WO2010060273A1 - Rinse solution composition for removing resist - Google Patents

Rinse solution composition for removing resist Download PDF

Info

Publication number
WO2010060273A1
WO2010060273A1 PCT/CN2009/001284 CN2009001284W WO2010060273A1 WO 2010060273 A1 WO2010060273 A1 WO 2010060273A1 CN 2009001284 W CN2009001284 W CN 2009001284W WO 2010060273 A1 WO2010060273 A1 WO 2010060273A1
Authority
WO
WIPO (PCT)
Prior art keywords
citrate
cleaning composition
ether
composition according
photoresist cleaning
Prior art date
Application number
PCT/CN2009/001284
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 CN2009801483641A priority Critical patent/CN102227690A/en
Publication of WO2010060273A1 publication Critical patent/WO2010060273A1/en

Links

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
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D7/22—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
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • 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
    • C11D7/266—Esters or carbonates
    • 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
    • C23G1/18—Organic inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • C11D2111/22—
    • 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
    • C11D7/34—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, etc., and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in a cleaning agent or rinsing the semiconductor wafer with a cleaning agent.
  • Strong bases such as potassium hydroxide, quaternary ammonium hydroxides and alcohol amines, etc., are capable of dissolving the photoresist residues produced by the photoresist and/or etching.
  • the cleaning agent 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.
  • the cleaning agent of potassium hydroxide is liable to cause corrosion of the wafer pattern and the substrate, and the removal of the photoresist is mainly in a peeling manner, so that the photoresist forms a chip-like peeling or a gel-like swelling, which easily causes the photoresist. Deposition or adhesion on the surface of the wafer, even leading to damage to the wafer pattern.
  • the cleaning agent containing the quaternary hinge 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 for negative photoresist is insufficient.
  • a photoresist cleaning agent composed of an alcohol amine, a water-soluble organic solvent, water, an organic phenol compound, a triazole compound, and a silicone antimony surfactant is proposed in U.S. Patent No. 6,140,027.
  • the semiconductor wafer is immersed in the cleaning agent, and the photoresist on the wafer and the photoresist residue generated by the etching are removed at 20 to 50 °C.
  • the cleaning agent uses an organic phenol compound and a triazole compound as corrosion inhibitors for inhibiting metal corrosion.
  • Organic phenolic compounds are harmful to the human body and cause environmental pollution.
  • the cleaning agent has insufficient cleaning ability for the negative photoresist.
  • Lithography 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 is proposed in US Pat. No. 5,962,197.
  • Glue cleaner 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 is formed by stripping the photoresist.
  • the flaky exfoliate or colloidal swell may deposit or stick on the surface of the wafer, causing residue of the photoresist and damage to the wafer pattern.
  • 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 uses N-methylmorpholine-N-oxide as an oxidizing agent and 2-mercaptobenzimidazole as a metal corrosion inhibitor.
  • the cleaning agent needs to clean the photoresist at a higher temperature, and the etching of the semiconductor wafer pattern and the substrate is slightly higher, and the cleaning ability of the photoresist is slightly insufficient.
  • a photoresist cleaning agent consisting of quaternary ammonium hydroxide, dimethyl sulfoxide, 1,3,-dimethyl-2-imidazolidinone and water is proposed in U.S. Patent No. 6,040,117.
  • the semiconductor wafer is immersed in the cleaning agent, and a photoresist having a thickness of ⁇ or more on the metal (gold, copper, lead or nickel) substrate is removed at 40 to 95 °C.
  • the cleaning agent uses 1,3'-dimethyl-2-imidazolium, which is relatively expensive, as an organic co-solvent, and does not contain a corrosion inhibitor that inhibits corrosion of metals, especially active metals such as aluminum.
  • the cleaning agent needs to clean the photoresist at a relatively high temperature, and the etching of the semiconductor wafer pattern and the substrate is slightly higher.
  • a photoresist cleaning agent composed of a quaternary ammonium hydroxide, a water-soluble organic solvent, an organic amine, a dihydric alcohol, and water is proposed in JP2001215736.
  • the semiconductor wafer was immersed in the cleaning agent, and a photoresist having a thickness of 20 ⁇ m to 40 ⁇ m on the wafer was removed at 20 to 90 °C.
  • the cleaning agent uses a glycol as a corrosion inhibitor for inhibiting metal corrosion, but the diol has a weak ability to inhibit metal corrosion and reduces the cleaning ability of the cleaning agent for the photoresist, especially the negative photoresist.
  • the cleaning agent has a slightly higher corrosion of the semiconductor wafer pattern and the substrate.
  • a photoresist cleaning agent consisting of quaternary ammonium hydroxide, ⁇ -methylpyrrolidone, diethanolamine or triethanolamine, water and methanol or ethanol is proposed in JP2004093678. Immersing the semiconductor wafer into the cleaning In the agent, a photoresist having a thickness of ⁇ or more on the wafer is removed at 15 to 80 °C.
  • the cleaning agent uses methanol or ethanol as a solubilizer for 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 corrosion of metals such as more reactive metals such as aluminum and copper.
  • the cleaning agent has a slightly higher corrosion of the semiconductor wafer pattern and the substrate.
  • the existing 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 kind of light for the defects that the existing photoresist cleaning agent has insufficient cleaning ability for the thick film photoresist, is highly corrosive to the semiconductor wafer pattern and the substrate, and is harmful to the environment.
  • a photoresist cleaning composition which has strong cleaning ability and is less corrosive to semiconductor wafer patterns and substrates and is environmentally friendly.
  • a photoresist cleaning composition comprising quaternary ammonium hydroxide, water, mercapto diol aryl ether, dimethyl sulfoxide and corrosion inhibitor, wherein At least one of the corrosion inhibitors is selected from the group consisting of citric acid, citrate, and citrate.
  • the citric acid, citric acid ester and citrate are preferably selected from the group consisting of citric acid, 2-hydroxy citric acid, trimethyl citrate, triethyl citrate, tripropyl citrate, and lemon.
  • citric acid 2-hydroxycitric acid, lauryl citrate, glyceryl citrate, ethanolamine citrate, triethanolamine citrate, diglycol citrate, tetramethylammonium citrate, citric acid
  • the content thereof is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight.
  • the corrosion inhibitor selected from the group consisting of citric acid, citric acid ester and citrate exhibits good inhibition to metal corrosion and is easily biodegradable, which is beneficial to environmental protection.
  • 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 can improve the solubility of the quaternary ammonium hydroxide in dimethyl sulfoxide, and the increase of the quaternary ammonium hydroxide content is advantageous for improving the cleaning agent combination in the present invention.
  • the mercapto diol aryl ether is less harmful to the environment than the ethylene glycol alkyl ether and ethylene glycol aryl ether used in the conventional photoresist cleaning agent.
  • the mercapto diol in the mercapto diol aryl ether has a carbon number of from 3 to 18.
  • 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, diisopropyl glycol monophenyl.
  • Ether triethylene glycol monophenyl ether, tripropylene glycol monophenyl ether, triisopropyl glycol monophenyl ether, hexadeethylene glycol monophenyl ether, hexapropylene glycol monophenyl ether, hexapropylene glycol monobenzene
  • a group of ether propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether and hexanediol mononaphthyl ether; more preferably selected from the group consisting of propylene glycol monophenyl ether, isopropyl glycol monophenyl ether, dipropylene glycol
  • the content is preferably from 0.1 to 65 wt%, more preferably from 0.5 to 20.0 wt%.
  • the content of the dimethyl sulfoxide is preferably from 1 to 98% by weight, more preferably from 30 to 90% by weight.
  • the photoresist cleaning composition may further contain one of a polar organic co-solvent, a surfactant, and other corrosion inhibitors other than citric acid, citrate and citrate.
  • 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 does not include 0wt%, more preferably 0.05 ⁇ 3.0wt%
  • the content of the corrosion inhibitor other than the corrosion inhibitors of citric acid, citrate and citrate is preferably 5% by weight, but not including 0% by weight. , more preferably 0.05-3.0wt
  • the polar organic co-solvent is preferably one or more selected from the group consisting of sulfoxide, sulfone, imidazolium, alcohol amine and mercaptodiol monodecyl ether.
  • the sulfoxide is preferably 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-imidazolidinone.
  • the alcohol amine is preferably selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, isopropanol
  • an amine, methylethanolamine, methyldiethanolamine, dimethylethanolamine and hydroxyethylethylenediamine more preferably selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine and methylethanolamine
  • the alkyl glycol monodecyl ethers are preferably selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene glycol monobutyl ether.
  • dipropylene glycol monomethyl ether dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether, more preferably selected from the group consisting of diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and dipropylene One or more alcohols monobutyl ether.
  • the surfactant is preferably selected from one or more of polyethylene glycol, polyvinylpyrrolidone and polyoxyethylene ether, more preferably polyvinylpyrrolidone and/or polyoxygen. Vinyl 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 citric acid, citrate and citrate is preferably selected from the group consisting 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-
  • tetramethylenephosphonic acid and diethylenetriamine penta methylene phosphonic acid more preferably selected from the group consisting of 2-phosphonium bromide-1,2,4-tricarboxylic acid, ethylenediamine
  • tetramethylenephosphonic acid and diethylenetriamine penta methylene phosphonic acid are preferably selected from the group consisting of 2-phosphonium bromide-1,2,4-tricarboxylic acid, ethylenediamine
  • tetramethylenephosphonic acid and diethylenetriamine penta methylene phosphonic acid more preferably selected from the group consisting of 2-phosphonium bromide-1,2,4-tricarboxylic acid, ethylenediamine
  • tetramethylenephosphonic acid and diethylenetriamine penta methylene phosphonic acid are preferably selected from the group consisting of 2-phosphonium bromide-1,2,4-tricarboxylic acid, ethylenediamine
  • 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 alcoholamine salt, a polyoxyethylene-modified acrylic polymer, an ester thereof and an alkanolammonium salt, 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 the corrosion of metals, especially 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 ° C).
  • 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 ⁇ m or more on a metal, metal alloy or dielectric substrate.
  • the alkyl 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, and the increase in the quaternary ammonium hydroxide content is advantageous.
  • the cleaning ability of the cleaning composition of the present invention to a photoresist, especially a highly cross-linked negative photoresist, is improved.
  • the mercapto diol aryl ether contained in the photoresist cleaning composition of the present invention exhibits a good inhibitory effect on corrosion of a metal such as copper.
  • the photoresist cleaning composition of the present invention exhibits extremely weak corrosiveness to non-metal materials such as silica.
  • the corrosion inhibitor selected from the group consisting of citric acid, citrate and citrate contained in the photoresist cleaning composition of the present invention exhibits a good inhibitory effect on corrosion of a metal, and can effectively suppress wafer patterns and bases. Corrosion of dark spots (pitting) on the material.
  • the corrosion inhibitor selected from the group consisting of citric acid, citric acid ester and citrate contained in the photoresist cleaning composition of the present invention is easily biodegradable and is environmentally friendly.
  • the polyacrylic corrosion inhibitor which can be contained in the photoresist cleaning composition of the present invention exhibits an extremely strong inhibitory effect on corrosion of metal, particularly aluminum, and can further suppress corrosion of the wafer pattern and the substrate.
  • the photoresist cleaning composition of the present invention can dissolve and remove a high-crosslinking thick film photoresist (especially a thick film negative photoresist) on a semiconductor wafer and other etching residues to avoid light.
  • a high-crosslinking thick film photoresist especially a thick film negative photoresist
  • the deposition or adhesion of the glue on the surface of the wafer without causing 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).
  • Methyl sulfone monoethanolamine tripropylene ethoxylate (tetrabutyl)
  • Polyacrylic acid (number average molecular weight is 500) acetyl lemon sulfolane citrate
  • Citric acid methacrylic acid-horse hydroxide 2.5 4.5 alcohol single 65 9.45 1
  • Trihexyl ester acid copolymer (number of ammonium 0.05
  • Phenyl average molecular weight is ether 1000
  • Ammonium hexyl ester is 10000
  • Polyacrylic acid triethanolamine salt (number average 0.15 sub-quantity 20000) citric acid
  • Ammonium molecular weight is 500
  • Ketone (number average molecular weight 0.09 is 20000) citric acid
  • Amino ester Dimercaptothiadiazole 1.2 Diisoethylene glycol (number average tetraethyl propylene two molecular weight 0.5 KOH 2.5 10 Alcohol single 5 72.3 20000)
  • Ethanolamine salt (number average 0.4 molecular weight is
  • Alcoholamine 0.6 (number average molecular weight is citrate 8000) diglycolamine 2 diethylene glycol monoethyl
  • the amount is 75000) Ammonium Dimethylethanolamine 0.1 Diethylene glycol monomethyl citrate 5
  • Tetrabutyl 1 ethanolamine salt (number average 0.5 ammonium molecular weight is
  • Ethanolamine salt (number average 0.5
  • Comparative Cleaning Agent Compositions 1, 7, and Cleaning Agent Compositions 27 to 42 of the Invention Table 2 shows comparative cleaning agent compositions ⁇ 7' and the cleaning composition compositions 27-42 of the present invention.
  • the formulations were prepared by simply mixing uniformly according to the components listed in Table 2 and their contents, that is, each detergent composition was prepared.
  • Oxide water phenyl citrate sulfone alcohol amine homotrienic acid trinitrogen acid (number average agent sulfone)
  • Ammonium ether ⁇ quantity is molecular weight
  • the comparative cleaning composition ⁇ 6' in Table 2 and the cleaning composition 27 ⁇ 42 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.
  • the comparative cleaning composition ⁇ 6' in Table 2 and the cleaning composition 27 ⁇ 42 of the present invention were used to clean a blank Cu wafer and test its corrosion to metallic Cu. Test methods and conditions: 4 X 4 cm blank Cu wafer was immersed in the cleaning agent composition, 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, using four The polar probe instrument was used to measure the change in surface resistance of the blank Cu wafer before and after etching. The results are shown in Table 3.
  • the comparative cleaning composition ⁇ 6' in Table 2 and the cleaning composition 27 ⁇ 42 of the present invention were used to clean the blank A1 wafer and test its corrosion to the metal A1.
  • Test methods and conditions 4 4 4 cm blank A1 wafer was immersed in the cleaning composition, 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, using four The polar probe instrument 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 cleaning composition ⁇ 6' in Table 2 and the cleaning composition 27 ⁇ 42 of the present invention were used to clean blank tetraethoxysilane (TEOS) wafers and tested for corrosion of non-metallic TEOS. happening. Test Methods and Conditions: A 4 X 4 cm blank TEOS wafer was dipped into the cleaning composition, 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. Determination of TEOS thickness before and after cleaning of blank TEOS wafers using Nanospec6100 thickness gauge The change in degree is calculated and the results are shown in Table 3.
  • the comparative cleaning composition ⁇ 6' in Table 2 and the cleaning composition 27 ⁇ 42 of the present invention are used to clean the photoresist on the semiconductor wafer.
  • the cleaning method is as follows: A semiconductor wafer (containing a pattern) containing a negative acrylate-based photoresist (having a thickness of about 60 ⁇ m and exposed and etched) is immersed in the cleaning composition shown in Table 2, at 20 The mixture was shaken at ⁇ 85 ° C for 1 to 30 minutes using a constant temperature oscillator, then washed with deionized water and then dried with high purity nitrogen.
  • the cleaning effect of the photoresist and the corrosion of the wafer pattern by the cleaning composition are shown in Table 3.
  • Condition no corrosion
  • condition removal
  • Table 4 The cleaning composition of the present invention in Table 2 32 ⁇ 42 pairs of negative acrylates
  • the cleaning of the present invention is compared with the comparative cleaning agent composition ⁇ 6.
  • the lotion compositions 27 to 42 have good cleaning ability for thick film negative acrylate photoresists, wide temperature range, low corrosivity to metal Cu and A1 and non-metal TEOS, and no corrosion to wafer patterns. Or damaged.
  • the photoresist cleaning composition of the present invention can remove a thick film photoresist and other etching residues of 20 ⁇ m or more at 20 to 85 ° C, and contains a mercapto diol.
  • a base ether and a corrosion inhibitor selected from the group consisting of citric acid, citrate and citrate can form a protective film on the surface of the wafer pattern and the substrate to prevent attack of the wafer pattern and the substrate by halogen atoms, hydroxide ions, and the like. , thereby reducing the corrosion of the wafer pattern and the substrate; in particular, the corrosion inhibitor selected from the group consisting of citric acid, citrate and citrate exhibits a good inhibition of corrosion of the metal, and can effectively suppress the wafer pattern and the base.
  • the photoresist cleaner composition of the present invention contains a corrosion inhibitor selected from the group consisting of citric acid, citrate and citrate, which is easily biodegradable and is environmentally friendly.
  • the photoresist cleaning composition of the present invention exhibits extremely weak corrosiveness to non-metallic materials such as silica.
  • the polyacrylic corrosion inhibitor which can be contained in the photoresist cleaning composition of the present invention exhibits an extremely strong inhibitory effect on corrosion of metals, particularly aluminum, and can further suppress corrosion of the wafer pattern and the substrate.
  • the photoresist cleaning composition of the present invention can dissolve and remove a high-crosslinking thick film negative photoresist on a semiconductor wafer, thereby avoiding deposition or adhesion of the photoresist on the surface of the wafer without causing wafer pattern and Corrosion or damage to the substrate.

Abstract

A rinse solution composition for removing resist includes quaternary ammonium hydroxide, water, alkyl diol aryl ether, dimethyl sulfoxide and corrosion inhibitor of at least one of citric acid, citrate ester and citrate salt. The alkyl glycol of alkyl glycol aryl ether has 3-18 carbon atoms. The rinse solution composition may further include polar organic co-solvent, surfactant and/or other corrosion inhibitor. The rinse solution composition for removing resist may clean more 20μm thickness resist (especially thick film negative resist) and other etching residues on a metal, metal alloy or dielectric substrate, and has low etch rate for metals such as A1 and Cu, and nonmetals such as SiO2. And the rinse solution composition can be used in micro electronic field for the cleaning of semiconductor wafer.

Description

一种光刻胶清洗剂组合物  Photoresist cleaning composition
技术领域 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。 BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning composition in a semiconductor manufacturing process, and in particular to a photoresist cleaning composition.
技术背景 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。 20μπι 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 20μπι 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。  Currently, the photoresist cleaning composition is mainly composed of a strong base, a polar organic solvent and/or water, etc., and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in a cleaning agent or rinsing the semiconductor wafer with a cleaning agent.
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。含有季铰氢氧化物的 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。 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. But contain The cleaning agent of potassium hydroxide is liable to cause corrosion of the wafer pattern and the substrate, and the removal of the photoresist is mainly in a peeling manner, so that the photoresist forms a chip-like peeling or a gel-like swelling, which easily causes the photoresist. Deposition or adhesion on the surface of the wafer, even leading to damage to the wafer pattern. The cleaning agent containing the quaternary hinge 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。但该清洗剂 中不含有水， 且其对负性光刻胶的清洗能力不足。  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. However, the cleaning agent does not contain water, and its cleaning ability for negative photoresist is insufficient.
US6140027中提出了由醇胺、 水溶性有机溶剂、 水、 有机酚化合物、 三 唑化合物和聚硅氧垸表面活性剂组成的光刻胶清洗剂。将半导体晶片浸入该 清洗剂中，在 20〜50°C下除去晶片上的光刻胶和刻蚀所产生的光刻胶残余物。 该清洗剂采用有机酚化合物和三唑化合物作为抑制金属腐蚀的缓蚀剂。有机 酚化合物对人体有害， 而且会对环境造成污染。该清洗剂对负性光刻胶的清 洗能力不足。  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 U.S. Patent No. 6,140,027. The semiconductor wafer is immersed in the cleaning agent, and the photoresist on the wafer and the photoresist residue generated by the etching are removed at 20 to 50 °C. The cleaning agent uses an organic phenol compound and a triazole compound as corrosion inhibitors for inhibiting metal corrosion. Organic phenolic compounds are harmful to the human body and cause environmental pollution. The cleaning agent has insufficient cleaning ability for the negative photoresist.
US5962197中提出了由氢氧化钾、 丙二醇醚、 N-甲基吡咯垸酮、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。 Lithography 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 is proposed in US Pat. No. 5,962,197. Glue cleaner. 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 is formed by stripping the photoresist. The flaky exfoliate or colloidal swell may deposit or stick on the surface of the wafer, causing residue of the photoresist and damage to the wafer pattern.
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。该清洗剂采用 N-甲基吗啡啉 -N-氧化物作为 氧化剂， 采用 2-巯基苯并咪唑作为金属腐蚀抑制剂。该清洗剂需在较高温度 下清洗光刻胶， 对半导体晶片图案和基材的腐蚀略高， '且对光刻胶的清洗能 力略显不足。  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 uses N-methylmorpholine-N-oxide as an oxidizing agent and 2-mercaptobenzimidazole as a metal corrosion inhibitor. The cleaning agent needs to clean the photoresist at a higher 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 ΙΟμηι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。  A photoresist cleaning agent consisting of quaternary ammonium hydroxide, dimethyl sulfoxide, 1,3,-dimethyl-2-imidazolidinone and water is proposed in U.S. Patent No. 6,040,117. The semiconductor wafer is immersed in the cleaning agent, and a photoresist having a thickness of ΙΟμηι 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, especially 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.
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 20μηι〜40μηι厚度的光刻胶。 该清洗剂采用二元醇作为抑制 金属腐蚀的缓蚀剂， 但二元醇对金属腐蚀的抑制能力很弱， 而且会降低清洗 剂对光刻胶尤其是负性光刻胶的清洗能力。该清洗剂对半导体晶片图案和基 材的腐蚀略高。  A photoresist cleaning agent composed of a quaternary ammonium hydroxide, a water-soluble organic solvent, an organic amine, a dihydric alcohol, and water is proposed in JP2001215736. The semiconductor wafer was immersed in the cleaning agent, and a photoresist having a thickness of 20 μm to 40 μm on the wafer was removed at 20 to 90 °C. The cleaning agent uses a glycol as a corrosion inhibitor for inhibiting metal corrosion, but the diol has a weak ability to inhibit metal corrosion and reduces the cleaning ability of the cleaning agent for the photoresist, especially the negative photoresist. The cleaning agent has a slightly higher corrosion of the semiconductor wafer pattern and the substrate.
JP2004093678中提出了由季铵氢氧化物、 Ν-甲基吡咯垸酮、二乙醇胺或 三乙醇胺、水和甲醇或乙醇组成的光刻胶清洗剂。将半导体晶片浸入该清洗 剂中， 在 15〜80°C下除去晶片上的 ΙΟμπι以上厚度的光刻胶。 该清洗剂采用 甲醇或乙醇作为季铵氢氧化物的增溶剂， 但甲醇或乙醇的闪点过低， 而且会 降低清洗剂对光刻胶尤其是负性光刻胶的清洗能力。该清洗剂不含有抑制金 属 （尤其是铝和铜等较活泼金属）腐蚀的缓蚀剂。 该清洗剂对半导体晶片图 案和基材的腐蚀略高。 综上所述， 现有的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。 A photoresist cleaning agent consisting of quaternary ammonium hydroxide, Ν-methylpyrrolidone, diethanolamine or triethanolamine, water and methanol or ethanol is proposed in JP2004093678. Immersing the semiconductor wafer into the cleaning In the agent, a photoresist having a thickness of ΙΟμπι 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 corrosion of metals such as more reactive metals such as aluminum and copper. The cleaning agent has a slightly higher corrosion of the semiconductor wafer pattern and the substrate. 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对厚膜光刻胶清 洗能力不足、 对半导体晶片图案和基材腐蚀性较强以及对环境有害的缺陷， 提供一种对光刻胶清洗能力强且对半导体晶片图案和基材腐蚀性较低、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 kind of light for the defects that the existing photoresist cleaning agent has insufficient cleaning ability for the thick film photoresist, is highly corrosive to the semiconductor wafer pattern and the substrate, and is harmful to the environment. A photoresist cleaning composition which has strong cleaning ability and 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、 垸基二醇芳基醚、 二甲基亚砜和缓蚀剂， 其中 缓蚀剂中的至少一种选自柠檬酸、 柠檬酸酯和柠檬酸盐。  The technical solution adopted by the present invention to solve the above technical problems is: a photoresist cleaning composition comprising quaternary ammonium hydroxide, water, mercapto diol aryl ether, dimethyl sulfoxide and corrosion inhibitor, wherein At least one of the corrosion inhibitors is selected from the group consisting of citric acid, citrate, and citrate.
本发明中， 所述的柠檬酸、 柠檬酸酯和柠檬酸盐较佳的选自柠檬酸、 2- 羟基柠檬酸、柠檬酸三甲酯、柠檬酸三乙酯、柠檬酸三丙酯、柠檬酸三丁酯、 柠檬酸三己酯、 柠檬酸三辛酯、 乙酰柠檬酸三乙酯、 乙酰柠檬酸三丙酯、 乙 酰柠檬酸三丁酯、 乙酰柠檬酸三己酯、 乙酰柠檬酸三辛酯、 丁酰柠檬酸三己 酯、柠檬酸月桂醇酯、柠檬酸甘油酯、柠檬酸乙醇胺酯、柠檬酸三乙醇胺酯、 柠檬酸二甘醇胺酯、柠檬酸异丙醇胺酯、壳聚糖柠檬酸酯、柠檬酸咪唑啉酯、 柠檬酸二氢铵、 柠檬酸氢二铵、 柠檬酸三铵、 柠檬酸四甲基铵、 柠檬酸四乙 基铰、 柠檬酸四丙基铰、 柠檬酸四丁基铵、 柠檬酸苄基三甲基铵、 乙醇胺柠 檬酸盐、 二乙醇胺柠檬酸盐、 三乙醇胺柠檬酸盐、 二甘醇胺柠檬酸盐、 异丙 醇胺柠檬酸盐、 甲基乙醇胺柠檬酸盐、 甲基二乙醇胺柠檬酸盐、三乙胺柠檬 酸盐、 柠檬酸哌嗪和 8-羟基喹啉柠檬酸盐中的一种或多种。 其中， 更佳的选 自柠檬酸、 2-羟基柠檬酸、 柠檬酸月桂醇酯、 柠檬酸甘油酯、 柠檬酸乙醇胺 酯、 柠檬酸三乙醇胺酯、 柠檬酸二甘醇胺酯、 柠檬酸四甲基铵、 柠檬酸四乙 基铵、 乙醇胺柠檬酸盐、 三乙醇胺柠檬酸盐和二甘醇胺柠檬酸盐中的一种或 多种。 其含量较佳的为 0.01〜10wt%， 更佳的为 0.1〜5wt%。 所述的选自柠檬 酸、柠檬酸酯和柠檬酸盐的缓蚀剂对金属的腐蚀表现出良好的抑制作用， 且 易于生物降解， 有利于环境保护。 In the present invention, the citric acid, citric acid ester and citrate are preferably selected from the group consisting of citric acid, 2-hydroxy citric acid, trimethyl citrate, triethyl citrate, tripropyl citrate, and lemon. Tributyl citrate, trihexyl citrate, trioctyl citrate, acetyl triethyl citrate, acetyl tripropyl citrate, acetyl tributyl citrate, acetyl trihexyl citrate, acetyl trisuccinate Ester, butyryl trihexyl citrate, lauryl citrate, glyceryl citrate, ethanolamine citrate, triethanolamine citrate, diglycol citrate, isopropanol citrate, shell poly Sugar citrate, imidazoline citrate, ammonium dihydrogen citrate, diammonium hydrogen citrate, triammonium citrate, tetramethylammonium citrate, tetraethyl citrate citrate, tetrapropyl citrate citrate, lemon Tetrabutylammonium acid, benzyltrimethylammonium citrate, ethanolamine citrate, diethanolamine citrate, triethanolamine citrate, diglycolamine citrate, isopropanolamine citrate, methyl Ethanolamine citrate, methyldiethanolamine citrate , Triethylamine citrate, citric acid, piperazine and 8-hydroxyquinoline citrate, one or more. Among them, better choice From citric acid, 2-hydroxycitric acid, lauryl citrate, glyceryl citrate, ethanolamine citrate, triethanolamine citrate, diglycol citrate, tetramethylammonium citrate, citric acid One or more of ethylammonium, ethanolamine citrate, triethanolamine citrate, and diglycolamine citrate. The content thereof is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight. The corrosion inhibitor selected from the group consisting of citric acid, citric acid ester and citrate exhibits good inhibition to metal corrosion and is easily biodegradable, which is beneficial to environmental protection.
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可以提高季铵氢氧化物在二甲基亚砜 中的溶解度，而季铵氢氧化物含量的增加有利于提高本发明中的清洗剂组合 物对光刻胶的清洗能力。所述的垸基二醇芳基醚对环境的危害低于常规光刻 胶清洗剂使用的乙二醇烷基醚和乙二醇芳基醚等， 更利于环境保护。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、 异丙二醇单苯基醚、 二丙二醇 单苯基醚、 二异丙二醇单苯基醚和丙二醇单苄基醚中的一种或多种。 其含量 较佳的为 0.1〜65wt%， 更佳的为 0.5〜20.0wt%。  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 can improve the solubility of the quaternary ammonium hydroxide in dimethyl sulfoxide, and the increase of the quaternary ammonium hydroxide content is advantageous for improving the cleaning agent combination in the present invention. The ability of the object to clean the photoresist. The mercapto diol aryl ether is less harmful to the environment than the ethylene glycol alkyl ether and ethylene glycol aryl ether used in the conventional photoresist cleaning agent. The mercapto diol in the mercapto diol aryl ether has a carbon number of from 3 to 18. 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, diisopropyl glycol monophenyl. Ether, triethylene glycol monophenyl ether, tripropylene glycol monophenyl ether, triisopropyl glycol monophenyl ether, hexadeethylene glycol monophenyl ether, hexapropylene glycol monophenyl ether, hexapropylene glycol monobenzene One or more of a group of ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether and hexanediol mononaphthyl ether; more preferably selected from the group consisting of propylene glycol monophenyl ether, isopropyl glycol monophenyl ether, dipropylene glycol One or more of monophenyl ether, diisopropyl glycol monophenyl ether, and propylene glycol monobenzyl ether. The content is preferably from 0.1 to 65 wt%, more preferably from 0.5 to 20.0 wt%.
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， 所述的光刻胶清洗剂组合物还可进一步含有极性有机共溶 剂、 表面活性剂和除柠檬酸、 柠檬酸酯和柠檬酸盐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%; 所述的除柠檬酸、 柠檬酸酯和柠檬酸盐的缓 蚀剂以外的其它缓蚀剂含量较佳的为 5wt%， 但不包括 0wt%， 更佳的为 0.05-3.0wt In the present invention, the photoresist cleaning composition may further contain one of a polar organic co-solvent, a surfactant, and other corrosion inhibitors other than citric acid, citrate and citrate. 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 does not include 0wt%, more preferably 0.05~3.0wt%; the content of the corrosion inhibitor other than the corrosion inhibitors of citric acid, citrate and citrate is preferably 5% by weight, but not including 0% by weight. , more preferably 0.05-3.0wt
本发明中， 所述的极性有机共溶剂较佳的选自亚砜、 砜、 咪唑垸酮、 醇 胺和垸基二醇单垸基醚中的一种或多种。 其中， 所述的亚砜较佳的为二乙基 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-咪唑烷酮中的一种或多种，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； 所述的烷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 sulfoxide, sulfone, imidazolium, alcohol amine and mercaptodiol monodecyl ether. 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-imidazolidinone. 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 One or more of an amine, methylethanolamine, methyldiethanolamine, dimethylethanolamine and hydroxyethylethylenediamine, more preferably selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine and methylethanolamine One or more of the alkyl glycol monodecyl ethers are preferably selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene glycol monobutyl ether. One or more of dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether, more preferably selected from the group consisting of diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and dipropylene One or more alcohols monobutyl ether.
本发明中， 所述的表面活性剂较佳的选自聚乙二醇、 聚乙烯吡咯烷酮和 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 polyethylene glycol, polyvinylpyrrolidone and polyoxyethylene ether, more preferably polyvinylpyrrolidone and/or polyoxygen. Vinyl 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， 所述的除柠檬酸、 柠檬酸酯和柠檬酸盐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 1-苯基 -5-巯基四氮唑中的一种或多种， 更佳的选自苯并三氮唑、 甲基苯并三 氮唑、 苯并三氮唑二乙醇胺盐、 3-氨基 -1,2,4-三氮唑、 4-氨基 -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 -1,1-二膦酸、 氨基三亚甲基膦酸、 2-膦酸丁 烷 -1,2,4-三羧酸、 乙二胺四亚甲基膦酸和二乙烯三胺五亚甲基膦酸中的一种 或多种， 更佳的选自 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。 In the present invention, the corrosion inhibitor other than citric acid, citrate and citrate is preferably selected from the group consisting of an alcohol amine, an azole, a phosphonic acid and a polyacrylic corrosion inhibitor. Or 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 1-phenyl-5-mercaptotetrazole 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 Or one or more of 4-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole and 5-amino-tetrazole; Phosphonic acid The corrosion inhibitor is preferably selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, 2-phosphonic acid butane-1,2,4-tricarboxylic acid, ethylenediamine. One or more of tetramethylenephosphonic acid and diethylenetriamine penta methylene phosphonic acid, more preferably selected from the group consisting of 2-phosphonium bromide-1,2,4-tricarboxylic acid, ethylenediamine One or more of tetramethylenephosphonic acid and diethylenetriamine penta methylene phosphonic acid.
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、 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、 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尤其是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 alcoholamine salt, a polyoxyethylene-modified acrylic polymer, an ester thereof and an alkanolammonium salt, a polyoxyethylene-modified methacrylic acid polymer, and an ester thereof and an alkanolammonium salt. Selected from an acrylic polymer or a copolymer thereof, an alcohol amine salt of an acrylic polymer, a polyoxyethylene modified acrylic polymer and an alkanolammonium salt thereof, a polyoxyethylene modified methacrylic acid polymer and an alkanolammonium salt thereof One or more. 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 the corrosion of metals, especially 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 °C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 ° C). 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.
本发明的积极进步效果在于：  The positive effects of the present invention are:
( 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 金或电介质基材上的 20μπι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 μm or more on a metal, metal alloy or dielectric substrate.
(2) 本发明的光刻胶清洗剂组合物含有的烷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，而季铵氢氧化物含量的增加有利于提 高本发明中的清洗剂组合物对光刻胶尤其是高交联度的负性光刻胶的清洗 能力。  (2) The alkyl 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, and the increase in the quaternary ammonium hydroxide content is advantageous. The cleaning ability of the cleaning composition of the present invention to a photoresist, especially a highly cross-linked negative photoresist, is improved.
(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对金属如 铜的腐蚀表现出良好的抑制作用。  (3) The mercapto diol aryl ether contained in the photoresist cleaning composition of the present invention exhibits a good inhibitory effect on corrosion of a metal such as copper.
(4) 本发明的光刻胶清洗剂组合物对二氧化硅等非金属材料表现出极 弱的腐蚀性。 (5 ) 本发明的光刻胶清洗剂组合物中含有的选自柠檬酸、 柠檬酸酯和 柠檬酸盐的缓蚀剂对金属的腐蚀表现出良好的抑制作用， 能够有效抑制晶片 图案和基材上腐蚀暗点 （点蚀） 的产生。 (4) The photoresist cleaning composition of the present invention exhibits extremely weak corrosiveness to non-metal materials such as silica. (5) The corrosion inhibitor selected from the group consisting of citric acid, citrate and citrate contained in the photoresist cleaning composition of the present invention exhibits a good inhibitory effect on corrosion of a metal, and can effectively suppress wafer patterns and bases. Corrosion of dark spots (pitting) on the material.
(6) 本发明的光刻胶清洗剂组合物中含有的选自柠檬酸、 柠檬酸酯和 柠檬酸盐的缓蚀剂易于生物降解， 有利于环境保护。  (6) The corrosion inhibitor selected from the group consisting of citric acid, citric acid ester and citrate contained in the photoresist cleaning composition of the present invention is easily biodegradable and is environmentally friendly.
(7) 本发明的光刻胶清洗剂组合物中可以含有的聚丙烯酸类缓蚀剂对 金属尤其是铝的腐蚀表现出极强的抑制作用，可以进一步抑制晶片图案和基 材的腐蚀。  (7) The polyacrylic corrosion inhibitor which can be contained in the photoresist cleaning composition of the present invention exhibits an extremely strong inhibitory effect on corrosion of metal, particularly aluminum, and can further suppress corrosion of the wafer pattern and the substrate.
( 8 ) 本发明的光刻胶清洗剂组合物可以溶解除去半导体晶片上的高交 联度的厚膜光刻胶（尤其是厚膜负性光刻胶）和其它刻蚀残留物， 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。  (8) The photoresist cleaning composition of the present invention can dissolve and remove a high-crosslinking thick film photoresist (especially a thick film negative photoresist) on a semiconductor wafer and other etching residues to avoid light. The deposition or adhesion of the glue on the surface of the wafer without causing corrosion or damage to the wafer pattern.
( 9 )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。  (9) The photoresist cleaning composition of the present invention can be used over a wide temperature range (20-85 ° C).
发明内容 下面通过实施例的方式进一步说明本发明。下述实施例中，百分比均为 质量百分比。 实施例 1~26 表 1给出了本发明的光刻胶清洗剂组合物实施例 1〜26的配方， 按表 1 中所列组分及其含量， 简单混合均匀， 即制得各清洗剂组合物。 本发明的光刻胶清洗剂组合物实施例 1~26 SUMMARY OF THE INVENTION The invention is further illustrated by the following examples. In the following examples, the percentages are all by mass. Examples 1 to 26 Table 1 shows the formulations of the photoresist cleaning composition examples 1 to 26 of the present invention, which are simply mixed uniformly according to the components listed in Table 1 and their contents, that is, each cleaning agent is prepared. combination. Photoresist cleaning composition composition of the present invention 1~26
水 垸基二醇芳基 二甲 柠檬酸、柠檬酸酯  Water sulfhydryl aryl dimethyl citrate, citric acid ester
季铰氢氧化物 其它  Quarter hinge hydroxide
实 含 醚 基亚 或柠檬酸盐 Contains ether or citrate
施 砜 Sulfone
具体 a 具体 ά 具体 ύ m 具体 a  Specific a specific ά specific ύ m specific a
例 wt 含量 Example wt content
物质 Wt% 物质 wt% 物质 wt% 物质 wt%  Substance Wt% substance wt% substance wt% substance wt%
% wt%  % wt%
异丙  Isopropyl
四甲基  Tetramethyl
二醇  Glycol
1 氢氧化 0.5 0.5 0.99 98 柠檬酸 0.01 1 /  1 Hydroxide 0.5 0.5 0.99 98 Citric acid 0.01 1 /
单苯  Monophenyl
铵  Ammonium
基醚 丙二 Ether C
四乙基 Tetraethyl
醇单  Alcohol single
氢氧化 7.9 90 柠檬酸 0 1 1 苯基 Hydroxide 7.9 90 citric acid 0 1 1 phenyl
铰  Hinge
醚  Ether
二丙  Dipropylene
四丙基 Tetrapropyl
二醇 羟基  Glycol hydroxyl
氢氧化 甲乙基亚砜 Methyl sulfoxide
单苯 柠檬酸  Monophenyl citric acid
铵  Ammonium
基醚  Ether
二异  Two different
四丁基 丙二 聚氧乙烯醚 (数 Tetrabutyl propylene di ethoxylate
柠檬酸  Citric acid
簡化 醇单 均分子量为 Simplified alcohol single average molecular weight
三乙酯  Triethyl ester
铰 苯基 10000)  Hinge phenyl 10000)
醚  Ether
柠檬酸 2.5  Citric acid 2.5
聚氧乙烯改性 二乙  Polyoxyethylene modification
柠檬酸 的聚丙烯酸一 二醇  Polyacrylic acid mono diol
甲基氢 三甲酯 Methyl hydrogen trimethyl ester
乙醇胺盐 (数均 单苯  Ethanolamine salt
氧化铵 二甘醇 分子量为 Ammonium oxide diethylene glycol
基醚  Ether
胺柠檬  Amine lemon
酸盐  Acid salt
柠檬酸 二乙基亚砜  Citric acid diethyl sulfoxide
1  1
三丁酯 三乙醇胺 3.5 丙二  Tributyl ester triethanolamine 3.5 propylene
四甲基 聚乙烯吡咯烷 Tetramethylpolyvinylpyrrolidine
醇单  Alcohol single
氢氧化 乙醇胺 酮 (数均分子量 Ethanolamine ketone (number average molecular weight)
苄基  Benzyl
铵 柠檬酸 为  Ammonium citrate
醚  Ether
±卜 甲基苯并三氮  ±Bumethylbenzotriazine
1 ¾  1 3⁄4
甲基砜 一乙醇胺 三丙 聚氧乙烯醚 (数 四丁基  Methyl sulfone monoethanolamine tripropylene ethoxylate (tetrabutyl)
二醇 柠檬酸 均分子量为 氢氧化  Glycol, citric acid, average molecular weight, hydroxide
单苯 三丙酯 10000)  Monophenyltripropyl 10000)
铰  Hinge
基醚  Ether
聚丙烯酸 (数均 分子量为 500) 乙酰柠 环丁砜 檬酸三  Polyacrylic acid (number average molecular weight is 500) acetyl lemon sulfolane citrate
二甘醇胺 三异 己酯  Diethylene glycol amine triisohexyl ester
四乙基 丙二 丙烯酸-马来酸 氢氧化 醇单 共聚物 (数均数 Tetraethyl propylene diacrylate-maleic acid hydroxide alcohol monocopolymer (number average)
乙酰柠  Acetyl
铰 苯基 均分子量为  Hind phenyl average molecular weight
檬酸三  Citric acid three
醚  Ether
乙酯  Ethyl ester
苯并三氮唑 乙基砜 15 六缩 异丙醇胺 1 四丙基 乙二 乙酰柠 聚乙二醇 (数均 氢氧化 2.8 3.5 醇单 6 71.08 檬酸三 0.5 分子量为 0.1 铰 苯基 丁酯 10000) Benzotriazole Ethyl sulfone 15 hexa-isopropanolamine 1 tetrapropyl ethylene diacetyl lemon polyethylene glycol (number average hydrogen 2.8 3.5 alcohol single 6 71.08 citric acid three 0.5 molecular weight 0.1 phenyl butyl 10000)
醚 聚甲基丙烯酸  Ether polymethacrylic acid
(数均分子量为 0.02 (number average molecular weight is 0.02
2500) 2500)
1,3-二甲基 -2-咪  1,3-dimethyl-2-mi
15 唑垸酮 六缩 二甲基乙醇胺 2 四甲基 丙二  15 oxazolone hexamethylethanolamine 2 tetramethyl propylene
柠檬酸 甲基丙烯酸-马 氢氧化 2.5 4.5 醇单 65 9.45 1  Citric acid methacrylic acid-horse hydroxide 2.5 4.5 alcohol single 65 9.45 1
三己酯 来酸共聚物 (数 铵 0.05  Trihexyl ester acid copolymer (number of ammonium 0.05
苯基 均分子量为 醚 1000)  Phenyl average molecular weight is ether 1000)
2-巯基苯并咪  2-mercaptobenzoimine
0.5 唑  0.5 azole
乙酰柠  Acetyl
檬酸三 0.1 2-咪唑烷酮 5 六缩 丙酯  Citric acid three 0.1 2-imidazolidinone 5 hexapropyl ester
四丙基 异丙 Tetrapropyl isopropyl
甲基二乙醇胺 10 氢氧化 2 15 二醇 20 46.5  Methyldiethanolamine 10 Hydroxide 2 15 diol 20 46.5
铵 单苯 柠檬酸 聚甲基丙烯酸  Ammonium monobenzene citric acid polymethacrylic acid
0.4  0.4
基醚 三辛酯 一乙醇胺盐 (数  Triyl ether monoethanolamine salt
1 均分子量为  1 average molecular weight is
10000)  10000)
1,3-二乙基 -2-咪  1,3-diethyl-2-mi
35 唑烷酮  35 oxazolidinone
一乙醇胺 30 己二  Monoethanolamine 30
四乙基 丁酰柠 聚乙烯吡咯烷 Tetraethyl butyryl chloride polyvinylpyrrolidine
醇单  Alcohol single
氢氧化 0.1 0.2 0.1 34.25 檬酸三 0.1 酮 (数均分子量 0.10 Hydroxide 0.1 0.2 0.1 34.25 citric acid three 0.1 ketone (number average molecular weight 0.10)
萘基  Naphthyl
铵 己酯 为 10000)  Ammonium hexyl ester is 10000)
醚  Ether
聚丙烯酸三乙 醇胺盐 (数均分 0.15 子量为 20000) 柠檬酸  Polyacrylic acid triethanolamine salt (number average 0.15 sub-quantity 20000) citric acid
乙醇胺 9 羟乙基乙二胺 8 酯  Ethanolamine 9 hydroxyethyl ethylenediamine 8 ester
异丙 5-氨基-四氮唑 0.5 苄基三 2-羟基  Isopropyl 5-amino-tetrazol 0.5 benzyl tri 2-hydroxy
二醇 0.5  Glycol 0.5
甲基氢 6.5 6 15 50.5 柠檬酸 苯并三氮唑二 Methyl hydrogen 6.5 6 15 50.5 citric acid benzotriazole II
单苄 0.5 氧化铵 乙醇胺盐  Monobenzyl 0.5 ammonium oxide ethanolamine salt
基醚  Ether
聚甲基丙烯酸 乙酰柠  Polymethacrylic acid
一乙醇胺盐 (数 檬酸三 0.5 3  Monoethanolamine salt (succinic acid three 0.5 3
均分子量为 辛酯 柠檬酸 Octyl ester Citric acid
四丁基 1.5 二'甘醇胺 3.5 Tetrabutyl 1.5 bis-glycolamine 3.5
甘油酯  Glyceryl ester
氢氧化 3 Hydroxide 3
2-巯基苯并噁 铵 0.5  2-mercaptobenzoic acid ammonium 0.5
二丙 唑  Dipropazole
二醇  Glycol
6 40 37 三乙醇  6 40 37 triethanol
单苯 聚氧乙烯改性 四甲基 胺柠檬 6  Monophenyl polyoxyethylene modified tetramethylamine lemon 6
基醚 的聚丙烯酸乙 氢氧化 1 酸盐 1.5  Polyether acrylate hydroxide 1 salt
酯 (数均分子量 铵  Ester (number average molecular weight ammonium
为 50000) For 50000)
* *
柠檬酸 异丙醇胺 1 月桂醇 0.2  Citric acid isopropanolamine 1 lauryl alcohol 0.2
酯 二巯基噻二唑 0.5 异丙 3-氨基 -5-巯基 四甲基 0.1  Ester dimercaptothiadiazole 0.5 isopropyl 3-amino -5-fluorenyl tetramethyl 0.1
二醇 -1,2，4-三氮唑 氢氧化 3.5 4 9 80.5  Glycol-1,2,4-triazole hydroxide 3.5 4 9 80.5
单苯 柠檬酸  Monophenyl citric acid
铵  Ammonium
基醚 二甘醇 0.2 聚氧乙烯改性  Ethylene glycol diethylene glycol 0.2 polyoxyethylene modification
胺酯 的聚甲基丙烯  Amine ester polymethacryl
1 酸 (数均分子量 为 10000) 三乙醇胺 1.5 柠檬酸  1 acid (number average molecular weight is 10000) triethanolamine 1.5 citric acid
三乙醇 0.05 4-氨基 -5-巯基  Triethanol 0.05 4-amino-5-fluorenyl
0.30 胺酯 -1,2, 4-三氮唑 丙二  0.30 amine ester -1,2,4-triazole
四丙基 Tetrapropyl
醇单  Alcohol single
氢氧化 2 3 8 85 聚乙二醇 (数均 0.01 Hydroxide 2 3 8 85 polyethylene glycol (number average 0.01
苯基  Phenyl
铵 分子量为 500)  Ammonium molecular weight is 500)
醚 冗聚糖  Ether
柠檬酸 0.05  Citric acid 0.05
聚乙烯吡咯垸 酯  Polyvinylpyrrolidone
酮 (数均分子量 0.09 为 20000) 柠檬酸  Ketone (number average molecular weight 0.09 is 20000) citric acid
丙二  C
咪唑啉 1 甲基乙醇胺 5 醇单  Imidazoline 1 methylethanolamine 5 alcohol
10 酯  10 ester
苄基  Benzyl
1-苯基 -5-巯基 醚 柠檬酸 3 1  1-phenyl-5-nonyl ether citric acid 3 1
四氮唑 甲基氢 8 9 41  Tetrazolium methyl hydrogen 8 9 41
氧化铰 丙二 甲基二 聚氧乙烯改性 Oxidation hinge propylene dimethicone modification
醇单 乙醇胺 的聚甲基丙烯  Alcohol monoethanolamine polymethyl methacrylate
15 5 2 苯基 柠檬酸 酸 (数均分子量 醚 ±卜 为 10000) 柠檬酸 甲基二乙醇胺 7.5 15 5 2 phenyl citrate (number average molecular weight ether ± 10,000) Citric acid methyl diethanolamine 7.5
异丙醇 0.3  Isopropyl alcohol 0.3
胺酯 二巯基噻二唑 1.2 二异 聚乙二醇 (数均 四乙基 丙二 分子量为 0.5 氢氧化 2.5 10 醇单 5 72.3 20000)  Amino ester Dimercaptothiadiazole 1.2 Diisoethylene glycol (number average tetraethyl propylene two molecular weight 0.5 KOH 2.5 10 Alcohol single 5 72.3 20000)
柠檬酸  Citric acid
铰 苯基 聚氧乙烯改性  Hinge phenyl polyoxyethylene modification
四甲基 0.3  Tetramethyl 0.3
醚 的聚丙烯酸三  Ether polyacrylic acid
铰  Hinge
乙醇胺盐 (数均 0.4 分子量为  Ethanolamine salt (number average 0.4 molecular weight is
100000)  100000)
柠檬酸  Citric acid
0.2 羟乙基乙二胺 6 三铵  0.2 hydroxyethyl ethylenediamine 6 triammonium
柠檬酸 3-氨基 -1，2,4-三  Citric acid 3-amino -1,2,4-three
0.2 2 二氢铵 氮唑 三乙  0.2 2 dihydrogen ammonium azole triethyl
四丁基 聚氧乙烯改性 Tetrabutyl polyoxyethylene modification
二醇  Glycol
氢氧化 4.5 5 10 67.5 的聚甲基丙烯 Polymethyl propylene oxide 4.5 5 10 67.5
单苯  Monophenyl
铵 甲基乙 酸二乙醇胺盐 2  Ammonium methyl acetate diethanolamine salt 2
基醚  Ether
醇胺柠 0.6 (数均分子量为 檬酸盐 8000) 二甘醇胺 2 二乙二醇单乙  Alcoholamine 0.6 (number average molecular weight is citrate 8000) diglycolamine 2 diethylene glycol monoethyl
30 柠檬酸 醚  30 citrate ether
0.5  0.5
氢二铵 1-羟基亚乙基  Diammonium hydroxide 1-hydroxyethylidene
0.5 -1,1-二膦酸 异丙  0.5 -1,1-diphosphonic acid isopropyl
四甲基 Tetramethyl
二醇 聚氧乙烯改性 氢氧化 2 3 15 48.2  Glycol polyoxyethylene modified hydroxide 2 3 15 48.2
单苯 的聚甲基丙烯 铰 柠檬酸 0.5  Monostyrene polymethacrylate hinge citric acid 0.5
基醚 酸甲酯 (数均分  Methyl ether ether (number average)
四乙基 0.2  Tetraethyl 0.2
子量为 75000) 铵 二甲基乙醇胺 0.1 二乙二醇单甲 柠檬酸 5  The amount is 75000) Ammonium Dimethylethanolamine 0.1 Diethylene glycol monomethyl citrate 5
醚  Ether
四丙基 1  Tetrapropyl 1
4-氨基 -1,2,4-三 铵 0.5 二丙 氮唑 四丙基  4-amino-1,2,4-triammonium 0.5 dipropazol tetrapropyl
二醇  Glycol
氢氧化 2.5 2.5 10 77 聚氧乙烯改性 Hydrogen peroxide 2.5 2.5 10 77 Polyoxyethylene modification
单苯  Monophenyl
铵 柠檬酸 的聚丙烯酸一  Ammonium citrate polyacrylic acid
基醚  Ether
四丁基 1 乙醇胺盐 (数均 0.5 铵 分子量为  Tetrabutyl 1 ethanolamine salt (number average 0.5 ammonium molecular weight is
40000) 柠檬酸 二乙二醇单丁 40000) Diethylene glycol citrate
2 苄基三 1 醚  2 benzyl tri-1 ether
甲基铰 一乙醇胺 20 二乙醇  Methyl hinge monoethanolamine 20 diethanol
乙二胺四亚甲 丙二 胺柠檬 4 0.5  Ethylenediamine tetramethylene propylenediamine lemon 4 0.5
基膦酸 醇单  Phosphonic acid alcohol
甲基氢 9 9 50 1 Methyl hydrogen 9 9 50 1
. 苯基  Phenyl
氧化铵 聚氧乙烯改性 Ammonium oxide polyoxyethylene modification
醚  Ether
的聚甲基丙烯  Polymethacryl
2-羟基  2-hydroxyl
1 酸二乙醇胺盐 2.5 柠檬酸  1 acid diethanolamine salt 2.5 citric acid
(数均分子量为  (the number average molecular weight is
8000) 二丙二醇单甲 异丙醇 30  8000) Dipropylene glycol monomethyl isopropanol 30
醚  Ether
胺柠檬 2  Amine lemon 2
二乙烯三胺五 酸盐 0.05  Diethylenetriamine pentarate 0.05
亚甲基膦酸 丙二  Methylene phosphonic acid
四丁基 8-羟基 聚氧乙烯醚 (数 Tetrabutyl 8-hydroxy polyoxyethylene ether
醇单  Alcohol single
氢氧化 5 5 12 41.95 喹啉柠 1 均分子量为 0.5 铵 檬酸盐 10000) Hydroxide 5 5 12 41.95 Quinoline Lime 1 Average molecular weight 0.5 Ammonium citrate 10000)
醚  Ether
聚氧乙烯改性 的聚甲基丙烯 柠檬酸 1 1.5  Polyoxyethylene modified polymethacrylic acid citric acid 1 1.5
酸 (数均分子量 为 10000) 三乙胺 丙二醇单丁醚 20 柠檬酸 0.5  Acid (number average molecular weight 10000) triethylamine propylene glycol monobutyl ether 20 citric acid 0.5
氨基三亚甲基 土卜 0.2  Aminotrimethylene terb 0.2
膦酸 异丙  Phosphonic acid
四甲基 聚氧乙烯改性 Tetramethyl polyoxyethylene modification
二醇  Glycol
氢氧化 2 12.5 7 54 的聚丙烯酸 (数 Polyacrylic acid 2 12.5 7 54
单苯  Monophenyl
铰 柠檬酸 0.5  Hinge citric acid 0.5
均分子量为 基醚  Average molecular weight
乙醇胺 0.3 5000)  Ethanolamine 0.3 5000)
酯 甲基乙醇胺 3 二丙二醇单丁 三乙醇 15  Ester methylethanolamine 3 dipropylene glycol monobutyl triethanol 15
醚  Ether
胺柠檬 0.25  Amine lemon 0.25
2-膦酸丁垸 酸盐 0.1 二丙 -1,2,4-三羧酸 四丙基  2-phosphonium butyrate 0.1 dipropylene -1,2,4-tricarboxylic acid tetrapropyl
二醇 3，5-二氨基 氢氧化 2.5 2.5 6 71.45 0.1  Diol 3,5-diamino hydroxide 2.5 2.5 6 71.45 0.1
单苯 -1,2,4-三氮唑 铵  Monophenyl-1,2,4-triazole ammonium
基醚 柠檬酸  Ethyl ether
1.5  1.5
哌嗉 聚氧乙烯醚 (数  Piperazine polyoxyethylene ether
0.6 均分子量为  0.6 average molecular weight is
10000) 二丙二醇单乙 10000) Dipropylene glycol single B
25 醚  25 ether
一乙醇胺 5  Monoethanolamine 5
丙二  C
四乙基 乙醇胺 2-巯基苯并噻  Tetraethylethanolamine 2-mercaptobenzothiophene
醇单 0.3  Alcohol single 0.3
26 氢氧化 3 3 10 48.2 柠檬酸 5 唑  26 Hydroxide 3 3 10 48.2 Citric acid 5 azole
苯基  Phenyl
铵 ±卜  Ammonium
聚氧乙烯改性  Polyoxyethylene modification
醚  Ether
的聚丙烯酸一  Polyacrylic acid
乙醇胺盐 (数均 0.5  Ethanolamine salt (number average 0.5
分子量为  Molecular weight
40000)  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 对比清洗剂组合物 1，~7，和本发明的清洗剂组合物 27〜42 表 2给出了对比清洗剂组合物 Γ~7'和本发明的清洗剂组合物 27~42的 配方，按表 2中所列组分及其含量，简单混合均匀， 即制得各清洗剂组合物。 对比清洗剂组合物 Γ~7'和本发明的清洗剂组合物 27~42的组分和含量  Advantageous effects of the present invention will be further hereinafter described by way of preferred effect embodiments of the present invention. Effect Examples Comparative Cleaning Agent Compositions 1, 7, and Cleaning Agent Compositions 27 to 42 of the Invention Table 2 shows comparative cleaning agent compositions Γ~7' and the cleaning composition compositions 27-42 of the present invention. The formulations were prepared by simply mixing uniformly according to the components listed in Table 2 and their contents, that is, each detergent composition was prepared. Comparative cleaning agent composition Γ~7' and the composition and content of the cleaning composition 27~42 of the present invention
聚氧乙 聚乙烯 烯改性 四甲 丙二 乙醇 吡咯垸 甲基 的聚甲 清 二甲  Polyoxyethylene styrene modified tetramethyl propylene diethanol pyrrole oxime methyl polymethyl dimethyl dimethyl
基氢 去离 醇单 柠檬 胺柠 环丁 单乙 酮（数 苯并 基丙烯 洗 基亚  Base hydrogen deionization alcohol mono lemon amine melamine cyclobutane monoethyl ketone (number benzo propylene propylene
氧化 子水 苯基 酸 檬酸 砜 醇胺 均分子 三氮 酸 (数均 剂 砜  Oxide water phenyl citrate sulfone alcohol amine homotrienic acid trinitrogen acid (number average agent sulfone)
铵 醚 ±卜 量为 分子量  Ammonium ether ± quantity is molecular weight
10000) 为  10000) for
10000) 10000)
1 ' 1.00 4.00 1 95.00 1 1 1 1 1 1 /1 ' 1.00 4.00 1 95.00 1 1 1 1 1 1 /
2' 1.50 4.00 1 94.30 1 1 1 1 0.20 12' 1.50 4.00 1 94.30 1 1 1 1 0.20 1
3， 2.00 4.00 1 93.55 1 1 1 1 0.10 0.35 13, 2.00 4.00 1 93.55 1 1 1 1 0.10 0.35 1
4， 2.00 6.00 1 71.65 1 20.00 1 1 0.35 14, 2.00 6.00 1 71.65 1 20.00 1 1 0.35 1
5， 2.00 3.00 1 93.70 1 1 / 1.00 1 0.30 15, 2.00 3.00 1 93.70 1 1 / 1.00 1 0.30 1
6' 3.00 6.00 5.00 86.00 1 1 1 1 1 16' 3.00 6.00 5.00 86.00 1 1 1 1 1 1
Τ 3.00 6.00 / 91.00 1 1 1 1 1 1 1Τ 3.00 6.00 / 91.00 1 1 1 1 1 1 1
27 1.00 4.00 2.00 92.90 0.10 1 1 1 1 1 127 1.00 4.00 2.00 92.90 0.10 1 1 1 1 1 1
28 1.50 4.00 3.00 91.35 1 0.15 1 1 1 1 128 1.50 4.00 3.00 91.35 1 0.15 1 1 1 1 1
29 1.50 2.00 4.00 92.30 0.20 1 1 1 1 1 129 1.50 2.00 4.00 92.30 0.20 1 1 1 1 1 1
30 2.00 4.00 4.50 87.50 / 0.30 1 1.50 1 1 0.2030 2.00 4.00 4.50 87.50 / 0.30 1 1.50 1 1 0.20
31 2.00 6.00 5.00 56.60 0.30 1 27.00 2.50 1 0.25 0.3531 2.00 6.00 5.00 56.60 0.30 1 27.00 2.50 1 0.25 0.35
32 2.00 3.00 6.00 83.20 0.20 1.00 1 4.50 0.10 1 132 2.00 3.00 6.00 83.20 0.20 1.00 1 4.50 0.10 1 1
33 3.00 6.00 5.00 61.25 0.30 0.60 16.00 7.00 0.30 1 0.5533 3.00 6.00 5.00 61.25 0.30 0.60 16.00 7.00 0.30 1 0.55
34 3.50 3.50 7.50 73.85 1 0.90 1 10.00 1 1 0.7534 3.50 3.50 7.50 73.85 1 0.90 1 10.00 1 1 0.75
35 4.00 4.00 8.00 66.40 0.50 1 1 15.50 0.10 0.50 1.0035 4.00 4.00 8.00 66.40 0.50 1 1 15.50 0.10 0.50 1.00
36 4.50 4.50 9.20 44.30 0.80 3.20 10.00 23.50 1 1 136 4.50 4.50 9.20 44.30 0.80 3.20 10.00 23.50 1 1 1
37 5.00 5.00 10.50 38.50 1.20 1.50 1 35.30 0.20 0.50 2.3037 5.00 5.00 10.50 38.50 1.20 1.50 1 35.30 0.20 0.50 2.30
38 2.30 2.50 5.50 83.45 0.30 1 1 5.50 1 1 0.45 39 2.90 3.00 6.00 74.60 1 2.20 1 10.20 0.20 1 0.9038 2.30 2.50 5.50 83.45 0.30 1 1 5.50 1 1 0.45 39 2.90 3.00 6.00 74.60 1 2.20 1 10.20 0.20 1 0.90
40 3.50 4.00 9.50 63.65 0.60 1 1 16.80 1 0.60 1.3540 3.50 4.00 9.50 63.65 0.60 1 1 16.80 1 0.60 1.35
41 1.80 2.50 4.50 82.35 1 1.20 1 7.50 - 0.15 1 1 41 1.80 2.50 4.50 82.35 1 1.20 1 7.50 - 0.15 1 1
42 2.60 2.90 6.50 75.60 0.25 1 1 11.50 1 1 0.65 将表 2中的各种组分按照比例混合均匀， 制得对比清洗剂组合物 Γ〜7' 和本发明的清洗剂组合物 27〜42。 其中， 除对比清洗剂组合物 7，中有少量未 溶解的颗粒状的四甲基氢氧化铵以外， 对比清洗剂组合物 Γ〜6，和本发明的 清洗剂组合物 27〜42均为澄清透明的均相溶液。  42 2.60 2.90 6.50 75.60 0.25 1 1 11.50 1 1 0.65 The components in Table 2 were uniformly mixed in proportion to obtain a comparative detergent composition Γ~7' and the cleaning composition 27~42 of the present invention. Wherein, in contrast to the comparative detergent composition 7, a small amount of undissolved granular tetramethylammonium hydroxide, the comparative cleaning composition Γ~6, and the cleaning composition 27~42 of the present invention are both clarified A transparent homogeneous solution.
将表 2中的对比清洗剂组合物 Γ~6'和本发明的清洗剂组合物 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 cleaning composition Γ~6' in Table 2 and the cleaning composition 27~42 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、 将表 2中的对比清洗剂组合物 Γ〜6'和本发明的清洗剂组合物 27〜42 用于清洗空白 Cu晶片， 测试其对金属 Cu的腐蚀情况。 测试方法和条件： 将 4 X 4cm空白 Cu晶片浸入清洗剂组合物中，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. The comparative cleaning composition Γ~6' in Table 2 and the cleaning composition 27~42 of the present invention were used to clean a blank Cu wafer and test its corrosion to metallic Cu. Test methods and conditions: 4 X 4 cm blank Cu wafer was immersed in the cleaning agent composition, 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, using four The polar probe instrument was used to measure the change in surface resistance of the blank Cu wafer before and after etching. The results are shown in Table 3.
2、 将表 2中的对比清洗剂组合物 Γ〜6'和本发明的清洗剂组合物 27~42 用于清洗空白 A1晶片， 测试其对金属 A1的腐蚀情况。 测试方法和条件： 将 4 X 4cm空白 A1晶片浸入清洗剂组合物中， 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. The comparative cleaning composition Γ~6' in Table 2 and the cleaning composition 27~42 of the present invention were used to clean the blank A1 wafer and test its corrosion to the metal A1. Test methods and conditions: 4 4 4 cm blank A1 wafer was immersed in the cleaning composition, 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, using four The polar probe instrument 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、 将表 2中的对比清洗剂组合物 Γ~6'和本发明的清洗剂组合物 27〜42 用于清洗空白的四乙氧基硅烷 （TEOS ) 晶片， 测试其对非金属 TEOS的腐 蚀情况。测试方法和条件：将 4 X 4cm空白 TEOS晶片浸入清洗剂组合物中， 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 cleaning composition Γ~6' in Table 2 and the cleaning composition 27~42 of the present invention were used to clean blank tetraethoxysilane (TEOS) wafers and tested for corrosion of non-metallic TEOS. Happening. Test Methods and Conditions: A 4 X 4 cm blank TEOS wafer was dipped into the cleaning composition, 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. Determination of TEOS thickness before and after cleaning of blank TEOS wafers using Nanospec6100 thickness gauge The change in degree is calculated and the results are shown in Table 3.
4、 将表 2中的对比清洗剂组合物 Γ〜6'和本发明的清洗剂组合物 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） 浸入表 2中所示的清洗剂组合物中，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 组合物对晶片图案的腐蚀情况如表 3所示。  4. The comparative cleaning composition Γ~6' in Table 2 and the cleaning composition 27~42 of the present invention are used to clean the photoresist on the semiconductor wafer. The cleaning method is as follows: A semiconductor wafer (containing a pattern) containing a negative acrylate-based photoresist (having a thickness of about 60 μm and exposed and etched) is immersed in the cleaning composition shown in Table 2, at 20 The mixture was shaken at ~85 ° C for 1 to 30 minutes using a constant temperature oscillator, then washed with deionized water and then dried with high purity nitrogen. The cleaning effect of the photoresist and the corrosion of the wafer pattern by the cleaning composition are shown in Table 3.
表 3 对比清洗剂组合物 Γ~6'和本发明的清洗剂组合物 27~42对金属 Cu和 A1以及  Table 3 Comparative cleaning agent composition Γ~6' and the cleaning composition of the present invention 27~42 pairs of metals Cu and A1 and
非金属 TEOS的腐蚀性及其对负性光刻胶 （厚度约为 60微米） 的清洗情况  Corrosion of non-metallic TEOS and its cleaning of negative photoresist (about 60 microns thick)
Figure imgf000017_0001
腐 蚀 情 ◎ 基本 清 洗 情 ◎ 完全
Figure imgf000017_0001
Corrosion ◎ Basic cleaning ◎ Complete
况： 无腐蚀； 况:. 去除；  Condition: no corrosion; condition: removal;
〇 略有 O 少量  略 slightly O small amount
腐蚀； ！ 残余；  Corrosion; Residual
△ 中等 Δ 较多  △ medium Δ more
腐蚀； \ 残余；  Corrosion; \ residual;
X 严重 1  X serious 1
1 < X 大量  1 < X mass
腐蚀。 残余。  corrosion. Residual.
且经过曝光和刻蚀） 的半导体晶片 （含有图案）浸入表 2中所示的本发明的 清洗剂组合物 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组合物对 晶片图案的腐蚀情况如表 4所示。 And exposed and etched semiconductor wafers (including patterns) are immersed in the cleaning composition 32 to 42 of the present invention shown in Table 2, and shaken at 40 to 85 ° C for 10 to 60 minutes using a constant temperature oscillator. It was then washed with deionized water and then dried with high purity nitrogen. The cleaning effect of the photoresist and the corrosion of the wafer pattern by the cleaning composition are shown in Table 4.
表 4 表 2中本发明的清洗剂组合物 32~42对负性丙烯酸酯类  Table 4 The cleaning composition of the present invention in Table 2 32~42 pairs of negative acrylates
光刻胶 （厚度约为 150微米） 的清洗情况  Cleaning of photoresist (about 150 microns thick)
Figure imgf000018_0001
Figure imgf000018_0001
从表 3和表 4可以看出， 与对比清洗剂组合物 Γ~6，相比， 本发明的清 洗剂组合物 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的腐蚀性很低， 对晶片 图案无腐蚀或损坏。 As can be seen from Tables 3 and 4, the cleaning of the present invention is compared with the comparative cleaning agent composition Γ~6. The lotion compositions 27 to 42 have good cleaning ability for thick film negative acrylate photoresists, wide temperature range, low corrosivity to metal Cu and A1 and non-metal TEOS, and no corrosion to wafer patterns. Or damaged.
综上所述， 本发明中的光刻胶清洗剂组合物， 可以在 20〜85 °C下除去 20μιη 以上的厚膜光刻胶和其它刻蚀残留物， 而且其含有的垸基二醇芳基醚 以及选自柠檬酸、柠檬酸酯和柠檬酸盐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柠檬酸、柠檬酸酯和 柠檬酸盐的缓蚀剂对金属的腐蚀表现出良好的抑制作用， 能够有效抑制晶片 图案和基材上腐蚀暗点 （点蚀） 的产生。 本发明的光刻胶清洗剂组合物中含 有的选自柠檬酸、 柠檬酸酯和柠檬酸盐的缓蚀剂易于生物降解， 有利于环境 保护。本发明的光刻胶清洗剂组合物对二氧化硅等非金属材料表现出极弱的 腐蚀性。本发明的光刻胶清洗剂组合物中可以含有的聚丙烯酸类缓蚀剂对金 属尤其是铝的腐蚀表现出极强的抑制作用，可以进一步抑制晶片图案和基材 的腐蚀。本发明中的光刻胶清洗剂组合物可以溶解除去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 晶片图案和基材的腐蚀或损坏。  In summary, the photoresist cleaning composition of the present invention can remove a thick film photoresist and other etching residues of 20 μm or more at 20 to 85 ° C, and contains a mercapto diol. A base ether and a corrosion inhibitor selected from the group consisting of citric acid, citrate and citrate can form a protective film on the surface of the wafer pattern and the substrate to prevent attack of the wafer pattern and the substrate by halogen atoms, hydroxide ions, and the like. , thereby reducing the corrosion of the wafer pattern and the substrate; in particular, the corrosion inhibitor selected from the group consisting of citric acid, citrate and citrate exhibits a good inhibition of corrosion of the metal, and can effectively suppress the wafer pattern and the base. Corrosion of dark spots (pitting) on the material. The photoresist cleaner composition of the present invention contains a corrosion inhibitor selected from the group consisting of citric acid, citrate and citrate, which is easily biodegradable and is environmentally friendly. The photoresist cleaning composition of the present invention exhibits extremely weak corrosiveness to non-metallic materials such as silica. The polyacrylic corrosion inhibitor which can be contained in the photoresist cleaning composition of the present invention exhibits an extremely strong inhibitory effect on corrosion of metals, particularly aluminum, and can further suppress corrosion of the wafer pattern and the substrate. The photoresist cleaning composition of the present invention can dissolve and remove a high-crosslinking thick film negative photoresist on a semiconductor wafer, thereby avoiding deposition or adhesion of the photoresist on the surface of the wafer without causing wafer pattern and Corrosion or damage to the substrate.

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， 所述的缓蚀剂包含选自柠檬酸、 柠 檬酸酯和柠檬酸盐中的一种或多种。 A photoresist cleaning composition comprising quaternary ammonium hydroxide, water, mercapto diol aryl ether, dimethyl sulfoxide and a corrosion inhibitor, wherein the corrosion inhibitor comprises From one or more of citric acid, citrate and citrate.
2、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于， 所述的柠 檬酸、 柠檬酸酯和柠檬酸盐选自柠檬酸、 2-羟基柠檬酸、 柠檬酸三甲酯、 柠 檬酸三乙酯、柠檬酸三丙酯、柠檬酸三丁酯、柠檬酸三己酯、柠檬酸三辛酯、 乙酰柠檬酸三乙酯、 乙酰柠檬酸三丙酯、 乙酰柠檬酸三丁酯、 乙酰柠檬酸三 己酯、 乙酰柠檬酸三辛酯、 丁酰柠檬酸三己酯、 柠檬酸月桂醇酯、 柠檬酸甘 油酯、 柠檬酸乙醇胺酯、 柠檬酸三乙醇胺酯、 柠檬酸二甘醇胺酯、 柠檬酸异 丙醇胺酯、 壳聚糖柠檬酸酯、 柠檬酸咪唑啉酯、 柠檬酸二氢铵、 柠檬酸氢二 铵、 柠檬酸三铵、 柠檬酸四甲基铵、 柠檬酸四乙基铵、 柠檬酸四丙基铵、 柠 檬酸四丁基铵、柠檬酸苄基三甲基铵、乙醇胺柠檬酸盐、二乙醇胺柠檬酸盐、 三乙醇胺柠檬酸盐、 二甘醇胺柠檬酸盐、 异丙醇胺柠檬酸盐、 甲基乙醇胺柠 檬酸盐、 甲基二乙醇胺柠檬酸盐、三乙胺柠檬酸盐、柠檬酸哌嗪和 8-羟基喹 啉柠檬酸盐中的一种或多种。  2. The photoresist cleaning composition according to claim 1, wherein the citric acid, citrate and citrate are selected from the group consisting of citric acid, 2-hydroxycitric acid, and trimethyl citrate. , triethyl citrate, tripropyl citrate, tributyl citrate, trihexyl citrate, trioctyl citrate, acetyl triethyl citrate, acetyl tripropyl citrate, acetyl citrate tributyl Ester, acetyl trihexyl citrate, acetyl trioctyl citrate, butyryl trihexyl citrate, lauryl citrate, glyceryl citrate, ethanolamine citrate, triethanolamine citrate, diethylene glycol citrate Alcoholamine ester, isopropanol citrate, chitosan citrate, imidazoline citrate, ammonium dihydrogen citrate, diammonium hydrogen citrate, triammonium citrate, tetramethylammonium citrate, lemon Tetraethylammonium acid, tetrapropylammonium citrate, tetrabutylammonium citrate, benzyltrimethylammonium citrate, ethanolamine citrate, diethanolamine citrate, triethanolamine citrate, diglycolamine Citrate, isopropanolamine citric acid One or more of a salt, methylethanolamine citrate, methyldiethanolamine citrate, triethylamine citrate, piperazine citrate, and 8-hydroxyquinoline citrate.
3、 如权利要求 2所述的光刻胶清洗剂组合物， 其特征在于， 所述的柠 檬酸、 柠檬酸酯和柠檬酸盐选自柠檬酸、 2-羟基柠檬酸、 柠檬酸月桂醇酯、 柠檬酸甘油酯、 柠檬酸乙醇胺酯、 柠檬酸三乙醇胺酯、 柠檬酸二甘醇胺酯、 柠檬酸四甲基铵、 柠檬酸四乙基铵、 乙醇胺柠檬酸盐、 三乙醇胺柠檬酸盐和 二甘醇胺柠檬酸盐中的一种或多种。  3. The photoresist cleaning composition according to claim 2, wherein the citric acid, citrate and citrate are selected from the group consisting of citric acid, 2-hydroxycitric acid, and lauryl citrate. , glyceryl citrate, ethanolamine citrate, triethanolamine citrate, diglycol citrate, tetramethylammonium citrate, tetraethylammonium citrate, ethanolamine citrate, triethanolamine citrate and One or more of diglycolamine citrate.
4、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于， 所述的柠 檬酸、 柠檬酸酯和柠檬酸盐的总含量为 0.01〜10wt%。  The photoresist cleaning composition according to claim 1, wherein the total content of the citric acid, citrate and citrate is 0.01 to 10% by weight.
5、 如权利要求 4所述的光刻胶清洗剂组合物， 其特征在于， 所述的柠 檬酸、 柠檬酸酯和柠檬酸盐的总含量为 0.1~5wt%。  The photoresist cleaning composition according to claim 4, wherein the total content of the citric acid, citrate and citrate is 0.1 to 5 wt%.
6、 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。  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.
7、 如权利要求 1所述的光刻胶清洗剂组合物， 其特征在于， 所述的季 铵氢氧化物的含量为 0.1~10wt%。 7. The photoresist cleaning composition according to claim 1, wherein said season The content of the ammonium hydroxide is 0.1 to 10% by weight.
8、 如权利要求 7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 7, wherein the quaternary ammonium hydroxide is contained in an amount of from 1 to 5 % by weight.
9、 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.
10、 如权利要求 9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 9, wherein the water is contained in an amount of from 0.5 to 10% by weight.
11、 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 基二醇芳基醚中的垸基二醇的碳原子数目为 3〜18。  The photoresist cleaning composition according to claim 1, wherein the mercapto diol in the mercapto glycol aryl ether has a carbon number of from 3 to 18.
12、 如权利要求 11 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、 六縮异丙二醇单苯基醚、 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 11, 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, hexapropylene glycol monophenyl ether, hexamethylene glycol monophenyl ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether, and hexanediol mono-naphthyl ether.
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 垸基二醇芳基醚选自丙二醇单苯基醚、 异丙二醇单苯基醚、二丙二醇单苯基 醚、 二异丙二醇单苯基醚和丙二醇单苄基醚中的一种或多种。  The photoresist cleaning composition according to claim 12, wherein the mercapto glycol aryl ether is selected from the group consisting of propylene glycol monophenyl ether, isopropyl glycol monophenyl ether, and dipropylene glycol monophenyl. One or more of a group ether, diisopropyl glycol monophenyl ether, and propylene glycol monobenzyl ether.
14、 如权利要求 11 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 11, wherein the mercapto glycol aryl ether is contained in an amount of 0.1 to 65 wt%.
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 垸基二醇芳基醚的含量为 0.5〜20wt%。  The photoresist cleaning composition according to claim 14, wherein the mercapto glycol aryl ether is contained in an amount of from 0.5 to 20% by weight.
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.
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 二甲基亚砜的含量为 30〜90wt%。  The photoresist cleaning composition according to claim 16, wherein the dimethyl sulfoxide is contained in an amount of from 30 to 90% by weight.
18、 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包含选自极性有机共溶剂、 表面活性剂和除柠檬 酸、 柠檬酸酯和柠檬酸盐以外的其它缓蚀剂中的一种或多种。  18. The photoresist cleaning composition according to claim 1, wherein the photoresist cleaning composition further comprises a polar organic cosolvent, a surfactant, and a citric acid, lemon, and the like. One or more of the other corrosion inhibitors other than the acid ester and citrate.
19、 如权利要求 18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%; 所述的除柠檬酸、 柠檬酸酯和柠檬酸盐的缓蚀 剂以外的其它缓蚀剂含量为 5wt%， 但不包括 0wt%。 The photoresist cleaning composition according to claim 18, 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 inhibition of the citric acid, citrate and citrate The corrosion inhibitor content other than the agent was 5 wt%, but did not include 0 wt%.
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 极性有机共溶剂含量为 5〜30wt%; 所述的表面活性剂含量为 0.05〜3.0wt%; 所述的除柠檬酸、 柠檬酸酯和柠檬酸盐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 19, wherein the polar organic co-solvent content is 5 to 30% by weight; the surfactant content is 0.05 to 3.0% by weight; The corrosion inhibitor content of the corrosion inhibitor other than citric acid, citrate ester and citrate is 0.05-3.0wt
21、 如权利要求 18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、 咪唑垸酮、 醇胺和烷基二醇单烷基醚中的一 种或多种。  The photoresist cleaning composition according to claim 18, wherein the polar organic co-solvent is selected from the group consisting of sulfoxide, sulfone, imidazolium, alcohol amine, and alkyl glycol monoalkyl. One or more of the ethers.
22、 如权利要求 21 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； 所述的咪唑垸酮选自 2-咪唑垸酮、 1,3-二甲基 -2-咪唑烷酮 和 1，3-二乙基 -2-咪唑垸酮中的一种或多种； 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； 所述的垸基二醇单烷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 21, 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 imidazolium is selected from the group consisting of 2-imidazolium, 1,3-dimethyl-2-imidazolidinone, and 1,3-diethyl-2 One or more of imidazolium; the alcohol amine is selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, isopropanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine, and hydroxy One or more of ethylethylenediamine; the mercaptodiol monoalkyl 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.
23、 如权利要求 18所述的光刻胶清洗剂组合物， 其特征在于， 所述的 表面活性剂选自聚二烯醇、 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 18, wherein the surfactant is selected from one or more of a polydienol, a polyvinylpyrrolidone, and a polyoxyethylene ether. Kind.
24、 如权利要求 18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 18, wherein the surfactant has a number average molecular weight of 500 to 20,000.
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 表面活性剂的数均分子量为 1000〜； 10000。  The photoresist cleaning composition according to claim 24, wherein the surfactant has a number average molecular weight of 1000 to 10,000.
26、 如权利要求 18所述的光刻胶清洗剂组合物， 其特征在于， 所述的 除柠檬酸、 柠檬酸酯和柠檬酸盐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 18, wherein the corrosion inhibitor other than citric acid, citrate and citrate is selected from the group consisting of alcohol amines, azoles, One or more of phosphonic acid and polyacrylic corrosion inhibitors.
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 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。 The photoresist cleaning composition according to claim 26, 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 azoles The corrosion 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 Oxazole, 3,5-diamino-1,2,4-triazole, 4-amino-5-mercapto-1,2,4-triazole, 5-amino-tetrazole and 1-phenyl- One or more of 5-mercaptotetrazole; the phosphonic acid corrosion inhibitor is selected from the group consisting of 1-hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, 2-phosphine One or more of butyrate-1,2,4-tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid.
28、 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、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 26, wherein the polyacrylic corrosion inhibitor is selected from the group consisting of acrylic polymers and copolymers thereof, methacrylic polymers and copolymers thereof, Alcohol amine salt of acrylic polymer, alcohol amine salt of methacrylic acid polymer, polyoxyethylene modified acrylic polymer and ester and alkanolammonium salt thereof, polyoxyethylene modified methacrylic acid polymer and ester thereof One or more of the alkanolammonium salts.
29、 如权利要求 28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 28, wherein the polyacrylic corrosion inhibitor has a number average molecular weight of 500 to 100,000.
30、 如权利要求 29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 29, wherein the polyacrylic corrosion inhibitor has a number average molecular weight of 1,000 to 50,000.
PCT/CN2009/001284 2008-11-28 2009-11-19 Rinse solution composition for removing resist WO2010060273A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009801483641A CN102227690A (en) 2008-11-28 2009-11-19 Rinse solution composition for removing photoresist

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200810203714A CN101750911A (en) 2008-11-28 2008-11-28 Photoresist detergent composition
CN200810203714.7 2008-11-28

Publications (1)

Publication Number Publication Date
WO2010060273A1 true WO2010060273A1 (en) 2010-06-03

Family

ID=42225210

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2009/001284 WO2010060273A1 (en) 2008-11-28 2009-11-19 Rinse solution composition for removing resist

Country Status (2)

Country Link
CN (2) CN101750911A (en)
WO (1) WO2010060273A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012168485A1 (en) * 2011-06-09 2012-12-13 Technic France Composition of solutions and conditions for use enabling the stripping and complete dissolution of photoresists
CN103571664A (en) * 2013-10-31 2014-02-12 合肥中南光电有限公司 Environment-friendly solar silicon wafer cleaning agent and preparation method thereof
EP2892967A4 (en) * 2012-09-07 2016-02-24 Cabot Microelectronics Corp Polyp yrrol1done polishing compost-ion and method

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102477359B (en) * 2010-11-26 2015-12-02 安集微电子（上海）有限公司 A kind of chemically mechanical polishing cleaning liquid
CN102012645A (en) * 2010-12-24 2011-04-13 东莞市智高化学原料有限公司 Photoresist stripping solution
CN102533474B (en) * 2010-12-30 2015-09-16 安集微电子（上海）有限公司 A kind of scavenging solution and purging method thereof
CN103513524A (en) * 2013-09-25 2014-01-15 杨桂望 Semiconductor remover
CN104656382A (en) * 2015-02-12 2015-05-27 陕西莱特光电材料股份有限公司 Stripping liquid capable of effectively removing photoresist of light-emitting diode (LED) chip, and stripping method for removing photoresist of LED chip
DE102015210481A1 (en) * 2015-06-09 2016-12-15 Henkel Ag & Co. Kgaa Use of citric acid esters as corrosion inhibitor in alcoholic aerosol-sprayable cosmetic compositions
CN105316120A (en) * 2015-11-24 2016-02-10 苏州盖德精细材料有限公司 General type glue dissolvent composition and preparation method thereof
CN105441200A (en) * 2015-12-04 2016-03-30 三达奥克化学股份有限公司 Semiconductor silicon wafer degumming cleaning fluid and preparation method
CN109375482A (en) * 2018-11-01 2019-02-22 博罗县东明新材料研究所 PCB developer solution and preparation method thereof
CN113741158A (en) * 2020-05-29 2021-12-03 昆山欣谷微电子材料有限公司 Aqueous stripping liquid composition and use method thereof
CN113568287B (en) * 2021-06-10 2023-07-04 江阴润玛电子材料股份有限公司 Photoresist cleaning agent for flexible panel and production process thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1724626A (en) * 2004-07-22 2006-01-25 气体产品与化学公司 Composition for removing photoresist and/or etching residue from a substrate and use thereof
CN1900146A (en) * 2005-07-21 2007-01-24 安集微电子（上海）有限公司 Chemical and mechanical polishing liquid
CN1982426A (en) * 2005-12-16 2007-06-20 安集微电子（上海）有限公司 Slow-releasing agent system for cleaning semiconductor chip
CN101187787A (en) * 2006-11-17 2008-05-28 安集微电子（上海）有限公司 Low etching photoresist cleaning agent and its cleaning method
CN101290482A (en) * 2007-04-19 2008-10-22 安集微电子（上海）有限公司 Cleaning fluid for cleaning plasma etching residue

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1724626A (en) * 2004-07-22 2006-01-25 气体产品与化学公司 Composition for removing photoresist and/or etching residue from a substrate and use thereof
CN1900146A (en) * 2005-07-21 2007-01-24 安集微电子（上海）有限公司 Chemical and mechanical polishing liquid
CN1982426A (en) * 2005-12-16 2007-06-20 安集微电子（上海）有限公司 Slow-releasing agent system for cleaning semiconductor chip
CN101187787A (en) * 2006-11-17 2008-05-28 安集微电子（上海）有限公司 Low etching photoresist cleaning agent and its cleaning method
CN101290482A (en) * 2007-04-19 2008-10-22 安集微电子（上海）有限公司 Cleaning fluid for cleaning plasma etching residue

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012168485A1 (en) * 2011-06-09 2012-12-13 Technic France Composition of solutions and conditions for use enabling the stripping and complete dissolution of photoresists
FR2976290A1 (en) * 2011-06-09 2012-12-14 Jerome Daviot COMPOSITION OF SOLUTIONS AND CONDITIONS OF USE FOR THE COMPLETE REMOVAL AND DISSOLUTION OF PHOTO-LITHOGRAPHIC RESINS
US20140076356A1 (en) * 2011-06-09 2014-03-20 Technic France Composition of solutions and conditions for use enabling the stripping and complete dissolution of photoresists
EP2892967A4 (en) * 2012-09-07 2016-02-24 Cabot Microelectronics Corp Polyp yrrol1done polishing compost-ion and method
CN103571664A (en) * 2013-10-31 2014-02-12 合肥中南光电有限公司 Environment-friendly solar silicon wafer cleaning agent and preparation method thereof

Also Published As

Publication number Publication date
CN102227690A (en) 2011-10-26
CN101750911A (en) 2010-06-23

Similar Documents

Publication Publication Date Title
WO2010060273A1 (en) Rinse solution composition for removing resist
TW556054B (en) Stripping composition
JP4741315B2 (en) Polymer removal composition
WO2010060274A1 (en) Detergent for removing photo resist
CN101076760B (en) Non-aqueous, non-corrosive microelectronic cleaning compositions containing polymeric corrosion inhibitors
WO2009006783A1 (en) Cleaning composition for removing resist
TWI461525B (en) Wet clean compositions for cowp and porous dielectrics
JP3302120B2 (en) Stripper for resist
JP4208924B2 (en) Non-aqueous, non-corrosive microelectronic cleaning composition
CN1985217B (en) Non-aqueous microelectronic cleaning compositions containing fructose
JP5276662B2 (en) Reduction of metal etch rate using stripping solution containing metal salt
JP2001523356A (en) Non-corrosive compositions for resist stripping and cleaning
WO2009046637A1 (en) Cleaning composition for removing resist
WO2008125003A1 (en) Low etch cleaning composition for removing resist
CN101750914A (en) Photoresist detergent composition
EP1154868A1 (en) Non-corrosive cleaning composition and method for removing plasma etching residues
WO2009155782A1 (en) Detergent for removing photoresist
WO2010037263A1 (en) Rinse solution for removing resist
KR101341701B1 (en) Resist stripper composition and a method of stripping resist using the same
CN102117025A (en) Photoresist detergent composition
WO2010051689A1 (en) Rinse solution for removing thick film resist
KR101341746B1 (en) Resist stripper composition and a method of stripping resist using the same
TWI387858B (en) Cleaning solution for photoresist
CN102117023A (en) Photoresist detergent
KR20070019604A (en) Polymer-stripping composition

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980148364.1

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09828534

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09828534

Country of ref document: EP

Kind code of ref document: A1