Composition, substrate processing method

Abstract

The present invention addresses the problem of providing: a composition having a low amount of residue when etching a Ru-containing material by bringing the composition into contact with the Ru-containing material; and a method for treating a substrate. A composition according to the present invention comprises: at least one periodic acid compound selected from the group consisting of a periodic acid, and a salt thereof; a quaternary ammonium salt represented by formula (A); and a trialkylamine or a salt thereof.

Description

[Technical Field]

[0001] The present invention relates to a composition and a method for processing a substrate. [Background technology]

[0002] As semiconductor products become increasingly miniaturized, there is a growing demand for highly efficient and precise processes to remove unwanted metal content from substrates during the semiconductor manufacturing process.

[0003] Patent Document 1 discloses a method for etching ruthenium or osmium, wherein the treatment solution contains periodic acid, has a pH of 2 or more and 10 or less, and the temperature of the treatment solution is 30°C or more and 100°C or less. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 3619745 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In recent years, when removing unwanted metal components from substrates using etching solutions, there has been a growing demand to reduce the amount of residue left after etching. Etching residue can lead to reduced yield during semiconductor product manufacturing, and the need for residue reduction is becoming increasingly stringent as semiconductor products become more miniaturized. The inventors of the present invention have found that when a Ru (ruthenium)-containing material placed on a substrate is treated with the etching solution disclosed in Patent Document 1, a large amount of residue remains after treatment, and the results do not meet the requirements demanded today.

[0006] The present invention aims to provide a composition that leaves less residue when etching a Ru-containing material by contacting it with the Ru-containing material. Furthermore, the present invention also aims to provide a method for processing substrates. [Means for solving the problem]

[0007] The inventors of the present invention have diligently studied and found that the above problems can be solved by the following configuration.

[0008] [1] One or more periodic acid compounds selected from the group consisting of periodic acid and its salts, A quaternary ammonium salt represented by formula (A), which will be described later, Trialkylamine or its salt, A composition containing the following: [2] The composition according to [1], used for removing ruthenium-containing material from a substrate. [3] The composition according to [1] or [2], wherein the periodic acid compound comprises at least one selected from the group consisting of orthoperiodic acid, metaperiodic acid, and salts thereof. [4] The composition according to any one of [1] to [3], wherein the content of the periodic acid compound is 0.01 to 5.0% by mass of the total mass of the composition. [5] The composition according to any one of [1] to [4], wherein the total number of carbon atoms contained in the above quaternary ammonium salt is 4 to 16. [6] The composition according to any one of [1] to [5], wherein the total number of carbon atoms contained in the above quaternary ammonium salt is 4 to 8. [7] The composition according to any one of [1] to [5], wherein the above-mentioned quaternary ammonium salt comprises at least one selected from the group consisting of tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, ethyltrimethylammonium salt, methyltriethylammonium salt, diethyldimethylammonium salt, methyltributylammonium salt, dimethyldipropylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, trimethyl(hydroxyethyl)ammonium salt, and triethyl(hydroxyethyl)ammonium salt. 〔8〕 The composition according to any one of 〔1〕 to 〔7〕, wherein the trialkylamine or its salt is a compound represented by the following formula (1) or its salt. 〔9〕 R in the above formula (1) 1 , R 2 , and R 3 are each independently an alkyl group having 1 to 4 carbon atoms and no substituent. The composition according to 〔8〕. 〔10〕 The composition according to any one of 〔1〕 to 〔9〕, wherein the content of the trialkylamine or its salt is 1.0 mass ppb to 1.5 mass% based on the total mass of the composition. 〔11〕 The composition according to any one of 〔1〕 to 〔10〕, wherein the content of the trialkylamine or its salt is 1.0 mass ppb to 0.2 mass% based on the total mass of the composition. 〔12〕 The composition according to any one of 〔1〕 to 〔11〕, further comprising a compound having at least one anion selected from the group consisting of IO3 - 、 I - and I3 - . 〔13〕 The mass ratio of the content of the trialkylamine to the total mass of the anion in the compound having the anion is 1×10 -5 to 1×10 5 . The composition according to 〔12〕. 〔14〕 The composition according to any one of 〔1〕 to 〔13〕, having a pH of 2.0 to 11.0. 〔15〕 The composition according to any one of 〔1〕 to 〔14〕, having a pH of 3.0 to 10.0. 〔16〕 The composition according to any one of 〔1〕 to 〔15〕, having a pH of 4.0 to 8.0. 〔17〕 A method for treating a substrate, comprising a step A of removing a ruthenium-containing substance on the substrate using the composition according to any one of 〔1〕 to 〔16〕.

[18] The substrate processing method according to

[17] , wherein step A is a recess etching step A1 of ruthenium-containing wiring or ruthenium-containing liner disposed on the substrate using the composition; a step A2 of removing the ruthenium-containing film from the outer edge of the substrate on which the ruthenium-containing film is disposed using the composition; a step A3 of removing ruthenium-containing material adhering to the back surface of the substrate on which the ruthenium-containing film is disposed using the composition; a step A4 of removing ruthenium-containing material on the substrate after dry etching using the composition; a step A5 of removing ruthenium-containing material on the substrate after chemical mechanical polishing using the composition; or a step A6 of removing ruthenium-containing material in areas other than the area on the substrate on which the ruthenium-containing film is to be disposed after depositing a ruthenium-containing film in the area on the substrate on which the ruthenium-containing film is to be disposed using the composition. [Effects of the Invention]

[0009] According to the present invention, a composition with less residue can be provided when etching a Ru-containing material by bringing it into contact with the Ru-containing material. Furthermore, the present invention provides a method for processing substrates. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic diagram of the upper cross-section showing an example of a workpiece used in process A1. [Figure 2] Figure 1 is a schematic diagram of the upper cross-section showing an example of the workpiece after process A1 has been performed. [Figure 3] This is a schematic diagram of the upper cross-section showing another example of the workpiece used in process A1. [Figure 4] This is a schematic diagram of the upper cross-section showing an example of the workpiece shown in Figure 3 after process A1 has been performed. [Figure 5] This is a schematic diagram showing an example of a workpiece used in process A2. [Figure 6] This is a schematic cross-sectional view showing an example of a workpiece used in process A4. [Figure 7]This is a schematic cross-sectional view showing an example of a workpiece before dry etching. [Figure 8] This is a schematic cross-sectional diagram showing another example of a workpiece used in process A4. [Figure 9] This is a schematic cross-sectional view showing an example of a workpiece before the formation of a Ru-containing film. [Figure 10] This is a schematic cross-sectional view showing an example of a workpiece used in process A6. [Modes for carrying out the invention]

[0011] The present invention will be described in detail below. The following description of the constituent elements represents a typical embodiment of the present invention, and the present invention is not limited to such embodiments.

[0012] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, ppm is an abbreviation for “parts per million”. -6 This means that. Also, in this specification, ppb is an abbreviation for "parts per billion," and 10 -9 It means... In this specification, if two or more components are present, the "content" of those components means the total content of those two or more components. "Preparation" includes not only preparing specific materials by synthesizing or mixing them, but also procuring the required items by purchasing them, etc. In this specification, unless otherwise specified, the compounds described may include structural isomers (compounds with the same number of atoms but different structures), optical isomers, and isotopes. Furthermore, the isomers and isotopes may include one or more types. In this specification, dry etching residue refers to by-products generated by dry etching (e.g., plasma etching), and includes, for example, organic residues derived from photoresist, Si-containing residues, and metal-containing residues (e.g., transition metal-containing residues).

[0013] {composition} The composition of the present invention comprises one or more periodic acid compounds selected from the group consisting of periodic acid and its salts (hereinafter also simply referred to as "periodic acid compounds"), a quaternary ammonium salt represented by formula (A) described later (hereinafter also referred to as "specific quaternary ammonium salt"), and a trialkylamine or a salt thereof.

[0014] The mechanism by which the problems of the present invention are solved by using the composition of the present invention is not entirely clear, but the inventors speculate as follows. It is presumed that the composition of the present invention, by containing a periodic acid compound, a specific quaternary ammonium salt, and a trialkylamine or a salt thereof, allows these components to act synergistically, resulting in less residue when the Ru-containing material is brought into contact with the composition of the present invention and etched. Hereinafter, when etching a Ru-containing material by bringing it into contact with another Ru-containing material, a smaller amount of residue is also referred to as "the effect of the present invention being superior." The various components contained in the composition are described in detail below.

[0015] [Periodate compounds] The composition of the present invention comprises one or more periodic acid compounds selected from the group consisting of periodic acid and its salts. Examples of periodic acid compounds include orthoperiodic acid (H5IO6), metaperiodic acid (HIO4), and their salts (e.g., sodium salts or potassium salts). From the viewpoint of achieving superior effects of the present invention, the periodic acid compound is preferably orthoperiodic acid or metaperiodic acid.

[0016] Periodate compounds may be used individually or in combination of two or more.

[0017] From the viewpoint of achieving superior effects of the present invention, the content of the periodic acid compound is preferably 0.001 to 15.0% by mass, more preferably 0.01 to 10.0% by mass, even more preferably 0.01 to 5.0% by mass, and particularly preferably 0.1 to 2.0% by mass, based on the total mass of the composition.

[0018] [Specific Quaternary Ammonium Salts] The composition of the present invention comprises a quaternary ammonium salt represented by formula (A).

[0019] [ka]

[0020] In formula (A), R a ~R d Each of these independently represents an alkyl group which may have substituents. The alkyl group may be linear, branched, or cyclic, with linear being preferred. As for the number of carbon atoms in the alkyl group, from the viewpoint of achieving superior effects of the present invention, 1 to 20 is preferred, 1 to 15 is more preferred, 1 to 10 is even more preferred, 1 to 5 is particularly preferred, and 1 to 2 is most preferred. The total number of carbon atoms in the specified quaternary ammonium salt is not particularly limited, but from the viewpoint of achieving superior effects of the present invention, 4 to 20 is preferred, 4 to 16 is more preferred, and 4 to 8 is even more preferred. The total number of carbon atoms in the above-mentioned specific quaternary ammonium salt is R a ~R d This corresponds to the total number of carbon atoms contained within.

[0021] Examples of substituents on the alkyl group include hydroxyl groups, carboxyl groups, amino groups, oxo groups, phosphonic acid groups, sulfo groups, aryl groups, heteroaryl groups, and mercapto groups. Among these substituents, hydroxyl groups or aryl groups are preferred. The number of substituents on the alkyl group is preferably 0 to 5, more preferably 0 to 3, and even more preferably 0 to 1.

[0022] R a ~R d Examples include alkyl groups such as methyl, ethyl, propyl, butyl, dodecyl, and tetradodecyl groups; hydroxyalkyl groups (alkyl groups having a hydroxyl group) such as hydroxymethyl, hydroxyethyl, and hydroxybutyl groups; and arylalkyl groups (alkyl groups having an aryl group) such as benzyl and phenethyl groups. In particular, from the viewpoint of having superior effects in the present invention, R a ~R d Preferably, the alkyl group is an alkyl group, a hydroxyalkyl group, or an arylalkyl group, and more preferably an alkyl group or a hydroxyalkyl group.

[0023] In formula (A), R a ~R d They may all be the same, or they may all be different. Among them, R a ~R d It is preferable that each of them is different. That is, R a ~R d It is preferable that not all of them are the same group. The above / R a ~R d "Not all of them are the same group" means R a ~R d This means that the group consisting of these four groups contains at least two different types of groups. a ~R d The group consisting of these four groups may contain any of 2 to 4 different types of groups. Furthermore, groups with different numbers of carbon atoms, such as methyl and ethyl groups, are considered different types of groups. Even if the number of carbon atoms is the same, groups with different bond positions, such as n-propyl and isopropyl groups; groups with different substituents, such as ethyl and 2-hydroxyethyl groups; and groups with different substituent positions, such as 2-hydroxypropyl and 3-hydroxypropyl groups, are all considered different groups.

[0024] n represents an integer of 1 or 2. n- , Br - Cl - F - CH3COO - HSO4 - , OH - NO3 - , or SO4 2- It represents. Therefore, X n- ga Br - Cl - F - CH3COO - HSO4 - , OH - In this case, n is 1, and X n- SO4 2- In this case, n is 2. In particular, from the viewpoint of having superior effects in the present invention, Br - Cl - F - , or OH - It is preferable.

[0025] Examples of specific quaternary ammonium salts include tetramethylammonium salt, triethyl(hydroxymethyl)ammonium salt, tetraethylammonium salt, triethyl(hydroxyethyl)ammonium salt, tetrabutylammonium salt, tetrapropylammonium salt, ethyltrimethylammonium salt, trimethyl(hydroxyethyl)ammonium salt, butyltrimethylammonium salt, trimethyl(hydroxybutyl)ammonium salt, propyltrimethylammonium salt, isopropyltrimethylammonium salt, butyltrimethylammonium salt, pentyltrimethylammonium salt, hexyltrimethylammonium salt, octyltrimethylammonium salt, dodecyltrimethylammonium salt, tetradecyltrimethylammonium salt, hexadecyltrimethylammonium salt, propyltriethylammonium salt, butyltriethylammonium salt, pentyltriethylammonium salt, hexyltriethylammonium salt, methyltriethylammonium salt, methyltripropylammonium salt, methyltributylammonium salt, diethyldimethylammonium salt, bishydroxyethyldimethylammonium salt, dimethyldipropylammonium salt, dibutyldimethylammonium salt, benzyltrimethylammonium salt, and benzyltriethylammonium salt. In particular, from the viewpoint of achieving superior effects of the present invention, tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, ethyltrimethylammonium salt, methyltriethylammonium salt, diethyldimethylammonium salt, methyltributylammonium salt, dimethyldipropylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, trimethyl(hydroxyethyl)ammonium salt, or triethyl(hydroxyethyl)ammonium salt are preferred.

[0026] A specific quaternary ammonium salt may be used alone or in combination of two or more types.

[0027] From the viewpoint of achieving superior effects of the present invention, the content of the specific quaternary ammonium salt is preferably 0.0001 to 10.0% by mass, more preferably 0.001 to 5.0% by mass, and even more preferably 0.01% to 2.0% by mass, based on the total mass of the composition.

[0028] [Trialkylamine or its salt] The composition of the present invention comprises a trialkylamine or a salt thereof. From the viewpoint of achieving superior effects of the present invention, the trialkylamine is preferably a compound represented by formula (1).

[0029] [ka]

[0030] In formula (1), R 1 , R 2 , and, R 3 Each of these independently represents an alkyl group which may have substituents. Examples of substituents on alkyl groups include hydroxyl groups, carboxyl groups, amino groups, oxo groups, phosphonic acid groups, sulfo groups, aryl groups, heteroaryl groups, and mercapto groups. Among these, hydroxyl groups or aryl groups are preferred substituents. The number of substituents on the alkyl group is preferably 0 to 3, more preferably 0 to 1, and even more preferably 0. In other words, alkyl groups without substituents are preferred.

[0031] The number of carbon atoms in the alkyl group, including substituents, is preferably 1 to 20, more preferably 1 to 4, and even more preferably 1 to 2.

[0032] R 1 ~R 3Examples of alkyl groups that may have substituents represented by include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, dodecyl, tetradodecyl, and hexadecyl groups; hydroxyalkyl groups (alkyl groups having a hydroxyl group) such as hydroxymethyl, hydroxyethyl, and hydroxybutyl groups; and arylalkyl groups (alkyl groups having an aryl group) such as benzyl and phenethyl groups. Among these, alkyl groups are preferred, and methyl, ethyl, or butyl groups are more preferred.

[0033] R 1 ~R 3 The three groups may all be the same, or two or three groups may be different from each other.

[0034] Examples of trialkylamines include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, ethyldimethylamine, dimethylpropylamine, diethylmethylamine, dimethylhydroxyethylamine, N-methyldiethanolamine, benzyldimethylamine, benzyldiethylamine, diethylhydroxyethylamine, dodecyldimethylamine, tetradecyldimethylamine, and hexadecyldimethylamine. Among these, trimethylamine, triethylamine, tri-n-butylamine, ethyldimethylamine, dimethylpropylamine, and diethylmethylamine are preferred from the viewpoint of achieving superior effects of the present invention.

[0035] Salts of trialkylamines are so-called tertiary ammonium salts, and include salts of trialkylamines with inorganic acids and salts of trialkylamines with organic acids. Among these, salts of the compound represented by formula (1) with an inorganic acid, or salts of the compound represented by formula (1) with an organic acid are preferred. Examples of salts of trialkylamines (or compounds represented by formula (1)) with inorganic acids include salts of trialkylamines (or compounds represented by formula (1)) with inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, hydroiodic acid, and perchloric acid. However, the above inorganic acids do not include periodic acid. Examples of salts of trialkylamines (or compounds represented by formula (1)) with organic acids include salts of trialkylamines (or compounds represented by formula (1)) with organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, oxalic acid, maleic acid, citric acid, fumaric acid, lactic acid, malic acid, succinic acid, tartaric acid, gluconic acid, ascorbic acid, and methanesulfonic acid. The trialkylamine (or the compound represented by formula (1)) may be separated into cations and anions in the composition.

[0036] A trialkylamine or its salt may be used alone or in combination of two or more types.

[0037] From the viewpoint of achieving superior effects of the present invention, the content of trialkylamine or its salt is preferably 0.01 ppb to 1.5% by mass, more preferably 1.0 ppb to 1.5% by mass, even more preferably 1.0 ppb to 0.2% by mass, and particularly preferably 1.0 ppb to 0.01% by mass, based on the total mass of the composition.

[0038] [Optional ingredients] The composition of the present invention may contain optional components in addition to the components included in the above composition. An optional component could be, for example, IO3. - 、 I - and I3 - Examples include compounds having at least one anion selected from the group consisting of (hereinafter also referred to as "compound X"), solvents, pH adjusters, water-soluble polymers, surfactants, metal corrosion inhibitors, and metal components.

[0039] (Compound X) The composition of the present invention, IO3 - 、 I - and I3 - The compound X may contain at least one anion selected from the group consisting of the following. Typically, compound X is a compound composed of an anion and a cation. In a solvent, compound X dissociates into IO3 - , I - or I3 - This corresponds to a compound that can supply [the necessary substance]. - Regarding this, by equilibrium, I - This could be the case. The composition of the present invention, IO3 - It may contain only compounds that include I - It may contain only compounds including I3 - The composition of the present invention may contain only compounds containing IO3, or a mixture thereof. In particular, the composition of the present invention contains IO3 - It is preferable that the compound contains the following:

[0040] Compound X is preferably a compound that dissociates in aqueous solution. Compound X can be represented as a compound denoted as ZIO3, ZI, or ZI3, where Z represents the cation in the compound.

[0041] The cation of compound X is not particularly limited, but examples include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, ethyltrimethylammonium cation, methyltriethylammonium cation, diethyldimethylammonium cation, methyltributylammonium cation, dimethyldipropylammonium cation, benzyltrimethylammonium cation, benzyltriethylammonium cation, trimethyl(hydroxyethyl)ammonium cation, triethyl(hydroxyethyl)ammonium cation, dodecyltrimethylammonium cation, tetradecyltrimethylammonium cation, and tetraalkylammonium cations such as hexadecyltrimethylammonium cation, as well as hydrogen cations.

[0042] Compound X may be used alone or in combination of two or more types.

[0043] The content of compound X is not particularly limited, but from the viewpoint of achieving superior effects of the present invention, it is preferably 0.01 ppb to 10% by mass, more preferably 1 ppb to 1% by mass, and even more preferably 5 ppm to 0.1% by mass, relative to the total mass of the composition.

[0044] The mass ratio of the content of trialkylamine or its salt to the total mass of the anion of compound X is not particularly limited, and 1 × 10 -6 ~1 × 10 6 In many cases, and from the viewpoint of having a better effect than the present invention, 1 × 10 -5 ~1 × 10 5 It is preferable.

[0045] (solvent) The composition of the present invention may contain a solvent. Examples of solvents include water and organic solvents, with water being preferred.

[0046] The water used is preferably distilled water, ion-exchanged water, or water that has undergone purification treatment such as ultrapure water, with ultrapure water used in semiconductor manufacturing being more preferable. The water contained in the composition may contain unavoidable trace amounts of mixed components. The water content is preferably 50% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 75% by mass or more, based on the total mass of the composition. There is no particular upper limit, but it is preferably 99.999% by mass or less, and more preferably 99.9% by mass or less, based on the total mass of the composition.

[0047] As the organic solvent, a water-soluble organic solvent is preferred. A water-soluble organic solvent is an organic solvent that can be mixed with water in any proportion. Examples of water-soluble organic solvents include ether-based solvents, alcohol-based solvents, ketone-based solvents, amide-based solvents, sulfur-containing solvents, and lactone-based solvents.

[0048] Examples of ether-based solvents 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, 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). The ether solvent preferably has 3 to 16 carbon atoms, more preferably 4 to 14, and even more preferably 6 to 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 preferably 1 to 8, and more preferably 1 to 4.

[0050] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0051] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0052] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0053] Examples of lactone-based solvents include γ-butyrolactone and δ-valerolactone.

[0054] Organic solvents may be used individually or in combination of two or more. The organic solvent content is preferably 0.1 to 10% by mass relative to the total mass of the composition. Even when using two or more organic solvents, it is preferable that the total content of the two or more organic solvents is within the above range.

[0055] (pH adjuster) The composition of the present invention may contain a pH adjuster. Examples of pH adjusters include basic compounds and acidic compounds, which are appropriately selected according to the pH of the target composition. However, the aforementioned specific quaternary ammonium salts and trialkylamines or their salts are not included in the category of basic compounds. Furthermore, periodate compounds are not included in the category of acidic compounds.

[0056] <Basic compounds> Basic compounds are compounds that exhibit alkalinity (pH greater than 7.0) in aqueous solutions. Examples of basic compounds include organic bases, inorganic bases, and their salts.

[0057] Examples of organic bases include amine compounds, alkanolamine compounds and their salts, amine oxide compounds, nitro compounds, nitroso compounds, oxime compounds, ketoxime compounds, aldoxime compounds, lactam compounds, and isocyanide compounds. Note that amine compounds refer to compounds having an amino group in their molecule that are not included in the above-mentioned alkanolamines, amine oxide compounds, and lactam compounds. However, the above organic bases do not include the above-mentioned specific quaternary ammonium salts, nor the above-mentioned trialkylamines or their salts.

[0058] Examples of amine compounds include primary amines having a primary amino group (-NH2) in the molecule, secondary amines having a secondary amino group (>NH) in the molecule, and alicyclic amine compounds having an alicyclic (non-aromatic ring) structure with a nitrogen atom in the molecule, as well as salts thereof. The alicyclic amine compound may be monocyclic or bicyclic. The alicyclic may also contain heteroatoms (e.g., nitrogen, oxygen, sulfur atoms). The alicyclic may also have substituents, and while there are no particular limitations on the substituents the alicyclic may have, examples include alkyl groups, arylalkyl groups, hydroxyalkyl groups, and aminoalkyl groups. Examples of salts of amine compounds include salts of the trialkylamines or their salts with the acids listed above, with hydrochloride salts, sulfate salts, or nitrate salts being preferred. Furthermore, the amine compound is preferably water-soluble, and preferably dissolves in 1 liter of water at a rate of 50 g or more.

[0059] Examples of primary amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, methoxyethylamine, methoxypropylamine, and tetrahydrofurfurylamine. Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, and dibutylamine (DBA). Examples of alicyclic amine compounds include 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO), N-(2-aminoethyl)piperazine, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidinemethanol, cyclohexylamine, and 1,5-diazabicyclo[4,3,0]-5-nonene.

[0060] An example of a lactam compound is ε-caprolactam.

[0061] Examples of inorganic bases include sodium hydroxide, alkali metal hydroxides such as potassium hydroxide, alkaline earth metal hydroxides, and ammonia or its salts.

[0062] <Acidic compounds> Acidic compounds are compounds that exhibit acidity (pH less than 7.0) in aqueous solutions. Examples of acidic compounds include inorganic acids, organic acids, and their salts.

[0063] Examples of inorganic acids include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, hydrofluoric acid, perchloric acid, hypochlorous acid, and their salts, with sulfuric acid, hydrochloric acid, phosphoric acid, or nitric acid being preferred, and nitric acid, sulfuric acid, or hydrochloric acid being more preferred.

[0064] Examples of organic acids include carboxylic acids, sulfonic acids, and their salts. Examples of carboxylic acids include lower (1-4 carbon atoms) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid, as well as their salts. Examples of sulfonic acids include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (tosylic acid), and their salts.

[0065] Preferred acidic compounds include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfonic acid, or salts thereof, with sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, or p-toluenesulfonic acid being more preferred.

[0066] pH adjusters may be used individually or in combination of two or more types. The pH adjusting agent content is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, relative to the total mass of the composition. There is no particular upper limit, but it is preferably 20% by mass or less, relative to the total mass of the composition. It is also preferable to adjust the content of the pH adjuster within the preferred range described above so that it falls within the preferred pH range of the composition described later.

[0067] (Water-soluble polymer) The composition of the present invention may contain a water-soluble polymer. However, the water-soluble polymer does not include compounds contained in the metal corrosion inhibitors described later. Examples of water-soluble polymers include polyacrylic acid, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, and carboxyvinyl polymer.

[0068] (Surfactants) The composition of the present invention may contain a surfactant. The surfactant is not particularly limited as long as it is a compound having both a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule. Examples include anionic surfactants, cationic surfactants, and nonionic surfactants.

[0069] The hydrophobic groups that surfactants possess are not particularly limited, but examples include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. When the hydrophobic group includes an aromatic hydrocarbon group, the number of carbon atoms in the hydrophobic group is preferably 6 or more, and more preferably 10 or more. When the hydrophobic group does not contain an aromatic hydrocarbon group and consists only of aliphatic hydrocarbon groups, the number of carbon atoms in the hydrophobic group is preferably 8 or more, and more preferably 10 or more. There is no particular upper limit to the number of carbon atoms in the hydrophobic group, but it is preferably 24 or less, and more preferably 20 or less.

[0070] Examples of anionic surfactants include anionic surfactants having at least one hydrophilic group selected from the group consisting of a sulfonic acid group, a carboxyl group, a sulfate ester group, and a phosphonic acid group within the molecule.

[0071] Examples of anionic surfactants having a sulfonic acid group include alkyl sulfonic acid, alkylbenzene sulfonic acid, alkylnaphthalene sulfonic acid, alkyldiphenyl ether sulfonic acid, fatty acid amide sulfonic acid, polyoxyethylene aryl ether sulfonic acid, polyoxyethylene alkyl ether sulfonic acid, polycyclic phenyl ether sulfate, and salts thereof. Examples of anionic surfactants having a phosphonic acid group include polyoxypropylene alkyl ether phosphonic acid, polyoxyethylene alkyl ether phosphonic acid, and their salts. Examples of anionic surfactants having a carboxyl group include polyoxyethylene alkyl ether carboxylic acid, polyoxyethylene alkyl ether acetic acid, polyoxyethylene alkyl ether propionic acid, fatty acids, and salts thereof. Examples of salts of anionic surfactants include ammonium salts, sodium salts, potassium salts, and tetramethylammonium salts.

[0072] 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 include alkylpyridium surfactants and alkylamine acetate surfactants.

[0073] Surfactants may be used individually or in combination of two or more types. The surfactant content is preferably 0.01% by mass or more, and more preferably 0.03% by mass or more, relative to the total mass of the composition. There is no particular upper limit, but from the viewpoint of suppressing foaming of the composition, it is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the composition.

[0074] (abrasive particles) The composition of the present invention preferably contains substantially no abrasive particles. Polishing particles refer to particles contained in a polishing solution used for polishing semiconductor substrates, whose average primary particle diameter is 5 nm or larger. Furthermore, the statement that the composition of the present invention is substantially free of abrasive particles means that, when the composition is measured using a commercially available measuring device in a light scattering liquid particle measurement method, there are 10 or fewer abrasive particles with an average primary particle diameter of 5 nm or more per 1 mL of the composition. Examples of abrasive particles include inorganic abrasives such as silica (including colloidal silica and fumed silica), alumina, zirconia, ceria, titania, germania, manganese oxide, and silicon carbide; and organic abrasives such as polystyrene, polyacrylic, and polyvinyl chloride.

[0075] The abrasive particle content is measured using a commercially available measuring device that employs a light scattering type liquid particle measurement method with a laser as the light source. Furthermore, the average primary particle diameter of particles such as polishing particles is determined by measuring the particle diameters (equivalent circle diameters) of 1000 primary particles arbitrarily selected from images acquired using a JEOL Ltd. transmission electron microscope TEM2010 (pressure voltage 200kV), and then taking the arithmetic mean of these measurements. The equivalent circle diameter is the diameter of a circle assumed to have the same projected area as the observed particle. Methods for removing abrasive particles from a composition include, for example, purification processes such as filtering.

[0076] (Metal corrosion inhibitor) The composition of the present invention may contain a metal corrosion inhibitor. The type of metal corrosion inhibitor is not particularly limited, and known metal corrosion inhibitors can be used. As a metal corrosion inhibitor, one containing nitrogen atoms is preferred. Examples include resins containing nitrogen atoms in repeating units and chelating agents, which will be described in detail later.

[0077] Examples of resins containing nitrogen atoms in repeating units include polyvinylamide, polyallylamine, polyacrylamide, polyethyleneimine, polyalkylene polyamine, and polyvinylpyrrolidone. Furthermore, the resin containing nitrogen atoms may also be the following resin (B).

[0078] <Resin (B)> The resin (B) has a first repeating unit having at least one specific amino group described later, and a second repeating unit different from the first repeating unit. The first repeating unit of resin (B) consists of a primary amino group (-NH2), a secondary amino group (-NH-), a tertiary amino group (>N-), and a quaternary ammonium cation (>N + It has at least one group selected from the group consisting of <) (hereinafter also referred to as "specific amino group"). The first repeating unit is not particularly limited as long as it has at least one specific amino group and constitutes the main chain of resin (B). Note that the chelating agent, which will be described in detail later, is not included in resin (B).

[0079] The first repeating unit may form a salt with the specified amino group and an acid selected from inorganic acids and organic acids. In other words, the first repeating unit of resin (B) has at least one group selected from the group consisting of primary amino groups, secondary amino groups, tertiary amino groups, and quaternary ammonium cations, and salts of these with inorganic or organic acids. Examples of inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid. Examples of organic acids include acetic acid, propionic acid, methanesulfonic acid, and ethanesulfonic acid. When the specific amino group is a salt, a salt with hydrochloric acid, acetic acid, propionic acid, methanesulfonic acid, or ethanesulfonic acid is preferred, and a salt with hydrochloric acid, acetic acid, or ethanesulfonic acid is more preferred. Furthermore, if the specific amino group is a quaternary ammonium cation, it forms a salt with the counterion corresponding to the inorganic or organic acid mentioned above.

[0080] The number of specific amino groups in the first repeating unit is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. Furthermore, when the specific amino group of the first repeating unit is a secondary amino group, a tertiary amino group, or a quaternary ammonium cation, the substituents having one, two, or three atoms on the nitrogen atom are not particularly limited, but aliphatic hydrocarbon groups are preferred, linear or branched alkyl groups having 1 to 6 carbon atoms are more preferred, and methyl or ethyl groups are even more preferred. The specific amino group possessed by the first repeating unit is preferably a primary amino group, a secondary amino group, or a tertiary amino group, with a primary amino group being more preferred.

[0081] An example of the first repeating unit is the repeating unit represented by the following formula (B-1). -(Q1(X1) i )- (B-1) In formula (B-1), Q1 represents a 2- to 4-carbon aliphatic hydrocarbon group with a (2+i) valency. X1 represents a monovalent group having at least one specific amino group, where i represents 1 or 2. When i represents 2, two X1s may be linked together with at least a portion of Q1 to form a ring structure having at least one specific amino group.

[0082] X1 may be a group consisting only of a specific amino group, or it may be a group consisting of a specific amino group and a linking group L. The linking group L is not particularly limited as long as it is a group having a valency corresponding to the number of specific amino groups, but examples include aliphatic hydrocarbon groups, and groups in which the methylene group contained in an aliphatic hydrocarbon group is substituted with a group selected from the group consisting of -O-, -CO-, -NH- and -NR- (where R represents an aliphatic hydrocarbon group). The linking group L is preferably a linear or branched alkyl group, or a group in which the methylene group contained in the alkyl group is substituted with -O-, -CO-, or -NH-, from which a number of hydrogen atoms corresponding to the number of specific amino groups to be substituted are removed. The number of carbon atoms in the above linear or branched alkyl group is preferably 1 to 8, and more preferably 1 to 4. The linking group L is more preferably a methylene group or an ethylene group, and even more preferably a methylene group. Examples of the ring structure formed by the linkage of two X1s together with at least a portion of Q1 include a 5- to 7-membered nitrogen-containing heterocycle, preferably a pyrrolidine ring, pyrrolidinium ring, 1-pyrroline ring, or piperidine ring, with pyrrolidine rings or pyrrolidinium rings being more preferred.

[0083] The aliphatic hydrocarbon group represented by Q1 is preferably an ethylene group, a propylene group, a trimethylene group, or a tetramethylene group, with the ethylene group being more preferred. Examples of the substituent that the aliphatic hydrocarbon group represented by Q1 may have include an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Preferably, i represents 1.

[0084] As the first repeating unit, a repeating unit represented by the following formula (1b) is preferable.

[0085]

Chemical formula

[0086] In formula (1b), X 11 represents a specific amino group, L1 represents a single bond or a divalent linking group, and A 11 , A 12 and A 13 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

[0087] Regarding the preferred embodiments of the specific amino group represented by X 11 , they are as described above. Regarding the divalent linking group represented by L1, including the preferred embodiments, it is as described for the linking group L above. As L1, a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms is preferable, a single bond, a methylene group or an ethylene group is more preferable, and a single bond or a methylene group is still more preferable. A 11 , A 12 and A 13 are preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom.

[0088] The content of the first repeating unit is preferably 1 to 99 mol%, more preferably 5 to 95 mol%, still more preferably 15 to 85 mol%, and particularly preferably 25 to 75 mol% based on all the repeating units in the resin (B).

[0089] Resin (B) has a second repeating unit that is different from the first repeating unit. Here, "different from the first repeating unit" means, for example, that it does not have the group that the first repeating unit has as a specific amino group, and / or that the structure of the main chain in the first repeating unit or the structure of the linking group that connects the main chain to the specific amino group is different. The second repeating unit may have a specific amino group different from the specific amino group currently present in the first repeating unit. Alternatively, the second repeating unit may have the same specific amino group as the first repeating unit, provided that the structure of the main chain or side chain differs from that of the first repeating unit. Preferably, the second repeating unit has a hydrophilic group different from the specific amino group currently present in the first repeating unit.

[0090] The second repeating unit preferably has at least one hydrophilic group. The number of hydrophilic groups in the second repeating unit is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. Examples of hydrophilic groups include specific amino groups, carboxyl groups, hydroxyl groups, alkoxy groups, polyoxyalkylene groups, amide groups, carbamoyl groups, nitrile groups, sulfo groups, sulfonyl groups, sulfonamide groups, and sulfamoyl groups. Examples of polyoxyalkylene groups include polyoxyethylene groups, polyoxypropylene groups, and polyoxyalkylene groups in which oxyethylene groups and oxypropylene groups are block-bonded or randomly bonded. Polyoxyethylene or polyoxypropylene is preferred, and polyoxyethylene is more preferred. The number of repeating oxyalkylene groups in a polyoxyalkylene group is not particularly limited, but 1 to 30 is preferred, and 1 to 10 is more preferred. The hydrophilic groups mentioned above may form salts. Salts of specific amino groups are as already described in the section on the first repeating unit. Examples of carboxyl and sulfo group salts include their alkali metal salts. The hydrophilic group described above may have further substituents. Examples of substituents that the hydrophilic group may have include aliphatic hydrocarbon groups and the hydrophilic group described above, with linear or branched alkyl groups having 1 to 4 carbon atoms being preferred, methyl or ethyl groups being more preferred, and methyl groups being even more preferred.

[0091] The hydrophilic group of the second repeating unit is preferably a hydroxyl group, carboxyl group, primary amino group, secondary amino group, tertiary amino group, amide group, polyoxyalkylene group, sulfo group, or sulfonyl group, more preferably a primary amino group, carboxyl group, hydroxyl group, or polyoxyethylene group, and even more preferably a carboxyl group.

[0092] An example of a second repeating unit is the repeating unit represented by the following formula (B-2). -(Q2(X2) j )- (B-2) In formula (B-2), Q2 represents a carbon-2 to carbon-4 aliphatic hydrocarbon group with a (2+j) valency. X2 represents a monovalent group having at least one hydrophilic group, and j represents 1 or 2. When j represents 2, two X2s may be linked together with at least a portion of Q2 to form a ring structure having at least one hydrophilic group.

[0093] X2 may be a group consisting only of hydrophilic groups, or it may be a group consisting of a hydrophilic group and a linking group L. The linking group L, including its preferred embodiment, is synonymous with the linking group L in formula (1) above. Examples of ring structures formed by the linkage of two X2 units together with at least a portion of Q2 include 5- to 7-membered nitrogen-containing heterocycles, preferably pyrrolidine rings, pyrrolidinium rings, 1-pyrroline rings, or piperidine rings, with pyrrolidine rings or pyrrolidinium rings being more preferred.

[0094] The aliphatic hydrocarbon group represented by Q2 is preferably an ethylene group, a propylene group, a trimethylene group, or a tetramethylene group, with the ethylene group being more preferred. Examples of the substituent that the aliphatic hydrocarbon group represented by Q2 may have include aliphatic hydrocarbon groups, preferably linear or branched alkyl groups having 1 to 4 carbon atoms, more preferably methyl or ethyl groups, and even more preferably a methyl group. j preferably represents 1.

[0095] The second repeating unit may be a divalent hydrophilic group. Examples of the divalent hydrophilic group serving as the second repeating unit include a sulfonyl group.

[0096] As the second repeating unit, a repeating unit represented by the following formula (2b) is preferable.

Chemical formula

[0097] Regarding the preferred embodiments of the hydrophilic group represented by X 21 , they are as described above. Regarding the divalent linking group represented by L2, including the preferred embodiments, it is as described for the linking group L above. As L2, a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms is preferable, a single bond, a methylene group or an ethylene group is more preferable, and a single bond or a methylene group is even more preferable. Also, A 21 , A 22 and A 23 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, or A 21 , A 22 and A 23One of them is -L2-X 21 Preferably, one represents a hydrogen atom, and the remaining two represent a linear or branched alkyl group having 1 to 4 carbon atoms. Among them, A 21 , A 22 and A 23 However, each independently represents a hydrogen atom, a methyl group, or an ethyl group, or A 21 , A 22 and A 23 It is more preferable that one of them represents a hydrophilic group, and the remaining two represent a hydrogen atom, a methyl group, or an ethyl group. 21 , A 22 and A 23 However, each independently represents either a hydrogen atom or a methyl group, or A 21 , A 22 and A 23 It is even more preferable that one of them represents a carboxyl group and the remaining two represent a hydrogen atom or a methyl group.

[0098] The content of the second repeating unit is preferably 1 to 99 mol%, more preferably 5 to 95 mol%, even more preferably 15 to 85 mol%, and particularly preferably 25 to 75 mol%, relative to the total repeating units in resin (B). The second repeating unit may be a single type or a combination of two or more types. When resin (B) has two or more types of second repeating units, it is preferable that it has at least one repeating unit represented by formula (B-2) or formula (2b). The content of the repeating units represented by formula (B-2) or formula (2b) above is preferably 1 to 99 mol%, more preferably 5 to 95 mol%, even more preferably 15 to 85 mol%, and particularly preferably 25 to 75 mol%, relative to the total repeating units in resin (B).

[0099] The ratio of first repeating units to second repeating units in resin (B) is not particularly limited, but from the viewpoint of providing superior corrosion resistance to the metal-containing layer (especially the tungsten-containing layer), the ratio of moles m of first repeating units to moles n of second repeating units (m / n) is preferably 20 / 1 to 1 / 20, more preferably 10 / 1 to 1 / 10, even more preferably 5 / 1 to 1 / 5, and particularly preferably 3 / 1 to 1 / 3.

[0100] A specific example of resin (B) is a resin having a skeletal structure represented by the following formulas (P-1) to (P-23). ​​In formulas (P-1) to (P-23), the repeating unit denoted by the sign m is the first repeating unit, and the repeating unit denoted by the sign n is the second repeating unit. The skeletal structures represented by formulas (P-1) to (P-23) include multiple repeating units, and the bonding pattern of these repeating units is not particularly limited. For example, the repeating units may be bonded randomly (a so-called random copolymer), alternately (a so-called alternating copolymer), or in a block-like structure (a so-called block copolymer).

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] In the above equations (P-1) to (P-23), the ratio of the number of moles m of the first repeating unit to the number of moles n of the second repeating unit (m / n) is between 1 / 20 and 20 / 1. Furthermore, in equation (P-7), l represents the number of repetitions of the oxyalkylene unit and is an integer between 1 and 30. In addition, in formula (P-20), X represents an amide group, a nitrile group, an amino hydrochloride, or a formamide group.

[0105] In particular, at least one selected from the group consisting of skeletal structures represented by formulas (P-1) to (P-18) is preferred, at least one selected from the group consisting of skeletal structures represented by formulas (P-8), (P-9), (P-10), and (P-11) is more preferred, and at least one selected from the group consisting of skeletal structures represented by formulas (P-8), (P-10), and (P-11) is even more preferred.

[0106] The structure and composition ratio (mol% ratio) of each repeating unit in resin (B) are as follows: 13 It can be measured by 13C-NMR.

[0107] The weight-average molecular weight of resin (B) is not particularly limited, but is preferably 500 to 200,000, more preferably 1,000 to 100,000, even more preferably 2,000 to 50,000, and particularly preferably 5,000 to 50,000. In this specification, "weight-average molecular weight" refers to the weight-average molecular weight in polystyrene terms, measured by GPC (gel permeation chromatography).

[0108] Resin (B) may be used alone or in combination of two or more types. The content of resin (B) is preferably 1 ppm to 10% by mass, more preferably 10 to 10,000 ppm by mass, and even more preferably 50 to 1,000 ppm by mass, relative to the total mass of the composition.

[0109] <Chelating agent> The chelating agent has at least two nitrogen-containing groups. Examples of nitrogen-containing groups include primary amino groups, secondary amino groups, imidazolyl groups, triazolyl groups, benzotriazolyl groups, piperazinyl groups, pyrrolyl groups, pyrrolidinyl groups, pyrazolyl groups, piperidinyl groups, guanidinyl groups, biguanidinyl groups, carbazatyl groups, hydrazidyl groups, semicarbazidyl groups, and aminoguanidinyl groups. A chelating agent only needs to have two or more nitrogen-containing groups, and these two or more nitrogen-containing groups may be different, partially the same, or all the same. Furthermore, the chelating agent may contain a carboxyl group. The nitrogen-containing groups and / or carboxyl groups of the chelating agent may be neutralized to form a salt.

[0110] The chelating agent may be a monocarboxylic acid compound containing a primary amino group or a secondary amino group and at least one nitrogen-containing group. The primary and secondary amino groups are neither directly bonded to nor part of the nitrogen-containing groups further present. Examples of nitrogen-containing groups include NH2, H2NC(=X), or H2NNHC(=X), where X is O, S, or NR, and R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The above monocarboxylic acid is preferably a monocarboxylic acid compound that contains a primary amino group or a primary amino group and at least one nitrogen-containing basic group selected from the group consisting of imidazolyl group, triazolyl group, benzotriazolyl group, piperazinyl group, pyrrolyl group, pyrrolidinyl group, pyrazolyl group, piperidinyl group, guanidinyl group, carbazatyl group, hydrazidyl group, semicarbazidyl group, aminoguanidinyl group, primary amino group, and secondary amino group.

[0111] The chelating agent may be a compound represented by the following formula (C-1). (R C3 NH)C(R C1 )(R C2 )CO2H (C-1) R C1 , and, R C2 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group containing a nitrogen atom. C3 R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group containing a nitrogen atom. C1 , R C2 , and, R C3 At least one of them represents a group that contains nitrogen. Compounds represented by formula (C-1) include, for example, lysine, 2,3-diaminobutyric acid, 2,4-diaminobutyric acid, ornithine, 2,3-diaminopropionic acid, 2,6-diaminoheptanoic acid, 4-methyllysine, 3-methyllysine, 5-hydroxylysine, 3-methyl-L-arginine, arginine, homoarginine, and N 5 -Monomethyl-L-arginine, N 5 -[imino(methylamino)methyl]-D-ornithine, canavanine, histidine, N-(2-aminoethyl)glycine, N-(2-aminopropyl)glycine, N 2 -methyllysine, N 2 -methyl-L-arginine, N 2 -(2-aminoethyl)-D-arginine, N 2 Examples include -(2-aminoethyl)-L-arginine, 2-methyllysine, 2-methyl-L-arginine, 3,4-diaminobutyric acid, and 3-amino-5-[(aminoiminomethyl)methylamino]pentanoic acid.

[0112] The chelating agent may be a compound containing a biguanide group represented by the following formula (C-2).

[0113] [ka]

[0114] In formula (C-2), R C10 , R C11 , R C12 , and, R C13Each of these independently represents a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cyclic alkyl group having 3 to 10 carbon atoms, and a substituted or unsubstituted aryl group. C14 R represents a hydrogen atom or C13 It binds to form an imidazole ring. However, R C10 , R C11 , R C12 , and, R C13 At least one of them is a substituted or unsubstituted aryl group, R C10 , R C11 , R C12 , and, R C13 At least two of them are hydrogen atoms. Examples of aryl groups include phenyl groups, naphthyl groups, and anthracenyl groups. Examples of substituents that alkyl groups and aryl groups may have include halogen atoms (e.g., Cl, Br, or F), nitro groups, thiol groups, dioxolyl groups, linear or branched alkyl groups having 1 to 10 carbon atoms, linear or branched alkoxy groups having 1 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, cyclic alkoxy groups having 3 to 10 carbon atoms, and substituted or unsubstituted phenyl groups.

[0115] Compounds containing a biguanide group having a substituted or unsubstituted aryl group include, for example, 1-phenyl biguanide, 1-(o-tolyl)biguanide, 1-(3-methylphenyl)biguanide, 1-(4-methylphenyl)biguanide, 1-(2-chlorophenyl)biguanide, 1-(4-chlorophenyl)biguanide, 1-(2,3-dimethylphenyl)biguanide, 1-(2,6-dimethylphenyl)biguanide, 1-(1-naphthyl)biguanide, 1-(4-methoxyphenyl)biguanide, and 1-(4-nitrophenyl)biguanide. Examples include biguanides, 1,1-diphenyl biguanides, 1,5-diphenyl biguanides, 1,5-bis(4-chlorophenyl)biguanides, 1,5-bis(3-chlorophenyl)biguanides, 1-(4-chloro)phenyl-5-(4-methoxy)phenyl biguanides, 1,1-bis(3-chloro-4-methoxyphenyl)biguanides, 1,5-bis(3,4-dichlorophenyl)biguanides, 1,5-bis(3,5-dichlorophenyl)biguanides, and 1,5-bis(4-bromophenyl)biguanides.

[0116] Compounds containing a substituted or unsubstituted aryl group and a biguanide group having a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms include, for example, 1-phenyl-1-methyl biguanide, 1-(4-chlorophenyl)-5-(1-methylethyl) biguanide (proguanyl), 1-(3,4-dichlorophenyl)-5-(1-methylethyl) biguanide, 1-(4-methylphenyl)-5-octyl biguanide, 1-(4-chlorophenyl)-2-(N'-propane-2-ylcarbamimidoyl)guanidine, dityl biguanide, dinaphthyl biguanide, and dibenzyl biguanide.

[0117] Compounds containing a biguanide group having a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms include, for example, 4-chlorobenzhydryl biguanide, 1-benzo[1,3]dioxol-5-ylmethyl biguanide, 1-benzyl-5-(pyridine-3-yl)methyl biguanide, 1-benzyl biguanide, 4-chlorobenzyl biguanide, 1-(2-phenylethyl) biguanide, 1-hexyl-5-benzyl biguanide, 1,1-dibenzyl biguanide, 1,5-dibenzyl biguanide, 1-(phenethyl)-5-propyl biguanide, and 1,5-bis(phenethyl)biguanide.

[0118] Compounds containing a biguanide group having a substituted or unsubstituted cyclic alkyl group having 1 to 10 carbon atoms include 1-cyclohexyl-5-phenyl biguanide, 1-(4-phenylcyclohexyl) biguanide, 1-(4-methyl)cyclohexyl-5-phenyl biguanide, and 1-cyclopentyl-5-(4-methoxyphenyl) biguanide, norbornyl biguanide, dinorbornyl biguanide, adamantyl biguanide, diadamantyl biguanide, and dicyclohexyl biguanide.

[0119] R C14 and R C13 Compounds represented by formula (C-2) in which a bond forms an imidazole ring include 2-guanidinobenzimidazole, 5-methyl-2-guanidinobenzimidazole, 4,6-dimethyl-2-guanidinobenzimidazole, 5,6-dimethyl-2-guanidinobenzimidazole, 5-chloro-2-guanidinobenzimidazole, 4,5-dichloro-2-guanidinobenzimidazole, 4,6-dichloro-2-guanidinobenzimidazole, 5-bromo-2-guanidinobenzimidazole, 5-phenyl-2-guanidinobenzimidazole, and 5-methoxy-2-guanidinobenzimidazole.

[0120] The chelating agent may be a compound containing two biguanide groups represented by the following formula (C-3) (bis-biguanide compound).

[0121] [ka]

[0122] R C20 , R C21 , R C22 , and, R C23 Each of these independently represents a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cyclic alkyl group having 3 to 10 carbon atoms, and a substituted or unsubstituted aryl group. 24 m represents a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted phenylethyl group, and a substituted or unsubstituted benzylalkyl group. m is an integer from 1 to 10. However, R C20 , R C21 , R C22 , R C23 , and, R C24 At least one of them is an aryl group, or contains an aryl group as a substituent, and R C20 , R C21 , R C22 , and, R C23 At least two of them are hydrogen atoms.

[0123] Examples of bis-biguanide compounds represented by formula (C-3) include ethylene dibiguanide, propylene dibiguanide, tetramethylene dibiguanide, pentamethylene dibiguanide, hexamethylene dibiguanide, heptamethylene dibiguanide, octamethylene dibiguanide, 1,6-bis-(4-chlorobenzyl biguanide)-hexane (fluorhexidine®), 1,1'-hexamethylenebis(5-(p-chlorophenyl)biguanide) (chlorhexidine), and 2-(benzyloxymethyl Examples include pentane-1,5-bis(5-hexylbiguanide), 2-(phenylthiomethyl)pentane-1,5-bis(5-phenethylbiguanide), 3-(phenylthio)hexane-1,6-bis(5-hexylbiguanide), 3-(phenylthio)hexane-1,6-bis(5-cyclohexylbiguanide), 3-(benzylthio)hexane-1,6-bis(5-hexylbiguanide), 3-(benzylthio)hexane-1,6-bis(5-cyclohexylbiguanide), and alexidine.

[0124] Examples of compounds containing two biguanide groups include phenylenyl dibiguanide, naphthyleneyl dibiguanide, pyridinyl dibiguanide, piperazinyl dibiguanide, phthalyl dibiguanide, 1,1'-[4-(dodecyloxy)-m-phenylene]bisbiguanide, 2-(decylthiomethyl)pentane-1,5-bis(5-isopropyl biguanide), and 2-(decylthiomethyl)pentane-1,5-bis(5,5-diethyl biguanide).

[0125] The chelating agent may be a compound containing repeating units represented by the following formula (C-4) (a high-molecular-weight biguanide compound).

[0126] [ka]

[0127] In equation (C-4), n is an integer greater than or equal to 2. C25 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.C26 This is an alkylene group which may have substituents having 1 to 20 carbon atoms. The term "alkylene group that may have substituents" indicates that the -CH2- group of the alkylene group may be replaced by a divalent substituent. Examples of divalent substituents include -O-, -S-, -CO-, -COO-, -OCO-, -NH-, -CONH-, -SO-, and -SO2-, as well as -CHR T - and -C(R T )2- is one example. T The symbol represents a monovalent substituent, and examples of monovalent substituents include hydroxyl groups, nitro groups, thiol groups, halogen atoms (e.g., Cl, Br, or F), amino groups, dioxolyl groups, biguanidyl groups, cyano groups, carboxyl groups, linear or branched alkyl groups having 1 to 10 carbon atoms, linear or branched alkoxy groups having 1 to 10 carbon atoms, cyclic alkyl groups having 3 to 10 carbon atoms, cyclic alkoxy groups having 3 to 10 carbon atoms, and substituted or unsubstituted phenyl groups. Among them, R C25 is a hydrogen atom, and R C26 A typical embodiment is one in which n is a hexylene group and n is 12 or 15.

[0128] Furthermore, the chelating agent may be a compound having a biguanide group in the side chain of the repeating unit. Examples of such compounds include polymerization products of biguanidyl-substituted α-olefin monomers and copolymers thereof. Examples of polymerization products of biguanidyl-substituted α-olefin monomers include poly(vinyl biguanide), poly(N-vinyl biguanide), and poly(allyl biguanide).

[0129] The chelating agent may be alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, diethylenetriamine, triethylenetetramine, and polyethyleneimine having at least two nitrogen-containing groups.

[0130] The chelating agent may form a salt with an inorganic acid and / or an organic acid. Examples of inorganic salts include hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, phosphonic acid, phosphoric acid, sulfonic acid, and sulfuric acid. Examples of organic acid salts include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, octanoic acid, 2-octenoic acid, lauric acid, 5-dodecenoic acid, myristic acid, pentadecanoic acid, palmitic acid, oleic acid, stearic acid, eicosanoic acid, heptadecanoic acid, palmitoleic acid, ricinoleic acid, 12-hydroxystearic acid, 16-hydroxyhexadecanoic acid, 2-hydroxycaproic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxydecanoic acid, 4-hydroxydecanoic acid, dodecanedionic acid, undecanedionic acid, sebacic acid, benzoic acid, hydroxybenzoic acid, and terephthalic acid.

[0131] A chelating agent may be used alone or in combination of two or more types. The chelating agent content is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass, and even more preferably 0.3 to 1.0% by mass, relative to the total mass of the treatment solution.

[0132] <Other metal corrosion inhibitors> The metal corrosion inhibitor may be a benzotriazole, which may have substituents. However, benzotriazole contained in the chelating agent is excluded. Benzotriazoles that may have substituents include benzotriazole (BTA), 5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-benzotriazole, 5-methyl-1H-benzotriazole, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, and 4-propylbenzotriazole. Examples include 5-propylbenzotriazole, 4-isopropylbenzotriazole, 5-isopropylbenzotriazole, 4-n-butylbenzotriazole, 5-n-butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole, 4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzotriazole, 5-hydroxybenzotriazole, dihydroxypropylbenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-t-butylbenzotriazole, 5-(1',1'-dimethylpropyl)-benzotriazole, 5-(1',1',3'-trimethylbutyl)benzotriazole, 5-n-octylbenzotriazole, and 5-(1',1',3',3'-tetramethylbutyl)benzotriazole.

[0133] (Metallic components) The composition may contain a metallic component. Examples of metallic components include metal particles and metal ions. For example, when referring to the content of metallic components, it indicates the total content of metal particles and metal ions. The composition may contain either metal particles or metal ions, or both.

[0134] Examples of metal atoms contained in the metal component include metal atoms selected from the group consisting of Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sn, Sr, Ti, Zn, and Zr. The metal component may contain one type of metal atom, or it may contain two or more types of metal atoms. Metal particles may be in elemental form, alloy form, or exist in a form in which the metal is associated with organic matter. The metal component may be a metal component that is inevitably present in each component (raw material) of the composition, or a metal component that is inevitably present during the manufacture, storage, and / or transport of the composition, or it may be added intentionally. When the composition contains a metal component, the amount of the metal component is often 0.01 ppt to 10 ppm relative to the total mass of the composition, preferably 0.1 ppt to 1 ppm, and more preferably 0.1 ppt to 100 ppb.

[0135] The type and content of metal components in the composition can be measured by ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry). In the ICP-MS method, the content of the target metal component is measured regardless of its form of existence. Therefore, the total mass of the target metal particles and metal ions is quantified as the content of the metal component. For ICP-MS measurements, for example, Agilent Technologies' Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) and Agilent 8900, as well as PerkinElmer's NexION350S, can be used.

[0136] The method for adjusting the content of each metal component in the composition is not particularly limited. For example, the content of metal components in the composition can be reduced by performing known treatments to remove metals from the composition and / or from the raw materials containing each component used in the preparation of the composition. Alternatively, the content of metal components in the composition can be increased by adding compounds containing metal ions to the composition.

[0137] [pH] The pH of the composition of the present invention is not particularly limited, and for example, it may be in the range of 1.0 to 14.0. From the viewpoint of achieving superior effects of the present invention, the pH of the composition of the present invention is preferably 2.0 to 11.0, more preferably 3.0 to 10.0, and even more preferably 4.0 to 8.0. In this specification, the pH of the composition is obtained by measuring it at 25°C using a pH meter (F-51 (product name) manufactured by Horiba, Ltd.).

[0138] [Manufacturing method] The method for producing the composition of the present invention is not particularly limited, and for example, it can be produced by mixing the above-mentioned components. The order or timing of mixing the components, as well as the order and timing, are not particularly limited. For example, one method is to produce the composition by sequentially adding a periodate compound, a specific quaternary ammonium salt, a trialkylamine or its salt, and an optional component to a stirrer such as a mixing mixer containing purified pure water, and then stirring thoroughly to mix the components. Methods for producing the composition include a method in which the pH of the washing solution is adjusted in advance using a pH adjusting agent before mixing each component, and a method in which the pH is adjusted to a set level using a pH adjusting agent after mixing each component.

[0139] Alternatively, the composition of the present invention may be produced by preparing a concentrated solution with a lower solvent content (such as water) than that used in the product, and then diluting it with a diluent (preferably water) at the time of use to adjust the content of each component to a predetermined level. The composition of the present invention may also be produced by diluting the concentrated solution with a diluent and then adjusting the pH to a set level using a pH adjusting agent. 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.

[0140] (Metal removal process) The above manufacturing method may include a metal removal step to remove metal components from the above components and / or composition (hereinafter also referred to as the "purified product"). For example, one embodiment may involve performing the metal removal step on the purified product containing the above periodic acid compound and water.

[0141] In the purified product containing the above-mentioned periodic acid compound and water, the content of the periodic acid compound is not particularly limited, but is preferably 0.0001 to 50% by mass, more preferably 1 to 45% by mass, and even more preferably 4 to 40% by mass, relative to the total mass of the purified product. From the viewpoint of excellent processing efficiency, the water content in the purified product is preferably 40% by mass or more and less than 100% by mass, preferably 50 to 99% by mass, and even more preferably 60 to 95% by mass. The purified product containing the above-mentioned periodic acid compound and water may further contain the components included in the above-mentioned composition, and / or optional components. One example of a metal removal process is step P, in which the material to be purified is subjected to an ion exchange method.

[0142] <Process P> In step P, the product to be purified as described above is subjected to an ion exchange method. The ion exchange method is not particularly limited as long as it can adjust (reduce) the amount of metal components in the purified product. However, from the perspective of easier production of the chemical solution, the ion exchange method preferably includes one or more of the following methods P1 to P3. More preferably, the ion exchange method includes two or more of methods P1 to P3, and even more preferably, it includes all of methods P1 to P3. When the ion exchange method includes all of methods P1 to P3, the order of implementation is not particularly limited, but it is preferable to implement them in the order of methods P1 to P3. Method P1: A method of passing the purified product through a first filling part filled with a mixed resin containing a cation exchange resin and an anion exchange resin. Method P2: A method of passing the purified product through at least one of the filling parts including a second filling part filled with a cation exchange resin, a third filling part filled with an anion exchange resin, and a fourth filling part filled with a chelating resin. Method P3: A method of passing the purified product through a membrane ion exchanger.

[0143] The procedures of methods P1 to P3 above will be detailed later. However, the ion exchange resins (cation exchange resin, anion exchange resin), chelating resin, and membrane ion exchanger used in each method are in the form of H + form or OH - If in a form other than the form, they are preferably used after being regenerated into the H + form or OH - form. Also, the space velocity (SV) of the purified product in each method is preferably 0.01 to 20.0 (1 / h), and more preferably 0.1 to 10.0 (1 / h). Also, the treatment temperature in each method is preferably 0 to 60°C, and more preferably 10 to 50°C.

[0144] Also, examples of the forms of the ion exchange resin and the chelating resin include granular, fibrous, and porous monolithic forms, and granular or fibrous forms are preferred. The average particle diameter of the particle diameters of the granular ion exchange resin and chelating resin is preferably 10 to 2000 μm, and more preferably 100 to 1000 μm. As for the particle size distribution of granular ion exchange resins and chelating resins, it is preferable that the resin particle existence rate within the range of ±200 μm of the average particle size is 90% or more. Examples of the above average particle size and particle size distribution include a method of measuring using water as a dispersion medium with a particle size distribution measuring device (Microtrac HRA3920, manufactured by Nikkiso Co., Ltd.).

[0145] -Method P1- Method P1 is a method of passing the crude product through a first filling section filled with a mixed resin containing a cation exchange resin and an anion exchange resin.

[0146] As the cation exchange resin, known cation exchange resins can be used, which may be gel type or MR type (macroporous type), and among them, gel type cation exchange resins are preferable. Specific examples of the cation exchange resin include sulfonic acid type cation exchange resins and carboxylic acid type cation exchange resins. Examples of the cation exchange resin include, for example, Amberlite IR-124, Amberlite IR-120B, Amberlite IR-200CT, ORLITE DS-1, and ORLITE DS-4 (manufactured by Organo Corporation), Duolite C20J, Duolite C20LF, Duolite C255LFH, and Duolite C-433LF (manufactured by Sumitomo Chemical Tex Co., Ltd.), C100, C150, and C100×16MBH (manufactured by Purolite Corporation), and DIAION SK-110, DIAION SK1B, DIAION SK1BH, DIAION PK216, and DIAION PK228 (manufactured by Mitsubishi Chemical Corporation), etc.

[0147] As the anion exchange resin, known anion exchange resins can be used, which may be gel type or MR type, and among them, it is preferable to use gel type anion exchange resins. Specific examples of the anion exchange resin include quaternary ammonium salt type anion exchange resins. Examples of anion exchange resins include Amberlite IRA-400J, Amberlite IRA-410J, Amberlite IRA-900J, Amberlite IRA67, ORLITE DS-2, ORLITE DS-5, and ORLITE DS-6 (manufactured by Organo Corporation), Duolite A113LF, Duolite A116, and Duolite A-375LF (manufactured by Sumika Chemtex Corporation), A400 and A500 (manufactured by Purolite Corporation), as well as DIAION SA12A, DIAION SA10AO, DIAION SA10AOH, DIAION SA20A, and DIAION WA10 (manufactured by Mitsubishi Chemical Corporation).

[0148] Examples of commercially available products that pre-mix a strong acid cation exchange resin and a strong alkaline anion exchange resin include Duolite MB5113, Duolite UP6000, and Duolite UP7000 (manufactured by Sumika Chemtex Co., Ltd.), Amberlite EG-4A-HG, Amberlite MB-1, Amberlite MB-2, Amberjet ESP-2, Amberjet ESP-1, ORLITE DS-3, ORLITE DS-7, and ORLITE DS-10 (manufactured by Organo Corporation), as well as DIAION SMNUP, DIAION SMNUPB, DIAION SMT100L, and DIAION SMT200L (both manufactured by Mitsubishi Chemical Corporation).

[0149] When preparing a mixed resin containing a cation exchange resin and an anion exchange resin, the mixing ratio of the two is preferably 1 / 4 to 4 / 1 in terms of the volume ratio of the cation exchange resin to the anion exchange resin, and more preferably 1 / 3 to 3 / 1. A suitable combination of cation exchange resin and anion exchange resin is, for example, a combination of a gel-type sulfonic acid-type cation exchange resin and a gel-type quaternary ammonium salt-type anion exchange resin.

[0150] The first filling section typically includes a container and a mixed resin containing the aforementioned cation exchange resin and anion exchange resin, which is filled into the container. Examples of containers include columns, cartridges, and packed towers, but any container other than those exemplified above is acceptable as long as it allows the material to be purified to pass through after the mixed resin has been packed into it.

[0151] In method P1, the substance to be purified only needs to be passed through at least one first-filled section. In particular, two or more first-filled sections may be passed through, as this makes the production of the drug solution easier.

[0152] -Method P2- Method P2 is a method of passing the substance to be purified through at least one (preferably two or more) of the following filling sections: a second filling section filled with a cation exchange resin, a third filling section filled with an anion exchange resin, and a fourth filling section filled with a chelate resin. Examples of cation exchange resins and anion exchange resins that can be used in Method P2 are the same as those listed in the description of Method P1.

[0153] The second filling section typically includes a container and the cation exchange resin described above, which is filled into the container. The third filling section typically includes a container and the aforementioned anion exchange resin filled in the container. The fourth filling section typically includes a container and the chelate resin described below, which is filled into the container.

[0154] Chelate resins generally refer to resins that have coordinating groups capable of forming chelate bonds with metal ions. For example, a resin in which chelate-forming groups are introduced into a styrene-divinylbenzene copolymer. The material of the chelate resin may be gel-type or MR-type. From the viewpoint of processing efficiency, the chelate resin is preferably in granular or fibrous form. Examples of chelating resins include various types such as iminodiacetic acid type, iminopropionic acid type, aminophosphonic acid type (including aminomethylphosphonic acid type), polyamine type, glucamine type (including N-methylglucamine type), aminocarboxylic acid type, dithiocarbamate type, thiol type, amidoxime type, and pyridine type. Specific examples include, for example, MC700 manufactured by Sumika Chemtex Co., Ltd. as an iminodiacetic acid type chelating resin, for example, Eporas MX-8 manufactured by Miyoshi Oil & Fat Co., Ltd. as an iminopropionic acid type chelating resin, for example, MC960 manufactured by Sumika Chemtex Co., Ltd. as an aminomethylphosphonic acid type chelating resin, for example, S985 manufactured by Purolite Co., Ltd. and Diaion CR-20 manufactured by Mitsubishi Chemical Corporation as polyamine type chelating resins, and for example, Amberlite IRA-743 manufactured by Organo Corporation as an N-methylglucamine type chelating resin.

[0155] The definition of a container in the second filling section, the third filling section, and the fourth filling section is as described above.

[0156] In method P2, the substance to be purified is passed through at least one of the second, third, and fourth filling sections. In particular, it is preferable to pass the substance to be purified through two or more of the second, third, and fourth filling sections. In method P2, it is preferable to pass the product to be purified through at least the second packed section. Furthermore, by passing the product to be purified through the fourth packing section in method P2, purification can be carried out efficiently even with fewer passes of the liquid to be purified through the packing section. When the product to be purified is passed through two or more packing sections in method P2, the order in which the product to be purified is passed through two or more of the second packing section, third packing section, and fourth packing section does not matter.

[0157] In Method P2, the crude product may be passed through at least one (preferably two or more) second filling parts, at least one (preferably two or more) third filling parts, and / or at least one fourth filling part. For example, from the viewpoint that the production of the chemical solution is easier, the crude product may be passed through one or more (preferably two or more) second filling parts and one or more (preferably two or more) third filling parts. In this case, there is no limitation on the order of passing the crude product. For example, the second filling part and the third filling part may be passed through alternately, or the crude product may be passed through continuously to one of the plurality of second filling parts and third filling parts, and then continuously passed through to the other of the plurality of second filling parts and third filling parts. Also, from the viewpoint that the production of the chemical solution is easier, the crude product may be passed through one or more second filling parts and one or more fourth filling parts. Also in this case, there is no limitation on the order of passing the crude product.

[0158] -Method P3- Method P3 is a method of passing a crude product through a membrane-type ion exchanger. The membrane-type ion exchanger is a membrane having an ion exchange group. Examples of the ion exchange group include a cation exchange group (such as a sulfonic acid group) and an anion exchange group (such as an ammonium group).

[0159] The membrane-type ion exchanger may be composed of the ion exchange resin itself, or may be one in which a cation exchange group and / or an anion exchange group is introduced into a membrane support. The membrane-type ion exchanger (including the support of the membrane-type ion exchanger) may be porous or non-porous. The membrane-type ion exchanger (including the support of the membrane-type ion exchanger) may be, for example, a membrane formed by molding an aggregate such as particles and / or fibers. Also, for example, the membrane-type ion exchanger may be any of an ion exchange membrane, an ion exchange non-woven fabric, an ion exchange filter paper, and an ion exchange filter cloth. As a form of using the membrane-type ion exchanger, for example, the membrane-type ion exchanger may be incorporated into a cartridge as a filter and an aqueous solution may be passed through it. It is preferable to use semiconductor-grade membrane ion exchangers. Examples of commercially available membrane ion exchangers include Mustang (manufactured by Pall) and Protego® Plus LT Purifier (manufactured by Entegris).

[0160] There are no particular restrictions on the thickness of the film-like ion exchanger; for example, 0.01 to 1 mm is preferred. The flow rate of the aqueous solution is, for example, 1 to 100 mL / (min·cm). 2 )

[0161] In method P3, the substance to be purified only needs to be passed through at least one membrane-type ion exchanger. In particular, two or more membrane-type ion exchangers may be used to pass the substance to be purified, as this makes the preparation of the drug solution easier. Furthermore, when using two or more membrane-type ion exchangers, at least one membrane-type ion exchanger having a cation exchange group and at least one ion exchanger having an anion exchange group may be used.

[0162] The ion exchange method is preferably carried out until the content of the metal component in the product to be purified falls within the range of the preferred metal component content described above.

[0163] (Filtration process) The above manufacturing method preferably includes a filtration step in which the liquid is filtered to remove foreign matter and coarse particles from the liquid. There are no particular restrictions on the filtration method, and known filtration methods can be used. Among these, filtering using a filter is preferred.

[0164] The filters used for filtering can be any type that has been conventionally used for filtration purposes, without any particular limitations. Examples of materials that make up the filters include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight), and polyarylsulfone. Among these, polyamide resins, PTFE, polypropylene (including high-density polypropylene), and polyarylsulfone are preferred. By using filters formed from these materials, highly polar foreign substances that are prone to causing defects can be more effectively removed from the composition.

[0165] The critical surface tension of the filter is preferably 70 mN / m or higher as the lower limit and 95 mN / m or lower as the upper limit. In particular, the critical surface tension of the filter is preferably 75 to 85 mN / m. Note that the critical surface tension value is the manufacturer's nominal value. By using a filter with a critical surface tension within the above range, highly polar foreign matter that is likely to cause defects can be more effectively removed from the composition.

[0166] The pore size of the filter is preferably about 0.001 to 1.0 μm, more preferably about 0.02 to 0.5 μm, and even more preferably about 0.01 to 0.1 μm. By setting the pore size of the filter within the above range, it is possible to reliably remove fine foreign matter contained in the composition while suppressing clogging during filtration.

[0167] When using filters, different filters may be combined. In this case, filtering with the first filter may be performed only once or two or more times. When different filters are combined and filtering is performed two or more times, each filter may be of the same type or of different types, but it is preferable that they be of different types. Typically, it is preferable that the first filter and the second filter differ in at least one of their pore size and constituent material. It is preferable that the pore size of subsequent filters is the same as or smaller than the pore size of the first filter. Alternatively, a combination of first filters with different pore sizes within the above range may be used. The pore size here can be referenced from the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by companies such as Nippon Pall Co., Ltd., Advantec Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), or Kitz Microfilter Corporation. In addition, polyamide "P-Nylon Filter (pore size 0.02 μm, critical surface tension 77 mN / m)" (manufactured by Nippon Pall Co., Ltd.), high-density polyethylene "PE-Clean Filter (pore size 0.02 μm)" (manufactured by Nippon Pall Co., Ltd.), and high-density polyethylene "PE-Clean Filter (pore size 0.01 μm)" (manufactured by Nippon Pall Co., Ltd.) can also be used.

[0168] The second filter can be made of the same material as the first filter described above. It can have the same pore size as the first filter described above. When using a second filter with a smaller pore size than the first filter, the ratio of the pore size of the second filter to the pore size of the first filter (pore size of the second filter / pore size of the first filter) is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and even more preferably 0.3 to 0.9. By setting the pore size of the second filter within the above range, fine foreign matter mixed in the composition can be removed more reliably.

[0169] For example, the first filtering may be performed on a mixture containing some of the components of the composition, and the remaining components may be mixed in to prepare the composition before the second filtering is performed. Furthermore, it is preferable that the filter used is treated before filtering the composition. The liquid used for this treatment is not particularly limited, but it is preferable that it contains the composition and the components contained in the composition.

[0170] When filtering is performed, the upper limit of the filtering temperature is preferably room temperature (25°C) or lower, more preferably 23°C or lower, and even more preferably 20°C or lower. The lower limit of the filtering temperature is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher. Filtering can remove particulate foreign matter and / or impurities, but when performed at the above temperature, the amount of particulate foreign matter and / or impurities dissolved in the composition is reduced, making the filtering more efficient.

[0171] [container] The container for containing the above composition is not particularly limited as long as corrosiveness due to the liquid is not a problem, and any known container can be used. For semiconductor applications, the above-mentioned containers are preferably those with a high degree of cleanliness inside the container and low elution of impurities. Examples of commercially available containers include the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd. Furthermore, to prevent contamination of raw materials and chemical solutions, it is also preferable to use multilayer containers with a six-layer structure made of six types of resin for the inner wall, or multilayer containers with a seven-layer structure made of six types of resin. Examples of such containers include, but are not limited to, the container described in Japanese Patent Publication No. 2015-123351. The inner wall of the above-mentioned container is preferably formed or coated with one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, other resins, and metals such as stainless steel, Hastelloy, Inconel, and Monel.

[0172] As for the different resins mentioned above, fluororesins (perfluororesins) can be preferably used. By using a container in which the inner wall is formed of or coated with a fluororesin, the occurrence of problems such as the elution of ethylene or propylene oligomers can be suppressed compared to using a container in which the inner wall is formed of or coated with polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin. Specific examples of containers having such inner walls include, for example, the FluoroPurePFA composite drum manufactured by Entegris. Containers described on page 4 of Japanese Patent Publication No. 3-502677, page 3 of International Publication No. 2004 / 016526, and pages 9 and 16 of International Publication No. 99 / 46309 can also be used.

[0173] These containers should preferably be cleaned inside before filling. The liquid used for cleaning can be appropriately selected depending on the application, but it is preferable to use the above composition, a diluted liquid of the above composition, or a liquid containing at least one of the components added to the above composition.

[0174] To prevent changes in the components of the composition during storage, the container may be purged with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. Gases with a low water content are particularly preferred. Furthermore, while the liquid container may be transported and stored at room temperature, the temperature may be controlled within the range of -20°C to 20°C to prevent deterioration.

[0175] {object to be processed} The composition of the present invention is preferably used to remove Ru-containing materials from a substrate. In this specification, "on the substrate" includes, for example, the front and back surfaces, sides, and inside grooves of the substrate. Furthermore, Ru-containing material on the substrate includes not only Ru-containing material directly present on the surface of the substrate, but also Ru-containing material present on the substrate via other layers. Hereinafter, grooves, holes, and other recesses provided in the substrate will also be referred to as "grooves, etc."

[0176] The type of substrate is not particularly limited, but a semiconductor substrate is preferred. Examples of substrates include semiconductor wafers, photomask glass substrates, liquid crystal display glass substrates, plasma display glass substrates, FED (Field Emission Display) substrates, optical disc substrates, magnetic disc substrates, and magneto-optical disc substrates. Materials that constitute semiconductor substrates include silicon, germanium, silicon-germanium, and group III-V compounds such as GaAs, as well as combinations thereof.

[0177] The applications of the workpiece treated with the composition of the present invention are not particularly limited. For example, it may be used in DRAM (Dynamic Random Access Memory), FRAM (Registered Trademark) (Ferroelectric Random Access Memory), MRAM (Magnetoresistive Random Access Memory), and PRAM (Phase Change Random Access Memory), as well as in logic circuits and processors.

[0178] Ru-containing materials are not particularly limited as long as they contain Ru (Ru atoms), and examples include elemental Ru, Ru-containing alloys, Ru oxides, Ru nitrides, and Ru oxynitrides. Furthermore, Ru oxides, Ru nitrides, and Ru oxynitrides may also be Ru-containing composite oxides, composite nitrides, and composite oxynitrides. The content of Ru atoms in the Ru-containing material is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the Ru-containing material. There is no particular upper limit, but it is preferably 100% by mass or less, based on the total mass of the Ru-containing material.

[0179] Ru-containing materials may also contain other transition metals. Examples of transition metals include Rh (rhodium), Ti (titanium), Ta (tantalum), Co (cobalt), Cr (chromium), Hf (hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Cu (copper), Zr (zirconium), Mo (molybdenum), La (lanthanum), W (tungsten), and Ir (iridium).

[0180] The form of the Ru-containing material on the substrate is not particularly limited and may be arranged in any form, for example, as a film, wiring, plate, columnar, or particulate. Examples of forms in which Ru-containing material is arranged in particulate form include, as described later, a substrate on which a Ru-containing film is placed, after which particulate Ru-containing material adheres as a residue after dry etching; a substrate on which a Ru-containing film is placed, after which particulate Ru-containing material adheres as a residue after CMP (chemical mechanical polishing) is performed; and a substrate on which a Ru-containing film is deposited, and particulate Ru-containing material adheres to areas other than the area where the Ru-containing film is intended to be formed.

[0181] The thickness of the Ru-containing film is not particularly limited and can be appropriately selected depending on the application. For example, it is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. There is no particular lower limit, but it is preferably 0.1 nm or more. The Ru-containing film may be placed on only one main surface of the substrate, or on both main surfaces. Furthermore, the Ru-containing film may be placed on the entire main surface of the substrate, or on only a portion of the main surface.

[0182] Furthermore, the material to be processed may contain various layers or structures other than the Ru-containing material, as desired. For example, one or more components selected from the group consisting of metal wiring, gate electrodes, source electrodes, drain electrodes, insulating films, ferromagnetic layers, and non-magnetic layers may be arranged on the substrate. The substrate may include an exposed integrated circuit structure. Examples of the integrated circuit structure include interconnection mechanisms such as metal wiring and dielectric materials. Examples of metals and alloys used in the interconnection mechanisms include aluminum, copper-aluminum alloy, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten and molybdenum. The substrate may include a layer of one or more materials selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.

[0183] There are no particular restrictions on the size, thickness, shape, or layer structure of the substrate; these can be selected as appropriate according to the requirements.

[0184] [Manufacturing method for the object to be processed] The method for manufacturing the product to be processed is not particularly limited, and known manufacturing methods can be used. Ru-containing films can be formed on a substrate using methods such as sputtering, chemical vapor deposition (CVD), molecular beam epitaxy (MBE), and atomic layer deposition (ALD) to manufacture the treated material. When forming a Ru-containing film using the above manufacturing method, if the substrate has an uneven structure, the Ru-containing film may be formed on all surfaces of the structure. Furthermore, when Ru-containing films are formed by sputtering or CVD methods, the Ru-containing film may also adhere to the back surface of the substrate on which it is placed (the surface opposite to the Ru-containing film side). Alternatively, the above method may be carried out through a predetermined mask to form Ru-containing wiring on the substrate. Furthermore, a substrate on which a Ru-containing film or Ru-containing wiring is arranged may be subjected to a predetermined treatment and used as a workpiece for the treatment method of the present invention. For example, a substrate on which a Ru-containing film or Ru-containing wiring is placed may be subjected to dry etching to produce a substrate having a dry etching residue containing Ru. Alternatively, a substrate on which a Ru-containing film or Ru-containing wiring is placed may be subjected to CMP to produce a substrate containing Ru. Furthermore, a Ru-containing film may be deposited on the region of the substrate where the Ru-containing film is to be formed by sputtering, CVD, molecular beam epitaxy, or atomic layer deposition, so that the Ru-containing film adheres to the region other than the planned Ru-containing film formation area, thereby producing a substrate containing Ru.

[0185] {Method for processing circuit boards} [Process A] The present invention relates to a method for processing a substrate (hereinafter also referred to as "this processing method"), which includes step A of removing Ru-containing substances from the substrate using the composition of the present invention. Furthermore, the same applies to the substrate on which the Ru-containing material is placed, which is the object to be processed by this processing method.

[0186] A specific method for step A is to bring the composition into contact with a substrate on which the Ru-containing material to be treated is placed. The method of contact is not particularly limited and includes, for example, immersing the object to be treated in a composition placed in a tank, spraying the composition onto the object to be treated, flowing the composition over the object to be treated, and combinations thereof. Among these, immersing the object to be treated in the composition is preferred.

[0187] Furthermore, a mechanical stirring method may be used to further enhance the cleaning ability of the composition. Examples of mechanical stirring methods include circulating the composition over the workpiece, flowing or spraying the composition over the workpiece, and locally stirring the composition near the substrate by irradiating it with ultrasonic waves (e.g., megasonic waves). The processing time for step A can be adjusted as appropriate. The processing time (contact time between the composition and the object to be processed) is not particularly limited, but is preferably 0.25 to 10 minutes, and more preferably 0.5 to 2 minutes. The temperature of the composition during the treatment is not particularly limited, but a temperature of 20 to 75°C is preferred, a temperature of 20 to 60°C is more preferred, a temperature of 40 to 65°C is even more preferred, and a temperature of 50 to 65°C is particularly preferred.

[0188] In step A, while measuring the concentration of one or more components selected from the group consisting of a periodic acid compound, a specific quaternary ammonium salt, a trialkylamine or its salt, and an optional component in the composition, if necessary, a treatment of adding a solvent and one or more selected from the group consisting of the components of the composition to the composition may be carried out. By carrying out this treatment, the component concentration in the composition can be stably maintained within a predetermined range. Water is preferred as the solvent.

[0189] Specific preferred embodiments of step A include, for example, step A1 of subjecting a Ru-containing wiring or a Ru-containing liner disposed on a substrate using the composition to a recess etching treatment, step A2 of removing the Ru-containing film on the outer edge of the substrate on which the Ru-containing film is disposed using the composition, step A3 of removing the Ru-containing substance adhering to the back surface of the substrate on which the Ru-containing film is disposed using the composition, step A4 of removing the Ru-containing substance on the substrate after dry etching using the composition, step A5 of removing the Ru-containing substance on the substrate after chemical mechanical polishing treatment using the composition, and step A6 of removing the Ru-containing substance in the region other than the region where the Ru-containing film is to be formed on the substrate after depositing the Ru-containing film on the region where the Ru-containing film is to be formed on the substrate using the composition. Hereinafter, the present treatment method used in each of the above treatments will be described.

[0190] (Step A1) As step A, there is step A1 of subjecting a Ru-containing wiring (wiring containing Ru) and a Ru-containing liner (liner containing Ru) disposed on a substrate using the composition to a recess etching treatment. Hereinafter, as examples of the object to be treated in step A1, a substrate having a Ru-containing wiring and a substrate having a Ru-containing liner will be specifically described.

[0191] <Substrate having a Ru-containing wiring> Figure 1 shows a schematic cross-sectional view of the upper part of a substrate having Ru-containing wiring (hereinafter also referred to as "Ru wiring substrate"), which is an example of a workpiece subjected to recess etching in process A1. The Ru wiring board 10a shown in Figure 1 comprises a substrate (not shown), an insulating film 12 having grooves or the like arranged on the substrate, a barrier metal layer 14 arranged along the inner wall of the grooves or the like, and Ru-containing wiring 16 filled inside the grooves or the like.

[0192] In a Ru wiring board, the Ru-containing wiring preferably contains elemental Ru, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The materials constituting the barrier metal layer in the Ru wiring substrate are not particularly limited and include, for example, Ti metal, Ti nitride, Ti oxide, Ti-Si alloy, Ti-Si composite nitride, Ti-Al alloy, Ta metal, Ta nitride, and Ta oxide. Although Figure 1 describes an embodiment in which the Ru wiring board has a barrier metal layer, a Ru wiring board without a barrier metal layer is also possible.

[0193] In step A1, recess etching can be performed on the Ru wiring substrate using the above-described composition to remove a portion of the Ru-containing wiring and form a recess. More specifically, when step A1 is performed, as shown in the Ru wiring substrate 10b of Figure 2, a portion of the barrier metal layer 14 and the Ru-containing wiring 16 are removed, and a recess 18 is formed. In Figure 2, the Ru wiring substrate 10b is shown in a configuration where the barrier metal layer 14 and a portion of the Ru-containing wiring 16 are removed. However, the barrier metal layer 14 may not be removed, and only a portion of the Ru-containing wiring 16 may be removed to form the recess 18.

[0194] The method for manufacturing the Ru wiring substrate is not particularly limited. For example, it includes a step of forming an insulating film on a substrate, a step of forming grooves or the like in the insulating film, a step of forming a barrier metal layer on the insulating film, a step of forming a Ru-containing film so as to fill the grooves or the like, and a step of performing a planarization treatment on the Ru-containing film.

[0195] <Substrate having a Ru-containing liner> FIG. 3 shows a schematic view of the upper part of a cross-section representing a substrate having a Ru-containing liner (hereinafter also referred to as “Ru liner substrate”), which is another example of the object to be processed in the recess etching treatment of step A1.

[0196] The Ru liner substrate 20a shown in FIG. 3 includes a substrate not shown, an insulating film 22 having grooves or the like disposed on the substrate, a Ru-containing liner 24 disposed along the inner walls of the grooves or the like, and a wiring portion 26 filled inside the grooves or the like.

[0197] The Ru-containing liner in the Ru liner substrate preferably contains Ru alone, an alloy of Ru, an oxide of Ru, a nitride of Ru, or an oxynitride of Ru. In the Ru liner substrate shown in FIG. 3, a separate barrier metal layer may be provided between the Ru-containing liner 24 and the insulating film 22. Examples of the material constituting the barrier metal layer are the same as those in the case of the Ru wiring substrate. The material constituting the wiring portion in the Ru liner substrate is not particularly limited. For example, Cu metal, W metal, Mo metal, and Co metal can be mentioned.

[0198] In step A1, by performing a recess etching treatment on the Ru liner substrate using the above-described composition, a part of the Ru-containing liner can be removed to form a recess. More specifically, when step A1 is carried out, as shown in the Ru liner substrate 20b of FIG. 4, a part of the Ru-containing liner 24 and the wiring portion 26 are removed to form a recess 28.

[0199] The method for manufacturing a Ru liner substrate is not particularly limited and includes a step of forming an insulating film on a substrate, a step of forming grooves or the like in the insulating film, a step of forming a Ru liner on the insulating film, a step of forming a metal film so as to fill the grooves or the like, and a step of performing a planarization treatment on the metal film.

[0200] A specific method for step A1 is to bring a Ru wiring board or Ru liner board into contact with the composition. The method of contact between the Ru wiring board or Ru liner board and the composition is as described above. The preferred contact time between the Ru wiring board or Ru liner board and the composition, and the preferred temperature range of the composition, are as described above.

[0201] (Process B) Furthermore, before or after step A1, step B may be performed to process the substrate obtained in step A1 using a predetermined solution (hereinafter also referred to as "specific solution"), if necessary. In particular, when a barrier metal layer is placed on a substrate, the solubility of the components constituting the Ru-containing wiring or Ru liner (hereinafter also referred to as "Ru-containing wiring, etc.") and the components constituting the barrier metal layer may differ depending on their type. In such cases, it is preferable to adjust the degree of dissolution of the Ru-containing wiring, etc. and the barrier metal layer using a solution that has superior solubility for the barrier metal layer. From this perspective, a specific solution is preferable that has poor dissolving ability for Ru-containing wiring and other materials, but excellent dissolving ability for materials constituting the barrier metal layer.

[0202] Examples of specific solutions include those 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 FPM is preferably within the range (by volume) of, for example, "hydrofluoric acid:hydrogen peroxide:water = 1:1:1" to "hydrofluoric acid:hydrogen peroxide:water = 1:1:200". The composition of the SPM is preferably within the range (by volume) of, for example, "sulfuric acid:hydrogen peroxide:water = 3:1:0" to "sulfuric acid:hydrogen peroxide:water = 1:1:10". The composition of APM is preferably within the range (by volume) of, for example, "ammonia water:hydrogen peroxide water:water = 1:1:1" to "ammonia water:hydrogen peroxide water:water = 1:1:30". The composition of HPM is preferably within the range (by volume) of, for example, "hydrochloric acid:hydrogen peroxide:water = 1:1:1" to "hydrochloric acid:hydrogen peroxide:water = 1:1:30". Furthermore, these preferred composition ratios refer to the composition ratios when hydrofluoric acid is 49% by mass, sulfuric acid is 98% by mass, aqueous ammonia is 28% by mass, hydrochloric acid is 37% by mass, and hydrogen peroxide is 31% by mass. Among these, SPM, APM, or HPM are preferred as specific solutions from the viewpoint of their ability to dissolve the barrier metal layer. As for the specific solution, APM, HPM, or FPM are preferred from the viewpoint of reducing roughness, with APM being more preferred. As for the specific solution, APM or HPM is preferred from the viewpoint of having an excellent balance of performance.

[0203] In step B, the preferred method for treating the substrate obtained in step A1 using a specific solution is to bring 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 for example, a method similar to that for bringing the composition into contact with the substrate can be used. The contact time between the specific solution and the substrate obtained in step A1 is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes.

[0204] In this processing method, steps A1 and B may be performed alternately and repeatedly. When the processes are performed alternately, it is preferable that each of processes A1 and B be performed 1 to 10 times. Furthermore, when processes A1 and B are performed alternately, the first and last processes may be either process A1 or process B.

[0205] (Process A2) Step A is, for example, step A2, which involves using the composition to remove the Ru-containing film from the outer edge of the substrate on which the Ru-containing film is placed. Figure 5 shows a schematic diagram (top view) of an example of a substrate on which the Ru-containing film, which is the material to be processed in process A2, is placed. The workpiece 30 in step A2 shown in Figure 5 is a laminate having a substrate 32 and a Ru-containing film 34 disposed on the main surface of one side of the substrate 32 (the entire area enclosed by the solid line). As will be described later, in step A2, the Ru-containing film 34 located at the outer edge 36 of the workpiece 30 (the area outside the dashed line) is removed.

[0206] The substrate and Ru-containing film in the workpiece are as described above. Furthermore, the Ru-containing film preferably contains elemental Ru, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides.

[0207] The specific method for step A2 is not particularly limited, and one example is a method of supplying the composition from a nozzle so that the composition comes into contact only with the Ru-containing film on the outer edge of the substrate. During the processing of step A2, the substrate processing apparatus and substrate processing method described in Japanese Patent Publication No. 2010-267690, Japanese Patent Publication No. 2008-080288, Japanese Patent Publication No. 2006-100368, and Japanese Patent Publication No. 2002-299305 can be preferably applied.

[0208] The method of contact between the composition and the object to be treated is as described above. The preferred contact time between the composition and the object to be treated, and the preferred temperature range of the composition, are as described above.

[0209] (Process A3) Step A includes step A3, which involves using the composition to remove Ru-containing substances adhering to the back surface of the substrate on which the Ru-containing film is placed. Examples of workpieces processed in process A3 include those used in process A2. When forming the workpiece used in process A2, which consists of a substrate and a Ru-containing film placed on one main surface of the substrate, the Ru-containing film is formed by sputtering and CVD, etc. In this process, Ru-containing material may adhere to the surface of the substrate opposite to the Ru-containing film side (the back surface). Process A3 is performed to remove such Ru-containing material from the workpiece.

[0210] The specific method for step A3 is not particularly limited, and one example is a method of spraying the composition so that it comes into contact only with the back surface of the substrate.

[0211] The method of contact between the composition and the object to be treated is as described above. The preferred contact time between the composition and the object to be treated, and the preferred temperature range of the composition, are as described above.

[0212] (Process A4) Step A includes step A4, which involves using the composition to remove Ru-containing material from the substrate after dry etching. Figures 6 and 8 show schematic diagrams illustrating examples of the workpieces processed in process A4. The following explains each of the figures.

[0213] The workpiece 40 shown in Figure 6 has a substrate 42 on which a Ru-containing film 44, an etching stop layer 46, an interlayer insulating film 48, and a metal hard mask 50 are arranged in this order, and after going through a dry etching process, a groove or the like 52 is formed at a predetermined position in which the Ru-containing film 44 is exposed. In other words, the workpiece shown in Figure 6 is a laminate comprising a substrate 42, a Ru-containing film 44, an etching stop layer 46, an interlayer insulating film 48, and a metal hard mask 50 in this order, and has a groove or the like 52 that penetrates from the surface of the metal hard mask 50 to the surface of the Ru-containing film 44 at the position of the opening of the metal hard mask 50. The inner wall 54 of the groove or the like 52 is composed of a cross-sectional wall 54a made of the etching stop layer 46, the interlayer insulating film 48, and the metal hard mask 50, and a bottom wall 54b made of the exposed Ru-containing film 44, and dry etching residue 56 is attached to the inner wall 54 of the groove or the like 52. Dry etching residue contains Ru-containing material.

[0214] The workpiece 60b shown in Figure 8 is obtained by dry etching the workpiece shown in Figure 7 before dry etching. The workpiece 60a shown in Figure 7 comprises an insulating film 62 disposed on a substrate (not shown), a Ru-containing film 66 filled in grooves or the like formed in the insulating film 62, and a metal hard mask 64 disposed on the insulating film 62 with the Ru-containing film 66 positioned in the openings. This workpiece 60a is obtained by forming the insulating film 62 and the metal hard mask 64 in that order on a substrate (not shown), forming grooves or the like in the insulating film 62 located in the openings of the metal hard mask 64, then filling the grooves or the like with Ru-containing material to form the Ru-containing film 66. When the workpiece 60a shown in Figure 7 is dry-etched, the Ru-containing film is etched, and the workpiece 60b shown in Figure 8 is obtained. The workpiece 60b shown in Figure 8 comprises an insulating film 62 placed on a substrate (not shown), a Ru-containing film 66 filled in a portion of grooves etc. 72 formed in the insulating film 62, and a metal hard mask 64 placed on the insulating film 62 with openings at the positions of the grooves etc. 72. Dry etching residue 76 is attached to the cross-sectional wall 74a made of the insulating film 62 and the metal hard mask 64 within the grooves etc. 72, and to the bottom wall 74b made of the Ru-containing film 66. Dry etching residue contains Ru-containing material.

[0215] The Ru-containing film of the workpiece subjected to step A4 preferably contains elemental Ru, Ru alloy, Ru oxide, Ru nitride, or Ru oxynitride. The Ru-containing material of the workpiece subjected to process A4 preferably includes elemental Ru, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The interlayer insulating film and the insulating film are selected from known materials. For the metal hard mask, known materials are selected. Although Figures 6, 7, and 8 describe an embodiment using a metal hard mask, a resist mask formed using a known photoresist material may also be used.

[0216] A specific method for step A4 is to bring the composition into contact with the object to be treated. The method of contact between the composition and the wiring board is as described above. The preferred contact time between the composition and the wiring board, and the preferred temperature range of the composition, are as described above.

[0217] (Process A5) Step A includes step A5, which involves using the composition to remove Ru-containing material from the substrate after chemical mechanical polishing (CMP). CMP (Chemical Polishing) technology is used in manufacturing processes such as planarization of insulating films, planarization of connection holes, and damascene wiring. After CMP, substrates may be contaminated with a large amount of abrasive particles and metal impurities. Therefore, it is necessary to remove these contaminants and clean the substrate before proceeding to the next processing stage. By performing step A5, it is possible to remove Ru-containing substances that are generated and adhere to the substrate when the CMP-treated object has Ru-containing wiring or a Ru-containing film.

[0218] As mentioned above, the workpiece in step A5 is a substrate containing Ru after CMP. The Ru-containing material preferably includes elemental Ru, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. A specific method for step A5 is to bring the composition into contact with the object to be treated. The method of contact between the composition and the wiring board is as described above. The preferred contact time between the composition and the wiring board, and the preferred temperature range of the composition, are as described above.

[0219] (Process A6) Step A includes step A6, which involves using the composition to deposit a Ru-containing film in the region on the substrate where the Ru-containing film is to be formed, and then removing Ru-containing materials from areas on the substrate other than the region where the Ru-containing film is to be formed. As described above, the method for forming the Ru-containing film is not particularly limited, and the Ru-containing film can be formed on the substrate using sputtering, CVD, MBE, and ALD methods. When a Ru-containing film is formed on a substrate in the area where the Ru-containing film is intended to be formed (the area where the Ru-containing film is to be formed), the Ru-containing film may also be formed in unintended areas (areas other than the area where the Ru-containing film is intended to be formed). Examples of unintended areas include the side walls of an insulating film when filling grooves in the insulating film with the Ru-containing film. An example of the workpiece to be processed in step A6 is shown in Figure 10. The workpiece 80b shown in Figure 10 is obtained by forming a Ru-containing film on the workpiece 80a shown in Figure 9 before the formation of the Ru-containing film. The workpiece 80a shown in Figure 9 has an insulating film 82 placed on a substrate (not shown) and a metal hard mask 84 placed on the insulating film 82, with the insulating film 82 having grooves or the like 86 at the openings of the metal hard mask 84. By forming a Ru-containing film to fill a portion of the grooves or the like 86 of this workpiece 80a, the workpiece 80b shown in Figure 10 is obtained. The workpiece 80b shown in Figure 10 comprises an insulating film 82 placed on a substrate (not shown), a Ru-containing film 88 filled in a portion of grooves etc. 86 formed in the insulating film 82, and a metal hard mask 84 placed on the insulating film 82 with openings at the positions of the grooves etc. 86. Residue 92 from the formation of the Ru-containing film adheres to the cross-sectional wall 90a made of the insulating film 82 and the metal hard mask 84 within the grooves etc. 86, and to the bottom wall 90b made of the Ru-containing film 88. In the above embodiment, the region where the Ru-containing film 88 is located corresponds to the region where the Ru-containing film is to be formed, while the cross-sectional wall 90a and the bottom wall 90b correspond to regions other than the region where the Ru-containing film is to be formed.

[0220] The Ru-containing film preferably contains elemental Ru, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The Ru-containing material preferably includes elemental Ru, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. For the metal hard mask, known materials are selected. Although Figures 9 and 10 describe an embodiment using a metal hard mask, a resist mask formed using a known photoresist material may also be used.

[0221] A specific method for step A6 is to bring the composition into contact with the object to be treated. The method of contact between the composition and the wiring board is as described above. The preferred contact time between the composition and the wiring board, and the preferred temperature range of the composition, are as described above.

[0222] [Process C] This processing step may include, if necessary, a step C in which the substrate obtained in step A is rinsed using a rinsing solution.

[0223] Suitable rinsing solutions include, for example, hydrofluoric acid (preferably 0.001 to 1% by mass hydrofluoric acid), hydrochloric acid (preferably 0.001 to 1% by mass hydrochloric acid), hydrogen peroxide (preferably 0.5 to 31% by mass hydrogen peroxide, more preferably 3 to 15% by mass hydrogen peroxide), 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), a mixture of hydrochloric acid and hydrogen peroxide (HPM), carbon dioxide water (preferably 10 to 60 ppm by mass carbon dioxide water), ozonated water (preferably 10 to 60 ppm by mass ozonated water), hydrogen water (preferably 10 to 20 ppm by mass hydrogen water), citric acid aqueous solution (preferably 0.01 to 10% by mass citric acid aqueous solution), and acetic acid (undiluted acetic acid or 0.01 to 10% by mass acetic acid). Aqueous solutions are preferred), sulfuric acid (1-10% by mass aqueous sulfuric acid solution is preferred), aqueous ammonia (0.01-10% by mass aqueous ammonia solution is preferred), isopropyl alcohol (IPA), aqueous hypochlorous acid solution (1-10% by mass aqueous hypochlorous acid solution is preferred), aqua regia (aqua regia corresponding to a volume ratio of 2.6 / 1.4-3.4 / 0.6 of 37% by mass hydrochloric acid to 60% by mass nitric acid is preferred), ultrapure water, nitric acid (0.001-1% by mass nitric acid is preferred), perchloric acid (0.001-1% by mass perchloric acid is preferred), aqueous oxalic acid solution (0.01-10% by mass aqueous solution is preferred), or aqueous periodic acid solution (0.5-10% by mass aqueous periodic acid solution is preferred, and examples of periodic acid include orthoperiodic acid and metaperiodic acid). The preferred conditions for FPM, SPM, APM, and HPM are, for example, the same as the preferred embodiments for FPM, SPM, APM, and HPM used as the specific solutions described above. Note that hydrofluoric acid, nitric acid, perchloric acid, and hydrochloric acid refer to aqueous solutions of HF, HNO3, HClO4, and HCl, respectively, dissolved in water. Ozone water, carbon dioxide water, and hydrogen water refer to aqueous solutions obtained by dissolving O3, CO2, and H2 in water, respectively. These rinsing solutions may be mixed and used insofar as they do not impair the purpose of the rinsing process.

[0224] In particular, as a rinsing solution, from the viewpoint of further reducing residual chlorine on the substrate surface after the rinsing process, carbon dioxide water, ozonated water, hydrogen water, hydrofluoric acid, citric acid aqueous solution, hydrochloric acid, sulfuric acid, ammonia water, hydrogen peroxide solution, SPM, APM, HPM, IPA, hypochlorous acid aqueous solution, aqua regia, or FPM are preferred, and hydrofluoric acid, hydrochloric acid, hydrogen peroxide solution, SPM, APM, HPM, or FPM are more preferred.

[0225] A specific method for step C is, for example, to bring the rinsing solution into contact with the substrate obtained in step A, which is the object to be processed. Methods of bringing the substrate into contact with the rinse solution include, for example, immersing the substrate in a rinse solution in a tank, spraying the rinse solution onto the substrate, pouring the rinse solution onto the substrate, and any combination thereof.

[0226] The processing time (contact time between the rinse solution and the object being processed) is not particularly limited, and can range from 5 seconds to 5 minutes, for example. The temperature of the rinse solution during processing is not particularly limited, but is generally preferred to be between 16 and 60°C, and more preferably between 18 and 40°C. When SPM is used as the rinse solution, its temperature is preferably between 90 and 250°C.

[0227] [Process D] This processing method may include a step D after step C, in which a drying process is carried out as needed. The drying method is not particularly limited, but examples include spin drying, flow of drying gas over the substrate, heating of the substrate (e.g., heating by a hot plate or infrared lamp), IPA (isopropyl alcohol) vapor drying, Marangoni drying, Rotagoni drying, and combinations thereof. The drying time can be adjusted as needed depending on the specific method used, for example, from 30 seconds to several minutes.

[0228] [Other processes] This processing method may be carried out in combination with other processes performed on the substrate, either before or after. It may also be incorporated into other processes, or the processing method of the present invention may be incorporated into other processes. Other processes include, for example, the formation of structures such as metal wiring, gate structures, source structures, drain structures, insulating films, ferromagnetic layers, and non-magnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and modification), the formation of resists, exposure and removal processes, heat treatment processes, cleaning processes, and inspection processes. This processing method may be performed at any stage of the backend process (BEOL), middle process (MOL), or frontend process (FEOL), but it is preferable to perform it in the frontend or middle process. [Examples]

[0229] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate 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 examples shown below.

[0230] {Preparation of composition} Examples and Comparative Examples To ultrapure water, orthoperiodic acid, B-1: tetraethylammonium hydroxide, and 2: triethylamine were added in the amounts shown in Tables 1 to 4 below to form a mixture. The mixture was then thoroughly stirred with a stirrer to obtain the composition of Example 1. The compositions of Examples 2-75 and Comparative Examples 1-4 were prepared using the same procedure as in Example 1, except that the type and amount of each component were changed according to Tables 1-4. Furthermore, the remainder of the compositions in each example and comparative example, other than the components listed in the table, is water. In addition, the "-" symbol in Comparative Examples 1-4 in Table 4 indicates that the component in question was not added. Furthermore, all of the main components listed in Tables 1-4 were classified as semiconductor grade or equivalent high-purity grade. The following provides a detailed explanation of each component listed in Tables 1-4.

[0231] [Periodate compounds] • Orthoperiodic acid Metaperiodic acid • Sodium orthoperiodate • Potassium orthoperiodate Sodium metaperiodate

[0232] [Specific Quaternary Ammonium Salts] · A-1: ​​Tetramethylammonium hydroxide A-3: Tetramethylammonium bromide ·B-1: Tetraethylammonium Hydroxide ·B-2: Tetraethylammonium chloride ·C-1: Tetrabutylammonium Hydroxide · D-1: Ethyltrimethylammonium hydroxide · D-2: Ethyltrimethylammonium chloride ·E-1: Diethyldimethylammonium hydroxyl ·E-2: Diethyldimethylammonium chloride ·F-1: Methyltriethylammonium hydroxyl ·F-2: Methyltriethylammonium chloride · G-1: Trimethyl(hydroxyethyl)ammonium hydroxide G-2: Trimethyl(hydroxyethyl)ammonium chloride H-2: Methyltributylammonium chloride ·I-4: Dimethyldibutylammonium fluoride ·J-1: Benzyltrimethylammonium hydroxide J-3: Benzyltrimethylammonium bromide K-1: Benzyltriethylammonium hydroxide • L-3: Triethyl(hydroxyethyl)ammonium bromide M-2: Dodecyltrimethylammonium chloride • N-4: Tetradecyltrimethylammonium fluoride O-2: Hexadecyltrimethylammonium chloride

[0233] [Trialkylamine] 1: Trimethylamine 2: Triethylamine 3: Diethylmethylamine 4: Ethyldimethylamine 5: Tri-n-butylamine 6: Dimethylhydroxyethylamine 7: Dimethylpropylamine 8: Benzyldimethylamine 9: Benzyl diethylamine 10: Diethylhydroxyethylamine 11: Dodecyldimethylamine 12: Tetradecyldimethylamine 13: Hexadecyldimethylamine 14: N-methyldiethanolamine

[0234] [solvent] ·Ultra pure water

[0235] [Compound X] IO3 - 、 I - and I3 - Compound X, which has at least one anion selected from the group consisting of the following, uses a compound that combines a quaternary ammonium cation and an anion as described below. For example, in Example 1, the cation is "B: tetraethylammonium cation" and the anion is "IO3 - A compound having the following properties was used.

[0236] ·A: Tetramethylammonium cation B: Tetraethylammonium cation ·C: Tetrabutylammonium cation ·D: Ethyltrimethylammonium cation • E: Diethyldimethylammonium cation F: Methyltriethylammonium cation G: Trimethyl(hydroxyethyl)ammonium cation ·H: Methyltributylammonium cation ·I: Dimethyldipropylammonium cation ·J: Benzyltrimethylammonium cation ·K: Benzyltriethylammonium cation L: Triethyl(hydroxyethyl)ammonium cation M: Dodecyltrimethylammonium cation • N: Tetradecyltrimethylammonium cation ·O: Hexadecyltrimethylammonium cation • Proton: Proton (H) + )

[0237] {test} [Ru residue removal ability] A substrate was prepared by forming a Ru layer (a layer composed solely of Ru) on one surface of a commercially available silicon wafer (diameter: 12 inches) using the PVD method. The thickness of the Ru layer was confirmed to be 30 nm using XRF (Rigaku AZX400). The obtained substrates were placed in containers filled with the compositions of each example or comparative example, and the compositions were stirred to remove the Ru layer for 2 minutes. The temperature of the compositions was 25°C. The processed substrate was observed using a scanning electron microscope (Hitachi High-Tech S-4800). Observation was performed directly above the surface where the Ru layer was formed, and backscattered electron images were acquired at a magnification of 200,000x (field of view: 0.5 μm × 0.6 μm). From the acquired images, areas showing bright contrast were identified as remaining Ru residue areas, and their area was calculated. The percentage of the remaining Ru residue area relative to the observed area (X%) was determined, and the Ru residue removal efficiency (100%-X%) was calculated. The Ru residue removal ability was evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1 to 4. (Evaluation criteria for Ru residue removal ability) 5: 100% removal rate of Ru film 4: Ru film removal rate is 80% or more but less than 100% 3: Ru film removal rate is 60% or more but less than 80% 2: Ru film removal rate is 40% or more but less than 60% 1: Ru film removal rate is less than 40%

[0238] [Particle suppression] The amount of particles in the compositions of each example or comparative example was evaluated using a particle counter (KS-42A, manufactured by Rion Co., Ltd.). Particles with a size of 0.10 μm or larger were measured. Particle suppression performance was evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 1-4. (Evaluation criteria for particle suppression) 4: Less than 100 cells / mL 3: 100 to less than 500 particles / mL 2: 500 to less than 2000 particles / mL 1:2000 pieces / mL or more

[0239] In the table, each entry represents the following: The "content" of each component represents the percentage of each component relative to the total mass of the composition. In the table, if there are entries separated by " / " in a single column, in the column for "Type of Compound," it indicates that multiple compounds listed are added, and in the column for "Amount of Compound," it indicates the amount of each compound listed to the left in that column, in order. In the column for trialkylamine (C), "Requirement X" is R in formula (1). 1 , R 2 , and, R 3 Independently, "A" represents an alkyl group having 1 to 4 carbon atoms without substituents, and "B" represents all other cases. If two symbols are listed in the "Cation" column of Compound X(D), it indicates that the compound contains a combination of a cation and anion derived from these two symbols, respectively. The "C / D" in compound X(D) represents the ratio of the mass of the trialkylamine to the mass of compound X. The notation "En" in the numerical value in the "C / D" column means "×10 -n This means "E+n" is written as "×10 n This means "n represents an integer". A "-" symbol in a column containing numerical values ​​indicates that the compound or substance was not added or that its value could not be calculated. The numerical values ​​listed in the Ru residue removal ability and particle suppression ability columns represent the results evaluated according to the above criteria.

[0240] [Table 1]

[0241] [Table 2]

[0242] [Table 3]

[0243] [Table 4]

[0244] From the results in Tables 1-4, a comparison of the results of the examples and comparative examples confirmed that the composition of the present invention exhibits excellent Ru residue removal properties. Furthermore, it was confirmed that the composition of the present invention exhibits excellent particle suppression properties. The results from Examples 1 to 17 confirmed that the effects of the present invention are superior when the total number of carbon atoms in the specific quaternary ammonium salt is 4 to 16 (preferably 4 to 8). Comparing the results of Examples 1 to 23, R in formula (1) 1 , R 2 , and, R 3 It was confirmed that the effects of the present invention are superior when each of these is an alkyl group having 1 to 4 carbon atoms and no substituents. Comparing the results of Examples 1-9 and Examples 30-39, it was confirmed that the effects of the present invention are superior when the pH of the composition is 2.0-11.0 (preferably 3.0-10.0, more preferably 4.0-8.0). The results from Examples 40 to 48 confirmed that the effects of the present invention are superior when the content of the periodic acid compound is 0.01 to 5.0% by mass (preferably 0.1 to 2.0% by mass) relative to the total mass of the composition. The results from Examples 49 to 59 confirmed that the effects of the present invention are superior when the trialkylamine content is 1.0 ppb to 1.5% by mass (preferably 1.0 ppb to 0.2% by mass). Based on the results of Examples 30, 44, and 56, IO3 - 、 I - and I3 - The mass ratio of the trialkylamine content to the total mass of anions in a compound having at least one anion selected from the group consisting of is 1 × 10 -5 ~1 × 10 5 In that case, it was confirmed that it exhibits excellent particle suppression properties. [Explanation of symbols]

[0245] 10a, 10b Ru wiring board 12 Insulating film 14 Barrier metal layer 16 Ru-containing wiring 18 recesses 20a, 20b Ru liner substrate 22 Insulating film 24 Ru-containing liner 26 Wiring section 28 recesses 30. Items to be processed 32 circuit boards 34 Ru-containing membrane 36 Outer edge 40. Items to be processed 42 circuit boards 44 Ru-containing membrane 46 Etching stop layer 48 Interlayer insulating film 50 Metal Hard Mask 52 Grooves, etc. 54 Inner wall 54a Sectional wall 54b Bottom wall 56 Dry etching residue 60a, 60b Materials to be processed 62 Insulating film 64 Metal Hard Mask 66 Ru-containing membrane 72 Grooves, etc. 74a Sectional wall 74b bottom 76 Dry etching residue 80a, 80b Materials to be processed 82 Insulating film 84 Metal Hard Mask 86 Grooves, etc. 88 Ru-containing membrane 90a Sectional wall 90b bottom wall 92 Residue

Claims

1. One or more periodic acid compounds selected from the group consisting of periodic acid and its salts, Quaternary ammonium salts represented by formula (A), A composition comprising a trialkylamine or a salt thereof, The above composition is IO ３ － 、 I － and I ３ － A composition further comprising a compound having at least one anion selected from the group consisting of the following, used for removing ruthenium-containing material from a substrate. 【Chemistry 1】 In formula (A), R ａ ~R ｄ each independently represents an alkyl group which may have a substituent. n represents an integer of 1 or 2. X ｎ－ is Br － , Cl － , F － , CH ３ COO － , HSO ４ － , OH － , NO ３ － , or SO ４ ２－ represents.

2. The composition according to claim 1, wherein the content of the trialkylamine or a salt thereof is 1.0 ppb to 1.5% by mass with respect to the total mass of the composition.

3. The composition according to claim 1 or 2, wherein the periodic acid compound comprises at least one selected from the group consisting of orthoperiodic acid, metaperiodic acid, and salts thereof.

4. The composition according to any one of claims 1 to 3, wherein the content of the periodic acid compound is 0.01 to 5.0% by mass of the total mass of the composition.

5. The composition according to any one of claims 1 to 4, wherein the total number of carbon atoms in the quaternary ammonium salt is 4 to 16.

6. The composition according to any one of claims 1 to 5, wherein the total number of carbon atoms in the quaternary ammonium salt is 4 to 8.

7. The composition according to any one of claims 1 to 6, wherein the quaternary ammonium salt comprises at least one selected from the group consisting of tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, ethyltrimethylammonium salt, methyltriethylammonium salt, diethyldimethylammonium salt, methyltributylammonium salt, dimethyldipropylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, trimethyl(hydroxyethyl)ammonium salt, and triethyl(hydroxyethyl)ammonium salt.

8. The composition according to any one of claims 1 to 7, wherein the trialkylamine or a salt thereof is a compound represented by formula (1) or a salt thereof. 【Chemistry 2】 In formula (1), R １ , R ２ , and, R ３ Each of these independently represents an alkyl group which may have substituents.

9. R in formula (1) １ , R ２ , and, R ３ The composition according to claim 8, wherein each is independently an alkyl group having 1 to 4 carbon atoms and no substituents.

10. The composition according to any one of claims 1 to 9, wherein the content of the trialkylamine or a salt thereof is 1.0 ppb to 0.2% by mass with respect to the total mass of the composition.

11. The mass ratio of the content of the trialkylamine to the total mass of the anion in the compound having the anion is 1 × 10 －５ ~1 x 10 ５ The composition according to any one of claims 1 to 10.

12. The composition according to any one of claims 1 to 11, wherein the pH is 2.0 to 11.

0.

13. The composition according to any one of claims 1 to 12, wherein the pH is 3.0 to 10.

0.

14. The composition according to any one of claims 1 to 13, wherein the pH is 4.0 to 8.

0.

15. A method for processing a substrate, comprising step A of removing ruthenium-containing material from the substrate using the composition described in any one of claims 1 to 14.

16. A method for processing a substrate according to claim 15, wherein step A is a recess etching process A1 of ruthenium-containing wiring or ruthenium-containing liner disposed on the substrate using the composition; a step A2 of removing the ruthenium-containing film from the outer edge of the substrate on which the ruthenium-containing film is disposed using the composition; a step A3 of removing ruthenium-containing material adhering to the back surface of the substrate on which the ruthenium-containing film is disposed using the composition; a step A4 of removing ruthenium-containing material on the substrate after dry etching using the composition; a step A5 of removing ruthenium-containing material on the substrate after chemical mechanical polishing using the composition; or a step A6 of removing ruthenium-containing material in areas other than the area on the substrate on which the ruthenium-containing film is to be disposed on the area on the substrate on which the ruthenium-containing film is to be disposed on the area on which the ruthenium-containing film is to be disposed

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