CN111989621A - Stripper composition for removing photoresist and method for stripping photoresist using the same - Google Patents
Stripper composition for removing photoresist and method for stripping photoresist using the same Download PDFInfo
- Publication number
- CN111989621A CN111989621A CN201980009806.8A CN201980009806A CN111989621A CN 111989621 A CN111989621 A CN 111989621A CN 201980009806 A CN201980009806 A CN 201980009806A CN 111989621 A CN111989621 A CN 111989621A
- Authority
- CN
- China
- Prior art keywords
- photoresist
- stripper composition
- compound
- triazole
- stripping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 122
- 239000000203 mixture Substances 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 32
- -1 amide compounds Chemical class 0.000 claims description 58
- 150000001875 compounds Chemical class 0.000 claims description 37
- 150000003852 triazoles Chemical class 0.000 claims description 33
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims description 32
- 229960002178 thiamazole Drugs 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 13
- 239000003495 polar organic solvent Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- ZUHDIDYOAZNPBV-UHFFFAOYSA-N 2-[2-hydroxyethyl-[(4-methylbenzotriazol-1-yl)methyl]amino]ethanol Chemical compound CC1=CC=CC2=C1N=NN2CN(CCO)CCO ZUHDIDYOAZNPBV-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 2
- CKRLKUOWTAEKKX-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2h-benzotriazole Chemical compound C1CCCC2=NNN=C21 CKRLKUOWTAEKKX-UHFFFAOYSA-N 0.000 claims description 2
- LBOQZDCAYYCJBU-UHFFFAOYSA-N 4-methyl-2h-benzotriazole;5-methyl-2h-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21.CC1=CC=CC2=NNN=C12 LBOQZDCAYYCJBU-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 54
- 238000005260 corrosion Methods 0.000 abstract description 54
- 229910052751 metal Inorganic materials 0.000 abstract description 29
- 239000002184 metal Substances 0.000 abstract description 29
- 230000001747 exhibiting effect Effects 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 74
- 239000010949 copper Substances 0.000 description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 29
- 229910052802 copper Inorganic materials 0.000 description 29
- 239000003112 inhibitor Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 239000011733 molybdenum Substances 0.000 description 10
- 229910052750 molybdenum Inorganic materials 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 238000000059 patterning Methods 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 4
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 4
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- RELOFIKZGIJATN-UHFFFAOYSA-N 2-imidazolidin-1-ylethanol Chemical compound OCCN1CCNC1 RELOFIKZGIJATN-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 229910001182 Mo alloy Inorganic materials 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-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
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- JKEHLQXXZMANPK-UHFFFAOYSA-N 1-[1-(1-propoxypropan-2-yloxy)propan-2-yloxy]propan-2-ol Chemical compound CCCOCC(C)OCC(C)OCC(C)O JKEHLQXXZMANPK-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- BQCCJWMQESHLIT-UHFFFAOYSA-N 1-propylsulfinylpropane Chemical compound CCCS(=O)CCC BQCCJWMQESHLIT-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- FMVOPJLFZGSYOS-UHFFFAOYSA-N 2-[2-(2-ethoxypropoxy)propoxy]propan-1-ol Chemical compound CCOC(C)COC(C)COC(C)CO FMVOPJLFZGSYOS-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- KCBPVRDDYVJQHA-UHFFFAOYSA-N 2-[2-(2-propoxyethoxy)ethoxy]ethanol Chemical compound CCCOCCOCCOCCO KCBPVRDDYVJQHA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YAWDTHHWAYBMCY-UHFFFAOYSA-N 2-imidazolidin-4-ylethanol Chemical compound OCCC1CNCN1 YAWDTHHWAYBMCY-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The present disclosure relates to a stripper composition for removing a photoresist capable of inhibiting corrosion of a lower metal film during a stripping process and effectively removing an oxide while being capable of exhibiting excellent stripping ability for the photoresist, and to a method for stripping a photoresist using the same.
Description
Technical Field
Cross Reference to Related Applications
This application claims the benefit of korean patent application No. 10-2019-0033204, filed on 22.3.2019 with the korean intellectual property office, the disclosure of which is incorporated herein by reference in its entirety.
The present disclosure relates to a stripper composition for removing photoresist and a method of stripping photoresist using the same. More particularly, it relates to a stripper composition for removing a photoresist, which can inhibit corrosion of a lower metal film during a stripping process and can effectively remove an oxide while being capable of exhibiting excellent stripping ability for the photoresist, and to a method for stripping a photoresist using the same.
Background
The process for manufacturing a microcircuit or a semiconductor integrated circuit of a liquid crystal display device includes the steps of: forming various lower films on a substrate, for example, a conductive metal film made of aluminum, an aluminum alloy, copper, a copper alloy, molybdenum, or a molybdenum alloy, or an insulating film (e.g., a silicon oxide film, a silicon nitride film, or an acrylic (acryl) insulating film); uniformly applying a photoresist on the lower film; optionally exposing and developing the applied photoresist to form a photoresist pattern; and patterning the lower film using the photoresist pattern as a mask. After the patterning step, a process of removing the photoresist remaining on the lower film is performed. For this purpose, a stripper composition for removing the photoresist is used.
Conventionally, a stripper composition containing an amine compound, a polar protic solvent, a polar aprotic solvent, and the like has been known and widely used. These stripper compositions are known to exhibit a certain degree of removal and stripping ability for photoresists.
However, these conventional stripper compositions promote decomposition of the amine compound over time when stripping a large amount of photoresist, and thus have a problem that stripping and rinsing capabilities are reduced over time. In particular, depending on the number of times the stripper composition is used, these problems may be further exacerbated if some residual photoresist is dissolved in the stripper composition.
Further, when the copper metal film is used as the lower film, stains and foreign matters are generated due to corrosion during peeling, which makes it difficult to use. In addition, there is a limitation such as not being able to effectively remove the copper oxide.
Disclosure of Invention
Technical problem
The present disclosure provides a stripper composition for removing a photoresist, which can inhibit corrosion of a lower metal film during a stripping process and can effectively remove an oxide while being capable of exhibiting excellent stripping ability for the photoresist.
The present disclosure provides a method of stripping photoresist using a stripper composition for removing photoresist.
Technical scheme
In the present disclosure, a stripper composition for removing photoresist is provided, comprising: amide compounds in which the nitrogen atom is substituted with 1 or 2 linear or branched alkyl groups having 1 to 5 carbon atoms; an amine compound; a polar organic solvent; methimazole; and triazole-based compounds.
In the present disclosure, there is also provided a method for stripping photoresist comprising the steps of: forming a photoresist pattern on the substrate having the lower film formed therein; patterning the lower film with a photoresist pattern; and stripping the photoresist using a stripper composition for removing the photoresist.
Hereinafter, a stripper composition for removing photoresist and a method for stripping photoresist using the same according to embodiments of the present invention will be described in detail.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular is intended to include the plural unless the context clearly indicates otherwise. It will be further understood that the terms "comprises," "comprising," "has," "having," or "having," when used in this specification, specify the presence of stated features, integers, steps, components, or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components, or groups thereof.
While the invention is amenable to various modifications and alternative forms, specifics thereof have been shown by way of example in the drawings and will be described in detail. However, it is not intended to limit the invention to the particular forms disclosed, but rather, the invention is to be understood to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
According to one embodiment of the present disclosure, there is provided a stripper composition for removing photoresist, comprising: amide compounds in which the nitrogen atom is substituted with 1 or 2 linear or branched alkyl groups having 1 to 5 carbon atoms; an amine compound; a polar organic solvent; methimazole; and triazole-based compounds.
The present inventors have studied on a stripper composition for removing a photoresist and found through experiments that: the stripper composition for removing photoresist comprising the above components suppresses corrosion of the lower metal film during the stripping process and effectively removes the oxide while having excellent stripping ability for photoresist, thereby completing the present invention.
As the number of high resolution display models increases, copper wiring having low resistance is used as a metal of the TFT. Herein, the copper wiring uses molybdenum (Mo) as a lower film of a barrier metal, and has a structure in which molybdenum having a low oxidation-reduction potential is corroded. However, during the stripping process, which is a process of removing the photoresist, damage occurs between copper and molybdenum due to the stripper, thereby causing quality problems. Therefore, there is a need for improved corrosion inhibitors for preventing corrosion by strippers.
As described above, the stripper composition for removing photoresist of the embodiment comprises an amide compound in which a nitrogen atom is substituted with 1 or 2 linear or branched alkyl groups having 1 to 5 carbon atoms, an amine compound, and a polar organic solvent to maintain excellent stripping ability over time and to thereby effectively remove metal oxide. In addition, methimazole and a triazole-based compound may be included to inhibit corrosion of the underlying metal film.
In particular, the stripper composition for removing photoresist of the embodiment contains both methimazole and a triazole-based compound to inhibit corrosion of a metal-containing underlying film, such as a copper-containing film (particularly a copper/molybdenum metal film), during removal of a photoresist pattern. Further, the corrosion of the metal-containing lower film can be more effectively inhibited even in an equal amount or less, as compared with the case where one of methimazole and a triazole-based compound is used or a conventionally known corrosion inhibitor is used.
The synergistic effect of methimazole and triazole-based compounds appears to be due to the following effects: the effect of inhibiting corrosion by binding of the non-covalent electron pair of the amino group of the triazole-based compound with the metal of the underlying film, such as copper; and an effect of protecting from damage caused by a stripper amine by binding a non-covalent electron pair of a thiol group of methimazole having a lower molecular weight than that of a triazole-based compound with a metal other than the above metals, such as molybdenum (Mo).
In addition, the stripper composition for removing photoresist of the embodiment includes both methimazole and the triazole-based compound, and thus may be removed in a DIW rinsing process immediately after a stripping process to improve contact resistance between the metal-containing lower film and the substrate. For example, the contact resistance between the gate (Cu) and pxl (ito) may be improved.
Herein, examples of the triazole-based compound are not particularly limited, but for example, the triazole-based compound may be at least one compound selected from the group consisting of: (2, 2' - [ [ (methyl-1H-benzotriazol-1-yl) methyl ] imino ] bisethanol, 4,5,6, 7-tetrahydro-1H-benzotriazole, 1H-1,2, 3-triazole and methyl 1H-benzotriazole.
Methimazole may be included at 0.001 wt% to 0.5 wt%, 0.001 wt% to 0.3 wt%, 0.001 wt% to 0.1 wt%, 0.005 wt% to 0.07 wt%, or 0.01 wt% to 0.05 wt% based on the total composition. When the content of methimazole is less than 0.001 wt% based on the entire composition, it may be difficult to effectively inhibit corrosion of the lower membrane. In addition, when the content of methimazole is more than 0.5 wt% based on the entire composition, a large amount of corrosion inhibitor may be adsorbed and remain on the lower film, thereby lowering the electrical characteristics of the copper-containing lower film, particularly the copper/molybdenum metal film. Further, it may be adsorbed on the photoresist to form a protective film and may not be decomposed by amine, so that peeling may not be properly performed and foreign substances may be generated, which may cause quality problems.
Meanwhile, methimazole can more effectively prevent corrosion of the metal-containing lower film even in an equal amount or less than the case of using a conventionally known corrosion inhibitor, and the effect can be maximized when used together with the below-described triazole-based compound in a specific amount.
The triazole-based compound may be included at 0.01 wt% to 5.0 wt%, 0.02 wt% to 2.0 wt%, 0.05 wt% to 1.0 wt%, 0.07 wt% to 0.6 wt%, or 0.1 wt% to 0.5 wt% based on the total composition. When the content of the triazole-based compound is less than 0.01 wt% based on the entire composition, it may be difficult to effectively inhibit corrosion of the lower film. Further, when the content of the triazole-based compound is more than 5.0 wt% based on the entire composition, a large amount of the corrosion inhibitor may be adsorbed and remain on the lower film, thereby lowering the electrical characteristics of the copper-containing lower film, particularly the copper/molybdenum metal film.
Meanwhile, the triazole-based compound may more effectively prevent corrosion of the metal-containing lower film even in an equal amount or less than the case of using the conventionally known corrosion inhibitor, and the effect may be maximized when used together with the aforementioned methimazole in a specific amount.
Meanwhile, the weight ratio of methimazole to the triazole-based compound may be 1:1 to 1:50, 1:1 to 1:40, 1:1.5 to 1:40, or 1:2 to 1: 30. When methimazole and the triazole-based compound have a specific weight ratio as described above, the ability to inhibit corrosion of the lower metal film by the stripper composition for removing photoresist can be maximized, and corrosion of the lower metal film can be more effectively inhibited than the case where one of methimazole and the triazole-based compound is used or one of methimazole and the triazole-based compound is used together with a conventionally known corrosion inhibitor.
In addition, the stripper composition for removing the photoresist may include an amine compound. The amine compound can impart a stripping ability to the photoresist to a stripper composition for removing the photoresist, and specifically, can dissolve the photoresist to remove it.
The amine compound may be included at about 0.1 wt% to 10 wt%, 0.5 wt% to 7 wt%, 1 wt% to 5 wt%, or 2 wt% to 4.6 wt% based on the total composition. The stripper composition of the embodiment within the above range may exhibit excellent stripping ability and the like, may reduce economic inefficiency due to an excessive amount of amine and a decrease in process efficiency, and may reduce generation of waste liquid and the like. When an excessively large amount of the amine compound is contained, this may cause corrosion of the lower metal film (e.g., the lower film containing copper), and it may be necessary to use a large amount of a corrosion inhibitor to inhibit it. In this case, a large amount of the corrosion inhibitor may be adsorbed and remain on the lower film, thereby degrading the electrical characteristics of the copper-containing lower film.
Specifically, when the content of the amine compound is less than 0.1% by weight based on the entire composition, the stripping ability of the stripper composition for removing the photoresist may be reduced. When the content is more than 10% by weight based on the entire composition, economic inefficiency and process efficiency may be reduced due to an excess of the amine compound.
Although the specific kind of the amine compound is not particularly limited, the amine compound may include a cyclic amine compound having a weight average molecular weight of 95g/mol or more.
Examples of the cyclic amine compound are not particularly limited, but may be, for example, 1-imidazolidineethanol, 4-imidazolidineethanol, Hydroxyethylpiperazine (HEP), aminoethylpiperazine, and the like.
Meanwhile, the amine compound may also include a chain amine compound having a weight average molecular weight of 95g/mol or more.
In addition to the stripping ability for photoresists, the chain amine compound having a weight average molecular weight of 95g/mol or more can further improve the adhesion between films (for example, between a copper-containing film and an insulating film thereon such as a silicon nitride film) by appropriately removing a natural oxide film on a lower film (for example, a copper-containing film).
Examples of the chain amine compound having a weight average molecular weight of 95g/mol or more are not particularly limited, but may be, for example, (2-aminoethoxy) -1-ethanol (AEE), aminoethylethanolamine (AEEA), Methyldiethanolamine (MDEA), Diethylenetriamine (DETA), Diethanolamine (DEA), Diethylaminoethanol (DEAE), Triethanolamine (TEA), triethylenetetramine (TETA), or a mixture of two or more thereof.
Meanwhile, the methimazole and the triazole-based compound may be included in a total of 1 to 30 parts by weight, 2 to 25 parts by weight, or 3 to 20 parts by weight, based on 100 parts by weight of the amine compound.
As described above, the amine compound is a component exhibiting stripping ability for the photoresist in the stripper composition for removing the photoresist, and can dissolve the photoresist to remove it. In addition, methimazole and triazole-based compounds inhibit corrosion of the underlying metal film. When the total amount of methimazole and the triazole-based compound is less than 1 part by weight based on 100 parts by weight of the amine compound, it may be difficult to effectively inhibit corrosion of the lower film. Further, when the total amount of methimazole and the triazole-based compound is more than 30 parts by weight based on 100 parts by weight of the amine compound, a large amount of the corrosion inhibitor may be adsorbed and remain on the lower film, thereby degrading the electrical characteristics of the copper-containing lower film, particularly the copper/molybdenum metal film.
Further, the stripper composition for removing the photoresist may comprise an amide compound in which a nitrogen atom is substituted with 1 or 2 linear or branched alkyl groups having 1 to 5 carbon atoms. The amide compound in which the nitrogen atom is substituted with 1 or 2 linear or branched alkyl groups having 1 to 5 carbon atoms can suitably dissolve the amine compound, and the stripper composition for removing the photoresist can effectively penetrate the lower film, thereby improving the stripping and rinsing capabilities of the stripper composition.
Specifically, the amide compound in which the nitrogen atom is substituted with 1 or 2 linear or branched alkyl groups having 1 to 5 carbon atoms may include an amide compound in which the nitrogen atom is substituted with 1 or 2 methyl groups. The amide compound in which a nitrogen atom is substituted with 1 or 2 methyl groups may have a chemical structure represented by the following chemical formula 1.
[ chemical formula 1]
In chemical formula 1, R1Is hydrogen, methyl, ethyl or propyl,
R2and R3Each is hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms, and R2And R3At least one of which is methyl.
Examples of the linear or branched alkyl group having 1 to 5 carbon atoms are not limited. For example, methyl, ethyl, propyl, butyl, isobutyl, pentyl, and the like can be used.
Examples of the amide compound in which the nitrogen atom is substituted with 1 or 2 methyl groups are not limited. For example, R in chemical formula 1 may be used2Is methyl and R1And R3A compound which is hydrogen.
The amide compound in which the nitrogen atom is substituted with 1 or 2 linear or branched alkyl groups having 1 to 5 carbon atoms may be included at 10 to 80% by weight, 15 to 70% by weight, or 25 to 60% by weight, based on the entire composition. The stripper composition for removing photoresist of the embodiment within the above range may exhibit excellent stripping ability, etc., and may maintain stripping and rinsing ability for a long time.
In addition, the stripper composition for removing the photoresist may include a polar organic solvent. The polar organic solvent can effectively penetrate the lower film for the stripper composition for removing the photoresist, thereby contributing to the excellent stripping ability of the stripper composition. In addition, it can effectively remove stains on underlying films such as copper-containing films to improve the rinsing ability of a stripper composition for removing a photoresist.
The polar organic solvent may comprise an alkylene glycol monoalkyl ether, a pyrrolidone, a sulfone, a sulfoxide, or a mixture of two or more thereof. More specifically, the alkylene glycol monoalkyl ether may include diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 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, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, or a mixture of two or more thereof.
In addition, in view of excellent wettability of the stripper composition for removing the photoresist and thus improved stripping and rinsing capabilities, diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl Ether (EDG), diethylene glycol monobutyl ether (BDG), and the like can be used as the alkylene glycol monoalkyl ether.
Examples of the pyrrolidone are not particularly limited, but for example, N-methylpyrrolidone, pyrrolidone, N-ethylpyrrolidone, and the like can be used. Examples of the sulfone are not particularly limited, but, for example, sulfolane may be used. Examples of the sulfoxide are not particularly limited, but for example, dimethyl sulfoxide (DMSO), diethyl sulfoxide, dipropyl sulfoxide, and the like can be used.
The polar organic solvent may be included at 10 to 80 wt%, 20 to 78 wt%, or 40 to 70 wt% based on the total composition. The stripper composition for removing photoresist of the embodiment within the above range may exhibit excellent stripping ability, etc., and may maintain stripping and rinsing ability for a long time.
Meanwhile, the stripper composition for removing the photoresist may further include a silicone-based nonionic surfactant. The silicone-based nonionic surfactant can be stable even in a highly alkaline stripper composition comprising an amine compound without causing chemical changes, denaturation or decomposition. In addition, it can exhibit excellent compatibility with the above-mentioned polar aprotic solvent or protic organic solvent. Thus, the silicone-based nonionic surfactant can be mixed with other components to reduce the surface tension of the stripper composition and to exhibit better wettability to the photoresist and underlying films thereof that the stripper composition is intended to remove. As a result, the stripper composition of the embodiment including the same can exhibit excellent stripping ability and can also exhibit excellent rinsing ability with respect to the lower film, so that little stains and foreign matters are generated and remain on the lower film even after the treatment with the stripper composition, and the stains and foreign matters can be effectively removed.
Further, the silicone-based nonionic surfactant can exhibit the above-described effects even at a very low content, and the generation of by-products due to denaturation or decomposition thereof can be minimized.
Specifically, the silicone-based nonionic surfactant may include a polysiloxane-based polymer. Examples of the polysiloxane-based polymer are not particularly limited, but for example, the following may be used: polyether modified acrylic functional polydimethylsiloxane, polyether modified siloxane, polyether modified polydimethylsiloxane, polyethyl alkyl siloxane, aralkyl modified polymethylalkyl siloxane, polyether modified hydroxy functional polydimethylsiloxane, polyether modified dimethylpolysiloxane, modified acrylic functional polydimethylsiloxane, or a mixture of two or more thereof.
The silicone-based nonionic surfactant can be included at 0.0005 wt% to 0.1 wt%, 0.001 wt% to 0.09 wt%, or 0.001 wt% to 0.01 wt%, based on the total composition. When the content of the silicone-based nonionic surfactant is less than 0.0005 wt% based on the entire composition, the ability to effectively improve peeling and rinsing of the stripper composition may not be sufficient. Further, when the content of the silicone-based nonionic surfactant is more than 0.1% by weight based on the entire composition, bubbles may be generated at high pressure during a peeling process using the peeling agent composition, thereby causing stains on the lower film or causing malfunction of the device sensor.
The stripper composition for removing the photoresist may further comprise conventional additives, as necessary. There is no particular limitation on the specific type or content of the additive.
Further, the photoresist stripper composition for removing photoresist may be prepared according to a general method of mixing the above components, and a specific method of preparing the stripper composition for removing photoresist is not particularly limited.
Meanwhile, according to another embodiment of the present disclosure, there is provided a method for stripping a photoresist including the step of stripping the photoresist by using the stripper composition for removing the photoresist of the embodiment.
The description relating to the stripper composition for removing photoresist includes the detailed description relating to the above embodiments.
The method for stripping photoresist may include the steps of: forming a photoresist pattern on a substrate whose upper and lower films are to be patterned through a photolithography process; patterning the lower film using the photoresist pattern as a mask; and stripping the photoresist by using the above stripper composition.
In the method for stripping the photoresist, the steps of forming the photoresist pattern and patterning the lower film may use a conventional manufacturing process of the device, and a specific method is not particularly limited.
Meanwhile, examples of the step of stripping the photoresist by using the stripper composition for removing the photoresist are not particularly limited, but for example, the following steps may be used: applying a stripper composition for removing the photoresist to the substrate where the photoresist pattern remains; and subjecting it to washing with an alkaline buffer solution; then washed with ultrapure water and dried. Since the above-mentioned stripper composition exhibits a rinsing ability to effectively remove stains on the lower film and an ability to remove a natural oxide film and an excellent stripping ability, it can satisfactorily maintain the surface state of the lower film while effectively removing a photoresist pattern remaining on the lower film. Accordingly, subsequent steps may be performed on the patterned lower film as appropriate to form a device.
Examples of the lower film formed on the substrate are not particularly limited, but may include aluminum or an aluminum alloy, copper or a copper alloy, molybdenum or a molybdenum alloy, a mixture thereof, a composite alloy thereof, a composite laminate thereof, and the like.
The kind, composition or physical properties of the photoresist to which the above-described stripping method can be applied are also not particularly limited. For example, the photoresist may be a photoresist known for a lower film including aluminum or an aluminum alloy, copper or a copper alloy, molybdenum or a molybdenum alloy, or the like. More specifically, the photoresist may include a photosensitive resin, such as a novolac resin, a resole resin, or an epoxy resin.
Advantageous effects
According to the present disclosure, a stripper composition for removing a photoresist capable of inhibiting corrosion of a lower metal film during a stripping process and effectively removing an oxide while being capable of exhibiting excellent stripping ability for the photoresist, and a method for stripping a photoresist using the same can be provided.
Detailed Description
The present invention will be explained in more detail in the following examples. However, these examples are for illustrative purposes only, and the present invention is not intended to be limited by these examples.
< examples 1 to 5: preparation of stripper composition for removing Photoresist >
The components were mixed according to the compositions of table 1 below to prepare the stripper compositions for removing photoresist of examples 1 to 5, respectively. The specific composition of the stripper composition for removing photoresist prepared is shown in table 1 below.
[ Table 1]
Composition of stripper composition for removing photoresist
LGA: 1-imidazolidineethanol
NMF: n-methylformamide
EDG: diethylene glycol monoethyl ether
MDG: diethylene glycol monomethyl ether
BDG: diethylene glycol monobutyl ether
Corrosion inhibitor 1: methimazole
Corrosion inhibitor 2: (2, 2' - [ [ (methyl-1H-benzotriazol-1-yl) methyl ] imino ] bis ethanol
Corrosion inhibitor 3: benzimidazole compounds
Corrosion inhibitor 4: imidazole
Corrosion inhibitor 5: 2-methylimidazole
Corrosion inhibitor 6: 2-mercaptobenzimidazoles
< comparative examples 1 to 5: preparation of stripper composition for removing Photoresist >
The components were mixed according to the compositions of table 2 below to prepare the stripper compositions for removing photoresist of comparative examples 1 to 5, respectively. The specific composition of the stripper composition for removing photoresist prepared is shown in the following table 2.
[ Table 2]
Composition of stripper composition for removing photoresist
LGA: 1-imidazolidineethanol
NMF: n-methylformamide
EDG: diethylene glycol monoethyl ether
MDG: diethylene glycol monomethyl ether
BDG: diethylene glycol monobutyl ether
Corrosion inhibitor 1: methimazole
Corrosion inhibitor 2: (2, 2' - [ [ (methyl-1H-benzotriazol-1-yl) methyl ] imino ] bis ethanol
Corrosion inhibitor 3: benzimidazole compounds
Corrosion inhibitor 4: imidazole
Corrosion inhibitor 5: 2-methylimidazole
Corrosion inhibitor 6: 2-mercaptobenzimidazoles
< experimental examples: measurement of physical characteristics of the stripper compositions for removing photoresists obtained in examples and comparative examples >
Physical properties of the stripper compositions obtained in examples and comparative examples were measured by the following methods, and the results are shown in the table.
1. Evaluation of peeling ability
First, 3.5ml of a photoresist composition (trade name: JC-800) was dropped to a 100mm by 100mm glass substrate and the photoresist composition was applied at 400rpm for 10 seconds in a spin coating apparatus. The glass substrate was mounted on a hot plate and hard-baked at a temperature of 150 ℃ or 140 ℃ for 20 minutes to form a photoresist. The glass substrate having the photoresist formed thereon was air-cooled at room temperature and then cut into a size of 30mm × 30mm to prepare a sample for evaluating the stripping ability of the new liquid of the stripper.
500g of the stripper composition obtained in examples 1 to 5 and one of comparative examples 1 to 4, 6 and 7 was prepared. The photoresist on the glass substrate was treated with the stripper composition in a state where the temperature was increased to 50 ℃. The time required to completely strip and remove the photoresist was measured to evaluate the stripping ability of the new liquid of stripper. At this time, completion of the peeling of the photoresist was confirmed by irradiating ultraviolet light on the glass substrate to observe whether or not the photoresist remained.
The stripping abilities of the stripper compositions of examples 1 to 5 and comparative examples 1 to 4, 6 and 7 were evaluated as described above, and the results are shown in the following tables 3 and 4.
[ Table 3]
| Categories | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Stripping time | 240 seconds | 240 seconds | 240 seconds | 240 seconds | 240 seconds |
[ Table 4]
| Categories | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 6 | Comparative example 7 |
| Stripping time | 240 seconds | 240 seconds | 240 seconds | 240 seconds | 360 seconds | 240 seconds |
As shown in the above tables 3 and 4, it was determined that the stripper compositions of examples 1 to 5 exhibited the same or superior level of stripping ability as compared to the stripper compositions of comparative examples 1 to 4, 6 and 7.
2. Corrosion evaluation of copper (Cu) metal
3.5ml of a photoresist composition (trade name: JC-800) was dropped to a 100mm by 100mm glass substrate having a copper-containing thin film formed thereon, and the photoresist composition was applied at 400rpm for 10 seconds in a spin-coating apparatus. The glass substrate was mounted on a hot plate and hard-baked at a temperature of 150 ℃ or 140 ℃ for 20 minutes to form a photoresist. The glass substrate formed with the photoresist was air-cooled at room temperature and then cut into a size of 30mm × 30mm to prepare a sample for corrosion evaluation.
500g of the stripper composition obtained in one of examples 1, 3, 4 and 5 and comparative examples 1 to 7 was heated to a temperature of 50 ℃, and the sample for corrosion evaluation was immersed in the stripper composition at a temperature of 50 ℃ for 10 minutes, and then washed with ultrapure water. The corrosion state of the washed sample surface was measured by SEM to evaluate the corrosion of copper metal, and the results are shown in tables 5 and 6 below.
[ Table 5]
[ Table 6]
As shown in tables 5 and 6 above, it was determined that the stripper compositions of examples 1, 3, 4 and 5 were less corrosive to copper metal than the stripper compositions of comparative examples 2 to 5 by including both methimazole and a triazole-based compound.
From these results, it can be seen that methimazole and the triazole-based compound contained in the stripper compositions of the examples have excellent ability to prevent corrosion of copper metal.
3. Corrosion evaluation of copper (Cu)/molybdenum (Mo) Metal bottom film
A section of the sample for corrosion evaluation obtained in one of examples 1 to 5 and comparative examples 1, 3, 4, 6 and 7 was observed using a transmission electron microscope (Helios NanoLab 650). Specifically, a thin sheet of the sample for corrosion evaluation was prepared using FIB (Focused Ion Beam), and then observed at an acceleration voltage of 2 kV. In order to prevent damage to the surface by the ion beam, a TEM thin plate was prepared after forming a Pt (platinum) protective layer on the surface (Cu layer) of the sample.
[ Table 7]
| Categories | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Size (nm) | <10nm | <10nm | <10nm | <10nm | <10nm |
[ Table 8]
| Categories | Comparative example 1 | Comparative example 3 | Comparative example 4 | Comparative example 7 |
| Size (nm) | 137nm | 292nm | 251nm | 283nm |
As shown in tables 7 and 8 above, it was determined that the stripper compositions of examples 1 to 5, which included both methimazole and a triazole-based compound, had reduced corrosion of the copper (Cu)/molybdenum (Mo) metal lower film, as compared to the stripper compositions of comparative example 1, which included methimazole and benzimidazole, and comparative examples 3, 4, and 7, which included one corrosion inhibitor.
From these results, it can be seen that methimazole and the triazole-based compound contained in the stripper composition of the example have excellent ability to prevent corrosion of the copper (Cu)/molybdenum (Mo) metal lower film.
Claims (10)
1. A stripper composition for removing photoresist comprising: amide compounds in which the nitrogen atom is substituted with 1 or 2 linear or branched alkyl groups having 1 to 5 carbon atoms;
an amine compound;
a polar organic solvent;
methimazole; and
a triazole-based compound.
2. The stripper composition for removing photoresist according to claim 1,
wherein the weight ratio of the methimazole to the triazole-based compound is from 1:1 to 1: 50.
3. The stripper composition for removing photoresist according to claim 1,
wherein the methimazole and the triazole-based compound are included in total in an amount of 1 to 30 parts by weight, based on 100 parts by weight of the amine compound.
4. The stripper composition for removing photoresist according to claim 1,
wherein the triazole-based compound includes at least one compound selected from the group consisting of: (2, 2' - [ [ (methyl-1H-benzotriazol-1-yl) methyl ] imino ] bisethanol, 4,5,6, 7-tetrahydro-1H-benzotriazole, 1H-1,2, 3-triazole and methyl 1H-benzotriazole.
5. The stripper composition for removing photoresist according to claim 1,
wherein the amine compound comprises a cyclic amine compound having a weight average molecular weight of 95g/mol or more.
6. The stripper composition for removing photoresist according to claim 5,
wherein the amine compound further includes a chain amine compound having a weight average molecular weight of 95g/mol or more.
7. The stripper composition for removing photoresist according to claim 1,
wherein the amide compound in which a nitrogen atom is substituted with 1 or 2 linear or branched alkyl groups having 1 to 5 carbon atoms includes a compound represented by the following chemical formula 1:
[ chemical formula 1]
Wherein, in chemical formula 1，R1Is hydrogen, methyl, ethyl or propyl,
R2and R3Each is hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms, and R2And R3At least one of which is methyl.
8. The stripper composition for removing photoresist according to claim 1,
wherein the polar organic solvent comprises at least one selected from the group consisting of alkylene glycol monoalkyl ethers, pyrrolidones, sulfones, and sulfoxides.
9. The stripper composition for removing photoresist according to claim 1, comprising, based on the entire composition:
10 to 80% by weight of the amide compound in which a nitrogen atom is substituted with 1 or 2 linear or branched alkyl groups having 1 to 5 carbon atoms;
0.1 to 10 wt% of the amine compound;
10 to 80 wt% of the polar organic solvent;
0.001 to 0.5% by weight of the methimazole; and
0.01 to 5.0 wt.% of the triazole-based compound.
10. A method for stripping a photoresist comprising a step of stripping the photoresist by using the stripper composition for removing a photoresist according to claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2019-0033204 | 2019-03-22 | ||
| KR1020190033204A KR20200112551A (en) | 2019-03-22 | 2019-03-22 | Stripper composition for removing photoresist and stripping method of photoresist using the same |
| PCT/KR2019/013124 WO2020197014A1 (en) | 2019-03-22 | 2019-10-07 | Photoresist-removing stripper composition and method for stripping photoresist using same |
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| Publication Number | Publication Date |
|---|---|
| CN111989621A true CN111989621A (en) | 2020-11-24 |
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| CN201980009806.8A Pending CN111989621A (en) | 2019-03-22 | 2019-10-07 | Stripper composition for removing photoresist and method for stripping photoresist using the same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7081739B2 (en) |
| KR (1) | KR20200112551A (en) |
| CN (1) | CN111989621A (en) |
| TW (1) | TWI805865B (en) |
| WO (1) | WO2020197014A1 (en) |
Citations (6)
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| CN1591199A (en) * | 2003-08-27 | 2005-03-09 | Lg.菲利浦Lcd有限公司 | Composition and method for removing copper-compatible resist |
| KR20050023163A (en) * | 2003-08-27 | 2005-03-09 | 엘지.필립스 엘시디 주식회사 | Composition for removing a (photo)resist |
| KR20100032993A (en) * | 2008-09-19 | 2010-03-29 | 에스케이에너지 주식회사 | Stripper composition for removing photoresist |
| KR20100033649A (en) * | 2008-09-22 | 2010-03-31 | 에스케이에너지 주식회사 | Stripper composition for removing photoresist |
| CN101692155A (en) * | 2007-12-28 | 2010-04-07 | 株式会社东进世美肯 | Composition for removing photoresist and method for manufacturing array substrate using the same |
| CN107924144A (en) * | 2015-08-13 | 2018-04-17 | Ltc有限公司 | For manufacturing the light carving rubber stripper composition of liquid crystal display |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4500657B2 (en) * | 2004-11-30 | 2010-07-14 | 旭化成イーマテリアルズ株式会社 | Pattern forming material, pattern forming apparatus and pattern forming method |
| JP2010000612A (en) * | 2008-06-18 | 2010-01-07 | Fujifilm Corp | Nanoimprinting curable composition and pattern forming method |
| KR101721262B1 (en) * | 2010-09-01 | 2017-03-29 | 동우 화인켐 주식회사 | Resist stripper composition and a method of stripping resist using the same |
| KR101668063B1 (en) * | 2013-05-07 | 2016-10-20 | 주식회사 엘지화학 | Stripper composition for removing photoresist and stripping mthod of photoresist using the same |
| KR102510370B1 (en) * | 2014-10-06 | 2023-03-17 | 도레이 카부시키가이샤 | Resin composition, method for producing heat-resistant resin film, and display device |
| CN107430335B (en) * | 2015-04-01 | 2021-04-02 | 东丽株式会社 | Photosensitive colored resin composition |
| KR102414295B1 (en) * | 2016-01-22 | 2022-06-30 | 주식회사 이엔에프테크놀로지 | Photoresist stripper composition |
-
2019
- 2019-03-22 KR KR1020190033204A patent/KR20200112551A/en not_active Application Discontinuation
- 2019-10-07 WO PCT/KR2019/013124 patent/WO2020197014A1/en active Application Filing
- 2019-10-07 JP JP2020537631A patent/JP7081739B2/en active Active
- 2019-10-07 CN CN201980009806.8A patent/CN111989621A/en active Pending
- 2019-10-21 TW TW108137869A patent/TWI805865B/en active
Patent Citations (6)
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|---|---|---|---|---|
| CN1591199A (en) * | 2003-08-27 | 2005-03-09 | Lg.菲利浦Lcd有限公司 | Composition and method for removing copper-compatible resist |
| KR20050023163A (en) * | 2003-08-27 | 2005-03-09 | 엘지.필립스 엘시디 주식회사 | Composition for removing a (photo)resist |
| CN101692155A (en) * | 2007-12-28 | 2010-04-07 | 株式会社东进世美肯 | Composition for removing photoresist and method for manufacturing array substrate using the same |
| KR20100032993A (en) * | 2008-09-19 | 2010-03-29 | 에스케이에너지 주식회사 | Stripper composition for removing photoresist |
| KR20100033649A (en) * | 2008-09-22 | 2010-03-31 | 에스케이에너지 주식회사 | Stripper composition for removing photoresist |
| CN107924144A (en) * | 2015-08-13 | 2018-04-17 | Ltc有限公司 | For manufacturing the light carving rubber stripper composition of liquid crystal display |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7081739B2 (en) | 2022-06-07 |
| TW202046028A (en) | 2020-12-16 |
| WO2020197014A1 (en) | 2020-10-01 |
| JP2021518922A (en) | 2021-08-05 |
| KR20200112551A (en) | 2020-10-05 |
| TWI805865B (en) | 2023-06-21 |
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