WO2010051689A1 - 一种厚膜光刻胶清洗剂 - Google Patents

一种厚膜光刻胶清洗剂 Download PDF

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Publication number
WO2010051689A1
WO2010051689A1 PCT/CN2009/001233 CN2009001233W WO2010051689A1 WO 2010051689 A1 WO2010051689 A1 WO 2010051689A1 CN 2009001233 W CN2009001233 W CN 2009001233W WO 2010051689 A1 WO2010051689 A1 WO 2010051689A1
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Prior art keywords
cleaning agent
ether
agent according
mass
corrosion inhibitor
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PCT/CN2009/001233
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English (en)
French (fr)
Inventor
彭洪修
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安集微电子（上海）有限公司
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Priority to CN200980145769XA priority Critical patent/CN102209938A/zh
Publication of WO2010051689A1 publication Critical patent/WO2010051689A1/zh

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    • 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
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—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
    • 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
    • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • 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
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

  • the present invention relates to a cleaning agent in a semiconductor manufacturing process, and in particular to a thick film photoresist cleaning agent.
  • a mask of a photoresist is formed on a surface of a metal such as silicon dioxide, copper (Cu), or a low dielectric (k) material, and is subjected to wet or dry etching after exposure.
  • a metal such as silicon dioxide, copper (Cu), or a low dielectric (k) material
  • k low dielectric
  • Thick film photoresists above ⁇ are increasingly used in semiconductor wafer fabrication processes, especially thick film negative photoresists above ⁇ are being used in semiconductor wafer fabrication processes, and currently most of the industry. None of the photoresist cleaners can completely remove the exposed photoresist with a cross-linked network structure on the wafer, so the cleaning agent for thick-film photoresist is increasingly becoming an important research technology in semiconductor wafer fabrication. direction.
  • the cleaning agent especially a cleaning agent containing a strong alkali such as potassium hydroxide
  • the cleaning agent often causes corrosion of the wafer pattern and the substrate.
  • metal corrosion is a common and very serious problem, which often leads to a significant decrease in wafer yield.
  • 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.
  • JP1998239865 Immersed wafer by alkaline cleaning agent consisting of tetramethylammonium hydroxide ( ⁇ ), dimethyl sulfoxide (DMSO), 1,3'-dimethyl-2-imidazolidinone (DMI) and water.
  • alkaline cleaning agent consisting of tetramethylammonium hydroxide ( ⁇ ), dimethyl sulfoxide (DMSO), 1,3'-dimethyl-2-imidazolidinone (DMI) and water.
  • ⁇ tetramethylammonium hydroxide
  • DMSO dimethyl sulfoxide
  • DI 1,3'-dimethyl-2-imidazolidinone
  • US5529887 consists of an alkaline cleaning agent consisting of potassium hydroxide ( ⁇ ), alkyl glycol monoalkyl ether, 7 soluble fluoride and water.
  • the wafer is immersed in the cleaning agent to remove metal and dielectric substrates at 40-90 Torr.
  • the thick film photoresist on the X-inch semiconductor wafer substrate has higher corrosion.
  • US5962197 consists of an alkaline cleaning agent consisting of potassium hydroxide, ⁇ -methylpyrrolidone (oxime), propylene glycol ether, water and a surfactant, immersing the wafer in the cleaning agent, and removing the metal and dielectric substrate at 105 ° C. Thick film photoresist. Due to its high cleaning temperature, it is easy to cause corrosion of the semiconductor wafer substrate.
  • US2004025976 and WO2004113486 comprise an alkaline cleaning agent from a quaternary ammonium hydroxide, a water-soluble organic solvent, water, a corrosion inhibitor and potassium hydroxide having a mass percentage of less than 1.0% by weight, and immersing the wafer in the cleaning agent at 20 ⁇ Immersed at 85 C for 1 to 40 minutes to remove thick film photoresist on metal and dielectric substrates, but it does not have good cleaning ability for thick film photoresists, especially thick film negative photoresists.
  • US5139607 consists of an alkaline cleaning agent consisting of potassium hydroxide, tetrahydrofuranol, ethylene glycol and water.
  • the wafer is immersed in the cleaning agent and immersed for less than 90 Torr for 1 to 40 minutes to remove thick films on metal and dielectric substrates.
  • Photoresist The corrosion of the semiconductor wafer substrate is slightly higher, and the thick film photoresist of the semiconductor wafer cannot be completely removed, and the cleaning ability is insufficient. Summary of invention
  • the technical problem to be solved by the present invention is that the present invention overcomes the existing conventional photoresist cleaning agent.
  • the pattern and substrate exhibit a very low corrosivity, environmentally friendly and a thick film photoresist cleaner that can be used over a wide temperature range.
  • the thick film photoresist cleaning agent of the invention comprises dimethyl sulfoxide, potassium hydroxide, an alcohol amine, an alkyl glycol aryl ether and a polyacrylic acid corrosion inhibitor, wherein the alkyl glycol aryl ether is The alkyl diol has a carbon number of from 3 to 18.
  • the content of the dimethyl sulfoxide is preferably from 1 to 97% by mass, more preferably from 30 to 90% by mass.
  • the content of the potassium hydroxide is preferably 0.1 to 5% by mass, more preferably 1 to 4% by mass.
  • the alcohol amine can effectively suppress corrosion of the wafer pattern.
  • the alcohol amine is preferably selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, isopropanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine and hydroxyethylethylenediamine. Or more, more preferably one or more selected from the group consisting of monoethanolamine, triethanolamine, diglycolamine, and methylethanolamine.
  • the content is preferably 0.1 to 50% by mass, more preferably 0.5 to 35% by mass.
  • the alkyl glycol aryl ether can improve the solubility of potassium hydroxide in dimethyl sulfoxide, and the increase of potassium hydroxide content is beneficial to improve the cleaning agent of the present invention to the photoresist. Cleaning ability.
  • the mercapto diol aryl ether is less harmful to the environment than the ethylene glycol alkyl ether and the ethylene glycol aryl ether used in the conventional photoresist cleaning agent.
  • Alkyl glycol aryl ether Preferred from 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, hexamethylene glycol monophenyl ether, propylene glycol monobenzyl ether, different One or more of propylene 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 polyacrylic corrosion inhibitor exhibits an extremely strong inhibitory effect on corrosion of a metal such as aluminum.
  • the polyacrylic corrosion inhibitor is preferably selected from the group consisting of polyacrylic acid, acrylic acid copolymer, polymethacrylic acid, methacrylic acid copolymer, alcoholic amine salt of polyacrylic acid, alcohol amine salt of acrylic acid copolymer, polymethyl Alcohol amine salt of acrylic acid, alcohol amine salt of methacrylic acid copolymer, polyoxyethylene modified acrylic polymer, polyoxyethylene modified acrylate polymer, alkoxy ammonium salt of polyoxyethylene modified acrylic polymer One or more of a polyoxyethylene-modified methacrylic acid polymer, a polyoxyethylene-modified methacrylate polymer, and an alkoxide ammonium salt of a polyoxyethylene-modified methacrylic acid polymer; More preferred are polyacrylic acid, acrylic acid copolymer, alcoholic amine salt of polyacrylic acid, polyoxyethylene modified acrylic polymer, alkoxy ammonium
  • the thick film photoresist cleaning agent may further comprise an aminoazole corrosion inhibitor, a polar organic cosolvent, a surfactant, and a polyacrylic acid corrosion inhibitor and an aminoazole.
  • an aminoazole corrosion inhibitor e.g., a polar organic cosolvent, a surfactant, and a polyacrylic acid corrosion inhibitor and an aminoazole.
  • the content of the aminoazole inhibitor is preferably 0.01 to 5% by mass, more preferably 0.05 to 2.5% by mass ; and the content of the polar organic cosolvent is preferably 0.01% by mass. 50%, more preferably 5 to 30% by mass; the surfactant content is preferably 5% by mass, more preferably 0.05% to 3.0% by mass; The content of the corrosion inhibitor other than the agent and the aminoazole corrosion inhibitor is preferably 5.0% by mass, more preferably 0.05 to 3.0% by mass; the above mass percentage does not include 0%.
  • the aminoazole corrosion inhibitor exhibits a strong inhibitory effect on corrosion of a metal such as copper, and further suppresses generation of corrosion dark spots (pitting) on the wafer pattern.
  • the aminoazole inhibitor is preferably selected from the group consisting of 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 5-amino-tetrazole, 1-methyl-5-amino-tetrazole, 3-amino-5-mercapto-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 , one or more of 4-thiadiazole, 2-amino-5-mercapto-1,3,4-thi
  • the polar organic co-solvent is preferably one or more selected from the group consisting of sulfoxides, sulfones, iridones and mercaptodiol monoalkyl ethers.
  • the sulfoxide is preferably selected from the group consisting of 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 imidazolidinone is preferably selected from the group consisting of 2-imidazolium, 1,3-dimethyl-2-imidazolidinone and 1,3-diethyl-2-imidazolidine
  • the ketones more preferably 1, 3-dimethyl-2-imidazolidinone
  • the mercaptodiol monoalkyl ether is preferably selected from the group consisting of ethylene glycol monobutyl ether, Two two One or more of alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether, Preferred are selected from the group consisting of diethylene glycol monomethyl ether and/or dipropylene glycol monomethyl ether.
  • the surfactant is preferably selected from one or more of polyvinyl alcohol, polyvinyl pyrrolidone and polyoxyethylene ether; more preferably selected from polyvinylpyrrolidone and/or polyoxyethylene ether.
  • the number average molecular weight of the surfactant is preferably from 500 to 20,000, more preferably from 1,000 to 10,000.
  • the corrosion inhibitor other than the polyacrylic corrosion inhibitor and the aminoazole corrosion inhibitor is preferably selected from the group consisting of an amine corrosion inhibitor and/or an azole other than the aminoazole corrosion inhibitor.
  • Corrosion inhibitor is preferably selected from one or more of diethylenetriamine, triethylenetetramine, pentaethylenehexamine, polyethenepolyamine and aminoethylpiperazine, more preferably
  • the azole-based corrosion inhibitor other than the aminoazole inhibitor is preferably selected from the group consisting of benzotriazole and methylbenzotriazine.
  • Oxazole benzotriazole triethanolamine salt, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and dimercaptothiadiazole
  • the reagents and starting materials used in the present invention are commercially available.
  • the thick film photoresist cleaning agent of the present invention can be obtained by simply mixing the components described above.
  • the method for using the thick film photoresist cleaning agent of the present invention can refer to the following steps: immersing the semiconductor wafer containing the photoresist in a cleaning agent, slowly oscillating at 45 to 90 ° C with a constant temperature oscillator, and then After washing with deionized water, it is blown with high purity nitrogen.
  • the thick film photoresist cleaning agent of the present invention can remove thick film photoresist (photoresist) and other etching residues of a thickness of ⁇ or more on a substrate such as a metal, a metal alloy or a dielectric, and is cleaned on a semiconductor wafer.
  • a substrate such as a metal, a metal alloy or a dielectric.
  • the thick film photoresist cleaning agent of the present invention while being cleaned, contains alkyl glycol aryl ether, alcohol amine and polyacrylic acid corrosion inhibitor to form a layer of protection on the wafer pattern and the surface of the substrate.
  • the film prevents halogen atoms, hydroxide ions and the like from attacking the wafer pattern and the substrate, and has low corrosivity to metals such as aluminum and copper and non-metal materials such as silicon dioxide, thereby reducing corrosion of the wafer pattern and the substrate.
  • the alkyl glycol aryl ether contained therein can increase the solubility of potassium hydroxide in dimethyl sulfoxide.
  • the increase of potassium hydroxide content is beneficial to improve the cleaning ability of the cleaning agent to the photoresist, and at the same time, it has a good inhibitory effect on the corrosion of metal such as copper, and the polyacrylic corrosion inhibitor exhibits extreme corrosion to aluminum and other metals. Strong inhibition, at the same time, the aminoazole inhibitor can also contain strong inhibition of copper and other metals, and can further inhibit the corrosion of dark spots on the wafer pattern.
  • the photoresist cleaning agent of the present invention is environmentally friendly and can be used over a wide temperature range (between 45 and 90 ° C). Summary of the invention
  • Table 1 shows Examples 1 to 25 of the thick film resist cleaning agent of the present invention, and the cleaning agents of the respective examples were prepared by simply mixing them in accordance with the components and their contents listed in Table 1.
  • Amine (number average molecular weight (number average molecular weight 5 monophenyl 10
  • Alcoholamine phenyl ether molecular weight (number average molecular weight 3
  • Phenyl ether salt (number average molecular aminoethyl pipe
  • Phenyl ether molecular weight is 0.5
  • Table 2 shows the comparison of the cleaning agent ⁇ 6' and the thick film photoresist cleaning agent 1 ⁇ 12 of the present invention, according to the components listed in Table 2 and their contents, simply mixed uniformly, that is, each detergent.
  • Table 2 compare cleaning agent 1, ⁇ 6, and the thick film photoresist cleaning agent of the present invention 1 ⁇ 12 components and content polyoxyethylene polyoxyethylene
  • the comparative cleaning agents 2' to 6' and the cleaning agents 1 to 12 of the present invention are clear and transparent homogeneous solutions except for the undissolved potassium hydroxide in the comparative cleaning agent.
  • the comparative cleaning agents 2' to 6' in Table 2 and the thick film photoresist cleaning agents 1 to 12 of the present invention were used to clean the blank Cu wafer and test the corrosion of the metal Cu.
  • Test methods and conditions 4 X4 cm blank Cu wafer was immersed in a cleaning agent, shaken at 45 to 90 ° C for 60 minutes using a constant temperature oscillator, then washed with deionized water and then dried with high purity nitrogen gas, using a quadrupole probe The change in surface resistance of the blank Cu wafer before and after etching was measured. The results are shown in Table 3.
  • the comparative cleaning agents 2' ⁇ 6' in Table 2 and the thick film photoresist cleaning agents 1 ⁇ 12 of the present invention were used to clean the blank A1 wafer and test its corrosion to the metal A1.
  • Test methods and conditions 4X 4cm blank A1 wafer was immersed in cleaning agent, shaken at 45 ⁇ 90 °C for 60 minutes with a constant temperature oscillator, then washed with deionized water and then dried with high purity nitrogen gas, using a quadrupole probe The change in surface resistance before and after etching of the blank A1 wafer was measured. The results are shown in Table 3.
  • the comparative cleaning agents 2, ⁇ 6' in Table 2 and the thick film photoresist cleaning agents 1 ⁇ 12 of the present invention were used to clean blank TEV wafers and tested for non-metallic TEOS. Corrosion. Test Methods and Conditions: A 4 X 4 cm blank TEOS wafer was immersed in a cleaning agent, shaken at 45 to 90 ° C for 60 minutes using a constant temperature oscillator, then washed with deionized water and then dried with high purity nitrogen. The change of TEOS thickness before and after cleaning of blank TEOS wafers was calculated by Nanospec 6100 thickness gauge. The results are shown in Table 3.
  • the method of cleaning the photoresist on the semiconductor wafer by using the comparative cleaning agents 2, 1-6 in Table 2 and the thick film photoresist cleaning agent 1 ⁇ 12 of the present invention is as follows: lithography containing negative acrylate A semiconductor wafer (containing a pattern of about 120 microns thick and exposed and etched) is immersed in a cleaning agent, oscillated at 45 to 90 Torr for 15 to 150 minutes using a constant temperature oscillator, and then washed with deionized water. High purity nitrogen is blown dry. 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 cleaning properties of cleaning agents 2, ⁇ 6, and the cleaning agents 1 to 12 of the present invention to metals Cu and A1 and non-metallic TEOS and their cleaning of thick film photoresists.
  • the thick film photoresist cleaning agents 1 to 12 of the present invention have a good cleaning effect on the thick film photoresist compared with the comparative cleaning agents 2' to 6', and the use temperature range is wide. At the same time, it has low corrosiveness to metal Cu and A1 and non-metal TEOS, no damage to wafer pattern and no corrosion dark spots.

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Description

一种厚膜光刻胶清洗剂 技术领域
本发明涉及一种半导体制造工艺中的清洗剂，具体涉及一种厚膜光刻胶 清洗剂。 技术背景
在通常的半导体制造工艺中， 通过在二氧化硅、 铜 (Cu)等金属以及低介 电 (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。 ΙΟΟμη 以上的厚膜光刻胶越来越多地应用于半导体晶片制造工艺中， 尤其是 ΙΟΟμπι以上的厚膜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都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， 因而用于厚膜光刻胶的清洗剂日益成 为半导体晶片制造工艺的重要研究方向。 另外， 在半导体晶片进行光刻胶的 化学清洗过程中， 清洗剂（尤其是含有氢氧化钾等强碱的清洗剂）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刻蚀残余物的过程 中， 金属腐蚀是较为普遍而且非常严重的问题，往往导致晶片良率的显著降 低。
目前，光刻胶清洗剂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。
JP1998239865 由四甲基氢氧化铵 (ΤΜΑΗ)、 二甲基亚砜 (DMSO)、 1,3'- 二甲基 _2-咪唑烷酮 (DMI)和水等组成碱性清洗剂， 将晶片浸入该清洗剂中， 在 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。但其对 半导体晶片基材的腐蚀略高， 且不能完全去除半导体晶片的光刻胶， 清洗能 力不足。
US5529887由氢氧化钾 (ΚΟΗ)、 烷基二醇单烷基醚、 7溶性氟化物和水 等组成碱性清洗剂， 将晶片浸入该清洗剂中， 在 40~90Ό下除去金属和电介 质基材上的厚膜光刻胶， X寸半导体晶片基材的腐蚀较高。
US5962197由氢氧化钾、 Ν-甲基吡咯烷酮 ( ΜΡ)、 丙二醇醚、 水和表面 活性剂等组成碱性清洗剂， 将晶片浸入该清洗剂中， 在 105°C下除去金属和 电介质基材上的厚膜光刻胶。 由于其清洗温度较高， 容易造成半导体晶片基 材的腐蚀。
US2004025976和 WO2004113486由季铵氢氧化物、 水溶性有机溶剂、 水、 缓蚀剂和质量百分含量小于 1.0wt%的氢氧化钾等组成碱性清洗剂， 将 晶片浸入该清洗剂中， 在 20~85 C下浸没 l〜40min， 除去金属和电介质基材 上的厚膜光刻胶，但其对于厚膜光刻胶尤其是厚膜负性光刻胶的清洗能力不 佳。
US5139607由氢氧化钾、 四氢呋喃醇、 乙二醇和水等组成碱性清洗剂， 将晶片浸入该清洗剂中，在低于 90Ό的温度下浸没 l〜40min， 除去金属和电 介质基材上的厚膜光刻胶。其对半导体晶片基材的腐蚀略高， 且不能完全去 除半导体晶片的厚膜光刻胶， 清洗能力不足。 发明概要
本发明所要解决的技术问题是本发明克服了现有传统的光刻胶清洗剂 对光刻胶尤其是负性光刻胶清洗能力不足， 或由于清洗时操作温度较高， 对 半导体晶片图案和基材的腐蚀较高等缺陷， 而提供了一种可以除去金属、金 属合金或电介质等基材上的厚膜光刻胶， 尤其是 lOO m 以上厚度的厚膜光 刻胶， 同时对铝和铜等金属以及二氧化硅等非金属材料具有很低的腐蚀性， 使其对晶片图案和基材表现出很低的腐蚀性，环境友好且可在较宽的温度范 围内使用的一种厚膜光刻胶清洗剂。
本发明的厚膜光刻胶清洗剂， 其包含二甲基亚砜、 氢氧化钾、 醇胺、 烷 基二醇芳基醚和聚丙烯酸类缓蚀剂，其中烷基二醇芳基醚中烷基二醇的碳原 子数目为 3〜18。
本发明中，所述的二甲基亚砜的含量较佳的为质量百分比 1~97%， 更佳 的为质量百分比 30〜90%。
本发明中， 所述的氢氧化钾的含量较佳的为质量百分比 0.1〜5%， 更佳 的为质量百分比 1〜4%。
本发明中， 所述的醇胺可以有效地抑制晶片图案的腐蚀。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。 其含量较佳的为质 量百分比 0.1〜50%， 更佳的为质量百分比 0.5~35%。
本发明中，所述的烷基二醇芳基醚可以提高氢氧化钾在二甲基亚砜中的 溶解度，而氢氧化钾含量的增加有利于提高本发明中的清洗剂对光刻胶的清 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。所述的烷基二醇芳基醚 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 含量较佳的为质量百分比 1〜50%， 更佳的为质量百分比 5〜30%。
本发明中，所述的聚丙烯酸类缓蚀剂对金属如铝的腐蚀表现出极强的抑 制作用。 所述的聚丙烯酸类缓蚀剂较佳的选自聚丙烯酸、 丙烯酸共聚物、 聚 甲基丙烯酸、 甲基丙烯酸共聚物、 聚丙烯酸的醇胺盐、 丙烯酸共聚物的醇胺 盐、 聚甲基丙烯酸的醇胺盐、 甲基丙烯酸共聚物的醇胺盐、 聚氧乙烯改性的 丙烯酸聚合物、聚氧乙烯改性的丙烯酸酯聚合物、聚氧乙烯改性的丙烯酸聚 合物的醇铵盐、聚氧乙烯改性的甲基丙烯酸聚合物、聚氧乙烯改性的甲基丙 烯酸酯聚合物、和聚氧乙烯改性的甲基丙烯酸聚合物的醇铵盐中的一种或多 种； 更佳的选自聚丙烯酸、 丙烯酸共聚物、 聚丙烯酸的醇胺盐、 聚氧乙烯改 性的丙烯酸聚合物、聚氧乙烯改性的丙烯酸聚合物的醇铵盐、聚氧乙烯改性 的甲基丙烯酸聚合物、和聚氧乙烯改性的甲基丙烯酸聚合物的醇铵盐中的一 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。 其含量较佳的为质量百分比 0.001~5%， 更佳的为质量 百分比 0.05~2.5%。
本发明中， 所述的厚膜光刻胶清洗剂还可以进一步包含氨基唑类缓蚀 剂、 极性有机共溶剂、表面活性剂、 以及除聚丙烯酸类缓蚀剂和氨基唑类缓 蚀剂以外的其它缓蚀剂中的一种或多种。
其中， 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%; 所述的极性有机共溶剂含量较佳的为质量百 分比 50%， 更佳的为质量百分比 5〜30%； 所述的表面活性剂含量较佳的为 质量百分比 5%， 更佳的为质量百分比 0.05~3.0%； 所述的除聚丙烯酸类缓 蚀剂和氨基唑类缓蚀剂以外的其它缓蚀剂含量较佳的为质量百分比 5.0%， 更佳的为质量百分比 0.05〜3.0%； 上述质量百分比不包括 0%。
本发明中，所述的氨基唑类缓蚀剂对金属如铜的腐蚀表现出很强的抑制 作用， 并且可以进一歩抑制晶片图案上腐蚀暗点 （点蚀）的产生。 所述的氨 基唑类缓蚀剂较佳的选自 3-氨基 -1,2，4-三氮唑、 4-氨基 -1,2,4-三氮唑、 5-氨基 -四氮唑、 1-甲基 -5-氨基-四氮唑、 3-氨基- 5-巯基 -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、 2-氨基 -5-巯基 -1,3，4-噻二唑和 5-氨基 -1,2，3-噻二唑中的一种或多种； 更佳的选自 3-氨基 -1，2,4-三氮唑、 4-氨基 -1 ,2,4-三氮唑、 5-氨基-四氮唑、 1- 甲基 -5-氨基-四氮唑和 3-氨基 -5-巯基 -1,2,4-三氮唑中的一种或多种。
本发明中， 所述的极性有机共溶剂较佳的选自亚砜、 砜、 咪 焼酮和垸 基二醇单烷基醚中的一种或多种。其中， 所述的亚砜较佳的选自二乙基亚砜 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； 所述的咪唑烷酮较佳的选自 2-咪唑垸酮、 1,3-二甲 基 -2-咪唑烷酮和 1，3-二乙基 -2-咪唑烷酮中的一种或多种，更佳的为 1 ,3-二甲 基- 2-咪唑烷酮；所述的垸基二醇单烷基醚较佳的选自乙二醇单丁醚、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 二醇单甲醚和 /或二丙二醇单甲醚。
本发明中， 所述的表面活性剂较佳的选自聚乙烯醇、聚乙烯吡咯烷酮和 聚氧乙烯醚中的一种或多种； 更佳的选自聚乙烯吡咯烷酮和 /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 o
本发明中，所述的除聚丙烯酸类缓蚀剂和氨基唑类缓蚀剂以外的其它缓 蚀剂较佳的选自胺类缓蚀剂和 /或除氨基唑类缓蚀剂以外的唑类缓蚀剂。 其 中， 所述的胺类缓蚀剂较佳的选自二乙烯三胺、 三乙烯四胺、 五乙烯六胺、 多乙烯多胺和氨基乙基哌嗪中的一种或多种，更佳的选自多乙烯多胺和 /或氨 基乙基哌嗪；所述的除氨基唑类缓蚀剂以外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-巯基苯并噁唑和二巯基噻二唑中的一种 或多种， 更佳的选自苯并三氮唑、 甲基苯并三氮唑、 1-苯基 -5-巯基四氮唑和 2-巯基苯并噻唑中的一种或多种。
本发明所用试剂和原料均市售可得。
本发明中， 上述的各成分的优选条件可以任意组合， 得到较佳的技术方 案用于制备厚膜光刻胶清洗剂。
本发明的厚膜光刻胶清洗剂由上面所述组分简单混合即可制得。
本发明的厚膜光刻胶清洗剂的使用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 45~90°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千。
本发明的积极进步效果在于：
(1)本发明的厚膜光刻胶清洗剂可以除去金属、金属合金或电介质等基材 上的 ΙΟΟμηι 以上厚度的厚膜光刻胶（光阻） 和其它刻蚀残留物， 在半导体 晶片清洗等微电子领域具有良好的应用前景。
(2)本发明的厚膜光刻胶清洗剂在清洗的同时， 其含有的烷基二醇芳基 醚、 醇胺和聚丙烯酸类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形和基材的攻击， 对铝和铜等金属以 及二氧化硅等非金属材料具有很低的腐蚀性，从而降低晶片图形和基材的腐 蚀；尤其是其含有的烷基二醇芳基醚可以提高氢氧化钾在二甲基亚砜中的溶 解度。氢氧化钾含量的增加有利于提高清洗剂对光刻胶的清洗能力， 同时其 对金属如铜的腐蚀表现出良好的抑制作用，而且聚丙烯酸类缓蚀剂对铝等金 属的腐蚀表现出极强的抑制作用， 同时可以含有的氨基唑类缓蚀剂对铜等金 属的腐蚀也表现出很强的抑制作用，并可以进一步抑制晶片图案上腐蚀暗点
(点蚀） 的产生。
(3)本发明的光刻胶清洗剂对环境友好，且其可以在较宽的温度范围内使 用 （45~90°C之间）。 发明内容
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在 所述的实施例范围之中。
下述实施例中， 百分比均为质量百分比。 实施例 1~25
表 1给出了本发明的厚膜光刻胶清洗剂的实施例 1〜25，按表 1中所列组 分及其含量， 简单混合均匀， 即可制得各实施例的清洗剂。
表 1 本发明厚膜光刻胶实施例 1〜25
Figure imgf000009_0001
三丙二 2-氨基咪唑 5 醇单苯 10 聚氧乙烯改
甲基砜 5 甲基 基醚 性的聚甲基
5 5 乙醇 45 丙烯酸甲酯 5 聚氧乙烯醚
丙二醇
胺 (数均分子量 (数均分子量 5 单苯基 10
为 75000) 为 10000) 醚
五乙稀六胺 5
2-氨基苯并
0.5 咪唑 聚氧乙烯改 乙基砜 10 甲基 三异丙 性的聚丙烯
76.5 1 二乙 0.5 二醇单 5 .酸乙酯 (数均 0.5 聚氧乙烯醚
醇胺 苯基醚 分子量为 (数均分子量 3
50000) 为 1000)
多乙烯多胺 3 二氨基苯并 1 聚氧乙烯改 咪哇 六缩乙 性的聚丙烯
一乙 环丁砜 23
35 3 25 二醇单 10 酸一乙醇胺 1
醇胺
苯基醚 盐 (数均分子 氨基乙基哌
1 量为 40000) 嚷
苯并三氮唑 1
2-氨基噻唑 0.5 聚氧乙烯改
2-咪唑垸酮 42 六缩丙 性的聚甲基
异丙
38.5 2 8 二醇单 8 丙烯酸 (数均 0.5
醇胺 甲基苯并三
苯基醚 分子量为 0.5
10000) 氮唑
2-氨基苯并
0.85 噻
聚氧乙烯改 1,3-二甲基 六缩异 16 二甲 性的聚丙烯 -2-咪唑烷酮
丙二醇
45 2.5 基乙 20 15 酸三乙醇胺 0.4
单苯基
醇胺 盐 (数均分子
醚
量^ 100000)
苯并三氮唑 0.25 三乙醇胺盐
2-氨基噁唑 0.01 聚氧乙烯改
丙二醇 性的聚甲基 1,3-二乙基
0.93 异丙
97 0.5 0.5 丙烯酸二乙 -2-咪唑烷酮
单苄基 1 0.01
醇胺 醇胺盐 (数均
分子量为
30000) 1-笨基 -5-巯
0.05 基四氮唑
Figure imgf000011_0001
Figure imgf000012_0001
效果实施例 对比清洗剂 1'~6 '和本发明的厚膜光刻胶清洗剂 1~12
表 2给出了对比清洗剂 Γ〜6'和和本发明的厚膜光刻胶清洗剂 1〜12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。 表 2对比清洗剂 1，〜6，和本发明的厚膜光刻胶清洗剂 1~12的组分和含量 聚氧乙 聚氧乙烯
烯改性 改性的聚 5-氮 1,3-二 苯 氢 丙二 3-氨基 聚乙 二甲 的聚丙 丙烯酸一 基- 甲基 并 单乙 乙 醇单 -1,2,4- 烯吡 洗 基亚 烯酸 (数 乙醇胺盐 四 -2-咪 三 化 醇胺 醇 苯基 三氮 咯垸 剂 砜 均分子 (数均分 氮 唑烷 氣 钾 胺 醚 唑 酮
量为 子量为 唑 酮 唑
5000) 40000)
1， 99.50 0.50 \ \ \ \ \ \ \ \ \ \
2' 59.00 \ 40.00 \ \ \ \ \ \ \ \ 1.00
3' 93.50 1.00 \ \ 5.00 \ \ \ \ \ \ 0.50
4' 93.50 1.00 5.00 \ \ \ \ \ \ \ \ 0.50
5， 93.50 1.00 0.50 \ 5.00 \ \ \ \ \ \ \
6' 88.00 1.00 0.50 \ 10.00 \ \ \ \ \ \ 0.50 1 93.40 1.00 0.50 \ 5.00 0.10 \ \ \ \ \ \
2 88.15 1.00 0.50 \ 10.00 \ 0.20 \ 0.15 \ \ \
3 85.80 2.00 1.00 \ 10.00 0.30 \ 0.40 \ \ \ 0.50
4 77.50 2.00 1.00 0.50 8.00 \ 0.50 0.50 \ 10.00 \ \
5 86.30 2.00 1.50 1.00 8.00 0.30 0.30 \ 0.50 \ 0.10 \
6 92.10 1.00 1 0.50 5.00 \ 0.40 0.50 \ \ \ 0.50
7 89.35 1.50 0.75 \ 7.00 0.80 \ 0.30 0.30 \ \ \
8 84.00 2.00 2.50 \ 10.00 0.30 0.60 \ 0.60 \ \ \
9 65.20 2.50 3.00 \ 12.00 0.50 0.50 \ 0.80 15.00 \ 0.50
10 77.70 3.00 5.00 2.00 10.00 1.00 \ 0.50 0.50 \ 0.30 \
11 73.20 3.50 8.00 \ 13.00 \ 0.80 \ 1.00 \ \ 0.50
12 58.10 4.00 15.00 1.50 16.00 1.00 1.00 0.90 1.50 \ \ 1.00 将表 2中的各种组分按照比例混合均匀， 制得对比清洗剂 Γ〜6'和本发 明的厚膜光刻胶清洗剂 1〜12。 其中， 除对比清洗剂 Γ中有未溶解的氢氧化 钾以外，对比清洗剂 2'〜6 '和本发明的清洗剂 1〜12均为澄清透明的均相溶液。
将表 2中的对比清洗剂 2'〜6 '和本发明的厚膜光刻胶清洗剂 1~12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 X4cm 空白 Cu晶片浸入清洗剂， 在 45〜90°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。
将表 2中的对比清洗剂 2'~6 '和本发明的厚膜光刻胶清洗剂 1〜12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 4X 4cm 空白 A1晶片浸入清洗剂， 在 45〜90°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。
将表 2中的对比清洗剂 2，~6 '和本发明的厚膜光刻胶清洗剂 1~12用于清 洗空白的四乙氧基硅垸（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， 在 45〜90°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。
本发明中， 利用表 2中的对比清洗剂 2，〜6，和本发明的厚膜光刻胶清洗 剂 1~12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光刻胶 (厚度约为 120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 45~90Ό下利用恒温振荡器振荡 15〜150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 2，〜6，和本发明的清洗剂 1〜12对金属 Cu和 A1 以及非金属 TEOS的腐蚀性及其对厚膜光刻胶的清洗情况 光刻胶
清洗 金属 Cu 金属 A1 非金属 光刻胶 晶片图
清洗时
洗 温度 的腐蚀 的腐蚀 TEOS的 清洗结 案的腐
间
剂 (°C) 情况 情况 腐蚀情况 果 蚀情况
(min)
V 90 Δ X 〇 150 X ◎
3， 80 〇 Δ ◎ 60 Δ Δ
4， 75 X X 〇 90 〇 〇
5， 75 〇 Δ 〇 90 ◎ ◎
6' 75 ◎ 〇 ◎ 90 ◎ ◎
1 80 〇 ◎ ◎ 90 ◎
2 85 ◎ ◎ 80 ◎ ◎
3 60 ◎ ◎ ◎ 100 ◎ ©
4 65 ◎ ◎ ◎ 120 ◎ 5 70 ◎ ◎ ◎ 70 ◎ ◎
6 55 ◎ ◎ ◎ 135 ◎ ◎
7 80 ◎ ◎ ® 30 ◎ ◎
8 90 ◎ ◎ ◎ 15 ◎ ◎
9 50 ◎ ◎ ◎ 150 ◎
10 65 ◎ ◎ ◎ 50 ◎ ◎
11 70 ◎ ◎ ◎ 65 ◎ ◎
12 45 ◎ ◎ ◎ 60 ◎ ◎ 腐蚀情况 清洗情况
© 基本无腐蚀 © 完全去除
o 略有腐蚀 o 少量残余
Δ 中等腐蚀 Δ 较多残余
X 严重腐蚀 X 大量残余
从表 3可以看出， 与对比清洗剂 2'〜6'相比， 本发明的厚膜光刻胶清洗 剂 1〜12对厚膜光刻胶具有良好的清洗效果， 使用温度范围较宽， 同时对金 属 Cu和 A1以及非金属 TEOS的腐蚀性低，对晶片图案无损坏且无腐蚀暗点
Figure imgf000015_0001

Claims

权利要求
1、 一种厚膜光刻胶清洗剂， 其特征在于： 其包含二甲基亚砜、 氢氧化 钾、 醇胺、烷基二醇芳基醚和聚丙烯酸类缓蚀剂， 其中烷基二醇芳基醚中烷 基二醇的碳原子数目为 3~18。
2、 如权利要求 1所述的清洗剂， 其特征在于： 所述的二甲基亚砜的含 量的为质量百分比 1〜97%。
3、 如权利要求 2所述的清洗剂， 其特征在于： 所述的二甲基亚砜的含 量的为质量百分比 30〜90%。
4、 如权利要求 1所述的清洗剂， 其特征在于： 所述的氢氧化钾的含量 为质量百分比 0.1~5%。
5、 如权利要求 4所述的清洗剂， 其特征在于： 所述的氢氧化钾的含量 为质量百分比 1~4%。
6、 如权利要求 1所述的清洗剂， 其特征在于： 所述的醇胺的含量为质 量百分比 0.1〜50%。
7、 如权利要求 6所述的清洗剂， 其特征在于： 所述的醇胺的含量为质 量百分比 0.5〜35%。
8、 如权利要求 1所述的清洗剂， 其特征在于： 所述的烷基二醇芳基醚 的含量为质量百分比 〜 50%。
9、 如权利要求 8所述的清洗剂， 其特征在于： 所述的烷基二醇芳基醚 的含量为质量百分比 5~30%。
10、如权利要求 1所述的清洗剂， 其特征在于： 所述的聚丙烯酸类缓蚀
11、 如权利要求 10所述的清洗剂， 其特征在于： 所述的聚丙烯酸类缓 蚀剂的含量为质量百分比 0.05〜2.5°/0。
12、如权利要求 1所述的清洗剂，其特征在于：所述的醇胺为一乙醇胺、 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。
13、 如权利要求 1所述的清洗剂， 其特征在于： 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、 六縮乙二醇单苯基醚、 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。
14、如权利要求 1所述的清洗剂， 其特征在于： 所述的聚丙烯酸类缓蚀 剂为聚丙烯酸、 丙烯酸共聚物、 聚甲基丙烯酸、 甲基丙烯酸共聚物、 聚丙烯 酸的醇胺盐、 丙烯酸共聚物的醇胺盐、聚甲基丙烯酸的醇胺盐、 甲基丙烯酸 共聚物的醇胺盐、聚氧乙烯改性的丙烯酸聚合物、聚氧乙烯改性的丙烯酸酯 聚合物、聚氧乙烯改性的丙烯酸聚合物醇铵盐、聚氧乙烯改性的甲基丙烯酸 聚合物、聚氧乙烯改性的甲基丙烯酸酯聚合物、和聚氧乙烯改性的甲基丙烯 酸聚合物醇铵盐中的一种或多种。
15、 如权利要求 1所述的清洗剂， 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。
16、 如权利要求 15所述的清洗剂， 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。
17、 如权利要求 1所述的清洗剂， 其特征在于： 所述的厚膜光刻胶清洗 剂还包含氨基唑类缓蚀剂、 极性有机共溶剂、 表面活性剂、 以及除聚丙烯酸 类缓蚀剂和氨基唑类缓蚀剂以外的其它缓蚀剂中的一种或多种。
18、 如权利要求 17所述的清洗剂， 其特征在于： 所述的氨基唑类缓蚀 剂的含量¾质量百分比 0.01~5%; 所述的极性有机共溶剂含量为质量百分比 50%;所述的表面活性剂含量为质量百分比 5%;所述的除聚丙烯酸类缓 蚀剂和氨基唑类缓蚀剂以外的其它缓蚀剂含量为质量百分比 5.0%;上述质 量百分比不包括 0%。
19、 如权利要求 18所述的清洗剂， 其特征在于： 所述的氨基唑类缓蚀 剂的含量为质量百分比 0.05〜2.5%； 所述的极性有机共溶剂含量为质量百分 比 5~30%； 所述的表面活性剂含量为质量百分比 0.05〜3.0%； 所述的除聚丙 烯酸类缓蚀剂和氨基唑类缓蚀剂以外的其它缓蚀剂含量为质量百分比 0.05-3.0%
20、 如权利要求 17所述的清洗剂， 其特征在于： 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、 1-甲基 -5- 氨基-四氮唑、 3-氨基 -5-巯基 -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、 2-氨基 -5-巯基 -1,3,4-噻二唑和 5-氨基 -1,2,3-噻二唑中的一种或多种； 所述的极性有 机共溶剂为亚砜、 砜、 咪唑垸酮和烷基二醇单垸基醚中的一种或多种； 所述 的表面活性剂为聚乙烯醇、 聚乙烯吡咯焼酮和聚氧乙烯醚中的一种或多种； 所述的除聚丙烯酸类缓蚀剂和氨基唑类缓蚀剂以外的其它缓蚀剂为胺类缓 蚀剂和 /或除氨基唑类缓蚀剂以外的唑类缓蚀剂。
21、 如权利要求 20所述的清洗剂， 其特征在于： 所述的亚砜为二乙基 亚砜和 /或甲乙基亚砜;所述的砜为甲基砜、乙基砜和环丁砜中的一种或多种； 所述的咪唑烷酮为 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； 所述的烷基二醇单烷基醚为乙二醇单丁醚、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； 所述的胺类缓蚀剂 为二乙烯三胺、三乙烯四胺、五乙烯六胺、 多乙烯多胺和氨基乙基哌嗪中的 一种或多种； 所述的除氨基唑类缓蚀剂以外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-巯基苯并噁唑和二巯基噻二唑中的一种或多种。
22、 如权利要求 17所述的清洗剂， 其特征在于： 所述的表面活性剂的 数均分子量为 500~20000。
23、 如权利要求 22所述的清洗剂， 其特征在于： 所述的表面活性剂的
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