JP6154398B2 - Photoresist composition - Google Patents
Photoresist composition Download PDFInfo
- Publication number
- JP6154398B2 JP6154398B2 JP2014547094A JP2014547094A JP6154398B2 JP 6154398 B2 JP6154398 B2 JP 6154398B2 JP 2014547094 A JP2014547094 A JP 2014547094A JP 2014547094 A JP2014547094 A JP 2014547094A JP 6154398 B2 JP6154398 B2 JP 6154398B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- photoresist composition
- unsaturated compound
- pattern
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 35
- 229920002120 photoresistant polymer Polymers 0.000 title claims description 30
- 238000000034 method Methods 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 20
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 17
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 15
- 229920006243 acrylic copolymer Polymers 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000003504 photosensitizing agent Substances 0.000 claims description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000012963 UV stabilizer Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000003623 enhancer Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical class OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 claims 1
- 239000011342 resin composition Substances 0.000 description 31
- 230000008569 process Effects 0.000 description 25
- -1 glycidyl α-ethyl acrylate Chemical compound 0.000 description 24
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910004205 SiNX Inorganic materials 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- KOVAQMSVARJMPH-UHFFFAOYSA-N 4-methoxybutan-1-ol Chemical class COCCCCO KOVAQMSVARJMPH-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000001174 ascending effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- IIHAWQOFHTYWGM-UHFFFAOYSA-N 1,4-diethoxybutane Chemical compound CCOCCCCOCC IIHAWQOFHTYWGM-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 description 2
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 2
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 description 2
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 2
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 2
- RVNBCIQRFGXLRD-UHFFFAOYSA-N 1-propoxypropan-2-yl propanoate Chemical compound CCCOCC(C)OC(=O)CC RVNBCIQRFGXLRD-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- BYVKCQBOHJQWIO-UHFFFAOYSA-N 2-ethoxyethyl propanoate Chemical class CCOCCOC(=O)CC BYVKCQBOHJQWIO-UHFFFAOYSA-N 0.000 description 2
- VAHNPAMCADTGIO-UHFFFAOYSA-N 2-methoxyethyl propanoate Chemical class CCC(=O)OCCOC VAHNPAMCADTGIO-UHFFFAOYSA-N 0.000 description 2
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 2
- WXYSZTISEJBRHW-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propan-2-yl]phenol Chemical compound C=1C=C(C(C)(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WXYSZTISEJBRHW-UHFFFAOYSA-N 0.000 description 2
- QRUOTIJTSNETKW-UHFFFAOYSA-N 4-ethoxybutan-1-ol Chemical compound CCOCCCCO QRUOTIJTSNETKW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- RHFOYRRUVLOOJP-UHFFFAOYSA-N ethoxyethane;propanoic acid Chemical compound CCOCC.CCC(O)=O RHFOYRRUVLOOJP-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- SSLASPHAKUVIRG-UHFFFAOYSA-N (2-methylcyclohexyl) prop-2-enoate Chemical compound CC1CCCCC1OC(=O)C=C SSLASPHAKUVIRG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PHPRWKJDGHSJMI-UHFFFAOYSA-N 1-adamantyl prop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C=C)C3 PHPRWKJDGHSJMI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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
- OCKQMFDZQUFKRD-UHFFFAOYSA-N 2-[(3-ethenylphenyl)methoxymethyl]oxirane Chemical compound C=CC1=CC=CC(COCC2OC2)=C1 OCKQMFDZQUFKRD-UHFFFAOYSA-N 0.000 description 1
- ZADXFVHUPXKZBJ-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxymethyl]oxirane Chemical compound C1=CC(C=C)=CC=C1COCC1OC1 ZADXFVHUPXKZBJ-UHFFFAOYSA-N 0.000 description 1
- OENZCYOCXAUZOT-UHFFFAOYSA-N 2-[2-(2-ethenylphenyl)-1-[2-(2-ethenylphenyl)-1-(oxiran-2-yl)ethoxy]ethyl]oxirane Chemical compound C=CC1=CC=CC=C1CC(C1OC1)OC(C1OC1)CC1=CC=CC=C1C=C OENZCYOCXAUZOT-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
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- SOWCDCVOWHCHMM-UHFFFAOYSA-N 3-isocyanatobutyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(C)N=C=O SOWCDCVOWHCHMM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PSRQSFVOFCKQJV-UHFFFAOYSA-N C(C)OCC[SiH3] Chemical compound C(C)OCC[SiH3] PSRQSFVOFCKQJV-UHFFFAOYSA-N 0.000 description 1
- ZQMWLEFYTOJTOI-UHFFFAOYSA-N CCCC[Si](OCC)(OCC)OCC.N=C=O Chemical compound CCCC[Si](OCC)(OCC)OCC.N=C=O ZQMWLEFYTOJTOI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- DCTLJGWMHPGCOS-UHFFFAOYSA-N Osajin Chemical compound C1=2C=CC(C)(C)OC=2C(CC=C(C)C)=C(O)C(C2=O)=C1OC=C2C1=CC=C(O)C=C1 DCTLJGWMHPGCOS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241001115903 Raphus cucullatus Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- AQNSVANSEBPSMK-UHFFFAOYSA-N dicyclopentenyl methacrylate Chemical compound C12CC=CC2C2CC(OC(=O)C(=C)C)C1C2.C12C=CCC2C2CC(OC(=O)C(=C)C)C1C2 AQNSVANSEBPSMK-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- YAPKLBSSEAZLGL-UHFFFAOYSA-N ethoxy(propyl)silane Chemical compound CCC[SiH2]OCC YAPKLBSSEAZLGL-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- OUHONEIDEVTEIG-UHFFFAOYSA-N ethyl(methoxy)silane Chemical compound CC[SiH2]OC OUHONEIDEVTEIG-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- BVKYCEVCMKTQBN-UHFFFAOYSA-N methoxy(propyl)silicon Chemical compound CCC[Si]OC BVKYCEVCMKTQBN-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
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- 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
- G03F7/075—Silicon-containing compounds
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Description
本発明はフォトレジスト組成物に関するものであって、より詳しくは基板のシリコン窒化膜(SiNx)上にハーフトーンを形成する工程を含む基板の微細パターン形成用フォトレジスト組成物であって、常温安定性に優れ、変色が少なくて透過度に優れており、シリコン窒化膜との接着力に優れていてHMDS工程を省略しても微細化されたパターンの現像工程時に遺失が発生したり、後工程時にパターンの崩壊が発生する虞がないフォトレジスト組成物およびこれを用いた微細パターン形成方法に関するものである。 The present invention relates to a photoresist composition, and more particularly, to a photoresist composition for forming a fine pattern of a substrate including a step of forming a halftone on a silicon nitride film (SiNx) of the substrate, which is stable at room temperature. Excellent in transparency, low discoloration, excellent transparency, excellent adhesion to silicon nitride film, and even if the HMDS process is omitted, loss may occur during the development process of the miniaturized pattern. The present invention relates to a photoresist composition that does not possibly cause pattern collapse and a fine pattern forming method using the same.
一般に、半導体または平板表示装置には絶縁膜または保護膜形成のためにフォトレジスト組成物が用いられ、フォトレジスト組成物は基板との接着力を向上させるためにメラミン系架橋剤またはシラン系架橋剤を含む。 In general, a photoresist composition is used for forming an insulating film or a protective film in a semiconductor or flat panel display device, and the photoresist composition is a melamine-based crosslinking agent or a silane-based crosslinking agent in order to improve adhesion to a substrate. including.
しかし、メラミン系架橋剤またはシラン系架橋剤を含むフォトレジスト組成物を用いて微細パターンを形成する場合には、フォトレジストの接着力が落ちてHMDS(hexamethyldisilazane)噴霧工程を通じて接着力を確保しなければならなかった。これは、HMDS噴霧工程を行わない場合、微細化されたパターンの現像工程時に遺失が発生したり、後工程時にパターンの崩壊が発生することがあるためである。 However, when a fine pattern is formed using a photoresist composition containing a melamine-based crosslinking agent or a silane-based crosslinking agent, the adhesive strength of the photoresist is reduced, and the adhesive strength must be ensured through a HMDS (hexylethylsilazane) spraying process. I had to. This is because when the HMDS spraying process is not performed, loss may occur during the development process of the miniaturized pattern, and pattern collapse may occur during the subsequent process.
前記問題点を解決するために、大韓民国公開特許公報第10−2009−39930号では有機高分子5〜50重量%;感光性物質10〜30重量%;および末端にイソシアネート基が含まれているシラン系カップリング剤3〜5重量%および残量の溶媒を含んでHMDS噴霧工程を省略することができるフォトレジスト組成物について記載している。しかし、前記出願の場合にも常温で安定性が落ち、形成されたパターンの色が変わって透過度が落ち、シリコン窒化膜上にハーフトーン工程を含む0.1〜10μmの微細パターンを形成しようとする場合、ハーフトーン部分でシリコン窒化膜との密着性に優れない問題点があった。 In order to solve the above problem, Korean Patent Application Publication No. 10-2009-39930 discloses an organic polymer in an amount of 5 to 50% by weight; a photosensitive material in an amount of 10 to 30% by weight; It describes a photoresist composition that includes 3-5 wt% of a system coupling agent and a remaining amount of solvent and that can omit the HMDS spraying step. However, even in the case of the above application, the stability is lowered at room temperature, the color of the formed pattern is changed, the transmittance is lowered, and a 0.1 to 10 μm fine pattern including a halftone process is formed on the silicon nitride film. In this case, there is a problem that the adhesion to the silicon nitride film is not excellent in the halftone portion.
本発明は前記のような従来技術の問題点を考慮して、基板のシリコン窒化膜(SiNx)上にハーフトーンを形成する工程を含む基板の微細パターン形成用フォトレジスト組成物であって、工程進行時HMDSによって発生するHMDS気体性気泡およびパーティクル性不良を根本的に減少させることができ、工程費用を減少させてパネルの製造費用を節減することができ、常温安定性に優れ、変色が少なくて透過度に優れており、シリコン窒化膜との接着力に優れていてHMDS工程を省略しても微細化されたパターンの現像工程時に遺失が発生したり、後工程時パターンの崩壊が発生する虞がないフォトレジスト組成物を提供することを目的とする。 The present invention is a photoresist composition for forming a fine pattern of a substrate including a step of forming a halftone on a silicon nitride film (SiNx) of the substrate in consideration of the problems of the prior art as described above. HMDS gas bubbles and particle defects generated by HMDS during the process can be drastically reduced, process costs can be reduced, panel manufacturing costs can be reduced, excellent room temperature stability, and less discoloration Therefore, even if the HMDS process is omitted, loss occurs during the development process of the miniaturized pattern, and the pattern collapses during the subsequent process. It is an object to provide a photoresist composition having no fear.
本発明の他の目的は、前記フォトレジストを用いて基板のシリコン窒化膜(SiNx)上にハーフトーンを形成する工程を含む微細パターン形成方法を提供することを目的とする。 Another object of the present invention is to provide a fine pattern forming method including a step of forming a halftone on a silicon nitride film (SiNx) of a substrate using the photoresist.
また本発明の他の目的は、前記本発明によって得られる微細回路パターンを有する電子素子を提供することを目的とする。 Another object of the present invention is to provide an electronic device having a fine circuit pattern obtained by the present invention.
前記目的を達成するために本発明は、
(a)i)不飽和カルボン酸またはその無水物;ii)エポキシ基含有不飽和化合物;およびiii)オレフィン系不飽和化合物を重合して製造した、重量平均分子量が4000〜9000であるアクリル系共重合体10〜30重量%;
(b)末端基にイソシアネート基(−NCO)を含有するシランカップリング剤0.1〜2重量%;
(c)感光剤1〜15重量%;および
(d)残量の溶媒を含むことを特徴とするフォトレジスト組成物を提供する。
In order to achieve the above object, the present invention provides:
(A) i) an unsaturated carboxylic acid or anhydride; ii) an epoxy group-containing unsaturated compound; and iii) an acrylic copolymer having a weight average molecular weight of 4000 to 9000 produced by polymerizing an olefinic unsaturated compound. 10-30% by weight of polymer;
(B) 0.1-2% by weight of a silane coupling agent containing an isocyanate group (—NCO) at the end group;
(C) 1 to 15% by weight of a photosensitizer; and (d) a photoresist composition comprising a remaining amount of solvent.
また本発明は、フォトレジスト組成物を用いて基板のシリコン窒化膜上にハーフトーンを形成する工程を含む基板の微細パターン形成方法において、
前記フォトレジスト組成物を用いることを特徴とする基板の微細パターン形成方法を提供する。
Further, the present invention provides a method for forming a fine pattern of a substrate including a step of forming a halftone on a silicon nitride film of the substrate using a photoresist composition.
There is provided a method for forming a fine pattern of a substrate, characterized by using the photoresist composition.
また、本発明は前記製造方法によって得られる微細な回路パターンを有する基板を含む電子素子を提供する。 The present invention also provides an electronic device including a substrate having a fine circuit pattern obtained by the manufacturing method.
本発明によるフォトレジスト組成物は、基板のシリコン窒化膜(SiNx)上にハーフトーンを形成する工程を含む基板の0.1〜10μmの微細パターン形成用フォトレジスト組成物であって、工程進行時HMDSによって発生するHMDS気体性気泡およびパーティクル性不良を根本的に減少させることができ、工程費用を減少させてパネルの製造費用を節減することができ、常温安定性に優れ、変色が少なくて透過度に優れており、シリコン窒化膜との接着力に優れていてHMDS工程を省略しても微細化されたパターンの現像工程時に遺失が発生したり、後工程時パターンの崩壊が発生する虞がない。 A photoresist composition according to the present invention is a photoresist composition for forming a fine pattern of 0.1 to 10 μm on a substrate including a step of forming a halftone on a silicon nitride film (SiNx) of the substrate, and the process proceeds. HMDS gas bubbles and particle defects generated by HMDS can be fundamentally reduced, process costs can be reduced, panel manufacturing costs can be reduced, excellent room temperature stability, little discoloration and transmission Even if the HMDS process is omitted, there is a risk that loss may occur during the development process of the miniaturized pattern, or the pattern may collapse during the subsequent process. Absent.
本発明のフォトレジスト組成物は、
(a)i)不飽和カルボン酸またはその無水物;ii)エポキシ基含有不飽和化合物;およびiii)オレフィン系不飽和化合物を重合して製造した重量平均分子量が4000〜9000であるアクリル系共重合体10〜30重量%;
(b)末端基にイソシアネート基(−NCO)を含有するシランカップリング剤0.1〜2重量%;
(c)感光剤1〜15重量%;および
(d)残量の溶媒を含むことを特徴とする。
The photoresist composition of the present invention comprises:
(A) i) unsaturated carboxylic acid or anhydride thereof; ii) epoxy group-containing unsaturated compound; and iii) an acrylic copolymer having a weight average molecular weight of 4000 to 9000 produced by polymerizing an olefinic unsaturated compound. 10-30 wt% coalescence;
(B) 0.1-2% by weight of a silane coupling agent containing an isocyanate group (—NCO) at the end group;
(C) 1 to 15% by weight of a photosensitizer; and (d) a residual solvent.
本発明で前記アクリル系共重合体は、i)不飽和カルボン酸またはその無水物、ii)エポキシ基含有不飽和化合物およびiii)オレフィン系不飽和化合物を単量体にして溶媒および重合開始剤の存在下で重合後、未反応単量体を除去して得ることができる。 In the present invention, the acrylic copolymer comprises i) an unsaturated carboxylic acid or an anhydride thereof, ii) an epoxy group-containing unsaturated compound, and iii) an olefinic unsaturated compound as a monomer and a solvent and a polymerization initiator. After polymerization in the presence, it can be obtained by removing unreacted monomers.
本発明に使用される前記i)不飽和カルボン酸、不飽和カルボン酸無水物またはこれらの混合物は、アクリル酸、メタクリル酸などの不飽和モノカルボン酸;マレイン酸、フマル酸、シトラコン酸、メタコン酸、イタコン酸などの不飽和ジカルボン酸;またはこれらの不飽和ジカルボン酸の無水物などを単独または2種以上混合して使用することができ、特にメタクリル酸を使用することが共重合反応性と現像液であるアルカリ水溶液に対する溶解性においてさらに好ましい。 The i) unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or mixture thereof used in the present invention is an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid; maleic acid, fumaric acid, citraconic acid, methaconic acid. , Unsaturated dicarboxylic acids such as itaconic acid; or anhydrides of these unsaturated dicarboxylic acids can be used singly or in combination of two or more, and in particular, the use of methacrylic acid can lead to copolymerization reactivity and development. It is further preferable in terms of solubility in an alkaline aqueous solution.
前記不飽和カルボン酸、不飽和カルボン酸無水物またはこれらの混合物は全体総単量体に対して15〜30重量部で含まれることが好ましい。その含量が前記範囲内である場合、製造された共重合体がイソシアネート基を含むシランカップリング剤との上昇作用でシリコン窒化膜上のハーフトーンでも接着力を確保することができ、形成されたパターンの透過度および常温安定性が優れる。 The unsaturated carboxylic acid, the unsaturated carboxylic acid anhydride, or a mixture thereof is preferably included in an amount of 15 to 30 parts by weight based on the total monomer. When the content is within the above range, the produced copolymer is able to secure adhesive force even in a halftone on the silicon nitride film due to an ascending action with a silane coupling agent containing an isocyanate group. Excellent pattern transparency and room temperature stability.
本発明に使用される前記ii)のエポキシ基含有不飽和化合物は、アクリル酸グリシジル、メタクリル酸グリシジル、α−エチルアクリル酸グリシジル、α−n−プロピルアクリル酸グリシジル、α−n−ブチルアクリル酸グリシジル、アクリル酸−β−メチルグリシジル、メタクリル酸−β−メチルグリシジル、アクリル酸−β−エチルグリシジル、メタクリル酸−β−エチルグリシジル、アクリル酸−3,4−エポキシブチル、メタクリル酸−3,4−エポキシブチル、アクリル酸−6,7−エポキシへプチル、メタクリル酸−6,7−エポキシへプチル、α−エチルアクリル酸−6,7−エポキシへプチル、o−ビニルベンジルグリシジルエーテル、m−ビニルベンジルグリシジルエーテル、またはp−ビニルベンジルグリシジルエーテル、メタクリル酸3,4−エポキシシクロヘキシルなどを使用することができ、前記化合物を単独または2種以上混合して使用することができる。 The epoxy group-containing unsaturated compound of ii) used in the present invention is glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate. , Acrylic acid-β-methylglycidyl, methacrylic acid-β-methylglycidyl, acrylic acid-β-ethylglycidyl, methacrylic acid-β-ethylglycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4- Epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycidyl ether, m-vinylbenzyl Glycidyl ether, or p-vinylbenzyl glycidyl ether, Methacrylic acid 3,4-epoxycyclohexyl and the like can be used, and the above compounds can be used alone or in admixture of two or more.
特に、前記エポキシ基含有不飽和化合物はメタクリル酸グリシジルを使用することが共重合反応性および得られるパターンの耐熱性を向上させるのにおいてさらに好ましい。 In particular, the epoxy group-containing unsaturated compound is more preferably glycidyl methacrylate in terms of improving copolymerization reactivity and heat resistance of the resulting pattern.
前記エポキシ基含有不飽和化合物は全体総単量体に対して15〜30重量部で含まれるのが好ましい。その含量が前記範囲内である場合、製造された共重合体がイソシアネート基を含むシランカップリング剤との上昇作用でシリコン窒化膜上のハーフトーンでも接着力を確保することができ、形成されたパターンの透過度および常温安定性が優れる。 The epoxy group-containing unsaturated compound is preferably contained in an amount of 15 to 30 parts by weight based on the total monomer. When the content is within the above range, the produced copolymer is able to secure adhesive force even in a halftone on the silicon nitride film due to an ascending action with a silane coupling agent containing an isocyanate group. Excellent pattern transparency and room temperature stability.
本発明に使用される前記iii)のオレフィン系不飽和化合物は、メチルメタクリレート、エチルメタクリレート、n−ブチルメタクリレート、sec−ブチルメタクリレート、tert−ブチルメタクリレート、メチルアクリレート、イソプロピルアクリレート、シクロヘキシルメタクリレート、2−メチルシクロヘキシルメタクリレート、ジシクロペンテニルアクリレート、ジシクロペンタニルアクリレート、ジシクロペンテニルメタクリレート、ジシクロペンタニルメタクリレート、1−アダマンチルアクリレート、1−アダマンチルメタクリレート、ジシクロペンタニルオキシエチルメタクリレート、イソボニルメタクリレート、シクロヘキシルアクリレート、2−メチルシクロヘキシルアクリレート、ジシクロペンタニルオキシエチルアクリレート、イソボニルアクリレート、2−ヒドロキシエチルアクリレート、フェニルメタクリレート、フェニルアクリレート、ベンジルアクリレート、2−ヒドロキシエチルメタクリレート、スチレン、σ−メチルスチレン、m−メチルスチレン、p−メチルスチレン、ビニルトルエン、p−メトキシスチレン、1,3−ブタジエン、イソプレン、または2,3−ジメチル1,3−ブタジエンなどを使用することができ、前記化合物を単独または2種以上混合して使用することができる。
特に、前記オレフィン系不飽和化合物はスチレン60〜80:イソボニルアクリレート5〜20:2−ヒドロキシエチルアクリレート15〜40の重量比率で混合して使用することが共重合反応性および現像液であるアルカリ水溶液に対する溶解性側面でさらに好ましい。
The olefinic unsaturated compound of iii) used in the present invention is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methyl Cyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyloxye Acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, σ-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p- Methoxystyrene, 1,3-butadiene, isoprene, 2,3-dimethyl 1,3-butadiene, or the like can be used, and the above compounds can be used alone or in admixture of two or more.
In particular, the olefinic unsaturated compound may be used by mixing in a weight ratio of styrene 60 to 80: isobornyl acrylate 5 to 20: 2-hydroxyethyl acrylate 15 to 40. It is further preferable in terms of solubility in an aqueous solution.
前記オレフィン系不飽和化合物は全体総単量体に対して40〜70重量部で含まれるのが好ましい。その含量が前記範囲内である場合、製造された共重合体がイソシアネート基を含むシランカップリング剤との上昇作用でシリコン窒化膜上のハーフトーンでも接着力を確保することができ、形成されたパターンの透過度および常温安定性が優れる。 The olefinically unsaturated compound is preferably contained in an amount of 40 to 70 parts by weight with respect to the total total monomers. When the content is within the above range, the produced copolymer is able to secure adhesive force even in a halftone on the silicon nitride film due to an ascending action with a silane coupling agent containing an isocyanate group. Excellent pattern transparency and room temperature stability.
前記のような単量体をソリューション(Solution)重合するために使用される溶媒は、メタノール、エタノール、ベンジルアルコール、ヘキシルアルコールなどのアルコール類;エチレングリコールメチルエーテルアセテート、エチレングリコールエチルエーテルアセテートなどのエチレングリコールアルキルエーテルアセテート類;エチレングリコールメチルエーテルプロピオネート、エチレングリコールエチルエーテルプロピオネートなどのエチレングリコールアルキルエーテルプロピオネート類、エチレングリコールメチルエーテル、エチレングリコールエチルエーテルなどのエチレングリコールモノアルキルエーテル類;ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテルなどのジエチレングリコールアルキルエーテル類;プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテートなどのプロピレングリコールアルキルエーテルアセテート類;プロピレングリコールメチルエーテルプロピオネート、プロピレングリコールエチルエーテルプロピオネート、プロピレングリコールプロピルエーテルプロピオネートなどのプロピレングリコールアルキルエーテルプロピオネート類;プロピレングリコールメチルエーテル、プロピレングリコールエチルエーテル、プロピレングリコールプロピルエーテル、プロピレングリコールブチルエーテルなどのプロピレングリコールモノアルキルエーテル類;ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテルなどのジプロピレングリコールアルキルエーテル類、ブチレングリコールモノメチルエーテル、ブチレングリコールモノエチルエーテルなどのブチレングリコールモノメチルエーテル類;ジブチレングリコールジメチルエーテル、ジブチレングリコールジエチルエーテルなどのジブチレングリコールアルキルエーテル類、テトラヒドロフラン、トルエン、ジオキサンなどを単独または2種以上混合して使用することができる。 Solvents used for solution polymerization of the above monomers include alcohols such as methanol, ethanol, benzyl alcohol and hexyl alcohol; ethylene such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate. Glycol alkyl ether acetates; ethylene glycol methyl ether propionates, ethylene glycol alkyl ether propionates such as ethylene glycol ethyl ether propionates, ethylene glycol monoalkyl ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether; Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Diethylene glycol alkyl ethers such as coal dimethyl ether and diethylene glycol methyl ethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol propyl ether acetate; propylene glycol methyl ether propionate, propylene glycol Propylene glycol alkyl ether propionates such as ethyl ether propionate and propylene glycol propyl ether propionate; such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether Dipropylene glycol monoalkyl ethers; dipropylene glycol dimethyl ether, dipropylene glycol alkyl ethers such as dipropylene glycol diethyl ether, butylene glycol monomethyl ethers such as butylene glycol monomethyl ether and butylene glycol monoethyl ether; dibutylene glycol dimethyl ether, di Dibutylene glycol alkyl ethers such as butylene glycol diethyl ether, tetrahydrofuran, toluene, dioxane and the like can be used alone or in admixture of two or more.
前記のような単量体をソリューション(Solution)重合するために使用される重合開始剤はラジカル重合開始剤を使用することができ、具体的に2,2−アゾビスイソブチロニトリル、2,2−アゾビス(2,4−ジメチルバレロニトリル)、2,2−アゾビス(4−メトキシ2,4−ジメチルバレロニトリル)、1,1−アゾビス(シクロヘキサン−1−カルボニトリル)、またはジメチル2,2'−アゾビスイソブチレートなどを使用することができる。 The polymerization initiator used for solution polymerization of the monomer as described above may be a radical polymerization initiator, specifically 2,2-azobisisobutyronitrile, 2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (4-methoxy2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), or dimethyl 2,2 '-Azobisisobutyrate and the like can be used.
前記のような単量体を溶媒と重合開始剤存在下でラジカル反応させ、沈殿およびろ過、真空乾燥(Vacuum Drying)工程によって未反応単量体を除去して得られたアクリル系共重合体はポリスチレン換算重量平均分子量(Mw)が4,000〜9,000であるのが好ましく、さらに好ましくは5,000〜7,000であるのが良い。前記範囲内である場合、イソシアネート基を含むシランカップリング剤との上昇作用でシリコン窒化膜上のハーフトーンでも接着力を確保することができ、形成されたパターンの透過度および常温安定性が優れる。 The acrylic copolymer obtained by radically reacting the monomer as described above in the presence of a solvent and a polymerization initiator, and removing the unreacted monomer by precipitation, filtration, and vacuum drying steps is obtained. The weight average molecular weight (Mw) in terms of polystyrene is preferably 4,000 to 9,000, more preferably 5,000 to 7,000. When it is within the above range, the ascending action with the silane coupling agent containing an isocyanate group can ensure adhesion even in halftone on the silicon nitride film, and the formed pattern has excellent transparency and room temperature stability. .
前記アクリル系共重合体は本発明の感光性樹脂組成物に10〜30重量%で含むことができ、この場合、パターンのプロファイルおよび現像性に優れ、シリコン窒化膜上のハーフトーンでも接着力を確保することができ、形成されたパターンの透過度および常温安定性が優れる。 The acrylic copolymer may be included in the photosensitive resin composition of the present invention at 10 to 30% by weight. In this case, the pattern profile and developability are excellent, and the adhesive strength is also obtained in the halftone on the silicon nitride film. The transparency of the formed pattern and the room temperature stability are excellent.
本発明の感光性樹脂組成物で(b)末端基にイソシアネート基(−NCO)を含有するシランカップリング剤を含む。前記末端基にイソシアネート基を含有するシランカップリング剤は、ジイソシアナートエトキシエチルシラン、ジイソシアナートメトキシエチルシラン、ジイソシアナートエトキシプロピルシラン、ジイソシアナートメトキシプロピルシラン、3−イソシアネートブチルトリメトキシシラン、3−イソシアネートオキシエチルエトキシシラン、3−イソシアネートオキシエチルメトキシシラン、3−イソシアネートプロピルトリエトキシシラン、3−イソシアネートプロピルメトキシシラン、3−イソシアネートエチルトリエトキシシラン、3−イソシアネートエチルトリメトキシシランおよび3−イソシアネートブチルトリエトキシシランからなる群より選択される1種または2種以上であるものを使用することができる。 The photosensitive resin composition of the present invention includes (b) a silane coupling agent containing an isocyanate group (—NCO) at the terminal group. The silane coupling agent containing an isocyanate group at the terminal group is diisocyanate ethoxyethyl silane, diisocyanate methoxyethyl silane, diisocyanate ethoxypropyl silane, diisocyanate methoxypropyl silane, 3-isocyanatobutyltrimethoxysilane. 3-isocyanateoxyethylethoxysilane, 3-isocyanateoxyethylmethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethoxysilane, 3-isocyanateethyltriethoxysilane, 3-isocyanateethyltrimethoxysilane and 3- What is 1 type (s) or 2 or more types selected from the group which consists of isocyanate butyltriethoxysilane can be used.
前記末端基にイソシアネート基を含有するシランカップリング剤は本発明の感光性樹脂組成物に0.1〜2重量%で含むことができ、その含量が0.1重量%未満である場合、シリコン窒化膜上のハーフトーンパターン部分で接着力を確保することができず、2重量%を超える場合には常温安定性が落ち、形成されたパターンの透過度が落ちる問題点がある。 The silane coupling agent containing an isocyanate group at the terminal group may be included in the photosensitive resin composition of the present invention in an amount of 0.1 to 2% by weight, and if the content is less than 0.1% by weight, silicon Adhesive strength cannot be ensured at the halftone pattern portion on the nitride film, and if it exceeds 2% by weight, there is a problem that the room temperature stability is lowered and the transmittance of the formed pattern is lowered.
本発明の感光性樹脂組成物で前記(c)感光剤は公知の感光剤化合物を使用することができ、具体的な例として1,2−キノンジアジド4−スルホン酸エステル、1,2−キノンジアジド5−スルホン酸エステル、または1,2−キノンジアジド6−スルホン酸エステルなどを使用することができる。 In the photosensitive resin composition of the present invention, a known photosensitizer compound can be used as the photosensitizer (c). Specific examples thereof include 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5 -Sulphonic acid ester or 1,2-quinonediazide 6-sulfonic acid ester can be used.
前記感光剤は本発明の感光性樹脂組成物に1〜30重量%で含むことができ、この場合、パターンのプロファイルおよび現像性を同時に満足させることができる。 The photosensitive agent can be contained in the photosensitive resin composition of the present invention in an amount of 1 to 30% by weight. In this case, the pattern profile and developability can be satisfied at the same time.
また、本発明に使用される前記(d)溶媒は、有機絶縁膜の平坦性とコーティング染みを発生しないようにして、均一なパターンプロファイル(pattern profile)を形成するようにする。 In addition, the solvent (d) used in the present invention does not generate flatness of the organic insulating film and coating stain, and forms a uniform pattern profile.
前記溶媒は感光性樹脂組成物に使用される公知の溶媒を使用することができ、具体的な例としてメタノール、エタノール、ベンジルアルコール、ヘキシルアルコールなどのアルコール類;エチレングリコールメチルエーテルアセテート、エチレングリコールエチルエーテルアセテートなどのエチレングリコールアルキルエーテルアセテート類;エチレングリコールメチルエーテルプロピオネート、エチレングリコールエチルエーテルプロピオネートなどのエチレングリコールアルキルエーテルプロピオネート類、エチレングリコールメチルエーテル、エチレングリコールエチルエーテルなどのエチレングリコールモノアルキルエーテル類;ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテルなどのジエチレングリコールアルキルエーテル類;プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテートなどのプロピレングリコールアルキルエーテルアセテート類;プロピレングリコールメチルエーテルプロピオネート、プロピレングリコールエチルエーテルプロピオネート、プロピレングリコールプロピルエーテルプロピオネートなどのプロピレングリコールアルキルエーテルプロピオネート類;プロピレングリコールメチルエーテル、プロピレングリコールエチルエーテル、プロピレングリコールプロピルエーテル、プロピレングリコールブチルエーテルなどのプロピレングリコールモノアルキルエーテル類;ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテルなどのジプロピレングリコールアルキルエーテル類、ブチレングリコールモノメチルエーテル、ブチレングリコールモノエチルエーテルなどのブチレングリコールモノメチルエーテル類;ジブチレングリコールジメチルエーテル、ジブチレングリコールジエチルエーテルなどのジブチレングリコールアルキルエーテル類などがある。 As the solvent, known solvents used for photosensitive resin compositions can be used. Specific examples include alcohols such as methanol, ethanol, benzyl alcohol, hexyl alcohol; ethylene glycol methyl ether acetate, ethylene glycol ethyl. Ethylene glycol alkyl ether acetates such as ether acetate; ethylene glycol alkyl ether propionates such as ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol such as ethylene glycol methyl ether and ethylene glycol ethyl ether Monoalkyl ethers; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Diethylene glycol alkyl ethers such as coal dimethyl ether and diethylene glycol methyl ethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol propyl ether acetate; propylene glycol methyl ether propionate, propylene glycol Propylene glycol alkyl ether propionates such as ethyl ether propionate and propylene glycol propyl ether propionate; such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether Dipropylene glycol monoalkyl ethers; dipropylene glycol dimethyl ether, dipropylene glycol alkyl ethers such as dipropylene glycol diethyl ether, butylene glycol monomethyl ethers such as butylene glycol monomethyl ether and butylene glycol monoethyl ether; dibutylene glycol dimethyl ether, di And dibutylene glycol alkyl ethers such as butylene glycol diethyl ether.
前記溶媒は全体感光性樹脂組成物の残量で含まれ、好ましくは50〜90重量%になるように含ませる。前記範囲内である場合、感光性樹脂組成物のコーティング性および補正安定性を同時に向上させることができる。 The solvent is included in the remaining amount of the entire photosensitive resin composition, and is preferably included so as to be 50 to 90% by weight. When it is within the above range, the coating property and correction stability of the photosensitive resin composition can be simultaneously improved.
前記のような成分からなる本発明の感光性樹脂組成物は必要によって可塑剤、UV安定化剤、ラジカルスカベンジャー、酸化防止剤、感度増進剤または界面活性剤を0.01〜10重量%さらに含むことができる。前記可塑剤、UV安定化剤、ラジカルスカベンジャー、酸化防止剤、感度増進剤または界面活性剤は感光性樹脂組成物に使用される公知の物質を使用することができるのはもちろんである。 The photosensitive resin composition of the present invention comprising the above components further contains 0.01 to 10% by weight of a plasticizer, UV stabilizer, radical scavenger, antioxidant, sensitivity enhancer or surfactant as necessary. be able to. As the plasticizer, UV stabilizer, radical scavenger, antioxidant, sensitivity enhancer, or surfactant, it is needless to say that known substances used for photosensitive resin compositions can be used.
前記のような成分からなる本発明の感光性樹脂組成物の固形分濃度は10〜50重量%であるのが好ましく、前記範囲の固形分を有する組成物は0.01〜0.2μmのミリポアフィルターなどでろ過した後に使用することが良い。 The solid content concentration of the photosensitive resin composition of the present invention comprising the above components is preferably 10 to 50% by weight, and the composition having the solid content in the above range is 0.01 to 0.2 μm Millipore. It is good to use after filtering with a filter.
また、本発明は前記感光性樹脂組成物を用いた微細パターン形成方法および前記方法によって形成された微細パターンを含む電気素子を提供する。好ましくは前記電気素子は0.1〜10μmの微細パターン、さらに好ましくは0.1〜4μm線幅大きさの微細パターンを有する半導体または平板表示装置である。 The present invention also provides a method for forming a fine pattern using the photosensitive resin composition and an electric device including the fine pattern formed by the method. Preferably, the electric element is a semiconductor or flat panel display device having a fine pattern of 0.1 to 10 μm, more preferably a fine pattern of 0.1 to 4 μm line width.
本発明の微細パターン形成方法はシリコン窒化膜(SiNx)上にハーフトーンを形成する工程を含む基板の微細パターン形成用フォトレジスト組成物として前記感光性樹脂組成物を使用することを特徴とする。前記感光性樹脂組成物を使用することを除いては公知の微細パターン形成方法を使用することができる。 The fine pattern forming method of the present invention is characterized in that the photosensitive resin composition is used as a photoresist composition for forming a fine pattern on a substrate including a step of forming a halftone on a silicon nitride film (SiNx). A known fine pattern forming method can be used except that the photosensitive resin composition is used.
具体的な一例として有機絶縁膜を形成する方法は次の通りである。
まず、本発明の感光性樹脂組成物をスプレー法、ロールコーター法、回転塗布法などでシリコン窒化膜が形成された基板表面に塗布し、プリベークによって溶媒を除去して塗布膜を形成する。この時、前記プリベークは80〜115℃の温度で1〜15分間実施するのが好ましい。
As a specific example, the method for forming the organic insulating film is as follows.
First, the photosensitive resin composition of the present invention is applied to the surface of the substrate on which the silicon nitride film is formed by a spray method, a roll coater method, a spin coating method, or the like, and the solvent is removed by prebaking to form a coating film. At this time, the pre-bake is preferably performed at a temperature of 80 to 115 ° C. for 1 to 15 minutes.
その後、予め準備されたパターンによって可視光線、紫外線、遠紫外線、電子線、X線などを前記形成された塗布膜に照射し、現像液で現像して、不必要な部分を除去することによって所定のパターンを形成する。 Thereafter, the formed coating film is irradiated with visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. according to a pattern prepared in advance, and developed with a developer to remove unnecessary portions. The pattern is formed.
前記現像液はアルカリ水溶液を使用することが良く、具体的に水酸化ナトリウム、水酸化カリウム、炭酸ナトリウムなどの無機アルカリ類;エチルアミン、n−プロピルアミンなどの1級アミン類;ジエチルアミン、n−プロピルアミンなどの2級アミン類;トリメチルアミン、メチルジエチルアミン、ジメチルエチルアミン、トリエチルアミンなどの3級アミン類;ジメチルエタノールアミン、メチルジエタノールアミン、トリエタノールアミンなどのアルコールアミン類;またはテトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシドなどの4級アンモニウム塩の水溶液などを使用することができる。この時、前記現像液はアルカリ性化合物を0.1〜10重量%の濃度に溶解して使用され、メタノール、エタノールなどのような水溶性有機溶媒および界面活性剤を適正量添加することもできる。 The developer is preferably an alkaline aqueous solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; primary amines such as ethylamine and n-propylamine; diethylamine and n-propyl. Secondary amines such as amines; tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine; alcohol amines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; or tetramethylammonium hydroxide, tetraethylammonium hydroxy An aqueous solution of a quaternary ammonium salt such as dodo can be used. At this time, the developer is used by dissolving an alkaline compound in a concentration of 0.1 to 10% by weight, and an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant can be added.
また、前記のような現像液で現像した後、超純水で30〜90秒間洗浄して不必要な部分を除去し乾燥してパターンを形成し、前記形成されたパターンに紫外線などの光を照射した後、パターンをオーブンなどの加熱装置によって150〜250℃の温度で30〜90分間加熱処理して最終パターンを得ることができる。 In addition, after developing with the developer as described above, washing with ultrapure water for 30 to 90 seconds to remove unnecessary portions and drying, a pattern is formed, and light such as ultraviolet rays is applied to the formed pattern. After the irradiation, the pattern can be heat-treated at a temperature of 150 to 250 ° C. for 30 to 90 minutes with a heating device such as an oven to obtain a final pattern.
本発明の感光性樹脂組成物を使用する微細パターンの形成方法は、0.1〜10μmの微細パターン形成時にHMDS噴霧工程を省略することができるので、HMDS工程によって発生するHMDS気体性気泡およびパーティクル性不良を根本的に減少させることができ、工程費用を減少させてパネルの製造費用を節減することができ、常温安定性に優れ、変色が少なくて透過度に優れ、シリコン窒化膜との接着力に優れていて、HMDS工程を省略しても微細化されたパターンの現像工程時に遺失が発生したり、後工程時パターンの崩壊が発生する虞がない。 The method for forming a fine pattern using the photosensitive resin composition of the present invention can omit the HMDS spraying process when forming a fine pattern of 0.1 to 10 μm, so HMDS gaseous bubbles and particles generated by the HMDS process Can be reduced fundamentally, process costs can be reduced and panel manufacturing costs can be reduced, excellent room temperature stability, less discoloration and excellent permeability, and adhesion to silicon nitride film Even if the HMDS process is omitted, there is no risk of loss during the development process of the miniaturized pattern or collapse of the pattern during the subsequent process.
以下、本発明の理解のために好ましい実施例を提示するが、下記の実施例は本発明を例示するものに過ぎず、本発明の範囲が下記の実施例に限定されるのではない。 Hereinafter, preferred examples will be presented for the understanding of the present invention. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.
実施例1
(アクリル系共重合体製造)
冷却管と攪拌機を備えたフラスコに2,2’−アゾビス(2,4−ジメチルバレロニトリル)10重量部、プロピレングリコールモノメチルエーテルアセテート200重量部、メタクリル酸20重量部、メタアクリル酸グリシジル25重量部、スチレン40重量部、2−ヒドロキシエチルアクリレート5重量部およびイソボニルアクリレート10重量部を入れて、窒素置換した後、緩慢に攪拌した。前記反応溶液を55℃まで昇温させて、24時間この温度を維持しながらアクリル系共重合体を含む重合体溶液を製造した。
前記アクリル系共重合体を含む重合体溶液の固形分濃度が50重量%であり、重合体の重量平均分子量は5,000であった。この時、重量平均分子量はGPCを使用して測定したポリスチレン換算平均分子量である。
Example 1
(Acrylic copolymer production)
In a flask equipped with a condenser and a stirrer, 10 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 20 parts by weight of methacrylic acid, 25 parts by weight of glycidyl methacrylate Then, 40 parts by weight of styrene, 5 parts by weight of 2-hydroxyethyl acrylate, and 10 parts by weight of isobornyl acrylate were added, and the mixture was purged with nitrogen, and then slowly stirred. The reaction solution was heated to 55 ° C., and a polymer solution containing an acrylic copolymer was produced while maintaining this temperature for 24 hours.
The solid content concentration of the polymer solution containing the acrylic copolymer was 50% by weight, and the weight average molecular weight of the polymer was 5,000. At this time, the weight average molecular weight is an average molecular weight in terms of polystyrene measured using GPC.
(1,2−キノンジアジド化合物製造)
4,4’−[1−[4−[1−[4−ヒドロキシフェニル]−1−メチルエチル]フェニル]エチリデン]ビスフェノール1モルと1,2−ナフトキノンジアジド−5−スルホン酸[クロライド]2モルを縮合反応させて、4,4’−[1−[4−[1−[4−ヒドロキシフェニル]−1−メチルエチル]フェニル]エチリデン]ビスフェノール1,2−ナフトキノンジアジド−5−スルホン酸エステルを製造した。
(Production of 1,2-quinonediazide compound)
4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1 mol and 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] 2 mol To give 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester. Manufactured.
(感光性樹脂組成物製造)
前記製造したアクリル系共重合体を含む重合体溶液100重量部および前記製造した4,4’−[1−[4−[1−[4−ヒドロキシフェニル]−1−メチルエチル]フェニル]エチリデン]ビスフェノール1,2−ナフトキノンジアジド−5−スルホン酸エステル25重量部、および末端にイソシアネート基を含有するシランカップリング剤5重量部を混合した。また、前記混合物の固形分濃度が30重量%になるようにジエチレングリコールジメチルエーテルを加えて溶解させ、0.05μmのミリポアフィルターでろ過して感光性樹脂組成物を製造した。本実施例で前記シランカップリング剤の含量は最終1.875重量%であった。
(Photosensitive resin composition production)
100 parts by weight of the polymer solution containing the produced acrylic copolymer and the produced 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] 25 parts by weight of bisphenol 1,2-naphthoquinonediazide-5-sulfonic acid ester and 5 parts by weight of a silane coupling agent containing an isocyanate group at the terminal were mixed. Further, diethylene glycol dimethyl ether was added and dissolved so that the solid content concentration of the mixture was 30% by weight, and the mixture was filtered through a 0.05 μm Millipore filter to produce a photosensitive resin composition. In this example, the content of the silane coupling agent was 1.875% by weight.
実施例2
前記実施例1の感光性樹脂組成物製造で末端にイソシアネート基を含有するシランカップリング剤1重量部を使用したことを除いては前記実施例1と同様な方法で実施して感光性樹脂組成物を製造した。本実施例で前記シランカップリング剤の含量は最終0.375重量%であった。
Example 2
The photosensitive resin composition was prepared in the same manner as in Example 1 except that 1 part by weight of a silane coupling agent containing an isocyanate group at the terminal was used in the production of the photosensitive resin composition of Example 1. The thing was manufactured. In this example, the content of the silane coupling agent was 0.375% by weight.
比較例1
前記実施例1の感光性樹脂組成物製造で末端にイソシアネート基を含有するシランカップリング剤の代わりにメラミン系架橋剤を使用したことを除いては前記実施例1と同様な方法で実施して感光性樹脂組成物を製造した。
Comparative Example 1
The same procedure as in Example 1 was performed except that a melamine-based crosslinking agent was used in place of the silane coupling agent containing an isocyanate group at the terminal in the production of the photosensitive resin composition of Example 1. A photosensitive resin composition was produced.
比較例2
前記実施例1の感光性樹脂組成物で末端にイソシアネート基を含有するシランカップリング剤の最終含量が0.05重量%になるようにしたことを除いては前記実施例1と同様な方法で実施して感光性樹脂組成物を製造した。
Comparative Example 2
The same method as in Example 1 except that the final content of the silane coupling agent containing an isocyanate group at the terminal in the photosensitive resin composition of Example 1 was 0.05% by weight. It carried out and manufactured the photosensitive resin composition.
比較例3
前記実施例1の感光性樹脂組成物で末端にイソシアネート基を含有するシランカップリング剤の最終含量が4重量%になるようにしたことを除いては前記実施例1と同様な方法で実施して感光性樹脂組成物を製造した。
Comparative Example 3
The same procedure as in Example 1 was carried out except that the final content of the silane coupling agent containing an isocyanate group at the terminal in the photosensitive resin composition of Example 1 was 4% by weight. Thus, a photosensitive resin composition was produced.
前記実施例1〜2および比較例1〜3の感光性樹脂組成物を用いてシリコン窒化膜との接着力、透過度、常温安定性を評価した。
a)接着力−SiNxが500〜3000Åが蒸着されたガラス基板上にHMDS溶液を塗布しない状態で前記実施例1〜2および比較例1〜2で製造された感光性樹脂組成物溶液を塗布した後、90〜100℃で50〜180秒間ホットプレート上でプリベークして膜を形成した。塗布された膜の厚さは0.2〜4μmとし、得られた膜に1〜5μmのラインアンドスペース(Line & Space)とコンタクトホールアンドドット(Contact Hole & Dot)パターンがあるマスクを使用して、365nmでの強度が10mW/cm2である紫外線を5〜20秒間照射した。以後、テトラメチルアンモニウムヒドロキシド水溶液で19〜27℃で50秒から180秒間現像した後、超純水で1分間洗浄した。その結果、図1に示されているように、実施例1の場合に2μmパターンで全く遺失されず、実施例2の場合にも、図面に示さなかったが実施例1と対等な結果を示した。
これに反して、比較例1の場合には4μmパターンで遺失がひどく発生し、比較例2の場合には図2に示されているように一部パターンの遺失が発生した。
Using the photosensitive resin compositions of Examples 1 to 2 and Comparative Examples 1 to 3, adhesion strength with silicon nitride film, permeability, and room temperature stability were evaluated.
a) Adhesive strength—The photosensitive resin composition solutions prepared in Examples 1-2 and Comparative Examples 1-2 were applied without applying the HMDS solution on a glass substrate on which 500 to 3000 N of SiNx was deposited. Thereafter, a film was formed by prebaking on a hot plate at 90 to 100 ° C. for 50 to 180 seconds. The applied film has a thickness of 0.2 to 4 μm, and a mask having a line and space (Line & Space) and contact hole and dot (Contact Hole & Dot) pattern of 1 to 5 μm is used on the obtained film. Then, ultraviolet rays having an intensity at 365 nm of 10 mW / cm 2 were irradiated for 5 to 20 seconds. Thereafter, the film was developed with an aqueous tetramethylammonium hydroxide solution at 19 to 27 ° C. for 50 to 180 seconds, and then washed with ultrapure water for 1 minute. As a result, as shown in FIG. 1, in the case of Example 1, the 2 μm pattern was not lost at all, and in the case of Example 2, the result not shown in the drawing but comparable to Example 1 It was.
On the contrary, in the case of the comparative example 1, the loss was severely generated in the 4 μm pattern, and in the case of the comparative example 2, the partial pattern was lost as shown in FIG.
b)透過度:ベアガラス(Bare Glass)基板上に前記実施例2と比較例1および3で製造された感光性樹脂組成物溶液を塗布した後、90〜100℃で50〜180秒間ホットプレート上でプリベークして膜を形成した。塗布された膜の厚さは3μmとし、マスクを使用せず膜がコーティングされたベアガラス全体を365nmでの強度が10mW/cm2である紫外線を0〜50秒間照射した。以後、コンベクションオーブンで220℃で1時間硬化した後、UVビジブルメーター(Uv Visible Meter)を使用して400nmで透過度を測定した。
透過度を測定して、400nmで90%以下である場合にはBad、93%以上である場合にはNormal、95%以上である場合にはGoodと判断される。
b) Transmittance: The photosensitive resin composition solution prepared in Example 2 and Comparative Examples 1 and 3 was applied on a bare glass substrate, and then on a hot plate at 90 to 100 ° C. for 50 to 180 seconds. And pre-baked to form a film. The applied film had a thickness of 3 μm, and the whole bare glass coated with the film was irradiated with ultraviolet rays having an intensity at 365 nm of 10 mW / cm 2 for 0 to 50 seconds without using a mask. Subsequently, after curing at 220 ° C. for 1 hour in a convection oven, the transmittance was measured at 400 nm using a UV visible meter (Uv Visible Meter).
The transmittance is measured, and when it is 90% or less at 400 nm, it is judged as Bad, when it is 93% or more, it is judged as Normal, and when it is 95% or more, it is judged as Good.
前記表1に示されているように、本発明の実施例の場合、比較例1および3に比べて顕著に向上した透過度を示すのを確認することができた。 As shown in Table 1, it was confirmed that the example of the present invention showed a significantly improved transmittance as compared with Comparative Examples 1 and 3.
c)常温保存性:保存安定性は実施例1と比較例1、2、3の感光性樹脂組成物を常温で120時間放置させた後、接着力を評価して、材料の安定性を確認した。接着力評価方法は前記a)で用いた方法と同様な方法を使用した。その結果は下記表2の通りであった。 c) Storage stability at normal temperature: Storage stability was determined by allowing the photosensitive resin compositions of Example 1 and Comparative Examples 1, 2, and 3 to stand at room temperature for 120 hours, and then evaluating the adhesive force to confirm the stability of the material. did. The adhesive strength evaluation method used was the same method as used in the above a). The results are shown in Table 2 below.
前記表2に示されているように、実施例では2μmパターンでも遺失が発生しなかったが、比較例1〜3では4μmパターンで遺失が発生することを確認した。 As shown in Table 2, no loss occurred even in the 2 μm pattern in the example, but it was confirmed that loss occurred in the 4 μm pattern in Comparative Examples 1 to 3.
前記に示されているように、本発明による実施例の感光性樹脂組成物はシリコン窒化膜との接着性に優れてシリコン窒化膜(SiNx)上にハーフトーンを形成する工程を含む基板の0.1〜10μmの微細パターン形成用フォトレジスト組成物であって、工程進行時HMDSによって発生するHMDS気体性気泡およびパーティクル性不良を根本的に減少させることができ、工程費用を減少させてパネルの製造費用を節減することができ、常温安定性に優れ、変色が少なくて透過度に優れる。 As described above, the photosensitive resin composition of the example according to the present invention has excellent adhesion to the silicon nitride film and includes a step of forming a halftone on the silicon nitride film (SiNx). .1-10 μm fine pattern forming photoresist composition, which can radically reduce HMDS gas bubbles and particle defects generated by HMDS during the process, and reduce process costs The manufacturing cost can be reduced, the room temperature stability is excellent, the discoloration is small, and the transmittance is excellent.
Claims (7)
(b)末端基にイソシアネート基(−NCO)を含有するシランカップリング剤0.1〜2重量%;
(c)感光剤1〜15重量%;および
(d)残量の溶媒を含むことを特徴とするフォトレジスト組成物。 (A) i) an unsaturated carboxylic acid or its anhydride; ii) an epoxy group-containing unsaturated compound; and iii) an acrylic copolymer having a weight average molecular weight of 5000 to 7000 produced by polymerizing an olefinic unsaturated compound. 10-30% by weight of polymer;
(B) 0.1-2% by weight of a silane coupling agent containing an isocyanate group (—NCO) at the end group;
(C) 1 to 15% by weight of a photosensitizing agent; and (d) a photoresist composition comprising a remaining amount of solvent.
前記フォトレジスト組成物が請求項1乃至6のうちのいずれか一項記載のフォトレジスト組成物であることを特徴とする基板の微細パターン形成方法。 In a method for forming a fine pattern of a substrate including a step of forming a halftone on a silicon nitride film of a substrate using a photoresist composition,
A method for forming a fine pattern on a substrate, wherein the photoresist composition is the photoresist composition according to any one of claims 1 to 6 .
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JPH11338157A (en) * | 1998-05-29 | 1999-12-10 | Hitachi Chemical Dupont Microsystems Ltd | Positive type photosensitive resin composition and production of relief pattern |
KR100809544B1 (en) * | 2001-10-24 | 2008-03-04 | 주식회사 동진쎄미켐 | Photosensitive resin composition comprising quinonediazide sulfate ester compound |
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KR20110040640A (en) * | 2009-10-12 | 2011-04-20 | 롬엔드하스전자재료코리아유한회사 | Photo-sensitivity resin composition, its dielectric insulating film and electronic device |
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- 2012-12-11 JP JP2014547094A patent/JP6154398B2/en active Active
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KR102025099B1 (en) | 2019-09-25 |
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