Processing liquid, method for processing object to be processed, method for processing pad, and method for manufacturing electronic device

Abstract

The problem addressed by this invention is to provide a processing liquid capable of suppressing corrosion of tungsten or molybdenum, excellent in organic matter residue removability, and also excellent in iron oxide residue removability. This processing liquid contains a specific compound represented by formula (1) and at least one phosphonic acid compound selected from the group consisting of phosphonic acid and organic phosphonic acid. The mass ratio of the content of the specific compound to the content of the phosphonic acid compound is 0.001-20.0.

Description

Treatment liquid, treatment method for object to be treated, treatment method for pad, and manufacturing method of electronic device

[0001] The present invention relates to a processing liquid, a processing method for an object to be processed, a processing method for a pad, and a manufacturing method for an electronic device.

[0002] In the semiconductor field, with the remarkable progress in integration and performance, even trace amounts of impurities (contamination) and / or deposits (particles) have come to have a significant impact on device performance and ultimately product yield. Various types of contamination and particles (hereinafter also referred to as residues) can be generated during each manufacturing process of semiconductor devices. During semiconductor manufacturing, substrate processing processes are appropriately performed to remove such residues.

[0003] For example, in the manufacture of semiconductor devices, a chemical mechanical polishing (CMP) process may be performed to planarize a semiconductor substrate surface having a metal wiring film, a barrier metal, an insulating film, etc., using a polishing slurry containing abrasive particles (e.g., silica, alumina, etc.). In the CMP process, metal components derived from the abrasive particles used in the CMP process, the polished wiring metal film and / or the barrier metal, etc., tend to remain on the polished semiconductor substrate surface and on the members used for polishing (e.g., a polishing pad). For this reason, a process of removing these residues using a treatment liquid is generally performed after the CMP process.

[0004] As described above, in the semiconductor manufacturing process, the processing liquid is used for processing such as removing unnecessary metal-containing substances, resist, and residues from various members used in the manufacturing of semiconductors.

[0005] As an example of such a treatment liquid, Patent Document 1 discloses an aqueous cleaning composition for cleaning post-plasma etching residues, which contains an etchant, water, a low-dielectric-constant passivator, a surfactant, and a silica source, and also contains a predetermined component (I), (II), or (III).

[0006] Special Publication No. 2010-515246

[0007] The present inventors have studied the composition specifically disclosed in Patent Document 1 and have found that it is not possible to achieve desired levels of corrosion inhibition for tungsten or molybdenum, organic residue removal, and iron oxide residue removal, and that there is room for improvement.

[0008] Therefore, an object of the present invention is to provide a treatment liquid that can suppress corrosion of tungsten or molybdenum, has excellent organic residue removal properties, and is also excellent in iron oxide residue removal properties. Another object of the present invention is to provide a method for treating an object to be treated, a method for treating a pad, and a method for manufacturing an electronic device using the treatment liquid.

[0009] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0010] [1] A treatment liquid comprising a specific compound represented by the formula (1) described below and at least one phosphonic acid compound selected from the group consisting of phosphonic acid and organic phosphonic acid, wherein the mass ratio of the content of the specific compound to the content of the phosphonic acid compound is 0.001 to 20.0. [2] The treatment liquid according to [1], wherein the log D value of the specific compound at pH 7.4 is -7.2 to -1.0. [3] The treatment liquid according to [1] or [2], wherein the pH is 3.0 to 9.0. [4] The treatment liquid according to any one of [1] to [3], further comprising at least one basic amino acid selected from the group consisting of arginine, histidine, and lysine. [5] The treatment liquid according to any one of [1] to [4], further comprising cyclodextrin or a derivative thereof. [6] The treatment solution according to [4], wherein the mass ratio of the content of the specific compound to the content of the basic amino acid is 0.2 to 10.0. [7] The treatment solution according to any one of [1] to [6], wherein the specific compound contains 2 or 3 nitrogen atoms. [8] The treatment solution according to any one of [1] to [7], wherein the specific compound contains 3 to 11 carbon atoms. [9] The treatment solution according to any one of [1] to [8], further comprising an antibacterial agent.

[10] The treatment solution according to any one of [1] to [9], further comprising an anionic polymer.

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

[10] , further comprising a low-molecular-weight organic acid different from the phosphonic acid compound.

[12] A method for treating a workpiece, comprising a step of contacting a workpiece containing at least one of tungsten and molybdenum that has been subjected to chemical mechanical polishing with the treatment solution according to any one of [1] to

[11] .

[13] A method for treating a pad, comprising a step of contacting a pad used for chemical mechanical polishing with the treatment liquid according to any one of [1] to

[11] .

[14] A method for manufacturing an electronic device, comprising the method for treating an object according to

[12] .

[0011] The present invention provides a treatment solution that can inhibit corrosion of tungsten or molybdenum, has excellent organic residue removal properties, and is also excellent in iron oxide residue removal properties. The present invention also provides a method for treating an object to be treated, a method for treating a pad, and a method for manufacturing an electronic device using the treatment solution.

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

[0013] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0014] In this specification, the "total mass of components in the treatment liquid excluding the solvent" means the total mass of all components contained in the treatment liquid other than the solvent, such as water and an organic solvent. Unless otherwise specified, the compounds described in this specification may contain structural isomers, optical isomers, and isotopes. Furthermore, the structural isomers, optical isomers, and isotopes may be contained singly or in combination of two or more types.

[0015] In this specification, when there are multiple substituents and linking groups, etc. (hereinafter referred to as substituents, etc.) represented by a specific symbol, or when multiple substituents, etc. are specified simultaneously, this means that the respective substituents, etc. may be the same or different from each other. The same applies to the specification of the number of substituents, etc. The bonding direction of a divalent group represented in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. Furthermore, the above compound may be either "X-CO-O-Z" or "X-O-CO-Z".

[0016] In this specification, "ppm" means "parts-per-million (10 －６ ) and "ppb" stands for "parts-per-billion (10 －９ "). In this specification, "weight average molecular weight" means a weight average molecular weight calculated as polyethylene glycol measured by GPC (gel permeation chromatography). In this specification, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, and "(meth)acrylamide" is a concept that includes both acrylamide and methacrylamide.

[0017] The treatment liquid of the present invention (hereinafter also referred to simply as "treatment liquid") contains a specific compound represented by formula (1) described below, and at least one phosphonic acid compound selected from the group consisting of phosphonic acid and organic phosphonic acid, and the mass ratio of the content of the specific compound to the content of the phosphonic acid compound is 0.001 to 20.0.

[0018] Although the reason why the treatment solution having the above-described configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is achieved. In other words, even if the effect is achieved by a mechanism other than the one described below, it is still within the scope of the present invention. The specific compound having a predetermined structure is excellent in removing oxide films formed on the surfaces of tungsten and molybdenum and iron oxide residues attached to the surfaces, and can efficiently remove organic residues, iron oxide residues, and oxide films to which residues are attached. While compounds that exhibit the ability to remove organic residues and oxide films may be prone to corroding tungsten and molybdenum, the specific compound also has low corrosiveness to tungsten and molybdenum. Furthermore, the phosphonic acid compound selectively coordinates to the iron oxide residues and exhibits excellent iron oxide residue removal. It is believed that the treatment solution, by containing the above-described specific compound and the phosphonic acid compound in a predetermined ratio, can achieve all of excellent tungsten and molybdenum corrosion inhibition, excellent organic residue removal, and excellent iron oxide residue removal. Hereinafter, the property of being able to inhibit corrosion of tungsten or molybdenum will be simply referred to as "corrosion-inhibiting property," and superiority in at least one of corrosion-inhibiting property, organic residue removability, and iron oxide residue removability will also be referred to as "excellent effects of the present invention." Each component contained in the treatment solution and the physical properties of the treatment solution will be described in detail below.

[0019] [Compound Represented by Formula (1) (Specific Compound)] The treatment liquid contains a specific compound represented by formula (1) (also simply referred to as "specific compound").

[0020]

[0021] In formula (1), X １ ~X ４and R each independently represent a hydrogen atom or an aliphatic hydrocarbon group which may have a hydroxyl group or an amino group. The aliphatic hydrocarbon group may be linear, branched, or cyclic, preferably linear or branched, and more preferably linear. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The carbon number of the aliphatic hydrocarbon group which may have a hydroxyl group or an amino group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3, in terms of achieving superior effects of the present invention. Note that when the aliphatic hydrocarbon group has an amino group, the carbon number of the aliphatic hydrocarbon group having the amino group includes the carbon number of the amino group. For example, the carbon number of a 2-(dimethylamino)ethyl group is 4. When the aliphatic hydrocarbon group has a hydroxyl group or an amino group, the number is preferably 1 to 3, more preferably 1.

[0022] The amino group that the aliphatic hydrocarbon group may have is a primary amino group (—NH ２ ), secondary amino group (—NR Ｎ H), and a tertiary amino group (—NR Ｎ ２ In terms of achieving better effects of the present invention, a primary amino group or a secondary amino group is preferred, and a primary amino group is more preferred. Ｎ R each independently represents a hydrocarbon group which may have a hydroxyl group. Ｎ Examples of the hydrocarbon group represented by R include an aliphatic hydrocarbon group and an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred and an alkyl group being more preferred. Ｎ The hydrocarbon group represented by the formula (I) preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 carbon atom.

[0023] X １ ~X ４is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a hydroxyl group or an amino group, and more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a hydroxyl group or an amino group. R is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. As mentioned above, multiple R may be the same or different.

[0024] A plurality of R may be bonded to each other to form a ring. Examples of the ring formed by bonding a plurality of R include an aliphatic hydrocarbon ring and a nitrogen-containing aliphatic ring, with an aliphatic hydrocarbon ring being preferred and a cycloalkane being more preferred. The ring is preferably a ring formed by bonding two R to each other. The number of ring members in the ring is preferably 3 to 8, more preferably 3 to 6.

[0025] n represents an integer of 2 or more, preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and even more preferably 2 or 3.

[0026] In terms of the effects of the present invention being more excellent, when n is 2, X １ ~X ４ and at least one of R preferably represents an aliphatic hydrocarbon group which may have a hydroxyl group or an amino group. In other words, the specific compound is preferably a compound different from ethylenediamine.

[0027] The molecular weight of the specific compound is preferably 60 to 290, more preferably 70 to 230, and even more preferably 80 to 180. The number of nitrogen atoms contained in the specific compound is 2 or more, and from the viewpoint of more excellent effects of the present invention, it is preferably 2 to 4, and more preferably 2 or 3. The number of carbon atoms contained in the specific compound is 2 or more, and from the viewpoint of more excellent effects of the present invention, it is preferably 3 to 18, more preferably 3 to 11, even more preferably 3 to 9, and particularly preferably 3 to 7.

[0028] The log D value of a specific compound at pH 7.4 is preferably -7.2 to -1.0, more preferably -6.0 to -2.0. The log D value at pH 7.4 is the logarithm of the octanol / water partition coefficient at pH 7.4, taking into account pH-dependent dissociation. The log D value at pH 7.4 is the value (ACD / log D) listed in the compound database ChemSpider (http: / / www.chemspider.com / ). If not listed above, a value calculated using the ACD / Log D module of Advanced Chemistry Development's ACD / Percepta platform software may be used.

[0029] Examples of the specific compounds include ethylenediamine (EDA), 1,3-propanediamine (13PDA), N-ethylethylenediamine (EEDA), 1,2-propanediamine (12PDA), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (TK2HEEDA), N,N,N',N'',N''',N'''-hexamethyltriethylenetetramine (HMTEEA), 1,3-diaminopentane (13DAP), N-(3-aminopropyl)diethanolamine (3APDEA), 3-(dibutylamino)propylamine (3DBAPA), bis(2-aminoethyl)amine (B2AEA), N,N ,N',N'',N''-pentamethyldiethylenetriamine (PMDETA), tris(2-aminoethyl)amine (T2AEA), N,N'-bis(3-aminopropyl)ethylenediamine (BAPEDA), bis(3-aminopropyl)amine (BAPA), tris(3-aminopropyl)amine (T3APA), 2,2-dimethyl-1,3-propanediamine, 2,2'-diamino-N-methyldiethylamine, 2-[(3-aminopropyl)amino]ethanol, 3,3'-diamino-N-methyldipropylamine, N,N-diethyl-1,3-propanediamine, and 1,4-cyclohexanediamine. Of these, EEDA, 13PDA, 12PDA, 3APDEA, B2AEA, BAPA, TK2HEEDA, 3DBAPA, BAPEDA, T3APA, or T2AEA is preferred, EEDA, 13PDA, 12PDA, 3APDEA, B2AEA, BAPA, TK2HEEDA, or 3DBAPA is more preferred, and EEDA, 13PDA, 12PDA, 3APDEA, B2AEA, or BAPA is even more preferred.

[0030] The specific compound may be used alone or in combination of two or more. The content of the specific compound is preferably 0.00005 to 10.0 mass%, more preferably 0.0001 to 1.0 mass%, and even more preferably 0.002 to 0.1 mass%, relative to the total mass of the components in the treatment liquid excluding the solvent. The content of the specific compound is preferably 0.1 to 95.0 mass%, more preferably 1.0 to 90.0 mass%, and even more preferably 10.0 to 40.0 mass%, relative to the total mass of the components in the treatment liquid excluding the solvent, in terms of better organic residue removal properties and corrosion inhibition properties.

[0031] [Phosphonic Acid Compound] The treatment liquid contains phosphonic acid (HPO ３ H ２ The treatment solution contains at least one phosphonic acid compound selected from the group consisting of phosphonic acids, organic phosphonic acids, and organic phosphonic acids. The phosphonic acid compound may be ionized in the treatment solution or may be in the form of a salt. Examples of the salt include metal salts (e.g., alkali metal salts and alkaline earth metal salts) and ammonium salts (e.g., salts with ammonium ions and salts with quaternary ammonium cations).

[0032] The phosphonic acid compound is preferably an organic phosphonic acid. An organic phosphonic acid is a compound containing one or more phosphonic acid groups and one or more carbon atoms. In this specification, when a compound contains a phosphonic acid group, it means a compound containing a phosphate group (—O—PO ３ H ２ An embodiment in which a phosphonic acid group is included as part of the phosphonic acid group is not intended. The number of phosphonic acid groups in the organic phosphonic acid is not particularly limited as long as it is 1 or more, and is preferably 1 to 8, and more preferably 1 to 6. The organic phosphonic acid may have a substituent other than a phosphonic acid group. Examples of the substituent other than a phosphonic acid group include an amino group, a carboxylic acid group, a sulfonic acid group, and a hydroxyl group. The number of carbon atoms in the organic phosphonic acid is 1 or more, preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 8.

[0033] An example of the organic phosphonic acid is a compound represented by the following formula (P1): M-(PO ３ H ２ ) ｍFormula (P1): In formula (P1), M represents an m-valent linking group, and m represents an integer of 1 or more.

[0034] Examples of the m-valent linking group include a group in which one or more methylene groups are bonded to an oxygen atom, a sulfur atom, —CO—, or —NR Ｔ -, or an m-valent hydrocarbon group which may have a substituent. Ｔ each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent. The m-valent linking group may be linear, branched, or cyclic. The hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred. Examples of the substituent which the m-valent hydrocarbon group may have include an amino group, a carboxylic acid group, a sulfonic acid group, and a hydroxyl group. The m-valent hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 8. The m-valent linking group may be one in which one or more methylene groups are -NR Ｔ An m-valent aliphatic hydrocarbon group which may be substituted with - and which may have a substituent is preferred.

[0035] m represents an integer of 1 or more, preferably 1 to 8, and more preferably 1 to 6.

[0036] Examples of the phosphonic acid compound include phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDPO), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentakis(methylphosphonic acid) (DTPMP), nitrilotris(methylenephosphonic acid) (NMPA), phytic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA), iminodi(methylenephosphonic acid) (IDMP), ethylamine bis(methylenephosphonic acid) (EABMP), methylamine di(methylenephosphonic acid) (MADP), N,N-dimethylaminomethylphosphonic acid (DAMP), hydroxymethylphosphonic acid (HMP), aminomethylphosphonic acid (AMPA), methylphosphonic acid (MP), ethylidene diphosphonic acid, 1-hydroxypropyl ethylene-1,1'-diphosphonic acid, 1-hydroxybutylidene-1,1'-diphosphonic acid, dodecylaminobis(methylenephosphonic acid), 1,3-propylenediaminebis(methylenephosphonic acid), ethylenediaminebis(methylenephosphonic acid) (EDDPO), ethylenediaminetetra(ethylenephosphonic acid), 1,3-propylenediaminetetra(methylenephosphonic acid) (PDTMP), 1,2-diaminopropanetetra(methylenephosphonic acid), 1,6-hexamethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) (DEPPO), diethylenetriaminepenta(ethylenephosphonic acid), triethylenetetraminehexa(methylenephosphonic acid), and triethylenetetraminehexa(ethylenephosphonic acid). Furthermore, the compounds described in paragraphs

[0026] to

[0036] of WO 2018 / 020878 can also be used as the phosphonic acid compound. Among them, HEDPO, EDTMP, DTPMP, NMPA, phytic acid, PBTCA, IDMP, EABMP, MADP, DAMP, HMP, AMPA, or MP is preferred as the phosphonic acid compound.

[0037] The phosphonic acid compound may be used alone or in combination of two or more. The content of the phosphonic acid compound is preferably 0.0001 to 40.0 mass%, more preferably 0.0005 to 10.0 mass%, and even more preferably 0.01 to 1.0 mass%, relative to the total mass of the treatment liquid, from the viewpoint of more excellent effects of the present invention. The content of the phosphonic acid compound is preferably 4.0 to 99.9 mass%, more preferably 10.0 to 95.0 mass%, and even more preferably 40.0 to 90.0 mass%, relative to the total mass of the components excluding the solvent in the treatment liquid, from the viewpoint of more excellent effects of the present invention.

[0038] The mass ratio of the content of the specific compound to the content of the phosphonic acid compound is 0.001 to 20.0 (0.0010 to 20.0), and is preferably 0.01 to 10.0, and more preferably 0.1 to 1.0, in terms of providing better effects of the present invention. If the mass ratio of the content of the specific compound to the content of the phosphonic acid compound is less than 0.001, this is undesirable in terms of poor organic residue removability, and if it exceeds 20.0, this is undesirable in terms of poor corrosion inhibition and iron oxide residue removability.

[0039] [Basic Amino Acid] The treatment solution preferably contains a basic amino acid, as this provides better corrosion inhibition. A basic amino acid that may have a positive charge adsorbs and protects the surface of tungsten or molybdenum, thereby further inhibiting corrosion of tungsten or molybdenum. Examples of basic amino acids include arginine, histidine, lysine, ornithine, 2,4-diaminobutyric acid, tryptophan, asparagine, and glutamine. The treatment solution preferably contains at least one basic amino acid selected from the group consisting of arginine, histidine, and lysine. The basic amino acid may be in any of the D-, L-, and DL-forms.

[0040] The basic amino acid may be used alone or in combination of two or more. The content of the basic amino acid is preferably 0.0001 to 5.0 mass%, more preferably 0.001 to 1.0 mass%, and even more preferably 0.001 to 0.01 mass%, relative to the total mass of the treatment solution. The content of the basic amino acid is preferably 1.0 to 60.0 mass%, more preferably 3.0 to 30.0 mass%, and even more preferably 3.0 to 10.0 mass%, relative to the total mass of the components in the treatment solution excluding the solvent, in order to achieve better effects of the present invention. The mass ratio of the content of the specific compound to the content of the basic amino acid is preferably 0.05 to 30.0, more preferably 0.2 to 10.0, and even more preferably 0.2 to 5.0.

[0041] [Cyclodextrin or Derivatives Thereof] The treatment solution preferably contains cyclodextrin or a derivative thereof, more preferably cyclodextrin, in terms of superior organic residue removal properties. By including cyclodextrin, which can encapsulate hydrophobic organic residues, the organic residue removal properties are superior. Cyclodextrin is a type of cyclic oligosaccharide in which multiple D-glucose units are bonded by glucoside bonds to form a cyclic structure. The number of glucose bonds is often 5 or more, and more often 6 to 8. Examples of cyclodextrin include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

[0042] Examples of cyclodextrin derivatives include compounds in which the hydrogen atoms of at least one or more hydroxyl groups of cyclodextrin are replaced with substituents (e.g., alkyl groups and acyl groups), and specific examples include 2-hydroxypropyl-cyclodextrin and 2-hydroxyethyl-cyclodextrin.

[0043] The cyclodextrin or derivative thereof may be used alone or in combination of two or more. The content of the cyclodextrin or derivative thereof is preferably 0.0001 to 5.0 mass% and more preferably 0.001 to 0.05 mass% relative to the total mass of the treatment liquid. The content of the cyclodextrin or derivative thereof is preferably 10.0 to 60.0 mass% and more preferably 25.0 to 50.0 mass% relative to the total mass of the components in the treatment liquid excluding the solvent.

[0044] [Antibacterial Agent] The treatment solution preferably further contains an antibacterial agent. The antibacterial agent is a compound having antibacterial activity against bacteria and / or antifungal activity against mold, and is a compound different from the various components described above and the various components described below. The antibacterial agent may be in the form of a salt (for example, a known salt).

[0045] Examples of antibacterial agents include quaternary ammonium antibacterial agents, carboxylic acid antibacterial agents, phenol antibacterial agents, biguanide antibacterial agents, sulfamide antibacterial agents, peroxide antibacterial agents, isothiazolinone antibacterial agents, imidazole antibacterial agents, ester antibacterial agents, alcohol antibacterial agents, carbamate antibacterial agents, iodine antibacterial agents, and antibiotics.

[0046] Quaternary ammonium antibacterial agents refer to compounds or salts thereof having at least one quaternary ammonium cation group in the molecule, which have antibacterial and / or antifungal properties. Examples of quaternary ammonium antibacterial agents include benzalkonium chloride, didecyldimethylammonium chloride (DDAC), hexadecylpyridinium chloride (CPC), 3,3'-(2,7-dioxaoctane)bis(1-dodecylpyridinium bromide) (Hygeria), benzethonium chloride, and domiphen bromide. Of these, benzethonium chloride is preferred. Examples of carboxylic acid antibacterial agents include unsaturated carboxylic acids such as sorbic acid (hexadienoic acid) and dehydroacetic acid, and aromatic carboxylic acids such as benzoic acid and salicylic acid. Of these, sorbic acid, dehydroacetic acid, or benzoic acid is preferred, sorbic acid or dehydroacetic acid is more preferred, and sorbic acid is even more preferred. Examples of phenolic antibacterial agents include 3-methyl-4-chlorophenol (PCMC), 3-methyl-4-isopropylphenol (Biosol), 4-chloro-3,5-dimethylphenol (PCMX), cresol, chlorothymol, dichloroxylenol, and hexachlorophene. Of these, cresol is preferred. Examples of biguanide antibacterial agents include bis(p-chlorophenyldiguanide)hexane digluconate (chlorhexidine gluconate) and poly(hexamethylenebiguanide) hydrochloride (hexamethylenebiguanidine hydrochloride). Of these, chlorhexidine gluconate is preferred. Examples of sulfamide antibacterial agents include N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide (dichloolanid) and N-dichlorofluoromethylthio-N',N'-dimethyl-N-p-tolylsulfamide (tolylfluanid). Among these, tolylfluanid is preferred. Examples of peroxide antibacterial agents include hydrogen peroxide, peracetic acid, and chlorine dioxide. Among these, peracetic acid is preferred.Examples of isothiazolinone antibacterial agents include 2-methyl-4-isothiazolin-3-one (MIT), 2-octyl-4-isothiazolin-3-one (OIT), 1,2-benzisothiazol-3(2H)-one (BIT), and 5-chloro-2-methyl-4-isothiazolin-3-one (CIT). Among these, MIT, OIT, or BIT are preferred, with MIT or OIT being more preferred. Examples of imidazole antibacterial agents include 2-(4-thiazolyl)-benzimidazole (TBZ) and 2-benzimidazole methylcarbamate (Preventol BCM). Examples of ester antibacterial agents include glycerol laurate (monoglyceride) and parahydroxybenzoic acid ethyl ester (ethylparaben). Examples of alcohol-based antibacterial agents include ethyl alcohol (ethanol), 2-propanol (IPA), phenoxyethanol, 1,2-pentanediol, and 1,2-hexanediol. Examples of carbamate-based antibacterial agents include 3-iodo-2-propynyl butylcarbamate (Glycical). Examples of iodine-based antibacterial agents include [(4-chlorophenoxy)methyl]-3-iodo-2-propynyl ether (IF1000).

[0047] The antibacterial agent is preferably a quaternary ammonium antibacterial agent, a carboxylic acid antibacterial agent, a phenol antibacterial agent, or an isothiazolinone antibacterial agent, and more preferably a carboxylic acid antibacterial agent or an isothiazolinone antibacterial agent. Among these, the antibacterial agent is preferably benzethonium chloride, sorbic acid, dehydroacetic acid, benzoic acid, salicylic acid, cresol, MIT, OIT, or BIT.

[0048] The antibacterial agent may be used alone or in combination of two or more. The content of the antibacterial agent is preferably 0.00001 to 2.0% by mass, more preferably 0.0001 to 0.1% by mass, based on the total mass of the treatment liquid. The content of the antibacterial agent is preferably 0.01 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, based on the total mass of the components in the treatment liquid excluding the solvent.

[0049] [Low Molecular Weight Organic Acid] The treatment liquid preferably further contains a low molecular weight organic acid other than the above-mentioned phosphonic acid compound, in order to obtain better iron oxide residue removal properties. The low molecular weight organic acid refers to a component other than the above-mentioned basic amino acid. The low molecular weight organic acid refers to an organic acid having a molecular weight of 700 or less. The molecular weight of the low molecular weight organic acid is preferably 600 or less, more preferably 450 or less, and even more preferably 300 or less. The lower limit of the molecular weight is preferably 50 or more, more preferably 100 or more. The low molecular weight organic acid preferably has 2 to 15 carbon atoms.

[0050] Examples of low-molecular-weight organic acids include carboxylic acid organic acids and sulfonic acid organic acids, with carboxylic acid organic acids being preferred. The carboxylic acid organic acid is preferably an aliphatic carboxylic acid, with saturated aliphatic carboxylic acids being more preferred. In other words, the carboxylic acid organic acid is preferably a compound different from aromatic carboxylic acids, and also preferably does not have a carbon-carbon unsaturated bond. The number of carboxylic acid groups in the carboxylic acid organic acid is 1 or more, preferably 2 or more. There is no particular upper limit, but it is often 8 or less. Examples of aliphatic carboxylic acids include polycarboxylic acids, hydroxycarboxylic acids, and aminopolycarboxylic acids, with polycarboxylic acids or hydroxycarboxylic acids being preferred, and polycarboxylic acids being more preferred.

[0051] Examples of polycarboxylic acids include tartaric acid, citric acid, malonic acid, succinic acid, malic acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, maleic acid, and isocitric acid. Examples of hydroxycarboxylic acids include gluconic acid, glycolic acid, lactic acid, heptonic acid, glyceric acid, and hydroxybutyric acid. Examples of aminopolycarboxylic acids include 1,4-butanediaminetetraacetic acid (BDTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, 1,3-propanediamine-N,N,N',N'-tetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylene-diamine-N,N,N',N'-tetraacetic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclododecane-tetraacetic acid, diaminopropanoltetraacetic acid, (hydroxyethyl)ethylenediaminetriacetic acid, and iminodiacetic acid (IDA).

[0052] Of the low molecular weight organic acids, tartaric acid, citric acid, malonic acid, succinic acid, or malic acid is preferred.

[0053] The low-molecular-weight organic acid may be used alone or in combination of two or more. The content of the low-molecular-weight organic acid is preferably 0.0001 to 3.0% by mass, more preferably 0.001 to 1.0% by mass, based on the total mass of the treatment liquid. The content of the low-molecular-weight organic acid is preferably 0.1 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, based on the total mass of the components in the treatment liquid excluding the solvent.

[0054] [Water] The treatment solution preferably contains water. The type of water may be any type that does not adversely affect the semiconductor substrate, and distilled water, deionized (DI) water, and pure water (ultrapure water) can be used. Pure water (ultrapure water) is preferred because it contains almost no impurities and has less of an effect on the semiconductor substrate during the semiconductor substrate manufacturing process. The water content may be the balance of the components that can be contained in the treatment solution. The water content is preferably 60.0 mass% or more, more preferably 80.0 mass% or more, even more preferably 90.0 mass% or more, and particularly preferably 97.0 mass% or more, based on the total mass of the treatment solution. The upper limit is preferably 99.99 mass% or less, and more preferably 99.9 mass% or less, in order to achieve better effects of the present invention.

[0055] [Other Components] The treatment liquid may contain other components in addition to those described above, such as a polymer, a surfactant, a pH adjuster, an anticorrosive, an organic solvent, a polyhydroxy compound having a molecular weight of 500 or more, an oxidizing agent, a reducing agent, and a fluoride.

[0056] <Polymer> In terms of superior organic residue removal properties, it is also preferable for the treatment solution to contain a polymer. The polymer is preferably a water-soluble polymer. The term "water-soluble polymer" refers to a compound in which two or more structural units are linked together in a linear or network-like manner via covalent bonds, and which dissolves in 100 g of water at 20°C at a mass of 0.1 g or more. More specific examples of water-soluble polymers include anionic polymers such as poly(meth)acrylic acid, polysulfonic acid, and copolymers thereof (e.g., acrylic acid-sulfonic acid copolymers), poly(meth)acrylamide, polyvinyl alcohol, hydroxyethyl cellulose, and polyvinylpyrrolidone. Anionic polymers are preferred as water-soluble polymers, with poly(meth)acrylic acid, polysulfonic acid, or copolymers thereof being preferred, and poly(meth)acrylic acid or polysulfonic acid being more preferred. Note that all or a portion of the anionic groups in the anionic polymer may form a salt. The weight-average molecular weight (Mw) of the water-soluble polymer is preferably 1,000 or more, more preferably 2,000 or more. The upper limit of the weight average molecular weight (Mw) of the water-soluble polymer is often 1.5 million or less, preferably 1.2 million or less, and more preferably 1 million or less. The weight average molecular weight of the water-soluble polymer is a value measured by GPC (gel permeation chromatography) in terms of polyethylene glycol.

[0057] The content of the polymer is preferably 0.0001 to 5.0% by mass, more preferably 0.001 to 0.1% by mass, based on the total mass of the treatment liquid, and is preferably 1.0 to 20.0% by mass, more preferably 3.0 to 15.0% by mass, and even more preferably 3.0 to 10.0% by mass, based on the total mass of the components in the treatment liquid excluding the solvent.

[0058] <Surfactant> The surfactant is not particularly limited as long as it is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule, and examples thereof include nonionic surfactants, cationic surfactants, and anionic surfactants. Surfactants often have at least one hydrophobic group selected from the group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. The total carbon number of the surfactant is preferably 16 to 100.

[0059] Examples of the nonionic surfactant include ester-type nonionic surfactants, ether-type nonionic surfactants, and ester-ether-type nonionic surfactants, and ether-type nonionic surfactants are preferred. Examples of the nonionic surfactant include the compounds exemplified in paragraph

[0126] of WO 2022 / 044893, the contents of which are incorporated herein by reference.

[0060] Examples of cationic surfactants include primary to tertiary alkylamine salts (e.g., monostearyl ammonium chloride, distearyl ammonium chloride, tristearyl ammonium chloride, etc.) and modified aliphatic polyamines (e.g., polyethylene polyamine, etc.).

[0061] Examples of anionic surfactants include sulfonic acid surfactants having a sulfonic acid group, sulfate ester surfactants having a sulfate ester group, and carboxylic acid surfactants having a carboxylic acid group. Examples of anionic surfactants include the compounds exemplified in paragraphs

[0116] to

[0123] of WO 2022 / 044893, the contents of which are incorporated herein by reference.

[0062] <pH Adjuster> The treatment liquid may contain a pH adjuster to adjust and maintain the pH of the treatment liquid. The pH adjuster is a basic compound or an acidic compound that is different from the compounds that may be contained in the treatment liquid (e.g., specific compounds, phosphonic acid compounds, basic amino acids, cyclodextrins, etc.). However, it is permissible to adjust the pH of the treatment liquid by adjusting the amount of each of the above components added.

[0063] A basic compound is a compound that exhibits basicity (a pH greater than 7.0) in an aqueous solution, and examples thereof include basic inorganic compounds and basic organic compounds. Examples of basic inorganic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides. Examples of basic organic compounds include quaternary ammonium compounds and amine compounds other than the compound represented by formula (1). Examples of quaternary ammonium compounds include tetraalkylammonium compounds such as tetramethylammonium hydroxide (TMAH), trimethylethylammonium hydroxide (TMEAH), dimethyldiethylammonium hydroxide (DMDEAH), methyltriethylammonium hydroxide (MTEAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), and tetrabutylammonium hydroxide (TBAH), tris(hydroxymethyl)aminomethane, 2-hydroxyethyltrimethylammonium hydroxide, and benzyltrimethylammonium hydroxide (BTMAH). Examples of amine compounds other than the compound represented by formula (1) include amine compounds having only one nitrogen atom, and specific examples thereof include 2-dimethylamino-2-methyl-1-propanol (DMAMP), trishydroxymethylaminomethane (Tris), 2-amino-2-methyl-1-propanol (AMP), monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA).

[0064] An acidic compound is a compound that exhibits acidity (pH less than 7.0) in an aqueous solution. Examples of the acidic compound include acidic inorganic compounds. Examples of the acidic inorganic compound include hydrochloric acid, sulfuric acid, nitric acid, nitrous acid, sulfurous acid, phosphoric acid, and boric acid. The acidic compound used as the pH adjuster may be a salt of an acidic compound, as long as it becomes an acid or an acid ion (anion) in an aqueous solution.

[0065] The pH adjuster may be used alone or in combination of two or more. The content of the pH adjuster can be selected depending on the type and amount of other components and the desired pH of the treatment liquid. For example, the content of the pH adjuster is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 1% by mass, relative to the total mass of the treatment liquid.

[0066] <Corrosion inhibitor> The corrosion inhibitor is not particularly limited as long as it has the function of preventing corrosion of the exposed surface of the workpiece (especially tungsten and molybdenum), and examples thereof include heterocyclic compounds. Heterocyclic compounds are preferably nitrogen-containing heterocyclic compounds in which at least one of the heteroatoms constituting the heterocycle is a nitrogen atom. Examples of nitrogen-containing heterocyclic compounds include azole compounds, purine compounds, pyrrole compounds, pyridine compounds, pyrazine compounds, pyrimidine compounds, indole compounds, indolizine compounds, indazole compounds, quinoline compounds, and oxazole compounds, with purine compounds or azole compounds being preferred. Specific examples of corrosion inhibitors include the compounds described in paragraphs

[0046] to

[0050] of WO 2021 / 166571, the contents of which are incorporated herein by reference.

[0067] <Organic Solvent> Examples of the organic solvent include known organic solvents, such as alcohol-based solvents, glycol-based solvents, glycol ether-based solvents, and ketone-based solvents. The organic solvent is preferably miscible with water at any ratio. Examples of the organic solvent include the compounds exemplified in paragraphs

[0135] to

[140] of WO 2022 / 044893, the contents of which are incorporated herein by reference.

[0068] The polyhydroxy compound having a molecular weight of 500 or more is a compound different from the compounds that may be contained in the treatment liquid. The polyhydroxy compound is an organic compound having two or more (e.g., 2 to 200) alcoholic hydroxyl groups per molecule. The molecular weight (weight average molecular weight when the polyhydroxy compound has a molecular weight distribution) of the polyhydroxy compound is 500 or more, preferably 500 to 100,000, and more preferably 500 to 3,000. The compounds exemplified in paragraphs

[0101] and

[0102] of WO 2022 / 014287 can also be used as the polyhydroxy compound, and the contents of these paragraphs are incorporated herein by reference.

[0069] Examples of the oxidizing agent include peroxides (such as hydrogen peroxide), persulfides (such as monopersulfides and dipersulfides), percarbonates, acids thereof, and salts thereof. Examples of the oxidizing agent include oxide halides (periodic acids such as iodic acid, metaperiodic acid, and orthoperiodic acid, and salts thereof), perboric acid, perborates, cerium compounds, and ferricyanides (such as potassium ferricyanide).

[0070] Examples of reducing agents include catechol or derivatives thereof (e.g., methylcatechol, gallic acid, pyrogallol, ellagic acid, catechol-4-acetic acid, catechin, and isoflavone), ascorbic acid or derivatives thereof (e.g., isoascorbic acid, ascorbic acid sulfate, and ascorbic acid phosphate), and mercapto compounds (e.g., mercaptosuccinic acid, 1-thioglycerol, 2-mercaptoethanol, 3-mercapto-1-propanol, and thioglycolic acid). Compounds described in paragraphs

[0054] to

[0065] of WO 2019 / 187868 can also be used as reducing agents, and the contents of these documents are incorporated herein by reference.

[0071] Fluorides are compounds that serve as a source of fluorine-containing ions, and examples thereof include compounds containing fluorine-containing ions and cations. Examples of the fluorine-containing ions include fluoride ions (F － ), bifluoride ion (HF ２ －), and fluoride-containing ions (e.g., MF ６ ｎ－ , M: any atom, n: 1 to 3). Examples of M include B, Al, Si, P, Ti, Zr, Nb, Sb, and Ta. Specific examples of fluorides include HF, NH ４ F, H ２ SiF ６ , H ２ TiF ６ , H ２ ZrF ６ , HPF ６ , and HBF ４ Examples include:

[0072] [Physical Properties of Treatment Solution] <pH> The treatment solution may be either alkaline or acidic. From the viewpoint of achieving superior effects of the present invention, the pH of the treatment solution is preferably 1.0 to 12.0, more preferably 3.0 to 9.0, even more preferably 5.0 to 8.0, and particularly preferably 7.0 to 8.0. By having the pH satisfy the above preferred range, the solubility of residues is improved and the dissolution of tungsten and molybdenum can be further suppressed. Furthermore, from the viewpoint of superior corrosion inhibition of tungsten, the pH of the treatment solution is preferably 9.0 or less, more preferably 8.0 or less. From the viewpoint of superior organic residue removability, the pH is preferably 3.0 or more, more preferably 5.0 or more, and even more preferably 7.0 or more. The pH of the treatment solution can be measured using a known pH meter according to a method in accordance with JIS Z8802-1984. The pH measurement temperature is 25°C.

[0073] <Metal Content> The content (measured as ion concentration) of metals (e.g., metal elements Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag) contained as impurities in the treatment solution is preferably 5 mass ppm or less, more preferably 1 mass ppm or less. Since it is expected that treatment solutions of even higher purity will be required in the manufacture of cutting-edge semiconductor devices, the content of the above metals is more preferably lower than 1 mass ppm, that is, on the order of ppb or less, particularly preferably 100 mass ppb or less, and most preferably less than 10 mass ppb. The lower limit is preferably 0.

[0074] Examples of methods for reducing the metal content include purification treatments such as distillation and filtration using an ion exchange resin or a filter at the stage of raw materials used in producing the treatment liquid or at the stage after the production of the treatment liquid. Another method for reducing the metal content includes using a container that is less likely to leach out impurities, as described below, as a container for containing the raw materials or the produced treatment liquid. Another method includes lining the inner wall of a pipe with a fluororesin to prevent metal components from leaching out from the pipe during production of the treatment liquid.

[0075] <Coarse Particles> The treatment liquid may contain coarse particles, but the content thereof is preferably low. Coarse particles refer to particles having a diameter (particle size) of 1 μm or more when the particle shape is considered to be a sphere. The coarse particles contained in the treatment liquid include particles such as dust, dirt, organic solids, and inorganic solids contained as impurities in the raw materials, as well as particles such as dust, dirt, organic solids, and inorganic solids brought in as contaminants during the preparation of the treatment liquid, and which ultimately exist as particles without dissolving in the treatment liquid.

[0076] The content of coarse particles in the treatment liquid is preferably 100 or less, more preferably 50 or less, particles with a particle size of 1 μm or more per mL of treatment liquid. The lower limit is preferably 0 or more, more preferably 0.01 or more, per mL of treatment liquid. The content of coarse particles present in the treatment liquid can be measured in the liquid phase using a commercially available measuring device that uses a laser as a light source for light scattering liquid particle measurement. Methods for removing coarse particles include, for example, purification processes such as filtering, which will be described later.

[0077] It is also preferable that the treatment liquid does not contain abrasive particles.

[0078] [Method for Producing Treatment Liquid] The treatment liquid of the present invention can be produced by a known method, which will be described in detail below.

[0079] [Liquid preparation step] The treatment liquid can be produced, for example, by mixing the above-mentioned components.As a method for preparing the treatment liquid, for example, a specific compound, a phosphonic acid compound, and, if necessary, optional components are sequentially added to a container containing purified pure water, and then the mixture is stirred and mixed, and, if necessary, a pH adjuster is added to adjust the pH of the mixture, thereby preparing the treatment liquid.In addition, when each component is added to a container, it may be added all at once, or may be added in multiple divided portions.

[0080] The stirring device and stirring method used to prepare the treatment solution may be a known device such as a stirrer or disperser. Examples of the stirrer include an industrial mixer, a portable stirrer, a mechanical stirrer, and a magnetic stirrer. Examples of the disperser include an industrial disperser, a homogenizer, an ultrasonic disperser, and a bead mill.

[0081] The mixing of the components in the preparation step of the treatment solution, the purification treatment described below, and storage of the produced treatment solution are preferably carried out at 40° C. or lower, more preferably at 30° C. or lower. The lower limit is preferably 5° C. or higher, more preferably 10° C. or higher. By preparing, treating, and / or storing the treatment solution within the above temperature range, the performance can be maintained stably for a long period of time.

[0082] <Purification> It is preferable to perform a purification treatment in advance on one or more of the raw materials used to prepare the treatment solution. Examples of purification treatment include known methods such as distillation, ion exchange, and filtration. The degree of purification is preferably such that the raw material has a purity of 99% by mass or more, and more preferably such that the raw solution has a purity of 99.9% by mass or more. The upper limit is preferably 99.9999% by mass or less.

[0083] Examples of purification methods include passing the raw material through an ion exchange resin or a reverse osmosis membrane (RO membrane), reprecipitation, distillation of the raw material, and filtering. A combination of the above purification methods may be used as the purification method. For example, the raw material may be subjected to primary purification by passing it through an RO membrane, and then subjected to secondary purification by passing it through a purification device consisting of a cation exchange resin, an anion exchange resin, or a mixed-bed ion exchange resin. Furthermore, the purification process may be performed multiple times.

[0084] The filter used for filtering is not particularly limited as long as it is one that has been conventionally used for filtering purposes. Examples include filters made of fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyallylsulfone (PAS), and polyolefin resins (including high-density or ultra-high molecular weight) such as polyethylene and polypropylene (PP). 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. Filtering raw materials using filters made of these materials can effectively remove highly polar foreign matter that is likely to cause defects.

[0085] <Container> The treatment liquid (including the diluted treatment liquid described below) can be filled into any container for storage, transport and use, as long as corrosiveness and other factors do not pose a problem.

[0086] As a container, a container with a high degree of cleanliness within the container for semiconductor applications and that suppresses the elution of impurities from the inner wall of the container's storage section into each liquid is preferred. Examples of such containers include various containers commercially available as containers for semiconductor processing liquids, such as the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited to these. In addition, the containers exemplified in paragraphs

[0121] to

[0124] of WO 2022 / 004217 can also be used as containers, and the contents of these containers are incorporated herein.

[0087] The interior of these containers is preferably washed before filling with the treatment liquid. The liquid used for washing is preferably one that has a reduced amount of metal impurities. After production, the treatment liquid may be bottled in a container such as a gallon bottle or a coated bottle, and then transported and stored.

[0088] To prevent changes in the components of the treatment solution during storage, the container may be filled with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. A gas with a low water content is particularly preferred. The treatment solution may be transported and stored at room temperature, or the temperature may be controlled to a range of -20°C to 20°C to prevent deterioration.

[0089] <Clean Room> It is preferable that all of the manufacturing of the treatment liquid, handling including opening and cleaning of containers, filling of the treatment liquid, treatment analysis, and measurement are carried out in a clean room. The clean room preferably meets the 14644-1 clean room standard. It is preferable that the clean room meets any of ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably ISO Class 1 or ISO Class 2, and even more preferably ISO Class 1.

[0090] [Dilution Step] The treatment liquid may be subjected to a dilution step in which the treatment liquid is diluted with a diluent such as water, and then the diluted treatment liquid (diluted treatment liquid) may be used to treat an object to be treated. Note that the diluted treatment liquid is also one form of the treatment liquid of the present invention as long as it satisfies the requirements of the present invention.

[0091] It is preferable to perform a purification treatment on the diluent used in the dilution step in advance. It is also more preferable to perform a purification treatment on the diluted treated solution obtained by the dilution step. Examples of the purification treatment include the ion component reduction treatment using an ion exchange resin or an RO membrane, etc., and the removal of foreign matter using filtering, which are described as purification treatments for the treated solution above. It is preferable to perform either of these treatments.

[0092] The dilution ratio of the treatment liquid in the dilution step may be adjusted as appropriate depending on the type and content of each component and the material to be treated, but the ratio of the diluted treatment liquid to the treatment liquid before dilution (dilution factor) is preferably 10 to 10,000 times, more preferably 20 to 3,000 times, even more preferably 50 to 1,000 times, and particularly preferably 75 to 150 times, in terms of mass ratio or volume ratio (volume ratio at 23° C.). In addition, the treatment liquid is preferably diluted with water (preferably ultrapure water) in order to obtain better residue removal properties.

[0093] The change in pH before and after dilution (the difference between the pH of the treatment liquid before dilution and the pH of the diluted treatment liquid) is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.8 or less. The pH of the treatment liquid before dilution and the pH of the diluted treatment liquid are preferably each in the preferred embodiment described above. The pH of the diluted treatment liquid may be adjusted using the pH adjuster described above.

[0094] The specific method for the dilution step of diluting the treatment liquid may be similar to that used in the above-mentioned treatment liquid preparation step. The stirring device and stirring method used in the dilution step may also be similar to those used in the above-mentioned treatment liquid preparation step, using the known stirring device.

[0095] [Uses] The treatment liquid is used to treat a workpiece in a semiconductor manufacturing process. Examples of the workpiece include a metal-containing workpiece (e.g., a semiconductor substrate) and a pad used to treat the semiconductor substrate. The metal-containing workpiece is preferably a workpiece that has been subjected to chemical mechanical polishing (CMP), and more preferably a workpiece containing at least one of tungsten and molybdenum that has been subjected to CMP. In other words, the treatment liquid is preferably used to treat a workpiece that has been subjected to CMP and contains at least one of tungsten and molybdenum. Examples of the pad include a polishing pad and a buffing pad, and more preferably a pad (polishing pad) used in CMP. In other words, the treatment liquid is also preferably used to treat a pad used in CMP. As described above, the treatment liquid may be used as a diluted treatment liquid obtained by diluting the treatment liquid.

[0096] [Workpiece containing metal] The workpiece containing metal is preferably a semiconductor substrate containing metal. When the semiconductor substrate contains metal, the metal may be located on the front, back, side, or in a groove of the semiconductor substrate. When the semiconductor substrate contains metal, the metal may be located not only on the surface of the semiconductor substrate but also on the semiconductor substrate via another layer.

[0097] Examples of the metal include tungsten (W), molybdenum (Mo), copper (Cu), cobalt (Co), ruthenium (Ru), aluminum (Al), titanium (Ti), tantalum (Ta), chromium (Cr), hafnium (Hf), osmium (Os), platinum (Pt), nickel (Ni), manganese (Mn), iron (Fe), zirconium (Zr), palladium (Pd), lanthanum (La), niobium (Nb), and at least one metal M selected from the group consisting of iridium (Ir), and at least one metal selected from the group consisting of W, Mo, Cu, Co, and Ru is preferred, at least one metal selected from the group consisting of W and Mo is more preferred, and W is even more preferred. In other words, the workpiece is preferably a workpiece containing at least one of W and Mo, and more preferably a workpiece containing W.

[0098] The metal is preferably present as a metal layer containing the metal. Examples of the form of the metal contained in the metal layer include a simple substance of metal M and an alloy containing metal M. In particular, the workpiece preferably has a metal layer containing metal M, more preferably has a metal layer containing W, Mo, Cu, Co, or Ru, further preferably has a metal layer containing W or Mo, and particularly preferably has a metal layer containing W.

[0099] Examples of metal layers containing W include a metal film made of tungsten alone (W metal film) and a metal film made of an alloy of tungsten and other metals (W alloy metal film). Examples of tungsten alloy metal films include a tungsten-titanium alloy metal film (WTi alloy metal film) and a tungsten-cobalt alloy metal film (WCo alloy metal film). W-containing films are used, for example, as barrier metals or in the connection between vias and wiring.

[0100] Examples of metal layers containing Mo include metal films made only of molybdenum (Mo metal films) and metal films made of alloys of molybdenum and other metals (Mo alloy metal films). Examples of other metals in Mo alloy metal films include Cu, Co, W, Ru, Al, Ti, and Ta. Mo-containing films are used, for example, as barrier metals or in the connection between vias and wiring.

[0101] The object to be treated with the treatment liquid may include, in addition to the above-mentioned metal layer, a semiconductor substrate, an insulating film, a metal wiring film, and a barrier metal, for example.

[0102] Examples of wafers constituting semiconductor substrates include wafers made of silicon-based materials such as silicon (Si) wafers, silicon carbide (SiC) wafers, and silicon-containing resin wafers (glass epoxy wafers), as well as 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 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.

[0103] The insulating film may be, for example, a silicon oxide film (e.g., silicon dioxide (SiO ２ ) film and tetraethyl orthosilicate (Si(OC ２ H ５ ) ４ ) film (TEOS film), silicon nitride film (e.g., silicon nitride (Si ３ N ４ ) and silicon carbide nitride (SiNC), etc.), and low dielectric constant (Low-k) films (for example, carbon-doped silicon oxide (SiOC) films, BD (black diamond) films, silicon carbide (SiC) films, etc.), with low dielectric constant (Low-k) films being preferred.

[0104] Examples of wiring metals include copper (Cu), copper-aluminum alloy (CuAl), copper-titanium alloy (CuTi), copper-chromium alloy (CuCr), copper-manganese alloy (CuMn), copper-tantalum alloy (CuTa), copper-niobium alloy (CuNb), copper-tungsten alloy (CuW), silver (Ag), and gold (Au).

[0105] Examples of barrier metals include tantalum (Ta), tantalum nitride (TaN), titanium nitride (TiN), cobalt (Co), cobalt alloys, ruthenium (Ru), and ruthenium alloys.

[0106] The method for forming the insulating film, W-containing film, Mo-containing film, etc. on a wafer constituting a semiconductor substrate is not particularly limited as long as it is a method commonly used in this field. Examples of the insulating film formation method include a method in which a silicon oxide film is formed on a wafer constituting a semiconductor substrate by heat treatment in the presence of oxygen gas, and then a silicon nitride film is formed by chemical vapor deposition (CVD) using silane and ammonia gases. Examples of the W-containing film and Mo-containing film formation method include a method in which a circuit is formed on a wafer having the insulating film by a known method such as resist, and then a metal layer is formed by plating, physical vapor deposition (PVD), CVD, or the like. The workpiece may have a layer for forming the W-containing film and Mo-containing film on the insulating film.

[0107] <CMP Treatment> The treatment liquid is preferably used on a workpiece that has been subjected to CMP treatment. That is, the workpiece is preferably a workpiece containing a metal that has been subjected to CMP treatment, and more preferably a semiconductor substrate containing a metal that has been subjected to CMP treatment.

[0108] CMP is a process for planarizing the surface of a substrate having a layer selected from, for example, a metal wiring film, a barrier metal, and an insulating film, by a combined action of chemical and mechanical polishing using a polishing slurry containing abrasive particles (abrasive grains). Specifically, for example, the surface of the workpiece is brought into contact with a polishing pad, and the workpiece and the polishing pad are slid relative to each other while the polishing slurry is supplied to the contact area. As a result, components on the surface of the workpiece are removed and planarized by the frictional forces between the polishing pad, the polishing slurry, and the surface of the workpiece, and the chemical action of the polishing slurry. The polishing pad is not particularly limited, and pads commonly used in CMP processes, such as nonwoven fabrics, polyurethane foams, and porous fluororesins, can be used. Residues such as metal impurities derived from the abrasive grains used in the CMP process (e.g., silica and alumina), the polished metal wiring film, and / or the barrier metal may remain on the surface of the workpiece after CMP. Organic matter derived from the CMP processing solution used during CMP may also remain as residue. These residues may, for example, cause short circuits between wirings and deteriorate the electrical properties of the semiconductor substrate, so semiconductor substrates that have undergone CMP are subjected to a cleaning treatment to remove these residues from the surface. The treatment liquid of the present invention is preferably used as a cleaning liquid for the cleaning treatment after the above-mentioned CMP treatment. In particular, when the metal in the workpiece contains at least one of tungsten and molybdenum, an iron oxide-containing material is often used in the CMP treatment, and the residues can be efficiently removed using the treatment liquid of the present invention. Specific examples of workpieces that have undergone CMP treatment include, but are not limited to, substrates that have undergone CMP treatment as described in Journal of the Japan Society for Precision Engineering, Vol. 84, No. 3, 2018.

[0109] <Pad Cleaning Treatment (Buff Cleaning Treatment)> After CMP treatment, the surface of the workpiece may be subjected to a pad cleaning treatment (buff cleaning treatment). Pad cleaning treatment (buff cleaning treatment) is a treatment that uses a pad to reduce residues present on the surface of the workpiece. Specifically, the surface of the workpiece that has been subjected to CMP treatment is brought into contact with a pad, and the workpiece and the pad are slid relative to each other while a pad cleaning composition is supplied to the contact area. As a result, residues on the surface of the workpiece are removed by the frictional force of the pad and the chemical action of the pad cleaning composition. In other words, the pad cleaning treatment is different from the treatment of a pad, which is the workpiece, using the treatment liquid of the present invention, which will be described later. The pad cleaning composition refers to a composition (pad cleaning treatment composition) used in the pad cleaning treatment (buff cleaning treatment).

[0110] The pad is not particularly limited and can be appropriately selected depending on the type of workpiece, the type of residue to be removed, and the equipment used. The pad may be a polishing pad used in CMP processing, or a buff pad such as a foam polyurethane buff pad, a nonwoven fabric buff pad, a suede buff pad, or a sponge buff pad. The pad cleaning process using a pad includes processes called rinse polishing, buff cleaning, or buff polishing.

[0111] Known cleaning compositions can be used as the pad cleaning composition, depending on the type of object to be treated and the type and amount of residue to be removed. Examples of components contained in the pad cleaning composition include a water-soluble polymer such as polyvinyl alcohol, a dispersion medium such as water, an acid such as nitric acid, a basic compound such as an amine, a surfactant, an antibacterial agent, and a phosphonic acid compound. The pad cleaning composition does not contain abrasive particles. The pad cleaning composition preferably contains a surfactant, as this provides excellent residue removal. Examples of surfactants include those that may be contained in the treatment liquid described above. Nonionic surfactants are preferred, ester-type nonionic surfactants are more preferred, and polyoxyethylene sorbitan fatty acid esters or sorbitan fatty acid esters are even more preferred. The content of the surfactant in the pad cleaning composition is preferably 0.01 to 20% by mass. The pad cleaning composition may be acidic, basic, or neutral, and is preferably acidic (preferably pH 6 or less) or basic (preferably pH 8 or more).

[0112] The apparatus and conditions used in the pad cleaning treatment can be appropriately selected from known apparatus and conditions depending on the type of material to be treated and the type and amount of residue to be removed. For example, the treatment method described in paragraphs

[0085] to

[0088] of WO 2017 / 169539 can be used, the contents of which are incorporated herein by reference.

[0113] In one embodiment of the pad cleaning treatment, it is also preferable to perform the pad cleaning treatment on an object to be treated using the treatment liquid of the present invention as a pad cleaning composition. The treatment liquid used in the pad cleaning treatment may be a diluted treatment liquid.

[0114] The pad cleaning process may be performed only once or may be performed two or more times. For example, the workpiece may be subjected to a pad cleaning process using a polishing pad and a pad cleaning process using a buffing pad after the CMP process.

[0115] [Pad] The pad to be treated with the treatment liquid is not particularly limited as long as it is used in the processing of semiconductor substrates, but is preferably a pad (polishing pad) used in CMP processing. After CMP processing, the polishing pad used in CMP processing may be contaminated with residues such as abrasive grains used in CMP processing, metal impurities derived from the polished metal wiring film and barrier metal, and organic matter derived from the CMP processing liquid. If the CMP processing of the next workpiece is performed with these residues attached to the polishing pad, defects such as polishing scratches and residue adhesion may occur on the surface of the workpiece. Therefore, it is preferable that the polishing pad be cleaned after or before the CMP processing. The treatment liquid is also preferably used as a cleaning liquid for cleaning the polishing pad used in the CMP processing. The treatment liquid used for the pad cleaning processing may be a diluted treatment liquid.

[0116] The pad to be treated with the treatment liquid may be a buff pad used in the pad cleaning treatment described above. In other words, the treatment liquid may be used as a treatment liquid for a pad used in buff cleaning.

[0117] [Method for treating object to be treated] The treatment liquid can be used by a known method. Examples of methods for using the treatment liquid include a method for treating an object to be treated that includes a step of contacting the object to be treated with the treatment liquid. Hereinafter, the step of contacting the object to be treated with the treatment liquid will also be referred to as a "contact step." The object to be treated is as described above, and may be, for example, a metal-containing object to be treated or a pad. The method for contacting the object to be treated with the treatment liquid is not particularly limited, and examples include a method of immersing the object to be treated in the treatment liquid contained in a tank, a method of spraying the treatment liquid onto the object to be treated, a method of flowing the treatment liquid onto the object to be treated, and combinations thereof. The above method may be appropriately selected depending on the purpose. The contact of the object to be treated with the treatment liquid in the contact step may be carried out only once or may be carried out two or more times. When carried out two or more times, the same method may be repeated, or different methods may be combined.

[0118] The temperature of the treatment liquid is not particularly limited, but is preferably 10 to 60°C, more preferably 15 to 50°C, in terms of providing better cleaning properties and further suppressing damage to components.

[0119] The pH of the treatment solution and the pH of the diluted treatment solution are preferably in the preferred pH ranges described above.

[0120] When treating a metal-containing workpiece, any method commonly used in this field may be used. For example, scrubbing may be used, in which a cleaning member such as a brush is brought into physical contact with the surface of the workpiece while a treatment liquid is being supplied to remove residues, or a spin (drop) method may be used, in which a treatment liquid is dropped onto the workpiece while it is rotating. In the immersion method, ultrasonic treatment is preferably performed on the workpiece immersed in the treatment liquid, as this method can further reduce impurities remaining on the surface of the workpiece.

[0121] The method for processing metal-containing workpieces may be either a single-wafer method or a batch method. The single-wafer method is a method in which workpieces are processed one by one, while the batch method is a method in which multiple workpieces are processed simultaneously.

[0122] For the pad treatment, any method commonly used in this field may be appropriately adopted, for example, a method in which the pad is brought into contact with and slid over an object that is not to be polished by the pad while supplying a treatment liquid.

[0123] The contact time between the object to be treated and the treatment liquid may be changed as appropriate depending on the type and content of each component contained in the treatment liquid, and the object and purpose of use of the treatment liquid, but is preferably 10 to 120 seconds, more preferably 20 to 90 seconds, and even more preferably 30 to 60 seconds.

[0124] The supply amount (supply rate) of the treatment liquid is preferably 50 to 5,000 mL / min, and more preferably 500 to 2,000 mL / min.

[0125] In the contact step, mechanical stirring may be used to further enhance the cleaning ability of the treatment liquid. Examples of mechanical stirring methods include circulating the treatment liquid above the object to be treated, flowing or spraying the treatment liquid above the object to be treated, and stirring the treatment liquid with ultrasonic waves or megasonics.

[0126] The treatment step is preferably a cleaning step in which the object to be treated is brought into contact with a treatment liquid to remove residues from the surface of the object to be treated. Preferred embodiments of the cleaning step are the same as those of the contact step described above.

[0127] Furthermore, after the contacting step, a step of contacting the workpiece with a rinse liquid (hereinafter also referred to as a "rinsing step") may be carried out. By carrying out the rinsing step, the workpiece obtained in the contacting step can be washed with the rinse liquid, and residual matter can be efficiently removed. The rinsing step is preferably carried out continuously after the semiconductor substrate cleaning step, and is a step of rinsing the workpiece with the rinse liquid. The rinsing step may be carried out using the mechanical stirring method described above.

[0128] Examples of rinse solutions include water (preferably DI water), methanol, ethanol, isopropyl alcohol (IPA), N-methylpyrrolidinone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Aqueous rinse solutions having a pH greater than 8.0 (such as diluted aqueous ammonium hydroxide) may also be used.

[0129] The method of contacting the rinse liquid with the object to be treated can be the same as the method of contacting the treatment liquid with the object to be treated. The contact time between the object to be treated and the rinse liquid can be appropriately changed depending on the type and content of each component contained in the treatment liquid, and the object and purpose of use of the treatment liquid. In practice, the contact time is preferably 10 to 120 seconds, more preferably 20 to 90 seconds, and even more preferably 30 to 60 seconds.

[0130] After the contacting step and / or the rinsing step, a drying step may be performed to dry the workpiece. Examples of the drying method include spin drying, flowing a dry gas over the workpiece, heating the substrate with a heating means such as a hot plate or an infrared lamp, Marangoni drying, Rotagoni drying, IPA drying, and any combination thereof.

[0131] [Electronic Device Manufacturing Method] The above-described method for processing a workpiece can be suitably applied to the manufacturing process of an electronic device. The above-described method for processing a workpiece can be performed before or after other processes performed on a substrate. The above-described method can be incorporated into other processes while the above-described method is being performed, or the above-described method can be incorporated into other processes. Examples of other processes include processes for forming structures such as metal wiring, gate structures, source structures, drain structures, insulating films, ferromagnetic layers, and nonmagnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and modification), resist formation processes, exposure processes, removal processes, heat treatment processes, cleaning processes, and inspection processes.

[0132] The above processing method may be performed at any stage of a back end process (BEOL: Back end of the line), a middle process (MOL: Middle of the line), or a front end process (FEOL: Front end of the line), and is preferably performed in a front end process or a middle process.

[0133] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate 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 following examples.

[0134] In the following examples, the pH of the treatment solution was measured at 25°C using a pH meter (Horiba, Ltd., model "F-74") in accordance with JIS Z8802-1984. In addition, in producing the treatment solutions of the examples and comparative examples, handling of containers, preparation, filling, storage and analytical measurements of the treatment solutions were all carried out in a clean room meeting ISO class 2 or lower.

[0135] [Raw materials for treatment solution] The following compounds were used to produce the treatment solution. Note that all of the components used in the examples and comparative examples were classified as semiconductor grade or equivalent high purity grade.

[0136] [Specific compounds and comparative compounds] N-ethylethylenediamine (EEDA) 1,2-propanediamine (12PDA) 1,3-propanediamine (13PDA) 1,3-diaminopentane (13DAP) N-(3-aminopropyl)diethanolamine (3APDEA) Bis(2-aminoethyl)amine (B2AEA) Bis(3-aminopropyl)amine (BAPA) N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (TK2HEEDA) 3-(dibutylamino)propylamine (3DBAPA) N,N'-bis(3-aminopropyl)ethylenediamine (BAPEDA) Tris(3-aminopropyl)amine (T3APA) N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) Tris(2-aminoethyl)amine (T2AEA) N,N,N',N'',N''',N'''-hexamethyltriethylenetetramine (HMTEEA) Ethylenediamine (EDA) Polyethyleneimine (Mw=600)

[0137] [Phosphonic acid compounds] 1-hydroxyethylidene-1,1-diphosphonic acid (HEDPO), ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentakis(methylphosphonic acid) (DTPMP), nitrilotris(methylenephosphonic acid) (NMPA), phytic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA), iminodi(methylenephosphonic acid) (IDMP), ethylaminebis(methylenephosphonic acid) (EABMP), methylaminedi(methylenephosphonic acid) (MADP), N,N-dimethylaminomethylphosphonic acid (DAMP), hydroxymethylphosphonic acid (HMP), aminomethylphosphonic acid (AMPA), methylphosphonic acid (MP)

[0138] [Basic amino acids] ・Arginine ・Histidine ・Lysine

[0139] [Antibacterial agents] Benzethonium chloride, sorbic acid, dehydroacetic acid, cresol, MIT (methylisothiazolinone), OIT (octylisothiazolinone), BIT (benzisothiazolinone), benzoic acid, salicylic acid

[0140] [Organic acids] ・Tartaric acid ・Citric acid ・Malic acid ・Succinic acid ・Malic acid

[0141] [Other additives] β-cyclodextrin (β-CD) Polyacrylic acid (Mw=5,000) Acrylic acid-sulfonic acid copolymer (product name: Aron A-6012 (manufactured by Toagosei Co., Ltd.)) Polysulfonic acid (Mw=12,000)

[0142] [Preparation of Treatment Solution] The method for preparing the treatment solution will be described. The above compounds were added in the amounts shown in the table below and thoroughly stirred to obtain concentrated solutions. The resulting concentrated solutions were diluted with deionized water at the dilution ratios (volume ratios) shown in the "Dilution Ratio" column in the table below to obtain treatment solutions for each Example and Comparative Example. The pH in the table is the pH of the treatment solution obtained by dilution, and was adjusted as needed by adding a pH adjuster selected from the group consisting of tris(hydroxymethyl)aminomethane, DMAMP, Tris, DEA, TEA, MEA, and sulfuric acid. The remaining components (remainder) of the treatment solution that are not explicitly listed as components of the treatment solution in the table are deionized water and a pH adjuster. In all treatment solutions, the content of the pH adjuster was less than 1% by mass relative to the total mass of the treatment solution.

[0143] [Evaluation 1] [Removability of organic residue] Using the treatment solution produced by the above method, the removability of organic residue was evaluated when a workpiece that had been subjected to CMP treatment was treated in the following procedure. Using a FREX300S-II (polishing device, manufactured by Ebara Corporation), and using FSL3400C (trade name, manufactured by Fujifilm Electronic Materials Co., Ltd.) containing 3% by mass of hydrogen peroxide as the polishing solution, the polishing pressure was 2.0 psi (138 hPa), and the polishing solution supply rate was 0.28 mL / (min cm ２ A wafer (12 inches in diameter) having a W film on its surface was polished under the conditions of a temperature of 1000 K, a polishing time of 60 seconds, and a polishing time of 60 seconds. The resulting CMP-treated wafer was then scrubbed for 60 seconds using the treatment solution of each Example or Comparative Example adjusted to room temperature (23° C.), washed for 30 seconds with deionized water, and then dried.

[0144] Using a defect detection device (ComPlus-II, manufactured by AMAT Corporation), the number of detected signal intensities corresponding to defects having a length of more than 0.1 μm was counted on the polished surface of the obtained wafer. The defects corresponding to the above were observed with a defect review SEM (SEMVISION G5, manufactured by AMAT Corporation), and those recognized as organic matter were counted to determine the number of organic residue defects on the polished surface of the wafer. From the obtained number of defects, the removability of organic residue was evaluated according to the following evaluation criteria. In practical terms, a rating of D or higher is preferable.

[0145] A: The number of defects per wafer is less than 20. B: The number of defects per wafer is 20 or more but less than 30. C: The number of defects per wafer is 30 or more but less than 50. D: The number of defects per wafer is 50 or more but less than 100. E: The number of defects per wafer is 100 or more.

[0146] [Corrosion Inhibition] Using the treatment solution produced by the above method, corrosion inhibition against tungsten was evaluated according to the following procedure. A 2 × 2 cm W wafer was prepared. The wafer was placed in a container filled with the treatment solution of each Example or Comparative Example and subjected to an immersion treatment at room temperature (25°C) for 30 minutes. The film thickness of the obtained wafer was then measured using a VR250 (resistivity meter, manufactured by Kokusai Electric Semiconductor Services Co., Ltd.), and the etching rate (Å / min) was calculated from the difference in film thickness before and after the immersion treatment. The corrosion inhibition was evaluated from the etching rate according to the following evaluation criteria. The lower the etching rate, the better the corrosion inhibition. In practical use, a rating of D or higher is preferable.

[0147] A: Less than 0.4 Å / min B: 0.4 Å / min or more and less than 0.6 Å / min C: 0.6 Å / min or more and less than 0.8 Å / min D: 0.8 Å / min or more and less than 1.0 Å / min E: 1.0 Å / min or more

[0148] [Iron oxide residue removability] Using the treatment solution prepared by the above method, the iron oxide residue removability was evaluated according to the following procedure. ２ O ３A wafer on which an (iron oxide) film was formed was prepared. The wafer was placed in a container filled with the treatment solution of each Example or Comparative Example, and subjected to an immersion treatment at room temperature (25°C) for 30 minutes. Thereafter, the film thickness of the obtained wafer was measured using an ellipsometer (M-2000XI manufactured by J.A. Woollam Japan Co., Ltd.), and the etching rate (Å / min) was calculated from the difference in film thickness before and after the immersion treatment. The removability of iron oxide residue was evaluated from the etching rate according to the following evaluation criteria. The higher the etching rate, the better the ability to dissolve iron oxide, i.e., the better the removability of iron oxide residue. In practical use, a rating of D or higher is preferable.

[0149] A: 10.0 Å / min or more B: 8.0 Å / min or more and less than 10.0 Å / min C: 6.0 Å / min or more and less than 8.0 Å / min D: 3.0 Å / min or more and less than 6.0 Å / min E: Less than 3.0 Å / min

[0150] [Results] Tables 1 to 4 show the compositions and evaluation results of each example and treatment solution. Table 4 is a continuation of Table 3. For example, the treatment solution of Example 51 was a solution obtained by diluting a concentrated solution containing 0.5% by mass of EEDA, 3.0% by mass of HEDPO, 0.5% by mass of arginine, 0.05% by mass of sorbic acid, 0.4% by mass of tartaric acid, and 0.5% by mass of polyacrylic acid 100 times. In the table, the "Amount" column indicates the content (% by mass) of each component relative to the total mass of the concentrated solution. In the table, the "a / b" column indicates the mass ratio of the content of the (a) specific compound to the content of the (b) phosphonic acid compound (content of specific compound / content of phosphonic acid compound). In the table, the "a / c" column indicates the mass ratio of the content of the (a) specific compound to the content of the (c) basic amino acid (content of specific compound / content of basic amino acid). In the table, the "Dilution ratio" column indicates the dilution ratio (volume ratio) of the concentrate when preparing the treatment solution, as described above. In the table, the numerical value in the pH column indicates the pH of the treatment solution at 25°C, measured using the pH meter described above. Note that the pH is the value measured for the treatment solution prepared by diluting the concentrate.

[0151]

[0152]

[0153]

[0154]

[0155] The results in the above table confirm that the treatment solution of the present invention can inhibit corrosion of tungsten or molybdenum, is excellent in organic residue removal properties, and is also excellent in iron oxide residue removal properties. On the other hand, the results of the comparative examples confirm that treatment solutions that do not satisfy the requirements of the present invention do not achieve the desired level in at least one of the inhibition of corrosion of tungsten or molybdenum, organic residue removal properties, and iron oxide residue removal properties.

[0156] A comparison of Examples 1 to 5 and Examples 32 and 33 confirmed that when the content of the specific compound was 0.002 mass% or more relative to the total mass of the treatment solution, the organic residue removability was superior, and when it was 0.1 mass% or less, the corrosion inhibition property was superior. A comparison of Examples 1 to 5 and Examples 33 to 36 confirmed that when the content of the phosphonic acid compound was 0.01 mass% or more relative to the total mass of the treatment solution, the iron oxide residue removability was superior. A comparison of Examples 21 and 22 and Example 18 confirmed that when the mass ratio of the content of the specific compound to the content of the basic amino acid was 0.2 or more, the organic residue removability and the iron oxide residue removability were superior, and when it was 10.0 or less, the corrosion inhibition property was superior. A comparison of Examples 18 and 22 to 29 confirmed that when the pH was 3.0 or higher, organic residue removability and iron oxide residue removability were superior, when the pH was 5.0 or higher, organic residue removability was even superior, when the pH was 9.0 or lower, corrosion inhibition was superior, and when the pH was 8.0 or lower, corrosion inhibition was even superior. A comparison of Examples 18 to 20 with Examples 30 and 31 confirmed that when the treatment solution contained cyclodextrin or a derivative thereof, organic residue removability was superior. A comparison of Examples 1 and 32 to 36 confirmed that when the mass ratio of the content of the specific compound to the content of the phosphonic acid compound was 0.01 or higher, organic residue removability was superior, when the mass ratio was 0.1 or higher, corrosion inhibition was superior, when the mass ratio was 10.0 or lower, iron oxide residue removability was superior, and when the mass ratio was 1.0 or lower, iron oxide residue removability was even superior. A comparison of Examples 37 to 50 confirmed that when the log D value of the specific compound at pH 7.4 is -6.0 or higher, the effect of the present invention is better, and when it is -2.0 or lower, the organic residue removability is better. A comparison of Examples 37 to 50 confirmed that when the specific compound has 2 or 3 nitrogen atoms, the effect of the present invention is better. A comparison of Examples 37 to 50 confirmed that when the specific compound has 3 to 11 carbon atoms, the organic residue removability is better, and when it has 3 to 9 carbon atoms, the organic residue removability is even better.A comparison of Examples 1 and 2 with Examples 51 to 68 confirmed that iron oxide residue removability was superior when the treatment solution contained a low-molecular-weight organic acid other than a phosphonic acid compound. A comparison of Examples 69 to 74 with Examples 51 to 68 confirmed that corrosion inhibition was superior when the anionic polymer was polyacrylic acid. A comparison of Examples 75 to 82 confirmed that corrosion inhibition was superior when the pH was 9.0 or less, and even superior when the pH was 8.0 or less. Furthermore, it was confirmed that organic residue removability was superior when the pH was 3.0 or higher, even superior when the pH was 5.0 or higher, and particularly superior when the pH was 7.0 or higher.

[0157] [Evaluation 2] The removability of organic residues in a system that had been subjected to buff cleaning was evaluated according to the following procedure.

[0158] Concentrated solutions 1 to 12 were prepared as aqueous solutions containing 10% by mass of Tween-20 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and having a pH of 1.6, 2, 2.5, 3, 3.5, 4, 5, 6, 7, 8, 8.4, or 9, respectively. Concentrated solution 13 was prepared as above, containing 10% by mass of Tween-20 and 3.0% by mass of HEDPO, and having a pH of 3. The pH of solutions 1 to 8 was adjusted using nitric acid, and the pH of solutions 9 to 13 was adjusted using Tris. Concentrated solutions 14 and 15 were prepared as aqueous solutions containing 10% by mass of Tween-40 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and having a pH of 1.6 or 3, respectively. Concentrated solution 16 was prepared as an aqueous solution containing 10% by mass of Tween-40 and 0.05% by mass of MIT, and having a pH of 8. The pH of chemical solutions 14 and 15 was adjusted using nitric acid, and the pH of chemical solution 16 was adjusted using Tris. Concentrated chemical solutions 17 and 18 were prepared as aqueous solutions containing 10% by mass of Tween-60 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and having a pH of 3 or 8, respectively. The pH of chemical solution 17 was adjusted using nitric acid, and the pH of chemical solution 18 was adjusted using Tris. Concentrated chemical solutions 19 and 20 were prepared as aqueous solutions containing 10% by mass of Tween-80 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and having a pH of 1.6 or 7, respectively. Concentrated chemical solution 21 was prepared as an aqueous solution containing 10% by mass of Tween-80 and 0.05% by mass of MIT and having a pH of 8.4. The pH of chemical solution 19 was adjusted using nitric acid, and the pH of chemical solutions 20 and 21 was adjusted using Tris. Concentrated chemical solutions 22 to 24 were prepared as aqueous solutions containing 0.3 mass%, 1 mass%, or 3 mass% Tween-20, 0.05 mass% MIT, and a pH of 7. The pH of chemical solutions 22 to 24 was adjusted using Tris. DIW was used as the water in the concentrated chemical solutions. The concentrated chemical solutions 1 to 24 were diluted 10 times with DIW to prepare chemical solutions 1 to 24.

[0159] [Organic Residue Removability] A wafer was prepared that had been subjected to CMP processing according to the procedure described in [Organic Residue Removability] in [Evaluation 1] above. Next, using a FREX300S-II (polishing device, manufactured by Ebara Corporation), the prepared chemical solution 1 was used, and the pressure was set to 0.5 psi (35 hPa) and the chemical solution supply rate was set to 0.28 mL / (min cm ２The resulting CMP-treated wafer (12 inches in diameter) was buffed under conditions of 1000 kJ / min, 1000 kcal / min, and 20 seconds of treatment time. The resulting CMP-treated and buff-cleaned wafer was then scrubbed for 60 seconds using the treatment solution of Example 28 adjusted to room temperature (23°C), rinsed for 30 seconds with deionized water, and then dried. When evaluation was performed according to the procedure described in [Evaluation 1] [Organic Residue Removability] above, the organic residue removability evaluation improved by one level, confirming that even better results were obtained. Similar results were also obtained when chemical solutions 2 to 23 were used instead of chemical solution 1, and when the treatment solution of Example 28 was used instead of the treatment solution of other Examples or Comparative Examples. Furthermore, the conditions for the buff-cleaning treatment were changed to a pressure of 0.1 to 4 psi and a polishing solution supply rate of 0.07 to 0.56 mL / (min cm). ２ ) Similar results were obtained even when the treatment time was changed between 5 and 60 seconds. These results confirm that by performing buff cleaning treatment using the above chemical solution, it is possible to improve the removability of organic residues under various treatment solutions and buff cleaning conditions.

Claims

1. A treatment liquid comprising a specific compound represented by formula (1) and at least one phosphonic acid compound selected from the group consisting of phosphonic acid and organic phosphonic acid, wherein the mass ratio of the content of the specific compound to the content of the phosphonic acid compound is 0.001 to 20.

0. In formula (1), X １ ~X ４ and R each independently represent a hydrogen atom, or an aliphatic hydrocarbon group which may have a hydroxyl group or an amino group. A plurality of R may be the same or different. A plurality of R may be bonded to each other to form a ring. n is an integer of 2 or more.

2. The treatment liquid according to claim 1, wherein the specific compound has a log D value of -7.2 to -1.0 at pH 7.

4.

3. The treatment liquid according to claim 1, having a pH of 3.0 to 9.

0.

4. The treatment solution according to claim 1, further comprising at least one basic amino acid selected from the group consisting of arginine, histidine, and lysine.

5. The treatment solution according to claim 1, further comprising cyclodextrin or a derivative thereof.

6. The treatment liquid according to claim 4, wherein the mass ratio of the content of the specific compound to the content of the basic amino acid is 0.2 to 10.

0.

7. The treatment liquid according to claim 1, wherein the specific compound contains two or three nitrogen atoms.

8. The treatment liquid according to claim 1, wherein the specific compound contains 3 to 11 carbon atoms.

9. The treatment solution according to claim 1, further comprising an antibacterial agent.

10. The treatment solution according to claim 1, further comprising an anionic polymer.

11. The treatment solution according to claim 1, further comprising a low molecular weight organic acid different from the phosphonic acid compound.

12. A method for treating an object, comprising a step of contacting the object, which contains at least one of tungsten and molybdenum and has been subjected to chemical mechanical polishing, with the treatment liquid according to any one of claims 1 to 11.

13. A method for treating a pad used in chemical mechanical polishing, comprising a step of contacting the pad with the treatment liquid according to any one of claims 1 to 11.

14. A method for manufacturing an electronic device, comprising the method for treating an object as defined in claim 12.

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