CN106997158B - Stripping liquid composition for removing photoresist - Google Patents
Stripping liquid composition for removing photoresist Download PDFInfo
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- CN106997158B CN106997158B CN201710053375.8A CN201710053375A CN106997158B CN 106997158 B CN106997158 B CN 106997158B CN 201710053375 A CN201710053375 A CN 201710053375A CN 106997158 B CN106997158 B CN 106997158B
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- photoresist
- liquid composition
- stripping liquid
- ether
- stripping
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 239000007788 liquid Substances 0.000 title claims abstract description 41
- -1 amine compound Chemical class 0.000 claims description 27
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 claims description 22
- 239000003586 protic polar solvent Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 7
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 7
- IQXXEPZFOOTTBA-UHFFFAOYSA-N 1-benzylpiperazine Chemical compound C=1C=CC=CC=1CN1CCNCC1 IQXXEPZFOOTTBA-UHFFFAOYSA-N 0.000 claims description 5
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims description 5
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 4
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 claims description 4
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 claims description 4
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 claims description 4
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical class OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 24
- 239000000758 substrate Substances 0.000 abstract description 17
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 16
- 239000002904 solvent Substances 0.000 abstract description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000001312 dry etching Methods 0.000 abstract description 2
- 238000001039 wet etching Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 16
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 6
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 6
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 2
- QZXIXSZVEYUCGM-UHFFFAOYSA-N 2-aminopropan-2-ol Chemical compound CC(C)(N)O QZXIXSZVEYUCGM-UHFFFAOYSA-N 0.000 description 2
- RELOFIKZGIJATN-UHFFFAOYSA-N 2-imidazolidin-1-ylethanol Chemical compound OCCN1CCNC1 RELOFIKZGIJATN-UHFFFAOYSA-N 0.000 description 2
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- IYUOYLLVOZNGKW-UHFFFAOYSA-N 2-azidonaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(N=[N+]=[N-])=CC(=O)C2=C1 IYUOYLLVOZNGKW-UHFFFAOYSA-N 0.000 description 1
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 1
- QGCDUBGOXJTXIU-UHFFFAOYSA-N 3-(2h-benzotriazol-4-yl)propane-1,1-diol Chemical compound OC(O)CCC1=CC=CC2=NNN=C12 QGCDUBGOXJTXIU-UHFFFAOYSA-N 0.000 description 1
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical compound [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- LKPFBGKZCCBZDK-UHFFFAOYSA-N n-hydroxypiperidine Chemical compound ON1CCCCC1 LKPFBGKZCCBZDK-UHFFFAOYSA-N 0.000 description 1
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
The stripping liquid composition for removing photoresist of the present invention has advantages that even if N-methylformamide (NMF) or N-methylpyrrolidone (NMP), which is harmful to the environment and human body, is not used as a main solvent, the modified photoresist can be rapidly stripped after the completion of dry or wet etching, and foreign substances and stains do not remain on the substrate, so that the process efficiency can be significantly improved. In addition, corrosion of the primary coating can be minimized, and process efficiency can be significantly improved.
Description
Technical Field
The present invention relates to a stripping liquid composition for removing a photoresist, which uses an amine compound, a polar solvent and a nonpolar solvent, which do not contain toxic substances harmful to the human body.
Background
The photolithography process is a series of photographing processes for transferring a pattern designed on a mask plate (mask) onto a substrate on which a thin film to be processed is formed. The photolithography process is used for manufacturing an integrated circuit, a highly integrated circuit, and the like.
In the photolithography process, a photoresist, which is a photosensitive material, is coated (coating) on a glass substrate on which a thin film is formed, a mask is placed on the substrate coated with the photoresist, exposure (exposure) is performed, and then the photoresist is developed (develop) to form a photoresist pattern. For example, the thin film may be a metal film, an insulating film, or the like. The photoresist pattern may be wet-etched or dry-etched using a mask blank to transfer the microcircuit pattern, thereby performing etching. Then, a step of removing an unnecessary photoresist pattern with a stripper (stripper) as a composition for removing a photoresist pattern is performed.
Among them, a photoresist removing stripper used in a process of forming a display and a semiconductor electrode circuit needs to be capable of stripping a photoresist at a low temperature for a short time, and after completion of cleaning (rinse), it is necessary to prevent a photoresist residue from remaining on a substrate, and the photoresist removing stripper needs to have a capability of stripping an organic insulating film and a metal wiring without damage. The resist removing stripping liquid may basically contain organic compounds such as amine compounds, alkylene glycol alkyl ether compounds, protic polar solvents, and preservatives. In the various stripping liquid compositions described above, in view of stripping properties and corrosiveness, aprotic solvents such as N-methylformamide (NMF) and N-methylpyrrolidinone (NMP) are mainly used as the main solvent (taiwan patent No. 10-2011 + 0124955, taiwan patent No. 10-2014 + 0028962, taiwan patent No. 10-2015 + 0102354, taiwan patent No. 10-0655108, etc.). Although such solvents have excellent peeling force, but have disadvantages harmful to the environment and human body, there is a need to develop alternative solvents for replacing aprotic polar solvents of the above solvents.
Documents of the prior art
Patent document
Taiwan patent No. 10-2011-
Taiwan granted patent No. 10-2014-0028962
Taiwan granted patent No. 10-2015-0102354
Taiwan laid-open patent No. 10-0655108
Disclosure of Invention
Technical problem
An object of the present invention is to solve the above problems and to provide a stripping liquid composition for removing a photoresist, which can improve the stripping rate without using solvents harmful to the environment and human body. More specifically, the present invention has an object to develop a stripping liquid composition for removing a photoresist, which is harmless to the environment and human body, excellent in stripping force, and minimizes corrosion of an underlying film, by using N-ethylformamide (NEF).
Another object of the present invention is to provide a method for stripping a photoresist by using the above-mentioned stripping liquid composition for removing a photoresist.
Means for solving the problems
In order to achieve the above object, the present invention provides a stripping liquid composition for removing a photoresist, comprising N-ethylformamide, an amine compound, and a protic polar solvent.
According to an embodiment of the present invention, the photoresist removing stripping liquid composition may include 10 wt% to 80 wt% of N-ethylformamide, 1 wt% to 30 wt% of amine compound, and 10 wt% to 80 wt% of protic polar solvent.
According to an embodiment of the present invention, the photoresist removing stripping liquid composition further comprises 1 to 30 weight percent of ultrapure water or deionized water, or further comprises 0.01 to 5 weight percent of an additive, or further comprises 1 to 30 weight percent of ultrapure water or deionized water and 0.01 to 5 weight percent of an additive.
According to an embodiment of the present invention, the amine compound may be one or a mixture of two or more selected from the group consisting of monoethanolamine, monoisopropanolamine, imidazolidineethanol, 2-amino-1-propanol, aminoisopropanol, N-methylaminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 2- (2-aminoethoxy) ethanol, diethanolamine, 1- (2-hydroxyethyl) piperazine, triethanolamine, 1-piperidineethanolamine, benzylpiperazine, and benzylamine.
According to an embodiment of the present invention, the protic polar solvent may be one or more of diethylene glycol monoethyl ether (diethylene glycol monoethyl ether), diethylene glycol monopropyl ether (diethylene glycol monopropyl ether), diethylene glycol Monobutyl ether (diethylene glycol Monobutyl ether), dipropylene glycol monomethyl ether (dipropylene glycol monomethyl ether), dipropylene glycol monoethyl ether (dipropylene glycol monoethyl ether), dipropylene glycol monopropyl ether (dipropylene glycol monopropyl ether), dipropylene glycol Monobutyl ether (dipropylene glycol Monobutyl ether), Ethylene glycol Propyl ether (Ethylene glycol monoethyl ether), Ethylene glycol monoethyl ether (Ethylene glycol monoethyl ether), and Ethylene glycol Tetraethyl ether (Ethylene glycol monoethyl ether), or a mixture thereof.
According to an embodiment of the present invention, the additive may be a triazole compound.
ADVANTAGEOUS EFFECTS OF INVENTION
The stripping liquid composition for removing photoresist of the present invention has the advantages that even if N-methylformamide or N-methylpyrrolidone harmful to the environment and human body is not used as a main solvent, the modified photoresist can be rapidly stripped after the completion of dry or wet etching, and foreign matters and stains are not left on the substrate, so that the efficiency of the process can be remarkably improved.
In addition, corrosion of the primary coating can be minimized, and process efficiency can be significantly improved.
Detailed Description
Hereinafter, preferred embodiments of the stripping liquid composition for removing a photoresist and a method for detecting physical properties will be described in detail. The present invention relates to a stripper composition for removing photoresist used in the process of manufacturing displays and semiconductors, and therefore, the present invention can be more clearly understood by the following examples, which are provided for illustrative purposes only and are not intended to limit the scope of protection defined by the appended claims.
The present inventors have conducted studies to develop a stripping solution composition which does not use N-methylformamide or N-methylpyrrolidone, which is harmful to the human body, as a main solvent and can improve the removal rate of a photoresist, and have found that the time consumed in the process of removing the photoresist can be reduced by using N-ethylformamide, and the process efficiency can be improved by minimizing foreign substances and stains remaining on a substrate, thereby completing the present invention.
Hereinafter, an embodiment of the present invention will be described in more detail.
In a first embodiment of the present invention, the stripping liquid composition for removing photoresist comprises N-ethylformamide, an amine compound, and a protic polar solvent.
In a second embodiment of the present invention, the resist removing stripping liquid composition includes N-ethylformamide, an amine compound, a protic polar solvent, and an additive.
In a third embodiment of the present invention, the photoresist removing stripping liquid composition comprises N-ethylformamide, an amine compound, a protic polar solvent, and ultrapure water or deionized water.
In a fourth embodiment of the present invention, the photoresist removing stripping solution composition comprises N-ethylformamide, an amine compound, a protic polar solvent, an additive, and ultrapure water or deionized water.
Although the content of N-ethylformamide is not limited in an embodiment of the present invention, N-ethylformamide may be included in an amount of 10 to 80 wt%. Preferably, from 15 to 70 weight percent of N-ethylformamide may be included. N-ethylformamide is included within the above range, whereby the peeling force can be improved, the photoresist removal time can be significantly shortened, and the corrosion of the underlying film can be minimized.
When the content of N-ethylformamide is less than 10 wt%, the peeling force is not sufficiently improved, and thus, a long time is required for removing the photoresist, and foreign substances, stains, and the like remain on the substrate. Also, when it is more than 80 weight%, there is a problem of corrosion of the under film.
According to an embodiment of the present invention, the stripping liquid composition for removing photoresist of the present invention may include an amine compound. The amine compound according to an embodiment of the present invention can improve the stripping force of the photoresist modified by mixing the above N-ethylformamide.
The amine compound functions to a relatively weak portion of the surface of the photoresist that has been modified, and thus functions to facilitate penetration of a solvent component.
The amine compound of the present invention is a compound known in the art, and is not limited thereto. For example, one or a mixture of two or more selected from the group consisting of monoethanolamine, monoisopropanolamine, imidazolidineethanol, 2-amino-1-propanol, aminoisopropanol, N-methylaminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, aminoethoxyethanol, 2- (2-aminoethoxy) -1-ethanol, diethanolamine, 1- (2-hydroxyethyl) piperazine, triethanolamine, 1-piperidineethanolamine, benzylpiperazine, and benzylamine can be used.
Preferably, the composition can be used by mixing one or a mixture of two or more selected from monoethanolamine, monoisopropanolamine, 2- (2-aminoethoxy) -1-ethanol, 1-piperidineethanolamine, diethanolamine, triethanolamine, N-methylaminoethanol, benzylpiperazine, 1- (2-hydroxyethyl) piperazine, and benzylamine with N-ethylformamide, thereby achieving a significant effect of further improving the long-term storage stability of the composition and further improving the peeling force.
The amine compound according to an embodiment of the present invention may be included in an amount of 1 to 30 wt% based on the total weight of the photoresist removing stripping liquid composition. Preferably, 3 to 25 weight percent may be included. The peeling force of the photoresist subjected to the modification can be significantly improved by including the above amine compound within the above range.
When the content of the amine compound is less than 1% by weight, the peeling force of the modified photoresist is reduced, and thus there is a risk that stains or foreign substances remain on the substrate, and when the content is more than 30% by weight, there is a risk that aluminum wiring and copper wiring under the photoresist are corroded.
In the case of the above-mentioned protic polar solvent, the protic polar solvent known in the art is not limited, and for example, one or a mixture of two or more selected from the group consisting of diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol propyl ether, ethylene glycol monobutyl ether, and tetraethyl hydrogenated furfuryl alcohol may be used.
Preferably, the solvent is one or more selected from diethylene glycol monobutyl ether, diethylene glycol monomethyl ether (diethylene glycol monomethyl ether), diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and tetraethyl furfuryl hydride.
More preferably, one or a mixture of two or more selected from the group consisting of diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether is used, and therefore, when the N-ethylformamide and the amine compound are used in a mixed manner, a significant effect of further improving the long-term storage stability of the composition, not causing metal corrosion, and further improving the peeling force can be achieved.
The stripping liquid composition for removing photoresist may include 10 to 80 wt% of the protic polar solvent according to an embodiment of the present invention, based on the total weight of the stripping liquid composition. Preferably, 25 to 78 weight percent may be included. The stripping force of the photoresist subjected to modification can be significantly improved by including the above-mentioned protic polar solvent in the above-mentioned range.
When the content of the protic polar solvent is less than 10% by weight, the peeling force of the photoresist after the modification is reduced, and thus there is a risk that stains or foreign substances remain on the substrate, and when the content is more than 80% by weight, there may be a problem that damage to the organic insulating film under the common electrode is increased.
The stripping liquid composition for removing a photoresist of the present invention may be an aqueous or non-aqueous composition known in the art, in addition to the above components, and therefore, the stripping liquid composition for removing a photoresist may further include ultrapure water or deionized water within a range not limiting the physical properties of the stripping liquid composition for removing a photoresist. More specifically, the above-mentioned ultrapure water or deionized water may be contained in an amount of 1 to 30% by weight, and preferably, 2 to 5% by weight, without being limited thereto.
The resist removing stripping liquid composition of the present invention may further contain one or more other additives, if necessary, in addition to the above components. For example, a triazole compound may be contained as the preservative. The triazole compound is not limited as long as it is a compound known in the art, and specific examples thereof include benzotriazole, tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole, dihydroxypropylbenzotriazole, and the like. Preferably, a significant effect of further improving long-term storage stability and further increasing peeling force can be achieved together with the anticorrosive effect by using tolyltriazole.
The photoresist removing stripping liquid composition may contain the triazole compound in an amount of 0.01 to 5 wt%, preferably 0.1 to 0.5 wt%, but is not limited thereto.
Also, according to still another embodiment of the present invention, there is provided a photoresist stripping method by which the above-mentioned stripping liquid composition for photoresist removal is treated.
The method for stripping the photoresist may include a step of using a photoresist pattern formed on an organic insulating film, a metal wiring, or a substrate including the metal wiring and an inorganic material layer as a mask, and stripping (striping) the photoresist pattern with the stripping liquid composition for removing the photoresist after etching the substrate.
The method of stripping a photoresist from a substrate having a microcircuit pattern transferred thereto using the stripper composition for a photoresist according to an embodiment of the present invention may use both a dipping method of simultaneously dipping (dipping) a plurality of substrates to be stripped in a large amount of stripper and a single wafer method of sputtering (spraying) a stripper on each substrate to remove a photoresist, but is not limited thereto.
Examples of the type of the resist that can be peeled off by the stripping liquid composition for resists of the present invention include a positive resist, a negative resist, and a dual-purpose positive/negative resist (dual tone photoresist), and although the composition thereof is not limited, a particularly effective resist to be used may be a resist composed of a photoactive compound containing a novolak type phenol resin and naphthoquinone azide.
For example, the metal wiring that can be applied to the above-mentioned stripping solution composition for removing a photoresist may include, as an under film, an Au/Al/Ni/Cr quadruple film, a Cu/dissimilar metal alloy, silver, a silver alloy, or the like, but is not limited thereto.
On the other hand, according to still another embodiment of the present invention, there is provided a liquid crystal display device or a semiconductor device manufactured by treating the above-mentioned stripping liquid composition for removing a photoresist.
In particular, the present invention can provide a liquid crystal display device or a semiconductor device manufactured by a conventional method including the lift-off method as described above.
Hereinafter, embodiments of the stripping liquid composition for removing a photoresist of the present invention and a method for detecting physical properties will be described in detail.
Physical property detection
1) Evaluation of Photoresist stripping Rate
In order to evaluate the photoresist stripping performance of the stripping liquid composition for removing photoresist prepared as shown in the following table 1, the preparation of experimental test pieces was completed by coating the photoresist composition on a glass substrate to a thickness of 1.5 μm and then prebaking it at 160 ℃ and 170 ℃ for 10 minutes (hard cake; H/B). The time required for complete stripping of the photoresist by the stripping solution was measured under a spray pressure of 0.4kgf using a single wafer spray type stripping apparatus maintained at a temperature of 60 ℃, and the evaluation results are shown in table 2.
2) Evaluation of insulating film Damage
After a photoresist composition was applied to a glass substrate to a thickness of 1.5 μm, prebaking was performed at 160 ℃ and 170 ℃ for 10 minutes, respectively, thereby completing preparation of an experimental test piece. After the photoresist was completely peeled by the stripping solution under a spray pressure of 0.4kgf using a single wafer spray type stripping apparatus maintaining a temperature of 60 ℃, the degree of damage of the insulating film of the dried test piece was confirmed by an optical microscope at 200 magnifications and an electric field emission scanning electron microscope (FE-SEM) at 10K to 50K magnifications. After completion of the confirmation, when there is no damage to the insulating film, it is described as "excellent" and when damage to the insulating film is found, it is described as "bad".
Examples and comparative examples
The stripping liquid composition for removing photoresist was prepared by mixing the components and ingredients described in table 1 below. At this time, the mixing process was performed at normal temperature and mixed for 1 hour or more to achieve sufficient dissolution, and then filtered through a polytetrafluoroethylene filter (polytetrafluoroethylene with pores of 1 μm (PTFA)) and used.
TABLE 1
Solvent(s)
NEF: n-ethylformamide
THFA: tetraethyl furfuryl hydride alcohol
NMPA: n-methylpropionamide
NMF: n-methylformamide
Amines as pesticides
MEA: monoethanolamine
MIPA: monoisopropanolamine
AEE: 2- (2-Aminoethoxy) ethanol
PPEtOH: 1-Piperidinol
DEA: diethanolamine (DEA)
TEA: triethanolamine
NMEA: n-methylaminoethanol
BP: benzylpiperazines
HEP: 1- (2-hydroxyethyl) piperazine
BA: benzylamine
Aprotic polar solvent
MDG: diethylene glycol monomethyl ether
BDG: diethylene glycol monobutyl ether
EDG (electro-deposition) of: diethylene glycol monoethyl ether
Additive agent
CHIDM: 1, 4-cyclohexanedimethanol
TT: tolyltriazole
TABLE 2
As shown in table 2, it was confirmed that the stripping liquid composition for removing a photoresist of the present invention has significantly excellent removal rate and primary coating corrosion resistance. Further, when the long-term storage stability was evaluated, the content of the stripping liquid composition did not change, and thus it was confirmed that the stripping liquid composition had excellent storage stability and had little loss due to evaporation in the process. As shown in comparative examples 6 and 7, it is understood that when N-ethylformamide is included in an amount of 85 wt% or 5 wt%, the N-ethylformamide is used in an amount of 10 to 80 wt%, preferably 15 to 70 wt%, because the removal rate is not increased and the insulating film is not damaged.
In comparative examples 1 to 5, the time required for removing the photoresist was longer than 50 seconds and 60 seconds at the temperature of 160 ℃ and 170 ℃, and thus about 5 to 6 times longer time was required as compared with the examples, and in comparative example 5, the etching of the primary coating was caused by the use of an excessive amount of amine. Therefore, according to the stripping liquid composition for removing the photoresist of the present invention, the photoresist can be rapidly removed without damaging the organic insulating film, and since foreign substances and stains do not remain in the process of removing, the efficiency and reliability of the process can be improved.
While the preferred embodiments of the present invention have been described, the present invention is susceptible to various modifications and equivalent arrangements, and the above embodiments may be suitably modified and applied in the same manner. Accordingly, the above description is not intended to limit the scope of the invention, which is defined by the limitations of the following claims.
Claims (3)
1. A stripping liquid composition for removing a resist, comprising 10 to 80% by weight of N-ethylformamide, 1 to 30% by weight of an amine compound, and 10 to 80% by weight of a protic polar solvent;
the amine compound is 1- (2-hydroxyethyl) piperazine or benzylpiperazine;
the protonic polar solvent is one or a mixture of more than two of dimethyl glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol propyl ether, ethylene glycol monobutyl ether and tetraethyl hydrogenated furfuryl alcohol;
the weight percentage is based on the total weight of the stripping liquid composition for removing the photoresist.
2. The stripping liquid composition for removing photoresist according to claim 1, wherein the stripping liquid composition for removing photoresist further comprises 1 to 30 weight percent of ultrapure water or deionized water or further comprises 0.01 to 5 weight percent of additive, or further comprises 1 to 30 weight percent of ultrapure water or deionized water and 0.01 to 5 weight percent of additive.
3. The stripping solution composition for removing photoresist according to claim 2, characterized in that the additive is a triazole compound.
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| KR10-2016-0007911 | 2016-01-22 | ||
| KR1020160007911A KR102414295B1 (en) | 2016-01-22 | 2016-01-22 | Photoresist stripper composition |
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| KR20200112551A (en) * | 2019-03-22 | 2020-10-05 | 주식회사 엘지화학 | Stripper composition for removing photoresist and stripping method of photoresist using the same |
| KR102753515B1 (en) * | 2020-01-20 | 2025-01-09 | 주식회사 엘지화학 | Stripper composition for removing photoresist and stripping method of photoresist using the same |
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| WO2003038529A1 (en) * | 2001-11-02 | 2003-05-08 | Mitsubishi Gas Chemical Company, Inc. | Method for releasing resist |
| KR100622294B1 (en) | 2002-01-11 | 2006-09-11 | 에이제토 엘렉토로닉 마티리알즈 가부시키가이샤 | Positive or negative photosensitive material cleaning composition |
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| DE10331033B4 (en) * | 2002-07-12 | 2010-04-29 | Ekc Technology K.K. R&D Business Park Bldg. D-3F, Kawasaki | A manufacturing method of a semiconductor device and a cleaning composition therefor |
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| TW201736988A (en) | 2017-10-16 |
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| KR102414295B1 (en) | 2022-06-30 |
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