KR101375100B1 - Stripper composition for thick negative photoresist - Google Patents
Stripper composition for thick negative photoresist Download PDFInfo
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- KR101375100B1 KR101375100B1 KR1020120096430A KR20120096430A KR101375100B1 KR 101375100 B1 KR101375100 B1 KR 101375100B1 KR 1020120096430 A KR1020120096430 A KR 1020120096430A KR 20120096430 A KR20120096430 A KR 20120096430A KR 101375100 B1 KR101375100 B1 KR 101375100B1
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- photoresist
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- stripper composition
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 54
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 claims description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 2
- ATLYKOUEGIGBCN-UHFFFAOYSA-N 1-ethylpyrrolidin-2-one 1-methylpyrrolidin-2-one Chemical compound C(C)N1C(CCC1)=O.CN1C(CCC1)=O ATLYKOUEGIGBCN-UHFFFAOYSA-N 0.000 claims 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 44
- 230000007797 corrosion Effects 0.000 abstract description 31
- 238000005260 corrosion Methods 0.000 abstract description 31
- 239000003112 inhibitor Substances 0.000 abstract description 14
- -1 hydroxide compound Chemical class 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000012805 post-processing Methods 0.000 abstract description 3
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 19
- 239000002184 metal Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000001312 dry etching Methods 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- AZLXQBNSOMJQEJ-UHFFFAOYSA-N 1,3-di(propan-2-yl)imidazolidin-2-one Chemical compound CC(C)N1CCN(C(C)C)C1=O AZLXQBNSOMJQEJ-UHFFFAOYSA-N 0.000 description 1
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 description 1
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- QQLILYBIARWEIF-UHFFFAOYSA-N 2-(2-hydroxyethylsulfonyl)ethanol Chemical compound OCCS(=O)(=O)CCO QQLILYBIARWEIF-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 150000008624 imidazolidinones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- 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
-
- 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
-
- 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
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
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- 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
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
본 발명은 포토레지스트 제거용 박리액 조성물에 관한 것으론, 본 발명에 따른 조성물은 1 내지 5 중량%의 화학식(1)로 표시되는 화합물, 70 내지 95 중량%의 극성 유기 용매, 0.1 내지 5 중량%의 하이드록사이드계 화합물 및 나머지량의 물을 포함하는 것을 특징으로 한다. 본 발명에 의한 박리액 조성물은 특히 박리액 조성물 내에 부식방지제를 포함하지 않고 화학식(1)로 표시되는 화합물을 적정량 포함함으로써 효과적으로 단시간 내에 박리 공정을 완료할 수 있으며 다른 공정에 비해 상대적으로 높은 공정온도에서 수행되는 박리 공정에서 조성변화를 최소화할 수 있다. 또한 부식방지제를 포함하지 않음으로써 비수용성인 부식방지제 흡착에 의한 증착 불량과 같은 후공정 불량을 방지하면서 전극 손상을 막을 수 있게 한다.The present invention relates to a stripper composition for removing photoresist, wherein the composition according to the present invention comprises 1 to 5% by weight of the compound represented by the formula (1), 70 to 95% by weight of a polar organic solvent, and 0.1 to 5% by weight. It is characterized by containing a hydroxide compound of% and the remaining amount of water. The stripper composition according to the present invention can effectively complete the stripping process in a short time by including a proper amount of the compound represented by the formula (1) without including a corrosion inhibitor in the stripper composition, and has a relatively higher process temperature than other processes. It is possible to minimize the change in composition in the peeling process performed in the. In addition, by not including a corrosion inhibitor, it is possible to prevent electrode damage while preventing post-processing defects such as poor deposition due to adsorption of a water-insoluble corrosion inhibitor.
Description
본 발명은 후막의 네가티브 포토레지스트를 효과적으로 제거할 수 있는 박리액 조성물에 관한 것이다. The present invention relates to a stripper composition that can effectively remove the negative photoresist of a thick film.
일반적으로, 반도체/LED/LCD 소자의 미세 회로는 일련의 리소그래피 공정을 거침으로써 완성된다. 리소그래피 공정은 기판에 금속막 또는 절연막 등을 균일하게 도포하고, 그 위에 포토레지스트를 균일하게 도포한 후, 패턴이 새겨진 마스크를 통하여 빛을 조사하고 현상공정을 통하여 원하는 패턴의 포토레지스트를 형성하는 공정이다. 이 때 건식/습식 에칭으로 포토레지스트 하부에 있는 금속막 및 절연막에 패턴을 전사한 후 필요없는 포토레지스트는 박리 공정에 의해 제거된다.Generally, the microcircuits of semiconductor / LED / LCD devices are completed by going through a series of lithography processes. In the lithography process, a metal film or an insulating film is uniformly applied to a substrate, a photoresist is uniformly applied thereon, and then a light is irradiated through a mask having a pattern engraved thereon, and a photoresist having a desired pattern is formed through a developing process. to be. At this time, after the pattern is transferred to the metal film and the insulating film under the photoresist by dry / wet etching, unnecessary photoresist is removed by a peeling process.
포토레지스트는 방사선의 조사에 따른 현상액에 대한 용해도의 차이에 따라 포지티브(positive) 포토레지스트와 네가티브(negative) 포토레지스트로 구분한다. 포지티브 포토레지스트는 노광된 부분의 용해도가 증가하는 것에 의해 현상이 이루어지며, 네가티브 포토레지스트는 노광된 부분의 경화에 의해 용해도가 감소하여 현상 후 패턴으로 남게 된다. The photoresist is classified into a positive photoresist and a negative photoresist according to a difference in solubility in a developer according to radiation. The positive photoresist develops by increasing the solubility of the exposed portion, and the negative photoresist decreases solubility due to curing of the exposed portion, leaving the pattern after development.
포지티브 포토레지스트의 경우, 일반적인 습식 공정에서는 통상적인 박리액에 의해 쉽게 제거가 되지만, 건식식각, 이온주입공정 등에 의해 경화 및 변성되면 제거가 어려워진다. 건식식각 공정은 습식식각에 비해 패턴의 제어가 용이하고 이방성의 패턴을 얻을 수 있는 장점이 있어 미세 패턴 형성에서 주로 사용되고 있는데, 플라즈마 가스와 도전층과 같은 물질막과의 사이의 기상-고상 반응을 이용하여 식각공정을 수행하기 때문에, 플라즈마 식각가스의 이온 및 라디칼이 포토레지스트와 화학반응을 일으켜 포토레지스트막을 경화 및 변성시키므로 제거가 어려워진다. 또한, 이온주입 공정은 반도체/LED/LCD 소자의 제조공정에 있어서 기판의 특정 영역에 도전성을 부여하기 위해서 인, 비소, 붕소, 등의 원소를 확산시키는 공정으로서, 이온들이 포지티브 포토레지스트와 화학반응을 일으켜 변성시키므로 역시 제거가 어려워진다.In the case of the positive photoresist, the general wet process is easily removed by a conventional stripping solution, but when hardened and modified by dry etching, ion implantation, or the like, the removal is difficult. The dry etching process is mainly used in the formation of fine patterns because it is easier to control the pattern than the wet etching and obtains the anisotropic pattern. The dry etching process is used for the gas phase-solid reaction between a plasma gas and a material film such as a conductive layer. Since the etching process is performed using the etch process, the ions and radicals of the plasma etching gas chemically react with the photoresist to cure and denature the photoresist film, thereby making it difficult to remove them. In addition, the ion implantation process is a process of diffusing elements such as phosphorous, arsenic, boron, etc. in order to impart conductivity to a specific region of the substrate in the manufacturing process of semiconductor / LED / LCD device, the ions are chemical reaction with the positive photoresist It is also difficult to remove because it causes degeneration.
한편, 네가티브 포토레지스트의 경우 리프트 오프(lift-off) 공정 등에 사용되며, 노광에 의해 가교가 되어 일반적인 용매를 이용하여 충분히 제거할 수 없고, 제거된다 하더라도 100℃ 이상의 고온과 장시간에 걸친 침지시간을 필요로 하므로 안정적으로 공정을 수행하기가 힘들다.On the other hand, the negative photoresist is used in a lift-off process and the like, and it is crosslinked by exposure and cannot be removed sufficiently using a general solvent. It is difficult to carry out the process stably because it is necessary.
또한, 일반적으로 식각공정에 사용되는 포토레지스트는 막 두께가 2㎛ 이내이나, 범프 전극 형성 공정이나 재배선공정(RDL: ReDistribution Line) 등의 전극에 사용되는 포토레지스트는 그 두께가 5㎛ 이상에서 수십 ㎛으로 형성되어야 하므로, 포토레지스트를 제거하기 위한 박리 공정이 오랜 시간 수행되어야 하고 이로 인하여 공정 효율이 저하된다. In general, the photoresist used in the etching process has a film thickness of 2 μm or less, but the photoresist used in an electrode such as a bump electrode forming process or a redistribution line (RDL) has a thickness of 5 μm or more. Since it should be formed to several tens of micrometers, the peeling process for removing the photoresist must be carried out for a long time, thereby reducing the process efficiency.
또한, 포토레지스트는 박리액에 의해 균일하지 않게 제거되지 않으면 반도체 소자의 불량을 초래할 수 있으므로 포토레지스트 제거 공정 중에 사용되는 박리액 조성물은 박리 및 용해 작용을 균형 있게 병행할 수 있어야 한다. In addition, since the photoresist is not uniformly removed by the stripping solution, it may cause defects in the semiconductor device, so that the stripping solution composition used during the photoresist removing process should be able to balance the peeling and dissolving action in parallel.
다양한 포토레지스트 박리액이 알려져 있다. 예를 들어, 특허출원공개 2004-0104033호에는 모노에탄올아민, 글리콜계 화합물, 극성용매 및 부식방지제로 구성되어 있는 포토레지스트 박리액 조성물이 개시되어 있다. 상기 조성물은 포지티브 포토레지스트를 박리할 수 있지만 네가티브 포토레지스트를 박리할 수 없는 특성을 가지고 있다. Various photoresist strippers are known. For example, Japanese Patent Application Laid-Open No. 2004-0104033 discloses a photoresist stripper composition composed of a monoethanolamine, a glycol-based compound, a polar solvent, and a corrosion inhibitor. The composition has the property of being able to strip positive photoresist but not of negative photoresist.
특허출원공개 2007-0019897호에는 히드라진, 극성 유기용제 및 염기성 화합물로 구성된 네가티브 포토레지스트용 박리액 조성물이 개시되어 있지만 환경관리 물질인 히드라진을 포함함으로써 공정 적용이 어려운 특성을 가지고 있다.Patent application publication 2007-0019897 discloses a stripper composition for negative photoresist composed of hydrazine, a polar organic solvent and a basic compound, but has a characteristic of being difficult to apply the process by including hydrazine as an environmental management substance.
특허출원공개 2006-117219호에는 하이드록사이드계 화합물, 글리콜류 및 디메틸설폭사이드로 구성된 네가티브 포토레지스트 박리액 조성물이 개시되어 있는데, 상기 조성물은 네가티브 포토레지스트를 박리할 수 있지만 120㎛ 이상의 두께를 갖는 후막의 포토레지스트를 제거하기 위해 60분 이상의 시간을 필요로 하기 때문에 공정 효율이 낮다.Japanese Patent Application Laid-Open No. 2006-117219 discloses a negative photoresist stripper composition composed of a hydroxide compound, glycols, and dimethyl sulfoxide, wherein the composition can strip a negative photoresist but has a thickness of 120 µm or more. The process efficiency is low because a time of 60 minutes or more is required to remove the photoresist of the thick film.
특허 등록 10-0770217호에는 테트라메틸암모늄 하이드록사이드(TMAH), 알칸올아민 및 극성 유기 용매로 구성된 범프 전극 형성용 후막의 포토레지스트 제거용 조성물을 게시하고 있다. 상기 조성은 후막의 네가티브 포토레지스트에 대한 박리력이 우수하며 폴리이미드 막의 손상을 최소화하였으나 메탈 전극에 대한 부식이 취약 하므로 폴리이미드로 전극을 보호하고 있지 않은 공정에 적용하기 어려운 단점을 가지고 있다.Patent registration 10-0770217 discloses a composition for removing photoresist of a thick film for forming a bump electrode composed of tetramethylammonium hydroxide (TMAH), an alkanolamine and a polar organic solvent. The composition has a disadvantage in that it is excellent in peeling force on the negative photoresist of the thick film and minimizes damage to the polyimide film, but it is difficult to be applied to a process in which the electrode is not protected by polyimide because the corrosion on the metal electrode is weak.
한편, 특허출원공개 1997-016836호는 히드록실아민류, 물, 산해리정수(pKa)가 7.5 내지 13인 아민류, 수용성 유기용매, 및 방식제로 이루어진 박리액 조성물을 개시하고 있지만, 환경관리 물질인 하이드록실아민류를 포함함으로써 폐수 처리에 어려운 단점을 가지고 있으며, 방식제를 사용함으로 인해 조성이 복잡해지고 공정 중 이들의 흡착으로 인하여 후속 공정에 증착 불량을 야기할 수 있는 단점을 가지고 있다.On the other hand, Patent Application Publication No. 1997-016836 discloses a peeling liquid composition consisting of hydroxylamines, water, amines having an acid dissociation constant (pKa) of 7.5 to 13, a water-soluble organic solvent, and an anticorrosive agent, but it is hydroxyl as an environmental management substance. The inclusion of amines has the disadvantage of being difficult to treat the wastewater, and the use of the anticorrosive agent has a disadvantage in that the composition is complicated and the adsorption of these in the process causes deposition failure in subsequent processes.
따라서 본 발명은 후막의 네가티브 포토레지스트를 단시간에 효과적으로 박리할 수 있는 박리액 조성물을 제공하고자 한다. Accordingly, the present invention seeks to provide a stripper composition capable of effectively peeling off a negative photoresist of a thick film in a short time.
상기 목적에 따라 본 발명은, 1 내지 5중량%의 화학식(1)로 표시되는 화합물, 70내지 95중량%의 극성 유기 용매, 0.1내지 5중량%의 하이드록사이드계 화합물 및 나머지량의 물을 포함하는 포토레지스트 박리액 조성물을 제공한다.According to the above object, the present invention, 1 to 5% by weight of the compound represented by the formula (1), 70 to 95% by weight of a polar organic solvent, 0.1 to 5% by weight of the hydroxide compound and the remaining amount of water It provides a photoresist stripping liquid composition comprising.
(1) (One)
상기 식 중, n은 2~8의 정수이다.In said formula, n is an integer of 2-8.
본 발명 따른 포토레지스트 박리액 조성물은 단시간 박리 공정을 진행하더라도 후막의 포토레지스트를 효율적으로 제거하여 공정 시간 단축에 따른 비용 절감을 얻을 수 있으며, 다른 공정에 비해 상대적으로 높은 공정온도에서 수행되는 박리 공정에서 조성변화를 최소화할 수 있다. 또한, 부식방지제를 포함하지 않음으로써 비수용성인 부식방지제 흡착에 의한 증착 불량과 같은 후공정 불량을 방지하면서 전극 손상을 막을 수 있게 한다.The photoresist stripper composition according to the present invention can remove the photoresist of the thick film efficiently even if the short time stripping process is carried out to obtain cost savings due to the shortening of the process time, and is performed at a relatively high process temperature compared to other processes. The change in composition can be minimized. In addition, by not including the corrosion inhibitor, it is possible to prevent electrode damage while preventing post-processing defects such as deposition failure by adsorption of the water-insoluble corrosion inhibitor.
도 1은 본 발명에 있어서 실시예 1의 박리액 조성 평가에 따른 범프 전극 표면의 FE-SEM 사진이다.
도2는 본 발명에 따르지 않는 비교예 1의 박리액 조성으로 박리 성능 평가에 따른 범프 전극 표면의 FE-SEM 사진이다.
도3은 본 발명에 따르지 않는 비교예 1의 박리액 조성으로 금속막 부식성 평가에 따른 범프 전극 표면의 FE-SEM 사진이다.1 is a FE-SEM photograph of the bump electrode surface according to the peeling liquid composition evaluation of Example 1 in the present invention.
Figure 2 is a FE-SEM picture of the surface of the bump electrode according to the peeling performance evaluation in the peeling liquid composition of Comparative Example 1 not according to the present invention.
Figure 3 is a FE-SEM picture of the surface of the bump electrode according to the evaluation of the metal film corrosive with the peeling liquid composition of Comparative Example 1 not according to the present invention.
본 발명은 후막의 네가티브 포토레지스트를 효과적으로 분해 제거할 수 있는 박리액 조성물을 제공한다. 본원 명세서에서 후막이란 일반적인 리소그래피 공정에서 사용되는 포토레지스트 두께인 1~2㎛을 초과하는 두께로 적층된 포토레지스트막을 의미한다. The present invention provides a stripper composition that can effectively decompose and remove a negative photoresist of a thick film. In the present specification, a thick film means a photoresist film laminated to a thickness exceeding 1 to 2 μm, which is a photoresist thickness used in a general lithography process.
본 발명에 따른 네가티브 포토레지스트 박리액 조성물은 1 내지 5중량%의 화학식(1)로 표시되는 화합물, 70 내지 95중량%의 극성 유기 용매, 0.1 내지 5 중량%의 하이드록사이드계 화합물 및 나머지량의 물을 포함하며 부식방지제를 포함하지 않는 것을 특징으로 한다. The negative photoresist stripper composition according to the present invention comprises 1 to 5% by weight of a compound represented by the formula (1), 70 to 95% by weight of a polar organic solvent, 0.1 to 5% by weight of a hydroxide compound and the remaining amount It contains water and does not contain corrosion inhibitors.
박리액 조성물 내에 부식방지제를 포함하지 않고 화학식(1)로 표시되는 화합물을 포함함으로써 효과적으로 단시간 내에 박리 공정을 완료할 수 있으며 다른 공정에 비해 상대적으로 높은 공정온도에서 수행되는 박리 공정에서 조성변화를 최소화할 수 있으며 부식방지제를 포함하지 않음으로써 비수용성인 부식방지제 흡착에 의한 증착 불량과 같은 후공정 불량을 방지하면서 전극 손상을 막을 수 있게 한다.By including the compound represented by the formula (1) without including the corrosion inhibitor in the peeling liquid composition, it is possible to effectively complete the peeling process in a short time and minimize the compositional change in the peeling process performed at a relatively high process temperature compared to other processes It is possible to prevent damage to the electrode while preventing post-processing defects, such as poor deposition due to adsorption of non-aqueous corrosion inhibitors by not containing corrosion inhibitors.
일반적으로 부식 방지제는 금속의 표면에 부착하여 부식을 억제하는 일종의 표면 보호제이다. 부식 방지제는 극성기가 금속 표면에 흡착하고 비극성기 배열에 의해 생긴 피막이 전하의 이동에 변화를 주어 또한 부식에 관계 있는 물질의 이동을 저지한다. 따라서 본 발명에서 사용된 상기 화학식(1)로 표시되는 화합물은 다수의 N(질소원자)으로 구성되는 아민 성분으로 알칼리(alkali)도에 의해 박리 성능을 극대화 시키며 다수의 -N기에 의해 금속 표면을 보호하여 금속 전극 손상을 최소화 할 수 있다. In general, corrosion inhibitors are a type of surface protector that adheres to the surface of the metal to inhibit corrosion. Corrosion inhibitors adsorb the polar groups on the metal surface and the coating resulting from the arrangement of the nonpolar groups alters the transfer of charges and also prevents the movement of materials involved in corrosion. Therefore, the compound represented by the formula (1) used in the present invention is an amine component composed of a plurality of N (nitrogen atoms) to maximize the peeling performance by the alkali (alkali) degree and the metal surface by a plurality of -N groups Protection can minimize metal electrode damage.
본 발명에 사용되는 화학식(1)로 표시되는 화합물은 수용성이므로 다른 부식방지제와 달리 후공정 불량을 방지할 수 있으며 그 예로는 디에틸렌트리아민, 트리에틸렌테트라아민, 테트라에틸렌펜타아민, 펜타에틸렌헥사아민, 헥사에틸렌헵타아민 등이 있으며 이들은 단독 또는 2종 이상을 조합하여 사용할 수 있다. 특히 화학식(1)에서 n은 2~8의 에틸렌 아민 계열이 바람직하다. n이 1인 화합물은 에틸렌디아민으로써 화합물 내에 포함되는 N(질소원자)가 부족하여 부식방지에 효과적이지 못하며 n이 9이상일 경우 분자량이 증가하여 포토레지스트에 침투하는 능력이 저하되므로 박리 성능을 저감시키게 된다.Since the compound represented by the formula (1) used in the present invention is water-soluble, unlike other corrosion inhibitors, post-process defects can be prevented, and examples thereof include diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, and pentaethylenehexa. Amine, hexaethyleneheptaamine, and the like, and these may be used alone or in combination of two or more thereof. In the formula (1), n is preferably 2 to 8 ethylene amine series. Compounds with n of 1 are ethylenediamine, which is not effective in preventing corrosion due to lack of N (nitrogen atoms) contained in the compound. When n is 9 or more, the molecular weight increases and the ability to penetrate the photoresist decreases, thereby reducing the peeling performance. do.
본 발명에 따른 박리액에 함유되는 화학식 (1) 화합물의 함량은 조성물 총중량을 기준으로 1 내지 5 중량% 인 것이 바람직하다. 1 중량% 미만인 경우에는 부식방지에 효과적이지 못하고, 5 중량%를 초과하는 경우에는 상대적으로 극성 유기 용매의 함량이 감소하게 되어 박리 성능을 저하 시키게 된다. The content of the compound of formula (1) contained in the stripper according to the present invention is preferably 1 to 5% by weight based on the total weight of the composition. If it is less than 1% by weight, it is not effective in preventing corrosion, and when it is more than 5% by weight, the content of the polar organic solvent is relatively decreased, thereby reducing the peeling performance.
본 발명에 따른 박리액 조성물에 함유되는 극성 유기 용제는 박리액 조성물에 사용되는 극성 유기용매라면 제한없이 사용될 수 있다. 구체적으로 예를 들면, The polar organic solvent contained in the peeling liquid composition according to the present invention can be used without limitation as long as it is a polar organic solvent used in the peeling liquid composition. Specifically, for example
디메틸설폭사이드 등의 설폭사이드류; 디메틸술폰, 디에틸술폰, 비스 (2-히드록시에틸)술폰, 테트라메틸렌술폰 등의 술폰류; N,N-디메틸포름아마이드, N-메틸포름아마이드, N,N-디메틸 아세트아마이드, N-메틸아세트아마이드, N,N-디에틸 아세트아마이드 등의 아마이드류; N,N’-디메틸 락탐아마이드, 2-피롤리돈, N-메틸-2-피롤리돈, N-에틸-2-피롤리돈, N-프로필-2-피롤리돈, N-히드록시메틸-2-피롤리돈, N-히드록시에틸-2-피롤리돈 등의 락탐류; 1,3-디메틸-2-이미다졸리디논, 1,3-디에틸-2-이미다졸리디논, 1,3-디이소프로필-2-이미다졸리디논 등의 이미다졸리디논류; 에틸렌글리콜, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노부틸에테르, 에틸렌글리콜모노메틸에테르아세테이트, 에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노부틸에테르 등의 다가알코올류 및 그의 유도체를 들 수 있다.Sulfoxides such as dimethyl sulfoxide; Sulfones such as dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone and tetramethylene sulfone; Amides such as N, N-dimethylformamide, N-methylformamide, N, N-dimethyl acetamide, N-methylacetamide, N, N-diethyl acetamide; N, N'-dimethyl lactamamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl Lactams such as 2-pyrrolidone and N-hydroxyethyl-2-pyrrolidone; Imidazolidinones, such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone; Ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol mono Polyhydric alcohols, such as ethyl ether and diethylene glycol monobutyl ether, and its derivative (s) are mentioned.
이들은 단독으로 사용하여도 좋고, 또는 2 종 이상을 조합하여도 좋다. 이 들 중에서도 디메틸설폭사이드, N,N-디메틸포름아마이드, N,N-디메틸아세트아마이드, N,N’-디에틸아세트아마이드, N-메틸포름아마이드, N,N’-디메틸락탐아마이드, 1,3-디메틸-2-이미다졸리디논, 디에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, N-메틸 피롤리돈, N-에틸 피롤리돈, 2-피롤리돈에서 선택되는 1종 이상의 것을 사용하는 것이 박리성이 우수하므로 더욱 바람직하다. These may be used independently, or may combine 2 or more types. Among these, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N'-diethylacetamide, N-methylformamide, N, N'-dimethyllactamamide, 1, At least one selected from 3-dimethyl-2-imidazolidinone, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, N-methyl pyrrolidone, N-ethyl pyrrolidone and 2-pyrrolidone It is more preferable to use since it is excellent in peelability.
본 발명에 따른 박리액 조성물에 함유되는 극성 유기 용제의 함량은 70 내지 95중량%인 것이 바람직하고, 보다 바람직하게는 80 내지 95중량%이다. 상기 함량이70중량% 미만인 경우에는 포토레지스트에 대한 용해도가 떨어지는 문제가 있어 깨끗하게 레지스트가 제거되지 않는 문제가 있고, 상기 함량이 95중량%를 초과할 경우에는 상대적으로 다른 구성 성분의 함량이 모자라게 되어 박리 성능이 떨어지게 되고, 부식 현상이 나타날 수 있는 문제점이 있다.It is preferable that the content of the polar organic solvent contained in the peeling liquid composition which concerns on this invention is 70 to 95 weight%, More preferably, it is 80 to 95 weight%. If the content is less than 70% by weight, there is a problem that the solubility of the photoresist is inferior, so that the resist is not removed cleanly, and when the content is more than 95% by weight, the content of other components is insufficient. The peeling performance is lowered, there is a problem that the corrosion phenomenon may appear.
본 발명에 따른 박리액에 함유되는 하이드록사이드계 화합물은 네가티브 포토레지스트의 박리성능을 보다 향상시키기 위해 첨가하는 것으로서, 테트라알킬암모늄하이드록사이드가 바람직하다. 이때 알킬은 C1~C5의 알킬기에서 선택될 수 있다. The hydroxide compound contained in the stripper according to the present invention is added to further improve the stripping performance of the negative photoresist, and tetraalkylammonium hydroxide is preferred. At this time, the alkyl may be selected from an alkyl group of C 1 ~ C 5 .
하이드록사이드계 화합물의 함량은 박리액 전체 조성물에 대하여 0.1 내지 5중량%인 것이 바람직하고, 보다 바람직하게는 1 내지 4중량% 이다. 상기 함량이 0.1 중량% 미만일 경우에는 박리성능이 저하되는 문제가 있으며, 상기 함량이 5중량%를 초과할 경우에는 하부 금속막에 대한 부식을 유발할 우려가 있다. The content of the hydroxide compound is preferably 0.1 to 5% by weight, more preferably 1 to 4% by weight based on the total composition of the stripping solution. If the content is less than 0.1% by weight, there is a problem that the peeling performance is lowered, if the content exceeds 5% by weight there is a risk of causing corrosion to the lower metal film.
본 발명의 조성물에 포함되는 물은 특별히 한정되지 않지만 탈이온수를 사용할 수 있으며, 바람직하게는 물 속 이온이 제거된 정도를 보여주는 물의 비저항 값이 18㏁/㎝ 이상인 탈이온수를 사용한다.
Although the water contained in the composition of the present invention is not particularly limited, deionized water may be used. Preferably, deionized water having a specific resistance of 18 ㏁ / cm or more that shows the degree of removal of ions in water is used.
이하, 본 발명을 실시예에 의해 상세히 설명한다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.
<< 실시예Example 1 내지 13과 1 to 13 lessons 비교예Comparative Example 1 내지 7> 1 to 7>
화학식 (1) 화합물, 극성 유기용매, 하이드록사이드계 화합물 및 물을 표 1에 나타낸 바와 같이 배합하여 네가티브 포토레지스트 박리액 조성물을 제조하였다. A negative photoresist stripper composition was prepared by combining the compound of formula (1), a polar organic solvent, a hydroxide compound and water as shown in Table 1.
[중량%]Compound of Formula (1)
[weight%]
[중량%]Polar organic solvent
[weight%]
[중량%]water
[weight%]
● 화학식(1) 화합물 - EDA:에틸렌디아민, DETA:디에틸렌트리아민, TETA:트리에틸렌테트라아민, TEPA:테트라에틸렌펜타아민, PEHA:펜타에틸렌헥사아민
● 극성 유기 용매 - DMSO:디메틸설폭사이드, NMP:N-메틸피롤리돈, PRD:2-피롤리돈, NEP:N-에틸 피롤리돈, DMAc:N,N-디메틸아세트아마이드, DMF:N,N-디메틸포름아마이드
● 하이드록사이드계 화합물 - TMAH:테트라메틸암모늄 하이드록사이드, TEAH:테트라에틸암모늄 하이드록사이드, TBAH:테트라부틸암모늄 하이드록사이드
Formula (1) Compound-EDA: ethylenediamine, DETA: diethylenetriamine, TETA: triethylenetetraamine, TEPA: tetraethylenepentaamine, PEHA: pentaethylenehexaamine
Polar organic solvents-DMSO: dimethylsulfoxide, NMP: N-methylpyrrolidone, PRD: 2-pyrrolidone, NEP: N-ethyl pyrrolidone, DMAc: N, N-dimethylacetamide, DMF: N , N-dimethylformamide
● Hydroxide compound-TMAH: Tetramethylammonium hydroxide, TEAH: Tetraethylammonium hydroxide, TBAH: Tetrabutylammonium hydroxide
<포토레지스트 박리 성능 평가><Photoresist peeling performance evaluation>
상기 표1과 같이 제조된 포토레지스트 박리액 조성에 대하여 포토레지스트 박리 성능을 평가하였다.Photoresist stripping performance of the photoresist stripper composition prepared as shown in Table 1 was evaluated.
상기 조성물의 포토레지스트 박리 성능을 평가하기 위해, 구리로 도금된 웨이퍼 상에 약 50 ~ 60㎛의 두께로 포토레지스트와 주석재질의 범프 전극을 형성하였다. 구체적으로, 구리로 UBM (Under Bump Metallurgy)층이 형성된 웨이퍼 상에 약 50 ~ 60㎛의 두께로 포토레지스트 막을 구성하였다. 상기에서 수행된 포토레지스트에 노광 공정으로 패턴을 형성한 후 현상공정을 거쳐 전기 도금법으로 주석재질의 범프 전극을 형성하였다.In order to evaluate the photoresist peeling performance of the composition, bump electrodes of photoresist and tin material were formed on a copper plated wafer with a thickness of about 50 to 60 μm. Specifically, a photoresist film was formed to a thickness of about 50 to 60 μm on a wafer on which an UBM (Under Bump Metallurgy) layer was formed of copper. After the pattern was formed on the photoresist carried out by the exposure process, a bump electrode of tin material was formed by an electroplating method through a developing process.
이어서, 포토레지스트와 범프 전극으로 구성된 웨이퍼를 3 cm x 3 cm의 크기로 절단하여 평가 시편을 제조하였다. 상기 시편을 표1과 같이 제조된 각각의 박리액 조성물에 60℃에서 3분간 침적하여 포토레지스트 막을 제거하였다. 포토레지스트 막이 제거된 상기 시편을 초순수로 약1분간 세정 후 질소로 건조하였다. 건조된 시편을 FE-SEM으로 포토레지스트 제거 여부를 확인하였다(도 1 및 도 2 참조). 도 1은 실시예 1의 박리액 조성 평가에 따른 범프 전극 표면의 FE-SEM 사진이고, 도2는 비교예 1 의 박리액 조성으로 박리 성능 평가에 따른 범프 전극 표면의 FE-SEM 사진이다.Subsequently, an evaluation specimen was prepared by cutting a wafer composed of a photoresist and a bump electrode to a size of 3 cm x 3 cm. The specimens were immersed at 60 ° C. for 3 minutes in each of the stripper compositions prepared as shown in Table 1 to remove the photoresist film. The specimen from which the photoresist film was removed was washed with ultrapure water for about 1 minute and then dried with nitrogen. The dried specimens were checked for photoresist removal by FE-SEM (see FIGS. 1 and 2). 1 is a FE-SEM picture of the bump electrode surface according to the peeling liquid composition evaluation of Example 1, Figure 2 is a FE-SEM picture of the bump electrode surface according to the peeling performance evaluation with the peeling liquid composition of Comparative Example 1.
상기 실험 조건은 통상적인 범프 전극 포토레지스트의 박리 공정이 10분 이상인 것에 비해 평이한 조건을 제공하여 박리 정도의 차이를 크게 보고자 한 것이다. 그 결과를 표2에 나타내었다.The experimental conditions are intended to provide a wider difference in the degree of peeling by providing a flat condition as compared to the peeling process of the conventional bump electrode photoresist is 10 minutes or more. The results are shown in Table 2.
◎ : 포토레지스트 100% 제거 되어 잔류물 없음 ◎: 100% photoresist removed, no residue
○ : 포토레지스트 80% 이상 제거되어 잔류물 거의 없음 ○: 80 80% or more of photoresist removed, almost no residue
△ : 포토레지스트 50% 이상 제거되어 상당량 잔류 함 △: 50% or more of photoresist removed
× : 포토레지스트 50% 미만 제거되어 다소 많은 양의 포토레지스트 잔류 함×: Less than 50% of photoresist removed, leaving a large amount of photoresist
<금속막 부식성 평가><Metal Film Corrosion Evaluation>
상기 표1과 같이 제조된 포토레지스트 박리액 조성에 대하여 범프 전극 금속의 부식성을 평가하였다.Corrosion property of the bump electrode metal was evaluated for the photoresist stripper composition prepared as shown in Table 1 above.
상기 조성물의 범프 전극 금속의 부식성을 평가하기 위해, 구리로 도금된 웨이퍼 상에 약 50~60㎛의 두께로 포토레지스트와 주석재질의 범프 전극을 형성하였다. 이어서, 포토레지스트와 범프 전극으로 구성된 웨이퍼를 3 X 3 cm의 크기로 절단하여 평가 시편을 제조하였다. In order to evaluate the corrosiveness of the bump electrode metal of the composition, a bump electrode of photoresist and tin material was formed on a copper plated wafer at a thickness of about 50 to 60 μm. Subsequently, an evaluation specimen was prepared by cutting a wafer composed of a photoresist and a bump electrode to a size of 3 × 3 cm.
상기 시편을 표1과 같이 제조된 각각의 박리액 조성물에 60℃에서 30분간 침적한 후 초순수로 1분간 세정하고 질소를 이용하여 건조하였다. 상기 건조된 시편을 FE-SEM으로 범프 전극 금속의 표면의 부식 정도를 확인하였다. 도3은 본 발명에 따르지 않는 비교예 1의 박리액 조성으로 금속막 부식성 평가에 따른 범프 전극 표면의 FE-SEM 사진이다.The specimens were immersed at 60 ° C. for 30 minutes in each of the stripper compositions prepared as shown in Table 1, washed with ultrapure water for 1 minute, and dried using nitrogen. The dried specimens were FE-SEM to determine the degree of corrosion of the surface of the bump electrode metal. Figure 3 is a FE-SEM picture of the surface of the bump electrode according to the evaluation of the metal film corrosive with the peeling liquid composition of Comparative Example 1 not according to the present invention.
상기 실험 조건은 통상적인 범프 전극 포토레지스트의 박리 공정이 10분 이내인 것에 비해 가혹한 부식조건을 제공하여 부식정도의 차이를 크게 보고자 한 것이다. 그 결과를 표2에 나타내었다.The experimental condition is to provide a severe corrosion condition compared to the conventional peeling process of the bump electrode photoresist within 10 minutes to see a large difference in the degree of corrosion. The results are shown in Table 2.
◎ : 구리 및 주석의 부식이 관찰되지 않음 ◎: No corrosion of copper and tin
○ : 구리 및 주석의 약간의 금속 부식이 관찰됨 : Slight metal corrosion of copper and tin is observed
△ : 구리 및 주석의 부분적인 금속 부식이 관찰됨 Δ: Partial metal corrosion of copper and tin is observed
× : 구리 및 주석의 전체적으로 금속 부식이 관찰됨×: Metal corrosion of copper and tin was observed as a whole
상기 결과로부터 알 수 있는 바와 같이, 본 발명 따른 포토레지스트 박리액 조성물은 부식방지제를 포함하지 않고 화학식(1)로 표시되는 화합물을 적정량 포함함으로써 단시간 박리 공정을 진행하더라도 후막의 포토레지스트를 효율적으로 제거하여 공정 시간 단축에 따른 비용 절감을 얻을 수 있다.As can be seen from the above results, the photoresist stripper composition according to the present invention does not contain a corrosion inhibitor and contains an appropriate amount of the compound represented by the formula (1), so that the photoresist of the thick film can be efficiently removed even if the stripping process is performed for a short time. In this way, the cost can be reduced by reducing the process time.
Claims (5)
(1)
상기 식 중 n은 2~8의 정수임. A photoresist stripper composition comprising 1 to 5% by weight of a compound represented by formula (1), 70 to 95% by weight of a polar organic solvent, 0.1 to 5% by weight of a hydroxide-based compound, and a balance of water:
(One)
N is an integer of 2-8.
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