KR20050071802A - Photoresist composition and method for forming photoresist pattern using the same - Google Patents
Photoresist composition and method for forming photoresist pattern using the same Download PDFInfo
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- KR20050071802A KR20050071802A KR1020040000123A KR20040000123A KR20050071802A KR 20050071802 A KR20050071802 A KR 20050071802A KR 1020040000123 A KR1020040000123 A KR 1020040000123A KR 20040000123 A KR20040000123 A KR 20040000123A KR 20050071802 A KR20050071802 A KR 20050071802A
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- Prior art keywords
- photoresist composition
- photoresist
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000001033 ether group Chemical group 0.000 claims abstract description 4
- 125000004185 ester group Chemical group 0.000 claims abstract description 3
- 150000001925 cycloalkenes Chemical class 0.000 claims description 9
- -1 diphenyl iodo hexafluorophosphate Chemical compound 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 3
- WTQHTDIBYAAFEX-UHFFFAOYSA-N 1-decylsulfonylsulfonyldecane Chemical compound CCCCCCCCCCS(=O)(=O)S(=O)(=O)CCCCCCCCCC WTQHTDIBYAAFEX-UHFFFAOYSA-N 0.000 claims description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical group CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- VUBUXALTYMBEQO-UHFFFAOYSA-N 2,2,3,3,3-pentafluoro-1-phenylpropan-1-one Chemical compound FC(F)(F)C(F)(F)C(=O)C1=CC=CC=C1 VUBUXALTYMBEQO-UHFFFAOYSA-N 0.000 claims description 2
- LOZJPUXMNANKIQ-UHFFFAOYSA-N 2-benzyl-3-nitro-4-(nitromethyl)benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C[N+]([O-])=O)C([N+]([O-])=O)=C1CC1=CC=CC=C1 LOZJPUXMNANKIQ-UHFFFAOYSA-N 0.000 claims description 2
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 claims description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- DRMAIBPBPJNFDH-UHFFFAOYSA-M [4-(2-methylpropyl)phenyl]-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(CC(C)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 DRMAIBPBPJNFDH-UHFFFAOYSA-M 0.000 claims description 2
- 229940000489 arsenate Drugs 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 2
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 238000010884 ion-beam technique Methods 0.000 claims description 2
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 claims description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- 125000006239 protecting group Chemical group 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000012953 triphenylsulfonium Substances 0.000 claims description 2
- 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 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims 2
- 239000004305 biphenyl Substances 0.000 claims 2
- 125000006267 biphenyl group Chemical group 0.000 claims 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims 1
- CYJCWQZJDBMRHW-UHFFFAOYSA-N [O-]S(=O)(=O)C(F)(F)F.[PH4+].S(=O)(=O)([O-])[O-].[PH4+].[PH4+] Chemical compound [O-]S(=O)(=O)C(F)(F)F.[PH4+].S(=O)(=O)([O-])[O-].[PH4+].[PH4+] CYJCWQZJDBMRHW-UHFFFAOYSA-N 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 9
- 239000003112 inhibitor Substances 0.000 abstract description 6
- 238000002835 absorbance Methods 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XEYVZLZWQFLSDZ-YIDVYQOGSA-N (3ar,5s,6s,6ar)-5-[(3r)-1,4-dioxaspiro[4.5]decan-3-yl]spiro[3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole-2,1'-cyclohexane]-6-ol Chemical compound O([C@H]1O[C@@H]([C@@H]([C@H]1O1)O)[C@@H]2OC3(CCCCC3)OC2)C21CCCCC2 XEYVZLZWQFLSDZ-YIDVYQOGSA-N 0.000 description 1
- WBUSZOLVSDXDOC-UHFFFAOYSA-M (4-methoxyphenyl)-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(OC)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WBUSZOLVSDXDOC-UHFFFAOYSA-M 0.000 description 1
- AWOATHYNVXCSGP-UHFFFAOYSA-M (4-methylphenyl)-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 AWOATHYNVXCSGP-UHFFFAOYSA-M 0.000 description 1
- AQTMPYCVJDXCIR-UHFFFAOYSA-N 2-hydroxyethyl bicyclo[2.2.2]oct-2-ene-5-carboxylate Chemical compound C1CC2C(C(=O)OCCO)CC1C=C2 AQTMPYCVJDXCIR-UHFFFAOYSA-N 0.000 description 1
- MCVRAVYDLNZUCY-UHFFFAOYSA-N 2-methylhept-5-enoic acid Chemical compound CC=CCCC(C)C(O)=O MCVRAVYDLNZUCY-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ACBDNFPUXYGKPT-UHFFFAOYSA-N bromomethyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OCBr ACBDNFPUXYGKPT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- FCYRSDMGOLYDHL-UHFFFAOYSA-N chloromethoxyethane Chemical compound CCOCCl FCYRSDMGOLYDHL-UHFFFAOYSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- JGEMYUOFGVHXKV-UPHRSURJSA-N malealdehyde Chemical compound O=C\C=C/C=O JGEMYUOFGVHXKV-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- 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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
-
- 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
-
- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
-
- 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
- G03F7/40—Treatment after imagewise removal, e.g. baking
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
Abstract
본 발명은 포토레지스트 조성물 및 이를 이용한 포토레지스트 패턴 형성 방법에 관한 것으로, 구체적으로는 (a)포토레지스트 수지, (b)광산발생제 및 (c)유기용매를 포함하는 포토레지스트 조성물에 (d)용해억제제(dissolution inhibitor)로 하기 화학식 1의 화합물을 더 포함시킨 포토레지스트 조성물 및 이를 이용한 패턴 형성방법에 관한 것이다.The present invention relates to a photoresist composition and a method of forming a photoresist pattern using the same, and specifically, to a photoresist composition comprising (a) a photoresist resin, (b) a photoacid generator, and (c) an organic solvent. It relates to a photoresist composition further comprising a compound of formula 1 as a dissolution inhibitor and a pattern forming method using the same.
이와 같은 본 발명의 포토레지스트 조성물은 248㎚ 및 193㎚ 파장에서 우수한 투과율, 에칭 내성, 내열성, 접착성 및 낮은 광흡수도를 가지며, 현상액에 대한 친화도가 높기 때문에, 패턴의 LER(line edge roughness)를 개선시킬 수 있다.The photoresist composition of the present invention has excellent transmittance, etching resistance, heat resistance, adhesiveness and low light absorbance at 248 nm and 193 nm wavelengths, and has high affinity for a developer, and thus, LER (line edge roughness) of the pattern ) Can be improved.
[화학식 1][Formula 1]
상기 식에서,Where
R은 C1∼C20의 알킬, C1∼C20의 에테르 그룹을 포함하는 알킬 및 C1∼C20의 에스테르 그룹을 포함하는 알킬로 이루어진 군에서 선택된다.R is selected from the group consisting of C 1 -C 20 alkyl, alkyl comprising C 1 -C 20 ether groups and alkyl comprising C 1 -C 20 ester groups.
Description
본 발명은 패턴의 LER(line edge roughness)을 향상시킴으로써 우수한 패턴을 형성할 수 있는 포토레지스트 조성물 및 이를 이용한 패턴 형성방법에 관한 것이다.The present invention relates to a photoresist composition capable of forming an excellent pattern by improving a line edge roughness (LER) of the pattern and a pattern forming method using the same.
반도체 칩의 집적도가 증가함에 따라 리소그래피 공정에서 서브-마이크론급의 미세 패턴 형성이 요구되고 있다. 특히 초고집적 회로의 제조를 위한 리소그래피 공정에 있어서는 단파장(DUV 영역)에서 더욱 높은 해상도를 요구하고 있다. 이에 따라, 기존의 g-라인(436nm) 및 i-라인(365nm)보다 더욱 단파장인 KrF (249nm), ArF (193nm), VUV(vacuum ultraviolet) 또는 EUV(Extremely Ultraviolet; 13nm)와 같은 화학증폭성인 원자외선 (DUV: Deep Ultra Violet) 영역의 광원을 사용하는 리소그래피 기술이 도입되었으며, 상기 광원에 대하여 고 감광도(sensitivity), 고 해상도(resolution)를 가지는 화학 증폭형 레지스트(Chemically Amplified Resist: CAR)라는 새로운 개념의 재료가 도입되었다.As the degree of integration of semiconductor chips increases, the formation of sub-micron fine patterns in a lithography process is required. In particular, in the lithography process for the manufacture of ultra-high integrated circuits, higher resolution is required in the short wavelength (DUV region). This results in chemical amplification such as KrF (249 nm), ArF (193 nm), VUV (vacuum ultraviolet) or EUV (Extremely Ultraviolet (13 nm)), which are shorter than conventional g-line (436 nm) and i-line (365 nm). A lithography technique using a light source in the deep ultra violet (DUV) region has been introduced, and a chemically amplified resist (CAR) having a high sensitivity and high resolution for the light source has been introduced. A new concept of material was introduced.
상기 화학 증폭형 레지스트는 노광에 의해 생성된 H+(proton)를 촉매로 이용하는 것으로서, H+의 확산 및 분해 반응이 연쇄적으로 일어나 고투명도를 유지하면서 패턴을 형성할 수 있는 재료이다. 이와 같은 화학 증폭형 레지스트로 이용되기 위해서는 193nm 및 157nm 파장에서 광 흡수도가 낮아야 하고, 내열성 및 접착성이 높아야 하며, 2.38wt% 및 2.6wt%의 테트라메틸 암모늄히드록사이드(TMAH) 수용액으로 현상이 가능해야 하고, 에칭 내성과 기판에 대한 접착성이 우수하여야 하는 등의 많은 요건을 충족시켜야 할뿐만 아니라, 에칭 내성이 노볼락 수지와 같은 수준의 수지를 탐색하는 것이다.The chemically amplified resist uses H + (proton) generated by exposure as a catalyst, and is a material capable of forming a pattern while maintaining a high transparency by causing a chain of diffusion and decomposition of H + . In order to be used as such chemically amplified resists, the light absorption at the wavelengths of 193 nm and 157 nm should be low, the heat resistance and adhesion should be high, and developed with 2.38 wt% and 2.6 wt% aqueous tetramethyl ammonium hydroxide (TMAH) solution. Not only must this be possible and meet many requirements, such as good etching resistance and good adhesion to the substrate, but also the search for resins at the same level as the novolak resin.
또한, 상기 화학증폭형 레지스트는 용해도를 억제하기 위하여 도입되는 용해억제 그룹을 갖는 베이스 수지 및 PAG(photoacid generator)로 이루어져 있다. 여기에 추가적으로 레지스트의 용해속도를 제어하기 위하여 용해억제제를 더 첨가하기도 한다. 이러한 용해억제제는 베이스 수지의 노광부와 비노광부에서의 용해속도 차이를 극대화시킴으로써 레지스트의 기능을 보강시키는 역할을 하므로 레지스트 조성물에서 매우 중요한 요소이다.In addition, the chemically amplified resist is composed of a base resin and a photoacid generator (PAG) having a dissolution inhibiting group introduced to inhibit solubility. In addition, dissolution inhibitors may be further added to control the dissolution rate of the resist. This dissolution inhibitor is a very important factor in the resist composition because it serves to reinforce the function of the resist by maximizing the difference in the dissolution rate in the exposed portion and the non-exposed portion of the base resin.
그러나 대부분의 이들 레지스트들은 소자의 회로가 점점 미세화 되면서 레지스트 두께도 낮아짐에 따라, 패턴의 LER(line edge roughness)을 개선하는 것이 어려울 뿐만 아니라, 베이스 수지의 노광부와 비노광부에서의 용해속도 차이를 극대화시켜 미세 패턴을 형성시킬 수 있는 용해억제제를 개발하는 것이 어려워졌다.However, most of these resists are not only difficult to improve the line edge roughness (LER) of the pattern as the circuit of the device becomes smaller and the thickness of the resist becomes smaller. It has become difficult to develop dissolution inhibitors that can be maximized to form fine patterns.
본 발명은 노광 영역과 비노광 영역간의 용해도의 대조비가 우수한 화합물을 포함하는 포토레지스트 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a photoresist composition comprising a compound having an excellent contrast ratio of solubility between an exposed region and a non-exposed region.
또한, 본 발명에서는 상기 포토레지스트 조성물을 이용한 패턴 형성방법을 제공하는 것을 목적으로 한다. In addition, an object of the present invention is to provide a pattern forming method using the photoresist composition.
상기 목적을 달성하기 위하여 본 발명에서는 (a)포토레지스트 수지, (b)광산발생제와, (c)유기용매를 포함하는 포토레지스트 조성물에 (d)용해억제제로 사용되는 화합물을 더 포함시킨 포토레지스트 조성물을 제공한다. In order to achieve the above object, in the present invention, a photoresist comprising (a) a photoresist resin, (b) a photoacid generator, and (c) an organic solvent, further comprising a compound used as a (d) dissolution inhibitor. It provides a resist composition.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
상기 용해억제제로 사용하는 화합물은 분자량 1000 이하의 화합물로서, 하기 화학식 1과 같이 나타낼 수 있다.The compound used as the dissolution inhibitor is a compound having a molecular weight of 1000 or less, can be represented by the following formula (1).
[화학식 1][Formula 1]
상기 식에서,Where
R은 C1∼C20의 알킬, C1∼C20의 에테르 그룹을 포함하는 알킬 및 C1∼C20의 에스테르 그룹을 포함하는 알킬로 이루어진 군에서 선택되며, 이때 상기 에테르 그룹을 포함하는 알킬은 C2H5OC2H4-, CH3OCH2CH 2-, CH3OCH2- 또는 테트라히드로퓨란과 같은 고리모양의 에테르도 가능하다.R is selected from the group consisting of C 1 -C 20 alkyl, alkyl containing C 1 -C 20 ether groups and alkyl comprising C 1 -C 20 ester groups, wherein alkyl comprising said ether groups Silver C 2 H 5 OC 2 H 4- , CH 3 OCH 2 CH 2- , CH 3 OCH 2- Or cyclic ethers such as tetrahydrofuran are also possible.
상기 화학식 1의 화합물은 바람직하게 하기 화학식 1a 내지 1c로 나타낼 수 있다.The compound of Chemical Formula 1 may be preferably represented by the following Chemical Formulas 1a to 1c.
[화학식 1a][Formula 1a]
[화학식 1b][Formula 1b]
[화학식 1c][Formula 1c]
상기 화학식 1의 화합물은 상기 포토레지스트 조성물 총 중량에 대하여 0.1∼3wt%, 바람직하게는 0.5∼2wt%의 비율로 포함된다.The compound of Formula 1 is included in a ratio of 0.1 to 3wt%, preferably 0.5 to 2wt% with respect to the total weight of the photoresist composition.
상기와 같은 화학식 1의 화합물을 종래 사용하던 포토레지스트 조성물에 혼합하여 사용하는 경우, 상기 화학식 1의 화합물이 노광 시에 포토레지스트 조성물 내에서 산과 공존하다가, 후속 PEB(post-exposure bake) 공정에서 하기 반응식 1과 같이 산과 반응하여 현상액에 녹는 물질로 변하게 된다. 그러면, 노광 영역과 비노광 영역 사이에서 현상액에 대한 대조비가 향상되어 패턴의 LER이 향상되고, 우수한 패턴을 형성할 수 있다. When the compound of Formula 1 is mixed with a photoresist composition used in the prior art, the compound of Formula 1 coexists with an acid in the photoresist composition at the time of exposure, and then is subjected to the following post-exposure bake (PEB) process. As shown in Scheme 1, the reaction product is converted into a substance that is dissolved in a developing solution. Then, the contrast ratio with respect to a developing solution is improved between an exposure area and a non-exposure area, LER of a pattern can be improved and an excellent pattern can be formed.
[반응식 1]Scheme 1
또한, 상기 화학식 1의 화합물은 포토레지스트 수지 사이의 공극을 잘 메워 주기 때문에, 일반적인 포토레지스트 조성물을 적용한 식각 공정(도 1 참조) 보다 본 발명의 포토레지스트 조성물을 사용하는 식각 공정을 수행하는 경우 에칭 내성이 향상되어 후속 식각 공정 시에 공정 마진을 크게 향상시킨다(도 2 참조).In addition, since the compound of Chemical Formula 1 fills the gaps between the photoresist resins well, the etching process is performed when the etching process using the photoresist composition of the present invention is performed rather than the etching process using the general photoresist composition (see FIG. 1). The resistance is improved to greatly improve the process margin during the subsequent etching process (see FIG. 2).
또한, 상기 화학식 1의 화합물은 248㎚ 및 193㎚ 파장에서 우수한 투과율, 내열성 및 접착성을 가지므로 포토레지스트 조성물에 첨가제로 사용하여도 문제가 없다.In addition, the compound of Formula 1 has excellent transmittance, heat resistance, and adhesion at wavelengths of 248 nm and 193 nm, and thus may be used as an additive in a photoresist composition.
상기 포토레지스트 조성물의 베이스인 포토레지스트 수지는 시클로올레핀계, 아크릴레이트계, 메타아크릴레이트계, 폴리(히드록시스티렌)계 및 노볼락계 화합물 등으로 이루어진 기존의 포토레지스트용 수지를 모두 사용할 수 있으며, 바람직하게는 (i) 산에 민감한 보호기를 갖는 시클로올레핀 모이어티 (moiety), (ii) 하이드록시알킬기를 갖는 시클로올레핀 모이어티, (iii) 카르복시 또는 카르복시알킬기를 갖는 시클로올레핀 모이어티 및 (iv) 말레익 안하이드라이드로 이루어진 반복단위를 포함하는 수지이고, 더욱 바람직하게는 싸이클로올레핀계 공단량체들이 부가 중합되어 고리 (ring) 구조가 깨지지 않고 주쇄 내에 유지되어 있는 폴리(t-부틸 바이사이클로[2.2.1]헵트-5-엔-2-카르복실레이트 / 2-히드록시에틸 바이사이클로[2.2.1]헵트-5-엔-2-카르복실레이트 / 바이사이클로[2.2.1]헵트-5-엔-2-카르복실산 / 말레익안하이드라이드) 또는 기판 접착성을 향상시키기 위하여 폴리(t-부틸 바이사이클로[2.2.1]헵트-5-엔-2-카르복실레이트 / 2-히드록시에틸 바이사이클로[2.2.2]옥트-5-엔-2-카르복실레이트 / 바이사이클로[2.2.1]헵트-5-엔-2-카르복실산 / 말레익안하이드라이드) 등을 사용하는 것이 바람직하다.The photoresist resin, which is the base of the photoresist composition, may use all of the existing photoresist resins consisting of cycloolefin-based, acrylate-based, methacrylate-based, poly (hydroxystyrene) -based, and novolac-based compounds. Preferably, (i) a cycloolefin moiety having a protecting group sensitive to acid, (ii) a cycloolefin moiety having a hydroxyalkyl group, (iii) a cycloolefin moiety having a carboxy or carboxyalkyl group, and (iv ) A poly (t-butyl bicyclo) resin containing a repeating unit composed of maleic anhydride, and more preferably a cycloolefin-based comonomer is polymerized by addition to maintain a ring structure without breaking the ring structure. 2.2.1] hept-5-ene-2-carboxylate / 2-hydroxyethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate Tri / bicyclo [2.2.1] hept-5-ene-2-carboxylic acid / maleic hydride) or poly (t-butyl bicyclo [2.2.1] hept-5- to improve substrate adhesion En-2-carboxylate / 2-hydroxyethyl bicyclo [2.2.2] oct-5-ene-2-carboxylate / bicyclo [2.2.1] hept-5-ene-2-carboxylic acid / Maleic anhydride) and the like.
또한, 상기 포토레지스트 수지는 포토레지스트 조성물의 전체 중량에 대하여 5∼20wt%, 바람직하게는 8∼15wt%의 비율로 포함된다.In addition, the photoresist resin is included in a ratio of 5 to 20 wt%, preferably 8 to 15 wt% with respect to the total weight of the photoresist composition.
또한, 상기 광산발생제는 빛에 의해 산을 발생할 수 있는 화합물이면 무엇이든 사용가능하며, US 5,212,043 (1993. 5. 18), WO 97/33198 (1997. 9. 12), WO 96/37526 (1996. 11. 28), EP 0 794 458 (1997. 9. 10) EP 0 789 278 (1997. 8. 13), US 5,750,680 (1998. 5. 12), US 6,051,678 (2000. 4. 18), GB 2,345,286 A (2000. 7. 5), US 6,132,926 (2000. 10. 17), US 6,143,463 (2000. 11. 7) 및 US 6,150,069 (2000. 11. 21) 등에 개시된 것을 포함하고, 주로 황화염계 또는 오니움염계 화합물을 사용한다. 특히, 157nm 및 193nm에서 흡광도가 적은 프탈이미도트리플루오로메탄술포네이트 (phthalimidotrifluoromethane sulfonate), 디니트로벤질토실레이트 (dinitrobenzyltosylate), n-데실디술폰 (n-decyl disulfone) 및 나프틸이미도트리플루오로메탄술포네이트 (naphthylimido trifluoromethane sulfonate)로 이루어진 군으로부터 선택된 것을 사용하는 것이 바람직하고, 이와 함께, 디페닐요도염 헥사플루오로포스페이트, 디페닐요도염 헥사플루오로 아르세네이트, 디페닐요도염 헥사플루오로 안티모네이트, 디페닐파라메톡시페닐설포늄 트리플레이트, 디페닐파라톨루에닐설포늄 트리플레이트, 디페닐파라이소부틸페닐설포늄 트리플레이트, 트리페닐설포늄 헥사플루오로 아르세네이트, 트리페닐설포늄 헥사플루오로 안티모네이트, 트리페닐설포늄 트리플레이트 및 디부틸나프틸설포늄 트리플레이트로 이루어진 군으로부터 선택된 광산발생제를 겸용할 수 있으며, 상기 포토레지스트 수지 100 중량부에 대해 0.1 내지 10 중량부의 비율로 사용한다. Further, the photoacid generator may be used as long as it is a compound capable of generating an acid by light, US 5,212,043 (May 18, 1993), WO 97/33198 (September 12, 1997), WO 96/37526 ( Nov. 28, 1996, EP 0 794 458 (October 10, 1997) EP 0 789 278 (August 13, 1997), US 5,750,680 (May 12, 1998), US 6,051,678 (April 18, 2000), GB 2,345,286 A (July 5, 2000), US 6,132,926 (October 17, 2000), US 6,143,463 (Nov. 7, 2000), and US 6,150,069 (November 21, 2000), and the like, and are mainly sulfur sulfide systems Or onium salt compounds. In particular, low absorbance phthalimidotrifluoromethane sulfonate, dinitrobenzyltosylate, n-decyl disulfone and naphthylimidotrifluoromethane at 157 nm and 193 nm Preference is given to using those selected from the group consisting of naphthylimido trifluoromethane sulfonate, together with diphenylurodoxyl hexafluorophosphate, diphenylurodoxyl hexafluoro arsenate, diphenylurodoxyl hexafluoro antimonate, Diphenylparamethoxyphenylsulfonium triflate, diphenylparatoluenylsulfonium triflate, diphenylparaisobutylphenylsulfonium triflate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium hexafluoro Antimonate, triphenylsulfonium triflate and dibutylnaphthylsulfonium tri A photoacid generator selected from the group consisting of plates may be used, and it is used in a ratio of 0.1 to 10 parts by weight based on 100 parts by weight of the photoresist resin.
이때, 광산발생제가 0.1 중량부 이하로 사용될 때에는 포토레지스트의 광에 대한 민감도가 취약하게 되고 10 중량부 이상으로 사용될 때에는 광산발생제가 원자외선을 많이 흡수하고 산이 다량 발생되어 단면이 좋지 않은 패턴을 얻게 된다.In this case, when the photoacid generator is used at 0.1 parts by weight or less, the sensitivity of the photoresist to light is weak. When the photoacid generator is used at 10 parts by weight or more, the photoacid generator absorbs a lot of ultraviolet rays and a large amount of acid is generated to obtain a pattern having a bad cross section. do.
상기 유기 용매는 통상적으로 사용되는 것은 무엇이든 사용가능하며, US 5,212,043 (1993. 5. 18), WO 97/33198 (1997. 9. 12), WO 96/37526 (1996. 11. 28), EP 0 794 458 (1997. 9. 10) EP 0 789 278 (1997. 8. 13), US 5,750,680 (1998. 5. 12), US 6,051,678 (2000. 4. 18), GB 2,345,286 A (2000. 7. 5), US 6,132,926 (2000. 10. 17), US 6,143,463 (2000. 11. 7) 및 US 6,150,069 (2000. 11. 21) 등에 개시된 것을 포함하고, 바람직하게는 디에틸렌글리콜디에틸에테르 (diethylene glycol diethyl ether), 메틸 3-메톡시프로피오네이트, 에틸 3-에톡시프로피오네이트, 프로필렌글리콜 메틸에테르아세테이트, 사이클로헥사논 또는 2-헵타논 등을 단독으로 또는 혼합하여 사용할 수 있으며, 상기 포토레지스트 수지 100 중량부에 대해 100 내지 2000 중량부의 비율로 사용되는데, 이는 원하는 두께의 포토레지스트 막을 얻기 위한 것이다.The organic solvent can be any one commonly used, US 5,212,043 (May 18, 1993), WO 97/33198 (September 12, 1997), WO 96/37526 (Nov. 28, 1996), EP 0 794 458 (September 10, 1997) EP 0 789 278 (August 13, 1997), US 5,750,680 (May 12, 1998), US 6,051,678 (April 18, 2000), GB 2,345,286 A (2000. 7. 5), US 6,132,926 (October 17, 2000), US 6,143,463 (11/7/2000) and US 6,150,069 (11/21/2000) and the like, preferably diethylene glycol diethyl ether diethyl ether), methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate, cyclohexanone or 2-heptanone, and the like can be used alone or in combination. It is used in the ratio of 100-2000 weight part with respect to 100 weight part of resin, in order to obtain the photoresist film of desired thickness.
또한, 본 발명에서는 하기와 같은 단계로 이루어지는 포토레지스트 패턴 형성방법을 제공한다:In addition, the present invention provides a method of forming a photoresist pattern consisting of the following steps:
(a) 상기 화학식 1의 화합물이 더 포함된 본 발명의 포토레지스트 조성물을 피식각층 상부에 도포하여 포토레지스트 막을 형성하는 단계;(a) forming a photoresist film by applying the photoresist composition of the present invention further comprising the compound of Formula 1 on the etched layer;
(b) 상기 포토레지스트 막을 노광하는 단계; 및(b) exposing the photoresist film; And
(c) 상기 결과물을 현상하여 원하는 패턴을 얻는 단계.(c) developing the result to obtain a desired pattern.
상기 과정에서, (b)단계의 노광전 및/또는 노광후에 베이크 공정을 실시하는 단계를 더 포함할 수 있으며, 이러한 베이크 공정은 70 내지 200℃에서 수행된다.In the above process, the method may further include performing a baking process before and / or after exposure in step (b), and the baking process is performed at 70 to 200 ° C.
또한, 상기 노광공정은 광원으로서 KrF(248nm), ArF(193nm), VUV(157nm), EUV(13nm), E-빔, X-선 또는 이온빔을 이용하여, 1 내지 100 mJ/cm2의 노광에너지로 수행되는 것이 바람직하다.In addition, the exposure process is an exposure of 1 to 100 mJ / cm 2 using KrF (248 nm), ArF (193 nm), VUV (157 nm), EUV (13 nm), E-beam, X-ray or ion beam as a light source. It is preferably carried out with energy.
또한 본 발명에서는 상기 본 발명의 포토레지스트 조성물을 이용하여 제조된 반도체 소자를 제공한다.The present invention also provides a semiconductor device manufactured using the photoresist composition of the present invention.
이하 본 발명을 실시예에 의하여 상세히 설명한다. 단 실시예는 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by examples. However, the examples are only to illustrate the invention and the present invention is not limited by the following examples.
제조예 1. 화학식 1a 화합물의 제조Preparation Example 1 Preparation of Compound of Formula 1a
1,2:5,6-디-오르소-사이클로헥실리덴-알파-디-클루코푸라노스[1,2:5,6-di-o-cyclohexylidene-α-D-glucofuranose](0.05M)와 디-터셔리-부틸-디카보네이트(di-tert- butyl-dicarbonate)(0.055M)를 벤젠 용액(50mL)에 녹이고, 상온에서 교반하면서 트리에틸아민(0.055M)을 천천히 가해주었다. 반응 6시간 후, 반응 혼합물에 1M NaOH 수용액을 첨가하여 5분 더 교반 시킨 다음, 수용액 층을 제거하였다. 남아있는 벤젠용액에 물 100mL를 다시 첨가하고, 제거한 후, 상기 벤젠 용액을 마그네슘설페이트(MgSO4)로 탈수시킨 다음, 여과 및 증류하여 상기 화학식 1a의 화합물을 얻었다(89%)1,2: 5,6-di-ortho-cyclohexylidene-alpha-di-glucofuranose [1,2: 5,6-di-o-cyclohexylidene-α-D-glucofuranose] (0.05M ) And di-tert-butyl-dicarbonate (0.055M) were dissolved in a benzene solution (50 mL), and triethylamine (0.055M) was added slowly with stirring at room temperature. After 6 hours of reaction, 1M NaOH aqueous solution was added to the reaction mixture, which was stirred for 5 minutes, and the aqueous solution layer was removed. 100 mL of water was added to the remaining benzene solution, and after removal, the benzene solution was dehydrated with magnesium sulfate (MgSO 4 ), filtered and distilled to obtain the compound of Chemical Formula 1a (89%).
제조예 2. 화학식 1b 화합물의 제조Preparation Example 2 Preparation of Compound of Formula 1b
1,2:5,6-디-오르소-사이클로헥실리덴-알파-디-클루코푸라노스(0.05M)를 테트라히드로퓨란에 녹인 후, 0℃에서 n-부틸 리튬(2.5M solution in hexane 20ml)(0.055M)과 브로모메틸-터셔리-부틸-카르복실레이트(bromomethyl-tert-butyl- carboxylate)(0.055M)를 가하였다. 상기 결과물 용액을 상온에서 10시간 교반한 후, 반응 혼합물을 증류하고, 벤젠 100ml 와 물 100ml를 첨가하여 저어 준 다음 물 층을 제거하였다. 상기 결과물에 물 100ml를 더 첨가하고, 상기 물 층을 제거한 다음, 벤젠 층을 탈수시키고, 여과 및 증류하여 상기 화학식 1b의 화합물을 얻었다(84%)1,2: 5,6-Di-ortho-cyclohexylidene-alpha-di-glucofuranose (0.05M) was dissolved in tetrahydrofuran and then n-butyl lithium (2.5M solution in 20 ml of hexane (0.055M) and bromomethyl-tert-butyl-carboxylate (0.055M) were added. After stirring the resulting solution at room temperature for 10 hours, the reaction mixture was distilled off, stirred by adding 100 ml of benzene and 100 ml of water, and then removing the water layer. 100 ml of water was further added to the resultant, the water layer was removed, the benzene layer was dehydrated, filtered and distilled to obtain the compound of Formula 1b (84%).
제조예 3. 화학식 1c 화합물의 제조Preparation Example 3 Preparation of Compound of Formula 1c
1,2:5,6-디-오르소-사이클로헥실리덴-알파-디-클루코푸라노스(0.05M)를 테트라히드로퓨란에 용해시킨 다음, 0℃에서 n-부틸 리튬(2.5M solution in hexane 20ml)(0.055M)과 클로로메틸-에틸 에테르(chloromethyl ethyl ether)(0.055M)을 가하였다. 상기 결과물 용액을 상온에서 10시간 교반한 후, 반응 혼합물을 증류하고, 벤젠 100ml 와 물 100ml를 첨가하고 저어 준 다음 물 층을 제거하였다. 상기 결과물에 물 100ml를 더 첨가한 후, 상기 물 층을 제거한 다음, 벤젠 층을 탈수시키고, 여과 및 증류하여 상기 화학식 1c의 화합물을 얻었다(92%)1,2: 5,6-di-ortho-cyclohexylidene-alpha-di-glucofuranose (0.05M) was dissolved in tetrahydrofuran and then n-butyl lithium (2.5M solution at 0 ° C). in hexane 20ml) (0.055M) and chloromethyl ethyl ether (0.055M) were added. After stirring the resulting solution at room temperature for 10 hours, the reaction mixture was distilled off, 100 ml of benzene and 100 ml of water were added and stirred, and then the water layer was removed. After further adding 100 ml of water to the resultant, the water layer was removed, the benzene layer was dehydrated, filtered and distilled to obtain the compound of Chemical Formula 1c (92%).
비교예 1. 종래 포토레지스트 조성물 및 이를 이용한 패턴 형성Comparative Example 1. Conventional Photoresist Composition and Pattern Formation Using the Same
포토레지스트 조성물(H200D4; 동진쎄미켐(주)) 20ml을 실리콘 웨이퍼에 스핀 코팅하고, 130℃에서 90초 동안 베이크하였다. 그리고, ArF 노광장비로 노광하고 이어서 130℃에서 90초 동안 다시 베이크하고 2.38 wt% TMAH 현상액에서 40초간 현상하여 0.08㎛ L/S의 패턴을 얻었다(도 3 참조).20 ml of a photoresist composition (H200D4; Dongjin Semichem Co., Ltd.) was spin coated on a silicon wafer and baked at 130 ° C. for 90 seconds. Then, the resultant was exposed with an ArF exposure apparatus and subsequently baked again at 130 ° C. for 90 seconds, and developed for 40 seconds in a 2.38 wt% TMAH developer to obtain a pattern of 0.08 μm L / S (see FIG. 3).
실시예 1. 포토레지스트 조성물의 제조 및 패턴 형성 방법Example 1 Preparation of Photoresist Composition and Forming Pattern
포토레지스트 조성물(H200D4) 20ml에 상기 제조예 1의 화학식 1a의 화합물(4g)을 용해시킨 후, 0.20㎛ 필터로 여과시켜 포토레지스트 조성물을 제조하였다.After dissolving the compound (4 g) of Chemical Formula 1a of Preparation Example 1 in 20 ml of the photoresist composition (H200D4), a photoresist composition was prepared by filtration with a 0.20 μm filter.
상기 조성물을 실리콘 웨이퍼에 3000rpm으로 스핀 코팅하고, 130℃에서 90초 동안 베이크하였다. 그리고, ArF 노광장비로 노광하고 이어서 130℃에서 90초 동안 다시 베이크하고 2.38 wt% TMAH 현상액에서 40초간 현상하여 LER이 개선된 0.08㎛ L/S의 패턴을 얻었다(도 4 참조).The composition was spin coated onto a silicon wafer at 3000 rpm and baked at 130 ° C. for 90 seconds. Then, it was exposed with an ArF exposure equipment and then baked again for 90 seconds at 130 ° C. and developed for 40 seconds in a 2.38 wt% TMAH developer to obtain a pattern of 0.08 μm L / S with improved LER (see FIG. 4).
실시예 2. 포토레지스트 조성물의 제조 및 패턴 형성 방법Example 2. Preparation of Photoresist Composition and Forming Pattern
포토레지스트 조성물(H200D4) 20ml에 상기 제조예 2의 화학식 1b의 화합물(4g)을 용해시킨 후, 0.20㎛ 필터로 여과시켜 포토레지스트 조성물을 제조하였다.After dissolving the compound (4 g) of Chemical Formula 1b of Preparation Example 2 in 20 ml of the photoresist composition (H200D4), a photoresist composition was prepared by filtration with a 0.20 μm filter.
상기 조성물을 실리콘 웨이퍼에 3000rpm으로 스핀 코팅하고, 130℃에서 90초 동안 베이크하였다. 그리고, ArF 노광장비로 노광하고 이어서 130℃에서 90초 동안 다시 베이크하고 2.38 wt% TMAH 현상액에서 40초간 현상하여 LER이 개선된 0.08㎛ L/S의 패턴을 얻었다(도 5 참조).The composition was spin coated onto a silicon wafer at 3000 rpm and baked at 130 ° C. for 90 seconds. Then, the resultant was exposed with an ArF exposure apparatus and subsequently baked again at 130 ° C. for 90 seconds and developed in 2.38 wt% TMAH developer for 40 seconds to obtain a pattern of 0.08 μm L / S with improved LER (see FIG. 5).
실시예 3. 본 발명의 포토레지스트 조성물의 제조 및 패턴 형성 방법Example 3 Preparation and Pattern Forming Method of Photoresist Composition of the Present Invention
포토레지스트 조성물(H200D4) 20ml에 상기 제조예 3의 화학식 1c의 화합물(4g)을 용해시킨 후, 0.20㎛ 필터로 여과시켜 포토레지스트 조성물을 제조하였다.After dissolving the compound (4 g) of Chemical Formula 1c of Preparation Example 3 in 20 ml of the photoresist composition (H200D4), a photoresist composition was prepared by filtration with a 0.20 μm filter.
상기 조성물을 실리콘 웨이퍼에 3000rpm으로 스핀 코팅하고, 130℃에서 90초 동안 베이크하였다. 그리고, ArF 노광장비로 노광하고 이어서 130℃에서 90초 동안 다시 베이크하고 2.38 wt% TMAH 현상액에서 40초간 현상하여 LER이 개선된 0.08㎛ L/S의 패턴을 얻었다(도 6 참조).The composition was spin coated onto a silicon wafer at 3000 rpm and baked at 130 ° C. for 90 seconds. Then, the resultant was exposed with an ArF exposure apparatus and subsequently baked again at 130 ° C. for 90 seconds and developed in 2.38 wt% TMAH developer for 40 seconds to obtain a pattern of 0.08 μm L / S with improved LER (see FIG. 6).
이상에서 살펴본 바와 같이, 상기 화학식 1의 화합물을 포함하는 포토레지스트 조성물은 248㎚ 및 193㎚ 파장에서 노광 영역과 비노광 영역의 현상액에 대한 대조비가 향상되어 LER이 향상된 우수한 패턴을 형성할 수 있다.As described above, the photoresist composition including the compound of Chemical Formula 1 may form an excellent pattern with improved LER by increasing the contrast ratio of the developer in the exposed region and the non-exposed region at wavelengths of 248 nm and 193 nm.
또한, 본 발명의 포토레지스트 조성물은 폴리머 사이의 공극을 잘 메워 주기 때문에 에칭 내성이 향상되어 후속 식각 공정 시에 공정 마진을 크게 향상시킬 수 있다.In addition, since the photoresist composition of the present invention fills the gaps between the polymers well, the etching resistance is improved, and thus the process margin may be greatly improved in the subsequent etching process.
도 1은 종래 일반적인 포토레지스트 조성물을 적용한 식각 공정 후의 남은 유기층 패턴 사진.1 is a photograph of the organic layer pattern remaining after the etching process to which the conventional photoresist composition is applied.
도 2는 본 발명의 포토레지스트 조성물을 적용한 식각 공정 후의 남은 유기층 패턴 사진.Figure 2 is a photograph of the organic layer pattern remaining after the etching process to which the photoresist composition of the present invention is applied.
도 3은 종래 포토레지스트 조성물을 이용한 비교예 1에 따른 패턴 사진.Figure 3 is a pattern photo according to Comparative Example 1 using a conventional photoresist composition.
도 4는 본 발명의 포토레지스트 조성물을 이용한 실시예 1에 따른 패턴 사진.Figure 4 is a pattern photo according to Example 1 using a photoresist composition of the present invention.
도 5는 본 발명의 포토레지스트 조성물을 이용한 실시예 2에 따른 패턴 사진.5 is a pattern photo according to Example 2 using the photoresist composition of the present invention.
도 6은 본 발명의 포토레지스트 조성물을 이용한 실시예 3에 따른 패턴 사진.6 is a pattern photo according to Example 3 using the photoresist composition of the present invention.
Claims (15)
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| KR1020040000123A KR20050071802A (en) | 2004-01-02 | 2004-01-02 | Photoresist composition and method for forming photoresist pattern using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20210053154A (en) * | 2019-10-30 | 2021-05-11 | 타이완 세미콘덕터 매뉴팩쳐링 컴퍼니 리미티드 | Negative tone photoresist for euv lithography |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20210053154A (en) * | 2019-10-30 | 2021-05-11 | 타이완 세미콘덕터 매뉴팩쳐링 컴퍼니 리미티드 | Negative tone photoresist for euv lithography |
| US11550220B2 (en) | 2019-10-31 | 2023-01-10 | Taiwan Semiconductor Manufacturing Co., Ltd. | Negative tone photoresist for EUV lithography |
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