WO2021039137A1 - Composition d'agent nettoyant - Google Patents

Composition d'agent nettoyant Download PDF

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Publication number
WO2021039137A1
WO2021039137A1 PCT/JP2020/026639 JP2020026639W WO2021039137A1 WO 2021039137 A1 WO2021039137 A1 WO 2021039137A1 JP 2020026639 W JP2020026639 W JP 2020026639W WO 2021039137 A1 WO2021039137 A1 WO 2021039137A1
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Prior art keywords
acid
compound
group
hydroxylamine
cleaning
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PCT/JP2020/026639
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English (en)
Japanese (ja)
Inventor
萌 成田
智威 高橋
篤史 水谷
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富士フイルム株式会社
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Priority to JP2021542602A priority Critical patent/JP7288511B2/ja
Priority to CN202080060051.7A priority patent/CN114341328A/zh
Publication of WO2021039137A1 publication Critical patent/WO2021039137A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
    • C23G1/18—Organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20—Other heavy metals
    • 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 agent composition.
  • the present invention relates to a cleaning agent composition that can be suitably used for manufacturing a semiconductor device.
  • Semiconductor devices such as CCD (Charge-Couple 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). By carrying out the above, a semiconductor device is manufactured.
  • CCD Charge-Couple 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).
  • a resist peeling step for peeling the resist film mainly composed of organic substances is performed by a peeling means such as a dry ashing step (for example, plasma ashing treatment), if necessary. Will be.
  • a dry ashing step for example, plasma ashing treatment
  • a residue containing a large amount of organic components derived from the resist film adheres to the wiring film and / or the interlayer insulating film, which hinders the next step.
  • a treatment for removing the residue is performed using a cleaning agent composition.
  • Patent Document 1 describes an oxidation-reducing agent, a first chelating agent which is a polyaminopolycarboxylic acid, a second chelating agent containing at least two nitrogen-containing groups, a metal corrosion inhibitor which is a benzotriazole, and an organic solvent.
  • a cleaning composition containing water and a desired pH adjuster is disclosed.
  • Patent Document 1 Based on the description of Patent Document 1, the present inventors have examined a cleaning agent composition used in a semiconductor device manufacturing process, and found that the cleaning agent composition has a further ability to remove organic residues after storage over time. We found that there was room for improvement.
  • the cleaning agent composition suppresses corrosion of the wiring metal (for example, one or more metals selected from the group consisting of Cu, W and Co) forming the metal layer of the semiconductor device to be cleaned. What to do (corrosion prevention) is required.
  • the wiring metal for example, one or more metals selected from the group consisting of Cu, W and Co
  • the present invention provides a cleaning agent composition for semiconductor devices, which is excellent in stability over time in removing organic residue and also excellent in corrosion prevention property for metal layers. Is an issue.
  • a cleaning composition for a semiconductor device which comprises one or more hydroxylamine compounds selected from the group consisting of hydroxylamine and hydroxylamine salts, carboxylic acid-based chelating agents other than polyaminocarboxylic acid, and phosphones.
  • a cleaning agent composition containing one or more chelating agents selected from the group consisting of acid-based chelating agents and a benzotriazole compound.
  • the cleaning composition according to any one of [1] to [10], wherein the mass ratio of the content of the hydroxylamine compound to the content of the chelating agent is 0.1 to 100.
  • a cleaning agent composition for a semiconductor device which is excellent in stability over time in removing organic residue and also has excellent corrosion resistance to a metal layer.
  • 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 term “preparation” as used herein means not only synthesizing or blending a specific material to prepare the material, but also procuring a predetermined material by purchase.
  • ppm means “parts-per-parts ( 10-6 )”
  • ppb means “parts-per-parts ( 10-9 )”
  • ppt means "parts-per-parts ( 10-9 )
  • the pH of the cleaning agent composition is a value measured by F-51 (trade name) manufactured by HORIBA, Ltd. at room temperature (25 ° C.).
  • radiation as used herein means an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, or electron beams.
  • light means active light rays or radiation.
  • exposure in the present invention refers not only to exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays or EUV light, but also for drawing with particle beams such as electron beams or ion beams. Include in exposure.
  • the cleaning agent composition of the present invention is a cleaning agent composition for a semiconductor device, in which one or more hydroxylamine compounds selected from the group consisting of hydroxylamine and hydroxylamine salt and a carboxylic acid (provided that polyaminocarboxylic acid) is used. It contains one or more chelating agents (hereinafter, also referred to as “specific chelating agents”) selected from the group consisting of (excluding acids) and phosphonic acids, and benzotriazole compounds.
  • chelating agents hereinafter, also referred to as “specific chelating agents” selected from the group consisting of (excluding acids) and phosphonic acids, and benzotriazole compounds.
  • the present inventors By containing the hydroxylamine compound, the specific chelating agent, and the benzotriazole compound, the present inventors surprisingly have excellent stability over time in the removal performance of organic residue and corrosion resistance to the metal layer. It was found that an excellent cleaning agent composition can be obtained.
  • the “organic residue” means a residue containing an organic substance as a main component, which is generated in the manufacturing process of a semiconductor device.
  • “having the organic substance as the main component” means that the content of the organic substance is 50% by mass or more with respect to the total amount of the residue.
  • the removal performance of organic residue is also simply referred to as "removal performance".
  • the cleaning composition of the present invention contains one or more hydroxylamine compounds selected from the group consisting of hydroxylamine and hydroxylamine salts. Hydroxylamine compounds have a function of promoting decomposition and solubilization of organic residues.
  • hydroxylamine according to a hydroxylamine compound refers to hydroxylamine in a broad sense including substituted or unsubstituted alkylhydroxylamine, and in any case, excellent removal performance with time and stability. , Excellent corrosion protection and can be obtained.
  • the hydroxylamine compound is not particularly limited, but preferred embodiments include an unsubstituted hydroxylamine and a hydroxylamine derivative, and salts thereof.
  • the hydroxylamine derivative is not particularly limited, but for example, O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, O-dimethylhydroxylamine, N-ethyl. Hydroxylamine, N, N-diethylhydroxylamine, N, O-diethylhydroxylamine, O, N, N-trimethylhydroxylamine, N, N-dicarboxyethyl hydroxylamine, and N, N-disulfoethyl hydroxylamine. Can be mentioned.
  • the salt of the unsubstituted hydroxylamine or the hydroxylamine derivative the above-mentioned inorganic acid salt or organic acid salt of the unsubstituted hydroxylamine or the hydroxylamine derivative is preferable, and non-metal atoms such as Cl, S, N or P and hydrogen atoms are used.
  • a salt with an inorganic acid formed by binding is more preferable, and a salt with any acid of hydrochloric acid, sulfuric acid and nitric acid is further preferable.
  • hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine phosphate, N, N-diethylhydroxylamine sulfate, N, N-diethylhydroxylamine nitrate, or a mixture thereof are preferable.
  • the above-mentioned unsubstituted hydroxylamine or an organic acid salt of a hydroxylamine derivative can also be used.
  • the organic acid salt include hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium fluoride.
  • hydroxylamine compound hydroxylamine, N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine, hydroxylamine sulfate, N, N-dimethylhydroxylamine sulfate, or N, N-diethylhydroxylamine sulfate is preferable. Hydroxylamine or hydroxylamine sulfate is more preferable from the viewpoint of more excellent removal performance, and hydroxylamine is further preferable from the viewpoint of more excellent corrosion prevention property.
  • the hydroxylamine compound one type may be used alone, or two or more types may be used. It is preferable to use two or more kinds of hydroxylamine compounds from the viewpoint of more excellent corrosion resistance.
  • the content of the hydroxylamine compound is, for example, 0.1 to 30% by mass with respect to the total mass of the cleaning agent composition. Above all, the content of the hydroxylamine compound is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the cleaning agent composition, from the viewpoint of more excellent removal performance. Further, the content of the hydroxylamine compound is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total mass of the cleaning agent composition, from the viewpoint of more excellent corrosion prevention.
  • the hydroxylamine compound may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above range.
  • the cleaning agent composition of the present invention contains, as a specific chelating agent, one or more compounds selected from the group consisting of carboxylic acids other than polyaminocarboxylic acids and phosphonic acid-based chelating agents.
  • a polyaminocarboxylic acid means a compound which has a plurality of amino groups and one or more carboxyl groups.
  • the specific chelating agent contained in the cleaning agent composition has a function of chelating with a metal in the cleaning step included in the manufacturing process of the semiconductor device.
  • a compound having two or more functional groups (coordinating groups) that coordinate-bond with a metal ion in one molecule is preferable.
  • the number of coordinating groups contained in the specific chelating agent is not particularly limited, but is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.
  • Phosphonate chelating agent are compounds that have one or more phosphonic acid groups and chelate with metals.
  • Examples of the phosphonic acid-based chelating agent include hydroxyphosphonic acid compounds, polyphosphonic acid compounds, aminophosphonic acid compounds, and phosphonocarboxylic acid compounds. Among them, a hydroxyphosphonic acid compound, an aminophosphonic acid compound, or a phosphonocarboxylic acid compound is preferable, and an aminophosphonic acid compound is more preferable.
  • a hydroxyphosphonic acid compound is a compound having one or more phosphonic acid groups and one or more hydroxyl groups in the molecule.
  • the polyphosphonic acid compound is a compound having two or more phosphonic acid groups in the molecule.
  • a compound having any of a hydroxyl group, an amino group and a carboxyl group in the molecule shall not be included in the polyphosphonic acid compound.
  • Examples of the hydroxyphosphonic acid compound and the polyphosphonic acid compound include compounds represented by the following formula (1).
  • X represents a hydroxy group and R 1 represents a hydrogen atom or an alkyl group.
  • Alkyl group represented by R 1 in Formula (1) is a linear, it may be any of branched and cyclic, preferably linear or branched.
  • the number of carbon atoms of the alkyl group represented by R 1 is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.
  • As the alkyl group represented by R 1 an ethyl group, an n-propyl group, or an isopropyl group is preferable.
  • n- represents a normal-form.
  • Examples of the compound represented by the formula (1) include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1,1-diphosphonic acid, and 1-hydroxybutane-1,1-diphosphonic acid. Be done.
  • Examples of the hydroxyphosphonic acid compound other than the compound represented by the formula (1) include 2-hydroxyethane-1,1-diphosphonic acid, 3-hydroxypropane-1,1-diphosphonic acid, and glycerol3-phosphate. And ethanehydroxy-1,1,2-triphosphonic acid.
  • As the hydroxyphosphonic acid compound 1-hydroxyethane-1,1-diphosphonic acid or glycerol 3-phosphate is preferable. Among them, 1-hydroxyethane-1,1-diphosphonic acid is more preferable from the viewpoint of being excellent in removal performance and corrosion prevention property, and glycerol 3-phosphate is more preferable from the viewpoint of being excellent in the time stability of removal performance.
  • An aminophosphonic acid compound is a compound having one or more phosphonic acid groups and one or more amino groups in the molecule.
  • the compound having a carboxyl group in the molecule is not included in the aminophosphonic acid compound.
  • Examples of the aminophosphonic acid compound include a compound represented by the following formula (2) and a compound represented by the formula (3).
  • Q represents a hydrogen atom or -R 3- PO 3 H 2
  • R 2 and R 3 each independently represent an alkylene group
  • Y represents a hydrogen atom, -PO 3 H 2
  • it represents a group represented by the following formula (4).
  • Q and R 3 are the same as Q and R 3 in formula (2).
  • Alkylene group represented by R 2 in formula (2) may be either linear or branched.
  • Y in the formula (2) -PO 3 H 2 or a group represented by the formula (4) is preferable, and -PO 3 H 2 is more preferable.
  • R 2 and Y in the formula (2) R 2 is a methylene group and Y is ⁇ PO 3 H 2 , or R 2 is an ethylene group and Y is the formula (4). ) Is preferred.
  • Alkylene group represented by R 3 in formula (2) and (4) may be either linear or branched.
  • an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 4 carbon atoms is more preferable, a methylene group or an ethylene group is further preferable, and a methylene group is particularly preferable.
  • aminophosphonic acid compound represented by the formula (2) examples include ethylaminobis (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid) (NTPO), and ethylenediaminebis (methylene).
  • EPDPO Phosphonic acid
  • 1,3-propylene diaminebis methylenephosphonic acid
  • EDTPO ethylenediaminetetra (methylenephosphonic acid)
  • PTMP 1,3-propylenediaminetetra (methylenephosphonic acid)
  • 1,2-diaminopropanetetra methylenephosphonic acid
  • 1,6-hexamethylenediaminetetra methylenephosphonic acid
  • R 4 and R 5 each independently represents an alkylene group having 1 to 4 carbon atoms
  • n represents an integer of 1-4
  • the number represents an alkyl group having a phosphonic acid group
  • the rest represents an alkyl group.
  • the alkylene group having 1 to 4 carbon atoms represented by R 4 and R 5 in the formula (3) may be either a linear chain or a branched chain chain.
  • an ethylene group is preferable.
  • n in the formula (3) 1 or 2 is preferable.
  • the alkyl group in the alkyl group represented by Z 1 to Z 5 in the formula (3) and the alkyl group having a phosphonic acid group may be either a linear alkyl group or a branched chain alkyl group, and may be carbon. Alkyl groups of numbers 1 to 4 are preferable, and methyl groups are more 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 or 2, and more preferably 1.
  • a monophosphonomethyl group or a monophosphonoethyl group is preferable, and a monophosphonomethyl group is more preferable.
  • Z 1 to Z 5 in the formula (3) it is preferable that all of Z 1 to Z 4 and n Z 5 are alkyl groups having the above phosphonic acid groups.
  • aminophosphonic acid compound represented by the formula (3) examples include diethylenetriaminepenta (methylenephosphonic acid) (DEPPO), diethylenetriaminepenta (ethylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), and triethylene. Tetramine hexa (ethylene phosphonic acid) can be mentioned.
  • aminophosphonic acid compounds include ethylaminobis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid) (NTPO), ethylenediaminebis (methylenephosphonic acid) (EDDPO), ethylenediaminetetra (methylenephosphonic acid) (EDTPO), and ethylenediamine.
  • NTPO nitrilotris
  • EDDPO ethylenediaminebis
  • EDTPO ethylenediaminetetra
  • ETDPO ethylenediaminetetra
  • ethylenediamine ethylenediaminetetra
  • ethylenediamine ethylenediamine.
  • Tetra (ethylene phosphonic acid), 1,3-propylene diamine tetra (methylene phosphonic acid) (PDTMP), or diethylene triaminepenta (methylene phosphonic acid) (DEPPO) is preferable, and NTPO or EDDPO is more preferable.
  • a phosphonocarboxylic acid compound is a compound having one or more carboxyl groups and one or more phosphonic acid groups in the molecule.
  • Examples of the phosphonocarboxylic acid compound include a compound represented by the following formula (5).
  • R 6 represents an (i + j) -valent aliphatic hydrocarbon group
  • i represents an integer of 1 to 4
  • j represents an integer of 1 to 4.
  • the aliphatic hydrocarbon group represented by R 6 may be linear, branched or cyclic, but is preferably linear or branched.
  • the aliphatic hydrocarbon group represented by R 6 may be either a saturated hydrocarbon or an unsaturated hydrocarbon, but a saturated hydrocarbon is preferable.
  • the aliphatic hydrocarbon group represented by R 6 may have a linking group containing one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, and may have an oxygen atom or a nitrogen atom.
  • the number of carbon atoms of the aliphatic hydrocarbon group represented by R 6 is not particularly limited, but is preferably 1 to 8, more preferably 2 to 6, and even more preferably 3 to 5.
  • I in the formula (5) is preferably an integer of 1 to 3.
  • J in the formula (5) is preferably an integer of 1 to 3, and more preferably 1 or 2.
  • the sum (i + j) of i and j in the formula (5) is preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.
  • Examples of the hydroxyphosphonic acid compound include 2-phosphonobutane-1,2,4-tricarboxylic acid, 4-phosphonobutyric acid, and glycine-N, N-bis (methylenephosphonic acid), 2-phosphonobutane-1, 2,4-Tricarboxylic acid, 4-phosphonobutyric acid, or glycine-N, N-bis (methylenephosphonic acid) is preferable.
  • 2-phosphonobutane-1,2,4-tricarboxylic acid or 4-phosphonobutyric acid is more preferable from the viewpoint of more excellent removal performance over time, and 2 from the viewpoint of excellent residue removal performance and corrosion prevention.
  • -Phosphonobtan-1,2,4-tricarboxylic acid or glycine-N, N-bis (methylenephosphonic acid) is more preferable.
  • hydroxyphosphonic acid compound 2-phosphonobutane-1,2,4-tricarboxylic acid is more preferable.
  • a polyphosphonic acid compound is a compound having two or more phosphonic acid groups in the molecule.
  • the above-mentioned hydroxyphosphonic acid compound, aminophosphonic acid compound, and phosphonocarboxylic acid compound are not included in the polyphosphonic acid compound.
  • Examples of the polyphosphonic acid compound include a compound represented by the following formula (6).
  • R 7 (-PO 3 H 2 ) k (6) R 7 represents a k-valent aliphatic hydrocarbon group, and k represents an integer of 2 to 6.
  • the aliphatic hydrocarbon group represented by R 7 may be linear, branched or cyclic, and is preferably linear or branched.
  • the aliphatic hydrocarbon group represented by R 7 may be either a saturated hydrocarbon or an unsaturated hydrocarbon, but a saturated hydrocarbon is preferable.
  • the number of carbon atoms of the aliphatic hydrocarbon group represented by R 7 is not particularly limited, but is preferably 1 to 10, and more preferably 2 to 6.
  • k is preferably an integer of 2 to 4, more preferably 2 or 3.
  • Examples of the polyphosphonic acid compound include ethylidenebisphosphonic acid, propylidenebisphosphonic acid, butylidenebisphosphonic acid, and isopropyridenebisphosphonic acid.
  • examples of the polyphosphonic acid compound include the compounds ((co) polymers) described in paragraphs [0031] to [0046] of International Publication No. 2018/030006, the contents of which are incorporated in the present specification. ..
  • a carboxylic acid chelating agent is a compound that has one or more carboxyl groups and chelate with a metal.
  • a carboxylic acid-based chelating agent excluding polyaminocarboxylic acid is simply referred to as a "carboxylic acid-based chelating agent”.
  • the compound having both a carboxyl group and a phosphonic acid group is not included in the carboxylic acid chelating agent, but is contained in the phosphonic acid chelating agent.
  • carboxylic acid-based chelating agent examples include polycarboxylic acid compounds, hydroxy acid compounds, aromatic carboxylic acid compounds, and amino acid compounds. Among them, a polycarboxylic acid compound, a hydroxy acid compound, or an aromatic carboxylic acid compound is preferable, and a hydroxy acid compound is more preferable.
  • a polycarboxylic acid compound is a compound having two or more carboxyl groups in the molecule. However, the hydroxy acid compound, aromatic carboxylic acid compound, and amino acid compound described later are not included in the polycarboxylic acid compound.
  • Examples of the polycarboxylic acid compound include a compound represented by the following formula (7).
  • R 8 (-COOH) p (7) R 8 represents a p-valent aliphatic hydrocarbon group, and p represents an integer of 2 to 6.
  • the aliphatic hydrocarbon group represented by R 8 may be linear, branched or cyclic, and is preferably linear or branched.
  • the aliphatic hydrocarbon group represented by R 8 may be either a saturated hydrocarbon or an unsaturated hydrocarbon, but a saturated hydrocarbon is preferable.
  • the aliphatic hydrocarbon group represented by R 8 may have a linking group containing one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, but contains a heteroatom. It is preferable to have no linking group.
  • the number of carbon atoms of the aliphatic hydrocarbon group represented by R 8 is not particularly limited, but is preferably 1 to 10, more preferably 2 to 6, and 2 to 4 because the removal performance is more excellent over time. More preferred.
  • p is preferably an integer of 2 to 4, more preferably 2 or 3, and even more preferably 2.
  • polycarboxylic acid compound examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 3-methyladipic acid, sebacic acid, maleic acid, and 1,3,5-pentanthricarboxylic acid.
  • Succinic acid, glutaric acid, adipic acid, pimelic acid, 3-methyladipic acid, or 1,3,5-pentanthricarboxylic acid are preferable, and succinic acid and glutaric acid are excellent in the time stability of removal performance.
  • adipic acid is more preferable.
  • 1,3,5-pentanetricarboxylic acid is more preferable.
  • a hydroxy acid compound is a compound having one or more carboxyl groups and one or more hydroxy groups in the molecule. However, compounds having an aromatic ring in the molecule are not included in the hydroxy acid compounds.
  • Examples of the hydroxy acid compound include a compound represented by the following formula (8).
  • R 9 (-COOH) m (-OH) n (8)
  • R 9 represents an (m + n) -valent aliphatic hydrocarbon group
  • m represents an integer of 1 to 4
  • n represents an integer of 1 to 4.
  • the aliphatic hydrocarbon group represented by R 9 may be linear, branched or cyclic, but is preferably linear or branched.
  • the aliphatic hydrocarbon group represented by R 9 may be either a saturated hydrocarbon or an unsaturated hydrocarbon, but a saturated hydrocarbon is preferable.
  • the aliphatic hydrocarbon group represented by R 9 may have a linking group containing one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, and may have an oxygen atom or a nitrogen atom. It is preferable to have a linking group which is, or does not have a linking group containing a hetero atom.
  • the number of carbon atoms of the aliphatic hydrocarbon group represented by R 9 is not particularly limited, but is preferably 1 to 8, more preferably 2 to 6, and further preferably 3 to 5 from the viewpoint of excellent corrosion resistance.
  • the m in the formula (8) is preferably 1 or 2, and more preferably 1.
  • N in the formula (8) is preferably an integer of 1 to 3, and more preferably 1 or 2.
  • the sum (m + n) of m and n in the formula (8) is preferably an integer of 2 to 4, and more preferably 2 or 3.
  • Examples of the hydroxy acid compound include malic acid, citric acid, glycolic acid, tartaric acid, lactic acid, and diethanol glycine.
  • Malic acid, citric acid, or diethanol glycine is preferable, and citric acid is excellent in corrosion resistance.
  • diethanolglycine is more preferable.
  • An aromatic carboxylic acid compound is a compound having one or more carboxyl groups and an aromatic ring in the molecule.
  • the aromatic carboxylic acid compound include a compound represented by the following formula (9).
  • Ar (-COOH) q (9) In the formula (9), Ar represents a q-valent aromatic hydrocarbon group which may have a substituent, and q represents an integer of 1 to 6. However, when q represents 1, the aromatic hydrocarbon group represented by Ar further has a coordinating group excluding the carboxyl group and the phosphonic acid group.
  • Examples of the substituent that the aromatic hydrocarbon group represented by Ar may have include one or more coordinating groups selected from the group consisting of a hydroxyl group, an amino group, and a sulfo group, and the above-mentioned Examples thereof include an aliphatic hydrocarbon group (preferably an alkyl group having 1 to 4 carbon atoms) which may have a coordinating group of.
  • the aliphatic hydrocarbon group contained in Ar may have a carboxy group in the formula (9).
  • the number of carbon atoms of the aromatic hydrocarbon group represented by Ar is not particularly limited, but is preferably 6 to 14, and more preferably 6 to 10. q is preferably an integer of 1 to 3, more preferably 1 or 2.
  • a benzene ring which may have a hydroxy group is preferable.
  • aromatic carboxylic acid compound examples include phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and gallic acid. Isophthalic acid or salicylic acid is preferable, and isophthalic acid is more preferable because it is excellent in corrosion prevention.
  • amino acid compound is a compound having one or more carboxyl groups and one or more amino groups as coordinating groups in the molecule. However, the above-mentioned hydroxy acid compound and aromatic carboxylic acid compound are not included in the amino acid compound.
  • amino acid compounds include glycine, serine, ⁇ -alanine (2-aminopropionic acid), ⁇ -alanine (3-aminopropionic acid), leucine, isoleucine, cysteine, ethionine, threonine, aspartic acid, glutamic acid, proline, and the like. Examples include methionine, phenylalanine, and salts thereof.
  • the salt include alkali metal salts such as sodium salt and potassium salt, ammonium salt, carbonate, and acetate.
  • a hydroxyphosphonic acid compound As the specific chelating agent, a hydroxyphosphonic acid compound, an aminophosphonic acid compound, a phosphonocarboxylic acid compound, a polycarboxylic acid compound, a hydroxy acid compound, or an aromatic carboxylic acid compound is preferable, and the removal performance and the removal performance over time are stable. From the viewpoint of superiority, an aminophosphonic acid compound or a hydroxy acid compound is more preferable.
  • the specific chelating agent may be used alone or in combination of two or more.
  • the content of the specific chelating agent is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and 0, based on the total mass of the cleaning agent composition, from the viewpoint of being more excellent in the stability over time of the removal performance. 5.5% by mass or more is more preferable.
  • the upper limit is not particularly limited, but is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably less than 2% by mass, based on the total mass of the cleaning agent composition from the viewpoint of being excellent in corrosion prevention. ..
  • the mass ratio of the content of the hydroxylamine compound to the content of the specific chelating agent is 0.1 from the viewpoint of being more excellent in corrosion prevention.
  • the above is preferable, and 1 or more is more preferable.
  • the mass ratio is preferably 100 or less, more preferably 10 or less, from the viewpoint of being more excellent in the stability over time of the removal performance.
  • the cleaning composition of the present invention contains a benzotriazole compound.
  • the benzotriazole compound is not particularly limited as long as it is a compound having a benzotriazole structure, and examples thereof include a compound represented by the following formula (A).
  • R 11 represents a substituent.
  • R 12 represents a hydrogen atom or a substituent.
  • n represents an integer of 0 to 4, and when n is 2 or more, n R 11s may be the same or different.
  • Examples of the substituent represented by R 11 in the formula (A) include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, and the following formula (B). Examples thereof include a group represented by, a hydroxyl group, a mercapto group, a carboxy group, and an alkoxycarbonyl group having 1 to 12 carbon atoms. Further, the substituent represented by R 11 may further have one or more substituents selected from the group consisting of a hydroxyl group and a carboxy group.
  • R 13 and R 14 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group.
  • R 15 represents a single bond or an alkylene group having 1 to 6 carbon atoms. * Represents the binding site.
  • R 13 and R 14 in the formula (B) are preferably an alkyl group having a hydrogen atom or a hydroxyl group and having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a 2-hydroxyethyl group.
  • R 15 in the formula (B) represents a single bond, or preferably an alkylene group having 1 to 3 carbon atoms, single bond, or an ethylene group is more preferable.
  • an amino group or an N, N-bis (hydroxyethyl) aminoethyl group is preferable.
  • N in the formula (A) is preferably an integer of 0 to 2, more preferably 0 or 1.
  • Examples of the substituent represented by R 12 include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a group represented by the above formula (B). , A hydroxyl group, a mercapto group, and an alkoxycarbonyl group having 1 to 12 carbon atoms. Further, the substituent represented by R 12 may further have one or more substituents selected from the group consisting of a hydroxyl group and a carboxy group.
  • R 12 in the formula (A) a hydrogen atom, a hydroxyl group, a group represented by the above formula (B), or an alkyl group having 1 to 6 carbon atoms which may have a carboxyl group is preferable, and a hydrogen atom. , Or a hydroxyl group is more preferred.
  • benzotriazole compound examples include benzotriazole, 5-methyl-1H-benzotriazole, 5-aminobenzotriazole, 1-hydroxybenzotriazole, 4-carboxybenzotriazole, 5,6-dimethylbenzotriazole, 1- [N, N-bis (hydroxyethyl) aminoethyl] benzotriazole, 1- (1,2-dicarboxyethyl) benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- [N , N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole, or 2,2'- ⁇ [(methyl-1H-benzotriazole-1-yl) methyl] imino ⁇ bisethanol is preferred, benzotriazole, 5- Methyl-1H-benzotriazole or 1-hydroxybenzotriazole is more preferred.
  • the benzotriazole compound may be used alone or in combination of two or more.
  • the content of the benzotriazole compound is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, based on the total mass of the cleaning agent composition, from the viewpoint of being more excellent in corrosion prevention.
  • the upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 3% by mass or less, and 0.5% by mass or less, based on the total mass of the cleaning agent composition, from the viewpoint of excellent residue removing performance. More preferred.
  • the mass ratio of the content of the hydroxylamine compound to the content of the benzotriazole compound is 1 or more because it is superior in residue removing performance.
  • the mass ratio is preferably 1000 or less, more preferably 100 or less, from the viewpoint of being more excellent in corrosion prevention.
  • the chemical solution may contain a solvent.
  • the solvent include water and organic solvents, and water is preferable.
  • the cleaning agent composition preferably contains water.
  • the type of water used in the cleaning agent composition is not particularly limited as long as it does not adversely affect the semiconductor substrate, and is distilled water, deionized water (DI (deionized) water), and pure water (ultrapure water). ). Pure water is preferable because it contains almost no impurities and has less influence on the semiconductor substrate in the manufacturing process of the semiconductor device.
  • the content of water in the cleaning agent composition is not particularly limited, but is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 85% by mass or more, based on the total mass of the cleaning agent composition.
  • the upper limit is not particularly limited, but is preferably 99% by mass or less, and more preferably 95% by mass or less.
  • the cleaning agent composition may contain an organic solvent.
  • an organic solvent a water-soluble organic solvent is preferable, an alcohol solvent, a ketone solvent, or an amide solvent is more preferable, and an alcohol solvent is further preferable.
  • alcohol solvent examples include alkanediol, alkylene glycol, alkoxyalcohol, saturated or unsaturated aliphatic alcohol, and trihydric or higher alcohol.
  • alkanediol examples include glycol, 2-methyl-1,3-propanediol, 1,2-propanediol, 1,3-propanediol (1,3-dihydroxypropane), and 2-methyl-2,4-.
  • Pentandiol 2,2-dimethyl-1,3-hexanediol, 1,4-butanediol (1,4-dihydroxybutane), 1,3-butanediol, 1,2-butanediol, 2,3-butane Examples include diols, 2,5-dihydroxy-2,5-dimethylhexane, pinacol, and alkylene glycols.
  • alkylene glycol examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol and tetraethylene glycol.
  • alkoxy alcohol examples include an alkylene glycol monoalkyl ether and an alkylene glycol dialkyl ether.
  • alkylene glycol monoalkyl ether examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol.
  • alkylene glycol dialkyl ether examples include diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene. Glycol dimethyl ether can be mentioned.
  • the alkylene glycol monoalkyl ether and the alkylene glycol dialkyl ether used in the cleaning agent composition preferably have 3 to 16 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • Saturated or unsaturated aliphatic alcohols include, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol. , 1-hexanol, allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.
  • trihydric or higher alcohols examples include glycerin.
  • Alkoxy alcohol is preferable as the alcohol solvent.
  • the alkoxy group for example, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group is preferable.
  • Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • Examples of the amide-based solvent include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.
  • alkylene glycol monoalkyl ether is preferable, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, or ethylene glycol monobutyl ether is more preferable, and ethylene glycol monobutyl ether is further preferable.
  • the organic solvent may be used alone or in combination of two or more.
  • the content of the organic solvent is preferably 0.001 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total mass of the cleaning agent composition.
  • the cleaning agent composition may contain a pH adjuster in order to adjust the pH of the cleaning agent composition.
  • a pH adjuster examples include inorganic acids, organic acids (excluding specific chelating agents), organic bases, and inorganic bases.
  • Examples of the inorganic acid include sulfuric acid, acetic acid, nitric acid, phosphoric acid, and hydrofluoric acid.
  • Examples of the organic acid include lower (1 to 4 carbon atoms) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid.
  • the above-mentioned carboxylic acid-based chelating agent may be used, which also serves as a pH adjuster for lowering the pH of the cleaning agent composition.
  • organic base examples include a quaternary ammonium salt compound, a nitrogen-containing heterocyclic compound, and a water-soluble amine.
  • quaternary ammonium salt compound a quaternary ammonium hydroxide is preferable, and a compound represented by the following formula (10) is more preferable.
  • R 4A to R 4D are independently alkyl groups having 1 to 6 carbon atoms (preferably methyl group, ethyl group, propyl group or butyl group) and hydroxyalkyl groups having 1 to 6 carbon atoms, respectively. It represents (preferably a hydroxymethyl group, a hydroxyethyl group or a hydroxybutyl group), a benzyl group, or an aryl group (preferably a phenyl group, a naphthyl group or a naphthalene group). Of these, an alkyl group having 1 to 6 carbon atoms, a hydroxyethyl group having 1 to 6 carbon atoms, or a benzyl group is preferable.
  • Examples of the compound represented by the formula (10) include tetramethylammonium hydroxide (TMAH), ethyltrimethylammonium hydroxide (ETMAH), tetraethylammonium hydroxide (TEAH), and tetrabutylammonium hydroxide (TEAH).
  • TMAH tetramethylammonium hydroxide
  • ETMAH ethyltrimethylammonium hydroxide
  • TEAH tetraethylammonium hydroxide
  • TEAH tetrabutylammonium hydroxide
  • TBAH dimethyldipropylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methyltri (hydroxyethyl) ammonium hydroxide, tetra (hydroxyethyl) ammonium hydroxide, trimethylbenzylammonium hydroxide, bishydroxyethyldimethyl
  • Examples include ammonium hydroxide and choline
  • the nitrogen-containing heterocyclic compound is a compound having a heterocycle in which at least one of the atoms constituting the ring is a nitrogen atom, and is intended to be a compound not included in the above-mentioned benzotriazole compound.
  • the nitrogen-containing heterocyclic compound include azole compounds other than benzotriazole compounds, pyridine compounds, pyrazine compounds, pyrimidine compounds, piperazine compounds, and cyclic amidin compounds, and cyclic amidin compounds are preferable.
  • Examples of the cyclic amidine compound include 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 1,5-diazabicyclo [4.3.0] nonene-5 (DBN).
  • the water-soluble amine is intended to be an amine capable of dissolving 50 g or more in 1 L of water.
  • the pKa of the water-soluble amine is not particularly limited, but is preferably 7.5 to 13.0.
  • the water-soluble amine does not contain the above-mentioned hydroxylamine compound and ammonia.
  • Examples of the inorganic base include alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia.
  • Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • Examples of the alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • a quaternary ammonium hydroxide As the pH adjusting agent for lowering the pH of the cleaning agent composition, a quaternary ammonium hydroxide, a nitrogen-containing heterocyclic compound, a water-soluble amine, or ammonia is preferable, and is represented by the above formula (10). Quaternary ammonium hydroxides, cyclic amidine compounds, or water-soluble amines are more preferred.
  • the pH adjuster may be used alone or in combination of two or more.
  • the type and content of the pH adjuster may be adjusted by appropriately selecting the type of pH adjuster to be used so that the pH of the cleaning agent composition is within a preferable range described later.
  • the content of the inorganic base is preferably 0.1% by mass or less based on the total mass of the cleaning agent composition.
  • the cleaning agent composition may contain additives other than the above-mentioned components, if necessary.
  • additives include surfactants, reducing agents, antifoaming agents, rust inhibitors, and preservatives.
  • the cleaning agent composition may contain a surfactant.
  • the type of the surfactant is not particularly limited, and examples thereof include an ionic surfactant (anionic surfactant, a cationic surfactant, and an amphoteric surfactant), and a nonionic surfactant.
  • the content of the surfactant is preferably 1% by mass or more and 3% by mass or less with respect to the total mass of the cleaning agent composition.
  • the cleaning agent composition may contain components other than the above-mentioned components as long as the effects of the present invention and the functions of each component are not impaired.
  • the content of the above-mentioned components contained in the cleaning agent composition is determined by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). It can be measured by a known method such as a method and an ion exchange chromatography (IC: (Ion-exchange Chromatography) method).
  • GC-MS gas chromatography-mass spectrometry
  • LC-MS liquid chromatography-mass spectrometry
  • the pH of the cleaning agent composition is not particularly limited, but is preferably more than 7 and more preferably 8 or more from the viewpoints of excellent removal performance over time and excellent corrosion prevention.
  • the upper limit of pH is not particularly limited, but is preferably 14 or less, and more preferably 12 or less.
  • the pH of the cleaning agent composition may be adjusted using the pH adjuster described above. In the present specification, the pH of the cleaning agent composition is obtained by measuring at 25 ° C. using a pH meter (F-51 (trade name) manufactured by HORIBA, Ltd.).
  • the method for producing the cleaning agent composition is not particularly limited, and for example, the composition 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.
  • a hydroxylamine compound, a specific chelating agent, a benzotriazole compound, and an optional component are sequentially added to a stirrer such as a mixing mixer containing purified pure water, and then sufficiently stirred to mix each component.
  • a stirrer such as a mixing mixer containing purified pure water
  • each raw material used for preparing the cleaning agent composition it is preferable to use one classified into a semiconductor grade or a high-purity grade equivalent thereto.
  • any one or more of the raw materials for producing the cleaning agent composition may be purified in advance by distillation, ion exchange, or filtration.
  • the purification method is not particularly limited, and examples thereof include a method of passing through an ion exchange resin or an RO membrane (Reverse Osmosis Membrane), distillation, and filtering. More specifically, after passing the liquid through a reverse osmosis membrane for primary purification, the liquid is passed through a purification device made of a cation exchange resin, an anion exchange resin, or a mixed bed type ion exchange resin for secondary purification. There is a method to carry out.
  • a purification device made of a cation exchange resin, an anion exchange resin, or a mixed bed type ion exchange resin for secondary purification.
  • the cleaning agent composition may be a kit in which the raw materials thereof are divided into a plurality of parts.
  • a liquid composition containing a hydroxylamine compound, a specific chelating agent and a benzotriazole compound is prepared as the first liquid, and as the second liquid.
  • An embodiment of preparing a liquid composition containing other components can be mentioned.
  • the cleaning agent composition may be prepared using a concentrated solution.
  • the concentration ratio thereof is appropriately determined depending on the composition to be composed, but is preferably 5 to 2000 times. That is, the cleaning agent composition is used by diluting the concentrated solution 5 to 2000 times.
  • it is preferable to reduce the amount of water that causes the decomposition of the hydroxylamine compound as much as possible so that the composition contains a large amount of alcohol solvent.
  • the cleaning composition can be stored, transported, and used in any container as long as it does not cause problems such as corrosiveness (whether it is a kit or a concentrate).
  • the container it is preferable that the container has a high degree of cleanliness and less elution of impurities for semiconductor applications. Examples of the container that can be used include, but are not limited to, the "clean bottle” series manufactured by Aicello Chemical Corporation and the “pure bottle” manufactured by Kodama Resin Industry.
  • the container a container whose inside has been cleaned before being filled with the cleaning agent composition is preferable.
  • the liquid used for cleaning preferably has a reduced amount of metal impurities in the liquid.
  • the cleaning agent composition may be bottling, transported, and stored in a container such as a gallon bottle or a coated bottle after production.
  • the clean room preferably meets the 146441 clean room standard, more preferably any of ISO (International Organization for Standardization) class 1, ISO class 2, ISO class 3, and ISO class 4, and ISO class 1 or ISO class. It is more preferable to satisfy 2 and it is particularly preferable to satisfy ISO class 1.
  • ISO International Organization for Standardization
  • cleaning step B examples of the cleaning method using the cleaning agent composition include an embodiment having a cleaning step (hereinafter, also referred to as “cleaning step B”) for cleaning a semiconductor substrate having a metal layer using the cleaning agent composition. Be done. Further, the cleaning method may include a cleaning agent composition preparation step (hereinafter, also referred to as “cleaning agent composition preparation step A”) for preparing the cleaning agent composition before the cleaning step B.
  • cleaning agent composition preparation step A a cleaning agent composition preparation step for preparing the cleaning agent composition before the cleaning step B.
  • the object to be cleaned is not particularly limited as long as it is used in the manufacturing process of a semiconductor device, and examples thereof include a semiconductor substrate having a metal layer formed by using a metal wiring material.
  • the metal wiring material include Cu (copper), W (tungsten), and Co (cobalt).
  • More specific objects to be cleaned include, for example, a laminate having the above-mentioned metal layer, interlayer insulating layer, and metal hard mask in this order on a substrate.
  • the laminate further has holes formed from the surface (opening) of the metal hard mask toward the substrate so as to expose the surface of the metal layer by undergoing a dry etching step.
  • the method for producing a laminate having holes as described above is not particularly limited.
  • a method of performing a dry etching process using a metal hard mask as a mask and etching the interlayer insulating layer so that the surface of the metal layer is exposed to provide holes penetrating the inside of the metal hard mask and the interlayer insulating layer. can be mentioned.
  • the method for producing the metal hard mask is not particularly limited. For example, first, a metal film containing a predetermined component is formed on the interlayer insulating layer, a resist film having a predetermined pattern is formed on the metal film, and then a resist film is formed.
  • An example is a method of producing a metal hard mask (that is, a film in which a metal film is patterned) by etching a metal film using the film as a mask.
  • a resist peeling step of peeling the resist film is performed by a dry ashing treatment such as a plasma ashing treatment.
  • a residue containing an organic component derived from the resist film is attached to the metal layer and / or the interlayer insulating layer. These adhered residues are removed from the laminate using the cleaning agent composition.
  • the laminate may have a layer other than the above-mentioned layer, and examples thereof include an etching stop layer and an antireflection layer.
  • FIG. 1 is a schematic cross-sectional view showing an example of a laminate that is a cleaning target of a cleaning method using the cleaning agent composition.
  • the laminate 10 shown in FIG. 1 is provided with a metal layer 2, an etching stop layer 3, an interlayer insulation layer 4, and a metal hard mask 5 in this order on a substrate 1, and a metal layer is formed at a predetermined position after undergoing a dry etching process. A hole 6 in which 2 is exposed is formed. That is, the laminate 10 shown in FIG. 1 includes a substrate 1, a metal layer 2, an etching stop layer 3, an interlayer insulating layer 4, and a metal hard mask 5 in this order, and an opening of the metal hard mask 5.
  • the inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a made of an etching stop layer 3, an interlayer insulating layer 4 and a metal hard mask 5, and a bottom wall 11b made of an exposed metal layer 2, to which a residue 12 adheres. ing.
  • the cleaning method can be suitably used for cleaning for the purpose of removing these residues 12. That is, the cleaning agent composition is excellent in the removal performance of the residue 12 and also in the corrosion prevention property for the inner wall 11 (for example, the metal layer 2 and the like) of the object to be cleaned.
  • the inner wall 11 for example, the metal layer 2 and the like
  • the metal hard mask preferably contains at least one component selected from the group consisting of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx.
  • Examples of the material of the metal hard mask include TiN, WO 2 and ZrO 2 .
  • the material of the interlayer insulating layer is not particularly limited, and examples thereof include those having a dielectric constant k of 3.0 or less, more preferably 2.6 or less.
  • Specific examples of the material of the interlayer insulating layer include organic polymers such as SiO 2 , SiOC materials and polyimide.
  • the material of the etching stop layer is not particularly limited. Specific examples of the etching stop layer material include SiN, SiON, SiOCN-based materials, and metal oxides such as AlOx.
  • the wiring material forming the metal layer is not particularly limited, and examples thereof include metals containing one or more selected from the group consisting of Cu (copper), W (tungsten), and Co (cobalt).
  • the wiring material may be a metal consisting only of Cu, W or Co, or may be an alloy of Cu, W or Co with another metal. Among them, a metal containing W or Co is preferable, and a metal containing Co is more preferable.
  • the wiring material may further contain a metal other than Cu, W and Co, a metal nitride or an alloy, for example, titanium, titanium-titanium, titanium nitride, tantalum, tantalum compound, chromium, chromium oxide, and It may further contain one or more selected from the group consisting of aluminum.
  • the “substrate” here includes, for example, a semiconductor substrate composed of a single layer and a semiconductor substrate composed of multiple layers.
  • the material constituting the semiconductor substrate composed of a single layer is not particularly limited, and is preferably composed of a Group III-V compound such as silicon, silicon germanium, or GaAs, or any combination thereof.
  • the configuration is not particularly limited, and for example, the above-mentioned integrated structure (interconnect features) such as a metal wire and a dielectric material is exposed on a semiconductor substrate such as silicon. It may have a circuit structure.
  • Metals and alloys used in interconnect structures include, but are limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. It's not a thing. Further, a layer such as an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide may be provided on the semiconductor substrate.
  • the cleaning agent composition preparation step A is a step of preparing the cleaning agent composition.
  • Each component used in this step is as described above.
  • the procedure of this step is not particularly limited, and for example, a method of preparing a cleaning agent composition by adding a hydroxylamine compound, a specific chelating agent, a benzotriazole compound, and other optional components and stirring and mixing them. Can be mentioned. When each component is added, it may be added all at once, or it may be added in multiple portions. Further, as each component contained in the cleaning agent composition, it is preferable to use one classified into a semiconductor grade or a high-purity grade equivalent thereto, and foreign matter removal by filtering and / or ions. It is preferable to use a resin obtained by reducing the ionic component with an exchange resin. Further, after mixing the raw material components, it is preferable to further remove foreign substances by filtering and / or reduce the ion components by an ion exchange resin.
  • the concentrated solution is diluted to obtain a diluted solution before performing the cleaning step B, and then the cleaning step B is performed using this diluted solution. carry out.
  • the above dilution is preferably carried out using a diluent containing water.
  • Cleaning step B Examples of the object to be cleaned to be cleaned in the cleaning step B include the above-mentioned laminate, and as described above, the laminate 10 in which holes are formed by performing a dry etching step and a dry ashing step is exemplified (FIG. 1). The residue 12 adheres to the hole 6 in the laminate 10.
  • the method of bringing the cleaning agent composition into contact with the cleaning object is not particularly limited, and for example, a method of immersing the cleaning object in the cleaning agent composition placed in a container, or spraying the cleaning agent composition on the cleaning object. Methods, methods of flowing the cleaning agent composition over the object to be cleaned, and combinations thereof can be mentioned. From the viewpoint of removal performance, a method of immersing the object to be cleaned in the cleaning agent composition is preferable.
  • the temperature of the cleaning agent composition is preferably 90 ° C. or lower, more preferably 25 to 80 ° C., further preferably 30 to 75 ° C., and particularly preferably 40 to 70 ° C.
  • the cleaning time can be adjusted according to the cleaning method used and the temperature of the cleaning agent composition.
  • the cleaning time is, for example, 60 minutes or less, preferably 1 to 60 minutes, and 3 to 3 to 60 minutes. 20 minutes is more preferred, and 4 to 15 minutes is even more preferred.
  • the washing time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, more preferably 15 seconds to 3 minutes, still more preferably 20 seconds to 2 minutes.
  • a mechanical stirring method may be used to further enhance the cleaning ability of the cleaning agent composition.
  • the mechanical stirring method include a method of circulating the cleaning agent composition on the object to be cleaned, a method of flowing or spraying the cleaning agent composition on the object to be cleaned, and cleaning by ultrasonic waves or megasonic. Examples thereof include a method of stirring the agent composition.
  • the method for cleaning the substrate using the cleaning agent composition may further include a step of rinsing and cleaning the object to be cleaned with a solvent (hereinafter referred to as “rinse step B2”) after the cleaning step.
  • the rinsing step B2 is preferably performed after the washing step, and is preferably a rinsing step with a rinsing solvent (rinsing solution) for 5 seconds to 5 minutes.
  • the rinsing step B2 may be performed by using the above-mentioned mechanical stirring method.
  • the rinsing solvent is not particularly limited, and examples thereof include deionized water, methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, ⁇ -butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Be done. Further, an aqueous rinse solution having a pH of more than 8 (diluted aqueous ammonium hydroxide or the like) may be used.
  • ammonium hydroxide aqueous solution, DI water, methanol, ethanol, or isopropyl alcohol is preferable, ammonium hydroxide aqueous solution, DI water, or isopropyl alcohol is more preferable, and ammonium hydroxide aqueous solution or DI water is further preferable.
  • a method of bringing the rinse solvent into contact with the object to be cleaned the above-mentioned method of bringing the cleaning agent composition into contact with the object to be cleaned can be similarly applied.
  • the temperature of the rinsing solvent in the rinsing step B2 is preferably 16 to 27 ° C.
  • the method for cleaning the substrate using the cleaning agent composition may include a drying step of drying the object to be cleaned after the rinsing step.
  • the drying method is not particularly limited, for example, a spin drying method, a method of flowing a dry gas over the surface of the object to be cleaned, a method of heating the substrate by a heating means such as a hot plate or an infrared lamp, and a flatulence drying method. , Rotagoni drying method, IPA (isopropyl alcohol) drying method, and combinations thereof.
  • the drying time varies depending on the drying method, but is preferably 30 seconds to several minutes.
  • the object to be cleaned in the method of cleaning a substrate using a cleaning agent composition is not limited to a laminate having a metal layer, an interlayer insulating layer, and a metal hard mask on the substrate in at least this order as described above.
  • it can also be used for removing residues derived from a photoresist film adhering to a laminate having a metal layer, an interlayer insulating layer, and a photoresist film on a substrate in at least this order.
  • a cleaning composition was prepared according to the following procedure. The contents of various components used in each cleaning agent composition (all based on mass) are as described in the table.
  • the raw materials used to prepare the cleaning composition are shown below.
  • the compounds used in the preparation of the cleaning agent composition those classified into the semiconductor grade or those classified into the high purity grade equivalent thereto were used.
  • HA Hydroxylamine HAS: Hydroxylamine Sulfate
  • DEHA N, N-diethylhydroxylamine
  • H 2 O 2 Hydrogen peroxide (not a hydroxylamine compound)
  • the resist film, metal hard mask (TiN layer), an etch stop layer (Al 2 O 3 layer), Co layer and an interlayer insulating (ILD) layer was prepared a multi-layer substrate are laminated in this order .
  • This multi-layer substrate is subjected to patterning treatment by lithography, etching treatment using a plasma etching apparatus for metal, and removal treatment of a resist film by oxygen plasma ashing, and a multi-layer substrate for evaluation test (hereinafter referred to as "test").
  • test a multi-layer substrate for evaluation test
  • a glass beaker having a volume of 500 mL was filled with 200 mL of the cleaning agent composition.
  • the temperature of the cleaning agent composition was raised to 65 ° C. while stirring with a stirrer.
  • the test piece was washed by immersing the test piece prepared above in the cleaning agent composition having a liquid temperature of 65 ° C. for 5 minutes with stirring. While the test piece was immersed in the cleaning agent composition, the test piece was held using 4-inch long plastic locking tweezers so that the side surface of the test piece from which the photoresist was removed faced the stir bar.
  • test piece was immediately removed from the cleaning composition and placed in 400 mL DI water (water temperature 17 ° C.) filled in a 500 mL plastic beaker and gently agitated. After immersing the test piece in DI water for 30 seconds, the test piece was immediately taken out and rinsed under a DI water stream at 17 ° C. for 30 seconds.
  • DI water water temperature 17 ° C.
  • test piece was removed from the holding portion of the plastic tweezers, and the test piece was placed in a plastic storage box with a lid with the element side facing up and stored.
  • the surface of the obtained test piece was subjected to composition analysis by X-ray Photoelectron Spectroscopy (XPS).
  • XPS X-ray Photoelectron Spectroscopy
  • the surface of the obtained test piece was measured using an XPS device (manufactured by ULVAC-PHI, trade name QuanteraSXM).
  • the reduction rate before and after the treatment was calculated and used as the residue removal rate.
  • the removal performance of organic residue was evaluated according to the following evaluation criteria. 5: Removal rate is 95% or more 4: Removal rate is 80% or more and less than 95% 3: Removal rate is 75% or more and less than 80% 2: Removal rate is 50% or more and less than 75% 1: Removal rate is less than 50%
  • a substrate (a substrate on which a metal layer was formed) having a layer made of Co (Co layer) formed by a CVD (Chemical Vapor Deposition) method was prepared on one surface of a substrate (silicon wafer (diameter: 12 inches)).
  • the substrate on which the Co layer was formed was immersed in the cleaning agent compositions (65 ° C.) of Examples and Comparative Examples for 5 minutes.
  • the etching rate ( ⁇ / min) of the cleaning agent composition with respect to the Co layer was calculated from the difference in the thickness of the Co layer before and after immersion in the cleaning agent composition. The lower the etching rate (ER) for Co measured in this test, the better the corrosion prevention property for Co.
  • the "ratio 1" column shows the ratio (mass ratio) of the content of the hydroxylamine compound (or redox agent) to the content of the chelating agent
  • the “ratio 2” column shows the ratio to the content of the benzotetrazole compound. The ratio (mass ratio) of the content of the hydroxylamine compound (or the redox agent) is shown.
  • the "removal performance” column shows the evaluation results of the removal performance of the organic residue using the cleaning agent compositions of each Example and each Comparative Example.
  • the “after preparation” column of “removal performance” shows the evaluation result of the removal performance performed immediately after preparing each cleaning agent composition, and the “after storage” column of “removal performance” shows each cleaning after the storage test. The evaluation result of the removal performance performed on the agent composition is shown.
  • the content of the specific chelating agent is 0.1% by mass or more based on the total mass of the cleaning agent composition, the removal performance is more excellent over time, and when it is 0.5% by mass or more, the removal performance is time-dependent. It was confirmed that the stability was further excellent (comparison of Examples 1 to 3 and comparison of Examples 24, 25 and 27). Further, it was confirmed that when the content of the specific chelating agent was 10% by mass or less with respect to the total mass of the cleaning agent composition, it was superior in corrosion prevention property (comparison of Examples 4 and 5).
  • the ratio 1 mass ratio of the content of the hydroxylamine compound to the content of the specific chelating agent
  • the removal performance is more excellent over time and the ratio 1 is 10 or less. It was confirmed that the removal performance was more excellent in stability over time (comparison of Examples 1 to 3 and comparison of Examples 24, 25 and 27). Further, it was confirmed that when the ratio 1 is 0.1 or more, the corrosion prevention property is superior, and when the ratio 1 is 1 or more, the corrosion prevention property is further excellent (comparison of Examples 2, 4 and 5). Comparison of Examples 28 and 35).

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Abstract

La présente invention aborde le problème de la fourniture d'une composition d'agent nettoyant pour dispositifs à semi-conducteurs, ladite composition d'agent nettoyant présentant une excellente stabilité à long terme en termes de performances d'élimination de résidus organiques, tout en présentant d'excellentes propriétés de prévention de la corrosion par rapport à une couche métallique. Une composition d'agent nettoyant selon la présente invention est une composition d'agent nettoyant pour dispositifs à semi-conducteurs contenant : un ou plusieurs composés hydroxylamine qui sont choisis dans le groupe constitué par l'hydroxylamine et des sels d'hydroxylamine ; un ou plusieurs agents de chélation qui sont choisis dans le groupe constitué par les agents de chélation à base d'acide phosphonique et les agents de chélation à base d'acide carboxylique à l'exclusion des acides polyamino-carboxyliques ; et un composé benzotriazole.
PCT/JP2020/026639 2019-08-23 2020-07-08 Composition d'agent nettoyant WO2021039137A1 (fr)

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WO2022190699A1 (fr) * 2021-03-11 2022-09-15 富士フイルム株式会社 Solution chimique et procédé de traitement

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JP2005307187A (ja) * 2004-03-19 2005-11-04 Air Products & Chemicals Inc 化学的機械的平坦化後用のアルカリ性洗浄組成物
JP2012072267A (ja) * 2010-09-28 2012-04-12 Sanyo Chem Ind Ltd 電子材料用洗浄剤
WO2018043440A1 (fr) * 2016-08-31 2018-03-08 富士フイルム株式会社 Liquide de traitement, procédé de nettoyage de substrat, et procédé de fabrication de dispositif à semi-conducteurs

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CN105873691B (zh) 2013-12-06 2018-04-20 富士胶片电子材料美国有限公司 用于去除表面上的残余物的清洗调配物
KR102027795B1 (ko) 2016-01-05 2019-10-02 후지필름 가부시키가이샤 처리액, 기판의 세정 방법, 및 반도체 디바이스의 제조 방법
JP6542393B2 (ja) 2016-01-05 2019-07-10 富士フイルム株式会社 処理液、基板の洗浄方法および半導体デバイスの製造方法

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JP2005307187A (ja) * 2004-03-19 2005-11-04 Air Products & Chemicals Inc 化学的機械的平坦化後用のアルカリ性洗浄組成物
JP2012072267A (ja) * 2010-09-28 2012-04-12 Sanyo Chem Ind Ltd 電子材料用洗浄剤
WO2018043440A1 (fr) * 2016-08-31 2018-03-08 富士フイルム株式会社 Liquide de traitement, procédé de nettoyage de substrat, et procédé de fabrication de dispositif à semi-conducteurs

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Publication number Priority date Publication date Assignee Title
WO2022190699A1 (fr) * 2021-03-11 2022-09-15 富士フイルム株式会社 Solution chimique et procédé de traitement

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