JP7405567B2 - polishing liquid composition - Google Patents
polishing liquid composition Download PDFInfo
- Publication number
- JP7405567B2 JP7405567B2 JP2019204229A JP2019204229A JP7405567B2 JP 7405567 B2 JP7405567 B2 JP 7405567B2 JP 2019204229 A JP2019204229 A JP 2019204229A JP 2019204229 A JP2019204229 A JP 2019204229A JP 7405567 B2 JP7405567 B2 JP 7405567B2
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- JP
- Japan
- Prior art keywords
- component
- liquid composition
- water
- polishing liquid
- polishing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005498 polishing Methods 0.000 title claims description 184
- 239000007788 liquid Substances 0.000 title claims description 125
- 239000000203 mixture Substances 0.000 title claims description 113
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 61
- 229910052710 silicon Inorganic materials 0.000 claims description 61
- 239000010703 silicon Substances 0.000 claims description 61
- -1 nitrogen-containing basic compound Chemical class 0.000 claims description 43
- 229920003169 water-soluble polymer Polymers 0.000 claims description 41
- 229920001223 polyethylene glycol Polymers 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 38
- 239000002202 Polyethylene glycol Substances 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 239000004065 semiconductor Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 11
- 229920002557 polyglycidol polymer Polymers 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 7
- 229920005591 polysilicon Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 79
- 230000003746 surface roughness Effects 0.000 description 47
- 230000007547 defect Effects 0.000 description 45
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 238000005259 measurement Methods 0.000 description 13
- 239000011164 primary particle Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000008119 colloidal silica Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000011163 secondary particle Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 3
- 230000021736 acetylation Effects 0.000 description 3
- 238000006640 acetylation reaction Methods 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 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 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 2
- ZHTZXROPWGWVRN-UHFFFAOYSA-N 2-(4-ethenylphenyl)propan-2-ylphosphonic acid Chemical compound CC(C)(c1ccc(C=C)cc1)P(O)(O)=O ZHTZXROPWGWVRN-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
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- 238000011156 evaluation Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000009304 pastoral farming Methods 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 238000004439 roughness measurement Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010421 standard material Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- DREPONDJUKIQLX-UHFFFAOYSA-N 1-[ethenyl(ethoxy)phosphoryl]oxyethane Chemical compound CCOP(=O)(C=C)OCC DREPONDJUKIQLX-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- CQCXMYUCNSJSKG-UHFFFAOYSA-N 1-dimethoxyphosphorylethene Chemical compound COP(=O)(OC)C=C CQCXMYUCNSJSKG-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- CZZFCPUIILFVEZ-UHFFFAOYSA-N 2-dimethoxyphosphorylethenylbenzene Chemical compound COP(=O)(OC)C=CC1=CC=CC=C1 CZZFCPUIILFVEZ-UHFFFAOYSA-N 0.000 description 1
- YTVSRKBGOSAAAS-UHFFFAOYSA-N 2-dimethoxyphosphoryloct-1-ene Chemical compound CCCCCCC(=C)P(=O)(OC)OC YTVSRKBGOSAAAS-UHFFFAOYSA-N 0.000 description 1
- IGUSXLGNCKJGFD-UHFFFAOYSA-N 2-dimethoxyphosphorylprop-1-ene Chemical compound COP(=O)(OC)C(C)=C IGUSXLGNCKJGFD-UHFFFAOYSA-N 0.000 description 1
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- WDLDITCLZJRMHH-UHFFFAOYSA-N [3-(4-ethenylphenyl)-2,4-dimethylpentan-3-yl]phosphonic acid Chemical compound C(C)(C)C(C1=CC=C(C=C1)C=C)(P(O)(O)=O)C(C)C WDLDITCLZJRMHH-UHFFFAOYSA-N 0.000 description 1
- VLHORJVZAKSXHV-UHFFFAOYSA-N [ethenyl(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(C=C)OC1=CC=CC=C1 VLHORJVZAKSXHV-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- DXGKKTKNDBFWLL-UHFFFAOYSA-N azane;2-[bis(carboxymethyl)amino]acetic acid Chemical compound N.N.N.OC(=O)CN(CC(O)=O)CC(O)=O DXGKKTKNDBFWLL-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- 229960001950 benzethonium chloride Drugs 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
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- 239000001630 malic acid Substances 0.000 description 1
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- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
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- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
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- BJLZAAWLLPMZQR-UHFFFAOYSA-N oxo-di(propan-2-yloxy)phosphanium Chemical compound CC(C)O[P+](=O)OC(C)C BJLZAAWLLPMZQR-UHFFFAOYSA-N 0.000 description 1
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- 238000000206 photolithography Methods 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
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- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
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- 239000005720 sucrose Substances 0.000 description 1
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- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Description
本開示は、研磨液組成物、並びにこれを用いた研磨方法、半導体基板の製造方法に関する。 The present disclosure relates to a polishing liquid composition, a polishing method using the same, and a method for manufacturing a semiconductor substrate.
近年、半導体メモリの高記録容量化に対する要求の高まりから半導体装置のデザインルールは微細化が進んでいる。このため半導体装置の製造過程で行われるフォトリソグラフィーにおいて焦点深度は浅くなり、シリコンウェーハ（ベアウェーハ）の表面欠陥（ＬＰＤ：Ｌｉｇｈｔ ｐｏｉｎｔ ｄｅｆｅｃｔｓ）や表面粗さ（ヘイズ）の低減に対する要求はますます厳しくなっている。 In recent years, the design rules for semiconductor devices have been becoming smaller due to the increasing demand for higher storage capacity of semiconductor memories. For this reason, the depth of focus in photolithography performed in the manufacturing process of semiconductor devices has become shallower, and requirements for reducing surface defects (LPD: light point defects) and surface roughness (haze) of silicon wafers (bare wafers) have become increasingly strict. It has become.
シリコンウェーハの品質を向上する目的で、シリコンウェーハの研磨は多段階で行われている。特に研磨の最終段階で行われる仕上げ研磨は、ヘイズの低減とパーティクルやスクラッチ、ピット等の表面欠陥の低減とを目的として行われている。 In order to improve the quality of silicon wafers, polishing of silicon wafers is performed in multiple stages. In particular, final polishing performed at the final stage of polishing is performed for the purpose of reducing haze and surface defects such as particles, scratches, and pits.
シリコンウェーハの研磨に用いられる研磨液組成物として、例えば、特許文献１では、シリカ粒子と、含窒素塩基性化合物と、水酸基由来の酸素原子数とポリオキシアルキレン由来の酸素原子数の比が０．８～１０の水溶性高分子と、を含有する研磨液組成物が提案されている。
特許文献２では、シリカ粒子と、塩基性化合物と、分岐度５９．８以上のポリグリセリン及びポリグリセリン誘導体から選ばれる少なくとも１種の化合物と、を含有する研磨液組成物が提案されている。
特許文献３では、シリカ粒子と、塩基性化合物と、水溶性高分子と、を含有する研磨液組成物が提案されている。
特許文献４では、砥粒と、水溶性ポリマーと、水とを含有する研磨液組成物が提案されている。
特許文献５では、分子量１０００以上１０００００未満でかつＨＬＢ値１７以上のノニオン活性剤、塩基性化合物及び水を含有する研磨液組成物が提案されている。
特許文献６では、ヒドロキシエチルセルロース、ポリエチレンオキサイド、アルカリ化合物、水、及び二酸化珪素を含有する研磨液組成物が提案されている。
As a polishing liquid composition used for polishing silicon wafers, for example, Patent Document 1 discloses a composition containing silica particles, a nitrogen-containing basic compound, and a ratio of the number of oxygen atoms derived from hydroxyl groups to the number of oxygen atoms derived from polyoxyalkylene of 0. A polishing liquid composition containing a water-soluble polymer of .8 to 10 has been proposed.
Patent Document 2 proposes a polishing liquid composition containing silica particles, a basic compound, and at least one compound selected from polyglycerin and polyglycerin derivatives having a degree of branching of 59.8 or more.
Patent Document 3 proposes a polishing liquid composition containing silica particles, a basic compound, and a water-soluble polymer.
Patent Document 4 proposes a polishing liquid composition containing abrasive grains, a water-soluble polymer, and water.
Patent Document 5 proposes a polishing liquid composition containing a nonionic activator having a molecular weight of 1,000 or more and less than 100,000 and an HLB value of 17 or more, a basic compound, and water.
Patent Document 6 proposes a polishing liquid composition containing hydroxyethyl cellulose, polyethylene oxide, an alkali compound, water, and silicon dioxide.
近年、シリコンウェーハの表面品質に対する要求はますます厳しくなっており、シリコンウェーハの表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減を両立可能な研磨液組成物が求められている。 In recent years, requirements for the surface quality of silicon wafers have become increasingly strict, and there is a need for a polishing liquid composition that can both reduce surface roughness (haze) and surface defects (LPD) of silicon wafers.
そこで、本開示は、シリコンウェーハの表面粗さ（ヘイズ）の低減と表面欠陥（ＬＰＤ）の低減を両立できる研磨液組成物、並びに、これを用いた研磨方法、及び半導体基板の製造方法を提供する。 Therefore, the present disclosure provides a polishing liquid composition that can reduce surface roughness (haze) and surface defects (LPD) of silicon wafers, a polishing method using the same, and a method for manufacturing a semiconductor substrate. do.
本開示は、一態様において、シリカ粒子（成分Ａ）、含窒素塩基性化合物（成分Ｂ）、ポリエチレングリコール（成分Ｃ）、ポリエチレングリコール以外の水溶性高分子（成分Ｄ）、及び水（成分Ｅ）を含有する研磨液組成物であって、前記研磨液組成物を孔径０．２μｍのＰＴＦＥフィルタを用いて濾過圧力０．２５ＭＰａで濾過したときのフィルタ単位面積あたりの通液量が０．２ｇ／ｓｅｃ・ｃｍ2以上である、研磨液組成物に関する。 In one aspect, the present disclosure provides silica particles (component A), a nitrogen-containing basic compound (component B), polyethylene glycol (component C), a water-soluble polymer other than polyethylene glycol (component D), and water (component E). ) is a polishing liquid composition containing the above-mentioned polishing liquid composition, in which the amount of liquid passed per unit area of the filter is 0.2 g when the polishing liquid composition is filtered at a filtration pressure of 0.25 MPa using a PTFE filter with a pore size of 0.2 μm. /sec·cm 2 or more.
本開示は、一態様において、シリカ粒子（成分Ａ）、含窒素塩基性化合物（成分Ｂ）、ポリエチレングリコール（成分Ｃ）、ポリエチレングリコール以外の水溶性高分子（成分Ｄ）、及び水（成分Ｅ）を含有する研磨液組成物であって、ポリエチレングリコール以外の水溶性高分子（成分Ｄ）とポリエチレングリコール（成分Ｃ）との質量比（Ｄ／Ｃ）が７以上５００未満である、研磨液組成物に関する。 In one aspect, the present disclosure provides silica particles (component A), a nitrogen-containing basic compound (component B), polyethylene glycol (component C), a water-soluble polymer other than polyethylene glycol (component D), and water (component E). ), wherein the mass ratio (D/C) of a water-soluble polymer other than polyethylene glycol (component D) to polyethylene glycol (component C) is 7 or more and less than 500. Regarding the composition.
本開示は、一態様において、本開示のシリコンウェーハ用研磨液組成物を用いて被研磨シリコンウェーハを研磨する工程を含む、研磨方法に関する。 In one embodiment, the present disclosure relates to a polishing method including a step of polishing a silicon wafer to be polished using the silicon wafer polishing liquid composition of the present disclosure.
本開示は、一態様において、本開示のシリコンウェーハ用研磨液組成物を用いて被研磨シリコンウェーハを研磨する工程を含む、半導体基板の製造方法に関する。 In one aspect, the present disclosure relates to a method for manufacturing a semiconductor substrate, including a step of polishing a silicon wafer to be polished using the silicon wafer polishing liquid composition of the present disclosure.
本開示によれば、研磨されたシリコンウェーハの表面粗さ（ヘイズ）の低減と表面欠陥（ＬＰＤ）の低減を両立できる研磨液組成物、及び該研磨液組成物を用いた研磨方法、並びに半導体基板の製造方法を提供できる。 According to the present disclosure, a polishing liquid composition that can reduce surface roughness (haze) and surface defects (LPD) of a polished silicon wafer, a polishing method using the polishing liquid composition, and a semiconductor A method for manufacturing a substrate can be provided.
本開示は、シリカ粒子及び塩基性化合物を含む研磨液組成物に、ポリエチレングリコール及びポリエチレングリコール以外の水溶性高分子を含有させることにより、該研磨液組成物で研磨されたシリコンウェーハの表面において、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の両方を低減できるという知見に基づく。 The present disclosure provides for the surface of a silicon wafer polished with the polishing liquid composition by containing polyethylene glycol and a water-soluble polymer other than polyethylene glycol in a polishing liquid composition containing silica particles and a basic compound. Based on the knowledge that both surface roughness (haze) and surface defects (LPD) can be reduced.
すなわち、本開示は、一態様において、シリカ粒子（成分Ａ）、含窒素塩基性化合物（成分Ｂ）、ポリエチレングリコール（成分Ｃ）、ポリエチレングリコール以外の水溶性高分子（成分Ｄ）、及び水（成分Ｅ）を含有する研磨液組成物であって、前記研磨液組成物を孔径０．２μｍのＰＴＦＥ（ポリテトラフルオロエチレン）フィルタを用いて濾過圧力０．２５ＭＰａで濾過したときのフィルタ単位面積あたりの通液量が０．２ｇ／ｓｅｃ・ｃｍ2以上である、又は、ポリエチレングリコール以外の水溶性高分子（成分Ｄ）とポリエチレングリコール（成分Ｃ）との質量比（Ｄ／Ｃ）が７以上５００未満である、研磨液組成物（以下、「本開示の研磨液組成物」ともいう）に関する。 That is, in one aspect, the present disclosure provides silica particles (component A), a nitrogen-containing basic compound (component B), polyethylene glycol (component C), a water-soluble polymer other than polyethylene glycol (component D), and water ( A polishing liquid composition containing component E), which is obtained by filtering the polishing liquid composition using a PTFE (polytetrafluoroethylene) filter with a pore size of 0.2 μm at a filtration pressure of 0.25 MPa per unit area of the filter. The amount of liquid passed through is 0.2 g/sec・cm 2 or more, or the mass ratio (D/C) of water-soluble polymer other than polyethylene glycol (component D) and polyethylene glycol (component C) is 7 or more 500 (hereinafter also referred to as "polishing liquid composition of the present disclosure").
本開示の効果発現機構の詳細は明らかではないが、以下のように推察される。
本開示では、ポリエチレングリコール以外の水溶性高分子（成分Ｄ）がシリコンウェーハ表面に吸着することにより、シリコンウェーハ表面の濡れ性を付与して、シリコンウェーハ表面の乾燥により生じるシリコンウェーハ表面へのパーティクルの付着を抑制し、表面欠陥（ＬＰＤ）を低減できると考えられる。また、成分Ｄがシリコンウェーハに吸着することで、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の悪化の原因となるシリカ粒子（成分Ａ）が直接シリコンウェーハに接触することが抑制され、かつ、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の悪化の原因となる含窒素塩基性化合物（成分Ｂ）によるウェーハ表面の腐食が抑制されると考えられる。さらに、成分Ｃもシリコンウェーハに吸着し、成分Ｂによるウェーハ表面の腐食を抑制しつつ、ウェーハ表面へのパーティクルの付着を抑制するよう作用することができると考えられる。表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）をより低減できると考えられる。
さらに、本開示の研磨液組成物は、孔径０．２μｍのＰＴＦＥフィルタの通液量が０．２ｇ／ｓｅｃ・ｃｍ2以上である、又は、成分Ｄと成分Ｃとの質量比Ｄ／Ｃが所定の範囲内であることにより、シリコンウェーハ表面の濡れ性を担保しつつ、過度なエッチングを抑制することにより、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の両方を低減できると考えられる。
ただし、本開示はこれらのメカニズムに限定して解釈されなくてもよい。
Although the details of the effect expression mechanism of the present disclosure are not clear, it is presumed as follows.
In the present disclosure, a water-soluble polymer other than polyethylene glycol (component D) is adsorbed onto the silicon wafer surface, thereby imparting wettability to the silicon wafer surface and eliminating particles on the silicon wafer surface that are generated due to drying of the silicon wafer surface. It is thought that it is possible to suppress the adhesion of and reduce surface defects (LPD). In addition, by adsorbing component D to the silicon wafer, direct contact of silica particles (component A), which causes deterioration of surface roughness (haze) and surface defects (LPD), with the silicon wafer is suppressed, and It is thought that corrosion of the wafer surface caused by the nitrogen-containing basic compound (component B), which causes deterioration of surface roughness (haze) and surface defects (LPD), is suppressed. Furthermore, component C is also adsorbed to the silicon wafer, and it is thought that it can act to suppress the corrosion of the wafer surface caused by component B and the adhesion of particles to the wafer surface. It is believed that surface roughness (haze) and surface defects (LPD) can be further reduced.
Furthermore, the polishing liquid composition of the present disclosure has a PTFE filter having a pore size of 0.2 μm in an amount of 0.2 g/sec·cm 2 or more, or a mass ratio D/C of component D and component C. By being within a predetermined range, it is considered that both surface roughness (haze) and surface defects (LPD) can be reduced by suppressing excessive etching while ensuring wettability of the silicon wafer surface.
However, the present disclosure does not need to be interpreted as being limited to these mechanisms.
［シリカ粒子（成分Ａ）］
本開示の研磨液組成物には、研磨材としてシリカ粒子（成分Ａ）が含まれる。成分Ａの具体例としては、コロイダルシリカ、フュームドシリカ等が挙げられるが、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、コロイダルシリカが好ましい。成分Ａは、１種でもよいし、２種以上の組合せでもよい。
[Silica particles (component A)]
The polishing liquid composition of the present disclosure contains silica particles (component A) as an abrasive. Specific examples of component A include colloidal silica, fumed silica, etc., and colloidal silica is preferred from the viewpoint of reducing surface roughness (haze) and surface defects (LPD). Component A may be used alone or in combination of two or more.
成分Ａの使用形態としては、操作性の観点から、スラリー状が好ましい。本開示の研磨液組成物に含まれる成分Ａがコロイダルシリカである場合、アルカリ金属やアルカリ土類金属等によるシリコンウェーハの汚染を防止する観点から、コロイダルシリカは、アルコキシシランの加水分解物から得たものであることが好ましい。アルコキシシランの加水分解物から得られるシリカ粒子は、従来から公知の方法によって作製できる。 From the viewpoint of operability, component A is preferably used in a slurry form. When component A contained in the polishing liquid composition of the present disclosure is colloidal silica, the colloidal silica is obtained from a hydrolyzate of alkoxysilane from the viewpoint of preventing contamination of silicon wafers with alkali metals, alkaline earth metals, etc. It is preferable that the Silica particles obtained from a hydrolyzate of alkoxysilane can be produced by conventionally known methods.
成分Ａの平均一次粒子径は、研磨速度の確保の観点から、１０ｎｍ以上が好ましく、１５ｎｍ以上がより好ましく、２０ｎｍ以上が更に好ましく、そして、研磨速度の確保、並びに、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、４０ｎｍ以下が好ましく、３５ｎｍ以下がより好ましく、３０ｎｍ以下が更に好ましい。より具体的には、成分Ａの平均一次粒子径は、１０ｎｍ以上４０ｎｍ以下が好ましく、１５ｎｍ以上３５ｎｍ以下がより好ましく、１５ｎｍ以上３０ｎｍ以下が更に好ましく、２０ｎｍ以上３０ｎｍ以下が更に好ましい。特に、成分Ａとしてコロイダルシリカを用いた場合、成分Ａの平均一次粒子径は、研磨速度の確保、並びに表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、１０ｎｍ以上が好ましく、１５ｎｍ以上がより好ましく、２０ｎｍ以上が更に好ましく、そして、同様の観点から、４０ｎｍ以下が好ましく、３５ｎｍ以下がより好ましく、３０ｎｍ以下が更に好ましい。 The average primary particle diameter of component A is preferably 10 nm or more, more preferably 15 nm or more, and even more preferably 20 nm or more, from the viewpoint of ensuring the polishing rate, and improving surface roughness (haze) and From the viewpoint of reducing surface defects (LPD), the thickness is preferably 40 nm or less, more preferably 35 nm or less, and even more preferably 30 nm or less. More specifically, the average primary particle diameter of component A is preferably 10 nm or more and 40 nm or less, more preferably 15 nm or more and 35 nm or less, even more preferably 15 nm or more and 30 nm or less, and even more preferably 20 nm or more and 30 nm or less. In particular, when colloidal silica is used as component A, the average primary particle diameter of component A is preferably 10 nm or more from the viewpoint of ensuring a polishing rate and reducing surface roughness (haze) and surface defects (LPD). 15 nm or more is more preferable, 20 nm or more is even more preferable, and from the same viewpoint, 40 nm or less is preferable, more preferably 35 nm or less, and even more preferably 30 nm or less.
本開示において、成分Ａの平均一次粒子径は、ＢＥＴ（窒素吸着）法によって算出される比表面積Ｓ（ｍ2／ｇ）を用いて算出される。比表面積は、例えば、実施例に記載の方法により測定できる。 In the present disclosure, the average primary particle diameter of component A is calculated using the specific surface area S (m 2 /g) calculated by the BET (nitrogen adsorption) method. The specific surface area can be measured, for example, by the method described in Examples.
成分Ａの会合度は、研磨速度の確保、並びに表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、３以下が好ましく、２．５以下がより好ましく、２．３以下が更に好ましく、そして、同様の観点から、１．１以上が好ましく、１．５以上がより好ましく、１．８以上が更に好ましい。成分Ａがコロイダルシリカである場合、その会合度は、研磨速度の確保、並びに表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、３以下が好ましく、２．５以下がより好ましく、２．３以下が更に好ましく、そして、同様の観点から、１．１以上が好ましく、１．５以上がより好ましく、１．８以上が更に好ましい。 The degree of association of component A is preferably 3 or less, more preferably 2.5 or less, and even more preferably 2.3 or less, from the viewpoint of ensuring a polishing rate and reducing surface roughness (haze) and surface defects (LPD). Preferably, and from the same viewpoint, it is preferably 1.1 or more, more preferably 1.5 or more, and even more preferably 1.8 or more. When component A is colloidal silica, its degree of association is preferably 3 or less, more preferably 2.5 or less, from the viewpoint of ensuring a polishing rate and reducing surface roughness (haze) and surface defects (LPD). , 2.3 or less is more preferable, and from the same viewpoint, 1.1 or more is preferable, 1.5 or more is more preferable, and 1.8 or more is still more preferable.
本開示において、成分Ａの会合度とは、シリカ粒子の形状を表す係数であり、下記式により算出される。平均二次粒子径は、動的光散乱法によって測定される値であり、例えば、実施例に記載の装置を用いて測定できる。
会合度＝平均二次粒子径／平均一次粒子径
In the present disclosure, the degree of association of component A is a coefficient representing the shape of silica particles, and is calculated by the following formula. The average secondary particle diameter is a value measured by a dynamic light scattering method, and can be measured, for example, using the apparatus described in Examples.
Degree of association = average secondary particle size / average primary particle size
成分Ａの会合度の調整方法としては、例えば、特開平６－２５４３８３号公報、特開平１１－２１４３３８号公報、特開平１１－６０２３２号公報、特開２００５－０６０２１７号公報、特開２００５－０６０２１９号公報等に記載の方法を採用することができる。 Examples of methods for adjusting the degree of association of component A include JP-A-6-254383, JP-A-11-214338, JP-A-11-60232, JP-A-2005-060217, and JP-A-2005-060219. The method described in the above publication can be adopted.
成分Ａの形状は、いわゆる球型及び／又はいわゆるマユ型であることが好ましい。 The shape of component A is preferably a so-called spherical shape and/or a so-called cocoon shape.
本開示の研磨液組成物に含まれる成分Ａの含有量は、研磨速度の確保の観点から、ＳｉＯ2換算で、０．０１質量％以上が好ましく、０．０７質量％以上がより好ましく、０．１０質量％以上が更に好ましく、そして、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、０．５質量％以下が好ましく、０．３質量％以下がより好ましく、０．２質量％以下が更に好ましい。より具体的には、成分Ａの含有量は、ＳｉＯ2換算で、０．０１質量％以上０．５質量％以下が好ましく、０．０７質量％以上０．３質量％以下がより好ましく、０．１０質量％以上０．２質量％以下が更に好ましい。成分Ａが２種以上の組合せの場合、成分Ａの含有量はそれらの合計含有量をいう。 From the viewpoint of ensuring a polishing rate, the content of component A contained in the polishing liquid composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.07% by mass or more, and more preferably 0.07% by mass or more in terms of SiO 2 . .10 mass % or more is more preferable, and from the viewpoint of reducing surface roughness (haze) and surface defects (LPD), 0.5 mass % or less is preferable, 0.3 mass % or less is more preferable, and 0.1 mass % or less is more preferable. More preferably, it is 2% by mass or less. More specifically, the content of component A is preferably 0.01 mass% or more and 0.5 mass% or less, more preferably 0.07 mass% or more and 0.3 mass% or less, and 0.01 mass% or more and 0.5 mass% or less, more preferably 0.07 mass% or more and 0.3 mass% or less, in terms of SiO2. More preferably, the content is .10% by mass or more and 0.2% by mass or less. When Component A is a combination of two or more types, the content of Component A refers to their total content.
［含窒素塩基性化合物（成分Ｂ）］
本開示の研磨液組成物に含まれる成分Ｂは、含窒素塩基性化合物であり、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、水溶性の含窒素塩基性化合物であることが好ましい。本開示において、「水溶性」とは、水（２０℃）に対して０．５ｇ／１００ｍＬ以上の溶解度、好ましくは２ｇ／１００ｍＬ以上の溶解度を有することをいう。本開示において、「水溶性の含窒素塩基性化合物」とは、水に溶解したとき、塩基性を示す含窒素化合物をいう。成分Ｂは、１種でもよいし、２種以上の組合せでもよい。
[Nitrogen-containing basic compound (component B)]
Component B contained in the polishing liquid composition of the present disclosure is a nitrogen-containing basic compound, and is a water-soluble nitrogen-containing basic compound from the viewpoint of reducing surface roughness (haze) and surface defects (LPD). It is preferable. In the present disclosure, "water-soluble" refers to having a solubility in water (20° C.) of 0.5 g/100 mL or more, preferably 2 g/100 mL or more. In the present disclosure, a "water-soluble nitrogen-containing basic compound" refers to a nitrogen-containing compound that exhibits basicity when dissolved in water. Component B may be used alone or in combination of two or more.
成分Ｂとしては、例えば、アミン化合物及びアンモニウム化合物から選ばれる少なくとも１種の含窒素塩基性化合物が挙げられる。アミン化合物及びアンモニウム化合物から選ばれる少なくとも１種の含窒素塩基性化合物としては、例えば、アンモニア、水酸化アンモニウム、炭酸アンモニウム、炭酸水素アンモニウム、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ－メチルエタノールアミン、Ｎ－メチル－Ｎ，Ｎ－ジエタノ－ルアミン、Ｎ，Ｎ－ジメチルエタノールアミン、Ｎ，Ｎ－ジエチルエタノールアミン、Ｎ，Ｎ－ジブチルエタノールアミン、Ｎ－（β－アミノエチル）エタノ－ルアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、エチレンジアミン、ヘキサメチレンジアミン、ピペラジン・六水和物、無水ピペラジン、１－（２－アミノエチル）ピペラジン、Ｎ－メチルピペラジン、ジエチレントリアミン、及び水酸化テトラメチルアンモニウムから選ばれる１種又は２種以上の組合せが挙げられる。本開示に係る研磨液組成物に含まれうる含窒素塩基性化合物としては、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減、保存安定性の向上、並びに研磨速度の確保の観点から、アンモニアが好ましい。 Component B includes, for example, at least one nitrogen-containing basic compound selected from amine compounds and ammonium compounds. At least one nitrogen-containing basic compound selected from amine compounds and ammonium compounds includes, for example, ammonia, ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monomer. Ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyl-N,N-diethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine , N-(β-aminoethyl)ethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethylenediamine, hexamethylenediamine, piperazine hexahydrate, anhydrous piperazine, 1-(2-aminoethyl)piperazine , N-methylpiperazine, diethylenetriamine, and tetramethylammonium hydroxide, or a combination of two or more thereof. As the nitrogen-containing basic compound that can be included in the polishing liquid composition according to the present disclosure, from the viewpoint of reducing surface roughness (haze) and surface defects (LPD), improving storage stability, and ensuring polishing rate, Ammonia is preferred.
本開示の研磨液組成物に含まれる成分Ｂの含有量は、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減、保存安定性の向上、並びに研磨速度の確保の観点から、０．００１質量％以上が好ましく、０．００５質量％以上がより好ましく、０．０１質量％以上が更に好ましく、そして、表面粗さ（ヘイズ）低減の観点から、０．１質量％以下が好ましく、０．０５質量％以下がより好ましく、０．０２５質量％以下が更に好ましい。より具体的には、成分Ｂの含有量は、０．００１質量％以上０．１質量％以下が好ましく、０．００５質量％以上０．０５質量％以下がより好ましく、０．０１質量％以上０．０２５質量％以下が更に好ましい。成分Ｂが２種以上の組合せの場合、成分Ｂの含有量はそれらの合計含有量をいう。 The content of component B contained in the polishing liquid composition of the present disclosure is 0.001% from the viewpoint of reducing surface roughness (haze) and surface defects (LPD), improving storage stability, and ensuring polishing rate. It is preferably at least 0.005% by mass, even more preferably at least 0.01% by mass, and from the viewpoint of reducing surface roughness (haze), preferably at most 0.1% by mass, and 0.005% by mass or more. The content is more preferably 0.05% by mass or less, and even more preferably 0.025% by mass or less. More specifically, the content of component B is preferably 0.001% by mass or more and 0.1% by mass or less, more preferably 0.005% by mass or more and 0.05% by mass or less, and 0.01% by mass or more. More preferably, it is 0.025% by mass or less. When component B is a combination of two or more types, the content of component B refers to their total content.
本開示の研磨液組成物に含まれる成分Ａと成分Ｂとの質量比（Ａ／Ｂ）は、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、０．１以上が好ましく、５以上がより好ましく、１０以上が更に好ましく、そして、５００以下が好ましく、１００以下がより好ましく、３０以下が更に好ましい。より具体的には、質量比Ａ／Ｂは、０．１以上５００以下が好ましく、５以上１００以下がより好ましく、１０以上３０以下が更に好ましい。 The mass ratio (A/B) between component A and component B contained in the polishing liquid composition of the present disclosure is preferably 0.1 or more from the viewpoint of reducing surface roughness (haze) and surface defects (LPD). , more preferably 5 or more, still more preferably 10 or more, preferably 500 or less, more preferably 100 or less, and still more preferably 30 or less. More specifically, the mass ratio A/B is preferably 0.1 or more and 500 or less, more preferably 5 or more and 100 or less, and even more preferably 10 or more and 30 or less.
［ポリエチレングリコール（成分Ｃ）］
本開示の研磨液組成物に含まれる成分Ｃは、ポリエチレングリコールである。
成分Ｃの分子量は、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、６００以上が好ましく、８００以上がより好ましく、１０００以上が更に好ましく、そして、１００００未満以下が好ましく、８０００以下がより好ましく、６０００以下が更に好ましく、３０００以下が更に好ましく、２０００以下が更に好ましく、１５００以下が更に好ましい。より具体的には、成分Ｃの分子量は、６００以上１００００未満が好ましく、８００以上８０００以下が好ましく、１０００以上６０００以下が更に好ましく、１０００以上２０００以下が更に好ましく、１０００以上１５００以下が更に好ましい。成分Ｃは、１種でもよいし、２種以上の組合せでもよい。
[Polyethylene glycol (component C)]
Component C contained in the polishing liquid composition of the present disclosure is polyethylene glycol.
From the viewpoint of reducing surface roughness (haze) and surface defects (LPD), the molecular weight of component C is preferably 600 or more, more preferably 800 or more, even more preferably 1,000 or more, and preferably less than 10,000, and 8,000 or more. The following is more preferable, 6000 or less is still more preferable, 3000 or less is even more preferable, 2000 or less is still more preferable, and 1500 or less is still more preferable. More specifically, the molecular weight of component C is preferably 600 or more and less than 10,000, preferably 800 or more and 8,000 or less, even more preferably 1,000 or more and 6,000 or less, still more preferably 1,000 or more and 2,000 or less, and even more preferably 1,000 or more and 1,500 or less. Component C may be used alone or in combination of two or more.
本開示の研磨液組成物に含まれる成分Ｃの含有量は、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、０．１質量ｐｐｍ以上が好ましく、１．０質量ｐｐｍ以上がより好ましく、３．０質量ｐｐｍ以上が更に好ましく、そして、１０００質量ｐｐｍ以下が好ましく、５００質量ｐｐｍ以下がより好ましく、１００質量ｐｐｍ以下が更に好ましい。より具体的には、成分Ｃの含有量は、０．１質量ｐｐｍ以上１０００質量ｐｐｍ以下が好ましく、１．０質量ｐｐｍ以上５００質量ｐｐｍ以下がより好ましく、３．０質量ｐｐｍ以上１００質量ｐｐｍ以下が更に好ましい。成分Ｃが２種以上の組合せの場合、成分Ｃの含有量はそれらの合計含有量をいう。 The content of component C contained in the polishing liquid composition of the present disclosure is preferably 0.1 mass ppm or more, and 1.0 mass ppm or more from the viewpoint of reducing surface roughness (haze) and surface defects (LPD). is more preferable, more preferably 3.0 mass ppm or more, still more preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, even more preferably 100 mass ppm or less. More specifically, the content of component C is preferably 0.1 mass ppm or more and 1000 mass ppm or less, more preferably 1.0 mass ppm or more and 500 mass ppm or less, and 3.0 mass ppm or more and 100 mass ppm or less. is even more preferable. When component C is a combination of two or more types, the content of component C refers to their total content.
［ポリエチレングリコール以外の水溶性高分子（成分Ｄ）］
本開示の研磨液組成物に含まれる成分Ｄは、ポリエチレングリコール（成分Ｃ）以外の水溶性高分子である。本開示において「水溶性」とは、水（２０℃）に対して０．５ｇ／１００ｍＬ以上の溶解度を有することをいい、好ましくは２ｇ／１００ｍＬ以上の溶解度を有することをいう。成分Ｄは、１種でもよいし、２種以上の組合せでもよい。
[Water-soluble polymer other than polyethylene glycol (component D)]
Component D contained in the polishing liquid composition of the present disclosure is a water-soluble polymer other than polyethylene glycol (component C). In the present disclosure, "water-soluble" refers to having a solubility in water (20° C.) of 0.5 g/100 mL or more, preferably 2 g/100 mL or more. Component D may be used alone or in combination of two or more.
成分Ｄは、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、下記式（Ｉ）で表される構成単位及び下記式（ＩＩ）で表される構成単位の少なくとも一方を含むことが好ましい。 Component D contains at least one of the structural unit represented by the following formula (I) and the structural unit represented by the following formula (II) from the viewpoint of reducing surface roughness (haze) and surface defects (LPD). It is preferable.
上記式（Ｉ）中、Ｒ1は、メチレン基（－ＣＨ2－）又は結合手であり、Ｒ2、Ｒ3、Ｒ4、Ｒ5はそれぞれ独立して、Ｈ（水素原子）、－ＯＨ（水酸基）、－ＣＨ2ＯＨ、又はポリビニルアルコールであるが、Ｒ2、Ｒ3、Ｒ4、Ｒ5が各々すべて同時にはＨ（水素原子）、－ＯＨ（水酸基）、又は－ＣＨ2ＯＨ、とはならない。
上記式（ＩＩ）中、Ｒ6及びＲ7はそれぞれ独立して、水素原子、メチル基、フェニル基、ベンジル基又はヘキシル基であり、Ｒ8及びＲ9はそれぞれ独立して、水素原子、炭素数が１～４のアルコキシ基、又はフェニル基であり、Ｘは、結合手、－ＣＨ2－、－Ｃ2Ｈ4－、又は－Ｐｈ－ＣＨ2－である。本開示において、「－Ｐｈ－」はフェニレン基を示す。
In the above formula (I), R 1 is a methylene group (-CH 2 -) or a bond, and R 2 , R 3 , R 4 and R 5 are each independently H (hydrogen atom), -OH (hydroxyl group), -CH 2 OH, or polyvinyl alcohol, but when R 2 , R 3 , R 4 , and R 5 are all simultaneously H (hydrogen atom), -OH (hydroxyl group), or -CH 2 OH, It is not.
In the above formula (II), R 6 and R 7 are each independently a hydrogen atom, a methyl group, a phenyl group, a benzyl group, or a hexyl group, and R 8 and R 9 are each independently a hydrogen atom, a carbon It is an alkoxy group of 1 to 4 or a phenyl group, and X is a bond, -CH 2 -, -C 2 H 4 -, or -Ph-CH 2 -. In this disclosure, "-Ph-" represents a phenylene group.
前記式（Ｉ）で表される構成単位を有する水溶性高分子である成分Ｄとしては、一又は複数の実施形態において、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、ポリグリシドール、ポリグリシドール誘導体、ポリグリセリン及びポリグリセリン誘導体から選ばれる少なくとも１種が挙げられる。ポリグリシドール誘導体としては、ポリ（１－メチルグリシドール）、ポリ（１－エチルグリシドール）、ポリ（１－プロピルグリシドール）、ポリ（１－ジメチルグリシドール）、ポリ（１－ジエチルグリシドール）、ポリ（１－ジプロピルグリシドール）、ポリ（３－フェニルグリシドール）等が挙げられる。ポリグリセリン誘導体としては、ポリグリセリンアルキルエーテル、ポリグリセリンジアルキルエーテル、ポリグリセリン脂肪酸エステル等が挙げられる。
前記式（ＩＩ）で表される構成単位を有する水溶性高分子である成分Ｄとしては、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、ポリジメチルビニルホスホナート（ポリビニルリン）、ポリジエチルビニルホスホナート、ポリジイソプロピルホスホナート、ポリ－１－（ジメトキシホスフィニル）－１－メチルエテン、ポリ－１－（ジメトキシホスフィニル）１－１フェニルエテン、ポリ－１－（ジメトキシホスフィニル）－２－フェニルエテン、ポリジメチル－ｐ－ビニルベンジルホスホナート、ポリジメチル－ｐ－ビニルベンジルホスホナート、ポリジイソプロピル－ｐ－ビニルベンジルホスホナート、ポリジフェニルビニルホスホナート、ポリ－２－（ジメトキシホスフィニル）－１－オクテン、ポリビニルリン酸等が挙げられる。
In one or more embodiments, component D, which is a water-soluble polymer having a structural unit represented by the formula (I), includes: At least one selected from polyglycidol, polyglycidol derivatives, polyglycerin, and polyglycerin derivatives can be mentioned. Examples of polyglycidol derivatives include poly(1-methylglycidol), poly(1-ethylglycidol), poly(1-propylglycidol), poly(1-dimethylglycidol), poly(1-diethylglycidol), and poly(1-diethylglycidol). dipropylglycidol), poly(3-phenylglycidol), and the like. Examples of polyglycerin derivatives include polyglycerin alkyl ethers, polyglycerin dialkyl ethers, polyglycerin fatty acid esters, and the like.
From the viewpoint of reducing surface roughness (haze) and surface defects (LPD), component D, which is a water-soluble polymer having a structural unit represented by formula (II), is polydimethylvinylphosphonate (polyvinyl phosphonate). ), polydiethyl vinylphosphonate, polydiisopropylphosphonate, poly-1-(dimethoxyphosphinyl)-1-methylethene, poly-1-(dimethoxyphosphinyl)-1-1 phenylethene, poly-1-(dimethoxy phosphinyl)-2-phenylethene, polydimethyl-p-vinylbenzylphosphonate, polydimethyl-p-vinylbenzylphosphonate, polydiisopropyl-p-vinylbenzylphosphonate, polydiphenylvinylphosphonate, poly-2- (dimethoxyphosphinyl)-1-octene, polyvinyl phosphoric acid, and the like.
成分Ｄの具体例としては、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、ポリビニルリン、ポリグリセリン、ポリグリセリンラウリルエーテルから選ばれる少なくとも１種が好ましい。 As a specific example of component D, at least one selected from polyvinyl phosphorus, polyglycerin, and polyglycerin lauryl ether is preferable from the viewpoint of reducing surface roughness (haze) and surface defects (LPD).
前記式（Ｉ）で表される構成単位の供給源である単量体としては、例えば、１－メチルグリシドール、１－エチルグリシドール、１－プロピルグリシドール、１－ジメチルグリシドール、１－ジエチルグリシドール、１－ジプロピルグリシドール、３－フェニルグリシドール、グリセリンアルキルエーテル、グリセリンジアルキルエーテル、グリセリン脂肪酸エステル等が挙げられる。これらは１種又は２種以上を組み合わせてよい。
前記式（ＩＩ）で表される構成単位の供給源である単量体としては、例えば、ジメチルビニルホスホナート、ジエチルビニルホスホナート、ジイソプロピルホスホナート、１－（ジメトキシホスフィニル）－１－メチルエテン、１－（ジメトキシホスフィニル）１－１フェニルエテン、１－（ジメトキシホスフィニル）－２－フェニルエテン、ジメチル－ｐ－ビニルベンジルホスホナート、ジメチル－ｐ－ビニルベンジルホスホナート、ジイソプロピル－ｐ－ビニルベンジルホスホナート、ジフェニルビニルホスホナート、２－（ジメトキシホスフィニル）－１－オクテン、ビニルリン酸等が挙げられる。これらは、１種でもよいし、２種以上の組合せでもよい。
Examples of the monomer that is the source of the structural unit represented by the formula (I) include 1-methylglycidol, 1-ethylglycidol, 1-propylglycidol, 1-dimethylglycidol, 1-diethylglycidol, 1 -dipropylglycidol, 3-phenylglycidol, glycerin alkyl ether, glycerin dialkyl ether, glycerin fatty acid ester and the like. These may be used alone or in combination of two or more.
Examples of the monomer that is a source of the structural unit represented by the formula (II) include dimethylvinylphosphonate, diethylvinylphosphonate, diisopropylphosphonate, and 1-(dimethoxyphosphinyl)-1-methylethene. , 1-(dimethoxyphosphinyl)1-1 phenylethene, 1-(dimethoxyphosphinyl)-2-phenylethene, dimethyl-p-vinylbenzylphosphonate, dimethyl-p-vinylbenzylphosphonate, diisopropyl-p -vinylbenzylphosphonate, diphenylvinylphosphonate, 2-(dimethoxyphosphinyl)-1-octene, vinyl phosphoric acid and the like. These may be used alone or in combination of two or more.
成分Ｄが、ポリグリシドール、ポリグリシドール誘導体、ポリグリセリン及びポリグリセリン誘導体から選ばれる少なくとも1種の水溶性高分子である場合、成分Ｄの水酸基価は、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）低減の観点から、６００ｍｇＫＯＨ／ｇ以上が好ましく、６２０ｍｇＫＯＨ／ｇ以上がより好ましく、６５０ｍｇＫＯＨ／ｇ以上が更に好ましく、そして、同様の観点から、８５０ｍｇＫＯＨ／ｇ以下が好ましく、８００ｍｇＫＯＨ／ｇ以下がより好ましく、７５０ｍｇＫＯＨ／ｇ以下が更に好ましい。より具体的には、成分Ｄの水酸基価は、６００ｍｇＫＯＨ／ｇ以上８５０ｍｇＫＯＨ／ｇ以下が好ましく、６２０ｍｇＫＯＨ／ｇ以上８００ｍｇＫＯＨ／ｇ以下がより好ましく、６５０ｍｇＫＯＨ／ｇ以上７５０ｍｇＫＯＨ／ｇ以下が更に好ましい。水酸基価は、例えば、実施例に記載の方法により測定できる。 When component D is at least one water-soluble polymer selected from polyglycidol, polyglycidol derivatives, polyglycerin, and polyglycerin derivatives, the hydroxyl value of component D is determined by surface roughness (haze) and surface defects (LPD). ) From the viewpoint of reduction, it is preferably 600 mgKOH/g or more, more preferably 620 mgKOH/g or more, even more preferably 650 mgKOH/g or more, and from the same viewpoint, it is preferably 850 mgKOH/g or less, more preferably 800 mgKOH/g or less. , more preferably 750 mgKOH/g or less. More specifically, the hydroxyl value of component D is preferably 600 mgKOH/g or more and 850 mgKOH/g or less, more preferably 620 mgKOH/g or more and 800 mgKOH/g or less, and even more preferably 650 mgKOH/g or more and 750 mgKOH/g or less. The hydroxyl value can be measured, for example, by the method described in Examples.
成分Ｄの重量平均分子量は、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、１，０００以上が好ましく、２，０００以上がより好ましく、２，５００以上が更に好ましく、そして、１５万以下が好ましく、８万以下がより好ましく、１万以下が更に好ましく、５，０００以下が更に好ましく、４，０００以下が更に好ましい。より具体的には、成分Ｄの重量平均分子量は、１，０００以上１５万以下が好ましく、２，０００以上８万以下がより好ましく、２，０００以上１万以下が更に好ましく、２，５００以上４，０００以下が更に好ましい。成分Ｄの重量平均分子量は後の実施例に記載の方法により測定される。 From the viewpoint of reducing surface roughness (haze) and surface defects (LPD), the weight average molecular weight of component D is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 2,500 or more, and , is preferably 150,000 or less, more preferably 80,000 or less, even more preferably 10,000 or less, even more preferably 5,000 or less, and even more preferably 4,000 or less. More specifically, the weight average molecular weight of component D is preferably 1,000 or more and 150,000 or less, more preferably 2,000 or more and 80,000 or less, still more preferably 2,000 or more and 10,000 or less, and 2,500 or more. More preferably, it is 4,000 or less. The weight average molecular weight of component D is measured by the method described in the Examples below.
本開示の研磨液組成物に含まれる成分Ｄの含有量は、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、０．００１質量％以上が好ましく、０．０１質量％以上がより好ましく、０．０２質量％以上が更に好ましく、そして、同様の観点から、１質量％以下が好ましく、０．５質量％以下がより好ましく、０．１質量％以下が更に好ましい。より具体的には、成分Ｄの含有量は、０．００１質量％以上１質量％以下が好ましく、０．０１質量％以上０．５質量％以下がより好ましく、０．０２質量％以上０．１質量％以下が更に好ましい。成分Ｄが２種以上の組合せの場合、成分Ｄの含有量はそれらの合計含有量をいう。 The content of component D contained in the polishing liquid composition of the present disclosure is preferably 0.001% by mass or more, and 0.01% by mass or more from the viewpoint of reducing surface roughness (haze) and surface defects (LPD). is more preferable, 0.02% by mass or more is still more preferable, and from the same viewpoint, 1% by mass or less is preferable, more preferably 0.5% by weight or less, and even more preferably 0.1% by weight or less. More specifically, the content of component D is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.01% by mass or more and 0.5% by mass or less, and 0.02% by mass or more and 0.5% by mass or less. More preferably, it is 1% by mass or less. When component D is a combination of two or more types, the content of component D refers to their total content.
本開示の研磨液組成物に含まれる成分Ａと成分Ｄとの質量比（Ａ／Ｄ）は、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、０．０１以上が好ましく、１．０以上がより好ましく、３．０以上が更に好ましく、そして、同様の観点から、５００以下が好ましく、５０以下がより好ましく、２０以下が更に好ましい。より具体的には、質量比Ａ／Ｄは、０．０１以上５００以下が好ましく、１．０以上５０以下がより好ましく、３．０以上２０以下が更に好ましい。 The mass ratio (A/D) between component A and component D contained in the polishing liquid composition of the present disclosure is preferably 0.01 or more from the viewpoint of reducing surface roughness (haze) and surface defects (LPD). , more preferably 1.0 or more, still more preferably 3.0 or more, and from the same point of view, preferably 500 or less, more preferably 50 or less, and even more preferably 20 or less. More specifically, the mass ratio A/D is preferably 0.01 or more and 500 or less, more preferably 1.0 or more and 50 or less, and even more preferably 3.0 or more and 20 or less.
本開示の研磨液組成物に含まれる成分Ｄと成分Ｃとの質量比（Ｄ／Ｃ）は、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、７以上が好ましく、７．５以上がより好ましく、８以上が更に好ましく、そして、同様の観点から、５００未満が好ましく、４００以下がより好ましく、１００以下が更に好ましく、５０以下が更に好ましく、３０以下が更に好ましく、２０以下が更に好ましい。より具体的には、質量比Ｄ／Ｃは、７以上５００未満が好ましく、７．５以上４００以下がより好ましく、８以上１００以下が更に好ましく、８以上２０以下が更に好ましい。 From the viewpoint of reducing surface roughness (haze) and surface defects (LPD), the mass ratio (D/C) between component D and component C contained in the polishing liquid composition of the present disclosure is preferably 7 or more, and 7 or more. .5 or more is more preferable, 8 or more is even more preferable, and from the same viewpoint, less than 500 is preferable, 400 or less is more preferable, 100 or less is still more preferable, 50 or less is still more preferable, 30 or less is still more preferable, 20 The following are more preferable. More specifically, the mass ratio D/C is preferably 7 or more and less than 500, more preferably 7.5 or more and 400 or less, still more preferably 8 or more and 100 or less, and even more preferably 8 or more and 20 or less.
［水（成分Ｅ）］
本開示の研磨液組成物に含まれる成分Ｅとしては、例えば、イオン交換水や超純水等の水が挙げられ、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、超純水が好ましい。本開示の研磨液組成物中の成分Ｅの含有量は、例えば、成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ及び後述する任意成分の残余とすることができる。
[Water (component E)]
Component E contained in the polishing liquid composition of the present disclosure includes, for example, water such as ion exchange water and ultrapure water, and from the viewpoint of reducing surface roughness (haze) and surface defects (LPD), Pure water is preferred. The content of component E in the polishing liquid composition of the present disclosure can be, for example, component A, component B, component C, component D, and the remainder of optional components described below.
［その他の成分］
本開示の研磨液組成物は、本開示の効果が妨げられない範囲で、その他の成分をさらに含んでもよい。その他の成分としては、一又は複数の実施形態において、成分Ｃ及び成分Ｄ以外の水溶性高分子、成分Ｂ以外のｐＨ調整剤、防腐剤、アルコール類、キレート剤、酸化剤、アニオン性界面活性剤、及びノニオン性界面活性剤から選ばれる少なくとも１種が挙げられる。前記その他の成分は、本開示の効果を損なわない範囲で研磨液組成物中に含有されることが好ましく、本開示の研磨液組成物中のその他の成分の含有量は、０質量％以上が好ましく、０質量％超がより好ましく、０．１質量％以上が更に好ましく、そして、１０質量％以下が好ましく、５質量％以下がより好ましい。
[Other ingredients]
The polishing liquid composition of the present disclosure may further contain other components as long as the effects of the present disclosure are not impaired. In one or more embodiments, other components include water-soluble polymers other than component C and component D, pH adjusters other than component B, preservatives, alcohols, chelating agents, oxidizing agents, and anionic surfactants. and nonionic surfactants. The other components are preferably contained in the polishing liquid composition within a range that does not impair the effects of the present disclosure, and the content of the other components in the polishing liquid composition of the present disclosure is 0% by mass or more. It is preferably more than 0% by mass, more preferably 0.1% by mass or more, still more preferably 10% by mass or less, and more preferably 5% by mass or less.
成分Ｃ及び成分Ｄ以外の水溶性高分子としては、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、例えば、ポリオキシアルキレン化合物が挙げられる。ポリオキシアルキレン化合物としては、例えば、ポリプロピレングリコール等の成分Ｃ以外のアルキレングリコールアルキレンオキシド付加物；グリセリンアルキレンオキシド付加物；及びペンタエリスリトールアルキレンオキシド付加物から選ばれる少なくとも１種が挙げられる。 Examples of water-soluble polymers other than component C and component D include polyoxyalkylene compounds from the viewpoint of reducing surface roughness (haze) and surface defects (LPD). Examples of the polyoxyalkylene compound include at least one selected from alkylene glycol alkylene oxide adducts other than component C such as polypropylene glycol; glycerin alkylene oxide adducts; and pentaerythritol alkylene oxide adducts.
成分Ｂ以外のｐＨ調整剤としては、例えば、酸性化合物及び成分Ｂ以外のアルカリが挙げられる。酸性化合物としては、硫酸、塩酸、硝酸、リン酸等の無機酸；酢酸、シュウ酸、コハク酸、グリコール酸、リンゴ酸、クエン酸、安息香酸等の有機酸；から選ばれる少なくとも１種が挙げられる。成分Ｂ以外のアルカリとしては、水酸化ナトリウム、水酸化カリウム等の無機アルカリが挙げられる。 Examples of pH adjusters other than component B include acidic compounds and alkalis other than component B. Examples of the acidic compound include at least one selected from inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; organic acids such as acetic acid, oxalic acid, succinic acid, glycolic acid, malic acid, citric acid, and benzoic acid. It will be done. Examples of alkalis other than component B include inorganic alkalis such as sodium hydroxide and potassium hydroxide.
防腐剤としては、例えば、ベンザルコニウムクロライド、ベンゼトニウムクロライド、１，２－ベンズイソチアゾリン－３－オン、（５－クロロ－）２－メチル－４－イソチアゾリン－３－オン、過酸化水素、及び次亜塩素酸塩から選ばれる少なくとも１種が挙げられる。 Examples of preservatives include benzalkonium chloride, benzethonium chloride, 1,2-benzisothiazolin-3-one, (5-chloro-)2-methyl-4-isothiazolin-3-one, hydrogen peroxide, and the following: At least one selected from chlorites is mentioned.
アルコール類としては、例えば、メタノール、エタノール、プロパノール、ブタノール、イソプロピルアルコール、２－メチル－２－プロパノオール、エチレングリコール、プロピレングリコール、ポリエチレングリコール及びグリセリンから選ばれる１種以上が挙げられる。 Examples of alcohols include one or more selected from methanol, ethanol, propanol, butanol, isopropyl alcohol, 2-methyl-2-propanol, ethylene glycol, propylene glycol, polyethylene glycol, and glycerin.
キレート剤としては、エチレンジアミン四酢酸、エチレンジアミン四酢酸ナトリウム、ニトリロ三酢酸、ニトリロ三酢酸ナトリウム、ニトリロ三酢酸アンモニウム、ヒドロキシエチルエチレンジアミン三酢酸、ヒドロキシエチルエチレンジアミン三酢酸ナトリウム、トリエチレンテトラミン六酢酸、及びトリエチレンテトラミン六酢酸ナトリウムから選ばれる１種以上が挙げられる。 Chelating agents include ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, nitrilotriacetic acid, sodium nitrilotriacetate, ammonium nitrilotriacetate, hydroxyethylethylenediaminetriacetic acid, sodium hydroxyethylethylenediaminetriacetate, triethylenetetraminehexaacetic acid, and triethylene. One or more types selected from sodium tetramine hexaacetate can be mentioned.
アニオン性界面活性剤としては、例えば、脂肪酸石鹸、アルキルエーテルカルボン酸塩等のカルボン酸塩；アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩等のスルホン酸塩；高級アルコール硫酸エステル塩、アルキルエーテル硫酸塩等の硫酸エステル塩；アルキルリン酸エステル等のリン酸エステル塩；から選ばれる１種以上が挙げられる。 Examples of anionic surfactants include fatty acid soaps, carboxylates such as alkyl ether carboxylates; sulfonates such as alkylbenzene sulfonates and alkylnaphthalene sulfonates; higher alcohol sulfate ester salts, and alkyl ether sulfates. and sulfuric acid ester salts; and phosphoric acid ester salts such as alkyl phosphoric acid esters.
ノニオン性界面活性剤としては、例えば、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビット脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシアルキレン（硬化）ヒマシ油等のポリエチレングリコール型；ショ糖脂肪酸エステル、ポリグリセリンアルキルエーテル、ポリグリセリン脂肪酸エステル、アルキルグリコシド等の多価アルコール型；及び脂肪酸アルカノールアミド；から選ばれる１種以上が挙げられる。 Examples of nonionic surfactants include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, One or more selected from polyoxyalkylene (hardened) polyethylene glycol type such as castor oil; polyhydric alcohol type such as sucrose fatty acid ester, polyglycerin alkyl ether, polyglycerin fatty acid ester, alkyl glycoside; and fatty acid alkanolamide; Can be mentioned.
本開示の研磨液組成物のｐＨは、研磨速度の確保の観点から、９以上が好ましく、９．５以上がより好ましく、１０以上が更に好ましく、そして、１２以下が好ましく、１１．５以下がより好ましく、１１以下が更に好ましい。より具体的には、本開示の研磨液組成物のｐＨは、９以上１２以下が好ましく、９．５以上１１．５以下がより好ましく、１０以上１１以下が更に好ましい。本開示の研磨液組成物のｐＨは、上述した成分Ｂや公知のｐＨ調整剤を用いて調整できる。本開示において、上記ｐＨは、２５℃における研磨液組成物のｐＨであり、ｐＨメータ（東亜電波工業株式会社、ＨＭ－３０Ｇ）を用いて測定でき、ｐＨメータの電極を研磨液組成物へ浸漬して１分後の数値とすることができる。 The pH of the polishing liquid composition of the present disclosure is preferably 9 or more, more preferably 9.5 or more, even more preferably 10 or more, and preferably 12 or less, and 11.5 or less from the viewpoint of ensuring a polishing rate. More preferably, it is 11 or less. More specifically, the pH of the polishing liquid composition of the present disclosure is preferably 9 or more and 12 or less, more preferably 9.5 or more and 11.5 or less, and even more preferably 10 or more and 11 or less. The pH of the polishing liquid composition of the present disclosure can be adjusted using the component B described above or a known pH adjuster. In the present disclosure, the above pH is the pH of the polishing liquid composition at 25°C, and can be measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and the electrode of the pH meter is immersed in the polishing liquid composition. The value can be calculated after 1 minute.
本開示の研磨液組成物を孔径０．２μｍのＰＴＦＥフィルタを用いて濾過圧力０．２５ＭＰａで濾過したときのフィルタ単位面積あたりの通液量は、０．２ｇ／ｓｅｃ・ｃｍ2以上であり、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の低減の観点から、０．２５ｇ／ｓｅｃ・ｃｍ2以上がより好ましく、０．３ｇ／ｓｅｃ・ｃｍ2以上が更に好ましく、０．３５ｇ／ｓｅｃ・ｃｍ2以上が更に好ましく、０．４ｇ／ｓｅｃ・ｃｍ2以上が更に好ましく、０．４５ｇ／ｓｅｃ・ｃｍ2以上が更に好ましい。本開示における通液量は、一又は複数の実施形態において、フィルタが閉塞状態になるまでの通液量（ｇ／ｓｅｃ・ｃｍ2）を示す。フィルタの閉塞状態は、一又は複数の実施形態において、研磨液組成物の通液が完全に停止した状態、又は、フィルタから通液される研磨液組成物の間隔が５秒以上になった状態を含む。本開示における通液量は、具体的には、実施例に記載の方法により測定できる。本開示における通液量は、例えば、成分Ｄとして上述した式（Ｉ）で表される構成単位及び式（ＩＩ）で表される構成単位の少なくとも一方を含む水溶性高分子を用いることにより０．２ｇ／ｓｅｃ・ｃｍ2以上とすることができる。 When the polishing liquid composition of the present disclosure is filtered using a PTFE filter with a pore size of 0.2 μm at a filtration pressure of 0.25 MPa, the amount of liquid passed per unit area of the filter is 0.2 g/sec cm 2 or more, From the viewpoint of reducing surface roughness (haze) and surface defects (LPD), 0.25 g/sec.cm 2 or more is more preferable, 0.3 g/sec.cm 2 or more is even more preferable, and 0.35 g/sec. cm 2 or more is more preferable, 0.4 g/sec·cm 2 or more is even more preferable, and even more preferably 0.45 g/sec·cm 2 or more. In one or more embodiments, the amount of liquid passed in the present disclosure indicates the amount of liquid passed (g/sec·cm 2 ) until the filter becomes blocked. In one or more embodiments, the blocked state of the filter is a state where the flow of the polishing liquid composition has completely stopped, or a state where the interval between the polishing liquid compositions flowing from the filter is 5 seconds or more. including. Specifically, the amount of liquid passed in the present disclosure can be measured by the method described in Examples. The amount of liquid passed in the present disclosure can be reduced to 0 by using, for example, a water-soluble polymer containing at least one of the structural unit represented by formula (I) and the structural unit represented by formula (II) as component D. .2 g/sec·cm 2 or more.
本開示の研磨液組成物は、例えば、成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ、及び成分Ｅと、さらに所望によりその他の成分とを公知の方法で配合することにより製造できる。すなわち、本開示は、その他の態様において、少なくとも成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ及び成分Ｅを配合する工程を含む、研磨液組成物の製造方法に関する。本開示において「配合する」とは、成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ及び成分Ｅ、並びに必要に応じてその他の成分を同時に又は任意の順に混合することを含む。前記配合は、例えば、ホモミキサー、ホモジナイザー、超音波分散機、湿式ボールミル、又はビーズミル等の撹拌機等を用いて行うことができる。上記本開示の研磨液組成物の製造方法における各成分の好ましい配合量は、上述した本開示の研磨液組成物中の各成分の好ましい含有量と同じとすることができる。 The polishing liquid composition of the present disclosure can be produced, for example, by blending component A, component B, component C, component D, component E, and other components if desired, by a known method. That is, in another aspect, the present disclosure relates to a method for producing a polishing liquid composition, which includes a step of blending at least component A, component B, component C, component D, and component E. In the present disclosure, "blending" includes mixing component A, component B, component C, component D, component E, and other components simultaneously or in any order as necessary. The blending can be carried out using, for example, a stirrer such as a homomixer, a homogenizer, an ultrasonic disperser, a wet ball mill, or a bead mill. The preferable blending amount of each component in the method for manufacturing the polishing liquid composition of the present disclosure can be the same as the preferable content of each component in the polishing liquid composition of the present disclosure described above.
本開示において、「研磨液組成物中の各成分の含有量」は、使用時、すなわち、研磨液組成物の研磨への使用を開始する時点における各成分の含有量をいう。 In the present disclosure, "the content of each component in the polishing liquid composition" refers to the content of each component at the time of use, that is, at the time when the polishing liquid composition starts to be used for polishing.
本開示の研磨液組成物は、貯蔵及び輸送の観点から、濃縮物として製造され、使用時に希釈されてもよい。希釈倍率としては、製造及び輸送コストの観点、保存安定性の観点から、２倍以上１８０倍以下が好ましい。本開示の研磨液組成物の濃縮物は、使用時に各成分の含有量が、上述した含有量（すなわち、使用時の含有量）となるように水（成分Ｅ）で希釈して使用することができる。本開示において研磨液組成物の濃縮物の「使用時」とは、研磨液組成物の濃縮物が希釈された状態をいう。 The polishing liquid composition of the present disclosure may be manufactured as a concentrate and diluted at the time of use for storage and transportation purposes. The dilution ratio is preferably 2 times or more and 180 times or less from the viewpoint of manufacturing and transportation costs and storage stability. The concentrate of the polishing liquid composition of the present disclosure can be used by diluting it with water (component E) so that the content of each component becomes the above-mentioned content (i.e., the content at the time of use). I can do it. In the present disclosure, "at the time of use" of the concentrate of the polishing liquid composition refers to a state in which the concentrate of the polishing liquid composition is diluted.
［被研磨シリコンウェーハ］
本開示の研磨液組成物は、一又は複数の実施形態において、シリコンウェーハ用研磨組成物であり、例えば、半導体基板の製造方法における、被研磨シリコンウェーハを研磨する研磨工程や、被研磨シリコンウェーハを研磨する研磨工程を含む研磨方法に用いられうる。本開示の研磨液組成物を用いて研磨される被研磨シリコンウェーハとしては、一又は複数の実施形態において、単結晶シリコンウェーハ又はポリシリコンウェーハが挙げられる。単結晶シリコンウェーハとしては、例えば、単結晶１００面シリコンウェーハ、１１１面シリコンウェーハ、１１０面シリコンウェーハ等が挙げられる。また、前記シリコンウェーハの抵抗率としては、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）低減の観点から、好ましくは０．０００１Ω・ｃｍ以上、より好ましくは０．００１Ω・ｃｍ以上、更に好ましくは０．０１Ω・ｃｍ以上、更に好ましくは０．１Ω・ｃｍ以上であり、そして、好ましくは１００Ω・ｃｍ以下、より好ましくは５０Ω・ｃｍ以下、更に好ましくは２０Ω・ｃｍ以下である。
[Silicon wafer to be polished]
In one or more embodiments, the polishing liquid composition of the present disclosure is a polishing composition for silicon wafers, and is used, for example, in a polishing step of polishing a silicon wafer to be polished in a method for manufacturing a semiconductor substrate, or in a polishing process for polishing a silicon wafer to be polished. It can be used in a polishing method including a polishing step of polishing. In one or more embodiments, the silicon wafer to be polished that is polished using the polishing liquid composition of the present disclosure includes a single crystal silicon wafer or a polysilicon wafer. Examples of the single crystal silicon wafer include a single crystal 100-sided silicon wafer, a 111-sided silicon wafer, and a 110-sided silicon wafer. Further, from the viewpoint of reducing surface roughness (haze) and surface defects (LPD), the resistivity of the silicon wafer is preferably 0.0001 Ω·cm or more, more preferably 0.001 Ω·cm or more, and even more preferably It is 0.01 Ω·cm or more, more preferably 0.1 Ω·cm or more, and preferably 100 Ω·cm or less, more preferably 50 Ω·cm or less, and even more preferably 20 Ω·cm or less.
［半導体基板の製造方法］
本開示は、その他の態様において、本開示の研磨液組成物を用いて被研磨シリコンウェーハを研磨する研磨工程を含む、半導体基板の製造方法（以下、「本開示の半導体基板製造方法」ともいう）に関する。本開示の半導体基板製造方法によれば、本開示の研磨液組成物を用いることで、研磨されたシリコンウェーハの表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）を低減できるため、高品質の半導体基板を高収率で、生産性よく製造できる。
[Method for manufacturing semiconductor substrate]
In another aspect, the present disclosure provides a semiconductor substrate manufacturing method (hereinafter also referred to as "semiconductor substrate manufacturing method of the present disclosure"), which includes a polishing step of polishing a silicon wafer to be polished using the polishing liquid composition of the present disclosure. ) regarding. According to the semiconductor substrate manufacturing method of the present disclosure, surface roughness (haze) and surface defects (LPD) of a polished silicon wafer can be reduced by using the polishing liquid composition of the present disclosure, so that high quality semiconductors can be produced. Substrates can be manufactured with high yield and productivity.
本開示の半導体基板製造方法における研磨工程は、例えば、単結晶シリコンインゴットを薄円板状にスライスすることにより得られた単結晶シリコンウェーハを平面化するラッピング（粗研磨）工程と、ラッピング単結晶されたシリコンウェーハをエッチングした後、単結晶シリコンウェーハ表面を鏡面化する仕上げ研磨工程とを含むことができる。本開示の研磨液組成物は、表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）低減の観点から、上記仕上げ研磨工程で用いられるとより好ましい。 The polishing step in the semiconductor substrate manufacturing method of the present disclosure includes, for example, a lapping (rough polishing) step of planarizing a single crystal silicon wafer obtained by slicing a single crystal silicon ingot into thin disk shapes, and After etching the single-crystal silicon wafer, the method may include a final polishing step of mirror-finishing the surface of the single-crystal silicon wafer. The polishing liquid composition of the present disclosure is more preferably used in the final polishing step from the viewpoint of reducing surface roughness (haze) and surface defects (LPD).
本開示の半導体基板製造方法は、被研磨シリコンウェーハを研磨する研磨工程の前に、本開示の研磨液組成物の濃縮物を希釈する希釈工程を含んでいてもよい。希釈媒には、例えば、水（成分Ｅ）を用いることができる。 The semiconductor substrate manufacturing method of the present disclosure may include a dilution step of diluting the concentrate of the polishing liquid composition of the present disclosure before the polishing step of polishing the silicon wafer to be polished. For example, water (component E) can be used as the diluent.
本開示の半導体基板製造方法における研磨工程では、例えば、研磨パッドを貼り付けた定盤で被研磨シリコンウェーハを挟み込み、３～２０ｋＰａの研磨圧力で被研磨シリコンウェーハを研磨することができる。本開示において、研磨圧力とは、研磨時に被研磨シリコンウェーハの被研磨面に加えられる定盤の圧力をいう。 In the polishing step in the semiconductor substrate manufacturing method of the present disclosure, for example, the silicon wafer to be polished can be polished by sandwiching the silicon wafer to be polished between surface plates to which a polishing pad is attached, and applying a polishing pressure of 3 to 20 kPa. In the present disclosure, polishing pressure refers to the pressure of a surface plate applied to the polished surface of a silicon wafer to be polished during polishing.
本開示の半導体基板製造方法における研磨工程では、例えば、研磨パッドを貼り付けた定盤で被研磨シリコンウェーハを挟み込み、１５℃以上４０℃以下の研磨液組成物及び研磨パッド表面温度で被研磨シリコンウェーハを研磨することができる。研磨液組成物の温度及び研磨パッド表面温度としては、ヘイズ及びＬＰＤの低減の観点から、１５℃以上又は２０℃以上が好ましく、ヘイズ低減の観点から、４０℃以下又は３０℃以下が好ましい。 In the polishing step in the semiconductor substrate manufacturing method of the present disclosure, for example, a silicon wafer to be polished is sandwiched between a surface plate to which a polishing pad is attached, and a polishing liquid composition of 15° C. or more and 40° C. or less and a polishing pad surface temperature are applied to the silicon wafer to be polished. Wafers can be polished. The temperature of the polishing liquid composition and the surface temperature of the polishing pad are preferably 15° C. or higher or 20° C. or higher from the viewpoint of reducing haze and LPD, and preferably 40° C. or lower or 30° C. or lower from the viewpoint of reducing haze.
本開示の半導体基板製造方法は、前記研磨工程の後に、研磨された被研磨シリコンウェーハを洗浄する工程を更に含むことができる。 The semiconductor substrate manufacturing method of the present disclosure can further include a step of cleaning the polished silicon wafer after the polishing step.
［研磨方法］
本開示は、その他の態様において、本開示の研磨液組成物を用いて被研磨シリコンウェーハを研磨する研磨工程を含む、研磨方法（以下、［本開示の研磨方法］ともいう）に関する。本開示の研磨方法における研磨工程は、上述した本開示の半導体基板製造方法における研磨工程と同様にして行うことができる。本開示の研磨方法によれば、本開示の研磨液組成物を用いるため、研磨されたシリコンウェーハの表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）を低減できる。
[Polishing method]
In another aspect, the present disclosure relates to a polishing method (hereinafter also referred to as [the polishing method of the present disclosure]) including a polishing step of polishing a silicon wafer to be polished using the polishing liquid composition of the present disclosure. The polishing step in the polishing method of the present disclosure can be performed in the same manner as the polishing step in the semiconductor substrate manufacturing method of the present disclosure described above. According to the polishing method of the present disclosure, since the polishing liquid composition of the present disclosure is used, surface roughness (haze) and surface defects (LPD) of a polished silicon wafer can be reduced.
［研磨液キット］
本開示は、その他の態様において、本開示の研磨液組成物を製造するための研磨液キット（以下、「本開示のキット」と略称する場合もある。）に関する。本開示のキットによれば、表面粗さ（ヘイズ）の低減及び表面欠陥（ＬＰＤ）の低減を両立できる研磨液組成物が得られうる。
本開示のキットの一実施形態としては、成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ及び成分Ｅを含む溶液を含有する研磨液キットが挙げられる。前記溶液に含まれる水（成分Ｅ）は、研磨液組成物の調製に使用する水の全量でもよいし、一部でもよい。前記溶液は、一又は複数の実施形態において、使用時に、必要に応じて水（成分Ｅ）を用いて希釈される。前記溶液には、必要に応じて上述したその他の成分が含まれていてもよい。
[Polishing liquid kit]
In other aspects, the present disclosure relates to a polishing liquid kit (hereinafter sometimes abbreviated as "kit of the present disclosure") for manufacturing the polishing liquid composition of the present disclosure. According to the kit of the present disclosure, a polishing liquid composition that can reduce both surface roughness (haze) and surface defects (LPD) can be obtained.
One embodiment of the kit of the present disclosure includes a polishing liquid kit containing a solution containing component A, component B, component C, component D, and component E. The water (component E) contained in the solution may be the entire amount of water used for preparing the polishing liquid composition, or may be a portion thereof. The solution, in one or more embodiments, is optionally diluted with water (component E) at the time of use. The solution may contain other components mentioned above as necessary.
以下、実施例により本開示をさらに詳細に説明するが、これらは例示的なものであって、本開示はこれら実施例に制限されるものではない。 Hereinafter, the present disclosure will be explained in more detail with reference to Examples, but these are merely illustrative and the present disclosure is not limited to these Examples.
１．水溶性高分子Ｄ１～Ｄ１６の調製
表１に示す水溶性高分子Ｄ１～Ｄ１６を以下のようにして調製した。
Ｄ１：ポリビニルリン［丸善石油化学社製、ポリジメチルビニルホスホナート、重量平均分子量１，０００］
Ｄ２：ポリビニルリン［丸善石油化学社製、ポリジメチルビニルホスホナート、重量平均分子量３，４００］
Ｄ３：ポリグリセリン（２０）［ダイセル社製、重合度２０、重量平均分子量１，５００］
Ｄ４：ポリグリセリン（４０）［ダイセル社製の「ＸＰＷ」、重合度４０、重量平均分子量２，９８０］
Ｄ５：ポリグリセリン（５０）［ダイセル社製、重合度５０、重量平均分子量３，７２０］
Ｄ６：ポリグリセリン（８０）［ダイセル社製、重合度８０、重量平均分子量５，９４０］
Ｄ７：ポリグリセリン（１００）［ダイセル社製、重合度１００、重量平均分子量７，４２０］
Ｄ８：ポリグリセリン（２０）ラウリルエーテル［ダイセル社製、重合度２０、重量平均分子量２，６００］
Ｄ９：下記のようにして合成した疎水変性ポリグリセリン (PG-BuGly)
Ｄ１０：ポリビニルピロリドン（Ｋ－９０）［富士フィルム和工純薬社製、重量平均分子量３６０，０００］
Ｄ１１：下記のようにして合成したＨＥＡＡ単独重合体（ｐＨＥＡＡ）
Ｄ１２：ＨＥＣ［ダイセル社製、ＳＥ４００、重量平均分子量２５０，０００］
Ｄ１３：ＨＥＣ［住友精化社製、ＣＦ－Ｖ、重量平均分子量８００，０００］
Ｄ１４：ＰＶＡ１０３［クラレ社製、重合度：３００］
Ｄ１５：ＰＶＡ１２４［クラレ社製、重合度：２，４００］
Ｄ１６：ポリビニルピロリドン（Ｋ－３０）［富士フィルム和工純薬社製、重量平均分子量４０，０００］
1. Preparation of water-soluble polymers D1 to D16 Water-soluble polymers D1 to D16 shown in Table 1 were prepared as follows.
D1: Polyvinyl phosphorus [manufactured by Maruzen Petrochemical Co., Ltd., polydimethylvinylphosphonate, weight average molecular weight 1,000]
D2: Polyvinyl phosphorus [manufactured by Maruzen Petrochemical Co., Ltd., polydimethylvinylphosphonate, weight average molecular weight 3,400]
D3: Polyglycerin (20) [manufactured by Daicel, polymerization degree 20, weight average molecular weight 1,500]
D4: Polyglycerin (40) [“XPW” manufactured by Daicel, polymerization degree 40, weight average molecular weight 2,980]
D5: Polyglycerin (50) [manufactured by Daicel, polymerization degree 50, weight average molecular weight 3,720]
D6: Polyglycerin (80) [manufactured by Daicel, polymerization degree 80, weight average molecular weight 5,940]
D7: Polyglycerin (100) [manufactured by Daicel, degree of polymerization 100, weight average molecular weight 7,420]
D8: Polyglycerin (20) lauryl ether [manufactured by Daicel, polymerization degree 20, weight average molecular weight 2,600]
D9: Hydrophobically modified polyglycerin (PG-BuGly) synthesized as follows
D10: Polyvinylpyrrolidone (K-90) [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight average molecular weight 360,000]
D11: HEAA homopolymer (pHEAA) synthesized as follows
D12: HEC [manufactured by Daicel, SE400, weight average molecular weight 250,000]
D13: HEC [manufactured by Sumitomo Seika Chemicals, CF-V, weight average molecular weight 800,000]
D14: PVA103 [manufactured by Kuraray Co., Ltd., degree of polymerization: 300]
D15: PVA124 [manufactured by Kuraray Co., Ltd., degree of polymerization: 2,400]
D16: Polyvinylpyrrolidone (K-30) [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., weight average molecular weight 40,000]
［水溶性高分子Ｄ９（PG-BuGly）の合成例］
ジムロート冷却管、温度計及び三日月形テフロン（登録商標）製撹拌翼を備えた２００ｍＬセパラブルフラスコに、ポリグリセリン（４０）３０ｇ（０．０１０１ｍｏｌ、ダイセル社製の「ＸＰＷ」、重合度４０、重量平均分子量２，９８０）を３６．７５ｇのジメチルホルムアミドに溶解し、さらに水酸化カリウム０．１１ｇ（０．０２ｍｏｌ、東京化成工業社製）を投入した。次いで、オイルバスを用いてセパラブルフラスコ内の温度を１３０℃に昇温した後、２Ｔｏｒｒの減圧条件下において、攪拌しながら脱水処理を３０分間行った。次いで、攪拌しながらセパラブルフラスコ内の温度を８０℃に降温した後、１－ブトキシ－２，３－エポキシプロパン６．６４ｇ（０．０５１ｍｏｌ、東京化成工業社製）を添加した後、反応溶液の温度及び攪拌を５時間保持した。反応終了後、酢酸０．１２ｇ（０．０２ｍｏｌ、東京化成工業社製）を添加して中和処理を実施した後、１００℃、２Ｔｏｒｒの条件下において、溶媒留去を行った。次いで、カラムに陽イオン交換樹脂（イオン交換樹脂：三菱ケミカル製 ＤＩＡＩＯＮ ＳＫ１ＢＨ）を１００ｍｌ充填し、反応終了物に対して、超純水を有効分濃度が２０％になるように添加し、空間速度ＳＶ値が４．０となる条件でイオン交換処理することにより、カリウム含有量が１ｐｐｍ以下の水溶性高分子Ｄ９（２０質量％水溶液、重量平均分子量：３，２４０）を得た。
[Synthesis example of water-soluble polymer D9 (PG-BuGly)]
In a 200 mL separable flask equipped with a Dimroth condenser, a thermometer, and a crescent-shaped Teflon (registered trademark) stirring blade, 30 g (0.0101 mol) of polyglycerin (40), "XPW" manufactured by Daicel, polymerization degree 40, weight (average molecular weight 2,980) was dissolved in 36.75 g of dimethylformamide, and 0.11 g (0.02 mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) of potassium hydroxide was further added. Next, the temperature inside the separable flask was raised to 130° C. using an oil bath, and then dehydration treatment was performed for 30 minutes with stirring under reduced pressure conditions of 2 Torr. Next, the temperature inside the separable flask was lowered to 80°C while stirring, and then 6.64 g (0.051 mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) of 1-butoxy-2,3-epoxypropane was added, and the reaction solution was The temperature and stirring were maintained for 5 hours. After the reaction was completed, 0.12 g (0.02 mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) of acetic acid was added to perform a neutralization treatment, and then the solvent was distilled off under conditions of 100° C. and 2 Torr. Next, the column was filled with 100 ml of cation exchange resin (ion exchange resin: DIAION SK1BH manufactured by Mitsubishi Chemical), and ultrapure water was added to the reaction product so that the effective concentration was 20%, and the space velocity was increased. Water-soluble polymer D9 (20% by mass aqueous solution, weight average molecular weight: 3,240) having a potassium content of 1 ppm or less was obtained by ion exchange treatment under conditions such that the SV value was 4.0.
［水溶性高分子Ｄ１１（ｐＨＥＡＡ）の合成例］
ヒドロキシエチルアクリルアミド１５０ｇ（１．３０ｍｏｌ、興人製)を１００ｇのイオン交換水に溶解し、モノマー水溶液を調製した。また、別に、２，２’－アゾビス（２－メチルプロピオンアミジン）ジヒドロクロリド ０．０３５ｇ（重合開始剤、「Ｖ－５０」、１．３０ｍｍｏｌ、和光純薬製）を７０ｇのイオン交換水に溶解し、重合開始剤水溶液を調製した。ジムロート冷却管、温度計及び三日月形テフロン（登録商標）製撹拌翼を備えた２Ｌセパラブルフラスコに、イオン交換水１，１８０ｇを投入した後、セパラブルフラスコ内を窒素置換した。次いで、オイルバスを用いてセパラブルフラスコ内の温度を６８℃に昇温した後、予め調製した上記モノマー水溶液と上記重合開始剤水溶液を各々３．５時間かけて撹拌を行っているセパラブルフラスコ内に滴下した。滴下終了後、反応溶液の温度及び撹拌を４時間保持し、無色透明の１０質量％ポリヒドロキシエチルアクリルアミド（ｐＨＥＡＡ、重量平均分子量：７００，０００）水溶液１，５００ｇを得た。
[Synthesis example of water-soluble polymer D11 (pHEAA)]
A monomer aqueous solution was prepared by dissolving 150 g (1.30 mol, manufactured by Kojin) of hydroxyethyl acrylamide in 100 g of ion-exchanged water. Separately, 0.035 g of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (polymerization initiator, "V-50", 1.30 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 70 g of ion-exchanged water. Then, an aqueous polymerization initiator solution was prepared. After 1,180 g of ion-exchanged water was put into a 2 L separable flask equipped with a Dimroth condenser, a thermometer, and a crescent-shaped Teflon (registered trademark) stirring blade, the inside of the separable flask was purged with nitrogen. Next, the temperature inside the separable flask was raised to 68°C using an oil bath, and then the monomer aqueous solution and the polymerization initiator aqueous solution prepared in advance were each stirred for 3.5 hours. dripped inside. After completion of the dropwise addition, the temperature and stirring of the reaction solution were maintained for 4 hours to obtain 1,500 g of a colorless and transparent 10% by mass polyhydroxyethyl acrylamide (pHEAA, weight average molecular weight: 700,000) aqueous solution.
２．研磨液組成物の調製
表１～３に示すシリカ粒子（成分Ａ）、表１～３に示す含窒素塩基性化合物（成分Ｂ）、ポリエチレングリコール（成分Ｃ）又は非成分Ｃ、表１～３に示す水溶性高分子（成分Ｄ）及び超純水を撹拌混合して実施例１～１７及び比較例１～９の研磨液組成物を得た。表１～３中の各成分の含有量は、研磨液組成物の使用時における各成分の含有量（質量％、有効分）である。超純水の含有量は、成分Ａ、成分Ｂ、成分Ｃ又は非成分Ｃ、成分Ｄを除いた残余である。各研磨液組成物（使用時）の２５℃におけるｐＨは、１０．０であった。
2. Preparation of polishing liquid composition Silica particles shown in Tables 1 to 3 (component A), nitrogen-containing basic compound shown in Tables 1 to 3 (component B), polyethylene glycol (component C) or non-component C, Tables 1 to 3 Polishing liquid compositions of Examples 1 to 17 and Comparative Examples 1 to 9 were obtained by stirring and mixing the water-soluble polymer shown in (Component D) and ultrapure water. The content of each component in Tables 1 to 3 is the content (% by mass, effective content) of each component when the polishing liquid composition is used. The content of ultrapure water is the remainder after removing component A, component B, component C, non-component C, and component D. The pH of each polishing liquid composition (when used) at 25° C. was 10.0.
各研磨液組成物の調製に用いた成分Ａ、成分Ｂ、成分Ｃ、非成分Ｃには下記のものを用いた。
（成分Ａ）
Ａ１：コロイダルシリカ［平均一次粒子径３５ｎｍ、平均二次粒子径７０ｎｍ、会合度２．０］
Ａ２：コロイダルシリカ［平均一次粒子径２４ｎｍ、平均二次粒子径４９ｎｍ、会合度２．０］
Ａ３：コロイダルシリカ［平均一次粒子径１６ｎｍ、平均二次粒子径２６ｎｍ、会合度１．６］
（成分Ｂ）
アンモニア［２８質量％アンモニア水、キシダ化学社製、試薬特級］
（成分Ｃ）
Ｃ１：ポリエチレングリコール［分子量１，０００、日油社製、ＰＥＧ＃１０００］
Ｃ２：ポリエチレングリコール［分子量２，０００、日油社製、ＰＥＧ＃２０００］
Ｃ３：ポリエチレングリコール［分子量６，０００、日油社製、ＰＥＧ＃６０００］
（非成分Ｃ）
Ｃ４：ポリエチレングリコール－ポリプロピレングリコール－ポリエチレングリコール（ＥＯ－ＰＯ－ＥＯ）［分子量２，２２０、日油社製、プロノン＃２０１］
The following components were used as component A, component B, component C, and non-component C used in preparing each polishing liquid composition.
(Component A)
A1: Colloidal silica [average primary particle diameter 35 nm, average secondary particle diameter 70 nm, degree of association 2.0]
A2: Colloidal silica [average primary particle diameter 24 nm, average secondary particle diameter 49 nm, degree of association 2.0]
A3: Colloidal silica [average primary particle diameter 16 nm, average secondary particle diameter 26 nm, degree of association 1.6]
(Component B)
Ammonia [28% by mass ammonia water, manufactured by Kishida Chemical Co., Ltd., special reagent grade]
(Component C)
C1: Polyethylene glycol [molecular weight 1,000, manufactured by NOF Corporation, PEG #1000]
C2: Polyethylene glycol [molecular weight 2,000, manufactured by NOF Corporation, PEG #2000]
C3: Polyethylene glycol [molecular weight 6,000, manufactured by NOF Corporation, PEG #6000]
(Non-component C)
C4: Polyethylene glycol-polypropylene glycol-polyethylene glycol (EO-PO-EO) [molecular weight 2,220, manufactured by NOF Corporation, Pronone #201]
２．各種パラメーターの測定方法
（１）シリカ粒子（成分Ａ）の平均一次粒子径の測定
成分Ａの平均一次粒子径（ｎｍ）は、ＢＥＴ（窒素吸着）法によって算出される比表面積Ｓ（ｍ2／ｇ）を用いて下記式で算出した。
平均一次粒子径（ｎｍ）＝２７２７／Ｓ
2. Methods for measuring various parameters (1) Measurement of average primary particle diameter of silica particles (component A) The average primary particle diameter (nm) of component A is determined by the specific surface area S (m 2 / g) using the following formula.
Average primary particle diameter (nm) = 2727/S
成分Ａの比表面積Ｓは、下記の［前処理］をした後、測定サンプル約０．１ｇを測定セルに小数点以下４桁まで精量し、比表面積の測定直前に１１０℃の雰囲気下で３０分間乾燥した後、比表面積測定装置（マイクロメリティック自動比表面積測定装置「フローソーブＩＩＩ２３０５」、島津製作所製）を用いて窒素吸着法（ＢＥＴ法）により測定した。
［前処理］
（ａ）スラリー状の成分Ａを硝酸水溶液でｐＨ２．５±０．１に調整する。
（ｂ）ｐＨ２．５±０．１に調整されたスラリー状の成分Ａをシャーレにとり１５０℃の熱風乾燥機内で１時間乾燥させる。
（ｃ）乾燥後、得られた試料をメノウ乳鉢で細かく粉砕する。
（ｄ）粉砕された試料を４０℃のイオン交換水に懸濁させ、孔径１μｍのメンブランフィルタで濾過する。
（ｅ）フィルタ上の濾過物を２０ｇのイオン交換水（４０℃）で５回洗浄する。
（ｆ）濾過物が付着したフィルタをシャーレにとり、１１０℃の雰囲気下で４時間乾燥させる。
（ｇ）乾燥した濾過物（成分Ａ）をフィルタ屑が混入しないようにとり、乳鉢で細かく粉砕して測定サンプルを得た。
The specific surface area S of component A is calculated by weighing approximately 0.1 g of a measurement sample into a measurement cell to four decimal places after the following [pretreatment], and heating it at 30°C in an atmosphere of 110°C immediately before measuring the specific surface area. After drying for a minute, measurement was performed by a nitrogen adsorption method (BET method) using a specific surface area measuring device (Micromeritic automatic specific surface area measuring device "Flowsorb III 2305", manufactured by Shimadzu Corporation).
[Preprocessing]
(a) Component A in slurry form is adjusted to pH 2.5±0.1 with an aqueous nitric acid solution.
(b) Component A in the form of slurry adjusted to pH 2.5±0.1 is placed in a Petri dish and dried in a hot air dryer at 150° C. for 1 hour.
(c) After drying, the obtained sample is finely ground in an agate mortar.
(d) The pulverized sample is suspended in ion-exchanged water at 40°C and filtered through a membrane filter with a pore size of 1 μm.
(e) Wash the filtrate on the filter 5 times with 20 g of ion-exchanged water (40°C).
(f) Take the filter with the filtrate attached to it in a petri dish and dry it in an atmosphere of 110° C. for 4 hours.
(g) The dried filtrate (component A) was taken to avoid contamination with filter debris, and finely ground in a mortar to obtain a measurement sample.
（２）シリカ粒子（成分Ａ）の平均二次粒子径
成分Ａの平均二次粒子径（ｎｍ）は、成分Ａの濃度が０．２５質量％となるように研磨材をイオン交換水に添加した後、得られた水分散液をＤｉｓｐｏｓａｂｌｅ Ｓｉｚｉｎｇ Ｃｕｖｅｔｔｅ（ポリスチレン製 １０ｍｍセル）に下底からの高さ１０ｍｍまで入れ、動的光散乱法（装置名：「ゼータサイザーＮａｎｏ ＺＳ」、シスメックス社製）を用いて測定した。
(2) Average secondary particle diameter of silica particles (component A) The average secondary particle diameter (nm) of component A is determined by adding an abrasive to ion-exchanged water so that the concentration of component A is 0.25% by mass. After that, the obtained aqueous dispersion was placed in a Disposable Sizing Cuvette (polystyrene 10 mm cell) to a height of 10 mm from the bottom, and subjected to dynamic light scattering method (device name: "Zetasizer Nano ZS", manufactured by Sysmex Corporation). Measured using
（３）水溶性高分子Ｄ１～１６の重量平均分子量の測定
成分Ｄ１～１６の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法を下記の条件で適用して得たクロマトグラム中のピークに基づき算出した。
＜水溶性高分子Ｄ１～Ｄ１０、Ｄ１２～Ｄ１６の測定条件＞
装置：ＨＬＣ－８３２０ ＧＰＣ（東ソー社製、検出器一体型）
カラム：α－Ｍ＋α－Ｍ（カチオン）
溶離液：０．１５ｍｏｌ／Ｌ Ｎａ２ＳＯ４，１質量％酢酸，溶媒：水
流量：１．０ｍＬ／ｍｉｎ
カラム温度：４０℃
検出器：ショーデックスＲＩ ＳＥ－６１示差屈折率検出器
標準物質：分子量が既知のプルラン
＜水溶性高分子Ｄ１１（ｐＨＥＡＡ）の測定条件＞
装置：ＨＬＣ－８３２０ ＧＰＣ（東ソー社製、検出器一体型）
カラム：ＧＭＰＷＸＬ＋ＧＭＰＷＸＬ（アニオン）
溶離液：０．２Ｍリン酸バッファー／ＣＨ3ＣＮ＝９／１
流量：０．５ｍＬ／ｍｉｎ
カラム温度：４０℃
検出器：ショーデックスＲＩ ＳＥ－６１示差屈折率検出器
標準物質：分子量が既知の単分散ポリエチレングリコール
(3) Measurement of weight average molecular weights of water-soluble polymers D1 to 16 The weight average molecular weights of components D1 to 16 are determined by the peaks in the chromatogram obtained by applying the gel permeation chromatography (GPC) method under the following conditions. Calculated based on.
<Measurement conditions for water-soluble polymers D1 to D10, D12 to D16>
Equipment: HLC-8320 GPC (manufactured by Tosoh Corporation, integrated detector)
Column: α-M+α-M (cation)
Eluent: 0.15 mol/L Na 2 SO 4 , 1% by mass acetic acid, solvent: water Flow rate: 1.0 mL/min
Column temperature: 40℃
Detector: Shodex RI SE-61 differential refractive index detector Standard material: Pullulan with known molecular weight <Measurement conditions for water-soluble polymer D11 (pHEAA)>
Equipment: HLC-8320 GPC (manufactured by Tosoh Corporation, integrated detector)
Column: GMPWXL + GMPWXL (anion)
Eluent: 0.2M phosphate buffer/CH 3 CN=9/1
Flow rate: 0.5mL/min
Column temperature: 40℃
Detector: Shodex RI SE-61 differential refractive index detector Standard material: Monodisperse polyethylene glycol with known molecular weight
（４）水溶性高分子（成分Ｄ）の水酸基価
成分Ｄの水酸基価は、ＪＩＳ Ｋ ００７０，ＡＯＣＳ Ｃｄ １３－６０に準拠して行い、以下の操作を実施した後、下記計算式により求めた。
［操作方法］
（ａ）成分Ｄをアセチル化フラスコへ精密にはかりとる。
（ｂ）３ ｍＬのアセチル化試薬を、ピペットで正確に加える。
（ｃ）アセチル化フラスコに小漏斗を乗せ、９５～１００℃のグリセリン浴にフラスコの底が約１ｃｍ浸かるようにして１時間反応させる。途中、時々振りまぜ反応を促進させる。
（ｄ）室温まで放冷後、小漏斗から約１ｍＬの水を駒込ピペットで加え、振り混ぜた後再びグリセリン浴に５分間浸け加水分解する。
（ｅ）
室温まで放冷後、約３０ｍＬの中性エタノ－ルで、小漏斗及びフラスコの口部を洗い込み溶解する。
（ｆ）０．５ ｍｏｌ／Ｌ アルコ－ル性水酸化カリウム標準溶液で滴定する。終点は無色から微紅色に変わった点とする。
（ｇ）同時に、並行して空試験をおこなう。
［計算式］
水酸基価（ＯＨＶ）（ｍｇＫＯＨ／ｇ）＝｛［（Ｂ－Ａ）×ｆ×２８．０５］／［試料採取量（ｇ）］｝ ＋ 酸価（ＡＶ）
Ａ：試料の滴定に要した０．５ ｍｏｌ／Ｌ アルコ－ル性水酸化カリウム標準溶液の使用量（ｍＬ）
Ｂ：空試験の滴定に要した０．５ ｍｏｌ／Ｌ アルコ－ル性水酸化カリウム標準溶液の使用量（ｍＬ）
ｆ：０．５ ｍｏｌ／Ｌ アルコ－ル性水酸化カリウム標準溶液のファクタ－
(4) Hydroxyl value of water-soluble polymer (component D) The hydroxyl value of component D was determined in accordance with JIS K 0070, AOCS Cd 13-60, and was calculated using the following calculation formula after performing the following operations. .
[Method of operation]
(a) Precisely weigh component D into the acetylation flask.
(b) Add 3 mL of acetylation reagent accurately with a pipette.
(c) Place a small funnel on the acetylation flask and allow to react for 1 hour in a glycerin bath at 95 to 100°C so that the bottom of the flask is submerged by about 1 cm. Stir occasionally during the process to promote reaction.
(d) After cooling to room temperature, add about 1 mL of water from a small funnel with a Komagome pipette, shake and mix, and then immerse in the glycerin bath again for 5 minutes to hydrolyze.
(e)
After cooling to room temperature, wash the small funnel and the mouth of the flask with about 30 mL of neutral ethanol to dissolve.
(f) Titrate with 0.5 mol/L alcoholic potassium hydroxide standard solution. The end point is the point where the color changes from colorless to slightly pink.
(g) At the same time, conduct a blank test in parallel.
[a formula]
Hydroxyl value (OHV) (mgKOH/g) = {[(B-A) x f x 28.05]/[Amount of sample collected (g)]} + Acid value (AV)
A: Amount of 0.5 mol/L alcoholic potassium hydroxide standard solution required for sample titration (mL)
B: Amount of 0.5 mol/L alcoholic potassium hydroxide standard solution required for titration in blank test (mL)
f: 0.5 mol/L Factor of alcoholic potassium hydroxide standard solution
（５）フィルタ通液量の測定
各研磨液組成物を、エアー圧力０．２５ＭＰａの一定圧力の下で、所定のフィルタ［アドバンテック社製、親水性ＰＴＦＥ０．２μｍ（孔径）フィルタ、型式：２５ＨＰ０２０ＡＮ］に通液させ、フィルタが閉塞するまでの通液量（ｇ／ｓｅｃ・ｃｍ2）を測定した。なお、閉塞しない研磨液組成物については、フィルタから通液される研磨液組成物の間隔が５秒間隔になるまでの通液量をフィルタ通液量とした。
(5) Measurement of amount of liquid passed through filter Each polishing liquid composition was applied to a specified filter [manufactured by Advantech, hydrophilic PTFE 0.2 μm (pore diameter) filter, model: 25HP020AN] under a constant air pressure of 0.25 MPa. The amount of liquid (g/sec·cm 2 ) until the filter became clogged was measured. In addition, regarding the polishing liquid composition that did not block, the amount of liquid passed through the filter until the interval of the polishing liquid composition passed from the filter became 5 seconds was defined as the amount of liquid passed through the filter.
３．研磨方法
各研磨液組成物について、それぞれ研磨直前にフィルタ（コンパクトカートリッジフィルタ「ＭＣＰ－ＬＸ－Ｃ１０Ｓ」、アドバンテック社製）にてろ過を行い、下記の研磨条件で下記のシリコンウェーハに対して仕上げ研磨を行った。当該仕上げ研磨に先立ってシリコンウェーハに対して市販の研磨液組成物を用いてあらかじめ粗研磨を実施した。粗研磨を終了し仕上げ研磨に供した単結晶シリコンウェーハのヘイズは、２～３ｐｐｍであり、ポリシリコンウェーハのヘイズは、３～５ｐｐｍであった。ヘイズは、ＫＬＡ Ｔｅｎｃｏｒ社製「Ｓｕｒｆｓｃａｎ ＳＰ１－ＤＬＳ」を用いて測定される暗視野ワイド斜入射チャンネル（ＤＷＯ）での値である。
＜シリコンウェーハ＞
単結晶シリコンウェーハ［直径２００ｍｍのシリコン片面鏡面ウェーハ、伝導型：Ｐ、結晶方位：１００、抵抗率：０．１Ω・ｃｍ以上１００Ω・ｃｍ未満］
ポリシリコンウェーハ［直径２００ｍｍのシリコン片面鏡面ウェーハ、伝導型：Ｐ、結晶方位：１００、抵抗率：０．１Ω・ｃｍ以上１００Ω・ｃｍ未満の上にＳｉＯ２膜を４４００Å分プラズマＣＶＤ法により堆積させ、続いてポリシリコン膜を８０００Å同じくプラズマＣＶＤ法により堆積させたウェーハ］
3. Polishing method Each polishing liquid composition is filtered using a filter (Compact Cartridge Filter "MCP-LX-C10S", manufactured by Advantech) immediately before polishing, and final polishing is performed on the following silicon wafers under the following polishing conditions. I did it. Prior to the final polishing, the silicon wafer was subjected to rough polishing using a commercially available polishing liquid composition. The haze of the single-crystal silicon wafer that was subjected to rough polishing and final polishing was 2 to 3 ppm, and the haze of the polysilicon wafer was 3 to 5 ppm. Haze is a value in a dark field wide grazing incidence channel (DWO) measured using "Surfscan SP1-DLS" manufactured by KLA Tencor.
<Silicon wafer>
Single-crystal silicon wafer [silicon single-sided mirror wafer with a diameter of 200 mm, conductivity type: P, crystal orientation: 100, resistivity: 0.1 Ω·cm or more and less than 100 Ω·cm]
A SiO 2 film of 4400 Å was deposited on a polysilicon wafer [silicon single-sided mirror wafer with a diameter of 200 mm, conductivity type: P, crystal orientation: 100, resistivity: 0.1 Ω·cm or more and less than 100 Ω·cm by plasma CVD method. , followed by a wafer on which a polysilicon film of 8000 Å was deposited using the same plasma CVD method]
＜仕上げ研磨条件＞
研磨機：片面８インチ研磨機「ＧＲＩＮＤ－Ｘ ＳＰＰ６００ｓ」（岡本工作製）
研磨パッド：スエードパッド（東レ コーテックス社製、アスカー硬度：６４、厚さ：１．３７ｍｍ、ナップ長：４５０ｕｍ、開口径：６０ｕｍ）
シリコンウェーハ研磨圧力：１００ｇ／ｃｍ2
定盤回転速度：６０ｒｐｍ
研磨時間：５分
研磨液組成物の供給速度：１５０ｇ／ｃｍ2
研磨液組成物の温度：２３℃
キャリア回転速度：６２ｒｐｍ
<Final polishing conditions>
Grinding machine: Single-sided 8-inch grinding machine "GRIND-X SPP600s" (manufactured by Okamoto Kosaku)
Polishing pad: Suede pad (manufactured by Toray Cortex, Asker hardness: 64, thickness: 1.37mm, nap length: 450um, opening diameter: 60um)
Silicon wafer polishing pressure: 100g/cm 2
Surface plate rotation speed: 60 rpm
Polishing time: 5 minutes Supply rate of polishing liquid composition: 150g/cm 2
Temperature of polishing liquid composition: 23°C
Carrier rotation speed: 62rpm
４．洗浄方法
仕上げ研磨後、シリコンウェーハに対して、オゾン洗浄と希フッ酸洗浄を下記のとおり行った。オゾン洗浄では、２０ｐｐｍのオゾンを含んだ水溶液をノズルから流速１Ｌ／ｍｉｎ、６００ｒｐｍで回転するシリコンウェーハの中央に向かって３分間噴射した。このときオゾン水の温度は常温とした。次に希フッ酸洗浄を行った。希フッ酸洗浄では、０．５質量％のフッ化水素アンモニウム（特級、ナカライテクス株式会社）を含んだ水溶液をノズルから流速１Ｌ／ｍｉｎ、６００ｒｐｍで回転するシリコンウェーハの中央に向かって６秒間噴射した。上記オゾン洗浄と希フッ酸洗浄を１セットとして計２セット行い、最後にスピン乾燥を行った。スピン乾燥では１，５００ｒｐｍでシリコンウェーハを回転させた。
4. Cleaning method After final polishing, the silicon wafer was subjected to ozone cleaning and dilute hydrofluoric acid cleaning as described below. In ozone cleaning, an aqueous solution containing 20 ppm of ozone was sprayed from a nozzle at a flow rate of 1 L/min toward the center of the silicon wafer rotating at 600 rpm for 3 minutes. At this time, the temperature of the ozonated water was set to room temperature. Next, dilute hydrofluoric acid cleaning was performed. In dilute hydrofluoric acid cleaning, an aqueous solution containing 0.5% by mass of ammonium hydrogen fluoride (special grade, Nacalai Techs Co., Ltd.) is sprayed from a nozzle at a flow rate of 1 L/min toward the center of the silicon wafer rotating at 600 rpm for 6 seconds. did. A total of two sets of the above ozone cleaning and dilute hydrofluoric acid cleaning were performed as one set, and finally spin drying was performed. In spin drying, the silicon wafer was rotated at 1,500 rpm.
５．シリコンウェーハの表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の評価
洗浄後のシリコンウェーハ表面の表面粗さ（ヘイズ）の評価には、表面粗さ測定装置「Ｓｕｒｆｓｃａｎ ＳＰ１－ＤＬＳ」（ＫＬＡ Ｔｅｎｃｏｒ社製）を用いて測定される、暗視野ワイド斜入射チャンネル（ＤＷＯ）での値（ＤＷＯヘイズ）を用いた。また、表面欠陥（ＬＰＤ）は、Ｈａｚｅ測定時に同時に測定され、シリコンウェーハ表面上の粒径が４５ｎｍ以上のパーティクル数を測定することによって評価した。表面欠陥（ＬＰＤ）の評価結果は、数値が小さいほど表面欠陥が少ないことを示す。また、ヘイズ（ＤＷＯ）の数値は小さいほど、表面の平滑性が高いことを示す。表面粗さ（ヘイズ）及び表面欠陥（ＬＰＤ）の測定は、各々２枚のシリコンウェーハに対して行い、各々平均値を表１及び表２に示した。表１は、実施例１～１６及び比較例１～８の研磨液組成物を用いて単結晶シリコンウェーハを研磨した場合の結果を示し、表２は、実施例１７及び比較例９の研磨液組成物を用いてポリシリコンウェーハを研磨した場合の結果を示す。
5. Evaluation of surface roughness (haze) and surface defects (LPD) of silicon wafers To evaluate the surface roughness (haze) of the silicon wafer surface after cleaning, a surface roughness measurement device “Surfscan SP1-DLS” (KLA Tencor Inc.) was used. The value (DWO haze) in a dark-field wide grazing incidence channel (DWO) measured using a digital camera (manufactured by Fujitsu, Ltd.) was used. Furthermore, surface defects (LPD) were measured at the same time as the Haze measurement, and were evaluated by measuring the number of particles with a particle size of 45 nm or more on the silicon wafer surface. The evaluation results for surface defects (LPD) indicate that the smaller the numerical value, the fewer surface defects. Further, the smaller the haze (DWO) value, the higher the surface smoothness. Surface roughness (haze) and surface defects (LPD) were measured on two silicon wafers, and the average values are shown in Tables 1 and 2. Table 1 shows the results when single crystal silicon wafers were polished using the polishing liquid compositions of Examples 1 to 16 and Comparative Examples 1 to 8, and Table 2 shows the results of polishing the polishing liquids of Example 17 and Comparative Example 9. The results are shown when polysilicon wafers were polished using the composition.
表１に示されるように、実施例１～１６の研磨液組成物は、比較例１～８の研磨液組成物に比べて、研磨された単結晶シリコンウェーハのヘイズ及びＬＰＤの両方が低減されていた。 As shown in Table 1, the polishing liquid compositions of Examples 1 to 16 reduced both the haze and LPD of polished single crystal silicon wafers compared to the polishing liquid compositions of Comparative Examples 1 to 8. was.
表２に示されるように、実施例１７の研磨液組成物は、比較例９の研磨液組成物に比べて、研磨されたポリシリコンウェーハのヘイズ及びＬＰＤの両方が低減されていた。 As shown in Table 2, the polishing liquid composition of Example 17 reduced both the haze and LPD of the polished polysilicon wafer compared to the polishing liquid composition of Comparative Example 9.
さらに、実施例３～７、１６及び比較例３に関して、上記ＤＷＯヘイズよりも高感度のＤＮＮヘイズを測定し、表面粗さ（ヘイズ）を評価した。ＤＮＮヘイズは、ＤＷＯヘイズと同じ表面粗さ測定装置「Ｓｕｒｆｓｃａｎ ＳＰ１－ＤＬＳ」（ＫＬＡ Ｔｅｎｃｏｒ社製）を用い、測定モード［暗視野垂直入射、垂直検出チャンネル（ＤＮＮ）での値］により測定される値である。測定結果を表３に示した。ＤＮＮヘイズの数値は小さいほど、表面の平滑性が高いことを示す。
また、実施例３～７、１６及び比較例３に関して、測定機「Ｚｙｇｏ Ｎｅｗ
Ｖｉｅｗ ７３００」（Ｚｙｇｏ Ｃｏｒｐｏｒａｔｉｏｎ社製）を用い、表面粗さ（二乗平均平方根：Ｒｑ）を測定した。測定結果を表３に示した。表面粗さＲｑの数値が小さいほど、表面の平滑性が高いことを示す。
Furthermore, for Examples 3 to 7, 16 and Comparative Example 3, DNN haze, which is more sensitive than the above DWO haze, was measured to evaluate surface roughness (haze). DNN haze is measured using the same surface roughness measurement device as DWO haze, "Surfscan SP1-DLS" (manufactured by KLA Tencor), in the measurement mode [dark field normal incidence, value in vertical detection channel (DNN)]. It is a value. The measurement results are shown in Table 3. The smaller the DNN haze value, the higher the surface smoothness.
In addition, regarding Examples 3 to 7, 16 and Comparative Example 3, the measuring device “Zygo New
Surface roughness (root mean square: Rq) was measured using "View 7300" (manufactured by Zygo Corporation). The measurement results are shown in Table 3. The smaller the numerical value of the surface roughness Rq, the higher the smoothness of the surface.
表３に示されるように、実施例３～７、１６の研磨液組成物は、通液性を確保しながら、シリコンウェーハ表面のヘイズ及びＬＰＤの両方を低減でき、さらに表面粗さも良好であることが示唆された。 As shown in Table 3, the polishing liquid compositions of Examples 3 to 7 and 16 can reduce both haze and LPD on the silicon wafer surface while ensuring liquid permeability, and also have good surface roughness. It has been suggested.
本開示の研磨液組成物を用いれば、研磨されたシリコンウェーハ表面のヘイズ及びＬＰＤの両方を低減できる。よって、本開示の研磨液組成物は、様々な半導体基板の製造過程で用いられる研磨液組成物として有用であり、なかでも、シリコンウェーハの仕上げ研磨用の研磨液組成物として有用である。 By using the polishing liquid composition of the present disclosure, both haze and LPD on the surface of a polished silicon wafer can be reduced. Therefore, the polishing liquid composition of the present disclosure is useful as a polishing liquid composition used in various semiconductor substrate manufacturing processes, and is particularly useful as a polishing liquid composition for final polishing of silicon wafers.
Claims (10)
前記研磨液組成物を孔径０．２μｍのＰＴＦＥフィルタを用いて濾過圧力０．２５ＭＰａで濾過したときのフィルタ単位面積あたりの通液量が０．２ｇ／ｓｅｃ・ｃｍ2以上であり、
前記水溶性高分子（成分Ｄ）は、ポリグリシドール、ポリグリシドール誘導体、ポリグリセリン、ポリグリセリン誘導体から選ばれる少なくとも１種であって、水酸基価が６００ｍｇＫＯＨ／ｇ以上８５０ｍｇＫＯＨ／ｇ以下の水溶性高分子であるか、又は、前記水溶性高分子（成分Ｄ）は、ポリジメチルビニルホスホナートである、研磨液組成物。 A polishing liquid composition containing silica particles (component A), a nitrogen-containing basic compound (component B), polyethylene glycol (component C), a water-soluble polymer other than polyethylene glycol (component D), and water (component E). And,
When the polishing liquid composition is filtered at a filtration pressure of 0.25 MPa using a PTFE filter with a pore size of 0.2 μm, the amount of liquid passed per unit area of the filter is 0.2 g/sec cm 2 or more ,
The water-soluble polymer (component D) is at least one selected from polyglycidol, polyglycidol derivatives, polyglycerin, and polyglycerin derivatives, and has a hydroxyl value of 600 mgKOH/g or more and 850 mgKOH/g or less. Alternatively, the water-soluble polymer (component D) is a polishing liquid composition, wherein the water-soluble polymer (component D) is polydimethylvinylphosphonate .
ポリエチレングリコール以外の水溶性高分子（成分Ｄ）とポリエチレングリコール（成分Ｃ）との質量比（Ｄ／Ｃ）が７以上５００未満であり、
前記水溶性高分子（成分Ｄ）は、ポリグリシドール、ポリグリシドール誘導体、ポリグリセリン、ポリグリセリン誘導体から選ばれる少なくとも１種であって、水酸基価が６００ｍｇＫＯＨ／ｇ以上８５０ｍｇＫＯＨ／ｇ以下の水溶性高分子であるか、又は、前記水溶性高分子（成分Ｄ）は、ポリジメチルビニルホスホナートである、研磨液組成物。 A polishing liquid composition containing silica particles (component A), a nitrogen-containing basic compound (component B), polyethylene glycol (component C), a water-soluble polymer other than polyethylene glycol (component D), and water (component E). And,
The mass ratio (D/C) of a water-soluble polymer other than polyethylene glycol (component D) and polyethylene glycol (component C) is 7 or more and less than 500,
The water-soluble polymer (component D) is at least one selected from polyglycidol, polyglycidol derivatives, polyglycerin, and polyglycerin derivatives, and has a hydroxyl value of 600 mgKOH/g or more and 850 mgKOH/g or less. Alternatively, the water-soluble polymer (component D) is a polishing liquid composition, wherein the water-soluble polymer (component D) is polydimethylvinylphosphonate .
上記式（ＩＩ）中、Ｒ6及びＲ7はそれぞれ独立して、水素原子、メチル基、フェニル基、ベンジル基、又はヘキシル基であり、Ｒ8及びＲ9はそれぞれ独立して、水素原子、炭素数が１～４のアルコキシ基、又はフェノキシ基であり、Ｘは、結合手、－ＣＨ2－、－Ｃ2Ｈ4－、又は－Ｐｈ－ＣＨ2－である。 Any of claims 1 to 3, wherein the water-soluble polymer other than polyethylene glycol (component D) contains at least one of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II). A polishing liquid composition according to claim 1.
In the above formula (II), R 6 and R 7 are each independently a hydrogen atom, a methyl group, a phenyl group, a benzyl group, or a hexyl group, and R 8 and R 9 are each independently a hydrogen atom, It is an alkoxy group or a phenoxy group having 1 to 4 carbon atoms, and X is a bond, -CH 2 -, -C 2 H 4 -, or -Ph-CH 2 -.
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