WO2022024714A1 - Solution de nettoyage de substrat semi-conducteur - Google Patents

Solution de nettoyage de substrat semi-conducteur Download PDF

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Publication number
WO2022024714A1
WO2022024714A1 PCT/JP2021/025893 JP2021025893W WO2022024714A1 WO 2022024714 A1 WO2022024714 A1 WO 2022024714A1 JP 2021025893 W JP2021025893 W JP 2021025893W WO 2022024714 A1 WO2022024714 A1 WO 2022024714A1
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Prior art keywords
group
acid
semiconductor substrate
cleaning liquid
mass
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PCT/JP2021/025893
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English (en)
Japanese (ja)
Inventor
直子 大内
哲也 上村
祐継 室
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富士フイルムエレクトロニクスマテリアルズ株式会社
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Priority to JP2022540127A priority Critical patent/JP7469474B2/ja
Publication of WO2022024714A1 publication Critical patent/WO2022024714A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a cleaning liquid for a semiconductor substrate.
  • Semiconductor elements such as CCD (Charge-Coupled Device) and memory are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, a resist film is formed on a laminate having a metal film as a wiring material, an etching stop layer, and an interlayer insulating layer on a substrate, and a photolithography step and a dry etching step (for example, plasma etching treatment). ) Is performed to manufacture a semiconductor element.
  • CCD Charge-Coupled Device
  • memory are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, a resist film is formed on a laminate having a metal film as a wiring material, an etching stop layer, and an interlayer insulating layer on a substrate, and a photolithography step and a dry etching step (for example, plasma etching treatment). ) Is performed to manufacture a semiconductor element.
  • a dry etching step for example, plasma etching treatment
  • CMP chemical mechanical polishing
  • a polishing slurry containing polishing fine particles for example, silica, alumina, etc.
  • Chemical Mechanical Polishing processing may be performed.
  • the polishing fine particles used in the CMP treatment, the polished wiring metal film, and / or the metal component derived from the barrier metal and the like tend to remain on the surface of the semiconductor substrate after the CMP treatment. Since these residues can short-circuit the wiring and affect the electrical characteristics of the semiconductor, a cleaning step of removing these residues from the surface of the semiconductor substrate is generally performed.
  • Patent Document 1 states that "a compound having a carboxyl group and / or a carboxylate group and having a structure in which a hydroxyl group is bonded to carbons at the ⁇ and ⁇ positions of the carboxyl group and / or the carboxylate group. (A) and a cleaning agent for electronic materials containing water. "
  • the present inventors have studied the cleaning liquid for semiconductor substrates described in Patent Document 1 and the like, and found that they show excellent cleaning performance for a semiconductor substrate having a metal film containing tungsten after CMP treatment, and that tungsten is used. It was found that it is difficult to achieve both excellent corrosion suppression performance against tungsten when cleaning the metal film containing it.
  • the present invention is for a semiconductor substrate which exhibits excellent cleaning performance for a semiconductor substrate having a metal film containing tungsten after CMP treatment and also has excellent corrosion suppressing performance against tungsten when cleaning a metal film containing tungsten.
  • the subject is to provide a cleaning solution.
  • the present inventor has found that the above problem can be solved by the following configuration.
  • a cleaning liquid for a semiconductor substrate used for cleaning a semiconductor substrate Contains polymers, alkanolamines, complexing agents with acid groups, and water.
  • the weight average molecular weight of the polymer is 2000-900000, and the polymer has a weight average molecular weight of 2000-90000.
  • the content of the complexing agent is 2.5% by mass or more and less than 20.0% by mass with respect to the total mass of the cleaning liquid for semiconductor substrates.
  • a cleaning liquid for a semiconductor substrate, wherein the pH of the cleaning liquid for a semiconductor substrate is less than 7.0.
  • a cleaning liquid for a substrate can be provided.
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the “content” of the component means the total content of the two or more kinds of components.
  • “ppm” means “parts-per-million ( 10-6 )” and “ppb” means “parts-per-billion ( 10-9 )”.
  • the described compounds may contain isomers (compounds having the same number of atoms but different structures), optical isomers, and isotopes, unless otherwise specified. Further, the isomers and isotopes may contain only one species, or may contain a plurality of species.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (both are trade names manufactured by Toso Co., Ltd.) as columns. Value converted using polystyrene, which is a standard material measured by a gel permeation chromatography (GPC) analyzer, using THF (tetrahydrogen) as an eluent, a differential refractometer as a detector, and polystyrene as a standard material.
  • GPC gel permeation chromatography
  • the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight.
  • the cleaning liquid for a semiconductor substrate (hereinafter, also referred to as "cleaning liquid") of the present invention is a cleaning liquid used for cleaning a semiconductor substrate, and has a predetermined polymer, an alkanolamine, and a predetermined amount of acid groups, which will be described later. It contains an agent and water, and the pH of the cleaning solution is less than 7.0.
  • the pH of the cleaning solution is less than 7.0.
  • the pH of the cleaning liquid is preferably 0.1 to 6.9, more preferably 1.0 to 6.9, and even more preferably 2.0 to 6.9 in that the effect of the present invention is more excellent.
  • 2.5 to 6.0 are particularly preferable, and 5.0 to 6.5 are most preferable.
  • the pH of the washing liquid can be measured by a method according to JIS Z8802-1984 using a known pH meter.
  • the pH is a value at a measurement temperature of 25 ° C.
  • the cleaning liquid contains a polymer.
  • the weight average molecular weight (Mw) of the polymer is 2000 to 900,000, and 2000 to 800,000 is preferable, 2000 to 500,000 is more preferable, 2000 to 50000 is further preferable, and 2000 to 30000 is more preferable in that the effect of the present invention is more excellent. Is particularly preferable.
  • the value of the weight average molecular weight is the value of the weight average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography).
  • a water-soluble polymer is preferable.
  • the "water-soluble polymer” is a compound in which two or more structural units are connected in a linear or network shape via covalent bonds, and the mass of the polymer dissolved in 100 g of water at 20 ° C. is 0.1 g. The above compounds are intended.
  • the cleaning performance of the cleaning liquid is improved by interacting with the substrate having a metal film or the polishing fine particles (for example, silica and alumina) contained in the polishing slurry.
  • water-soluble polymer examples include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polystyrene sulfonic acid, and salts thereof; styrene, ⁇ -methylstyrene, and / or.
  • Polymers of monomers such as 4-methylstyrene and monomers of (meth) acrylic acid and / or acids such as maleic acid and salts thereof; (meth) acrylic acid and malein.
  • Polymers with acids and salts thereof benzenesulfonic acid and / or polymers having structural units having aromatic hydrocarbon groups condensed with naphthalenesulfonic acid and the like with formalin, and salts thereof.
  • Vinyl-based synthetic polymers such as polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyacrylamide, polyvinylformamide, polyethyleneimine, polyvinyloxazoline, polyvinylimidazole, and polyallylamine; hydroxyethylcellulose, carboxymethylcellulose, and processing. Examples thereof include modified products of natural polysaccharides such as starch.
  • the water-soluble polymer a polymer having an acid group (for example, a carboxy group, a phosphoric acid group, and a sulfonic acid group) is preferable, and polyacrylic acid, polymaleic acid, styrene and (meth) acrylic acid, And / or a polymer with an acid monomer such as maleic acid, a copolymer of (meth) acrylic acid with maleic acid, or salts thereof are more preferred.
  • an acid group for example, a carboxy group, a phosphoric acid group, and a sulfonic acid group
  • polyacrylic acid, polymaleic acid, styrene and (meth) acrylic acid, And / or a polymer with an acid monomer such as maleic acid, a copolymer of (meth) acrylic acid with maleic acid, or salts thereof are more preferred.
  • the water-soluble polymer may be a homopolymer or a copolymer obtained by copolymerizing two or more kinds of monomers.
  • the monomer include a monomer having a carboxy group, a monomer having a sulfonic acid group, a monomer having a hydroxyl group, a monomer having a polyethylene oxide chain, and a monomer having an amino group.
  • a monomer selected from the group consisting of monomers having a heterocycle As the water-soluble polymer, a polymer consisting substantially only of structural units derived from the monomers selected from the above group is preferable.
  • the water-soluble polymer is substantially only the structural unit derived from the monomer selected from the above group means that, for example, the content of the structural unit derived from the monomer selected from the above group is It means that it is 95 to 100% by mass (preferably 99 to 100% by mass) with respect to the total mass of the polymer.
  • the polymer preferably has a structural unit having a carboxy group (a structural unit derived from (meth) acrylic acid, etc.).
  • the content of the structural unit having a carboxy group is preferably 30 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 85 to 100% by mass, based on the total mass of the polymer.
  • polymer examples include water-soluble polymers described in paragraphs [0043] to [0047] of JP-A-2016-171294, and the contents thereof are incorporated in the present specification.
  • the polymer may be used alone or in combination of two or more.
  • the content of the polymer is preferably 0.01 to 10% by mass, more preferably 0.05 to 3% by mass, still more preferably 0.5 to 2% by mass, based on the total mass of the washing liquid.
  • the content of the polymer is within the above range, the polymer is appropriately adsorbed on the surface of the substrate and can contribute to the improvement of the corrosion suppressing performance of the cleaning liquid, and the viscosity and / or the cleaning performance of the cleaning liquid is well balanced. Can be done.
  • the content of the polymer is preferably 1.0 to 45.0% by mass, more preferably 10.0 to 45.0% by mass, and 10.0 to 40% by mass with respect to the total mass of the washing liquid excluding the solvent. 0% by mass is more preferable.
  • the cleaning solution contains an alkanolamine.
  • the alkanolamine is a compound having at least one of a primary amino group to a tertiary amino group and further having at least one hydroxyl group (preferably a hydroxyalkyl group) in the molecule.
  • Alkanolamines do not contain the quaternary ammonium compounds described below.
  • the number of hydroxyl groups contained in the alkanolamine is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2.
  • the total number of primary amino groups to tertiary amino groups contained in the alkanolamine is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.
  • the alkanolamine preferably has any of a primary amino group to a tertiary amino group, and more preferably has any of a primary amino group and a secondary amino group. It is more preferable to have a primary amino group.
  • the compound represented by the formula (A) is preferable.
  • Ra1 and Ra2 each independently represent an alkyl group which may have a hydrogen atom or a hydroxyl group.
  • the alkyl group may be linear or branched.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
  • the number of hydroxyl groups contained in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.
  • La1 represents an alkylene group which may have a hydroxyl group.
  • the alkylene group may be linear or branched.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the number of hydroxyl groups contained in the alkylene group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 0.
  • alkanolamine examples include monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), tris (hydroxymethyl) aminomethane, N-methylethanolamine, N-methyl-N, N-diethanolamine, and the like.
  • alkanolamines are isopropanolamine, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), tris (hydroxymethyl) aminomethane, N-ethylethanolamine, monopropanolamine and triisopropanolamine.
  • MEA monoethanolamine
  • DEA diethanolamine
  • TEA triethanolamine
  • N-Methylethanolamine, 2-amino-2-methyl-1-propanol, and 2- (dimethylamino) -2-methyl-1-propanol preferably at least one selected from the group.
  • the pKa (acid dissociation constant) of the alkanolamine is preferably 5.00 to 20.00, more preferably 7.50 to 15.00, and 9.00 to 14.50 from the viewpoint of excellent stability of the washing solution over time. More preferred.
  • at least one alkanolamine satisfies the above pKa range, more preferably the alkanolamine having the highest content satisfies the above pKa range, and the total mass of the alkanolamine.
  • pKa is a value obtained by using SC-Database (http://acadsoft.co.uk/scdbase/SCDB_software/scdb_download.htm).
  • the ClogP value of the alkanolamine is preferably -5.00 to 1.00, more preferably -2.00 to 1.00, and even more preferably -1.00 to 1.00.
  • the LogP value is a value obtained by calculating the common logarithm logP of 1-octanol and the partition coefficient P to water.
  • known ones can be used.
  • the Clog value is a value using the ClogP program incorporated in ChemBioDrowUltra12.0 of Cambridgest.
  • the alkanolamine may be used alone or in combination of two or more.
  • the content of alkanolamine is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 7.0% by mass, based on the total mass of the cleaning liquid, because the performance of the cleaning liquid is well-balanced. 0.01 to 5.0% by mass is more preferable, 0.01 to 3.0% by mass is particularly preferable, and 0.01 to 2.0% by mass is most preferable.
  • the content of alkanolamine is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 30.0% by mass, and 1.0 to 30% with respect to the total mass of the cleaning liquid excluding the solvent. 0% by mass is more preferable, and 1.0 to 25.0% by mass is particularly preferable.
  • the cleaning liquid contains a complexing agent having an acid group (hereinafter, also referred to as "specific complexing agent").
  • the specific complexing agent is a compound having an acid group and binding to a metal ion to form a complex ion.
  • the specific complexing agent is a compound different from the components contained in the cleaning liquid described above, the surfactant, the anticorrosive agent, the preservative, and the pH adjuster described later.
  • the content of the specific complexing agent is 2.5% by mass or more and less than 20.0% by mass with respect to the total mass of the cleaning liquid, and 2.5 to 18.5% by mass is used from the viewpoint of improving the cleaning performance.
  • the content of the specific complexing agent is preferably 45.0 to 98.0% by mass, more preferably 50.0 to 95.0% by mass, and 50.0 to 50.0 to 98.0% by mass with respect to the total mass of the cleaning liquid excluding the solvent. 90.0% by mass is more preferable, 50.0 to 85.0% by mass is particularly preferable, and 50.0 to 70.0% by mass is most preferable.
  • the acid group contained in the specific complexing agent examples include a carboxy group, a phosphoric acid group, a sulfonic acid group, a phosphonic acid group, a sulfinic acid group, and a sulfenic acid group.
  • the specific complexing agent preferably has at least one selected from the group consisting of a carboxy group, a phosphoric acid group, a phosphonic acid group, and a sulfonic acid group, and preferably has a carboxy group, a phosphonic acid group, and a sulfonic acid group.
  • the specific complexing agent preferably has any one of a carboxy group, a phosphoric acid group, a phosphonic acid group, and a sulfonic acid group.
  • the number of acid groups contained in the specific complexing agent is preferably 1 to 10, more preferably 1 to 7, further preferably 1 to 6, and particularly preferably 1 to 4.
  • a complexing agent having a carboxy group is a complexing agent having at least one carboxy group in the molecule.
  • the specific complexing agent having a carboxy group include aminopolycarboxylic acid, amino acid, aliphatic carboxylic acid, and aromatic carboxylic acid. Among them, as the specific complexing agent having a carboxy group, an aminopolycarboxylic acid or an amino acid is preferable, and an aminopolycarboxylic acid is more preferable.
  • the amino acid When the specific complexing agent contains an amino acid, the amino acid has a coordination portion and a hydrophilic portion in the molecule, so that the amino acid is applied to the abrasive fine particles (for example, silica, alumina, etc.) contained in the substrate having a metal film or the polishing slurry.
  • the abrasive fine particles for example, silica, alumina, etc.
  • the number of carboxy groups contained in the specific complexing agent is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 4.
  • aminopolycarboxylic acid a compound represented by the formula (B1) is preferable.
  • n 1 represents an integer from 1 to 10. Among them, as n 1 , an integer of 1 to 5 is preferable, an integer of 1 to 3 is more preferable, and an integer of 2 to 3 is further preferable.
  • aminopolycarboxylic acid examples include nitrilotriacetic acid, butylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexacacetic acid, 1,3-diamino-2-hydroxypropane-N, N.
  • N', N'-tetraacetic acid propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediaminetetraacetic acid, ethylenediaminediaminepropionic acid, 1,6-hexamethylene-diamine -N, N, N', N'-tetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetate, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclo Included are dodecane-tetraacetic acid, diaminopropanol tetraacetic acid, (hydroxyethyl) ethylenediaminetriacetic acid, and iminodiacetic acid (IDA).
  • DTPA or EDTA is preferable as the aminopolycarboxylic acid
  • the compound represented by the formula (B2) is preferable, and the compound represented by the formula (B3) is more preferable.
  • R b1 represents a hydrocarbon group which may have a hydrogen atom or a hetero atom.
  • the hydrocarbon group may be linear, branched, or cyclic (may be monocyclic or polycyclic).
  • the hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms.
  • Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
  • an alkyl group, an alkenyl group, an alkylene group, or an aryl group which may have a heteroatom is preferable, and an alkyl group which may have a heteroatom is more preferable.
  • R b2 and R b3 independently represent a hydrogen atom or a hydroxyalkyl group, respectively.
  • the hydroxyl alkyl group (alkyl group having a hydroxy group) has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms.
  • Examples of the hydroxylalkyl group include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl group. Of these, a hydroxyethyl group is preferable.
  • R b4 represents a hydrogen atom, a hydroxyl group, a carboxy group, or -SR b7 .
  • R b7 represents a hydrogen atom or an alkyl group.
  • the alkyl group may be linear, branched or cyclic.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably a methyl group.
  • L b1 represents a single bond or an alkylene group.
  • the alkylene group may be linear, branched, or cyclic.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • R b5 and R b6 are synonymous with R b2 and R b3 in the above-mentioned formula (B2), and the preferable range is also the same.
  • amino acids examples include alanine (2-aminopropionic acid or 3-aminopropionic acid), arginine, asparagine, aspartic acid, cystine, cysteine, glutamine, glutamic acid, glycine or its derivatives, isoleucine, leucine, lysine, methionine, phenylalanine. , Serin, etionin, threonine, tyrosine, valine, tryptophan, histidine or derivatives thereof, 2-amino-3-aminopropaneic acid, and proline.
  • the amino acid include the compounds described in paragraphs [0021] to [0023] of JP-A-2016-086094.
  • the glycine derivative examples include N, N-di (2-hydroxyethyl) glycine.
  • the histidine derivative the compounds described in JP-A-2015-165561 and JP-A-2015-165562 can be incorporated, and the contents thereof are incorporated in the present specification.
  • the amino acid may contain at least one selected from the group consisting of serine, alanine, glycine or a derivative thereof, methionine, histidine or a derivative thereof, arginine, glutamic acid, asparagine, aspartic acid, glutamic acid, and cysteine.
  • the aliphatic carboxylic acid is a compound having a carboxy group and an aliphatic group in the molecule. Moreover, it is preferable that the aliphatic carboxylic acid further has a hydroxyl group.
  • a compound represented by the formula (B4) is preferable.
  • L b2 represents a single bond or a divalent linking group.
  • the divalent linking group represented by L b2 include an ether group, a carbonyl group, an ester group, a thioether group, -SO 2- , and -NT- (T is a substitution of, for example, a hydrogen atom or an alkyl group).
  • Group a divalent hydrocarbon group (for example, an alkylene group, an alkenylene group, an alkynylene group, and an arylene group), and a group combining these groups can be mentioned.
  • the divalent linking group may be linear, branched or cyclic.
  • the divalent linking group represented by L b2 may further have a substituent.
  • substituents examples include an alkyl group, an aryl group, a hydroxyl group, a carboxy group, an amino group, and a halogen atom.
  • divalent linking group a single bond or a divalent hydrocarbon group is preferable, and an alkylene group is more preferable.
  • the number of carbon atoms of the divalent linking group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5.
  • the aliphatic carboxylic acid examples include gluconic acid, glycolic acid, glyceric acid, citric acid, maleic acid, malic acid, tartaric acid, oxalic acid, malonic acid, and succinic acid.
  • the aliphatic carboxylic acid is preferably contained at least one selected from the group consisting of citric acid, tartaric acid, and succinic acid.
  • Aromatic carboxylic acid is a compound having a carboxy group and an aromatic group in the molecule.
  • Examples of the aromatic carboxylic acid include phenyllactic acid, hydroxyphenyllactic acid, and phenylsuccinic acid.
  • a complexing agent having a phosphoric acid group is a complexing agent having at least one phosphoric acid group in the molecule.
  • the complexing agent having a phosphoric acid group is a compound different from the above-mentioned complexing agent.
  • the number of phosphoric acid groups contained in the specific complexing agent is preferably 1 to 10, more preferably 2 to 8, and even more preferably 4 to 7.
  • the complexing agent having a phosphoric acid group examples include polyphosphoric acid such as diphosphoric acid, metaphosphoric acid, and hexametaphosphoric acid, and phytic acid.
  • polyphosphoric acid such as diphosphoric acid, metaphosphoric acid, and hexametaphosphoric acid
  • phytic acid examples include diphosphate, hexametaphosphoric acid, or phytic acid.
  • diphosphate, hexametaphosphoric acid, or phytic acid is preferable, and phytic acid is more preferable.
  • a complexing agent having a sulfonic acid group is a complexing agent having at least one sulfonic acid group in the molecule.
  • the complexing agent having a sulfonic acid group is a compound different from the above-mentioned complexing agent.
  • the number of sulfonic acid groups contained in the specific complexing agent is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
  • a compound represented by the formula (C) is preferable.
  • RC represents an alkyl or aryl group which may have a substituent.
  • the alkyl group which may have a substituent represented by RC may be linear, branched or cyclic (may be monocyclic or polycyclic).
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • the aryl group which may have a substituent represented by RC may be a monocyclic ring, a polycyclic ring, or a fused ring.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 8 carbon atoms.
  • substituent having the alkyl group and the aryl group include an alkyl group, an aryl group, a hydroxyl group, a carboxy group, an amino group and a halogen atom, and an alkyl group is preferable.
  • the complexing agent having a sulfonic acid group examples include naphthalene sulfonic acid, p-toluene sulfonic acid, camphor sulfonic acid, benzene sulfonic acid, methane sulfonic acid, and ethane sulfonic acid. Among them, p-toluenesulfonic acid, methanesulfonic acid, or ethanesulfonic acid is preferable as the complexing agent having a sulfonic acid group.
  • a complexing agent having a phosphonic acid group is a complexing agent having at least one phosphonic acid group in the molecule.
  • the complexing agent having a phosphonic acid group is a compound different from the complexing agent described above.
  • the number of phosphonic acid groups contained in the specific complexing agent is preferably 1 or more, more preferably 2 or more, further preferably 2 to 10, particularly preferably 2 to 4, and most preferably 2 to 3.
  • Examples of the complexing agent having a phosphonic acid group include a compound represented by the formula (P1), a compound represented by the formula (P2), and a compound represented by the formula (P3).
  • X represents a hydrogen atom or a hydroxyl group.
  • a hydroxyl group is preferable.
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • the alkyl group having 1 to 10 carbon atoms represented by R 11 may be linear, branched or cyclic.
  • R11 an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable.
  • n- represents a normal-form.
  • Examples of the compound represented by the formula (P1) include ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropyriden-1,1'-diphosphonic acid, or 1 -Hydroxybutylidene-1,1'-diphosphonic acid is preferred.
  • HEDPO 1-hydroxyethylidene-1,1'-diphosphonic acid
  • 1-hydroxypropyriden-1,1'-diphosphonic acid or 1 -Hydroxybutylidene-1,1'-diphosphonic acid is preferred.
  • Q represents a hydrogen atom or R 13 -PO 3 H 2 .
  • R 12 and R 13 each independently represent an alkylene group.
  • Examples of the alkylene group represented by R 12 include an alkylene group having 1 to 12 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, and is preferably linear or branched.
  • an alkylene group having 1 to 6 carbon atoms is preferable, an alkylene group having 1 to 4 carbon atoms is more preferable, and an ethylene group is further preferable.
  • Examples of the alkylene group represented by R 13 include an alkylene group having 1 to 10 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, and is preferably linear or branched.
  • an alkylene group having 1 to 4 carbon atoms is preferable, a methylene group or an ethylene group is more preferable, and a methylene group is further preferable.
  • Y represents a hydrogen atom, -R 13 -PO 3 H 2 , or a group represented by the formula (P4).
  • a group represented by -R 13 -PO 3 H 2 or the formula (P4) is preferable, and a group represented by the formula (P4) is more preferable.
  • Q and R 13 are synonymous with Q and R 13 in formula (P2).
  • Examples of the compound represented by the formula (P2) include ethylaminobis (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid) (NTPO), and ethylenediaminebis (methylenephosphonic acid) (EDDPO).
  • 1,3-propylene diaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) (EDTPO), ethylenediaminetetra (ethylenephosphonic acid), 1,3-propylenediaminetetra (methylenephosphonic acid) (PDTMP), 1,2-Diaminopropanetetra (methylenephosphonic acid) or 1,6-hexamethylenediaminetetra (methylenephosphonic acid) is preferable.
  • R 14 and R 15 each independently represent an alkylene group having 1 to 4 carbon atoms.
  • the alkylene group having 1 to 4 carbon atoms represented by R 14 and R 15 may be linear or branched.
  • Examples of the alkylene group having 1 to 4 carbon atoms represented by R 14 and R 15 include a methylene group, an ethylene group, a propylene group, a trimethylene group, an ethylmethylene group, a tetramethylene group, a 2-methylpropylene group and 2-. Examples thereof include a methyltrimethylene group and an ethylethylene group, and an ethylene group is preferable.
  • n represents an integer of 1 to 4. Among them, n is preferably an integer of 1 to 2.
  • At least four of Z 1 to Z 4 and n Z 5s represent an alkyl group having a phosphonic acid group, and the rest represent an alkyl group.
  • Examples of the alkyl group in the alkyl group having an alkyl group and a phosphonic acid group represented by Z 1 to Z 5 include a linear alkyl group having 1 to 4 carbon atoms and a branched chain having 1 to 4 carbon atoms. Alkyl groups are mentioned, and methyl groups are preferable.
  • the number of phosphonic acid groups in the alkyl group having a phosphonic acid group represented by Z 1 to Z 5 is preferably 1 to 2, more preferably 1.
  • Examples of the alkyl group having a phosphonic acid group represented by Z 1 to Z 5 include a linear or branched alkyl group having 1 to 4 carbon atoms and having 1 or 2 phosphonic acid groups.
  • the (mono) phosphonomethyl group or the (mono) phosphonoethyl group is preferable, and the (mono) phosphonomethyl group is more preferable.
  • Z 1 to Z 5 it is preferable that all of Z 1 to Z 4 and n Z 5 are the above-mentioned alkyl groups having a phosphonic acid group.
  • Examples of the compound represented by the formula (P3) include diethylenetriaminepenta (methylenephosphonic acid) (DEPPO), diethylenetriaminepenta (ethylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), or triethylenetetraminehexa (ethylenephosphon). Acid) is preferred.
  • Examples of the complexing agent having a phosphonic acid group include the compounds described in paragraphs [0026] to [0036] of International Publication No. 2018/020878, and paragraphs [0031] of International Publication No. 2018/030006.
  • the compounds ((co) polymers) described in [0046] can be incorporated, and the contents thereof are incorporated in the present specification.
  • the carbon number of the complexing agent having a phosphonic acid group is preferably 12 or less, more preferably 10 or less, still more preferably 8 or less.
  • the lower limit is not particularly limited, and 1 or more is preferable, and 2 or more is more preferable.
  • the complexing agent having a phosphonic acid group the compound represented by the above formula (P1), the compound represented by the formula (P2), or the compound represented by the formula (P3) is preferable, and HEDPO is more preferable. preferable.
  • the specific complexing agent includes a compound represented by the formula (B1), a compound represented by the formula (B2), a compound represented by the formula (B4), a compound represented by the formula (C), and a phosphoric acid group. It is preferable to contain at least one selected from the group consisting of the complexing agent having and the compound represented by the formula (P1), and the compound represented by the formula (B1) and the compound represented by the formula (B3). It is selected from the group consisting of a compound, a compound represented by the formula (B4), a compound represented by the formula (C), diphosphate, hexametaphosphate, phytic acid, and a compound represented by the formula (P1).
  • the specific complexing agent may form a salt.
  • the salt include alkali metal salts such as sodium salt and potassium salt, ammonium salt, hydrochloride, carbonate, and acetate.
  • the molecular weight of the specific complexing agent is preferably 600 or less, more preferably 450 or less, still more preferably 300 or less.
  • the lower limit of the molecular weight is not particularly limited, and is preferably 50 or more.
  • the carbon number of the specific complexing agent is preferably 15 or less, more preferably 10 or less.
  • the lower limit of the number of carbon atoms is not particularly limited, and is preferably 2 or more.
  • the specific complexing agent may be used alone or in combination of two or more.
  • the mass ratio of the content of the specific complexing agent to the content of the alkanolamine [content of the specific complexing agent / content of alkanolamine] is preferably 0.1 to 2000.0, preferably 0.1 to 1850. 0 is more preferable, 0.1 to 1500.0 is even more preferable, 0.1 to 1000.0 is further preferable, 0.1 to 400.0 is particularly preferable, and 20.0 to 400.0 is most preferable.
  • the mass ratio of the content of the specific complexing agent to the content of the polymer [content of the specific complexing agent / content of the polymer] is preferably 0.03 to 200.0, preferably 1.0 to 100. 0 is more preferable, and 1.5 to 50.0 is even more preferable.
  • the cleaning liquid contains water as a solvent.
  • the water is not particularly limited as long as it does not adversely affect the semiconductor substrate, and distilled water, deionized water, and pure water (preferably ultrapure water) can be used.
  • pure water or ultrapure 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.
  • the water content may be the balance of the components contained in the cleaning liquid.
  • the water content is preferably 1.0% by mass or more, more preferably 30.0% by mass or more, further preferably 60.0% by mass or more, and 85.0% by mass or more with respect to the total mass of the cleaning liquid.
  • the upper limit is not particularly limited, and is preferably 99.0% by mass or less, more preferably 97.0% by mass or less, based on the total mass of the cleaning liquid.
  • the cleaning liquid may contain a surfactant.
  • the surfactant is a compound different from the components contained in the above-mentioned cleaning liquid.
  • the surfactant is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule.
  • examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
  • the surfactant preferably contains an anionic surfactant, more preferably contains a phosphate ester-based surfactant, and is at least selected from the group consisting of an alkyl phosphate ester and a polyoxyethylene alkyl phosphate ester.
  • the cleaning liquid contains one, and it is particularly preferable to contain an alkyl phosphate ester.
  • the cleaning liquid contains a surfactant, it is possible to improve the corrosion suppressing performance of the metal film and the cleaning performance of the abrasive fine particles and the like.
  • Surfactants often have hydrophobic groups selected from the group consisting of aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups in combination thereof.
  • the hydrophobic group of the surfactant is not particularly limited, but when the hydrophobic group contains an aromatic hydrocarbon group, the number of carbon atoms is preferably 6 or more, and more preferably 10 or more. When the hydrophobic group does not contain an aromatic hydrocarbon group and is composed only of an aliphatic hydrocarbon group, the number of carbon atoms is preferably 9 or more, and more preferably 12 or more.
  • the upper limit of the number of carbon atoms of the hydrophobic group is not particularly limited, but is preferably 20 or less, and more preferably 18 or less.
  • the total carbon number of the surfactant is preferably 16 to 100.
  • anionic surfactant examples include a phosphate ester-based surfactant having a phosphate ester group, a phosphonic acid-based surfactant having a phosphonic acid group, a sulfonic acid-based surfactant having a sulfonic acid group, and a carboxy group.
  • examples thereof include a carboxylic acid-based surfactant having a sulfate ester group and a sulfate ester-based surfactant having a sulfate ester group.
  • phosphoric acid ester-based surfactant examples include an alkyl phosphate ester, a polyoxyalkylene alkyl ether phosphoric acid ester, and salts thereof. Of these, alkyl phosphate esters are preferred.
  • the phosphoric acid ester and the polyoxyalkylene alkyl ether phosphoric acid ester may be a monoester or a diester alone, or may be a mixture of the monoester and the diester.
  • the salt of the phosphoric acid ester-based surfactant include a sodium salt, a potassium salt, an ammonium salt, and an organic amine salt.
  • an alkyl group contained in the alkyl phosphate ester and the polyoxyalkylene alkyl ether phosphoric acid ester an alkyl group having 2 to 24 carbon atoms is preferable, an alkyl group having 6 to 18 carbon atoms is more preferable, and an alkyl having 12 to 18 carbon atoms is more preferable. The group is more preferred.
  • alkylene group contained in the polyoxyalkylene alkyl ether phosphoric acid ester an alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group or a 1,2-propanediyl group is more preferable.
  • the number of repetitions of the oxyalkylene group in the polyoxyalkylene ether phosphoric acid ester is preferably 1 to 12, more preferably 1 to 10.
  • Examples of the phosphoric acid ester-based surfactant include octyl phosphate, lauryl phosphate, tridecyl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, polyoxyethylene octyl ether phosphate, and polyoxyethylene.
  • Lauryl ether phosphate ester, polyoxyethylene tridecyl ether phosphate ester, or polyoxyethylene myristyl ether phosphate ester is preferable, and lauryl phosphate ester, tridecyl phosphate ester, myristyl phosphate ester, cetyl phosphate ester, stearyl phosphate are preferable.
  • Esters or polyoxyethylene myristyl ether phosphate esters are more preferred, and lauryl phosphate esters, cetyl phosphate esters, stearyl phosphate esters, or polyoxyethylene myristyl ether phosphate esters are even more preferred.
  • phosphonic acid-based surfactant examples include alkylphosphonic acid, polyvinylphosphonic acid, and aminomethylphosphonic acid described in JP-A-2012-057108.
  • sulfonic acid-based surfactant examples include alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, alkyl methyl taurine, sulfosuccinic acid diester, polyoxyalkylene alkyl ether sulfonic acid, and salts thereof. Can be mentioned.
  • alkyl group contained in the sulfonic acid-based surfactant an alkyl group having 2 to 24 carbon atoms is preferable, and an alkyl group having 6 to 18 carbon atoms is more preferable.
  • alkylene group contained in the polyoxyalkylene alkyl ether sulfonic acid an ethylene group or a 1,2-propanediyl group is preferable.
  • the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether sulfonic acid is preferably 1 to 12, more preferably 1 to 6.
  • sulfonic acid-based surfactant examples include hexanesulfonic acid, octanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid (DBSA), and dinitrobenzene.
  • DBSA dodecylbenzenesulfonic acid
  • LDPEDSA laurildodecylphenyl ether disulfonic acid
  • dodecane sulfonic acid, DBSA, DNBSA, or LDPEDSA is preferable, and DBSA, DNBSA, or LDPEDSA is more preferable.
  • Carboxylic acid-based surfactant examples include an alkylcarboxylic acid, an alkylbenzenecarboxylic acid, a polyoxyalkylene alkyl ether carboxylic acid, and salts thereof.
  • alkyl group contained in the carboxylic acid-based surfactant an alkyl group having 7 to 25 carbon atoms is preferable, and an alkyl group having 11 to 17 carbon atoms is more preferable.
  • alkylene group of the polyoxyalkylene alkyl ether carboxylic acid an ethylene group or a 1,2-propanediyl group is preferable.
  • the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether carboxylic acid is preferably 1 to 12, more preferably 1 to 6.
  • carboxylic acid-based surfactant examples include lauric acid, myristic acid, palmitic acid, stearic acid, polyoxyethylene lauryl ether acetic acid, and polyoxyethylene tridecyl ether acetic acid.
  • sulfuric acid ester-based surfactant examples include an alkyl sulfate ester, a polyoxyalkylene alkyl ether sulfuric acid ester, and salts thereof.
  • alkyl group contained in the alkyl sulfate ester and the polyoxyalkylene alkyl ether sulfuric acid ester an alkyl group having 2 to 24 carbon atoms is preferable, and an alkyl group having 6 to 18 carbon atoms is more preferable.
  • alkylene group contained in the polyoxyalkylene alkyl ether sulfuric acid ester an ethylene group or a 1,2-propanediyl group is preferable.
  • the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether sulfuric acid ester is preferably 1 to 12, more preferably 1 to 6.
  • sulfate ester-based surfactant examples include lauryl sulfate ester, myristyl sulfate ester, and polyoxyethylene lauryl ether sulfate ester.
  • surfactant examples include paragraphs [0092] to [0090] of JP-A-2015-158662, paragraphs [0045]-[0046] of JP-A-2012-151273, and JP-A-2009-147389.
  • the compounds described in paragraphs [0014] to [0020] of the publication may also be incorporated, and the contents thereof are incorporated in the present specification.
  • the surfactant may be used alone or in combination of two or more.
  • the content of the surfactant is preferably 0.001 to 8.0% by mass, more preferably 0.005 to 5.0% by mass, based on the total mass of the cleaning liquid, because the performance of the cleaning liquid is well-balanced. , 0.01-3.0% by mass is more preferable.
  • the content of the surfactant is preferably 1.0 to 30.0% by mass, more preferably 5.0 to 20.0% by mass, and 10.0 to 20% by mass with respect to the total mass of the cleaning liquid excluding the solvent. .0% by mass is more preferable.
  • the cleaning liquid may contain an anticorrosive agent.
  • the anticorrosion agent include a carboxylic acid, a heterocyclic compound having a heterocyclic structure in the molecule, a catechol compound, a hydroxylamine compound, a biguanide compound, a hydrazide compound, an ascorbic acid compound, a reducing sulfur compound, and a molecular weight of 500 or more. Polyhydroxy compounds of.
  • Carboxylic acid is a compound having a carboxy group in the molecule.
  • Carboxylic acid is a compound different from the components contained in the above-mentioned cleaning liquid.
  • Examples of the carboxylic acid include propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexaneic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid and 2-.
  • Examples thereof include methylhexanoic acid, n-octanoic acid, and 2-ethylhexanoic acid.
  • a heterocyclic compound is a compound having a heterocyclic structure in the molecule.
  • the heterocyclic compound is a compound different from the components contained in the above-mentioned cleaning solution.
  • Examples of the heterocyclic structure of a heterocyclic compound include a heterocycle (nitrogen-containing heterocycle) in which at least one of the atoms constituting the ring is a nitrogen atom.
  • Examples of the heterocyclic compound having a nitrogen-containing heterocycle include an azole compound, a pyridine compound, a pyrazine compound, a pyrimidine compound, a piperazine compound, and a cyclic amidin compound.
  • the heterocyclic compound at least one selected from the group consisting of an azole compound, a pyridine compound, a pyrazine compound, and a pyrimidine compound is preferable.
  • the azole compound is a compound having at least one nitrogen atom and having an aromatic 5-membered ring.
  • the number of nitrogen atoms contained in the hetero 5-membered ring of the azole compound is preferably 1 to 4, more preferably 1 to 3.
  • the azole compound may have a substituent on the hetero 5-membered ring. Examples of the substituent include a hydroxyl group, a carboxy group, a mercapto group, an amino group, an alkyl group having 1 to 4 carbon atoms which may have an amino group, and a 2-imidazolyl group.
  • Examples of the azole compound include an imidazole compound in which one of the atoms constituting the azole ring is a nitrogen atom, a pyrazole compound in which two of the atoms constituting the azole ring are nitrogen atoms, and one of the atoms constituting the azole ring.
  • One is a nitrogen atom
  • the other is a thiazole compound which is a sulfur atom
  • three of the atoms constituting the azole ring are triazole compounds which are nitrogen atoms
  • four of the atoms constituting the azole ring are nitrogen atoms.
  • Examples include tetrazole compounds.
  • imidazole compound examples include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole and 4-hydroxy.
  • Examples of the pyrazole compound include pyrazole, 4-pyrazolecarboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-aminopyrazole, and Examples include 4-aminopyrazole.
  • thiazole compound examples include 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole.
  • triazole compound examples include 1,2,4-triazol, 3-methyl-1,2,4-triazole, 3-amino-1,2,4-triazole and 1,2,3-triazol.
  • -L 1-methyl-1,2,3-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4
  • examples thereof include -carboxybenzotriazole, 5-methylbenzotriazole, and 2,2'- ⁇ [(5-methyl-1H-benzotriazole-1-yl) methyl] imino ⁇ diethanol.
  • tetrazole compound examples include 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1,2,3,4-tetrazole and 5-amino-1,2,3.
  • examples thereof include 4-tetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, and 1- (2-dimethylaminoethyl) -5-mercaptotetrazole.
  • the azole compound at least one selected from the group consisting of an imidazole compound, a pyrazole compound, a thiazole compound, a triazole compound and a tetrazole compound is preferable, and imidazole, pyrazole, 2,4-dimethylthiazole, 1,2,4-triazole and the like. 1H-tetrazole (1,2,3,4-tetrazole) or adenin is more preferable.
  • the pyridine compound is a compound having a hetero 6-membered ring (pyridine ring) containing one nitrogen atom and having aromaticity.
  • the pyridine compound may have a substituent on the pyridine ring. Examples of the substituent include a hydroxyl group, an amino group, a cyano group, an alkyl group having 1 to 4 carbon atoms, and an alkylamide group having 1 to 4 carbon atoms.
  • pyridine compound examples include pyridine, 3-aminopyridine, 4-aminopyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-acetamidopyridine, 2-cyanopyridine, 2-carboxypyridine, and 4-carboxypyridine.
  • pyridine is preferable.
  • the pyrazine compound is a compound having aromaticity and having a hetero 6-membered ring (pyrazine ring) containing two nitrogen atoms located at the para position.
  • the pyrimidine compound is a compound having aromaticity and having a hetero 6-membered ring (pyrimidine ring) containing two nitrogen atoms located at the meta position.
  • the pyrazine compound and the pyrimidine compound may have a substituent on the ring. Examples of the substituent include a hydroxyl group, an amino group, a carboxy group, and an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group.
  • pyrazine compound examples include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2,3,5,6-tetramethylpyrazine and 2-ethyl-3-methylpyrazine. , And 2-amino-5-methylpyrazine, with pyrazine being preferred.
  • Examples of the pyrimidine compound include pyrimidine, 2-methylpyrimidine, 2-aminopyrimidine, and 4,6-dimethylpyrimidine, and pyrimidine is preferable.
  • the piperazine compound is a compound having a hetero 6-membered ring (piperazine ring) in which the opposite -CH- group of the cyclohexane ring is replaced with a nitrogen atom.
  • the piperazine compound may have a substituent on the piperazine ring. Examples of such a substituent include a hydroxyl group, an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and an aryl group having 6 to 10 carbon atoms.
  • piperazine compound examples include piperazine, 1-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1-butylpiperazine, 2-methylpiperazine, 1,4-dimethylpiperazine, 2,5-dimethylpiperazine, 2, 6-Dimethylpiperazine, 1-phenylpiperazine, 2-hydroxypiperazine, 2-hydroxymethylpiperazine, 1- (2-hydroxyethyl) piperazine (HEP), and 1,4-bis (3-aminopropyl) piperazine (BAP). ), And piperazine, 1-methylpiperazine, 2-methylpiperazine, HEP, or BAP is preferable, and HEP or BAP is more preferable.
  • the number of ring members of the above heterocycle contained in the cyclic amidine compound is preferably 5 to 6, more preferably 6.
  • the cyclic amidine compound may have a substituent on the above heterocycle. Examples of the substituent include an amino group, an oxo group, and an alkyl group having 1 to 4 carbon atoms. Further, the two substituents on the above heterocycle may be bonded to each other to form a divalent linking group (preferably an alkylene group having 3 to 6 carbon atoms).
  • Examples of the cyclic amidine compound include diazabicycloundecene (1,8-diazabicyclo [5.4.0] undec-7-en: DBU) and diazabicyclononene (1,5-diazabicyclo [4.3.
  • Nona-5-en DBN
  • 3,4,6,7,8,9,10,11-octahydro-2H-pyrimid [1.2-a] azocin
  • 3,4,6,7,8 9-Hexahydro-2H-pyrido [1.2-a] pyrimidine
  • 2,5,6,7-tetrahydro-3H-pyrrolo [1.2-a] imidazole 3-ethyl-2,3,4,6 , 7,8,9,10-octahydropyrimid [1.2-a] azepine
  • creatinine with DBU or DBN being preferred.
  • heterocyclic compound examples include 1,3-dimethyl-2-imidazolidinone, a compound having a hetero5-membered ring having no aromaticity such as imidazolidinethione, and a 7-membered ring containing a nitrogen atom. Also mentioned are compounds having.
  • Examples of the compound having a 7-membered ring containing a nitrogen atom include hexahydro-1H-1,4-diazepine, 1-methylhexahydro-1H-1,4-diazepine, and 2-methylhexahydro-1H-1,4.
  • -Diazepine, 6-methylhexahydro-1H-1,4-diazepine, 2,7-diazabicyclo [3.2.1] octane, and 1,3-diazabicyclo [3.2.2] nonane can be mentioned.
  • the catechol compound means at least one selected from the group consisting of pyrocatechol (benzene-1,2-diol) and catechol derivatives.
  • the catechol derivative means a compound in which at least one substituent is substituted with pyrocatechol.
  • the catechol compound is a compound different from the components contained in the above-mentioned cleaning solution. Examples of the substituent contained in the catechol derivative include a hydroxyl group, a carboxy group, a carboxylic acid ester group, a sulfo group, a sulfonic acid ester group, and an alkyl group (preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms).
  • the carboxy group and the sulfo group that the catechol derivative has as a substituent may be a salt with a cation. Further, the alkyl group and the aryl group that the catechol derivative has as a substituent may further have a substituent.
  • catechol compound examples include pyrocatechol, 4-tert-butylcatechol, pyrogallol, gallate, methyl gallate, 1,2,4-benzenetriol, and Tyrone. Of these, pyrocatechol, pyrogallol, or gallic acid is preferable.
  • Hydroxylamine compound means at least one selected from the group consisting of hydroxylamine (NH 2 OH), hydroxylamine derivatives, and salts thereof.
  • the hydroxylamine compound is a compound different from the components contained in the above-mentioned cleaning liquid.
  • the hydroxylamine derivative means a compound in which at least one organic group is substituted with hydroxylamine (NH 2 OH). Examples of the hydroxylamine or the salt of the hydroxylamine derivative include inorganic acid salts and organic acid salts.
  • a salt with an inorganic acid in which at least one non-metal selected from the group consisting of Cl, S, N, and P is bonded to hydrogen is preferable.
  • Hydrochloride, sulfate, or nitrate is more preferred.
  • Examples of the hydroxylamine compound include a compound represented by the general formula (5).
  • R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms represented by R 6 and R 7 may be linear, branched or cyclic.
  • Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group and an isopentyl group.
  • Se-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert -Hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, and cyclohexyl group can be mentioned.
  • R 6 and R 7 an alkyl group having 1 to 6 carbon atoms is preferable, an ethyl group or an n-propyl group is more preferable, and an ethyl group is further preferable.
  • hydroxylamine compound examples include hydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N-ethylhydroxylamine, N, N-diethylhydroxylamine (DEHA), Nn-propylhydroxylamine, and the like.
  • Roxylamine N, N-bis (2-methylpentyl) hydroxylamine, N-1,2-dimethylbutylhydroxylamine, N, N-bis (1,2-dimethylbutyl) hydroxylamine, N-2,3-dimethyl Butyl hydroxylamine, N, N-bis (2,3-dimethylbutyl) hydroxylamine, N-1-ethylbutylhydroxylamine, N, N-bis (1-ethylbutyl) hydroxylamine, N-cyclohexylhydroxylamine, and Examples include N, N-dicyclohexylhydroxylamine.
  • hydroxylamine compound hydroxylamine, N-ethylhydroxylamine, DEHA, or Nn-propylhydroxylamine is preferable, and hydroxylamine is more preferable.
  • hydroxylamine compound a commercially available compound may be used, or a compound appropriately synthesized by a known method may be used.
  • the biguanide compound is a compound having a biguanide group and a biguanide compound which is a salt thereof.
  • the number of biguanide groups contained in the biguanide compound may be singular or plural.
  • Examples of the biguanide compound include the compounds described in paragraphs [0034] to [0055] of JP-A-2017-504190, the contents of which are incorporated in the present specification.
  • Examples of the compound having a biguanide group include ethylene diviguanide, propylene diviguanide, tetramethylene diviguanide, pentamethylene diviguanide, hexamethylene diviguanide, heptamethylene diviguanide, octamethylene diviguanide, and 1,1'-hexamethylenebis ( 5- (p-chlorophenyl) biguanide) (chlorhexidine), 2- (benzyloxymethyl) pentane-1,5-bis (5-hexylbiguanide), 2- (phenylthiomethyl) pentane-1,5-bis (5) -Phenetyl biguanide), 3- (phenylthio) hexane-1,6-bis (5-hexylbiguanide), 3- (phenylthio) hexane-1,6-bis (5-cyclohexylbiguanide), 3- (benzylthio) hexane-
  • a hydrochloride salt, an acetate salt, or a gluconate salt is preferable, and a gluconate salt salt is more preferable.
  • a gluconate salt salt is more preferable.
  • chlorhexidine gluconate (CHG) is preferable.
  • the hydrazide compound means a compound in which the hydroxyl group of an acid is substituted with a hydrazino group (-NH-NH 2 ), and a derivative thereof (a compound in which at least one substituent is substituted with a hydrazino group).
  • the hydrazide compound may have one or more hydrazino groups. Examples of the hydrazide compound include carboxylic acid hydrazide and sulfonic acid hydrazide, and carbohydrazide (CHZ) is preferable.
  • the ascorbic acid compound means at least one selected from the group consisting of ascorbic acid, ascorbic acid derivatives, and salts thereof.
  • the ascorbic acid derivative include ascorbic acid phosphate ester and ascorbic acid sulfate ester. Among them, ascorbic acid is preferable as ascorbic acid.
  • the reducing sulfur compound is a compound having reducing property and containing a sulfur atom.
  • the reducing sulfur compound include thioglycolic acid, dithiodiglycolic acid, bis (2,3-dihydroxypropylthio) ethylene, and 3- (2,3-dihydroxypropylthio) -2-methyl-propylsulfonate sodium. , 1-thioglycerol, 2-mercaptoethanol, and 3-mercapto-1-propanol.
  • a compound having an SH group mercapto compound
  • thioglycolic acid or dithiodiglycolic acid is more preferable.
  • the polyhydroxy compound is an organic compound having two or more (for example, 2 to 200) alcoholic hydroxyl groups in one molecule.
  • the polyhydroxy compound is a compound different from the components contained in the cleaning liquid described above.
  • the molecular weight of the polyhydroxy compound (meaning a weight average molecular weight when it has a molecular weight distribution) is 500 or more, preferably 500 to 3000.
  • polyhydroxy compound examples include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; Oligosaccharides such as; polysaccharides such as starch, glycogen, cellulose, chitin, and chitosan, and hydrolyzates thereof, and polyethylene glycol is preferable.
  • polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol
  • Oligosaccharides such as; polysaccharides such as starch, glycogen, cellulose, chitin, and chitosan, and hydrolyzates thereof, and polyethylene glycol is preferable.
  • Cyclodextrin is also preferable as the polyhydroxy compound.
  • Cyclodextrin is a kind of cyclic oligosaccharide having a cyclic structure in which a plurality of D-glucoses are bound by a glucosidic bond.
  • a compound in which 5 or more glucoses (for example, 6 to 8 glucoses) are bound can be mentioned.
  • Examples of the cyclodextrin include ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin, and ⁇ -cyclodextrin is preferable.
  • the anticorrosion agent may include at least one selected from the group consisting of catechol compounds, heterocyclic compounds, hydroxyamine compounds, biguanide compounds, ascorbic acid, reducing sulfur compounds, and polyhydroxy compounds having a molecular weight of 500 or more. It is preferable to include a heterocyclic compound.
  • the anticorrosive agent may be used alone or in combination of two or more.
  • the content of the anticorrosive agent is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and 0.05 to 3.0% by mass with respect to the total mass of the cleaning liquid. More preferred.
  • the content of the anticorrosive agent is preferably 0.2 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, and 1.5 to 5. 0% by mass is more preferable.
  • the cleaning solution may contain a preservative.
  • the preservative is a compound different from the components contained in the above-mentioned cleaning liquid.
  • Examples of preservatives include benzoic acid, sodium benzoate, salicylic acid, propionic acid, isopropyl paraoxybenzoate, isobutyl paraoxybenzoate, ethyl paraoxybenzoate, methyl paraoxybenzoate, butyl paraoxybenzoate, propyl paraoxybenzoate, and sulfite.
  • examples include substances, tea catechins, apple polyphenols, pectin degradation products, chitosan, lysoteam, and ⁇ -polylysine.
  • benzoic acid, sorbic acid, salicylic acid, or propionic acid is preferable as the preservative.
  • Benzoic acid, sorbic acid, salicylic acid, and propionic acid may also be used as a pH adjuster and a metal dissolving agent described later.
  • the preservative may be used alone or in combination of two or more.
  • the content of the preservative is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and 0.05 to 3.0% by mass with respect to the total mass of the cleaning liquid. More preferred.
  • the content of the anticorrosive agent is preferably 0.2 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, and 1.5 to 5. 0% by mass is more preferable.
  • the cleaning liquid preferably contains at least one selected from the group consisting of a surfactant, an anticorrosive agent, and an antiseptic, and contains at least one selected from the group consisting of a surfactant and an anticorrosive agent. It is more preferable, it is more preferable to contain an anticorrosive agent, and it is particularly preferable to contain a heterocyclic compound.
  • the cleaning liquid may contain an oxidizing agent.
  • the oxidizing agent is a compound different from the components contained in the cleaning liquid described above.
  • the oxidizing agent include peroxides, persulfides (for example, monopersulfides and dipersulfides, etc.), percarbonates, their acids, and salts thereof.
  • the oxidizing agent include oxidized halide (periodic acid such as iodic acid, metaperiodic acid and orthoperiodic acid, and salts thereof), periodic acid, periodic acid salt, cerium compound, and the like.
  • ferricyanides potassium ferricyanide, etc.
  • the oxidizing agent may be used alone or in combination of two or more.
  • the content of the oxidizing agent is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, still more preferably 0.1 to 3% by mass, based on the total mass of the cleaning liquid.
  • the cleaning solution may contain a pH regulator to adjust and maintain the pH of the cleaning solution.
  • the pH adjuster is a compound different from the components contained in the cleaning solution described above.
  • Examples of the pH adjuster include a quaternary ammonium compound, a basic compound, and an acidic compound. Of these, a quaternary ammonium compound, sulfuric acid, or potassium hydroxide is preferable. However, it is permissible to adjust the pH of the cleaning solution by adjusting the amount of each component added as described above.
  • the quaternary ammonium compound is a compound different from the components contained in the above-mentioned cleaning liquid.
  • the quaternary ammonium compound is preferably a compound having a quaternary ammonium cation in which a nitrogen atom is substituted with four hydrocarbon groups (preferably an alkyl group).
  • the quaternary ammonium compound is a compound having a quaternary ammonium cation in which a nitrogen atom in the pyridine ring is bonded to a substituent (hydrocarbon group such as an alkyl group and an aryl group), such as an alkylpyridinium. May be good.
  • Examples of the quaternary ammonium compound include a quaternary ammonium hydroxide, a quaternary ammonium fluoride, a quaternary ammonium bromide, a quaternary ammonium iodide, a quaternary ammonium acetate, and a quaternary ammonium compound.
  • Examples include carbonates of quaternary ammonium.
  • a quaternary ammonium hydroxide represented by the formula (4) is preferable.
  • R 8 represents an alkyl group which may have a hydroxyl group or a phenyl group as a substituent.
  • the four R8s may be the same or different from each other.
  • alkyl group represented by R 8 an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
  • alkyl group represented by R8 which may have a hydroxyl group or a phenyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-hydroxyethyl group, or a benzyl group is preferable, and a methyl group is used.
  • Ethyl group, propyl group, butyl group, or 2-hydroxyethyl group is more preferable, and methyl group, ethyl group, or 2-hydroxyethyl group is further preferable.
  • quaternary ammonium compound examples include tetramethylammonium hydroxide (TMAH), trimethylethylammonium hydroxide (TMEAH), dimethyldiethylammonium hydroxide (DMDEAH), methyltriethylammonium hydroxide (MTEAH), and tetraethylammonium hydroxide.
  • TMAH tetramethylammonium hydroxide
  • TAEAH trimethylethylammonium hydroxide
  • DMDEAH dimethyldiethylammonium hydroxide
  • MTEAH methyltriethylammonium hydroxide
  • TMAH tetramethylammonium hydroxide
  • TAEAH trimethylethylammonium hydroxide
  • DMDEAH dimethyldiethylammonium hydroxide
  • MTEAH methyltriethylammonium hydroxide
  • tetraethylammonium hydroxide examples include tetramethyl
  • TEAH Tetrapropyl Ammonium Hydroxide
  • TBAH Tetrabutyl Ammonium Hydroxide
  • 2-Hydroxyethyl Trimmonium Ammonium Hydroxide Cold
  • Bis (2-Hydroxyethyl) Dimethyl Ammonium Hydroxide Tri (2-) Examples thereof include hydroxyethyl) methylammonium hydroxide, tetra (2-hydroxyethyl) ammonium hydroxide, benzyltrimethylammonium hydroxide (BTMAH), and cetyltrimethylammonium hydroxide.
  • TMAH, TEAH, choline, TBAH, MTEAH, DMDEAH, or TPAH is preferable, and TMAH, TEAH, or choline is more preferable.
  • the quaternary ammonium compound preferably has an asymmetric structure from the viewpoint of excellent damage resistance.
  • having an asymmetric structure in a quaternary ammonium compound is meant that none of the four hydrocarbon groups substituting for nitrogen atoms are the same.
  • Examples of the quaternary ammonium compound having an asymmetric structure include TMEAH, DEDHH, TEMAH, choline, and bis (2-hydroxyethyl) dimethylammonium hydroxide.
  • Examples of the basic compound include a basic organic compound and a basic inorganic compound.
  • Examples of the basic organic compound include amine oxides, nitros, nitroso, oximes, ketooximes, aldoximes, lactams, isocyanides, and ureas.
  • Examples of the basic inorganic compound include alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia.
  • Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide.
  • Examples of the alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • the acidic compound examples include inorganic acids.
  • a salt of the acidic compound may be used as long as it becomes an acid or an acid ion (anion) in an aqueous solution.
  • inorganic acid examples include hydrochloric acid, sulfuric acid, sulfite, nitric acid, nitrite, phosphoric acid, boric acid, and hexafluorophosphate.
  • the inorganic acid may form a salt.
  • the salt of the inorganic acid include an ammonium salt of an inorganic acid, and specifically, ammonium chloride, ammonium sulfate, ammonium sulfite, ammonium nitrate, ammonium nitrite, ammonium phosphate, ammonium borate, and phosphorus hexafluoride. Ammonium sulphate can be mentioned.
  • the pH adjuster may be used alone or in combination of two or more.
  • the content of the pH adjuster is not particularly limited, and is appropriately adjusted according to the type and amount of other components and the pH of the target cleaning solution.
  • the content of the pH adjuster is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and 0.05 to 3.0% by mass with respect to the total mass of the cleaning liquid. Is more preferable.
  • the content of the pH adjuster is preferably 0.2 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, and 1.5 to 5 to the total mass of the cleaning liquid excluding the solvent. .0% by mass is more preferable.
  • the cleaning liquid may contain an organic solvent.
  • the organic solvent is a compound different from the components contained in the cleaning liquid described above.
  • a known organic solvent can be used, and a hydrophilic organic solvent is preferable.
  • the hydrophilic organic solvent include alcohol-based solvents, ketone-based solvents, ester-based solvents, sulfone-based solvents, sulfoxide-based solvents, nitrile-based solvents, and amide-based solvents.
  • the hydrophilic organic solvent is preferably an alcohol solvent or a nitrile solvent.
  • alcohol-based solvent examples include alkanediol such as alkylene glycol, alkoxy alcohol such as glycol monoether, saturated aliphatic monohydric alcohol, unsaturated non-aromatic monohydric alcohol, and low molecular weight alcohol containing a cyclic structure. Can be mentioned.
  • alkanediol examples include glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-diol, 1,4-butanediol, and 1,3-.
  • alkanediol examples include butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycol.
  • alkylene glycol examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.
  • alkoxy alcohol examples include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and glycol monoether.
  • glycol monoether examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol.
  • Monobutyl ether triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy- 1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene Examples thereof include glycol monobenzyl ether and diethylene glycol monobenzyl ether.
  • saturated aliphatic monohydric alcohol examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, and t-pentyl alcohol. And 1-hexanol.
  • unsaturated non-aromatic monohydric alcohols examples include allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.
  • low molecular weight alcohols containing a cyclic structure examples include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.
  • ketone solvent examples include acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, and 1,3-cyclohexane.
  • examples include dione and cyclohexanone.
  • ester solvent examples include glycol monoesters such as ethyl acetate, ethylene glycol monoacetate, and diethylene glycol monoacetate; propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. , And glycol monoether monoesters such as ethylene glycol monoethyl ether acetate.
  • sulfone solvent examples include sulfolane, 3-methylsulfolane, and 2,4-dimethylsulfolane.
  • sulfoxide-based solvent examples include dimethyl sulfoxide.
  • a sulfoxide solvent it is preferable to use a grade in which inorganic ions such as sulfate ion, chloride ion, or nitrate ion and metal ion are reduced, or further purify the solvent.
  • nitrile solvent examples include acetonitrile.
  • amide solvent examples include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, and N.
  • -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide can be mentioned.
  • the organic solvent may be used alone or in combination of two or more.
  • the content of the organic solvent is preferably 0.01 to 80% by mass, more preferably 0.01 to 50% by mass, further preferably 0.01 to 10% by mass, and 0.01 to the total mass of the cleaning liquid. ⁇ 1% by mass is particularly preferable.
  • the cleaning liquid may contain a fluorine compound.
  • the fluorine compound include the compounds described in paragraphs [0013] to [0015] of JP-A-2005-150236, and the contents thereof are incorporated in the present specification.
  • the amount of the fluorine compound used is not particularly limited and can be appropriately adjusted as long as the effect of the present invention is not impaired.
  • the content of each of the above components is determined by gas chromatography-mass spectrometry (GC-MS: Gas Chromatography-Mass Spectrometry) method, liquid chromatography-mass spectrometry (LC-MS: Liquid Chromatography-Mass Spectrometry) method, and ion exchange. It can be measured by a known method such as a chromatography (IC: Ion-exchange Chromatography) method.
  • GC-MS Gas Chromatography-Mass Spectrometry
  • LC-MS Liquid Chromatography-Mass Spectrometry
  • ion exchange ion exchange
  • the cleaning liquid may contain a metal as an impurity.
  • Content of the above metals eg, metal elements such as Fe, Co, Na, K, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag
  • it is preferably 5 mass ppm or less, and more preferably 1 mass ppm or less, based on the total mass of the cleaning liquid. Since it is assumed that a higher-purity cleaning liquid is required in the manufacture of the most advanced semiconductor element, the metal content is lower than 1 mass ppm (that is, the total mass of the cleaning liquid).
  • the lower limit of the metal content is not particularly limited, but 0 is preferable with respect to the total mass of the cleaning liquid.
  • the content of potassium (K) is preferably 1000 mass ppb or less, and more preferably 100 mass ppb or less, based on the total mass of the washing liquid.
  • the lower limit is not particularly limited, but 0 is preferable.
  • the mass ratio of the content of potassium (K) to the content of sodium (Na) [(potassium content) / sodium content] is preferably 0.1 to 10.
  • a method for reducing the metal content for example, a method of performing purification treatment such as filtration using an ion exchange resin or a filter at the stage of raw materials used in producing the cleaning liquid or at the stage after the production of the cleaning liquid.
  • the cleaning liquid may contain particles.
  • the particle means a particle having a diameter (particle size) of 0.01 ⁇ m or more when the shape of the particle is regarded as a sphere.
  • the content of particles having a particle size of 0.01 ⁇ m or more is preferably 1000 or less, and more preferably 500 or less, per 1 mL of the cleaning liquid.
  • the lower limit is not particularly limited, and 0 is preferable. It is also preferable that the content of particles having a particle size of 0.01 ⁇ m or more measured by the measuring method described later is not more than the detection limit.
  • the particle content can be measured in the liquid phase by using a commercially available measuring device in a light scattering type submerged particle measuring method using a laser as a light source.
  • the particles include, for example, particles such as dust, dust, organic solids, and inorganic solids contained as impurities in the raw material of the cleaning liquid, and dust, dust, and organic solids brought in as contaminants during the preparation of the cleaning liquid. , And particles such as inorganic solids, and those that finally exist as particles without being dissolved in the cleaning liquid fall under this category.
  • Examples of the method for removing particles include purification treatment such as filtering described later.
  • the cleaning liquid may be a kit in which the raw material is divided into a plurality of parts.
  • the cleaning liquid can be produced by a known method. Hereinafter, the method for producing the cleaning liquid will be described in detail.
  • the method for preparing the cleaning liquid is not particularly limited, and for example, the cleaning liquid can be produced by mixing the above-mentioned components.
  • the order and / or timing of mixing each of the above-mentioned components is not particularly limited, and for example, the polymer, alkanolamine, specific complexing agent, and water are sequentially added to a container containing purified pure water. After that, a mixed solution is prepared by stirring, and a pH adjusting agent is further added to the obtained mixed solution to adjust the pH. Further, when water and each component are added to the container, they may be added all at once or divided into a plurality of times.
  • the stirring device and stirring method used for preparing the cleaning liquid are not particularly limited, and a known device as a stirrer or a disperser can be used.
  • a known device as a stirrer or a disperser can be used.
  • the stirrer include an industrial mixer, a portable stirrer, a mechanical stirrer, and a magnetic stirrer.
  • the disperser include an industrial disperser, a homogenizer, an ultrasonic disperser, and a bead mill.
  • the mixing of each component in the preparation step of the cleaning liquid, the purification treatment described later, and the storage temperature of the produced cleaning liquid are preferably 40 ° C. or lower, more preferably 30 ° C. or lower.
  • the lower limit of the storage temperature is not particularly limited, and is preferably 5 ° C. or higher, more preferably 10 ° C. or higher.
  • Refining process It is preferable to perform a purification treatment in advance on any one or more of the raw materials for preparing the cleaning liquid.
  • the purification treatment include known methods such as distillation, ion exchange, and filtration.
  • the degree of purification for example, it is preferable to purify until the purity of the raw material is 99% by mass or more, and it is more preferable to purify until the purity of the stock solution is 99.9% by mass or more.
  • the purification treatment method examples include a method of passing a raw material through an ion exchange resin or an RO membrane (Reverse Osmosis Membrane), distillation of the raw material, and filtering described later.
  • a purification treatment a plurality of the above-mentioned purification methods may be combined and carried out.
  • the raw material is subjected to primary purification by passing it through an RO membrane, and then passed through a purification device made of a cation exchange resin, an anion exchange resin, or a mixed bed type ion exchange resin. You may.
  • the purification treatment may be carried out a plurality of times.
  • the filter used for filtering is not particularly limited as long as it is used for filtration purposes and the like.
  • the filter include fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyethylene and polypropylene (PP), and the like.
  • fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyethylene and polypropylene (PP), and the like.
  • the filter is made of a material selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesin (including PTFE and PFA), and polyamide-based resin (including nylon).
  • the critical surface tension of the filter is preferably 70 to 95 mN / m, more preferably 75 to 85 mN / m.
  • the value of the critical surface tension of the filter is the manufacturer's nominal value.
  • the pore diameter of the filter is preferably 2 to 20 nm, more preferably 2 to 15 nm. Within the above range, it is possible to reliably remove fine foreign substances such as impurities and agglomerates contained in the raw material while suppressing clogging of filtration.
  • the nominal value of the filter manufacturer can be referred to.
  • Filtering may be performed only once or twice or more. When filtering is performed twice or more, the filters used may be the same or different.
  • Filtering is preferably performed at 25 ° C. or lower, more preferably room temperature (23 ° C.) or lower, and even more preferably 20 ° C. or lower.
  • the upper limit is not particularly limited, and is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and even more preferably 10 ° C. or higher.
  • the cleaning liquid (including the aspect of the kit) can be filled in any container, stored, transported, and used as long as corrosiveness is not a problem.
  • a container having a high degree of cleanliness inside the container and suppressing elution of impurities from the inner wall of the container's accommodating portion into each liquid is preferable for semiconductor applications.
  • the container include various containers commercially available as a container for a semiconductor cleaning liquid. Specific examples thereof include the "clean bottle” series manufactured by Aicello Chemical Corporation and the "pure bottle” manufactured by Kodama Resin Industry.
  • the inner wall of the container accommodating portion and the wetted portion between each liquid are formed of a fluororesin (perfluororesin) or a metal that has been subjected to rust prevention and metal elution prevention treatment.
  • a container is preferable.
  • the inner wall of the container is made of one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a resin different from this, stainless steel, hasteroi, inconel, monel, and the like. It is preferably formed from a metal that has been subjected to rust-preventive and metal elution-preventing treatments.
  • a fluororesin (perfluororesin) is preferable.
  • a container whose inner wall is a fluororesin When a container whose inner wall is a fluororesin is used, the occurrence of a problem of elution of ethylene or propylene oligomer can be suppressed as compared with a container whose inner wall is a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin.
  • Examples of the container whose inner wall is a fluororesin include, for example, a FluoroPure PFA composite drum manufactured by Entegris, page 4 of JP-A-3-502677, page 3 of International Publication No. 2004/016526, and Examples include the containers described on pages 9 and 16 of International Publication No. 99/46309.
  • quartz and an electropolished metal material are also preferably used for the inner wall of the container.
  • the metal material used in the production of 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 the total mass of the metal material. , 25% by mass or more of the metal material is preferable, and 30% by mass or more of the metal material is more preferable.
  • the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, and is preferably 90% by mass or less. Examples of the metal material include stainless steel and nickel-chromium alloy.
  • the inside of the container is cleaned before filling with the cleaning liquid.
  • the liquid used for the cleaning preferably has a reduced amount of metal impurities in the liquid.
  • the cleaning liquid may be bottling, transported and stored in a container such as a gallon bottle or a coated bottle after production.
  • the inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) having a purity of 99.99995% by volume or more.
  • the inert gas preferably has a low water content.
  • the temperature for transportation and storage may be room temperature, or may be ⁇ 20 ° C. to 20 ° C. from the viewpoint of preventing deterioration. Further, the temperature may be controlled in order to obtain the above temperature.
  • the clean room preferably meets the 14644-1 clean room standard. It is preferable to satisfy any one of ISO (International Organization for Standardization) class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably to satisfy ISO class 1 or ISO class 2, and satisfy ISO class 1. Is even more preferable.
  • ISO International Organization for Standardization
  • the cleaning liquid is preferably used in a cleaning step for cleaning a semiconductor substrate that has been subjected to chemical mechanical polishing (CMP) treatment.
  • CMP chemical mechanical polishing
  • the cleaning liquid can also be used for cleaning the semiconductor substrate in the semiconductor substrate manufacturing process. Further, it can also be used for buffing treatment as described later.
  • Examples of the object to be cleaned by the cleaning liquid include a semiconductor substrate having a metal film containing tungsten.
  • “on the semiconductor substrate” includes, for example, any of the front and back surfaces, the side surfaces, the inside of the groove, and the like of the semiconductor substrate.
  • the metal film on the semiconductor substrate includes not only the case where the metal film is directly on the surface of the semiconductor substrate but also the case where the metal film is present on the semiconductor substrate via another layer.
  • Examples of the metal contained in the metal film include W (tungsten).
  • the metal film may contain a metal other than W.
  • Other metals include, for example, Cu (copper), Co (cobalt), Ti (tantalum), Ta (tantalum), Ru (ruthenium), Cr (chromium), Hf (hafnium), Os (osmium), Pt ( At least one metal selected from the group consisting of platinum), Ni (nickel), Mn (manganese), Cu (copper), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium). M is mentioned.
  • Examples of the semiconductor substrate to be cleaned by the cleaning liquid include a substrate having a metal wiring film, a barrier metal, and an insulating film on the surface of the wafer constituting the semiconductor substrate.
  • Examples of the wafer constituting the semiconductor substrate include a silicon (Si) wafer, a silicon carbide (SiC) wafer, a wafer made of a silicon-based material such as a resin-based wafer containing silicon (glass epoxy wafer), and gallium phosphorus (GaP). ) Wafers, gallium arsenic (GaAs) wafers, and indium phosphorus (InP) wafers.
  • the silicon wafer include an n-type silicon wafer in which a silicon wafer is doped with a pentavalent atom (for example, phosphorus (P), arsenic (As), antimony (Sb), etc.), and a silicon wafer is trivalent.
  • Examples thereof include a p-type silicon wafer doped with an atom of (for example, boron (B), gallium (Ga), etc.).
  • Examples of silicon for silicon wafers include amorphous silicon, single crystal silicon, polycrystalline silicon, and polysilicon.
  • the wafer a wafer made of a silicon-based material such as a silicon wafer, a silicon carbide wafer, and a resin-based wafer (glass epoxy wafer) containing silicon is preferable.
  • the semiconductor substrate may further have an insulating film on the above-mentioned wafer.
  • the insulating film include a silicon oxide film (for example, a silicon dioxide (SiO 2 ) film, a tetraethyl orthosilicate (Si (OC 2 H 5 ) 4 ) film (TEOS film), etc.), and a silicon nitride film (for example, a silicon nitride film).
  • Silicon nitride (Si 3N 4 ), silicon nitride carbide ( SiNC ), etc.), and low dielectric constant (Low-k) films eg, carbon-doped silicon oxide (SiOC) films, and silicon carbide (SiC). Membrane, etc.).
  • Examples of the metal film containing tungsten include a metal film made of only metallic tungsten (tungsten metal film) and a metal film made of an alloy of tungsten and a metal other than tungsten (tungsten alloy metal film). ).
  • Examples of the tungsten alloy metal film include a tungsten-titanium alloy metal film (WTi alloy metal film) and a tungsten-cobalt alloy metal film (WCo alloy metal film).
  • the tungsten-containing film can be used, for example, at the connection portion between the barrier metal or via and the wiring.
  • the method for forming the above-mentioned insulating film and the tungsten-containing film on the wafer constituting the semiconductor substrate is not particularly limited as long as it is a known method.
  • a method for forming the insulating film for example, a silicon oxide film is formed by heat-treating a wafer constituting a semiconductor substrate in the presence of oxygen gas, and then silane and ammonia gas are introduced to form a chemical vapor deposition. Examples thereof include a method of forming a silicon nitride film by a vapor deposition (CVD) method.
  • CVD vapor deposition
  • a method for forming the tungsten-containing film for example, a circuit is formed on a wafer having the above-mentioned insulating film by a known method such as a resist, and then a tungsten-containing film and a cobalt-containing film are contained by a method such as plating and a CVD method. Examples include a method of forming a film.
  • a substrate having a metal wiring film, a barrier metal, and an insulating film is formed by a combined action of a chemical action using a polishing slurry containing polishing fine particles (abrasive grains) and a mechanical action by mechanical polishing. It is a process of flattening the surface of.
  • abrasive grains for example, silica and alumina
  • a polished metal wiring film for example, metal impurities (metal residue) derived from the barrier metal, etc. Impurities may remain.
  • organic residues derived from the CMP treatment liquid used in the CMP treatment may remain.
  • the semiconductor substrate subjected to the CMP treatment is used for cleaning treatment for removing these impurities from the surface.
  • Examples of the semiconductor substrate subjected to the CMP treatment include Vol. 84, No. 3.
  • the substrate subjected to the CMP treatment according to 2018 can be mentioned.
  • the surface of the semiconductor substrate which is the object to be cleaned by the cleaning liquid, may be further subjected to buffing treatment after being subjected to CMP treatment.
  • the buffing process is a process of reducing impurities on the surface of a semiconductor substrate by using a polishing pad. Specifically, the surface of the semiconductor substrate subjected to the CMP treatment is brought into contact with the polishing pad, and the semiconductor substrate and the polishing pad are relatively slid while supplying the buffing composition to the contact portion. .. As a result, impurities on the surface of the semiconductor substrate are removed by the frictional force of the polishing pad and the chemical action of the buffing composition.
  • a known buffing composition can be appropriately used depending on the type of the semiconductor substrate and the type and amount of impurities to be removed.
  • the components contained in the buffing composition include water-soluble polymers such as polyvinyl alcohol, water as a dispersion medium, and acids such as nitric acid.
  • the buffing treatment it is preferable to buff the semiconductor substrate using the above-mentioned cleaning liquid as the buffing composition.
  • the polishing device and polishing conditions used in the buffing process can be appropriately selected from known devices and conditions according to the type of semiconductor substrate, the object to be removed, and the like. Examples of the buffing process include the processes described in paragraphs [805] to [0088] of International Publication No. 2017/169539, and these contents are incorporated in the present specification.
  • the method for cleaning the semiconductor substrate is not particularly limited as long as it includes a cleaning step of cleaning the semiconductor substrate subjected to the CMP treatment using the above-mentioned cleaning liquid.
  • the cleaning step of cleaning the semiconductor substrate using the cleaning liquid is not particularly limited as long as it is a known method performed on the semiconductor substrate treated with CMP, and a cleaning member such as a brush is used while supplying the cleaning liquid to the semiconductor substrate.
  • Scrub cleaning that physically contacts the surface of the semiconductor substrate to remove residues
  • immersion type that immerses the semiconductor substrate in the cleaning liquid
  • spin (drop) type that drops the cleaning liquid while rotating the semiconductor substrate
  • cleaning liquid A spray type for spraying can be mentioned.
  • the immersion type cleaning it is preferable to perform ultrasonic treatment on the cleaning liquid in which the semiconductor substrate is immersed from the viewpoint of further reducing impurities remaining on the surface of the semiconductor substrate.
  • the cleaning step may be performed only once or twice or more. When washing twice or more, the same method may be repeated, or different methods may be combined.
  • the semiconductor substrate cleaning method may be either a single-wafer method or a batch method.
  • the single-wafer method is a method of processing semiconductor substrates one by one
  • the batch method is a method of processing a plurality of semiconductor substrates at the same time.
  • the temperature of the cleaning liquid used for cleaning the semiconductor substrate is not particularly limited as long as it is a temperature usually used in this field.
  • the temperature of the cleaning liquid may be room temperature (23 ° C.), and the temperature may be arbitrarily selected in order to improve the cleaning property and suppress the damage resistance to the member.
  • the temperature of the cleaning liquid is preferably 10 to 60 ° C, more preferably 15 to 50 ° C.
  • the cleaning time in cleaning the semiconductor substrate can be appropriately adjusted depending on the type and content of the components contained in the cleaning liquid, and from the viewpoint of practicality, the cleaning time is preferably 10 seconds to 2 minutes, preferably 20 seconds to 1 minute 30 seconds. Is more preferable, and 30 seconds to 1 minute is further preferable.
  • the supply amount (supply rate) of the cleaning liquid in the cleaning step of the semiconductor substrate is not particularly limited, and is preferably 50 to 5000 mL / min, more preferably 500 to 2000 mL / min.
  • a mechanical stirring method may be used in order to further enhance the cleaning ability of the cleaning liquid.
  • the mechanical stirring method include a method of circulating the cleaning liquid on the semiconductor substrate, a method of flowing or spraying the cleaning liquid on the semiconductor substrate, and a method of stirring the cleaning liquid by ultrasonic waves or megasonics.
  • a step of rinsing and cleaning the semiconductor substrate with a solvent may be performed.
  • the rinsing step is preferably performed continuously after the cleaning step of the semiconductor substrate, and is preferably a rinsing step using a rinsing solvent (rinsing solution) for 5 seconds to 5 minutes.
  • the rinsing step may be performed using the above-mentioned mechanical stirring method.
  • the rinsing solution examples include water (preferably De Ionize water), methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, ⁇ -butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether. Acetate can be mentioned. Further, the rinsing solution may be an aqueous rinsing solution having a pH of more than 8.0 (diluted aqueous ammonium hydroxide or the like). As a method of contacting the rinsing liquid with the semiconductor substrate, the above-mentioned method of contacting the cleaning liquid with the semiconductor substrate can be similarly applied.
  • a drying step of drying the semiconductor substrate may be performed.
  • the drying method include a spin drying method, a method of flowing a dry gas over a semiconductor substrate, a method of heating a substrate by a heating means such as a hot plate or an infrared lamp, a marangoni drying method, a rotagoni drying method, and IPA (isopropyl). Alcohol) drying method and combinations thereof can be mentioned.
  • the pH of the cleaning solution was measured at 25 ° C. using a pH meter (manufactured by HORIBA, Ltd., model “F-74”) in accordance with JIS Z8802-1984. Further, in the production of the cleaning liquids of Examples and Comparative Examples, the handling of the container, the preparation, filling, storage, and analysis measurement of the cleaning liquid were all performed in a clean room at a level satisfying ISO class 2 or less.
  • Asparagin L-asparagin, Fuji Film Wako Pure Chemical Industries, Ltd.
  • Asparaginic acid L-asparaginic acid, Fuji Film Wako Pure Chemical Industries, Ltd.
  • Glutamic acid L-glutamic acid, Fuji Film Wako Pure Chemical Industries, Ltd.
  • Cysteine L-cysteine, Fujifilm Wako Pure Chemical Industries, Ltd.
  • Citrate Fujifilm Wako Pure Chemical Industries, Ltd.
  • Tartrate acid L-Tartrate acid
  • DTPA Diethylenetriamine pentaacetic acid, Wako Pure Chemical Industries, Ltd.
  • ⁇ HEDPO 1-hydroxyethylidene-1,1-diphosphonic acid
  • Thermophos "Dequest 2000" ⁇ EDTA: ethylenediamine tetraacetic acid, manufactured by Kirest Co., Ltd.
  • ⁇ DHEG N, N-bis (2-hydroxyethyl) glycine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • Sodium acid Fujifilm Wako Pure Chemical Industries, Ltd.
  • Diphosphate Fujifilm Wako Pure Chemical Industries, Ltd.
  • ⁇ p-Toluenesulfonic acid Fujifilm Wako Pure Chemical Industries, Ltd.
  • Methanesulfonic acid Fujifilmwa Made by Kojunyaku Co., Ltd.
  • ⁇ Etansulfonic acid Made by Fujifilm Wako Pure Chemical Industries, Ltd.
  • ⁇ Salicylic acid manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Made ⁇ Anti-corrosion agent>
  • ⁇ Pyrocatecol Made by Fujifilm Wako Pure Chemical Industries, Ltd.
  • ⁇ Pyrogalol Made by Fujifilm Wako Pure Chemical Industries, Ltd.
  • ⁇ Gluttonous acid Made by Fujifilm Wako Pure Chemical Industries, Ltd. ⁇ Pyrazole: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ⁇ 2,4-dimethylthiazole: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ⁇ 1,2,4-triazol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • the cleaning performance (residue removal performance) when the metal film after the CMP treatment was cleaned was evaluated using the cleaning liquids of each Example or Comparative Example.
  • FREX-300SII polishing equipment, manufactured by Ebara Corporation
  • W2000 polishing liquid
  • the supply speed of the polishing liquid is 0.28 ml / (min ⁇ cm 2 )
  • the polishing pressure is 2.
  • a wafer (12 inches in diameter) having a metal film made of tungsten on the surface was subjected to CMP treatment under the conditions of 0.0 psi and a polishing time of 60 seconds.
  • each cleaning solution was adjusted to room temperature (23 ° C.), scrubbed with each cleaning solution for 60 seconds, and dried.
  • a defect detection device the number of defects on the polished surface of the obtained wafer was detected, and each defect was observed with an SEM (scanning electron microscope) to classify the defects. If necessary, the constituent elements were analyzed by EDAX (energy dispersive X-ray analyzer) to identify the components. As a result, the number of defects based on the residue was determined, and the cleaning performance was evaluated according to the following evaluation criteria (evaluation 6 is the most excellent in cleaning performance).
  • the number of target defects is less than 20 5: The number of target defects is 20 or more and less than 50 4: The number of target defects is 50 or more and less than 100 3: The number of target defects is 100 or more and less than 200 2: The number of target defects is 200 or more and less than 300 1: The number of target defects is 300 or more
  • Corrosion suppression performance The corrosion suppression performance when the metal film was washed was evaluated using the cleaning liquids of each Example or Comparative Example. Wafers (12 inches in diameter) having a metal film made of tungsten on the surface were cut, and 2 cm ⁇ wafer coupons were prepared respectively. The thickness of each metal film was 200 nm. The wafer was immersed in each cleaning liquid at room temperature (23 ° C.) at a stirring rotation speed of 250 rpm, and 30 minutes after being immersed in each cleaning liquid of a metal film made of tungsten, the thickness of the disappeared metal film was determined. .. From the disappeared film thickness, the corrosion rate of the metal film per unit time was calculated. Corrosion suppression performance was evaluated according to the following evaluation criteria.
  • Corrosion rate is 0.2 ⁇ / min or less 5: Corrosion rate is more than 0.2 ⁇ / min, 0.5 ⁇ / min or less 4: Corrosion rate is more than 0.5 ⁇ / min or less, 1 ⁇ / min or less 3: Corrosion rate is More than 1 ⁇ / min, less than 3 ⁇ / min 2: Corrosion rate is more than 3 ⁇ / min, less than 5 ⁇ / min 1: Corrosion rate is more than 5 ⁇ / min
  • the table below shows the composition and evaluation results of the cleaning liquids of each Example and Comparative Example.
  • the "Mw” column indicates the weight average molecular weight.
  • the “content (% by mass)” column indicates the content (unit: mass%) of each component with respect to the total mass of the cleaning liquid.
  • the “active ingredient amount (% by mass)” column shows the content of each component with respect to the total mass of the cleaning liquid excluding the solvent.
  • the column “(C) / (B)” represents the mass ratio of the content of the specific complexing agent to the content of the alkanolamine [content of the specific complexing agent / content of alkanolamine].
  • the column “(C) / (A)” represents the mass ratio of the content of the specific complexing agent to the content of the polymer [content of the specific complexing agent / content of the polymer].
  • the numerical value in the “pH” column indicates the pH of the cleaning solution measured by the above pH meter at 25 ° C.
  • “* 1” in the “pH” column means that, if necessary, H 2 SO 4 (sulfuric acid) was added in an amount so that the pH of the prepared cleaning solution would be the value in the “pH” column.
  • the “remaining portion” in the "water” column means that water constitutes the rest of the cleaning liquid other than each component.
  • the cleaning solution of the present invention obtained the desired effect. From the comparison between Examples 1 and 60 to 63 and Examples 64 to 66, it was confirmed that the effect was more excellent when the weight average molecular weight of the polymer was 2000 to 500,000. From the comparison between Examples 1 and 17 to 21 and Examples 22 to 23, the mass ratio of the content of the specific complexing agent to the content of the alkanolamine [(C) / (B)] is 0. When it was 1 to 1000.0, it was confirmed that the effect was more excellent. Further, when [(C) / (B)] was 0.1 to 400.0, it was confirmed that the effect was further excellent.
  • the specific complexing agent is a compound represented by the formula (B1), a compound represented by the formula (B3), and a compound represented by the formula (B4).
  • the effect is more excellent when it contains at least one selected from the group consisting of the compound represented by the formula (C), diphosphate, hexamethaphosphate, phytic acid, and the compound represented by the formula (P1). It was confirmed that. From the comparison between Examples 29 to 30 and Example 1 and the like, it was confirmed that the effect was more excellent when the cleaning liquid further contained a surfactant. From the comparison with Examples 83 to 102 and 106 to 107, it was confirmed that the cleaning liquid was more effective when it further contained an anticorrosive agent.
  • the buffed wafer was washed over 30 seconds using a sample of each diluted washing solution adjusted to room temperature (23 ° C.), and then dried.
  • the cleaning performance of the cleaning liquid was evaluated on the polished surface of the obtained wafer according to the evaluation test method of [Evaluation of cleaning performance] described above, it was confirmed that the same evaluation results as the cleaning liquid of each of the above-mentioned Examples were shown. Was done.

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Abstract

La présente invention concerne une solution de nettoyage de substrat semi-conducteur qui présente une excellente performance de nettoyage pour des substrats semi-conducteurs traités par CMP qui comportent un film métallique contenant du tungstène, et qui présentent également une excellente performance d'inhibition de la corrosion par rapport au tungstène pendant le nettoyage d'un film métallique contenant du tungstène. Une solution de nettoyage de substrat semi-conducteur selon la présente invention est utilisée pour nettoyer des substrats semi-conducteurs et contient un polymère, une alcanolamine, un agent complexant contenant un groupe acide et de l'eau. Le poids moléculaire moyen en poids du polymère est de 2 000 à 900 000, la teneur en agent complexant par rapport à la masse totale de la solution de nettoyage de substrat semi-conducteur est d'au moins 2,5 % en masse et inférieure à 20,0 % en masse, et le pH de la solution de nettoyage de substrat semi-conducteur est inférieur à 7,0.
PCT/JP2021/025893 2020-07-30 2021-07-09 Solution de nettoyage de substrat semi-conducteur WO2022024714A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7145351B1 (ja) 2022-03-25 2022-09-30 富士フイルム株式会社 組成物、半導体素子の製造方法
WO2023182142A1 (fr) * 2022-03-25 2023-09-28 富士フイルム株式会社 Composition, procédé de fabrication d'élément semi-conducteur et procédé de lavage de substrat semi-conducteur
WO2023210579A1 (fr) * 2022-04-26 2023-11-02 富士フイルム株式会社 Procédé de formation de motif et procédé de production de dispositif électronique

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JP2006041494A (ja) * 2004-06-25 2006-02-09 Jsr Corp 半導体部品洗浄用組成物および半導体装置の製造方法
WO2018020878A1 (fr) * 2016-07-26 2018-02-01 株式会社フジミインコーポレーテッド Composition de traitement de surface et procédé de traitement de surface utilisant ladite composition de traitement de surface

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006041494A (ja) * 2004-06-25 2006-02-09 Jsr Corp 半導体部品洗浄用組成物および半導体装置の製造方法
WO2018020878A1 (fr) * 2016-07-26 2018-02-01 株式会社フジミインコーポレーテッド Composition de traitement de surface et procédé de traitement de surface utilisant ladite composition de traitement de surface

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7145351B1 (ja) 2022-03-25 2022-09-30 富士フイルム株式会社 組成物、半導体素子の製造方法
WO2023182142A1 (fr) * 2022-03-25 2023-09-28 富士フイルム株式会社 Composition, procédé de fabrication d'élément semi-conducteur et procédé de lavage de substrat semi-conducteur
WO2023181739A1 (fr) * 2022-03-25 2023-09-28 富士フイルム株式会社 Composition et procédé de production d'élément semi-conducteur
KR20230139384A (ko) * 2022-03-25 2023-10-05 후지필름 가부시키가이샤 조성물, 반도체 소자의 제조 방법
JP2023143208A (ja) * 2022-03-25 2023-10-06 富士フイルム株式会社 組成物、半導体素子の製造方法
KR102605200B1 (ko) * 2022-03-25 2023-11-24 후지필름 가부시키가이샤 조성물, 반도체 소자의 제조 방법
WO2023210579A1 (fr) * 2022-04-26 2023-11-02 富士フイルム株式会社 Procédé de formation de motif et procédé de production de dispositif électronique

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