WO2023133876A1 - 一种无氟清洗剂、其制备方法及应用 - Google Patents

一种无氟清洗剂、其制备方法及应用 Download PDF

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WO2023133876A1
WO2023133876A1 PCT/CN2022/072276 CN2022072276W WO2023133876A1 WO 2023133876 A1 WO2023133876 A1 WO 2023133876A1 CN 2022072276 W CN2022072276 W CN 2022072276W WO 2023133876 A1 WO2023133876 A1 WO 2023133876A1
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acid
fluorine
cleaning agent
triazole
amino
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PCT/CN2022/072276
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English (en)
French (fr)
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张爱强
陈婷
奈舍马克
卢聪杰
罗松松
赖委舜
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嘉庚创新实验室
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Priority to PCT/CN2022/072276 priority Critical patent/WO2023133876A1/zh
Publication of WO2023133876A1 publication Critical patent/WO2023133876A1/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—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
    • C11D7/50—Solvents
    • 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

Definitions

  • the invention belongs to the technical field of electronic industry, and in particular relates to a fluorine-free cleaning agent, its preparation method and application.
  • Integrated circuit chip manufacturing is a key link in the downstream of the semiconductor industry chain. With the gradual shrinking of the critical dimensions of integrated circuits, the industry has higher and higher requirements for chip manufacturing processes. Among them, after all kinds of materials on the wafer are etched or ashed, the residues after etching on the wafer surface are removed, which is the key technology to keep the follow-up process stable and ensure the performance, yield and reliability of the finished chip.
  • Etching is an important process for transferring patterns to metal or dielectric layers such as aluminum, silicon dioxide, and silicon nitride after photoresist development. After patterning is introduced, a large amount of photoresist, metal, etc. Residues such as reaction by-products and inorganic oxides that affect subsequent processes. These residues need to be removed by a special cleaning agent. In order to ensure the cleanliness and integrity of the wafer, it is not only required that the cleaning agent can completely remove all the residues, but also that the cleaning agent must not damage the metal layer on the wafer surface. , Dielectric layer and other base materials cause attack or damage.
  • fluorine-containing cleaning agents have the advantage of strong residue removal ability, but the existence of fluorine-containing compounds has a high risk of substrate corrosion, and the use of fluorine-containing cleaning agents is likely to cause wafer defects.
  • fluorine-containing cleaning agents after using a fluorine-containing cleaning agent, the wafer has the problem of poor weather resistance. This is because the surface of the wafer often remains after cleaning. Further reaction with the wafer substrate produces by-products such as aluminum fluoride, which are difficult to remove, resulting in reduced yield and some related chip quality issues.
  • fluorine-containing cleaning agents have higher requirements for production safety and machine equipment, which leads to an increase in production costs to a certain extent.
  • fluorine-free cleaning agents At present, many manufacturers have also developed fluorine-free cleaning agents, but the existing fluorine-free cleaning agents have disadvantages such as long cleaning time, high operating temperature, poor residue removal ability, and short service life, which cannot be applied to etching residues after multiple processes removal of matter. Therefore, a new type of fluorine-free post-etching residue cleaning agent has been developed to improve its ability to remove residues, prolong the life of the cleaning agent bath or shorten the process time, provide safer and easier operation techniques, control reasonable production process costs, and improve The overall price/performance ratio of products is a key strategy for improving one's own competitiveness in the rapidly developing semiconductor industry.
  • the technical problem to be solved by the present invention is to provide a fluorine-free cleaning agent with low cleaning temperature and high cleaning ability, its preparation method and application.
  • the invention provides a fluorine-free cleaning agent, the fluorine-free cleaning agent is an aqueous cleaning agent; the fluorine-free cleaning agent includes water, an organic solvent and an amine compound;
  • the quality of the organic solvent is 15% to 85% of the quality of the fluorine-free cleaning agent
  • the mass of the amine compound is 5% to 50% of the mass of the fluorine-free cleaning agent
  • It also includes one or more of corrosion inhibitors, acids and alcohol compounds.
  • the mass of the corrosion inhibitor is 0.1% to 10% of the mass of the fluorine-free cleaning agent
  • the mass of the acid is 0.5% to 5% of the mass of the fluorine-free cleaning agent
  • the mass of the alcohol compound is 0.5% to 10% of the mass of the fluorine-free cleaning agent
  • the alcohol compound is a dihydric alcohol compound and/or a polyhydric alcohol compound.
  • the corrosion inhibitor includes at least one of triazole groups, amino groups, hydroxyl groups, carboxyl groups or mercapto groups;
  • the acid is selected from one or more of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, citric acid, boric acid and carbonic acid;
  • the alcohol compound is selected from ethylene glycol, glycerol, 1,3-butanediol, 1,2-pentanediol, pentaerythritol, 2,5-hexanediol, polycaprolactone diol, 1 ,6-Hexanediol, Sorbitol, Neopentyl Glycol, 1,4-Butanediol, 1,2,6-Hexanetriol, Xylitol, L-Mannitol, D(+)-Arabic Sugar alcohol, geraniol, sweet alcohol, 1,2,4-butanetriol, furfuryl alcohol, phytol, dipentaerythritol, L-threoninol, L-talitol, glucose, erythritol and xylose one or more of these.
  • the corrosion inhibitor is selected from 1,2,4-triazole, benzotriazole, 1H-1,2,3-triazole, 5-methylbenzotriazole, 5- Hydroxybenzotriazole, 1H-1,2,3-triazole-1-amine, 3-cyano-1,2,4-triazole, 1,2,4-triazole-3- Formamide, 1-ethyl-1H-1,2,3-triazole, 1-phenyl-1H-1,2,4-triazole, 1H-1,2,4-triazole-3 -Carboxylic acid, 2-phenyl-2H-1,2,3-triazole, 3-methyl-1H-1,2,4-triazole, 3-phenyl-1,2,4-1H -Triazole, 4-methyl-1H-1,2,3-triazole, 1H-1,2,3-triazole-4-carboxylic acid, 2H-2-acetic acid-1,2,3 -Triazole, 3,5-diamino-1,2,4-triazole, 1,2,3-triazole, 1,2,
  • the amine compound is selected from methylamine, ethylamine, hydroxylamine, octylamine, triethylamine, acetamide, diethylamine, tert-butylamine, butyramide, dopamine, isobutylamine, isoamylamine, n-propylamine, n-hexylamine, cyclopropylamine, cyclohexylamine, cycloheptylamine, cyclopentylamine, heptylamine, ethanolamine, diethanolamine, diglycolamine, isopropanolamine, triisopropanolamine, diisopropanolamine, N- Ethylethanolamine, N-phenylethanolamine, N-acetylethanolamine, N-butyldiethanolamine, N-cyclohexylethanolamine, N-benzyldiethanolamine, N-phenyldiethanolamine, N,N-di
  • a stabilizer is also included; the quality of the stabilizer is 2% to 20% of the quality of the fluorine-free cleaning agent; the stabilizer is selected from the group consisting of ethanol, 2-hydroxypyridine, 4-hydroxypyridine, p-hydroxybenzaldehyde, Salicylic acid, thiosalicylic acid, 2,6-dimethyl-3-hydroxypyridine, 2,3-dihydroxypyridine, 5-amino-2-hydroxypyridine, gelatin, trishydroxymethylaminomethane, 3 -Morpholinopropanesulfonic acid, 4-hydroxyethylpiperazineethanesulfonic acid, ammonium borate, ammonium acetate, ammonium formate, ammonium borate, ammonium formate, ammonium phosphate, ammonium dihydrogen phosphate, ammonium citrate and barbituric acid one or more of
  • the quality of the surfactant is 0.5% to 10% of the mass of the fluorine-free cleaning agent; the surfactant is selected from 3,5-dimethyl-1-hexyn-3-alcohol, Laureth Phosphate, Diethanolamide Cocoate, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Lauramidopropyl Hydroxysultaine, Acetone Oxime, Lauramidopropyl Hydroxybetaine One or more of amine, monoglyceride, span, dodecylbenzenesulfonic acid and polyoxy-15 hydroxystearate.
  • the quality of the antioxidant is 0.1% to 10% of the quality of the fluorine-free cleaning agent; the antioxidant is selected from butyl hydroxyanisole, 2,6-di-tert-butyl p-cresol , one or more of hydroquinone, D-isoascorbic acid, sorbitol, phytic acid, chitosan and chitosan oligosaccharide.
  • the present invention also provides a preparation method of the above-mentioned fluorine-free cleaning agent, comprising:
  • the fluorine-free cleaning agent is obtained by mixing water, an organic solvent, an amine compound, and one or more of corrosion inhibitors, acids and alcohol compounds.
  • the present invention also provides the application of the above-mentioned fluorine-free cleaning agent in the field of electronic industry including but not limited to semiconductor integrated circuits.
  • the present invention also provides a cleaning method, comprising: using the above-mentioned fluorine-free cleaning agent to clean the wafer by soaking method or single wafer method.
  • the invention provides a fluorine-free cleaning agent, the fluorine-free cleaning agent is an aqueous cleaning agent; the fluorine-free cleaning agent includes water, an organic solvent and an amine compound; the quality of the organic solvent is the quality of the fluorine-free cleaning agent 15% to 85% of the mass of the amine compound; the mass of the amine compound is 5% to 50% of the mass of the fluorine-free cleaning agent; it also includes one or more of corrosion inhibitors, acids and alcohol compounds.
  • the fluorine-free cleaning agent provided by the present invention has better performance without containing fluorine through the synergistic effect of one or more of specific amine compounds and corrosion inhibitors, acids and alcohols. At the same time, it can also reduce the corrosion of the metal by the cleaning solution, prevent damage to the substrate medium, and improve the weather resistance of the wafer after cleaning. Compared with existing similar products, it has obvious advantages such as lower cleaning temperature, cleaning time and higher cost performance.
  • Figure 1 is a SEM image of the wafer after metal aluminum etching and before cleaning
  • Fig. 2 is the SEM picture of the wafer after cleaning metal aluminum etching by using Embodiment 1 of the present invention
  • Fig. 3 is the SEM image of the wafer after the metal aluminum etching is cleaned by using the fluorine-free cleaning agent provided in Comparative Example 1;
  • Fig. 4 is the SEM image before wafer cleaning after silicon dioxide film etching
  • FIG. 5 is an SEM image of a wafer after silicon oxide film etching is cleaned using the fluorine-free cleaning agent provided in Embodiment 7 of the present invention
  • Fig. 6 is the SEM image of the wafer after silicon dioxide etching by using the fluorine-free cleaning agent provided in Comparative Example 1 to clean;
  • FIG. 7 is a SEM image of the silicon nitride film before wafer cleaning after etching
  • FIG. 8 is a SEM image of a silicon nitride etched wafer cleaned by using the fluorine-free cleaning agent provided in Embodiment 7 of the present invention.
  • FIG. 9 is an SEM image of a silicon nitride etched wafer cleaned with the fluorine-free cleaning agent provided in Comparative Example 1.
  • FIG. 9 is an SEM image of a silicon nitride etched wafer cleaned with the fluorine-free cleaning agent provided in Comparative Example 1.
  • the invention provides a fluorine-free cleaning agent, the fluorine-free cleaning agent is an aqueous cleaning agent; the fluorine-free cleaning agent includes water, an organic solvent and an amine compound;
  • the quality of the organic solvent is 15% to 85% of the quality of the fluorine-free cleaning agent
  • the mass of the amine compound is 5% to 50% of the mass of the fluorine-free cleaning agent
  • It also includes one or more of corrosion inhibitors, acids and alcohol compounds.
  • the fluorine-free cleaning agent provided by the present invention also has good cleaning ability without fluorine element through the synergistic effect of one or more of specific amine compounds and corrosion inhibitors, acids and alcohols, and can also Reduce the corrosion of the metal by the cleaning solution, prevent damage to the substrate medium, and improve the weather resistance of the wafer after cleaning. Compared with existing similar products, it has obvious advantages such as lower cleaning temperature, cleaning time and higher cost performance.
  • the pH value of the fluorine-free cleaning agent provided by the present invention is preferably 7-13, more preferably 7.9-13; in the examples provided by the present invention, the pH value of the fluorine-free cleaning agent is specifically 11.5, 11.8, 10.6, 11.7, 11.3, 12.8, 12.5, 12.7, 12.0, 13.0, 7.9, 10.5, 10.7, 8.6, 11.2, 11.1, or 8.0.
  • the fluorine-free cleaning agent provided by the present invention is an aqueous cleaning agent; the cleaning agent includes an organic solvent; the quality of the organic solvent is preferably 15% to 85% of the quality of the fluorine-free cleaning agent, more preferably 15% to 70% , preferably 15% to 60%; in the embodiments provided by the present invention, the quality of the organic solvent is specifically 15%, 25%, 60%, 35%, 38% or 40% of the quality of the fluorine-free cleaning agent
  • the organic solvent is an organic solvent well known to those skilled in the art, and there is no special limitation.
  • the alcohol ether organic solvent is preferably ethylene glycol monomethyl One or more of ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, dipropylene glycol butyl ether and tripropylene glycol butyl ether; in the present invention
  • the organic solvent is preferably ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, dipropylene glycol butyl ether, three Propylene glycol butyl ether, propylene glycol methyl ether acetate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylpropionamide, N,N- One or
  • the fluorine-free cleaning agent provided by the invention contains amine compounds; the quality of the amine compounds is preferably 5% to 40% of the quality of the fluorine-free cleaning agent; in the examples provided by the invention, the amine compounds The quality is specifically 15%, 25%, 22%, 50%, 5%, 32% or 40% of the quality of the fluorine-free cleaning agent; the amine compound is selected from methylamine, ethylamine, hydroxylamine, octylamine, triethylamine Amine, acetamide, diethylamine, tert-butylamine, butyramide, dopamine, isobutylamine, isopentylamine, n-propylamine, n-hexylamine, cyclopropylamine, cyclohexylamine, cycloheptylamine, cyclopentylamine, heptylamine, ethanolamine, Diethanolamine, diglycolamine, isopropanolamine, triiso
  • the fluorine-free cleaning agent provided by the invention also includes at least one or more of corrosion inhibitors, acids and alcohol compounds.
  • the quality of the corrosion inhibitor is preferably 0.5% to 10% of the quality of the fluorine-free cleaning agent, more preferably 1% to 7%, and more preferably 1% to 5%; in the embodiments provided by the present invention, the corrosion inhibitor is specifically 1%, 4%, 2%, 5% or 10% of the mass of the fluorine-free cleaning agent; in the present invention, the The corrosion inhibitor preferably includes at least one of triazole groups, amino groups, hydroxyl groups, carboxyl groups or mercapto groups, more preferably 1,2,4-triazole, benzotriazole , 1H-1,2,3-triazole, 5-methylbenzotriazole, 5-hydroxybenzotriazole, 1H-1,2,3-triazol-1-amine, 3- Cyano-1,2,4-triazole, 1,2,4-triazole-3-carboxamide, 1-ethyl-1H-1,2,3-triazole, 1-
  • adding acid can also reduce the metal etching rate while improving the cleaning ability of the cleaning agent;
  • the quality of the acid is preferably 0.5% to 5% of the quality of the fluorine-free cleaning agent, more preferably 1% to 4%, more preferably 2% to 3.5%, most preferably 2.5% to 3%; in the examples provided by the present invention, the quality of the acid is specifically 2.8% of the mass of the fluorine-free cleaning agent, 3% or 2%;
  • described acid can be inorganic acid also can be organic acid, does not have special limitation, is preferably sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, citric acid, One or more of boric acid and carbonic acid.
  • the quality of the alcohol compound is preferably 0.5% to 10% of the mass of the fluorine-free cleaning agent, more preferably 1% to 5%, and more preferably 1% to 4%; In an example, the quality of the alcohol compound is specifically 1%, 4%, 3% or 2% of the mass of the fluorine-free cleaning agent; the alcohol compound is preferably a dihydric alcohol compound and/or a polyhydric alcohol compound, More preferably ethylene glycol, glycerol, 1,3-butanediol, 1,2-pentanediol, pentaerythritol, 2,5-hexanediol, polycaprolactonediol, 1,6-hexanediol Alcohol, Sorbitol, Neopentyl Glycol, 1,4-Butanediol, 1,2,6-Hexanetriol, Xylitol, L-Mannitol, D(+)-Arabitol, Geranium
  • the fluorine-free cleaning agent provided by the present invention preferably also includes a stabilizer; the quality of the stabilizer is preferably 2% to 20% of the quality of the fluorine-free cleaning agent; the stabilizer can adjust the acidity and alkalinity of the cleaning agent and maintain its stability, while also having The role of keeping the physical and chemical properties of the cleaning agent consistent is beneficial to prolonging the storage life of the cleaning agent and the life of the bath solution.
  • the stabilizer is preferably ethanol, 2-hydroxypyridine, 4-hydroxypyridine, p-hydroxybenzaldehyde, salicylic acid, thiosalicylic acid, 2,6-dimethyl-3-hydroxypyridine, 2,3- Dihydroxypyridine, 5-amino-2-hydroxypyridine, gelatin, trishydroxymethylaminomethane, 3-morpholinepropanesulfonic acid, 4-hydroxyethylpiperazineethanesulfonic acid, ammonium borate, ammonium acetate, ammonium formate, One or more of ammonium borate, ammonium formate, ammonium phosphate, ammonium dihydrogen phosphate, ammonium citrate, barbituric acid, etc.
  • the fluorine-free cleaning agent provided by the present invention preferably further includes a surfactant, which can promote the dispersibility and stability of each component in the cleaning agent.
  • the quality of the surfactant is preferably 0.5% to 10% of the mass of the fluorine-free cleaning agent; in the examples provided by the present invention, the quality of the surfactant is specifically 2% of the mass of the fluorine-free cleaning agent; Surfactant selected from 3,5-dimethyl-1-hexyn-3-ol, lauryl ether phosphate, cocoic acid diethanolamide, cocamidopropyl betaine, cocamidopropyl sulfone betaine, lauryl amidopropyl hydroxysultaine, acetone oxime, lauryl amidopropyl amine oxide, monoglyceride, span, dodecylbenzenesulfonic acid and polyoxy-15 hydroxystearate, etc. one or more of.
  • the fluorine-free cleaning agent provided by the present invention preferably further includes an antioxidant, which can improve the oxidation resistance and discoloration resistance of the cleaning agent.
  • the quality of the antioxidant is preferably 0.1% to 5% of the mass of the fluorine-free cleaning agent; in the embodiments provided by the present invention, the quality of the antioxidant is specifically 1% of the mass of the fluorine-free cleaning agent;
  • the antioxidant is preferably one of butyl hydroxyanisole, 2,6-di-tert-butyl p-cresol, hydroquinone, D-isoascorbic acid, sorbitol, phytic acid, chitosan and chitosan oligosaccharide or more.
  • the present invention also provides a preparation method of the above-mentioned fluorine-free cleaning agent, comprising: mixing water, an organic solvent, an amine compound with one or more of corrosion inhibitors, acids and alcohol compounds to obtain a fluorine-free cleaning agent agent.
  • the present invention has no special limitation on the sources of all raw materials, which can be commercially available.
  • the water, organic solvents, amine compounds and corrosion inhibitors are all the same as those described above, and will not be repeated here.
  • the present invention also provides a kind of application of the above-mentioned fluorine-free cleaning agent in the integrated circuits including but not limited to the semiconductor field; further preferably, the application in cleaning after the semiconductor etching process; the semiconductor etching process can be metal Etching, dielectric material etching, and etching of inorganic media such as silicon are not particularly limited.
  • the semiconductor etching process can be metal Etching, dielectric material etching, and etching of inorganic media such as silicon are not particularly limited.
  • it may specifically include cleaning residues after metal etching processes such as aluminum, titanium, and tantalum, and may also include two Cleaning of residues after the etching process of dielectric layers such as silicon oxide and silicon nitride; the types of residues to be cleaned include but are not limited to photoresist residues, inorganic residues, metal reaction by-products, etc.
  • the present invention also provides a cleaning method of the fluorine-free cleaning agent, comprising: using the above-mentioned fluorine-free cleaning agent to clean the wafer by soaking method or single wafer method.
  • the dry-etched wafer is soaked in the above-mentioned fluorine-free cleaning agent;
  • the soaking temperature is preferably 20°C to 70°C, more preferably 25°C to 70°C;
  • the soaking time is preferably 1-60 min, more preferably 1-40 min, more preferably 1-20 min, most preferably 1-10 min;
  • the etched wafer is specifically a metal or an inorganic medium
  • the etched wafers can be specifically etched wafers of aluminum, titanium, tantalum, nickel, silicon dioxide, silicon nitride, etc.; the soaked wafers are preferably rinsed with ultrapure water, etc. , blow dry with nitrogen to complete the cleaning.
  • the fluorine-free cleaning agent of the present invention can also be cleaned by a single wafer method, specifically: the etched wafer is rotated by means of equipment such as a spin coater, and the fluorine-free cleaning agent and super Pure water is used for cleaning; the rotation speed is 50-5000 rpm/min, and the operating temperature of the instrument is preferably 20°C-70°C; the single-wafer cleaning time is 1-60min.
  • the fluorine-free cleaning agent provided by the invention has strong cleaning ability, and can reduce the cleaning temperature and cleaning time of the cleaning agent.
  • the total amount of each chemical reagent is 100g, and add to the beaker one by one and shake well.
  • the solid reagent can be weighed first, and then dissolved by adding a solvent.
  • the total amount of each chemical reagent is 100g, and add to the beaker one by one and shake well.
  • the solid reagent can be weighed first, and then dissolved by adding a solvent.
  • the total amount of each chemical reagent is 100g, and add to the beaker one by one and shake well.
  • the solid reagent can be weighed first, and then dissolved by adding a solvent.
  • the total amount of each chemical reagent is 100g, and add to the beaker one by one and shake well.
  • the solid reagent can be weighed first, and then dissolved by adding a solvent.
  • each chemical reagent Contains 10wt% monoethanolamine, 7wt% 1,3-propanediamine, 5wt% isopropanolamine, 25wt% diethylene glycol monobutyl ether, 2.8wt% boric acid, 1wt% benzotriazole and the balance of super Pure water, the total amount of each chemical reagent is 100g, and add to the beaker one by one and shake well. Among them, the solid reagent can be weighed first, and then dissolved by adding a solvent.
  • the total amount of each chemical reagent is 100g, and press Add one by one to the beaker and shake well. Among them, the solid reagent can be weighed first, and then dissolved by adding a solvent.
  • the total amount of each chemical reagent is 100g, and press Add one by one to the beaker and shake well. Among them, the solid reagent can be weighed first, and then dissolved by adding a solvent.
  • the total amount of each chemical reagent is 100g, and added to the beaker one by one Shake well.
  • the solid reagent can be weighed first, and then dissolved by adding a solvent.
  • the total amount of each chemical reagent is 100g, and Add one by one to the beaker and shake well. Among them, the solid reagent can be weighed first, and then dissolved by adding a solvent.
  • compositions of the fluorine-free cleaning agents provided in Examples 1 to 8 and Comparative Examples 1 and 2 are shown in Table 1 and Table 2.
  • Example 2 Example 3
  • Example 4 D-Sorbitol 1 1 1 1
  • Fig. 1 is the SEM image of the wafer before cleaning after metal aluminum etching
  • Fig. 2 is the SEM image of cleaning the wafer after metal aluminum etching by using the fluorine-free cleaning agent provided in Example 1 of the present invention
  • Fig. 3 is a comparative example 1.
  • Example 1 remove completely
  • Example 2 remove completely
  • Example 3 remove completely
  • Example 4 remove completely
  • Example 5 remove completely Example 6 remove completely Example 7 remove completely Example 8 remove completely Comparative example 1 Not completely removed, complete removal needs to increase the working temperature to 90°C Comparative example 2 Not completely cleared
  • the silicon dioxide etched wafer was immersed in a fluorine-free cleaning agent, the experimental temperature was 70° C., and the immersion time was 10 minutes. After the completion, take out the sample piece, wash it with water and blow nitrogen gas immediately, and then use a scanning tunneling microscope (SEM) to observe the cleaning of the residue on the wafer surface.
  • SEM scanning tunneling microscope
  • the silicon nitride etched wafer was immersed in a fluorine-free cleaning agent, the experimental temperature was 70° C., and the immersion time was 10 minutes. After the end, remove the sample piece, wash it with water and blow nitrogen gas immediately, and then use a scanning tunneling microscope (SEM) to observe the cleaning of the residue after etching.
  • SEM scanning tunneling microscope
  • Figure 7 shows the silicon nitride film etching
  • Figure 8 is the SEM image of the wafer after silicon nitride etching by using the fluorine-free cleaning agent provided in Example 7 of the present invention
  • Figure 9 is the nitrogen-cleaning image using the fluorine-free cleaning agent provided in Comparative Example 1
  • the SEM image of the wafer after silicon oxide etching it can be seen from Figure 9 that the sidewall is not cleaned.
  • test temperature is 70°C
  • take out the sample piece after the end wash it with water and dry it with nitrogen , and then use the four-probe method to test the corrosion rate of the metal film and observe the surface corrosion by SEM.
  • Table 6 The results are shown in Table 6.
  • the present invention is used in the etched wafer, wherein the thickness of metal aluminum, silicon oxide and silicon nitride is 1 micron; the metal aluminum is introduced into the wafer by plasma sputtering, and chlorine gas and Boron trichloride is subjected to plasma dry etching; the silicon oxide and silicon nitride are prepared by chemical vapor deposition, and fluorine-containing gas, oxygen and argon are used to perform plasma dry etching.
  • the application of the fluorine-free cleaning agent of the present invention includes but not limited to the removal of residues on the wafer surface after dry etching, and the application object can also be the wafer after wet etching.
  • Example 10 Example 11
  • Example 12 Example 13 Comparative example 3 Comparative example 4 boric acid 0 0 3 3 3 3 0
  • Diethylene glycol monobutyl ether 35 0 35 35 0 0 35
  • Dimethyl sulfoxide 0 35 0 0 0 0 0
  • Dimethylacetamide 0 0 0 0 35
  • 1,3-Propanediamine 50 35 7 0 0
  • the fluorine-free cleaning agents of Examples 14-18 and Comparative Examples 5-6 were prepared according to the methods of the above-mentioned examples and the composition formulations in Table 10.
  • Example 14 Example 15
  • Example 16 Example 17
  • Example 18 Comparative example 5
  • Comparative example 6 formic acid 2 0 0 0 2 0 2 boric acid 0 2 2 2 0 0 0

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Abstract

本发明提供了一种无氟清洗剂，所述无氟清洗剂为水性清洗剂；所述无氟清洗剂包括水、有机溶剂与胺类化合物；所述有机溶剂的质量为无氟清洗剂质量的15％～85％；所述胺类化合物的质量为无氟清洗剂质量的5％～50％；还包括腐蚀抑制剂、酸与醇类化合物中的一种或多种。与现有技术相比，本发明提供的无氟清洗剂通过特定的胺类化合物与腐蚀抑制剂、酸及醇中的一种或多种协同作用在不含有氟元素的情况下也具有较好的清洗能力，同时还可降低清洗液对金属的腐蚀，防止对基底介质产生破坏，提高清洗后晶圆的耐候性。与现有同类产品比，本发明提供的无氟清洗剂具有降低清洗温度、清洗时间以及更高性价比等明显优势。

Description

一种无氟清洗剂、其制备方法及应用 技术领域
本发明属于电子工业技术领域，尤其涉及一种无氟清洗剂、其制备方法及应用。
背景技术
集成电路芯片制造是半导体产业链下游的关键环节。随着集成电路关键尺寸的逐渐缩小，产业界对于芯片制造的工艺要求也越来越高。其中，晶圆上各类材料经过刻蚀或灰化等工艺后，对晶圆表面蚀刻后残留物进行去除，是保持后续工艺稳定进行，保证芯片成品性能、良率和可靠性的关键技术。
刻蚀是在光刻胶显影之后，将图案转移到铝、二氧化硅、氮化硅等金属或介质层的一个重要工艺，在图案化引入之后，晶圆表面会附着大量光刻胶、金属反应副产物、无机氧化物等影响后道工艺的残留物。这些残留物需要通过特殊的清洗剂来进行清除，为了保证晶圆的洁净度与完整性，在清除时不仅要求清洗剂能够完全去除所有的残留物，同时要求清洗剂不能对晶圆表面金属层、介质层等基底材料造成攻击或破坏。
随着集成电路的发展，用于清除刻蚀工艺后晶圆表面残留物的清洗剂也同样在更新换代。其中含氟清洗剂具有残留物去除能力强的优点，然而含氟化合物的的存在对基底腐蚀风险高，含氟清洗剂的使用容易造成晶圆的缺陷产生。同时，在实际生产中也发现在使用含氟清洗剂之后，晶圆存在着耐候性差的问题，这是由于在清洗之后晶圆表面往往会残留由清洗剂带来的含氟化合物，含氟化合物进一步与晶圆基底发生反应产生氟化铝等副产物，这些副产物难以清除，造成良率下降以及一些相关的芯片质量问题。此外，含氟清洗剂对于生产安全、机台设备的要求也更高，在一定程度上导致了生产成本的提高。
目前不少厂家也开发了无氟清洗剂，但现有无氟清洗剂存在着清洗时间长、操作温度高、残留物去除能力差、使用寿命短等缺点，无法应用于多个制程后蚀刻残留物的去除。因此开发出新型无氟后蚀刻残留物清洗剂，提高其对残留物的去除能力，延长清洗剂槽液寿命或缩短制程时间，提供更安全、简便的操作工艺，控制合理的生产工艺成本，提高产品的总性价比，是在快速发展的半导体产业中提升自身竞争力的关键策略。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种清洗温度较低且清洗能力较高的无氟清洗剂、其制备方法及应用。
本发明提供了一种无氟清洗剂，所述无氟清洗剂为水性清洗剂；所述无氟清洗剂包括水、有机溶剂与胺类化合物；
所述有机溶剂的质量为无氟清洗剂质量的15％～85％；
所述胺类化合物的质量为无氟清洗剂质量的5％～50％；
还包括腐蚀抑制剂、酸与醇类化合物中的一种或多种。
优选的，所述腐蚀抑制剂的质量为无氟清洗剂质量的0.1％～10％；
所述酸的质量为无氟清洗剂质量的0.5％～5％；
所述醇类化合物的质量为无氟清洗剂质量的0.5％～10％；
所述醇类化合物为二元醇类化合物和/或多元醇类化合物。
优选的，所述腐蚀抑制剂至少包括含有***基团、氨基基团、羟基基团、羧基基团或巯基基团中一种；
所述酸选自硫酸、硝酸、盐酸、磷酸、甲酸、乙酸、柠檬酸、硼酸与碳酸中的一种或多种；
所述醇类化合物选自为乙二醇、丙三醇、1,3-丁二醇、1,2-戊二醇、季戊四醇、2,5-己二醇、聚己内酯二醇、1,6-己二醇、山梨糖醇、新戊二醇、1,4-丁二醇、1,2,6-己三醇、木糖醇、L-甘露糖醇、D(+)-***糖醇、香叶醇、甜醇、1,2,4-丁三醇、糠醇、植醇、双季戊四醇、L-苏氨醇、L-塔罗糖醇、葡萄糖、赤藓糖醇与木糖等中的一种或多种。
优选的，所述腐蚀抑制剂选自1,2,4-三氮唑、苯并三氮唑、1H-1,2,3-三氮唑、5-甲基苯并三氮唑、5-羟基苯并三氮唑、1H-1,2,3-三氮唑-1-胺、3-氰基-1,2,4-三氮唑、1,2,4-三氮唑-3-甲酰胺、1-乙基-1H-1,2,3-三氮唑、1-苯基-1H-1,2,4-三氮唑、1H-1,2,4-三氮唑-3-羧酸、2-苯基-2H-1,2,3-三氮唑、3-甲基-1H-1,2,4-三氮唑、3-苯基-1,2,4-1H-三氮唑、4-甲基-1H-1,2,3-三氮唑、1H-1,2,3-三氮唑-4-羧酸、2H-2-乙酸-1,2,3-三氮唑、3,5-二氨基-1,2,4-三氮唑、1,2,3-三氮唑-4-甲酸甲酯、1,2,4-三氮唑-3-羧酸甲酯、N,N’-羰基二(1,2,3-三氮唑)、1,4-二甲基-1H-1,2,3-三氮唑、2H-1,2,3-三氮唑-4-羧酸甲酯、3,5-二苯基-1H-1,2,4-三氮唑、 3-巯基-5-甲基-1,2,4-三氮唑、3-氨基-5-巯基-1,2,4-三氮唑、3-(1,2,4-三氮唑-1-基)苯甲酸、3-(1,2,4-三氮唑-1-基)苯甲醛、4-(4H-1,2,4-三氮唑-3-基)苯胺、1-羟基苯丙***、3-(1H-(1,2,3)三氮唑-4-基)-苯腈、3-巯基-1,2,4-***、3-氨基-1,2,4-***、3-氨基-1H-1,2,4-三氮唑-5-羧酸、4-(4H-1,2,4-三氮唑-4-基)苯甲酸、1-羟基-7-偶氮苯并三氮唑、[1,2,4]三氮唑[1,5-a]吡啶-6-甲醛、[1,2,4]三氮唑并[1,5-a]吡啶-7-醇、1-甲基-1,2,3-三氮唑-5-甲酸甲酯、5-环己基-1H-3-氨基-1,2,4-三氮唑、4-氨基-4H-1,2,4-***、5-氨基-2,4-二氢-[1,2,4]三氮唑-3-酮、4,5,6,7-四氢-1,2,3-三氮唑并[1,5-a]吡嗪、2-巯基吡啶、2-巯基吡嗪、2-巯基咪唑、2-巯基噻唑、2-巯基烟酸、3-巯基丁酸、3-巯基丙酸、3-巯基吲哚、4-巯基吡啶、4-巯基尿苷、6-巯基嘌呤、6-巯基己酸、β-巯基乙胺、二巯基丙醇、巯基尼古胺、1,5-二巯基萘、2-巯基-3-丁醇、2-巯基-3-戊酮、2-巯基噻唑啉、2-巯基苯甲醇、2-甲巯基苯胺、3-巯基-1-己醇、3-巯基-2-丁酮、3-巯基-2-戊酮、2-巯基苯甲酸、3-巯基苯甲酸、4-巯基苯甲酸、4-巯基苯甲醇、4-巯基苯甲醛、6-巯基己-1-醇、6-甲巯基嘌呤、2,4-二巯基嘧啶、2,6-二巯基嘌呤、2-巯基苯并咪唑、2-巯基苯并噻唑、2-巯基苯并恶唑、4-巯基苯基乙酸、乙酸3-巯基己酯、3-巯基-1,2,4-***、邻氨基苯酚、邻苯二酚、多巴胺、4-乙基儿茶酚、3,4-二羟基苯甲酸、去甲二氢愈创木酸、2,3-二羟基吡啶、2,4-二羟基喹啉、3,4-二羟基苯乙酮、2,3-二羟基喹喔啉、3,4-二羟基苯甲腈、1,2-二羟基萘、3,4-二羟基苯甲醛、5,6-二羟基吲哚、4-氨基-6-羟基-2-巯基嘧啶、2-甲基巯基-4-氨基-6-羟基嘧啶、2-巯基苯甲醇、2-巯基胞嘧啶、6-巯基-1-己醇、6-氨基-2-巯基嘧啶-4-醇、3-巯基-1-己醇、硫代水杨酸、3-巯基-1-丙醇、3-巯基丙酸、2-巯基-5-甲基苯并咪唑、4,6-二甲基-2-巯基嘧啶、3-巯基-3-甲基-1-丁醇、3-巯基-4-甲基-4H-1,2,4-***、5-甲氧基-2-巯基苯并咪唑、3-巯基苯基硼酸、聚乙二醇、聚酰亚胺、2-苯基-4-五亚乙基六胺-2-醇、3-氨基-5-羟基吡唑、2-氨基-3-羟基吩嗪、4-氨基-3-羟基苯甲酸、3-氨基-4-羟基吡啶、2'-氨基-3'-羟基苯乙酮、5-氨基-2-羟基吡啶、4-氨基-6-羟基嘧啶、2-氨基-8-羟基喹啉、2-氨基-3-羟基吡啶、3'-氨基-2'-羟基联苯基-3-甲酸、2-氨基-4-羟基苯并噻唑、2-乙酰氨基-6-羟基嘌呤、2-氨基-N-羟基丙酰胺、2-氨基-N-羟基戊酰胺、3-氨基-5-羟基吡啶、4-乙酰氨基-3-羟基苯甲酸与2-氨基-4-羟基-6-甲基嘧啶等中的一种或多种。
优选的，所述胺类化合物选自甲胺、乙胺、羟胺、辛胺、三乙胺、乙酰胺、二乙胺、叔丁胺、丁酰胺、多巴胺、异丁胺、异戊胺、正丙胺、正己胺、环丙胺、环己胺、环庚胺、环戊胺、庚胺、乙醇胺、二乙醇胺、二甘醇胺、异丙醇胺、三异丙醇胺、二异丙醇胺、N-乙基乙醇胺、N-苯基乙醇胺、N-乙酰乙醇胺、N-丁基二乙醇胺、N-环己基乙醇胺、N-苄基二乙醇胺、N-苯基二乙醇胺、N,N-二苄基乙醇胺、N-叔丁基二乙醇胺、N-叔丁基异丙醇胺、N-甲基二异丙醇胺、1,6-己二胺、1,2-丙二胺、1,3-丙二胺、1,4-丁二胺、1,8-辛二胺、三乙烯二胺、三正十二胺、二乙烯三胺、己二酰二胺、马来酸二胺、2-辛基十二胺、N-乙基乙二胺、N-甲基乙二胺、N-苄基乙二胺、N-苯基乙二胺、精胺、N-乙酰乙二胺、五乙烯六胺、四乙烯五胺、1H-吡唑-3,5-二胺、3-二乙胺基丙胺、3-二甲胺基丙胺、N-丁基乙烯二胺、N-异丙基乙二胺、N-甲基对苯二胺、四甲基甲烷二胺、四丁基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四甲基氢氧化铵、2-[(羟甲基)氨基]乙醇、苄基三甲基氢氧化铵、N-(苄羰氧基)羟基胺与N,N-二苄基羟基胺中的一种或多种；所述有机溶剂选自乙二醇单甲醚、乙二醇单***、乙二醇单丁醚、二乙二醇甲醚、二乙二醇丁醚、二丙二醇丁醚、三丙二醇丁醚、丙二醇甲醚醋酸酯、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基丙酰胺、N,N-二甲基丙酰胺、N,N-二乙基乙酰胺、环丁砜、二甲基亚砜与1,4-丁内酯中的一种或多种。
优选的，还包括稳定剂；所述稳定剂的质量为无氟清洗剂质量的2％～20％；所述稳定剂选自乙醇、2-羟基吡啶、4-羟基吡啶、对羟基苯甲醛、水杨酸、硫代水杨酸、2,6-二甲基-3-羟基吡啶、2,3-二羟基吡啶、5-氨基-2-羟基吡啶、明胶、三羟甲基氨基甲烷、3-吗啉丙磺酸、4-羟乙基哌嗪乙磺酸、硼酸铵、乙酸铵、甲酸铵、硼酸铵、甲酸铵、磷酸铵、磷酸二氢铵、柠檬酸铵与巴比妥酸中的一种或多种；
还包括表面活性剂；所述表面活性剂的质量为无氟清洗剂质量的0.5％～10％；所述表面活性剂选自3,5-二甲基-1-己炔-3-醇、月桂醇醚磷酸酯、椰油酸二乙醇酰胺、椰油酰胺丙基甜菜碱、椰油酰胺丙基羟磺基甜菜碱、月桂酰胺丙基羟磺基甜菜碱、丙酮肟、月桂酰胺丙基氧化胺、单甘脂、司班、十二烷基苯磺酸与聚氧基-15羟基硬脂酸酯等中的一种或多种。
优选的，还包括抗氧化剂；所述抗氧化剂的质量为无氟清洗剂质量的0.1％～10％；所述抗氧化剂选自丁基羟基茴香醚、2,6-二叔丁基对甲酚、对苯二酚、D-异抗坏血酸、山梨醇、植酸、壳聚糖与壳寡糖中的一种或多种。
本发明还提供了一种上述无氟清洗剂的制备方法，包括：
将水、有机溶剂、胺类化合物与腐蚀抑制剂、酸及醇类化合物中的一种或多种混合，得到无氟清洗剂。
本发明还提供了上述无氟清洗剂在电子工业领域包括但不限于半导体集成电路中的应用。
本发明还提供了一种清洗方法，包括：使用上述无氟清洗剂通过浸泡法或单晶圆法对晶圆进行清洗。
本发明提供了一种无氟清洗剂，所述无氟清洗剂为水性清洗剂；所述无氟清洗剂包括水、有机溶剂与胺类化合物；所述有机溶剂的质量为无氟清洗剂质量的15％～85％；所述胺类化合物的质量为无氟清洗剂质量的5％～50％；还包括腐蚀抑制剂、酸与醇类化合物中的一种或多种。与现有技术相比，本发明提供的无氟清洗剂通过特定的胺类化合物与腐蚀抑制剂、酸及醇中的一种或多种协同作用在不含有氟元素的情况下也具有较好的清洗能力，同时还可降低清洗液对金属的腐蚀，防止对基底介质产生破坏，提高清洗后晶圆的耐候性。与现有同类产品比，具有降低清洗温度、清洗时间以及更高性价比等明显优势。
附图说明
图1为金属铝刻蚀后晶圆清洗前的SEM图；
图2为采用本发明实施例1清洗金属铝刻蚀后晶圆的SEM图；
图3为采用对比例1提供的无氟清洗剂清洗金属铝刻蚀后晶圆的SEM图；
图4为二氧化硅膜刻蚀后晶圆清洗前的SEM图；
图5为采用本发明实施例7提供的无氟清洗剂清洗氧化硅膜刻蚀后晶圆的SEM图；
图6为采用对比例1提供的无氟清洗剂清洗二氧化硅刻蚀后晶圆的SEM图；
图7为氮化硅膜刻蚀后晶圆清洗前的SEM图；
图8为采用本发明实施例7提供的无氟清洗剂清洗氮化硅刻蚀后晶圆的 SEM图；
图9为采用对比例1提供的无氟清洗剂清洗氮化硅刻蚀后晶圆的SEM图。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供了一种无氟清洗剂，所述无氟清洗剂为水性清洗剂；所述无氟清洗剂包括水、有机溶剂与胺类化合物；
所述有机溶剂的质量为无氟清洗剂质量的15％～85％；
所述胺类化合物的质量为无氟清洗剂质量的5％～50％；
还包括腐蚀抑制剂、酸与醇类化合物中的一种或多种。
本发明提供的无氟清洗剂通过特定的胺类化合物与腐蚀抑制剂、酸及醇中的一种或多种协同作用在不含有氟元素的情况下也具有较好的清洗能力，同时还可降低清洗液对金属的腐蚀，防止对基底介质产生破坏，提高清洗后晶圆的耐候性。与现有同类产品比，具有降低清洗温度、清洗时间以及更高性价比等明显优势。
本发明提供的无氟清洗剂的pH值优选为7～13，更优选为7.9～13；在本发明提供的实施例中，所述无氟清洗剂的pH值具体为11.5、11.8、10.6、11.7、11.3、12.8、12.5、12.7、12.0、13.0、7.9、10.5、10.7、8.6、11.2、11.1或8.0。
本发明提供的无氟清洗剂为水性清洗剂；所述清洗剂中包括有机溶剂；所述有机溶剂的质量优选为无氟清洗剂质量的15％～85％，更优选为15％～70％，再优选为15％～60％；在本发明提供的实施例中，所述有机溶剂的质量具体为无氟清洗剂质量的15％、25％、60％、35％、38％或40％；所述有机溶剂为本领域技术人员熟知的有机溶剂即可，并无特殊的限制，在本发明中优选至少包括醇醚类有机溶剂；所述醇醚类有机溶剂优选为乙二醇单甲醚、乙二醇单***、乙二醇单丁醚、二乙二醇甲醚、二乙二醇丁醚、二丙二醇丁醚与三丙二醇丁醚中的一种或多种；在本发明中进一步优选地，所述有机溶剂优选为乙二醇单甲醚、乙二醇单***、乙二醇单丁醚、二乙二醇甲醚、二乙二醇丁醚、二丙二醇 丁醚、三丙二醇丁醚、丙二醇甲醚醋酸酯、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基丙酰胺、N,N-二甲基丙酰胺、N,N-二乙基乙酰胺、环丁砜、二甲基亚砜与1,4-丁内酯中的一种或多种。
本发明提供的无氟清洗剂中包含胺类化合物；所述胺类化合物的质量优选为无氟清洗剂质量的5％～40％；在本发明提供的实施例中，所述胺类化合物的质量具体为无氟清洗剂质量的15％、25％、22％、50％、5％、32％或40％；所述胺类化合物选自甲胺、乙胺、羟胺、辛胺、三乙胺、乙酰胺、二乙胺、叔丁胺、丁酰胺、多巴胺、异丁胺、异戊胺、正丙胺、正己胺、环丙胺、环己胺、环庚胺、环戊胺、庚胺、乙醇胺、二乙醇胺、二甘醇胺、异丙醇胺、三异丙醇胺、二异丙醇胺、N-乙基乙醇胺、N-苯基乙醇胺、N-乙酰乙醇胺、N-丁基二乙醇胺、N-环己基乙醇胺、N-苄基二乙醇胺、N-苯基二乙醇胺、N,N-二苄基乙醇胺、N-叔丁基二乙醇胺、N-叔丁基异丙醇胺、N-甲基二异丙醇胺、1,6-己二胺、1,2-丙二胺、1,3-丙二胺、1,4-丁二胺、1,8-辛二胺、三乙烯二胺、三正十二胺、二乙烯三胺、己二酰二胺、马来酸二胺、2-辛基十二胺、N-乙基乙二胺、N-甲基乙二胺、N-苄基乙二胺、N-苯基乙二胺、精胺、N-乙酰乙二胺、五乙烯六胺、四乙烯五胺、1H-吡唑-3,5-二胺、3-二乙胺基丙胺、3-二甲胺基丙胺、N-丁基乙烯二胺、N-异丙基乙二胺、N-甲基对苯二胺、四甲基甲烷二胺、四丁基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四甲基氢氧化铵、2-[(羟甲基)氨基]乙醇、苄基三甲基氢氧化铵、N-(苄羰氧基)羟基胺与N,N-二苄基羟基胺中的一种或多种；在本发明中进一步优选的，所述胺类化合物优选包括醇胺类化合物。
本发明提供的无氟清洗剂至少还包括腐蚀抑制剂、酸与醇类化合物中的一种或多种。
无氟清洗液中加入腐蚀抑制剂可降低清洗剂对金属的腐蚀；所述腐蚀抑制剂的质量优选为无氟清洗剂质量的0.5％～10％，更优选为1％～7％，再优选为1％～5％；在本发明提供的实施例中，所述腐蚀抑制剂具体为无氟清洗剂质量的1％、4％、2％、5％或10％；在本发明中，所述腐蚀抑制剂优选至少包括含有***基团、氨基基团、羟基基团、羧基基团或巯基基团中一种，更优选为1,2,4-三氮唑、苯并三氮唑、1H-1,2,3-三氮唑、5-甲基苯并三氮唑、5-羟基苯并 三氮唑、1H-1,2,3-三氮唑-1-胺、3-氰基-1,2,4-三氮唑、1,2,4-三氮唑-3-甲酰胺、1-乙基-1H-1,2,3-三氮唑、1-苯基-1H-1,2,4-三氮唑、1H-1,2,4-三氮唑-3-羧酸、2-苯基-2H-1,2,3-三氮唑、3-甲基-1H-1,2,4-三氮唑、3-苯基-1,2,4-1H-三氮唑、4-甲基-1H-1,2,3-三氮唑、1H-1,2,3-三氮唑-4-羧酸、2H-2-乙酸-1,2,3-三氮唑、3,5-二氨基-1,2,4-三氮唑、1,2,3-三氮唑-4-甲酸甲酯、1,2,4-三氮唑-3-羧酸甲酯、N,N’-羰基二(1,2,3-三氮唑)、1,4-二甲基-1H-1,2,3-三氮唑、2H-1,2,3-三氮唑-4-羧酸甲酯、3,5-二苯基-1H-1,2,4-三氮唑、3-巯基-5-甲基-1,2,4-三氮唑、3-氨基-5-巯基-1,2,4-三氮唑、3-(1,2,4-三氮唑-1-基)苯甲酸、3-(1,2,4-三氮唑-1-基)苯甲醛、4-(4H-1,2,4-三氮唑-3-基)苯胺、1-羟基苯丙***、3-(1H-(1,2,3)三氮唑-4-基)-苯腈、3-巯基-1,2,4-***、3-氨基-1,2,4-***、3-氨基-1H-1,2,4-三氮唑-5-羧酸、4-(4H-1,2,4-三氮唑-4-基)苯甲酸、1-羟基-7-偶氮苯并三氮唑、[1,2,4]三氮唑[1,5-a]吡啶-6-甲醛、[1,2,4]三氮唑并[1,5-a]吡啶-7-醇、1-甲基-1,2,3-三氮唑-5-甲酸甲酯、5-环己基-1H-3-氨基-1,2,4-三氮唑、4-氨基-4H-1,2,4-***、5-氨基-2,4-二氢-[1,2,4]三氮唑-3-酮、4,5,6,7-四氢-1,2,3-三氮唑并[1,5-a]吡嗪、硫代水杨酸、2-巯基吡啶、2-巯基吡嗪、2-巯基咪唑、2-巯基噻唑、2-巯基烟酸、3-巯基丁酸、3-巯基丙酸、3-巯基吲哚、4-巯基吡啶、4-巯基尿苷、6-巯基嘌呤、6-巯基己酸、β-巯基乙胺、二巯基丙醇、巯基尼古胺、1,5-二巯基萘、2-巯基-3-丁醇、2-巯基-3-戊酮、2-巯基噻唑啉、2-巯基苯甲醇、2-甲巯基苯胺、3-巯基-1-己醇、3-巯基-2-丁酮、3-巯基-2-戊酮、2-巯基苯甲酸、3-巯基苯甲酸、4-巯基苯甲酸、4-巯基苯甲醇、4-巯基苯甲醛、6-巯基己-1-醇、6-甲巯基嘌呤、2,4-二巯基嘧啶、2,6-二巯基嘌呤、2-巯基苯并咪唑、2-巯基苯并噻唑、2-巯基苯并恶唑、4-巯基苯基乙酸、乙酸3-巯基己酯、3-巯基-1,2,4-***、邻氨基苯酚、邻苯二酚、多巴胺、4-乙基儿茶酚、3,4-二羟基苯甲酸、去甲二氢愈创木酸、2,3-二羟基吡啶、2,4-二羟基喹啉、3,4-二羟基苯乙酮、2,3-二羟基喹喔啉、3,4-二羟基苯甲腈、1,2-二羟基萘、3,4-二羟基苯甲醛、5,6-二羟基吲哚、4-氨基-6-羟基-2-巯基嘧啶、2-甲基巯基-4-氨基-6-羟基嘧啶、2-巯基苯甲醇、2-巯基胞嘧啶、6-巯基-1-己醇、6-氨基-2-巯基嘧啶-4-醇、3-巯基-1-己醇、3-巯基-1-丙醇、3-巯基丙酸、2-巯基-5-甲基苯并咪唑、4,6-二甲基-2-巯基嘧啶、3-巯基-3-甲基-1-丁醇、3-巯基-4-甲基-4H-1,2,4-***、5-甲氧基-2-巯基苯并咪唑、3- 巯基苯基硼酸、聚乙二醇、聚酰亚胺、2-苯基-4-五亚乙基六胺-2-醇、3-氨基-5-羟基吡唑、2-氨基-3-羟基吩嗪、4-氨基-3-羟基苯甲酸、3-氨基-4-羟基吡啶、2'-氨基-3'-羟基苯乙酮、5-氨基-2-羟基吡啶、4-氨基-6-羟基嘧啶、2-氨基-8-羟基喹啉、2-氨基-3-羟基吡啶、3'-氨基-2'-羟基联苯基-3-甲酸、2-氨基-4-羟基苯并噻唑、2-乙酰氨基-6-羟基嘌呤、2-氨基-N-羟基丙酰胺、2-氨基-N-羟基戊酰胺、3-氨基-5-羟基吡啶、4-乙酰氨基-3-羟基苯甲酸与2-氨基-4-羟基-6-甲基嘧啶等中的一种或多种。
在本发明提供的无氟清洗剂中，添加酸可在提高清洗剂清洗能力的同时还可降低金属蚀刻速率；所述酸的质量优选为无氟清洗剂质量的0.5％～5％，更优选为1％～4％，再优选为2％～3.5％，最优选为2.5％～3％；在本发明提供的实施例中，所述酸的质量具体为无氟清洗剂质量的2.8％、3％或2％；在本发明中，所述酸可为无机酸也可为有机酸，并无特殊的限制，本发明中优选为硫酸、硝酸、盐酸、磷酸、甲酸、乙酸、柠檬酸、硼酸与碳酸中的一种或多种。
在本发明中，所述醇类化合物的质量优选为无氟清洗剂质量的0.5％～10％，更优选为1％～5％，再优选为1％～4％；在本发明提供的实施例中，所述醇类化合物的质量具体为无氟清洗剂质量的1％、4％、3％或2％；所述醇类化合物优选为二元醇类化合物和/或多元醇类化合物，更优选为乙二醇、丙三醇、1,3-丁二醇、1,2-戊二醇、季戊四醇、2,5-己二醇、聚己内酯二醇、1,6-己二醇、山梨糖醇、新戊二醇、1,4-丁二醇、1,2,6-己三醇、木糖醇、L-甘露糖醇、D(+)-***糖醇、香叶醇、甜醇、1,2,4-丁三醇、糠醇、植醇、双季戊四醇、L-苏氨醇、L-塔罗糖醇、葡萄糖、赤藓糖醇与木糖中的一种或多种。
本发明提供的无氟清洗剂优选还包括稳定剂；所述稳定剂质量优选为无氟清洗剂质量的2％～20％；稳定剂可调节清洗剂酸碱性并维持其稳定，同时还具有保持清洗剂物理化学特性一致的作用，对延长清洗剂贮藏寿命、槽液寿命等有增益。所述稳定剂优选为乙醇、2-羟基吡啶、4-羟基吡啶、对羟基苯甲醛、水杨酸、硫代水杨酸、2,6-二甲基-3-羟基吡啶、2,3-二羟基吡啶、5-氨基-2-羟基吡啶、明胶、三羟甲基氨基甲烷、3-吗啉丙磺酸、4-羟乙基哌嗪乙磺酸、硼酸铵、乙酸铵、甲酸铵、硼酸铵、甲酸铵、磷酸铵、磷酸二氢铵、柠檬酸铵、巴比妥酸等中的一种或多种。
本发明提供的无氟清洗剂优选还包括表面活性剂，可促进清洗剂中各组分的分散性及稳定性。所述表面活性剂的质量优选为无氟清洗剂质量的0.5％～10％；在本发明提供的实施例中，所述表面活性剂的质量具体为无氟清洗剂质量的2％；所述表面活性剂选自3,5-二甲基-1-己炔-3-醇、月桂醇醚磷酸酯、椰油酸二乙醇酰胺、椰油酰胺丙基甜菜碱、椰油酰胺丙基羟磺基甜菜碱、月桂酰胺丙基羟磺基甜菜碱、丙酮肟、月桂酰胺丙基氧化胺、单甘脂、司班、十二烷基苯磺酸与聚氧基-15羟基硬脂酸酯等中的一种或多种。
本发明提供的无氟清洗剂优选还包括抗氧剂，可提高清洗剂的抗氧化性能与抗变色能力。所述抗氧剂的质量优选为无氟清洗剂质量的0.1％～5％；在本发明提供的实施例中，所述抗氧剂的质量具体为无氟清洗剂质量的1％；所述抗氧剂优选为丁基羟基茴香醚、2,6-二叔丁基对甲酚、对苯二酚、D-异抗坏血酸、山梨醇、植酸、壳聚糖与壳寡糖中的一种或多种。
本发明还提供了一种上述无氟清洗剂的制备方法，包括：将水、有机溶剂、胺类化合物与腐蚀抑制剂、酸及醇类化合物中的一种或多种混合，得到无氟清洗剂。
本发明对所有原料的来源并没有特殊的限制，为市售即可。所述水、有机溶剂、胺类化合物与腐蚀抑制剂均同上所述，在此不再赘述。
本发明还提供了一种上述无氟清洗剂在包括电子工业但不限于半导体领域集成电路中的应用；进一步优选为在半导体刻蚀工艺后清洗中的应用；所述半导体刻蚀工艺可为金属刻蚀、介电材料刻蚀和硅等无机介质的刻蚀，并无特殊的限制，在本发明中具体可包括铝、钛、钽等金属刻蚀制程后残留物的清洗，也可包括二氧化硅、氮化硅等介质层刻蚀制程后残留物的清洗；清洗的残留物种类包括但不限于光刻胶残留物、无机残留物、金属反应副产物等。
本发明还提供了无氟清洗剂的清洗方法，包括：使用上述无氟清洗剂通过浸泡法或单晶圆法对晶圆进行清洗。
在本发明中，具体为将经干法刻蚀后的晶圆在上述无氟清洗剂中浸泡；所述浸泡的温度优选为20℃～70℃，更优选为25℃～70℃；所述浸泡的时间优选为1～60min，更优选为1～40min，再优选为1～20min，最优选为1～10min；在本发明中，所述经刻蚀后的晶圆具体为金属或无机介质材料，刻蚀后的晶圆 具体可为铝、钛、钽、镍、二氧化硅、氮化硅等刻蚀后的晶圆；将浸泡后的晶圆优选用超纯水等进行润洗后，氮气吹干即完成清洗。
本发明所述无氟清洗剂还可通过单晶圆法进行清洗，具体为：借助如旋涂机等设备对刻蚀后的晶圆进行旋转，在晶圆表面滴入无氟清洗剂和超纯水进行清洗；所述旋转的速度为50～5000rpm/min，所述仪器工作温度优选为20℃～70℃；所述单晶圆法清洗时间为1～60min。
本发明提供的无氟清洗剂具有较强的清洗能力，可降低清洗剂的清洗温度及清洗时间。
为了进一步说明本发明，以下结合实施例对本发明提供的一种无氟清洗剂、其制备方法及应用进行详细描述。
以下实施例中所用的试剂均为市售。
实施例1
包含15wt％单乙醇胺，15wt％二乙二醇单丁醚，1wt％D-山梨糖醇，1wt％苯并三氮唑，2wt％乙二醇和余量的超纯水，各化学试剂总量为100g，并按逐一加入烧杯中摇匀。其中，固体试剂可先称量，再加入溶剂溶解。
实施例2
包含25wt％单乙醇胺，15wt％二乙二醇单丁醚，1wt％D-山梨糖醇，1wt％苯并三氮唑，2wt％乙二醇和余量的超纯水，各化学试剂总量为100g，并按逐一加入烧杯中摇匀。其中，固体试剂可先称量，再加入溶剂溶解。
实施例3
包含15wt％单乙醇胺，25wt％二乙二醇单丁醚，1wt％D-山梨糖醇，1wt％苯并三氮唑，2wt％乙二醇和余量的超纯水，各化学试剂总量为100g，并按逐一加入烧杯中摇匀。其中，固体试剂可先称量，再加入溶剂溶解。
实施例4
包含15wt％单乙醇胺，60wt％二乙二醇单丁醚，1wt％D-山梨糖醇，1wt％苯并三氮唑，2wt％乙二醇和余量的超纯水，各化学试剂总量为100g，并按逐一加入烧杯中摇匀。其中，固体试剂可先称量，再加入溶剂溶解。
实施例5
包含10wt％单乙醇胺，7wt％1,3-丙二胺，5wt％异丙醇胺，25wt％二乙 二醇单丁醚，2.8wt％硼酸，1wt％苯并三氮唑和余量的超纯水，各化学试剂总量为100g，并按逐一加入烧杯中摇匀。其中，固体试剂可先称量，再加入溶剂溶解。
实施例6
包含10wt％单乙醇胺，12wt％1,3-丙二胺，25wt％二乙二醇单丁醚，2.8wt％硼酸，1wt％苯并三氮唑和余量的超纯水，各化学试剂总量为100g，并按逐一加入烧杯中摇匀。其中，固体试剂可先称量，再加入溶剂溶解。
实施例7
包含5wt％单乙醇胺，17wt％1,3-丙二胺，35wt％二乙二醇单丁醚，4wt％苯并***和余量的超纯水，各化学试剂总量为100g，并按逐一加入烧杯中摇匀。其中，固体试剂可先称量，再加入溶剂溶解。
实施例8
包含5wt％单乙醇胺，17wt％1,3-丙二胺，60wt％二乙二醇单丁醚，4wt％苯并***和余量的超纯水，各化学试剂总量为100g，并按逐一加入烧杯中摇匀。其中，固体试剂可先称量，再加入溶剂溶解。
对比例1
包含17wt％1,3-丙二胺，35wt％二乙二醇单丁醚，4wt％苯并三氮唑和余量的超纯水，各化学试剂总量为100g，并按逐一加入烧杯中摇匀。其中，固体试剂可先称量，再加入溶剂溶解。
对比例2
包含5wt％单乙醇胺，30wt％1,3-丙二胺，35wt％二乙二醇单丁醚，1wt％苯并三氮唑和余量的超纯水，各化学试剂总量为100g，并按逐一加入烧杯中摇匀。其中，固体试剂可先称量，再加入溶剂溶解。
实施例1～实施例8及对比例1、2提供的无氟清洗剂的组成见表1及表2。
表1 无氟清洗剂的组成
清洗剂(wt％) 实施例1 实施例2 实施例3 实施例4
D-山梨糖醇 1 1 1 1
二乙二醇单丁醚 15 15 25 60
苯并三氮唑 1 1 1 1
单乙醇胺 15 25 15 15
乙二醇 2 2 2 2
pH值 11.5 11.8 11.5 10.6
表2 无氟清洗剂的组成
清洗剂(wt％) 实施例5 实施例6 实施例7 实施例8 对比例1 对比例2
硼酸 2.8 2.8 0 0 0 0
二乙二醇单丁醚 25 25 35 60 35 35
苯并三氮唑 1 1 4 4 4 1
单乙醇胺 10 10 5 5 0 5
异丙醇胺 5 0 0 0 0 0
1,3-丙二胺 7 12 17 17 17 30
pH值 11.7 11.3 12.8 12.5 11.8 12.5
将实施例1～实施例8及对比例1中得到的无氟清洗剂用于铝干法刻蚀后残留物清洗试验:
将金属铝刻蚀后的晶圆浸入无氟清洗剂中，实验温度为70℃，浸渍时间为10分钟。结束后取出试样片，即刻水洗、吹氮气，然后用扫描隧道显微镜SEM观察晶圆表面残留物的清洗情况，得到结果见表3、图1～图3。其中图1为金属铝刻蚀后晶圆清洗前的SEM图，图2为采用本发明实施例1提供的无氟清洗剂清洗金属铝刻蚀后晶圆的SEM图，图3为采用对比例1提供的无氟清洗剂清洗金属铝刻蚀后晶圆的SEM图，由图3可知晶圆表面有残留物未完全清除；特说明，本发明的蚀刻后残留物在清洗后不需异丙醇等溶剂的漂洗，可以直接水洗，简化了操作工艺，节省化学品消耗成本。
表3 铝刻蚀后残留物清洗试验结果
清洗剂 金属铝刻蚀后晶圆表面残留物去除情况
实施例1 完全去除
实施例2 完全去除
实施例3 完全去除
实施例4 完全去除
实施例5 完全去除
实施例6 完全去除
实施例7 完全去除
实施例8 完全去除
对比例1 未完全清除，完全去除需提高工作温度至90℃
对比例2 未完全清除
将实施例5～实施例8及对比例1中得到的无氟清洗剂用于二氧化硅刻蚀后残留物清洗试验：
将二氧化硅刻蚀后的晶圆浸入无氟清洗剂中，实验温度为70℃，浸渍时间为10分钟。结束后取出试样片，即刻水洗、吹氮气，然后用扫描隧道显微镜SEM观察晶圆表面残留物的清洗情况，得到结果见表4与图4～6；图4为二氧化硅膜刻蚀后晶圆清洗前的SEM图；图5为采用本发明实施例7提供的无氟清洗剂清洗二氧化硅刻蚀后晶圆的SEM图；图6为采用对比例1提供的无氟清洗剂清洗二氧化硅刻蚀后晶圆的SEM图。
表4 二氧化硅刻蚀后残留物清洗试验结果
Figure PCTCN2022072276-appb-000001
将实施例7～实施例8及对比例1中得到的无氟清洗剂用于氮化硅刻蚀后残留物清洗试验：
将氮化硅刻蚀后的晶圆浸入无氟清洗剂中，实验温度为70℃，浸渍时间为10分钟。结束后捞出试样片，即刻水洗、吹氮气，然后用扫描隧道显微镜SEM观察蚀刻后残留物的清洗情况，得到结果见表5、图7～图9；图7为氮化硅膜刻蚀后晶圆的SEM图，图8为采用本发明实施例7提供的无氟清洗剂清洗氮化硅刻蚀后晶圆的SEM图，图9为采用对比例1提供的无氟清洗剂清洗氮化硅刻蚀后晶圆的SEM图，由图9可见侧壁未清洗干净。
表5 氮化硅刻蚀后残留物清洗试验结果
清洗剂 实施例7 实施例8 对比例1 对比例2
氮化硅刻蚀后晶圆表面残留物去 完全去除 完全去除 未完全清除 未完全清除
除情况        
清洗后金属膜腐蚀情况评价：
将带有铝膜的试样片浸渍在实施例1～实施例9及对比例1制备的无氟清洗剂中15分钟，实验温度为70℃，结束后取出试样片，水洗并氮气吹干，然后使用四探针法测试金属膜腐蚀速率及SEM观察表面腐蚀情况，得到结果见表6。
表6 清洗后金属膜腐蚀评价结果
Figure PCTCN2022072276-appb-000002
本发明实施例中用于刻蚀后的晶圆中，其中金属铝、氧化硅和氮化硅的厚度均为1微米；所述金属铝通过等离子体溅射引入晶圆中，并使用氯气与三氯化硼进行等离子体干法刻蚀；所述氧化硅和氮化硅使用化学气相沉积法制备得到，并使用含氟气体、氧气及氩气进行等离子体干法刻蚀。本发明无氟清洗剂的应用包括但不限于干法刻蚀后晶圆表面残留物的去除，应用对象还可为湿法刻蚀后晶圆。
实施例9～13及对比例3～4
按照上述实施例的方法及表7中的组成配方制备实施例9～13和对比例3～4的无氟清洗剂。
表7 无氟清洗剂的组成
清洗剂(wt％) 实施例9 实施例10 实施例11 实施例12 实施例13 对比例3 对比例4
硼酸 0 0 3 3 3 3 0
二乙二醇单丁醚 35 0 35 35 0 0 35
二甲基亚砜 0 35 0 0 0 0 0
二甲基乙酰胺 0 0 0 0 35 35 0
1,3-丙二胺 50 50 35 7 0 0 35
羟胺 0 0 15 15 0 0 15
四甲基氢氧化铵 0 0 0 0 5 0 0
山梨糖醇 4 4 4 0 2 2 4
硫代水杨酸 2 6 10 0 0 0 0
邻苯二酚 0 0 0 2 10 10 0
pH值 12.0 13.0 7.9 10.5 10.7 12.3 13.8
按照上述实施例的检测方法对实施例9～13中得到的无氟清洗剂的清洗能力及腐蚀速率进行检测，得到结果见表8与表9。
表8 实施例9～13无氟清洗剂清洗能力检测结果
Figure PCTCN2022072276-appb-000003
表9 实施例9～13无氟清洗剂腐蚀速率检测结果
清洗剂 实施例9 实施例10 实施例11 实施例12 实施例13 对比例3 对比例4
腐蚀速率-70℃ <3 <1 <6 <1 <1 <20 ＞30
铝表面形貌 几乎不腐蚀 几乎不腐蚀 几乎不腐蚀 几乎不腐蚀 几乎不腐蚀 部分腐蚀 严重腐蚀
实施例14～18
按照上述实施例的方法及表10中的组成配方制备实施例14～18及对比例5～6的无氟清洗剂。
表10 无氟清洗剂的组成
清洗剂(wt％) 实施例14 实施例15 实施例16 实施例17 实施例18 对比例5 对比例6
甲酸 2 0 0 0 2 0 2
硼酸 0 2 2 2 0 0 0
二甲基亚砜 0 0 0 40 40 40 40
二甲基乙酰胺 40 0 0 0 0 0 0
N-甲基吡咯烷酮 0 40 40 0 0 0 26
羟胺 20 0 0 0 20 20 0
四甲基氢氧化铵 1 0 0 0 1 1 0
三乙胺 0 20 0 0 0 0 0
乙醇胺 0 10 0 0 0 0 0
二乙烯三胺 0 0 20 0 0 0 0
三乙烯四胺 0 0 0 20 0 0 0
乙二醇 2 0 0 0 2 2 2
葡萄糖 0 2 2 2 0 0 0
1,2,3-三氮唑 5 0 0 0 5 0 5
邻苯二酚 0 3 3 3 0 0 0
对羟基苯甲醛 2 0 0 0 2 2 2
丙酮肟 2 0 0 0 0 0 0
司班 0 2 2 2 0 0 0
十二烷基苯磺酸 0 0 0 0 2 2 2
对苯二酚 1 0 0 0 0 0 0
丁基茴香醚 0 1 1 1 0 0 0
二叔丁基对甲酚 0 0 0 0 1 1 1
pH值 8.6 11.2 11.3 11.1 8.0 13.5 11.2
按照上述实施例的检测方法对实施例14～18和对比例5～6中得到的无氟清洗剂的清洗能力及腐蚀速率进行检测，得到结果见表11与表12。
表11 实施例14～18及对比例5～6无氟清洗剂腐蚀速率检测结果
清洗剂 实施例14 实施例15 实施例16 实施例17 实施例18 对比例5 对比例6
腐蚀速率-70℃ <1 <6 <6 <5 <1 ＞30 <1
铝表面形貌 几乎不腐蚀 几乎不腐蚀 几乎不腐蚀 几乎不腐蚀 几乎不腐蚀 严重腐蚀 几乎不腐蚀
表12 实施例14～18及对比例5～6无氟清洗剂清洗能力检测结果
Figure PCTCN2022072276-appb-000004
Figure PCTCN2022072276-appb-000005

Claims (10)

  1. 一种无氟清洗剂，其特征在于，所述无氟清洗剂为水性清洗剂；所述无氟清洗剂包括水、有机溶剂与胺类化合物；
    所述有机溶剂的质量为无氟清洗剂质量的15％～85％；
    所述胺类化合物的质量为无氟清洗剂质量的5％～50％；
    还包括腐蚀抑制剂、酸与醇类化合物中的一种或多种。
  2. 根据权利要求1所述的无氟清洗剂，其特征在于，
    所述腐蚀抑制剂的质量为无氟清洗剂质量的0.1％～10％；
    所述酸的质量为无氟清洗剂质量的0.5％～5％；
    所述醇类化合物的质量为无氟清洗剂质量的0.5％～10％；
    所述醇类化合物为二元醇类化合物和/或多元醇类化合物。
  3. 根据权利要求1所述的无氟清洗剂，其特征在于，所述腐蚀抑制剂至少包括含有***基团、氨基基团、羟基基团、羧基基团或巯基基团中一种；
    所述酸选自硫酸、硝酸、盐酸、磷酸、甲酸、乙酸、柠檬酸、硼酸与碳酸中的一种或多种；
    所述醇类化合物选自为乙二醇、丙三醇、1,3-丁二醇、1,2-戊二醇、季戊四醇、2,5-己二醇、聚己内酯二醇、1,6-己二醇、山梨糖醇、新戊二醇、1,4-丁二醇、1,2,6-己三醇、木糖醇、L-甘露糖醇、D(+)-***糖醇、香叶醇、甜醇、1,2,4-丁三醇、糠醇、植醇、双季戊四醇、L-苏氨醇、L-塔罗糖醇、葡萄糖、赤藓糖醇与木糖等中的一种或多种。
  4. 根据权利要求1所述的无氟清洗剂，其特征在于，所述腐蚀抑制剂选自1,2,4-三氮唑、苯并三氮唑、1H-1,2,3-三氮唑、5-甲基苯并三氮唑、5-羟基苯并三氮唑、1H-1,2,3-三氮唑-1-胺、3-氰基-1,2,4-三氮唑、1,2,4-三氮唑-3-甲酰胺、1-乙基-1H-1,2,3-三氮唑、1-苯基-1H-1,2,4-三氮唑、1H-1,2,4-三氮唑-3-羧酸、2-苯基-2H-1,2,3-三氮唑、3-甲基-1H-1,2,4-三氮唑、3-苯基-1,2,4-1H-三氮唑、4-甲基-1H-1,2,3-三氮唑、1H-1,2,3-三氮唑-4-羧酸、2H-2-乙酸-1,2,3-三氮唑、3,5-二氨基-1,2,4-三氮唑、1,2,3-三氮唑-4-甲酸甲酯、1,2,4-三氮唑-3-羧酸甲酯、N,N’-羰基二(1,2,3-三氮唑)、1,4-二甲基-1H-1,2,3-三氮唑、2H-1,2,3- 三氮唑-4-羧酸甲酯、3,5-二苯基-1H-1,2,4-三氮唑、3-巯基-5-甲基-1,2,4-三氮唑、3-氨基-5-巯基-1,2,4-三氮唑、3-(1,2,4-三氮唑-1-基)苯甲酸、3-(1,2,4-三氮唑-1-基)苯甲醛、4-(4H-1,2,4-三氮唑-3-基)苯胺、1-羟基苯丙***、3-(1H-(1,2,3)三氮唑-4-基)-苯腈、3-巯基-1,2,4-***、3-氨基-1,2,4-***、3-氨基-1H-1,2,4-三氮唑-5-羧酸、4-(4H-1,2,4-三氮唑-4-基)苯甲酸、1-羟基-7-偶氮苯并三氮唑、[1,2,4]三氮唑[1,5-a]吡啶-6-甲醛、[1,2,4]三氮唑并[1,5-a]吡啶-7-醇、1-甲基-1,2,3-三氮唑-5-甲酸甲酯、5-环己基-1H-3-氨基-1,2,4-三氮唑、4-氨基-4H-1,2,4-***、5-氨基-2,4-二氢-[1,2,4]三氮唑-3-酮、4,5,6,7-四氢-1,2,3-三氮唑并[1,5-a]吡嗪、2-巯基吡啶、2-巯基吡嗪、2-巯基咪唑、2-巯基噻唑、2-巯基烟酸、3-巯基丁酸、3-巯基丙酸、3-巯基吲哚、4-巯基吡啶、4-巯基尿苷、6-巯基嘌呤、6-巯基己酸、β-巯基乙胺、二巯基丙醇、巯基尼古胺、1,5-二巯基萘、2-巯基-3-丁醇、2-巯基-3-戊酮、硫代水杨酸、2-巯基噻唑啉、2-巯基苯甲醇、2-甲巯基苯胺、3-巯基-1-己醇、3-巯基-2-丁酮、3-巯基-2-戊酮、2-巯基苯甲酸、3-巯基苯甲酸、4-巯基苯甲酸、4-巯基苯甲醇、4-巯基苯甲醛、6-巯基己-1-醇、6-甲巯基嘌呤、2,4-二巯基嘧啶、2,6-二巯基嘌呤、2-巯基苯并咪唑、2-巯基苯并噻唑、2-巯基苯并恶唑、4-巯基苯基乙酸、乙酸3-巯基己酯、3-巯基-1,2,4-***、邻氨基苯酚、邻苯二酚、多巴胺、4-乙基儿茶酚、3,4-二羟基苯甲酸、去甲二氢愈创木酸、2,3-二羟基吡啶、2,4-二羟基喹啉、3,4-二羟基苯乙酮、2,3-二羟基喹喔啉、3,4-二羟基苯甲腈、1,2-二羟基萘、3,4-二羟基苯甲醛、5,6-二羟基吲哚、4-氨基-6-羟基-2-巯基嘧啶、2-甲基巯基-4-氨基-6-羟基嘧啶、2-巯基苯甲醇、2-巯基胞嘧啶、6-巯基-1-己醇、6-氨基-2-巯基嘧啶-4-醇、3-巯基-1-己醇、3-巯基-1-丙醇、3-巯基丙酸、2-巯基-5-甲基苯并咪唑、4,6-二甲基-2-巯基嘧啶、3-巯基-3-甲基-1-丁醇、3-巯基-4-甲基-4H-1,2,4-***、5-甲氧基-2-巯基苯并咪唑、3-巯基苯基硼酸、聚乙二醇、聚酰亚胺、2-苯基-4-五亚乙基六胺-2-醇、3-氨基-5-羟基吡唑、2-氨基-3-羟基吩嗪、4-氨基-3-羟基苯甲酸、3-氨基-4-羟基吡啶、2'-氨基-3'-羟基苯乙酮、5-氨基-2-羟基吡啶、4-氨基-6-羟基嘧啶、2-氨基-8-羟基喹啉、2-氨基-3-羟基吡啶、3'-氨基-2'-羟基联苯基-3-甲酸、2-氨基-4-羟基苯并噻唑、2-乙酰氨基-6-羟基嘌呤、2-氨基-N-羟基丙酰胺、2-氨基-N-羟基戊酰胺、3-氨基-5-羟基吡啶、4-乙酰氨基-3-羟基苯甲酸与2-氨基-4-羟基-6-甲基嘧啶等 中的一种或多种。
  5. 根据权利要求1所述的无氟清洗剂，其特征在于，所述胺类化合物选自甲胺、乙胺、羟胺、辛胺、三乙胺、乙酰胺、二乙胺、叔丁胺、丁酰胺、多巴胺、异丁胺、异戊胺、正丙胺、正己胺、环丙胺、环己胺、环庚胺、环戊胺、庚胺、乙醇胺、二乙醇胺、二甘醇胺、异丙醇胺、三异丙醇胺、二异丙醇胺、N-乙基乙醇胺、N-苯基乙醇胺、N-乙酰乙醇胺、N-丁基二乙醇胺、N-环己基乙醇胺、N-苄基二乙醇胺、N-苯基二乙醇胺、N,N-二苄基乙醇胺、N-叔丁基二乙醇胺、N-叔丁基异丙醇胺、N-甲基二异丙醇胺、1,6-己二胺、1,2-丙二胺、1,3-丙二胺、1,4-丁二胺、1,8-辛二胺、三乙烯二胺、三正十二胺、二乙烯三胺、己二酰二胺、马来酸二胺、2-辛基十二胺、N-乙基乙二胺、N-甲基乙二胺、N-苄基乙二胺、N-苯基乙二胺、精胺、N-乙酰乙二胺、五乙烯六胺、四乙烯五胺、1H-吡唑-3,5-二胺、3-二乙胺基丙胺、3-二甲胺基丙胺、N-丁基乙烯二胺、N-异丙基乙二胺、N-甲基对苯二胺、四甲基甲烷二胺、四丁基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四甲基氢氧化铵、2-[(羟甲基)氨基]乙醇、苄基三甲基氢氧化铵、N-(苄羰氧基)羟基胺与N,N-二苄基羟基胺中的一种或多种；所述有机溶剂选自乙二醇单甲醚、乙二醇单***、乙二醇单丁醚、二乙二醇甲醚、二乙二醇丁醚、二丙二醇丁醚、三丙二醇丁醚、丙二醇甲醚醋酸酯、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基丙酰胺、N,N-二甲基丙酰胺、N,N-二乙基乙酰胺、环丁砜、二甲基亚砜与1,4-丁内酯中的一种或多种。
  6. 根据权利要求1所述的无氟清洗剂，其特征在于，还包括稳定剂；所述稳定剂的质量为无氟清洗剂质量的2％～20％；所述稳定剂选自乙醇、2-羟基吡啶、4-羟基吡啶、对羟基苯甲醛、水杨酸、硫代水杨酸、2,6-二甲基-3-羟基吡啶、2,3-二羟基吡啶、5-氨基-2-羟基吡啶、明胶、三羟甲基氨基甲烷、3-吗啉丙磺酸、4-羟乙基哌嗪乙磺酸、硼酸铵、乙酸铵、甲酸铵、硼酸铵、甲酸铵、磷酸铵、磷酸二氢铵、柠檬酸铵与巴比妥酸中的一种或多种；
    还包括表面活性剂；所述表面活性剂的质量为无氟清洗剂质量的0.5％～10％；所述表面活性剂选自3,5-二甲基-1-己炔-3-醇、月桂醇醚磷酸酯、椰油酸二乙醇酰胺、椰油酰胺丙基甜菜碱、椰油酰胺丙基羟磺基甜菜碱、月桂 酰胺丙基羟磺基甜菜碱、丙酮肟、月桂酰胺丙基氧化胺、单甘脂、司班、十二烷基苯磺酸与聚氧基-15羟基硬脂酸酯等中的一种或多种。
  7. 根据权利要求1所述的无氟清洗剂，其特征在于，还包括抗氧化剂；所述抗氧化剂的质量为无氟清洗剂质量的0.1％～10％；所述抗氧化剂选自丁基羟基茴香醚、2,6-二叔丁基对甲酚、对苯二酚、D-异抗坏血酸、山梨醇、植酸、壳聚糖与壳寡糖中的一种或多种。
  8. 一种权利要求1所述的无氟清洗剂的制备方法，其特征在于，包括：
    将水、有机溶剂、胺类化合物与腐蚀抑制剂、酸及醇类化合物中的一种或多种混合，得到无氟清洗剂。
  9. 权利要求1～7任意一项所述的无氟清洗剂或权利要求8所述制备方法制备的无氟清洗剂在电子工业领域包括但不限于半导体集成电路中的应用。
  10. 一种清洗方法，其特征在于，包括：
    使用权利要求1～7任意一项所述的无氟清洗剂或权利要求8所述制备方法制备的无氟清洗剂通过浸泡法或单晶圆法对晶圆进行清洗。
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US20050202987A1 (en) * 2000-07-10 2005-09-15 Small Robert J. Compositions for cleaning organic and plasma etched residues for semiconductor devices
CN104099194A (zh) * 2013-04-03 2014-10-15 东莞市剑鑫电子材料有限公司 一种线路板清洗剂及其制备方法
CN105785725A (zh) * 2014-12-23 2016-07-20 安集微电子（上海）有限公司 一种光阻残留物清洗液
CN108255026A (zh) * 2016-12-28 2018-07-06 安集微电子（上海）有限公司 一种低刻蚀光阻残留物清洗液组合物
CN114317127A (zh) * 2022-01-17 2022-04-12 嘉庚创新实验室 一种无氟清洗剂、其制备方法及应用

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US20050202987A1 (en) * 2000-07-10 2005-09-15 Small Robert J. Compositions for cleaning organic and plasma etched residues for semiconductor devices
CN104099194A (zh) * 2013-04-03 2014-10-15 东莞市剑鑫电子材料有限公司 一种线路板清洗剂及其制备方法
CN105785725A (zh) * 2014-12-23 2016-07-20 安集微电子（上海）有限公司 一种光阻残留物清洗液
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