Processing liquid

Abstract

To provide a treatment liquid which has a large ratio of a dissolution rate of TiN to a dissolution rate of W, and has a large dissolution rate of TiN.SOLUTION: A treatment liquid contains water, a cationic compound, an anionic compound selected from the group consisting of a resin having a carboxy group or its salt, a resin having a sulfo group or its salt, a resin having a phosphite group or its salt, and a resin having a phosphate group or its salt, and an oxidant, has a pH of 7.0 or less, and does not substantially contain abrasive grains.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a processing liquid. [Background technology]

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

[0003] For example, Patent Document 1 discloses a composition comprising an oxidizing agent, an etchant, a corrosion inhibitor, and a solution, for selectively removing titanium nitride without dissolving tungsten or the like. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] U.S. Publication No. 10392560 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present inventors investigated the composition (treatment solution) described in the above-mentioned patent document and found that the ratio of the dissolution rate of titanium nitride (TiN) to the dissolution rate of tungsten (W) was not necessarily sufficient, and that the dissolution rate of TiN was insufficient.

[0006] Therefore, the object of the present invention is to provide a processing solution in which the ratio of the dissolution rate of TiN to the dissolution rate of W is large, and the dissolution rate of TiN is large. [Means for solving the problem]

[0007] The inventors of this invention have diligently studied and developed the present invention to solve the above problems. Specifically, they have found that the above problems can be solved by the following configuration.

[0008] [1] Water and, Cationic compounds and An anionic compound selected from the group consisting of resins having a carboxyl group or a salt thereof, resins having a sulfo group or a salt thereof, resins having a phosphite group or a salt thereof, and resins having a phosphate group or a salt thereof, Contains an oxidizing agent, The pH is 7.0 or lower. A processing solution that contains virtually no abrasive particles. [2] The treatment solution according to [1], wherein the cationic compound includes a compound having a nitrogen atom. [3] The treatment solution according to [1] or [2], wherein the cationic compound includes a compound having a structure selected from the group consisting of structures represented by formulas (1) to (4) described later. [4] The treatment solution according to any one of [1] to [3], wherein the cationic compound includes a compound selected from the group consisting of compounds represented by formulas (A) to (G) described later. [5] The treatment solution according to any one of [1] to [3], wherein the cationic compound includes a compound having a structure represented by formula (3-4) described later. [6] The treatment solution according to [5], wherein the cationic compound includes a compound represented by formula (H) described later. [7] The treatment solution according to any one of [1] to [3], wherein the cationic compound comprises a resin having repeating units selected from the group consisting of repeating units represented by formulas (I) to (L) described later. [8] The treatment solution according to [7], wherein the cationic compound contains a resin having repeating units represented by formula (L), which will be described later. [9] The treatment solution according to any one of [1] to [8], wherein the mass ratio of the content of the cationic compound to the content of the anionic compound is 1 to 100.

[10] The treatment solution according to any one of [1] to [9], wherein the oxidizing agent comprises one or more oxidizing agents selected from the group consisting of hydrogen peroxide, nitric acid, cerium nitrate, iron nitrate, peracetic acid, periodic acid, periodate, perchloric acid, perchlorate, chloric acid, hypochlorous acid, hypochlorite, persulfuric acid, persulfate, peroxodisulfuric acid, peroxodisulfate, isocyanuric acid, isocyanurate, trichloroisocyanuric acid, and trichloroisocyanurate.

[11] The treatment solution according to any one of [1] to

[10] , further comprising a fluoride source.

[12] The treatment solution according to

[11] , wherein the fluoride source comprises a compound selected from the group consisting of HF, H2SiF6, H2TiF6, H2ZrF6, HPF6, and HBF4.

[13] A treatment solution according to any one of [1] to

[12] , further comprising a corrosion inhibitor.

[14] A treatment solution according to any one of [1] to

[13] , further comprising an organic solvent.

[15] A processing solution according to any one of [1] to

[14] , used as an etching residue removal solution, a resist stripping agent, a cleaning solution after chemical mechanical polishing, or an etching solution. [Effects of the Invention]

[0009] According to the present invention, the ratio of the dissolution rate of TiN to the dissolution rate of W is large, and a processing solution with a high dissolution rate of TiN can be provided. [Modes for carrying out the invention]

[0010] 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.

[0011] The following definitions are used within 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, if two or more components are present, the "content" of those components means the total content of those two or more components. In this specification, "ppm" means "parts-per-million (10 -6 ) means "ppb" stands for "parts-per-billion (10 -9 It means ")". Unless otherwise specified, the compounds described herein may include isomers (compounds with the same number of atoms but different structures), optical isomers, and isotopes. Furthermore, only one isomer or multiple isotopes may be included. In this specification, the bonding direction of the divalent group (e.g., -COO-) is not limited unless otherwise specified. For example, if Y in a compound represented by the formula "XYZ" is -COO-, the compound may be "XO-CO-Z" or "X-CO-OZ".

[0012] In this specification, "weight-average molecular weight" means the weight-average molecular weight on a polyethylene glycol basis, as measured by GPC (gel permeation chromatography).

[0013] The present invention will be described in detail below. Furthermore, a large ratio of the dissolution rate of TiN to the dissolution rate of W is also referred to as "excellent TiN dissolution selectivity."

[0014] <Processing solution> The treatment solution of the present invention comprises water, a cationic compound, an anionic compound selected from the group consisting of a resin having a carboxyl group or a salt thereof, a resin having a sulfo group or a salt thereof, a resin having a phosphite group or a salt thereof, and a resin having a phosphate group or a salt thereof, and an oxidizing agent, has a pH of 7.0 or less, and substantially contains no abrasive particles. The mechanism by which the processing solution of the present invention exhibits excellent TiN dissolution selectivity and increases the dissolution rate of TiN is not entirely clear, but the inventors speculate as follows. The treatment solution of the present invention is thought to have solubility for TiN because it contains water and an oxidizing agent and has a pH of 7.0 or lower. Furthermore, by including both cationic and anionic compounds simultaneously, a protective layer is formed at the interface between W and the treatment solution, reducing the dissolution rate of W. On the other hand, no such protective layer is formed on the surface between TiN and the treatment solution, allowing for the selective dissolution of TiN. The reason why a protective layer is formed only at the interface between W and the treatment solution is that W tends to become negatively charged at the interface with the treatment solution in the presence of an oxidizing agent and water, making it easier for a protective layer to form from the two compounds. The processing solution of the present invention will be described below.

[0015] [Components of the treatment solution] The treatment solution of the present invention comprises water, a cationic compound, the above-mentioned anionic compound, and an oxidizing agent. The following describes each component of the treatment solution.

[0016] (water) The processing solution contains water. The water contained in the processing solution is not particularly limited, but distilled water, deionized water, pure water, or ultrapure water is preferred, and pure water or ultrapure water is more preferred, as it does not affect the object being processed. The water content should be the remainder of the components that may be present in the treatment solution. The water content is preferably 1.0% by mass or more, more preferably 30.0% by mass or more, even more preferably 60.0% by mass or more, and particularly preferably 80.0% by mass or more, relative to the total mass of the treatment liquid. The upper limit is preferably 99.99% by mass or less, more preferably 99.9% by mass or less, even more preferably 99.0% by mass or less, and particularly preferably 97.0% by mass or less, relative to the total mass of the treatment liquid.

[0017] (Cationic compounds) The treatment solution contains cationic compounds. Cationic compounds are compounds that have a group with a cationized structure. Furthermore, the cationized structure includes structures that can be cationized in the treatment solution. That is, cationic compounds also include compounds that do not have a cationized structure in themselves, but have a group with a structure that can be cationized in the treatment solution. The cationic compound is not particularly limited, but it is preferable to include a compound having a nitrogen atom in order to have superior TiN solubility selectivity. The compounds containing nitrogen atoms are not particularly limited and may be low-molecular-weight compounds or high-molecular-weight compounds (resins).

[0018] Among compounds containing nitrogen atoms, compounds having the structures represented by the following formulas (1) to (4) are preferred because they exhibit superior TiN solubility selectivity.

[0019] [ka]

[0020] In equations (1) to (4), * indicates the bonding position. In formulas (1), (2), and (4), R independently represents a hydrogen atom or a monovalent substituent. Examples of monovalent substituents represented by R include optionally substituted alkyl groups, optionally substituted aryl groups, and hydroxyl groups. Furthermore, monovalent substituents represented by R include the above monovalent substituents, as well as -O-, -S-, -NH-, and -NR N -, -CO-, -COO-, -CONH-, -SO2-, and -PO4R P - May also be a monovalent substituent combined with a divalent linking group such as R. N and R P Each of these represents a monovalent substituent, and examples include alkyl groups that may have substituents. The optionally substituted alkyl group may be cyclic or linear. The optionally substituted cyclic alkyl group may be monocyclic or polycyclic. The optionally substituted linear alkyl group may be linear or branched. The number of carbon atoms in the optionally substituted cyclic alkyl group (cycloalkyl group) is not particularly limited, but is preferably 4 to 25, and more preferably 5 to 20. The number of carbon atoms in the chain alkyl group, which may have substituents, is not particularly limited, but is preferably 1 to 25, and more preferably 1 to 20. Examples of substituents on optionally substituted alkyl groups include halogen atoms, hydroxyl groups, optionally substituted alkyl groups, and optionally substituted aryl groups. Furthermore, the methylene groups constituting the optionally substituted alkyl groups may be substituted with -O-, -S-, -CO-, -COO-, -CONH-, -SO2-, and divalent linking groups such as those in formulas (1) to (4) above. As for alkyl groups that may have substituents, linear alkyl groups that do not have substituents are preferred. The optionally substituted aryl group may be a heteroaryl group containing atoms other than carbon atoms in its ring members. The optionally substituted aryl group may be polycyclic or monocyclic. The number of ring member atoms of the optionally substituted aryl group is not particularly limited, but is preferably 5 to 15, and more preferably 5 to 10. Examples of substituents on the optionally substituted aryl group include those similar to those on the optionally substituted alkyl group, with halogen atoms, hydroxyl groups, or unsubstituted alkyl groups being preferred. The group represented by R is preferably a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group.

[0021] Furthermore, the bond positions represented by * in formulas (1) to (4) may each be independently bonded to other substituents. That is, they may be monovalent or divalent groups represented by the following formulas (1-1), (2-1), (3-1), (3-2), (4-1), and (4-2).

[0022] [ka]

[0023] In equations (1-1), (2-1), (3-2), (4-1), and (4-2), R is the same as R in equations (1) to (4) above. In equations (3-1) and (4-2), R S represents a divalent substituent. Examples of divalent substituents include those obtained by removing one hydrogen atom from a carbon atom at a bonding position of an alkyl group which may have the above substituent.

[0024] Among the structures represented by the above formulas, compounds having the structure represented by the following formula (3-3) are preferred because they exhibit superior TiN solubility selectivity.

[0025] [ka]

[0026] In equation (3-3), * represents the bonding position. In equation (3-3), n represents an integer between 1 and 3. In particular, the embodiment in which n in formula (3-3) is 2, that is, the compound having the structure represented by the following formula (3-4), is more preferred because it exhibits superior TiN solubility selectivity.

[0027] [ka]

[0028] In equation (3-4), * represents the bonding position.

[0029] Furthermore, other linking groups may be bonded to the bonding positions in formulas (1) to (4) to form a ring. The formed ring may or may not have an aromatic property as a whole. Examples of ring structures having the structure of formula (1) include pyrrolidine rings, imidazolidine rings, pyrazolidine rings, piperidine rings, morpholine rings, thiaidine rings, pyrrole rings, indole rings, and carbazole rings. An example of a ring structure having the structure of formula (2) is a ring structure having the structure of formula (1) in which the nitrogen atom has been cationized. Examples of ring structures having the structure of formula (3) include imidazole rings, pyrazole rings, oxazole rings, thiazole rings, imidazoline rings, triazole rings, tetrazole rings, pyridine rings, pyrimidine rings, pyrazine rings, benzimidazole rings, benzotriazole rings, quinoline rings, quinazoline rings, quinoxaline rings, purine rings, pteridine rings, and acridine rings. An example of a ring structure having the structure of formula (4) is a ring structure having the structure of formula (3) in which the nitrogen atom has been cationized.

[0030] Examples of compounds having the structure of formula (1) include ammonia, primary amines, secondary amines, tertiary amines, hydroxyamines, and hydrazine compounds, as well as compounds having a ring structure with the structure of formula (1) described above. Examples of compounds having the structure of formula (2) include ammonium salts and quaternary ammonium salts, as well as compounds having a ring structure with the structure of formula (2) described above. Examples of compounds having the structure of formula (3) include imines, amidines, guanidines, biguanides, triguanides, and oximes, as well as compounds having a ring structure with the structure of formula (3) described above. Examples of the compound having the structure of formula (4) include an iminium salt, an aminidinium salt, a guanidinium salt, a biguanide salt, a tribiguanide salt, and a compound having a ring structure with the structure of formula (4). The compounds having the structures of formulas (1) to (4) may be a resin containing a repeating unit having the above structure. Further, the above compounds may be in the form of a salt bonded to a suitable anion. Hereinafter, the compounds having the structures of formulas (1) to (4) will be described.

[0031] As the compound having the above structure, compounds represented by the following formulas (A) to (G) are preferable in terms of excellent TiN dissolution selectivity. Hereinafter, the compounds represented by each formula will be described in detail.

[0032] [Chemical formula]

[0033] In formula (A), R A1 ~R A3 each independently represents a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent represented by R A1 ~R<​​​​​​​​​​​​The monovalent substituent represented by may have two or more groups bonded to each other to form a ring. Note, R A3 A monovalent substituent represented by -L A1 -N(-R A1 )(-R A2 It is also preferable that the group is represented by ). In the above formula, L A1 This represents a divalent linking group, as shown below L H1 Examples include divalent linking groups similar to those represented by , with alkylene groups being preferred. The alkylene group preferably has 1 to 10 carbon atoms.

[0034] In formula (B), R B1 ~R B4 Each of these independently represents a hydrogen atom or a monovalent substituent. R B1 ~R B4 Examples of monovalent substituents represented by the above R A1 ~R A3 Examples of monovalent substituents represented by the above R include groups similar to those listed above. A1 ~R A3 A similar embodiment to that represented by the monovalent substituent is preferred. Note, R B1 ~R B4 In a preferred configuration, one of the groups represented is a linear alkyl group having 8 or more carbon atoms and no substituents, while the other three groups are linear alkyl groups having 3 or fewer carbon atoms and no substituents. Note, R B1 ~R B4 The monovalent substituent represented by may have two or more groups bonded to each other to form a ring. In formula (B), A y- represents an anion with y valence. Also, in equation (B), y represents an integer from 1 to 6. Therefore, equation (B) is an anion A with y valence. y- This indicates that the compound is formed by ion bonding between y cations, as shown in the square brackets. y is preferably 1 to 4, preferably 1 to 3, and more preferably 1 or 2. The anion is not particularly limited and may be an inorganic ion or an organic ion, but an inorganic ion is preferred. Examples of inorganic ions include chloride ions, bromide ions, iodide ions, and sulfate ions. Among these, chloride ions, bromide ions, or iodide ions are preferred as anions.

[0035] In formula (B-1), R B5 ~R B10 Each of these independently represents a hydrogen atom or a monovalent substituent. B5 ~R B10 Examples of monovalent substituents represented by the above R A1 ~R A3 Examples of monovalent substituents represented by the above R include groups similar to those listed above. A1 ~R A3 A similar embodiment to that represented by the monovalent substituent is preferred. In formula (B-1), L B1 This represents a divalent linking group. A1 The divalent linking group represented by is L below. H1 Examples include divalent linking groups similar to those represented by , with alkylene groups being preferred. The alkylene group preferably has 1 to 10 carbon atoms. In formula (B-1), A - represents a monovalent anion. The anion is not particularly restricted, as described above A y- Examples of monovalent ions represented by include, among which the anion is preferably a chloride ion, a bromide ion, or an iodide ion.

[0036] In formula (C), R C1 represents a hydrogen atom or a monovalent substituent. R C1 Examples of monovalent substituents represented by the above R A1 ~R A3 Examples of monovalent substituents represented by the above R include groups similar to those listed above. A1 ~R A3 A similar embodiment to that represented by the monovalent substituent is preferred. Also, R C1 It is also preferable that this represents a hydrogen atom. In formula (C), X independently represents either a nitrogen atom or CH. In formula (C), it is preferable that one or two of the X values ​​are N.

[0037] In formula (D), R D1 and R D2 represents a hydrogen atom or a monovalent substituent. R D1 and R D2 Examples of monovalent substituents represented by the above R A1 ~R A3 Examples of monovalent substituents represented by the above R include groups similar to those listed above. A1 ~R A3 A similar embodiment to that represented by the monovalent substituent is preferred. In equation (D), X independently represents either a nitrogen atom or CH. In equation (D), it is preferable that one or two of the X values ​​are N. In formula (D), A y- represents an anion with y valence. In equation (D), y represents an integer from 1 to 6. Since y and the anion are the same as those explained in equation (B), their explanation will be omitted.

[0038] In formula (E), R E1 This represents a monovalent substituent. R E1 Examples of monovalent substituents represented by include groups similar to R described above, with alkyl groups, hydroxyl groups, or halogen atoms being preferred, even if substituted. The alkyl groups that may have substituents are as described above. In equation (E), m represents an integer between 0 and 5. m is preferably 0 to 3, more preferably 0 or 1, and even more preferably 0.

[0039] In formula (F), R F1 This represents a monovalent substituent. R F1 Examples of monovalent substituents represented by the above R E1Examples of monovalent substituents represented by the above R include groups similar to those listed above. E1 A similar embodiment to that represented by the monovalent substituent is preferred. In formula (F), R F2 represents a hydrogen atom or a monovalent substituent. R F2 Examples of monovalent substituents represented by the above R A1 ~R A3 Examples of monovalent substituents represented by the above R include groups similar to those listed above. A1 ~R A3 A similar embodiment to that represented by a monovalent substituent is preferred. In particular, R F2 A preferred embodiment is in which the monovalent substituent represented by is a linear alkyl group having 8 to 20 carbon atoms. In equation (F), m represents an integer between 0 and 5. m is preferably 0 to 3, more preferably 0 or 1, and even more preferably 0. In formula (F), A y- represents an anion with y valence. In equation (F), y represents an integer from 1 to 6. Since y and the anion are the same as those explained in equation (B), their explanation will be omitted.

[0040] In formula (G), R G1 and R G2 Each of these independently represents a hydrogen atom or a monovalent substituent. R G1 and R G2 Examples of monovalent substituents represented by R include groups similar to those described above, and among these, optionally substituted alkyl groups or optionally substituted aryl groups are preferred. The optionally substituted alkyl group preferably has 1 to 8 carbon atoms, and it is also preferable that it has a hydroxyl group as a substituent. The optionally substituted aryl group preferably has an optionally substituted phenyl group, and it is also preferable that it has an alkyl group with 1 to 3 carbon atoms as a substituent. G1 and R G2 It is also preferable that either one of them represents a hydrogen atom. In equation (G), n represents an integer between 1 and 3. n is preferably 2 or 3, more preferably 2, in terms of excellent TiN dissolution selectivity.

[0041] As the compound represented by formula (G), a compound represented by the following formula (H) is preferable in terms of excellent TiN dissolution selectivity.

[0042]

Chemical formula

[0043] In formula (H), R H1 represents a hydrogen atom or a monovalent substituent. As the monovalent substituent represented by R H1 , for example, the same groups as those exemplified for the monovalent substituents represented by the above R G1 and R G2 can be mentioned, and the same embodiments as the monovalent substituents represented by the above R G1 and R G2 are preferable. It is also preferable that R H1 represents a hydrogen atom. In formula (H), L H1 represents a single bond or a divalent linking group. As the divalent linking group represented by L H1 , for example, an alkylene group, a cycloalkylene group, an arylene group, and a group 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, and an arylene group can be mentioned. Among them, as the divalent linking group represented by L H1 , an alkylene group is preferable. The number of carbon atoms of the above alkylene group is not particularly limited, but is preferably 1 to 15, more preferably 3 to 10. In formula (H), Z represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a group represented by the following formula (3-5). Among them, a group represented by the following formula (3-5) is preferable in terms of excellent TiN dissolution selectivity.

[0044] [Chemical formula]

[0045] In formula (3-5), * represents the bonding position. In formula (3-5), R3 represents a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent represented by R3 include, for example, the above R G1 and R G2 The same groups as those listed for the monovalent substituents represented by and the above R G1 and R G2 The same embodiments as those of the monovalent substituents represented by are preferred. Among them, the monovalent substituent represented by R3 is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, and more preferably an aryl group which may have a substituent. As the substituent of the aryl group which may have a substituent, an alkyl group having 1 to 3 carbon atoms, a hydroxy group, or a halogen atom is preferred, and a halogen atom is more preferred.

[0046] Specific examples of the above cationic compound include, for example, tributylamine, didodecylmethylamine, hexadecyltrimethylammonium chloride, cetylpyridinium chloride, hexamethonium chloride dihydrate, guanidinoacetic acid, 4-guanidinobutyric acid, 3-methyl-L-arginine, arginine, homoarginine, N 5 -monomethyl-L-arginine, canavanine, N 2 -methyl-L-arginine, N 2 -(2-aminoethyl)-D-arginine, N 2-(2-aminoethyl)-L-arginine, 2-methyl-L-arginine, 1-phenyl biguanide, 1-(o-tolyl)biguanide, 1-(3-methylphenyl)biguanide, 1-(4-methylphenyl)biguanide, 1-(2-chlorophenyl)biguanide, 1-(4-chlorophenyl)biguanide, 1-(2,3-dimethylphenyl)biguanide, 1-(2,6-dimethylphenyl)biguanide, 1-(1-naphthyl)biguanide, 1-(4-methoxyphenyl) Biguanides, 1-(4-nitrophenyl)biguanide, 1-diphenylbiguanide, 1,5-diphenylbiguanide, 1,5-bis(4-chlorophenyl)biguanide, 1,5-bis(3-chlorophenyl)biguanide, 1-(4-chloro)phenyl-5-(4-methoxy)phenylbiguanide, 1,1-bis(3-chloro-4-methoxyphenyl)biguanide, 1,5-bis(3,4-dichlorophenyl)biguanide, 1,5-bis(3,5-dichlorophenyl)biguanide Nido, 1,5-bis(4-bromophenyl)biguanide, 1-1-phenyl-1-methylbiguanide, 1-(4-chlorophenyl)-5-(1-methylethyl)biguanide (also known as proguanil), 1-(3,4-dichlorophenyl)-5-(1-methylethyl)biguanide, 1-(4-methylphenyl)-5-octylbiguanide, 1-(4-chlorophenyl)-2-(N'-propane-2-ylcarbamimidoyl)guanidine, ditylbiguanide, dinaphthylbi Guanide, dibenzyl biguanide, 4-chlorobenzhydryl biguanide, 1-benzo[1,3]dioxol-5-ylmethyl biguanide, 1-benzyl-5-(pyridine-3-yl)methyl biguanide, 1-benzyl biguanide, 4-chlorobenzyl biguanide, 1-(2-phenylethyl) biguanide, 1-hexyl-5-benzyl biguanide, 1,1-dibenzyl biguanide, 1,5-dibenzyl biguanide, 1-(phenethyl)-5-propyl biguanide, 1,5-Bis(phenethyl)biguanide, 1-Cyclohexyl-5-phenylbiguanide, 1-(4-phenylcyclohexyl)biguanide, 1-(4-methyl)cyclohexyl-5-phenylbiguanide, 1-Cyclopentyl-5-(4-methoxyphenyl)biguanide, norbornylbiguanide, dinorbornylbiguanide, adamantylbiguanide, diadamantylbiguanide, dicyclohexylbiguanide, ethylenedigiguanide, propylenedibiguanide, tetramethyl Densebiguanide, pentamethylenedibiguanide, hexamethylenedibiguanide, heptamethylenedibiguanide, octamethylenedibiguanide, 1,6-bis-(4-chlorobenzylbiguanide)-hexane, 1,1'-hexamethylenebis(5-(p-chlorophenyl)biguanide) (also known as chlorhexidine), 2-(benzyloxymethyl)pentane-1,5-bis(5-hexylbiguanide), 2-(phenylthiomethyl)pentane-1,5-bis(5-phenethylbiguanide) Guanide, 3-(phenylthio)hexane-1,6-bis(5-hexylbiguanide), 3-(phenylthio)hexane-1,6-bis(5-cyclohexylbiguanide), 3-(benzylthio)hexane-1,6-bis(5-hexylbiguanide), 3-(benzylthio)hexane-1,6-bis(5-cyclohexylbiguanide), phenylenyl dibiguanide, naphthyleneyl dibiguanide, pyridinyl dibiguanide, piperazinyl dibiguanide, phthalyl dibiguanide Examples include 1,1'-[4-(dodecyloxy)-m-phenylene]bis-biguanide, 2-(decylthiomethyl)pentane-1,5-bis(5-isopropyl biguanide), 2-(decylthiomethyl)pentane-1,5-bis(5,5-diethyl biguanide), 1,1-dimethyl biguanide (also known as metformin), 1-(2-phenylethyl) biguanide (also known as phenformin), and polyalkylene biguanides (e.g., polyhexamethylene biguanide).

[0047] The following describes resins containing repeating units having the structures of formulas (1) to (4) above. The repeating units are preferably those represented by formulas (I) to (L) below. Each of these repeating units will be described in detail below.

[0048] [ka]

[0049] In formula (I), L I1 This represents a single bond or a divalent linking group. L I1 Examples of the divalent linking group represented by the above L H1 Examples of divalent linking groups include those represented by , with alkylene groups or arylene groups being preferred, and alkylene groups being more preferred. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 6 is preferred, and 1 to 4 is more preferred. The number of carbon atoms in the arylene group is not particularly limited, but 6 to 10 is preferred. In formula (I), Y represents a group having the structure represented by formula (1-1), formula (2-1), formula (3-1), or formula (4-2). Y is preferably a group having the structure represented by formula (1-1) or formula (2-1), and more preferably a group having the structure represented by formula (1-1).

[0050] In formula (J), L J1 ~L J4 Each of these independently represents a single bond or a divalent linking group. L J1 and L J2 Examples of the divalent linking group represented by the above L H1 Examples include divalent linking groups represented by , with alkylene groups being preferred. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 6 is preferred, and 1 to 4 is more preferred. L J3 and L J4 Examples of the divalent linking group represented by the above L H1Examples include divalent linking groups represented by , with alkylene groups being preferred. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 3 is preferred, and 1 or 2 is more preferred. In formula (J), R J1 represents a hydrogen atom or a monovalent substituent. R J1 Examples of monovalent substituents represented by the above R A1 ~R A3 Examples of monovalent substituents represented by the above R include groups similar to those listed above. A1 ~R A3 A similar embodiment to that represented by the monovalent substituent is preferred. Also, R J1 It is also preferable that this represents a hydrogen atom.

[0051] In formula (K), L K1 ~L K4 Each of these independently represents a single bond or a divalent linking group. L K1 ~L K4 The divalent linking groups represented by are the corresponding L J1 ~L J4 Since this is similar to the divalent linking group represented by , the explanation is omitted. In formula (K), R K1 and R K2 Each of these independently represents a hydrogen atom or a monovalent substituent. R K1 and R K2 Examples of monovalent substituents represented by the above R A1 ~R A3 Examples of monovalent substituents represented by the above R include groups similar to those listed above. A1 ~R A3 A similar embodiment to that represented by the monovalent substituent is preferred. In formula (K), A - This represents a monovalent anion. A - The monovalent anions represented by are monovalent anions, and among those explained in formula (B), those that are monovalent anions are listed. In particular, A - The monovalent anion represented by is preferably a chloride ion, a bromide ion, or an iodide ion.

[0052] In formula (L), L L1 This represents a single bond or a divalent linking group. The above L H1 Examples of divalent linking groups include those represented by , with alkylene groups or arylene groups being preferred, and alkylene groups being more preferred. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 15 is preferred, and 4 to 10 is more preferred. The number of carbon atoms in the arylene group is not particularly limited, but 6 to 10 is preferred. In equation (L), k represents an integer between 0 and 3. k is preferably 1 or 2, and more preferably 2.

[0053] Specific examples of resins having repeating units represented by the above formulas (I) to (L) include, for example, polymerization products of allylamine, polymerization products of diallylamine, polymerization products of diallylalkylamine (e.g., polymerization product of diallylmethylamine), polymerization products of diallyldialkylammonium salts (e.g., polymerization product of diallyldimethylammonium chloride), polymerization products of biguanidyl-substituted α-olefin monomers (e.g., poly(vinyl biguanide), poly(N-vinyl biguanide), poly(allyl biguanide)), and copolymers of the compounds prior to polymerization.

[0054] Furthermore, resins having repeating units represented by the above formulas (I) to (K) include paragraphs

[0036] to

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

[0025] to

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

[0062] to

[0065] of Japanese Patent Publication No. 2004-115675, and paragraphs

[0051] to

[0039] of Japanese Patent Publication No. 2005-002196.

[0055] Resins described in 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. 2017-75243, and paragraphs

[0062] to

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

[0055] In a resin containing repeating units represented by formulas (I) to (L) above, the mass ratio of one or more repeating units selected from the group consisting of repeating units represented by formulas (I) to (L) above is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and more preferably 70 to 100% by mass, with respect to the total mass of the resin. In the above resin, repeating units other than those represented by formulas (I) to (L) above can be appropriately selected from known repeating units. The weight-average molecular weight of the resin containing the repeating units represented by the above formulas (I) to (L) is preferably 500 to 200,000, more preferably 1,600 to 15,000, and even more preferably 3,000 to 8,000.

[0056] The content of cationic compounds is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.03% by mass or more, based on the total mass of the treatment solution. The upper limit is preferably 5.00% by mass or less, more preferably 1.00% by mass or less, even more preferably 0.50% by mass or less, and particularly preferably 0.10% by mass or less, based on the total mass of the treatment solution. The content of cationic compounds is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.03% by mass or more, based on the total mass of solids excluding the solvent in the treatment solution. The upper limit is preferably 5.00% by mass or less, more preferably 1.00% by mass or less, even more preferably 0.50% by mass or less, and particularly preferably 0.10% by mass or less, based on the total mass of the treatment solution. Cationic compounds may be used individually or in combination of two or more. When using two or more cationic compounds, it is preferable that their total amount is within the preferred content range described above.

[0057] (Anionic compounds) The treatment solution of the present invention contains an anionic compound. The above anionic compound is a compound selected from the group consisting of resins having a carboxyl group or a salt thereof, resins having a sulfo group or a salt thereof, resins having a phosphite group or a salt thereof, and resins having a phosphate group or a salt thereof. Note that a phosphate group is a group represented by -PO4H2, and a phosphite group is a group represented by -PO3H2. The anionic compound may be any resin having the above-mentioned group or a salt thereof, and may also be a resin having two or more of the above-mentioned groups or salts thereof. For example, it may be a resin (polymer) having a carboxyl group and a sulfo group.

[0058] The anionic compound is preferably a resin having repeating units represented by the following formula (1A).

[0059] [ka]

[0060] In formula (1A), L 1A Each of these independently represents a single bond or a divalent linking group. L 1A Examples of the divalent linking group represented by the above L H1 Examples of divalent linking groups are represented by . Among them, L 1A The divalent linking group represented by is preferably an alkylene group, an arylene group, a group formed by combining -COO- and an alkylene group, or a group formed by combining -CONH- and an alkylene group, and more preferably an arylene group or a group formed by combining -CONH- and an alkylene group. In formula (1A), R 1A R represents a hydrogen atom or a monovalent substituent. 1A The monovalent substituent represented by is preferably an alkyl group having 1 to 3 carbon atoms. In formula (1A), W represents either a hydrogen atom or an anionic group, independently. The anionic group represented by W is -COOH, -COO - Ct + -SO3H, -SO3 - Ct+ -PO4H2, -PO3H2, -PO4 2- (Ct + )2, and -PO3 2- (Ct + ) is one of the following. In particular, -COOH, -COO - Ct + -SO3H or -PO3H2 is preferred. Note: Ct + Ct represents a monovalent cation. + As for Na + , or K + It is preferable.

[0061] Examples of repeating units represented by the above formula (1A) include acrylic acid, methacrylic acid, maleic acid, 4-vinylbenzoic acid, p-styrenesulfonic acid, vinyl phosphite, and vinyl phosphate, 2-(acryloylamino)-2-methyl-1-propanesulfonic acid, as well as repeating units derived from the sodium salts of these compounds.

[0062] The content of the repeating unit represented by formula (1A) above is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass, based on the total mass of the anionic compound. Other repeating units besides the repeating unit represented by formula (1A) above that the anionic compound contains can be appropriately selected from known repeating units. The anionic compound may contain two or more repeating units represented by the above formula (1A).

[0063] The weight-average molecular weight of the anionic compound is preferably 2000 or more, more preferably 10000 or more, even more preferably 50000 or more, and particularly preferably 100000 or more. There is no particular upper limit, but it is generally 1,000,000 or less.

[0064] The mass ratio of the cationic compound content to the anionic compound content is preferably 0.8 to 120.0, more preferably 1.0 to 100.0, even more preferably 2.0 to 50.0, and particularly preferably 3.0 to 20.0, in terms of superiority in terms of TiN dissolution rate and / or TiN solubility.

[0065] (Oxidizing agent) The treatment solution of the present invention contains an oxidizing agent. The oxidizing agent is a compound different from the cationic and anionic compounds mentioned above. The oxidizing agent is not particularly limited as long as it has oxidizing ability, but it is preferable that the oxidizing agent includes one or more oxidizing agents selected from the group consisting of hydrogen peroxide, nitric acid, cerium nitrate, iron nitrate, peracetic acid, periodic acid, periodate, perchloric acid, perchlorate, chloric acid, hypochlorous acid, hypochlorite, persulfuric acid, persulfate, peroxodisulfate, peroxodisulfate, isocyanuric acid, isocyanurate, trichloroisocyanuric acid, and trichloroisocyanurate. The above periodic acid includes metaperiodic acid (HIO4) and orthoperiodic acid (H5IO6). The above periodate includes metaperiodic acid and orthoperiodic acid. In particular, in terms of superiority in the dissolution rate of TiN and / or superiority in TiN dissolution selectivity, it is more preferable that the oxidizing agent includes one or more oxidizing agents selected from the group consisting of nitric acid, peracetic acid, periodic acid, perchloric acid, peroxodisulfate, and trichloroisocyanuric acid, and even more preferable that it includes one or more oxidizing agents selected from the group consisting of peracetic acid, periodic acid, perchloric acid, peroxodisulfate, and trichloroisocyanuric acid.

[0066] The oxidizing agent content is preferably 0.0001 to 5.00% by mass, more preferably 0.001 to 1.00% by mass, and even more preferably 0.001 to 0.10% by mass, relative to the total mass of the treatment solution.

[0067] (Abrasive grains) The processing solution of the present invention substantially does not contain abrasive particles. The term "abrasive grains" above refers to fine abrasive particles, which are inorganic solids or similar particles that ultimately remain as particles in the processing solution without dissolving. The phrase "substantially absent" above means that the abrasive content is 0.1% by mass or less of the total mass of the treatment solution. Preferably, the abrasive content is 0.01% by mass or less of the total mass of the treatment solution, and more preferably 0.001% by mass or less. There is no particular lower limit to the abrasive content, but it can be 0.0% by mass or more. The abrasive content can be measured in the liquid phase using a commercially available measuring device that employs a light scattering type liquid particle measurement method with a laser as the light source.

[0068] (Fluoride source) The treatment solution of the present invention may contain a fluoride source. By including a fluoride source in the treatment solution, the dissolution rate of TiN can be increased. The fluoride source is a compound different from the cationic and anionic compounds mentioned above. A fluoride source refers to a compound that can supply fluoride ions. Fluoride sources are generally compounds containing fluoride ions and cations. Examples of the above fluoride ions include fluoride ions (F - ), bifluoride ion (HF2 - ), and fluoride-containing ions (e.g., MF6) n- Examples of M include B (boron), Al (aluminum), Si (silicon), P (phosphorus), Ti (titanium), Zr (zirconium), Nb (niobium), Sb (antimony), and Ta (tantalum). Examples of cations include H + Li + kaNa + , K + , and NH4 + H + It is preferable. Among the above fluoride sources, it is preferable that the fluoride source includes a compound selected from the group consisting of HF, H2SiF6, H2TiF6, H2ZrF6, HPF6, and HBF4. The fluoride source content is preferably 0.001 to 5.00% by mass, more preferably 0.005 to 3.00% by mass, and even more preferably 0.10 to 1.00% by mass, relative to the total mass of the treatment solution. The fluoride source may be used alone or in combination of two or more types. When using two or more fluoride sources, it is preferable that their total amount is within the preferred content range described above.

[0069] (Corrosion inhibitor) The treatment solution of the present invention may contain a corrosion inhibitor. By including a corrosion inhibitor in the treatment solution, it is possible to obtain a treatment solution with superior TiN dissolution selectivity. The corrosion inhibitor is a compound different from the cationic and anionic compounds mentioned above. While there are no particular limitations on the corrosion inhibitor, compounds containing silicate ions, polysilicate ions, phosphate ions, polyphosphate ions, or borate ions are preferred. Among these, tetramethylammonium silicate, tetraethylammonium silicate, or boric acid are preferred as corrosion inhibitors. The content of the corrosion inhibitor is preferably 0.001 to 5.00% by mass, more preferably 0.005 to 3.00% by mass, and even more preferably 0.10 to 1.00% by mass, relative to the total mass of the treatment solution. The corrosion inhibitor may be used alone or in combination of two or more types. When using two or more types of corrosion inhibitors, it is preferable that their total amount is within the preferred content range described above.

[0070] (Organic solvents) The processing solution of the present invention may contain an organic solvent. Organic solvents are compounds different from the cationic and anionic compounds mentioned above. The organic solvent is preferably miscible with water in any ratio. Examples of organic solvents include alcohol-based solvents, glycol-based solvents, glycol ether-based solvents, ketone-based solvents, amide-based solvents, and sulfur-containing solvents.

[0071] Examples of alcohol-based solvents include methanol, ethanol, propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, and tert-butyl alcohol.

[0072] Examples of glycol-based solvents include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.

[0073] Examples of glycol ether-based solvents include glycol monoethers. Examples of glycol monoethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether.

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

[0075] Examples of amide solvents include N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide.

[0076] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0077] The organic solvent content is preferably 1 to 5.00% by mass, more preferably 0.005 to 3.00% by mass, and even more preferably 0.10 to 1.00% by mass, relative to the total mass of the treatment solution. Organic solvents may be used individually or in combination of two or more types. When using two or more types of organic solvents, it is preferable that their total amount is within the preferred content range described above.

[0078] (pH adjuster) The treatment solution of the present invention may contain a pH adjusting agent. The pH of the treatment solution may be adjusted to a preferred pH range described later using the pH adjusting agent. The pH adjuster is preferably a compound different from the above-mentioned compound. Examples of pH adjusters include acidic compounds and basic compounds.

[0079] -Acidic compounds- Acidic compounds are compounds that exhibit acidity (pH less than 7.0) in aqueous solutions. Examples of acidic compounds include inorganic acids, organic acids, and their salts. Examples of inorganic acids include sulfuric acid, hydrochloric acid, and their salts. 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. The content of the acidic compound is preferably 0.1 to 10.0% by mass, and more preferably 0.3 to 5.0% by mass, relative to the total mass of the treatment solution.

[0080] -Basic compounds- Basic compounds are compounds that exhibit alkalinity (pH greater than 7.0) in aqueous solutions. Examples of basic compounds include inorganic bases and their salts. Examples of inorganic bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides. The content of the basic compound is preferably 0.1 to 10.0% by mass, and more preferably 0.3 to 5.0% by mass, relative to the total mass of the treatment solution.

[0081] (Other additives) The processing solution may contain other additives besides the components mentioned above. The following describes other additives.

[0082] -Polyhydroxy compounds with a molecular weight of 500 or more- The processing solution may contain polyhydroxy compounds with a molecular weight of 500 or more. The polyhydroxy compound mentioned above is a different compound from the compound that may be contained in the treatment solution. The above polyhydroxy compounds are organic compounds having two or more (e.g., 2 to 200) alcoholic hydroxyl groups in one molecule. The molecular weight (or weight-average molecular weight if a molecular weight distribution exists) of the above polyhydroxy compound is 500 or more, preferably 500 to 100,000, and more preferably 500 to 3,000.

[0083] Examples of the polyhydroxy compounds mentioned above include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; oligosaccharides such as mannitorioose, cellotriose, gentianose, raffinose, meletitose, cellotetrose, and stachyose; and polysaccharides such as starch, glycogen, cellulose, chitin, and chitosan, as well as their hydrolysates.

[0084] Cyclodextrin is also preferred as the polyhydroxy compound mentioned above. Cyclodextrins are a type of cyclic oligosaccharide in which multiple D-glucose molecules are linked together by glucosidic bonds, forming a cyclic structure. Compounds with five or more glucose molecules (e.g., 6-8 molecules) linked together are known. Examples of cyclodextrins include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, with γ-cyclodextrin being preferred.

[0085] The above polyhydroxy compounds may be used individually or in combination of two or more. The content of the above polyhydroxy compound is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 3% by mass, based on the total mass of the treatment solution. The content of the above polyhydroxy compound is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and even more preferably 0.5 to 20% by mass, based on the total mass of the components excluding the solvent in the treatment solution.

[0086] - Surfactants - The processing solution of the present invention may contain a surfactant. The polyhydroxy compound mentioned above is a different compound from the compound that may be contained in the treatment solution. 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; for example, nonionic surfactants can be mentioned.

[0087] 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. The total number of carbon atoms in the surfactant is preferably between 16 and 100.

[0088] Examples of nonionic surfactants include ester-type nonionic surfactants, ether-type nonionic surfactants, ester-ether-type nonionic surfactants, and alkanolamine-type nonionic surfactants, with ether-type nonionic surfactants being preferred.

[0089] Examples of nonionic surfactants include polyethylene glycol, alkyl polyglucoside (Triton BG-10 and Triton CG-110 surfactants from Dow Chemical Company), octylphenol ethoxylate (Triton X-114 from Dow Chemical Company), silane polyalkylene oxide (copolymer) (Y-17112-SGS sample from Momentive Performance Materials), nonylphenol ethoxylate (Tergitol NP-12 from Dow Chemical Company, as well as Triton® X-102, X-100, X-45, X-15, BG-10 and CG-119), Silwet® HS-312 (from Momentive Performance Materials), and tristyrylphenol ethoxylate (MAKON from Stepan Company). TSP-20), polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, alkylallylformaldehyde condensed polyoxyethylene ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of sorbitol ester, polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, sorbitan ester, propylene glycol ester, sucrose ester, aliphatic acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamide, BRIJ (registered trademark) 56 (C 16 H 33 (OCH2CH2) 10 OH), BRIJ(Registered Trademark) 58(C 16 H 33 (OCH2CH2) 20 OH), BRIJ (Registered Trademark) 35(C 12 H 25 (OCH2CH2) 23Examples include alcohol ethoxylates such as OH), primary and secondary alcohol ethoxylates, amine ethoxylates, glucosides, glucamides, polyethylene glycol, poly(ethylene glycol-co-propylene glycol), cetyl alcohol, stearyl alcohol, cetostearyl alcohol (cetyl and stearyl alcohol), oleyl alcohol, octaethylene glycol monododecyl ether, pentaethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ether, decyl glucoside, lauryl glucoside, octyl glucoside, polyoxyethylene glycol octylphenol ether, nonoxynol-9, glycerol alkyl esters, glyceryl laurate, polyoxyethylene glycol sorbitan alkyl esters, polysorbate, sorbitan alkyl esters, span, cocamide MEA, cocamide DEA, dodecyldimethylamine oxide, block copolymers of polypropylene glycol, and mixtures thereof.

[0090] The surfactant content is preferably 0.001 to 8.0% by mass, more preferably 0.005 to 5.0% by mass, and even more preferably 0.01 to 3.0% by mass, relative to the total mass of the treatment solution.

[0091] -Antibacterial agent- The treatment solution may contain an antibacterial agent. The antibacterial agent is a compound different from the above-mentioned compounds that may be contained in the treatment solution. Examples of antibacterial agents include sorbic acid, benzoic acid, dehydroacetic acid, fosfomycin, penicillin, sulbactam, and diaphenylsulfone.

[0092] -Reducing sulfur compounds- The treatment solution may contain reducing sulfur compounds. Reducing sulfur compounds are compounds different from the above-mentioned compounds that may be present in the treatment solution. Reducing sulfur compounds are compounds that possess reducing properties and contain sulfur atoms. Reducing sulfur compounds can improve the corrosion-preventive effect of treatment solutions. In other words, reducing sulfur compounds can act as corrosion inhibitors.

[0093] Examples of reducing sulfur compounds include mercaptosuccinic acid, dithiodiglycerol, bis(2,3-dihydroxypropylthio)ethylene, sodium 3-(2,3-dihydroxypropylthio)-2-methylpropylsulfonate, 1-thioglycerol, sodium 3-mercapto-1-propanesulfonate, 2-mercaptoethanol, thioglycolic acid, and 3-mercapto-1-propanol. Among these, compounds having an SH group (mercapto compounds) are preferred, with 1-thioglycerol, sodium 3-mercapto-1-propanesulfonate, 2-mercaptoethanol, 3-mercapto-1-propanol, or thioglycolic acid being more preferred.

[0094] The above reducing sulfur compounds may be used individually or in combination of two or more. The content of reducing sulfur compounds is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 3% by mass, based on the total mass of the treatment solution. The content of reducing sulfur compounds is preferably 0.01 to 30.0% by mass, more preferably 0.05 to 25.0% by mass, and even more preferably 0.5 to 20.0% by mass, based on the total mass of the components excluding the solvent in the treatment solution.

[0095] [Physical properties of the processing solution] The following describes the physical properties of the processing solution.

[0096] (pH) The pH of the treatment solution of the present invention is 7.0 or lower. Here, the pH of the treatment solution can be measured using a known pH meter in accordance with the method compliant with JIS Z8802-1984. The measurement temperature shall be 25°C. The pH of the processing solution is preferably 1.0 to 6.5, more preferably 1.5 to 5.5, even more preferably 1.5 to 4.0, and particularly preferably 2.0 to 3.0, in terms of superiority in terms of TiN dissolution rate and / or TiN dissolution selectivity.

[0097] (metal content) The processing solution of the present invention preferably contains (measured as an ion concentration) 5 ppm by mass or less of metals (metal elements Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag) as impurities in the solution, and more preferably 1 ppm by mass or less. Since even higher purity processing solutions are expected to be required in the manufacture of state-of-the-art semiconductor devices, it is even more preferable that the metal content be lower than 1 ppm by mass, i.e., on the order of ppb by mass or less, particularly preferably 100 ppb by mass or less, and most preferably less than 10 ppb by mass. A lower limit of 0 is preferred.

[0098] Methods for reducing metal content include, for example, performing purification treatments such as distillation and filtration using ion exchange resins or filters at the stage of raw material production or after production of the treatment solution. Other methods for reducing metal content include using containers that minimize the leaching of impurities (as described later) to hold the raw materials or the manufactured processing liquid. Additionally, fluororesin lining can be applied to the inner walls of pipes to prevent metal components from leaching out during the manufacturing of the processing liquid.

[0099] (Coarse particles) The processing solution may contain coarse particles, but it is preferable that the content of coarse particles be low. Coarse particles refer to particles whose diameter (particle size) is 0.03 μm or larger when the particle shape is considered to be spherical. The abrasive grains mentioned above may be included in the category of coarse particles. The content of coarse particles in the treatment solution is preferably 10,000 or less, and more preferably 5,000 or less, of particles with a particle size of 0.1 μm or larger per 1 mL of treatment solution. The lower limit is preferably 0 or more, and more preferably 0.01 or more, per 1 mL of treatment solution. Coarse particles contained in the processing solution include dust, dirt, organic solids, and inorganic solids that are present as impurities in the raw materials, as well as dust, dirt, organic solids, and inorganic solids that are introduced as contaminants during the preparation of the processing solution and that ultimately remain as particles in the processing solution without dissolving. The amount of coarse particles present in the processing solution can be measured in the liquid phase using a commercially available measuring device that employs a light scattering method for measuring particles in a liquid, with a laser as the light source. Methods for removing coarse particles include purification processes such as filtering, which will be described later.

[0100] <Method for producing the treatment solution> The treatment solution can be manufactured by known methods. The manufacturing method for the treatment solution is described in detail below.

[0101] [Liquid preparation process] For example, the processing solution can be prepared by mixing the above-mentioned components. The order and / or timing of mixing the above components is not particularly limited. For example, one method of preparation involves sequentially adding a cationic compound, anionic compound, and oxidizing agent to a container containing purified water, stirring to mix them, and then adding a pH adjuster to adjust the pH of the mixture. When adding water and each component to the container, they may be added all at once or in multiple separate additions.

[0102] For preparing the processing liquid, any known agitator or disperser may be used. Examples of agitators include industrial mixers, portable agitators, mechanical stirrers, and magnetic stirrers. Examples of dispersers include industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.

[0103] The mixing of each component in the preparation of the processing solution, the purification process described later, and the storage of the manufactured processing solution are preferably carried out at 40°C or below, and more preferably at 30°C or below. The lower limit is preferably 5°C or above, and more preferably 10°C or above. By preparing, processing, and / or storing the processing solution within the above temperature range, the performance can be maintained stably for a long period of time.

[0104] (Purification process) It is preferable to pre-purify one or more of the raw materials for preparing the processing solution. Examples of known purification methods include distillation, ion exchange, and filtration. The degree of purification should preferably be such that the purity of the raw material is 99% by mass or higher, and more preferably that the purity of the stock solution is 99.9% by mass or higher.

[0105] Purification methods include, for example, passing the raw material through an ion exchange resin or RO membrane (Reverse Osmosis Membrane), distillation of the raw material, and filtering as described later. As a purification process, multiple purification methods described above may be combined. For example, after primary purification by passing the raw material through an RO membrane, secondary purification may be performed by passing it through a purification apparatus consisting of a cation exchange resin, anion exchange resin, or mixed-bed ion exchange resin. Furthermore, the purification process may be carried out multiple times.

[0106] (filtering) The filters used for filtering are not particularly limited as long as they are conventionally used for filtration purposes. For example, filters made of fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, and polyolefin resins (including high-density or ultra-high molecular weight) such as polyethylene and polypropylene (PP) are examples. Among these materials, materials selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesins (including PTFE and PFA), and polyamide resins (including nylon) are preferred, and fluororesin filters are more preferred. By filtering raw materials using filters made of these materials, highly polar foreign substances that are likely to cause defects can be effectively removed.

[0107] The critical surface tension of the filter is preferably 70 to 95 mN / m, and more preferably 75 to 85 mN / m. Note that the critical surface tension value of the filter is the manufacturer's nominal value. By using a filter with a critical surface tension within the above range, highly polar foreign matter that is prone to causing defects can be effectively removed.

[0108] The pore size of the filter is preferably 2 to 20 nm, and more preferably 2 to 15 nm. This range allows for the reliable removal of fine foreign matter such as impurities and aggregates contained in the raw material while suppressing clogging. The pore size here can be referenced from the filter manufacturer's nominal value.

[0109] Filtering may be performed only once or more times. If filtering is performed more than once, the filters used may be the same or different.

[0110] Furthermore, filtering is preferably performed at room temperature (25°C) or below, more preferably at 23°C or below, and even more preferably at 20°C or below. Also, it is preferably at 0°C or above, more preferably at 5°C or above, and even more preferably at 10°C or above. By performing filtering within the above temperature range, the amount of particulate foreign matter and impurities dissolved in the raw material can be reduced, and foreign matter and impurities can be efficiently removed.

[0111] (container) The processing solution (including the form of the diluted processing solution described later) can be filled into any container and stored, transported, and used, as long as corrosiveness or other issues do not pose a problem.

[0112] As for the container, a container with a high degree of cleanliness inside and suppressed elution of impurities from the inner wall of the container's compartment into each liquid is preferred for semiconductor applications. Examples of such containers include, but are not limited to, various containers commercially available for semiconductor processing solutions, such as the "Clean Bottle" series from Aicello Chemical Co., Ltd. and the "Pure Bottle" from Kodama Resin Industry Co., Ltd. Furthermore, as a container for containing the processing liquid, it is preferable that the parts in contact with the liquid, such as the inner wall of the container, are made of fluororesin (perfluororesin) or metal that has been treated to prevent rust and metal leaching. The inner wall of the container is preferably formed from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or from a different resin or from a metal that has been treated to prevent rust and metal leaching, such as stainless steel, Hastelloy, Inconel, and Monel.

[0113] Among the different resins mentioned above, fluororesin (perfluororesin) is preferred. By using a container with an inner wall made of fluororesin in this way, the occurrence of problems such as the elution of ethylene or propylene oligomers can be suppressed compared to a container with an inner wall made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin. Examples of containers with fluororesin inner walls include the FluoroPurePFA composite drum manufactured by Entegris. Containers described on page 4 of Japanese Patent Publication No. 3-502677, page 3 of International Publication No. 2004 / 016526, and pages 9 and 16 of International Publication No. 99 / 46309 can also be used.

[0114] In addition to the fluororesin mentioned above, quartz and electropolished metal materials (i.e., electropolished metal materials) are also preferably used for the inner wall of the container. The metal material used in the manufacture of the electropolished metal material described above preferably contains at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is more than 25% by mass of the total mass of the metal material. Examples include stainless steel and nickel-chromium alloys. The combined content of chromium and nickel in the metallic material is more preferably 30% by mass or more relative to the total mass of the metallic material. In addition, the upper limit for the total chromium and nickel content in metallic materials is generally preferably 90% by mass or less.

[0115] Known methods can be used for electropolishing metal materials. For example, the methods described in paragraphs

[0011] to

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

[0036] to

[0042] of Japanese Patent Publication No. 2008-264929 can be used.

[0116] These containers are preferably cleaned inside before being filled with the processing liquid. The liquid used for cleaning is preferably one in which the amount of metal impurities is reduced. The processing liquid may be bottled in containers such as gallon bottles or coated bottles after production for transport and storage.

[0117] To prevent changes in the components of the processing solution during storage, the container may be purged with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. Gases with a particularly low water content are preferred. During transportation and storage, the temperature may be room temperature, or it may be controlled to a range of -20°C to 20°C to prevent deterioration.

[0118] (Cleanroom) It is preferable that all handling, including the manufacture of the processing solution, opening and cleaning of containers, filling of the processing solution, processing analysis, and measurement, be carried out in a cleanroom. The cleanroom should preferably meet the 14644-1 cleanroom standard. It is preferable that it meets one of the ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, and ISO Class 4 standards, more preferably ISO Class 1 or ISO Class 2, and even more preferably ISO Class 1.

[0119] [Dilution process] The above-mentioned treatment solution may be used as a diluted treatment solution (diluted treatment solution) after undergoing a dilution step in which it is diluted with a diluent. Furthermore, a diluted treatment solution is also a form of the treatment solution of the present invention, as long as it satisfies the requirements of the present invention.

[0120] Examples of diluents include water and aqueous solutions containing isopropanolamine (1-amino-2-propanol) or ammonia. It is preferable to perform a purification treatment on the diluent used in the dilution step beforehand. Furthermore, it is even more preferable to perform a purification treatment on the diluted solution obtained in the dilution step. As for the purification process, examples of purification processes for the above-mentioned treatment solution include ion component reduction using ion exchange resin or RO membrane, and removal of foreign matter using filtering, and it is preferable to perform one of these processes.

[0121] The dilution ratio of the treatment solution in the dilution step should be adjusted as appropriate depending on the type and content of each component, as well as the target and purpose of use of the treatment solution. The ratio of the diluted treatment solution to the treatment solution before dilution (dilution ratio) is preferably 1.5 to 10,000 times by mass ratio or volume ratio (volume ratio at 23°C), more preferably 2 to 2,000 times, and even more preferably 50 to 1,000 times.

[0122] Furthermore, a treatment solution (diluted treatment solution) containing each component (excluding water) in an amount obtained by dividing the preferred content of each component that can be contained in the above treatment solution by a dilution ratio within the above range (for example, 100) can also be suitably put into practical use. In other words, the preferred content of each component (excluding water) relative to the total mass of the diluted treatment solution is, for example, the amount described as the preferred content of each component relative to the total mass of the treatment solution (treatment solution before dilution) divided by the dilution ratio within the above range (e.g., 100).

[0123] The change in pH before and after dilution (the difference between the pH of the treatment solution before dilution and the pH of the diluted treatment solution) is preferably 2.0 or less, more preferably 1.8 or less, and even more preferably 1.5 or less. The pH of the treatment solution before dilution and the pH of the diluted treatment solution are preferably as described above.

[0124] The specific method for the dilution step in which the processing solution is diluted may be carried out in accordance with the processing solution preparation step described above. The stirring device and stirring method used in the dilution step may also be carried out using the known stirring device mentioned in the processing solution preparation step described above.

[0125] <Applications of the processing solution> The applications of the processing solution of the present invention are not particularly limited, but it can be suitably used in processes for removing specific components from semiconductor substrates. In particular, the processing solution of the present invention is preferably used as a post-etching residue removal solution, a resist stripping agent, a post-chemical mechanical polishing (CMP) cleaning solution, or an etching solution. As mentioned above, when using the treatment solution, a diluted treatment solution obtained by diluting the treatment solution may be used.

[0126] [Object to be processed] Examples of objects to be treated in which the processing solution of the present invention can be suitably used include semiconductor substrates having metal-containing materials on the semiconductor substrate. Furthermore, "on the semiconductor substrate" includes, for example, the front and back surfaces, sides, and inside grooves of the semiconductor substrate. In addition, "metal-containing material on the semiconductor substrate" includes not only cases where the metal-containing material is directly on the surface of the semiconductor substrate, but also cases where the metal-containing material is present on the semiconductor substrate via other layers. Furthermore, the semiconductor substrate may simultaneously contain multiple types of metal-containing materials as described above. In other words, the semiconductor substrate may contain multiple types of metal-containing materials.

[0127] Examples of metals included in the metal-containing material include at least one metal M selected from the group consisting of Al (aluminum), Ti (titanium), Cr (chromium), Mn (manganese), Co (cobalt), Ni (nickel), Cu (copper), Zr (zirconium), Mo (molybdenum), Ru (ruthenium), La (lanthanum), Hf (hafnium), Ta (tantalum), W (tungsten), Os (osmium), Pt (platinum), and Ir (iridium). A metal-containing substance can be any substance that contains a metal (metal atom), for example, elemental metal M, alloys containing metal M, oxides of metal M, nitrides of metal M, and oxynitrides of metal M. Furthermore, the metal-containing material may be a mixture containing two or more of these elements or compounds. The above oxides, nitrides, and oxynitrides may also be composite oxides, composite nitrides, and composite oxynitrides that contain metals. The content of metal atoms in the metal-containing material is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, based on the total mass of the metal-containing material. The upper limit is 100% by mass, since the metal-containing material may be the metal itself.

[0128] The semiconductor substrate preferably has a metal content containing at least one metal selected from the group consisting of Al, Ti, Co, Cu, Mo, Ta, and W, more preferably has a metal content containing at least one metal selected from the group consisting of Ti, Co, Ta, and W, and even more preferably has a metal content containing at least one metal selected from the group consisting of Ti, Co, and W.

[0129] The semiconductor substrate to be processed is not particularly limited, and examples include a substrate having a metal wiring film, a barrier film, and an insulating film on the surface of a wafer constituting the semiconductor substrate.

[0130] Examples of wafers that make up a semiconductor substrate include silicon (Si) wafers, silicon carbide (SiC) wafers, silicon-based wafers such as resin-based wafers containing silicon (glass epoxy wafers), gallium phosphide (GaP) wafers, gallium arsenide (GaAs) wafers, and indium phosphide (InP) wafers. Examples of silicon wafers include n-type silicon wafers doped with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb)), and p-type silicon wafers doped with trivalent atoms (e.g., boron (B) and gallium (Ga)). Examples of silicon used in silicon wafers include amorphous silicon, single-crystal silicon, polycrystalline silicon, and polysilicon. Among these, wafers made of silicon-based materials such as silicon wafers, silicon carbide wafers, and silicon-containing resin wafers (glass epoxy wafers) are preferred.

[0131] The semiconductor substrate may have an insulating film on the wafer. Examples of insulating films include silicon oxide films (e.g., silicon dioxide (SiO2) films and tetraethyl orthosilicate (Si(OC2H5)4) films (TEOS films), etc.), silicon nitride films (e.g., silicon nitride (Si3N4) and silicon carbide nitride (SiNC), etc.), and low-dielectric constant (Low-k) films (e.g., carbon-doped silicon oxide (SiOC) films and silicon carbide (SiC) films, etc.), with low-dielectric constant (Low-k) films being preferred.

[0132] The metal-containing material may also preferably be a metal film containing metal. The metal film on the semiconductor substrate is preferably a metal film containing metal M, more preferably a metal film containing at least one metal selected from the group consisting of Al, Ti, Co, Cu, Mo, Ru, Ta, and W, even more preferably a metal film containing at least one metal selected from the group consisting of Al, Ti, Co, Cu, Ru, Ta, and W, particularly preferably a metal film containing at least one metal selected from the group consisting of Ti, Co, Cu, Ru, and W, and most preferably a metal film containing Ti or a metal film containing W. Examples of metal films containing at least one metal selected from the group consisting of Ti, Co, Cu, Ru, and W include films mainly composed of titanium (Ti-containing films), films mainly composed of cobalt (Co-containing films), films mainly composed of copper (Cu-containing films), films mainly composed of ruthenium (Ru-containing films), and films mainly composed of tungsten (W-containing films).

[0133] Examples of titanium-containing films (metal films with titanium as the main component) include metal films made solely of metal Ti (titanium metal films) and metal films made of alloys of metallic titanium and other metals (titanium alloy metal films). Examples of titanium alloy metal films include metal films made of titanium and one or more metals selected from Al (aluminum), Si (silicon), Cr (chromium), Cu (copper), Mo (molybdenum), and tungsten (W). More specifically, examples include titanium-aluminum alloy metal films (TiAl alloy metal films), titanium-silicon alloy metal films (TiSi alloy metal films), titanium-chromium alloy metal films (TiCr alloy metal films), titanium-copper alloy metal films (TiCu alloy metal films), titanium-molybdenum alloy metal films (TiMo alloy metal films), and titanium-tungsten alloy metal films (TiW alloy metal films).

[0134] Examples of cobalt-containing films (metal films with cobalt as the main component) include metal films made solely of metallic cobalt (cobalt metal films) and metal films made of alloys consisting of metallic cobalt and other metals (cobalt alloy metal films). Examples of cobalt alloy metal films include metal films made of alloys consisting of cobalt and one or more metals selected from titanium (Ti), chromium (Cr), iron (Fe), nickel (Ni), molybdenum (Mo), palladium (Pd), tantalum (Ta), and tungsten (W). More specifically, examples include cobalt-titanium alloy metal films (CoTi alloy metal films), cobalt-chromium alloy metal films (CoCr alloy metal films), cobalt-iron alloy metal films (CoFe alloy metal films), cobalt-nickel alloy metal films (CoNi alloy metal films), cobalt-molybdenum alloy metal films (CoMo alloy metal films), cobalt-palladium alloy metal films (CoPd alloy metal films), cobalt-tantalum alloy metal films (CoTa alloy metal films), and cobalt-tungsten alloy metal films (CoW alloy metal films).

[0135] It is also preferable that the semiconductor substrate has a copper-containing film (a metal film mainly composed of copper). Examples of copper-containing films include wiring films made solely of metallic copper (copper wiring films) and wiring films made of alloys of metallic copper and other metals (copper alloy wiring films). Examples of the copper alloy wiring film include a wiring film made of an alloy of copper and one or more metals selected from aluminum (Al), titanium (Ti), chromium (Cr), manganese (Mn), tantalum (Ta), and tungsten (W). More specifically, examples include a copper-aluminum alloy wiring film (CuAl alloy wiring film), a copper-titanium alloy wiring film (CuTi alloy wiring film), a copper-chromium alloy wiring film (CuCr alloy wiring film), a copper-manganese alloy wiring film (CuMn alloy wiring film), a copper-tantalum alloy wiring film (CuTa alloy wiring film), and a copper-tungsten alloy wiring film (CuW alloy wiring film).

[0136] Examples of the ruthenium-containing film include a metal film composed only of metallic ruthenium (ruthenium metal film) and a metal film made of an alloy of metallic ruthenium and another metal (ruthenium alloy metal film). The ruthenium-containing film is often used as a barrier metal.

[0137] Examples of the tungsten-containing film (a metal film having tungsten as a main component) include a metal film composed only of tungsten (tungsten metal film) and a metal film made of an alloy of tungsten and another metal (tungsten alloy metal film). Examples of the tungsten alloy metal film include a tungsten-titanium alloy metal film (WTi alloy metal film) and a tungsten-cobalt alloy metal film (WCo alloy metal film). The tungsten-containing film is used, for example, as a barrier metal or at the connection part between the via and the wiring.

[0138] The metal inclusion is preferably a metal compound film containing a compound containing a metal. Examples of the metal compound film include a titanium nitride film (TiN film) and a tantalum nitride film (TaN). The metal compound film is used, for example, as a barrier film.

[0139] Among the above objects to be processed, an object to be processed containing a titanium nitride film and a tungsten metal film or a tungsten alloy metal film is preferable.

[0140] (Method of manufacturing the object to be processed) There are no particular restrictions on the method for forming the above-mentioned insulating film, titanium-containing film, cobalt-containing film, copper-containing film, ruthenium-containing film, tungsten-containing film, and metal compound film on a wafer constituting a semiconductor substrate, as long as it is a method commonly used in this field. One method for forming an insulating film is to form a silicon oxide film on a wafer constituting a semiconductor substrate by heat treatment in the presence of oxygen gas, and then to form a silicon nitride film by introducing silane and ammonia gases using the chemical vapor deposition (CVD) method. Methods for forming titanium-containing films, cobalt-containing films, copper-containing films, ruthenium-containing films, tungsten-containing films, and metal compound films include, for example, forming circuits on a wafer having the above-mentioned insulating film using known methods such as resist, and then forming titanium-containing films, cobalt-containing films, copper-containing films, ruthenium-containing films, tungsten-containing films, and metal compound films by methods such as plating, sputtering, CVD, molecular beam epitaxy (MBE), and atomic layer deposition (ALD).

[0141] Furthermore, the workpiece may be a substrate manufactured by the above method that has undergone a predetermined treatment. Examples of predetermined treatments include etching, CMP treatment, and resist pattern formation treatment.

[0142] <How to use the processing solution> One method of using the processing liquid is to bring the object to be processed into contact with the processing liquid. Hereafter, a process that includes bringing the object to be processed into contact with the processing liquid will also be referred to as the "contact process." When the contact process is performed, if the workpiece contains a W metal film, the W metal film will not dissolve, and the desired treatment (such as residue removal and washing) can be carried out. Furthermore, metals having chemical properties similar to W will not dissolve in the treatment solution of the present invention, just like W. In other words, the treatment solution of the present invention has corrosion-preventive properties against these metals. Examples of metals for which the treatment solution of the present invention can exhibit corrosion-preventive properties include V, Cr, Nb, Mo, and Ta. When the contact process is performed, if the material being treated contains TiN, the TiN will be dissolved. Furthermore, materials having chemical properties similar to TiN will be dissolved by the treatment solution of the present invention, similar to TiN. In other words, the treatment solution of the present invention has the ability to dissolve these materials. Materials that can be dissolved by the treatment solution of the present invention include Al, Ti, Zr, Hf, and Ru, as well as their oxides or nitrides. When a contact process is performed, if the workpiece contains W and TiN, TiN is selectively dissolved relative to W. Furthermore, materials capable of exhibiting the above-mentioned dissolving ability can be selectively dissolved relative to metals in which the treatment solution of the present invention can exhibit corrosion-preventive properties. Therefore, the treatment solution of the present invention can be suitably used as an etching solution that selectively dissolves TiN and the like relative to W and the like. The materials to be processed are as described above.

[0143] There are no particular limitations on the method of bringing the object to be treated into contact with the treatment liquid. Examples include immersing the object to be treated in the treatment liquid in a tank, spraying the treatment liquid onto the object to be treated, flowing the treatment liquid over the object to be treated, and combinations thereof. The above methods may be selected as appropriate depending on the purpose. Furthermore, the above method may appropriately adopt any format commonly used in this field. For example, it may be a scrubbing method in which a cleaning member such as a brush is physically brought into contact with the surface of the object to be treated while supplying the treatment liquid to remove residues, or a spin (dropping) method in which the treatment liquid is dripped onto the object to be treated while it is rotated. In the immersion method, it is preferable to apply ultrasonic treatment to the object to be treated while it is immersed in the treatment liquid, as this can further reduce impurities remaining on the surface of the object to be treated. In the contact process, contact between the workpiece and the treatment liquid may be performed only once or two or more times. If contact is performed two or more times, the same method may be repeated, or different methods may be combined.

[0144] The contact process may be carried out using either a single-wafer or batch method. A single-wafer system generally processes one sheet of material at a time, while a batch system generally processes multiple sheets of material simultaneously.

[0145] The temperature of the processing solution is not particularly limited, as long as it is within the range of temperatures typically used in this field. Generally, cleaning is performed at room temperature (approximately 25°C), but the temperature can be arbitrarily selected to improve cleaning performance and minimize damage to the components. For example, the temperature of the processing solution is preferably 10 to 60°C, and more preferably 15 to 50°C.

[0146] The pH of the treatment solution is preferably 7.0 or lower, and is in the preferred state of pH of the treatment solution as described above. The pH of the diluted treatment solution is also preferably in the preferred state of pH of the treatment solution as described above.

[0147] The contact time between the object to be treated and the treatment solution can be appropriately changed depending on the type and content of each component contained in the treatment solution, as well as the target and purpose of use of the treatment solution. In practice, 10 to 120 seconds is preferred, 20 to 90 seconds is more preferred, and 30 to 60 seconds is even more preferred.

[0148] The supply rate (feed rate) of the processing solution is preferably 50 to 5000 mL / min, and more preferably 500 to 2000 mL / min.

[0149] In the contact process, a mechanical stirring method may be used to further enhance the cleaning ability of the processing liquid. Examples of mechanical stirring methods include circulating the treatment liquid over the workpiece, flowing or spraying the treatment liquid over the workpiece, and stirring the treatment liquid using ultrasound or megasonic waves.

[0150] Also, after the contacting step, a step of rinsing the object to be treated with a solvent for cleaning (hereinafter also referred to as the "rinsing step") may be performed. The rinsing step is preferably performed continuously after the contacting step and is a step of rinsing for 5 to 300 seconds using a rinsing solvent (rinsing liquid). The rinsing step may be performed using the above-described mechanical stirring method.

[0151] Examples of the rinsing solvent include water (preferably deionized (DI) water), methanol, ethanol, isopropyl alcohol, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Further, an aqueous rinsing liquid (diluted aqueous ammonium hydroxide or the like) having a pH exceeding 8.0 may be used. As a method of bringing the rinsing solvent into contact with the object to be treated, the method of bringing the above-described treatment liquid into contact with the object to be treated can be similarly applied.

[0152] Also, after the above-described rinsing step, a drying step of drying the object to be treated may be performed. Examples of the drying method include a spin drying method, a method of flowing a dry gas over the object to be treated, a method of heating the substrate by heating means such as a hot plate and an infrared lamp, a Marangoni drying method, a Rotagoni drying method, an IPA (isopropyl alcohol) drying method, and any combination of these methods.

Example

[0153] The present invention will be described in more detail based on the following examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0154] In the following examples, the pH of the treatment solution was measured at 25°C in accordance with JIS Z8802-1984 using a pH meter (Horiba, Ltd., model "F-74"). Furthermore, in the preparation of the treatment solutions for the examples and comparative examples, the handling of containers, preparation of the treatment solutions, filling, storage, and analytical measurements were all carried out in a cleanroom meeting ISO Class 2 or lower standards.

[0155] <Preparation of the treatment solution> The treatment solutions used in each example and comparative example were prepared by mixing the components listed below. The content of each component in the treatment solution is as shown in Tables 1-1 to 1-5 below. In the case of a mixture of the component and the solvent listed below, the content of the component excluding the solvent is shown. Furthermore, all of the components used in the examples were classified as semiconductor grade or equivalent high-purity grade.

[0156] [water] ·Ultra pure water

[0157] [Cationic compounds] The cationic compounds used were those with C1 to C13 as shown below. Compounds with repeating units indicated represent compounds composed of those repeating units.

[0158] [ka] JPEG0007871031000011.jpg9189 JPEG0007871031000012.jpg10480

[0159] [Anionic compounds] A1: Compound consisting of the following repeating units

[0160] [ka]

[0161] A5: Poly(vinyl phosphate) (weight-average molecular weight: 10,000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) A6: Polymaleic acid (weight-average molecular weight: 2000, manufactured by NOF Corporation, product name "Nonpol PWA-50W") A7: Polyacrylic acid (weight-average molecular weight: 2000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • A8: Polyacrylic acid (weight-average molecular weight: 8000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) A9: Acrylic acid-maleic acid copolymer (weight-average molecular weight: 10,000, manufactured by Nippon Shokubai, product name "Aquaric TL37") A10: Polyacrylic acid (weight-average molecular weight: 50,000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) A11: Poly(styrene sulfonic acid) (weight-average molecular weight: 75,000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) A12: Polyacrylic acid (weight-average molecular weight: 100,000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) A13: Polyacrylic acid (weight-average molecular weight: 125,000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0162] [Low molecular weight anionic compounds] In Comparative Examples 5 to 7, the following compounds (low molecular weight anionic compounds) were used instead of the above-mentioned anionic compounds.

[0163] A2: The following compounds

[0164] [ka]

[0165] • A3: The following compounds

[0166] [ka]

[0167] A4: The following compounds

[0168] [ka]

[0169] [Fluoride source] • E1: Hydrofluoric acid (hydrogen fluoride (HF) aqueous solution) • E2: Hexafluorozirconium acid (H2ZrF6) aqueous solution • E3: Hexafluorotitanium acid (H2TiF6) aqueous solution • E4: Hexafluorophosphate (HPF6) aqueous solution • E5: Tetrafluoroboric acid (HBF4) aqueous solution • E6: Hexafluorosilicic acid (H2SiF6) aqueous solution

[0170] [Oxidizing agent] • O1: Periodic acid (H5IO6 aqueous solution) O2: Hydrogen peroxide O3: Nitric acid • O4: Peracetic acid ·O5: Perchloric acid • O6: Ammonium peroxodisulfate • O7: Trichloroisocyanuric acid

[0171] [Corrosion inhibitor] I1: Tetramethylammonium silicate • I2: Tetraethylammonium silicate • I3: Sodium silicate (Na2SiO3) ·I4: Boric acid (H3BO3)

[0172] [Organic solvents] • S1: Ethylene glycol ·S2: Dimethyl sulfoxide S3: N,N-dimethylformamide S4: Glycerol S5: Sulfolane

[0173] [pH adjuster] R1: Methanesulfonic acid R2: Sodium hydroxide

[0174] <Rating> [TiN dissolution rate] A TiN-layered substrate was prepared by forming a 30 nm titanium nitride (TiN) layer on one surface of a commercially available silicon wafer (diameter: 12 inches) using the CVD method. The obtained TiN-layered substrates were placed in containers filled with the processing solution for each example or comparative example, and the processing solution was stirred to remove the TiN layer for 3 minutes. The temperature of the composition was 40°C. The dissolution rate of TiN was calculated by comparing the thickness of the TiN layer before and after the above treatment, using a spectroscopic ellipsometer (Vace, manufactured by J.A. Woolam Japan). The dissolution rates of TiN in each example and comparative example are shown in Tables 1-1 to 1-5. Furthermore, the dissolution rate of TiN was evaluated according to the evaluation criteria below. The evaluation results are shown in Tables 1-1 to 1-5. In practical terms, an evaluation of D or higher is preferable.

[0175] (Evaluation criteria for TiN dissolution rate) A: Dissolution rate of TiN is 80 Å / min or higher B: Dissolution rate of TiN is between 50 Å / min and less than 80 Å / min The dissolution rate of C:TiN is between 30 Å / min and less than 50 Å / min. D:Dissolution rate of TiN is between 10 Å / min and less than 30 Å / min E:TiN dissolution rate is less than 1 Å / min

[0176] [W dissolution rate] A substrate with a 30 nm tungsten (W) layer was prepared by forming a tungsten (W) layer on one surface of a commercially available silicon wafer (diameter: 12 inches) using the CVD method. The obtained substrates with the W layer were placed in a container filled with the processing solution for each example or comparative example, and the processing solution was stirred to remove the W layer for 3 minutes. The temperature of the composition was 40°C. The dissolution rate of W was calculated in the same manner as the dissolution rate of TiN. The dissolution rates of W in each example and comparative example are shown in Tables 1-1 to 1-5.

[0177] [Dissolution rate ratio] Using the dissolution rates of W and TiN obtained by the above method, the ratio of the dissolution rate of TiN to the dissolution rate of W (dissolution rate ratio) was calculated. The dissolution rate ratios for each example and each comparative example are shown in Tables 1-1 to 1-5. Furthermore, the dissolution rate ratio was evaluated according to the evaluation criteria below. The evaluation results are shown in Tables 1-1 to 1-5. In practical terms, an evaluation of D or higher is preferable.

[0178] (Evaluation criteria for dissolution rate ratio) The ratio of the dissolution rate of TiN to the dissolution rate of AA:W is 100 or more. The ratio of the dissolution rate of TiN to the dissolution rate of A:W is between 60 and 100. The ratio of the dissolution rate of TiN to the dissolution rate of B:W is between 30 and 60. The ratio of the dissolution rate of TiN to the dissolution rate of C:W is between 10 and 30. The ratio of the dissolution rate of TiN to the dissolution rate of D:W is between 1 and 10. The ratio of the dissolution rate of TiN to the dissolution rate of E:W is less than 1.

[0179] <Result> Tables 1-1 to 1-5 show the components of the treatment solutions used in each example and comparative example, as well as the evaluation results for each example and comparative example. In each table, the notation "Remainder" in the "Water" column indicates that the component in the treatment solution other than the specified component is water. Note that if the above component is an aqueous solution, the water contained within that component is considered the remainder. In each table, the "C / A" column represents the ratio of the content of cationic compounds to the content of anionic compounds. In each table, the notation "2~3" in the "pH" column indicates that the pH of the treatment solution was between 2.0 and 3.0.

[0180] [Table 1]

[0181] [Table 2]

[0182] [Table 3]

[0183] [Table 4]

[0184] [Table 5]

[0185] The results in each table confirm that the treatment solution of the present invention produces the desired effect. From a comparison of Example 13 with other examples, it was confirmed that when the cationic compound contains a compound with a nitrogen atom, the ratio of the dissolution rate of TiN to the dissolution rate of W increases. From a comparison of Examples 11 and 12 with other examples, it was confirmed that when the cationic compound contains a compound having the structure represented by the above formula (3-4), the ratio of the dissolution rate of TiN to the dissolution rate of W is large, and the dissolution rate of TiN is excellent. From a comparison between Example 10 and other examples, it was confirmed that when the cationic compound is a resin having repeating units represented by the above formula (L), the ratio of the dissolution rate of TiN to the dissolution rate of W is large, and the dissolution rate of TiN is excellent. From a comparison of Examples 23 and 29 with Examples 24-28, it was confirmed that when the mass ratio of the cationic compound content to the anionic compound content is between 1 and 100, the ratio of the dissolution rate of TiN to the dissolution rate of W is large, indicating superior dissolution rate of TiN. From a comparison of Example 34 with other examples, it was confirmed that when the treatment solution further contains a fluoride source, the ratio of the dissolution rate of TiN to the dissolution rate of W is large, and the dissolution rate of TiN is superior. From a comparison of Example 46 with other examples, it was confirmed that when the treatment solution further contains a corrosion inhibitor, the ratio of the dissolution rate of TiN to the dissolution rate of W is large. From a comparison of Example 50 with other examples, it was confirmed that when the treatment solution further contains an organic solvent, the ratio of the dissolution rate of TiN to the dissolution rate of W is large.

[0186] <Dry etching residue removal> A laminate is prepared in which a 100 nm thick SiO2 film is layered on a substrate (Si). Using a TiN metal hard mask as a mask, plasma etching is performed on this laminate with a fluorine-containing gas to etch the SiO2 film to a thickness of approximately 50 nm, thereby creating a test specimen for evaluation testing in which a 2 cm square grid pattern is formed. After etching, a fluorine-containing dry etching residue adheres to the test specimen. This fluorine-containing dry etching residue can be analyzed by detecting fluorine using X-ray photoelectron spectroscopy (XPS). The fluorine content on the surface of the etched test specimen is approximately 4-5 atomic percent.

[0187] Next, the dry etching residue removal performance of each of the above embodiments' processing solutions is evaluated according to the following procedure. While stirring the treatment solution, the test specimen is immersed in the treatment solution at a liquid temperature of 65°C for a predetermined washing time to wash the test specimen. After 90 seconds, the test specimen is immediately removed from the treatment solution, rinsed with deionized water, and the surface of the test specimen is dried with a nitrogen gas stream.

[0188] The surface composition of the obtained test specimens is analyzed using an XPS instrument (Ulvac-PHI, product name QuanteraSXM) to measure the content (atomic %) of fluorine atoms derived from dry etching residues on the surface of the test specimens. After 90 seconds of washing, the fluorine atom content is reduced to 1 atomic percent or less, and the processing solution in each of the above examples can sufficiently remove dry etching residue.

[0189] <Chemical mechanical polishing residue removal> A pattern with grooves 0.18 μm wide and 0.5 μm deep is fabricated on the surface of a Si wafer (8 inches in diameter), and a metal film made of W is formed on the surface by vapor deposition. The surface of the wafer with the metal film is polished using a FREX300S-II (polishing machine, manufactured by Ebara Corporation). Polishing (CMP treatment) is performed using CSL9044C and BSL8176C (product names, both manufactured by Fujifilm Planar Solutions Co., Ltd.) as polishing solutions. In the CMP treatment of the wafer with the metal film on its surface, the polishing pressure is 2.0 psi, and the supply rate of the polishing solution is 0.28 mL / (min·cm). 2 The grinding time will be 60 seconds. Note that "psi" means "pound-force per square inch," and 1 psi = 6894.76 Pa. Subsequently, the CMP-treated wafers are scrubbed for 30 seconds using the treatment solution of each example, which has been adjusted to room temperature (23°C), and then dried. After drying, a defect detection device (AMAT, ComPlus-II) is used to measure the number of detected signal strengths corresponding to defects with a length of 0.1 μm or more on the polished surface of the wafer. When wafers are scrubbed after CMP treatment using the treatment solutions of each embodiment, the number of defects per wafer on the polished surface of the wafer is less than 300. Furthermore, W remaining in the grooves after CMP treatment is not corroded.

Claims

1. Water and, A cationic compound which is a resin, An anionic compound selected from the group consisting of resins having a carboxyl group or a salt thereof, resins having a sulfo group or a salt thereof, resins having a phosphite group or a salt thereof, and resins having a phosphate group or a salt thereof, Contains an oxidizing agent, The oxidizing agent is one or more oxidizing agents selected from the group consisting of cerium nitrate, iron nitrate, peracetic acid, periodic acid, periodate, perchloric acid, perchlorate, chloric acid, hypochlorous acid, hypochlorite, persulfate, persulfate, peroxodisulfate, peroxodisulfate, isocyanuric acid, isocyanurate, trichloroisocyanuric acid, and trichloroisocyanurate. The pH is 7.0 or lower. A processing solution that contains virtually no abrasive particles.

2. The treatment solution according to claim 1, wherein the cationic compound includes a compound having a nitrogen atom.

3. The treatment solution according to claim 1 or 2, wherein the cationic compound comprises a compound having a structure selected from the group consisting of structures represented by the following formulas (1) to (4). 【Chemistry 1】 In equations (1) to (4), * indicates the bonding position. In formulas (1), (2), and (4), R independently represents a hydrogen atom or a monovalent substituent.

4. The treatment solution according to any one of claims 1 to 3, wherein the cationic compound comprises a resin having repeating units selected from the group consisting of repeating units represented by the following formulas (I) to (L). 【Chemistry 2】 In formula (I), L Ｉ１ represents a single bond or a divalent linking group. In formula (I), Y represents a group having the structure shown in formula (1-1), formula (2-1), formula (3-1), or formula (4-2) below. In formula (J), L Ｊ１ ~L Ｊ４ Each of these independently represents a single bond or a divalent linking group. In formula (J), R Ｊ１ represents a hydrogen atom or a monovalent substituent. In formula (K), L Ｋ１ to L Ｋ４ each independently represents a single bond or a divalent linking group. In formula (K), R Ｋ１ and R Ｋ２ each independently represents a hydrogen atom or a monovalent substituent. In formula (K), A － represents a monovalent anion. In formula (L), L Ｌ１ represents a single bond or a divalent linking group. In formula (L), k represents an integer from 0 to 3. 【Transformation 3】 In equations (1-1), (2-1), (3-1), and (4-2), * indicates a bonding position. In formulas (1-1) and (2-1), R independently represents a hydrogen atom or a monovalent substituent. In equations (3-1) and (4-2), R Ｓ This represents a divalent substituent.

5. The treatment solution according to claim 4, wherein the cationic compound comprises a resin having repeating units represented by formula (L).

6. The treatment solution according to any one of claims 1 to 5, wherein the mass ratio of the content of the cationic compound to the content of the anionic compound is 1 to 100.

7. The treatment solution according to any one of claims 1 to 6, further comprising a fluoride source.

8. The fluoride source is HF, H ２ SiF ６ H ２ TiF ６ H ２ ZrF ６ HPF ６ , and HBF ４ The treatment solution according to claim 7, comprising a compound selected from the group consisting of the following.

9. The treatment solution according to any one of claims 1 to 8, further comprising a corrosion inhibitor.

10. The treatment solution according to any one of claims 1 to 9, further comprising an organic solvent.

11. A processing solution according to any one of claims 1 to 10, used as a post-etching residue removal solution, a resist stripping agent, a post-chemical mechanical polishing cleaning solution, and an etching solution.

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