KR101008373B1 - Stripper composition for photoresist and method for stripping photoresist - Google Patents
Stripper composition for photoresist and method for stripping photoresist Download PDFInfo
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- KR101008373B1 KR101008373B1 KR1020090115243A KR20090115243A KR101008373B1 KR 101008373 B1 KR101008373 B1 KR 101008373B1 KR 1020090115243 A KR1020090115243 A KR 1020090115243A KR 20090115243 A KR20090115243 A KR 20090115243A KR 101008373 B1 KR101008373 B1 KR 101008373B1
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- South Korea
- Prior art keywords
- photoresist
- group
- formula
- stripper composition
- carbon atoms
- Prior art date
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 124
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000007797 corrosion Effects 0.000 claims abstract description 28
- 238000005260 corrosion Methods 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- -1 amine compound Chemical class 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical group 0.000 claims description 8
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 6
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 5
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 5
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 229940043237 diethanolamine Drugs 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 2
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 claims description 2
- QZXIXSZVEYUCGM-UHFFFAOYSA-N 2-aminopropan-2-ol Chemical compound CC(C)(N)O QZXIXSZVEYUCGM-UHFFFAOYSA-N 0.000 claims description 2
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical group CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000004492 methyl ester group Chemical group 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 239000010949 copper Substances 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 229910001182 Mo alloy Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- IAJLTMBBAVVMQO-UHFFFAOYSA-N 1h-benzimidazol-2-ylmethanol Chemical compound C1=CC=C2NC(CO)=NC2=C1 IAJLTMBBAVVMQO-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- SILNNFMWIMZVEQ-UHFFFAOYSA-N 1,3-dihydrobenzimidazol-2-one Chemical compound C1=CC=C2NC(O)=NC2=C1 SILNNFMWIMZVEQ-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 description 1
- XEGAKAFEBOXGPV-UHFFFAOYSA-N 2,3,3a,4-tetrahydro-1h-benzotriazole Chemical compound C1C=CC=C2NNNC12 XEGAKAFEBOXGPV-UHFFFAOYSA-N 0.000 description 1
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D9/00—Chemical paint or ink removers
- C09D9/005—Chemical paint or ink removers containing organic solvents
-
- 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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
-
- 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
-
- 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
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- C11D2111/22—
Abstract
Description
본 발명은 포토레지스트 스트리퍼 조성물 및 이를 이용한 포토레지스트 박리방법에 관한 것이다.The present invention relates to a photoresist stripper composition and a photoresist stripping method using the same.
반도체 집적회로 또는 액정 표시 소자의 미세 회로 제조 공정은 기판상에 형성된 알루미늄, 알루미늄 합금, 구리, 구리 합금, 몰리브덴, 몰리브덴 합금 등의 도전성 금속막, 또는 실리콘 산화막, 실리콘 질화막 등의 절연막에 포토레지스트를 균일하게 도포하고, 이것을 선택적으로 노광, 현상 처리하여 포토레지스트 패턴을 형성한 다음, 패턴화된 포토레지스트막을 마스크로 하여 상기 도전성 금속막이나 절연막을 습식 또는 건식으로 에칭하여 미세 회로 패턴을 포토레지스트 하부층에 전사한 후 불필요해진 포토레지스트층을 스트리퍼(박리액)로 제거하는 공정으로 진행된다.The process of manufacturing a semiconductor integrated circuit or a microcircuit of a liquid crystal display device is performed by applying a photoresist to a conductive metal film such as aluminum, aluminum alloy, copper, copper alloy, molybdenum, molybdenum alloy, or an insulating film such as a silicon oxide film or a silicon nitride film formed on a substrate. Apply uniformly, selectively expose and develop the photoresist pattern, and then wet or dry etch the conductive metal film or the insulating film using the patterned photoresist film as a mask to form a fine circuit pattern underlayer of photoresist. The transfer proceeds to a step of removing the unnecessary photoresist layer after stripping with a stripper (peeling liquid).
상기 반도체 소자 및 액정 표시 소자 제조용 포토레지스트를 제거하기 위한 스트리퍼가 갖추어야 할 기본 특성은 다음과 같다.Basic characteristics of the stripper for removing the photoresist for manufacturing the semiconductor device and the liquid crystal display device are as follows.
먼저, 저온에서 단시간 내에 포토레지스트를 박리할 수 있어야 하고, 세 척(rinse) 후 기판 상에 포토레지스트 잔류물을 남기지 않아야 하는 우수한 박리 능력을 가져야 한다. 또한, 포토레지스트 하부층의 금속막이나 절연막을 손상시키지 않아야 하는 저부식성을 가져야 한다. 또한, 스트리퍼를 이루는 용제간에 상호반응이 일어나면 스트리퍼의 저장 안정성이 문제되고 스트리퍼 제조시의 혼합순서에 따라 다른 물성을 보일 수 있으므로, 혼합 용제간의 무반응성 및 고온 안정성이 있어야 한다. 또한, 작업자의 안전이나 폐기 처리시의 환경 문제를 고려하여 저독성이어야 한다. 또한, 고온 공정에서 포토레지스트 박리가 진행될 경우 휘발이 많이 일어나면 구성 성분비가 빨리 변하게 되어 스트리퍼의 공정 안정성과 작업 재현성이 저하되므로, 저휘발성이어야 한다. 또한, 일정 스트리퍼 양으로 처리할 수 있는 기판 수가 많아야 하고, 스트리퍼를 구성하는 성분의 수급이 용이하고 저가이며 폐스트리퍼의 재처리를 통한 재활용이 가능하여 경제성이 있어야 한다.First, it must be able to delaminate the photoresist in a short time at low temperature and have a good delamination capability that should not leave photoresist residue on the substrate after rinse. In addition, it should have low corrosion resistance that should not damage the metal film or insulating film of the photoresist underlayer. In addition, if the interaction between the solvent constituting the stripper occurs, the storage stability of the stripper may be a problem and may exhibit different physical properties depending on the mixing sequence in the stripper manufacturing, there should be a non-reactive and high temperature stability between the mixed solvent. In addition, it should be low toxicity in consideration of the safety of the worker or environmental problems in disposal. In addition, when the photoresist stripping proceeds in a high temperature process, if a lot of volatilization occurs, the component ratio changes rapidly, and thus the process stability and work reproducibility of the stripper are lowered, and therefore, it must be low volatility. In addition, the number of substrates that can be processed with a certain amount of stripper should be large, the supply of the components constituting the stripper is easy, low cost, and can be recycled through the reprocessing of the waste stripper to be economical.
이러한 조건들을 충족시키기 위해 다양한 포토레지스트용 스트리퍼 조성물이 개발되고 있다. 그러나, 보다 우수한 포토레지스트 스트리퍼 조성물로서, 조성물 내 다른 성분들과 반응하지 않고, 불필요한 부산물을 발생시키지 않으며, 특히 포토레지스트 하부층의 금속막이나 절연막을 손상시키지 않아야 하는 저부식성을 갖는 포토레지스트 스트리퍼 조성물의 개발이 필요한 실정이다.Various stripper compositions for photoresists have been developed to meet these conditions. However, as a better photoresist stripper composition, it has a low corrosion resistance that does not react with other components in the composition, does not generate unnecessary by-products, and in particular does not damage the metal film or insulating film of the photoresist underlayer. Development is needed.
본 발명은 포토레지스트 박리 효과가 우수하면서, 포토레지스트 박리 공정을 반복하는 경우에도 포토레지스트의 하부막을 부식시키지 않는 포토레지스트 스트리퍼 조성물을 제공하는 것을 목적으로 한다. 특히, 포토레지스트 하부막으로서 Cu막/Mo막 다층막을 사용하는 경우에도 하부막의 부식 없이 효율적으로 포토레지스트를 박리할 수 있는 포토레지스트 스트리퍼 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a photoresist stripper composition which is excellent in photoresist stripping effect and which does not corrode a lower film of the photoresist even when the photoresist stripping process is repeated. In particular, an object of the present invention is to provide a photoresist stripper composition capable of efficiently peeling photoresist without corrosion of the lower film even when a Cu film / Mo film multilayer film is used as the lower photoresist film.
상기 목적을 달성하기 위하여, 본 발명은In order to achieve the above object, the present invention
1) 하기 화학식 1로 표시되는 화합물, 및1) a compound represented by the following formula (1), and
2) 용매2) solvent
를 포함하는 포토레지스트 스트리퍼 조성물을 제공한다.It provides a photoresist stripper composition comprising a.
[화학식 1][Formula 1]
상기 화학식 1에서, R, R' 및 R"은 서로 동일하거나 상이하고, 각각 독립적으로 탄소수 1 내지 6의 직쇄 또는 분지쇄의 알킬렌이다.In Formula 1, R, R 'and R "are the same as or different from each other, and are each independently a linear or branched alkylene having 1 to 6 carbon atoms.
또한, 본 발명은 상기 포토레지스트 스트리퍼 조성물을 이용하여 포토레지스트를 박리하는 방법을 제공한다.The present invention also provides a method of peeling a photoresist using the photoresist stripper composition.
본 발명에 따른 포토레지스트 스트리퍼 조성물은 포토레지스트 박리 속도, 박리 효율 등이 우수할 뿐만 아니라, 포토레지스트의 하부막에 대한 부식 방지력이 우수하다.The photoresist stripper composition according to the present invention is not only excellent in photoresist peeling rate, peeling efficiency, etc., but also excellent in corrosion protection of the lower layer of the photoresist.
이하에서 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
디스플레이의 고해상도, 대화면화가 진행되면서 저저항인 구리(Cu) 배선이 필수적으로 요구되고 있다. Cu의 경우, 유리와 밀착력이 낮고 하부막으로의 확산이 심하여 확산 방지막으로서 다른 금속막이 필요하다. 일반적으로, 몰리브덴(Mo) 합금을 이용한 Cu/Mo합금의 이중막 구조가 현재 적용되고 있다.As high resolution and large screens of displays progress, low resistance copper (Cu) wiring is indispensable. In the case of Cu, the adhesion to glass is low and the diffusion into the lower film is severe, and another metal film is needed as the diffusion preventing film. In general, a double film structure of a Cu / Mo alloy using a molybdenum (Mo) alloy is currently applied.
그러나, Mo 합금의 경우, 증착 장치 내 파티클(particle) 오염, 예컨대 Ti 입자에 의한 파티클 오염이 잦아 수율을 저하시키는 단점이 있으며, 또한 타겟(target)의 단가가 높은 단점이 있다.However, in the case of Mo alloy, particle contamination in the deposition apparatus, for example, particle contamination by Ti particles is frequent, which lowers the yield, and also has a disadvantage in that the cost of the target is high.
Mo 합금 대신 Mo를 하부막에 적용하는 경우, Mo가 Cu와 갈바닉 커플(galvanic couple)을 형성하므로, 고온 염기성인 포토레지스트 스트리퍼를 이용하는 경우 부식이 크게 발생될 수 있다. 따라서, 포토레지스트 스트리퍼에 의한 부식 문제로 인하여, 포토레지스트 하부막으로써 아직까지 Cu/Mo를 적용한 업체는 없었다.When Mo is applied to the lower layer instead of the Mo alloy, since Mo forms a galvanic couple with Cu, corrosion may occur greatly when using a high temperature basic photoresist stripper. Therefore, due to the problem of corrosion by the photoresist stripper, no company has applied Cu / Mo as a photoresist underlayer yet.
그러나, 본 발명에 따른 포토레지스트 스트리퍼 조성물은 상기 화학식 1로 표시되는 화합물을 포함함으로써, 포토레지스트 하부막의 부식 문제를 해결할 수 있을 뿐만 아니라, 종래의 유기 아민 화합물을 이용하는 경우보다 박리 속도가 우수한 특성이 있다.However, the photoresist stripper composition according to the present invention includes a compound represented by Chemical Formula 1, which not only solves the problem of corrosion of the photoresist underlayer, but also exhibits superior peeling properties than those of conventional organic amine compounds. have.
종래에는 Mo막의 두께가 10nm 이하인 수준에서는 갈바닉 현상이 너무 심해서, 포토레지스트 스트리퍼 조성물의 적용 자체가 불가능하였으나, 본 발명에서는 갈바닉 현상을 제어할 수 있으므로 Mo막이 10nm 이하인 경우에도 적용이 가능하다.Conventionally, the galvanic phenomenon is too severe at the level of 10 nm or less of the Mo film, the application of the photoresist stripper composition itself is impossible, but the galvanic phenomenon can be controlled in the present invention can be applied even when the Mo film is 10 nm or less.
또한, 공정 중 불량이 발생하면 재작업(rework)을 하게 되는데, 포토레지스트 박리공정의 횟수에 따라 부식이 더 심해져 폐기 처분할 수 밖에 없었으나, 본 발명에서는 포토레지스트 박리공정을 수 회 반복하는 경우에도 부식의 문제를 일으키지 않으므로 재작업이 가능하다.In addition, if a defect occurs during the process is to be reworked, depending on the number of times the photoresist stripping process is more severe corrosion, but was forced to discard, but in the present invention if the photoresist stripping process is repeated several times Even though it does not cause the problem of corrosion, it is possible to rework.
본 발명에 따른 포토레지스트 스트리퍼 조성물은 1) 상기 화학식 1로 표시되는 화합물 및 2) 용매를 포함하는 것을 특징으로 한다.Photoresist stripper composition according to the invention is characterized in that it comprises 1) the compound represented by the formula (1) and 2) a solvent.
상기 화학식 1에 있어서, R은 메틸렌인 것이 바람직하고, R'는 탄소수 2 이상의 알킬렌, 더욱 바람직하게는 에틸렌인 것이 바람직하다. 바람직한 화합물의 구조식은 하기 화학식 1-1과 같다.In Formula 1, R is preferably methylene, and R 'is preferably C2 or more alkylene, more preferably ethylene. Structural formula of a preferred compound is represented by the formula 1-1.
[화학식 1-1][Formula 1-1]
상기 화학식 1-1에서, R"는 탄소수 1 내지 6의 직쇄 또는 분지쇄의 알킬렌이다.In Formula 1-1, R ″ is a linear or branched alkylene having 1 to 6 carbon atoms.
상기 화학식 1-1로 표시되는 화합물은 하기 화학식 1-2로 표시되는 것이 더욱 바람직하다.The compound represented by Chemical Formula 1-1 is more preferably represented by the following Chemical Formula 1-2.
[화학식 1-2][Formula 1-2]
상기 화학식 1로 표시되는 화합물은 끓는점(b.p.)이 54 ~ 58℃/3.3torr 인 것이 바람직하다.It is preferable that the compound represented by Chemical Formula 1 has a boiling point (b.p.) of 54 to 58 ° C / 3.3torr.
상기 화학식 1로 표시되는 화합물은 하기 화학식 2로 표시되는 화합물을 (RO)n (여기서, R은 탄소수 1 내지 6의 알킬렌이고, n은 1 내지 20의 정수임) 및 용매의 존재하에서 환류(reflux)시키는 단계를 포함하는 방법에 의하여 제조될 수 있다.The compound represented by Chemical Formula 1 is a compound represented by the following Chemical Formula 2 (RO) n (wherein R is alkylene having 1 to 6 carbon atoms, n is an integer of 1 to 20) and reflux in the presence of a solvent (reflux It may be prepared by a method comprising the step of).
[화학식 2][Formula 2]
H2N-R'-NH-R"-OHH 2 N-R'-NH-R "-OH
상기 화학식 2에서, R' 및 R"은 서로 동일하거나 상이하고, 각각 독립적으로 탄소수 1 내지 6의 직쇄 또는 분지쇄의 알킬렌이다.In Formula 2, R ′ and R ″ are the same as or different from each other, and are each independently a linear or branched alkylene having 1 to 6 carbon atoms.
상기 방법에 있어서, R은 메틸렌, R' 및 R"은 에틸렌, n은 1인 것이 바람직하다.In the above method, it is preferable that R is methylene, R 'and R "are ethylene, and n is 1.
상기 방법에 있어서, 용매는 특별히 한정되는 것은 아니나, 벤젠, 메탄올과 같은 알코올류 등이 바람직하다.In the above method, the solvent is not particularly limited, but alcohols such as benzene and methanol are preferable.
상기 방법에 있어서, 상기 환류를 위하여 상기 반응물들을 가열할 수 있다. 상기 환류 온도는 용매의 끓는점에 따라 당업자가 용이하게 결정할 수 있다. 예컨대, 용매가 벤젠인 경우에는 85 ~ 95℃인 것이 바람직하다. 상기 환류 시간은 30분 내지 2시간이 바람직하고, 약 1시간인 것이 더욱 바람직하다. 상기 방법은 상압에서 수행될 수 있다.In this method, the reactants may be heated for the reflux. The reflux temperature can be readily determined by one skilled in the art depending on the boiling point of the solvent. For example, when the solvent is benzene, it is preferable that it is 85-95 degreeC. The reflux time is preferably 30 minutes to 2 hours, more preferably about 1 hour. The method can be carried out at atmospheric pressure.
상기 제조방법의 일 구체예를 하기 반응식 1에 나타내었다.One embodiment of the preparation method is shown in Scheme 1 below.
[반응식 1]Scheme 1
상기 화학식 1로 표시되는 화합물의 함량은 전체 조성물 총중량 중 1 ~ 35 중량%인 것이 바람직하며, 더욱 바람직하게는 3 ~ 30 중량%이다. 만일, 상기 1) 유기 아민 화합물의 함량이 1 중량% 미만인 경우에는 변성된 포토레지스트에 대한 박리력이 충분치 못하고, 35 중량%를 초과하는 경우에는 점도값이 증가하여 포토레지스트 침투력이 낮아 박리시간이 증가하고, 또한 포토레지스트 하부층의 도전성 금속막에 대한 부식성이 커지는 문제점이 발생할 수 있다.The content of the compound represented by Formula 1 is preferably 1 to 35% by weight of the total composition, more preferably 3 to 30% by weight. If 1) the content of the organic amine compound is less than 1% by weight, the peeling force on the modified photoresist is not sufficient, and when the content of the organic amine compound is higher than 35% by weight, the viscosity value increases and the peeling time is low due to the low photoresist penetration force. In addition, the problem that the corrosion resistance of the photoresist underlayer to the conductive metal film may increase.
본 발명에 따른 포토레지스트 스트리퍼 조성물은 상기 화학식 1로 표시되는 화합물 이외에 당 기술분야에 알려진 유기 아민 화합물을 추가로 포함할 수 있다. 보다 구체적인 예로는 모노에탄올 아민(MEA), 1-아미노이소프로판올(AIP), 2-아미노-1-프로판올, N-메틸아미노에탄올(N-MAE), 3-아미노-1-프로판올, 4-아미노-1-부 탄올, 2-(2-아미노에톡시)-1-에탄올(AEE), 2-(2-아미노에틸아미노)-1-에탄올, 디에탄올 아민(DEA), 트리에탄올 아민(TEA), 히드록시에틸피페라진(HEP) 등을 들 수 있으나, 이에만 한정되는 것은 아니다.The photoresist stripper composition according to the present invention may further include an organic amine compound known in the art in addition to the compound represented by Chemical Formula 1. More specific examples include monoethanol amine (MEA), 1-aminoisopropanol (AIP), 2-amino-1-propanol, N-methylaminoethanol (N-MAE), 3-amino-1-propanol, 4-amino- 1-butanol, 2- (2-aminoethoxy) -1-ethanol (AEE), 2- (2-aminoethylamino) -1-ethanol, diethanol amine (DEA), triethanol amine (TEA), hydroxide Oxyethylpiperazine (HEP) and the like, but are not limited thereto.
본 발명에 따른 포토레지스트 스트리퍼 조성물에 있어서, 상기 추가의 유기 아민 화합물을 포함하는 경우에는 상기 화학식 1로 표시되는 화합물 및 추가의 유기 아민 화합물의 총 함량은 전체 조성물 총중량 중 1 ~ 35 중량%인 것이 바람직하며, 더욱 바람직하게는 3 ~ 30 중량%이다.In the photoresist stripper composition according to the present invention, when the additional organic amine compound is included, the total content of the compound represented by Formula 1 and the additional organic amine compound is 1 to 35% by weight of the total weight of the composition. Preferably, it is 3-30 weight% more preferably.
본 발명에 따른 포토레지스트 스트리퍼 조성물에 있어서, 상기 2) 용매는 물과 유기 화합물과의 상용성이 뛰어나고 포토레지스트를 용해시키는 용제 역할을 한다. 또한, 스트리퍼의 표면장력을 저하시켜 포토레지스트막에 대한 습윤성(wetting property)을 향상시켜 준다.In the photoresist stripper composition according to the present invention, 2) the solvent is excellent in compatibility between water and the organic compound and serves as a solvent for dissolving the photoresist. In addition, the surface tension of the stripper is reduced to improve the wettability of the photoresist film.
상기 2) 용매는 당 기술분야에 알려진 용매를 이용할 수 있다. 이의 구체적인 예로는 N-메틸피롤리돈(NMP), 1,3-디메틸-2-이미다졸리디논(DMI), 디메틸설폭사이드(DMSO), 디메틸아세트아마이드(DMAc), 디메틸포름아마이드(DMF), N-메틸포름아마이드(NMF), 테트라메틸렌설폰, 부틸 디글리콜(butyl diglycol, BDG), 에틸 디글리콜(ethyl diglycol, EDG), 메틸 디글리콜(methyl diglycol, MDG), 트리에틸렌 글리콜(triethylene glycol, TEG), 디에틸렌글리콜 모노에틸에테르(diethyleneglycol monoethylether, DEM), 디에틸렌글리콜 모노부틸에테르(diethyleneglycol monoethylether), 또는 이들의 혼합물 등을 들 수 있으나, 이에만 한정되는 것은 아니다.The solvent 2) may be a solvent known in the art. Specific examples thereof include N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylacetamide (DMAc), dimethylformamide (DMF) , N-methylformamide (NMF), tetramethylenesulfone, butyl diglycol (BDG), ethyl diglycol (EDG), methyl diglycol (MDG), triethylene glycol , TEG), diethyleneglycol monoethylether (DEM), diethyleneglycol monoethylether, or mixtures thereof, and the like, but are not limited thereto.
상기 2) 용매의 함량은 전체 조성물 총중량 중 65 ~ 99 중량%인 것이 바람직하고, 70 ~ 97 중량%인 것이 더욱 바람직하다. 만일 용매의 함량이 65 중량% 미만인 경우에는 스트리퍼의 점도가 상승하여 스트리퍼의 박리력이 저하되는 문제점이 발생할 수 있다.2) The content of the solvent is preferably 65 to 99% by weight, more preferably 70 to 97% by weight of the total weight of the composition. If the content of the solvent is less than 65% by weight, the viscosity of the stripper may be increased to reduce the peeling force of the stripper.
본 발명에 따른 포토레지스트 스트리퍼 조성물은 하기 화학식 3, 화학식 4, 화학식 5, 화학식 6 및 화학식 7로 표시되는 화합물로 이루어진 군으로부터 선택되는 1종 이상의 부식 방지제를 추가로 포함할 수 있다.The photoresist stripper composition according to the present invention may further include at least one corrosion inhibitor selected from the group consisting of compounds represented by the following Chemical Formulas 3, 4, 5, 6 and 7.
[화학식 3](3)
상기 화학식 3에서,In Chemical Formula 3,
R1은 수소, 탄소수 1 내지 12의 알킬기, 티올기 또는 하이드록시기이고,R1 is hydrogen, an alkyl group having 1 to 12 carbon atoms, a thiol group or a hydroxyl group,
R2는 수소, 탄소수 1 내지 12의 알킬기, 알콕시기 또는 탄소수 6 내지 20의 아릴기이며,R2 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group or an aryl group having 6 to 20 carbon atoms,
R3는 수소, 탄소수 1 내지 12의 알킬기, 알콕시기 또는 하이드록시기이다.R3 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group or a hydroxy group.
상기 벤즈이미다졸계 화합물로는 벤즈이미다졸, 2-히드록시벤즈이미다졸, 2-메틸벤즈이미다졸, 2-(히드록시메틸)벤즈이미다졸, 2-머캡토벤즈이미다졸 등을 들 수 있고, 벤즈이미다졸 또는 2-(히드록시메틸)벤즈이미다졸인 것이 바람직하나, 이 에만 한정되는 것은 아니다.Examples of the benzimidazole compound include benzimidazole, 2-hydroxybenzimidazole, 2-methylbenzimidazole, 2- (hydroxymethyl) benzimidazole, 2-mercaptobenzimidazole, and the like. , Benzimidazole or 2- (hydroxymethyl) benzimidazole, but is not limited thereto.
[화학식 4][Formula 4]
상기 화학식 4에서,In Chemical Formula 4,
R4은 수소 또는 탄소수 1 내지 4의 알킬기이며,R4 is hydrogen or an alkyl group having 1 to 4 carbon atoms,
R5 및 R6는 서로 동일하거나 상이하고, 각각 독립적으로 탄소수 1 내지 4의 히드록시알킬기이고,R5 and R6 are the same as or different from each other, and each independently a hydroxyalkyl group having 1 to 4 carbon atoms,
[화학식 5][Chemical Formula 5]
상기 화학식 5에서, R7은 수소 또는 탄소수 1 내지 4의 알킬기이고,In Formula 5, R7 is hydrogen or an alkyl group having 1 to 4 carbon atoms,
[화학식 6][Formula 6]
상기 화학식 6에서, R8은 수소 또는 탄소수 1 내지 4의 알킬기이다.In Formula 6, R8 is hydrogen or an alkyl group having 1 to 4 carbon atoms.
[화학식 7][Formula 7]
상기 화학식 7에서,In Chemical Formula 7,
R9 및 R10은 서로 동일하거나 상이하고, 각각 독립적으로 수소 또는 히드록시기이고,R9 and R10 are the same as or different from each other, and are each independently hydrogen or a hydroxyl group,
R11은 수소, t-부틸기, 카르복실산기(-COOH), 메틸에스테르기(-COOCH3), 에틸에스테르기(-COOC2H5) 또는 프로필에스테르기(-COOC3H7)이다.R11 is hydrogen, t-butyl group, carboxylic acid group (-COOH), methyl ester group (-COOCH 3 ), ethyl ester group (-COOC 2 H 5 ) or propyl ester group (-COOC 3 H 7 ).
본 발명에 따른 포토레지스트 스트리퍼 조성물에 있어서, 상기 부식 방지제의 함량은 전체 조성물 총중량 중 0.01 ~ 5 중량%인 것이 바람직하며, 더욱 바람직하게는 0.1 ~ 1 중량%이다. 만일 상기 부식 방지제의 함량이 0.01 중량% 미만인 경우에는 박리하고자 하는 기판이 장시간 박리액과 접촉할 때 금속 배선에서 부분적인 부식 현상이 일어날 수 있고, 5 중량%를 초과하는 경우에는 점도가 증가하여 박리력을 감소시킬 수 있으며 조성물 가격이 상승하여 가격대비 성능면에서 비효율적이다.In the photoresist stripper composition according to the present invention, the content of the corrosion inhibitor is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight of the total weight of the composition. If the amount of the corrosion inhibitor is less than 0.01% by weight, partial corrosion may occur in the metal wiring when the substrate to be peeled is in contact with the stripping solution for a long time, and when the amount of the corrosion inhibitor exceeds 5% by weight, the viscosity increases and the peeling occurs. Force can be reduced and the cost of the composition rises, which is inefficient in terms of price / performance.
본 발명에 따른 포토레지스트 스트리퍼 조성물은 포토레지스트 박리 능력이 우수할 뿐만 아니라, 포토레지스트 하부의 도전성 금속막 및 절연막에 손상을 주지 않으며, 포토레지스트 하부의 도전성 금속막 또는 절연막에 대한 부식 방지력이 우수하다.The photoresist stripper composition according to the present invention not only has excellent photoresist peeling ability, but also does not damage the conductive metal film and the insulating film under the photoresist, and has excellent corrosion protection against the conductive metal film or the insulating film under the photoresist. Do.
상기 도전성 금속막 또는 절연막은 알루미늄, 구리, 네오디뮴, 몰리브덴 등의 금속 또는 이들 금속의 합금으로 이루어진 단일막 또는 2층 이상의 다층막일 수 있다. 보다 바람직하게는 알루미늄, 구리 또는 이들의 합금을 포함하는 단일막, 또는 2층 이상의 다층막이거나, 알루미늄, 구리 또는 이들의 합금과 네오디뮴, 몰리브덴 또는 이들의 합금을 포함하는 단일막, 또는 2층 이상의 다층막일 수 있다.The conductive metal film or insulating film may be a single film made of a metal such as aluminum, copper, neodymium, molybdenum, or an alloy of these metals, or a multilayer film of two or more layers. More preferably, a single film containing aluminum, copper or an alloy thereof, or a multilayer film of two or more layers, or a single film containing aluminum, copper or an alloy thereof, and neodymium, molybdenum or an alloy thereof, or a multilayer film of two or more layers Can be.
본 발명에 따른 포토레지스트의 박리방법은 전술한 본 발명에 따른 포토레지스트 스트리퍼 조성물을 이용하는 것을 특징으로 한다.The peeling method of the photoresist according to the present invention is characterized by using the above-described photoresist stripper composition according to the present invention.
본 발명의 하나의 실시상태에 따른 포토레지스트의 박리방법은 1) 기판 상에 형성된 도전성 금속막 또는 절연막에 포토레지스트를 도포하는 단계, 2) 상기 기판에 포토레지스트 패턴을 형성하는 단계, 3) 상기 패턴이 형성된 포토레지스트를 마스크로 하여, 상기 도전성 금속막 또는 절연막을 에칭하는 단계, 및 4) 본 발명의 포토레지스트 스트리퍼 조성물을 이용하여 포토레지스트를 박리하는 단계를 포함한다.According to one embodiment of the present invention, a method of peeling a photoresist includes: 1) applying a photoresist to a conductive metal film or an insulating film formed on a substrate, 2) forming a photoresist pattern on the substrate, and 3) Etching the conductive metal film or the insulating film using a patterned photoresist as a mask, and 4) peeling the photoresist using the photoresist stripper composition of the present invention.
본 발명의 또 하나의 실시상태에 따른 포토레지스트의 박리방법은 1) 기판 상에 포토레지스를 전면 도포하는 단계, 2) 상기 기판에 포토레지스트 패턴을 형성하는 단계, 3) 상기 포토레지스트 패턴이 형성된 기판에 도전성 금속막 또는 절연막을 형성하는 단계, 및 4) 본 발명의 포토레지스트 스트리퍼 조성물을 이용하여 포토레지스트를 박리하는 단계를 포함한다.According to another embodiment of the present invention, a method of peeling a photoresist may include: 1) applying a photoresist to the entire surface of a substrate, 2) forming a photoresist pattern on the substrate, and 3) forming a photoresist pattern on the substrate. Forming a conductive metal film or insulating film on the substrate, and 4) peeling the photoresist using the photoresist stripper composition of the present invention.
상기 본 발명에 따른 포토레지스트의 박리방법에 있어서, 상기 도전성 금속막 또는 절연막은 알루미늄, 구리, 네오디뮴, 몰리브덴 등의 금속 또는 이들 금속의 합금으로 이루어진 단일막 또는 2층 이상의 다층막일 수 있다. 구체적으로는 Al-Nd/Mo 이중막, Cu/Mo 이중막 등이 바람직하다.In the method of peeling a photoresist according to the present invention, the conductive metal film or the insulating film may be a single film or a multilayer film made of a metal such as aluminum, copper, neodymium, molybdenum, or an alloy of these metals or two or more layers. Specifically, an Al-Nd / Mo double film, a Cu / Mo double film, or the like is preferable.
본 발명의 포토레지스트 스트리퍼 조성물을 이용하여 미세 회로 패턴이 새겨진 기판으로부터 포토레지스트를 박리하는 방법은, 많은 양의 스트리퍼액에 박리하고자 하는 기판을 동시에 여러 장 침지(dipping)하는 딥 방식과 한 장씩 박리액을 기판에 스프레이(분무)시켜 포토레지스트를 제거하는 매엽식 방식 모두 사용할 수 있다.The method of peeling photoresist from a substrate engraved with a fine circuit pattern using the photoresist stripper composition of the present invention includes a dip method of dipping several sheets of the substrate to be peeled simultaneously in a large amount of stripper liquid and peeling one by one. Both single-layer methods of spraying (spraying) the liquid onto the substrate to remove the photoresist can be used.
본 발명의 포토레지스트 스트리퍼 조성물을 이용하여 박리할 수 있는 포토레지스트의 종류로는, 포지형 포토레지스트, 네가형 포토레지스트, 포지형/네가형 겸용 포토레지스트(dual tone photoresist)가 있고, 구성 성분에 제약을 받지 않지만, 특히 효과적으로 적용되는 포토레지스트는 노볼락계 페놀 수지와 디아조나프토퀴논을 근간으로 하는 광활성 화합물로 구성된 포토레지스트이다.Examples of the photoresist that can be peeled off using the photoresist stripper composition of the present invention include a positive photoresist, a negative photoresist, and a positive / negative dual tone photoresist. A photoresist that is not restricted but particularly effective is a photoresist composed of a novolak-based phenol resin and a photoactive compound based on diazonaphthoquinone.
본 발명에 따라 상기 포토레지스트 스트리퍼 조성물을 이용하여 포토레지스트를 박리하여 제조된 액정 표시 장치 또는 반도체 소자는 포토레지스트 박리시 미세 패턴을 갖는 기판이 부식 또는 손상되지 않으면서, 잔류 포토레지스트가 적은 특징이 있다.According to the present invention, a liquid crystal display device or a semiconductor device manufactured by peeling a photoresist using the photoresist stripper composition is characterized in that the substrate having a fine pattern does not corrode or be damaged when the photoresist is peeled off, and thus there is little residual photoresist. have.
이와 같이, 본 발명에 따르면 식각 공정 동안 변성된 포토레지스트막을 고온 및 저온에서도 짧은 시간 내에 용이하게 제거 가능하며, 포토레지스트 하부의 알루 미늄 또는 알루미늄 합금, 구리 또는 구리 합금, 몰리브덴 또는 몰리브덴 합금과 같은 도전성막 및 절연막에 대한 부식이 적은 포토레지스트 스트리퍼 조성물을 제공할 수 있다.As described above, according to the present invention, the photoresist film modified during the etching process can be easily removed even at a high temperature and a low temperature within a short time, and a conductive material such as aluminum or aluminum alloy, copper or copper alloy, molybdenum or molybdenum alloy under the photoresist can be easily removed. It is possible to provide a photoresist stripper composition having less corrosion on the film formation and the insulating film.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나, 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.
<< 실시예Example >>
<< 제조예Production Example > 유기 아민 화합물의 제조> Preparation of Organic Amine Compounds
상기 반응식 1에 따라 화학식 1-2로 표시되는 화합물을 제조하였다. 이 때, 상압하에서 반응온도는 85 ~ 95℃ 이었고, 환류 시간은 1시간 이었다. 제조된 화합물의 물성은 하기와 같으며, 그 NMR 데이터를 도 1 및 도 2에 나타내었다.According to Scheme 1, a compound represented by Chemical Formula 1-2 was prepared. At this time, the reaction temperature was 85 ~ 95 ℃ under normal pressure, the reflux time was 1 hour. Physical properties of the prepared compound are as follows, the NMR data are shown in Figs.
화학식: C5H12N2OChemical Formula: C 5 H 12 N 2 O
Mass: 116.09Mass: 116.09
Mol. Wt.: 116.16Mol. Wt .: 116.16
m/e: 116.09(100.0%), 117.10(5.6%)m / e: 116.09 (100.0%), 117.10 (5.6%)
C, 51.70; H, 10.41; N, 24.12; O, 13.77C, 51.70; H, 10.41; N, 24.12; O, 13.77
<< 실시예Example 1 ~ 2> 1 to 2
하기 표 1에 기재되어 있는 성분과 조성비를 이용하고, 상온에서 2시간 동안 교반한 후 0.1㎛로 여과하여 스트리퍼 용액을 제조하였다.Using the components and composition ratios shown in Table 1 below, the mixture was stirred at room temperature for 2 hours and then filtered at 0.1 μm to prepare a stripper solution.
<< 비교예Comparative example 1 ~ 3> 1 to 3
하기 표 1에 기재되어 있는 성분과 조성비를 이용하여 상기 실시예 1 ~ 2와 동일한 방법으로 스트리퍼 용액을 제조하였다.A stripper solution was prepared in the same manner as in Examples 1 and 2 using the components and the composition ratios shown in Table 1 below.
[표 1]TABLE 1
AEE: 아미노에톡시에탄올(aminoethoxyethanol)AEE: aminoethoxyethanol
HEP: 히드록시에틸피페라진(Hydroxyethylpiperazine)HEP: hydroxyethylpiperazine (Hydroxyethylpiperazine)
IME: 1-이미다졸리딘 에탄올(1-imidazolidine ethanol)IME: 1-imidazolidine ethanol
NMEA: N-메틸에탄올아민(N-methylethanolamine)NMEA: N-methylethanolamine
BDG: 디에틸렌 글리콜 모노 부틸 에테르(Diethylene glycol mono butyl ether)BDG: Diethylene glycol mono butyl ether
NMF: N-메틸 포름아마이드(N-methylformamide)NMF: N-methylformamide
THBTA: 테트라하이드로벤조트리아졸(Tetrahydrobenzotriazole)THBTA: Tetrahydrobenzotriazole
BzI: 벤즈이미다졸(benzimidazole)BzI: benzimidazole
<< 실험예Experimental Example >>
1) 박리 속도 평가1) Peel rate evaluation
상기 실시예 1 및 비교예 1 ~ 3에서 제조한 포토레지스트 스트리퍼 조성물을 이용하고, 각각 140℃, 150℃ 및 160℃에서 5분간 하드 베이크(hard bake)한 포토레지스트에 대한 박리 공정을 수행하였고, 포토레지스트가 완전히 박리되는데 걸리는 시간을 측정하였다. 평가 결과는 하기 표 2 및 도 3에 나타내었다.Using the photoresist stripper compositions prepared in Example 1 and Comparative Examples 1 to 3, a peeling process was performed on the photoresist hard baked at 140 ° C, 150 ° C and 160 ° C for 5 minutes, respectively. The time taken for the photoresist to peel completely was measured. Evaluation results are shown in Table 2 and FIG. 3.
[표 2]TABLE 2
상기 표 1 및 도 3의 결과로부터, 본 발명에 따른 포토레지스트 스트리퍼 조성물은 박리 능력이 우수하여 박리 속도가 빠름을 알 수 있다.From the results of Table 1 and FIG. 3, it can be seen that the photoresist stripper composition according to the present invention has excellent peeling ability and a fast peeling speed.
2) 부식 정도 평가2) Corrosion degree evaluation
상기 실시예 1 및 비교예 1 ~ 3에서 제조한 포토레지스트 스트리퍼 조성물을 이용하여 포토레지스트 박리 공정을 수행한 후, 시편의 표면, 측면 및 단면의 부식 정도를 관찰하고, 그 결과를 하기 표 3에 나타내었다. 이 때, 상기 부식 정도는 하기와 같은 기준으로 평가하였다.After performing the photoresist stripping process using the photoresist stripper composition prepared in Example 1 and Comparative Examples 1 to 3, the degree of corrosion of the surface, side and cross-section of the specimen was observed, and the results are shown in Table 3 below. Indicated. At this time, the corrosion degree was evaluated based on the following criteria.
◎: 표면과 측면에 부식이 전혀 없는 경우◎: no corrosion on the surface and side
○: 표면과 측면에 약간의 부식이 있는 경우○: slight corrosion on the surface and sides
△: 표면과 측면에 부분적인 부식이 있는 경우△: partial corrosion on surface and side
×: 표면과 측면에 전체적으로 심한 부식이 일어난 경우×: When severe corrosion occurred on the surface and side as a whole
[표 3][Table 3]
상기 표 3의 결과로부터, 본 발명에 따른 포토레지스트 조성물은 포토레지스트 하부막의 종류에 상관 없이 모두 부식 방지력이 우수함을 알 수 있다.From the results of Table 3, it can be seen that the photoresist composition according to the present invention is excellent in corrosion protection, regardless of the type of the photoresist underlayer.
도 1 및 도 2는 화학식 1-2로 표시되는 화합물의 NMR 데이터이다.1 and 2 are NMR data of the compound represented by Chemical Formula 1-2.
도 3은 포토레지스트 스트리퍼 조성물의 아민 화합물에 따른 박리 속도를 평가한 결과를 나타낸 도이다.3 is a view showing the results of evaluating the peeling rate according to the amine compound of the photoresist stripper composition.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140044728A (en) | 2012-10-05 | 2014-04-15 | 동우 화인켐 주식회사 | A photoresist stripper composition restraining galvanic corrosion |
| KR20150087642A (en) | 2014-01-22 | 2015-07-30 | 동우 화인켐 주식회사 | Resist stripper composition and method of stripping resist using the same |
| KR20170011803A (en) | 2015-07-24 | 2017-02-02 | 동우 화인켐 주식회사 | Composition of stripper for photoresist |
| KR20190050957A (en) | 2019-05-03 | 2019-05-14 | 동우 화인켐 주식회사 | A photoresist stripper composition restraining galvanic corrosion |
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| KR101679030B1 (en) * | 2009-12-16 | 2016-11-23 | 주식회사 동진쎄미켐 | Stripper composition of photoresist |
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| TW200741031A (en) * | 2006-03-03 | 2007-11-01 | Mec Co Ltd | Surface treating agent and method for manufacturing coating using the same |
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| WO2005109107A1 (en) * | 2004-05-07 | 2005-11-17 | Dongjin Semichem Co., Ltd. | Composition for removing a (photo)resist |
| KR20060024478A (en) * | 2004-09-13 | 2006-03-17 | 주식회사 동진쎄미켐 | Composition for removing a photoresist |
| KR20090022071A (en) * | 2007-08-29 | 2009-03-04 | 주식회사 엘지화학 | Stripper composition for photoresist and method for stripping photoresist |
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| KR20150087642A (en) | 2014-01-22 | 2015-07-30 | 동우 화인켐 주식회사 | Resist stripper composition and method of stripping resist using the same |
| KR20170011803A (en) | 2015-07-24 | 2017-02-02 | 동우 화인켐 주식회사 | Composition of stripper for photoresist |
| KR20190050957A (en) | 2019-05-03 | 2019-05-14 | 동우 화인켐 주식회사 | A photoresist stripper composition restraining galvanic corrosion |
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