WO2021049330A1 - Liquide de traitement, procédé de traitement - Google Patents

Liquide de traitement, procédé de traitement Download PDF

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Publication number
WO2021049330A1
WO2021049330A1 PCT/JP2020/032679 JP2020032679W WO2021049330A1 WO 2021049330 A1 WO2021049330 A1 WO 2021049330A1 JP 2020032679 W JP2020032679 W JP 2020032679W WO 2021049330 A1 WO2021049330 A1 WO 2021049330A1
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WIPO (PCT)
Prior art keywords
group
treatment liquid
compound
metal
acid
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PCT/JP2020/032679
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English (en)
Japanese (ja)
Inventor
智美 高橋
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富士フイルム株式会社
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Priority to JP2021545217A priority Critical patent/JPWO2021049330A1/ja
Publication of WO2021049330A1 publication Critical patent/WO2021049330A1/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
    • 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
    • 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
    • C11D7/34—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • 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
    • 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
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • 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
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks

Definitions

  • the present invention relates to a treatment liquid and a treatment method.
  • CCD Charge-Coupled Device
  • semiconductor devices such as memories are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology.
  • a substrate, a metal layer formed on the substrate as a wiring material, an etching stop layer formed on the metal layer, and an interlayer insulating film formed on the etching stop layer are used between layers.
  • a dry etching step is performed on a laminate containing a metal hard mask formed on an insulating film using the metal hard mask as a mask, and each member is etched so that the surface of the metal layer is exposed.
  • a method of providing a metal hard mask, an interlayer insulating film, and a hole penetrating the etching stop layer can be mentioned.
  • a process of removing an unnecessary portion (removal target object) from such a laminated body may be performed.
  • a residue (dry etching residue) of each member may be attached to at least one of the metal layer constituting the hole and the interlayer insulating film. Therefore, a treatment for removing the residue of each member as a removal target may be performed using a treatment liquid.
  • Patent Document 1 discloses "an aqueous cleaning composition containing at least one kind of corrosion inhibitor, water ... in some cases, at least one kind of etchant ... (Claim 1)". .. Hydrofluoric acid and the like have been proposed as the etchant in the aqueous cleaning composition (treatment liquid) (claim 4).
  • the laminate that has undergone the dry etching step contains a cobalt-containing substance (Co-containing substance), a copper-containing substance (Cu-containing substance), or the like as a metal layer
  • the purpose of removal is to use a treatment liquid.
  • Co-containing substance a cobalt-containing substance
  • Cu-containing substance copper-containing substance
  • the purpose of removal is to use a treatment liquid.
  • the present invention includes one or more first metals selected from the group consisting of Co and Cu while having excellent removability of the object to be removed (for example, dry etching residue and / or metal hard mask).
  • An object of the present invention is to provide a treatment liquid capable of suppressing etching of a first metal-containing material and a treatment method.
  • Etchant and With organic solvent Contains anticorrosive agents, The content of the organic solvent is 80% by mass or more with respect to the total mass of the treatment liquid.
  • a treatment liquid in which the anticorrosive agent is one or more compounds selected from the group consisting of compound X, compound Y, and compound Z.
  • Compound X One substituent XA which is a group represented by any of the general formulas (XA1) to (XA3) and a substituent which is a group represented by any of the general formulas (XB1) to (XB7).
  • * represents a bonding position.
  • R independently represents a hydrogen atom or an alkyl group.
  • Compound Y A compound represented by the general formula (Y). Y Q- COOH (Y) In the general formula (Y), Y Q represents an aromatic ring group having an oxyphosphonate group, an aromatic ring group having a boronate group, or a phosphonic acid group-alkylene group.
  • Compound Z One or more compounds selected from the group consisting of mellitic acid and oxalic acid.
  • the above etchant is selected from the group consisting of hydrogen fluoride, ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, hexafluorosilicic acid, hexafluorophosphoric acid, and tetrafluoroboric acid.
  • the treatment solution according to [1] or [2] which is one or more compounds to be treated.
  • the organic solvents are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, hexanol, 1-octanol, 2-octanol, and 2-ethylhexanol.
  • the object to be treated further contains a second metal-containing material containing one or more second metals selected from the group consisting of Zr, Ti, Hf, and Ta.
  • a treatment method comprising a step of bringing the treatment liquid according to any one of [1] to [9] into contact with the object to be treated to remove the second metal-containing substance.
  • the object to be treated further contains a dry etching residue
  • a treatment method comprising a step of bringing the treatment liquid according to any one of [1] to [9] into contact with the object to be processed to remove the dry etching residue.
  • the treatment method according to any one of [10] to [12], wherein the removal rate of the first metal-containing substance when the treatment liquid is brought into contact with the object to be treated is 10 ⁇ / min or less.
  • a treatment liquid capable of suppressing etching of a first metal-containing material containing one or more first metals selected from the group consisting of Co and Cu, while having excellent removability of the object to be removed, and A processing method 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 term "preparation” means not only preparing a specific material by synthesizing or blending it, but also procuring a predetermined material by purchasing or the like.
  • 1 ⁇ corresponds to 0.1 nm.
  • the group not described as substituted or unsubstituted includes a group containing a substituent as well as a group containing no substituent as long as the effect of the present invention is not impaired.
  • the "hydrocarbon group” includes not only a hydrocarbon group containing no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group containing a substituent (substituted hydrocarbon group). This is also synonymous with each compound.
  • the "pH” in the present invention is a value measured at 23 ° C. using a pH meter (product name “pH Meter F-51", manufactured by HORIBA, Ltd.). The value read after starting the measurement and stabilizing the displayed value is defined as pH.
  • the treatment liquid of the present invention is a treatment liquid used for treating an object to be treated containing a first metal-containing material containing one or more first metals selected from the group consisting of Co and Cu. , Etchant, organic solvent, and anticorrosive agent.
  • the content of the organic solvent is 80% by mass or more with respect to the total mass of the treatment liquid.
  • the anticorrosive agent is one or more compounds selected from the group consisting of Compound X described later, Compound Y described later, and Compound Z described later.
  • an etchant and a predetermined anticorrosive agent are present in a high-concentration organic solvent.
  • etching of the first metal-containing material is suppressed (corrosion prevention) by a predetermined anticorrosive agent while enabling removal of the object to be removed mainly by etching.
  • the above-mentioned anticorrosive agent can realize a particularly good anticorrosive action in a high concentration organic solvent, and such a feature realizes the effect of the present invention.
  • the treatment liquid of the present invention has good corrosion resistance against aluminum-based materials such as Al or Al 2 O 3.
  • examples of the object to be removed include a metal hard mask and an etching residue.
  • any one of corrosion resistance to the first metal-containing material for example, corrosion resistance to the Co-containing material and corrosion resistance to the Cu-containing material
  • corrosion resistance to the aluminum-based material for example, corrosion resistance to the Co-containing material and corrosion resistance to the Cu-containing material
  • removal property to the object to be removed for example, corrosion resistance to the aluminum-based material
  • the effect of the present invention is more excellent when it is more excellent than the above.
  • the treatment liquid of the present invention contains an etchant.
  • the etchant has a function of removing (dissolving) objects to be removed (metal hard mask, etching residue, etc.).
  • the etchant is preferably a halogen-containing compound (a compound containing a halogen atom in the compound), and more preferably a fluorine-containing compound.
  • the fluorine-containing compound is not particularly limited as long as the compound contains a fluorine atom, and a known fluorine-containing compound can be used. Among them, as the fluorine-containing compound, a compound that dissociates in the treatment liquid and releases fluoride ions is also preferable.
  • fluorine-containing compound examples include hydrogen fluoride (HF), ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, hexafluorosilicic acid, hexafluorophosphate, and tetrafluoroboric acid. , Ammonium hexafluorophosphate, ammonium hexafluorosilicate and the like.
  • the fluorine-containing compound is hydrogen fluoride (HF), ammonium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, hexafluorosilicic acid, because the effect of the present invention is more excellent.
  • HF hydrogen fluoride
  • ammonium fluoride tetramethylammonium fluoride
  • tetraethylammonium fluoride tetrabutylammonium fluoride
  • hexafluorosilicic acid because the effect of the present invention is more excellent.
  • Hexafluorophosphoric acid or tetrafluoroboric acid is preferable, and hydrogen fluoride is more preferable.
  • the content of the etchant (preferably a fluorine-containing compound) in the treatment liquid is preferably 0.01% by mass or more, preferably 0.05% by mass, based on the total mass of the treatment liquid.
  • the above is more preferable, and 0.1% by mass or more is further preferable.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.
  • the etchant (preferably a fluorine-containing compound) may be used alone or in combination of two or more. When two or more kinds of etchants (preferably fluorine-containing compounds) are used, the total content is preferably within the above range.
  • the treatment liquid of the present invention contains an organic solvent.
  • the content of the organic solvent (preferably an alcohol solvent) in the treatment liquid of the present invention is 80% by mass or more, preferably 80 to 99.9% by mass, and 80 to 99% by mass, based on the total mass of the treatment liquid.
  • the mass% is more preferable, and 90 to 98% by mass is further preferable.
  • the organic solvent may be used alone or in combination of two or more. When two or more kinds of organic solvents are used, the total content is preferably within the above range.
  • the organic solvent any known organic solvent can be used, but a hydrophilic organic solvent is preferable.
  • the hydrophilic organic solvent means an organic solvent that can be uniformly mixed with water in any ratio.
  • examples of the organic solvent include alcohol-based solvents, ketone-based solvents, ester-based solvents, ether-based solvents (for example, glycol diether), sulfone-based solvents, sulfoxide-based solvents, nitrile-based solvents, and amide-based solvents. Be done. It is also preferable that these organic solvents are hydrophilic organic solvents.
  • the organic solvent is preferably an alcohol solvent.
  • the alcohol-based solvent examples include alkanediol (including, for example, alkylene glycol), alkoxyalcohol (including, for example, glycol monoether), saturated aliphatic monohydric alcohol, unsaturated non-aromatic monohydric alcohol, and ring. Examples thereof include low molecular weight alcohols containing a structure. Among them, the alcohol solvent is preferably glycol monoether or saturated aliphatic monohydric alcohol.
  • alkanediol examples include glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, and 1,3.
  • -Butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, alkylene glycol and the like can be mentioned.
  • alkylene glycol examples include ethylene glycol, propylene glycol, hexylene 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, glycol monoether and the like.
  • glycol monoether examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monon-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl 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 and ethylene glycol mono Benzyl ether and diethylene glycol monobenzyl ether, 1-octanol, 2-octanol, 2-ethylhexanol and the like can be mentioned.
  • Saturated aliphatic monohydric 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, and , Hexanol and the like.
  • unsaturated non-aromatic monohydric alcohols examples include allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, 4-pentene-2-ol and the like.
  • low molecular weight alcohols containing a ring 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-hydroxyacetphenone, and 1,3-cyclohexane.
  • dione and cyclohexanone 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.
  • glycol monoether monoesters such as ethylene glycol monoethyl ether acetate.
  • ethylene glycol monobutyl ether, tri (propylene glycol) methyl ether, and diethylene glycol monoethyl ether are preferable.
  • sulfone solvent examples include sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane and the like.
  • sulfoxide solvent examples include dimethyl sulfoxide and the like.
  • nitrile solvent examples include acetonitrile and the like.
  • 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, hexamethylphosphoric triamide and the like can be mentioned.
  • ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, hexanol, 1-octanol, 2-octanol, and 2-ethylhexanol.
  • One or more compounds selected from are preferred.
  • the organic solvent it is preferable to use a high-purity organic solvent having a reduced metal ion content, and it may be further purified and used.
  • the purification method is not particularly limited, but known methods such as filtration, ion exchange, distillation, adsorption purification, recrystallization, reprecipitation, sublimation, and purification using a column can be used, and these can be applied in combination. You may.
  • the treatment liquid of the present invention contains an anticorrosive agent.
  • the anticorrosive agent is one or more compounds selected from the group consisting of compound X, compound Y, and compound Z.
  • the above-mentioned anticorrosive agent may be used alone or in combination of two or more.
  • the two or more kinds of the above-mentioned anticorrosive agents may be compound X alone, compound Y alone, or compound Z alone, among compound X, compound Y, and compound Z. 2 or 3 types may be used.
  • compound X, compound Y, and compound Z will be described in detail.
  • Compound X is "one substituent XA, which is a group represented by any of the general formulas (XA1) to (XA3), and a group represented by any of the general formulas (XB1) to (XB7).
  • substituent XA which is a group represented by any of the general formulas (XA1) to (XA3), and a group represented by any of the general formulas (XB1) to (XB7).
  • One or more compounds selected from the group consisting of "a compound containing one or more substituents XB (Compound X1)” and "a compound containing two or more substituents XA (Compound X2)". is there.
  • R in the general formulas (XA1), (XA2), (XB4), and (XB5) independently represents a hydrogen atom or an alkyl group.
  • the alkyl group may be linear or branched, and may have a wholly or partially cyclic structure.
  • the alkyl group preferably has 1 to 6 carbon atoms, and more preferably 1.
  • the alkyl group is preferably unsubstituted.
  • R is preferably a hydrogen atom in that the etching of the first metal-containing material can be further suppressed.
  • the substituent XA is a group represented by the general formula (XA1), a group represented by the general formula (XA2), and R is a hydrogen atom, in that the etching of the first metal-containing material can be further suppressed.
  • a group represented by the general formula (XA3) is preferable.
  • the substituent XB is not a group contained in the substituent XA. That is, when examining whether the partial structure in the compound contains either the substituent XA or the substituent XB, first, it is examined whether or not the partial structure contains the substituent XA, and the case where the substituent XA is not contained is examined. Next, it is examined whether or not the substituent XB is contained. In other words, the substituent XB can only be present in the partial structure in which the group corresponding to the substituent XA in the compound is absent.
  • the carboxyhydroxymethyl group corresponds to the substituent XA (group represented by the general formula (XA3)), and the above carboxy -OH as a part of the hydroxymethyl group does not correspond to the substituent XB (group represented by the general formula (XB1)).
  • the group represented by the general formula (XB1) is neither a group contained in the group represented by the general formula (XB2) nor a group contained in the group represented by the general formula (XB6).
  • -OH which is a part of such -COOH corresponds to the group represented by the general formula (XB1).
  • the group represented by the general formula (XB1) is preferably other than -OH, which is a part of -COOH.
  • the group represented by the general formula (XB1) is preferably bonded to a carbon atom (preferably a carbon atom other than the carbonyl carbon atom, more preferably a sp3 carbon atom). From the viewpoint that the effect of the present invention is more excellent, the substituent XB is preferably a group represented by any of the general formulas (XB1) and (XB3) to (XB7).
  • Compound X1 which is a form of compound X, has one substituent XA represented by any of the general formulas (XA1) to (XA3) and is represented by any of the general formulas (XB1) to (XB7). It is a compound containing one or more substituents XB.
  • the number of substituents XA contained in compound X1 is 1.
  • the number of substituents XB contained in compound X1 is preferably 1 to 10. When a plurality of substituents XB are present, the plurality of substituents XB may be the same or different from each other.
  • Compound X2 which is a form of compound X, is a compound containing two or more substituents XA represented by any of the general formulas (XA1) to (XA3).
  • the number of substituents XA contained in compound X2 is preferably 2 to 10, and more preferably 2.
  • the plurality of substituents XA may be the same or different from each other.
  • Compound X2 may contain a substituent XB. When the compound X2 contains a substituent XB, the number of the substituents XB contained in the compound X2 is preferably 1 to 10. When a plurality of substituents XB are present, the plurality of substituents XB may be the same or different from each other.
  • the compound X is preferably a compound represented by the following general formula (X).
  • X A represents a substituent XA (a group represented by any of the general formulas (XA1) to (XA3)).
  • X AB is a substituent XA (a group represented by any of the general formulas (XA1) to (XA3)) or a substituent XB (general formulas (XB1) to (XB7)). Represents a group represented by either.
  • XAB the substituent XB is preferable.
  • X C represents a single bond or an alkylene group.
  • one or more (preferably 1 to 5) of -CH 2- constituting the alkylene chain may be replaced with -CO- and / or -S-.
  • -CO- does not bond continuously.
  • the alkylene group may be linear or branched. Further, the alkylene group may be partially or wholly cyclic.
  • the alkylene group is preferably linear.
  • the alkylene group may contain a substituent, and the substituent is preferably a hydroxyl group. It is also preferable that the alkylene group does not contain a substituent other than a hydroxyl group.
  • the alkylene group preferably has 1 to 10 carbon atoms.
  • the number of carbon atoms includes the number of carbon atoms in -CH 2 -replaced with -S-.
  • X C is "- (L X) mx -" group represented by are preferred.
  • "- (L X) mx -" in, mx represents an integer of 0 to 10. If mx is 0, "- (L X) mx -" is a single bond.
  • "- (L X) mx -" in, L X is, -CR X 2 -, - CO- , or represents -S-. However, -CO- does not bond continuously.
  • -CR X 2 - represents two R X are each independently a hydrogen atom or a substituent of the medium (preferably hydroxyl groups).
  • One -CR X 2 - 2 one R X medium is preferably one or both are hydrogen atoms. If there are a plurality, -CR X 2 there are a plurality of - - L X in -CR X 2 to may each be the same or different.
  • X A and X AB in the general formula (X) include, for example, “XA1 / XB2", “XA1 / XB3", “XA1 / XB6", “XA1 / XB7", and “XA1 /”.
  • "XA1”, “XA2 / XB3", “XA2 / XB4", “XA2 / XB5", or "XA3 / XB1" is preferable, and "XA1 / XB3", “XA1 / XB6", “XA1 / XB7", “"XA2 / XB4" or "XA2 / XB5" is more preferable.
  • XA1 / XB2 means a combination in which X A is a group represented by the general formula (XA1) and X AB is a group represented by the general formula (XB2). Other similar descriptions have the same meaning.
  • X A is a group represented by the general formula (XA1) and X AB is a group represented by the general formula (XB7)
  • X C is a single bond or an alkylene group having 1 to 3 carbon atoms. Is also preferable.
  • the compound X is preferably a compound containing 1 to 5 partial structures represented by ⁇ COOH, and more preferably a compound containing only one.
  • the partial structure represented by -COOH is intended for all -COOH present in the compound.
  • -COOH which exists as a part of the substituent XA, is also counted as a partial structure represented by -COOH.
  • Compound X may be used alone or in combination of two or more. When two or more kinds of compounds X are used, two or more kinds of compounds X may be only compound X1 or both may be only compound X2, and both compound X1 and compound X2 may be used. There may be.
  • Compound Y is a compound represented by the general formula (Y). Y Q- COOH (Y)
  • Y Q represents an aromatic ring group having a phosphonate oxy group (-OPO (OH) 2 ), an aromatic ring group having a boronic acid group (-B (OH) 2 ), or a phosphonic acid group-alkylene group. ..
  • the aromatic ring group having an oxyphosphonate group and the aromatic ring group in the aromatic ring group having a boronate group may be independently an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and may be an aromatic hydrocarbon ring. Groups are preferred.
  • the aromatic ring group may be monocyclic or polycyclic, and a monocyclic ring is preferable.
  • the number of ring members of the aromatic ring group is preferably 5 to 15, and more preferably 6.
  • the COOH specified in the general formula (Y) directly bonds with the ring member atom of the aromatic ring group. Further, in the aromatic ring group having a phosphonate oxy group, the phosphonate oxy group and COOH specified in the general formula (Y) are directly bonded to the ring member atom of the aromatic ring group.
  • the aromatic ring group having a phosphonate oxy group may or may not contain a substituent other than these, and is preferably not contained.
  • the boronic acid group and COOH specified in the general formula (Y) are directly bonded to the ring member atom of the aromatic ring group.
  • the aromatic ring group having a boronic acid group may or may not contain a substituent other than these, and preferably does not contain it.
  • the alkylene group in the "phosphonic acid group-alkylene group-" may be linear or branched, and the number of carbon atoms is preferably 1 to 10.
  • the phosphonic acid group and COOH specified in the general formula (Y) are directly bonded to the carbon atom constituting the alkylene chain of the alkylene group.
  • the "phosphonic acid group-alkylene group-” may or may not contain a substituent other than these, and is preferably not contained.
  • Compound Z is one or more compounds selected from the group consisting of mellitic acid (benzenehexacarboxylic acid) and oxalic acid (HOOC-COOH). Compound Z may be used alone or in combination of two.
  • anti-corrosion agent in the present invention L- cysteic acid, O- carboxyphenyl boronic acid, creatine, N- acetyl glycine (acetamido acetate), homoarginine, N 6 - (aminocarbonyl) -L- lysine (homocitrulline) , LO-phosphoserine, 2-phosphonooxybenzoic acid, melitonic acid, oxalic acid, gluconic acid, L-citrulin, DL-alanylglycine, d-cystine, and dl-diencoric acid.
  • More than a species of compound is preferred and is selected from the group consisting of L-cysteine acid, gluconic acid, homoarginine, L-citrulin, DL-alanylglycine, O-carboxyphenylboronic acid, melitonic acid, and oxalic acid 1 More than a species of compound is more preferred.
  • the content of the anticorrosive agent in the treatment liquid is preferably 0.01 to 7% by mass, preferably 0.01, based on the total mass of the treatment liquid. It is more preferably ⁇ 5% by mass, further preferably 0.05 to 3% by mass, and particularly preferably 0.07 to 3% by mass. Above all, the content of compound Y is particularly preferably 0.07% by mass or more and less than 1% by mass with respect to the total mass of the treatment liquid.
  • the treatment liquid of the present invention may further contain water.
  • the water is not particularly limited, but it is preferable to use ultrapure water used for semiconductor production, and it is more preferable to use water obtained by further purifying the ultrapure water to reduce inorganic anions, metal ions and the like. ..
  • the purification method is not particularly limited, but purification using a filtration membrane or an ion exchange membrane and purification by distillation are preferable. Further, for example, it is preferable to carry out purification by the method described in JP-A-2007-254168.
  • the content of water in the treatment liquid is preferably 0.01 to 18% by mass, more preferably 0.05 to 14% by mass, still more preferably 0.1 to 9% by mass, based on the total mass of the treatment liquid. ..
  • the treatment liquid of the present invention may contain a pH adjuster.
  • the pH adjuster is a component other than the above-mentioned components.
  • a quaternary ammonium salt such as choline, an alkali hydroxide or alkaline earth salt such as potassium hydroxide, 2-aminoethanol, and an amino compound such as guanidine can be used to raise the pH. ..
  • metal ions for example, ammonium hydroxide, choline compounds, monoamines, imines (eg, 1,8-diazabicyclo [5.4.0] undecane-7-.
  • a hydroxylamine salt is preferable from the viewpoint of remarkably obtaining the desired effect of the present application.
  • examples of lowering the pH include inorganic acids and organic acids such as carboxylic acids and organic sulfuric acids.
  • the inorganic acid include hydrochloric acid, sulfuric acid, carbonic acid, hypophosphorous acid, phosphoric acid, phosphoric acid and the like.
  • Specific examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-.
  • Heptanoic acid 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, glutaric acid, adipic acid, pimelli acid, maleic acid, phthalic acid, malic acid, tartrate acid , Lactic acid, diglycolic acid, 2-furancarboxylic acid, 2,5-furandicarboxylic acid, 3-furancarboxylic acid, 2-tetracarboxylic acid, methoxyacetic acid, methoxyphenylacetic acid, phenoxyacetic acid and the like.
  • Specific examples of the organic sulfuric acid include methanesulfonic acid, ethanesulfonic acid, isethionic acid and the like.
  • 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 may be appropriately determined so that the pH of the treatment liquid is within a predetermined range, for example.
  • the pH of the treatment liquid is preferably 5.0 or less, more preferably 4.0 or less, further preferably 0.00 to 4.0, and particularly preferably 0.05 or more and less than 3.5.
  • the treatment liquid of the present invention does not substantially contain coarse particles.
  • the coarse particles refer to particles having a diameter of 0.2 ⁇ m or more, for example, when the shape of the particles is regarded as a sphere.
  • the fact that coarse particles are not substantially contained means that when the treatment liquid is measured using a commercially available measuring device in the light scattering type in-liquid particle measurement method, particles of 0.2 ⁇ m or more in 1 mL of the treatment liquid are measured. Is 10 or less.
  • the coarse particles contained in the treatment liquid include particles such as dust, dust, organic solids and inorganic solids contained as impurities in the raw material, and dust and dirt brought in as contaminants during the preparation of the treatment liquid.
  • the amount of coarse particles present in the treatment liquid can be measured in the liquid phase by using a commercially available measuring device in the light scattering type liquid particle measurement method using a laser as a light source. Examples of the method for removing coarse particles include processing such as filtering described later.
  • the treatment liquid of the present invention may contain other components as components other than those described above.
  • Other components include, for example, anticorrosive agents other than those described above (anticorrosive agents that do not fall under any of compounds X, Y, Z), surfactants, oxidizing agents, chelating agents, defoaming agents, rust preventives, and , Preservatives and the like.
  • the treatment liquid of the present invention is, for example, based on the total mass of the treatment liquid.
  • the etchant is contained in an amount of 0.01 to 10% by mass (more preferably 0.05 to 5% by mass, still more preferably 0.1 to 3% by mass).
  • the organic solvent is contained in an amount of 80 to 99.9% by mass (more preferably 80 to 99% by mass, still more preferably 90 to 99% by mass).
  • the anticorrosive agent is contained in an amount of 0.01 to 5% by mass (more preferably 0.05 to 3% by mass, still more preferably 0.07 to 3% by mass).
  • a treatment liquid containing 0.01 to 18% by mass (more preferably 0.05 to 14% by mass, still more preferably 0.1 to 9% by mass) of water is preferable.
  • the treatment liquid may contain components (pH adjuster, etc.) other than the components (etchant, organic solvent, anticorrosive agent, and water) listed in the examples.
  • the treatment liquid of the present invention is typically a treatment liquid for semiconductor devices used in the manufacture of semiconductor devices.
  • “for semiconductor devices” means that it is used in the manufacture of semiconductor devices.
  • the treatment liquid of the present invention can be used in any step for manufacturing a semiconductor device, in addition to removing a metal hard mask and an etching residue.
  • the treatment liquid is a pre-wet liquid, a solution used for removing a permanent film (for example, a color filter, a transparent insulating film, a resin lens) or the like from a semiconductor substrate (for example, a removing liquid and a stripping liquid). It may also be used as a pCMP (after chemical mechanical polishing) cleaning solution or the like. Since the semiconductor substrate after the removal of the permanent film may be used again for the use of the semiconductor device, the removal of the permanent film is included in the manufacturing process of the semiconductor device. The specific application method of the treatment liquid of the present invention will be described later.
  • the treatment liquid of the present invention may be a kit obtained by dividing the raw material into a plurality of parts. Further, the treatment liquid may be prepared as a concentrated liquid. In this case, it can be diluted with water and / or an organic solvent at the time of use.
  • the treatment liquid of the present invention is a kit or a concentrated liquid, it can be stored, transported, and / or used by filling it in an arbitrary container as long as corrosiveness does not matter.
  • a container having a high degree of cleanliness in the container and less elution of impurities is preferable 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 inner wall of this 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, or stainless steel, hasteloy, inconel, monel, etc., for rust prevention and It is preferably formed from a metal that has been subjected to a metal elution prevention treatment.
  • a fluororesin (perfluororesin) can be preferably used.
  • ethylene or propylene oligomer is eluted as compared with the case where a container whose inner wall is a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin is used.
  • the occurrence of defects can be suppressed.
  • Specific examples of such a container whose inner wall is a fluororesin include a FluoroPure PFA composite drum manufactured by Entegris.
  • the metal material used for producing the electropolished metal material contains at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is 25 with respect to the total mass of the metal material.
  • Metallic materials having a mass% of more than% are preferable, and examples thereof include stainless steel and nickel-chromium alloys.
  • the total content of chromium and nickel in the metal material is preferably 25% by mass or more, more preferably 30% by mass or more, based on the total mass of the metal material.
  • the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90% by mass or less.
  • the stainless steel is not particularly limited, and known stainless steel can be used. Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable.
  • austenitic stainless steels include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), and SUS316 ( Ni content 10% by mass, Cr content 16% by mass), SUS316L (Ni content 12% by mass, Cr content 16% by mass) and the like.
  • the nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used. Of these, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferable. Examples of the nickel-chromium alloy include Hastelloy (trade name, the same shall apply hereinafter), Monel (trade name, the same shall apply hereinafter), Inconel (trade name, the same shall apply hereinafter) and the like.
  • Hastelloy C-276 Ni content 63% by mass, Cr content 16% by mass
  • Hastelloy-C Ni content 60% by mass, Cr content 17% by mass
  • Hastelloy C-22 Ni content 61% by mass, Cr content 22% by mass
  • the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt and the like in addition to the above alloys, if necessary.
  • the method for electrolytically polishing a metal material is not particularly limited, and a known method can be used.
  • a known method can be used.
  • the methods described in paragraphs [0011] to [0014] of JP2015-227501 and paragraphs [0036] to [0042] of JP2008-264929 can be used.
  • the content of chromium in the passivation layer on the surface of the metal material is higher than the content of chromium in the matrix by electropolishing. Therefore, since metal elements do not easily flow out into the treatment liquid from the inner wall coated with the electrolytically polished metal material, a chemical liquid for semiconductors having a low content of specific metal elements such as Ca atom, Fe atom and Na atom is used. It is presumed that it will be obtained.
  • the metal material is preferably buffed.
  • the method of buffing is not particularly limited, and a known method can be used.
  • the size of the abrasive grains used for finishing the buffing is not particularly limited, but # 400 or less is preferable because the unevenness on the surface of the metal material tends to be smaller.
  • the buffing is preferably performed before the electrolytic polishing.
  • the metal material may be a material processed by combining one or more of a plurality of stages of buffing, acid cleaning, magnetic fluid polishing, etc., which are performed by changing the count such as the size of abrasive grains. ..
  • the container containing the container and the treatment liquid contained in the container may be referred to as a treatment liquid container.
  • the liquid may be appropriately selected depending on the intended use, but contains at least one of the treatment liquid of the present invention itself, a liquid obtained by diluting the treatment liquid of the present invention, or a component added to the treatment liquid of the present invention. When it is a liquid, the effect of the present invention can be remarkably obtained.
  • the treatment liquid of the present invention 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 (chisso, argon, etc.) having a purity of 99.99995% by volume or more for the purpose of preventing changes in the components in the treatment liquid during storage.
  • an inert gas chisso, argon, etc.
  • a gas having a low water content is preferable.
  • the temperature may be at room temperature, but in order to prevent deterioration, the temperature may be controlled in the range of ⁇ 20 ° C. to 20 ° C.
  • ⁇ Clean room> It is preferable that the production of the treatment liquid of the present invention, the opening and / or cleaning of the storage container, the handling including the filling of the treatment liquid, the treatment analysis, and the measurement are all performed in a clean room.
  • the clean room preferably meets the ISO (International Organization for Standardization) 14644-1 clean room standard. It is preferable to satisfy any one of ISO class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably ISO class 1 or ISO class 2, and even more preferably ISO class 1.
  • the treatment liquid of the present invention is preferably a filtered treatment liquid in order to remove foreign substances, coarse particles and the like.
  • the filter used for filtering can be used without particular limitation as long as it is a filter conventionally used for filtration purposes and the like.
  • the material constituting the filter include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (high density and ultrahigh molecular weight). Including) and the like.
  • polyamide-based resin, PTFE, or polypropylene is preferable, and by using a filter formed of these materials, a highly polar foreign substance that easily causes residue defects and particle defects. Can be removed more effectively.
  • the lower limit value is preferably 70 mN / m or more, and the upper limit value is preferably 95 mN / m or less.
  • the critical surface tension of the filter is preferably 75 to 85 mN / m.
  • the value of the critical surface tension is the nominal value of the manufacturer.
  • the pore size of the filter is preferably about 0.001 to 1.0 ⁇ m, more preferably about 0.02 to 0.5 ⁇ m, and even more preferably about 0.01 to 0.1 ⁇ m.
  • different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more. When different filters are combined and filtering is performed twice or more, each filter may be the same type of filter, different types of filters, or different types of filters. Is preferable. Typically, it is preferable that the first filter and the second filter differ in at least one of the pore diameter and the constituent material. It is preferable that the pore diameters of the second and subsequent filters are the same or smaller than the pore diameter of the first filtering. Further, first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to.
  • a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd.
  • P-nylon filter (pore diameter 0.02 ⁇ m, critical surface tension 77 mN / m) made of polyamide; (manufactured by Nippon Pole Co., Ltd.), "PE clean filter (pore diameter 0.02 ⁇ m)” made of high-density polyethylene; (Manufactured by Nippon Pole Co., Ltd.) and "PE / Clean Filter (hole diameter 0.01 ⁇ m)” made of high-density polyethylene; (manufactured by Nippon Pole Co., Ltd.) can also be used.
  • the second filter a filter made of the same material as the first filter described above can be used.
  • a filter having a pore diameter similar to that of the first filter described above can be used.
  • the ratio of the pore diameter of the second filter to the pore diameter of the first filter (the pore diameter of the second filter / the pore diameter of the first filter). ) Is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and even more preferably 0.3 to 0.9.
  • filtering with the first filter is performed with a mixed solution containing a part of the components of the treatment solution, and after mixing the remaining components with the mixed solution to prepare the treatment solution, filtering with the second filter is performed. May be done.
  • the filter used is treated before filtering the treatment liquid.
  • the liquid used for this treatment is not particularly limited, but the treatment liquid itself of the present invention, a liquid obtained by diluting the treatment liquid of the present invention, or a liquid containing a part of the components of the treatment liquid is desired in the present application. The effect of is remarkably obtained.
  • the upper limit of the temperature at the time of filtering is preferably room temperature (25 ° C.) or lower, more preferably 23 ° C. or lower, and even more preferably 20 ° C. or lower.
  • the lower limit of the temperature at the time of filtering is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and even more preferably 10 ° C. or higher. Filtering can remove particulate foreign matter and impurities, but when performed at the above temperature, the amount of particulate foreign matter and impurities dissolved in the treatment liquid is reduced, so filtering is performed more efficiently. ..
  • the treatment liquid of the present invention is used for treating an object to be treated containing a first metal-containing material containing one or more first metals selected from the group consisting of Co and Cu.
  • the object to be treated to which the treatment liquid of the present invention is applied is not limited as long as it contains a first metal-containing material containing one or more first metals selected from the group consisting of Co and Cu.
  • the object to be treated is a second metal-containing material containing one or more second metals selected from the group consisting of Zr, Ti, Hf, and Ta, and / or Al or Al 2 O 3 . It may contain an aluminum-based material. Further, the object to be treated may further contain a dry etching residue.
  • the first metal-containing material containing one or more first metals selected from the group consisting of Co (cobalt) and Cu (copper) contained in the object to be treated to which the treatment liquid of the present invention is applied may be a single substance of one kind of first metal, an alloy of first metals, or an alloy of one or more kinds of first metals and metals other than the first metal, and one or more kinds of first metals.
  • Oxide composite oxide
  • nitride composite nitride
  • oxynitride composite oxynitride
  • the first metal-containing material may be a Co-containing material in which the first metal is Co, or may be a Cu-containing material in which the first metal is Cu.
  • the Co-containing material is the same as the first metal-containing material except that the first metal is only Co and Cu is a metal other than the first metal.
  • the Cu-containing material is the same as the first metal-containing material except that the first metal is only Cu and Co is a metal other than the first metal.
  • the content of the first metal is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, still more preferably 99 to 100% by mass, based on the total mass of the metal components contained in the first metal-containing material. ..
  • the first metal-containing material preferably contains at least Co, and it is also preferable that the first metal-containing material contains Co.
  • the first metal-containing material include Co and Cu, with Co being preferred.
  • the removal rate of the first metal-containing substance is preferably 10 ⁇ / min or less, more preferably 5 ⁇ / min or less. It is preferable, and 1 ⁇ / min or less is more preferable. The lower limit is not limited, but is, for example, 0.001 ⁇ / min or more.
  • the second metal-containing material containing the two metals may be, for example, one kind of the second metal alone or an alloy of the second metals, and one or more kinds of the second metal and a metal other than the second metal. It may be an alloy, or may be an oxide (composite oxide), a nitride (composite nitride), or an oxynitride (composite oxynitride) of one or more kinds of second metals, and may be with one or more kinds of second metals.
  • the second metal-containing material may be a Zr-containing material in which the second metal is Zr, a Ti-containing material in which the second metal is Ti, and an Hf-containing material in which the second metal is Hf. It may be a Ta-containing material in which the second metal is Ta.
  • the content of the second metal is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, still more preferably 99 to 100% by mass, based on the total mass of the metal components contained in the second metal content. ..
  • the second metal-containing material examples include ZrOx (ZrO 2, etc.), Ti, TiN, HfOx, and TaOx.
  • the second metal-containing material may be a dry etching residue.
  • the second metal-containing material having such a dry etching residue include the residue of the metal hard mask produced by performing dry etching when the second metal-containing material is used as the metal hard mask. ..
  • the aluminum-based material that can be contained in the object to be treated to which the treatment liquid of the present invention is applied is Al (elemental substance) or Al 2 O 3 (alumina), and may be both Al and Al 2 O 3. .. If both of Al and Al 2 O 3, may be present in contact with Al and Al 2 O 3, may be present separately.
  • the removal rate of the aluminum-based material is preferably 10 ⁇ / min or less, more preferably 5 ⁇ / min or less, and 3 ⁇ or less. It is more preferably less than / minute.
  • the lower limit is not limited, but is, for example, 0.001 ⁇ / min or more.
  • the removal rate ratio ER1 / ER2 is It is preferably 0.5 to 1000, more preferably 0.8 to 800, and even more preferably 1 to 500.
  • the removal rate ratio ER1 / ER2 is within the above range, the effect of the present invention is more excellent.
  • the material to be treated is preferably a laminate for semiconductor devices.
  • the laminate includes, for example, a substrate, a third layer formed on the substrate, a second layer formed on the third layer, and a first layer formed on the second layer.
  • the third layer is preferably a material containing the first metal-containing material. It is also preferable that the third layer further contains an aluminum-based material (preferably Al).
  • the third layer is preferably a metal layer (wiring).
  • the second layer is preferably composed of a Si-containing substance containing Si (SiOx, SiOC, SiN, and / or SiON, etc.). Further, it is preferable that the first layer and the second layer are made of different materials.
  • the second layer is preferably an interlayer insulating film.
  • the first layer preferably contains a second metal-containing material.
  • the first layer is preferably a metal hard mask.
  • the second layer and / or the first layer may be omitted.
  • the laminated body may contain a layer other than the above-mentioned layer, and examples thereof include an etching stop layer and an antireflection layer.
  • the etching stop layer contains an aluminum-based material (preferably Al 2 O 3 ) and / or a first metal-containing substance (preferably a Co-containing substance, more preferably a simple substance of Co).
  • the metal layer may also function as an etching stop layer.
  • the laminate may further contain a dry etching residue. The dry etching residue is present, for example, adhering to the surface portion of the first layer, the second layer, and / or the third layer of the laminate.
  • the laminate includes a substrate, a metal layer (corresponding to the third layer), an interlayer insulating film (corresponding to the second layer), and a metal hard mask (corresponding to the first layer) in this order.
  • a metal layer corresponding to the third layer
  • an interlayer insulating film corresponding to the second layer
  • a metal hard mask corresponding to the first layer
  • Examples thereof include a laminate for a semiconductor device.
  • the laminate further contains 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 or the like.
  • the method for producing a laminate containing holes as described above is not particularly limited, but usually, the laminate before treatment containing a substrate, a metal layer, an interlayer insulating film, and a metal hard mask in this order.
  • a dry etching process is performed using a metal hard mask as a mask, and the interlayer insulating film is etched so that the surface of the metal layer is exposed, thereby forming holes penetrating the inside of the metal hard mask and the interlayer insulating film.
  • the method of providing is mentioned.
  • the method for producing the metal hard mask is not particularly limited. For example, first, a metal hard mask precursor layer containing a predetermined component is formed on an interlayer insulating film, and a resist film having a predetermined pattern is formed on the metal hard mask precursor layer. To do.
  • the laminated body may contain a layer other than the above-mentioned layer, and examples thereof include an etching stop layer and an antireflection layer.
  • FIG. 1 shows a schematic cross-sectional view showing an example of a laminated body for a semiconductor device to be processed.
  • the laminate 10 shown in FIG. 1 is provided with a metal layer 2, an etching stop layer 3, an interlayer insulating film 4, and a metal hard mask 5 in this order on a substrate 1, and is placed in a predetermined position after undergoing a dry etching step or the like.
  • a hole 6 is formed in which a part of the metal layer 2 is exposed. 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 film 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 film 4 and a metal hard mask 5, and a bottom wall 11b made of an exposed metal layer 2, and the dry etching residue 12 is formed. It is attached.
  • the treatment method of the present invention can be suitably used for cleaning for the purpose of removing these dry etching residues 12 and / or for removing the metal hard mask 5. That is, it is possible to suppress the etching of the inner wall 11 (for example, the metal layer 2 or the like) of the laminated body while excellent in the removal performance of the dry etching residue 12 and / or the metal hard mask 5.
  • the metal hard mask contains a second metal-containing material.
  • the metal hard mask may be the second metal-containing material itself.
  • the interlayer insulating film (sometimes referred to as an "insulating film” in the present specification) is preferably a material having a dielectric constant k of 3.0 or less, and more preferably a material having a dielectric constant k of 2.6 or less.
  • Specific examples of the interlayer insulating film material include Si-containing substances containing Si (SiOx, SiOC, SiN, and / or SiON, etc.).
  • x is a number represented by 1 to 3.
  • the material of the etching stop layer is not particularly limited.
  • Specific materials for the etching stop layer include an aluminum-based material, a first metal-containing substance (preferably a Co-containing substance, more preferably a simple substance of Co), TEOS (tetraethoxysilane), SiN, SiOC, poly-Si (preferably a Co-containing substance, more preferably a simple substance of Co). Polycrystalline silicon), a-Si (amorphous silicon), and the like.
  • Al 2 O 3 is preferable as the aluminum-based material constituting the etching stop layer.
  • the wiring material forming the metal layer contains a first metal-containing material.
  • the metal layer may be the first metal-containing material itself. It is also preferable that the metal layer contains an aluminum-based material. Al is preferable as the aluminum-based material constituting the metal layer.
  • the “substrate” here includes, for example, a semiconductor substrate made of a single layer and a semiconductor substrate made of multiple layers.
  • the material constituting the semiconductor substrate composed of a single layer is not particularly limited, and is generally 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, an exposed integrated circuit such as an interconnect feature such as a metal wire and a dielectric material on the above-mentioned semiconductor substrate such as silicon. It may contain a structure.
  • Metals and alloys used in the interconnect structure include, but are not limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten.
  • the semiconductor substrate may contain layers such as an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide and carbon-doped silicon oxide.
  • the first embodiment of the treatment method of the present invention includes a first metal-containing material (the above-mentioned third layer (metal layer) and the like) and a second metal-containing material other than the dry etching residue (the above-mentioned first layer (the above-mentioned first layer (metal layer)).
  • the treatment liquid is brought into contact with the object to be treated containing the first metal-containing material (the above-mentioned third layer (metal layer) and the like) and the dry etching residue.
  • a treatment method including a step (step Bb) of removing the dry etching residue.
  • the dry etching residue may include a dry etching residue of a metal hard mask.
  • the metal hard mask is composed of a second metal-containing material, it can be said that the dry etching residue of the metal hard mask is also a form of the second metal-containing material.
  • a part or all of the dry etching residue may or may not be a second metal-containing substance.
  • both the first and second treatment methods may be carried out on one object to be treated, or the step Ba and the step Bb may be carried out at the same time.
  • the object to be processed is a first metal-containing material, a second metal-containing material other than the dry etching residue, and a dry etching residue (a dry etching residue which is a second metal-containing residue, and / or it.
  • the second metal-containing material other than the dry etching residue is obtained by contacting the treatment liquid with the object to be treated.
  • step Bc of simultaneously removing the dry etching residue (the dry etching residue which is the second metal-containing substance and / or the other dry etching residue) may be carried out.
  • the step Ba, the step Bb, and the step Bc are collectively referred to as a processing step B.
  • the treatment method of the present invention may include a step A for preparing the above-mentioned treatment liquid before the treatment step B.
  • a step A for preparing the above-mentioned treatment liquid before the treatment step B is shown as an example, but the present invention is not limited to this, and the treatment method of the present invention is prepared in advance. It may be carried out using the above-mentioned treatment liquid.
  • the second metal-containing substance other than the dry etching residue is removed, and the dry etching residue (the dry etching residue which is the second metal-containing substance and / or the other dry etching residue). ) Is removed at least one of them. Since the treatment method of the present invention uses the above-mentioned treatment liquid, it is excellent in removability of the object to be removed and can suppress etching of the first metal-containing material (preferably the metal layer). Further, when the object to be treated contains an aluminum-based material (preferably in the metal layer and / or the etching stop layer), etching on the aluminum-based material can also be suppressed.
  • the treatment liquid preparation step A is a step of preparing the above-mentioned treatment liquid.
  • 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 treatment liquid by adding an etchant, an anticorrosive agent, and other optional components to a solvent such as water and / or an organic solvent and stirring and mixing them. Can be mentioned.
  • a raw material used for preparing the treatment liquid it is preferable to use a raw material classified into a semiconductor grade or a raw material classified into a high-purity grade equivalent thereto. Further, it is preferable to use the raw material having a large amount of impurities after removing foreign substances by filtering and / or reducing the ionic component by an ion exchange resin or the like.
  • Process step B In the treatment step B, the treatment liquid is brought into contact with the object to be treated. As a result, at least one of cleaning for the purpose of removing the dry etching residue and removal of the metal hard mask (wet etching) are performed.
  • the method of bringing the treatment liquid into contact with the object to be treated is not particularly limited. A method of flowing the treatment liquid into the water, or any combination thereof can be mentioned.
  • the temperature of the treatment liquid when the treatment liquid is brought into contact with the object to be treated is preferably 90 ° C. or lower, more preferably 25 to 60 ° C.
  • the treatment time can be adjusted according to the contact method of the treatment liquid and the temperature of the treatment liquid.
  • the processing time is, for example, 60 minutes or less, preferably 1 to 60 minutes, and 3 to 3 to 60 minutes. 20 minutes is more preferable, and 4 to 15 minutes is even more preferable.
  • the processing time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, more preferably 15 seconds to 3 minutes, and even more preferably 20 seconds to 2 minutes.
  • a mechanical stirring method may be used in order to further increase the processing capacity of the processing liquid.
  • the mechanical stirring method include a method of circulating the treatment liquid on the object to be treated, a method of flowing or spraying the treatment liquid on the object to be treated, a method of stirring the treatment liquid by ultrasonic waves or megasonics, and the like. Can be mentioned.
  • the treatment method of the present invention may further include a step of rinsing and cleaning the object to be treated with a solvent (rinse step B2) after the treatment step B.
  • the rinsing step B2 is preferably performed continuously in the treatment step B and is a step of rinsing 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.
  • rinsing solvent examples include, but are not limited to, deionized water, methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, ⁇ -butyrolactone, dimethyl sulfoxide, ethyl lactate and propylene glycol monomethyl ether acetate.
  • An aqueous rinse solution having a pH> 8 (diluted aqueous ammonium hydroxide, etc.) may be used.
  • the rinsing solvent is preferably an aqueous solution of ammonium hydroxide, deionized water, methanol, ethanol, or isopropyl alcohol, more preferably an aqueous solution of ammonium hydroxide, deionized water, or isopropyl alcohol, and an aqueous solution of ammonium hydroxide or deionization. Water is more preferred.
  • a method of bringing the rinse solvent into contact with the object to be treated the above-mentioned method of bringing the treatment liquid into contact with the object to be treated can be similarly applied.
  • the temperature of the rinsing solvent in the rinsing step B2 is preferably 16 to 27 ° C.
  • the above-mentioned treatment liquid may be used as a rinsing solvent in the rinsing step B2.
  • the treatment method of the present invention may include a drying step B3 for drying the object to be treated after the rinsing step B2.
  • the drying method is not particularly limited. Examples of the drying method include a spin drying method, a method of flowing a dry gas over an object to be treated, a method of heating a substrate by a heating means such as a hot plate or an infrared lamp, a flatulence drying method, a rotagoni drying method, and an IPA. (Isopropyl alcohol) drying method and any combination thereof can be mentioned.
  • the drying time depends on the specific method used, but is generally preferably 30 seconds to several minutes.
  • the treatment method of the present invention may include a coarse particle removing step H for removing coarse particles in the treatment liquid before performing the treatment step B.
  • a coarse particle removing step H for removing coarse particles in the treatment liquid before performing the treatment step B.
  • the amount of coarse particles remaining on the object to be treated after the treatment step B can be reduced.
  • Specific methods for removing coarse particles include, for example, a method of filtering and purifying the treatment liquid that has undergone the treatment liquid preparation step A using a particle removal film having a predetermined particle removal diameter.
  • the definition of coarse particles is as described above.
  • Static elimination steps I, J water is used in the preparation of the treatment liquid in the treatment liquid preparation step A, and the static elimination step I and / / in which static elimination is performed on the water before the treatment liquid preparation step A.
  • a static elimination step J for statically eliminating the treated liquid may be contained after the treatment liquid preparation step A and before the treatment step B is performed.
  • the material of the wetted portion for supplying the treatment liquid to the object to be treated may be a resin having no metal elution with respect to the treatment liquid.
  • the static elimination method include a method in which water and / or a treatment liquid is brought into contact with a conductive material.
  • the contact time for contacting the water and / or the treatment liquid with the conductive material is preferably 0.001 to 1 second, more preferably 0.01 to 0.1 second.
  • the resin examples include high-density polyethylene (HDPE), high-density polypropylene (PP), 6,6-nylon, tetrafluoroethylene (PTFE), and a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA). ), Polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), ethylene / tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene / hexafluoride propylene co-weight. Coalescence (FEP) and the like can be mentioned.
  • the conductive material include stainless steel, gold, platinum, diamond, glassy carbon and the like.
  • the drainage of the treatment liquid used in the treatment step B can be reused and further used for cleaning other objects to be treated.
  • the treatment method of the present invention preferably comprises the following steps when the drainage of the treatment liquid is reused.
  • a drainage recovery step E for recovering the drainage of the treatment liquid used in the treatment step D, and a drainage recovery step E. Contains, It includes a step of repeating the above-mentioned processing step D and the above-mentioned drainage recovery step E.
  • the treatment step B has the same meaning as the treatment step B described in the above-described mode, and the same applies to the preferred mode. Further, even in the mode of reusing the drainage liquid, the coarse particle removing step H and the static elimination steps I and J may be contained. Further, the treatment liquid preparation step A described in the above-described embodiment may be contained before the treatment step B.
  • the treatment step D has the same meaning as the treatment step B in the above-described embodiment, and the preferred embodiment is also the same.
  • the drainage recovery means in the drainage recovery steps C and E is not particularly limited.
  • the collected drainage may be stored in the resin container described above in the static elimination step J, and at this time, the same static elimination step as in the static elimination step J may be performed. Further, a step of filtering the collected drainage liquid to remove impurities may be provided.
  • the pH adjuster should be an appropriate amount of either MSA or DBU (relative to the total mass in the treatment liquid) so that the pH of the treatment liquid becomes the value in the table. 1% by mass or less) was added. DBU was used only in the treatment liquid of Comparative Example 2, and MSA was used in the other treatment liquids.
  • a model film (each film of Co or Al 2 O 3 ) made of each material shown in Table 1 was prepared, and the etching property was evaluated based on the etching rate.
  • the film thickness of each model film is 1000 ⁇ .
  • Each model film was etched using each of the treatment solutions of Examples and Comparative Examples. Specifically, each model film was immersed in the treatment liquid at 25 ° C. for 10 minutes, and the etching rate ( ⁇ / min) was calculated based on the difference in film thickness of the model film before and after the immersion of the treatment liquid.
  • the model film was Co
  • the film thickness of the model film before and after the treatment was calculated by measuring the resistivity.
  • Lorester GP manufactured by Mitsubishi Chemical Corporation
  • the film thickness of the model film before and after the treatment is measured in a measurement range of 250 using ellipsometry (spectral ellipsometer, trade name "Vase", manufactured by JA Woolam Japan Co., Ltd.). The measurement was performed under the conditions of ⁇ 1000 nm and measurement angles of 70 degrees and 75 degrees.
  • the calculated etching rate was compared with the following categories to evaluate the corrosion resistance against Co and Al 2 O 3 (Co corrosion resistance and Al 2 O 3 corrosion resistance). Higher etching rate with respect to Co or Al 2 O 3 is small, it can be determined that the corrosion resistance of the treatment liquid to Co or Al 2 O 3 are excellent.
  • plasma etching using an etching gas containing nitrogen gas and halogen gas is performed using the first layer as a mask, and etching of the second layer is performed until the surface of the third layer is exposed.
  • etching gas containing nitrogen gas and halogen gas is performed using the first layer as a mask, and etching of the second layer is performed until the surface of the third layer is exposed.
  • Washing is less than 50% (residues confirmed by SEM before immersion, less than 50% removed after immersion)
  • Table 1 shows the formulation of the treatment liquid and the test results.
  • the "amount” column indicates the content (mass%) of each component.
  • the "XA” column under the “Compound X” column indicates the type of substituent XA contained in the anticorrosive agent when the anticorrosive agent used corresponds to the compound X.
  • the "XB” column under the “Compound X” column indicates the type of substituent XB contained in the anticorrosive agent when the anticorrosive agent used corresponds to the compound X.
  • the "COOH number” column under the “Compound X” column indicates the number of COOH partial structures contained in the anticorrosive agent when the anticorrosive agent used corresponds to the compound X.
  • the "YQ” column under the “Compound Y” column indicates the type of group represented by YQ contained in the anticorrosive agent when the anticorrosive agent used corresponds to the compound Y.
  • the description of "phosphon-O-Ar-” means “aromatic ring group having a phosphonate oxy group”
  • the description of "boron-Ar-” means “aromatic ring group having a boronate group”.
  • the “Amount of organic solvent (DEGBE) + pH adjuster (MSA or DBU)” column indicates the total content (mass%) of the organic solvent and the pH adjuster with respect to the total mass of the treatment agent in the treatment agent.
  • the content of the pH adjuster is adjusted so as to be the value shown in the "pH” column of the treatment liquid, and the specific content of any treatment liquid is based on the total mass of the treatment liquid. It was 1% by mass or less.
  • the treatment liquid of the present invention has good anticorrosion property against the first metal-containing substance (Co-containing substance). It was also confirmed that the treatment liquid of the present invention has good removability with respect to the object to be removed. Furthermore, it was confirmed that the treatment liquid of the present invention also has good anticorrosion properties against aluminum-based materials.
  • Example 6 a treatment liquid was prepared in the same manner except that the water content of 15.0% by mass was changed to 18.0% by mass, and evaluation was performed. As a result, the same results as in Example 6 were obtained. ..
  • Comparative Example 10 a treatment liquid was prepared in the same manner except that the water content of 25.0% by mass was changed to 19.2% by mass, and evaluation was performed. As a result, the same results as in Comparative Example 10 were obtained. ..
  • Example 10 a treatment liquid was prepared in the same manner except that the pH was changed from 3.5 to 3.8, and the evaluation was performed. As a result, the same result as in Example 10 was obtained.
  • Example 10 a treatment liquid was prepared in the same manner except that the pH was changed from 3.5 to 4.2, and the evaluation was performed. As a result, the same result as in Example 10 was obtained except that the removal performance was C. Obtained.
  • Example 8 a treatment liquid was prepared in the same manner except that HF was changed to ammonium fluoride, and the evaluation was performed. As a result, the same results as in Example 8 were obtained except that the removal performance was C.
  • Example 8 the content of L-cysteine is 1.0% by mass, and the total content of L-cysteine and O-carboxyphenylboronic acid is 1.0% by mass (L-cysteine / O-carboxyphenylboronic acid).
  • a treatment solution was prepared in the same manner except that the treatment solution was changed to 8/2 (mass ratio), and the evaluation was performed. As a result, the same result as in Example 8 was obtained.
  • Example 8 a treatment liquid was prepared in the same manner except that the L-cysteine content of 1.0% by mass was changed to 2.7% by mass, and evaluation was performed. As a result, the same results as in Example 8 were obtained. Was done.
  • Example 8 a treatment liquid was prepared in the same manner except that the L-cysteine content of 1.0% by mass was changed to 3.5% by mass, and the evaluation was performed. Obtained the same result as in Example 8.
  • Example 8 a treatment liquid was prepared in the same manner except that the L-cysteine content of 1.0% by mass was changed to 4.2% by mass, and the evaluation was performed. Obtained the same result as in Example 8.
  • Example 8 a treatment liquid was prepared in the same manner except that the L-cysteine content of 1.0% by mass was changed to 5.2% by mass, and the evaluation was performed. As a result, the removal performance was C. Obtained the same result as in Example 8.
  • ⁇ Test Y The above-mentioned ⁇ etching performance (corrosion resistance)> test was carried out using a Cu film as a model film. When the tests were carried out using the treatment solutions of Examples 1 to 36, all the treatment solutions showed good anticorrosion properties, and the results of the same tendency as when Co was used as the model film were confirmed.
  • ⁇ Test Z The test shown in ⁇ PER (Post Etching Resolution) removal performance> described above was carried out in the same manner except that the first layer (metal hard mask) was changed from ZrO 2 to TiN or TaO. (In this case, a dry etching residue containing Ti or Ta was observed on the surface of the laminate before immersion in the treatment liquid, not a dry etching residue containing Zr).
  • the metal hard mask was TiN or TaO, each treatment liquid showed good detergency (removal performance), and ZrO 2 was used as the metal hard mask. Results of the same tendency as when used were confirmed.

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Abstract

La présente invention concerne un liquide de traitement qui, tout en étant excellent en termes d'aptitude au retrait d'un objet à retirer, peut supprimer la gravure d'une première substance contenant du métal qui contient un ou plusieurs types d'un premier métal choisi dans le groupe constitué par Co et Cu, et un procédé de traitement. Le liquide de traitement de la présente invention est le liquide de traitement utilisé pour traiter un objet à traiter contenant une première substance contenant du métal qui contient un ou plusieurs types du premier métal choisi dans le groupe constitué par Co et Cu, et contient un agent de gravure, un solvant organique et un agent anticorrosif. La teneur en solvant organique est supérieure ou égale à 80 % en masse par rapport à la masse totale du liquide de traitement, et l'agent anticorrosif est un ou plusieurs types de composé choisis dans le groupe constitué par un composé X, un composé Y, et un composé Z.
PCT/JP2020/032679 2019-09-11 2020-08-28 Liquide de traitement, procédé de traitement WO2021049330A1 (fr)

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