Composition, method for treating object to be treated

Abstract

The objective of this invention is to provide a composition that exhibits excellent ruthenium removal performance from tungsten when applied to a workpiece containing tungsten and ruthenium. The composition of this invention comprises periodic acid or a salt thereof, a quaternary ammonium salt, a resin containing nitrogen atoms, and a solvent.

Description

[Technical Field]

[0001] This invention relates to a composition and a method for processing the composition. [Previous Technology]

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

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

[0004] For example, Patent Document 1 discloses a removal composition suitable for removing Ru from a substrate. More specifically, it discloses a removal composition comprising water, periodic acid, tetramethylammonium hydroxide, etc.

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-087945 [Summary of the Invention]

[0006] Ru can be used in wiring materials, etc., and sometimes tungsten (hereinafter also simply referred to as "W") can also be used in wiring materials, etc. In cases where both Ru and W are present on a substrate such as a semiconductor, it is necessary to selectively remove only Ru without corroding W. The inventors' research on the removal composition described in Patent Document 1 shows that its ability to selectively remove Ru relative to W is insufficient and further improvement is needed.

[0007] Therefore, the object of the present invention is to provide a composition in which Ru exhibits excellent removal properties of W when applied to a workpiece containing W and Ru. Furthermore, the object of the present invention is to provide a method for processing a workpiece using the above-described composition.

[0008] The inventors conducted in-depth research to solve the above-mentioned problems, and as a result, completed the present invention. That is, they discovered that the above-mentioned problems can be solved by the following configuration.

[0009] [1] A composition comprising: periodic acid or a salt thereof; a quaternary ammonium salt; a resin containing a nitrogen atom; and a solvent. [2] The composition of [1] for use in a ruthenium-containing material. [3] The composition of [1] or [2] wherein the resin has repeating units containing nitrogen atoms. [4] The composition of any one of [1] to [3] wherein the resin contains repeating units selected from the group consisting of repeating units represented by formula (1), repeating units represented by formula (2), repeating units represented by formula (3), and repeating units represented by formula (4). [5] The composition of [4] wherein the resin contains repeating units selected from the group consisting of repeating units represented by formula (1), repeating units represented by formula (2), and repeating units represented by formula (3). [6] A composition as described in [4], wherein the resin comprises a repeating unit represented by formula (1) described later. [7] A composition as described in [4], wherein the resin comprises a repeating unit represented by formula (3) described later. [8] A composition as described in any one of [1] to [7], wherein the resin has a repeating unit comprising a quaternary ammonium salt structure. [9] A composition as described in any one of [1] to [8], wherein the resin comprises a nitrogen atom in the main chain.

[10] A composition as described in any one of [1] to [9], wherein the periodic acid or a salt thereof comprises at least one selected from the group consisting of orthoperiodic acid, metaperiodic acid, and salts thereof.

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

[10] , wherein the quaternary ammonium salt comprises at least one selected from the group consisting of tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, ethyltrimethylammonium salt, triethylmethylammonium salt, diethyldimethylammonium salt, tributylmethylammonium salt, dimethyldipropylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, (2-hydroxyethyl)trimethylammonium salt, and (2-hydroxyethyl)triethylammonium salt.

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

[11] has a pH of 3.0 to 10.0.

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

[12] has a weight-average molecular weight of 1,000 to 200,000.

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

[13] has a content of the resin relative to the total mass of the composition of 1 to 1,000 ppm by mass.

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

[14] substantially does not contain insoluble particles.

[16] A method for treating a sample comprising ruthenium and tungsten by contacting the sample comprising any one of [1] to

[15] to remove ruthenium. [Effects of the Invention]

[0010] According to the present invention, a composition in which Ru exhibits excellent removal properties of W when applied to a workpiece containing W and Ru is provided. Furthermore, according to the present invention, a method for processing a workpiece containing W and Ru is also provided.

Implementation Method

[0012] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0013] The following explains the meaning of each statement in this specification. In this specification, the numerical range indicated by “~” refers to the range including the values ​​before and after “~” as lower and upper limits. In this specification, “ppm” is an abbreviation for “parts per million” and refers to 10⁻⁶. Also, “ppb” is an abbreviation for “parts per billion” and refers to 10⁻⁹. “ppt” is an abbreviation for “parts per trillion” and refers to 10⁻¹². In this specification, when a certain component exists in two or more forms, the “content” of that component refers to the total content of the two or more components.

[0014] Unless otherwise specified, “exposure” includes exposure based on mercury lamps, far-ultraviolet light such as excimer lasers, X-rays or EUV light, and depiction based on particle beams such as electron beams or ion beams. “Preparation” includes not only the synthesis or blending of specific materials, but also the acquisition of predetermined items through purchase.

[0015] The compounds described in this specification are not particularly limited and may include structural isomers (compounds with the same number of atoms but different structures), optical isomers, and isotopes. Furthermore, isomers and isotopes may include one or more types. In this specification, dry etching residue refers to byproducts generated by dry etching (e.g., plasma etching), such as organic residues derived from photoresist, Si-containing residues, and metal-containing residues (e.g., transition metal-containing residues). In this specification, regarding the bonding direction of divalent groups (e.g., -COO-), unless otherwise specified, in compounds represented by "XYZ" where Y is -COO-, the compound can be either "XO-CO-Z" or "X-CO-OZ".

[0016] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​converted from the polystyrene content of the standard material measured by gel permeation chromatography (GPC) using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all trade names manufactured by TOSOHCORPORATION) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard material. In this specification, unless otherwise specified, the molecular weight of compounds exhibiting molecular weight distribution is the weight-average molecular weight (Mw).

[0017] <Composition> The composition of the present invention comprises periodic acid or a salt thereof, a quaternary ammonium salt, a resin containing nitrogen atoms, and a solvent. When the composition of the present invention has the above-described structure and is applied to a workpiece containing W and Ru, the mechanism by which Ru exhibits excellent removal performance of W is not clearly understood, but the inventors speculate as follows: The composition, by comprising periodic acid or a salt thereof and a solvent, can exhibit removal energy (etching energy) for both W and Ru. However, it is believed that by comprising a resin containing nitrogen atoms, the composition can primarily inhibit the etching of W and selectively etch Ru. Furthermore, it is believed that by comprising a quaternary ammonium salt, the composition can promote the dissolution of Ru and selectively etch Ru. Hereinafter, the components that may be included in the composition will be described in detail. Furthermore, hereafter, the excellent removal performance of Ru of W when applied to a workpiece containing W and Ru will also be referred to as "excellent Ru / W selectivity".

[0018] [Periodic acid or its salts] The composition of the present invention comprises periodic acid or its salts. Examples of periodic acid or its salts include orthoperiodic acid (H5IO6), metaperiodic acid (HIO4), and salts thereof (e.g., sodium or potassium salts). Among these, orthoperiodic acid, orthoperiodate, or metaperiodic acid are preferred from the viewpoint of excellent Ru / W selectivity, with orthoperiodic acid being more preferred. One type of periodic acid or its salt may be used, or two or more may be used in combination. The content of periodic acid or its salt relative to the total mass of the composition is preferably 0.01 to 15.00% by mass, more preferably 0.10 to 10.00% by mass, and further preferably 0.10 to 5.00% by mass. When using two or more types of periodic acid or its salts, the total content of periodic acid or its salts is preferably within the above-mentioned preferred range. Furthermore, a portion of the periodic acid in the composition can also form a salt structure with the nitrogen-containing resin described later.

[0019] [Quadrivalent Ammonium Salts] The composition of the present invention comprises quadrivalent ammonium salts. Quadrivalent ammonium salts are compounds composed of quadrivalent ammonium cations and anions. There are no particular limitations on quadrivalent ammonium salts, but it is preferred to include quadrivalent ammonium salts represented by the following formula (a).

[0020] [Chemical Formula 1]

[0021] In formula (a), Ra to Rd each independently represent an alkyl group that may have substituents. The alkyl group can be linear or branched, with linear being preferred. The alkyl portion of the alkyl group is preferably 1 to 20 carbons, more preferably 1 to 8, and even more preferably 1 to 4. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl. Substituents include, for example, hydroxyl and phenyl. Examples of alkyl groups having substituents include 2-hydroxyethyl, 2-hydroxypropyl, and benzyl. Furthermore, the methylene group constituting the alkyl group can be substituted with divalent substituents such as -O-. The total number of carbons contained in the quaternary ammonium salt represented by formula (a) is not particularly limited, but 4 to 20 is preferred, and 4 to 14 is even more preferred. Furthermore, two alkyl groups selected from Ra to Rd that may have substituents may bond together to form a ring.

[0022] In formula (a), A- represents a monovalent anion. Examples of monovalent anions represented by A- include F-, Cl-, Br-, OH-, NO3-, CH3COO-, and CH3CH2SO4-, with F-, Cl-, Br-, or OH- being preferred, Cl- or OH- being more preferred, and OH- being even more preferred.

[0023] Examples of quaternary ammonium salts represented by formula (a) include tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, ethyltrimethylammonium salt, triethylmethylammonium salt, diethyldimethylammonium salt, tributylmethylammonium salt, dimethyldipropylammonium salt, dodecyltrimethylammonium salt, trimethyltetradecylammonium salt, hexadecyltrimethylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, (2-hydroxyethyl)trimethylammonium salt (also known as "choline"), (2-hydroxyethyl)triethylammonium salt, diethylbis(2-hydroxyethyl)ammonium salt, ethyltri(2-hydroxyethyl)ammonium salt, tri(2-hydroxyethyl)methylammonium salt, etc. From the viewpoint of excellent Ru / W selectivity, it is preferable that the quaternary ammonium salt includes at least one salt selected from the group consisting of tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, ethyltrimethylammonium salt, triethylmethylammonium salt, diethyldimethylammonium salt, tributylmethylammonium salt, dimethyldipropylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, (2-hydroxyethyl)trimethylammonium salt, and (2-hydroxyethyl)triethylammonium salt. It is also preferable that the anion contained in the above salt is F-, Cl-, Br-, or OH-, with Cl- or OH- being more preferred, and OH- being even more preferred.

[0024] One type of quaternary ammonium salt may be used, or two or more types may be used in combination. The total content of the quaternary ammonium salt relative to the total mass of the composition is preferably 0.01 to 10.00% by mass, more preferably 0.10 to 5.00% by mass, and further preferably 0.10 to 2.50% by mass. The molecular weight of the quaternary ammonium salt is preferably 90 to 1000, more preferably 90 to 500, further preferably 90 to 300, and particularly preferably 90 to 200.

[0025] [Resin Containing Nitrogen Atoms] The composition of the present invention comprises a resin containing nitrogen atoms (hereinafter also referred to as "nitrogen-containing resin"). Nitrogen-containing resin is a compound different from quaternary ammonium salts. Nitrogen-containing resin refers to a resin in which nitrogen atoms are contained in a portion of the resin. Resin refers to a compound polymerized from monomers, specifically a compound with a weight average molecular weight of 500 or more. Nitrogen-containing resin only needs to have nitrogen atoms in a portion of the resin, but it is preferable to include repeating units containing nitrogen atoms (hereinafter also referred to as "nitrogen-containing units"). Furthermore, nitrogen-containing resin may contain repeating units other than nitrogen-containing units (hereinafter also referred to as "other units").

[0026] (Nitrogen-containing unit) There are no particular restrictions on the form of the nitrogen atom in the nitrogen-containing unit, and the nitrogen atom can be cationic. Furthermore, in the nitrogen atom of the nitrogen-containing unit, the bonds between the nitrogen atom and the surrounding atoms can be all single bonds, or may include double bonds, or may include triple bonds. As for the form of the nitrogen atom in the nitrogen-containing unit, the structures represented by the following formulas (A) to (D) can be cited.

[0027] [Chemical Formula 2]

[0028] In formulas (A) to (D), * indicates the bonding position. In formulas (A), (B), and (D), R independently represents a hydrogen atom or a monovalent substituent, respectively. Examples of structures having the structure represented by formula (A) include primary amine structures, secondary amine structures, and tertiary amine structures. Furthermore, a primary amine structure refers to a structure in which two of the three atoms bonded to the nitrogen atom are hydrogen atoms, and one atom is an atom other than hydrogen (e.g., a carbon atom). A secondary amine structure refers to a structure in which one of the three atoms bonded to the nitrogen atom is a hydrogen atom, and two atoms are atoms other than hydrogen (e.g., a carbon atom). A tertiary amine structure refers to a structure in which the three atoms bonded to the nitrogen atom are atoms other than hydrogen (e.g., a carbon atom). An example of a structure having the structure represented by formula (B) is a quaternary ammonium salt structure. Furthermore, a quaternary ammonium salt structure refers to a salt in which the nitrogen atom is cationized, and the four atoms bonded to the nitrogen atom are atoms other than hydrogen atoms (e.g., carbon atoms), forming an anion through electrostatic bonding. Examples of structures having the structure represented by formula (C) include imine structures and aromatic imine structures (nitrogen atoms in pyridine rings and azole rings, etc.). Furthermore, an imine structure refers to a structure in which the nitrogen atom is bonded to two atoms, one as a single bond and the other as a double bond. Examples of structures having the structure represented by formula (D) include ammonium imide structures (salt structures in which the nitrogen atom in an imine structure is cationized and electrostatically bonded to an anion) and aromatic ammonium imide structures (salt structures in which the nitrogen atom in pyridine rings and azole rings, etc., is cationized and electrostatically bonded to an anion).

[0029] From the viewpoint of superior Ru / W selectivity, the structure represented by formula (A) or formula (B) is preferred as the form of the nitrogen atom in the nitrogen-containing unit. Therefore, a primary amine structure, a secondary amine structure, a tertiary amine structure, or a quaternary ammonium salt structure is preferred as the form of the nitrogen atom in the nitrogen-containing unit. From the viewpoint of superior Ru / W selectivity, a secondary amine structure, a tertiary amine structure, or a quaternary ammonium salt structure is more preferred as the form of the nitrogen atom in the nitrogen-containing unit, a tertiary amine structure or a quaternary ammonium salt structure is further preferred, and a quaternary ammonium salt structure is particularly preferred.

[0030] Furthermore, the nitrogen atom in the nitrogen-containing unit may be contained in either the main chain or the side chain, or in both. Moreover, in this specification, "main chain" refers to the longest bond in the molecule constituting the polymer of the resin, and "side chain" refers to a branch group of atoms that branches from the main chain. From the viewpoint of superior Ru / W selectivity, it is preferable that the nitrogen atom in the nitrogen-containing unit is at least contained in the main chain.

[0031] As a more specific structure of nitrogen-containing unit, the repeating unit represented by the following formulas (1) to (4) can be cited.

[0032] [Chemical Formula 3]

[0033] In formula (1), L11 to L15 independently represent single bonds or divalent linking groups. Examples of divalent linking groups represented by L11 and L12 include alkyl groups, cycloalkyl groups, aryl groups, -O-, -S-, -CO-, -COO-, -CONH-, and -SO2-, as well as groups formed by combining one or more divalent linking groups selected from the group including -O-, -S-, -CO-, -COO-, -CONH-, and -SO2- with alkyl groups, cycloalkyl groups, and aryl groups. The alkyl groups can be either linear or branched, with linear being preferred. There is no particular limitation on the number of carbon atoms in the alkyl group, but 1 to 10 is preferred, 1 to 5 is more preferred, and 1 to 3 is further preferred. The cycloalkyl groups can be either monocyclic or polycyclic, with monocyclic being preferred. The number of carbon atoms in the cycloalkyl group is not particularly limited, but 5 to 12 is preferred, and 5 to 8 is even more preferred. The aryl group can be either monocyclic or polycyclic, with monocyclic being preferred. Furthermore, the aryl group can be a heteroaryl group in which the ring member atoms include atoms other than carbon atoms. The number of ring member atoms in the aryl group is not particularly limited, but 5 to 15 is preferred, and 5 to 10 is even more preferred. In the above, L11 and L12 are preferably single bonds, alkyl groups, or groups formed by combining alkyl groups with -SO2-, with alkyl groups being even more preferred. More specifically, as the alkyl groups represented by L11 and L12, methylene, ethyl, or propyl groups are preferred. In formula (1), L13 to L15 independently represent single bonds or divalent linkage groups, respectively. Examples of divalent linking groups represented by L13 to L15 include alkyl groups, -O-, -S-, -CO-, -COO-, -CONH-, and -SO2-, as well as groups formed by combining one or more divalent linking groups selected from the group including -O-, -S-, -CO-, -COO-, -CONH-, and -SO2- with an alkyl group. Preferred alkyl groups are as described above. In the above, it is preferred that L13 is a single bond or an alkyl group, with a single bond being more preferred. It is preferred that L14 and L15 are single bonds or alkyl groups, with an alkyl group being more preferred. More specifically, methylene or ethyl groups are preferred as alkyl groups represented by L14 and L15.

[0034] In formula (1), X represents a divalent linker containing a nitrogen atom. Preferably, the divalent linker containing a secondary amine structure, a tertiary amine structure, or a quaternary ammonium salt structure is a divalent linker. More specifically, the divalent linker represented by formula (X1) or the divalent linker represented by formula (X2) is preferred.

[0035] [Chemical Formula 4]

[0036] In formulas (X1) and (X2), * indicates the bond position. In formula (X1), R12 represents a hydrogen atom or a monovalent substituent. Examples of monovalent substituents represented by R12 include alkyl groups having 1 to 6 carbon atoms. The alkyl group can be linear or branched, with linear being preferred. It is preferred that the alkyl group has 1 to 4 carbon atoms, and more preferably 1 to 3. Examples of substituents for alkyl groups that can have substituents include halogen atoms, carboxyl groups, sulfonyl groups, and hydroxyl groups. In the above, it is preferred that R12 is a hydrogen atom or an unsubstituted alkyl group, with unsubstituted alkyl being more preferred. More specifically, it is preferred that the unsubstituted alkyl group is methyl, ethyl, or propyl. Furthermore, the divalent linker group represented by formula (X1) can form a salt with an acid. Examples of acids that form salts with the divalent linker represented by formula (X1) include sulfuric acid, sulfurous acid, iodic acid, hydrogen chloride, hydrogen bromide, nitric acid, aminosulfonic acid, acetic acid, ethyl sulfuric acid, and methanesulfonic acid.

[0037] In formula (X2), R13 and R14 independently represent monovalent substituents. Examples of monovalent substituents represented by R13 and R14 include R12, and the preferred form is also the same. In formula (X2), A- represents a monovalent anion. The monovalent anion represented by A- can be an inorganic anion or an organic anion. Examples of inorganic anions include bisulfate ion (HSO4-), bisulfite ion (HSO3-), iodate ion (IO3-), halide ion, and nitrate ion. Examples of organic anions include acetate ion, ethyl sulfate ion, and methanesulfonate ion. Among these, halide ion or ethyl sulfate ion is preferred. Examples of halide ions include fluoride ion, chloride ion, bromide ion, and iodide ion, with chloride ion being preferred.

[0038] In formula (1), R11 represents a monovalent substituent, and the presence of multiple R11s independently represents a monovalent substituent. Examples of monovalent substituents represented by R11 include alkyl groups, halogen atoms, and hydroxyl groups. The alkyl groups that can have substituents are the same as those described for monovalent substituents represented by R12. In formula (1), n1 represents an integer from 0 to 5. It is preferred that n1 is 0 to 3, more preferred that it is 0 to 2, further preferred that it is 0 or 1, and especially preferred that it is 0.

[0039] In formula (2), L21 represents a divalent linker. Examples of divalent linkers represented by L21 include L11 and L12, with the same preferred form. That is, alkyl groups are preferred as divalent linkers represented by L21, with methylene, ethyl, or propyl groups being more preferred. Furthermore, regarding the hydrogen atom of the alkyl group, one or more can be replaced by a monovalent substituent, such as a halogen atom and a hydroxyl group. In formula (2), L22 represents a single bond or a divalent linker. Examples of divalent linkers represented by L22 include L11 and L12. As the divalent linker represented by L22, it is preferable to use a group consisting of -COO-, -CONH-, or an alkyl group, or a group formed by combining one or more divalent linkers selected from the group consisting of -O-, -S-, -CO-, -COO-, -CONH-, and -SO2- with an alkyl group. In the above, it is preferable that L22 is a single bond, an alkyl group, or -COO-alkyl, with an alkyl group being more preferred.

[0040] In formula (2), R21 represents a hydrogen atom or a monovalent substituent. Examples of monovalent substituents represented by R21 include halogen atoms and alkyl groups having 1 to 3 carbon atoms. Preferably, R21 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In formula (2), R22 represents a monovalent substituent containing a nitrogen atom. Preferably, the monovalent substituent containing a nitrogen atom represented by R22 is a monovalent substituent containing the structure represented by formulas (A) to (D) above, and more preferably, a monovalent substituent represented by formulas (B1) to (B8) below.

[0041] [Chemical Formula 5]

[0042] In formulas (B1) to (B8), * indicates a bond position. In formulas (B1) and (B3), R23 to R25 independently represent a hydrogen atom or a monovalent substituent. R12 can be cited as a monovalent substituent represented by R23 to R25. Preferably, R23 to R25 are hydrogen atoms or unsubstituted alkyl groups, with hydrogen atoms being more preferred. In formulas (B5) to (B8), R26 to R29 independently represent a monovalent substituent. R12 can be cited as a monovalent substituent represented by R26 to R29. Preferably, R26 to R29 are unsubstituted alkyl groups in formulas (B5) to (B8).

[0043] In formulas (B2) to (B4) and (B6) to (B8), R2 represents a monovalent substituent. The presence of multiple R2s independently represents monovalent substituents. Groups identical to those represented by R11 can be cited as monovalent substituents represented by R2. In formulas (B3), (B4), (B7), and (B8), m represents an integer from 0 to 4. n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0. In formulas (B5) to (B8), A- represents a monovalent anion. Regarding A- in formulas (B5) to (B8), anions identical to those in formula (X2) above can be cited, and the preferred forms are also the same.

[0044] Furthermore, the monovalent substituents represented by formulas (B1) to (B4) can form salts with acids. As an acid that forms a salt with the monovalent substituents represented by formulas (B1) to (B4), an acid that forms a salt with the divalent linking group represented by formula (X1) can be cited.

[0045] In the above, as the substituent containing a nitrogen atom represented by R22, the substituent represented by formula (B1), the substituent represented by formula (B2) or the substituent represented by formula (B5) is preferred, and the substituent represented by formula (B1) is even more preferred.

[0046] In formula (3), L31 represents a divalent linker. Examples of divalent linkers represented by L31 include L11 and L12, with alkyl groups being preferred. The carbon number of the alkyl group is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 6. That is, propyl, butyl, pentyl, or hexyl are preferred. Furthermore, regarding the hydrogen atom of the alkyl group, one or more can be replaced by a monovalent substituent, such as halogen atoms and hydroxyl groups. Examples of the state in which the hydrogen atom of the alkyl group is replaced by a monovalent substituent include -CH2-CHOH-CH2- and -CH2-CH2-CHOH-CH2-. In formula (3), R31 and R32 each independently represent a monovalent substituent. As a monovalent substituent represented by R31 and R32, a monovalent substituent represented by R12 can be cited, and the preferred state is also the same. That is, as a monovalent substituent represented by R31 and R32, an unsubstituted alkyl group is preferred, and methyl, ethyl or propyl is even more preferred. In formula (3), A- represents a monovalent anion. Regarding A- in formula (3), the same anion as A- in the above formula (X2) can be cited, and the preferred state is also the same.

[0047] In formula (4), L41 represents a divalent linker. Examples of divalent linkers represented by L41 include L11 and L12, with alkyl groups being preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 2 to 4. In formula (4), R41 represents a hydrogen atom or a monovalent substituent. Examples of monovalent substituents represented by R41 include R12, with the same preferred form. That is, as a monovalent substituent represented by R41, an unsubstituted alkyl group is preferred, with methyl, ethyl, or propyl being more preferred. Hydrogen atoms are preferred.

[0048] Furthermore, the repeating units represented by formulas (1) and (2) are in the form of having nitrogen atoms in the side chain, and the repeating units represented by formulas (3) and (4) are in the form of having nitrogen atoms in the main chain.

[0049] As the nitrogen-containing unit contained in the nitrogen-containing resin, from the viewpoint of Ru / W selectivity, the repeating unit represented by formula (1) to (3) is better, the repeating unit represented by formula (1) or formula (3) is more preferred, and the repeating unit represented by formula (1) is even better.

[0050] Furthermore, the nitrogen-containing resin may contain other nitrogen-containing units besides those mentioned above. There are no particular limitations on other nitrogen-containing units, and they may be known nitrogen-containing units. Other nitrogen-containing units may be repeating units formed by crosslinking repeating units represented by formulas (1) to (4) above through crosslinking groups or crosslinking molecules. Examples of crosslinking groups include epoxy groups and vinyl unsaturated groups. Examples of crosslinking molecules include isocyanate compounds, epichlorohydrin, and formaldehyde.

[0051] The nitrogen-containing resin may contain a plurality of nitrogen-containing units. The total content of the nitrogen-containing units relative to the total mass of the nitrogen-containing resin is preferably 5-100% by mass, more preferably 20-100% by mass, and further preferably 40-100% by mass. The total content of the nitrogen-containing units relative to all repeating units of the nitrogen-containing resin is preferably 5-100 moles, more preferably 20-100 moles, and further preferably 40-100 moles.

[0052] (Other Units) There are no particular limitations on the other units that the nitrogen-containing resin may contain, and they may be known repeating units. Examples of other units include repeating units based on monomers having vinyl unsaturated groups. Examples of monomers having vinyl unsaturated groups include carboxylic acids having vinyl unsaturated groups. Examples of the aforementioned carboxylic acids having vinyl unsaturated groups include acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid, and maleic anhydride, as well as their salts. Furthermore, they may be condensation or addition compounds of the aforementioned carboxylic acids with compounds having hydroxyl groups, compounds having amino groups, and compounds having glycidyl groups. Examples of the aforementioned compounds include ester compounds of acrylic acid or methacrylic acid with compounds having hydroxyl groups, amide compounds of acrylic acid or methacrylic acid with compounds having primary or secondary amino groups, and half-ester compounds of maleic acid with compounds having hydroxyl groups. Furthermore, as other units, repeating units based on vinyl acetate can also be cited, and these repeating units based on vinyl acetate can also be decarboxylated through modification such as hydrolysis. That is, they can also be considered as constituent units based on vinyl alcohol.

[0053] The nitrogen-containing resin may contain a plurality of other units. The content of other units relative to the total mass of the nitrogen-containing resin is preferably 0-95% by mass, more preferably 0-80% by mass, and further preferably 0-60% by mass. The content of nitrogen-containing units relative to all repeating units of the nitrogen-containing resin is preferably 5-100% by mass, more preferably 20-100% by mass, and further preferably 40-100% by mass.

[0054] Specific examples of nitrogen-containing resins include resins synthesized using each of the following monomers as monomers: allylamine and its salt, N-alkylallylamine and its salt, N,N-dialkylallylamine and its salt, trialkylallylammonium salt, diallylamine and its salt, N-alkyldiallylamine and its salt, and N,N-dialkylammonium salt. Furthermore, regarding the alkyl group in each of the above monomers, methyl and ethyl groups can be independently cited. Also, compounds that form salts with the above amines include hydrogen chloride (hydrochloric acid), aminosulfonic acid, acetic acid, and ethyl sulfuric acid. Chloride ions can be cited as the relative anions of the above ammonium salts.

[0055] Furthermore, resins synthesized using diallylamine and the like as monomers can be polymerized with accompanying cyclization to become resins containing repeating units represented by formula (1). Specific compound names for the above-mentioned resins include polyallylamine, polyallylamine hydrochloride, polydiallylamine, polydiallylamine hydrochloride, poly(diallyldimethylammonium chloride), and poly(methylethyldimethylethylammonium sulfate). Furthermore, the resins listed above are resins containing repeating units having a cyclic structure.

[0056] Furthermore, the resin synthesized using the above-mentioned N,N-dialkylammonium salt as a monomer can be polymerized to become a resin containing repeating units represented by formula (3). A specific compound name for the above-mentioned resin is poly(diallyldimethylammonium chloride). Moreover, the resins listed above are resins containing repeating units with a chain structure.

[0057] Furthermore, as a nitrogen-containing resin, copolymers synthesized from two or more monomers selected from the above-mentioned monomers can also be cited. For example, copolymers synthesized using allylamine and diallylamine as monomers, and copolymers synthesized using allylamine salts and diallylamine salts as monomers can be cited. In addition, as a nitrogen-containing resin, copolymers synthesized using the above-mentioned monomers and maleic acid as monomers can also be cited. For example, copolymers synthesized using diallylamine and maleic acid as monomers can be cited.

[0058] As a specific example of a nitrogen-containing resin, a resin having the framework structure represented by the following formulas (P-1) to (P-23) can also be cited. In formulas (P-1) to (P-23), the repeating unit marked with the symbol m is designated as the first repeating unit, and the repeating unit marked with the symbol n is designated as the second repeating unit. Furthermore, the framework structure represented by formulas (P-1) to (P-23) contains a plurality of repeating units, and there are no particular restrictions on the bonding pattern of the plurality of repeating units. For example, the plurality of repeating units can be randomly bonded (so-called, random copolymer), alternately bonded (so-called, alternating copolymer), or block-shaped bonded (so-called, block copolymer).

[0059] [Chemical Formula 6]

[0060] In the above formulas (P-1) to (P-23), the ratio (m / n) of the mole number m of the first repeating unit to the mole number n of the second repeating unit is 1 / 20 to 20 / 1. Also, in formula (P-7), l represents the number of repeats of the oxy-p-alkyl unit and is an integer from 1 to 30. Also, in formula (P-20), X represents a nitrile, nitrile, amino hydrochloride, or methylamino group.

[0061] As another specific example of a nitrogen-containing resin, a resin formed by the condensation polymerization of dimethylamine and epichlorohydrin (poly(2-hydroxypropyl)dimethylammonium chloride) can be cited. Furthermore, a resin formed by the condensation polymerization of dimethylamine and epichlorohydrin is a resin containing the repeating unit represented by formula (3).

[0062] Furthermore, as another specific example of a nitrogen-containing resin, polyethyleneimine obtained by ring-opening polymerization of ethyleneimine can be cited. Polyethyleneimine can be in linear, branched, and dendritic polymeric forms, and in the linear form, it has repeating units represented by formula (4). Furthermore, regarding branched polyethyleneimine, a resin composed of units represented by formulas (4-a), (4-b), and (4-c) can be cited. Furthermore, * and ** in each formula indicate the bonding position, with * and ** bonded. Regarding dendritic polymeric polyethyleneimine, a resin composed of units represented by formulas (4-a) and (4-c) can be cited. Furthermore, * and ** in each formula indicate the bonding position, with * and ** bonded. Furthermore, the resin ends in **-CH2-CH2-NH2.

[0063] [Chemical Formula 7]

[0064] Furthermore, as well-known nitrogen-containing resins, examples include paragraphs

[0036] to

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

[0040] to

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

[0025] to

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

[0062] to

[0065] of Japanese Patent Application Publication No. 2004-27162, and paragraphs

[0068] to

[0069] of Japanese Patent Application Publication No. 2004-115675. Nitrogen-containing resins described in paragraph 84, paragraphs

[0051] to

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

[0097] to

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

[0026] to

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

[0037] to

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

[0062] to

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

[0065] Commercially available nitrogen-containing resins may also be used. Examples of commercially available nitrogen-containing resins include PAA-HCL-01, PAA-HCL-03, PAA-HCL-05, PAA-SA, PAA-01, PAA-03, PAA-05, PAA-08, PAA-15C, PAA-25, PAA-D19A, PAA-D11, PAA-1123, PAA-U5000, PAA-U7030, and PAA-N5000 manufactured by NITTOBOMEDICAL CO., LTD. PAS-21CL, PAS-21, PAS-M-1L, PAS-M-1, PAS-M-1A, PAS-H-1L, PAS-H-5L, PAS-H10L, PAS-24, PAS-92, PAS-92A, PAS-240 1. PAS-A-1, PAS-A-5, PAS-2141CL, PAS-2223, PAS-880, PAA-1151, PAS-410L, PAS-410SA, PAS-2251, PAS-84 and PAS-2351. Other commercially available nitrogen-containing resins besides those mentioned above include, for example, the Catiomaster (registered trademark) PD series (PD-7, and PD-30), Catiomaster (registered trademark) series (PE-30, EPA-SK01, and PAE-01) manufactured by Yokkaichi Chemical Co., Ltd.; the Unisense (registered trademark) series (KHE100L, KHE107L, KHE1000L, FPA100L, FPA101L, FPA1000L, FCA1003L, FCA1001L, and KCA100L) manufactured by SENKA corporation; and the ACRIT (registered trademark) series (1SX-1055F, 1SX-6000, and 1WX-1020) manufactured by TAISEI FINE CHEMICAL CO.,LTD.

[0066] It is preferable that the weight average molecular weight of the nitrogen-containing resin is 1,000 or more, and even more preferable that it is 1,500 or more. There is no particular upper limit to the weight average molecular weight of the nitrogen-containing resin, but it is preferable that it is 500,000 or less, 200,000 or less, even more preferable that it is 20,000 or less, and even more preferable that it is 8,000 or less.

[0067] One type of nitrogen-containing resin may be used, or two or more types may be used in combination. The content of the nitrogen-containing resin relative to the total mass of the composition is preferably 0.1 to 1500 ppm by mass, more preferably 1 to 1000 ppm by mass, further preferably 1 to 500 ppm by mass, particularly preferably 1 to 200 ppm by mass, and optimally 5 to 200 ppm by mass. When using two or more types of nitrogen-containing resins, the total content of the nitrogen-containing resin within the above-mentioned preferred range is preferable.

[0068] The mass ratio of periodic acid or its salt content to nitrogen-containing resin content is preferably 5 to 150,000, more preferably 5 to 20,000, further preferably 10 to 20,000, especially preferably 30 to 10,000, and best preferably 50 to 2,000.

[0069] [Solvent] The composition of the present invention includes a solvent. Examples of solvents include water and organic solvents, with water being preferred. As water, purified water such as distilled water, ion-exchanged water, and ultrapure water is preferred, and ultrapure water used in semiconductor manufacturing is even more preferred. The water contained in the composition may contain unavoidable trace amounts of mixed components. The water content relative to the total mass of the composition is preferably 50% by mass or more, more preferably 65% ​​by mass or more, and further preferably 75% by mass or more. There is no particular upper limit, but it is preferred to be 99.999% by mass or less relative to the total mass of the composition, and even more preferably 99.9% by mass or less.

[0070] Water-soluble organic solvents are preferred as organic solvents. Water-soluble organic solvents refer to organic solvents that can be mixed with water in any proportion. Examples of water-soluble organic solvents include ether solvents, alcohol solvents, ketone solvents, amide solvents, sulfur-containing solvents, and lactone solvents.

[0071] Examples of ether solvents include diethyl ether, diisopropyl ether, dibutyl ether, tributyl methyl ether, cyclohexyl methyl ether, tetrahydrofuran, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, alkyl glycol monoalkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether), and alkyl 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 number of carbon atoms in the ether solvent is preferably 3 to 16, more preferably 4 to 14, and further preferably 6 to 12.

[0072] Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, propylene glycol, glycerol, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol. The number of carbon atoms in the alcohol solvent is preferably 1 to 8, and more preferably 1 to 4.

[0073] Examples of acetamide solvents include methylamine, monomethylmethylamine, dimethylmethylamine, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0074] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0075] Examples of sulfur-containing solvents include dimethyl sulfide, dimethyl sulfide and cyclobutane.

[0076] Examples of lactone solvents include γ-butyrolactone and δ-valerolactone.

[0077] One organic solvent may be used alone, or two or more may be used in combination. The content of the organic solvent relative to the total mass of the composition is preferably 0.1% to 10% by mass. Even when using two or more organic solvents, the total content of the two or more organic solvents is preferably within the above range.

[0078] [Any Components] In addition to the components described above, the composition may also contain any other components. The following is a detailed description of any other components that may be contained in the composition.

[0079] (Basic Compound) The composition may include a basic compound. A basic compound is a compound that exhibits basicity (pH greater than 7.0) in aqueous solution. Examples of basic compounds include organic bases, inorganic bases, and their salts. However, the basic compound does not contain the aforementioned quaternary ammonium salts, solvents, or the aforementioned nitrogen-containing resins.

[0080] 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, lactamine compounds, and isonitrile compounds. Furthermore, amine compounds are compounds having an amino group within their molecule, meaning compounds not included in the aforementioned alkanolamines, amine oxide compounds, and lactamine compounds. However, the aforementioned organic bases do not include the aforementioned quaternary ammonium salts or the aforementioned resins containing nitrogen atoms.

[0081] Examples of amine compounds include primary amines having a primary amino group (-NH2) within the molecule, secondary amines having a secondary amino group (>NH) within the molecule, and tertiary amines having a tertiary amino group (>N-) within the molecule. Examples of primary, secondary, and tertiary amines include alkylamines, dialkylamines, and trialkylamines, respectively. The alkyl group may have substituents. Also, examples of alicyclic amine compounds having an alicyclic (non-aromatic) structure with a nitrogen atom within the molecule, and salts of such compounds, may be given. Furthermore, the alicyclic ring in the alicyclic amine compound may be monocyclic or polycyclic. Also, the alicyclic ring may contain heteroatoms (e.g., nitrogen atom, oxygen atom, sulfur atom). Also, the alicyclic ring may have substituents; there are no particular limitations on the substituents that the alicyclic ring may have, but examples of alkyl, aralkyl, hydroxyalkyl, and aminealkyl groups may be given. Salts of amine compounds include, for example, salts of acids that form salts with the divalent linkage group represented by formula (X1) above, among which hydrochloride, sulfate, or nitrate salts are preferred. Furthermore, it is preferable that the amine compound is water-soluble, preferably dissolving at least 50g in 1L of water.

[0082] Examples of primary amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, methoxyethylamine, methoxypropylamine, and tetrahydrofurfurylamine. Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, and dibutylamine (DBA). Examples of tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylethylamine, dimethylpropylamine, diethylmethylamine, dimethylhydroxyethylamine, N-methyldiethanolamine, and benzyldimethylamine. Examples of alicyclic amine compounds include 1,8-diazinobicyclo[5.4.0]-7-undecene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO), N-(2-aminoethyl)piperidine, hydroxyethylpiperidine, piperidine, 2-methylpiperidine, trans-2,5-dimethylpiperidine, cis-2,6-dimethylpiperidine, 2-piperidinemethanol, cyclohexylamine, and 1,5-diazabicyclo[4,3,0]-5-nonene.

[0083] Examples of lactamine compounds include ε-caprolactam.

[0084] Examples of inorganic bases include, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, and ammonia or its salts.

[0085] There is no particular limitation on the content of the alkaline compound, but it is preferable to be 0.1% by mass or more relative to the total mass of the composition, and even more preferable to be 0.5% by mass or more. There is no particular upper limit, but it is preferable to be 20.0% by mass or less relative to the total mass of the composition. It is also preferable to adjust the alkaline compound within the above-mentioned preferred range to the preferred pH range of the composition described later.

[0086] (Acidic Compound) The composition may include an acidic compound. An acidic compound is defined as an acidic compound that exhibits acidity (pH less than 7.0) in aqueous solution. However, the acidic compound does not contain periodic acid or its salts, or resins containing nitrogen atoms. Examples of acidic compounds include inorganic acids, organic acids, and their salts.

[0087] As inorganic acids, examples include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, fluoric acid, iodic acid, perchloric acid, hypochlorous acid, and salts thereof, with sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, or iodic acid being preferred, and nitric acid, sulfuric acid, hydrochloric acid, or iodic acid being even more preferred.

[0088] Examples of organic acids include carboxylic acids, sulfonic acids, and their salts. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, and butyric acid, which are lower (1 to 4 carbon atoms) aliphatic monocarboxylic acids, and their salts. Examples of sulfonic acids include methanesulfonic acid, benzenesulfonic acid, p-tosicacid, and their salts.

[0089] As an acidic compound, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfonic acid, or salts thereof are preferred, and sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, or p-toluenesulfonic acid are even more preferred.

[0090] There is no particular limitation on the content of acidic compounds, but it is preferable to be 0.1% by mass or more relative to the total mass of the composition, and more preferably 0.5% by mass or more. There is no particular upper limit, but it is preferable to be 20.0% by mass or less relative to the total mass of the composition. It is also preferable to adjust the acidic compounds within the above-mentioned preferred range to the preferred pH range of the composition described later.

[0091] (Water-soluble polymer) The composition of the present invention may include a water-soluble polymer. However, the water-soluble polymer does not include the compounds contained in the aforementioned nitrogen-containing resin and the metal corrosion inhibitor described later. Examples of water-soluble polymers include polyacrylic acid, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, and carboxyethylene polymers.

[0092] (Surfactant) The composition of the present invention may include a surfactant. However, the surfactant does not include the aforementioned nitrogen-containing resin. As a surfactant, there are no particular limitations as long as it is a compound having both a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule; for example, anionic surfactants and nonionic surfactants can be cited.

[0093] There are no particular limitations on the hydrophobic group possessed by the surfactant; examples include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. When the hydrophobic group includes an aromatic hydrocarbon group, it is preferable that the hydrophobic group has 6 or more carbon atoms, and more preferably 10 or more. When the hydrophobic group does not contain an aromatic hydrocarbon group and is composed only of an aliphatic hydrocarbon group, it is preferable that the hydrophobic group has 8 or more carbon atoms, and more preferably 10 or more. There is no particular upper limit to the number of carbon atoms in the hydrophobic group, but 24 or less is preferable, and 20 or less is even more preferable.

[0094] Examples of anionic surfactants include anionic surfactants having a hydrophilic group selected from the group consisting of sulfonic acid group, carboxyl group, sulfate ester group and phosphonic acid group within the molecule.

[0095] Examples of anionic surfactants having sulfonic acid groups include alkyl sulfonic acids, alkylbenzene sulfonic acids, alkylnaphthalene sulfonic acids, alkyl diphenyl ether sulfonic acids, fatty acid amide sulfonic acids, polyoxyethylene aryl ether sulfonic acids, polyoxyethylene alkyl ether sulfonic acids, polycyclic phenyl ether sulfates, and their salts. Examples of anionic surfactants having phosphonic acid groups include polyoxypropylene alkyl ether phosphonic acids, polyoxyethylene alkyl ether phosphonic acids, and their salts. Examples of anionic surfactants having carboxyl groups include polyoxyethylene alkyl ether carboxylic acids, polyoxyethylene alkyl ether acetic acids, polyoxyethylene alkyl ether propionic acids, fatty acids, and their salts. Examples of salts of anionic surfactants include ammonium salts, sodium salts, potassium salts, and tetramethylammonium salts.

[0096] A single surfactant may be used alone, or two or more may be used in combination. It is preferable that the surfactant content is 0.01% by mass or more relative to the total mass of the composition, and more preferably 0.03% by mass or more. There is no particular upper limit, but from the viewpoint of inhibiting foaming of the composition, it is preferable that it is 10% by mass or less relative to the total mass of the composition, and more preferably 5% by mass or less.

[0097] (Insoluble particles) It is preferable that the composition of the present invention does not substantially contain insoluble particles. The term "insoluble particles" refers to particles of inorganic solids and organic solids, etc., which are particles that ultimately do not dissolve in the composition but exist as particles. "Substantially not containing insoluble particles" means that when the composition is diluted 10,000 times using a solvent contained in the composition to obtain the composition for measurement, the number of particles with a diameter of 50 nm or larger contained in 1 mL of the composition for measurement is 40,000 or less. Furthermore, the number of particles contained in the composition for measurement can be determined in the liquid phase using a commercially available particle counter. Commercially available particle counter devices include those manufactured by RION Co., Ltd. and PMS Inc. Examples of the former include the KS-19F, and examples of the latter include the Chem20. For measuring larger particles, devices such as the KS-42 series and the LiQuilaz II S series can be used. Examples of insoluble particles include inorganic solids such as silicon dioxide (including colloidal silicon dioxide and fumed silicon dioxide), alumina, zirconium dioxide, cerium oxide, titanium dioxide, germanium oxide, manganese oxide, and silicon carbide; and organic solids such as polystyrene, polyacrylic acid resin, and polyvinyl chloride. Methods for removing insoluble particles from the composition include purification processes such as filtration.

[0098] (Metal Corrosion Inhibitor) The composition may contain a metal corrosion inhibitor. However, the aforementioned nitrogen-containing resin is not included in the metal corrosion inhibitor. There are no particular limitations on the type of metal corrosion inhibitor, and known metal corrosion inhibitors can be used. As a metal corrosion inhibitor, a metal corrosion inhibitor containing nitrogen atoms is preferred. For example, chelating agents, which are described in detail later, can be cited.

[0099] - 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, piperazine groups, pyrrole groups, pyrrolidyl groups, pyrrolidyl groups, piperidine groups, guanidine groups, biguanidine groups, carbazole groups, hydrazine groups, hemicarbazine groups, and aminoguanidine groups. The chelating agent may have two or more nitrogen-containing groups, and the 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 can be neutralized to form a salt. As a chelating agent, the chelating agents described in paragraphs

[0021] to

[0047] of Japanese Patent Application Publication No. 2017-504190 can be used, and such contents are incorporated in this specification.

[0100] A chelating agent may be used alone or in combination of two or more. The content of the chelating agent relative to the total mass of the composition is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass, and further preferably 0.3 to 1.0% by mass.

[0101] -Other Metal Corrosion Inhibitors- The metal corrosion inhibitor may be a benzotriazole that may have substituents. However, this excludes the benzotriazoles included in the above-mentioned chelating agents. Examples of benzotriazoles that can have substituents include benzotriazole (BTA), 5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenyl sulfide-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthiazole, 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, 4-propylbenzotriazole, 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-tert-butylbenzotriazole, 5-(1',1'-dimethylpropyl)-benzotriazole, 5-(1',1',3'-trimethylbutyl)benzotriazole, 5-n-octylbenzotriazole, and 5-(1',1',3',3'-tetramethylbutyl)benzotriazole.

[0102] There is no particular limitation on the content of the metal corrosion inhibitor, but it is preferable to be 0.1% by mass or more relative to the total mass of the composition, and even more preferably 1% by mass or more. There is no particular upper limit, but it is preferable to be 10% by mass or less relative to the total mass of the composition, and even more preferably 5% by mass or less.

[0103] (Metallic Component) The composition may contain a metallic component. Examples of metallic components include metal particles and metal ions. For example, the content of a metallic component refers to the total content of metal particles and metal ions. The composition may contain either metal particles or metal ions, or both.

[0104] The metal atoms included in the metallic component may be, for example, metal atoms selected from the group consisting of Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sn, Sr, Ti, Zn, and Zr. The metallic component may contain one type of metal atom or two or more types. The metal particles may be monomers or alloys, or may exist in the form of a combination of metal and organic matter. The metallic component may be a metallic component that is unavoidably included in each component (raw material) included in the composition, or a metallic component that is unavoidably included during the manufacture, storage, and / or transfer of the composition, or a metallic component that is intentionally added. When the composition contains a metallic component, the content of the metallic component relative to the total mass of the composition is typically 0.01 mass ppt to 10 mass ppm, preferably 0.1 mass ppt to 1 mass ppm, and more preferably 0.1 mass ppt to 100 mass ppb.

[0105] The types and contents of metal components in the composition can be determined by ICP-MS (Inductively Coupled Plasma Mass Spectrometry). In ICP-MS, the content of the metal component being measured is determined regardless of its form. Therefore, the total mass of the metal particles and metal ions being measured is quantified as the content of the metal component. For example, Agilent Technologies Japan, Ltd.'s Agilent 8800 triple quadrupole ICP-MS (Inductively Coupled Plasma Mass Spectrometry, for semiconductor analysis, Option #200), Agilent 8900, and PerkinElmer Co., Ltd.'s NexION350S can be used for the determination.

[0106] The method for adjusting the content of each metal component in the composition is not particularly limited. For example, by performing known processes to remove metals from the composition and / or from raw materials containing each component used in the preparation of the composition, the content of metal components in the composition can be reduced. Furthermore, by adding a compound containing metal ions to the composition, the content of metal components in the composition can be increased.

[0107] <Shape of the composition> The chemical and physical properties exhibited by the composition will be described below.

[0108] [pH] The pH of the composition of the present invention is not particularly limited, for example, a range of 1.0 to 14.0 can be cited. Among these, from the viewpoint of superior Ru / W selectivity, a pH of 1.0 to 12.0 is preferred, 3.0 to 10.0 is more preferred, and 4.0 to 7.5 is further preferred. In this specification, the pH of the composition is a value obtained by measurement at 25°C using a pH meter (manufactured by HORIBA, Ltd., F-51 (trade name)).

[0109] [Coarse Particles] It is preferable that the composition does not substantially contain coarse particles. "Coarse particles" refers to particles with a diameter of 0.2 μm or more when the particle shape is considered as spheres. Furthermore, particles included in the aforementioned insoluble particles may be included in coarse particles. Also, "substantially does not contain coarse particles" means that when the composition is measured using a commercially available measuring device in a light scattering liquid particle determination method, there are 10 or fewer particles larger than 0.2 μm in 1 mL of the composition. It is preferable that the lower limit is 0 or more. The coarse particles contained in the composition include particles such as garbage, dust, organic solids and inorganic solids contained as impurities in the raw materials, as well as particles such as garbage, dust, organic solids and inorganic solids introduced as contaminants during the preparation of the composition, which are equivalent to particles that are ultimately insoluble in the composition and exist as particles. One method for determining the content of coarse particles is, for example, the light scattering liquid particle determination method using a laser as a light source, which involves measuring the particles in the liquid phase using a commercially available measuring device. Another method for removing coarse particles is, for example, filtration.

[0110] <Method for Manufacturing the Composition> There are no particular limitations on the method for manufacturing the composition of the present invention. For example, it can be manufactured by mixing the above-described components. The order or timing of mixing the components, as well as the order and timing, are not particularly limited. For example, a method can be given where periodic acid or its salt, a quaternary ammonium salt, a nitrogen-containing resin, and any other component are added sequentially to a mixer containing purified pure water, and then the mixture is stirred thoroughly to mix the components and manufacture the composition. As a method for manufacturing the composition, a method can also be given where the pH of the cleaning solution is pre-adjusted using the above-described basic or acidic compounds before mixing the components, and a method can also be given where the pH is adjusted to a set value using the above-described basic or acidic compounds after mixing the components.

[0111] Furthermore, the composition of the present invention can be manufactured by producing a concentrate with a lower content of solvents such as water compared to that used in the present invention, and then adjusting the content of each component to a predetermined content by diluting it with a diluent (preferably water) during use. The composition of the present invention can be manufactured by diluting the concentrate with a diluent and then adjusting the pH to a predetermined value using the aforementioned alkaline or acidic compound. When diluting the concentrate, a predetermined amount of diluent can be added to the concentrate, or a predetermined amount of concentrate can be added to the diluent.

[0112] [Metal Removal Step] Regarding the above manufacturing method, a metal removal step can be performed to remove metal components from the above-mentioned ingredients and / or compositions (hereinafter also referred to as "purified material"). For example, an example of performing a metal removal step on a purified material containing the above-mentioned periodic acid or its salt and water can be given.

[0113] In the purified product comprising periodic acid or its salt and water, the content of periodic acid or its salt is not particularly limited, but it is preferable to be 0.0001 to 50% by mass relative to the total mass of the purified product, more preferably 1 to 45% by mass, and further preferably 4 to 40% by mass. From the viewpoint of excellent processing efficiency, it is preferable that the water content in the purified product is 40% by mass or more and less than 100% by mass, preferably 50 to 99% by mass, and further preferably 60 to 95% by mass. In the purified product comprising periodic acid or its salt and water, the components and / or any components contained in the above composition may be further included. As a metal removal step, step P, which involves ion exchange of the purified product, can be cited.

[0114] (Step P) In step P, an ion exchange method is performed on the purified substance described above. As for the ion exchange method, there are no particular limitations as long as it is a method that can adjust (reduce) the amount of metal components in the purified substance. However, from the viewpoint of making it easier to manufacture the solution, it is preferable that the ion exchange method includes one or more of the following methods P1 to P3. It is even more preferable that the ion exchange method includes two or more of methods P1 to P3, and it is further preferable that it includes all of methods P1 to P3. Furthermore, when the ion exchange method includes all of methods P1 to P3, there are no particular limitations on the order of implementation, but it is preferable to implement methods P1 to P3 in sequence. Method P1: A method of passing the purified substance through a first filling section filled with a mixed resin containing two or more resins selected from the group consisting of cation exchange resins, anion exchange resins, and chelating resins. Method P2: A method for passing the purified substance through at least one of a second filling section filled with cation exchange resin, a third filling section filled with anion exchange resin, and a fourth filling section filled with chelating resin. Method P3: A method for passing the purified substance through a membrane ion exchanger.

[0115] The steps of methods P1 to P3 described in detail in the following section, but if the ion exchange resin (cation exchange resin, anion exchange resin), chelating resin, and membrane ion exchanger used in each method are in a form other than H+ or OH-, it is preferable to regenerate them into H+ or OH- forms before use. Furthermore, a space velocity (SV) of 0.01 to 20.0 (L / h) for the purified substance in each method is preferred, and 0.1 to 10.0 (L / h) is more preferred. Also, a processing temperature of 0 to 60°C is preferred, and 10 to 50°C is more preferred.

[0116] Furthermore, examples of the forms of ion exchange resins and chelating resins include granular, fibrous, and porous bulk forms, with granular or fibrous forms being more preferred. For granular ion exchange resins and chelating resins, an average particle size of 10–2000 μm is preferred, and 100–1000 μm is more preferred. For the particle size distribution of granular ion exchange resins and chelating resins, a resin particle presence rate of 90% or more within a range of ±200 μm of the average particle size is preferred. Regarding the aforementioned average particle size and particle size distribution, for example, a method using a particle size distribution measuring device (MICROTRAC HRA3920, manufactured by Nikkiso Co., Ltd.) with water as the dispersion medium can be used for measurement.

[0117] -Method P1- Method P1 is a method of passing the purified substance through a first filling section filled with a mixed resin comprising two or more resins selected from the group consisting of cation exchange resins, anion exchange resins, and chelating resins. As the chelating resin, a known chelating resin can be used, specifically, the chelating resin described later can be used.

[0118] As a cation exchange resin, a known cation exchange resin can be used, which can be gel type or MR type (giant network type), with gel type cation exchange resin being preferred. Specifically, sulfonic acid type cation exchange resins and carboxylic acid type cation exchange resins can be cited as examples of cation exchange resins. Examples of cation exchange resins include Amberlite IR-124, Amberlite IR-120B, Amberlite IR-200CT, ORLITE DS-1, and ORLITE DS-4 (manufactured by Organo Corporation), Duolite C20J, Duolite C20LF, Duolite C255LFH, and Duolite C-433LF (manufactured by Sumika Chemtex Co., Ltd.), C100, C150, and C100×16MBH (manufactured by Purolite Corporation), as well as DIAION SK-110, DIAION SK1B, DIAION SK1BH, DIAION PK216, and DIAION PK228 (manufactured by Mitsubishi Chemical Corporation).

[0119] As an anion exchange resin, known anion exchange resins can be used, including gel-type and MR-type resins, with gel-type anion exchange resins being preferred. As a cation exchange resin, specifically, a fourth-order ammonium salt type anion exchange resin can be cited. Examples of anion exchange resins include Amberlite IRA-400J, Amberlite IRA-410J, Amberlite IRA-900J, Amberlite IRA67, ORLITE DS-2, ORLITE DS-5, and ORLITE DS-6 (manufactured by Organo Corporation), Duolite A113LF, Duolite A116, and Duolite A-375LF (manufactured by Sumika Chemtex Co., Ltd.), A400 and A500 (manufactured by Purolite Corporation), and DIAION SA12A, DIAION SA10AO, DIAION SA10AOH, DIAION SA20A, and DIAION WA10 (manufactured by Mitsubishi Chemical Corporation).

[0120] Commercially available products that are premixed with strong acidic cation exchange resin and strong basic anion exchange resin include, for example, Duolite MB5113, Duolite UP6000, and Duolite UP7000 (manufactured by Sumika Chemtex Co., Ltd.), Amberlite EG-4A-HG, Amberlite MB-1, Amberlite MB-2, Amberjet ESP-2, Amberjet ESP-1, ORLITE DS-3, ORLITE DS-7, and ORLITE DS-10 (manufactured by Organo Corporation), and DIAION SMNUP, DIAION SMNUPB, DIAION SMT100L, and DIAION SMT200L (all manufactured by Mitsubishi Chemical Corporation).

[0121] The mixed resin is preferably in the form of containing both cation exchange resin and anion exchange resin, or in the form of containing both cation exchange resin and chelating resin. When preparing a mixed resin containing both cation exchange resin and anion exchange resin, the mixing ratio of the two is preferably 1 / 4 to 4 / 1, and more preferably 1 / 3 to 3 / 1, in terms of the capacity ratio of cation exchange resin to anion exchange resin. Furthermore, a preferred combination of cation exchange resin and anion exchange resin is, for example, a combination of a gel-type sulfonic acid-type cation exchange resin and a gel-type quadrivalent ammonium salt-type anion exchange resin. When preparing a mixed resin containing both cation exchange resin and chelating resin, the mixing ratio of the two is preferably 1 / 4 to 4 / 1, and more preferably 1 / 3 to 3 / 1, in terms of the capacity ratio of cation exchange resin to chelating resin. Furthermore, a preferred combination of cation exchange resin and chelating resin may be a combination of gel-type sulfonic acid cation exchange resin and gel-type aminophosphonic acid chelating resin.

[0122] The first filling section typically includes a container and a mixed resin filled in the container, the mixed resin comprising two or more resins selected from the group consisting of cation exchange resins, anion exchange resins, and chelating resins. Examples of containers include columns, cylinders, and filling towers, but any container other than those exemplified above can be used as long as it allows the purified material to flow through after being filled with the aforementioned mixed resin.

[0123] In method P1, it is sufficient to pass the purified substance through at least one first filling section. From the viewpoint of making it easier to prepare the drug solution, the purified substance may be passed through two or more first filling sections.

[0124] -Method P2- Method P2 is a method for passing the purified substance through at least one (preferably two or more) of a filling section filled with a second filling section containing a cation exchange resin, a third filling section containing an anion exchange resin, and a fourth filling section containing a chelating resin. Examples of cation exchange resins and anion exchange resins that can be used in Method P2 include those listed in the description of Method P1.

[0125] The second filling section typically includes a container and the aforementioned cation exchange resin filled in the container. The third filling section typically includes a container and the aforementioned anion exchange resin filled in the container. The fourth filling section typically includes a container and a chelating resin, which will be described below, filled in the container.

[0126] A chelating resin generally refers to a resin having a coordinating group that can form a chelating bond with metal ions. For example, it is a resin obtained by introducing chelating-forming groups into styrene-divinylbenzene copolymers. The chelating resin can be gel-type or MR-type. From the viewpoint of processing efficiency, chelating resins are preferred to be granular or fibrous. Examples of chelating resins include various types such as iminodiacetic acid type, iminopropionic acid type, aminomethylphosphonic acid type, polyamine type, N-methylglucosamine type, glucosamine type, aminocarboxylic acid type, dithiocarbamate type, thiol type, acetaminophen type, pyridine type, and phosphonic acid type. Specific examples include: MC700 (manufactured by Sumika Chemtex Co., Ltd.), ORLITE DS-22 (manufactured by Organo Corporation), and D5843 (manufactured by Purolite Corporation); Epirus MX-8 (manufactured by MIYOSHI & FAT CO.,LTD.); MC960 (manufactured by Sumika Chemtex Co., Ltd.); ORLITE DS-21 (manufactured by Organo Corporation) and D5817 (manufactured by Purolite Corporation); and S985 (manufactured by Purolite Corporation), DIAION CR-20 (manufactured by Mitsubishi Chemical Corporation), and Sumika Chemtex Co., Ltd., as iminodiacetic acid type chelating resins. MC850 manufactured by Ltd. is an N-methylglucosamine type chelating resin. Examples of N-methylglucosamine type chelating resins include Amberlite IRA-743 manufactured by Organo Corporation, and S955 manufactured by Purolite Corporation is a phosphonic acid type chelating resin. From the viewpoint of being able to remove heavy metal elements contained in periodic acid, aminophosphonic acid type chelating resins are preferred.

[0127] The containers in the second filling section, the third filling section and the fourth filling section are defined as described above.

[0128] In method P2, the purified substance is passed through at least one of the second, third, and fourth filling sections. It is preferable that the purified substance is passed through two or more of the second, third, and fourth filling sections. In method P2, it is preferable that the purified substance is passed through at least the second filling section. Furthermore, in method P2, if the purified substance is passed through the fourth filling section, purification can be effectively performed even if the number of times the purified solution passes through the filling section is small. In method P2, when the purified substance is passed through two or more filling sections, the order in which the purified substance passes through two or more of the second, third, and fourth filling sections can be arbitrary.

[0129] In method P2, the purified substance is passed through at least one (preferably two or more) second filling sections, at least one (preferably two or more) third filling sections, and / or at least one fourth filling section. For example, from the viewpoint of easier preparation of the drug solution, the purified substance is passed through at least one (preferably two or more) second filling sections and at least one (preferably two or more) third filling sections. In this case, the order in which the purified substance is passed is not limited; for example, it can be passed alternately through the second and third filling sections, or it can be passed continuously through one of a plurality of second and third filling sections, and then continuously through another of a plurality of second and third filling sections. Furthermore, from the viewpoint of easier preparation of the drug solution, the purified substance can be passed through at least one second filling section and at least one fourth filling section. In this case, the order in which the purified substance is passed is also not limited.

[0130] -Method P3- Method P3 is a method for passing the purified substance through a membrane ion exchanger. The membrane ion exchanger is a membrane having ion exchange groups. Examples of ion exchange groups include cation exchange groups (sulfonic acid groups, etc.) and anion exchange groups (ammonium groups, etc.).

[0131] Membrane ion exchangers can be composed of ion exchange resin itself, or they can be formed by introducing cation exchange groups and / or anion exchange groups into a membrane support. The membrane ion exchanger (including the support containing the membrane ion exchanger) can be porous or non-porous. For example, the membrane ion exchanger (including the support containing the membrane ion exchanger) can be an aggregate of particles and / or fibers molded into a membrane. Furthermore, for example, the membrane ion exchanger can be any of the following: ion exchange membrane, ion exchange nonwoven fabric, ion exchange filter paper, and ion exchange filter cloth. As a form of using the membrane ion exchanger, for example, it can be assembled as a filter inside a cartridge to allow aqueous solution to pass through. Semiconductor-grade membrane ion exchangers are preferred. Examples of commercially available membrane ion exchangers include Mustang (manufactured by Pall Corporation) and Protego (registered trademark) Plus LT Purifier (manufactured by Entegris Corporation).

[0132] There are no particular limitations on the thickness of the membrane ion exchanger, but for example, 0.01 to 1 mm is preferred. The flow rate of the aqueous solution is, for example, 1 to 100 mL / (min·cm2).

[0133] In method P3, it is sufficient to pass the purified substance through at least one membrane ion exchanger. From the viewpoint of facilitating the preparation of the drug solution, the purified substance may be passed through two or more membrane ion exchangers. Furthermore, when using two or more membrane ion exchangers, at least one membrane ion exchanger having a cation exchange group and an ion exchanger having an anion exchange group may be used respectively.

[0134] It is preferable to carry out the ion exchange method until the content of the metal component contained in the purified substance is within the range of the preferred metal component content mentioned above.

[0135] [Filtration Step] The above manufacturing method preferably includes a filtration step to remove foreign matter and coarse particles from the liquid. There are no particular limitations on the filtration method, and known filtration methods can be used. Among them, filtration using a filter is preferred.

[0136] The filter used in the filtration process can be any type that has been used for filtration purposes in the past, without any particular limitations. Examples of materials constituting the filter include fluoropolymers such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight resins), and polyarylates. Among these, polyamide resins, PTFE, polypropylene (including high-density polypropylene), and polyarylates are preferred. By using a filter formed from these materials, highly polar foreign matter that is prone to causing defects can be removed from the composition more effectively.

[0137] The critical surface tension of the filter is preferably 70 mN / m or higher at the lower limit and 95 mN / m or lower at the upper limit. In particular, the critical surface tension of the filter is preferably 75 to 85 mN / m. Furthermore, the value of the critical surface tension is the manufacturer's nominal value. By using a filter with a critical surface tension within the above range, highly polar foreign matter that is prone to causing defects can be removed from the composition more effectively.

[0138] It is preferable that the pore size of the filter is 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 suppress filter clogging while reliably removing fine foreign matter contained in the components.

[0139] When using filters, different filters can be combined. Filtration using the first filter can be performed only once or more than twice. When combining different filters for filtration more than twice, the filters can be of the same type or different types, but it is preferable that they are different types. Typically, it is preferable that at least one of the pore size and constituent materials of the first and second filters are different. It is preferable that the pore size of subsequent filters is the same as or smaller than that of the first filter. Furthermore, first filters with different pore sizes can be combined within the above-mentioned range. The pore size can be referred to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by companies such as NIHON PALL LTD., Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (formerly Nippon micro squirrel Co., Ltd.), or KITZMICROFILTER CORPORATION. Furthermore, it is also possible to use polyamide to make "P-nylon filter (pore size 0.02μm, critical surface tension 77mN / m)"; (manufactured by NIHON PALL LTD.), high-density polyethylene to make "PE·Kleen filter (pore size 0.02μm)"; (manufactured by NIHON PALL LTD.), and high-density polyethylene to make "PE·Kleen filter (pore size 0.01μm)"; (manufactured by NIHON PALL LTD.).

[0140] Regarding the second filter, a filter made of the same material as the first filter described above can be used. It is possible to use a filter with the same pore size as the first filter described above. When using a second filter with a smaller pore size than the first filter, the ratio of the pore size of the second filter to the pore size of the first filter (pore size of the second filter / pore size of the first filter) is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and further preferably 0.3 to 0.9. By setting the pore size of the second filter within the above range, fine foreign matter mixed into the composition can be removed more reliably.

[0141] For example, the filtration in the first filter is carried out by a mixture containing a portion of the components of the composition, and after the remaining components are mixed therein to prepare the composition, a second filtration is performed. Furthermore, it is preferable that the filter used is treated before filtering the composition. There are no particular limitations on the liquid used in this treatment, but the composition and the liquid containing the components contained in the composition are preferred.

[0142] When filtration is performed, the upper limit of the filtration temperature is preferably below room temperature (25°C), more preferably below 23°C, and further preferably below 20°C. Furthermore, the lower limit of the filtration temperature is preferably above 0°C, more preferably above 5°C, and further preferably above 10°C. During filtration, particulate matter and / or impurities can be removed, but if the filtration is performed at the above-mentioned temperatures, the amount of particulate matter and / or impurities dissolved in the composition is reduced, thus allowing for more effective filtration.

[0143] [Electrostatic removal step] The method for manufacturing the composition may also include an electrostatic removal step for removing static electricity from the composition.

[0144] [Container] As a container for holding the components, a known container can be used, for example. A semiconductor-specific container with high cleanliness and minimal leaching of impurities is preferred. Examples of such containers include the "cleanbottle" series (manufactured by AICELLOCORPORATION) and "purebottle" (manufactured by KODAMAPLASTICS Co., Ltd.). Furthermore, from the viewpoint of preventing impurities from contaminating the raw materials and components, it is preferable to use a multi-layer container with a 6-layer structure made of 6 types of resin or a multi-layer container with a 7-layer structure made of 7 types of resin. Examples of multi-layer containers include those described in Japanese Patent Application Publication No. 2015-123351, the contents of which are incorporated herein by reference. For example, materials used for the inner wall of a container include at least one first resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin; a second resin different from the first resin; and metals such as stainless steel, Herstal alloy, Ingonane nickel, and Monel alloy. Furthermore, it is preferable that the inner wall of the container be formed or covered using the aforementioned materials.

[0145] Fluoropolymer (perfluoropolymer) is preferred as the second resin. When using a fluoropolymer, the leaching of ethyl or propyl oligomers can be suppressed. Examples of containers described above include the FluoroPure PFA composite roller (manufactured by Entegris Corporation), page 4 of Japanese Patent Publication No. 3-502677, page 3 of Japanese Time Publication No. 2004 / 016526, and pages 9 and 16 of Japanese Time Publication No. 99 / 046309.

[0146] For the inner wall of the container, in addition to fluororesin, quartz and electropolished metal materials are also preferred. The electropolished metal material is preferably one selected from the group consisting of at least one of chromium (Cr) and nickel (Ni), and the total content of Cr and Ni is more than 25% by mass relative to the total mass of the metal material. Examples include stainless steel and Ni-Cr alloys. The total content of Cr and Ni in the metal material is preferably 25% by mass or more relative to the total mass of the metal material, and more preferably 30% by mass or more. The maximum content is preferably 90% by mass or less relative to the total mass of the metal material.

[0147] As stainless steel, known stainless steels can be cited as examples. Among them, stainless steel containing 8% by mass or more of Ni is preferred, and Worsfield stainless steel containing 8% by mass or more of Ni is even more preferred. Examples of Worsfield stainless steels include SUS (Steel Use Stainless) 304 (Ni content: 8% by mass, Cr content: 18% by mass), SUS304L (Ni content: 9% by mass, Cr content: 18% by mass), SUS316 (Ni content: 10% by mass, Cr content: 16% by mass) and SUS316L (Ni content: 12% by mass, Cr content: 16% by mass).

[0148] Examples of Ni-Cr alloys include known Ni-Cr alloys. Ni-Cr alloys with a Ni content of 40–75% by mass and a Cr content of 1–30% by mass are preferred. Examples of Ni-Cr alloys include Hoechst alloys, Monel alloys, and Ingonane alloys. Specifically, examples include Hoechst alloy C-276 (Ni content: 63% by mass, Cr content: 16% by mass), Hoechst alloy-C (Ni content: 60% by mass, Cr content: 17% by mass), and Hoechst alloy C-22 (Ni content: 61% by mass, Cr content: 22% by mass). Depending on the requirements, Ni-Cr alloys may also contain boron, silicon, tungsten, molybdenum, copper, or cobalt in addition to the above-mentioned alloys.

[0149] As a method for electrolytic polishing of metallic materials, known methods can be cited, for example. Specifically, methods described in paragraphs

[0011] to

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

[0036] to

[0042] of Japanese Patent Application Publication No. 2008-264929 are cited, and such contents are incorporated in this specification.

[0150] Polishing is preferable for metallic materials. Known methods can be cited as examples of polishing methods. From the viewpoint that the surface roughness of metallic materials is more easily reduced, it is preferable that the size of the abrasive grains used in fine polishing is #400 or less. Polishing is preferable to be performed before electrolytic polishing. For metallic materials, one or more of the following processes can be combined: polishing, pickling, and magnetic fluid polishing, which involve multiple stages of polishing, pickling, and other treatments involving varying the size and coarseness of the abrasive grains.

[0151] For containers, it is preferable to clean the inside of the container before filling with the composition. The liquid used for cleaning can be appropriately selected according to the application, preferably a liquid containing at least one of the composition or components added to the composition.

[0152] From the viewpoint of preventing changes in the composition of the components during storage, the interior of the container can be replaced with an inert gas (e.g., nitrogen and argon) with a purity of 99.99995% by volume or higher. In particular, gases with low moisture content are preferred. Furthermore, the container for transporting and storing the components can be either at room temperature or under temperature control. From the viewpoint of preventing deterioration, controlling the temperature within the range of -20 to 20°C is preferred.

[0153] <Processing Method of the Processed Item> Hereinafter, a processing method for a processed item (processed item) containing Ru and W using the composition of the present invention will be described. First, the processed item will be described.

[0154] <Workpiece> The workpiece contains Ru and W. It is preferable that the Ru and W in the workpiece are present on the substrate. Furthermore, the Ru in the workpiece can be a Ru-containing compound containing Ru and other elements. Furthermore, the W in the workpiece can be a W-containing compound containing W and other elements. That is, it is preferable that the workpiece is a substrate containing Ru and W. It is preferable that the composition of the present invention is used to selectively remove Ru-containing compounds from the substrate relative to the W-containing compounds. Furthermore, "on the substrate" in this specification means, for example, including any one of the back surface, side surface, and groove of the substrate. Furthermore, the Ru-containing compounds on the substrate include not only the case where the Ru-containing compounds are directly present on the surface of the substrate, but also the case where the Ru-containing compounds are present on the substrate through other layers. Hereinafter, the recesses of the substrate provided in grooves and holes, etc., are referred to as "grooves, etc." Furthermore, the presence of Ru-containing compounds and W-containing compounds in the workpiece means that when the workpiece is brought into contact with the composition, the Ru-containing compounds and W-containing compounds can come into contact with the composition. Furthermore, the accessible state includes not only the state in which the Ru-containing and W-containing substances are exposed to the outside, but also the state in which the Ru-containing or W-containing substances can be exposed by removing the components covering them through some action.

[0155] There are no particular limitations on the type of substrate, but semiconductor substrates are preferred. Examples of substrates include semiconductor wafers, glass substrates for photomasks, glass substrates for liquid crystal displays, glass substrates for plasma displays, substrates for FEDs (Field Emission Displays), substrates for optical discs, substrates for magnetic discs, and substrates for optical-to-magnetic discs. Examples of materials constituting semiconductor substrates include group III-V compounds such as silicon, germanium, silicon-germanium, and GaAs, as well as combinations thereof.

[0156] The use of the processed object that has undergone processing based on the composition of the present invention is not particularly limited. For example, it can be used in DRAM (Dynamic Random Access Memory), FRAM (Ferroelectric Random Access Memory), MRAM (Magnetoresistive Random Access Memory), PRAM (Phase Change Random Access Memory), and can also be used in logic circuits and processors, etc.

[0157] As a Ru-containing compound, there are no particular limitations as long as it contains Ru (Ru atoms), such as Ru monomers, Ru-containing alloys, Ru oxides, Ru nitrides, and Ru nitrides. Furthermore, Ru oxides, Ru nitrides, and Ru nitrides can be Ru-containing complex oxides, complex nitrides, and complex nitrides. It is preferable that the content of Ru atoms in the Ru-containing compound is 10% by mass or more relative to the total mass of the Ru-containing compound, more preferably 30% by mass or more, further preferably 50% by mass or more, and especially preferably 90% by mass or more. There are no particular upper limits, but it is preferable that it is 100% by mass or less relative to the total mass of the Ru-containing compound.

[0158] Ru-containing compounds may contain other transition metals. Examples of transition metals include Rh (rhodium), Ti (titanium), Ta (tantalum), Co (cobalt), Cr (chromium), Hf (hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Cu (copper), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium).

[0159] The morphology of the Ru-containing material on the substrate is not particularly limited, and it can be configured as any of the following: film-like, wire-like, plate-like, columnar, and particle-like forms. Furthermore, as an example of the Ru-containing material being configured as particles, examples include, as described below, a substrate with particle-like Ru-containing material adhering as residue after dry etching of a substrate with a Ru-containing film; a substrate with particle-like Ru-containing material adhering as residue after CMP (chemical mechanical polishing) of a Ru-containing film; and a substrate with particle-like Ru-containing material adhering in areas other than the predetermined area where the Ru-containing film is formed after a Ru-containing film is deposited on the substrate.

[0160] There is no particular limitation on the thickness of the Ru-containing film; it can be selected appropriately according to the application. For example, 200 nm or less is preferred, 100 nm or less is even better, and 50 nm or less is further preferred. There is no particular limitation on the lower limit, but 0.1 nm or more is preferred. The Ru-containing film can be disposed on only one side of the main surface of the substrate, or it can be disposed on both sides of the main surface. Furthermore, the Ru-containing film can be disposed on the entire surface of the main surface of the substrate, or it can be disposed on a part of the main surface of the substrate.

[0161] As a W-containing material, there are no particular limitations as long as it contains W (W atoms), such as W monomers, W-containing alloys, W oxides, W nitrides, W oxynitrides, W carbides, and W borides. Furthermore, W oxides, W nitrides, W oxynitrides, and W carbides can be W-containing composite oxides, composite nitrides, composite oxynitrides, and composite carbides. It is preferable that the W atom content in the W-containing material is 10% by mass or more relative to the total mass of the W-containing material, more preferably 30% by mass or more, further preferably 50% by mass or more, and especially preferably 90% by mass or more. There are no particular upper limits, but it is preferable that it is 100% by mass or less relative to the total mass of the W-containing material.

[0162] W-containing compounds may contain other transition metals. Examples of transition metals include Rh (rhodium), Ti (titanium), Ta (tantalum), Co (cobalt), Cr (chromium), Hf (hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Cu (copper), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium).

[0163] The shape of the W-containing material on the substrate is not particularly limited, for example, it can be configured as a film, wire, plate, column, or particle.

[0164] There is no particular limitation on the thickness of the W-containing film; it can be selected appropriately according to the application. For example, 200 nm or less is preferred, 100 nm or less is even better, and 50 nm or less is further preferred. There is no particular limitation on the lower limit, but 0.1 nm or more is preferred. The W-containing film can be disposed on only one side of the main surface of the substrate, or it can be disposed on both sides of the main surface. Furthermore, the W-containing film can be disposed on the entire surface of the main surface of the substrate, or it can be disposed on a part of the main surface of the substrate.

[0165] Furthermore, the processed material may include various layers or structures as needed, in addition to Ru-containing and W-containing materials. For example, one or more components selected from the group consisting of metal wiring, gate electrode, source electrode, drain electrode, insulating film, strongly magnetic layer, and non-magnetic layer may be disposed on the substrate. The substrate may include an exposed integrated circuit structure. Examples of integrated circuit structures include interconnection mechanisms such as metal wiring and dielectric materials. Examples of metals and alloys used for interconnection mechanisms include aluminum, copper-aluminum alloy, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and molybdenum. The substrate may include layers of materials selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.

[0166] There are no particular restrictions on the size, thickness, shape, and layer structure of the substrate, and it can be selected appropriately according to the needs.

[0167] [Manufacturing Method of the Processed Object] There are no particular limitations on the manufacturing method of the processed object, and known manufacturing methods can be used. For example, sputtering, chemical vapor deposition (CVD), molecular beam epitaxy (MBE), and atomic layer deposition (ALD) can be used to form Ru-containing films and / or W-containing films on a substrate. When forming a Ru-containing film using the above-described manufacturing methods, if the substrate has a structure with uneven surfaces, the Ru-containing film may sometimes be formed on all surfaces of the structure. Furthermore, especially when forming a Ru-containing film by sputtering and CVD, the Ru-containing film may sometimes also be attached to the back side of the substrate where the Ru-containing film is disposed (the surface opposite to the Ru-containing film side). Also, by performing the above methods with a predetermined mask, Ru-containing wiring and / or W-containing wiring can be formed on the substrate. Furthermore, a predetermined process can be performed on a substrate having a Ru-containing film, Ru-containing wiring, a W-containing film, and / or W-containing wiring to serve as the workpiece in the processing method of the present invention. For example, the substrate can be dry-etched to produce a substrate having dry etching residue containing Ru and W-containing material. Alternatively, CMP can be performed on the substrate to produce a substrate having Ru-containing material and W-containing material. Furthermore, by depositing a Ru-containing film in a predetermined area of ​​the Ru-containing film formation on the substrate using sputtering, CVD, molecular beam epitaxy, or atomic layer deposition, a substrate having Ru-containing material attached to areas other than the predetermined Ru-containing film formation area and having W-containing material can be produced.

[0168] <Processing Method for the Work to be Processed> Regarding the processing method for a work to be processed (the work to be processed) containing Ru and W using the composition of the present invention, a processing method for a substrate containing Ru and W will be described, on a representative basis. Furthermore, the substrate containing Ru and W will also be referred to as "the substrate to be processed" below.

[0169] [Step A] The method for processing the substrate (hereinafter also referred to as "this processing method") includes step A, which involves removing the Ru-containing material from the substrate using the composition of the present invention. Furthermore, the substrate (the substrate being processed) containing both the Ru-containing material and the W-containing material, which is the subject of this processing method, is as described above.

[0170] As a specific method for step A, a method of bringing the composition into contact with the substrate to be processed, which is the object to be processed, can be cited. The method of contact is not particularly limited; for example, a method of immersing the object to be processed in the composition placed in a container, a method of spraying the composition onto the object to be processed, a method of causing the composition to flow onto the object to be processed, and combinations thereof can be cited. Among these, the method of immersing the object to be processed in the composition is preferred.

[0171] Furthermore, mechanical stirring can be used to further enhance the cleaning ability of the composition. Examples of mechanical stirring methods include circulating the composition over the workpiece, flowing or spraying the composition over the workpiece, and locally stirring the composition near the substrate by irradiation with ultrasonic waves (e.g., megaphones). The processing time in step A can be adjusted appropriately. There is no particular limitation on the processing time (the contact time between the composition and the workpiece), but 0.25 to 10 minutes is preferred, and 0.5 to 2 minutes is even better. There is no particular limitation on the temperature of the composition during processing, but 20 to 75°C is preferred, 20 to 60°C is even better, 40 to 65°C is further preferred, and 50 to 65°C is particularly preferred.

[0172] In step A, while determining the concentration of one or more components selected from the group consisting of periodic acid or its salt, quaternary ammonium salt, nitrogen-containing resin, solvent, and any other components, a process of adding one or more components selected from the group consisting of solvent and other components can be performed as needed. By performing this process, the concentration of the components in the composition can be stably maintained within a predetermined range. Water is preferred as a solvent.

[0173] As a specific preferred embodiment of step A, examples include step A1, which involves using the composition to perform a rest etching process on a Ru-containing wiring or Ru-containing pad disposed on a substrate; step A2, which involves using the composition to remove the Ru-containing film from the outer edge of a substrate with a Ru-containing film disposed on it; step A3, which involves using the composition to remove Ru-containing material adhering to the back side of a substrate with a Ru-containing film disposed on it; step A4, which involves using the composition to remove Ru-containing material from a substrate after dry etching; step A5, which involves using the composition to remove Ru-containing material from a substrate after chemical mechanical polishing; and step A6, which involves using the composition to remove Ru-containing material from areas other than the predetermined Ru-containing film formation area on the substrate after a Ru-containing film has been deposited in the predetermined Ru-containing film formation area on the substrate. In the substrate processing method using the composition of the present invention, the Ru-containing material present in the substrate being processed is not removed in the above steps. Hereinafter, the processing method of the present invention used in each of the above processes will be described.

[0174] (Step A1) As step A, step A1 can be described as using the composition to perform a rest etching process on Ru-containing wiring (wiring containing Ru) and Ru-containing pads (pads containing Ru) disposed on a substrate. Hereinafter, as examples of the work processed in step A1, a substrate having Ru-containing wiring and a substrate having Ru-containing pads will be specifically described.

[0175] <Substrate with Ru-containing wiring> FIG1 shows an example of the workpiece to be processed in step A1, a schematic diagram of the upper part of a cross-section of a substrate with Ru-containing wiring (hereinafter also referred to as "Ru wiring substrate"). The Ru wiring substrate 10a shown in FIG1 has: a substrate (not shown), an insulating film 12 having trenches or the like disposed on the substrate, a barrier metal layer 14 disposed along the inner wall of the trenches or the like, and Ru-containing wiring 16 filling the interior of the trenches or the like. Furthermore, a W-containing substance (not shown) is present in the Ru wiring substrate 10a.

[0176] It is preferable that the Ru-containing wiring in the Ru wiring substrate includes Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. There are no particular limitations on the material constituting the barrier metal layer in the Ru wiring substrate; examples include Ti metal, Ti nitrides, Ti oxides, Ti-Si alloys, Ti-Si composite nitrides, Ti-Al alloys, Ta metal, Ta nitrides, and Ta oxides. Furthermore, while FIG. 1 describes a Ru wiring substrate having a barrier metal layer, it can also be a Ru wiring substrate without a barrier metal layer.

[0177] In step A1, the Ru wiring substrate is subjected to a rest etching process using the above-described composition, thereby removing a portion of the Ru-containing wiring to form a recess. More specifically, as shown in the Ru wiring substrate 10b of FIG2, if step A1 is performed, the barrier metal layer 14 and a portion of the Ru-containing wiring 16 are removed to form a recess 18. Furthermore, FIG2 shows the Ru wiring substrate 10b in which the barrier metal layer 14 and a portion of the Ru-containing wiring 16 are removed, but it is also possible to remove only a portion of the Ru-containing wiring 16 without removing the barrier metal layer 14 to form the recess 18. Furthermore, in the above process, the W-containing material is not removed.

[0178] There are no particular limitations on the manufacturing method of Ru wiring substrate. For example, a method having the following steps can be cited: a step of forming an insulating film on a substrate, a step of forming a groove on the insulating film, a step of forming a barrier metal layer on the insulating film, a step of forming a Ru-containing film to fill the groove, and a step of performing planarization treatment on the Ru-containing film.

[0179] <Substrate with Ru Pad> FIG3 shows a schematic diagram of the upper part of a cross section of a substrate with a Ru pad (hereinafter also referred to as "Ru pad substrate"), which is another example of the workpiece to be processed in the respite etching process of step A1.

[0180] The Ru pad substrate 20a shown in FIG3 includes: a substrate (not shown), an insulating film 22 having grooves or the like disposed on the substrate, a Ru-containing pad 24 disposed along the inner wall of the grooves or the like, and a wiring portion 26 filling the interior of the grooves or the like. Furthermore, a W-containing substance (not shown) is present in the Ru pad substrate 20a.

[0181] It is preferable that the Ru-containing pad in the Ru pad substrate contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. Furthermore, in the Ru pad substrate shown in FIG3, a barrier metal layer may be additionally provided between the Ru-containing pad 24 and the insulating film 22. An example of the material constituting the barrier metal layer is the same as that in the case of the Ru wiring substrate. There are no particular limitations on the material constituting the wiring portion in the Ru pad substrate, but examples include Cu metal, W metal, Mo metal, and Co metal.

[0182] In step A1, the Ru pad substrate is subjected to a rest etching process using the above-described composition, thereby removing a portion of the Ru-containing pad to form a recess. More specifically, as shown in the Ru pad substrate 20b of FIG4, if step A1 is performed, a portion of the Ru-containing pad 24 and the wiring portion 26 is removed to form a recess 28. Furthermore, in the above process, the W-containing material is not removed.

[0183] There are no particular limitations on the manufacturing method of the Ru pad substrate, and a method having the following steps can be cited: a step of forming an insulating film on the substrate, a step of forming a groove on the insulating film, a step of forming a Ru pad on the insulating film, a step of forming a metal film to fill the groove, and a step of performing planarization treatment on the metal film.

[0184] As a specific method for step A1, a method for contacting the Ru wiring substrate or Ru pad substrate with the composition can be described. The method for contacting the Ru wiring substrate or Ru pad substrate with the composition is as described above. The preferred ranges for the contact time between the Ru wiring substrate or Ru pad substrate and the composition, and the temperature of the composition are as described above.

[0185] (Step B) Furthermore, Step B can be performed as needed before or after Step A1. Step B involves processing the substrate obtained in Step A1 using a predetermined solution (hereinafter also referred to as "specific solution"). In particular, when a barrier metal layer is disposed on the substrate, the solubility of the components constituting the Ru-containing wiring or Ru pads (hereinafter also referred to as "Ru-containing wiring, etc.") and the components constituting the barrier metal layer may differ depending on their type. In this case, it is preferable to use a solution with a better solubility than the barrier metal layer to adjust the degree of solubility of the Ru-containing wiring, etc. and the barrier metal layer. From this point of view, it is preferable to use a specific solution with poor solubility for the Ru-containing wiring, etc., but excellent solubility for the material constituting the barrier metal layer. Furthermore, it is preferable that the specific solution has a low solubility for the W-containing material.

[0186] As a specific solution, examples include solutions selected from the group consisting of a mixture of hydrofluoric acid and hydrogen peroxide water (FPM), a mixture of sulfuric acid and hydrogen peroxide water (SPM), a mixture of ammonia and hydrogen peroxide water (APM), and a mixture of hydrochloric acid and hydrogen peroxide water (HPM). The composition of FPM is preferably in the range of "hydrofluoric acid:hydrogen peroxide water:water = 1:1:1" to "hydrofluoric acid:hydrogen peroxide water:water = 1:1:200" (volume ratio). The composition of SPM is preferably in the range of "sulfuric acid:hydrogen peroxide water:water = 3:1:0" to "sulfuric acid:hydrogen peroxide water:water = 1:1:10" (volume ratio). The composition of APM is preferably in the range of "ammonia water:hydrogen peroxide water:water = 1:1:1" to "ammonia water:hydrogen peroxide water:water = 1:1:30" (volume ratio). The composition of HPM is preferably within the range of "hydrochloric acid:hydrogen peroxide water:water = 1:1:1" to "hydrochloric acid:hydrogen peroxide water:water = 1:1:30" (volume ratio). Furthermore, the preferred composition ratios mentioned refer to the following: 49% by mass of hydrofluoric acid, 98% by mass of sulfuric acid, 28% by mass of ammonia, 37% by mass of hydrochloric acid, and 31% by mass of hydrogen peroxide water. From the viewpoint of the dissolution energy of the barrier metal layer, SPM, APM, or HPM are preferred for a specific solution. From the viewpoint of reducing roughness, APM, HPM, or FPM are preferred for a specific solution, with APM being more preferred. From the viewpoint of excellent performance balance, APM or HPM are preferred for a specific solution.

[0187] In step B, the method of treating the substrate obtained in step A1 with a specific solution is preferably a method of contacting the specific solution with the substrate obtained in step A1. There are no particular limitations on the method of contacting the specific solution with the substrate obtained in step A1; for example, methods similar to those used to contact the composition 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.

[0188] In this processing method, steps A1 and B can be performed alternately. When performing the alternating repetition, it is preferable to perform steps A1 and B 1 to 10 times respectively. Furthermore, when performing steps A1 and B alternately, the first and last steps can be either steps A1 or B.

[0189] (Step A2) As step A, for example, step A2 can be described as removing the Ru-containing film from the outer edge of a substrate on which the Ru-containing film is disposed using a composition. FIG5 shows a schematic diagram (top view) of an example of a substrate on which the Ru-containing film is disposed as the workpiece to be processed in step A2. The workpiece 30 to be processed in step A2 shown in FIG5 is a laminate having a substrate 32 and a Ru-containing film 34 disposed on a single main surface of the substrate 32 (the entire area surrounded by solid lines). As will be described later, in step A2, the Ru-containing film 34 located at the outer edge 36 (the area outside the dashed lines) of the workpiece 30 is removed. Also, a W-containing substance (not shown) is present in the workpiece 30.

[0190] The substrate and the Ru-containing film in the processed object are as described above. Furthermore, it is preferable that the Ru-containing film contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides.

[0191] There are no particular limitations on the specific method of step A2. For example, a method in which the composition is supplied from a nozzle so that the composition only contacts the Ru-containing film on the outer edge of the substrate can be used. When performing the process of step A2, the substrate processing apparatus and substrate processing method described in Japanese Patent Application Publication Nos. 2010-267690, 2008-080288, 2006-100368, and 2002-299305 can be preferred.

[0192] The contact method between the composition and the treated object is as described above. The preferred ranges for the contact time between the composition and the treated object and the temperature of the composition are as described above. Furthermore, the W-containing substance is not removed in step A2.

[0193] (Step A3) As step A, step A3 can be described as using a composition to remove the Ru-containing material adhering to the back side of a substrate on which the Ru-containing film is disposed. As the workpiece to be processed in step A3, the workpiece used in step A2 can be described. When the substrate used in step A2 is formed and the workpiece on which the Ru-containing film is disposed on one side of the main surface of the substrate, the Ru-containing film is formed by sputtering and CVD, etc. At this time, Ru-containing material sometimes adheres to the surface on the side opposite to the Ru-containing film side of the substrate (back side). Step A3 is performed in order to remove the Ru-containing material from such workpiece.

[0194] There are no particular limitations on the specific method of step A3. For example, a method of spraying the composition so that the composition only contacts the back side of the substrate can be cited.

[0195] The contact method between the composition and the treated object is as described above. The preferred ranges for the contact time between the composition and the treated object and the temperature of the composition are as described above. Furthermore, the W-containing substance is not removed in step A3.

[0196] (Step A4) As step A, step A4 can be described as removing Ru-containing substances from the substrate after dry etching using a composition. Figures 6 and 8 show schematic diagrams illustrating an example of the workpiece processed in step A4. Each figure will be explained below.

[0197] The workpiece 40 shown in FIG. 6 has a Ru-containing film 44, an etch stop layer 46, an interlayer insulating film 48, and a metal hard mask 50 sequentially on a substrate 42. Through a dry etching process, grooves 52 exposing the Ru-containing film 44 are formed at predetermined positions. That is, the workpiece shown in FIG. 6 has a substrate 42, a Ru-containing film 44, an etch stop layer 46, an interlayer insulating film 48, and a metal hard mask 50 sequentially. At the opening of the metal hard mask 50, there is a stack of grooves 52 extending from its surface to the surface of the Ru-containing film 44. The inner wall 54 of the grooves 52 is composed of a cross-sectional wall 54a including the etch stop layer 46, the interlayer insulating film 48, and the metal hard mask 50, and a bottom wall 54b including the exposed Ru-containing film 44. Dry etching residue 56 is attached to the inner wall 54 of the grooves. The dry etching residue contains Ru. Furthermore, a W-containing substance (not shown) is present in the processed material 40.

[0198] The workpiece 60b shown in FIG8 is obtained by dry etching the workpiece shown in FIG7 before dry etching. The workpiece 60a shown in FIG7 has an insulating film 62 disposed on a substrate (not shown), a Ru-containing film 66 filling the grooves formed in the insulating film 62, and a metal hard mask 64 located at the opening of the Ru-containing film 66 disposed on the insulating film 62. The workpiece 60a is obtained by sequentially forming the insulating film 62 and the metal hard mask 64 on a substrate (not shown), forming grooves in the insulating film 62 located at the opening of the metal hard mask 64, and filling the grooves with Ru-containing material to form the Ru-containing film 66. If the workpiece 60a shown in FIG7 is dry etched, the Ru-containing film is etched to obtain the workpiece 60b shown in FIG8. The workpiece 60b shown in Figure 8 has an insulating film 62 disposed on a substrate (not shown), a Ru-containing film 66 filling a portion of a groove or the like formed in the insulating film 62, and a metal hard mask 64 having an opening at the location of the groove or the like on the insulating film 62. Dry etching residue 76 is attached to the cross-sectional wall 74a composed of the insulating film 62 and the metal hard mask 64 within the groove or the like, and the bottom wall 74b composed of the Ru-containing film 66. The dry etching residue contains Ru. Furthermore, a W-containing substance (not shown) is present in the workpiece 60b.

[0199] The Ru-containing film supplied to the workpiece in step A4 preferably contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The Ru-containing material supplied to the workpiece in step A4 preferably contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The interlayer insulating film and the insulating film can be made of known materials. The metal hard mask can be made of known materials. Furthermore, in Figures 6, 7, and 8, the use of a metal hard mask is described, but a resist mask formed using a known photoresist material can also be used.

[0200] As a specific method for step A4, a method of contacting the composition with the object to be processed can be cited. The method of contacting the composition with the wiring board is as described above. The preferred ranges for the contact time between the composition and the wiring board and the temperature of the composition are as described above. Furthermore, the W-containing material is not removed in step A4.

[0201] (Step A5) Step A5 involves using a composition to remove Ru-containing contaminants from the substrate after chemical mechanical polishing (CMP). CMP technology is incorporated into manufacturing steps such as planarization of insulating films, planarization of interconnects, and inlay wiring. The substrate after CMP is sometimes contaminated with particles from the polishing process and metallic impurities. Therefore, these contaminants need to be removed and the substrate cleaned before proceeding to the next processing stage. Therefore, by performing step A5, Ru-containing contaminants that adhere to the substrate when the CMP-treated object has Ru-containing wiring or a Ru-containing film can be removed.

[0202] Regarding the workpiece to be processed in step A5, as described above, a substrate containing a Ru-containing compound after CMP can be cited. It is preferable that the Ru-containing compound includes Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. Furthermore, a W-containing compound is present on the Ru-containing substrate after CMP. As a specific method for step A5, a method of contacting the composition with the workpiece can be cited. The method of contacting the composition with the wiring substrate is as described above. The preferred ranges for the contact time between the composition and the wiring substrate and the temperature of the composition are as described above. Furthermore, the W-containing compound is not removed in step A5.

[0203] (Step A6) As step A, step A6 can be described as using a composition to remove the Ru-containing material from areas other than the Ru-containing film formation predetermined area on the substrate after the Ru-containing film has been deposited on the substrate. As described above, there are no particular limitations on the method of forming the Ru-containing film, and sputtering, CVD, MBE, and ALD methods can be used to form the Ru-containing film on the substrate. When the Ru-containing film is formed in the Ru-containing film formation predetermined area (the predetermined area for forming the Ru-containing film) on the substrate by the above method, the Ru-containing film can also be formed in areas that are not intended to be formed (areas other than the Ru-containing film formation predetermined area). For example, the sidewall of the insulating film when filling the groove of the insulating film, etc., with the Ru-containing film can be described. An example of the workpiece processed in step A6 is shown in FIG10. The workpiece 80b shown in FIG10 can be obtained by forming a Ru-containing film on the workpiece 80a before the Ru-containing film formation shown in FIG9. The workpiece 80a shown in FIG9 has an insulating film 82 disposed on a substrate (not shown) and a metal hard mask 84 disposed on the insulating film 82. The insulating film 82 has grooves or the like at the openings of the metal hard mask 84. A Ru-containing film is formed by filling a portion of the grooves or the like 86 of the workpiece 80a, thereby obtaining the workpiece 80b shown in FIG10. The workpiece 80b shown in FIG10 has an insulating film 82 disposed on a substrate (not shown), a Ru-containing film 88 filling a portion of the grooves or the like 86 formed on the insulating film 82, and a metal hard mask 84 having openings at the positions of the grooves or the like 86 disposed on the insulating film 82. Residue 92 from the formation of the Ru-containing film is attached to the cross-sectional wall 90a composed of the insulating film 82 and the metal hard mask 84 and the bottom wall 90b composed of the Ru-containing film 88 in the grooves or the like 86. In the above-described sample, the region containing the Ru-containing film 88 corresponds to the predetermined region for Ru-containing film formation, and the cross-sectional wall 90a and bottom wall 90b correspond to the regions other than the predetermined region for Ru-containing film formation. Furthermore, a W-containing substance (not shown) exists in the treated object 80b.

[0204] The Ru-containing film preferably contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The Ru-containing material preferably contains Ru monomers, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The hard metal mask can be made of a known material. Furthermore, while Figures 9 and 10 describe the use of a hard metal mask, a resist mask formed using a known photoresist material can also be used.

[0205] As a specific method for step A6, a method of contacting the composition with the object to be processed can be cited. The method of contacting the composition with the wiring board is as described above. The preferred ranges for the contact time between the composition and the wiring board and the temperature of the composition are as described above. Furthermore, the W-containing material is not removed in step A6.

[0206] [Step C] This processing step may include step C, after step A, rinsing the substrate obtained in step A with rinsing solution as needed.

[0207] As rinsing solutions, for example, hydrofluoric acid (0.001-1% by mass is preferred), hydrochloric acid (0.001-1% by mass is preferred), hydrogen peroxide solution (0.5-31% by mass is preferred, 3-15% by mass is more preferred), a mixture of hydrofluoric acid and hydrogen peroxide solution (FPM), a mixture of sulfuric acid and hydrogen peroxide solution (SPM), a mixture of ammonia and hydrogen peroxide solution (APM), a mixture of hydrochloric acid and hydrogen peroxide solution (HPM), carbon dioxide (10-60 ppm by mass is preferred), ozone solution (10-60 ppm by mass is preferred), hydrogen water (10-20 ppm by mass is preferred), citric acid aqueous solution (0.01-10% by mass is preferred), acetic acid (acetic acid stock solution, or... The preferred solutions are: 0.01–10% by mass acetic acid aqueous solution, sulfuric acid (1–10% by mass sulfuric acid aqueous solution), ammonia (0.01–10% by mass ammonia solution), isopropanol (IPA), hypochlorous acid aqueous solution (1–10% by mass hypochlorous acid aqueous solution), aqua regia (preferably a solution in which the volume ratio of 37% by mass hydrochloric acid to 60% by mass nitric acid is equivalent to 2.6 / 1.4–3.4 / 0.6), ultrapure water, nitric acid (0.001–1% by mass nitric acid is preferred), perchloric acid (0.001–1% by mass perchloric acid is preferred), oxalic acid aqueous solution (0.01–10% by mass aqueous solution is preferred), or periodic acid aqueous solution (0.5–10% by mass periodic acid aqueous solution is preferred; for example, orthoperiodic acid and metaperiodic acid can be used as periodic acid). Preferred conditions for FPM, SPM, APM, and HPM are, for example, the same as preferred conditions for the specific solutions used above for FPM, SPM, APM, and HPM. Furthermore, fluorine, nitric acid, perchloric acid, and hydrochloric acid refer to aqueous solutions of HF, HNO3, HClO4, and HCl dissolved in water, respectively. Ozone water, carbon dioxide, and hydrogen water refer to aqueous solutions of O3, CO2, and H2 dissolved in water, respectively. These rinsing solutions can be mixed without impairing the purpose of the rinsing step.

[0208] Among them, from the viewpoint of further reducing residual chlorine on the substrate surface after the rinsing step, carbon dioxide, ozone water, hydrogen water, hydrofluoric acid, citric acid aqueous solution, hydrochloric acid, sulfuric acid, ammonia water, hydrogen peroxide water, SPM, APM, HPM, IPA, hypochlorous acid aqueous solution, aqua regia, or FPM are preferred as rinsing fluids, and hydrofluoric acid, hydrochloric acid, hydrogen peroxide water, SPM, APM, HPM, or FPM are even more preferred.

[0209] As a specific method for step C, for example, a method of bringing the rinsing liquid into contact with the substrate obtained in step A, which is the object to be treated. As a contact method, for example, a method of immersing the substrate in the rinsing liquid placed in a tank, a method of spraying the rinsing liquid onto the substrate, a method of flowing the rinsing liquid onto the substrate, and any combination thereof.

[0210] There is no particular limitation on the treatment time (the contact time between the rinsing solution and the treated object), for example, it can be between 5 seconds and 5 minutes. There is no particular limitation on the temperature of the rinsing solution during treatment, but it is generally preferred to be between 16 and 60°C, and even better to be between 18 and 40°C. When using SPM as the rinsing solution, the temperature is preferably between 90 and 250°C.

[0211] [Step D] This processing method may include step D, which involves performing a drying process as needed after step C. The drying method is not particularly limited, but examples include rotary drying, flow of drying gas on the substrate, heating of the substrate (e.g., heating based on a heating plate or infrared lamp), IPA (isopropyl alcohol) vapor drying, marangoni drying, notagononi drying, and combinations thereof. The drying time can be appropriately varied depending on the specific method used, for example, from approximately 30 seconds to several minutes.

[0212] (Other Steps) This processing method can be implemented in combination before or after other steps performed on the substrate. Other steps can be incorporated into the implementation of this processing method, or the processing method of this invention can be incorporated into other steps. Examples of other steps include the formation steps of structures such as metal wiring, gate structures, source structures, drain structures, insulating films, strongly magnetic layers, and non-magnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and modification), resist formation steps, exposure steps and removal steps, heat treatment steps, cleaning steps, and inspection steps. This processing method can be performed at any stage of the backend of the line (BEOL), middleend of the line (MOL), and frontend of the line (FEOL), with performance in the frontend or middleend of the line being preferred. [Example]

[0213] Hereinafter, the present invention will be described in further detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0214] <Preparation of the Composition> After obtaining a mixture by mixing ultrapure water and each component in the amounts shown in Table 1 (to be continued), the mixture was thoroughly stirred using a stirrer to obtain the composition used in each embodiment and comparative example. Furthermore, the contents of the composition in Table 1 are based on mass, and the residual portion of the total of each component is water. Hereinafter, each component shown in Table 1 (to be continued) will be specifically described.

[0215] [Periodic acid or its salts] ·IO⁻¹: Orthoperiodic acid ·IO⁻²: Sodium orthoperiodate ·IO⁻³: Metaperiodic acid

[0216] [Quadrivalent Ammonium Salts] ·A-1: Tetramethylammonium hydroxide ·B-1: Tetraethylammonium hydroxide ·B-2: Tetraethylammonium chloride ·B-3: Tetramethylammonium bromide ·B-4: Tetraethylammonium fluoride ·C-1: Tetrabutylammonium hydroxide ·D-1: Ethyltrimethylammonium hydroxide ·D-2: Ethyltrimethylammonium chloride ·E-1: Diethyldimethylammonium hydroxide ·F-1: Triethylmethylammonium hydroxide ·G-1: (2-hydroxyethyl)trimethylammonium hydroxide ·H-1: Tributylmethylammonium hydroxide ·I-1: Dimethyldipropylammonium hydroxide ·J-1: Benzyltrimethylammonium hydroxide ·K-1: Benzyltriethylammonium hydroxide ·L-1: (2-hydroxyethyl)triethylammonium hydroxide ·M-1: Dodecyltrimethylammonium hydroxide ·N-1: Tetradecyltrimethylammonium hydroxide ·O-1: Hexadecyltrimethylammonium hydroxide

[0217] [Nitrogen-containing resin] The following compounds were used as nitrogen-containing resins. Furthermore, the weight-average molecular weight of each compound is shown in Table 1 below. • PA-1 to PA-9: Compounds comprising repeating units represented by the following formulas.

[0218] [Chemical Formula 8]

[0219] ·PB-1~PB-4: Compounds comprising repeating units represented by the following formulas.

[0220] [Chemical Formula 9]

[0221] ·PC-1 and PC-2: Compounds comprising repeating units represented by the following formulas.

[0222] [Chemical Formula 10]

[0223] ·PD-1 and PD-2: Compounds comprising repeating units represented by the following formulas.

[0224] [Chemical Formula 11]

[0225] ·PE-1~PE-3: Compounds comprising repeating units represented by the following formulas.

[0226] [Chemical Formula 12]

[0227] ·PF-1 and PF-2: Compounds comprising repeating units represented by the following formulas.

[0228] [Chemical Formula 13]

[0229] [Water] · Ultrapure Water

[0230] [Additives] The additives used in Examples 71, 72, and Comparative Example 4 are as follows: • IA: Iodic acid • TEA: Triethylamine • BMPC: 1-Butyl-1-methylpyrrolidone chloride

[0231] <Evaluation> The evaluation of Ru / W selectivity based on the ratio of the etch rate of Ru (ERRu) to the etch rate of W (ERW) of the composition was carried out according to the following steps. A substrate with a Ru layer (a layer composed of Ru monomers) formed by PVD was prepared on one surface of a commercially available silicon wafer (diameter: 12 inches). The obtained substrate was placed in a container filled with a 1% by mass citric acid aqueous solution and the citric acid aqueous solution was stirred for pretreatment. The pretreated substrate was placed in a container filled with the composition of each example or comparative example and the composition was stirred for 1 minute to remove the Ru layer. The temperature of the composition was 25°C. The thickness of the Ru layer before and after the removal treatment was measured using a thin film evaluation fluorescence X-ray analysis device (XRF AZX-400, manufactured by Rigaku Corporation), and the etch rate of the Ru layer (ERRu Å / min) was calculated based on the difference in the thickness of the Ru layer before and after the removal treatment. Furthermore, a W layer (a layer composed of W monomers) was formed using CVD. The W layer was then removed in the same manner as described above. The thickness of the W layer before and after the removal process was determined using a resistivity meter (VR300DE, manufactured by Kokusai Electric Semiconductor Service Inc.). Based on the determined W layer thickness, the etching rate (ERW Å / min) of the W layer was calculated. The ratio of ERRu to ERW (ERR(Ru / W)) was calculated by dividing the ERRu calculated using the above method by ERW. Based on the determined ERR(Ru / W), the Ru / W selectivity was evaluated according to the following criteria.

[0232] [Evaluation criteria for ERR (Ru / W)] A: 30.0 or higher B: 10.0 or higher and less than 30.0 C: 5.0 or higher and less than 10.0 D: 2.0 or higher and less than 5.0 E: 0.0 or higher and less than 2.0

[0233] <Results> Regarding the formulation of the components and the above evaluation results, Table 1 is divided into Table 1-1, Table 1-2, and Table 1-3. In the tables, the "content" of each component indicates the content (mass % or mass ppm) relative to the total mass of the components. Furthermore, the total residual of the contents of each component is water. In the tables, in one embodiment, an embodiment describing multiple types of components indicates that multiple types of components were added at the contents described separately. In the tables, the "molecular weight" of the nitrogen-containing resin indicates the weight average molecular weight calculated by GPC. In the tables, "pH" indicates the pH value of the components measured using a pH meter (HORIBA, Ltd., F-51 (trade name)). Furthermore, the measurement temperature was 25°C.

[0234] [Table 1] periodic acid or its salt Quaternary ammonium salts Nitrogen-containing resins PH RuER WER Ru / W evaluate type content (quality%) type content (quality%) type molecular weight content (quality in ppm) Example 1 IO-1 2.00 B-1 1.00 PA-1 3000 25 6.5 187 6.5 28.8 B Example 2 IO-1 2.00 D-1 1.00 PA-2 5000 25 6.2 188 8.0 23.5 B Example 3 IO-1 2.00 B-1 1.00 PA-3 6000 25 6.5 160 13.0 12.3 B Example 4 IO-1 2.00 D-1 1.00 PA-4 2000 25 6.3 145 11.0 13.2 B Example 5 IO-1 2.00 B-1 1.00 PA-5 2500 25 6.4 132 9.0 14.7 B Example 6 IO-1 2.00 D-1 1.00 PA-6 7000 25 6.8 175 10.0 17.5 B Example 7 IO-1 2.00 B-1 1.00 PA-7 2000 25 6.5 155 8.0 19.4 B Example 8 IO-1 2.00 D-1 1.00 PA-8 3000 25 6.9 180 10.0 18.0 B Example 9 IO-1 2.00 B-1 1.00 PA-9 5000 25 6.7 175 11.0 15.9 B Example 10 IO-1 2.00 D-1 1.00 PB-1 10000 25 6.1 164 18.0 9.1 C Example 11 IO-1 2.00 B-1 1.00 PB-1 5000 25 6.0 163 18.0 9.1 C Example 12 IO-1 2.00 D-1 1.00 PB-1 6000 25 6.2 165 20.0 8.3 C Example 13 IO-1 2.00 B-1 1.00 PB-1 3000 25 6.5 155 17.0 9.1 C Example 14 IO-1 2.00 D-1 1.00 PB-2 7500 25 6.4 152 25.0 6.1 C Example 15 IO-1 2.00 B-1 1.00 PB-3 6000 25 6.1 170 26.0 6.5 C Example 16 IO-1 2.00 D-1 1.00 PB-4 5000 25 6.2 132 16.0 8.3 C Example 17 IO-1 2.00 B-1 1.00 PC-1 10000 25 6.3 75 15.0 5.0 C Example 18 IO-1 2.00 D-1 1.00 PC-2 9000 25 6.7 52 23.0 2.3 D Example 19 IO-1 2.00 B-1 1.00 PC-1 3000 25 6.2 105 26.0 4.0 D Example 20 IO-1 2.00 D-1 1.00 PD-1 2000 25 6.5 64 19.0 3.4 D Example 21 IO-1 2.00 B-1 1.00 PD-1 4000 25 6.8 80 20.0 4.0 D Example 22 IO-1 2.00 D-1 1.00 PD-2 5000 25 6.9 92 35.0 2.6 D Example 23 IO-1 2.00 B-1 1.00 PE-1 6500 25 6.4 177 4.5 39.3 A Example 24 IO-1 2.00 D-1 1.00 PE-2 7000 25 6.3 160 4.3 37.2 A Example 25 IO-1 2.00 D-1 1.00 PE-3 3000 25 6.8 132 2.5 52.8 A Example 26 IO-1 2.00 B-1 1.00 PF-1 8000 25 6.0 87 19.0 4.6 D Example 27 IO-1 2.00 D-1 1.00 PF-2 2000 25 6.1 96 15.0 6.4 C Example 28 IO-1 2.00 D-1 1.00 PE-3 650 25 6.4 182 42.0 4.3 D Example 29 IO-1 2.00 B-1 1.00 PE-3 1500 25 6.4 165 5.0 33.0 A Example 30 IO-1 2.00 D-1 1.00 PE-3 6000 25 6.3 150 3.5 42.9 A Example 31 IO-1 2.00 B-1 1.00 PE-3 10000 25 6.6 132 7.5 17.6 B Example 32 IO-1 2.00 D-1 1.00 PE-3 20000 25 6.8 125 10.0 12.5 B Example 33 IO-1 2.00 B-1 1.00 PE-3 50000 25 6.1 105 12.0 8.8 C Example 34 IO-1 2.00 D-1 1.00 PE-3 100000 25 6.6 112 15.0 7.5 C Example 35 IO-1 2.00 B-1 1.00 PE-3 170000 25 6.8 95 19.0 5.0 C Example 36 IO-1 2.00 B-1 1.00 PE-3 250000 25 6.1 65 22.0 3.0 D Example 37 IO-1 2.00 D-1 0.20 PE-2 7000 25 1.5 32 9.5 3.4 D Example 38 IO-1 2.00 B-1 0.50 PE-2 7000 25 3.2 105 6.5 16.2 B Example 39 IO-1 2.00 D-1 0.78 PE-2 7000 25 4.5 145 4.5 32.2 A Example 40 IO-1 2.00 D-1 1.20 PE-2 7000 25 7.5 155 4.2 36.9 A

[0235] [Table 2] periodic acid or its salt Quaternary ammonium salts Nitrogen-containing resins PH RuER WER Ru / W evaluate type content (quality%) type content (quality%) type molecular weight content (mass ppm) Example 41 IO-1 2.00 B-1 1.70 PE-2 7000 25 8.0 98 3.5 28.0 B Example 42 IO-1 2.00 D-1 2.00 PE-2 7000 25 10.5 85 9.0 9.4 C Example 43 IO-1 2.00 B-1 2.50 PE-2 7000 25 12.0 45 20.0 2.3 D Example 44 IO-2 2.00 B-1 1.00 PA-1 3000 25 6.3 165 7.0 23.6 B Example 45 IO-3 2.00 B-1 1.00 PA-1 3000 25 6.4 175 6.0 29.2 B Example 46 IO-1 2.00 A-1 1.00 PE-3 3000 25 6.8 132 3.0 44.0 A Example 47 IO-1 2.00 C-1 1.00 PE-3 3000 25 6.5 105 3.8 27.6 B Example 48 IO-1 2.00 E-1 1.00 PE-3 3000 25 6.7 145 4.5 32.2 A Example 49 IO-1 2.00 F-1 1.00 PE-3 3000 25 6.2 120 4.0 30.0 A Example 50 IO-1 2.00 G-1 1.00 PE-3 3000 25 6.1 150 3.5 42.9 A Example 51 IO-1 2.00 H-1 1.00 PE-3 3000 25 6.2 135 3.7 36.5 A Example 52 IO-1 2.00 I-1 1.00 PE-3 3000 25 6.5 143 4.5 31.8 A Example 53 IO-1 2.00 J-1 1.00 PE-3 3000 25 6.3 130 4.2 31.0 A Example 54 IO-1 2.00 K-1 1.00 PE-3 3000 25 6.4 147 3.6 40.8 A Example 55 IO-1 2.00 L-1 1.00 PE-3 3000 25 6.8 150 3.1 48.4 A Example 56 IO-1 2.00 M-1 1.00 PE-3 3000 25 6.5 98 15.0 6.5 C Example 57 IO-1 2.00 N-1 1.00 PE-3 3000 25 6.4 102 19.0 5.4 C Example 58 IO-1 2.00 O-1 1.00 PE-3 3000 25 6.1 85 14.0 6.1 C Example 59 IO-1 2.00 B-2 1.00 PE-3 3000 25 6.2 137 5.1 26.9 B Example 60 IO-1 2.00 D-2 1.00 PE-3 3000 25 6.4 140 4.8 29.2 B Example 61 IO-1 2.00 B-3 1.00 PE-3 3000 25 6.8 120 17.0 7.1 C Example 62 IO-1 2.00 B-4 1.00 PE-3 3000 25 6.5 135 16.0 8.4 C Example 63 IO-1 2.00 B-1 1.00 PE-1 3000 0.1 6.6 204 29.0 7.0 C Example 64 IO-1 2.00 D-1 1.00 PE-1 3000 5 6.9 201 6.0 33.5 A Example 65 IO-1 2.00 B-1 1.00 PE-1 3000 200 6.2 165 5.4 30.6 A Example 66 IO-1 2.00 D-1 1.00 PE-1 3000 800 6.3 158 7.2 21.9 B Example 67 IO-1 2.00 D-1 1.00 PE-1 3000 1500 6.1 72 11.0 6.5 C Example 68 IO-1 0.20 D-1 0.10 PE-2 7000 5 6.5 twenty four 0.8 30.0 A Example 69 IO-1 1.00 D-1 0.50 PE-2 7000 15 6.4 89 2.5 35.6 A Example 70 IO-1 5.00 D-1 2.40 PE-2 7000 100 6.3 268 7.5 35.7 A Example 71 IO-1 2.00 B-1 1.00 PA-1 3000 10 6.9 137 2.5 54.8 A PE-2 7000 15 Example 72 IO-1 2.00 B-1 1.00 PA-1 3000 20 6.2 156 4.2 37.1 A PE-3 3000 5 Example 73 IO-1 2.00 B-1 0.50 PA-1 3000 25 6.2 170 6.5 26.2 B D-1 0.50 Example 74 IO-1 2.00 B-1 0.50 PE-3 7000 25 6.2 145 3.7 39.2 A E-1 0.50 Comparative Example 1 IO-1 2.00 B-1 1.00 - - - 6.2 227 199.0 1.1 E Comparative Example 2 - - B-1 1.00 PF-1 3000 25 11.7 0.1 15.0 0.01 E Comparative Example 3 IO-1 2.00 - - PF-1 3000 25 2.7 twenty one 35.0 0.6 E

[0236] [Table 3] periodic acid or its salt Quaternary ammonium salts Nitrogen-containing resins additive PH RuER WER Ru / W evaluate type content (quality%) type content (quality%) type molecular weight content (mass ppm) type content (quality in ppm) Example 75 IO-1 2.00 B-1 1.00 PE-1 6500 25 IA 10 6.8 165 4.2 39.3 A Example 76 IO-1 2.00 B-1 1.00 PE-1 6500 25 TEA 10 6.8 179 4.7 38.1 A Comparative Example 4 IO-1 2.00 B-1 1.00 - - - BMPC 10000 6.4 182 168.0 1.1 E

[0237] The results in Table 1 confirm that the Ru / W selectivity of the compositions of the present invention is excellent. A comparison of Examples 10-22, 26, and 27 with Examples 1-9, 23-25, and 71-76 confirms that the Ru / W selectivity is even better when the nitrogen-containing resin has a quaternary ammonium salt structure. A comparison of Examples 1-9 and 73 with Examples 23-25, 71, 72, and 74-76 confirms that the Ru / W selectivity is even better when the nitrogen-containing resin contains nitrogen atoms in the main chain. A comparison of Examples 56-58 with Examples 23-25, 46-55, 59-62, and 71-76 confirmed that the Ru / W selectivity of the quaternary ammonium salt is superior when it contains at least one salt selected from the group consisting of tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, ethyltrimethylammonium salt, triethylmethylammonium salt, diethyldimethylammonium salt, tributylmethylammonium salt, dimethyldipropylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, (2-hydroxyethyl)trimethylammonium salt, and (2-hydroxyethyl)triethylammonium salt. A comparison of Examples 37, 42, and 43 with Examples 38-41 confirmed that the Ru / W selectivity is superior at pH values ​​of 3.0-10.0. A comparison of Examples 28 and 36 with Examples 29-35 confirmed that the Ru / W selectivity is superior when the weight-average molecular weight of the nitrogen-containing resin is between 1000 and 200000. A comparison of Examples 63 and 67 with Examples 64 to 66 confirmed that the Ru / W selectivity was superior when the content of the nitrogen-containing resin was 1 to 1000 ppm by mass relative to the total mass of the composition.

[0238] <Purification Treatment> Furthermore, the compositions of Examples 1 to 76 were purified using methods 1 to 6 as described below, thereby obtaining 500g of purified compositions for each. The same evaluation results as described above were obtained for each purified composition, yielding the same evaluation as for each example.

[0239] [Method 1] ORLITE DS-4 (75 ml) manufactured by Organo Corporation was filled into a vertically positioned column (300 ml capacity) as a cation exchange resin. The composition was passed through the column at a space velocity (SV) of 1.4 (1 / h). Throughout the series of operations, the temperature of the cation exchange resin and the composition was maintained at 25°C.

[0240] [Method 2] ORLITE DS-21 (75 ml) manufactured by Organo Corporation was filled into a vertically positioned column (300 ml capacity) as a chelating resin. The composition was passed through the column at a space velocity (SV) of 1.4 (1 / h). Throughout the series of operations, the temperature of the chelating resin and the composition was 25°C.

[0241] [Method 3] A resin mixture consisting of 75 ml of ORLITE DS-21 and 75 ml of DS-4 manufactured by Organo Corporation was filled into a vertically positioned column (300 ml capacity) as a mixed resin. The composition was passed through the column at a space velocity (SV) of 1.4 (1 / h). Throughout the series of operations, the temperature of the mixed resin and the composition was maintained at 25°C.

[0242] [Method 4] The composition was passed through a Mustang Q ion exchange resin membrane manufactured by Pall Corporation (0.02 m2) at a rate of 100 mL / min. Throughout the series of operations, the temperature of the ion exchangers and the composition on the membrane was maintained at 25 °C.

[0243] [Method 5] 75 ml of ORLITE DS-4 manufactured by Organo Corporation was filled into a vertically arranged column (300 ml capacity) as a cation exchange resin. This was used as a cation exchange column. 75 ml of ORLITE DS-21 manufactured by Organo Corporation was filled into a vertically arranged column (300 ml capacity) as a chelating resin. This was used as a chelating resin column. The composition was passed through the cation exchange column, and then through the chelating resin column. In each pass, the space velocity (SV) was 1.4 (1 / h). Throughout the series of operations, the temperature of the cation exchange resin, chelating resin, and composition was 25°C.

[0244] [Method 6] The composition was passed through the chelating resin column of Method 5 described above, and then through the cation exchange column of Method 5 described above. In any passage, the passage was carried out at a space velocity (SV) of 1.4 (1 / h). Throughout the series of operations, the temperature of the cation exchange resin, chelating resin, and composition was 25°C. [Simplified Explanation of the Diagram]

[0011] Figure 1 is a schematic diagram of the upper cross-section of an example of the workpiece used in step A1. Figure 2 is a schematic diagram of the upper cross-section of an example of the workpiece shown in Figure 1 after step A1 is performed. Figure 3 is a schematic diagram of the upper cross-section of another example of the workpiece used in step A1. Figure 4 is a schematic diagram of the upper cross-section of an example of the workpiece shown in Figure 3 after step A1 is performed. Figure 5 is a schematic diagram of an example of the workpiece used in step A2. Figure 6 is a schematic cross-section of an example of the workpiece used in step A4. Figure 7 is a schematic cross-section of an example of the workpiece before dry etching. Figure 8 is a schematic cross-section of another example of the workpiece used in step A4. Figure 9 is a schematic cross-section of an example of the workpiece before Ru-containing film formation. Figure 10 is a schematic cross-section of an example of the workpiece used in step A6.

Claims

1. A composition for removing ruthenium-containing material from a substrate, comprising: periodic acid or a salt thereof; a quaternary ammonium salt; a nitrogen-containing resin; and a solvent, wherein the content of the periodic acid or its salt is 0.01 to 15.00% by mass relative to the total mass of the composition, the content of the quaternary ammonium salt is 0.01 to 10.00% by mass relative to the total mass of the composition, the content of the nitrogen-containing resin is 0.1 to 1500 ppm by mass relative to the total mass of the composition, and the content of the solvent is 50% by mass or more relative to the total mass of the composition.

2. The composition as claimed in claim 1, wherein the aforementioned resin has repeating units comprising nitrogen atoms.

3. The composition as claimed in claim 1, wherein the aforementioned resin comprises a repeating unit selected from the group consisting of repeating units represented by formula (1), repeating units represented by formula (2), repeating units represented by formula (3), and repeating units represented by formula (4), wherein in formula (1), L11 to L15 each independently represent a single bond or a divalent linking group, in formula (1), X represents a divalent linking group containing a nitrogen atom, in formula (1), R11 each independently represents a monovalent substituent, in formula (1), n1 represents an integer from 0 to 5, in formula (2), L21 represents a divalent linking group, in formula (2), L22 represents a single bond or a divalent linking group, in formula (2), R21 represents a hydrogen atom or a monovalent substituent, in formula (2), R22 represents a monovalent substituent containing a nitrogen atom. In formula (3), L31 represents a divalent linker. In formula (3), R31 and R32 independently represent monovalent substituents. In formula (3), A- represents a monovalent anion. In formula (4), L41 represents a divalent linker. In formula (4), R41 represents a hydrogen atom or a monovalent substituent.

4. The composition as claimed in claim 3, wherein the aforementioned resin comprises repeating units selected from the group consisting of repeating units represented by the aforementioned formula (1), repeating units represented by the aforementioned formula (2), and repeating units represented by the aforementioned formula (3).

5. The composition as described in claim 3, wherein the aforementioned resin comprises the repeating unit represented by the aforementioned formula (1).

6. The composition as described in claim 3, wherein the aforementioned resin comprises the repeating unit represented by the aforementioned formula (3).

7. The composition as claimed in claim 1, wherein the aforementioned resin has repeating units comprising a quaternary ammonium salt structure.

8. The composition as claimed in claim 1, wherein the aforementioned resin contains nitrogen atoms in the main chain.

9. The composition as claimed in claim 1, wherein the aforementioned periodic acid or a salt thereof comprises at least one selected from the group consisting of orthoperiodic acid, metaperiodic acid, and salts thereof.

10. The composition as claimed in claim 1, wherein the aforementioned quaternary ammonium salt comprises at least one selected from the group consisting of tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, ethyltrimethylammonium salt, triethylmethylammonium salt, diethyldimethylammonium salt, tributylmethylammonium salt, dimethyldipropylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, (2-hydroxyethyl)trimethylammonium salt, and (2-hydroxyethyl)triethylammonium salt.

11. The composition as described in claim 1, having a pH of 3.0 to 10.

0.

12. The composition as claimed in claim 1, wherein the weight average molecular weight of the aforementioned resin is 1,000 to 200,000.

13. The composition as claimed in claim 1, wherein the content of the aforementioned resin is 1 to 1000 ppm by mass relative to the total mass of the aforementioned composition.

14. The composition as described in claim 1 does not substantially contain insoluble particles.

15. A method for treating a workpiece, wherein the workpiece containing ruthenium and tungsten is brought into contact with the composition described in any one of claims 1 to 14 to remove ruthenium.

16. A composition comprising: periodic acid or a salt thereof; a quaternary ammonium salt; a resin containing nitrogen atoms; and a solvent, wherein the content of the periodic acid or its salt is 0.01 to 15.00% by mass relative to the total mass of the composition, the content of the quaternary ammonium salt is 0.01 to 10.00% by mass relative to the total mass of the composition, the content of the nitrogen-containing resin is 0.1 to 1500 ppm by mass relative to the total mass of the composition, and the solvent comprises water, wherein the content of water is 50% by mass or more relative to the total mass of the composition.

17. The composition as described in claim 16 does not substantially contain insoluble particles.

18. The composition as described in claim 16 has a pH of 4.5 or higher.

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