Composition, kit, and method for treating substrate

Abstract

To provide a composition superior in the capability of dissolving metal inclusion (especially, Ru inclusion) and the etching selectivity (especially the etching selectivity of Ru inclusion and another metal inclusion), a kit for preparing the composition, and a substrate processing method by using the composition.SOLUTION: A composition according to the present invention is arranged for removing metal inclusion. The composition comprises: one or more periodic acid compounds selected from a group consisting of periodic acid and its salt; an azole compound; and an alkali compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to compositions, kits, and methods for treating substrates. [Background technology]

[0002] As semiconductor products become increasingly miniaturized, there is an increasing demand for highly efficient and accurate removal of unwanted metal inclusions from substrates during the semiconductor product manufacturing process.

[0003] Patent Document 1 describes a method for patterning a ruthenium film formed on an upper surface of a substrate using a copper mask, the method comprising: step (a) of supplying a Cu corrosion inhibitor BTA to the upper surface of the substrate, supplying an aqueous solution of orthoperiodic acid to the lower surface, and removing the ruthenium film on the lower surface; step (b) of supplying the Cu corrosion inhibitor BTA to the upper surface of the substrate after step (a), supplying an aqueous solution of orthoperiodic acid to the outer periphery of the substrate, and removing the ruthenium film on the outer periphery; step (c) of supplying pure water to the upper and lower surfaces of the substrate after step (b) to remove the aqueous solution of orthoperiodic acid; and step (d) of rotating the substrate to dry after step (c). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2009-081247 A Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, when removing unnecessary metal-containing substances on a substrate, compositions used as etching solutions are increasingly required to have excellent dissolving ability (etching performance) for metal-containing substances, and in particular, to have excellent etching performance for a workpiece having ruthenium (Ru)-containing substances. Furthermore, in the process of removing unwanted metal inclusions on a substrate, while the etching performance for the target metal inclusions is good, the etching performance for metal-containing layers other than the target metal inclusions (e.g., metal wiring, barrier metal layers, etc.) is restricted, i.e., there is a demand for improved etching selectivity.

[0006] Therefore, an object of the present invention is to provide a composition that is excellent in dissolving ability of metal-containing substances (particularly Ru-containing substances) and etching selectivity (particularly etching selectivity between Ru-containing substances and other metal-containing substances). Another object of the present invention is to provide a kit for preparing the composition, and a method for treating a substrate using the composition. [Means for solving the problem]

[0007] As a result of intensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0008] [1] A composition for removing metal inclusions, comprising one or more periodate compounds selected from the group consisting of periodic acid and its salts, an azole compound, and an alkali compound. [2] The composition according to claim 1, wherein the metal-containing material comprises a ruthenium-containing material. [3] The composition according to [1] or [2], wherein a ratio of the content of the periodic acid compound to the content of the azole compound is 10 to 300 in terms of mass ratio. [4] The composition according to any one of [1] to [3], wherein the ratio of the content of the periodate compound to the content of the alkali compound is 0.5 to 2.0 in terms of mass ratio. [5] The composition according to any one of [1] to [4], further comprising a water-soluble organic solvent. [6] The composition according to [5], wherein the water-soluble organic solvent comprises an alkylene glycol dialkyl ether. [7] The composition according to [5] or [6], wherein the ratio of the content of the water-soluble organic solvent to the content of the azole compound is 10 to 2000 in terms of mass ratio. [8] The composition according to any one of [1] to [7], wherein the azole compound includes at least one selected from the group consisting of a triazole compound, a pyrazole compound, and an imidazole compound. [9] The composition according to any one of [1] to [8], wherein the alkaline compound includes at least one selected from the group consisting of a quaternary ammonium hydroxide, an amino alcohol, ammonia, and potassium hydroxide.

[10] The composition according to any one of [1] to [9], further comprising a surfactant.

[11] The composition according to any one of [1] to

[10] , further comprising an organic acid.

[12] The composition according to

[11] , wherein the organic acid comprises at least one selected from the group consisting of carboxylic acids and phosphonic acids.

[13] The composition according to

[11] or

[12] , wherein the organic acid comprises at least one carboxylic acid and at least one phosphonic acid.

[14] The composition according to any one of [1] to

[13] , wherein the pH of the composition is 7.0 to 14.0.

[15] A kit for preparing a composition used to remove metal inclusions on a substrate, the kit comprising: a first liquid containing one or more periodate compounds selected from the group consisting of periodic acid and its salts and an alkali compound; and a second liquid containing an azole compound.

[16] A method for treating a substrate, comprising a step A of removing metal inclusions on the substrate by using the composition according to any one of [1] to

[14] .

[17] The method for processing a substrate according to

[16] , wherein the metal-containing material includes a ruthenium-containing material.

[18] The method for treating a substrate according to

[16] or

[17] , wherein two or more types of metal-containing substances are present on the substrate on which step A is performed.

[19] The method for treating a substrate according to

[18] , wherein the two or more kinds of metal-containing substances include at least a ruthenium-containing substance and a copper-containing substance or a cobalt-containing substance.

[20] The method for treating a substrate according to

[16] , wherein the metal-containing material comprises a particulate metal oxide. 〔twenty one〕 The method for treating a substrate according to any one of

[16] to

[20] , wherein step A is step A1 of performing a recess etching treatment on a metal-containing wiring disposed on a substrate using the composition, step A2 of removing the metal-containing film from an outer edge of the substrate on which the metal-containing film is disposed using the composition, step A3 of removing metal inclusions adhering to the back surface of the substrate on which the metal-containing film is disposed using the composition, step A4 of removing metal inclusions on the substrate after dry etching using the composition, or step A5 of removing metal inclusions on the substrate after chemical mechanical polishing using the composition. 〔twenty two〕 Step A is Step A1, Two or more kinds of metal-containing substances are present on the substrate on which step A1 is performed, The substrate processing method according to

[21] , wherein step A1 comprises steps A1a for removing at least one of two or more types of metal inclusions, and A1b for removing a metal inclusion different from the metal inclusion removed in step A1a. 〔twenty three〕 Step A is Step A1, The method for treating a substrate according to

[21] or

[22] , further comprising a step B, before or after step A1, of treating the substrate obtained in step A1 with a solution selected from the group consisting of a mixture of hydrofluoric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of ammonia water and hydrogen peroxide, and a mixture of hydrochloric acid and hydrogen peroxide. Effect of the Invention

[0009] According to the present invention, a composition having excellent dissolving ability and etching selectivity for metal-containing materials can be provided. Furthermore, the present invention can provide a kit for preparing the composition, and a method for treating a substrate using the composition. [Brief description of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram of an upper cross-section showing an example of a workpiece used in step A1. [Diagram 2] FIG. 2 is a schematic diagram of a cross-sectional upper portion of an example of a workpiece after step A1 has been performed. [Diagram 3] FIG. 2 is a schematic diagram showing an example of a processing object used in step A2. [Figure 4] FIG. 4 is a schematic cross-sectional view showing an example of a processing object used in step A4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In the description of groups (atomic groups) in this specification, the description that does not indicate whether substituted or unsubstituted includes both unsubstituted and substituted groups, as long as it does not impair the effects of the present invention. For example, "alkyl group" includes not only alkyl groups that do not have a substituent (unsubstituted alkyl groups), but also alkyl groups that have a substituent (substituted alkyl groups). This also applies to each compound. In this specification, unless otherwise specified, "exposure" includes not only exposure to far ultraviolet light represented by a mercury lamp, an excimer laser, X-rays, and EUV (Extreme ultraviolet) light, but also drawing with particle beams such as electron beams and ion beams. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0012] In this specification, dry etching residues refer to by-products generated by performing dry etching (e.g., plasma etching), and include, for example, organic residues derived from photoresist, Si-containing residues, and metal-containing residues (e.g., metal-containing residues).

[0013] [Composition] The composition of the present invention (hereinafter also referred to as "the composition") is a composition comprising one or more periodate compounds selected from the group consisting of periodic acid and its salts, an azole compound, and an alkali compound. Although the mechanism by which the object of the present invention is achieved by using this composition is not entirely clear, the inventors speculate that the inclusion of a periodate compound in the composition realizes excellent solubility of metal-containing substances, and the inclusion of an alkali compound in the composition reduces the solubility of the metal-containing layer of the substrate, thereby improving etching selectivity.

[0014] <Periodate compounds> The compositions of the present invention include a periodate compound. In this specification, the periodic acid compound is a general term for compounds selected from the group consisting of periodic acid and its salts. The periodic acid compound is not particularly limited, but from the viewpoint of excellent solubility of transition metal-containing substances represented by ruthenium, one or more compounds selected from the group consisting of orthoperiodic acid (H5IO6), salts of orthoperiodic acid, metaperiodic acid (HIO4), and salts of metaperiodic acid are preferred, and orthoperiodic acid or metaperiodic acid is more preferred. Among them, orthoperiodic acid is even more preferred from the viewpoint of not containing an alkali metal such as sodium (Na) and having a stable composition.

[0015] The periodate compounds may be used alone or in combination of two or more. The content of the periodate compound (the total content when multiple periodate compounds are included) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 2.0 mass% or more, based on the total mass of the composition, in terms of better ability to dissolve metal-containing substances. Furthermore, the content of the periodate compound is preferably 40.0 mass% or less, more preferably 30.0 mass% or less, even more preferably 20.0 mass% or less, and particularly preferably 10.0 mass% or less, relative to the total mass of the composition, in terms of better etching selectivity.

[0016] <Azole compounds> The composition of the present invention comprises an azole compound. An azole compound is a compound having at least one nitrogen atom and a five-membered heterocyclic ring having aromaticity. The number of nitrogen atoms contained in the five-membered hetero ring of the azole compound is not particularly limited, and is preferably 1 to 4, and more preferably 2 to 4.

[0017] The azole compound may have a substituent on the 5-membered hetero ring. Examples of such a substituent include a hydroxyl group, a carboxyl group, a mercapto group, an amino group, and a substituted or unsubstituted hydrocarbon group. In addition, when two substituents are adjacent to each other on the 5-membered hetero ring, the two substituents may be bonded to each other to form a ring. Examples of the hydrocarbon group that the 5-membered hetero ring has as a substituent include an alkyl group (preferably having 1 to 12 carbon atoms, and more preferably having 1 to 6 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, and more preferably having 2 to 6 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms, and more preferably having 2 to 6 carbon atoms), an aryl group (preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), and an aralkyl group (preferably having 7 to 23 carbon atoms, and more preferably having 7 to 11 carbon atoms). Examples of the substituents on the hydrocarbon group include a hydroxy group, a carboxy group, and -N(R a )(R b ) are listed. R a and R beach independently represents a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms, more preferably having 1 to 4 carbon atoms), or a hydroxyalkyl group (preferably having 1 to 6 carbon atoms, more preferably having 1 to 4 carbon atoms).

[0018] The ring formed by bonding two adjacent substituents on the hetero 5-membered ring is not particularly limited, but is preferably an aromatic ring (either monocyclic or polycyclic), more preferably a benzene ring. The ring formed by bonding two of the above-mentioned substituents may have a substituent. The substituent is not particularly limited, but may be, for example, the substituents exemplified as the substituents of the hydrocarbon group of the hetero 5-membered ring.

[0019] Examples of the azole compound include an imidazole compound in which one of the atoms constituting the azole ring is a nitrogen atom, a pyrazole compound in which two of the atoms constituting the azole ring are nitrogen atoms, a thiazole compound in which one of the atoms constituting the azole ring is a nitrogen atom and the other is a sulfur atom, a triazole compound in which three of the atoms constituting the azole ring are nitrogen atoms, and a tetrazole compound in which four of the atoms constituting the azole ring are nitrogen atoms.

[0020] Examples of imidazole compounds include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole, 4-hydroxyimidazole, 2,2'-biimidazole, 4-imidazolecarboxylic acid, histamine, benzimidazole compounds having a benzimidazole skeleton formed by condensing an imidazole ring with a benzene ring, and purine compounds having a purine skeleton formed by condensing an imidazole ring with a pyrimidine ring. Among these, the imidazole compound is preferably a benzimidazole compound or a purine compound, and more preferably a purine compound. Benzimidazole compounds include, for example, benzimidazole, 2-aminobenzimidazole, and 2-mercaptobenzimidazole azole. Purine compounds include adenine, guanine, and purine.

[0021] Examples of pyrazole compounds include pyrazole, 4-pyrazole carboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-aminopyrazole, and 4-aminopyrazole.

[0022] Thiazole compounds include, for example, 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole.

[0023] As the triazole compound, a compound having a benzotriazole skeleton in which two adjacent substituents on the triazole ring are bonded to each other to form a benzene ring is preferable. Examples of compounds having a benzotriazole skeleton include benzotriazole, 5-methyl-1H-benzotriazole (CAS Registry Number: 136-85-6), tolyltriazole (CAS Registry Number: 29385-43-1), 5-aminobenzotriazole, 1-hydroxybenzotriazole, 4-carboxybenzotriazole, 5,6-dimethylbenzoatriazole, 1-[N,N-bis(hydroxyethyl)aminoethyl]benzotriazole, 1-(1,2-dicarboxyethyl)benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole, 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol, and carboxybenzotriazole. Examples of triazole compounds other than compounds having a benzotriazole skeleton include 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3-amino-1,2,4-triazole, 1,2,3-triazole, and 1-methyl-1,2,3-triazole.

[0024] Examples of tetrazole 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-mercaptotetrazole, and 1-(2-dimethylaminoethyl)-5-mercaptotetrazole.

[0025] As the azole compound, triazole compound or tetrazole compound is preferred because it has excellent anticorrosive ability against copper and cobalt.In another embodiment, as the azole compound, triazole compound, pyrazole compound or imidazole compound is preferred.Among them, triazole compound is more preferred, and compound having benzotriazole skeleton is even more preferred. In this specification, the azole compounds having the above specific structures include their tautomers.

[0026] The azole compounds may be used alone or in combination of two or more. The content of the azole compound (the total content when multiple azole compounds are included) is preferably 0.005 mass % or more, more preferably more than 0.02 mass %, and even more preferably 0.08 mass % or more, based on the total mass of the composition, in terms of better etching selectivity. In addition, the content of the azole compound is preferably 5.0 mass% or less, more preferably 2.0 mass% or less, even more preferably less than 1.0 mass%, and particularly preferably 0.3 mass% or less, relative to the total mass of the composition, in order to obtain a better ability to dissolve metal-containing substances.

[0027] In order to obtain a well-balanced combination of the ability to dissolve metal-containing substances and the etching selectivity, the ratio of the content of the periodic acid compound to the content of the azole compound (content of the periodic acid compound / content of the azole compound) is preferably 1 to 500, more preferably 10 to 200, and even more preferably 15 to 100, in terms of mass ratio.

[0028] <Alkaline compounds> The composition of the present invention comprises an alkaline compound. The alkaline compound is not particularly limited as long as it is a compound that, when dissolved in water, gives an aqueous solution with a pH of greater than 7, and examples thereof include organic bases, inorganic bases, and salts thereof. The alkaline compound may be ionized in the composition.

[0029] Examples of the organic base include quaternary ammonium salt compounds, water-soluble amines, and quaternary phosphonium salt compounds, with quaternary ammonium salt compounds and water-soluble amines being preferred.

[0030] (Quaternary ammonium salt compounds) The quaternary ammonium salt compound is not particularly limited as long as it is a compound having a quaternary ammonium cation in which four hydrocarbon groups (preferably alkyl groups) are substituted on a nitrogen atom, or a salt thereof. Examples of the quaternary ammonium salt compound include quaternary ammonium hydroxide, quaternary ammonium fluoride, quaternary ammonium bromide, quaternary ammonium iodide, quaternary ammonium acetate, and quaternary ammonium carbonate. Quaternary ammonium hydroxide is preferred, and a compound represented by the following formula (1) is more preferred.

[0031] [ka]

[0032] In formula (1), R 4A ~R 4Deach independently represents an alkyl group having 1 to 6 carbon atoms (preferably a methyl group, an ethyl group, a propyl group, or a butyl group), a hydroxyalkyl group having 1 to 6 carbon atoms (preferably a hydroxymethyl group, a hydroxyethyl group, or a hydroxybutyl group), a benzyl group, or an aryl group (preferably a phenyl group, a naphthyl group, or a naphthalene group). Among these, an alkyl group having 1 to 6 carbon atoms, a hydroxyethyl group having 1 to 6 carbon atoms, or a benzyl group is preferred.

[0033] The compound represented by formula (1) is preferably at least one quaternary ammonium hydroxide salt selected from the group consisting of tetramethylammonium hydroxide (TMAH), ethyltrimethylammonium hydroxide (ETMAH), tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), dimethyldipropylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methyltri(hydroxyethyl)ammonium hydroxide, tetra(hydroxyethyl)ammonium hydroxide, trimethylbenzylammonium hydroxide, bishydroxyethyldimethylammonium hydroxide, and choline, and more preferably at least one selected from the group consisting of TMAH, ETMAH, TEAH, and TBAH. In addition, the quaternary ammonium hydroxide compounds described in JP-A-2015-518068 may be used. In terms of the effect of removing metal-containing substances, the small amount of metal remaining after use, economic efficiency, and stability of the composition, TMAH (tetramethylammonium hydroxide), ETMAH (ethyltrimethylammonium hydroxide), TEAH (triethylammonium hydroxide), dimethyldipropylammonium hydroxide, bishydroxyethyldimethylammonium hydroxide, or trimethyl(hydroxyethyl)ammonium hydroxide are preferred.

[0034] The quaternary ammonium salt compounds may be used alone or in combination of two or more kinds.

[0035] (Water-soluble amine) In this specification, the water-soluble amine refers to an amine that can dissolve 50 g or more in 1 L of water. The pKa of the water-soluble amine is not particularly limited, but is preferably 7.5 to 13.0. In addition, the water-soluble amine does not contain ammonia. Examples of water-soluble amines having a pKa of 7.5 to 13.0 include diglycolamine (DGA) (pKa=9.80), methylamine (pKa=10.6), ethylamine (pKa=10.6), propylamine (pKa=10.6), butylamine (pKa=10.6), pentylamine (pKa=10.0), monoethanolamine (pKa=9.3), propanolamine (pKa=9.3), butanolamine (pKa=9.3), methoxyethylamine (pKa=10.0), methoxypropylamine (pKa=10.0), dimethylamine (pKa=10.8), diethylamine (pKa=10.9), dipropylamine (pKa=10.8), trimethylamine (pKa=9.80), and triethylamine (pKa=10.72). As the water-soluble amine, unsubstituted hydroxylamine and hydroxylamine derivatives may also be used. In this specification, the pKa of a water-soluble amine is the acid dissociation constant in water, which can be measured by a combination of a spectrometer and potentiometric measurement.

[0036] The water-soluble amine is preferably an amino alcohol, which is a water-soluble amine compound further having at least one hydroxyl alkyl group in the molecule. Examples of the amino alcohols contained in the water-soluble amines include monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), diethylene glycolamine (DEGA), trishydroxymethylaminomethane (Tris), 2-(methylamino)-2-methyl-1-propanol (N-MAMP), 2-(dimethylamino)-2-methyl-1-propanol (DMAMP), 2-(aminoethoxy)ethanol (AEE), and 2-(2-aminoethylamino)ethanol (AAE). Of these, N-MAMP, DMAMP, MEA, DEA, AEE, or AAE is preferred, and N-MAMP, DMAMP, MEA, or AEE is more preferred.

[0037] (Quaternary phosphonium salt compounds) The quaternary phosphonium salt compound is not particularly limited as long as it is a compound having a quaternary phosphonium cation in which four hydrocarbon groups are substituted on a phosphorus atom, or a salt thereof. Examples of the quaternary phosphonium salt compound include quaternary phosphonium hydroxide, quaternary phosphonium fluoride, quaternary phosphonium bromide, quaternary phosphonium iodide, quaternary phosphonium acetate, and quaternary phosphonium carbonate, with quaternary phosphonium hydroxide being preferred.

[0038] Examples of the four hydrocarbon groups that the quaternary phosphonium salt compound has on the phosphorus atom include an alkyl group having 1 to 6 carbon atoms (preferably, a methyl group, an ethyl group, a propyl group, or a butyl group), a hydroxyalkyl group having 1 to 6 carbon atoms (preferably, a hydroxymethyl group, a hydroxyethyl group, or a hydroxybutyl group), a benzyl group, and an aryl group (preferably, a phenyl group, a naphthyl group, or a naphthalene group). Among these, an alkyl group having 1 to 6 carbon atoms, a hydroxyethyl group having 1 to 6 carbon atoms, or a benzyl group is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred.

[0039] The quaternary phosphonium salt compound is preferably tetramethylphosphonium hydroxide, ethyltrimethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, dimethyldipropylphosphonium hydroxide, trimethylhydroxyethylphosphonium hydroxide, methyltri(hydroxyethyl)phosphonium hydroxide, tetra(hydroxyethyl)phosphonium hydroxide, trimethylbenzylphosphonium hydroxide, or bishydroxyethyldimethylphosphonium hydroxide. The quaternary phosphonium salt compounds may be used alone or in combination of two or more.

[0040] (Inorganic Bases) Inorganic bases include, for example, alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide, strontium hydroxide, and barium hydroxide. The inorganic base is preferably ammonia, sodium hydroxide or potassium hydroxide, more preferably ammonia or potassium hydroxide.

[0041] The alkaline compound is preferably a quaternary ammonium hydroxide, a water-soluble amine (more preferably an amino alcohol), ammonia, or potassium hydroxide, and more preferably a quaternary ammonium hydroxide, ammonia, or a water-soluble amine. Among these, in terms of the effect of removing metal-containing substances, the small amount of metal remaining after use, economic efficiency, and stability of the composition, quaternary ammonium hydroxides are more preferable, and tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldipropylammonium hydroxide, and tetraethylammonium hydroxide are particularly preferable.

[0042] The alkaline compounds may be used alone or in combination of two or more. The content of the alkali compound (the total content when a plurality of alkali compounds are contained) is preferably 0.1 mass % or more, more preferably more than 0.5 mass %, and even more preferably 2.0 mass % or more, based on the total mass of the composition, in terms of better etching selectivity. Furthermore, the content of the alkali compound is preferably 20.0 mass % or less, more preferably 12.0 mass % or less, and even more preferably 8.0 mass % or less, based on the total mass of the composition, in terms of superior stability over time of the composition. It is also preferable to adjust the content of the alkaline compound in the composition within the above-mentioned preferred range so that the composition has a preferred pH range described below.

[0043] In order to obtain a well-balanced composition having an excellent etching selectivity and stability over time, the ratio of the content of the periodate compound to the content of the alkali compound (content of the periodate compound / content of the alkali compound) is preferably 0.3 to 3.0, more preferably 0.5 to 2.0, and even more preferably more than 1.0 and less than 1.8, by mass.

[0044] <Optional ingredients> The composition may contain other optional components in addition to the above-mentioned components. The optional components will be described below.

[0045] (solvent) The composition may include a solvent. The solvent includes water and water-soluble organic solvents.

[0046] -water- The water is not particularly limited, but is preferably water that has been subjected to a purification treatment, such as distilled water, ion-exchanged water, or ultrapure water, and more preferably ultrapure water used in semiconductor manufacturing. The water contained in the composition may contain unavoidable trace amounts of mixed components. The content of water in the composition is not particularly limited, but is preferably 50% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 75% by mass or more. The upper limit is not particularly limited, but is preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

[0047] -Water-soluble organic solvent- The composition preferably contains a water-soluble organic solvent, which has a superior ability to dissolve metal-containing substances. Examples of the water-soluble organic solvent include ether-based solvents, alcohol-based solvents, ketone-based solvents, amide-based solvents, sulfur-containing solvents, and lactone-based solvents. The water-soluble organic solvent is preferably an organic solvent that can be mixed with water in any ratio.

[0048] The ether solvent is not particularly limited as long as it is a compound having an ether bond (-O-), and examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, tetrahydrofuran, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, alkylene glycol monoalkyl ethers (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 diethylene glycol monobutyl ether), and alkylene glycol dialkyl ethers (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). In this specification, a compound having both a hydroxy group and an ether bond (-O-) is included in the ether solvent. The number of carbon atoms in the ether solvent is not particularly limited, but is preferably 3-16, more preferably 4-14, and even more preferably 6-12.

[0049] Examples of alcohol-based solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol. The number of carbon atoms in the alcohol-based solvent is not particularly limited, but is preferably 1 to 8, and more preferably 1 to 4.

[0050] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone. Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane. Examples of lactone solvents include γ-butyrolactone and δ-valerolactone.

[0051] The water-soluble organic solvent is preferably an ether-based solvent or an alcohol-based solvent, more preferably an alkylene glycol monoalkyl ether or an alkylene glycol dialkyl ether, and even more preferably an alkylene glycol dialkyl ether. The molecular weight of the water-soluble organic solvent (weight average molecular weight when the solvent has a molecular weight distribution) is preferably less than 500, and preferably not more than 300. There is no particular lower limit, but a value of 30 or more is preferable.

[0052] The water-soluble organic solvent is also preferably a compound represented by the following formula (2). R 21 -(-OR 23 -) m2 -OR 22 (2) In formula (2), R 21 and R 22 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 21 and R 22 At least one of R is preferably an alkyl group having 1 to 5 carbon atoms. 21 and R 22 More preferably, both of R represent an alkyl group having 1 to 5 carbon atoms,21 and R 22 It is more preferable that both of these represent an alkyl group having 1 to 4 carbon atoms. R 23 represents a linear or branched alkylene group having 1 to 4 carbon atoms. 23 When present, each may be the same or different. 23 As the alkyl group, an ethylene group or a 1,2-propylene group is preferable, and an ethylene group is more preferable. m2 represents an integer of 1 to 6. As m2, an integer of 1 to 4 is preferable, and an integer of 2 to 4 is more preferable.

[0053] R contained in the compound represented by formula (2) 21 and R 22 and R 23 The total number of carbon atoms in the alkylene group represented by the following formula is preferably 3 to 16, more preferably 4 to 14, and even more preferably 6 to 12.

[0054] Of these, the water-soluble organic solvent is preferably diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol diethyl ether, or tetraethylene glycol dimethyl ether, and more preferably diethylene glycol diethyl ether, diethylene glycol dibutyl ether, or tetraethylene glycol dimethyl ether.

[0055] When the composition contains a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, based on the total mass of the composition, in order to provide a better ability to dissolve metal-containing substances (particularly Ru-containing substances).The upper limit is not particularly limited, but is preferably 30% by mass or less, more preferably less than 20% by mass, and even more preferably 18% by mass or less, based on the total mass of the composition, in order to provide a better ability to dissolve metal-containing substances (particularly Ru-containing substances). The water-soluble organic solvent may be used alone or in combination of two or more. When two or more water-soluble organic solvents are used, the total content is preferably within the above range.

[0056] In terms of excellent dissolving ability of metal-containing substances, the ratio of the content of the water-soluble organic solvent to the content of the azole compound (content of the water-soluble organic solvent / content of the azole compound) is, in mass ratio, preferably 10 or more, more preferably 15 or more, and even more preferably 30 or more. There is no particular upper limit, but it is preferably 600 or less, more preferably 400 or less, and even more preferably 160 or less.

[0057] (Surfactant) The composition may also include a surfactant. The surfactant is not particularly limited as long as it is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule, and examples thereof include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. In terms of better etching selectivity, the composition preferably contains a surfactant.

[0058] The hydrophobic group of the surfactant is not particularly limited, but may be, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. When the hydrophobic group contains an aromatic hydrocarbon group, it preferably has 6 or more carbon atoms, more preferably 10 or more carbon atoms. When the hydrophobic group does not contain an aromatic hydrocarbon group and is composed only of an aliphatic hydrocarbon group, it preferably has 8 or more carbon atoms, more preferably 10 or more carbon atoms. The upper limit of the carbon number of the hydrophobic group is not particularly limited, but is preferably 24 or less, more preferably 20 or less.

[0059] The anionic surfactant may be an anionic surfactant having at least one hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxy group, a sulfate ester group, and a phosphonic acid group in the molecule.

[0060] Examples of the anionic surfactant having a sulfonic acid group in the molecule include alkylsulfonic acids, alkylbenzenesulfonic acids, alkylnaphthalenesulfonic acids, alkyldiphenylethersulfonic acids, fatty acid amidesulfonic acids, and salts thereof. Examples of the anionic surfactant having a carboxylic acid group in the molecule include polyoxyethylene alkyl ether carboxylic acids, polyoxyethylene alkyl ether acetic acids, polyoxyethylene alkyl ether propionic acids, fatty acids, and salts thereof. The salts given as specific examples of the above anionic surfactants are not particularly limited, and examples thereof include ammonium salts, sodium salts, potassium salts, and tetramethylammonium salts. As the anionic surfactant, a sulfonic acid-based anionic surfactant is preferable, and an alkylsulfonic acid, an alkylbenzenesulfonic acid, or a salt thereof is more preferable.

[0061] The cationic surfactant is not particularly limited as long as it is a compound having a cationic hydrophilic group and the above-mentioned hydrophobic group, and examples thereof include quaternary ammonium salt surfactants and alkylpyridinium surfactants.

[0062] Examples of amphoteric surfactants include betaine-based surfactants, amino acid-based surfactants, and amine oxide-based surfactants. Examples of betaine surfactants include compounds having a cationic structure (preferably a quaternary ammonium cationic structure) selected from a quaternary ammonium cation and an imidazole cation, and an anionic structure (preferably an anionic structure which is a carboxy group or a salt thereof) selected from a carboxy group, a sulfo group, and salts thereof. As the betaine surfactant, alkyl-N,N-dimethylaminoacetic acid betaine, alkylamidopropyl-N,N-dimethylaminoacetic acid betaine, or 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine is preferred, and lauryl dimethylaminoacetic acid betaine, stearyl dimethylaminoacetic acid betaine, coconut oil alkyl dimethylaminoacetic acid betaine, or N-lauric acid amidopropyl dimethylaminoacetic acid betaine is more preferred.

[0063] Examples of amino acid surfactants include alkylamino fatty acids, alkylamino difatty acids, and salts thereof. Among these, sodium N-laurylaminopropionate or sodium N-laurylaminodipropionate is preferred. Examples of amine oxide surfactants include alkyl dimethyl amine oxides and alkyl amidopropyl dimethyl amine oxides, particularly N-lauric acid amidopropyl dimethyl amine oxide.

[0064] Examples of nonionic surfactants include polyalkylene oxide alkyl phenyl ether surfactants, polyalkylene oxide alkyl ether surfactants, block polymer surfactants consisting of polyethylene oxide and polypropylene oxide, polyoxyalkylene distyrene-type phenyl ether surfactants, polyalkylene tribenzyl phenyl ether surfactants, and acetylene polyalkylene oxide surfactants.

[0065] The surfactant is preferably an anionic surfactant or an amphoteric surfactant, more preferably an amphoteric surfactant, and even more preferably a betaine surfactant having a quaternary ammonium cation structure and an anion structure which is a carboxy group or a salt thereof.

[0066] When the composition contains a surfactant, the content of the water-soluble organic solvent is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, based on the total mass of the composition, in terms of better etching selectivity. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, in terms of suppressing foaming of the composition. The surfactant may be used alone or in combination of two or more. When two or more surfactants are used, the total content is preferably within the above range.

[0067] (organic acid) The composition may include an organic acid. An organic acid is an organic compound that has an acidic functional group and exhibits acidity (pH less than 7.0) in an aqueous solution. Examples of the acidic functional group include a carboxyl group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a mercapto group. In this specification, periodic acid, compounds that function as anionic surfactants, and oxidizing agents described below are not included in the organic acid.

[0068] The organic acid is not particularly limited, but examples thereof include carboxylic acids having a carboxyl group in the molecule, phosphonic acids having a phosphonic acid group in the molecule, and sulfonic acids having a sulfo group in the molecule, with carboxylic acids or phosphonic acids being preferred. The number of functional groups that the organic acid has is not particularly limited, but is preferably 1 to 4, and more preferably 1 to 3. The organic acid is preferably a compound having a function of chelating with a metal, and is preferably a compound having two or more functional groups (coordination groups) in the molecule that form coordinate bonds with metal ions. Examples of the coordination groups include the above-mentioned functional groups, and a carboxylic acid group or a phosphonic acid group is preferred.

[0069] -Carboxylic acid- The composition may include a carboxylic acid. The carboxylic acid is a compound having one or more carboxy groups or a salt thereof. Note that the carboxylic acid does not include the above-mentioned anionic surfactant having a carboxylic acid group and a hydrophobic group in the molecule. In terms of better etching selectivity, the composition preferably contains a carboxylic acid. The carboxylic acids may be used alone or in combination of two or more.

[0070] The carboxylic acid is preferably a carboxylic acid having no nitrogen atom. Examples of carboxylic acids that do not have a nitrogen atom include citric acid, lactic acid, acetic acid, propionic acid, malic acid, tartaric acid, malonic acid, oxalic acid, succinic acid, gluconic acid, glycolic acid, diglycolic acid, maleic acid, benzoic acid, phthalic acid, salicylic acid, salicylhydroxamic acid, phthalhydroxamic acid, and formic acid. Of these, citric acid, lactic acid, acetic acid, malic acid, tartaric acid, malonic acid, oxalic acid, glycolic acid, phthalic acid, salicylhydroxamic acid, and phthalhydroxamic acid are preferred, and citric acid, lactic acid, acetic acid, malic acid, tartaric acid, malonic acid, oxalic acid, and glycolic acid are more preferred.

[0071] Examples of carboxylic acids having a nitrogen atom include amino acids and aminopolycarboxylic acids. Examples of amino acids include glycine, alanine, asparagine, aspartic acid, arginine, glutamine, glutamic acid, histidine, serine, cysteine, tyrosine, and phenylalanine. Examples of aminopolycarboxylic acids include ethylenediaminetetraacetate, diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetate, dihydroxyethylethylenediaminetetraacetate, nitriloic acid acetate, hydroxyethyliminodiacetate, β-alanine diacetate, aspartic acid diacetate, methylglycine diacetate, iminodisuccinate, serine diacetate, hydroxyiminodisuccinate, dihydroxyethylglycine, aspartate, and glutamate.

[0072] -Phosphonic acid- The phosphonic acid may be a monophosphonic acid having one phosphonic acid group, or a polyphosphonic acid having two or more phosphonic acid groups. Among these, a polyphosphonic acid having two or more phosphonic acid groups is preferred.

[0073] The number of phosphonic acid groups in the phosphonic acid is preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the phosphonic acid is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. There is no particular lower limit, and the number is preferably 1 or more. Examples of polyphosphonic acids that can be used include the compounds represented by the general formulas [1] to [3] described in paragraphs

[0013] to

[0023] of WO 2013 / 162020, the compounds described in paragraphs

[0026] to

[0036] of WO 2018 / 020878, and the compounds ((co)polymers) described in paragraphs

[0031] to

[0046] of WO 2018 / 030006, the contents of which are incorporated herein by reference.

[0074] Polyphosphonic acids include ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDP), 1-hydroxypropylidene-1,1'-diphosphonic acid, 1-hydroxybutylidene-1,1'-diphosphonic acid, ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrilotris(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), 1,3-propylenediaminebis(methylenephosphonic acid), and ethylenediaminetetra(methylenephosphonic acid). (EDTPO), ethylenediaminetetra(ethylenephosphonic acid), 1,3-propylenediaminetetra(methylenephosphonic acid) (PDTMP), 1,2-diaminopropanetetra(methylenephosphonic acid), 1,6-hexamethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) (DEPPO), diethylenetriaminepenta(ethylenephosphonic acid), triethylenetetraminehexa(methylenephosphonic acid), and triethylenetetraminehexa(ethylenephosphonic acid), with HEDP being preferred.

[0075] When the composition contains an organic acid (preferably a carboxylic acid), the content of the organic acid (preferably a carboxylic acid) is not particularly limited, but is preferably 0.001 to 10 mass%, more preferably 0.01 to 5 mass%, and even more preferably 0.01 to 3 mass%, relative to the total mass of the composition. The organic acid may be used alone or in combination of two or more. When two or more organic acids are used, the total content is preferably within the above range. When the composition contains two or more organic acids, an embodiment in which the organic acids contain at least one carboxylic acid and at least one phosphonic acid is also preferred.

[0076] (Oxidizing agents other than periodate compounds) The composition may contain an oxidizing agent other than the periodate compound. Examples of oxidizing agents other than periodate compounds include hydrogen peroxide, peroxides, nitric acid and its salts, iodic acid and its salts, hypochlorous acid and its salts, chlorous acid and its salts, chloric acid and its salts, perchloric acid and its salts, persulfuric acid and its salts, dichromate and its salts, permanganic acid and its salts, ozone water, silver(II) salts, and iron(III) salts. When the composition contains an oxidizing agent other than a periodic acid compound, it is preferable that the total content of the periodic acid and the content of the oxidizing agent other than a periodic acid compound is within the range of the periodic acid content described above. Furthermore, the content of oxidizing agents other than periodate compounds contained in the composition is preferably less than the content of periodic acid, and it is more preferable that the composition does not contain any oxidizing agents other than periodate compounds.

[0077] (pH adjuster) The present composition may contain a pH adjuster other than the above-mentioned alkaline compound and organic acid. Examples of pH adjusters other than alkaline compounds and organic acids include inorganic acids such as sulfuric acid, hydrochloric acid, and acetic acid.

[0078] (Additives) The present composition may contain, as additives, components other than those described above, so long as they do not impair the effects of the present invention or the functions of the respective components.

[0079] The composition may contain a polymeric compound as an additive. The polymer compound is an organic compound other than the above-mentioned components, and is a compound having a molecular weight (weight average molecular weight when the molecular weight distribution is present) of 500 or more. Examples of the polymer compound include a polyhydroxy compound and an anionic polymer compound. In this specification, the weight average molecular weight is a polystyrene-equivalent value by GPC (gel permeation chromatography). The GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) as columns, and THF (tetrahydrofuran) as an eluent.

[0080] -Polyhydroxy compounds- A polyhydroxy compound is an organic compound having two or more (for example, 2 to 200) alcoholic hydroxyl groups in the molecule. The molecular weight of the polyhydroxy compound (weight average molecular weight when the compound has a molecular weight distribution) is 500 or more, and preferably 500 to 3,000.

[0081] Examples of the polyhydroxy compounds include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; oligosaccharides such as mannitol, cellotriose, gentianose, raffinose, melezitose, cerotetrose, and stachyose; and polysaccharides and hydrolysates thereof such as starch, glycogen, cellulose, chitin, and chitosan.

[0082] Cyclodextrin is also preferred as a polyhydroxy compound. Cyclodextrin is a type of cyclic oligosaccharide in which multiple D-glucose units are bonded together through glucoside bonds to form a cyclic structure. Known cyclodextrins are compounds in which five or more glucose units (e.g., six to eight) are bonded together. Examples of cyclodextrin include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, with γ-cyclodextrin being preferred.

[0083] -Anionic polymer compounds- The anionic polymer compound is a compound having an anionic group and a weight average molecular weight of 500 or more. Examples of the anionic polymer compound include polymers and their salts that have a monomer having a carboxyl group as a basic structural unit, and copolymers containing them.Specific examples include polyacrylic acid and its salts, and copolymers containing them; polymethacrylic acid and its salts, and copolymers containing them; polyamic acid and its salts, and copolymers containing them; polycarboxylic acid such as polymaleic acid, polyitaconic acid, polyfumaric acid, poly(p-styrene carboxylic acid) and polyglyoxylic acid, and its salts, and copolymers containing them. Among these, at least one selected from the group consisting of polyacrylic acid, polymethacrylic acid, copolymers containing polyacrylic acid and polymethacrylic acid, and salts thereof is preferred.

[0084] The weight average molecular weight of the anionic polymer compound is preferably from 1,000 to 100,000, and more preferably from 2,000 to 50,000. The anionic polymer compound may be ionized in the composition.

[0085] The polymer compounds may be used alone or in combination of two or more. When the present composition contains a polymer compound, the content thereof is preferably from 0.001 to 10 mass %, and more preferably from 0.005 to 5 mass %, relative to the total mass of the present composition.

[0086] <ph> The pH of the composition is not particularly limited, but is preferably 7.0 or more, more preferably 7.5 or more, and even more preferably 8.0 or more, in terms of excellent etching selectivity. The upper limit is not particularly limited, and may be 14.0 or less. In terms of excellent stability over time of the composition, the pH of the composition is preferably 13.0 or less, and more preferably 11.5 or less. In this specification, the pH of the composition and the first and second liquids described below are measured at 25° C. using a pH meter (F-51 (product name) manufactured by HORIBA, Ltd.).

[0087] <Kit> The present composition may be prepared as a kit in which each component (raw material) is divided into a plurality of parts. The kit of the present invention includes at least a first liquid and a second liquid, and the periodate compound, the azole compound, and the alkali compound are contained in either the first liquid or the second liquid. The kit of the present invention is used for preparing the present composition by mixing the first liquid and the second liquid. As the kit, a kit including at least a first liquid containing a periodate compound and an alkali compound, and a second liquid containing an azole compound is preferable in terms of excellent storage stability.

[0088] (1st liquid) The first liquid preferably contains a periodic acid compound and an alkaline compound, and more preferably further contains a solvent (more preferably water). The content of the periodate compound in the first liquid is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and even more preferably 4.0% by mass or more, based on the total mass of the first liquid. The upper limit is not particularly limited, but is preferably 60.0% by mass or less, more preferably 40.0% by mass or less, and even more preferably 20.0% by mass or less. By setting the content within this range, the liquid can be made suitable for mixing with the second liquid, and the mixed liquid with the second liquid has the above-mentioned suitable content range of the periodate compound. Also,

[0089] The content of the alkali compound in the first liquid is not particularly limited, but in terms of excellent stability over time of the first liquid, it is preferably 0.3% by mass or more, more preferably 1.0% by mass or more, and even more preferably 3.0% by mass or more, based on the total mass of the first liquid. The upper limit is not particularly limited, but it is preferably 40.0% by mass or less, more preferably 20.0% by mass or less, and even more preferably 12.0% by mass or less. It is also preferable to adjust the content of the alkaline compound so that the pH of the first liquid falls within a suitable range described below.

[0090] The first liquid preferably contains no components other than a periodic acid compound, an alkaline compound, and a solvent, and more preferably contains no components other than a periodic acid compound, an alkaline compound, and water. The content of water in the first liquid may be the remainder other than the periodic acid compound and the alkali compound, and is not particularly limited, but is preferably 50 to 95 mass %, more preferably 65 to 90 mass %.

[0091] The pH of the first liquid is not particularly limited, but in terms of excellent stability over time of the first liquid, it is preferably 5 or more, and more preferably 8 or more. There is no particular upper limit, but it is preferably 14 or less, and more preferably 12 or less.

[0092] (2nd liquid) The second liquid preferably contains at least an azole compound, and more preferably further contains a solvent (more preferably water). The content of the azole compound in the second liquid is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.04% by mass or more, and even more preferably 0.1% by mass or more, based on the total mass of the second liquid. The upper limit is not particularly limited, but is preferably 10.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less. By setting it in this range, it can be made suitable for mixing with the first liquid, and the mixed liquid with the first liquid has the above-mentioned suitable content range of the azole compound.

[0093] The water-soluble organic solvent may be contained in either liquid, but is preferably contained in the second liquid. The content of the water-soluble organic solvent in the second liquid is not particularly limited, but is preferably 0.2 to 50 mass %, more preferably 2 to 40 mass %, and even more preferably 5 to 30 mass %, based on the total mass of the second liquid.

[0094] The surfactant may be contained in either liquid, but is preferably contained in the second liquid. The content of the surfactant in the second liquid is not particularly limited, but is preferably 0.02% by mass or more, and more preferably 0.05% by mass or more, based on the total mass of the second liquid. The upper limit is not particularly limited, but is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the second liquid, in order to suppress foaming of the composition.

[0095] The carboxylic acid may be contained in either liquid, but when the first liquid contains an alkaline compound, it is preferable that the carboxylic acid is contained in the second liquid. By containing the carboxylic acid in the second liquid, the composition obtained by mixing the first liquid containing the alkaline compound and the second liquid can be easily adjusted to satisfy the above-mentioned preferable pH range. The content of the carboxylic acid in the second liquid is not particularly limited, and is preferably 0.002 to 20 mass %, and more preferably 0.02 to 10 mass %, relative to the total mass of the second liquid. When the first liquid contains an alkaline compound, it is preferable to adjust the content of the carboxylic acid in the second liquid so that the pH of the mixture of the first liquid and the second liquid falls within the suitable pH range of the composition described above.

[0096] The second liquid may further contain water. The content of water in the second liquid may be the balance other than the azole compound, the water-soluble organic solvent, the surfactant, and the carboxylic acid, and is not particularly limited, but is preferably 50 to 95 mass %, more preferably 65 to 90 mass %.

[0097] The pH of the second liquid is not particularly limited, but is preferably not more than 9, and more preferably not more than 7. The lower limit is not particularly limited, and may be 0 or more.

[0098] The kit may be a three or more liquid system kit further comprising a third liquid containing at least water in addition to the first and second liquids. A two-liquid kit including only the first liquid and the second liquid is preferred in that the process for producing the composition is simpler.

[0099] (Kit Creation) The method for preparing the kit is not particularly limited. For example, after preparing the first and second liquids described above, they may be placed in different containers to prepare a composition preparation kit. The method for preparing the first liquid is not particularly limited, and examples thereof include a method in which periodic acid and an alkaline compound are added to pure water obtained by purification, and then the mixture is stirred or the like to prepare the first liquid as a homogeneous aqueous solution. The method for preparing the second liquid is not particularly limited, and may be the same as the method for preparing the first liquid.

[0100] <Container> The composition and the first and second liquids included in the kit can be filled in any container for storage, transportation, and use. The container is preferably one that is highly clean and has little elution of impurities. Examples of containers in which the composition can be filled include, but are not limited to, the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd.

[0101] <Manufacturing method> The method for producing the composition is not particularly limited, and for example, the composition can be produced by mixing the above-mentioned components. The order and / or timing of mixing the above-mentioned components is not particularly limited. For example, a method of producing the composition includes adding a periodic acid compound, an azole compound, an alkali compound, and an optional component in order to a stirrer such as a mixing mixer containing purified pure water, and then thoroughly stirring the mixture to mix the components.

[0102] The composition is preferably produced by mixing the first liquid containing a periodate compound and an alkali compound and the second liquid containing an azole compound, which are included in the above-mentioned kit. The first liquid and the second liquid are stored separately, and when the composition is used, they are mixed and applied to the workpiece, so that the dissolving ability of the metal content and the etching selectivity are maintained even after long-term storage, and a composition having excellent storage stability can be obtained.

[0103] Other examples of methods for producing the composition include a method in which the components are mixed after the pH is adjusted to a set value using at least a portion of an alkaline compound and / or a pH adjuster, and a method in which the components are mixed and then adjusted to a set pH using at least a portion of an alkaline compound and / or a pH adjuster.

[0104] Alternatively, the composition may be produced by preparing a concentrated solution having a lower water content than that at the time of use, and diluting it with a diluent (preferably water) at the time of use to adjust the content to a predetermined value. Alternatively, the composition may be produced by diluting the concentrated solution with a diluent, and then adjusting the pH to a set value using at least a part of the alkaline compound and / or a pH adjuster. When diluting the concentrated solution, a predetermined amount of the diluent may be added to the concentrated solution, or a predetermined amount of the concentrated solution may be added to the diluent.

[0105] [Processing object] The composition is used to remove metal inclusions on a substrate. In this specification, "on the substrate" includes, for example, the front and back surfaces, side surfaces, and inside grooves of the substrate. Furthermore, the metal inclusions on the substrate include not only cases where the metal inclusions are directly present on the surface of the substrate, but also cases where the metal inclusions are present on the substrate via another layer.

[0106] Examples of the metal contained in the metal inclusion include metal M selected from Ru (ruthenium), 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), W (tungsten), and Ir (iridium). In other words, the metal-containing material is preferably a material containing metal M.

[0107] The metal-containing material may be any substance that contains a metal (metal atom), and examples thereof include a simple substance of metal M, an alloy containing metal M, an oxide of metal M, a nitride of metal M, and an oxynitride of metal M. The metal-containing material may also be a mixture containing two or more of these compounds. The oxides, nitrides, and oxynitrides may be complex oxides, complex nitrides, and complex oxynitrides that contain a metal. The content of metal atoms in the metal-containing material is preferably 10 mass% or more, more preferably 30 mass% or more, and even more preferably 50 mass% or more, based on the total mass of the metal-containing material. The upper limit is 100 mass% because the metal-containing material may be the metal itself.

[0108] The metal-containing material is preferably a Ru-containing material, that is, the composition is preferably used for removing a Ru-containing material on a substrate. Examples of Ru-containing substances include simple Ru, Ru alloys, Ru oxides, Ru nitrides, and Ru oxynitrides. The content of Ru atoms in the Ru-containing material is preferably 10 mass% or more, more preferably 30 mass% or more, and even more preferably 50 mass% or more, based on the total mass of the Ru-containing material. The upper limit is not particularly limited, but is 100 mass% because the Ru-containing material may be simple Ru.

[0109] The workpiece is a substrate having metal inclusions, that is, the workpiece includes at least the substrate and the metal inclusions on the substrate. The type of substrate is not particularly limited, but a semiconductor substrate is preferred. The above substrates include various substrates such as 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 disks, substrates for magnetic disks, and substrates for magneto-optical disks. Materials that may comprise the semiconductor substrate include silicon, silicon germanium, and III-V compounds such as GaAs, or any combination thereof.

[0110] The types of metal inclusions on the substrate are as described above. The form of the metal inclusions on the substrate is not particularly limited, and may be, for example, a film-like arrangement (metal-containing film), a wiring-like arrangement (metal-containing wiring), or a particle-like arrangement. As described above, the metal is preferably Ru (ruthenium), and the workpiece is preferably a workpiece having a substrate and a Ru-containing film, Ru-containing wiring, or particulate Ru-containing material disposed on the substrate. Also preferred as the metal is Cu (copper) or Co (cobalt), and also preferred as the workpiece is a workpiece having a substrate and a Cu- or Co-containing film, a Cu- or Co-containing wiring, or a particulate Cu- or Co-containing material disposed on the substrate.

[0111] It is also preferable that two or more kinds of metal inclusions are present on the substrate. For example, the substrate may have at least a Ru-inclusion (Ru-inclusion film, Ru-inclusion wiring, and / or particulate Ru-inclusion, etc.) and a Cu-inclusion (Cu-inclusion film, Cu-inclusion wiring, and / or particulate Cu-inclusion, etc.) or a Co-inclusion (Co-inclusion film, Co-inclusion wiring, and / or particulate Co-inclusion, etc.) on the substrate. When two or more kinds of metal inclusions are present on the substrate, the two or more kinds of metal inclusions may be present separately or in a uniformly mixed form. In addition, two or more kinds of metal-containing substances may be present in different forms. For example, a Ru-containing film and a Cu-containing wiring or a Co-containing wiring may be present on a substrate.

[0112] Examples of forms in which metal inclusions are arranged in particulate form include a substrate having a metal-containing film and having particulate metal inclusions attached as a residue after dry etching, as described below, and a substrate having particulate metal inclusions (particulate metal oxides, etc.) attached as a residue after chemical mechanical polishing (CMP) is performed on a metal-containing film. The thickness of the metal-containing film is not particularly limited and can be appropriately selected depending on the application. For example, the thickness is preferably 50 nm or less, more preferably 20 nm or less, and even more preferably 10 nm or less. The metal-containing film may be disposed on only one main surface of the substrate, or on both main surfaces of the substrate, and may be disposed over the entire main surface of the substrate, or over a portion of the main surface of the substrate.

[0113] In addition to the metal-containing substance, the substrate may have various layers and / or structures as desired. For example, the substrate may have metal wiring, a gate electrode, a source electrode, a drain electrode, an insulating layer, a ferromagnetic layer, and / or a nonmagnetic layer. The substrate may have exposed integrated circuit structures, such as interconnect features, such as metal wiring and dielectric materials. Metals and alloys used in the interconnect features include, for example, aluminum, copper aluminum alloys, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. The substrate may have layers of silicon oxide, silicon nitride, silicon carbide, and / or carbon-doped silicon oxide.

[0114] The size, thickness, shape, layer structure, etc. of the substrate are not particularly limited and can be appropriately selected as desired.

[0115] As described above, the workpiece used in the processing method of the present invention has a metal-containing substance on the substrate. The method for manufacturing the substrate having the metal inclusion is not particularly limited. For example, the metal-containing film can be formed on the substrate by sputtering, chemical vapor deposition (CVD), molecular beam epitaxy (MBE), etc. In addition, when the metal-containing film is formed by sputtering, CVD, etc., the metal inclusion may also adhere to the back surface (the surface opposite to the metal-containing film side) of the substrate having the metal-containing film. The above method may also be carried out through a predetermined mask to form metal-containing wiring on a substrate. Furthermore, after a metal-containing film or metal-containing wiring is formed on a substrate, the substrate may be subjected to a different process or treatment before being used as a processing target for the processing method. For example, a substrate having a metal-containing film or metal-containing interconnects may be subjected to dry etching to produce a substrate having dry etching residues containing metal, or a substrate having a metal-containing film or metal-containing interconnects may be subjected to CMP to produce a substrate having metal inclusions.

[0116] [Substrate processing method] The substrate treating method of the present invention (hereinafter also referred to as "the present treating method") includes a step A of removing metal inclusions on a substrate using the above-mentioned composition. As described above, the present treatment method is particularly suitable for use when the metal-containing material includes a Ru-containing material. The composition used in the present treatment method is as described above. The substrate having metal inclusions, which is the object to be treated by this treatment method, is also as described above.

[0117] A specific example of the method for step A is a method in which the composition is brought into contact with a substrate having a metal-containing substance, which is the object to be treated. The method of contacting is not particularly limited, and examples thereof include a method of immersing the object to be treated in the composition placed in a tank, a method of spraying the composition onto a substrate, a method of pouring the composition onto a substrate, or any combination thereof. Among these, a method of immersing the substrate having the metal-containing material as the object to be treated in the composition is preferred.

[0118] Additionally, mechanical agitation methods may be used to further enhance the cleaning ability of the composition. Examples of the mechanical stirring method include a method of circulating the composition on a substrate, a method of flowing or spraying the composition on a substrate, and a method of stirring the composition by ultrasonic or megasonic means.

[0119] The treatment time in step A can be adjusted depending on the method for contacting the composition with the substrate, the temperature of the composition, etc. The treatment time (contact time between the composition and the substrate) is not particularly limited, but is preferably 0.25 to 10 minutes, more preferably 0.5 to 2 minutes. The temperature of the composition during the treatment is not particularly limited, but is preferably from 20 to 75°C, more preferably from 20 to 60°C.

[0120] In step A, the metal-containing substances to be removed from the substrate may be of one type or of two or more types. When two or more kinds of metal-containing substances are removed in step A, the two or more kinds of metal-containing substances may be simultaneously removed in one treatment, or may be treated separately. The composition is preferably used in a removal treatment carried out to remove at least one of the metal-containing substances in step A in which two or more kinds of metal-containing substances on a substrate are removed by multiple removal treatments. Examples of combinations of two or more metal-containing materials include combinations of materials containing two or more of the above-mentioned metal M (materials containing two or more metal M materials). Among these, combinations containing at least a Ru-containing material and a Cu-containing material or a Co-containing material are preferred.

[0121] In step A, a treatment of adding a solvent (preferably water) to the composition may be carried out as necessary while measuring the contents of the periodate compound, azole compound, and / or alkali compound in the composition. By carrying out this treatment, the component contents in the composition can be stably maintained within a predetermined range. The content of the periodic acid compound, the azole compound, the alkali compound, and the optional components in the composition can be measured by ion chromatography. A specific example of the apparatus used is Thermo Fisher's Dionex ICS-2100.

[0122] Specific preferred embodiments of step A include step A1 of using the composition to perform a recess etching treatment on a metal-containing wiring disposed on a substrate, step A2 of using the composition to remove a metal-containing film from the outer edge of a substrate on which the metal-containing film is disposed, step A3 of using the composition to remove metal inclusions adhering to the back surface of a substrate on which the metal-containing film is disposed, step A4 of using the composition to remove metal inclusions on a substrate after dry etching, and step A5 of using the composition to remove metal inclusions on a substrate after chemical mechanical polishing. Among them, as step A, step A1 is more preferable. The processing method used in each of the above processes will now be described.

[0123] <Process A1> Step A includes step A1 of performing a recess etching treatment on a metal-containing wiring disposed on a substrate using a composition. FIG. 1 shows a schematic diagram of the upper cross section of an example of a substrate having metal-containing wiring (hereinafter also referred to as a "wiring substrate") which is an object to be treated in the recess etching treatment in step A1. The wiring substrate 10a shown in FIG. 1 includes a substrate (not shown), an insulating film 12 having a groove disposed on the substrate, a barrier metal layer 14 disposed along the inner wall of the groove, and a metal-containing wiring 16 filled inside the groove.

[0124] The substrate and metal-containing interconnects in the interconnect substrate are as described above. The metal-containing wiring is preferably a Ru-containing wiring (a wiring containing Ru), a Cu-containing wiring, or a Co-containing wiring. The Ru-containing wiring preferably contains a simple substance of Ru, an alloy of Ru, an oxide of Ru, a nitride of Ru, or an oxynitride of Ru. The material constituting the barrier metal layer in the wiring board is not particularly limited, and examples thereof include titanium nitride (TiN) and tantalum nitride (TaN). Although the wiring board has a barrier metal layer in FIG. 1, the wiring board may not have a barrier metal layer. 1, a liner layer may be disposed between the barrier metal layer 14 and the metal-containing wiring 16. The material constituting the liner layer is not particularly limited, and examples thereof include a Ru-containing material, a Cu-containing material, and a Co-containing material.

[0125] The method for manufacturing the wiring board is not particularly limited, and examples of the method include a method including 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 barrier metal layer on the insulating film, a step of forming a metal-containing film so as to fill the groove, and a step of performing a planarization process on the metal-containing film.

[0126] In step A1, the above-mentioned composition is used to perform a recess etching process on the metal-containing wiring in the wiring substrate, thereby removing a part of the metal-containing wiring to form a recess. More specifically, when step A1 is performed, a portion of the barrier metal layer 14 and the metal-containing interconnect 16 is removed, forming a recess 18, as shown in the wiring substrate 10b of FIG.

[0127] A specific example of the method for step A1 is to bring the composition into contact with the wiring board. The method for 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.

[0128] (Steps A1a and A1b) As step A1, it is also preferable to carry out step A1a of removing at least one metal inclusion from two or more types of metal inclusions (e.g., two or more types of metal M-containing materials, preferably a combination of a Ru-containing material and a Cu-containing material or a Co-containing material) arranged on a substrate, and step A1b of removing a metal inclusion different from the metal inclusion removed in step A1a. Steps A1a and A1b are performed on a wiring substrate in which a liner layer is disposed between a metal-containing wiring and a barrier metal layer, and the metal-containing wiring and the liner layer are different metal-containing materials. When the metal-containing wiring and the liner layer are composed of different metal inclusions, the components constituting the metal-containing wiring and the components constituting the liner layer may have different solubility in the processing solution depending on their types. In such a case, it is preferable to carry out step A1a of removing the metal-containing wiring using solution A, which has a higher solubility in the metal-containing wiring than the liner layer, and step A1b of removing the liner layer using solution B, which has a higher solubility in the liner layer than the metal-containing wiring. By carrying out the two-step removal process consisting of steps A1a and A1b, the degree of removal of the metal-containing wiring and the liner layer can be finely adjusted, and uniformity within the wafer can be ensured.

[0129] As the wiring board having the above-mentioned metal-containing wiring and a liner layer, a combination in which the metal-containing wiring is a Cu-containing wiring or a Co-containing wiring and the liner layer is a Ru-containing material, or a combination in which the metal-containing wiring is a Ru-containing wiring and the liner layer is a Cu-containing material or a Co-containing material is preferred, and a combination in which the metal-containing wiring is a Cu-containing wiring or a Co-containing wiring and the liner layer is a Ru-containing material is more preferred. In addition, since the etching selectivity of Ru-containing materials relative to Cu-containing materials and Co-containing materials is high, when the metal-containing wiring is a Ru-containing wiring and the liner layer is a Cu-containing or Co-containing material, it is preferable to use this composition as solution A used in step A1a to remove the metal-containing wiring, and when the metal-containing wiring is a Cu-containing or Co-containing wiring and the liner layer is a Ru-containing material, it is preferable to use this composition as solution B used in step A1b to remove the liner layer.

[0130] In particular, since the present composition has high etching selectivity for the material (preferably TiN or TaN) constituting the barrier metal layer, it is more preferable to use it as solution B used in step A1b for removing the liner layer in contact with the barrier metal layer for a wiring board having a liner layer between the metal-containing wiring and the barrier metal layer.

[0131] When steps A1a and A1b are performed as step A1, one of the solutions A and B is the present composition, and the other is a solution other than the present composition. The solution other than the present composition that can be used as solution A or B in step A1a or A1b is not particularly limited, and a known solution can be used depending on the types of two or more metal-containing substances arranged on the substrate and the etching selectivity of the present composition. For example, when a wiring board in which the metal-containing wiring is a Cu-containing wiring or a Co-containing wiring and the liner layer is Ru-containing is subjected to step A1b of removing the liner layer using the present composition, examples of solutions other than the present composition that can be used in step A1a of removing the metal-containing wiring include, for example, a mixture of sulfuric acid and hydrogen peroxide (SPM), a mixture of ammonia water and hydrogen peroxide (SC-1 or APM), and repeated treatment with hydrogen peroxide and an acidic aqueous solution.

[0132] In this processing method, step A1a and step A1b may be performed alternately. When step A1a and step A1b are performed alternately, each of step A1a and step A1b is preferably performed 1 to 10 times.

[0133] (Process B) Before or after step A1, step B may be performed as necessary to treat the wiring board using a predetermined solution (hereinafter, also referred to as a "specific solution"). In particular, as described above, when a barrier metal layer is disposed on a substrate, the components constituting the metal-containing wiring and the components constituting the barrier metal layer may have different solubilities in the composition depending on their types. In such a case, it is preferable to adjust the degree of dissolution of the metal-containing wiring and the barrier metal layer by using a solution that has a higher solubility in the barrier metal layer. From this point of view, the specific solution is preferably a solution that has poor solubility in the metal-containing wiring and excellent solubility in the material that constitutes the barrier metal layer.

[0134] The specific solution may be a solution selected from the group consisting of a mixture of hydrofluoric acid and hydrogen peroxide (FPM), a mixture of sulfuric acid and hydrogen peroxide (SPM), a mixture of ammonia water and hydrogen peroxide (APM), and a mixture of hydrochloric acid and hydrogen peroxide (HPM). The composition of the FPM is preferably within the range of "hydrofluoric acid:hydrogen peroxide:water=1:1:1" to "hydrofluoric acid:hydrogen peroxide:water=1:1:200" (volume ratio), for example. The composition of the SPM is preferably within the range of "sulfuric acid:hydrogen peroxide:water=3:1:0" to "sulfuric acid:hydrogen peroxide:water=1:1:10" (volume ratio), for example. The composition of the APM is preferably within the range of "ammonia water: hydrogen peroxide water: water = 1:1:1" to "ammonia water: hydrogen peroxide water: water = 1:1:30" (volume ratio), for example. The composition of HPM is preferably within the range of "hydrochloric acid:hydrogen peroxide:water=1:1:1" to "hydrochloric acid:hydrogen peroxide:water=1:1:30" (volume ratio), for example. Note that these preferred composition ratios are intended to mean composition ratios in which hydrofluoric acid is 49 mass% hydrofluoric acid, sulfuric acid is 98 mass% sulfuric acid, ammonia water is 28 mass% ammonia water, hydrochloric acid is 37 mass% hydrochloric acid, and hydrogen peroxide water is 31 mass% hydrogen peroxide water.

[0135] In step B, the method of treating the substrate obtained in step A1 with the specific solution is preferably a method of bringing the specific solution into contact with the substrate obtained in step A1. The method for bringing the specific solution into contact with the substrate obtained in step A1 is not particularly limited, and examples thereof include the same methods as those for bringing the composition into contact with the substrate. The contact time between the specific solution and the substrate obtained in step A1 is, for example, preferably from 0.25 to 10 minutes, and more preferably from 0.5 to 5 minutes.

[0136] In this processing method, step A1 and step B may be performed alternately. When they are performed alternately, each of step A1 and step B is preferably performed 1 to 10 times.

[0137] When step A1 includes steps A1a and A1b, the above-mentioned step B may be performed before steps A1a and A1b or after steps A1a and A1b. In addition, step A1 consisting of steps A1a and A1b and the above-mentioned step B may be performed alternately.

[0138] <Process A2> Step A includes step A2 of removing the metal-containing film from the outer edge of the substrate on which the metal-containing film is disposed, using a composition. FIG. 3 is a schematic diagram (top view) showing an example of a substrate on which a metal-containing film, which is the object to be processed in step A2, is disposed. 3, the workpiece 20 in step A2 is a laminate having a substrate 22 and a metal-containing film 24 disposed on one main surface (the entire area surrounded by the solid line) of the substrate 22. As will be described later, in step A2, the metal-containing film 24 located on the outer edge portion 26 (the area outside the dashed line) of the workpiece 20 is removed.

[0139] The substrate and the metal-containing film in the workpiece are as described above. The metal-containing film is preferably a Ru-containing film (a film containing Ru). The Ru-containing film preferably contains a simple substance of Ru, a Ru alloy, a Ru oxide, a Ru nitride, or a Ru oxynitride.

[0140] The specific method for step A2 is not particularly limited, but examples include a method in which the composition is supplied from a nozzle so that the composition comes into contact with only the metal-containing film on the outer edge of the substrate. In the treatment of step A2, the substrate processing apparatus and substrate processing method described in JP-A-2010-267690, JP-A-2008-080288, JP-A-2006-100368, and JP-A-2002-299305 can be preferably used.

[0141] The method for contacting the composition with the object to be treated is as described above. The preferred ranges for the contact time between the composition and the object to be treated and the temperature of the composition are as described above.

[0142] <Process A3> Step A includes step A3 of removing metal inclusions adhering to the back surface of a substrate on which a metal-containing film is disposed, using a composition. The workpiece used in step A3 may be the workpiece used in step A2. When forming the workpiece used in step A2, which is a substrate and a metal-containing film disposed on one main surface of the substrate, the metal-containing film is formed by sputtering, CVD, or the like. At that time, metal-containing substances may adhere to the surface (back surface) of the substrate opposite to the metal-containing film side. In order to remove such metal-containing substances from the workpiece, step A3 is performed.

[0143] The specific method for step A3 is not particularly limited, but may be, for example, a method in which the composition is sprayed onto the back surface of the substrate so that the composition comes into contact with only the back surface of the substrate.

[0144] The method for contacting the composition with the object to be treated is as described above. The preferred ranges for the contact time between the composition and the object to be treated and the temperature of the composition are as described above.

[0145] <Process A4> Step A includes step A4 of removing metal inclusions on a substrate after dry etching using a composition. FIG. 4 is a schematic diagram showing an example of the object to be processed in step A4. The workpiece 30 shown in Fig. 4 includes a metal-containing film 34, an etching stop layer 36, an interlayer insulating film 38, and a metal hard mask 40 on a substrate 32 in this order, and a hole 42 in which the metal-containing film 34 is exposed at a predetermined position is formed by a dry etching process or the like. That is, the workpiece shown in Fig. 4 is a laminate including a substrate 32, a metal-containing film 34, an etching stop layer 36, an interlayer insulating film 38, and a metal hard mask 40 in this order, and includes a hole 42 penetrating from the surface of the metal hard mask 40 to the surface of the metal-containing film 34 at the position of the opening of the metal hard mask 40. An inner wall 44 of the hole 42 is composed of a cross-sectional wall 44a consisting of the etching stop layer 36, the interlayer insulating film 38, and the metal hard mask 40, and a bottom wall 44b consisting of the exposed metal-containing film 34, and has dry etching residue 46 attached thereto. The dry etch residue contains metal inclusions.

[0146] The metal-containing film is preferably a Ru-containing film (a film containing Ru). The Ru-containing film preferably contains a simple substance of Ru, an alloy of Ru, an oxide of Ru, a nitride of Ru, or an oxynitride of Ru. The metal-containing material is preferably a Ru-containing material. The Ru-containing material preferably includes a simple Ru element, a Ru alloy, a Ru oxide, a Ru nitride, or a Ru oxynitride. The interlayer insulating film and the metal hard mask are made of known materials. Although a metal hard mask is used in the embodiment shown in FIG. 4, a resist mask formed from a known photoresist material may also be used.

[0147] A specific example of the method for step A4 is a method in which the composition is brought into contact with the object to be treated. The method for 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.

[0148] <Process A5> Step A includes step A5 of removing metal inclusions on a substrate after chemical mechanical polishing (CMP) using the composition. CMP technology is introduced into the manufacturing process of planarizing an insulating film, planarizing a connection hole, and damascene wiring. The substrate after CMP may be contaminated by a large amount of particles used as abrasive particles and metal impurities. Therefore, it is necessary to remove these contaminants and clean the substrate before entering the next processing stage. Therefore, by performing step A5, it is possible to remove metal-containing substances that are generated and adhere to the substrate when the CMP processing object has a metal-containing wiring or a metal-containing film.

[0149] As described above, the workpiece in step A5 is a substrate having metal inclusions after CMP. The metal-containing material is preferably a Ru-containing material. The Ru-containing material preferably includes a simple Ru element, a Ru alloy, a Ru oxide, a Ru nitride, or a Ru oxynitride.

[0150] A specific example of the method for step A5 is a method in which the composition is brought into contact with the object to be treated. The method for 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.

[0151] <Process C> This treatment process may include, after the above-mentioned step A, a step C of performing a rinsing treatment on the substrate obtained in step A using a rinsing liquid, if necessary. When the composition is brought into contact with a substrate, iodine compounds derived from the composition may adhere to the surface of the substrate as residual iodine (I residue). Such residual iodine (I residue) may adversely affect subsequent processes and / or the final product. By performing a rinsing step, the residual iodine (I residue) can be removed from the surface of the substrate.

[0152] Examples of the rinsing liquid include hydrofluoric acid, hydrochloric acid, hydrogen peroxide, a mixture of hydrofluoric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of ammonia water and hydrogen peroxide, a mixture of hydrochloric acid and hydrogen peroxide, carbon dioxide water, ozone water, hydrogen water, a citric acid solution, sulfuric acid, ammonia water, isopropyl alcohol, a hypochlorous acid solution, aqua regia, ultrapure water, nitric acid, perchloric acid, an oxalic acid solution, and an orthoperiodic acid solution. These rinsing liquids may be mixed and used as long as the purpose of the rinsing step is not impaired. It should be noted that hydrofluoric acid, nitric acid, perchloric acid, and hydrochloric acid refer to aqueous solutions in which HF, HNO3, HClO4, and HCl are dissolved in water, respectively. The sulfuric acid may be an aqueous solution of H2SO4 in water. Ozone water, carbon dioxide water, and hydrogen water refer to aqueous solutions in which O3, CO2, and H2 are dissolved in water, respectively.

[0153] Among these, from the viewpoint of further reducing the amount of iodine remaining on the substrate surface after the rinsing step, the rinsing liquid is preferably carbon dioxide water, ozone water, hydrogen water, hydrofluoric acid, citric acid aqueous solution, hydrochloric acid, sulfuric acid, ammonia water, hydrogen peroxide aqueous solution, SPM, APM, HPM, IPA, hypochlorous acid aqueous solution, aqua regia, or FPM, and more preferably hydrofluoric acid, hydrochloric acid, hydrogen peroxide aqueous solution, SPM, APM, HPM, or FPM.

[0154] A specific example of the method for step C is to bring the substrate obtained in step A, which is the object to be treated, into contact with a rinsing liquid. The contact may be performed by immersing the substrate in the rinse liquid contained in a tank, spraying the rinse liquid onto the substrate, flowing the rinse liquid onto the substrate, or any combination of these methods.

[0155] The treatment time (contact time between the rinse liquid and the object to be treated) is not particularly limited, but is from 5 seconds to 5 minutes. The temperature of the rinse solution during the treatment is not particularly limited, but is preferably from 16 to 60°C, more preferably from 18 to 40°C.

[0156] Furthermore, the present processing method may include a step D of performing a drying process, if necessary, after the step C. The method of the drying process is not particularly limited, and examples thereof include spin drying, flowing a dry gas over the substrate, heating the substrate with a heating means such as a hot plate or an infrared lamp, IPA (isopropyl alcohol) vapor drying, Marangoni drying, Rotagoni drying, or a combination thereof. Drying times vary depending on the particular method used, but are typically on the order of 30 seconds or more and up to a few minutes.

[0157] The present processing method may be carried out in combination with other processes carried out on the substrate, before or after the other processes, or may be incorporated into other processes while carrying out the present processing method, or may be incorporated into other processes. Other processes include, for example, processes for forming each structure such as metal wiring, gate structure, source structure, drain structure, insulating layer, ferromagnetic layer and / or non-magnetic layer (layer formation, etching, chemical mechanical polishing, modification, etc.), resist formation process, exposure process and removal process, heat treatment process, cleaning process, and inspection process. The present processing method may be performed in a back-end process (BEOL: Back end of the line) or a front-end process (FEOL: Front end of the line). From the viewpoint of better exerting the effects of the present invention, however, it is preferable to perform the processing in a front-end process. EXAMPLES

[0158] The present invention will be described in more detail below based on examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0159] Example A [Preparation of Composition] Compositions having the formulations shown in Tables 1 to 3 below were prepared, and the following tests were carried out using the prepared compositions. The meanings of the abbreviations used in Tables 1 to 3 for the oxidizing agent (periodic acid compound), azole compound, water-soluble organic solvent, surfactant, organic acid, and alkaline compound used in the preparation of the composition are shown below. The following components used in preparing the compositions were all commercially available.

[0160] (Oxidizing agent (O)) O1: Orthoperiodic acid (contained in periodate compounds) O2: Metaperiodic acid (contained in periodate compounds) O3: Hydrogen peroxide (not included in periodate compounds) O4: Iodic acid (not included in periodic acid compounds)

[0161] (Azole compound (A)) A1: 1H-benzotriazole A2: 5-methyl-1H-benzotriazole A3: Tolyltriazole A4: 2,2'-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol A5: 1,2,4-triazole A6: Adenine A7: Guanine

[0162] (Water-soluble organic solvent (B)) B1: Diethylene glycol diethyl ether B2: Tetraethylene glycol dimethyl ether B3: Diethylene glycol dibutyl ether B4: Diethylene glycol monobutyl ether

[0163] (Surfactant (C)) C1: Lauryl dimethylaminoacetic acid betaine C2: Stearyl dimethylaminoacetate betaine C3: 2-Lauryl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine C4: Dodecylbenzenesulfonic acid C5: Lauryl phosphate ester ("Hostene HLP" manufactured by Nikko Chemicals Co., Ltd.) C6:C 12 ~C 14 Alkyl diphenyl ether disulfonic acid ("Takesurf A43-NQ" manufactured by Takemoto Oil Co., Ltd.) C7: (CH3)2Ph-(OE)6OPO3H2: Takemoto Oil Co., Ltd., product name "Phosphanol FS-3PG"

[0164] (Organic acid (D)) D1: Citric acid D2: Tartaric acid D3: Acetic acid D4: 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) D5: Diethylenetriaminepentaacetic acid (DTPA) D6: Succinic acid D7: Adipic acid

[0165] (Alkaline Compounds (E)) E1: Tetramethylammonium hydroxide E2: Ethyltrimethylammonium hydroxide E3: Tetraethylammonium hydroxide E4: Tetrabutylphosphonium hydroxide (TBPH) E5: 2-amino-2-methyl-1-propanol (AMP) E6: 2-(dimethylamino)-2-methyl-1-propanol (DMAMP) In Comparative Example 1, citric acid (D1) was used in place of the alkaline compound.

[0166] (Additive (F)) F1: γ-cyclodextrin (γ-CD) F2: Polyacrylic acid (weight average molecular weight (Mw): 6,000) F3: Polyacrylic acid (weight average molecular weight (Mw): 30,000)

[0167] In Tables 1 to 3, the "amount" column indicates the content of each component relative to the total mass of the composition. In each of the examples and comparative examples, the content of the alkali compound (citric acid in Comparative Example 1) was adjusted so that the pH of the composition was the value described in the "composition pH" column of Tables 1 to 3. In Examples A22 to A38, A40 to A58, A60, and A61, the contents of the two alkali compounds were adjusted so that the ratio of the contents of the respective alkali compounds was 1:1 by mass ratio. In Examples A39 and A59, the contents of the three alkali compounds were adjusted so that the ratio of the contents of the respective alkali compounds was 1:1:1 by mass ratio. The remainder of the composition is water.

[0168] In the table, the numerical value in the "Ratio 1 (O / A)" column indicates the ratio (mass ratio) of the content of the oxidizing agent (periodic acid) to the content of the azole compound. The numerical value in the "Ratio 2 (B / A)" column indicates the ratio (mass ratio) of the content of the water-soluble organic solvent to the content of the azole compound when a water-soluble organic solvent is used. The numerical value in the "Ratio 3 (O / E)" column indicates the ratio (mass ratio) of the content of the oxidizing agent (periodic acid) to the content of the alkali compound.

[0169] [Test] On one surface of a commercially available silicon wafer (diameter: 12 inches), a substrate having a Ru layer (a layer composed of Ru alone) formed by CVD (Chemical Vapor Deposition) method was prepared. The obtained substrate was placed in a container filled with the composition of each example or each comparative example, and the composition was stirred to perform a Ru layer removal treatment for 1 minute. The temperature of the composition was the temperature (°C) described in the "treatment temperature" column in the table.

[0170] [Evaluation] <Ru dissolution ability> From the difference in the thickness of the Ru layer before and after the treatment, the etching rate (Å / min) of the Ru layer was calculated. The calculated etching rate of the Ru layer was evaluated according to the following criteria. The evaluation results are shown in Tables 1 to 3. AA: Etching rate is 30 Å / min or more A: Etching rate is 20 Å / min or more and less than 30 Å / min B: Etching rate is 10 Å / min or more and less than 20 Å / min C: Etching rate is 5 Å / min or more and less than 10 Å / min D: Etching rate is less than 5 Å / min

[0171] <Etching selectivity> Substrates were prepared according to the above method, except that a Cu layer, a TaN layer, or a Co layer was formed by CVD instead of the Ru layer, and the etching rates (Å / min) of the Cu layer, the TaN layer, and the Co layer were calculated.

[0172] From the calculated etching rates of the Ru layer, Cu layer, TaN layer, and Co layer, the ratio (etching selectivity) of the etching rate of the Ru layer to the etching rate of the Cu layer, TaN layer, or Co layer was calculated for each composition. Based on the calculated etching selectivity of the Ru layer to the Cu layer (Ru / Cu), the etching selectivity of the Ru layer to the TaN layer (Ru / TaN), and the etching selectivity of the Ru layer to the Co layer (Ru / Co), the etching selectivity was evaluated according to the following criteria. The evaluation results are shown in Tables 1 to 3.

[0173] (Ru / Cu) AA: Etching selectivity of Ru layer to Cu layer is 100 or more A: The etching selectivity of the Ru layer to the Cu layer is 50 or more and less than 100. B: The etching selectivity of the Ru layer to the Cu layer is 20 or more and less than 50. C: The etching selectivity of the Ru layer to the Cu layer is 2 or more and less than 20. D: The etching selectivity of the Ru layer to the Cu layer is less than 2.

[0174] (Ru / TaN) AA: Etching selectivity of Ru layer to TaN layer is 250 or more A: The etching selectivity of the Ru layer to the TaN layer is 150 or more and less than 250. B: The etching selectivity of the Ru layer to the TaN layer is 50 or more and less than 150. C: The etching selectivity of the Ru layer to the TaN layer is 10 or more and less than 50. D: The etching selectivity of the Ru layer to the TaN layer is less than 10

[0175] (Ru / Co) AA: Etching selectivity of Ru layer to Co layer is 60 or more A: The etching selectivity of the Ru layer to the Co layer is 40 or more and less than 60. B: The etching selectivity of the Ru layer to the Co layer is 20 or more and less than 40. B: The etching selectivity of the Ru layer to the Co layer is 1 or more and less than 20. B: The etching selectivity of the Ru layer to the Co layer is less than 1.

[0176] The results are shown in the table below.

[0177] [Table 1]

[0178] [Table 2]

[0179] [Table 3]

[0180] [Table 4]

[0181] [Table 5]

[0182] [Table 6]

[0183] [Table 7]

[0184] From the results shown in the table, it was confirmed that the composition of the present invention has excellent dissolving ability for Ru-containing substances and excellent etching selectivity.

[0185] In particular, it was confirmed that the content of the azole compound is more preferably less than 1.0 mass % in terms of superior dissolving ability and etching selectivity for metal-containing materials (comparison between Example A4 and Example A8). Also, it was confirmed that the content of the azole compound is more preferably 0.08 mass % or more in terms of superior etching selectivity (comparison between Example A4 and Example A17).

[0186] From the viewpoint of achieving a good balance between the ability to dissolve metal-containing materials and etching selectivity, it was confirmed that the ratio of the content of the periodate compound to the content of the azole compound (ratio 1) is more preferably 15 to 100 by mass ratio (comparison of Examples A2, A3, A7, A10 and A17).

[0187] It was confirmed that the inclusion of a water-soluble organic solvent is preferable in terms of superior ability to dissolve metal-containing substances (comparison of Examples A1 and A4 with Example A7). It was confirmed that the content of the water-soluble organic solvent is preferably less than 20 mass % in terms of superior dissolving ability and etching selectivity of metal-containing substances (comparison between Example A6 and Example A11). From the viewpoint of obtaining a superior ability to dissolve metal-containing substances, it was confirmed that the ratio of the content of the water-soluble organic solvent to the content of the azole compound (Ratio 3) is more preferably 15 to 160 by mass ratio (Comparison of Examples A4, A6, A10, A11, A13 and A14). It was confirmed that alkylene glycol dialkyl ether is preferable as the water-soluble organic solvent in terms of superior ability to dissolve metal-containing substances (comparison of Examples A2, A4, and A15 with Example A18).

[0188] It was confirmed that the inclusion of a surfactant is preferable in terms of superior etching selectivity (comparison between Example A2 and Example A5).

[0189] It was confirmed that the inclusion of a carboxylic acid is preferable in terms of better etching selectivity of Ru-containing materials relative to Cu-containing materials and of Ru-containing materials relative to Co-containing materials (Comparison of Examples A8 and A9 with Example A1).

[0190] It was confirmed that a pH of the composition of 7.0 or higher is preferable in terms of better etching selectivity (comparison of Examples A1 and A4 with Example A13).

[0191] A composition was prepared in the same manner as in Example A1, except that dimethylbis(2-hydroxyethyl)ammonium hydroxide (AH-212) (manufactured by Yokkaichi Chemical Co., Ltd.) was used as the alkaline compound (E) instead of tetramethylammonium hydroxide (E1), and the above-mentioned tests and evaluations were carried out. As a result, the same evaluation results as those of Example A1 were obtained.

[0192] A composition was prepared in the same manner as in Example A1, except that monoethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the alkaline compound (E) instead of tetramethylammonium hydroxide (E1), and the above-mentioned tests and evaluations were carried out. As a result, the same evaluation results as those of Example A1 were obtained.

[0193] A composition was prepared in the same manner as in Example A1, except that 2-amino-2-ethoxy-ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the alkaline compound (E) instead of tetramethylammonium hydroxide (E1), and the above-mentioned tests and evaluations were carried out. As a result, the same evaluation results as in Example A1 were obtained, except that the etching selectivity of Ru / TaN was evaluated as "A".

[0194] A composition was prepared in the same manner as in Example A1, except that sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the alkaline compound (E) instead of tetramethylammonium hydroxide (E1), and the above-mentioned tests and evaluations were carried out. As a result, the same evaluation results as in Example A1 were obtained, except that the etching selectivity of Ru / TaN was evaluated as "B".

[0195] Example B [Kit Creation] A first liquid and a second liquid having the composition shown in Table 4 below were prepared to produce a kit of Example B1 including the first liquid and the second liquid. Also prepared was a one-liquid composition of Comparative Example B1 having the composition shown in the following Table 4. The pH of the composition of Comparative Example B1 was 8.2. The abbreviations used in Table 4 have the same meanings as those in Example A. In addition, the "Composition (%)" column in Table 4 indicates the content of each component when the total amount of the first liquid and the second liquid is taken as 100 mass% in Example B1, and indicates the content of each component when the total mass of the one-liquid composition of Comparative Example B1 is taken as 100 mass% in Comparative Example B1.

[0196] [Testing and Evaluation] First, for the one-liquid composition of Comparative Example B1 immediately after production, a removal process of the Ru layer and the Cu layer was carried out according to the method described in Example A, and the etching rate of the Ru layer (Å / min) and the etching selectivity of the Ru layer to the Cu layer (Ru / Cu) were calculated. In Table 4, the "immediately after manufacture" columns for "etching rate" and "etching selectivity" show the calculated etching rate (Å / min) of the Ru layer and the etching selectivity (Ru / Cu) of the Ru layer relative to the Cu layer, respectively.

[0197] Next, a storage test was carried out using the first and second liquids of Example B1 and the one-liquid composition of Comparative Example B1 as test liquids to evaluate the storage stability of each test liquid. 500 mL of each test liquid was filled into a 1000 mL polypropylene container and sealed. The container filled with the test liquid was stored in an environment of 50° C. for 24 hours.

[0198] The first and second liquids of Example B1 that had undergone the storage test were mixed to prepare the composition of Example B1. Using the obtained composition of Example B1, the Ru layer and Cu layer were removed according to the method described in Example A, and the etching rate (Å / min) of the Ru layer and the etching selectivity (Ru / Cu) of the Ru layer relative to the Cu layer were calculated. Similarly, the etching rate (Å / min) of the Ru layer and the etching selectivity (Ru / Cu) of the Ru layer to the Cu layer were calculated using the one-liquid composition of Comparative Example B1 that had undergone the storage test.

[0199] The etching rate and etching selectivity (Ru / Cu) of the Ru layer were determined by the following formulas for the rate of decrease before and after the storage test. Decrease rate of etching rate (%)=(etching rate of the composition of Comparative Example B1 immediately after preparation−etching rate of the composition of Example B1 prepared after the storage test (or the composition of Comparative Example B1 after the storage test)) / (etching rate of the composition of Comparative Example B1 immediately after preparation)×100 Decrease rate of etching selectivity (%)=(etching selectivity of the composition of Comparative Example B1 immediately after preparation−etching selectivity of the composition of Example B1 prepared after storage test (or the composition of Comparative Example B1 after storage test)) / (etching selectivity of the composition of Comparative Example B1 immediately after preparation)×100

[0200] [Table 8]

[0201] From the results shown in the table, it was confirmed that the kit of the present invention has excellent storage stability.

[0202] Example C [Testing and Evaluation] A stopper film and an interlayer insulating film (SiO2) were formed in this order on an 8-inch silicon wafer. After forming a wiring groove (width: 50 nm, depth: 400 nm) in the interlayer insulating film of this silicon wafer, a barrier metal layer (thickness: 3 nm) made of a tantalum nitride (TaN) film was deposited on the entire surface by a sputtering method. Next, a liner layer (thickness: 3 nm) made of a ruthenium (Ru) film was deposited on the surface of the TaN film by a sputtering method, and further, a Cu-containing wiring was deposited on the surface of the liner layer until the wiring groove was filled. Then, the silicon wafer having the Cu-containing wiring, the liner layer, and the barrier metal layer was subjected to CMP processing until the interlayer insulating film was exposed. The obtained patterned wafer had a barrier metal layer made of a TaN film and a liner layer made of a Ru film along the inner walls of the wiring grooves of the interlayer insulating film from the side close to the inner walls, and the Cu-containing wiring was filled further inside.

[0203] The patterned wafer was immersed for 30 seconds in a glass container filled with a hydrogen peroxide solution (concentration 3% by mass, solution A) at 23°C, and then immersed for 30 seconds in a glass container filled with hydrochloric acid (concentration 1% by mass, solution A) at 23°C. The immersion in the hydrogen peroxide solution and the immersion in hydrochloric acid were repeated three times in total to perform the removal process of the Cu-containing wiring (step A1a above). This removal process reduced the thickness of the Cu-containing wiring by 10 nm. Next, the patterned wafer obtained was immersed for 180 seconds in a glass container filled with the composition (solution B) of Example A8 to remove the liner layer made of the Ru film exposed on the surface due to the removal of the Cu-containing wiring (step A1b above). The temperature of the composition (solution B) of Example A8 at this time was 60°C.

[0204] The processed patterned wafer was observed with a TEM (Transmission Electron Microscope) to check whether the Cu-containing wiring and the liner layer made of the Ru film had been removed. It was found that both the Cu-containing wiring and the liner layer made of the Ru film had been successfully removed. From these results, it was confirmed that the composition of the present invention is suitable for use in the stepwise sequential removal of two or more metal-containing substances (particularly Cu-containing substances and Ru-containing substances). [Explanation of symbols]

[0205] 10a Wiring board before wiring recess etching process 10b Wiring board after wiring recess etching process 12 Interlayer insulating film 14 Barrier metal layer 16 Metal-containing wiring 18 Recess 20,30 Workpiece 22 Substrate 24 Metal-containing membrane 26 Outer edge 32 Substrate 34 Metal-containing film 36 Etch stop layer 38 Interlayer insulating film 40 Metal Hard Mask 42 holes 44 Inner wall 44a Sectional wall 44b Bottom wall 46 Dry etching residue< / ph>

Claims

1. A composition for removing ruthenium-containing material, comprising: one or more periodate compounds selected from the group consisting of periodic acid and its salts; An azole compound; and an alkaline compound, A composition having a pH of 7.5 to 14.0 (excluding the cases where the composition is a polishing slurry containing abrasive grains and where the composition contains a bromine-containing compound).

2. A composition for use as an etching solution for dissolving and removing ruthenium-containing material on a substrate, comprising: one or more periodate compounds selected from the group consisting of periodic acid and its salts; An azole compound; and an alkaline compound, A composition, wherein the pH of the composition is from 7.5 to 14.0 (provided that the composition does not include a bromine-containing compound).

3. The composition according to claim 1 or 2, wherein a ratio of the content of the periodic acid compound to the content of the azole compound is 10 to 300 in terms of mass ratio.

4. A composition for removing metal inclusions, comprising: one or more periodate compounds selected from the group consisting of periodic acid and its salts; An azole compound; and an alkaline compound, a ratio of the content of the periodic acid compound to the content of the azole compound is 15 to 100 in terms of mass ratio; A composition having a pH of 7.5 to 14.0 (excluding the cases where the composition is a polishing slurry containing abrasive grains and where the composition contains a bromine-containing compound).

5. A composition used as an etching solution for dissolving and removing metal inclusions on a substrate, comprising: one or more periodate compounds selected from the group consisting of periodic acid and its salts; An azole compound; and an alkaline compound, a ratio of the content of the periodic acid compound to the content of the azole compound is 15 to 100 in terms of mass ratio; A composition having a pH of 7.5 to 14.0 (provided that said composition does not contain a bromine-containing compound).

6. 6. The composition of claim 4 or 5, wherein the metal content comprises ruthenium content.

7. The composition according to any one of claims 4 to 6, wherein the ratio of the content of the periodate compound to the content of the alkali compound is 0.5 to 2.0 in terms of mass ratio.

8. The composition according to any one of claims 4 to 7, further comprising a water-soluble organic solvent.

9. The composition of claim 8 , wherein the water-soluble organic solvent comprises an alkylene glycol dialkyl ether.

10. The composition according to claim 8 or 9, wherein a ratio of a content of the water-soluble organic solvent to a content of the azole compound is 10 to 2000 in terms of a mass ratio.

11. The composition according to any one of claims 4 to 10, wherein the azole compound comprises at least one selected from the group consisting of a triazole compound, a pyrazole compound, and an imidazole compound.

12. The composition according to any one of claims 4 to 11, wherein the alkaline compound comprises at least one selected from the group consisting of quaternary ammonium hydroxide, amino alcohol, ammonia, and potassium hydroxide.

13. The composition according to any one of claims 4 to 12, further comprising a surfactant.

14. The composition according to any one of claims 4 to 13, further comprising an organic acid.

15. 15. The composition of claim 14, wherein the organic acid comprises at least one selected from the group consisting of carboxylic acids and phosphonic acids.

16. 16. The composition of claim 14 or 15, wherein the organic acid comprises at least one carboxylic acid and at least one phosphonic acid.

17. A composition used to remove ruthenium-containing material from a substrate (excluding polishing slurries containing abrasive grains). A kit for preparing A first liquid containing one or more periodic acid compounds selected from the group consisting of periodic acid and salts thereof, and an alkali compound; and a second liquid containing an azole compound.

18. A kit for preparing a composition used as an etching solution for dissolving and removing ruthenium-containing material on a substrate, comprising: A first liquid containing one or more periodic acid compounds selected from the group consisting of periodic acid and salts thereof, and an alkali compound; and a second liquid containing an azole compound.

19. The kit according to claim 17 or 18, wherein the pH of the composition is from 7.5 to 14.

20. A method for treating a substrate, comprising a step A of removing metal inclusions on the substrate using the composition according to any one of claims 1 to 16.

21. The method for treating a substrate according to claim 20 , wherein two or more types of metal inclusions are present on the substrate on which the step A is performed.

22. The method for processing a substrate according to claim 21 , wherein the two or more kinds of metal-containing substances include at least a ruthenium-containing substance and a copper-containing substance or a cobalt-containing substance.

23. The method of claim 20 , wherein the metal inclusions comprise particulate metal oxides.

24. The method for treating a substrate according to any one of claims 20 to 23, wherein the step A is a step A1 of performing a recess etching treatment on a metal-containing wiring disposed on a substrate using the composition, a step A2 of removing the metal-containing film from an outer edge portion of the substrate on which the metal-containing film is disposed using the composition, a step A3 of removing metal inclusions adhering to a back surface of the substrate on which the metal-containing film is disposed using the composition, a step A4 of removing metal inclusions on a substrate after dry etching using the composition, or a step A5 of removing metal inclusions on a substrate after chemical mechanical polishing using the composition.

25. The step A is the step A1, Two or more kinds of metal-containing substances are present on the substrate on which the step A1 is performed, The substrate processing method according to claim 24, wherein, as the step A1, a step A1a of removing at least one metal inclusion among the two or more types of metal inclusions and a step A1b of removing a metal inclusion different from the metal inclusion removed in the step A1a are carried out.

26. The step A is the step A1, 26. The method for processing a substrate according to claim 24 or 25, further comprising a step B of processing the substrate obtained in step A1 using a solution selected from the group consisting of a mixture of hydrofluoric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of ammonia water and hydrogen peroxide, and a mixture of hydrochloric acid and hydrogen peroxide, before or after step A1.

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