KR20090098776A - Acid generator for chemically amplified resist compositions - Google Patents
Acid generator for chemically amplified resist compositions Download PDFInfo
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- KR20090098776A KR20090098776A KR1020090078095A KR20090078095A KR20090098776A KR 20090098776 A KR20090098776 A KR 20090098776A KR 1020090078095 A KR1020090078095 A KR 1020090078095A KR 20090078095 A KR20090078095 A KR 20090078095A KR 20090098776 A KR20090098776 A KR 20090098776A
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- South Korea
- Prior art keywords
- group
- formula
- difluoro
- sulfo
- reaction
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- 239000002253 acid Substances 0.000 title abstract description 20
- 239000000203 mixture Substances 0.000 title abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims 1
- 125000002950 monocyclic group Chemical group 0.000 abstract description 7
- 125000001424 substituent group Chemical group 0.000 abstract description 7
- 150000001450 anions Chemical class 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 125000003367 polycyclic group Chemical group 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 125000002723 alicyclic group Chemical group 0.000 abstract description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 abstract 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 57
- 239000002904 solvent Substances 0.000 description 42
- 230000015572 biosynthetic process Effects 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 39
- 238000003786 synthesis reaction Methods 0.000 description 39
- 238000005160 1H NMR spectroscopy Methods 0.000 description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 238000003756 stirring Methods 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 125000004432 carbon atom Chemical group C* 0.000 description 22
- -1 thiophenoxy Chemical group 0.000 description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 125000000217 alkyl group Chemical group 0.000 description 18
- 239000012044 organic layer Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 13
- 125000003545 alkoxy group Chemical group 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 11
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 10
- 150000007523 nucleic acids Chemical class 0.000 description 10
- 102000039446 nucleic acids Human genes 0.000 description 10
- 108020004707 nucleic acids Proteins 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 159000000000 sodium salts Chemical class 0.000 description 9
- 238000004293 19F NMR spectroscopy Methods 0.000 description 8
- LJOODBDWMQKMFB-UHFFFAOYSA-N cyclohexylacetic acid Chemical compound OC(=O)CC1CCCCC1 LJOODBDWMQKMFB-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- JIMXXGFJRDUSRO-UHFFFAOYSA-N adamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2CC1(C(=O)O)C3 JIMXXGFJRDUSRO-UHFFFAOYSA-N 0.000 description 7
- 239000007810 chemical reaction solvent Substances 0.000 description 7
- PREAJPIKNPDDON-APAIHEESSA-N dideuterio-[dichloro(deuterio)methyl]-lambda3-chlorane Chemical compound C(Cl([2H])[2H])(Cl)(Cl)[2H] PREAJPIKNPDDON-APAIHEESSA-N 0.000 description 7
- OVGMTYOPHVFYEG-UHFFFAOYSA-M sodium 1,2-difluoro-1-hydroxyethanesulfonate Chemical compound [Na+].FCC(S(=O)(=O)[O-])(O)F OVGMTYOPHVFYEG-UHFFFAOYSA-M 0.000 description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- YIFMBUGZDPGTSZ-UHFFFAOYSA-N 2-(adamantane-1-carbonyloxy)-1,1-difluoroethanesulfonic acid;sodium Chemical compound [Na].C1C(C2)CC3CC2CC1(C(=O)OCC(F)(F)S(=O)(=O)O)C3 YIFMBUGZDPGTSZ-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- BXVCJUUFCOHVBH-UHFFFAOYSA-N C1(=CC=CC=C1)C=1C(=C(C=CC1)[SH+]C)C1=CC=CC=C1.FC(COC(=O)C12CC3CC(CC(C1)C3)C2)(S(=O)(=O)[O-])F Chemical compound C1(=CC=CC=C1)C=1C(=C(C=CC1)[SH+]C)C1=CC=CC=C1.FC(COC(=O)C12CC3CC(CC(C1)C3)C2)(S(=O)(=O)[O-])F BXVCJUUFCOHVBH-UHFFFAOYSA-N 0.000 description 4
- AZMVIEBJTBYCMH-UHFFFAOYSA-N CSC1=CC=CC=C1.FC(F)F.S Chemical compound CSC1=CC=CC=C1.FC(F)F.S AZMVIEBJTBYCMH-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- AOTQGWFNFTVXNQ-UHFFFAOYSA-N 2-(1-adamantyl)acetic acid Chemical compound C1C(C2)CC3CC2CC1(CC(=O)O)C3 AOTQGWFNFTVXNQ-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000005309 thioalkoxy group Chemical group 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GYMCGFBJMCUOIO-UHFFFAOYSA-N C1(=CC=CC=C1)C=1C(=C(C=CC1)[SH+]F)C1=CC=CC=C1.FC(COC(=O)C12CC3CC(CC(C1)C3)C2)(S(=O)(=O)[O-])F Chemical compound C1(=CC=CC=C1)C=1C(=C(C=CC1)[SH+]F)C1=CC=CC=C1.FC(COC(=O)C12CC3CC(CC(C1)C3)C2)(S(=O)(=O)[O-])F GYMCGFBJMCUOIO-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000004036 acetal group Chemical group 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- JESWDXIHOJGWBP-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3-carboxylic acid Chemical compound C1CC2C(C(=O)O)CC1C2 JESWDXIHOJGWBP-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- OMFCOSZFMGSRQK-UHFFFAOYSA-M sodium;2-(cyclohexanecarbonyloxy)-1,1-difluoroethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)COC(=O)C1CCCCC1 OMFCOSZFMGSRQK-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UVWOMJWSGBCQLR-UHFFFAOYSA-N (2,3-diphenylphenyl) thiohypofluorite trifluoromethanesulfonic acid Chemical compound FC(S(=O)(=O)[O-])(F)F.C1(=CC=CC=C1)C=1C(=C(C=CC1)[SH+]F)C1=CC=CC=C1 UVWOMJWSGBCQLR-UHFFFAOYSA-N 0.000 description 1
- ZXKYNEWQPBBZOF-UHFFFAOYSA-M (2,3-diphenylphenyl)-methoxy-[(2-methylpropan-2-yl)oxycarbonyl]sulfanium trifluoromethanesulfonate Chemical compound FC(S(=O)(=O)[O-])(F)F.C1(=CC=CC=C1)C=1C(=C(C=CC1)[S+](OC)C(=O)OC(C)(C)C)C1=CC=CC=C1 ZXKYNEWQPBBZOF-UHFFFAOYSA-M 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KQPQZWKCUWVZDD-UHFFFAOYSA-N 1-methyladamantane;prop-2-enoic acid Chemical compound OC(=O)C=C.C1C(C2)CC3CC2CC1(C)C3 KQPQZWKCUWVZDD-UHFFFAOYSA-N 0.000 description 1
- HLQSEJBREPQBRW-UHFFFAOYSA-N 2-(1-adamantyl)acetyl chloride Chemical compound C1C(C2)CC3CC2CC1(CC(=O)Cl)C3 HLQSEJBREPQBRW-UHFFFAOYSA-N 0.000 description 1
- FYHBMPWRHCWNBC-UHFFFAOYSA-N 2-(3-bicyclo[2.2.1]heptanyl)acetic acid Chemical compound C1CC2C(CC(=O)O)CC1C2 FYHBMPWRHCWNBC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910015892 BF 4 Inorganic materials 0.000 description 1
- AXZRJVMXKZAPCQ-UHFFFAOYSA-N C(C)(=O)Cl.C12CCC(CC1)C2 Chemical compound C(C)(=O)Cl.C12CCC(CC1)C2 AXZRJVMXKZAPCQ-UHFFFAOYSA-N 0.000 description 1
- DNSBOPGEODRUJC-UHFFFAOYSA-N C1(=CC=CC=C1)C=1C(=C(C=CC1)[SH+]C)C1=CC=CC=C1.FC(COC(CC1C2CCC(C1)C2)=O)(S(=O)(=O)[O-])F Chemical compound C1(=CC=CC=C1)C=1C(=C(C=CC1)[SH+]C)C1=CC=CC=C1.FC(COC(CC1C2CCC(C1)C2)=O)(S(=O)(=O)[O-])F DNSBOPGEODRUJC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- YBVRUEQLVWXBOU-UHFFFAOYSA-M [Na+].C(C)OC(C(S(=O)(=O)[O-])(F)F)=O Chemical compound [Na+].C(C)OC(C(S(=O)(=O)[O-])(F)F)=O YBVRUEQLVWXBOU-UHFFFAOYSA-M 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- MIBQYWIOHFTKHD-UHFFFAOYSA-N adamantane-1-carbonyl chloride Chemical compound C1C(C2)CC3CC2CC1(C(=O)Cl)C3 MIBQYWIOHFTKHD-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- ADEWYRHNJCWZDZ-UHFFFAOYSA-N bicyclo[2.2.1]heptane-4-carbonyl chloride Chemical compound C1CC2CCC1(C(=O)Cl)C2 ADEWYRHNJCWZDZ-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Inorganic materials [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ULWOJODHECIZAU-UHFFFAOYSA-N n,n-diethylpropan-2-amine Chemical compound CCN(CC)C(C)C ULWOJODHECIZAU-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- NJTFMXRQXUMBLJ-UHFFFAOYSA-M sodium;2-(2-cyclohexylacetyl)oxy-1,1-difluoroethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)COC(=O)CC1CCCCC1 NJTFMXRQXUMBLJ-UHFFFAOYSA-M 0.000 description 1
- RDNAJAJPHREQSI-UHFFFAOYSA-M sodium;2-(bicyclo[2.2.1]heptane-3-carbonyloxy)-1,1-difluoroethanesulfonate Chemical compound [Na+].C1CC2C(C(=O)OCC(F)(F)S(=O)(=O)[O-])CC1C2 RDNAJAJPHREQSI-UHFFFAOYSA-M 0.000 description 1
- JXBUYGMVVWINRS-UHFFFAOYSA-M sodium;2-[2-(3-bicyclo[2.2.1]heptanyl)acetyl]oxy-1,1-difluoroethanesulfonate Chemical compound [Na+].C1CC2C(CC(=O)OCC(F)(F)S(=O)(=O)[O-])CC1C2 JXBUYGMVVWINRS-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 1
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Abstract
Description
본 발명은 산발생제에 관한 것으로서, 보다 상세하게는 반도체 공정에서 사용하는 화학증폭형 레지스트 조성물에 포함되는 산발생제로서 적합한 염에 관한 것이다. The present invention relates to an acid generator, and more particularly, to a salt suitable as an acid generator included in a chemically amplified resist composition used in a semiconductor process.
리소그래피를 이용한 반도체 미세 가공에 있어서 화학증폭형 레지스트 조성물은 산 발생제를 함유하며, 반도체 미세 가공에 있어서는 세대가 바뀜에 따라 더욱 고해상도의 레지스트가 요구되고 있다. In semiconductor microfabrication using lithography, the chemically amplified resist composition contains an acid generator, and in semiconductor microfabrication, higher resolution resists are required as generations change.
따라서, 레지스트의 해상도의 증가와 원하는 물성을 갖는 레지스트를 제조하기 위하여 그동안 많은 종류의 산 발생제가 발명되어 왔으며 이에 결부되는 물성중에 하나인 산의 확산 속도와 투명도를 개선하기 위하여 광산발생제로 사용되어지는 염의 양이온 부분에 많은 디자인의 변화와 실험이 진행되었다. Therefore, many kinds of acid generators have been invented to increase the resolution of resists and to manufacture resists having desired physical properties, and are used as photoacid generators to improve the diffusion rate and transparency of acid, which is one of the physical properties. Many design changes and experiments have been carried out on the cationic portion of the salt.
하지만 최근 레지스트 조성물의 연구에 있어서 광산발생제의 양이온 쪽에는 점점 레지스트의 물성 개선의 한계를 갖게 되었으며 또한 이머젼 ArF공정에서 물을 사용함에 따라 요구되는 물로의 용출을 줄이는 문제가 발생하게 되었다. However, in the recent study of the resist composition, the cation side of the photoacid generator has gradually become the limit of improving the physical properties of the resist, and also the problem of reducing the elution to the water required by using water in the immersion ArF process.
따라서, 실질적으로 산의 유동성과 레지스트의 조성물의 물성을 개선하는 물리적, 화학적 성질로써 양이온쪽 보다는 음이온 쪽이 더 많은 영향을 줄 수 있다는 다수의 실험결과와 논문에 입각하여 최근에는 산 발생제의 음이온 부분에 대한 발명이 새로이 이루어지고 있으며 이는 산의 확산 속도를 줄이고 193nm ArF광에 대하여 투과성이 좋은 광산발생제의 발명에 초점이 맞추어지고 있다. 따라서 광산 발생제로 적합한 염의 음이온에 벌키(bulky)한 알리사이클릭(alicyclic) 링을 도입하는 시도가 급속히 이루어지고 있다.Therefore, in recent years, based on a number of experimental results and papers that the anion side can have more influence than the cation side as a physical and chemical property that substantially improves the fluidity of the acid and the physical properties of the resist composition. The invention of the part has been newly made, and this focuses on the invention of the photoacid generator which reduces the diffusion rate of acid and has good permeability for 193 nm ArF light. Attempts have therefore been made to introduce bulky alicyclic rings to the anions of salts suitable as photoacid generators.
상기와 같은 문제점을 극복하기 위하여, 본 발명은 화학증폭형 레지스트 조성물에 있어서 우수한 해상도와 라인 위드 러프니스(line width roughness)를 갖고, ArF 이머젼의 공정에 있어서 물로의 용출이 적은 신규한 산발생제를 제공하는데 그 목적이 있다.In order to overcome the above problems, the present invention is a novel acid generator having excellent resolution and line width roughness in the chemically amplified resist composition and less dissolution into water in the process of ArF immersion. The purpose is to provide.
또한, 산발생제 제조시 사용되는 중간체 및 중간체 물질을 합성하는 제조방법을 제공하는 것을 또 다른 목적으로 삼고 있다. Another object is to provide a process for the synthesis of intermediates and intermediate materials used in the production of acid generators.
본 발명에 따른 산발생제는 하기 화학식 1로 표시된다.The acid generator according to the present invention is represented by the following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서, X는 탄소수 3 내지 30의 일환식 또는 다환식 탄화수소기이고, 상기 X의 적어도 하나 이상의 수소가 치환기로 치환될 수 있고, 상기 치환기는 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 알콕시기, 탄소수 1 내지 4의 퍼플로우로 알킬기, 탄소수 1 내지 10의 하이드록시알킬기 및 시아노기로 이루어진 군으로부터 선택된 하나 이상을 포함하고, 상기 치환기는 에테르기, 에스테르기, 카르보닐기, 아세탈기, 에폭시기, 나이트릴기 또는 알데히드기를 더 포함할 수 있고, R6는 탄소수가 1 내지 10의 알킬기, 탄소수 1 내지 10의 알콕시 또는 N, S 및 F로 이루어진 군으로부터 선택된 헤테로 원자이고, m은 0 내지 2의 정수이며, A+는 유기 짝이온이다.In Formula 1, X is a monocyclic or polycyclic hydrocarbon group having 3 to 30 carbon atoms, at least one hydrogen of X may be substituted with a substituent, the substituent is an alkyl group having 1 to 10 carbon atoms, 1 to 10 carbon atoms An alkoxy group, a C1 to C4 perflow alkyl group, a C1 to C10 hydroxyalkyl group and a cyano group including at least one selected from the group consisting of, the substituent is an ether group, ester group, carbonyl group, acetal group, It may further comprise an epoxy group, a nitrile group or an aldehyde group, R 6 is an alkyl group having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms or a hetero atom selected from the group consisting of N, S and F, m is 0 to 2 Is an integer, and A + is an organic counterion.
바람직하게는, 상기 X는, 아다만틸기, 노보닐기 또는 사이클로알킬기일 수 있다.Preferably, X may be an adamantyl group, a norbornyl group, or a cycloalkyl group.
구체적으로, 상기 환 X의 예로는 탄소수 3 내지 12의 일환식 탄화수소 그룹, 탄소수 8 내지 20의 이환식 탄화수소 그룹, 탄소수 10 내지 30의 삼환식 탄화수소 그룹, 탄소수 10 내지 30의 사환식 탄화수소 그룹 등이 포함될 수 있다.Specifically, examples of the ring X include a monocyclic hydrocarbon group having 3 to 12 carbon atoms, a bicyclic hydrocarbon group having 8 to 20 carbon atoms, a tricyclic hydrocarbon group having 10 to 30 carbon atoms, a tetracyclic hydrocarbon group having 10 to 30 carbon atoms, and the like. Can be.
이와 같은 일환식, 이환식, 삼환식, 사환식의 예는 다음과 같은 1-a 내지 1-h와 같은 형태를 나타낼 수 있다. Examples of such a monocyclic, bicyclic, tricyclic, tetracyclic may be represented as follows 1-a to 1-h.
또한, 상기 환 X는 어느 위치에 있는 수소가 되든 하나는 인접그룹으로부터 결합된 형태를 갖고, 인접그룹으로부터 결합된 형태를 제외한 환에 존재하는 수소 중 적어도 하나의 수소가 탄소수 1에서 10개까지의 알킬 혹은 알콕시, 탄소수 1에서 10개까지의 하이드록시 알킬 등을 포함한다. In addition, the ring X has a form in which one is bonded from an adjacent group regardless of the hydrogen in any position, and at least one hydrogen in the ring except for the form bonded from the adjacent group has 1 to 10 carbon atoms. Alkyl or alkoxy, C1-C10 hydroxy alkyl, etc. are included.
또한, 본 발명의 화학식 1에 나타내어지는 음이온은 하기와 같은 1-i 내지 1-xx의 구조를 갖는 것을 그 예로 들 수 있다.In addition, examples of the anion represented by the formula (1) of the present invention having a structure of 1-i to 1-xx as follows.
또한, 상기 화학식 1에서 A+는 유기 짝이온을 나타내며 그 예로는 하기 화학 식 2a, 2b 또는 3a, 3b 등을 들 수 있다.In addition, in Formula 1, A + represents an organic counterion, and examples thereof include the following Chemical Formulas 2a, 2b, or 3a, 3b.
[화학식 2a][Formula 2a]
[화학식 2b][Formula 2b]
상기 화학식 2a 또는 2b에서 R1과 R2는 각각 독립적으로 알킬기, 알릴기, 퍼플루오로알킬기, 벤질기, 또는 아릴기를 나타내고, R3, R4 및 R5는 각각 독립적으로 수소, 알킬기, 할로겐기, 알콕시기, 아릴기, 티오페녹시기(thiophenoxy), 티오알콕시기(thioalkoxy), 또는 알콕시카르보닐메톡시기(alkoxycarbonylmethoxy)를 나타낸다.In Formula 2a or 2b, R 1 and R 2 each independently represent an alkyl group, an allyl group, a perfluoroalkyl group, a benzyl group, or an aryl group, and R 3 , R 4, and R 5 each independently represent a hydrogen, an alkyl group, or a halogen. Group, alkoxy group, aryl group, thiophenoxy, thioalkoxy, or alkoxycarbonylmethoxy group.
그리고, 이러한 치환기를 보다 구체적으로 예시하면 알킬 그룹은 메틸 그룹, 에틸 그룹, 프로필 그룹, 이소프로필 그룹, n-부틸 그룹, 페닐 그룹, 헥실 그룹, 옥틸 그룹 등이 있을 수 있고, 알콕시 그룹은 메톡시 그룹, 에톡시 그룹, 프로폭시 그룹, 부톡시 그룹, 헥실옥시 그룹, 옥틸옥시 그룹 등이 있을 수 있다.In more detail, the alkyl group may include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a phenyl group, a hexyl group, an octyl group, and the alkoxy group may be a methoxy group. Groups, ethoxy groups, propoxy groups, butoxy groups, hexyloxy groups, octyloxy groups and the like.
[화학식 3a][Formula 3a]
[화학식 3b][Formula 3b]
상기 화학식 3a 또는 3b에서 R1과 R4는 각각 독립적으로 알킬기, 알릴기, 퍼플루오로알킬기, 벤질기, 또는 아릴기를 나타내고, R2 와 R3는 각각 독립적으로 수소, 알킬기, 할로겐기, 알콕시기, 아릴기, 티오페녹시기, 티오알콕시기, 또는 알콕시카르보닐메톡시기를 나타낸다.In Formula 3a or 3b, R 1 and R 4 each independently represent an alkyl group, an allyl group, a perfluoroalkyl group, a benzyl group, or an aryl group, and R 2 and R 3 each independently represent a hydrogen, an alkyl group, a halogen group, or an alkoxy group. Group, an aryl group, a thiophenoxy group, a thioalkoxy group, or an alkoxycarbonylmethoxy group.
그리고, 이러한 치환기를 보다 구체적으로 예시하면 알킬 그룹은 메틸 그룹, 에틸 그룹, 프로필 그룹, 이소프로필 그룹, n-부틸 그룹, 페닐 그룹, 헥실 그룹, 옥틸 그룹 등이 있을 수 있고, 알콕시 그룹은 메톡시 그룹, 에톡시 그룹, 프로폭시 그룹, 부톡시 그룹, 헥실옥시 그룹, 옥틸옥시 그룹 등이 있을 수 있다.In more detail, the alkyl group may include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a phenyl group, a hexyl group, an octyl group, and the alkoxy group may be a methoxy group. Groups, ethoxy groups, propoxy groups, butoxy groups, hexyloxy groups, octyloxy groups and the like.
한편, 상기 화학식 2a 또는 2b의 구체적인 예로는 하기 2-i 내지 2-xx로 이루어진 군으로부터 선택된 것일 수 있다. On the other hand, specific examples of Formula 2a or 2b may be selected from the group consisting of 2-i to 2-xx.
그리고, 화학식 3a 또는 3b의 구체적인 예로는 하기 3-i 내지 3-ix로 이루어진 군으로부터 선택된 것일 수 있다.And, specific examples of the formula 3a or 3b may be selected from the group consisting of 3-i to 3-ix.
본 발명에 있어서, 상기 신규한 산발생제의 구체적인 예는 하기 4a, 4b, 4c 또는 4d인 염일 수 있다.In the present invention, specific examples of the novel acid generator may be a salt of the following 4a, 4b, 4c or 4d.
[화학식 4a][Formula 4a]
[화학식 4b][Formula 4b]
[화학식 4c][Formula 4c]
[화학식 4d][Formula 4d]
상기 화학식 4a와 4b에서 R1과 R2, 화학식 4c와 4d에서 R1은 각각 독립적으로 알킬기, 알릴기, 퍼플루오로알킬기, 벤질기, 또는 아릴기를 나타내고, 화학식 4a와 4b에서 R3, R4, R5, 화학식 4c와 4d에서 R2, R3, R4는 각각 독립적으로 수소, 알킬기, 할로겐기, 알콕시기, 아릴기, 티오페녹시기, 티오알콕시기, 또는 알콕시카르보닐메톡시기를 나타내고, B는 하기 화학식 5, 6 또는 7을 나타낸다.In the general formula 4a and 4b in the R 1 and R 2, the formula 4c and 4d R 1 are each an alkyl group independently, an allyl group, a perfluoroalkyl group, a represents a benzyl group, or an aryl group, in the general formula 4a and 4b R 3, R 4 , R 5, R 2 , R 3 , and R 4 in Formulas 4c and 4d are each independently hydrogen, an alkyl group, a halogen group, an alkoxy group, an aryl group, a thiophenoxy group, a thioalkoxy group, or an alkoxycarbonylmethoxy group And B represents the following formula (5), (6) or (7).
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
이하, 상기 화학식 1로 표시되는 산발생제의 제조방법에 대해 살펴보도록 한다.Hereinafter, a method of preparing the acid generator represented by Chemical Formula 1 will be described.
본 발명에 있어서, 상기 화학식 1로 표시되는 염의 제조 방법으로는 0 내지 100℃의 온도에서 디클로로메탄, 클로로포름, 디클로로 에탄등을 물과 함께 섞어 사용하여 하기 화학식 8과 화학식 12의 반응물을 섞어 반응시키는 단계를 포함하는 방법이 사용될 수 있다.In the present invention, as a method for preparing a salt represented by the formula (1) by using a mixture of dichloromethane, chloroform, dichloro ethane and the like at a temperature of 0 to 100 ℃ with water to react the mixture of the formula (8) and formula (12) A method comprising the steps can be used.
[화학식 8][Formula 8]
[화학식 12][Formula 12]
A+Z-A + Z-
상기 화학식 8 및 12에서, X는 탄소수 3 내지 30의 일환식 또는 다환식 탄화수소기이고, 상기 X의 적어도 하나 이상의 수소가 치환기로 치환될 수 있고, 상기 치환기는 탄소수 1 내지 10의 알킬기, 탄소수 1 내지 10의 알콕시기, 탄소수 1 내지 4의 퍼플로우로 알킬기, 탄소수 1 내지 10의 하이드록시알킬기 및 시아노기로 이루어진 군으로부터 선택된 하나 이상을 포함하고, 상기 치환기는 에테르기, 에스테르기, 카르보닐기, 아세탈기, 에폭시기, 나이트릴기 또는 알데히드기를 더 포함할 수 있고, R6는 탄소수가 1 내지 10의 알킬기, 탄소수 1 내지 10의 알콕시 또는 N, S 및 F로 이루어진 군으로부터 선택된 헤테로 원자이고, m은 0 내지 2의 정수이며, M은 Li, Na 또는 K이고, Z는 OSO2CF3, OSO2C4F9, OSO2C8F17, N(CF3)2, N(C2F5)2, N(C4F9)2, C(CF3)3, C(C2F5)3, C(C4F9)3,, F, Cl, Br, I, BF4, ASF6 또는 PF6 이고, A+는 유기 짝이온이다.In
상기 화학식 8의 사용양은 화학식 12에 대하여 1몰 ~ 2몰 정도를 사용한다. 수득된 화학식 1의 염은 고체인 경우는 재결정법, 내지는 수득된 염을 잘 녹이는 용매와 녹이지 못하는 용매를 혼합 사용하여 고체화 법을 사용하여 회수하고 오일인 경우는 용매로 추출하거나 농축하여 회수할 수 있다.The amount of the formula (8) is used in about 1 to 2 moles relative to the formula (12). The obtained salt of formula (1) is recovered by recrystallization in the case of solid, or by solidification using a solvent that dissolves well with the obtained salt, and in the case of oil, it can be recovered by extracting or concentrating with solvent. Can be.
그리고, 화학식 8의 염의 제조 방법의 예로는 하기 화학식 10의 알코올과 화학식 11의 카보닐 클로라이드와 반응시키는 방법이 사용될 수 있다.In addition, as an example of a method for preparing a salt of Formula 8, a method of reacting an alcohol of Formula 10 with a carbonyl chloride of Formula 11 may be used.
[화학식 10][Formula 10]
[화학식 11][Formula 11]
상기 화학식 10에서 M은 Li, Na 또는 K이고, 화학식 11의 환X는 탄소수 3 내지 30개의 일환식 또는 다환식 탄화수소 그룹이고, 일환식 또는 다환식 탄화수소 그룹에서 적어도 하나 이상의 수소가 에테르기, 에스테르기, 카르보닐기, 아세탈기, 에폭시기, 나이트릴기, 또는 알데히드기를 포함하거나 포함하지 않은 탄소원자가 1에서 10개까지의 알킬 또는 알콕시 그룹, 1 내지 4의 퍼플로우로 알킬 그룹, 탄소수 1 내지 10의 하이드록시 알킬 그룹 또는 시아노 그룹을 나타내며, R6는 탄소수가 1 내지 10의 알킬기, 탄소수 1 내지 10의 알콕시 또는 N, S 및 F로 이루어진 군으로부터 선택된 헤테로 원자이고, m은 0 내지 2의 정수이다. M in Formula 10 is Li, Na or K, ring X of Formula 11 is a monocyclic or polycyclic hydrocarbon group having 3 to 30 carbon atoms, at least one hydrogen in the monocyclic or polycyclic hydrocarbon group is an ether group, ester Alkyl or alkoxy groups having from 1 to 10 carbon atoms with or without groups, carbonyl groups, acetal groups, epoxy groups, nitrile groups, or aldehyde groups, alkyl groups with a perflow of 1 to 4, hydroxy having 1 to 10 carbon atoms An alkyl group or a cyano group, R 6 is a hetero atom selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms or N, S and F, and m is an integer of 0 to 2.
구체적으로, 이러한 반응의 방법으로는 일반적으로 0 내지 100℃의 온도에서 반응 용매로 디클로로메탄, 클로로포름, 디클로로 에탄, 아세트니트릴, 톨루엔 등 에 화학식 10의 알코올과 화학식 12의 카르보닐 클로라이드를 녹인 후 염기성 촉매로 트리에틸아민, 디에틸아민, 피리딘, 디에틸이소프로필 아민등을 반응물 화학식 12에 대하여 1몰 ~ 2몰까지 사용하여 반응 할 수 있고 N,N-디메틸 아미노 피리딘을 화합물에 대하여 0.1몰에서 0.5몰까지의 양을 촉매로 사용하여 제조할 수 있다.Specifically, the method of the reaction is generally dissolved in dichloromethane, chloroform, dichloroethane, acetonitrile, toluene and the like of alcohol of formula 10 and carbonyl chloride of formula 12 in a reaction solvent at a temperature of 0 to 100 ℃ As a catalyst, triethylamine, diethylamine, pyridine, diethylisopropyl amine and the like can be reacted using 1 to 2 mol of the reactant formula 12, and N, N-dimethyl amino pyridine is reacted at 0.1 mol with respect to the compound. Up to 0.5 moles can be prepared using the catalyst.
그리고, 상기 화학식 10의 알코올의 제조 방법으로는 하기 화학식 9와 같은 에스테르 화합물을 테트라하이드로 퓨란과 메탄올, 에탄올, 프로판올 등과 같은 알코올성 용매를 사용하여 녹이고 얼음 bath하에서 소듐 보로 하이드라이드(NaBH4)를 서서히 적가한다. 상기 소듐 보로 하이드라이드(NaBH4)는 환원제로서, 이러한 환원제는 소듐 보로하이드라이드이외에도, 리튬 알루미늄 하이드라이드(LiAlH4), BH3-THF, NaBH4-AlCl3, NaBH4-LiCl 및 LiAl(OMe)3로 이루어진 군으로부터 선택될 수 있다. 적가가 완료되면 60℃ 오일 베쓰(bath)하에서 4시간 정도 교반을 한 후 반응 혼합액을 증류수로 quenching하여 용매를 제거한다. 증류수로 다시 용매가 제거된 반응 혼합액을 녹인 후 진한 염산을 사용하여 pH값이 5 내지 6이 될 때까지 산성화 시킨다. 다시 상기의 혼합액을 농축한 후 메탄올을 넣어 슬러리 상태로 만들어 여과한다. 여액은 핵산을 사용하여 세척 후 다시 농축하고 디에틸 에테르를 사용하여 결정화 한 후 여과 건조하여 화학식 10과 같은 알코올을 제조 할 수 있다. In addition, as a method for preparing an alcohol of Formula 10, an ester compound represented by Formula 9 is dissolved using an alcoholic solvent such as tetrahydrofuran, methanol, ethanol, propanol, and the like, and sodium borohydride (NaBH 4 ) is gradually dissolved in an ice bath. Add it down. The sodium borohydride (NaBH 4 ) is a reducing agent, and in addition to sodium borohydride, the reducing agent is lithium aluminum hydride (LiAlH 4 ), BH 3- THF, NaBH 4- AlCl 3 , NaBH 4- LiCl and LiAl (OMe) 3 can be selected from the group consisting of. After the dropping is completed, the mixture is stirred for about 4 hours in a 60 ° C oil bath, and the reaction mixture is quenched with distilled water to remove the solvent. After dissolving the reaction mixture in which the solvent is removed again with distilled water, acidification is performed using concentrated hydrochloric acid until the pH value is 5-6. The mixture is concentrated again and methanol is added to make a slurry and filtered. The filtrate can be washed with nucleic acid, concentrated again, crystallized with diethyl ether, filtered and dried to prepare an alcohol as shown in Formula 10.
[화학식 9][Formula 9]
여기서, R1은 수소, 메틸, 트리플로오르메틸, 트리클로로메틸, 트리브로모메틸, 트리요오드메틸로 이루어진 군으로부터 선택된 것이고, M은 Li, Na, 또는 K이다.Wherein R 1 is selected from the group consisting of hydrogen, methyl, trifluoromethyl, trichloromethyl, tribromomethyl, triiomethyl, and M is Li, Na, or K.
본 발명에 따른 산발생제는 음이온에 알리사이클릭 링을 도입함으로써 산의 확산 속도를 조절하고, ArF 광원의 사용시 고투과성의 특성을 나타낼 수 있는 이점이 있다.The acid generator according to the present invention has the advantage of controlling the diffusion rate of the acid by introducing an alicyclic ring to the anion and exhibiting high permeability characteristics when using an ArF light source.
이하, 본 발명을 바람직한 합성예 및 실시예를 통해 구체적으로 설명하도록 한다. 그러나 본 발명이 이와 같은 실시예에 의해 한정되지 않음은 주지되어야 할 것이다.Hereinafter, the present invention will be described in detail through preferred synthesis examples and examples. It should be noted, however, that the present invention is not limited by this embodiment.
[합성예 1]Synthesis Example 1
아다만탄-1-카르복실릭 산-2,2-디플로우로-2-설포-에틸 에스터 디페닐 메틸페닐 설포늄 염(Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester diphenyl methylphenyl sulfonium salt)Adamantane-1-carboxylic acid-2,2-difluoro-2- sulfo-ethyl ester diphenyl methyl phenyl sulfonium salt (Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo- ethyl ester diphenyl methylphenyl sulfonium salt)
<1> 얼음중탕하에 디플로우로 설포 아세틱 산 에틸 에스터 나트륨 염(difluoro sulfo acetic acid ethyl ester sodium salt) 83g을 메탄올 160ml와 1.2L의 THF에 녹이고 나트륨 보로 하이드라이드(NaBH4) 44g을 천천히 적가한다. 적가를 마친 후 얼음중탕을 제거하고 승온하여 60℃에서 약 4시간 동안 교반하여 준다.<1> 83 g of difluoro sulfo acetic acid ethyl ester sodium salt was dissolved in 160 ml of methanol and 1.2 L of THF under distilled water and 44 g of sodium borohydride (NaBH 4 ) was slowly added dropwise. do. After completion of the dropping, remove the ice bath and raise the temperature and stir at 60 ° C. for about 4 hours.
반응 후 반응 혼합액을 증류수로 quenching한 후 용매를 제거한다. 증류수로 다시 크루드한 혼합 반응물을 녹이고 진한 염산으로 pH값을 5 내지 6이 되도록 산성화한다. 농축한 후 메탄올을 넣어 슬러리를 여과하여 무기 염을 제거하고 여액을 핵산으로 2회 세척하고 메탄올층을 다시 농축한 다음 디에틸 에테르를 사용하여 결정화한다. 여과 후 얻은 횐색 고체를 진공 건조하고 도 1에 나타낸 1H-NMR에 의하여 그 구조를 확인하였다. 건조 여과 후 디플로우로 하이드록시 에탄 설포닉 산 나트륨 염(difluoro hydroxyl ethane sulfonic acid sodium salt) 68.5g(수율 95%)을 얻었다.After the reaction, the reaction mixture is quenched with distilled water and then the solvent is removed. The reacted mixed reactant is again dissolved in distilled water and acidified to
1H-NMR (D2O): δ(ppm) 4.18(t, 2H) 1 H-NMR (D 2 O): δ (ppm) 4.18 (t, 2H)
<2> 상기에서 제조한 디플로우로 하이드록시 에탄 설포닉 산 나트륨 염 (difluoro hydroxyl ethane sulfonic acid sodium salt) 20g과 아다만탄 카보닐 클로라이드 29g을 디클로로에탄 400ml에 녹이고 상온에서 교반시켜 준다. 트리에틸아민 23ml를 상온에서 서서히 적가 시킨 후 반응 온도를 60℃까지 승온시켜 2시간 동안 가열 교반한다.<2> 20 g of difluoro hydroxyl ethane sulfonic acid sodium salt and 29 g of adamantane carbonyl chloride were dissolved in 400 ml of dichloroethane and stirred at room temperature. 23 ml of triethylamine was slowly added dropwise at room temperature, and the reaction temperature was raised to 60 ° C., followed by heating and stirring for 2 hours.
반응종결 후 반응 용매를 제거하고 에틸 에테르에 슬러리를 만들어 여과한다. 여과 후 증류수와 에틸 에테르를 사용하여 세척하여 주고 진공 건조하여 도 2에 나타낸1H-NMR에 의하여 그 구조를 확인하였고 하기의 구조식과 같은 아다만탄-1-카르복실릭 산-2,2-디플로우로-2-설포-에틸-에스터 나트륨 염(Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester sodium salt)을 30g(수율 80%) 수득하였다.After completion of the reaction, the reaction solvent is removed, and a slurry is made of ethyl ether and filtered. After filtration, the mixture was washed with distilled water and ethyl ether, and dried in vacuo to confirm the structure by 1 H-NMR shown in FIG. 2. Adamantane-1-carboxylic acid-2,2- 30g (yield 80%) of difluoro-2-sulfo-ethyl-ester sodium salt was obtained. (Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester sodium salt)
1H-NMR (디메틸설폭사이드-d6, 내부기준: 테트라메틸실란): δ(ppm) 1.67-1.98(m, 15H), 4.52(t, 2H) 1 H-NMR (dimethylsulfoxide-d 6 , internal standard: tetramethylsilane): δ (ppm) 1.67-1.98 (m, 15H), 4.52 (t, 2H)
<3> 상기<2>에서 제조한 아다만탄-1-카르복실릭 산-2,2-디플로우로-2-설포-에틸 에스터 나트륨 염(Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester sodium salt) 8.5g과 디페닐 메틸페닐 설포늄 트리플루오르 메탄 설포네이트 염(dipenyl methylphenyl sulfonium trifluoro methane sulfonium salt) 10g을 디클로로메탄 100ml, 물 100ml에 녹여 넣어 두층 반응을 하여 격렬하게 3시간 동안 교반시켜 준다.<3> Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester sodium salt prepared in <2> above (Adamantane-1-carboxylic acid-2,2-difluoro 8.5g of -2-sulfo-ethyl ester sodium salt and 10g of diphenylyl methylphenyl sulfonium trifluoro methane sulfonium salt were dissolved in 100ml of dichloromethane and 100ml of water, followed by vigorous reaction. Stir for 3 hours.
교반이 끝나면 유기층을 취하여 19F NMR에 의하여 반응의 진행 정도를 확인한다. 반응이 종결되면 유기층을 모아 용매를 제거하고 good 용매인 디클로로 메탄과 poor 용매인 핵산을 사용하여 세척하여 내고 용매를 제거하고 감압건조하여 아다만탄-1-카르복실릭 산-2,2-디플로우로-2-설포-에틸-에스터 디페닐 플로오르페닐 설포늄 염(Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester diphenyl fluorophenyl sulfonium salt)을 13.3g(수율 94.3%)을 수득하였고 그 구조를 도 3에 나타낸 1H-NMR에 의하여 확인하였다.After stirring, the organic layer was taken and the progress of the reaction was confirmed by 19F NMR. After the reaction is completed, the organic layer is collected to remove the solvent, washed with dichloromethane as a good solvent and nucleic acid as a poor solvent, and the solvent is removed and dried under reduced pressure to add adamantane-1-carboxylic acid-2,2-di. 13.3g of Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester diphenyl fluorophenyl sulfonium salt (yield 94.3%) with flowo-2-sulfo-ethyl-ester diphenyl fluorophenyl sulfonium salt ) Was obtained and its structure was confirmed by 1 H-NMR shown in FIG.
1H-NMR (클로로포름-d3, 내부기준: 테트라메틸실란): δ(ppm) 1.67-1.98(m, 15H), 2.47(s, 3H), 4.76(t, 2H), 7.48(d, 2H), 7.65-7.76(m, 12H) 1 H-NMR (chloroform-d 3 , internal standard: tetramethylsilane): δ (ppm) 1.67-1.98 (m, 15H), 2.47 (s, 3H), 4.76 (t, 2H), 7.48 (d, 2H ), 7.65-7.76 (m, 12H)
[합성예 2]Synthesis Example 2
<1> [합성예 1]의 <1>에서 제조한 디플로우로 하이드록시 에탄 설포닉 산 나트륨 염(difluoro hydroxyl ethane sulfonic acid sodium salt) 10g과 시클로핵산 카보닐 클로라이드 8.7ml를 디클로로에탄 400ml에 녹이고 상온에서 교반시켜 준다. 트리에틸아민 23ml를 상온에서 서서히 적가 시킨 후 반응 온도를 60℃까지 승온시켜 2시간 동안 교반한다.<1> 10 g of difluoro hydroxyl ethane sulfonic acid sodium salt and 8.7 ml of cyclonucleic acid carbonyl chloride were dissolved in 400 ml of dichloroethane by diflow prepared in <1> of Synthesis Example 1. Stir at room temperature. 23 ml of triethylamine was slowly added dropwise at room temperature, and the reaction temperature was raised to 60 ° C. and stirred for 2 hours.
반응종결 후 반응 용매를 제거하고 에틸 에테르에 슬러리를 만들어 여과한다. 여과 후 증류수와 에틸 에테르를 사용하여 세척하여 주고 진공 건조하여 도 4에 나타낸 1H-NMR에 의하여 그 구조를 확인하였고 하기의 구조식과 같은 시클로헥산 카르복실릭 산 2,2-디플로우로-2-설포-에틸-에스터 나트륨 염(cyclohexane carboxylic acid, 2,2-difluoro-2-sulfo-ethyl ester sodium salt)을 12.9g(수율 81.2%) 수득하였다.After completion of the reaction, the reaction solvent is removed, and a slurry is made of ethyl ether and filtered. After filtration, the mixture was washed with distilled water and ethyl ether, and dried in vacuo to confirm the structure by 1 H-NMR shown in FIG. 4, and cyclohexane
1H-NMR (디메틸설폭사이드-d6, 내부기준: 테트라메틸실란): δ(ppm) 1.21-1.92(m, 10H), 2.40(m, 1H), 4.52(t, 2H) 1 H-NMR (dimethylsulfoxide-d 6 , internal standard: tetramethylsilane): δ (ppm) 1.21-1.92 (m, 10H), 2.40 (m, 1H), 4.52 (t, 2H)
<2> 상기<1>에서 제조한 시클로헥산 카르복실릭 산 2,2-디플로우로-2-설포-에틸-에스터 나트륨 염(cyclohexane carboxylic acid, 2,2-difluoro-2-sulfo-ethyl ester sodium salt) 8.3g 과 디페닐 메틸페닐 설포늄 트리플루오르 메탄 설포네이트 염(dipenyl methylphenyl sulfonium trifluoro methane sulfonium salt) 10g을 디클로로메탄 100ml, 물 100ml에 녹여 넣어 두층 반응을 하여 격렬하게 3시간 동안 교반시켜 준다.<2> cyclohexane
교반이 끝나면 유기층을 취하여 19F NMR에 의하여 반응의 진행 정도를 확인한다. 반응이 종결되면 유기층을 모아 용매를 제거하고 good 용매인 디클로로메탄과 poor 용매인 핵산을 사용하여 세척하여 내고 용매를 제거하고 감압건조하여 시클로헥산 카르복실릭 산 2,2-디플로우로-2-설포-에틸-에스터 디페닐메틸페닐 설포늄 염 12g(수율95.2%)을 수득하였고 그 구조를 도 5에 나타낸 1H-NMR에 의하여 확인하였다.After stirring, the organic layer was taken and the progress of the reaction was confirmed by 19F NMR. After the reaction is completed, the organic layer is collected, the solvent is removed, washed with dichloromethane as a good solvent and nucleic acid as a poor solvent, and the solvent is removed and dried under reduced pressure to remove cyclohexane
1H-NMR (클로로포름-d3, 내부기준: 테트라메틸실란): δ(ppm) 1.18-2.05(m, 10H), 2.42(m, 1H), 2.46(s, 3H), 4.77(t, 2H), 7.48(d, 2H), 7.65-7.76(m, 12H) 1 H-NMR (chloroform-d 3 , internal standard: tetramethylsilane): δ (ppm) 1.18-2.05 (m, 10H), 2.42 (m, 1H), 2.46 (s, 3H), 4.77 (t, 2H ), 7.48 (d, 2H), 7.65-7.76 (m, 12H)
[합성예 3]Synthesis Example 3
<1> [합성예 1]의 <1>에서 제조한 디플로우로 히드록시 에탄 설포닉 산 나트륨 염(difluoro hydroxyl ethane sulfonic acid sodium salt) 20g과 노보난 카보닐 클로라이드(norbornane carboxylic chloride) 26g를 디클로로에탄 400ml에 녹이고 상온에서 교반시켜 준다. 트리에틸아민 30.4ml를 상온에서 서서히 적가 시킨 후 반응 온도를 60℃까지 승온시켜 2시간 동안 가열 교반한다.<1> 20 g of difluoro hydroxyl ethane sulfonic acid sodium salt and 26 g of norbornane carboxylic chloride were diluted with diflow prepared in <1> of Synthesis Example 1. Dissolve in 400ml of ethane and stir at room temperature. 30.4 ml of triethylamine was slowly added dropwise at room temperature, and the reaction temperature was raised to 60 ° C., followed by heating and stirring for 2 hours.
반응종결 후 반응 용매를 제거하고 에틸 에테르에 슬러리를 만들어 여과한다. 여과 후 증류수와 에틸 에테르를 사용하여 세척하여 주고 진공 건조하여 도 6에 나타낸 1H-NMR에 의하여 그 구조를 확인하고 하기의 구조식과 같은 바이사이클로[2.2.1]헵탄-2-카르복실릭 산 2,2-디플로우로-2-설포-에틸 에스터 나트륨 염(Bicyclo[2.2.1]heptane-2-carboxylic acid 2,2-difluoro-2-sulfo-ethyl ester salt)을 28.9g(수율 86.2%) 수득하였다.After completion of the reaction, the reaction solvent is removed, and a slurry is made of ethyl ether and filtered. After filtration, the mixture was washed with distilled water and ethyl ether, dried in vacuo to confirm the structure by 1 H-NMR as shown in FIG. 6, and then subjected to bicyclo [2.2.1] heptan-2-carboxylic acid as shown in 28.9 g of 2,2-difluoro-2-sulfo-ethyl ester sodium salt (Bicyclo [2.2.1] heptane-2-
1H-NMR (디메틸설폭사이드-d6, 내부기준: 테트라메틸실란): δ(ppm) 1.15-2.82(m, 11H), 4.57(m, 2H) 1 H-NMR (dimethylsulfoxide-d 6 , internal standard: tetramethylsilane): δ (ppm) 1.15-2.82 (m, 11H), 4.57 (m, 2H)
<2> 상기<1>에서 제조한 바이사이클로[2.2.1]헵탄-2-카르복실릭 산 2,2-디플로우로-2-설포-에틸 에스터 나트륨 염(Bicyclo[2.2.1]heptane-2-carboxylic acid 2,2-difluoro-2-sulfo-ethyl ester salt) 15.1g과 디페닐 메틸페닐 설포늄 트리플루오르 메탄 설포네이트 염(dipenyl methylphenyl sulfonium trifluoro methane sulfonium salt) 15g을 디클로로메탄 150ml, 물 150ml에 녹여 넣어 두층 반응을 하여 격렬하게 3시간 동안 교반시켜 준다.<2> Bicyclo [2.2.1] heptan-2-
교반이 끝나면 유기층을 취하여 19F NMR에 의하여 반응의 진행 정도를 확인한다. 반응이 종결되면 유기층을 모아 용매를 제거하고 good 용매인 디클로로메탄과 poor 용매인 핵산을 사용하여 세척하여 내고 용매를 제거하고 감압건조하여 바이사이클로[2.2.1]헵탄-2-카르복실릭 산 2,2-디플로우로-2-설포-에틸 에스터 디페 닐 메틸페닐 설포늄 염(Bicyclo[2.2.1]heptane-2-carboxylic acid 2,2-difluoro-2-sulfo-ethyl ester diphenyl methylphenyl sulfonium salt)을 18.8g(수율 95.2%)을 수득하였고 그 구조를 도 7에 나타낸 1H-NMR에 의하여 확인하였다.After stirring, the organic layer was taken and the progress of the reaction was confirmed by 19F NMR. After completion of the reaction, the organic layer was collected, the solvent was removed, washed with a good solvent, dichloromethane, and a poor solvent, a nucleic acid. The solvent was removed, and the residue was dried under reduced pressure to yield a bicyclo [2.2.1] heptan-2-
1H-NMR (클로로포름-d3, 내부기준: 테트라메틸실란): δ(ppm) 1.51-2.84(m, 11H), 2.46(s, 3H), 4.77(m, 2H), 7.48(d, 2H), 7.65-7.76(m, 12H) 1 H-NMR (chloroform-d 3 , internal standard: tetramethylsilane): δ (ppm) 1.51-2.84 (m, 11H), 2.46 (s, 3H), 4.77 (m, 2H), 7.48 (d, 2H ), 7.65-7.76 (m, 12H)
[합성예 4]Synthesis Example 4
<1> [합성예 1]의 <2>에서 제조한 아다만탄-1-카르복실릭 산-2,2-디플로우로-2-설포-에틸 에스터 나트륨 염(Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester) 7g과 디페닐t-부톡시 카보닐 메톡시 페닐 설포늄 트리플루오르 메탄 설포네이트 염 10g을 디클로로메탄 100ml, 물 100ml에 녹여 넣어 두층 반응을 하여 격렬하게 3시간 동안 교반시켜 준다.<1> Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester sodium salt prepared in <2> of Synthesis Example 1 (Adamantane-1-carboxylic acid- 7 g of 2,2-difluoro-2-sulfo-ethyl ester) and 10 g of diphenylt-butoxy carbonyl methoxy phenyl sulfonium trifluoromethane sulfonate salt were dissolved in 100 ml of dichloromethane and 100 ml of water, followed by a double layer reaction. Stir for 3 hours.
교반이 끝나면 유기층을 취하여 19F NMR에 의하여 반응의 진행 정도를 확인한다. 반응이 종결되면 유기층을 모아 용매를 제거하고 good 용매인 디클로로메탄 과 poor 용매인 핵산을 사용하여 세척하여 내고 용매를 제거하고 감압건조하여 아다만탄-1-카르복실릭 산-2,2-디플로우로-2-설포-에틸-에스터 디페닐t-부톡시 카보닐 메톡시 페닐 설포늄 염(Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester diphenyl t-buthoxy carbonyl methoxy phenyl sulfonium salt) 12.2g(수율 94.6%)을 수득하였고 그 구조를 도 8에 나타낸 1H-NMR에 의하여 확인하였다.After stirring, the organic layer was taken and the progress of the reaction was confirmed by 19F NMR. After the reaction is completed, the organic layer is collected and the solvent is removed. The solvent is washed with dichloromethane as a good solvent and nucleic acid as a poor solvent. The solvent is removed and dried under reduced pressure to form adamantane-1-carboxylic acid-2,2-di. Flowo-2-sulfo-ethyl-ester diphenylt-butoxy carbonyl methoxy phenyl sulfonium salt (Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester diphenyl t-buthoxy carbonyl methoxy phenyl sulfonium salt) 12.2 g (yield 94.6%) was obtained and its structure was confirmed by 1 H-NMR shown in FIG.
1H-NMR (클로로포름-d3, 내부기준: 테트라메틸실란): δ(ppm) 1.48(s, 9H), 1.67-1.98(m, 15H), 2.47(s, 3H), 4.62(s, 2H), 4.76(t, 2H), 7.17(d, 2H), 7.65-7.77(m, 12H) 1 H-NMR (chloroform-d 3 , internal standard: tetramethylsilane): δ (ppm) 1.48 (s, 9H), 1.67-1.98 (m, 15H), 2.47 (s, 3H), 4.62 (s, 2H ), 4.76 (t, 2H), 7.17 (d, 2H), 7.65-7.77 (m, 12H)
[합성예 5]Synthesis Example 5
<1> [합성예 1]의 <2>에서 제조한 아다만탄-1-카르복실릭 산-2,2-디플로우로-2-설포-에틸 에스터 나트륨 염(Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester sodium salt) 8.9g과 디페닐 플로오르페닐 설포늄 트리플루오르 메탄 설포네이트 염 10g을 디클로로메탄 100ml, 물 100ml에 녹여 넣어 두층 반응을 하여 격렬하게 3시간 동안 교반시켜 준다.<1> Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester sodium salt prepared in <2> of Synthesis Example 1 (Adamantane-1-carboxylic acid- 8.9 g of 2,2-difluoro-2-sulfo-ethyl ester sodium salt) and 10 g of diphenyl fluorophenyl sulfonium trifluoromethane sulfonate salt were dissolved in 100 ml of dichloromethane and 100 ml of water, followed by a two-layered reaction. Stir while.
교반이 끝나면 유기층을 취하여 19F NMR에 의하여 반응의 진행 정도를 확인한다. 반응이 종결되면 유기층을 모아 용매를 제거하고 good 용매인 디클로로메탄과 poor 용매인 핵산을 사용하여 세척하여 내고 용매를 제거하고 감압건조하여 아다만탄-1-카르복실릭 산-2,2-디플로우로-2-설포-에틸 에스터 디페닐 플로오르페닐 설포늄 염(Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester diphenyl fluorophenyl sulfonium salt) 12.8g(수율 92.1%)을 수득하였고 그 구조를 도 9에 나타낸 1H-NMR에 의하여 확인하였다.After stirring, the organic layer was taken and the progress of the reaction was confirmed by 19F NMR. After the reaction is completed, the organic layer is collected to remove the solvent, washed with dichloromethane as a good solvent and nucleic acid as a poor solvent, and the solvent is removed and dried under reduced pressure to form adamantane-1-carboxylic acid-2,2-di. 12.8 g (Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester diphenyl fluorophenyl sulfonium salt) of flowo-2-sulfo-ethyl ester diphenyl fluorophenyl sulfonium salt (yield 92.1%) Was obtained and its structure was confirmed by 1 H-NMR shown in FIG.
1H-NMR (클로로포름-d3, 내부기준: 테트라메틸실란): δ(ppm) 1.67-1.98(m, 15H), 4.76(t, 2H), 7.36-7.91(m, 14H) 1 H-NMR (chloroform-d 3 , internal standard: tetramethylsilane): δ (ppm) 1.67-1.98 (m, 15H), 4.76 (t, 2H), 7.36-7.91 (m, 14H)
[합성예 6]Synthesis Example 6
<1> [합성예 1]의 <1>에서 제조한 디플로우로 하이드록시 에탄 설포닉 산 나트륨 염(difluoro hydroxyl ethane sulfonic acid sodium salt) 10g과 시클로핵산 아세틸 클로라이드 10.5ml를 디클로로에탄 150ml에 녹이고 상온에서 교반시켜 준다. 트리에틸아민 11ml를 상온에서 서서히 적가 시킨 후 상온에서 12시간 동안 교반한다.<1> 10 g of difluoro hydroxyl ethane sulfonic acid sodium salt and 10.5 ml of cyclonucleic acid acetyl chloride were dissolved in 150 ml of dichloroethane by diflow prepared in <1> of Synthesis Example 1. Stir at 11 ml of triethylamine was slowly added dropwise at room temperature, followed by stirring at room temperature for 12 hours.
반응종결 후 반응 용매를 제거하고 에틸 에테르에 슬러리를 만들어 여과한다. 여과 후 증류수와 에틸 에테르를 사용하여 세척하여 주고 진공 건조하여 도 10에 나타낸 1H-NMR에 의하여 그 구조를 확인하였고 하기의 구조식과 같은 시클로헥실 아세틱 산 2,2-디플로우로-2-설포-에틸-에스터 나트륨 염(cyclohexyl acetic acid, 2,2-difluoro-2-sulfo-ethyl ester sodium salt)을 15g(수율 89.6%) 수득하였다.After completion of the reaction, the reaction solvent is removed, and a slurry is made of ethyl ether and filtered. After filtration, the mixture was washed with distilled water and ethyl ether, dried in vacuo to confirm the structure by 1 H-NMR shown in FIG. 10, and cyclohexyl
1H-NMR (디메틸설폭사이드-d6, 내부기준: 테트라메틸실란): δ(ppm) 0.82-1.75(m, 11H), 2.26(d, 2H), 4.53(t, 2H) 1 H-NMR (dimethylsulfoxide-d 6 , internal standard: tetramethylsilane): δ (ppm) 0.82-1.75 (m, 11H), 2.26 (d, 2H), 4.53 (t, 2H)
<2> 상기<1>에서 제조한 시클로헥실 아세틱 산 2,2-디플로우로-2-설포-에틸-에스터 나트륨 염(cyclohexyl acetic acid, 2,2-difluoro-2-sulfo-ethyl ester sodium salt) 9.1g과 디페닐 메틸페닐 설포늄 트리플루오르 메탄 설포네이트 염(dipenyl methylphenyl sulfonium trifluoro methane sulfonium salt) 9g을 디클 로로메탄 90ml, 물 90ml에 녹여 넣어 두층 반응을 하여 격렬하게 3시간 동안 교반시켜 준다.<2> cyclohexyl
교반이 끝나면 유기층을 취하여 19F NMR에 의하여 반응의 진행 정도를 확인한다. 반응이 종결되면 유기층을 모아 용매를 제거하고 good 용매인 디클로로메탄과 poor 용매인 핵산을 사용하여 세척하여 내고 용매를 제거하고 감압건조하여 시클로헥실 아세틱 산 2,2-디플로우로-2-설포-에틸-에스터 디페닐메틸페닐 설포늄 염 11.6g(수율98.1%)을 수득하였고 그 구조를 도 11에 나타낸 1H-NMR에 의하여 확인하였다.After stirring, the organic layer was taken and the progress of the reaction was confirmed by 19F NMR. After the reaction is completed, the organic layer is collected, the solvent is removed, washed with dichloromethane as a good solvent and nucleic acid as a poor solvent, and the solvent is removed and dried under reduced pressure to remove cyclohexyl
1H-NMR (클로로포름-d3, 내부기준: 테트라메틸실란): δ(ppm) 0.82-1.67(m, 11H), 2.24(d, 2H), 2.62(s, 3H), 4.79(t, 2H), 7.49(d, 2H), 7.65-7.76(m, 12H) 1 H-NMR (chloroform-d 3 , internal standard: tetramethylsilane): δ (ppm) 0.82-1.67 (m, 11H), 2.24 (d, 2H), 2.62 (s, 3H), 4.79 (t, 2H ), 7.49 (d, 2H), 7.65-7.76 (m, 12H)
[합성예 7]Synthesis Example 7
<1> [합성예 1]의 <1>에서 제조한 디플로우로 하이드록시 에탄 설포닉 산 나트륨 염(difluoro hydroxyl ethane sulfonic acid sodium salt) 20g과 노보난 아세틸 클로라이드(norbornane acetyl chloride) 28.3g를 디클로로에탄 400ml에 녹이고 상온에서 교반시켜 준다. 트리에틸아민 30.4ml를 상온에서 서서히 적가 시킨 후 반응 온도를 60℃까지 승온시켜 2시간 동안 가열 교반한다.<1> 20 g of difluoro hydroxyl ethane sulfonic acid sodium salt and 28.3 g of norbornane acetyl chloride were prepared by diflow prepared in <1> of Synthesis Example 1. Dissolve in 400ml of ethane and stir at room temperature. 30.4 ml of triethylamine was slowly added dropwise at room temperature, and the reaction temperature was raised to 60 ° C., followed by heating and stirring for 2 hours.
반응종결 후 반응 용매를 제거하고 에틸 에테르에 슬러리를 만들어 여과한다. 여과 후 증류수와 에틸 에테르를 사용하여 세척하여 주고 진공 건조하여 도 12에 나타낸 1H-NMR에 의하여 그 구조를 확인하고 하기의 구조식과 같은 바이사이클로[2.2.1]헵탄-2-아세틱 산 2,2-디플로우로-2-설포-에틸 에스터 나트륨 염(Bicyclo[2.2.1]heptane-2-acetic acid 2,2-difluoro-2-sulfo-ethyl ester salt)을 32g(수율 91.7%) 수득하였다.After completion of the reaction, the reaction solvent is removed, and a slurry is made of ethyl ether and filtered. After filtration, the mixture was washed with distilled water and ethyl ether and dried in vacuo to confirm the structure by 1 H-NMR shown in FIG. Obtained 32 g (yield 91.7%) of 2,2-difluoro-2-sulfo-ethyl ester salt of 2,2-difluoro-2-sulfo-ethyl ester sodium salt (Bicyclo [2.2.1] heptane-2-
1H-NMR (디메틸설폭사이드-d6, 내부기준: 테트라메틸실란): δ(ppm) 0.81-2.42(m, 13H), 4.53(t, 2H) 1 H-NMR (dimethylsulfoxide-d 6 , internal standard: tetramethylsilane): δ (ppm) 0.81-2.42 (m, 13H), 4.53 (t, 2H)
<2> 상기<1>에서 제조한 바이사이클로[2.2.1]헵탄-2-아세틱 산 2,2-디플로우로-2-설포-에틸 에스터 나트륨 염(Bicyclo[2.2.1]heptane-2-acetic acid 2,2-difluoro-2-sulfo-ethyl ester salt) 15.8g과 디페닐 메틸페닐 설포늄 트리플루오르 메탄 설포네이트 염(dipenyl methylphenyl sulfonium trifluoro methane sulfonium salt) 15g을 디클로로메탄 150ml, 물 150ml에 녹여 넣어 두층 반응을 하여 격렬하게 3시간 동안 교반시켜 준다.<2> Bicyclo [2.2.1] heptan-2-
교반이 끝나면 유기층을 취하여 19F NMR에 의하여 반응의 진행 정도를 확인한다. 반응이 종결되면 유기층을 모아 용매를 제거하고 good 용매인 디클로로메탄과 poor 용매인 핵산을 사용하여 세척하여 내고 용매를 제거하고 감압건조하여 바이사이클로[2.2.1]헵탄-2-아세틱 산 2,2-디플로우로-2-설포-에틸 에스터 디페닐 메틸페닐 설포늄 염(Bicyclo[2.2.1]heptane-2-acetic acid 2,2-difluoro-2-sulfo-ethyl ester diphenyl methylphenyl sulfonium salt )을 17g(수율 81.7%)을 수득하였고 그 구조를 도 13에 나타낸 1H NMR에 의하여 확인하였다.After stirring, the organic layer was taken and the progress of the reaction was confirmed by 19F NMR. After the reaction is completed, the organic layer is collected and the solvent is removed. The solvent is washed with dichloromethane as a good solvent and nucleic acid as a poor solvent. The solvent is removed and dried under reduced pressure to remove bicyclo [2.2.1] heptan-2-
1H-NMR (클로로포름-d3, 내부기준: 테트라메틸실란): δ(ppm) 0.81-2.18(m, 13H), 2.32(s, 3H), 4.78(t, 2H), 7.49(d, 2H), 7.65-7.76(m, 12H) 1 H-NMR (chloroform-d 3 , internal standard: tetramethylsilane): δ (ppm) 0.81-2.18 (m, 13H), 2.32 (s, 3H), 4.78 (t, 2H), 7.49 (d, 2H ), 7.65-7.76 (m, 12H)
[합성예 8]Synthesis Example 8
<1> [합성예 1]의 <1>에서 제조한 디플로우로 하이드록시 에탄 설포닉 산 나 트륨 염(difluoro hydroxyl ethane sulfonic acid sodium salt) 10g과 아다만탄 아세틸 클로라이드 12g을 디클로로에탄 150ml에 녹이고 상온에서 교반시켜 준다. 트리에틸아민 11ml를 상온에서 서서히 적가 시킨 후 상온에서 12시간 동안 교반한다.<1> 10 g of difluoro hydroxyl ethane sulfonic acid sodium salt and 12 g of adamantane acetyl chloride were dissolved in 150 ml of dichloroethane by diflow prepared in <1> of Synthesis Example 1. Stir at room temperature. 11 ml of triethylamine was slowly added dropwise at room temperature, followed by stirring at room temperature for 12 hours.
반응종결 후 반응 용매를 제거하고 에틸 에테르에 슬러리를 만들어 여과한다. 여과 후 증류수와 에틸 에테르를 사용하여 세척하여 주고 진공 건조하여 도 14에 나타낸 1H-NMR에 의하여 그 구조를 확인하고 하기의 구조식과 같은 아다만틸 아세틱 산 2,2-디플로우로-2-설포-에틸-에스터 나트륨 염(adamantyl acetic acid, 2,2-difluoro-2-sulfo-ethyl ester sodium salt)을 16g(수율 79%) 수득하였다.After completion of the reaction, the reaction solvent is removed, and a slurry is made of ethyl ether and filtered. After filtration, the mixture was washed with distilled water and ethyl ether, dried in vacuo to confirm the structure by 1 H-NMR shown in FIG. 14, and then added to the following formula. 16 g (79% yield) of adamantyl acetic acid (2,2-difluoro-2-sulfo-ethyl ester sodium salt) were obtained.
<2> 상기<1>에서 제조한 아다만틸 아세틱 산 2,2-디플로우로-2-설포-에틸-에스터 나트륨 염(adamantyl acetic acid, 2,2-difluoro-2-sulfo-ethyl ester sodium salt) 10g과 디페닐 메틸페닐 설포늄 트리플루오르 메탄 설포네이트 염(dipenyl methylphenyl sulfonium trifluoro methane sulfonium salt) 12g을 디클로로메탄 90ml, 물 90ml에 녹여 넣어 두층 반응을 하여 격렬하게 3시간 동안 교반시켜 준다.<2> adamantyl
교반이 끝나면 유기층을 취하여 19F NMR에 의하여 반응의 진행 정도를 확인한다. 반응이 종결되면 유기층을 모아 용매를 제거하고 good 용매인 디클로로메탄과 poor 용매인 핵산을 사용하여 세척하여 내고 용매를 제거하고 감압건조하여 아 다만틸 아세틱 산 2,2-디플로우로-2-설포-에틸-에스터 디페닐메틸페닐 설포늄 염 20g(수율95%)을 수득하였고 그 구조를 도 15에 나타낸 1H-NMR에 의하여 확인하였다.After stirring, the organic layer was taken and the progress of the reaction was confirmed by 19F NMR. After the reaction is completed, the organic layer is collected and the solvent is removed. The solvent is washed with dichloromethane as a good solvent and nucleic acid as a poor solvent. The solvent is removed and dried under reduced pressure to give amanyl
<수지 합성예 1><Resin Synthesis Example 1>
3-바이시클로[2.2.1]헵트-5-엔-2-닐-3-히드록시 프로피오닉 산 t-부틸 에스터(3-Bicyclo[2.2.1]hept-5-en-2-yl-3-hydroxy-propionic acid t-butyl ester, 이하 BHP라 명명한다), 1-메틸 아다만탄 아크릴레이트(1-methyl adamantane acrylate), 감마-부티로락톤 메틸 아크릴레이트(감마-butyrolactone acrylate)을 1:1:1(33부:33부:33부)의 몰비로 충진시키고 중합용매로는 1,4-디옥산을 반응 단량체 총 질량의 3배를 사용하고 개시제로는 아조비스이소부티로니트릴을 단량체 총 몰량을 기준으로 4mol%의 비율로 사용하여 65oC에서 16시간 동안 반응한다.3-bicyclo [2.2.1] hept-5-en-2-yl-3-hydroxy propionic acid t-butyl ester (3-Bicyclo [2.2.1] hept-5-en-2-yl-3 -hydroxy-propionic acid t-butyl ester (hereinafter referred to as BHP), 1-methyl adamantane acrylate, and gamma-butyrolactone methyl acrylate (gamma-butyrolactone acrylate): It was filled at a molar ratio of 1: 1 (33 parts: 33 parts: 33 parts), and 1,4-dioxane was used as the polymerization solvent and 3 times the total mass of the reaction monomer, and azobisisobutyronitrile was used as the initiator. The reaction is carried out at 65 ° C. for 16 hours using a ratio of 4 mol% based on the total molar amount.
반응 후 반응용액은 n-헥산에서 침전을 실시하고, 진공 건조하여 하기와 같은 수지를 얻었다. 그 결과 약 8,500의 중량 평균 분자량을 갖는 공중합체를 수득하였다.After the reaction, the reaction solution was precipitated in n-hexane, and dried in vacuo to obtain the following resin. As a result, a copolymer having a weight average molecular weight of about 8,500 was obtained.
<레지스트 조제, 실시예 1 내지 3 및 비교예 1> <Resist Preparation, Examples 1 to 3 and Comparative Example 1>
[실시예 1] 레지스트 조제Example 1 Resist Preparation
수지 합성예 1에서 얻어진 수지 100 중량부에 대하여 산발생제로 합성예 1에서 만들어진 아다만탄-1-카르복실릭 산-2,2-디플로우로-2-설포-에틸 에스터 디페닐 메틸페닐 설포늄 염 4 중량부와 염기성 첨가제로 테트라메틸 암모니움히드록시드 0.5 중량부를 프로필렌 글리콜 메틸 에테르 아세테이트 1,000 중량부에 용해시킨 다음 0.2um 막 필터로 여과하여 레지스트를 조제하였다. Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester diphenyl methylphenyl sulfonium made in Synthesis Example 1 as an acid generator based on 100 parts by weight of the resin obtained in Synthesis Example 1 4 parts by weight of salt and 0.5 parts by weight of tetramethyl ammonium hydroxide were dissolved in 1,000 parts by weight of propylene glycol methyl ether acetate, followed by filtration with a 0.2 um membrane filter to prepare a resist.
얻어진 레지스트액을 스피너를 사용하여 기판에 도포하고 110℃에서 90초간 건조시켜 0.20um 두께의 피막을 형성하였다. 형성된 피막에 ArF 엑시머 레이저 스텝퍼(렌즈 개구수 : 0.78)를 사용하여 노광시킨 후 110℃에서 90초간 열처리하였다. 이어서 2.38wt% 테트라메틸암모늄히드록시드 수용액으로 40초간 현상, 세척, 건조하여 레지스트 패턴을 형성하였다. The obtained resist liquid was applied to a substrate using a spinner, and dried at 110 ° C. for 90 seconds to form a 0.20 um thick film. The formed film was exposed to light using an ArF excimer laser stepper (lens numerical aperture: 0.78), and then heat-treated at 110 ° C. for 90 seconds. Subsequently, it was developed, washed and dried for 40 seconds with an aqueous 2.38 wt% tetramethylammonium hydroxide solution to form a resist pattern.
테트라메틸암모늄히드록시드 수용액에 대한 현상성과 형성된 레지스트 패턴 의 기판에 대한 접착성은 양호하였으며, 해상도는 0.07um, 감도는 12 mJ/cm2이었다. The developability of the aqueous tetramethylammonium hydroxide solution and the adhesion of the formed resist pattern to the substrate were good. The resolution was 0.07 μm and the sensitivity was 12 mJ / cm 2 .
실시예 결과에서 LER의 경우, 현상 후 형성된 0.10um 라인 앤드 스페이스 (L/S) 패턴에 대하여 패턴의 조도를 관찰하고, 비교예에서 얻은 패턴을 1로 할 경우 LER의 관점에서 좋아진 정도를 1 내지 5로 표기하였다(숫자가 클수록 좋은 LER). In the case of LER, the roughness of the pattern was observed for the 0.10 um line-and-space (L / S) pattern formed after development, and when the pattern obtained in the comparative example was 1, the degree of improvement in terms of LER was 1 to 1. 5 is indicated (the higher the number, the better LER).
감도의 경우, 현상 후 형성된 0.10um 라인 앤드 스페이스 (L/S) 패턴을 1 대 1의 선폭으로 형성하는 노광량을 최적노광량으로 하고 이 최적노광량을 감도로 하였으며, 이때 해상되는 최소 패턴 치수를 해상도라 하였다. In the case of sensitivity, the exposure amount that forms the 0.10 um line-and-space (L / S) pattern formed after development with a line width of 1 to 1 is used as the optimum exposure amount, and this optimal exposure amount is used as the sensitivity. It was.
[실시예 1 내지 3] [Examples 1-3]
합성예 1, 2 및 3에서 얻어진 PAG을 사용하여, 상기 수지 합성예 1에서 만들어진 수지, 염기성 첨가제를 프로필렌 글리콜 메틸 에테르 아세테이트 1,000 중량부에 용해 후 0.2um 막 필터로 여과하여 표 1로 표시되는 레지스트 조성물(단, 부는 중량 기준이다)을 조제한 후 실시예 1과 동일하게 실시하여 양성 레지스트 패턴을 형성한 후 각종 평가를 실시하였다. 평가 결과는 표 1에 나타내었다. Using the PAG obtained in Synthesis Examples 1, 2 and 3, the resin and basic additive prepared in Synthesis Example 1 were dissolved in 1,000 parts by weight of propylene glycol methyl ether acetate, and then filtered using a 0.2um membrane filter to obtain a resist shown in Table 1. After the composition (wherein parts are by weight) was prepared, the same procedure as in Example 1 was carried out to form a positive resist pattern, followed by various evaluations. The evaluation results are shown in Table 1.
[표 1] TABLE 1
* 표 1에서 사용한 PAG의 종류* Type of PAG used in Table 1
실시예 1: 합성예 1의 아다만탄-1-카르복실릭 산-2,2-디플로우로-2-설포-에틸 에스터 디페닐 메틸페닐 설포늄 염Example 1 Adamantane-1-carboxylic acid-2,2-difluoro-2-sulfo-ethyl ester diphenyl methylphenyl sulfonium salt of Synthesis Example 1
실시예 2: 합성예 2의 시클로헥산 카르복실릭 산 2,2-디플로우로-2-설포-에틸-에스터 나트륨 염Example 2:
실시예 3: 바이사이클로[2.2.1]헵탄-2-카르복실릭 산 2,2-디플로우로-2-설포-에틸 에스터 디페닐 메틸페닐 설포늄 염Example 3: Bicyclo [2.2.1] heptan-2-
비교예 1: 트리페닐 설포늄 트리플레이트Comparative Example 1: Triphenyl Sulfonium Triflate
도 1은 [합성예 1]-1에 따라 제조된 화합물의 1H-NMR 사진이다.1 is a 1 H-NMR picture of the compound prepared according to [Synthesis Example 1] -1.
도 2는 [합성예 1]-2에 따라 제조된 화합물의 1H-NMR 사진이다.2 is a 1 H-NMR photograph of the compound prepared according to [Synthesis Example 1] -2.
도 3은 [합성예 1]-3에 따라 제조된 화합물의 1H-NMR 사진이다.3 is a 1 H-NMR photograph of the compound prepared according to [Synthesis Example 1] -3.
도 4는 [합성예 2]-1에 따라 제조된 화합물의 1H-NMR 사진이다.4 is a 1 H-NMR photograph of the compound prepared according to [Synthesis Example 2] -1.
도 5는 [합성예 2]-2에 따라 제조된 화합물의 1H-NMR 사진이다.5 is a 1 H-NMR photograph of the compound prepared according to [Synthesis Example 2] -2.
도 6은 [합성예 3]-1에 따라 제조된 화합물의 1H-NMR 사진이다.6 is a 1 H-NMR photograph of the compound prepared according to [Synthesis Example 3] -1.
도 7은 [합성예 3]-2에 따라 제조된 화합물의 1H-NMR 사진이다.7 is a 1 H-NMR photograph of the compound prepared according to [Synthesis Example 3] -2.
도 8은 [합성예 6]-1에 따라 제조된 화합물의 1H-NMR 사진이다.8 is a 1 H-NMR photograph of the compound prepared according to [Synthesis Example 6] -1.
도 9는 [합성예 6]-2에 따라 제조된 화합물의 1H-NMR 사진이다.9 is a 1 H-NMR image of the compound prepared according to [Synthesis Example 6] -2.
도 10은 [합성예 7]-1에 따라 제조된 화합물의 1H-NMR 사진이다.10 is a 1 H-NMR photograph of the compound prepared according to [Synthesis Example 7] -1.
도 11은 [합성예 7]-2에 따라 제조된 화합물의 1H-NMR 사진이다.11 is a 1 H-NMR photograph of the compound prepared according to [Synthesis Example 7] -2.
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