JP6087442B2 - Semiconductor wetting agent and polishing composition - Google Patents
Semiconductor wetting agent and polishing composition Download PDFInfo
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- JP6087442B2 JP6087442B2 JP2015541562A JP2015541562A JP6087442B2 JP 6087442 B2 JP6087442 B2 JP 6087442B2 JP 2015541562 A JP2015541562 A JP 2015541562A JP 2015541562 A JP2015541562 A JP 2015541562A JP 6087442 B2 JP6087442 B2 JP 6087442B2
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- carbon atoms
- water
- formula
- soluble polymer
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- 238000005498 polishing Methods 0.000 title claims description 76
- 239000000203 mixture Substances 0.000 title claims description 58
- 239000004065 semiconductor Substances 0.000 title claims description 40
- 239000000080 wetting agent Substances 0.000 title claims description 40
- 229920003169 water-soluble polymer Polymers 0.000 claims description 82
- 125000004432 carbon atom Chemical group C* 0.000 claims description 52
- 125000000217 alkyl group Chemical group 0.000 claims description 39
- 238000007127 saponification reaction Methods 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000006061 abrasive grain Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 125000003282 alkyl amino group Chemical group 0.000 claims description 10
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000008119 colloidal silica Substances 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 125000005011 alkyl ether group Chemical group 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 235000012431 wafers Nutrition 0.000 description 71
- 229920001577 copolymer Polymers 0.000 description 56
- 238000004519 manufacturing process Methods 0.000 description 39
- 238000006116 polymerization reaction Methods 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 229920002451 polyvinyl alcohol Polymers 0.000 description 23
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 description 18
- -1 acryl Chemical group 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000005530 etching Methods 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 238000009499 grossing Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- 239000005871 repellent Substances 0.000 description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 5
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 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
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- NSOAQRMLVFRWIT-UHFFFAOYSA-N 1-ethenoxydecane Chemical compound CCCCCCCCCCOC=C NSOAQRMLVFRWIT-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
- MIMKRVLJPMYKID-UHFFFAOYSA-N 1-ethenoxynonane Chemical compound CCCCCCCCCOC=C MIMKRVLJPMYKID-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000278 alkyl amino alkyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 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
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- YHOSNAAUPKDRMI-UHFFFAOYSA-N n,n-di(propan-2-yl)prop-2-enamide Chemical compound CC(C)N(C(C)C)C(=O)C=C YHOSNAAUPKDRMI-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror polishing
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
関連出願の相互参照
本出願は、２０１３年１０月７日に出願された日本国特許出願である特願２０１３−２０９７７８の関連出願であり、この日本出願に基づく優先権を主張するものであり、この日本出願に記載された全ての内容を参照により本明細書に組み込まれたものとする。
本発明は、半導体用濡れ剤及び研磨用組成物に関し、さらに詳しくは、シリコンウェーハの仕上げ研磨等に用いられる半導体用濡れ剤及び研磨用組成物に関する。This application is a related application of Japanese Patent Application No. 2013-209778, which is a Japanese patent application filed on October 7, 2013, and claims priority based on this Japanese application, All the contents described in this Japanese application are incorporated herein by reference.
The present invention relates to a wetting agent for semiconductors and a polishing composition, and more particularly to a wetting agent for semiconductors and a polishing composition used for final polishing of a silicon wafer.
パソコン及び携帯電話等の情報通信機器、並びに、デジタルカメラ及びテレビ等のデジタル家電製品では、シリコンウェーハを基板とする半導体デバイスが広く用いられている。近年の半導体チップの高集積化、大容量化に伴い、半導体デバイスの加工精度は微細化の一途をたどっており、デバイス形成前のウェーハに対しては、その平滑性、及びキズ等の欠陥を有さないいわゆる無傷性の要求がますます厳しいものとなっている。 Semiconductor devices using a silicon wafer as a substrate are widely used in information communication devices such as personal computers and mobile phones, and digital home appliances such as digital cameras and televisions. As semiconductor chips have been highly integrated and increased in capacity in recent years, the processing accuracy of semiconductor devices has been continually miniaturized. Wafers prior to device formation have defects such as smoothness and scratches. The so-called intactness requirement that does not exist is becoming increasingly severe.
ウェーハの平滑化技術としては、ＣＭＰ（ケミカルメカニカルポリッシング：化学機械研磨）と呼ばれる研磨プロセスがよく用いられている。ＣＭＰによる平滑化処理では、微細な砥粒と塩基性化合物を含有した研磨用組成物が使用される。この研磨用組成物を研磨パッド表面に供給しながら、圧接した研磨パッドと被研磨物であるウェーハとを相対移動させて表面を研磨する。このとき、砥粒によるメカニカル研磨と、塩基性化合物によるケミカル研磨とが同時に進行することにより、広範囲にわたりウェーハ表面を高精度に平滑化することができる。
一般に、ＣＭＰによるウェーハ研磨では、３〜４段階の研磨を行うことにより、高精度の平滑化を実現している。第１段階および第２段階に行う１次研磨および２次研磨では、表面の平滑化を主な目的としていることから、研磨速度が重要視される傾向がある。これに対し、第３段階または第４段階の仕上げ研磨では、ウェーハ表面のヘイズ及びＣＯＰ（Ｃｒｙｓｔａｌ Ｏｒｉｇｉｎａｔｅｄ Ｐａｒｔｉｃｌｅｓ；結晶欠陥）の抑制、更には凝集した研磨砥粒、研磨パッド屑、研磨により除去されたシリコン粉といったいわゆるパーティクルの付着による汚染防止などについても重要視される。As a wafer smoothing technique, a polishing process called CMP (Chemical Mechanical Polishing) is often used. In the smoothing treatment by CMP, a polishing composition containing fine abrasive grains and a basic compound is used. While supplying this polishing composition to the surface of the polishing pad, the surface is polished by relatively moving the polishing pad in pressure contact with the wafer as the object to be polished. At this time, since the mechanical polishing by the abrasive grains and the chemical polishing by the basic compound proceed simultaneously, the wafer surface can be smoothed over a wide range with high accuracy.
Generally, in wafer polishing by CMP, high-precision smoothing is realized by performing polishing in 3 to 4 stages. In primary polishing and secondary polishing performed in the first stage and the second stage, since the main purpose is to smooth the surface, the polishing rate tends to be regarded as important. On the other hand, in the final polishing in the third stage or the fourth stage, the haze and COP (Crystal Originated Particles) of the wafer surface are suppressed, and further, agglomerated abrasive grains, polishing pad debris, and polishing are removed. Emphasis is also placed on the prevention of contamination caused by the adhesion of so-called particles such as silicon powder.
上記仕上げ研磨に使用される研磨用組成物としては、研磨用組成物中に水溶性高分子化合物を添加する方法が有効であることが知られている。特許文献１には、分子量１０万以上の水溶解性の高分子化合物及び水溶解性の塩類等を含有してなる研磨用組成物が開示されている。また、特許文献２には、水溶性高分子化合物を含む研磨用組成物が記載され、該水溶性高分子化合物として、セルロース誘導体又はポリビニルアルコールを用いることができる旨が示されている。 As a polishing composition used for the above-mentioned finish polishing, it is known that a method of adding a water-soluble polymer compound to the polishing composition is effective. Patent Document 1 discloses a polishing composition comprising a water-soluble polymer compound having a molecular weight of 100,000 or more and water-soluble salts. Patent Document 2 describes a polishing composition containing a water-soluble polymer compound, and indicates that a cellulose derivative or polyvinyl alcohol can be used as the water-soluble polymer compound.
しかし、特許文献１に記載の発明では、用いられる水溶解性高分子化合物のウェーハ表面への吸着性が十分ではなく、仕上げ研磨後のウェーハ表面のヘイズ及びＣＯＰが満足できるものではなかった。また、研磨性向上の目的で添加される水溶解性の塩類もシリカ砥粒の分散性の観点からは好ましくないものであった。シリカ砥粒の分散性が不十分な場合、仕上げ研磨後のウェーハ表面の表面粗さが大きくなり、さらにはスクラッチ傷が発生するなどの問題が起こり易くなる傾向がある。
また、特許文献２に記載のセルロース誘導体又はポリビニルアルコールも同様にウェーハ表面に対する吸着性は十分なものではなかった。加えて、特許文献２の実施例では、具体的な水溶性高分子化合物としてヒドロキシエチルセルロースを用いた実験例が開示されているが、天然物由来の化合物であるために品質のばらつきが大きいという問題もあった。However, in the invention described in Patent Document 1, the water-soluble polymer compound used is not sufficiently adsorbed to the wafer surface, and the haze and COP of the wafer surface after finish polishing are not satisfactory. Also, water-soluble salts added for the purpose of improving the polishing properties are not preferable from the viewpoint of dispersibility of the silica abrasive grains. If the dispersibility of the silica abrasive grains is insufficient, the surface roughness of the wafer surface after finish polishing tends to increase, and problems such as scratches tend to occur.
Similarly, the cellulose derivative or polyvinyl alcohol described in Patent Document 2 is not sufficiently adsorbable on the wafer surface. In addition, in the Example of Patent Document 2, an experimental example using hydroxyethyl cellulose as a specific water-soluble polymer compound is disclosed, but since it is a compound derived from a natural product, there is a problem in that quality variation is large. There was also.
本発明は、このような事情に鑑みてなされたものであり、シリコンウェーハの表面研磨において、ウェーハ表面を高精度に平滑化し、ＣＯＰの抑制に有効な半導体用濡れ剤及び研磨用組成物を提供することを課題とするものである。 The present invention has been made in view of such circumstances, and provides a wetting agent for semiconductor and a polishing composition effective in smoothing the wafer surface with high accuracy and effective in suppressing COP in surface polishing of a silicon wafer. It is an object to do.
上記課題を解決するために鋭意検討した結果、本発明者らは、特定の構造単位を含むポリビニルアルコール系重合体を含む半導体用濡れ剤を用いることにより、研磨後のウェーハ表面の平滑化及びＣＯＰ抑制に効果を奏することを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have made use of a wetting agent for a semiconductor containing a polyvinyl alcohol polymer containing a specific structural unit, thereby smoothing the wafer surface after polishing and COP. It has been found that there is an effect on suppression, and the present invention has been completed.
本発明は以下の通りである。
〔１〕分子中に、式（１）で表される構造単位７０〜９９ｍｏｌ％及び式（２）で表される構造単位１〜３０ｍｏｌ％を有する水溶性高分子を含む半導体用濡れ剤。
［−ＣＨ2ＣＨ（ＯＨ）−］ （１）
［−ＣＨ2ＣＨ（Ｘ）−］ （２）
〔式（２）中、Ｘは炭素数１〜１０のアルキル基を有するアルキルエーテル基、炭素数６〜１０のアリール基、式（３）若しくは式（４）で表される有機基、炭素数１〜１０のアルキル基を有するウレタンアルキル基、炭素数３以上のアルキレン基を有するアルキレンオキシド基、水素又は炭素数１〜３のアルキル基を表す。〕
−Ｃ（＝Ｏ）Ｏ−（ＣＨ2）m−Ｒ1 （３）
〔式（３）中、Ｒ1は炭素数１〜８のアルキル基、炭素数１〜４のアルキル基を有するアルキルアミノ基又はジアルキルアミノ基、ｍは０〜３の整数を表す。〕
−Ｃ（＝Ｏ）ＮＨ−（ＣＨ2）n−Ｒ2 （４）
〔式（４）中、Ｒ2は炭素数１〜８のアルキル基、炭素数１〜４のアルキル基を有するアルキルアミノ基又はジアルキルアミノ基、ｎは０〜３の整数を表す。〕
〔２〕前記水溶性高分子が、酢酸ビニル及び他のビニル系単量体を共重合した後、鹸化することにより得られることを特徴とする前記〔１〕に記載の半導体用濡れ剤。
〔３〕前記水溶性高分子の数平均分子量が１，０００〜２００，０００であることを特徴とする前記〔１〕又は〔２〕に記載の半導体用濡れ剤。
〔４〕前記〔１〕〜〔３〕のいずれかに記載の半導体用濡れ剤、水、砥粒及びアルカリ化合物を含んでなることを特徴とする研磨用組成物。
〔５〕前記砥粒がコロイダルシリカである前記〔４〕に記載の研磨用組成物。
〔６〕シリコンウェーハの仕上げ研磨用である、〔４〕又は〔５〕に記載の研磨用組成物。
〔７〕 分子中に、式（１）で表される構造単位７０〜９９ｍｏｌ％及び式（２）で表される構造単位１〜３０ｍｏｌ％を有する水溶性高分子を用いて、シリコンウエーハを研磨する方法。
［−ＣＨ2ＣＨ（ＯＨ）−］ （１）
［−ＣＨ2ＣＨ（Ｘ）−］ （２）
〔式（２）中、Ｘは炭素数１〜１０のアルキル基を有するアルキルエーテル基、炭素数６〜１０のアリール基、式（３）若しくは式（４）で表される有機基、炭素数１〜１０のアルキル基を有するウレタンアルキル基、炭素数３以上のアルキレン基を有するアルキレンオキシド基、水素又は炭素数１〜３のアルキル基を表す。〕
−Ｃ（＝Ｏ）Ｏ−（ＣＨ2）m−Ｒ1 （３）
〔式（３）中、Ｒ1は炭素数１〜８のアルキル基、炭素数１〜４のアルキル基を有するアルキルアミノ基又はジアルキルアミノ基、ｍは０〜３の整数を表す。〕
−Ｃ（＝Ｏ）ＮＨ−（ＣＨ2）n−Ｒ2 （４）
〔式（４）中、Ｒ2は炭素数１〜８のアルキル基、炭素数１〜４のアルキル基を有するアルキルアミノ基又はジアルキルアミノ基、ｎは０〜３の整数を表す。〕The present invention is as follows.
[1] A wetting agent for a semiconductor containing a water-soluble polymer having 70 to 99 mol% of the structural unit represented by the formula (1) and 1 to 30 mol% of the structural unit represented by the formula (2) in the molecule.
[—CH 2 CH (OH) —] (1)
[—CH 2 CH (X) —] (2)
[In Formula (2), X is an alkyl ether group having an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an organic group represented by Formula (3) or Formula (4), and the number of carbon atoms. A urethane alkyl group having 1 to 10 alkyl groups, an alkylene oxide group having an alkylene group having 3 or more carbon atoms, hydrogen, or an alkyl group having 1 to 3 carbon atoms is represented. ]
-C (= O) O- (CH 2) m -R 1 (3)
[In Formula (3), R 1 represents an integer of alkylamino group or a dialkylamino group, m is 0 to 3 with an alkyl group, an alkyl group having 1 to 4 carbon atoms having 1 to 8 carbon atoms. ]
-C (= O) NH- (CH 2) n -R 2 (4)
[In Formula (4), R 2 represents an alkyl group having 1 to 8 carbon atoms, an alkylamino group having a C 1 to 4 alkyl group or a dialkylamino group, and n represents an integer of 0 to 3. ]
[2] The semiconductor wetting agent according to [1], wherein the water-soluble polymer is obtained by copolymerization of vinyl acetate and another vinyl monomer and then saponification.
[3] The semiconductor wetting agent as described in [1] or [2] above, wherein the water-soluble polymer has a number average molecular weight of 1,000 to 200,000.
[4] A polishing composition comprising the semiconductor wetting agent according to any one of [1] to [3], water, abrasive grains, and an alkali compound.
[5] The polishing composition according to [4], wherein the abrasive grains are colloidal silica.
[6] The polishing composition according to [4] or [5], which is for finish polishing of a silicon wafer.
[7] Polishing a silicon wafer using a water-soluble polymer having 70 to 99 mol% of the structural unit represented by the formula (1) and 1 to 30 mol% of the structural unit represented by the formula (2) in the molecule. how to.
[—CH 2 CH (OH) —] (1)
[—CH 2 CH (X) —] (2)
[In Formula (2), X is an alkyl ether group having an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an organic group represented by Formula (3) or Formula (4), and the number of carbon atoms. A urethane alkyl group having 1 to 10 alkyl groups, an alkylene oxide group having an alkylene group having 3 or more carbon atoms, hydrogen, or an alkyl group having 1 to 3 carbon atoms is represented. ]
-C (= O) O- (CH 2) m -R 1 (3)
[In Formula (3), R 1 represents an integer of alkylamino group or a dialkylamino group, m is 0 to 3 with an alkyl group, an alkyl group having 1 to 4 carbon atoms having 1 to 8 carbon atoms. ]
-C (= O) NH- (CH 2) n -R 2 (4)
[In Formula (4), R 2 represents an alkyl group having 1 to 8 carbon atoms, an alkylamino group having a C 1 to 4 alkyl group or a dialkylamino group, and n represents an integer of 0 to 3. ]
本発明の半導体用濡れ剤は、研磨後のウェーハ表面への吸着性に優れるものである。このため、該半導体用濡れ剤を含む研磨用組成物を用いることにより、研磨後のウェーハ表面の平滑性を高め、かつ、耐エッチング性に優れることからＣＯＰを抑制することが可能となる。さらに、シリカの分散性も良好であることから、凝集したシリカ砥粒による擦傷や表面荒れも少なく、無傷性に優れたウェーハ表面を得ることができる。 The wetting agent for semiconductors of the present invention has excellent adsorptivity to the wafer surface after polishing. For this reason, by using the polishing composition containing the semiconductor wetting agent, it is possible to increase the smoothness of the polished wafer surface and to suppress the COP because of excellent etching resistance. Furthermore, since the dispersibility of silica is also good, there are few scratches and surface roughness due to the agglomerated silica abrasive grains, and a wafer surface with excellent scratch resistance can be obtained.
以下、本開示の代表的かつ非限定的な具体例について、詳細に説明する。この詳細な説明は、本発明の好ましい例を実施するための詳細を当業者に示すことを単純に意図しており、本開示の範囲を限定することを意図したものではない。また、以下に開示される追加的な特徴ならびに発明は、さらに改善された半導体用濡れ剤及び研磨用組成物を提供するために、他の特徴や発明とは別に、又は共に用いることができる。 Hereinafter, representative and non-limiting specific examples of the present disclosure will be described in detail. This detailed description is intended merely to provide those skilled in the art with details for practicing the preferred embodiments of the present invention and is not intended to limit the scope of the present disclosure. Also, the additional features and inventions disclosed below can be used separately from or together with other features and inventions to provide further improved semiconductor wetting agents and polishing compositions.
また、以下の詳細な説明で開示される特徴や工程の組み合わせは、最も広い意味において本開示を実施する際に必須のものではなく、特に本開示の代表的な具体例を説明するためにのみ記載されるものである。さらに、上記及び下記の代表的な具体例の様々な特徴、ならびに、独立及び従属クレームに記載されるものの様々な特徴は、本開示の追加的かつ有用な実施形態を提供するにあたって、ここに記載される具体例のとおりに、あるいは列挙された順番のとおりに組合せなければならないものではない。 Further, the combinations of features and steps disclosed in the following detailed description are not essential in carrying out the present disclosure in the broadest sense, and are particularly only for explaining representative specific examples of the present disclosure. It is described. Moreover, various features of the representative embodiments described above and below, as well as those described in the independent and dependent claims, are described herein in providing additional and useful embodiments of the present disclosure. They do not have to be combined in the specific examples given or in the order listed.
本明細書及び／又はクレームに記載された全ての特徴は、実施例及び／又はクレームに記載された特徴の構成とは別に、出願当初の開示ならびにクレームされた特定事項に対する限定として、個別に、かつ互いに独立して開示されることを意図するものである。さらに、全ての数値範囲及びグループ又は集団に関する記載は、出願当初の開示ならびにクレームされた特定事項に対する限定として、それらの中間の構成を開示する意図を持ってなされている。 All features described in this specification and / or claims, apart from the configuration of the features described in the examples and / or claims, are individually disclosed as limitations on the original disclosure and claimed specific matters. And are intended to be disclosed independently of each other. Further, all numerical ranges and group or group descriptions are intended to disclose intermediate configurations thereof as a limitation to the original disclosure and claimed subject matter.
以下、本発明を詳しく説明する。尚、本明細書において、「（メタ）アクリル」とは、アクリル及びメタクリルを意味し、「（メタ）アクリレート」とは、アクリレート及びメタクリレートを意味する。また、「（メタ）アクリロイル基」とは、アクリロイル基及びメタクリロイル基を意味する。 The present invention will be described in detail below. In the present specification, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate. The “(meth) acryloyl group” means an acryloyl group and a methacryloyl group.
＜水溶性高分子＞
本発明の半導体用濡れ剤は、以下の式（１）で表される構造単位７０〜９９ｍｏｌ％及び式（２）で表される構造単位１〜３０ｍｏｌ％を有する水溶性高分子を含む。
［−ＣＨ2ＣＨ（ＯＨ）−］ （１）
［−ＣＨ2ＣＨ（Ｘ）−］ （２）
〔式（２）中、Ｘは炭素数１〜１０のアルキル基を有するアルキルエーテル基、炭素数６〜１０のアリール基、式（３）若しくは式（４）で表される有機基、炭素数１〜１０のアルキル基を有するウレタンアルキル基、炭素数３以上のアルキレン基を有するアルキレンオキシド基、水素又は炭素数１〜３のアルキル基を表す。〕
−Ｃ（＝Ｏ）Ｏ−（ＣＨ2）m−Ｒ1 （３）
〔式（３）中、Ｒ1は炭素数１〜８のアルキル基、炭素数１〜４のアルキル基を有するアルキルアミノ基又はジアルキルアミノ基、ｍは０〜３の整数を表す。〕
−Ｃ（＝Ｏ）ＮＨ−（ＣＨ2）n−Ｒ2 （４）
〔式（４）中、Ｒ2は炭素数１〜８のアルキル基、炭素数１〜４のアルキル基を有するアルキルアミノ基又はジアルキルアミノ基、ｎは０〜３の整数を表す。〕<Water-soluble polymer>
The wetting agent for semiconductors of the present invention contains a water-soluble polymer having 70 to 99 mol% of structural units represented by the following formula (1) and 1 to 30 mol% of structural units represented by formula (2).
[—CH 2 CH (OH) —] (1)
[—CH 2 CH (X) —] (2)
[In Formula (2), X is an alkyl ether group having an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an organic group represented by Formula (3) or Formula (4), and the number of carbon atoms. A urethane alkyl group having 1 to 10 alkyl groups, an alkylene oxide group having an alkylene group having 3 or more carbon atoms, hydrogen, or an alkyl group having 1 to 3 carbon atoms is represented. ]
-C (= O) O- (CH 2) m -R 1 (3)
[In Formula (3), R 1 represents an integer of alkylamino group or a dialkylamino group, m is 0 to 3 with an alkyl group, an alkyl group having 1 to 4 carbon atoms having 1 to 8 carbon atoms. ]
-C (= O) NH- (CH 2) n -R 2 (4)
[In Formula (4), R 2 represents an alkyl group having 1 to 8 carbon atoms, an alkylamino group having a C 1 to 4 alkyl group or a dialkylamino group, and n represents an integer of 0 to 3. ]
本発明における水溶性高分子は、式（１）で表される構造単位を７０〜９９ｍｏｌ％の範囲で有する。該構造単位の好ましい範囲は７０〜９５ｍｏｌ％であり、より好ましい範囲は７５〜９０ｍｏｌ％である。式（１）で表される構造単位は、ウェーハへの吸着性が良好であるとともに、水溶性高分子の水への溶解性を確保する点で重要である。
水溶性高分子における式（１）で表される構造単位が７０ｍｏｌ％未満の場合、水への溶解性が十分でなく、本発明の半導体用濡れ剤の効果が得られない場合がある。また、９９ｍｏｌ％を超える場合、式（２）で表される構造単位が１ｍｏｌ％未満となるため、ウェーハへの吸着性が不十分となることがある。The water-soluble polymer in the present invention has a structural unit represented by the formula (1) in a range of 70 to 99 mol%. A preferable range of the structural unit is 70 to 95 mol%, and a more preferable range is 75 to 90 mol%. The structural unit represented by the formula (1) is important in that the adsorptivity to the wafer is good and the solubility of the water-soluble polymer in water is ensured.
When the structural unit represented by the formula (1) in the water-soluble polymer is less than 70 mol%, the solubility in water is not sufficient, and the effect of the semiconductor wetting agent of the present invention may not be obtained. Moreover, when it exceeds 99 mol%, since the structural unit represented by Formula (2) will be less than 1 mol%, the adsorptivity to a wafer may become inadequate.
式（２）において、Ｘは炭素数１〜１０のアルキル基を有するアルキルエーテル基、炭素数６〜１０のアリール基、式（３）若しくは式（４）で表される有機基、炭素数１〜１０のアルキル基を有するウレタンアルキル基、炭素数３以上のアルキレン基を有するアルキレンオキシド基、水素又は炭素数１〜３のアルキル基である。Ｘは、これらの内の１種でもよく、又２種以上を併用してもよい。上記の内、ウェーハに対する吸着性が良好であり、かつ、対応する原料が入手し易い点から、炭素数１〜１０のアルキル基を有するアルキルエーテル基、式（３）若しくは式（４）で表される有機基が好ましい。また、耐アルカリ加水分解性が良好である点から炭素数１〜１０のアルキル基を有するアルキルエーテル基がさらに好ましい。 In Formula (2), X is an alkyl ether group having an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an organic group represented by Formula (3) or Formula (4), and 1 carbon atom. A urethane alkyl group having 10 to 10 alkyl groups, an alkylene oxide group having 3 or more alkylene groups, hydrogen, or an alkyl group having 1 to 3 carbon atoms. X may be one of these, or two or more may be used in combination. Among the above, from the point that the adsorptivity to the wafer is good and the corresponding raw material is easily available, the alkyl ether group having an alkyl group having 1 to 10 carbon atoms, represented by formula (3) or formula (4) Preferred are organic groups. Moreover, the alkyl ether group which has a C1-C10 alkyl group from a point with favorable alkali hydrolysis resistance is further more preferable.
また、水溶性高分子において、式（２）で表される構造単位は１〜３０ｍｏｌ％の範囲にあることが必要である。該構造単位の好ましい範囲は５〜３０ｍｏｌ％であり、より好ましい範囲は１０〜２５ｍｏｌ％である。式（２）で表される構造単位は、ウェーハへの吸着性を付与するために重要な構造単位である。
式（２）で表される構造単位が１ｍｏｌ％未満の場合はウェーハへの吸着性が不十分となる場合があり、３０ｍｏｌ％を超える場合は水への溶解性が不十分となることが懸念される。In the water-soluble polymer, the structural unit represented by the formula (2) needs to be in the range of 1 to 30 mol%. A preferable range of the structural unit is 5 to 30 mol%, and a more preferable range is 10 to 25 mol%. The structural unit represented by the formula (2) is an important structural unit for imparting adsorptivity to the wafer.
If the structural unit represented by formula (2) is less than 1 mol%, the adsorptivity to the wafer may be insufficient, and if it exceeds 30 mol%, the solubility in water may be insufficient. Is done.
水溶性高分子の数平均分子量は、１，０００〜２００，０００の範囲であることが好ましく、より好ましくは１，５００〜１００，０００の範囲であり、さらに好ましくは２，０００〜５０，０００の範囲である。数平均分子量が１，０００以上の場合、ウェーハの濡れ性が良好となる傾向があり、２００，０００以下であれば、研磨砥粒の分散性を確保することができる。なお、数平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー、例えば、ＨＬＣ−８２２０、東ソー製）を用いて、ポリスチレン換算により測定できる。 The number average molecular weight of the water-soluble polymer is preferably in the range of 1,000 to 200,000, more preferably in the range of 1,500 to 100,000, still more preferably 2,000 to 50,000. Range. When the number average molecular weight is 1,000 or more, the wettability of the wafer tends to be good, and when it is 200,000 or less, the dispersibility of the abrasive grains can be ensured. The number average molecular weight can be measured by polystyrene conversion using GPC (gel permeation chromatography, for example, HLC-8220, manufactured by Tosoh Corporation).
＜水溶性高分子の製造方法＞
本発明における水溶性高分子は、例えば、重合溶媒中、重合開始剤等の存在下でギ酸ビニル、酢酸ビニル及びプロピオン酸ビニル等のビニルエステル類と式（２）で表される構造単位を有する単量体からなる単量体混合物を共重合した後、ビニルエステル類由来の構造単位を鹸化することにより得ることができる。尚、ビニルエステル類としては、重合安定性等の観点から酢酸ビニルが好ましい。
また、これとは別に、ポリビニルアルコール類の水酸基の一部を炭素数１〜１０のアルキル基を有するイソシアネート化合物と反応させ、ウレタン変性することによっても得ることができる。
さらに、ポリビニルアルコール類の水酸基の一部に炭素数３以上の酸化アルキレンを付加することによっても得ることができる。付加する酸化アルキレンは、炭素数３〜６のものが好ましく、炭素数３〜４のものがより好ましい。<Method for producing water-soluble polymer>
The water-soluble polymer in the present invention has, for example, a vinyl ester such as vinyl formate, vinyl acetate and vinyl propionate in the polymerization solvent in the presence of a polymerization initiator and the like and a structural unit represented by the formula (2). It can be obtained by copolymerizing a monomer mixture comprising monomers and then saponifying the structural units derived from vinyl esters. The vinyl esters are preferably vinyl acetate from the viewpoint of polymerization stability.
Apart from this, it can also be obtained by reacting a part of the hydroxyl groups of polyvinyl alcohol with an isocyanate compound having an alkyl group having 1 to 10 carbon atoms and modifying it with urethane.
Furthermore, it can be obtained by adding an alkylene oxide having 3 or more carbon atoms to a part of hydroxyl groups of polyvinyl alcohols. The alkylene oxide to be added preferably has 3 to 6 carbon atoms, and more preferably has 3 to 4 carbon atoms.
式（２）で表される構造単位を有する単量体の具体的な化合物としては、メチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、イソプロピルビニルエーテル、ｎ−ブチルビニルエーテル、イソブチルビニルエーテル、ｔ−ブチルビニルエーテル、ｎ−ヘキシルビニルエーテル、２−エチルヘキシルビニルエーテル、ｎ−オクチルビニルエーテル、ｎ−ノニルビニルエーテル及びｎ−デシルビニルエーテル等の炭素数１〜１０のアルキル基を有するアルキルビニルエーテル類；スチレン、ビニルトルエン及びビニルキシレン等の芳香族ビニル化合物；メチル（メタ）アクリルアミド、エチル（メタ）アクリルアミド、ｎ−プロピル（メタ）アクリルアミド、イソプロピル（メタ）アクリルアミド、ｎ−ブチル（メタ）アクリルアミド及び２−エチルヘキシル（メタ）アクリルアミド等のＮ−アルキル（メタ）アクリルアミド；メチルアミノプロピル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、エチルアミノプロピル（メタ）アクリルアミド及びジエチルアミノプロピル（メタ）アクリルアミド等の（ジ）アルキルアミノアルキルアミド類；メチルアミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、エチルアミノエチル（メタ）アクリレート及びジエチルアミノエチル（メタ）アクリレート等の（ジ）アルキルアミノアルキル（メタ）アクリレート類；エチレン、プロピレン、ブチレン等のα―オレフィン類等が挙げられ、これらの内の１種又は２種以上を用いることができる。 Specific examples of the monomer having the structural unit represented by the formula (2) include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, Alkyl vinyl ethers having an alkyl group having 1 to 10 carbon atoms such as n-hexyl vinyl ether, 2-ethylhexyl vinyl ether, n-octyl vinyl ether, n-nonyl vinyl ether and n-decyl vinyl ether; fragrances such as styrene, vinyl toluene and vinyl xylene Group vinyl compounds; methyl (meth) acrylamide, ethyl (meth) acrylamide, n-propyl (meth) acrylamide, isopropyl (meth) acrylamide, n-butyl (meth) N-alkyl (meth) acrylamides such as chloramide and 2-ethylhexyl (meth) acrylamide; methylaminopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, ethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide (Di) alkylaminoalkylamides of (di) alkylaminoalkyl (meth) acrylate such as methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate ) Acrylates; α-olefins such as ethylene, propylene, butylene and the like can be mentioned, and one or more of them can be used.
また、前記単量体混合物は、本発明の効果が得られる範囲において、ビニルエステル類及び式（２）で表される構造単位を有する単量体以外の単量体を含んでいてもよい。具体的な化合物としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル及び（メタ）アクリル酸２−エチルヘキシル等の（メタ）アクリル酸アルキルエステル類；（メタ）アクリル酸、クロトン酸、マレイン酸、イタコン酸及びフマル酸等の不飽和酸並びにこれらのアルキルエステル類；無水マレイン酸等の不飽和酸無水物；２−アクリルアミド−２−メチルプロパンスルホン酸及びその塩類等のスルホン酸基含有単量体などが挙げられる。
水溶性高分子におけるこれらの単量体の使用量は、０〜２５ｍｏｌ％の範囲が好ましく、０〜１５ｍｏｌ％の範囲がより好ましい。Moreover, the said monomer mixture may contain monomers other than the monomer which has a structural unit represented by vinylesters and Formula (2) in the range in which the effect of this invention is acquired. Specific compounds include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; (meth) Unsaturated acids such as acrylic acid, crotonic acid, maleic acid, itaconic acid and fumaric acid and their alkyl esters; unsaturated acid anhydrides such as maleic anhydride; 2-acrylamido-2-methylpropanesulfonic acid and its salts And sulfonic acid group-containing monomers such as
The amount of these monomers used in the water-soluble polymer is preferably in the range of 0 to 25 mol%, more preferably in the range of 0 to 15 mol%.
前記共重合方法は特に制限されるものではないが、溶液重合法が好ましい。溶液重合によれば、均一な溶液として本発明の水溶性高分子たる共重合体を得ることができる。
溶液重合の際の重合溶媒には、メタノール、エタノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、及びＮ，Ｎ−ジメチルホルムアミド等のアミド類等が挙げられ、これらの内の１種、又は２種以上を併用して用いてもよい。上記の中でも、重合後のポリマー溶液をそのまま後述する鹸化反応に用いることができる点からメタノールが好ましい。The copolymerization method is not particularly limited, but a solution polymerization method is preferable. By solution polymerization, the copolymer which is the water-soluble polymer of the present invention can be obtained as a uniform solution.
Examples of the polymerization solvent for the solution polymerization include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and amides such as N, N-dimethylformamide, and one of these, or Two or more kinds may be used in combination. Among these, methanol is preferable because the polymer solution after polymerization can be used as it is for the saponification reaction described later.
また、重合の際には公知の重合開始剤を使用出来るが、特にラジカル重合開始剤が好ましく用いられる。
ラジカル重合開始剤としては、例えば、過硫酸ナトリウム、過硫酸カリウム及び過硫酸アンモニウム等の過硫酸塩類、ｔ−ブチルハイドロパーオキサイド等のハイドロパーオキサイド類、過酸化水素等の水溶性過酸化物、メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド等のケトンパーオキサイド類、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド等のジアルキルパーオキサイド類、ｔ−ブチルパーオキシピバレート、ｔ−ヘキシルパーオキシピバレート等のパーオキシエステル類等の油溶性の過酸化物、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）等のアゾ化合物等が挙げられる。
前記ラジカル重合開始剤は１種類のみ使用しても又は２種以上を併用してもよい。
前記ラジカル重合開始剤の中でも、重合反応の制御が行い易い点より過硫酸塩類やアゾ化合物が好ましく、特に好ましくはアゾ化合物である。
ラジカル重合開始剤の使用割合は特に制限されないが、水溶性高分子全体を構成する全単量体の合計重量に基づいて、０．１〜１０質量％の割合で使用することが好ましく、０．１〜５質量％の割合がより好ましく、０．２〜３質量％の割合がさらに好ましい。In the polymerization, a known polymerization initiator can be used, and a radical polymerization initiator is particularly preferably used.
Examples of the radical polymerization initiator include persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate, hydroperoxides such as t-butyl hydroperoxide, water-soluble peroxides such as hydrogen peroxide, and methyl ethyl ketone. Ketone peroxides such as peroxide and cyclohexanone peroxide, dialkyl peroxides such as di-t-butyl peroxide and t-butylcumyl peroxide, t-butyl peroxypivalate, t-hexyl peroxypivalate, etc. Oil-soluble peroxides such as peroxyesters, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2 -Methylbutyronitrile) and the like.
The radical polymerization initiator may be used alone or in combination of two or more.
Among the radical polymerization initiators, persulfates and azo compounds are preferable from the viewpoint of easy control of the polymerization reaction, and azo compounds are particularly preferable.
The ratio of the radical polymerization initiator used is not particularly limited, but is preferably 0.1 to 10% by mass based on the total weight of all monomers constituting the entire water-soluble polymer. A ratio of 1 to 5% by mass is more preferable, and a ratio of 0.2 to 3% by mass is more preferable.
本発明における水溶性高分子の製造において、分子量を調整するために、連鎖移動剤を重合系に適宜添加してもよい。連鎖移動剤としては、例えば、メルカプト酢酸、メルカプトプロピオン酸、２−プロパンチオール、２−メルカプトエタノールが挙げられる。
上記した連鎖移動剤は１種類のみ使用しても又は２種以上を併用してもよい。連鎖移動剤を用いる際、その好ましい使用量は、全単量体の量に対して０．１〜１０質量％であり、さらに好ましくは０．５〜５質量％である。In the production of the water-soluble polymer in the present invention, a chain transfer agent may be appropriately added to the polymerization system in order to adjust the molecular weight. Examples of the chain transfer agent include mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, and 2-mercaptoethanol.
The above chain transfer agents may be used alone or in combination of two or more. When using a chain transfer agent, the preferable usage-amount is 0.1-10 mass% with respect to the quantity of all the monomers, More preferably, it is 0.5-5 mass%.
重合時における反応温度としては、３０〜１００℃が好ましく、４０〜９０℃がより好ましく、５０〜８０℃がさらに好ましい。 As reaction temperature at the time of superposition | polymerization, 30-100 degreeC is preferable, 40-90 degreeC is more preferable, and 50-80 degreeC is further more preferable.
上記共重合の後、得られた共重合体を、有機溶媒中において、触媒の存在下で鹸化する。この鹸化工程で使用する有機溶媒(以下、鹸化溶媒という。)としては、メタノール、エタノール、プロパノール、エチレングリコール、プロピレングリコール、グリセリン及びジエチレングリコールなどのアルコール類を使用することができるが、特に、メタノールが好ましい。 After the copolymerization, the obtained copolymer is saponified in the presence of a catalyst in an organic solvent. As the organic solvent used in this saponification step (hereinafter referred to as saponification solvent), alcohols such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol can be used. preferable.
また、鹸化触媒としては、例えば、水酸化ナトリウム、水酸化カリウム、ナトリウムアルコラート及び炭酸ナトリウムなどのアルカリ触媒、硫酸、燐酸及び塩酸などの酸触媒が挙げられる。これら鹸化触媒の中でも、アルカリ触媒を使用することが好ましく、水酸化ナトリウム又は水酸化カリウムを使用することがより好ましい。これにより、鹸化速度を早くして、生産性を向上させることができる。 Examples of the saponification catalyst include alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium alcoholate and sodium carbonate, and acid catalysts such as sulfuric acid, phosphoric acid and hydrochloric acid. Among these saponification catalysts, an alkali catalyst is preferably used, and sodium hydroxide or potassium hydroxide is more preferably used. Thereby, the saponification rate can be increased and the productivity can be improved.
この鹸化により、共重合体におけるビニルエステル単位の一部又は全部が鹸化されて、ビニルアルコール単位となる。なお、鹸化度は、特に限定されるものではなく、水溶性高分子の組成などに応じて適宜設定することができるが、一般には、７０〜９９．９ｍｏｌ％、好ましく８０〜９９ｍｏｌ％、さらに好ましくは９０〜９９ｍｏｌ％である。 By this saponification, a part or all of the vinyl ester units in the copolymer are saponified into vinyl alcohol units. The degree of saponification is not particularly limited and can be appropriately set according to the composition of the water-soluble polymer, but generally 70 to 99.9 mol%, preferably 80 to 99 mol%, more preferably Is 90-99 mol%.
鹸化により得られた水溶性高分子は、有機溶媒及び水等を公知の方法により乾燥除去し、固体の状態で扱うこともできる。乾燥後、必要に応じて粉砕及び分級等の工程を経てもよい。
また、乾燥前に、例えば酢酸メチル、メタノール及び水等を洗浄液として洗浄することにより、塩類や揮発成分等を低減することもできる。The water-soluble polymer obtained by saponification can be handled in a solid state by drying and removing an organic solvent and water by a known method. After drying, steps such as pulverization and classification may be performed as necessary.
In addition, before drying, for example, methyl acetate, methanol, water, and the like are washed as a washing solution, whereby salts, volatile components, and the like can be reduced.
＜半導体用濡れ剤＞
本発明の半導体用濡れ剤は、前記水溶性高分子を含んでなる。概して、半導体用濡れ剤は、水を含むことができる。また、半導体用濡れ剤は、水溶性高分子が水に溶解した水溶液であることが好ましい。水は、濡れ剤としての効果を損なわないよう、純度の高いものを用いることが好ましい。具体的には、イオン交換樹脂により不純物イオンを除去した後、濾過により異物を除去した純水若しくは超純水、又は、蒸留水を使用することが好ましい。濡れ剤には、この他に、水との混和性が高いアルコール及びケトン類等の有機溶剤等を含んでいてもよい。
半導体用濡れ剤中の水溶性高分子の割合は、水溶液として扱いやすい粘度であれば特に限定されないが、１〜５０質量％の範囲が好ましく、３〜４０質量％の範囲がより好ましく、５〜３０質量％の範囲がさらに好ましい。<Wetting agent for semiconductors>
The wetting agent for semiconductor of the present invention comprises the water-soluble polymer. In general, semiconductor wetting agents can include water. The semiconductor wetting agent is preferably an aqueous solution in which a water-soluble polymer is dissolved in water. It is preferable to use high-purity water so as not to impair the effect as a wetting agent. Specifically, it is preferable to use pure water, ultrapure water, or distilled water from which foreign ions are removed by filtration after removing impurity ions with an ion exchange resin. In addition to this, the wetting agent may contain an organic solvent such as alcohol and ketone having high miscibility with water.
Although the ratio of the water-soluble polymer in the wetting agent for semiconductor is not particularly limited as long as it is a viscosity that can be easily handled as an aqueous solution, the range is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, The range of 30% by mass is more preferable.
本発明における水溶性高分子は、ウェーハ表面等への吸着性に優れ、特に完全に酸化膜が除去された状態のウェーハ表面に対して高い吸着性を示す。このため、ウェーハの表面処理工程に本発明の半導体用濡れ剤を用いた場合、研磨後のウェーハ表面の平滑性を高め、ＣＯＰ及びパーティクル付着による汚染等を低減することができる。これらの効果が得られる理由として、以下のメカニズムを想定している。
ウェーハ表面の平滑性に関しては、半導体用濡れ剤中の水溶性高分子がウェーハ表面に吸着することで、ＣＭＰのメカニカル研磨においてウェーハ表面と砥粒との間の摩擦が緩和される。このため、メカニカル研磨によりウェーハ表面に形成される微小な凹凸が低減され、平滑性が向上すると考えられる。The water-soluble polymer in the present invention is excellent in adsorptivity to the wafer surface and the like, and particularly exhibits high adsorptivity to the wafer surface in a state where the oxide film is completely removed. For this reason, when the semiconductor wetting agent of the present invention is used in the wafer surface treatment process, the smoothness of the polished wafer surface can be improved, and contamination caused by COP and particle adhesion can be reduced. The following mechanism is assumed as a reason why these effects can be obtained.
Regarding the smoothness of the wafer surface, the water-soluble polymer in the semiconductor wetting agent is adsorbed on the wafer surface, so that the friction between the wafer surface and the abrasive grains is reduced in the mechanical polishing of CMP. For this reason, it is considered that the minute unevenness formed on the wafer surface by mechanical polishing is reduced and the smoothness is improved.
また、上述した通り、メカニカル研磨では、ウェーハ表面に研磨用組成物が供給されるとともに研磨パッドがウェーハ表面に押し付けられて回転することにより、ウェーハ表面を物理的に研磨する。よって、ウェーハ表面ではＣＯＰ以外の箇所に研磨パッドが押し付けられ、ウェーハ表面に対して垂直方向に研磨されることとなる。メカニカル研磨の進行に伴いＣＯＰは次第に小さくなり、その深さ以上にウェーハ表面が研磨されたときにＣＯＰは消滅することとなる。したがって、メカニカル研磨は、ＣＯＰの数を減少させ、又その大きさを低減する効果を示すと考えられる。
一方、ケミカル研磨では、研磨の際にＣＯＰ内に研磨用組成物が入り込み、塩基性化合物がＣＯＰ内部を腐食又はエッチングする。このように、ＣＯＰ内部では、その内部壁に対して垂直方向に研磨されるため、ケミカル研磨の進行に伴いウェーハ表面のＣＯＰは大きくなると考えられる。
本発明では、ウェーハ表面に吸着した水溶性高分子は、メカニカル研磨以上にケミカル研磨を抑制する働きを有するものと想定している。ウェーハに対する水溶性高分子の吸着性が高いほどこの傾向は強くなり、結果として平滑性が高くＣＯＰの少ないウェーハ表面を得ることができると推察される。In addition, as described above, in mechanical polishing, the polishing composition is supplied to the wafer surface and the polishing pad is pressed against the wafer surface and rotated to physically polish the wafer surface. Therefore, the polishing pad is pressed against a portion other than the COP on the wafer surface and polished in a direction perpendicular to the wafer surface. As the mechanical polishing proceeds, the COP gradually decreases, and the COP disappears when the wafer surface is polished beyond the depth. Therefore, it is considered that the mechanical polishing shows the effect of reducing the number of COPs and the size thereof.
On the other hand, in chemical polishing, the polishing composition enters the COP during polishing, and the basic compound corrodes or etches the inside of the COP. As described above, since the polishing is performed in the direction perpendicular to the inner wall of the COP, it is considered that the COP on the wafer surface increases with the progress of chemical polishing.
In the present invention, it is assumed that the water-soluble polymer adsorbed on the wafer surface has a function of suppressing chemical polishing more than mechanical polishing. It is presumed that this tendency becomes stronger as the water-soluble polymer adsorbability to the wafer becomes higher, and as a result, a wafer surface having high smoothness and low COP can be obtained.
さらに、ウェーハ表面に水溶性高分子が吸着することにより、その表面が親水化される。これにより、研磨の際のパーティクルの付着による汚染も防止することができる。 Furthermore, when the water-soluble polymer is adsorbed on the wafer surface, the surface is hydrophilized. Thereby, contamination due to adhesion of particles during polishing can also be prevented.
なお、本発明によれば、こうした水溶性高分子をウェーハに対して吸着させてウェーハを研磨する方法も提供される。水溶性高分子をウェーハに対して吸着させる形態としては、水溶性高分子と水とを含む半導体用濡れ剤として供給するほか、本開示の水溶性高分子、水、砥粒及びアルカリ化合物を含む研磨用組成物をウエーハに対して供給する形態が含まれる。 The present invention also provides a method for polishing a wafer by adsorbing such a water-soluble polymer to the wafer. As a form in which the water-soluble polymer is adsorbed to the wafer, the water-soluble polymer is supplied as a semiconductor wetting agent containing water-soluble polymer and water, and includes the water-soluble polymer of the present disclosure, water, abrasive grains, and an alkali compound. The form which supplies polishing composition with respect to a wafer is contained.
＜研磨用組成物＞
本発明の研磨用組成物は、上記半導体用濡れ剤、水、砥粒及びアルカリ化合物を含んでなるものである。研磨用組成物中の半導体用濡れ剤の割合は、特に限定されるものではないが、研磨用組成物がＣＭＰにおける扱い上、又ウェーハ表面に吸着するにあたり適度な粘度とすることが好ましい。研磨用組成物の具体的な粘度は、０．１〜１０ｍＰａ・ｓの範囲であることが好ましく、０．３〜８ｍＰａ・ｓの範囲であることがより好ましく、０．５〜５ｍＰａ・ｓの範囲であることがさらに好ましい。
また、上記水溶性高分子は、研磨剤用組成物全体の０．００１〜１０質量％の範囲となるよう用いることが好ましく、０．００５〜５質量％の範囲であることがより好ましい。<Polishing composition>
The polishing composition of the present invention comprises the semiconductor wetting agent, water, abrasive grains, and an alkali compound. The ratio of the semiconductor wetting agent in the polishing composition is not particularly limited, but it is preferable that the polishing composition has an appropriate viscosity for handling in CMP and adsorbing to the wafer surface. The specific viscosity of the polishing composition is preferably in the range of 0.1 to 10 mPa · s, more preferably in the range of 0.3 to 8 mPa · s, and 0.5 to 5 mPa · s. More preferably, it is in the range.
Moreover, it is preferable to use the said water-soluble polymer so that it may become the range of 0.001-10 mass% of the whole composition for abrasive | polishing agents, and it is more preferable that it is the range of 0.005-5 mass%.
砥粒としてはコロイダルシリカ等を用いることができる。砥粒としてコロイダルシリカを用いる場合、研磨用組成物におけるその含有量は、０．１〜５０質量％であることが好ましく、１〜３０質量％であることがより好ましく、３〜２０質量％であることがさらに好ましい。コロイダルシリカの使用量が０．１質量％以上であればメカニカル研磨の研磨速度が良好なものとなる。また、５０質量％以下であれば、砥粒の分散性が保持され、ウェーハ表面の平滑性が良好なものとすることができる。 Colloidal silica or the like can be used as the abrasive. When colloidal silica is used as the abrasive, the content in the polishing composition is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and 3 to 20% by mass. More preferably it is. If the usage-amount of colloidal silica is 0.1 mass% or more, the polishing rate of mechanical polishing will become favorable. Moreover, if it is 50 mass% or less, the dispersibility of an abrasive grain is hold | maintained and the smoothness of a wafer surface can be made favorable.
コロイダルシリカの平均粒子径は、必要とする研磨速度と研磨後のウェーハ表面の平滑性から適宜選択されるが、一般的には、２〜５００ｎｍの範囲であり、５〜３００ｎｍの範囲が好ましく、５〜２００ｎｍの範囲がより好ましい。 The average particle size of the colloidal silica is appropriately selected from the required polishing rate and the smoothness of the polished wafer surface, but is generally in the range of 2 to 500 nm, preferably in the range of 5 to 300 nm. A range of 5 to 200 nm is more preferable.
アルカリ化合物としては、水溶性のアルカリ化合物であれば特に制限はなく、アルカリ金属水酸化物、アミン類又はアンモニア若しくは４級水酸化アンモニウム塩等を使用することができる。アルカリ金属水酸化物としては、水酸化カリウム、水酸化ナトリウム、水酸化ルビジウム及び水酸化セシウム等が挙げられる。アミン類としては、トリエチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジイソプロパノールアミン、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチルペンタミン及びテトラエチルペンタミン等が挙げられる。４級水酸化アンモニウム塩としては、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム及び水酸化テトラブチルアンモニウム等が挙げられる。これらの内では、半導体基板に対する汚染が少ないという点からアンモニア又は４級水酸化アンモニウム塩が好ましい。
本発明の研磨用組成物は、前記アルカリ化合物を添加することにより、そのｐＨが８〜１３となるように調整されるのが好ましい。ｐＨの範囲は８．５〜１２に調整するのがより好ましい。The alkali compound is not particularly limited as long as it is a water-soluble alkali compound, and alkali metal hydroxides, amines, ammonia, quaternary ammonium hydroxide salts, and the like can be used. Examples of the alkali metal hydroxide include potassium hydroxide, sodium hydroxide, rubidium hydroxide and cesium hydroxide. Examples of amines include triethylamine, monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylpentamine, and tetraethylpentamine. Examples of the quaternary ammonium hydroxide salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Among these, ammonia or a quaternary ammonium hydroxide salt is preferable from the viewpoint of less contamination of the semiconductor substrate.
The polishing composition of the present invention is preferably adjusted to have a pH of 8 to 13 by adding the alkali compound. More preferably, the pH range is adjusted to 8.5-12.
研磨剤用組成物には、上記以外にも、必要に応じて有機溶剤、各種キレート剤及び界面活性剤等を添加することができる。 In addition to the above, an organic solvent, various chelating agents, surfactants, and the like can be added to the abrasive composition as necessary.
以下、実施例に基づいて本発明を具体的に説明する。尚、本発明は、これらの実施例により限定されるものではない。尚、以下において「部」及び「％」は、特に断らない限り質量部及び質量％を意味する。
製造例で得られた水溶性高分子の分析方法並びに、実施例及び比較例における半導体用濡れ剤又は研磨用組成物の評価方法について以下に記載する。Hereinafter, the present invention will be specifically described based on examples. In addition, this invention is not limited by these Examples. In the following, “parts” and “%” mean mass parts and mass% unless otherwise specified.
It describes below about the analysis method of the water-soluble polymer obtained by the manufacture example, and the evaluation method of the wetting agent for semiconductors or polishing composition in an Example and a comparative example.
＜鹸化度＞
ＪＩＳ Ｋ６７２６に従って測定した。<Degree of saponification>
It measured according to JIS K6726.
＜数平均分子量（Ｍｎ）＞
各製造例で得られた鹸化前の共重合体について、ＧＰＣ（ゲルパーミエーションクロマトグラフィー ＨＬＣ−８２２０、東ソー製）を用いて、ポリスチレン換算により測定した。<Number average molecular weight (Mn)>
The copolymer before saponification obtained in each production example was measured by polystyrene conversion using GPC (gel permeation chromatography HLC-8220, manufactured by Tosoh Corporation).
＜耐エッチング性（Ｅ．Ｒ．）＞
ガラスカッターで３×６ｃｍに切出したウェーハの重量を測定後、３％フッ酸水溶液に２０秒浸漬してウェーハ表面の酸化膜を除去し、その後純水で１０秒洗浄した。この工程をウェーハの表面が完全撥水になるまで繰り返した。次いで、アンモニア：水の重量比が１：１９であるアンモニア水に、水溶性高分子の濃度が０．１８ｗｔ％となるように半導体用濡れ剤を加えて、エッチング薬液を調整した。ウェーハをエッチング薬液に完全に浸漬させ、２５℃、１２時間静置してエッチングした。エッチング前後のウェーハ重量変化から、次式に従いエッチングレート（Ｅ．Ｒ．）を算出した。
After measuring the weight of the wafer cut to 3 × 6 cm with a glass cutter, it was immersed in a 3% hydrofluoric acid aqueous solution for 20 seconds to remove the oxide film on the wafer surface, and then washed with pure water for 10 seconds. This process was repeated until the wafer surface was completely water repellent. Next, an etching chemical solution was prepared by adding a semiconductor wetting agent to ammonia water having an ammonia: water weight ratio of 1:19 so that the concentration of the water-soluble polymer was 0.18 wt%. The wafer was completely immersed in an etching chemical solution and left to stand at 25 ° C. for 12 hours for etching. From the wafer weight change before and after etching, the etching rate (E.R.) was calculated according to the following formula.
＜濡れ性＞
耐エッチング性と同様の方法にてウェーハ表面の酸化膜を除去後、０．１８ｗｔ％の水溶性高分子溶液中に５分間浸漬した。浸漬後、ピンセットを用いて、ウェーハの表面が液面に対して垂直になるように引き上げ、１０秒経過時点におけるウェーハ端部からの撥水距離を目視で確認し、以下の基準により判定した。
○：撥水距離 ５ｍｍ未満
△：撥水距離 ５〜１０ｍｍ
×：撥水距離 １０ｍｍ超<Wettability>
The oxide film on the wafer surface was removed by the same method as etching resistance, and then immersed in a 0.18 wt% water-soluble polymer solution for 5 minutes. After immersion, the surface of the wafer was pulled up using a tweezers so as to be perpendicular to the liquid level, and the water-repellent distance from the end of the wafer at the time when 10 seconds had passed was visually confirmed, and judged according to the following criteria.
○: Water repellent distance less than 5 mm △: Water repellent distance 5 to 10 mm
×: Water repellent distance> 10mm
＜ウェーハ外観＞
耐エッチング性と同様の方法でエッチングを行った後の、ウェーハ表面を目視で確認し、以下の基準により判定した。
○：表面に荒れが認められない
△：表面がやや荒れている
×：表面が著しく荒れている<Wafer appearance>
The wafer surface after etching was performed by the same method as the etching resistance was visually confirmed, and judged according to the following criteria.
○: No roughening on the surface △: The surface is slightly rough ×: The surface is extremely rough
＜耐アルカリ性＞
５０ｃｃのスクリュー瓶に水酸化ナトリウムを水に溶かして調整したｐＨ１０のアルカリ水溶液４０ｇに水溶性高分子５．０ｇを加え、蓋をして良く混合した。アルミブロックヒーター内で５０℃、１ヶ月静置後の加水分解率をＧＣ、（ガスクロマトグラフィー ＧＣ−２０１４、島津製作所製）で評価し、以下の基準より判定した。
○：水溶性高分子の加水分解率が１％未満
△：水溶性高分子の加水分解質が１％以上５％未満
×：水溶性高分子の加水分解率が５％以上<Alkali resistance>
5.0 g of a water-soluble polymer was added to 40 g of an aqueous alkali solution adjusted to pH 10 by dissolving sodium hydroxide in water in a 50 cc screw bottle, and the mixture was covered well and mixed. The hydrolysis rate after standing at 50 ° C. for 1 month in an aluminum block heater was evaluated by GC (Gas Chromatography GC-2014, manufactured by Shimadzu Corporation), and judged according to the following criteria.
○: Hydrolysis rate of water-soluble polymer is less than 1% Δ: Hydrolyzate of water-soluble polymer is 1% or more and less than 5% ×: Hydrolysis rate of water-soluble polymer is 5% or more
＜シリカ分散性＞
９ｃｃスクリュー瓶にコロイダルシリカ（１次粒子径：３０〜５０ｎｍ）５．０ｇに樹脂固形分２０％の水溶性高分子水溶液を０．５ｇ加えて、良く混合した。一晩静置後のシリカの粒子径（Ａ）を動的光散乱法（ＥＬＳＺ−１０００、大塚電子製）により測定し、水溶性高分子を加えていないコロイダルシリカの粒子径（Ｂ）からの変化率を下式に従って算出し、以下の基準より判定した。
変化率（％）＝｛（Ａ−Ｂ）／Ｂ｝×１００
○：変化率が１０％未満
△：変化率が１０％以上〜３０％未満
×：変化率が３０％以上<Silica dispersibility>
In a 9 cc screw bottle, 0.5 g of a water-soluble polymer aqueous solution having a resin solid content of 20% was added to 5.0 g of colloidal silica (primary particle size: 30 to 50 nm) and mixed well. The particle size (A) of the silica after standing overnight was measured by a dynamic light scattering method (ELSZ-1000, manufactured by Otsuka Electronics Co., Ltd.), and from the particle size (B) of colloidal silica not added with a water-soluble polymer. The rate of change was calculated according to the following formula and judged according to the following criteria.
Rate of change (%) = {(A−B) / B} × 100
○: Change rate is less than 10% Δ: Change rate is 10% to less than 30% ×: Change rate is 30% or more
製造例１
≪酢酸ビニルとアルキルビニルエーテル共重合体の合成≫
攪拌翼、還流冷却管、温度計、各種導入管を備えた３Ｌの４つ口フラスコを用意し、初期モノマーとして酢酸ビニル（日本酢ビ・ポバール社製、以下「ＶＡｃ」という）３７５部及びｎ−プロピルビニルエーテル（日本カーバイド社製、以下「ＮＰＶＥ」という）２５０部、重合溶剤としてメタノールを２５０部を仕込み、攪拌混合した。さらに窒素導入管から１０ｍｌ／ｍｉｎの流量にて窒素を吹き込みつつ、４０ｍｉｎかけて混合液を６０℃に昇温した。
昇温を確認後、２，２−アゾビス−２，４−ジメチルバレロニトリル（和光純薬工業製、商品名「Ｖ−６５」）２．０部をメタノール５０部に溶解した初期開始剤の溶液を一括で加え、重合を開始した。
重合の開始と共に、滴下モノマーとしてＶＡｃ４５０部をモノマー導入管から６時間かけて滴下しながら重合した。一方で、２−メルカプトエタノール（以下、「ＭＴＧ」という）４．０部をメタノール１５０部に溶解した連鎖移動剤溶液、及びＶ−６５の８．０部をメタノール１２０部に溶解した滴下開始剤の溶液も、重合開始共にそれぞれの導入管から６時間かけて滴下した。
６時間重合させた後、フラスコを室温まで冷却し、４−メトキシフェノールを０．３部加えて重合を停止し、共重合体１Ａを得た。この共重合体１Ａの数平均分子量はＭｎ＝１０，０００であり、重合収率は８５％であった。共重合体１Ａに含まれる残モノマーは、真空ポンプをフラスコに繋いで、減圧下、５０℃で加熱することでメタノールと共に除去した。
≪水溶性高分子の合成（共重合体の鹸化）≫
フラスコから共重合体１Ａを抜出さずに、引き続き鹸化反応を行った。窒素導入管から１０ｍｌ／ｍｉｎの流量にて窒素を吹き込みつつ、３０ｍｉｎかけて混合液を６０℃に昇温した。昇温を確認後、水酸化ナトリウム３．９部をメタノール７５部に溶かしたアルカリ溶液を一括で加えて鹸化反応を開始した。４時間後、温度を下げて反応を停止した。溶剤をロータリーエバポレーターにてカット後、６０℃で一晩真空乾燥して、黄褐色固体の水溶性高分子１Ｂを得た。
水溶性高分子１Ｂについて1Ｈ−ＮＭＲで組成を測定したところ、ポリビニルアルコール／ＮＰＶＥ＝７７／２３ｍｏｌ％の共重合体であり、鹸化率は９８．０ｍｏｌ％であった。Production Example 1
≪Synthesis of vinyl acetate and alkyl vinyl ether copolymer≫
A 3 L four-necked flask equipped with a stirring blade, a reflux condenser, a thermometer, and various introduction tubes was prepared, and 375 parts of vinyl acetate (manufactured by Nihon Acetate / Poval, hereinafter referred to as “VAc”) as an initial monomer and n -250 parts of propyl vinyl ether (manufactured by Nippon Carbide Co., Ltd., hereinafter referred to as “NPVE”) and 250 parts of methanol as a polymerization solvent were mixed and stirred. Further, the mixture was heated to 60 ° C. over 40 min while nitrogen was blown from the nitrogen introduction tube at a flow rate of 10 ml / min.
After confirming the temperature rise, a solution of an initial initiator in which 2.0 parts of 2,2-azobis-2,4-dimethylvaleronitrile (trade name “V-65” manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 50 parts of methanol. Was added all at once to initiate polymerization.
At the start of the polymerization, 450 parts of VAc was dropped as a dropped monomer from the monomer introduction tube over 6 hours. On the other hand, a chain transfer agent solution in which 4.0 parts of 2-mercaptoethanol (hereinafter referred to as “MTG”) is dissolved in 150 parts of methanol, and a dropping initiator in which 8.0 parts of V-65 are dissolved in 120 parts of methanol. The solution was also dropped over 6 hours from the respective introduction tubes at the start of polymerization.
After polymerization for 6 hours, the flask was cooled to room temperature, 0.3 parts of 4-methoxyphenol was added to terminate the polymerization, and copolymer 1A was obtained. The number average molecular weight of this copolymer 1A was Mn = 10,000, and the polymerization yield was 85%. The residual monomer contained in copolymer 1A was removed together with methanol by connecting a vacuum pump to the flask and heating at 50 ° C. under reduced pressure.
≪Synthesis of water-soluble polymer (saponification of copolymer) ≫
The saponification reaction was subsequently performed without extracting the copolymer 1A from the flask. While nitrogen was blown from the nitrogen introduction tube at a flow rate of 10 ml / min, the mixture was heated to 60 ° C. over 30 min. After confirming the temperature rise, an alkaline solution in which 3.9 parts of sodium hydroxide was dissolved in 75 parts of methanol was added all at once to start the saponification reaction. After 4 hours, the temperature was lowered to stop the reaction. The solvent was cut with a rotary evaporator and then vacuum-dried at 60 ° C. overnight to obtain a water-soluble polymer 1B as a tan solid.
When the composition of the water-soluble polymer 1B was measured by 1 H-NMR, it was a copolymer of polyvinyl alcohol / NPVE = 77/23 mol%, and the saponification rate was 98.0 mol%.
製造例２
製造例１において、使用したＭＴＧの量を１０．０部に変更した以外は同様にして、共重合体２Ａを得た。共重合体２Ａの分子量は、Ｍｎ＝２，２００であり、重合収率は７８％であった。
共重合体２Ａを製造例１と同様に鹸化して、水溶性高分子２Ｂを得た。水溶性高分子２Ｂの組成について測定したところ、ポリビニルアルコール／ＮＰＶＥ＝７７／２３ｍｏｌ％の共重合体であり、鹸化率は９８．０ｍｏｌ％であったProduction Example 2
A copolymer 2A was obtained in the same manner as in Production Example 1 except that the amount of MTG used was changed to 10.0 parts. The molecular weight of the copolymer 2A was Mn = 2,200, and the polymerization yield was 78%.
Copolymer 2A was saponified in the same manner as in Production Example 1 to obtain water-soluble polymer 2B. When the composition of the water-soluble polymer 2B was measured, it was a copolymer of polyvinyl alcohol / NPVE = 77/23 mol%, and the saponification rate was 98.0 mol%.
製造例３
製造例１において、使用したモノマーのうち、初期モノマーをＶＡｃ４８０部、ＮＰＶＥ２００部、滴下モノマーをＶＡｃ３２０部に変更した以外は同様にして、共重合体３Ａを得た。共重合体３Ａの分子量は、Ｍｎ＝１１，０００であり、重合収率は８３％であった。
共重合体３Ａを製造例１と同様に鹸化して、水溶性高分子３Ｂを得た。水溶性高分子３Ｂの組成について測定したところ、ポリビニルアルコール／ＮＰＶＥ＝８４／１６ｍｏｌ％の共重合体であり、鹸化率は９８．４ｍｏｌ％であった。Production Example 3
In Production Example 1, a copolymer 3A was obtained in the same manner except that, among the monomers used, the initial monomer was changed to VAc 480 parts, NPVE 200 parts, and the dropped monomer was changed to VAc 320 parts. The molecular weight of the copolymer 3A was Mn = 11,000, and the polymerization yield was 83%.
Copolymer 3A was saponified in the same manner as in Production Example 1 to obtain water-soluble polymer 3B. When the composition of the water-soluble polymer 3B was measured, it was a copolymer of polyvinyl alcohol / NPVE = 84/16 mol%, and the saponification rate was 98.4 mol%.
製造例４
製造例１において、使用したモノマーのうち、初期モノマーをＶＡｃ７２０部、ＮＰＶＥ１００部、滴下モノマーをＶＡｃ１８０部に変更した以外は同様にして、共重合体４Ａを得た。共重合体４Ａの分子量は、Ｍｎ＝１０，０００であり、重合収率は８１％であった。
共重合体４Ａを製造例１と同様に鹸化して、水溶性高分子４Ｂを得た。水溶性高分子４Ｂの組成について測定したところ、ポリビニルアルコール／ＮＰＶＥ＝９１／９ｍｏｌ％の共重合体であり、鹸化率は９８．０ｍｏｌ％であった。Production Example 4
In Production Example 1, a copolymer 4A was obtained in the same manner except that the initial monomer was changed to VAc 720 parts, NPVE 100 parts, and the dropped monomer was changed to VAc 180 parts among the used monomers. The molecular weight of the copolymer 4A was Mn = 10,000, and the polymerization yield was 81%.
Copolymer 4A was saponified in the same manner as in Production Example 1 to obtain water-soluble polymer 4B. When the composition of the water-soluble polymer 4B was measured, it was a copolymer of polyvinyl alcohol / NPVE = 91/9 mol%, and the saponification rate was 98.0 mol%.
製造例５
製造例４において、ＮＰＶＥをｎ−ブチルビニルエーテル（日本カーバイド社製、以下「ＮＢＶＥ」という）１００部に変更した以外は同様にして、共重合体５Ａを得た。共重合体５Ａの分子量は、Ｍｎ＝９，０００であり、重合収率は８０％であった。
共重合体５Ａを製造例１と同様に鹸化して、水溶性高分子５Ｂを得た。水溶性高分子５Ｂの組成について測定したところ、ポリビニルアルコール／ＮＢＶＥ＝９０／１０ｍｏｌ％の共重合体であり、鹸化率は９８．１ｍｏｌ％であった。Production Example 5
A copolymer 5A was obtained in the same manner as in Production Example 4 except that NPVE was changed to 100 parts of n-butyl vinyl ether (manufactured by Nippon Carbide, hereinafter referred to as “NBVE”). The molecular weight of the copolymer 5A was Mn = 9,000 and the polymerization yield was 80%.
Copolymer 5A was saponified in the same manner as in Production Example 1 to obtain water-soluble polymer 5B. When the composition of the water-soluble polymer 5B was measured, it was a copolymer of polyvinyl alcohol / NBVE = 90/10 mol%, and the saponification rate was 98.1 mol%.
製造例６
製造例１において、使用したモノマーのうち、初期モノマーをＶＡｃ４７５部、２−エチルヘキシルビニルエーテル（日本カーバイド社製、以下「ＥＨＶＥ」という）５０部、滴下モノマーをＶＡｃ４７５部に変更した以外は同様にして、共重合体６Ａを得た。共重合体６Ａの分子量は、Ｍｎ＝８，０００であり、重合収率は７５％であった。
共重合体６Ａを製造例１と同様に鹸化して、水溶性高分子６Ｂを得た。水溶性高分子６Ｂの組成について測定したところ、ポリビニルアルコール／ＥＨＶＥ＝９７／３ｍｏｌ％の共重合体であり、鹸化率は９９．０ｍｏｌ％であった。Production Example 6
In Production Example 1, among the monomers used, the initial monomer was changed to VAc 475 parts, 2-ethylhexyl vinyl ether (manufactured by Nippon Carbide Corporation, hereinafter referred to as “EHVE”), and the dropped monomer was changed to VAc 475 parts in the same manner. A copolymer 6A was obtained. The molecular weight of the copolymer 6A was Mn = 8,000, and the polymerization yield was 75%.
Copolymer 6A was saponified in the same manner as in Production Example 1 to obtain water-soluble polymer 6B. When the composition of the water-soluble polymer 6B was measured, it was a copolymer of polyvinyl alcohol / EHVE = 97/3 mol%, and the saponification rate was 99.0 mol%.
製造例７
製造例４において、連鎖移動剤の滴下を行わず、初期開始剤０．４部及び滴下開始剤１．６部を用い、さらに溶剤をｔｅｒｔ−ブタノールに変更した以外は同様の操作を行い、共重合体７Ａを得た。共重合体７Ａの分子量は、Ｍｎ＝１７０，０００であり、重合収率は６９％であった。
共重合体７Ａを製造例１と同様に鹸化して、水溶性高分子７Ｂを得た。水溶性高分子７Ｂの組成について測定したところ、ポリビニルアルコール／ＮＰＶＥ＝９１／９ｍｏｌ％の共重合体であり、鹸化率は９８．１ｍｏｌ％であった。Production Example 7
In Production Example 4, the same procedure was performed except that the chain transfer agent was not dropped, 0.4 parts of the initial initiator and 1.6 parts of the drop initiator were used, and the solvent was changed to tert-butanol. A polymer 7A was obtained. The molecular weight of the copolymer 7A was Mn = 170,000, and the polymerization yield was 69%.
Copolymer 7A was saponified in the same manner as in Production Example 1 to obtain water-soluble polymer 7B. When the composition of the water-soluble polymer 7B was measured, it was a copolymer of polyvinyl alcohol / NPVE = 91/9 mol%, and the saponification rate was 98.1 mol%.
製造例８
製造例７において、初期開始剤を０．２部、滴下開始剤を０．８に変更した以外は同様の操作を行い、共重合体８Ａを得た。共重合体８Ａの分子量は、Ｍｎ＝２２０，０００であり、重合収率は５２％であった。
共重合体８Ａを製造例１と同様に鹸化して、水溶性高分子８Ｂを得た。水溶性高分子８Ｂの組成について測定したところ、ポリビニルアルコール／ＮＰＶＥ＝９１／９ｍｏｌ％の共重合体であり、鹸化率は９８．１ｍｏｌ％であった。Production Example 8
The same operation as in Production Example 7 was carried out except that the initial initiator was changed to 0.2 parts and the dropping initiator was changed to 0.8 to obtain a copolymer 8A. The molecular weight of the copolymer 8A was Mn = 220,000, and the polymerization yield was 52%.
Copolymer 8A was saponified in the same manner as in Production Example 1 to obtain water-soluble polymer 8B. When the composition of the water-soluble polymer 8B was measured, it was a copolymer of polyvinyl alcohol / NPVE = 91/9 mol%, and the saponification rate was 98.1 mol%.
製造例９
攪拌翼、還流冷却管、温度計、窒素導入管を備えた３Ｌの４つ口フラスコに、ＶＡｃ４７５部、Ｎ，Ｎ−ジイソプロピルアクリルアミド（興人製、以下「ＮＩＰＡＭ」という）２５部、重合溶剤としてＮ，Ｎ−ジメチルホルムアミド（以下「ＤＭＦ」という）１１５０部を仕込み、攪拌混合した。さらに窒素導入管から１０ｍｌ／ｍｉｎの流量にて窒素を吹き込みつつ、４０ｍｉｎかけて混合液を６０℃に昇温した。
昇温を確認後、Ｖ−６５ ０．５部をＤＭＦ５０部に溶解した開始剤溶液を一括で加え、重合を開始した。
１時間重合させた後、フラスコを室温まで冷却し、４−メトキシフェノールを０．１８部加えて重合を停止し、共重合体９Ａを得た。この共重合体９Ａの分子量は、Ｍｎ＝１６，０００であり、重合収率は１７％であった。共重合体９Ａに含まれる溶剤及び残モノマーは、ロータリーエバポレーターにてカット後、８０℃、一晩真空乾燥して除去した。
共重合体９Ａを製造例１と同様に鹸化して、水溶性高分子９Ｂを得た。水溶性高分子９Ｂの組成について測定したところ、ポリビニルアルコール／ＮＩＰＡＭ＝７５／２５ｍｏｌ％の共重合体であり、鹸化率は９８．３ｍｏｌ％であった。Production Example 9
In a 3 L four-necked flask equipped with a stirring blade, a reflux condenser, a thermometer, and a nitrogen introduction tube, 475 parts of VAc, 25 parts of N, N-diisopropylacrylamide (manufactured by Kojin, hereinafter referred to as “NIPAM”), as a polymerization solvent 1150 parts of N, N-dimethylformamide (hereinafter referred to as “DMF”) was charged and mixed with stirring. Further, the mixture was heated to 60 ° C. over 40 min while nitrogen was blown from the nitrogen introduction tube at a flow rate of 10 ml / min.
After confirming the temperature rise, an initiator solution prepared by dissolving 0.5 part of V-65 in 50 parts of DMF was added all at once to initiate polymerization.
After polymerization for 1 hour, the flask was cooled to room temperature, 0.18 part of 4-methoxyphenol was added to terminate the polymerization, and copolymer 9A was obtained. The molecular weight of this copolymer 9A was Mn = 16,000, and the polymerization yield was 17%. The solvent and residual monomer contained in copolymer 9A were removed by vacuum drying at 80 ° C. overnight after cutting with a rotary evaporator.
Copolymer 9A was saponified in the same manner as in Production Example 1 to obtain water-soluble polymer 9B. When the composition of the water-soluble polymer 9B was measured, it was a copolymer of polyvinyl alcohol / NIPAM = 75/25 mol%, and the saponification rate was 98.3 mol%.
製造例１０
調圧弁を備えたオートクレーブ中に、メタノールを５００部、ＶＡｃを１８０部、Ｖ−６５を０．２部加えて良く混合した。次いで、窒素を吹き込んでオートクレーブ中の空気を置換した後、調圧弁を通してエチレンを圧入した。オートクレーブを攪拌しながら、６０℃に昇温して重合を行った。
重合中のエチレン圧を３０ｋｇ／ｃｍ2に保持しながら、３時間重合させた後、オートクレーブを室温まで冷却した。次いで、４−メトキシフェノールを０．１部加えて重合を停止し、共重合体１０Ａを得た。この共重合体１０Ａの分子量は、Ｍｎ＝１５，０００であり、重合収率は６３％であった。共重合体１０Ａに含まれる溶剤及び残モノマーは、８０℃、一晩真空乾燥して除去した。
共重合体１０Ａを製造例１と同様に鹸化して、水溶性高分子１０Ｂを得た。水溶性高分子１０Ｂの組成について測定したところ、ポリビニルアルコール／エチレン＝９２／８ｍｏｌ％の共重合体であり、鹸化率は９８．５ｍｏｌ％であった。Production Example 10
In an autoclave equipped with a pressure regulating valve, 500 parts of methanol, 180 parts of VAc, and 0.2 part of V-65 were added and mixed well. Next, nitrogen was blown in to replace air in the autoclave, and then ethylene was injected through a pressure regulating valve. While stirring the autoclave, the temperature was raised to 60 ° C. to carry out polymerization.
The polymerization was carried out for 3 hours while maintaining the ethylene pressure during polymerization at 30 kg / cm 2 , and then the autoclave was cooled to room temperature. Next, 0.1 part of 4-methoxyphenol was added to terminate the polymerization, and a copolymer 10A was obtained. The molecular weight of this copolymer 10A was Mn = 15,000, and the polymerization yield was 63%. The solvent and residual monomer contained in copolymer 10A were removed by vacuum drying at 80 ° C. overnight.
Copolymer 10A was saponified in the same manner as in Production Example 1 to obtain water-soluble polymer 10B. When the composition of the water-soluble polymer 10B was measured, it was a copolymer of polyvinyl alcohol / ethylene = 92/8 mol%, and the saponification rate was 98.5 mol%.
製造例１１
製造例１において、使用したモノマーのうち、初期モノマーをＶＡｃ２２７．５部、ＮＰＶＥ３５０部、滴下モノマーをＶＡｃ４２２．５部に変更した以外は同様にして、共重合体１１Ａを得た。共重合体１１Ａの分子量は、Ｍｎ＝１０，０００であり、重合収率は７０％であった。
共重合体１１Ａを製造例１と同様に鹸化して、高分子１１Ｂを得た。高分子１１Ｂの組成について測定したところ、ポリビニルアルコール／ＮＰＶＥ＝６５／３５ｍｏｌ％の共重合体であり、鹸化率は９８．５ｍｏｌ％であった。Production Example 11
In Production Example 1, a copolymer 11A was obtained in the same manner except that, among the monomers used, the initial monomer was changed to VAc 227.5 parts, NPVE 350 parts, and the dropped monomer was changed to VAc 422.5 parts. The molecular weight of the copolymer 11A was Mn = 10,000, and the polymerization yield was 70%.
The copolymer 11A was saponified in the same manner as in Production Example 1 to obtain a polymer 11B. When the composition of the polymer 11B was measured, it was a copolymer of polyvinyl alcohol / NPVE = 65/35 mol%, and the saponification rate was 98.5 mol%.
製造例１２
製造例１において、使用したモノマーのうち、初期モノマーをＶＡｃ４７５部、ｎ−ドデシルビニルエーテル（ＢＡＳＦ社製、以下「ＮＤＶＥ」という）５０部、滴下モノマーをＶＡｃ４７５部に変更した以外は同様にして、重合体１２Ａを得た。重合体１２Ａの分子量は、Ｍｎ＝１０，０００であり、重合収率は９０％であった。
重合体１２Ａを製造例１と同様に鹸化して、高分子１２Ｂを得た。高分子１２Ｂの鹸化率は９７．５ｍｏｌ％であった。Production Example 12
In Production Example 1, the initial monomer was changed to VAc 475 parts, n-dodecyl vinyl ether (manufactured by BASF, hereinafter referred to as “NDVE”) 50 parts, and the dropping monomer was changed to VAc 475 parts in the same manner. Combined 12A was obtained. The molecular weight of the polymer 12A was Mn = 10,000, and the polymerization yield was 90%.
The polymer 12A was saponified in the same manner as in Production Example 1 to obtain a polymer 12B. The saponification rate of the polymer 12B was 97.5 mol%.
製造例１３
製造例９において、使用したモノマーをＶＡｃ４４０部、ＮＩＰＡＭ６０部に変更した以外は同様にして、共重合体１３Ａを得た。共重合体１３Ａの分子量は、Ｍｎ＝１０，０００であり、重合収率は２４％であった。
共重合体１３Ａを製造例１と同様に鹸化して、水溶性高分子１３Ｂを得た。水溶性高分子１３Ｂの組成について測定したところ、ポリビニルアルコール／ＮＩＰＡＭ＝５０／５０ｍｏｌ％の共重合体であり、鹸化率は９８．０ｍｏｌ％であった。Production Example 13
A copolymer 13A was obtained in the same manner as in Production Example 9 except that the monomers used were changed to 440 parts of VAc and 60 parts of NIPAM. The molecular weight of the copolymer 13A was Mn = 10,000, and the polymerization yield was 24%.
The copolymer 13A was saponified in the same manner as in Production Example 1 to obtain a water-soluble polymer 13B. When the composition of the water-soluble polymer 13B was measured, it was a copolymer of polyvinyl alcohol / NIPAM = 50/50 mol%, and the saponification rate was 98.0 mol%.
実施例１
水溶性高分子１Ｂの濃度が１５質量％となるように水を加え、半導体用濡れ剤を調整した。得られた半導体用濡れ剤について、耐エッチング性、濡れ性、ウェーハ外観及び耐アルカリ性の評価を行った。得られた結果について表１に示した。
また、アンモニア水を加えてｐＨを１０．０に調整したコロイダルシリカ分散液（１次粒子系３０〜５０ｎｍ、シリカ固形分１０％）１０．０ｇ、上記半導体用濡れ剤を０．１ｇ添加して、研磨剤用組成物を得た。得られた研磨剤用組成物についてシリカ分散性を評価し、表１に結果を示した。Example 1
Water was added so that the concentration of the water-soluble polymer 1B was 15% by mass to prepare a semiconductor wetting agent. About the obtained wetting agent for semiconductors, etching resistance, wettability, wafer appearance and alkali resistance were evaluated. The results obtained are shown in Table 1.
Also, 10.0 g of colloidal silica dispersion (primary particle system 30-50 nm, silica solid content 10%) adjusted to pH 10.0 by adding aqueous ammonia and 0.1 g of the above-mentioned wetting agent for semiconductor were added. A composition for an abrasive was obtained. The obtained abrasive composition was evaluated for silica dispersibility, and Table 1 shows the results.
実施例２〜１０及び比較例１〜７
表１に示された水溶性高分子を用いた以外は実施例１と同様に半導体用濡れ剤及び研磨剤組成物を調製した。ただし、比較例１及び２では、鹸化後の高分子の一部もしくは大部分が水に溶解しないため、濡れ剤及び研磨剤組成物としての評価ができなかった。各試料の評価結果について表１に示した。Examples 2 to 10 and Comparative Examples 1 to 7
A semiconductor wetting agent and abrasive composition were prepared in the same manner as in Example 1 except that the water-soluble polymer shown in Table 1 was used. However, in Comparative Examples 1 and 2, since a part or most of the polymer after saponification was not dissolved in water, evaluation as a wetting agent and an abrasive composition could not be performed. The evaluation results of each sample are shown in Table 1.
表１に示された水溶性高分子の詳細は以下の通り。
ＰＶＡ１０５：完全鹸化ポリビニルアルコール（クラレ社製、商品名「クラレポバール
ＰＶＡ１０５」、鹸化度９８．５ｍｏｌ％、重合度５００）
ＰＶＡ５０５：低鹸化ポリビニルアルコール（クラレ社製、商品名「クラレポバール
ＰＶＡ５０５」、鹸化度７３．５ｍｏｌ％、重合度５００）
ＨＥＣ：ヒドロキシエチルセルロース（和光純薬工業社製、重量平均分子量９０，０００）
ＰＶＰ Ｋ３０：ポリビニルピロリドン（東京化成工業社製）Details of the water-soluble polymer shown in Table 1 are as follows.
PVA105: Completely saponified polyvinyl alcohol (Kuraray Co., Ltd., trade name “Kuraray Poval”
PVA105 ", saponification degree 98.5 mol%, polymerization degree 500)
PVA505: low saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name “Kuraray Poval”
PVA505 ”, saponification degree 73.5 mol%, polymerization degree 500)
HEC: hydroxyethyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 90,000)
PVP K30: Polyvinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.)
実施例１〜１０は、本発明で規定する水溶性高分子を用いた実験例であり、ウェーハへの吸着性が高いため、耐エッチング性、濡れ性及びウェーハへの外観に優れる結果が得られている。また、研磨剤組成物とした場合のシリカ分散性にも優れることが確認された。
一方、式（２）で表される構造単位を有さない水溶性高分子を用いた比較例４は、ウェーハ表面への吸着性が不十分であるため、耐エッチング性、濡れ性及びウェーハ外観の点で劣る結果となった。また、鹸化率の低いポリビニルアルコールを用いた比較例５は、酢酸ビニル由来のユニットの加水分解が生じるため、耐アルカリ性が不足するものであった。本発明の水溶性高分子と構造単位の異なる水溶性高分子を用いた比較例６及び７は、ウェーハ表面への吸着性及びシリカ分散性の点で、満足するものではなかった。
また、上記の通り、比較例１及び２では、鹸化後の高分子が水に溶解しないため、濡れ剤及び研磨剤組成物としての評価ができなかった。比較例１は、式（２）で表される構造単位が多く、鹸化後に得られた高分子の水への溶解性が不十分であったためと思われる。比較例２は、酢酸ビニルとｎ-ドデシルビニルエーテルとの共重合性が悪いことから、ｎ−ドデシルビニルエーテルを主成分とする水に不溶な高分子成分が生成したためと推察される。Examples 1 to 10 are experimental examples using the water-soluble polymer defined in the present invention, and because the adsorptivity to the wafer is high, results excellent in etching resistance, wettability and appearance on the wafer are obtained. ing. Moreover, it was confirmed that the silica dispersibility is excellent in the case of an abrasive composition.
On the other hand, Comparative Example 4 using the water-soluble polymer not having the structural unit represented by the formula (2) has insufficient adsorbability on the wafer surface, so that the etching resistance, wettability and wafer appearance are reduced. The result was inferior. Further, in Comparative Example 5 using polyvinyl alcohol having a low saponification rate, hydrolysis of a unit derived from vinyl acetate occurred, so that the alkali resistance was insufficient. Comparative Examples 6 and 7 using a water-soluble polymer having a structural unit different from that of the water-soluble polymer of the present invention were not satisfactory in terms of adsorptivity to the wafer surface and silica dispersibility.
Further, as described above, in Comparative Examples 1 and 2, since the polymer after saponification did not dissolve in water, evaluation as a wetting agent and an abrasive composition could not be performed. It seems that Comparative Example 1 had a large number of structural units represented by the formula (2), and the solubility of the polymer obtained after saponification in water was insufficient. In Comparative Example 2, it is presumed that water-insoluble polymer components containing n-dodecyl vinyl ether as a main component were generated due to poor copolymerization of vinyl acetate and n-dodecyl vinyl ether.
本発明の半導体用濡れ剤は、研磨後のウェーハ表面への吸着性に優れるため、該半導体用濡れ剤を含む研磨用組成物を用いることにより、研磨後のウェーハ表面の平滑性を高め、かつ、ＣＯＰを抑制することが可能となる。さらに、シリカの分散性も良好であることから、シリコンウェーハの仕上げ研磨用組成物として特に有用である。 Since the wetting agent for semiconductors of the present invention is excellent in the adsorptivity to the wafer surface after polishing, by using a polishing composition containing the wetting agent for semiconductors, the smoothness of the wafer surface after polishing is improved, and , COP can be suppressed. Furthermore, since the dispersibility of silica is also good, it is particularly useful as a composition for final polishing of silicon wafers.
Claims (7)
［−ＣＨ２ＣＨ（ＯＨ）−］ （１）
［−ＣＨ２ＣＨ（Ｘ）−］ （２）
〔式（２）中、Ｘは炭素数１〜１０のアルキル基を有するアルキルエーテル基、炭素数６〜１０のアリール基、式（３）若しくは式（４）で表される有機基、炭素数１〜１０のアルキル基を有するウレタンアルキル基、炭素数３以上のアルキレン基を有するアルキレンオキシド基、水素又は炭素数１〜３のアルキル基を表す。〕
−Ｃ（＝Ｏ）Ｏ−（ＣＨ２）ｍ−Ｒ１ （３）
〔式（３）中、Ｒ１は炭素数１〜８のアルキル基、炭素数１〜４のアルキル基を有するアルキルアミノ基又はジアルキルアミノ基、ｍは０〜３の整数を表す。〕
−Ｃ（＝Ｏ）ＮＨ−（ＣＨ２）ｎ−Ｒ２ （４）
〔式（４）中、Ｒ２は炭素数１〜８のアルキル基、炭素数１〜４のアルキル基を有するアルキルアミノ基又はジアルキルアミノ基、ｎは０〜３の整数を表す。〕 A wetting agent for a semiconductor containing a water-soluble polymer having 70 to 9 7 mol% of a structural unit represented by the formula (1) and 3 to 30 mol% of a structural unit represented by the formula (2) in the molecule.
[—CH 2 CH (OH) —] (1)
[—CH 2 CH (X) —] (2)
[In Formula (2), X is an alkyl ether group having an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an organic group represented by Formula (3) or Formula (4), and the number of carbon atoms. A urethane alkyl group having 1 to 10 alkyl groups, an alkylene oxide group having an alkylene group having 3 or more carbon atoms, hydrogen, or an alkyl group having 1 to 3 carbon atoms is represented. ]
-C (= O) O- (CH 2) m -R 1 (3)
[In formula (3), R 1 represents an alkyl group having 1 to 8 carbon atoms, an alkylamino group having 1 to 4 carbon atoms or a dialkylamino group, and m represents an integer of 0 to 3. ]
-C (= O) NH- (CH 2) n -R 2 (4)
Wherein (4), R 2 represents an integer of alkylamino group or a dialkylamino group, n represents 0 to 3 with an alkyl group, an alkyl group having 1 to 4 carbon atoms having 1 to 8 carbon atoms. ]
［−ＣＨ２ＣＨ（ＯＨ）−］ （１）
［−ＣＨ２ＣＨ（Ｘ）−］ （２）
〔式（２）中、Ｘは炭素数１〜１０のアルキル基を有するアルキルエーテル基、炭素数６〜１０のアリール基、式（３）若しくは式（４）で表される有機基、炭素数１〜１０のアルキル基を有するウレタンアルキル基、炭素数３以上のアルキレン基を有するアルキレンオキシド基、水素又は炭素数１〜３のアルキル基を表す。〕
−Ｃ（＝Ｏ）Ｏ−（ＣＨ２）ｍ−Ｒ１ （３）
〔式（３）中、Ｒ１は炭素数１〜８のアルキル基、炭素数１〜４のアルキル基を有するアルキルアミノ基又はジアルキルアミノ基、ｍは０〜３の整数を表す。〕
−Ｃ（＝Ｏ）ＮＨ−（ＣＨ２）ｎ−Ｒ２ （４）
〔式（４）中、Ｒ２は炭素数１〜８のアルキル基、炭素数１〜４のアルキル基を有するアルキルアミノ基又はジアルキルアミノ基、ｎは０〜３の整数を表す。〕 In the molecule, using a water-soluble polymer having a structural unit 3 30 mol% represented by the structural unit 70 to 9 7 mol% and represented by Formula (1) (2) to polish the silicon wafer Method.
[—CH 2 CH (OH) —] (1)
[—CH 2 CH (X) —] (2)
[In Formula (2), X is an alkyl ether group having an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an organic group represented by Formula (3) or Formula (4), and the number of carbon atoms. A urethane alkyl group having 1 to 10 alkyl groups, an alkylene oxide group having an alkylene group having 3 or more carbon atoms, hydrogen, or an alkyl group having 1 to 3 carbon atoms is represented. ]
-C (= O) O- (CH 2) m -R 1 (3)
[In formula (3), R 1 represents an alkyl group having 1 to 8 carbon atoms, an alkylamino group having 1 to 4 carbon atoms or a dialkylamino group, and m represents an integer of 0 to 3. ]
-C (= O) NH- (CH 2) n -R 2 (4)
Wherein (4), R 2 represents an integer of alkylamino group or a dialkylamino group, n represents 0 to 3 with an alkyl group, an alkyl group having 1 to 4 carbon atoms having 1 to 8 carbon atoms. ]
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