the present invention will be described.
The manufacturing method of the present invention includes steps 1 to 4 described below.
＜本発明の製造方法＞
＜工程１＞
工程１ではシリカ微粒子が溶媒に分散してなるシリカ微粒子分散液を用意する。
本発明の製造方法により、半導体デバイスなどの研磨に適用するシリカ系複合微粒子分散液を調製しようとする場合は、シリカ微粒子分散液として、アルコキシシランの加水分解により製造したシリカ微粒子が溶媒に分散してなるシリカ微粒子分散液を用いることが好ましい。なお、従来公知のシリカ微粒子分散液（水硝子を原料として調製したシリカ微粒子分散液等）を原料とする場合は、シリカ微粒子分散液を酸処理し、更に脱イオン処理して使用することが好ましい。この場合、シリカ微粒子に含まれるＮａ、Ａｇ、Ａｌ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｋ、Ｍｇ、Ｎｉ、Ｔｉ、Ｚｎ、Ｚｒ、Ｕ、Ｔｈ、Ｃｌ、ＮＯ3、ＳＯ4及びＦの含有率が少なくなり、具体的には、１００ｐｐｍ以下となり得るからである。
なお、具体的には、工程１で使用する原料であるシリカ微粒子分散液中のシリカ微粒子として、次の（ａ）と（ｂ）の条件を満たすものが好適に使用される。
（ａ）Ｎａ、Ａｇ、Ａｌ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｋ、Ｍｇ、Ｎｉ、Ｔｉ、Ｚｎ及びＺｒの含有率が、それぞれ１００ｐｐｍ以下。
（ｂ）Ｕ、Ｔｈ、Ｃｌ、ＮＯ3、ＳＯ4及びＦの含有率が、それぞれ５ｐｐｍ以下。
<Manufacturing method of the present invention>
<Step 1>
In step 1, a silica fine particle dispersion liquid in which silica fine particles are dispersed in a solvent is prepared.
When a silica-based composite fine particle dispersion to be applied to polishing a semiconductor device or the like is to be prepared by the production method of the present invention, the silica fine particles produced by hydrolysis of alkoxysilane are dispersed in a solvent as the silica fine particle dispersion. It is preferable to use a silica fine particle dispersion liquid. When a conventionally known silica fine particle dispersion (such as a silica fine particle dispersion prepared from water glass as a raw material) is used as a raw material, it is preferable to use the silica fine particle dispersion after acid treatment and further deionization. .. In this case, the content of Na, Ag, Al, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn, Zr, U, Th, Cl, NO 3 , SO 4 and F contained in the silica fine particles. This is because, specifically, it can be 100 ppm or less.
Specifically, as the silica fine particles in the silica fine particle dispersion liquid which is the raw material used in the step 1, those satisfying the following conditions (a) and (b) are preferably used.
(A) The contents of Na, Ag, Al, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn and Zr are 100 ppm or less, respectively.
(B) The contents of U, Th, Cl, NO 3 , SO 4 and F are 5 ppm or less, respectively.
工程１では、上記のようなシリカ微粒子が溶媒に分散したシリカ微粒子分散液を撹拌し、温度を５〜９８℃、ｐＨ範囲を７．０〜９．０に維持しながら、ここへセリウムの金属塩を連続的又は断続的に添加し、前駆体粒子を含む前駆体粒子分散液を得る。 In step 1, the silica fine particle dispersion liquid in which the silica fine particles are dispersed in the solvent as described above is stirred, and the temperature is maintained at 5 to 98 ° C. and the pH range is maintained at 7.0 to 9.0, and the metal of cerium is here. The salt is added continuously or intermittently to obtain a precursor particle dispersion containing the precursor particles.
前記シリカ微粒子分散液における分散媒は水を含むことが好ましく、水系のシリカ微粒子分散液（水ゾル）を使用することが好ましい。 The dispersion medium in the silica fine particle dispersion liquid preferably contains water, and it is preferable to use an aqueous silica fine particle dispersion liquid (water sol).
前記シリカ微粒子分散液における固形分濃度は、ＳｉＯ2換算基準で１〜４０質量％であることが好ましい。この固形分濃度が低すぎると、製造工程でのシリカ濃度が低くなり生産性が悪くなり得る。 The solid content concentration in the silica fine particle dispersion is preferably 1 to 40% by mass based on the SiO 2 conversion standard. If the solid content concentration is too low, the silica concentration in the manufacturing process may be low and the productivity may be deteriorated.
また、陽イオン交換樹脂又は陰イオン交換樹脂、あるいは鉱酸、有機酸等で不純物を抽出し、限外ろ過膜などを用いて、必要に応じて、シリカ微粒子分散液の脱イオン処理を行うことができる。脱イオン処理により不純物イオンなどを除去したシリカ微粒子分散液は表面にケイ素を含む水酸化物を形成させやすいのでより好ましい。なお、脱イオン処理はこれらに限定されるものではない。 In addition, impurities are extracted with cation exchange resin or anion exchange resin, mineral acid, organic acid, etc., and the silica fine particle dispersion is deionized as necessary using an ultrafiltration membrane or the like. Can be done. A silica fine particle dispersion from which impurity ions and the like have been removed by a deionization treatment is more preferable because a hydroxide containing silicon is likely to be formed on the surface. The deionization treatment is not limited to these.
工程１では、上記のようなシリカ微粒子分散液を撹拌し、温度を５〜９８℃、ｐＨ範囲を７．０〜９．０に維持しながら、ここへセリウムの金属塩を連続的又は断続的に添加する。
セリウムの金属塩は限定されるものではないが、セリウムの塩化物、硝酸塩、硫酸塩、酢酸塩、炭酸塩、金属アルコキシドなどを用いることができる。具体的には、硝酸第一セリウム、炭酸セリウム、硫酸第一セリウム、塩化第一セリウムなどを挙げることができる。なかでも、硝酸第一セリウムや塩化第一セリウムが好ましい。中和と同時に過飽和となった溶液から、結晶性セリウム酸化物が生成し、それらは速やかにシリカ微粒子に凝集沈着機構で付着するので結合性酸化物形成の効率が高く好ましい。しかしこれら金属塩に含まれる硫酸イオン、塩化物イオン、硝酸イオンなどは、腐食性を示す。そのため調合後に後工程で洗浄し５ｐｐｍ以下に除去する必要がある。一方、炭酸塩は炭酸ガスとして調合中に放出され、またアルコキシドは分解してアルコールとなるため、好ましい。
In step 1, the silica fine particle dispersion as described above is stirred, and the metal salt of cerium is continuously or intermittently added thereto while maintaining the temperature at 5 to 98 ° C. and the pH range at 7.0 to 9.0. Add to.
The metal salt of cerium is not limited, but chloride, nitrate, sulfate, acetate, carbonate, metal alkoxide and the like of cerium can be used. Specific examples thereof include primary cerium nitrate, cerium carbonate, primary cerium sulfate, and primary cerium chloride. Of these, first cerium nitrate and first cerium chloride are preferable. Crystalline cerium oxides are produced from the solution that becomes supersaturated at the same time as neutralization, and they rapidly adhere to the silica fine particles by a coagulation deposition mechanism, so that the efficiency of bond oxide formation is high and preferable. However, sulfate ions, chloride ions, nitrate ions and the like contained in these metal salts are corrosive. Therefore, it is necessary to wash the mixture in a subsequent step after preparation and remove it to 5 ppm or less. On the other hand, carbonate is preferable because it is released as carbon dioxide gas during preparation and the alkoxide is decomposed into alcohol.
シリカ微粒子分散液に対するセリウムの金属塩の添加量は、得られる本発明の複合微粒子におけるシリカとセリアとの質量比が、前述のように、１００：１１〜３１６の範囲となる量とする。
なお、本発明のシリカ系複合微粒子分散液の製造方法において、セリウムの金属塩は、通常、セリウムの金属塩に水又は水系溶媒を加えてセリウム金属塩水溶液としたものが使用される。セリウム金属塩水溶液のセリア濃度は、格別に制限されるものではないが、作業性等を考慮すると、セリア濃度は１〜４０質量％の範囲が好ましい。
The amount of the metal salt of cerium added to the silica fine particle dispersion is such that the mass ratio of silica and ceria in the obtained composite fine particles of the present invention is in the range of 100: 11 to 316 as described above.
In the method for producing a silica-based composite fine particle dispersion of the present invention, the metal salt of cerium is usually a cerium metal salt aqueous solution obtained by adding water or an aqueous solvent to the metal salt of cerium. The ceria concentration of the cerium metal salt aqueous solution is not particularly limited, but the ceria concentration is preferably in the range of 1 to 40% by mass in consideration of workability and the like.
シリカ微粒子分散液にセリウムの金属塩を添加した後、撹拌する際の温度は５〜９８℃であり、１０〜９５℃であることが好ましい。また、撹拌する際の温度は１〜３０℃であることが好ましい。この温度が低すぎるとシリカの溶解度が著しく低下するため、セリアの結晶化が制御されなくなり、粗大なセリアの結晶性酸化物が生成して、シリカ微粒子（母粒子）への付着が起こり難くなる事が考えられる。
逆に、この温度が高すぎるとシリカの溶解度が著しく増し、結晶性のセリア酸化物の生成が抑制される事が考えられる。更に、反応器壁面にスケールなどが生じやすくなり好ましくない。
After adding the metal salt of cerium to the silica fine particle dispersion, the temperature at the time of stirring is 5 to 98 ° C, preferably 10 to 95 ° C. Further, the temperature at the time of stirring is preferably 1 to 30 ° C. If this temperature is too low, the solubility of silica will be significantly reduced, so that the crystallization of ceria will not be controlled, and coarse crystalline oxides of ceria will be generated, making it difficult for adhesion to silica fine particles (mother particles) to occur. Things can be considered.
On the contrary, if this temperature is too high, the solubility of silica is remarkably increased, and it is considered that the formation of crystalline ceria oxide is suppressed. Further, scale and the like are likely to occur on the wall surface of the reactor, which is not preferable.
また、撹拌する際の時間は０．５〜２４時間であることが好ましく、０．５〜１８時間であることがより好ましい。この時間が短すぎると結晶性の酸化セリウムが十分に形成できないため好ましくない。逆に、この時間が長すぎても結晶性の酸化セリウムの形成はそれ以上反応が進まず不経済となる。なお、前記セリウム金属塩の添加後に、所望により５〜９８℃で熟成しても構わない。熟成により、セリウム化合物が母粒子に沈着する反応をより促進させることができる。 The time for stirring is preferably 0.5 to 24 hours, more preferably 0.5 to 18 hours. If this time is too short, crystalline cerium oxide cannot be sufficiently formed, which is not preferable. On the contrary, even if this time is too long, the formation of crystalline cerium oxide is uneconomical because the reaction does not proceed any further. After the addition of the cerium metal salt, it may be aged at 5 to 98 ° C. if desired. By aging, the reaction of depositing the cerium compound on the mother particles can be further promoted.
また、シリカ微粒子分散液にセリウムの金属塩を添加し、撹拌する際のシリカ微粒子分散液のｐＨ範囲は７．０〜９．０とするが、７．６〜８．６とすることが好ましい。ｐＨが高すぎても低すぎても、安定性が低下する傾向がある。この際、アルカリ等を添加しｐＨ調整を行うことが好ましい。このようなアルカリの例としては、公知のアルカリを使用することができる。具体的には、アンモニア水溶液、水酸化アルカリ、アルカリ土類金属、アミン類の水溶液などが挙げられるが、これらに限定されるものではない。 Further, the pH range of the silica fine particle dispersion when the metal salt of cerium is added to the silica fine particle dispersion and stirred is set to 7.0 to 9.0, but preferably 7.6 to 8.6. .. If the pH is too high or too low, the stability tends to decrease. At this time, it is preferable to add an alkali or the like to adjust the pH. As an example of such an alkali, a known alkali can be used. Specific examples thereof include, but are not limited to, an aqueous solution of ammonia, an alkali hydroxide, an alkaline earth metal, and an aqueous solution of amines.
このような工程１によって、本発明の複合微粒子の前駆体である粒子（前駆体粒子）を含む分散液（前駆体粒子分散液）が得られる。 By such step 1, a dispersion liquid (precursor particle dispersion liquid) containing particles (precursor particles) which are precursors of the composite fine particles of the present invention can be obtained.
工程１で得られた前駆体粒子分散液を、工程２に供する前に、純水やイオン交換水などを用いて、さらに希釈あるいは濃縮して、次の工程２に供してもよい。 The precursor particle dispersion obtained in step 1 may be further diluted or concentrated with pure water, ion-exchanged water, or the like before being subjected to step 2, and then subjected to the next step 2.
なお、前駆体粒子分散液における固形分濃度は１〜２７質量％であることが好ましい。 The solid content concentration in the precursor particle dispersion is preferably 1 to 27% by mass.
また、所望により、前駆体粒子分散液を、陽イオン交換樹脂、陰イオン交換樹脂、限外ろ過膜、イオン交換膜、遠心分離などを用いて脱イオン処理してもよい。 Further, if desired, the precursor particle dispersion may be deionized using a cation exchange resin, an anion exchange resin, an ultrafiltration membrane, an ion exchange membrane, centrifugation or the like.
工程１は、より好適には、シリカ微粒子分散液の温度範囲を４８〜５２℃とし、ｐＨ範囲を７．０〜９．０に維持しながら、セリウムの金属塩を連続的又は断続的に添加し、前駆体粒子分散液を調製し、更に該前駆体粒子分散液を温度９０〜９８℃で熟成することにより行われる。工程１をこのような条件で行った場合、シリカ微粒子の表面に低結晶度の酸化セリウムが均一に付着し、酸化セリウム同士の凝集体を形成する事を防ぐことが出来る。 In step 1, more preferably, the temperature range of the silica fine particle dispersion is 48 to 52 ° C., and the metal salt of cerium is continuously or intermittently added while maintaining the pH range of 7.0 to 9.0. Then, a precursor particle dispersion is prepared, and the precursor particle dispersion is further aged at a temperature of 90 to 98 ° C. When step 1 is performed under such conditions, it is possible to prevent cerium oxide having low crystallinity from uniformly adhering to the surface of the silica fine particles and forming aggregates of cerium oxides.
＜工程２＞
工程２では、前駆体粒子分散液を乾燥させた後、４００〜１,２００℃で焼成する。
<Process 2>
In step 2, the precursor particle dispersion is dried and then fired at 400 to 1,200 ° C.
乾燥する方法は特に限定されない。従来公知の乾燥機を用いて乾燥させることができる。具体的には、箱型乾燥機、バンド乾燥機、スプレードライアー等を使用することができる。
なお、好適には、さらに乾燥前の前駆体粒子分散液のｐＨを６．０〜７．０とすることが推奨される。乾燥前の前駆体粒子分散液のｐＨを６．０〜７．０とした場合、表面活性を抑制できるからである。
乾燥後、焼成する温度は４００〜１２００℃であるが、８００〜１１００℃であることが好ましく、１０００〜１０９０℃であることがより好ましい。このような温度範囲において焼成すると、セリアの結晶化が十分に進行し、また、セリア微粒子の表面に存在するシリカ被膜が、適度に厚膜化し、母粒子と子粒子とが強固に結合する。この温度が高すぎると、セリアの結晶が異常成長したり、セリア粒子上のシリカ被膜が厚くなり母粒子との結合が進むが、セリアの子粒子を厚く覆う事も予想され、母粒子を構成する非晶質シリカが結晶化したり、粒子同士の融着が進む可能性もある。
The method of drying is not particularly limited. It can be dried using a conventionally known dryer. Specifically, a box dryer, a band dryer, a spray dryer and the like can be used.
Preferably, it is recommended that the pH of the precursor particle dispersion before drying is 6.0 to 7.0. This is because the surface activity can be suppressed when the pH of the precursor particle dispersion before drying is set to 6.0 to 7.0.
After drying, the firing temperature is 400 to 1200 ° C., preferably 800 to 1100 ° C., more preferably 1000 to 1090 ° C. When fired in such a temperature range, crystallization of ceria proceeds sufficiently, the silica film existing on the surface of the ceria fine particles becomes an appropriate thick film, and the mother particles and the child particles are firmly bonded. If this temperature is too high, ceria crystals will grow abnormally or the silica film on the ceria particles will become thicker and bond with the mother particles will progress, but it is expected that the ceria child particles will be thickly covered, forming the mother particles. Amorphous silica may crystallize or the particles may be fused together.
工程２では、焼成して得られた焼成体に次の（ｉ）又は（ｉｉ）の処理をして焼成体解砕分散液を得る。
（ｉ）乾式で解砕・粉砕処理し、溶媒を加えて溶媒分散処理する。
（ｉｉ）溶媒を加えて、湿式で解砕・粉砕処理する。
乾式の解砕・粉砕装置としては従来公知の装置を使用することができるが、例えば、アトライター、ボールミル、振動ミル、振動ボールミル等を挙げることができる。
湿式の解砕・粉砕装置としても従来公知の装置を使用することができるが、例えば、バスケットミル等のバッチ式ビーズミル、横型・縦型・アニュラー型の連続式のビーズミル、サンドグラインダーミル、ボールミル等、ロータ・ステータ式ホモジナイザー、超音波分散式ホモジナイザー、分散液中の微粒子同士をぶつける衝撃粉砕機等の湿式媒体攪拌式ミル（湿式解砕機）が挙げられる。湿式媒体攪拌ミルに用いるビーズとしては、例えば、ガラス、アルミナ、ジルコニア、スチール、フリント石等を原料としたビーズを挙げることができる。
前記（ｉ）又は前記（ｉｉ）の何れの処理においても、溶媒としては、水及び／又は有機溶媒が使用される。例えば、純水、超純水、イオン交換水のような水を用いることが好ましい。また、（ｉ）又は（ｉｉ）の処理により得られる焼成体解砕分散液の固形分濃度は、格別に制限されるものではないが、例えば、０．３〜５０質量％の範囲にあることが好ましく、１０〜３０質量％とすることがより好ましい。（ｉ）又は（ｉｉ）の処理のうち、実用上は（ｉｉ）の湿式による処理がより好適に用いられる。
In step 2, the fired body obtained by firing is subjected to the following treatment (i) or (ii) to obtain a fired body crushed dispersion liquid.
(I) It is crushed and pulverized by a dry method, and a solvent is added to disperse the solvent.
(Ii) A solvent is added, and the mixture is crushed and pulverized in a wet manner.
As the dry type crushing / crushing device, a conventionally known device can be used, and examples thereof include an attritor, a ball mill, a vibration mill, and a vibration ball mill.
Conventionally known equipment can also be used as a wet crushing / crushing apparatus. For example, a batch type bead mill such as a basket mill, a horizontal / vertical / annual type continuous bead mill, a sand grinder mill, a ball mill, etc. , Rotor-stator type homogenizer, ultrasonic dispersion type homogenizer, wet medium stirring type mill (wet crusher) such as an impact crusher that collides fine particles in a dispersion liquid with each other. Examples of beads used in the wet medium stirring mill include beads made of glass, alumina, zirconia, steel, flint stone and the like.
In either the treatment (i) or the treatment (ii), water and / or an organic solvent is used as the solvent. For example, it is preferable to use water such as pure water, ultrapure water, and ion-exchanged water. Further, the solid content concentration of the fired body crushed dispersion obtained by the treatment of (i) or (ii) is not particularly limited, but is, for example, in the range of 0.3 to 50% by mass. Is preferable, and it is more preferably 10 to 30% by mass. Of the treatments (i) or (ii), the wet treatment of (ii) is more preferably used in practice.
なお、前記（ｉｉ）の湿式による解砕・粉砕を行う場合は、溶媒のｐＨを９．０〜１０．６に維持しながら湿式による解砕・粉砕を行うことが好ましい。ｐＨをこの範囲に維持すると、カチオンコロイド滴定を行った場合に、前記式（１）で表される、流動電位変化量（ΔＰＣＤ）と、クニックにおけるカチオンコロイド滴定液の添加量（Ｖ）との比（ΔＰＣＤ／Ｖ）が−１１０．０〜−１５．０となる流動電位曲線が得られるシリカ系複合微粒子分散液を、最終的により容易に得ることができる。
すなわち、前述の好ましい態様に該当する本発明の分散液が得られる程度に、解砕・粉砕を行うことが好ましい。前述のように、好ましい態様に該当する本発明の分散液を研磨剤に用いた場合、研磨速度がより向上するからである。これについて本発明者は、本発明の複合微粒子表面におけるシリカ被膜が適度に薄くなること、及び／又は複合微粒子表面の一部に子粒子が適度に露出することで、研磨速度がより向上し、且つセリアの子粒子の脱落を制御できると推定している。また、シリカ被膜が薄いか剥げた状態であるため、子粒子が研磨時にある程度脱離しやすくなると推定している。ΔＰＣＤ／Ｖは、−１００．０〜−１５．０であることがより好ましく、−１００．０〜−２０．０であることがさらに好ましい。
When the wet crushing / crushing of (ii) is carried out, it is preferable to carry out the wet crushing / crushing while maintaining the pH of the solvent at 9.0 to 10.6. When the pH is maintained in this range, when cation colloid titration is performed, the flow potential change amount (ΔPCD) represented by the above formula (1) and the addition amount (V) of the cation colloid titration solution in the knick Finally, a silica-based composite fine particle dispersion having a flow potential curve having a ratio (ΔPCD / V) of -110.0 to -15.0 can be obtained more easily.
That is, it is preferable to carry out crushing and pulverization to the extent that the dispersion liquid of the present invention corresponding to the above-mentioned preferred embodiment can be obtained. This is because, as described above, when the dispersion liquid of the present invention corresponding to the preferred embodiment is used as the polishing agent, the polishing speed is further improved. Regarding this, the present inventor has further improved the polishing rate by appropriately thinning the silica film on the surface of the composite fine particles of the present invention and / or appropriately exposing the child particles to a part of the surface of the composite fine particles. Moreover, it is presumed that the shedding of ceria child particles can be controlled. In addition, since the silica film is thin or peeled off, it is estimated that the child particles are likely to be detached to some extent during polishing. ΔPCD / V is more preferably -100.0 to -15.0, and even more preferably -100.0 to -20.0.
＜工程３＞
工程３では、工程２において得られた前記焼成体解砕分散液について、相対遠心加速度３００Ｇ以上にて遠心分離処理を行い、続いて沈降成分を除去し、上澄液を得る。
<Step 3>
In step 3, the fired body crushed dispersion obtained in step 2 is subjected to a centrifugal separation treatment at a relative centrifugal acceleration of 300 G or more, and then the sedimentation component is removed to obtain a supernatant.
具体的には、前記焼成体解砕分散液について、遠心分離処理による分級を行う。遠心分離処理における相対遠心加速度は３００Ｇ以上とする。遠心分離処理後、沈降成分を除去し、上澄液を得ることができる。相対遠心加速度の上限は格別に制限されるものではないが、実用上は１０，０００Ｇ以下で使用される。 Specifically, the fired body crushed dispersion is classified by centrifugation. The relative centrifugal acceleration in the centrifugation process is 300 G or more. After the centrifugation treatment, the sedimentation component can be removed to obtain a supernatant. The upper limit of the relative centrifugal acceleration is not particularly limited, but it is practically used at 10,000 G or less.
工程３において遠心分離処理を行う時間は１〜３０分であることが好ましく、３〜１０分であることがより好ましい。
なお、工程３（遠心分離処理）は所望により、１回または複数回行って構わない。工程３を複数回行う場合は、上澄液と沈降品を分離し、その都度、上澄液を回収して、その上澄液を工程３に供することにより行う。
The time for centrifuging in step 3 is preferably 1 to 30 minutes, more preferably 3 to 10 minutes.
In addition, step 3 (centrifugation treatment) may be performed once or a plurality of times as desired. When the step 3 is performed a plurality of times, the supernatant and the precipitated product are separated, the supernatant is collected each time, and the supernatant is subjected to the step 3.
＜工程４＞
工程４では、工程３において得られた上澄液について、相対遠心加速度３００Ｇ以上にて遠心分離処理を行い、続いて沈降成分を回収し、シリカ系複合微粒子分散液を得る。
<Step 4>
In step 4, the supernatant obtained in step 3 is subjected to a centrifugation treatment at a relative centrifugal acceleration of 300 G or more, and then the sedimentation component is recovered to obtain a silica-based composite fine particle dispersion.
具体的には、前記上澄液について、遠心分離処理による分級を行う。遠心分離処理における相対遠心加速度は３００Ｇ以上とする。遠心分離処理後、沈降成分を回収し、これをシリカ系複合微粒子分散液として得ることができる。相対遠心加速度の上限は格別に制限されるものではないが、実用上は１０，０００Ｇ以下で使用される。 Specifically, the supernatant is classified by centrifugation. The relative centrifugal acceleration in the centrifugation process is 300 G or more. After the centrifugation treatment, the precipitated component can be recovered and obtained as a silica-based composite fine particle dispersion. The upper limit of the relative centrifugal acceleration is not particularly limited, but is practically used at 10,000 G or less.
工程４において遠心分離処理を行う時間は１〜３０分であることが好ましく、３〜１０分であることがより好ましい。
なお、工程４（遠心分離処理）は所望により、１回または複数回行って構わない。工程４を複数回行う場合は、上澄液と沈降品を分離し、その都度、沈降品を回収して、その沈降品を工程４に供することにより行う。
The time for centrifuging in step 4 is preferably 1 to 30 minutes, more preferably 3 to 10 minutes.
In addition, step 4 (centrifugation treatment) may be performed once or a plurality of times as desired. When the step 4 is performed a plurality of times, the supernatant and the settled product are separated, the settled product is collected each time, and the settled product is subjected to the step 4.
本発明の製造方法では、上記のように、工程３および工程４において遠心分離処理を行うが、さらに別の遠心分離処理を行ってもよく、この場合でも本発明の製造方法の範囲内である。 In the production method of the present invention, the centrifugation treatment is performed in steps 3 and 4 as described above, but another centrifugation treatment may be performed, and even in this case, it is within the scope of the production method of the present invention. ..
工程３および工程４では、上記の条件を満たす遠心分離処理を備えることが必要である。遠心加速度（および好ましくは処理時間）が上記の条件に満たない場合は、工程４によって得られるシリカ系複合微粒子分散液中に三次元構造の粒子（すなわち、一次粒子が４個以上結合したもの）が相対的に多く残存するため、シリカ系複合微粒子分散液を用いた研磨材などの研磨用途に使用した際に、スクラッチが発生する原因となる。本発明の製造方法では、一次粒子が２個または３個連結した結合粒子を多く含む本発明の分散液を得ることができ、このような本発明の分散液では、三次元構造の粒子が少ないため、研磨剤として使用した時にスクラッチが発生し難い。
本発明では、上記の製造方法によって得られるシリカ系複合微粒子分散液を、更に乾燥させて、シリカ系複合微粒子を得ることができる。乾燥方法は特に限定されず、例えば、従来公知の乾燥機を用いて乾燥させることができる。
In step 3 and step 4, it is necessary to provide a centrifugation treatment satisfying the above conditions. When the centrifugal acceleration (and preferably the treatment time) does not meet the above conditions, particles having a three-dimensional structure (that is, four or more primary particles bonded) in the silica-based composite fine particle dispersion obtained in step 4). Since a relatively large amount of the particles remain, it causes scratches when used for polishing applications such as abrasives using a silica-based composite fine particle dispersion. In the production method of the present invention, it is possible to obtain the dispersion liquid of the present invention containing a large amount of bonded particles in which two or three primary particles are linked, and in such a dispersion liquid of the present invention, there are few particles having a three-dimensional structure. Therefore, scratches are unlikely to occur when used as an abrasive.
In the present invention, the silica-based composite fine particle dispersion obtained by the above production method can be further dried to obtain silica-based composite fine particles. The drying method is not particularly limited, and for example, it can be dried using a conventionally known dryer.
このような本発明の製造方法によって、本発明の分散液を得ることができる。
また、シリカ微粒子分散液にセリウムの金属塩を添加した際に、調合液の還元電位が正の値をとることが望ましい。酸化還元電位が負となった場合、セリウム合物がシリカ粒子表面に沈着せずに板状・棒状などのセリウム単独粒子が生成するからである。酸化還元電位を正に保つ方法として過酸化水素などの酸化剤を添加したり、エアーを吹き込む方法が挙げられるが、これらに限定されるものではない。
The dispersion liquid of the present invention can be obtained by such a production method of the present invention.
Further, it is desirable that the reduction potential of the preparation liquid takes a positive value when the metal salt of cerium is added to the silica fine particle dispersion liquid. This is because when the redox potential becomes negative, the cerium mixture does not deposit on the surface of the silica particles, and cerium single particles such as plates and rods are generated. Examples of the method of keeping the redox potential positive include, but are not limited to, a method of adding an oxidizing agent such as hydrogen peroxide and a method of blowing air.
＜研磨用スラリー＞
本発明の分散液を含む液体は、研磨スラリー（以下では「本発明の研磨用スラリー」ともいう）として好ましく用いることができる。特にはＳｉＯ2絶縁膜が形成された半導体基板の平坦化用の研磨スラリーとして好適に使用することができる。
<Slurry for polishing>
The liquid containing the dispersion liquid of the present invention can be preferably used as a polishing slurry (hereinafter, also referred to as "polishing slurry of the present invention"). In particular, it can be suitably used as a polishing slurry for flattening a semiconductor substrate on which a SiO 2 insulating film is formed.
本発明の研磨用スラリーは半導体基板などを研磨する際の研磨速度が高く、また研磨時に研磨面のキズ（スクラッチ）が少ない、基板への砥粒の残留が少ないなどの効果に優れている。 The polishing slurry of the present invention has excellent effects such as a high polishing speed when polishing a semiconductor substrate or the like, less scratches (scratches) on the polished surface during polishing, and less residual abrasive grains on the substrate.
本発明の研磨用スラリーは分散溶媒として、水及び／又は有機溶媒を含む。この分散溶媒として、例えば純水、超純水、イオン交換水のような水を用いることが好ましい。さらに、本発明の研磨用スラリーは、添加剤として、研磨促進剤、界面活性剤、複素環化合物、ｐＨ調整剤及びｐＨ緩衝剤からなる群より選ばれる１種以上を含んでいてもよい。 The polishing slurry of the present invention contains water and / or an organic solvent as a dispersion solvent. As the dispersion solvent, it is preferable to use water such as pure water, ultrapure water, or ion-exchanged water. Further, the polishing slurry of the present invention may contain, as an additive, one or more selected from the group consisting of a polishing accelerator, a surfactant, a heterocyclic compound, a pH adjuster and a pH buffer.
＜研磨促進剤＞
本発明に係る研磨用スラリーには、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研磨促進剤を使用することができる。この様な例としては、過酸化水素、過酢酸、過酸化尿素など及びこれらの混合物を挙げることができる。このような過酸化水素等の研磨促進剤を含む研磨剤組成物を用いると、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。
<Abrasive accelerator>
In the polishing slurry according to the present invention, a conventionally known polishing accelerator can be used, if necessary, although it depends on the type of the material to be polished. Examples of such include hydrogen peroxide, peracetic acid, urea peroxide and the like, and mixtures thereof. When such an abrasive composition containing a polishing accelerator such as hydrogen peroxide is used, the polishing rate can be effectively improved when the material to be polished is a metal.
研磨促進剤の別の例としては、硫酸、硝酸、リン酸、シュウ酸、フッ酸等の無機酸、酢酸等の有機酸、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、アミン塩及びこれらの混合物などを挙げることができる。これらの研磨促進剤を含む研磨用組成物の場合、複合成分からなる被研磨材を研磨する際に、被研磨材の特定の成分についての研磨速度を促進することにより、最終的に平坦な研磨面を得ることができる。 Other examples of polishing accelerators include inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, oxalic acid and hydrofluoric acid, organic acids such as acetic acid, or sodium salts, potassium salts, ammonium salts, amine salts and the like of these acids. A mixture of the above can be mentioned. In the case of a polishing composition containing these polishing accelerators, when polishing a material to be polished composed of composite components, by accelerating the polishing rate for a specific component of the material to be polished, finally flat polishing is performed. You can get a face.
本発明に係る研磨用スラリーが研磨促進剤を含有する場合、その含有量としては、０．１〜１０質量％であることが好ましく、０．５〜５質量％であることがより好ましい。 When the polishing slurry according to the present invention contains a polishing accelerator, the content thereof is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.
＜界面活性剤及び／又は親水性化合物＞
研磨用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又は親水性化合物を添加することができる。界面活性剤と親水性化合物は、いずれも被研磨面への接触角を低下させる作用を有し、均一な研磨を促す作用を有する。界面活性剤及び／又は親水性化合物としては、例えば、以下の群から選ばれるものを使用することができる。
<Surfactant and / or hydrophilic compound>
Cationic, anionic, nonionic, amphoteric and hydrophilic surfactants or hydrophilic compounds can be added to improve the dispersibility and stability of the polishing slurry. Both the surfactant and the hydrophilic compound have an action of lowering the contact angle with the surface to be polished and an action of promoting uniform polishing. As the surfactant and / or hydrophilic compound, for example, those selected from the following groups can be used.
陰イオン界面活性剤として、カルボン酸塩、スルホン酸塩、硫酸エステル塩、リン酸エステル塩が挙げられ、カルボン酸塩として、石鹸、Ｎ−アシルアミノ酸塩、ポリオキシエチレン又はポリオキシプロピレンアルキルエーテルカルボン酸塩、アシル化ペプチド；スルホン酸塩として、アルキルスルホン酸塩、アルキルベンゼン及びアルキルナフタレンスルホン酸塩、ナフタレンスルホン酸塩、スルホコハク酸塩、α−オレフィンスルホン酸塩、Ｎ−アシルスルホン酸塩；硫酸エステル塩として、硫酸化油、アルキル硫酸塩、アルキルエーテル硫酸塩、ポリオキシエチレン又はポリオキシプロピレンアルキルアリルエーテル硫酸塩、アルキルアミド硫酸塩；リン酸エステル塩として、アルキルリン酸塩、ポリオキシエチレン又はポリオキシプロピレンアルキルアリルエーテルリン酸塩を挙げることができる。 Anionic surfactants include carboxylates, sulfonates, sulfates, phosphates, and carboxylates include soaps, N-acylamino acids, polyoxyethylene or polyoxypropylene alkyl ether carboxylic acids. Acidates, acylated peptides; as sulfonates, alkyl sulfonates, alkylbenzene and alkylnaphthalene sulfonates, naphthalene sulfonates, sulfosuccinates, α-olefin sulfonates, N-acyl sulfonates; sulfates. Sulfate oil, alkyl sulfate, alkyl ether sulfate, polyoxyethylene or polyoxypropylene alkylallyl ether sulfate, alkylamide sulfate as salts; alkyl phosphate, polyoxyethylene or poly as phosphate ester salts Oxypropylene alkylallyl ether phosphate can be mentioned.
陽イオン界面活性剤として、脂肪族アミン塩、脂肪族４級アンモニウム塩、塩化ベンザルコニウム塩、塩化ベンゼトニウム、ピリジニウム塩、イミダゾリニウム塩；両性界面活性剤として、カルボキシベタイン型、スルホベタイン型、アミノカルボン酸塩、イミダゾリニウムベタイン、レシチン、アルキルアミンオキサイドを挙げることができる。 As cationic surfactants, aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium chloride salts, benzethonium chloride, pyridinium salts, imidazolinium salts; as amphoteric tenside agents, carboxybetaine type, sulfobetaine type, Aminocarboxylates, imidazolinium betaine, lecithin, alkylamine oxides can be mentioned.
非イオン界面活性剤として、エーテル型、エーテルエステル型、エステル型、含窒素型が挙げられ、エーテル型として、ポリオキシエチレンアルキル及びアルキルフェニルエーテル、アルキルアリルホルムアルデヒド縮合ポリオキシエチレンエーテル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ポリオキシエチレンポリオキシプロピレンアルキルエーテルが挙げられ、エーテルエステル型として、グリセリンエステルのポリオキシエチレンエーテル、ソルビタンエステルのポリオキシエチレンエーテル、ソルビトールエステルのポリオキシエチレンエーテル、エステル型として、ポリエチレングリコール脂肪酸エステル、グリセリンエステル、ポリグリセリンエステル、ソルビタンエステル、プロピレングリコールエステル、ショ糖エステル、含窒素型として、脂肪酸アルカノールアミド、ポリオキシエチレン脂肪酸アミド、ポリオキシエチレンアルキルアミド等が例示される。その他に、フッ素系界面活性剤などが挙げられる。 Examples of the nonionic surfactant include ether type, ether ester type, ester type, and nitrogen-containing type, and examples of the ether type are polyoxyethylene alkyl and alkylphenyl ether, alkylallyl formaldehyde condensed polyoxyethylene ether, and polyoxyethylene poly. Examples thereof include oxypropylene block polymer and polyoxyethylene polyoxypropylene alkyl ether. Examples of the ether ester type include polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of sorbitol ester, and ester type. Examples of polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, sorbitan ester, propylene glycol ester, sucrose ester, and nitrogen-containing type include fatty acid alkanolamide, polyoxyethylene fatty acid amide, and polyoxyethylene alkylamide. In addition, a fluorine-based surfactant and the like can be mentioned.
界面活性剤としては陰イオン界面活性剤もしくは非イオン系界面活性剤が好ましく、また、塩としては、アンモニウム塩、カリウム塩、ナトリウム塩等が挙げられ、特にアンモニウム塩及びカリウム塩が好ましい。 The surfactant is preferably an anionic surfactant or nonionic surfactant, and examples of the salt include ammonium salt, potassium salt, sodium salt and the like, and ammonium salt and potassium salt are particularly preferable.
さらに、その他の界面活性剤、親水性化合物等としては、グリセリンエステル、ソルビタンエステル及びアラニンエチルエステル等のエステル；ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリエチレングリコールアルキルエーテル、ポリエチレングリコールアルケニルエーテル、アルキルポリエチレングリコール、アルキルポリエチレングリコールアルキルエーテル、アルキルポリエチレングリコールアルケニルエーテル、アルケニルポリエチレングリコール、アルケニルポリエチレングリコールアルキルエーテル、アルケニルポリエチレングリコールアルケニルエーテル、ポリプロピレングリコールアルキルエーテル、ポリプロピレングリコールアルケニルエーテル、アルキルポリプロピレングリコール、アルキルポリプロピレングリコールアルキルエーテル、アルキルポリプロピレングリコールアルケニルエーテル、アルケニルポリプロピレングリコール等のエーテル；アルギン酸、ペクチン酸、カルボキシメチルセルロース、カードラン及びプルラン等の多糖類；グリシンアンモニウム塩及びグリシンナトリウム塩等のアミノ酸塩；ポリアスパラギン酸、ポリグルタミン酸、ポリリシン、ポリリンゴ酸、ポリメタクリル酸、ポリメタクリル酸アンモニウム塩、ポリメタクリル酸ナトリウム塩、ポリアミド酸、ポリマレイン酸、ポリイタコン酸、ポリフマル酸、ポリ（ｐ−スチレンカルボン酸）、ポリアクリル酸、ポリアクリルアミド、アミノポリアクリルアミド、ポリアクリル酸アンモニウム塩、ポリアクリル酸ナトリウム塩、ポリアミド酸、ポリアミド酸アンモニウム塩、ポリアミド酸ナトリウム塩及びポリグリオキシル酸等のポリカルボン酸及びその塩；ポリビニルアルコール、ポリビニルピロリドン及びポリアクロレイン等のビニル系ポリマ；メチルタウリン酸アンモニウム塩、メチルタウリン酸ナトリウム塩、硫酸メチルナトリウム塩、硫酸エチルアンモニウム塩、硫酸ブチルアンモニウム塩、ビニルスルホン酸ナトリウム塩、１−アリルスルホン酸ナトリウム塩、２−アリルスルホン酸ナトリウム塩、メトキシメチルスルホン酸ナトリウム塩、エトキシメチルスルホン酸アンモニウム塩、３−エトキシプロピルスルホン酸ナトリウム塩等のスルホン酸及びその塩；プロピオンアミド、アクリルアミド、メチル尿素、ニコチンアミド、コハク酸アミド及びスルファニルアミド等のアミド等を挙げることができる。 Further, as other surfactants, hydrophilic compounds and the like, esters such as glycerin ester, sorbitan ester and alanine ethyl ester; polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol alkyl ether, polyethylene glycol alkenyl ether, alkyl. Polyethylene glycol, alkyl polyethylene glycol alkyl ether, alkyl polyethylene glycol alkenyl ether, alkenyl polyethylene glycol, alkenyl polyethylene glycol alkyl ether, alkenyl polyethylene glycol alkenyl ether, polypropylene glycol alkyl ether, polypropylene glycol alkenyl ether, alkyl polypropylene glycol, alkyl polypropylene glycol alkyl ether , Alkyl Polypropylene Glycol Alkenyl Ether, Ethers such as Alkenyl Polypropylene Glycol; Polysaccharides such as Arginic Acid, Pectinic Acid, Carboxymethyl Cellulose, Cardran and Purulane; Polylysine, polyapple acid, polymethacrylic acid, polyammonium methacrylate salt, polysodium methacrylate salt, polyamic acid, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid), polyacrylic acid, polyacrylamide, amino Polycarboxylic acids such as polyacrylamide, ammonium polyacrylic acid salt, sodium polyacrylic acid salt, polyamic acid, ammonium polyamic acid salt, sodium polyamic acid salt and polyglyoxylic acid and their salts; polyvinyl alcohol, polyvinylpyrrolidone and polyacrolein and the like. Vinyl-based polyma; ammonium methyltaurate salt, sodium methyltaurate salt, methylsodium sulfate salt, ethylammonium sulfate salt, butylammonium sulfate salt, sodium vinylsulfonic acid salt, sodium 1-allylsulfonic acid salt, 2-allylsulfonic acid Sulphonic acids such as sodium salt, sodium methoxymethylsulfonic acid salt, ammonium ethoxymethylsulfonic acid salt, sodium 3-ethoxypropylsulfonic acid salt and salts thereof; propionamide, acrylamide, methylurea, nicotineamide, succinic acid amide and sulf Examples thereof include amides such as ananylamide.
なお、適用する被研磨基材がガラス基板等である場合は、何れの界面活性剤であっても好適に使用できるが、半導体集積回路用シリコン基板などの場合であって、アルカリ金属、アルカリ土類金属又はハロゲン化物等による汚染の影響を嫌う場合にあっては、酸もしくはそのアンモニウム塩系の界面活性剤を使用することが望ましい。 When the base material to be applied is a glass substrate or the like, any surfactant can be preferably used, but in the case of a silicon substrate for a semiconductor integrated circuit or the like, alkali metal or alkaline soil can be used. When the influence of contamination by metals or halides is disliked, it is desirable to use an acid or an ammonium salt-based surfactant thereof.
本発明に係る研磨用スラリーが界面活性剤及び／又は親水性化合物を含有する場合、その含有量は、総量として、研磨用スラリーの１Ｌ中、０．００１〜１０ｇとすることが好ましく、０．０１〜５ｇとすることがより好ましく０．１〜３ｇとすることが特に好ましい。 When the polishing slurry according to the present invention contains a surfactant and / or a hydrophilic compound, the total content thereof is preferably 0.001 to 10 g in 1 L of the polishing slurry. It is more preferably 01 to 5 g, and particularly preferably 0.1 to 3 g.
界面活性剤及び／又は親水性化合物の含有量は、充分な効果を得る上で、研磨用スラリーの１Ｌ中、０．００１ｇ以上が好ましく、研磨速度低下防止の点から１０ｇ以下が好ましい。 The content of the surfactant and / or the hydrophilic compound is preferably 0.001 g or more in 1 L of the polishing slurry, and preferably 10 g or less from the viewpoint of preventing a decrease in the polishing rate, in order to obtain a sufficient effect.
界面活性剤又は親水性化合物は１種のみでもよいし、２種以上を使用してもよく、異なる種類のものを併用することもできる。 Only one type of surfactant or hydrophilic compound may be used, two or more types may be used, or different types may be used in combination.
＜複素環化合物＞
本発明の研磨用スラリーについては、被研磨基材に金属が含まれる場合に、金属に不動態層又は溶解抑制層を形成させて、被研磨基材の侵食を抑制する目的で、複素環化合物を含有させても構わない。ここで、「複素環化合物」とはヘテロ原子を１個以上含んだ複素環を有する化合物である。ヘテロ原子とは、炭素原子、又は水素原子以外の原子を意味する。複素環とはヘテロ原子を少なくとも一つ持つ環状化合物を意味する。ヘテロ原子は複素環の環系の構成部分を形成する原子のみを意味し、環系に対して外部に位置していたり、少なくとも一つの非共役単結合により環系から分離していたり、環系のさらなる置換基の一部分であるような原子は意味しない。ヘテロ原子として好ましくは、窒素原子、硫黄原子、酸素原子、セレン原子、テルル原子、リン原子、ケイ素原子、及びホウ素原子などを挙げることができるがこれらに限定されるものではない。複素環化合物の例として、イミダゾール、ベンゾトリアゾール、ベンゾチアゾール、テトラゾールなどを用いることができる。より具体的には、１，２，３，４−テトラゾール、５−アミノ−１，２，３，４−テトラゾール、５−メチル−１，２，３，４−テトラゾール、１，２，３−トリアゾール、４−アミノ−１，２，３−トリアゾール、４，５−ジアミノ−１，２，３−トリアゾール、１，２，４−トリアゾール、３−アミノ１，２，４−トリアゾール、３，５−ジアミノ−１，２，４−トリアゾールなどを挙げることができるが、これらに限定されるものではない。
<Heterocyclic compound>
The polishing slurry of the present invention is a heterocyclic compound for the purpose of suppressing erosion of the base material to be polished by forming a passivation layer or a dissolution suppressing layer on the metal when the base material to be polished contains a metal. May be contained. Here, the "heterocyclic compound" is a compound having a heterocycle containing one or more heteroatoms. Heteroatom means an atom other than a carbon atom or a hydrogen atom. A heterocycle means a cyclic compound having at least one heteroatom. Heteroatoms refer only to the atoms that form the constituents of the heterocyclic ring system, and may be located outside the ring system, separated from the ring system by at least one unconjugated single bond, or the ring system. It does not mean an atom that is part of a further substituent of. Preferred heteroatoms include, but are not limited to, nitrogen atoms, sulfur atoms, oxygen atoms, selenium atoms, tellurium atoms, phosphorus atoms, silicon atoms, and boron atoms. As an example of the heterocyclic compound, imidazole, benzotriazole, benzothiazole, tetrazole and the like can be used. More specifically, 1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 5-methyl-1,2,3,4-tetrazole, 1,2,3- Triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-triazole, 1,2,4-triazole, 3-amino1,2,4-triazole, 3,5 −Diamino-1,2,4-triazole and the like can be mentioned, but are not limited thereto.
本発明に係る研磨用スラリーに複素環化合物を配合する場合の含有量については、０．００１〜１．０質量％であることが好ましく、０．００１〜０．７質量％であることがより好ましく、０．００２〜０．４質量％であることがさらに好ましい。 The content of the heterocyclic compound in the polishing slurry according to the present invention is preferably 0.001 to 1.0% by mass, more preferably 0.001 to 0.7% by mass. It is preferably 0.002 to 0.4% by mass, and more preferably 0.002 to 0.4% by mass.
＜ｐＨ調整剤＞
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又は塩基を添加して研磨用組成物のｐＨを調節することができる。
<pH adjuster>
The pH of the polishing composition can be adjusted by adding an acid or a base as necessary to enhance the effect of each of the above additives.
研磨用スラリーをｐＨ７以上に調整するときは、ｐＨ調整剤として、アルカリ性のものを使用する。望ましくは、水酸化ナトリウム、アンモニア水、炭酸アンモニウム、エチルアミン、メチルアミン、トリエチルアミン、テトラメチルアミンなどのアミンが使用される。 When adjusting the pH of the polishing slurry to 7 or higher, an alkaline one is used as the pH adjuster. Desirably, amines such as sodium hydroxide, aqueous ammonia, ammonium carbonate, ethylamine, methylamine, triethylamine, tetramethylamine and the like are used.
研磨用スラリーをｐＨ７未満に調整するときは、ｐＨ調整剤として、酸性のものが使用される。例えば、酢酸、乳酸、クエン酸、リンゴ酸、酒石酸、グリセリン酸などのヒドロキシ酸類の様な、塩酸、硝酸などの鉱酸が使用される。 When adjusting the polishing slurry to a pH of less than 7, an acidic one is used as the pH adjuster. For example, mineral acids such as hydrochloric acid and nitric acid such as hydroxy acids such as acetic acid, lactic acid, citric acid, malic acid, tartaric acid and glyceric acid are used.
＜ｐＨ緩衝剤＞
研磨用スラリーのｐＨ値を一定に保持するために、ｐＨ緩衝剤を使用しても構わない。ｐＨ緩衝剤としては、例えば、リン酸２水素アンモニウム、リン酸水素２アンモニウム、４ホウ酸アンモ四水和水などのリン酸塩及びホウ酸塩又は有機酸などを使用することができる。
<pH buffer>
A pH buffer may be used to keep the pH value of the polishing slurry constant. As the pH buffer, for example, phosphates such as ammonium dihydrogen phosphate, ammonium hydrogen phosphate, quaternary ammonium tetrahydrate, and borate or organic acids can be used.
また、本発明の研磨用スラリーの分散溶媒として、例えばメタノール、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、イソオクタン、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の有機溶媒を用いることができる。これらを水と混合して用いてもよい。 Further, as the dispersion solvent of the polishing slurry of the present invention, alcohols such as methanol, ethanol, isopropanol, n-butanol and methyl isocarbinol; acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone and cyclohexanone. Ketones such as; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H-pyran Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether; glycol ether acetates such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate; acetic acid Ethers such as methyl, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, ethylene carbonate; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, isooctane and cyclohexane; chloride Halogenized hydrocarbons such as methylene, 1,2-dichloroethane, dichloropropane, chlorobenzene; sulfoxides such as dimethylsulfoxide; organics such as pyrrolidones such as N-methyl-2-pyrrolidone, N-octyl-2-pyrrolidone A solvent can be used. These may be mixed with water and used.
本発明の研磨用スラリーに含まれる固形分濃度は０．３〜５０質量％の範囲にあることが好ましい。この固形分濃度が低すぎると研磨速度が低下する可能性がある。逆に固形分濃度が高すぎても研磨速度はそれ以上向上する場合は少ないので、不経済となり得る。 The solid content concentration contained in the polishing slurry of the present invention is preferably in the range of 0.3 to 50% by mass. If this solid content concentration is too low, the polishing rate may decrease. On the contrary, even if the solid content concentration is too high, the polishing rate is rarely improved further, which may be uneconomical.
以下、本発明について実施例に基づき説明する。本発明はこれらの実施例に限定されない。 Hereinafter, the present invention will be described based on examples. The present invention is not limited to these examples.
初めに、実施例及び比較例における各測定方法及び試験方法の詳細について説明する。各実施例及び比較例について、以下の各測定結果及び試験結果を第１表に記す。 First, details of each measurement method and test method in Examples and Comparative Examples will be described. For each example and comparative example, the following measurement results and test results are shown in Table 1.
[成分の分析]
[シリカ微粒子（母粒子）]
後述するシリカ微粒子分散液のＳｉＯ2重量について、珪酸ナトリウムを原料としたシリカ微粒子の場合は１０００℃灼熱減量を行って秤量により求めた。またアルコキシシランを原料としたシリカ微粒子の場合は、シリカ微粒子分散液を１５０℃で１時間乾燥させた後に秤量して求めた。
[Analysis of ingredients]
[Silica fine particles (mother particles)]
The weight of SiO 2 of the silica fine particle dispersion liquid described later was determined by weighing in the case of silica fine particles made from sodium silicate by performing a burning weight loss of 1000 ° C. In the case of silica fine particles using alkoxysilane as a raw material, the silica fine particle dispersion was dried at 150 ° C. for 1 hour and then weighed.
[シリカ系複合微粒子]
各元素の含有率は、以下の方法によって測定するものとする。
初めに、シリカ系複合微粒子分散液からなる試料約１ｇ（固形分２０質量％)を白金皿に採取する。リン酸３ｍｌ、硝酸５ｍｌ、弗化水素酸１０ｍｌを加えて、サンドバス上で加熱する。乾固したら、少量の水と硝酸５０ｍｌを加えて溶解させて１００ｍｌのメスフラスコにおさめ、水を加えて１００ｍｌとする。この溶液でＮａ、Ｋは原子吸光分光分析装置（例えば日立製作所社製、Ｚ−２３１０）で測定する。次に、１００ｍｌにおさめた溶液から分液１０ｍｌを２０ｍｌメスフラスコに採取する操作を５回繰り返し、分液１０ｍｌを５個得る。そして、これを用いて、Ａｌ、Ａｇ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｍｇ、Ｎｉ、Ｔｉ、Ｚｎ、Ｚｒ、Ｕ及びＴｈについてＩＣＰプラズマ発光分析装置（例えばＳＩＩ製、ＳＰＳ５５２０）にて標準添加法で測定を行う。ここで、同様の方法でブランクも測定して、ブランク分を差し引いて調整し、各元素における測定値とする。
以下、特に断りがない限り、本発明におけるＮａ、Ａｌ、Ａｇ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｋ、Ｍｇ、Ｎｉ、Ｔｉ、Ｚｎ、Ｚｒ、Ｕ及びＴｈの成分の含有率（含有量）は、このような方法で測定して得た値を意味するものとする。
[Silica-based composite fine particles]
The content of each element shall be measured by the following method.
First, about 1 g (solid content 20% by mass) of a sample composed of a silica-based composite fine particle dispersion is collected in a platinum dish. Add 3 ml of phosphoric acid, 5 ml of nitric acid, and 10 ml of hydrofluoric acid, and heat on a sand bath. After drying, add a small amount of water and 50 ml of nitric acid to dissolve and put in a 100 ml volumetric flask, and add water to make 100 ml. In this solution, Na and K are measured by an atomic absorption spectrophotometer (for example, Z-2310 manufactured by Hitachi, Ltd.). Next, the operation of collecting 10 ml of the separated solution in a 20 ml volumetric flask from the solution contained in 100 ml is repeated 5 times to obtain 5 10 ml separated solutions. Then, using this, a standard addition method for Al, Ag, Ca, Cr, Cu, Fe, Mg, Ni, Ti, Zn, Zr, U and Th using an ICP plasma emission spectrometer (for example, SII, SPS5520). Measure with. Here, the blank is also measured by the same method, and the blank is subtracted and adjusted to obtain the measured value for each element.
Hereinafter, unless otherwise specified, the content (content) of the components Na, Al, Ag, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn, Zr, U and Th in the present invention is , It shall mean the value obtained by measuring by such a method.
各陰イオンの含有率は、以下の方法によって測定するものとする。
＜Ｃｌ＞
シリカ系複合微粒子分散液からなる試料２０ｇ（固形分２０質量％）にアセトンを加え１００ｍｌに調整し、この溶液に、酢酸５ｍｌ、０．００１モル塩化ナトリウム溶液４ｍｌを加えて０．００２モル硝酸銀溶液で電位差滴定法（京都電子製：電位差滴定装置ＡＴ−６１０）で分析を行う。
別途ブランク測定として、アセトン１００ｍｌに酢酸５ｍｌ、０．００１モル塩化ナトリウム溶液４ｍｌを加えて０．００２モル硝酸銀溶液で滴定を行った場合の滴定量を求めておき、試料を用いた場合の滴定量から差し引き、試料の滴定量とした。
The content of each anion shall be measured by the following method.
<Cl>
20 g of a sample (solid content 20% by mass) consisting of a silica-based composite fine particle dispersion is adjusted to 100 ml by adding acetone, and 5 ml of acetic acid and 4 ml of 0.001 mol sodium chloride solution are added to this solution to make a 0.002 mol silver nitrate solution. The analysis is performed by the potentiometric titration method (manufactured by Kyoto Electronics: Potentiometric Titration Device AT-610).
As a separate blank measurement, the titration amount when 5 ml of acetic acid and 4 ml of 0.001 mol sodium chloride solution are added to 100 ml of acetone and titration is performed with 0.002 mol silver nitrate solution is obtained, and the titration amount when a sample is used is obtained. Was subtracted from the sample titration.
＜ＮＯ3、ＳＯ4、Ｆ＞
シリカ系複合微粒子分散液からなる試料５ｇ（固形分２０質量％）を水で希釈して１００ｍｌにおさめ、遠心分離機（日立製 ＨＩＭＡＣ ＣＴ０６Ｅ）にて４０００ｒｐｍで２０分遠心分離して、沈降成分を除去して得た液をイオンクロマトグラフ（ＤＩＯＮＥＸ製 ＩＣＳ−１１００）にて分析した。
<NO 3 , SO 4 , F>
A sample consisting of a silica-based composite fine particle dispersion (solid content 20% by mass) is diluted with water, contained in 100 ml, and centrifuged at 4000 rpm for 20 minutes with a centrifuge (HIMAC CT06E manufactured by Hitachi) to remove the sedimented components. The liquid obtained by removal was analyzed by an ion chromatograph (ICS-1100 manufactured by DIONEX).
＜ＳｉＯ2、ＣｅＯ2＞
シリカ系複合微粒子におけるシリカとセリアの含有率を求める場合、まずシリカ系複合微粒子の分散液の固形分濃度を、１０００℃灼熱減量を行って秤量により求める。次にＣｅについて、Ａｌ〜Ｔｈ等と同様にＩＣＰプラズマ発光分析装置（例えば、ＳＩＩ製、ＳＰＳ５５２０）を用いて標準添加法で測定を行い、得られたＣｅ含有率からＣｅＯ2質量％を算出する。そして、本発明の複合微粒子を構成するＣｅＯ2以外の成分はＳｉＯ2であるとして、ＳｉＯ2質量％を算出する。
なお、シリカ微粒子（母粒子）における各元素又は各陰イオンの含有率は、上記シリカ系複合微粒子の分析方法において、試料をシリカ系複合微粒子分散液に代えて、シリカ微粒子分散液を用いることにより行った。
<SiO 2 , CeO 2 >
When determining the content of silica and ceria in the silica-based composite fine particles, first, the solid content concentration of the dispersion liquid of the silica-based composite fine particles is determined by weighing by performing a burning reduction of 1000 ° C. Next, Ce is measured by a standard addition method using an ICP plasma emission spectrometer (for example, SII, SPS5520) in the same manner as Al to Th, and CeO 2 % by mass is calculated from the obtained Ce content. .. Then, it is assumed that the component other than CeO 2 constituting the composite fine particles of the present invention is SiO 2 , and the mass% of SiO 2 is calculated.
The content of each element or each anion in the silica fine particles (mother particles) is determined by using a silica fine particle dispersion instead of the silica composite fine particle dispersion in the above method for analyzing silica composite fine particles. went.
［Ｘ線回折法、結晶子径の測定］
前述の方法に則り、実施例及び比較例で得られたシリカ系複合微粒子分散液を従来公知の乾燥機を用いて乾燥し、得られた粉体を乳鉢にて１０分粉砕し、Ｘ線回折装置（理学電気(株)製、ＲＩＮＴ１４００）によってＸ線回折パターンを得て、結晶型を特定した。
また、前述のように、得られたＸ線回折パターンにおける２θ＝２８度近傍の（１１１）面（２θ＝２８度近傍）のピークの半価幅を測定し、Ｓｃｈｅｒｒｅｒの式により、結晶子径を求めた。
[X-ray diffraction method, measurement of crystallite diameter]
According to the above method, the silica-based composite fine particle dispersions obtained in Examples and Comparative Examples are dried using a conventionally known dryer, and the obtained powder is pulverized in a mortar for 10 minutes and X-ray diffraction is performed. An X-ray diffraction pattern was obtained by an apparatus (RINT1400 manufactured by Rigaku Denki Co., Ltd.), and the crystal type was specified.
Further, as described above, the half-value width of the peak of the (111) plane (near 2θ = 28 degrees) near 2θ = 28 degrees in the obtained X-ray diffraction pattern is measured, and the crystallite diameter is measured by Scherrer's equation. Asked.
＜平均粒子径＞
実施例及び比較例で得られたシリカ微粒子分散液及びシリカ系複合微粒子分散液について、これに含まれる粒子の平均粒子径を前述の方法で測定した。具体的にはシリカ母粒子は大塚電子社製ＰＡＲ−ＩＩＩ及びＨＯＲＩＢＡ社製ＬＡ９５０を用い、シリカ系複合微粒子については日機装株式会社製マイクロトラックＵＰＡ装置を用いた。
<Average particle size>
With respect to the silica fine particle dispersion and the silica-based composite fine particle dispersion obtained in Examples and Comparative Examples, the average particle size of the particles contained therein was measured by the above-mentioned method. Specifically, PAR-III manufactured by Otsuka Electronics Co., Ltd. and LA950 manufactured by HORIBA Co., Ltd. were used as the silica mother particles, and a Microtrack UPA device manufactured by Nikkiso Co., Ltd. was used as the silica-based composite fine particles.
［研磨試験方法］
＜ＳｉＯ2膜の研磨＞
実施例及び比較例の各々において得られたシリカ系複合微粒子分散液を含むスラリー（研磨用スラリー）を調整した。ここで固形分濃度は０．６質量％で硝酸を添加してｐＨは５．０とした。
次に、被研磨基板として、熱酸化法により作製したＳｉＯ2絶縁膜（厚み１μｍ）基板を準備した。
次に、この被研磨基板を研磨装置（ナノファクター株式会社製、ＮＦ３００）にセットし、研磨パッド（ニッタハース社製「ＩＣ-１０００／ＳＵＢＡ４００同心円タイプ」）を使用し、基板荷重０．５ＭＰａ、テーブル回転速度９０ｒｐｍで研磨用スラリーを５０ｍｌ／分の速度で１分間供給して研磨を行った。
そして、研磨前後の被研磨基材の重量変化を求めて研磨速度を計算した。
また、研磨基材の表面の平滑性（表面粗さＲａ）を原子間力顕微鏡（ＡＦＭ、株式会社日立ハイテクサイエンス社製）を用いて測定した。
なお研磨傷の観察は、光学顕微鏡を用いて絶縁膜表面を観察することで行った。
[Polishing test method]
<Polishing of SiO 2 film>
A slurry (polishing slurry) containing the silica-based composite fine particle dispersion obtained in each of Examples and Comparative Examples was prepared. Here, the solid content concentration was 0.6% by mass, and nitric acid was added to adjust the pH to 5.0.
Next, as a substrate to be polished, a SiO 2 insulating film (thickness 1 μm) substrate prepared by a thermal oxidation method was prepared.
Next, this substrate to be polished is set in a polishing device (NF300 manufactured by Nanofactor Co., Ltd.), and a polishing pad (“IC-1000 / SUBA400 concentric circle type” manufactured by Nitta Hearth Co., Ltd.) is used, and the substrate load is 0.5 MPa, the table. Polishing was performed by supplying a polishing slurry at a rotation speed of 90 rpm for 1 minute at a rate of 50 ml / min.
Then, the polishing rate was calculated by obtaining the weight change of the substrate to be polished before and after polishing.
Further, the smoothness (surface roughness Ra) of the surface of the polishing substrate was measured using an atomic force microscope (AFM, manufactured by Hitachi High-Tech Science Corporation).
The polishing scratches were observed by observing the surface of the insulating film using an optical microscope.
＜アルミハードディスクの研磨＞
実施例及び比較例の各々において得られたシリカ系複合微粒子分散液を含むスラリー（研磨用スラリー）を調整した。ここで固形分濃度は９質量％で硝酸を添加してｐＨを２．０に調整した。
アルミハードディスク用基板を研磨装置（ナノファクター株式会社製、ＮＦ３００）にセットし、研磨パッド（ニッタハース社製「ポリテックスφ１２」）を使用し、基板負荷０．０５ＭＰａ、テーブル回転速度３０ｒｐｍで研磨スラリーを２０ｍｌ／分の速度で５分間供給して研磨を行い、超微細欠陥・可視化マクロ装置（ＶＩＳＩＯＮ ＰＳＹＴＥＣ社製、製品名：Ｍａｉｃｒｏ―Ｍａｘ）を使用し、Ｚｏｏｍ１５にて全面観察し、６５．９７ｃｍ2に相当する研磨処理された基板表面に存在するスクラッチ（線状痕）の個数を数えて合計し、次の基準に従って評価した。
線状痕の個数 評価
５０個未満 「非常に少ない」
８０個未満、５０個以上 「少ない」
８０個以上 「多い」
＊少なくとも８０個以上で総数をカウントできないほど多い 「※」
<Aluminum hard disk polishing>
A slurry (polishing slurry) containing the silica-based composite fine particle dispersion obtained in each of Examples and Comparative Examples was prepared. Here, the solid content concentration was 9% by mass, and nitric acid was added to adjust the pH to 2.0.
Set the substrate for aluminum hard disk in a polishing device (NF300 manufactured by Nanofactor Co., Ltd.), and use a polishing pad (“Polytex φ12” manufactured by Nitta Hearth Co., Ltd.) to prepare a polishing slurry at a substrate load of 0.05 MPa and a table rotation speed of 30 rpm. Polishing is performed by supplying at a rate of 20 ml / min for 5 minutes, and the entire surface is observed with Zoom15 using an ultrafine defect / visualization macro device (manufactured by VISION PSYTEC, product name: Micro-Max), and 65.97 cm 2 The number of scratches (linear marks) existing on the surface of the polished substrate corresponding to the above was counted and totaled, and evaluated according to the following criteria.
Number of linear marks Evaluation Less than 50 "Very few"
Less than 80, 50 or more "less"
80 or more "many"
* At least 80 or more, too many to count the total number "*"
＜流動電位＞
実施例及び比較例で得られた各シリカ系複合微粒子分散液について、流動電位の測定及びカチオンコロイド滴定を行った。滴定装置として、流動電位滴定ユニット（ＰＣＤ−５００）を搭載した自動滴定装置ＡＴ−５１０（京都電子工業製）を用いた。
まず、固形分濃度を１質量％に調整したシリカ系複合微粒子分散液を０．０５％の塩酸水溶液を添加してｐＨ６に調整した。その液の固形分として０．８ｇに相当する量を流動電位測定装置のセルにとり、流動電位の測定を行った。次にカチオンコロイド滴定液（０．００２５Ｎポリ塩化ジアリルジメチルアンモニウム溶液）を添加して滴定を行った。そして、カチオンコロイド滴定液の添加量（ｍｌ）をＸ軸、シリカ系複合微粒子分散液の流動電位（ｍＶ）をＹ軸にプロットして、流動電位曲線の開始点における流動電位Ｉ（ｍＶ）、ならびにクニックにおける流動電位Ｃ（ｍＶ）及びカチオンコロイド滴定液の添加量Ｖ（ｍｌ）を求め、ΔＰＣＤ／Ｖ＝（Ｉ−Ｃ）／Ｖを算出した。結果を第１表に示す。
また、実施例及び比較例で得られた各シリカ系複合微粒子分散液について、流動電位の測定及びカチオンコロイド滴定を行った。滴定装置として、流動電位滴定ユニット（ＰＣＤ−５００）を搭載した自動滴定装置ＡＴ−５１０（京都電子工業製）を用いた。
まず、固形分濃度を１質量％に調整したシリカ系複合微粒子分散液を０．０５％の塩酸水溶液を添加してｐＨ６に調整した。その液の固形分として０．８ｇに相当する量を流動電位測定装置のセルにとり、流動電位の測定を行った。次にカチオンコロイド滴定液（０．００２５Ｎポリ塩化ジアリルジメチルアンモニウム溶液）を添加して滴定を行った。そして、カチオンコロイド滴定液の添加量（ｍｌ）をＸ軸、シリカ系複合微粒子分散液の流動電位（ｍＶ）をＹ軸にプロットして、流動電位曲線の開始点における流動電位Ｉ（ｍＶ）、ならびにクニックにおける流動電位Ｃ（ｍＶ）及びカチオンコロイド滴定液の添加量Ｖ（ｍｌ）を求め、ΔＰＣＤ／Ｖ＝（Ｉ−Ｃ）／Ｖを算出した。結果を第１表に示す。
<Flow potential>
The flow potential of each silica-based composite fine particle dispersion obtained in Examples and Comparative Examples was measured and cationic colloid titration was performed. As the titrator, an automatic titrator AT-510 (manufactured by Kyoto Denshi Kogyo Co., Ltd.) equipped with a flow potential titration unit (PCD-500) was used.
First, a silica-based composite fine particle dispersion having a solid content concentration adjusted to 1% by mass was adjusted to pH 6 by adding a 0.05% aqueous hydrochloric acid solution. An amount corresponding to 0.8 g of the solid content of the liquid was taken in a cell of the flow potential measuring device, and the flow potential was measured. Next, a cationic colloid titration solution (0.0025N polychlorinated diallyldimethylammonium solution) was added for titration. Then, the addition amount (ml) of the cationic colloid titration solution is plotted on the X-axis, and the flow potential (mV) of the silica-based composite fine particle dispersion is plotted on the Y-axis, and the flow potential I (mV) at the start point of the flow potential curve, In addition, the flow potential C (mV) in the knick and the addition amount V (ml) of the cationic colloid titration solution were determined, and ΔPCD / V = (IC) / V was calculated. The results are shown in Table 1.
In addition, the flow potential of each silica-based composite fine particle dispersion obtained in Examples and Comparative Examples was measured and cationic colloid titration was performed. As the titrator, an automatic titrator AT-510 (manufactured by Kyoto Denshi Kogyo Co., Ltd.) equipped with a flow potential titration unit (PCD-500) was used.
First, a silica-based composite fine particle dispersion having a solid content concentration adjusted to 1% by mass was adjusted to pH 6 by adding a 0.05% aqueous hydrochloric acid solution. An amount corresponding to 0.8 g of the solid content of the liquid was taken in a cell of the flow potential measuring device, and the flow potential was measured. Next, a cationic colloid titration solution (0.0025N polychlorinated diallyldimethylammonium solution) was added for titration. Then, the addition amount (ml) of the cationic colloid titration solution is plotted on the X-axis, and the flow potential (mV) of the silica-based composite fine particle dispersion is plotted on the Y-axis, and the flow potential I (mV) at the start point of the flow potential curve, In addition, the flow potential C (mV) in the knick and the addition amount V (ml) of the cationic colloid titration solution were determined, and ΔPCD / V = (IC) / V was calculated. The results are shown in Table 1.
＜合成例＞
《高純度珪酸液》の調製
ＳｉＯ2濃度が２４．０６質量％、Ｎａ2Ｏ濃度が７．９７質量％の珪酸ナトリウム水溶液を用意した。そして、この珪酸ナトリウム水溶液にＳｉＯ2濃度が５．０質量％となるように純水を添加した。
<Synthesis example>
"High-purity silicic acid solution" is prepared SiO 2 concentration of 24.06 wt%, Na 2 O concentration was prepared aqueous solution of sodium silicate of 7.97 wt%. Then, pure water was added to the sodium silicate aqueous solution so that the SiO 2 concentration was 5.0% by mass.
［酸性珪酸液］
得られた５．０質量％の珪酸ナトリウム水溶液１８ｋｇを、６Ｌの強酸性陽イオン交換樹脂（ＳＫ１ＢＨ、三菱化学社製）に空間速度３．０ｈ-1で通液させ、ｐＨが２．７の酸性珪酸液１８ｋｇを得た。
得られた酸性珪酸液のＳｉＯ2濃度は４．７質量％であった。
[Acid silicic acid solution]
18 kg of the obtained 5.0 mass% sodium silicate aqueous solution was passed through a 6 L strong acid cation exchange resin (SK1BH, manufactured by Mitsubishi Chemical Corporation) at a space velocity of 3.0 h -1 to have a pH of 2.7. 18 kg of an acidic silicic acid solution was obtained.
The SiO 2 concentration of the obtained acidic silicic acid solution was 4.7% by mass.
［高純度珪酸液］
次に、酸性珪酸液を、強酸性陽イオン交換樹脂（ＳＫ１ＢＨ、三菱化学社製）に空間速度３．０ｈ-1で通液させ、ｐＨが２．７の高純度珪酸液を得た。得られた高純度珪酸液のＳｉＯ2濃度は４．４質量％であった。
[High-purity silicic acid solution]
Next, the acidic silicic acid solution was passed through a strongly acidic cation exchange resin (SK1BH, manufactured by Mitsubishi Chemical Corporation) at a space velocity of 3.0 h -1 to obtain a high-purity silicic acid solution having a pH of 2.7. The SiO 2 concentration of the obtained high-purity silicic acid solution was 4.4% by mass.
《シリカ微粒子分散液（シリカ微粒子の平均粒子径：２５ｎｍ）》の調製
純水４２ｇに高純度珪酸液を攪拌しながら５１４．５ｇ添加し、次いで１５％のアンモニア水を１，５８４．６ｇ添加し、その後８３℃に昇温して３０分保持した。
次に高純度珪酸液１３，７００ｇを１８時間かけて添加し、添加終了後に８３℃を保持したまま熟成を行い、２５ｎｍのシリカ微粒子分散液を得た。
得られたシリカ微粒子分散液を４０℃まで冷却し、限外ろ過膜（旭化成製ＳＩＰ１０１３）にてＳｉＯ2濃度を１２質量％まで濃縮した。
Preparation of << Silica fine particle dispersion (average particle size of silica fine particles: 25 nm) >> 514.5 g of high-purity silicic acid solution was added to 42 g of pure water with stirring, and then 1,584.6 g of 15% aqueous ammonia was added. After that, the temperature was raised to 83 ° C. and held for 30 minutes.
Next, 13,700 g of a high-purity silicic acid solution was added over 18 hours, and after the addition was completed, aging was carried out while maintaining 83 ° C. to obtain a silica fine particle dispersion of 25 nm.
The obtained silica fine particle dispersion was cooled to 40 ° C., and the SiO 2 concentration was concentrated to 12% by mass with an ultrafiltration membrane (SIP1013 manufactured by Asahi Kasei Corporation).
《シリカ微粒子分散液（シリカ微粒子の平均粒子径：４５ｎｍ）》の調製
純水９９１ｇに攪拌しながら１２質量％の２５ｎｍシリカ微粒子分散液を９６３ｇ加えた。次いで１５％アンモニア水１，４１４ｇを添加し、その後８７℃に昇温して３０分保持した。
次に高純度珪酸液１２，８１２ｇを１８時間かけて添加し、添加終了後に８７℃を保持したまま熟成を行い、４５ｎｍのシリカ微粒子分散液を得た。
得られたシリカ微粒子分散液を４０℃まで冷却し、限外ろ過膜（旭化成製ＳＩＰ１０１３）にてＳｉＯ2濃度を１２質量％まで濃縮した。
Preparation of << Silica Fine Particle Dispersion (Average Particle Diameter of Silica Fine Particles: 45 nm) >> 963 g of 12 mass% 25 nm silica fine particle dispersion was added to 991 g of pure water with stirring. Then, 1,414 g of 15% aqueous ammonia was added, and then the temperature was raised to 87 ° C. and maintained for 30 minutes.
Next, 12,812 g of a high-purity silicic acid solution was added over 18 hours, and after the addition was completed, aging was carried out while maintaining 87 ° C. to obtain a silica fine particle dispersion of 45 nm.
The obtained silica fine particle dispersion was cooled to 40 ° C., and the SiO 2 concentration was concentrated to 12% by mass with an ultrafiltration membrane (SIP1013 manufactured by Asahi Kasei Corporation).
《シリカ微粒子分散液（シリカ微粒子の平均粒子径：７０ｎｍ）》の調製
純水７０５ｇに攪拌しながら平均粒子径４５ｎｍのシリカ微粒子が溶媒に分散してなるシリカ微粒子分散液（ＳｉＯ2濃度１２質量％）を７０５ｇ加えた。次いで１５％アンモニア水５０ｇを添加し、その後８７℃に昇温して３０分保持した。
次に高純度珪酸液７，１６８ｇを１８時間かけて添加し、添加終了後に８７℃を保持したまま熟成を行い、平均粒子径７０ｎｍのシリカ微粒子が溶媒に分散してなるシリカ微粒子分散液を得た。
得られたシリカ微粒子分散液を４０℃まで冷却し、限外ろ過膜（旭化成製ＳＩＰ１０１３）にてＳｉＯ2濃度を１２質量％まで濃縮した。
Preparation of << Silica Fine Particle Dispersion Liquid (Average Particle Size of Silica Fine Particles: 70 nm) >> A silica fine particle dispersion liquid (SiO 2 concentration 12% by mass) in which silica fine particles having an average particle diameter of 45 nm are dispersed in a solvent while stirring with 705 g of pure water. ) Was added. Then, 50 g of 15% aqueous ammonia was added, and then the temperature was raised to 87 ° C. and maintained for 30 minutes.
Next, 7,168 g of a high-purity silicic acid solution was added over 18 hours, and after the addition was completed, aging was carried out while maintaining 87 ° C. to obtain a silica fine particle dispersion liquid in which silica fine particles having an average particle diameter of 70 nm were dispersed in a solvent. It was.
The obtained silica fine particle dispersion was cooled to 40 ° C., and the SiO 2 concentration was concentrated to 12% by mass with an ultrafiltration membrane (SIP1013 manufactured by Asahi Kasei Corporation).
《シリカ微粒子分散液（シリカ微粒子の平均粒子径：９６ｎｍ）》の調製
純水１，０８１ｇに攪拌しながら平均粒子径７０ｎｍのシリカ微粒子が溶媒に分散してなる分散液（ＳｉＯ2濃度：１２質量％）を１，０８１ｇ加えた。次いで１５％アンモニア水５０ｇを添加し、その後８７℃に昇温して３０分保持した。
次に高純度珪酸液６，１４３ｇを１８時間かけて添加し、添加終了後に８７℃を保持したまま熟成を行い、動的光散乱法（動的光散乱粒子径測定装置：ＰＡＲ−III）で測定された平均粒子径９６ｎｍのシリカ微粒子が溶媒に分散してなるシリカ微粒子分散液を得た。
得られたシリカ微粒子分散液を４０℃まで冷却し、限外ろ過膜（旭化成製ＳＩＰ１０１３）にてＳｉＯ2濃度を１２質量％まで濃縮した。濃縮後のシリカ微粒子分散液に陰イオン交換樹脂 三菱化学社製 ＳＡＮＵＰ Ｂを添加して陰イオンを除去した。
得られたシリカ微粒子分散液に超純水を加えて、ＳｉＯ2固形分濃度３質量％のＡ液６,０００ｇを得た。（以下、シリカ系複合微粒子分散液の製造工程において、後記Ｂ液を投入するシリカ微粒子分散液を「Ａ液」とする。）
Preparation of << Silica Fine Particle Dispersion Liquid (Average Particle Size of Silica Fine Particles: 96 nm) >> A dispersion liquid in which silica fine particles having an average particle diameter of 70 nm are dispersed in a solvent while stirring in 1,081 g of pure water (SiO 2 concentration: 12 mass). %) Was added in an amount of 1,081 g. Then, 50 g of 15% aqueous ammonia was added, and then the temperature was raised to 87 ° C. and maintained for 30 minutes.
Next, 6,143 g of a high-purity silicic acid solution was added over 18 hours, and after the addition was completed, aging was performed while maintaining 87 ° C. by a dynamic light scattering method (dynamic light scattering particle size measuring device: PAR-III). A silica fine particle dispersion prepared by dispersing the measured silica fine particles having an average particle diameter of 96 nm in a solvent was obtained.
The obtained silica fine particle dispersion was cooled to 40 ° C., and the SiO 2 concentration was concentrated to 12% by mass with an ultrafiltration membrane (SIP1013 manufactured by Asahi Kasei Corporation). An anion exchange resin SANUP B manufactured by Mitsubishi Chemical Corporation was added to the concentrated silica fine particle dispersion to remove anions.
Ultrapure water was added to the obtained silica fine particle dispersion to obtain 6,000 g of solution A having a SiO 2 solid content concentration of 3% by mass. (Hereinafter, in the manufacturing process of the silica-based composite fine particle dispersion liquid, the silica fine particle dispersion liquid into which the liquid B is added will be referred to as “liquid A”).
次に、硝酸セリウム（III）６水和物（関東化学社製、４Ｎ高純度試薬）にイオン交換水を加え、ＣｅＯ2換算で２．５質量％のＢ液を得た。（以下、セリウム金属塩分散液を「Ｂ液」とする。） Next, ion-exchanged water was added to cerium nitrate (III) hexahydrate (4N high-purity reagent manufactured by Kanto Chemical Co., Inc.) to obtain 2.5% by mass of B solution in terms of CeO 2 . (Hereinafter, the cerium metal salt dispersion liquid is referred to as "B liquid".)
次に、Ａ液（６，０００ｇ）を５０℃まで昇温して、撹拌しながら、ここへＢ液（８，４５３ｇ、ＳｉＯ2の１００質量部に対して、ＣｅＯ2が１１７．４質量部に相当）を１８時間かけて添加した。この間、液温を５０℃に維持しておき、また、必要に応じて３％アンモニア水を添加して、ｐＨ７．８５を維持するようにした。
そして、Ｂ液の添加が終了したら、液温を９３℃へ上げて４時間熟成を行った。熟成終了後に室内に放置することで放冷し、室温まで冷却した後に、限外膜にてイオン交換水を補給しながら洗浄を行った。洗浄を終了して得られた前駆体粒子分散液は、固形分濃度が７質量％、ｐＨが９．１（２５℃にて）、電導度が６７μｓ／ｃｍ（２５℃にて）であった。
Next, the temperature of solution A (6,000 g) was raised to 50 ° C., and while stirring, the amount of CeO 2 was 117.4 parts by mass with respect to 100 parts by mass of solution B (8,453 g, SiO 2 ). Equivalent to) was added over 18 hours. During this period, the liquid temperature was maintained at 50 ° C., and 3% aqueous ammonia was added as needed to maintain pH 7.85.
Then, when the addition of the liquid B was completed, the liquid temperature was raised to 93 ° C. and aging was carried out for 4 hours. After the aging was completed, the mixture was allowed to cool by leaving it indoors, cooled to room temperature, and then washed with an ultrafiltration membrane while supplying ion-exchanged water. The precursor particle dispersion obtained after washing had a solid content concentration of 7% by mass, a pH of 9.1 (at 25 ° C), and a conductivity of 67 μs / cm (at 25 ° C). ..
次に得られた前駆体粒子分散液に５質量％酢酸を加えてｐＨを６．５に調整して、１２０℃の乾燥機中で１６時間乾燥させた後、１０９０℃のマッフル炉を用いて２時間焼成を行い、粉体（焼成体）を得た。 Next, 5% by mass acetic acid was added to the obtained precursor particle dispersion to adjust the pH to 6.5, and the mixture was dried in a dryer at 120 ° C. for 16 hours, and then used in a muffle furnace at 1090 ° C. Baking was carried out for 2 hours to obtain a powder (baked product).
得られた粉体１２５ｇにイオン交換水３７５ｇを加え、さらに３％アンモニア水溶液を用いてｐＨを９に調整した後、φ０．２２ｍｍの高純度シリカビーズ（大研化学工業株式会社製）にて湿式解砕、粉砕を行い、固形分濃度２０質量％の焼成体解砕分散液５４０ｇを得た。 375 g of ion-exchanged water was added to 125 g of the obtained powder, and the pH was adjusted to 9 using a 3% aqueous ammonia solution, and then wet with high-purity silica beads (manufactured by Daiken Kagaku Kogyo Co., Ltd.) having a diameter of 0.22 mm. Crushing and crushing were carried out to obtain 540 g of a calcined product crushed dispersion having a solid content concentration of 20% by mass.
＜実施例１＞
前記合成例で得られた固形分濃度２０質量％の焼成体解砕分散液を、ＨＩＴＡＣＨＩ社製遠心分離装置ＣＲ２１Ｇ（ローター型式Ｒ２１Ａ）にて、２０００ｒｐｍ（６２０Ｇ）で３分間遠心分離を行い、上澄液と沈降品を分離し、上澄液を回収した。
次に、回収した上澄液を２５００ｒｐｍ（９８０Ｇ）で３分間遠心分離を行い、上澄液と沈降品を分離し、上澄液を回収した。
続いて、回収した上澄液を２８００ｒｐｍ（１２５０Ｇ）で５分間遠心分離を行い、上澄液と沈降品を分離し、沈降品を回収した。
得られた沈降品としてのシリカ系複合微粒子分散液に含まれるシリカ系複合微粒子の平均粒子径を測定したところ、２８０ｎｍ、ΔＰＣＤ／Ｖは−５１、初期流動電位は−５５０ｍＶであった。
また、電子顕微鏡観察写真の画像解析法にて１〜４個玉の割合を測定した。さらに前記の２種類の研磨試験を行い、研磨速度およびスクラッチの個数を計測した。
結果を第１表に示す。
また、実施例１で得られたシリカ系複合微粒子分散液の透過型電子顕微鏡写真（倍率１０万倍）を図１に示す。
<Example 1>
The calcined body crushed dispersion obtained in the above synthesis example having a solid content concentration of 20% by mass was centrifuged at 2000 rpm (620 G) for 3 minutes using a Hitachi Centrifuge CR21G (rotor model R21A). The supernatant and the precipitated product were separated, and the supernatant was recovered.
Next, the recovered supernatant was centrifuged at 2500 rpm (980 G) for 3 minutes to separate the supernatant from the precipitated product, and the supernatant was recovered.
Subsequently, the recovered supernatant was centrifuged at 2800 rpm (1250 G) for 5 minutes to separate the supernatant from the precipitated product, and the precipitated product was recovered.
When the average particle size of the silica-based composite fine particles contained in the obtained silica-based composite fine particle dispersion as a precipitated product was measured, it was 280 nm, ΔPCD / V was −51, and the initial flow potential was −550 mV.
In addition, the ratio of 1 to 4 balls was measured by the image analysis method of the electron microscope observation photograph. Further, the above two types of polishing tests were performed, and the polishing speed and the number of scratches were measured.
The results are shown in Table 1.
In addition, a transmission electron micrograph (magnification of 100,000 times) of the silica-based composite fine particle dispersion obtained in Example 1 is shown in FIG.
＜実施例２＞
前記合成例で得られた固形分濃度２０質量％の焼成体解砕分散液を、ＨＩＴＡＣＨＩ社製遠心分離装置ＣＲ２１Ｇ（ローター型式Ｒ２１Ａ）にて、２０００ｒｐｍ（６２０Ｇ）で３分間遠心分離を行い、上澄液と沈降品を分離し、上澄液を回収した。
次に、回収した上澄液を２５００ｒｐｍ（９８０Ｇ）で３分間遠心分離を行い、上澄液と沈降品を分離し、上澄液を回収した。
続いて、回収した上澄液を２８００ｒｐｍ（１２５０Ｇ）で５分間遠心分離処理し、上澄液と沈降品を分離し、上澄液を回収した。
続いて、回収した上澄液を３２００ｒｐｍ（１６５０Ｇ）で５分間遠心分離を行い、上澄液と沈降品を分離し、沈降品を回収した。
得られた沈降品としてのシリカ系複合微粒子分散液に含まれるシリカ系複合微粒子の平均粒子径を後述する方法で測定したところ、２４５ｎｍであり、ΔＰＣＤ／Ｖは−５５、初期流動電位は−５６３ｍＶであった。
また、電子顕微鏡観察写真の画像解析法にて１〜４個玉の割合を測定した。さらに前記の２種類の研磨試験を行い、研磨速度およびスクラッチの個数を計測した。
結果を第１表に示す。
また、実施例２で得られたシリカ系複合微粒子分散液の透過型電子顕微鏡写真（倍率１０万倍）を図２に示す。
<Example 2>
The calcined body crushed dispersion obtained in the above synthesis example having a solid content concentration of 20% by mass was centrifuged at 2000 rpm (620 G) for 3 minutes using a Hitachi Centrifuge CR21G (rotor model R21A). The supernatant and the precipitated product were separated, and the supernatant was recovered.
Next, the recovered supernatant was centrifuged at 2500 rpm (980 G) for 3 minutes to separate the supernatant from the precipitated product, and the supernatant was recovered.
Subsequently, the recovered supernatant was centrifuged at 2800 rpm (1250 G) for 5 minutes to separate the supernatant from the precipitated product, and the supernatant was recovered.
Subsequently, the recovered supernatant was centrifuged at 3200 rpm (1650 G) for 5 minutes to separate the supernatant from the precipitated product, and the precipitated product was recovered.
The average particle size of the silica-based composite fine particles contained in the obtained silica-based composite fine particle dispersion as a precipitated product was measured by the method described later and found to be 245 nm, ΔPCD / V was -55, and the initial flow potential was -563 mV. Met.
In addition, the ratio of 1 to 4 balls was measured by the image analysis method of the electron microscope observation photograph. Further, the above two types of polishing tests were performed, and the polishing speed and the number of scratches were measured.
The results are shown in Table 1.
Further, FIG. 2 shows a transmission electron micrograph (magnification of 100,000 times) of the silica-based composite fine particle dispersion obtained in Example 2.
実施例１で得られたシリカ系複合微粒子分散液に含まれるシリカ系複合微粒子について、エネルギー分散型Ｘ線分光測定（ＥＤＳ）を行い、元素分布図（図３）を得た。
エネルギー分散型Ｘ線分光測定（ＥＤＳ）の測定条件を以下に示す。
試料作製は、シリカ系複合微粒子を純水中で分散させた後、カーボン支持膜付きＣｕメッシュに載せて、以下の測定装置にて測定を行った。
測定装置：日本電子社製、ＵＴＷ型Ｓｉ（Ｌｉ）半導体検出器、ビーム径０．２ｎｍ
Energy dispersive X-ray spectroscopy (EDS) was performed on the silica-based composite fine particles contained in the silica-based composite fine particle dispersion obtained in Example 1 to obtain an element distribution diagram (FIG. 3).
The measurement conditions for energy dispersive X-ray spectroscopy (EDS) are shown below.
The sample was prepared by dispersing silica-based composite fine particles in pure water, placing them on a Cu mesh with a carbon support film, and measuring with the following measuring device.
Measuring device: UTW type Si (Li) semiconductor detector manufactured by JEOL Ltd., beam diameter 0.2 nm
図３に示す元素分布図から、Ｃｅ元素の外側（粒子の表面側）に、Ｓｉ及びＯ（酸素）が存在していることが確認できた。 From the element distribution diagram shown in FIG. 3, it was confirmed that Si and O (oxygen) were present on the outside of the Ce element (on the surface side of the particles).
次に、実施例１で得られたシリカ系複合微粒子分散液が含むシリカ系複合微粒子について、透過型電子顕微鏡（日本電子社製、ＪＥＭ−２１００Ｆ、電界放射型透過電子顕微鏡（Ｃｓ補正付属）、加速電子：１２０ｋＶ、倍率：５０，０００倍）を用いて観察し、子粒子（セリア結晶粒子）の外側に被膜が存在することを確認し、その後、この被膜の部分へ選択的に電子ビームを当てたＥＤＳ測定を行った。
エネルギー分散型Ｘ線分光測定（ＥＤＳ）の測定条件を以下に示す。
シリカ系複合微粒子を純水中で分散させた後、カーボン支持膜付きＣｕメッシュに載せて、以下の測定装置にて測定を行った。
測定装置：日本電子社製、ＵＴＷ型Ｓｉ（Ｌｉ）半導体検出器
ビーム系：０．２ｎｍ
Next, regarding the silica-based composite fine particles contained in the silica-based composite fine particle dispersion obtained in Example 1, a transmission electron microscope (manufactured by JEOL Ltd., JEM-2100F, electric field radiation type transmission electron microscope (Cs correction included)). Observation using accelerated electrons (120 kV, magnification: 50,000 times), it was confirmed that a film was present on the outside of the child particles (ceria crystal particles), and then an electron beam was selectively applied to this film. The applied EDS measurement was performed.
The measurement conditions for energy dispersive X-ray spectroscopy (EDS) are shown below.
After the silica-based composite fine particles were dispersed in pure water, they were placed on a Cu mesh with a carbon support film and measured with the following measuring device.
Measuring device: UTW type Si (Li) semiconductor detector manufactured by JEOL Ltd. Beam system: 0.2 nm
透過型電子顕微鏡を用いて観察して得た写真（ＴＥＭ像）を図４に示す。そして、図４によって確認された子粒子（セリア結晶粒子）の外側にシリカ被膜の部分へ選択的に電子ビームを当てたＥＤＳ測定結果を図３に示す。図３に示すように１．７３９ｋｅＶにＳｉの強度ピークが現れ、４．８３９ｋｅＶにＣｅの強度ピークが現れた。そして、求められたＳｉの原子数％は２３．２２atom％、Ｃｅの原子数％は２５．６４atom％であり、Ｓｉの原子数％／Ｃｅの原子数％は０．９０５６と算出された。 A photograph (TEM image) obtained by observing with a transmission electron microscope is shown in FIG. Then, FIG. 3 shows the EDS measurement result in which an electron beam was selectively applied to the silica-coated portion on the outside of the child particles (ceria crystal particles) confirmed in FIG. As shown in FIG. 3, the intensity peak of Si appeared at 1.739 keV and the intensity peak of Ce appeared at 4.839 keV. Then, the calculated atomic number% of Si was 23.22 atom%, the atomic number% of Ce was 25.64 atom%, and the atomic number% of Si / the atomic number% of Ce was 0.9056.
＜比較例１＞
前記合成例で得られた固形分濃度２０質量％の焼成体解砕分散液（遠心分離処理無し）について、平均粒子径を測定したところ２１１ｎｍであり、ΔＰＣＤ／Ｖは−５３、初期流動電位は−５７５ｍＶであった。
また、電子顕微鏡観察写真の画像解析法にて１〜４個玉の割合を測定した。さらに後述する２種類の研磨試験を行い、研磨速度およびスクラッチの個数を計測した。
結果を第１表に示す。
<Comparative example 1>
The average particle size of the calcined body crushed dispersion (without centrifugation) obtained in the above synthesis example having a solid content concentration of 20% by mass was 211 nm, ΔPCD / V was −53, and the initial flow potential was It was -575 mV.
In addition, the ratio of 1 to 4 balls was measured by the image analysis method of the electron microscope observation photograph. Further, two types of polishing tests described later were performed, and the polishing speed and the number of scratches were measured.
The results are shown in Table 1.
＜比較例２＞
前記合成例で得られた固形分濃度２０質量％の焼成体解砕分散液を１１００ｒｐｍ（２００Ｇ）で４０分間遠心分離処理し、上澄液と沈降品を分離した。
回収した上澄液（シリカ系複合微粒子分散液）に含まれるシリカ系複合微粒子の平均粒子径を測定したところ、１９４ｎｍであり、ΔＰＣＤ／Ｖは−５８、初期流動電位は−５７０ｍＶであった。また、電子顕微鏡観察写真の画像解析法にて１〜４個玉の割合を測定した。さらに前記の２種類の研磨試験を行い、研磨速度およびスクラッチの個数を計測した。
結果を第１表に示す。
<Comparative example 2>
The calcined body crushed dispersion having a solid content concentration of 20% by mass obtained in the above synthesis example was centrifuged at 1100 rpm (200 G) for 40 minutes to separate the supernatant and the precipitated product.
The average particle size of the silica-based composite fine particles contained in the recovered supernatant (silica-based composite fine particle dispersion) was measured and found to be 194 nm, ΔPCD / V was −58, and the initial flow potential was −570 mV. In addition, the ratio of 1 to 4 balls was measured by the image analysis method of the electron microscope observation photograph. Further, the above two types of polishing tests were performed, and the polishing speed and the number of scratches were measured.
The results are shown in Table 1.
＜比較例３＞
前記合成例で得られた固形分濃度２０質量％の焼成体解砕分散液を、２０００ｒｐｍ（６２０Ｇ）で３分間行って、上澄液と沈降品を分離した。得られた沈降品の平均粒子径を後述する方法で測定したところ、２０８ｎｍであり、ΔＰＣＤ／Ｖは−５０、初期流動電位は−５６７ｍＶであった。
また、電子顕微鏡観察写真の画像解析法にて１〜４個玉の割合を測定した。さらに前記の２種類の研磨試験を行い、研磨速度およびスクラッチの個数を計測した。
結果を第１表に示す。
<Comparative example 3>
The calcined body crushed dispersion obtained in the above synthesis example having a solid content concentration of 20% by mass was carried out at 2000 rpm (620 G) for 3 minutes to separate the supernatant and the precipitated product. When the average particle size of the obtained precipitated product was measured by the method described later, it was 208 nm, ΔPCD / V was −50, and the initial flow potential was −567 mV.
In addition, the ratio of 1 to 4 balls was measured by the image analysis method of the electron microscope observation photograph. Further, the above two types of polishing tests were performed, and the polishing speed and the number of scratches were measured.
The results are shown in Table 1.
本発明の複合微粒子は、不純物を含まないため、半導体基板、配線基板などの半導体デバイスの表面の研磨に好ましく用いることができる。 Since the composite fine particles of the present invention do not contain impurities, they can be preferably used for polishing the surface of semiconductor devices such as semiconductor substrates and wiring substrates.
Claims (11)
［１］前記シリカ系複合微粒子は、シリカとセリアとの質量比が１００：１１〜３１６であること。
［２］前記シリカ系複合微粒子は、Ｘ線回折に供すると、セリアの結晶相のみが検出されること。
［３］前記シリカ系複合微粒子に含まれる、一次粒子が直接的または間接的に２個または３個連結した結合粒子の重量割合が６０％以上であること。 A silica-based particle having an average particle diameter of 50 to 350 nm having child particles mainly composed of crystalline ceria on the surface of a mother particle mainly composed of amorphous silica and having the following characteristics [1] to [3]. A silica-based composite fine particle dispersion containing composite fine particles.
[1] The silica-based composite fine particles have a mass ratio of silica to ceria of 100: 11-316.
[2] When the silica-based composite fine particles are subjected to X-ray diffraction, only the crystal phase of ceria is detected.
[3] The weight ratio of the bonded particles contained in the silica-based composite fine particles in which two or three primary particles are directly or indirectly linked is 60% or more.
（ａ）Ｎａ、Ａｇ、Ａｌ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｋ、Ｍｇ、Ｎｉ、Ｔｉ、Ｚｎ及びＺｒの含有率が、それぞれ１００ｐｐｍ以下。
（ｂ）Ｕ、Ｔｈ、Ｃｌ、ＮＯ3、ＳＯ4及びＦの含有率が、それぞれ５ｐｐｍ以下。 The silica-based composite fine particle dispersion liquid according to claim 1, wherein the content ratio of impurities contained in the silica-based composite fine particles is as follows (a) and (b).
(A) The contents of Na, Ag, Al, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn and Zr are 100 ppm or less, respectively.
(B) The contents of U, Th, Cl, NO 3 , SO 4 and F are 5 ppm or less, respectively.
ΔＰＣＤ／Ｖ＝（Ｉ−Ｃ）／Ｖ・・・式（１）
Ｃ：前記クニックにおける流動電位（ｍＶ）
Ｉ：前記流動電位曲線の開始点における流動電位（ｍＶ）
Ｖ：前記クニックにおける前記カチオンコロイド滴定液の添加量（ｍｌ） When cationic colloid titration is performed, the ratio (ΔPCD / V) of the flow potential change amount (ΔPCD) represented by the following formula (1) to the addition amount (V) of the cationic colloid titration solution in the knick is −110. The silica-based composite fine particle dispersion according to any one of claims 1 to 5, wherein a flow potential curve of 0 to -15.0 can be obtained.
ΔPCD / V = (IC) / V ... Equation (1)
C: Flow potential (mV) in the knick
I: Flow potential (mV) at the start point of the flow potential curve
V: Addition amount (ml) of the cationic colloid titration solution in the knick
工程１：シリカ微粒子が溶媒に分散してなるシリカ微粒子分散液を撹拌し、温度を５〜９８℃、ｐＨを範囲７．０〜９．０に維持しながら、ここへセリウムの金属塩を連続的又は断続的に添加し、前駆体粒子を含む前駆体粒子分散液を得る工程。
工程２：前記前駆体粒子分散液を乾燥させ、４００〜１,２００℃で焼成し、得られた焼成体に、次の（ｉ）又は（ｉｉ）の処理をして焼成体解砕分散液を得る工程。
（ｉ）乾式で解砕・粉砕処理し、溶媒を加えて溶媒分散処理する。
（ｉｉ）溶媒を加えて、湿式で解砕・粉砕処理する。
工程３：前記焼成体解砕分散液を、相対遠心加速度３００Ｇ以上にて遠心分離処理を行い、続いて沈降成分を除去することにより上澄液を得る工程。
工程４：前記上澄液を、相対遠心加速度３００Ｇ以上にて遠心分離処理を行い、続いて沈降成分を回収し、シリカ系複合微粒子分散液を得る工程。 A method for producing a silica-based composite fine particle dispersion, which comprises the following steps 1 to 4.
Step 1: The silica fine particle dispersion liquid in which the silica fine particles are dispersed in the solvent is stirred, and the metal salt of cerium is continuously added thereto while maintaining the temperature at 5 to 98 ° C. and the pH in the range of 7.0 to 9.0. A step of obtaining a precursor particle dispersion liquid containing precursor particles by adding the particles intermittently or intermittently.
Step 2: The precursor particle dispersion is dried and fired at 400 to 1,200 ° C., and the obtained fired body is subjected to the following treatment (i) or (ii) to crush and disperse the fired body. The process of obtaining.
(I) It is crushed and pulverized by a dry method, and a solvent is added to disperse the solvent.
(Ii) A solvent is added, and the mixture is crushed and pulverized in a wet manner.
Step 3: A step of centrifuging the fired body crushed dispersion at a relative centrifugal acceleration of 300 G or more, and subsequently removing a sedimentation component to obtain a supernatant.
Step 4: A step of centrifuging the supernatant at a relative centrifugal acceleration of 300 G or more, and then recovering the sedimented components to obtain a silica-based composite fine particle dispersion.
（ａ）Ｎａ、Ａｇ、Ａｌ、Ｃａ、Ｃｒ、Ｃｕ、Ｆｅ、Ｋ、Ｍｇ、Ｎｉ、Ｔｉ、Ｚｎ及びＺｒの含有率が、それぞれ１００ｐｐｍ以下。
（ｂ）Ｕ、Ｔｈ、Ｃｌ、ＮＯ3、ＳＯ4及びＦの含有率が、それぞれ５ｐｐｍ以下。 The method for producing a silica-based composite fine particle dispersion liquid according to claim 9, wherein the content ratio of impurities contained in the silica fine particles is as follows (a) and (b).
(A) The contents of Na, Ag, Al, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn and Zr are 100 ppm or less, respectively.
(B) The contents of U, Th, Cl, NO 3 , SO 4 and F are 5 ppm or less, respectively.
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