WO2022163350A1 - 組成物、基板の洗浄方法 - Google Patents

組成物、基板の洗浄方法 Download PDF

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WO2022163350A1
WO2022163350A1 PCT/JP2022/000716 JP2022000716W WO2022163350A1 WO 2022163350 A1 WO2022163350 A1 WO 2022163350A1 JP 2022000716 W JP2022000716 W JP 2022000716W WO 2022163350 A1 WO2022163350 A1 WO 2022163350A1
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composition
group
mass
content
composition according
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French (fr)
Japanese (ja)
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篤史 水谷
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富士フイルム株式会社
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Priority to JP2022578214A priority Critical patent/JPWO2022163350A1/ja
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Priority to US18/357,360 priority patent/US20230365902A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • 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
    • C11D7/261—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5013—Organic solvents 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
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers

Definitions

  • the present invention relates to a composition and a method for cleaning a substrate.
  • a semiconductor device for example, arranges a laminate having a metal layer as a wiring material, an etching stop film, and an interlayer insulating film on a substrate, forms a resist film on the laminate, and performs a photolithography process and dry etching. It is manufactured by performing a process (for example, a plasma etching process). Specifically, in the photolithography process, the obtained resist film is used as a mask to etch the metal layer and/or the interlayer insulating film on the substrate by dry etching.
  • a process for example, a plasma etching process
  • residues derived from the metal layer and/or the interlayer insulating film may adhere to the substrate, the metal layer and/or the interlayer insulating film.
  • cleaning using a processing liquid is often performed.
  • the resist film used as a mask during etching is then removed from the laminate by a dry method (dry ashing) using ashing (ashing), a wet method, or the like.
  • Residue derived from the resist film or the like may adhere to the laminate from which the resist has been removed using the dry ashing method.
  • cleaning using a processing liquid is often performed.
  • the processing liquid is used for removing residues (etching residue and ashing residue) and/or resist films in the semiconductor device manufacturing process.
  • Patent Document 1 discloses a stripper composition containing a combination of alkanolamines, aromatic alcohols, and an anticorrosive agent.
  • the present inventors have studied the composition described in Patent Document 1, and found that there is room for further improvement in the residue removability (especially residue removability after dry etching) of the composition. clarified.
  • a composition for a semiconductor device comprising an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, and water.
  • the composition of [1] which has a pH of 9-11.
  • the alcohol is a monoalcohol having a main chain skeleton consisting of an aliphatic hydrocarbon group and an alcoholic hydroxyl group, or a polyhydric alcohol having a main chain skeleton consisting of an aliphatic hydrocarbon group and an alcoholic hydroxyl group.
  • composition according to [1] or [2], comprising: [5] The composition according to any one of [1] to [4], wherein the aprotic polar solvent contains at least one selected from the group consisting of dimethylsulfoxide and sulfolane. [6] The composition according to any one of [1] to [5], wherein the aprotic polar solvent contains sulfolane. [7] The composition according to any one of [1] to [6], further comprising component A selected from the group consisting of sulfolene and dipropylsulfone. [8] The composition according to [7], wherein the content of component A is 100 mass ppt or more and 100 mass ppm or less relative to the total mass of the composition.
  • any one of [7] to [9], wherein the mass ratio of the content of the aprotic polar solvent to the content of Component A is 1.0 ⁇ 10 4 to 1.0 ⁇ 10 10 The composition according to . [11] the alcohol is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 3-pentanol and cyclopentanol; The composition according to any one of [1] to [10].
  • the azole compound is 1,2,4-triazole, 1,2,3-triazole, 1H-tetrazole, 5-aminotetrazole, 1H-benzotriazole, tolyltriazole, 5-methyltriazole, carboxybenzotriazole and 2,2'-[ ⁇ (methyl-1H-benzotriazol-1-yl)methyl ⁇ imino]bisethanol according to any one of [1] to [13], including at least one selected from the group consisting of composition.
  • the alkanolamine is diethanolamine, 2-(2-aminoethylamino)ethanol, 2-(2-aminoethoxy)ethanol, triethanolamine, 2-aminoethanol, N,N-dimethylethanolamine, N,
  • the chelating agent contains at least one selected from the group consisting of aminopolycarboxylic acids and polycarboxylic acids.
  • a method for cleaning a substrate comprising a cleaning step of cleaning a substrate provided with a metal layer using the composition according to any one of [1] to [21].
  • composition for semiconductor devices Comprising: It can provide the composition which is excellent in residue removability (in particular, residue removability after dry etching). Further, according to the present invention, a method for cleaning a substrate using the above composition can be provided.
  • a numerical range represented by "to” means a range including the numerical values before and after "to” as lower and upper limits.
  • the term “preparation” includes not only preparing specific materials by synthesizing or mixing them, but also procuring predetermined items by purchasing or the like.
  • the "content" of that component means the total content of those two or more kinds of components.
  • ppm means “parts-per-million ( 10-6 )
  • ppb means “parts-per-billion ( 10-9 )
  • ppt means “ parts-per-trillion (10 ⁇ 12 )”.
  • 1 ⁇ corresponds to 0.1 nm.
  • the notation not describing substitution and unsubstituted includes those not having substituents as well as those having substituents, as long as the effects of the present invention are not impaired. It is something to do.
  • hydrocarbon group includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group). .
  • light means actinic rays or radiation.
  • radiation means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, or electron beams.
  • exposure means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, X-rays or EUV light, but also by particle beams such as electron beams or ion beams. Including drawing.
  • composition of the present invention is a composition containing at least an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, and water.
  • this composition is a composition containing at least an alcohol, an aprotic polar solvent, an azole compound, an alkanolamine, and water.
  • the present inventors have found that when the composition contains a combination of the above components, the residue removability (especially the residue removability after dry etching) is excellent (hereinafter also referred to as "the effect of the present invention is excellent"). , completed the present invention.
  • Alcohols included in the composition are compounds having at least one alcoholic hydroxyl group.
  • alkanolamines and azole compounds described later are not included in alcohol.
  • alcohols include compounds having a main chain skeleton containing a linear or cyclic aliphatic hydrocarbon group and at least one alcoholic hydroxyl group.
  • main chain skeleton one or more methanediyl groups (--CH.sub.2--) constituting a chain or cyclic aliphatic hydrocarbon group may be substituted with heteroatoms.
  • Heteroatoms include, for example, -O- and -S-.
  • the alcoholic hydroxyl group is bonded to the main chain skeleton.
  • the alcohol may be a monoalcohol having one alcoholic hydroxyl group, or a polyhydric alcohol having two or more alcoholic hydroxyl groups.
  • the alcohol is preferably a monoalcohol or a polyhydric alcohol having two or three alcoholic hydroxyl groups, more preferably a monoalcohol or a polyhydric alcohol having two alcoholic hydroxyl groups, and still more preferably a monoalcohol.
  • the alcohol has a main chain skeleton composed of an aliphatic hydrocarbon group that does not have a heteroatom such as an ether group (-O-), and an alcohol bonded to the main chain skeleton, in that the effects of the present invention are more excellent. It is preferably a compound (monoalcohol or polyhydric alcohol) having a functional hydroxyl group.
  • a chain-like main chain skeleton having no cyclic structure is preferable in that the anticorrosion property (Co anticorrosion property) to the metal layer containing Co is more excellent.
  • the alcohol is a compound having a main chain skeleton and an alcoholic hydroxyl group bonded to the main chain skeleton, the main chain skeleton being an aliphatic hydrocarbon group, and/or , preferably a chain main chain skeleton, and more preferably a compound having a main chain skeleton composed of a chain aliphatic hydrocarbon group having no heteroatom and an alcoholic hydroxyl group.
  • the number of carbon atoms in the aliphatic hydrocarbon group constituting the main chain skeleton is not particularly limited, but is preferably 1-8, more preferably 2-6.
  • Monoalcohols having a main chain skeleton composed of a chain aliphatic hydrocarbon group include, for example, methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 1-butanol, 2-butanol, isobutyl alcohol, tert- Butyl alcohol, 2-pentanol, t-pentyl alcohol, 1-hexanol, allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol and 4-penten-2-ol.
  • Examples of the polyhydric alcohol having a main chain skeleton composed of a linear aliphatic hydrocarbon group include ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2 -dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol and pinacol.
  • Examples of alcohols having a main chain skeleton composed of an aliphatic hydrocarbon group and having a cyclic structure include cyclopentanol, cyclohexanol, and 1,3-cyclopentanediol.
  • Examples of alcohols having a main chain structure in which one or more carbon atoms constituting a chain aliphatic hydrocarbon group are substituted with an ether group include mono- or poly(alkyleneoxy) alkyl ethers.
  • ethylene glycol monoalkyl ether diethylene glycol, diethylene glycol monoalkyl ether, triethylene glycol, triethylene glycol monoalkyl ether, tetraethylene glycol, hexylene glycol, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, ethylene glycol mono Benzyl ether and diethylene glycol monobenzyl ether are included.
  • alcohols having a cyclic structure and a main chain structure in which one or more carbon atoms constituting an aliphatic hydrocarbon group are substituted with an ether group include tetrahydrofurfuryl alcohol. are mentioned.
  • Preferred alcohols are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 3-pentanol and cyclopentanol, and ethanol, 1-propanol, More preferred are 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 3-pentanol or cyclopentanol, and even more preferred is 1-butanol, 2-butanol or t-butanol.
  • a hydrophilic alcohol is preferable.
  • the term “hydrophilic” means that 0.1 g or more of a substance dissolves in 100 g of water under conditions of 25°C. Among them, an alcohol that dissolves 10 g or more in 100 g of water under the condition of 25° C. or an alcohol that can be uniformly mixed with water at any mixing ratio is preferable.
  • Alcohol may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of the alcohol used in combination of two or more include the above-described combinations of alcohols.
  • the alcohol content is not particularly limited, but is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and 55 to 75% by mass, based on the total mass of the composition, in terms of better cleaning properties. is more preferred.
  • composition comprises an aprotic polar solvent.
  • an aprotic polar solvent means a compound that does not have proton (hydrogen ion) donating properties and has an electrical bias in its molecule.
  • Aprotic polar solvents include, for example, sulfur-containing solvents and ketone solvents.
  • sulfur-containing solvents include dimethylsulfone, dimethylsulfoxide and sulfolane.
  • Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
  • the aprotic polar solvent is preferably a sulfur-containing solvent, more preferably dimethylsulfoxide or sulfolane, and still more preferably sulfolane.
  • An aprotic polar solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the aprotic polar solvent is preferably 0.1 to 40% by mass, more preferably 1 to 20% by mass, more preferably 5 to 15% by mass, relative to the total mass of the composition, in terms of more excellent residue removability. % by mass is more preferred.
  • An azole compound is a compound having at least one nitrogen atom and having an aromatic five-membered hetero ring.
  • the number of nitrogen atoms contained in the five-membered hetero ring of the azole compound is not particularly limited, and is preferably 1 to 4, more preferably 2 to 4.
  • the azole compound may have a substituent on the hetero 5-membered ring.
  • substituents include, for example, hydroxy groups, carboxy groups, mercapto groups, amino groups, and substituted or unsubstituted hydrocarbon groups.
  • the two substituents may combine with each other to form a ring.
  • the hydrocarbon group that the hetero 5-membered ring has as a substituent includes an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, 2 to 6 are more preferred), alkynyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), aryl groups (preferably 6 to 18 carbon atoms, more preferably 6 to 10 carbon atoms), and , and aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 11 carbon atoms).
  • an alkyl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms
  • an alkenyl group preferably having 2 to 12 carbon atoms, 2 to 6 are more preferred
  • alkynyl groups preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms
  • aryl groups preferably 6 to 18 carbon atoms, more
  • substituents possessed by the above hydrocarbon groups include a hydroxy group, a carboxy group, and —N(R a )(R b ).
  • R a and R b each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms), or a hydroxyalkyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms).
  • the ring formed by binding two adjacent substituents on the hetero 5-membered ring to each other is not particularly limited, but an aromatic ring (either monocyclic or polycyclic) is preferable, and a benzene ring is more preferred.
  • the ring formed by combining the above two substituents may have a substituent.
  • the substituent is not particularly limited, and examples thereof include those exemplified as the substituent of the hydrocarbon group of the hetero 5-membered ring.
  • azole compounds include imidazole compounds in which one of the atoms constituting the azole ring is a nitrogen atom, pyrazole compounds in which two of the atoms constituting the azole ring are nitrogen atoms, and one of the atoms constituting the azole ring.
  • imidazole compounds include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole, 4-hydroxy Imidazole, 2,2'-biimidazole, 4-imidazole carboxylic acid, histamine and benzimidazole.
  • pyrazole compounds include pyrazole, 4-pyrazolecarboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-aminopyrazole and 4-aminopyrazole.
  • Thiazole compounds include, for example, 2,4-dimethylthiazole, benzothiazole and 2-mercaptobenzothiazole.
  • Triazole compounds include, for example, compounds having a benzotriazole skeleton formed by bonding two adjacent substituents on the triazole ring to form a benzene ring.
  • Compounds having a benzotriazole skeleton include, for example, 1H-benzotriazole, 2H-benzotriazole, and an alkyl group (preferably having a carbon number of 1 to 8 alkyl group), an amino group, a hydroxy group, a carboxy group, a halogen atom, an aryl group, and a compound substituted with at least one substituent selected from the group consisting of a combination of these. .
  • 1H-benzotriazole 1H-benzotriazole, 2H-benzotriazole, 5-methyl-1H-benzotriazole (CAS Registry Number: 136-85-6), tolyltriazole (CAS Registry Number: 29385-43-1), 5-aminobenzotriazole, 1-hydroxybenzotriazole, carboxybenzotriazole (such as benzotriazole-5-carboxylic acid and 4-carboxybenzotriazole), 5,6-dimethylbenzotriazole, 1-[N,N -bis(hydroxyethyl)aminoethyl]benzotriazole, 1-(1,2-dicarboxyethyl)benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-[N, N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole as well as 2,2'- ⁇ [(methyl-1H-benzotriazol-1
  • triazole compounds other than compounds having a benzotriazole skeleton examples include 1,2,4-triazole, 3-methyl-1,2,4-triazole, and 3-amino-1,2,4-triazole. , 1,2,3-triazole, and 1-methyl-1,2,3-triazole.
  • Tetrazole compounds include, for example, 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1H-tetrazole, 5-amino-1H-tetrazole, 1,5-pentamethylenetetrazole, 1- phenyl-5-mercaptotetrazole, and 1-(2-dimethylaminoethyl)-5-mercaptotetrazole.
  • the azole compound is preferably a triazole compound or a tetrazole compound, such as 1,2,4-triazole, 1,2,3-triazole, 1H-tetrazole, 5-aminotetrazole, 1H-benzotriazole, tolyltriazole, 5-methyltriazole.
  • carboxybenzotriazole and 2,2′-[ ⁇ (methyl-1H-benzotriazol-1-yl)methyl ⁇ imino]bisethanol is more preferably at least one selected from the group consisting of 1,2,4-triazole , 1H-benzotriazole, tolyltriazole, 5-methyltriazole, or 2,2′-[ ⁇ (methyl-1H-benzotriazol-1-yl)methyl ⁇ imino]bisethanol are more preferred.
  • said azole compound shall include the tautomer.
  • An azole compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the azole compound is preferably from 0.01 to 10% by mass, preferably from 0.1 to 6% by mass is more preferable, 0.1 to 5% by mass is more preferable, and 0.2 to 3% by mass is even more preferable.
  • Alkanolamine The composition contains an alkanolamine.
  • Alkanolamines are amine compounds having at least one amino group in the molecule and further having at least one hydroxy group (preferably a hydroxylalkyl group).
  • Examples of the alkanolamine include, for example, a main chain skeleton composed of a chain aliphatic hydrocarbon group, at least one amino group bonded to the main chain skeleton, and at least one alcoholic group bonded to the main chain skeleton. and a compound having a hydroxyl group.
  • one or more methanediyl groups (--CH.sub.2--) constituting the chain-like aliphatic hydrocarbon group may be substituted with heteroatoms.
  • Heteroatoms include, for example, -O-, -S- and -NH-, with -O- or -NH- being preferred.
  • the number of amino groups that the alkanolamine has is, for example, 1 to 5, preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.
  • the amino group possessed by the alkanolamine may be any of a primary amino group (—NH 2 ), a secondary amino group (>NH), and a tertiary amino group (>N—).
  • the alkanolamine preferably has at least one selected from the group consisting of a primary amino group and a secondary amino group, and the amino group possessed by the alkanolamine is either a primary amino group or a secondary An amino group is more preferred.
  • the number of hydroxy groups possessed by the aminoalcohol is, for example, 1 to 5, preferably 1 to 3, more preferably 1 or 2.
  • Alkanolamines include, for example, 2-aminoethanol, diethanolamine (DEA), triethanolamine (TEA), trishydroxymethylaminomethane (Tris), 2-(2-aminoethoxy)ethanol, 2-(2-aminoethyl amino) ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methylethanolamine, 2-amino-2-methyl-1-propanol, 2- Amino-2-methyl-1,3-dipropanol, 2-amino-2-ethyl-1,3-dipropanol, and 2-(methylamino)-2-methyl-1-propanol.
  • diethanolamine, 2-(2-aminoethylamino)ethanol, 2-(2-aminoethoxy)ethanol, triethanolamine, 2-aminoethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine , N-methyldiethanolamine, N-ethyldiethanolamine or N-methylethanolamine are preferred, diethanolamine, 2-(2-aminoethoxy)ethanol, 2-aminoethanol, 2-(2-aminoethylamino)ethanol, N,N -dimethylethanolamine or N-methylethanolamine are more preferred.
  • Alkanolamine may be used alone or in combination of two or more.
  • the content of alkanolamine is preferably 0.1 to 30% by mass, more preferably 0.1 to 15% by mass, more preferably 0.3 to 0.3%, based on the total mass of the composition, in terms of better Co corrosion resistance 10% by mass is more preferred, and 1 to 10% by mass is even more preferred.
  • the composition contains water.
  • Water is not particularly limited, and distilled water, deionized water, and pure water (ultra-pure water) can be used. Pure water is preferable because it contains almost no impurities and has less influence on the semiconductor substrate in the manufacturing process of the semiconductor substrate.
  • deionized water (DIW) with reduced inorganic anions and metal ions is preferable, and Fe, Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni and Zn It is more preferable that the concentration of ions derived from the metal atoms of is reduced.
  • the concentration of ions derived from metal atoms in water is on the order of ppt or less (in one embodiment, the metal content is less than 0.001 ppt by mass).
  • purification using a filtration membrane or an ion exchange membrane, or purification by distillation is preferred. Examples of the adjustment method include the method described in JP-A-2011-110515, paragraphs [0074] to [0084], and the method described in JP-A-2007-254168.
  • the content of water is not particularly limited, but is, for example, 1 to 90% by mass, preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 15 to 35% by mass relative to the total mass of the composition. % by mass is more preferred.
  • the water used in the embodiment of the present invention is preferably water prepared as described above.
  • the above water is preferably used not only for the composition but also for cleaning the container, and may also be used for the manufacturing process of the composition, measurement of the components of the composition, and measurement for evaluation of the composition. preferable.
  • composition may further contain components other than those described above.
  • Optional components that the composition may contain are described below.
  • the composition may further contain component A selected from the group consisting of sulfolene and dipropylsulfone, and preferably contains component A in terms of better Co corrosion resistance.
  • component A selected from the group consisting of sulfolene and dipropylsulfone, and preferably contains component A in terms of better Co corrosion resistance.
  • sulfolene is a generic term that includes all isomers such as 2-sulfolene and 3-sulfolene, and sulfolene includes all isomers.
  • the composition preferably comprises as component A a compound selected from the group consisting of 2-sulfolene and dipropylsulfone.
  • the composition may contain component A singly or in combination of two or more.
  • the content of component A is not particularly limited, but is preferably 10 mass ppt or more, and 100 mass ppt or more, based on the total mass of the composition, in terms of further improving Co corrosion resistance. is more preferable, and 1000 mass ppt or more is even more preferable.
  • the upper limit is not particularly limited, it is preferably 1000 ppm by mass or less, more preferably 100 ppm by mass or less, and still more preferably 10 ppm by mass or less, based on the total mass of the composition in terms of better defect suppression ability.
  • the ratio of the content of the azole compound to the content of component A is 1. 0 ⁇ 10 2 to 1.0 ⁇ 10 12 are preferred, 1.0 ⁇ 10 3 to 1.0 ⁇ 10 10 are more preferred, and 1.0 ⁇ 10 4 to 1.0 ⁇ 10 8 are even more preferred.
  • the ratio of the content of the aprotic polar solvent to the content of component A is the metal layer containing tungsten 1.0 ⁇ 10 3 to 1.0 ⁇ 10 12 is preferable, 1.0 ⁇ 10 4 to 1.0 ⁇ 10 10 is more preferable, and 1.0 ⁇ 10 4 to 1.0 ⁇ 10 9 is more preferable.
  • the composition may contain a chelating agent.
  • a chelating agent is a compound having a function of chelating with a metal element.
  • the composition preferably contains a chelating agent because the function of the chelating agent further improves the performance of removing residues such as etching residues and ashing residues.
  • the composition contains a chelating agent, it is possible to remove the above-described residues in a short period of time, which is also preferable from the viewpoint of anticorrosion to the metal layer.
  • the chelating agent is not particularly limited as long as it is a compound having a function of chelating with the metal element, but a compound having two or more functional groups (coordination groups) that coordinately bond with the metal element in one molecule is preferable.
  • the chelating agent does not include compounds corresponding to the above alkanolamines.
  • Coordinating groups possessed by the chelating agent include acid groups and cationic groups.
  • Acid groups include, for example, carboxy groups, phosphonic acid groups, phosphoric acid groups, sulfo groups and phenolic hydroxy groups.
  • Cationic groups include, for example, amino groups.
  • the chelating agent contained in the composition preferably has a coordinating group selected from the group consisting of a carboxy group, a phosphonic acid group, a phosphoric acid group, and an amino group, and more preferably has a carboxy group.
  • Chelating agents are preferably of low molecular weight.
  • the molecular weight of the chelating agent is preferably 600 or less, more preferably 450 or less, and even more preferably 300 or less.
  • the lower limit is not particularly limited, 85 or more is preferable.
  • the number of carbon atoms in the chelating agent is preferably 15 or less, more preferably 12 or less, and even more preferably 8 or less.
  • the lower limit is not particularly limited, 1 or more is preferable.
  • Chelating agents include, for example, a carboxylic acid-based chelating agent having a carboxy group, a phosphonic acid-based chelating agent having a phosphonic acid group, a phosphoric acid-based chelating agent having a phosphoric acid group, and a polyamine-based chelating agent having a plurality of amino groups. agents.
  • a carboxylic acid-based chelating agent is a chelating agent having a carboxy group as a coordinating group in the molecule, and includes, for example, polycarboxylic acids, aminopolycarboxylic acids, amino acids, and hydroxycarboxylic acids.
  • a polycarboxylic acid is a compound having multiple carboxy groups in the molecule.
  • aminopolycarboxylic acids which will be described later, are not included in polycarboxylic acids.
  • Polycarboxylic acids include, for example, citric acid, malonic acid, maleic acid, succinic acid, malic acid, tartaric acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, and sebacic acid.
  • Aminopolycarboxylic acids are compounds having one or more amino groups and multiple carboxy groups in the molecule.
  • As the aminopolycarboxylic acid a polyaminopolycarboxylic acid having multiple amino groups and multiple carboxy groups in the molecule is preferred.
  • Polyaminopolycarboxylic acids include, for example, mono- or polyalkylenepolyaminepolycarboxylic acids and polyaminoalkanepolycarboxylic acids.
  • polyaminopolycarboxylic acids include butylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N,N,N ',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid (Cy-DTA), ethylenediaminediacetic acid, ethylenediaminedipropionic acid, diaminopropanetetraacetic acid, and 1,4,7,10-tetraazacyclododecane-tetraacetic acid.
  • Aminopolycarboxylic acids other than polyaminopolycarboxylic acids include, for example, iminodiacetic acid, n
  • Amino acids include compounds having one or more amino groups and one carboxy group in the molecule. More specifically, amino acids include glycine, serine, ⁇ -alanine (2-aminopropionic acid), ⁇ -alanine (3-aminopropionic acid), lysine, leucine, isoleucine, cystine, cysteine, ethionine, threonine, Tryptophan, tyrosine, valine, histidine, histidine derivatives, asparagine, glutamine, arginine, proline, methionine, phenylalanine, compounds described in paragraphs [0021] to [0023] of JP-A-2016-086094, and salts thereof. .
  • Salts also include alkali metal salts such as sodium and potassium salts, ammonium salts, carbonates, and acetates.
  • a hydroxycarboxylic acid is a compound having one carboxy group and one or more hydroxy groups in the molecule.
  • Hydroxycarboxylic acids include, for example, gluconic acid, heptonic acid, glycolic acid and lactic acid.
  • the carboxylic acid-based chelating agent is preferably polycarboxylic acid or aminopolycarboxylic acid, more preferably polycarboxylic acid or polyaminopolycarboxylic acid.
  • a phosphonic acid-based chelating agent is a chelating agent having at least one phosphonic acid group as a coordinating group in the molecule.
  • a chelating agent having both a phosphonic acid group and a carboxyl group is classified as a carboxylic acid-based chelating agent.
  • Examples of phosphonic acid-based chelating agents include ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropylidene-1,1'-diphosphonic acid, and 1-hydroxybutylidene.
  • Phosphonic acid-based chelating agents used in the composition include not only the above compounds, but also the compounds described in paragraphs [0026] to [0036] of International Publication No. 2018/020878, and International Publication No. 2018/030006.
  • the compounds ((co)polymers) described in paragraphs [0031] to [0046] of the specification can be cited and their contents are incorporated herein.
  • the number of phosphonic acid groups possessed by the phosphonic acid-based chelating agent is preferably 2 to 5, more preferably 2 to 4, and still more preferably 2 or 3.
  • the carbon number of the phosphonic acid-based chelating agent is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the lower limit is not particularly limited, and 1 or more is preferable.
  • As the phosphonic acid-based chelating agent HEDPO, NTPO, EDTPO, or DEPPO is more preferred, and EDTPO is even more preferred.
  • Phosphonic acid-based chelating agents may be used singly or in combination of two or more.
  • Phosphate-based chelating agents include, for example, condensed phosphoric acid and salts thereof, more specifically pyrophosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid, and salts thereof.
  • a polyamine-based chelating agent is a chelating agent having only a plurality of amino groups as coordinating groups in its molecule.
  • examples of polyamine-based chelating agents include lower alkylenediamines such as ethylenediamine (EDA), 1,3-propanediamine (PDA), 1,2-propanediamine, 1,3-butanediamine and 1,4-butanediamine; and polyalkylpolyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), bis(aminopropyl)ethylenediamine (BAPEDA) and tetraethylenepentamine.
  • DETA diethylenetriamine
  • TETA triethylenetetramine
  • BAPEDA bis(aminopropyl)ethylenediamine
  • tetraethylenepentamine Among them, lower alkylenediamine is preferable, and 1,4-butanediamine is more preferable.
  • Polyamine-based chelating agents other than the above include at least one biguanide compound selected from the group consisting of compounds having a biguanide group and salts thereof.
  • the number of biguanide groups in the biguanide compound is not particularly limited, and the biguanide compound may have a plurality of biguanide groups.
  • the biguanide compound compounds described in paragraphs [0034] to [0055] of JP-A-2017-504190 can also be used, and the contents described in the above documents are incorporated herein.
  • Examples of compounds having a biguanide group include ethylene dibiguanide, propylene dibiguanide, tetramethylene dibiguanide, pentamethylene dibiguanide, hexamethylene dibiguanide, heptamethylene dibiguanide, octamethylene dibiguanide, 1,1′-hexamethylene.
  • chelating agents other than the above include compounds represented by the following formula (A) and compounds represented by the following formula (B).
  • R 1A to R 5A each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a hydroxy group, a carboxy group, or a substituted or unsubstituted amino group. However, the structure contains at least one group selected from a hydroxy group, a carboxy group and a substituted or unsubstituted amino group.
  • R 1B to R 4B each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
  • Compounds represented by formula (A) include, for example, 1-thioglycerol and thiomalic acid.
  • Compounds represented by formula (B) include, for example, catechol and t-butylcatechol.
  • the chelating agent is preferably a carboxylic acid-based chelating agent or a phosphonic acid-based chelating agent, more preferably a carboxylic acid-based chelating agent, more preferably a polycarboxylic acid or an aminopolycarboxylic acid, and a polyaminopolycarboxylic acid or , polycarboxylic acids are particularly preferred.
  • the chelating agents may be used singly or in combination of two or more. Since the coordinating groups possessed by the chelating agent differ in the specificity of the metals to be adsorbed for each type, the composition has two different coordinating groups in that the residue containing a plurality of metals can be removed more effectively. It is preferred to include a combination of the above chelating agents. When the composition contains a combination of two or more of the above chelating agents, the mass ratio of the content of the other chelating agent to the content of one chelating agent is preferably 0.01 to 100, and 0.1. ⁇ 10 is more preferred.
  • the content of the chelating agent is preferably 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total mass of the composition in terms of more excellent residue removability. is more preferred, and 0.1 to 3% by mass is even more preferred.
  • the chelating agent has the effect of further improving the residue removability of the composition when the residue contains a large amount of metal, such as when the object to be cleaned is a dry etching residue. For this reason, a composition containing a chelating agent is preferably used for treating such objects to be cleaned.
  • the composition may contain a basic compound.
  • basic compound is intended a compound whose solution pH is greater than 7 when dissolved in water.
  • a basic compound functions as a pH adjuster to adjust the pH of the composition.
  • the basic compound is not particularly limited and includes, for example, ammonium hydroxide, amine compounds (excluding the azole compounds, alkanolamines, and compounds contained in the chelating agents), and quaternary ammonium compounds. .
  • the composition may contain ammonium hydroxide (NH 4 OH) as the basic compound.
  • ammonium hydroxide NH 4 OH
  • its content is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 5.0% by mass, relative to the total mass of the composition. .
  • the amine compound is a compound having an amino group in the molecule and is intended to be a compound that is not included in the azole compound, alkanolamine, or chelating agent.
  • examples of amine compounds include primary amines having a primary amino group (—NH 2 ) in the molecule, secondary amines having a secondary amino group (>NH) in the molecule, and secondary amines having a secondary amino group (>NH) in the molecule.
  • salts of amine compounds include salts with inorganic acids in which at least one non-metal selected from the group consisting of Cl, S, N and P is combined with hydrogen, and hydrochlorides and sulfates. , or nitrates are preferred.
  • the amine compound is preferably a water-soluble amine that can dissolve 50 g or more in 1 L of water.
  • Amine compounds include, for example, alicyclic amine compounds, hydroxylamine compounds, and amine compounds other than these compounds.
  • An alicyclic amine compound intends a compound having an alicyclic (non-aromatic ring) structure in the molecule among amine compounds.
  • Examples of alicyclic amine compounds include 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), ⁇ -caprolactam, compound 1 below, compound 2 below, compound 3 below, 1,4- diazabicyclo[2.2.2]octane (DABCO), tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2 ,6-dimethylpiperazine, 2-piperidinemethanol, cyclohexylamine, and 1,5-diazabicyclo[4,3,0]-5-nonene.
  • DBU 1,8-diazabicyclo[5.4.0]-7-undecene
  • the hydroxylamine compound is at least one compound selected from the group consisting of hydroxylamine (NH 2 OH), hydroxylamine derivatives, and salts thereof.
  • hydroxylamine derivatives include, but are not limited to, O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,O-dimethylhydroxylamine, and N-ethylhydroxyl.
  • Salts of hydroxylamine and hydroxylamine derivatives include inorganic acid salts or organic acid salts, preferably inorganic acid salts formed by bonding a nonmetallic atom such as Cl, S, N, or P to a hydrogen atom. Acid salts of either , sulfuric acid or nitric acid are more preferred.
  • examples of primary amines other than alicyclic amine compounds and hydroxylamine compounds include methylamine, ethylamine, propylamine, butylamine, pentylamine, methoxyethylamine, and methoxypropylamine.
  • Secondary amines other than alicyclic amine compounds and hydroxylamine compounds include, for example, dimethylamine, diethylamine, dipropylamine, and dibutylamine (DBA).
  • Tertiary amines other than alicyclic amine compounds and hydroxylamine compounds include, for example, trimethylamine, triethylamine, and tributylamine (TBA).
  • An amine compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • its content is not particularly limited, but is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total mass of the composition.
  • the composition may contain a quaternary ammonium compound that is a compound or salt thereof having one quaternary ammonium cation in the molecule.
  • the quaternary ammonium compound is not particularly limited as long as it is a compound or a salt thereof having one quaternary ammonium cation in which a nitrogen atom is substituted with four hydrocarbon groups (preferably alkyl groups).
  • Examples of quaternary ammonium compounds include quaternary ammonium hydroxide, quaternary ammonium fluoride, quaternary ammonium bromide, quaternary ammonium iodide, quaternary ammonium acetate, and quaternary Carbonates of ammonium are mentioned.
  • the quaternary ammonium compound is preferably a quaternary ammonium hydroxide, more preferably a compound represented by the following formula (a1).
  • R a1 to R a4 are each independently an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or 1 to 1 carbon atoms. 16 hydroxyalkyl groups are shown. At least two of R a1 to R a4 may combine with each other to form a cyclic structure.
  • the above alkyl group may be linear, branched or cyclic.
  • Examples of the compound represented by the formula (a1) include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide (TBAH), methyl hydroxide tripropylammonium, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide (BzTMAH), hexadecyltrimethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, and , spiro-(1,1′)-bipyrrolidinium hydroxide.
  • TMAH tetramethylammonium hydroxide
  • TEAH tetraethylammonium hydroxide
  • TBAH tetrabutylam
  • a quaternary ammonium compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • its content is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, relative to the total mass of the composition.
  • a basic compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • its content is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, relative to the total mass of the composition.
  • the composition may contain an acidic compound as a pH adjuster.
  • the acidic compound may be an inorganic acid or an organic acid (excluding the above chelating agent).
  • Inorganic acids include sulfuric acid, hydrochloric acid, acetic acid, nitric acid and phosphoric acid, with sulfuric acid, hydrochloric acid, or acetic acid being preferred.
  • Organic acids include lower (C 1-4) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid.
  • the chelating agent may also serve as an acidic compound.
  • the acidic compounds may be used singly or in combination of two or more.
  • the type and content of the acidic compound may be appropriately selected and the content adjusted so that the pH of the composition falls within the range described later.
  • the composition may contain a fluorine-containing compound.
  • the fluorine-containing compound include hydrofluoric acid (hydrofluoric acid), ammonium fluoride, tetramethylammonium fluoride, and tetrabutylammonium fluoride, with hydrofluoric acid being preferred.
  • a fluorine-containing compound may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the composition contains a fluorine-containing compound, its content is preferably 0.01 to 5.0% by mass relative to the total mass of the composition.
  • the composition may contain a metal component.
  • Metal components include metal particles and metal ions.
  • the composition may contain either one of metal particles and metal ions, or may contain both.
  • metal atoms contained in the metal component include Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na , Ni, Pb, Sn, Sr, Ti, and Zn.
  • the metal component may contain one type of metal atom, or may contain two or more types.
  • the metal particles may be a single substance or an alloy, and may exist in a form in which the metal is associated with an organic substance.
  • the metal component may be a metal component that is inevitably contained in each component (raw material) contained in the composition, or a metal component that is inevitably contained during production, storage, and/or transportation of the composition. and may be added intentionally.
  • the content of the metal component is often 0.01 mass ppt to 10 mass ppm, preferably 0.1 mass ppt to 1 mass ppm, relative to the total mass of the composition. , from 0.1 mass ppt to 100 mass ppb.
  • the type and content of metal components in the composition can be measured by ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry) method.
  • ICP-MS Single Nano Particle Inductively Coupled Plasma Mass Spectrometry
  • the content of the metal component to be measured is measured regardless of its existence form. Therefore, the total mass of the metal particles and metal ions to be measured is quantified as the content of the metal component.
  • ICP-MS measurement for example, Agilent Technologies, Inc., Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200), Agilent 8900, and PerkinElmer Manufactured by NexION350S can be used.
  • the method of adjusting the content of each metal component in the composition is not particularly limited.
  • the content of metal components in the composition can be reduced by performing known treatments for removing metals from the composition and/or from raw materials containing each component used to prepare the composition.
  • the content of the metal component in the composition can be increased.
  • the composition preferably contains an anticorrosive agent.
  • the anticorrosive agent has the function of preventing corrosion of the metal layer due to overetching or the like by forming a film by coordinating on the surface of the metal layer (especially the W-containing layer or the Co-containing layer) that will become the wiring of the semiconductor device. have.
  • the azole compounds and chelating agents are not included in anticorrosive agents.
  • Anticorrosive agents include, for example, tritolyl phosphate, adenine, cytosine, guanine, thymine, phosphate inhibitors, propanethiol, silanes, benzohydroxamic acids, heterocyclic nitrogen inhibitors, ascorbic acid, thiourea, 1,1, 3,3-tetramethylurea, urea, urea derivatives, uric acid, potassium ethylxanthate, dodecylphosphonic acid, boric acid, 2,3,5-trimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, quinoxaline, Acetylpyrrole, pyridazine, histadine, pyrazine, glutathione (reduced), thiophene, mercaptopyridine N-oxide, thiamine HCl, tetraethylthiuram disulfide, and phenol.
  • Corrosion inhibitors also include, for example, substituted or unsubstituted tetrazoles.
  • Substituted or unsubstituted tetrazoles include, for example, unsubstituted tetrazoles and tetrazoles having a hydroxy group, a carboxy group, or a substituted or unsubstituted amino group as a substituent.
  • substituent when the amino group is substituted an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.
  • the anticorrosive may be used singly or in combination of two or more.
  • the content of the anticorrosive agent is preferably 0.01 to 5% by mass, more preferably 0.05 to 5% by mass, more preferably 0.1 to 5% by mass, based on the total mass of the composition. 3% by mass is more preferred.
  • the method for purifying the anticorrosive agent is not particularly limited, but known methods such as filtration, ion exchange, distillation, adsorption purification, recrystallization, reprecipitation, sublimation and purification using a column are used, and these methods are used. They can also be applied in combination.
  • composition may contain additives other than the above ingredients.
  • Additives include, for example, surfactants, defoamers, rust inhibitors and preservatives.
  • the composition is preferably used at pH 7 or higher.
  • the pH of the composition is preferably 9-11.
  • the pH of the composition is preferably from 9.2 to 11, more preferably from 9.5 to 11, from the viewpoint of more excellent Co corrosion resistance and W corrosion resistance.
  • the pH of the composition is a value obtained by measuring at 25°C using a known pH meter.
  • the composition is substantially free of coarse particles.
  • Coarse particles refer to particles having a diameter of 0.2 ⁇ m or more, for example, when the shape of the particles is assumed to be spherical.
  • substantially free of coarse particles means that when the composition is measured using a commercially available measuring device in a light scattering type liquid particle measurement method, particles of 0.2 ⁇ m or more in 1 mL of the composition is 10 or less.
  • the coarse particles contained in the composition are particles such as dust, dirt, organic solids and inorganic solids contained as impurities in the raw materials, and dust, dust, and the like brought in as contaminants during preparation of the composition.
  • the amount of coarse particles present in the composition can be measured in the liquid phase using a commercially available measurement device in the light scattering type in-liquid particle measurement system using a laser as a light source.
  • processing such as filtering is exemplified.
  • the composition may be prepared as a kit for preparing the composition by dividing the raw material into a plurality of parts.
  • a kit for preparing the composition for example, a kit comprising a first liquid containing at least an azole compound and an alkanolamine and a second liquid containing at least an aprotic polar solvent (hereinafter also referred to as "kit A" do.)
  • the first liquid of kit A may contain components other than the azole compound and alkanolamine, but preferably does not contain an aprotic polar solvent.
  • the second liquid of kit A may contain components other than the aprotic polar solvent, it preferably contains neither an azole compound nor an alkanolamine.
  • the content of each component contained in the first liquid and the second liquid provided in the kit is not particularly limited, but the content of each component in the composition prepared by mixing the first liquid and the second liquid is the above. It is preferable that it is an amount that becomes a preferable content.
  • the pH of the first liquid and the second liquid provided in the kit is not particularly limited, and the pH of the composition prepared by mixing the first liquid and the second liquid is within the above range. should be adjusted.
  • the composition may be prepared as a concentrate. In this case, it can be diluted with a diluent before use.
  • a diluent include, but are not particularly limited to, diluents composed of alcohol, aprotic polar solvents, water, or mixtures thereof.
  • the kit for preparing the composition may be a kit comprising the above composition in the form of a concentrate and the above diluent.
  • the above composition is a composition for semiconductor devices.
  • the term "for semiconductor devices” means used in the manufacture of semiconductor devices.
  • the above composition can be used in any process for manufacturing semiconductor devices, and can be used, for example, to treat insulating films, resists, antireflection films, etching residues, ashing residues, etc. present on substrates. In this specification, etching residue and ashing residue are collectively referred to as residue. Further, the above composition may be used for treating a substrate after chemical mechanical polishing, and may be used as an etchant.
  • the composition is applied onto a substrate in order to improve the coatability of the composition prior to the step of forming a resist film using an actinic ray-sensitive or radiation-sensitive composition.
  • Liquids, compositions used for removing residues adhering to metal layers, solutions used for removing various resist films for pattern formation (e.g., removers and strippers), and permanent films e.g., It is used as a processing liquid such as a solution (for example, a remover, a stripper, etc.) used for removing color filters, transparent insulating films, and resin lenses from a semiconductor substrate.
  • the above composition can also be used as a composition for removing residues such as metal impurities or fine particles from a substrate after chemical mechanical polishing.
  • the above composition can also be used as an etchant for metal oxides (including composite oxides composed of multiple metal oxides) such as cobalt oxide and copper oxide.
  • the composition can be suitably used as a composition for removing residues adhering to metal layers (especially Co-containing layers or W-containing layers).
  • the composition may be used for only one of the above uses, or may be used for two or more uses.
  • composition preparation step> The method for producing the above composition is not particularly limited, and known production methods can be used.
  • the method for producing the composition include a method having at least a composition preparation step of mixing the above components to prepare a composition.
  • the order of mixing each component is not particularly limited. It is preferable that the concentrated liquid and each liquid included in the kit are also produced by the same method as described above.
  • the method of preparing the kit is not particularly limited. For example, after preparing the first liquid and the second liquid, the composition is prepared by housing the first liquid and the second liquid in different containers. A kit for this should be prepared.
  • each component Prior to use in the composition preparation step, each component is preferably subjected to a metal removal step of removing metals from a raw material containing each component to obtain a refined product containing each component.
  • a metal removal step of removing metals from a raw material containing each component to obtain a refined product containing each component.
  • the method for removing metals from a raw material containing each component (hereinafter also referred to as "substance to be purified”) is not particularly limited, and the substance to be purified is selected from the group consisting of chelate resins and ion exchange resins. well-known methods such as a method of passing the substance through a metal ion adsorption filter, and a method of passing the substance to be purified through a metal ion adsorption filter.
  • the components to be subjected to the metal removal step are not particularly limited as long as they are contained in the above composition (excluding metal components).
  • the content of the metal component contained in the raw material containing the chelating agent tends to be higher than that of other components. It is more preferable to prepare a composition using a purified product containing a chelating agent obtained by the method.
  • the object to be purified to be subjected to the metal removal step may contain a compound other than the object, and preferably contains a solvent. Solvents include water and organic solvents, with water being preferred.
  • the content of the target substance in the substance to be purified can be appropriately determined according to the type of the target substance and the specific metal removal treatment. ⁇ 50% by mass is preferred.
  • the method of passing the substance to be purified through at least one resin selected from the group consisting of chelate resins and ion exchange resins is not particularly limited, but the substance to be purified is passed through the chelate resin and/or ion exchange resin packed in a container. can be passed through.
  • the chelate resin and/or ion exchange resin through which the substance to be purified is passed may be used alone or in combination of two or more.
  • the substance to be purified may be passed through the same chelate resin and/or ion exchange resin two or more times. Both chelating resins and ion exchange resins may be used in the metal removal step. In that case, the chelating resin and the ion exchange resin may be used in multiple or mixed beds.
  • the container is not particularly limited as long as it can be filled with a chelate resin and/or an ion exchange resin and the substance to be purified can pass through the packed chelate resin and/or ion exchange resin. , packed towers.
  • Ion exchange resins used in the metal removal step include cation exchange resins and anion exchange resins.
  • a cation exchange resin may be used in a single bed, or a cation exchange resin and an anion exchange resin may be used in a double bed or a mixed bed.
  • known cation exchange resins can be used, and examples thereof include sulfonic acid type cation exchange resins and carboxylic acid type cation exchange resins.
  • the material of the cation exchange resin is not particularly limited, but a gel-type cation exchange resin is preferred.
  • the cation exchange resin commercially available products can be used.
  • Duolite registered trademark, hereinafter the same
  • C20J Duolite C20LF
  • Duolite C255LFH Duolite C-433LF
  • DIAION registered trademark, hereinafter the same
  • SK-110 DIAION SK1B
  • DIAION SK1BH manufactured by Mitsubishi Chemical Corporation
  • the chelate resin is not particularly limited as long as it has a chelate group capable of chelating a metal.
  • Chelate groups include, for example, iminodiacetic acid groups, iminopropionic acid groups, aminophosphonic acid groups such as aminomethylenephosphonic acid groups (—NH—CH 3 —PO 3 H 2 ), polyamine groups, and N-methylglucamine groups.
  • glucamine group, aminocarboxy group, dithiocarbamic acid group, thiol group, amidoxime group, and pyridine group such as, preferably an iminodiacetic acid group or an aminophosphonic acid group, more preferably an aminophosphonic acid group.
  • the chelate resin is preferably an H-type chelate resin.
  • the H-type chelate resin is obtained by contacting a metal ion-type chelate resin such as Na-type, Ca-type and Mg-type with a mineral acid for acid treatment.
  • the base of the chelate resin is not particularly limited, and examples thereof include styrene-divinylbenzene copolymers and styrene-ethylstyrene-divinylbenzene copolymers.
  • chelate resin commercially available products can be used. and Sumichelate MC960 (manufactured by Sumika Chemtex Co., Ltd.); Purolite S106, Purolite S910, Purolite S914, Purolite S920, Purolite S930, Purolite S950, Purolite S957, and Purolite S985 (manufactured by Purolite); DS-21, Amberlite IRC748, and Amberlite IRC747 (manufactured by Organo Corporation).
  • the metal removal step performed on the raw material containing the chelating agent is selected from the group consisting of chelating resins and ion exchange resins, since the content of metal components in the composition can be further reduced. It is preferable to include a step of passing the substance to be purified through at least one resin, and more preferably a step of passing the substance to be purified through a chelating resin. Among them, it is more preferable to include a step of passing the substance to be purified through a chelating resin having an aminophosphonic acid group, since the content of Ca and/or Zn contained in the raw material containing the chelating agent can be further reduced.
  • Orlyte DS-21 is an H-type chelate resin obtained by introducing an aminomethylphosphonic acid group as a chelate group into a base material made of a styrene-ethylstyrene-divinylbenzene copolymer, and contains 30 to 45% by mass of the above It is commercially available in a state containing a chelate resin and 55-70% by weight of water.
  • Conditions for passing the substance to be purified through the ion exchange resin are not particularly limited, and may be performed according to a known method.
  • the space velocity (SV: Space Velocity) when the material to be purified passes through the ion exchange resin is preferably 1-20, more preferably 1-10.
  • the temperature of the substance to be purified that contacts the ion exchange resin is preferably 10 to 40°C, more preferably 15 to 30°C.
  • an adsorption purification treatment step for metal components using silicon carbide which is described in International Publication No. 2012/043496, may be carried out, and this description is herein incorporated by reference. incorporated.
  • metal particles contained in the substance to be purified may be removed using a filter that is exemplified as a filter used in the filtration step described later.
  • the metal removed from the object to be purified by the metal removing step is not particularly limited, and metals such as Li, Na, Mg, Al, K, Ca, Cr, Mn, Fe, Ni, Zn and Pb can be mentioned.
  • the purified product obtained by the metal removal step has a reduced metal content compared to the product to be purified.
  • the content of the metal in the purified product is not particularly limited, but for example, the ratio of the content of each metal element of the metal component to the content of the chelating agent in the purified product containing the chelating agent is 1.0 in mass ratio. It is preferably 1.0 ⁇ 10 ⁇ 6 or less, more preferably 1.0 ⁇ 10 ⁇ 7 or less, and even more preferably 1.0 ⁇ 10 ⁇ 8 or less.
  • the ratio of the content of the Ca component to the content of the Na component is 1.0 or more in mass ratio (the content of the Na component is Ca content is preferably large, more preferably 1.1 or more, and even more preferably 1.2 or more.
  • the upper limit is not particularly limited, but the ratio of the content of the Ca component to the content of the Na component is preferably 50 or less in terms of mass ratio.
  • the type and content of metals in the material to be purified and the material to be purified can be measured according to the method described as the method for measuring the type and content of metal components in the composition.
  • the manufacturing method preferably includes a filtration step of filtering the liquid in order to remove foreign matter, coarse particles, and the like from the liquid.
  • the filtration method is not particularly limited, and known filtration methods can be used. Among them, filtering using a filter is preferable.
  • the filter used for filtering can be used without any particular limitation as long as it is conventionally used for filtration.
  • Materials constituting the filter include, for example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultrahigh molecular weight),
  • PP polypropylene
  • polyarylsulfone and the like are included.
  • polyamide resin, PTFE, polypropylene (including high-density polypropylene), and polyarylsulfone are preferred.
  • the lower limit is preferably 70 mN/m or more, and the upper limit is preferably 95 mN/m or less.
  • the critical surface tension of the filter is preferably 75-85 mN/m.
  • the critical surface tension value is the manufacturer's nominal value.
  • the pore size of the filter is preferably about 0.001 to 1.0 ⁇ m, more preferably about 0.02 to 0.5 ⁇ m, even more preferably about 0.01 to 0.1 ⁇ m.
  • different filters may be combined.
  • filtering by the first filter may be performed only once, or may be performed twice or more.
  • the filters may be of the same type or of different types, but are preferably of different types.
  • the first filter and the second filter differ in at least one of pore size and materials of construction. It is preferable that the pore size for the second and subsequent filtering is the same as or smaller than the pore size for the first filtering.
  • the first filters having different pore diameters within the above range may be combined.
  • the pore size here can refer to the nominal value of the filter manufacturer.
  • filters can be selected from various filters provided by Nippon Pall Co., Ltd., Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., and the like.
  • polyamide P-nylon filter (pore diameter 0.02 ⁇ m, critical surface tension 77 mN / m)"; (manufactured by Nippon Pall Co., Ltd.), high-density polyethylene "PE clean filter (pore diameter 0.02 ⁇ m)”; (manufactured by Nippon Pall Co., Ltd.) and "PE Clean Filter (pore size: 0.01 ⁇ m)” made of high-density polyethylene; (manufactured by Nippon Pall Co., Ltd.) can also be used.
  • the second filter can use a filter made of the same material as the first filter described above.
  • a pore size similar to that of the first filter described above can be used.
  • the ratio of the pore size of the second filter to the pore size of the first filter is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and still more preferably 0.3 to 0.9.
  • filtering with the first filter is performed with a mixture containing some components of the composition, and the remaining components are mixed to prepare the composition, and then filtering with the second filter. may be performed.
  • the filters used are preferably treated prior to filtering the composition.
  • the liquid used for this treatment is not particularly limited, but liquids containing the components contained in the composition, concentrate and composition are preferred.
  • the upper limit of the temperature during filtering is preferably room temperature (25° C.) or lower, more preferably 23° C. or lower, and even more preferably 20° C. or lower.
  • the lower limit of the temperature during filtering is preferably 0° C. or higher, more preferably 5° C. or higher, and even more preferably 10° C. or higher. Filtering can remove particulate contaminants and/or impurities, but filtering is more efficient when performed at the above temperatures, as less particulate contaminants and/or impurities are dissolved in the composition. done on purpose.
  • the production method may further include a static elimination step of static eliminating at least one selected from the group consisting of the composition, the concentrate, and the kit. A specific method of static elimination will be described later.
  • the cleanroom preferably meets 14644-1 cleanroom standards.
  • ISO International Organization for Standardization
  • ISO Class 2 ISO Class 3
  • ISO Class 4 ISO Class 1 or ISO Class 2 is more preferable
  • ISO Class 1 is preferable. More preferred.
  • the container for containing the above composition, concentrate or kit is not particularly limited as long as corrosiveness due to the liquid is not a problem, and known containers can be used.
  • a container having a high degree of cleanliness in the container and less elution of impurities is preferable for use in semiconductors.
  • Examples of commercially available containers include the "Clean Bottle” series manufactured by Aicello Chemical Co., Ltd. and the “Pure Bottle” manufactured by Kodama Resin Industry.
  • a multi-layer container with a 6-layer structure made of 6 types of resin and a 7-layer structure made of 6 types of resin are used for the inner wall of the container. is also preferred.
  • Examples of these containers include, but are not limited to, the containers described in JP-A-2015-123351.
  • the inner wall of the container is made of one or more resins selected from the group consisting of polyethylene resins, polypropylene resins and polyethylene-polypropylene resins, resins different from these, and metals such as stainless steel, Hastelloy, Inconel and Monel. or coated.
  • a fluororesin perfluoro resin
  • the inner wall is formed of or coated with polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin.
  • a specific example of a container having such an inner wall is a FluoroPure PFA composite drum manufactured by Entegris.
  • quartz and electropolished metal material are preferably used in addition to the above fluorine-based resin.
  • the metal material used for producing the electropolished metal material contains at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is 25 masses with respect to the total mass of the metal material. %, such as stainless steel and nickel-chromium alloys.
  • the total content of chromium and nickel in the metal material is preferably 25% by mass or more, more preferably 30% by mass or more, relative to the total mass of the metal material.
  • the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90% by mass or less.
  • the stainless steel is not particularly limited, and known stainless steel can be used. Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable.
  • austenitic stainless steel include SUS (Steel Use Stainless) 304 (Ni content: 8% by mass, Cr content: 18% by mass), SUS304L (Ni content: 9% by mass, Cr content : 18% by mass), SUS316 (Ni content: 10% by mass, Cr content: 16% by mass), SUS316L (Ni content: 12% by mass, Cr content: 16% by mass), etc. is mentioned.
  • Nickel-chromium alloys are not particularly limited, and known nickel-chromium alloys can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferable. Examples of nickel-chromium alloys include Hastelloy (trade name, hereinafter the same), Monel (trade name, the same hereinafter), and Inconel (trade name, the same hereinafter).
  • Hastelloy C-276 (Ni content: 63% by mass, Cr content: 16% by mass), Hastelloy-C (Ni content: 60% by mass, Cr content: 17% by mass %), Hastelloy C-22 (Ni content: 61% by mass, Cr content: 22% by mass), and the like.
  • the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, etc. in addition to the alloys described above, if necessary.
  • the method for electropolishing the metal material is not particularly limited, and known methods can be used. For example, the methods described in paragraphs [0011] to [0014] of JP-A-2015-227501 and paragraphs [0036]-[0042] of JP-A-2008-264929 can be used.
  • the metal material is preferably buffed.
  • the buffing method is not particularly limited, and any known method can be used.
  • the size of the abrasive grains used for the buffing finish is not particularly limited, but #400 or less is preferable because the unevenness of the surface of the metal material tends to be smaller. Buffing is preferably performed before electropolishing.
  • the metal material may be processed by combining one or more of multi-stage buffing, acid cleaning, magnetic fluid polishing, and the like, which are performed by changing the count such as the size of the abrasive grains.
  • the liquid used for washing may be appropriately selected according to the application, but the above composition, a liquid obtained by diluting the above composition, or a liquid containing at least one of the components added to the above composition is preferable. .
  • the inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) with a purity of 99.99995% by volume or more.
  • an inert gas nitrogen, argon, etc.
  • a gas with a low water content is particularly preferred.
  • the liquid container may be transported and stored at room temperature, but the temperature may be controlled within the range of -20°C to 20°C in order to prevent deterioration.
  • the composition is typically applied to a substrate containing a metal-based material, which is a metal-containing material. Can be used in contact.
  • the substrate may contain a plurality of types of metallic materials.
  • the composition may dissolve at least one of the metal-based materials that may be contained in a plurality of types.
  • Metallic materials include metal atoms (cobalt (Co), ruthenium (Ru), molybdenum (Mo), aluminum (Al), copper (Cu), titanium (Ti), tungsten (W), and/or tantalum (Ta ), etc.), and examples thereof include single metals, alloys, metal oxides (which may be composite oxides), and metal nitrides (which may be composite nitrides).
  • the metallic material contained in the substrate is at least one selected from the group consisting of single metals, alloys, metal oxides and metal nitrides, and the dopant is selected from the group consisting of carbon, nitrogen, boron and phosphorus.
  • the content of metal atoms in the metallic material is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, even more preferably 50 to 100% by mass, relative to the total mass of the metallic material.
  • the content of the dopant of metal atoms is preferably 0.1 to 50% by mass, more preferably 10 to 40% by mass, based on the total mass of the metallic material.
  • the content of metal atoms in the metal-based material is preferably 30 to 99.9% by mass, more preferably 60 to 90% by mass, relative to the total mass of the metal-based material.
  • Examples of this treatment method include a substrate cleaning method having a cleaning step B of cleaning a substrate provided with a metal layer using the above composition (hereinafter also simply referred to as a “cleaning method”. Cleaning the substrate.
  • the method may include, prior to the washing step B, a composition manufacturing step A of preparing the above composition.
  • the substrate cleaning method the case where the composition production step A is performed before the cleaning step B is shown as an example, but the substrate cleaning method is not limited to this. It may be done using objects.
  • An object to be cleaned in the cleaning method is not particularly limited as long as it is a substrate having a metal layer, and a substrate having a metal layer containing at least Co or W is preferable. Moreover, as an object to be cleaned, a substrate provided with a metal layer containing Cu is also preferable, and a substrate further provided with a SiOx layer in addition to the metal layer is also preferable.
  • Examples of the object to be cleaned include a laminate having at least a metal layer, an interlayer insulating film, and a metal hard mask on a substrate in this order. The laminate may further have a hole formed from the surface (opening) of the metal hard mask toward the substrate so as to expose the surface of the metal layer through a dry etching process or the like.
  • the method for manufacturing a laminate having a hole as described above is not particularly limited, but usually, for an unprocessed laminate having a substrate, a metal layer, an interlayer insulating film, and a metal hard mask in this order, A dry etching process is performed using the metal hard mask as a mask to etch the interlayer insulating film so that the surface of the metal layer is exposed, thereby providing a hole penetrating through the metal hard mask and the interlayer insulating film. mentioned.
  • the method of manufacturing the metal hard mask is not particularly limited. For example, first, a metal layer containing a predetermined component is formed on the interlayer insulating film, and a resist film having a predetermined pattern is formed thereon.
  • a metal hard mask that is, a film in which a metal layer is patterned
  • the laminate may also have layers other than the layers described above, for example, layers such as an etch stop film, a barrier layer, and/or an antireflection layer.
  • FIG. 1 shows a schematic cross-sectional view showing an example of a laminate, which is an object to be cleaned in the above substrate cleaning method.
  • a laminate 10 shown in FIG. 1 includes a metal layer 2, an etching stop layer 3, an interlayer insulating film 4, and a metal hard mask 5 on a substrate 1 in this order.
  • a hole 6 is formed through which the layer 2 is exposed.
  • 1 includes a substrate 1, a metal layer 2, an etching stop layer 3, an interlayer insulating film 4, and a metal hard mask 5 in this order.
  • the inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a composed of the etching stop layer 3, the interlayer insulating film 4 and the metal hard mask 5, and a bottom wall 11b composed of the exposed metal layer 2.
  • the inner wall 11 is dry-etched. A residue 12 is attached.
  • the cleaning method can be suitably used for cleaning for the purpose of removing these dry etching residues 12 . That is, while being excellent in the removal performance (residue removability) of the dry etching residue 12, it is also excellent in corrosion resistance to the inner wall 11 (for example, the metal layer 2 etc.) of the object to be cleaned. Further, the substrate cleaning method described above may be applied to a laminate subjected to a dry ashing process after a dry etching process. Each layer constituent material of the laminate will be described below.
  • Metal hard masks include copper, cobalt, cobalt alloys, tungsten, tungsten alloys, ruthenium, ruthenium alloys, tantalum, tantalum alloys, aluminum oxide, aluminum nitride, aluminum nitride oxide, titanium aluminum, titanium, titanium nitride, titanium oxide, zirconium oxide. , hafnium oxide, tantalum oxide, lanthanum oxide, and yttrium alloy (preferably YSiOx).
  • Examples of materials for the metal hard mask include TiN, WO2 and ZrO2 .
  • the material of the interlayer insulating film is not particularly limited, and preferably has a dielectric constant k of 3.0 or less, more preferably 2.6 or less.
  • Specific materials for the interlayer insulating film include SiOx, SiN, SiOC, and organic polymers such as polyimide. Note that x is preferably a number represented by 1 to 3.
  • the material of the etching stop layer is not particularly limited. Specific materials for the etching stop layer include SiN, SiON, SiOCN-based materials, and metal oxides such as AlOx. Note that x is preferably a number represented by 1 to 3.
  • the material forming the metal layer that serves as the wiring material and/or the plug material is not particularly limited, but preferably contains one or more selected from the group consisting of cobalt, tungsten, molybdenum and copper. Also, the material forming the metal layer may be cobalt, tungsten, molybdenum, or an alloy of copper and other metals. The metal layer may further comprise metals other than cobalt, tungsten, molybdenum and copper, metal nitrides and/or alloys.
  • Metals other than cobalt, tungsten, molybdenum and copper that the metal layer may contain include, for example, titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxides, and aluminum.
  • the metal layer may contain at least one dopant selected from the group consisting of carbon, nitrogen, boron and phosphorous in addition to one or more selected from the group consisting of cobalt, tungsten, molybdenum and copper.
  • the “substrate” used herein includes, for example, a single-layer semiconductor substrate and a multi-layer semiconductor substrate.
  • the material constituting the single-layer semiconductor substrate is not particularly limited, and is generally preferably composed of silicon, silicon germanium, III-V group compounds such as GaAs, or any combination thereof.
  • its configuration is not particularly limited, for example, exposed integration of interconnect features such as metal lines and dielectric materials on a semiconductor substrate such as silicon as described above. It may have a circuit structure.
  • Metals and alloys used in interconnect structures include, but are not limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. not something.
  • the semiconductor substrate may also have layers such as interlevel dielectric layers, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.
  • the laminate may have a barrier layer.
  • a barrier layer is a layer formed between a metal layer that serves as a wiring material and/or a plug material provided on a substrate and an interlayer insulating film, and is a layer for preventing the wiring material and/or the plug material from diffusing ( membrane).
  • Materials for the barrier layer include low-resistance metal materials, and preferably contain at least one selected from the group consisting of tantalum or tantalum compounds, titanium or titanium compounds, tungsten or tungsten compounds, and ruthenium. It more preferably contains at least one selected from the group consisting of TiN, TiW, Ta, TaN, W, WN and Ru, and TiN is even more preferable.
  • the method for manufacturing the object to be cleaned is not particularly limited as long as it is a known method in the field of semiconductor substrates.
  • Methods for forming a metal layer (metal-containing film or metal-containing wiring) on a substrate include, for example, a sputtering method, a physical vapor deposition (PVD) method, and an atomic layer deposition (ALD) method. , chemical vapor deposition (CVD), and molecular beam epitaxy (MBE).
  • PVD physical vapor deposition
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • MBE molecular beam epitaxy
  • metal-containing substances are also present on the back surface of the substrate having the metal-containing film (the surface opposite to the metal-containing film side).
  • the metal-containing wiring may be formed on the substrate by carrying out the above method through a predetermined mask.
  • the substrate may be subjected to a different step or treatment and then used as the object to be treated in the present treatment method.
  • a substrate having a metal layer may be subjected to dry etching to produce a substrate having dry etching residue containing metal.
  • the dry etching residue is a by-product generated by dry etching (e.g., plasma etching), and includes, for example, photoresist-derived organic residue, interlayer insulating film-derived Si-containing residue, and , and metal-containing residues.
  • a substrate having a metal layer may be subjected to CMP to produce a substrate having metal inclusions.
  • composition manufacturing step A is a step of preparing the composition.
  • Each component used in this step is as described above. Further, the details of this step are as described in the section [Production method of composition] above.
  • the procedure of this step is not particularly limited, and examples thereof include a method of preparing a composition by stirring and mixing predetermined components.
  • each component may be added all at once, or may be added in portions over a plurality of times.
  • each component contained in the composition uses those classified as semiconductor grade or those classified as high-purity grade equivalent thereto, and removes foreign substances by filtering and / or reduces ionic components by ion exchange resin, etc. is preferably used.
  • after mixing the raw material components it is preferable to further remove foreign substances by filtering and/or reduce ion components by using an ion exchange resin or the like.
  • the composition is a concentrated solution
  • the concentrated solution is diluted 5 to 2000 times to obtain a diluted solution before carrying out the washing step B, and then the diluted solution is used to carry out the washing step B.
  • a solvent for diluting the concentrate at least one selected from the group consisting of water, alcohol and aprotic polar solvents contained in the composition is preferable.
  • Examples of the object to be cleaned in the cleaning step B include the laminate described above, and more specifically, a substrate provided with a metal layer containing at least one metal selected from the group consisting of Co and W. is mentioned. Further, as the object to be cleaned, as described above, the laminated body 10 in which holes are formed by the dry etching process is exemplified (see FIG. 1). A dry etching residue 12 adheres to the inside of the hole 6 in the laminate 10 . Also, a laminate subjected to a dry ashing process after a dry etching process may be used as an object to be cleaned.
  • the method of bringing the composition into contact with the object to be cleaned is not particularly limited. Methods of flowing the composition onto an object and any combination thereof are included. A method of immersing the object to be cleaned in the composition is preferred from the viewpoint of residue removability.
  • the temperature of the composition is preferably 90°C or less, more preferably 25 to 80°C, still more preferably 30 to 75°C, and particularly preferably 40 to 65°C.
  • the cleaning time can be adjusted depending on the cleaning method used and the temperature of the composition.
  • the washing time is, for example, within 90 minutes, preferably 10 to 90 minutes, and 5 to 90 minutes. 60 minutes is more preferred, and 10 to 45 minutes is even more preferred.
  • the washing time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, more preferably 15 seconds to 3 minutes, and even more preferably 20 seconds to 2 minutes.
  • Mechanical stirring methods include, for example, a method of circulating the composition over the object to be cleaned, a method of flowing or spraying the composition over the object to be cleaned, and stirring the composition with ultrasonic waves or megasonics. methods and the like.
  • the substrate cleaning method of the present invention may further include, after the cleaning step B, a step of cleaning the object to be cleaned by rinsing it with a solvent (hereinafter referred to as "rinsing step B2").
  • the rinsing step B2 is performed continuously with the washing step B, and is preferably a step of rinsing with a rinsing solvent (rinsing liquid) for 5 seconds to 5 minutes.
  • the rinsing step B2 may be performed using the mechanical agitation method described above.
  • solvents for the rinse solution include deionized water (DIW), methanol, ethanol, isopropanol, N-methylpyrrolidinone, ⁇ -butyrolactone, dimethylsulfoxide, ethyl lactate and propylene glycol monomethyl ether acetate.
  • DIW deionized water
  • methanol, ethanol, isopropanol, or a mixture thereof is preferable
  • DIW, isopropanol, or a mixture of DIW and isopropanol is more preferable.
  • the method of bringing the composition into contact with the object to be cleaned can be similarly applied.
  • the temperature of the rinsing solvent in the rinsing step B2 is preferably 10 to 40°C.
  • the substrate cleaning method of the present invention may have a drying step B3 for drying the object to be cleaned after the rinsing step B2.
  • a drying method is not particularly limited. Drying methods include, for example, a spin drying method, a method of flowing a dry gas over the object to be cleaned, a method of heating the substrate with a heating means such as a hot plate or an infrared lamp, a Marangoni drying method, a Rotagoni drying method, and IPA. (Isopropanol) drying methods, and any combination thereof.
  • the drying time in the drying step B3 depends on the specific drying method, but is preferably 20 seconds to 5 minutes.
  • the heating temperature for drying the substrate by heating is not particularly limited, but is, for example, 50 to 350.degree. C., preferably 150 to 250.degree.
  • the substrate cleaning method preferably includes a coarse particle removing step H for removing coarse particles in the composition after the composition producing step A and before the cleaning step B.
  • a coarse particle removing step H for removing coarse particles in the composition after the composition producing step A and before the cleaning step B.
  • the amount of coarse particles remaining on the object to be cleaned after the cleaning step B can be reduced.
  • Specific methods for removing coarse particles include, for example, a method of filtering and purifying the composition that has passed through the composition manufacturing step A using a particle-removing membrane having a predetermined particle-removing diameter.
  • the definition of coarse particles is as described above.
  • the method for cleaning the substrate includes, before the composition manufacturing step A, a static elimination step I in which static electricity is eliminated from water used for preparing the composition, and after the composition manufacturing step A, the cleaning Before the step B, it is preferable to include at least one step selected from the group consisting of a static elimination step J for performing static elimination on the composition.
  • the material of the wetted part for supplying the composition to the object to be cleaned is preferably formed or coated with a material that does not dissolve metals with respect to the composition. Examples of the above materials include the materials already described as the materials for the inner wall of the container that can be used for the liquid container. Note that the material may be a resin.
  • the resin When the material is a resin, the resin often has low electrical conductivity and is insulating. Therefore, for example, when the composition is passed through a pipe whose inner wall is formed or coated with a resin, or when it is filtered and purified by a resin particle removal membrane and a resin ion exchange resin membrane. In such a case, the electrification potential of the composition may increase and cause an electrostatic accident. Therefore, in the substrate cleaning method of the present invention, it is preferable to reduce the charge potential of the composition by performing at least one of the static elimination step I and the static elimination step J described above. In addition, by performing static elimination, adhesion of foreign matter (coarse particles, etc.) to the substrate and/or damage (corrosion) to the object to be cleaned can be further suppressed.
  • static elimination methods include a method of bringing water and/or a composition into contact with a conductive material.
  • the contact time for contacting water and/or the composition with the conductive material is preferably 0.001 to 1 second, more preferably 0.01 to 0.1 second.
  • resins examples include high-density polyethylene (HDPE), high-density polypropylene (PP), 6,6-nylon, tetrafluoroethylene (PTFE), copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), poly Chlorotrifluoroethylene (PCTFE), ethylene/chlorotrifluoroethylene copolymer (ECTFE), ethylene/tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene/propylene hexafluoride copolymer (FEP ).
  • Conductive materials include stainless steel, gold, platinum, diamond, and glassy carbon.
  • the substrate cleaning method includes a composition manufacturing step A, a cleaning step B, a waste liquid recovery step C for recovering the waste liquid of the composition used in the cleaning step B, and using the collected waste liquid of the composition.
  • a cleaning step D for cleaning a newly prepared substrate provided with a predetermined layer; and a waste liquid collecting step E for collecting waste liquid of the composition used in the cleaning step D
  • the substrate cleaning method may include repeating the cleaning step D and the waste liquid recovery step E to recycle the waste liquid of the composition.
  • composition manufacturing step A and the cleaning step B are as described above. Also in the embodiment in which the waste liquid is reused, it is preferable to have the coarse particle removal step H and the static elimination steps I and J.
  • the embodiment of the cleaning step D in which the substrate is cleaned using the collected waste liquid of the composition, is as described for the cleaning step B.
  • the collected waste liquid is preferably stored in the container in the static elimination step J, and a static elimination step similar to the static elimination step J may be performed at this time. Further, a step of removing impurities by filtering the recovered waste liquid may be provided.
  • Examples 1 to 30, Comparative Example 1 [Preparation of composition] Each component described in Table 1 was prepared, added at the blending ratio described in Table 1, and mixed to prepare each composition of Examples and Comparative Examples. In addition, in each composition, the content of each component (both based on mass) is as described in the table. Here, all of the various components shown in Table 1 used those classified as semiconductor grade or those classified as high-purity grade according thereto.
  • a laminate was prepared in which a SiO 2 film with a thickness of 100 nm, a metal hard mask (TiN), and a resist film were laminated in this order on a substrate (Si). This laminate is subjected to patterning processing by lithography, dry etching processing using a plasma etching apparatus for metal, and removal processing of the resist film by oxygen plasma ashing to form predetermined openings in the metal hard mask. A laminate for the evaluation test was produced.
  • plasma etching is performed with a fluorine-containing gas using a metal hard mask as a mask to etch the SiO2 film to a depth of about 50 nm, thereby forming a lattice pattern of 2 cm square.
  • a test piece for the evaluation test was manufactured.
  • fluorine was detected, which was presumed to be derived from dry etching residue.
  • the dry etching residue formed by plasma etching using the fluorine-containing gas is presumed to be an organic/inorganic mixed residue containing Si and O derived from SiO2 and C and F derived from the etching gas. be.
  • each composition was evaluated according to the following procedure. 200 mL of the composition was filled into a glass beaker with a volume of 500 mL. The temperature of the composition was raised to 40° C. while stirring with a stir bar. Then, while stirring, the test piece prepared above was immersed in the composition at a liquid temperature of 40°C for 2 minutes to wash the test piece. While the specimen was immersed in the composition, the specimen was held with 4 inch long plastic locking tweezers so that the side of the specimen from which the debris had been removed faced the stirrer.
  • the specimen was immediately removed from the composition and placed in 400 mL of gently stirred DI water (20° C. water temperature) filled in a 500 mL capacity plastic beaker. While immersing the specimen in DI water, the specimen was held with 4 inch long plastic locking tweezers so that the side of the specimen from which the debris had been removed faced the stirrer. After immersing the specimen in DI water for 30 seconds, the specimen was immediately removed and rinsed under DI water flow at 20°C for 30 seconds. While rinsing the specimen under the DI water stream, the specimen was held with 4-inch long plastic locking tweezers so that the side of the specimen from which the debris had been removed faced the DI water stream.
  • test piece was removed from the holding portion of the plastic tweezers, and placed in a lidded plastic storage box with the element side up for storage.
  • the composition analysis of the surface of the obtained test piece was performed by XPS.
  • the surface of the test piece is measured using an XPS device (manufactured by Ulvac-PHI, trade name Quantera SXM), and the content of fluorine atoms derived from the dry etching residue on the surface of the test piece (atomic %) From the measurement results, the residue Removability (removability of dry etching residue) was evaluated. It can be said that when the fluorine atom content on the surface of the test piece is small, the residue removability is excellent, and when the fluorine atom content is large, the residue removability is poor.
  • a substrate was prepared by forming a cobalt film (Co film) on one surface of a commercially available silicon wafer (diameter: 12 inches) by CVD (Chemical Vapor Deposition). The thickness of the formed Co film was 30 nm.
  • the obtained Co films were etched using the compositions of Examples and Comparative Examples. Specifically, the Co film was immersed in the compositions of Examples and Comparative Examples for 10 minutes, and then rinsed twice in pure water for 15 seconds, followed by drying the substrate with nitrogen gas. The etching rate ( ⁇ /min) was calculated based on the difference in film thickness of the Co film before and after immersion in the composition. The corrosion resistance of the composition was evaluated from the measured etching rate of each film. It can be said that when the etching rate is low, the corrosion resistance is excellent, and when the etching rate is high, the corrosion resistance is inferior.
  • Substrates having a film made of W (W film), a film made of TiN (TiN film), a film made of AlOx (AlOx film), and a film made of Mo (Mo film) were prepared in the same manner as above. , each substrate was immersed in each composition, and the etching rate ( ⁇ /min) of each film was measured.
  • the W film, the TiN film and the AlOx film were formed by the CVD method, and the Mo film was formed by the PVD (Physical Vapor Deposition) method.
  • the thickness of each film formed on the substrate was measured by the following method.
  • the thicknesses of the Co film, W film and TiN film were measured by X-ray fluorescence analysis (XRF) using an X-ray fluorescence spectrometer ("AZX400” manufactured by Rigaku).
  • the thickness of the AlOx film was measured using ellipsometry (spectroscopic ellipsometer, trade name "Vase", manufactured by JA Woollam Japan) under the conditions of a measurement range of 250-1000 nm and a measurement angle of 70 degrees and 75 degrees. It was measured.
  • the thickness of the Mo film was measured by a four-probe method using a resistivity measuring device (“VR300DE” manufactured by Kokusai Denki Semiconductor Service Co., Ltd.). Table 1 summarizes the measurement results.
  • a wafer surface inspection device (SP-5, manufactured by KLA-Tencor) was used to measure the number of particles with a diameter of 19 nm or more present on the surface of a silicon substrate (wafer) with a diameter of 300 mm and the address of each particle. Then, the wafer whose number of particles existing on the silicon substrate surface was measured was set in a spin rotary wafer processing apparatus (manufactured by ECK Technology Co., Ltd.). Next, each composition of Examples and Comparative Examples adjusted to 40° C. was discharged onto the surface of the set wafer at a flow rate of 1.5 L/min for 1 minute.
  • Table 1 shows the compositions of the compositions used and the evaluation results in each example and each comparative example.
  • the "ratio 1" column indicates the ratio of the content of the azole compound to the content of component A in each composition (azole compound/component A) in terms of mass ratio
  • the "ratio 2" column indicates each composition.
  • the ratio of the content of the aprotic polar solvent to the content of component A in (aprotic polar solvent/component A) is shown as a mass ratio.
  • the expression “5.0E+04" in the column “ratio 1" in Example 8 means that the ratio 1 (azole compound/component A) was "5.0 ⁇ 10 4 " by mass. means.
  • the "pH” column shows the pH at 25°C of each composition measured using a pH meter.
  • Examples 31 to 41 [Preparation of composition] Prepare t-butanol, sulfolane, 1,2,4-triazole, 2-aminoethanol, deionized water, and a chelating agent described in Table 2 below, mix these components, and prepare Examples 31 to 41 respective compositions were prepared.
  • the contents of t-butanol, sulfolane, 1,2,4-triazole and deionized water contained in each composition of Examples 31 to 41 are shown in Table 1 for each component contained in the composition of Example 2. was the same as the content of The content of 2-aminoethanol was adjusted so that the pH of each composition of Examples 31 to 41 was the value shown in Table 2, "pH" column.
  • Table 2 shows the type and content of the chelating agent contained in each composition.
  • the chelating agents used in the preparation of the compositions of Examples 31-41 are shown below.
  • As the chelating agent a compound classified as a semiconductor grade or a compound classified as a high-purity grade corresponding thereto was used.
  • ⁇ CA1 ethylenediaminetetraacetic acid
  • ⁇ CA2 diethylenetriaminepentaacetic acid
  • ⁇ CA3 citric acid
  • ⁇ CA4 N,N,N',N'-ethylenediaminetetrakis (methylene phosphonic acid)
  • ⁇ CA5 gluconic acid
  • ⁇ CA6 malonic acid
  • ⁇ CA7 iminodiacetic acid
  • Table 2 shows the evaluation results of the composition of each example.
  • the meaning of each column in Table 2 other than the "chelating agent” column is the same as in Table 1.
  • Example 42-45 [Preparation of composition]
  • the compositions of Examples 42-45 were prepared by the following procedure.
  • the chelating agent used was the same as the chelating agent used in the preparation of the compositions of Examples 31-41.
  • the notation of each chelating agent is also the same as described above.
  • Example 11 In the formulation of Example 11, except that the content of deionized water was adjusted, 0.1% by mass of CA1 was added as a chelating agent, and the pH of the composition was adjusted to 10.5 by the content of 2-aminoethanol. , the composition of Example 42 was prepared in the same manner as the composition of Example 11.
  • a composition of Example 43 was prepared in the same manner as in Example 42, except that the chelating agent in the formulation of Example 42 was changed to 1.0% by mass of CA1.
  • a composition of Example 44 was prepared in the same manner as in Example 42, except that the chelating agent in the formulation of Example 42 was changed to 0.1% by mass of CA3.
  • a composition of Example 45 was prepared in the same manner as in Example 42, except that the chelating agent in the formulation of Example 42 was changed to a mixture of 0.05% by mass of CA2 and 0.05% by mass of CA6.

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WO2017126554A1 (ja) * 2016-01-22 2017-07-27 富士フイルム株式会社 処理液

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