WO2010060274A1 - Detergent for removing photo resist - Google Patents

Detergent for removing photo resist Download PDF

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Publication number
WO2010060274A1
WO2010060274A1 PCT/CN2009/001285 CN2009001285W WO2010060274A1 WO 2010060274 A1 WO2010060274 A1 WO 2010060274A1 CN 2009001285 W CN2009001285 W CN 2009001285W WO 2010060274 A1 WO2010060274 A1 WO 2010060274A1
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WO
WIPO (PCT)
Prior art keywords
acid
borate
ether
cleaning composition
composition according
Prior art date
Application number
PCT/CN2009/001285
Other languages
French (fr)
Chinese (zh)
Inventor
彭洪修
Original Assignee
安集微电子（上海）有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 安集微电子（上海）有限公司 filed Critical 安集微电子（上海）有限公司
Priority to CN2009801483637A priority Critical patent/CN102227689A/en
Publication of WO2010060274A1 publication Critical patent/WO2010060274A1/en

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • 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
    • C11D7/3209—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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • 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
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3445—Organic compounds containing sulfur containing sulfino groups, e.g. dimethyl sulfoxide
    • 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
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • 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
    • C11D7/34—Organic compounds containing sulfur

Definitions

  • the present invention relates to a cleaning composition in a semiconductor manufacturing process, and in particular to a photoresist cleaning composition.
  • 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.
  • the negative photoresist having a cross-linked network structure after exposure and etching is especially a thick film negative photoresist.
  • 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, 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 potassium hydroxide, quaternary ammonium hydroxides and alcohol amines, etc., are capable of dissolving the photoresist residues produced by the photoresist and/or etching.
  • a cleaning agent containing potassium hydroxide or a quaternary ammonium hydroxide has a better ability to remove photoresist residues generated by photoresist and/or etching than a cleaning agent composed of an alcohol amine.
  • the cleaning agent containing potassium hydroxide is liable to cause corrosion of the wafer pattern and the substrate, and the removal of the photoresist is mainly performed by peeling, so that the photoresist forms a chip-like peeling or a gel-like swelling, which easily causes light.
  • the deposition or adhesion of the glue on the surface of the wafer even leading to damage to the wafer pattern.
  • the cleaning agent containing quaternary ammonium hydroxide has both stripping and dissolving effects on the photoresist, and does not cause deposition or adhesion of the photoresist on the surface of the wafer.
  • 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 to the 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.
  • the organic phenolic compound is harmful to the human body and pollutes the environment, and the cleaning agent has insufficient cleaning
  • No. 5,962,197 proposes photoresist cleaning consisting of potassium hydroxide, propylene glycol ether, N-methylpyrrolidone, surfactant, 1,3-butanediol, diglycolamine and water in an amount of less than 1% by mass. Agent.
  • the semiconductor wafer is immersed in the cleaning agent, and the photoresist on the wafer is removed at 90 to 110 °C.
  • the cleaning agent contains potassium hydroxide, which has high corrosion to the wafer substrate, and the chip-like peeling or colloidal swelling formed by the stripping photoresist is deposited or adhered on the surface of the wafer, resulting in photoresist. Damage to residual and wafer patterns.
  • a photoresist cleaning agent consisting of tetramethylammonium hydroxide, N-methylmorpholine-N-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 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 US Pat. 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-imidazolium, which is relatively expensive, 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 glycol, and water is proposed in JP2001215736.
  • the semiconductor wafer is immersed in the cleaning agent, and 20 ⁇ on the wafer is removed at 20 to 90 ° C! ⁇ 40 ⁇ thickness of photoresist.
  • 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 the cleaning ability of the cleaning agent for the photoresist, especially the negative photoresist, is lowered.
  • 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 of 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 the quaternary ammonium hydroxide, but the flash point of methanol or ethanol is too low, and the cleaning ability of the cleaning agent for the photoresist, especially the negative photoresist, is lowered.
  • the cleaning agent does not contain a corrosion inhibitor that inhibits the corrosion of metals, especially active metals such as aluminum and copper.
  • the cleaning agent has a slightly higher corrosion on the semiconductor wafer pattern and substrate.
  • the existing photoresist cleaning agent has insufficient cleaning ability for a photoresist having a relatively high thickness, or is highly corrosive to a semiconductor wafer pattern and a substrate, and has a large defect.
  • the technical problem to be solved by the present invention is to provide a defect for the thick photoresist cleaning ability of the existing photoresist cleaning agent, the corrosion resistance to the semiconductor wafer pattern and the substrate, and the environmental harmful defects.
  • a photoresist cleaning composition which is strong in cleaning ability of a thick film photoresist and which is less corrosive to semiconductor wafer patterns and substrates and is environmentally friendly.
  • a photoresist cleaning composition comprising quaternary ammonium hydroxide, water, alkyl glycol aryl ether, dimethyl sulfoxide and a corrosion inhibitor;
  • the mercapto glycol aryl ether has a number of carbon atoms of 3 to 18, and the sustained release agent is selected from the group consisting of 3 to 18 carbon atoms.
  • the quaternary ammonium hydroxide is preferably selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylhydroxide.
  • One or more of ammonium more preferably one or more selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide, most preferably tetramethylammonium hydroxide .
  • the content thereof is preferably from 0.1 to 10% by weight, more preferably from 1 to 5% by weight.
  • the water content is preferably from 0.2 to 15% by weight, more preferably from 0.5 to 10% by weight.
  • 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 diisomeric.
  • Propylene glycol monophenyl ether triethylene glycol monophenyl ether, tripropylene glycol monophenyl ether, triisopropyl glycol monophenyl ether, hexadeethylene glycol monophenyl ether, hexapropylene glycol monophenyl ether, hexagonal
  • isopropyl glycol monophenyl ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether and hexanediol mono-naphthyl ether more preferably selected from propylene glycol monophenyl ether, dipropylene glycol monophenyl group One or more of ether and propylene glycol monobenzyl ether.
  • the content of the mercapto glycol aryl ether is preferably from 0.1 to 65 wt%, more preferably from 0.5 to 20.0 wt%.
  • 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 protecting the environment.
  • the content of the dimethyl sulfoxide is preferably from 1 to 98% by weight, more preferably from 30 to 90% by weight.
  • the boric acid, borate and boric acid ester are preferably selected from the group consisting of boric acid, phenylboronic acid, 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 2,3.
  • the photoresist cleaning composition may further comprise one selected from the group consisting of a polar organic cosolvent, a surfactant, and a corrosion inhibitor other than boric acid, borate and boric acid ester.
  • a polar organic co-solvent content is preferably 50% by weight, but does not include 0% by weight, more preferably 5 to 30% by weight
  • the surfactant content is preferably 5% by weight, but not including 0% by weight. More preferably, it is 0.05 to 3.0% by weight; the content of the corrosion inhibitor other than the corrosion inhibitor of boric acid, borate and boric acid ester is preferably 5.0% by weight, but does not include 0% by weight, more Preferably, it is 0.05 to 3.0% by weight.
  • the polar organic co-solvent is preferably one or more selected from the group consisting of sulfoxides, sulfones, imidazoles, alcoholamines, and mercaptodiol monodecyl ethers.
  • the sulfoxide is preferably diethyl sulfoxide and/or methyl ethyl sulfoxide; and the sulfone is preferably one or more selected from the group consisting of methyl sulfone, ethyl sulfone and sulfolane.
  • the imidazolium is preferably selected from the group consisting of 2-imidazolium, 1,3-dimethyl-2-imidazolium and 1,3-diethyl-2-imidazolium One or more of them, more preferably 1,3-dimethyl-2-imidazolium;
  • the alcohol amine is preferably selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, isopropanol In amines, methylethanolamine, methyldiethanolamine, dimethylethanolamine and hydroxyethylethylenediamine One or more, more preferably one or more selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, and methylethanolamine;
  • the mercaptodiol monodecyl ether is preferably selected from the group consisting of One or more of ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol
  • the surfactant is preferably selected from one or more of polyvinyl alcohol, polyvinylpyrrolidone and polyoxyethylene ether, more preferably polyvinylpyrrolidone and/or poly. Oxyethylene 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 boric acid, borate and boric acid ester is preferably selected from one of an alcohol amine, an azole, a phosphonic acid and a polyacrylic corrosion inhibitor.
  • the alcohol amine corrosion inhibitor is preferably selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, isopropanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine and hydroxyethylethyl
  • the diamines more preferably one or more selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, and methylethanolamine
  • the azole inhibitor is preferably selected from the group consisting of Benzotriazole, methylbenzotriazole, benzotriazole diethanolamine salt, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, dimercaptothiadiazole , 3-amino-1,2,4-triazo
  • 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, and methacrylic polymers. More preferably, one or more of an alcohol amine salt, a polyoxyethylene-modified acrylic polymer, an ester thereof and an alkanolammonium salt, and a polyoxyethylene-modified methacrylic acid polymer, and an ester thereof and an alkanolammonium salt.
  • the polyacrylic corrosion inhibitor preferably has a number average molecular weight of from 500 to 100,000, more preferably from 1,000 to 50,000.
  • the polyacrylic corrosion inhibitor exhibits a strong inhibitory effect on corrosion of metals such as aluminum.
  • the reagents and starting materials used in the present invention are commercially available.
  • the photoresist cleaning composition of the present invention can be obtained by simply mixing the components described above.
  • the photoresist cleaner composition of the present invention can be used over a wide temperature range (between 20 and 85).
  • the cleaning method can be referred to the following steps: The semiconductor wafer containing the photoresist is immersed in the cleaning composition, 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 composition of the present invention can relatively quickly clean photoresist and other etching residues having a thickness of 20 ⁇ or more on a substrate such as a metal, a metal alloy or a dielectric.
  • the mercapto diol aryl ether contained in the photoresist cleaning composition of the present invention can improve the solubility of the quaternary ammonium hydroxide in dimethyl sulfoxide.
  • the increase in the solubility of quaternary ammonium hydroxide is beneficial to The cleaning ability of the photoresist cleaning composition of the present invention to a photoresist, especially a thick film photoresist.
  • the protective film prevents the attack of the wafer pattern and the substrate by halogen atoms, hydroxide ions, etc., thereby reducing the corrosion of the wafer pattern and the substrate; in particular, it contains corrosion inhibition selected from the group consisting of boric acid, borate and boric acid ester.
  • the agent exhibits a good inhibitory effect on the corrosion of metals such as aluminum. Therefore, it exhibits extremely weak corrosiveness to metals such as aluminum and copper and non-metal materials such as silica.
  • the photoresist cleaning composition of the present invention can remove a high-crosslinking thick film negative photoresist on a semiconductor wafer by dissolution to prevent deposition or adhesion of the photoresist on the surface of the wafer, and It can cause corrosion or damage to the wafer pattern.
  • the photoresist cleaning composition of the present invention can be used over a wide temperature range (20-85 ° C). 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.
  • Ammonium oxide enoic acid (number average molecular weight is 10,000)
  • Methylbenzotriazole 0.5 benzotriazole 0.5 Methyl sulfone 5 monoethanolamine 30 tetrabutyl hydride tripropylene glycol
  • Polyacrylic acid (number average molecular weight is
  • Polyoxyethylene modified polymethyl methacrylate (number average molecular weight is 0.5 75000)
  • Monoethanolamine salt (number average molecular weight is 1 40000) Isopropanolamine 1.5
  • Oleic acid (number average molecular weight is 10000) methylethanolamine 7.5 tetraethylammonium borate 0.3
  • Hinge diisopropyl glycol boronic acid isopropanolamine enoic acid diethanolamine salt (number average molecule 2
  • Monophenyl ether ⁇ Bu amount is 8000) Dimethylethanolamine 2 Boric acid diethylene glycol amine Diethylene glycol monomethyl ether 30
  • Ammonium borate 0.2 (number average molecular weight is 10000)
  • the quantity is 8000
  • Tributyl borate 1 polyoxyethylene modified polymethyl propyl 1.5
  • Oleic acid number average molecular weight 10000
  • Polyoxyethylene ether (number average molecular weight is
  • Polyoxyethylene modified polyacrylic acid monoethanolamine salt (number average molecular weight is 0.5 40000)
  • Table 2 shows comparative cleaning agents ⁇ 7, and the photoresist cleaning composition embodiment of the present invention
  • the formula of 27 ⁇ 42 is simply mixed evenly according to the components listed in Table 2 and their contents, that is, each cleaning agent is prepared.
  • Comparative Example Cleaning Agents 1, -6, and the cleaning agent of the present invention 27-42 are clear and transparent homogeneous solutions.
  • the comparative example cleaning agent ⁇ 6, and the cleaning agent 27 ⁇ 42 of the embodiment of the present invention were used to clean the three blank wafers and the semiconductor wafer containing the photoresist, and the test results are shown in Table 3.
  • Comparative Example Cleaner ⁇ 6' and Inventive Example Cleaner 27 ⁇ 42 were used to clean the blank Cu wafer and measure its corrosion to metallic Cu. Test methods and conditions: 4 4 4 cm blank Cu wafer was immersed in a cleaning agent, oscillated with a constant temperature oscillator at 20 to 85 ° C for 60 minutes, then washed with deionized water and then dried with high purity nitrogen gas. The needle gauge measures the change of the surface resistance of the blank Cu wafer before and after etching. The results are shown in Table 3.
  • Comparative Example Cleaner ⁇ 6' and Inventive Example Cleaner 27 ⁇ 42 were used to clean the blank A1 wafer and determine its corrosion to metal A1.
  • Test methods and conditions The 4 X 4 cm blank A1 wafer was immersed in a cleaning agent, shaken at 20 to 85 ° C for 60 minutes using a constant temperature oscillator, then washed with deionized water and then dried with high purity nitrogen gas, using a quadrupole probe. The needle gauge was used to measure the change in surface resistance of the blank A1 wafer before and after etching. The results are shown in Table 3.
  • the comparative example cleaning agent ⁇ 6' and the cleaning agent 27 ⁇ 42 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, shaken at 20 to 85 ° C for 60 minutes using a constant temperature oscillator, and then washed with deionized water and then dried with high purity nitrogen.
  • the thickness of the TEOS thickness before and after cleaning of the blank TEOS wafer was calculated using a Nanospec 6100 thickness gauge. The results are shown in Table 3.
  • the comparative example cleaning agents 1, -6, and the cleaning agents 27 to 42 of the present invention are used to clean the photoresist on the semiconductor wafer.
  • the cleaning method is as follows: Immerse the semiconductor wafer (containing pattern) containing a negative acrylate photoresist (having a thickness of about 60 ⁇ m and exposed and etched) into the cleaning agent. The mixture was shaken at 20 to 85 ° C for 1 to 30 minutes using a constant temperature oscillator, and then washed with deionized water and then dried with high purity nitrogen gas. The cleaning effect of the photoresist and the corrosion of the wafer pattern by the cleaning agent are shown in Table 3.
  • Corrosion ⁇ Basically non-corrosive; Cleaning condition: ⁇ Completely removed;
  • a semiconductor wafer (containing a pattern) containing a high degree of crosslinking of a negative acrylate-based photoresist (having a thickness of about 150 ⁇ m and exposed and etched) was immersed in the cleaning agent 32 of the present invention shown in Table 2.
  • Table 2 A semiconductor wafer (containing a pattern) containing a high degree of crosslinking of a negative acrylate-based photoresist (having a thickness of about 150 ⁇ m and exposed and etched) was immersed in the cleaning agent 32 of the present invention shown in Table 2.
  • Table 2 A semiconductor wafer (containing a pattern) containing a high degree of crosslinking of a negative acrylate-based photoresist (having a thickness of about 150 ⁇ m and exposed and etched) was immersed in the cleaning agent 32 of the present invention shown in Table 2.
  • ⁇ 42 it was shaken at 40 to 85 ° C for 10 to 60 minutes using a constant temperature oscillator, and then washed with deionized water and then dried with
  • Corrosion ⁇ Basically non-corrosive; Cleaning condition: ⁇ Completely removed;
  • the cleaning agent 27 ⁇ 42 of the embodiment of the present invention has good cleaning ability for the thick film negative acrylate photoresist, and is used. Warm Wide range of degrees, low corrosivity to metallic Cu and A1 and non-metallic TEOS, no corrosion or damage to the wafer pattern.
  • the photoresist cleaning composition of the present invention can relatively quickly clean photoresist and other etching residues having a thickness of 20 ⁇ m or more on a substrate such as a metal, a metal alloy or a dielectric. It exhibits extremely weak corrosive properties to metals such as aluminum and copper and non-metallic materials such as silicon dioxide, and does not cause corrosion or damage to the wafer pattern, and can be used in a wide temperature range (20 to 85 ° C). use.

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Abstract

A detergent for removing photo resist includes quaternary ammonium hydroxide, water, alkyl glycol aryl ether in which the alkyl glycol has 3-18 carbon atoms, dimethyl sulfoxide and corrosion inhibitor. At least one corrosion inhibitor is selected from boric acid, borate and boric acid ester. The detergent for removing photo resist further includes polar organic co-solvent, surfactant and /or other corrosion inhibitor. The detergent can clean photo resist and residues on a metal, metal alloy and dielectric substrate.

Description

一种光刻胶清洗剂组合物  Photoresist cleaning composition
技术领域 Technical field
本发明涉及半导体制造工艺中一种清洗剂组合物，具体地涉及一种光刻 胶清洗剂组合物。 技术背景  The present invention relates to a cleaning composition in a semiconductor manufacturing process, and in particular to a photoresist cleaning composition. technical background
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尤其是厚 膜负性光刻胶。  In a typical semiconductor manufacturing process, 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 20μηι are gradually being used in semiconductor wafer fabrication processes. Currently, most of the photoresist cleaners in the industry have better cleaning ability for positive photoresists, but cannot completely remove the wafers. The negative photoresist having a cross-linked network structure after exposure and etching is especially a thick film negative photoresist.
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。  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. .
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。 强碱如氢氧化钾、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。与由醇胺组成的清洗剂相比， 含有氢氧化钾或季铵氢氧化物 的清洗剂对光刻胶和 /或刻蚀所产生的光刻胶残余物的去除能力较好。但含有 氢氧化钾的清洗剂易造成晶片图案和基材的腐蚀，而且其对光刻胶的去除以 剥离方式为主， 使光刻胶形成碎片状剥离物或胶状溶胀物， 容易造成光刻胶 在晶片表面的沉积或粘连， 甚至导致晶片图案的损坏。含有季铵氢氧化物的 清洗剂对光刻胶的去除兼具剥离和溶解两种作用，不会造成光刻胶在晶片表 面的沉积或粘连。 Currently, the photoresist cleaning composition is mainly composed of a strong base, a polar organic solvent, and/or water, 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 potassium hydroxide, quaternary ammonium hydroxides and alcohol amines, etc., are capable of dissolving the photoresist residues produced by the photoresist and/or etching. When the content of the strong base is too low, 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 cleaning agent containing potassium hydroxide or a quaternary ammonium hydroxide has a better ability to remove photoresist residues generated by photoresist and/or etching than a cleaning agent composed of an alcohol amine. However, the cleaning agent containing potassium hydroxide is liable to cause corrosion of the wafer pattern and the substrate, and the removal of the photoresist is mainly performed by peeling, so that the photoresist forms a chip-like peeling or a gel-like swelling, which easily causes light. The deposition or adhesion of the glue on the surface of the wafer, even leading to damage to the wafer pattern. The cleaning agent containing quaternary ammonium hydroxide has both stripping and dissolving effects on the photoresist, and does not cause deposition or adhesion of the photoresist on the surface of the wafer.
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。  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. When the content of the polar organic solvent is too low, 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.
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。  In order to increase the ability of the cleaning agent to hydrolyze and/or dissolve the photoresist residues produced by the photoresist and/or etching, water in the chemical cleaning agent is sometimes necessary. However, when the water content is too high, the cleaning agent has insufficient ability to remove the photoresist residue generated by the photoresist and/or etching, and is liable to cause corrosion of the wafer pattern and the substrate.
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。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， 且该清洗剂对负性光刻胶的 清洗能力不足。 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 to the 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. The organic phenolic compound is harmful to the human body and pollutes the environment, and the cleaning agent has insufficient cleaning ability for the negative photoresist.
US5962197中提出了由氢氧化钾、 丙二醇醚、 N-甲基吡咯烷酮、表面活 性剂、 1,3-丁二醇、二甘醇胺和质量百分含量小于 1%的水组成的光刻胶清洗 剂。将半导体晶片浸入该清洗剂中，在 90〜110°C下除去晶片上的光刻胶。该 清洗剂中含有氢氧化钾， 对晶片基材的腐蚀较高， 而且其剥离光刻胶所形成 的碎片状剥离物或胶状溶胀物会在晶片表面上沉积或粘连，造成光刻胶的残 留和晶片图案的损坏。  No. 5,962,197 proposes photoresist cleaning consisting of potassium hydroxide, propylene glycol ether, N-methylpyrrolidone, surfactant, 1,3-butanediol, diglycolamine and water in an amount of less than 1% by mass. Agent. The semiconductor wafer is immersed in the cleaning agent, and the photoresist on the wafer is removed at 90 to 110 °C. The cleaning agent contains potassium hydroxide, which has high corrosion to the wafer substrate, and the chip-like peeling or colloidal swelling formed by the stripping photoresist is deposited or adhered on the surface of the wafer, resulting in photoresist. Damage to residual and wafer patterns.
WO2004059700中提出了由四甲基氢氧化铵、 N-甲基吗啡啉 -N-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。  A photoresist cleaning agent consisting of tetramethylammonium hydroxide, N-methylmorpholine-N-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 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.
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 ΙΟμιη以上厚度的光刻胶。 该清洗 剂采用价格较为昂贵的 1，3'-二甲基 -2-咪唑垸酮作为有机共溶剂， 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 20μη！〜 40μιη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。 A photoresist cleaning agent consisting of quaternary ammonium hydroxide, dimethyl sulfoxide, 1,3,-dimethyl-2-imidazolidinone and water is proposed in US Pat. No. 6,040,117. The semiconductor wafer is immersed in the cleaning agent, and a photoresist having a thickness of ΙΟμη 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-imidazolium, which is relatively expensive, 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 glycol, and water is proposed in JP2001215736. The semiconductor wafer is immersed in the cleaning agent, and 20 μη on the wafer is removed at 20 to 90 ° C! ~ 40μιη thickness of photoresist. 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 the cleaning ability of the cleaning agent for the photoresist, especially the negative photoresist, is lowered. The cleaning agent has a slightly higher corrosion of the semiconductor wafer pattern and the substrate.
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 ΙΟμηι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。 A photoresist cleaning agent consisting of quaternary ammonium hydroxide, Ν-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 of a thickness of ΙΟμηι or more on the wafer is removed at 15 to 80 °C. The cleaning agent uses methanol or ethanol as a solubilizer for the quaternary ammonium hydroxide, but the flash point of methanol or ethanol is too low, and the cleaning ability of the cleaning agent for the photoresist, especially the negative photoresist, is lowered. The cleaning agent does not contain a corrosion inhibitor that inhibits the corrosion of metals, especially active metals such as aluminum and copper. The cleaning agent has a slightly higher corrosion on the semiconductor wafer pattern and substrate.
综上所述， 现有的光刻胶清洗剂对厚度较高的光刻胶的清洗能力不足， 或者对半导体晶片图案和基材的腐蚀性较强， 存在较大的缺陷。  In summary, the existing photoresist cleaning agent has insufficient cleaning ability for a photoresist having a relatively high thickness, or is highly corrosive to a semiconductor wafer pattern and a substrate, and has a large defect.
发明概要 Summary of invention
本发明要解决的技术问题是针对现有的光刻胶清洗剂存在的对厚膜光 刻胶清洗能力不足、对半导体晶片图案和基材的腐蚀性较强以及对环境有害 的缺陷，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的腐 蚀性较低、 利于环保的光刻胶清洗剂组合物。  The technical problem to be solved by the present invention is to provide a defect for the thick photoresist cleaning ability of the existing photoresist cleaning agent, the corrosion resistance to the semiconductor wafer pattern and the substrate, and the environmental harmful defects. A photoresist cleaning composition which is strong in cleaning ability of a thick film photoresist and which is less corrosive to semiconductor wafer patterns and substrates and is environmentally friendly.
本发明解决上述技术问题所采用的技术方案是： 一种光刻胶清洗剂组合 物， 包含季铵氢氧化物、水、烷基二醇芳基醚、二甲基亚砜和缓蚀剂； 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，所述的缓释剂选自 硼酸、 硼酸盐和硼酸酯中的一种或多种。 The technical solution adopted by the present invention to solve the above technical problems is: a photoresist cleaning composition comprising quaternary ammonium hydroxide, water, alkyl glycol aryl ether, dimethyl sulfoxide and a corrosion inhibitor; The mercapto glycol aryl ether has a number of carbon atoms of 3 to 18, and the sustained release agent is selected from the group consisting of 3 to 18 carbon atoms. One or more of boric acid, borate and borate.
本发明中， 所述的季铵氢氧化物较佳的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。 其含量较佳的为 0.1〜10wt%， 更 佳的为 l~5wt%。  In the present invention, the quaternary ammonium hydroxide is preferably selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylhydroxide. One or more of ammonium, more preferably one or more selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide, most preferably tetramethylammonium hydroxide . The content thereof is preferably from 0.1 to 10% by weight, more preferably from 1 to 5% by weight.
本发明中，所述的水的含量较佳的为 0.2~15wt%，更佳的为 0.5〜10wt %。 本发明中， 所述的垸基二醇芳基醚较佳的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、 异丙二醇单苄基醚和己二醇单萘基醚中的一种或多种，更佳的选自丙二醇单 苯基醚、 二丙二醇单苯基醚和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 0.1〜65wt%， 更佳的为 0.5〜20.0wt%。 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， 更利于保护环境。  In the present invention, the water content is preferably from 0.2 to 15% by weight, more preferably from 0.5 to 10% by weight. In the present invention, 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 diisomeric. Propylene glycol monophenyl ether, triethylene glycol monophenyl ether, tripropylene glycol monophenyl ether, triisopropyl glycol monophenyl ether, hexadeethylene glycol monophenyl ether, hexapropylene glycol monophenyl ether, hexagonal One or more of isopropyl glycol monophenyl ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether and hexanediol mono-naphthyl ether, more preferably selected from propylene glycol monophenyl ether, dipropylene glycol monophenyl group One or more of ether and propylene glycol monobenzyl ether. The content of the mercapto glycol aryl ether is preferably from 0.1 to 65 wt%, more preferably from 0.5 to 20.0 wt%. 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 protecting the environment.
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%。  In the present invention, the content of the dimethyl sulfoxide is preferably from 1 to 98% by weight, more preferably from 30 to 90% by weight.
本发明中， 所述的硼酸、 硼酸盐和硼酸酯较佳的选自硼酸、 苯硼酸、 2- 甲基苯硼酸、 3-甲基苯硼酸、 4-甲基苯硼酸、 2,3-二甲基苯硼酸、 4-乙基苯硼 酸、 4-丙基苯硼酸、 4-丁基苯硼酸、 2-甲氧基苯硼酸、 3-甲氧基苯硼酸、 4- 甲氧基苯硼酸、 3，4-二甲氧基苯硼酸、 2-羧基苯硼酸、 3-羧基苯硼酸、 4-羧基 苯硼酸、 2-羟甲基苯硼酸、 3-羟甲基苯硼酸、 4-羟甲基苯硼酸、 2-噻吩硼酸、 3-噻吩硼酸、 萘硼酸、 硼酸铵、 四甲基硼酸铵、 四乙基硼酸铵、 四丙基硼酸 铵、 四丁基硼酸铵、 苄基三甲基硼酸铵、 硼酸乙醇胺盐、 硼酸二乙醇胺盐、 硼酸三乙醇胺盐、 硼酸二甘醇胺盐、 硼酸异丙醇胺盐、 硼酸甲基乙醇胺盐、 硼酸甲基二乙醇胺盐、硼酸三甲酯、硼酸三乙酯、硼酸三丙酯、硼酸三丁酯、 异戊二醇硼酸酯、双联邻苯二酚硼酸酯、 硼酸频哪醇酯和硼酸咪唑啉酯中的 一种或多种， 更佳的选自硼酸、 苯硼酸、 2-羧基苯硼酸、 2-羟甲基苯硼酸、 四甲基硼酸铵、 四乙基硼酸铵、 硼酸乙醇胺盐、 硼酸三乙醇胺盐、 硼酸二甘 醇胺盐和双联邻苯二酚硼酸酯中的一种或多种。 其含量较佳的为 0.01-10wt%， 更佳的为 0.1 ~5wt%。 In the present invention, the boric acid, borate and boric acid ester are preferably selected from the group consisting of boric acid, phenylboronic acid, 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 2,3. - dimethylphenylboronic acid, 4-ethylbenzeneboronic acid, 4-propylbenzeneboronic acid, 4-butylbenzeneboronic acid, 2-methoxybenzeneboronic acid, 3-methoxyphenylboronic acid, 4-methoxybenzene Boric acid, 3,4-dimethoxybenzeneboronic acid, 2-carboxybenzeneboronic acid, 3-carboxybenzeneboronic acid, 4-carboxybenzeneboronic acid, 2-hydroxymethylphenylboronic acid, 3-hydroxymethylphenylboronic acid, 4-hydroxyl Methylbenzeneboronic acid, 2-thiopheneboronic acid, 3-thiopheneboronic acid, naphthaleneboronic acid, ammonium borate, ammonium tetramethylborate, ammonium tetraethylborate, ammonium tetrapropylborate, ammonium tetrabutylborate, ammonium benzyltrimethylborate, ethanolamine borate, diethanolamine borate Salt, triethanolamine borate, diglycolamine borate, isopropanolamine borate, methylethanolamine borate, methyldiethanolamine borate, trimethyl borate, triethyl borate, tripropyl borate, boric acid One or more of tributyl ester, isoprene glycol borate, bis catechol borate, pinacol borate and imidazoline borate, more preferably selected from boric acid, phenylboronic acid, 2-carboxybenzeneboronic acid, 2-hydroxymethylbenzeneboronic acid, ammonium tetramethylborate, ammonium tetraethylborate, ethanolamine borate, triethanolamine borate, diglycolamine borate and bis-catechol borate One or more of the esters. The content thereof is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight.
本发明中，所述的光刻胶清洗剂组合物还可进一步含有选自极性有机共 溶剂、表面活性剂和除硼酸、 硼酸盐和硼酸酯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 50wt%， 但不包括 0wt%， 更 佳的为 5〜30wt%;所述的表面活性剂含量较佳的为 5wt%，但不包括 0wt%， 更佳的为 0.05〜3.0wt%; 所述的除硼酸、 硼酸盐和硼酸酯的缓蚀剂以外的其 它缓蚀剂含量较佳的为 5.0wt%， 但不包括 0wt%， 更佳的为 0.05~3.0wt%。  In the present invention, the photoresist cleaning composition may further comprise one selected from the group consisting of a polar organic cosolvent, a surfactant, and a corrosion inhibitor other than boric acid, borate and boric acid ester. Or a variety. The polar organic co-solvent content is preferably 50% by weight, but does not include 0% by weight, more preferably 5 to 30% by weight; the surfactant content is preferably 5% by weight, but not including 0% by weight. More preferably, it is 0.05 to 3.0% by weight; the content of the corrosion inhibitor other than the corrosion inhibitor of boric acid, borate and boric acid ester is preferably 5.0% by weight, but does not include 0% by weight, more Preferably, it is 0.05 to 3.0% by weight.
本发明中， 所述的极性有机共溶剂较佳的选自亚砜、 砜、 咪唑院酮、 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二乙基 亚砜和 /或甲乙基亚砜；所述的砜较佳的选自甲基砜、乙基砜和环丁砜中的一 种或多种， 更佳的为环丁砜； 所述的咪唑垸酮较佳的选自 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；所述的醇胺较佳的选自一乙醇胺、三乙醇胺、二甘醇胺、 异丙醇胺、 甲基乙醇胺、 甲基二乙醇胺、 二甲基乙醇胺和羟乙基乙二胺中的 一种或多种， 更佳的选自一乙醇胺、 三乙醇胺、 二甘醇胺和甲基乙醇胺中的 一种或多种； 所述的垸基二醇单垸基醚较佳的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， 更佳的选自二乙二醇单甲醚、 二丙 二醇单甲醚和二丙二醇单丁醚中的一种或多种。 In the present invention, the polar organic co-solvent is preferably one or more selected from the group consisting of sulfoxides, sulfones, imidazoles, alcoholamines, and mercaptodiol monodecyl ethers. Wherein, the sulfoxide is preferably diethyl sulfoxide and/or methyl ethyl sulfoxide; and the sulfone is preferably one or more selected from the group consisting of methyl sulfone, ethyl sulfone and sulfolane. More preferably, it is sulfolane; the imidazolium is preferably selected from the group consisting of 2-imidazolium, 1,3-dimethyl-2-imidazolium and 1,3-diethyl-2-imidazolium One or more of them, more preferably 1,3-dimethyl-2-imidazolium; the alcohol amine is preferably selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, isopropanol In amines, methylethanolamine, methyldiethanolamine, dimethylethanolamine and hydroxyethylethylenediamine One or more, more preferably one or more selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, and methylethanolamine; the mercaptodiol monodecyl ether is preferably selected from the group consisting of One or more of ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether More preferably, it is one or more selected from the group consisting of diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monobutyl ether.
本发明中， 所述的表面活性剂较佳的选自聚乙烯醇、 聚乙烯吡咯垸酮和 聚氧乙烯醚中的一种或多种，更佳的为聚乙烯吡咯垸酮和 /或聚氧乙烯醚。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。  In the present invention, the surfactant is preferably selected from one or more of polyvinyl alcohol, polyvinylpyrrolidone and polyoxyethylene ether, more preferably polyvinylpyrrolidone and/or poly. Oxyethylene ether. The number average molecular weight of the surfactant is preferably from 500 to 20,000, more preferably from 1,000 to 10,000.
本发明中， 所述的除硼酸、 硼酸盐和硼酸酯以外的其它缓蚀剂较佳的选 自醇胺类、 唑类、 膦酸类和聚丙烯酸类缓蚀剂中的一种或多种。 其中， 所述 的醇胺类缓蚀剂较佳的选自一乙醇胺、 三乙醇胺、 二甘醇胺、 异丙醇胺、 甲 基乙醇胺、 甲基二乙醇胺、 二甲基乙醇胺和羟乙基乙二胺中的一种或多种， 更佳的选自一乙醇胺、 三乙醇胺、 二甘醇胺和甲基乙醇胺中的一种或多种； 所述的唑类缓蚀剂较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、 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 i_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 -1,2,4-三氮唑、 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 缓蚀剂较佳的选自 1-羟基亚乙基 -U-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， 更佳的选自 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。 In the present invention, the corrosion inhibitor other than boric acid, borate and boric acid ester is preferably selected from one of an alcohol amine, an azole, a phosphonic acid and a polyacrylic corrosion inhibitor. A variety. Wherein, the alcohol amine corrosion inhibitor is preferably selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, isopropanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine and hydroxyethylethyl One or more of the diamines, more preferably one or more selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, and methylethanolamine; the azole inhibitor is preferably selected from the group consisting of Benzotriazole, methylbenzotriazole, benzotriazole diethanolamine salt, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, dimercaptothiadiazole , 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3,5 -diamino-1,2,4-triazole, 4-amino-5-mercapto-1,2,4-triazole, 5-amino-tetrazole and i_phenyl-5-fluorenyltetrazine One or more of the azoles, more preferably selected from the group consisting of benzotriazole, methylbenzotriazole, benzotriazole diethanolamine salt, 3-amino-1,2,4-triazole , one of 4-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole and 5-amino-tetrazole a plurality of; the phosphonic acid corrosion inhibitor is preferably selected from the group consisting of 1-hydroxyethylidene-U-diphosphonic acid, aminotrimethylenephosphonic acid, 2-phosphonium bromide-1, 2,4- One of tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriamine pentamethylenephosphonic acid Or a plurality, more preferably one selected from the group consisting of 2-phosphonobutane-1,2,4-tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid Or a variety.
本发明中，所述的聚丙烯酸类缓蚀剂较佳的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，更佳的选自丙 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铵盐中的一 种或多种。所述的聚丙烯酸类缓蚀剂的数均分子量较佳的为 500〜100000，更 佳的为 1000~50000。所述的聚丙烯酸类缓蚀剂对金属如铝的腐蚀表现出极强 的抑制作用。  In the present invention, 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, and methacrylic polymers. More preferably, one or more of an alcohol amine salt, a polyoxyethylene-modified acrylic polymer, an ester thereof and an alkanolammonium salt, and a polyoxyethylene-modified methacrylic acid polymer, and an ester thereof and an alkanolammonium salt. An alcohol amine polymer or 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 an alkanolammonium thereof One or more of the salts. The polyacrylic corrosion inhibitor preferably has a number average molecular weight of from 500 to 100,000, more preferably from 1,000 to 50,000. The polyacrylic corrosion inhibitor exhibits a strong inhibitory effect on corrosion of metals such as aluminum.
本发明所用试剂及原料均市售可得。  The reagents and starting materials used in the present invention are commercially available.
本发明的光刻胶清洗剂组合物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组合物可在较宽的温度范围内使用 （ 20~85 之 间）。 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组 合物中， 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。  The photoresist cleaning composition of the present invention can be obtained by simply mixing the components described above. The photoresist cleaner composition of the present invention can be used over a wide temperature range (between 20 and 85). The cleaning method can be referred to the following steps: The semiconductor wafer containing the photoresist is immersed in the cleaning composition, slowly shaken at 20 to 85 ° C with a constant temperature oscillator, then washed with deionized water and then dried with high purity nitrogen.
相比于现有技术， 本发明的有益效果如下：  Compared with the prior art, the beneficial effects of the present invention are as follows:
( 1 ) 本发明的光刻胶清洗剂组合物可以较为迅速地清洗金属、 金属合 金或电介质等基材上的 20μπ 以上厚度的光刻胶和其它刻蚀残留物。  (1) The photoresist cleaning composition of the present invention can relatively quickly clean photoresist and other etching residues having a thickness of 20 μπ or more on a substrate such as a metal, a metal alloy or a dielectric.
(2) 本发明的光刻胶清洗剂组合物含有的垸基二醇芳基醚可以提高季 铵氢氧化物在二甲基亚砜中的溶解度。季铵氢氧化物溶解度的增加有利于提 高本发明中光刻胶清洗剂组合物对光刻胶尤其是厚膜光刻胶的清洗能力。(2) The mercapto diol aryl ether contained in the photoresist cleaning composition of the present invention can improve the solubility of the quaternary ammonium hydroxide in dimethyl sulfoxide. The increase in the solubility of quaternary ammonium hydroxide is beneficial to The cleaning ability of the photoresist cleaning composition of the present invention to a photoresist, especially a thick film photoresist.
( 3 ) 本发明的光刻胶清洗剂组合物中含有的垸基二醇芳基醚以及选自 硼酸、 硼酸盐和硼酸酯的缓蚀剂能够在晶片图案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案和基材的攻击， 从而降低晶片 图案和基材的腐蚀； 尤其是其含有的选自硼酸、硼酸盐和硼酸酯的缓蚀剂对 金属如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 硅等非金属材料表现出极弱的腐蚀性。 (3) a mercapto diol aryl ether contained in the photoresist cleaning composition of the present invention and a corrosion inhibitor selected from the group consisting of boric acid, borate and boric acid ester capable of forming a layer on the wafer pattern and the surface of the substrate The protective film prevents the attack of the wafer pattern and the substrate by halogen atoms, hydroxide ions, etc., thereby reducing the corrosion of the wafer pattern and the substrate; in particular, it contains corrosion inhibition selected from the group consisting of boric acid, borate and boric acid ester. The agent exhibits a good inhibitory effect on the corrosion of metals such as aluminum. Therefore, it exhibits extremely weak corrosiveness to metals such as aluminum and copper and non-metal materials such as silica.
(4 ) 本发明的光刻胶清洗剂组合物可以通过溶解的方式去除半导体晶 片上的高交联度的厚膜负性光刻胶， 避免光刻胶在晶片表面的沉积或粘连， 且不会造成晶片图案的腐蚀或损坏。  (4) The photoresist cleaning composition of the present invention can remove a high-crosslinking thick film negative photoresist on a semiconductor wafer by dissolution to prevent deposition or adhesion of the photoresist on the surface of the wafer, and It can cause corrosion or damage to the wafer pattern.
( 5 )本发明的光刻胶清洗剂组合物可以在较宽的温度范围内（ 20-85。C ) 使用。 发明内容  (5) The photoresist cleaning composition of the present invention can be used over a wide temperature range (20-85 ° C). Summary of the invention
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在 所述的实施例范围之中。 下述实施例中， 百分比均为质量百分比。  The invention is further illustrated by the following examples, which are not intended to limit the invention. In the following examples, the percentages are all by mass.
实施例 1~26  Example 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。  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.
本发明光刻胶实施例 1~26  Photoresist embodiment 1~26 of the present invention
季铵氢氧化物 垸基二醇芳基醚 二甲 硼酸、硼酸盐或 Ϊ ffl酸酯 其它  Quaternary ammonium hydroxide, mercapto diol aryl ether, dimethylboronic acid, borate or Ϊffl acid ester, other
实 水 基亚  Real water
施 具体 ύ m. 含量 具体 砜 具体 含量 具体  Specific ύ m. content specific sulfone specific content specific
例 物质 wt% wt% 物质 wt% a M 物质 wt% 物质 Wt% wt% 四甲基氢氧化 丙二醇单苯 Example material wt% wt% substance wt% a M substance wt% substance Wt% wt% Tetramethyl propylene glycol monobenzene
0.5 0.5 0.99 98 硼酸 0.01 1 1 铰 基醚  0.5 0.5 0.99 98 boric acid 0.01 1 1 hinge ether
四乙基氢氧化 异丙二醇单 Tetraethyl hydroxide
1 1 7.9 90 苯硼酸 0.1 1 1 铰 苯基魅  1 1 7.9 90 phenylboronic acid 0.1 1 1 hinge phenyl charm
四丙基氢氧化 二乙二醇单 Tetrapropyl hydroxide diethylene glycol single
1.5 5 0.5 42.5 2-甲基苯硼酸 0.5 二乙基亚砜 50 铰 苯基 四丁基氢氧化 二丙二醇单 聚乙烯醇 (数均分子量为  1.5 5 0.5 42.5 2-methylbenzeneboronic acid 0.5 diethyl sulfoxide 50 hinge phenyl tetrabutyl hydride dipropylene glycol monovinyl alcohol (number average molecular weight is
2 2 10 85.75 3-甲基苯硼酸 0.2 0.05 铰 苯基醚 500)  2 2 10 85.75 3-methylbenzeneboronic acid 0.2 0.05 hinged phenyl ether 500)
4-甲基苯硼酸 3 4-methylbenzeneboronic acid 3
苄基三甲基氢 二异丙二醇 聚氧乙烯改性的聚甲基丙 Benzyltrimethylhydrogen diisopropyl glycol polyoxyethylene modified polymethyl propylene
10 15 30 30 5  10 15 30 30 5
单苯基醚 硼酸 1  Monophenyl ether boric acid 1
氧化铵 烯酸 (数均分子量为 10000)  Ammonium oxide enoic acid (number average molecular weight is 10,000)
硼酸乙醇胺盐 6  Borate ethanolamine salt 6
2,3-二甲基苯硼 甲乙基亚砜 30  2,3-dimethylphenylboron methylethyl sulfoxide 30
1  1
酸 三乙醇胺 4 四甲基氢氧化 三乙二醇单  Acid triethanolamine 4 tetramethyl hydroxide triethylene glycol single
5 5 20 30 聚乙烯吡咯垸酮 (数均分子 3 铵 苯基醚  5 5 20 30 Polyvinylpyrrolidone (number average molecule 3 ammonium phenyl ether)
4-乙基苯硼酸 1 量为 20000)  4-ethylbenzeneboronic acid 1 amount is 20000)
甲基苯并三氮唑 0.5 苯并三氮唑 0.5 甲基砜 5 一乙醇胺 30 四丁基氢氧化 三丙二醇单  Methylbenzotriazole 0.5 benzotriazole 0.5 Methyl sulfone 5 monoethanolamine 30 tetrabutyl hydride tripropylene glycol
2.2 7 8 42.04 4-丙基苯硼酸 0.75 聚氧乙烯醚 (数均分子量为  2.2 7 8 42.04 4-propylbenzeneboronic acid 0.75 polyoxyethylene ether (number average molecular weight is
5 铰 苯基 ffi 10000)  5 hinge phenyl ffi 10000)
聚丙烯酸 (数均分子量为  Polyacrylic acid (number average molecular weight is
0.01 0.01
500) 500)
乙基砜 40 Ethyl sulfone 40
4-丁基苯硼酸 0.25 4-butylbenzeneboronic acid 0.25
二甘醇胺 5 四乙基氢氧化 三异丙二醇  Diethylene glycolamine 5 tetraethyl hydroxide triisopropyl glycol
2.5 2.5 5 44.44 聚乙烯醇 (数均分子量为  2.5 2.5 5 44.44 Polyvinyl alcohol (number average molecular weight is
0.01 铵 单苯基醚 2-甲氧基苯硼 500)  0.01 ammonium monophenyl ether 2-methoxyphenyl boron 500)
0.25  0.25
酸 丙烯酸-马来酸共聚物 (数均  Acid acrylic acid-maleic acid copolymer
0.05 分子量为 1500)  0.05 molecular weight is 1500)
四丙基氢氧化 六缩乙二醇 Tetrapropyl hydroxide hexaethylene glycol
1.5 2 环丁砜 15 铵 单苯基醚  1.5 2 sulfolane 15 ammonium monophenyl ether
3-甲氧基苯硼  3-methoxyphenyl boron
3.5 70.98 0.5 异丙醇胺 1 苄基三甲基氢 六缩丙二醇 酸  3.5 70.98 0.5 isopropanolamine 1 benzyltrimethylhydrogen hexapropylene glycol acid
1.5 4 聚甲基丙烯酸 (数均分子量 氧化 单苯基醚 0.02  1.5 4 Polymethacrylic acid (number average molecular weight oxidation monophenyl ether 0.02
为 2500) 四甲基氢氧化 2500) Tetramethyl hydroxide
2.5 2-咪唑垸酮 30 铵  2.5 2-imidazolium 30 ammonium
甲基亡乙醇胺 2 六缩异丙二 4-甲氧基苯硼  Methyl-decanolamine 2 hexa-isopropylidene 4-methoxyphenyl boron
4.5 12 46.45 1  4.5 12 46.45 1
四乙基氢氧化 醇单苯基醚 酸 甲基丙烯酸-马来酸共聚物 Tetraethyl hydroxide alcohol monophenyl ether acid methacrylic acid-maleic acid copolymer
1 0.05 铰 (数均分子量为 1000)  1 0.05 hinge (number average molecular weight is 1000)
2-巯基苯并噻唑 0.52-mercaptobenzothiazole 0.5
3,4-二甲氧基苯 3,4-dimethoxybenzene
0.1 1,3-二甲基 -2-咪唑烷酮 5 硼酸  0.1 1,3-dimethyl-2-imidazolidinone 5 boric acid
四丙基氢氧化 丙二醇单苄 Tetrapropyl hydroxide propylene glycol monobenzyl
3 3 65 12.5 二甲基乙醇胺 10 铵 基醚  3 3 65 12.5 Dimethylethanolamine 10 Ammonium ether
2-羧基苯硼酸 0.4 聚丙烯酸三乙醇胺盐 (数均  2-carboxybenzeneboronic acid 0.4 polyacrylic acid triethanolamine salt (number average
1 分子量为 20000) 1 molecular weight is 20000)
3-羧基苯硼酸 0.5 1,3-二乙基 -2-咪唑垸酮 42 苄基三甲基氢 异丙二醇单 3-carboxybenzeneboronic acid 0.5 1,3-diethyl-2-imidazolium 42 benzyltrimethylhydropropanediol
6.5 6 15 18 4-羧基苯硼酸 0.5 羟乙基乙二胺 8 氧化铰 苄基醚  6.5 6 15 18 4-Carboxyphenylboronic acid 0.5 Hydroxyethylethylenediamine 8 Oxidized hinge Benzyl ether
2-羟甲基苯硼 聚甲基丙烯酸一乙醇胺盐  2-hydroxymethylbenzene boron polyethyl methacrylate monoethanolamine salt
0.5 3 酸 (数均分子量为 10000)  0.5 3 acid (number average molecular weight is 10000)
一乙醇胺 20 Monoethanolamine 20
2-巯基苯并咪唑 0.5 四乙基氢氧化 己二醇单萘 3-羟甲基苯硼 2-巯基苯并噁唑 0.5 2-mercaptobenzimidazole 0.5 tetraethyl hydroxide hexanediol mononaphthalene 3-hydroxymethylphenyl boron 2-mercaptobenzoxazole 0.5
0.1 0.2 0.1 78 0.1  0.1 0.2 0.1 78 0.1
铵 基醚 酸  Ammonium ether acid
聚氧乙烯改性的聚甲基丙 烯酸甲酯 (数均分子量为 0.5 75000)  Polyoxyethylene modified polymethyl methacrylate (number average molecular weight is 0.5 75000)
三乙醇胺 3.5 苯并三氮唑二乙醇胺盐 0.5 四丁基氢氧化 丙二醇单苯 4-羟甲基苯硼  Triethanolamine 3.5 benzotriazole diethanolamine salt 0.5 tetrabutyl hydroxide propylene glycol monophenyl 4-hydroxymethyl boron boron
7 6 40 40 1.5  7 6 40 40 1.5
铵 基醚 酸 聚氧乙烯改性的聚丙烯酸  Ammonium ether acid polyoxyethylene modified polyacrylic acid
1.5 乙酯 (数均分子量为 50000) 二甘醇胺 1 1.5 ethyl ester (number average molecular weight is 50000) diethylene glycol amine 1
2-噻吩硼酸 0.2 2-thiopheneboronic acid 0.2
1-苯基 -5-巯基四氮唑 0.5 1-phenyl-5-mercaptotetrazole 0.5
3-氨基 -5-巯基 -1,2,4-三氮唑 0.1 四甲基氢氧化 二丙二醇单 3-amino-5-mercapto-1,2,4-triazole 0.1 tetramethyl hydroxide dipropylene glycol single
3.5 4 9 80.5  3.5 4 9 80.5
铰 苯基醚  Hinge phenyl ether
3-噻吩硼酸 0.2 聚氧乙烯改性的聚丙烯酸  3-thiophene boric acid 0.2 polyoxyethylene modified polyacrylic acid
一乙醇胺盐 (数均分子量为 1 40000) 异丙醇胺 1.5 Monoethanolamine salt (number average molecular weight is 1 40000) Isopropanolamine 1.5
萘硼酸 0.05  Naphthalene borate 0.05
二巯基噻二唑 0.30 四丙基 it氧化 丙二醇单苄  Dimercaptothiadiazole 0.30 tetrapropyl it oxidation propylene glycol monobenzyl
2 3 8 85 聚氧乙烯醚 (数均分子量为  2 3 8 85 polyoxyethylene ether (number average molecular weight is
0.05 铵 基醚 硼酸二乙醇胺 10000)  0.05 ammonium ether boric acid diethanolamine 10000)
0.05  0.05
±卜  ±卜
聚乙烯吡咯烷酮 (分子量为  Polyvinylpyrrolidone (molecular weight is
0.05 0.05
20000) 20000)
异丙二醇单 硼酸 1.5 甲基二乙醇胺 5  Isopropanediol monoboric acid 1.5 methyldiethanolamine 5
10  10
苯基醚 四甲基硼酸铰 1 5-氨基-四氮唑 1.5 苄基三甲基氢  Phenyl ether tetramethylborate hinge 1 5-amino-tetrazol 1.5 benzyl trimethyl hydrogen
8.5 8 46.5  8.5 8 46.5
氧化铰 丙二醇单苯 硼酸三乙醇胺  Oxidized hinge propylene glycol monophenyl borate triethanolamine
15 2 聚氧乙烯改性的聚甲基丙 1 基醚 ±卜  15 2 Polyoxyethylene modified polymethyl propyl 1-ether ether
烯酸 (数均分子量为 10000) 甲基乙醇胺 7.5 四乙基硼酸铵 0.3  Oleic acid (number average molecular weight is 10000) methylethanolamine 7.5 tetraethylammonium borate 0.3
二巯基噻二唑 1.2 四乙基氢氧化 二乙二醇单  Dimercaptothiadiazole 1.2 tetraethyl hydroxide diethylene glycol single
2.5 10 5 72.8  2.5 10 5 72.8
铰 苯基醚 聚氧乙烯改性的聚丙烯酸  Hindyl ether polyoxyethylene modified polyacrylic acid
四丙基硼酸铰 0.3 三乙醇胺盐 (数均分子量为 0.4  Tetrapropylboronic acid hinge 0.3 Triethanolamine salt (number average molecular weight is 0.4
100000) 二丙二醇单 四丁基硼酸铰 0.2 羟乙基乙二胺 6  100000) dipropylene glycol monotetrabutylborate hinge 0.2 hydroxyethyl ethylenediamine 6
5  5
苯基醚 硼酸三甲酯 0.2 3-氨基 -1,2,4-三氮唑 2 四丁基氢氧化 聚氧乙烯改性的聚甲基丙  Phenyl ether Trimethyl borate 0.2 3-Amino -1,2,4-triazole 2 Tetrabutyl hydroxide Polyoxyethylene modified polymethyl propylene
4.5 5 67.5  4.5 5 67.5
铰 二异丙二醇 硼酸异丙醇胺 烯酸二乙醇胺盐 (数均分子 2  Hinge diisopropyl glycol boronic acid isopropanolamine enoic acid diethanolamine salt (number average molecule 2
5 0.6  5 0.6
单苯基醚 ±卜 量为 8000) 二甲基乙醇胺 2 硼酸二甘醇胺 二乙二醇单甲醚 30  Monophenyl ether ± Bu amount is 8000) Dimethylethanolamine 2 Boric acid diethylene glycol amine Diethylene glycol monomethyl ether 30
0.5  0.5
4-氨基 -1,2,4-三氮唑 0.5 四甲基氢氧化 三乙二醇单  4-amino-1,2,4-triazole 0.5 tetramethyl hydroxide triethylene glycol single
2 3 15 48.69 聚甲基丙烯酸一乙醇胺盐 铰 苯基醚 0.01  2 3 15 48.69 polyethyl methacrylate monoethanolamine salt phenyl ether 0.01
硼酸铵 0.2 (数均分子量为 10000)  Ammonium borate 0.2 (number average molecular weight is 10000)
二甘醇胺 0.1 三丙二醇单 异戊二醇硼酸 二乙二醇单乙醚 5  Diethylene glycolamine 0.1 tripropylene glycol monoisopentanediol boric acid diethylene glycol monoethyl ether 5
6  6
苯基醚 酯 1-羟基亚乙基 -1,1-二膦酸 0.5 四丙基氢氧化  Phenyl ether ester 1-hydroxyethylidene-1,1-diphosphonic acid 0.5 tetrapropyl hydroxide
2.5 2.5 77  2.5 2.5 77
铰  Hinge
三异丙二醇 硼酸甲基二乙 聚氧乙烯改性的聚丙烯酸  Triisopropyl diol boric acid methyl diethylene polyoxyethylene modified polyacrylic acid
4 1 0.5 单苯基醚 醇胺盐 一乙醇胺盐 (数均分子量为  4 1 0.5 monophenyl ether alcohol amine salt monoethanolamine salt (number average molecular weight is
40000) 丙二醇单苯 苄基三甲基硼 二乙二醇单丁醚 2.4 40000) Propylene glycol monophenylbenzyltrimethylborane diethylene glycol monobutyl ether 2.4
25 1  25 1
基醚 酸铰 一乙醇胺 20  Base ether acid hinge monoethanolamine 20
硼酸甲基乙醇  Boric acid methyl alcohol
苄基三甲基氢 4 氨基三亚甲基膦酸 0.1 Benzyltrimethylhydrogen 4 aminotrimethylenephosphonic acid 0.1
9 9 1 胺盐  9 9 1 amine salt
氧化铵 二丙二醇单  Ammonium oxide dipropylene glycol single
25 聚氧乙烯改性的聚甲基丙 苯基醚 双联邻苯二酚  25 polyoxyethylene modified polymethyl propyl ether double catechol
1 烯酸二乙醇胺盐 (数均分子 2.5 硼酸酯  1 enoic acid diethanolamine salt (number average molecule 2.5 borate
量为 8000)  The quantity is 8000)
六缩乙二醇 丙二醇单丁醚 30  Hexaethylene glycol propylene glycol monobutyl ether 30
8 硼酸频哪醇酯 2  8 Boronic acid pinacol ester 2
单苯基醚 2-膦酸丁垸 -1,2，4-三羧酸 0.05 四丁基氢氧化 聚氧乙烯醚 (数均分子量为  Monophenyl ether 2-butylphosphonium bromide -1,2,4-tricarboxylic acid 0.05 tetrabutyl hydroxide polyoxyethylene ether (number average molecular weight is
5 5 41.95 硼酸三乙酯 1 0.5 铵 10000)  5 5 41.95 Triethyl borate 1 0.5 ammonium 10000)
六缩丙二醇  Hexapropylene glycol
4  4
单苯基醚  Monophenyl ether
硼酸三丁酯 1 聚氧乙烯改性的聚甲基丙 1.5  Tributyl borate 1 polyoxyethylene modified polymethyl propyl 1.5
烯酸 (数均分子量为 10000) 六缩异丙二 二丙二醇单甲醚 20  Oleic acid (number average molecular weight 10000) hexaisopropylidene dipropylene glycol monomethyl ether 20
4 苯硼酸 0.5  4 phenylboronic acid 0.5
醇单苯基醚 乙二胺四亚甲基膦酸 0.2 四甲基氢氧化  Alcohol monophenyl ether ethylenediamine tetramethylene phosphonic acid 0.2 tetramethyl hydroxide
2 12.5 53 聚氧乙烯改性的聚丙烯酸 铵 丙二醇单苄 0.5  2 12.5 53 Polyoxyethylene modified polyacrylic acid ammonium Propylene glycol monobenzyl 0.5
4 硼酸三丙酯 0.3 (数均分子量为 5000) 基醚  4 Tripropyl borate 0.3 (number average molecular weight is 5000)
甲基乙醇胺 3 二丙二醇单乙醚 15 Methylethanolamine 3 dipropylene glycol monoethyl ether 15
2-羧基苯硼酸 0.25 2-carboxybenzeneboronic acid 0.25
二乙烯三胺五亚甲基膦酸 0.2 四丙基氢氧化 丙二醇单苯  Diethylenetriamine penta methylene phosphonic acid 0.2 tetrapropyl hydroxide propylene glycol monobenzene
2.5 2.5 8 70.5 3,5-二氨基 -1 ,2,4-三氮唑 0.2 铵 基醚  2.5 2.5 8 70.5 3,5-diamino-1,2,4-triazole 0.2 ammonium ether
硼酸咪唑啉酯 0.25  Imidazolium borate 0.25
聚氧乙烯醚 (数均分子量为  Polyoxyethylene ether (number average molecular weight is
0.6 10000)  0.6 10000)
二丙二醇单丁魅 25 一乙醇胺 5 四乙基氢氧化 异丙二醇单 4-氨基 -5-巯基 -1 ,2,4-三氮唑 0.3  Dipropylene glycol monobutanol 25 monoethanolamine 5 tetraethyl hydroxide isopropyl glycol mono 4-amino-5-mercapto-1,2,4-triazole 0.3
3 3 10 48.2 硼酸乙醇胺盐 5  3 3 10 48.2 Borate ethanolamine salt 5
铵 苯基魅  Ammonium phenyl charm
聚氧乙烯改性的聚丙烯酸 一乙醇胺盐 (数均分子量为 0.5 40000)  Polyoxyethylene modified polyacrylic acid monoethanolamine salt (number average molecular weight is 0.5 40000)
下面通过本发明优选的效果实施例来进一步说明本发明的有益效果。 效果实施例 Advantageous effects of the present invention will be further hereinafter described by way of preferred effect embodiments of the present invention. Effect embodiment
表 2 给出了对比清洗剂 Γ〜7，和本发明的光刻胶清洗剂组合物实施例 27~42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。 Table 2 shows comparative cleaning agents Γ~7, and the photoresist cleaning composition embodiment of the present invention The formula of 27~42 is simply mixed evenly according to the components listed in Table 2 and their contents, that is, each cleaning agent is prepared.
表 2 对比实施例清洗剂 Γ~7'和本发明光刻胶清洗剂组合物实施例 27~42的组分和  Table 2 Comparative Example Cleaning Agent Γ~7' and the composition of the photoresist cleaning composition of the present invention, examples 27 to 42 and
Figure imgf000015_0001
将表 2中的各组分按照比例混合均匀， 制得对比实施例清洗剂 Γ〜7，和 本发明实施例清洗剂 27〜42。 其中， 除对比实施例清洗剂 7'中有少量颗粒状 的四甲基氢氧化铰以外， 对比实施例清洗剂 1，〜6，和本发明实施例清洗剂 27-42均为澄清透明的均相溶液。
Figure imgf000015_0001
The components in Table 2 were uniformly mixed in proportion to obtain a comparative example of the cleaning agent Γ~7, and the cleaning agents 27 to 42 of the present invention. Wherein, in addition to a small amount of granular tetramethylammonium hydroxide hinge in the cleaning agent 7' of the comparative example, Comparative Example Cleaning Agents 1, -6, and the cleaning agent of the present invention 27-42 are clear and transparent homogeneous solutions.
将对比实施例清洗剂 Γ~6，与本发明实施例清洗剂 27〜42对三种空白晶 片和含有光刻胶的半导体晶片进行清洗， 测试结果见表 3。  The comparative example cleaning agent Γ~6, and the cleaning agent 27~42 of the embodiment of the present invention were used to clean the three blank wafers and the semiconductor wafer containing the photoresist, and the test results are shown in Table 3.
1、将对比实施例清洗剂 Γ〜6'和本发明实施例清洗剂 27〜42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晶片浸入清洗剂中， 在 20〜85°C下利用恒温振荡器振荡 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。  1. Comparative Example Cleaner Γ~6' and Inventive Example Cleaner 27~42 were used to clean the blank Cu wafer and measure its corrosion to metallic Cu. Test methods and conditions: 4 4 4 cm blank Cu wafer was immersed in a cleaning agent, oscillated with a constant temperature oscillator at 20 to 85 ° C for 60 minutes, then washed with deionized water and then dried with high purity nitrogen gas. The needle gauge measures the change of the surface resistance of the blank Cu wafer before and after etching. The results are shown in Table 3.
2、将对比实施例清洗剂 Γ〜6'和本发明实施例清洗剂 27~42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晶片浸入清洗剂中， 在 20〜85°C下利用恒温振荡器振荡 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。  2. Comparative Example Cleaner Γ~6' and Inventive Example Cleaner 27~42 were used to clean the blank A1 wafer and determine its corrosion to metal A1. Test methods and conditions: The 4 X 4 cm blank A1 wafer was immersed in a cleaning agent, shaken at 20 to 85 ° C for 60 minutes using a constant temperature oscillator, then washed with deionized water and then dried with high purity nitrogen gas, using a quadrupole probe. The needle gauge was used to measure the change in surface resistance of the blank A1 wafer before and after etching. The results are shown in Table 3.
3、将对比实施例清洗剂 Γ〜6'和本发明实施例清洗剂 27〜42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晶片浸入清洗剂中， 在 20〜85°C下 利用恒温振荡器振荡 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。  3. The comparative example cleaning agent Γ~6' and the cleaning agent 27~42 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, shaken at 20 to 85 ° C for 60 minutes using a constant temperature oscillator, and then washed with deionized water and then dried with high purity nitrogen. The thickness of the TEOS thickness before and after cleaning of the blank TEOS wafer was calculated using a Nanospec 6100 thickness gauge. The results are shown in Table 3.
4、将对比实施例清洗剂 1，〜6，和本发明实施例清洗剂 27〜42用于清洗半 导体晶片上的光刻胶。 清洗方法如下： 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。 4. The comparative example cleaning agents 1, -6, and the cleaning agents 27 to 42 of the present invention are used to clean the photoresist on the semiconductor wafer. The cleaning method is as follows: Immerse the semiconductor wafer (containing pattern) containing a negative acrylate photoresist (having a thickness of about 60 μm and exposed and etched) into the cleaning agent. The mixture was shaken at 20 to 85 ° C for 1 to 30 minutes using a constant temperature oscillator, and then washed with deionized water and then dried with high purity nitrogen gas. The cleaning effect of the photoresist and the corrosion of the wafer pattern by the cleaning agent are shown in Table 3.
表 3 对比实施例清洗剂 1 '〜6'和本发明实施例清洗剂 27~42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  Table 3 Corrosion of the cleaning agent 1 '~6' of the comparative example and the cleaning agent 27~42 of the embodiment of the invention on the metal Cu and A1 and the non-metallic TEOS and the cleaning of the negative photoresist
Figure imgf000017_0001
Figure imgf000017_0001
腐蚀情况： ◎ 基本无腐蚀； 清洗情况： ◎ 完全去除;  Corrosion: ◎ Basically non-corrosive; Cleaning condition: ◎ Completely removed;
o 略有腐蚀； ' 〇 少量残余: Δ 中等腐蚀; △较多残余; o slightly corroded; ' 〇 a small amount of residue: Δ medium corrosion; △ more residual;
X 严重腐蚀。 X 大量残余。  X is severely corroded. X has a lot of residuals.
将含有高交联度的负性丙烯酸酯类光刻胶（厚度约为 150微米， 且经过 曝光和刻蚀） 的半导体晶片 （含有图案）浸入表 2中所示的本发明实施例清 洗剂 32~42中， 在 40〜85°C下利用恒温振荡器振荡 10〜60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 4所示。 A semiconductor wafer (containing a pattern) containing a high degree of crosslinking of a negative acrylate-based photoresist (having a thickness of about 150 μm and exposed and etched) was immersed in the cleaning agent 32 of the present invention shown in Table 2. In ~42, it was shaken at 40 to 85 ° C for 10 to 60 minutes using a constant temperature oscillator, and then washed with deionized water and then dried with high purity nitrogen gas. The cleaning effect of the photoresist and the corrosion of the wafer pattern by the cleaning agent are shown in Table 4.
表 2中实施例清洗剂 32〜42对负性丙烯酸酯类光刻胶  Example 2 cleaning agent 32~42 negative acrylate photoresist
(厚度约为 150微米） 的清洗情况  Cleaning (about 150 microns thick)
Figure imgf000018_0001
Figure imgf000018_0001
腐蚀情况： ◎ 基本无腐蚀; 清洗情况： ◎ 完全去除;  Corrosion: ◎ Basically non-corrosive; Cleaning condition: ◎ Completely removed;
o 略有腐蚀； o 少量残余;  o slightly corroded; o a small amount of residue;
△ 中等腐蚀； Δ较多残余;  △ medium corrosion; Δ more residual;
X 严重腐蚀。 X 大量残余。  X is severely corroded. X has a lot of residuals.
从表 3和表 4可以看出， 与对比实施例清洗剂 Γ〜6，相比， 本发明实施 例清洗剂 27~42对厚膜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 无腐蚀或损坏。 It can be seen from Table 3 and Table 4 that compared with the cleaning agent Γ~6 of the comparative example, the cleaning agent 27~42 of the embodiment of the present invention has good cleaning ability for the thick film negative acrylate photoresist, and is used. Warm Wide range of degrees, low corrosivity to metallic Cu and A1 and non-metallic TEOS, no corrosion or damage to the wafer pattern.
综上所述， 本发明的光刻胶清洗剂组合物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以上厚度的光刻胶和其它刻蚀残留物。 其 对铝和铜等金属以及二氧化硅等非金属材料表现出极弱的腐蚀性， 并不会造 成晶片图案的腐蚀或损坏， 且可在较宽的温度范围 （20〜85°C ) 内使用。  In summary, the photoresist cleaning composition of the present invention can relatively quickly clean photoresist and other etching residues having a thickness of 20 μm or more on a substrate such as a metal, a metal alloy or a dielectric. It exhibits extremely weak corrosive properties to metals such as aluminum and copper and non-metallic materials such as silicon dioxide, and does not cause corrosion or damage to the wafer pattern, and can be used in a wide temperature range (20 to 85 ° C). use.

Claims

权利要求 Rights request
1、 一种光刻胶清洗剂组合物， 包含季铵氢氧化物、 水、 垸基二醇芳基 醚、 二甲基亚砜和缓蚀剂， 其特征在于， 所述的垸基二醇芳基醚中烷基二醇 的碳原子数目为 3〜18，所述的缓蚀剂包含选自硼酸、硼酸盐和硼酸酯中的一 种或多种。 A photoresist cleaning composition comprising quaternary ammonium hydroxide, water, mercapto diol aryl ether, dimethyl sulfoxide and a corrosion inhibitor, characterized in that the mercapto diol is aromatic The alkyl diol in the ether has a carbon number of from 3 to 18, and the corrosion inhibitor comprises one or more selected from the group consisting of boric acid, borate and boric acid ester.
2、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于， 所述的季 铵氢氧化物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。  2. The photoresist cleaning composition according to claim 1, wherein the quaternary ammonium hydroxide is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. One or more of ammonium, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide.
3、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于， 所述的季 铵氢氧化物的含量为 0.1~10wt%。  The photoresist cleaning composition according to claim 1, wherein the quaternary ammonium hydroxide is contained in an amount of 0.1 to 10% by weight.
4、 如权利要求 3所述的光刻胶清洗剂组合物， 其特征在于， 所述的季 铵氢氧化物的含量为 l~5wt%。  The photoresist cleaning composition according to claim 3, wherein the quaternary ammonium hydroxide is contained in an amount of from 1 to 5 % by weight.
5、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于， 所述的水 的含量为 0.2〜15wt%。  The photoresist cleaning composition according to claim 1, wherein the water is contained in an amount of 0.2 to 15% by weight.
6、 如权利要求 5所述的光刻胶清洗剂组合物， 其特征在于， 所述的水 的含量为 0.5~10wt %。  The photoresist cleaning composition according to claim 5, wherein the water is contained in an amount of from 0.5 to 10% by weight.
7、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于， 所述的垸 基二醇芳基醚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、 异丙二醇单苄基醚和己二醇单萘 基醚中的一种或多种。  The photoresist cleaning composition according to claim 1, wherein the mercapto glycol aryl ether is selected from the group consisting of propylene glycol monophenyl ether, isopropyl glycol monophenyl ether, and diethylene glycol. Monophenyl ether, dipropylene glycol monophenyl ether, diisopropyl glycol monophenyl ether, triethylene glycol monophenyl ether, tripropylene glycol monophenyl ether, triisopropyl glycol monophenyl ether, hexaethylene glycol single One or more of phenyl ether, propylene glycol monophenyl ether, hexamethylene glycol monophenyl ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether, and hexanediol mono-naphthyl ether.
8、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于， 所述的垸 基二醇芳基醚的含量为 0.1〜65wt%。  The photoresist cleaning composition according to claim 1, wherein the mercapto glycol aryl ether is contained in an amount of from 0.1 to 65 % by weight.
9、 如权利要求 8所述的光刻胶清洗剂组合物， 其特征在于， 所述的垸 基二醇芳基醚的含量为 0.5~20.0wt%。 The photoresist cleaning composition according to claim 8, wherein the mercapto glycol aryl ether is contained in an amount of from 0.5 to 20.0% by weight.
10、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于, 所述的二 甲基亚砜的含量为 l〜98wt%。 The photoresist cleaning composition according to claim 1, wherein the dimethyl sulfoxide is contained in an amount of from 1 to 98% by weight.
11、 如权利要求 10所述的光刻胶清洗剂组合物， 其特征在于， 所述的 二甲基亚砜的含量为 30〜90wt%。  The photoresist cleaning composition according to claim 10, wherein the dimethyl sulfoxide is contained in an amount of 30 to 90% by weight.
12、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于， 所述的硼 酸、 硼酸盐和硼酸酯选自硼酸、 苯硼酸、 2-甲基苯硼酸、 3-甲基苯硼酸、 4- 甲基苯硼酸、 2,3-二甲基苯硼酸、 4-乙基苯硼酸、 4-丙基苯硼酸、 4-丁基苯硼 酸、 2-甲氧基苯硼酸、 3-甲氧基苯硼酸、 4-甲氧基苯硼酸、 3，4-二甲氧基苯硼 酸、 2-羧基苯硼酸、 3-羧基苯硼酸、 4-羧基苯硼酸、 2-羟甲基苯硼酸、 3-羟甲 基苯硼酸、 4-羟甲基苯硼酸、 2-噻吩硼酸、 3-噻吩硼酸、 萘硼酸、 硼酸铵、 四甲基硼酸铵、 四乙基硼酸铵、 四丙基硼酸铵、 四丁基硼酸铵、 苄基三甲基 硼酸铵、 硼酸乙醇胺盐、 硼酸二乙醇胺盐、 硼酸三乙醇胺盐、 硼酸二甘醇胺 盐、 硼酸异丙醇胺盐、 硼酸甲基乙醇胺盐、 硼酸甲基二乙醇胺盐、 硼酸三甲 酯、 硼酸三乙酯、 硼酸三丙酯、 硼酸三丁酯、 异戊二醇硼酸酯、 双联邻苯二 酚硼酸酯、 硼酸频哪醇酯和硼酸咪唑啉酯中的一种或多种。  The photoresist cleaning composition according to claim 1, wherein the boric acid, borate and boric acid ester are selected from the group consisting of boric acid, phenylboronic acid, 2-methylphenylboronic acid, 3-methyl Benzobenzeneboronic acid, 4-methylbenzeneboronic acid, 2,3-dimethylphenylboronic acid, 4-ethylbenzeneboronic acid, 4-propylbenzeneboronic acid, 4-butylbenzeneboronic acid, 2-methoxybenzeneboronic acid, 3-methoxybenzeneboronic acid, 4-methoxybenzeneboronic acid, 3,4-dimethoxybenzeneboronic acid, 2-carboxybenzeneboronic acid, 3-carboxybenzeneboronic acid, 4-carboxybenzeneboronic acid, 2-hydroxymethyl Phenylboronic acid, 3-hydroxymethylbenzeneboronic acid, 4-hydroxymethylbenzeneboronic acid, 2-thiopheneboronic acid, 3-thiopheneboronic acid, naphthalene boronic acid, ammonium borate, ammonium tetramethylborate, ammonium tetraethylborate, tetrapropyl Ammonium borate, ammonium tetrabutylborate, ammonium benzyltrimethylborate, ethanolamine borate, diethanolamine borate, triethanolamine borate, diglycolamine borate, isopropanolamine borate, methylethanolamine borate , methyl diethanolamine borate, trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, isoprene glycol boron Esters, double catechol boronic ester, pinacol boronic ester and one or more imidazoline ester.
13、 如权利要求 12所述的光刻胶清洗剂组合物， 其特征在于， 所述的 硼酸、硼酸盐和硼酸酯选自硼酸、 苯硼酸、 2-羧基苯硼酸、 2-羟甲基苯硼酸、 四甲基硼酸铵、 四乙基硼酸铵、 硼酸乙醇胺盐、 硼酸三乙醇胺盐、 硼酸二甘 醇胺盐和双联邻苯二酚硼酸酯中的一种或多种。  The photoresist cleaning composition according to claim 12, wherein the boric acid, borate and boric acid ester are selected from the group consisting of boric acid, phenylboronic acid, 2-carboxybenzeneboronic acid, 2-hydroxyl One or more of phenylboronic acid, ammonium tetramethylborate, ammonium tetraethylborate, ethanolamine borate, triethanolamine borate, diglycolamine borate and biscatechol borate.
14、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于， 所述的硼 酸、 硼酸盐和硼酸酯的总含量为 0.01~10wt%。  The photoresist cleaning composition according to claim 1, wherein the total content of the boric acid, borate and boric acid ester is 0.01 to 10% by weight.
15、 如权利要求 14所述的光刻胶清洗剂组合物， 其特征在于， 所述的 硼酸、 硼酸盐和硼酸酯的总含量为 0.1〜5wt%。  The photoresist cleaning composition according to claim 14, wherein the total content of the boric acid, borate and boric acid ester is 0.1 to 5 wt%.
16、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于， 所述的光 刻胶清洗剂组合物进一步含有选自极性有机共溶剂、 表面活性剂和除硼酸、 硼酸盐和硼酸酯以外的其它缓蚀剂中的一种或多种。  The photoresist cleaning composition according to claim 1, wherein the photoresist cleaning composition further comprises a polar organic cosolvent, a surfactant, and a boronic acid, boric acid One or more of a corrosion inhibitor other than a salt and a borate.
17、 如权利要求 16所述的光刻胶清洗剂组合物， 其特征在于， 所述的 极性有机共溶剂含量为 50wt%， 但不包括 0wt%; 所述的表面活性剂含量 为 5wt%， 但不包括 0wt%; 所述的除硼酸、 硼酸盐和硼酸酯的缓蚀剂以外 的其它缓蚀剂含量为 5.0wt%， 但不包括 0wt%。 The photoresist cleaning composition according to claim 16, wherein The polar organic co-solvent content is 50% by weight, but does not include 0% by weight ; the surfactant content is 5% by weight, but does not include 0% by weight; the corrosion inhibitor for removing boric acid, borate and boric acid ester The corrosion inhibitor content other than the content was 5.0% by weight, but did not include 0% by weight.
18、 如权利要求 17所述的光刻胶清洗剂组合物， 其特征在于， 所述的 极性有机共溶剂的含量为 5〜30wt%;所述的表面活性剂含量为 0.05~3.0wt%; 所述的除硼酸、 硼酸盐和硼酸酯的缓蚀剂以外的其它缓蚀剂含量为 0.05〜3.0wt%。 The photoresist cleaning composition according to claim 17, wherein the polar organic co-solvent is contained in an amount of 5 to 30% by weight ; and the surfactant content is 0.05 to 3.0% by weight. The content of the corrosion inhibitor other than the corrosion inhibitor of boric acid, borate and boric acid ester is 0.05 to 3.0 wt%.
19、 如权利要求 16所述的光刻胶清洗剂组合物， 其特征在于， 所述的 极性有机共溶剂选自亚砜、 砜、 咪唑烷酮、 醇胺和垸基二醇单烷基醚中的一 种或多种。  The photoresist cleaning composition according to claim 16, wherein the polar organic co-solvent is selected from the group consisting of sulfoxides, sulfones, imidazolidinones, alcohol amines, and mercaptodiol monoalkyl groups. One or more of the ethers.
20、 如权利要求 19所述的光刻胶清洗剂组合物， 其特征在于， 所述的 亚砜为二乙基亚砜和 /或甲乙基亚砜；所述的砜选自甲基砜、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； 所述的醇胺选自一乙醇胺、 三乙 醇胺、 二甘醇胺、 异丙醇胺、 甲基乙醇胺、 甲基二乙醇胺、 二甲基乙醇胺和 羟乙基乙二胺中的一种或多种；所述的烷基二醇单垸基醚选自二乙二醇单甲 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。  The photoresist cleaning composition according to claim 19, wherein the sulfoxide is diethyl sulfoxide and/or methyl ethyl sulfoxide; and the sulfone is selected from methyl sulfone. One or more of ethyl sulfone and sulfolane; the imidazolidinone is selected from the group consisting of 2-imidazolium, 1,3-dimethyl-2-imidazolium and 1,3-diethyl-2 One or more of the imidazolidinone; the alcoholamine is selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, isopropanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine, and hydroxy One or more of ethyl ethylene diamine; the alkyl glycol monodecyl ether is selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol One or more of monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
21、 如权利要求 16所述的光刻胶清洗剂组合物， 其特征在于， 所述的 表面活性剂选自聚乙烯醇、 聚乙烯吡咯垸酮和聚氧乙烯醚中的一种或多种。  The photoresist cleaning composition according to claim 16, wherein the surfactant is one or more selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, and polyoxyethylene ether. .
22、 如权利要求 16所述的光刻胶清洗剂组合物， 其特征在于， 所述的 表面活性剂的数均分子量为 500~20000。  The photoresist cleaning composition according to claim 16, wherein the surfactant has a number average molecular weight of 500 to 20,000.
23、 如权利要求 22所述的光刻胶清洗剂组合物， 其特征在于， 所述的 表面活性剂的数均分子量为 1000〜10000。  The photoresist cleaning composition according to claim 22, wherein the surfactant has a number average molecular weight of 1,000 to 10,000.
24、 如权利要求 16所述的光刻胶清洗剂组合物， 其特征在于， 所述的 除硼酸、 硼酸盐和硼酸酯以外的其它缓蚀剂选自醇胺类、 唑类、 膦酸类和聚 丙烯酸类缓蚀剂中的一种或多种。 The photoresist cleaning composition according to claim 16, wherein the corrosion inhibitor other than boric acid, borate and boric acid ester is selected from the group consisting of alcohol amines, azoles, and phosphines. One or more of an acid and a polyacrylic corrosion inhibitor.
25、 如权利要求 24所述的光刻胶清洗剂组合物， 其特征在于， 所述的 醇胺类缓蚀剂选自一乙醇胺、三乙醇胺、二甘醇胺、异丙醇胺、 甲基乙醇胺、 甲基二乙醇胺、 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；所述的聚丙烯酸类缓蚀剂选自丙烯酸聚合 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。 The photoresist cleaning composition according to claim 24, wherein the alcohol amine corrosion inhibitor is selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, isopropanolamine, and methyl group. One or more of ethanolamine, methyldiethanolamine, dimethylethanolamine and hydroxyethylethylenediamine; the azole inhibitor is selected from the group consisting of benzotriazole, methylbenzotriazole, Benzotriazole diethanolamine salt, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, dimercaptothiadiazole, 3-amino-1,2,4-triazole , 4-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, One or more of 4-amino-5-mercapto-1,2,4-triazole, 5-amino-tetrazole and 1-phenyl-5-mercaptotetrazole; The corrosion inhibitor is selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, 2-phosphonic acid butyl phosphonium-1,2,4-tricarboxylic acid, ethylenediaminetetra One or more of methylphosphonic acid and diethylenetriamine penta methylene phosphonic acid; said polyacrylic acid corrosion inhibitor is selected from the group consisting of Alkene polymer and copolymer thereof, methacrylic acid polymer and copolymer thereof, alcohol amine salt of acrylic polymer, alcohol amine salt of methacrylic acid polymer, polyoxyethylene modified acrylic polymer and ester thereof An alkanolammonium salt, and one or more of a polyoxyethylene-modified methacrylic acid polymer and an ester thereof and an alkanolammonium salt.
26、 如权利要求 24所述的光刻胶清洗剂组合物， 其特征在于， 所述的 聚丙烯酸类缓蚀剂的数均分子量为 500~100000。  The photoresist cleaning composition according to claim 24, wherein the polyacrylic corrosion inhibitor has a number average molecular weight of 500 to 100,000.
27、 如权利要求 26所述的光刻胶清洗剂组合物， 其特征在于， 所述的 聚丙烯酸类缓蚀剂的数均分子量为 1000〜50000。  The photoresist cleaning composition according to claim 26, wherein the polyacrylic corrosion inhibitor has a number average molecular weight of 1,000 to 50,000.
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