WO2010037263A1 - 一种光刻胶清洗剂 - Google Patents
一种光刻胶清洗剂 Download PDFInfo
- Publication number
- WO2010037263A1 WO2010037263A1 PCT/CN2009/001082 CN2009001082W WO2010037263A1 WO 2010037263 A1 WO2010037263 A1 WO 2010037263A1 CN 2009001082 W CN2009001082 W CN 2009001082W WO 2010037263 A1 WO2010037263 A1 WO 2010037263A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cleaning agent
- ether
- agent according
- photoresist cleaning
- photoresist
- Prior art date
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- -1 alkyl diol aryl ether Chemical class 0.000 claims abstract description 86
- 230000007797 corrosion Effects 0.000 claims abstract description 60
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- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 14
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 2
- 229920002120 photoresistant polymer Polymers 0.000 claims description 125
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 53
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- 150000003839 salts Chemical class 0.000 claims description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 11
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- 229920000642 polymer Polymers 0.000 claims description 10
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 8
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- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 7
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
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- DODWVZSLOOEOKB-UHFFFAOYSA-N 1-benzothiophene-2-thiol Chemical compound C1=CC=C2SC(S)=CC2=C1 DODWVZSLOOEOKB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- DIGCWYGXBRVXIW-UHFFFAOYSA-O 1-sulfanyl-2H-tetrazol-1-ium Chemical compound S[NH+]1N=NN=C1 DIGCWYGXBRVXIW-UHFFFAOYSA-O 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- WFPZIINOVNWKHW-UHFFFAOYSA-N 2-(2-aminoethylamino)ethanol 2-[bis(2-hydroxyethyl)amino]ethanol Chemical compound N(CCO)(CCO)CCO.NCCNCCO WFPZIINOVNWKHW-UHFFFAOYSA-N 0.000 description 1
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- WRDGHPPVRSKOPK-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-phenoxypropoxy)propoxy]propoxy]propoxy]propoxy]propan-1-ol Chemical compound C1(=CC=CC=C1)OC(C)COC(C)COC(C)COC(C)COC(C)COC(C)CO WRDGHPPVRSKOPK-UHFFFAOYSA-N 0.000 description 1
- CBVDPTYIDMQDEO-UHFFFAOYSA-N 2-decoxyethanol Chemical compound CCCCCCCCCCOCCO CBVDPTYIDMQDEO-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ICMXLULYJOYALF-UHFFFAOYSA-N 2h-benzotriazole;2-(2-hydroxyethylamino)ethanol Chemical compound OCCNCCO.C1=CC=CC2=NNN=C21 ICMXLULYJOYALF-UHFFFAOYSA-N 0.000 description 1
- DLLBXBCKFUPBJE-UHFFFAOYSA-N 4-amino-1h-1,2,4-triazole-5-thione Chemical compound NN1C=NNC1=S DLLBXBCKFUPBJE-UHFFFAOYSA-N 0.000 description 1
- IVNPXOUPZCTJAK-UHFFFAOYSA-N 4-methylmorpholin-4-ium;hydroxide Chemical compound O.CN1CCOCC1 IVNPXOUPZCTJAK-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- YJXSVVOEHLIPEJ-UHFFFAOYSA-N C(CCC)OCC(C)O.N(CCO)(CCO)CCO Chemical compound C(CCC)OCC(C)O.N(CCO)(CCO)CCO YJXSVVOEHLIPEJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical group NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OXYMMMUMVUNYHF-UHFFFAOYSA-N OP(O)=O.CC(O)COC(C)CO Chemical compound OP(O)=O.CC(O)COC(C)CO OXYMMMUMVUNYHF-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WCQHQSDQMWPNLB-UHFFFAOYSA-N benzene;2-(2-hydroxyethoxy)ethanol Chemical compound C1=CC=CC=C1.OCCOCCO WCQHQSDQMWPNLB-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- XTEBISFIAYHLQY-UHFFFAOYSA-N ethene;2-(2-hydroxyethoxy)ethanol Chemical group C=C.OCCOCCO XTEBISFIAYHLQY-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 238000005406 washing 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
-
- 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
- C11D7/5022—Organic solvents containing oxygen
-
- 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
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
- C23G1/18—Organic inhibitors
-
- 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
-
- 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
-
- C11D2111/22—
Definitions
- the present invention relates to a cleaning agent in a semiconductor manufacturing process, and in particular to a photoresist cleaning agent.
- a photoresist coating is first formed on a surface of a metal such as silicon dioxide, Cu (copper), or a low-k material, and exposed and developed using a suitable mask, depending on the photoresist used.
- the photoresist is removed from the exposed or unexposed portions, a photoresist pattern is formed at a desired portion, and then plasma etching or reactive gas etching is performed on the photoresist pattern to perform pattern transfer.
- the low temperature and fast cleaning process is an important direction for the development of semiconductor wafer fabrication processes.
- Negative photoresists with thicknesses above 20 ⁇ are gradually being used in semiconductor wafer fabrication processes.
- most of the photoresist cleaners in the industry have better cleaning ability for positive photoresists, but cannot completely remove the wafers.
- cleaning agents In the chemical cleaning of photoresists on semiconductor wafers, cleaning agents often cause corrosion of the wafer pattern and substrate. Especially in the process of removing photoresist and etching residues by chemical cleaning agents, corrosion of metals (especially active metals such as aluminum and copper) is a common and very serious problem, which often leads to a significant decrease in wafer yield. .
- the photoresist cleaning composition is mainly composed of a strong base, a polar organic solvent and/or water, etc., and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in a cleaning agent or rinsing the semiconductor wafer with a cleaning agent.
- Strong bases such as quaternary ammonium hydroxides and alcohol amines, capable of dissolving lithography produced by photoresist and/or etching Glue residue.
- the cleaning agent has insufficient ability to remove the photoresist residue generated by the photoresist and/or the etching; however, when the content of the strong alkali is too high, the cleaning agent is liable to cause corrosion of the wafer pattern and the substrate.
- a photoresist cleaning agent containing a quaternary ammonium hydroxide has better ability to remove photoresist residues generated by photoresist and/or etching than a photoresist cleaning agent containing an alcohol amine.
- the polar organic solvent is capable of dissolving the photoresist residues generated by the photoresist and/or etching, and improving the cleaning ability of the chemical cleaning agent for organic substances.
- the cleaning agent has insufficient ability to remove the photoresist residue generated by the photoresist and/or the etching; but when the content of the polar organic solvent is too high, the strong alkali content in the cleaning agent Correspondingly, the ability of the cleaning agent to remove photoresist residues from photoresist and/or etching is reduced.
- a photoresist cleaning agent composed of an alkanolamine and an organic polar solvent is proposed in US 4,761,251.
- the semiconductor wafer was immersed in the cleaning agent, and the positive photoresist on the wafer was removed at 95 °C.
- the cleaning agent does not contain water, and its cleaning ability for negative photoresist is insufficient.
- a photoresist cleaning agent composed of an alcohol amine, a water-soluble organic solvent, water, an organic phenol compound, a triazole compound, and a silicone antimony surfactant is proposed in US Pat. No. 6,140,027.
- the semiconductor wafer is immersed in the cleaning agent, and the photoresist on the wafer and the photoresist residue generated by the etching are removed at 20 to 50 °C.
- the cleaning agent uses an organic phenol compound and a triazole compound as corrosion inhibitors for inhibiting metal corrosion.
- Organic phenolic compounds are harmful to the human body and cause environmental pollution.
- the cleaning agent has insufficient cleaning ability for the negative photoresist.
- a photoresist cleaning agent consisting of tetramethylammonium hydroxide, N-methylmorpholine oxide, water and 2-mercaptobenzimidazole is proposed in WO2004059700.
- the semiconductor wafer was immersed in the cleaning agent, and the photoresist on the wafer was removed at 70 °C.
- the cleaning agent uses N-methylmorpholine-N-oxide as an oxidizing agent and 2-mercaptobenzimidazole as a metal corrosion inhibitor.
- the cleaning agent needs to clean the photoresist at a relatively high temperature, and the etching of the semiconductor wafer pattern and the substrate is slightly higher, and the cleaning ability of the photoresist is slightly insufficient.
- a photoresist cleaning agent consisting of quaternary ammonium hydroxide, dimethyl sulfoxide, 1,3,-dimethyl-2-imidazolidinone and water is proposed in U.S. Patent No. 6,040,117.
- the semiconductor wafer is immersed in the cleaning agent, and a photoresist having a thickness of ⁇ or more on the metal (gold, copper, lead or nickel) substrate is removed at 40 to 95 °C.
- the cleaning agent uses 1,3,-dimethyl-2-imidazolidinone as an organic co-solvent, and does not contain a corrosion inhibitor that inhibits corrosion of metals such as more active metals such as aluminum.
- the cleaning agent needs to clean the photoresist at a relatively high temperature, and the etching of the semiconductor wafer pattern and the substrate is slightly higher.
- a photoresist cleaning agent composed of a quaternary ammonium hydroxide, a water-soluble organic solvent, an organic amine, a dihydric alcohol, and water is proposed in JP2001215736.
- the semiconductor wafer was immersed in the cleaning agent, and a photoresist of 20 ⁇ M to 40 ⁇ m thick on the wafer was removed at 20 to 90 °C.
- the cleaning agent uses a glycol as a corrosion inhibitor for inhibiting metal corrosion, but the diol has a weak ability to inhibit metal corrosion and reduces the cleaning ability of the cleaning agent for the photoresist, especially the negative photoresist.
- the cleaning agent has a slightly higher corrosion of the semiconductor wafer pattern and the substrate.
- a photoresist cleaning agent consisting of quaternary ammonium hydroxide, ⁇ -methylpyrrolidone, diethanolamine or triethanolamine, water and methanol or ethanol is proposed in JP2004093678.
- the semiconductor wafer is immersed in the cleaning agent, and the photoresist having a thickness of ⁇ or more on the wafer is removed at 15 to 80 °C.
- the cleaning agent uses methanol or ethanol as a solubilizer for quaternary ammonium hydroxide, but the flash point of methanol or ethanol is too low, and The cleaning ability of the cleaning agent to the photoresist, especially the negative photoresist, is reduced.
- the cleaning agent does not contain a corrosion inhibitor that inhibits corrosion of metals such as more reactive metals such as aluminum and copper.
- the cleaning agent has a slightly higher corrosion of the semiconductor wafer pattern and the substrate.
- the existing industrial photoresist cleaning agents still have the ability to completely remove photoresist and other residues on the wafer, especially after exposure and etching of a negative photoresist having a crosslinked network structure. Defects, as well as corrosion problems with semiconductor wafer patterns and substrates. Summary of invention
- the technical problem to be solved by the present invention is to provide a lithography for the defects of insufficient cleaning power of photoresist (resistance) and other residues in the existing semiconductor manufacturing process and the corrosion of the wafer pattern and the substrate.
- Glue cleaner which removes photoresist (especially thick film negative photoresist) and other etch residues on metals, metal alloys or dielectric substrates faster, while on aluminum and copper
- Non-metallic materials such as metals and silica have extremely weak corrosive properties.
- a photoresist cleaning agent comprising: quaternary ammonium hydroxide, water, mercapto diol aryl ether, dimethyl sulfoxide and polyacrylic acid corrosion inhibition
- the alkyl diol aryl ether in the alkyl diol aryl ether has a carbon number of 3 to 18.
- the quaternary ammonium hydroxide is preferably selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylhydrogen.
- One or more of ammonium oxides more preferably one or more selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide, most preferably tetramethylhydrogen Ammonium oxide.
- the content of the quaternary ammonium hydroxide is preferably from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight.
- the water content is preferably from 0.2 to 5% by weight, more preferably from 0.5 to 3% by weight.
- the photoresist cleaning agent of the invention has a low water content, further reducing the corrosiveness of the cleaning agent to metals such as aluminum and copper, and improving the cleaning ability of the positive and negative photoresists, especially High cross-linking degree of negative photoresist cleaning ability.
- the mercapto glycol aryl ether is preferably selected from the group consisting of propylene glycol monophenyl ether, isopropyl glycol monophenyl ether, diethylene glycol monophenyl ether, dipropylene glycol monophenyl ether, and Isopropylene glycol monophenyl ether, triethylene glycol monophenyl ether, tripropylene glycol monophenyl ether, triisopropyl glycol monophenyl ether, hexadeethylene glycol monophenyl ether, hexapropylene glycol monophenyl ether, six One or more of isopropyl glycol monophenyl ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether or hexanediol mono-naphthyl ether, more preferably selected from propylene glycol monophenyl group One or more of ether, dipropylene glycol group One
- the content of the mercapto glycol aryl ether is preferably from 0.5 to 30% by weight, more preferably from 2.0 to 15.0% by weight.
- the mercapto diol aryl ether can improve the solubility of tetramethylammonium hydroxide in dimethyl sulfoxide, and the environmental damage is lower than that of ethylene glycol decyl ether and ethylene glycol aryl ether. More conducive to environmental protection.
- the content of the dimethyl sulfoxide is preferably from 1 to 98% by weight, more preferably from 30 to 90% by weight.
- the polyacrylic corrosion inhibitor is preferably selected from the group consisting of acrylic polymers and copolymers thereof, methacrylic polymers and copolymers thereof, alcohol amine salts of acrylic polymers, methacrylic acid polymers.
- Alkanolamine salt, polyoxyethylene-modified acrylic polymer and ester and alkanolammonium salt thereof, and polyoxyethylene-modified methacrylic acid polymer and one or more of ester and alcohol hinge salt thereof Preferred are an acrylic acid polymer or a copolymer thereof, an alcohol amine salt of an acrylic polymer, a polyoxyethylene modified acrylic polymer and an alkanolammonium salt thereof, and a polyoxyethylene modified methacrylic acid polymer and One or more of the alcohol hinge salts;
- the polyacrylic acid compound preferably has a number average molecular weight of 500 to 20,000, More preferably, it is 1000 ⁇ 10000.
- the content of the polyacrylic compound is preferably from 0.01 to 5.0% by weight, more preferably from 0.05 to 2.5% by weight.
- the polyacrylic corrosion inhibitor exhibits a good inhibitory effect on the corrosion of aluminum.
- the polyacrylic acid corrosion inhibitor and the mercapto glycol aryl ether contained in the photoresist cleaning agent of the present invention can form a protective film on the wafer pattern and the surface of the substrate to prevent the halogen atom, the hydroxide ion and the like from being opposite to the wafer. Attack of graphics and substrates, thereby reducing corrosion of the wafer pattern and substrate.
- the polyacrylic corrosion inhibitors therein exhibit a good inhibitory effect on the corrosion of metals, especially aluminum.
- the photoresist cleaning agent may further contain one or more selected from the group consisting of polar organic co-solvents, surfactants, and other corrosion inhibitors other than polyacrylic corrosion inhibitors.
- the polar organic co-solvent content is preferably 50%, more preferably 5 to 30%; and the surfactant content is preferably 5%, more preferably 0.05 to 3.0%;
- the content of the corrosion inhibitor other than the polyacrylic corrosion inhibitor is preferably 5.0%, more preferably 0.10 to 3.0%; the above percentage is a mass percentage, excluding 0%.
- the polar organic co-solvent is preferably one or more selected from the group consisting of sulfoxide, sulfone, imidazolium, alcohol amine and mercaptodiol monodecyl ether.
- the sulfoxide is preferably one or more selected from the group consisting of diethyl sulfoxide or methyl sulfoxide; and the sulfone is preferably selected from the group consisting of methyl sulfone, ethyl sulfone and sulfolane.
- the imidazolidinone is preferably selected from the group consisting of 2-imidazolium, 1,3-dimethyl-2-imidazolidinone and 1,3- One or more of diethyl-2-imidazolium, more preferably 1,3-dimethyl-2-imidazolium;
- the alcohol amine is preferably selected from the group consisting of monoethanolamine, three One or more of ethanolamine, diglycolamine, isopropanolamine, methyldiethanolamine, methylethanolamine, dimethylethanolamine and hydroxyethylethylenediamine, more preferably selected from the group consisting of monoethanolamine, three One or more of ethanolamine, diglycolamine, and methyldiethanolamine;
- Preferred is selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol
- the surfactant is a surfactant commonly used in the art, preferably one or more selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and polyoxyethylene ether, more preferably It is one or more selected from the group consisting of polyvinylpyrrolidone and polyoxyethylene ether.
- the number average molecular weight of the surfactant is preferably from 500 to 20,000, more preferably from 1,000 to 10,000.
- the corrosion inhibitor other than the polyacrylic corrosion inhibitor is preferably one or more selected from the group consisting of alcohol amines, azoles, and phosphonic acid corrosion inhibitors.
- the alcohol amine corrosion inhibitor is preferably selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, isopropanolamine, methyldiethanolamine, methylethanolamine, dimethylethanolamine and hydroxyethylethyl
- the diamines more preferably one or more selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, and methyldiethanolamine
- the azole inhibitor is preferred It is selected from the group consisting of benzotriazole, methylbenzotriazole, benzotriazole diethanolamine salt, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, dimercapto Thiadiazole, 3-amino-1,2,4-triazole, 4-amino-1,2,
- the reagents and starting materials used in the present invention are commercially available.
- the photoresist cleaning agent of the present invention can be obtained by simply mixing the components described above.
- the photoresist cleaning agent of the present invention can be used in a relatively large temperature range (between 20 and 85 ° C), and the photoresist and other etching residues having a thickness of 20 ⁇ m or more can be washed more quickly.
- the cleaning method refer to the following steps: The semiconductor wafer containing the photoresist is immersed in a cleaning agent, slowly shaken at 20 to 85 ° C with a constant temperature oscillator, then washed with deionized water and then dried with high purity nitrogen.
- the photoresist cleaning agent of the present invention can relatively quickly clean a photoresist (especially a thick film negative photoresist) having a thickness of 20 ⁇ m or more on a substrate such as a metal, a metal alloy or a dielectric, and other etching residues. Things.
- the photoresist cleaning agent of the present invention contains a mercapto diol aryl ether and a polyacrylic acid corrosion inhibitor which can form a protective film on the wafer pattern and the surface of the substrate when the photoresist is cleaned, thereby preventing Halogen atoms, hydroxide ions and the like attack the wafer pattern and the substrate, thereby reducing the corrosion of the wafer pattern and the substrate, especially the polyacrylic corrosion inhibitor contained therein exhibits good suppression of corrosion of metals, especially aluminum. effect. Therefore, it has extremely weak corrosive properties to metals such as aluminum and copper and non-metal materials such as silica.
- the photoresist cleaning agent of the present invention has a low water content, further reducing the corrosiveness of the cleaning agent to metals such as aluminum and copper, and improving the cleaning ability of the positive and negative photoresists. In particular, the ability to clean negative photoresists with a high degree of crosslinking.
- the photoresist cleaning agent of the present invention is environmentally friendly and can be used over a wide temperature range (20 to 85 ° C). (5) Based on the above advantages, the photoresist cleaning agent of the present invention has a good application prospect in the field of microelectronics such as semiconductor wafer cleaning. Summary of the invention
- Table 1 shows the formulations of the photoresist cleaning agents of Examples 1 to 26 of the present invention, which were simply mixed uniformly according to the components and their contents listed in Table 1, to prepare each cleaning agent.
- Table 1 Embodiments of the photoresist of the present invention 1 ⁇ 26
- the average molecular weight is 5 10000
- Phenyl ether polyvinyl alcohol (number of hinges is 5000) 0.05
- the amount is 5000
- Oxazolidinone molecular weight is 3000
- Ammonium oxide (number average molecular weight is hydroxyethylethylenediamine 8
- Ether benzotriazole three hinge amount is 1000) 0.42
- Ethanolamine salt Tetramethyl isopropyl glycol monobenzene Polymethic acid Triethylenetriethanolamine 1 Hydroxide 1 .5 2 5 88.5 Alkanolamine salt (number average molecule 1. 5
- the ether 1 -phenyl -5-fluorenyl hinge amount is 10000) 0.5
- Polyvinyl alcohol (number average hydrogen peroxide 2 3 8 85 enoic acid (number average molecular weight 0.05 0.05)
- the molecular weight of the ether is 500).
- the hinge is 5000)
- Polyvinylpyrrolidone (number average molecular weight 0.05 is 20000) Polyoxyethylene modified polypropyl methyldiethanolamine 5 Propylene glycol monophenyl
- Ether 2-mercaptobenzothiazide ammonium oxide amount is 5000) 1.5
- the average molecular weight of the ether is 2500) 2-mercaptobenzopyrene hinge 2.2
- Ether salt (number average molecular weight is 2-amino-5-mercapto ammonium 0.5
- the amount of oxidized hinge is 10000) aminotrimethylene
- Methyl hydrogen 3 3 10 52.5 Alkanolamine salt (number average molecule 1. 5
- Ether hexapropylene glycol single oxidation hinge amount is 10000) 5
- Table 2 shows the comparison of the photoresist cleaning agent ⁇ 7' and the photoresist cleaning agent 1 ⁇ 16 of the present invention, according to the components listed in Table 2 and their contents, simply mixed uniformly, that is, each obtained detergent.
- the comparative cleaning agent ⁇ 6' and the cleaning agents 1 ⁇ 16 of the present invention are clear and transparent except that a small amount of tetramethylammonium hydroxide in the comparative cleaning agent 7' cannot be dissolved. A homogeneous solution.
- the comparative cleaning agent ⁇ 6' and the cleaning agents 1 to 16 of the present invention were used to clean the blank Cu wafer, and the corrosion of the metal Cu was measured.
- Test methods and conditions A 4 X 4 cm blank Cu wafer was immersed in a cleaning agent, and shaken at a vibration frequency of about 60 rpm for 60 minutes at 20 to 85 ° C using a constant temperature oscillator, and then washed with deionized water and then used for high purity. The nitrogen was blown dry, and the change in surface resistance of the blank Cu wafer before and after etching was measured by a quadrupole probe. The results are shown in Table 3.
- the comparative cleaning agent ⁇ 6' and the cleaning agent 1 ⁇ 16 of the present invention were used to clean the blank A1 wafer, and the corrosion of the metal A1 was measured.
- Test methods and conditions The 4 X 4 cm blank A1 wafer was immersed in a cleaning agent, oscillated at a vibration frequency of about 60 rpm for 60 minutes at 20 to 85 ° C using a constant temperature oscillator, and then washed with deionized water and then used for high purity. The nitrogen was blown dry, and the change in surface resistance of the blank A1 wafer before and after etching was measured by a quadrupole prober. The results are shown in Table 3.
- the comparative cleaning agent ⁇ 6' and the cleaning agents 1 ⁇ 16 of the present invention were used to clean the blank tetraethoxysilane (TEOS) wafer, and the corrosion of the non-metallic TEOS was measured.
- Test Methods and Conditions A 4 X 4 cm blank TEOS wafer was immersed in a cleaning agent, oscillated at a vibration frequency of about 60 rpm for 60 minutes at 20 to 85 ° C using a constant temperature oscillator, and then washed with deionized water and then used for high purity. Blow dry with nitrogen. The thickness of the TEOS thickness before and after cleaning of the blank TEOS wafer was measured using a Nanospec 6100 thickness gauge. The results are shown in Table 3.
- a method of cleaning a photoresist on a semiconductor wafer by using a photoresist cleaning agent is as follows: a semiconductor wafer containing a negative acrylate-based photoresist (having a thickness of about 60 ⁇ m and exposed and etched) Pattern) immersed in the cleaning agent, using a constant temperature oscillator at 20 to 85 ° C for about 60 The vibration frequency of the revolution/minute was oscillated for 1 to 30 minutes, then washed with deionized water and then dried with high purity nitrogen.
- Corrosion ⁇ Basically non-corrosive; Cleaning condition: ⁇ Completely removed;
- the cleaning agents of Examples 1 to 16 have good cleaning ability for the negative acrylate-based photoresist, and the use temperature range is wide, and at the same time
- the metal Cu and A1 and the non-metal TEOS have low corrosivity and no damage to the wafer pattern.
Description
一种光刻胶清洗剂 技术领域
本发明涉及半导体制造工艺中一种清洗剂, 具体地涉及一种光刻胶清洗 剂。 技术背景
在通常的半导体制造工艺中, 首先在二氧化硅、 Cu (铜)等金属以及低 k材料等表面上形成光刻胶的涂层, 利用适当的掩模进行曝光、 显影, 根据 所用光刻胶的特性, 除去曝光或者未曝光部分的光刻胶, 在所要求的部位形 成光刻胶图案, 然后在该光刻胶图案上进行等离子刻蚀或反应性气体刻蚀, 进行图形转移。 低温快速的清洗工艺是半导体晶片制造工艺发展的重要方 向。 20μηι 以上厚度的负性光刻胶正逐渐应用于半导体晶片制造工艺中, 而 目前工业上大部分的光刻胶清洗剂对正性光刻胶的清洗能力较好,但不能彻 底去除晶片上经曝光和刻蚀后的具有交联网状结构的负性光刻胶。
在半导体晶片进行光刻胶的化学清洗过程中,清洗剂常会造成晶片图案 和基材的腐蚀。 特别是在利用化学清洗剂除去光刻胶和刻蚀残余物的过程 中, 金属 (尤其是铝和铜等较活泼金属)腐蚀是较为普遍而且非常严重的问 题, 往往导致晶片良率的显著降低。
目前, 光刻胶清洗剂组合物主要由强碱、 极性有机溶剂和 /或水等组成, 通过将半导体晶片浸入清洗剂中或者利用清洗剂冲洗半导体晶片,去除半导 体晶片上的光刻胶。
强碱如季铵氢氧化物和醇胺等,能够溶解光刻胶和 /或刻蚀所产生的光刻
胶残余物。强碱含量过低时,清洗剂对光刻胶和 /或刻蚀所产生的光刻胶残余 物的去除能力不足; 但强碱含量过高时, 清洗剂易造成晶片图案和基材的腐 蚀。 与含有醇胺的光刻胶清洗剂相比, 含有季铵氢氧化物的光刻胶清洗剂对 光刻胶和 /或刻蚀所产生的光刻胶残余物的去除能力较好。
极性有机溶剂能够溶解光刻胶和 /或刻蚀所产生的光刻胶残余物,提高化 学清洗剂对有机物的清洗能力。 极性有机溶剂含量过低时, 清洗剂对光刻胶 和 /或刻蚀所产生的光刻胶残余物的去除能力不足;但极性有机溶剂含量过高 时,清洗剂中的强碱含量相应降低,使得清洗剂对光刻胶和 /或刻蚀所产生的 光刻胶残余物的去除能力减弱。
为了提高清洗剂对光刻胶和 /或刻蚀所产生的光刻胶残余物的水解和 /或 溶解能力, 化学清洗剂中的水有时是必需的。 但水含量过高时, 清洗剂对光 刻胶和 /或刻蚀所产生的光刻胶残余物的去除能力不足,且易造成晶片图案和 基材的腐蚀。
US4617251中提出了由醇胺和有机极性溶剂组成的光刻胶清洗剂。将半 导体晶片浸入该清洗剂中,在 95°C下除去晶片上的正性光刻胶。但该清洗剂 中不含有水, 且其对负性光刻胶的清洗能力不足。
US6140027中提出了由醇胺、 水溶性有机溶剂、 水、 有机酚化合物、 三 唑化合物和聚硅氧垸表面活性剂组成的光刻胶清洗剂。将半导体晶片浸入该 清洗剂中,在 20〜50°C下除去晶片上的光刻胶和刻蚀所产生的光刻胶残余物。 该清洗剂采用有机酚化合物和三唑化合物作为抑制金属腐蚀的缓蚀剂。有机 酚化合物对人体有害, 而且会对环境造成污染。该清洗剂对负性光刻胶的清 洗能力不足。
WO2004059700中提出了由四甲基氢氧化铵、 N-甲基吗啡啉 氧化物、 水和 2-巯基苯并咪唑组成的光刻胶清洗剂。 将半导体晶片浸入该清洗剂中, 在 70°C下除去晶片上的光刻胶。该清洗剂采用 N-甲基吗啡啉 -N-氧化物作为 氧化剂, 采用 2-巯基苯并咪唑作为金属腐蚀抑制剂。该清洗剂需在较高温度 下清洗光刻胶, 对半导体晶片图案和基材的腐蚀略高, 且对光刻胶的清洗能 力略显不足。
US6040117中提出了由季铵氢氧化物、二甲基亚砜、 1,3,-二甲基 -2-咪唑 烷酮和水组成的光刻胶清洗剂。 将半导体晶片浸入该清洗剂中, 在 40〜95°C 下除去金属 (金、 铜、 铅或镍) 基材上的 ΙΟμηι以上厚度的光刻胶。 该清洗 剂采用 1,3,-二甲基 -2-咪唑烷酮作为有机共溶剂, 而且不含有抑制金属 (尤 其是铝等较活泼金属)腐蚀的缓蚀剂。该清洗剂需在较高温度下清洗光刻胶, 对半导体晶片图案和基材的腐蚀略高。
JP2001215736中提出了由季铵氢氧化物、 水溶性有机溶剂、有机胺、二 元醇和水组成的光刻胶清洗剂。 将半导体晶片浸入该清洗剂中, 在 20〜90°C 下除去晶片上的 20μΐΏ~40μηι厚度的光刻胶。 该清洗剂采用二元醇作为抑制 金属腐蚀的缓蚀剂, 但二元醇对金属腐蚀的抑制能力很弱, 而且会降低清洗 剂对光刻胶尤其是负性光刻胶的清洗能力。该清洗剂对半导体晶片图案和基 材的腐蚀略高。
JP2004093678中提出了由季铵氢氧化物、 Ν-甲基吡咯垸酮、二乙醇胺或 三乙醇胺、 水和甲醇或乙醇组成的光刻胶清洗剂。 将半导体晶片浸入该清洗 剂中, 在 15〜80°C下除去晶片上的 ΙΟμπι以上厚度的光刻胶。 该清洗剂采用 甲醇或乙醇作为季铵氢氧化物的增溶剂, 但甲醇或乙醇的闪点过低, 而且会
降低清洗剂对光刻胶尤其是负性光刻胶的清洗能力。该清洗剂不含有抑制金 属 (尤其是铝和铜等较活泼金属)腐蚀的缓蚀剂。 该清洗剂对半导体晶片图 案和基材的腐蚀略高。
综上所述,现有的工业光刻胶清洗剂还存在不能彻底去除晶片上光刻胶 和其它残留物,尤其是经曝光和刻蚀后的具有交联网状结构的负性光刻胶的 缺陷, 以及对半导体晶片图案和基材的腐蚀问题。 发明概要
因此,本发明要解决的技术问题就是针对现有的半导体制造工艺中光刻 胶(光阻)和其它残留物的清洗力不足以及存在晶片图案和基材的腐蚀的缺 陷, 提供一种光刻胶清洗剂, 该光刻胶清洗剂可以较快除去金属、 金属合金 或电介质基材上的光刻胶(尤其是厚膜负性光刻胶)和其它刻蚀残留物, 同 时对铝和铜等金属以及二氧化硅等非金属材料具有极弱的腐蚀性。
本发明解决上述技术问题所采用的技术方案是: 一种光刻胶清洗剂, 含 有: 季铵氢氧化物、水、垸基二醇芳基醚、二甲基亚砜和聚丙烯酸类缓蚀剂; 其中所述的烷基二醇芳基醚中垸基二醇的碳原子数目为 3~18。
本发明中, 所述的季铵氢氧化物较佳的为选自四甲基氢氧化铵、 四乙基 氢氧化铵、 四丙基氢氧化铵、 四丁基氢氧化铵和苄基三甲基氢氧化铵中的一 种或多种, 更佳的为选自四甲基氢氧化铵、 四乙基氢氧化铵和四丁基氢氧化 铵中的一种或多种, 最佳的为四甲基氢氧化铵。所述的季铵氢氧化物的含量 较佳的为 0.1~10wt%, 更佳的为 0.5~5wt%。
本发明中, 所述的水的含量较佳的为 0.2〜5wt%, 更佳的为 0.5〜3wt %。
本发明的光刻胶清洗剂中的水含量较低,进一步降低了清洗剂对铝和铜等金 属的腐蚀性, 而且提高了其对正性和负性光刻胶的清洗能力, 尤其是对高交 联度的负性光刻胶的清洗能力。
本发明中, 所述的垸基二醇芳基醚较佳的为选自丙二醇单苯基醚、 异丙 二醇单苯基醚、 二乙二醇单苯基醚、 二丙二醇单苯基醚、 二异丙二醇单苯基 醚、 三乙二醇单苯基醚、 三丙二醇单苯基醚、 三异丙二醇单苯基醚、 六缩乙 二醇单苯基醚、 六缩丙二醇单苯基醚、 六缩异丙二醇单苯基醚、 丙二醇单苄 基醚、 异丙二醇单苄基醚或己二醇单萘基醚中的一种或多种, 更佳的为选自 更佳的为丙二醇单苯基醚、二丙二醇单苯基醚或丙二醇单苄基醚中的一种或 多种。 所述的垸基二醇芳基醚的含量较佳的为 0.5~30wt%, 更佳的为 2.0~15.0wt%。 所述的垸基二醇芳基醚可以提高四甲基氢氧化铵在二甲基亚 砜中的溶解度, 且对环境的危害低于乙二醇垸基醚和乙二醇芳基醚等, 更利 于环境的保护。
本发明中, 所述的二甲基亚砜的含量较佳的为 l〜98wt% , 更佳的为 30~90wt
本发明中,所述的聚丙烯酸类缓蚀剂较佳的为选自丙烯酸聚合物及其共 聚物、 甲基丙烯酸聚合物及其共聚物, 丙烯酸聚合物的醇胺盐, 甲基丙烯酸 聚合物的醇胺盐, 聚氧乙烯改性的丙烯酸聚合物及其酯和醇铵盐, 以及聚氧 乙烯改性的甲基丙烯酸聚合物及其酯和醇铰盐中的一种或多种,更佳的为选 自丙烯酸聚合物或其共聚物, 丙烯酸聚合物的醇胺盐, 聚氧乙烯改性的丙烯 酸聚合物及其醇铵盐, 以及聚氧乙烯改性的甲基丙烯酸聚合物及其醇铰盐中 的一种或多种;所述的聚丙烯酸类化合物的数均分子量较佳的为 500〜20000,
更佳的为 1000〜10000。 所述的聚丙烯酸类化合物的含量较佳的为 0.01~5.0wt%, 更佳的为 0.05~2.5wt%。 所述的聚丙烯酸类缓蚀剂对铝的腐蚀 表现出很好的抑制作用。本发明的光刻胶清洗剂中含有的聚丙烯酸类缓蚀剂 和垸基二醇芳基醚能够在晶片图形和基材表面形成一层保护膜, 阻止卤素原 子、氢氧根离子等对晶片图形和基材的攻击, 从而降低晶片图案和基材的腐 蚀。尤其是其中的聚丙烯酸类缓蚀剂对金属尤其是铝的腐蚀表现出良好的抑 制作用。
本发明中, 所述的光刻胶清洗剂还可进一步含有选自极性有机共溶剂、 表面活性剂和除聚丙烯酸类缓蚀剂以外的其它缓蚀剂中的一种或多种。所述 的极性有机共溶剂含量较佳的为 50%, 更佳的为 5~30%; 所述的表面活性 剂含量较佳的为 5%, 更佳的为 0.05~3.0%; 所述的除聚丙烯酸类缓蚀剂以 外的其它缓蚀剂含量较佳的为 5.0%, 更佳的为 0.10〜3.0%; 上述百分比为 质量百分比, 不包括 0%。
本发明中, 所述的极性有机共溶剂较佳的为选自亚砜、 砜、 咪唑垸酮、 醇胺和垸基二醇单垸基醚中的一种或多种。 其中, 所述的亚砜较佳的为选自 二乙基亚砜或甲乙基亚砜中的一种或多种; 所述的砜较佳的为选自甲基砜、 乙基砜和环丁砜中的一种或多种, 更佳的为环丁砜; 所述的咪唑烷酮较佳的 为选自 2-咪唑垸酮、 1,3-二甲基 -2-咪唑烷酮和 1,3-二乙基 -2-咪唑垸酮中的一 种或多种, 更佳的为 1,3-二甲基 -2-咪唑垸酮; 所述的醇胺较佳的为选自一乙 醇胺、 三乙醇胺、 二甘醇胺、 异丙醇胺、 甲基二乙醇胺、 甲基乙醇胺、 二甲 基乙醇胺和羟乙基乙二胺中的一种或多种, 更佳的为选自一乙醇胺、 三乙醇 胺、 二甘醇胺和甲基二乙醇胺中的一种或多种; 所述的垸基二醇单烷基醚较
佳的为选自二乙二醇单甲醚、 二乙二醇单乙醚、 二乙二醇单丁醚、 丙二醇单 丁醚、二丙二醇单甲醚、二丙二醇单乙醚和二丙二醇单丁醚中的一种或多种, 更佳的为选自二乙二醇单甲醚和二丙二醇单甲醚中的一种或多种。
本发明中, 所述的表面活性剂为本领域常用的表面活性剂, 较佳的为选 自聚乙烯醇、 聚乙烯吡咯垸酮和聚氧乙烯醚中的一种或多种, 更佳的为选自 聚乙烯吡咯垸酮和聚氧乙烯醚中的一种或多种。所述的表面活性剂的数均分 子量较佳的为 500~20000, 更佳的为 1000~10000。
本发明中,所述的除聚丙烯酸类缓蚀剂以外的其它缓蚀剂较佳的为选自 醇胺、 唑类和膦酸类缓蚀剂中的一种或多种。 其中, 所述的醇胺缓蚀剂较佳 的为选自一乙醇胺、 三乙醇胺、 二甘醇胺、 异丙醇胺、 甲基二乙醇胺、 甲基 乙醇胺、 二甲基乙醇胺和羟乙基乙二胺中的一种或多种, 更佳的为选自一乙 醇胺、 三乙醇胺、 二甘醇胺和甲基二乙醇胺中的一种或多种; 所述的唑类缓 蚀剂较佳的为选自苯并三氮唑、 甲基苯并三氮唑、 苯并三氮唑二乙醇胺盐、 2-巯基苯并咪唑、 2-巯基苯并噻唑、 2-巯基苯并噁唑、 二巯基噻二唑、 3-氨 基 -1,2,4-三氮唑、 4-氨基- 1,2,4-三氮唑、 3-氨基 -5-巯基 -1,2,4-三氮唑、 3,5-二 氨基 -1,2,4-三氮唑、 4-氨基 -5-巯基 -1,2,4-三氮唑、 5-氨基-四氮唑和 1-苯基 -5- 巯基四氮唑中的一种或多种, 更佳的选自苯并三氮唑、 甲基苯并三氮唑、 苯 并三氮唑二乙醇胺盐、 3-氨基 -1,2,4-三氮唑、 4-氨基 -】,2,4-三氮唑、 3-氨基 -5- 巯基 -1,2,4-三氮唑和 5-氨基 -四氮唑中的一种或多种;所述的膦酸类缓蚀剂较 佳的为选自 1-羟基亚乙基 -1,1-二膦酸、氨基三亚甲基膦酸、2-膦酸丁烷 -1,2,4- 三羧酸、 乙二胺四亚甲基膦酸和二乙烯三胺五亚甲基膦酸中的一种或多种, 更佳的为选自 2-膦酸丁烷- 1 ,2,4-三羧酸、 乙二胺四亚甲基膦酸和二乙烯三胺
五亚甲基膦酸中的一种或多种。
本发明所用试剂及原料均市售可得。本发明的光刻胶清洗剂由上面所述 组分简单混合即可制得。
本发明的光刻胶清洗剂可在较大的温度范围内使用(20〜85°C之间), 较 为迅速地清洗 20μπι以上厚度的光刻胶和其它刻蚀残留物。 清洗方法可参照 如下步骤: 将含有光刻胶的半导体晶片浸入清洗剂中, 在 20〜85'C下利用恒 温振荡器缓慢振荡, 然后经去离子水洗涤后用高纯氮气吹干。
相比于现有技术, 本发明的有益效果如下:
( 1 ) 本发明的光刻胶清洗剂可以较为迅速地清洗金属、 金属合金或电 介质等基材上的 20μηι以上厚度的光刻胶 (尤其是厚膜负性光刻胶) 和其它 刻蚀残留物。
(2 ) 本发明的光刻胶清洗剂在清洗光刻胶时, 其含有的垸基二醇芳基 醚和聚丙烯酸类缓蚀剂能够在晶片图形和基材表面形成一层保护膜, 阻止卤 素原子、 氢氧根离子等对晶片图形和基材的攻击, 从而降低晶片图案和基材 的腐蚀, 尤其是其含有的聚丙烯酸类缓蚀剂对金属尤其是铝的腐蚀表现出良 好的抑制作用。所以其对铝和铜等金属以及二氧化硅等非金属材料具有极弱 的腐蚀性。
(3 ) 本发明的光刻胶清洗剂中的含水量较低, 进一步降低了清洗剂对 铝和铜等金属的腐蚀性, 而且提高了其对正性和负性光刻胶的清洗能力, 尤 其是对高交联度的负性光刻胶的清洗能力。
(4) 本发明的光刻胶清洗剂对环境友好, 且其可以在较大的温度范围 内 (20〜85°C ) 使用。
( 5 ) 基于上述优点, 本发明的光刻胶清洗剂在半导体晶片清洗等微电 子领域具有良好的应用前景。 发明内容
下面用实施例来进一步说明本发明, 但本发明并不受其限制。
下述实施例中, 百分比均为质量百分比。
实施例 1〜26
表 1给出了本发明的光刻胶清洗剂实施例 1〜26的配方, 按表 1中所列 组分及其含量, 简单混合均匀, 即制得各清洗剂。 表 1 本发明光刻胶实施例 1~26
三丙二醇单苯 聚氧乙烯改性聚丙 三乙醇胺 30
1 1 2 55.7 烯酸 (数均分子量 0.3
基醚 聚氧乙烯醚 (数
为 5000)
均分子量为 5 10000)
乙基砜 40 四乙基 聚氧乙烯改性聚丙
三异丙二醇单 二甘醇胺 5 氢氧化 2.5 2.5 5 44.45 烯酸酯 (数均分子 0.5
苯基醚 聚乙烯醇 (数均 铰 量为 5000) 0.05
分子量为 500) 四丙基
六缩乙二醇单
氢氧化 1 2 聚氧乙烯改性聚丙 环丁砜 15
苯基醚
铰 烯酸酯一乙醇胺盐
2 69.5 0.5
(数均分子量为
六縮丙二醇单
甲基氢 1 4 5000) 异丙醇胺 5
苯基醚
氧化
四甲基
氢氧化 1.5 2-咪唑垸酮 30
聚氧乙烯改性聚甲
铰 六縮异丙二醇
2 3 60 基丙烯酸 (数均分 1
四乙基 单苯基醚
子量为 5000)
氢氧化 0.5 甲基二乙醇胺 2 铰 聚氧乙烯改性聚甲
1,3-二甲基 -2-咪 基丙烯酸酯 (数均 0.1 5
唑烷酮 分子量为 3000)
四丙基
丙二醇单苄基
氢氧化 3 3 10 68.5
醚
铵 聚氧乙烯改性聚甲 甲基乙醇胺 5
基丙烯酸二乙醇胺
0.4
盐 (数均分子量为
5000 ) 二甲基乙醇胺 5
1,3-二乙基 -2-咪
42 箱三 异丙二醇单苄 聚氧乙烯改性聚丙 唑垸酮 甲基氢 6.5 3.5 15 24.95 烯酸酯一乙醇胺盐 0.05
基醚
氧化铵 (数均分子量为 羟乙基乙二胺 8
5000)
一乙醇胺 20 四乙基 丙烯酸-马来酸共 甲基苯并三氮
1 氢氧化 0.5 1 1 75.48 聚物 (数均分子量 0.02 1唑
醚 :
铵 为 1500) 2-巯基苯并噻
1 唑
四丁基 丙二醇单苯基 甲基丙烯酸 -马来 三乙醇胺 3.5 氢氧化 1 3 2 90 酸共聚物 (数均分 0.08
醚 苯并三氮唑三 铰 子量为 1000) 0.42
乙醇胺盐 四甲基 异丙二醇单苯 聚甲基丙烯酸三乙 三乙醇胺 1 氢氧化 1 .5 2 5 88.5 醇胺盐 (数均分子 1 .5
基醚 1 -苯基 -5-巯基 铰 量为 10000) 0.5
四氮唑
异丙醇胺 1 .5
2-巯基苯并咪
0.35 四丙基 二丙二醇单苯 聚氧乙烯改性聚丙
聚乙烯醇 (数均 氢氧化 2 3 8 85 烯酸 (数均分子量 0.05 0.05
基醚 分子量为 500) 铰 为 5000)
聚乙烯吡咯垸 酮 (数均分子量 0.05 为 20000) 聚氧乙烯改性聚丙 甲基二乙醇胺 5 丙二醇单苯基
甲基氢 8.5 5 25 54.5 烯酸酯 (数均分子 0.5
醚 2-巯基苯并噻 氧化铵 量为 5000) 1.5
唑
四乙基 异丙二醇单苯 甲基乙醇胺 7.5
聚甲基丙烯酸 (数
氢氧化 1.5 1.5 5 82 0.3
基醚 均分子量为 2500) 2-巯基苯并噁 铰 2.2
唑
四丁基 二丙二醇单苯 聚丙烯酸三乙醇胺 羟乙基乙二胺 8 氢氧化 2 2 10 73 盐 (数均分子量为 3
基醚
铵 20000) 二巯基噻二唑 2
聚氧乙烯改性聚甲 二乙二醇单甲 四甲基 30
丙二醇单苯基 基丙烯酸二乙醇胺 醚
氢氧化 1 3 15 50 0.5
醚 盐 (数均分子量为 2-氨基 -5-巯基 铵 0.5
5000 ) -1 ,3,4-噻二唑
二乙二醇单乙 四丙基 聚氧乙烯改性聚丙 5
二异丙二醇单 醚
氢氧化 2.5 2.5 10 78.5 烯酸 (数均分子量 1
苯基醚 1 -羟基亚乙基 铰 为 5000) 0.5
-1,1 -二膦酸 二乙二醇单丁
19.8 丙二醇单苯基 聚甲基丙烯酸三乙 醚
甲基氢 9 5 30 1 醇胺盐 (数均分子 5 一乙醇胺 30
醚
氧化铰 量为 10000) 氨基三亚甲基
0.2 膦酸 四丁基 聚丙烯酸三乙醇胺 丙二醇单丁醚 30
二乙二醇单苯
氢氧化 5 5 6 49.9 盐 (数均分子量为 4
基醚 2-膦酸丁垸 铰 20000) 0.1
-1,2,4-三羧酸 二丙二醇单甲 四甲基 聚氧乙烯改性聚丙 20
二丙二醇单苯 醚
氢氧化 2 2 5 70.55 烯酸 (数均分子量 0.4
基醚 乙二胺四亚甲 铰 为 5000) 0.05
基膦酸 二丙二醇单乙 四丙基 15
丙二醇单苯基 聚丙烯酸三乙醇胺 醚
氢氧化 2.5 2.5 10 67.95 盐 (数均分子量为 2
醚 二乙烯三胺五 铰 20000) 0.05
亚甲基膦酸 二丙二醇单丁 丙二醇单苄基 聚甲基丙烯酸三乙 25
醚
甲基氢 3 3 10 52.5 醇胺盐 (数均分子 1 .5
醚 六縮丙二醇单 氧化铰 量为 10000) 5
丁醚
) 1
效果实施例
表 2给出了对比光刻胶清洗剂 Γ~7'和本发明的光刻胶清洗剂 1〜16的配 方, 按表 2中所列组分及其含量, 简单混合均匀, 即制得各清洗剂。
对比光刻胶清洗剂 Γ~7'和本发明光刻胶清洗剂 1~16的组分和含量
聚氧乙
聚氧乙
烯改性 1-羟基 四甲 烯醚
清 丙二醇 聚丙烯 苯并 亚乙
基氢 去离 (数均
洗 单苯基 酸 (数均 环丁砜 三氮
氧化 子水 亚砜 胺醇 分子量
剂 醚 分子量 唑 二
铰 έ
为
为
10000)
5000)
1 ' 1.00 5.00 1 94.00 1 / 1 1 1 1
2, 1.00 5.00 1 93.50 1 1 1 1 0.50 1
3' 2.00 8.00 1 89.50 1 1 1 1 0.50 1
4' 2.00 5.00 1 92.50 1 1 1 1 0.50 1
5, 2.00 5.00 1 92.50 1 1 1 1 1 0.50
6, 3.00 6.00 5.00 86.00 1 1 1 1 1 1
Τ 3.00 6.00 1 91.00 1 1 1 1 1 1
1 1.00 5.00 2.00 91.99 0.01 1 1 1 1 1
2 1.00 5.00 4.00 89.95 0.05 1 1 1 1 1
3 1.50 1.50 4.00 82.95 0.05 10.00 1 1 1 1
4 2.00 2.00 5.00 86.80 0.20 1 4.00 1 1 1
5 2.50 2.50 5.00 82.60 0.30 1 7.00 0.10 1 1
6 3.00 4.00 6.00 76.20 0.60 1 10.00 1 0.20 1
7 3.00 5.00 6.00 65.20 0.60 10.00 10.00 1 1 0.20
8 3.50 3.50 8.00 72.00 0.90 1 12.00 0.10 1 1
9 4.00 4.00 8.00 70.50 0.90 1 12.00 0.10 0.50 1
10 4.50 4.50 10.00 64.70 1.20 1 15.00 1 1 0.10
11 5.00 5.00 10.00 63.00 1.50 1 15.00 1 0.50 1
12 2.30 3.00 6.00 82.00 0.50 1 6.00 0.20 1 1
13 2.90 3.00 6.00 79.20 0.70 1 8.00 0.20 1 1
14 3.50 4.00 9.00 71.90 1.00 1 10.00 1 0.60 1
15 1.80 2.50 7.00 83.00 0.60 1 5.00 1 1 0.10
16 2.60 2.90 8.00 76.40 0.80 1 9.00 0.30 1 1
由表 2制得的各清洗剂中,除对比清洗剂 7'中有少量四甲基氢氧化铵不 能溶解以外,对比清洗剂 Γ〜6'和本发明清洗剂 1~16均为澄清透明的均相溶 液。
将对比清洗剂 Γ〜6'和本发明清洗剂 1〜16用于清洗空白 Cu晶片, 测定 其对于金属 Cu的腐蚀情况。测试方法和条件: 将 4 X 4cm空白 Cu晶片浸入 清洗剂,在 20〜85°C下利用恒温振荡器以约 60转 /分的振动频率振荡 60分钟, 然后经去离子水洗涤后用高纯氮气吹干, 利用四极探针仪测定空白 Cu晶片 蚀刻前后表面电阻的变化计算得到。 结果如表 3所示。
将对比清洗剂 Γ〜6'和本发明清洗剂 1~16用于清洗空白 A1晶片, 测定 其对于金属 A1的腐蚀情况。 测试方法和条件: 将 4 X 4cm空白 A1晶片浸入 清洗剂,在 20〜85 °C下利用恒温振荡器以约 60转 /分的振动频率振荡 60分钟, 然后经去离子水洗涤后用高纯氮气吹干, 利用四极探针仪测定空白 A1 晶片 蚀刻前后表面电阻的变化计算得到。 结果如表 3所示。
将对比清洗剂 Γ〜6 '和本发明清洗剂 1~16用于清洗空白的四乙氧基硅垸 (TEOS ) 晶片, 测定其对于非金属 TEOS的腐蚀情况。 测试方法和条件: 将 4 X 4cm空白 TEOS晶片浸入清洗剂, 在 20〜85°C下利用恒温振荡器以约 60转 /分的振动频率振荡 60分钟, 然后经去离子水洗涤后用高纯氮气吹干。 利用 Nanospec6100测厚仪测定空白 TEOS晶片清洗前后 TEOS厚度的变化 计算得到, 结果如表 3所示。
本发明中, 利用光刻胶清洗剂清洗半导体晶片上光刻胶的方法如下: 将 含有负性丙烯酸酯类光刻胶 (厚度约为 60微米, 且经过曝光和刻蚀) 的半 导体晶片 (含有图案)浸入清洗剂中, 在 20〜85°C下利用恒温振荡器以约 60
转 /分的振动频率振荡 1~30分钟, 然后经去离子水洗涤后用高纯氮气吹干。 光刻胶的清洗效果和清洗剂对晶片图案的腐蚀情况如表 3所示。 表 3 对比光刻胶清洗剂 Γ〜6'和本发明光刻胶清洗剂 1~16对金属 Cu和 A1 以及非金属 TEOS的腐蚀性及其对负性光刻胶的清洗情况
〇 略有腐蚀; 〇 少量残余;
△ 中等腐蚀; Δ 较多残余;
X 严重腐蚀。 X 大量残余。
从表 3可以看出, 与对比实施例 1,〜6,清洗剂相比, 实施例 1〜16清洗剂 对负性丙烯酸酯类光刻胶具有良好的清洗能力, 使用温度范围广, 同时对金 属 Cu和 A1以及非金属 TEOS的腐蚀性低, 对晶片图案无损坏。
Claims
权利要求
K 一种光刻胶清洗剂, 含有: 季铵氢氧化物、 水、 垸基二醇芳基醚、 二甲基亚砜和聚丙烯酸类缓蚀剂; 其中所述的垸基二醇芳基醚中垸基二醇的 碳原子数目为 3~18。
2、 根据权利要求 1 所述的光刻胶清洗剂, 其特征在于, 所述的季铵氢 氧化物为选自四甲基氢氧化铵、 四乙基氢氧化铵、 四丙基氢氧化铵、 四丁基 氢氧化铵和苄基三甲基氢氧化铵中的一种或多种。
3、 根据权利要求 1 所述的光刻胶清洗剂, 其特征在于, 所述的季铵氢 氧化物的含量为 0.1〜10wt%。
4、 根据权利要求 3所述的光刻胶清洗剂, 其特征在于, 所述的季铵氢 氧化物的含量为 0.5~5wt%。
5、 根据权利要求 1 所述的光刻胶清洗剂, 其特征在于, 所述的水的含 量为 0.2〜5wt%。
6、 根据权利要求 5所述的光刻胶清洗剂, 其特征在于, 所述的水的为 0.5〜3wt %。
7、 根据权利要求 1 所述的光刻胶清洗剂, 其特征在于, 所述的垸基二 醇芳基醚为选自丙二醇单苯基醚、 异丙二醇单苯基醚、 二乙二醇单苯基醚、 二丙二醇单苯基醚、 二异丙二醇单苯基醚、 三乙二醇单苯基醚、 三丙二醇单 苯基醚、三异丙二醇单苯基醚、六缩乙二醇单苯基醚、六缩丙二醇单苯基醚、 六缩异丙二醇单苯基醚、 丙二醇单苄基醚、 异丙二醇单苄基醚或己二醇单萘 基醚中的一种或多种。
8、 根据权利要求 1 所述的光刻胶清洗剂, 其特征在于, 所述的垸基二
醇芳基醚的含量为 0.5~30wt%,
9、 根据权利要求 8所述的光刻胶清洗剂, 其特征在于, 所述的烷基二 醇芳基醚的含量为 2.0~15.0wt%。
10、 根据权利要求 1所述的光刻胶清洗剂, 其特征在于, 所述的二甲基 亚砜的含量为 l〜98wt%。
11、 根据权利要求 10所述的光刻胶清洗剂, 其特征在于, 所述的二甲 基亚砜的含量为 30〜90wt%。
12、 根据权利要求 1所述的光刻胶清洗剂, 其特征在于, 所述的聚丙烯 酸类缓蚀剂为选自丙烯酸聚合物及其共聚物、 甲基丙烯酸聚合物及其共聚 物, 丙烯酸聚合物的醇胺盐, 甲基丙烯酸聚合物的醇胺盐, 聚氧乙烯改性的 丙烯酸聚合物及其酯和醇铵盐, 以及聚氧乙烯改性的甲基丙烯酸聚合物及其 酯和醇铵盐中的一种或多种。
13、 根据权利要求 1所述的光刻胶清洗剂, 其特征在于, 所述的聚丙烯 酸类化合物的数均分子量为 500〜20000。
14、 根据权利要求 13所述的光刻胶清洗剂, 其特征在于, 所述的聚丙 烯酸类化合物的数均分子量为 1000~10000。
15、 根据权利要求 1所述的光刻胶清洗剂, 其特征在于, 所述的聚丙烯 酸类化合物的含量为 0.01~5.0wt%。
16、 根据权利要求 15所述的光刻胶清洗剂, 其特征在于, 所述的聚丙 烯酸类化合物的含量为 0.05〜2.5wt%。
17、 根据权利要求 1所述的光刻胶清洗剂, 其特征在于, 所述的光刻胶 清洗剂还含有选自极性有机共溶剂、表面活性剂和除聚丙烯酸类缓蚀剂以外
的其它缓蚀剂中的一种或多种。
1 8、 根据权利要求 17所述的光刻胶清洗剂, 其特征在于, 所述的极性 有机共溶剂为选自亚砜、 砜、 咪唑垸酮、 醇胺和烷基二醇单烷基醚中的一种 或多种。
19、 根据权利要求 18所述的光刻胶清洗剂, 其特征在于, 所述的亚砜 为选自二乙基亚砜或甲乙基亚砜中的一种或多种; 所述的砜为选自甲基砜、 乙基砜和环丁砜中的一种或多种; 所述的咪唑烷酮为选自 2-咪唑垸酮、 1 ,3- 二甲基 -2-咪唑垸酮和 1 ,3-二乙基 -2-咪唑烷酮中的一种或多种;所述的醇胺为 选自一乙醇胺、 三乙醇胺、 二甘醇胺、 异丙醇胺、 甲基二乙醇胺、 甲基乙醇 胺、 二甲基乙醇胺和羟乙基乙二胺中的一种或多种; 所述的垸基二醇单垸基 醚为选自二乙二醇单甲醚、 二乙二醇单乙醚、 二乙二醇单丁醚、 丙二醇单丁 醚、 二丙二醇单甲醚、 二丙二醇单乙醚和二丙二醇单丁醚中的一种或多种。
20、 根据权利要求 17所述的光刻胶清洗剂, 其特征在于, 所述的极性 有机共溶剂含量为 50%, 上述百分比为质量百分比, 不包括 0%。
21、 根据权利要求 20所述的光刻胶清洗剂, 其特征在于, 所述的极性 有机共溶剂含量为质量百分比 5〜30%。
22、 根据权利要求 17所述的光刻胶清洗剂, 其特征在于, 所述的表面 活性剂为选自聚乙烯醇、 聚乙烯吡咯垸酮和聚氧乙烯醚中的一种或多种。
23、 根据权利要求 17所述的光刻胶清洗剂, 其特征在于, 所述的表面 活性剂的数均分子量为 500~20000。
24、 根据权利要求 23所述的光刻胶清洗剂, 其特征在于, 所述的表面
25、 根据权利要求 17所述的光刻胶清洗剂, 其特征在于, 所述的表面 活性剂含量为 5%, 上述百分比为质量百分比, 不包括 0%。
26、 根据权利要求 25所述的光刻胶清洗剂, 其特征在于, 所述的表面 活性剂含量为质量百分比 0.05~3.0%。
27、 根据权利要求 17所述的光刻胶清洗剂, 其特征在于, 所述的除聚 丙烯酸类缓蚀剂以外的其它缓蚀剂为选自醇胺、唑类和膦酸类缓蚀剂中的一 种或多种。
28、 根据权利要求 27所述的光刻胶清洗剂, 其特征在于, 所述的醇胺 缓蚀剂为选自一乙醇胺、 三乙醇胺、 二甘醇胺、 异丙醇胺、 甲基二乙醇胺、 甲基乙醇胺、 二甲基乙醇胺和羟乙基乙二胺中的一种或多种; 所述的唑类缓 蚀剂为选自苯并三氮唑、 甲基苯并三氮唑、 苯并三氮唑二乙醇胺盐、 2-巯基 苯并咪唑、 2-巯基苯并噻唑、 2-巯基苯并噁唑、 二巯基噻二唑、 3-氨基 -1 ,2,4- 三氮唑、 4-氨基 -1 ,2,4-三氮唑、 3-氨基 -5-巯基 -1,2,4-三氮唑、 3,5-二氨基 -1 ,2,4- 三氮唑、 4-氨基 -5-巯基 -1 ,2,4-三氮唑、 5-氨基-四氮唑和 1-苯基 -5-巯基四氮唑 中的一种或多种; 所述的膦酸类缓蚀剂为选自 1-羟基亚乙基 -1 ,1-二膦酸、 氨 基三亚甲基膦酸、 2-膦酸丁垸 -1 ,2,4-三羧酸、 乙二胺四亚甲基膦酸和二乙烯 三胺五亚甲基膦酸中的一种或多种。
29、 根据权利要求 17所述的光刻胶清洗剂, 其特征在于, 所述的除聚 丙烯酸类缓蚀剂以外的其它缓蚀剂含量为 5.0%, 上述百分比为质量百分 比, 不包括 0%。
30、 根据权利要求 29所述的光刻胶清洗剂, 其特征在于, 所述的除聚 丙烯酸类缓蚀剂以外的其它缓蚀剂含量为质量百分比 0.10~3.0%。
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CN104093824B (zh) | 2012-02-06 | 2018-05-11 | 巴斯夫欧洲公司 | 包含具体含硫化合物和糖醇或多元羧酸的化学机械抛光后的清洗组合物 |
CN107121901A (zh) * | 2017-06-23 | 2017-09-01 | 昆山欣谷微电子材料有限公司 | 一种富水基清洗液组合物 |
CN112558434B (zh) * | 2020-12-22 | 2023-03-07 | 江苏奥首材料科技有限公司 | 一种光刻胶清洗剂组合物 |
CN112764330B (zh) * | 2021-01-08 | 2022-08-02 | 绵阳艾萨斯电子材料有限公司 | Pfa光刻胶再生剥离液及其制备方法与应用 |
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