WO2017183452A1 - シリカ系複合微粒子分散液及びその製造方法 - Google Patents
シリカ系複合微粒子分散液及びその製造方法 Download PDFInfo
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- WO2017183452A1 WO2017183452A1 PCT/JP2017/014187 JP2017014187W WO2017183452A1 WO 2017183452 A1 WO2017183452 A1 WO 2017183452A1 JP 2017014187 W JP2017014187 W JP 2017014187W WO 2017183452 A1 WO2017183452 A1 WO 2017183452A1
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- WIPO (PCT)
- Prior art keywords
- silica
- composite fine
- based composite
- particles
- fine particle
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 758
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 357
- 239000010419 fine particle Substances 0.000 title claims abstract description 334
- 239000006185 dispersion Substances 0.000 title claims abstract description 331
- 239000002131 composite material Substances 0.000 title claims abstract description 220
- 238000000034 method Methods 0.000 title claims description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 39
- 239000002245 particle Substances 0.000 claims abstract description 304
- 238000005498 polishing Methods 0.000 claims abstract description 180
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 86
- 239000000758 substrate Substances 0.000 claims abstract description 59
- 238000005259 measurement Methods 0.000 claims abstract description 37
- 239000004065 semiconductor Substances 0.000 claims abstract description 29
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims description 98
- 239000011248 coating agent Substances 0.000 claims description 46
- 238000000576 coating method Methods 0.000 claims description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- 229910052684 Cerium Inorganic materials 0.000 claims description 43
- 239000002243 precursor Substances 0.000 claims description 42
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 38
- 238000011282 treatment Methods 0.000 claims description 33
- 239000012535 impurity Substances 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 26
- 238000004448 titration Methods 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 24
- 239000000084 colloidal system Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 230000001133 acceleration Effects 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 125000002091 cationic group Chemical group 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 238000000926 separation method Methods 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
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 12
- 229910052708 sodium 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
- 230000005540 biological transmission Effects 0.000 claims description 10
- 238000010494 dissociation reaction Methods 0.000 claims description 10
- 230000005593 dissociations Effects 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 238000010298 pulverizing process Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 238000003703 image analysis method Methods 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 5
- 238000010894 electron beam technology Methods 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 63
- -1 3,4-dihydro-2H-pyran Glycol ethers Chemical class 0.000 description 55
- 239000007787 solid Substances 0.000 description 43
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 32
- 235000011114 ammonium hydroxide Nutrition 0.000 description 30
- 229910004298 SiO 2 Inorganic materials 0.000 description 28
- 235000012239 silicon dioxide Nutrition 0.000 description 26
- 125000004429 atom Chemical group 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- 239000011324 bead Substances 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 230000032683 aging Effects 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000000790 scattering method Methods 0.000 description 18
- 229910000420 cerium oxide Inorganic materials 0.000 description 16
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 235000011054 acetic acid Nutrition 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 238000005342 ion exchange Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 239000000126 substance Substances 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
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 239000000047 product 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
- 238000010304 firing Methods 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 239000012528 membrane Substances 0.000 description 11
- 239000010453 quartz Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000011734 sodium 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
- 239000002585 base Substances 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 238000002296 dynamic light scattering Methods 0.000 description 10
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- 239000006104 solid solution Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- 150000002433 hydrophilic molecules Chemical class 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000004576 sand Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 239000006061 abrasive grain Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 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 8
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 150000003863 ammonium salts Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000002391 heterocyclic compounds Chemical class 0.000 description 7
- 238000009616 inductively coupled plasma Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 150000005215 alkyl ethers Chemical class 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000011246 composite particle Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
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- 229910021642 ultra pure water Inorganic materials 0.000 description 6
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- 229910019142 PO4 Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
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- 235000021317 phosphate Nutrition 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- IBMCQJYLPXUOKM-UHFFFAOYSA-N 1,2,2,6,6-pentamethyl-3h-pyridine Chemical compound CN1C(C)(C)CC=CC1(C)C IBMCQJYLPXUOKM-UHFFFAOYSA-N 0.000 description 4
- 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
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- 239000004115 Sodium Silicate Substances 0.000 description 4
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- 238000002474 experimental method Methods 0.000 description 4
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- 229910052731 fluorine Inorganic materials 0.000 description 4
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- 239000010703 silicon Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
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- 229910002651 NO3 Inorganic materials 0.000 description 3
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- 125000000623 heterocyclic group Chemical group 0.000 description 3
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
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- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 235000019316 curdlan Nutrition 0.000 description 1
- 229940078035 curdlan Drugs 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- ZGARNLJTTXHQGS-UHFFFAOYSA-N ethanamine;sulfuric acid Chemical compound CCN.CCN.OS(O)(=O)=O ZGARNLJTTXHQGS-UHFFFAOYSA-N 0.000 description 1
- ROBXZHNBBCHEIQ-BYPYZUCNSA-N ethyl (2s)-2-aminopropanoate Chemical compound CCOC(=O)[C@H](C)N ROBXZHNBBCHEIQ-BYPYZUCNSA-N 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- LCLHHZYHLXDRQG-ZNKJPWOQSA-N pectic acid Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)O[C@H](C(O)=O)[C@@H]1OC1[C@H](O)[C@@H](O)[C@@H](OC2[C@@H]([C@@H](O)[C@@H](O)[C@H](O2)C(O)=O)O)[C@@H](C(O)=O)O1 LCLHHZYHLXDRQG-ZNKJPWOQSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 239000010318 polygalacturonic acid Substances 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 1
- QJEOJNTXXKYIDP-UHFFFAOYSA-M sodium;3-ethoxypropane-1-sulfonate Chemical compound [Na+].CCOCCCS([O-])(=O)=O QJEOJNTXXKYIDP-UHFFFAOYSA-M 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- NFOSJIUDGCORCI-UHFFFAOYSA-M sodium;methoxymethanesulfonate Chemical compound [Na+].COCS([O-])(=O)=O NFOSJIUDGCORCI-UHFFFAOYSA-M 0.000 description 1
- DZXBHDRHRFLQCJ-UHFFFAOYSA-M sodium;methyl sulfate Chemical compound [Na+].COS([O-])(=O)=O DZXBHDRHRFLQCJ-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- JDVPQXZIJDEHAN-UHFFFAOYSA-N succinamic acid Chemical compound NC(=O)CCC(O)=O JDVPQXZIJDEHAN-UHFFFAOYSA-N 0.000 description 1
- 150000003445 sucroses Chemical class 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
- C01B33/149—Coating
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/06—Other polishing compositions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Definitions
- the present invention relates to a silica-based composite fine particle dispersion suitable as an abrasive used in semiconductor device production, and in particular, a film to be polished formed on a substrate is planarized by chemical mechanical polishing (CMP).
- CMP chemical mechanical polishing
- the present invention relates to a silica-based composite fine particle dispersion, a manufacturing method thereof, and a polishing abrasive dispersion containing silica-based composite fine particles.
- CMP chemical mechanical polishing
- an abrasive for CMP comprises abrasive grains and a chemical component, and the chemical component plays a role of promoting polishing by oxidizing or corroding a target film.
- abrasive grains have a role of polishing by mechanical action, and colloidal silica, fumed silica, and ceria particles are used as abrasive grains.
- colloidal silica, fumed silica, and ceria particles are used as abrasive grains.
- ceria particles exhibit a high polishing rate specifically with respect to a silicon oxide film, they are applied to polishing in a shallow trench element separation step. In the shallow trench isolation process, not only the silicon oxide film but also the silicon nitride film is polished. In order to facilitate element isolation, 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.
- a polishing method for such a member after performing a relatively rough primary polishing process and then performing a precise secondary polishing process, a smooth surface or a highly accurate surface with few scratches such as scratches can be obtained.
- the way to get done Conventionally, for example, the following methods have been proposed for the abrasive used for the secondary polishing as the finish polishing.
- Patent Document 1 an aqueous solution of cerium nitrate and a base are stirred and mixed at a quantitative ratio of pH 5 to 10, followed by rapid heating to 70 to 100 ° C. and aging at that temperature.
- a method for producing cerium oxide ultrafine particles (average particle size of 10 to 80 nm) composed of a single crystal of cerium oxide characterized by the following is described: Furthermore, according to this production method, the particle size is highly uniform and the particle shape It is described that ultrafine cerium oxide particles can be provided.
- Non-Patent Document 1 discloses a method for producing ceria-coated silica including 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 have a firing-dispersing step as included in the production method described in Patent Document 1.
- Patent Document 2 discloses that the surface of the amorphous silica particles A has at least one selected from zirconium, titanium, iron, manganese, zinc, cerium, yttrium, calcium, magnesium, fluorine, lanthanum, and strontium.
- a silica-based composite particle characterized by having a crystalline oxide layer B containing an element is described.
- 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, yttrium, calcium, magnesium, fluorine, lanthanum, and strontium Silica-based composite particles characterized by having B are described. And since such a silica type composite particle has the crystalline oxide layer B on the surface of the amorphous silica particle A, it can improve a grinding
- the dispersibility in the polishing slurry can be improved, and further, the amount of cerium oxide used can be greatly reduced without containing cerium oxide. Therefore, it is described that it is possible to provide an abrasive 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 particles and the effect of improving the polishing rate.
- the cerium oxide ultrafine particles described in Patent Document 1 were actually manufactured and examined by the inventor, and the polishing rate was low. Further, the surface of the polishing base material had defects (deterioration of surface accuracy, increased scratches, It has been found that the residue of the abrasive on the surface of the polishing substrate tends to occur. This is because the method for producing ultrafine cerium oxide particles described in Patent Document 1 does not include a firing step as compared with a method for producing ceria particles including a firing step (the degree of crystallinity of ceria particles is increased by firing).
- the cerium oxide particles are only crystallized with (an aqueous solution containing cerium nitrate), the cerium oxide particles that are produced have a low degree of crystallinity, and the cerium oxide is firmly fixed to the mother particles because it does not undergo firing.
- the present inventor presumes that the main factor is that cerium oxide falls off and remains on the surface of the polishing substrate.
- Non-Patent Document 1 since the ceria-coated silica described in Non-Patent Document 1 is not fired, it is considered that the actual polishing rate is low because of the low degree of crystallinity of ceria. There is also concern about residual particles.
- the present invention aims 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 has high surface accuracy (low scratch, little abrasive grains remaining on the substrate, and improved substrate Ra value. Etc.) and a silica-based composite fine particle dispersion that can be preferably used for polishing the surface of a semiconductor device such as a semiconductor substrate or a wiring substrate, a method for producing the same, and a polishing abrasive dispersion containing the silica-based composite fine particles The purpose is to do.
- the inventor has intensively studied to solve the above-mentioned problems, and has completed the present invention.
- the present invention includes the following (1) to (21).
- the silica-based composite fine particles have a mass ratio of silica to ceria of 100: 11 to 316.
- the silica-based composite fine particles are subjected to X-ray diffraction, only the ceria crystal phase is detected.
- the silica-based composite fine particles have a crystallite diameter of the crystalline ceria of 10 to 25 nm measured by X-ray diffraction.
- the silica-based composite fine particle dispersion according to (1) further comprising the following feature [4].
- the silica-based composite fine particles have a ratio of the number of particles having a minor axis / major axis ratio of 0.8 or less measured by an image analysis method of 35% or less.
- the silica-based composite fine particles have a silica coating on the surface of the child particles.
- ⁇ PCD / V (IC) / V (1)
- C Streaming potential (mV) at the nick
- I Streaming potential (mV) at the starting point of the streaming potential curve
- V Amount of the colloid titration solution added in the nick (ml)
- the polishing abrasive dispersion according to (10) which is used for planarizing a semiconductor substrate on which a silica film is formed.
- a method for producing a silica-based composite fine particle dispersion comprising the following steps 1 to 3.
- Step 1 A silica fine particle dispersion in which silica fine particles are dispersed in a solvent is stirred, and a cerium metal salt is continuously added thereto while maintaining a temperature of 5 to 98 ° C. and a pH of a range of 7.0 to 9.0.
- grain dispersion liquid which adds regularly or intermittently and contains a precursor particle.
- Step 2 The precursor particle dispersion is dried and calcined at 400 to 1,200 ° C., and the calcined product obtained by subjecting the obtained calcined product to the following treatment (i) or (ii): Obtaining. (I) Crushing is performed by a dry method, and a solvent is added to carry out a solvent dispersion treatment.
- Step 3 A step of obtaining a silica-based composite fine particle dispersion by subjecting the calcined dispersion to a centrifugal separation treatment at a relative centrifugal acceleration of 300 G or more and subsequently removing a sediment component.
- step (ii) The silica-based composite fine particle dispersion according to (12), wherein in step (ii), the solvent is added and the wet pulverization treatment is performed in the range of pH 8.6 to 10.8. Liquid manufacturing method.
- a silica-based composite fine particle dispersion that can be preferably used for polishing the surface of a semiconductor device such as a semiconductor substrate or a wiring substrate, a method for producing the same, and a polishing abrasive dispersion containing the silica-based composite fine particles are provided. Can do.
- the silica-based composite fine particle dispersion of the present invention is effective for planarizing the surface of a semiconductor device, and is particularly suitable for polishing a substrate on which a silica insulating film is formed.
- FIG. 1A is an SEM image obtained in Example 4, and FIG. 1B is a TEM image obtained in Example 4.
- 4 is an X-ray diffraction pattern obtained in Example 4.
- 3A is an SEM image obtained in Comparative Example 2, and FIG. 3B is a TEM image obtained in Comparative Example 2.
- 3 is an X-ray diffraction pattern obtained in Comparative Example 2.
- FIG. 5A is a TEM obtained in Example 4, and FIG. 5B is an enlarged TEM image of a part of FIG. It is a titration diagram of streaming potential.
- the present invention has child particles mainly containing crystalline ceria on the surface of mother particles mainly containing amorphous silica (hereinafter referred to as “silica fine particles”).
- the silica-based composite fine particles have a mass ratio of silica to ceria of 100: 11 to 316.
- the silica-based composite fine particles are subjected to X-ray diffraction, only the ceria crystal phase is detected.
- the silica-based composite fine particles have a crystallite diameter of the crystalline ceria of 10 to 25 nm measured by X-ray diffraction.
- a silica-based composite fine particle dispersion is also referred to as “the dispersion of the present invention”.
- the silica-based composite fine particles contained in the dispersion of the present invention are also referred to as “composite fine particles of the present invention” below.
- the present invention also provides a method for producing a silica-based composite fine particle dispersion, comprising the following steps 1 to 3.
- Step 1 A silica fine particle dispersion in which silica fine particles are dispersed in a solvent is stirred, and a cerium metal salt is continuously added thereto while maintaining a temperature of 5 to 98 ° C. and a pH of a range of 7.0 to 9.0.
- grain dispersion liquid which adds regularly or intermittently and contains a precursor particle.
- Step 2 The precursor particle dispersion is dried and calcined at 400 to 1,200 ° C., and the calcined product obtained by subjecting the obtained calcined product to the following treatment (i) or (ii): Obtaining.
- Step 3 A step of obtaining a silica-based composite fine particle dispersion by subjecting the calcined dispersion to a centrifugal separation treatment at a relative centrifugal acceleration of 300 G or more and subsequently removing a sediment component.
- the relative centrifugal acceleration is expressed as a ratio of the earth's gravitational acceleration 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”.
- the dispersion of the present invention is preferably produced by the production method of the present invention.
- the present invention means any of the dispersion of the present invention, the composite fine particles of the present invention, and the production method of the present invention.
- the mother particles are mainly composed of amorphous silica.
- the silica contained in the mother particles in the present invention is amorphous.
- the dispersion liquid (silica microparticle dispersion liquid) containing the mother particles (silica microparticles) is dried and then pulverized using a mortar.
- a conventionally known X-ray diffractometer for example, RINT1400 manufactured by Rigaku Corporation
- RINT1400 manufactured by Rigaku Corporation
- 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.
- the “main component” means that the content is 90% by mass or more. That is, in the mother particles, the content of amorphous silica is 90% by mass or more.
- the content is preferably 95% by mass or more, more preferably 98% by mass or more, and more preferably 99.5% by mass or more. In the following description of the present invention, the term “main component” is used in this sense.
- the mother particles are mainly composed of amorphous silica and may contain other materials such as crystalline silica and impurity elements.
- 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”).
- specific impurity group 1 is preferably 100 ppm or less, more preferably 50 ppm or less, more preferably 25 ppm or less, more preferably 5 ppm or less, and 1 ppm or less. Is more preferable.
- the content of each element of U, Th, Cl, NO 3 , SO 4 and F (hereinafter sometimes referred to as “specific impurity group 2”) in the base particles (silica fine particles) is 5 ppm or less, respectively. Preferably there is.
- silica fine particles prepared using water glass as a raw material contain about a few thousand ppm in total of the specific impurity group 1 and the specific impurity group 2 derived from the raw water glass.
- silica fine particle dispersion in which silica fine particles are dispersed in a solvent, it is possible to reduce the contents of the specific impurity group 1 and the specific impurity group 2 by performing ion exchange treatment.
- the specific impurity group 1 and the specific impurity group 2 remain several ppm to several hundred ppm in total. Therefore, when silica particles using water glass as a raw material are used, impurities are also reduced by acid treatment or the like.
- the content of each element and each anion in the specific impurity group 1 and the specific impurity group 2 is usually Are each 20 ppm or less.
- 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) are used.
- Each of the contents of F and F is a value determined by measurement 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 method
- ⁇ NO 3 , SO 4 and F Ion chromatograph
- 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 necessarily smaller than 350 nm.
- the average particle diameter of the mother particles is the same as the average particle diameter 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 diameter of 30 to 330 nm are preferably used.
- the average particle diameter of the mother particles is in the above range, scratches are reduced when the dispersion of the present invention is used as an abrasive.
- the average particle diameter of the mother particles is smaller than 30 nm, the polishing rate is insufficient.
- the average particle diameter is larger than 330 nm, the polishing rate is lowered.
- the surface accuracy of the substrate tends to deteriorate.
- the average particle diameter of the base 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 means a value obtained by measurement by the following method. Silica fine particles are dispersed in water or the like to obtain a silica fine particle dispersion, and then the silica fine particle dispersion is separated from a particle size measuring device by a known dynamic light scattering method (for example, Microtrack UPA device manufactured by Nikkiso Co., Ltd., The measurement is performed using a PAR-III (manufactured by Otsuka Electronics Co., Ltd.) or a measuring apparatus using a known laser diffraction scattering method (for example, LA-950 manufactured by HORIBA).
- a known dynamic light scattering method for example, Microtrack UPA device manufactured by Nikkiso Co., Ltd.
- a measuring apparatus is properly used according to the objective of each process, the assumed particle diameter, and particle size distribution.
- monodisperse silica fine particles of a raw material having a uniform particle size of about 100 nm or less are obtained by using a known particle size measuring apparatus (preferably PAR-III) by a dynamic light scattering method.
- Raw material silica fine particles are measured with a known laser diffraction scattering method (preferably LA-950), and in the crushing process where the particle diameter varies widely from micrometer to nanometer by crushing, known dynamic light scattering It is preferable to use a particle size measuring device by the method or a measuring device by a known laser diffraction scattering method (preferably Microtrac UPA or LA-950).
- the shape of the base particles is not particularly limited, and for example, those having ridge-like projections on the surface in addition to spherical, bowl-shaped, tetrahedral (triangular pyramid), hexahedral, octahedral, and irregular shapes Alternatively, it may be confetti-like or porous, but is preferably spherical.
- the term “spherical” means that the ratio of the number of particles having a minor axis / major axis ratio of 0.8 or less is 10% or less.
- the mother particles preferably have a minor axis / major axis ratio of 0.8 or less and a number ratio of particles of 5% or less, more preferably 0%.
- the minor axis / major axis ratio is measured by the same method as the measuring method (image analysis method) of the minor axis / major axis ratio of the composite fine particles of the present invention described later.
- the composite fine particles of the present invention have child particles on the surface of the mother particles as described above.
- the child particles that are entirely covered by the silica coating may be bonded to the mother particles via the silica coating. Further, the child particles may be bonded to the surface of the mother particle. Even such an embodiment is an embodiment in which child particles are present on the surface of the mother particle, and is included in the technical scope of the present invention.
- the child particles are mainly composed of crystalline ceria.
- the fact that the child particles are crystalline ceria is, for example, that the dispersion liquid of the present invention is dried and then pulverized using a mortar, for example, a conventionally known X-ray diffractometer (for example, RINT1400 manufactured by Rigaku Corporation).
- a mortar for example, a conventionally known X-ray diffractometer (for example, RINT1400 manufactured by Rigaku Corporation).
- RINT1400 manufactured by Rigaku Corporation
- the child particles are mainly composed of crystalline ceria (crystalline Ce oxide), and may contain other elements, for example, elements other than cerium.
- crystalline ceria crystalline Ce oxide
- the composite fine particles of the present invention are subjected to X-ray diffraction, only the ceria crystal phase is detected. That is, even if a crystal phase other than ceria is included, its content is small, and thus it is outside the detection range by X-ray diffraction.
- the definition of “principal component” is as described above.
- the crystallite diameter of the crystalline ceria measured by subjecting the composite fine particles of the present invention to X-ray diffraction is 10 to 25 nm, preferably 11 to 23 nm, and preferably 12 to 20 nm. More preferred.
- the crystallite diameter of crystalline ceria is determined from the full width at half maximum of the maximum peak of the X-ray diffraction pattern.
- the average crystallite diameter of the (111) plane is 10 to 25 nm (full width at half maximum is 0.86 to 0.34 °), and 11 to 23 nm (full width at half maximum is 0.78 to 0.37 °). More preferably, it is more preferably 12 to 20 nm (full width at half maximum is 0.79 to 0.43 °).
- the calculation can be performed in the same manner, and the average crystallite diameter in that case may be the same as the average crystallite diameter of the (111) plane.
- the composite fine particles of the present invention are pulverized using a mortar, and an X-ray diffraction pattern is obtained by using, for example, a conventionally known X-ray diffractometer (for example, RINT1400 manufactured by Rigaku Corporation).
- the size of the child particles is smaller than that of the mother particles, preferably an average particle diameter of 11 to 26 nm, and more preferably 12 to 23 nm.
- the size of the child particles is a value obtained by measuring the average particle diameter of any 50 child particles in a photograph projection view enlarged 300,000 times using a scanning electron microscope, and simply averaging them. means.
- the composite fine particles of the present invention preferably have the child particles on the surface of the mother particles, and further have a silica coating on the surface of the child particles.
- the child particles may be bonded to the surface of the mother particles, and may further have a silica coating covering them. That is, the silica coating may cover a part or the whole of the composite particles formed by bonding the child particles to the surface of the mother particles. Therefore, it is more preferable that a silica coating is present on the outermost surface of the composite fine particles of the present invention.
- the composite fine particle of the present invention has a silica coating on the surface of the child particle
- an image obtained by observation using a transmission electron microscope has a dark image of the child particle on the surface of the mother particle.
- a silica coating appears as a relatively thin image outside the child particle, that is, on the surface side of the composite fine particle of the present invention.
- the child particles ceria fine particles
- the mother particles silicon fine particles
- the child particles whose silica coating covers all or part of the mother particles are formed on the mother particles via the silica coating. It may be bonded.
- the composite fine particles of the present invention have a silica coating on the surface of the child particles
- the composite fine particles of the present invention are subjected to EDS analysis and the element distribution is obtained, a portion with a high Ce concentration is present on the surface side of the particles. Although it appears, a portion with a high Si concentration appears further outside.
- the Si atom number% and Ce atom number% of the part were obtained. It can be confirmed that several percent is very high. Specifically, the ratio of Si atom number% to Ce atom number% (Si atom number% / Ce atom number%) is preferably 0.9 or more.
- Such a silica coating is considered to promote 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 of the present invention, the silica-based composite fine particles obtained by firing are crushed by a wet method to obtain a silica-based composite fine particle dispersion. It is considered that there is an effect of preventing the particles (ceria crystal particles) from coming off from the mother particles (silica fine particles). In this case, local dropout of the child particles is not a problem, and the entire surface of the child particles may not be covered with the silica coating. It is sufficient that the child particles are strong enough not to be separated from the mother particles in the crushing process.
- the polishing rate is high, and the surface accuracy and scratch are less deteriorated.
- the composite fine particles of the present invention at least a part of the surface of the child particles is covered with a silica layer, so that the OH group of silica is present on the outermost surface (outermost shell) of the composite fine particles of the present invention. Become. Therefore, when used as an abrasive, the composite fine particles of the present invention are repelled by charges due to —OH groups on the surface of the polishing substrate, and as a result, adhesion to the surface of the polishing substrate is considered to be reduced.
- free ceria has a positive charge and is likely to adhere to the substrate.
- the composite fine particles of the present invention have a silica coating on the surface of the child particles, even if the ceria particles of the child particles fall off during polishing, the surface is covered with silica and thus has a negative charge.
- ceria has a potential different from that of silica, a polishing substrate, and a polishing pad, and the pH decreases from a negative zeta potential in the vicinity of neutral to neutral, and has a reverse positive potential in a weakly acidic region.
- the silica-based composite fine particle of the present invention is such that the ceria which is the child particle is at least partially covered with the silica coating.
- the pH is maintained at a negative potential from alkaline to acidic, it is difficult for abrasive grains to remain on the polishing substrate and polishing pad.
- the thickness of the silica coating is roughly determined from the TEM image or SEM image by the degree of coverage of the ceria child particles on the mother particles by the silica coating. It is done. That is, as described above, in the TEM image, a child particle having a particle size of about 20 nm appears on the surface of the mother particle, and a silica coating appears as a relatively thin image outside the child particle. The thickness of the silica coating can be roughly determined by comparing with the size of.
- the thickness of the silica coating may be much less than 20 nm if the child particles can be clearly confirmed as irregularities from the SEM image and the contours of the silica composite fine particles are seen from the TEM image. Conceivable. On the other hand, if the irregularities of the child particles are not clear from the SEM image, and the irregularities are not seen in the outline of the silica-based composite fine particles from the TEM image, the thickness of the silica coating is considered to be about 20 nm.
- the silica coating of the outermost layer is a child particle (ceria fine particles). It is not necessary to completely cover the whole. That is, when the composite fine particle of the present invention has a silica coating on the surface of the child particle, the silica coating is present on the outermost surface of the composite fine particle of the present invention, but the portion where the silica coating is not present is present. There may be. Further, there may be a portion where the base particle of the silica-based composite fine particle is exposed.
- the composite fine particles of the present invention have the above child particles on the surface of the mother particles.
- the mass ratio of silica to ceria is 100: 11 to 316, preferably 100: 30 to 230, more preferably 100: 30 to 150, and more preferably 100: 60 to More preferably, it is 120.
- the mass ratio between silica and ceria is considered to be approximately the same as the mass ratio between the mother particles and the child particles.
- the mother particles may be bonded to generate coarse particles.
- the abrasive (polishing abrasive dispersion) containing the dispersion of the present invention may cause defects (decrease in surface accuracy such as an increase in scratches) on the surface of the polishing substrate.
- the silica that is the target in calculating the mass ratio includes all of the following (I) to (III).
- the content (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 composite fine particle dispersion of the present invention (dispersion of the present invention) at 1000 ° C. Calculate the weight loss after losing heat. 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 to CeO 2 mass%. Then, assuming that the components other than CeO 2 constituting the composite fine particles of the present invention are SiO 2 , SiO 2 mass% can be calculated.
- the mass ratio of silica and ceria can be calculated from the amount of silica source material and ceria source material used when the dispersion of the present invention is prepared. This can be applied when ceria and silica are not dissolved and removed, or when ceria and silica are dissolved and removed but the amount of dissolution is very small. The amount of silica used and the analytical value agree well.
- the composite fine particles of the present invention may be those in which particulate crystalline ceria (child particles) are bonded to the surface of silica fine particles (mother particles) by sintering or the like.
- the composite fine particles of the present invention 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 sinter-bonded and firmly bonded at their contact points.
- the child particles covered with the silica coating may be bonded to the mother particles through the silica coating.
- silicon atoms are preferably dissolved in crystalline ceria which is the main component of the child particles.
- elements other than silicon atoms may be dissolved in crystalline ceria.
- solid solution means that two or more kinds of elements (metal or non-metal) are dissolved in each other and the whole is a uniform solid phase. And classified into substitutional solid solution and interstitial solid solution.
- substitution-type solid solutions can easily occur in atoms with a close atomic radius, but Ce and Si have a large difference in atomic radii, so at least substitution-type solid solutions are unlikely to occur.
- the coordination number of Ce as viewed from the Ce center is 8.
- the coordination number of Ce when Si is substituted with Ce on a one-to-one basis, the coordination number of Ce should be 7.
- the average coordination number of Ce viewed from the Ce center when analyzed, the average coordination number of Ce viewed from the Ce center is, for example, 7.9, and the average coordination number of Si is, for example, 1.1. Therefore, when the composite fine particle of the present invention is a preferred embodiment, it is presumed that the solid solution form is an interstitial type.
- the distance between adjacent Ce—Si atoms is smaller than the distance between adjacent Ce—Ce atoms, and therefore the composite fine particle of the present invention is a preferred embodiment.
- the interatomic distance between cerium atoms and silicon atoms such as R 1 and R 2 described above means an average bond distance obtained by measurement by the method described in Examples described later.
- the ratio of the number of particles having a minor axis / major axis ratio measured by an image analysis method of 0.80 or less may be 35% or less.
- particles having a minor axis / major axis ratio measured by an image analysis method of 0.80 or less are considered to be of a particle-binding type in principle, and particles exceeding 0.80 are true spherical single particles. It is considered a thing.
- the fact that the number ratio of particles having a minor axis / major axis ratio of 0.80 or less is 35% or less is considered to be true single particles.
- the shape of the composite fine particle of the present invention may be a true single particle, or may include other shapes such as a particle-linked type in addition to the true spherical shape.
- true spherical single particles it can be easily achieved that the ratio of the minor axis / major axis ratio is 0.8 or less is 35% or less.
- polishing is performed using such particles, since there is no coarse agglomerate that causes scratches, there is no polishing flaw on the polished substrate surface, and the smoothness tends to be very good.
- the proportion of the particles having a minor axis / major axis ratio of 0.8 or less is 35% or less, there is substantially no adverse effect on polishing scratches and surface roughness.
- a method for measuring the minor axis / major axis ratio by the image analysis method will be described.
- a photograph projection view obtained by photographing a composite fine particle of the present invention at a magnification of 250,000 times (or 500,000 times) with a transmission electron microscope the maximum diameter of the particles is taken as the major axis, and the length is measured. The value is taken as the major axis (DL).
- a point that bisects the major axis on the major axis is determined, two points where a straight line perpendicular to the major axis intersects the outer edge of the particle are obtained, and the distance between the two points is measured to obtain a minor axis (DS).
- the minor axis / major axis ratio (DS / DL) is obtained. Then, the number ratio (%) of particles having a minor axis / major axis ratio of 0.80 or less in any 50 particles observed in the photographic projection diagram is obtained.
- the composite fine particles of the present invention preferably have a specific surface area of 4 to 100 m 2 / g, more preferably 20 to 60 m 2 / g.
- BET specific surface area a method for measuring the specific surface area (BET specific surface area) will be described.
- a dried sample (0.2 g) is put in a measurement cell, degassed in a nitrogen gas stream at 250 ° C. for 40 minutes, and then the sample is a mixed gas of 30% by volume of nitrogen and 70% by volume of helium. Liquid nitrogen temperature is maintained in a stream of air, and nitrogen is adsorbed to the sample by equilibrium.
- the temperature of the sample is gradually raised to room temperature while flowing the mixed gas, the amount of nitrogen desorbed during that time is detected, and the specific surface area of the sample is measured using a calibration curve prepared in advance.
- Such a BET specific surface area measurement method nitrogen adsorption method
- the specific surface area means a value obtained by such a method unless otherwise specified.
- the average particle size of the composite fine particles of the present invention is preferably 50 to 350 nm, and more preferably 170 to 260 nm.
- the polishing rate becomes high when applied as an abrasive, which is preferable.
- the average particle diameter 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 means a value obtained by measurement by the following method.
- the composite fine particles of the present invention are dispersed in water, and this composite fine particle dispersion is used as a particle size measuring device by a known dynamic light scattering method (for example, Microtrack UPA device manufactured by Nikkiso Co., Ltd. or PAR-III manufactured by Otsuka Electronics Co., Ltd.). ) Or a measurement apparatus using a laser diffraction scattering method (for example, LA-950 manufactured by HORIBA).
- a known dynamic light scattering method for example, Microtrack UPA device manufactured by Nikkiso Co., Ltd. or PAR-III manufactured by Otsuka Electronics Co., Ltd.
- a measurement apparatus using a laser diffraction scattering method for example, LA-950 manufactured by HORIBA
- the content of each element of the specific impurity group 1 is preferably 100 ppm or less, more preferably 50 ppm or less, more preferably 25 ppm or less, and more preferably 5 ppm or less. More preferably, it is more preferably 1 ppm or less. Moreover, it is preferable that the content rate of each element of the said specific impurity group 2 in the composite fine particle of this invention is 5 ppm or less, respectively.
- the method described for the mother particles (silica fine particles) can be applied.
- each element of the specific impurity group 1 and the specific impurity group 2 in the composite fine particles of the present invention is the same as in the case of the mother particle described above, by atomic absorption spectrometry, ICP (inductively coupled plasma emission spectroscopy). Analytical apparatus), potentiometric titration method, and ion chromatograph are used for measurement and determination.
- the composite fine particle of the present invention is a composite oxide fine particle 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.
- the composite oxide fine particles do not necessarily satisfy this condition.
- the former can be suitably used as an abrasive in applications where application of high-purity abrasives is required, for example, polishing applications such as semiconductor devices such as semiconductor substrates and wiring substrates.
- polishing applications such as semiconductor devices such as semiconductor substrates and wiring substrates.
- the latter is applied to applications where application of a high-purity abrasive is not required, such as glass polishing.
- the former is naturally applicable to applications where application of a high-purity abrasive is not required.
- the dispersion liquid of the present invention will be described.
- the dispersion liquid of the present invention is such that the composite fine particles of the present invention as described above are dispersed in a dispersion solvent.
- the dispersion of the present invention contains water and / or an organic solvent as a dispersion solvent.
- water such as pure water, ultrapure water, or ion exchange water is preferably used as the dispersion solvent.
- the dispersion of the present invention is polished by adding one or more selected from the group consisting of a polishing accelerator, a surfactant, a pH adjuster and a pH buffer as an additive for controlling the polishing performance. It is suitably used as a slurry.
- Examples of the dispersion solvent provided with the dispersion of the present invention include alcohols such as methanol, ethanol, isopropanol, n-butanol, and methyl isocarbinol; acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone, and cyclohexanone.
- alcohols such as methanol, ethanol, isopropanol, n-butanol, and methyl isocarbinol
- Ketones such as N; N-dimethylformamide, amides such as N, N-dimethylacetamide; ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, and 3,4-dihydro-2H-pyran
- Glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-but Glycol ether acetates such as ciethyl acetate; Esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate and ethylene carbonate; Aromatic hydrocarbons such as benzene, toluene and xylene; Hexane, heptane and isooctane
- the solid content concentration contained in the dispersion of the present invention is preferably in the range of 0.3 to 50% by mass.
- ⁇ PCD change in flow potential
- V addition amount of the cationic colloid titrant in the knick
- ⁇ PCD / V (IC) / V (1)
- C Streaming potential (mV) at the nick
- I Streaming potential (mV) at the starting point of the streaming potential curve
- V Amount of the colloid titration solution added in the nick (ml)
- the cation colloid titration is performed by adding the cation colloid titration liquid 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 polydiallyldimethylammonium chloride solution is used as the cationic colloid titrant.
- Other measurement conditions are performed by a method suitable for the literature and the standard method recommended by the manufacturer.
- the flow potential curve obtained by the cation colloid titration is a graph in which the addition amount (ml) of the cation titrant is taken on the X axis and the flow potential (mV) of the dispersion of the present invention is taken on the Y axis.
- a knick is a point (inflection point) where the streaming potential changes suddenly in the streaming potential curve obtained by cationic colloid titration.
- the flow potential at the inflection point is C (mV)
- the addition amount of the cation colloid titrant at the inflection point is V (ml).
- the starting point of the streaming potential curve is the streaming potential in the dispersion of the present invention before titration. Specifically, the point where the addition amount of the cationic colloid titrant is 0 is set as the starting point.
- the streaming potential at this point is I (mV).
- the polishing rate of the polishing agent is further improved when the dispersion of the present invention is used as the polishing agent.
- This ⁇ PCD / V is considered to reflect the degree of coating of the silica coating on the surface of the composite fine particles of the present invention and / or the degree of exposure of the child particles on the surface of the composite fine particles or the presence of silica that is easily detached.
- the present inventor presumes that the child particles are hardly detached at the time of pulverization by wet and the polishing rate is high.
- ⁇ PCD / V is more preferably ⁇ 100.0 to ⁇ 15.0, and further preferably ⁇ 100.0 to ⁇ 20.0.
- the dispersion of the present invention has a negative flow potential before cation colloid titration, that is, when the titer is zero, when the pH value is in the range of 3 to 8. Is preferred. This is because when this flow potential is maintained at a negative potential, it is difficult for abrasive grains (silica-based composite fine particles) to remain on the polishing substrate that also exhibits a negative surface potential.
- the method for producing the dispersion of the present invention is not particularly limited, but it is preferably produced by the production method of the present invention described below.
- the production method of the present invention will be described.
- the production method of the present invention includes steps 1 to 3 described below.
- step 1 a silica fine particle dispersion in which silica fine particles are dispersed in a solvent is prepared.
- 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.
- the silica fine particle dispersion is preferably acid-treated and further deionized.
- 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 it can be reduced to 100 ppm or less.
- those satisfying the following conditions (a) and (b) are preferably used as the silica fine particles in the silica fine particle dispersion, which is the raw material used in step 1.
- the silica fine particles preferably have an average particle diameter in the range of 30 to 330 nm and a minor axis / major axis ratio measured by an image analysis method in the range of 0.95 to 1.0.
- step 1 the silica fine particle dispersion in which the silica fine particles are dispersed in a 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.
- a salt is added continuously or intermittently to obtain a precursor particle dispersion containing precursor particles.
- the dispersion medium in the silica fine particle dispersion preferably contains water, and an aqueous silica fine particle dispersion (water sol) is preferably used.
- the solid concentration in the silica fine particle dispersion is preferably 1 to 40% by mass in terms of SiO 2 .
- this solid content concentration is too low, the silica concentration in the production process becomes low, and the productivity may deteriorate.
- a silica fine particle dispersion from which impurity ions and the like are removed by deionization treatment is more preferable because a hydroxide containing silicon is easily formed on the surface.
- the deionization process is not limited to these.
- Step 1 the silica fine particle dispersion as described above is stirred, and the cerium metal salt 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.
- the metal salt of cerium is not limited, but cerium chloride, nitrate, sulfate, acetate, carbonate, metal alkoxide, and the like can be used. Specific examples include cerium nitrate, cerium carbonate, cerium sulfate, and cerium chloride. Of these, ceric nitrate and ceric chloride are preferred.
- cerium hydroxide and crystalline cerium oxide are produced, and they quickly adhere to the silica fine particles by an agglomeration and deposition mechanism.
- sulfate ions, chloride ions, nitrate ions, etc. contained in these metal salts are corrosive. For this reason, it is necessary to wash it in a post-process after preparation and remove it to 5 ppm or less.
- carbonate is released during the preparation as carbon dioxide, and alkoxide is decomposed to become alcohol, which is preferable.
- the amount of cerium metal salt added to the silica fine particle dispersion is such that the mass ratio of silica and ceria in the resulting composite fine particles of the present invention is in the range of 100: 11 to 316 as described above.
- the cerium metal salt is usually a cerium metal salt aqueous solution obtained by adding water, an aqueous solvent, an acid or the like to the cerium metal salt.
- the ceria concentration of the aqueous cerium metal salt 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.
- the temperature at the time of stirring after adding the cerium metal salt to the silica fine particle dispersion is 5 to 98 ° C., preferably 10 to 95 ° C. If the temperature is too low, the solubility of the silica is remarkably reduced, so that ceria crystallization is not controlled, and coarse ceria crystalline oxides are formed, making it difficult to adhere to silica fine particles (mother particles). Things can be considered. On the other hand, if this temperature is too high, the solubility of silica is remarkably increased, and the formation of crystalline ceria oxide is considered to be suppressed. Furthermore, scale and the like are likely to occur on the reactor wall surface, which is not preferable.
- the stirring time is preferably 0.5 to 24 hours, and more preferably 0.5 to 18 hours. If this time is too short, crystalline cerium oxide cannot be formed sufficiently, which is not preferable. Conversely, even if this time is too long, the formation of crystalline cerium oxide is uneconomical because the reaction does not proceed any further.
- the cerium metal salt it may be aged at 5 to 98 ° C. if desired. By aging, the reaction in which the cerium compound is deposited on the mother particles can be further promoted.
- the pH range of the silica fine particle dispersion when adding a cerium metal salt to the silica fine particle dispersion and stirring is 7.0 to 9.0, preferably 7.6 to 8.6. . If the pH is too high, the salt concentration of the system becomes too high, and particle aggregation proceeds, which is not preferable. In the case of 7.0 or less, cerium remains in the solution in the form of cerium ions and is not preferred because it does not deposit on the particle surface. At this time, it is preferable to adjust the pH by adding an alkali or the like.
- a publicly known alkali can be used as an example of such an alkali. Specific examples include aqueous ammonia, alkali hydroxide, alkaline earth metal, and aqueous amines, but are not limited thereto.
- a dispersion (precursor particle dispersion) containing particles (precursor particles) that are precursors of the composite fine particles of the present invention is obtained.
- the precursor particle dispersion obtained in step 1 may be further diluted or concentrated using pure water, ion-exchanged water or the like before being subjected to step 2, and may be subjected to the next step 2.
- the solid content concentration in the precursor particle dispersion is preferably 1 to 27% by mass.
- 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.
- the cerium metal salt is added continuously or intermittently while the temperature range of the silica fine particle dispersion is set to 5 to 52 ° C. and the pH range is maintained at 7.0 to 9.0. Then, a precursor particle dispersion is prepared, and the precursor particle dispersion is aged at a temperature of 5 to 52 ° C.
- the metal salt of cerium or cerium hydroxide reacts with silica in a liquid phase to produce a cerium silicate compound, which inhibits ceria crystal growth. At the same time, ceria microcrystals are generated, and cerium silicate compound and ceria microcrystals are formed on the mother particles.
- step 2 the precursor particle dispersion is dried and then calcined at 400 to 1,200 ° C.
- the method for drying is not particularly limited. It can be dried using a conventionally known dryer. Specifically, a box-type dryer, a band dryer, a spray dryer or the like can be used.
- a box-type dryer, a band dryer, a spray dryer or the like can be used.
- the pH of the precursor particle dispersion before drying is 6.0 to 7.0. This is because when the pH of the precursor particle dispersion before drying is 6.0 to 7.0, the formation of strong aggregates can be suppressed.
- the drying temperature after drying is 400 to 1200 ° C., preferably 800 to 1100 ° C., more preferably 1000 to 1090 ° C.
- step 2 the fired body obtained by firing is subjected to the following treatment (i) or (ii) to obtain a fired body crushed dispersion.
- Crushing is performed by a dry method, and a solvent is added to carry out a solvent dispersion treatment.
- a solvent is added and pulverized by a wet process.
- Conventionally known devices can be used as the dry crushing device, and examples thereof include an attritor, a ball mill, a vibration mill, and a vibration ball mill.
- Conventionally known devices can be used as wet crushing devices. For example, batch type bead mills such as basket mills, horizontal, vertical and annular type continuous bead mills, sand grinder mills, ball mills, etc.
- wet crushers such as an impact crusher that collides fine particles in a dispersion.
- beads used in the wet medium stirring mill include beads made of glass, alumina, zirconia, steel, flint stone, and the like.
- water and / or an organic solvent are used as the solvent.
- water such as pure water, ultrapure water, or ion exchange water.
- the solid content concentration of the pulverized dispersion of the fired body obtained by the treatment (i) or (ii) is not particularly limited, but it is, for example, in the range of 0.3 to 50% by mass. It is preferably 10 to 30% by mass.
- the wet treatment of (ii) is more preferably used in practice.
- the polishing rate is further improved.
- the inventor is that the silica coating on the surface of the composite fine particles of the present invention is moderately thin, and / or the child particles are exposed to a part of the surface of the composite fine particles, the polishing rate is further improved, In addition, it is estimated that the falling of ceria particles can be controlled.
- ⁇ PCD / V is more preferably ⁇ 100.0 to ⁇ 15.0, and further preferably ⁇ 100.0 to ⁇ 20.0.
- Step 3 the fired body disintegrated dispersion obtained in Step 2 is subjected to a centrifugal separation process at a relative centrifugal acceleration of 300 G or more, and then the sediment component is removed to obtain a silica-based composite fine particle dispersion.
- coarse particles and connected particles having a minor axis / major axis ratio of less than 0.8 are removed from the fired body pulverized dispersion by classification by centrifugation.
- the relative centrifugal acceleration in the centrifugation process is set to 300 G or more. After the centrifugal separation treatment, the precipitated components can be removed to obtain 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. In step 3, it is necessary to provide a centrifugal separation process that satisfies the above conditions.
- the silica-based composite fine particles can be obtained by further drying the silica-based composite fine particle dispersion obtained by the above production method.
- the drying method is not particularly limited, and for example, it can be dried using a conventionally known dryer.
- the dispersion of the present invention can be obtained by the production method of the present invention.
- a cerium metal salt is added to the silica fine particle dispersion, it is desirable that the redox potential of the preparation liquid take a positive value. This is because, when the oxidation-reduction potential becomes negative, the cerium compound does not deposit on the surface of the silica particles and tends to produce single cerium particles such as plates and rods.
- Examples of a method for keeping the oxidation-reduction potential positive include a method of adding an oxidizing agent such as hydrogen peroxide and a method of blowing air, but is not limited thereto.
- the liquid containing the dispersion of the present invention can be preferably used as a polishing abrasive dispersion (hereinafter also referred to as “the polishing abrasive dispersion of the present invention”).
- the polishing abrasive dispersion of the present invention can be suitably used as a polishing abrasive dispersion for planarizing a semiconductor substrate or glass substrate on which a SiO 2 insulating film is formed.
- the pH of the polishing abrasive dispersion of the present invention is preferably 3-8.
- the polishing abrasive dispersion of the present invention has a high polishing rate when polishing a semiconductor substrate, etc., and has excellent effects such as few scratches (scratches) on the polishing surface and little residual abrasive on the substrate during polishing. ing.
- the polishing abrasive dispersion of the present invention contains water and / or an organic solvent as a dispersion solvent.
- water such as pure water, ultrapure water, or ion exchange water is preferably used as the dispersion solvent.
- the polishing abrasive dispersion of the present invention is selected from the group consisting of a polishing accelerator, a surfactant, a heterocyclic compound, a pH adjuster and a pH buffer as an additive for controlling polishing performance. By adding seeds or more, it is suitably used as a polishing slurry.
- the polishing abrasive dispersion of the present invention preferably contains the composite fine particles of the present invention, and further contains an acidic compound having an acid dissociation constant (pKa) of 1.5 or more.
- the content of the acidic compound is preferably 0.0002 to 0.1% by mass.
- Examples of acidic compounds having an acid dissociation constant (pKa) of 1.5 or more include acetic acid, lactic acid, formic acid, malic acid, benzoic acid, citric acid, tartaric acid, phosphoric acid, and carbonic acid.
- examples of acidic compounds having an acid dissociation constant (pKa) of less than 1.5 include nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, hydrobromic acid, and trichloroacetic acid.
- an acid dissociation constant shall mean the acid dissociation constant in case a solvent is water and 25 degreeC.
- the polishing abrasive dispersion of the present invention preferably contains the composite fine particles of the present invention and has an ionic strength of 0.007 or more.
- the polishing abrasive dispersion of the present invention may contain components other than the composite fine particles of the present invention. Examples of such an additive include various additives such as ionic strength adjusting additives, polishing accelerators, surfactants, hydrophilic compounds, heterocyclic compounds, pH adjusting agents, and pH buffering agents described later. .
- the ionic strength of the polishing abrasive dispersion of the present invention is 0.007 or more, the polishing rate is improved.
- the upper limit of this ionic strength may be 0.1 and is preferably 0.04.
- the ionic strength of the polishing abrasive dispersion of the present invention means a value calculated from the following equation.
- J in the formula represents ionic strength.
- Ci represents the molar concentration of each ion
- Zi represents the valence of each ion.
- the molar concentration of each ion is the ion concentration of the substance that dissociates at the pH of the polishing abrasive dispersion of each substance, and is calculated using the acid dissociation constant pKa or base dissociation constant pKb of each substance.
- a salt that dissociates into A ⁇ and B + to the abrasive dispersion for polishing separate into acid AH and base BOH, and calculate ion concentrations of A ⁇ and H + , and B + and OH ⁇ respectively. To do.
- AH is calculated separately from A ⁇ and H +, and is calculated by applying the above formula.
- the polishing abrasive dispersion of the present invention preferably contains an ionic strength adjusting agent.
- An ionic strength adjusting agent may be added in order to make the ionic strength of the abrasive dispersion for polishing of the present invention 0.007 or more.
- the polishing abrasive dispersion of the present invention preferably contains one or two selected from the group consisting of ammonium nitrate and ammonium acetate as an ionic strength adjusting agent.
- the content of the ionic strength adjusting agent in the polishing abrasive dispersion of the present invention is not particularly limited, but is preferably, for example, 200 to 2000 ppm, and more preferably 300 to 1500 ppm.
- the polishing abrasive dispersion according to the present invention can be used as a polishing slurry by adding a conventionally known polishing accelerator, if necessary, depending on the type of material to be polished.
- polishing accelerators include hydrogen peroxide, peracetic acid, urea peroxide, and mixtures thereof.
- the polishing rate can be effectively improved when the material to be polished is a metal.
- 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, potassium, ammonium and amine salts of these acids And the like.
- inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, oxalic acid and hydrofluoric acid
- organic acids such as acetic acid, or sodium, potassium, ammonium and amine salts of these acids And the like.
- the polishing rate is accelerated for a specific component of the material to be polished, thereby finally achieving flat polishing. You can get a plane.
- the polishing abrasive dispersion of the present invention contains a polishing accelerator, its content is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass. .
- a cationic, anionic, nonionic or amphoteric surfactant or hydrophilic compound can be added. Both the surfactant and the hydrophilic compound have an action of reducing a contact angle to the surface to be polished and an action of promoting uniform polishing.
- the surfactant and / or the hydrophilic compound for example, those selected from the following groups can be used.
- anionic surfactant examples include carboxylate, sulfonate, sulfate ester salt, and phosphate ester salt.
- carboxylate salt soap, N-acyl amino acid salt, polyoxyethylene or polyoxypropylene alkyl ether carboxyl Acid salt, acylated peptide; as sulfonate, alkyl sulfonate, alkylbenzene and alkyl naphthalene sulfonate, naphthalene sulfonate, sulfosuccinate, ⁇ -olefin sulfonate, N-acyl sulfonate; sulfate ester Salts include sulfated oil, alkyl sulfates, alkyl ether sulfates, polyoxyethylene or polyoxypropylene alkyl allyl ether sulfates, alkyl amide sulfates; phosphate ester salts such as alkyl phosphate salt
- cationic surfactant aliphatic amine salt, aliphatic quaternary ammonium salt, benzalkonium chloride salt, benzethonium chloride, pyridinium salt, imidazolinium salt; as amphoteric surfactant, carboxybetaine type, sulfobetaine type, Mention may be made of aminocarboxylates, imidazolinium betaines, lecithins, alkylamine oxides.
- Nonionic surfactants include ether type, ether ester type, ester type and nitrogen-containing type.
- Ether type includes polyoxyethylene alkyl and alkylphenyl ether, alkylallyl formaldehyde condensed polyoxyethylene ether, polyoxyethylene poly Examples include oxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, ether ester type, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester polyoxyethylene ether, ester type, Polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, sorbitan ester, propylene glycol ester Le, sucrose esters, nitrogen-containing type, fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amide, and the like.
- a fluorine-type surfactant etc. are mentioned.
- an anionic surfactant or a nonionic surfactant is preferable, and as the salt, ammonium salt, potassium salt, sodium salt and the like can be mentioned, and ammonium salt and potassium salt are particularly preferable.
- 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 Ethers such as glycol, alkyl polypropylene glycol alkyl ether, alkyl polypropylene glycol alkenyl ether, alkenyl polypropylene glycol; polysaccharides such as alginic acid, pec
- the substrate to be polished is a glass substrate or the like
- any surfactant can be suitably used.
- alkali metal, alkaline earth In the case where the influence of contamination by a metal or a halide is disliked, it is desirable to use an acid or an ammonium salt surfactant.
- the polishing abrasive dispersion of the present invention contains a surfactant and / or a hydrophilic compound
- the total content is 0.001 to 10 g in 1 L of the polishing abrasive dispersion. It is preferably 0.01 to 5 g, more preferably 0.1 to 3 g.
- the content of the surfactant and / or the hydrophilic compound is preferably 0.001 g or more in 1 liter of the abrasive dispersion for polishing, and is preferably 10 g or less from the viewpoint of preventing reduction in the polishing rate. .
- a heterocyclic compound may be contained in the polishing abrasive dispersion of the invention.
- the “heterocyclic compound” is a compound having a heterocyclic ring containing one or more heteroatoms.
- a hetero atom means an atom other than a carbon atom or a hydrogen atom.
- a heterocycle means a cyclic compound having at least one heteroatom.
- a heteroatom means only those atoms that form part of a heterocyclic ring system, either external to the ring system, separated from the ring system by at least one non-conjugated single bond, Atoms that are part of a further substituent of are not meant.
- Preferred examples of the hetero atom include, but are not limited to, a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom.
- imidazole, benzotriazole, benzothiazole, tetrazole, and the like can be used.
- 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.
- the content of the heterocyclic compound in the polishing abrasive dispersion of the present invention is preferably 0.001 to 1.0% by mass, and preferably 0.001 to 0.7% by mass. Is more preferably 0.002 to 0.4% by mass.
- ⁇ PH adjuster> In order to enhance the effects of the above additives, an acid or a base can be added as necessary to adjust the pH of the polishing composition.
- an alkaline one is used as a pH adjuster.
- amines such as sodium hydroxide, aqueous ammonia, ammonium carbonate, ethylamine, methylamine, triethylamine, tetramethylamine are used.
- an acidic one is used as a pH adjuster.
- mineral acids such as hydrochloric acid and nitric acid
- hydroxy acids such as acetic acid, lactic acid, citric acid, malic acid, tartaric acid and glyceric acid are used.
- a pH buffering agent may be used.
- the pH buffering agent that can be used include phosphates and borates such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium tetraborate tetrahydrate, and organic acids.
- Examples of the dispersion solvent that can be used in the polishing abrasive dispersion of the present invention include alcohols such as methanol, ethanol, isopropanol, n-butanol, and methyl isocarbinol; acetone, 2-butanone, ethyl amyl ketone, and diacetone.
- Ketones such as alcohol, isophorone and cyclohexanone; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H- Ethers such as pyran; glycol ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol and ethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate Glycol ether acetates such as 2-butoxyethyl acetate; esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate, and ethylene carbonate; aromatic hydrocarbons such as benzene, toluene, and xylene; Aliphatic hydrocarbons
- the solid content concentration contained in the polishing abrasive dispersion 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. Conversely, even if the solid content concentration is too high, the polishing rate is rarely improved further, which can be uneconomical.
- silica fine particles (mother particles) Regarding the SiO 2 weight of the silica fine particle dispersion described later, in the case of silica fine particles using sodium silicate as a raw material, the amount was reduced by 1000 ° C. and measured by weighing. 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.
- [Silica composite fine particles] The content rate of each element shall be measured with 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. Once dry, add a small amount of water and 50 ml of nitric acid to dissolve and place 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 spectrometer (for example, Z-2310, manufactured by Hitachi, Ltd.).
- an atomic absorption spectrometer for example, Z-2310, manufactured by Hitachi, Ltd.
- the content (content) of the components of Na, Al, Ag, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn, Zr, U and Th in the present invention is as follows. The value obtained by measurement by such a method is meant.
- the content rate of each anion shall be measured by the following method.
- ⁇ Cl> Acetone is added to a 20 g sample (solid content of 20% by mass) composed of a silica-based composite fine particle dispersion to adjust to 100 ml, and 5 ml of acetic acid and 4 ml of 0.001 molar sodium chloride solution are added to this solution to form a 0.002 molar silver nitrate solution.
- the analysis is carried out by potentiometric titration (Kyoto Electronics: potentiometric titrator AT-610).
- the content of each element or each anion in the silica fine particles is determined by using the silica fine particle dispersion instead of the silica composite fine particle dispersion in the method for analyzing silica-based composite fine particles. went.
- ⁇ Average particle size> For the silica fine particle dispersions and silica-based composite fine particle dispersions obtained in the examples and comparative examples, the average particle size of the particles contained therein was measured by the method described above. Specifically, PAR-III manufactured by Otsuka Electronics Co., Ltd. was used for the silica fine particle dispersion, and LA950 apparatus manufactured by HORIBA was used for the silica-based composite fine particle dispersion.
- the measurement conditions of PAR-III are as follows. A preliminarily prepared 0.56% by mass ammonia water was added to the silica fine particle dispersion to adjust the solid content concentration to 1.0% by mass and filled in a plastic measuring cell.
- the amount of light was adjusted so that the scattering intensity was 8000 to 12000 with PINHOLE SELECTOR and ATTENUATOR FILTER, and the refractive index of the solvent was measured using the value of water.
- the LA-950 measurement conditions are as follows. LA-950V2 version is 7.02, algorithm options are standard calculation, solid refractive index 1.450, solvent (pure water) refractive index 1.333, 15 iterations, sample injection bath circulation rate 5 The stirring speed was 2, and measurement was performed using a measurement sequence in which these were set in advance. And the measurement sample was thrown into the sample insertion port of the apparatus with the dropper with the stock solution.
- the transmittance (R) was added so that the numerical value was 90%. And after the numerical value of the transmittance
- a transmission electron microscope Transmission Electron Microscope; Hitachi Ltd. make, model number: S-5500
- a point that bisects the major axis on the major axis was determined, two points where a straight line perpendicular to the major axis intersected with the outer edge of the particle were determined, and a distance between the two points was measured to obtain a minor axis (DS). And ratio (DS / DL) was calculated
- this substrate to be polished is set in a polishing apparatus (NF300, manufactured by Nano Factor Co., Ltd.), and a polishing pad ("IC-1000 / SUBA400 concentric type" manufactured by Nitta Haas) is used. Polishing was performed by supplying a polishing abrasive dispersion at a rotation speed of 90 rpm at a rate of 50 ml / min for 1 minute. And the grinding
- AFM atomic force microscope
- the polishing scratches were observed by polishing five substrates and observing the insulating film surface using an optical microscope.
- the evaluation criteria are as follows. ⁇ Observation of 5 sheets, there are too many linear traces and cannot be counted visually. ⁇ Since 5 sheets were observed, even one line was found to have a linear mark ... "Yes” ⁇ Since 5 sheets were observed, no linear traces were observed.
- a dispersion (polishing abrasive dispersion) containing the silica-based composite fine particle dispersion obtained in each of the examples and comparative examples was prepared.
- the solid content concentration was 9% by mass and the pH was adjusted to 2.0 by adding nitric acid.
- An aluminum hard disk substrate is set in a polishing apparatus (NF300 manufactured by Nano Factor Co., Ltd.), and a polishing pad (“Polytex ⁇ 12” manufactured by Nitta Haas Co., Ltd.) is used. Polishing abrasive at a substrate load of 0.05 MPa and a table rotation speed of 30 rpm.
- Polishing by supplying the particle dispersion at a rate of 20 ml / min for 5 minutes, using an ultra-fine defect / visualization macro device (manufactured by VISION PSYTEC, product name: Micro-Max), and an expansion level of Zoom 15 on the adjustment ring
- the total number of scratches (linear traces) present on the polished substrate surface corresponding to 65.97 cm 2 was counted and totaled, and evaluated according to the following criteria. Number of linear marks Evaluation Less than 50 “Very few” 50 to less than 80 80 or more "Many” At least 80 and so many that the total number cannot be counted
- ⁇ Preparation process 1> ⁇ Preparation of High-Purity Silicic Acid Solution> An aqueous sodium silicate solution having an SiO 2 concentration of 24.06% by mass and an Na 2 O concentration of 7.97% by mass was prepared. Then, pure water was added so that SiO 2 concentration of 5.0 wt% to the aqueous solution of sodium silicate.
- [Acid silicic acid solution] 18 kg of the obtained 5.0 mass% sodium silicate aqueous solution was passed through 6 L of strongly acidic cation exchange resin (SK1BH, manufactured by Mitsubishi Chemical Corporation) at a space velocity of 3.0 h ⁇ 1 , and the pH was 2.7. 18 kg of acidic silicic acid solution was obtained.
- the obtained acidic silicic acid solution had a SiO 2 concentration of 4.7% by mass.
- silica fine particle dispersion (average particle diameter of silica fine particles: 45 nm) >> 963 g of 12% by mass of 25 nm silica fine particle dispersion was added to 991 g of pure water while stirring. Subsequently, 1,414 g of 15% ammonia water was further added, and then the temperature was raised to 87 ° C. and held for 30 minutes. Next, 12,812 g of a high-purity silicic acid solution was further added over 18 hours, and after completion of the addition, aging was performed while maintaining 87 ° C. to obtain a 45 nm silica fine particle dispersion. 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).
- SIP1013 ultrafiltration membrane
- silica fine particle dispersion (average particle diameter of silica fine particles: 70 nm) >> 705 g of a silica fine particle dispersion (SiO 2 concentration 12 mass%) prepared by dispersing silica fine particles with an average particle diameter of 45 nm in a solvent was prepared.
- 50 g of 15% ammonia water was further added, and then the temperature was raised to 87 ° C. and held for 30 minutes.
- the average particle diameter of the silica fine particles is a value obtained by measurement by a dynamic light scattering method (dynamic light scattering particle diameter measuring apparatus: PAR-III).
- 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).
- silica fine particle dispersion (average particle diameter of silica fine particles: 96 nm) >> 1,081 g of a dispersion liquid (SiO 2 concentration: 12% by mass) in which silica fine particles having an average particle diameter of 70 nm are dispersed in a solvent is prepared, This was added to 1,081 g of pure water while stirring. Subsequently, 50 g of 15% ammonia water was further added, and then the temperature was raised to 87 ° C. and held for 30 minutes.
- a dispersion liquid SiO 2 concentration: 12% by mass
- the average particle diameter of the silica fine particles is a value obtained by measurement by a dynamic light scattering method (dynamic light scattering particle diameter measuring apparatus: PAR-III).
- 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).
- Anion exchange resin SANUP B manufactured by Mitsubishi Chemical Corporation was added to the silica fine particle dispersion after concentration to remove anions.
- cerium (III) nitrate hexahydrate manufactured by Kanto Chemical Co., Inc., 4N high-purity reagent
- 2.5 mass% B liquid in terms of CeO 2 was obtained.
- the liquid A (6,000 g) was heated to 50 ° C. and stirred, while the liquid B (8,453 g, 100 parts by mass of SiO 2) was equivalent to 117.4 parts by mass of CeO 2. Was added over 18 hours. During this time, the liquid temperature was maintained at 50 ° C., and 3% ammonia water was added as necessary to maintain pH 7.85. And when addition of B liquid was complete
- Precursor particle dispersion A obtained after completion of washing had a solid content concentration of 7% by mass, and a laser diffraction scattering method particle size (LA-950 manufactured by HORIBA) was 4.6 ⁇ m [median diameter]. .
- ⁇ Preparation process 3> Next, 3% by mass acetic acid was added to the precursor particle dispersion A obtained in Preparatory Step 2 to adjust the pH to 6.5, followed by drying in a 120 ° C. dryer for 15 hours, and then at 1062 ° C. Firing was performed using a muffle furnace for 2 hours to obtain a powdery fired body.
- the fired product pulverized dispersion obtained was treated at 675 G for 3 minutes with a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., model number “CR21G”), and a light liquid (the supernatant liquid from which the sediment component was removed) was recovered.
- a silica-based composite fine particle dispersion was obtained.
- the average particle diameter (median diameter) of the silica-based composite fine particle dispersion was measured using a laser diffraction scattering method (LA-950, manufactured by HORIBA), and was 0.208 ⁇ m (208 nm).
- Example 1 the silica-based composite fine particle dispersion obtained in the preparation step 3 was subjected to a second crushing treatment and a centrifugal separation treatment. The method will be described below.
- the silica-based composite fine particle dispersion obtained by performing the second crushing treatment and the centrifugal separation treatment also corresponds to the dispersion of the present invention.
- 1 kg of a liquid prepared by adding ion exchange water to the silica-based composite fine particle dispersion obtained in the preparation step 3 to adjust the solid content concentration to 20% by mass was prepared. Then, this liquid was crushed using a crusher (LMZ-06 manufactured by Ashizawa Finetech Co., Ltd.).
- pulverization was performed using quartz beads having a diameter of 0.25 mm, a filling rate of 85%, a peripheral speed of 10 m / s, and circulation at 1 L / min for 80 cracks.
- concentration at the time of crushing was 10% by mass.
- 3% ammonia was added to maintain the pH at 9.2.
- the solid content recovered by pushing the crushing chamber with water was 9.3% by mass.
- the crushed dispersion was treated with a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., model number “CR21G”) at a relative centrifugal acceleration of 1700 G for 102 seconds.
- the average particle diameter (median diameter) of the obtained silica-based composite fine particle dispersion was measured using a laser diffraction scattering method (LA-950, manufactured by HORIBA), and found to be 0.196 ⁇ m (196 nm).
- silica-based composite fine particles contained in the obtained silica-based composite fine particle dispersion were measured by an X-ray diffraction method, a Ceriaite diffraction pattern was observed.
- Example 2 the silica-based composite fine particle dispersion obtained in the preparation step 3 was subjected to a second crushing treatment and a centrifugal separation treatment. The method will be described below. Of course, the silica-based composite fine particle dispersion obtained by performing the second crushing treatment and the centrifugal separation treatment also corresponds to the dispersion of the present invention. Ion exchange water was added to the silica-based composite fine particle dispersion obtained in the preparation step 3 to adjust the solid content concentration to 5% by mass.
- a 4 L rotor was used with a high-speed centrifuge H-660 manufactured by KOKUSAN Corporation, and the mixture was allowed to pass through at a relative centrifugal acceleration of 10,000 G and a flow rate of 1 L / min, followed by centrifugation.
- the silica fine particle dispersion obtained after centrifuging had a solid content of 1.8%, and the average particle size measured by the laser diffraction scattering method was 0.200 ⁇ m (200 nm) [median diameter].
- Example 3 4.0 kg of the precursor particle dispersion A obtained in the preparation step 2 was prepared. Then, this was crushed using a crusher (LMZ-06 manufactured by Ashizawa Finetech Co., Ltd.). Here, the crushing was performed using quartz beads having a diameter of 0.25 mm, a filling rate of 60%, a peripheral speed of 8 m / s, and 20 passes under conditions of 2 L / min. During the pulverization of the precursor particle dispersion A, ammonia water or the like was not added here. The pH of the precursor fine particle dispersion A after pulverization was 9.0.
- the average particle diameter (median diameter) of the pulverized precursor fine particle dispersion A was measured using a laser diffraction scattering method (LA-950, manufactured by HORIBA) and found to be 0.225 ⁇ m.
- LA-950 laser diffraction scattering method
- 3% by mass acetic acid was added to the pulverized precursor fine particle dispersion A to adjust the pH to 6.5, followed by drying in a 120 ° C. drier for 15 hours, and then a 1062 ° C. muffle furnace. And baked for 2 hours to obtain a powdery fired body.
- the fired body pulverized dispersion liquid was treated with a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., model number “CR21G”) at a relative centrifugal acceleration of 1700 G for 102 seconds, and the light liquid was recovered.
- a centrifugal separator manufactured by Hitachi Koki Co., Ltd., model number “CR21G”
- the average particle diameter (median diameter) of the obtained silica-based composite fine particle dispersion was measured using a laser diffraction scattering method (LA-950, manufactured by HORIBA), it was 0.198 ⁇ m (198 nm).
- cerium (III) nitrate hexahydrate manufactured by Kanto Chemical Co., Inc., 4N high-purity reagent
- 2.5 mass% B liquid in terms of CeO 2 was obtained.
- the obtained precursor particle dispersion was dried in a dryer at 120 ° C. for 16 hours, and then baked for 2 hours using a muffle furnace at 1030 ° C. to obtain a powdery fired body.
- the fired body pulverized dispersion liquid was treated with a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., model number “CR21G”) at a relative centrifugal acceleration of 1700 G for 102 seconds, and the light liquid was recovered.
- a centrifugal separator manufactured by Hitachi Koki Co., Ltd., model number “CR21G”
- the average particle diameter (median diameter) of the obtained silica-based composite fine particle dispersion was measured using a laser diffraction scattering method (LA-950, manufactured by HORIBA) and found to be 0.194 ⁇ m (194 nm).
- silica-based composite fine particles contained in the silica-based composite fine particle dispersion obtained in Example 4 were observed using SEM and TEM.
- An SEM image and a TEM image (50,000 times) are shown in FIGS.
- FIG. 2 shows an X-ray diffraction pattern of the silica-based composite fine particles contained in the silica-based composite fine particle dispersion obtained in Example 4.
- Example 5 Ion exchange water was added to the silica fine particle dispersion obtained in the preparation step 1 to obtain 6,000 g of A liquid having a SiO 2 solid content concentration of 3 mass%.
- cerium (III) nitrate hexahydrate manufactured by Kanto Chemical Co., Inc., 4N high-purity reagent
- 2.5 mass% B liquid in terms of CeO 2 was obtained.
- the liquid A (6,000 g) was heated to 50 ° C. and stirred, while the liquid B (8,453 g, 100 parts by mass of SiO 2) was equivalent to 117.4 parts by mass of CeO 2. Was added over 18 hours. During this time, the liquid temperature was maintained at 50 ° C., and 3% ammonia water was added as necessary to maintain pH 7.85. And when addition of B liquid was complete
- the precursor particle dispersion obtained after the washing was finished had a solid content concentration of 7% by mass, a pH of 9.1 (at 25 ° C.), and a laser diffraction scattering particle size (LA-950 manufactured by HORIBA). It was 4.6 ⁇ m.
- acetic acid aqueous solution was added to the obtained precursor particle dispersion to adjust the pH to 6.5, followed by drying in a 120 ° C. dryer for 15 hours, and then using a 1062 ° C. muffle furnace. Was fired for 2 hours to obtain a powdery fired body.
- concentration at the time of crushing is 25 mass%. Then, wet crushing was performed under the conditions that the peripheral speed of the disk in the crusher was 12 m / sec, the number of passes was 25, and the residence time per pass was 0.43 minutes. Further, a 3% aqueous ammonia solution was added for each pass so that the pH of the suspension during crushing was maintained at 10. In this way, a fired body pulverized dispersion having a solid content concentration of 22% by mass was obtained.
- the obtained pulverized dispersion was centrifugated for 3 minutes at a relative centrifugal acceleration of 675 G in a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., model number “CR21G”) to remove sediment components, and silica.
- a system composite fine particle dispersion was obtained.
- the average particle diameter (median diameter) of the obtained silica-based composite fine particle dispersion was measured using a laser diffraction scattering method (LA-950, manufactured by HORIBA) and found to be 0.208 ⁇ m (208 nm).
- Example 6 Ion exchange water was added to the silica fine particle dispersion having an average particle diameter of 70 nm obtained in the process of preparation step 1 to obtain 6,000 g of liquid A having a SiO 2 solid content concentration of 3.0 mass%. Ion exchange water was added to cerium (III) hexahydrate to obtain 3.0 mass% B liquid in terms of CeO 2 . Next, 6,000 g (dry 180.0 g) of Liquid A was cooled to 15.5 ° C., and 7044.2 g (dry 211.3 g) of Liquid B was added thereto over 18 hours while stirring.
- Example 2 After crushing, the beads were separated through a 44 mesh wire mesh. During pulverization, an aqueous ammonia solution was added to maintain the pH at 10.0. In this way, 1151 g of a fired body pulverized dispersion having a solid content concentration of 6.6% by mass was obtained. Furthermore, the fired body pulverized dispersion was treated with a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., model number “CR21G”) at a relative centrifugal acceleration of 1700 G for 102 seconds, and a light liquid (supernatant liquid from which sediment components were removed) The silica composite fine particle dispersion was recovered. Then, the obtained silica-based composite fine particle dispersion was evaluated in the same manner as in Example 1.
- a centrifugal separator manufactured by Hitachi Koki Co., Ltd., model number “CR21G”
- cerium (III) nitrate hexahydrate manufactured by Kanto Chemical Co., Inc., 4N high-purity reagent
- 3.0 mass% B liquid in terms of CeO 2 was obtained.
- the average particle diameter (median diameter) of the precursor particle dispersion after completion of washing was measured using a laser diffraction scattering method (LA-950, manufactured by HORIBA) and found to be 0.33 ⁇ m.
- 3% by mass acetic acid was added to the obtained precursor particle dispersion to adjust the pH to 6.5, followed by drying in a 120 ° C. dryer for 15 hours, and then using a muffle furnace at 1028 ° C. for 2 hours. Time firing was performed to obtain a powdery fired body.
- the fired body disintegrated dispersion liquid was subjected to a relative centrifugal acceleration: 675 G for 3 minutes using a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., model number “CR21G”), and a light liquid (the supernatant liquid from which the sediment component was removed) was recovered.
- a silica-based composite fine particle dispersion was obtained.
- the obtained silica-based composite fine particle dispersion was evaluated in the same manner as in Example 1.
- ⁇ Comparative Example 3> 3.63 kg of 0.7 mass% ammonia water was prepared, and this was heated up to 93 degreeC (A liquid). Next, 5.2% of 1.6 mass% cerium nitrate solution (liquid B) was prepared as CeO 2 , and liquid B was added to liquid A over 1 hour. After completion of the addition, aging was performed for 3 hours while maintaining 93 ° C. The pH of the solution after aging was 8.4. The aged solution was cooled and then centrifuged at a relative centrifugal acceleration of 5000 G, and the supernatant was removed.
- ion-exchanged water was added to the precipitated cake and stirred to perform reslurry, and the process of centrifuging again at a relative centrifugal acceleration of 5000 G was repeated until the conductivity of the slurry became 100 ⁇ S / cm or less.
- the slurry having an electric conductivity of 100 ⁇ S / cm or less was adjusted to a solid content concentration of 6.0% by mass and dispersed with an ultrasonic wave to obtain a ceria fine particle dispersion.
- the average particle diameter (median diameter) of the obtained ceria fine particle dispersion was measured using a laser diffraction scattering method (LA-950, manufactured by HORIBA), and found to be 0.116 ⁇ m.
- the crystallite diameter and the crystal form were measured by X-ray, the crystallite diameter was 18 nm, which showed the Ceriaite crystal form.
- the ceria fine particle dispersion was adjusted to pH 5.0 with nitric acid to obtain a polishing abrasive dispersion having a solid content of 0.6 mass.
- the thermal oxide film was polished with this polishing abrasive dispersion. The results are shown in Tables 1 to 3.
- the fired product pulverized dispersion obtained was treated at 675 G for 3 minutes with a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., model number “CR21G”), and a light liquid (the supernatant liquid from which the sediment component was removed) was recovered.
- a silica-based composite fine particle dispersion was obtained.
- the average particle diameter (median diameter) of the silica-based composite fine particle dispersion was measured using a laser diffraction scattering method (LA-950, manufactured by HORIBA), and was 0.221 ⁇ m (221 nm).
- the fired product pulverized dispersion obtained was treated at 675 G for 3 minutes with a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., model number “CR21G”), and a light liquid (the supernatant liquid from which the sediment component was removed) was recovered.
- a silica-based composite fine particle dispersion was obtained.
- the average particle diameter (median diameter) of the silica-based composite fine particle dispersion was measured using a laser diffraction scattering method (LA-950, manufactured by HORIBA), and found to be 0.194 ⁇ m (194 nm).
- a fired body pulverized dispersion having a solid content concentration of 20% by mass was obtained.
- the obtained pulverized dispersion was centrifugated with a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., CR21G) at a relative centrifugal acceleration of 675G for 3 minutes to remove sediment components, and silica-based composite fine particle dispersion A liquid was obtained.
- Example 2 EDS Composition Analysis of Coating Film
- JEM-2100F field emission transmission electron microscope, manufactured by JEOL Ltd.
- accelerating electron 120 kV
- magnification 50,000 times
- EDS measurement was performed by selectively applying an electron beam.
- the measurement conditions for energy dispersive X-ray spectrometry (EDS) are shown below.
- 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 manufactured by JEOL Ltd., UTW type Si (Li) semiconductor detector Beam system: 0.2 nm
- FIGS. 5A and 5B A photograph (TEM image) obtained by observation using a transmission electron microscope is shown in FIGS. Then, as a result of EDS measurement in which an electron beam was selectively applied to the silica coating portion on the outer side of the child particles (ceria crystal particles) confirmed by FIGS. 5A and 5B, the intensity of Si was around 1.74 keV. A peak appeared and an intensity peak of Ce appeared near 4.84 keV. The Si atom number% was 0.836 atom%, the Ce atom number% was 0.277, and the Si atom number% / Ce atom number% was calculated to be 3.018. Similarly, Table 4 shows the results of similar measurements for Examples 1 and 7 and Comparative Examples 1 and 3. In Comparative Examples 1 and 3, no film was confirmed.
- titration was performed by adding a cationic colloid titration solution (0.001N polydiallyldimethylammonium chloride solution) at intervals of 5 seconds, 20 ml at an injection rate of 0.2 ml, and an injection rate of 2 seconds / ml.
- a cationic colloid titration solution 0.001N polydiallyldimethylammonium chloride solution
- the addition amount (ml) of the cation colloid titrant 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 starting point of the flow potential curve,
- Table 5 Further, the flow potential curve is shown in FIG.
- 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.
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Abstract
Description
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。
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。
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)で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強固に固着せず、酸化セリウムが脱落し、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。
本発明は以下の(1)~(21)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[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。
[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は、X線回折に供して測定される、前記結晶性セリアの結晶子径が10~25nmであること。
(2)さらに、下記[4]の特徴を備える、上記(1)に記載のシリカ系複合微粒子分散液。
[4]前記シリカ系複合微粒子は、画像解析法で測定された短径/長径比が0.8以下である粒子の個数割合が35%以下であること。
(3)さらに、下記[5]の特徴を備える、上記(1)または(2)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は、前記子粒子の表面にシリカ被膜を有していること。
(4)さらに、下記[6]の特徴を備える、上記(1)~(3)のいずれかに記載のシリカ系複合微粒子分散液。
[6]前記子粒子の主成分である結晶性セリアにケイ素原子が固溶していること。
(5)前記子粒子に含まれるセリウム原子およびケイ素原子について、隣接するセリウム-ケイ素原子間距離をR1とし、隣接するセリウム-セリウム原子間距離をR2としたときに、R1<R2の関係を満たす、上記(4)に記載のシリカ系複合微粒子分散液。
(6)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(3)~(5)のいずれかに記載のシリカ系複合微粒子分散液。
(7)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)~(6)のいずれか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。
(8)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)~(7)のいずれかに記載のシリカ系複合微粒子分散液。
(9)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、上記(1)~(8)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)
(10)上記(1)~(9)のいずれかに記載のシリカ系複合微粒子分散液を含む研磨用砥粒分散液。
(11)シリカ膜が形成された半導体基板の平坦化用に用いることを特徴とする上記(10)に記載の研磨用砥粒分散液。
(12)下記の工程1~工程3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。
(13)前記工程2の(ii)において、前記溶媒を加えて、pH8.6~10.8の範囲にて、前記湿式で解砕処理する、上記(12)に記載のシリカ系複合微粒子分散液の製造方法。
(14)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(13)に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。
(15)上記(1)~(9)のいずれかに記載のシリカ系複合微粒子を含む、イオン強度が0.007以上である研磨用砥粒分散液。
(16)イオン強度調整剤として硝酸アンモニウムおよび酢酸アンモニウムからなる群から選ばれる1種または2種を含むことを特徴とする、上記(15)に記載の研磨用砥粒分散液。
(17)上記(1)~(9)のいずれかに記載のシリカ系複合微粒子を含み、さらに酸解離定数(pKa)が1.5以上の酸性化合物を含むことを特徴する研磨用砥粒分散液。
(18)前記酸性化合物の含有率が0.0002~0.1質量%であることを特徴とする、上記(17)に記載の研磨用砥粒分散液。
(19)前記酸性化合物が酢酸であることを特徴とする、上記(17)または(18)に記載の研磨用砥粒分散液。
(20)シリカ膜が形成された半導体基板の平坦化用に用いることを特徴とする上記(15)~(19)のいずれかに記載の研磨用砥粒分散液。
(21)pHが3~8であり、シリカ膜が形成された半導体基板の平坦化用に用いることを特徴とする上記(20)に記載の研磨用砥粒分散液。
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。
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は、X線回折に供して測定される、前記結晶性セリアの結晶子径が10~25nm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。
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。
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。
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。
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。
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く、50ppm以下であることがより好ましく、25ppm以下であることがより好ましく、5ppm以下であることがより好ましく、1ppm以下であることがさらに好ましい。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。
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、酸処理等で不純物を低減させることも行われている。
・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
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30nmよりも小さいと研磨レートが不足する。平均粒子径が330nmよりも大きいと、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。
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)あるいは公知の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公知の動的光散乱法による粒子径測定装置(好ましくは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公知のレーザー回折散乱法による測定装置(好ましくは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、公知の動的光散乱法による粒子径測定装置や公知のレーザー回折散乱法による測定装置(好ましくはマイクロトラックUPAやLA-950)を用いることが好ましい。
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。
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、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。また、母粒子の表面に子粒子が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。
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。
子粒子の平均結晶子径の測定方法を、(111)面(2θ=28度近傍)の場合を例として以下に示す。
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)面のピークの半値全幅を測定し、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(ここでは、K=0.94)
λ:X線波長(1.7889オングストローム、Cuランプ)
β:半値全幅(rad)
θ:反射角
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てもよい。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てもよい。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。
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、本発明の複合微粒子では子粒子の表面の少なくとも一部はシリカ層によって被覆されているので、本発明の複合微粒子の最表面(最外殻)にはシリカのOH基が存在することになる。このため研磨剤として利用した場合に、本発明の複合微粒子は研磨基板表面の-OH基による電荷で反発しあい、その結果、研磨基板表面への付着が少なくなると考えられる。
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、子粒子のセリア粒子が研磨時に脱落しても、その表面はシリカで覆われているため負の電荷を有しており、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。
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。
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)~(III)の全てを含むものである。
(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
(III)セリア子粒子中に固溶しているシリカ成分
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やセリアやシリカが溶解し除去されるプロセスであっても溶解量が非常に少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。
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。
本発明の複合微粒子が好ましい態様である場合、その外表面側に存在する子粒子(セリア微粒子)において、Si原子がCeO2結晶に侵入型の固溶をしていると見られる。Si原子の固溶により、CeO2結晶の結晶歪みが生じることで、CeO2の化学反応性を助長する結果、上記の高い研磨速度を示すものと推察される。
なお、上記のR1、R2等のセリウム原子およびケイ素原子の原子間距離は、後述する実施例に説明する方法で測定して得た平均結合距離を意味するものとする。
ここで、画像解析法で測定された短径/長径比が0.80以下である粒子は、原則的に粒子結合型のものと考えられ0.80を超える粒子は真球状の単粒子であるものと考えられる。また短径/長径比が0.80以下の粒子の個数割合が35%以下であるこということは、主成分は真球状の単粒子であると考えられる。
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。
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。
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、前述の母粒子の場合と同様に、原子吸光分光分析、ICP(誘導結合プラズマ発光分光分析装置)、電位差滴定法、イオンクロマトグラフを用いて測定して求める値とする。
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。
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)
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、その変曲点における流動電位をC(mV)とし、変曲点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。
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3を備える。
<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。
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、水酸化セリウムや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。
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、酸など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。
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。
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。
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、強固な凝集体が生成すること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、母粒子上のセリウムシリケート化合物からセリウムが拡散してセリアの結晶化が十分に進行し、その結果セリア粒子はシリカ層で被覆される。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。
(i)乾式で解砕処理し、溶媒を加えて溶媒分散処理する。
(ii)溶媒を加えて、湿式で解砕処理する。
乾式の解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。
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。
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、シリカ系複合微粒子散液を得る。
工程3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。遠心加速度が上記の条件に満たない場合は、シリカ系複合微粒子分散液中に粗大粒子が残存するため、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。
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、調合液の酸化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傾向があるからである。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。
本発明の分散液を含む液体は、研磨用砥粒分散液(以下では「本発明の研磨用砥粒分散液」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、ガラス基板の平坦化用の研磨用砥粒分散液として好適に使用することができる。ここで本発明の研磨用砥粒分散液を用いてシリカ膜が形成された半導体基板を平坦化する場合、本発明の研磨用砥粒分散液のpHを3~8とすることが好ましい。
研磨用砥粒分散液が、酸解離定数(pKa)が1.5以上の酸性化合物を含む場合、研磨速度の改善が見られる。
酸解離定数(pKa)が1.5以上の酸性化合物として、酢酸、乳酸、ギ酸、リンゴ酸、安息香酸、クエン酸、酒石酸、リン酸、炭酸などが挙げられる。
逆に、酸解離定数(pKa)が1.5未満の酸性化合物として、硝酸、硫酸、塩酸、過塩素酸、臭化水素酸、トリクロロ酢酸などが挙げられる。
なお、本発明において酸解離定数は、溶媒が水で25℃の場合の酸解離定数を意味するものとする。
本発明の研磨用砥粒分散液のイオン強度が0.007以上である場合、研磨速度の改善が見られる。このイオン強度の上限は0.1であってよく、0.04であることが好ましい。
本発明の研磨用砥粒分散液のイオン強度は、下式から算出される値を意味するものとする。
本発明の研磨用砥粒分散液はイオン強度調整剤として硝酸アンモニウムおよび酢酸アンモニウムからなる群から選ばれる1種または2種を含むことが好ましい。
本発明の研磨用砥粒分散液には、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添加し、研磨スラリーとして使用することができる。この様な研磨促進剤の例としては、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。
本発明の研磨用砥粒分散液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。
本発明の研磨用砥粒分散液を適用する被研磨基材に金属が含まれる場合、金属に不動態層又は溶解抑制層を形成させることで被研磨基材の侵食を抑制するために、本発明の研磨用砥粒分散液へ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。
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。
本発明の研磨用砥粒分散液の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。
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。
[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。
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のメスフラスコ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。
<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。
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のメスフラスコにおさめ、50mlの遠沈管に入れて、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。
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。
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)のピークの半値全幅を測定し、Scherrerの式により、結晶子径を求めた。
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、シリカ微粒子分散液については大塚電子社製PAR-IIIを用い、シリカ系複合微粒子分散液についてはHORIBA社製LA950装置を用いた。
ここで、PAR-IIIの測定条件は以下の通りである。
あらかじめ準備しておいた0.56質量%濃度のアンモニア水をシリカ微粒子分散液へ添加して固形分濃度が1.0質量%となるように調整し、プラスチック製の測定セルに充填した。測定時はPINHOLE SELECTORとATTENUATOR FILTERで散乱強度が8000~12000となるように光量を調整し、溶媒の屈折率は水の値を使用して測定を行った。
また、LA-950測定条件は以下の通りである。
LA-950V2のバージョンは7.02、アルゴリズムオプションは標準演算、固体の屈折率1.450、溶媒(純水)の屈折率1.333、反復回数は15回、サンプル投入バスの循環速度は5、撹拌速度は2とし、あらかじめこれらを設定した測定シーケンスを使用して測定を行った。そして、測定サンプルをスポイトを使用して原液のまま装置のサンプル投入口に投入した。ここで透過率(R)の数値が90%になるように投入した。そして、透過率(R)の数値が安定した後、超音波を5分間照射し粒子径の測定を行った。
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が含む各粒子について、透過型電子顕微鏡(Transmission Electron Microscope;日立製作所社製、型番:S-5500)を用いて倍率25万倍(ないしは50万倍)で写真撮影して得られる写真投影図において、粒子の最大径を長軸とし、その長さを測定して、その値を長径(DL)とした。また、長軸上にて長軸を2等分する点を定め、それに直交する直線が粒子の外縁と交わる2点を求め、同2点間の距離を測定し短径(DS)とした。そして、比(DS/DL)を求めた。この測定を任意の50個の粒子について行い、単一粒子としての短径/長径比が0.8以下の粒子の個数比率(%)を求めた。
<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分散液(研磨用砥粒分散液)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で研磨用砥粒分散液を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、5枚の基板を研磨し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。評価基準は以下の通り。
・5枚を観察して、線状痕が多すぎて目視でカウントできない・・・「非常に多い」
・5枚を観察して、1枚でも線状痕が認められた・・・「有り」
・5枚を観察して、線状痕が認められなかった・・・・「明確には認められない」
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分散液(研磨用砥粒分散液)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で研磨用砥粒分散液を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、調整リングでZoom15の拡大レベルに調整して全面観察し、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」
50個から80個未満 「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程多い 「※」
《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。
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。
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。
514.5gの高純度珪酸液を攪拌しながら、純水42gへ添加し、次いで、さらに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、さらに高純度珪酸液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。
963gの12質量%の25nmシリカ微粒子分散液を攪拌しながら、純水991gへ加えた。次いで、さらに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、さらに高純度珪酸液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。
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用意し、これを撹拌しながら、純水705gへ加えた。次いで、さらに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、さらに高純度珪酸液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。なお、ここでシリカ微粒子の平均粒子径は、動的光散乱法(動的光散乱法粒子径測定装置:PAR-III)によって測定して得られた値である。
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。
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用意し、これを撹拌しながら、純水1,081gへ加えた。次いで、さらに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、さらに高純度珪酸液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、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。なお、ここでシリカ微粒子の平均粒子径は、動的光散乱法(動的光散乱法粒子径測定装置:PAR-III)によって測定して得られた値である。
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。
準備工程1で得られた96nmの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。
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し電気伝導度が75μS/cmまで洗浄を行った。洗浄を終了して得られた前駆体粒子分散液Aは、固形分濃度が7質量%で、レーザー回折散乱法粒子径(HORIBA社製LA-950)は4.6μm[メジアン径]であった。
次に準備工程2で得られた前駆体粒子分散液Aに3質量%酢酸を加えてpHを6.5に調整して、120℃の乾燥機中で15時間乾燥させた後、1062℃のマッフル炉を用いて2時間焼成を行い、粉状の焼成体を得た。
次いで得られた焼成体解砕分散液を遠心分離装置(日立工機株式会社製、型番「CR21G」)にて、675Gで3分間処理し、軽液(沈降成分を除去した上澄み液)を回収し、シリカ系複合微粒子分散液を得た。シリカ系複合微粒子分散液についてレーザー回折散乱法(HORIBA社製LA-950)を用いて平均粒子径(メジアン径)を測定したところ、0.208μm(208nm)であった。
実施例1では、準備工程3で得られたシリカ系複合微粒子分散液について2回目の解砕処理および遠心分離処理を行った。その方法について以下に説明する。なお、2回目の解砕処理および遠心分離処理を行って得られたシリカ系複合微粒子分散液も、当然、本発明の分散液に相当する。
準備工程3で得られたシリカ系複合微粒子分散液にイオン交換水を添加して固形分濃度を20質量%に調整した液を1kg準備した。そして、この液について、解砕機(アシザワファインテック社製、LMZ-06)を用いて解砕した。ここで解砕はφ0.25mmの石英ビーズを用い、充填率を85%とし、周速を10m/sとし、1L/分の条件で循環させて80分解砕した。なお、解砕機の粉砕室及び配管中にイオン交換水が残存するため解砕時の濃度は10質量%であった。また解砕中は3%のアンモニアを添加してpHを9.2に保った。解砕後に粉砕室を水押しして回収した固形分は9.3質量%であった。
次いで解砕した分散液を、遠心分離装置(日立工機株式会社製、型番「CR21G」)にて、相対遠心加速度:1700Gで102秒処理した。そして、軽液を回収し、シリカ系複合微粒子分散液を得た。得られたシリカ系複合微粒子分散液についてレーザー回折散乱法(HORIBA社製LA-950)を用いて平均粒子径(メジアン径)を測定したところ、0.196μm(196nm)であった。
なお、原料とした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、シリカ微粒子の不純物の含有率、シリカ系複合微粒子におけるシリカ100質量部に対するセリアの質量部、シリカ系複合微粒子調製時の焼成温度、シリカ系複合微粒子の結晶子径、結晶型、シリカ系複合微粒子に含まれる不純物の含有率、シリカ系複合微粒子の平均粒子径、シリカ系複合微粒子の短径/長径比が0.8以下の粒子個数比及び研磨性能(研磨速度、表面粗さ、SiO2膜の研磨における研磨傷の観察結果、アルミハードディスクの研磨におけるスクラッチ個数)の測定結果を第1表~第3表に示す。以降の実施例、比較例も同様である。
実施例2では、準備工程3で得られたシリカ系複合微粒子分散液について2回目の解砕処理および遠心分離処理を行った。その方法について以下に説明する。なお、2回目の解砕処理および遠心分離処理を行って得られたシリカ系複合微粒子分散液も、当然、本発明の分散液に相当する。
準備工程3で得られたシリカ系複合微粒子分散液にイオン交換水を添加して固形分濃度5質量%に調整した。次いでKOKUSAN社製、高速遠心分離機H-660で4Lローターを使用し、相対遠心加速度:10,000G、通液速度1L/分の条件で通液させ、遠心分離を行った。遠心分離した後に得られたシリカ微粒子分散液は、固形分が1.8%濃度であり、レーザー回折散乱法で測定した平均粒子径が0.200μm(200nm)[メジアン径]であった。
準備工程2で得られた前駆体粒子分散液Aを4.0kg準備した。そして、これを解砕機(アシザワファインテック社製、LMZ-06)を用いて解砕した。ここで解砕はφ0.25mmの石英ビーズを用い、充填率を60%とし、周速を8m/sとし、2L/分の条件で20パスさせて解砕を行った。なお、前駆体粒子分散液Aの解砕中は、ここへアンモニア水などの添加は行わなかった。解砕後の前駆体微粒子分散液AのpHは9.0であった。また、解砕後の前駆体微粒子分散液Aについてレーザー回折散乱法(HORIBA社製LA-950)を用いて平均粒子径(メジアン径)を測定したところ、0.225μmであった。
次に、解砕後の前駆体微粒子分散液Aに3質量%酢酸を加えてpHを6.5に調整し、120℃の乾燥機中で15時間乾燥させた後、1062℃のマッフル炉を用いて2時間焼成を行い、粉状の焼成体を得た。
得られた焼成体100gにイオン交換水300gを加え、さらに3%アンモニア水溶液を用いてpHを9.2に調整した後、解砕機(カンペ(株)製、バッチ式卓上サンドミル)を用いて湿式で60分間、解砕処理を行った。解砕処理では、φ0.25mmの石英ビーズ(大研化学工業株式会社製)を用いた。なお、解砕中にはアンモニア水溶液を添加してpHを9.2に保った。このようにして固形分濃度2.4質量%の焼成体解砕分散液1020gを得た。
さらに焼成体解砕分散液を遠心分離装置(日立工機株式会社製、型番「CR21G」)にて、相対遠心加速度:1700Gで102秒処理し、軽液を回収し、シリカ系複合微粒子分散液を得た。得られたシリカ系複合微粒子分散液についてレーザー回折散乱法(HORIBA社製LA-950)を用いて平均粒子径(メジアン径)を測定したところ、0.198μm(198nm)であった。
準備工程1で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。
さらに焼成体解砕分散液を遠心分離装置(日立工機株式会社製、型番「CR21G」)にて、相対遠心加速度:1700Gで102秒処理し、軽液を回収し、シリカ系複合微粒子分散液を得た。得られたシリカ系複合微粒子分散液についてレーザー回折散乱法(HORIBA社製LA-950)を用いて平均粒子径(メジアン径)を測定したところ、0.194μm(194nm)であった。
また、図1からは、シリカ系複合微粒子の最表面に、薄いシリカ被膜が覆うように存在している様子が観察された。
準備工程1で得られたシリカ微粒子分散液にイオン交換水を加えて、SiO2固形分濃度3質量%のA液6,000gを得た。
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し、電気伝導度が75μS/cmまで洗浄を行った。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)、レーザー回折散乱法粒子径(HORIBA社製LA-950)は4.6μmであった。
次に、事前に設備洗浄を行った解砕機(アシザワファインテック株式会社製、LMZ06)にφ0.25mmの石英ビーズ595gを投入し、水運転を行った。さらに上記の懸濁液を解砕機のチャージタンクに充填した(充填率85%)。なお、解砕機の粉砕室及び配管中に残留したイオン交換水を考慮すると、解砕時の濃度は25質量%である。そして、解砕機におけるディスクの周速を12m/sec、パス回数を25回、及び1パス当たりの滞留時間を0.43分間とする条件で湿式解砕を行った。また、解砕時の懸濁液のpHを10に維持するように、パス毎に3%アンモニア水溶液を添加した。このようにして、固形分濃度22質量%の焼成体解砕分散液を得た。
次いで得られた焼成体解砕分散液を遠心分離装置(日立工機株式会社製、型番「CR21G」)にて、相対遠心加速度675Gで3分間、遠心分離処理し、沈降成分を除去し、シリカ系複合微粒子分散液を得た。得られたシリカ系複合微粒子分散液についてレーザー回折散乱法(HORIBA社製LA-950)を用いて平均粒子径(メジアン径)を測定したところ、0.208μm(208nm)であった。
準備工程1の過程において得られた平均粒子径70nmのシリカ微粒子分散液にイオン交換水を添加してSiO2固形分濃度が3.0質量%のA液6,000gを得た
次に、硝酸セリウム(III)6水和物にイオン交換水を加え、CeO2換算で3.0質量%のB液を得た。
次に、A液6,000g(dry180.0g)を15.5℃に冷却して、撹拌しながら、ここへB液7044.2g(dry211.3g)を18時間かけて添加した。この間、液温を15.5℃に維持しておき、また必要に応じて3.0質量%のアンモニア水を添加して、pHを8.3~8.6となるように保った。そして、B液の添加が終了したら、液温を15.5℃に保ったまま4時間熟成を行った。なお、A液へB液を添加している間および熟成中は調合液にエアーを吹き込みつづけ、酸化還元電位を100~200mVに保った。
熟成終了後は、限外膜を用いてろ過した後にイオン交換水を補給して洗浄する作業を、電気伝導度が26μS/cmまで繰り返し行い、前駆体粒子分散液を得た。
次に、得られた前駆体粒子分散液に3.0質量%の酢酸を加えてpHを6.5に調整し、120℃の乾燥機中で15時間乾燥させた後、1064℃のマッフル炉を用いて2時間焼成を行い、粉状の焼成体を得た。
得られた焼成体100gにイオン交換水300gを加え、さらに3.0質量%のアンモニア水溶液を加えてpH10.0に調整した後、解砕機(カンペ(株)製、バッチ式卓上サンドミル)を用いて湿式で270分間、解砕処理を行った。解砕処理では、φ0.25mmの石英ビーズを用いた。そして、解砕後に44メッシュの金網を通してビーズを分離した。なお、解砕中はアンモニア水溶液を添加して、pHを10.0に保った。このようにして固形分濃度6.6質量%の焼成体解砕分散液1151gを得た。
さらに焼成体解砕分散液を遠心分離装置(日立工機株式会社製、型番「CR21G」)にて、相対遠心加速度:1700Gで102秒処理し、軽液(沈降成分を除去した上澄み液)を回収し、シリカ系複合微粒子分散液を得た。そして、得られたシリカ系複合微粒子分散液について実施例1と同様に評価を行った。
準備工程1で得られた96nmの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2,500gを得た。
熟成終了後は、限外膜を用いてろ過した後にイオン交換水を補給して洗浄する作業を、電気伝導度が26μS/cmまで繰り返し行い、前駆体粒子分散液を得た。洗浄終了後の前駆体粒子分散液についてレーザー回折散乱法(HORIBA社製LA-950)を用いて平均粒子径(メジアン径)を測定したところ、0.33μmであった。
さらに焼成体解砕分散液を遠心分離装置(日立工機株式会社製、型番「CR21G」)にて、相対遠心加速度:675Gで3分間し、軽液(沈降成分を除去した上澄み液)を回収し、シリカ系複合微粒子分散液を得た。そして、得られたシリカ系複合微粒子分散液について実施例1と同様に評価を行った。
準備工程1で得られた96nmのシリカ微粒子分散液について、平均粒子径等の各測定を行った。
準備工程2で得られた前駆体粒子分散液Aについて、平均粒子径等の各測定を行った。
0.7質量%のアンモニア水3.63kgを準備し、これを93℃に昇温した(A液)。次いでCeO2として1.6質量%の硝酸セリウム溶液5.21kg(B液)を準備し、A液にB液を1時間かけて添加した。添加終了後は93℃を保持して3時間熟成を行った。熟成後の溶液のpHは8.4であった。熟成した溶液を冷却後、相対遠心加速度:5000Gで遠心分離し、上澄み液を除去した。そして、沈殿したケーキにイオン交換水を加えて撹拌してレスラリーを行い、再度、相対遠心加速度:5000Gで遠心分離を行う処理を、スラリーの電導度が100μS/cm以下になるまで繰り返した。電導度が100μS/cm以下となったスラリーを固形分濃度6.0質量%に調整して超音波で分散し、セリア微粒子分散液を得た。
得られたセリア微粒子分散液についてレーザー回折散乱法(HORIBA社製LA-950)を用いて平均粒子径(メジアン径)を測定したところ、0.116μmであった。
またX線で結晶子径、結晶型を測定したところ、結晶子径は18nmで、Cerianiteの結晶型を示した。
このセリア微粒子分散液を硝酸でpHを5.0に調整し、固形分濃度0.6質量の研磨用砥粒分散液を得た。この研磨用砥粒分散液で熱酸化膜の研磨を行った。結果を第1表~第3表に示す。
次に準備工程2で得られた前駆体粒子分散液Aに3質量%酢酸を加えてpHを6.5に調整して、120℃の乾燥機中で15時間乾燥させた後、1250℃のマッフル炉を用いて2時間焼成を行い、粉状の焼成体を得た。
次いで得られた焼成体解砕分散液を遠心分離装置(日立工機株式会社製、型番「CR21G」)にて、675Gで3分間処理し、軽液(沈降成分を除去した上澄み液)を回収し、シリカ系複合微粒子分散液を得た。シリカ系複合微粒子分散液についてレーザー回折散乱法(HORIBA社製LA-950)を用いて平均粒子径(メジアン径)を測定したところ、0.221μm(221nm)であった。
次に準備工程2で得られた前駆体粒子分散液Aに3質量%酢酸を加えてpHを6.5に調整して、120℃の乾燥機中で15時間乾燥させた後、390℃のマッフル炉を用いて2時間焼成を行い、粉状の焼成体を得た。
次いで得られた焼成体解砕分散液を遠心分離装置(日立工機株式会社製、型番「CR21G」)にて、675Gで3分間処理し、軽液(沈降成分を除去した上澄み液)を回収し、シリカ系複合微粒子分散液を得た。シリカ系複合微粒子分散液についてレーザー回折散乱法(HORIBA社製LA-950)を用いて平均粒子径(メジアン径)を測定したところ、0.194μm(194nm)であった。
準備工程2で得られた前駆体粒子Aに3質量%酢酸を加えてpHを6.5に調整して、120℃の乾燥機中で15時間乾燥させた後、1250℃のマッフル炉を用いて2時間焼成を行い、粉状の焼成体を得た。
得られた焼成体310gにイオン交換水430gを加え、さらに3.0質量%のアンモニア水を加えて、pH11.0に調整した後、撹拌しながら超音波浴槽中で10分間超音波を照射して懸濁液を得た。
次に事前に設備洗浄をおこなった解砕機(アシザワファインテック株式会社製、LMZ06)にφ0.25mmの石英ビーズ595gを投入し、水運転を行った。さらに上記懸濁液を解砕機のチャージタンクに充填した(充填率85%)。なお、解砕機の粉砕室及び配管中に残留したイオン交換水を考慮すると、解砕時の濃度は25質量%である。そして、解砕機におけるディスクの周速を14m/秒、パス回数30回とする条件で湿式解砕を行った。また解砕時の懸濁液のpHを11に維持するように、パス毎に3%アンモニア水溶液を添加した。このようにして、固形分濃度20質量%の焼成体解砕分散液を得た。
次いで得られた焼成体解砕分散液を遠心分離装置(日立工機株式会社製、CR21G)にて相対遠心加速度675Gで3分間、遠心分離を行い、沈降成分を除去し、シリカ系複合微粒子分散液を得た。
実施例4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
実施例2、4、7及び比較例3、6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へ0.05%の塩酸水溶液を添加してpH6に調整した。次に、その液の固形分として0.8gに相当する量を100mlのトールビーカーに入れ、流動電位の測定を行った。次にカチオンコロイド滴定液(0.001Nポリ塩化ジアリルジメチルアンモニウム溶液)を5秒間隔、1回の注入量0.2ml、注入速度2秒/mlで20ml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5表に示す。また流動電位曲線を図4に示す。
[Si固溶状態の測定]
実施例5で調製したシリカ系複合微粒子分散液を、X線吸収分光測定装置(Rigaku社製のR-XAS Looper)を用いて、CeL III吸収端(5727eV)におけるX線吸収スペクトルを測定し、そのX線吸収スペクトルに現れるEXAFS振動を得た。解析にはRigaku製ソフトウエアREX-2000を使用し、セリウム周辺の酸素及びセリウムの平均配位原子数N、平均結合距離Rを得た。結果を第6表に示す。
第6表の結果から、セリウムの周辺には酸素、ケイ素およびセリウムが存在し、セリウム-酸素原子間距離は2.4Åで、セリウム―セリウム原子間距離は3.8Åであるのに対して、セリウム-ケイ素の原子間距離は3.2Åであることが確認された。またXRDの分析結果から、セリウムはCerianiteの結晶型でCeO2として存在していることから、酸化セリウム中にSiが固溶していると考えられる。
実施例1、実施例4、比較例3、比較例4についても同様に測定を行った。結果を第6表に示す。
Claims (21)
- 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[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。
[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は、X線回折に供して測定される、前記結晶性セリアの結晶子径が10~25nmであること。 - さらに、下記[4]の特徴を備える、請求項1に記載のシリカ系複合微粒子分散液。
[4]前記シリカ系複合微粒子は、画像解析法で測定された短径/長径比が0.8以下である粒子の個数割合が35%以下であること。 - さらに、下記[5]の特徴を備える、請求項1または2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は、前記子粒子の表面にシリカ被膜を有していること。 - さらに、下記[6]の特徴を備える、請求項1または2に記載のシリカ系複合微粒子分散液。
[6]前記子粒子の主成分である結晶性セリアにケイ素原子が固溶していること。 - 前記子粒子に含まれるセリウム原子およびケイ素原子について、隣接するセリウム-ケイ素原子間距離をR1とし、隣接するセリウム-セリウム原子間距離をR2としたときに、R1<R2の関係を満たす、請求項4に記載のシリカ系複合微粒子分散液。
- 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請求項3に記載のシリカ系複合微粒子分散液。
- 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請求項1または2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。 - 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、請求項1または2に記載のシリカ系複合微粒子分散液。
- 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または2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) - 請求項1または2に記載のシリカ系複合微粒子分散液を含む研磨用砥粒分散液。
- シリカ膜が形成された半導体基板の平坦化に用いることを特徴とする請求項10に記載の研磨用砥粒分散液。
- 下記の工程1~工程3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。 - 前記工程2の(ii)において、前記溶媒を加えて、pH8.6~10.8の範囲にて、前記湿式で解砕処理する、請求項12に記載のシリカ系複合微粒子分散液の製造方法。
- 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請求項13に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。 - 請求項1または2に記載のシリカ系複合微粒子を含む、イオン強度が0.007以上である研磨用砥粒分散液。
- イオン強度調整剤として硝酸アンモニウムおよび酢酸アンモニウムからなる群から選ばれる1種または2種を含むことを特徴とする、請求項15に記載の研磨用砥粒分散液。
- 請求項1または2に記載のシリカ系複合微粒子を含み、さらに酸解離定数(pKa)が1.5以上の酸性化合物を含むことを特徴する研磨用砥粒分散液。
- 前記酸性化合物の含有率が0.0002~0.1質量%であることを特徴とする、請求項17に記載の研磨用砥粒分散液。
- 前記酸性化合物が酢酸であることを特徴とする、請求項17に記載の研磨用砥粒分散液。
- シリカ膜が形成された半導体基板の平坦化用に用いることを特徴とする請求項15または17に記載の研磨用砥粒分散液。
- pHが3~8であり、シリカ膜が形成された半導体基板の平坦化用に用いることを特徴とする請求項15または17に記載の研磨用砥粒分散液。
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JP2019081672A (ja) * | 2017-10-30 | 2019-05-30 | 日揮触媒化成株式会社 | セリア系複合微粒子分散液、その製造方法及びセリア系複合微粒子分散液を含む研磨用砥粒分散液 |
JP7020865B2 (ja) | 2017-10-30 | 2022-02-16 | 日揮触媒化成株式会社 | セリア系複合微粒子分散液、その製造方法及びセリア系複合微粒子分散液を含む研磨用砥粒分散液 |
JP2019127405A (ja) * | 2018-01-23 | 2019-08-01 | 日揮触媒化成株式会社 | セリア系複合中空微粒子分散液、その製造方法及びセリア系複合中空微粒子分散液を含む研磨用砥粒分散液 |
JP7002350B2 (ja) | 2018-01-23 | 2022-01-20 | 日揮触媒化成株式会社 | セリア系複合中空微粒子分散液、その製造方法及びセリア系複合中空微粒子分散液を含む研磨用砥粒分散液 |
US20200048551A1 (en) * | 2018-08-09 | 2020-02-13 | Versum Materials Us, Llc | Chemical Mechanical Planarization Composition For Polishing Oxide Materials And Method Of Use Thereof |
US11718767B2 (en) * | 2018-08-09 | 2023-08-08 | Versum Materials Us, Llc | Chemical mechanical planarization composition for polishing oxide materials and method of use thereof |
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KR20220034255A (ko) | 2022-03-17 |
KR102394895B1 (ko) | 2022-05-04 |
TWI656096B (zh) | 2019-04-11 |
SG11201809175PA (en) | 2018-11-29 |
US10844259B2 (en) | 2020-11-24 |
CN109155246B (zh) | 2024-01-05 |
EP3447790B1 (en) | 2023-05-24 |
TW201800339A (zh) | 2018-01-01 |
US20190153279A1 (en) | 2019-05-23 |
KR20180134889A (ko) | 2018-12-19 |
CN109155246A (zh) | 2019-01-04 |
EP3447790A4 (en) | 2020-04-08 |
EP3447790A1 (en) | 2019-02-27 |
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