WO2024004781A1 - Solution chimique, procédé de traitement de substrat, procédé de fabrication de dispositif à semi-conducteur, composé et résine - Google Patents

Solution chimique, procédé de traitement de substrat, procédé de fabrication de dispositif à semi-conducteur, composé et résine Download PDF

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Publication number
WO2024004781A1
WO2024004781A1 PCT/JP2023/022956 JP2023022956W WO2024004781A1 WO 2024004781 A1 WO2024004781 A1 WO 2024004781A1 JP 2023022956 W JP2023022956 W JP 2023022956W WO 2024004781 A1 WO2024004781 A1 WO 2024004781A1
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group
chemical solution
film
metal
solution
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PCT/JP2023/022956
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English (en)
Japanese (ja)
Inventor
直也 下重
泰雄 杉島
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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Publication of WO2024004781A1 publication Critical patent/WO2024004781A1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a chemical solution, a substrate processing method, a semiconductor device manufacturing method, a compound, and a resin.
  • a laminate including a metal layer serving as a wiring material, an etching stopper film, and an insulating film is placed on a substrate, a resist film is formed on the laminate, and a photolithography process and a dry etching process are performed. Manufactured by carrying out.
  • a method of etching or removing foreign matter adhering to the surface of a substrate using a chemical solution that dissolves metal-containing materials is widely known.
  • a metal layer and/or an insulating film on a substrate may be etched by dry etching using a resist film as a mask.
  • residues originating from the metal layer and/or the insulating film may adhere to the substrate, the metal layer, and the insulating film.
  • cleaning using a chemical solution is often performed.
  • the resist film used as a mask during etching is removed from the laminate by a dry method (dry ashing) using ashing (ashing) or a wet method. Residues originating from the resist film or the like may adhere to the laminate from which the resist has been removed using the dry ashing method. Furthermore, recently, in order to realize further miniaturization of semiconductor devices, resist films based on metal materials such as TiN and AlOx (so-called metal hard masks) have also been used as the above-mentioned resist films.
  • a dry etching process (e.g., plasma etching treatment) is usually performed using the metal hard mask as a mask to form holes based on the pattern shape of the metal hard mask for wiring.
  • a step is performed to expose the surface of the metal film that will become the film.
  • Etching residues and/or ashing residues are deposited on a substrate that has undergone a dry etching process or a dry ashing process.
  • a metal hard mask is used as a resist film, it contains a large amount of metal components such as titanium-based metals as a residual component, and when a photoresist film is used, it contains a large amount of organic components as a residual component. It is.
  • a cleaning process is often performed to remove the residues using a chemical solution.
  • a chemical solution is used in processes such as removing metal-containing substances (etching residues and ashing residues) and/or resist films on substrates in semiconductor device manufacturing processes.
  • Patent Document 1 describes a cleaning liquid used in the cleaning process of semiconductor device substrates, which is selected from organic acids, sulfonic acid type anionic surfactants, polyvinylpyrrolidone, and polyethylene oxide-polypropylene oxide block copolymers.
  • a semiconductor device substrate cleaning liquid containing at least one polymer flocculant and water is described.
  • the present inventors studied chemical solutions for semiconductor devices with reference to Patent Document 1, and found that further improvements in the performance of suppressing tungsten dissolution when a chemical solution is applied to a laminate having a tungsten-containing layer were found. We found that there was room.
  • the present inventor has completed the present invention as a result of intensive studies to solve the above problems. That is, it has been found that the above problem can be solved by the following configuration.
  • [1] A chemical solution for semiconductor devices, containing a resin having a repeating unit A derived from a compound represented by formula (1) described below, and water.
  • [2] The drug solution according to [1], wherein X represents a group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and a salt thereof.
  • [3] The drug solution according to [1] or [2], wherein X represents a primary amino group or a salt thereof.
  • [5] The drug solution according to any one of [1] to [4], wherein n is an integer of 2 to 5.
  • the present invention it is possible to provide a chemical solution for semiconductor devices that has excellent ability to remove residues and further suppresses dissolution of tungsten. Further, the present invention can provide a method for treating a substrate, a method for manufacturing a semiconductor device, a compound, and a resin using the above chemical solution.
  • FIG. 2 is a schematic cross-sectional view showing an example of a laminate that is a workpiece in a substrate processing method.
  • a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
  • the “content” of the component means the total content of the two or more types of components.
  • the compounds described herein may include structural isomers, optical isomers, and isotopes, unless otherwise specified. Moreover, one type of structural isomer, optical isomer, and isotope may be contained alone or two or more types may be included.
  • total solid content means the total content of all components contained in a drug solution other than solvents such as water and organic solvents.
  • preparation includes not only providing a predetermined product through processing such as synthesis or blending of raw materials, but also procuring a predetermined product through purchase or the like.
  • ppm means “parts-per-million ( 10-6 )
  • ppb means “parts-per-billion ( 10-9 )
  • ppt means “parts-per-million (10-6)”. parts-per-trillion ( 10-12 ). In this specification, 1 ⁇ (angstrom) corresponds to 0.1 nm.
  • weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all manufactured by Tosoh Corporation) as a column, and using tetrahydrofuran as a column.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • This is a value calculated using polystyrene as a standard material measured by a gel permeation chromatography (GPC) analyzer using a differential refractometer as an eluent, a differential refractometer as a detector, and polystyrene as a standard material.
  • the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight.
  • the chemical solution of the present invention (hereinafter also referred to as “the present chemical solution”) is a resin (hereinafter referred to as “polymerizable compound”) having a repeating unit A derived from a compound represented by formula (1) described below (hereinafter also referred to as “polymerizable compound”). , also referred to as “specific resin”), and water for semiconductor devices.
  • the present inventors have found that the present chemical solution containing the above-mentioned specific resin together with water has the effect that it has excellent residue removal properties and further suppresses the dissolution of tungsten (hereinafter also referred to as "effect of the present invention").
  • effect of the present invention was completed based on the finding that the following can be obtained.
  • the present inventors speculate as follows.
  • the specific resin is a resin having a repeating unit A, and the repeating unit A is derived from a compound represented by the following formula (1).
  • X is a group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, salts thereof, and a quaternary ammonium base (hereinafter referred to as a "specific amino group").
  • n represents an integer from 1 to 5.
  • L represents a (n+1)-valent linking group.
  • L is a divalent linking group containing a nitrogen-containing linking group selected from the group consisting of -NR L - and a divalent linking group represented by formula (L1) described below. or Y is the above heterocycle containing a nitrogen atom.
  • R L represents a hydrogen atom or a monovalent substituent.
  • n is an integer from 2 to 5
  • the plurality of X's may be the same or different.
  • examples of the monovalent substituent represented by R include an aliphatic hydrocarbon group, an aromatic group, and a halogen atom.
  • R is preferably a hydrogen atom, an aliphatic hydrocarbon group, or a halogen atom, more preferably a hydrogen atom, an alkyl group, or a halogen atom, and a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or More preferred is a halogen atom.
  • the aliphatic hydrocarbon ring having a carbon-carbon double bond in the ring (hereinafter also referred to as "ring C1") represented by Y may be a single ring, or may be a ring in which multiple rings are condensed. It may have a similar structure.
  • the number of ring members in ring C1 is preferably 4 to 10, more preferably 5 to 10, and even more preferably 5 or 6.
  • a cycloalkene ring having one carbon-carbon double bond in the ring is preferable, and examples thereof include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, and a norbornene ring.
  • Ring C1 may have a substituent. Examples of the substituent that ring C1 has include an alkyl group having 1 to 4 carbon atoms and a hydroxy group.
  • the heterocycle represented by Y and having a carbon-carbon double bond in the ring may be a single ring or may have a structure in which multiple rings are condensed. There may be.
  • the number of ring members in ring C2 is preferably 4 to 10, more preferably 5 to 10, and even more preferably 5 or 6. Further, the number of carbon atoms in ring C2 is preferably 3 to 9, more preferably 4 to 8, and even more preferably 4 to 6.
  • Examples of the heteroatom contained in ring C2 include a nitrogen atom, a sulfur atom, an oxygen atom, a phosphorus atom, a silicon atom, and a boron atom.
  • Ring C2 may have a carbonyl group (-CO-). Ring C2 is preferably an aliphatic heterocycle having one carbon-carbon double bond within the ring, such as a pyrroline ring and a maleimide ring. Ring C2 may have a substituent. Examples of the substituent that ring C2 has include an alkyl group having 1 to 4 carbon atoms and a hydroxy group.
  • X represents a group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, salts thereof, and a quaternary ammonium base.
  • n represents an integer from 1 to 5.
  • the above primary amino group is a group represented by -NH 2
  • the secondary amino group is a group represented by -NHR 2 (R 2 each independently represents a monovalent substituent).
  • the tertiary amino group is a group represented by -NR 3 2 (R 3 each independently represents a monovalent substituent)
  • the quaternary ammonium base is a group represented by the following It is a group represented by formula (A1) (* represents the bonding position).
  • R 4 each independently represents a monovalent substituent.
  • a ⁇ represents a monovalent anion.
  • the monovalent substituent represented by R 2 is not particularly limited, but is preferably a hydrocarbon group that may have a substituent, and a straight-chain hydrocarbon group having 1 to 8 carbon atoms that may have a substituent.
  • a branched aliphatic hydrocarbon group is more preferred, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent is even more preferred, and a methyl group is most preferred.
  • a plurality of R 2 may be the same or different.
  • the monovalent substituent represented by R 3 is not particularly limited, and preferred embodiments of the monovalent substituent represented by R 3 are the same as the preferred embodiments of the monovalent substituent represented by R 2 above. be.
  • a plurality of R 3 's may be the same or different.
  • the monovalent substituent represented by R 4 is not particularly limited, and preferred embodiments of the monovalent substituent represented by R 4 are the same as the preferred embodiments of the monovalent substituent represented by R 2 above. be. Moreover, a plurality of R 4 may be the same or different.
  • a ⁇ include halogen ions (eg, Cl ⁇ ), sulfate ions, nitrate ions, acetate ions, and hydroxide ions.
  • the above-mentioned salt is a salt formed by a primary amino group, a secondary amino group, or a tertiary amino group and an acidic compound.
  • the acidic compound may be either an inorganic acid or an organic acid.
  • Inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid.
  • Organic acids include acetic acid, propionic acid, methanesulfonic acid, ethanesulfonic acid, allylglycine, maleic acid, citraconic acid, fumaric acid, and itaconic acid.
  • the acid is preferably hydrochloric acid, acetic acid, propionic acid, methanesulfonic acid, or ethanesulfonic acid. , acetic acid, or ethanesulfonic acid are more preferred.
  • X is preferably a group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and salts thereof, in that the effects of the present invention are more excellent; A class amino group or a salt thereof is more preferred.
  • n represents an integer of 1 to 5, preferably an integer of 2 to 5, and more preferably 2 or 3.
  • L represents a (n+1)-valent linking group.
  • the number of atoms other than hydrogen atoms in L is preferably 1 to 25, more preferably 1 to 20, even more preferably 1 to 10.
  • L is not particularly limited as long as it is a group with a valence corresponding to the number of a divalent to pentavalent aromatic hydrocarbon group which may have a substituent, a divalent to pentavalent aromatic heterocyclic group which may have a substituent, -O-, -CO-, -SO 2 -, -NR L -, -N ⁇ , a divalent linking group represented by formula (L1) described below, and a group formed by combining these.
  • R L will be explained in detail later.
  • Examples of the substituents that the divalent to pentavalent aliphatic hydrocarbon group, aromatic hydrocarbon group, and aromatic heterocyclic group may have include a hydroxy group.
  • the divalent linking group represented by L is, for example, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, - Examples include O-, -CO-, -SO 2 -, -NR L -, a divalent linking group represented by formula (L1) described below, and a group formed by combining these.
  • Examples of the above-mentioned combined groups include -CO-NR L - divalent aliphatic hydrocarbon group optionally having a substituent, divalent aliphatic hydrocarbon group optionally having a - substituent Hydrocarbon group -NR L - divalent aliphatic hydrocarbon group optionally having a substituent - and -CO-NR L - divalent aromatic hydrocarbon group optionally having a substituent Examples include the group -.
  • the trivalent linking group represented by L includes -a divalent aromatic hydrocarbon group which may have a substituent -a trivalent aliphatic hydrocarbon which may have an O-substituent Group ⁇ , -CO-NR L - Trivalent aliphatic hydrocarbon group optionally having a substituent ⁇ , - Divalent aromatic hydrocarbon group optionally having a substituent - Substituent Divalent aliphatic hydrocarbon group that may have -N (divalent aliphatic hydrocarbon group that may have a -substituent-) 2 , -N that may have a substituent 2 valent aromatic hydrocarbon group -N (divalent aliphatic hydrocarbon group optionally having a substituent) 2 , trivalent aromatic heterocyclic group, -CO-O- having a substituent trivalent aliphatic hydrocarbon group which may have ⁇ , and divalent aromatic hydrocarbon group which may have a - substituent -SO 2 -N (even if it has a - substituent
  • Examples of the aromatic ring constituting the divalent to pentavalent aromatic hydrocarbon group include a benzene ring and a naphthalene ring, with a benzene ring being preferred.
  • Examples of the aromatic ring constituting the divalent to pentavalent aromatic heterocyclic group include an imidazole ring, a pyrazole ring, a thiazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring.
  • an imidazole ring, a pyridine ring, or a triazine ring is preferred.
  • the divalent to pentavalent aliphatic hydrocarbon group may be linear, branched or cyclic, but preferably linear or branched.
  • the number of carbon atoms in the divalent to pentavalent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 3 to 12, and even more preferably 3 to 6.
  • the divalent aliphatic hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms).
  • L includes a nitrogen-containing linking group selected from the group consisting of -NR L - and a divalent linking group represented by formula (L1) described below. It is a divalent linking group, or Y is the above-mentioned heterocycle containing a nitrogen atom (heterocycle having a carbon-carbon double bond in the ring).
  • R L represents a hydrogen atom or a monovalent substituent.
  • R L examples include an aliphatic hydrocarbon group.
  • R L is preferably a hydrogen atom or a linear or branched aliphatic hydrocarbon group, more preferably a hydrogen atom or a linear or branched alkyl group, and a hydrogen atom or , linear alkyl groups are more preferred.
  • R L1 each independently represents a hydrogen atom or a monovalent substituent.
  • a ⁇ represents a monovalent anion. * represents the bonding position.
  • R L1 examples include an aliphatic hydrocarbon group.
  • R L1 is preferably a hydrogen atom or a linear or branched aliphatic hydrocarbon group, more preferably a hydrogen atom or a linear or branched alkyl group, and a hydrogen atom or , linear alkyl groups are more preferred.
  • a ⁇ examples include halogen ions (eg, Cl ⁇ ), sulfate ions, nitrate ions, acetate ions, and hydroxide ions.
  • n is an integer of 2 to 5
  • the number of atoms in the shortest linking chain connecting two Xs among the plurality of Xs is 5 or less.
  • the shortest linking chain mentioned above means the number of atoms located on the shortest path among the atomic groups involved in linking two Xs. For example, in -CHX-CO-CH 2 -CH 2 , CH 2 X, so the number of atoms in the shortest connected chain is four. Also, for example, in -CHX-CHX-CH 2 -CH 2 -CH 3 , the shortest path of two Xs includes the carbon atom to which X in CHX is bonded and the two carbon atoms in CHX. Because of the positions of the atoms, the number of atoms in the shortest connected chain is two.
  • the number of atoms other than hydrogen atoms in L 1 is preferably 1 to 20, more preferably 1 to 10.
  • L 1 is not particularly limited as long as it is a divalent linking group, but for example, a divalent aliphatic hydrocarbon group that may have a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, etc.
  • the definition of R L is as described above.
  • Examples of the substituents that the above divalent aliphatic hydrocarbon group, aromatic hydrocarbon group, and aromatic heterocyclic group may have include a hydroxy group.
  • the number of carbon atoms in the divalent aliphatic hydrocarbon group is not particularly limited, and is preferably 1 to 6, more preferably 1 to 3.
  • the divalent aliphatic hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms).
  • a phenylene group is preferred.
  • L 1 is - divalent aromatic hydrocarbon group optionally having a substituent - O - divalent aliphatic hydrocarbon group optionally having substituent -, -CO- NR L - divalent aliphatic hydrocarbon group which may have a substituent -, - divalent aromatic hydrocarbon group which may have a substituent - Divalent aliphatic hydrocarbon group -NR L -Divalent aliphatic hydrocarbon group optionally having a substituent-, -Divalent aromatic hydrocarbon group optionally having a substituent- NR L - divalent aliphatic hydrocarbon group which may have a substituent -, divalent aromatic hydrocarbon group, divalent aromatic heterocyclic group, and -CO-O- substituent
  • Examples include divalent aliphatic hydrocarbon groups that may be present.
  • n1 represents an integer of 0 to 5, preferably 1 to 3, and more preferably 1 or 2.
  • L 2 represents -NH- or an oxygen atom.
  • X 2 represents a primary amino group or a hydroxy group. However, when L 2 is an oxygen atom, X 2 represents a primary amino group.
  • the compound represented by formula (1) preferably has an aromatic ring since the effects of the present invention are more excellent.
  • the above-mentioned aromatic ring may be, for example, either the aromatic ring possessed by R when Y represents CH 2 ⁇ CR-, or the aromatic ring possessed by L in the above formula (1). Among these, it is preferable that L in formula (1) has an aromatic ring.
  • the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle. Examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, with a benzene ring being preferred.
  • Examples of the aromatic heterocycle include an imidazole ring, a pyrazole ring, a thiazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a triazine ring.
  • the imidazole ring , a pyridine ring, or a triazine ring are preferred.
  • the specific resin may have only one type of repeating unit A, or may have two or more types of repeating units A.
  • the content of repeating unit A in the specific resin is preferably 1 mol% or more, more preferably 5 mol% or more, and 10 mol% or more, based on all repeating units in the specific resin, in order to improve the effect of the invention. The above is more preferable, and 25 mol% or more is even more preferable.
  • the upper limit of the content of repeating unit A is not particularly limited, but is preferably 99 mol% or less, more preferably 95 mol% or less, even more preferably 80 mol% or less, and 70 mol% or less, based on all repeating units in the specific resin. % or less is particularly preferable.
  • the specific resin has two or more types of repeating units A, the total content is preferably within the above range.
  • composition ratio (mole fraction) of each repeating unit contained in the specific resin can be measured by, for example, 13 C-NMR.
  • the specific resin may have other repeating units different from the above-mentioned repeating unit A, and among them, it is preferable to have a repeating unit B having an acid group.
  • a repeating unit B By having the repeating unit B in the specific resin, the solubility of the specific resin in a post-treatment liquid such as a rinsing liquid that is performed after treatment using a chemical solution is improved, and the solubility of the specific resin is improved after treatment is performed using a post-treatment liquid The amount of chemical solution-derived residue on the surface of a substrate such as a metal film can be further reduced.
  • Examples of the acid group that the repeating unit B has include a carboxyl group, a phosphonic acid group, a sulfo group, and a phenolic hydroxy group.
  • a carboxy group or a sulfo group is preferable, and the solubility of the specific resin in the post-treatment liquid is A carboxy group is more preferred in terms of its superiority.
  • the number of acid groups that the repeating unit B has is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.
  • repeating unit B examples include a repeating unit represented by the following formula (b).
  • R b1 , R b2 and R b3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acid group.
  • L b represents a single bond or a (k+1)-valent linking group.
  • A represents an acid group.
  • k represents an integer from 1 to 4.
  • R b1 , R b2 and R b3 are preferably a hydrogen atom, a methyl group, an ethyl group, or a carboxy group, and more preferably a hydrogen atom, a methyl group, or a carboxy group.
  • the (k+1)-valent linking group represented by L b is not particularly limited as long as it has a valence corresponding to the number of A, but for example, a divalent to pentavalent linking group that may have a substituent.
  • R L is as described above.
  • the divalent linking group includes a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, -O-, -CO-, - Examples thereof include SO 2 -, -NR L -, and a group formed by a combination thereof.
  • the divalent aliphatic hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms).
  • Lb a single bond, a methylene group, or a phenylene group is more preferable.
  • k is preferably an integer of 1 to 3, more preferably 1 or 2.
  • the specific resin may have only one type of the above-mentioned repeating unit B, or may have two or more types of the above-mentioned repeating unit B.
  • the specific resin has two or more types of repeating units B, it is preferable to have at least one repeating unit represented by the above formula (b).
  • the content of repeating unit B is preferably 1 mol% or more, more preferably 5 mol% or more, and 20% by mole or more, based on all repeating units in the specific resin. It is more preferably mol % or more, particularly preferably 30 mol % or more.
  • the upper limit is not particularly limited, but is preferably 99 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less, particularly preferably 75 mol% or less, based on all repeating units in the specific resin.
  • the ratio of the repeating unit A to the repeating unit B in the specific resin is not particularly limited, the ratio a/b of the number of moles of the repeating unit A to the number of moles of the repeating unit B is a/b in that the effect of the present invention is more excellent. is preferably 1/99 or more, more preferably 5/95 or more, even more preferably 10/90 or more, and particularly preferably 25/75 or more.
  • the lower limit of the ratio a/b is not particularly limited, but in terms of better solubility of the specific resin in the post-treatment liquid, the ratio a/b is preferably 99/1 or less, more preferably 95/5 or less, and 80/b.
  • the ratio is more preferably 20 or less, particularly preferably 70/30 or less.
  • repeating units A and repeating units B may be bonded randomly (so-called random copolymer), may be bonded alternately (so-called alternating copolymer), or in block form. They may also be combined (so-called block copolymers).
  • the specific resin may have a repeating unit different from both repeating unit A and repeating unit B.
  • the content of repeating units different from either repeating unit A or repeating unit B in the specific resin is preferably 20 mol% or less, more preferably 0 to 10 mol%, and 0 to 10 mol%, based on all repeating units in the specific resin. More preferably 5 mol%. It is preferable that the specific resin does not have a repeating unit different from either repeating unit A or repeating unit B.
  • Specific examples of the specific resin include resins represented by the following formulas (E-1) to (E-19).
  • the weight average molecular weight Mw of the specific resin is not particularly limited, and is preferably 500 to 1,000,000.
  • the above-mentioned weight average molecular weight Mw is more preferably 1,000 or more, still more preferably 2,000 or more, and particularly preferably 3,000 or more, since the effects of the present invention are more excellent.
  • the above-mentioned weight average molecular weight Mw is more preferably 500,000 or less, still more preferably 100,000 or less, and particularly preferably 50,000 or less, in terms of better solubility of the specific resin in the post-treatment liquid.
  • the content of the specific resin is preferably 1 mass ppm to 10 mass %, more preferably 10 to 10000 mass ppm (1 mass %), even more preferably 50 to 5000 mass ppm, based on the total mass of the chemical solution. 2000 ppm by mass is most preferred.
  • the content of the specific resin is preferably 0.1 to 10.0% by mass, and 0.1% to 10.0% by mass, based on the total solid content in the chemical solution. More preferably 3 to 3.0% by mass.
  • This drug solution contains water.
  • the content of water is not particularly limited, but is preferably 1 to 99.9999% by mass, more preferably 50 to 98% by mass, and even more preferably 80 to 97% by mass, based on the total mass of the chemical solution.
  • the water is preferably ultrapure water used in semiconductor device manufacturing.
  • the water is preferably water containing reduced amounts of inorganic anions and metal ions, and among them, Fe, Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, and It is more preferable that the ion concentration derived from the metal atoms of Zn is reduced, and when used for preparing a chemical solution, it is adjusted to the ppt order or less (in one form, the metal content is less than 0.001 mass ppt). It is more preferable that As a method of adjustment, purification using a filtration membrane or ion exchange membrane, or purification by distillation is preferable. Examples of the adjustment method include the method described in JP-A No. 2011-110515, paragraphs [0074] to [0084], and the method described in JP-A No. 2007-254168.
  • the water is preferably water in which the content of each ion is adjusted. Moreover, from the viewpoint that the desired effects of the present invention can be significantly obtained, it is more preferable that the above-mentioned water is used not only for cleaning the chemical solution but also for cleaning the container. Furthermore, it is preferable that the water described above is also used in the manufacturing process of the chemical liquid, the measurement of the components of the chemical liquid, the measurement for evaluating the chemical liquid, and the like.
  • the drug solution may further contain components other than the above components.
  • Components that may be included in the chemical solution include a removing agent, an oxidizing agent, a corrosion inhibitor, a surfactant, an antifoaming agent, and an organic solvent.
  • the present chemical solution may contain a removing agent, and preferably contains a removing agent since it has better residue removal properties.
  • the removing agent is not particularly limited as long as it is a compound that has the function of removing residues such as etching residues and ashing residues, but examples include fluorine-containing compounds, hydroxylamine compounds, basic compounds, and acidic compounds. Can be mentioned.
  • the fluorine-containing compound is not particularly limited as long as it contains a fluorine atom, and may be an inorganic compound containing a fluorine atom or an organic compound containing a fluorine atom.
  • the fluorine-containing compound include hydrofluoric acid (hydrofluoric acid), ammonium fluoride, tetramethylammonium fluoride, and tetrabutylammonium fluoride.
  • the fluorine-containing compound has the function of removing residues from the chemical solution. As a result, when the chemical solution contains a fluorine-containing compound, the residue removal performance is better.
  • the fluorine-containing compound is preferably hydrofluoric acid, ammonium fluoride, or tetramethylammonium fluoride, and more preferably hydrofluoric acid or ammonium fluoride.
  • the fluorine-containing compounds may be used alone or in combination of two or more.
  • the content of the fluorine-containing compound is preferably 0.01 to 15.0% by mass, more preferably 0.1 to 10.0% by mass, based on the total mass of the chemical solution.
  • the chemical solution may contain a hydroxylamine compound as a removing agent.
  • the hydroxylamine compound is at least one compound selected from the group consisting of hydroxylamine (NH 2 OH), hydroxylamine derivatives, and salts thereof. Since the hydroxylamine compound has the function of promoting decomposition and solubilization of residues and removing residues such as etching residues and ashing residues, the chemical solution preferably contains a hydroxylamine compound as a removing agent. .
  • Hydroxylamine derivatives are not particularly limited, but include, for example, O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,O-dimethylhydroxylamine, and N-ethylhydroxylamine.
  • salts of hydroxylamine and hydroxylamine derivatives include inorganic acid salts and organic acid salts, and inorganic acid salts formed by bonding nonmetallic atoms such as Cl, S, N, and P with hydrogen atoms are preferable, and hydrochloric acid, More preferred are acid salts of either sulfuric acid or nitric acid.
  • Inorganic acid salts of hydroxylamine and hydroxylamine derivatives include hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine phosphate, N,N-diethylhydroxylamine sulfate, N,N-diethylhydroxylamine nitrate, or Mixtures of these are preferred.
  • hydroxylamine and organic acid salts of hydroxylamine derivatives include hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium fluoride.
  • hydroxylamine compound hydroxylamine or hydroxylamine sulfate is preferable from the viewpoint of better residue removal properties.
  • hydroxylamine compound may be used alone, or two or more types may be used in combination.
  • the content of the hydroxylamine compound is preferably 0.01 to 30% by mass, more preferably 0.5 to 25% by mass, based on the total mass of the drug solution.
  • the chemical solution may contain a basic compound as a removing agent.
  • a basic compound is intended to be a compound whose solution pH exceeds 7 when dissolved in water.
  • the basic compound also functions as a pH adjuster that adjusts the pH of the chemical solution.
  • the compound contained in the corrosion inhibitor mentioned later shall not be contained in a basic compound.
  • the basic compound may form a salt with the acid group of the repeating unit B of the specific resin.
  • the basic compound is not particularly limited, and examples thereof include ammonium hydroxide, water-soluble amines, and quaternary ammonium compounds. Below, ammonium hydroxide, a water-soluble amine, and a quaternary ammonium compound are each explained in detail.
  • the chemical solution may contain ammonium hydroxide (NH 4 OH) as a basic compound.
  • ammonium hydroxide NH 4 OH
  • the content of ammonium hydroxide is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, based on the total mass of the chemical solution.
  • the chemical solution may contain a water-soluble amine as a basic compound.
  • water-soluble amine is a compound having an amino group in the molecule, and is intended to be a compound that can dissolve 50 g or more in 1 L of water.
  • water-soluble amines include primary amines having a primary amino group in the molecule, secondary amines having a secondary amino group in the molecule, and tertiary amines having a tertiary amino group in the molecule. amines and salts thereof.
  • the above-mentioned amine salts include salts with inorganic acids in which at least one nonmetal selected from the group consisting of Cl, S, N, and P is bonded to hydrogen, such as hydrochloride, sulfate, etc. Or nitrate is preferred.
  • the water-soluble amine is preferably a low molecular compound.
  • the term "low molecular compound” means a compound having substantially no molecular weight distribution.
  • the molecular weight of the low molecular weight compound is preferably 1000 or less. All of the specific examples of water-soluble amines listed below are low-molecular compounds with a molecular weight of 1000 or less.
  • the water-soluble amine may be an alicyclic amine compound having a ring structure in the molecule, or an alkanolamine having at least one hydroxyalkyl group in the molecule.
  • water-soluble amine may be used alone, or two or more types may be used in combination.
  • the content of the water-soluble amine is preferably 0.01 to 10% by mass, more preferably 0.1 to 5.0% by mass, based on the total mass of the chemical solution.
  • the chemical solution may contain a quaternary ammonium compound having one quaternary ammonium cation group in the molecule as a removing agent.
  • the quaternary ammonium compound is not particularly limited as long as it is a compound having at least one quaternary ammonium cation group formed by substituting four hydrocarbon groups (preferably alkyl groups) on the nitrogen atom.
  • Examples of the quaternary ammonium compound include quaternary ammonium hydroxide, quaternary ammonium fluoride, quaternary ammonium bromide, quaternary ammonium iodide, quaternary ammonium acetate, and quaternary ammonium acetate. Examples include ammonium carbonate.
  • quaternary ammonium compound a quaternary ammonium hydroxide is preferable, and a compound represented by the following formula (a1) is more preferable.
  • R a1 to R a4 are each independently an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or an aralkyl group having 1 to 16 carbon atoms. ⁇ 16 hydroxyalkyl groups. At least two of R a1 to R a4 may be bonded to each other to form a ring structure.
  • the compounds represented by the above formula (a1) include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide (TBAH), methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide (BzTMAH), hexadecyltrimethylammonium hydroxide, (2-hydroxy) At least one selected from the group consisting of ethyl)trimethylammonium and spiro-(1,1')-bipyrrolidinium hydroxide is preferred, TMAH, TEAH, TBAH, or BzTMAH is more preferred, and TMAH, TEAH, or TB
  • One type of quaternary ammonium compound may be used alone, or two or more types may be used in combination.
  • the content of the quaternary ammonium compound is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the chemical solution.
  • the basic compounds may be used alone or in combination of two or more.
  • the content of the basic compound is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total mass of the drug solution.
  • the chemical solution may contain an acidic compound as a removing agent.
  • the acidic compound is intended to be a compound that, when dissolved in water, causes the pH of the solution to be less than 7.
  • the acidic compound also functions as a pH adjuster that adjusts the pH of the chemical solution. Note that, in this specification, a compound included in either an oxidizing agent or an anionic surfactant described later is not included in the acidic compound.
  • the acidic compound may be an inorganic acid or an organic acid. As mentioned above, the inorganic acid or organic acid may form a salt with the amino group that repeating unit A of the specific resin has.
  • Inorganic acids include nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid, with sulfuric acid being preferred.
  • One type of inorganic acid may be used alone, or two or more types may be used in combination.
  • the content of the inorganic acid is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total mass of the chemical solution.
  • An organic acid is an organic compound that has an acidic functional group and exhibits acidity (pH less than 7.0) in an aqueous solution.
  • the acidic functional group include a carboxy group, a phosphonic acid group, a sulfo group, and a phenolic hydroxy group.
  • organic acids include, but are not limited to, carboxylic acids having a carboxy group in the molecule (organic carboxylic acids), phosphonic acids having a phosphonic acid group in the molecule (organic phosphonic acids), and sulfones having a sulfo group in the molecule.
  • examples include acids (organic sulfonic acids), and organic carboxylic acids are preferred.
  • the number of acidic functional groups that the organic acid has is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3. Further, the organic acid is preferably a compound that has a function of chelating with the metal contained in the residue, and the organic acid is preferably a compound that has two or more functional groups (coordination groups) that coordinate with metal ions in the molecule. preferable. Examples of the coordinating group include the above-mentioned acidic functional groups and amino groups.
  • carboxylic acids examples include polyaminopolycarboxylic acids, amino acids, polycarboxylic acids, and monocarboxylic acids.
  • the phosphonic acid may be a monophosphonic acid having only one phosphonic acid group in the molecule, or a polyphosphonic acid having two or more phosphonic acid groups in the molecule.
  • the number of phosphonic acid groups that the phosphonic acid has is preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 or 3.
  • the sulfonic acid may be a monosulfonic acid having only one sulfo group in the molecule, or a polysulfonic acid having two or more sulfo groups in the molecule.
  • the number of sulfo groups that the sulfonic acid has is preferably 1 or 2, and more preferably 1.
  • sulfonic acids examples include methanesulfonic acid (MSA), ethanesulfonic acid, isethionic acid (2-hydroxyethanesulfonic acid), benzenesulfonic acid, and p-toluenesulfonic acid (tosylic acid). Isethionic acid is preferred.
  • the organic acid has a low molecular weight.
  • the molecular weight of the organic acid is preferably 600 or less, more preferably 450 or less.
  • the lower limit is not particularly limited, but is preferably 85 or more.
  • the number of carbon atoms in the organic acid is preferably 15 or less, more preferably 12 or less, and even more preferably 8 or less.
  • the lower limit is not particularly limited, but is preferably 2 or more.
  • the above carboxylic acids are preferable, the above polyaminopolycarboxylic acids, the above amino acids, or the above polycarboxylic acids are more preferable, and the above amino acids or the above polycarboxylic acids are still more preferable.
  • One type of organic acid may be used alone, or two or more types may be used in combination.
  • the content of the organic acid is preferably 0.001 to 20% by mass, more preferably 0.005 to 10% by mass, based on the total mass of the chemical solution.
  • the chemical solution may contain other removing agents than those mentioned above.
  • Other removing agents include, for example, compounds having at least two nitrogen-containing groups and no carboxy groups. Specific examples of such compounds include at least one biguanide compound selected from the group consisting of compounds having a biguanide group and salts thereof.
  • a chelating agent described in Japanese Patent Publication No. 2017-504190 can also be used, and the contents described in the above document are incorporated herein.
  • the removing agent is preferably at least one selected from the group consisting of fluorine-containing compounds, hydroxylamine compounds, basic compounds, and acidic compounds, including hydrofluoric acid, ammonium fluoride, hydroxylamine compounds, ammonium hydroxide, At least one selected from the group consisting of water-soluble amines, quaternary ammonium compounds, sulfuric acid, and organic carboxylic acids is more preferred.
  • the chemical solution further improves the removal of dry etching residue when used as a cleaning solution. It is preferable to contain at least one selected from the group consisting of grade ammonium compounds, and it is more preferable to contain hydroxylamine, ammonium hydroxide, TMAH, or hydrofluoric acid.
  • One type of removing agent may be used alone, or two or more types may be used in combination.
  • the content of the removing agent is preferably 0.001 to 20% by mass, more preferably 0.005 to 10% by mass, based on the total mass of the chemical solution. Further, the content of the removing agent is preferably 0.1 to 98.0% by mass, more preferably 0.3 to 85.0% by mass, based on the total solid content in the chemical solution.
  • the chemical solution may contain an oxidizing agent.
  • the chemical liquid is an etching liquid, it is preferable that the chemical liquid contains an oxidizing agent.
  • oxidizing agents include peroxides such as hydrogen peroxide and peracetic acid, nitric acid, iodic acid, periodic acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, persulfuric acid, and dichromic acid. , permanganic acid, ozonated water, silver (II) salts, and iron (III) salts such as iron nitrate.
  • the above oxidizing agent may form a salt with a counterion.
  • the oxidizing agent contained in the chemical solution is preferably hydrogen peroxide, nitric acid, peracetic acid, periodic acid, perchloric acid, chloric acid, hypochlorous acid, cerium ammonium nitrate, iron nitrate, or ammonium persulfate. More preferred are hydrogen oxide, nitric acid, peracetic acid, periodic acid, or perchloric acid.
  • the oxidizing agents may be used alone or in combination of two or more.
  • the content of the oxidizing agent is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, based on the total mass of the chemical solution. Further, the content of the oxidizing agent is preferably 10 to 80% by mass, more preferably 30 to 60% by mass, based on the total solid content in the chemical solution.
  • the chemical solution may contain a corrosion inhibitor, and preferably contains a corrosion inhibitor.
  • the corrosion inhibitor is not particularly limited as long as it is a compound that has the function of preventing corrosion of the metal-containing layer due to over-etching by coordinating with the surface of the metal-containing layer to form a film. Examples thereof include group compounds, thiol compounds, and catechol compounds.
  • the heteroaromatic compound is not particularly limited as long as it has a heteroaromatic ring structure in the molecule, but nitrogen-containing heteroaromatic compounds in which at least one of the heteroatoms constituting the heteroaromatic ring is a nitrogen atom are preferred.
  • nitrogen-containing heteroaromatic compound include azole compounds, pyridine compounds, pyrazine compounds, and pyrimidine compounds, with azole compounds being preferred.
  • An azole compound is a compound having a 5-membered hetero ring containing one or more nitrogen atoms and having aromaticity.
  • the number of nitrogen atoms contained in the five-membered hetero ring of the azole compound is preferably 1 to 4, more preferably 1 to 3.
  • the azole compound may have a substituent on the 5-membered hetero ring. Examples of the above substituent include a hydroxy group, a carboxy group, a mercapto group, an amino group, an alkyl group having 1 to 4 carbon atoms which may have an amino group, and a 2-imidazolyl group.
  • azole compounds include imidazole compounds in which one of the atoms constituting the azole ring is a nitrogen atom, pyrazole compounds in which two of the atoms constituting the azole ring are nitrogen atoms, and one of the atoms constituting the azole ring Thiazole compounds in which one is a nitrogen atom and the other is a sulfur atom, triazole compounds in which three of the atoms constituting the azole ring are nitrogen atoms, and four of the atoms constituting the azole ring are nitrogen atoms. Examples include tetrazole compounds.
  • imidazole compounds include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole, 4-hydroxy
  • examples include imidazole, 2,2'-biimidazole, 4-imidazolecarboxylic acid, histamine, and benzimidazole.
  • pyrazole compounds include 2,4-dimethylthiazole, benzothiazole and 2-mercaptobenzothiazole.
  • thiazole compounds include 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole.
  • triazole compounds examples include 1,2,4-triazole, 3-methyl-1,2,4-triazole, 5-amino-1H-tetrazole, 3-amino-1,2,4-triazole, 1,2 , 3-triazole, 1-methyl-1,2,3-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4 -carboxybenzotriazole, 5-methyl-1H-benzotriazole, and 2,2'- ⁇ [(5-methyl-1H-benzotriazol-1-yl)methyl]imino ⁇ diethanol.
  • benzotriazole 5-methyl-1H-benzotriazole or tolyltriazole is preferred, and 5-methyl-1H-benzotriazole is more preferred.
  • the tetrazole compound include 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, Examples include 1,5-pentamethylenetetrazole, 5-mercapto-1-phenyltetrazole, and 1-(2-dimethylaminoethyl)-5-mercaptotetrazole. Among them, 5-mercapto-1-phenyltetrazole is preferred.
  • a pyridine compound is a compound having a 6-membered hetero ring (pyridine ring) that contains one nitrogen atom and has an aromatic property.
  • a pyrimidine compound is a compound that has an aromatic 6-membered hetero ring (pyrimidine ring) containing two nitrogen atoms located at the meta position. be.
  • Thiol compound means a compound having at least one thiol group and a hydrocarbon group.
  • the number of thiol groups that the thiol compound has is not particularly limited, but is preferably 1 or 2, and more preferably 1.
  • the hydrocarbon group possessed by the thiol compound includes an alkyl group (preferably having 4 to 20 carbon atoms), an alkenyl group (preferably having 4 to 12 carbon atoms), an alkynyl group (preferably having 4 to 12 carbon atoms), an aryl group (preferably having 4 to 12 carbon atoms), and an aryl group (preferably having 4 to 12 carbon atoms). (preferably 6 to 14 carbon atoms), and aralkyl groups (preferably 7 to 16 carbon atoms).
  • the hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxy group, and an amino group that may have an alkyl group.
  • the catechol compound means at least one selected from the group consisting of pyrocatechol (benzene-1,2-diol) and catechol derivatives.
  • Catechol derivative means a compound obtained by substituting pyrocatechol with at least one substituent.
  • Substituents that the catechol derivative has include a hydroxy group, a carboxy group, a carboxylic acid ester group, a sulfo group, a sulfonic acid ester group, an alkyl group (preferably having 1 to 6 carbon atoms), and an aryl group (preferably a phenyl group).
  • the carboxy group and sulfo group that the catechol derivative has as a substituent may be a salt with a cation.
  • the alkyl group and aryl group that the catechol derivative has as a substituent may further have a substituent.
  • a heteroaromatic compound or a thiol compound is preferable, and a triazole compound, a tetrazole compound, or a thiol compound is more preferable.
  • One type of corrosion inhibitor may be used alone, or two or more types may be used in combination.
  • the content of the corrosion inhibitor is preferably 0.001 to 10% by mass, more preferably 0.002 to 5% by mass, and 0.03 to 5% by mass, based on the total mass of the chemical solution. 1% by mass is more preferred. Further, the content of the corrosion inhibitor is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 10.0% by mass, based on the total solid content in the chemical solution.
  • the method for purifying the corrosion inhibitor is not particularly limited, but for example, known methods such as filtration, ion exchange, distillation, adsorption purification, recrystallization, reprecipitation, sublimation, and purification using a column are used, and these methods Can also be applied in combination.
  • the chemical solution may contain a surfactant.
  • the chemical solution preferably contains a surfactant, since it can further suppress dissolution of the metal film.
  • the surfactant is not particularly limited as long as it is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in the molecule, such as anionic surfactants, cationic surfactants, and nonionic surfactants. , and amphoteric surfactants.
  • Surfactants often have hydrophobic groups selected from aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof.
  • the hydrophobic group that the surfactant has is not particularly limited, but when the hydrophobic group includes an aromatic hydrocarbon group, it preferably has 6 or more carbon atoms, and more preferably 10 or more carbon atoms.
  • the number of carbon atoms is preferably 10 or more, and more preferably 12 or more.
  • the upper limit of the number of carbon atoms in the hydrophobic group is not particularly limited, but is preferably 20 or less.
  • anionic surfactant examples include phosphate ester surfactants, phosphonic acid surfactants, sulfonic acid surfactants, carboxylic acid surfactants, and sulfate ester surfactants. Examples include agents. As the anionic surfactant, a phosphate ester surfactant, a sulfonic acid surfactant, a carboxylic acid surfactant, or a sulfate ester surfactant is preferable.
  • cationic surfactant examples include primary to tertiary alkylamine salts (e.g., monostearylammonium chloride, distearylammonium chloride, tristearylammonium chloride, etc.), quaternary ammonium salts (e.g., dodecyltrimethylammonium chloride, etc.), and modified aliphatic polyamines (eg, polyethylene polyamine, etc.).
  • primary to tertiary alkylamine salts e.g., monostearylammonium chloride, distearylammonium chloride, tristearylammonium chloride, etc.
  • quaternary ammonium salts e.g., dodecyltrimethylammonium chloride, etc.
  • modified aliphatic polyamines eg, polyethylene polyamine, etc.
  • Nonionic surfactant examples include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkylphenyl ether, polyoxyalkylene glycol, polyoxyalkylene monoalkylate, polyoxyalkylene dialkylate, bispolyoxy Examples include alkylene alkylamides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethylene oxypropylene block copolymers, acetylene glycol surfactants, and acetylene polyoxyethylene oxides.
  • amphoteric surfactants examples include carboxybetaines (for example, alkyl-N,N-dimethylaminoacetic acid betaines and alkyl-N,N-dihydroxyethylaminoacetic acid betaines), sulfobetaines (for example, alkyl-N,N- dimethylsulfoethylene ammonium betaine, etc.), and imidazolinium betaine (eg, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidasolinium betaine, etc.).
  • carboxybetaines for example, alkyl-N,N-dimethylaminoacetic acid betaines and alkyl-N,N-dihydroxyethylaminoacetic acid betaines
  • sulfobetaines for example, alkyl-N,N- dimethylsulfoethylene ammonium betaine, etc.
  • imidazolinium betaine eg, 2-alkyl-N-carboxymethyl
  • surfactants include paragraphs [0092] to [0096] of JP-A No. 2015-158662, paragraphs [0045]-[0046] of JP-A No. 2012-151273, and paragraphs of JP-A No. 2009-147389.
  • Compounds described in [0014] to [0020] can also be referred to, the contents of which are incorporated herein.
  • One type of surfactant may be used alone, or two or more types may be used in combination.
  • the content of the surfactant is preferably 0.001 to 3% by mass, and 0.005 to 2% by mass, based on the total mass of the chemical solution, in order to obtain better effects of the present invention. Mass% is more preferred. Further, the content of the surfactant is preferably 1.0 to 40.0% by mass, more preferably 5.0 to 30.0% by mass, based on the total solid content in the chemical solution.
  • the chemical solution may contain an antifoaming agent.
  • Surfactants may cause foaming depending on how they are used. Therefore, the chemical solution containing a surfactant preferably contains an antifoaming agent that suppresses the occurrence of foaming, shortens the life of the generated foam, and suppresses the remaining foam.
  • the antifoaming agent is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include silicone antifoaming agents, acetylene diol antifoaming agents, fatty acid ester antifoaming agents, and long chain aliphatic alcohol antifoaming agents. Examples include foaming agents. Among these, silicone antifoaming agents are preferred because they have a more excellent effect of suppressing residual foam. Note that the antifoaming agent does not include the compounds contained in the above-mentioned surfactants.
  • the antifoaming agents may be used alone or in combination of two or more.
  • the content of the antifoaming agent is preferably 0.0001 to 3% by mass, and 0.001 to 2% by mass based on the total mass of the chemical solution, in terms of better suppression of residual foam. Mass% is more preferred.
  • the content of the antifoaming agent is preferably 1.0 to 40.0% by mass, more preferably 5.0 to 30.0% by mass, based on the total solid content in the chemical solution.
  • the chemical solution may contain an organic solvent, and preferably contains an organic solvent.
  • the organic solvent is preferably a water-soluble organic solvent. When the organic solvent is water-soluble, it is intended that water at 25° C. and the organic solvent can be mixed (dissolved) in any ratio.
  • the organic solvent include alcohol solvents, ketone solvents, ester solvents, ether solvents (eg, glycol diether), sulfone solvents, sulfoxide solvents, nitrile solvents, and amide solvents. These solvents may be water-soluble.
  • the chemical solution preferably contains one or more organic solvents selected from the group consisting of alcohol solvents, ketone solvents, ester solvents, and ether solvents.
  • alcoholic solvents include alkanediols (including alkylene glycols), alkoxy alcohols (including glycol monoethers), saturated aliphatic monohydric alcohols, unsaturated non-aromatic monohydric alcohols, and cyclic alcohols. Examples include low molecular weight alcohols containing structures.
  • alkanediol examples include glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3 -butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycol.
  • alkylene glycol examples include ethylene glycol, propylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol, with propylene glycol or hexylene glycol being preferred.
  • alkoxy alcohol examples include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and glycol monoether, with glycol monoether being preferred.
  • glycol monoethers include ethylene glycol mono C1-C4 alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol monomethyl Diethylene glycol mono C1-C4 alkyl ethers such as ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; triethylene glycol mono C1-C4 alkyl ethers such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether; 1-methoxy-2-propanol,
  • Examples of the saturated aliphatic monohydric alcohol include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, and , hexanol.
  • Examples of the unsaturated non-aromatic monohydric alcohol include allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.
  • Examples of the low molecular weight alcohol containing a ring structure include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.
  • One type of organic solvent may be used alone, or two or more types may be used in combination.
  • the content of the organic solvent is preferably 0.1 to 30% by mass, more preferably 1 to 15% by mass, based on the total mass of the chemical solution.
  • the chemical solution may contain a metal component.
  • Metal components include metal particles and metal ions.
  • the content of metal components refers to the total content of metal particles and metal ions.
  • the chemical solution may contain either metal particles or metal ions, or both.
  • metal atoms contained in the metal component include Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, and Na. , Ni, Pb, Sn, Sr, Ti, and Zn.
  • the metal component may contain one type of metal atom, or may contain two or more types of metal atoms.
  • the metal particles may be a single substance or an alloy, and may exist in a form in which metal is associated with an organic substance.
  • the metal component may be a metal component that is unavoidably included in each component (raw material) contained in the chemical solution, or a metal component that is unavoidably included during the production, storage, and/or transportation of the drug solution, May be added
  • the content of the metal component is often 0.01 mass ppt to 10 mass ppm, preferably 0.1 mass ppt to 1 mass ppm, based on the total mass of the chemical solution. .1 mass ppt to 100 mass ppb is more preferable.
  • the type and content of metal components in the chemical solution can be measured by SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry).
  • SP-ICP-MS Single Nano Particle Inductively Coupled Plasma Mass Spectrometry
  • the SP-ICP-MS method uses the same equipment as the normal ICP-MS method (inductively coupled plasma mass spectrometry), and differs only in data analysis. Data analysis of the SP-ICP-MS method can be performed using commercially available software.
  • the content of the metal component to be measured is measured regardless of its existing form. Therefore, the total mass of the metal particles and metal ions to be measured is determined as the content of the metal component.
  • the SP-ICP-MS method allows the content of metal particles to be measured. Therefore, the content of metal ions in the sample can be calculated by subtracting the content of metal particles from the content of metal components in the sample.
  • Agilent 8800 triple quadrupole ICP-MS inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200
  • Agilent Technologies, Inc As a measurement method using the SP-ICP-MS method, for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies, Inc. It can be measured by the method described.
  • Agilent 8900 manufactured by Agilent Technologies can also be used.
  • the method for adjusting the content of each metal component in the chemical solution is not particularly limited.
  • the content of metal components in the chemical solution can be reduced by performing a known treatment for removing metals from the chemical solution and/or from the raw materials containing each component used for preparing the chemical solution.
  • the content of metal components in the chemical solution can be increased.
  • the drug solution may contain additives other than the above-mentioned components.
  • additives include antibacterial agents, rust preventives, and preservatives.
  • the chemical solution may contain the compound represented by formula (1) as an unreacted monomer. More specifically, the drug solution may contain a compound represented by formula (2) or a compound represented by formula (3).
  • the content of each of the above components (excluding metal components) in the drug solution can be determined by gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-mass spectrometry (LC-MS). It can be measured by known methods such as mass spectrometry and ion-exchange chromatography (IC).
  • GC-MS gas chromatography-mass spectrometry
  • LC-MS liquid chromatography-mass spectrometry
  • the pH of the chemical solution is not particularly limited, and is preferably 2.0 to 12.0. When used as a cleaning solution, the pH of the chemical solution is more preferably 3.0 to 10.0. This is because a chemical solution having a pH within the above range is more effective in the present invention.
  • the pH of the chemical solution is a value obtained by measuring at 25° C. in accordance with JIS Z8802-1984 using a pH meter (for example, model "F-74" manufactured by Horiba, Ltd.).
  • the chemical solution does not substantially contain coarse particles.
  • Coarse particles refer to particles having a diameter of 0.2 ⁇ m or more when the shape of the particles is considered to be spherical, for example.
  • substantially free of coarse particles means that when a chemical solution is measured using a commercially available measuring device using a light scattering particle-in-liquid measurement method, particles of 0.2 ⁇ m or more in 1 mL of the drug solution are 10 This means that the number is less than 1.
  • Coarse particles contained in chemical solutions include particles such as dust, dirt, organic solids, and inorganic solids contained as impurities in raw materials, as well as dust, dirt, and organic solids brought in as contaminants during the preparation of drug solutions.
  • the amount of coarse particles present in a chemical solution can be measured in the liquid phase using a commercially available measurement device using a light scattering particle-in-liquid measurement method using a laser as a light source. Examples of methods for removing coarse particles include processing such as filtering.
  • the drug solution may be prepared as a kit by dividing the raw material into a plurality of parts.
  • a specific method for preparing a kit of chemical solutions includes, for example, a mode in which a composition containing water and a removing agent is prepared as a first liquid, and a chemical solution containing a specific resin is prepared as a second liquid. Can be mentioned.
  • the content of each component contained in the first liquid and the second liquid included in the kit is not particularly limited, but the content of each component in the drug solution prepared by mixing the first liquid and the second liquid is preferably as described above. It is preferable that the amount is such as the content.
  • the pH of the first liquid and the second liquid provided in the kit is not particularly limited, and the pH of each is adjusted so that the pH of the drug solution prepared by mixing the first liquid and the second liquid becomes a desired value. All you have to do is stay there.
  • the drug solution may be prepared as a concentrated solution.
  • a diluted solution obtained by diluting with a diluting liquid before use is used.
  • the kit may include the above-mentioned drug solution in the form of a concentrated liquid and the above-mentioned liquid for dilution.
  • the diluting liquid is preferably a liquid selected from the group consisting of water, isopropanol, a mixture of water and isopropanol, and a solvent containing ammonium hydroxide, and water, isopropanol, or a mixture of water and isopropanol is preferable. More preferred, and even more preferred is water.
  • the dilution ratio of the chemical solution is not particularly limited, but is preferably 1 to 2000 times, more preferably 1 to 100 times.
  • a chemical solution containing each component in an amount obtained by dividing the suitable content of each component (excluding water) that can be contained in the chemical solution by the dilution ratio (for example, 100) in the above range (hereinafter also referred to as "diluent"). ) can also be suitably used.
  • the preferred content of each component (excluding water) relative to the total mass of the diluted solution is, for example, the amount explained as the preferred content of each component relative to the total mass of the drug solution before dilution, at a dilution ratio within the above range (for example, 100 ).
  • a specific method for diluting the chemical solution may be carried out in accordance with the chemical solution preparation process described below.
  • the stirring device and stirring method used in the dilution step the known stirring device mentioned in the below-mentioned chemical solution preparation step may be used.
  • This chemical solution is a chemical solution for semiconductor devices.
  • "for semiconductor devices” means used for manufacturing semiconductor devices.
  • This chemical solution can be used in any process for manufacturing a semiconductor device, for example, in a process for treating a semiconductor substrate included in a method for manufacturing a semiconductor device. More specifically, the chemical solution is used to treat insulating films, resists, antireflection films, etching residues, ashing residues, and residues derived from resist films such as photoresists and metal hard masks that exist on the substrate.
  • residues etching residues, ashing residues, resist film-derived residues, and the like are collectively referred to as residues.
  • the present chemical solution may be used in an etching process to remove metal-containing substances on a substrate, or may be used in processing a substrate after chemical mechanical polishing.
  • the chemical liquid is, for example, a pre-wet liquid that is applied on a substrate to improve the coating properties of the chemical liquid before the step of forming a resist film using an actinic ray-sensitive or radiation-sensitive chemical liquid, or a pre-wet liquid that is applied on a metal layer.
  • the present chemical solution can also be used as a cleaning solution for removing residues such as metal impurities or fine particles from a substrate after chemical mechanical polishing.
  • this chemical solution can also be used as an etching solution for metal-containing materials (including metal oxides and composite oxides made of multiple metal oxides) on a substrate.
  • a cleaning solution for removing residues a solution for removing a resist film used for pattern formation, a cleaning solution for removing residues from a substrate after chemical mechanical polishing, or It can be suitably used as an etching solution.
  • the chemical solution may be used for only one of the above uses, or may be used for two or more of the above uses.
  • a diluted solution obtained by diluting the chemical solution can also be used for the above purpose. Among these, it can be suitably used as a cleaning solution for removing residues on a substrate (more preferably a substrate subjected to chemical mechanical polishing).
  • This chemical solution can be suitably used for processing a substrate including a metal layer containing W for a semiconductor device, and a substrate including a metal layer containing Mo for a semiconductor device.
  • This chemical solution can also be used to treat a substrate including a metal layer containing Co for semiconductor devices, and a substrate including a metal layer containing Cu for semiconductor devices.
  • the present chemical solution has excellent corrosion prevention properties for insulating films, for example, if a semiconductor device is made of at least one material selected from the group consisting of SiO x , SiN, and SiOC (x represents a number from 1 to 3). It can also be used to treat substrates with seed-containing layers.
  • the method for producing the present drug solution is not particularly limited, and the present drug solution can be produced by a known production method.
  • the method for producing the present drug solution include a method that includes at least a step of preparing a drug solution by mixing the above-mentioned components.
  • the order in which the components are mixed is not particularly limited. It is preferable that the concentrated liquid and each liquid included in the kit are also manufactured by the same method as above.
  • the method for preparing the kit is not particularly limited, and for example, a drug solution can be prepared by preparing the first solution and the second solution, and then storing each of the first solution and the second solution in different containers. All you need to do is make a kit.
  • the above manufacturing method preferably includes a filtration step of filtering the liquid in order to remove foreign substances, coarse particles, etc. from the liquid.
  • the filtration method is not particularly limited, and any known filtration method can be used. Among these, filtering using a filter is preferable.
  • the filter used for filtering can be used without any particular restriction as long as it has been conventionally used for filtration purposes.
  • Materials constituting the filter include, for example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP). ) etc.
  • fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP). ) etc.
  • polyamide resins, PTFE, and polypropylene including high-density polypropylene are preferred.
  • the lower limit of the critical surface tension of the filter is preferably 70 mN/m or more, and the upper limit is preferably 95 mN/m or less.
  • the critical surface tension of the filter is preferably 75 to 85 mN/m.
  • the critical surface tension value is the manufacturer's nominal value.
  • the pore diameter 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.
  • the filter used be treated before filtering the chemical solution.
  • the liquid used in this treatment is not particularly limited, but preferably includes a chemical liquid, a concentrated liquid, and a liquid containing components contained in the chemical liquid.
  • the upper limit of the temperature during filtering is preferably at most room temperature (25°C), more preferably at most 23°C, even more preferably at most 20°C.
  • the lower limit of the temperature during filtering is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher. Filtering can remove particulate foreign matter and/or impurities, but when performed at the above temperature, the amount of particulate foreign matter and/or impurities dissolved in the chemical solution is reduced, making filtering more efficient. It will be held on.
  • the above manufacturing method may further include a static eliminating step of static neutralizing at least one selected from the group consisting of a chemical solution, a concentrated solution, and a kit. Note that a specific method of static elimination will be described later.
  • the clean room meets 14644-1 clean room standards. It is preferable that it satisfies ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, or ISO Class 4, more preferably that it satisfies ISO Class 1 or ISO Class 2, and that it satisfies ISO Class 1. More preferred.
  • ISO International Organization for Standardization
  • the container for storing the above-mentioned chemical solution, concentrated solution, or kit is not particularly limited as long as the corrosivity caused by the solution is not a problem, and any known container can be used.
  • any known container can be used.
  • the inside of the container has a high degree of cleanliness and that little impurity is leached out.
  • Specific examples of the containers include the "Clean Bottle” series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle” manufactured by Kodama Resin Industries.
  • multilayer containers whose inner walls have a 6-layer structure made of 6 types of resin, and multilayer containers whose inner walls have a 7-layer structure made of 6 types of resin. It is also preferable.
  • these containers include, but are not limited to, the containers described in JP-A-2015-123351. Further, as the container, containers illustrated in paragraphs [0121] to [0124] of International Publication No. 2022/004217 can also be used, and the contents of these are incorporated herein.
  • the liquid used for cleaning may be appropriately selected depending on the intended use, but preferably the present drug, a liquid obtained by diluting the present drug, or a liquid containing at least one of the components added to the present drug.
  • the inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) with a purity of 99.99995% by volume or more.
  • an inert gas nitrogen, argon, etc.
  • a gas with a low water content is preferred.
  • the temperature when transporting and storing the liquid container, the temperature may be at room temperature, but the temperature may be controlled within the range of -20°C to 20°C to prevent deterioration.
  • the present treatment method In a method for treating a substrate using a chemical solution (hereinafter also simply referred to as the "present treatment method"), the present chemical solution is typically applied to a substrate having a metal-containing material, which is a material containing metal (hereinafter referred to as “the subject treatment method”). (Also referred to as “processed material”). At this time, the object to be treated may contain multiple types of metal-containing substances.
  • the object to be processed which is the object to be processed using the chemical solution, is not particularly limited as long as it is a substrate having a metal-containing substance.
  • “on the substrate” in this specification includes, for example, the front and back sides of the substrate, the side surfaces, and inside the grooves.
  • the metal-containing substance on the substrate includes not only the case where the metal-containing substance exists directly on the surface of the substrate, but also the case where the metal-containing substance exists on the substrate via another layer.
  • substrate in this specification includes, for example, a single-layer semiconductor substrate and a multi-layer semiconductor substrate.
  • the expression "object to be removed” in this specification means at least one kind selected from the group consisting of metal-containing substances that exist on the substrate and are the object of removal using a chemical solution.
  • a metal-containing material is a material containing a metal (metal atom) as a main component.
  • metals contained in the metal-containing material include Cu (copper), Co (cobalt), W (tungsten), Ti (titanium), Ta (tantalum), Ru (ruthenium), Cr (chromium), and Hf (hafnium). , Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium).
  • One type of metal M is mentioned.
  • the metal-containing substance only needs to be a substance containing a metal (metal atom), for example, a simple substance of metal M, an alloy containing metal M, an oxide of metal M, a nitride of metal M, and a substance containing metal M.
  • a metal metal atom
  • Examples include a substance composed of at least one selected from the group consisting of oxynitrides.
  • More specific metal inclusions include copper, cobalt, cobalt alloy, tungsten, tungsten alloy, ruthenium, ruthenium alloy, tantalum, tantalum alloy, aluminum oxide, aluminum nitride, aluminum nitride oxide, titanium aluminum, titanium, titanium nitride, Examples include metal-containing materials containing at least one component selected from the group consisting of titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide, and yttrium alloy. Further, the metal-containing material may be a mixture containing two or more of these compounds.
  • the form of the metal-containing material is not particularly limited, and may be, for example, a film-like (layered) form, a wire-like form, or a particulate form.
  • the metal-containing material may be arranged only on one main surface of the substrate, or may be arranged on both main surfaces. Further, the metal-containing substance may be arranged on the entire main surface of the substrate, or may be arranged on a part of the main surface of the substrate.
  • the substrate preferably has a metal M-containing substance containing metal M, and preferably has a metal-containing substance containing at least one metal selected from the group consisting of W, Mo, Cu, Co, Ti, Ta, and Ru. It is more preferable to have a metal inclusion containing at least one metal selected from the group consisting of W, Mo, Cu, and Co, and it is even more preferable to have a metal inclusion containing at least one of W and a W alloy (W It is particularly preferable to have the following.
  • the substrate preferably has a W-containing film, a Mo-containing film, a copper-containing film, a Co-containing film, or a Ti-containing film, and more preferably a W-containing film or a Mo-containing film.
  • the W-containing film include a metal film made of only tungsten (W metal film) and a metal film made of an alloy made of tungsten and another metal (W alloy metal film).
  • W alloy metal film include a WTi alloy metal film and a WCo alloy metal film. Tungsten-containing films are often used as wiring films or barrier metals.
  • Mo-containing film examples include a metal film made only of molybdenum (Mo metal film) and a metal film made of an alloy made of molybdenum and other metals (Mo alloy metal film).
  • Mo alloy metal film A specific example of the Mo alloy metal film is a MoCo alloy metal film.
  • Examples of the copper-containing film include a wiring film made of only metallic copper (copper wiring film) and a wiring film made of an alloy made of metallic copper and another metal (copper alloy wiring film).
  • a specific example of the copper alloy wiring film includes a wiring film made of an alloy made of copper and one or more metals selected from Al, Ti, Cr, Mn, Ta, and W. More specifically, examples include a CuAl alloy wiring film, a CuTi alloy wiring film, a CuCr alloy wiring film, a CuMn alloy wiring film, a CuTa alloy wiring film, and a CuW alloy wiring film.
  • the Co-containing film examples include a metal film made only of metallic cobalt (Co metal film) and a metal film made of an alloy made of metallic cobalt and another metal (Co alloy metal film).
  • a specific example of the Co alloy metal film is a metal film made of an alloy made of cobalt and one or more metals selected from Ti, Cr, Fe, Ni, Mo, Pd, Ta, and W. More specifically, examples include CoTi alloy metal film, CoCr alloy metal film, CoFe alloy metal film, CoNi alloy metal film, CoMo alloy metal film, CoPd alloy metal film, CoTa alloy metal film, and CoW alloy metal film.
  • the Co metal film is often used as a wiring film
  • the Co alloy metal film is often used as a barrier metal.
  • the Ti-containing film examples include a metal film containing an alloy of Ti and another metal such as Al, and a Ti alloy metal film that may further contain the above dopant.
  • Specific examples of the Ti alloy metal film include a TiAl film, a TiAlC film, and a TiAlN film. Ti alloy metal films are often used for gates and structures around them.
  • a more specific example of the object to be processed is a laminate including at least a metal layer, an insulating film, and a metal hard mask in this order on a substrate.
  • the laminate may further have a hole formed from the surface (opening) of the metal hard mask toward the substrate so as to expose the surface of the metal layer through a dry etching process or the like.
  • the method for manufacturing a laminate having holes as described above is not particularly limited, usually a pre-processing laminate including a substrate, a metal layer, an insulating film, and a metal hard mask in this order is An example of this method is to perform a dry etching process using a hard mask as a mask to etch the insulating film so that the surface of the metal layer is exposed, thereby providing a hole penetrating the metal hard mask and the insulating film.
  • the method for manufacturing the metal hard mask is not particularly limited, and for example, first, a metal layer containing a predetermined component is formed on an insulating film, and a resist film with a predetermined pattern is formed thereon.
  • a metal hard mask that is, a film in which a metal layer is patterned
  • the laminate may have layers other than the above-mentioned layers, such as an etching stop film, an antireflection film, and the like.
  • FIG. 1 is a schematic cross-sectional view showing an example of a laminate, which is an object to be treated in this treatment method.
  • the laminate 10 shown in FIG. 1 includes a metal layer 2, an etching stopper layer 3, an insulating film 4, and a metal hard mask 5 in this order on a substrate 1, and the metal layer 2 is placed in a predetermined position through a dry etching process or the like.
  • a hole 6 is formed through which the is exposed. That is, the object to be processed shown in FIG. 1 includes a substrate 1, a metal layer 2, an etching stop layer 3, an insulating film 4, and a metal hard mask 5 in this order. It is a laminate with a hole 6 penetrating from its surface to the surface of the metal layer 2 at the position.
  • the inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a made of an etching stop layer 3, an insulating film 4, and a metal hard mask 5, and a bottom wall 11b made of an exposed metal layer 2, on which dry etching residue 12 adheres. are doing.
  • This treatment method can be suitably used to remove these dry etching residues 12. That is, it is excellent in the removability of the dry etching residue 12 (residue removability) and is also excellent in corrosion prevention against the inner wall 11 (for example, the metal layer 2, etc.) of the object to be processed. Further, the above substrate processing method may be performed on a laminate that has been subjected to a dry ashing process after a dry etching process. The materials constituting each layer of the above-mentioned laminate will be explained below.
  • Metal hard masks include copper, cobalt, cobalt alloy, tungsten, tungsten alloy, ruthenium, ruthenium alloy, tantalum, tantalum alloy, aluminum oxide, aluminum nitride, aluminum nitride oxide, titanium aluminum, titanium aluminum carbide, titanium, titanium nitride, oxide It is preferable that at least one component selected from the group consisting of titanium, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide, and yttrium alloy (preferably YSiOx) is included.
  • Examples of the material of the metal hard mask include TiN, TiAl, TiAlC, WO2 , and ZrO2 .
  • the material of the insulating film is not particularly limited, and examples thereof include those having a dielectric constant k of preferably 3.0 or less, more preferably 2.6 or less. Specific examples of the material of the insulating film include SiOx, SiN, SiOC, and organic polymers such as polyimide. Note that x is preferably a number represented by 1 to 3.
  • the insulating film may be composed of a plurality of films. An example of an insulating film composed of a plurality of films is an insulating film formed by combining a film containing silicon oxide and a film containing silicon oxide carbide.
  • the material of the etching stop layer is not particularly limited. Specific materials for the etching stop layer include SiN, SiON, SiOCN-based materials, and metal oxides such as AlOx.
  • the material forming the metal layer serving as the wiring material and/or the plug material is not particularly limited, but preferably includes one or more selected from the group consisting of cobalt, tungsten, and copper. Further, the material forming the metal layer may be cobalt, tungsten, or an alloy of copper and other metals. The metal layer may further include metals other than cobalt, tungsten and copper, metal nitrides and/or alloys. Examples of metals other than cobalt, tungsten, and copper that the metal layer may contain include titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxide, and aluminum. The metal layer may include at least one dopant selected from the group consisting of carbon, nitrogen, boron, and phosphorous in addition to one or more dopants selected from the group consisting of cobalt, tungsten, and copper.
  • wafers constituting the substrate include silicon (Si) wafers, silicon carbide (SiC) wafers, wafers made of silicon-based materials such as silicon-containing resin wafers (glass epoxy wafers), and gallium phosphide (GaP) wafers. , gallium arsenide (GaAs) wafers, and indium phosphide (InP) wafers.
  • silicon wafers include n-type silicon wafers doped with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb), etc.), and silicon wafers doped with trivalent atoms (e.g. , boron (B), gallium (Ga), etc.) may be a p-type silicon wafer.
  • the silicon of the silicon wafer may be, for example, any of amorphous silicon, single crystal silicon, polycrystalline silicon, and polysilicon.
  • the object to be processed may contain various layers and/or structures as desired in addition to those described above.
  • the substrate may contain metal wiring, a gate electrode, a source electrode, a drain electrode, an insulating layer, a ferromagnetic layer, a nonmagnetic layer, and the like.
  • the substrate may contain exposed integrated circuit structures, such as interconnect features such as metal traces and dielectric materials.
  • Metals and alloys used in interconnect mechanisms include, for example, aluminum, copper-aluminum alloys, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten.
  • the substrate may contain layers of silicon oxide, silicon nitride, silicon carbide, and/or carbon-doped silicon oxide.
  • the method for producing the object to be processed is not particularly limited as long as it is a method commonly used in this field.
  • a method for forming the above-mentioned insulating film on the wafer constituting the substrate for example, the wafer constituting the substrate is heat-treated in the presence of oxygen gas to form a silicon oxide film, and then a silane film is formed on the wafer constituting the substrate. and a method of forming a silicon nitride film by a chemical vapor deposition (CVD) method by flowing ammonia gas.
  • CVD chemical vapor deposition
  • a method for forming the above-mentioned metal-containing layer on the wafer constituting the substrate for example, a circuit is formed on the wafer having the above-mentioned insulating film by a known method such as resist, and then plating or sputtering method is used.
  • methods include forming the metal-containing layer by methods such as , CVD, and molecular beam epitaxy (MBE).
  • the object to be processed may be a substrate on which an insulating film, a barrier metal, and a metal-containing film are provided on a wafer, and then a planarization process such as a CMP process is performed.
  • the CMP process is a process in which the surface of a substrate having a metal-containing film, a barrier metal, and an insulating film is planarized by a combined action of chemical action and mechanical polishing using a polishing slurry containing abrasive particles (abrasive grains).
  • Impurities such as abrasive grains (e.g.
  • metal impurities metal residue derived from the polished metal-containing film and barrier metal are present on the surface of the substrate that has been subjected to the CMP process. It may remain. These impurities can, for example, cause short circuits between wiring lines and deteriorate the electrical characteristics of the board, so a board that has been subjected to CMP processing should be subjected to a cleaning process to remove these impurities from the surface. Ru.
  • a substrate subjected to CMP processing see the Journal of Precision Engineering Vol. 84, No. 3, 2018, but is not limited thereto.
  • Examples of this treatment method include a treatment method including step A of bringing a chemical solution into contact with a substrate having a metal-containing substance. By performing this step A, metal-containing substances on the substrate can be removed.
  • the chemical solution used in step A is as described above.
  • the substrate having a metal-containing substance which is the object to be processed in step A, is also as described above.
  • a substrate having a metal-containing substance a substrate having a W-containing substance or a substrate having a Mo-containing substance is preferable.
  • the method of bringing the chemical solution into contact with the object to be treated is not particularly limited. Examples include a method of flowing a chemical solution onto the surface, or any combination thereof. Among these, a method in which a substrate having a metal-containing material to be treated is immersed in a chemical solution is preferred.
  • a mechanical stirring method may be used to further improve the throughput of the chemical solution.
  • mechanical stirring methods include a method of circulating a chemical solution on a substrate, a method of flowing or spraying a chemical solution on a substrate, and a method of stirring a chemical solution using ultrasonic waves or megasonic waves.
  • the treatment by dipping may be a batch method in which a plurality of objects to be treated are immersed in a processing tank for treatment, or may be a single wafer method.
  • the processing time of step A can be adjusted depending on the method of bringing the chemical into contact with the substrate, the temperature of the chemical, and the like.
  • the treatment time time of contact between the chemical solution and the object to be treated
  • the temperature of the chemical solution during treatment is not particularly limited, but the lower limit is preferably 15°C or higher, more preferably 20°C or higher, and even more preferably 30°C or higher.
  • the upper limit of the temperature is preferably 90°C or lower, more preferably 80°C or lower, and even more preferably 70°C or lower.
  • step A includes step A1 of recess etching the wiring made of a metal-containing substance placed on the substrate using a chemical solution; Step A2 of removing the film on the outer edge; Step A3 of removing the metal-containing material adhering to the back surface of the substrate on which the film made of metal-containing material is arranged using a chemical solution; Examples include step A4 of removing metal-containing materials, and step A5 of removing metal-containing materials on the substrate after chemical mechanical polishing using a chemical solution.
  • steps A1 to A5 the descriptions in paragraphs [0049] to [0072] of International Publication No. 2019/138814 can be cited, and the contents thereof are incorporated herein.
  • this treatment method further includes a step (hereinafter referred to as "step B") of rinsing the object to be treated using a rinsing liquid (rinsing with a solvent to clean it). It's okay. It is preferable that step B is carried out consecutively to step A, and is a step of rinsing with a rinsing liquid for 5 seconds to 5 minutes. Step B may be performed using the mechanical stirring method described above.
  • Examples of the solvent for the rinse solution include deionized (DI) water, methanol, ethanol, isopropanol, N-methylpyrrolidinone, ⁇ -butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate.
  • the solvent for the rinse solution is preferably DI water, methanol, ethanol, isopropanol, or a mixture thereof, and more preferably DI water, isopropanol, or a mixture of DI water and isopropanol.
  • the method of bringing the chemical solution into contact with the object to be processed described above can be similarly applied.
  • the temperature of the rinsing solvent in step B is preferably 16 to 27°C.
  • This treatment method may include a step C of drying the object to be treated after step B.
  • the drying method is not particularly limited, and includes, for example, a spin drying method, a method of passing a drying gas over the object to be processed, a method of heating the substrate with a heating means such as a hot plate or an infrared lamp, a Marangoni drying method, Examples include Rotagoni drying method, IPA (isopropanol) drying method, and any combination thereof.
  • the drying time in step C depends on the drying method, but is preferably 20 seconds to 5 minutes.
  • step C it is preferable to dry the substrate by heating it with a heating means, since the chemical solution in the SiOx layer is excellent in removability.
  • the heating temperature in that case is not particularly limited, but is preferably 50 to 350°C, more preferably more than 100°C and less than 400°C, from the viewpoint of achieving a better balance between chemical removal properties in the SiOx layer and film reduction in the Co film and SiOx layer.
  • the temperature is more preferably 150 to 250° C. from the viewpoint of better removability of the chemical solution in the Co film and the SiOx layer.
  • the present invention also includes inventions of compounds.
  • the compound of the present invention is a compound represented by the above formula (3).
  • the present invention also includes inventions of resins.
  • the resin of the present invention is a resin having repeating units derived from the compound represented by the above formula (3).
  • a solution obtained by dissolving bis(2-methoxyethyl) azodicarboxylate (DMEAD (registered trademark), 88.9 g, 0.38 mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in THF (105 mL) was prepared separately. While maintaining the internal temperature of the reaction solution obtained above at 5° C. or lower, the above solution was added dropwise to the reaction solution over 2 hours. After the dropwise addition was completed, the resulting reaction solution was stirred at 0° C. for 2 hours. Next, the solvent was distilled off from the obtained reaction solution under reduced pressure of 40° C./10 hPa.
  • Ethyl acetate 300 mL, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • distilled water 400 mL
  • the lower phase aqueous phase
  • the upper phase organic phase
  • Distilled water 400 mL was added to the obtained organic phase and stirred, and the solution obtained after stirring was allowed to stand, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was collected.
  • the solvent was distilled off from the obtained organic phase under reduced pressure of 40° C./10 hPa to obtain intermediate E-1C.
  • a solution obtained by dissolving DMEAD (registered trademark) (40.4 g, 0.6 mol, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in THF (111 mL) was separately prepared. While maintaining the internal temperature of the reaction solution obtained above at 5° C. or lower, the above solution was added dropwise to the reaction solution over 2 hours. After the dropwise addition was completed, the resulting reaction solution was stirred at 0° C. for 2 hours. Next, the solvent was distilled off from the obtained reaction solution under reduced pressure of 40° C./10 hPa.
  • the pH of the chemical solution was measured at 25° C. using a pH meter (manufactured by Horiba, Ltd., model "F-74") in accordance with JIS Z8802-1984.
  • a pH meter manufactured by Horiba, Ltd., model "F-74”
  • handling of containers, preparation of chemical solutions, filling, storage, and analytical measurements were all performed in a clean room meeting ISO class 2 or lower.
  • Resins CE-1 to CE-2 are resins that do not fall under specific resins.
  • Mw is the weight average molecular weight of each resin measured by the method described above.
  • the numbers appended to repeating units indicate the composition ratio (mole fraction) of each repeating unit in the resin. The composition ratio of each repeating unit in the resin was measured by 13 C-NMR.
  • ⁇ Removal agent> ⁇ Hydroxylamine (corresponds to hydroxylamine compounds) ⁇ Ammonium hydroxide (corresponds to basic compounds) ⁇ Tetramethylammonium hydroxide (TMAH) (corresponds to a basic compound) ⁇ Hydrofluoric acid (corresponds to fluorine-containing compounds) ⁇ Sulfuric acid (corresponds to inorganic acid) ⁇ Citric acid (corresponds to organic acid) ⁇ Tartaric acid (corresponds to organic acid) ⁇ Succinic acid (corresponds to organic acid) ⁇ Ethylenediaminetetraacetic acid (EDTA) (corresponds to organic acid) ⁇ Trishydroxymethylaminomethane (Tris) (corresponds to a basic compound) ⁇ Monoethanolamine (corresponds to basic compounds) ⁇ Tris(2-hydroxyethyl)methylammonium hydroxide (corresponds to a basic compound) ⁇ 2-dimethyl
  • ⁇ Corrosion inhibitor> ⁇ 5-Methyl-1H-benzotriazole ⁇ 5-mercapto-1-phenyl-1H-tetrazole (corresponds to a tetrazole compound) ⁇ n-dodecyl mercaptan (corresponds to a thiol compound)
  • ⁇ Surfactant> ⁇ Persoft (registered trademark) SF-T (alkyl sulfate triethanolamine salt, anionic surfactant, manufactured by NOF Corporation) ⁇ Nissan Cation (registered trademark) BB (dodecyltrimethylammonium chloride, cationic surfactant, manufactured by NOF Corporation) ⁇ Nonion K-220 (polyoxyethylene lauryl ether, nonionic surfactant, manufactured by NOF Corporation) ⁇ Nissan Anon (registered trademark) BL (lauryldimethylaminoacetic acid betaine, amphoteric surfactant, manufactured by NOF Corporation)
  • ⁇ pH adjuster> ⁇ Citric acid, monoethanolamine, nitric acid ( HNO3 ) ⁇ Potassium hydroxide (KOH)
  • Example A [Preparation of chemical solution] The preparation method of each chemical solution of Examples A1 to A19 and Comparative Examples A1 to A2 will be explained using Example A1 as an example. Hydroxylamine, 5-methyl-1H-benzotriazole, Persoft SF-T, and ultrapure water were mixed in the amounts shown in Table 2 below to obtain a mixed solution C-1. Thereafter, the chemical solution of Example A1 (cleaning A treatment solution) was prepared. Table 1 shows the content of resin E-1 in the resulting chemical solution. In the obtained chemical solution, the remainder other than the resin E-1 and the pH adjuster is the mixed solution C-1.
  • Example A1 According to the method for preparing the chemical solution of Example A1, the chemical solutions of Examples A2 to A19 and Comparative Examples A1 to A2 having the compositions shown in Tables 1 and 2 were prepared, respectively.
  • Table 1 shows the pH at 25° C. of the prepared chemical solutions of Examples A1 to A19 and Comparative Examples A1 to A2.
  • a test specimen was prepared by cutting it into the shape of .
  • Each of the obtained test specimens was immersed in each chemical solution (liquid temperature: 80° C.) for 10 minutes. Before and after the above immersion test, the film thickness of each film was measured using a fluorescent X-ray analyzer for evaluating thin films (XRF AZX-400, manufactured by Rigaku Co., Ltd.).
  • the dissolution rate ( ⁇ /min) of each film when each chemical solution was used was calculated from the measured film thickness before and after immersion. Based on the calculated dissolution rate, the solubility of the W film and the TiAlC film was evaluated based on the following evaluation criteria. Table 1 shows the evaluation results of the solubility of the obtained W film and TiAlC film. The slower the dissolution rate, the more the dissolution into each film is suppressed, and "S" has the highest evaluation of solubility.
  • the dissolution rate of the W film is 0.2 ⁇ /min or less
  • W film dissolution Speed is over 5.0 ⁇ /min
  • the dissolution rate of the TiAlC film is 0.1 ⁇ /min or less.
  • a laminate (corresponding to a pre-processing laminate) including a W film, a SiO 2 film, and a metal hard mask (TiN) having a predetermined opening in this order was formed on a substrate (Si).
  • a metal hard mask As a mask, dry etching was performed using a metal hard mask as a mask, and the SiO 2 film was etched until the surface of the W film was exposed, forming a hole to fabricate Sample 1 (Fig. (see 1).
  • SEM scanning electron microscope
  • the removability of dry etching residues was evaluated according to the following procedure. First, a prepared section of Sample 1 (square shape of approximately 2.0 cm x 2.0 cm) was immersed in each chemical solution whose temperature was adjusted to 80°C. Immediately after 5 minutes had elapsed from the start of immersion, the section of Sample 1 was taken out, immediately washed with ultrapure water, and dried with N2 . Thereafter, the surface of the immersed section of Sample 1 was observed using a SEM to confirm the presence or absence of dry etching residue.
  • the section of sample 1 that had been immersed for 10 minutes was washed with ultrapure water and dried with N2 , and then the surface of the section was observed with SEM to confirm the presence or absence of dry etching residue. did. Based on the observation results of the sections of each sample 1, the residue removability was evaluated according to the following criteria.
  • a substrate (Si) having an SiO 2 film was prepared, and the substrate with the SiO 2 film was immersed in each chemical solution adjusted to 80° C. for 10 minutes. Next, the SiO 2 film was rinsed by immersing the immersed substrate in a rinsing liquid made of isopropanol for 0.5 minutes.
  • the surface of the rinsed SiO 2 film was analyzed by X-ray photoelectron spectroscopy to determine the number of nitrogen atoms derived from each chemical solution (especially specific resin) relative to the number of all atoms on the surface of the SiO 2 film.
  • the ratio (unit: atom%) was measured.
  • the measurement conditions for X-ray photoelectron spectroscopy are shown below.
  • the persistence of the chemical solution after the rinsing treatment was evaluated from the measurement results of the number ratio of nitrogen atoms to all atoms on the surface of the SiO 2 film.
  • the obtained evaluation results are shown in Table 1.
  • the number ratio of nitrogen atoms to all atoms is preferably smaller. The smaller the number ratio of nitrogen atoms to all the atoms mentioned above, the higher the solubility of each component of the chemical solution (especially the specific resin) in the rinsing solution, and the smaller the amount of the chemical solution remaining on the SiO 2 film surface after rinsing treatment. means.
  • Tables 1 and 2 show the compositions of each chemical solution used in Examples A1 to A19 and Comparative Examples A1 to A2, and Table 1 shows the evaluation results of Examples A1 to A19 and Comparative Examples A1 to A2.
  • Table 2 shows the formulations of the components of the mixtures C-1 to C-6 used in the preparation of each of the chemical solutions of Examples A1 to A19 and Comparative Examples A1 to A2.
  • Table 1 shows the content of the resin, pH adjuster, and mixed liquid contained in each chemical solution, and Table 2 shows the type and content of each component contained in each mixed liquid.
  • the "ratio a/b” column for “resin” indicates the ratio a/b of the number of moles of repeating unit A to the number of moles of repeating unit B in a specific resin having repeating units A and B. b.
  • the "Amount (parts)” column indicates the resin content (unit: “parts by mass”) when the total mass of the chemical solution is 100 parts by mass.
  • “Yes” in the “pH adjuster” column means that the pH of the mixed solution obtained by mixing the resin and mixed solution is measured as described above, and the pH of the mixed solution is determined from the value shown in Table 1.
  • the "mixture” column indicates the number of the mixture used to prepare the drug solution.
  • the "remainder” in the “mixed solution” column means that the remainder of the chemical solution other than the resin and the pH adjuster is the mixed solution shown in the "mixed solution” column.
  • the "pH” column indicates the pH of the chemical solution at 25°C.
  • the numerical values shown in each column mean the content of each component (unit: “parts by mass”) when the total mass of each mixture is 100 parts by mass.
  • the chemical solutions of Examples A1 to A19 of the present invention have good solubility in W film, solubility in TiAlC film, removability of etching residue, and persistence of chemical solution after rinsing treatment. It was confirmed that it is excellent.
  • the chemical solutions of Comparative Examples A1 and A2 containing resins having repeating units that do not correspond to the repeating unit A derived from the compound represented by formula (1) have a pyrrolidone skeleton, a primary amino group, or a secondary amine.
  • X in formula (1) is selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and a salt thereof.
  • X in formula (1) represents a group
  • it has been confirmed that the solubility in the TiAlC film is suppressed (comparison between Example A2 and Example A3, etc.).
  • X in formula (1) represents a primary amino group or a salt thereof, the solubility in the W film is suppressed (comparison between Example A3 and Example A4, etc.) .
  • Example B [Preparation of chemical solution] The preparation method of each chemical solution of Examples B1 to B5 and Comparative Examples B1 to B2 will be explained using Example B1 as an example. After mixing resin E-1, citric acid, trishydroxymethylaminomethane (Tris), and ultrapure water in the amounts shown in Table 3 below, the pH of the prepared chemical solution is 6. Potassium hydroxide or nitric acid was added as a pH adjuster to adjust the pH to 0, and the resulting mixture was sufficiently stirred using a stirrer to prepare a chemical solution of Example B1.
  • Tris trishydroxymethylaminomethane
  • Example B1 According to the method for preparing the chemical solution of Example B1, the chemical solutions of Examples B2 to B5 and Comparative Examples B1 to B2 having the compositions shown in Table 3 were prepared, respectively.
  • each chemical solution was adjusted to room temperature (23° C.), and scrubbing was performed using each chemical solution for 60 seconds, followed by drying.
  • the number of defects on the polished surface of the obtained wafer was detected using a defect detection device, and each defect was observed using a SEM (scanning electron microscope) to classify the defects. If necessary, constituent elements were analyzed using EDAX (energy dispersive X-ray analyzer) to identify the components. Thereby, the number of defects based on the residue caused by the CMP treatment was determined, and the cleaning performance was evaluated according to the following evaluation criteria (rating 6 is the most excellent cleaning performance).
  • Number of target defects is less than 20 5: Number of target defects is 20 or more and less than 50 4: Number of target defects is 50 or more and less than 100 3: Number of target defects is 100 or more and less than 200 2: Number of target defects 200 or more but less than 300 1: Number of target defects is 300 or more
  • the dissolution rate ( ⁇ /min) of the W film when each chemical solution was used was calculated from the measured film thickness before and after immersion. From the calculated dissolution rate, the solubility of the W film (ability to suppress dissolution of the W film) was evaluated based on the following evaluation criteria. The slower the dissolution rate, the more the dissolution of the W film by the chemical solution is suppressed (rating 6 has the best solubility).
  • the dissolution rate of the W film is 0.2 ⁇ /min or less 5: The dissolution rate of the W film is more than 0.2 ⁇ /min and less than or equal to 0.5 ⁇ /min 4: The dissolution rate of the W film is more than 0.5 ⁇ /min 1. 0 ⁇ /min or less 3: W film dissolution rate is more than 1.0 ⁇ /min and 3.0 ⁇ /min or less 2: W film dissolution rate is more than 3.0 ⁇ /min and 5.0 ⁇ /min or less 1: W film dissolution Speed is over 5.0 ⁇ /min
  • Table 3 shows the composition and evaluation results of each chemical solution used in Examples B1 to B5 and Comparative Examples B1 to B2.
  • the "amount (%)” column for each component indicates the content (unit: mass %) of each component relative to the total mass of the chemical solution.
  • the numerical values in the "Organic acid/amine” column indicate the content of the organic acid (removal agent) relative to the content of the basic compound (removal agent).
  • "remainder” in the "water” column indicates that the water content is the remainder of the chemical solution other than the resin, remover, and pH adjuster.
  • the numerical value in the "pH” column indicates the pH of the chemical solution at 25° C. as measured by the above-mentioned pH meter.

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Abstract

La présente invention concerne une solution chimique pour dispositifs à semi-conducteur, la solution chimique ayant des propriétés exceptionnelles pour éliminer des résidus et étant telle que la dissolution du tungstène dans celle-ci est supprimée. Une solution chimique pour dispositifs à semi-conducteur selon la présente invention contient une résine ayant une unité de répétition A dérivée d'un composé représenté par la formule (1), ainsi que de l'eau.　Formule (1) : Y-L-(X)n
PCT/JP2023/022956 2022-06-28 2023-06-21 Solution chimique, procédé de traitement de substrat, procédé de fabrication de dispositif à semi-conducteur, composé et résine WO2024004781A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010251680A (ja) * 2009-03-25 2010-11-04 Fujifilm Corp 研磨液及び研磨方法
JP2011243610A (ja) * 2010-05-14 2011-12-01 Fujifilm Corp 洗浄組成物、半導体装置の製造方法及び洗浄方法
JP2015144230A (ja) * 2013-06-04 2015-08-06 富士フイルム株式会社 エッチング液およびそのキット、これらを用いたエッチング方法、半導体基板製品の製造方法および半導体素子の製造方法
JP2018064093A (ja) * 2016-09-30 2018-04-19 富士フイルム株式会社 半導体チップの製造方法、キット
JP2019156990A (ja) * 2018-03-14 2019-09-19 Jsr株式会社 半導体表面処理用組成物および半導体表面処理方法
WO2022044893A1 (fr) * 2020-08-24 2022-03-03 富士フイルム株式会社 Liquide de traitement et procédé de traitement de substrat

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010251680A (ja) * 2009-03-25 2010-11-04 Fujifilm Corp 研磨液及び研磨方法
JP2011243610A (ja) * 2010-05-14 2011-12-01 Fujifilm Corp 洗浄組成物、半導体装置の製造方法及び洗浄方法
JP2015144230A (ja) * 2013-06-04 2015-08-06 富士フイルム株式会社 エッチング液およびそのキット、これらを用いたエッチング方法、半導体基板製品の製造方法および半導体素子の製造方法
JP2018064093A (ja) * 2016-09-30 2018-04-19 富士フイルム株式会社 半導体チップの製造方法、キット
JP2019156990A (ja) * 2018-03-14 2019-09-19 Jsr株式会社 半導体表面処理用組成物および半導体表面処理方法
WO2022044893A1 (fr) * 2020-08-24 2022-03-03 富士フイルム株式会社 Liquide de traitement et procédé de traitement de substrat

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