JP2024073235A - Polishing composition - Google Patents
Polishing composition Download PDFInfo
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- JP2024073235A JP2024073235A JP2022184336A JP2022184336A JP2024073235A JP 2024073235 A JP2024073235 A JP 2024073235A JP 2022184336 A JP2022184336 A JP 2022184336A JP 2022184336 A JP2022184336 A JP 2022184336A JP 2024073235 A JP2024073235 A JP 2024073235A
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- Japan
- Prior art keywords
- polishing
- component
- present disclosure
- substrate
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005498 polishing Methods 0.000 title claims abstract description 244
- 239000000203 mixture Substances 0.000 title claims abstract description 106
- 239000000758 substrate Substances 0.000 claims abstract description 113
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000012736 aqueous medium Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 description 61
- 239000000377 silicon dioxide Substances 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000007517 polishing process Methods 0.000 description 13
- 238000004220 aggregation Methods 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- -1 phosphonium salt compound Chemical class 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000011163 secondary particle Substances 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 229910018104 Ni-P Inorganic materials 0.000 description 6
- 229910018536 Ni—P Inorganic materials 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002904 solvent 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000006061 abrasive grain Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 description 2
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-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
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 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 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- RJWLLQWLBMJCFD-UHFFFAOYSA-N 4-methylpiperazin-1-amine Chemical compound CN1CCN(N)CC1 RJWLLQWLBMJCFD-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000005407 aluminoborosilicate glass Substances 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- JCXKHYLLVKZPKE-UHFFFAOYSA-N benzotriazol-1-amine Chemical compound C1=CC=C2N(N)N=NC2=C1 JCXKHYLLVKZPKE-UHFFFAOYSA-N 0.000 description 1
- YYZVLEJDGSWXII-UHFFFAOYSA-N benzotriazol-2-amine Chemical compound C1=CC=CC2=NN(N)N=C21 YYZVLEJDGSWXII-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- BNQRPLGZFADFGA-UHFFFAOYSA-N benzyl(triphenyl)phosphanium Chemical class C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 BNQRPLGZFADFGA-UHFFFAOYSA-N 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- ZGTNBBQKHJMUBI-UHFFFAOYSA-N bis[tetrakis(hydroxymethyl)-lambda5-phosphanyl] sulfate Chemical compound OCP(CO)(CO)(CO)OS(=O)(=O)OP(CO)(CO)(CO)CO ZGTNBBQKHJMUBI-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 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
- 239000012153 distilled water Substances 0.000 description 1
- 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 1
- 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 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007518 final polishing process Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 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 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 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 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KYCGURZGBKFEQB-UHFFFAOYSA-N n',n'-dibutylpropane-1,3-diamine Chemical compound CCCCN(CCCC)CCCN KYCGURZGBKFEQB-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical group [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 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
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical class CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical class C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- CYABZYIVQJYRDT-UHFFFAOYSA-N trimorpholin-4-ylphosphane Chemical compound C1COCCN1P(N1CCOCC1)N1CCOCC1 CYABZYIVQJYRDT-UHFFFAOYSA-N 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
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Magnetic Record Carriers (AREA)
- Manufacturing Of Magnetic Record Carriers (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
【課題】一態様において、研磨速度を確保しつつ、研磨後の基板表面のスクラッチを低減できる保存安定性に優れた研磨液組成物を提供する。【解決手段】本開示は、一態様において、シリカ粒子（成分Ａ）と、酸（成分Ｂ）と、酸化剤（成分Ｃ）と、置換基のない炭化水素基を少なくとも１つ有する第４級ホスホニウム塩（成分Ｄ）と、水系媒体と、を含有する、磁気ディスク基板用研磨液組成物に関する。【選択図】なし[Problem] In one aspect, there is provided a polishing composition with excellent storage stability that can reduce scratches on the substrate surface after polishing while ensuring the removal rate. [Solution] In one aspect, the present disclosure relates to a polishing composition for magnetic disk substrates, which contains silica particles (component A), an acid (component B), an oxidizing agent (component C), a quaternary phosphonium salt having at least one unsubstituted hydrocarbon group (component D), and an aqueous medium. [Selected Figures] None
Description
本開示は、研磨液組成物、並びにこれを用いた基板の製造方法及び研磨方法に関する。 This disclosure relates to a polishing composition, and a method for manufacturing and polishing a substrate using the same.
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、表面粗さ、うねり、端面ダレ（ロールオフ）の低減に代表される平滑性・平坦性の向上とスクラッチ、突起、ピット等の低減に代表される欠陥低減に対する要求が厳しくなっている。 In recent years, magnetic disk drives have become smaller and have larger capacities, and there is a demand for higher recording density. To achieve higher recording density, technological developments are underway to reduce the unit recording area and lower the flying height of the magnetic head in order to improve the detection sensitivity of weakened magnetic signals. To accommodate the lower flying height of the magnetic head and ensure the recording area, there are increasingly strict requirements for magnetic disk substrates in terms of improved smoothness and flatness, as typified by reduced surface roughness, waviness, and edge sagging (roll-off), as well as reduced defects, as typified by reduced scratches, protrusions, pits, etc.
磁気ディスク基板以外の基板においても、研磨速度や平坦性を向上できる研磨液が開発されている。
例えば、特許文献１には、ポリシリコンを含むストッパと、絶縁材料（例えば酸化ケイ素）を含む部材とを有する基体の研磨に用いられるＣＭＰ（化学機械研磨）用研磨液であって、金属酸化物を含む砥粒と、リン原子に結合する炭素数２以上の炭化水素基を有する第４級ホスホニウムカチオンと、液状媒体と、を含有する研磨液が提案されている。
特許文献２には、コバルトを含む被研磨面の研磨に用いられるＣＭＰ用研磨剤であって、砥粒と、第４級ホスホニウム塩と、水と、を含有し、ｐＨが４．０を超える研磨剤が提案されている。
特許文献３には、層間絶縁膜とバリア膜と導電性物質を有する基板の、導電性物質を研磨してバリア膜を露出させる第１研磨工程後、バリア膜を研磨して層間絶縁膜を露出させる第２研磨工程で用いられるＣＭＰ用研磨液であって、特定の第４級ホスホニウム塩化合物と、負電荷を有する砥粒と、酸化金属溶解剤と、酸化剤と、を含有する研磨液が提案されている。
特許文献４には、タングステン含有表面を処理するための化学機械研磨組成物であって、液体キャリアと、特定のシリカ研磨剤粒子と、特定のカチオン性界面活性剤とを含む研磨液が提案されている。
Polishing solutions capable of improving the polishing rate and flatness of substrates other than magnetic disk substrates have also been developed.
For example, Patent Document 1 proposes a polishing liquid for CMP (chemical mechanical polishing) used for polishing a substrate having a stopper containing polysilicon and a member containing an insulating material (e.g., silicon oxide), the polishing liquid containing abrasive grains containing a metal oxide, a quaternary phosphonium cation having a hydrocarbon group having two or more carbon atoms bonded to a phosphorus atom, and a liquid medium.
Patent Document 2 proposes a CMP polishing agent used for polishing a surface containing cobalt, the polishing agent containing abrasive grains, a quaternary phosphonium salt, and water and having a pH of more than 4.0.
Patent Document 3 proposes a polishing liquid for CMP used in a second polishing step of polishing the barrier film to expose the interlayer insulating film after a first polishing step of polishing the conductive material of a substrate having an interlayer insulating film, a barrier film, and a conductive material, the second polishing step of polishing the barrier film to expose the interlayer insulating film, the polishing liquid containing a specific quaternary phosphonium salt compound, negatively charged abrasive grains, a metal oxide dissolving agent, and an oxidizing agent.
Patent Document 4 proposes a chemical mechanical polishing composition for treating a tungsten-containing surface, the polishing liquid including a liquid carrier, specific silica abrasive particles, and a specific cationic surfactant.
磁気ディスクドライブの大容量化に伴い、基板の表面品質に対する要求特性はさらに厳しくなっており、基板表面のスクラッチをいっそう低減できる研磨液組成物の開発が求められている。また、一般的に、研磨速度とスクラッチとはトレードオフの関係にあり、一方が改善すれば一方が悪化するという問題がある。 As the capacity of magnetic disk drives increases, the requirements for the surface quality of substrates are becoming more stringent, and there is a demand for the development of polishing compositions that can further reduce scratches on the substrate surface. In addition, there is generally a trade-off between polishing speed and scratches, and there is a problem that improving one will worsen the other.
そこで、本開示は、研磨速度を確保しつつ、研磨後の基板表面のスクラッチを低減できる研磨液組成物、並びにこれを用いた磁気ディスク基板の製造方法及び基板の研磨方法を提供する。 Therefore, the present disclosure provides a polishing composition that can reduce scratches on the substrate surface after polishing while maintaining the polishing rate, as well as a method for manufacturing a magnetic disk substrate and a method for polishing a substrate using the same.
本開示は、一態様において、シリカ粒子（成分Ａ）と、酸（成分Ｂ）と、酸化剤（成分Ｃ）と、置換基のない炭化水素基を少なくとも１つ有する第４級ホスホニウム塩（成分Ｄ）と、水系媒体と、を含有する、磁気ディスク基板用研磨液組成物に関する。 In one aspect, the present disclosure relates to a polishing liquid composition for magnetic disk substrates, which contains silica particles (component A), an acid (component B), an oxidizing agent (component C), a quaternary phosphonium salt having at least one unsubstituted hydrocarbon group (component D), and an aqueous medium.
本開示は、一態様において、本開示の研磨液組成物を用いて被研磨基板を研磨する工程を含む、磁気ディスク基板の製造方法に関する。 In one aspect, the present disclosure relates to a method for manufacturing a magnetic disk substrate, comprising a step of polishing a substrate to be polished using the polishing composition of the present disclosure.
本開示は、一態様において、本開示の研磨液組成物を用いて被研磨基板を研磨することを含み、前記被研磨基板は、磁気ディスク基板の製造に用いられる基板である、基板の研磨方法に関する。 In one aspect, the present disclosure relates to a method for polishing a substrate, the method comprising polishing a substrate to be polished with the polishing composition of the present disclosure, the substrate to be polished being a substrate used in the manufacture of magnetic disk substrates.
本開示の研磨組成物によれば、一又は複数の実施形態において、研磨速度を確保しつつ、研磨後の基板表面のスクラッチを低減できるという効果が奏されうる。 In one or more embodiments, the polishing composition of the present disclosure can achieve the effect of reducing scratches on the substrate surface after polishing while maintaining the polishing rate.
本開示は、シリカ粒子、酸、酸化剤、特定の第４級ホスホニウム塩及び水系媒体を含有する研磨液組成物を用いると、研磨速度を確保しつつ、研磨後の基板表面のスクラッチを低減できるという知見に基づく。 This disclosure is based on the finding that the use of a polishing composition containing silica particles, an acid, an oxidizing agent, a specific quaternary phosphonium salt, and an aqueous medium can reduce scratches on the substrate surface after polishing while maintaining the polishing rate.
すなわち、本開示は、一態様において、シリカ粒子（成分Ａ）と、酸（成分Ｂ）と、酸化剤（成分Ｃ）と、置換基のない炭化水素基を少なくとも１つ有する第４級ホスホニウム塩（成分Ｄ）と、水系媒体と、を含有する、磁気ディスク基板用研磨液組成物（以下、「本開示の研磨液組成物」ともいう）に関する。 That is, in one aspect, the present disclosure relates to a polishing liquid composition for magnetic disk substrates (hereinafter also referred to as the "polishing liquid composition of the present disclosure") that contains silica particles (component A), an acid (component B), an oxidizing agent (component C), a quaternary phosphonium salt having at least one unsubstituted hydrocarbon group (component D), and an aqueous medium.
本開示の効果発現のメカニズムの詳細は明らかではないが、以下のように推察される。
置換基のない炭化水素基を少なくとも1つ有する第４級ホスホニウム塩（成分Ｄ）が、被研磨基板（例えば、Ｎｉ-Ｐメッキされたアルミニウム合金基板）表面へ吸着することで、基板表面に疎水性を付与する。そして、基板表面への疎水性の付与によって過剰な化学反応を抑制することでスクラッチ数及び点欠陥数（ＬＰＤ）を減少させるものと推察される。基板表面への疎水性の付与という点において、第４級ホスホニウム塩が水酸基のような親水性置換基を有する場合はその抑制能の低下が発生するために効果が減弱されるものと考えられる。
但し、本開示はこれらのメカニズムに限定して解釈されなくてもよい。
Although the details of the mechanism by which the effects of the present disclosure are manifested are not clear, it is presumed as follows.
A quaternary phosphonium salt (component D) having at least one unsubstituted hydrocarbon group is adsorbed to the surface of a substrate to be polished (e.g., an aluminum alloy substrate plated with Ni-P), thereby imparting hydrophobicity to the substrate surface. It is presumed that imparting hydrophobicity to the substrate surface suppresses excessive chemical reactions, thereby reducing the number of scratches and the number of point defects (LPDs). In terms of imparting hydrophobicity to the substrate surface, when the quaternary phosphonium salt has a hydrophilic substituent such as a hydroxyl group, the suppression ability is reduced, and therefore the effect is weakened.
However, the present disclosure need not be construed as being limited to these mechanisms.
本開示において、基板表面のスクラッチは、例えば、光学式欠陥検査装置により検出可能であり、スクラッチ数として定量評価できる。スクラッチ数は、具体的には実施例に記載した方法で評価できる。 In the present disclosure, scratches on the substrate surface can be detected, for example, by an optical defect inspection device and can be quantitatively evaluated as the number of scratches. Specifically, the number of scratches can be evaluated by the method described in the examples.
［シリカ粒子（成分Ａ）］
本開示の研磨液組成物は、シリカ粒子（以下「成分Ａ」ともいう）を含有する。成分Ａとしては、研磨速度向上及びスクラッチ低減の観点から、コロイダルシリカ、ヒュームドシリカ、粉砕シリカ、それらを表面修飾したシリカ等が挙げられるが、コロイダルシリカが好ましい。成分Ａは、１種でもよいし、２種以上の組合せでもよい。
[Silica particles (component A)]
The polishing composition of the present disclosure contains silica particles (hereinafter also referred to as "Component A"). From the viewpoint of improving the polishing rate and reducing scratches, Component A may include colloidal silica, fumed silica, pulverized silica, and silica surface-modified with these, with colloidal silica being preferred. Component A may be one type or a combination of two or more types.
成分Ａの平均二次粒子径は、研磨速度向上の観点から、１ｎｍ以上が好ましく、５ｎｍ以上がより好ましく、１０ｎｍ以上が更に好ましく、そして、スクラッチ低減の観点から、５００ｎｍ以下が好ましく、３００ｎｍ以下がより好ましく、１００ｎｍ以下が更に好ましく、７０ｎｍ以下が更に好ましく、４０ｎｍ以下が更に好ましい。より具体的には、成分Ａの平均二次粒子径は、１ｎｍ以上５００ｎｍ以下が好ましく、１ｎｍ以上３００ｎｍ以下がより好ましく、１ｎｍ以上１００ｎｍ以下が更に好ましく、５ｎｍ以上７０ｎｍ以下が更に好ましく、１０ｎｍ以上４０ｎｍ以下が更に好ましい。本開示において、「シリカ粒子の平均二次粒子径」とは、動的光散乱法により測定される値であり、例えば、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二次粒子径とすることができる。シリカ粒子の平均二次粒子径は、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。 From the viewpoint of improving the polishing rate, the average secondary particle diameter of component A is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more, and from the viewpoint of reducing scratches, it is preferably 500 nm or less, more preferably 300 nm or less, even more preferably 100 nm or less, even more preferably 70 nm or less, and even more preferably 40 nm or less. More specifically, the average secondary particle diameter of component A is preferably 1 nm or more and 500 nm or less, more preferably 1 nm or more and 300 nm or less, even more preferably 1 nm or more and 100 nm or less, even more preferably 5 nm or more and 70 nm or less, and even more preferably 10 nm or more and 40 nm or less. In this disclosure, the "average secondary particle diameter of silica particles" is a value measured by a dynamic light scattering method, and can be, for example, the average secondary particle diameter based on the scattering intensity distribution measured at a detection angle of 90° in the dynamic light scattering method. The average secondary particle diameter of silica particles can be specifically determined by the method described in the examples.
本開示の研磨液組成物中の成分Ａの含有量は、研磨速度向上の観点から、ＳｉＯ2換算で、０．１質量％以上が好ましく、１質量％以上がより好ましく、３質量％以上が更に好ましく、そして、スクラッチ低減の観点から、ＳｉＯ2換算で、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下が更に好ましい。より具体的には、本開示の研磨液組成物中の成分Ａの含有量は、ＳｉＯ2換算で、０．１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１０質量％以下が更に好ましい。成分Ａが２種以上のシリカ粒子からなる場合、成分Ａの含有量は、それらの合計含有量をいう。 The content of component A in the polishing composition of the present disclosure is preferably 0.1 mass% or more, more preferably 1 mass% or more, and even more preferably 3 mass% or more, calculated as SiO2 , from the viewpoint of improving the polishing rate, and is preferably 20 mass% or less, more preferably 15 mass% or less, and even more preferably 10 mass% or less, calculated as SiO2 , from the viewpoint of reducing scratches. More specifically, the content of component A in the polishing composition of the present disclosure is preferably 0.1 mass% or more and 20 mass% or less, more preferably 1 mass% or more and 15 mass% or less, and even more preferably 3 mass% or more and 10 mass% or less, calculated as SiO2. When component A is composed of two or more types of silica particles, the content of component A refers to the total content thereof.
［酸（成分Ｂ）］
本開示の研磨液組成物は、酸（以下、「成分Ｂ」ともいう）を含有する。本開示において、酸の使用は、酸又はその塩の使用を含む。成分Ｂは１種でもよいし、２種以上の組合せでもよい。
[Acid (Component B)]
The polishing composition of the present disclosure contains an acid (hereinafter also referred to as "component B"). In the present disclosure, the use of an acid includes the use of an acid or a salt thereof. Component B may be one type or a combination of two or more types.
成分Ｂとしては、例えば、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；有機リン酸、有機ホスホン酸、カルボン酸等の有機酸；等が挙げられる。中でも、研磨速度の確保及びスクラッチ低減の観点から、無機酸及び有機ホスホン酸から選ばれる少なくとも１種が好ましい。無機酸としては、硝酸、硫酸、塩酸、過塩素酸及びリン酸から選ばれる少なくとも１種が好ましく、硫酸及びリン酸から選ばれる少なくとも１種がより好ましく、リン酸が更に好ましい。有機ホスホン酸としては、１－ヒドロキシエチリデン－１，１－ジホスホン酸（ＨＥＤＰ）、アミノトリ（メチレンホスホン酸）、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）から選ばれる少なくとも１種が好ましく、ＨＥＤＰがより好ましい。これらの酸の塩としては、例えば、上記の酸と、金属、アンモニア及びアルキルアミンから選ばれる少なくとも１種との塩が挙げられる。上記金属としては、周期表の１～１１族に属する金属が挙げられる。 Component B includes, for example, 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, and organic acids such as organic phosphoric acid, organic phosphonic acid, and carboxylic acid. Among them, from the viewpoint of ensuring the polishing rate and reducing scratches, at least one selected from inorganic acids and organic phosphonic acids is preferred. As inorganic acids, at least one selected from nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, and phosphoric acid is preferred, at least one selected from sulfuric acid and phosphoric acid is more preferred, and phosphoric acid is even more preferred. As organic phosphonic acids, at least one selected from 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), and diethylenetriaminepenta(methylenephosphonic acid) is preferred, and HEDP is more preferred. As salts of these acids, for example, salts of the above acids and at least one selected from metals, ammonia, and alkylamines are included. Examples of the metals include those in groups 1 to 11 of the periodic table.
本開示の研磨液組成物中の成分Ｂの含有量は、研磨速度の確保及びスクラッチ低減の観点から、０．０１質量％以上が好ましく、０．１質量％以上がより好ましく、１質量％以上が更に好ましく、そして、同様の観点から、５質量％以下が好ましく、４質量％以下がより好ましく、３質量％以下が更に好ましい。より具体的には、本開示の研磨液組成物中の成分Ｂの含有量は、０．０１質量％以上５質量％以下が好ましく、０．１質量％以上４質量％以下がより好ましく、１質量％以上３質量％以下が更に好ましい。成分Ｂが２種以上の組合せである場合、成分Ｂの含有量はそれらの合計含有量をいう。 From the viewpoints of ensuring the polishing rate and reducing scratches, the content of component B in the polishing composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more, and from the same viewpoint, it is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. More specifically, the content of component B in the polishing composition of the present disclosure is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 4% by mass or less, and even more preferably 1% by mass or more and 3% by mass or less. When component B is a combination of two or more types, the content of component B refers to the total content thereof.
本開示の研磨液組成物中の成分Ａの含有量と成分Ｂの含有量との質量比Ａ／Ｂは、研磨速度向上及びスクラッチ低減の観点から、０．２以上が好ましく、０．５以上がより好ましく、１以上が更に好ましく、そして、同様の観点から、１０以下が好ましく、７以下がより好ましく、４以下が更に好ましい。より具体的には、本開示の研磨液組成物中の質量比Ａ／Ｂは、０．２以上１０以下が好ましく、０．５以上７以下がより好ましく、１以上４以下が更に好ましい。 The mass ratio A/B of the content of component A to the content of component B in the polishing liquid composition of the present disclosure is preferably 0.2 or more, more preferably 0.5 or more, and even more preferably 1 or more, from the viewpoint of improving the polishing rate and reducing scratches, and from the same viewpoint, is preferably 10 or less, more preferably 7 or less, and even more preferably 4 or less. More specifically, the mass ratio A/B in the polishing liquid composition of the present disclosure is preferably 0.2 or more and 10 or less, more preferably 0.5 or more and 7 or less, and even more preferably 1 or more and 4 or less.
［酸化剤（成分Ｃ）］
本開示の研磨液組成物は、研磨速度向上及びスクラッチ低減の観点から、酸化剤（以下、「成分Ｃ」ともいう）を含有する。成分Ｃは、１種でもよいし、２種以上の組合せでもよい。
[Oxidizing agent (component C)]
The polishing composition of the present disclosure contains an oxidizing agent (hereinafter also referred to as “component C”) from the viewpoints of improving the polishing rate and reducing scratches. Component C may be one type or a combination of two or more types.
成分Ｃとしては、研磨速度向上及びスクラッチ低減の観点から、例えば、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。これらの中でも、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）から選ばれる少なくとも１種が好ましく、研磨速度の更なる向上の観点、被研磨基板の表面に金属イオンが付着しない観点及び入手容易性の観点から、過酸化水素がより好ましい。 Component C, from the viewpoint of improving the polishing rate and reducing scratches, may, for example, be peroxides, permanganic acid or its salts, chromic acid or its salts, peroxoacids or their salts, oxyacids or their salts, metal salts, nitric acids, sulfuric acids, etc. Among these, at least one selected from hydrogen peroxide, iron (III) nitrate, peracetic acid, ammonium peroxodisulfate, iron (III) sulfate, and ammonium iron (III) sulfate is preferred, and hydrogen peroxide is more preferred from the viewpoint of further improving the polishing rate, from the viewpoint of not adhering metal ions to the surface of the substrate to be polished, and from the viewpoint of easy availability.
本開示の研磨液組成物中の成分Ｃの含有量は、研磨速度向上及びスクラッチ低減の観点から、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましく、そして、４質量％以下が好ましく、２質量％以下がより好ましく、１．５質量％以下が更に好ましい。より具体的には、本開示の研磨液組成物中の成分Ｃの含有量は、０．０１質量％以上４質量％以下が好ましく、０．０５質量％以上２質量％以下がより好ましく、０．１質量％以上１．５質量％以下が更に好ましい。成分Ｃが２種以上の組合せである場合、成分Ｃの含有量はそれらの合計含有量をいう。 From the viewpoint of improving the polishing rate and reducing scratches, the content of component C in the polishing composition of the present disclosure is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more, and preferably 4 mass% or less, more preferably 2 mass% or less, and even more preferably 1.5 mass% or less. More specifically, the content of component C in the polishing composition of the present disclosure is preferably 0.01 mass% or more and 4 mass% or less, more preferably 0.05 mass% or more and 2 mass% or less, and even more preferably 0.1 mass% or more and 1.5 mass% or less. When component C is a combination of two or more types, the content of component C refers to the total content thereof.
［第４級ホスホニウム塩（成分Ｄ）］
本開示の研磨液組成物は、置換基のない炭化水素基を少なくとも１つ有する第４級ホスホニウム塩（以下、「成分Ｄ」ともいう）を含有する。前記炭素水素基とは、リン原子に結合する基、すなわち、リン原子の置換基を指す。また、前記「置換基がない」における置換基は、水素及び／又は炭素のみで構成される基を含まない。成分Ｄは、１種でもよいし、２種以上の組合せでもよい。
前記炭化水素基の１つの基における炭素数は、研磨速度向上及びスクラッチ低減の観点から、１以上が好ましく、３以上がより好ましく、４以上が更に好ましく、そして、シリカの凝集抑制の観点から、１２以下が好ましく、６以下がより好ましい。
前記炭化水素基としては、研磨速度向上及びスクラッチ低減の観点から、アルキル基、アリール基又はアラルキル基が好ましく、アルキル基又はアリール基がより好ましい。前記アルキル基は、研磨速度向上、スクラッチ低減及びシリカの凝集抑制の観点から、炭素数１以上１２以下のアルキル基が好ましく、炭素数４以上７以下のアルキル基がより好ましく、炭素数４以上６以下のアルキル基が更に好ましく、例えば、ブチル基等が挙げられる。前記アリール基としては、研磨速度向上、スクラッチ低減及びシリカの凝集抑制の観点から、炭素数６以上１２以下のアリール基が好ましく、例えば、フェニル基等が挙げられる。前記アラルキル基としては、研磨速度向上、スクラッチ低減及びシリカの凝集抑制の観点から、炭素数７以上１２以下のアラルキル基が好ましく、例えば、ベンジル基等が挙げられる。
前記第４級ホスホニウム塩における対イオンとしては、特に制限されないが、例えば、塩化物イオン（Ｃｌ-）、水酸化物イオン（ＯＨ-）等が挙げられる。
[Quaternary phosphonium salt (component D)]
The polishing composition of the present disclosure contains a quaternary phosphonium salt having at least one unsubstituted hydrocarbon group (hereinafter also referred to as "Component D"). The hydrocarbon group refers to a group bonded to a phosphorus atom, i.e., a substituent of the phosphorus atom. Moreover, the substituent in the "unsubstituted" does not include a group composed only of hydrogen and/or carbon. Component D may be one type or a combination of two or more types.
The number of carbon atoms in one group of the hydrocarbon group is preferably 1 or more, more preferably 3 or more, and even more preferably 4 or more, from the viewpoint of improving the polishing rate and reducing scratches, and is preferably 12 or less, and more preferably 6 or less, from the viewpoint of suppressing aggregation of silica.
The hydrocarbon group is preferably an alkyl group, an aryl group or an aralkyl group, more preferably an alkyl group or an aryl group, from the viewpoint of improving the polishing rate and reducing scratches and suppressing the aggregation of silica. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 4 to 7 carbon atoms, and even more preferably an alkyl group having 4 to 6 carbon atoms, such as a butyl group, from the viewpoint of improving the polishing rate, reducing scratches and suppressing the aggregation of silica. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, such as a phenyl group, from the viewpoint of improving the polishing rate, reducing scratches and suppressing the aggregation of silica. The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, from the viewpoint of improving the polishing rate, reducing scratches and suppressing the aggregation of silica.
The counter ion in the quaternary phosphonium salt is not particularly limited, but examples thereof include a chloride ion (Cl − ) and a hydroxide ion (OH − ).
成分Ｄの合計炭素数としては、研磨速度向上及びスクラッチ低減の観点から、１０以上が好ましく、１３以上がより好ましく、１５以上が更に好ましく、そして、シリカの凝集抑制の観点から、２５以下が好ましく、２４以下がより好ましく、１６以下が更に好ましい。より具体的には、成分Ｄの合計炭素数は、１０以上２５以下が好ましく、１３以上２４以下がより好ましい。 The total number of carbon atoms in component D is preferably 10 or more, more preferably 13 or more, and even more preferably 15 or more, from the viewpoint of improving the polishing rate and reducing scratches, and is preferably 25 or less, more preferably 24 or less, and even more preferably 16 or less, from the viewpoint of suppressing silica aggregation. More specifically, the total number of carbon atoms in component D is preferably 10 or more and 25 or less, and more preferably 13 or more and 24 or less.
成分Ｄは、一又は複数の実施形態において、下記式（Ｉ）で表される化合物であることが好ましい。
上記式（Ｉ）において、Ｒ1、Ｒ2、Ｒ3及びＲ4はそれぞれ独立に、研磨速度向上、スクラッチ低減及びシリカの凝集抑制の観点から、アルキル基、アリール基、又はアラルキル基が好ましく、炭素数１以上１２以下のアルキル基、炭素数６以上１２以下のアリール基、又は炭素数７以上１２以下のアラルキル基がより好ましく、炭素数１以上１２以下のアルキル基、又は炭素数６以上１２以下のアリール基が更に好ましく、炭素数４以上６以下のアルキル基、又は炭素数６のアリール基（フェニル基）が更に好ましい。
Ｒ1、Ｒ2、Ｒ3及びＲ4のうちの少なくとも３つは、研磨速度向上、スクラッチ低減及びシリカの凝集抑制の観点から、同じ基であることが好ましい。
Ｘ-は、研磨速度向上及びスクラッチ低減の観点から、Ｃｌ-（塩化物イオン）又はＯＨ-（水酸化物イオン）が好ましい。
In one or more embodiments, Component D is preferably a compound represented by the following formula (I).
In the above formula (I), R 1 , R 2 , R 3 and R 4 are each independently preferably an alkyl group, an aryl group or an aralkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, still more preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and still more preferably an alkyl group having 4 to 6 carbon atoms or an aryl group having 6 carbon atoms (phenyl group).
From the viewpoints of improving the polishing rate, reducing scratches, and suppressing the aggregation of silica, it is preferable that at least three of R 1 , R 2 , R 3 and R 4 are the same group.
From the viewpoints of improving the polishing rate and reducing scratches, X − is preferably Cl − (chloride ion) or OH − (hydroxide ion).
成分Ｄの分子量は、研磨速度向上及びスクラッチ低減の観点から、２５０以上が好ましく、２８０以上がより好ましく、３００以上が更に好ましく、そして、シリカの凝集抑制の観点からは特に限定はないが、４５０以下が好ましい。 From the viewpoint of improving the polishing rate and reducing scratches, the molecular weight of component D is preferably 250 or more, more preferably 280 or more, and even more preferably 300 or more, and from the viewpoint of suppressing silica aggregation, there is no particular limitation, but 450 or less is preferable.
成分Ｄとしては、一又は複数の実施形態において、研磨速度向上、スクラッチ低減及びシリカの凝集抑制の観点から、テトラブチルホスホニウム塩、テトラフェニルホスホニウム塩、及びトリフェニルベンジルホスホニウム塩から選ばれる少なくとも１種が挙げられる。 In one or more embodiments, component D may be at least one selected from tetrabutylphosphonium salts, tetraphenylphosphonium salts, and triphenylbenzylphosphonium salts, from the viewpoints of improving the polishing rate, reducing scratches, and suppressing silica aggregation.
本開示の研磨液組成物中の成分Ｄの含有量は、研磨速度向上及びスクラッチ低減の観点から、０．０１質量％以上が好ましく、０．０２質量％以上がより好ましく、０．０５質量％以上が更に好ましく、そして、シリカの凝集抑制の観点から、１．０質量％以下が好ましく、０．５質量％以下がより好ましく、０．１質量％以下が更に好ましい。より具体的には、本開示の研磨液組成物中の成分Ｄの含有量は、０．０２質量％以上０．１質量％以下が好ましく、０．０５質量％以上０．１質量％以下がより好ましい。成分Ｄが２種以上の組合せである場合、成分Ｄの含有量はそれらの合計含有量である。 The content of component D in the polishing composition of the present disclosure is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, and even more preferably 0.05 mass% or more, from the viewpoint of improving the polishing rate and reducing scratches, and is preferably 1.0 mass% or less, more preferably 0.5 mass% or less, and even more preferably 0.1 mass% or less, from the viewpoint of suppressing silica aggregation. More specifically, the content of component D in the polishing composition of the present disclosure is preferably 0.02 mass% or more and 0.1 mass% or less, and more preferably 0.05 mass% or more and 0.1 mass% or less. When component D is a combination of two or more types, the content of component D is the total content thereof.
本開示の研磨液組成物中の成分Ａの含有量と成分Ｄの含有量との質量比Ａ／Ｄは、研磨速度向上及びスクラッチ低減の観点から、特に制限は無く、１０以上が好ましく、そして、同様の観点から、１５０以下が好ましく、５０以下がより好ましく、３０以下が更に好ましい。より具体的には、本開示の研磨液組成物中の質量比Ａ／Ｄは、１０以上１５０以下が好ましく、１０以上５０以下がより好ましく、１０以上３０以下が更に好ましい。 The mass ratio A/D of the content of component A to the content of component D in the polishing liquid composition of the present disclosure is not particularly limited from the viewpoint of improving the polishing rate and reducing scratches, and is preferably 10 or more, and from the same viewpoint, is preferably 150 or less, more preferably 50 or less, and even more preferably 30 or less. More specifically, the mass ratio A/D in the polishing liquid composition of the present disclosure is preferably 10 or more and 150 or less, more preferably 10 or more and 50 or less, and even more preferably 10 or more and 30 or less.
［水系媒体］
本開示の研磨液組成物に含まれる水系媒体としては、蒸留水、イオン交換水、純水及び超純水等の水、又は、水と溶媒との混合溶媒等が挙げられる。上記溶媒としては、水と混合可能な溶媒（例えば、エタノール等のアルコール）が挙げられる。水系媒体が、水と溶媒との混合溶媒の場合、混合媒体全体に対する水の割合は、本開示の効果が妨げられない範囲であれば特に限定されなくてもよく、経済性の観点から、例えば、９５質量％以上が好ましく、９８質量％以上がより好ましく、実質的に１００質量％が更に好ましい。被研磨基板の表面清浄性の観点から、水系媒体としては、イオン交換水及び超純水が好ましい。本開示の研磨液組成物中の水系媒体の含有量は、成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ及び必要に応じて配合される後述する任意成分を除いた残余とすることができる。
[Aqueous medium]
The aqueous medium contained in the polishing liquid composition of the present disclosure includes water such as distilled water, ion-exchanged water, pure water, and ultrapure water, or a mixed solvent of water and a solvent. The above-mentioned solvent includes a solvent that can be mixed with water (for example, alcohol such as ethanol). When the aqueous medium is a mixed solvent of water and a solvent, the ratio of water to the entire mixed medium is not particularly limited as long as the effect of the present disclosure is not hindered. From the viewpoint of economic efficiency, for example, 95% by mass or more is preferable, 98% by mass or more is more preferable, and substantially 100% by mass is even more preferable. From the viewpoint of surface cleanliness of the polished substrate, ion-exchanged water and ultrapure water are preferable as the aqueous medium. The content of the aqueous medium in the polishing liquid composition of the present disclosure can be the remainder excluding component A, component B, component C, component D, and optional components described below that are blended as necessary.
［複素環芳香族化合物（成分Ｅ）］
本開示の研磨液組成物は、スクラッチの更なる低減の観点から、複素環芳香族化合物（その塩も含む）（以下、「成分Ｅ」ともいう）をさらに含有してもよい。成分Ｅは１種でもよいし、２種以上の組合せでもよい。
[Heterocyclic aromatic compound (component E)]
From the viewpoint of further reducing scratches, the polishing composition of the present disclosure may further contain a heterocyclic aromatic compound (including a salt thereof) (hereinafter also referred to as "Component E"). Component E may be one type or a combination of two or more types.
成分Ｅとしては、スクラッチの更なる低減の観点から、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ることが好ましく、複素環内に窒素原子を３個以上有することがより好ましく、３個以上９個以下が更に好ましく、３個以上５個以下が更に好ましく、３又は４個が更に好ましい。 From the viewpoint of further reducing scratches, component E is preferably a heterocyclic aromatic compound containing two or more nitrogen atoms in the heterocycle, more preferably three or more nitrogen atoms in the heterocycle, even more preferably three to nine nitrogen atoms, even more preferably three to five nitrogen atoms, and even more preferably three or four nitrogen atoms.
成分Ｅとしては、一又は複数の実施形態において、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（ＢＴＡ）、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、及びこれらのアルキル置換体若しくはアミン置換体から選ばれる少なくとも１種が好ましい。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、一又は複数の実施形態において、メチル基、エチル基が挙げられる。前記アミン置換体としては、一又は複数の実施形態において、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。 In one or more embodiments, component E is preferably at least one selected from 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 (BTA), 1H-tolyltriazole, 2-aminobenzotriazole, 3-aminobenzotriazole, and alkyl- or amine-substituted derivatives thereof. Examples of the alkyl group of the alkyl substituent include lower alkyl groups having 1 to 4 carbon atoms, and in one or more embodiments, examples of the alkyl group include methyl and ethyl groups. In one or more embodiments, examples of the amine substituent include 1-[N,N-bis(hydroxyethylene)aminomethyl]benzotriazole and 1-[N,N-bis(hydroxyethylene)aminomethyl]tolyltriazole.
本開示の研磨液組成物が成分Ｅを含有する場合、本開示の研磨液組成物中の成分Ｅの含有量は、スクラッチの更なる低減の観点から、０．００５質量％以上が好ましく、０．０１質量％以上がより好ましく、０．０２質量％以上が更に好ましく、そして、研磨速度低下抑制の観点から、１０質量％以下が好ましく、５質量％以下がより好ましく、１質量％以下が更に好ましく、０．２質量％以下が更に好ましい。より具体的には、本開示の研磨液組成物中の成分Ｅの含有量は、スクラッチの更なる低減及び研磨速度低下抑制の観点から、０．００５質量％以上１０質量％以下が好ましく、０．０１質量％以上５質量％以下がより好ましく、０．０２質量％以上１質量％以下が更に好ましく、０．０２質量％以上０．２質量％以下が更に好ましい。成分Ｅが２種以上の組合せである場合、成分Ｅの含有量はそれらの合計含有量をいう。 When the polishing liquid composition of the present disclosure contains component E, the content of component E in the polishing liquid composition of the present disclosure is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.02% by mass or more from the viewpoint of further reducing scratches, and is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.2% by mass or less from the viewpoint of suppressing a decrease in the polishing rate. More specifically, the content of component E in the polishing liquid composition of the present disclosure is preferably 0.005% by mass or more and 10% by mass or less, more preferably 0.01% by mass or more and 5% by mass or less, even more preferably 0.02% by mass or more and 1% by mass or less, and even more preferably 0.02% by mass or more and 0.2% by mass or less from the viewpoint of further reducing scratches and suppressing a decrease in the polishing rate. When component E is a combination of two or more types, the content of component E refers to the total content thereof.
［脂肪族アミン化合物又は脂環式アミン化合物（成分Ｆ）］
本開示の研磨液組成物は、スクラッチの更なる低減の観点から、脂肪族アミン化合物及び脂環式アミン化合物から選ばれる少なくとも１種（以下、「成分Ｆ」ともいう）をさらに含有してもよい。スクラッチの更なる低減の観点から、成分Ｆの分子内の窒素原子数又はアミノ基若しくはイミノ基の併せた数は、２個以上４個以下が好ましい。成分Ｆは１種でもよいし、２種以上の組合せでもよい。
[Aliphatic amine compound or alicyclic amine compound (component F)]
From the viewpoint of further reducing scratches, the polishing composition of the present disclosure may further contain at least one selected from an aliphatic amine compound and an alicyclic amine compound (hereinafter also referred to as "Component F"). From the viewpoint of further reducing scratches, the number of nitrogen atoms or the total number of amino groups or imino groups in the molecule of Component F is preferably 2 to 4. Component F may be one type or a combination of two or more types.
前記脂肪族アミン化合物としては、一又は複数の実施形態において、スクラッチの更なる低減の観点から、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、及びＮ－アミノエチル－Ｎ－メチルエタノールアミンから選ばれる少なくとも１種が好ましく、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、及びＮ－アミノエチル－Ｎ－メチルエタノールアミンから選ばれる少なくとも１種がより好ましく、Ｎ－アミノエチルエタノールアミン（ＡＥＡ）が更に好ましい。 In one or more embodiments, the aliphatic amine compound is preferably at least one selected from 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, and N-aminoethyl-N-methylethanolamine, more preferably at least one selected from N-aminoethylethanolamine, N-aminoethylisopropanolamine, and N-aminoethyl-N-methylethanolamine, and even more preferably N-aminoethylethanolamine (AEA).
前記脂環式アミン化合物としては、一又は複数の実施形態において、スクラッチの更なる低減の観点から、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、及びヒドロキシエチルピペラジン（ＨＥＰ）から選ばれる少なくとも１種が好ましく、ヒドロキシエチルピペラジン（ＨＥＰ）がより好ましい。 In one or more embodiments, the alicyclic amine compound is preferably at least one selected from piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 1-amino-4-methylpiperazine, N-methylpiperazine, and hydroxyethylpiperazine (HEP), from the viewpoint of further reducing scratches, and more preferably hydroxyethylpiperazine (HEP).
本開示の研磨液組成物が成分Ｆを含有する場合、本開示の研磨液組成物中の成分Ｆの含有量は、スクラッチの更なる低減の観点から、０．００５質量％以上が好ましく、０．０１質量％以上がより好ましく、０．０２質量％以上が更に好ましく、そして、研磨速度低下抑制の観点から、１０質量％以下が好ましく、５質量％以下がより好ましく、１質量％以下が更に好ましく、０．１質量％以下が更に好ましい。より具体的には、本開示の研磨液組成物中の成分Ｆの含有量は、スクラッチの更なる低減及び研磨速度低下抑制の観点から、０．００５質量％以上１０質量％以下が好ましく、０．０１質量％以上５質量％以下がより好ましく、０．０２質量％以上１質量％以下が更に好ましくは、０．０２質量％以上０．１質量％以下が更に好ましい。成分Ｆが２種以上の組合せである場合、成分Ｆの含有量はそれらの合計含有量をいう。 When the polishing liquid composition of the present disclosure contains component F, the content of component F in the polishing liquid composition of the present disclosure is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.02% by mass or more from the viewpoint of further reducing scratches, and is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.1% by mass or less from the viewpoint of suppressing a decrease in the polishing rate. More specifically, the content of component F in the polishing liquid composition of the present disclosure is preferably 0.005% by mass or more and 10% by mass or less, more preferably 0.01% by mass or more and 5% by mass or less, even more preferably 0.02% by mass or more and 1% by mass or less, and even more preferably 0.02% by mass or more and 0.1% by mass or less from the viewpoint of further reducing scratches and suppressing a decrease in the polishing rate. When component F is a combination of two or more types, the content of component F refers to the total content thereof.
［その他の成分］
本開示の研磨液組成物は、一又は複数の実施形態において、必要に応じてさらにその他の成分を含有していてもよい。その他の成分としては、例えば、高分子化合物、増粘剤、分散剤、防錆剤、塩基性物質、界面活性剤、可溶化剤等が挙げられる。
[Other ingredients]
In one or more embodiments, the polishing composition of the present disclosure may further contain other components as necessary. Examples of the other components include a polymer compound, a thickener, a dispersant, a rust inhibitor, a basic substance, a surfactant, a solubilizer, etc.
［研磨液組成物のｐＨ］
本開示の研磨液組成物のｐＨは、研磨速度の向上及びスクラッチ低減の観点から、５以下が好ましく、４以下がより好ましく、３以下が更に好ましく、ｐＨ２未満が更に好ましく、そして、同様の観点から、０．５以上が好ましく、０．８以上がより好ましく、１以上が更に好ましい。同様の観点から、本開示の研磨液組成物のｐＨは、０．５以上５以下が好ましく、０．８以上４以下がより好ましく、１以上３以下が更に好ましく、１以上２未満が更に好ましい。ｐＨは、上述した酸（成分Ｂ）や公知のｐＨ調整剤等を用いて調整することができる。本開示において、上記ｐＨは、２５℃における研磨液組成物のｐＨであり、ｐＨメータを用いて測定でき、例えば、ｐＨメータの電極を研磨液組成物へ浸漬して２分後の数値とすることができる。
[pH of polishing composition]
The pH of the polishing composition of the present disclosure is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, and even more preferably less than pH 2, from the viewpoint of improving the polishing rate and reducing scratches, and from the same viewpoint, it is preferably 0.5 or more, more preferably 0.8 or more, and even more preferably 1 or more. From the same viewpoint, the pH of the polishing composition of the present disclosure is preferably 0.5 or more and 5 or less, more preferably 0.8 or more and 4 or less, even more preferably 1 or more and 3 or less, and even more preferably 1 or more and less than 2. The pH can be adjusted using the above-mentioned acid (component B) or a known pH adjuster. In the present disclosure, the above pH is the pH of the polishing composition at 25 ° C., and can be measured using a pH meter, and can be, for example, the value after 2 minutes of immersing the electrode of the pH meter in the polishing composition.
［研磨液組成物の製造方法］
本開示の研磨液組成物は、例えば、成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ及び水系媒体と、さらに所望により任意成分（成分Ｅ、成分Ｆ及びその他の成分）とを公知の方法で配合することにより製造できる。すなわち、本開示は、その他の態様において、少なくとも成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ及び水系媒体を配合する工程を含む、研磨液組成物の製造方法に関する。本開示において「配合する」とは、成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ及び水系媒体、並びに必要に応じて任意成分（成分Ｅ、成分Ｆ及びその他の成分）を同時に又は任意の順に混合することを含む。成分Ａ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。成分Ａが複数種類のシリカ粒子からなる場合、複数種類のシリカ粒子は、同時に又はそれぞれ別々に配合できる。成分Ｂが複数種類の酸からなる場合、複数種類の酸は同時に又はそれぞれ別々に配合できる。成分Ｃが複数種類の酸化剤からなる場合、複数種類の酸化剤は同時に又はそれぞれ別々に配合できる。成分Ｄが複数種類の第４級ホスホニウム塩からなる場合、複数種類の第４級ホスホニウム塩は、同時に又はそれぞれ別々に配合できる。前記配合は、例えば、ホモミキサー、ホモジナイザー、超音波分散機及び湿式ボールミル等の混合器を用いて行うことができる。研磨液組成物の製造方法における各成分の好ましい配合量は、上述した本開示の研磨液組成物中の各成分の好ましい含有量と同じとすることができる。
[Method of producing the polishing composition]
The polishing liquid composition of the present disclosure can be produced, for example, by blending component A, component B, component C, component D, and an aqueous medium, and, if desired, optional components (component E, component F, and other components) by a known method. That is, in another aspect, the present disclosure relates to a method for producing a polishing liquid composition, which includes a step of blending at least component A, component B, component C, component D, and an aqueous medium. In the present disclosure, "blending" includes mixing component A, component B, component C, component D, and an aqueous medium, and optional components (component E, component F, and other components) simultaneously or in any order as necessary. Component A may be mixed in the form of a concentrated slurry, or may be mixed after diluting with water or the like. When component A is composed of multiple types of silica particles, the multiple types of silica particles can be blended simultaneously or separately. When component B is composed of multiple types of acids, the multiple types of acids can be blended simultaneously or separately. When component C is composed of multiple types of oxidizing agents, the multiple types of oxidizing agents can be blended simultaneously or separately. When component D is composed of multiple types of quaternary phosphonium salts, the multiple types of quaternary phosphonium salts can be blended simultaneously or separately. The blending can be carried out using a mixer such as a homomixer, a homogenizer, an ultrasonic disperser, or a wet ball mill. The preferred blending amount of each component in the method for producing the polishing composition can be the same as the preferred content of each component in the polishing composition of the present disclosure described above.
本開示において「研磨液組成物中の各成分の含有量」とは、使用時、すなわち、研磨液組成物の研磨への使用を開始する時点における前記各成分の含有量をいう。
本開示の研磨液組成物は、その保存安定性が損なわれない範囲で濃縮された状態で保存及び供給されてもよい。この場合、製造及び輸送コストを更に低くできる点で好ましい。本開示の研磨液組成物の濃縮物は、使用時に、必要に応じて前述の水系媒体で適宜希釈して使用すればよい。希釈倍率は、希釈した後に上述した各成分の含有量（使用時）を確保できれば特に限定されるものではなく、例えば、１０～１００倍とすることができる。
In the present disclosure, "the content of each component in the polishing liquid composition" refers to the content of each component at the time of use, that is, at the time when the use of the polishing liquid composition for polishing is started.
The polishing composition of the present disclosure may be stored and supplied in a concentrated state to the extent that its storage stability is not impaired. In this case, it is preferable in that the manufacturing and transportation costs can be further reduced. The concentrated polishing composition of the present disclosure may be appropriately diluted with the above-mentioned aqueous medium when used as necessary. The dilution ratio is not particularly limited as long as the content (when used) of each of the above-mentioned components can be secured after dilution, and may be, for example, 10 to 100 times.
［研磨液キット］
本開示は、その他の態様において、本開示の研磨液組成物を製造するためのキット（以下、「本開示の研磨液キット」ともいう）に関する。
本開示の研磨液キットとしては、例えば、成分Ａ及び水系媒体を含むシリカ分散液と、成分Ｂ、成分Ｃ及び成分Ｄを含む添加剤水溶液と、を相互に混合されない状態で含み、これらが使用時に混合され、必要に応じて水系媒体を用いて希釈される、研磨液キット（２液型研磨液組成物）が挙げられる。前記シリカ分散液に含まれる水系媒体は、研磨液組成物の調製に使用する水の全量でもよいし、一部でもよい。前記添加剤水溶液には、研磨液組成物の調製に使用する水系媒体の一部が含まれていてもよい。前記シリカ分散液及び前記添加剤水溶液にはそれぞれ必要に応じて、上述した任意成分（成分Ｅ、成分Ｆ及びその他の成分）が含まれていてもよい。本開示の研磨液キットによれば、研磨速度を確保しつつ、研磨後の基板表面のスクラッチを低減可能な研磨液組成物を得ることができる。
[Polishing liquid kit]
In another aspect, the present disclosure relates to a kit for producing the polishing liquid composition of the present disclosure (hereinafter also referred to as the "polishing liquid kit of the present disclosure").
The polishing liquid kit of the present disclosure includes, for example, a polishing liquid kit (two-liquid type polishing liquid composition) that contains a silica dispersion containing component A and an aqueous medium and an additive aqueous solution containing component B, component C, and component D in a mutually unmixed state, which are mixed at the time of use and diluted with an aqueous medium as necessary. The aqueous medium contained in the silica dispersion may be the entire amount of water used in the preparation of the polishing liquid composition, or may be a part of the amount. The additive aqueous solution may contain a part of the aqueous medium used in the preparation of the polishing liquid composition. The silica dispersion and the additive aqueous solution may each contain the above-mentioned optional components (component E, component F, and other components) as necessary. According to the polishing liquid kit of the present disclosure, it is possible to obtain a polishing liquid composition that can reduce scratches on the substrate surface after polishing while ensuring the polishing rate.
［被研磨基板］
被研磨基板は、一又は複数の実施形態において、磁気ディスク基板の製造に用いられる基板である。一又は複数の実施形態において、被研磨基板の表面を本開示の研磨液組成物を用いて研磨する工程の後、スパッタ等でその基板表面に磁性層を形成する工程を行うことにより磁気ディスク基板を製造できる。
[Polished substrate]
In one or more embodiments, the substrate to be polished is a substrate used for manufacturing a magnetic disk substrate. In one or more embodiments, the surface of the substrate to be polished is polished with the polishing composition of the present disclosure, and then a magnetic layer is formed on the substrate surface by sputtering or the like, thereby manufacturing a magnetic disk substrate.
本開示において好適に使用される被研磨基板の材質としては、例えばシリコン、アルミニウム、ニッケル、タングステン、銅、タンタル、チタン等の金属若しくは半金属、又はこれらの合金や、ガラス、ガラス状カーボン、アモルファスカーボン等のガラス状物質や、アルミナ、二酸化珪素、窒化珪素、窒化タンタル、炭化チタン等のセラミック材料や、ポリイミド樹脂等の樹脂等が挙げられる。中でも、アルミニウム、ニッケル、タングステン、銅等の金属及びこれらの金属を主成分とする合金を含有する被研磨基板に好適である。被研磨基板としては、例えば、Ｎｉ－Ｐメッキされたアルミニウム合金基板や、結晶化ガラス、強化ガラス、アルミノシリケートガラス、アルミノボロシリケートガラス等のガラス基板がより適しており、Ｎｉ－Ｐメッキされたアルミニウム合金基板が更に適している。本開示において「Ｎｉ－Ｐメッキされたアルミニウム合金基板」とは、アルミニウム合金基材の表面を研削後、無電解Ｎｉ－Ｐメッキ処理したものをいう。 Materials of the substrate to be polished that are preferably used in the present disclosure include, for example, metals or semimetals such as silicon, aluminum, nickel, tungsten, copper, tantalum, and titanium, or alloys thereof, glassy materials such as glass, glassy carbon, and amorphous carbon, ceramic materials such as alumina, silicon dioxide, silicon nitride, tantalum nitride, and titanium carbide, and resins such as polyimide resins. In particular, the substrate to be polished is preferably one containing metals such as aluminum, nickel, tungsten, and copper, and alloys mainly composed of these metals. As the substrate to be polished, for example, Ni-P plated aluminum alloy substrates and glass substrates such as crystallized glass, reinforced glass, aluminosilicate glass, and aluminoborosilicate glass are more suitable, and Ni-P plated aluminum alloy substrates are even more suitable. In the present disclosure, the term "Ni-P plated aluminum alloy substrate" refers to an aluminum alloy substrate whose surface is ground and then electrolessly plated with Ni-P.
被研磨基板の形状としては、例えば、ディスク状、プレート状、スラブ状、プリズム状等の平面部を有する形状や、レンズ等の曲面部を有する形状が挙げられる。中でも、ディスク状の被研磨基板が適している。ディスク状の被研磨基板の場合、その外径は例えば２～１００ｍｍ程度であり、その厚さは例えば０．４～２ｍｍ程度である。 The shape of the substrate to be polished can be, for example, a disk, plate, slab, prism, or other shape with a flat surface, or a lens or other shape with a curved surface. Of these, a disk-shaped substrate to be polished is suitable. In the case of a disk-shaped substrate to be polished, the outer diameter is, for example, about 2 to 100 mm, and the thickness is, for example, about 0.4 to 2 mm.
［磁気ディスク基板の製造方法］
一般に、磁気ディスクは、研削工程を経た被研磨基板が、粗研磨工程、仕上げ研磨工程を経て研磨され、記録部形成工程にて磁気ディスク化されて製造される。本開示における研磨液組成物は、磁気ディスク基板の製造方法における、被研磨基板を研磨する研磨工程、好ましくは仕上げ研磨工程に使用されうる。すなわち、本開示は、一態様において、本開示の研磨液組成物を用いて被研磨基板を研磨する工程（以下、「本開示の研磨液組成物を用いた研磨工程」ともいう）を含む、磁気ディスク基板の製造方法（以下、「本開示の基板製造方法」ともいう）に関する。本開示の基板製造方法は、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。
[Method of manufacturing magnetic disk substrate]
In general, a magnetic disk is manufactured by polishing a substrate to be polished through a grinding process, a rough polishing process, and a finish polishing process, and forming a magnetic disk in a recording part forming process. The polishing liquid composition of the present disclosure can be used in a polishing process, preferably a finish polishing process, for polishing a substrate to be polished in a method for manufacturing a magnetic disk substrate. That is, in one aspect, the present disclosure relates to a method for manufacturing a magnetic disk substrate (hereinafter also referred to as a "substrate manufacturing method of the present disclosure") including a process for polishing a substrate to be polished using the polishing liquid composition of the present disclosure (hereinafter also referred to as a "polishing process using the polishing liquid composition of the present disclosure"). The substrate manufacturing method of the present disclosure is particularly suitable for a method for manufacturing a magnetic disk substrate for a perpendicular magnetic recording system.
本開示の研磨液組成物を用いた研磨工程は、一又は複数の実施形態において、本開示の研磨液組成物を被研磨基板の研磨対象面に供給し、前記研磨対象面に研磨パッドを接触させ、前記研磨パッド及び前記被研磨基板の少なくとも一方を動かして研磨する工程である。また、本開示の研磨液組成物を用いた研磨工程は、その他の一又は複数の実施形態において、不織布状の有機高分子系研磨布等の研磨パッドを貼り付けた定盤で被研磨基板を挟み込み、本開示の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工程である。 In one or more embodiments, the polishing process using the polishing liquid composition of the present disclosure is a process in which the polishing liquid composition of the present disclosure is supplied to the surface of the substrate to be polished, a polishing pad is brought into contact with the surface to be polished, and at least one of the polishing pad and the substrate to be polished is moved to perform polishing. In another one or more embodiments, the polishing process using the polishing liquid composition of the present disclosure is a process in which the substrate to be polished is sandwiched between a platen to which a polishing pad such as a nonwoven organic polymer-based polishing cloth is attached, and the platen and the substrate to be polished are moved while the polishing liquid composition of the present disclosure is supplied to the polishing machine to polish the substrate to be polished.
被研磨基板の研磨工程が多段階で行われる場合は、本開示の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、最終研磨工程又は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。さらに、使用した研磨液を再利用する循環研磨においても、本開示の研磨液組成物は使用できる。研磨機としては、特に限定されず、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 liquid composition of the present disclosure is preferably performed in the second stage or later, and more preferably in the final polishing process or finish polishing process. In this case, a separate polishing machine may be used for each step to avoid contamination of the abrasive or polishing liquid composition from the previous step, and when a separate polishing machine is used, it is preferable to clean the substrate to be polished after each polishing process. Furthermore, the polishing liquid composition of the present disclosure can be used in circulating polishing in which the used polishing liquid is reused. There are no particular limitations on the polishing machine, and any known polishing machine for substrate polishing can be used.
本開示で使用される研磨パッドとしては、特に制限はなく、例えば、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、研磨速度の観点から、スエードタイプの研磨パッドが好ましい。 There are no particular limitations on the polishing pad used in the present disclosure, and polishing pads of, for example, suede type, nonwoven fabric type, polyurethane independent foam type, or two-layer type laminated with these can be used, with suede type polishing pads being preferred from the viewpoint of polishing speed.
本開示の研磨液組成物を用いた研磨工程における研磨荷重は、研磨速度の確保の観点から、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以上であり、そして、スクラッチ低減の観点から、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。本開示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、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。 The polishing load in the polishing process using the polishing liquid composition of the present disclosure is preferably 5.9 kPa or more, more preferably 6.9 kPa or more, and even more preferably 7.5 kPa or more, from the viewpoint of ensuring the polishing rate, and is preferably 20 kPa or less, more preferably 18 kPa or less, and even more preferably 16 kPa or less, from the viewpoint of reducing scratches. In the manufacturing method of the present disclosure, the polishing load refers to the pressure of the platen applied to the polishing surface of the substrate to be polished during polishing. The polishing load can be adjusted by applying air pressure or a weight to at least one of the platen and the substrate to be polished.
本開示の研磨液組成物を用いた研磨工程における本開示の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、更に好ましくは０．０７ｍＬ／分以上１ｍＬ／分以下、更に好ましくは０．０７ｍＬ／分以上０．５ｍＬ／分以下である。 In a polishing process using the polishing liquid composition of the present disclosure, the supply rate of the polishing liquid composition of the present disclosure is, from the viewpoint of reducing scratches, preferably 0.05 mL/min or more and 15 mL/min or less, more preferably 0.06 mL/min or more and 10 mL/min or less, even more preferably 0.07 mL/min or more and 1 mL/min or less, and even more preferably 0.07 mL/min or more and 0.5 mL/min or less, per 1 cm2 of the substrate to be polished.
本開示の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、本開示の研磨液組成物となる。 The polishing composition of the present disclosure can be supplied to the polishing machine, for example, by continuously supplying the composition using a pump or the like. When supplying the polishing composition to the polishing machine, in addition to supplying the composition as a single liquid containing all the components, the composition can be divided into multiple blending component liquids and supplied as two or more liquids, taking into consideration the stability of the polishing composition. In the latter case, the multiple blending component liquids are mixed, for example, in the supply pipe or on the substrate to be polished, to produce the polishing composition of the present disclosure.
本開示の基板製造方法によれば、研磨速度を確保しつつ、研磨後の基板表面のスクラッチを低減可能な本開示における研磨液組成物を用いることで、高品質の磁気ディスク基板を高収率で、生産性よく製造できるという効果が奏されうる。 According to the substrate manufacturing method of the present disclosure, by using the polishing composition of the present disclosure, which can reduce scratches on the substrate surface after polishing while maintaining the polishing rate, it is possible to produce high-quality magnetic disk substrates with high yield and good productivity.
［研磨方法］
本開示は、一態様として、本開示の研磨液組成物を用いて被研磨基板を研磨することを含む、基板の研磨方法（以下、「本開示の研磨方法」ともいう）に関する。本開示の研磨方法によれば、研磨速度を確保しつつ、研磨後の基板表面のスクラッチを低減可能な本開示の研磨液組成物を用いることで、高品質の磁気ディスク基板を高収率で、生産性よく製造できる。本開示の研磨方法における前記被研磨基板としては、上述のとおり、磁気ディスク基板の製造に使用されるものが挙げられ、なかでも、垂直磁気記録方式用磁気ディスク基板の製造に用いる基板が好ましい。本開示の研磨方法における、研磨の方法及び条件は、上述した本開示の基板製造方法と同じ方法及び条件とすることができる。
[Polishing method]
The present disclosure relates to a method for polishing a substrate (hereinafter also referred to as the "polishing method of the present disclosure"), which includes polishing a substrate to be polished using the polishing composition of the present disclosure. According to the polishing method of the present disclosure, a high-quality magnetic disk substrate can be produced with high yield and good productivity by using the polishing composition of the present disclosure, which can reduce scratches on the substrate surface after polishing while ensuring the polishing rate. As described above, the substrate to be polished in the polishing method of the present disclosure includes those used in the manufacture of magnetic disk substrates, and among them, substrates used in the manufacture of magnetic disk substrates for perpendicular magnetic recording systems are preferred. The polishing method and conditions in the polishing method of the present disclosure can be the same as those in the substrate manufacturing method of the present disclosure described above.
本開示の研磨液組成物を用いて被研磨基板を研磨することは、一又は複数の実施形態において、本開示の研磨液組成物を被研磨基板の研磨対象面に供給し、前記研磨対象面に研磨パッドを接触させ、前記研磨パッド及び前記被研磨基板の少なくとも一方を動かして研磨することであり、或いは、不織布状の有機高分子系研磨布等の研磨パッドを貼り付けた定盤で被研磨基板を挟み込み、本開示の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ことである。 In one or more embodiments, polishing a substrate to be polished using the polishing liquid composition of the present disclosure means supplying the polishing liquid composition of the present disclosure to the surface of the substrate to be polished, contacting the surface to be polished with a polishing pad, and moving at least one of the polishing pad and the substrate to be polished to perform polishing, or sandwiching the substrate to be polished between plates to which a polishing pad such as a nonwoven organic polymer-based polishing cloth is attached, and polishing the substrate to be polished by moving the platen and the substrate to be polished while supplying the polishing liquid composition of the present disclosure to a polishing machine.
以下、実施例により本開示をさらに詳細に説明するが、これらは例示的なものであって、本開示はこれら実施例に制限されるものではない。 The present disclosure will be explained in more detail below with reference to examples, but these are merely illustrative and the present disclosure is not limited to these examples.
１．第４級ホスホニウム塩又は化合物（成分Ｄ又は非成分Ｄ）
表１に示す第４級ホスホニウム塩又は化合物（Ｄ１～Ｄ９）には、以下のものを用いた。
Ｄ１：テトラブチルホスホニウムクロリド［分子量：２９４．８８］
Ｄ２：テトラフェニルホスホニウムクロリド［分子量：３７４．８４］
Ｄ３：トリフェニルベンジルホスホニウムクロリド［分子量：３８８．８７］
Ｄ４：テトラブチルホスホニウムハイドロキサイド［分子量２７６．４４］
Ｄ５：テトラキスヒドロキシメチルホスホニウムスルファート［分子量：４０６．２８］
Ｄ６：トリモルホリノホスフィン［分子量：２８９．３１６］
Ｄ７：トリスルホニルフェニルホスフィン－３，３'，３''－トリスルホン酸三ナトリウム［分子量：５６８．４１］
Ｄ８：トリフェニルホスフィン［分子量：２６２．２９］
Ｄ９：ベンゾトリアゾール［分子量１１９．１２］
1. Quaternary phosphonium salts or compounds (component D or non-component D)
The following quaternary phosphonium salts or compounds (D1 to D9) shown in Table 1 were used.
D1: Tetrabutylphosphonium chloride [Molecular weight: 294.88]
D2: Tetraphenylphosphonium chloride [Molecular weight: 374.84]
D3: Triphenylbenzylphosphonium chloride [Molecular weight: 388.87]
D4: Tetrabutylphosphonium hydroxide [molecular weight 276.44]
D5: Tetrakishydroxymethylphosphonium sulfate [Molecular weight: 406.28]
D6: Trimorpholinophosphine [Molecular weight: 289.316]
D7: Trisulfonylphenylphosphine-3,3',3''-trisulfonic acid trisodium salt [molecular weight: 568.41]
D8: Triphenylphosphine [Molecular weight: 262.29]
D9: Benzotriazole [molecular weight 119.12]
２．研磨液組成物の調製（実施例１～６、比較例１～６）
成分Ａ（コロイダルシリカ）、成分Ｂ（リン酸）、成分Ｃ（過酸化水素）、成分Ｄ又は非成分Ｄ（表１に示すＤ１～Ｄ９）及び水を配合して撹拌することにより、表１に示す実施例１～６及び比較例１～６の研磨液組成物を調製した。各研磨液組成物中の各成分の含有量（質量％、有効量）は、表２に示すとおりである。水の含有量は、成分Ａと成分Ｂと成分Ｃと成分Ｄ又は非成分Ｄとを除いた残余である。
2. Preparation of polishing compositions (Examples 1 to 6, Comparative Examples 1 to 6)
Polishing liquid compositions of Examples 1 to 6 and Comparative Examples 1 to 6 shown in Table 1 were prepared by mixing and stirring component A (colloidal silica), component B (phosphoric acid), component C (hydrogen peroxide), component D or non-component D (D1 to D9 shown in Table 1), and water. The content (mass %, effective amount) of each component in each polishing liquid composition is as shown in Table 2. The content of water is the remainder excluding component A, component B, component C, and component D or non-component D.
各研磨液組成物の調製において、成分Ｂ及び成分Ｃには以下のものを使用した。
（成分Ｂ）
リン酸［和光純薬工業社製、特級］
（成分Ｃ）
過酸化水素水［濃度３５質量％、ADEKA社製］
In preparing each polishing composition, the following components B and C were used.
(Component B)
Phosphoric acid [Wako Pure Chemical Industries, Ltd., special grade]
(Component C)
Hydrogen peroxide solution [concentration 35% by mass, manufactured by ADEKA]
２．各パラメータの測定
［コロイダルシリカ（成分Ａ）の平均二次粒子径］
研磨液組成物の調製に用いた成分Ａ（コロイダルシリカ）と成分Ｂ（リン酸）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。標準試料中における成分Ａ及び成分Ｂの含有量はそれぞれ、１質量％、２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二次粒子径とした。結果を表２に示す。
2. Measurement of each parameter [average secondary particle size of colloidal silica (component A)]
A standard sample was prepared by adding component A (colloidal silica) and component B (phosphoric acid) used in preparing the polishing composition to ion-exchanged water and stirring. The contents of components A and B in the standard sample were 1% by mass and 2% by mass, respectively. The standard sample was subjected to a dynamic light scattering device (DLS-6500 manufactured by Otsuka Electronics Co., Ltd.) according to the manufacturer's attached instructions, and the particle size at which the area of the scattering intensity distribution obtained by the Cumulant method at a detection angle of 90° when integrated 200 times was 50% of the total was determined, and this was taken as the average secondary particle size of the colloidal silica. The results are shown in Table 2.
［ｐＨの測定］
研磨液組成物のｐＨは、ｐＨメータ（東亜ディーケーケー社製）を用いて２５℃にて測定し、電極を研磨液組成物へ浸漬して２分後の数値を採用した。結果を表２に示す。
[pH Measurement]
The pH of the polishing composition was measured at 25° C. using a pH meter (manufactured by DKK-TOA Corporation), and the value measured 2 minutes after the electrode was immersed in the polishing composition was recorded. The results are shown in Table 2.
３．研磨方法
前記のように調製した実施例１～６及び比較例１～６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（仕上げ研磨）した。次いで、研磨速度及びスクラッチ数を測定した。その結果を表２に示す。
なお、比較例５ではシリカが凝集していたため、比較例５の研磨液組成物を用いた研磨は行っていない。
3. Polishing Method Using the polishing compositions of Examples 1 to 6 and Comparative Examples 1 to 6 prepared as described above, the following substrates were polished (finish polished) under the polishing conditions shown below. Then, the polishing rate and the number of scratches were measured. The results are shown in Table 2.
In addition, since silica aggregated in Comparative Example 5, polishing was not performed using the polishing composition of Comparative Example 5.
［被研磨基板］
被研磨基板として、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。この被研磨基板は、厚さが０．６ｍｍ、外径が９７ｍｍ、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であった。
[Polished substrate]
The substrate to be polished was a Ni-P plated aluminum alloy substrate that had been roughly polished with a polishing composition containing an alumina abrasive. The substrate had a thickness of 0.6 mm, an outer diameter of 97 mm, an inner diameter of 25 mm, and a center line average roughness Ra of 1 nm as measured by an AFM (Digital Instrument NanoScope IIIa Multi Mode AFM).
［研磨条件（仕上げ研磨条件）］
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（発泡層：ポリウレタンエラストマー、厚さ０．９ｍｍ、平均開孔径１０μｍ）
研磨液組成物供給量：１００ｍＬ／分（被研磨基板１ｃｍ2あたりの供給速度：０．０７２ｍＬ／分）
下定盤回転数：２５ｒｐｍ
研磨荷重：１３．０ｋＰａ
研磨時間：５分間
基板の枚数：１０枚
[Polishing conditions (finish polishing conditions)]
Polishing test machine: Speedfam's "Double-sided 9B polishing machine"
Polishing pad: Fujibo suede type (foam layer: polyurethane elastomer, thickness 0.9 mm, average pore size 10 μm)
Amount of polishing composition supplied: 100 mL/min (supply rate per cm2 of substrate to be polished: 0.072 mL/min)
Lower platen rotation speed: 25 rpm
Polishing load: 13.0 kPa
Polishing time: 5 minutes Number of substrates: 10
４．評価
［研磨速度の評価］
研磨前後の各基板１枚当たりの重さを計り（Ｓａｒｔｏｒｉｕｓ社製、「ＢＰ－２１０Ｓ」）を用いて測定し、各基板の質量変化から質量減少量を求めた。全１０枚の平均の質量減少量を研磨時間で割った値を研磨速度とし、下記式により算出した。研磨速度の測定結果を、比較例１を１００とした相対値として表２に示す。
質量減少量（ｍｇ）＝｛研磨前の質量（ｍｇ）－ 研磨後の質量（ｍｇ）｝
研磨速度（ｍｇ／分）＝質量減少量（ｍｇ）／ 研磨時間（分）
4. Evaluation [Evaluation of polishing rate]
The weight of each substrate was measured before and after polishing using a Sartorius BP-210S, and the mass loss was calculated from the change in mass of each substrate. The polishing rate was calculated by dividing the average mass loss of all 10 substrates by the polishing time using the following formula. The polishing rate measurement results are shown in Table 2 as relative values with Comparative Example 1 set to 100.
Mass loss (mg) = {mass before polishing (mg) - mass after polishing (mg)}
Polishing rate (mg/min) = mass reduction (mg) / polishing time (min)
［スクラッチの評価］
測定機器：KLA ・テンコール社製、「Ｃａｎｄｅｌａ ＯＳＡ７１００」
評価：研磨試験機に投入した基板のうち、無作為に４枚を選択し、各々の基板を１０,０００ｒｐｍにてレーザーを照射してスクラッチ数を測定した。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、基板面当たりのスクラッチ数を算出した。スクラッチ数の評価結果を、比較例１を１００とした相対値として表２に示す。
[Scratch Evaluation]
Measuring equipment: KLA Tencor "Candela OSA7100"
Evaluation: Four of the substrates were randomly selected from those placed in the polishing tester, and each substrate was irradiated with a laser at 10,000 rpm to measure the number of scratches. The total number of scratches on both sides of each of the four substrates was divided by 8 to calculate the number of scratches per substrate surface. The evaluation results of the number of scratches are shown in Table 2 as a relative value with Comparative Example 1 taken as 100.
［保存安定性の評価］
調製した研磨液を室温にて６０分静置したのち、析出物の有無を目視で確認した。下部に沈降物が確認された場合は析出物ありと判断し、表２において「×」と表記した。沈降物が確認されなかった場合は保存安定性に優れると判断し、表２において「○」と表記した。
[Evaluation of storage stability]
The prepared polishing liquid was left to stand at room temperature for 60 minutes, and then the presence or absence of precipitate was visually confirmed. If precipitate was confirmed at the bottom, it was determined that precipitate was present, and this was indicated as "x" in Table 2. If no precipitate was confirmed, it was determined that the storage stability was excellent, and this was indicated as "○" in Table 2.
上記表２に示すとおり、実施例１～６の研磨液組成物は、比較例１～４、６の研磨液組成物に比べて、保存安定性に優れ、研磨速度を確保しつつ、スクラッチが低減していた。 As shown in Table 2 above, the polishing compositions of Examples 1 to 6 had superior storage stability and reduced scratches while maintaining the polishing rate, compared to the polishing compositions of Comparative Examples 1 to 4 and 6.
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。 This disclosure makes it possible to provide, for example, a magnetic disk substrate suitable for high recording density.
Claims (6)
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