CN115403696A - 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
- Publication number
- CN115403696A CN115403696A CN202210585560.2A CN202210585560A CN115403696A CN 115403696 A CN115403696 A CN 115403696A CN 202210585560 A CN202210585560 A CN 202210585560A CN 115403696 A CN115403696 A CN 115403696A
- Authority
- CN
- China
- Prior art keywords
- protective layer
- formula
- structural unit
- represented
- alkali
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011347 resin Substances 0.000 title claims abstract description 162
- 229920005989 resin Polymers 0.000 title claims abstract description 162
- 239000011241 protective layer Substances 0.000 title claims abstract description 108
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 68
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 60
- 239000010410 layer Substances 0.000 claims description 77
- 229920002120 photoresistant polymer Polymers 0.000 claims description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 125000004432 carbon atom Chemical group C* 0.000 claims description 51
- 125000001153 fluoro group Chemical group F* 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 30
- 229910052731 fluorine Inorganic materials 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- 125000002947 alkylene group Chemical group 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 16
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 15
- 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
- 238000006467 substitution reaction Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000000732 arylene group Chemical group 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000004210 ether based solvent Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 45
- 239000003513 alkali Substances 0.000 description 30
- 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
- 238000006243 chemical reaction Methods 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 239000000243 solution Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 238000000671 immersion lithography Methods 0.000 description 8
- -1 methylene, ethylene, propylene Chemical group 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
- 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
- 239000011541 reaction mixture Substances 0.000 description 6
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000002161 passivation Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical group CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000011109 contamination Methods 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 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
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-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
- 235000019400 benzoyl peroxide Nutrition 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
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010438 heat treatment 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
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 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
- 238000005406 washing Methods 0.000 description 2
- 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 1
- 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 1
- 239000001618 (3R)-3-methylpentan-1-ol Substances 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 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
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- 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
- 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 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
- LRRBANSQUYNJTH-UHFFFAOYSA-N 2-tert-butylperoxy-2-methylpropane;2-ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O.CC(C)(C)OOC(C)(C)C LRRBANSQUYNJTH-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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- 239000004793 Polystyrene Substances 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- GTMWGXABXQTZRJ-UHFFFAOYSA-N cyclohexene-1-carbonitrile Chemical compound N#CC1=CCCCC1 GTMWGXABXQTZRJ-UHFFFAOYSA-N 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 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
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N 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 ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-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
- 125000001147 pentyl group Chemical group C(CCCC)* 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
- 229920002223 polystyrene Polymers 0.000 description 1
- 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
- UWNNZXDNLPNGQJ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)C UWNNZXDNLPNGQJ-UHFFFAOYSA-N 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
- 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
- 239000003643 water by type Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
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
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- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Electron Beam Exposure (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention provides an alkali-soluble resin, a protective layer composition, a protective layer, a laminate, and a method for forming a resist 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 represented by the following formula (1)(a1) A structural unit (a 2) represented by the following formula (2), and a structural unit (a 3) represented by the following formula (3).
Description
Technical Field
The present invention relates to an alkali-soluble resin, a protective layer composition, a protective layer, a laminate, and a method for forming a resist pattern, and particularly relates to an alkali-soluble resin, a protective layer composition, a protective layer, a laminate, and a method for forming a resist pattern, which are used in Immersion Lithography (Immersion Lithography).
Background
In the conventional semiconductor process, dry development technology is mainly used, air is used as a medium between a lens assembly and a wafer, and a pattern on a photomask is formed on the wafer. However, with the development of semiconductor processes, from 0.13 μm, 90 nm to 65 nm, not only the technical breakthrough of 157 nm dry exposure apparatus is difficult, but also the requirements for the material of the lens assembly and the transparency of the photoresist are higher.
In view of the limitations of dry development, the semiconductor industry in 2002 proposed an immersion lithography technique that uses water with a refractive index of 1.44 as a medium between the mirror assembly and the wafer to shorten 193nm wavelength light to 134 nm wavelength light, thereby forming finer patterns on the wafer.
In the immersion lithography technique, photo-acid (Photo-acid) and quencher (quencher) in the photoresist are dissolved in water, thereby causing contamination or damage to the lens assembly. Therefore, a method for forming a protection layer on the surface of the photoresist is developed in the semiconductor industry, so that the protection layer prevents the photoresist from contacting with water, and prevents the photo acid and the quencher in the photoresist from dissolving in water to cause the contamination or damage of the lens assembly.
However, in the exposure process of the immersion lithography, in addition to considering that the refractive index of the passivation layer must be matched with the water and the photoresist, the relative motion between the water and the wafer is also considered, so the passivation layer must have a high receding contact angle with respect to the water to ensure the velocity of the relative motion between the water and the 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 attacked by water. Further, the protective layer must be sufficiently alkali soluble to ensure that the protective layer peels off after subsequent development processes.
Therefore, how to improve the receding contact angle of the protective layer to water, the water resistance, and the alkali solubility is a problem to be solved by those skilled in the art on the premise that the refractive index of the protective layer can be matched with water and the photoresist.
Disclosure of Invention
In view of the above, the present invention provides an alkali-soluble resin, a protective layer composition comprising the alkali-soluble resin, a protective layer formed from the protective layer composition, a laminate, and a method for forming a resist pattern, in which 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 a resist.
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 fluorinated alkyl group having 1 to 10 carbon atoms, and represents a bonding site.
In the formula (2), R 3 Is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Y 1 Is alkylene having 1 to 10 carbon atoms, cycloalkylene having 5 to 10 carbon atoms, or arylene, wherein when Y is a bonding position 1 When it is alkylene with 2 to 10 carbon atoms or cycloalkylene with 5 to 10 carbon atoms, one or more-CH 2 May be-O-or
And (4) substitution.
In the 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 a carbon number of 2 to 8,* Represents a bonding position wherein at Y 2 In which one or more-CH 2 May be-via-O-or
And (4) substitution.
In one embodiment of the present invention, the molar ratio of 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 to 90:1 to 20.
In one embodiment of the present invention, R of formula (1) 2 In the (C1-C10) fluoroalkyl group, 3 or more fluorine atoms are contained.
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 alkyl with carbon number of 1 to 10, cycloalkyl or aryl with carbon number of 5 to 10, and represents bonding position, wherein when R is 6 When it is an alkyl group having a carbon number of 2 to 10 or a cycloalkyl group having a carbon number of 5 to 10, wherein one or more-CH groups 2 May be-via-O-or
And (4) substitution.
In the formula (5), R 7 Is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R 8 A fluorine-containing alkyl group having 1 to 10 carbon atoms, wherein denotes a bonding site.
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 to 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 alcoholic 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 of the alcohol solvent (C1) to the ether solvent (C2) is 1 to 50:50 to 99 percent.
In one embodiment of the present invention, the 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.
The invention provides a protective layer, which is formed by the protective layer composition.
In one embodiment of the present invention, on the premise that the thickness of the protective layer is 50nm, the protective layer is completely dissolved after being immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 1 second.
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 protective layer is arranged on the substrate, and the photoresist layer is arranged 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 resist composition comprising an alkali-soluble resin having specific structural units (e.g., a structural unit (a 1) having a fluoroalkyl group, a structural unit (a 2) having an α -trifluoromethylalcohol, and a structural unit (a 3) having a long carbon chain carboxyl group), a resist layer formed from the resist composition, a laminate, and a method for forming a resist pattern, in which the resist layer has a high receding contact angle, good water resistance, and good alkali solubility on the premise that the refractive index of the resist layer can be matched with water and a resist, and thus is suitable for immersion lithography.
Drawings
Fig. 1 to 4 are flow charts illustrating a method of forming a photoresist pattern according to an embodiment of the present invention.
Detailed Description
The following terms describe the present specification:
in the present specification, "(meth) acrylic acid" means "acrylic acid" and/or "methacrylic acid".
In the present specification, "alkyl" may be a substituted or unsubstituted straight or branched chain alkyl group. Alkyl is for example but not limited to methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or pentyl.
In the present 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 the present specification, "cycloalkyl" may be a substituted or unsubstituted cycloalkyl. Cycloalkyl groups are for example, but not limited to, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl.
In the present specification, "cycloalkylene" may be a substituted or unsubstituted cycloalkylene. Cycloalkylene radicals are, for example, but not limited to, for example cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, or cyclodecylene.
In the present specification, "aryl" 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 the present 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 diyl.
In the present specification, the term "structural unit" refers to 1 or more units present in a 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) (also referred to as a "structural unit (a 1) having a fluoroalkyl group" in the present specification), a structural unit (a 2) represented by the following formula (2) (also referred to as an "α -trifluoromethylalcohol-containing structural unit (a 2)" in the present specification), and a structural unit (a 3) represented by the following formula (3) (also referred to as a "long-carbon-chain carboxyl-containing structural unit (a 3)" in the present specification).
[ structural Unit (a 1) represented by formula (1) ]
The structural unit (a 1) represented by the formula (1) has a fluoroalkyl group, and introduction of a fluorine atom into the structural unit can lower the refractive index of a resin layer or a protective layer formed of the alkali-soluble resin (a), and improve hydrophobicity and water resistance. It is to be noted that hydrophobicity is related to a contact angle with water, and therefore introduction of fluorine atoms into the structural unit can also increase the contact angle with water and the receding contact angle with water of the alkali-soluble resin (a). On the other hand, if fluorine atoms are not introduced into the structural unit, the refractive index is too high and the receding contact angle is too low, which is disadvantageous for the alkali-soluble resin (a) to be used 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 reaction mixture is,
R 1 hydrogen atom, fluorine atom, methyl group or trifluoromethyl group, preferably hydrogen atom or methyl group;
R 2 a fluoroalkyl group having 1 to 10 carbon atoms, preferably 5 to 10 carbon atoms;
* Indicating the bonding position.
When R is 2 In the case of a fluoroalkyl group having 5 to 10 carbon atoms, the alkali-soluble resin (a) can further increase the hydrophobicity and water resistance.
R of formula (1) 2 In the (b), the fluoroalkyl group having 1 to 10 carbon atoms may contain 1 or more fluorine atoms, preferably 3 or more fluorine atoms, and 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 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 formula (1) is, for example, a structural unit (a 1-1) represented by formula (1-1) below.
In the formula (1), the reaction mixture is,
r' is a fluorine atom or a trifluoromethyl group, preferably a fluorine atom;
r' is a hydrogen atom or a fluorine atom;
r is an integer of 0 to 3, preferably 1 or 2;
s is an integer of 0 to 7, preferably an integer of 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 a combination thereof. Specific examples of the structural unit (a 1-1) represented by the formula (1-1) preferably include the structural unit 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 α -trifluoromethylalcohol, wherein the refractive index of the alkali-soluble resin (a) can be lowered by introducing a fluorine atom into the structural unit. It is to be noted that hydrogen of the-OH group in the α -trifluoromethylalcohol has acidity, and therefore 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 reaction mixture is,
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 alkylene having 1 to 10 carbon atoms, cycloalkylene having 5 to 10 carbon atoms, or arylene, preferably alkylene having 3 to 10 carbon atoms;
* Indicating the position of the bond to the substrate,
wherein when Y is 1 When it is alkylene with 2 to 10 carbon atoms or cycloalkylene with 5 to 10 carbon atoms, one or more-CH 2 May be-O-or
And (4) substitution.
When Y is 1 Is alkylene with 3 to 10 carbon atomsIn this case, 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 formula (2) include the structural unit represented by formula (2-1-1) to the structural unit represented by formula (2-1-16), the structural unit represented by formula (2-2-1) to the structural unit represented by formula (2-2-5), the structural unit represented by formula (2-3), or a combination thereof. Specific examples of the structural unit (a 2) represented by the formula (2) preferably include a structural unit represented by the following formula (2-1-3), a structural unit represented by the following formula (2-1-5), or a combination thereof.
[ structural Unit (a 3) represented by formula (3) ]
The structural unit (a 3) represented by the formula (3) contains a long carbon chain carboxyl group, wherein the alkali solubility of the alkali-soluble resin (A) can be improved and a suitable development rate can be obtained by introducing the long carbon chain carboxyl group into the structural unit. On the other hand, if all the structural units containing a carboxyl group in the alkali-soluble resin (a) are structural units derived from (meth) acrylic acid, the receding contact angle of the protective layer formed of the alkali-soluble resin (a) decreases due to excessively high hydrophilicity of the carboxyl group.
Specifically, the structural unit (a 3) represented by formula (3) is as follows:
in the formula (3), the reaction mixture is,
R 4 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, preferably a hydrogen atom orA methyl group;
Y 2 is alkylene with 2 to 8 carbon atoms, preferably alkylene with 5 to 8 carbon atoms;
* Indicating the position of the bond to the substrate,
wherein at Y 2 In which one or more-CH 2 May be-O-or
Substituted, preferably one of-CH 2 Warp of
And (4) substitution.
When Y is 2 In the case of an alkylene group having 5 to 8 carbon atoms, the alkali-soluble resin (a) can be made to have appropriate alkali solubility and development rate, and the hydrophobicity, water resistance, and receding contact angle can be further improved.
The structural unit (a 3) represented by the formula (3) is, for example, a structural unit (a 3-1) represented by the formula (3-1), a structural unit (a 3-2) represented by the formula (3-2), a structural unit (a 3-3) represented by the formula (3-3), a 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 formula (3) are described in detail below, wherein the specific examples of the structural unit (a 3) represented by formula (3) preferably include the structural units represented by the following formulae (3-3-5).
In the formula (3-1),
R 4 is a hydrogen atom or a methyl group;
Y 3 is alkylene having 2 to 8 carbon atoms;
* Indicates the bonding position.
Specific examples of the structural unit represented by formula (3-1) include the structural units represented by formula (3-1-1) to formula (3-1-7).
In the formula (3-2), the compound,
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 m is,
* Indicating the bonding position.
Specific examples of the structural unit represented by the formula (3-2) include the structural unit represented by the formula (3-2-1) to the structural unit 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 formula (3-3) include structural units represented by formula (3-3-1) to structural units represented by formula (3-3-14).
In the formula (3-4), the metal oxide,
R 4 is a hydrogen atom or a methyl group;
Y 8 is alkylene 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 the structural unit represented by the formula (3-4-1) to the structural unit 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 to 90:1 to 20, preferably 20 to 40:50 to 70:1 to 10. When the molar ratio among 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 range, the resin layer formed of the alkali-soluble resin (a) or the protective layer described later can be well balanced in refractive index, alkali developability, and development rate. However, if the receding contact angle required for a protective layer of a photoresist is to be obtained, it is still necessary to use the hydrophobic resin (B) described later.
The structural unit constituting the alkali-soluble resin (a) may further include other structural units than 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), as long as the effects of the present embodiment are not impaired.
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, a resin layer formed of the alkali-soluble resin (a) or a protective layer described later can have both good water resistance and alkali solubility.
On the premise that the thickness of the resin layer formed of the alkali-soluble resin (a) was 50nm, the resin layer was immersed in a 2.38 mass% aqueous solution of tetramethylammonium 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) can be polymerized from a first monomer mixture including a monomer derived from the structural unit (a 1) represented by formula (1), a monomer derived from the structural unit (a 2) represented by formula (2), and a monomer derived from the structural unit (a 3) represented by formula (3). The polymerization method is not particularly limited, and an appropriate polymerization method may be selected as required. 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 in the formula (I) 1 、R 2 And R in the formula (1) 1 、R 2 The same is not repeated herein.
Specific examples of the monomer represented by the formula (I) include monomers derived from the structural unit represented by the above formula (1-1-1) to the structural unit represented by the above formula (1-1-9), and will not be described in detail.
The monomer derived as the structural unit (a 2) represented by the formula (2) is, for example, a monomer represented by the formula (II).
R in the formula (II) 3 、Y 1 And R in the formula (2) 3 、Y 1 The same is not described 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 will not be described in detail herein.
The monomer derived as the structural unit (a 3) represented by the formula (3) is, for example, a monomer represented by the formula (III).
R in the formula (III) 4 、Y 2 And R in the formula (3) 4 、Y 2 The same is not repeated herein.
Specific examples of the monomer represented by the formula (III) include a monomer derived from the structural unit represented by the formula (3-1-1) to the structural unit represented by the formula (3-1-7), the structural unit represented by the formula (3-2-1) to the structural unit represented by the formula (3-2-6), the structural unit represented by the formula (3-3-1) to the structural unit represented by the formula (3-3-14), and 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.
Further, the first monomer mixture may further include other monomers than the monomer represented by the formula (I), the monomer represented by the formula (II), and the monomer represented by the 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 can dissolve the monomer. Specific examples of the solvent include acetone, methyl isobutyl ketone, 2-heptanone, cyclohexanone, or a combination 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 can be dissolved in the solvent monomer without reacting with the monomer. Specific examples of the polymerization initiator include organic peroxides such as 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 peroxyisopropylcarbonate (t-butyl peroxide), t-amyl 2-ethylhexanoate peroxide (t-amyl peroxy-2-ethylhexanoate), t-butyl 2-ethylhexanoate (t-butyl peroxide-2-ethylhexanoate), and the like; 2,2'-azobis (isobutyronitrile) (2,2' -azobiss (isobutryronitrile)), 1,1'-azobis (cyclohexanecarbonitrile) (1,1' -azobiss (cyclohexenecarbonitrile)), 2,2'-azobis (2,4-dimethylvaleronitrile) (2,2' -azobis (2,4-dimethylmaleonitril)), dimethyl 2,2'-azobis (2-methylpropionate) (dimethyl 2,2' -azobis (2-methyl propioniate)), and the like. The polymerization initiator is preferably tert-butyl peroxy-2-ethylhexanoate. The amount of the polymerization initiator 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 ℃, preferably 60 ℃ to 130 ℃.
In the case of synthesizing the alkali-soluble resin (a) by a 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 comprising: 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 respective 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 herein.
Hydrophobic resin (B)
The hydrophobic resin (B) includes a structural unit (B1) represented by the following formula (4) (also referred to as a "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 a "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) relates to the solubility of the hydrophobic resin (B) in the solvent (C). Specifically, the structural unit (B1) represented by 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 smoothly dissolved in the solvent (C).
Specifically, the structural unit (b 1) represented by formula (4) is as follows:
in the formula (4), the reaction mixture is,
R 5 hydrogen atom, fluorine atom, methyl group or trifluoromethyl group, preferably hydrogen atom or methyl group;
R 6 alkyl with carbon number of 1 to 10, cycloalkyl with carbon number of 5 to 10 or aryl, preferably alkyl with carbon number of 1 to 10 or cycloalkyl with carbon number of 5 to 10, more preferably alkyl with carbon number of 1 to 10;
* Indicating the position of the bond to the substrate,
wherein when R is 6 When it is an alkyl group having 2 to 10 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, wherein one or more-CH groups 2 May be-O-or
And (4) substitution.
In one embodiment, in formula (4), R 6 Is an alkyl group having 1 to 10 carbon atoms. When R is 6 In the case of an alkyl group having 1 to 10 carbon atoms, the structural unit (B1) represented by formula (4) has a carbon chain, and therefore has good compatibility with a solvent (C) having a long carbon chain described later (particularly, an alcohol solvent (C1)), and the hydrophobic resin (B) can be smoothly dissolved in the solvent (C).
In one embodiment of the method of the present invention,in the formula (4), R 6 An alkyl group having 5 to 10 carbon atoms. When R is 6 In the case of an alkyl group having 5 to 10 carbon atoms, the structural unit (B1) represented by formula (4) has a long carbon chain, and therefore has better compatibility with a solvent (C) having a long carbon chain described later (particularly, an alcohol solvent (C1)), and the hydrophobic resin (B) can be more smoothly dissolved in the solvent (C).
In one embodiment, in formula (4), R 6 Is a cycloalkyl group having a carbon number of 5 to 10. When R is 6 In the case of a cycloalkyl group having 5 to 10 carbon atoms, the receding contact angle of the resin layer or the protective layer formed of the hydrophobic resin (B) can be further increased.
Specific examples of the structural unit represented by formula (4) include a structural unit represented by formula (4-4-1) to a structural unit represented by formula (4-4-34), a structural unit represented by formula (4-2-1) to a structural unit represented by formula (4-2-14), a structural unit represented by formula (4-3-1) to a structural unit represented by formula (4-3-2), or a combination thereof. Specific examples of the structural unit represented by formula (4) preferably include structural units represented by the following formulae (4-1 to 29), structural units represented by the following formulae (4-2 to 7), or a combination thereof.
[ structural Unit (b 2) represented by formula (5) ]
The structural unit (B2) represented by the formula (5) contains a fluorine atom, and by introducing a fluorine atom into the structural unit, the refractive index of the hydrophobic resin (B) can be lowered, and the hydrophobicity and water resistance can be improved. It is to be noted that hydrophobicity is related to a contact angle with water, and therefore, introduction of fluorine atoms in the structural unit can also increase a contact angle with water and a receding contact angle with water of the hydrophobic resin (B). On the other hand, if fluorine atoms are not introduced into the structural unit, 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 reaction mixture is,
R 7 hydrogen atom, fluorine atom, methyl group or trifluoromethyl group, preferably hydrogen atom or methyl group;
R 8 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 is 8 In the case of a fluoroalkyl group having 5 to 10 carbon atoms, the hydrophobicity and water resistance of the hydrophobic resin (B) can be further increased.
R of formula (5) 8 In the (b), the fluoroalkyl group having 1 to 10 carbon atoms may contain 1 or more fluorine atoms, preferably 3 or more fluorine atoms, and 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 protective layer formed of the hydrophobic resin (B) can be further decreased, and the hydrophobicity and water resistance can be improved.
Specific examples of the structural unit (b 2) represented by formula (5) are the same as those of the structural unit (a 1) represented by 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 formulae (1-1-1) to (1-1-9) are described above, and are not described herein again. Specific examples of the structural unit (b 2) represented by the formula (5) preferably include structural units represented by the following formulae (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 to 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 range, a resin layer formed of a hydrophobic resin or a protective layer described later can be well balanced in solubility, refractive index, and receding contact angle. However, if the alkali solubility and the developing rate required for the protective layer of the photoresist are to be obtained, the resin (A) needs to be used together with the alkali-soluble resin.
The constituent unit constituting the hydrophobic resin (B) may further include other constituent units than the constituent unit (B1) represented by the formula (4) and the constituent 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, a resin layer formed of the hydrophobic resin (B) or a protective layer described later can 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 in the above range, a better balance between the receding contact angle of the protective layer and the alkali-solubility can be obtained on the premise that the refractive index of the protective layer can be matched with that of water and the photoresist.
On the premise that the thickness of the resin layer formed of the hydrophobic resin (B) is 50nm, the receding contact angle of the resin layer with respect to water is 69.5 degrees or more.
[ 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 formula (4) and a monomer derived from the structural unit (B2) represented by formula (5). The polymerization method is not particularly limited, and an appropriate polymerization method may be selected as required. The polymerization method is, for example, a solution polymerization method.
The monomer derived as the structural unit (b 1) represented by the formula (4) is, for example, a monomer represented by the formula (IV).
R in the formula (IV) 5 、R 6 And R in the formula (4) 5 、R 6 The same is not repeated 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 will not be described in detail.
The monomer derived to the structural unit (b 2) represented by the formula (5) is, for example, a monomer represented by the formula (V).
R in the formula (V) 7 、R 8 And R in the formula (5) 7 、R 8 The same is not repeated 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 examples of the monomer represented by the formula (V) include monomers derived from the structural unit represented by the above formula (1-1-1) to the structural unit represented by the above formula (1-1-9), and will not be described again.
Further, the second monomer mixture may further include other monomers than the monomer represented by the formula (IV) and the monomer represented by the formula (V), and 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 can dissolve the monomer without reacting with the monomer. Specific examples of the solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, or a combination 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 can be dissolved in the solvent monomer without reacting with the 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 herein.
In the case of synthesizing the hydrophobic resin (B) by the solution polymerization method, the polymerization temperature may be 40 ℃ to 150 ℃, preferably 60 ℃ to 130 ℃.
In the case of synthesizing the hydrophobic resin (B) by the solution polymerization method, the polymerization time may be 1 hour to 12 hours, preferably 2 hours to 6 hours.
Further, 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 alcoholic 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 therefore has good compatibility with the structural unit represented by formula (4) in the hydrophobic resin (B), and 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, di-iso-pentyl ether, di-n-pentyl ether, methylcyclopentyl ether, methylcyclohexyl ether, di-sec-butyl ether, di-sec-pentyl ether, di-tert-pentyl 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 properties, so that the protective layer formed by the protective layer composition does not interact with the photoresist layer, and the protective layer can fully play a role in protecting the photoresist layer.
The weight ratio of the alcohol solvent (C1) to the ether solvent (C2) may be 1 to 50:50 to 99, preferably 5 to 15:85 to 95.
It is to be noted that, in the present embodiment, a two-solvent system is employed, with the ether solvent (C2) as a main solvent and the alcohol solvent (C1) as a sub solvent, whereby the solvent (C) exhibits excellent solubility to the alkali-soluble resin (a) and the hydrophobic resin (B). In particular, when the weight ratio between the alcohol solvent (C1) and 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 protective layer formed from the protective layer composition does not interact with the photoresist layer, thereby further exhibiting the function of protecting the photoresist layer with the protective 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, from the viewpoint 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 to the photoresist layer.
Additive (D)
The protective layer composition may further contain, in addition to the above components, an additive (D) such as a surfactant, if necessary, without affecting the efficacy of the present embodiment.
< preparation of overcoat layer composition >
The method for preparing 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 stirred in a stirrer to be uniformly mixed into a solution state, and the additive (D) may be added if necessary and uniformly mixed to obtain a protective layer composition in a solution state.
< protective layer >
The present embodiment provides a protective layer formed from the above-described protective layer composition.
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, provided that the protective layer has a thickness of 50nm. 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 with respect 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 to water and photoresist.
< method for Forming laminate and 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; and step (iv): and developing the photoresist layer and the protective layer to form a photoresist pattern on the substrate. The following will detail each step with reference to fig. 1 to 4:
step (i)
As shown in fig. 1, the photoresist layer 120 is formed on the substrate 110, wherein the method of forming the photoresist layer 120 is not particularly limited, 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 may be, 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 that generally contains 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 above-described protective layer 130 is formed on the photoresist layer 120. Thus, the stacked body 100 including the substrate 110, the photoresist layer 120, and the protection layer 130 can be formed, wherein the photoresist layer 120 is located between the substrate 110 and the protection layer 130.
The method of forming the protective layer 130 is not particularly limited, and baking is performed after a coating method such as spin coating, spray coating, or roll coating, for example. The baking method is not particularly limited, and for example, the laminated body 100 is placed on a hot 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 above-described protective layer composition. The passivation layer 130 is coated on the photoresist layer 120 to prevent water used as an immersion medium in the immersion lithography technique from penetrating into the photoresist layer, and prevent the photo acid and the quencher in the photoresist from dissolving in water to cause the contamination or damage of the lens assembly. In addition, in order to reduce the surface tension of water and increase the surface activity, an aliphatic alcohol such as methanol, ethanol, or isopropyl alcohol 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 passivation layer 130 preferably does not mix 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 passes through the mask 200 having a pattern and water (not shown) as a wetting medium to expose the photoresist layer 120 and the passivation layer 130.
The exposure wavelength may be 250 nm or less, preferably 220 nm or less, such as KrF excimer laser (248 nm), arF excimer laser (193 nm), F 2 Excimer laser (157 nm), or X-ray.
The exposure dose may be 1 mj/cm to 100 mj/cm.
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 photoresist, after the photoresist layer 120 is exposed, the exposed portion of the photoresist layer 120 and the protection layer 130 will be dissolved in a developing solution during development, thereby leaving the unexposed photoresist pattern 120a after development. When the photoresist layer 120 is a negative photoresist, after the photoresist layer 120 is exposed, the unexposed portion of the photoresist layer 120 and the protection layer 130 are dissolved in a developing solution during development, thereby leaving the exposed photoresist pattern 120a after development.
The developer is, for example, an inorganic alkaline aqueous solution. Specific examples of the alkali 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; aliphatic tertiary amines such as trimethylamine, diethylaminomethyl, dimethylethylamine, and triethylamine; tertiary aliphatic cyclic acids such as pyrrole, piperidine, N-methylpiperidine, N-methyl 1,8-diazabicyclo [5.4.0] -7-undecene or 1,5-diazabicyclo [4.3.0] -5-nonene; aromatic tertiary amines such as pyridine, methylpyrimidine, lutidine, and quinoline; and quaternary ammonium salt basic compounds such as aqueous solutions of tetramethylammonium hydroxide or tetraethylammonium 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 tetramethylammonium hydroxide.
After step (iv), a further washing step may be carried out. Specifically, the developing solution adhering to the substrate 110 and the photoresist pattern 120a is removed with pure water and/or supercritical fluid.
Hereinafter, the present invention will be described more specifically by way of examples. 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 restrictively based on the experimental examples described below.
Examples
< Synthesis of alkali-soluble resin (A) >
The following describes synthesis example A-1 of the alkali-soluble resin (A) and comparative synthesis examples A ' -1 and A ' -2 of the resin (A ') as a comparative example.
[ Synthesis example A-1]
2.34 g of octafluoropentyl methacrylate, 4.35 g of 1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-methyl-acrylate, 4.01 g of 1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-5-methyl-acrylate and 0.63 g of mono [2- [ (2-methyl-acryloyl) oxy ] ethyl ] succinate were dissolved in 19 ml of cyclohexanone, to which 0.67 g of tert-butyl peroxy 2-ethylhexanoate was added as a polymerization initiator. Subsequently, the mixed solution was stirred at 90 ℃ for 4 hours under a nitrogen atmosphere to carry out a reaction. Then, the solution obtained by the reaction was poured into 36 g of n-hexane while vigorously stirring, after the polymer was settled, the upper layer solvent was removed, and finally dried in vacuum to obtain a white alkali-soluble resin (A-1).
The alkali-soluble resin (A-1) contains the following structural units in the following molar ratios:
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 each evaluation manner described below, and are shown in Table 1.
Note that the refractive index, receding contact angle, water resistance, and alkali solubility of the resin were evaluated in the form of a "film". Specifically, after mixing 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 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 together with the above coating film was placed on a hot plate and baked at 80 ℃ for 60 seconds to form a film (film thickness 50 nm). Next, the film was evaluated for refractive index, receding contact angle, water resistance, and alkali solubility.
[ comparative Synthesis example A' -1]
2.47 g of octafluoropentyl methacrylate, 4.48 g of 1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-methyl-acrylate, 3.99 g of 1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-5-methyl-acrylate and 0.35 g of methacrylic acid were dissolved in 19 ml of cyclohexanone, to which 0.71 g of tert-butyl peroxy 2-ethylhexanoate was added as a polymerization initiator. Subsequently, the mixed solution was stirred at 90 ℃ for 4 hours under a nitrogen atmosphere to carry out a reaction. Then, the solution obtained by the reaction was poured into 36 g of n-hexane while vigorously stirring, after the polymer was settled, the upper layer solvent was removed, and finally dried in vacuum to obtain a white resin (A' -1).
The structural units contained in the resin (A' -1) and the molar ratio thereof are 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 evaluation methods described below, and are shown in Table 1.
[ comparative Synthesis example A' -2]
2.30 g of octafluoropentyl methacrylate, 4.74 g of 1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-methyl-acrylate and 4.29 g of 1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-5-methyl-acrylate were dissolved in 19 ml of cyclohexanone, to which 0.66 g of tert-butyl peroxy 2-ethylhexanoate was added as a polymerization initiator. Subsequently, the mixed solution was stirred at 90 ℃ for 4 hours under a nitrogen atmosphere to carry out a reaction. Then, the solution obtained by the reaction was poured into 36 g of n-hexane while vigorously stirring, after the polymer was settled, the upper layer solvent was removed, and finally dried in vacuum to obtain a white resin (A' -2).
The structural units contained in the resin (A' -2) and the molar ratio thereof are 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 each evaluation manner described below, 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 octafluoropentyl methacrylate and 2.49 g of 2-ethylhexyl methacrylate were dissolved in 19.56 ml of propylene glycol monomethyl ether, to which 0.72 g of tert-butyl peroxy-2-ethylhexanoate was added as a polymerization initiator. Subsequently, the mixed solution was stirred at 90 ℃ for 4 hours under a nitrogen atmosphere to carry out a reaction. Then, the solution obtained by the reaction was poured into 36 g of n-hexane while vigorously stirring, after the polymer was settled, the upper layer solvent was removed, and finally dried in vacuum to obtain a white hydrophobic resin (B-1).
The hydrophobic resin (B-1) contains the following structural units in the following molar ratios:
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 octafluoropentyl methacrylate and 2.70 g of tricyclo [5.2.1.0 ] methacrylate are reacted 2,6 ]Decan-8-yl ester in 19.56 ml of propaneTo glycol monomethyl ether, 0.71 g of t-butyl peroxy-2-ethylhexanoate was added as a polymerization initiator. Subsequently, the mixed solution was stirred at 90 ℃ for 4 hours under a nitrogen atmosphere to effect a reaction. Then, the solution obtained by the reaction was poured into 36 g of n-hexane while vigorously stirring, after the polymer was settled, the upper layer solvent was removed, and finally dried in vacuum to obtain a white hydrophobic resin (B-2).
The hydrophobic resin (B-2) contains the following structural units in the following molar ratios:
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 | |
| Name of resin | 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 | ○ | ○ |
| Solubility in alkali | × | × |
< preparation of composition and evaluation results >
Next, experimental examples 1 to 4 and comparative examples 1 to 5 concerning the composition and the film will be 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 together with the above coating film was placed on a hot plate 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 in experimental example 1, and they were different in that: the types of the components of the composition and the amounts thereof used were changed (as shown in tables 3 and 4). The prepared compositions and films were evaluated in the evaluation manners described below, and the results are shown in tables 3 and 4.
TABLE 3
TABLE 4
[ evaluation methods ]
1. Weight average molecular weight
Using a Gel Permeation Chromatograph (GPC) (model 1515 (autosampler), 2707 (GPC pump) +2414 (Refractive Index (RI) detector), manufactured by Waters Corporation), tetrahydrofuran (THF) (stabilized with 2,6-dibutyl-p-cresol (BHT), available from deshan (Duksan) Corporation) as a washing liquid at a column temperature of 40 ℃, the weight average molecular weight of the resin was obtained through conversion of time passing through polystyrene.
2. Refractive index
The refractive index of the film for light having a wavelength of 193nm was measured using an ellipsometer (model M2000DI, manufactured by j.a. Wu Lanmu (j.a. woollam), ltd.).
3. Receding contact angle
Water was injected into the needles at normal temperature and pressure using a contact angle meter (model DSA100, manufactured by KRUSS corporation), and the positions of the needles were finely adjusted to initial positions at which water droplets were formed on the silicon substrate film. Subsequently, water was drained from the needles to form 25 μ L of water droplets on the film of the silicon substrate, the needles were once pulled out of the water droplets, and the needles were again pulled down and arranged in the water droplets at the initial positions. Subsequently, the contact angle was measured 1 time per second while sucking a water droplet with a needle for 90 seconds at a speed of 10. Mu.L/min (90 times in total). In this manner, the average value of the contact angle between 20 seconds after the time point when the measured value of the contact angle was stable was calculated as the receding contact angle (°).
4. Water resistance
The membrane 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;
and (delta): partial dissolution;
x: and completely dissolving.
5. Solubility in alkali
The membrane 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 are as follows:
o: completely dissolving;
and (delta): partial dissolution;
x: it is completely insoluble.
[ evaluation results ]
According to tables 3 and 4, the 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, compared to the compositions containing no alkali-soluble resin (a) (comparative examples 1 to 5), on the premise that the refractive index can be matched to that of water and a photoresist.
Further, comparative example 1 contains resin (a '-1), which has good alkali solubility, but since resin (a' -1) contains a structural unit derived from (meth) acrylic acid, the receding contact angle is too low because of the excessively high hydrophilicity of the carboxyl group. In comparative examples 2 and 3 containing the resin (A '-1), the proportion of the hydrophobic resin (B) was increased, but the alkali solubility was poor because the proportion of the resin (A' -1) was decreased. 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 the alkali solubility was poor.
Further, it is understood from experimental example 3, comparative example 2 and comparative example 5 that the alkali-soluble resin (a-1) has a structural unit (a 3) having a long carbon chain carboxyl group (experimental example 3) on the premise that the proportion of the hydrophobic resin (B) is the same, and thus the alkali-solubility is excellent.
Furthermore, it is understood from experimental examples 2 and 4 that the film formed by the hydrophobic resin (B) containing a cycloalkyl group-containing structural unit (experimental example 4) has a higher receding contact angle than the hydrophobic resin (B) containing no cycloalkyl group-containing structural unit (experimental example 2).
On the other hand, it is understood from experimental examples 1 to 3 that the higher the proportion of the hydrophobic resin (B), the higher the receding contact angle of the formed film.
As described above, the present invention provides an alkali-soluble resin, a resist composition comprising an alkali-soluble resin having specific structural units (e.g., a structural unit (a 1) having a fluoroalkyl group, a structural unit (a 2) having an α -trifluoromethylalcohol, and a structural unit (a 3) having a long carbon chain carboxyl group), a resist layer formed from the resist composition, a laminate, and a method for forming a resist pattern, in which the resist layer has a high receding contact angle, good water resistance, and good alkali solubility on the premise that the refractive index of the resist layer can be matched with that of water and a resist, and thus is suitable for 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 to the embodiments, and various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the invention.
[ notation ] to show
100 laminate
110 base plate
120 photoresist layer
120a photoresist pattern
130 protective layer
200 mask
300 light source
L is light
Claims (18)
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 a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R 2 A fluorine-containing alkyl group having 1 to 10 carbon atoms, which represents a bonding site,
in the formula (2), R 3 Is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Y 1 Is alkylene having 1 to 10 carbon atoms, cycloalkylene having 5 to 10 carbon atoms, or arylene, wherein when Y is a bonding position 1 When it is an alkylene group having a carbon number of 2 to 10 or a cycloalkylene group having a carbon number of 5 to 10, wherein one or more-CH groups 2 May be-O-or
The substitution is carried out by the following steps,
in the formula (3), R 4 Is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, Y 2 Is alkylene with 2 to 8 carbon atoms, represents bonding position, wherein in Y 2 In which one or more-CH 2 May be-O-or
And (4) substitution.
2. The alkali-soluble resin (A) according to claim 1, 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 to 90:1 to 20.
3. The base according to claim 1A soluble resin (A), wherein R of the formula (1) 2 In the (C1-C10) fluoroalkyl group, 3 or more fluorine atoms are contained.
4. A protective layer composition comprising:
an alkali-soluble resin (A) as claimed in any one of claim 1 to claim 3;
a hydrophobic resin (B); and
a solvent (C).
5. The protective layer composition according to claim 4, 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 alkyl with carbon number of 1 to 10, cycloalkyl or aryl with carbon number of 5 to 10, and represents bonding position, wherein when R is 6 When it is an alkyl group having 2 to 10 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, wherein one or more-CH groups 2 May be-O-or
The substitution is carried out by the following steps,
in the formula (5), R 7 Is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R 8 A fluorine-containing alkyl group having 1 to 10 carbon atoms, wherein denotes a bonding site.
6. The protective layer composition according to claim 5, wherein 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 10 to 50:50 to 90.
7. The protective layer composition as claimed in claim 5, wherein in formula (4), R is 6 Is an alkyl group having 1 to 10 carbon atoms.
8. The protective layer composition according to claim 4, wherein the solvent (C) comprises an alcohol solvent (C1) and an ether solvent (C2).
9. The protective layer composition of claim 8, wherein the alcoholic solvent (C1) is at least one selected from the group consisting of alcohols having a carbon number of 4 to 6.
10. The protective layer composition of claim 8, wherein the ether-based solvent (C2) is at least one selected from the group consisting of ethers having a carbon number of 8 to 12.
11. The protective layer composition according to claim 8, wherein the weight ratio between the alcohol solvent (C1) and the ether solvent (C2) is 1 to 50:50 to 99.
12. The protective layer composition of claim 4, wherein 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.
13. A protective layer formed from the protective layer composition of any one of claims 4 to 12.
14. The protective layer according to claim 13, 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 50nm.
15. The protective layer of claim 13, wherein the protective layer has a receding contact angle with water of 69.5 degrees or more.
16. The protective layer of claim 13, wherein the protective layer has a refractive index of 1.54 to 1.55 for light having a wavelength of 193 nm.
17. A laminate, comprising:
a substrate;
a photoresist layer; and
the protective layer of any one of claims 13 to 16,
wherein the photoresist layer is located between the substrate and the protective layer.
18. 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 13 to 16 on the photoresist layer;
exposing the photoresist layer and the protective layer; and
and developing the photoresist layer and the protective layer to form a photoresist pattern on the substrate.
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| KR20090023155A (en) * | 2007-08-30 | 2009-03-04 | 샌트랄 글래스 컴퍼니 리미티드 | Positive resist composition |
| CN102311344A (en) * | 2010-06-25 | 2012-01-11 | 锦湖石油化学株式会社 | Compound, polymer comprising the same and resist protective film composition comprising the polymer |
| CN103923426A (en) * | 2013-01-16 | 2014-07-16 | Jsr株式会社 | Resin Composition, Cured Film, Forming Method Thereof, Semiconductor Element And Display Element |
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| JP4300847B2 (en) * | 2003-04-01 | 2009-07-22 | Ｊｓｒ株式会社 | Photosensitive resin film and cured film comprising the same |
| CN102597878B (en) * | 2009-11-18 | 2015-09-02 | Jsr株式会社 | Radiation sensitive resin composition, polymkeric substance and Resist patterns formation method |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20090023155A (en) * | 2007-08-30 | 2009-03-04 | 샌트랄 글래스 컴퍼니 리미티드 | Positive resist composition |
| US20090061353A1 (en) * | 2007-08-30 | 2009-03-05 | Central Glass Company, Limited | Positive-Type Resist Composition |
| CN102311344A (en) * | 2010-06-25 | 2012-01-11 | 锦湖石油化学株式会社 | Compound, polymer comprising the same and resist protective film composition comprising the polymer |
| CN103923426A (en) * | 2013-01-16 | 2014-07-16 | Jsr株式会社 | Resin Composition, Cured Film, Forming Method Thereof, Semiconductor Element And Display Element |
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