Composition

Abstract

The objective of this invention is to provide a composition with a high Ru / W ratio and excellent Ru solubility. The composition of this invention comprises hypochlorous acid or a salt thereof, a first onium salt compound, and one or more compounds X selected from the group consisting of a second onium salt compound having a cyclic structure (including a compound different from the first onium salt compound), a resin A containing repeating units having an onium salt structure (different from the first onium salt compound), and a compound B having a nitrogen atom but not an onium salt structure.

Description

[Technical Field]

[0001] This invention relates to a composition. [Previous Technology]

[0002] When forming circuits and components, an etching process using components such as solutions is usually performed. At this time, there are sometimes multiple materials on the substrate, so it is better to use a component for etching that can selectively remove only specific materials.

[0003] In recent years, ruthenium (hereinafter also referred to as "Ru") has been used as an electrode material and wiring material for semiconductor devices. Like other wiring materials, it is necessary to carry out a process to remove Ru present in unwanted parts. In the process of removing Ru, components are often used.

[0004] For example, Patent Document 1 discloses a semiconductor processing solution containing ruthenium hypochlorite ions.

[0005] [Patent Document 1] International Publication No. 2021 / 059666

[0006] Ru can be used in wiring materials, etc. On the other hand, tungsten (hereinafter, also referred to as "W") can sometimes be used in wiring materials, etc. In cases where both Ru and W are present on a substrate such as a semiconductor, it is difficult to corrode W, and Ru needs to be selectively removed. Specifically, a high ratio of Ru dissolution rate to W dissolution rate (hereinafter, also referred to as "Ru / W") is required. Furthermore, excellent Ru dissolution ability (Ru dissolution rate) is also required.

[0007] The inventors have studied the composition described in Patent Document 1 and found that it is difficult to balance both Ru / W and Ru solubility, and further improvements are needed. [Summary of the Invention]

[0008] Therefore, the objective of the present invention is to provide a composition with a high Ru / W ratio and excellent Ru solubility.

[0009] The inventors conducted in-depth research to solve the above-mentioned problems, and as a result, completed the present invention. That is, they discovered that the above-mentioned problems can be solved by the following configuration.

[0010] [1] A composition comprising: hypochlorous acid or a salt thereof; a first onium salt compound; and one or more compounds X selected from the group consisting of a second onium salt compound having a cyclic structure, a resin A having a repeating unit having an onium salt structure, a compound B having a nitrogen atom and not having an onium salt structure. [2] The composition as described in [1], wherein the first onium salt compound is a compound represented by any one of the following formulas (Z1) to (Z3). [3] The composition as described in [2], wherein the first onium salt compound is a compound represented by the above formula (Z1) or the above formula (Z3), and A Z11, A Z31 and A Z32 are nitrogen atoms. [4] The composition as described in [2] or [3], wherein the first onium salt compound is a compound represented by formula (Z1) or formula (Z3), and R Z11 to R Z14 and R Z31 to R Z36 are each independently a linear alkyl group that may have substituents. [5] The composition as described in any one of [2] to [4], wherein the first onium salt compound is a compound represented by formula (Z1) or formula (Z3), and R Z11 to R Z14 and R Z31 to R Z36 are each independently an alkyl group having 1 to 18 carbon atoms that may have substituents. [6] The composition as described in any one of [2] to [5], wherein the first onium salt compound is a compound represented by formula (Z1) or formula (Z3), and R Z11 to R Z14 and R Z31 to R Z36 are each independently alkyl groups having 1 to 10 carbon atoms that may have substituents. [7] The composition as described in any one of [1] to [6], wherein the compound X is selected from one or more compounds selected from the group consisting of resin A, the second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, biguanide compounds, alkanolamine compounds, amino acids, aliphatic amine compounds, alicyclic amine compounds, polyamino polycarboxylic acids, azole compounds, guanidine compounds, quinoline compounds and pyridine compounds. [8] The composition as described in any one of [1] to [7], wherein the compound X is selected from one or more compounds selected from the group consisting of the resin A, the second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, biguanide compounds, alkanolamine compounds, amino acids, aliphatic amine compounds, alicyclic amine compounds and polyamine polycarboxylic acids. [9] The composition as described in any one of [1] to [8], wherein the compound X is selected from one or more compounds selected from the group consisting of the resin A, the second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, biguanide compounds and alkanolamine compounds.

[10] The composition of any one of [7] to [9], wherein the weight average molecular weight of the resin A and the resin B is 1,000 to 200,000.

[11] The composition of any one of [7] to

[10] , wherein the resin B comprises a repeating unit having a nitrogen atom.

[12] The composition of any one of [1] to

[10] , wherein the resin A comprises a repeating unit having an onium salt structure, the repeating unit having a cationized nitrogen atom.

[13] The composition of

[12] , wherein the resin A comprises a repeating unit having a quaternary ammonium salt structure.

[14] The composition of

[13] , wherein the resin comprises a repeating unit of A having a quaternary ammonium salt structure in the main chain.

[15] The composition of any one of [1] to

[14] , further comprising a compound having a carbonyl group that is different from the first onium salt compound and the compound X.

[16] The composition of any one of [1] to

[15] , wherein the mass ratio of the content of the hypochlorous acid or its salt to the content of the compound X is 1 to 10,000.

[17] The composition of any one of [1] to

[16] , wherein the pH is 7.0 to 14.0.

[18] The composition of any one of [1] to

[17] substantially does not contain abrasive particles.

[19] The composition of any one of [1] to

[18] is used for a processed material containing ruthenium. [Effects of the Invention].

[0011] The present invention can provide a composition with high Ru / W ratio and excellent Ru solubility.

Implementation Method

[0013] Hereinafter, the present invention will be described in detail. The description of the constituent elements set forth below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0014] The following explains the meaning of each statement in this specification. In this specification, the numerical range indicated by “~” refers to the range including the values ​​before and after “~” as the lower and upper limits. In this specification, “ppm” is an abbreviation for “parts per million” and refers to 10⁻⁶. Also, “ppb” is an abbreviation for “parts per billion” and refers to 10⁻⁹. “ppt” is an abbreviation for “parts per trillion” and refers to 10⁻¹².

[0015] Unless otherwise specified, “exposure” includes exposure based on mercury lamps, far-ultraviolet light such as excimer lasers, X-rays or EUV light, and depiction based on particle beams such as electron beams or ion beams. “Preparation” includes not only the synthesis and blending of specific materials, but also the acquisition of predetermined items through purchase.

[0016] Unless otherwise stated, the compounds described in this specification may include structural isomers (compounds with the same number of atoms but different structures), optical isomers, and isotopes. Furthermore, the isomers and isotopes may include one or more types. In this specification, dry etching residue refers to byproducts generated by dry etching (e.g., plasma etching), such as organic residues derived from photoresist, Si-containing residues, and metal-containing residues (e.g., transition metal-containing residues). In this specification, unless otherwise stated, the bonding orientation of divalent groups (e.g., -COO-) is such that, when Y in the compound represented by "XYZ" is -COO-, the compound can be either "XO-CO-Z" or "X-CO-OZ". In this specification, unless otherwise stated, substituents may be monovalent or divalent or higher, with monovalent substituents being preferred.

[0017] In this specification, unless otherwise stated, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​obtained by converting the polystyrene content of the standard material measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all manufactured by TOSOH CORPORATION) as the column, tetrahydrofuran as the eluent, a differential refractometer as the detector, and polystyrene as the standard material. In this specification, unless otherwise stated, the molecular weight of compounds having a molecular weight distribution is the weight-average molecular weight (Mw).

[0018] <Composition> The composition of the present invention comprises hypochlorous acid or a salt thereof, a first onium salt compound, and one or more compounds X selected from the group consisting of a second onium salt compound having a cyclic structure (hereinafter, simply referred to as "the second onium salt compound"), a resin A having a repeating unit having an onium salt structure, a compound different from the first onium salt compound, and a compound B having a nitrogen atom but not having an onium salt structure. When the composition is the present invention, the mechanism by which the desired effect of the present invention can be obtained is not necessarily clear, but the inventors speculate as follows. Regarding the composition, the solubility of Ru and W is improved by hypochlorous acid or a salt thereof and the first onium salt compound, and on the other hand, the solubility of W can be suppressed by compound X. Therefore, it is speculated that the Ru / W ratio is high and the Ru solubility is also excellent. Hereinafter, the effect of at least one of the increased Ru / W ratio and the excellent Ru solubility will be obtained, also referred to as "the excellent effect of the present invention". Furthermore, as mentioned above, Ru / W represents the ratio of the dissolution rate of Ru to the dissolution rate of W. The various components that can be included in the composition are described in detail below.

[0019] [Hypochlorous acid or its salt] The composition contains hypochlorous acid or its salt. Examples of hypochlorous acid or its salt include hypochlorous acid and inorganic salts of hypochlorous acid containing alkali metals and alkaline earth metals, with sodium hypochlorite, potassium hypochlorite, or calcium hypochlorite being preferred. In the composition, hypochlorous acid or its salt may be in the form of hypochlorite ions (ClO-). In the composition, when hypochlorous acid or its salt is a hypochlorite ion, it may also form salts with various components of the composition described below.

[0020] Hypochlorous acid or its salts may be used alone or in combination with two or more. The content of hypochlorous acid or its salts relative to the total mass of the composition is typically 0.02–20% by mass, preferably 0.05–20% by mass, more preferably 0.1–15% by mass, and further preferably 1–10% by mass. When hypochlorous acid or its salts are hypochlorous acid ions, the content of hypochlorous acid ions relative to the total mass of the composition is typically 0.02–20% by mass, preferably 0.05–20% by mass, more preferably 0.1–15% by mass, and further preferably 1–10% by mass. The aforementioned hypochlorous acid or its salts and the aforementioned hypochlorous acid ions can be determined, for example, using known methods such as ion chromatography.

[0021] [First Onium Salt Compound] The composition includes a first onium salt compound. The first onium salt compound is a compound that is different from the various components mentioned above.

[0022] The first onium salt compound has an onium salt structure consisting of a cation and an anion. The cation can be any of an organic cation and an inorganic cation, with an organic cation being preferred. The valence of the cation can be monovalent or divalent or higher, with monovalent being preferred. Examples of cations include quaternary ammonium cations (preferably tetraalkylquaternary ammonium cations), phosphonium cations, strontium cations, imidazolium cations, pyrrolidine onium cations, pyridinium cations, piperidinium cations, fluoroonium cations, chloroonium cations, bromonium cations, iodonium cations, positive oxygen cations, selenonium cations, tellurium cations, arsonium cations, antimonyonium cations, and bismuthonium cations, with quaternary ammonium cations, strontium cations, or phosphonium cations being preferred, and quaternary ammonium cations being more preferred. The anion can be either organic or inorganic, with inorganic anions being preferred. The anion can be monovalent or divalent or higher, with monovalent being preferred. Examples of anions include halides such as fluoride ions, chloride ions, bromide ions, and iodide ions, as well as hydroxide ions, nitrate ions, phosphate ions, sulfate ions, hydrogen sulfate ions, methanesulfate ions, perchlorate ions, chlorate ions, chlorite ions, hypochlorous acid ions, bromite ions, bromate ions, periodate ions, partial periodate ions, iodate ions, iodate ions, hypoiodate ions, acetate ions, carbonate ions, bicarbonate ions, fluoroborate ions, and trifluoroacetic acid ions, with halide or hydroxide ions being preferred.

[0023] As the first onium salt compound, a quaternary ammonium salt compound (preferably a tetraalkyl quaternary ammonium salt compound), a phosphonium salt compound, or a strontium salt compound is preferred. From the viewpoint of superior effect of the present invention, a compound represented by any one of formulas (Z1) to (Z3) is more preferred, a compound represented by formula (Z1) or a compound represented by formula (Z3) is further preferred, and a compound represented by formula (Z1) is particularly preferred.

[0024] [Chemical 1]

[0025] In formula (Z1), AZ11 represents a nitrogen atom or a phosphorus atom. RZ11 to RZ14 each independently represent an alkyl group that may have substituents or an aryl group that may have substituents. XZ11 represents an anion. In formula (Z2), RZ21 to RZ23 each independently represent an alkyl group that may have substituents or an aryl group that may have substituents. XZ21 represents an anion. In formula (Z3), AZ31 and AZ32 each independently represent a nitrogen atom or a phosphorus atom. RZ31 to RZ36 each independently represent an alkyl group that may have substituents or an aryl group that may have substituents. nZ31 represents an integer from 1 to 10. XZ31 represents an anion.

[0026] In formula (Z1), AZ11 represents a nitrogen atom or a phosphorus atom. That is, AZ11+ in formula (Z1) represents N+ or P+. Nitrogen atom is preferred as AZ11. When AZ11 is a nitrogen atom, "AZ11+" in formula (Z1) refers to a quaternary ammonium cation. When AZ11 is a phosphorus atom, "AZ11+" in formula (Z1) refers to a phosphorus cation.

[0027] R Z11 to R Z14 independently represent alkyl groups that may have substituents or aryl groups that may have substituents. The alkyl group can be linear, branched, or cyclic, with linear being preferred. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 18, and even more preferably 1 to 10. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl. Substituents that the alkyl group may have include halogen atoms such as fluorine and chlorine atoms, hydroxyl, alkenyl, alkoxy, and groups combining these. The substituents may also have other substituents (e.g., the substituents and alkyl groups). Examples of alkyl groups with substituents include allyl, alkoxy, 2-hydroxyethyl, and 2-hydroxypropyl. The methylene group constituting the above-mentioned alkyl group can be substituted with a divalent linker such as -O-. As the above-mentioned alkyl group, a straight-chain alkyl group having substituents is preferred, and a straight-chain alkyl group without substituents is even more preferred. Furthermore, as the above-mentioned alkyl group, an alkyl group having 1 to 18 carbon atoms having substituents (preferably unsubstituted) is also preferred, and an alkyl group having 1 to 10 carbon atoms having substituents (preferably unsubstituted) is even more preferred. When R Z11 to R Z14 represent alkyl groups that can have substituents, it is preferable that at least one of the alkyl groups represented by R Z11 to R Z14 has 2 or more carbon atoms.

[0028] The aryl group described above can be either monocyclic or polycyclic, with monocyclic being preferred. The ring number of the aryl group is preferably 5 to 20, and more preferably 5 to 8. The carbon number of the aryl group is preferably 6 to 30, more preferably 6 to 18, and even more preferably 6 to 10. Examples of the aryl group include benzyl, naphthyl, anthracene, and pyrene, with benzyl being preferred. Substituents that the aryl group may have include, for example, halogen atoms such as fluorine and chlorine atoms, hydroxyl, alkyl, alkenyl, alkoxy, and groups combining these, with halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkoxy groups having 1 to 9 carbon atoms, or alkenyloxy groups having 2 to 9 carbon atoms being preferred. The substituent group may also have substituents (e.g., the aforementioned substituents). An unsubstituent aryl group is also preferred. The total carbon number of R Z11 to R Z14 is preferably 4 to 100, even better is 4 to 72, and further better is 4 to 40.

[0029] X Z11 - represents anion. Examples of the anions described above include monovalent anions found in the first onium salt compound, with halide ions or hydroxide ions being preferred.

[0030] In formula (Z2), R Z21 to R Z23 independently represent an alkyl group that may have substituents or an aryl group that may have substituents. Examples of the alkyl group and the aryl group represented by any one of R Z11 to R Z14 can be cited as examples.

[0031] X Z21 - represents an anion. Examples of such anions include those possessed by the first onium salt compound, preferably monovalent anions, halide ions, or hydroxide ions.

[0032] In formula (Z3), AZ31 and AZ32 independently represent nitrogen atoms or phosphorus atoms, respectively. That is, AZ31+ and AZ32+ in formula (Z3) independently represent N+ or P+, respectively. Nitrogen atoms are preferred as AZ31 and AZ32. When AZ31 and AZ32 are nitrogen atoms, "AZ31+" and "AZ32+" in formula (Z3) refer to quaternary ammonium cations. When AZ31 and AZ32 are phosphorus atoms, "AZ31+" and "AZ32+" in formula (Z3) refer to phosphonium cations.

[0033] R Z31 to R Z36 each independently represent an alkyl group that may have substituents or an aryl group that may have substituents. Examples of the alkyl and aryl groups represented by any one of R Z11 to R Z14 can be cited as examples.

[0034] n Z31 represents an integer from 1 to 10. As n Z31, integers from 1 to 8 are preferred, and integers from 1 to 5 are even better.

[0035] X Z31 - represents an anion. Examples of the anions described above include monovalent anions found in the first onium salt compound, with halide ions or hydroxide ions being preferred.

[0036] From the viewpoint of further superior effect of the present invention, it is preferable that the first onium salt compound is represented by formula (Z1) or formula (Z3), and satisfies at least one of requirements 1 to 4. Requirement 1: A Z11, A Z31, and A Z32 are nitrogen atoms. Requirement 2: R Z11 to R Z14 and R Z31 to R Z36 are each independently a linear alkyl group that may have substituents. Requirement 3: R Z11 to R Z14 and R Z31 to R Z36 are each independently an alkyl group with 1 to 18 carbon atoms that may have substituents. Requirement 4: R Z11 to R Z14 and R Z31 to R Z36 are each independently an alkyl group with 1 to 10 carbon atoms that may have substituents.

[0037] Examples of the first onium salt compound include the second onium salt compound described later and resin A described later. As the first onium salt compound, a quaternary ammonium salt compound is preferred, a tetraalkyl quaternary ammonium salt compound or a quaternary ammonium salt compound having a cyclic structure containing a cationized nitrogen atom as a ring member (preferably a pyrrolidine onium salt compound) is more preferred, and a tetraalkyl quaternary ammonium salt compound is even more preferred. Regarding quaternary ammonium salt compounds having a cyclic structure containing a cationized nitrogen atom as a ring member, the second onium salt compound is described later. It is preferred that the carbon number of any alkyl group constituting the above-mentioned tetraalkyl quaternary ammonium salt compound is 1 to 30, more preferably 1 to 18, and even more preferably 1 to 10. Examples of first-order onium salt compounds include tetramethylammonium salts, tetrabutylammonium salts, ethyltrimethylammonium salts, triethylmethylammonium salts, diethyldimethylammonium salts, tributylmethylammonium salts, dimethyldipropylammonium salts, dodecyltrimethylammonium salts, hexadecyltrimethylammonium salts, benzyltrimethylammonium salts, benzyltriethylammonium salts, (2-hydroxyethyl)trimethylammonium salts, (2-hydroxyethyl)triethylammonium salts, diethylbis(2-hydroxyethyl)ammonium salts, and ethyltri(2-)trimethylammonium salts. Hydroxyethyl)ammonium salt compounds, tris(2-hydroxyethyl)methylammonium salt compounds, tetrapropylammonium salt compounds, n-octyltrimethylammonium salt compounds, tetramethylammonium salt compounds, tetraethylammonium salt compounds, hexamethylammonium salt compounds, decyltrimethylammonium salt compounds, didecyltrimethylammonium salt compounds, octadecyltrimethylammonium salt compounds, tetradecyltrimethylammonium salt compounds, eicosyltrimethylammonium salt compounds, tetrabutylphosphonium salt compounds, triphenylsilane salt compounds, butyltriphenylphosphonium salt compounds, trimethylphenylammonium salt compounds, and 1-butyl-1-methylpyrrolidineonium salt compounds.The first onium salt compound is preferably a compound selected from the group consisting of tetrapropylammonium hydroxide, n-octyltrimethylammonium chloride, tetrapropylammonium chloride, tetramethylammonium hydroxide, tetraethylammonium chloride, hexamethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, eicosyltrimethylammonium chloride, tetrabutylphosphonium hydroxide, triphenylsilane chloride, butyltriphenylphosphonium chloride, trimethylphenylammonium hydroxide, and 1-butyl-1-methylpyrrolidine onium chloride, and preferably selected from the group consisting of tetrapropylammonium hydroxide, n-octyltrimethylammonium chloride, tetrapropylammonium chloride, tetramethylammonium hydroxide, tetraethylammonium chloride, hexamethylammonium chloride, decyltrimethylammonium chloride, etc. Compounds selected from the group consisting of dodecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, and eicosyltrimethylammonium chloride are preferred; compounds selected from the group consisting of tetrapropylammonium hydroxide, n-octyltrimethylammonium chloride, tetrapropylammonium chloride, tetramethylammonium hydroxide, tetraethylammonium chloride, hexamethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, and tetradecyltrimethylammonium chloride are further preferred; and compounds selected from the group consisting of tetrapropylammonium hydroxide, n-octyltrimethylammonium chloride, tetrapropylammonium chloride, tetramethylammonium hydroxide, tetraethylammonium chloride, hexamethylammonium chloride, and decyltrimethylammonium chloride are particularly preferred.

[0038] It is preferable that the molecular weight of the first onium salt compound is 90 to 2,000, and even more preferably 90 to 1,000.

[0039] The first onium salt compound may be used alone or in combination with two or more. The content of the first onium salt compound relative to the total mass of the composition is preferably 0.001 to 50% by mass, more preferably 0.1 to 50% by mass, further preferably 1 to 30% by mass, and especially preferably 1 to 20% by mass.

[0040] [Compound X] The composition comprises compound X. Compound X is one or more compounds selected from the group consisting of a second onium salt compound, resin A, and compound B. It is preferable that compound X is one or more compounds selected from the group consisting of resin A, a second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, biguanide compound, alkanolamine compound, amino acid, aliphatic amine compound, alicyclic amine compound, polyamino polycarboxylic acid, azole compound, guanidine compound, quinoline compound, pyridine compound, indole compound, and carbazole compound, and is selected from the group consisting of resin A, a second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, biguanide compound, alkanolamine compound, amino acid, aliphatic amine compound, etc. It is more preferable to select one or more compounds from the group consisting of alicyclic amine compounds, polyamino polycarboxylic acids, azole compounds, guanidine compounds, quinoline compounds and pyridine compounds; it is further preferable to select one or more compounds from the group consisting of resin A, a second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, biguanide compounds, alkanolamine compounds, amino acids, aliphatic amine compounds, alicyclic amine compounds and polyamino polycarboxylic acids; it is especially preferable to select one or more compounds from the group consisting of resin A and a second onium salt compound; and resin A is the most preferred.

[0041] (Second Onium Salt Compound) The second onium salt compound is a compound different from the first onium salt compound, and is an onium salt compound having a cyclic structure. The second onium salt compound is a component different from the above-mentioned components.

[0042] The second onium salt compound has a cyclic structure and is an onium salt structure composed of cations and anions. Examples of the cations and anions described above include those of the first onium salt compound. The cyclic structure can be a cyclic structure containing cationized atoms as ring members, or a cyclic structure containing no cationized atoms as ring members. That is, the second onium salt compound can be a compound having a cyclic structure containing cationized atoms as ring members, or a compound having a cyclic structure containing cationized atoms other than ring members. Specifically, the second onium salt compound can be 1-butyl-1-methylpyrrolidine onium chloride, which has a pyrrolidine onium cation containing cationized nitrogen atoms as ring members; or benzalkonium chloride, which has a quaternary ammonium cation containing cationized nitrogen atoms other than ring members and a benzene ring as a cyclic structure.

[0043] The above-mentioned cyclic structure is either a monocyclic or polycyclic ring. It is preferred that the number of ring members in the above-mentioned cyclic structure is 3 to 15, more preferably 5 to 10, and even more preferably 5 or 6. As the ring constituting the above-mentioned cyclic structure, an alicyclic, aromatic, or heterocyclic ring is preferred, with aromatic or heterocyclic rings being more preferred. Examples of the above-mentioned alicyclic rings include cyclohexane rings, cycloheptene rings, cyclooctane rings, cyclododecane rings, and cyclodocosahexanes. Examples of the above-mentioned aromatic rings include benzene rings, naphthalene rings, anthracene rings, and pyrene rings, with benzene rings being preferred. The above-mentioned heterocyclic ring can be either non-aromatic or aromatic. Examples of heteroatoms in the above-mentioned heterocyclic ring include nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms, with nitrogen atoms being preferred. Examples of the aforementioned heterocycles include aromatic heterocycles such as furan rings, thiophene rings, pyrrole rings, acetazole rings, isoacetazole rings, acediazole rings, thiazole rings, isothiazole rings, thiadiazole rings, imidazole rings, pyrazole rings, triazole rings, furazolidone rings, tetraazole rings, pyridine rings, pyrazolidine rings, pyrimidine rings, pyrazolidine rings, triazolidine rings, tetraazolidine rings, and benzothiazole rings; and non-aromatic heterocycles such as pyrrolidine rings, pyrazolidine rings, imidazoleidine rings, piperidine rings, piperidine rings, tetrahydrofuran rings, and diacetyl rings, with pyridine, pyrazolidine, or pyrimidine rings being preferred. It is preferable that at least one of the heteroatoms constituting the aforementioned heterocycle is cationized. In other words, it is preferable that a hydrogen atom or a substituent is added to at least one of the heteroatoms constituting the aforementioned heterocycle to cationize it.

[0044] As a second onium salt compound, examples include quaternary ammonium salt compounds having a cyclic structure in which a cationized nitrogen atom is included as a ring member atom. Specifically, examples include pyrrolidine onium salt compounds such as 1-butyl-1-methylpyrrolidine onium chloride; piperidinium salt compounds such as 1,1-dimethylpiperidine onium chloride and 6-aza-oniumspiro[5,5]undecyl chloride. Examples of second onium salt compounds also include benzalkonium chloride, benzyl chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, 1,1'-diheptyl-4,4'-bipyridinium dibromide, amphenicol hydrochloride, butyltriphenylphosphonium chloride, butyltriphenylsilane chloride, and 5-aza-oniumspiro[4,4]nonane chloride. As the second onium salt compound, benzalkonium chloride, benzyl chloride, 1-butyl-1-methylpyrrolidine onium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1,1-dimethylpiperidinium chloride, 6-azaspiro[5,5]undecyl chloride, 1-hexyl-3-methylimidazolium chloride, 1,1'-diheptyl-4,4'-bipyridine dibromide, amphenicol hydrochloride, or 5-azaspiro[4,4]nonane chloride are preferred.

[0045] The molecular weight of the second onium salt compound is usually 1 to 1000, preferably 10 to 1000, more preferably 50 to 500, and even more preferably 100 to 500.

[0046] (Resin A) Resin A is a compound different from the first onium salt compound, and is a resin containing repeating units having an onium salt structure. Also, Resin A is a component different from the above-mentioned components. Resin A is a polymeric compound having repeating units derived from monomers, which can be obtained by polymerizing monomers. It is preferable that the weight average molecular weight of Resin A is 500 or more, more preferably 1,000 or more, and even more preferably 1,500 or more. It is preferable that the upper limit is 500,000 or less, more preferably 200,000 or less, even more preferably 20,000 or less, and particularly preferably 8,000 or less. Furthermore, when compound X is a resin containing repeating units having a cyclic structure and having an onium salt structure, compound X is classified as Resin A. Specifically, a resin containing repeating units represented by formula (1) is equivalent to Resin A.

[0047] - Repeating Units with Onium Salt Structures - Resin A comprises repeating units having onium salt structures composed of cations and anions. Examples of the cations and anions described above include those of the first onium salt compound. Resin A may have an onium salt structure in the repeating units comprising onium salt structures in either the main chain or the side chains, and preferably, it may have it in either the main chain or the side chains, but preferably in the main chain. "Main chain" refers to the longest bond chain in the molecule constituting the resin, and "side chain" refers to atomic groups branching from the main chain. Resin A preferably comprises repeating units comprising onium salt structures having cationized nitrogen atoms, more preferably, it comprises repeating units having quaternary ammonium salt structures, and even more preferably, it comprises repeating units having quaternary ammonium salt structures in the main chain.

[0048] It is preferable that resin A contains repeating units having a structure represented by formula (A1) or repeating units having a structure represented by formula (A2), and it is even more preferable that repeating units have a structure represented by formula (A1).

[0049] [Chemical 2]

[0050] In formula (A1), * indicates the bond position. RA11 and RA12 independently represent a hydrogen atom or a substituent, respectively. XA11 - represents an anion. In formula (A2), * indicates the bond position. RA21 represents a hydrogen atom or a substituent. XA21 - represents an anion.

[0051] As substituents represented by RA11, RA12, and RA21, examples include alkyl groups having 1 to 6 carbon atoms. The alkyl group can be either straight-chain or branched, with straight-chain being preferred. The alkyl group having 1 to 4 carbon atoms is preferred, and 1 to 3 is more preferred. Examples of alkyl groups include methyl, ethyl, propyl, and butyl. Examples of substituents that the alkyl group can have include halogen atoms, carboxyl groups, sulfonyl groups, and hydroxyl groups. As RA11, RA12, and RA21, hydrogen atoms or unsubstituted alkyl groups are preferred, with unsubstituted alkyl groups being more preferred.

[0052] X A11- and X A21- represent anions. Examples of such anions include those possessed by the first onium salt compound, preferably monovalent anions, such as halide ions or hydroxide ions.

[0053] As a structure having the structure represented by formula (A1), a quaternary ammonium salt structure can be cited as an example. As a structure having the structure represented by formula (A2), an imine salt structure (a salt structure in which the nitrogen atom in the imine structure is cationic and electrostatically bonded to an anion) and an aromatic imine salt structure (a salt structure in which the nitrogen atom in the pyridine ring and azole ring, etc., is cationic and electrostatically bonded to an anion) can be cited as examples.

[0054] As a repeating unit with an onium salt structure, it is preferable to use a repeating unit represented by any one of equations (1) to (3), and it is even more preferable to use a repeating unit represented by equation (1) or a repeating unit represented by equation (3).

[0055] [Chemical 3]

[0056] In formula (1), L11 to L15 independently represent single-bonded or divalent linking groups, and R11 represents a substituent. R12 and R13 independently represent hydrogen atoms or substituents. n1 represents an integer from 0 to 5. X- represents an anion. In formula (2), L21 represents a divalent linking group. L22 represents a single-bonded or divalent linking group. R21 represents a hydrogen atom or substituent. R22 represents a substituent having a cationized nitrogen atom. X- represents an anion. In formula (3), L31 represents a divalent linking group. R31 and R32 independently represent hydrogen atoms or substituents. X- represents anion.

[0057] In formula (1), L11 to L15 independently represent single-bonded or divalent linking groups. Examples of linking groups represented by L11 and L12 include alkyl groups, cycloalkyl groups, aryl groups, -O-, -S-, -CO-, -COO-, -CONH-, and -SO2-, as well as groups formed by combining at least one divalent linking group selected from the group including -O-, -S-, -CO-, -COO-, -CONH-, and -SO2- with at least one divalent linking group selected from the group including alkyl groups, cycloalkyl groups, and aryl groups. The alkyl groups, cycloalkyl groups, and aryl groups may also have substituents. Examples of substituents include halogen atoms and hydroxyl groups. The alkyl groups may be either linear or branched, with linear being preferred. The number of carbon atoms in the aforementioned alkyl group is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. Examples of the aforementioned alkyl group include methylene, ethyl, and propyl. The aforementioned cycloalkyl group can be any of monocyclic and polycyclic, with monocyclic being preferred. The number of carbon atoms in the aforementioned cycloalkyl group is preferably 5 to 12, more preferably 5 to 8. The aforementioned aryl group can be any of monocyclic and polycyclic, with monocyclic being preferred. The number of ring members in the aforementioned aryl group is preferably 5 to 15, more preferably 5 to 10. The aforementioned aryl group can be a heteroaryl group having atoms other than carbon atoms as ring members. As L11 and L12, a single bond, an alkyl group, or a group formed by combining an alkyl group with -SO2- is preferred, with an alkyl group being more preferred. As L13, a single bond or an alkyl group is preferred, with a single bond being more preferred. For L14 and L15, single bonds or extended alkyl groups are preferred, with extended alkyl groups being even more preferred.

[0058] R11 represents a substituent. R12 and R13 independently represent a hydrogen atom or a substituent, respectively. Examples of substituents represented by R11, R12, and R13 include alkyl groups, halogen atoms, and hydroxyl groups that can have substituents. Examples of alkyl groups that can have substituents include alkyl groups that can have substituents represented by any one of R11, R12, and R21. In the presence of a plurality of R11s, R11s may be the same or different from each other.

[0059] n1 represents an integer from 0 to 5. As n1, integers from 0 to 3 are preferred, integers from 0 to 2 are even better, 0 or 1 are further preferred, and 0 is the best.

[0060] In formula (2), L 21 represents a divalent linker. L 22 represents a single bond or a divalent linker. As a divalent linker represented by L 21 and L 22, examples of divalent linkers represented by either L 11 or L 12 can be cited. As L 21, a single bond, an alkyl group, or a group formed by combining an alkyl group with -SO 2- is preferred, with an alkyl group being more preferred. As a divalent linker represented by L 22, -COO-, -CONH-, or an alkyl group, or a group formed by combining at least one divalent linker selected from the group including -O-, -S-, -CO-, -COO-, -CONH-, and -SO 2- with an alkyl group is preferred. As L 22, a single bond, an alkyl group, or -COO-alkyl- is preferred, with an alkyl group being more preferred.

[0061] R 21 represents a hydrogen atom or a substituent. Examples of substituents include halogen atoms and alkyl groups having 1 to 3 carbon atoms. Hydrogen atoms or alkyl groups having 1 to 3 carbon atoms are preferred as R 21.

[0062] R 22 represents a substituent having a cationized nitrogen atom. As the above-mentioned substituent having a cationized nitrogen atom, a substituent having a structure represented by formula (A1) or a substituent having a structure represented by formula (A2) is preferred, a group represented by any one of formulas (a1) to (a4) is more preferred, and a group represented by formula (a1) is even more preferred.

[0063] [Chemical 4]

[0064] In formula (a1), * indicates the bond position. R26 to R28 independently represent hydrogen atoms or substituents. In formula (a2), * indicates the bond position. R29 represents a hydrogen atom or a substituent. R2 represents a substituent. n represents an integer from 0 to 4. In formula (a3), * indicates the bond position. R29 and R30 independently represent hydrogen atoms or substituents. R2 represents a substituent. m represents an integer from 0 to 3. In formula (a4), * indicates the bond position. R29 represents a hydrogen atom or a substituent. R2 represents a substituent. m represents an integer from 0 to 3.

[0065] R 26 to R 30 each independently represent a hydrogen atom or a substituent. Examples of substituents represented by R 26 to R 30 include any one of R 11, R 12, and R 13, with unsubstituted alkyl groups being preferred. R 2 represents a substituent. Examples of substituents represented by R 2 include any one of R 11, R 12, and R 13. In the case of a plurality of R 2s, the R 2s may be the same or different from each other.

[0066] n represents an integer from 0 to 4. m represents an integer from 0 to 3. For n and m, integers from 0 to 2 are preferred, 0 or 1 are even better, and 0 is further preferred.

[0067] In formula (3), L 31 represents a divalent linker. Examples of divalent linkers include those represented by either L 11 or L 12, with an alkyl group being preferred. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 2 to 8, and even more preferably 3 to 6. Alkyl, propyl, butyl, pentyl, or hexyl groups are preferred. The alkyl group may also have substituents. Examples of substituents include halogen atoms and hydroxyl groups. Examples of alkyl groups having substituents include -CH 2-CHOH-CH 2- and -CH 2-CH 2-CHOH-CH 2-. R 31 and R 32 independently represent hydrogen atoms or substituents, respectively. As the substituents mentioned above, examples include substituents represented by any one of R11, R12 and R13, with unsubstituted alkyl groups being preferred, and methyl, ethyl or propyl groups being even more preferred.

[0068] In formulas (1) to (3), X - represents an anion. Examples of the anions mentioned above are monovalent anions possessed by the first onium salt compound, with halogen compound ions or hydroxide ions being preferred.

[0069] The repeating unit having an onium salt structure can be a repeating unit formed by crosslinking of crosslinking groups or crosslinking molecules. Examples of crosslinking groups include epoxy groups and vinyl unsaturated groups. Examples of crosslinking molecules include isocyanate compounds, epichlorohydrin, and formaldehyde.

[0070] The content of repeating units having an onium salt structure relative to the total mass of resin A is preferably 5-100% by mass, more preferably 20-100% by mass, and further preferably 40-100% by mass. The content of repeating units having an onium salt structure relative to all repeating units of resin A is preferably 5-100 mol%, more preferably 20-100 mol%, and further preferably 40-100 mol%.

[0071] -Other Repeating Units- In addition to the repeating units having onium salt structures described above, resin A may also contain other repeating units. Examples of other repeating units include repeating units derived from monomers having vinyl unsaturated groups. Examples of monomers having vinyl unsaturated groups include carboxylic acids having vinyl unsaturated groups. Examples of carboxylic acids having vinyl unsaturated groups include acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid, and maleic anhydride, as well as their salts. Furthermore, it may be a condensation compound or addition compound of the above carboxylic acid with a compound having a hydroxyl group, a compound having an amino group, or a compound having a glycidyl group. Examples of condensation compounds and addition compounds include ester compounds of acrylic acid or methacrylic acid with a compound having a hydroxyl group, amide compounds of acrylic acid or methacrylic acid with a compound having a primary or secondary amino group, and half-ester compounds of maleic acid with a compound having a hydroxyl group. Furthermore, other repeating units, such as those derived from vinyl acetate, can also be cited. These repeating units derived from vinyl acetate can also be modified by hydrolysis or other methods to remove carboxyl groups. That is, they can be considered repeating units derived from vinyl alcohol.

[0072] The content of other repeating units relative to the total mass of resin A is preferably 0-95% by mass, more preferably 0-80% by mass, and further preferably 0-60% by mass. The content of other repeating units relative to all repeating units of resin A is preferably 0-95 mol%, more preferably 0-80 mol%, and further preferably 0-60 mol%.

[0073] As resin A, examples include resins obtained by polymerizing monomers such as allylamine salt, N-alkylallylamine salt, N,N-dialkylallylamine salt, trialkylallylammonium salt, diallylamine salt, N-alkyldiallylamine salt, and N,N-dialkylammonium salt. Examples of alkyl groups in the monomers mentioned above include methyl and ethyl groups. Furthermore, examples of anions constituting the amine salt include monovalent anions found in the first onium salt compound mentioned above.

[0074] Resin A obtained by polymerizing monomers such as diallylamine salts can be polymerized with cyclization to become a resin containing repeating units represented by formula (1). Examples of resin A include polyallylamine hydrochloride, polydiallylamine hydrochloride, poly(diallyldimethylammonium chloride) and poly(methylethyldimethylethylammonium sulfate).

[0075] Resin A obtained by polymerizing the above-mentioned N,N-dialkylammonium salt monomer can be polymerized into a resin containing repeating units represented by formula (3). As an example of the above-mentioned resin A, poly(diallyldimethylammonium chloride) can be cited.

[0076] Resin A may be a copolymer obtained by polymerizing two or more monomers selected from the above-mentioned monomers. Specifically, a copolymer obtained by polymerizing allylamine salt and diallylamine salt may be given as an example. In addition, it may be a copolymer obtained by polymerizing the above-mentioned monomers with maleic acid. For example, a copolymer obtained by polymerizing diallylamine salt and maleic acid may be given as an example.

[0077] As resin A, for example, a resin having a structure represented by any one of formulas (P-15) to (P-23) can also be cited. In formulas (P-15) to (P-23), the repeating unit marked with m is designated as the first repeating unit, and the repeating unit marked with n is designated as the second repeating unit. The structure represented by any one of formulas (P-15) to (P-23) includes a plurality of repeating units, and there are no particular restrictions on the bonding pattern of the plurality of repeating units; it can be any one of random bonding, alternating bonding, and block bonding.

[0078] [Chemical 5]

[0079] [Chemical 6]

[0080] In formulas (P-15) to (P-23), the ratio (m / n) of the mole number m of the first repeating unit to the mole number n of the second repeating unit is preferably 1 / 20 to 20 / 1. In formula (P-21), X represents a nitrile group, a nitrile group, an amino hydrochloride, or a methylamino group.

[0081] As resin A, for example, a resin formed by the condensation polymerization of dimethylamine and epichlorohydrin (poly(2-hydroxypropyl)dimethylammonium chloride) can be cited. The above resin A is a resin containing repeating units represented by formula (3).

[0082] Also, as resin A, examples include paragraphs

[0036] to

[0071] of Japanese Patent Application Publication No. 11-255841, paragraphs

[0040] to

[0088] of Japanese Patent Application Publication No. 2000-063435, paragraphs

[0025] to

[0039] of Japanese Patent Application Publication No. 2001-106714, paragraphs

[0062] to

[0065] of Japanese Patent Application Publication No. 2004-027162, and paragraphs

[0068] to

[0089] of Japanese Patent Application Publication No. 2004-115675. Resin A described in paragraph 84, paragraphs

[0051] to

[0055] of Japanese Patent Application Publication No. 2005-002196, paragraphs

[0097] to

[0111] of Japanese Patent Application Publication No. 2005-097636, paragraphs

[0026] to

[0027] of Japanese Patent Application Publication No. 2015-166463, paragraphs

[0037] to

[0048] of Japanese Patent Application Publication No. 2017-075243, and paragraphs

[0062] to

[0069] of Japanese Patent Application Publication No. 2021-021020.

[0083] Commercially available products of resin A include, for example, the PAA (registered trademark) series manufactured by NITTOBO MEDICAL CO.,LTD. (e.g., PAA-HCL-01, PAA-HCL-03, PAA-HCL-05, PAA-SA, PAA-01, PAA-D19A, and PAA-1123, etc.); NITTOBO MEDICAL PAS series manufactured by CO.,LTD. (e.g., PAS-21CL, PAS-M-1L, PAS-M-1, PAS-M-1A, PAS-H-1L, PAS-H-5L, PAS-H10L, PAS-24, PAS-92A, PAS-2401, PAS-A-1, PAS-A-5, PAS-2141CL, PAS-2223, PAS-880, PAS-410L, PAS-410SA, PAS-84, and PAS-2351, etc.); Catiomaster (registered trademark) series manufactured by Yokkaichi Chemical Company Limited (e.g., PD series (e.g., PD-7 and PD-30, etc.), PE-30, EPA-SK01, and PAE-01, etc.); SENKA Unisense (registered trademark) series manufactured by corporation (e.g., KHE100L, KHE107L, KHE1000L, FPA100L, FPA101L, FPA1000L, FCA1003L, FCA1001L and KCA100L, etc.); ACRIT (registered trademark) series manufactured by TAISEI FINE CHEMICAL CO,.LTD. (e.g., 1SX-1055F, 1SX-6000 and 1WX-1020, etc.).

[0084] (Compound B) Compound B is a compound having a nitrogen atom and not having an onium salt structure. Compound B is a component different from the above-mentioned components. Compound B can be resin B having a nitrogen atom and not having an onium salt structure. Resin B is a polymer compound having repeating units derived from the monomer (except for repeating units having an onium salt structure) obtained by polymerizing a monomer. It is preferable that the weight average molecular weight of resin B is 500 or more, more preferably 1,000 or more, and even more preferably 1,500 or more. It is preferable that the upper limit is 500,000 or less, more preferably 200,000 or less, even more preferably 20,000 or less, and particularly preferably 8,000 or less.

[0085] Examples of compound B include resin B, biguanide compounds, alkanolamine compounds, amino acids, aliphatic amine compounds, alicyclic amine compounds, polyaminopolycarboxylic acids, azole compounds, guanidine compounds, quinoline compounds, pyridine compounds, indole compounds, and carbazole compounds. It is preferable that compound B is selected from one or more compounds grouped together with resin B, biguanide compounds, alkanolamine compounds, amino acids, aliphatic amine compounds, alicyclic amine compounds, polyaminopolycarboxylic acids, azole compounds, guanidine compounds, quinoline compounds, and pyridine compounds; it is even more preferable that compound B is selected from one or more compounds grouped together with resin B, biguanide compounds, alkanolamine compounds, amino acids, aliphatic amine compounds, alicyclic amine compounds, and polyaminopolycarboxylic acids; and it is further preferable that compound B is selected from one or more compounds grouped together with resin B, biguanide compounds, and alkanolamine compounds.

[0086] -Resin B- Resin B is a resin having nitrogen atoms but not having an onium salt structure. Resin B only needs to have nitrogen atoms in a part of the resin, and it is preferable to include repeating units with nitrogen atoms (hereinafter also referred to as "nitrogen-containing units").

[0087] The nitrogen-containing unit may have nitrogen atoms in either the main chain or the side chain, or in both the main chain and the side chain. "Main chain" refers to the longest bond chain in the molecule that makes up the resin, and "side chain" refers to the atomic group that branches off from the main chain.

[0088] It is preferable that resin B contains repeating units having a structure represented by formula (B1) or repeating units having a structure represented by formula (B2), and it is even more preferable that repeating units have a structure represented by formula (B1).

[0089] [Chemical 7]

[0090] In formula (B1), * indicates the bond position. RB represents a hydrogen atom or a substituent. In formula (B2), * indicates the bond position. As a substituent represented by RB above, examples include any one of RA11, RA12, and RA21.

[0091] As a nitrogen-containing unit, a repeating unit represented by any one of equations (B3) to (B5) is preferred, and a repeating unit represented by equation (B4) or a repeating unit represented by equation (B5) is even more preferred.

[0092] [Chemical 8]

[0093] In formula (B3), Lb11 to Lb15 independently represent single bonds or divalent linking groups. Rb11 represents a substituent. Rb12 represents a hydrogen atom or a substituent. nb1 represents an integer from 0 to 5. In formula (B4), Lb21 represents a divalent linking group. Lb22 represents a single bond or a divalent linking group. Rb21 represents a hydrogen atom or a substituent. Rb22 represents a substituent having a nitrogen atom. In formula (B5), Lb31 represents a divalent linking group. Rb31 represents a hydrogen atom or a substituent.

[0094] In formula (B3), L b11~L b15, R b11, R b12 and n b1 have the same meaning as L 11~L 15, R 11, R 12 and n 1 in formula (1), and the better state is also the same.

[0095] In formula (B4), Lb21, Lb22, and Rb21 have the same meaning as L21, L22, and R21 in formula (2), and the preferred state is also the same. Rb22 represents a substituent having a nitrogen atom. The above-mentioned substituent having a nitrogen atom does not have an onium salt structure. As the above-mentioned substituent having a nitrogen atom, it is preferred to have a substituent having the structure represented by formula (B1) or a substituent having the structure represented by formula (B2), and it is even more preferred to have a group represented by any of formulas (b1) to (b4), and the group represented by formula (b1) is even more preferred.

[0096] [Chemical 9]

[0097] In formula (b1), * indicates the bond position. R23 and R24 independently represent hydrogen atoms or substituents, respectively. In formula (b2), * indicates the bond position. R2 represents a substituent. n represents an integer from 0 to 4. In formula (b3), * indicates the bond position. R25 represents a hydrogen atom or substituent. R2 represents a substituent. m represents an integer from 0 to 3. In formula (b4), * indicates the bond position. R2 represents a substituent. m represents an integer from 0 to 3.

[0098] As substituents represented by R 23, R 24, and R 25, examples of substituents represented by any one of R 11, R 12, and R 13 can be cited. In formulas (b2) to (b4), R 2 has the same meaning as R 2 in formulas (a2) to (a4), and the preferred state is also the same. In formula (b2), n has the same meaning as n in formula (a2), and the preferred state is also the same. In formulas (b3) and (b4), m has the same meaning as m in formulas (a3) ​​and (a4), and the preferred state is also the same.

[0099] In formula (B5), Lb31 represents a divalent linking group. Rb31 represents a hydrogen atom or a substituent. Examples of divalent linking groups represented by Lb31 include either L11 or L12. Examples of substituents represented by Rb31 include either R11, R12, or R13.

[0100] The nitrogen-containing unit can be a repeating unit formed by crosslinking of crosslinking groups or crosslinking molecules. Examples of crosslinking groups include epoxy groups and vinyl unsaturated groups. Examples of crosslinking molecules include isocyanate compounds, epichlorohydrin, and formaldehyde.

[0101] The content of nitrogen-containing units relative to the total mass of resin B is preferably 5-100% by mass, more preferably 20-100% by mass, and further preferably 40-100% by mass. The content of nitrogen-containing units relative to all repeating units of resin B is preferably 5-100 mol%, more preferably 20-100 mol%, and further preferably 40-100 mol%.

[0102] In addition to the nitrogen-containing unit mentioned above, resin B may also contain other repeating units. Examples of other repeating units include those that resin A may have.

[0103] The content of other repeating units relative to the total mass of resin B is preferably 0-95% by mass, more preferably 0-80% by mass, and further preferably 0-60% by mass. The content of other repeating units relative to all repeating units of resin B is preferably 0-95 mol%, more preferably 0-80 mol%, and further preferably 0-60 mol%.

[0104] As resin B, examples include resins obtained by polymerizing monomers such as allylamine, N-alkylallylamine, N,N-dialkylallylamine, diallylamine, and N-alkyldiallylamine. As alkyl groups contained in the above monomers, examples include methyl and ethyl groups.

[0105] Resin B obtained by polymerizing monomers such as diallylamine can be polymerized with cyclization to become a resin containing repeating units represented by formula (B3). Examples of resin B include polyallylamine and polydiallylamine.

[0106] Resin B may be a copolymer obtained by polymerizing two or more monomers selected from the above-mentioned monomers. Specifically, a copolymer obtained by polymerizing allylamine and diallylamine may be given as an example. In addition, it may be a copolymer obtained by polymerizing the above-mentioned monomers with maleic acid. For example, a copolymer obtained by polymerizing diallylamine and maleic acid may be given as an example.

[0107] As resin B, for example, a resin having a structure represented by any one of formulas (P-1) to (P-14) can also be cited. In formulas (P-1) to (P-14), the repeating unit marked with m is designated as the first repeating unit, and the repeating unit marked with n is designated as the second repeating unit. The structure represented by any one of formulas (P-1) to (P-14) includes a plurality of repeating units, and there are no particular restrictions on the bonding pattern of the plurality of repeating units; it can be any one of random bonding, alternating bonding, and block bonding.

[0108] [Chemical 10]

[0109] In equations (P-1) to (P-14), the ratio (m / n) of the mole number m of the first repeating unit to the mole number n of the second repeating unit is preferably 1 / 20 to 20 / 1. In equation (P-7), l represents an integer from 1 to 30.

[0110] As resin B, for example, polyethyleneimine obtained by ring-opening polymerization of ethyleneimine can be cited. Polyethyleneimine can be linear, branched, or dendritic. As a linear polyethyleneimine, for example, a resin comprising repeating units represented by formula (B5) can be cited. As a branched polyethyleneimine, for example, a resin comprising the structure represented by formula (4-a), the structure represented by formula (4-b), and the structure represented by formula (4-c) can be cited. As a dendritic polyethyleneimine, for example, a resin comprising the structure represented by formula (4-a) and the structure represented by formula (4-c) can be cited.

[0111] [Chemistry 11]

[0112] In formulas (4-a), (4-b) and (4-c), * and ** represent the bonding positions. Among them, * and ** are bonded, and the ends of each resin become **-CH 2-CH 2-NH 2.

[0113] Also, as resin B, examples include paragraphs

[0036] to

[0071] of Japanese Patent Application Publication No. 11-255841, paragraphs

[0040] to

[0088] of Japanese Patent Application Publication No. 2000-063435, paragraphs

[0025] to

[0039] of Japanese Patent Application Publication No. 2001-106714, paragraphs

[0062] to

[0065] of Japanese Patent Application Publication No. 2004-027162, and paragraphs

[0068] to

[0069] of Japanese Patent Application Publication No. 2004-115675. Resin B described in paragraph 84, paragraphs

[0051] to

[0055] of Japanese Patent Application Publication No. 2005-002196, paragraphs

[0097] to

[0111] of Japanese Patent Application Publication No. 2005-097636, paragraphs

[0026] to

[0027] of Japanese Patent Application Publication No. 2015-166463, paragraphs

[0037] to

[0048] of Japanese Patent Application Publication No. 2017-075243, and paragraphs

[0062] to

[0069] of Japanese Patent Application Publication No. 2021-021020.

[0114] Commercially available products of resin B include, for example, the PAA (registered trademark) series manufactured by NITTOBO MEDICAL CO.,LTD. (e.g., PAA-03, PAA-05, PAA-08, PAA-15C, PAA-25, PAA-D11, PAA-U5000, PAA-U7030, PAA-N5000 and PAA-1151, etc.); and the PAS series manufactured by NITTOBO MEDICAL CO.,LTD. (e.g., PAS-21, PAS-92 and PAS-2251, etc.).

[0115] -Biguanide Compounds- Biguanide compounds are compounds having a biguanide group. Examples of biguanide compounds include chlorhexidine, 1-(o-tolyl)biguanide, phenethylamine, 1-phenylbiguanide, 1-(3-methylphenyl)biguanide, 1-(4-methylphenyl)biguanide, 1-(2-chlorophenyl)biguanide, 1-(4-chlorophenyl)biguanide, 1-(2,3-dimethylphenyl)biguanide, 1-(2,6-dimethylphenyl)biguanide, 1-(1-naphthyl)biguanide, 1-(4-methyl)biguanide, etc. 1-(4-nitrophenyl)biguanide, 1,1-diphenylbiguanide, 1,5-diphenylbiguanide, 1,5-bis(4-chlorophenyl)biguanide, 1,5-bis(3-chlorophenyl)biguanide, 1-(4-chlorophenyl)phenyl-5-(4-methoxyphenyl)biguanide, 1,1-bis(3-chloro-4-methoxyphenyl)biguanide, 1,5-bis(3,4-dichlorophenyl)biguanide, 1,5-bis(3-chlorophenyl)biguanide 5-Dichlorophenyl)biguanide, 1,5-bis(4-bromophenyl)biguanide, ethylene biguanide, propylene biguanide, tetramethylene biguanide, pentamethylene biguanide, hexamethylene biguanide, heptamethylene biguanide, octamethylene biguanide, 1,1'-hexamethylenebis(5-(p-chlorophenyl)biguanide)(chlorhexidine), 2-(benzyloxymethyl)pentane-1,5-bis(5-hexylbiguanide), 2-(phenylthiomethyl) Pentane-1,5-bis(5-phenylethylbiguanidine), 3-(phenylthio)hexane-1,6-bis(5-hexylbiguanidine), 3-(phenylthio)hexane-1,6-bis(5-cyclohexylbiguanidine), 3-(benzylthio)hexane-1,6-bis(5-hexylbiguanidine), and 3-(benzylthio)hexane-1,6-bis(5-cyclohexylbiguanidine), chlorhexidine, 1-(o-tolyl)biguanidine, or phenethylamine are preferred.

[0116] - Alkanolamine Compounds - Alkanolamine compounds are compounds having one or more amino groups selected from the group consisting of primary, secondary, and tertiary amino groups and one or more hydroxyl groups. Alkanolamine compounds are compounds that differ from the various components mentioned above. Examples of alkanolamine compounds include primary, secondary, and tertiary alkanolamine compounds, with primary alkanolamine compounds being preferred. Furthermore, in the case of amino groups with different orders, the alkanolamine compound is classified as having the highest order.

[0117] As a primary alkanolamine compound, examples include 2-amino-1-butanol, 2-amino-2-hydroxymethyl-1,3-propanediol (Tris), monoethanolamine (MEA), 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 1,3-diamino-2-propanol, 2-amino-2-methyl-1-propanol (AMP), 3-amino-1-propanol, 1-amino-2-propanol, diethylene glycolamine (DEGA), 2-(aminoethoxy)ethanol (AEE), and 1-amino-4-hydroxyadamantane, with 2-amino-1-butanol, 2-amino-2-hydroxymethyl-1,3-propanediol (Tris), or 1-amino-4-hydroxyadamantane being preferred.

[0118] Examples of secondary alkanolamine compounds include 1,3-bis[tris(hydroxymethyl)methylamino]propane, uracil, N-methylethanolamine, 2-(ethylamino)ethanol, 2-[(hydroxymethyl)amino]ethanol, 2-(propylamino)ethanol, N,N'-bis(2-hydroxyethyl)ethylenediamine, diethanolamine, 2-(2-aminoethylamino)ethanol (AAE), N-butylethanolamine and N-cyclohexylethanolamine.

[0119] Examples of tertiary alkanolamine compounds include bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane (Bis-Tris-Propane), N-methyldiethanolamine (MDEA), 2-(dimethylamino)ethanol (DMAE), N-ethyldiethanolamine (EDEA), 2-diethylaminoethanol, 2-(dibutylamino)ethanol, 2-[2-(dimethylamino)ethoxy]ethanol, 2-[2-(diethylamino)ethoxy]ethanol, triethanolamine, N-butyldiethanolamine (BDEA), and N-tertiary alkanolamine. Butyl diethanolamine (t-BDEA), 1-[bis(2-hydroxyethyl)amino]-2-propanol (Bis-HEAP), 1-(2-hydroxyethyl)piperazine (HEP), 1,4-bis(2-hydroxyethyl)piperazine (BHEP), 2-(N-ethylanilino)ethanol, N-phenyl diethanolamine (Ph-DEA), N-benzyl diethanolamine, p-tolyl diethanolamine, m-tolyl diethanolamine, 2-(dimethylamino)-1,3-propanediol, 2-[[2-(dimethylamino)ethyl]methylamino]ethanol, and stearyl diethanolamine.

[0120] -Amino Acid- Examples of amino acids include arginine, ricin, aspartic acid, glycine, serine, α-alanine (2-aminopropionic acid), β-alanine (3-aminopropionic acid), leucine, isoleucine, cystine, cysteine, ethionine, threonine, tryptophan, tyrosine, valine, histidine, histidine derivatives, asparagine, glutamine, glutamine, proline, methionine, phenylalanine, and compounds described in paragraphs

[0021] to

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

[0121] -Aliphatic Amine Compounds- Examples of aliphatic amine compounds include primary amines having a primary amino group (-NH₂), secondary amines having a secondary amino group (>NH), and tertiary amines having a tertiary amino group (>N-). Examples of primary, secondary, and tertiary amines include alkylamines, dialkylamines, and trialkylamines, respectively. The alkyl groups may have substituents. Examples of primary amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, methoxyethylamine, methoxypropylamine, and tetrahydrofurfurylamine. Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, and dibutylamine (DBA). Examples of tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylethylamine, dimethylpropylamine, diethylmethylamine, dimethylhydroxyethylamine, N-methyldiethanolamine, and benzyldimethylamine.

[0122] -Alicyclic Amine Compounds- Examples of alicyclic amine compounds include piperazine compounds and cyclic amidine compounds. Piperazine compounds are compounds with a heterocyclic 6-membered ring (piperazine ring) in which the -CH- group of a cyclohexane ring is replaced by a nitrogen atom. 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. These substituents may be bonded to each other.

[0123] Examples of piperazine compounds include piperazine, 1-methyl piperazine, 1-ethyl piperazine, 1-propyl piperazine, 1-butyl piperazine, 2-methyl piperazine, 1,4-dimethyl piperazine, 2,5-dimethyl piperazine, 2,6-dimethyl piperazine, 1-phenyl piperazine, 2-hydroxy piperazine, 2-hydroxymethyl piperazine, 1-(2-hydroxyethyl) piperazine (HEP), and N-(2-aminoethyl) piperazine (AEP). ), 1,4-bis(2-hydroxyethyl)piperidine (BHEP), 1,4-bis(2-aminoethyl)piperidine (BAEP), 1,4-bis(3-aminopropyl)piperidine (BAPP), N-methyl-N'-(2-dimethylaminoethyl)piperidine, N,N',N''-tris(3-dimethylaminopropyl)-hexahydro-s-trisidine and 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0124] A cyclic amidine compound is a compound having a heterocycle containing an amidine structure (>NC=N-) within the ring. It is preferred that the number of ring members of the aforementioned heterocycle in the cyclic amidine compound is 5 or 6, with 6 being more preferred. Examples of cyclic amidine compounds include diazabicycloundecene (1,8-diazabicyclo[5.4.0]undec-7-ene: DBU), diazabicyclononene (1,5-diazabicyclo[4.3.0]non-5-ene: DBN), 3,4,6,7,8,9,10,11-octahydro-2H-pyrimidino[1.2-a]acoctocin, 3,4,6,7,8,9-hexahydro-2H-pyridino[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-octahydropyrimidino[1.2-a]azopon, and creatine anhydride.

[0125] Examples of alicyclic amine compounds include compounds having a heterocyclic 5-membered ring without aromaticity such as 1,3-dimethyl-2-imidazolidineone and imidazolidinethione, compounds having a 6-membered ring containing oxygen atoms such as oxoline (e.g., N-(2-hydroxyethyl)oxoline and 4-(2-cyanoethyl)oxoline), and compounds having a 7-membered ring containing nitrogen atoms.

[0126] -Polyaminopolycarboxylic acid- Polyaminopolycarboxylic acid can be a salt. Examples of such salts include hydrochloride, sulfate, and nitrate. Polyaminopolycarboxylic acid is a compound having 2 or more amino groups and 2 or more carboxyl groups. Examples of polyamine-based polycarboxylic acids include, for example, butanediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraaminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-cyclohexanediaminetetraacetic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylenediamine-N,N,N',N'-tetraacetic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diaacetic acid, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclododecane-tetraacetic acid, diaminopropanoltetraacetic acid, and (hydroxyethyl)ethylenediaminetriacetic acid, with ethylenediaminetetraacetic acid being preferred.

[0127] -Azolium Compound- Azolium compound is a compound containing at least one nitrogen atom and an aromatic 5-membered ring. Azolium compounds function as preservatives and can enhance the preservative effect of compositions. It is preferable that the number of nitrogen atoms in the 5-membered ring of the azole compound is 1 to 4, and more preferably 1 to 3. The azole compound may have substituents on the 5-membered ring. Examples of such substituents include hydroxyl, carboxyl, mercapto, amino, alkyl groups having 1 to 4 carbon atoms, and 2-imidazolium groups.

[0128] Examples of azole compounds include imidazole compounds in which one of the atoms constituting the azole ring is a nitrogen atom, pyrazole compounds in which two of the atoms constituting the azole ring are nitrogen atoms, thiazole compounds in which one of the atoms constituting the azole ring is a nitrogen atom and the other is a sulfur atom, triazole compounds in which three of the atoms constituting the azole ring are nitrogen atoms, and tetraazole compounds in which four of the atoms constituting the azole ring are nitrogen atoms.

[0129] Examples of imidazole compounds include imidazole, 1-methylimidazolium, 2-methylimidazolium, 5-methylimidazolium, 1,2-dimethylimidazolium, 2-mercaptoimidazolium, 4,5-dimethyl-2-mercaptoimidazolium, 4-hydroxyimidazolium, 2,2'-biimidazole, 4-imidazolium carboxylic acid, histamine, and benzimidazole.

[0130] Examples of pyrazole compounds include pyrazole, 4-pyrazole carboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-aminopyrazole and 4-aminopyrazole.

[0131] Examples of thiazole compounds include 2,4-dimethylthiazole, benzothiazole and 2-mercaptobenzothiazole.

[0132] Examples of triazole compounds include 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3-amino-1,2,4-triazole, 1,2,3-triazole, 1-methyl-1,2,3-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxybenzotriazole, 5-methylbenzotriazole and 2,2'-{[(5-methyl-1H-benzotriazole-1-yl)methyl]imino}diethanol.

[0133] Examples of tetrazolium compounds include 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-pyroxytetrazole and 1-(2-dimethylaminoethyl)-5-pyroxytetrazole.

[0134] As an azole compound, triazole or imidazole compounds are preferred, with triazole being even better.

[0135] -Guidinium compounds- Examples of guanidine compounds include 1,3-diphenylguanidine, 1,2,3-tris(tert-butoxycarbonyl)guanidine, 1-acetylguanidine, 7-methyl-1,5,7-triazabiscyclic[4.4.0]dec-5-ene and 1,1,3,3-tetramethylguanidine.

[0136] -Quinoline compounds- Examples of quinoline compounds include 2-aminoquinoline, 2-quinoline carboxylic acid, 8-hydroxyquinaldinic acid, 8-quinoline carboxylic acid, 5-quinoline carboxylic acid, 6,7-dimethoxyisoquinoline, 5-aminoquinoline, 7-chloroquinoline, and 1,4-dihydro-4-oxoquinoline-3-carboxylic acid.

[0137] -Pyridine compounds- Examples of pyridine compounds include 2,6-pyridinedicarboxylic acid, bis(2-pyridylmethyl)amine, 3H-1,2,3-triazolo[4,5-b]pyridine-3-ol, 2,6-diaminopyridine, 6-amino-2-pyridinecarboxylic acid, 6-methylpyridine-2-carboxylic acid, 3-methylpyridine-2-carboxylic acid, pyridine-2-carboxylic acid, pyridine-4-carboxylic acid, 2,6-diacetylbyridine, 3,5-pyridinedicarboxylic acid methyl, 2,6-dimethoxypyridine, and 2,4-pyridinedicarboxylic acid diethyl.

[0138] -Indole compounds- Examples of indole compounds include indole-3-butyric acid, 2,5-dimethylindole, 5,6-dimethoxyindole, 1-methylindole-2-carboxylic acid, 5-aminoindole, 5,6-diacetoxyindole and 5-methoxyindole-3-carboxylic acid.

[0139] -Carbazole compounds- Examples of carbazole compounds include carbazole, 3,6-dimethylcarbazole, 3,6-dimethoxycarbazole and 3-amino-9-ethylcarbazole.

[0140] Compound X may be used alone or in combination with two or more. The content of compound X relative to the total mass of the composition is typically 0.1 to 15,000 ppm by mass, preferably 1 to 7,000 ppm by mass, more preferably 1 to 2,000 ppm by mass, even more preferably 1 to 1,000 ppm by mass, even more preferably 1 to 500 ppm by mass, particularly preferably 1 to 200 ppm by mass, and best preferably 5 to 200 ppm by mass.

[0141] The mass ratio of hypochlorous acid or its salt to the content of compound X (content of hypochlorous acid or its salt / content of compound X) is preferably 1 to 10,000, more preferably 5 to 2,000, and further preferably 10 to 1,000. The mass ratio of the content of the first onium salt compound to the content of compound X (content of the first onium salt compound / content of compound X) is preferably 0.001 to 50,000, more preferably 1 to 10,000, and further preferably 1 to 5,000.

[0142] [Any Component] In addition to the components mentioned above, the composition may contain any component. Any component may be used alone or in combination with two or more other components. The following describes any component in detail.

[0143] (Compounds with carbonyl groups) The composition is a compound different from both the first onium salt compound and compound X, and may also include compounds with carbonyl groups. Compounds with carbonyl groups are compounds different from the various components mentioned above. Compounds with carbonyl groups can suppress the generation of RuO₄ gas. In the case of treating a substance containing ruthenium by means of the composition, for example, ruthenium is dissolved in the composition as RuO₄⁻ and RuO₄²⁻. Subsequently, RuO₄⁻ and RuO₄²⁻ are converted to RuO₄ in the composition, a portion of which is vaporized and released into the gas phase. RuO₄ gas has adverse effects on the human body, and RuO₄ gas is easily reduced to produce RuO₂ particles (RuO₂ particles). Compounds with carbonyl groups are effective in suppressing this phenomenon. Compounds with carbonyl groups can be either compounds with ketones (-CO⁻) or compounds with esters (-COO⁻).

[0144] Examples of compounds having a carbonyl group include monocarboxylic acids or their esters such as acetic acid, formic acid, lactic acid, glycolic acid, 2,2-bis(hydroxymethyl)propionic acid, gluconic acid, α-glucoheponic acid, heptanoic acid, phenylacetic acid, phenylethanolic acid, diphenylhydroxyacetic acid, gallic acid, cinnamic acid, naphtholic acid, p-anisolic acid, salicylic acid, creatine, acrylic acid, and benzoic acid; dicarboxylic acids or their esters such as malic acid, adipic acid, succinic acid, maleic acid, tartaric acid, oxalic acid, dimethyl oxalate, glutaric acid, malonic acid, 1,3-adamantanedicarboxylic acid, diethanolic acid, and phthalic acid; tricarboxylic acids or their esters such as citric acid; tetracarboxylic acids or their esters such as butane-1,2,3,4-tetracarboxylic acid; hexacarboxylic acids or their esters such as 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; and carbonyl compounds such as ethyl acetate and dimethylmalonic acid. As compounds containing a carbonyl group, oxalic acid, dimethyl oxalate, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid, succinic acid, acetic acid, butane-1,2,3,4-tetracarboxylic acid, dimethylmalonic acid, glutaric acid, diethanolic acid, citric acid, malonic acid, 1,3-adamantanedicarboxylic acid, or 2,2-bis(hydroxymethyl)propionic acid are preferred.

[0145] The content of the carbonyl compound relative to the total mass of the composition is preferably 0.0001 to 60% by mass, more preferably 0.01 to 35% by mass, and even more preferably 0.1 to 20% by mass.

[0146] (Solvent) The composition may contain a solvent. Examples of solvents include water and organic solvents, with water being preferred. Water that has undergone purification treatment, such as distilled water, ion-exchanged water, and ultrapure water, is preferred, and ultrapure water used in semiconductor manufacturing is even more preferred. The water contained in the composition may contain unavoidable trace amounts of mixed components. A water content of 50% by mass or more relative to the total mass of the composition is preferred, 65% by mass or more is more preferred, and 75% by mass or more is even more preferred. An upper limit of 99.999% by mass or less relative to the total mass of the composition is preferred, and 99.9% by mass or less is even more preferred.

[0147] Water-soluble organic solvents are preferred as organic solvents. Water-soluble organic solvents refer to organic solvents that can be mixed with water in any proportion. Examples of water-soluble organic solvents include ether solvents, alcohol solvents, ketone solvents, amide solvents, sulfur-containing solvents, and lactone solvents.

[0148] Examples of ether solvents include diethyl ether, diisopropyl ether, dibutyl ether, tributyl methyl ether, cyclohexyl methyl ether, tetrahydrofuran, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, alkyl glycol monoalkyl ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether and triethylene glycol monobutyl ether, etc.) and alkyl glycol dialkyl ethers (e.g., diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, etc.). The carbon number of the ether solvent is preferably 3 to 16, more preferably 4 to 14, and even more preferably 6 to 12.

[0149] Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, propylene glycol, glycerol, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol. It is preferable that the alcohol solvent has 1 to 8 carbon atoms, and more preferably 1 to 4.

[0150] Examples of acetamide solvents include methylamine, monomethylmethylamine, dimethylmethylamine, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide and N-methylpyrrolidone.

[0151] Examples of sulfur-containing solvents include dimethyl sulfide, dimethyl sulfide and cyclobutane.

[0152] Furthermore, organic solvents with low relative permittivity can also be cited. A relative permittivity of 45 or less is preferred, 20 or less is more preferred, and 10 or less is even more preferred. The lower limit is generally 0 or more. Examples of organic solvents with the aforementioned low relative permittivity include cyclobutane (relative permittivity 43), acetonitrile (relative permittivity 37), carbon tetrachloride (relative permittivity 2.2), and 1,4-dimethylalkanes (relative permittivity 2.2). Furthermore, the relative permittivity is a value at 25°C.

[0153] The content of organic solvent relative to the total mass of the composition is preferably 0.1 to 10% by mass.

[0154] (Basic Inorganic Compound) The composition may include a basic inorganic compound. The basic inorganic compound is a compound that is different from the various components mentioned above. Examples of basic inorganic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, as well as alkaline earth metal hydroxides.

[0155] The content of the basic inorganic compound is preferably 0.1% by mass or more relative to the total mass of the composition, and more preferably 0.5% by mass or more. It is also preferable that the content is at least 20.0% by mass relative to the total mass of the composition. Adjusting the basic inorganic compound within the above-mentioned preferred range to the preferred pH range of the composition described later is also preferable.

[0156] (Acidic Compound) The composition may include an acidic compound. An acidic compound is a compound that differs from the various components described above. An acidic compound refers to an acidic compound that exhibits acidity (pH less than 7.0) in aqueous solution. Examples of acidic compounds include inorganic acids, organic acids, and their salts.

[0157] As inorganic acids, examples include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, fluoric acid, iodic acid, perchloric acid and their salts, with sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid or iodic acid being preferred, and nitric acid, sulfuric acid, hydrochloric acid or iodic acid being even more preferred.

[0158] As an acidic compound, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfonic acid or salts thereof are preferred, and sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid or p-toluenesulfonic acid are even more preferred.

[0159] The content of the acidic compound is preferably 0.1% by mass or more relative to the total mass of the composition, and more preferably 0.5% by mass or more. It is also preferable that the content of the acidic compound is at least 20.0% by mass relative to the total mass of the composition. Adjusting the pH of the acidic compound within the above-mentioned preferred range to the preferred pH range of the composition described later is also preferable.

[0160] (Water-soluble resin) The composition may include a water-soluble resin. The water-soluble resin is a compound that is different from the various components mentioned above. Examples of water-soluble resins include polyacrylic acid, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, and carboxyethylene polymers.

[0161] (Surfactant) The composition may include a surfactant. The surfactant is a compound that differs from the various components described above. As a surfactant, any compound having both a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule can be cited as an example, such as anionic surfactants and nonionic surfactants. As anionic surfactants, for example, anionic surfactants having at least one hydrophilic group selected from the group consisting of sulfonic acid groups, carboxyl groups, sulfate ester groups, and phosphonic acid groups in the molecule can be cited as an example.

[0162] Examples of hydrophobic groups in surfactants include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. When the hydrophobic group includes an aromatic hydrocarbon group, it is preferable that the hydrophobic group has 6 or more carbon atoms, and more preferably 10 or more. When the hydrophobic group does not contain an aromatic hydrocarbon group and is composed only of an aliphatic hydrocarbon group, it is preferable that the hydrophobic group has 8 or more carbon atoms, and more preferably 10 or more. It is preferable that the upper limit of the number of carbon atoms in the hydrophobic group is 24 or less, and more preferably 20 or less.

[0163] The content of surfactant is preferably 0.01% by mass or more relative to the total mass of the composition, and more preferably 0.03% by mass or more. From the viewpoint of inhibiting foaming of the composition, the upper limit is preferably 10% by mass or less relative to the total mass of the composition, and more preferably 5% by mass or less.

[0164] (Abrasive particles) It is preferable that the composition does not substantially contain abrasive particles. Abrasive particles refer to particles contained in the polishing slurry used for polishing semiconductor substrates, and whose average primary particle size is 5 nm or more. Furthermore, it is preferable that the composition does not substantially contain abrasive particles, with the content of abrasive particles being less than 0.1% by mass or less, and preferably less than 0.01% by mass, and even more preferably less than 0.001% by mass, relative to the total mass of the composition. The lower limit is usually 0% by mass or more relative to the total mass of the composition. Examples of abrasive particles include inorganic materials such as silicon dioxide (including colloidal silicon dioxide and fumed silicon dioxide), alumina, zirconium dioxide, cerium oxide, titanium dioxide, germanium oxide, manganese oxide, and silicon carbide; and organic materials such as polystyrene, polyacrylic resin, and polyvinyl chloride.

[0165] The content of abrasive particles was determined using a commercially available measuring device in a light scattering liquid particle determination method using a laser as the light source. Furthermore, the average primary particle size of the abrasive particles was determined by measuring the particle size (equivalent circle diameter) of 1000 primary particles randomly selected from an image acquired using a transmission electron microscope (TEM2010, 200kV) manufactured by JEOL Ltd., and then averaging these measurements. Moreover, the equivalent circle diameter refers to the diameter of a circle estimated to have a projected area equal to the projected area of ​​the particle at the time of observation. Methods for removing abrasive particles from the composition include, for example, purification processes such as filtration.

[0166] (Metallic Component) The composition may contain a metallic component. Examples of metallic components include metal particles and metal ions. For example, the content of a metallic component refers to the total content of metal particles and metal ions. The composition may contain either metal particles or metal ions, or both.

[0167] The metal atoms included in the metallic component may be, for example, metal atoms selected from the group consisting of Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sn, Sr, Ti, Zn, and Zr. The metallic component may contain one or more types of metal atoms. The metal particles may be monomers or alloys, or may exist in a form combining metal and organic matter. The metallic component may be a metallic component that is unavoidably included in the various components (raw materials) included in the composition, or a metallic component that is unavoidably included during the manufacture, storage, and / or transfer of the composition, or a metallic component that is intentionally added. The content of the metallic component relative to the total mass of the composition is usually 0.01 mass ppt to 10 mass ppm, preferably 0.1 mass ppt to 1 mass ppm, and more preferably 0.1 mass ppt to 100 mass ppb.

[0168] The contents of sodium, potassium, and aluminum relative to the total mass of the composition (preferably, the contents of sodium, potassium, aluminum, magnesium, iron, nickel, copper, silver, cadmium, and lead) are all below 20 ppb by mass, and more preferably below 1 ppb by mass. The lower limit is usually above 0 ppb by mass.

[0169] The types and contents of metal components in the composition can be determined by ICP-MS (Inductively Coupled Plasma Mass Spectrometry). In ICP-MS, the content of the metal component being measured is determined regardless of its form. Therefore, the total mass of the metal particles and metal ions being measured is quantified as the content of the metal component. For example, in the determination by ICP-MS, the Agilent 8800 triple quadrupole ICP-MS (Inductively Coupled Plasma Mass Spectrometry, for semiconductor analysis, Option #200) and Agilent 8900 manufactured by Agilent Technologies Japan, Ltd., and the NexION350S manufactured by PerkinElmer Co., Ltd. can be used.

[0170] There are no particular limitations on the method for adjusting the content of each metal component in the composition. For example, by performing known processes to remove metals from the composition and / or from raw materials containing various components used in the preparation of the composition, the content of metal components in the composition can be reduced. Furthermore, by adding a compound containing metal ions to the composition, the content of metal components in the composition can be increased.

[0171] <Properties of the Composition> [pH] The pH of the composition is generally 1.0 to 14.0. From the viewpoint of superior effect of the present invention, 7.0 to 14.0 is preferred, 8.0 to 13.5 is more preferred, and 10.0 to 13.0 is further preferred. In this specification, the pH of the composition can be measured using a pH meter (F-71S, manufactured by HORIBA, Ltd.) at 25°C.

[0172] [Coarse Particles] It is preferable that the composition does not substantially contain coarse particles. "Coarse particles" refers to particles with a diameter of 0.2 μm or more when the particle shape is considered to be spherical. Furthermore, "substantially not containing coarse particles" means that when the composition is measured using a commercially available measuring device in a light scattering liquid particle determination method, there are 10 or fewer particles larger than 0.2 μm in 1 mL of the composition. It is preferable that the lower limit is 0 or more. Coarse particles that may be contained in the composition include particles such as garbage, dust, and organic solid matter contained as impurities in the raw materials, as well as particles such as garbage, dust, and inorganic solid matter introduced as contaminants during the preparation of the composition, which are equivalent to particles that do not dissolve in the composition. As a method for determining the content of coarse particles, for example, a method using a commercially available measuring device in the liquid phase in a light scattering liquid particle determination method using a laser as a light source can be cited. As a method for removing coarse particles, for example, filtration treatment can be cited.

[0173] <Method for Manufacturing the Composition> The method for manufacturing the composition of the present invention can be, for example, by mixing the various components described above. There are no particular limitations on the order or timing of mixing the various components, or the order and timing. For example, a method can be described where various components that may be included in the composition are sequentially added to a mixer such as a mixer containing purified pure water, and then thoroughly stirred to mix the various components and manufacture the composition. Other methods for manufacturing the composition include mixing the various components after adjusting the pH of the composition in advance using the aforementioned alkaline inorganic compound or acidic compound, and adjusting the pH to a set value using the aforementioned alkaline inorganic compound or acidic compound after mixing the various components.

[0174] Furthermore, the composition of the present invention can be manufactured by producing a concentrate with a lower content of solvents such as water compared to that used in the present invention, and then adjusting the content of each component to a predetermined content by diluting it with a diluent (preferably water) during use. The composition of the present invention can be manufactured by diluting the concentrate with a diluent and then adjusting the pH to a predetermined value using the aforementioned alkaline inorganic compound or acidic compound. When diluting the concentrate, a predetermined amount of diluent can be added to the concentrate, or a predetermined amount of concentrate can be added to the diluent.

[0175] [Metal Removal Step] Regarding the above manufacturing method, a metal removal step can be performed to remove metal components from the above-described ingredients and / or compositions (hereinafter also referred to as "purified material"). For example, an example of performing a metal removal step on a purified material containing the above-described hypochlorous acid or its salt and water can be given.

[0176] In the purified product comprising the above-mentioned hypochlorous acid or its salt and water, the content of hypochlorous acid or its salt relative to the total mass of the purified product is preferably 0.0001 to 50% by mass, more preferably 1 to 45% by mass, and further preferably 4 to 40% by mass. From the viewpoint of excellent processing efficiency, the water content in the purified product is preferably 40% by mass or more and less than 100% by mass, preferably 50 to 99% by mass, and further preferably 60 to 95% by mass. In the purified product comprising the above-mentioned hypochlorous acid or its salt and water, the components and / or any components that may be included in the above-mentioned composition may be further included. As a metal removal step, step P, which involves performing an ion exchange method on the purified product, can be cited.

[0177] (Step P) In step P, an ion exchange method is performed on the purified substance described above. As an ion exchange method, any method that can adjust (reduce) the amount of metal components in the purified substance is acceptable; however, from the viewpoint of easier preparation of the composition, it is preferable that the ion exchange method includes one or more of the following methods P1 to P3. It is even more preferable that the ion exchange method includes two or more of methods P1 to P3, and it is further preferable that it includes all of methods P1 to P3. Furthermore, when the ion exchange method includes all of methods P1 to P3, it is preferable that the methods are performed in the order of P1, P2, and P3. Method P1: A method of passing the purified substance through a first filling section filled with a mixed resin containing two or more resins selected from the group consisting of cation exchange resins, anion exchange resins, and chelating resins. Method P2: A method for passing the purified substance through at least one of a second packing section filled with cation exchange resin, a third packing section filled with anion exchange resin, and a fourth packing section filled with chelating resin. Method P3: A method for passing the purified substance through a membrane ion exchanger.

[0178] The steps of methods P1 to P3 described in detail in the following section, but if the ion exchange resin (cation exchange resin, anion exchange resin), chelating resin, and membrane ion exchanger used in each method are in a form other than H+ or OH-, it is preferable to regenerate them into H+ or OH- forms before use. Furthermore, a space velocity (SV) of 0.01 to 20.0 (L / h) for the purified substance in each method is preferable, and 0.1 to 10.0 (L / h) is more preferable. Also, a processing temperature of 0 to 60°C is preferable, and 10 to 50°C is more preferable.

[0179] Furthermore, examples of the forms of ion exchange resins and chelating resins include granular, fibrous, and porous bulk forms, with granular or fibrous forms being more preferred. For granular ion exchange resins and chelating resins, an average particle size of 10–2000 μm is preferred, and 100–1000 μm is more preferred. For the particle size distribution of granular ion exchange resins and chelating resins, a resin particle presence rate of 90% or more within a range of ±200 μm of the average particle size is preferred. Regarding the aforementioned average particle size and particle size distribution, for example, a method using a particle size distribution measuring device (MICROTRAC HRA3920, manufactured by Nikkiso Co., Ltd.) with water as the dispersion medium can be used for measurement.

[0180] -Method P1- Method P1 is a method of passing the purified substance through a first filling section filled with a mixed resin comprising two or more resins selected from the group consisting of cation exchange resins, anion exchange resins, and chelating resins. As the chelating resin, a known chelating resin can be used, specifically, a chelating resin described later can be used.

[0181] As a cation exchange resin, a known cation exchange resin can be used, which can be gel type or MR type (giant network type), with gel type cation exchange resin being preferred. Specifically, sulfonic acid type cation exchange resin and carboxylic acid type cation exchange resin can be cited as examples of cation exchange resins. Examples of cation exchange resins include Amberlite IR-124, Amberlite IR-120B, Amberlite IR-200CT, ORLITE DS-1, and ORLITE DS-4 (manufactured by Organo Corporation), Duolite C20J, Duolite C20LF, Duolite C255LFH, and Duolite C-433LF (manufactured by Sumika Chemtex Co., Ltd.), C100, C150, and C100×16MBH (manufactured by Purolite Corporation), and DIAION SK-110, DIAION SK1B, DIAION SK1BH, DIAION PK216, and DIAION PK228 (manufactured by Mitsubishi Chemical Corporation).

[0182] As an anion exchange resin, known anion exchange resins can be used, including gel-type and MR-type resins, with gel-type anion exchange resins being preferred. As a cation exchange resin, specifically, quaternary ammonium salt type anion exchange resins can be cited. Examples of anion exchange resins include Amberlite IRA-400J, Amberlite IRA-410J, Amberlite IRA-900J, Amberlite IRA67, ORLITE DS-2, ORLITE DS-5, and ORLITE DS-6 (manufactured by Organo Corporation), Duolite A113LF, Duolite A116, and Duolite A-375LF (manufactured by Sumika Chemtex Co., Ltd.), A400 and A500 (manufactured by Purolite Corporation), and DIAION SA12A, DIAION SA10AO, DIAION SA10AOH, DIAION SA20A, and DIAION WA10 (manufactured by Mitsubishi Chemical Corporation).

[0183] Examples of commercially available products that are pre-mixed with strong acidic cation exchange resin and strong basic anion exchange resin include Duolite MB5113, Duolite UP6000, and Duolite UP7000 (manufactured by Sumika Chemtex Co., Ltd.), Amberlite EG-4A-HG, Amberlite MB-1, Amberlite MB-2, Amberjet ESP-2, Amberjet ESP-1, ORLITE DS-3, ORLITE DS-7, and ORLITE DS-10 (manufactured by Organo Corporation), and DIAION SMNUP, DIAION SMNUPB, DIAION SMT100L, and DIAION SMT200L (all manufactured by Mitsubishi Chemical Corporation).

[0184] The mixed resin is preferably in the form of containing both cation exchange resin and anion exchange resin, or in the form of containing both cation exchange resin and chelating resin. When preparing a mixed resin containing both cation exchange resin and anion exchange resin, the mixing ratio of the two is preferably 1 / 4 to 4 / 1, and more preferably 1 / 3 to 3 / 1, in terms of the capacity ratio of cation exchange resin to anion exchange resin. Furthermore, a preferred combination of cation exchange resin and anion exchange resin is, for example, a combination of a gel-type sulfonic acid-type cation exchange resin and a gel-type quaternary ammonium salt-type anion exchange resin. When preparing a mixed resin containing both cation exchange resin and chelating resin, the mixing ratio of the two is preferably 1 / 4 to 4 / 1, and more preferably 1 / 3 to 3 / 1, in terms of the capacity ratio of cation exchange resin to chelating resin. Furthermore, a preferred combination of cation exchange resin and chelating resin may be a combination of gel-type sulfonic acid cation exchange resin and gel-type aminophosphonic acid chelating resin.

[0185] The first filling section typically includes a container and a mixed resin filled in the container, the mixed resin comprising two or more resins selected from the group consisting of cation exchange resins, anion exchange resins and chelating resins. Examples of containers include columns, cylinders, and filling towers; any container other than those exemplified above can be used as long as it allows the purified material to flow through after being filled with the aforementioned mixed resin.

[0186] In method P1, it is sufficient to pass the purified substance through at least one first filling section. From the viewpoint of making it easier to manufacture the composition, the purified substance may be passed through two or more first filling sections.

[0187] -Method P2- Method P2 is a method for passing the purified substance through at least one (preferably two or more) of a packing section filled with a second packing section filled with a cation exchange resin, a third packing section filled with an anion exchange resin, and a fourth packing section filled with a chelating resin. Examples of cation exchange resins and anion exchange resins that can be used in Method P2 include those listed in the description of Method P1.

[0188] The second filling section typically includes a container and the aforementioned cation exchange resin filled in the container. The third filling section typically includes a container and the aforementioned anion exchange resin filled in the container. The fourth filling section typically includes a container and a chelating resin, which will be described below, filled in the container.

[0189] A chelating resin generally refers to a resin having a coordinating group that can form a chelating bond with metal ions. For example, it is a resin obtained by introducing chelating-forming groups into styrene-divinylbenzene copolymers. The chelating resin can be gel-type or MR-type. From the viewpoint of processing efficiency, granular or fibrous chelating resins are preferred. Examples of chelating resins include various types such as iminodiacetic acid type, iminopropionic acid type, aminomethylphosphonic acid type, polyamine type, N-methylglucosamine type, aminocarboxylic acid type, dithiocarbamate type, thiol type, acetaminophen type, pyridine type, and phosphonic acid type. Specific examples include: MC700 manufactured by Sumika Chemtex Co., Ltd., ORLITE DS-22 manufactured by Organo Corporation, and D5843 manufactured by Purolite Corporation; Epirus MX-8 manufactured by MIYOSHI & FAT CO.,LTD., an example of an iminopropionic acid type chelating resin; MC960 manufactured by Sumika Chemtex Co., Ltd., an example of an aminomethylphosphonic acid type chelating resin; ORLITE DS-21 manufactured by Organo Corporation and D5817 manufactured by Purolite Corporation, an example of an aminophosphonic acid type chelating resin; and S985 manufactured by Purolite Corporation, DIAION CR-20 manufactured by Mitsubishi Chemical Corporation, and Sumika Chemtex Co., Ltd., an example of a polyamine type chelating resin. MC850, manufactured by Ltd., is an N-methylglucosamine type chelating resin, and Amberlite IRA-743, manufactured by Organo Corporation, is another example. S955, manufactured by Purolite Corporation, is a phosphonic acid type chelating resin.

[0190] The containers in the second filling section, the third filling section and the fourth filling section are defined as described above.

[0191] In method P2, the purified substance is passed through one of the second, third, and fourth filling sections. It is preferable to pass the purified substance through two or more of the second, third, and fourth filling sections. In method P2, it is preferable to pass the purified substance through at least the second filling section. Furthermore, in method P2, if the purified substance is passed through the fourth filling section, purification can be effectively performed even if the number of times the purified solution passes through the filling section is small. In method P2, when the purified substance is passed through two or more filling sections, the order in which the purified substance passes through two or more of the second, third, and fourth filling sections can be arbitrary.

[0192] In method P2, the purified substance is passed through at least one (preferably two or more) second filling sections, at least one (preferably two or more) third filling sections, and / or at least one fourth filling section. For example, from the viewpoint of easier composition manufacturing, the purified substance is passed through one or more (preferably two or more) second filling sections and one or more (preferably two or more) third filling sections. In this case, the order in which the purified substance is passed is not limited; for example, it can be passed alternately through the second and third filling sections, or it can be passed continuously through one of a plurality of second and third filling sections, and then continuously through another of a plurality of second and third filling sections. Furthermore, from the viewpoint of easier composition manufacturing, the purified substance can be passed through one or more second filling sections and one or more fourth filling sections. In this case, the order in which the purified substance is passed is not limited.

[0193] -Method P3- Method P3 is a method for passing the purified substance through a membrane ion exchanger. The membrane ion exchanger is a membrane having ion exchange groups. Examples of ion exchange groups include cation exchange groups (sulfonic acid groups, etc.) and anion exchange groups (ammonium groups, etc.).

[0194] Membrane ion exchangers can be composed of ion exchange resins themselves, or they can be formed by introducing cation exchange groups and / or anion exchange groups into a membrane support. The membrane ion exchanger (including the support containing the membrane ion exchanger) can be porous or non-porous. For example, the membrane ion exchanger (including the support containing the membrane ion exchanger) can be an aggregate of particles and / or fibers molded into a membrane. Furthermore, for example, the membrane ion exchanger can be any of the following: ion exchange membrane, ion exchange nonwoven fabric, ion exchange filter paper, and ion exchange filter cloth. As a form of using the membrane ion exchanger, for example, it can be assembled as a filter inside a cartridge to allow aqueous solutions to pass through. Semiconductor-grade membrane ion exchangers are preferred. Examples of commercially available membrane ion exchangers include Mustang (manufactured by Pall Corporation) and Protego Plus LT Purifier (manufactured by Entegris Corporation).

[0195] There are no particular limitations on the thickness of the membrane ion exchanger, but for example, 0.01 to 1 mm is preferred. The flow rate of the aqueous solution is, for example, 1 to 100 mL / (min·cm 2).

[0196] In method P3, it is sufficient to pass the purified substance through at least one membrane ion exchanger. From the viewpoint of facilitating the preparation of the composition, the purified substance may be passed through two or more membrane ion exchangers. Furthermore, when using two or more membrane ion exchangers, at least one membrane ion exchanger having a cation exchange group and an ion exchanger having an anion exchange group may be used respectively.

[0197] It is preferable to carry out the ion exchange method until the content of the metal component contained in the purified substance is within the range of the preferred metal component content mentioned above.

[0198] [Filtration Step] The above manufacturing method preferably includes a filtration step to remove foreign matter and coarse particles from the liquid. Known filtration methods can be used as the filtration method. Filtration using a filter is preferred.

[0199] The filter used in the filtration process can be any type that has been used for filtration purposes in the past, without any particular limitations. Examples of materials constituting the filter include fluoropolymers such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight resins), and polyarylates. Polyamide resins, PTFE, polypropylene (including high-density polypropylene), and polyarylates are preferred. By using a filter formed from these materials, highly polar foreign matter that is prone to causing defects can be removed from the composition more effectively.

[0200] It is preferable that the lower limit of the critical surface tension of the filter is 70 mN / m or more, and the upper limit is preferably 95 mN / m or less. In particular, it is preferable that the critical surface tension of the filter is 75 to 85 mN / m. Furthermore, the value of the critical surface tension is the manufacturer's nominal value. By using a filter with a critical surface tension within the above range, highly polar foreign matter that is prone to causing defects can be removed from the composition more effectively.

[0201] The pore size of the filter is preferably 0.001 to 1.0 μm, more preferably 0.02 to 0.5 μm, and even more preferably 0.01 to 0.1 μm. By setting the pore size of the filter within the above range, it is possible to suppress filter clogging while reliably removing fine foreign matter contained in the components.

[0202] When using filters, different filters can be combined. Filtration using the first filter can be performed only once or more than twice. When combining different filters for filtration more than twice, the filters can be of the same type or different types, but it is preferable that they are different types. Typically, it is preferable that at least one of the pore size and constituent materials of the first and second filters are different. It is preferable that the pore size of subsequent filters is the same as or smaller than that of the first filter. Furthermore, first filters with different pore sizes can be combined within the above-mentioned range. The pore size can be referred to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by companies such as Pall Corporation, Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (formerly Nippon micro squirrel Co., Ltd.), or KITZMICROFILTER CORPORATION. Furthermore, it is also possible to use polyamide to make "P-nylon filter (pore size 0.02μm, critical surface tension 77mN / m)"; (manufactured by Pall Corporation); high-density polyethylene to make "PE·Kleen filter (pore size 0.02μm)"; (manufactured by Pall Corporation); and high-density polyethylene to make "PE·Kleen filter (pore size 0.01μm)"; (manufactured by Pall Corporation).

[0203] Regarding the second filter, a filter made of the same material as the first filter described above can be used. It is possible to use a filter with the same pore size as the first filter described above. When using a second filter with a smaller pore size than the first filter, the ratio of the pore size of the second filter to the pore size of the first filter (pore size of the second filter / pore size of the first filter) is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and further preferably 0.3 to 0.9. By setting the pore size of the second filter within the above range, fine foreign matter mixed into the composition can be removed more reliably.

[0204] For example, filtration using the first filter can be performed by mixing a portion of the components of the composition with a mixture, and then, after preparing the composition by mixing the remaining components therein, a second filtration is performed. Furthermore, it is preferable that the filter used is treated before filtering the composition. It is preferable that the liquid used in this treatment is a liquid containing the composition and the components contained in the composition.

[0205] When filtration is performed, the upper limit of the filtration temperature is preferably below room temperature (25°C), more preferably below 23°C, and further preferably below 20°C. Furthermore, the lower limit of the filtration temperature is preferably above 0°C, more preferably above 5°C, and further preferably above 10°C. During filtration, particulate matter and / or impurities can be removed, but if the filtration is performed at the above-mentioned temperatures, the amount of particulate matter and / or impurities dissolved in the composition is reduced, thus allowing for more effective filtration.

[0206] [Electrostatic removal step] The method for manufacturing the composition may also include an electrostatic removal step for removing static electricity from the composition.

[0207] [Container] As a container for holding the components, a known container can be used, for example. A semiconductor-specific container with high cleanliness and minimal leaching of impurities is preferred. Examples of such containers include the "cleanbottle" series (manufactured by AICELLO CORPORATION) and "purebottle" (manufactured by KODAMA PLASTICS Co., Ltd.). Furthermore, from the viewpoint of preventing impurities from contaminating the raw materials and components, it is preferable to use a multi-layer container with a 6-layer structure made of 6 types of resin or a multi-layer container with a 7-layer structure made of 7 types of resin. Examples of multi-layer containers include those described in Japanese Patent Application Publication No. 2015-123351, the contents of which are incorporated herein by reference. For example, materials used for the inner wall of a container include at least one first resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin; a second resin different from the first resin; and metals such as stainless steel, Herstal alloy, Ingonane nickel, and Monel alloy. Furthermore, it is preferable that the inner wall of the container be formed or covered using the aforementioned materials.

[0208] As the second resin, a fluoropolymer (perfluoropolymer) is preferred. When using a fluoropolymer, the leaching of ethyl or propyl oligomers can be suppressed. Examples of containers described above include the FluoroPure PFA composite roller (manufactured by Entegris Corporation), page 4 of Japanese Patent Publication No. 3-502677, page 3 of Japanese Time Publication No. 2004 / 016526, and pages 9 and 16 of Japanese Time Publication No. 99 / 046309.

[0209] For the inner wall of the container, in addition to fluororesin, quartz and electropolished metal materials are also preferred. The electropolished metal material is preferably one selected from at least one of the group consisting of chromium (Cr) and nickel (Ni), and the combined content of Cr and Ni is more than 25% by mass relative to the total mass of the metal material. Examples include stainless steel and Ni-Cr alloys. The combined content of Cr and Ni in the metal material is preferably 25% by mass or more, and more preferably 30% by mass or more, relative to the total mass of the metal material. The maximum content is preferably 90% by mass or less relative to the total mass of the metal material.

[0210] As stainless steel, examples of known stainless steels can be cited. Stainless steel containing 8% by mass or more of Ni is preferred, and Worsfield stainless steel containing 8% by mass or more of Ni is even more preferred. Examples of Worsfield stainless steels include SUS (Steel Use Stainless) 304 (Ni content: 8% by mass, Cr content: 18% by mass), SUS304L (Ni content: 9% by mass, Cr content: 18% by mass), SUS316 (Ni content: 10% by mass, Cr content: 16% by mass) and SUS316L (Ni content: 12% by mass, Cr content: 16% by mass).

[0211] Examples of Ni-Cr alloys include known Ni-Cr alloys. Ni-Cr alloys with a Ni content of 40–75% by mass and a Cr content of 1–30% by mass are preferred. Examples of Ni-Cr alloys include Hoechst alloys, Monel alloys, and Ingonane alloys. Specifically, examples include Hoechst alloy C-276 (Ni content: 63% by mass, Cr content: 16% by mass), Hoechst alloy-C (Ni content: 60% by mass, Cr content: 17% by mass), and Hoechst alloy C-22 (Ni content: 61% by mass, Cr content: 22% by mass). Depending on the requirements, Ni-Cr alloys may also contain boron, silicon, tungsten, molybdenum, copper, or cobalt in addition to the above alloys.

[0212] As a method for electrolytic polishing of metallic materials, known methods can be cited, for example. Specifically, 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 are cited, and such contents are incorporated in this specification.

[0213] Polishing is preferable for metallic materials. Known methods can be cited as examples of polishing methods. From the viewpoint that the surface roughness of metallic materials is more easily reduced, it is preferable that the size of the abrasive grains used in fine polishing is #400 or less. Polishing is preferable to be performed before electrolytic polishing. For metallic materials, one or more of the following processes can be combined: polishing, pickling, and magnetic fluid polishing, which involve multiple stages of polishing, pickling, and other processes involving varying the size of the abrasive grains.

[0214] For containers, it is preferable to clean the inside of the container before filling with the composition. The cleaning liquid can be appropriately selected according to the application, preferably a liquid containing at least one of the composition or components added to the composition.

[0215] From the viewpoint of preventing changes in the composition of the components during storage, the interior of the container can be replaced with an inert gas (e.g., nitrogen and argon) with a purity of 99.99995% by volume or higher. In particular, gases with low moisture content are preferred. Furthermore, when transporting and storing containers containing the components, either ambient temperature or temperature control can be used. From the viewpoint of preventing deterioration, controlling the temperature within the range of -20 to 20°C is preferred.

[0216] <Processing Method for the Work to be Processed> Regarding the processing method for a work to be processed (the work to be processed) containing Ru and W using the composition of the present invention, a processing method for a substrate containing Ru and W will be described in detail. Hereinafter, the substrate containing Ru and W will also be referred to simply as the "substrate to be processed". Hereinafter, the work to be processed will be described in detail.

[0217] (The processed object) The processed object contains Ru and W. It is preferable that the Ru and W in the processed object are present on the substrate. Furthermore, the Ru in the processed object can be a Ru-containing compound containing Ru and other elements. Furthermore, the W in the processed object can be a W-containing compound containing W and other elements. That is, it is preferable that the processed object is a substrate containing Ru and W. In this case, the composition of the present invention is preferably used to selectively remove Ru-containing compounds on the substrate relative to W-containing compounds. Furthermore, "on the substrate" in this specification refers to, for example, any one of the back surface, side surface, and groove of the substrate. Furthermore, the Ru-containing compounds on the substrate include not only the case where the Ru-containing compounds are directly present on the surface of the substrate, but also the case where the Ru-containing compounds are present on the substrate through other layers. Hereinafter, the recesses provided in the substrate such as grooves and holes are referred to as "grooves, etc." Furthermore, the presence of Ru-containing compounds and W-containing compounds in the processed object means that when the processed object comes into contact with the composition, the Ru-containing compounds and W-containing compounds can come into contact with the composition. Furthermore, the accessible state includes not only the state in which the Ru-containing and W-containing substances are exposed to the outside, but also the state in which the Ru-containing or W-containing substances can be exposed by removing the components covering them through some action.

[0218] Semiconductor substrates are preferred as the type of substrate. Examples of substrates include semiconductor wafers, glass substrates for photomasks, glass substrates for liquid crystal displays, glass substrates for plasma displays, substrates for FEDs (Field Emission Displays), substrates for optical discs, substrates for magnetic discs, and substrates for optical-to-magnetic discs. Examples of materials constituting semiconductor substrates include group III-V compounds such as silicon, germanium, silicon-germanium, and GaAs, as well as combinations thereof.

[0219] Regarding the use of the processed object after processing based on the composition of the present invention, for example, it can be used in DRAM (Dynamic Random Access Memory), FRAM (Ferroelectric Random Access Memory), MRAM (Magnetoresistive Random Access Memory), PRAM (Phase Change Random Access Memory), and can also be used in logic circuits and processors, etc.

[0220] As a Ru-containing compound, it can be any substance containing Ru (Ru atoms), such as Ru monomers, Ru-containing alloys, Ru oxides, Ru nitrides, and Ru nitrides. Furthermore, Ru oxides, Ru nitrides, and Ru nitrides can be Ru-containing complex oxides, complex nitrides, and complex nitrides. The content of Ru atoms in the Ru-containing compound is preferably 10% by mass or more relative to the total mass of the Ru-containing compound, more preferably 30% by mass or more, further preferably 50% by mass or more, and especially preferably 90% by mass or more. The upper limit is preferably 100% by mass or less relative to the total mass of the Ru-containing compound.

[0221] Ru-containing compounds may contain other transition metals. Examples of transition metals include Rh (rhodium), Ti (titanium), Ta (tantalum), Co (cobalt), Cr (chromium), Hf (hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Cu (copper), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium).

[0222] The morphology of the Ru-containing material on the substrate can be, for example, any one of the following: film-like, wire-like, plate-like, columnar, and particle-like forms. Furthermore, as an example of the Ru-containing material being configured in a particle-like form, examples include, as described below, a substrate with particle-like Ru-containing material adhering as residue after dry etching of a substrate on which a Ru-containing film is disposed; a substrate with particle-like Ru-containing material adhering as residue after CMP (chemical mechanical polishing) of a Ru-containing film; and a substrate with particle-like Ru-containing material adhering in areas other than the predetermined area where the Ru-containing film is formed after a Ru-containing film is deposited on the substrate.

[0223] The thickness of the Ru-containing film can be appropriately selected according to the application. For example, 200 nm or less is preferred, 100 nm or less is even better, and 50 nm or less is further preferred. A minimum thickness of 0.1 nm or more is preferred. The Ru-containing film can be disposed on only one side of the main surface of the substrate, or it can be disposed on both sides of the main surface. Furthermore, the Ru-containing film can be disposed on the entire main surface of the substrate, or it can be disposed on a portion of the main surface of the substrate.

[0224] As a W-containing material, if it is a substance containing W (W atoms), examples include W monomers, W-containing alloys, W oxides, W nitrides, W oxynitrides and W carbides, and W borides. Furthermore, W oxides, W nitrides, W oxynitrides and W carbides can be any of the following: W-containing composite oxides, composite nitrides, composite oxynitrides and composite carbides. The content of W atoms in the W-containing material is preferably 10% by mass or more relative to the total mass of the W-containing material, more preferably 30% by mass or more, further preferably 50% by mass or more, and especially preferably 90% by mass or more. The upper limit relative to the total mass of the W-containing material is preferably 100% by mass or less.

[0225] W-containing compounds may contain other transition metals. Examples of transition metals include Rh (rhodium), Ti (titanium), Ta (tantalum), Co (cobalt), Cr (chromium), Hf (hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Cu (copper), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium).

[0226] The W-containing material on the substrate can be configured as any one of the following: film, wire, plate, column, and particle.

[0227] The thickness of the W-containing film can be appropriately selected according to the application. A thickness of 200 nm or less is preferred, 100 nm or less is even better, and 50 nm or less is further preferred. A minimum thickness of 0.1 nm or more is preferred. The W-containing film can be disposed on only one side of the main surface of the substrate, or on both sides of the main surface. Furthermore, the W-containing film can be disposed on the entire main surface of the substrate, or on a portion of the main surface of the substrate.

[0228] Furthermore, the processed material may include various layers or structures as needed, in addition to Ru-containing and W-containing materials. For example, one or more components selected from the group consisting of metal wiring, gate electrode, source electrode, drain electrode, insulating film, ferromagnetic layer, and non-magnetic layer may be disposed on the substrate. The substrate may include an exposed integrated circuit structure. Examples of integrated circuit structures include interconnection mechanisms such as metal wiring and dielectric materials. Examples of metals and alloys used for interconnection mechanisms include aluminum, copper-aluminum alloy, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and molybdenum. The substrate may include layers of materials selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.

[0229] There are no particular restrictions on the size, thickness, shape and layer structure of the substrate, and it can be selected appropriately according to the needs.

[0230] The manufacturing method of the workpiece can employ known manufacturing methods. For example, sputtering, chemical vapor deposition (CVD), molecular beam epitaxy (MBE), and atomic layer deposition (ALD) can be used to form Ru-containing films and / or W-containing films on a substrate. When forming a Ru-containing film using the above-described manufacturing methods, if the substrate has a structure with uneven surfaces, the Ru-containing film may sometimes be formed on all surfaces of the structure. Furthermore, especially when forming a Ru-containing film by sputtering and CVD, the Ru-containing film may sometimes also adhere to the back side of the substrate where the Ru-containing film is disposed (the surface opposite to the Ru-containing film side). Also, by performing the above methods with a predetermined mask, Ru-containing wiring and / or W-containing wiring can be formed on the substrate. Furthermore, a predetermined process can be performed on a substrate having a Ru-containing film, Ru-containing wiring, a W-containing film, and / or W-containing wiring to serve as the workpiece in the processing method of the present invention. For example, the substrate can be dry-etched to produce a substrate having dry etching residue containing Ru and W-containing material. Alternatively, CMP can be performed on the substrate to produce a substrate having Ru-containing material and W-containing material. Furthermore, a Ru-containing film can be deposited in a predetermined area of ​​the Ru-containing film formation on the substrate using sputtering, CVD, molecular beam epitaxy, or atomic layer deposition to produce a substrate having Ru-containing material and W-containing material attached to areas other than the predetermined Ru-containing film formation area.

[0231] The following describes in detail the steps that may be included in the treatment method for the object being treated.

[0232] [Step A] The method for processing the substrate to be processed (hereinafter also referred to as "this processing method") includes step A, which removes the Ru-containing material on the substrate using the composition of the present invention. Furthermore, the substrate (the substrate to be processed) containing the Ru-containing material and the W-containing material, which is the subject of this processing method, is as described above.

[0233] As a specific method for step A, a method of contacting the composition with the substrate to be treated, which is the object to be treated, can be cited as follows: immersing the object to be treated in the composition placed in a container, spraying the composition onto the object to be treated, allowing the composition to flow onto the object to be treated, and combinations thereof. Immersing the object to be treated in the composition is preferred.

[0234] Furthermore, mechanical stirring can be used to further enhance the cleaning ability of the composition. Examples of mechanical stirring methods include circulating the composition over the workpiece, flowing or spraying the composition over the workpiece, and locally stirring the composition near the substrate by irradiation with ultrasonic waves (e.g., megaphones). The processing time in step A can be adjusted appropriately. A processing time (contact time between the composition and the workpiece) of 0.25 to 10 minutes is preferred, and 0.5 to 2 minutes is more preferred. The temperature of the composition during processing is preferably 20 to 75°C, more preferably 20 to 60°C, further preferably 40 to 65°C, and particularly preferably 50 to 65°C.

[0235] In step A, while measuring the concentration of one or more components selected from the group consisting of hypochlorous acid or its salt, the first onium salt compound, compound B, solvent, and any other components, a process of adding one or more components selected from the group consisting of solvent and components can be performed as needed. By performing this process, the concentration of the components in the composition can be stably maintained within a predetermined range. Water is preferred as a solvent.

[0236] As a specific preferred embodiment of step A, examples include step A1, which involves using the composition to perform a rest etching process on a Ru-containing wiring or Ru-containing pad disposed on a substrate; step A2, which involves using the composition to remove the Ru-containing film from the outer edge of a substrate with a Ru-containing film disposed on it; step A3, which involves using the composition to remove Ru-containing material adhering to the back side of a substrate with a Ru-containing film disposed on it; step A4, which involves using the composition to remove Ru-containing material from a substrate after dry etching; step A5, which involves using the composition to remove Ru-containing material from a substrate after chemical mechanical polishing; and step A6, which involves using the composition to remove Ru-containing material from areas other than the predetermined Ru-containing film formation area on the substrate after a Ru-containing film has been deposited in the predetermined Ru-containing film formation area on the substrate. In the substrate processing method using the composition of the present invention, the Ru-containing material present in the substrate being processed is not removed during the above steps. Hereinafter, the processing method of the present invention used in each of the above processes will be described in detail.

[0237] (Step A1) As step A, step A1 can be described as using the composition to perform a rest etching process on the Ru-containing wiring (wiring containing Ru) and the Ru-containing pad (pad containing Ru) disposed on the substrate. Hereinafter, as examples of the work processed in step A1, a substrate having Ru-containing wiring and a substrate having Ru-containing pad will be specifically described in detail.

[0238] <Substrate with Ru-containing wiring> FIG1 shows an example of the workpiece to be processed in step A1, a schematic diagram of the upper part of a cross-section of a substrate with Ru-containing wiring (hereinafter also referred to as "Ru wiring substrate"). The Ru wiring substrate 10a shown in FIG1 has: a substrate (not shown); an insulating film 12 having trenches or the like disposed on the substrate; a barrier metal layer 14 disposed along the inner wall of the trenches or the like; and Ru-containing wiring 16 filling the interior of the trenches or the like. Furthermore, a W-containing substance (not shown) is present in the Ru wiring substrate 10a.

[0239] It is preferable that the Ru-containing wiring in the Ru wiring substrate includes Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. Regarding the materials constituting the barrier metal layer in the Ru wiring substrate, examples include Ti metal, Ti nitrides, Ti oxides, Ti-Si alloys, Ti-Si composite nitrides, Ti-Al alloys, Ta metal, Ta nitrides, and Ta oxides. Furthermore, while FIG. 1 describes a Ru wiring substrate having a barrier metal layer, it can also be a Ru wiring substrate without a barrier metal layer.

[0240] In step A1, the Ru wiring substrate is subjected to a rest etching process using the above-described composition, thereby removing a portion of the Ru-containing wiring to form a recess. More specifically, as shown in the Ru wiring substrate 10b of FIG2, if step A1 is performed, the barrier metal layer 14 and a portion of the Ru-containing wiring 16 are removed to form a recess 18. Furthermore, FIG2 shows the Ru wiring substrate 10b in which the barrier metal layer 14 and a portion of the Ru-containing wiring 16 are removed, but it is also possible to remove only a portion of the Ru-containing wiring 16 without removing the barrier metal layer 14 to form the recess 18. Furthermore, in the above process, it is difficult to remove W-containing substances.

[0241] As a method for manufacturing Ru wiring substrate, a method having the following steps can be cited, for example: forming an insulating film on a substrate, forming a groove on the insulating film, forming a barrier metal layer on the insulating film, forming a Ru-containing film to fill the groove, and performing a planarization process on the Ru-containing film.

[0242] <Substrate with Ru Pad> FIG3 shows a schematic diagram of the upper part of a cross section of a substrate with a Ru pad (hereinafter also referred to as "Ru pad substrate"), which is another example of the workpiece to be processed in the rest etching process of step A1.

[0243] The Ru pad substrate 20a shown in FIG3 has: a substrate (not shown); an insulating film 22 having grooves or the like disposed on the substrate; a Ru-containing pad 24 disposed along the inner wall of the grooves or the like; and a wiring portion 26 filling the interior of the grooves or the like. Furthermore, a W-containing substance (not shown) is present in the Ru pad substrate 20a.

[0244] It is preferable that the Ru-containing pad in the Ru pad substrate contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. Furthermore, in the Ru pad substrate shown in FIG. 3, a barrier metal layer may be additionally provided between the Ru-containing pad 24 and the insulating film 22. An example of the material constituting the barrier metal layer is the same as that in the Ru wiring substrate. For example, Cu metal, W metal, Mo metal, and Co metal can be used as materials constituting the wiring portion in the Ru pad substrate.

[0245] In step A1, the Ru pad substrate is subjected to a rest etching process using the above-described composition, thereby removing a portion of the Ru-containing pad to form a recess. More specifically, as shown in the Ru pad substrate 20b of FIG4, if step A1 is performed, a portion of the Ru-containing pad 24 and the wiring portion 26 is removed to form a recess 28. Furthermore, in the above process, the W-containing material is not removed.

[0246] As a method for manufacturing a Ru pad substrate, a method having the following steps can be cited: a step of forming an insulating film on a substrate; a step of forming a groove in the insulating film; a step of forming a Ru pad on the insulating film; a step of forming a metal film to fill the groove; and a step of performing a planarization treatment on the metal film.

[0247] As a specific method for step A1, a method for contacting the Ru wiring substrate or Ru pad substrate with the composition can be cited. The method for contacting the Ru wiring substrate or Ru pad substrate with the composition is as described above. The preferred ranges for the contact time between the Ru wiring substrate or Ru pad substrate and the composition, and the temperature of the composition are as described above.

[0248] (Step B) Furthermore, Step B can be performed as needed before or after Step A1. Step B involves processing the substrate obtained in Step A1 using a predetermined solution (hereinafter also referred to as "specific solution"). In particular, when a barrier metal layer is disposed on the substrate, the solubility of the components constituting the Ru-containing wiring or Ru pads (hereinafter also referred to as "Ru-containing wiring, etc.") and the components constituting the barrier metal layer may differ depending on their type. In this case, it is preferable to use a solution with superior solubility relative to the barrier metal layer to adjust the degree of solubility of the Ru-containing wiring, etc., and the barrier metal layer. From this perspective, it is preferable that the specific solution has poor solubility for the Ru-containing wiring, etc., but excellent solubility for the substances constituting the barrier metal layer. Furthermore, it is preferable that the specific solution has poor solubility for W-containing substances.

[0249] As a specific solution, examples include solutions selected from the group consisting of a mixture of hydrofluoric acid and hydrogen peroxide water (FPM), a mixture of sulfuric acid and hydrogen peroxide water (SPM), a mixture of ammonia and hydrogen peroxide water (APM), and a mixture of hydrochloric acid and hydrogen peroxide water (HPM). The composition of FPM is preferably in the range of "hydrofluoric acid:hydrogen peroxide water:water = 1:1:1" to "hydrofluoric acid:hydrogen peroxide water:water = 1:1:200" (volume ratio). The composition of SPM is preferably in the range of "sulfuric acid:hydrogen peroxide water:water = 3:1:0" to "sulfuric acid:hydrogen peroxide water:water = 1:1:10" (volume ratio). The composition of APM is preferably in the range of "ammonia water:hydrogen peroxide water:water = 1:1:1" to "ammonia water:hydrogen peroxide water:water = 1:1:30" (volume ratio). The composition of HPM is preferably within the range of "hydrochloric acid:hydrogen peroxide water:water = 1:1:1" to "hydrochloric acid:hydrogen peroxide water:water = 1:1:30" (volume ratio). Furthermore, the preferred composition ratios mentioned refer to the following: 49% by mass of hydrofluoric acid, 98% by mass of sulfuric acid, 28% by mass of ammonia, 37% by mass of hydrochloric acid, and 31% by mass of hydrogen peroxide water. As a specific solution, from the viewpoint of the dissolution capacity of the barrier metal layer, SPM, APM, or HPM are preferred. As a specific solution, from the viewpoint of reducing roughness, APM, HPM, or FPM are preferred, with APM being more preferred. As a specific solution, from the viewpoint of excellent performance balance, APM or HPM are preferred.

[0250] In step B, the method of treating the substrate obtained in step A1 with a specific solution is preferably a method of contacting the specific solution with the substrate obtained in step A1. For example, a method similar to the method of contacting the composition with the substrate can be used to bring the specific solution into contact with the substrate. The contact time between the specific solution and the substrate obtained in step A1 is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes.

[0251] In this processing method, steps A1 and B can be performed alternately. When performing the alternating repetition, it is preferable to perform steps A1 and B 1 to 10 times respectively. Furthermore, when performing steps A1 and B alternately, the first and last steps can be either steps A1 or B.

[0252] (Step A2) As step A, for example, step A2 can be described as removing the Ru-containing film from the outer edge of a substrate on which the Ru-containing film is disposed using a composition. FIG5 shows a schematic diagram (top view) of an example of a substrate on which the Ru-containing film is disposed as the workpiece to be processed in step A2. The workpiece 30 to be processed in step A2 shown in FIG5 is a laminate having a substrate 32 and a Ru-containing film 34 disposed on one side of the main surface of the substrate 32 (the entire area surrounded by solid lines). As will be described later, in step A2, the Ru-containing film 34 located at the outer edge 36 (the area outside the dashed lines) of the workpiece 30 is removed. Also, a W-containing substance (not shown) is present in the workpiece 30.

[0253] The substrate and the Ru-containing film in the processed object are as described above. Furthermore, it is preferable that the Ru-containing film contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides.

[0254] As a specific method for step A2, for example, a method in which the composition is supplied from a nozzle so that the composition contacts only the Ru-containing film at the outer edge of the substrate can be used. When performing the process of step A2, the substrate processing apparatus and substrate processing method described in Japanese Patent Application Publication Nos. 2010-267690, 2008-080288, 2006-100368, and 2002-299305 can be preferred.

[0255] The contact method between the composition and the treated object is as described above. The preferred ranges for the contact time between the composition and the treated object and the temperature of the composition are as described above. Furthermore, it is difficult to remove the W-containing substance in step A2.

[0256] (Step A3) As step A, step A3 can be described as using a composition to remove the Ru-containing material adhering to the back side of a substrate on which the Ru-containing film is disposed. As the workpiece to be processed in step A3, the workpiece used in step A2 can be described. When the substrate used in step A2 is formed and the workpiece on which the Ru-containing film is disposed on one side of the main surface of the substrate, the Ru-containing film is formed by sputtering and CVD, etc. At this time, Ru-containing material sometimes adheres to the surface on the side opposite to the Ru-containing film side of the substrate (back side). Step A3 is performed in order to remove the Ru-containing material from such workpiece.

[0257] As a specific method for step A3, for example, a method of spraying the composition so that the composition only contacts the back side of the substrate can be cited.

[0258] The contact method between the composition and the treated object is as described above. The preferred ranges for the contact time between the composition and the treated object and the temperature of the composition are as described above. Furthermore, the W-containing substance is not removed in step A3.

[0259] (Step A4) As step A, step A4 can be described as removing Ru-containing substances from the substrate after dry etching using a composition. Figures 6 and 8 show schematic diagrams of an example of the workpiece processed in step A4. Each figure will be described in detail below.

[0260] The workpiece 40 shown in FIG. 6 has a Ru-containing film 44, an etch stop layer 46, an interlayer insulating film 48, and a metal hard mask 50 sequentially on a substrate 42. Through a dry etching process, grooves 52 exposing the Ru-containing film 44 are formed at predetermined positions. That is, the workpiece shown in FIG. 6 has a substrate 42, a Ru-containing film 44, an etch stop layer 46, an interlayer insulating film 48, and a metal hard mask 50 sequentially. At the opening of the metal hard mask 50, there is a stack of grooves 52 extending from its surface to the surface of the Ru-containing film 44. The inner wall 54 of the grooves 52 is composed of a cross-sectional wall 54a including the etch stop layer 46, the interlayer insulating film 48, and the metal hard mask 50, and a bottom wall 54b including the exposed Ru-containing film 44. Dry etching residue 56 is attached to the inner wall 54 of the grooves. The dry etching residue contains Ru. Furthermore, a W-containing substance (not shown) is present in the processed material 40.

[0261] The workpiece 60b shown in FIG8 is obtained by dry etching the workpiece shown in FIG7 before dry etching. The workpiece 60a shown in FIG7 has an insulating film 62 disposed on a substrate (not shown), a Ru-containing film 66 filling the grooves formed in the insulating film 62, and a metal hard mask 64 located at the opening of the Ru-containing film 66 disposed on the insulating film 62. The workpiece 60a is obtained by sequentially forming the insulating film 62 and the metal hard mask 64 on a substrate (not shown), forming grooves in the insulating film 62 located at the opening of the metal hard mask 64, and filling the grooves with Ru-containing material to form the Ru-containing film 66. If the workpiece 60a shown in FIG7 is dry etched, the Ru-containing film is etched to obtain the workpiece 60b shown in FIG8. The workpiece 60b shown in Figure 8 has an insulating film 62 disposed on a substrate (not shown), a Ru-containing film 66 filling a portion of a groove or the like formed in the insulating film 62, and a metal hard mask 64 having an opening at the location of the groove or the like on the insulating film 62. Dry etching residue 76 is attached to the cross-sectional wall 74a composed of the insulating film 62 and the metal hard mask 64 within the groove or the like, and the bottom wall 74b composed of the Ru-containing film 66. The dry etching residue contains Ru. Furthermore, a W-containing substance (not shown) is present in the workpiece 60b.

[0262] The Ru-containing film supplied to the workpiece in step A4 preferably contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The Ru-containing material supplied to the workpiece in step A4 preferably contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The interlayer insulating film and the insulating film can be made of known materials. The metal hard mask can be made of known materials. Furthermore, while Figures 6, 7, and 8 describe the use of a metal hard mask, a resist mask formed using a known photoresist material can also be used.

[0263] As a specific method for step A4, a method of contacting the composition with the object to be processed can be cited. The method of contacting the composition with the wiring board is as described above. The preferred ranges for the contact time between the composition and the wiring board and the temperature of the composition are as described above. Furthermore, the W-containing material is not removed in step A4.

[0264] (Step A5) As step A, step A5 involves using a composition to remove Ru-containing contaminants from the substrate after chemical mechanical polishing (CMP). CMP technology is incorporated into manufacturing steps such as planarization of insulating films, planarization of interconnects, and inlay wiring. The substrate after CMP is sometimes contaminated with a large amount of particles used in the polishing process and metallic impurities. Therefore, these contaminants need to be removed and the substrate cleaned before proceeding to the next processing stage. Therefore, by performing step A5, Ru-containing contaminants that adhere to the substrate when the CMP-treated object has Ru-containing wiring or a Ru-containing film can be removed.

[0265] Regarding the workpiece to be processed in step A5, as described above, a substrate containing a Ru-containing compound after CMP can be cited. It is preferable that the Ru-containing compound includes Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. Furthermore, a W-containing compound is present on the Ru-containing substrate after CMP. As a specific method for step A5, a method of contacting the composition with the workpiece can be cited. The method of contacting the composition with the wiring substrate is as described above. The preferred ranges for the contact time between the composition and the wiring substrate and the temperature of the composition are as described above. Furthermore, the W-containing compound is not removed in step A5.

[0266] (Step A6) As step A, step A6 can be described as using a composition to remove the Ru-containing material from areas other than the Ru-containing film formation predetermined area on the substrate after the Ru-containing film has been deposited in the Ru-containing film formation predetermined area on the substrate. As described above, regarding the Ru-containing film formation method, sputtering, CVD, MBE and ALD methods can be used to form the Ru-containing film on the substrate. When the Ru-containing film is formed in the Ru-containing film formation predetermined area (the predetermined area for forming the Ru-containing film) on the substrate by the above methods, the Ru-containing film can also be formed in areas that are not intended to be formed (areas other than the Ru-containing film formation predetermined area). For example, the sidewall of the insulating film when filling the groove of the insulating film, etc., with the Ru-containing film can be described. An example of the workpiece processed in step A6 is shown in FIG10. The workpiece 80b shown in FIG10 can be obtained by forming a Ru-containing film on the workpiece 80a before the Ru-containing film formation shown in FIG9. The workpiece 80a shown in FIG9 has an insulating film 82 disposed on a substrate (not shown) and a metal hard mask 84 disposed on the insulating film 82. The insulating film 82 has grooves or the like at the openings of the metal hard mask 84. A Ru-containing film is formed by filling a portion of the grooves or the like 86 of the workpiece 80a, thereby obtaining the workpiece 80b shown in FIG10. The workpiece 80b shown in FIG10 has an insulating film 82 disposed on a substrate (not shown), a Ru-containing film 88 filling a portion of the grooves or the like 86 formed on the insulating film 82, and a metal hard mask 84 having openings at the positions of the grooves or the like 86 disposed on the insulating film 82. Residue 92 from the formation of the Ru-containing film is attached to the cross-sectional wall 90a composed of the insulating film 82 and the metal hard mask 84 and the bottom wall 90b composed of the Ru-containing film 88 in the grooves or the like 86. In the above-described sample, the region containing the Ru-containing film 88 corresponds to the predetermined region for Ru-containing film formation, and the cross-sectional wall 90a and bottom wall 90b correspond to the regions other than the predetermined region for Ru-containing film formation. Furthermore, a W-containing substance (not shown) exists in the treated object 80b.

[0267] The Ru-containing film preferably contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The Ru-containing material preferably contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The hard metal mask can be made of a known material. Furthermore, while Figures 9 and 10 describe the use of a hard metal mask, a resist mask formed using a known photoresist material can also be used.

[0268] As a specific method for step A6, a method of contacting the composition with the object to be processed can be cited. The method of contacting the composition with the wiring board is as described above. The preferred ranges for the contact time between the composition and the wiring board and the temperature of the composition are as described above. Furthermore, it is difficult to remove the W-containing material in step A6.

[0269] [Step C] This processing step may include step C, which, after step A, uses a rinsing solution to rinse the substrate obtained in step A, if necessary.

[0270] As rinsing solutions, for example, hydrofluoric acid (0.001 to 1% by mass is preferred), hydrochloric acid (0.001 to 1% by mass is preferred), hydrogen peroxide solution (0.5 to 31% by mass is preferred, 3 to 15% by mass is more preferred), a mixture of hydrofluoric acid and hydrogen peroxide solution (FPM), a mixture of sulfuric acid and hydrogen peroxide solution (SPM), a mixture of ammonia and hydrogen peroxide solution (APM), a mixture of hydrochloric acid and hydrogen peroxide solution (HPM), carbon dioxide (10 to 60 ppm by mass is preferred), ozone solution (10 to 60 ppm by mass is preferred), hydrogen water (10 to 20 ppm by mass is preferred), citric acid aqueous solution (0.01 to 10% by mass is preferred), acetic acid (acetic acid stock solution, or... The preferred solutions are: 0.01–10% by mass acetic acid aqueous solution, sulfuric acid (1–10% by mass sulfuric acid aqueous solution), ammonia (0.01–10% by mass ammonia solution), isopropanol (IPA), hypochlorous acid aqueous solution (1–10% by mass hypochlorous acid aqueous solution), aqua regia (preferably a solution in which the volume ratio of 37% by mass hydrochloric acid to 60% by mass nitric acid is equivalent to 2.6 / 1.4–3.4 / 0.6), ultrapure water, nitric acid (0.001–1% by mass nitric acid is preferred), perchloric acid (0.001–1% by mass perchloric acid is preferred), oxalic acid aqueous solution (0.01–10% by mass aqueous solution is preferred), or periodic acid aqueous solution (0.5–10% by mass periodic acid aqueous solution is preferred; for example, orthoperiodic acid and metaperiodic acid can be used as periodic acid). The preferred conditions for FPM, SPM, APM, and HPM are, for example, the same as the preferred conditions for the specific solutions used above for FPM, SPM, APM, and HPM. Furthermore, fluorine, nitric acid, perchloric acid, and hydrochloric acid refer to aqueous solutions of HF, HNO3, HClO4, and HCl dissolved in water, respectively. Ozone water, carbon dioxide, and hydrogen water refer to aqueous solutions of O3, CO2, and H2 dissolved in water, respectively. These rinsing solutions can be mixed without impairing the purpose of the rinsing step.

[0271] As a rinsing fluid, from the viewpoint of further reducing residual chlorine on the substrate surface after the rinsing step, carbon dioxide, ozone water, hydrogen water, hydrofluoric acid, citric acid aqueous solution, hydrochloric acid, sulfuric acid, ammonia water, hydrogen peroxide water, SPM, APM, HPM, IPA, hypochlorous acid aqueous solution, aqua regia or FPM are preferred, and hydrofluoric acid, hydrochloric acid, hydrogen peroxide water, SPM, APM, HPM or FPM are even more preferred.

[0272] As a specific method for step C, for example, a method of bringing the rinsing liquid into contact with the substrate obtained in step A, which is the object to be treated. As a contact method, for example, a method of immersing the substrate in the rinsing liquid placed in a tank, a method of spraying the rinsing liquid onto the substrate, a method of flowing the rinsing liquid onto the substrate, and any combination thereof.

[0273] The treatment time (the contact time between the rinsing solution and the treated object) is, for example, 5 seconds to 5 minutes. The temperature of the rinsing solution during treatment is usually preferred to be 16 to 60°C, and more preferably 18 to 40°C. When using SPM as the rinsing solution, the temperature is preferably 90 to 250°C.

[0274] [Step D] This processing method may include step D, which involves performing a drying process as needed after step C. Examples of drying methods include rotary drying, flow of drying gas on a substrate, heating of the substrate (e.g., heating based on a heating plate or infrared lamp), IPA (isopropyl alcohol) vapor drying, marangoni drying, notagononi drying, and combinations thereof. The drying time can be appropriately varied depending on the specific method used, for example, from approximately 30 seconds to 10 minutes.

[0275] (Other Steps) In addition to the steps described above, this processing method may include other steps. Examples of other steps include the formation of structures such as metal wiring, gate structures, source structures, drain structures, insulating films, ferromagnetic layers, and non-magnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and etching), resist formation, exposure and removal, heat treatment, cleaning, and inspection. This processing method can be performed at any stage of the back end of the line (BEOL), middle end of the line (MOL), and front end of the line (FEOL), but is preferably performed in the front end or middle end of the line. [Example]

[0276] Hereinafter, the present invention will be described in further detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limited by the embodiments shown below.

[0277] <Preparation of Compositions> After obtaining a mixture by mixing ultrapure water and various components in the amounts shown in the table below, the mixture was thoroughly stirred using a stirrer to obtain the compositions of each embodiment and each comparative example. Furthermore, the contents of the compositions in the table are based on mass, and the residual portion of the total of various components is water. The residual portion refers to the value obtained by subtracting the total content of various components contained in the composition other than water when the total mass of the composition is set to 100% by mass. Also, hydrochloric acid or potassium hydroxide was added in such a way that the pH of each composition was the pH shown in the table. In any composition, the total content of the above-mentioned hydrochloric acid and the above-mentioned potassium hydroxide was also 2% by mass or less relative to the total mass of the composition. Hereinafter, the various components in the table below are shown.

[0278] [Hypochlorous acid or its salts] ·Sodium hypochlorite ·Potassium hypochlorite ·Hypochlorous acid ·Tetramethylammonium hypochlorite

[0279] [First Onium Salt Compound] ·Tetrapropylammonium hydroxide ·n-Octyltrimethylammonium chloride ·Tetrapropylammonium chloride ·Tetramethylammonium hydroxide ·Tetraethylammonium chloride ·Hexamethylammonium chloride ·Decyltrimethylammonium chloride ·Dodecyltrimethylammonium chloride ·Octyltrimethylammonium chloride ·Tetradecyltrimethylammonium chloride ·Eicosyltrimethylammonium chloride ·Tetrabutylphosphonium hydroxide ·Triphenylsilane chloride ·Butyltriphenylphosphonium chloride ·Trimethylphenylammonium hydroxide ·1-Butyl-1-methylpyrrolidine onium chloride ·Tetramethylammonium bromide

[0280] [Compound X] (Resin A)

[0281] [Chemical 12]

[0282] (Compound B)

[0283] [Chemical 13]

[0284] ·Chlorhexidine·1-(o-tolyl)biguanide·phenethylamine·arginine·ricin·aspartic acid·dipropylamine·ethylenediaminetetraacetic acid·cis-2,6-dimethylpiperazine·1,3-diphenylguanidine·1,2,3-tris(tert-butoxycarbonyl)guanidine·1-acetylguanidine·7-methyl1,5,7-triazabicyclo[4.4.0]dec-5-ene·1,2,3-benzotriazole·1-[N,N-bis(2 [-Ethylhexyl)aminomethyl]methylbenzotriazole·5-amino-1H-tetrazole·2-aminoquinoline·2-quinolinecarboxylic acid·8-hydroxyquinaldinic acid·2,6-pyridinic acid·bis(2-pyridylmethyl)amine·3H-1,2,3-triazolo[4,5-b]pyridine-3-ol·indole-3-butyric acid·carbazole·2-amino-1-butanol·2-amino-2-hydroxymethyl-1,3-propanediol·1-amino-4-hydroxyadamantane

[0285] (Second onion salt compound) ·Benzalkonium chloride ·Benzalkonium chloride ·1-Butyl-1-methylpyrrolidine onion chloride ·1-Butyl-2,3-dimethylimidazolium chloride ·1,1-Dimethylpiperidine onion chloride ·6-azaspiro[5,5]undecyl chloride ·1-Hexyl-3-methylimidazolium chloride ·1,1'-Diheptyl-4,4'-Bipyridine dibromide ·Ampoule hydrochloride ·Butyltriphenylphosphonium chloride ·Butyltriphenylsilane chloride ·5-azaspiro[4,4]nonane chloride

[0286] (Compounds containing a carbonyl group) ·Malonic acid·1,2,3,4,5,6-cyclohexanehexacarboxylic acid·dimethyl oxalate

[0287] (Abrasive Particles) · Colloidal Silicon Dioxide: Ultra-high purity colloidal silicon dioxide PL-3, average primary particle size 35nm, manufactured by FUSO CHEMICAL CO., LTD.

[0288] (Other ingredients) ·Catechol

[0289] [Solvent] ·Ultrapure water

[0290] <Evaluation> The evaluation of ERR(Ru / W) and RuER is based on the ratio of the etching rate of Ru (RuER, Ru dissolution rate) to the etching rate of W (WER, W dissolution rate) of the composition. The evaluation is performed in the following order: A substrate with a Ru layer (a layer composed of Ru monomers) formed by PVD was prepared on one surface of a commercially available silicon wafer (diameter: 12 inches). The obtained substrate was placed in a container filled with a 1% (w / w) aqueous citric acid solution, and the aqueous citric acid solution was stirred for pretreatment. The pretreated substrate was then placed in a container filled with the compositions of each embodiment or comparative example, and the composition was stirred for 1 minute to remove the Ru layer. The temperature of the composition was 25°C. The thickness of the Ru layer before and after the removal process was measured using a thin film evaluation X-ray fluorescence analyzer (XRF AZX-400, manufactured by Rigaku Corporation). The etch rate (RuER) of the Ru layer before and after the removal process was calculated based on the difference in Ru layer thickness before and after the removal process, and the RuER was evaluated according to the following evaluation criteria. Furthermore, a W layer (a layer composed of W monomers) was formed by CVD, and the W layer removal process was performed in the same manner as described above. The thickness of the W layer before and after the removal process was determined using a resistivity meter (VR300DE, manufactured by Kokusai Electric Semiconductor Service Inc.). The etch rate (WER) of the W layer (Å / min) was calculated based on the determined W layer thickness. The ratio of RuER to WER (ERR(Ru / W)) was obtained by dividing the RuER calculated by the above method by the WER. Based on the determined ERR(Ru / W), the ERR(Ru / W) was evaluated according to the following criteria.

[0291] [Evaluation criteria for RuER] A: RuER is above 200 Å / min B: RuER is above 150 Å / min and below 200 Å / min C: RuER is above 100 Å / min and below 150 Å / min D: RuER is above 50 Å / min and below 100 Å / min E: RuER is above 30 Å / min and below 50 Å / min F: RuER is above 0 Å / min and below 30 Å / min

[0292] [Evaluation Criteria for ERR (Ru / W)] A: ERR (Ru / W) ≥ 50.0 B: ERR (Ru / W) ≥ 30.0 and < 50.0 C: ERR (Ru / W) ≥ 20.0 and < 30.0 D: ERR (Ru / W) ≥ 10.0 and < 20.0 E: ERR (Ru / W) ≥ 5.0 and < 10.0 F: ERR (Ru / W) ≥ 2.0 and < 5.0 G: ERR (Ru / W) ≥ 0.0 and < 2.0

[0293] <Results> The various components and evaluation results of the composition are shown in the table below. The “content” of each component means the content of each component relative to the total mass of the composition (mass% or mass ppm). Furthermore, the total residual of the contents of each component is water. The “cation atom” of “first onium salt compound” means a cationized atom among the cations present in the first onium salt compound. N represents a nitrogen atom, S represents a sulfur atom, and P represents a phosphorus atom. The “maximum number of carbon atoms of a specific alkyl group” of “first onium salt compound” means that the first onium salt compound is a compound represented by formula (Z1) or a compound represented by formula (Z3), where R Z11~R Z14 and R Z31~R Z36 are alkyl groups that may have substituents, and the maximum number of carbon atoms in the above alkyl groups. Specifically, when the first onium salt compound is n-octyltrimethylammonium chloride, n-octyltrimethylammonium chloride is a compound represented by formula (Z1), and is a compound having three methyl groups and an n-octyl group, as an alkyl group represented by R Z11 to R Z14. Therefore, the maximum number of carbon atoms in the specific alkyl group is "8" times the number of carbon atoms in the n-octyl group. The "cation atom" in "compound X" refers to the cation that has been cationized in compound X. N represents a nitrogen atom, S represents a sulfur atom, and P represents a phosphorus atom. The "molecular weight" of "compound X" represents the weight-average molecular weight calculated by GPC. "pH" represents the pH value obtained by measuring the composition using a pH meter (F-71S, manufactured by HORIBA, Ltd.). Furthermore, the measurement temperature is 25°C. "Content ratio" represents the mass ratio of the content of hypochlorous acid or its salt to the content of compound X (content of hypochlorous acid or its salt / content of compound X).

[0294] [Table 1] Hypochlorous acid or its salts First onium salt compound Compound X pH Content ratio Evaluation results type content (quality%) type Cation atoms Maximum number of carbon atoms in a specific alkyl group content (quality%) type molecular weight content (mass ppm) RuER ERR (Ru / W) Example 1-1 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 2000 25 12.0 400 A A Examples 1-2 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Resin A2 Resin A 3000 25 13.0 400 A A Examples 1-3 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 Resin A3 Resin A 2000 25 12.0 400 A A Examples 1-4 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Resin A4 Resin A 4000 25 12.0 400 A B Examples 1-5 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 polyallylamine Compound B 3500 25 13.0 400 A C Examples 1-6 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Polyethyleneimine Compound B 2000 25 13.0 400 A C Examples 1-7 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Compound B1 Compound B 3000 25 12.0 400 A C Examples 1-8 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Compound B2 Compound B 5000 25 12.0 400 A D Examples 1-9 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 2500 25 13.0 400 A A Examples 1-10 Sodium hypochlorite 1 Tetramethylammonium hydroxide N 1 5 Resin A3 Resin A 3000 25 13.0 400 A A Examples 1-11 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Resin A1 Resin A 2000 25 13.0 400 A A Examples 1-12 Sodium hypochlorite 1 Tetraethylammonium chloride N 2 5 Resin A3 Resin A 3500 25 12.0 400 A A Examples 1-13 Sodium hypochlorite 1 Hexamethylammonium chloride N 1 5 Resin A2 Resin A 3000 25 12.0 400 B A Examples 1-14 Sodium hypochlorite 1 Decyltrimethylammonium chloride N 10 5 Resin A3 Resin A 2000 25 12.0 400 A A Examples 1-15 Sodium hypochlorite 1 Dodecyltrimethylammonium chloride N 12 5 Resin A2 Resin A 2500 25 12.0 400 B A Examples 1-16 Sodium hypochlorite 1 Octadecyltrimethylammonium chloride N 18 5 Resin A1 Resin A 4000 25 13.0 400 B A Examples 1-17 Sodium hypochlorite 1 Tetradecyltrimethylammonium chloride N 14 5 Resin A1 Resin A 5000 25 13.0 400 B A Examples 1-18 Sodium hypochlorite 1 Eicosyltrimethylammonium chloride N 20 5 Resin A2 Resin A 3500 25 12.0 400 C A

[0295] [Table 2] Hypochlorous acid or its salts First onium salt compound Compound X pH Content ratio Evaluation results type content (quality%) type cation atom Specific alkyl Maximum number of carbons content (quality%) type molecular weight content (mass ppm) RuER ERR (Ru / W) Examples 1-19 Sodium hypochlorite 1 Tetrabutylphosphonium hydroxide P 4 5 Resin A1 Resin A 4000 25 12.0 400 D A Examples 1-20 Sodium hypochlorite 1 Triphenylsilane chloride S - 5 Resin A1 Resin A 2500 25 13.0 400 D A Examples 1-21 Sodium hypochlorite 1 Butyltriphenylphosphonium chloride P - 5 Resin A1 Resin A 3500 25 12.0 400 D A Examples 1-22 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A2 Resin A 1000 25 12.0 400 A C Examples 1-23 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Resin A2 Resin A 1400 25 12.0 400 A B Examples 1-24 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A3 Resin A 8500 25 12.0 400 A B Examples 1-25 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A2 Resin A 10000 25 13.0 400 A B Examples 1-26 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Resin A2 Resin A 22000 25 13.0 400 A C Examples 1-27 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A2 Resin A 100000 25 13.0 400 A C Examples 1-28 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Resin A3 Resin A 250000 25 13.0 400 A D Examples 1-29 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Resin A1 Resin A 3000 25 6.0 400 C B Examples 1-30 Sodium hypochlorite 1 Tetraethylammonium chloride N 2 5 Resin A3 Resin A 3000 25 7.0 400 B B Examples 1-31 Sodium hypochlorite 1 Tetraethylammonium chloride N 2 5 Resin A1 Resin A 3000 25 8.0 400 B A Examples 1-32 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A3 Resin A 3000 25 10.0 400 A A Examples 1-33 Sodium hypochlorite 1 Tetraethylammonium chloride N 2 5 Resin A1 Resin A 3000 25 11.5 400 A A Examples 1-34 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 3000 25 13.5 400 B A Examples 1-35 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Resin A1 Resin A 3000 25 13.9 400 B B Examples 1-36 Sodium hypochlorite 1 Tetraethylammonium chloride N 2 5 Resin A1 Resin A 3000 1 12.0 10000 A C

[0296] [Table 3] Hypochlorous acid or its salts First onium salt compound Compound X pH Content ratio Evaluation results type content (quality%) type cation atom Specific alkyl Maximum number of carbons content (quality%) type molecular weight content (mass ppm) RuER ERR (Ru / W) Examples 1-37 Sodium hypochlorite 1 Tetraethylammonium chloride N 2 5 Resin A1 Resin A 3000 5 13.0 2000 A B Examples 1-38 Sodium hypochlorite 1 Tetraethylammonium chloride N 2 5 Resin A1 Resin A 3000 10 13.0 1000 A A Examples 1-39 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 3000 100 13.0 100 A A Examples 1-40 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Resin A1 Resin A 3000 500 12.0 20 A A Examples 1-41 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A3 Resin A 3000 1000 13.0 10 A A Examples 1-42 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A3 Resin A 3000 2000 12.0 5 B A Examples 1-43 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 3000 10000 12.0 1 C B Examples 1-44 Sodium hypochlorite 2 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 3000 25 12.0 800 A A Examples 1-45 Sodium hypochlorite 5 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 3000 50 12.5 1000 A A Examples 1-46 Sodium hypochlorite 10 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 3000 200 13.0 500 A A Examples 1-47 Sodium hypochlorite 15 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 3000 200 13.5 750 A B Examples 1-48 Sodium hypochlorite 20 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 3000 500 13.5 400 A C Examples 1-49 Sodium hypochlorite 0.2 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 3000 5 12.0 400 B A Examples 1-50 Sodium hypochlorite 0.07 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 3000 2.5 12.0 280 C A Examples 1-51 Sodium hypochlorite 0.02 Tetrapropylammonium hydroxide N 3 5 Resin A1 Resin A 3000 0.5 12.0 400 D A Examples 1-52 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 0.5 Resin A1 Resin A 2000 25 11.0 400 C A Examples 1-53 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 1 Resin A1 Resin A 2000 25 12.0 400 A A Examples 1-54 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 20 Resin A1 Resin A 2000 25 13.0 400 A A Examples 1-55 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 30 Resin A1 Resin A 2000 25 13.0 400 B A Examples 1-56 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 50 Resin A1 Resin A 2000 25 13.5 400 C A Examples 1-57 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 0.01 Resin A1 Resin A 2000 25 11.0 400 D A Examples 1-58 Sodium hypochlorite 1 Trimethylphenylammonium chloride N - 5 Resin A1 Resin A 3000 25 12.5 400 C A Examples 1-59 Potassium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Resin A2 Resin A 3000 25 13.0 400 A A Examples 1-60 hypochlorous acid 1 Tetrapropylammonium hydroxide N 3 9 Resin A2 Resin A 3000 25 11.5 400 A A

[0297] [Table 4] Hypochlorous acid or its salts First onium salt compound Compound X pH Content ratio Evaluation results type content (quality%) type Cation atoms Maximum number of carbon atoms in a specific alkyl group content (quality%) type Cation atoms content (mass ppm) RuER ERR (Ru / W) Example 2-1 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 benzalkonium chloride Second onium salt compound N 100 12.0 100 A B Example 2-2 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Benzyl chloride Second onium salt compound N 100 12.0 100 A B Example 2-3 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 100 12.0 100 A B Examples 2-4 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 5-Azamonite[4,4]nonane chloride Second onium salt compound N 100 12.0 100 A B Examples 2-5 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 1-Butyl-2,3-dimethylimidazolium chloride Second onium salt compound N 100 13.0 100 A B Examples 2-6 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1,1-Dimethylpiperidinium chloride Second onium salt compound N 100 12.0 100 A B Examples 2-7 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 6-Aza-spiro[5,5]undecyl chloride Second onium salt compound N 100 12.0 100 A B Examples 2-8 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1-Hexyl-3-methylimidazolium chloride Second onium salt compound N 100 12.0 100 A B Examples 2-9 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 1,1'-Diheptyl-4,4'-Bipyridine dibromide Second onium salt compound N 100 13.0 100 A B Example 2-10 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Anpoxetine Hydrochloride Second onium salt compound N 100 13.0 100 A B Example 2-11 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 Butyltriphenylsilane chloride Second onium salt compound P 100 13.0 100 A C Example 2-12 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Butyltriphenylphosphonium chloride Second onium salt compound P 100 13.0 100 A C Example 2-13 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 100 12.0 100 A B Example 2-14 Sodium hypochlorite 1 Tetramethylammonium hydroxide N 1 5 Benzyl chloride Second onium salt compound N 100 12.0 100 A B Example 2-15 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 100 12.0 100 A B Example 2-16 Sodium hypochlorite 1 Tetraethylammonium chloride N 2 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 100 13.0 100 A B Example 2-17 Sodium hypochlorite 1 Hexamethylammonium chloride N 1 5 Benzyl chloride Second onium salt compound N 100 13.0 100 B B Example 2-18 Sodium hypochlorite 1 Decyltrimethylammonium chloride N 10 5 Benzyl chloride Second onium salt compound N 100 13.0 100 A B Example 2-19 Sodium hypochlorite 1 Dodecyltrimethylammonium chloride N 12 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 100 12.0 100 B B Example 2-20 Sodium hypochlorite 1 Octadecyltrimethylammonium chloride N 18 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 100 13.0 100 B B Example 2-21 Sodium hypochlorite 1 Tetradecyltrimethylammonium chloride N 14 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 100 12.0 100 B B Example 2-22 Sodium hypochlorite 1 Eicosyltrimethylammonium chloride N 20 5 Benzyl chloride Second onium salt compound N 100 12.0 100 C B

[0298] [Table 5] Hypochlorous acid or its salts First onium salt compound Compound X pH Content ratio Evaluation results type content (quality%) type Cation atoms Maximum number of carbon atoms in a specific alkyl group content (quality%) type Cation atoms content (mass ppm) RuER ERR (Ru / W) Example 2-23 Sodium hypochlorite 1 Tetrabutylphosphonium hydroxide P 4 5 Benzyl chloride Second onium salt compound N 100 12.0 100 E B Example 2-24 Sodium hypochlorite 1 Trimethylphenylammonium hydroxide N - 5 Benzyl chloride Second onium salt compound N 100 13.0 100 D B Example 2-25 Sodium hypochlorite 1 1-Butyl-1-methylpyrrolidine onium chloride N - 5 Benzyl chloride Second onium salt compound N 100 13.0 100 D B Example 2-26 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 Butyltriphenylsilane chloride Second onium salt compound S 100 12.0 100 A C Example 2-27 Sodium hypochlorite 1 Decyltrimethylammonium chloride N 10 5 Butyltriphenylsilane chloride Second onium salt compound S 100 12.0 100 A C Example 2-28 Sodium hypochlorite 1 Tetradecyltrimethylammonium chloride N 14 5 Butyltriphenylsilane chloride Second onium salt compound S 100 12.0 100 B C Example 2-29 Sodium hypochlorite 1 Tetrabutylphosphonium hydroxide P 4 5 Butyltriphenylsilane chloride Second onium salt compound S 100 13.0 100 E C Examples 2-30 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 5-Azamonite[4,4]nonane chloride Second onium salt compound N 100 6.0 100 C C Example 2-31 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 5-Azamonite[4,4]nonane chloride Second onium salt compound N 100 7.5 100 B B Example 2-32 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 5-Azamonite[4,4]nonane chloride Second onium salt compound N 100 10.5 100 A B Example 2-33 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 5-Azamonite[4,4]nonane chloride Second onium salt compound N 100 13.4 100 B B Examples 2-34 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 2 12.0 5000 A D Example 2-35 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 4.5 13.0 2222 A C Examples 2-36 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 10 12.5 1000 A B Example 2-37 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 20 12.0 500 A B Example 2-38 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 100 12.0 100 A B Example 2-39 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 500 12.0 20 A B Example 2-40 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 1000 12.0 10 A B Example 2-41 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1-Butyl-1-methylpyrrolidine onium chloride Second onium salt compound N 7000 12.0 1.4 A C

[0299] [Table 6] Hypochlorous acid or its salts First onium salt compound Compound X pH Content ratio result type content (quality%) type Cation atoms Maximum number of carbon atoms in a specific alkyl group content (quality%) type content (mass ppm) RuER ERR (Ru / W) Example 3-1 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 Chlorhexidine Compound B Biguanide 100 12.0 100 A C Example 3-2 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1-(o-tolyl)biguanide Compound B Biguanide 100 13.0 100 A C Example 3-3 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 Phenylephrine Compound B Biguanide 100 12.0 100 A C Examples 3-4 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Arginine Compound B amino acids 100 12.0 100 A D Examples 3-5 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Ricin Compound B amino acids 100 12.0 100 A D Examples 3-6 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 Aspartic acid Compound B amino acids 100 13.0 100 A D Examples 3-7 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 dipropylamine Compound B Aliphatic amines 100 13.0 100 A D Examples 3-8 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 EDTA-1,5-diaminetetraacetic acid Compound B Polyamine polycarboxylic acid 100 12.0 100 A D Examples 3-9 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 cis-2,6-dimethylpiperazine Compound B Alicyclic amines 100 12.0 100 A D Examples 3-10 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1,3-Diphenylguanidine Compound B guanidine 100 13.0 100 A E Example 3-11 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 1,2,3-Tris(tert-butoxycarbonyl)guanidine Compound B guanidine 100 12.0 100 A E Example 3-12 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1-Acetylguanidine Compound B guanidine 100 13.0 100 A E Example 3-13 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene Compound B guanidine 100 12.0 100 A E Example 3-14 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 1,2,3-Benztriazole Compound B azole 100 12.0 100 A E Example 3-15 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole Compound B azole 100 12.0 100 A E Example 3-16 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 5-Amino-1H-tetrazole Compound B azole 100 13.0 100 A E

[0300] [Table 7] Hypochlorous acid or its salts First onium salt compound Compound X pH Content ratio result type content (quality%) type Cation atoms Maximum number of carbon atoms in a specific alkyl group content (quality%) type content (mass ppm) RuER ERR (Ru / W) Example 3-17 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 2-Aminoquinoline Compound B Quinoline 100 12.0 100 A E Example 3-18 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 2-Quinoline carboxylic acid Compound B Quinoline 100 12.0 100 A E Example 3-19 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 8-Hydroxyquinalidin Compound B Quinoline 100 12.0 100 A E Example 3-20 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 2,6-Pyridinedicarboxylic acid Compound B Pyridine 100 13.0 100 A E Example 3-21 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Bis(2-pyridylmethyl)amine Compound B Pyridine 100 13.0 100 A E Example 3-22 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 3H-1,2,3-triazolo[4,5-b]pyridine-3-ol Compound B Pyridine 100 12.0 100 A E Example 3-23 Sodium hypochlorite 1 Tetrapropylammonium hydroxide N 3 5 Indole-3-butyric acid Compound B Indole 100 13.0 100 A F Example 3-24 Sodium hypochlorite 1 octyltrimethylammonium chloride N 8 5 carbazole Compound B carbazole 100 13.0 100 A F Example 3-25 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 Phenylephrine Compound B Biguanide 100 12.0 100 A C Example 3-26 Sodium hypochlorite 1 Decyltrimethylammonium chloride N 10 5 Phenylephrine Compound B Biguanide 100 13.0 100 A C Example 3-27 Sodium hypochlorite 1 Tetradecyltrimethylammonium chloride N 14 5 1-(o-tolyl)biguanide Compound B Biguanide 100 12.0 100 B C Example 3-28 Sodium hypochlorite 1 Triphenylsilane chloride S - 5 Phenylephrine Compound B Biguanide 100 13.0 100 E C Example 3-29 Sodium hypochlorite 1 Butyltriphenylphosphonium chloride P - 5 1-(o-tolyl)biguanide Compound B Biguanide 100 12.0 100 E C Examples 3-30 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 2-Amino-1-butanol Compound B Alkylamine 100 12.0 100 A C Example 3-31 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 2-Amino-2-hydroxymethyl-1,3-propanediol Compound B Alkylamine 100 12.0 100 A C Example 3-32 Sodium hypochlorite 1 Tetrapropylammonium chloride N 3 5 1-Amino-4-hydroxyadamantane Compound B Alkylamine 100 12.0 100 A C

[0301] [Table 8] hypochlorous acid or its salts First onium salt compound Compound X Compounds containing carbonyl groups Grinding particles Evaluation results type content (quality%) type content (quality%) type content (mass ppm) type content (quality%) type content (quality%) RuER ERR (Ru / W) Example 4-1 Sodium hypochlorite 1 Tetrapropylammonium hydroxide 5 Resin A1 Resin A 25 malonic acid 5 - - A A Example 4-2 Sodium hypochlorite 1 octyltrimethylammonium chloride 5 Resin A2 Resin A 25 malonic acid 5 - - A A Example 4-3 Sodium hypochlorite 1 octyltrimethylammonium chloride 5 Resin A2 Resin A 25 1,2,3,4,5,6-Cyclohexanehexacarboxylic acid 5 - - A A Example 4-4 Sodium hypochlorite 1 Tetrapropylammonium hydroxide 5 benzalkonium chloride Second onium salt compound 100 malonic acid 5 - - A B Examples 4-5 Sodium hypochlorite 1 octyltrimethylammonium chloride 5 Benzyl chloride Second onium salt compound 100 Dimethyl oxalate 5 - - A B Examples 4-6 Sodium hypochlorite 1 octyltrimethylammonium chloride 5 Benzyl chloride Second onium salt compound 100 - - Colloidal silicon dioxide 0.1 A F Examples 4-7 Sodium hypochlorite 1 Tetrapropylammonium hydroxide 5 Resin A1 Resin A 25 - - Colloidal silicon dioxide 0.1 A F

[0302] [Table 9] Hypochlorous acid or its salts First onium salt compound additive Evaluation results type content (quality%) type content (quality%) type content (mass ppm) RuER ERR (Ru / W) Comparative Example 1 Sodium hypochlorite 1 Tetrapropylammonium hydroxide 5 - - A G Comparative Example 2 Sodium hypochlorite 1 - - Resin A2 100 F B Comparative Example 3 Sodium hypochlorite 1 - - - - F G Comparative Example 4 Sodium hypochlorite 1 Tetrapropylammonium hydroxide 5 Catechol 100 B G Comparative Example 5 Sodium hypochlorite 1 Tetrapropylammonium hydroxide 5 malonic acid 5000 B G Comparative Example 6 Tetramethylammonium hypochlorite 3.51 Tetramethylammonium hydroxide 0.09 Tetramethylammonium bromide 7700 C G Comparative Example 7 Sodium hypochlorite 2.15 Tetramethylammonium hydroxide 3.09 Tetradecyltrimethylammonium chloride 100 C G

[0303] The results in the table confirm that the composition of the present invention has a high Ru / W ratio and excellent Ru solubility. When compound X is one or more compounds selected from the group consisting of resin A, a second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, biguanide compound, alkanolamine compound, amino acid, aliphatic amine compound, alicyclic amine compound, polyaminopolycarboxylic acid, azole compound, guanidine compound, quinoline compound, and pyridine compound, the effect of the present invention is confirmed to be even better. Furthermore, when compound X is one or more compounds selected from the group consisting of resin A, a second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, biguanide compound, alkanolamine compound, amino acid, aliphatic amine compound, alicyclic amine compound, and polyaminopolycarboxylic acid, the effect of the present invention is confirmed to be even better (Examples 1-1 to 1-8, Examples 2-1 to 2-13, Examples 3-1 to 3-32). When resin A contains repeating units with a quaternary ammonium salt structure in the main chain, the effects of the present invention are confirmed to be superior (Examples 1-1 to 1-4). When resin B contains repeating units represented by any of formulas (B3) to (B5), the effects of the present invention are confirmed to be superior (Examples 1-5 to 1-8). When the first onium salt compound is a compound represented by formula (Z1), the effects of the present invention are confirmed to be superior (Examples 1-1, 1-13, 1-20, Examples 2-2, 2-17). When the first onium salt compound is a compound represented by formula (Z1) or a compound represented by formula (Z3), and A Z11, A Z31, and A Z32 are nitrogen atoms, the effects of the present invention are confirmed to be superior (Examples 1-1, 1-19 to 1-21). When the first onnnage salt compound is a compound represented by formula (Z1) or formula (Z3), and R Z11 to R Z14 and R Z31 to R Z36 are each independently an alkyl group having 1 to 18 carbon atoms that can have substituents, the effects of the present invention are confirmed to be even better. Furthermore, when the first onnnage salt compound is a compound represented by formula (Z1) or formula (Z3), and R Z11 to R Z14 and R Z31 to R Z36 are each independently an alkyl group having 1 to 10 carbon atoms that can have substituents, the effects of the present invention are confirmed to be even better (Examples 1-1 to 1-18, 1-58). When the pH is 7.0 to 14.0, the effects of the present invention are confirmed to be even better (Examples 1-1, 1-29 to 1-35, Examples 2-4, 2-31 to 2-33). When the mass ratio of hypochlorous acid or its salt to compound X (content of hypochlorous acid or its salt / content of compound X) is 5 to 2,000, the superior effect of the present invention is confirmed (Examples 1-1, 1-36 to 1-43, Examples 2-3, 2-34 to 2-41).When the content of hypochlorous acid or its salt is 0.05 to 20% by mass relative to the total mass of the composition, the effects of the present invention are confirmed to be superior (Examples 1-1, 1-44 to 1-51). When the content of the first onium salt compound is 0.1 to 50% by mass relative to the total mass of the composition, the effects of the present invention are confirmed to be superior (Examples 1-1, 1-52 to 1-57). When the present invention does not substantially contain abrasive particles, the effects of the present invention are confirmed to be superior (Examples 1-1, 2-1, 4-6 to 4-7). [Simplified Explanation of the Diagram]

[0012] Figure 1 is a schematic diagram of the upper cross-section of an example of the workpiece used in step A1. Figure 2 is a schematic diagram of the upper cross-section of an example of the workpiece shown in Figure 1 after step A1 is performed. Figure 3 is a schematic diagram of the upper cross-section of another example of the workpiece used in step A1. Figure 4 is a schematic diagram of the upper cross-section of an example of the workpiece shown in Figure 3 after step A1 is performed. Figure 5 is a schematic diagram of an example of the workpiece used in step A2. Figure 6 is a schematic cross-section of an example of the workpiece used in step A4. Figure 7 is a schematic cross-section of an example of the workpiece before dry etching. Figure 8 is a schematic cross-section of another example of the workpiece used in step A4. Figure 9 is a schematic cross-section of an example of the workpiece before Ru-containing film formation. Figure 10 is a schematic cross-section of an example of the workpiece used in step A6.

Claims

1. A composition comprising: hypochlorous acid or a salt thereof; a first onium salt compound; and one or more compounds X selected from the group consisting of a second onium salt compound having a cyclic structure, a compound different from the first onium salt compound, a resin A having a repeating unit having an onium salt structure, a resin B having a nitrogen atom and not having an onium salt structure, polyamine polycarboxylic acid, guanidine compounds, and quinoline compounds.

2. A composition comprising: hypochlorous acid or a salt thereof; a first onium salt compound; and one or more compounds X selected from the group consisting of a second onium salt compound having a cyclic structure, a resin A having a repeating unit having an onium salt structure, and a compound B having a nitrogen atom but not having an onium salt structure, wherein the mass ratio of the content of the hypochlorous acid or its salt to the content of the compound X is 1 to 10,000.

3. The composition as claimed in claim 1 or 2, wherein the aforementioned first onium salt compound is a compound represented by any one of formulas (Z1) to (Z3), in formula (Z1), AZ11 represents a nitrogen atom or a phosphorus atom, RZ11 to RZ14 each independently represent an alkyl group that may have substituents or an aryl group that may have substituents, and XZ11- represents an anion; in formula (Z2), RZ21 to RZ23 each independently represent an alkyl group that may have substituents or an aryl group that may have substituents, and XZ21- represents an anion; in formula (Z3), AZ31 and AZ32 each independently represent a nitrogen atom or a phosphorus atom, RZ31 to RZ36 each independently represent an alkyl group that may have substituents or an aryl group that may have substituents, nZ31 represents an integer from 1 to 10, and XZ31- represents an anion.

4. The composition as described in claim 3, wherein the first onium salt compound is a compound represented by the aforementioned formula (Z1) or a compound represented by the aforementioned formula (Z3), and AZ11, AZ31 and AZ32 are nitrogen atoms.

5. The composition as claimed in claim 3, wherein the first onium salt compound is a compound represented by the aforementioned formula (Z1) or a compound represented by the aforementioned formula (Z3), and RZ11 to RZ14 and RZ31 to RZ36 are each independently a straight-chain alkyl group that may have substituents.

6. The composition as claimed in claim 3, wherein the first onium salt compound is a compound represented by the aforementioned formula (Z1) or a compound represented by the aforementioned formula (Z3), and RZ11 to RZ14 and RZ31 to RZ36 are each independently an alkyl group having 1 to 18 carbon atoms that may have substituents.

7. The composition as claimed in claim 3, wherein the first onium salt compound is a compound represented by the aforementioned formula (Z1) or a compound represented by the aforementioned formula (Z3), and RZ11 to RZ14 and RZ31 to RZ36 are each independently alkyl groups having 1 to 10 carbon atoms that may have substituents.

8. The composition as claimed in claim 2, wherein the aforementioned compound X is selected from one or more compounds selected from the group consisting of the aforementioned resin A, the aforementioned second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, biguanide compounds, alkanolamine compounds, amino acids, aliphatic amine compounds, alicyclic amine compounds, polyamino polycarboxylic acids, azole compounds, guanidine compounds, quinoline compounds and pyridine compounds.

9. The composition as claimed in claim 2, wherein the aforementioned compound X is one or more compounds selected from the group consisting of the aforementioned resin A, the aforementioned second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, biguanide compounds, alkanolamine compounds, amino acids, aliphatic amine compounds, alicyclic amine compounds and polyamine polycarboxylic acids.

10. The composition as claimed in claim 2, wherein the aforementioned compound X is selected from one or more compounds selected from the group consisting of the aforementioned resin A, the aforementioned second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, biguanide compounds and alkanolamine compounds.

11. The composition as claimed in claim 1, wherein the aforementioned compound X is selected from one or more compounds selected from the group consisting of the aforementioned resin A, the aforementioned second onium salt compound, resin B having a nitrogen atom and not having an onium salt structure, and polyamine polycarboxylic acid.

12. The composition as claimed in claim 1, wherein the aforementioned compound X is one or more compounds selected from the group consisting of the aforementioned resin A, the aforementioned second onium salt compound, and resin B having a nitrogen atom and not having an onium salt structure.

13. The composition as claimed in claim 1 or 8, wherein the weight average molecular weight of the aforementioned resin A and the aforementioned resin B is 1,000 to 200,000.

14. The composition as claimed in claim 1 or 8, wherein the aforementioned resin B comprises repeating units containing nitrogen atoms.

15. The composition as claimed in claim 1 or 2, wherein the aforementioned resin A comprises repeating units having an onium salt structure, the repeating units having cationized nitrogen atoms.

16. The composition as claimed in claim 15, wherein the aforementioned resin A comprises repeating units having a quaternary ammonium salt structure.

17. The composition as claimed in claim 16, wherein the aforementioned resin A comprises repeating units having a quaternary ammonium salt structure in the main chain.

18. The composition as described in claim 1 or 2, further comprising a compound having a carbonyl group that is different from both the aforementioned first onium salt compound and the aforementioned compound X.

19. The composition as claimed in claim 1, wherein the mass ratio of the content of the aforementioned hypochlorous acid or its salt to the content of the aforementioned compound X is 1 to 10,000.

20. The composition as described in claim 1 or 2, wherein the pH is 7.0 to 14.

0.

21. The composition as described in claim 1 or 2 does not substantially contain abrasive particles.

22. A composition as described in claim 1 or 2, used for a processed article containing ruthenium.

Images