WO2012075686A1 - 一种厚膜光刻胶清洗液 - Google Patents
一种厚膜光刻胶清洗液 Download PDFInfo
- Publication number
- WO2012075686A1 WO2012075686A1 PCT/CN2011/002055 CN2011002055W WO2012075686A1 WO 2012075686 A1 WO2012075686 A1 WO 2012075686A1 CN 2011002055 W CN2011002055 W CN 2011002055W WO 2012075686 A1 WO2012075686 A1 WO 2012075686A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- cleaning solution
- solution according
- corrosion inhibitor
- group
- Prior art date
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 33
- 238000004140 cleaning Methods 0.000 claims abstract description 48
- 238000005260 corrosion Methods 0.000 claims abstract description 42
- 230000007797 corrosion Effects 0.000 claims abstract description 42
- -1 alcohol amine Chemical class 0.000 claims abstract description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000003112 inhibitor Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 23
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 20
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 16
- 229920002125 Sokalan® Polymers 0.000 claims description 14
- 239000004584 polyacrylic acid Substances 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000005711 Benzoic acid Substances 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- 235000010233 benzoic acid Nutrition 0.000 claims description 10
- 150000003462 sulfoxides Chemical class 0.000 claims description 10
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 9
- 239000012964 benzotriazole Substances 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 6
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 6
- 229960001553 phloroglucinol Drugs 0.000 claims description 6
- 150000003457 sulfones Chemical class 0.000 claims description 6
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 108010064470 polyaspartate Proteins 0.000 claims description 5
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 claims description 4
- ILUJQPXNXACGAN-UHFFFAOYSA-N O-methylsalicylic acid Chemical compound COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 claims description 4
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical group CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims description 3
- 235000010235 potassium benzoate Nutrition 0.000 claims description 3
- 239000004300 potassium benzoate Substances 0.000 claims description 3
- 229940103091 potassium benzoate Drugs 0.000 claims description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 3
- 235000010234 sodium benzoate Nutrition 0.000 claims description 3
- 239000004299 sodium benzoate Substances 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 claims description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-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
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- BPHYZRNTQNPLFI-UHFFFAOYSA-N 2,4,6-trihydroxytoluene Chemical compound CC1=C(O)C=C(O)C=C1O BPHYZRNTQNPLFI-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
- JLNDHRCFOWTTQO-UHFFFAOYSA-N 2-butylbenzene-1,3,5-triol Chemical compound CCCCC1=C(O)C=C(O)C=C1O JLNDHRCFOWTTQO-UHFFFAOYSA-N 0.000 claims description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-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
- LPELBDSLUUVSGT-UHFFFAOYSA-N 4-tert-butyl-2h-benzotriazole Chemical compound CC(C)(C)C1=CC=CC2=C1N=NN2 LPELBDSLUUVSGT-UHFFFAOYSA-N 0.000 claims description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- HDVRLUFGYQYLFJ-UHFFFAOYSA-N flamenol Chemical compound COC1=CC(O)=CC(O)=C1 HDVRLUFGYQYLFJ-UHFFFAOYSA-N 0.000 claims description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 2
- BVNTWNJMEAAYBL-UHFFFAOYSA-M potassium;3-methoxybenzoate Chemical compound [K+].COC1=CC=CC(C([O-])=O)=C1 BVNTWNJMEAAYBL-UHFFFAOYSA-M 0.000 claims description 2
- AETSDHMVQHOYPB-UHFFFAOYSA-M sodium;4-methoxybenzoate Chemical compound [Na+].COC1=CC=C(C([O-])=O)C=C1 AETSDHMVQHOYPB-UHFFFAOYSA-M 0.000 claims description 2
- GNCGTEQGBYYYBX-UHFFFAOYSA-M sodium;4-methylbenzoate Chemical compound [Na+].CC1=CC=C(C([O-])=O)C=C1 GNCGTEQGBYYYBX-UHFFFAOYSA-M 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
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- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims 1
- XRHRHTXIPOVCTD-UHFFFAOYSA-N [K].COC(=O)C1=CC=CC=C1 Chemical compound [K].COC(=O)C1=CC=CC=C1 XRHRHTXIPOVCTD-UHFFFAOYSA-N 0.000 claims 1
- 229940027987 antiseptic and disinfectant phenol and derivative Drugs 0.000 claims 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
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- 239000010949 copper Substances 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
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- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- RKHQZMOCQHXUBC-UHFFFAOYSA-N phenol;potassium Chemical compound [K].OC1=CC=CC=C1 RKHQZMOCQHXUBC-UHFFFAOYSA-N 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- JAVYIZSIGHZDOT-UHFFFAOYSA-M potassium;3-methylbenzoate Chemical compound [K+].CC1=CC=CC(C([O-])=O)=C1 JAVYIZSIGHZDOT-UHFFFAOYSA-M 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- 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
- C11D7/06—Hydroxides
-
- 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
- C11D7/3218—Alkanolamines or alkanolimines
-
- 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
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
- C23G5/036—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds having also nitrogen
-
- 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
Definitions
- This invention relates to a photoresist cleaning agent, and more particularly to a relatively thick (greater than 100 micron thick) photoresist cleaning agent.
- a mask of a photoresist is formed on a surface of a metal such as silicon dioxide, Cu (copper), or a low-k material, and the pattern is transferred after exposure to obtain a desired circuit pattern.
- the remaining photoresist needs to be stripped off before the next process.
- a photoresist is required to form a mask, which needs to be removed after the microsphere is successfully implanted, but since the photoresist is thick, it is completely removed. More difficult.
- a more common method for improving the removal is to extend the soaking time, increase the soaking temperature, and use a more aggressive solution, but this often results in corrosion of the ruthenium substrate and corrosion of the microspheres, resulting in a significant reduction in wafer yield. :: ::
- the photoresist cleaning liquid is mainly composed of a polar organic solvent, a strong alkali, and/or water, and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in the cleaning liquid or rinsing the semiconductor wafer with the cleaning liquid.
- the strong bases commonly used are mainly inorganic metal hydroxides (such as potassium hydroxide and the like) and organic hydroxides such as tetramethylammonium hydroxide.
- JP1998239865 consists of an alkaline cleaning solution consisting of tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMSOX 1,3-dimethyl-2-imidazolium (DMI) and water, etc., and the wafer is immersed in the cleaning.
- TMAH tetramethylammonium hydroxide
- water etc.
- the thick film photoresist of 20 ⁇ or more on the metal and dielectric substrate is removed at 50 ⁇ 100 ° C.
- the corrosion of the semiconductor wafer substrate is slightly higher, and the photoresist on the semiconductor wafer cannot be completely removed.
- WO2006/056298A1 utilizes alkaline cleaning solution consisting of tetramethylammonium hydroxide (TMAH), dimethyl sulfoxide (DMSO), ethylene glycol (EG) and water for cleaning 50 ⁇ 100 microns thick Photoresist, which is substantially non-corrosive to metallic copper;
- CN200610118465.2 reports an alkaline composition containing potassium hydroxide, dimethyl sulfoxide, benzyl alcohol and ethanolamine, which can remove metals and at 45 to 65 ° C Thick film photoresist on a dielectric substrate, but when the operating temperature is further increased, metal corrosion problems occur.
- US5529887 consists of an alkaline cleaning solution consisting of potassium hydroxide (KOH), a mercaptodiol monoalkyl ether, a water-soluble fluoride and water, etc., the wafer is immersed in the cleaning solution, and the metal is removed at 40 to 90 °C. And a thick film photoresist on a dielectric substrate. It has a high corrosion to the semiconductor wafer substrate.
- KOH potassium hydroxide
- a mercaptodiol monoalkyl ether a water-soluble fluoride and water, etc.
- the technical problem to be solved by the invention is to provide a thick film light for the existing thick film photoresist cleaning liquid which has insufficient cleaning ability or strong corrosion to the semi-conducting pattern and the substrate.
- a photoresist cleaning agent that has a strong cleaning ability and is less corrosive to semiconductor wafer patterns and substrates.
- a thick film photoresist cleaning liquid comprising: potassium hydroxide, a solvent, an alcohol amine, and a multi-component compounding corrosion inhibitor system.
- the multi-component complex corrosion inhibitor system contains an organic phenol and a polycarboxylic acid corrosion inhibitor.
- the content of each component is as follows: a, potassium hydroxide 0.1-6wt%;
- the content of the organic phenol is 0.0001-8wt%; and the content of the polycarboxylic acid corrosion inhibitor is 0.000 l-2wt%, respectively.
- the content of the organic phenol is 0.005-2wt%; and the content of the polycarboxylic acid corrosion inhibitor is 0.005-0.6wt%, respectively.
- the solvent described in the present invention may be selected from one or more of sulfoxide, sulfone, pyrrolidone, imidazolium, imidazolidinone, alcohol, ether, amide.
- the sulfoxide is preferably dimethyl sulfoxide
- the sulfone is preferably sulfolane
- the pyrrolidone is preferably N-methylpyrrolidone or N-ethylpyrrolidone.
- the imidazolidinone is 1,3-dimethyl-2-imidazolium: the imidazolidinone is preferably Is 1,3-dimethyl-2-imidazolidinone (DMI); the amide is preferably methylformamide, dimethylacetamide; the alcohol is preferably propylene glycol, diethylene glycol Alcohol, dipropylene glycol; the ether is preferably propylene glycol monomethyl ether, dipropylene glycol monomethyl ether.
- DMI 1,3-dimethyl-2-imidazolium
- the imidazolidinone is preferably Is 1,3-dimethyl-2-imidazolidinone (DMI)
- the amide is preferably methylformamide, dimethylacetamide
- the alcohol is preferably propylene glycol, diethylene glycol Alcohol, dipropylene glycol
- the ether is preferably propylene glycol monomethyl ether, dipropylene glycol monomethyl ether.
- the alcohol amine described in the present invention is one of monoethanolamine, diethanolamine, triethanolamine, n-propanolamine, isopropanolamine, 2-(diethylamino)ethanol, ethyldiethanol oxime and diglycolamine. kind or several.
- the presence of an alcoholamine is beneficial to increase the solubility of potassium hydroxide in the system and to protect the metal microspheres.
- the organic phenol described in the present invention is preferably one or more of phenol and its derivatives, resorcinol and its derivatives, and phloroglucin and its derivatives.
- the phenol and its derivatives are preferred Is phenol, 2-methylphenol, 3-methoxyphenol, 4-tert-butylphenol; the resorcinol and its derivatives are preferably resorcinol, 5-methyl-m-phenylene Diphenol, 5-methoxy-resorcinol, 5-tert-butyl
- Resorcinol; the phloroglucinol and its derivatives are preferably phloroglucinol, methyl phloroglucinol and butyl phloroglucinol.
- the polycarboxylic acid corrosion inhibitor described in the present invention is preferably polyacrylic acid or a copolymer thereof, polymethacrylic acid or a copolymer thereof, polyacrylic acid alcohol amine salt, polymethacrylic acid amine salt, polyoxyethylene Modified polyacrylic acid or a derivative thereof, polyoxyethylene modified polymethacrylic acid or a derivative thereof, polyepoxysuccinic acid, polyaspartic acid, carboxyl group-containing polycaprolactone and/or carboxyl group-containing polypropylene cross More preferred are polyacrylic acid, polymethacrylic acid, polyacrylic acid alcohol amine salt, polymethacrylic acid amine salt, carboxyl group-containing polycaprolactone and/or carboxyl group-containing polylactide.
- the polycarboxylic acid corrosion inhibitor preferably has a molecular weight (Mn) of from 500 to 20,000, more preferably from 1,000 to 10,000.
- Mn molecular weight
- the polycarboxylic acid corrosion inhibitor exhibits a good inhibitory effect on the corrosion of aluminum.
- the multicomponent complex corrosion inhibitor system described in the present invention further contains benzoic acid and derivatives thereof or salts thereof and/or benzotriazole and derivatives thereof.
- the benzoic acid and the derivative thereof or a salt thereof according to the present invention are selected from the group consisting of benzoic acid, potassium benzoate, sodium benzoate, 2-methylbenzoic acid, potassium 3-methylbenzoate, and sodium 4-methylbenzoate.
- the content of the benzoic acid and its derivative or its salt described in the present invention is not more than 3% by weight.
- the benzotriazole and its derivative described in the present invention are selected from the group consisting of benzotriazole, methylbenzotriazole, methoxybenzotriazole, and tert-butylbenzotriazole.
- the content of the benzotriazole and its derivative described in the present invention is not more than 3% by weight.
- the remarkable effect of the present invention is that the low etching thick film photoresist cleaning liquid of the present invention can The photoresist of a thickness of ⁇ or more is cleaned at room temperature to 90 ° C, and the multi-component system formed by containing an organic phenol and a polycarboxylic acid corrosion inhibitor can simultaneously suppress copper, aluminum, tin, lead, and the like. Corrosion of metals such as silver reduces corrosion of the substrate. Benzoic acid and its derivatives or salts thereof, as well as benzotriazole and its derivatives, can further optimize the multi-component corrosion inhibition system. Summary of the invention
- the specific use method of the cleaning liquid of the present invention is as follows: the semiconductor wafer containing the photoresist is immersed in the low-etching photoresist cleaning agent of the present invention, and immersed at room temperature to 90 ° C for a suitable time, and then taken out and washed. High purity nitrogen is blown dry.
- Hydrogen benzotriazine benzoic acid and its oxidizing solvent alcohol amine, polycarboxylic acid corrosion inhibitor, organic phenol, azole, and bribe, organisms and their salts
- Examples include the name including the name d drought ' name name content a name .
- Alcohol Alcoholamine Phenol
- Alcoholamine lactone (Mn 6500) potassium salt
- the present invention adopts the following technical means: immersing a semiconductor wafer (bump package wafer) containing a negative acrylate-based photoresist (having a thickness of about 120 ⁇ m) in a cleaning agent It was shaken at 25 to 90 ° C for 15 to 120 minutes at a vibration frequency of about 60 rpm using a constant temperature oscillator, and then washed with deionized water and then dried with high purity nitrogen.
- the cleaning effect of the photoresist and the corrosion of the cleaning solution on the wafer are shown in Table 2.
- Example 1 90 120 ⁇ ⁇ ⁇ . ⁇ .
- Example 5 90 105 ⁇ ⁇ . ⁇ ⁇
- Example 22 90 120 ⁇ ⁇ ⁇ O
- Example 30 80 100 ⁇ ⁇ ⁇ ⁇ Example 32 75 45 ⁇ ⁇ ⁇ ⁇ ⁇
- the cleaning liquid of the present invention has a good cleaning effect on a thick film photoresist, and has a wide temperature range, and can effectively suppress corrosion of metals such as copper, aluminum, tin, lead, and silver.
- a multi-component system composed of organic phenol and polycarboxylic acid corrosion inhibitor can effectively inhibit the corrosion of metals such as copper, aluminum, tin-lead, silver, etc.; benzoic acid and its derivatives or their salts and benzene And the triazole and its derivatives can further optimize the corrosion inhibition system of the multi-component compound.
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- Oil, Petroleum & Natural Gas (AREA)
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- Physics & Mathematics (AREA)
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- Cleaning Or Drying Semiconductors (AREA)
Description
一种厚膜光刻胶清洗液
技术领域
本发明涉及一种光刻胶清洗剂, 尤其涉及较厚(厚度大于 100微米) 的 光刻胶清洗剂。 技术背景
在通常的半导体制造工艺中, 通过在二氧化硅、 Cu (铜)等金属以及低 k材料等表面上形成光刻胶的掩膜, 曝光后进行图形转移, 在得到需要的电 路图形之后, 进行下一道工序之前, 需要剥去残留的光刻胶。 例如, 在晶圆 微球植入工艺(bumping technology) 中, 需要光刻胶形成掩膜, 该掩膜在微 球成功植入后同样需要去除, 但由于该光刻胶较厚, 完全去除常较为困难。 改善去除效果较为常用的方法是采用延长浸泡时间、提高浸泡温度和采用更 富有攻击性的溶液, 但这常会造成 Λ片基材的腐蚀和微球的腐蚀, 从而导致 晶片良率的显著降低。:: ::
目前, 光刻胶清洗液主要由极性有机溶剂、强碱和 /或水等组成, 通过将 半导体晶片浸入清洗液中或者利用清洗液冲洗半导体晶片, 去餘半导体晶片 上的光刻胶。 其中其常用的强碱主要是无机金属氢氧化物 (如氢氧化钾等) 和有机氢氧化物如四甲基氢氧化胺等。
如 JP1998239865由四甲基氢氧化铵 (TMAH)、 二甲基亚砜 (DMSOX 1,3-二甲基 -2-咪唑垸酮 (DMI) 和水等组成碱性清洗液, 将晶片浸入该清洗 液中, 于 50~100°C下除去金属和电介质基材上的 20μπ 以上的厚膜光刻胶。 其对半导体晶片基材的腐蚀略高, 且不能完全去除半导体晶片上的光刻胶,
清洗能力不足; WO2006/056298A1利用由四甲基氢氧化铵 (TMAH)、 二甲 基亚砜 (DMSO) , 乙二醇 (EG) 和水组成碱性清洗液, 用于清洗 50〜100 微米厚的光刻胶, 同时对金属铜基本无腐蚀; CN200610118465.2 报道了含 有氢氧化钾、 二甲基亚砜、 苯甲醇和乙醇胺的碱性组合物, 可以在 45〜65°C 下除去金属和电介质基材上的厚膜光刻胶, 但是当操作温度进一步提高时, 会发生金属腐蚀的问题。 又例如 US5529887由氢氧化钾 (KOH)、 垸基二醇 单烷基醚、 水溶性氟化物和水等组成碱性清洗液, 将晶片浸入该清洗液中, 在 40〜90°C下除去金属和电介质基材上的厚膜光刻胶。 其对半导体晶片基材 的腐蚀较高。
由此可见, 寻找更为有效的金属腐蚀抑制剂和清洗能力更强的溶剂体系 是该类光刻胶清洗液努力改进的优先方向。 发明概要
本发明要解决的技术问题就是针对现有的厚膜光刻胶清洗液存在的清 洗能力不足或者对半导 ^晶^图案和基材腐蚀性较强的缺陷,而提供一种对 厚膜光刻胶清洗能力强且对半导体晶片图案和基材腐蚀性较低的光刻胶清 洗剂。
本发明解决上述技术问题所采用的技术方案是: 一种厚膜光刻胶清洗 液, 该清洗液含有: 氢氧化钾、 溶剂、 醇胺以及一种多元复配腐蚀抑制剂体 系。
其中, 所述多元复配腐蚀抑制剂体系含有有机酚和聚羧酸类缓蚀剂。 其中, 各组分的含量如下:
a, 氢氧化钾 0.1-6wt%;
b, 溶剂 30-98wt%;
c, 醇胺 l-55wt%;
d,三元复配体系腐蚀抑制剂 0.01-10wt%。
其中, 所述有机酚含量为 0.0001-8wt%; 所述聚羧酸类缓蚀剂的含量分 别为 0.000 l-2wt%。
其中, 所述有机酚含量为 0.005-2wt%; 所述聚羧酸类缓蚀剂的含量分别 为 0.005- 0.6wt%。
本发明中所述的溶剂可选自亚砜、砜、吡咯垸酮、咪唑垸酮、咪唑啉酮、 醇、 醚、 酰胺中的一种或多种。 其中, 所述的亚砜较佳的为二甲基亚砜; 所 述的砜较佳的为环丁砜; 所述的吡咯垸酮较佳的为 N-甲基吡咯烷酮、 N-乙 基吡咯垸酮、 N-羟乙基吡咯垸酮、 N-环己基吡咯垸酮; 所述的咪唑烷酮较佳 的为 1,3-二甲基 -2-咪唑垸酮: 所述的咪唑啉酮较佳的为 1,3-二甲基 -2-咪唑啉 酮 ( DMI ); 所述的酰胺较佳的为 甲基甲酰胺、 二甲基乙酰胺; 所述的醇 较佳的丙二醇、 二乙二醇、 二丙二醇; 所述的醚较佳的为丙二醇单甲醚、:二 丙二醇单甲醚。
本发明中所述的醇胺为单乙醇胺、 二乙醇胺、 三乙醇胺、 正丙醇胺、 异 丙醇胺、 2- (二乙氨基) 乙醇、 乙基二乙醇餒和二甘醇胺中的一种或几种。 醇胺的存在有利于提高氢氧化钾在体系中的溶解度, 并有利于金属微球的保 护。
本发明中所述的有机酚较佳的为苯酚及其衍生物、间苯二酚及其衍生物 和间苯三酚及其衍生物中的一种或几种。其中所述的苯酚及其衍生物较佳的
为苯酚、 2-甲基苯酚、 3-甲氧基苯酚、 4-叔丁基苯酚; 所述的间苯二酚及其 衍生物较佳的为间苯二酚、 5-甲基 -间苯二酚、 5-甲氧基-间苯二酚、 5-叔丁基
-间苯二酚; 所述的间苯三酚及其衍生物较佳的为间苯三酚、 甲基间苯三酚 和丁基间苯三酚。 本发明中所述的聚羧酸类缓蚀剂较佳的为聚丙烯酸或其共聚物、聚甲基 丙烯酸或其共聚物、 聚丙烯酸醇胺盐、 聚甲基丙烯酸醇胺盐、 聚氧乙烯改性 聚丙烯酸或其衍生物、 聚氧乙烯改性聚甲基丙烯酸或其衍生物、 聚环氧琥珀 酸、聚天冬氨酸、含羧基的聚己内酯和 /或含羧基的聚丙交酯; 更佳的为聚丙 烯酸、 聚甲基丙烯酸、 聚丙烯酸醇胺盐、 聚甲基丙烯酸醇胺盐、 含羧基的聚 己内酯和 /或含羧基的聚丙交酯。 所述的聚羧酸类缓蚀剂的分子量 (Mn) 较 佳的为 500〜20000, 更佳的为 1000~10000。所述的聚羧酸类缓蚀剂对铝的腐 蚀表现出很好的抑制作用。 本发明中所述的多元复配腐蚀抑制剂体系还含有苯甲酸及其衍生物或 其盐类和 /或苯并三氮唑及其衍生物。 本发明中所述的苯甲酸及其衍生物或其盐类为选自苯甲酸、 苯甲酸钾、 苯甲酸钠、 2-甲基苯甲酸、 3-甲基苯甲酸钾、 4-甲基苯甲酸钠、 2-甲氧基苯 甲酸、 3-甲氧基苯甲酸钾和 4-甲氧基苯甲酸钠中的一种或几种。 本发明中所述的苯甲酸及其衍生物或其盐类的含量不超过 3wt%。 : 本发明中所述的苯并三氮唑及其衍生物为选自苯并三氮唑、 甲基苯并三 氮唑、 甲氧基苯并三氮唑、 叔丁基苯并三氮唑、 1-羟基苯并三氮唑和 5-羧基 苯并三氮唑中的一种或多种。
本发明中所述的苯并三氮唑及其衍生物的含量不超过 3wt%。 本发明的显著效果是, 本发明所述的低蚀刻性厚膜光刻胶清洗液, 可以
在室温至 90°C下清洗 ΙΟΟμηι以上厚度的光刻胶, 而且由于其中含有有机酚 和聚羧酸类缓蚀剂等形成的多元复配体系, 能同时有效抑制铜、铝、锡、铅、 银等金属的腐蚀, 从而降低基材的腐蚀。 苯甲酸及其衍生物或其盐类以及苯 并三氮唑及其衍生物, 可以进一步优化该多元复配的腐蚀抑制体系。 发明内容
下面通过具体实施方式来进一步阐述本发明。
本发明清洗液的具体使用方法如下:将含有光刻胶的半导体晶片浸入本 发明中的低蚀刻性的光刻胶清洗剂,在室温至 90°C下浸泡合适的时间后,取 出洗涤后用高纯氮气吹干。
表 1各实施例 (Examples) 中的清洗剂的组分和含量
氢 苯并 _三氮 苯甲酸及其衍 氧 溶剂 醇胺 聚羧酸类缓蚀剂 有机酚 唑及-賄 实 生物和其盐类
化 生 施
钾
例 含 名 名 含 含 名称 d旱' 名称 名称 含量 a 名称 .
称 称 量
3- 甲
N-乙基■■
二乙 聚丙烯酸
1 ■■■0.1. 吡咯烷 · 98 1 0,0001 氧: 0.8999 ■■■ 1 1 ,
'醇胺. · (Mn=500) 、基
: 酮
苯
酚
2- 丙烯酸-马来酸 甲
三乙
2 6 丙二醇 43,95 50 共聚物 0.0499 基 0.0001 / · 1 ' Ί
.醇胺
(Mn=1000) 苯
酚
聚丙烯酸三乙
■二乙二■ 单乙 '苯
3 5 30 55 醇胺盐 2 8 1 1 . 醇 醇胺 酚
(Mn=20000)
4- 叔
甲基丙烯酸-马
二丙二 正丙
4 0.5 48.499 45 来酸共聚物 0.001 丁 6 1 · 1 1
醇 醇胺 基
(Mn=2500 )
苯
酚
间
N-羟乙
异丙 聚甲基丙烯酸 苯
5 1 基吡咯 58.99 40 0.005 0.005 1 1 1
醇胺 (Mn=1500)
烷酮
酚
5- 甲
Ν-环己 乙基 聚甲基丙烯酸 基-
2 基吡咯 66.99 二乙 30 三乙醇胺盐 0.01 间 1 1 1 1 1 烷酮 醇胺 (Μη= 10000) 苯
酚
5- 甲
1,3-二 氧
聚氧乙烯改性
甲基 -2- 单乙 基-
3 71.94 25 聚丙烯酸 0.05 0.01 1 1 1 1 咪唑烷 醇胺 间
(Μη=5000)
酮 苯
酚
5- 叔
1,3-二 2- (二' 丁
聚氧乙烯改性
甲基 -2- 乙氨 基-
2 77.85 20 聚丙烯酸酯 0.1 0.05 1 1 1 1 咪唑啉 基) 间
(Μη=5000)
酮 乙醇 苯
酚
苯 间
聚氧乙烯改性
二甲基 单乙 并
1.5 63 苯 苯甲
35 聚甲基丙烯酸 0.2 0.1 0.1 0.1 甲酰胺 醇胺 酸
(Μη=5000) 氮
酚
唑 甲
聚氧乙烯改性
二甲基 二甘
0.8 间
82.6 苯甲
15 聚甲基丙烯酸 0.6 0.5 0.5 1 1 乙酰胺 醇胺 苯 酸钾
(Μη=5000)
酚 .
: 丁
基
■二甲基 单乙 ' ' 聚环氧琥珀酸'
ί.8 间
85 '苯甲
10 0.2 , 2 . " 1 1 . ■1 亚砜 · •醇胺 · .. (Μη=3000) ; '苯 酸钠 .
酚.
间 ' 2-甲
Ν-甲基■■
单乙 聚天冬氨酸
4 苯 基苯
2.2 吡咯烷 89. 5 0.1 0.3 3 1 1 醇胺 · ( η=4500) 甲 画
酚 酸、
甲 基 间. 3-甲
'单乙■ 苯 基苯, 苯.'
' ·含羧基的聚己
环丁砜: 69.6 26 0.1 0.1 0.2 . 3
氮 唑:'
3 - 甲 4 -甲
聚丙烯酸三乙
丙二醇 正丙
4 50 41 醇胺盐 1 .5 氧 基苯
3 1.5 1 1 单甲醚 醇胺 酸
(Μη=20000 ) 基 甲
苯 钠
叔
酸 苯
L3-- 丁
聚氧乙烯改性
甲基 -2- 并
基-
2 71.25 25 聚丙烯酸酯 0.1 0.05 1 0.6 咪唑啉 间
(Mn=5000) 氮 酮 苯
唑 酚
苯 甲 甲
基 间 酸
聚氧乙烯改性 苯 二甲基 单乙 苯
3 74 20 聚甲基丙烯酸 0.3 0.1 2 并 0.6 甲酰胺 醇胺
(Mn=5000)
酚
氮 唑 甲
基 苯
3-甲
聚氧乙烯改性 并 二甲基 二甘 间
0.8 氧基
79.1 15 聚甲基丙烯酸 0.6 0.5 3 1 乙酰胺 醇胺 苯 苯甲
( n=5000) ί
酸钾
唑 酚 丁 甲 基 基
3-甲
间 苯 二甲基 单乙 聚环氧琥珀酸 基苯
2.3 85 10 0.2 苯 2 0.5
亚砜 000) 并
醇胺 (Mn=3 甲酸
钾
酚 氮
坐 间
.甲基.亚.
单乙 聚天冬氨酸. .苯 苯甲 ' ·
2.6 90 5 0.1 0.3 ■2 ■■■/ /■
'砜 :醇胺 (Mn=4500) '酸
酚
.伺 '
甲¾亚
单乙 含¾基的聚己 '苯:
1 苯甲
80 18 0.1 0.1 0.8 1 ■ · • 1 砜. 醇胺 内酯(Mn=6500) 酸钾
酚 间
聚甲基丙烯酸
二甲基 单乙 苯
2 81.7 15 三乙醇胺盐 1 0.3 1 : / ·■/■ 1 . 亚砜 · . .醇月安
(Mn^lOOOO)
酚 间
二甲基 ' - 单乙 聚天冬氨酸
2.6 77 20 0.2 苯 0.2 ■ 1 : / / · /■ •亚砜 醇胺- (Mn=4500)
酚
苯 间
聚甲基丙烯酸 并 二甲基 单乙 苯
1.5 82.4 ] 5 三乙醇胺盐 0.3 0.3 1 1 0.5 亚砜 醇胺
( n= 10000) 氮
酚
间
二甲基 苯
36.8 0.05
亚砜
聚甲基丙烯酸
单乙 酚 苯甲
32 2 25 三乙醇胺盐 0.3 0.3 0.5 醇胺 间 酸
N-甲基 (Mn= 10000 )
苯
吡咯垸 35 0.05
酮
酚
为了进一步考察该类清洗液的清洗情况, 本发明采用了如下技术手段: 即将含有负性丙烯酸酯类光刻胶(厚度约为 120微米) 的半导体晶片 (凸点 封装晶圆) 浸入清洗剂中, 在 25~90°C下利用恒温振荡器以约 60转 /分的振 动频率振荡 15〜120分钟, 然后经去离子水洗漆后用高纯氮气吹干。 光刻胶 的清洗效果和清洗液对晶片的腐蚀情况如表 2所示。
表 2实施例对晶圆清洗情况
清 光刻胶
洗 清洗时 晶片清洗结果
实施例 、〉曰 间 A1基材
(min) Cu基材腐
度 光刻胶清 金属微球
腐蚀情
CC) . 蚀情况 . 洗结果 . 腐蚀情况
况 氮基三苯并 ¾甲 实施例 1 90 120 © ◎ 〇 .◎ . 实施例 5 ' 90 105 ◎ ◎ .◎ ■
.实施例 6 85 90 ◎ © . © ◎
实施例 7 80 45 ◎ ◎ ◎ ◎
实施例 8 75 60 ◎ ◎ ◎ ◎
实施例 9 70 90 ◎ ©
实施例 10 65 30 ◎ ◎ 〇 ◎
实施例 12 60 75 ◎ ◎ ◎ ◎
实施例 15 55 90 ◎ ◎ ◎ ◎
实施例 16 . 50 45 ◎ ◎ ◎
实施例 18 45 15 ◎ . ◎ 〇 ◎
实施例 18 . 40 110 ◎ - ◎ ◎
实施例 19 35 120 ◎ ◎ ◎ ◎
实施例 20 25 120 ◎ ◎ ◎ ◎
实施例 22 90 120 ◎ ◎ ◎ O
实施例 23 70 60 ◎ ◎ ◎ ◎
实施例 26 90 120 ◎ ◎ ◎ ◎
实施例 27 85 60 ◎ ◎ ◎ ◎
实施例 30 80 100 © ◎ ◎ ◎
实施例 32 75 45 ◎ ◎ ◎ ◎
从表 2可以看出, 本发明的清洗液对厚膜光刻胶具有良好的清洗效果, 使用温度范围广, 能同时有效抑制铜、 铝、 锡、 铅、 银等金属的腐蚀。
综上, 本发明相对现有技术的创新之处是:
1 ) 采用了醇胺作为溶剂溶解氢氧化钾, 并作为金属微球 (bump) 的 保护剂;
2) 采用了有机酚、 聚羧酸类缓蚀剂形成的多元复配体系, 能同时有 效抑制铜、 铝、 锡 铅、 银等金属的腐蚀; 苯甲酸及其衍生物或其盐类以及 苯并三氮唑及其衍生物, 可以进一步优化该多元复配的腐蚀抑制体系。
Claims
1、 一种厚膜光刻胶清洗液, 该清洗液含有: 氢氧化钾、 溶剂、 醇胺以 及一种多元复配腐蚀抑制剂体系。
2、 如权利要求 1所述清洗液, 其特征在于, 所述多元复配腐蚀抑制剂 体系含有有机酚和聚羧酸类缓蚀剂。
3、 .如权利要求 1或 2所述清洗液, 其特征在于, 各组分的含量如下: a,氢氧化钾 0.1-6wt%;
b, 溶剂 30-98wt%;
c, 醇胺 l-55wt%;
d, 三元复配体系腐蚀抑制剂 0.01-10wt%。
4、 如权利要求 3 所述清洗液, 其特征在于, 所述有机酚含量为 0.0001- 8wt%; 所述聚羧酸类缓蚀剂的含量分别为 0.0001-2wt%。
5、 如权利要求 4 所述清洗液, 其特征在于, 所述有机酚含量为 0.005-2wt%: 所述聚羧酸类缓蚀剂的含量分别为 0.005-0.6wt。/0。
6、 如权利要求 1所述清洗液, 其特征在于, 所述的溶剂选自亚砜、 砜、 吡咯烷酮、 咪唑烷酮、 咪唑啉酮、 醇、 醚、 酰胺中的一种或多种。 .
7、如权利要求 6所述清洗液, 其特征在于, 所述的亚砜为二甲基亚砜; 所述的砜为环丁砜; 所述的吡咯垸酮为 N-甲基吡咯垸酮、 N-乙基吡咯垸酮、 N-羟乙基吡咯垸酮和 /或 N-环己基吡咯烷酮; 所述的咪唑烷酮为 1,3-二甲基 -2-咪唑烷酮; 所述的咪唑啉酮为 1,3-二甲基 -2-咪唑啉酮; 所述的酰胺为二甲 基甲酰胺和 /或二甲基乙酰胺; 所述的醇为丙二醇、 二乙二醇和 /或二丙二醇; 所述的醚为丙二醇单甲醚和 /或二丙二醇单甲醚; 所述的醇胺为选自单乙醇 胺、 二乙醇胺、 三乙醇胺、 正丙醇胺、 异丙醇胺、 2- (二乙氨基) 乙醇、 乙 基二乙醇胺和二甘醇胺中的一种或几种。
8、 如权利要求 2所述清洗液, 其特征在于, 所述的有机酚为选自苯酚 及其衍生物、 间苯二酚及其衍生物和间苯三酚及其衍生物中的一种或几种。
9、 如权利要求 8所述清洗液, 其特征在于, 所述的苯酚及其衍生物为 选自苯酚、 2-甲基苯酚、 3-甲氧基苯酚和 4-叔丁基苯酚中的一种或多种; 所 述的间苯二酚及其衍生物为选自间苯二酚、 5-甲基 -间苯二酚、 5-甲氧基-间 苯二酚和 5-叔丁基-间苯二酚中的一种或多种; 所述的间苯三酚及其衍生物 为间苯三酚、 甲基间苯三酚和 /或丁基间苯三酚。
10、 如权利要求 2所述清洗液, 其特征在于, 所述的聚羧酸类缓蚀剂为 选自聚丙烯酸或其共聚物、 聚甲基丙烯酸或其共聚物、 聚丙烯酸醇胺盐、 聚 甲基丙烯酸醇胺盐、 聚氧乙烯改性聚丙烯酸或其衍生物、 聚氧乙烯改性聚甲 基丙烯酸或其衍生物、 聚环氧琥珀酸、 聚天冬氨酸、 含羧基的聚己内酯和含 羧基的聚丙交酯中的一种或多种。
1 如权利要求 10所述清洗液, 其特征在于, 所述的聚羧酸类缓蚀剂 为选自聚丙烯酸、 聚甲基丙烯酸、 聚丙烯酸醇胺盐、 聚甲基丙烯酸醇胺盐、 含羧基的聚己内酯和含羧基的聚丙交酯中的一种或多种。
12、 如权利要求 2所述清洗液, 其特征在于,:所述的聚羧酸类缓蚀剂的 分子量为 500〜20000。
13、 如权利要求 12所述清洗液, 其特征在于, 所述的聚羧酸类缓蚀剂 的分子量为 1000〜10000。
14、 如权利要求 2所述清洗液, 其特征在于, 所述多元复配腐蚀抑制剂
J 2 体系还含有苯甲酸及其衍生物或其盐类和 /或苯并三氮唑及其衍生物。
15、 如权利要求 14所述清洗液, 其特征在于, 所述的苯甲酸及其衍生 物或其盐类为选自苯甲酸、 苯甲酸钾、 苯甲酸钠、 2-甲基苯甲酸、 3-甲基苯 甲酸钾、 4-甲基苯甲酸钠、 2-甲氧基苯甲酸、 3-甲氧基苯甲酸钾和 4-甲氧基 苯甲酸钠中的一种或几种。
16、 如权利要求 14所述清洗液, 其特征在于, 所述的苯甲酸及其衍生 物或其盐类的含量不超过 3wt%。
17、 如权利要求 14所述清洗液, 其特征在于, 所述的苯并三氮唑及其 衍生物为选自苯并三氮唑、 甲基苯并三氮唑、 甲氧基苯并三氮唑、 叔丁基苯 并三氮唑、 1-羟基苯并三氮唑和 5-羧基苯并三氮唑中的一种或多种。
18、 如权利要求 14所述清洗液, 其特征在于, 所述的苯并三氮唑及其 衍生物的含量不超过 3wt%。
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CN101364056A (zh) * | 2007-08-10 | 2009-02-11 | 安集微电子(上海)有限公司 | 一种光刻胶清洗剂 |
CN101412948A (zh) * | 2007-10-19 | 2009-04-22 | 安集微电子(上海)有限公司 | 一种等离子刻蚀残留物清洗剂 |
-
2011
- 2011-12-09 WO PCT/CN2011/002055 patent/WO2012075686A1/zh active Application Filing
- 2011-12-09 TW TW100145440A patent/TW201224138A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050119143A1 (en) * | 1999-01-27 | 2005-06-02 | Egbe Matthew I. | Compositions for the removal of organic and inorganic residues |
TW583719B (en) * | 2002-10-11 | 2004-04-11 | Wako Pure Chem Ind Ltd | Agent for cleaning substrate |
JP2006082253A (ja) * | 2004-09-14 | 2006-03-30 | Toyota Motor Corp | 金型洗浄方法 |
CN101364056A (zh) * | 2007-08-10 | 2009-02-11 | 安集微电子(上海)有限公司 | 一种光刻胶清洗剂 |
CN101412948A (zh) * | 2007-10-19 | 2009-04-22 | 安集微电子(上海)有限公司 | 一种等离子刻蚀残留物清洗剂 |
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