TWI805865B - Stripper composition for removing photoresists and method for stripping photoresists using the same - Google Patents
Stripper composition for removing photoresists and method for stripping photoresists using the same Download PDFInfo
- Publication number
- TWI805865B TWI805865B TW108137869A TW108137869A TWI805865B TW I805865 B TWI805865 B TW I805865B TW 108137869 A TW108137869 A TW 108137869A TW 108137869 A TW108137869 A TW 108137869A TW I805865 B TWI805865 B TW I805865B
- Authority
- TW
- Taiwan
- Prior art keywords
- photoresist
- weight
- stripping
- compound
- composition
- Prior art date
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 119
- 239000000203 mixture Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 30
- -1 amide compound Chemical class 0.000 claims description 72
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims description 31
- 229960002178 thiamazole Drugs 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000003495 polar organic solvent Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 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
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- 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
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 2
- 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 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
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- CKRLKUOWTAEKKX-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2h-benzotriazole Chemical compound C1CCCC2=NNN=C21 CKRLKUOWTAEKKX-UHFFFAOYSA-N 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 48
- 238000005260 corrosion Methods 0.000 abstract description 48
- 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 4
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 78
- 239000010949 copper Substances 0.000 description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 30
- 229910052802 copper Inorganic materials 0.000 description 30
- 239000003112 inhibitor Substances 0.000 description 19
- 150000003852 triazoles Chemical class 0.000 description 18
- 239000000758 substrate Substances 0.000 description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 14
- 229920001296 polysiloxane Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052750 molybdenum Inorganic materials 0.000 description 10
- 239000011733 molybdenum Substances 0.000 description 10
- 239000002736 nonionic surfactant Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000059 patterning Methods 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-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
- 230000005540 biological transmission Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 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
- 230000015556 catabolic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 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
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 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
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002829 reductive effect Effects 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
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 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
- 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 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
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 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
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 230000000593 degrading effect Effects 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 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
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 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)
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Abstract
Description
本揭露是有關於一種用於移除光阻的剝離劑組成物以及一種使用其剝離光阻之方法。更具體而言，本揭露是有關於一種用於移除光阻的剝離劑組成物且有關於一種使用其剝離光阻之方法，所述用於移除光阻的剝離劑組成物能夠抑制在剝離製程期間下部金屬膜的腐蝕，且能夠在對光阻表現出極佳剝離能力的同時有效地移除氧化物。 The present disclosure relates to a stripper composition for removing photoresist and a method for stripping photoresist using the same. More specifically, the present disclosure relates to a stripper composition for removing photoresist capable of suppressing Erosion of the underlying metal film during the lift-off process, and can effectively remove oxide while exhibiting excellent lift-off capability for photoresist.
[相關申請案的交叉參考] [CROSS-REFERENCE TO RELATED APPLICATIONS]
本申請案主張2019年3月22日向韓國智慧財產局提出申請的韓國專利申請案第10-2019-0033204號的權益，所述韓國專利申請案的揭露內容全文併入本案供參考。 This application claims the rights and interests of the Korean Patent Application No. 10-2019-0033204 filed with the Korea Intellectual Property Office on March 22, 2019, the disclosure of which is incorporated herein by reference in its entirety.
液晶顯示裝置的微電路或半導體積體電路的製造製程包括以下若干步驟：在基板上形成各種下部膜，例如由鋁、鋁合 金、銅、銅合金、鉬或鉬合金製成的導電金屬膜或者例如氧化矽膜、氮化矽膜或丙烯醯基絕緣膜等絕緣膜；在下部膜上均勻地施加光阻；可選地對所施加的光阻進行曝光及顯影以形成光阻圖案；以及以光阻圖案作為遮罩來圖案化下部膜。在圖案化步驟之後，進行移除餘留於下部膜上的光阻的製程。為達成此目的，使用用於移除光阻的剝離劑組成物。 The manufacturing process of the microcircuit or semiconductor integrated circuit of the liquid crystal display device includes the following steps: forming various lower films on the substrate, such as aluminum, aluminum alloy A conductive metal film made of gold, copper, copper alloy, molybdenum or molybdenum alloy or an insulating film such as a silicon oxide film, a silicon nitride film, or an acryl-based insulating film; a photoresist is uniformly applied on the lower film; optionally exposing and developing the applied photoresist to form a photoresist pattern; and using the photoresist pattern as a mask to pattern the lower film. 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 photoresist is used.
以前，包括胺化合物、極性質子性溶劑、極性非質子性溶劑等的剝離劑組成物已眾所習知且被廣泛使用。已知該些剝離劑組成物對光阻表現出某種程度的移除及剝離能力。 Heretofore, stripper compositions including amine compounds, polar protic solvents, polar aprotic solvents, etc. have been known and widely used. These stripper compositions are known to exhibit a certain degree of removal and stripping ability for photoresists.
然而，當剝離大量光阻時，該些傳統剝離劑組成物促進胺化合物隨著時間推移而分解，因此存在剝離及漂洗能力隨著時間的推移而降低的問題。具體而言，視剝離劑組成物的使用次數而定，若殘留光阻中的一些溶解於剝離劑組成物中，則該些問題可能會進一步加速。 However, these conventional stripper compositions promote the decomposition of amine compounds over time when stripping a large amount of photoresist, and thus have a problem that stripping and rinsing capabilities decrease over time. Specifically, depending on the number of uses of the stripper composition, these problems may be further accelerated if some of the residual photoresist dissolves in the stripper composition.
此外，當使用銅金屬膜作為下部膜時，由於剝離製程中的腐蝕，會產生污漬及異物，此使得難以使用下部膜。此外，存在例如不能夠有效地移除銅的氧化物的限制。 In addition, when a copper metal film is used as the lower film, stains and foreign matter are generated due to corrosion in the lift-off process, which makes it difficult to use the lower film. In addition, there are limitations such as inability to efficiently remove oxides of copper.
本揭露旨在提供一種用於移除光阻的剝離劑組成物，所述用於移除光阻的剝離劑組成物能夠抑制在剝離製程期間下部金 屬膜的腐蝕，且能夠在對光阻表現出極佳剝離能力的同時有效地移除氧化物。 The present disclosure aims to provide a stripper composition for removing photoresist, which can inhibit the underlying gold Etch of metal film, and can effectively remove oxide while exhibiting excellent stripping ability for photoresist.
本揭露旨在提供一種使用用於移除光阻的剝離劑組成物剝離光阻的方法。 The present disclosure aims to provide a method for stripping photoresist using a stripper composition for removing photoresist.
在本揭露中，提供一種用於移除光阻的剝離劑組成物，所述用於移除光阻的剝離劑組成物包括：醯胺化合物，其中具有1至5個碳原子的直鏈或支鏈烷基被1或2個氮原子取代；胺化合物；極性有機溶劑；甲巰咪唑(methimazole)；以及***系(triazole-based)化合物。 In the present disclosure, a stripper composition for removing photoresist is provided, and the stripper composition for removing photoresist includes: an amide compound having a straight chain or Branched chain alkyl substituted with 1 or 2 nitrogen atoms; amine compounds; polar organic solvents; methimazole; and triazole-based compounds.
在本揭露中，亦提供一種剝離光阻的方法，所述方法包括以下步驟：在其中形成下部膜的基板上形成光阻圖案；以光阻圖案來圖案化下部膜；以及使用用於移除光阻的剝離劑組成物剝離光阻。 In the present disclosure, there is also provided a method of stripping a photoresist, the method including the steps of: forming a photoresist pattern on a substrate in which a lower film is formed; patterning the lower film with the photoresist pattern; The photoresist stripper composition strips the photoresist.
在下文中，將詳細闡述根據本發明具體實施例的一種用於移除光阻的剝離劑組成物以及一種使用其剝離光阻之方法。 Hereinafter, a stripper composition for removing photoresist and a method for stripping photoresist using the stripper composition according to specific embodiments of the present invention will be described in detail.
本文中所使用的術語僅用於闡述特定實施例的目的，且不旨在限制本發明。除非上下文另外清楚地作出指示，否則單數形式旨在亦包括複數形式。更將理解，當在本說明書中使用用語「包括」、「具有」及「擁有」時是指定所陳述特徵、數目、步驟、組件或其組合的存在，但不排除一或多個其他特徵、數目、步驟、組件或其組合的存在或添加。 The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless the context clearly dictates otherwise, singular forms are intended to include plural forms as well. It will be further understood that when the terms "comprise", "have" and "have" are used in this specification, they designate the presence of stated features, numbers, steps, components or combinations thereof, but do not exclude one or more other features, The presence or addition of numbers, steps, components or combinations thereof.
由於本發明可進行各種修改且具有各種形式，因此以實例的方式示出本發明的具體實施例且將對本發明的具體實施例進行詳細闡述。然而，本發明不旨在將本發明限制於所揭露的特定形式，且應理解，本發明包括處於本發明的理念及技術範圍內的所有修改、等效形式及替換。 Since the invention is susceptible to various modifications and forms, specific embodiments of the invention are shown by way of example and will be described in detail. However, the present invention is not intended to limit the present invention to the specific forms disclosed, and it should be understood that the present invention includes all modifications, equivalent forms and replacements within the concept and technical scope of the present invention.
根據本揭露的一個實施例，提供一種用於移除光阻的剝離劑組成物，所述用於移除光阻的剝離劑組成物包括：醯胺化合物，其中具有1至5個碳原子的直鏈或支鏈烷基被1或2個氮原子取代；胺化合物；極性有機溶劑；甲巰咪唑；以及***系化合物。 According to an embodiment of the present disclosure, there is provided a stripper composition for removing photoresist, the stripper composition for removing photoresist includes: an amide compound, wherein a compound having 1 to 5 carbon atoms Straight chain or branched chain alkyl substituted by 1 or 2 nitrogen atoms; amine compounds; polar organic solvents; methimazole; and triazole compounds.
本發明者對一種用於移除光阻的剝離劑組成物進行了研究，且藉由實驗發現，包括上述組分的用於移除光阻的剝離劑組成物會抑制在剝離製程期間下部金屬膜的腐蝕，且在對光阻具有極佳剝離能力的同時有效地移除氧化物，藉此完成本發明。 The present inventors conducted research on a stripper composition for removing photoresist, and found through experiments that the stripper composition for removing photoresist including the above-mentioned components can inhibit the lower metal during the stripping process. The etching of the film, and effectively removes the oxide while having excellent stripping ability to the photoresist, thereby completing the present invention.
隨著高解析度顯示模型的數目增加，具有低電阻的銅配線被用作薄膜電晶體(thin film transistor，TFT)的金屬。此處，銅配線使用鉬(Mo)作為障壁金屬的下部膜，且具有其中具有低氧化還原電位的鉬發生腐蝕的結構。然而，在作為移除光阻的製程的剝離製程期間，剝離劑在銅與鉬之間造成損壞，從而導致質量問題。因此，需要改進腐蝕抑制劑以防止剝離劑的腐蝕。 As the number of high-resolution display models increases, copper wiring having low resistance is used as a metal of a thin film transistor (TFT). Here, the copper wiring uses molybdenum (Mo) as the lower film of the barrier metal, and has a structure in which molybdenum having a low oxidation-reduction potential corrodes. However, the stripper causes damage between copper and molybdenum during the stripping process, which is a process of removing the photoresist, thereby causing quality problems. Therefore, there is a need for improved corrosion inhibitors to prevent corrosion of strippers.
如上所述，所述實施例的用於移除光阻的剝離劑組成物包括醯胺化合物、胺化合物以及極性有機溶劑，以隨著時間的推 移維持極佳剝離能力以及有效地移除金屬氧化物，在醯胺化合物中，具有1至5個碳原子的直鏈或支鏈烷基被1或2個氮原子取代。此外，可包括甲巰咪唑及***系化合物以抑制下部金屬膜的腐蝕。 As described above, the stripper composition for removing photoresist of the embodiment includes an amide compound, an amine compound, and a polar organic solvent, to To maintain excellent stripping ability and effectively remove metal oxides, in the amide compound, a linear or branched alkyl group having 1 to 5 carbon atoms is substituted by 1 or 2 nitrogen atoms. In addition, methimazole and triazole compounds may be included to inhibit corrosion of the lower metal film.
具體而言，所述實施例的用於移除光阻的剝離劑組成物一起包括甲巰咪唑及***系化合物，以在移除光阻圖案期間抑制含金屬下部膜(例如含銅膜，尤其是銅/鉬金屬膜)的腐蝕。此外，相較於使用甲巰咪唑及***系化合物中的一者或使用傳統上已知的腐蝕抑制劑的情形，即使使用等效的量或更少的量，亦可更有效地抑制含金屬下部膜的腐蝕。 Specifically, the stripper composition for removing photoresist of the embodiment includes methimazole and a triazole-based compound together to suppress the metal-containing lower film (such as a copper-containing film, Especially the corrosion of copper/molybdenum metal film). In addition, compared with the case of using one of methimazole and triazole-based compounds or using a conventionally known corrosion inhibitor, even with an equivalent amount or less, it is possible to more effectively inhibit the corrosion inhibitor containing Corrosion of the underlying metal film.
甲巰咪唑及***系化合物的協同作用(synergism)似乎是由於以下而造成：藉由將***系化合物的胺基的非共價電子對與下部膜的金屬(例如銅)連結來抑制腐蝕的效應，以及藉由將分子量低於***系化合物的甲巰咪唑的硫醇基的非共價電子對與除上述金屬(例如鉬(Mo))以外的金屬連結來保護免受由剝離劑胺引起的損壞的效應。 The synergism between methimazole and triazoles appears to be due to the inhibition of corrosion by linking the non-covalent electron pairs of the amine groups of the triazoles to the metal of the underlying film, such as copper. effect, and by linking the non-covalent electron pair of the thiol group of methimazole, which has a molecular weight lower than that of the triazole-based compound, to metals other than the above-mentioned metals (such as molybdenum (Mo)) to protect from the release agent Damaged effects caused by amines.
此外，所述實施例的用於移除光阻的剝離劑組成物一起包括甲巰咪唑及***系化合物，且因此可在剝離製程之後立即在去離子水(deionized water，DIW)漂洗製程中移除，以提高含金屬下部膜與基板之間的接觸電阻。舉例而言，可改善閘極(Cu)與畫素(PXL)(ITO)之間的接觸電阻。 In addition, the stripper composition for removing photoresist of the embodiments includes methimazole and triazole compounds together, and thus can be rinsed in deionized water (DIW) immediately after the stripping process removed to increase the contact resistance between the metal-containing lower film and the substrate. For example, the contact resistance between the gate (Cu) and the pixel (PXL) (ITO) can be improved.
在本文中，***系化合物的實例並無特別限制，但是舉 例而言，***系化合物可為選自由2,2’-[[(甲基-1H-苯並***-1-基)甲基]亞胺基]雙乙醇(2,2’-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol)、4,5,6,7-四氫-1H-苯並***(4,5,6,7-tetrahydro-1H-benzotriazole)、1H-苯並***、1H-1,2,3-***及甲基1H-苯並***組成的群組的至少一種化合物。 Herein, examples of triazole compounds are not particularly limited, but For example, the triazole compound may be selected from 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol (2,2'-[ [(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol), 4,5,6,7-tetrahydro-1H-benzotriazole (4,5,6,7-tetrahydro-1H-benzotriazole ), 1H-benzotriazole, 1H-1,2,3-triazole and at least one compound of the group consisting of methyl 1H-benzotriazole.
以總組成物計，甲巰咪唑的含量可為0.001重量%(wt%)至0.5重量%、0.001重量%至0.3重量%、0.001重量%至0.1重量%、0.005重量%至0.07重量%或0.01重量%至0.05重量%。以總組成物計，當甲巰咪唑的含量小於0.001重量%時，可能難以有效地抑制下部膜的腐蝕。此外，以總組成物計，當甲巰咪唑的含量大於0.5重量%時，顯著量的腐蝕抑制劑可能被吸附並保留於下部膜上，從而降低含銅下部膜(尤其是銅/鉬金屬膜)的電性性質。此外，腐蝕抑制劑可能被吸附於光阻上而形成保護膜，且可能無法藉由胺來分解，因此無法恰當地進行剝離，且可能產生異物，此可能引起質量問題。 Based on the total composition, the content of methimazole can be 0.001% by weight (wt%) to 0.5% by weight, 0.001% by weight to 0.3% by weight, 0.001% by weight to 0.1% by weight, 0.005% by weight to 0.07% by weight or 0.01% by weight % by weight to 0.05% by weight. When the content of methimazole is less than 0.001% by weight based on the total composition, it may be difficult to effectively suppress corrosion of the lower film. In addition, based on the total composition, when the content of methimazole is greater than 0.5% by weight, a significant amount of corrosion inhibitors may be adsorbed and retained on the lower film, thereby reducing the copper-containing lower film (especially the copper/molybdenum metal film). ) electrical properties. In addition, the corrosion inhibitor may be adsorbed on the photoresist to form a protective film, and may not be decomposed by amine, so the peeling cannot be performed properly, and foreign matter may be generated, which may cause quality problems.
同時，相較於使用傳統上已知的腐蝕抑制劑的情形，即使使用等效的量或更少的量，甲巰咪唑亦可更高效地防止含金屬下部膜的腐蝕，且當以特定量與下述***系化合物一起使用時，此種效果可最大化。 Meanwhile, compared with the case of using conventionally known corrosion inhibitors, methimazole can prevent the corrosion of the metal-containing lower film more efficiently even when using an equivalent amount or less, and when used in a specific amount This effect can be maximized when used together with the following triazole-based compounds.
以總組成物計，***系化合物的含量可為0.01重量%至5.0重量%、0.02重量%至2.0重量%、0.05重量%至1.0重量%、 0.07重量%至0.6重量%或0.1重量%至0.5重量%。以總組成物計，當***系化合物的含量小於0.01重量%時，可能難以有效地抑制下部膜的腐蝕。此外，以總組成物計，當***系化合物的含量大於5.0重量%時，顯著量的腐蝕抑制劑可被吸附並保留於下部膜上，從而降低含銅下部膜(尤其是銅/鉬金屬膜)的電性性質。 Based on the total composition, the content of the triazole compound can be 0.01% by weight to 5.0% by weight, 0.02% by weight to 2.0% by weight, 0.05% by weight to 1.0% by weight, 0.07% by weight to 0.6% by weight or 0.1% by weight to 0.5% by weight. When the content of the triazole-based compound is less than 0.01% by weight based on the total composition, it may be difficult to effectively suppress corrosion of the lower film. In addition, based on the total composition, when the triazole compound content is greater than 5.0% by weight, a significant amount of corrosion inhibitors can be adsorbed and retained on the lower film, thereby reducing the copper-containing lower film (especially copper/molybdenum metal corrosion). film) electrical properties.
同時，相較於使用傳統上已知的腐蝕抑制劑的情形，即使使用等效的量或更少的量，***系化合物亦可更高效地防止含金屬下部膜的腐蝕，且當以特定量與上述甲巰咪唑一起使用時，此種效果可最大化。 Meanwhile, compared with the case of using conventionally known corrosion inhibitors, the triazole-based compound can prevent the corrosion of the metal-containing lower film more efficiently even when using an equivalent amount or less, and when used in a specific This effect can be maximized when used in combination with the above-mentioned methimazole.
同時，甲巰咪唑與***系化合物的重量比可為1：1至1：50、1：1至1：40、1：1.5至1：40或1：2至1：30。由於甲巰咪唑及***系化合物具有如上所述的特定重量比，因此抑制由用於移除光阻的剝離劑組成物形成的下部金屬膜的腐蝕的能力可最大化，且相較於使用甲巰咪唑及***系化合物中的一者或者將甲巰咪唑及***系化合物中的一者與傳統上已知的腐蝕抑制劑一起使用的情形，可更有效地抑制下部金屬膜的腐蝕。 Meanwhile, the weight ratio of methimazole to the triazole 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. Since methimazole and the triazole-based compound have the specific weight ratio as described above, the ability to suppress the corrosion of the lower metal film formed by the stripper composition for removing photoresist can be maximized, and compared with the use of When one of methimazole and triazole-based compounds or one of methimazole and triazole-based compounds is used together with conventionally known corrosion inhibitors, the corrosion of the lower metal film can be more effectively inhibited .
此外，用於移除光阻的剝離劑組成物可包括胺化合物。胺化合物可使得用於移除光阻的剝離劑組成物能夠對光阻具有剝離能力，且具體而言，可溶解光阻以移除光阻。 In addition, the stripper composition for removing photoresist may include an amine compound. The amine compound can enable the stripping agent composition for removing the photoresist to have stripping ability on the photoresist, and specifically, can dissolve the photoresist to remove the photoresist.
以總組成物計，胺化合物的含量可為約0.1重量%至10重量%、0.5重量%至7重量%、1重量%至5重量%或2重量%至4.6重量%。在所述實施例的剝離劑組成物可在以上範圍內表現出 極佳剝離能力等的同時，可減少由於過量的胺導致的製程的經濟無效率及效率劣化，且可減少廢液等的產生。當含有量過大的胺化合物時，此可能導致下部金屬膜(例如含銅下部膜)的腐蝕，且可能有必要使用大量的腐蝕抑制劑來抑制腐蝕。在此種情形中，顯著量的腐蝕抑制劑可能被吸附並保留於下部膜上，從而降低含銅下部膜的電性性質。 Based on the total composition, the content of the amine compound may be about 0.1% to 10% by weight, 0.5% to 7% by weight, 1% to 5% by weight or 2% to 4.6% by weight. The release agent composition in the described embodiment can show in the above range While having excellent peeling ability, etc., it can reduce the economic inefficiency and efficiency degradation of the process caused by excessive amine, and can reduce the generation of waste liquid, etc. When the amine compound is contained in an excessive amount, this may lead to corrosion of the lower metal film (eg, copper-containing lower film), and it may be necessary to use a large amount of corrosion inhibitor to suppress the corrosion. In such cases, significant amounts of corrosion inhibitors may be adsorbed and retained on the lower film, thereby degrading the electrical properties of the copper-containing lower film.
具體而言，以總組成物計，當胺化合物的含量小於0.1重量%時，用於移除光阻的剝離劑組成物的剝離能力可能降低。以總組成物計，當含量大於10重量%時，由於過量的胺化合物，製程的經濟無效率及效率劣化可能降低。 Specifically, when the content of the amine compound is less than 0.1% by weight based on the total composition, the stripping ability of the stripper composition for removing photoresist may decrease. Based on the total composition, when the content is greater than 10% by weight, the economical inefficiency and efficiency degradation of the process may be reduced due to the excess amine compound.
儘管胺化合物的具體種類並無特別限制，然而胺化合物可包括重量平均分子量為95克/莫耳(g/mol)或大於95克/莫耳的一種種類的環狀胺化合物。 Although a specific kind of the amine compound is not particularly limited, the amine compound may include a kind of cyclic amine compound having a weight average molecular weight of 95 grams/mole (g/mol) or more.
環狀胺化合物的實例並無特別限制，但是可為例如1-咪唑啶乙醇、4-咪唑啶乙醇、羥乙基哌嗪(hydroxyethylpiperazine，HEP)、胺基乙基哌嗪等。 Examples of the cyclic amine compound are not particularly limited, but may be, for example, 1-imidazolidine ethanol, 4-imidazolidine ethanol, hydroxyethylpiperazine (HEP), aminoethylpiperazine, and the like.
同時，胺化合物可更包括重量平均分子量為95克/莫耳或大於95克/莫耳的鏈狀胺化合物。 Meanwhile, the amine compound may further include a chain amine compound with a weight average molecular weight of 95 g/mole or greater than 95 g/mole.
除對光阻的剝離能力以外，重量平均分子量為95克/莫耳或大於95克/莫耳的鏈狀胺化合物，可藉由適宜地移除下部膜(例如含銅膜)上的天然氧化物膜來進一步改進膜之間(例如，含銅膜與其上的絕緣膜(例如氮化矽膜)之間)的黏合。 In addition to the stripping ability to photoresist, the chain amine compound having a weight average molecular weight of 95 g/mole or more can effectively remove natural oxidation on the lower film (such as a copper-containing film) film to further improve adhesion between films (eg, between a copper-containing film and an overlying insulating film such as a silicon nitride film).
重量平均分子量為95克/莫耳或大於95克/莫耳的鏈狀胺化合物的實例並無特別限制，但是可為例如(2-胺基乙氧基)-1-乙醇((2-aminoethoxy)-1-ethanol，AEE)、胺基乙基乙醇胺(aminoethyl ethanol amine，AEEA)、甲基二乙醇胺(methyl diethanolamine，MDEA)、二伸乙基三胺(diethylene triamine，DETA)、二乙醇胺(diethanolamine，DEA)、二乙胺基乙醇(diethylaminoethanol，DEAE)、三乙醇胺(triethanolamine，TEA)、三伸乙基四胺(triethylene tetraamine，TETA)或其中的兩者或多多者的混合物。 Examples of chain amine compounds having a weight average molecular weight of 95 g/mol or more are not particularly limited, but may be, for example, (2-aminoethoxy)-1-ethanol ((2-aminoethoxy )-1-ethanol, AEE), aminoethylethanolamine (AEEA), methyldiethanolamine (MDEA), diethylenetriamine (DETA), diethanolamine (diethanolamine , DEA), diethylaminoethanol (diethylaminoethanol, DEAE), triethanolamine (triethanolamine, TEA), triethylene tetraamine (triethylene tetraamine, TETA) or a mixture of two or more thereof.
同時，以100重量份的胺化合物計，甲巰咪唑及***系化合物的總含量可為1重量份至30重量份、2重量份至25重量份或3重量份至20重量份。 Meanwhile, based on 100 parts by weight of the amine compound, the total content of methimazole and triazole compounds may be 1 to 30 parts by weight, 2 to 25 parts by weight or 3 to 20 parts by weight.
如上所述，胺化合物是用於移除光阻的剝離劑組成物中對光阻表現出剝離能力的組分，且可溶解光阻以移除光阻。此外，甲巰咪唑及***系化合物抑制下部金屬膜的腐蝕。以100重量份的胺化合物計，當甲巰咪唑及***系化合物的總量小於1重量份時，可能難以有效地抑制下部膜的腐蝕。此外，以100重量份的胺化合物計，當甲巰咪唑及***系化合物的總量大於30重量份時，顯著量的腐蝕抑制劑可能被吸附並保留於下部膜上，從而降低含銅下部膜(尤其是銅/鉬金屬膜)的電性性質。 As described above, the amine compound is a component in the stripper composition for removing the photoresist that exhibits stripping ability to the photoresist, and can dissolve the photoresist to remove the photoresist. In addition, methimazole and triazole-based compounds suppress corrosion of the lower 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 suppress corrosion of the lower film. In addition, based on 100 parts by weight of the amine compound, when the total amount of methimazole and triazole-based compounds is greater than 30 parts by weight, a significant amount of corrosion inhibitors may be adsorbed and retained on the lower film, thereby reducing the copper-containing lower film. Electrical properties of films, especially copper/molybdenum metal films.
此外，用於移除光阻的剝離劑組成物可包括其中具有1至5個碳原子的直鏈或支鏈烷基被1或2個氮原子取代的醯胺化 合物。其中具有1至5個碳原子的直鏈或支鏈烷基被1或2個氮原子取代的醯胺化合物可恰當地溶解胺化合物，且可使得用於移除光阻的剝離劑組成物能夠有效地穿透下部膜，藉此改進剝離劑組成物的剝離及漂洗能力。 In addition, the stripper composition for removing photoresist may include amidation in which a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 or 2 nitrogen atoms. compound. An amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 or 2 nitrogen atoms can properly dissolve an amine compound and can enable a stripper composition for removing a photoresist Effectively penetrates the lower film, thereby improving the stripping and rinsing ability of the stripper composition.
具體而言，其中具有1至5個碳原子的直鏈或支鏈烷基被1或2個氮原子取代的醯胺化合物可包括其中甲基被1或2個氮原子取代的醯胺化合物。其中甲基被1或2個氮原子取代的醯胺化合物可具有由以下化學式1表示的化學結構。 Specifically, amide compounds in which a linear or branched chain alkyl group having 1 to 5 carbon atoms is substituted with 1 or 2 nitrogen atoms may include amide compounds in which a methyl group is substituted with 1 or 2 nitrogen atoms. An amide compound in which a methyl group is substituted with 1 or 2 nitrogen atoms may have a chemical structure represented by Chemical Formula 1 below.
在化學式1中，R1是氫、甲基、乙基或丙基，R2及R3中的每一者是氫或具有1至5個碳原子的直鏈或支鏈烷基，且R2及R3中的至少一者是甲基。 In Chemical Formula 1, R 1 is hydrogen, methyl, ethyl or propyl, each of R 2 and R 3 is hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms, and R At least one of 2 and R 3 is methyl.
具有1至5個碳原子的直鏈或支鏈烷基的實例不受限制。舉例而言，可使用甲基、乙基、丙基、丁基、異丁基、戊基等。 Examples of linear or branched alkyl groups having 1 to 5 carbon atoms are not limited. For example, methyl, ethyl, propyl, butyl, isobutyl, pentyl, etc. can be used.
其中甲基被1或2個氮原子取代的醯胺化合物的實例不受限制。舉例而言，可使用化學式1中的其中R2是甲基且R1及R3是氫的化合物。 Examples of amide compounds in which the methyl group is substituted with 1 or 2 nitrogen atoms are not limited. For example, a compound in Chemical Formula 1 in which R 2 is methyl and R 1 and R 3 are hydrogen may be used.
以總組成物計，其中具有1至5個碳原子的直鏈或支鏈 烷基被1或2個氮原子取代的醯胺化合物的含量可為10重量%至80重量%、15重量%至70重量%或25重量%至60重量%。所述實施例的用於移除光阻的剝離劑組成物可在以上範圍內表現出極佳剝離能力等，且可長時間維持剝離及漂洗能力。 Based on the total composition, straight or branched chains with 1 to 5 carbon atoms The content of the amide compound in which the alkyl group is substituted by 1 or 2 nitrogen atoms may be 10% by weight to 80% by weight, 15% by weight to 70% by weight, or 25% by weight to 60% by weight. The stripper composition for removing photoresist of the embodiment can exhibit excellent stripping ability and the like within the above range, and can maintain the stripping and rinsing ability for a long time.
此外，所述用於移除光阻的剝離劑組成物可包括極性有機溶劑。極性有機溶劑可使得用於移除光阻的剝離劑組成物能夠有效地穿透下部膜，藉此有助於剝離劑組成物的極佳剝離能力。此外，所述用於移除光阻的剝離劑組成物可有效地移除下部膜(例如含銅膜)上的污漬，以改進用於移除光阻的剝離劑組成物的漂洗能力。 In addition, the stripper composition for removing photoresist may include a polar organic solvent. The polar organic solvent may allow the stripper composition for removing photoresist to effectively penetrate the lower film, thereby contributing to the excellent stripping ability of the stripper composition. In addition, the stripper composition for removing photoresist can effectively remove stains on an underlying film (eg, a copper-containing film) to improve the rinsing ability of the stripper composition for removing photoresist.
極性有機溶劑可包括伸烷基二醇單烷基醚(alkylene glycol monoalkyl ether)、吡咯啶酮(pyrrolidone)、碸(sulfone)、亞碸(sulfoxide)或其中的兩者或更多者的混合物。更具體而言，伸烷基二醇單烷基醚可包括二乙二醇單甲基醚(diethylene glycol monomethyl ether，MDG)、乙二醇單乙基醚、乙二醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丁基醚、二乙二醇單乙基醚(diethylene glycol monoethyl ether，EDG)、二乙二醇單丙基醚、二乙二醇單丁基醚(diethylene glycol monobutyl ether，BDG)、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單丙基醚、二丙二醇單丁基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、三乙二醇單丙基醚、三乙二醇單丁基醚、三丙二醇單甲基醚、三丙二醇單乙基醚、三丙二醇單丙基醚、三丙二醇單丁基醚或其中 的兩者或更多者的混合物。 The polar organic solvent may include alkylene glycol monoalkyl ether, pyrrolidone, sulfone, sulfoxide, or a mixture of two or more thereof. More specifically, the alkylene glycol monoalkyl ether may include diethylene glycol monomethyl ether (MDG), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether (EDG), diethylene glycol monopropyl ether, diethylene glycol monobutyl ether Ether (diethylene glycol monobutyl ether, BDG), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol Alcohol 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 ether or a mixture of two or more of them.
此外，慮及用於移除光阻的剝離劑組成物的極佳潤濕性以及因此改進的剝離及漂洗能力，伸烷基二醇單烷基醚可使用二乙二醇單甲基醚(MDG)、二乙二醇單乙基醚(EDG)、二乙二醇單丁基醚(BDG)等。 In addition, alkylene glycol monoalkyl ethers may use diethylene glycol monomethyl ether ( MDG), diethylene glycol monoethyl ether (EDG), diethylene glycol monobutyl ether (BDG), etc.
吡咯啶酮的實例並無特別限制，但是舉例而言，可使用N-甲基吡咯啶酮、吡咯啶酮、N-乙基吡咯啶酮等。碸的實例並無特別限制，但是舉例而言，可使用環丁碸。亞碸的實例並無特別限制，但是舉例而言，可使用二甲基亞碸(dimethyl sulfoxide，DMSO)、二乙基亞碸、二丙基亞碸等。 Examples of pyrrolidone are not particularly limited, but for example, N-methylpyrrolidone, pyrrolidone, N-ethylpyrrolidone, and the like can be used. Examples of thorium are not particularly limited, but for example, cyclobutane can be used. Examples of sulfoxide are not particularly limited, but for example, dimethylsulfoxide (DMSO), diethylsulfoxide, dipropylsulfoxide, etc. can be used.
以總組成物計，極性有機溶劑的含量可為10重量%至80重量%、20重量%至78重量%或40重量%至70重量%。所述實施例的用於移除光阻的剝離劑組成物可在以上範圍內表現出極佳剝離能力等，且可長時間維持剝離及漂洗能力。 Based on the total composition, the content of the polar organic solvent may be 10 wt % to 80 wt %, 20 wt % to 78 wt % or 40 wt % to 70 wt %. The stripper composition for removing photoresist of the embodiment can exhibit excellent stripping ability and the like within the above range, and can maintain the stripping and rinsing ability for a long time.
同時，所述用於移除光阻的剝離劑組成物可更包括矽酮系非離子性表面活性劑。矽酮系非離子性表面活性劑可為穩定的，即使在包括胺化合物的高鹼性剝離劑組成物中亦不會引起化學變化、變性或分解。此外，矽酮系非離子性表面活性劑可表現出與上述極性非質子性溶劑或質子性有機溶劑的極佳相容性。因此，矽酮系(silicone-based)非離子性表面活性劑可與其它組分混合，以降低剝離劑組成物的表面張力，且對剝離劑組成物欲被移除的光阻及其下部膜表現出更佳的潤濕性。因此，所述實施例 的包括矽酮系非離子性表面活性劑的剝離劑組成物可表現出極佳剝離能力，且亦可表現出相對於下部膜的極佳漂洗能力，因此即使在剝離劑組成物被處理之後，污漬及異物亦很少產生並保留於下部膜上，且污漬及異物可被有效地移除。 Meanwhile, the stripper composition for removing photoresist may further include a silicone-based nonionic surfactant. The silicone-based nonionic surfactant can be stable without causing chemical change, denaturation, or decomposition even in a highly alkaline release agent composition including an amine compound. In addition, silicone-based nonionic surfactants can exhibit excellent compatibility with the aforementioned polar aprotic solvents or protic organic solvents. Therefore, silicone-based non-ionic surfactants can be mixed with other components to reduce the surface tension of the stripper composition, and have good performance on the photoresist and its underlying film to be removed by the stripper composition. for better wettability. Therefore, the example The release agent composition including the silicone-based nonionic surfactant can exhibit excellent peeling ability, and can also exhibit excellent rinsing ability with respect to the lower film, so even after the release agent composition is treated, Stains and foreign matter are also rarely generated and remain on the lower film, and the stains and foreign matter can be effectively removed.
此外，矽酮系非離子性表面活性劑即使在含量非常低的情況下亦可表現出上述效果，且由於其變性或分解而產生的副產物可最小化。 In addition, the silicone-based nonionic surfactant can exhibit the above effects even at a very low content, and by-products due to its denaturation or decomposition can be minimized.
具體而言，矽酮系非離子性表面活性劑可包括聚矽氧烷系聚合物。聚矽氧烷系聚合物的實例並無特別限制，但是舉例而言，可使用聚醚改性丙烯酸官能聚二甲基矽氧烷、聚醚改性矽氧烷、聚醚改性聚二甲基矽氧烷、聚乙基烷基矽氧烷、芳烷基改性聚甲基烷基矽氧烷、聚醚改性羥基官能聚二甲基矽氧烷、聚醚改性二甲基聚矽氧烷、改性丙烯酸官能聚二甲基矽氧烷或其中的兩者或更多者的混合物。 Specifically, the silicone-based nonionic surfactant may include polysiloxane-based polymers. Examples of polysiloxane-based polymers are not particularly limited, but for example, polyether-modified acrylic-functional polydimethylsiloxane, polyether-modified siloxane, polyether-modified polydimethylsiloxane, Polysiloxane, polyethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified hydroxyl-functional polydimethylsiloxane, polyether-modified dimethylpolysiloxane Silicone, modified acrylic functional polydimethylsiloxane, or a mixture of two or more thereof.
以總組成物計，矽酮系非離子性表面活性劑的含量可為0.0005重量%至0.1重量%、0.001重量%至0.09重量%或0.001重量%至0.01重量%。以總組成物計，當矽酮系非離子性表面活性劑的含量小於0.0005重量%時，其可能不足以有效地改進剝離劑組成物的剝離及漂洗能力。此外，以總組成物計，當矽酮系非離子性表面活性劑的含量大於0.1重量%時，在使用剝離劑組成物的剝離製程期間，在高壓下會產生氣泡，因而導致下部膜上出現污漬或導致裝備感測器故障。 Based on the total composition, the content of the silicone-based nonionic surfactant may be 0.0005% to 0.1% by weight, 0.001% to 0.09% by weight, or 0.001% to 0.01% by weight. Based on the total composition, when the content of the silicone-based nonionic surfactant is less than 0.0005% by weight, it may not be sufficient to effectively improve the stripping and rinsing capabilities of the stripping agent composition. In addition, when the content of the silicone-based nonionic surfactant is more than 0.1% by weight based on the total composition, air bubbles are generated under high pressure during the peeling process using the peeling agent composition, thus resulting in the formation of bubbles on the lower film. Dirt may cause the equipment sensor to malfunction.
若有必要，則所述用於移除光阻的剝離劑組成物可更包括傳統添加劑。添加劑的具體類型或含量並無特別限制。 If necessary, the stripper composition for removing photoresist may further include conventional additives. The specific type or content of additives is not particularly limited.
此外，所述用於移除光阻的光阻剝離劑組成物可根據混合上述組分的一般方法來製備，且製備所述用於移除光阻的剝離劑組成物的具體方法並無特別限制。 In addition, the photoresist stripper composition for removing photoresist can be prepared according to the general method of mixing the above components, and the specific method for preparing the photoresist stripper composition for removing photoresist is not particularly specific. limit.
同時，根據本揭露的另一實施例，提供一種剝離光阻的方法，所述方法包括使用所述實施例的用於移除光阻的剝離劑組成物剝離光阻的步驟。 Meanwhile, according to another embodiment of the present disclosure, a method for stripping photoresist is provided, the method includes the step of stripping photoresist using the stripper composition for removing photoresist of the embodiment.
與所述用於移除光阻的剝離劑組成物相關的說明包括與以上實施例相關的詳細說明。 The description related to the stripper composition for removing photoresist includes the detailed description related to the above embodiments.
所述剝離光阻的方法可包括以下步驟：藉由光刻製程在其上欲圖案化下部膜的基板上形成光阻圖案；以光阻圖案作為遮罩來圖案化下部膜；以及使用上述剝離劑組成物剝離光阻。 The method for stripping the photoresist may include the steps of: forming a photoresist pattern on a substrate on which the lower film is to be patterned by a photolithography process; patterning the lower film with the photoresist pattern as a mask; The agent composition strips the photoresist.
在剝離光阻的方法中，形成光阻圖案及圖案化下部膜的步驟可使用裝置的傳統製造製程，且具體方法並無特別限制。 In the method of stripping the photoresist, the steps of forming the photoresist pattern and patterning the lower film can use the traditional manufacturing process of the device, and the specific method is not particularly limited.
同時，使用用於移除光阻的剝離劑組成物剝離光阻的步驟的實例並無特別限制，但是舉例而言，可使用以下步驟：將用於移除光阻的剝離劑組成物施加至其中保留光阻圖案的基板；以及以鹼性緩衝溶液使基板經歷洗滌，然後以超純水(ultrapure water)進行洗滌並乾燥。由於上述剝離劑組成物表現出有效地移除下部膜上的污漬的漂洗能力及移除天然氧化物膜的能力以及極佳剝離能力，因此上述剝離劑組成物可在有效地移除保留於下部 膜上的光阻圖案的同時，令人滿意地維持下部膜的表面狀態。因此，可對圖案化的下部膜適宜地執行後續步驟以形成裝置。 Meanwhile, an example of the step of stripping the photoresist using the stripper composition for removing the photoresist is not particularly limited, but for example, the following step may be used: applying the stripper composition for removing the photoresist to the substrate in which the photoresist pattern remains; and subjecting the substrate to washing with an alkaline buffer solution, followed by washing with ultrapure water and drying. Since the above-mentioned stripper composition exhibits the rinsing ability to effectively remove the stains on the lower film and the ability to remove the natural oxide film and excellent stripping ability, the above-mentioned stripper composition can be effectively removed while remaining on the lower film. While maintaining the photoresist pattern on the film, the surface state of the underlying film is satisfactorily maintained. Accordingly, subsequent steps may be suitably performed on the patterned lower film to form the device.
形成於基板上的下部膜的實例並無特別限制，但是可包括鋁或鋁合金、銅或銅合金、鉬或鉬合金、其混合物、其複合合金、其複合積層體等。 Examples of the lower film formed on the substrate are not particularly limited, but may include aluminum or aluminum alloys, copper or copper alloys, molybdenum or molybdenum alloys, mixtures thereof, composite alloys thereof, composite laminates thereof, and the like.
以上剝離方法所可應用於的光阻的種類、成分或物理性質亦並無特別限制。舉例而言，光阻可為已知用於包括鋁或鋁合金、銅或銅合金、鉬或鉬合金等在內的下部膜的光阻。更具體而言，光阻可包括例如酚醛清漆樹脂、酚醛樹脂或環氧樹脂等感光性樹脂。 The type, composition or physical properties of the photoresist to which the above stripping method can be applied are not particularly limited. For example, the photoresist may be a photoresist known for use with underlying films including aluminum or aluminum alloys, copper or copper alloys, molybdenum or molybdenum alloys, and the like. More specifically, the photoresist may include a photosensitive resin such as novolac resin, phenolic resin, or epoxy resin.
根據本揭露，可提供一種用於移除光阻的剝離劑組成物以及一種使用其剝離光阻之方法，所述用於移除光阻的剝離劑組成物能夠抑制在剝離製程期間下部金屬膜的腐蝕，且能夠在對光阻表現出極佳剝離能力的同時有效地移除氧化物。 According to the present disclosure, there can be provided a stripper composition for removing a photoresist capable of suppressing the lower metal film during a stripping process and a method of stripping a photoresist using the same. Etch, and can effectively remove oxide while exhibiting excellent stripping ability to photoresist.
在以下實例中將更詳細地闡釋本發明。然而，該些實例 僅用於例示目的，且本發明並不旨在受該些實例所限制。 The invention will be explained in more detail in the following examples. However, these instances These are for illustrative purposes only and the invention is not intended to be limited by these examples.
<實例1至5：用於移除光阻的剝離劑組成物的製備><Examples 1 to 5: Preparation of Stripper Composition for Removing Photoresist>
根據以下表1所示組成，將組分進行了混合，以分別製備實例1至5的用於移除光阻的剝離劑組成物。所製備的用於移除光阻的剝離劑組成物的具體組成示出於以下表1中。 According to the compositions shown in Table 1 below, the components were mixed to prepare the stripping agent compositions for removing photoresist of Examples 1 to 5, respectively. The specific composition of the prepared stripper composition for removing photoresist is shown in Table 1 below.
*腐蝕抑制劑1：甲巰咪唑 *Corrosion inhibitor 1: Methimazole
*腐蝕抑制劑2：2,2’-[[(甲基-1H-苯並***-1-基)甲基]亞胺基]雙乙醇 *Corrosion inhibitor 2: 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol
*腐蝕抑制劑3：苯並咪唑 *Corrosion Inhibitor 3: Benzimidazole
*腐蝕抑制劑4：咪唑 *Corrosion inhibitor 4: imidazole
*腐蝕抑制劑5：2-甲基咪唑 *Corrosion inhibitor 5: 2-methylimidazole
*腐蝕抑制劑6：2-巰基苯並咪唑 *Corrosion Inhibitor 6: 2-Mercaptobenzimidazole
<比較例1至5：用於移除光阻的剝離劑組成物的製備><Comparative Examples 1 to 5: Preparation of Stripper Compositions for Removing Photoresist>
根據以下表2所示組成，將組分進行了混合，以分別製備比較例1至5的用於移除光阻的剝離劑組成物。所製備的用於移除光阻的剝離劑組成物的具體組成示出於以下表2中。 According to the compositions shown in Table 2 below, the components were mixed to prepare stripper compositions for removing photoresists of Comparative Examples 1 to 5, respectively. The specific composition of the prepared stripper composition for removing photoresist is shown in Table 2 below.
<實驗實例：對在實例及比較例中獲得的用於移除光阻的剝離劑組成物的物理性質的量測> <Experimental Example: Measurement of Physical Properties of Stripper Compositions for Removing Photoresist Obtained in Examples and Comparative Examples>
藉由以下方法量測了在實例及比較例中獲得的剝離劑組成物的物理性質，且結果示出於表中。 The physical properties of the release agent compositions obtained in Examples and Comparative Examples were measured by the following methods, and the results are shown in the table.
1.剝離能力評價1. Evaluation of stripping ability
首先，以滴落的方式將3.5毫升(ml)的光阻組成物(商 標名：JC-800)添加至100毫米(mm)×100毫米玻璃基板，且在旋塗設備中以400轉/分鐘(revolutions per minute，rpm)施加光阻組成物達10秒。將玻璃基板安裝於熱板上，並在150℃或140℃的溫度下硬烘焙了20分鐘以形成光阻。在室溫下對其上形成光阻的玻璃基板進行了空氣冷卻，且接著切割成了30毫米×30毫米的尺寸，以製備用於評價剝離劑新液體剝離能力的樣品。 First, drop 3.5 milliliters (ml) of the photoresist composition (quotient Designation: JC-800) was added to a 100 millimeter (mm) x 100 mm glass substrate, and the photoresist composition was applied for 10 seconds at 400 revolutions per minute (rpm) in a spin-coating device. The glass substrate was mounted on a hot plate, and hard baked at a temperature of 150° C. or 140° C. for 20 minutes to form a photoresist. The glass substrate on which the photoresist was formed was air-cooled at room temperature, and then cut into a size of 30 mm x 30 mm to prepare a sample for evaluation of the new liquid peeling ability of the stripper.
製備了500克在實例1至5及比較例1至4、6及7中的一者中獲得的剝離劑組成物。在溫度升高至50℃的狀態下，以剝離劑組成物對玻璃基板上的光阻進行了處理。量測了完全剝離並移除光阻所需的時間，以評價剝離劑新液體的剝離能力。此時，藉由利用在玻璃基板上輻射紫外光來觀察光阻是否保留下來而確定了光阻剝離的完成。 500 g of the release agent composition obtained in Examples 1 to 5 and one of Comparative Examples 1 to 4, 6 and 7 were prepared. In the state where the temperature was raised to 50° C., the photoresist on the glass substrate was treated with the release agent composition. The time required to completely strip and remove the photoresist was measured to evaluate the stripping ability of the new liquid of the stripper. At this time, the completion of the photoresist stripping was confirmed by observing whether the photoresist remained by irradiating ultraviolet light on the glass substrate.
如上所述評價了實例1至5及比較例1至4、6及7的剝離劑組成物的剝離能力，且結果示出於以下表3及表4中。 The release abilities of the release agent 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 Table 3 and Table 4 below.
如以上表3及表4中所示，證實了實例1至5的剝離劑組成物相較於比較例1至4、6及7的剝離劑組成物而言表現出等效的或更高水準的剝離能力。 As shown in Table 3 and Table 4 above, it was confirmed that the release agent compositions of Examples 1 to 5 exhibited equivalent or higher levels compared to the release agent compositions of Comparative Examples 1 to 4, 6 and 7 stripping ability.
2.銅(Cu)金屬腐蝕評價2. Corrosion evaluation of copper (Cu) metal
以滴落的方式將3.5毫升的光阻組成物(商標名：JC-800)添加至其上形成含銅薄膜的100毫米×100毫米玻璃基板，且在旋塗設備中以400轉/分鐘施加光阻組成物達10秒。將玻璃基板安裝於熱板上，並在150℃或140℃的溫度下硬烘焙了20分鐘以形成光阻。在室溫下對其上形成光阻的玻璃基板進行了空氣冷卻，且接著切割成30毫米×30毫米的尺寸，以製備用於腐蝕評價的樣品。 3.5 ml of a photoresist composition (trade name: JC-800) was added dropwise to a 100 mm x 100 mm glass substrate on which a copper-containing thin film was formed, and applied at 400 rpm in a spin coating device Photoresist composition for 10 seconds. The glass substrate was mounted on a hot plate, and hard baked at a temperature of 150° C. or 140° C. for 20 minutes to form a photoresist. The glass substrate on which the photoresist was formed was air-cooled at room temperature, and then cut into a size of 30 mm×30 mm to prepare a sample for corrosion evaluation.
將500克的在實例1、3、4及5以及比較例1至7中的一者中獲得的剝離劑組成物加熱至50℃的溫度，並將用於腐蝕評價的樣品在50℃的溫度下浸漬於剝離劑組成物中達10分鐘，然後以超純水進行了洗滌。藉由掃描式電子顯微鏡(scanning electron microscope，SEM)量測了所洗滌樣品表面的腐蝕狀態，以評價銅金屬的腐蝕，且結果示出於以下表5及表6中。 500 g 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° C., and the sample used for corrosion evaluation was heated to a temperature of 50° C. It was immersed in the stripping agent composition for 10 minutes, and then washed with ultrapure water. The corrosion state of the washed sample surface was measured by scanning electron microscope (SEM) to evaluate the corrosion of copper metal, and the results are shown in Table 5 and Table 6 below.
如以上表5及表6中所示，證實了藉由包含甲巰咪唑與***系化合物二者，實例1、3、4及5的剝離劑組成物對於銅金屬的腐蝕性小於比較例2至5的剝離劑組成物。 As shown in Table 5 and Table 6 above, it was confirmed that the stripper compositions of Examples 1, 3, 4, and 5 were less corrosive to copper metal than Comparative Example 2 by including both methimazole and a triazole-based compound to 5 stripping agent compositions.
自該些結果可看出，所述實例的剝離劑組成物中所包含的甲巰咪唑及***系化合物具有極佳的防止銅金屬腐蝕的能力。 It can be seen from these results that the methimazole and the triazole-based compounds included in the stripper composition of the example have an excellent ability to prevent copper metal corrosion.
3.銅(Cu)/鉬(Mo)金屬下部膜腐蝕評價3. Corrosion evaluation of copper (Cu)/molybdenum (Mo) metal lower film
使用透射式電子顯微鏡(transmission electron microscope，TEM)(赫利俄斯奈米實驗室650(Helios Nanolab650))對在實例1至5及比較例1、3、4、6及7中的一者中獲得的用於腐蝕評價的樣品的橫截面進行了觀察。具體而言，使用聚焦離子束(Focused Ion Beam，FIB)製備了用於腐蝕評價的樣品的薄片(flake)，且接著在2千伏特(kV)的加速電壓下進行了觀察。為防止由離子束造成的表面損壞，在樣品(Cu層)的表面上形成鉑(Pt)保護層之後，製備了透射式電子顯微鏡薄片。 Using a transmission electron microscope (transmission electron microscope, TEM) (Helios Nanolab 650 (Helios Nanolab650)) in one of Examples 1 to 5 and Comparative Examples 1, 3, 4, 6 and 7 The cross-sections of the samples obtained for corrosion evaluation were observed. Specifically, flakes of samples for corrosion evaluation were prepared using a Focused Ion Beam (FIB), and then observed at an acceleration voltage of 2 kilovolts (kV). In order to prevent surface damage caused by ion beams, after forming a platinum (Pt) protective layer on the surface of the sample (Cu layer), a transmission electron microscope thin section was prepared.
如以上表7及表8中所示，證實了相較於比較例1的包含甲巰咪唑及苯並咪唑的剝離劑組成物以及比較例3、4及7的包含一種種類的腐蝕抑制劑的剝離劑組成物，實例1至5的包含甲巰咪唑與***系化合物二者的剝離劑組成物降低了銅(Cu)/鉬(Mo)金屬下部膜的腐蝕。 As shown in Table 7 and Table 8 above, compared with the stripper composition containing methimazole and benzimidazole in Comparative Example 1 and the corrosion inhibitor containing one type in Comparative Examples 3, 4, and 7, it was confirmed that The stripper compositions, the stripper compositions of Examples 1 to 5 including both methimazole and triazole-based compounds, reduced the corrosion of the copper (Cu)/molybdenum (Mo) metal lower film.
自該些結果可看出，所述實例的剝離劑組成物中所包含 的甲巰咪唑及***系化合物具有極佳的防止銅(Cu)/鉬(Mo)金屬下部膜腐蝕的能力。 As can be seen from these results, the stripping agent composition contained in the example The methimazole and triazole compounds have excellent ability to prevent corrosion of copper (Cu)/molybdenum (Mo) metal lower film.
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| KR101668063B1 (en) * | 2013-05-07 | 2016-10-20 | 주식회사 엘지화학 | Stripper composition for removing photoresist and stripping mthod of photoresist using the same |
| KR101764577B1 (en) * | 2015-08-13 | 2017-08-23 | 엘티씨 (주) | Composition of stripping solution for liquid crystal display process photoresist |
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| TW201407283A (en) * | 2004-11-30 | 2014-02-16 | Asahi Kasei E Materials Corp | Pattern-forming material, pattern-forming device, and pattern-forming method |
| TW200941158A (en) * | 2007-12-28 | 2009-10-01 | Dongjin Semichem Co Ltd | Composition for removing photoresist and method of manufacturing an array substrate using the same |
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