KR20210086113A - Cleaning agent composition for removing oxide film and mask forming method using the same - Google Patents
Cleaning agent composition for removing oxide film and mask forming method using the same Download PDFInfo
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- KR20210086113A KR20210086113A KR1020190179821A KR20190179821A KR20210086113A KR 20210086113 A KR20210086113 A KR 20210086113A KR 1020190179821 A KR1020190179821 A KR 1020190179821A KR 20190179821 A KR20190179821 A KR 20190179821A KR 20210086113 A KR20210086113 A KR 20210086113A
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- South Korea
- Prior art keywords
- sulfate
- oxide film
- cleaning composition
- cleaning
- sulfuric acid
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000012459 cleaning agent Substances 0.000 title abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 8
- 239000012498 ultrapure water Substances 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- BGYGXCUCWAXMNO-UHFFFAOYSA-N azane;2h-tetrazole Chemical compound N.C=1N=NNN=1 BGYGXCUCWAXMNO-UHFFFAOYSA-N 0.000 claims description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 7
- 239000012964 benzotriazole Substances 0.000 claims description 7
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- -1 azole compound Chemical class 0.000 claims description 5
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 3
- KAQHZJVQFBJKCK-UHFFFAOYSA-L potassium pyrosulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OS([O-])(=O)=O KAQHZJVQFBJKCK-UHFFFAOYSA-L 0.000 claims description 3
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 claims description 2
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 claims description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 2
- NAXUFNXWXFZVSI-UHFFFAOYSA-N 4-aminobutan-2-ol Chemical compound CC(O)CCN NAXUFNXWXFZVSI-UHFFFAOYSA-N 0.000 claims description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 150000004885 piperazines Chemical class 0.000 claims description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- 229940099596 manganese sulfate Drugs 0.000 claims 1
- 235000007079 manganese sulphate Nutrition 0.000 claims 1
- 239000011702 manganese sulphate Substances 0.000 claims 1
- OJSWEKSDNUORPG-UHFFFAOYSA-H neodymium(3+);trisulfate Chemical compound [Nd+3].[Nd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OJSWEKSDNUORPG-UHFFFAOYSA-H 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000059 patterning Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 229910001374 Invar Inorganic materials 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- RHVPCSSKNPYQDU-UHFFFAOYSA-H neodymium(3+);trisulfate;hydrate Chemical compound O.[Nd+3].[Nd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RHVPCSSKNPYQDU-UHFFFAOYSA-H 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910016876 Fe(NH4)2(SO4)2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
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- C11D11/0047—
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/3042—Imagewise removal using liquid means from printing plates transported horizontally through the processing stations
- G03F7/3057—Imagewise removal using liquid means from printing plates transported horizontally through the processing stations characterised by the processing units other than the developing unit, e.g. washing units
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
본 발명은 산화막 제거용 세정제 조성물 및 이를 이용한 마스크 형성 방법에 관한 것으로서, 더욱 상세하게는 OLED에 사용되는 산화막 제거용 세정제 조성물 및 이를 이용한 마스크 형성 방법에 관한 것이다.The present invention relates to a cleaning composition for removing an oxide film and a method for forming a mask using the same, and more particularly, to a cleaning composition for removing an oxide film used for an OLED and a method for forming a mask using the same.
본 발명은 모바일 산업이 증가되면서 소형 집적회로의 색 구현 능력이 향상되어야 하므로, 미세한 EL증착이 범용적으로 사용해야 하는 미세한 패턴닝을 위한 마스크의 세정제가 필요하게 되었다. 즉, 본 발명에서는 미세 패턴용 마스크 제작시 발생되는 산화물 및 유기물을 깨끗이 제거하기 위한 조성물에 대한 내용을 설명한다. 본 발명은 FFM strick을 제작하는데 있어서 현재 적용 가능하고 일반화되어 있는 제작 기법인 에칭(Etching)법이다. In the present invention, since the color realization ability of a small integrated circuit needs to be improved as the mobile industry increases, a cleaning agent for a mask for fine patterning that must be used universally for fine EL deposition is required. That is, in the present invention, the content of the composition for cleanly removing oxides and organic matter generated during the manufacturing of the mask for fine patterns will be described. The present invention is an etching method, which is a fabrication technique that is currently applicable and generalized in manufacturing an FFM strick.
에칭(Etching)법은 Stick의 모재로 사용되고 있는 재료를 가지고, 에첸트(Etchant)를 스프레이(Spray) 분사 또는 디핑(Dipping)등의 방법으로 에칭(Etching)하여 패터닝(Patterning)하는 방식이다. 에칭(Etching)법의 경우, Stick 제작 기법 자체가 에첸트(Etchant)를 이용한 습식법이기 때문에 Stick 제작 후 DI 및 알코올류(IPA) Rinse 정도의 마무리로 충분하다.The etching method is a method of patterning by etching an etchant using a method such as spray spraying or dipping with a material used as a base material of a stick. In the case of the etching method, since the stick production method itself is a wet method using an etchant, finishing with DI and alcohol (IPA) rinse after stick production is sufficient.
하지만, 장치가 커서 사용하기 위한 위치적인 제한이 있으며, 정밀한 방식의 Patterning에 제약이 있어 차세대 패터닝(Patterning) 기술이 필요하다. However, since the device is large, there is a positional limitation for use, and there is a restriction on precise patterning, a next-generation patterning technology is required.
따라서, 본 발명과 같이 미세 패턴을 구현하기 위해 레이저를 이용한 마스크를 패턴하는 과정이 점점 늘어나고 있는 추세이다.Therefore, as in the present invention, the process of patterning a mask using a laser to implement a fine pattern is gradually increasing.
따라서, 본 발명의 목적은 표면에 잔류하는 유기물 및 무기물에 대한 세정 효과가 우수하며, 레이저로 발생된 산화막이 포함되어 있어도 세정 효과가 우수한 세정제 조성물을 제공하는 것이다.Accordingly, it is an object of the present invention to provide a cleaning composition that has excellent cleaning effect on organic and inorganic materials remaining on the surface, and has excellent cleaning effect even when an oxide film generated by laser is included.
본 발명의 다른 목적은 단시간내에 세정이 가능하며, 두꺼운 산화막도 사용시간내에는 제거가 가능하며, 마스크(Mask)에는 영향성을 최소화하여 부식에는 영향성이 없는 세정제 조성물을 제공하는 것이다.Another object of the present invention is to provide a cleaning composition that can be cleaned within a short time, even a thick oxide film can be removed within a usage time, and has no influence on corrosion by minimizing the influence on the mask.
상기 목적을 달성하기 위하여, 본 발명은 황산계 산화제 0.1 내지 5 중량%; 아졸계 화합물 0.1 내지 5 중량%; 및 나머지 함량의 초순수를 포함하는 산화막 제거용 세정제 조성물을 제공한다. In order to achieve the above object, the present invention is a sulfuric acid-based oxidizing agent 0.1 to 5% by weight; 0.1 to 5 wt% of an azole compound; And it provides a cleaning composition for removing the oxide film comprising the remaining content of ultrapure water.
또한 본 발명은 철 및 아연을 포함하는 금속 마스크 표면에 레이저로 패턴을 새기는 단계; 및 상기 패턴이 새겨진 금속 마스크 표면에 황산계 산화제 0.1 내지 5 중량%, 아졸계 화합물 0.1 내지 5 중량% 및 나머지 함량의 초순수를 포함하는 산화막 제거용 세정제 조성물을 도포하여 세정하는 단계를 포함하는 마스크 세정 방법을 제공한다.In addition, the present invention includes the steps of engraving a pattern with a laser on the surface of a metal mask containing iron and zinc; and applying a cleaning agent composition for removing an oxide film comprising 0.1 to 5 wt% of a sulfuric acid-based oxidizing agent, 0.1 to 5 wt% of an azole-based compound and the remaining amount of ultrapure water to the surface of the metal mask on which the pattern is engraved and cleaning the mask. provide a way
본 발명에 따른 산화막 제거용 세정제 조성물은 표면에 잔류하는 유기물, 무기물 및 금속 산화물에 대한 세정 효과가 우수하며, 마스크(Mask)에는 영향성을 최소화하여 부식에는 영향성이 없다.The cleaning composition for removing an oxide film according to the present invention has an excellent cleaning effect on organic, inorganic and metal oxides remaining on the surface, and has no effect on corrosion by minimizing the effect on the mask.
도 1은 금속막이 형성된 금속 표면을 나타낸 사진.
도 2는 본원발명에 따른 세정제를 통해 금속막이 제거된 금속 표면을 나타낸 사진.1 is a photograph showing a metal surface on which a metal film is formed.
Figure 2 is a photograph showing the metal surface from which the metal film is removed through the cleaning agent according to the present invention.
이하, 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 세정제 조성물은 황산계 산화제, 아졸계 화합물 및 초순수를 포함한다. 상기 황산계 산화제는 황산염과 과황산염을 포함할 수 있으며, 상기 황산계 산화제를 통해서 본 발명의 세정제 조성물이 마스크를 패턴하는 과정에서 발생된 부산물을 제거할 수 있다. The cleaning composition according to the present invention includes a sulfuric acid-based oxidizing agent, an azole-based compound, and ultrapure water. The sulfuric acid-based oxidizing agent may include sulfate and persulfate, and through the sulfuric acid-based oxidizing agent, by-products generated in the process of patterning the mask by the cleaning composition of the present invention may be removed.
상기 황산계 산화제는, 황산수소칼륨(KHSO4), 황산칼륨(K2SO4), 이황산칼륨(PDS, Potassium disulfate, K2S2O7), 과산화이황산칼륨(Potassium persulfate, K2S2O8), 황산(H2SO4), 황산암모늄((NH4)2SO4), 과황산암모늄(APS, ammonium persulfate, (NH4)2S2O8), 황산나트륨(Na2SO4), 황산수소나트륨(NaHSO4), 황산암모늄알루미늄(AlNH4(SO4)2), 황산알루미늄(Al2(SO4)3), 황산암모늄철(II)(Fe(NH4)2(SO4)2), 황산바륨(BaSO4), 황산칼슘(CaSO4), 과황산칼슘(CaS2O8), 황산철(FeSO4), 황산리튬(Li2SO4), 황산마그네슘(MgSO4), 황산망간(MnSO4), 황산네오디뮴(III)(Nd2(SO4)3), 황산아연(ZnSO4), 황산구리(CuSO4) 등을 1종 이상, 바람직하게는 2종 이상 포함할 수 있으며, 더욱 바람직하게는, 과산화이황산칼륨과 과황산암모늄 2종의 산화제를 포함할 수 있다. 일 예로, 상기 과산화이황산칼륨과 과황산암모늄은 1:1,000 내지 1,000:1, 바람직하게는, 1:100 내지 100:1의 중량비율로 혼합하여 사용할 수 있다. 상기 과산화이황산암모늄은 상대적으로 약한 산화제이고, 상기 과황산암모늄은 강한 산화제로써, 이들을 상기의 중량비율로 혼합하여 사용할 경우, 혼합비율에 따라 특히 마스크에 대한 데미지를 경감시키는 효과가 있다.The sulfuric acid-based oxidizing agent, potassium hydrogen sulfate (KHSO 4 ), potassium sulfate (K 2 SO 4 ), potassium disulfate (PDS, Potassium disulfate, K 2 S 2 O 7 ), potassium peroxide disulfate (Potassium persulfate, K 2 S) 2 O 8 ), sulfuric acid (H 2 SO 4 ), ammonium sulfate ((NH 4 ) 2 SO 4 ), ammonium persulfate (APS, ammonium persulfate, (NH 4 ) 2 S 2 O 8 ), sodium sulfate (Na 2 SO 4 ), sodium hydrogen sulfate (NaHSO 4 ), aluminum ammonium sulfate (AlNH 4 (SO 4 ) 2 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), iron ammonium sulfate (II)(Fe(NH 4 ) 2 ( SO 4 ) 2 ), barium sulfate (BaSO 4 ), calcium sulfate (CaSO 4 ), calcium persulfate (CaS 2 O 8 ), iron sulfate (FeSO 4 ), lithium sulfate (Li 2 SO 4 ), magnesium sulfate (MgSO) 4 ), manganese sulfate (MnSO 4 ), neodymium sulfate (III) (Nd 2 (SO 4 ) 3 ), zinc sulfate (ZnSO 4 ), copper sulfate (CuSO 4 ), etc. at least one, preferably two or more and more preferably, potassium peroxide and ammonium persulfate may include two types of oxidizing agents. For example, the potassium peroxide disulfate and ammonium persulfate may be mixed and used in a weight ratio of 1:1,000 to 1,000:1, preferably, 1:100 to 100:1. The ammonium peroxide disulfate is a relatively weak oxidizing agent, and the ammonium persulfate is a strong oxidizing agent.
상기 황산계 산화제의 함량은 세정제 조성물에 대하여, 0.1 내지 5 중량%, 바람직하게는 0.5 내지 2 중량%이다. 상기 함량보다 적으면 레이저로 발생된 부산물의 제거가 느려 세정에 적합하지 않은 문제가 있고, 과량일 경우에는 금속 재질의 마스크를 부식시키는 문제가 있다.The content of the sulfuric acid-based oxidizing agent is 0.1 to 5% by weight, preferably 0.5 to 2% by weight, based on the cleaning composition. If the content is less than the above content, there is a problem in that the removal of by-products generated by the laser is slow and not suitable for cleaning.
상기 아졸계 화합물은 부식 방지제로써 포함되며, 상기 부식방지제는 각각의 아졸계 화합물에 포함되어 있는 질소 원자가 금속막과 킬레이팅 작용(chelating effect)을 함으로써, 결합력을 증가시킬 수 있어, 세정 공정 시 세정제 조성물에 의한 금속의 부식이나 손상을 방지하는 작용을 할 수 있다.The azole-based compound is included as a corrosion inhibitor, and the corrosion inhibitor can increase bonding strength by chelating the nitrogen atom contained in each azole-based compound with the metal film, so that the cleaning agent is a cleaning agent during the cleaning process. It can act to prevent corrosion or damage to the metal by the composition.
상기 아졸계 화합물은, 이미다졸(imidazole), 암모늄테트라졸(ATZ, Ammonium tetrazole), 아미노테트라졸(aminotetrazole), 인돌(indole), 푸린(purine), 피라졸(pyrazole), 피리딘(pyridine), 피리미딘(pyrimidine), 피롤(pyrrole), 피롤리딘(pyrrolidine), 피롤린(pyrroline), 벤조트리아졸(benzotriazole), 톨릴트리아졸(Tolyltriazole) 등을 1종 이상 포함할 수 있으며, 바람직하게는 암모늄테트라졸(ATZ, Ammonium tetrazole), 벤조트리아졸(benzotriazole)을 포함할 수 있다. The azole-based compound is imidazole, ammonium tetrazole (ATZ, Ammonium tetrazole), aminotetrazole (aminotetrazole), indole (indole), purine (purine), pyrazole (pyrazole), pyridine (pyridine), It may include one or more of pyrimidine, pyrrole, pyrrolidine, pyrroline, benzotriazole, tolyltriazole, and the like, preferably Ammonium tetrazole (ATZ, Ammonium tetrazole), and may include benzotriazole (benzotriazole).
상기 아졸계 화합물은, 일 예로 암모늄테트라졸과 벤조트리아졸 2종을 포함할 수 있으며, 상기 암모늄테트라졸과 벤조트리아졸은 1:2 내지 2:1의 중량비로 혼합된 것일 수 있으나, 이에 제한되는 것은 아니다. The azole-based compound may include, for example, two types of ammonium tetrazole and benzotriazole, and the ammonium tetrazole and benzotriazole may be mixed in a weight ratio of 1:2 to 2:1, but limited thereto. it's not going to be
상기 아졸계 화합물의 함량은 세정제 조성물에 대하여, 0.1 내지 5 중량%, 바람직하게는 0.5 내지 3 중량%이다. 상기 함량보다 적으면 마스크에 부식을 발생시킬 수 있는 문제가 있고, 과량일 경우레이저로 인해 발생된 부산물을 제거하는 효율이 저하되는 문제가 있다.The content of the azole-based compound is 0.1 to 5% by weight, preferably 0.5 to 3% by weight, based on the cleaning composition. If it is less than the above content, there is a problem that may cause corrosion of the mask, and if it is excessive, there is a problem that the efficiency of removing by-products generated by the laser is reduced.
본 발명은 필요에 따라, 아민계 화합물을 더욱 포함할 수 있으며, 이를 통해세정제 조성물의 pH를 조절할 수 있다. 상기 아민계 화합물은 약염기성으로, 소량 사용하여 pH를 조절함으로서, 인바(inbar) 재질의 금속 마스크 손상(damage)을 방지할 수 있다. 상기 세정제 조성물의 바람직한 pH는 2 내지 7 이다. 상기 pH를 만족하지 못하면, 레이저로 발생된 부산물의 제거가 어려운 문제가 있다.The present invention may further include an amine-based compound, if necessary, through which the pH of the detergent composition can be adjusted. The amine-based compound is weakly basic, and by using a small amount to adjust the pH, it is possible to prevent damage to the metal mask of the inbar material. The preferred pH of the cleaning composition is 2 to 7. If the pH is not satisfied, there is a problem in that it is difficult to remove by-products generated by the laser.
상기 아민계 화합물은 1, 2 내지 3차 아민을 모두 포함할 수 있으며, 구체적으로는 아미노에탄올(aminoethanol); 디에탄올아민(diethanolamine); 트리에탄올아민(triethanolamine); 글리콜아민(glycolamine); 디글리콜아민(diglycolamine); 모노이소프로판올아민(monoisopropanolamine); 아미노에톡시에탄올(aminoethoxylethanol); 아미노에틸에탄올(aminoethylethanol); 피레라진(piperazine), 아미노메틸피페라진(Aminomethylpiperazine), 아미노에틸피페라진(aminoethylpiperazine) 등의 피페라진 계열 등이다. The amine-based compound may include all of primary, secondary, and tertiary amines, and specifically, aminoethanol; diethanolamine; triethanolamine; glycolamine; diglycolamine; monoisopropanolamine; aminoethoxylethanol; aminoethylethanol; Piperazine series such as pyrerazine, aminomethylpiperazine, and aminoethylpiperazine.
상기 아민계 화합물의 함량은 세정제 조성물에 대하여, 0.1 내지 5 중량%, 바람직하게는 0.1 내지 2 중량%이다. 상기 함량보다 적으면 마스크에 부식 현상이 발생될 수 있는 문제가 있고, 많으면 레이저로 발생된 부산물이 제거되지 않는 문제가 있다.The content of the amine-based compound is 0.1 to 5% by weight, preferably 0.1 to 2% by weight, based on the cleaning composition. If it is less than the above content, there is a problem that corrosion may occur in the mask, and if it is more, there is a problem that by-products generated by the laser are not removed.
본 발명에서 물은 명시적인 언급이 없더라도, 전체 조성물에서 물을 제외한 기타 나머지 성분의 중량%의 합과 물의 중량%의 합이 100 중량%가 되도록, 전체 세정제 조성물 중 물 이외의 기타 나머지 성분의 중량%합 외의 전부를 차지한다. 상기 세정제 조성물에 사용되는 물로는 반도체용 등급의 물 또는 초순수를 사용하는 것이 바람직하다.In the present invention, even if there is no explicit mention of water, the weight of the remaining components other than water in the total detergent composition so that the sum of the weight% of the other components except water and the weight% of water in the total composition is 100% by weight Occupies everything except the % sum. As water used in the cleaning composition, it is preferable to use semiconductor grade water or ultrapure water.
본 발명에 따른 세정제 조성물은, 미세 패턴용 마스크를 제조시, 레이저로 인하여 발생되는 산화막 및 마스크 표면에 잔류하는 유기물 및 무기물에 대한 세정력이 우수하다. 단시간내에 세정이 가능하며, 두꺼운 산화막의 잔류물도 사용시간 내에 제거가 가능하다. 또한, 마스크에는 영향이 최소화되어, 부식에 영향성을 미치지 않을 수 있다. The cleaning composition according to the present invention has excellent cleaning power for the organic and inorganic materials remaining on the surface of the mask and the oxide film generated by the laser when manufacturing a mask for a fine pattern. It can be cleaned within a short time, and even the residue of a thick oxide film can be removed within a period of use. In addition, the effect on the mask is minimized, so it may not affect the corrosion.
본 발명에 따른 세정제 조성물을 사용하여, 통상적인 방법으로 미세 패턴을 포함한 금속 마스크를 세정할 수 있다. 예를 들면, 금속 마스크 상에 원하는 미세 패턴을 새기고, 상기 세정제 조성물을 도포하여 세정함으로써, 패턴이 새겨진 금속 마스크 표면의 잔류물을 세정할 수 있다. Using the cleaning composition according to the present invention, it is possible to clean the metal mask including the fine pattern in a conventional method. For example, by engraving a desired fine pattern on a metal mask, applying the cleaning agent composition and cleaning, the residue on the surface of the metal mask on which the pattern is engraved can be cleaned.
상기 미세 패턴은 통상적인 방법으로 새길 수 있으며, 예를 들면, 레이저를 사용할 수 있다. 구체적으로, 상기 미세 패턴 형성 시, 레이저로 인해 발생되는 금속 또는 금속 산화물을 상기 세정제 조성물에 1시간 정도 침지하여, 불순물을 제거할 수 있다. 이를 통해, 예를 들어 도 1과 같이 검은색의 산화막이 형성된 인바 재질의 금속표면을, 도 2와 같이 산화막을 제거할 수 있다.The fine pattern may be engraved by a conventional method, for example, a laser may be used. Specifically, when the fine pattern is formed, the metal or metal oxide generated by the laser is immersed in the cleaning composition for about 1 hour to remove impurities. Through this, for example, the oxide film as shown in FIG. 2 can be removed from the metal surface of the Invar material on which the black oxide film is formed as shown in FIG. 1 .
상기 금속 마스크(Mask)는 철, 아연 등이 포함된 얇은 막 구조, 구체적으로는 0.1T 내지 0.5T, 바람직하게는 0.1T 내지 0.3T, 더욱 바람직하게는 0.2T의 두께로 이루어진 막 구조이다. 상기 금속 마스크 표면은 은색을 나타내나, 산화될 경우에는 검정색으로 변화하여, 본 발명의 세정제 조성물로 세정시 다시 은색을 나타낸다. The metal mask has a thin film structure containing iron, zinc, etc., specifically, a film structure having a thickness of 0.1T to 0.5T, preferably 0.1T to 0.3T, and more preferably 0.2T. The surface of the metal mask is silver, but when it is oxidized, it changes to black, and shows silver again when cleaned with the cleaning composition of the present invention.
금속 마스크는 철, 아연 등을 포함하는 인바(Invar) 재질일 수 있으나, 이에 제한되는 것은 아니며, 철, 아연 등의 금속 성분을 포함하는 금속 재질 마스크를 세정해낼 수 있다.The metal mask may be made of an Invar material including iron, zinc, etc., but is not limited thereto, and the metal mask including a metal component such as iron or zinc may be cleaned.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하나, 본 발명이 하기 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through Examples, but the present invention is not limited by the Examples.
[실시예 1 내지 5, 비교예 1 내지 4] 세정액 조성물. [Examples 1 to 5, Comparative Examples 1 to 4] Cleaning liquid composition.
하기 표 1에 기재된 조성물의 함량으로 혼합하여, 세정액 조성물을 제조하였다. 하기 표 1에 기재된 함량의 단위는 중량%이다. A cleaning solution composition was prepared by mixing the contents of the compositions shown in Table 1 below. The unit of the content shown in Table 1 below is weight %.
(K2S2O8)Potassium peroxide disulfate
(K 2 S 2 O 8 )
((NH4)2S2O8)Ammonium Persulfate
((NH 4 ) 2 S 2 O 8 )
(CH3N5)aminotetrazole
(CH 3 N 5 )
(C6H5N3)benzotriazole
(C 6 H 5 N 3 )
[실험예] 세정액 조성물의 특성 비교. [Experimental Example] Comparison of properties of cleaning liquid compositions.
상기 제조한 실시예 1 내지 6 및 비교예 1 내지 7의 세정액 조성물을 사용하여, 산화된 인바(Invar) 재질의 마스크에서 금속막의 제거시간을 측정하였으며, 금속막의 직경 크기(size) 및 단면을 샘플링 후, 전자주사현미경(FE-SEM 분석기)로 측단면의 관찰을 통해 직경 크기(Hole size) 및 표면 변화를 측정하여 선택적인 산화막 제거를 확인할 수 있었으며, 상기 세정액 조성물의 특성을 비교한 결과를 하기 표 2에 기재하였다. Using the cleaning solution compositions of Examples 1 to 6 and Comparative Examples 1 to 7 prepared above, the removal time of the metal film from the mask made of oxidized Invar material was measured, and the diameter size and cross section of the metal film were sampled. After that, it was possible to confirm the selective oxide film removal by measuring the diameter size (hole size) and surface change through observation of the side cross-section with a scanning electron microscope (FE-SEM analyzer), and the results of comparing the properties of the cleaning solution composition are as follows: Table 2 shows.
◎: 매우 우수(hole 직경 ≤1.0㎛) / 세정력(≤2hr)/ 산화막 제거(color_White), ○: 우수(hole 직경 1.1 ~ ≤1.5 ㎛) / 세정력(≤3hr)/ 산화막 제거(color_White), △: 불량(hole 직경 ≥2.5㎛) / 세정력(≥6hr)/ 산화막 제거(color_Black)◎: Very good (hole diameter ≤1.0㎛) / cleaning power (≤2hr) / oxide film removal (color_White), ○: excellent (hole diameter 1.1 ~ ≤1.5㎛) / cleaning power (≤3hr) / oxide film removal (color_White), △ : Poor (hole diameter ≥2.5㎛) / cleaning power (≥6hr) / oxide film removal (color_Black)
상기 표 2에 따르면, 홀 사이즈 변화로부터 인바 재질의 금속 마스크에 큰 데미지를 발생시키지 않음을 알 수 있으며 이와 함께 세정력, 산화막 제거능 또한 우수한 것을 알 수 있다. According to Table 2, it can be seen that no significant damage is caused to the metal mask made of the Invar material from the change in the hole size, and it can be seen that the cleaning power and the oxide film removal ability are also excellent.
반면, 비교예 1 및 2의 경우, 금속 마스크에 데미지는 크지 않은 반면, 세정력, 산화막 제거능이 부족한 단점이 확인되었으며, 비교예 3 내지 7의 경우, 황산계 산화제 또는 아졸계 화합물의 함량에 따라, 데미지 발생 또는 세정력 부족 등의 단점이 확인되었다. On the other hand, in the case of Comparative Examples 1 and 2, the damage to the metal mask was not large, but the disadvantage was confirmed that the cleaning power and the ability to remove the oxide film were insufficient. Disadvantages such as damage generation or lack of cleaning power were confirmed.
따라서, 상기 표 2의 분석결과로부터 본 발명의 세정제가 금속 마스크에 대한 데미지를 최소화하며, 산화막을 효과적으로 제거할 수 있는 효과가 있음을 확인할 수 있다.Therefore, it can be confirmed from the analysis results of Table 2 that the cleaning agent of the present invention has an effect of minimizing damage to the metal mask and effectively removing the oxide film.
Claims (8)
아졸계 화합물 0.1 내지 5 중량%; 및
나머지 함량의 초순수를 포함하는 산화막 제거용 세정제 조성물.0.1 to 5 wt% of a sulfuric acid-based oxidizing agent;
0.1 to 5 wt% of an azole compound; and
A cleaning composition for removing an oxide film comprising the remaining content of ultrapure water.
상기 패턴이 새겨진 금속 마스크 표면에 황산계 산화제 0.1 내지 5 중량%, 아졸계 화합물 0.1 내지 5 중량% 및 나머지 함량의 초순수를 포함하는 산화막 제거용 세정제 조성물을 도포하여 세정하는 단계를 포함하는 마스크 세정 방법.engraving a pattern with a laser on a metal mask surface including iron and zinc; and
A method for cleaning a mask comprising the step of applying and cleaning a cleaning composition for removing an oxide film comprising 0.1 to 5 wt% of a sulfuric acid-based oxidizing agent, 0.1 to 5 wt% of an azole-based compound, and the remaining content of ultrapure water on the surface of the metal mask on which the pattern is engraved .
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