WO2009046637A1 - Cleaning composition for removing resist - Google Patents

Cleaning composition for removing resist Download PDF

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Publication number
WO2009046637A1
WO2009046637A1 PCT/CN2008/001693 CN2008001693W WO2009046637A1 WO 2009046637 A1 WO2009046637 A1 WO 2009046637A1 CN 2008001693 W CN2008001693 W CN 2008001693W WO 2009046637 A1 WO2009046637 A1 WO 2009046637A1
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WO
WIPO (PCT)
Prior art keywords
ether
cleaning agent
agent according
acid
photoresist cleaning
Prior art date
Application number
PCT/CN2008/001693
Other languages
French (fr)
Chinese (zh)
Inventor
Robert Yongtao Shi
Libbert Hongxiu Peng
Jenny Huiying Cao
Original Assignee
Anji Microelectronics (Shanghai) Co., Ltd
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 Anji Microelectronics (Shanghai) Co., Ltd filed Critical Anji Microelectronics (Shanghai) Co., Ltd
Priority to CN200880109166.XA priority Critical patent/CN101842746B/en
Publication of WO2009046637A1 publication Critical patent/WO2009046637A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • 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
    • 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
    • C11D7/5022—Organic solvents containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
    • 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
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • 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
    • 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
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds
    • 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
    • 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
    • C11D7/36—Organic compounds containing phosphorus

Definitions

  • the present invention relates to a cleaning agent in a semiconductor manufacturing process, and in particular to a photoresist cleaning agent.
  • a pattern of photoresist is formed on a surface of a metal such as silicon dioxide, Cu (copper) or the like and a low-k material, and the pattern is transferred by wet or dry etching after exposure.
  • the low temperature and fast cleaning process is an important direction for the development of semiconductor wafer manufacturing processes.
  • Negative photoresists with thicknesses above 20 ⁇ are gradually being used in semiconductor wafer fabrication processes.
  • most of the photoresist cleaners in the industry have better cleaning ability for positive photoresists, but cannot completely remove the wafers.
  • cleaning agents often cause corrosion of the wafer pattern and substrate during the chemical cleaning of the photoresist by the semiconductor wafer.
  • oxidation and corrosion of metals especially active metals such as aluminum and copper
  • metals especially active metals such as aluminum and copper
  • the photoresist cleaning agent is mainly composed of a polar organic solvent, a strong alkali, and/or water, and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in a cleaning agent or rinsing the semiconductor wafer with a cleaning agent.
  • Patent document WO03104901 immerses a wafer into the cleaning agent by using an alkaline cleaning agent such as tetramethylammonium hydroxide ( ⁇ ), sulfolane (SFL), water, and trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA).
  • an alkaline cleaning agent such as tetramethylammonium hydroxide ( ⁇ ), sulfolane (SFL), water, and trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA).
  • ⁇ tetramethylammonium hydroxide
  • SFL sulfolane
  • CDTA trans-1,2-cyclohexanediaminetetraacetic acid
  • WO04059700 uses an alkaline cleaning agent such as tetramethylammonium hydroxide (TMAH), N-methylmorpholine-N-oxide (MO), water and 2-mercaptobenzimidazole (MBI) to immerse crystals and tablets.
  • TMAH tetramethylammonium hydroxide
  • MO N-methylmorpholine-N-oxide
  • MBI 2-mercaptobenzimidazole
  • the alkaline cleaning agent has a high cleaning temperature, slightly corrodes the semiconductor wafer substrate, and the cleaning speed is relatively slow, which is disadvantageous for improving the cleaning efficiency of the semiconductor wafer.
  • JP1998239865 utilizes TMAH, dimethyl sulfoxide (DMSO), 1,3,-dimethyl-2-imidazolium (DMO and water to form an alkaline cleaning agent, immersing the wafer in the cleaning agent, 50 ⁇ 100 A thick film photoresist of 20 ⁇ m or more on the metal and dielectric substrate is removed at ° C.
  • the alkaline cleaner has a severe corrosion of the semiconductor wafer substrate at a higher cleaning temperature.
  • JP2001215736 uses an alkaline cleaning agent composed of hydrazine, dimethyl sulfoxide (DMSO:), ethylene glycol (EG) and water to immerse the wafer in the cleaning agent to remove metal and dielectric substrates at 50 to 70 ° C. On the photoresist.
  • the alkaline cleaner has a severe corrosion of the semiconductor wafer substrate at higher cleaning temperatures.
  • JP200493678 uses an alkaline cleaning agent consisting of TMAH, N-methylpyrrolidone (NMP:), water or methanol to immerse the wafer in the cleaning agent to remove light on metal and dielectric substrates at 25-85 ° C. Engraved.
  • the alkaline cleaning agent significantly enhances the corrosion of the semiconductor wafer substrate as the cleaning temperature increases.
  • the purpose of the invention is to solve the problem that the photoresist cleaning agent of the prior art has insufficient cleaning ability for the photoresist and the corrosiveness to the semiconductor wafer substrate, and provides a high photoresist cleaning.
  • the photoresist cleaning agent of the present invention comprises: a quaternary ammonium hydroxide, water, a mercapto glycol aryl ether, dimethyl sulfoxide, a polycarboxylic acid corrosion inhibitor, and an aminoazole corrosion inhibitor.
  • the quaternary ammonium hydroxide is preferably tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and/or benzyltrimethylammonium hydroxide. More preferably, it is tetramethylammonium hydroxide, tetraethylammonium hydroxide and/or tetrabutylammonium hydroxide, and most preferably tetramethylammonium hydroxide.
  • the content of the quaternary ammonium hydroxide is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 5% by mass.
  • the content of the water is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass.
  • alkyl diol aryl ether has an alkyl diol having a carbon number of from 3 to 18, and the decyl diol aryl ether is preferably propylene glycol monophenyl ether or isopropyl glycol monobenzene.
  • 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 , hexaethylene glycol monophenyl ether, hexapropylene glycol monophenyl ether, hexamethylene glycol monophenyl ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether and/or hexanediol mononaphthyl ether More preferred are propylene glycol monophenyl ether, dipropylene glycol monophenyl ether and/or propylene glycol monobenzyl ether.
  • the content of the mercapto diol aryl ether is preferably from 1 to 60% by mass, more preferably from 5 to 30% by mass.
  • Mercaptodiol aryl ether can improve the solubility of tetramethylammonium hydroxide in dimethyl sulfoxide, and the environmental harm is lower than that of mercapto glycol alkyl ether, which is more conducive to environmental protection.
  • the content of the dimethyl sulfoxide is preferably from 1 to 98% by mass, more preferably from 50 to 90% by mass.
  • the polycarboxylic acid corrosion inhibitor is preferably polyacrylic acid (PAA) or a copolymer thereof, polymethacrylic acid (PMAA) or a copolymer thereof, polyacrylic acid alcohol amine salt, polymethacrylic acid amine amine Salt, polyoxyethylene modified polyacrylic acid or a derivative thereof, polyoxyethylene modified polymethacrylic acid or a derivative thereof, polyepoxysuccinic acid, polyaspartic acid, carboxyl group-containing polycaprolactone and/or
  • the carboxyl group-containing polylactide is more preferably polyacrylic acid, polymethacrylic acid, polyacrylic acid alcoholamine salt, polymethacrylic acid amine salt, carboxyl group-containing polycaprolactone, and/or carboxyl group-containing polylactide.
  • the polycarboxylic acid corrosion inhibitor preferably has a molecular weight of from 500 to 20,000, more preferably from 1,000 to 10,000.
  • the content of the polycarboxylic acid corrosion inhibitor is preferably 0.01 to 5% by mass, more preferably 0.05 to 2.5% by mass.
  • the polycarboxylic acid corrosion inhibitor exhibited a good inhibitory effect on the corrosion of aluminum.
  • the aminoazole corrosion inhibitor is 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 5-amino-tetrazole, 3, 5-diamino-1,2,4-triazole, 2-aminoimidazole, 2-aminobenzimidazole, diaminobenzimidazole, 2-aminothiazole, 2-aminobenzothiazole, 2-aminooxazole , 2-aminobenzoxazole, 3-aminopyrazole, 3-aminocarbazole, 6-aminocarbazole, 2-amino-1,3,4-thiadiazole and/or 5-amino-1,2 , 3-thiadiazole.
  • 3-amino-1,2,4-triazole preferred are 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole and/or 5-amino-tetrazole.
  • the content of the aminoazole inhibitor is preferably 0.01-5% by mass, more preferably 0.05 to 2.5% by mass.
  • the aminoazole inhibitor is very effective in preventing the generation of oxides on the metal surface and improving the surface state of the wafer.
  • the photoresist cleaning agent may further contain one or more of a polar organic co-solvent, a surfactant, and a corrosion inhibitor other than the polycarboxylic acid and the aminoazole.
  • the content of the polar organic co-solvent is preferably from 0 to 50% by mass, more preferably from 5 to 30% by mass; and the content of the surfactant is preferably a mass percentage. 0-5%, more preferably 0.05 to 3% by mass; the content of the corrosion inhibitor other than the polycarboxylic acid and the aminoazole is preferably 0 to 10% by mass, more preferably For the mass percentage 0. Bu 5%.
  • the polar organic co-solvent is preferably one or more of sulfoxide, sulfone, imidazolium, alcohol amine and mercaptodiol monodecyl ether; alkyl glycol monodecyl ether The number of carbon atoms in the decyl diol is 3 to 18.
  • the sulfoxide is preferably diethyl sulfoxide and/or methyl ethyl sulfoxide;
  • the sulfone is preferably methyl sulfone, ethyl sulfone and/or sulfolane, more preferably sulfolane;
  • the imidazolidinone is preferably 2-imidazolidinone, 1,3-dimethyl-2-imidazolium and/or 1,3-diethyl-2-imidazolidinone, more preferably 1,3-Dimethyl-2-imidazolidinone;
  • the alkanolamine is preferably monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, methyldiethanolamine, dimethylethanolamine and/or hydroxyl Ethyl ethylenediamine, more preferably monoethanolamine, triethanolamine and/or methyldiethanolamine;
  • the alkyl glycol monoalkyl ether is preferably diethylene glycol monomethyl
  • the surfactant is preferably polyvinyl alcohol (PVG), polyvinylpyrrolidone (PVP) and/or polyoxyethylene ether (POE).
  • PVG polyvinyl alcohol
  • PVP polyvinylpyrrolidone
  • POE polyoxyethylene ether
  • the surfactant preferably has a molecular weight of from 500 to 20,000, more preferably from 1,000 to 10,000.
  • the other corrosion inhibitors are preferably alcohol amines, azoles other than aminoazoles, carboxylic acids other than polycarboxylic acids, and/or phosphonic acid corrosion inhibitors.
  • the alcohol amine corrosion inhibitor is preferably monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), isopropanolamine, methyldiethanolamine, dimethylethanolamine and/or Hydroxyethylethylenediamine, more preferably monoethanolamine, triethyl Alcoholamine and/or methyldiethanolamine;
  • the azole inhibitors other than the aminoazoles are preferably benzotriazole (BTA), methylbenzotriazole (TTA), benzo Triazole triethanolamine salt (BTA-TEA), 1-phenyl-5-mercaptotetrazole (PMTA), 2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole (MBT), 2-mercapto Benzooxazole (MBO) and/or dimercap
  • the photoresist cleaning agent of the present invention can be obtained by simply mixing and mixing the components described above.
  • the reagents and starting materials used in the present invention are commercially available.
  • the photoresist cleaner of the present invention can be used over a wide temperature range (between room temperature and 85 ° C).
  • the cleaning method can be referred to the following steps: The semiconductor wafer containing the photoresist is immersed in a cleaning agent, slowly shaken with a constant temperature oscillator at room temperature to 85 ° C, then washed with deionized water and then dried with high purity nitrogen gas.
  • the positive progressive effect of the present invention is that the cleaning agent of the present invention can clean and remove the photoresist (photoresist) and other etchings of a thickness of 20 ⁇ m or more on a metal, a metal alloy or a dielectric substrate at room temperature to 85 ° C. Residue; At the same time, the alkyl diol aryl ether and polycarboxylic acid corrosion inhibitor can form a protective film on the wafer pattern and the surface of the substrate, preventing halogen atoms, hydroxide ions, etc.
  • the photoresist cleaning agent of the invention has good application prospects in the field of microelectronics such as semiconductor wafer cleaning.
  • Table 1 shows the formulations of the photoresist cleaning agents of Examples 1 to 29, which are simply mixed uniformly according to the components and their contents listed in Table 1, to prepare each cleaning agent.
  • the amount of ether is triazole
  • the amount of imidazole is ammonium oxide
  • the amount is one ethanol ether 5
  • the amount of ether is glycolic acid 1
  • 1 benzylamine hinge amount is azole
  • Glycolic acid (3-aminoimidazolidine hydroxide 3 6 10 24.7 0.3 0.08
  • the amount of single benzyl is pyrazolone ammonium
  • the amount of ether is 2-mercapto
  • the amount of azole is
  • Monophenylamine salt (ethanolamine ammonium oxide-triazole)
  • the amount of ether is 1,3- (hydroxy
  • the amount of ether is methylene 0.1
  • the amount of hinged phenyl group is dimercapto
  • the amount of ether is Ding ⁇ 0.5
  • Monophenylene polymer (diethylenediamine ammonium triazole)
  • the amount of ethers is tetramethylene 0.5
  • the amount is 0.5 ether methylene
  • the amount of ether is (molecule 0.05
  • Table 2 shows the formulations of Comparative Cleaning Agents 77' and the photoresist cleaning agents 30 to 45 of the present invention, According to the components listed in Table 1 and their contents, they are simply mixed uniformly, that is, each cleaning agent is prepared.
  • Table 2 compares the composition and content of the cleaning agent 1, 7 and the photoresist cleaning agent 30 to 45 of the present invention.
  • the components in Table 2 were uniformly mixed in proportion to obtain a comparative cleaning agent 1, 7' and a cleaning agent 30-45, wherein a small amount of tetramethylammonium hydroxide in the comparative cleaning agent 7' was insoluble,
  • the comparative cleaning agents 1, 6 and the cleaning agents 30 to 45 are both clear and transparent homogeneous solutions.
  • the comparative cleaning agent ⁇ 6' and the cleaning agent 30 ⁇ 45 were used to clean the blank Cu wafer, and the corrosion of the metal Cu was measured.
  • the comparative cleaning agent ⁇ 6' and the cleaning agent 30 ⁇ 45 were used to clean the blank A1 wafer and the corrosion of the metal A1 was measured.
  • Test methods and conditions 4 4 4 cm blank A1 wafer was immersed in the cleaning agent, and oscillated at a vibration frequency of about 60 rpm for 60 minutes at 23 to 85 Torr using a constant temperature oscillator, then washed with deionized water and then blown with high purity nitrogen gas. Dry, using a quadrupole prober to measure the change in surface resistance of the blank A1 wafer before and after etching. The results are shown in Table 3.
  • Comparative cleaning agents 1, ⁇ 6, and cleaning agents 30 ⁇ 45 were used to clean the blank tetraethoxysilane (TEOS) wafers for corrosion of non-metallic TEOS.
  • Test Methods and Conditions A 4 X4 cm blank TEOS wafer was immersed in a cleaning agent, oscillated at a vibration frequency of about 60 rpm for 60 minutes at 23 to 85 ° C using a constant temperature oscillator, and then washed with deionized water and then with high purity nitrogen. Blow dry. The thickness of the TEOS thickness before and after cleaning of the blank TEOS wafer was measured using a Nanospec 6100 thickness gauge. The results are shown in Table 3.
  • a method of cleaning a photoresist on a semiconductor wafer by using a photoresist cleaning agent is as follows: A semiconductor wafer containing a negative acrylate-based photoresist (having a thickness of about 50 ⁇ m and exposed and etched) The pattern is immersed in the cleaning agent, and shaken at 23 to 85 ° C for 1 to 30 minutes at a vibration frequency of about 60 rpm using a constant temperature oscillator, then washed with deionized water and then dried with high purity nitrogen gas.
  • the cleaning effect of the photoresist and the corrosion of the wafer pattern by the cleaning agent are shown in Table 3.
  • Table 3 compares the corrosiveness of cleaning agent 1,6, and cleaning agent 30 ⁇ 45 to metallic Cu and A1 and non-metallic TEOS and the cleaning of negative photoresist
  • the photoresist cleaning agent 30 to 45 of the present invention has a good cleaning ability for a negative acrylate-based photoresist, and has a wide temperature range.
  • the corrosion of metal Cu and A1 and non-metal TEOS is low, and the wafer pattern is not damaged.

Abstract

A cleaning composition for removing resist includes quaternary ammonium hydroxide, water, alkyl glycol aryl ether, dimethylsulfoxide, poly carboxylic acid corrosion inhibitor and amino azole corrosion inhibitor. The cleaning composition may clean resist and other residues from metal, metal alloy and dielectric substrate, and has low etch rate for metal, such as Al and Cu and the like, and nonmetal, such as silicon dioxide and the like, as well as suppress generation of oxide on the surface of the metal.

Description

一种光刻胶清洗剂 技术领域  Photoresist cleaning agent
本发明涉及半导体制造工艺中一种清洗剂，具体的涉及一种光刻胶清洗 剂。 技术背景  The present invention relates to a cleaning agent in a semiconductor manufacturing process, and in particular to a photoresist cleaning agent. technical background
在通常的半导体制造工艺中， 通过在二氧化硅、 Cu (铜）等金属以及低 k材料等表面上形成光刻胶的掩模， 曝光后利用湿法或干法刻蚀进行图形转 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。 另外， 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） 氧化和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 a conventional semiconductor manufacturing process, a pattern of photoresist is formed on a surface of a metal such as silicon dioxide, Cu (copper) or the like and a low-k material, and the pattern is transferred by wet or dry etching after exposure. The low temperature and fast cleaning process is an important direction for the development of semiconductor wafer manufacturing 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. A negative photoresist having a crosslinked network structure after exposure and etching. In addition, cleaning agents often cause corrosion of the wafer pattern and substrate during the chemical cleaning of the photoresist by the semiconductor wafer. Especially in the process of removing photoresist and etching residues by chemical cleaning agents, oxidation and corrosion of metals (especially active metals such as aluminum and copper) are common and very serious problems, often leading to wafer yield. Significantly lower.
目前， 光刻胶清洗剂主要由极性有机溶剂、强碱和 /或水等组成，通过将 半导体晶片浸入清洗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 agent is mainly composed of a polar organic solvent, a strong alkali, and/or water, and the photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in a cleaning agent or rinsing the semiconductor wafer with a cleaning agent.
专利文献 WO03104901利用四甲基氢氧化铵（ΤΜΑΗ)、环丁砜（SFL)、 水和反 -1,2-环己垸二胺四乙酸（CyDTA)等组成碱性清洗剂， 将晶片浸入该 清洗剂中，于 50〜70°C下浸没 20~30min，除去金属和电介质基材上的光刻胶。 该碱性清洗剂对半导体晶片基材的腐蚀略高，且不能完全去除半导体晶片的 光刻胶， 清洗能力不足。 Patent document WO03104901 immerses a wafer into the cleaning agent by using an alkaline cleaning agent such as tetramethylammonium hydroxide (ΤΜΑΗ), sulfolane (SFL), water, and trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA). The photoresist on the metal and dielectric substrates is removed by immersion at 50 to 70 ° C for 20 to 30 minutes. The alkaline cleaning agent has a slightly high corrosion to the semiconductor wafer substrate, and the photoresist of the semiconductor wafer cannot be completely removed, and the cleaning ability is insufficient.
WO04059700利用四甲基氢氧化铵 （TMAH)、 N-甲基吗啡啉 -N-氧化物 (MO)、 水和 2-巯基苯并咪唑（MBI)等组成碱性清洗剂， 将晶、片浸入该清 洗剂中， 于 70°C下浸没 15~60min， 除去金属和电介质基材上的光刻胶。 该 碱性清洗剂的清洗温度较高， 对半导体晶片基材的腐蚀略高， 且清洗速度相 对较慢， 不利于提高半导体晶片的清洗效率。  WO04059700 uses an alkaline cleaning agent such as tetramethylammonium hydroxide (TMAH), N-methylmorpholine-N-oxide (MO), water and 2-mercaptobenzimidazole (MBI) to immerse crystals and tablets. The cleaning agent was immersed at 70 ° C for 15 to 60 minutes to remove the photoresist on the metal and dielectric substrates. The alkaline cleaning agent has a high cleaning temperature, slightly corrodes the semiconductor wafer substrate, and the cleaning speed is relatively slow, which is disadvantageous for improving the cleaning efficiency of the semiconductor wafer.
JP1998239865利用 TMAH、 二甲基亚砜（DMSO)、 1，3，-二甲基 -2-咪唑 垸酮（DMO和水等组成碱性清洗剂， 将晶片浸入该清洗剂中， 于 50~100°C 下除去金属和电介质基材上的 20μπι以上的厚膜光刻胶。 该碱性清洗剂在较 高的清洗温度下对半导体晶片基材的腐蚀较严重。  JP1998239865 utilizes TMAH, dimethyl sulfoxide (DMSO), 1,3,-dimethyl-2-imidazolium (DMO and water to form an alkaline cleaning agent, immersing the wafer in the cleaning agent, 50~100 A thick film photoresist of 20 μm or more on the metal and dielectric substrate is removed at ° C. The alkaline cleaner has a severe corrosion of the semiconductor wafer substrate at a higher cleaning temperature.
JP2001215736利用 ΤΜΑΗ、 二甲基亚砜（DMSO：)、 乙二醇（EG)和 水等组成碱性清洗剂， 将晶片浸入该清洗剂中， 于 50〜70°C下除去金属和电 介质基材上的光刻胶。该碱性清洗剂在较高的清洗温度下对半导体晶片基材 的腐蚀较严重。  JP2001215736 uses an alkaline cleaning agent composed of hydrazine, dimethyl sulfoxide (DMSO:), ethylene glycol (EG) and water to immerse the wafer in the cleaning agent to remove metal and dielectric substrates at 50 to 70 ° C. On the photoresist. The alkaline cleaner has a severe corrosion of the semiconductor wafer substrate at higher cleaning temperatures.
JP200493678利用 TMAH、 N-甲基吡咯垸酮 （NMP：)、 水或甲醇等组成 碱性清洗剂， 将晶片浸入该清洗剂中， 于 25~85°C下除去金属和电介质基材 上的光刻胶。 该碱性清洗剂随着清洗温度的升高， 对半导体晶片基材的腐蚀 明显增强。  JP200493678 uses an alkaline cleaning agent consisting of TMAH, N-methylpyrrolidone (NMP:), water or methanol to immerse the wafer in the cleaning agent to remove light on metal and dielectric substrates at 25-85 ° C. Engraved. The alkaline cleaning agent significantly enhances the corrosion of the semiconductor wafer substrate as the cleaning temperature increases.
以上清洗剂或者清洗能力不足， 或者对半导体晶片基材腐蚀较强， 不能 满足半导体晶片清洗技术的发展要求。 发明概要 The above cleaning agent or cleaning ability is insufficient, or the semiconductor wafer substrate is strongly corroded, and the development requirements of the semiconductor wafer cleaning technology cannot be satisfied. Summary of invention
本发明的目的是为了解决现有技术中的光刻胶清洗剂对光刻胶的清洗 能力不足和对半导体晶片基材的腐蚀性较强的问题，提供一种具有较高的光 刻胶清洗能力和较低的基材腐蚀性的光刻胶清洗剂。  The purpose of the invention is to solve the problem that the photoresist cleaning agent of the prior art has insufficient cleaning ability for the photoresist and the corrosiveness to the semiconductor wafer substrate, and provides a high photoresist cleaning. A photoresist cleaner with low ability and low substrate corrosion.
本发明的光刻胶清洗剂含有： 季铵氢氧化物、 水、 垸基二醇芳基醚、 二 甲基亚砜、 聚羧酸类缓蚀剂和氨基唑类缓蚀剂。  The photoresist cleaning agent of the present invention comprises: a quaternary ammonium hydroxide, water, a mercapto glycol aryl ether, dimethyl sulfoxide, a polycarboxylic acid corrosion inhibitor, and an aminoazole corrosion inhibitor.
其中，所述的季铵氢氧化物较佳的为四甲基氢氧化铵、四乙基氢氧化铵、 四丙基氢氧化铵、四丁基氢氧化铵和 /或苄基三甲基氢氧化铵，更佳的为四甲 基氢氧化铵、四乙基氢氧化铵和 /或四丁基氢氧化铵，最佳的为四甲基氢氧化 铵。 所述的季铵氢氧化物的含量较佳的为质量百分比 0.1~10%， 更佳的为质 量百分比 0.5~5%。  Wherein, the quaternary ammonium hydroxide is preferably tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and/or benzyltrimethylammonium hydroxide. More preferably, it is tetramethylammonium hydroxide, tetraethylammonium hydroxide and/or tetrabutylammonium hydroxide, and most preferably tetramethylammonium hydroxide. The content of the quaternary ammonium hydroxide is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 5% by mass.
其中， 所述的水的含量较佳的为质量百分比 0.1~30%， 更佳的为质量百 分比 0.5〜15%。  The content of the water is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass.
其中，所述的烷基二醇芳基醚中烷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为丙二醇单苯基醚、 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 /或己二醇单萘基醚， 更佳的为丙二醇单苯基醚、 二丙二醇单苯基醚和 /或丙 二醇单苄基醚。 所述的垸基二醇芳基醚的含量较佳的为质量百分比 1~60%， 更佳的为质量百分比 5~30%。垸基二醇芳基醚可以提高四甲基氢氧化铵在二 甲基亚砜中的溶解度， 且对环境的危害低于垸基二醇烷基醚等， 更利于环境 的保护。 其中，所述的二甲基亚砜的含量较佳的为质量百分比 1~98%， 更佳的为 质量百分比 50~90 %。 Wherein the alkyl diol aryl ether has an alkyl diol having a carbon number of from 3 to 18, and the decyl diol aryl ether is preferably propylene glycol monophenyl ether or isopropyl glycol monobenzene. 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 , hexaethylene glycol monophenyl ether, hexapropylene glycol monophenyl ether, hexamethylene glycol monophenyl ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether and/or hexanediol mononaphthyl ether More preferred are propylene glycol monophenyl ether, dipropylene glycol monophenyl ether and/or propylene glycol monobenzyl ether. The content of the mercapto diol aryl ether is preferably from 1 to 60% by mass, more preferably from 5 to 30% by mass. Mercaptodiol aryl ether can improve the solubility of tetramethylammonium hydroxide in dimethyl sulfoxide, and the environmental harm is lower than that of mercapto glycol alkyl ether, which is more conducive to environmental protection. The content of the dimethyl sulfoxide is preferably from 1 to 98% by mass, more preferably from 50 to 90% by mass.
其中， 所述的聚羧酸类缓蚀剂较佳的为聚丙烯酸 （PAA) 或其共聚物、 聚甲基丙烯酸（PMAA) 或其共聚物、 聚丙烯酸醇胺盐、 聚甲基丙烯酸醇胺 盐、 聚氧乙烯改性聚丙烯酸或其衍生物、 聚氧乙烯改性聚甲基丙烯酸或其衍 生物、聚环氧琥珀酸、聚天冬氨酸、含羧基的聚己内酯和 /或含羧基的聚丙交 酯， 更佳的为聚丙烯酸、 聚甲基丙烯酸、 聚丙烯酸醇胺盐、 聚甲基丙烯酸醇 胺盐、含羧基的聚己内酯和 /或含羧基的聚丙交酯。所述的聚羧酸类缓蚀剂的 分子量较佳的为 500~20000， 更佳的为 1000~10000。所述的聚羧酸类缓蚀剂 的含量较佳的为质量百分比 0.01~5%， 更佳的为质量百分比 0.05~2.5%。 所 述的聚羧酸类缓蚀剂对铝的腐蚀表现出很好的抑制作用。  Wherein, the polycarboxylic acid corrosion inhibitor is preferably polyacrylic acid (PAA) or a copolymer thereof, polymethacrylic acid (PMAA) or a copolymer thereof, polyacrylic acid alcohol amine salt, polymethacrylic acid amine amine Salt, polyoxyethylene modified polyacrylic acid or a derivative thereof, polyoxyethylene modified polymethacrylic acid or a derivative thereof, polyepoxysuccinic acid, polyaspartic acid, carboxyl group-containing polycaprolactone and/or The carboxyl group-containing polylactide is more preferably polyacrylic acid, polymethacrylic acid, polyacrylic acid alcoholamine salt, polymethacrylic acid amine salt, carboxyl group-containing polycaprolactone, and/or carboxyl group-containing polylactide. The polycarboxylic acid corrosion inhibitor preferably has a molecular weight of from 500 to 20,000, more preferably from 1,000 to 10,000. The content of the polycarboxylic acid corrosion inhibitor is preferably 0.01 to 5% by mass, more preferably 0.05 to 2.5% by mass. The polycarboxylic acid corrosion inhibitor exhibited a good inhibitory effect on the corrosion of aluminum.
其中，所述的氨基唑类缓蚀剂为 3-氨基 -1,2,4-三氮唑、 4-氨基 -1,2,4-三氮 唑、 5-氨基-四氮唑、 3，5-二氨基 -1,2,4-三氮唑、 2-氨基咪唑、 2-氨基苯并咪唑、 二氨基苯并咪唑、 2-氨基噻唑、 2-氨基苯并噻唑、 2-氨基噁唑、 2-氨基苯并 噁唑、 3-氨基吡唑、 3-氨基咔唑、 6-氨基吲唑、 2-氨基 -1,3,4-噻二唑和 /或 5- 氨基 -1,2,3-噻二唑。 其中， 较佳的为 3-氨基 -1，2，4-三氮唑、 4-氨基 -1，2，4-三氮 唑和 /或 5-氨基-四氮唑。 所述的氨基唑类缓蚀剂的含量较佳的为质量百分比 0.01-5%,更佳的为质量百分比 0.05~2.5%。所述的氨基唑类缓蚀剂能够非常 有效地防止金属表面氧化物的产生， 改善晶片表面状态。  Wherein, the aminoazole corrosion inhibitor is 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 5-amino-tetrazole, 3, 5-diamino-1,2,4-triazole, 2-aminoimidazole, 2-aminobenzimidazole, diaminobenzimidazole, 2-aminothiazole, 2-aminobenzothiazole, 2-aminooxazole , 2-aminobenzoxazole, 3-aminopyrazole, 3-aminocarbazole, 6-aminocarbazole, 2-amino-1,3,4-thiadiazole and/or 5-amino-1,2 , 3-thiadiazole. Among them, preferred are 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole and/or 5-amino-tetrazole. The content of the aminoazole inhibitor is preferably 0.01-5% by mass, more preferably 0.05 to 2.5% by mass. The aminoazole inhibitor is very effective in preventing the generation of oxides on the metal surface and improving the surface state of the wafer.
本发明中， 所述的光刻胶清洗剂还可含有极性有机共溶剂、表面活性剂 和除聚羧酸类以及氨基唑类以外的其它缓蚀剂中的一种或多种。  In the present invention, the photoresist cleaning agent may further contain one or more of a polar organic co-solvent, a surfactant, and a corrosion inhibitor other than the polycarboxylic acid and the aminoazole.
其中， 所述的极性有机共溶剂的含量较佳的为质量百分比 0~50%， 更佳 的为质量百分比 5~30%； 所述的表面活性剂的含量较佳的为质量百分比 0-5%,更佳的为质量百分比 0.05~3%；所述的除聚羧酸类以及氨基唑类以外 的其它缓蚀剂的含量较佳的为质量百分比 0~10%， 更佳的为质量百分比 0.卜 5%。 Wherein, the content of the polar organic co-solvent is preferably from 0 to 50% by mass, more preferably from 5 to 30% by mass; and the content of the surfactant is preferably a mass percentage. 0-5%, more preferably 0.05 to 3% by mass; the content of the corrosion inhibitor other than the polycarboxylic acid and the aminoazole is preferably 0 to 10% by mass, more preferably For the mass percentage 0. Bu 5%.
其中， 所述的极性有机共溶剂较佳的为亚砜、 砜、 咪唑垸酮、 醇胺和垸 基二醇单垸基醚中的一种或多种；烷基二醇单垸基醚中垸基二醇的碳原子数 目为 3~18。 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 的砜较佳的为甲基砜、 乙基砜和 /或环丁砜， 更佳的为环丁砜； 所述的咪唑烷 酮较佳的为 2-咪唑烷酮、 1，3-二甲基 -2-咪唑垸酮和 /或 1,3-二乙基 -2-咪唑烷 酮， 更佳的为 1，3-二甲基 -2-咪唑烷酮； 所述的醇胺较佳的为一乙醇胺、 二乙 醇胺、三乙醇胺、异丙醇胺、 甲基二乙醇胺、 二甲基乙醇胺和 /或羟乙基乙二 胺， 更佳的为一乙醇胺、三乙醇胺和 /或甲基二乙醇胺； 所述的烷基二醇单烷 基醚较佳的为二乙二醇单甲醚、 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、 二丙二醇单丁醚、三乙二醇单 甲醚、 三丙二醇单甲基醚、 三丙二醇单乙醚、 三丙二醇单丁醚、 六缩乙二醇 单甲醚、六缩丙二醇单甲醚和 /或六缩异丙二醇单甲醚，更佳的为二乙二醇单 甲醚和 /或二丙二醇单甲醚。  Wherein, the polar organic co-solvent is preferably one or more of sulfoxide, sulfone, imidazolium, alcohol amine and mercaptodiol monodecyl ether; alkyl glycol monodecyl ether The number of carbon atoms in the decyl diol is 3 to 18. Wherein, the sulfoxide is preferably diethyl sulfoxide and/or methyl ethyl sulfoxide; the sulfone is preferably methyl sulfone, ethyl sulfone and/or sulfolane, more preferably sulfolane; The imidazolidinone is preferably 2-imidazolidinone, 1,3-dimethyl-2-imidazolium and/or 1,3-diethyl-2-imidazolidinone, more preferably 1,3-Dimethyl-2-imidazolidinone; the alkanolamine is preferably monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, methyldiethanolamine, dimethylethanolamine and/or hydroxyl Ethyl ethylenediamine, more preferably monoethanolamine, triethanolamine and/or methyldiethanolamine; the alkyl glycol monoalkyl ether is preferably diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol More preferably diethyl ether, tripropylene glycol monobutyl ether, hexadediol ethylene monomethyl ether, hexapropylene glycol monomethyl ether and/or hexamethylene glycol monomethyl ether. Diethylene glycol monomethyl ether and / or dipropylene glycol monomethyl ether.
其中， 所述的表面活性剂较佳的为聚乙烯醇 （PVG)、 聚乙烯吡咯垸酮 (PVP) 和 /或聚氧乙烯醚 （POE)。 所述的表面活性剂的分子量较佳的为 500-20000, 更佳的为 1000~10000。  Among them, the surfactant is preferably polyvinyl alcohol (PVG), polyvinylpyrrolidone (PVP) and/or polyoxyethylene ether (POE). The surfactant preferably has a molecular weight of from 500 to 20,000, more preferably from 1,000 to 10,000.
其中， 所述的其它缓蚀剂较佳的为醇胺类、 除氨基唑类以外的唑类、 除 聚羧酸类以外的羧酸类和 /或膦酸类缓蚀剂。其中，所述的醇胺类缓蚀剂较佳 的为一乙醇胺 （MEA)、 二乙醇胺 （DEA)、 三乙醇胺 （TEA)、 异丙醇胺、 甲基二乙醇胺、二甲基乙醇胺和 /或羟乙基乙二胺， 更佳的为一乙醇胺、三乙 醇胺和 /或甲基二乙醇胺;所述的除氨基唑类以外的唑类缓蚀剂较佳的为苯并 三氮唑（BTA)、甲基苯并三氮唑（TTA)、苯并三氮唑三乙醇胺盐（BTA-TEA)、 1-苯基 -5-巯基四氮唑 （PMTA)、 2-巯基苯并咪唑 （MBI)、 2-巯基苯并噻唑 (MBT)、 2-巯基苯并噁唑（MBO)和 /或二巯基噻二唑（DMTDA), 更佳的 为苯并三氮唑、 甲基苯并三氮唑、 1-苯基 -5-巯基四氮唑和 /或 2-巯基苯并噻 所述的除聚羧酸类以外的羧酸类缓蚀剂较佳的为邻苯二甲酸、没食子酸、 柠檬酸、 苹果酸和 /或乙醇酸， 更佳的为柠檬酸和 /或乙醇酸； 所述的膦酸类 缓蚀剂较佳的为 1，3- (羟乙基） -2,4，6-三膦酸、 氨基三亚甲基膦酸、 2-膦酸 丁綜 -1，2，4-三羧酸、 乙二胺四亚甲基膦酸和 /或二乙烯三胺五亚甲基膦酸， 更 佳的为 2-膦酸丁垸 -1,2,4-三羧酸、乙二胺四亚甲基膦酸和 /或二乙烯三胺五亚 甲基膦酸。 Among them, the other corrosion inhibitors are preferably alcohol amines, azoles other than aminoazoles, carboxylic acids other than polycarboxylic acids, and/or phosphonic acid corrosion inhibitors. Wherein, the alcohol amine corrosion inhibitor is preferably monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), isopropanolamine, methyldiethanolamine, dimethylethanolamine and/or Hydroxyethylethylenediamine, more preferably monoethanolamine, triethyl Alcoholamine and/or methyldiethanolamine; the azole inhibitors other than the aminoazoles are preferably benzotriazole (BTA), methylbenzotriazole (TTA), benzo Triazole triethanolamine salt (BTA-TEA), 1-phenyl-5-mercaptotetrazole (PMTA), 2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole (MBT), 2-mercapto Benzooxazole (MBO) and/or dimercaptothiadiazole (DMTDA), more preferably benzotriazole, methylbenzotriazole, 1-phenyl-5-mercaptotetrazole and/or Or a carboxylic acid corrosion inhibitor other than the polycarboxylic acid described in 2- or 2-mercaptothiophene is preferably phthalic acid, gallic acid, citric acid, malic acid and/or glycolic acid, more preferably Citric acid and/or glycolic acid; the phosphonic acid corrosion inhibitor is preferably 1,3-(hydroxyethyl)-2,4,6-triphosphonic acid, aminotrimethylenephosphonic acid, 2- Phosphonic acid butyl-1,2,4-tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid and/or diethylenetriaminepentamethylenephosphonic acid, more preferably 2-phosphonium bromide-1 2,4-tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid and/or diethylenetriamine penta methylene phosphonic acid.
本发明的光刻胶清洗剂由上面所述组分简单混合均匀即可制得。本发明 所用试剂及原料均市售可得。本发明的光刻胶清洗剂可在较大的温度范围内 使用 （室温至 85°C之间）。 清洗方法可参照如下步骤： 将含有光刻胶的半导 体晶片浸入清洗剂中，在室温至 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 agent of the present invention can be obtained by simply mixing and mixing the components described above. The reagents and starting materials used in the present invention are commercially available. The photoresist cleaner of the present invention can be used over a wide temperature range (between room temperature and 85 ° C). The cleaning method can be referred to the following steps: The semiconductor wafer containing the photoresist is immersed in a cleaning agent, slowly shaken with a constant temperature oscillator at room temperature to 85 ° C, then washed with deionized water and then dried with high purity nitrogen gas.
本发明的积极进步效果在于：本发明的清洗剂可以在室温至 85 "C下较为 迅速地清洗除去金属、金属合金或电介质基材上 20μπι以上厚度的光刻胶 (光 阻）和其它刻蚀残留物； 同时， 所含的烷基二醇芳基醚和聚羧酸类缓蚀剂能 够在晶片图形和基材表面形成一层保护膜， 阻止卤素原子、氢氧根离子等对 晶片图形和基材的攻击， 从而降低对晶片图形和对铝和铜等金属， 以及二氧 化硅等非金属基材的腐蚀，尤其是其含有的聚羧酸类缓蚀剂对金属铝的腐蚀 表现出良好的抑制作用，而氨基唑类缓蚀剂能够非常有效地防止金属表面氧 化物的产生， 改善晶片表面状态。本发明的光刻胶清洗剂在半导体晶片清洗 等微电子领域具有良好的应用前景。 The positive progressive effect of the present invention is that the cleaning agent of the present invention can clean and remove the photoresist (photoresist) and other etchings of a thickness of 20 μm or more on a metal, a metal alloy or a dielectric substrate at room temperature to 85 ° C. Residue; At the same time, the alkyl diol aryl ether and polycarboxylic acid corrosion inhibitor can form a protective film on the wafer pattern and the surface of the substrate, preventing halogen atoms, hydroxide ions, etc. from being on the wafer pattern and The attack of the substrate, thereby reducing the corrosion of the wafer pattern and the metal such as aluminum and copper, and the non-metal substrate such as silicon dioxide, especially the polycarboxylic acid corrosion inhibitor contained therein exhibits good corrosion to the metal aluminum. Inhibition, while aminoazole inhibitors are very effective in preventing metal surface oxygen The formation of a compound improves the surface state of the wafer. The photoresist cleaning agent of the invention has good application prospects in the field of microelectronics such as semiconductor wafer cleaning.
发明内容 Summary of the invention
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在 所述的实施例范围之中。  The invention is further illustrated by the following examples, which are not intended to limit the invention.
实施例 1~29 Example 1~29
表 1给出了光刻胶清洗剂实施例 1~29的配方， 按表 1中所列组分及其 含量， 简单混合均匀， 即制得各清洗剂。  Table 1 shows the formulations of the photoresist cleaning agents of Examples 1 to 29, which are simply mixed uniformly according to the components and their contents listed in Table 1, to prepare each cleaning agent.
表 1 光刻胶清洗剂实施例 1~29 垸基二醇芳 二甲 聚羧酸类缓蚀 氨基唑类缓蚀  Table 1 Photoresist cleaning agent example 1~29 mercapto diol aromatic dimethyl polycarboxylic acid corrosion inhibition aminoazole corrosion inhibition
季铰氢氧化物 水  Quarter hinge hydroxide water
头 其他 基醚 基亚 剂 剂  Other other ether-based sub-agent
施 砜含  Sulfone
具体物 含  Specific content
例 含量 含量 具体 含量 具体物 含量 具体物 具体物 含量 里 ' 里  Example content content specific content concrete content specific material specific content
质 wt% wt% 物质 wt% wt% 质 wt% wt% 质 质  Quality wt% wt% substance wt% wt% quality wt% wt% quality
wt%  Wt%
丙二 聚丙炜  Propylene
四甲基  Tetramethyl
1 醇单  1 alcohol list
0.1 0.1 1.78 酸（分子  0.1 0.1 1.78 acid (molecule
氢氧化 98 0.01 0.01 \ \  Hydroxide 98 0.01 0.01 \ \
苯基 量为  The amount of phenyl is
铰 三氮唑  Hinge triazole
醚 500)  Ether 500)
丙烯酸- 异丙 马来酸  Acrylic acid - isopropyl maleic acid
四乙基  Tetraethyl
二醇  Glycol
2 0.5 共聚物  2 0.5 copolymer
氢氧化 0.5 8.9 90 0.05 -l5,4- 0.05 \ \  Hydroxide 0.5 8.9 90 0.05 -l5,4- 0.05 \ \
单苯 (分子  Monobenzene
铰 三氮唑  Hinge triazole
基醚 量为  The amount of ether is
1500)  1500)
聚丙烯  Polypropylene
二乙 酸三乙  Triethyl succinate
四丙基  Tetrapropyl
二醇 醇胺盐  Glycol alkoxide
3 氢氧化 10 25 30 30 2.5 2.5 \ \  3 Hydroxide 10 25 30 30 2.5 2.5 \ \
单苯 (分子 四氮唑  Monophenyl (molecular tetrazolium)
铵  Ammonium
基醚 量为  The amount of ether is
20000)  20000)
1.4 二丙 3,5-二 亚砜 四丁基  1.4 dipropyl 3,5-disulfoxide tetrabutyl
二醇  Glycol
4 三乙醇  4 triethanol
氢氧化 15 30 30 8.5 5 氨基 5 邻苯二  Hydroxide 15 30 30 8.5 5 amino 5 phthalic acid
0.1 单苯 胺盐（分 -1,2,4- 铵 甲酸  0.1 monophenylamine salt (min -1,2,4-ammonic acid
基醚 子量为 三氮唑  The amount of ether is triazole
10000) 柠檬酸 5 甲乙基 10000) Citric acid 5 Methyl
15.82 亚砜 二异  15.82 sulfoxide diiso
聚乙炼 丙二 丙烯酸  Polyacetone
2-氨基 醇 （分 甲基氢 8 15 醇单 60 1 (分子 0.01 0.02 0.05  2-amino alcohol (molecular hydrogen 8 15 alcohol single 60 1 (molecule 0.01 0.02 0.05
咪唑 子量为 氧化铵 苯基 量为  The amount of imidazole is ammonium oxide
500)  500)
醚 2500)  Ether 2500)
羟乙基  Hydroxyethyl
0.1 乙二胺 聚乙稀 甲基丙  0.1 ethylenediamine, polyethylene, methyl propyl
三乙 吡咯垸  Triethylpyrrole
烯酸-马  Oleic acid-horse
四甲基 2-氨基 酮 （分 3 Tetramethyl 2-amino ketone (3
二醇 来酸共  Glycol
氢氧化 2 5 1 85.85 0.05 苯并咪 3 子量为 Hydroxide 2 5 1 85.85 0.05 benzopyrene 3
单苯 聚物（分  Monophenylene polymer
铰 唑 20000)  Hindazole 20000)
基醚 子量为  The amount of ethers is
1000) 没食子  1000) No fruit
0.1 酸 聚氧乙  0.1 acid polyoxyethylene
三丙 烯改性  Tripropylene modification
四乙基 Tetraethyl
二醇 聚丙烯  Glycol polypropylene
8 50 苯并三 氢氧化 6 25.8 0.1 0.1 10  8 50 benzotrioxide 6 25.8 0.1 0.1 10
单苯 酸（分子  Monophenyl acid
铰 唑 氮唑  Thiazole
基醚 量为  The amount of ether is
5000)  5000)
聚氧乙  Polyoxyethylene
三异  Three different
烯改性  Ene modification
四丙基 丙二 甲基砜 30 Tetrapropyl propylene dimethyl sulfone 30
2-氨基  2-amino
氢氧化 7 20 醇单 10 27.6 聚丙烯 Hydroxide 7 20 alcohol single 10 27.6 polypropylene
0.1 0.3  0.1 0.3
酸酯（分 噻唑  Acid ester
铵 苯基  Ammonium phenyl
子量为 一乙醇 醚 5  The amount is one ethanol ether 5
5000 ) 胺 聚氧乙  5000 ) Amine Polyoxyethylene
六縮 烯改性 乙基砜 5 四丁基 乙二  Hexarene modified ethyl sulfone 5 tetrabutyl ethane
氢氧化 9 28 醇单 15 33.92 烯酸 0.08 苯 1 二乙醇 Hydroxide 9 28 alcohol mono 15 33.92 enoic acid 0.08 benzene 1 diethanol
7 铵 苯基 (分子 唑 胺  7 ammonium phenyl (molecular azole amine
醚 量为 乙醇酸 1  The amount of ether is glycolic acid 1
5000)  5000)
六縮  Six shrinkage
四丙基 丙二 Tetrapropyl propylene
聚氧乙  Polyoxyethylene
氢氧化 1 醇单 10 环丁砜 40 Hydroxide 1 alcohol mono 10 sulfolane 40
烯改性  Ene modification
铰 苯基  Hinge
醚  Ether
10 24.2 烯酸 0.2 1.5  10 24.2 Acrylic acid 0.2 1.5
六縮 噁唑 三乙醇  Hexaoxazole
酯（分子 2 四甲基 异丙 胺  Ester (molecule 2 tetramethylisopropylamine)
量为  Quantity is
氢氧化 1 二醇 10 Hydroxide 1 diol 10
5000 )  5000 )
铰 单苯 苹果酸 0.1  Hinge mono benzene malic acid 0.1
基醚  Ether
2-咪唑 聚环氧 20 丙二 垸酮 四丁基 琥珀酸 2-氨基  2-imidazole polyepoxy 20 propane ketone tetrabutyl succinic acid 2-amino
醇单  Alcohol single
氢氧化 3 10 6 57.2 (分子 0.5 苯并噁 2 异丙醇 Hydroxide 3 10 6 57.2 (molecular 0.5 benzox 2 isopropyl alcohol
1 苄基 胺 铰 量为 唑  1 benzylamine hinge amount is azole
醚  Ether
3000 ) 邻苯二  3000 ) phthalic acid
0.3 甲酸 1，3-二 异丙 聚天冬 甲基 -2- 四丙基 50 0.3 formic acid 1,3-diisopropyl polyaspartic methyl-2-tetrapropyl 50
二醇 氨酸（分 3-氨基 咪唑烷 氢氧化 3 6 10 24.7 0.3 0.08  Glycolic acid (3-aminoimidazolidine hydroxide 3 6 10 24.7 0.3 0.08
单苄 子量为 吡唑 酮 铵  The amount of single benzyl is pyrazolone ammonium
基醚 4500)  Ether ether 4500)
0.2 乙醇胺  0.2 ethanolamine
1,3-二 己二 乙基 -2- 四甲基 35  1,3-dihexylethyl-2-tetramethyl 35
醇单 基 咪唑烷 氢氧化 5 10 10 32.5 内 ½Si 3-氨  Alcohol mono group imidazolidine hydroxide 5 10 10 32.5 1⁄2Si 3-ammonia
酯（分 1 0.5  Ester (1 0.5
咔唑 酮 铰 子量为  The amount of oxazolone hinge is
醚 .  Ether .
6500) 6  6500) 6
乙醇胺 二乙二 醇单甲 10 丙二 醚 四丙基  Ethanolamine diethylene glycol monomethyl 10 propylene dicarboxylate tetrapropyl
醇单  Alcohol single
氢氧化 4 一乙醇 Hydroxide 4 - ethanol
8 15 56.4 交酯（分 0.5 0.1 1 苯基 吲唑 胺 铵 子量为  8 15 56.4 lactide (minute 0.5 0.1 1 phenyl carbazole amine ammonium amount is
醚  Ether
8000) 甲基苯  8000) methylbenzene
并三氮 5 唑 二乙二 聚氧乙 醇单乙 10 烯改性 醚 异丙  And triazole 5 azole diethylene glycol polyoxyethylene glycol monoethylene olefin modified ether isopropyl
四丁基 二乙醇 Tetrabutyl diethanol
二醇 1 氢氧化 3 20 20 43.2 烯酸 0.5 ,4- 2.2 胺  Glycol 1 hydroxide 3 20 20 43.2 enoic acid 0.5 , 4- 2.2 amine
单苯  Monophenyl
铵 (分子 噻二唑  Ammonium (molecular thiadiazole)
基醚 苯并三  Benzotriene
量为 氮唑三  Azotriazole
0.1 5000) 乙醇胺  0.1 5000) Ethanolamine
盐 二乙二 醇单丁  Salt diethylene glycol monobutyl
10 醚 二丙 聚丙烯  10 ether dipropylene polypropylene
四丙基 5-氨基 三乙醇 Tetrapropyl 5-amino triethanol
二醇 酸（分子  Glycolic acid
氢氧化 5 18 5 52.4 0.8 1,2,3-噻 1.8 胺 2 Hydroxide 5 18 5 52.4 0.8 1,2,3-thia 1.8 amine 2
单苯  Monophenyl
铵 二唑  Ammonium diazole
基醚 500)  Carboxyl ether 500)
1-苯基  1-phenyl
-5-巯基  -5-巯基
5 四氮唑 丙二醇 单丁醚 10 聚丙烯  5 tetrazolium propylene glycol monobutyl ether 10 polypropylene
丙二 酸三乙  Triethyl malonate
四甲基 异丙醇 Tetramethyl isopropanol
3-氨基  3-amino
醇单 醇胺盐  Alcohol monoamine amine salt
氢氧化 5 12 5 55.9 1.5 -1,2,4- 0.06 胺 2 Hydroxide 5 12 5 55.9 1.5 -1,2,4- 0.06 amine 2
苯基 (分子  Phenyl group
铰 三氮唑  Hinge triazole
醚 量为 2-巯基  The amount of ether is 2-mercapto
20000) 苯并咪 8  20000) Benzopyrene 8
唑 二丙二 Azole Dipropylene
聚丙烯  Polypropylene
醇单甲 10 酸（分子  Alcohol monomethyl acid
0.1 -1,2,4- 1 醚 量为  The amount of 0.1 -1,2,4- 1 ether is
三氮唑  Triazole
丙二 500) 3 四甲基 乙醇胺  Propylene 2 500) 3 tetramethylethanolamine
醇单  Alcohol single
氢氧化 5 15 8 56.35 聚丙烯 Hydroxide 5 15 8 56.35 polypropylene
苯基  Phenyl
铵 酸三乙  Ammonium triacetate
醚 2-巯基  Ether 2-mercapto
醇胺盐 5-氨基- Alcoholamine salt 5-amino-
0.5 0.05 苯并噻 1 (分子 四氮唑 0.5 0.05 benzothiazepine 1 (molecule tetrazolium)
唑 量为  The amount of azole is
20000)  20000)
二丙二 醇单乙 15 醚 异丙  Dipropylene glycol monoethyl 15 ether isopropyl
3-氨基  3-amino
二醇 三乙醇 1.5 Glycol triethanol 1.5
5 10 8 55.7 2 -1,2,4- 2.5 5 10 8 55.7 2 -1,2,4- 2.5
单苯 胺盐（分 乙醇胺 氧化铵 - 三氮唑  Monophenylamine salt (ethanolamine ammonium oxide-triazole)
基醚 子量为 1,3- (羟  The amount of ether is 1,3- (hydroxy
10000) 乙基）  10000) Ethyl)
0.3 -2,4,6- 三膦酸 聚氧乙 二丙二 二丙 烯改性 醇单丁 10 四乙基  0.3 -2,4,6-triphosphonic acid polyoxyethylene dipropylene dipropylene modified alcohol monobutyl 10 tetraethyl
二醇 聚丙烯 5-氨基- 醚 氢氧化 4 10 10 63 0.5 2.4  Glycol polypropylene 5-amino-ether hydroxide 4 10 10 63 0.5 2.4
单苯 酸（分子 四氮唑  Monobenzoic acid
铰 氨基三  Hinge
基醚 量为 亚甲基 0.1  The amount of ether is methylene 0.1
5000) 膦酸 丙烯酸- 三乙二 丙二 马来酸 醇单甲 10 四甲基 4-氨基  5000) Phosphonic acid Acrylic acid - Triethylenedipropane Maleic acid Alcohol monomethyl 10 Tetramethyl 4-amino
醇单 共聚物 醚 氢氧化 3 21 12 50 1 -1,2,4- 1  Alcohol mono copolymer ether hydroxide 3 21 12 50 1 -1,2,4- 1
苯基 (分子 2-巯基 铵 三氮唑  Phenyl (molecular 2-mercapto ammonium triazole)
醚 量为 苯并噁 2  The amount of ether is benzox 2
1500) 唑 二异 聚甲基 三丙二 四甲基 丙二 丙烯酸 醇单甲 10  1500) azole diisomeric polymethyl tripropylene ditetramethyl propylene di acrylate alcohol monomethyl 10
5-氨基- 氢氧化 3 10 醇单 13 60.95 (分子 0.05 2 基醚  5-amino-hydroxide 3 10 alcohol mono 13 60.95 (molecule 0.05 2 ether
四氮唑  Tetrazolium
铰 苯基 量为 二巯基  The amount of hinged phenyl group is dimercapto
1 醚 2500) 噻二唑  1 ether 2500) thiadiazole
三丙二 醇单乙 10 丙二 聚丙烯  Tripropylene glycol monoethyl 10 propylene dipropylene
苄基三 3-氨基 醚 Benzyl tris 3-amino ether
醇单 酸（分子  Alcoholic acid
5 15 15 53 0.5 -1,2,4- 0.5  5 15 15 53 0.5 -1,2,4- 0.5
苯基 量为  The amount of phenyl is
氧化铰 三氮唑 Oxidizing hinge
醚 -5- Ether -5-
500) 巯基 500) 巯基
1 -1,3,4- 三丙二 聚丙烯  1 -1,3,4-tripropylene dipropylene
二乙 醇单丁 10  Diethanol monobutyl 10
酸三乙  Acid triethyl
四乙基 醚 Tetraethyl ether
醇胺盐  Alcoholamine salt
氢氧化 5 10 10 61.2 2 -1,2,4- 1.3 2-膦酸 Hydroxide 5 10 10 61.2 2 -1,2,4-1.3 2-phosphonic acid
单苯 (分子  Monobenzene
铰 三氮唑  Hinge triazole
基醚 量为 丁垸 0.5  The amount of ether is Ding 垸 0.5
-1,2,4- 20000)  -1,2,4- 20000)
三羧酸 甲基丙 六縮乙 Tricarboxylic acid Methyl hexafluoride
二丙 烯酸-马 二醇单 30 四甲基 3-氨基  Diacrylic acid-horsediol mono 30 tetramethyl 3-amino
二醇 来酸共 甲醚  Glycolic acid methyl ether
25 氢氧化 2 6 5 54.65 0.05 -1,2,4- 1.8  25 Hydroxide 2 6 5 54.65 0.05 -1,2,4- 1.8
单苯 聚物（分 乙二胺 铵 三氮唑  Monophenylene polymer (diethylenediamine ammonium triazole)
基醚 子量为 四亚甲 0.5  The amount of ethers is tetramethylene 0.5
1000 ) 基膦酸  1000) phosphinic acid
六縮丙 二异 二醇单 】5 四丁基 丙二 m m 4-氨基 甲醚  Hexapropyl diisodiol 】5 tetrabutyl propylene di m m 4-amino methyl ether
三乙醇  Triethanol
26 氢氧化 6 15 醇单 10 48.3 3 -1,2,4- 2.2 二乙稀  26 Hydroxide 6 15 Alcohol single 10 48.3 3 -1,2,4- 2.2 Diethylene
胺盐（分  Amine salt
铰 苯基 三氮唑 三胺五  Hind phenyl triazole triamine
子量为 0.5 醚 亚甲基  The amount is 0.5 ether methylene
10000)  10000)
膦酸 六縮异 聚丙烯 丙二醇 5 异丙 酸三乙 单甲醚 四甲基 4-氨基  Phosphonic acid Hexapoly polypropylene Propylene glycol 5 Triethyl isopropyl monomethyl ether Tetramethyl 4-amino
二醇 醇胺盐  Glycol alkoxide
27 氢氧化 5 10 10 65.45 0.5 -1,2,4- 4 聚氧乙  27 Hydroxide 5 10 10 65.45 0.5 -1,2,4- 4 Polyoxyethylene B
单苯 (分子 烯醚 铰 三氮唑  Monophenylene (molecular ether)
基醚 量为 (分子 0.05  The amount of ether is (molecule 0.05
20000) 量为  20000) The quantity is
10000) 丙烯酸- 异丙 马来酸  10000) Acrylic acid - isopropyl maleic acid
四甲基  Tetramethyl
二醇 共聚物 5-氨基- Glycol copolymer 5-amino-
28 氢氧化 0.5 0.5 8.9 70 0.05 0.05 甲基砜 20 28 Hydroxide 0.5 0.5 8.9 70 0.05 0.05 Methyl sulfone 20
单苯 (分子 四氮唑  Monophenyl (molecular tetrazolium)
铰  Hinge
基醚 量为  The amount of ether is
1500)  1500)
聚丙烯  Polypropylene
聚氧乙 二乙 酸三乙  Polyoxyethylene triacetate
四乙基 烯醚  Tetraethyl enolate
二醇 醇胺盐  Glycol alkoxide
29 氢氧化 10 25 30 25 2.5 -1,2,4- 2.5 (分子 5  29 Hydroxide 10 25 30 25 2.5 -1,2,4- 2.5 (Molecule 5
单苯 (分子  Monobenzene
铵 三氮唑 量为  Ammonium triazole
基醚 量为  The amount of ether is
10000) 20000)  10000) 20000)
效果实施例 对比清洗剂 1，〜7，和本发明的光刻胶清洗剂 30~45 表 2给出了对比清洗剂 Γ〜7'和本发明的光刻胶清洗剂 30〜45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。 Effect Example Comparative Cleaning Agents 1, -7, and Photoresist Cleaning Agents 30 to 45 of the Present Invention Table 2 shows the formulations of Comparative Cleaning Agents 77' and the photoresist cleaning agents 30 to 45 of the present invention, According to the components listed in Table 1 and their contents, they are simply mixed uniformly, that is, each cleaning agent is prepared.
u 表 2对比清洗剂 1，~7，和本发明的光刻胶清洗剂 30~45的组分和含量 u Table 2 compares the composition and content of the cleaning agent 1, 7 and the photoresist cleaning agent 30 to 45 of the present invention.
Figure imgf000013_0001
Figure imgf000013_0001
注： \是没有加入该组分。  Note: \ is not added to this component.
将表 2中的各组分按照比例混合均匀， 制得对比清洗剂 1，~7'和清洗剂 30-45 其中， 除对比清洗剂 7'中有少量四甲基氢氧化铵不能溶解以外， 对 比清洗剂 1，~6，和清洗剂 30~45均为澄清透明的均相溶液。 将对比清洗剂 ~6'和清洗剂 30〜45用于清洗空白 Cu晶片，测定其对于 金属 Cu的腐蚀情况。测试方法和条件：将 4 X4cm空白 Cu晶片浸入清洗剂， 在 23〜85°C下利用恒温振荡器以约 60转 /分的振动频率振荡 60分钟，然后经 去离子水洗涤后用高纯氮气吹干， 利用四极探针仪测定空白 Cu晶片蚀刻前 后表面电阻的变化计算得到。 结果如表 3所示。 The components in Table 2 were uniformly mixed in proportion to obtain a comparative cleaning agent 1, 7' and a cleaning agent 30-45, wherein a small amount of tetramethylammonium hydroxide in the comparative cleaning agent 7' was insoluble, The comparative cleaning agents 1, 6 and the cleaning agents 30 to 45 are both clear and transparent homogeneous solutions. The comparative cleaning agent ~6' and the cleaning agent 30~45 were used to clean the blank Cu wafer, and the corrosion of the metal Cu was measured. Test methods and conditions: 4 X4 cm blank Cu wafer was immersed in a cleaning agent, oscillated at a vibration frequency of about 60 rpm for 60 minutes at 23 to 85 ° C using a constant temperature oscillator, and then washed with deionized water and then with high purity nitrogen. Blow drying, using a quadrupole prober to measure the change in surface resistance of the blank Cu wafer before and after etching. The results are shown in Table 3.
将对比清洗剂 Γ~6'和清洗剂 30~45用于清洗空白 A1晶片，测定其对于 金属 A1的腐蚀情况。测试方法和条件：将 4 X 4cm空白 A1晶片浸入清洗剂， 在 23~85Ό下利用恒温振荡器以约 60转 /分的振动频率振荡 60分钟，然后经 去离子水洗涤后用高纯氮气吹干， 利用四极探针仪测定空白 A1晶片蚀刻前 后表面电阻的变化计算得到。 结果如表 3所示。  The comparative cleaning agent Γ~6' and the cleaning agent 30~45 were used to clean the blank A1 wafer and the corrosion of the metal A1 was measured. Test methods and conditions: 4 4 4 cm blank A1 wafer was immersed in the cleaning agent, and oscillated at a vibration frequency of about 60 rpm for 60 minutes at 23 to 85 Torr using a constant temperature oscillator, then washed with deionized water and then blown with high purity nitrogen gas. Dry, using a quadrupole prober to measure the change in surface resistance of the blank A1 wafer before and after etching. The results are shown in Table 3.
将对比清洗剂 1，~6，和清洗剂 30~45 用于清洗空白的四乙氧基硅垸 (TEOS) 晶片， 测定其对于非金属 TEOS的腐蚀情况。 测试方法和条件： 将 4 X4cm空白 TEOS晶片浸入清洗剂， 在 23~85°C下利用恒温振荡器以约 60转 /分的振动频率振荡 60分钟， 然后经去离子水洗涤后用高纯氮气吹干。 利用 Nanospec6100测厚仪测定空白 TEOS晶片清洗前后 TEOS厚度的变化 计算得到， 结果如表 3所示。  Comparative cleaning agents 1,~6, and cleaning agents 30~45 were used to clean the blank tetraethoxysilane (TEOS) wafers for corrosion of non-metallic TEOS. Test Methods and Conditions: A 4 X4 cm blank TEOS wafer was immersed in a cleaning agent, oscillated at a vibration frequency of about 60 rpm for 60 minutes at 23 to 85 ° C using a constant temperature oscillator, and then washed with deionized water and then with high purity nitrogen. Blow dry. The thickness of the TEOS thickness before and after cleaning of the blank TEOS wafer was measured using a Nanospec 6100 thickness gauge. The results are shown in Table 3.
本发明中， 利用光刻胶清洗剂清洗半导体晶片上光刻胶的方法如下： 将 含有负性丙烯酸酯类光刻胶 （厚度约为 50微米， 且经过曝光和刻蚀） 的半 导体晶片（含有图案）浸入清洗剂中， 在 23~85°C下利用恒温振荡器以约 60 转 /分的振动频率振荡 1~30分钟， 然后经去离子水洗涤后用高纯氮气吹干。 光刻胶的清洗效果和清洗剂对晶片图案的腐蚀情况如表 3所示。 表 3对比清洗剂 1，~6，和清洗剂 30~45对金属 Cu和 A1 以及非金属 TEOS的腐蚀性及其对负性光刻胶的清洗情况
Figure imgf000015_0001
Figure imgf000016_0001
从表 3可以看出，与对比清洗剂 1 '~6'相比，本发明的光刻胶清洗剂 30〜45 对负性丙烯酸酯类光刻胶具有良好的清洗能力， 使用温度范围广， 同时对金 属 Cu和 A1以及非金属 TEOS的腐蚀性低， 对晶片图案无损坏。 In the present invention, a method of cleaning a photoresist on a semiconductor wafer by using a photoresist cleaning agent is as follows: A semiconductor wafer containing a negative acrylate-based photoresist (having a thickness of about 50 μm and exposed and etched) The pattern is immersed in the cleaning agent, and shaken at 23 to 85 ° C for 1 to 30 minutes at a vibration frequency of about 60 rpm using a constant temperature oscillator, then washed with deionized water and then dried with high purity nitrogen gas. The cleaning effect of the photoresist and the corrosion of the wafer pattern by the cleaning agent are shown in Table 3. Table 3 compares the corrosiveness of cleaning agent 1,6, and cleaning agent 30~45 to metallic Cu and A1 and non-metallic TEOS and the cleaning of negative photoresist
Figure imgf000015_0001
Figure imgf000016_0001
As can be seen from Table 3, compared with the comparative cleaning agent 1 '~6', the photoresist cleaning agent 30 to 45 of the present invention has a good cleaning ability for a negative acrylate-based photoresist, and has a wide temperature range. At the same time, the corrosion of metal Cu and A1 and non-metal TEOS is low, and the wafer pattern is not damaged.

Claims

权利要求 Rights request
1. 一种光刻胶清洗剂， 含有： 季铵氢氧化物、 水、 烷基二醇芳基醚、 二甲 基亚砜、 聚羧酸类缓蚀剂和氨基唑类缓蚀剂。 A photoresist cleaning agent comprising: a quaternary ammonium hydroxide, water, an alkyl glycol aryl ether, a dimethyl sulfoxide, a polycarboxylic acid corrosion inhibitor, and an aminoazole corrosion inhibitor.
2. 如权利要求 1所述的光刻胶清洗剂， 所述的季铵氢氧化物为四甲基氢氧 化铵、 四乙基氢氧化铵、 四丙基氢氧化铵、 四丁基氢氧化铵和 /或苄基三 甲基氢氧化铵。  2. The photoresist cleaning agent according to claim 1, wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and / or benzyl trimethyl ammonium hydroxide.
3. 如权利要求 1所述的光刻胶清洗剂， 所述的季铵氢氧化物的含量为质量 百分比 0.1~10%。  The photoresist cleaning agent according to claim 1, wherein the quaternary ammonium hydroxide is contained in an amount of 0.1 to 10% by mass.
4. 如权利要求 3所述的光刻胶清洗剂， 所述的季铵氢氧化物的含量为质量 百分比 0.5~5%。  The photoresist cleaning agent according to claim 3, wherein the quaternary ammonium hydroxide is contained in an amount of 0.5 to 5% by mass.
5. 如权利要求 1 所述的光刻胶清洗剂， 所述的水的含量为质量百分比 0.卜 30%。  5. The photoresist cleaning agent according to claim 1, wherein the water is contained in an amount of 0% by weight.
6. 如权利要求 5 所述的光刻胶清洗剂， 所述的水的含量为质量百分比 0.5〜15%。  6. The photoresist cleaning agent according to claim 5, wherein the water is contained in an amount of 0.5 to 15% by mass.
7. 如权利要求 1所述的光刻胶清洗剂， 所述的垸基二醇芳基醚中垸基二醇 的碳原子数目为 3〜18。  The photoresist cleaning agent according to claim 1, wherein the mercapto glycol aryl ether has a number of carbon atoms of from 3 to 18 in the mercapto diol.
8. 如权利要求 7所述的光刻胶清洗剂， 所述的烷基二醇芳基醚为丙二醇单 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 /或己二醇单萘基 醚。 8. The photoresist cleaning agent according to claim 7, wherein the alkyl glycol aryl ether is 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 monophenyl ether, propylene glycol monobenzyl ether, isopropyl glycol monobenzyl ether and/or hexanediol mononaphthyl ether.
. 如权利要求 1所述的光刻胶清洗剂， 所述的烷基二醇芳基醚的含量为质 量百分比 1~60%。 The photoresist cleaning agent according to claim 1, wherein the alkyl glycol aryl ether is contained in an amount of from 1 to 60% by mass.
10.如权利要求 9所述的光刻胶清洗剂， 所述的垸基二醇芳基醚的含量为质 量百分比 5~30%。  The photoresist cleaning agent according to claim 9, wherein the mercapto glycol aryl ether is contained in an amount of 5 to 30% by mass.
11.如权利要求 1所述的光刻胶清洗剂， 所述的二甲基亚砜的含量为质量百 分比 1~98%。  The photoresist cleaning agent according to claim 1, wherein the dimethyl sulfoxide is present in a mass ratio of from 1 to 98% by mass.
12.如权利要求 11所述的光刻胶清洗剂，所述的二甲基亚砜的含量为质量百 分比 50~90%。  The photoresist cleaning agent according to claim 11, wherein the dimethyl sulfoxide is contained in an amount of 50 to 90% by mass.
13.如权利要求 1所述的光刻胶清洗剂， 所述的聚羧酸类缓蚀剂为聚丙烯酸 或其共聚物、 聚甲基丙烯酸或其共聚物、 聚丙烯酸醇胺盐、 聚甲基丙烯 酸醇胺盐、 聚氧乙烯改性聚丙烯酸或其衍生物、 聚氧乙烯改性聚甲基丙 烯酸或其衍生物、 聚环氧琥珀酸、 聚天冬氨酸、 含羧基的聚己内酯和 /或 含羧基的聚丙交酯。  The photoresist cleaning agent according to claim 1, wherein the polycarboxylic acid corrosion inhibitor is polyacrylic acid or a copolymer thereof, polymethacrylic acid or a copolymer thereof, polyacrylic acid alcohol amine salt, polymethylation Acrylate amine salt, polyoxyethylene modified polyacrylic acid or its derivative, polyoxyethylene modified polymethacrylic acid or its derivative, polyepoxysuccinic acid, polyaspartic acid, carboxyl group-containing polycap Ester and/or carboxyl group-containing polylactide.
14.如权利要求 1所述的光刻胶清洗剂， 所述的聚羧酸类缓蚀剂的含量为质 量百分比 0.01〜5%。  The photoresist cleaning agent according to claim 1, wherein the polycarboxylic acid corrosion inhibitor is contained in an amount of 0.01 to 5% by mass.
15.如权利要求 14所述的光刻胶清洗剂，所述的聚羧酸类缓蚀剂的含量为质 量百分比 0.05~2.5%。  The photoresist cleaning agent according to claim 14, wherein the polycarboxylic acid corrosion inhibitor is contained in an amount of 0.05 to 2.5% by mass.
16.如权利要求 1 所述的光刻胶清洗剂， 所述的氨基唑类缓蚀剂为 3-氨基 -1，2，4-三氮唑、 4-氨基 -1，2，4-三氮唑、 5-氨基-四氮唑、 3,5-二氨基 -1，2，4- 三氮唑、 2-氨基咪唑、 2-氨基苯并咪唑、 二氨基苯并咪唑、 2-氨基噻唑、 2-氨基苯并噻唑、 2-氨基噁唑、 2-氨基苯并噁唑、 3-氨基吡唑、 3-氨基咔 唑、 6-氨基吲唑、 2-氨基 -1，3，4-噻二唑和 /或 5-氨基 -1，2,3-噻二唑。  The photoresist cleaning agent according to claim 1, wherein the aminoazole inhibitor is 3-amino-1,2,4-triazole or 4-amino-1,2,4-tri Azole, 5-amino-tetrazole, 3,5-diamino-1,2,4-triazole, 2-aminoimidazole, 2-aminobenzimidazole, diaminobenzimidazole, 2-aminothiazole , 2-aminobenzothiazole, 2-aminooxazole, 2-aminobenzoxazole, 3-aminopyrazole, 3-aminocarbazole, 6-aminocarbazole, 2-amino-1,3,4- Thiadiazole and / or 5-amino-1,2,3-thiadiazole.
17.如权利要求 1所述的光刻胶清洗剂， 所述的氨基唑类缓蚀剂的含量为质 量百分比 0.01~5%。 The photoresist cleaning agent according to claim 1, wherein the content of the aminoazole inhibitor is qualitative The percentage is 0.01~5%.
18.如权利要求 17所述的光刻胶清洗剂，所述的氨基唑类缓蚀剂的含量为质 量百分比 0.05〜2.5%。  The photoresist cleaning agent according to claim 17, wherein the aminoazole inhibitor is contained in an amount of 0.05 to 2.5% by mass.
19.如权利要求 1所述的光刻胶清洗剂， 所述的光刻胶清洗剂还含有极性有 机共溶剂、 表面活性剂和除聚羧酸类以及氨基唑类以外的其它缓蚀剂中 的一种或多种。  The photoresist cleaning agent according to claim 1, wherein the photoresist cleaning agent further comprises a polar organic co-solvent, a surfactant, and a corrosion inhibitor other than the polycarboxylic acid and the aminoazole. One or more of them.
20.如权利要求 19所述的光刻胶清洗剂，所述的极性有机共溶剂的含量为质 量百分比 0~50%；所述的表面活性剂的含量为质量百分比 0~5%；所述的 除聚羧酸类以及氨基唑类以外的其它缓蚀剂的含量为质量百分比 0~10%。  The photoresist cleaning agent according to claim 19, wherein the content of the polar organic co-solvent is 0 to 50% by mass; the content of the surfactant is 0 to 5% by mass; The content of the corrosion inhibitor other than the polycarboxylic acid and the aminoazole is 0 to 10% by mass.
21.如权利要求 20所述的光刻胶清洗剂，所述的极性有机共溶剂的含量为质 量百分比 5~30%； 所述的表面活性剂的含量为质量百分比 0.05~3%； 所 述的除聚羧酸类以及氨基唑类以外的其它缓蚀剂的含量为质量百分比 0.卜 5%。  The photoresist cleaning agent according to claim 20, wherein the content of the polar organic co-solvent is 5 to 30% by mass; and the content of the surfactant is 0.05 to 3% by mass; The content of the corrosion inhibitor other than the polycarboxylic acid and the aminoazole is 5% by mass.
22.如权利要求 19所述的光刻胶清洗剂，所述的极性有机共溶剂为亚砜、砜、 咪唑烷酮、 醇胺和烷基二醇单烷基醚中的一种或多种， 其中烷基二醇单 垸基醚中垸基二醇的碳原子数目为 3~18；所述的表面活性剂为聚乙烯醇、 聚乙烯吡咯垸酮和 /或聚氧乙烯醚； 所述的其它缓蚀剂为醇胺类、 除氨基 唑类以外的唑类、 除聚羧酸类以外的羧酸类和 /或膦酸类缓蚀剂。  The photoresist cleaning agent according to claim 19, wherein the polar organic co-solvent is one or more of a sulfoxide, a sulfone, an imidazolidinone, an alkanolamine, and an alkyl glycol monoalkyl ether. , wherein the alkyl diol monodecyl ether has a number of carbon atoms of from 3 to 18; the surfactant is polyvinyl alcohol, polyvinylpyrrolidone and/or polyoxyethylene ether; The other corrosion inhibitors described are alcohol amines, azoles other than aminoazoles, carboxylic acids other than polycarboxylic acids, and/or phosphonic acid corrosion inhibitors.
23.如权利要求 22所述的光刻胶清洗剂，所述的亚砜为二乙基亚砜和 /或甲乙 基亚砜。  The photoresist cleaning agent according to claim 22, wherein the sulfoxide is diethyl sulfoxide and/or methyl ethyl sulfoxide.
24.如权利要求 22所述的光刻胶清洗剂，所述的砜为甲基砜、乙基砜和 /或环 丁砜。 24. The photoresist cleaner of claim 22, wherein the sulfone is methyl sulfone, ethyl sulfone and/or sulfolane.
25.如权利要求 22所述的光刻胶清洗剂，所述的咪唑垸酮为 2-咪唑烷酮、 1,3- 二甲基 -2-咪唑垸酮和 /或 1,3-二乙基 -2-咪唑垸酮。 The photoresist cleaning agent according to claim 22, wherein the imidazolium is 2-imidazolidinone, 1,3-dimethyl-2-imidazolium and/or 1,3-diethyl Base-2-imidazolium.
26.如权利要求 22所述的光刻胶清洗剂，所述的醇胺为一乙醇胺、二乙醇胺、 三乙醇胺、异丙醇胺、 甲基二乙醇胺、二甲基乙醇胺和 /或羟乙基乙二胺。  The photoresist cleaning agent according to claim 22, wherein the alcohol amine is monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, methyldiethanolamine, dimethylethanolamine and/or hydroxyethyl group. Ethylenediamine.
27.如权利要求 22所述的光刻胶清洗剂，所述的垸基二醇单垸基醚为二乙二 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、 二丙二醇单丁醚、 三乙二醇单甲醚、 三丙 二醇单甲基醚、 三丙二醇单乙醚、 三丙二醇单丁醚、 六缩乙二醇单甲醚、 六缩丙二醇单甲醚和 /或六缩异丙二醇单甲醚。  The photoresist cleaning agent according to claim 22, wherein the mercapto diol monodecyl ether is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, hexamethylene Ethylene glycol monomethyl ether, hexapropylene glycol monomethyl ether and/or hexamethylene glycol monomethyl ether.
28.如权利要求 22所述的光刻胶清洗剂， 所述的醇胺类缓蚀剂为一乙醇胺、 二乙醇胺、 三乙醇胺、 异丙醇胺、 甲基二乙醇胺、 二甲基乙醇胺和 /或羟 乙基乙二胺。  The photoresist cleaning agent according to claim 22, wherein the alcohol amine corrosion inhibitor is monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, methyldiethanolamine, dimethylethanolamine and/or Or hydroxyethyl ethylenediamine.
29.如权利要求 22所述的光刻胶清洗剂， 所述的唑类缓蚀剂为苯并三氮唑、 甲基苯并三氮唑、 苯并三氮唑三乙醇胺盐、 1-苯基 -5-巯基四氮唑、 2-巯 基苯并咪唑、 2-巯基苯并噻唑、 2-巯基苯并噁唑和 /或二巯基噻二唑。  The photoresist cleaning agent according to claim 22, wherein the azole inhibitor is benzotriazole, methylbenzotriazole, benzotriazole triethanolamine salt, 1-benzene 5--5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and/or dimercaptothiadiazole.
30.如权利要求 22所述的光刻胶清洗剂，所述的羧酸类缓蚀剂为邻苯二甲酸、 没食子酸、 柠檬酸、 苹果酸和 /或乙醇酸。  The photoresist cleaning agent according to claim 22, wherein the carboxylic acid corrosion inhibitor is phthalic acid, gallic acid, citric acid, malic acid, and/or glycolic acid.
31.如权利要求 22所述的光刻胶清洗剂， 所述的膦酸类缓蚀剂为 1,3- (羟乙 基） -2,4,6-三膦酸、 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 /或二乙烯三胺五亚甲基膦酸。  The photoresist cleaning agent according to claim 22, wherein the phosphonic acid corrosion inhibitor is 1,3-(hydroxyethyl)-2,4,6-triphosphonic acid or aminotrimethylenephosphine. Acid, butan-1,2,4-tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid and/or diethylenetriaminepentamethylenephosphonic acid.
PCT/CN2008/001693 2007-09-29 2008-10-06 Cleaning composition for removing resist WO2009046637A1 (en)

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