JP2016084428A - Polishing liquid composition - Google Patents
Polishing liquid composition Download PDFInfo
- Publication number
- JP2016084428A JP2016084428A JP2014218644A JP2014218644A JP2016084428A JP 2016084428 A JP2016084428 A JP 2016084428A JP 2014218644 A JP2014218644 A JP 2014218644A JP 2014218644 A JP2014218644 A JP 2014218644A JP 2016084428 A JP2016084428 A JP 2016084428A
- Authority
- JP
- Japan
- Prior art keywords
- polishing
- acid
- mass
- less
- composition according
- 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.)
- Granted
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- 238000005498 polishing Methods 0.000 title claims abstract description 322
- 239000000203 mixture Substances 0.000 title claims abstract description 139
- 239000007788 liquid Substances 0.000 title claims abstract description 67
- 239000000758 substrate Substances 0.000 claims abstract description 106
- 229920001577 copolymer Polymers 0.000 claims abstract description 52
- 150000003839 salts Chemical class 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 26
- 229910018104 Ni-P Inorganic materials 0.000 claims abstract description 20
- 229910018536 Ni—P Inorganic materials 0.000 claims abstract description 20
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 unsaturated sulfonic acid compound Chemical class 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 29
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 13
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 8
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 6
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 5
- HOWXFKMMBYLEOM-UHFFFAOYSA-N 4-(1-methylcyclohexa-2,4-dien-1-yl)-2h-triazole Chemical compound C=1NN=NC=1C1(C)CC=CC=C1 HOWXFKMMBYLEOM-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 claims description 3
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 claims description 3
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 claims description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 3
- RJWLLQWLBMJCFD-UHFFFAOYSA-N 4-methylpiperazin-1-amine Chemical compound CN1CCN(N)CC1 RJWLLQWLBMJCFD-UHFFFAOYSA-N 0.000 claims description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000005700 Putrescine Substances 0.000 claims description 3
- JCXKHYLLVKZPKE-UHFFFAOYSA-N benzotriazol-1-amine Chemical compound C1=CC=C2N(N)N=NC2=C1 JCXKHYLLVKZPKE-UHFFFAOYSA-N 0.000 claims description 3
- YYZVLEJDGSWXII-UHFFFAOYSA-N benzotriazol-2-amine Chemical compound C1=CC=CC2=NN(N)N=C21 YYZVLEJDGSWXII-UHFFFAOYSA-N 0.000 claims description 3
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 3
- 150000002390 heteroarenes Chemical class 0.000 claims description 3
- KYCGURZGBKFEQB-UHFFFAOYSA-N n',n'-dibutylpropane-1,3-diamine Chemical compound CCCCN(CCCC)CCCN KYCGURZGBKFEQB-UHFFFAOYSA-N 0.000 claims description 3
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 3
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 2
- RDTCWQXQLWFJGY-UHFFFAOYSA-N 1-(methylamino)butan-2-ol Chemical compound CCC(O)CNC RDTCWQXQLWFJGY-UHFFFAOYSA-N 0.000 claims 1
- 150000003852 triazoles Chemical class 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 35
- 238000005299 abrasion Methods 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 5
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical class O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 abstract 1
- 150000003457 sulfones Chemical class 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007800 oxidant agent Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- 230000003746 surface roughness Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 239000008119 colloidal silica Substances 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 159000000000 sodium salts Chemical class 0.000 description 7
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 238000007517 polishing process Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 150000003009 phosphonic acids Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000013585 weight reducing agent Substances 0.000 description 4
- IQEKRNXJPCBUAT-UHFFFAOYSA-N 2-[hydroperoxy(hydroxy)phosphoryl]acetic acid Chemical compound OOP(O)(=O)CC(O)=O IQEKRNXJPCBUAT-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical group 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical group 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical compound [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 description 2
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 2
- XYJVGUKOTPNESI-UHFFFAOYSA-N 2-[2-aminoethyl(methyl)amino]ethanol Chemical compound NCCN(C)CCO XYJVGUKOTPNESI-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 2
- 238000007518 final polishing process Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SFRLSTJPMFGBDP-UHFFFAOYSA-N 1,2-diphosphonoethylphosphonic acid Chemical compound OP(O)(=O)CC(P(O)(O)=O)P(O)(O)=O SFRLSTJPMFGBDP-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- INJFRROOFQOUGJ-UHFFFAOYSA-N 2-[hydroxy(methoxy)phosphoryl]butanedioic acid Chemical compound COP(O)(=O)C(C(O)=O)CC(O)=O INJFRROOFQOUGJ-UHFFFAOYSA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- OOOLSJAKRPYLSA-UHFFFAOYSA-N 2-ethyl-2-phosphonobutanedioic acid Chemical compound CCC(P(O)(O)=O)(C(O)=O)CC(O)=O OOOLSJAKRPYLSA-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- HXMVNCMPQGPRLN-UHFFFAOYSA-N 2-hydroxyputrescine Chemical compound NCCC(O)CN HXMVNCMPQGPRLN-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical class CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- 244000233967 Anethum sowa Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical class [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- GTTBQSNGUYHPNK-UHFFFAOYSA-N hydroxymethylphosphonic acid Chemical compound OCP(O)(O)=O GTTBQSNGUYHPNK-UHFFFAOYSA-N 0.000 description 1
- GEOVEUCEIQCBKH-UHFFFAOYSA-N hypoiodous acid Chemical compound IO GEOVEUCEIQCBKH-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- RGHXWDVNBYKJQH-UHFFFAOYSA-N nitroacetic acid Chemical compound OC(=O)C[N+]([O-])=O RGHXWDVNBYKJQH-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
本発明は、Ｎｉ−Ｐメッキされたアルミニウム合金基板用研磨液組成物、これを用いた磁気ディスク基板の研磨方法及び磁気ディスク基板の製造方法に関する。 The present invention relates to a Ni-P plated polishing composition for an aluminum alloy substrate, a magnetic disk substrate polishing method using the same, and a magnetic disk substrate manufacturing method.
近年、磁気ディスクドライブは小型化・大容量化が進み、高記録密度化が求められている。高記録密度化するために、単位記録面積を縮小し、弱くなった磁気信号の検出感度を向上するため、磁気ヘッドの浮上高さをより低くするための技術開発が進められている。磁気ディスク基板には、磁気ヘッドの低浮上化と記録面積の確保に対応するため、平滑性及び平坦性の向上（表面粗さ、うねり、端面ダレの低減）と欠陥低減（スクラッチ、突起、ピット等の低減）に対する要求が厳しくなっている。 In recent years, magnetic disk drives have been reduced in size and capacity, and high recording density has been demanded. In order to increase the recording density, the unit recording area is reduced, and in order to improve the detection sensitivity of the weakened magnetic signal, technological development for lowering the flying height of the magnetic head has been advanced. Magnetic disk substrates have improved smoothness and flatness (reduced surface roughness, waviness and edge sag) and reduced defects (scratches, protrusions, pits) to reduce the flying height of the magnetic head and secure a recording area. Etc.) is becoming stricter.
磁気ディスク基板の研磨に用いる研磨パッドの劣化を及びそれにともなううねりの発生を抑制することを目的として、特許文献１は、所定のアミン化合物からなるパッド劣化抑制剤を含有する研磨液組成物を開示する。 Patent Document 1 discloses a polishing liquid composition containing a pad deterioration inhibitor made of a predetermined amine compound for the purpose of suppressing the deterioration of a polishing pad used for polishing a magnetic disk substrate and the generation of waviness associated therewith. To do.
一方、磁気ディスク基板の研磨とは要求特性が異なる半導体デバイスのＣＭＰ加工プロセスにおいては、銅膜、タンタル化合物のバリア層、及びＳｉＯ2の絶縁層を研磨除去するための研磨用組成物が開示されている。特許文献２は、（ａ）スルホン酸（塩）基を有する単量体、カルボン酸（塩）基を有する単量体、水酸基を有する単量体、エチレンオキサイドもしくはプロピレンオキサイドに由来する骨格を有する単量体、および窒素原子を有する単量体の群から選ばれた少なくとも１種の単量体、ならびに、（ｂ）ビニルホスホン酸（塩）、からなる単量体成分を共重合してなる共重合体（塩）を主成分とする半導体部品用洗浄剤を開示する。 On the other hand, a polishing composition for polishing and removing a copper film, a barrier layer of a tantalum compound, and an insulating layer of SiO 2 is disclosed in a CMP processing process of a semiconductor device having different characteristics from polishing of a magnetic disk substrate. ing. Patent Document 2 has (a) a monomer having a sulfonic acid (salt) group, a monomer having a carboxylic acid (salt) group, a monomer having a hydroxyl group, a skeleton derived from ethylene oxide or propylene oxide. A monomer component comprising at least one monomer selected from the group consisting of a monomer and a monomer having a nitrogen atom, and (b) vinylphosphonic acid (salt); Disclosed is a cleaning agent for semiconductor parts, the main component of which is a copolymer (salt).
磁気ディスク基板の研磨では、しばしば、経時的に研磨パッドが摩耗して変形し、研磨後の基板表面の品質が低下することがあることが見出された。具体的には、ポリウレタン製の研磨パッドの開口径が拡大し、研磨後の基板表面の短波長うねりが増大することが見出された。 It has been found that in polishing a magnetic disk substrate, the polishing pad often wears and deforms over time, and the quality of the substrate surface after polishing may be degraded. Specifically, it has been found that the opening diameter of the polishing pad made of polyurethane is enlarged, and the short wavelength waviness of the substrate surface after polishing is increased.
そこで、本発明は、一又は複数の実施形態において、研磨速度の低下並びに研磨後の基板表面のスクラッチ及びナノ突起欠陥の悪化を起こすことなく、研磨パッドの摩耗を抑制できる磁気ディスク基板用研磨液組成物、及びこれを用いた磁気ディスク基板の製造方法を提供する。 Therefore, in one or a plurality of embodiments, the present invention provides a polishing liquid for a magnetic disk substrate capable of suppressing polishing pad wear without causing a reduction in polishing rate and a deterioration in scratches and nanoprotrusion defects on the substrate surface after polishing. A composition and a method for producing a magnetic disk substrate using the composition are provided.
本発明は、一又は複数の実施形態において、シリカ粒子と、酸と、（メタ）アクリル酸又はその塩に由来する構成単位及びヒドロキシ基を有するエチレン性不飽和スルホン酸化合物又はその塩に由来する構成単位を有する共重合体とを含む、Ｎｉ−Ｐメッキされたアルミニウム合金基板用の研磨液組成物（以下、「本開示に係る研磨液組成物」ともいう。）に関する。 In one or a plurality of embodiments, the present invention is derived from a silica particle, an acid, a structural unit derived from (meth) acrylic acid or a salt thereof, and an ethylenically unsaturated sulfonic acid compound having a hydroxy group or a salt thereof. The present invention relates to a polishing liquid composition for an Ni-P plated aluminum alloy substrate (hereinafter also referred to as “polishing liquid composition according to the present disclosure”) including a copolymer having a structural unit.
また、本発明は、一又は複数の実施形態において、本開示に係る研磨液組成物を用いてＮｉ−Ｐメッキされたアルミニウム合金基板を研磨する工程を有する磁気ディスク基板の製造方法に関し、或いは、本開示に係る研磨液組成物を用いてＮｉ−Ｐメッキされたアルミニウム合金基板を研磨することを含む磁気ディスク基板の研磨方法に関する。 In one or a plurality of embodiments, the present invention relates to a method of manufacturing a magnetic disk substrate including a step of polishing a Ni-P plated aluminum alloy substrate using the polishing composition according to the present disclosure, or The present invention relates to a method for polishing a magnetic disk substrate, including polishing a Ni-P plated aluminum alloy substrate using a polishing liquid composition according to the present disclosure.
本開示に係る研磨液組成物によれば、一又は複数の実施形態において、研磨速度を大きく損なうことなく、かつ、研磨後の基板表面のスクラッチ数及びナノ突起欠陥数の増大を抑制しつつ、研磨パッドの摩耗を抑制できるという効果が奏されうる。 According to the polishing composition according to the present disclosure, in one or a plurality of embodiments, without significantly reducing the polishing rate, and while suppressing the increase in the number of scratches and nanoprojection defects on the substrate surface after polishing, The effect that the abrasion of the polishing pad can be suppressed can be exhibited.
本開示は、一又は複数の実施形態において、磁気ディスク基板の研磨に、ＡＡ／ＡＭＰＳ共重合体を含有する研磨液組成物とともにポリウレタン製のスエードタイプの研磨パッドを使用すると、該研磨パッドの摩耗が発生する場合があるという問題点の知見に起因する。本開示は、一又は複数の実施形態において、該研磨パッドの摩耗が、研磨液組成物の研磨パッドに対する表面張力を制御することで抑制されうるという知見に基づく。 In one or a plurality of embodiments of the present disclosure, when a suede type polishing pad made of polyurethane is used together with a polishing liquid composition containing an AA / AMPS copolymer for polishing a magnetic disk substrate, the wear of the polishing pad is reduced. This is due to the knowledge of the problem that this may occur. The present disclosure is based on the finding that, in one or a plurality of embodiments, the abrasion of the polishing pad can be suppressed by controlling the surface tension of the polishing composition with respect to the polishing pad.
すなわち、該研磨パッドの摩耗は、研磨液組成物が研磨液パッドに浸透しすぎてしまい、研磨パットと被研磨基板との間における研磨液組成物が枯渇することが原因の一つであるという知見が得られた。そして、研磨液組成物に添加する該共重合体の構成単位にヒドロキシ基を導入することで研磨パッドに対する研磨液組成物の表面張力が高くなるように制御でき、これにより、研磨パッドの摩耗が抑制されると推定される。但し、本発明はこのメカニズムに限定されなくてもよい。 That is, the abrasion of the polishing pad is one of the causes that the polishing liquid composition permeates the polishing liquid pad too much and the polishing liquid composition between the polishing pad and the substrate to be polished is depleted. Knowledge was obtained. And by introducing a hydroxy group into the constituent unit of the copolymer to be added to the polishing liquid composition, it is possible to control the surface tension of the polishing liquid composition with respect to the polishing pad to be high, thereby reducing the abrasion of the polishing pad. Presumed to be suppressed. However, the present invention need not be limited to this mechanism.
なお、本開示において、研磨パッドの摩耗は、一又は複数の実施形態において、研磨パッドの変形であり、さらなる一又は複数の実施形態において、研磨パッドの開口径の変化、及び／又は、研磨パッドの表面粗さの変化をいう。 In the present disclosure, the abrasion of the polishing pad is a deformation of the polishing pad in one or a plurality of embodiments, and in one or more embodiments, the change in the opening diameter of the polishing pad and / or the polishing pad is performed. This is the change in surface roughness.
［共重合体］
本開示に係る研磨液組成物は、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、（メタ）アクリル酸又はその塩に由来する構成単位（Ａ）、及び、ヒドロキシ基を有するエチレン性不飽和スルホン酸化合物又はその塩に由来する構成単位（Ｂ）を有する共重合体（以下、「本開示に係る共重合体」ともいう）を含有する。本開示に係る共重合体は、水溶性であって、本開示に係る研磨液組成物に溶解する。
[Copolymer]
The polishing liquid composition according to the present disclosure is a (meth) acrylic acid or a salt thereof from the viewpoint of reducing scratches and nano-defects on the polished surface after polishing without impairing the polishing rate and suppressing abrasion of the polishing pad. And a copolymer having a structural unit (A) derived from an ethylenically unsaturated sulfonic acid compound having a hydroxy group or a salt thereof (hereinafter referred to as “copolymer according to the present disclosure”). (Also called). The copolymer according to the present disclosure is water-soluble and dissolves in the polishing liquid composition according to the present disclosure.
本開示において、（メタ）アクリル酸及びスルホン酸化合物が塩を形成する場合、及び／又は、本開示に係る共重合体が塩を形成する場合、特に限定はなく、具体的には、金属、アンモニウム、アルキルアンモニウム等との塩が挙げられる。金属の具体例としては、周期律表（長周期型）１Ａ、１Ｂ、２Ａ、２Ｂ、３Ａ、３Ｂ、４Ａ、６Ａ、７Ａ又は８族に属する金属等が挙げられる。これらの金属の中でも、ナノスクラッチ低減の観点から１Ａ、３Ｂ、又は８族に属する金属が好ましく、１Ａ族に属するナトリウム及びカリウムがより好ましい。アルキルアンモニウムの具体例としては、テトラメチルアンモニウム、テトラエチルアンモニウム、テトラブチルアンモニウム等が挙げられる。これらの中では、アンモニウム塩、ナトリウム塩及びカリウム塩がより好ましい。 In the present disclosure, when the (meth) acrylic acid and the sulfonic acid compound form a salt and / or when the copolymer according to the present disclosure forms a salt, there is no particular limitation, specifically, a metal, And salts with ammonium, alkylammonium and the like. Specific examples of the metal include metals belonging to the periodic table (long period type) 1A, 1B, 2A, 2B, 3A, 3B, 4A, 6A, 7A, or Group 8. Among these metals, metals belonging to Group 1A, 3B, or Group 8 are preferable from the viewpoint of reducing nanoscratches, and sodium and potassium belonging to Group 1A are more preferable. Specific examples of alkylammonium include tetramethylammonium, tetraethylammonium, tetrabutylammonium and the like. Among these, ammonium salts, sodium salts, and potassium salts are more preferable.
なお、本開示に係る共重合体における構成単位（Ａ）及び（Ｂ）の重合は、ランダム、ブロック、又はグラフトのいずれでもよい。また、構成単位（Ａ）及び（Ｂ）は、それぞれ、１種類から構成されてもよく、複数種類から構成されてもよい。 The polymerization of the structural units (A) and (B) in the copolymer according to the present disclosure may be random, block, or graft. Each of the structural units (A) and (B) may be composed of one type or a plurality of types.
［構成単位（Ａ）］
本開示に係る共重合体の構成単位（Ａ）は、（メタ）アクリル酸又はその塩に由来する構成単位であって、メタクリル酸、アクリル酸、及びこれらの塩から選択される一種類又は複数種類に由来する構成単位である。構成単位（Ａ）は、一又は複数の実施形態において、下記一般式（Ｉ）で表すことができる。
[Structural unit (A)]
The structural unit (A) of the copolymer according to the present disclosure is a structural unit derived from (meth) acrylic acid or a salt thereof, and one or more selected from methacrylic acid, acrylic acid, and salts thereof A structural unit derived from a type. In one or more embodiments, the structural unit (A) can be represented by the following general formula (I).
［構成単位（Ｂ）］
本開示に係る共重合体の構成単位（Ｂ）は、ヒドロキシ基を有するエチレン性不飽和スルホン酸化合物又はその塩に由来する構成単位である。ポリウレタン製の研磨パッドは通常疎水的であるため、共重合体がヒドロキシ基を含有することにより、研磨液組成物の研磨パッドに対する表面張力が高くなるように制御することができる。
[Structural unit (B)]
The structural unit (B) of the copolymer according to the present disclosure is a structural unit derived from an ethylenically unsaturated sulfonic acid compound having a hydroxy group or a salt thereof. Since a polyurethane polishing pad is usually hydrophobic, the surface tension of the polishing composition with respect to the polishing pad can be controlled to be high when the copolymer contains a hydroxy group.
構成単位（Ｂ）におけるヒドロキシ基の数若しくは平均数は、一又は複数の実施形態において、１〜４、１〜３、１〜２、又は１である。 The number or average number of hydroxy groups in the structural unit (B) is 1 to 4, 1 to 3, 1 to 2, or 1 in one or more embodiments.
構成単位（Ｂ）は、一又は複数の実施形態において、下記一般式（ＩＩ）で表すことができる。 The structural unit (B) can be represented by the following general formula (II) in one or more embodiments.
構成単位（Ｂ）は、一又は複数の実施形態において、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、３−アリロキシ−２−ヒドキシプロパンスルホン酸（ＨＡＰＳ）又はその塩に由来する構成単位であることが好ましい。 In one or more embodiments, the structural unit (B) is 3-allyloxy from the viewpoint of reducing scratches and nano-defects on the polished surface after polishing without impairing the polishing rate and suppressing abrasion of the polishing pad. It is preferably a structural unit derived from 2-hydroxypropanesulfonic acid (HAPS) or a salt thereof.
本開示に係る共重合体は、一又は複数の実施形態において、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、下記式（Ｉ）で表される構成単位（Ａ）、及び、下記式（ＩＩＩ）で表される構成単位（Ｂ）を有する共重合体であることが好ましい。
本開示に係る共重合体を構成する構成単位（Ａ）及び（Ｂ）の合計に対する構成単位（Ｂ）の割合は、一又は複数の実施形態において、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、１５モル％以上が好ましく、より好ましくは２０モル％以上、更に好ましくは３０モル％以上であり、同様の観点から、７０モル％以下が好ましく、より好ましくは６０モル％以下、更に好ましくは５０モル％以下であり、同様の観点から、好ましくは１５モル％以上７０モル％以下、より好ましくは２０モル％以上６０モル以下、更に好ましくは３０モル％以上５０モル％以下である。 The ratio of the structural unit (B) to the total of the structural units (A) and (B) constituting the copolymer according to the present disclosure is the polished surface after polishing without impairing the polishing rate in one or a plurality of embodiments. From the viewpoint of reducing scratches and nano-defects and suppressing abrasion of the polishing pad, it is preferably at least 15 mol%, more preferably at least 20 mol%, still more preferably at least 30 mol%, from the same viewpoint. 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less, and from the same viewpoint, preferably 15 mol% or more and 70 mol% or less, more preferably 20 mol% or more and 60 mol% or less. It is 30 mol% or less, More preferably, it is 30 mol% or more and 50 mol% or less.
本開示に係る共重合体を構成する全構成単位中に占める構成単位（Ａ）及び（Ｂ）の合計構成単位の含有率は、一又は複数の実施形態において、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、８０モル％以上が好ましく、より好ましくは９０モル％以上、更に好ましくは９５モル％以上、更により好ましくは実質的に１００モル％である。 The content of the total structural unit of the structural units (A) and (B) in all the structural units constituting the copolymer according to the present disclosure is after polishing without impairing the polishing rate in one or more embodiments. From the viewpoint of reducing scratches and nano-defects on the polishing surface and suppressing abrasion of the polishing pad, it is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and even more preferably. Is substantially 100 mol%.
[共重合体の重量平均分子量]
本重合体に係る共重合体の重量平均分子量は、一又は複数の実施形態において、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、５，０００以上５０，０００以下であることが好ましく、より好ましくは６０００以上４０００００以下、更に好ましくは７０００以上３０００００以下、より更に好ましくは１００００以上２００００以下である。該重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて実施例に記載の方法により測定した値である。
[Weight average molecular weight of copolymer]
The weight average molecular weight of the copolymer according to the present polymer, in one or a plurality of embodiments, reduces scratches and nano defects on the polished surface without impairing the polishing rate, and suppresses abrasion of the polishing pad. From this viewpoint, it is preferably 5,000 or more and 50,000 or less, more preferably 6000 or more and 400,000 or less, still more preferably 7000 or more and 300,000 or less, and still more preferably 10,000 or more and 20,000 or less. The weight average molecular weight is a value measured by the method described in Examples using gel permeation chromatography (GPC).
［共重合体の含有量］
本開示に係る研磨液組成物における本開示に係る共重合体の含有量は、一又は複数の実施形態において、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、０．００１質量％以上１質量％以下が好ましく、より好ましくは０．００５質量％以上０．５質量％以下、更に好ましくは０．０１質量％以上０．２質量％以下、更により好ましくは０．０１質量％以上０．１質量％以下、更により好ましくは０．０１質量％以上０．０７５質量％以下である。
[Content of copolymer]
In one or a plurality of embodiments, the content of the copolymer according to the present disclosure in the polishing liquid composition according to the present disclosure reduces scratches and nano defects on the polished surface without impairing the polishing rate, and From the viewpoint of suppressing abrasion of the polishing pad, the content is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.005% by mass or more and 0.5% by mass or less, and still more preferably 0.01% by mass or more and 0% by mass. .2% by mass or less, still more preferably 0.01% by mass or more and 0.1% by mass or less, and still more preferably 0.01% by mass or more and 0.075% by mass or less.
また、本開示に係る研磨液組成物における、シリカ粒子と本開示に係る共重合体との含有量比［シリカ粒子の含有量（質量％）／共重合体の含有量（質量％）］は、一又は複数の実施形態において、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、５以上５０００以下が好ましく、１０以上１５００以下がより好ましく、２５以上７５０以下が更に好ましい。 Further, in the polishing composition according to the present disclosure, the content ratio of the silica particles and the copolymer according to the present disclosure [content of silica particles (mass%) / content of copolymer (mass%)] is In one or a plurality of embodiments, from the viewpoint of reducing scratches and nano defects on the polished surface after polishing without impairing the polishing rate and suppressing abrasion of the polishing pad, preferably 5 or more and 5000 or less. 1500 or less is more preferable, and 25 or more and 750 or less are more preferable.
さらに、本開示に係る研磨液組成物が複素環芳香族化合物（後述）を含有する場合、複素環芳香族化合物と本開示に係る共重合体との含有量比［複素環芳香族化合物の含有量（質量％）／共重合体の含有量（質量％）］は、一又は複数の実施形態において、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、０．１以上３００以下が好ましく、１以上１００以下がより好ましく、２以上２５以下が更に好ましい。 Further, when the polishing liquid composition according to the present disclosure contains a heterocyclic aromatic compound (described later), the content ratio of the heterocyclic aromatic compound to the copolymer according to the present disclosure [containing the heterocyclic aromatic compound] Amount (mass%) / content of copolymer (mass%)] reduces the scratches and nano-defects on the polished surface after polishing without impairing the polishing rate in one or more embodiments, and polishing. From the viewpoint of suppressing pad wear, it is preferably 0.1 or more and 300 or less, more preferably 1 or more and 100 or less, and even more preferably 2 or more and 25 or less.
さらに、本開示に係る研磨液組成物が脂肪族ジアミン又は脂環式ジアミン化合物（後述）を含有する場合、脂肪族ジアミン又は脂環式ジアミン化合物と本開示に係る共重合体との含有量比［脂肪族ジアミン又は脂環式ジアミン化合物の含有量（質量％）／共重合体の含有量（質量％）］は、一又は複数の実施形態において、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、０．１以上１００以下が好ましく、０．２５以上５０以下がより好ましく０．５、以１０上以下が更に好ましい。なお、本開示に係る研磨液組成物が脂肪族ジアミン及び脂環式ジアミン化合物を含有する場合、「脂肪族ジアミン又は脂環式ジアミン化合物の含有量」は、脂肪族ジアミン及び脂環式ジアミン化合物の合計の含有量となる（以下同様）。 Furthermore, when the polishing liquid composition according to the present disclosure contains an aliphatic diamine or an alicyclic diamine compound (described later), the content ratio between the aliphatic diamine or the alicyclic diamine compound and the copolymer according to the present disclosure. [Content of aliphatic diamine or cycloaliphatic diamine compound (% by mass) / content of copolymer (% by mass)] is a polished surface after polishing without impairing the polishing rate in one or more embodiments. From the viewpoint of reducing scratches and nano-defects and suppressing abrasion of the polishing pad, it is preferably 0.1 or more and 100 or less, more preferably 0.25 or more and 50 or less, and even more preferably 0.5 or more and 10 or less. . When the polishing composition according to the present disclosure contains an aliphatic diamine and an alicyclic diamine compound, “content of aliphatic diamine or alicyclic diamine compound” means an aliphatic diamine and an alicyclic diamine compound. (The same applies hereinafter).
［シリカ粒子］
本発明の研磨液組成物は、研磨材（砥粒）としてシリカ粒子を含有する。シリカ粒子としては、一又は複数の実施形態において、コロイダルシリカ、ヒュームドシリカ、表面修飾したシリカ等が挙げられるが、研磨後の基板のスクラッチ及びナノ突起欠陥の低減の観点から、コロイダルシリカが好ましい。コロイダルシリカは、１種類からなるものであっても、２種類以上のコロイダルシリカを混合したものであってもよい。
[Silica particles]
The polishing composition of the present invention contains silica particles as an abrasive (abrasive grains). Examples of the silica particles include colloidal silica, fumed silica, and surface-modified silica in one or a plurality of embodiments, but colloidal silica is preferable from the viewpoint of reducing scratches on the substrate after polishing and nanoprotrusion defects. . The colloidal silica may be composed of one type or a mixture of two or more types of colloidal silica.
研磨液組成物におけるシリカ粒子の含有量は、一又は複数の実施形態において、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、研磨材の含有量は、０．５質量％以上２０質量％以下が好ましく、１質量％以上１５質量％以下がより好ましく、３質量％以上１３質量％以下が更に好ましく、４質量％以上１０質量％以下が更により好ましい。 In one or a plurality of embodiments, the content of the silica particles in the polishing composition is a viewpoint that reduces scratches and nano defects on the polished surface without impairing the polishing rate, and suppresses abrasion of the polishing pad. Therefore, the content of the abrasive is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, further preferably 3% by mass or more and 13% by mass or less, and more preferably 4% by mass or more. 10 mass% or less is still more preferable.
［研磨材の平均粒径］
本開示における「研磨材の平均粒径」とは、特に言及しない限り、動的光散乱法において検出角９０°で測定される散乱強度分布に基づく平均粒径をいう（以下、「散乱強度分布に基づく平均粒径」ともいう）。研磨材の平均粒径は、研磨後の基板表面のスクラッチを低減する観点から、１ｎｍ以上４０ｎｍ以下が好ましく、より好ましくは５ｎｍ以上３７ｎｍ以下、さらに好ましくは１０ｎｍ以上３５ｎｍ以下である。なお、研磨材の平均粒径は、具体的には実施例に記載の方法により求めることができる。
[Average particle size of abrasive]
The “average particle diameter of the abrasive” in the present disclosure refers to an average particle diameter based on a scattering intensity distribution measured at a detection angle of 90 ° in the dynamic light scattering method (hereinafter referred to as “scattering intensity distribution” unless otherwise specified). Also referred to as “average particle size based on”). The average particle size of the abrasive is preferably from 1 nm to 40 nm, more preferably from 5 nm to 37 nm, and even more preferably from 10 nm to 35 nm, from the viewpoint of reducing scratches on the substrate surface after polishing. The average particle size of the abrasive can be specifically obtained by the method described in the examples.
［酸］
本開示に係る研磨液組成物は、酸を含有する。本開示において、酸の使用は、酸及び又はその塩の使用を含む。酸としては、研磨速度の向上の観点から、その酸のｐＫ１が２以下の化合物が好ましく、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、好ましくはｐＫ１が１．５以下、より好ましくは１以下、更に好ましくはｐＫ１で表せない程の強い酸性を示す化合物である。好ましい酸は、硝酸、硫酸、亜硫酸、過硫酸、塩酸、過塩素酸、リン酸、ホスホン酸、ホスフィン酸、ピロリン酸、トリポリリン酸、アミド硫酸等の無機酸、２−アミノエチルホスホン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、アミノトリ（メチレンホスホン酸）、ヒドロキシホスホノ酢酸、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、エタン−１，１，−ジホスホン酸、エタン−１，１，２−トリホスホン酸、エタン−１−ヒドロキシ−１，１−ジホスホン酸、エタン−１−ヒドロキシ−１，１，２−トリホスホン酸、エタン−１，２−ジカルボキシ−１，２−ジホスホン酸、メタンヒドロキシホスホン酸、２−ホスホノブタン−１，２−ジカルボン酸、１−ホスホノブタン−２，３，４−トリカルボン酸、α−メチルホスホノコハク酸等の有機ホスホン酸、グルタミン酸、ピコリン酸、アスパラギン酸等のアミノカルボン酸、クエン酸、酒石酸、シュウ酸、ニトロ酢酸、マレイン酸、オキサロ酢酸等のカルボン酸等が挙げられる。中でも、スクラッチ低減の観点から、無機酸、カルボン酸、有機ホスホン酸が好ましく、酸化剤の安定性向上及び廃液処理性向上の観点から、無機酸、有機ホスホン酸がより好ましい。また、無機酸の中では、硝酸、硫酸、塩酸、過塩素酸がより好ましく、リン酸、硫酸が更に好ましい。カルボン酸の中では、クエン酸、酒石酸、マレイン酸がより好ましく、クエン酸が更に好ましい。有機ホスホン酸の中では、１−ヒドロキシエチリデン−１，１−ジホスホン酸、アミノトリ（メチレンホスホン酸）、ヒドロキシホスホノ酢酸、エチレンジアミンテトラ（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）及びそれらの塩がより好ましく、１−ヒドロキシエチリデン−１，１−ジホスホン酸、アミノトリ（メチレンホスホン酸）、ヒドロキシホスホノ酢酸が更に好ましい。これらの酸及びその塩は単独で又は２種以上を混合して用いてもよいが、研磨速度の向上、ナノ突起低減及び基板の洗浄性向上の観点から、２種以上を混合して用いることが好ましく、ナノ突起低減、スクラッチ低減、酸化剤の安定性向上及び廃液処理性向上の観点から、リン酸、硫酸、クエン酸及び１−ヒドロキシエチリデン−１，１−ジホスホン酸からなる群から選択される２種以上の酸を混合して用いることが更に好ましい。ここで、ｐＫ１とは有機化合物又は無機化合物の第一酸解離定数（２５℃）の逆数の対数値である。各化合物のｐＫ１は例えば改訂４版化学便覧（基礎編）ＩＩ、ｐｐ３１６−３２５（日本化学会編）等に記載されている。
[acid]
The polishing liquid composition according to the present disclosure contains an acid. In the present disclosure, the use of an acid includes the use of an acid and / or a salt thereof. The acid is preferably a compound having a pK1 of 2 or less from the viewpoint of improving the polishing rate, and preferably has a pK1 of 1.5 or less from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing. More preferably, it is 1 or less, and still more preferably a compound exhibiting strong acidity that cannot be expressed by pK1. Preferred acids are inorganic acids such as nitric acid, sulfuric acid, sulfurous acid, persulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, tripolyphosphoric acid, amidosulfuric acid, 2-aminoethylphosphonic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), hydroxyphosphonoacetic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), ethane-1,1, -diphosphonic acid, ethane- 1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2- Diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phospho Organic phosphonic acids such as honobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, aminocarboxylic acids such as glutamic acid, picolinic acid, aspartic acid, citric acid, tartaric acid, oxalic acid, nitroacetic acid, maleic acid And carboxylic acids such as oxaloacetic acid. Among these, inorganic acids, carboxylic acids, and organic phosphonic acids are preferable from the viewpoint of reducing scratches, and inorganic acids and organic phosphonic acids are more preferable from the viewpoint of improving the stability of the oxidizing agent and improving the waste liquid processability. Among inorganic acids, nitric acid, sulfuric acid, hydrochloric acid, and perchloric acid are more preferable, and phosphoric acid and sulfuric acid are more preferable. Among carboxylic acids, citric acid, tartaric acid, and maleic acid are more preferable, and citric acid is more preferable. Among organic phosphonic acids, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), hydroxyphosphonoacetic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and their salts 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), and hydroxyphosphonoacetic acid are more preferable. These acids and salts thereof may be used alone or in combination of two or more, but from the viewpoint of improving the polishing rate, reducing nanoprotrusions and improving the cleaning property of the substrate, use two or more in combination. Preferably selected from the group consisting of phosphoric acid, sulfuric acid, citric acid, and 1-hydroxyethylidene-1,1-diphosphonic acid from the viewpoints of reducing nanoprotrusions, reducing scratches, improving the stability of oxidizing agents, and improving waste liquid treatment properties. It is more preferable to use a mixture of two or more acids. Here, pK1 is a logarithmic value of the reciprocal of the first acid dissociation constant (25 ° C.) of the organic compound or inorganic compound. The pK1 of each compound is described in, for example, the revised 4th edition, Chemical Handbook (Basic Edition) II, pp316-325 (Edited by Chemical Society of Japan).
これらの酸の塩を用いる場合の対イオンとしては、特に限定はなく、具体的には、金属、アンモニウム、アルキルアンモニウム等のイオンが挙げられる。上記金属の具体例としては、周期律表（長周期型）１Ａ、１Ｂ、２Ａ、２Ｂ、３Ａ、３Ｂ、４Ａ、６Ａ、７Ａ又は８族に属する金属が挙げられる。これらの中でも、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から１Ａ族に属する金属又はアンモニウムとの塩が好ましい。 There are no particular limitations on the counter ion when these acid salts are used, and specific examples include ions of metals, ammonium, alkylammonium, and the like. Specific examples of the metal include metals belonging to the periodic table (long-period type) 1A, 1B, 2A, 2B, 3A, 3B, 4A, 6A, 7A, or Group 8. Among these, from the viewpoint of reducing scratches on the substrate surface after polishing and nanoprotrusion defects, salts belonging to Group 1A metals or ammonium are preferable.
研磨液組成物における前記酸及びその塩の含有量は、研磨速度向上、並びに研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、０．００１質量％以上５質量％以下が好ましく、より好ましくは０．０１質量％以上４質量％以下であり、更に好ましくは０．０５質量％以上３質量％以下、更により好ましくは０．１質量％以上２．０質量％以下である。 The content of the acid and the salt thereof in the polishing composition is preferably 0.001% by mass or more and 5% by mass or less from the viewpoint of improving the polishing rate and reducing scratches and nanoprotrusion defects on the substrate surface after polishing. More preferably, it is 0.01 mass% or more and 4 mass% or less, More preferably, it is 0.05 mass% or more and 3 mass% or less, More preferably, it is 0.1 mass% or more and 2.0 mass% or less.
［酸化剤］
本開示に係る研磨液組成物は、酸化剤を含んでもよい。本酸化剤としては、研磨速度向上、並びに研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、過酸化物、過マンガン酸又はその塩、クロム酸又はその塩、ペルオキソ酸又はその塩、酸素酸又はその塩、金属塩類、硝酸類、硫酸類等が挙げられる。
[Oxidant]
The polishing liquid composition according to the present disclosure may include an oxidizing agent. The oxidizing agent includes peroxide, permanganic acid or a salt thereof, chromic acid or a salt thereof, peroxo acid or a salt thereof from the viewpoint of improving the polishing rate and reducing scratches and nanoprotrusion defects on the substrate surface after polishing. Oxygen acids or salts thereof, metal salts, nitric acids, sulfuric acids and the like.
前記過酸化物としては、過酸化水素、過酸化ナトリウム、過酸化バリウム等が挙げられ、過マンガン酸又はその塩としては、過マンガン酸カリウム等が挙げられ、クロム酸又はその塩としては、クロム酸金属塩、重クロム酸金属塩等が挙げられ、ペルオキソ酸又はその塩としては、ペルオキソ二硫酸、ペルオキソ二硫酸アンモニウム、ペルオキソ二硫酸金属塩、ペルオキソリン酸、ペルオキソ硫酸、ペルオキソホウ酸ナトリウム、過ギ酸、過酢酸、過安息香酸、過フタル酸等が挙げられ、酸素酸又はその塩としては、次亜塩素酸、次亜臭素酸、次亜ヨウ素酸、塩素酸、臭素酸、ヨウ素酸、次亜塩素酸ナトリウム、次亜塩素酸カルシウム等が挙げられ、金属塩類としては、塩化鉄（ＩＩＩ）、硝酸鉄（ＩＩＩ）、硫酸鉄（ＩＩＩ）、クエン酸鉄（ＩＩＩ）、硫酸アンモニウム鉄（ＩＩＩ）等が挙げられる。 Examples of the peroxide include hydrogen peroxide, sodium peroxide, barium peroxide, etc., examples of the permanganic acid or salt thereof include potassium permanganate, and examples of the chromic acid or salt thereof include chromium. Acid metal salts, metal dichromates, and the like. Peroxo acids or salts thereof include peroxodisulfuric acid, ammonium peroxodisulfate, peroxodisulfate metal salts, peroxophosphoric acid, peroxosulfuric acid, sodium peroxoborate, and performic acid. Peroxyacetic acid, perbenzoic acid, perphthalic acid, etc., and oxygen acids or salts thereof include hypochlorous acid, hypobromite, hypoiodous acid, chloric acid, bromic acid, iodic acid, hypochlorous acid. Examples include sodium chlorate, calcium hypochlorite, and metal salts include iron (III) chloride, iron (III) nitrate, iron (III) sulfate, and iron citrate. III), ammonium iron (III), and the like.
研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から好ましい酸化剤としては、過酸化水素、硝酸鉄（ＩＩＩ）、過酢酸、ペルオキソ二硫酸アンモニウム、硫酸鉄（ＩＩＩ）及び硫酸アンモニウム鉄（ＩＩＩ）等が挙げられる。より好ましい酸化剤としては、表面に金属イオンが付着せず汎用に使用され安価であるという観点から過酸化水素が挙げられる。これらの酸化剤は、単独で又は２種以上を混合して使用してもよい。 Preferable oxidizing agents from the viewpoint of reducing scratches on the substrate surface after polishing and nanoprotrusion defects include hydrogen peroxide, iron (III) nitrate, peracetic acid, ammonium peroxodisulfate, iron (III) sulfate, and iron (III) ammonium sulfate. Etc. As a more preferable oxidizing agent, hydrogen peroxide is mentioned from the viewpoint that metal ions do not adhere to the surface and are generally used and inexpensive. These oxidizing agents may be used alone or in admixture of two or more.
研磨液組成物における前記酸化剤の含有量は、研磨速度向上の観点から、０．００１質量％以上５質量％以下が好ましく、より好ましくは０．０１質量％以上４質量％以下であり、更に好ましくは０．０５質量％以上３質量％以下、更により好ましくは０．１質量％以上２．０質量％以下である。 The content of the oxidizing agent in the polishing liquid composition is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.01% by mass or more and 4% by mass or less, from the viewpoint of improving the polishing rate. Preferably they are 0.05 mass% or more and 3 mass% or less, More preferably, they are 0.1 mass% or more and 2.0 mass% or less.
［水］
本開示に係る研磨液組成物中の水は、媒体として使用されるものであり、蒸留水、イオン交換水、超純水等が挙げられる。被研磨基板の表面清浄性の観点からイオン交換水及び超純水が好ましく、超純水がより好ましい。研磨液組成物中の水の含有量は、６０質量％以上９９．４質量％以下が好ましく、７０質量％以上９８．９質量％以下がより好ましい。また、本開示に係る効果を阻害しない範囲内でアルコール等の有機溶剤を配合してもよい。
[water]
Water in the polishing composition according to the present disclosure is used as a medium, and examples thereof include distilled water, ion exchange water, and ultrapure water. From the viewpoint of the surface cleanliness of the substrate to be polished, ion exchange water and ultrapure water are preferable, and ultrapure water is more preferable. 60 mass% or more and 99.4 mass% or less are preferable, and, as for content of the water in polishing liquid composition, 70 mass% or more and 98.9 mass% or less are more preferable. Moreover, you may mix | blend organic solvents, such as alcohol, in the range which does not inhibit the effect which concerns on this indication.
［複素芳香族化合物］
本開示に係る研磨液組成物は、一又は複数の実施形態において、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、複素環芳香族化合物を含有してもよい。複素環芳香族化合物は、同様の観点から、複素環内に窒素原子を２個以上含む複素環芳香族化合物であり、複素環内に窒素原子を３個以上有することが好ましく、３〜９個がより好ましく、３〜５個が更に好ましく、３又は４個が更により好ましい。
[Heteroaromatic compounds]
In one or a plurality of embodiments, the polishing liquid composition according to the present disclosure may contain a heterocyclic aromatic compound from the viewpoint of reducing scratches on the substrate surface after polishing and reducing nanoprotrusion defects. From the same viewpoint, the heterocyclic aromatic compound is a heterocyclic aromatic compound containing 2 or more nitrogen atoms in the heterocyclic ring, and preferably has 3 or more nitrogen atoms in the heterocyclic ring. Is more preferable, 3 to 5 is more preferable, and 3 or 4 is still more preferable.
本開示に係る研磨液組成物に含有される複素環芳香族化合物は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、１，２，４−トリアゾール、３−アミノ−１，２，４−トリアゾール、５−アミノ−１，２，４−トリアゾール、３−メルカプト−１，２，４−トリアゾール、１Ｈ−テトラゾール、５−アミノテトラゾール、１Ｈ−ベンゾトリアゾール、１Ｈ−トリルトリアゾール、２−アミノベンゾトリアゾール、３−アミノベンゾトリアゾール、及び、こられのアルキル置換体若しくはアミン置換体、並びに、これらの組み合わせが好ましく、１Ｈ−テトラゾール、１Ｈ−ベンゾトリアゾール、１Ｈ−トリルトリアゾールがより好ましく、１Ｈ−テトラゾール、１Ｈ−ベンゾトリアゾールが更に好ましい。前記アルキル置換体のアルキル基としては例えば、炭素数１〜４の低級アルキル基が挙げられ、より具体的にはメチル基、エチル基が挙げられる。また、前記アミン置換体としては１−[Ｎ，Ｎ−ビス（ヒドロキシエチレン）アミノメチル]ベンゾトリアゾール、１−[Ｎ，Ｎ−ビス（ヒドロキシエチレン）アミノメチル]トリルトリアゾールが挙げられる。なお、プロトン化された複素環芳香族化合物のｐＫａは、例えば、『芳香族へテロ環化合物の化学』（坂本尚夫著、講談社サイエンティフィク）等に記載される。 The heterocyclic aromatic compound contained in the polishing liquid composition according to the present disclosure contains 1,2,4-triazole, 3-amino-1, from the viewpoint of reducing scratches on the substrate surface after polishing and reducing nanoprotrusion defects. 2,4-triazole, 5-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 1H-tetrazole, 5-aminotetrazole, 1H-benzotriazole, 1H-tolyltriazole, 2 -Aminobenzotriazole, 3-aminobenzotriazole, and these alkyl or amine substituents, and combinations thereof are preferred, 1H-tetrazole, 1H-benzotriazole, 1H-tolyltriazole are more preferred, and 1H More preferred are -tetrazole and 1H-benzotriazole. Examples of the alkyl group of the alkyl-substituted product include a lower alkyl group having 1 to 4 carbon atoms, and more specifically, a methyl group and an ethyl group. Examples of the amine-substituted product include 1- [N, N-bis (hydroxyethylene) aminomethyl] benzotriazole and 1- [N, N-bis (hydroxyethylene) aminomethyl] tolyltriazole. The pKa of the protonated heterocyclic aromatic compound is described in, for example, “Aromatic Heterocyclic Compound Chemistry” (Nao Sakamoto, Kodansha Scientific).
本開示に係る研磨液組成物における複素環芳香族化合物の含有量は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、研磨液組成物全体の質量に対して０．０１質量％以上１０質量％以下であることが好ましく、０．０５質量％以上５質量％以下がより好ましく、０．１質量％以上１質量％以下が更に好ましい。なお、研磨液組成物中の複素環芳香族化合物は１種類であってもよく、２種類以上であってもよい。 The content of the heterocyclic aromatic compound in the polishing liquid composition according to the present disclosure is 0.01 mass with respect to the total mass of the polishing liquid composition from the viewpoint of reducing scratches on the surface of the substrate after polishing and reducing nanoprotrusion defects. % To 10% by mass, more preferably 0.05% to 5% by mass, and still more preferably 0.1% to 1% by mass. In addition, the heterocyclic aromatic compound in the polishing composition may be one kind or two or more kinds.
また、研磨液組成物における、シリカ粒子と複素環芳香族化合物との含有量比［シリカ粒子の含有量（質量％）／複素環芳香族化合物の含有量（質量％）］は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、２以上１０００以下が好ましく、５以上２００以下がより好ましく、１０以上１００以下が更に好ましい。 Further, the content ratio of silica particles to the heterocyclic aromatic compound [content of silica particles (mass%) / heterocyclic aromatic compound content (mass%)] in the polishing composition is determined after polishing. From the viewpoint of reducing scratches on the substrate surface and nanoprotrusion defects, it is preferably 2 or more and 1000 or less, more preferably 5 or more and 200 or less, and still more preferably 10 or more and 100 or less.
［脂肪族ジアミン又は脂環式ジアミン化合物］
本開示に係る研磨液組成物は、一又は複数の実施形態において、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、脂肪族ジアミン化合物又は脂環式ジアミン化合物を含有してもよい。
[Aliphatic diamine or alicyclic diamine compound]
In one or a plurality of embodiments, the polishing liquid composition according to the present disclosure may contain an aliphatic diamine compound or an alicyclic diamine compound from the viewpoint of reducing scratches and nanoprotrusion defects on the substrate surface after polishing. Good.
脂肪族ジアミン化合物としては、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、エチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、１，２-ジアミノプロパン、１，３−ジアミノプロパン、１，４−ジアミノブタン、ヘキサメチレンジアミン、３−（ジエチルアミノ）プロピルアミン、３−（ジブチルアミノ）プロピルアミン、３−（メチルアミノ）プロピルアミン、３−（ジメチルアミノ）プロピルアミン、Ｎ−アミノエチルエタノールアミン、Ｎ−アミノエチルイソプロパノールアミン、Ｎ−アミノエチル−Ｎ−メチルエタノールアミン、及びこれらの組み合わせが好ましく、Ｎ−アミノエチルエタノールアミンがより好ましい。 Examples of the aliphatic diamine compound include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-diaminopropane, 1,3 from the viewpoint of reducing scratches on the substrate surface after polishing and reducing nanoprotrusion defects. -Diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 3- (diethylamino) propylamine, 3- (dibutylamino) propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, N-aminoethylethanolamine, N-aminoethylisopropanolamine, N-aminoethyl-N-methylethanolamine, and combinations thereof are preferred, and N-aminoethylethanolamine is more preferred.
脂環式ジアミン化合物は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、ピペラジン、２−メチルピペラジン、２、５−ジメチルピペラジン、１−アミノ−４−メチルピペラジン、Ｎ−メチルピペラジン、Ｎ−ヒドロキシエチルピペラジン、及びこれらの組み合わせが好ましく、Ｎ−ヒドロキシエチルピペラジンがより好ましい。 The alicyclic diamine compounds are piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 1-amino-4-methylpiperazine, N-methyl from the viewpoint of reducing scratches on the surface of the substrate after polishing and reducing nanoprotrusion defects. Piperazine, N-hydroxyethylpiperazine, and combinations thereof are preferred, and N-hydroxyethylpiperazine is more preferred.
本発明の研磨液組成物における脂肪族ジアミン又は脂環式ジアミン化合物の含有量は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、研磨液組成物全体の質量に対して０．００５質量％以上５質量％以下であることが好ましく、０．０１質量％以上２質量％以下がより好ましく、０．０２質量％以上１質量％以下が更に好ましい。 The content of the aliphatic diamine or alicyclic diamine compound in the polishing liquid composition of the present invention is 0 with respect to the total mass of the polishing liquid composition from the viewpoint of reducing scratches on the substrate surface after polishing and reducing nanoprotrusion defects. It is preferable that it is 0.005 mass% or more and 5 mass% or less, 0.01 mass% or more and 2 mass% or less are more preferable, and 0.02 mass% or more and 1 mass% or less are still more preferable.
また、研磨液組成物における、シリカ粒子と脂肪族ジアミン又は脂環式ジアミン化合物との含有量比［シリカ粒子の含有量（質量％）／脂肪族ジアミン又は脂環式ジアミン化合物の含有量（質量％）］は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、５以上１０００以下が好ましく、２５以上５００以下がより好ましく、５０以上２５０以下が更に好ましい。 Further, the content ratio of silica particles to aliphatic diamine or alicyclic diamine compound in the polishing composition [content of silica particles (mass%) / content of aliphatic diamine or alicyclic diamine compound (mass) %)] Is preferably 5 or more and 1000 or less, more preferably 25 or more and 500 or less, and even more preferably 50 or more and 250 or less, from the viewpoint of reducing scratches on the substrate surface after polishing and reducing nanoprotrusion defects.
さらに、研磨液組成物における、複素環芳香族化合物と脂肪族ジアミン又は脂環式ジアミン化合物との含有量比［複素環芳香族化合物の含有量（質量％）／脂肪族ジアミン又は脂環式ジアミン化合物の含有量（質量％）］は、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減の観点から、０．１以上５０以下が好ましく、０．５以上２５以下がより好ましく、１以上１０以下が更に好ましい。 Furthermore, the content ratio of the heterocyclic aromatic compound and the aliphatic diamine or alicyclic diamine compound in the polishing composition [content of heterocyclic aromatic compound (mass%) / aliphatic diamine or alicyclic diamine The content (% by mass) of the compound] is preferably 0.1 or more and 50 or less, more preferably 0.5 or more and 25 or less, and more preferably 1 or more and 10 from the viewpoint of reducing scratches on the substrate surface after polishing and reducing nanoprotrusion defects. The following is more preferable.
［その他の成分］
本開示に係る研磨液組成物には、必要に応じて他の成分を配合することができる。他の成分としては、増粘剤、分散剤、防錆剤、塩基性物質、界面活性剤等が挙げられる。研磨液組成物中のこれら他の任意成分の含有量は、０を超え１０質量％以下好ましく、０を超え５質量％以下がより好ましい。但し、本開示の研磨液組成物は、他の成分、とりわけ界面活性剤を含むことなく、研磨後の基板表面のスクラッチ及びナノ突起欠陥の低減効果を発揮し得る。さらに、本開示に係る研磨液組成物は、アルミナ砥粒を含ませることができ、最終研磨工程より前の粗研磨工程に使用することもできる。
[Other ingredients]
In the polishing composition according to the present disclosure, other components can be blended as necessary. Examples of other components include a thickener, a dispersant, a rust inhibitor, a basic substance, and a surfactant. The content of these other optional components in the polishing composition is more than 0 and preferably 10% by mass or less, more preferably more than 0 and 5% by mass or less. However, the polishing liquid composition of the present disclosure can exhibit the effect of reducing scratches and nanoprotrusion defects on the substrate surface after polishing without containing other components, particularly a surfactant. Furthermore, the polishing composition according to the present disclosure can contain alumina abrasive grains, and can also be used in a rough polishing step prior to the final polishing step.
［研磨液組成物のｐＨ］
本開示に係る研磨液組成物のｐＨは、一又は複数の実施形態において、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、０．５以上３．５以下が好ましく、より好ましくは０．８以上３．０以下、更に好ましくは１．０以上２．５以下、更により好ましくは１．２以上２．０以下である。本開示において、研磨液組成物のｐＨは、２５℃における値であって、ｐＨメータを用いて測定した値である。本開示における研磨液組成物のｐＨは、具体的には、実施例に記載の方法で測定できる。
[PH of polishing composition]
In one or a plurality of embodiments, the pH of the polishing composition according to the present disclosure is a viewpoint that reduces scratches and nano-defects on the polished surface after polishing without impairing the polishing rate, and suppresses abrasion of the polishing pad. From 0.5 to 3.5, preferably from 0.8 to 3.0, more preferably from 1.0 to 2.5, and even more preferably from 1.2 to 2.0. is there. In the present disclosure, the pH of the polishing composition is a value at 25 ° C. and is a value measured using a pH meter. Specifically, the pH of the polishing composition in the present disclosure can be measured by the method described in Examples.
［研磨液組成物の調製方法］
本開示に係る研磨液組成物は、例えば、シリカ粒子、酸、水、及び、本開示に係る共重合体、必要に応じて、酸化剤、複素環芳香族化合物、脂肪族ジアミン又は脂環式ジアミン化合物を、さらに所望により他の成分を含めて、公知の方法で混合することにより調製できる。この際、シリカ粒子は、濃縮されたスラリーの状態で混合されてもよいし、水等で希釈してから混合されてもよい。本開示に係る研磨液組成物における各成分の含有量や濃度は、上述した範囲であるが、その他の態様として、本発明の研磨液組成物を濃縮物として調製してもよい。
[Method for preparing polishing liquid composition]
The polishing liquid composition according to the present disclosure includes, for example, silica particles, acid, water, and a copolymer according to the present disclosure, as necessary, an oxidizing agent, a heterocyclic aromatic compound, an aliphatic diamine, or an alicyclic type. The diamine compound can be further prepared by mixing by a known method including other components as desired. At this time, the silica particles may be mixed in a concentrated slurry state, or may be mixed after being diluted with water or the like. The content and concentration of each component in the polishing liquid composition according to the present disclosure are in the above-described ranges, but as another aspect, the polishing liquid composition of the present invention may be prepared as a concentrate.
［研磨対象（被研磨基板）］
本開示に係る研磨液組成物が研磨の対象とする被研磨基板は、Ｎｉ−Ｐメッキされたアルミニウム合金基板である。「Ｎｉ−Ｐメッキされたアルミニウム合金基板」とは、一又は複数の実施形態において、磁気ディスク基板用アルミニウム合金板材の表面を研削後、無電解Ｎｉ−Ｐメッキ処理したものをいう。Ｎｉ−Ｐメッキされたアルミニウム合金基板の表面を研磨し、さらに、スパッタ等でその基板表面に磁性膜を形成することにより磁気ディスク基板を製造することができる。
[Polishing target (substrate to be polished)]
The substrate to be polished by the polishing composition according to the present disclosure is a Ni-P plated aluminum alloy substrate. The “Ni—P plated aluminum alloy substrate” refers to an electroless Ni—P plating process after grinding the surface of an aluminum alloy plate for a magnetic disk substrate in one or a plurality of embodiments. A magnetic disk substrate can be manufactured by polishing the surface of the Ni-P plated aluminum alloy substrate and forming a magnetic film on the substrate surface by sputtering or the like.
［磁気ディスク基板の製造方法］
本開示は、その他の態様として、本開示に係る研磨液組成物を用いてＮｉ−Ｐメッキされたアルミニウム合金基板を研磨する研磨工程を有する磁気ディスク基板の製造方法に関する。該研磨工程があることにより、研磨パッドの摩耗が抑制されつつ、かつ、研磨速度が大きく損なうことなく、研磨後の基板表面のスクラッチ及びナノ突起欠陥が低減された磁気ディスク基板を好ましくは提供できる。本発明の製造方法は、とりわけ、垂直磁気記録方式用磁気ディスク基板の製造方法に適している。よって、本発明の製造方法は、その他の態様として、本発明の研磨液組成物を用いた研磨工程を含む垂直磁気記録方式用磁気ディスク基板の製造方法である。
[Method of manufacturing magnetic disk substrate]
As another aspect, the present disclosure relates to a method for manufacturing a magnetic disk substrate having a polishing step of polishing an Ni-P plated aluminum alloy substrate using the polishing composition according to the present disclosure. By providing the polishing step, it is possible to preferably provide a magnetic disk substrate in which scratches on the surface of the substrate after polishing and nano-protrusion defects are reduced while suppressing wear of the polishing pad and without greatly reducing the polishing rate. . The manufacturing method of the present invention is particularly suitable for a method for manufacturing a magnetic disk substrate for perpendicular magnetic recording. Therefore, as another aspect, the manufacturing method of the present invention is a method of manufacturing a magnetic disk substrate for a perpendicular magnetic recording system including a polishing step using the polishing composition of the present invention.
本開示に係る研磨液組成物を用いて被研磨基板を研磨する方法の具体例としては、研磨パッドを貼り付けた定盤で被研磨基板を挟み込み、本開示に係る研磨液組成物を研磨機に供給しながら、定盤や被研磨基板を動かして被研磨基板を研磨する方法が挙げられる。 As a specific example of a method of polishing a substrate to be polished using the polishing liquid composition according to the present disclosure, the substrate to be polished is sandwiched between a surface plate to which a polishing pad is attached, and the polishing liquid composition according to the present disclosure is polished by a polishing machine. There is a method of polishing the substrate to be polished by moving the surface plate or the substrate to be polished while supplying to the substrate.
被研磨基板の研磨工程が多段階で行われる場合は、本開示に係る研磨液組成物を用いた研磨工程は２段階目以降に行われるのが好ましく、最終研磨工程、いわゆる仕上げ研磨工程で行われるのがより好ましい。その際、前工程の研磨材や研磨液組成物の混入を避けるために、それぞれ別の研磨機を使用してもよく、またそれぞれ別の研磨機を使用した場合では、研磨工程毎に被研磨基板を洗浄することが好ましい。なお、研磨機としては、特に限定されず、磁気ディスク基板研磨用の公知の研磨機が使用できる。 When the polishing process of the substrate to be polished is performed in multiple stages, the polishing process using the polishing composition according to the present disclosure is preferably performed in the second and subsequent stages, and is performed in the final polishing process, so-called final polishing process. More preferably. At that time, in order to avoid mixing of the polishing material and polishing liquid composition in the previous process, different polishing machines may be used, and in the case of using different polishing machines, polishing is performed for each polishing process. It is preferable to clean the substrate. The polishing machine is not particularly limited, and a known polishing machine for polishing a magnetic disk substrate can be used.
［研磨パッド］
使用される研磨パッドとしては、特に制限はなく、スエードタイプ、不織布タイプ、ポリウレタン独立発泡タイプ、又はこれらを積層した二層タイプ等の研磨パッドを使用することができるが、研磨速度を損なうことなく研磨後の研磨表面のスクラッチ及びナノ欠陥を低減し、かつ、研磨パットの摩耗を抑制する観点から、ポリウレタン製のスエードタイプの研磨パッドが好ましい。
[Polishing pad]
The polishing pad to be used is not particularly limited, and a suede type, non-woven fabric type, polyurethane closed-cell foam type, or a two-layer type polishing pad laminated with these can be used, but without impairing the polishing rate. From the viewpoint of reducing scratches and nano defects on the polished surface after polishing and suppressing wear of the polishing pad, a suede type polishing pad made of polyurethane is preferred.
研磨パッドの表面部材の平均気孔径は、スクラッチ低減及びパッド寿命の観点から、５０μｍ以下が好ましく、より好ましくは４５μｍ以下、更に好ましくは４０μｍ以下、更により好ましくは３５μｍ以下である。パッドの研磨液保持性の観点から、気孔で研磨液を保持し液切れを起こさないようにするために、平均気孔径は０．０１μｍ以上が好ましく、より好ましくは０．１μｍ以上、更に好ましくは１μｍ以上、更により好ましくは５μｍ以上である。また、研磨パッドの気孔径の最大値は、研磨速度維持の観点から、１００μｍ以下が好ましく、より好ましくは５０μｍ以下、更に好ましくは４０μｍ以下、特に好ましくは３０μｍ以下である。 The average pore diameter of the surface member of the polishing pad is preferably 50 μm or less, more preferably 45 μm or less, still more preferably 40 μm or less, and even more preferably 35 μm or less, from the viewpoint of scratch reduction and pad life. From the viewpoint of holding the polishing liquid of the pad, the average pore diameter is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably in order to keep the polishing liquid in the pores and prevent the liquid from running out. It is 1 μm or more, and more preferably 5 μm or more. The maximum pore diameter of the polishing pad is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 40 μm or less, and particularly preferably 30 μm or less from the viewpoint of maintaining the polishing rate.
［研磨荷重］
本開示に係る研磨液組成物を用いた研磨工程における研磨荷重は、好ましくは５．９ｋＰａ以上、より好ましくは６．９ｋＰａ以上、更に好ましくは７．５ｋＰａ以上である。これにより、研磨速度の低下を抑制できるため、生産性の向上が可能となる。なお、本発明の製造方法において研磨荷重とは、研磨時に被研磨基板の研磨面に加えられる定盤の圧力をいう。また、本発明の研磨液組成物を用いた研磨工程において、研磨荷重は２０ｋＰａ以下が好ましく、より好ましくは１８ｋＰａ以下、更に好ましくは１６ｋＰａ以下である。これにより、スクラッチの発生を抑制することができる。したがって、本発明の研磨液組成物を用いた研磨工程において研磨荷重は５．９ｋＰａ以上２０ｋＰａ以下が好ましく、６．９ｋＰａ以上１８ｋＰａ以下がより好ましく、７．５ｋＰａ以上１６ｋＰａ以下が更に好ましい。研磨荷重の調整は、定盤及び被研磨基板のうち少なくとも一方に空気圧や重りを負荷することにより行うことができる。
[Polishing load]
The polishing load in the polishing step using the polishing liquid composition according to the present disclosure is preferably 5.9 kPa or more, more preferably 6.9 kPa or more, and further preferably 7.5 kPa or more. Thereby, since the fall of a grinding | polishing speed | rate can be suppressed, productivity can be improved. In the production method of the present invention, the polishing load refers to the pressure of the surface plate applied to the polishing surface of the substrate to be polished during polishing. In the polishing step using the polishing composition of the present invention, the polishing load is preferably 20 kPa or less, more preferably 18 kPa or less, and still more preferably 16 kPa or less. Thereby, generation | occurrence | production of a scratch can be suppressed. Therefore, in the polishing step using the polishing composition of the present invention, the polishing load is preferably from 5.9 kPa to 20 kPa, more preferably from 6.9 kPa to 18 kPa, and even more preferably from 7.5 kPa to 16 kPa. The polishing load can be adjusted by applying air pressure or weight to at least one of the surface plate and the substrate to be polished.
［研磨液組成物の供給］
研磨工程における本開示に係る研磨液組成物の供給速度は、スクラッチ低減の観点から、被研磨基板１ｃｍ2当たり、好ましくは０．０５ｍＬ／分以上１５ｍＬ／分以下であり、より好ましくは０．０６ｍＬ／分以上１０ｍＬ／分以下であり、更に好ましくは０．０７ｍＬ／分以上１ｍＬ／分以下、更により好ましくは０．０７ｍＬ／分以上０．５ｍＬ／分以下である。
[Supply of polishing liquid composition]
The supply rate of the polishing composition according to the present disclosure in the polishing step is preferably 0.05 mL / min or more and 15 mL / min or less, more preferably 0.06 mL per 1 cm 2 of the substrate to be polished from the viewpoint of reducing scratches. / Min to 10 mL / min, more preferably 0.07 mL / min to 1 mL / min, even more preferably 0.07 mL / min to 0.5 mL / min.
本開示に係る研磨液組成物を研磨機へ供給する方法としては、例えばポンプ等を用いて連続的に供給を行う方法が挙げられる。研磨液組成物を研磨機へ供給する際は、全ての成分を含んだ１液で供給する方法の他、研磨液組成物の安定性等を考慮して、複数の配合用成分液に分け、２液以上で供給することもできる。後者の場合、例えば供給配管中又は被研磨基板上で、上記複数の配合用成分液が混合され、本発明の研磨液組成物となる。 As a method of supplying the polishing composition according to the present disclosure to a polishing machine, for example, a method of continuously supplying using a pump or the like can be mentioned. When supplying the polishing composition to the polishing machine, in addition to the method of supplying one component containing all the components, considering the stability of the polishing composition, etc., it is divided into a plurality of compounding component liquids, Two or more liquids can be supplied. In the latter case, for example, the plurality of compounding component liquids are mixed in the supply pipe or on the substrate to be polished to obtain the polishing liquid composition of the present invention.
［研磨方法］
本開示は、その他の態様として、本開示に係る研磨液組成物を用いてＮｉ−Ｐメッキされたアルミニウム合金基板を研磨することを含む研磨方法に関する。該研磨方法を使用することにより、研磨パッドの摩耗が抑制されつつ、かつ、研磨速度が大きく損なうことなく、研磨後の基板表面のスクラッチ及びナノ突起欠陥が低減される研磨が行える。具体的な研磨方法、被研磨基板は、上述のとおである。
[Polishing method]
As another aspect, the present disclosure relates to a polishing method including polishing an Ni-P plated aluminum alloy substrate using the polishing composition according to the present disclosure. By using this polishing method, polishing with reduced scratches and nanoprotrusion defects on the substrate surface after polishing can be performed while suppressing wear of the polishing pad and without greatly reducing the polishing rate. The specific polishing method and the substrate to be polished are as described above.
本開示は更に以下の一又は複数の実施形態に関する。 The present disclosure further relates to one or more of the following embodiments.
＜１＞ シリカ粒子と、酸と、（メタ）アクリル酸又はその塩に由来する構成単位（Ａ）、及び、ヒドロキシ基を有するエチレン性不飽和スルホン酸化合物又はその塩に由来する構成単位（Ｂ）を有する共重合体とを含む、Ｎｉ−Ｐメッキされたアルミニウム合金基板用の研磨液組成物。 <1> A structural unit (B) derived from silica particles, an acid, a structural unit (A) derived from (meth) acrylic acid or a salt thereof, and an ethylenically unsaturated sulfonic acid compound having a hydroxy group or a salt thereof (B A polishing composition for a Ni-P plated aluminum alloy substrate.
＜２＞ 前記ヒドロキシ基を有するエチレン性不飽和スルホン酸化合物が、３−アリロキシ−２−ヒドキシプロパンスルホン酸（ＨＡＰＳ）である、＜１＞に記載の研磨液組成物。
＜３＞ 前記構成単位（Ｂ）におけるヒドロキシ基の数若しくは平均数が、好ましくは１〜４、より好ましくは１〜３、更に好ましくは１〜２、更により好ましくは１である、＜１＞又は＜２＞に記載の研磨液組成物。
＜４＞ 前記共重合体を構成する構成単位（Ａ）及び（Ｂ）の合計に対する構成単位（Ｂ）の割合が、好ましくは１５モル％以上、より好ましくは２０モル％以上、更に好ましくは３０モル％以上である、＜１＞から＜３＞のいずれかに記載の研磨液組成物。
＜５＞ 前記共重合体を構成する構成単位（Ａ）及び（Ｂ）の合計に対する構成単位（Ｂ）の割合が、好ましくは７０モル％以下、より好ましくは６０モル％以下、更に好ましくは５０モル％以下である、＜１＞から＜４＞のいずれかに記載の研磨液組成物。
＜６＞ 前記共重合体を構成する構成単位（Ａ）及び（Ｂ）の合計に対する構成単位（Ｂ）の割合が、好ましくは１５モル％以上７０モル％以下、より好ましくは２０モル％以上６０モル以下、更に好ましくは３０モル％以上５０モル％以下である、＜１＞から＜５＞のいずれかに記載の研磨液組成物。
＜７＞ 前記共重合体を構成する全構成単位中に占める構成単位（Ａ）及び（Ｂ）の合計構成単位の含有率が、好ましくは８０モル％以上、より好ましくは９０モル％以上、更に好ましくは９５モル％以上、更により好ましくは実質的に１００モル％である、＜１＞から＜６＞のいずれかに記載の研磨液組成物。
＜８＞ 前記共重合体の重量平均分子量が、好ましくは５，０００以上５０，０００以下、より好ましくは６０００以上４０００００以下、更に好ましくは７０００以上３０００００以下、更により好ましくは１００００以上２００００以下である、＜１＞から＜７＞のいずれかに記載の研磨液組成物。
＜９＞ 前記共重合体の含有量が、好ましくは０．００１質量％以上１質量％以下、より好ましくは０．００５質量％以上０．５質量％以下、更に好ましくは０．０１質量％以上０．２質量％以下、更により好ましくは０．０１質量％以上０．１質量％以下、更により好ましくは０．０１質量％以上０．０７５質量％以下である、＜１＞から＜８＞のいずれかに記載の研磨液組成物。
＜１０＞ 研磨液組成物における前記シリカ粒子と前記共重合体との含有量比［シリカ粒子の含有量（質量％）／共重合体の含有量（質量％）］が、好ましくは５以上５０００以下、より好ましくは１０以上１５００以下、更に好ましくは２５以上７５０以下である、＜１＞から＜９＞のいずれかに記載の研磨液組成物。
＜１１＞ さらに、複素芳香族化合物、及び、脂肪族ジアミン又は脂環式ジアミン化合物を含有する、＜１＞から＜１０＞のいずれかに記載の研磨液組成物。
＜１２＞ 前記複素環芳香族化合物が、１，２，４−トリアゾール、３−アミノ−１，２，４−トリアゾール、５−アミノ−１，２，４−トリアゾール、３−メルカプト−１，２，４−トリアゾール、１Ｈ−テトラゾール、５−アミノテトラゾール、１Ｈ−ベンゾトリアゾール、１Ｈ−トリルトリアゾール、２−アミノベンゾトリアゾール、３−アミノベンゾトリアゾール、及びこられのアルキル置換体、並びにこれらの組み合わせからなる群から選択される、＜１１＞に記載の研磨液組成物。
＜１３＞ 前記脂肪族ジアミン化合物が、エチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、１，２-ジアミノプロパン、１，３−ジアミノプロパン、１，４−ジアミノブタン、ヘキサメチレンジアミン、３−（ジエチルアミノ）プロピルアミン、３−（ジブチルアミノ）プロピルアミン、３−（メチルアミノ）プロピルアミン、３−（ジメチルアミノ）プロピルアミン、Ｎ−アミノエチルエタノールアミン、Ｎ−アミノエチルイソプロパノールアミン、Ｎ−アミノエチル−Ｎ−メチルエタノールアミン、及びこれらの組み合わせからなる群から選択され、前記脂環式ジアミン化合物が、ピペラジン、２−メチルピペラジン、２、５−ジメチルピペラジン、１−アミノ−４−メチルピペラジン、Ｎ−メチルピペラジン、Ｎ−ヒドロキシエチルピペラジン、及びこれらの組み合わせからなる群から選択される、＜１１＞又は＜１２＞に記載の研磨液組成物。
＜１４＞ 研磨液組成物における前記複素環芳香族化合物と前記共重合体との含有量比［複素環芳香族化合物の含有量（質量％）／共重合体の含有量（質量％）］が、好ましくは０．１以上３００以下、より好ましくは１以上１００以下、更に好ましくは２以上２５以下である、＜１１＞から＜１３＞のいずれかに記載の研磨液組成物。
＜１５＞ 研磨液組成物における前記複素環芳香族化合物の含有量が、研磨液組成物全体の質量に対して好ましくは０．０１質量％以上１０質量％以下、より好ましくは０．０５質量％以上５質量％以下、更に好ましくは０．１質量％以上１質量％以下である、＜１１＞から＜１４＞のいずれかに記載の研磨液組成物。
＜１６＞ 研磨液組成物における前記シリカ粒子と前記複素環芳香族化合物との含有量比［シリカ粒子の含有量（質量％）／複素環芳香族化合物の含有量（質量％）］が、好ましくは２以上１０００以下、より好ましくは５以上２００以下、更に好ましくは１０以上１００以下である、＜１１＞から＜１５＞のいずれかに記載の研磨液組成物。
＜１７＞ 研磨液組成物における前記脂肪族ジアミン又は脂環式ジアミン化合物と前記共重合体との含有量比［脂肪族ジアミン又は脂環式ジアミン化合物の含有量（質量％）／共重合体の含有量（質量％）］が、好ましくは０．１以上１００以下、より好ましくは０．２５以上５０以下、更に好ましく０．５、以１０上以下である、＜１１＞から＜１６＞のいずれかに記載の研磨液組成物。
＜１８＞ 研磨液組成物における前記脂肪族ジアミン又は脂環式ジアミン化合物の含有量が、研磨液組成物全体の質量に対して好ましくは０．００５質量％以上５質量％以下、より好ましくは０．０１質量％以上２質量％以下、更に好ましくは０．０２質量％以上１質量％以下である、＜１１＞から＜１７＞のいずれかに記載の研磨液組成物。
＜１９＞ 研磨液組成物における前記シリカ粒子と前記脂肪族ジアミン又は脂環式ジアミン化合物との含有量比［シリカ粒子の含有量（質量％）／脂肪族ジアミン又は脂環式ジアミン化合物の含有量（質量％）］が、好ましくは５以上１０００以下、より好ましくは２５以上５００以下、更に好ましくは５０以上２５０以下である、＜１１＞から＜１８＞のいずれかに記載の研磨液組成物。
＜２０＞ 研磨液組成物における前記複素環芳香族化合物と前記脂肪族ジアミン又は脂環式ジアミン化合物との含有量比［複素環芳香族化合物の含有量（質量％）／脂肪族ジアミン又は脂環式ジアミン化合物の含有量（質量％）］が、好ましくは０．１以上５０以下、より好ましくは０．５以上２５以下、更に好ましくは１以上１０以下である、＜１１＞から＜１９＞のいずれかに記載の研磨液組成物。
＜２１＞ 研磨液組成物におけるシリカ粒子の含有量が、好ましくは０．５質量％以上２０質量％以下、より好ましくは１質量％以上１５質量％以下、更に好ましくは３質量％以上１３質量％以下、更により好ましくは４質量％以上１０質量％以下である、＜１＞から＜２０＞のいずれかに記載の研磨液組成物。
＜２２＞ 前記シリカ粒子の平均粒径が、好ましくは１ｎｍ以上４０ｎｍ以下、より好ましくは５ｎｍ以上３７ｎｍ以下、さらに好ましくは１０ｎｍ以上３５ｎｍ以下である、＜１＞から＜２１＞のいずれかに記載の研磨液組成物。
＜２３＞ 研磨液組成物中における前記酸及びその塩の含有量が、好ましくは０．００１質量％以上５質量％以下、より好ましくは０．０１質量％以上４質量％以下であり、更に好ましくは０．０５質量％以上３質量％以下、更により好ましくは０．１質量％以上２．０質量％以下である、＜１＞から＜２２＞のいずれかに記載の研磨液組成物。
＜２４＞ さらに、酸化剤含む、＜１＞から＜２３＞のいずれかに記載の研磨液組成物。
＜２５＞ ＜１＞から＜２４＞のいずれかに記載の研磨液組成物を用いてＮｉ−Ｐメッキされたアルミニウム合金基板を研磨する工程を有する、磁気ディスク基板の製造方法。
＜２６＞ ＜１＞から＜２４＞のいずれかに記載の研磨液組成物を用いてＮｉ−Ｐメッキされたアルミニウム合金基板を研磨することを含む、磁気ディスク基板の研磨方法。
<2> The polishing composition according to <1>, wherein the ethylenically unsaturated sulfonic acid compound having a hydroxy group is 3-allyloxy-2-hydroxypropanesulfonic acid (HAPS).
<3> The number or average number of hydroxy groups in the structural unit (B) is preferably 1 to 4, more preferably 1 to 3, still more preferably 1 to 2, and still more preferably 1. <1> Or the polishing liquid composition as described in <2>.
<4> The ratio of the structural unit (B) to the total of the structural units (A) and (B) constituting the copolymer is preferably 15 mol% or more, more preferably 20 mol% or more, and still more preferably 30. The polishing composition according to any one of <1> to <3>, which is at least mol%.
<5> The ratio of the structural unit (B) to the total of the structural units (A) and (B) constituting the copolymer is preferably 70 mol% or less, more preferably 60 mol% or less, and still more preferably 50. The polishing composition according to any one of <1> to <4>, which is not more than mol%.
<6> The ratio of the structural unit (B) to the total of the structural units (A) and (B) constituting the copolymer is preferably 15 mol% or more and 70 mol% or less, more preferably 20 mol% or more and 60 mol%. The polishing composition according to any one of <1> to <5>, which is not more than mol, more preferably not less than 30 mol% and not more than 50 mol%.
<7> The content of the total constituent units of the constituent units (A) and (B) in all the constituent units constituting the copolymer is preferably 80 mol% or more, more preferably 90 mol% or more, and further The polishing composition according to any one of <1> to <6>, which is preferably 95 mol% or more, and still more preferably substantially 100 mol%.
<8> The weight average molecular weight of the copolymer is preferably 5,000 or more and 50,000 or less, more preferably 6000 or more and 400,000 or less, still more preferably 7000 or more and 300,000 or less, and even more preferably 10,000 or more and 20000 or less. <1> to <7> The polishing composition in any one of <7>.
<9> The content of the copolymer is preferably 0.001% by mass to 1% by mass, more preferably 0.005% by mass to 0.5% by mass, and still more preferably 0.01% by mass or more. <1> to <8> 0.2 mass% or less, still more preferably 0.01 mass% or more and 0.1 mass% or less, and still more preferably 0.01 mass% or more and 0.075 mass% or less. A polishing composition according to any one of the above.
<10> Content ratio [silica particle content (mass%) / copolymer content (mass%)] of the silica particles and the copolymer in the polishing composition is preferably 5 or more and 5000. The polishing composition according to any one of <1> to <9>, more preferably 10 or more and 1500 or less, and further preferably 25 or more and 750 or less.
<11> The polishing composition according to any one of <1> to <10>, further comprising a heteroaromatic compound and an aliphatic diamine or an alicyclic diamine compound.
<12> The heterocyclic aromatic compound is 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, 3-mercapto-1,2 , 4-triazole, 1H-tetrazole, 5-aminotetrazole, 1H-benzotriazole, 1H-tolyltriazole, 2-aminobenzotriazole, 3-aminobenzotriazole, and alkyl substituents thereof, and combinations thereof The polishing composition according to <11>, selected from the group.
<13> The aliphatic diamine compound is ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine. 3- (diethylamino) propylamine, 3- (dibutylamino) propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, N-aminoethylethanolamine, N-aminoethylisopropanolamine, N-aminoethyl-N-methylethanolamine, and combinations thereof, wherein the alicyclic diamine compound is piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 1-amino-4- Methylpiperazine, N-methylpiperazine, N- The polishing composition according to <11> or <12>, which is selected from the group consisting of hydroxyethylpiperazine and combinations thereof.
<14> The content ratio of the heterocyclic aromatic compound to the copolymer in the polishing liquid composition [the content of the heterocyclic aromatic compound (% by mass) / the content of the copolymer (% by mass)]. The polishing composition according to any one of <11> to <13>, preferably from 0.1 to 300, more preferably from 1 to 100, still more preferably from 2 to 25.
<15> The content of the heterocyclic aromatic compound in the polishing liquid composition is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass with respect to the total mass of the polishing liquid composition. The polishing composition according to any one of <11> to <14>, which is 5% by mass or less and more preferably 0.1% by mass or more and 1% by mass or less.
<16> The content ratio of the silica particles and the heterocyclic aromatic compound [the content of silica particles (% by mass) / the content of heterocyclic aromatic compound (% by mass)] in the polishing composition is preferably Is a polishing composition according to any one of <11> to <15>, which is 2 or more and 1000 or less, more preferably 5 or more and 200 or less, and still more preferably 10 or more and 100 or less.
<17> Content ratio of the aliphatic diamine or alicyclic diamine compound and the copolymer in the polishing composition [content of aliphatic diamine or alicyclic diamine compound (% by mass) / copolymer] Content (mass%)] is preferably 0.1 or more and 100 or less, more preferably 0.25 or more and 50 or less, further preferably 0.5 or more and 10 or less, any one of <11> to <16> A polishing liquid composition according to claim 1.
<18> The content of the aliphatic diamine or alicyclic diamine compound in the polishing composition is preferably 0.005% by mass to 5% by mass, more preferably 0%, based on the total mass of the polishing composition. The polishing composition according to any one of <11> to <17>, which is 0.01% to 2% by mass, more preferably 0.02% to 1% by mass.
<19> Content ratio of the silica particles and the aliphatic diamine or alicyclic diamine compound in the polishing composition [content of silica particles (% by mass) / content of aliphatic diamine or alicyclic diamine compound (Mass%)] is preferably 5 or more and 1000 or less, more preferably 25 or more and 500 or less, and still more preferably 50 or more and 250 or less, according to any one of <11> to <18>.
<20> Content ratio of the heterocyclic aromatic compound and the aliphatic diamine or alicyclic diamine compound in the polishing composition [content of heterocyclic aromatic compound (% by mass) / aliphatic diamine or alicyclic The content (% by mass) of the formula diamine compound] is preferably 0.1 or more and 50 or less, more preferably 0.5 or more and 25 or less, and further preferably 1 or more and 10 or less, from <11> to <19> The polishing liquid composition in any one.
<21> The content of silica particles in the polishing composition is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and even more preferably 3% by mass to 13% by mass. Hereinafter, the polishing composition according to any one of <1> to <20>, which is more preferably 4% by mass or more and 10% by mass or less.
<22> The average particle diameter of the silica particles is preferably 1 nm to 40 nm, more preferably 5 nm to 37 nm, and still more preferably 10 nm to 35 nm, according to any one of <1> to <21>. Polishing liquid composition.
<23> The content of the acid and the salt thereof in the polishing composition is preferably 0.001% by mass to 5% by mass, more preferably 0.01% by mass to 4% by mass, and still more preferably. The polishing composition according to any one of <1> to <22>, which is 0.05% by mass or more and 3% by mass or less, and more preferably 0.1% by mass or more and 2.0% by mass or less.
<24> The polishing composition according to any one of <1> to <23>, further comprising an oxidizing agent.
<25> A method for producing a magnetic disk substrate, comprising a step of polishing an Ni-P plated aluminum alloy substrate using the polishing composition according to any one of <1> to <24>.
<26> A method for polishing a magnetic disk substrate, comprising polishing an Ni-P plated aluminum alloy substrate using the polishing composition according to any one of <1> to <24>.
［実施例１〜９、及び、比較例１〜５］
実施例１〜９及び比較例１〜５の研磨液組成物（表２）を調製して被研磨基板の研磨を行い、研磨速度、研磨後の基板のスクラッチ、ナノ突起欠陥、及び研磨パッドの表面粗さを評価した。評価結果を下記表２に示す。使用した（共）重合体の組成を表１に示す。また、研磨液組成物の調製方法、各パラメータの測定方法、研磨条件（研磨方法）及び評価方法は以下のとおりである。なお、下記表２において、ＢＴＡは１Ｈ−ベンゾトリアゾール、ＡＥＥＡはＮ−アミノエチルエタノールアミン、ＨＥＰはＮ−ヒドロキシエチルピペラジン、ＤＴＰＡ・Ｎａはジエチレントリアミン５酢酸ナトリウム塩を示す。
[Examples 1 to 9 and Comparative Examples 1 to 5]
The polishing liquid compositions (Table 2) of Examples 1 to 9 and Comparative Examples 1 to 5 were prepared to polish the substrate to be polished, and the polishing rate, scratches on the substrate after polishing, nanoprotrusion defects, and polishing pads The surface roughness was evaluated. The evaluation results are shown in Table 2 below. The composition of the (co) polymer used is shown in Table 1. Moreover, the preparation method of polishing liquid composition, the measuring method of each parameter, polishing conditions (polishing method), and an evaluation method are as follows. In Table 2 below, BTA represents 1H-benzotriazole, AEEA represents N-aminoethylethanolamine, HEP represents N-hydroxyethylpiperazine, and DTPA · Na represents diethylenetriaminepentaacetic acid sodium salt.
［共重合体］
研磨液組成物に使用した（共）重合体は下記のＡ〜Ｃの水溶性重合体である。これらの重合体の重量平均分子量は下記の条件で測定した。
＜共重合体＞
Ａ：アクリル酸（ＡＡ）／３−アリロキシ−２−ヒドロキシプロパンスルホン酸（ＨＡＰＳ）共重合体ナトリウム塩
Ａ１：モル比６７／３３、重量平均分子量１３０００
Ａ２：モル比６０／４０、重量平均分子量１８０００
Ｂ：アクリル酸（ＡＡ）／２−アクリルアミド−２−メチルプロパンスルホン酸（ＡＭＰＳ）共重合体ナトリウム塩
Ｂ１：モル比９０／１０、重量平均分子量１８０００
Ｂ２：モル比８０／２０、重量平均分子量２４０００
Ｃ：ポリアクリル酸、重量平均分子量１９０００
[Copolymer]
The (co) polymer used in the polishing composition is a water-soluble polymer of the following AC. The weight average molecular weight of these polymers was measured under the following conditions.
<Copolymer>
A: Acrylic acid (AA) / 3-allyloxy-2-hydroxypropanesulfonic acid (HAPS) copolymer sodium salt A1: molar ratio 67/33, weight average molecular weight 13000
A2: molar ratio 60/40, weight average molecular weight 18000
B: acrylic acid (AA) / 2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer sodium salt B1: molar ratio 90/10, weight average molecular weight 18000
B2: molar ratio 80/20, weight average molecular weight 24000
C: polyacrylic acid, weight average molecular weight 19000
〔ＡＡ／ＨＡＰＳ共重合体ナトリウム塩、ポリアクリル酸ナトリウム塩の製造方法〕
ＡＡ／ＨＡＰＳ共重合体ナトリウム塩及びポリアクリル酸ナトリウム塩は特開平１１−１２８７１５の実施例の開示、及び、特開２０１０−１３２７２３の実施例（比較例５）の開示を参照して作製した。
[Method of producing AA / HAPS copolymer sodium salt, polyacrylic acid sodium salt]
AA / HAPS copolymer sodium salt and polyacrylic acid sodium salt were prepared with reference to the disclosure of Examples of JP-A-11-128715 and the disclosure of Examples of JP-A-2010-132723 (Comparative Example 5).
［重合体の重量平均分子量の測定方法］
上記の重合体の重量平均分子量は、下記測定条件におけるゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定した。
カラム：Ｇ４０００ＳＷＸＬ＋Ｇ２５００ＳＷＸＬ（東ソー製）
溶離液：０．２Ｍリン酸バッファー／ＣＨ3ＣＮ＝７／３体積比
温度：４０℃
流速：１．０ｍｌ／分
試料サイズ：５ｍｇ／ｍｌ
検出器：ＲＩ
標準物質：ポリエチレングリコール（２．４万、１０．１万、１８．５万、５４万：東ソー製、２５．８万、８７．５万 創和科学製）
[Method for measuring weight average molecular weight of polymer]
The weight average molecular weight of the polymer was measured by a gel permeation chromatography (GPC) method under the following measurement conditions.
Column: G4000SWXL + G2500SWXL (manufactured by Tosoh)
Eluent: 0.2 M phosphate buffer / CH 3 CN = 7/3 volume ratio Temperature: 40 ° C.
Flow rate: 1.0 ml / min Sample size: 5 mg / ml
Detector: RI
Standard substance: Polyethylene glycol (24,000, 101,000, 185,000, 540,000: manufactured by Tosoh Corporation, 2580, 875,000, manufactured by Sowa Kagaku)
〔コロイダルシリカの平均粒径〕
研磨液組成物の調製に用いたコロイダルシリカと、硫酸と、過酸化水素水とをイオン交換水に添加し、撹拌することにより、標準試料を作製した（ｐＨ１．５）。標準試料中におけるコロイダルシリカ、硫酸、ＨＥＤＰ、過酸化水素の含有量は、それぞれ５質量％、０．５質量％、０．５質量％とした。この標準試料を動的光散乱装置（大塚電子社製DLS-6500）により、同メーカーが添付した説明書に従って、２００回積算した際の検出角９０°におけるCumulant法によって得られる散乱強度分布の面積が全体の５０％となる粒径を求め、コロイダルシリカの平均粒径とした。
[Average particle size of colloidal silica]
Colloidal silica, sulfuric acid, and hydrogen peroxide solution used for the preparation of the polishing composition were added to ion-exchanged water and stirred to prepare a standard sample (pH 1.5). The contents of colloidal silica, sulfuric acid, HEDP, and hydrogen peroxide in the standard sample were 5% by mass, 0.5% by mass, and 0.5% by mass, respectively. The area of the scattering intensity distribution obtained by the cumulant method at a detection angle of 90 ° when this standard sample is integrated 200 times with a dynamic light scattering device (DLS-6500 manufactured by Otsuka Electronics Co., Ltd.) according to the instructions attached by the manufacturer. Was determined as the average particle size of colloidal silica.
［研磨液組成物の調製方法］
６．０質量％のコロイダルシリカ（平均粒径２５ｎｍ）、０．４質量％の酸（硫酸）、０．４質量％の酸化剤（過酸化水素）、表１の（共）重合体、水、並びに、必要に応じて、下記表２に記載の複素環芳香族化合物及び脂肪族アミン化合物若しくは脂環式アミン化合物を混合して実施例１〜９及び比較例１〜５の研磨液組成物を調製した。なお、実施例１、２、７、８及び比較例１及び５には、複素環芳香族化合物及び脂肪族アミン化合物若しくは脂環式アミン化合物を添加していない。また、比較例５には（共）重合体を使用していない。実施例１〜９及び比較例１〜５の研磨液組成物のｐＨは１．５であった。なお、ｐＨは、研磨液組成物の２５℃における値であって、ｐＨメータ（東亜電波工業株式会社、ＨＭ−３０Ｇ）を用い、電極の研磨液組成物への浸漬後１分後に測定した数値である。
[Method for preparing polishing liquid composition]
6.0 mass% colloidal silica (average particle size 25 nm), 0.4 mass% acid (sulfuric acid), 0.4 mass% oxidant (hydrogen peroxide), (co) polymer of Table 1, water In addition, as necessary, the polishing liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 5 were mixed by mixing the heterocyclic aromatic compound and the aliphatic amine compound or alicyclic amine compound described in Table 2 below. Was prepared. In Examples 1, 2, 7, 8 and Comparative Examples 1 and 5, no heterocyclic aromatic compound and aliphatic amine compound or alicyclic amine compound were added. In Comparative Example 5, no (co) polymer is used. The pH of the polishing composition of Examples 1 to 9 and Comparative Examples 1 to 5 was 1.5. In addition, pH is a value at 25 ° C. of the polishing composition, and is a numerical value measured 1 minute after immersion of the electrode in the polishing composition using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G). It is.
［研磨］
上記のように調製した実施例１〜９及び比較例１〜５の研磨液組成物を用いて、以下に示す研磨条件にて下記被研磨基板を研磨した。次いで、研磨速度、研磨された基板のナノ突起欠陥及びスクラッチ、並びに、研磨パッドの表面粗さの変化率を以下に示す条件に基づいて測定し、評価を行った。結果を下記表２に示す。下記表２に示すデータは、各実施例及び各比較例につき４枚の被研磨基板を研磨した後、各被研磨基板の両面について測定し、４枚（表裏合わせて計８面）のデータの平均とした。
[Polishing]
Using the polishing liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 5 prepared as described above, the following substrates to be polished were polished under the following polishing conditions. Next, the polishing rate, the nanoprojection defects and scratches on the polished substrate, and the rate of change of the surface roughness of the polishing pad were measured and evaluated based on the following conditions. The results are shown in Table 2 below. The data shown in the following Table 2 is obtained by polishing four substrates for each example and each comparative example, and measuring both surfaces of each substrate to be polished. Averaged.
［被研磨基板］
被研磨基板としては、Ｎｉ−Ｐメッキされたアルミニウム合金基板を予めアルミナ研磨材を含有する研磨液組成物で粗研磨した基板を用いた。なお、この被研磨基板は、厚さが１．２７ｍｍ、外径が９５ｍｍ、内径が２５ｍｍであり、ＡＦＭ（Ｄｉｇｉｔａｌ Ｉｎｓｔｒｕｍｅｎｔ ＮａｎｏＳｃｏｐｅ ＩＩＩａ Ｍｕｌｔｉ Ｍｏｄｅ ＡＦＭ）により測定した中心線平均粗さＲａが１ｎｍ、長波長うねり（波長０．４〜２ｍｍ）の振幅は２ｎｍ、短波長うねり（波長５０〜４００μｍ）の振幅は２ｎｍであった。
[Polished substrate]
As the substrate to be polished, a substrate obtained by rough polishing an aluminum alloy substrate plated with Ni-P in advance with a polishing composition containing an alumina abrasive was used. The substrate to be polished has a thickness of 1.27 mm, an outer diameter of 95 mm, an inner diameter of 25 mm, a center line average roughness Ra measured by AFM (Digital Instrument Nanoscope IIIa Multi Mode AFM), 1 nm, and a long wavelength. The amplitude of the undulation (wavelength 0.4 to 2 mm) was 2 nm, and the amplitude of the short wavelength undulation (wavelength 50 to 400 μm) was 2 nm.
［研磨条件］
研磨試験機：スピードファム社製「両面９Ｂ研磨機」
研磨パッド：フジボウ社製スエードタイプ（ポリウレタン製、厚さ０．９ｍｍ、平均開孔径３０μｍ）
研磨液組成物供給量：５０ｍＬ／分（被研磨基板１ｃｍ2あたりの供給速度：０．０７５ｍＬ／分）
下定盤回転数：３２．５ｒｐｍ
研磨荷重：１２．５ｋＰａ
研磨時間：５分間
[Polishing conditions]
Polishing tester: "Fast double-sided 9B polishing machine" manufactured by Speedfam
Polishing pad: Fujibow Suede type (Polyurethane, thickness 0.9mm, average pore diameter 30μm)
Polishing liquid composition supply amount: 50 mL / min (supply rate per 1 cm 2 of polishing substrate: 0.075 mL / min)
Lower platen rotation speed: 32.5 rpm
Polishing load: 12.5kPa
Polishing time: 5 minutes
［研磨速度の測定方法］
研磨前後の各基板の重さを重量計（Ｓａｒｔｏｒｉｕｓ社製「ＢＰ−２１０Ｓ」）を用いて測定し、各基板の重量変化を求め、１０枚の平均値を重量減少量とし、それを研磨時間で割った値を重量減少速度とした。この重量減少速度を下記の式に導入し、研磨速度（μｍ／ｍｉｎ）に変換した。
研磨速度（μｍ／ｍｉｎ）＝重量減少速度（ｇ／ｍｉｎ）／基板片面面積（ｍｍ2）／Ｎｉ−Ｐメッキ密度（ｇ／ｃｍ3）×１０6
（基板片面面積：６５９７ｍｍ2、Ｎｉ−Ｐメッキ密度：７．９９ｇ／ｃｍ3として算出）
[Measurement method of polishing rate]
The weight of each substrate before and after polishing was measured using a weigh scale ("BP-210S" manufactured by Sartorius) to determine the weight change of each substrate, and the average value of 10 substrates was used as the weight reduction amount, which was used as the polishing time. The value obtained by dividing by was used as the weight reduction rate. This weight reduction rate was introduced into the following formula and converted into a polishing rate (μm / min).
Polishing rate (μm / min) = weight reduction rate (g / min) / substrate one side area (mm 2 ) / Ni—P plating density (g / cm 3 ) × 10 6
(Substrate single-sided area: 6597 mm 2 , Ni—P plating density: calculated as 7.9 g / cm 3 )
［ナノ突起欠陥及びスクラッチの評価方法］
測定機器：ＫＬＡ Ｔｅｎｃｏｒ社製、ＯＳＡ７１００
評価：研磨試験機に投入した基板の中、無作為に４枚を選択し、各々の基板を１００００ｒｐｍにてレーザーを照射してナノ突起欠陥及びスクラッチを測定した。その４枚の基板の各々両面にあるスクラッチ数（本）の合計を８で除して、基板面当たりのナノ突起欠陥及びスクラッチの数を算出した。その結果を、下記表２に、比較例１を１００％とした相対値として示す。
[Evaluation method of nanoprotrusion defects and scratches]
Measuring instrument: OSA7100, manufactured by KLA Tencor
Evaluation: Four substrates were randomly selected from the substrates put in the polishing tester, and each substrate was irradiated with a laser at 10,000 rpm to measure nanoprotrusion defects and scratches. The total number of scratches (lines) on each of the four substrates was divided by 8 to calculate the number of nanoprotrusion defects and scratches per substrate surface. The results are shown in Table 2 below as relative values with Comparative Example 1 taken as 100%.
［研磨パットの変形抑制の評価方法］
使用前と、使用開始から上記の研磨条件で２００バッチの研磨を行った後の研磨パッドの表面粗さ（Ｒａ）の変化を触診式の表面粗さ計（商品名：ＳＵＲＦＴＥＳＴ ＳＪ−２１０、ミツトヨ社製）を用いて測定した。
＜測定条件＞
粗さ規格：ＩＳＯ１９９７
測定速度：０．５ｍｍ／ｓ
カットオフ値：０．８ｍｍ
＜評価基準＞
研磨パッドの表面粗さの変化率を下記の式により求めた。
表面粗さ変化率＝（２００バッチ後の表面粗さ）／（研磨開始前の表面粗さ）×１００
[Evaluation method for deformation suppression of polishing pad]
Changes in the surface roughness (Ra) of the polishing pad before use and after 200 batches of polishing were performed under the above-described polishing conditions from the start of use were measured by a palpable surface roughness meter (trade name: SURFTEST SJ-210, Mitutoyo Corporation). The measurement was performed using
<Measurement conditions>
Roughness standard: ISO1997
Measurement speed: 0.5 mm / s
Cut-off value: 0.8mm
<Evaluation criteria>
The change rate of the surface roughness of the polishing pad was determined by the following formula.
Surface roughness change rate = (surface roughness after 200 batches) / (surface roughness before starting polishing) × 100
表２に示すとおり、実施例１〜９の研磨液組成物は、比較例１〜４の研磨液組成物と比較して、研磨速度を損なうことなく、また、ナノ欠陥数及びスクラッチ数が増大することなく、研磨パッドの摩耗を抑制できた。また、比較例５は、実施例１と比べると、研磨パッドの摩耗は抑制できたが、ナノ欠陥数及びスクラッチ数が著しく増大した。 As shown in Table 2, the polishing liquid compositions of Examples 1 to 9 increase the number of nano defects and the number of scratches without impairing the polishing rate as compared with the polishing liquid compositions of Comparative Examples 1 to 4. Thus, the wear of the polishing pad could be suppressed. Moreover, compared with Example 1, the comparative example 5 was able to suppress abrasion of the polishing pad, but the number of nano defects and the number of scratches were remarkably increased.
本開示によれば、例えば、高記録密度化に適した磁気ディスク基板を提供できる。 According to the present disclosure, for example, a magnetic disk substrate suitable for increasing the recording density can be provided.
Claims (8)
酸と、
（メタ）アクリル酸又はその塩に由来する構成単位、及び、ヒドロキシ基を有するエチレン性不飽和スルホン酸化合物又はその塩に由来する構成単位を有する共重合体と、
を含む、Ｎｉ−Ｐメッキされたアルミニウム合金基板用の研磨液組成物。 Silica particles;
Acid,
A copolymer having a structural unit derived from (meth) acrylic acid or a salt thereof, and an ethylenically unsaturated sulfonic acid compound having a hydroxy group or a salt thereof;
A polishing composition for a Ni-P plated aluminum alloy substrate.
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| WO2019004161A1 (en) * | 2017-06-26 | 2019-01-03 | 花王株式会社 | Silica slurry for polishing-liquid composition |
| JP2019007000A (en) * | 2017-06-26 | 2019-01-17 | 花王株式会社 | Silica slurry for polishing liquid composition |
| JP7440326B2 (en) | 2020-04-01 | 2024-02-28 | 山口精研工業株式会社 | Abrasive composition |
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