CN115403696B - Alkali-soluble resin, protective layer composition, protective layer, laminate, and method for forming resist pattern - Google Patents
Alkali-soluble resin, protective layer composition, protective layer, laminate, and method for forming resist pattern Download PDFInfo
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- CN115403696B CN115403696B CN202210585560.2A CN202210585560A CN115403696B CN 115403696 B CN115403696 B CN 115403696B CN 202210585560 A CN202210585560 A CN 202210585560A CN 115403696 B CN115403696 B CN 115403696B
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- protective layer
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- 239000011347 resin Substances 0.000 title claims abstract description 160
- 229920005989 resin Polymers 0.000 title claims abstract description 160
- 239000011241 protective layer Substances 0.000 title claims abstract description 122
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 80
- 239000002904 solvent Substances 0.000 claims abstract description 68
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 239000010410 layer Substances 0.000 claims description 61
- 125000001153 fluoro group Chemical group F* 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 125000002947 alkylene group Chemical group 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 17
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000004210 ether based solvent Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 45
- 239000003513 alkali Substances 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003505 polymerization initiator Substances 0.000 description 13
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000000671 immersion lithography Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000003275 alpha amino acid group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- -1 methylene, ethylene, propylene Chemical group 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical group CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 2
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- IWTBVKIGCDZRPL-UHFFFAOYSA-N 3-methylpentanol Chemical compound CCC(C)CCO IWTBVKIGCDZRPL-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000001618 (3R)-3-methylpentan-1-ol Substances 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- VTSWSQGDJQFXHB-UHFFFAOYSA-N 2,4,6-trichloro-5-methylpyrimidine Chemical compound CC1=C(Cl)N=C(Cl)N=C1Cl VTSWSQGDJQFXHB-UHFFFAOYSA-N 0.000 description 1
- HBHVBOUUMCIGMG-UHFFFAOYSA-N 2,6-Dibutyl-p-cresol Natural products CCCCC1=CC(O)=CC(CCCC)=C1O HBHVBOUUMCIGMG-UHFFFAOYSA-N 0.000 description 1
- LZFZQYNTEZSWCP-UHFFFAOYSA-N 2,6-dibutyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC(CCCC)=C1O LZFZQYNTEZSWCP-UHFFFAOYSA-N 0.000 description 1
- UBUGVCHNTKFULW-UHFFFAOYSA-N 2-(2-carboxypropan-2-yldiazenyl)-2,3-dimethylbutanoic acid;methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC.CC(C)C(C)(C(O)=O)N=NC(C)(C)C(O)=O UBUGVCHNTKFULW-UHFFFAOYSA-N 0.000 description 1
- HOFODIXLYOLQOA-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N.N#CC(C)(C)N=NC(C)(C)C#N HOFODIXLYOLQOA-UHFFFAOYSA-N 0.000 description 1
- HHBZZTKMMLDNDN-UHFFFAOYSA-N 2-butan-2-yloxybutane Chemical compound CCC(C)OC(C)CC HHBZZTKMMLDNDN-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- BUWXUSLQPDDDSD-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-yloxy)butane Chemical compound CCC(C)(C)OC(C)(C)CC BUWXUSLQPDDDSD-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- UVEFRWMGQRNNDB-UHFFFAOYSA-N 2-pentan-2-yloxypentane Chemical compound CCCC(C)OC(C)CCC UVEFRWMGQRNNDB-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- ZEWLHMQYEZXSBH-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobutanoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)CCC(O)=O ZEWLHMQYEZXSBH-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004977 cycloheptylene group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004978 cyclooctylene group Chemical group 0.000 description 1
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- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- LJZJMIZQMNDARW-UHFFFAOYSA-N decan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCCCC(CC)OC(=O)C(C)=C LJZJMIZQMNDARW-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 125000006264 diethylaminomethyl group Chemical group [H]C([H])([H])C([H])([H])N(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
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- 150000003139 primary aliphatic amines Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- 238000002834 transmittance Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Photolithography (AREA)
- Electron Beam Exposure (AREA)
Abstract
The invention provides an alkali-soluble resin, a protective layer composition, a protective layer, a laminate and a method for forming a photoresist pattern. The protective layer composition comprises an alkali-soluble resin (A), a hydrophobic resin (B) and a solvent (C), wherein the alkali-soluble resin (A) comprises a structural unit (a 1) shown in the following formula (1), a structural unit (a 2) shown in the following formula (2) and a structural unit (a 3) shown in the following formula (3).
Description
Technical Field
The present invention relates to a method for forming an alkali-soluble resin, a resist composition, a resist, a laminate, and a photoresist (photoresist, resist) pattern, and more particularly, to a method for forming an alkali-soluble resin, a resist composition, a resist, a laminate (laminate ), and a photoresist pattern used in immersion lithography (Immersion Lithography) technology.
Background
In the conventional semiconductor process, a dry developing technique is mainly used, and air is used as a medium between the lens set and the wafer to form a pattern on the photomask on the wafer. However, with the development of semiconductor process, from 0.13 μm, 90 nm to 65 nm, not only is the technology of 157 nm dry exposure machine difficult to break through, but also the requirements of the material of the lens group and the transparency of the photoresist are higher.
In view of the limitations of dry development, in 2002, an immersion lithography technique has been proposed, which uses water with a refractive index of 1.44 as a medium between a lens set and a wafer, and shortens 193 nm wavelength light to 134 nm wavelength light, thereby forming finer patterns on the wafer.
In immersion lithography, photoacid (Photo-acid) and a quencher (quencher) in the photoresist can be dissolved in water, thus causing contamination or damage to the lens set. In this regard, the current semiconductor industry has developed a method for forming a protective layer on the surface of a photoresist, thereby isolating water from contact with the photoresist by the protective layer, and preventing the photoacid and the quencher in the photoresist from being dissolved in water to cause pollution or damage to the lens group.
However, in the exposure process of immersion lithography, in addition to the fact that the refractive index of the protective layer must be matched with that of water and photoresist, there is also a concern that there will be relative movement between water and wafer, so the protective layer must have a high receding contact angle with water to ensure the rate of relative movement between water and wafer, thereby increasing the exposure rate. Also, the protective layer needs to be sufficiently water-resistant to ensure that the structure of the protective layer itself is not corroded by water. Furthermore, the protective layer must be sufficiently alkali-soluble to ensure that the protective layer peels off after a subsequent development process.
Therefore, how to improve the receding contact angle of the protective layer to water, water resistance and alkali solubility is a problem to be solved by those skilled in the art at present on the premise that the refractive index of the protective layer can be matched with that of water and photoresist.
Disclosure of Invention
In view of the above, the present invention provides an alkali-soluble resin, a protective layer composition containing the alkali-soluble resin, a protective layer formed from the protective layer composition, a laminate, and a method for forming a photoresist pattern, wherein the protective layer has a high receding contact angle, good water resistance, and good alkali solubility on the premise that the refractive index of the protective layer can be matched with that of water and photoresist.
The present invention provides an alkali-soluble resin (A) comprising a structural unit (a 1) represented by the following formula (1), a structural unit (a 2) represented by the following formula (2), and a structural unit (a 3) represented by the following formula (3).
In the formula (1), R 1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R 2 is a fluoroalkyl group having 1 to 10 carbon atoms, and represents a bonding position.
In formula (2), R 3 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Y 1 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 10 carbon atoms or an arylene group, and represents a bonding position, wherein when Y 1 is an alkylene group having 2 to 10 carbon atoms or a cycloalkylene group having 5 to 10 carbon atoms, one or more of them-CH 2 -may be represented by-O-orAnd (3) substitution.
In formula (3), R 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Y 2 is an alkylene group having 2 to 8 carbon atoms, which represents a bonding position, wherein in Y 2, one or more of-CH 2 -may be via-O-orAnd (3) substitution.
In one embodiment of the present invention, the molar ratio between the structural unit (a 1) represented by formula (1), the structural unit (a 2) represented by formula (2), and the structural unit (a 3) represented by formula (3) is 10 to 50: 50-90: 1 to 20.
In one embodiment of the present invention, in R 2 of the formula (1), the fluoroalkyl group having 1 to 10 carbon atoms contains 3 or more fluorine atoms.
The present invention provides a protective layer composition comprising: the alkali-soluble resin (A), the hydrophobic resin (B) and the solvent (C).
In one embodiment of the present invention, the hydrophobic resin (B) includes a structural unit (B1) represented by the following formula (4) and a structural unit (B2) represented by the following formula (5).
In the formula (4), R 5 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R 6 is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or an aryl group, and represents a bonding position, wherein when R 6 is an alkyl group having 2 to 10 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, one or more of them-CH 2 -may be represented by-O-orAnd (3) substitution.
In the formula (5), R 7 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R 8 is a fluoroalkyl group having 1 to 10 carbon atoms, and represents a bonding position.
In one embodiment of the present invention, the molar ratio between the structural unit (b 1) represented by formula (4) and the structural unit (b 2) represented by formula (5) is 10 to 50: 50-90.
In one embodiment of the present invention, in formula (4), R 6 is an alkyl group having 1 to 10 carbon atoms.
In one embodiment of the present invention, the solvent (C) includes an alcohol solvent (C1) and an ether solvent (C2).
In one embodiment of the present invention, the alcohol solvent (C1) is at least one selected from the group consisting of alcohols having 4 to 6 carbon atoms.
In one embodiment of the present invention, the ether solvent (C2) is at least one selected from the group consisting of ethers having 8 to 12 carbon atoms.
In one embodiment of the present invention, the weight ratio between the alcohol solvent (C1) and the ether solvent (C2) is 1 to 50:50 to 99.
In one embodiment of the present invention, the weight ratio (B/a) between the hydrophobic resin (B) and the alkali-soluble resin (a) is greater than 0.1 and less than 0.43.
The invention provides a protective layer which is formed by the protective layer composition.
In one embodiment of the present invention, the protective layer was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 1 second and then dissolved completely, on the premise that the thickness of the protective layer was 50 nm.
In one embodiment of the present invention, the receding contact angle of the protective layer with respect to water is 69.5 degrees or more.
In one embodiment of the present invention, the protective layer has a refractive index of 1.54 to 1.55 with respect to light having a wavelength of 193 nm.
The present invention provides a laminate comprising: the substrate, the photoresist layer and the protective layer, wherein the photoresist layer is positioned between the substrate and the protective layer.
The invention provides a method for forming a photoresist pattern, which comprises the following steps: forming a photoresist layer on a substrate; forming the protective layer on the photoresist layer; exposing the photoresist layer and the protective layer; and developing the photoresist layer and the protective layer to form a photoresist pattern on the substrate.
In view of the above, the present invention provides an alkali-soluble resin, a protective layer composition comprising an alkali-soluble resin having specific structural units (e.g., structural unit (a 1) having a fluoroalkyl group, structural unit (a 2) having an α -trifluoromethyl alcohol group, and structural unit (a 3) having a long carbon chain carboxyl group), a protective layer formed from the protective layer composition, a laminate, and a method for forming a resist pattern, wherein the protective layer has a high receding contact angle, good water resistance, and good alkali solubility on the premise that the refractive index of the protective layer can be matched with water and the resist, and is therefore suitable for use in immersion lithography.
Drawings
Fig. 1 to 4 are flow charts of a method of forming a photoresist pattern according to an embodiment of the present invention.
Detailed Description
The following terms in the specification are used:
In the present specification, the term "(meth) acrylic" means "acrylic" and/or "methacrylic".
In this specification, "alkyl" may be a substituted or unsubstituted straight or branched alkyl group. Alkyl groups are for example but not limited to methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or pentyl.
In this specification, "alkylene" may be a substituted or unsubstituted straight or branched alkyl group. Alkylene is, for example, but not limited to, methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, or pentylene.
In this specification, "cycloalkyl" may be substituted or unsubstituted cycloalkyl. Cycloalkyl groups are for example, but not limited to, as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl.
In this specification, "cycloalkylene" may be substituted or unsubstituted cycloalkylene. Cycloalkylene is, for example, but not limited to, as cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, or cyclodecylene.
In this specification, an "aryl" group is a substituted or unsubstituted monovalent group having at least one aromatic ring. Aryl is for example but not limited to phenyl, 1-naphthyl, or 2-naphthyl.
In this specification, "arylene" is a substituted or unsubstituted divalent group having at least one aromatic ring. Arylene is, for example, but not limited to, phenylene, or naphthylene.
In the present specification, the "structural unit" is 1 or more units present in the polymer.
< Alkali-soluble resin (A) >)
The present embodiment provides an alkali-soluble resin (a) comprising a structural unit (a 1) represented by the following formula (1) (in this specification, also referred to as "structural unit (a 1) having a fluoroalkyl group"), a structural unit (a 2) represented by the following formula (2) (in this specification, also referred to as "structural unit (a 2) having an α -trifluoromethyl alcohol"), and a structural unit (a 3) represented by the following formula (3) (in this specification, also referred to as "structural unit (a 3) having a long carbon chain carboxyl group").
[ Structural unit (a 1) represented by formula (1) ]
The structural unit (a 1) represented by the formula (1) has a fluorine-containing alkyl group, wherein the refractive index of a resin layer or a protective layer formed of the alkali-soluble resin (a) can be reduced, and the hydrophobicity and the water resistance can be improved by introducing fluorine atoms into the structural unit. It is noted that hydrophobicity is related to the contact angle with water, and thus the introduction of fluorine atoms in the structural unit can also increase the contact angle of the alkali-soluble resin (a) with water and the receding contact angle with water. In contrast, if the structural unit does not incorporate fluorine atoms, the refractive index is too high and the receding contact angle is too low, which is disadvantageous for the use of the alkali-soluble resin (a) as a component of the protective layer.
Specifically, the structural unit (a 1) represented by formula (1) is as follows:
In the formula (1), the components are as follows,
R 1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom or a methyl group;
R 2 is a fluoroalkyl group having 1 to 10 carbon atoms, preferably a fluoroalkyl group having 5 to 10 carbon atoms;
* Indicating the bonding position.
When R 2 is a fluoroalkyl group having 5 to 10 carbon atoms, the hydrophobicity and water resistance of the alkali-soluble resin (A) can be further increased.
In R 2 of the formula (1), the fluoroalkyl group having 1 to 10 carbon atoms may contain 1 or more fluorine atoms, preferably 3 or more fluorine atoms, more preferably 8 or more fluorine atoms. When the fluoroalkyl group having 1 to 10 carbon atoms contains 3 or more fluorine atoms, the refractive index of the resin layer or the protective layer formed of the alkali-soluble resin (a) can be further reduced, and the hydrophobicity and water resistance can be improved.
The structural unit (a 1) represented by the formula (1) is, for example, a structural unit (a 1-1) represented by the following formula (1-1).
In the formula (1), the components are as follows,
R' is a fluorine atom or trifluoromethyl, preferably a fluorine atom;
R' is a hydrogen atom or a fluorine atom;
r is an integer from 0 to 3, preferably 1 or 2;
s is an integer from 0 to 7, preferably an integer from 3 to 7;
* Indicating the bonding position.
Specific examples of the structural unit (a 1-1) represented by the formula (1-1) include structural units represented by the following formula (1-1-1) to structural units represented by the following formula (1-1-23), or combinations thereof. Specific examples of the structural unit (a 1-1) represented by the formula (1-1) preferably include structural units represented by the following formula (1-1-5).
[ Structural unit (a 2) represented by formula (2) ]
The structural unit (a 2) represented by the formula (2) contains an α -trifluoromethyl alcohol, wherein the refractive index of the alkali-soluble resin (a) can be reduced by introducing fluorine atoms into the structural unit. Notably, the hydrogen of the-OH group in the α -trifluoromethyl alcohol is acidic, and thus the alkali-soluble resin (A) can be made alkali-soluble and have an appropriate development rate.
Specifically, the structural unit (a 2) represented by formula (2) is as follows:
In the formula (2), the amino acid sequence of the compound,
R 3 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom or a methyl group;
Y 1 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 10 carbon atoms, or an arylene group, preferably an alkylene group having 3 to 10 carbon atoms;
* The position of the bond is indicated and,
Wherein when Y 1 is an alkylene group having 2 to 10 carbon atoms or a cycloalkylene group having 5 to 10 carbon atoms, one or more of them-CH 2 -may be-O-orAnd (3) substitution.
When Y 1 is an alkylene group having 3 to 10 carbon atoms, the hydrophobicity and water resistance of the alkali-soluble resin (A) can be further increased.
Specific examples of the structural unit (a 2) represented by the formula (2) include structural units represented by the formula (2-1-1) to the structural units represented by the formula (2-1-16), structural units represented by the formula (2-2-1) to the structural units represented by the formula (2-2-5), and structural units represented by the formula (2-3), or a combination thereof. Specific examples of the structural unit (a 2) represented by the formula (2) preferably include structural units represented by the following formulas (2-1-3), structural units represented by the following formulas (2-1-5), or combinations thereof.
[ Structural unit (a 3) represented by formula (3) ]
The structural unit (a 3) shown in the formula (3) contains long carbon chain carboxyl, wherein the alkali solubility of the alkali soluble resin (A) can be improved and the development rate is proper by introducing the long carbon chain carboxyl into the structural unit. In contrast, if the carboxyl group-containing structural units in the alkali-soluble resin (a) are structural units derived from (meth) acrylic acid, the receding contact angle of the protective layer formed by the alkali-soluble resin (a) is lowered due to the excessive hydrophilicity of the carboxyl group.
Specifically, the structural unit (a 3) represented by formula (3) is as follows:
in the formula (3), the amino acid sequence of the compound,
R 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom or a methyl group;
Y 2 is an alkylene group having 2 to 8 carbon atoms, preferably an alkylene group having 5 to 8 carbon atoms;
* The position of the bond is indicated and,
Wherein in Y 2, one or more of-CH 2 -may be via-O-orSubstituted, preferably one of them-CH 2 -isAnd (3) substitution.
When Y 2 is an alkylene group having 5 to 8 carbon atoms, the hydrophobicity, water resistance, and receding contact angle can be further improved on the premise that the alkali-soluble resin (a) has an appropriate alkali solubility and development rate.
The structural unit (a 3) represented by the formula (3) is, for example, the structural unit (a 3-1) represented by the formula (3-1), the structural unit (a 3-2) represented by the formula (3-2), the structural unit (a 3-3) represented by the formula (3-3), the structural unit (a 3-4) represented by the formula (3-4), or a combination thereof. Specific examples of the structural unit (a 3) represented by the formula (3) are described in detail below, and the structural unit (a 3) represented by the formula (3) preferably includes structural units represented by the following formulas (3-3-5).
In the formula (3-1),
R 4 is a hydrogen atom or a methyl group;
y 3 is an alkylene group having 2 to 8 carbon atoms;
* Indicating the bonding position.
Specific examples of the structural unit represented by the formula (3-1) include structural units represented by the formula (3-1-1) to structural units represented by the formula (3-1-7).
In the formula (3-2),
R 4 is a hydrogen atom or a methyl group;
y 4 is an alkylene group having 1 to 3 carbon atoms;
y 5 is an alkylene group having 1 to 4 carbon atoms;
m is 1 or 2, and the number of the m is 1 or 2,
* Indicating the bonding position.
Specific examples of the structural unit represented by the formula (3-2) include structural units represented by the formula (3-2-1) to structural units represented by the formula (3-2-6).
In the formula (3-3),
R 4 is a hydrogen atom or a methyl group;
y 6 is an alkylene group having 1 to 5 carbon atoms;
y 7 is an alkylene group having 1 to 4 carbon atoms;
* Indicating the bonding position.
Specific examples of the structural unit represented by the formula (3-3) include structural units represented by the formula (3-3-1) to structural units represented by the formula (3-3-14).
In the formula (3-4),
R 4 is a hydrogen atom or a methyl group;
Y 8 is an alkylene group having 1 to 5 carbon atoms;
y 9 is an alkylene group having 1 to 4 carbon atoms;
* Indicating the bonding position.
Specific examples of the structural unit represented by the formula (3-4) include structural units represented by the formula (3-4-1) to structural units represented by the formula (3-4-2).
In one embodiment, the molar ratio between the structural unit (a 1) represented by formula (1), the structural unit (a 2) represented by formula (2), and the structural unit (a 3) represented by formula (3) may be 10 to 50: 50-90: 1 to 20, preferably 20 to 40: 50-70: 1 to 10. When the molar ratio between the structural unit (a 1) represented by the formula (1), the structural unit (a 2) represented by the formula (2), and the structural unit (a 3) represented by the formula (3) is within the above-mentioned range, the resin layer formed of the alkali-soluble resin (a) or the later-described protective layer can be well balanced in refractive index, alkali developability, and development rate. However, in order to obtain a receding contact angle satisfying the requirements for a protective layer for a photoresist, it is still necessary to use a hydrophobic resin (B) to be described later.
The structural unit constituting the alkali-soluble resin (a) may further include other structural units than the structural unit (a 1) shown in the formula (1), the structural unit (a 2) shown in the formula (2), the structural unit (a 3) shown in the formula (3), and the like, without affecting the efficacy of the present embodiment.
The alkali-soluble resin (A) may be a random copolymer or a block copolymer.
The weight average molecular weight of the alkali-soluble resin (A) is 2,000 to 30,000. When the weight average molecular weight of the alkali-soluble resin (a) is within the above range, the resin layer formed of the alkali-soluble resin (a) or a protective layer described later can be made to have both good water resistance and alkali solubility.
On the premise that the thickness of the resin layer formed by the alkali-soluble resin (A) is 50nm, the resin layer is immersed in a 2.38 mass% aqueous solution of tetramethyl ammonium hydroxide for 1 second and then dissolved completely. That is, the alkali-soluble resin (a) has good alkali solubility.
[ Synthesis of alkali-soluble resin (A) ]
The alkali-soluble resin (a) may be polymerized from a first monomer mixture including a monomer derived from the structural unit (a 1) represented by the formula (1), a monomer derived from the structural unit (a 2) represented by the formula (2), and a monomer derived from the structural unit (a 3) represented by the formula (3). The polymerization method is not particularly limited, and an appropriate polymerization method may be selected according to the need. The polymerization method is, for example, a solution polymerization method.
The monomer derived from the structural unit (a 1) represented by the formula (1) is, for example, a monomer represented by the formula (I).
R 1、R2 in formula (I) is the same as R 1、R2 in formula (1), and is not described in detail herein.
Specific examples of the monomer represented by the formula (I) include monomers derived from the structural unit represented by the above-mentioned (1-1-1) to the structural unit represented by the above-mentioned formula (1-1-9), and the details thereof will not be repeated here.
The monomer derived from the structural unit (a 2) represented by the formula (2) is, for example, a monomer represented by the formula (II).
R 3、Y1 in formula (II) is the same as R 3、Y1 in formula (2), and is not described in detail herein.
Specific examples of the monomer represented by the formula (II) include monomers derived from the structural unit represented by the formula (2-1-1) to the structural unit represented by the formula (2-1-16), the structural unit represented by the formula (2-2-1) to the structural unit represented by the formula (2-2-5), and the structural unit represented by the formula (2-3), and are not described in detail herein.
The monomer derived into the structural unit (a 3) represented by the formula (3) is, for example, a monomer represented by the formula (III).
R 4、Y2 in formula (III) is the same as R 4、Y2 in formula (3), and is not described in detail herein.
Specific examples of the monomer represented by the formula (III) include those derived from the structural unit represented by the formula (3-1-1) to the structural unit represented by the formula (3-1-7), those derived from the structural unit represented by the formula (3-2-1) to the structural unit represented by the formula (3-2-6), those derived from the structural unit represented by the formula (3-3-1) to the structural unit represented by the formula (3-3-14), and those derived from the structural unit represented by the formula (3-4-1) to the structural unit represented by the formula (3-4-2), and will not be described in detail herein.
The first monomer mixture may further include a monomer represented by formula (I), a monomer represented by formula (II), a monomer represented by formula (III), and other monomers other than the monomer represented by formula (III) without affecting the efficacy of the present embodiment.
The mixture constituting the alkali-soluble resin (a) may include a solvent. The kind of the solvent is not particularly limited as long as it does not react with the monomer and dissolves the monomer. Specific examples of solvents include acetone, methyl isobutyl ketone, 2-heptanone, cyclohexanone, or combinations thereof. Specific examples of the solvent preferably include cyclohexanone.
The mixture constituting the alkali-soluble resin (a) may include a polymerization initiator. The kind of the polymerization initiator is not particularly limited as long as it is not reactive with the monomer and is soluble in the solvent monomer. Specific examples of the polymerization initiator include organic peroxides such as cumene hydroperoxide (cumene hydroperoxide, CHP), diisopropylbenzene hydroperoxide (diisopropylbenzene hydroperoxide), di-t-butyl peroxide (di-t-butyl peroxide), lauroyl peroxide (lauroyl peroxide), benzoyl peroxide (benzoyl peroxide), t-butyl peroxyisopropyl carbonate (t-butylperoxyisopropyl carbonate), t-amyl peroxy-2-ethylhexanoate (t-amylperoxy-2-ethylhexanoate), t-butyl peroxy-2-ethylhexanoate (t-butylperoxy-2-ethylhexanoate), and the like; azo compounds such as 2,2'-azobis (isobutyronitrile) (2, 2' -azobis (isobutyronitrile)), 1'-azobis (cyclohexane carbonitrile) (1, 1' -azobis (cyclohexanecarbonitrile)), 2'-azobis (2, 4-dimethylvaleronitrile) (2, 2' -azobis (2, 4-dimethylvaleronitrile)), dimethyl 2,2'-azobis (2-methylpropionate) (dimethyl 2,2' -azobis (2-methyl propionate)), and the like. The polymerization initiator is preferably tert-butyl peroxy-2-ethylhexanoate. The amount of the polymerization initiator to be used is not particularly limited, and may be 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the total monomers in the mixture.
In the case of synthesizing the alkali-soluble resin (A) by the solution polymerization method, the polymerization temperature may be 40℃to 150℃and preferably 60℃to 130 ℃.
In the case of synthesizing the alkali-soluble resin (A) by the solution polymerization method, the polymerization time may be 1 hour to 12 hours, preferably 2 hours to 6 hours.
In one embodiment, the synthesis of the alkali-soluble resin (a) may be performed under a nitrogen atmosphere.
< Protective layer composition >
The present embodiment provides a protective layer composition including: an alkali-soluble resin (A), a hydrophobic resin (B), and a solvent (C). In addition, the protective layer composition may further include other additives (D), if necessary. The components of the protective layer composition will be described in detail below.
Alkali-soluble resin (A)
The alkali-soluble resin (A) is described above and will not be described in detail herein.
Hydrophobic resin (B)
The hydrophobic resin (B) includes a structural unit (B1) represented by the following formula (4) (also referred to as "structural unit (B1) containing no fluorine atom" in the present specification) and a structural unit (B2) represented by the following formula (5) (also referred to as "structural unit (B2) containing a fluorine atom" in the present specification).
[ Structural unit (b 1) represented by formula (4) ]
The structural unit (B1) represented by formula (4) is related to the solubility of the hydrophobic resin (B) in the solvent (C). Specifically, the structural unit (B1) represented by the formula (4) has a carbon chain, and therefore has good compatibility with a solvent (C) having a long carbon chain, which will be described later, and the hydrophobic resin (B) can be dissolved in the solvent (C) smoothly.
Specifically, the structural unit (b 1) represented by formula (4) is as follows:
In the formula (4), the amino acid sequence of the compound,
R 5 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom or a methyl group;
R 6 is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms;
* The position of the bond is indicated and,
Wherein when R 6 is an alkyl group having 2 to 10 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, one or more of-CH 2 -may be via-O-orAnd (3) substitution.
In one embodiment, in formula (4), R 6 is an alkyl group having 1 to 10 carbon atoms. When R 6 is an alkyl group having 1 to 10 carbon atoms, the structural unit (B1) represented by the formula (4) has a carbon chain and thus has good compatibility with a solvent (C) having a long carbon chain (particularly, an alcohol solvent (C1)) described later, so that the hydrophobic resin (B) can be dissolved in the solvent (C) smoothly.
In one embodiment, in formula (4), R 6 is an alkyl group having 5 to 10 carbon atoms. When R 6 is an alkyl group having 5 to 10 carbon atoms, the structural unit (B1) represented by the formula (4) has a long carbon chain and thus has better compatibility with a solvent (C) having a long carbon chain (particularly, an alcohol solvent (C1)) described later, so that the hydrophobic resin (B) can be dissolved in the solvent (C) more smoothly.
In one embodiment, in formula (4), R 6 is cycloalkyl having 5to 10 carbon atoms. When R 6 is cycloalkyl having 5to 10 carbon atoms, the receding contact angle of the resin layer or protective layer formed by the hydrophobic resin (B) may be further increased.
Specific examples of the structural unit represented by the formula (4) include a structural unit represented by the following formula (4-4-1) to a structural unit represented by the following formula (4-4-34), a structural unit represented by the following formula (4-2-1) to a structural unit represented by the following formula (4-2-14), a structural unit represented by the following formula (4-3-1) to a structural unit represented by the following formula (4-3-2), or a combination thereof. Specific examples of the structural unit represented by the formula (4) preferably include structural units represented by the following formulas (4-1 to 29), structural units represented by the formulas (4-2 to 7), or combinations thereof.
[ Structural unit (b 2) represented by formula (5) ]
The structural unit (B2) represented by the formula (5) contains a fluorine atom, wherein the refractive index of the hydrophobic resin (B) can be reduced, and the hydrophobicity and water resistance can be improved by introducing the fluorine atom into the structural unit. It is noted that hydrophobicity is related to the contact angle with water, and thus the introduction of fluorine atoms in the structural unit also increases the contact angle of the hydrophobic resin (B) with water and the receding contact angle with water. In contrast, if the structural unit does not incorporate fluorine atoms, the refractive index is too high and the receding contact angle is too low, which is disadvantageous for the use of the hydrophobic resin (B) as a component of the protective layer.
In the formula (5), the amino acid sequence of the compound,
R 7 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom or a methyl group;
R 8 is a fluoroalkyl group having 1 to 10 carbon atoms, preferably a fluoroalkyl group having 5 to 10 carbon atoms,
* Indicating the bonding position.
When R 8 is a fluoroalkyl group having 5 to 10 carbon atoms, the hydrophobicity and water resistance of the hydrophobic resin (B) can be further increased.
In R 8 of the formula (5), the fluoroalkyl group having 1 to 10 carbon atoms may contain 1 or more fluorine atoms, preferably 3 or more fluorine atoms, more preferably 8 or more fluorine atoms. When the fluoroalkyl group having 1 to 10 carbon atoms contains 3 or more fluorine atoms, the refractive index of the resin layer or the protective layer formed of the hydrophobic resin (B) can be further reduced, and the hydrophobicity and water resistance can be improved.
Specific examples of the structural unit (b 2) represented by the formula (5) are the same as specific examples of the structural unit (a 1) represented by the formula (1). Further, the structural unit (b 2) represented by the formula (5) is, for example, a structural unit represented by the formula (1-1), and specific examples of the structural unit (a 1) represented by the formula (1-1) include structural units represented by the formula (1-1-1) to structural units represented by the formula (1-1-9). The structural unit represented by the formula (1-1) and the structural units represented by the formula (1-1-1) to the structural units represented by the formula (1-1-9) are described above, and are not described in detail herein. Specific examples of the structural unit (b 2) represented by the formula (5) preferably include structural units represented by the following formulas (1-1-5).
In one embodiment, the molar ratio between the structural unit (b 1) represented by formula (4) and the structural unit (b 2) represented by formula (5) may be 10 to 50:50 to 90, preferably 20 to 30: 70-80. When the molar ratio between the structural unit (b 1) represented by the formula (4) and the structural unit (b 2) represented by the formula (5) is within the above-mentioned range, the solubility, refractive index and receding contact angle of the resin layer formed of the hydrophobic resin or the protective layer described later can be well balanced. However, if it is desired to obtain alkali solubility and development rate which meet the requirements for a protective layer for a photoresist, it is still necessary to use the alkali-soluble resin (A) in combination.
The structural unit constituting the hydrophobic resin (B) may further include other structural units than the structural unit (B1) represented by the formula (4) and the structural unit (B2) represented by the formula (5) without affecting the efficacy of the present embodiment.
In one embodiment, the hydrophobic resin (B) has a weight average molecular weight of 2,000 to 3,0000. When the weight average molecular weight of the hydrophobic resin (B) is within the above range, the resin layer formed of the hydrophobic resin (B) or a protective layer described later can be made to have both good water resistance and alkali solubility.
In one embodiment, the weight ratio (B/a) between the hydrophobic resin (B) and the alkali-soluble resin (a) is greater than 0.1 and less than 0.43. When the weight ratio (B/a) between the hydrophobic resin (B) and the alkali-soluble resin (a) is within the above range, the protective layer can be balanced with alkali solubility in terms of receding contact angle on the premise that the refractive index of the protective layer can be matched with that of water and photoresist.
The receding contact angle of the resin layer to water is 69.5 DEG or more on the premise that the thickness of the resin layer formed by the hydrophobic resin (B) is 50 nm.
[ Synthesis of hydrophobic resin (B) ]
The hydrophobic resin (B) may be polymerized from a second monomer mixture including a monomer derived from the structural unit (B1) represented by the formula (4) and a monomer derived from the structural unit (B2) represented by the formula (5). The polymerization method is not particularly limited, and an appropriate polymerization method may be selected according to the need. The polymerization method is, for example, a solution polymerization method.
The monomer derived into the structural unit (b 1) represented by the formula (4) is, for example, a monomer represented by the formula (IV).
R 5、R6 in the formula (IV) is the same as R 5、R6 in the formula (4), and is not described in detail herein.
Specific examples of the monomer represented by the formula (IV) include monomers derived from the structural unit represented by the formula (4-4-1) to the structural unit represented by the formula (4-4-34), the structural unit represented by the formula (4-2-1) to the structural unit represented by the formula (4-2-14), and the structural unit represented by the formula (4-3-1) to the structural unit represented by the formula (4-3-2), and are not described in detail herein.
The monomer derived from the structural unit (b 2) represented by the formula (5) is, for example, a monomer represented by the formula (V).
R 7、R8 in formula (V) is the same as R 7、R8 in formula (5), and is not described in detail herein.
Since the specific example of the structural unit (b 2) represented by the formula (5) is the same as the specific example of the structural unit (a 1) represented by the formula (1), the specific example package of the monomer represented by the formula (V) is derived from the structural unit represented by the formula (1-1-1) to the monomer represented by the formula (1-1-9), and the description thereof will not be repeated here.
Further, the second monomer mixture may further include monomers other than the monomer represented by formula (IV) and the monomer represented by formula (V) or the like without affecting the efficacy of the present embodiment.
The mixture constituting the hydrophobic resin (B) may include a solvent. The kind of the solvent is not particularly limited as long as it does not react with the monomer and dissolves the monomer. Specific examples of solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, or combinations thereof. Specific examples of the solvent preferably include propylene glycol monomethyl ether.
The mixture constituting the hydrophobic resin (B) may include a polymerization initiator. The kind of the polymerization initiator is not particularly limited as long as it is not reactive with the monomer and is soluble in the solvent monomer. Specific examples of the polymerization initiator for the hydrophobic resin (B) may be the same as those for the alkali-soluble resin (a), and will not be described in detail here.
In the case of synthesizing the hydrophobic resin (B) by the solution polymerization method, the polymerization temperature may be 40℃to 150℃and preferably 60℃to 130 ℃.
In the case of synthesizing the hydrophobic resin (B) by the solution polymerization method, the polymerization time may be 1 to 12 hours, preferably 2 to 6 hours.
In addition, the synthesis of the hydrophobic resin (B) may be performed under a nitrogen atmosphere.
Solvent (C)
The solvent (C) includes an alcohol solvent (C1) and an ether solvent (C2).
The alcohol solvent (C1) is at least one selected from the group consisting of alcohols having 4 to 6 carbon atoms.
Specific examples of the alcohol solvent (C1) include 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 2-ethyl-1-butanol, or a combination thereof. Specific examples of the alcohol solvent (C1) preferably include 2-methyl-1-butanol.
The alcohol solvent (C1) has a long carbon chain, and thus has good compatibility with the structural unit represented by formula (4) in the hydrophobic resin (B), so that the hydrophobic resin (B) can be smoothly dissolved in the solvent (C).
The ether solvent (C2) is at least one selected from the group consisting of ethers having 8 to 12 carbon atoms.
Specific examples of the ether solvent (C2) include di-n-butyl ether, diisobutyl ether, diisoamyl ether, di-n-amyl ether, methylcycloamyl ether, methylcyclohexyl ether, di-sec-butyl ether, di-sec-amyl ether, di-tert-amyl ether, di-n-hexyl ether, or a combination thereof. Specific examples of the ether solvent (C2) preferably include di-n-butyl ether.
The ether solvent (C2) has stable property, so that the protective layer formed by the protective layer composition can not interact with the photoresist layer, and the function of protecting the photoresist layer by the protective layer can be fully exerted.
The weight ratio between the alcohol solvent (C1) and the ether solvent (C2) may be 1 to 50:50 to 99, preferably 5 to 15: 85-95.
It is noted that in the present embodiment, a bi-solvent system is employed, in which an ether solvent (C2) is used as a main solvent and an alcohol solvent (C1) is used as a secondary solvent, thereby making the solvent (C) exhibit excellent solubility to the alkali-soluble resin (a) and the hydrophobic resin (B). In particular, when the weight ratio of the alcohol solvent (C1) to the ether solvent (C2) is within the above range, the alkali-soluble resin (a) and the hydrophobic resin (B) can be more smoothly dissolved in the solvent (C), and the resist layer formed from the resist composition does not interact with the resist layer, thereby further exhibiting the function of protecting the resist layer by the resist layer.
In one embodiment, the weight ratio ((a+b)/C) between the sum of the hydrophobic resin (B) and the alkali-soluble resin (a) and the solvent (C) may be 0.01 to 0.06, preferably 0.02 to 0.04, more preferably 0.025 to 0.035, in terms of the solubility of the alkali-soluble resin (a) and the hydrophobic resin (B) in the solvent (C) and the coatability of the protective layer composition on the photoresist layer.
Additive (D)
The protective layer composition may optionally contain an additive (D) such as a surfactant, in addition to the above components, without affecting the efficacy of the present embodiment.
< Preparation of protective layer composition >
The method for producing the protective layer composition is not particularly limited, and for example, the alkali-soluble resin (a), the hydrophobic resin (B), and the solvent (C) are placed in a stirrer and stirred to be mixed uniformly in a solution state, and if necessary, the additive (D) may be added to be mixed uniformly, whereby the protective layer composition in a solution state can be obtained.
< Protective layer >
The present embodiment provides a protective layer formed from the protective layer composition described above.
In one embodiment, the protective layer is completely dissolved after being immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 1 second on the premise that the thickness of the protective layer is 50 nm. That is, the protective layer of the present embodiment has good alkali solubility.
In one embodiment, the receding contact angle of the protective layer with respect to water is 69.5 degrees or more. In another embodiment, the receding contact angle of the protective layer to water is 72 degrees or more, 76 degrees or more, or 78 degrees or more. That is, the protective layer of the present embodiment has a high receding contact angle.
In one embodiment, the protective layer has a refractive index of 1.54 to 1.55 for light having a wavelength of 193 nm. That is, the refractive index of the protective layer of the present embodiment can be matched with that of water and photoresist.
< Laminate and method for Forming Photoresist Pattern >
The present embodiment provides a method for forming a photoresist pattern, including: step (i): forming a photoresist layer on a substrate; step (ii): forming a protective layer on the photoresist layer; step (iii): exposing the photoresist layer and the protective layer; step (iv): the photoresist layer and the protective layer are developed to form a photoresist pattern on the substrate. The following describes the steps in detail with reference to fig. 1 to 4:
Step (i)
As shown in fig. 1, a photoresist layer 120 is formed on a substrate 110, wherein a method of forming the photoresist layer 120 is not particularly limited, and is, for example, a coating method such as a spin coating method, a spray coating method, or a roll coating method.
The substrate 110 is not particularly limited, and is, for example, a glass substrate, a silicon wafer (wafer) substrate, a ceramic substrate, or a quartz substrate.
The photoresist layer 120 is not particularly limited, and is, for example, a photoresist generally containing a photoacid and a quencher. In addition, the photoresist layer 120 may be a positive photoresist or a negative photoresist.
Step (ii)
As shown in fig. 2, the protective layer 130 described above is formed on the photoresist layer 120. Thus, a laminate 100 including the substrate 110, the photoresist layer 120, and the protective layer 130 may be formed, wherein the photoresist layer 120 is located between the substrate 110 and the protective layer 130.
The method of forming the protective layer 130 is not particularly limited, and for example, baking is performed after a coating method such as a spin coating method, a spray coating method, or a roll coating method. The baking method is not particularly limited, and for example, the laminate 100 is placed on a heating plate. The heating temperature is 60 ℃ to 120 ℃. The heating time is 30 seconds to 120 seconds.
The protective layer 130 is formed of the protective layer composition described above. The protective layer 130 is coated on the photoresist layer 120 to prevent water, which is an immersion medium in immersion lithography, from penetrating into the photoresist layer and to prevent contamination or damage of the lens set due to dissolution of the photo-acid and the quencher in the photoresist in water. In order to reduce the surface tension of water and increase the surface activity, a fatty alcohol such as methanol, ethanol, or isopropanol may be added to water.
The thickness of the protective layer 130 is not particularly limited, but is 10nm to 150nm in terms of developability and light transmittance.
The protective layer 130 is preferably not mixed with the photoresist layer 120 and covers the photoresist layer 120.
Step (iii)
As shown in fig. 3, the photoresist layer 120 and the protective layer 130 on the substrate 110 are exposed. Specifically, the light L emitted from the light source 300 is passed through the patterned mask 200 and water (not shown) as an immersion medium to expose the photoresist layer 120 and the protective layer 130.
The wavelength of exposure may be 250 nm or less, more preferably 220 nm or less, for example, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F 2 excimer laser (157 nm), or X-rays.
The exposure dose may be 1 mJ/sq.min to 100 mJ/sq.min.
Step (iv)
As shown in fig. 4, the photoresist layer 120 and the protective layer 130 are developed to form a photoresist pattern 120a on the substrate 110.
The photoresist layer 120 may be a positive photoresist or a negative photoresist. When the photoresist layer 120 is a positive type photoresist, after the photoresist layer 120 is exposed, the exposed portions of the photoresist layer 120 and the protective layer 130 will be dissolved in a developing solution at the time of development, thus leaving an unexposed photoresist pattern 120a after development. When the photoresist layer 120 is a negative photoresist, after the photoresist layer 120 is exposed, the unexposed portions of the photoresist layer 120 and the protective layer 130 will dissolve in a developing solution upon development, thus leaving an exposed photoresist pattern 120a after development.
The developer is, for example, an inorganic alkaline aqueous solution. Specific examples of the base contained in the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, or amine; primary aliphatic amines such as ethylamine and n-propylamine; secondary aliphatic amines such as diethylamine and n-propylamine; fatty tertiary amines such as trimethylamine, diethylaminomethyl, dimethylethylamine and triethylamine; tertiary alicyclic acids such as pyrrole, piperidine, N-methylpiperidine, N-methyl-1, 8-diazabicyclo [5.4.0] -7-undecene and 1, 5-diazabicyclo [4.3.0] -5-nonene; aromatic tertiary amines such as pyridine, methylpyrimidine, lutidine, and quinoline; quaternary ammonium salt basic compounds such as aqueous solutions of tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide.
The alkali concentration of the developer may be 0.1 to 20 mass%.
The pH of the developer may be 10.0 to 15.0.
In one embodiment, the developer is a 2.38 mass% aqueous solution of tetramethyl ammonium hydroxide.
After step (iv), a further washing step may be performed. Specifically, the developing solution adhering to the substrate 110 and the photoresist pattern 120a is removed with pure water and/or supercritical fluid.
Experimental examples will be listed below to more specifically describe the present invention. Although the following experimental examples are described, the materials used, the amounts and ratios thereof, the details of the treatment, the flow of the treatment, and the like may be appropriately changed without departing from the scope of the present invention. Therefore, the present invention should not be construed as being limited in accordance with the experimental examples described below.
Examples
< Synthesis of alkali-soluble resin (A) >
Synthesis examples A-1 of the alkali-soluble resin (A) and comparative Synthesis examples A ' -1 and A ' -2 of the resin (A ') as comparative examples are described below.
Synthesis example A-1
2.34 G of octafluoropentanyl methacrylate, 4.35 g of pentyl 1, 1-trifluoro-2-trifluoromethyl-2-hydroxy-4-methacrylate, 4.01 g of pentyl 1, 1-trifluoro-2-hydroxy-5-methacrylate and 0.63 g of mono [2- [ (2-methyl-acryl) oxy ] ethyl ] succinate were dissolved in 19ml of cyclohexanone, and 0.67 g of tert-butyl peroxy-2-ethylhexanoate was added thereto as a polymerization initiator. Then, the above mixed solution was stirred at 90℃for 4 hours under nitrogen atmosphere to carry out a reaction. Then, the reaction solution was poured into 36 g of n-hexane while vigorously stirring, and after the polymer was settled, the upper layer solvent was removed, and finally dried in vacuo to give a white alkali-soluble resin (A-1).
The alkali-soluble resin (A-1) contains the following structural units in terms of molar ratio:
The weight average molecular weight, refractive index, receding contact angle, water resistance, and alkali solubility of the alkali-soluble resin (A-1) were evaluated in the following evaluation methods, and are shown in Table 1.
It is noted that the refractive index, receding contact angle, water resistance, and alkali solubility of the resin are evaluated in the form of a "film". Specifically, after 100 parts by weight of a resin, 323 parts by weight of 2-methyl-1-butanol, and 2910 parts by weight of di-n-butyl ether were mixed with a mechanical stirrer, the resin was coated on a silicon substrate by a spin coating method to form a coating film, and the silicon substrate was then placed on a heating plate together with the above coating film, and baked at 80 ℃ for 60 seconds to form a film (film thickness 50 nm). Next, the refractive index, receding contact angle, water resistance, and alkali solubility were evaluated with the film.
Comparative Synthesis example A' -1
2.47 G of octafluoropentanyl methacrylate, 4.48 g of pentyl 1, 1-trifluoro-2-trifluoromethyl-2-hydroxy-4-methacrylate, 3.99 g of pentyl 1, 1-trifluoro-2-hydroxy-5-methacrylate and 0.35 g of methacrylic acid were dissolved in 19 ml of cyclohexanone and 0.71 g of tert-butyl peroxy-2-ethylhexanoate was added thereto as a polymerization initiator. Then, the above mixed solution was stirred at 90℃for 4 hours under nitrogen atmosphere to carry out a reaction. Then, the reaction solution was poured into 36 g of n-hexane while vigorously stirring, and after the polymer was settled, the upper layer solvent was removed, and finally dried in vacuo to give a white resin (A' -1).
The structural unit contained in the resin (A' -1) is as follows:
The weight average molecular weight, refractive index, receding contact angle, water resistance, and alkali solubility of the resin (a' -1) were evaluated in the following evaluation methods, and are shown in table 1.
Comparative Synthesis example A' -2
2.30 G of octafluoropentanyl methacrylate, 4.74 g of pentyl 1, 1-trifluoro-2-trifluoromethyl-2-hydroxy-4-methacrylate and 4.29 g of pentyl 1, 1-trifluoro-2-trifluoromethyl-2-hydroxy-5-methacrylate were dissolved in 19 ml of cyclohexanone, and 0.66 g of tert-butyl peroxy-2-ethylhexanoate was added thereto as a polymerization initiator. Then, the above mixed solution was stirred at 90℃for 4 hours under nitrogen atmosphere to carry out a reaction. Then, the reaction solution was poured into 36 g of n-hexane while vigorously stirring, and after the polymer was settled, the upper layer solvent was removed, and finally dried in vacuo to give a white resin (A' -2).
The structural unit contained in the resin (A' -2) is as follows:
the weight average molecular weight, refractive index, receding contact angle, water resistance, and alkali solubility of the resin (a' -2) were evaluated in the following evaluation methods, and are shown in table 1.
TABLE 1
< Preparation of hydrophobic resin (B) >
Synthesis examples B-1 and B-2 of the hydrophobic resin (B) are described below.
Synthesis example B-1
8.79 G of octafluoropentane methacrylate and 2.49 g of 2-ethylhexyl methacrylate were dissolved in 19.56 ml of propylene glycol monomethyl ether, and 0.72 g of t-butyl peroxy-2-ethylhexanoate was added thereto as a polymerization initiator. Then, the above mixed solution was stirred at 90℃for 4 hours under nitrogen atmosphere to carry out a reaction. Then, the reaction solution was poured into 36 g of n-hexane while vigorously stirring, and after the polymer was settled, the upper layer solvent was removed, and finally dried in vacuo to give a white hydrophobic resin (B-1).
The structural unit contained in the hydrophobic resin (B-1) is as follows in molar ratio:
the weight average molecular weight, refractive index, receding contact angle, water resistance and alkali solubility of the hydrophobic resin (B-1) are shown in Table 2.
Synthesis example B-2
8.59 G of octafluoropentane methacrylate and 2.70 g of tricyclo [5.2.1.0 2,6 ] dec-8-yl methacrylate were dissolved in 19.56 ml of propylene glycol monomethyl ether, and 0.71 g of t-butyl peroxy-2-ethylhexanoate was added thereto as a polymerization initiator. Then, the above mixed solution was stirred at 90℃for 4 hours under nitrogen atmosphere to carry out a reaction. Then, the reaction solution was poured into 36 g of n-hexane while vigorously stirring, and after the polymer was settled, the upper solvent was removed, and finally dried in vacuo to give a white hydrophobic resin (B-2).
The structural unit contained in the hydrophobic resin (B-2) is as follows in molar ratio:
The weight average molecular weight, refractive index, receding contact angle, water resistance and alkali solubility of the hydrophobic resin (B-2) are shown in Table 2.
TABLE 2
| Synthesis example B-1 | Synthesis example B-2 | |
| Resin name | Hydrophobic resin (B-1) | Hydrophobic resin (B-2) |
| Weight average molecular weight | 11,000 | 10,000 |
| Refractive index | 1.54 | 1.54 |
| Receding contact angle | 81 | 84 |
| Water resistance | ○ | ○ |
| Alkali-solubility | × | × |
< Preparation of composition and evaluation results >
Next, experimental examples 1 to 4 and comparative examples 1 to 5 concerning the composition and the film are described.
Experimental example 1
A. Preparation of the composition
The composition of experimental example 1 was obtained by mixing 90 parts by weight of the alkali-soluble resin (A-1), 10 parts by weight of the hydrophobic resin (B-1), 323 parts by weight of 2-methyl-1-butanol, and 2910 parts by weight of di-n-butyl ether with a mechanical stirrer.
B. preparation of the film
The composition of experimental example 1 was coated on a silicon substrate by a spin coating method to form a coating film, and then the silicon substrate was put on a heating plate together with the above coating film, and baked at 80 ℃ for 60 seconds to form a film (film thickness 50 nm) of experimental example 1.
Experimental examples 2 to 4 and comparative examples 1 to 5
The compositions and films of experimental examples 2 to 4 and comparative examples 1 to 5 were prepared in the same procedure as experimental example 1, and they were different in that: the types of components of the compositions and the amounts thereof used were varied (as shown in tables 3 and 4). The prepared composition and film were evaluated in the following evaluation methods, and the results are shown in tables 3 and 4.
TABLE 3 Table 3
TABLE 4 Table 4
Evaluation mode
1. Weight average molecular weight
Using a gel permeation chromatograph (Gel Permeation Chromatography, GPC) (model 1515 (autosampler), 2707 (GPC pump) +2414 (refractive index (REFRACTIVE INDEX, RI) detector), manufactured by waters company (Waters Corporation), tetrahydrofuran (THF) was stabilized (as 2, 6-dibutyl-p-cresol (Butylated hydroxytoluene, BHT)) as a rinse solution at a column temperature of 40 ℃, and the weight average molecular weight of the resin was obtained by converting the time passed through polystyrene.
2. Refractive index
The refractive index of the film for light having a wavelength of 193nm was measured using an ellipsometer (ellipsometer) (model M2000DI, manufactured by j.a. Wu Lanmu (manufactured by j.a. woollam) inc.
3. Receding contact angle
Water was injected into the needle at normal temperature and pressure using a contact angle meter (model DSA100, manufactured by austdenburg corporation (KRUSS), inc.) to finely adjust the position of the needle to an initial position where water droplets were formed on the film of the silicon substrate. Subsequently, 25. Mu.L of water droplets were formed on the film of the silicon substrate by discharging water from the needle, the needle was once pulled out from the water droplets, and the needle was again pulled down and placed in the water droplets at the initial position. Then, the contact angle was measured at a rate of 10. Mu.L/min by sucking the water droplets with a needle for 90 seconds and at the same time at 1 time per second (total 90 times). Thus, the average value of the contact angle between 20 seconds after the point at which the measured value of the contact angle was stabilized was calculated as the receding contact angle (°).
4. Water resistance
The film was immersed in ultrapure water for 5 minutes, and the dissolved state was observed.
The evaluation criteria for water resistance were as follows:
o: completely insoluble;
Delta: partially dissolving;
X: completely dissolved.
5. Alkali-solubility
The film was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 1 second, and the dissolved state was observed.
The evaluation criteria for alkali solubility were as follows:
O: completely dissolving;
Delta: partially dissolving;
x: is not dissolved at all.
[ Evaluation results ]
According to tables 3 and 4, films formed from the compositions containing the alkali-soluble resin (a) (experimental examples 1 to 4) have a high receding contact angle, good water resistance, and good alkali solubility, on the premise that the refractive index can be matched with that of water and photoresist, as compared with the compositions not containing the alkali-soluble resin (a) (comparative examples 1 to 5).
Further, comparative example 1 contains the resin (a '-1) which has good alkali solubility, but since the resin (a' -1) contains a structural unit derived from (meth) acrylic acid, the receding contact angle is low due to the hydrophilicity of the carboxyl group being too high. In comparative examples 2 and 3 containing the resin (A '-1), although the proportion of the hydrophobic resin (B) was increased, the proportion of the resin (A' -1) was decreased, and the alkali solubility was poor. Comparative examples 4 and 5 contained the resin (a '-2), but the resin (a' -2) did not contain a structural unit having a carboxyl group, and thus had poor alkali solubility.
Further, as is clear from experimental example 3, comparative example 2 and comparative example 5, the alkali-soluble resin (a-1) has the structural unit (a 3) containing a long carbon chain carboxyl group (experimental example 3) on the premise that the proportion of the hydrophobic resin (B) is the same, so that the alkali solubility is excellent.
Further, as is clear from examples 2 and 4, the film formed had a higher receding contact angle when the structural unit (example 4) of the hydrophobic resin (B) contained a cycloalkyl group than when the structural unit (example 2) of the hydrophobic resin (B) contained no cycloalkyl group.
On the other hand, as is clear from experimental examples 1 to 3, the higher the proportion of the hydrophobic resin (B), the higher the receding contact angle of the formed film.
In summary, the present invention provides an alkali-soluble resin, a protective layer composition comprising an alkali-soluble resin having specific structural units (e.g., structural unit (a 1) having a fluoroalkyl group, structural unit (a 2) having an α -trifluoromethyl alcohol group, and structural unit (a 3) having a long carbon chain carboxyl group), a protective layer formed from the protective layer composition, a laminate, and a method for forming a resist pattern, wherein the protective layer has a high receding contact angle, good water resistance, and good alkali solubility on the premise that the refractive index of the protective layer can be matched with that of water and the resist, and is therefore suitable for use in immersion lithography.
Although the present invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, but rather is capable of modification in detail without departing from the spirit and scope of the present invention as defined by the appended claims.
[ Symbolic description ]
100 Laminate
110 Substrate
120 Photoresist layer
120A photoresist pattern
130 Protective layer
200 Photomask
300 Light source
L light
Claims (16)
1. An alkali-soluble resin (A) comprising a structural unit (a 1) represented by the following formula (1), a structural unit (a 2) represented by the following formula (2), and a structural unit (a 3) represented by the following formula (3),
In the formula (1), R 1 is hydrogen atom, fluorine atom, methyl or trifluoromethyl, R 2 is fluorine-containing straight-chain alkyl or fluorine-containing branched-chain alkyl with carbon number of 1-10, which represents bonding position,
In formula (2), R 3 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Y 1 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 10 carbon atoms or an arylene group, and represents a bonding position, wherein when Y 1 is an alkylene group having 2 to 10 carbon atoms or a cycloalkylene group having 5 to 10 carbon atoms, one or more of them-CH 2 -may be represented by-O-orInstead of the above-mentioned,
In formula (3), R 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Y 2 is an unsubstituted alkylene group having 2 to 8 carbon atoms, which represents a bonding position, wherein in Y 2, one or more of-CH 2 -may be via-O-orInstead of the above-mentioned,
Wherein the molar ratio between the structural unit (a 1) represented by the formula (1), the structural unit (a 2) represented by the formula (2), and the structural unit (a 3) represented by the formula (3) is 10 to 50: 50-90: 1 to 20.
2. The alkali-soluble resin (a) according to claim 1, wherein in R 2 of the formula (1), a fluorine-containing linear alkyl group or a fluorine-containing branched alkyl group having 1 to 10 carbon atoms contains 3 or more fluorine atoms.
3. A protective layer composition comprising:
the alkali-soluble resin (a) as claimed in claim 1 or 2;
A hydrophobic resin (B); and
A solvent (C),
Wherein the hydrophobic resin (B) comprises a structural unit (B1) represented by the following formula (4) and a structural unit (B2) represented by the following formula (5),
In the formula (4), R 5 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R 6 is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or an aryl group, and represents a bonding position, wherein when R 6 is an alkyl group having 2 to 10 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, one or more of them-CH 2 -may be represented by-O-orInstead of the above-mentioned,
In the formula (5), R 7 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R 8 is a fluoroalkyl group having 1 to 10 carbon atoms, and represents a bonding position.
4. The protective layer composition according to claim 3, wherein a molar ratio between the structural unit (b 1) represented by the formula (4) and the structural unit (b 2) represented by the formula (5) is 10 to 50: 50-90.
5. The protective layer composition according to claim 3, wherein in the formula (4), R 6 is an alkyl group having 1 to 10 carbon atoms.
6. The protective layer composition according to claim 3, wherein the solvent (C) comprises an alcohol solvent (C1) and an ether solvent (C2).
7. The protective layer composition according to claim 6, wherein the alcohol solvent (C1) is at least one selected from the group consisting of alcohols having 4 to 6 carbon atoms.
8. The protective layer composition according to claim 6, wherein the ether-based solvent (C2) is at least one selected from the group consisting of ethers having 8 to 12 carbon atoms.
9. The protective layer composition according to claim 6, wherein a weight ratio between the alcohol solvent (C1) and the ether solvent (C2) is 1 to 50:50 to 99.
10. The protective layer composition according to claim 3, wherein a weight ratio (B/a) between the hydrophobic resin (B) and the alkali-soluble resin (a) is more than 0.1 and less than 0.43.
11. A protective layer formed from the protective layer composition of any one of claims 3 to 10.
12. The protective layer according to claim 11, wherein the protective layer is completely dissolved after being immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 1 second on the premise that the thickness of the protective layer is 50 nm.
13. The protective layer of claim 11, wherein the receding contact angle of the protective layer to water is 69.5 degrees or more.
14. The protective layer of claim 11, wherein the protective layer has a refractive index of 1.54 to 1.55 for light having a wavelength of 193 nm.
15. A laminate, comprising:
A substrate;
a photoresist layer; and
The protective layer as claimed in any one of claim 11 to claim 14,
Wherein the photoresist layer is located between the substrate and the protective layer.
16. A method of forming a photoresist pattern, comprising:
forming a photoresist layer on a substrate;
forming a protective layer as claimed in any one of claims 11 to 14 on the photoresist layer;
exposing the photoresist layer and the protective layer; and
Developing the photoresist layer and the protective layer to form a photoresist pattern on the substrate.
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| TW110119105A TWI791224B (en) | 2021-05-26 | 2021-05-26 | Alkali-soluble resin, protective layer composition, protective layer, laminate, and method for forming photoresist pattern |
| TW110119105 | 2021-05-26 |
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| KR100991312B1 (en) * | 2007-08-30 | 2010-11-01 | 샌트랄 글래스 컴퍼니 리미티드 | Positive resist composition |
| JP5758301B2 (en) * | 2009-11-18 | 2015-08-05 | Jsr株式会社 | Radiation-sensitive resin composition, polymer, and resist pattern forming method |
| CN102311344B (en) * | 2010-06-25 | 2014-05-28 | 锦湖石油化学株式会社 | Compound, polymer comprising the same and resist protective film composition comprising the polymer |
| KR20150033793A (en) * | 2013-09-24 | 2015-04-02 | 롬엔드하스전자재료코리아유한회사 | Negative-type photosensitive resin composition and insulating film using same |
| CN112679653B (en) * | 2020-12-28 | 2021-09-14 | 甘肃华隆芯材料科技有限公司 | Photoresist film-forming resin and preparation method of photoresist composition thereof |
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