Method for processing compositions and materials to be processed

Abstract

The present invention addresses the problem of providing a composition which exhibits excellent removability of ruthenium with respect to tungsten if applied to an object to be processed containing tungsten and ruthenium. A composition according to the present invention contains periodic acid or a salt thereof, a quaternary ammonium salt, a resin containing a nitrogen atom, and a solvent.

Description

[Technical Field]

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

[0002] When forming circuits and components, it is common to perform an etching process using chemical solutions. In this case, since multiple materials may be present on the substrate, it is desirable that the etching solution used is capable of selectively removing only specific materials.

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

[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, and tetramethylammonium hydroxide, etc. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-087945 [Overview of the project] [Problems that the invention aims to solve]

[0006] While Ru is used in wiring materials, tungsten (hereinafter also simply referred to as "W") is sometimes used in wiring materials. When both Ru and W are present on a semiconductor substrate, there is a need to selectively remove only Ru without corroding W. When the present inventors examined the removal composition described in Patent Document 1, they found that it did not have sufficient ability to selectively remove Ru from W, and further improvements were needed.

[0007] Therefore, the object of the present invention is to provide a composition that exhibits excellent removal properties of Ru from W when applied to a workpiece containing W and Ru. Furthermore, the present invention also aims to provide a method for processing an object to be processed using the above-mentioned composition. [Means for solving the problem]

[0008] The inventors of this invention have diligently studied and, as a result, completed the present invention. Specifically, they have found that the above problems can be solved by the following configuration.

[0009] [1] Periodic acid or a salt thereof, Quaternary ammonium salts and A resin containing nitrogen atoms, A composition containing a solvent. [2] The composition according to [1], for use on an object containing ruthenium. [3] The composition according to [1] or [2], wherein the resin has repeating units containing nitrogen atoms. [4] The composition according to any one of [1] to [3], wherein the resin comprises repeating units selected from the group consisting of repeating units represented by formula (1) described later, repeating units represented by formula (2) described later, repeating units represented by formula (3) described later, and repeating units represented by formula (4) described later. [5] The composition according to [4], wherein the resin comprises repeating units selected from the group consisting of repeating units represented by formula (1) described later, repeating units represented by formula (2) described later, and repeating units represented by formula (3) described later. [6] The composition according to [4], wherein the resin contains a repeating unit represented by formula (1) described later. [7] The composition according to [4], wherein the resin contains a repeating unit represented by formula (3) described later. [8] The composition according to any one of [1] to [7], wherein the resin has repeating units containing a quaternary ammonium salt structure. [9] The composition according to any one of [1] to [8], wherein the resin contains nitrogen atoms in its main chain.

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

[10] , wherein the above 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 triethyl(2-hydroxyethyl)ammonium salt.

[12] A composition according to any one of [1] to

[11] , wherein the pH is 3.0 to 10.0.

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

[12] , wherein the weight-average molecular weight of the resin is 1,000 to 200,000.

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

[13] , wherein the content of the above resin is 1 to 1000 ppm by mass relative to the total mass of the above composition.

[15] A composition according to any one of [1] to

[14] , which is substantially free of insoluble particles.

[16] A method for treating an object containing ruthenium and tungsten, comprising contacting the object with any one of [1] to

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

[0010] According to the present invention, when applied to a workpiece containing W and Ru, a composition can be provided that exhibits excellent removal properties of Ru from W. Furthermore, according to the present invention, a method for processing a material containing W and Ru can also be provided. [Brief explanation of the drawing]

[0011] [Figure 1] This is a schematic diagram of the upper cross-section showing an example of a workpiece used in process A1. [Figure 2] Figure 1 is a schematic diagram of the upper cross-section showing an example of the workpiece after process A1 has been performed. [Figure 3] This is a schematic diagram of the upper cross-section showing another example of the workpiece used in process A1. [Figure 4] This is a schematic diagram of the upper cross-section showing an example of the workpiece shown in Figure 3 after process A1 has been performed. [Figure 5] This is a schematic diagram showing an example of a workpiece used in process A2. [Figure 6] This is a schematic cross-sectional view showing an example of a workpiece used in process A4. [Figure 7] This is a schematic cross-sectional view showing an example of a workpiece before dry etching. [Figure 8] This is a schematic cross-sectional diagram showing another example of a workpiece used in process A4. [Figure 9] This is a schematic cross-sectional view showing an example of a workpiece before the formation of a Ru-containing film. [Figure 10] This is a schematic cross-sectional view showing an example of a workpiece used in process A6. [Modes for carrying out the invention]

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

[0013] The following definitions are used in this specification. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, "ppm" is an abbreviation for "parts per million," and 10 -6 It means that. Also, "ppb" is an abbreviation for "parts per billion," which means 10 -9 It means that. "ppt" is an abbreviation for "parts per trillion," and 10 -12 It means... In this specification, if two or more components are present, the "content" of those components means the total content of those two or more components.

[0014] Unless otherwise specified, "exposure" includes exposure using far-ultraviolet light such as mercury lamps and excimer lasers, X-rays, or EUV light, and drawing using particle beams such as electron beams or ion beams. "Preparation" includes not only preparing specific materials by synthesizing or mixing them, but also procuring the required items by purchasing them, etc.

[0015] In this specification, unless otherwise specified, the compounds described may include structural isomers (compounds with the same number of atoms but different structures), optical isomers, and isotopes. Furthermore, the isomers and isotopes may include one or more types. In this specification, dry etching residue refers to by-products generated by dry etching (e.g., plasma etching), and includes, for example, organic residues derived from photoresist, Si-containing residues, and metal-containing residues (e.g., transition metal-containing residues). In this specification, unless otherwise specified, the bonding direction of a divalent group (e.g., -COO-) is such that if Y in a compound represented as "XYZ" is -COO-, the compound may 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 calculated using polystyrene as the standard substance, measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names of Tosoh Corporation) as the column, THF (tetrahydrofuran) as the eluent, a differential refractometer as the detector, and polystyrene as the standard substance. In this specification, unless otherwise specified, the molecular weight of a compound with a 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. The mechanism by which the composition of the present invention exhibits excellent removal of Ru from W when applied to a workpiece containing W and Ru is not entirely clear, but the inventors speculate as follows. The composition, by containing periodic acid or its salts and a solvent, can exhibit removal (etching) ability for both W and Ru. However, it is believed that the inclusion of a resin containing nitrogen atoms in the composition primarily suppresses the etching of W and selectively etches Ru. Furthermore, it is believed that the inclusion of a quaternary ammonium salt in the composition promotes the dissolution of Ru, thereby enabling selective etching of Ru. The following provides a detailed explanation of the components that may be included in the composition. Furthermore, when applied to materials containing both W and Ru, the superior ability to remove Ru from W is also referred to as "excellent Ru / W selectivity."

[0018] [Periodic acid or its salts] The composition of the present invention comprises periodic acid or a salt thereof. Examples of periodic acid or its salts include orthoperiodic acid (H5IO6), metaperiodic acid (HIO4), and their salts (e.g., sodium salts or potassium salts). Among these, orthoperiodate, orthoperiodate salt, or metaperiodate are preferred due to their excellent Ru / W selectivity, with orthoperiodate being more preferred. Periodic acid or its salts may be used individually, or in combination of two or more types. The content of periodic acid or its salt is preferably 0.01 to 15.00% by mass, more preferably 0.10 to 10.00% by mass, and even more preferably 0.10 to 5.00% by mass, based on the total mass of the composition. When using two or more types of periodic acid or its salts, it is preferable that the total content of periodic acid or its salts is within the above preferred range. Furthermore, in the composition, a portion of the periodic acid may form a salt structure with a resin containing nitrogen atoms, as described later.

[0019] [Quaternary ammonium salts] The composition of the present invention contains a quaternary ammonium salt. A quaternary ammonium salt is a compound composed of a quaternary ammonium cation and an anion. While quaternary ammonium salts are not particularly limited, they preferably include those represented by the following formula (a).

[0020] [ka]

[0021] In formula (a), R a ~R d Each of these independently represents an alkyl group which may have substituents. The above alkyl group may be linear or branched, with linear being preferred. The number of carbon atoms in the alkyl group moiety of the above alkyl group is preferably 1 to 20, more preferably 1 to 8, and still more preferably 1 to 4. Specific examples of the above alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and a hexadecyl group. Examples of the above substituent include a hydroxy group and a phenyl group. Examples of the alkyl group having a substituent include a 2-hydroxyethyl group, a 2-hydroxypropyl group, and a benzyl group. Further, a methylene group constituting the above alkyl group may be substituted with a divalent substituent such as -O-. The total number of carbon atoms contained in the quaternary ammonium salt represented by formula (a) is not particularly limited, but is preferably 4 to 20, and more preferably 4 to 14. Further, R a to R d the alkyl group which may have two substituents selected from the above may be bonded to each other to form a ring.

[0022] In formula (a), A - represents a monovalent anion. A - Examples of the monovalent anion represented by include F - , Cl - , Br - , OH - , NO3 - , CH3COO - , and CH3CH2SO4 - and the like. F - , Cl - , Br - , or OH - is preferable, Cl - or OH - is more preferable, and OH - is even more preferable.

[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 called "choline"), triethyl(2-hydroxyethyl)ammonium salt, diethylbis(2-hydroxyethyl)ammonium salt, ethyltris(2-hydroxyethyl)ammonium salt, and tris(2-hydroxyethyl)methylammonium salt. In particular, in terms of excellent Ru / W selectivity, the quaternary ammonium salt preferably contains 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 triethyl(2-hydroxyethyl)ammonium salt. The anion contained in the above salt is F - Cl - , Br - , or OH - Preferably, Cl - or OH - More preferably, OH - That is even more preferable.

[0024] A single quaternary ammonium salt may be used, or two or more may be used in combination. The total content of quaternary ammonium salts is preferably 0.01 to 10.00% by mass, more preferably 0.10 to 5.00% by mass, and even more preferably 0.10 to 2.50% by mass, based on the total mass of the composition. The molecular weight of the quaternary ammonium salt is preferably 90 to 1000, more preferably 90 to 500, even more preferably 90 to 300, and particularly preferably 90 to 200.

[0025] [Resin containing nitrogen atoms] The composition of the present invention contains a resin containing nitrogen atoms (hereinafter also referred to as "nitrogen-containing resin"). The nitrogen-containing resin is a compound different from a quaternary ammonium salt. Nitrogen-containing resins are resins that contain nitrogen atoms as part of their composition. A resin is a compound formed by the polymerization of monomers, and specifically refers to a compound with a weight-average molecular weight of 500 or more. A nitrogen-containing resin may have nitrogen atoms in part of the resin, but it is preferable that it contains repeating units having nitrogen atoms (hereinafter also referred to as "nitrogen-containing units"). Furthermore, a nitrogen-containing resin may also contain repeating units other than nitrogen-containing units (hereinafter also referred to as "other units").

[0026] (Nitrogen-containing units) The form of the nitrogen atom in a nitrogen-containing unit is not particularly limited, and the nitrogen atom may be cationized. Furthermore, the bonds between the nitrogen atom and the surrounding atoms in the nitrogen-containing unit may be all single bonds, may include double bonds, or may include triple bonds. The nitrogen atom in a nitrogen-containing unit can be represented by the structures shown in the following formulas (A) to (D).

[0027] [ka]

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

[0029] In terms of superior Ru / W selectivity, the nitrogen atom structure represented by formula (A) or formula (B) is preferred for the nitrogen atom structure of the nitrogen-containing unit. Therefore, the primary amine structure, secondary amine structure, tertiary amine structure, or quaternary ammonium salt structure is preferred for the nitrogen atom structure of the nitrogen-containing unit. In terms of superior Ru / W selectivity, the secondary amine structure, tertiary amine structure, or quaternary ammonium salt structure is more preferred for the nitrogen atom structure of the nitrogen-containing unit, the tertiary amine structure or quaternary ammonium salt structure is even more preferred, and the quaternary ammonium salt structure is particularly preferred.

[0030] Furthermore, the nitrogen atoms in a nitrogen-containing unit may be contained in either the main chain or the side chain, or in both the main chain and the side chain. In this specification, "main chain" refers to the relatively longest bonding chain in the polymer compound molecule constituting the resin, and "side chain" refers to an atomic group branching off from the main chain. In terms of superior Ru / W selectivity, it is preferable that the nitrogen atoms in the nitrogen-containing units are included in the main chain at least.

[0031] A more specific example of a nitrogen-containing unit is the repeating unit represented by the following equations (1) to (4).

[0032] [ka]

[0033] In formula (1), L 11 ~L 15 Each of these independently represents a single bond or a divalent linking group. L 11 and L 12Examples of divalent linking groups represented by include alkylene groups, cycloalkylene groups, arylene 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 consisting of -O-, -S-, -CO-, -COO-, -CONH-, and -SO2- with an alkylene group, a cycloalkylene group, or an arylene group. The alkylene group may be linear or branched, with linear being preferred. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The cycloalkylene group may be monocyclic or polycyclic, with monocyclic being preferred. The number of carbon atoms in the cycloalkylene is not particularly limited, but 5 to 12 is preferred, and 5 to 8 is more preferred. The above-mentioned arylene group may be monocyclic or polycyclic, with monocyclic being preferred. Furthermore, the arylene group may be a heteroarylene group containing atoms other than carbon atoms as ring member atoms. The number of ring member atoms in the arylene group is not particularly limited, but 5 to 15 is preferred, and 5 to 10 is more preferred. Among the above, L 11 and L 12 The group is preferably a single bond, an alkylene group, or a group combining an alkylene group and -SO2-, with the alkylene group being more preferred. More specifically, L 11 and L 12 The alkylene group represented is preferably a methylene group, an ethylene group, or a propylene group. In formula (1), L 13 ~L 15 Each of these independently represents a single bond or a divalent linking group. L 13 ~L 15Examples of divalent linking groups represented by include alkylene groups, -O-, -S-, -CO-, -COO-, -CONH-, and -SO2-, as well as groups in which one or more divalent linking groups selected from the group consisting of -O-, -S-, -CO-, -COO-, -CONH-, and -SO2- are combined with an alkylene group. Preferred embodiments of the alkylene group are as described above. Among the above, L 13 The single bond or alkylene group is preferred, with the single bond being preferred. 14 and L 15 The single bond or alkylene group is preferred, and the alkylene group is preferred. More specifically, L 14 and L 15 The alkylene group represented is preferably a methylene group or an ethylene group.

[0034] In formula (1), X represents a divalent linking group containing a nitrogen atom. As for divalent linking groups containing a nitrogen atom, divalent linking groups containing a secondary amine structure, a tertiary amine structure, or a quaternary ammonium salt structure are preferred. More specifically, divalent linking groups represented by the following formula (X1) or divalent linking groups represented by the following formula (X2) are preferred.

[0035] [ka]

[0036] In equations (X1) and (X2), * represents the join position. In formula (X1), R 12 represents a hydrogen atom or a monovalent substituent. R 12 Examples of monovalent substituents include C1-C6 alkyl groups that may have substituents. The alkyl group may be linear or branched, with linear being preferred. The number of carbon atoms in the alkyl group is preferably 1-4, and more preferably 1-3. Examples of substituents on the alkyl group that may have substituents include halogen atoms, carboxyl groups, sulfo groups, and hydroxyl groups. Among the above, R 12 The alkyl group is preferably a hydrogen atom or an unsubstituted alkyl group, and more preferably an unsubstituted alkyl group. More specifically, the unsubstituted alkyl group is preferably a methyl group, an ethyl group, or a propyl group. The divalent linking group represented by formula (X1) may also form a salt with an acid. Examples of acids that form a salt with the divalent linking group represented by formula (X1) include sulfuric acid, sulfurous acid, iodic acid, hydrogen chloride, hydrogen bromide, nitric acid, amidosulfuric acid, acetic acid, ethyl sulfuric acid, and methanesulfonic acid.

[0037] In formula (X2), R 13 and R 14 Each of these independently represents a monovalent substituent. 13 and R 14 The monovalent substituent represented by is R 12 Examples include monovalent substituents represented by , and the same applies to preferred embodiments. In formula (X2), A - This represents a monovalent anion. A - The monovalent anion represented by can be either an inorganic or organic anion. An example of an inorganic anion is the hydrogen sulfate ion (HSO4). - ), bisulfite ions (HSO3 - ), iodate ion (IO3 - Examples of organic anions include halogen ions and nitrate ions. Examples of organic anions include acetate ions, ethyl sulfate ions and methanesulfonate ions. Among these, halogen ions or ethyl sulfate ions are preferred. Examples of halogen ions include fluoride ions, chloride ions, bromide ions and iodide ions, with chloride ions being preferred.

[0038] In formula (1), R 11 R represents a monovalent substituent. 11 If multiple instances exist, each independently represents a monovalent substituent. R 11Examples of monovalent substituents represented by include optionally substituted alkyl groups, halogen atoms, and hydroxyl groups. For optionally substituted alkyl groups, R 12 The monovalent substituent represented by is similar to the alkyl group which may have substituents as described above. In equation (1), n1 represents an integer between 0 and 5. n1 is preferably 0 to 3, more preferably 0 to 2, even more preferably 0 or 1, and particularly preferably 0.

[0039] In formula (2), L 21 This represents a divalent linking group. L 21 The divalent linking group represented by is L 11 and L 12 Examples include the divalent linking group represented by , and the preferred embodiment is similar. That is, L 21 The divalent linking group represented by is preferably an alkylene group, and more preferably a methylene group, an ethylene group, or a propylene group. One or more hydrogen atoms of the alkylene group may be substituted with monovalent substituents, and examples of monovalent substituents include halogen atoms and hydroxyl groups. In formula (2), L 22 This represents a single bond or a divalent linking group. L 22 The divalent linking group represented by is L 11 and L 12 The divalent linking group represented by L is an example. 22 The divalent linking group represented by is preferably -COO-, -CONH-, or an alkylene group, or a group that combines one or more divalent linking groups selected from the group consisting of -O-, -S-, -CO-, -COO-, -CONH-, and -SO2- with an alkylene group. Among the above, L 22 is a single bond, an alkylene group, or a -COO-alkylene group A group is preferred, and an alkylene group is more preferred.

[0040] In formula (2), R 21 represents a hydrogen atom or a monovalent substituent. R 21 Examples of the monovalent substituent represented by include a halogen atom and an alkyl group having 1 to 3 carbon atoms. Among these, R 21 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In formula (2), R 22 represents a nitrogen atom-containing monovalent substituent. R 22 As the nitrogen atom-containing monovalent substituent represented by , monovalent substituents including structures represented by the above formulas (A) to (D) are preferred, and monovalent substituents represented by the following formulas (B1) to (B8) are more preferred.

[0041]

Chemical formula

[0042] In formulas (B1) to (B8), * represents a bonding position. In formulas (B1) and (B3), R 23 to R 25 each independently represent a hydrogen atom or a monovalent substituent. R 23 to R 25 Examples of the monovalent substituent represented by include the monovalent substituent represented by R 12 . Among these, R 23 to R 25 is preferably a hydrogen atom or an unsubstituted alkyl group, and more preferably a hydrogen atom. In formulas (B5) to (B8), R 26 to R 29 each independently represent a monovalent substituent. R 26 to R 29 Examples of the monovalent substituent represented by include the monovalent substituent represented by R 12 . Among these, in formulas (B5) to (B8), R 26 to R 29 is preferably an unsubstituted alkyl group.

[0043] In formulas (B2) to (B4) and (B6) to (B8), R2 represents a monovalent substituent. When a plurality of R2 are present, each R2 independently represents a monovalent substituent. As the monovalent substituent represented by R2, R11 examples include the same groups as the monovalent substituent represented by . In formulas (B3), (B4), (B7) and (B8), m represents an integer of 0 to 4. n is preferably 0 to 2, more preferably 0 or 1, and still more preferably 0. In formulas (B5) to (B8), A - represents a monovalent anion. A in formulas (B5) to (B8) - is the same as A in formula (X2) above - includes the same anions, and preferred embodiments are also the same.

[0044] Note that the monovalent substituents represented by formulas (B1) to (B4) may form a salt with an acid. Examples of the acid that forms a salt with the monovalent substituent represented by formulas (B1) to (B4) include acids that form a salt with the divalent linking group represented by formula (X1) above.

[0045] Among the above, R 22 As the monovalent substituent containing a nitrogen atom represented by, a monovalent substituent represented by formula (B1), a monovalent substituent represented by formula (B2), or a monovalent substituent represented by formula (B5) is preferred, and a monovalent substituent represented by formula (B1) is more preferred.

[0046] In formula (3), L 31 represents a divalent linking group. L 31 As the divalent linking group represented by, L 11 and L 12 examples include the divalent linking groups represented by, with an alkylene group being preferred. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 3 to 6 carbon atoms. That is, a propylene group, butylene group, pentylene group or hexylene group is more preferred. Note that one or more hydrogen atoms of the alkylene group may be substituted with a monovalent substituent, and examples of the monovalent substituent include a halogen atom and a hydroxy group. Examples of embodiments in which a hydrogen atom of an alkylene group is substituted with a monovalent substituent include -CH2-CHOH-CH2- and -CH2-CH2-CHOH-CH2-. In formula (3), R31 and R 32 Each of these independently represents a monovalent substituent. R 31 and R 32 The monovalent substituent represented by is R 12 Examples include monovalent substituents represented by R, and the same applies to preferred embodiments. That is, R 31 and R 32 The monovalent substituent represented by is preferably an unsubstituted alkyl group, and more preferably a methyl group, an ethyl group, or a propyl group. In formula (3), A - This represents a monovalent anion. A in equation (3) - A in the above equation (X2) is - Similar anions can be cited, and the preferred embodiments are also similar.

[0047] In formula (4), L 41 This represents a divalent linking group. L 41 The divalent linking group represented by is L 11 and L 12 Examples include divalent linking groups represented by , with alkylene groups being preferred. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 2 to 4. In formula (4), R 41 represents a hydrogen atom or a monovalent substituent. R 41 The monovalent substituent represented by is R 12 Examples include monovalent substituents represented by R, and the same applies to preferred embodiments. That is, R 41 The monovalent substituent represented by is preferably an unsubstituted alkyl group, more preferably a methyl group, an ethyl group, or a propyl group. Among these, a hydrogen atom is preferred.

[0048] The repeating units represented by formulas (1) and (2) are embodiments having nitrogen atoms in the side chains, while the repeating units represented by formulas (3) and (4) are embodiments having nitrogen atoms in the main chain.

[0049] As for the nitrogen-containing units to be included in the nitrogen-containing resin, among the above formulas (1) to (4), the repeating units represented by formulas (1) to (3) are preferred in terms of superior Ru / W selectivity, the repeating units represented by formula (1) or formula (3) are more preferred, and the repeating units represented by formula (1) are even more preferred.

[0050] Furthermore, nitrogen-containing resins may contain other nitrogen-containing units besides those mentioned above. Other nitrogen-containing units are not particularly limited and may be known nitrogen-containing units. Other nitrogen-containing units may be repeating units represented by formulas (1) to (4) above, which are crosslinked with a crosslinkable group or a crosslinkable molecule. Examples of crosslinkable groups include epoxy groups and ethylenically unsaturated groups. Examples of crosslinkable molecules include isocyanate compounds, epichlorohydrin, and formaldehyde.

[0051] Nitrogen-containing resins may contain multiple types of nitrogen-containing units. The total nitrogen content is preferably 5 to 100% by mass, more preferably 20 to 100% by mass, and even more preferably 40 to 100% by mass, relative to the total mass of the nitrogen-containing resin. The total nitrogen-containing unit content is preferably 5 to 100 mol%, more preferably 20 to 100 mol%, and even more preferably 40 to 100 mol%, relative to the total repeating units of the nitrogen-containing resin.

[0052] (Other units) Other units that the nitrogen-containing resin may contain are not particularly limited and may be known repeating units. Other units include, for example, repeating units based on monomers having an ethylenically unsaturated group. Examples of monomers having an ethylenically unsaturated group include carboxylic acids having an ethylenically unsaturated group. Examples of carboxylic acids having the above-mentioned ethylenically unsaturated group include acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic acid, and maleic anhydride, as well as salts thereof. Alternatively, the above-mentioned carboxylic acid may be condensed or added compounds of a compound having a hydroxyl group, a compound having an amino group, or a compound having a glycidyl group. Examples of such compounds include ester compounds of acrylic acid or methacrylic acid and a compound having a hydroxyl group, amide compounds of acrylic acid or methacrylic acid and a compound having a primary or secondary amino group, and half-ester compounds of maleic acid and a compound having a hydroxyl group. Other units include repeating units based on vinyl acetate, in which the carboxyl group may be removed by modification such as hydrolysis. In other words, they may be constituent units that can be considered to be based on vinyl alcohol.

[0053] Nitrogen-containing resins may contain multiple types of other units. The content of other units is preferably 0 to 95% by mass, more preferably 0 to 80% by mass, and even more preferably 0 to 60% by mass, relative to the total mass of the nitrogen-containing resin. The nitrogen-containing unit content is preferably 5 to 100% by mass, more preferably 20 to 100% by mass, and even more preferably 40 to 100% by mass, relative to the total repeating units of the nitrogen-containing resin.

[0054] Specific examples of nitrogen-containing resins include resins synthesized using allylamine and its salts, N-alkylallylamine and its salts, N,N-dialkylallylamine and its salts, trialkylallylammonium salts, diallylamine and its salts, N-alkyldiallylamine and its salts, and N,N-dialkylammonium salts as monomers. The alkyl group in each of the above monomers can be independently a methyl group or an ethyl group. Compounds that form salts with the above amines include hydrogen chloride (hydrochloric acid), amidosulfuric acid, acetic acid, and ethylsulfuric acid. A chloride ion can be used as a counteranion for the above ammonium salts.

[0055] Furthermore, resins synthesized using diallylamine or the like as monomers can become resins containing repeating units represented by formula (1) through polymerization involving cyclization. Specific compound names of the above resins include polyallylamine, polyallylamine hydrochloride, polydiallylamine, polydiallylamine hydrochloride, poly(dimethyldiallylammonium chloride), and poly(methylethyldimethylammonium ethyl sulfate). Note that the resins listed above are resins containing repeating units with a cyclic structure.

[0056] Furthermore, resins synthesized using the above N,N-dialkylammonium salt as monomers can be polymerized to form resins containing repeating units represented by formula (3). A specific example of the above-mentioned resin is poly(diallyldimethylammonium chloride). Note that the resins listed above contain repeating units in a chain-like structure.

[0057] Furthermore, copolymers synthesized from two or more monomers selected from the above monomers can also be cited as nitrogen-containing resins. Examples include copolymers synthesized using allylamine and diallylamine as monomers, and copolymers synthesized using allylamine salt and diallylamine salt as monomers. Furthermore, copolymers synthesized using the above monomers and maleic acid as monomers can also be cited as nitrogen-containing resins. For example, copolymers synthesized using diallylamine and maleic acid as monomers can be cited.

[0058] Specific examples of nitrogen-containing resins include resins having a skeletal structure represented by the following formulas (P-1) to (P-23). ​​In formulas (P-1) to (P-23), the repeating unit denoted by the symbol m is the first repeating unit, and the repeating unit denoted by the symbol n is the second repeating unit. The skeletal structures represented by formulas (P-1) to (P-23) include multiple repeating units, and the bonding pattern of these repeating units is not particularly limited. For example, the repeating units may be bonded randomly (a so-called random copolymer), alternately (a so-called alternating copolymer), or in a block-like structure (a so-called block copolymer).

[0059] [ka] TIFF0007920170000007.tif102154 TIFF0007920170000008.tif65154

[0060] In the above equations (P-1) to (P-23), the ratio of the number of moles m of the first repeating unit to the number of moles n of the second repeating unit (m / n) is between 1 / 20 and 20 / 1. Furthermore, in equation (P-7), l represents the number of repetitions of the oxyalkylene unit and is an integer between 1 and 30. In addition, in formula (P-20), X represents an amide group, a nitrile group, an amino hydrochloride, or a formamide group.

[0061] Another specific example of a nitrogen-containing resin is a resin formed by the condensation polymerization of dimethylamine and epichlorohydrin (poly(2-hydroxypropyldimethylammonium chloride)). The resin formed by the condensation polymerization of dimethylamine and epichlorohydrin contains repeating units represented by formula (3).

[0062] Another specific example of nitrogen-containing resin is polyethyleneimine, which is obtained by ring-opening polymerization of ethyleneimine. Polyethyleneimine can be in linear, branched, or dendrimer forms, and in the linear form, it has repeating units represented by formula (4). Branched polyethyleneimine is a resin consisting of units represented by the following formulas (4-a), (4-b), and (4-c). In each formula, * and ** represent bond positions, and * and ** are bonded together. Dendrimer-like polyethyleneimines include resins composed of units represented by the following formulas (4-a) and (4-c). * and ** in each formula represent bonding positions, where * and ** are bonded. The end of the resin is **-CH2-CH2-NH2.

[0063] JPEG0007920170000009.jpg2797

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

[0036] to

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

[0040] to

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

[0025] to

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

[0062] to

[0039] of Japanese Patent Publication No. 2004-27162.

[0065] Nitrogen-containing resins described in paragraphs

[0068] to

[0084] of Japanese Patent Publication No. 2004-115675, paragraphs

[0051] to

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

[0097] to

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

[0026] to

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

[0037] to

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

[0062] to

[0069] of Japanese Patent Publication No. 2021-021020 are also examples.

[0065] Nitrogen-containing resins can also be commercially available. 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, PAA-N5000, and PAS-21CL, all manufactured by Nitto Boseki Medical Co., Ltd. , 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-2401, 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 include, for example, the Kathiomaster® PD series (PD-7 and PD-30), Kathiomaster® series (PE-30, EPA-SK01, and PAE-01) manufactured by Yokkaichi Gosei Co., Ltd., the Unisense® series (KHE100L, KHE107L, KHE1000L, FPA100L, FPA101L, FPA1000L, FCA1003L, FCA1001L, and KCA100L) manufactured by Senka Co., Ltd., and the Acrit® series (1SX-1055F, 1SX-6000, and 1WX-1020) manufactured by Taisei Fine Chemical Co., Ltd.

[0066] The weight-average molecular weight of the nitrogen-containing resin is preferably 1000 or more, and more preferably 1500 or more. There is no particular upper limit to the weight-average molecular weight of the nitrogen-containing resin, but examples include 500,000 or less, preferably 200,000 or less, more preferably 20,000 or less, and even more preferably 8,000 or less.

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

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

[0069] [solvent] The composition of the present invention contains a solvent. Examples of solvents include water and organic solvents, with water being preferred. The water used is preferably distilled water, ion-exchanged water, or water that has undergone purification treatment such as ultrapure water, with ultrapure water used in semiconductor manufacturing being more preferable. The water contained in the composition may contain unavoidable trace amounts of mixed components. The water content is preferably 50% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 75% by mass or more, based on the total mass of the composition. There is no particular upper limit, but it is preferably 99.999% by mass or less, and more preferably 99.9% by mass or less, based on the total mass of the composition.

[0070] As the organic solvent, a water-soluble organic solvent is preferred. A water-soluble organic solvent is an organic solvent that can be mixed with water in any proportion. Examples of water-soluble organic solvents include ether-based solvents, alcohol-based solvents, ketone-based solvents, amide-based solvents, sulfur-containing solvents, and lactone-based solvents.

[0071] Examples of ether-based solvents include diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, tetrahydrofuran, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, alkylene glycol monoalkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether), and alkylene glycol dialkyl ethers (diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether). The ether solvent preferably has 3 to 16 carbon atoms, more preferably 4 to 14, and even more preferably 6 to 12.

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

[0073] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, 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 sulfone, dimethyl sulfoxide, and sulfolane.

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

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

[0078] [Optional ingredients] The composition may contain any components other than those listed above. The following details the optional components that the composition may contain.

[0079] (Basic compounds) The composition may contain basic compounds. Basic compounds are compounds that exhibit alkalinity (pH greater than 7.0) in aqueous solutions. Examples of basic compounds include organic bases, inorganic bases, and their salts. However, the basic compounds do not include the above-mentioned quaternary ammonium salts, solvents, and 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, lactam compounds, and isocyanide compounds. Note that amine compounds refer to compounds having an amino group in their molecule that are not included in the above-mentioned alkanolamines, amine oxide compounds, and lactam compounds. However, the above organic bases do not include the above quaternary ammonium salts and the above resins containing nitrogen atoms.

[0081] Examples of amine compounds include primary amines having a primary amino group (-NH2) in the molecule, secondary amines having a secondary amino group (>NH) in the molecule, and tertiary amines having a tertiary amino group (>N-) in the molecule. Examples of primary amines, secondary amines, and tertiary amines include alkylamines, dialkylamines, and trialkylamines, respectively. The alkyl group may have substituents. Also included are alicyclic amine compounds having an alicyclic (non-aromatic) structure containing a nitrogen atom within the molecule, and salts thereof. The alicyclic amine compound may be monocyclic or bicyclic. The alicyclic may also contain heteroatoms (e.g., nitrogen, oxygen, or sulfur atoms). The alicyclic may also have substituents, and while there are no particular limitations on the substituents the alicyclic may have, examples include alkyl groups, arylalkyl groups, hydroxyalkyl groups, and aminoalkyl groups. Examples of salts of amine compounds include salts of the divalent linking group represented by formula (X1) above with the acids listed as forming a salt, among which hydrochloride salts, sulfate salts, or nitrate salts are preferred. Furthermore, the amine compound is preferably water-soluble, and preferably dissolves in 50 g or more of water per liter.

[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, ethyldimethylamine, dimethylpropylamine, diethylmethylamine, dimethylhydroxyethylamine, N-methyldiethanolamine, and benzyldimethylamine. Examples of alicyclic amine compounds include 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO), N-(2-aminoethyl)piperazine, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidinemethanol, cyclohexylamine, and 1,5-diazabicyclo[4,3,0]-5-nonene.

[0083] An example of a lactam compound is ε-caprolactam.

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

[0085] The content of the basic compound is not particularly limited, but it is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, relative to the total mass of the composition. There is no particular upper limit, but it is preferably 20.0% by mass or less, relative to the total mass of the composition. It is also preferable to adjust the basic compound within the preferred range described above so that it falls within the preferred pH range of the composition described later.

[0086] (acidic compound) The composition may contain acidic compounds. Acidic compounds are compounds that exhibit acidity (pH less than 7.0) in aqueous solutions. However, acidic compounds do not include periodic acid or its salts, or resins containing nitrogen atoms. Examples of acidic compounds include inorganic acids, organic acids, and their salts.

[0087] Examples of inorganic acids include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, hydrofluoric acid, iodic acid, perchloric acid, hypochlorous acid, and their salts. Sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, or iodic acid are preferred, and nitric acid, sulfuric acid, hydrochloric acid, or iodic acid are more preferred.

[0088] Examples of organic acids include carboxylic acids, sulfonic acids, and their salts. Examples of carboxylic acids include lower (1-4 carbon atoms) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid, as well as their salts. Examples of sulfonic acids include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (tosylic acid), and their salts.

[0089] Preferred acidic compounds include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfonic acid, or salts thereof, with sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, or p-toluenesulfonic acid being more preferred.

[0090] The content of the acidic compound is not particularly limited, but it is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, relative to the total mass of the composition. There is no particular upper limit, but it is preferably 20.0% by mass or less, relative to the total mass of the composition. It is also preferable to adjust the acidic compound to a pH range suitable for the composition described later, within the preferred range described above.

[0091] (Water-soluble polymer) The composition of the present invention may contain a water-soluble polymer. However, the water-soluble polymer does not include the nitrogen-containing resin mentioned above, nor the compounds contained in the metal corrosion inhibitor described later. Examples of water-soluble polymers include polyacrylic acid, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, and carboxyvinyl polymer.

[0092] (Surfactants) The composition of the present invention may contain a surfactant. However, the surfactant does not include the nitrogen-containing resin mentioned above. The surfactant is not particularly limited as long as it is a compound having both a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule. Examples include anionic surfactants and nonionic surfactants.

[0093] The hydrophobic groups that surfactants possess are not particularly limited, but examples include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. When the hydrophobic group includes an aromatic hydrocarbon group, the number of carbon atoms in the hydrophobic group is preferably 6 or more, and more preferably 10 or more. When the hydrophobic group does not contain an aromatic hydrocarbon group and consists only of aliphatic hydrocarbon groups, the number of carbon atoms in the hydrophobic group is preferably 8 or more, and more preferably 10 or more. There is no particular upper limit to the number of carbon atoms in the hydrophobic group, but it is preferably 24 or less, and more preferably 20 or less.

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

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

[0096] Surfactants may be used individually or in combination of two or more types. The surfactant content is preferably 0.01% by mass or more, and more preferably 0.03% by mass or more, relative to the total mass of the composition. There is no particular upper limit, but from the viewpoint of suppressing foaming of the composition, it is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the composition.

[0097] (Insoluble particles) The composition of the present invention preferably contains substantially no insoluble particles. The term "insoluble particles" as used above refers to particles such as inorganic solids and organic solids that ultimately remain as particles in the composition without dissolving. The phrase "substantially free of insoluble particles" means that when the composition is diluted 10,000 times with the solvent it contains to prepare a measurement composition, the number of particles with a particle size of 50 nm or larger contained in 1 mL of the measurement composition is 40,000 or less. The number of particles contained in the measurement composition can be measured in the liquid phase using a commercially available particle counter. Commercially available particle counter devices include those manufactured by Rion and PMS. Representative examples of the former include the KS-19F, and representative examples of the latter include the Chem20. For measuring larger particles, the KS-42 series and LiQuilaz are available. Equipment such as the II S series can be used. Examples of insoluble particles include inorganic solids such as silica (including colloidal silica and fumed silica), alumina, zirconia, ceria, titania, germania, manganese oxide, and silicon carbide; and organic solids such as polystyrene, polyacrylic resin, and polyvinyl chloride. Methods for removing insoluble particles from a composition include, for example, purification processes such as filtering.

[0098] (Metal corrosion inhibitor) The composition may contain a metal corrosion inhibitor. However, the metal corrosion inhibitor shall not contain the nitrogen-containing resin mentioned above. The type of metal corrosion inhibitor is not particularly limited, and known metal corrosion inhibitors can be used. As a metal corrosion inhibitor, one containing nitrogen atoms is preferred. For example, chelating agents, which will be described in detail later, are a good choice.

[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, piperazinyl groups, pyrrolyl groups, pyrrolidinyl groups, pyrazolyl groups, piperidinyl groups, guanidinyl groups, biguanidinyl groups, carbazatyl groups, hydrazidyl groups, semicarbazidyl groups, and aminoguanidinyl groups. A chelating agent only needs to have two or more nitrogen-containing groups, and these two or more nitrogen-containing groups may be different, partially the same, or all the same. Furthermore, the chelating agent may contain a carboxyl group. The nitrogen-containing groups and / or carboxyl groups of the chelating agent may be neutralized to form a salt. As chelating agents, those described in paragraphs

[0021] to

[0047] of Japanese Patent Publication No. 2017-504190 can be used, and their contents are incorporated herein by reference.

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

[0101] -Other metal corrosion inhibitors- The metal corrosion inhibitor may be a benzotriazole, which may have substituents. However, benzotriazole contained in the chelating agent is excluded. Benzotriazoles that may have substituents include benzotriazole (BTA), 5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-benzotriazole, 5-methyl-1H-benzotriazole, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, and 4-propylbenzotriazole. Examples include 5-propylbenzotriazole, 4-isopropylbenzotriazole, 5-isopropylbenzotriazole, 4-n-butylbenzotriazole, 5-n-butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole, 4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzotriazole, 5-hydroxybenzotriazole, dihydroxypropylbenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-t-butylbenzotriazole, 5-(1',1'-dimethylpropyl)-benzotriazole, 5-(1',1',3'-trimethylbutyl)benzotriazole, 5-n-octylbenzotriazole, and 5-(1',1',3',3'-tetramethylbutyl)benzotriazole.

[0102] The content of the metal corrosion inhibitor is not particularly limited, but it is preferably 0.1% by mass or more, and more preferably 1% by mass or more, relative to the total mass of the composition. There is no particular upper limit, but it is preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the composition.

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

[0104] Examples of metal atoms contained in the metal component include metal atoms selected from the group consisting of Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sn, Sr, Ti, Zn, and Zr. The metal component may contain one type of metal atom, or it may contain two or more types of metal atoms. The metal particles may be in elemental form, an alloy, or in a form where the metal is associated with organic matter. The metal component may be a metal component that is inevitably present in each component (raw material) of the composition, or a metal component that is inevitably present during the manufacture, storage, and / or transport of the composition, or it may be added intentionally. When the composition contains a metal component, the content of the metal component is often 0.01 ppt to 10 ppm by mass, preferably 0.1 ppt to 1 ppm by mass, and more preferably 0.1 ppt to 100 ppb by mass, relative to the total mass of the composition.

[0105] The type and content of metal components in the composition can be measured by ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry). In the ICP-MS method, the content of the target metal component is measured regardless of its form of existence. Therefore, the total mass of the target metal particles and metal ions is quantified as the content of the metal component. For ICP-MS measurements, for example, Agilent Technologies' Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) and Agilent 8900, as well as PerkinElmer's NexION350S, can be used.

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

[0107] <Properties of the composition> The following describes the chemical and physical properties of the composition.

[0108] [pH] The pH of the composition of the present invention is not particularly limited, and for example, it may be in the range of 1.0 to 14.0. In particular, the pH of the composition is preferably 1.0 to 12.0, more preferably 3.0 to 10.0, and even more preferably 4.0 to 7.5, in terms of superior Ru / W selectivity. In this specification, the pH of the composition is defined as the value obtained by measuring it at 25°C using a pH meter (F-51 (product name) manufactured by Horiba, Ltd.).

[0109] [Coarse particles] The composition preferably contains substantially no coarse particles. "Coarse particles" refers to particles with a diameter of 0.2 μm or larger, assuming the particle shape is spherical. Note that particles contained in the insoluble particles mentioned above may also be included in the coarse particle category. Furthermore, "substantially free of coarse particles" means that when the composition is measured using a commercially available measuring device in a light scattering liquid particle measurement method, there are 10 or fewer particles of 0.2 μm or larger per 1 mL of the composition. The lower limit is preferably 0 or more. Coarse particles contained in the composition include particles such as dust, dirt, organic solids, and inorganic solids that are present as impurities in the raw materials, as well as particles such as dust, dirt, organic solids, and inorganic solids that are introduced as contaminants during the preparation of the composition, and which ultimately remain as particles in the composition without dissolving. One method for measuring the content of coarse particles is to use a commercially available measuring device that employs a light scattering type liquid particle measurement method with a laser as the light source, and measure the particle content in the liquid phase. One method for removing coarse particles is filtering.

[0110] <Method for producing the composition> The method for producing the composition of the present invention is not particularly limited, and for example, it can be produced by mixing the above-mentioned components. The order or timing of mixing the components, as well as the order and timing, are not particularly limited. For example, one method of producing the composition is to sequentially add periodic acid or its salt, a quaternary ammonium salt, a resin containing nitrogen atoms, and an optional component to a stirrer such as a mixing mixer containing purified pure water, and then mix the components thoroughly to produce the composition. Methods for producing the composition include a method in which the pH of the washing solution is pre-adjusted using the above-mentioned basic compound or acidic compound, and then the components are mixed; and a method in which the pH is adjusted to the set value using the above-mentioned basic compound or acidic compound after the components have been mixed.

[0111] Alternatively, the composition of the present invention may be produced by preparing a concentrated solution with a lower solvent content (such as water) than that used, and then diluting it with a diluent (preferably water) at the time of use to adjust the content of each component to a predetermined level. The composition of the present invention may also be produced by diluting the concentrated solution with a diluent and then adjusting the pH to a set level using the basic compound or acidic compound mentioned above. When diluting the concentrated solution, a predetermined amount of the diluent may be added to the concentrated solution, or a predetermined amount of the concentrated solution may be added to the diluent.

[0112] [Metal removal process] The above manufacturing method may include a metal removal step to remove metal components from the above components and / or composition (hereinafter also referred to as the "purified product"). For example, one embodiment may involve performing the metal removal step on the purified product containing the above periodic acid or a salt thereof and water.

[0113] In the purified product containing periodic acid or a salt thereof and water, the content of periodic acid or a salt thereof is not particularly limited, but is preferably 0.0001 to 50% by mass, more preferably 1 to 45% by mass, and even more preferably 4 to 40% by mass, relative to the total mass of the purified product. From the viewpoint of excellent processing efficiency, the water content in the purified product is preferably 40% by mass or more and less than 100% by mass, preferably 50 to 99% by mass, and even more preferably 60 to 95% by mass. The purified product containing the above-mentioned periodic acid or a salt thereof and water may further contain the components included in the above composition, and / or optional components. One example of a metal removal process is step P, in which the material to be purified is subjected to an ion exchange method.

[0114] (Process P) In step P, the product to be purified as described above is subjected to an ion exchange method. The ion exchange method is not particularly limited as long as it can adjust (reduce) the amount of metal components in the product to be purified. However, from the viewpoint of making the production of the chemical solution easier, the ion exchange method preferably includes one or more of the following methods P1 to P3. It is more preferable that the ion exchange method includes two or more of the methods P1 to P3, and even more preferable that it includes all of the methods P1 to P3. When the ion exchange method includes all of the methods P1 to P3, the order in which they are performed is not particularly limited, but it is preferable to perform them in the order of methods P1 to P3. Method P1: A method of passing the substance to be purified through a first packed section filled with a mixed resin containing two or more resins selected from the group consisting of cation exchange resins, anion exchange resins, and chelate resins. Method P2: A method of passing the substance to be purified through at least one of the following packed sections: a second packed section filled with a cation exchange resin, a third packed section filled with an anion exchange resin, and a fourth packed section filled with a chelate resin. Method P3: A method of passing the substance to be purified through a membrane-type ion exchanger.

[0115] The procedures for methods P1 to P3 described above will be explained in detail later, but the ion exchange resins (cation exchange resins, anion exchange resins), chelate resins, and membrane ion exchangers used in each method are H + Shape or OH - If the form is anything other than shape, then H + Shape or OH - It is preferable to use it after it has been restored to its original shape. Furthermore, the space velocity (SV) of the product being purified in each method is preferably 0.01 to 20.0 (1 / h), and more preferably 0.1 to 10.0 (1 / h). Furthermore, the processing temperature for each method is preferably 0 to 60°C, and more preferably 10 to 50°C.

[0116] Furthermore, examples of ion exchange resins and chelating resins include granular, fibrous, and porous monolithic forms, with granular or fibrous forms being preferred. The average particle size of the granular ion exchange resin and chelate resin is preferably 10 to 2000 μm, and more preferably 100 to 1000 μm. In terms of the particle size distribution of the granular ion exchange resin and chelate resin, it is preferable that the proportion of resin particles within a range of ±200 μm of the average particle size is 90% or more. The average particle size and particle size distribution mentioned above can be measured, for example, using a particle size distribution analyzer (Microtrac HRA3920, manufactured by Nikkiso Co., Ltd.) with water as the dispersion medium.

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

[0118] As the cation exchange resin, a known cation exchange resin can be used, and it may be a gel type or an MR type (large network type), with the gel type cation exchange resin being preferred. Examples of cation exchange resins include sulfonic acid-type cation exchange resins and carboxylic acid-type 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 Corporation), 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 the anion exchange resin, a known anion exchange resin can be used, and it may be a gel type or an MR type, but it is preferable to use a gel type anion exchange resin. Examples of cation exchange resins include quaternary ammonium salt type anion exchange resins. Examples of anion exchange resins include Amberlite IRA-400J, Amberlite IRA-410J, Amberlite IRA-900J, Amberlite IRA67, ORLITE DS-2, ORLITE DS-5, and ORLITE DS-6 (manufactured by Organo Corporation), Duolite A113LF, Duolite A116, and Duolite A-375LF (manufactured by Sumika Chemtex Corporation), A400 and A500 (manufactured by Purolite Corporation), as well as DIAION SA12A, DIAION SA10AO, DIAION SA10AOH, DIAION SA20A, and DIAION WA10 (manufactured by Mitsubishi Chemical Corporation).

[0120] Examples of commercially available products that pre-mix a strong acid cation exchange resin and a strong alkaline anion exchange resin include Duolite MB5113, Duolite UP6000, and Duolite UP7000 (manufactured by Sumika Chemtex Co., Ltd.), Amberlite EG-4A-HG, Amberlite MB-1, Amberlite MB-2, Amberjet ESP-2, Amberjet ESP-1, ORLITE DS-3, ORLITE DS-7, and ORLITE DS-10 (manufactured by Organo Corporation), as well as DIAION SMNUP, DIAION SMNUPB, DIAION SMT100L, and DIAION SMT200L (both manufactured by Mitsubishi Chemical Corporation).

[0121] The mixed resin is preferably an embodiment comprising a cation exchange resin and an anion exchange resin, or an embodiment comprising a cation exchange resin and a chelate resin. When preparing a mixed resin containing a cation exchange resin and an anion exchange resin, the mixing ratio of the two is preferably 1 / 4 to 4 / 1 in terms of the volume ratio of the cation exchange resin to the anion exchange resin, and more preferably 1 / 3 to 3 / 1. A suitable combination of cation exchange resin and anion exchange resin is, for example, a combination of a gel-type sulfonic acid-type cation exchange resin and a gel-type quaternary ammonium salt-type anion exchange resin. When preparing a mixed resin containing a cation exchange resin and a chelating resin, the mixing ratio of the two is preferably 1 / 4 to 4 / 1 in terms of the volume ratio of the cation exchange resin to the chelating resin, and more preferably 1 / 3 to 3 / 1. A suitable combination of cation exchange resin and chelating resin is, for example, a combination of a gel-type sulfonic acid-type cation exchange resin and a gel-type aminophosphonic acid-type chelating resin.

[0122] The first filling section typically includes a container and a mixed resin containing two or more resins selected from the group consisting of cation exchange resins, anion exchange resins, and chelate resins, which are filled into the container. Examples of containers include columns, cartridges, and packed towers, but any container other than those exemplified above is acceptable as long as it allows the material to be purified to pass through after the mixed resin has been packed into it.

[0123] In method P1, the substance to be purified only needs to be passed through at least one first-filled section. In particular, two or more first-filled sections may be passed through, as this makes the production of the drug solution easier.

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

[0125] The second filling section typically includes a container and the cation exchange resin described above, which is filled into the container. The third filling section typically includes a container and the aforementioned anion exchange resin filled in the container. The fourth filling section typically includes a container and the chelate resin described below, which is filled into the container.

[0126] Chelate resins generally refer to resins that have coordinating groups capable of forming chelate bonds with metal ions. For example, a resin in which chelate-forming groups are introduced into a styrene-divinylbenzene copolymer. The material of the chelate resin may be gel-type or MR-type. From the viewpoint of processing efficiency, the chelate resin is preferably in granular or fibrous form. Examples of chelating resins include various types such as iminodiacetic acid type, iminopropionic acid type, aminophosphonic acid type (including aminomethylphosphonic acid type), polyamine type, glucamine type (including N-methylglucamine type), aminocarboxylic acid type, dithiocarbamate type, thiol type, amidoxime type, pyridine type, and phosphonic acid type. Specific examples include, as iminodiacetic acid type chelating resins, MC700 from Sumika Chemtex, ORLITE DS-22 from Organo, and D5843 from Purolite; as iminopropionic acid type chelating resins, Epolas MX-8 from Miyoshi Oil & Fat Co., Ltd.; as aminomethylphosphonic acid type chelating resins, MC960 from Sumika Chemtex, and as aminophosphonic acid type chelating resins, ORLITE from Organo. Examples include DS-21 and D5817 manufactured by Purolite, while examples of polyamine-type chelating resins include S985 manufactured by Purolite, Diaion CR-20 manufactured by Mitsubishi Chemical Corporation, and MC850 manufactured by Sumika Chemtex, while examples of N-methylglucamine-type chelating resins include Amberlite IRA-743 manufactured by Organo, and examples of phosphonic acid-type chelating resins include S955 manufactured by Purolite. Among these, aminophosphonic acid type chelating resins are preferred because they can remove heavy metal elements contained in periodic acid.

[0127] The definition of a container in the second filling section, the third filling section, and the fourth filling section is as described above.

[0128] In method P2, the substance to be purified is passed through at least one of the second, third, and fourth filling sections. In particular, it is preferable to pass the substance to be purified through two or more of the second, third, and fourth filling sections. In method P2, it is preferable to pass the product to be purified through at least the second packed section. Furthermore, by passing the product to be purified through the fourth packing section in method P2, purification can be carried out efficiently even with fewer passes of the liquid to be purified through the packing section. When the product to be purified is passed through two or more packing sections in method P2, the order in which the product to be purified is passed through two or more of the second packing section, third packing section, and fourth packing section does not matter.

[0129] In method P2, the substance to be purified is passed through at least one (preferably two or more) second packing section, at least one (preferably two or more) third packing section, and / or at least one fourth packing section. For example, the product to be purified may be passed through one or more (preferably two or more) second filling sections and one or more (preferably two or more) third filling sections, as this makes the production of the drug solution easier. In this case, there are no restrictions on the order in which the material to be purified is passed through the liquid. For example, the material may be passed through the second and third filling sections alternately, or it may be passed through one of the multiple second and third filling sections consecutively, and then through the other of the multiple second and third filling sections consecutively. Furthermore, since the production of the chemical solution is easier, the material to be purified may be passed through one or more second filling sections and one or more fourth filling sections. In this case as well, there are no restrictions on the order in which the substances to be purified are passed through the liquid.

[0130] -Method P3- Method P3 involves passing the substance to be purified through a membrane-type ion exchanger. A membrane-type ion exchanger is a membrane containing ion exchange groups. Examples of ion exchange groups include cation exchange groups (such as sulfonic acid groups) and anion exchange groups (such as ammonium groups).

[0131] The membrane-type ion exchanger may be composed of the ion exchange resin itself, or it may be a membrane-type support into which cation exchange groups and / or anion exchange groups have been introduced. The membrane-type ion exchanger (including the support for the membrane-type ion exchanger) may be porous or non-porous. The membrane-type ion exchanger (including the support for the membrane-type ion exchanger) may be formed into a membrane, for example, by forming an aggregate of particles and / or fibers into a membrane. Furthermore, the membrane-type ion exchanger may be any of the following: an ion exchange membrane, an ion exchange nonwoven fabric, an ion exchange filter paper, or an ion exchange filter cloth. One possible configuration for using a membrane-type ion exchanger is to incorporate the membrane-type ion exchanger as a filter into a cartridge and pass an aqueous solution through it. It is preferable to use semiconductor-grade membrane ion exchangers. Examples of commercially available membrane ion exchangers include Mustang (manufactured by Pall) and Protego® Plus LT Purifier (manufactured by Entegris).

[0132] There are no particular restrictions on the thickness of the film-like ion exchanger; for example, 0.01 to 1 mm is preferred. The flow rate of the aqueous solution is, for example, 1 to 100 mL / (min·cm). 2 )

[0133] In method P3, the substance to be purified only needs to be passed through at least one membrane-type ion exchanger. In particular, two or more membrane-type ion exchangers may be used to pass the substance to be purified, as this makes the preparation of the drug solution easier. Furthermore, when using two or more membrane-type ion exchangers, at least one membrane-type ion exchanger having a cation exchange group and at least one ion exchanger having an anion exchange group may be used.

[0134] The ion exchange method is preferably carried out until the content of the metal component in the product to be purified falls within the range of the preferred metal component content described above.

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

[0136] The filters used for filtering can be any type that has been conventionally used for filtration purposes, without any particular limitations. Examples of materials that make up the filters include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight), and polyarylsulfone. Among these, polyamide resins, PTFE, polypropylene (including high-density polypropylene), and polyarylsulfone are preferred. By using filters formed from these materials, highly polar foreign substances that are prone to causing defects can be more effectively removed from the composition.

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

[0138] The pore size of the filter is preferably about 0.001 to 1.0 μm, more preferably about 0.02 to 0.5 μm, and even more preferably about 0.01 to 0.1 μm. By setting the pore size of the filter within the above range, it is possible to reliably remove fine foreign matter contained in the composition while suppressing clogging during filtration.

[0139] When using filters, different filters may be combined. In this case, filtering with the first filter may be performed only once or two or more times. When different filters are combined and filtering is performed two or more times, each filter may be of the same type or of different types, but it is preferable that they be of different types. Typically, it is preferable that the first filter and the second filter differ in at least one of their pore size and constituent material. It is preferable that the pore size of subsequent filters is the same as or smaller than the pore size of the first filter. Alternatively, a combination of first filters with different pore sizes within the above range may be used. The pore size here can be referenced from the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by companies such as Nippon Pall Co., Ltd., Advantec Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), or Kitz Microfilter Corporation. In addition, polyamide "P-Nylon Filter (pore size 0.02 μm, critical surface tension 77 mN / m)" (manufactured by Nippon Pall Co., Ltd.), high-density polyethylene "PE-Clean Filter (pore size 0.02 μm)" (manufactured by Nippon Pall Co., Ltd.), and high-density polyethylene "PE-Clean Filter (pore size 0.01 μm)" (manufactured by Nippon Pall Co., Ltd.) can also be used.

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

[0141] For example, the first filtering may be performed on a mixture containing some of the components of the composition, and the remaining components may be mixed in to prepare the composition before the second filtering is performed. Furthermore, it is preferable that the filter used is treated before filtering the composition. The liquid used for this treatment is not particularly limited, but it is preferable that it contains the composition and the components contained in the composition.

[0142] When filtering is performed, the upper limit of the filtering temperature is preferably room temperature (25°C) or lower, more preferably 23°C or lower, and even more preferably 20°C or lower. The lower limit of the filtering temperature is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher. Filtering can remove particulate foreign matter and / or impurities, but when performed at the above temperature, the amount of particulate foreign matter and / or impurities dissolved in the composition is reduced, making the filtering more efficient.

[0143] [Static elimination process] The method for producing the composition may further include a static elimination step for removing static electricity from the composition.

[0144] [container] For example, a known container can be used as the container for housing the composition. The container should preferably be one that is clean inside and has low impurity leaching, suitable for semiconductor applications. Examples of suitable containers include the "Clean Bottle" series (manufactured by Aicello Chemical Co., Ltd.) and the "Pure Bottle" (manufactured by Kodama Resin Industry Co., Ltd.). Furthermore, in terms of preventing contamination of raw materials and compositions, it is also preferable to use a multilayer container with a six-layer structure made of six types of resins for the inner wall, or a multilayer container with a seven-layer structure made of seven types of resins. Examples of multilayer containers include those described in Japanese Patent Publication No. 2015-123351, the contents of which are incorporated herein by reference. Examples of materials for the inner wall of the container include, for example, 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, Hastelloy, Inconel, and Monel. Furthermore, it is preferable that the inner wall of the container be formed or coated using the above materials.

[0145] As the second resin, fluororesin (perfluororesin) is preferred. When a fluororesin is used, elution of ethylene or propylene oligomers can be suppressed. Examples of the above container include the containers described in, for example, FluoroPure PFA composite drums (manufactured by Entegris), page 4 of Japanese National Publication of International Patent Application No. 3-502677, page 3 of WO 2004 / 016526 pamphlet, and pages 9 and 16 of WO 99 / 046309 pamphlet.

[0146] As the inner wall of the container, in addition to fluororesin, for example, quartz and an electrolytically polished metal material (a metal material that has been electrolytically polished) are also preferable. The metal material used for the electrolytically polished metal material contains at least one selected from the group consisting of chromium (Cr) and nickel (Ni), and a metal material in which the total content of Cr and Ni is more than 25% by mass relative to the total mass of the metal material is preferable. Examples thereof 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, more preferably 30% by mass or more, relative to the total mass of the metal material. The upper limit is preferably 90% by mass or less relative to the total mass of the metal material.

[0147] As the stainless steel, for example, known stainless steels can be mentioned. Among these, stainless steel containing 8% by mass or more of Ni is preferable, and austenitic stainless steel containing 8% by mass or more of Ni is more preferable. Examples of the austenitic stainless steel 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] As the Ni-Cr alloy, for example, known Ni-Cr alloys can be mentioned. Among these, Ni-Cr alloys having a Ni content of 40 to 75% by mass and a Cr content of 1 to 30% by mass are preferable. Examples of Ni-Cr alloys include Hastelloy, Monel, and Inconel. Specific examples include Hastelloy C-276 (Ni content: 63% by mass, Cr content: 16% by mass), Hastelloy C (Ni content: 60% by mass, Cr content: 17% by mass), and Hastelloy C-22 (Ni content: 61% by mass, Cr content: 22% by mass). The Ni-Cr alloy may further contain boron, silicon, tungsten, molybdenum, copper, or cobalt in addition to the above components, as necessary.

[0149] As a method of electrolytic polishing a metal material, for example, known methods can be used. Specific examples include the methods described in paragraphs

[0011] to

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

[0036] to

[0042] of Japanese Unexamined Patent Publication No. 2008-264929, the contents of which are incorporated herein by reference.

[0150] The metal material is preferably buff-polished. As a method of buff polishing, for example, known methods can be used. The size of the abrasive grains used for finishing buff polishing is preferably #400 or less from the viewpoint that irregularities on the surface of the metal material tend to be smaller. Buff polishing is preferably performed before electrolytic polishing. The metal material may be treated by combining one or more of multi-step buff polishing performed by changing the grain size (i.e., grit size) of abrasive grains, acid cleaning, magnetic fluid polishing, and the like.

[0151] It is preferable to clean the inside of the container before filling the container with the composition. The liquid used for cleaning can be appropriately selected depending on the application, and a liquid containing at least one of the composition or a component added to the composition is preferable.

[0152] To prevent changes in the components of the composition during storage, the container may be purged with an inert gas (e.g., nitrogen and argon) with a purity of 99.99995% by volume or higher. Gases with a particularly low water content are preferred. Furthermore, during the transport and storage of the container containing the composition, either room temperature or temperature control may be used. Among these, temperature control within the range of -20 to 20°C is preferred in order to prevent deterioration.

[0153] <Processing method for the object to be processed> The following describes a method for treating a workpiece containing Ru and W using the composition of the present invention. First, the workpiece will be described.

[0154] <Object to be processed> The material being processed contains Ru and W. It is preferable that Ru and W in the workpiece are present on the substrate. Furthermore, the Ru in the workpiece may be a Ru-containing material containing Ru and other elements. Similarly, the W in the workpiece may be a W-containing material containing W and other elements. In other words, it is preferable that the workpiece is a substrate in which Ru-containing material and W-containing material are present. Here, it is preferable that the composition of the present invention be used to selectively remove Ru-containing substances from W-containing substances on a substrate. In this specification, "on the substrate" includes, for example, the front and back surfaces, sides, and inside grooves of the substrate. Furthermore, Ru-containing material on the substrate includes not only Ru-containing material directly present on the surface of the substrate, but also Ru-containing material present on the substrate via other layers. Hereinafter, grooves, holes, and other recesses provided in the substrate will also be referred to as "grooves, etc." Furthermore, the presence of Ru-containing and W-containing materials in the workpiece means that when the workpiece is brought into contact with the composition, the Ru-containing and W-containing materials can come into contact with the composition. In addition, the state in which contact can occur includes not only the case in which the Ru-containing and W-containing materials are exposed to the outside, but also the case in which a component covering the Ru-containing or W-containing material is removed by some action, and the Ru-containing or W-containing material can be exposed.

[0155] The type of substrate is not particularly limited, but a semiconductor substrate is preferred. Examples of substrates include semiconductor wafers, photomask glass substrates, liquid crystal display glass substrates, plasma display glass substrates, FED (Field Emission Display) substrates, optical disc substrates, magnetic disc substrates, and magneto-optical disc substrates. Materials that constitute semiconductor substrates include silicon, germanium, silicon-germanium, and Group III-V compounds such as GaAs, as well as combinations thereof.

[0156] The applications of the workpiece treated with the composition of the present invention are not particularly limited, and include, for example, DRAM (Dynamic Random Access Memory), FRAM (Registered Trademark) (Ferroelectric Random Access Memory), MRAM (Magnetoresistive Random Access Memory), and PRAM (Phase Change Random Access Memory). It may be used in memory, logic circuits, processors, etc.

[0157] Ru-containing materials are not particularly limited as long as they contain Ru (Ru atoms), and examples include elemental Ru, Ru-containing alloys, Ru oxides, Ru nitrides, and Ru oxynitrides. Furthermore, Ru oxides, Ru nitrides, and Ru oxynitrides may also be Ru-containing composite oxides, composite nitrides, and composite oxynitrides. The content of Ru atoms in the Ru-containing material is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the Ru-containing material. There is no particular upper limit, but it is preferably 100% by mass or less, based on the total mass of the Ru-containing material.

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

[0159] The form of the Ru-containing material on the substrate is not particularly limited and may be arranged in any form, for example, as a film, wiring, plate, columnar, or particulate. Examples of forms in which Ru-containing material is arranged in particulate form include, as described later, a substrate on which a Ru-containing film is placed, after which particulate Ru-containing material adheres as a residue after dry etching; a substrate on which a Ru-containing film is placed, after which particulate Ru-containing material adheres as a residue after CMP (chemical mechanical polishing) is performed; and a substrate on which a Ru-containing film is deposited, and particulate Ru-containing material adheres to areas other than the area where the Ru-containing film is intended to be formed.

[0160] The thickness of the Ru-containing film is not particularly limited and can be appropriately selected depending on the application. For example, it is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. There is no particular lower limit, but it is preferably 0.1 nm or more. The Ru-containing film may be placed on only one main surface of the substrate, or on both main surfaces. Furthermore, the Ru-containing film may be placed on the entire main surface of the substrate, or on only a portion of the main surface.

[0161] The W-containing material is not particularly limited as long as it contains W (W atoms), and examples include elemental W, W-containing alloys, W oxides, W nitrides, W oxynitrides, and W carbides and W borides. Furthermore, W oxides, W nitrides, W oxynitrides, and W carbides may also be composite oxides, composite nitrides, composite oxynitrides, and composite carbides containing W. The content of W atoms in the W-containing material is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the W-containing material. The upper limit is not particularly limited, and is preferably 100% by mass or less based on the total mass of the W-containing material.

[0162] The W-containing material may contain other transition metals. Examples of the transition metal 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 form of the W-containing material on the substrate is not particularly limited, and may be, for example, any of a film form, a wiring form, a plate form, a columnar form, and a form arranged in particles.

[0164] The thickness of the W-containing film is not particularly limited and may be appropriately selected depending on the application. For example, it is preferably 200 nm or less, more preferably 100 nm or less, and still more preferably 50 nm or less. The lower limit is not particularly limited, and is preferably 0.1 nm or more. The W-containing film may be disposed only on the main surface on one side of the substrate, or may be disposed on the main surfaces on both sides of the substrate. Further, the W-containing film may be disposed on the entire main surface of the substrate, or may be disposed on a part of the main surface of the substrate.

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

[0166] There are no particular restrictions on the size, thickness, shape, or layer structure of the substrate; these can be selected as appropriate according to the requirements.

[0167] [Method of manufacturing the object to be processed] The method for manufacturing the product to be processed is not particularly limited, and known manufacturing methods can be used. For example, Ru-containing films and / or W-containing films can be formed on a substrate using sputtering, chemical vapor deposition (CVD), molecular beam epitaxy (MBE), and atomic layer deposition (ALD) as methods for manufacturing the treated material. When forming a Ru-containing film using the above manufacturing method, if the substrate has an uneven structure, the Ru-containing film may be formed on all surfaces of the structure. Furthermore, when Ru-containing films are formed by sputtering or CVD methods, the Ru-containing film may also adhere to the back surface of the substrate on which it is placed (the surface opposite to the Ru-containing film side). Alternatively, the above method may be carried out through a predetermined mask to form Ru-containing wiring and / or W-containing wiring on the substrate. Furthermore, a substrate on which a Ru-containing film, Ru-containing wiring, W-containing film, and / or W-containing wiring are arranged may be subjected to a predetermined treatment and used as a workpiece for the treatment method of the present invention. For example, the above substrate may be subjected to dry etching to produce a substrate having dry etching residue containing Ru and W-containing material. Alternatively, the above substrate may be subjected to CMP to produce a substrate having Ru-containing material and W-containing material. Furthermore, a Ru-containing film may be deposited on the region of the substrate where the Ru-containing film is to be formed by sputtering, CVD, molecular beam epitaxy, or atomic layer deposition to produce a substrate having Ru-containing material and W-containing material adhering to regions other than the region where the Ru-containing film is to be formed.

[0168] <Processing method for the object to be processed> This document describes a method for processing a workpiece containing Ru and W using the composition of the present invention, specifically focusing on a method for processing a substrate containing Ru and W. Hereinafter, the substrate containing Ru and W will also be simply referred to as the "workpiece."

[0169] [Process A] The processing method for a substrate to be processed (hereinafter also referred to as "this processing method") includes step A, which involves removing Ru-containing substances from the substrate using the composition of the present invention. Furthermore, the substrates (substrates to be treated) on which Ru-containing and W-containing materials are placed, which are the objects to be treated by this processing method, are as described above.

[0170] A specific method for step A is to bring the composition into contact with the substrate to be treated. The method of contact is not particularly limited and includes, for example, immersing the object to be treated in a composition placed in a tank, spraying the composition onto the object to be treated, flowing the composition over the object to be treated, and combinations thereof. Among these, immersing the object to be treated in the composition is preferred.

[0171] Furthermore, a mechanical stirring method may be used to further enhance the cleaning ability of the composition. Examples of mechanical stirring methods include circulating the composition over the workpiece, flowing or spraying the composition over the workpiece, and locally stirring the composition near the substrate by irradiating it with ultrasonic waves (e.g., megasonic waves). The processing time for step A can be adjusted as appropriate. The processing time (contact time between the composition and the object to be processed) is not particularly limited, but is preferably 0.25 to 10 minutes, and more preferably 0.5 to 2 minutes. The temperature of the composition during processing is not particularly limited, but 20 to 75°C is preferred, 20 to 60°C is more preferred, 40 to 65°C is even more preferred, and 50 to 65°C is particularly preferred.

[0172] In step A, while measuring the concentration of one or more components selected from the group consisting of periodic acid or its salts, quaternary ammonium salts, resins containing nitrogen atoms, solvents, and arbitrary components in the composition, a process may be carried out in which the solvent and one or more components selected from the group consisting of the components of the composition are added to the composition as needed. By performing this process, the concentration of components in the composition can be stably maintained within a predetermined range. Water is preferred as the solvent.

[0173] Specific preferred embodiments of step A include, for example, step A1 of recess etching Ru-containing wiring or Ru-containing liner placed on a substrate using the composition; step A2 of removing the Ru-containing film on the outer edge of the substrate on which the Ru-containing film is placed using the composition; step A3 of removing Ru-containing material adhering to the back surface of the substrate on which the Ru-containing film is placed using the composition; step A4 of removing Ru-containing material on the substrate after dry etching using the composition; step A5 of removing Ru-containing material on the substrate after chemical mechanical polishing using the composition; and step A6 of removing ruthenium-containing material in areas of the substrate other than the area on which the Ruthenium-containing film is to be formed after depositing a Ruthenium-containing film in the area on the substrate on which the Ruthenium-containing film is to be formed using the composition. According to the substrate processing method using the composition of the present invention, W-containing substances present on the substrate to be processed are not removed during the above step. The following describes the processing methods used in each of the above processes.

[0174] (Step A1) Examples of Step A include Step A1, in which the composition is used to perform recess etching treatment on Ru-containing wiring (wiring containing Ru) and a Ru-containing liner (liner containing Ru) disposed on a substrate. Hereinafter, substrates having Ru-containing wiring and substrates having a Ru-containing liner will be specifically described as examples of objects to be processed in Step A1.

[0175] <Substrate having Ru-containing wiring> FIG. 1 is a schematic cross-sectional top view showing a substrate having Ru-containing wiring (hereinafter, also referred to as a "Ru wiring substrate"), which is an example of an object to be subjected to recess etching treatment in Step A1. The Ru wiring substrate 10a shown in FIG. 1 comprises an unillustrated substrate, an insulating film 12 having grooves or the like disposed on the substrate, a barrier metal layer 14 disposed along the inner walls of the grooves or the like, and Ru-containing wiring 16 filled inside the grooves or the like. Further, a W-containing material (not shown) is present in the Ru wiring substrate 10a.

[0176] The Ru-containing wiring in the Ru wiring substrate preferably contains elemental Ru, a Ru alloy, a Ru oxide, a Ru nitride, or a Ru oxynitride. The material constituting the barrier metal layer in the Ru wiring substrate is not particularly limited, and examples thereof include Ti metal, Ti nitride, Ti oxide, Ti-Si alloys, Ti-Si composite nitrides, Ti-Al alloys, Ta metal, Ta nitride, and Ta oxide. Although FIG. 1 describes an embodiment where the Ru wiring substrate has a barrier metal layer, a Ru wiring substrate that does not have a barrier metal layer is also acceptable.

[0177] In Step A1, by performing recess etching treatment on the Ru wiring substrate using the composition described above, part of the Ru-containing wiring can be removed to form a recess. More specifically, when step A1 is performed, as shown in the Ru wiring substrate 10b of FIG. 2, part of the barrier metal layer 14 and the Ru-containing wiring 16 is removed to form a recess 18. Note that although FIG. 2 shows the Ru wiring substrate 10b in which part of the barrier metal layer 14 and the Ru-containing wiring 16 is removed, the barrier metal layer 14 may not be removed, and only part of the Ru-containing wiring 16 may be removed to form the recess 18. Note that in the above treatment, the W-containing material is not removed.

[0178] The method for manufacturing a Ru wiring substrate is not particularly limited, and examples thereof include a method including: a step of forming an insulating film on a substrate; a step of forming a groove or the like in the insulating film; a step of forming a barrier metal layer on the insulating film; a step of forming a Ru-containing film so as to fill the groove or the like; and a step of performing a planarization treatment on the Ru-containing film.

[0179] <Substrate having Ru-containing liner> FIG. 3 is a schematic diagram of an upper cross-section showing another example of an object to be subjected to recess etching treatment in step A1, which is a substrate having a Ru-containing liner (hereinafter also referred to as a "Ru liner substrate").

[0180] The Ru liner substrate 20a shown in FIG. 3 includes a substrate (not shown), an insulating film 22 having a groove or the like disposed on the substrate, a Ru-containing liner 24 disposed along the inner wall of the groove or the like, and a wiring portion 26 filled inside the groove or the like. The Ru liner substrate 20a also includes a W-containing material (not shown).

[0181] The Ru-containing liner in the Ru liner substrate preferably contains elemental Ru, a Ru alloy, a Ru oxide, a Ru nitride, or a Ru oxynitride. Note that in the Ru liner substrate shown in FIG. 3, a separate barrier metal layer may be provided between the Ru-containing liner 24 and the insulating film 22. Examples of the material constituting the barrier metal layer are the same as those in the case of the Ru wiring substrate. The materials used to constitute the wiring portion in the Ru liner substrate are not particularly limited, but examples include Cu metal, W metal, Mo metal, and Co metal.

[0182] In step A1, by performing a recess etching treatment on the Ru liner substrate using the above-described composition, a portion of the Ru-containing liner can be removed to form a recess. More specifically, when step A1 is performed, as shown in the Ru liner substrate 20b of Figure 4, a portion of the Ru-containing liner 24 and the wiring portion 26 is removed, and a recess 28 is formed. Note that W-containing substances are not removed during the above process.

[0183] The method for manufacturing a Ru liner substrate is not particularly limited and includes a step of forming an insulating film on a substrate, a step of forming grooves or the like in the insulating film, a step of forming a Ru liner on the insulating film, a step of forming a metal film so as to fill the grooves or the like, and a step of performing a planarization treatment on the metal film.

[0184] A specific method for step A1 is to bring a Ru wiring board or Ru liner board into contact with the composition. The method of contact between the Ru wiring board or Ru liner board and the composition is as described above. The preferred contact time between the Ru wiring board or Ru liner board and the composition, and the preferred temperature range of the composition, are as described above.

[0185] (Process B) Furthermore, before or after step A1, step B may be performed to process the substrate obtained in step A1 using a predetermined solution (hereinafter also referred to as "specific solution"), if necessary. In particular, when a barrier metal layer is placed on a substrate, the solubility of the components constituting the Ru-containing wiring or Ru liner (hereinafter also referred to as "Ru-containing wiring, etc.") and the components constituting the barrier metal layer may differ depending on their type. In such cases, it is preferable to adjust the degree of dissolution of the Ru-containing wiring, etc. and the barrier metal layer using a solution that has superior solubility for the barrier metal layer. From this perspective, a specific solution is preferable that has poor dissolving ability for Ru-containing wiring and other materials, but excellent dissolving ability for materials constituting the barrier metal layer. Furthermore, it is preferable that the specific solution has low solubility for W-containing substances.

[0186] Examples of specific solutions include those selected from the group consisting of a mixture of hydrofluoric acid and hydrogen peroxide (FPM), a mixture of sulfuric acid and hydrogen peroxide (SPM), a mixture of ammonia water and hydrogen peroxide (APM), and a mixture of hydrochloric acid and hydrogen peroxide (HPM). The composition of FPM is preferably within the range (by volume) of, for example, "hydrofluoric acid:hydrogen peroxide:water = 1:1:1" to "hydrofluoric acid:hydrogen peroxide:water = 1:1:200". The composition of the SPM is preferably within the range (by volume) of, for example, "sulfuric acid:hydrogen peroxide:water = 3:1:0" to "sulfuric acid:hydrogen peroxide:water = 1:1:10". The composition of APM is preferably within the range (by volume) of, for example, "ammonia water:hydrogen peroxide water:water = 1:1:1" to "ammonia water:hydrogen peroxide water:water = 1:1:30". The composition of HPM is preferably within the range (by volume) of, for example, "hydrochloric acid:hydrogen peroxide:water = 1:1:1" to "hydrochloric acid:hydrogen peroxide:water = 1:1:30". Furthermore, these preferred composition ratios refer to the composition ratios when hydrofluoric acid is 49% by mass, sulfuric acid is 98% by mass, aqueous ammonia is 28% by mass, hydrochloric acid is 37% by mass, and hydrogen peroxide is 31% by mass. Among these, SPM, APM, or HPM are preferred as specific solutions from the viewpoint of their ability to dissolve the barrier metal layer. As for the specific solution, APM, HPM, or FPM are preferred from the viewpoint of reducing roughness, with APM being more preferred. As for the specific solution, APM or HPM is preferred from the viewpoint of having an excellent balance of performance.

[0187] In step B, the preferred method for treating the substrate obtained in step A1 using a specific solution is to bring the specific solution into contact with the substrate obtained in step A1. The method for bringing the specific solution into contact with the substrate obtained in step A1 is not particularly limited, and for example, a method similar to that for bringing the composition into contact with the substrate can be used. The contact time between the specific solution and the substrate obtained in step A1 is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes.

[0188] In this processing method, steps A1 and B may be performed alternately and repeatedly. When the processes are performed alternately, it is preferable that each of processes A1 and B be performed 1 to 10 times. Furthermore, when processes A1 and B are performed alternately, the first and last processes may be either process A1 or process B.

[0189] (Process A2) Step A is, for example, step A2, which involves using the composition to remove the Ru-containing film from the outer edge of the substrate on which the Ru-containing film is placed. Figure 5 shows a schematic diagram (top view) of an example of a substrate on which the Ru-containing film, which is the material to be processed in process A2, is placed. The workpiece 30 in step A2 shown in Figure 5 is a laminate having a substrate 32 and a Ru-containing film 34 disposed on the main surface of one side of the substrate 32 (the entire area enclosed by the solid line). As will be described later, in step A2, the Ru-containing film 34 located at the outer edge 36 of the workpiece 30 (the area outside the dashed line) is removed. Furthermore, the processed material 30 contains W-containing substances, which are not shown in the illustration.

[0190] The substrate and Ru-containing film in the workpiece are as described above. Furthermore, the Ru-containing film preferably contains elemental Ru, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides.

[0191] The specific method for step A2 is not particularly limited, and one example is a method of supplying the composition from a nozzle so that the composition comes into contact only with the Ru-containing film on the outer edge of the substrate. During the processing of step A2, the substrate processing apparatus and substrate processing method described in Japanese Patent Publication No. 2010-267690, Japanese Patent Publication No. 2008-080288, Japanese Patent Publication No. 2006-100368, and Japanese Patent Publication No. 2002-299305 can be preferably applied.

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

[0193] (Process A3) Step A includes step A3, which involves using the composition to remove Ru-containing substances adhering to the back surface of the substrate on which the Ru-containing film is placed. Examples of workpieces processed in process A3 include those used in process A2. When forming the workpiece used in process A2, which consists of a substrate and a Ru-containing film placed on one main surface of the substrate, the Ru-containing film is formed by sputtering and CVD, etc. In this process, Ru-containing material may adhere to the surface of the substrate opposite to the Ru-containing film side (the back surface). Process A3 is performed to remove such Ru-containing material from the workpiece.

[0194] The specific method for step A3 is not particularly limited, and one example is a method of spraying the composition so that it comes into contact only with the back surface of the substrate.

[0195] The method of contact between the composition and the object to be treated is as described above. The preferred contact time between the composition and the object to be treated, and the preferred temperature range of the composition, are as described above. Note that W-containing substances are not removed in process A3.

[0196] (Process A4) Step A includes step A4, which involves using the composition to remove Ru-containing material from the substrate after dry etching. Figures 6 and 8 show schematic diagrams illustrating examples of the workpieces processed in process A4. The following explains each of the figures.

[0197] The workpiece 40 shown in Figure 6 has a substrate 42 on which a Ru-containing film 44, an etching stop layer 46, an interlayer insulating film 48, and a metal hard mask 50 are arranged in this order, and after going through a dry etching process, a groove or the like 52 is formed at a predetermined position in which the Ru-containing film 44 is exposed. In other words, the workpiece shown in Figure 6 is a laminate comprising a substrate 42, a Ru-containing film 44, an etching stop layer 46, an interlayer insulating film 48, and a metal hard mask 50 in this order, and has a groove or the like 52 that penetrates from the surface of the metal hard mask 50 to the surface of the Ru-containing film 44 at the position of the opening of the metal hard mask 50. The inner wall 54 of the groove or the like 52 is composed of a cross-sectional wall 54a made of the etching stop layer 46, the interlayer insulating film 48, and the metal hard mask 50, and a bottom wall 54b made of the exposed Ru-containing film 44, and dry etching residue 56 is attached to the inner wall 54 of the groove or the like 52. Dry etching residue contains Ru-containing material. Furthermore, the processed material 40 contains W-containing substances, which are not shown in the illustration.

[0198] The workpiece 60b shown in Figure 8 is obtained by dry etching the workpiece shown in Figure 7 before dry etching. The workpiece 60a shown in Figure 7 comprises an insulating film 62 disposed on a substrate (not shown), a Ru-containing film 66 filled in grooves or the like formed in the insulating film 62, and a metal hard mask 64 disposed on the insulating film 62 with the Ru-containing film 66 positioned in the openings. This workpiece 60a is obtained by forming the insulating film 62 and the metal hard mask 64 in that order on a substrate (not shown), forming grooves or the like in the insulating film 62 located in the openings of the metal hard mask 64, then filling the grooves or the like with Ru-containing material to form the Ru-containing film 66. When the workpiece 60a shown in Figure 7 is dry-etched, the Ru-containing film is etched, and the workpiece 60b shown in Figure 8 is obtained. The workpiece 60b shown in Figure 8 comprises an insulating film 62 placed on a substrate (not shown), a Ru-containing film 66 filled in a portion of grooves etc. 72 formed in the insulating film 62, and a metal hard mask 64 placed on the insulating film 62 with openings at the positions of the grooves etc. 72. Dry etching residue 76 is attached to the cross-sectional wall 74a made of the insulating film 62 and the metal hard mask 64 within the grooves etc. 72, and to the bottom wall 74b made of the Ru-containing film 66. Dry etching residue contains Ru-containing material. Furthermore, the material to be treated 60b contains W-containing substances, which are not shown in the illustration.

[0199] The Ru-containing film of the workpiece subjected to step A4 preferably contains elemental Ru, Ru alloy, Ru oxide, Ru nitride, or Ru oxynitride. The Ru-containing material of the workpiece subjected to process A4 preferably includes elemental Ru, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The interlayer insulating film and the insulating film are selected from known materials. For the metal hard mask, known materials are selected. Although Figures 6, 7, and 8 describe an embodiment using a metal hard mask, a resist mask formed using a known photoresist material may also be used.

[0200] A specific method for step A4 is to bring the composition into contact with the object to be treated. The method of contact between the composition and the wiring board is as described above. The preferred contact time between the composition and the wiring board, and the preferred temperature range of the composition, are as described above. Note that W-containing substances are not removed in process A4.

[0201] (Process A5) Step A involves chemical mechanical polishing (CMP) using the composition. A5 step is to remove Ru-containing material from the substrate after mechanical polishing. CMP (Chemical Polishing) technology is used in manufacturing processes such as planarization of insulating films, planarization of connection holes, and damascene wiring. After CMP, substrates may be contaminated with particles used for polishing and metal impurities. Therefore, it is necessary to remove these contaminants and clean the substrate before proceeding to the next processing stage. By performing step A5, it is possible to remove Ru-containing substances that are generated and adhere to the substrate when the CMP-processed material has Ru-containing wiring or a Ru-containing film.

[0202] As mentioned above, the workpiece to be processed in step A5 is a substrate containing Ru after CMP. The Ru-containing material preferably includes elemental Ru, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. Furthermore, substrates containing Ru after CMP (Chemical Polishing) also contain W (W). A specific method for step A5 is to bring the composition into contact with the object to be treated. The method of contact between the composition and the wiring board is as described above. The preferred contact time between the composition and the wiring board, and the preferred temperature range of the composition, are as described above. Note that W-containing substances are not removed in step A5.

[0203] (Process A6) Step A includes step A6, which involves using the composition to deposit a Ru-containing film in the region on the substrate where the Ru-containing film is to be formed, and then removing Ru-containing materials from areas on the substrate other than the region where the Ru-containing film is to be formed. As described above, the method for forming the Ru-containing film is not particularly limited, and the Ru-containing film can be formed on the substrate using sputtering, CVD, MBE, and ALD methods. When a Ru-containing film is formed on a substrate in the area where the Ru-containing film is intended to be formed (the area where the Ru-containing film is to be formed), the Ru-containing film may also be formed in unintended areas (areas other than the area where the Ru-containing film is intended to be formed). Examples of unintended areas include the side walls of an insulating film when filling grooves in the insulating film with the Ru-containing film. An example of the workpiece to be processed in step A6 is shown in Figure 10. The workpiece 80b shown in Figure 10 is obtained by forming a Ru-containing film on the workpiece 80a shown in Figure 9 before the formation of the Ru-containing film. The workpiece 80a shown in Figure 9 has an insulating film 82 placed on a substrate (not shown) and a metal hard mask 84 placed on the insulating film 82, with the insulating film 82 having grooves or the like 86 at the openings of the metal hard mask 84. By forming a Ru-containing film to fill a portion of the grooves or the like 86 of this workpiece 80a, the workpiece 80b shown in Figure 10 is obtained. The workpiece 80b shown in Figure 10 comprises an insulating film 82 placed on a substrate (not shown), a Ru-containing film 88 filled in a portion of grooves etc. 86 formed in the insulating film 82, and a metal hard mask 84 placed on the insulating film 82 with openings at the positions of the grooves etc. 86. Residue 92 from the formation of the Ru-containing film adheres to the cross-sectional wall 90a made of the insulating film 82 and the metal hard mask 84 within the grooves etc. 86, and to the bottom wall 90b made of the Ru-containing film 88. In the above embodiment, the region where the Ru-containing film 88 is located corresponds to the region where the Ru-containing film is to be formed, while the cross-sectional wall 90a and the bottom wall 90b correspond to regions other than the region where the Ru-containing film is to be formed. Furthermore, the material to be treated 80b contains W-containing substances, which are not shown in the illustration.

[0204] The Ru-containing film preferably contains elemental Ru, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. The Ru-containing material preferably includes elemental Ru, Ru alloys, Ru oxides, Ru nitrides, or Ru oxynitrides. For the metal hard mask, known materials are selected. Although Figures 9 and 10 describe an embodiment using a metal hard mask, a resist mask formed using a known photoresist material may also be used.

[0205] A specific method for step A6 is to bring the composition into contact with the object to be treated. The method of contact between the composition and the wiring board is as described above. The preferred contact time between the composition and the wiring board, and the preferred temperature range of the composition, are as described above. Note that the W-containing substance is not removed in step A6.

[0206] [Process C] This processing step may include, if necessary, a step C in which the substrate obtained in step A is rinsed using a rinsing solution.

[0207] Suitable rinsing solutions include, for example, hydrofluoric acid (preferably 0.001 to 1% by mass hydrofluoric acid), hydrochloric acid (preferably 0.001 to 1% by mass hydrochloric acid), hydrogen peroxide (preferably 0.5 to 31% by mass hydrogen peroxide, more preferably 3 to 15% by mass hydrogen peroxide), a mixture of hydrofluoric acid and hydrogen peroxide (FPM), a mixture of sulfuric acid and hydrogen peroxide (SPM), a mixture of ammonia water and hydrogen peroxide (APM), a mixture of hydrochloric acid and hydrogen peroxide (HPM), carbon dioxide water (preferably 10 to 60 ppm by mass carbon dioxide water), ozonated water (preferably 10 to 60 ppm by mass ozonated water), hydrogen water (preferably 10 to 20 ppm by mass hydrogen water), citric acid aqueous solution (preferably 0.01 to 10% by mass citric acid aqueous solution), and acetic acid (undiluted acetic acid or 0.01 to 10% by mass acetic acid). Aqueous solutions are preferred), sulfuric acid (1-10% by mass aqueous sulfuric acid solution is preferred), aqueous ammonia (0.01-10% by mass aqueous ammonia solution is preferred), isopropyl alcohol (IPA), aqueous hypochlorous acid solution (1-10% by mass aqueous hypochlorous acid solution is preferred), aqua regia (aqua regia corresponding to a volume ratio of 2.6 / 1.4-3.4 / 0.6 of 37% by mass hydrochloric acid to 60% by mass nitric acid is preferred), ultrapure water, nitric acid (0.001-1% by mass nitric acid is preferred), perchloric acid (0.001-1% by mass perchloric acid is preferred), aqueous oxalic acid solution (0.01-10% by mass aqueous solution is preferred), or aqueous periodic acid solution (0.5-10% by mass aqueous periodic acid solution is preferred, and examples of periodic acid include orthoperiodic acid and metaperiodic acid). The preferred conditions for FPM, SPM, APM, and HPM are, for example, the same as the preferred embodiments for FPM, SPM, APM, and HPM used as the specific solutions described above. Note that hydrofluoric acid, nitric acid, perchloric acid, and hydrochloric acid refer to aqueous solutions of HF, HNO3, HClO4, and HCl, respectively, dissolved in water. Ozone water, carbon dioxide water, and hydrogen water refer to aqueous solutions obtained by dissolving O3, CO2, and H2 in water, respectively. These rinsing solutions may be mixed and used insofar as they do not impair the purpose of the rinsing process.

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

[0209] A specific method for step C is, for example, to bring the rinsing solution into contact with the substrate obtained in step A, which is the object to be processed. Methods of bringing the substrate into contact with the rinse solution include, for example, immersing the substrate in a rinse solution in a tank, spraying the rinse solution onto the substrate, pouring the rinse solution onto the substrate, and any combination thereof.

[0210] The processing time (contact time between the rinse solution and the object being processed) is not particularly limited, and can range from 5 seconds to 5 minutes, for example. The temperature of the rinse solution during processing is not particularly limited, but is generally preferred to be between 16 and 60°C, and more preferably between 18 and 40°C. When SPM is used as the rinse solution, its temperature is preferably between 90 and 250°C.

[0211] [Process D] This processing method may include a step D after step C, in which a drying process is carried out as needed. The drying method is not particularly limited, but examples include spin drying, flow of drying gas over the substrate, heating of the substrate (e.g., heating by a hot plate or infrared lamp), IPA (isopropyl alcohol) vapor drying, Marangoni drying, Rotagoni drying, and combinations thereof. The drying time can be adjusted as needed depending on the specific method used, for example, from 30 seconds to several minutes.

[0212] [Other processes] This processing method may be carried out in combination with other processes performed on the substrate, either before or after. It may also be incorporated into other processes, or the processing method of the present invention may be incorporated into other processes. Other processes include, for example, the formation of structures such as metal wiring, gate structures, source structures, drain structures, insulating films, ferromagnetic layers, and non-magnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and modification), the formation of resists, exposure and removal processes, heat treatment processes, cleaning processes, and inspection processes. This processing method may be performed at any stage of the backend process (BEOL), middle process (MOL), or frontend process (FEOL), but it is preferable to perform it in the frontend or middle process. [Examples]

[0213] The present invention will be described in more detail below based on examples. The materials, quantities, proportions, processing details, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0214] <Preparation of composition> The ultrapure water and each component were mixed to obtain the content shown in Table 1 below, and the mixture was then thoroughly stirred with a stirrer to obtain the compositions used in each example and comparative example. Note that the content of each component in Table 1 is based on mass, and the remainder of the total of each component is water. The components shown in Table 1 below are described in detail.

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

[0216] [Quaternary ammonium salts] · A-1: ​​Tetramethylammonium hydroxide ·B-1: Tetraethylammonium Hydroxide ·B-2: Tetraethylammonium chloride ·B-3: Tetraethylammonium bromide B-4: Tetraethylammonium fluoride ·C-1: Tetrabutylammonium Hydroxide · D-1: Ethyltrimethylammonium hydroxide · D-2: Ethyltrimethylammonium chloride ·E-1: Diethyldimethylammonium hydroxyl ·F-1: Triethylmethylammonium hydroxyl · G-1: (2-hydroxyethyl)trimethylammonium hydroxide ·H-1: Tributylmethylammonium hydroxide ·I-1: Dimethyldipropylammonium hydroxyl ·J-1: Benzyltrimethylammonium hydroxide K-1: Benzyltriethylammonium hydroxide L-1: Triethyl(2-hydroxyethyl)ammonium 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. The weight-average molecular weight of each compound is shown in Table 1 below. PA-1 to PA-9: Compounds consisting of repeating units represented by the following formulas.

[0218] [ka]

[0219] • PB-1 to PB-4: Compounds consisting of repeating units represented by the following formulas.

[0220] [ka]

[0221] • PC-1 and PC-2: Compounds consisting of repeating units represented by the following formula.

[0222] [ka]

[0223] • PD-1 and PD-2: Compounds consisting of repeating units represented by the following formulas.

[0224] [ka]

[0225] PE-1 to PE-3: Compounds consisting of repeating units represented by the following formulas.

[0226] [ka]

[0227] • PF-1 and PF-2: Compounds consisting of repeating units represented by the following formula.

[0228] [ka]

[0229] [water] ·Ultra pure water

[0230] [Additives] The additives used in Example 71, Example 72, and Comparative Example 4 are as follows. IA: Iodate TEA: Triethylamine BMPC: 1-Butyl-1-methylpyrrolidinium chloride

[0231] <Rating> The ratio of the etching rate of Ru (ERRu) to the etching rate of W (ERW), i.e., the Ru / W selectivity, for each composition was evaluated using the following procedure. A substrate was prepared by forming a Ru layer (a layer composed solely of Ru) on one surface of a commercially available silicon wafer (diameter: 12 inches) using the PVD method. The 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 to perform pretreatment. The pre-treated 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 X-ray fluorescence analyzer (XRF AZX-400, Rigaku Corporation), and the etching rate of the Ru layer (ERRu Å / min) was calculated from the difference in thickness of the Ru layer before and after the removal treatment. Furthermore, the W layer removal process was carried out in the same manner as described above, except that the W layer (a layer composed solely of W) was formed by the CVD method. The thickness of the W layer before and after the removal process was determined using a resistivity meter (VR300DE, manufactured by Kokusai Electric Semiconductor Services Co., Ltd.). From the determined thickness of the W layer, the etching rate of the W layer (ERW Å / min) was calculated. The ratio of ERRu to ERW (ERR(Ru / W)) was calculated by dividing the ERRu calculated using the method described above by ERW. Based on the obtained ERR(Ru / W), the Ru / W selectivity was evaluated according to the following criteria.

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

[0233] <Result> The composition and the evaluation results are shown in Table 1, divided into Table 1-1, Table 1-2, and Table 1-3. In the table, the "content" of each component represents its content relative to the total mass of the composition (mass % or mass ppm). The remainder of the sum of the contents of each component is water. In the table, examples where multiple types of components are listed indicate that each of those multiple types of components was added in the stated amounts. In the table, the "molecular weight" for nitrogen-containing resins represents the weight-average molecular weight calculated by GPC. In the table, "pH" indicates the pH of the composition measured using a pH meter (Horiba, Ltd., F-51 (product name)). The measurement temperature was 25°C.

[0234] [Table 1]

[0235] [Table 2]

[0236] [Table 3]

[0237] The results in Table 1 confirm that the composition of the present invention exhibits excellent Ru / W selectivity. A comparison of Examples 10-22, 26, and 27 with Examples 1-9, 23-25, and 71-76 confirmed that nitrogen-containing resins exhibit superior Ru / W selectivity when they have a quaternary ammonium salt structure. A comparison of Examples 1-9 and 73 with Examples 23-25, 71, 72, and 74-76 confirmed that nitrogen-containing resins exhibit superior Ru / W selectivity when nitrogen atoms are present in the main chain. From a comparison of Examples 56-58 with Examples 23-25, 46-55, 59-62, and 71-76, it was confirmed that superior Ru / W selectivity was achieved when the quaternary ammonium salt contained 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 triethyl(2-hydroxyethyl)ammonium salt. A comparison of Examples 37, 42, and 43 with Examples 38-41 confirmed that Ru / W selectivity is superior when the pH is between 3.0 and 10.0. A comparison of Examples 28 and 36 with Examples 29-35 confirmed that when the weight-average molecular weight of the nitrogen-containing resin is between 1,000 and 200,000, the Ru / W selectivity is superior. A comparison of Examples 63 and 67 with Examples 64-66 confirmed that when the nitrogen-containing resin content is 1 to 1000 ppm by mass relative to the total mass of the composition, the Ru / W selectivity is superior.

[0238] <Purification process> Furthermore, the compositions of Examples 1 to 76 were each subjected to the purification treatments described in Methods 1 to 6 below, yielding 500 g of each purified composition. Each purified composition was evaluated in the same manner as described above, and the evaluations were the same as those for each of the examples.

[0239] [Method 1] A vertically set column (300 ml capacity) was packed with Organo's ORLITE DS-4 (75 ml) as the cation exchange resin. The composition was passed through this column at a space velocity (SV) of 1.4 (1 / h). Throughout the entire procedure, the temperature of the cation exchange resin and the composition was 25°C.

[0240] [Method 2] A vertically set column (300 ml capacity) was packed with Organo's ORLITE DS-21 (75 ml) as the chelating resin. The composition was passed through this column at a space velocity (SV) of 1.4 (1 / h). Throughout the entire procedure, the temperature of the chelating resin and the composition was 25°C.

[0241] [Method 3] A vertically mounted column (300 ml capacity) was filled with a resin mixture consisting of Organo's ORLITE DS-21 (75 ml) and DS-4 (75 ml). The composition was then passed through this column at a space velocity (SV) of 1.4 (1 / h). Throughout the entire procedure, the temperature of the resin mixture and the composition remained at 25°C.

[0242] [Method 4] Ion exchange resin membrane Pall Mustang Q (0.02m 2 The composition was passed through the ion exchanger on the membrane at a rate of 100 mL / min. Throughout the series of operations, the temperature of the ion exchanger on the membrane and the composition were both 25°C.

[0243] [Method 5] A vertically positioned column (300 ml capacity) was filled with Organo's ORLITE DS-4 (75 ml) as the cation exchange resin. This was used as the cation exchange column. Furthermore, a vertically set column (300 ml capacity) was filled with Organo's ORLITE DS-21 (75 ml) as the chelating resin. This was designated as the chelating resin column. The composition was passed through a cation exchange column, and then through a chelate resin column. In both cases, the space velocity (SV) was 1.4 (1 / h). Throughout the series of operations, the temperature of the cation exchange resin, chelate resin, and composition was 25°C.

[0244] [Method 6] The composition was passed through the chelate resin column of Method 5 above, and then through the cation exchange column of Method 5 above. In both cases, the space velocity (SV) was 1.4 (1 / h). Throughout the series of operations, the temperature of the cation exchange resin, chelate resin, and composition was all 25°C. [Explanation of symbols]

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

Claims

1. Periodic acid or its salts, Quaternary ammonium salts, A resin containing nitrogen atoms, A solvent is included, A composition that is substantially free of insoluble particles, A composition in which the water content is 50% by mass or more of the total mass of the composition.

2. The composition according to claim 1, for use with a material to be treated that contains ruthenium.

3. The composition according to claim 1, wherein the resin has repeating units containing nitrogen atoms.

4. The composition according to claim 1, wherein the resin comprises repeating units selected from the group consisting of repeating units represented by the following formula (1), repeating units represented by the following formula (2), repeating units represented by the following formula (3), and repeating units represented by the following formula (4). 【Chemistry 1】 In formula (1), L １１ ~L １５ Each of these independently represents a single bond or a divalent linking group. In formula (1), X represents a divalent linking group containing a nitrogen atom. In formula (1), R １１ Each of these independently represents a monovalent substituent. In formula (1), n １ This represents an integer from 0 to 5. In formula (2), L ２１ This represents a divalent linking group. In formula (2), L ２２ This represents a single bond or a divalent linking group. In formula (2), R ２１ represents a hydrogen atom or a monovalent substituent. In formula (2), R ２２ This represents a monovalent substituent containing a nitrogen atom. In formula (3), L ３１ represents a divalent linking group. In formula (3), R ３１ and R ３２ Each of these independently represents a monovalent substituent. In formula (3), A － This represents a monovalent anion. In formula (4), L ４１ This represents a divalent linking group. In formula (4), R ４１ represents a hydrogen atom or a monovalent substituent.

5. The composition according to claim 4, wherein the resin comprises 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. The composition according to claim 4, wherein the resin comprises a repeating unit represented by formula (1).

7. The composition according to claim 4, wherein the resin comprises a repeating unit represented by formula (3).

8. The composition according to claim 1, wherein the resin has repeating units comprising a quaternary ammonium salt structure.

9. The composition according to claim 1, wherein the resin contains nitrogen atoms in its main chain.

10. The composition according to claim 1, 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 according to claim 1, 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 triethyl(2-hydroxyethyl)ammonium salt.

12. The composition according to claim 1, wherein the pH is 3.0 to 10.

0.

13. The composition according to claim 1, wherein the weight-average molecular weight of the resin is 1,000 to 200,000.

14. The composition according to claim 1, wherein the content of the resin is 1 to 1,000 ppm by mass relative to the total mass of the composition.

15. A method for treating an object containing ruthenium and tungsten, comprising contacting the object with the composition described in any one of claims 1 to 14 to remove ruthenium.

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