Method for manufacturing treating liquid

Abstract

The objective of this invention is to provide a method for manufacturing a processing liquid with excellent filterability. The method for manufacturing the processing liquid of this invention uses a first filter having a first filter material to filter a purified material containing a surfactant to manufacture a processing liquid for a semiconductor substrate. In this method, the first filter material comprises at least one selected from the group consisting of nylon, polyallyl sulfonic acid, hydrophilically treated perfluoroalkoxyalkane, hydrophilically treated polytetrafluoroethylene, hydrophilically treated polyolefin, and hydrophilically treated polyvinylidene fluoride. The surfactant comprises at least one selected from the group consisting of a nonionic surfactant containing a group represented by formula (1) and anionic surfactants containing a group represented by formula (1). Formula (1) (LO)nL represents an alkyl group. n represents 3 to 55.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a processing liquid. Prior Art

[0002] When manufacturing semiconductor devices, a processing liquid for semiconductor substrates is used as a pre-wetting liquid, a resist liquid (resist composition), a developer, a rinsing liquid, a stripping liquid, a chemical liquid used in chemical mechanical polishing (CMP), and a cleaning liquid after CMP.

[0003] As an example of such a processing liquid, a post-CMP cleaning composition having specified characteristics is disclosed in Patent Document 1. It is disclosed that the post-CMP cleaning composition may contain a surfactant (Claim 2).

[0004] [Prior Art Documents]

[0005] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-526153 Summary of the Invention Problems to be Solved by the Invention

[0007] With the recent high performance of semiconductor devices, there is sometimes a requirement to reduce the content of impurities (such as coarse particles) in the processing liquid for semiconductor substrates.

[0008] In order to obtain such a processing liquid with a reduced content of impurities, sometimes the refined product is refined by filtration or the like to manufacture the processing liquid.

[0009] In a method for manufacturing a processing liquid in which a refined product is filtered to obtain a processing liquid, excellent filtration performance is required (that is, a processing liquid with sufficiently reduced impurities can be obtained smoothly). However, the inventors of the present invention conducted research and confirmed that: when the refined product contains a specified surfactant, sometimes the filtration performance becomes insufficient.

[0010] Therefore, an object of the present invention is to provide a method for manufacturing a processing liquid with excellent filtration performance. Means for Solving the Problems

[0011] The inventors have discovered that the aforementioned problem can be solved by the following structure.

[0012] [1]

[0013] A method for manufacturing a processing liquid, comprising filtering a purified material containing a surfactant using a first filter having a first filter material to manufacture a processing liquid for a semiconductor substrate, wherein the first filter material comprises at least one selected from the group consisting of nylon, polyallyl sulfonic acid, hydrophilically treated perfluoroalkoxyalkane, hydrophilically treated polytetrafluoroethylene, hydrophilically treated polyolefin, and hydrophilically treated polyvinylidene fluoride, and the surfactant comprises at least one selected from the group consisting of a nonionic surfactant containing a base represented by formula (1) and an anionic surfactant containing a base represented by formula (1), wherein formula (1) (LO)n

[0014] In formula (1), L represents an alkyl group; n represents 3~55.

[0015] [2]

[0016] The method for manufacturing a processing liquid as described in [1], wherein the processing liquid is applied to a semiconductor substrate after chemical mechanical polishing.

[0017] [3]

[0018] The method for manufacturing the treatment liquid as described in [1] or [2], wherein the purified material further comprises an amine compound.

[0019] [4]

[0020] The method for manufacturing the treatment liquid as described in [3], wherein the mass ratio of the content of the amine compound to the content of the surfactant in the purified product is 2 to 1000.

[0021] [5]

[0022] The method for manufacturing the treatment liquid as described in any one of [1] to [4], wherein the nonionic surfactant and the anionic surfactant comprise the base represented by formula (2), formula (2) -Ph-O-(LO)n-

[0023] In formula (2), Ph represents phenyl; L represents alkyl; and n represents 3~55.

[0024] [6]

[0025] The method for manufacturing the treatment liquid as described in any one of [1] to [4], wherein in the formula (1), n ​​represents 6 to 20.

[0026] [7]

[0027] A method for manufacturing a treatment liquid as described in any one of [1] to [6], wherein the purified material comprises an aliphatic carboxylic acid chelating agent having 3 or more carbon atoms.

[0028] [8]

[0029] The method for manufacturing the treatment liquid as described in any one of [1] to [7], wherein the pH value of the purified substance is 8 to 12.

[0030] [9]

[0031] A method for manufacturing a treatment liquid as described in any one of [1] to [8], wherein the first filter material comprises at least one selected from the group consisting of the nylon, the polyallyl sulfonic acid, the hydrophilically treated perfluoroalkoxyalkane, and the hydrophilically treated polytetrafluoroethylene.

[0032]

[10]

[0033] A method for manufacturing a treatment liquid as described in any one of [1] to [9], wherein the first filter material comprises the polyallyl sulfonic acid.

[0034]

[11]

[0035] A method for manufacturing a treatment liquid as described in any one of [1] to

[10] , wherein the purified material is filtered using the first filter and a second filter containing a second filter material different from the first filter.

[0036]

[12]

[0037] The method for manufacturing a treatment liquid as described in

[11] , wherein the pore diameter of the second filter medium is larger than the pore diameter of the first filter medium, and the liquid to be refined is passed through the second filter and the first filter in this order to filter the liquid to be refined.

[0038] 〔13〕

[0039] The method for manufacturing a treatment liquid as described in

[12] , wherein the ratio of the pore diameter of the second filter medium to the pore diameter of the first filter medium is 2 to 500.

[0040] 〔14〕

[0041] The method for manufacturing a treatment liquid as described in any one of [1] to

[13] , wherein the filtration pressure for filtering the liquid to be refined using the first filter is 0.4 MPa or less.

[0042] 〔15〕

[0043] The method for manufacturing a treatment liquid as described in any one of [1] to

[14] , wherein the filtration pressure for filtering the liquid to be refined using the first filter is 0.05 MPa or more. Advantages of the Invention

[0044] According to the present invention, a method for manufacturing a treatment liquid with excellent filterability can be provided. Brief Explanation of the Drawings

[0045] Figure 1 is a partially cut-away perspective view of a typical first filter. Embodiments

[0046] Hereinafter, an example of a form for implementing the present invention will be described.

[0047] In this specification, the numerical range indicated by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

[0048] In this specification, when there are two or more kinds of a certain component, the "content" of the component means the total content of these two or more kinds of components.

[0049] In this specification, "ppm" means "parts per million (10⁻⁶)" and "ppb" means "parts per billion (10⁻⁹)".

[0050] Unless otherwise specified, the compounds described in this specification may also include isomers (compounds with the same number of atoms but different structures), optical isomers, and isotopes. Furthermore, there may be only one isomer or multiple isotopes.

[0051] In this specification, psi refers to pound-force per square inch, which means 1 psi = 6894.76 Pa.

[0052] [Manufacturing method of the treatment fluid]

[0053] The manufacturing method of the processing liquid of the present invention (hereinafter also referred to as the "manufacturing method") is a method for manufacturing a processing liquid for semiconductor substrates by filtering a purified material containing a surfactant. In the manufacturing method of the processing liquid, the first filter material contains at least one selected from the group consisting of nylon, polyallyl sulfonic acid, perfluoroalkoxyalkane after hydrophilic treatment, polytetrafluoroethylene after hydrophilic treatment, polyolefin after hydrophilic treatment, and polyvinylidene fluoride after hydrophilic treatment. The surfactant includes at least one selected from the group consisting of nonionic surfactants containing the base represented by formula (1) and anionic surfactants containing the base represented by formula (1).

[0054] (Formula (1) (LO)n: L is an alkyl group, and n is 3~55)

[0055] The mechanism by which the structure solves the problem of the present invention may not be clear, and the inventors speculate as follows.

[0056] In other words, firstly, when the refined material contains a specified surfactant, bubbles are generated during filtration due to the presence of the surfactant, causing bubble clogging of the filter media. As a result, it is presumed that filtration performance deteriorates, leading to a decrease in filtration flow rate and / or an inability to perform filtration. Therefore, if a filter with a specified filter media having high hydrophilicity is used, impurities (such as coarse particles) can be effectively removed, and bubbles are less likely to be generated during filtration, or even if bubbles are generated, bubble clogging is less likely to occur, thus presumably improving filtration performance.

[0057] [Refined product]

[0058] The components contained in the refined product used in the manufacturing method of the present invention will be described.

[0059] <surfactants>

[0060] The refined product includes at least one of the group consisting of nonionic surfactants containing a base represented by formula (1) and anionic surfactants containing a base represented by formula (1) (hereinafter also referred to as "specific surfactants").

[0061] A specific surfactant can be used alone or in combination with two or more.

[0062] The content of a specific surfactant relative to the total mass of the refined product is preferably 0.00001% to 10% by mass, more preferably 0.0001% to 3% by mass, and even more preferably 0.002% to 1.5% by mass.

[0063] In addition, relative to the total mass of the components after solvent removal from the refined product, the content of the specific surfactant is preferably 0.00001% to 50% by mass, more preferably 0.005% to 40% by mass, and even more preferably 0.03% to 35% by mass.

[0064] Furthermore, the so-called "total mass of the components of the refined product after solvent removal" refers to the total content of all components contained in the refined product other than water and organic solvents.

[0065] (Nonionic surfactants containing the base represented by formula (1))

[0066] Nonionic surfactants, as specific surfactants, include the base represented by formula (1).

[0067] Equation (1) (LO)n

[0068] In formula (1), L represents an alkyl group. The alkyl group can be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 2 to 3, and even more preferably 2. In formula (1), there may be multiple Ls, which may be the same or different.

[0069] In formula (1), n ​​represents 3~55, preferably 3~30, and even more preferably 6~20.

[0070] Furthermore, n represents the value of an integer.

[0071] In other words, the base represented by formula (1) is a polyoxyalkylene group with a repeating number of n (e.g., polyoxyethylene, polyoxypropylene, and polyoxyethylenepolyoxypropylene).

[0072] Among them, the base represented by formula (1) is preferably a polyoxyethylene with n of 3 to 30, and more preferably a polyoxyethylene with n of 6 to 20.

[0073] The base that is bonded to the end of the base on the O side of the base represented by Equation (1) (i.e., the base that is bonded to the right side of the base represented by Equation (1)) is preferably a base other than "*1-LO-*2". L in "*1-LO-*2" is the same as L in Equation (1), *1 is the bond position with O present at the end of the base represented by Equation (1), and *2 is the bond position on the opposite side to *1.

[0074] The group bonded to the end of the O side of the group represented by formula (1) (i.e., the group bonded to the left side of the group represented by formula (1)) is preferably a hydrogen atom, an alkyl group, or an aromatic cyclic group. The alkyl group may be straight-chain or branched-chain, and preferably has 1 to 30 carbon atoms. The aromatic cyclic group may have substituents, such as hydrocarbon groups (alkyl groups, preferably having 1 to 30 carbon atoms).

[0075] The base with the terminal bond on the L side of the base represented by Equation (1) is preferably a base other than "*3-OLO-*3". The L in "*3-OLO-*3" is the same as the L in Equation (1), and *3 is the bond position.

[0076] The group that is terminally bonded to the L-side of the group represented by formula (1) is preferably a hydroxyl, alkoxy, or a group represented by -O- of an aromatic ring. The alkoxy group may be linear or branched, and preferably has 1 to 30 carbon atoms. The aromatic ring may have substituents, such as hydrocarbon groups (alkyl groups, preferably having 1 to 30 carbon atoms).

[0077] The nonionic surfactant used as a specific surfactant is preferably one containing the base represented by formula (2).

[0078] Equation (2) -Ph-O-(LO)n-

[0079] In formula (2), Ph represents phenylene. L represents alkylene. n represents 3~55.

[0080] In equation (2), "(LO)n" is the same basis as that represented in equation (1).

[0081] The group bonded to the end of the Ph side of the group represented by formula (2) is preferably a hydrogen atom or an alkyl group. The alkyl group can be straight-chain or branched-chain, and the number of carbon atoms is preferably 1 to 30, more preferably 6 to 22.

[0082] The structures of nonionic surfactants that are specific surfactants can be enumerated as compounds represented by formula (N).

[0083] Formula (N) RNI-LNI-(LO)nH

[0084] In equation (N), "(LO)n" is the same basis as that represented by equation (1).

[0085] In formula (N), RNI represents alkyl, allyl, aryl, or a combination thereof (alkylaryl, etc.). These groups may have one or more substituents. The alkyl group may be linear or branched. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 6 to 22 carbon atoms. One or more of the ethyl groups in the alkyl group may be substituted with vinyl groups. The aryl group preferably has 6 to 12 carbon atoms. The allyl group preferably has 2 or more carbon atoms, more preferably 2 to 22 carbon atoms.

[0086] In formula (N), LNI represents a single bond or a divalent linker. Preferably, the divalent linker is -O-, -CO-, -NR11-, -S-, -SO2-, -PO(OR12)-, alkyl, aryl, or a combination thereof. Here, R11 represents a hydrogen atom, alkyl, aryl, or aralkyl. R12 represents an alkyl, aryl, or aralkyl group.

[0087] Nonionic surfactants used as specific surfactants include, for example: polyoxyalkylene alkyl ethers (e.g., polyoxyethyl lauryl ether, polyoxyethyl stearyl ether, etc.), polyoxyalkylene alkenyl ethers (e.g., polyoxyethyl oleyl alkenyl ether, etc.), polyoxyethylene alkylphenyl ethers (e.g., polyoxyethylene nonylphenyl ether, etc.), polyoxyalkylene diols (e.g., polyoxypropyl polyoxyethylene diol, etc.), and polyoxyalkylene monoalkylates (polyoxyalkylene monoalkyl fatty acid esters) (e.g., polyoxyethylene...). Polyoxyethylene monoalkylates, polyoxyethylene monooleate, etc., polyoxyethylene alkyl dialkylates (polyoxyethylene alkyl dialkyl fatty acid esters) (e.g., polyoxyethylene distearate, polyoxyethylene dioleate, etc.), bispolyoxyethylene alkyl alkylamides (e.g., bispolyoxyethylene stearylamide), polyoxyethylene dehydrated sorbitol fatty acid esters, polyoxyethylene alkylamides, oxyethylene oxypropyl block copolymers, and acetylene-based polyoxyethylene oxides. All of these nonionic surfactants contain the group represented by formula (1).

[0088] Among them, the preferred nonionic surfactant for use as a specific surfactant is polyoxyethylene alkylphenyl ether.

[0089] The alkyl portion of the polyoxyethylene alkylphenyl ether can be linear or branched, preferably branched. The alkyl portion preferably has 5 or more carbon atoms, more preferably 8 or more. The upper limit of the number of carbon atoms is, for example, 20 or less.

[0090] The polyoxyethyl alkyl phenyl ether preferably has 5 or more repeating units in the polyoxyethyl portion, more preferably 8 or more. The upper limit of the number of repeating units is, for example, 20 or less.

[0091] (Anionic surfactants containing the group represented by formula (1))

[0092] Anionic surfactants, as specific surfactants, include the base represented by formula (1).

[0093] The group represented by formula (1) in the anionic surfactant, which is a specific surfactant, is the same as the group represented by formula (1) described in the description of the nonionic surfactant.

[0094] Furthermore, the anionic surfactant is preferably composed of the group represented by formula (2). The group represented by formula (2) in the anionic surfactant is the same as the group represented by formula (2) described in the description of the nonionic surfactant.

[0095] The structures of anionic surfactants that are specific surfactants can be enumerated as compounds represented by formula (A).

[0096] Formula (A) RNA-LNA1-(LO)n-LNA2-QNA

[0097] In equation (A), "(LO)n" is the same basis as that represented by equation (1).

[0098] In formula (A), RNA represents an alkyl, aryl, or a combination thereof (alkylaryl, etc.). These groups may have one or more substituents. Examples of substituents include halogen atoms such as fluorine atoms and hydroxyl groups. The alkyl group may be linear or branched. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 6 to 22 carbon atoms. The aryl group preferably has 6 to 12 carbon atoms. One or more of the ethyl groups in the alkyl group may be substituted with vinyl groups.

[0099] In formula (A), LNA1 and LNA2 independently represent single bonds or divalent linkages. Preferably, the divalent linkage is -O-, -CO-, -NR11-, -S-, -SO2-, -PO(OR12)-, alkyl (preferably with 1 to 6 carbon atoms), aryl (preferably with 6 to 12 carbon atoms), or a combination thereof. Here, R11 represents a hydrogen atom, alkyl, aryl, or aralkyl group. R12 represents an alkyl, aryl, or aralkyl group. The alkyl and aryl groups may each independently have substituents; for example, they may have one or more anionic groups as substituents.

[0100] Among them, LNA1 is preferably -O-. LNA2 is preferably a single bond or an alkyl group.

[0101] In formula (A), QNA represents an anionic group. Examples of such anionic groups include -COOM, -OSO3M, -P(=O)(ORNA2)OM, and -SO3M. M represents a hydrogen atom or a counter cation. Examples of such counter cations include alkali metal ions (lithium, sodium, or potassium, etc.). RNA2 represents an alkyl group with 1 to 3 carbon atoms, a hydrogen atom, the counter cation, or the group represented by "RNA-LNA1-(LO)n-LNA2-". The RNA, LNA1, (LO)n, and LNA2 in the group represented by "RNA-LNA1-(LO)n-LNA2-" are as described above.

[0102] Examples of anionic surfactants include: phosphate ester surfactants with a phosphate ester group as a hydrophilic (acidic) group, phosphonic acid surfactants with a phosphonic acid group as a hydrophilic (acidic) group, sulfonic acid surfactants with a sulfonate group as a hydrophilic (acidic) group, carboxylic acid surfactants with a carboxyl group as a hydrophilic (acidic) group, and sulfate ester surfactants with a sulfate ester group as a hydrophilic (acidic) group. Compounds equivalent to these anionic surfactants and containing the group represented by formula (1) can also be used as specific surfactants.

[0103] Phosphate ester surfactants

[0104] Examples of phosphate ester surfactants include polyoxyalkylene alkyl ether phosphates and their salts. Polyoxyalkylene alkyl ether phosphates typically comprise both monoesters and diesters, and either monoester or diester can be used alone.

[0105] Salts that can be used as phosphate ester surfactants include, for example, sodium salts, potassium salts, ammonium salts, and organic amine salts.

[0106] The monovalent alkyl group in the polyoxyalkylene alkyl ether phosphate is not particularly limited, but it is preferably an alkyl group with 2 to 24 carbon atoms, more preferably an alkyl group with 6 to 18 carbon atoms, and even more preferably an alkyl group with 12 to 18 carbon atoms.

[0107] The divalent alkyl group in the polyoxyalkylene ether phosphate is not particularly limited, but it is preferably an alkyl group with 2 to 6 carbon atoms, more preferably an ethyl alkyl group or a 1,2-propanediol alkyl group. In addition, the repeating number of the alkyl group in the polyoxyalkylene ether phosphate is preferably 3 to 12, more preferably 3 to 6.

[0108] As a phosphate ester-based surfactant, polyoxyethylene ethyl octyl ether phosphate, polyoxyethylene ethyl lauryl ether phosphate, polyoxyethylene ethyl tridecyl ether phosphate, or polyoxyethylene ethyl myristyl ether phosphate are preferred, lauryl phosphate, tridecyl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, or polyoxyethylene ethyl myristyl ether phosphate are even more preferred, and lauryl phosphate, cetyl phosphate, stearyl phosphate, or polyoxyethylene ethyl myristyl ether phosphate are even more preferred.

[0109] As a phosphate ester-based surfactant, compounds that meet the necessary conditions for being a specific surfactant can also be cited from paragraphs

[0012] to

[0019] of Japanese Patent Application Publication No. 2011-040502, and these contents are incorporated into this specification.

[0110] Sulfonic acid surfactants

[0111] Examples of sulfonic acid surfactants include polyoxyalkylene alkyl ether sulfonic acid and its salts.

[0112] The monovalent alkyl group of the sulfonic acid surfactant is not particularly limited, but it is preferably an alkyl group with 2 to 24 carbon atoms, and more preferably an alkyl group with 6 to 18 carbon atoms.

[0113] Furthermore, there are no particular limitations on the divalent alkyl group in the polyoxyalkylene alkyl ether sulfonic acid, but it is preferably ethyl or 1,2-propanediol. Additionally, the number of repeating alkyl groups in the polyoxyalkylene alkyl ether sulfonic acid is preferably 3 to 12, more preferably 3 to 6.

[0114] Carboxylic acid surfactants

[0115] Examples of carboxylic acid surfactants include polyoxyalkylene alkyl ether carboxylic acids and their salts.

[0116] The monovalent alkyl group in the carboxylic acid surfactant is not particularly limited, but it is preferably an alkyl group with 7 to 25 carbon atoms, and more preferably an alkyl group with 11 to 17 carbon atoms.

[0117] Furthermore, there are no particular limitations on the divalent alkyl group in the polyoxyalkylene alkyl ether carboxylic acid, but it is preferably ethyl or 1,2-propanediol. Additionally, the number of repeating alkyl groups in the polyoxyalkylene alkyl ether carboxylic acid is preferably 3 to 12, more preferably 3 to 6.

[0118] Specific examples of carboxylic acid surfactants include polyoxyethylene ethyl lauryl ether acetic acid and polyoxyethylene ethyl tridecyl ether acetic acid.

[0119] Sulfate-based surfactants

[0120] Examples of sulfate-based surfactants include polyoxyalkylene alkyl ether sulfates and their salts.

[0121] There are no particular limitations on the monovalent alkyl group in the polyoxyalkylene alkyl ether sulfate, but it is preferably an alkyl group with 2 to 24 carbon atoms, and more preferably an alkyl group with 6 to 18 carbon atoms.

[0122] The divalent alkyl group in the polyoxyalkylene alkyl ether sulfate is not particularly limited, but is preferably ethyl or 1,2-propanediol. Furthermore, the number of repetitions of the alkyl group in the polyoxyalkylene alkyl ether sulfate is preferably 1 to 12, more preferably 1 to 6.

[0123] As a specific example of a sulfate-based surfactant, polyoxyethylene lauryl ether sulfate can be cited.

[0124] (Physical properties of surfactants)

[0125] The specific surfactant is preferably an aqueous solution of a specific surfactant with a surface tension of 10 mN / m to 60 mN / m, more preferably 10 mN / m to 50 mN / m, and even more preferably 15 mN / m to 45 mN / m.

[0126] <Amine compounds>

[0127] The refined product is preferably one containing amine compounds.

[0128] Amine compounds are compounds that are different from specific surfactants.

[0129] The amine compound is selected from at least one of the group consisting of primary amines having a primary amino group (-NH2) in the molecule, secondary amines having a secondary amino group (>NH) in the molecule, tertiary amines having a tertiary amino group (>N-) in the molecule, and salts thereof.

[0130] Examples of amine compounds include: amino alcohols, amine compounds with cyclic structures, and other monoamine or polyamine compounds.

[0131] In addition, as a salt of a primary, secondary, or tertiary amine, for example, a salt of an inorganic acid can be listed, wherein the inorganic acid is formed by bonding at least one nonmetal selected from the group consisting of Cl, S, N, and P with hydrogen, preferably a hydrochloride, sulfate, or nitrate.

[0132] (amino alcohols)

[0133] In terms of superior defect suppression performance, amine compounds preferably contain amino alcohols. An amino alcohol is an amine compound that has at least one hydroxyl alkyl group within its molecule.

[0134] The amino alcohol may have any of the primary to tertiary amino groups, preferably having a primary amino group.

[0135] Furthermore, it is preferable that the amino alcohol has a quaternary carbon atom at the α-position of the amino group (primary, secondary, or tertiary amino group). That is, preferably, the carbon atom bonded to the amino group is not bonded to a hydrogen atom, but to three organic groups.

[0136] Examples of amino alcohols include: monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), diethanolamine (DEA), triethanolamine (TEA), diethylene glycolamine (DEGA), trishydroxymethylamino methane (Tris), 2-(methylamino)-2-methyl-1-propanol (N-MAMP), dimethylbis(2-hydroxyethyl)ammonium hydroxide (AH212), 2-(2-aminoethylamino)ethanol, and N,N-dimethyl-2-amino-2-methyl-1-propanol (DMAMP).

[0137] Among them, AMP, N-MAMP, MEA, DEA, Tris, or DEGA are preferred, and AMP, MEA, DEA, or DEGA are even more preferred.

[0138] When the refined product contains amino alcohols as amine compounds, it may contain only one amino alcohol or two or more amino alcohols.

[0139] (Amine compounds with cyclic structures)

[0140] There are no particular limitations on the cyclic structure of amine compounds with cyclic structures. For example, heterocycles in which at least one of the atoms constituting the ring is a nitrogen atom (nitrogen-containing heterocycles) can be listed.

[0141] Examples of amine compounds with cyclic structures include azole compounds, pyridine compounds, pyrazine compounds, pyrimidine compounds, piperazine compounds, and cyclic amidine compounds.

[0142] Azole compounds are compounds containing a hetero five-membered ring with at least one nitrogen atom and exhibiting aromaticity. The number of nitrogen atoms in the hetero five-membered ring of the azole compound is not particularly limited, but is preferably 2 to 4, more preferably 3 or 4.

[0143] Examples of azole compounds include imidazole compounds, pyrazole compounds, thiazole compounds, triazole compounds, and tetraazole compounds.

[0144] The preferred azole compound is a triazole compound or a tetraazole compound, more preferably a 1,2,4-triazole, a 5-aminotetrazole, or a 1H-tetrazole.

[0145] Pyridine compounds are compounds containing a hetero-six-membered ring (pyridine ring) that has an aromaticity and includes a nitrogen atom.

[0146] As pyridine compounds, specifically, examples include: pyridine, 3-aminopyridine, 4-aminopyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-acetaminopyridine, 2-cyanopyridine, 2-carboxypyridine, and 4-carboxypyridine.

[0147] Pyrazine compounds are compounds containing an aromatic six-membered ring (pyrazine ring) with two nitrogen atoms in the para position, while pyrimidine compounds are compounds containing an aromatic six-membered ring (pyrimidine ring) with two nitrogen atoms in the meta position.

[0148] Examples of pyrazine compounds include: pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2,3,5,6-tetramethylpyrazine, 2-ethyl-3-methylpyrazine, and 2-amino-5-methylpyrazine, with pyrazine being preferred.

[0149] Examples of pyrimidine compounds include pyrimidine, 2-methylpyrimidine, 2-aminopyrimidine, and 4,6-dimethylpyrimidine, with 2-aminopyrimidine being preferred.

[0150] Piperazine compounds are compounds having a hetero-six-membered ring (piperazine ring) formed by replacing the opposing CH groups of the cyclohexane ring with nitrogen atoms. Piperazine compounds are preferred for their superior effects according to the present invention.

[0151] Piperazine compounds may have substituents on the piperazine ring. Examples of such substituents include: hydroxyl groups, alkyl groups having 1 to 4 carbon atoms, and aryl groups having 6 to 10 carbon atoms.

[0152] Examples of piperazine compounds include: piperazine, 1-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1-butylpiperazine, 2-methylpiperazine, 1,4-dimethylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 1-phenylpiperazine, 2-hydroxypiperazine, 2-hydroxymethylpiperazine, 1-(2-hydroxyethyl)piperazine (HEP), N-(2-aminoethyl)piperazine (AEP), 1,4-bis(2-hydroxyethyl)piperazine (HEP). The following are preferred: 1-Bis(2-hydroxyethyl)piperazine (BHEP), 1,4-bis(2-aminoethyl)piperazine (BAEP), and 1,4-bis(3-aminopropyl)piperazine (BAPP), with piperazine, 1-methylpiperazine, 2-methylpiperazine, HEP, AEP, BHEP, BAEP, or BAPP being more preferred.

[0153] Cyclic amidine compounds are compounds having heterocycles containing amidine structures (>NC=N-) within the ring.

[0154] The number of ring members of the heterocycle in the cyclic amidine compound is not particularly limited, but preferably five or six, more preferably six.

[0155] Examples of cyclic amidine compounds include: 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 3 4,6,7,8,9,10,11-octahydro-2H-pyrimido[1,2-a]acoxine, 3,4,6,7,8,9-hexahydro-2H-pyrido[1,2-a]pyrimidine, 2,5,6,7-tetrahydro-3H-pyrrolo[1,2-a]imidazole, 3-ethyl-2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azopon, and creatinine, preferably DBU or DBN.

[0156] In addition to those mentioned above, other examples of amine compounds with cyclic structures include compounds containing heterocyclic five-membered rings that are not aromatic, such as 1,3-dimethyl-2-imidazolidinone and imidazolidinethione, and compounds containing seven-membered rings containing nitrogen atoms.

[0157] The preferred amine compounds having a cyclic structure are triazole compounds, tetraazole compounds, piperazine compounds, or cyclic amidine compounds, with piperazine compounds being more preferred.

[0158] (Monoamine compounds)

[0159] There are no particular limitations on monoamine compounds other than amino alcohols and amine compounds with cyclic structures, for example, compounds represented by the following formula (a) (hereinafter also referred to as "compound (a)").

[0160] NHxR(3-x) (a)

[0161] In the formula, R represents an alkyl group with 1 to 3 carbon atoms, and x represents an integer from 0 to 2.

[0162] Examples of alkyl groups having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, and isopropyl, with ethyl or n-propyl being preferred.

[0163] Compound (a) may include, for example, methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, and triethylamine, with ethylamine, propylamine, diethylamine, or triethylamine being preferred.

[0164] Regarding the superior defect suppression performance of the obtained treatment solution on the metal film, it is preferable that the purified material contains two or more amine compounds, and at least one of the two or more amine compounds is compound (a). Although theoretically not restricted, it is speculated that this is because compound (a) is a low molecular weight compound with high water solubility and excellent coordination rate with metals (e.g., Co, W, and Cu).

[0165] Examples of monoamine compounds other than compound (a) include: benzylamine, diethylamine, n-butylamine, 3-methoxypropylamine, tributylamine, n-hexylamine, cyclohexylamine, n-octylamine, 2-ethylhexylamine, and 4-(2-aminoethyl)morpholine (AEM).

[0166] (Polyamine compounds)

[0167] Examples of polyamine compounds other than amino alcohols and amine compounds with cyclic structures include: ethylenediamine (EDA), 1,3-propanediamine (PDA), 1,2-propanediamine, 1,3-butanediamine, and 1,4-butanediamine, as well as polyalkyl polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine.

[0168] In addition, as amine compounds, the amine compounds described in paragraphs

[0034] to

[0056] of International Publication No. 2013 / 162020 may be cited and incorporated into this specification.

[0169] In terms of excellent defect suppression performance, amine compounds preferably have one or more hydrophilic groups in addition to one primary to tertiary amino group. Examples of hydrophilic groups include primary to tertiary amino groups, hydroxyl groups, and carboxyl groups, with primary to tertiary amino groups or hydroxyl groups being more preferred.

[0170] Examples of such amine compounds include: polyamine compounds having two or more primary to tertiary amino groups, amino alcohols having one or more primary to tertiary amino groups and one or more hydroxyl groups, and amine compounds with cyclic structures having two or more hydrophilic groups.

[0171] There is no particular limit to the total number of hydrophilic groups in an amine compound, but it is preferably 5 or less, and more preferably 4 or less.

[0172] In addition, when the obtained treatment solution is diluted with water or the like, the pH value of the treatment solution can be suppressed and the deviation of the defect suppression performance can be suppressed. The purified product is preferably an amine compound containing a first acid dissociation constant (hereinafter also referred to as "pKa1") of the conjugate acid of 7.0 or more (more preferably 7.5 to 13.0, even more preferably 8.0 to 12.0, and especially preferably 8.5 to 11.0).

[0173] Furthermore, in this specification, the first acid dissociation constant (pKa1) is a value obtained using the SC-Database (The IUPAC Stability Constants Database) (http: / / acadsoft.co.uk / scdbase / SCDB_software / scdb_download.htm).

[0174] The preferred amine compounds contained in the purified product are: monoethanolamine (MEA) (pKa1: 9.55 for the conjugate acid), 2-amino-2-methyl-1-propanol (AMP) (pKa1: 9.72 for the conjugate acid), 2-(methylamino)-2-methyl-1-propanol (N-MAMP) (pKa1: 9.70 for the conjugate acid), diethanolamine (DEA) (pKa1: 8.88 for the conjugate acid), diethylene glycolamine (DEGA) (pKa1: 9.02 for the conjugate acid), tris(hydroxymethyl)aminomethane (Tris) (pKa1: 8.30 for the conjugate acid), ethylenediamine (EDA) (pKa1: 10.7 for the conjugate acid), 1,3-propanediamine (PDA) (pKa1: 10.94 for the conjugate acid), diethylenetriamine (DETA) (pKa1: 10.45 for the conjugate acid), triethylenetetramine (... TETA (pKa1: 10.6 for conjugate acid), N-(2-aminoethyl)piperazine (AEP) (pKa1: 10.5 for conjugate acid), 1,4-bis(2-hydroxyethyl)piperazine (BHEP) (pKa1: 9.6 for conjugate acid), 1,4-bis(2-aminoethyl)piperazine (BAEP) (pKa1: 10.6 for conjugate acid), 1,4-bis(3-aminopropyl)piperazine (BAPP) (pKa1: 10.3 for conjugate acid), bis(aminopropyl)ethylenediamine (BAPEDA) (pKa1: 10.5 for conjugate acid), ethylamine (pKa1: 10.6 for conjugate acid), triethylamine (pKa1: 10.75 for conjugate acid), or propylamine (pKa1: 10.6 for conjugate acid).

[0175] Among them, MEA, AMP, DEGA, PDA, DETA, TETA, AEP, BHEP, BAEP, BAPP, or BAPEDA are preferred in terms of superior defect suppression performance.

[0176] The refined product may contain only one amine compound or two or more amine compounds.

[0177] The content of amine compounds in the refined product of the present invention is preferably 0.01% to 20% by mass, more preferably 0.1% to 10% by mass, and even more preferably 2% to 4% by mass, relative to the total mass of the refined product.

[0178] In addition, relative to the total mass of the components after solvent removal from the refined product, the content of amine compounds is preferably 1% to 99% by mass, more preferably 15% to 98% by mass, and even more preferably 35% to 97% by mass.

[0179] Chelating agents

[0180] The refined product is also preferably a chelating agent as a component different from the stated ingredient.

[0181] Chelating agents are compounds that have the function of chelating with metals that can exist on a semiconductor substrate. Preferably, they are compounds having two or more functional groups (ligands) that coordinate with metal ions in one molecule.

[0182] The ligands that a chelating agent may possess include, for example, acidic groups and cationic groups. Examples of acidic groups include carboxyl groups, phosphonic acid groups, sulfonyl groups, and phenolic hydroxyl groups. Examples of cationic groups include amino groups.

[0183] The chelating agent preferably has an acid group as a ligand, and more preferably has at least one ligand selected from carboxyl and phosphonic acid groups.

[0184] Examples of chelating agents include organic chelating agents and inorganic chelating agents.

[0185] Organic chelating agents are chelating agents containing organic compounds, such as carboxylic acid chelating agents with carboxyl groups as ligands and phosphonic acid chelating agents with phosphonic acid groups as ligands.

[0186] As inorganic chelating agents, condensed phosphates and their salts can be listed.

[0187] As a chelating agent, it is preferably an organic chelating agent, more preferably an organic chelating agent having at least one ligand selected from carboxyl and phosphonic acid groups, and even more preferably an organic chelating agent having only a carboxyl group as a ligand.

[0188] The chelating agent is also preferably of low molecular weight. Specifically, the molecular weight of the chelating agent is preferably below 600, more preferably below 450, and even more preferably below 300. The lower limit is preferably above 90, and more preferably above 100.

[0189] Furthermore, when the chelating agent is an organic chelating agent, its carbon number is preferably 15 or less, more preferably 12 or less, and even more preferably 8 or less. The lower limit of the carbon number is, for example, preferably 2 or more, more preferably 3 or more.

[0190] (Carboxylic acid chelating agents)

[0191] Carboxylic acid chelating agents are chelating agents with a carboxyl group as a ligand in the molecule. Examples include: amino polycarboxylic acid chelating agents, amino acid chelating agents, hydroxy carboxylic acid chelating agents, aliphatic carboxylic acid chelating agents, and aromatic carboxylic acid chelating agents. Preferably, they are aliphatic carboxylic acid chelating agents with 3 or more carbon atoms.

[0192] The number of carboxyl groups in a carboxylic acid chelating agent is preferably 2 or more, more preferably 2 to 10, and even more preferably 2.

[0193] Examples of chelating agents based on amino polycarboxylic acids include: butanediaminetetraacetic acid (TDAA), diethylenetriamine pentaacetic acid (DTPA), ethylenediaminetetrapropionic acid (EDTA), triethylenetetraaminehexaacetic acid (TTPA), 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid (PDTA), ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid (DTA), ethylenediaminediacetic acid (EDTA), ethylenediaminediacetic acid (EDTA), ethylenediaminediacetic acid (EDTA), ethylenediaminedipropionic acid (EDTA), 1,6-hexamethylenediamine-N,N,N',N'-tetraacetic acid (DTA), N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid (DTA), diaminopropanetetraacetic acid (DTA), 1,4,7,10-tetraazacyclododecanetetraacetic acid (DTA), diaminopropanoltetraacetic acid (DTA), (hydroxyethyl)ethylenediaminetriacetic acid (EDTA), and imino diacetic acid (IDA).

[0194] Among them, the preferred are diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, or iminodiacetic acid (IDA).

[0195] Examples of amino acid chelating agents include: glycine, serine, α-alanine (2-aminopropionic acid), β-alanine (3-aminopropionic acid), lysine, leucine, isoleucine, cystine, cysteine, ethionine, threonine, tryptophan, tyrosine, valine, histidine, histidine derivatives, asparagine, aspartic acid, glutamine, and glutamic acid. Histidine, arginine, proline, methionine, phenylalanine, compounds described in paragraphs

[0021] to

[0023] of Japanese Patent Application Publication No. 2016-086094, and their salts. Furthermore, as histidine derivatives, compounds described in Japanese Patent Application Publication Nos. 2015-165561 and 2015-165562, etc., are cited and incorporated herein by reference. Additionally, examples of salts include: sodium salts, alkali metal salts such as potassium salts, ammonium salts, carbonates, and acetates.

[0196] Regarding the excellent corrosion prevention performance of metal films, sulfur-containing amino acids are preferred as amino acid chelating agents. Examples of sulfur-containing amino acids include cystine, cysteine, ethionine, and methionine. Among these, cystine or cysteine ​​are preferred.

[0197] Examples of hydroxycarboxylic acid chelating agents include: malic acid, citric acid, glycolic acid, gluconic acid, heptonic acid, tartaric acid, and lactic acid, with citric acid or tartaric acid being preferred.

[0198] As an aliphatic carboxylic acid chelating agent, it is preferably an aliphatic polycarboxylic acid, and more preferably an aliphatic dicarboxylic acid.

[0199] Examples of aliphatic carboxylic acid chelating agents include: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, and maleic acid.

[0200] As an aromatic carboxylic acid chelating agent, it is preferably an aromatic polycarboxylic acid, and more preferably a compound formed by substituting 2 to 6 carboxyl groups on an aromatic ring (more preferably a benzene ring). Furthermore, an aromatic polycarboxylic acid refers to a compound having at least one aromatic ring and multiple carboxyl groups.

[0201] Examples of aromatic carboxylic acid chelating agents include: phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and their derivatives.

[0202] As a carboxylic acid chelating agent, it is preferred to be an amino polycarboxylic acid chelating agent or an aliphatic carboxylic acid chelating agent, more preferably DTPA, oxalic acid, malonic acid, succinic acid, or adipic acid, and even more preferably malonic acid, succinic acid, or adipic acid.

[0203] (Phosonic acid chelating agents)

[0204] Phosphonic acid chelating agents are chelating agents that have at least one phosphonic acid group in their molecule. Furthermore, chelating agents that have both a phosphonic acid group and a carboxyl group are classified as carboxylic acid chelating agents.

[0205] Phosphonic acid chelating agents include, for example, aliphatic phosphonic acid chelating agents and aminophosphonic acid chelating agents.

[0206] Furthermore, aliphatic phosphonic acid chelating agents can have hydroxyl groups in addition to phosphonic acid groups and aliphatic groups.

[0207] Examples of phosphonic acid chelating agents include: ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDP), 1-hydroxypropylidene-1,1'-diphosphonic acid, 1-hydroxybutylidene-1,1'-diphosphonic acid, ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrilotris(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), 1,3-propanediaminebis(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) (EDTPO), ethylenediaminetetra(methylenephosphonic acid), and 1,3-propylenediaminetetra(methylenephosphonic acid). (acid), PDTMP), 1,2-diaminopropanetetra(methylenephosphonic acid), 1,6-hexamethylenediaminetetra(methylenephosphonic acid), diethylenetriamine penta(methylene phosphonic acid), DEPPO, diethylenetriamine penta(methylene phosphonic acid), triethylenetetramine hexa(methylenephosphonic acid), or triethylenetetramine hexa(methylene phosphonic acid), preferably HEDP.

[0208] The number of phosphonic acid groups in the phosphonic acid chelating agent is preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 or 3.

[0209] Furthermore, the carbon number of phosphonic acid chelating agents is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. There is no particular limitation on the lower limit, but it is preferably 1 or more.

[0210] As a phosphonic acid chelating agent, not only the aforementioned compounds can be used, but also the compounds described in paragraphs

[0026] to

[0036] of International Publication No. 2018 / 020878 and the compounds described in paragraphs

[0031] to

[0046] of International Publication No. 2018 / 030006 (copolymers) can be incorporated into this specification.

[0211] Furthermore, phosphonic acid chelating agents can be used alone or in combination of two or more.

[0212] In addition, among commercially available phosphonic acid chelating agents, there are also chelating agents that contain water such as distilled water, deionized water, and ultrapure water in addition to phosphonic acid chelating agents. Even if you use such a water-containing phosphonic acid chelating agent, there will be no problem.

[0213] When the refined product contains a phosphonic acid chelating agent, it is also preferable to further contain other chelating agents (preferably carboxylic acid chelating agents as described). In this case, the mass ratio of the content of the carboxylic acid chelating agent to the content of the phosphonic acid chelating agent (carboxylic acid chelating agent / phosphonic acid chelating agent) is preferably 0.1 to 10, more preferably 0.2 to 5, and even more preferably 0.6 to 1.3.

[0214] In addition, the chelating agent is preferably selected from one or more of the group consisting of DTPA, oxalic acid, malonic acid, succinic acid, adipic acid and HEDP, and more preferably selected from one or more of the group consisting of oxalic acid, malonic acid, succinic acid and adipic acid.

[0215] Chelating agents can be used alone or in combination with two or more.

[0216] The content of chelating agent in the refined product is preferably 0.0005% to 25% by mass, more preferably 0.001% to 5% by mass, and even more preferably 0.005% to 3% by mass, relative to the total mass of the refined product.

[0217] In addition, the content of the chelating agent is preferably 0.01% to 70% by mass, more preferably 0.05% to 60% by mass, and even more preferably 0.1% to 50% by mass, relative to the total mass of the components after solvent removal from the refined product.

[0218] <Polymer>

[0219] The refined product may also contain polymers.

[0220] The polymer is a component that is different from the individual components.

[0221] The molecular weight (weight average molecular weight in the case of a molecular weight distribution) of the polymer is preferably greater than 600, more preferably greater than 1000, even more preferably greater than 1000, and most preferably greater than 3000. The upper limit of the molecular weight is, for example, less than 1,500,000, and also preferably less than 100,000.

[0222] In the case where the polymer is a water-soluble polymer as described later, the weight-average molecular weight of the water-soluble polymer is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 3,000 or more. There is no upper limit to the weight-average molecular weight of the water-soluble polymer, for example, it is 1,500,000 or less, preferably 1,200,000 or less, more preferably 1,000,000 or less, and even more preferably 10,000 or less.

[0223] Furthermore, the "weight-average molecular weight" in this specification refers to the weight-average molecular weight of polyethylene glycol as determined by gel permeation chromatography (GPC).

[0224] The polymer preferably contains repeating units with carboxyl groups (such as repeating units derived from (meth)acrylic acid). The content of repeating units with carboxyl groups relative to the total mass of the polymer is preferably 30% to 100% by mass, more preferably 70% to 100% by mass, and even more preferably 85% to 100% by mass.

[0225] In addition to containing repeating units with carboxyl groups, the polymer is preferably also containing repeating units based on (meth)acrylamide propanesulfonic acid.

[0226] The polymer is preferably a water-soluble polymer.

[0227] Furthermore, the term "water-soluble polymer" refers to a compound in which two or more repeating units are connected by covalent bonds in a linear or network manner, and the mass of the compound that dissolves in 100g of water at 20°C is more than 0.1g.

[0228] Examples of water-soluble polymers include: polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polystyrene sulfonic acid, and their salts; copolymers of monomers such as styrene, α-methylstyrene, and / or 4-methylstyrene with acid monomers such as (meth)acrylic acid and / or maleic acid, and their salts; polymers containing repeating units with aromatic hydrocarbon groups formed by condensing benzenesulfonic acid and / or naphthalenesulfonic acid using formalin, and their salts; vinyl-based synthetic polymers such as polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyacrylamide, polyvinylmethylamine, polyethylimide, polyvinyl oxazoline, polyvinyl imidazole, and polyallylamine; and modified natural polysaccharides such as hydroxyethyl cellulose, carboxymethyl cellulose, and processed starch.

[0229] The water-soluble polymer can be a homopolymer or a copolymer formed by copolymerizing two or more monomers. Examples of such monomers include monomers selected from the group consisting of monomers having carboxyl groups, monomers having sulfonic acid groups, monomers having hydroxyl groups, monomers having polyethylene oxide chains, monomers having amine groups, and monomers having heterocycles.

[0230] The water-soluble polymer is preferably a polymer consisting substantially only of structural units derived from monomers selected from the group. The polymer is defined as consisting substantially only of structural units derived from monomers selected from the group; for example, the content of structural units derived from monomers selected from the group is preferably 95% to 100% by mass, more preferably 99% to 100% by mass, relative to the mass of the polymer.

[0231] Commercially available polymers can also be used. Examples of usable polymers include: the DISPERBYK series manufactured by BYK-Chemie, the DL series, YS series, and HL series manufactured by Nippon Shokubai Co., Ltd., the DEQUEST series manufactured by Thermophos, and the Aron (registered trademark) series manufactured by Toa Synthetic Co., Ltd.

[0232] In addition, as a polymer, the water-soluble polymer described in paragraphs

[0043] to

[0047] of Japanese Patent Application Publication No. 2016-171294 may also be cited, and this content is incorporated into this specification.

[0233] One polymer may be used alone, or two or more polymers may be used.

[0234] When the refined product contains a polymer, the polymer content is preferably 0.01% to 10% by mass, more preferably 0.05% to 5% by mass, and even more preferably 0.1% to 3% by mass, relative to the total mass of the refined product.

[0235] In addition, when the refined product contains a polymer, the polymer content is preferably 0.1% to 50% by mass, more preferably 1% to 40% by mass, and even more preferably 10% to 30% by mass, relative to the total mass of the components of the refined product after solvent removal.

[0236] If the polymer content is within the range described, when the obtained treatment solution is used, the polymer is moderately adsorbed onto the surface of the substrate, which can help improve the corrosion prevention performance of the treatment solution and also ensure a good balance of the viscosity of the treatment solution.

[0237] Oxidizing agents

[0238] The refined product may also contain oxidizing agents.

[0239] The oxidizing agent is a component that is different from the components mentioned above.

[0240] Examples of oxidizing agents include: peroxides, persulfides (e.g., monopersulfides and dipersulfides), percarbonates, acids of these, and salts of these.

[0241] Examples of oxidizing agents include: oxidized halides (iodic acid, metaperiodic acid and orthoperiodic acid, and their salts), perboric acid, perborate, cerium compounds, and ferricyanides (potassium ferricyanide, etc.).

[0242] When the refined product contains an oxidizing agent, the content of the oxidizing agent relative to the total mass of the refined product is preferably 0.01% to 10% by mass, more preferably 0.05% to 5% by mass, and even more preferably 0.1% to 3% by mass.

[0243] In addition, when the refined product contains an oxidant, the content of the oxidant is preferably 0.1% to 50% by mass, more preferably 1% to 40% by mass, and even more preferably 10% to 30% by mass, relative to the total mass of the components of the refined product after solvent removal.

[0244] <pH adjuster>

[0245] In order to adjust and maintain the pH value of the purified substance, the purified substance may also contain a pH adjuster. As the pH adjuster, alkaline compounds and acidic compounds other than the above components can be cited.

[0246] The pH adjuster refers to a component different from the above components. Among them, it is allowed to adjust the pH value of the purified substance by adjusting the addition amount of the above components.

[0247] As the alkaline compound, alkaline organic compounds and alkaline inorganic compounds can be cited.

[0248] The alkaline organic compound is an alkaline organic compound different from the above components. As the alkaline organic compound, for example, amine oxide compounds, nitro compounds, nitroso compounds, oxime compounds, ketoxime compounds, aldoxime compounds, lactam compounds, isocyanide compounds, and urea compounds can be cited.

[0249] As the alkaline inorganic compound, for example, alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia can be cited.

[0250] As the alkali metal hydroxide, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide can be cited. As the alkaline earth metal hydroxide, for example, calcium hydroxide, strontium hydroxide, and barium hydroxide can be cited.

[0251] As the acidic compound, for example, inorganic acids can be cited.

[0252] As the inorganic acid, for example, hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, boric acid, and hexafluorophosphoric acid can be cited. In addition, salts of inorganic acids can also be used. For example, ammonium salts of inorganic acids can be cited. More specifically, ammonium chloride, ammonium sulfate, ammonium sulfite, ammonium nitrate, ammonium nitrite, ammonium phosphate, ammonium borate, and ammonium hexafluorophosphate can be cited.

[0253] As the acidic compound, if it is a compound that becomes an acid or an acid radical ion (anion) in an aqueous solution, a salt of the acidic compound can also be used.

[0254] The pH adjuster can be used alone or in combination of two or more.

[0255] When the purified product contains a pH adjuster, its content can be selected based on the type and amount of other components and the pH value of the target purified product or treatment solution. Relative to the total mass of the purified product, it is preferably 3% by mass or less, more preferably 2% by mass or less. The lower limit of the pH adjuster content relative to the total mass of the purified product is, for example, more than 0% by mass, but can be 0.01% by mass or more, and preferably 0.05% by mass or more.

[0256] When the refined product contains a pH adjuster, the content of the pH adjuster is preferably more than 0% by mass and less than 50% by mass, and more preferably more than 0% by mass and less than 25% by mass, relative to the total mass of the components of the refined product after solvent removal.

[0257] <Water>

[0258] The refined material preferably contains water as a solvent.

[0259] There are no particular restrictions on the type of water used in the refining process if it will not adversely affect the semiconductor substrate; distilled water, deionized water, and pure water (ultrapure water) can be used. Pure water is preferred in terms of being virtually free of impurities and having less impact on the semiconductor substrate during the manufacturing process.

[0260] The water content in the refined product is simply the remainder of any of the components described later. Relative to the total mass of the refined product, the water content is preferably 1% by mass or more, more preferably 30% by mass or more, further preferably 60% by mass or more, and particularly preferably 85% by mass or more. There is no particular upper limit, but relative to the total mass of the refined product, it is preferably 99% by mass or less, more preferably 97% by mass or less.

[0261] <Other Ingredients>

[0262] In addition, the refined product may also contain other components besides the aforementioned components, such as quaternary ammonium compounds, polyhydroxy compounds such as cyclodextrins, fluorine compounds, monocarboxylic acids, and / or organic solvents.

[0263] As quaternary ammonium compounds, the compounds described in paragraphs

[0028] to

[0032] of International Publication No. 2017 / 119244 can be listed, and this content is incorporated into this specification.

[0264] As fluorine compounds, the compounds described in paragraphs

[0013] to

[0015] of Japanese Patent Application Publication No. 2005-150236 can be listed, and this content is incorporated into this specification.

[0265] As an organic solvent, any known organic solvent can be used, preferably a hydrophilic organic solvent such as alcohols and ketones. The organic solvent can be used alone or in combination of two or more.

[0266] Monocarboxylic acids are compounds that have only one carboxyl group.

[0267] The monocarboxylic acid preferably does not have an acid group other than the carboxyl group (phosphonic acid group, etc.), preferably does not have a hydroxyl group, and preferably does not have a cationic group (amine group, etc.).

[0268] The molecular weight of the monocarboxylic acid is preferably 600 or less, more preferably 450 or less, and even more preferably 300 or less. The lower limit is preferably 50 or more, and even more preferably 80 or more. Furthermore, the number of carbon atoms in the monocarboxylic acid is preferably 15 or less, more preferably 12 or less, and even more preferably 8 or less. The lower limit for the number of carbon atoms is preferably 2 or more, and even more preferably 3 or more.

[0269] The monocarboxylic acid and the chelating agent are preferably different components.

[0270] The preferred monocarboxylic acid is an aliphatic monocarboxylic acid, and even more preferably sorbic acid.

[0271] There are no particular restrictions on the amount of the various other ingredients used, as long as they are appropriately set within the range that does not impair the effect of the present invention.

[0272] Furthermore, the content of each component in the purified product can be determined using known methods such as gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), and ion-exchange chromatography (IC).

[0273] <ratio>

[0274] To achieve better filtration performance, the refined material preferably contains the specified components in a specified ratio.

[0275] In the refined product, the mass ratio of amine compound content to surfactant content (amine compound content / surfactant content) is preferably 0.1~5000, more preferably 1~3000, and even more preferably 2~1000.

[0276] If the mass ratio is within the specified range, the deterioration of the filter is suppressed, and the filtration performance is better.

[0277] <The physical properties of refined objects>

[0278] (pH value)

[0279] In terms of superior filtration, the pH value of the purified material is preferably 6-14, more preferably 7-13, and even more preferably 8-12.

[0280] If the pH of the purified material is within the specified range, the deterioration of the filter is suppressed, and the filtration performance is better.

[0281] Furthermore, the pH value can be measured using a known pH meter and according to the method of Japanese Industrial Standards (JIS) Z8802-1984.

[0282] In this instruction manual, the pH measurement temperature is set to 25°C.

[0283] <Preparation solution for refined products>

[0284] There are no particular limitations on the method for preparing the purified substance. For example, the purified substance can be prepared by mixing the components. There are no particular limitations on the order and / or timing of mixing the components. For example, the following method can be used: In a container containing purified water, a specific surfactant, amine compound, chelating agent, polymer, oxidant, and / or other components are added sequentially, stirred and mixed, and a pH adjuster is added to adjust the pH of the mixture, thereby preparing the solution. Alternatively, when adding water and the components to the container, they can be added all at once or in multiple portions.

[0285] There are no particular restrictions on the stirring device and method used in preparing the solution; any known device can be used as a mixer or disperser. Examples of mixers include: industrial mixers, mobile mixers, mechanical stirrers, and magnetic stirrers. Examples of dispersers include: industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.

[0286] [Treatment solution]

[0287] The processing liquid produced by the manufacturing method of the present invention is preferably a refined product in which the content of impurities contained in the refined product has been reduced.

[0288] That is, except for the reduction of impurity content, the treatment solution is preferably substantially the same as the refined product, and the preferred conditions of the components and contents contained in the treatment solution are also the same as the preferred conditions of the refined product.

[0289] In the case where the treatment liquid becomes the diluted treatment liquid described later, the appropriate content of each component (excluding water) relative to the total mass of the diluted treatment liquid is, for example, the amount obtained by dividing the amount described as the appropriate content of each component relative to the total mass of the purified product by the dilution ratio of the range (e.g., 100).

[0290] [Filter]

[0291] Next, the filter used in the manufacturing method of the present invention will be described.

[0292] <First Filter>

[0293] In the method of the present invention, at least a first filter is used.

[0294] The first filter is a filter having at least a first filter material, and an example of its structure is illustrated using Figure 1.

[0295] Figure 1 is a partially cut-out perspective view of a typical first filter.

[0296] In the first filter 40, a cylindrical first filter material 41 and a cylindrical core 42 supporting it are disposed inside the cylindrical filter material. The cylindrical core 42 is formed into a mesh to allow liquid to pass through easily. The first filter material 41 and the core 42 are concentric circles. In addition, a cover 43 is disposed at the upper part of the cylindrical first filter material 41 and the core 42 to prevent liquid from entering from the top. In addition, a liquid outlet 44 for extracting liquid from the inside of the core 42 is disposed at the lower part of the first filter material 41 and the core 42.

[0297] The liquid (refined material) flowing into the first filter 40 is obstructed by the cover 43, so it passes through the first filter material 41 and the core 42, flows into the inside of the core 42, and flows out from the liquid outlet 44 to the outside of the first filter 40.

[0298] Furthermore, in the first filter 40, a core 42 is disposed inside the first filter material 41, but it is not limited to the described form. A protector (with the same form as the core 42 but a different radius) may also be provided on the outside of the first filter material 41.

[0299] (First filter material)

[0300] The first filter material comprises at least one material selected from the group consisting of nylon, polyallyl sulfonic acid, hydrophilically treated perfluoroalkoxyalkane, hydrophilically treated polytetrafluoroethylene, hydrophilically treated polyolefin, and hydrophilically treated polyvinylidene fluoride. The first filter material may also be the aforementioned at least one material itself.

[0301] Examples of nylons include nylon 6 and nylon 6,6, etc.

[0302] Examples of the polyolefins include polyethylene and polypropylene. Examples of the polyethylenes include ultra-high-density polyethylene (UPE) and high-density polyethylene (HDPE).

[0303] The hydrophilic treatment of the perfluoroalkoxyalkane, the hydrophilic treatment of the polytetrafluoroethylene, the hydrophilic treatment of the polyolefin, and the hydrophilic treatment of the polyvinylidene fluoride is not particularly limited if it is a treatment to make the surface of the material hydrophilic.

[0304] Examples of hydrophilic treatments include: plasma treatment, ultraviolet irradiation treatment, corona treatment, electron beam irradiation treatment, acid treatment, alkali treatment, and ozone treatment.

[0305] These hydrophilic treatments can be performed individually or in combination.

[0306] The plasma treatment involves applying a high-frequency voltage in the presence of gas to generate plasma, and then using the gas excited by the plasma to perform surface modification.

[0307] Plasma treatment can be atmospheric pressure plasma treatment (e.g., plasma treatment performed at a pressure of 0.9 atm to 1.1 atm) or vacuum plasma treatment.

[0308] Examples of processing gases used in the plasma process include: oxygen, air, nitrogen, argon, helium, ammonia, carbon monoxide, water vapor, and mixtures of two or more of these.

[0309] This processing gas is supplied between opposing electrodes, and simultaneously an electric field such as a high frequency, pulse wave, or microwave is applied to generate glow discharge plasma, thereby producing plasma-encapsulated gas.

[0310] The temperature for plasma treatment is, for example, 10℃~50℃.

[0311] The processing time for plasma treatment is, for example, 1 second to 1000 seconds.

[0312] Examples of light sources for ultraviolet irradiation treatment include: metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, low-pressure mercury lamps, or high-pressure mercury lamps.

[0313] The wavelength range of the ultraviolet light emitted is preferably in the range of far ultraviolet light (280nm~100nm). Specifically, for example, low-pressure mercury lamps that emit far ultraviolet light of 185nm and 254nm, or xenon excimer lamps that emit far ultraviolet light of 172nm, can preferably be used.

[0314] When irradiating these ultraviolet rays, it is also preferable to do so in the presence of oxygen.

[0315] Irradiation conditions vary depending on the lamp and are not particularly limited. For example, the following methods can be listed: irradiating a low-pressure mercury lamp for 5 seconds to 10 minutes with a light intensity range of 5 mJ / cm2 to 5,000 mJ / cm2; and irradiating an excimer lamp for 1 second to 3 minutes with a light intensity range of 1 mJ / cm2 to 3,000 mJ / cm2.

[0316] Furthermore, the nylon and / or polyallyl sulfonic acid in the first filter material can also be subjected to the aforementioned hydrophilic treatment.

[0317] In addition, the first filter material may be treated in addition to hydrophilic treatment, depending on the need.

[0318] The first filter material is preferably a material selected from the group consisting of nylon, polyallyl sulfonic acid, hydrophilically treated perfluoroalkoxyalkane, and hydrophilically treated polytetrafluoroethylene, more preferably containing nylon or polyallyl sulfonic acid, and even more preferably containing polyallyl sulfonic acid. The first filter material is also preferably the materials themselves.

[0319] The contact angle between the first filter material and water is preferably 0°~70°, more preferably 0°~50°, and even more preferably 0°~35°.

[0320] Furthermore, the contact angle with water is obtained by adding a 1μL water droplet to the surface of the first filter material in an environment with normal atmospheric pressure, temperature of 25℃ and relative humidity of 60%, and measuring the static contact angle after 1 second of adding the droplet.

[0321] Regarding superior filtration performance, the pore size of the first filter material is preferably 50 μm or less, more preferably 200 nm or less, even more preferably 50 nm or less, and particularly preferably 25 nm or less. There are no particular limitations on the lower limit, but for production purposes, it is, for example, preferably 1 nm or more.

[0322] Furthermore, in this specification, the pore size of the filter refers to the pore size determined by the foaming point of isopropanol (IPA).

[0323] <Second Filter>

[0324] In the method of the present invention, a first filter and a second filter containing a second filter material, different from the first filter, can also be used to filter the refined material.

[0325] As an example of the structure of the second filter, a structure in the first filter in which the first filter material is replaced with the second filter material can be cited.

[0326] The second filter may or may not meet the general requirements for serving as the first filter. That is, the second filter material may or may not meet the general requirements for serving as the first filter material.

[0327] If the second filter satisfies the necessary conditions for being the first filter, then the preferred conditions for such a second filter are the same as the preferred conditions for being the first filter.

[0328] For example, the second filter material of the second filter may include at least one material selected from the group consisting of nylon, polyallyl sulfonic acid, perfluoroalkoxyalkane after hydrophilic treatment, polytetrafluoroethylene after hydrophilic treatment, polyolefin after hydrophilic treatment, and polyvinylidene fluoride after hydrophilic treatment. The conditions and preferred conditions for such a second filter material are the same as those described for the conditions and preferred conditions for the first filter material.

[0329] In cases where the second filter material does not meet the necessary conditions for being the first filter material, for example, the second filter material comprises at least one material selected from the group consisting of untreated perfluoroalkoxyalkanes, untreated polytetrafluoroethylene, untreated polyolefins, and untreated polyvinylidene fluoride. The second filter material may also be the aforementioned at least one material itself.

[0330] Examples of polyolefins include polyethylene and polypropylene. Examples of polyethylene include ultra-high density polyethylene (UPE) and high density polyethylene (HDPE).

[0331] If the second filter material does not meet the necessary conditions for being the first filter material, in terms of superior filtration performance, the pore size of the second filter material is preferably 1000 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. There is no particular limitation on the lower limit, but to easily avoid bubble clogging, it is preferably more than 10 nm, and more preferably more than 25 nm.

[0332] 〔filter〕

[0333] The manufacturing method of the present invention uses a first filter to filter the refined material to manufacture a processing liquid for semiconductor substrates.

[0334] The first filter, the refined material, and the processing liquid are as described above.

[0335] The filtration may also be a filtration that uses only the first filter.

[0336] Alternatively, the filtration may be a process of filtering the refined material using a first filter and a second filter containing a second filter material different from the first filter, or a process using multiple (e.g., 2 to 5) filters.

[0337] Regarding the second filter, it is as described above.

[0338] In the case of filtration using multiple filters, at least one of the multiple filters is a filter that satisfies the general necessary conditions for being a first filter.

[0339] Hereinafter, a filter that meets the necessary conditions for being the first filter will also be called a "necessary condition sufficient filter".

[0340] When a necessary condition sufficient filter is defined as a first filter, the filter existing upstream or downstream of the first filter in the filter flow path can be a second filter, preferably the filter existing upstream.

[0341] Furthermore, the second filter can also be a filter that meets the necessary conditions.

[0342] In the manufacturing method of the present invention, it is also preferred that the pore size of the second filter material is the same as or larger than that of the first filter material, and the refined material is filtered by passing liquid through the second filter and the first filter in sequence.

[0343] Specifically, the ratio of the pore size of the second filter material of the second filter to the pore size of the first filter material of the first filter (pore size of the second filter material / pore size of the first filter material) is preferably 1 to 1000, more preferably 2 to 500, and even more preferably 3 to 50.

[0344] In the case where there may be a combination of multiple first filters and second filters that are more present on the upstream side within the filter flow path, it is preferable that at least one of the combinations satisfies the general relationship, more preferably that two or more combinations satisfy the general relationship, and even more preferably that all the combinations satisfy the general relationship.

[0345] The pressure difference (hereinafter also referred to as "filtration pressure") across the filter when the purified material is passed through it is preferably 0.005 MPa or more, more preferably 0.01 MPa or more, even more preferably 0.05 MPa or more, and particularly preferably 0.2 MPa or more. Furthermore, the filtration pressure is preferably 1 MPa or less, more preferably 0.6 MPa or less, and even more preferably 0.4 MPa or less.

[0346] When the filtration is performed using multiple filters, it is preferable that the filtration pressure of at least one filter is within the specified range, more preferably that the filtration pressure of at least the first filter is within the specified range, and even more preferably that the filtration pressures of both the first and second filters are within the specified range.

[0347] The filtration may be cyclic filtration or non-cyclic filtration.

[0348] There is no particular limitation on the number of cyclic filtrations (cycle count), but it is preferably 2 to 10 times. Furthermore, the cyclic filtration is preferably performed by repeatedly filtration using the first filter before returning the refined material upstream, and more preferably by repeatedly filtration using both the first and second filters before returning the refined material upstream.

[0349] In the manufacturing method of the present invention, other processing may also be performed before, after, or midway through the filtration process. For example, the purified material may be filtered using methods other than the filtration method. Furthermore, ion exchange steps and / or electrostatic removal steps may also be performed.

[0350] As an ion exchange step, the steps described in paragraphs

[0078] to

[0081] of International Publication No. 2018 / 180735 may be referenced and incorporated herein by reference.

[0351] As a de-energizing step, the steps described in paragraph

[0082] of International Publication No. 2018 / 180735 may be referenced and incorporated into this specification.

[0352] (container)

[0353] Provided that corrosivity and other properties are not a problem, the refined product supplied by the manufacturing method of the present invention and / or the treatment liquid manufactured by the manufacturing method of the present invention can be filled into any container for storage, handling and use.

[0354] As a container, it is preferable to have a high degree of cleanliness for semiconductor applications, and to suppress the leaching of impurities from the inner wall of the container's containing part into each liquid. Examples of such containers include various commercially available containers for semiconductor cleaning solutions, such as the "clean bottle" series manufactured by Aicello Chemicals Co., Ltd., and the "pure bottle" manufactured by Kodama Resin Industries, Ltd., but are not limited to these.

[0355] In addition, as a container, it is preferable that the inner wall of its containing part and other liquid contact parts that come into contact with each liquid are made of fluorinated resin (perfluororesin) or metal that has been treated to prevent rust and metal leaching.

[0356] The inner wall of the container is preferably formed of a resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a resin different from the resin, or a metal formed after rust prevention and metal leaching prevention treatment of stainless steel, Hastelloy, Inconel, and Monel.

[0357] As the different resins mentioned, fluorinated resins (perfluorinated resins) are preferred. Thus, by using a container with an inner wall made of fluorinated resin, compared to a container with an inner wall made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin, the undesirable situation of leaching of ethylene or propylene oligomers can be suppressed.

[0358] Specific examples of containers with fluorinated resin inner walls include the FluoroPure perfluoroalkoxyalkane (PFA) composite container manufactured by Entecris. Alternatively, containers described in Japanese Patent Publication No. 3-502677 (page 4), International Publication No. 2004 / 016526 (page 3), and International Publication No. 99 / 046309 (pages 9 and 16) may also be used.

[0359] In addition to the fluorinated resin, quartz and electrolytically polished metal materials (i.e., electrolytically polished metal materials) can also be used in the inner wall of the container.

[0360] The metal material used in the manufacture of the electrolytically ground metal material is preferably a metal material that includes at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is more than 25% by mass relative to the total mass of the metal material, such as stainless steel and nickel-chromium alloys.

[0361] The combined chromium and nickel content in the metal material should ideally be 30% or more by mass relative to the total mass of the metal material.

[0362] Furthermore, there is no particular upper limit to the combined chromium and nickel content in metallic materials, but it is generally preferred to be below 90% by mass.

[0363] There are no particular limitations on the method for electrolytic polishing of metallic materials, and known methods can be used. For example, the methods described in paragraphs

[0011] to

[0014] of Japanese Patent Application Publication No. 2015-227501 and paragraphs

[0036] to

[0042] of Japanese Patent Application Publication No. 2008-264929 can be used.

[0364] These containers are preferably cleaned internally before being filled with the material to be filled. The liquid used for cleaning is preferably one in which metallic impurities are reduced. The refined material or treatment solution can be bottled after manufacturing into containers such as gallon bottles or coating bottles for transport and storage.

[0365] To prevent changes in the composition of the refined material or processing liquid during storage, the container can be purged with an inert gas (nitrogen, argon, etc.) with a purity of 99.99995% by volume or higher. A gas with low water content is particularly preferred. Furthermore, transportation and storage can be at room temperature, or the temperature can be controlled within a range of -20°C to 20°C to prevent deterioration.

[0366] (clean room)

[0367] The operations, processing analysis, and measurements, including the implementation of the manufacturing method of the present invention, the opening and cleaning of the container, and the filling of the refined material and the processing solution, are preferably all performed in a cleanroom. The cleanroom preferably meets the 14644-1 cleanroom standard. It is more preferably to meet any one of ISO (International Standardization Organization) Level 1, ISO Level 2, ISO Level 3, and ISO Level 4, and even more preferably to meet ISO Level 1 or ISO Level 2, and even more preferably to meet ISO Level 1.

[0368] [Applications of the treatment fluid]

[0369] The processing liquid manufactured using the manufacturing method of the present invention is a processing liquid for semiconductor substrates, preferably a processing liquid applied to semiconductor substrates after chemical mechanical polishing (CMP) treatment.

[0370] In addition, the processing liquid manufactured using the manufacturing method of the present invention is preferably a cleaning liquid for semiconductor substrates in the manufacturing process of semiconductor substrates.

[0371] The processing solution is preferably a cleaning solution used in the cleaning step of cleaning a semiconductor substrate after chemical mechanical polishing (CMP) treatment.

[0372] Furthermore, when using the processing solution (such as for cleaning semiconductor substrates), additional components can be added to the processing solution before use.

[0373] Alternatively, the treatment solution can be used after dilution.

[0374] The diluted treatment solution obtained by diluting the treatment solution in this way is also a form of treatment solution.

[0375] The dilution rate of the diluted treatment solution can be adjusted appropriately according to the type and content of each component, as well as the semiconductor substrate or other object to be treated, such as for cleaning. The ratio of the diluted treatment solution to the original treatment solution (dilution ratio) is preferably 10 to 10,000 times by mass or volume (volume ratio at 25°C), more preferably 20 to 3,000 times, and even more preferably 50 to 1,000 times.

[0376] In addition, the treatment solution is preferably diluted with water.

[0377] That is, a treatment solution (diluted treatment solution) containing each component in an amount obtained by dividing the appropriate content of each component (excluding water) that may be contained in the refined material by a dilution ratio (e.g., 100) within the range can also be suitably used.

[0378] In other words, the appropriate content of each component (excluding water) relative to the total mass of the diluent is, for example, the amount obtained by dividing the amount described as the appropriate content of each component relative to the total mass of the purified product by the dilution ratio of the range (e.g., 100).

[0379] Furthermore, the same object (the object to be cleaned, etc.) can be treated with other processing solutions before and / or after (preferably after) the processing solution manufactured by the manufacturing method of the present invention is used (such as for cleaning semiconductor substrates).

[0380] If at least one treatment is performed using a treatment liquid manufactured using the manufacturing method of the present invention, then other treatment liquids used before and / or after that treatment on the same object may or may not be equivalent to the treatment liquid manufactured using the manufacturing method of the present invention.

[0381] Hereinafter, the other treatment fluid will also be referred to as the second treatment fluid.

[0382] It is believed that by performing a two-stage process, a cleaner object with higher precision and less damage can be obtained. In the two-stage process, in addition to the treatment using a treatment liquid manufactured by the manufacturing method of the present invention, a second treatment liquid without surfactants is also performed, or a second treatment liquid containing a damage inhibitor (such as a corrosion inhibitor) during the cleaning of the object is performed.

[0383] In the two-stage processing, it is preferable that the first stage processing is performed using a processing liquid manufactured by the manufacturing method of the present invention, and the second stage processing is performed using a second processing liquid that does not contain surfactants, or a second processing liquid containing metal contents present in the object to be protected (such as the object to be cleaned).

[0384] In particular, regarding the removal of residues from the treated object, it is preferable to use a second treatment solution that does not contain surfactants. In particular, regarding the suppression of damage to the object during finishing, it is preferable to use a second treatment solution containing components that protect against metal inclusions.

[0385] The second processing solution may contain each of the components described as components that may be contained in the refined product. Furthermore, the second processing solution may also contain each of the components as described in terms of their content in the refined product.

[0386] (In this case, appropriate and reasonable substitutions may be made: the description of the content of each component in the refined product as "relative to the total mass of the refined product" may be replaced with the description of "relative to the total mass of the second processing liquid", or the description of "relative to the total mass of the components after solvent removal from the refined product" may be replaced with the description of "relative to the total mass of the components after solvent removal from the second processing liquid", etc.)

[0387] The second treatment solution may also be free of specific surfactants.

[0388] As described above, the second treatment solution may or may not contain a surfactant. The surfactant that the second treatment solution may contain may be a specific surfactant or a surfactant other than a specific surfactant.

[0389] The second treatment solution may contain surfactants other than the specific surfactants, such as cationic surfactants, anionic surfactants other than the specific surfactants, and nonionic surfactants other than the specific surfactants.

[0390] Cationic surfactants are preferably nonpolymeric compounds having one or more (preferably one to two) cationic nitrogen atoms (N+).

[0391] The cationic nitrogen atom (N+) may also be contained in the pyridinium ring.

[0392] In addition, cationic surfactants containing only cationic nitrogen atoms (N+) in the form not present in the pyridinium ring are preferably those with 5 or more carbon atoms, more preferably 5 to 50.

[0393] Cationic surfactants containing cationic nitrogen atoms (N+) in the form of pyridinium rings preferably have 5 or more carbon atoms, more preferably 5 to 50, and even more preferably 10 to 50.

[0394] The cationic nitrogen atom (N+) is preferably formed into a salt together with the counter anion. Examples of counter anions include OH-, as well as halide anions such as Cl- and Br-.

[0395] Cationic surfactants are preferably salts (e.g., one or more of hydroxides, chlorides, and bromides) selected from the group consisting of cetyltrimethylammonium, stearyltrimethylammonium, laurylpyridinium, cetylpyridinium, 4-(4-diethylaminophenylazo)-1-(4-nitrobenzyl)pyridinium, benzalkonium, benzenethonium, benzyl dimethyl dodecylammonium, benzyl dimethyl hexadecylammonium, hexadecyltrimethylammonium, dimethyl dioctadecylammonium, dodecyltrimethylammonium, decylmethyl polyoxyethylammonium, di-dodecyl dimethylammonium, tetraheptylammonium, tetra(decyl)ammonium, and dimethyl dihexadecylammonium.

[0396] Cationic surfactants can be commercially available products. Examples of cationic surfactants that can be used include the Quartamin series manufactured by Kao Corporation, the Pionin series manufactured by Takemoto Oils & Fats Corporation, and the Surflon series manufactured by AGC Seimi Chemical Co., Ltd.

[0397] In the second treatment solution, a single surfactant may be used, or two or more surfactants may be used. When the second treatment solution contains a surfactant, the surfactant may be a specific surfactant, a surfactant other than a specific surfactant, or both.

[0398] When the second treatment solution contains a surfactant, the surfactant content is preferably 0.00001% to 10% by mass, more preferably 0.0001% to 3% by mass, and even more preferably 0.002% to 1.5% by mass relative to the total mass of the second treatment solution.

[0399] In addition, when the second treatment liquid contains a surfactant, the content of the surfactant is preferably 0.001% to 50% by mass, more preferably 0.05% to 20% by mass, and even more preferably 1% to 10% by mass, relative to the total mass of the components of the second treatment liquid after solvent removal.

[0400] Furthermore, the so-called "total mass of the components of the second treatment liquid after solvent removal" refers to the total content of all components contained in the second treatment liquid other than water and organic solvents.

[0401] The second treatment solution is also preferably a compound containing amines.

[0402] The amine compounds that may be contained in the second treatment liquid are the same as those described in the description of the treatment liquid.

[0403] In the second treatment solution, an amine compound may be used alone or in combination with two or more.

[0404] When the second treatment liquid contains an amine compound, the content of the amine compound relative to the total mass of the second treatment liquid is preferably 0.01% to 30% by mass, more preferably 0.1% to 20% by mass, and even more preferably 1% to 10% by mass.

[0405] In addition, when the second treatment liquid contains amine compounds, the content of amine compounds is preferably 5% to 90% by mass, more preferably 20% to 80% by mass, and even more preferably 40% to 70% by mass, relative to the total mass of the components after solvent removal in the second treatment liquid.

[0406] In addition, the second treatment liquid is preferably a compound (hereinafter also referred to as "specific nitrogen-containing compound") contained in either the amine compound or the amino acid chelating agent described in the description of the treatment liquid.

[0407] The specific nitrogen-containing compound contained in the second treatment liquid is preferably an amino alcohol, an amine compound with a cyclic structure, or an amino acid chelating agent, and more preferably an amino alcohol.

[0408] The specific nitrogen-containing compound contained in the second treatment solution may be used alone or in combination with two or more compounds.

[0409] When the second treatment solution contains only one specific nitrogen-containing compound, the second treatment solution preferably contains an amino alcohol. Furthermore, when the second treatment solution contains two or more specific nitrogen-containing compounds, the second treatment solution preferably contains at least two compounds selected from the group consisting of amino alcohols, cyclic amine compounds, and amino acid chelating agents; more preferably, it contains at least one compound selected from the group consisting of amino alcohols and amino acid chelating agents.

[0410] The amino alcohols contained in the second treatment liquid as specific nitrogen-containing compounds are the same as those described in the description of the treated liquid.

[0411] The cyclic amine compound included in the second treatment liquid as a specific nitrogen-containing compound may be the same as the cyclic amine compound described in the description of the treatment liquid, for example: pyridine compounds, pyrazine compounds, pyrimidine compounds, and triazine compounds. Here, a triazine compound is a compound having a triazine ring.

[0412] Examples of pyridine, pyrazine, pyrimidine, and triazine compounds include compounds formed by substituting at least one substituent selected from the group consisting of amino, hydroxyl, and carboxyl groups onto their respective hetero-six-membered rings (pyridine, pyrazine, pyrimidine, and triazine rings), as well as their proton tautomers. For example, uracil is a proton tautomer of 2,4-dihydroxypyrimidine, and cytosine is a proton tautomer of 4-aminopyrimidine-2-ol.

[0413] The cyclic amine compound contained in the second treatment liquid is preferably a pyridine compound or a pyrimidine compound, more preferably 2-aminopyrimidine, 2,4-diaminopyrimidine, 2,4,6-triaminopyrimidine, 2,6-dihydroxypyridine, uracil, or cytosine.

[0414] The amino acid chelating agent included in the second treatment solution as a specific nitrogen-containing compound is the same as the amino acid chelating agent described in the description of the treatment solution.

[0415] Among them, the amino acid is preferably alkaline, and more preferably histidine, arginine, or lysine.

[0416] When the second treatment liquid contains the nitrogen-containing compound, the content of the nitrogen-containing compound relative to the total mass of the second treatment liquid is preferably 0.01% to 30% by mass, more preferably 0.1% to 20% by mass, and even more preferably 1% to 10% by mass.

[0417] Furthermore, when the second treatment liquid contains the nitrogen-containing compound, the content of the nitrogen-containing compound is preferably 5% to 90% by mass, more preferably 20% to 80% by mass, and even more preferably 40% to 70% by mass, relative to the total mass of the components of the second treatment liquid after solvent removal.

[0418] The second treatment solution is also preferably one that contains a chelating agent.

[0419] The chelating agent that may be contained in the second treatment solution is the same as that described in the description of the treatment solution.

[0420] In the second treatment solution, a single chelating agent may be used, or two or more chelating agents may be used.

[0421] When the second treatment solution contains a chelating agent, the content of the chelating agent relative to the total mass of the second treatment solution is preferably 0.01% to 30% by mass, more preferably 0.1% to 20% by mass, and even more preferably 1% to 10% by mass.

[0422] In addition, when the second treatment solution contains a chelating agent, the content of the chelating agent is preferably 1% to 70% by mass, more preferably 10% to 60% by mass, and even more preferably 20% to 50% by mass, relative to the total mass of the components after solvent removal in the second treatment solution.

[0423] The second treatment solution is also preferably a polymer-containing solution.

[0424] The polymers that may be contained in the second treatment liquid are the same as those described in the description of the liquid being treated.

[0425] In the second treatment solution, a single polymer may be used, or two or more polymers may be used.

[0426] When the second treatment liquid contains a polymer, the polymer content is preferably 0.001% to 20% by mass, more preferably 0.01% to 10% by mass, and even more preferably 0.1% to 5% by mass, relative to the total mass of the second treatment liquid.

[0427] In addition, when the second treatment liquid contains a polymer, the polymer content is preferably 0.01% to 40% by mass, more preferably 0.1% to 30% by mass, and even more preferably 1% to 20% by mass, relative to the total mass of the components of the second treatment liquid after solvent removal.

[0428] The second treatment solution is also preferably one that contains a pH adjuster.

[0429] The pH adjuster that may be included in the second treatment solution is the same as the pH adjuster described in the instructions for the treated solution.

[0430] In the second treatment solution, a single pH adjuster may be used, or two or more may be used.

[0431] When the second treatment solution contains a pH adjuster, the content of the pH adjuster relative to the total mass of the second treatment solution is preferably more than 0% by mass and less than 3% by mass, and more preferably more than 0% by mass and less than 2% by mass.

[0432] In addition, when the second treatment solution contains a pH adjuster, the content of the pH adjuster is preferably more than 0% by mass and less than 50% by mass, and more preferably more than 0% by mass and less than 25% by mass, relative to the total mass of the components of the second treatment solution after solvent removal.

[0433] The second treatment solution is also preferably water-containing.

[0434] The water that the second treatment liquid may contain is the same as the water described in the description of the treated liquid.

[0435] When the second treatment solution contains water, the water content is preferably 1% by mass or more, more preferably 30% by mass or more, more preferably 60% by mass or more, and particularly preferably 85% by mass or more, relative to the total mass of the second treatment solution. There is no particular upper limit, but it is preferably 99% by mass or less, more preferably 97% by mass or less, relative to the total mass of the second treatment solution.

[0436] The second treatment solution is also preferably composed of monocarboxylic acids.

[0437] The monocarboxylic acids that may be contained in the second treatment solution are the same as those described in the description of the treated solution.

[0438] In the second treatment solution, a single monocarboxylic acid may be used alone, or two or more may be used.

[0439] When the second treatment solution contains monocarboxylic acid, the content of monocarboxylic acid relative to the total mass of the second treatment solution is preferably 0.0001% to 10% by mass, more preferably 0.001% to 2% by mass, and even more preferably 0.005% to 0.5% by mass.

[0440] In addition, when the second treatment liquid contains monocarboxylic acid, the content of monocarboxylic acid is preferably 0.001% to 25% by mass, more preferably 0.01% to 10% by mass, and even more preferably 0.1% to 3% by mass, relative to the total mass of the components after solvent removal in the second treatment liquid.

[0441] In cases where the second treatment solution contains two or more specific nitrogen-containing compounds, and for aspects of the invention being more effective, the second treatment solution is also preferably further comprising polycarboxylic acids.

[0442] Examples of polycarboxylic acids include polymers containing repeating units with carboxyl groups, as well as aromatic polycarboxylic acids.

[0443] Polymers containing repeating units with carboxyl groups can be listed as polymers described in the instructions for the treated liquid that contain repeating units with carboxyl groups (e.g., repeating units derived from (meth)acrylic acid). Commercially available examples of such polymers include: the YS series manufactured by Nippon Shokubai Co., Ltd.; the Aron series manufactured by Toa Gosei Co., Ltd.; the DISPERBYK series manufactured by BYK-Chemie Co., Ltd.; the DL series and HL series manufactured by Nippon Shokubai Co., Ltd.; and the DEQUEST series manufactured by Thermophos Co., Ltd.

[0444] The aromatic polycarboxylic acids contained in the second treatment solution, including their preferred forms, are the same as those described in the description of the treated solution. Preferably, the aromatic polycarboxylic acids contained in the second treatment solution are phthalic acid, trimellitic acid, or pyromellitic acid.

[0445] The optimal pH value for the second treatment solution is above 2 and below 7.

[0446] The second processing solution can be manufactured, for example, by mixing the various components that may be contained in the second processing solution. There are no particular restrictions on the order and / or timing of mixing the components; the components can be added together or added in multiple stages.

[0447] Alternatively, the second treatment liquid may be filtered according to the same procedure as described in the manufacturing method of the present invention, or it may be omitted.

[0448] Alternatively, the second treatment solution can be used after dilution. This diluted second treatment solution is also considered a form of the second treatment solution.

[0449] The dilution rate of the diluted second processing solution can be adjusted appropriately according to the type and content of each component and the semiconductor substrate or other object to be cleaned. The ratio of the diluted second processing solution to the undiluted second processing solution (dilution ratio) is preferably 10 to 10,000 times by mass or volume (volume ratio at 25°C), more preferably 20 to 3,000 times, and even more preferably 50 to 1,000 times.

[0450] In addition, the second treatment solution is preferably diluted with water.

[0451] That is, a second treatment solution (diluted second treatment solution) containing each component can also be suitably used, which is obtained by dividing the appropriate content of each component (excluding water) that may be contained in the second treatment solution by the dilution ratio (e.g., 100) of the range.

[0452] In other words, the appropriate content of each component (excluding water) relative to the total mass of the diluted second treatment liquid is, for example, the amount described as the appropriate content of each component relative to the total mass of the second treatment liquid (the second treatment liquid before dilution) divided by the dilution ratio of the range (e.g., 100).

[0453] The following describes in detail the method of using the treatment solution when cleaning a semiconductor substrate after chemical mechanical polishing (CMP).

[0454] <Object to be cleaned>

[0455] Examples of objects to be cleaned by the treatment liquid include semiconductor substrates containing metals.

[0456] Furthermore, the term "on the semiconductor substrate" in this specification includes, for example, any of the surface, sides, and trenches of the semiconductor substrate. Additionally, the term "metal inclusions on the semiconductor substrate" includes not only metal inclusions directly present on the surface of the semiconductor substrate, but also metal inclusions present on the semiconductor substrate through other layers.

[0457] Metals contained in a metal inclusion may include, for example, at least one metal M selected from the group consisting of Cu (copper), Co (cobalt), W (tungsten), Ti (titanium), Ta (tantalum), Ru (ruthenium), Cr (chromium), Hf (hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium).

[0458] Metal-containing substances are any substances that contain metal (metal atoms), such as elemental metal M, alloys containing metal M, oxides of metal M, nitrides of metal M, and nitrogen oxides of metal M.

[0459] In addition, the metal inclusions may be mixtures containing two or more of these compounds.

[0460] Furthermore, the oxides, nitrides, and nitrogen oxides may also be complex oxides, complex nitrides, and complex nitrogen oxides containing metals.

[0461] The content of metal atoms in the metal inclusion relative to the total mass of the metal inclusion is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. Since the metal inclusion can be the metal itself, the upper limit is 100% by mass.

[0462] The semiconductor substrate is preferably a metal containing a metal M, more preferably a metal containing at least one metal selected from the group consisting of W, Co, Cu, Ti, Ta, and Ru (copper inclusion, cobalt inclusion, tungsten inclusion, titanium inclusion, tantalum inclusion, and ruthenium inclusion, etc.), and even more preferably a metal containing at least one metal selected from the group consisting of W and Co.

[0463] There are no particular limitations on the semiconductor substrate that can be cleaned by the treatment liquid. For example, substrates with metal wiring films, barrier metals, and insulating films on the surface of the wafer that constitutes the semiconductor substrate can be listed.

[0464] Specific examples of wafers constituting semiconductor substrates include: silicon (Si) wafers, silicon carbide (SiC) wafers, silicon-containing resin-based wafers (glass epoxy wafers), gallium phosphide (GaP) wafers, gallium arsenide (GaAs) wafers, and indium phosphide (InP) wafers.

[0465] The silicon wafer can be an n-type silicon wafer doped with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb)) or a p-type silicon wafer doped with trivalent atoms (e.g., boron (B) and gallium (Ga)). The silicon used in the silicon wafer can be, for example, any of amorphous silicon, single-crystal silicon, polycrystalline silicon, and polysilicon.

[0466] The processing solution is useful for silicon-based wafers, such as silicon wafers, silicon carbide wafers, and silicon-containing resin-based wafers (glass epoxy wafers).

[0467] The semiconductor substrate may also have an insulating film on the wafer.

[0468] Specific examples of insulating films include: silicon oxide films (e.g., silicon dioxide (SiO2) films, and tetraethyl orthosilicate (Si(OC2H5)4) films (TEOS (tetraethyl orthosilicate) films), silicon nitride films (e.g., silicon nitride (Si3N4), and silicon carbonitride (SiNC) films), and low-k dielectric films (e.g., carbon-doped silicon oxide (SiOC) films, and silicon carbide (SiC) films).

[0469] The metal inclusions are preferably metal-containing films (metal films).

[0470] Examples of metal films used in semiconductor substrates include: metal films containing at least one metal selected from the group consisting of tungsten (W) and cobalt (Co); for example, films with tungsten as the main component (tungsten-containing films); films with cobalt as the main component (cobalt-containing films); and metal films made of alloys containing one or more alloys selected from the group consisting of W and Co.

[0471] The semiconductor substrate is also preferably one having at least one of a metal film containing tungsten and a metal film containing cobalt.

[0472] Examples of tungsten-containing films (metal films with tungsten as the main component) include: metal films containing only tungsten (tungsten metal films), and metal films made of alloys containing tungsten and other metals (tungsten alloy metal films).

[0473] Specific examples of tungsten alloy metal films include tungsten-titanium alloy metal films (WTi alloy metal films) and tungsten-cobalt alloy metal films (WCo alloy metal films).

[0474] Tungsten-containing films are used, for example, in barrier metals or in the connection between vias and wiring.

[0475] Examples of cobalt-containing films (metal films with cobalt as the main component) include: metal films containing only metallic cobalt (cobalt metal films), and metal films made of alloys containing metallic cobalt and other metals (cobalt alloy metal films).

[0476] Specific examples of cobalt alloy metal films include metal films made of alloys of cobalt with one or more metals selected from titanium (Ti), chromium (Cr), iron (Fe), nickel (Ni), molybdenum (Mo), palladium (Pd), tantalum (Ta), and tungsten (W). More specifically, examples include: cobalt-titanium alloy metal films (CoTi alloy metal films), cobalt-chromium alloy metal films (CoCr alloy metal films), cobalt-iron alloy metal films (CoFe alloy metal films), cobalt-nickel alloy metal films (CoNi alloy metal films), cobalt-molybdenum alloy metal films (CoMo alloy metal films), cobalt-palladium alloy metal films (CoPd alloy metal films), cobalt-tantalum alloy metal films (CoTa alloy metal films), and cobalt-tungsten alloy metal films (CoW alloy metal films), etc.

[0477] The processing solution is useful for substrates with cobalt-containing films. Among cobalt-containing films, cobalt metal films are mostly used as wiring films, while cobalt alloy metal films are mostly used as barrier metals.

[0478] The semiconductor substrate preferably also has a copper-containing film (a metal film mainly composed of copper).

[0479] Examples of the copper-containing film include a wiring film containing only metallic copper (copper wiring film) and a wiring film made of an alloy of metallic copper and other metals (copper alloy wiring film).

[0480] Specific examples of the copper alloy wiring film include a wiring film made of an alloy of one or more metals selected from aluminum (Al), titanium (Ti), chromium (Cr), manganese (Mn), tantalum (Ta), and tungsten (W), and copper. More specifically, examples include a copper-aluminum alloy wiring film (CuAl alloy wiring film), a copper-titanium alloy wiring film (CuTi alloy wiring film), a copper-chromium alloy wiring film (CuCr alloy wiring film), a copper-manganese alloy wiring film (CuMn alloy wiring film), a copper-tantalum alloy wiring film (CuTa alloy wiring film), and a copper-tungsten alloy wiring film (CuW alloy wiring film).

[0481] In addition, it is sometimes preferable to use the treatment liquid for cleaning a substrate that has at least a copper-containing wiring film and a metal film (cobalt barrier metal) made only of metallic cobalt and serving as a barrier metal for the copper-containing wiring film on the upper part of the wafer constituting the semiconductor substrate, and the copper-containing wiring film and the cobalt barrier metal are in contact on the substrate surface.

[0482] As a method for forming the insulating film, tungsten-containing film, cobalt-containing film, etc. on the wafer constituting the semiconductor substrate, there is no particular limitation as long as it is a method usually carried out in this field.

[0483] As a method for forming the insulating film, for example, the following method can be cited: the wafer constituting the semiconductor substrate is heat-treated in the presence of oxygen to form a silicon oxide film, and then, gases of silane and ammonia are introduced, and a silicon nitride film is formed by chemical vapor deposition (CVD) method.

[0484] As a method for forming the tungsten-containing film and cobalt-containing film, for example, the following method can be cited: on the wafer having the insulating film, a circuit is formed by a known method such as a resist, and then, a tungsten-containing film and a cobalt-containing film are formed by methods such as plating and CVD method.

[0485] <CMP process>

[0486] CMP processing, for example, is a process that planarizes the surface of a substrate having a metal wiring film, a barrier metal, and an insulating film by using a combination of chemical action and mechanical polishing with an abrasive slurry containing abrasive microparticles (abrasive particles).

[0487] On the surface of a semiconductor substrate after CMP treatment, impurities may sometimes remain, originating from the abrasive particles used in the CMP process (e.g., silicon dioxide and alumina), the polished metal wiring film, and metal impurities (metal residues) from barrier metals. Additionally, organic residues from the CMP treatment solution may also remain. These impurities pose a concern, for example, as they could cause short circuits between wirings, thus degrading the electrical characteristics of the semiconductor substrate. Therefore, the CMP-treated semiconductor substrate is subjected to a cleaning process to remove these impurities from its surface.

[0488] As a specific example of a semiconductor substrate after CMP treatment, the substrate after CMP treatment described in the "Journal of the Japan Society of Precision Engineering" (Vol.84, No.3, 2018) can be cited, but it is not limited to this.

[0489] <Methods for cleaning semiconductor substrates>

[0490] The method for cleaning a semiconductor substrate may simply include a cleaning step of cleaning the semiconductor substrate after CMP treatment using the aforementioned treatment solution. Preferably, the method for cleaning a semiconductor substrate also includes a step of cleaning the semiconductor substrate after CMP treatment using a diluted treatment solution (cleaning step).

[0491] Furthermore, as described below, the washing step may be performed only once or more. Moreover, at least one of the washing steps performed only once or more is a washing step using a treatment solution manufactured using the manufacturing method of the present invention. Provided the aforementioned necessary conditions are met, the treatment solution mentioned in the following description of the washing step may be a treatment solution manufactured using the manufacturing method of the present invention, or it may be the second treatment solution.

[0492] The cleaning step of using a processing solution to clean a semiconductor substrate is not particularly limited if it is a known method for CMP-treated semiconductor substrates. Suitable methods include those commonly used in the field, such as scrubbing (where a brush or other cleaning component physically contacts the surface of the semiconductor substrate while the processing solution is supplied to it to remove residues); immersion cleaning (where the semiconductor substrate is immersed in the processing solution); rotation cleaning (where the processing solution is dripped while the semiconductor substrate is rotated); and spray cleaning (where the processing solution is sprayed). In immersion cleaning, to further reduce impurities remaining on the surface of the semiconductor substrate, it is preferable to perform ultrasonic treatment on the processing solution in which the semiconductor substrate is immersed.

[0493] The cleaning method for semiconductor substrates in the cleaning step can be either a wafer-by-wafer method or a batch method. The wafer-by-wafer method usually processes semiconductor substrates one by one, while the batch method usually processes multiple semiconductor substrates simultaneously.

[0494] In the cleaning step, there are no particular restrictions on the temperature of the treatment solution used to clean the semiconductor substrate if it is the temperature typically used in this field. Cleaning is mostly carried out at room temperature (about 25°C), but the temperature can be arbitrarily selected to improve cleaning performance and / or suppress damage to the components. For example, the temperature of the treatment solution is preferably 10°C to 60°C, and more preferably 15°C to 50°C.

[0495] The washing time in the washing step depends on the type and content of the components contained in the treatment solution, so it cannot be generalized. In practical terms, it is better to be 10 seconds to 2 minutes, more preferably 20 seconds to 1 minute or 30 seconds, and even better to be 30 seconds to 1 minute.

[0496] There is no particular limitation on the supply rate (supply speed) of the treatment solution in the washing step, but it is preferably 50 mL / min to 5000 mL / min, and more preferably 500 mL / min to 2000 mL / min.

[0497] In the washing step, mechanical agitation can also be used to further enhance the washing ability of the treatment solution.

[0498] Examples of mechanical stirring methods include: circulating the processing liquid on a semiconductor substrate, flowing or spraying the processing liquid over a semiconductor substrate, and stirring the processing liquid using ultrasound or mega-frequency ultrasound.

[0499] The washing step may be performed only once or more than twice. If the washing step is performed more than twice, the same method may be repeated or different methods may be combined.

[0500] In the case where only one washing step is performed, the treatment liquid used in the washing step is a treatment liquid manufactured using the manufacturing method of the present invention.

[0501] When performing more than two cleaning steps, the treatment solution used in each step may also be different.

[0502] In cases where more than one washing step is performed, it is acceptable as long as at least one of the washing steps uses a treatment solution manufactured using the manufacturing method of the present invention.

[0503] For example, the washing step using the second treatment solution can be performed before and / or after (preferably after) the washing step using the treatment solution manufactured by the manufacturing method of the present invention.

[0504] More specifically, for example, the following method can be listed, in which a first-stage washing step is performed using a treatment liquid manufactured by the manufacturing method of the present invention, and a second-stage washing step is performed using a second treatment liquid.

[0505] Alternatively, after the semiconductor substrate is cleaned (performing only one or more cleaning steps), a step of rinsing the semiconductor substrate with a solvent can be performed to clean it (hereinafter referred to as the "rinsing step").

[0506] The rinsing step is preferably performed immediately after the cleaning step of the semiconductor substrate, and consists of rinsing with a rinsing solvent (rinsing solution) for 5 seconds to 5 minutes. The rinsing step can also be performed using the mechanical stirring method described above.

[0507] Examples of rinsing solvents include: water (preferably deionized water), methanol, ethanol, isopropyl alcohol, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Alternatively, aqueous rinsing solutions with a pH value exceeding 8 (such as diluted aqueous ammonium hydroxide) can also be used.

[0508] As a method for contacting the rinsing solvent with the semiconductor substrate, the same method for contacting the treatment liquid with the semiconductor substrate can be applied.

[0509] Alternatively, a drying step to dry the semiconductor substrate can be performed after the rinsing step.

[0510] There are no particular limitations on the drying method. Examples include: rotary drying, a method of passing a drying gas through a semiconductor substrate, a method of heating the substrate by means of a heating plate or an infrared lamp-like heating mechanism, Marangoni drying, Rotagoni drying, IPA (isopropyl alcohol) drying, and any combination thereof.

[0511] [Example]

[0512] The present invention will now be described in more detail based on embodiments. The materials, amounts, and proportions shown in the following embodiments may be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the invention is not to be limited by the embodiments shown below.

[0513] In the following examples, the pH value was measured at 25°C using a pH meter (manufactured by Horiba Manufacturing Co., Ltd., model "F-74") in accordance with JIS Z8802-1984.

[0514] In addition, when manufacturing the treatment solutions of the examples and comparative examples, the operation, preparation, filling, storage and analysis of the containers were all carried out in a clean room that met the ISO Class 2 or lower standards.

[0515] [The raw materials of the refined product]

[0516] The following shows the compounds used in preparing the purified material for testing. Furthermore, all components used in the examples are either classified as semiconductor grade or as high-purity grades based on this classification. Additionally, the compounds used in preparing the second treatment solution, described later, are also shown below.

[0517] [Surfactants]

[0518] Among the surfactants listed below, anionic surfactants A and B are anionic surfactants, cationic surfactants A through E are cationic surfactants, and all other surfactants are nonionic surfactants.

[0519] .C12H25O(EO)nH:C12H25O(CH2CH2O)nH

[0520] (n is 6, 20, 30, or 50)

[0521] Anionic system A: C12H25O(CH2CH2O)10PO3H2

[0522] Anionic system B: C12H25O(CH2CH2O)7CH2COOH

[0523] Nonionic system X: The following compounds

[0524] [Chemistry 1]

[0525] Cation system A: Benzophenone chloride

[0526] Cation-based B: Quartamin 60W (manufactured by Kao Corporation)

[0527] Cationic C: Pionin B-0012-H (manufactured by Takemoto Oils & Fats Co., Ltd.)

[0528] Cationic D: Pionin B-251 (manufactured by Takemoto Oils & Fats Co., Ltd.)

[0529] Cation-based E: Surflon S-221 (manufactured by AGC Seimi Chemical Co., Ltd.)

[0530] Non-ionic Y: Blaunon S-204 (manufactured by Aoki Oils & Fats Co., Ltd.)

[0531] Non-ionic Z: Amite 320 (manufactured by Kao Corporation)

[0532] [Chlorinating agents]

[0533] adipic acid

[0534] succinic acid

[0535] malonic acid

[0536] .oxalic acid

[0537] Citric acid

[0538] Phthalic acid

[0539] Trimeric tricarboxylic acid

[0540] Pyromellitic acid

[0541] DTPA: Diethylenetriaminepentaacetic acid

[0542] HEDP: 1-Hydroxyethane-1,1-Diphosphonic acid

[0543] [Amine compounds]

[0544] MEA: Monoethanolamine

[0545] Tris: Tris(hydroxymethyl)aminomethane

[0546] .2-Aminopyrimidine

[0547] .2,4-Diaminopyrimidine

[0548] .2,4,6-Triaminepyrimidine

[0549] 2,6-Dihydroxypyridine

[0550] uracil

[0551] .cytosine

[0552] 〔additive〕

[0553] Polyacrylic acid (weight average molecular weight: 6000)

[0554] BYK 2012: Disperbyk 2012 (manufactured by BYK-Chemie).

[0555] BYK 2013: Disperbyk - 2013 (manufactured by BYK-Chemie).

[0556] DL-30 (Nippon Shokubai Manufacturing)

[0557] YS-100 (Made by Nippon Shokubai)

[0558] HL-415 (Made by Nippon Shokubai)

[0559] Aron-SD10 (manufactured by Dong-A Synthetic)

[0560] .P9300: DEQUEST P9300 (manufactured by Thermophos)

[0561] periodic acid

[0562] Sorbic acid

[0563] L-histidine

[0564] L-arginine

[0565] L-lysine

[0566] [pH adjuster, water]

[0567] In addition, in the preparation of the refined product (or the second treatment liquid described later), either potassium hydroxide (KOH) or sulfuric acid (H2SO4) as pH adjusters, and commercially available ultrapure water (manufactured by Fujifilm and Koichi Chemical Co., Ltd.) are used.

[0568] Furthermore, the content of pH adjuster (potassium hydroxide or sulfuric acid) in the purified product (or the second treatment solution described later) in any of the embodiments or comparative examples is less than 2% by mass relative to the total mass of the purified product (or the second treatment solution described later).

[0569] <<Examples 1-44, Comparative Example 1>>

[0570] [Manufacturing Tests of the Treatment Fluid]

[0571] [Filter Material]

[0572] The following shows the materials that the filters used in the tests may have.

[0573] Polyallyl sulfonic acid

[0574] .nylon

[0575] Perfluoroalkoxyalkanes after hydrophilic treatment

[0576] Polytetrafluoroethylene after hydrophilic treatment

[0577] Polyethylene after hydrophilic treatment

[0578] Polyvinylidene fluoride after hydrophilic treatment

[0579] Untreated PTFE: Polytetrafluoroethylene that has not undergone hydrophilic treatment.

[0580] In the case of the materials described, the hydrophilic treatment described as "after hydrophilic treatment" is carried out by contacting each material with plasma formed by oxygen.

[0581] [Experimental Procedure]

[0582] <Preparation of the refined product>

[0583] The components were mixed in the manner described in Table 1 below, with the amounts and pH values ​​as shown in the following section, to obtain the purified products used in each experiment. For example, in the purified product of Example 1, relative to the total mass of the purified product, it contained 1% by mass of a chelating agent (adipic acid), 0.1% by mass of a surfactant (Triton X-100), 3% by mass of an amine compound (MEA), and an amount of pH adjuster (potassium hydroxide or sulfuric acid) to set the pH value of the purified product to 6, with the remainder being water.

[0584] <Manufacturing of the treatment fluid>

[0585] The obtained 10L of each purified material is circulated and filtered using a filter (filter A only, or filter A and filter B) with the filter media as described in the table to obtain a processed liquid.

[0586] In this embodiment using both filter A and filter B, the following cyclic filtration is performed: the purified material is passed through the filter in the order of filter A and filter B, and the purified material filtered by filter B is circulated to the upstream side of filter A, and then filtered again in the order of filter A and filter B.

[0587] The cyclic filtering is implemented by repeating the process three times.

[0588] Furthermore, the filters used in the experiment (filter A and / or filter B) were pre-flushed with IPA (isopropyl alcohol), and then replaced with pure water before being used in the experiment.

[0589] For the obtained treatment solution, a liquid particle counter was used to count the number of particles (LPC) with a diameter of 100 nm (0.1 μm) or larger contained in 10 L of the obtained treatment solution.

[0590] The filtration performance of the examples or comparative examples was distinguished based on the LPC measured from the obtained processed liquid and the smoothness of circulation filtration, as shown below.

[0591] AAAA: The circulating filtration process ends without any problems, and the LPC of the treated liquid is less than 10.

[0592] AAA: The circulating filtration process ends without problems, and the LPC of the treated liquid is more than 10 and less than 20.

[0593] AA: The circulating filtration ends without any problems, and the LPC of the treated liquid is more than 20 and less than 30.

[0594] A: The circulating filtration ended without any problems, and the LPC of the treated liquid was more than 30 and less than 50.

[0595] B: The circulating filtration ends without any problems, and the LPC of the treated liquid is more than 50 and less than 100.

[0596] C: The circulating filtration ends without any problems, and the LPC of the treated liquid is more than 100 and less than 300.

[0597] D: After the circulation filtration begins, a short while later, bubble interlocking occurs due to bubbles originating from the purified material, and the filtration ends midway. (No treated solution obtained)

[0598] Furthermore, the number of particles with a diameter of 100 nm (0.1 μm) or larger (LPC) contained in 10 L of each purified product before filtration is 1 to 100.

[0599] [result]

[0600] The following table shows the formulation of the refined material, the type of filter used, the filtration pressure, and the evaluation results (filterability) in each embodiment or comparative example.

[0601] Furthermore, information regarding pH adjusters and water is omitted from the table.

[0602] Each refined product contains the amount of pH adjuster (either potassium hydroxide or sulfuric acid) required to achieve the pH value of each refined product as stated in the "pH value" column of the table. Furthermore, the content of pH adjuster in any refined product is less than 2% by mass relative to the total mass of the refined product.

[0603] The remaining portion of the refined product, excluding the components listed in the table and the pH adjuster, is water.

[0604] The "Amine Compounds / Surfactants" column in the table indicates the mass ratio of the amine compound content to the surfactant content.

[0605]

[0606]

[0607]

[0608]

[0609]

[0610]

[0611] As is evident from Table 1, it is confirmed that the manufacturing method of the present invention has good filtering properties.

[0612] In addition, it was confirmed that, in terms of excellent filtration performance, the pH value of the purified material is preferably 7 to 13, and more preferably 8 to 12 (refer to the results of Examples 1 to 9, etc.).

[0613] It was confirmed that, in terms of superior filtration, n in the base represented by Equation (1) is preferably 3 to 30, and more preferably 6 to 20 (refer to the results of Examples 15 to 18, etc.).

[0614] It was confirmed that, in terms of superior filtration performance, the purified material preferably contains an aliphatic carboxylic acid chelating agent with 3 or more carbon atoms (see the results of Examples 5, 37 to 44, etc.).

[0615] It was confirmed that, in terms of superior filterability, the mass ratio of the content of the amine compound to the content of the surfactant in the purified product is preferably 1 to 3000, more preferably 2 to 1000 (refer to the results of Examples 5, 19 to 24, etc.).

[0616] It was confirmed that, in terms of superior filtration performance, the first filter material preferably comprises at least one of the group consisting of nylon, polyallyl sulfonic acid, hydrophilicated perfluoroalkoxyalkane, and hydrophilicated polytetrafluoroethylene, and more preferably comprises polyallyl sulfonic acid (see the results of Examples 5, 10 to 14, etc.).

[0617] It was confirmed that, in terms of superior filtration performance, it is preferable to use a first filter containing a first filter material and a second filter containing a second filter material for filtering the refined material (see the results of Examples 5, 32 to 36, etc.).

[0618] It was confirmed that, in terms of superior filtration performance, the pore size of the second filter material is preferably larger than that of the first filter material, and the purified material is filtered by passing liquid through the second filter and the first filter in sequence (see the results of Examples 33, 35, and 36, etc.).

[0619] It was confirmed that, in terms of particularly excellent filtration performance, the second filter material preferably comprises at least one selected from the group consisting of nylon and polyallyl sulfonic acid, and more preferably comprises polyallyl sulfonic acid (see the results of Examples 32 to 34, etc.).

[0620] It was confirmed that, in terms of superior filtration performance, the filtration pressure is preferably 0.05 MPa or higher and 0.4 MPa or lower (refer to the results of Examples 5, 28, and 29, etc.).

[0621] <<Examples 45~68>>

[0622] Then, the prepared processing solution was used to perform a cleaning test on the semiconductor substrate after CMP treatment.

[0623] [test]

[0624] [Manufacturing of the treatment fluid]

[0625] The treatment liquid (the treatment liquid of Example 1) was prepared using the method described in Example 1.

[0626] [Manufacturing of the second treatment fluid]

[0627] The components listed in Table 2, along with water and a pH adjuster (potassium hydroxide or sulfuric acid), were mixed to obtain the second treatment solution used in each test, in the manner described in Table 2 below, with the same content and pH value. For example, in the second treatment solution of Example 46, relative to the total mass of the second treatment solution, it contained 3% by mass of a chelating agent (citric acid), 4.75% by mass of an amine compound (Tris), 0.05% by mass of sorbic acid, and an amount of pH adjuster (potassium hydroxide or sulfuric acid) to set the pH value of the second treatment solution to 6, with the remainder being water.

[0628] Furthermore, in Example 45, the second treatment liquid is not used.

[0629] [Evaluation of Cleansing Properties]

[0630] The semiconductor substrate with a metal film after chemical mechanical polishing was cleaned using the processing solution (the processing solution of Example 1 and the second processing solution) prepared by the method described above, and the cleaning performance (defect suppression performance) was evaluated.

[0631] First, take 1L of the treatment solution from Example 1 and dilute it with ultrapure water at a volume ratio of 100 times to prepare a sample of the diluted treatment solution.

[0632] In addition, 1L of the second treatment solution from each embodiment was taken and diluted with ultrapure water by a ratio of 100 times by volume to prepare a sample of the diluted second treatment solution.

[0633] Furthermore, the pH value of the diluted treatment solution is above 6 and below 7.

[0634] In addition, in any embodiment, the pH value of the diluted second treatment solution is greater than and less than 7, which is the pH value of the second treatment solution before dilution.

[0635] Using a FREX300S-II polishing unit (manufactured by Ebara Corporation), a silicon wafer (10-inch diameter) with a tungsten-containing metal film on its surface was polished under the following conditions: polishing pressure set to 2.0 psi, polishing slurry supply rate set to 0.28 ml / (min.cm2), and polishing time set to 60 seconds. W2000 (trade name, manufactured by Cabot Corporation) was used as the polishing slurry.

[0636] Subsequently, the diluted treatment solution of Example 1, adjusted to room temperature (23°C), was used to scrub and clean for 60 seconds (first stage cleaning step), followed by scrubbing and cleaning for 60 seconds using any of the diluted second treatment solutions of each example (second stage cleaning step), and then drying.

[0637] In Example 45, the washing step using a diluted second treatment solution was omitted.

[0638] The number of defects in the polished surface of the obtained wafer is detected using a defect detection device. Each defect is observed using a scanning electron microscope (SEM) and classified. If necessary, the constituent elements are analyzed using an energy dispersive X-ray analyzer (EDAX) to determine the composition.

[0639] In this way, the number of defects based on metal residues (residues mainly composed of metal), the number of defects based on organic residues (residues mainly composed of organic matter), and the number of defects based on corrosion of the tungsten (metal film) surface were calculated in the polished surface of the wafer. The calculated defect numbers were classified according to the following distinctions, and the cleanliness (defect suppression) of each embodiment was evaluated.

[0640] A: The number of defects in the object is less than 20.

[0641] B: The number of object defects exceeds 20 but is less than 30.

[0642] C: The number of object defects exceeds 30 but is less than 50

[0643] D: Number of object defects exceeds 50

[0644] [result]

[0645] The following table shows the preparation of the second treatment solution (the second treatment solution before dilution) and the test results in each embodiment.

[0646] Furthermore, information regarding pH adjusters and water is omitted from the table.

[0647] Each secondary treatment solution contains the amount of pH adjuster (either potassium hydroxide or sulfuric acid) required to achieve the pH value as specified in the "pH Value" column of the table. Furthermore, the content of the pH adjuster in any secondary treatment solution is less than 2% by mass relative to the total mass of the secondary treatment solution.

[0648] The remaining portion of the second treatment solution, excluding the components listed in the table and the pH adjuster, is water.

[0649]

[0650] Based on the results of Examples 45 to 68, it was confirmed that the processing liquid manufactured using the manufacturing method of the present invention has good cleaning properties (defect suppression properties) when applied to semiconductor substrates after chemical mechanical polishing (CMP) treatment.

[0651] It was found that better cleaning performance can be achieved by performing cleaning with a treatment liquid manufactured by the manufacturing method of the present invention and cleaning with a second treatment liquid.

[0652] Furthermore, it was confirmed that when the second treatment liquid contains two or more polymers, better cleaning performance can be achieved (see the results of Example 68, etc.).

[0653] <<Examples 69~101>>

[0654] Then, the prepared processing solution was used to perform a cleaning test on the semiconductor substrate after CMP treatment.

[0655] [test]

[0656] [Manufacturing of the treatment fluid]

[0657] The treatment liquid (the treatment liquid of Example 1) was prepared using the method described in Example 1.

[0658] [Manufacturing of the second treatment fluid]

[0659] The components listed in Table 3, along with water and a pH adjuster (potassium hydroxide or sulfuric acid), are mixed to produce the second treatment solution used in each test, in the manner described in Table 3 below, with the same content and pH value. For example, in the second treatment solution of Example 46, relative to the total mass of the second treatment solution, it contains 3% by mass of a chelating agent (citric acid), 4.2% by mass of an amine compound (Tris), 0.05% by mass of sorbic acid, 1.5% by mass of an amino acid (L-histidine), and an amount of pH adjuster (potassium hydroxide or sulfuric acid) to set the pH value of the second treatment solution to 6, with the remainder being water.

[0660] [Evaluation of Cleansing Properties]

[0661] Using the processing solution (processing solution of Example 1 and second processing solution) manufactured by the method described above, the semiconductor substrate with metal film after chemical mechanical polishing was cleaned according to the method described in Examples 45 to 68, and the cleaning performance (defect suppression performance) was evaluated.

[0662] Furthermore, 1L of the second treatment liquid from each embodiment was taken and diluted with ultrapure water at a volume ratio of 100 times. The pH value of the diluted second treatment liquid obtained in this way was higher than and less than 7 of the pH value of the second treatment liquid before dilution in any embodiment.

[0663] [result]

[0664] The following table shows the preparation of the second treatment solution (the second treatment solution before dilution) and the test results in each embodiment.

[0665] Furthermore, information regarding pH adjusters and water is omitted from the table.

[0666] Each secondary treatment solution contains the amount of pH adjuster (either potassium hydroxide or sulfuric acid) required to achieve the pH value as specified in the "pH Value" column of the table. Furthermore, the content of the pH adjuster in any secondary treatment solution is less than 2% by mass relative to the total mass of the secondary treatment solution.

[0667] The remaining portion of the second treatment solution, excluding the components listed in the table and the pH adjuster, is water.

[0668]

[0669]

[0670] Based on the results of Examples 69 to 101, it was confirmed that the processing liquid manufactured using the manufacturing method of the present invention has good cleaning properties (defect suppression properties) when applied to a semiconductor substrate after chemical mechanical polishing (CMP) treatment.

[0671] It was found that better cleaning performance can be achieved by performing cleaning with a treatment liquid manufactured by the manufacturing method of the present invention and cleaning with a second treatment liquid.

[0672] Furthermore, it was confirmed that when the second treatment solution contains two or more specific nitrogen-containing compounds and polycarboxylic acids, better cleaning performance can be achieved (see the results of Examples 78 to 101, etc.).

[0673] 40: Filter

[0674] 41: Filter media

[0675] 42:Core

[0676] 43: Cover

[0677] 44: Liquid outlet

Claims

1. A method for manufacturing a processing liquid, wherein a first filter having a first filter material is used to filter a purified material containing a surfactant to manufacture a processing liquid for a semiconductor substrate, wherein the first filter material comprises at least one selected from the group consisting of polyallyl sulfonic acid and perfluoroalkoxyalkanes subjected to hydrophilic treatment, the pore size of the first filter material is 50 μm or less, the surfactant comprises at least one selected from the group consisting of a nonionic surfactant containing a base represented by formula (1) and an anionic surfactant containing a base represented by formula (1), the content of the surfactant is 0.00001% by mass to 10% by mass relative to the total mass of the purified material, the pH value of the purified material is 6 to 14, and formula (1) (LO)n In formula (1), L represents an alkyl group; n represents 6 to 20.

2. A method for manufacturing a processing liquid as claimed in claim 1, wherein the processing liquid is applied to a semiconductor substrate after chemical mechanical polishing.

3. A method for manufacturing a treatment liquid as described in claim 1 or claim 2, wherein the purified material further comprises an amine compound.

4. A method for manufacturing the treatment liquid as claimed in claim 3, wherein the mass ratio of the content of the amine compound to the content of the surfactant in the purified product is 2 to 1000.

5. A method for manufacturing a treatment liquid as claimed in claim 1 or claim 2, wherein the nonionic surfactant and the anionic surfactant comprise a group represented by formula (2), where -Ph-O-(LO)n- in formula (2), Ph represents phenyl; L represents alkyl; and n represents 3 to 55.

6. A method for manufacturing a treatment liquid as claimed in claim 1 or claim 2, wherein the purified material comprises an aliphatic carboxylic acid chelating agent having 3 or more carbon atoms.

7. A method for manufacturing a treatment liquid as described in claim 1 or claim 2, wherein the pH value of the purified substance is 8 to 12.

8. A method for manufacturing a treatment liquid as claimed in claim 1 or claim 2, wherein the first filter material comprises at least one selected from the group consisting of the nylon, the polyallyl sulfonic acid, the hydrophilically treated perfluoroalkoxyalkane, and the hydrophilically treated polytetrafluoroethylene.

9. A method for manufacturing a treatment liquid as described in claim 1 or claim 2, wherein the first filter material comprises the polyallyl sulfonic acid.

10. A method for manufacturing a processing liquid as claimed in claim 1 or claim 2, wherein the purified material is filtered using the first filter and a second filter comprising a second filter material different from the first filter.

11. A method for manufacturing a processing liquid as claimed in claim 10, wherein the pore size of the second filter material is larger than that of the first filter material, and the refined material is filtered by passing the liquid through the second filter and the first filter in sequence.

12. A method for manufacturing a treatment liquid as claimed in claim 11, wherein the ratio of the pore size of the second filter material to the pore size of the first filter material is 2 to 500.

13. A method for manufacturing a treatment liquid as described in claim 1 or claim 2, wherein the filtration pressure of the purified material performed using the first filter is 0.4 MPa or less.

14. A method for manufacturing a treatment liquid as described in claim 1 or claim 2, wherein the filtration pressure of the purified material performed using the first filter is 0.05 MPa or higher.

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