Treatment liquid, method for producing treatment liquid, method for treating substrate, and method for manufacturing semiconductor device

Abstract

Provided are a treatment liquid which not only has excellent removability of a metal component and a residue to be removed but also has excellent anticorrosion properties for a metal containing a Cu atom, a method for producing a treatment liquid, a method for treating a substrate using the treatment liquid, and a method for manufacturing a semiconductor device.SOLUTION: Provided are a treatment liquid containing an alkali compound, water, and a corrosion inhibitor, in which the amount of oxygen dissolved after a lapse of one week from the preparation of the treatment liquid is 0. 2mg / L or more and 1. 5mg / L or less, and the corrosion inhibitor is at least one selected from the group consisting of N, N-diethylhydroxylamine, 1-thioglycerol, 1-amino-4-methylpiperazine, carbohydrazide, methyl ethyl ketoxime, erythorbic acid, and salts thereof, a method for producing a treatment liquid, and a method for treating a substrate and a method for manufacturing a semiconductor device using the treatment liquid.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a processing liquid, a method for manufacturing a processing liquid, a method for processing a substrate, and a method for manufacturing a semiconductor device. [Background technology]

[0002] In the manufacturing process of semiconductor substrates, wiring is formed by patterning a substrate on which various metal layers are laminated. In this wiring formation process, unnecessary resist films, filling materials, etching residues, etc. are removed using a processing solution so as not to interfere with the next process. The etching residues to be removed include residues containing metals.

[0003] As a technology relating to such a processing liquid, for example, Patent Document 1 discloses a cleaning liquid used in forming a dual damascene structure, in which a low-dielectric layer (Low-k layer) stacked on a substrate having a metal layer is etched to form a first etching space, a sacrificial layer is filled in the first etching space, and then the low-dielectric layer and the sacrificial layer are partially etched to form a second etching space communicating with the first etching space, and then the sacrificial layer remaining in the first etching space is removed, the cleaning liquid containing (a) 1 to 25 mass % of a quaternary ammonium hydroxide, (b) 30 to 70 mass % of a water-soluble organic solvent, and (c) 20 to 60 mass % of water.

[0004] Furthermore, Patent Document 2 discloses a stripping and cleaning solution containing a quaternary ammonium hydroxide, a water-soluble organic solvent, water, an anticorrosive agent, and potassium hydroxide in an amount of 1 mass % or less relative to the total amount. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-103771 [Patent Document 2] Special Publication No. 2006-527783 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the above-mentioned conventional processing solutions have a problem in that even if they can remove the resist film, the filling material, and the metal residues, they can damage (corrode) the substrate having a metal layer. For example, in the case of processing a substrate having a metal layer containing Cu atoms or a substrate containing Cu atoms, even if they can remove the resist film, the filling material, and the residues to some extent, the metal layer and the substrate may be damaged.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a processing liquid that is not only excellent in removing metal components and residues to be removed, but also has excellent corrosion prevention properties for metals containing Cu atoms, a method for manufacturing the processing liquid, and a method for processing substrates and manufacturing semiconductor devices using the processing liquid. [Means for solving the problem]

[0008] As a result of extensive research into achieving the above-mentioned object, the present inventors have discovered that a treatment solution containing an alkaline compound, water, and a corrosion inhibitor has a dissolved oxygen content of 0.2 mg / L or more and 1.5 mg / L or less one week after the time of preparation of the treatment solution, and the corrosion inhibitor is at least one selected from the group consisting of N,N-diethylhydroxylamine, 1-thioglycerol, 1-amino-4-methylpiperazine, carbohydrazide, methyl ethyl ketoxime, erythorbic acid, and salts thereof, and have completed the present invention.

[0009] That is, the present invention is as follows. <1> The treatment solution contains an alkaline compound, water, and a corrosion inhibitor, wherein the amount of dissolved oxygen in the treatment solution one week after preparation is 0.2 mg / L or more and 1.5 mg / L or less, and the corrosion inhibitor is at least one selected from the group consisting of N,N-diethylhydroxylamine, 1-thioglycerol, 1-amino-4-methylpiperazine, carbohydrazide, methyl ethyl ketoxime, erythorbic acid, and salts thereof. <2> further comprising an antioxidant, <1> The processing solution is as described in <3> The content of the alkali compound is more than 10% by mass and not more than 20% by mass. <1> The processing solution is as described in <4> The water content is 50% by mass or more and 85% by mass or less. <1> The processing solution is as described in <5> The content of the corrosion inhibitor is 0.005% by mass or more and 5% by mass or less. <1> The processing solution is as described in <6> The content of the antioxidant is 0.001% by mass or more and 5% by mass or less. <2> The processing solution is as described in <7> The amount of dissolved oxygen in the treatment solution at the time of preparation is 0.2 mg / L or more and 6 mg / L or less. <1> The processing solution is as described in <8> the processing liquid is a processing liquid for processing a substrate having a metal layer, and the substrate and / or the metal layer contains Cu atoms; <1> The processing solution is as described in <9> the processing liquid is used to remove residues generated after etching processing is performed on the substrate having the metal layer; <8> The processing solution is as described in <10> The method for producing a treatment liquid includes a preparation step of mixing an alkaline compound, water, and a corrosion inhibitor to prepare a treatment liquid, wherein the amount of dissolved oxygen in the treatment liquid one week after preparation is 0.2 mg / L or more and 1.5 mg / L or less, and the corrosion inhibitor is at least one selected from the group consisting of N,N-diethylhydroxylamine, 1-thioglycerol, 1-amino-4-methylpiperazine, carbohydrazide, methyl ethyl ketoxime, erythorbic acid, and salts thereof. <11> The amount of dissolved oxygen in the treatment solution during the preparation step is 0.2 mg / L or more and 6 mg / L or less. <10> 2. A method for producing the treatment liquid according to claim 1. <12> providing a substrate having a metal layer; etching the metal layer; and after the etching, <1> and removing impurities from the substrate by bringing the processing liquid described in the above into contact with the substrate. <13> providing a substrate having a metal layer; etching the metal layer; and after the etching, <1> and removing impurities from the substrate by bringing the treatment liquid described in item 1 into contact with the substrate. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a processing liquid that is not only excellent in removing metal components and residues to be removed, but also has excellent corrosion prevention properties for metals containing Cu atoms, a method for manufacturing the processing liquid, and a method for processing a substrate and a method for manufacturing a semiconductor device using the processing liquid. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be practiced by appropriately modifying it within the scope of its gist. Furthermore, unless otherwise specified, the configurations and parameters disclosed in this specification can be arbitrarily combined. Furthermore, unless otherwise specified, the upper and lower limits of the values ​​disclosed in this specification can be arbitrarily combined.

[0012] <Processing liquid>

[0013] The treatment liquid according to this embodiment contains an alkaline compound, water, and a corrosion inhibitor, and has a dissolved oxygen content of 0.2 mg / L to 1.5 mg / L one week after preparation of the treatment liquid, and the corrosion inhibitor is at least one selected from the group consisting of N,N-diethylhydroxylamine, 1-thioglycerol, 1-amino-4-methylpiperazine, carbohydrazide, methyl ethyl ketoxime, erythorbic acid, and salts thereof. The treatment liquid according to this embodiment may also be called a cleaning liquid, a stripping liquid, or the like.

[0014] The treatment solution according to this embodiment not only excels in the removal of metal components and residues to be removed, but also in the corrosion prevention of metals containing Cu atoms. Regarding the corrosion prevention, for example, damage to metal layers containing Cu atoms and substrates containing Cu atoms can be suppressed. Furthermore, regarding the removability, for example, the treatment solution can remove metal components to be removed, such as resist films and filling materials, and residues from etching, etc. (However, the functions and effects according to this embodiment are not limited to these).

[0015] Furthermore, the treatment solution according to this embodiment is expected to suppress damage to low-k materials and the like. For example, a low-dielectric constant film such as a low-k film may also be formed on a substrate on which the above-mentioned metal layer containing Cu atoms is wired. The treatment solution according to this embodiment is expected to remove resist film, filling material, and metal residues while suppressing damage to the low-k film.

[0016] The components and properties of the treatment liquid according to this embodiment will be described below.

[0017] (alkali compounds)

[0018] The treatment liquid according to this embodiment contains an alkaline compound. The alkaline compound is not particularly limited as long as it exhibits basicity when dissolved in water, and both organic and inorganic alkaline compounds can be used.

[0019] Examples of organic alkaline compounds include quaternary ammonium salts such as organic quaternary ammonium hydroxides; alkanolamines; and organic amines other than alkanolamines such as primary amines, secondary amines, tertiary amines, and amidines.

[0020] Examples of organic quaternary ammonium hydroxides include tetramethylammonium hydroxide (TMAH), bis(2-hydroxyethyl)dimethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, trimethyl(hydroxyethyl)ammonium hydroxide, triethyl(hydroxyethyl)ammonium hydroxide, tetrapentylammonium hydroxide, monomethyl triple ammonium hydroxide, trimethylethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, (2-hydroxyethyl)triethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide, and (1-hydroxypropyl)trimethylammonium hydroxide.

[0021] Examples of alkanolamines include diisopropanolamine, aminoethylethanolamine, monoethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, monoisopropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-amino-propan-1-ol, N-ethyl-2-amino-propan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutan-2-ol, 2-aminobutan-1-ol, and N-methyl-2-aminobutan-1-ol. N-ethyl-2-aminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutan-4-ol, N-methyl-1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino 4-methylpentan-1-ol, 2-aminohexan-1-ol, 3-aminoheptan-4-ol, 1-aminooctan-2-ol, 5-aminooctan-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(oxymethyl)aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2-(2-aminoethoxy)ethanol, and the like.

[0022] Other organic amines include, for example, diazabicycloundecene.

[0023] Among the organic alkaline compounds, quaternary ammonium salts are preferred, organic quaternary ammonium hydroxides are more preferred, and tetramethylammonium hydroxide is even more preferred.

[0024] Examples of inorganic alkali compounds include inorganic compounds containing ammonia, alkali metals, or alkaline earth metals, and salts thereof. Examples of inorganic compounds containing alkali metals or alkaline earth metals and salts thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Among these, potassium hydroxide is preferred.

[0025] The alkaline compounds may be used alone or in combination of two or more.

[0026] The content of the alkali compound in the treatment liquid according to this embodiment is not particularly limited, but is preferably more than 10% by mass and not more than 20% by mass. The lower limit of this content is more preferably 11% by mass or more, and even more preferably 12% by mass or more. The upper limit of this content is more preferably 18% by mass or less, and even more preferably 16% by mass or less. By setting the content of the alkali compound within the above-mentioned range, it is possible to further improve the balance between the removability of the metal components and residues to be removed and the corrosion prevention of metals containing Cu atoms. When two or more alkali compounds are used in combination, it is preferable that the total amount of the alkali compounds is within the above-mentioned content range.

[0027] The content of the organic alkali compound in the treatment solution according to this embodiment is not particularly limited, but is preferably more than 10% by mass and not more than 20% by mass. The lower limit of this content is more preferably 11% by mass or more, and even more preferably 12% by mass or more. The upper limit of this content is more preferably 18% by mass or less, and even more preferably 16% by mass or less. By setting the content of the organic alkali compound within the above-mentioned range, it is possible to further improve the balance between the removability of the metal components and residues to be removed and the corrosion prevention of metals containing Cu atoms. When two or more organic alkali compounds are used in combination, it is preferable that the total amount of the organic alkali compounds is within the above-mentioned content range.

[0028] The content of the inorganic alkali compound in the treatment solution according to this embodiment is not particularly limited, but is preferably 0.01% by mass or more and 10% by mass or less. The lower limit of this content is more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. The upper limit of this content is more preferably 5% by mass or less, and even more preferably 1% by mass or less. By setting the content of the inorganic alkali compound within the above-mentioned range, it is possible to further improve the balance between the removability of the metal components and residues to be removed and the corrosion prevention of metals containing Cu atoms. When two or more inorganic alkali compounds are used in combination, it is preferable that the total amount of the inorganic alkali compounds be within the above-mentioned content range.

[0029] (water)

[0030] The treatment liquid according to this embodiment contains water. The water is preferably water from which metal ions, organic impurities, and particles have been removed, or the content of these impurities has been reduced, by distillation, ion exchange treatment, filtering, various adsorption treatments, or the like. Examples of water that can be used include pure water, ultrapure water, and deionized water (DIW). By including water as a solvent, the treatment liquid according to this embodiment can be suitably used as a so-called aqueous treatment liquid (sometimes referred to as an aqueous treatment liquid, etc.).

[0031] The content of water can be selected to be a suitable amount depending on the type of component to be treated and the intended use. During preparation, necessary components other than water may be added, with water being added as the remainder.

[0032] The water content in the treatment liquid according to this embodiment is preferably 50% by mass or more and 85% by mass or less. The lower limit is more preferably 52% by mass or more, and even more preferably 55% by mass or more. The upper limit is more preferably 80% by mass or less, and even more preferably 70% by mass or less. By keeping the water content within the above range, the advantages of the aqueous treatment liquid can be more effectively exhibited. Furthermore, by keeping the water content within the above range, the balance between the removability of the metal components and residues to be removed and the corrosion prevention properties of metals containing Cu atoms can be further improved.

[0033] (corrosion inhibitor)

[0034] The treatment solution according to this embodiment contains a corrosion inhibitor. The corrosion inhibitor is at least one selected from the group consisting of N,N-diethylhydroxylamine, 1-thioglycerol, 1-amino-4-methylpiperazine, carbohydrazide, methyl ethyl ketoxime, erythorbic acid, and salts thereof. Examples of these salts include sodium salts, potassium salts, calcium salts, barium salts, ammonium salts, and tetraalkylammonium salts. A preferred example of such a salt is sodium erythorbate. When a corrosion inhibitor is added, a hydrate may also be added.

[0035] The content of the corrosion inhibitor in the treatment solution according to this embodiment is not particularly limited, but is preferably 0.005% by mass or more and 5% by mass or less. The lower limit of this content is more preferably 0.05% by mass or more, and even more preferably 0.4% by mass or more. The upper limit of this content is more preferably 2% by mass or less, and even more preferably 1% by mass or less. By setting the content of the corrosion inhibitor within this range, it is possible to further improve the balance between corrosion prevention of metals containing Cu atoms and removability of the metal components and residues to be removed. When a hydrate is added as the corrosion inhibitor, it is preferable that the net content excluding the water of hydration contained in the hydrate be within the above-mentioned range.

[0036] (Other corrosion inhibitors)

[0037] The treatment solution according to this embodiment may further contain other corrosion inhibitors in addition to the corrosion inhibitors described above. Examples of other corrosion inhibitors include compounds containing a nitrogen-containing heterocycle such as a triazole ring, an imidazole ring, a pyridine ring, a phenanthroline ring, a tetrazole ring, a pyrazole ring, a pyrimidine ring, or a purine ring.

[0038] Examples of compounds containing a triazole ring include triazoles such as 1,2,3-triazole, 1,2,4-triazole, 3-amino-1H-1,2,4-triazole, 1-acetyl-1H-1,2,3-triazolo[4,5-b]pyridine, 1H-1,2,3-triazolo[4,5-b]pyridine, 1,2,4-triazolo[4,3-a]pyridin-3(2H)-one, and 3H-1,2,3-triazolo[4,5-b]pyridin-3-ol; 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 1-hydroxybenzotriazole, 1-hydroxypropylbenzotriazole, and 2,3-dicarboxypropylbenzotriazole. and benzotriazoles such as 1,2,3-benzotriazole, 4-hydroxybenzotriazole, 4-carboxyl-1H-benzotriazole, 4-carboxyl-1H-benzotriazole methyl ester, 4-carboxyl-1H-benzotriazole butyl ester, 4-carboxyl-1H-benzotriazole octyl ester, 5-hexylbenzotriazole, [1,2,3-benzotriazolyl-1-methyl][1,2,4-triazolyl-1-methyl][2-ethylhexyl]amine, tolyltriazole, naphthotriazole, bis[(1-benzotriazolyl)methyl]phosphonic acid, and 3-aminotriazole.

[0039] Examples of compounds containing an imidazole ring include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-propylimidazole, 2-butylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 2-aminoimidazole; and biimidazoles such as 2,2'-biimidazole.

[0040] Examples of compounds containing a pyridine ring include pyridines such as 1H-1,2,3-triazolo[4,5-b]pyridine, 1-acetyl-1H-1,2,3-triazolo[4,5-b]pyridine, 3-aminopyridine, 4-aminopyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-acetamidopyridine, 4-pyrrolidinopyridine, 2-cyanopyridine, 2,6-pyridinecarboxylic acid, and 2,4,6-trimethylpyridine; and bipyridyls such as 2,2′-bipyridyl, 4,4′-dimethyl-2,2′-bipyridyl, 4,4′-di-tert-butyl-2,2′-bipyridyl, 4,4′-dinonyl-2,2′-bipyridyl, 2,2″-bipyridine-6,6′-dicarboxylic acid, and 4,4′-dimethoxy-2,2′-bipyridyl.

[0041] An example of a compound containing a phenanthroline ring is 1,10-phenanthroline.

[0042] Examples of compounds containing a tetrazole ring include 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, and 1-(2-diaminoethyl)-5-mercaptotetrazole.

[0043] Examples of compounds containing a pyrazole ring include 3,5-dimethylpyrazole, 3-amino-5-methylpyrazole, 4-methylpyrazole, and 3-amino-5-hydroxypyrazole.

[0044] Examples of compounds containing a pyrimidine ring include pyrimidine, 4-methylpyrimidine, 1,2,4-triazolo[1,5-a]pyrimidine, 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine, 1,3-diphenyl-pyrimidine-2,4,6-trione, 1,4,5,6-tetrahydropyrimidine, 2,4,5,6-tetraaminopyrimidine sulfate, 2,4,5-trihydroxypyrimidine, 2,4,6-triaminopyrimidine, 2,4,6-trichloropyrimidine, 2,4,6-trimethoxypyrimidine, 2, Examples include 4,6-triphenylpyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4-diaminopyrimidine, 2-acetamidopyrimidine, 2-aminopyrimidine, 2-methyl-5,7-diphenyl-(1,2,4)triazolo(1,5-a)pyrimidine, 2-methylsulfanyl-5,7-diphenyl-(1,2,4)triazolo(1,5-a)pyrimidine, 2-methylsulfanyl-5,7-diphenyl-4,7-dihydro-(1,2,4)triazolo(1,5-a)pyrimidine, and 4-aminopyrazolo[3,4-d]pyrimidine.

[0045] Compounds containing a purine ring include adenine, guanine, hypoxanthine, xanthine, uric acid, theophylline, and the like.

[0046] The above-mentioned corrosion inhibitors may be used alone or in combination of two or more.

[0047] The treatment solution according to this embodiment can achieve sufficient corrosion prevention properties even without the corrosion inhibitors described above. For example, the treatment solution according to this embodiment may not contain one or more compounds selected from the group consisting of compounds containing nitrogen-containing heterocycles (such as triazole rings, imidazole rings, pyridine rings, phenanthroline rings, tetrazole rings, pyrazole rings, pyrimidine rings, and purine rings), ascorbic acids, catechols, sugars, and polycarboxylic acids. Furthermore, the treatment solution according to this embodiment may not contain one or more compounds selected from the group consisting of hydroquinone, catechol, 4-amino-3-methylphenol, sodium sulfite, and ammonium sulfite.

[0048] (antioxidant)

[0049] The treatment liquid according to this embodiment may further contain an antioxidant. The antioxidant is not particularly limited, and any conventionally known antioxidant may be used, such as a phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or an alcohol amine-based antioxidant.

[0050] Examples of phenolic antioxidants include 4,4-thiobis(6-tert-butyl-m-cresol), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), alkylated bisphenols, 2,6-di-t Examples of hindered phenol antioxidants include ert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], and tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate.

[0051] Examples of the hindered amine antioxidant include bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate.

[0052] Examples of phosphorus-based antioxidants include tris(2,4-di-tert-butylphenyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene phosphite, trisnonylphenyl phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and distearyl pentaerythritol diphosphite.

[0053] Examples of sulfur-based antioxidants include dilauryl 3,3-thiodipropionate, dimyristyl 3,3-thiodipropionate, distearyl 3,3-thiodipropionate, ditridecyl 3,3-thiodipropionate, pentaerythrityl tetrakis(3-laurylthiodipropionate), and 2-mercaptobenzimidazole.

[0054] Examples of the alcohol amine antioxidant include monoethanolamine, diethanolamine, triethanolamine, aminoethylethanolamine, tris-(hydroxyl-methyl)amino-methane, methyldiethanolamine, dimethylethanolamine, and N-methyldiethanolamine.

[0055] Among these, from the viewpoints of preventing oxidation, preventing thermal oxidation, and suppressing odor, alcoholamine-based antioxidants are preferred, and monoethanolamine is more preferred.

[0056] The content of the antioxidant in the treatment liquid according to this embodiment is not particularly limited, but is preferably 0.001% by mass or more and 5% by mass or less. The lower limit of this content is more preferably 0.05% by mass or more, and even more preferably 0.2% by mass or more. The upper limit of this content is more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less. When this content is equal to or greater than the above-mentioned lower limit, a greater antioxidant effect can be obtained. When this content is equal to or less than the above-mentioned upper limit, the substrate can be cleaned more efficiently.

[0057] (dissolved oxygen content)

[0058] The treatment solution according to this embodiment has a dissolved oxygen content of 0.2 mg / L or more and 1.5 mg / L or less one week after preparation of the treatment solution (hereinafter, sometimes simply referred to as "dissolved oxygen content after one week"). By blending the above-described components and controlling the dissolved oxygen content after one week to fall within this range, the treatment solution according to this embodiment not only has excellent removability of the target metal components and residues, but also suppresses corrosion (damage) of metals containing Cu atoms. Furthermore, by appropriately controlling the components contained in the treatment solution according to this embodiment and their contents, it is expected that the dissolved oxygen content after one week can be controlled even more effectively.

[0059] The lower limit of the dissolved oxygen content after one week is preferably 0.25 mg / L or more, more preferably 0.30 mg / L or more, and even more preferably 0.35 mg / L or more. The upper limit is preferably 1.49 mg / L or less. By keeping the dissolved oxygen content after one week within the above range, it is possible to further improve the balance between the removability of the metal components and residues to be removed and the corrosion prevention of metals containing Cu atoms.

[0060] Furthermore, the amount of dissolved oxygen during preparation of the treatment solution (hereinafter sometimes simply referred to as "dissolved oxygen amount during preparation") is not particularly limited, but is preferably 0.2 mg / L or more and 6 mg / L or less. The lower limit of the amount of dissolved oxygen during preparation is preferably 0.22 mg / L or more, more preferably 0.23 mg / L or more. The upper limit is preferably 5.8 mg / L or less, more preferably 5.5 mg / L or less. In addition to controlling the amount of dissolved oxygen after one week, by controlling the amount of dissolved oxygen during preparation to be within the above-mentioned range, the balance between the removability of metal components and residues to be removed and the corrosion prevention of metals containing Cu atoms can be further improved. Furthermore, in the treatment solution according to this embodiment, by appropriately controlling the components contained and their contents, it is expected that the amount of dissolved oxygen during preparation can be more effectively controlled.

[0061] (Other ingredients)

[0062] The treatment solution according to this embodiment may further contain optional components other than the components described above, as long as the effects of this embodiment can be obtained. Such optional components can be appropriately selected in consideration of the composition of the treatment solution, the intended use, the material and structure of the semiconductor substrate to be treated, and the like. Examples of such optional components include surfactants, pH adjusters, buffers, and the like.

[0063] (surfactant)

[0064] The treatment liquid according to this embodiment may contain a surfactant for the purposes of preventing foaming, adjusting the wettability of the treatment liquid with respect to the substrate, etc. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

[0065] Examples of nonionic surfactants include polyalkylene oxide alkyl phenyl ether surfactants, polyalkylene oxide alkyl ether surfactants, block polymer surfactants consisting of polyethylene oxide and polypropylene oxide, polyoxyalkylene distyrene-substituted phenyl ether surfactants, polyalkylene tribenzyl phenyl ether surfactants, and acetylene polyalkylene oxide surfactants.

[0066] These surfactants may be commercially available products, etc. One surfactant may be used alone, or two or more surfactants may be used in combination.

[0067] When the treatment liquid according to the present embodiment contains a surfactant, the content of the surfactant is not particularly limited, but is typically, for example, 0.0001 to 5% by mass relative to the total mass of the treatment liquid. When the content of the surfactant is within the above range, the bubbles generated by the foaming agent tend to be dense.

[0068] The treatment liquid according to this embodiment may not contain one or more surfactants selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and may not contain one or more of the compounds exemplified above as these surfactants. The treatment liquid according to this embodiment may not contain a surfactant.

[0069] (pH adjuster)

[0070] The treatment solution according to this embodiment may contain a pH adjuster. Examples of pH adjusters include acidic compounds and basic compounds. The basic compound may be an organic basic compound or an inorganic basic compound. However, the basic compound used as the pH adjuster is a compound other than the alkaline compound used in this embodiment. Examples of pH adjusters include methanesulfonic acid (MSA), phosphoric acid (H3PO4, H4P2O7, HPO3), carboxylic acids, boric acid (H3BO3, B(OH)3), phosphorous acid (H3PO3), carbonic acid (H2CO3), orthocarbonic acid (H4CO4, C(OH)4CH4O4), sulfuric acid, and hydrochloric acid. Carboxylic acids are acids having at least one carboxy group (-COOH). Preferred examples of carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, and valeric acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid; and tricarboxylic acids such as citric acid.

[0071] The treatment liquid according to this embodiment may not contain a pH adjuster. For example, the treatment liquid according to this embodiment may not contain one or more of the compounds exemplified above as pH adjusters, or may not contain one or more selected from the group consisting of methanesulfonic acid, phosphoric acid, carboxylic acids, boric acid, phosphorous acid, carbonic acid, orthocarbonic acid, sulfuric acid, and hydrochloric acid.

[0072] (buffering agent)

[0073] The treatment liquid according to this embodiment may contain a buffering agent. The buffering agent is a compound that has the effect of suppressing changes in the pH of the solution. As the buffering agent, a compound having pH buffering ability can be used as appropriate.

[0074] The buffering agent may be used alone or in combination of two or more. When the treatment liquid according to this embodiment contains a buffering agent, the content of the buffering agent is not particularly limited, but is typically 0.001 to 10% by mass relative to the total mass of the treatment liquid. The treatment liquid according to this embodiment does not necessarily contain a buffering agent.

[0075] (organic solvent)

[0076] The treatment liquid according to this embodiment may further contain an organic solvent. The type of organic solvent is not particularly limited, and an appropriate organic solvent can be selected taking into consideration the type and content of other components used. As the organic solvent, for example, an organic solvent that is miscible with the above-mentioned alkaline compound, water, corrosion inhibitor, and other added components can be used. As the organic solvent, a water-soluble organic solvent is preferred.

[0077] Specific examples of the water-soluble organic solvent include alcohols such as isopropanol, ethanol, ethylene glycol, propylene glycol, glycerin, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, furfuryl alcohol, and 2-methyl-2,4-pentanediol; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; and dimethyl sulfoxide (DMSO). sulfones such as dimethyl sulfone, diethyl sulfone, bis(2-hydroxyethyl) sulfone, and tetramethylene sulfone; amides such as N,N-dimethylformamide (DMF), N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, and N,N-diethylacetamide; lactams such as N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone; imidazolidinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone; lactones such as γ-butyrolactone and δ-valerolactone, and derivatives thereof. Among these, sulfoxides are preferred, and dimethyl sulfoxide is more preferred.

[0078] These organic solvents may be used alone or in combination of two or more.

[0079] The treatment liquid according to this embodiment is preferably an aqueous treatment liquid from the viewpoints of component solubility, environmental load reduction, and cost efficiency. A suitable example of an aqueous treatment liquid is a treatment liquid containing water and an organic solvent, in which the organic solvent content is lower than the water content. From these viewpoints, the organic solvent content relative to the total water content and organic solvent content is preferably 0.1% by mass or more and 50% by mass or less. The upper limit of this content is more preferably 40% by mass or less, and even more preferably 35% by mass or less. The lower limit of this content may be 0.1% by mass or more, or may be 1% by mass or more.

[0080] Furthermore, the content of the organic solvent in the treatment liquid according to this embodiment is preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, and even more preferably 28% by mass or less. By setting the content of the organic solvent within the above-mentioned range, the advantages of the aqueous treatment liquid can be more effectively exhibited. Furthermore, by setting the content of the organic solvent within the above-mentioned range, the balance between the removability of the metal components and residues to be removed and the corrosion prevention properties of metals containing Cu atoms can be further improved.

[0081] (Impurities, etc.)

[0082] The treatment liquid according to this embodiment may contain metal impurities, including metal atoms such as Fe atoms, Cr atoms, Ni atoms, Zn atoms, Ca atoms, or Pb atoms. The total content of the metal atoms in the treatment liquid according to this embodiment is preferably 100 mass ppt or less, based on the total mass of the treatment liquid. The lower limit of the total metal atom content is preferably as low as possible, and may be, for example, 0.001 mass ppt or more. The total metal atom content may be, for example, 0.001 mass ppt to 100 mass ppt. By setting the total metal atom content to the above-mentioned preferred upper limit or less, the defect suppression and residue suppression properties of the treatment liquid are improved. By setting the total metal atom content to the above-mentioned preferred lower limit or more, it is thought that metal atoms are less likely to be isolated and present in the system, which is less likely to adversely affect the overall production yield of the object to be cleaned.

[0083] The content of metal impurities can be adjusted, for example, by a purification treatment such as filtering, etc. The purification treatment such as filtering may be performed on a part or all of the raw materials before preparing the treatment liquid, or may be performed after preparing the treatment liquid.

[0084] The treatment liquid according to this embodiment may contain, for example, impurities derived from organic substances (organic impurities). The total content of the organic impurities in the treatment liquid according to this embodiment is preferably 5000 mass ppm or less. The lower limit of the content of the organic impurities is preferably as low as possible, and may be, for example, 1 mass ppq or more. The total content of the organic impurities may be, for example, 1 mass ppq to 5000 mass ppm.

[0085] The treatment liquid according to this embodiment may contain countable entities of a size that can be counted by, for example, a light-scattering liquid-borne particle counter. The size of the countable entities is, for example, 0.04 μm or more. The number of countable entities in the treatment liquid according to this embodiment is, for example, 1,000 or less per mL of treatment liquid, with the lower limit being, for example, 0.1 or more. By keeping the number of countable entities in the treatment liquid within the above-mentioned ranges, it is believed that the metal corrosion suppression effect and defect suppression effect of the treatment liquid will be improved (however, the effects of this embodiment are not limited to these).

[0086] The size of the objects to be counted may be a size that can be detected by a light scattering liquid particle counter, for example, 0.001 μm or more.

[0087] The organic impurities and / or the entities to be counted may be added to the treatment liquid, or may be inevitably mixed into the treatment liquid during the manufacturing process of the treatment liquid. Examples of cases where organic impurities are inevitably mixed into the treatment liquid during the manufacturing process of the treatment liquid include, but are not limited to, cases where organic impurities are contained in raw materials (e.g., organic solvents) used to manufacture the treatment liquid, and cases where organic impurities are mixed in from the external environment during the manufacturing process of the treatment liquid (e.g., contamination).

[0088] When the objects to be counted are added to the processing solution, the abundance ratio may be adjusted for each specific size, taking into consideration the surface roughness of the object to be cleaned, etc.

[0089] <Method of manufacturing the treatment liquid>

[0090] The method for producing a treatment liquid according to this embodiment includes a preparation step of mixing an alkaline compound, water, and a corrosion inhibitor to prepare a treatment liquid, wherein the amount of dissolved oxygen one week after the preparation of the treatment liquid (the completion of the preparation step) is 0.2 mg / L or more and 1.5 mg / L or less, and the corrosion inhibitor is at least one selected from the group consisting of N,N-diethylhydroxylamine, 1-thioglycerol, 1-amino-4-methylpiperazine, carbohydrazide, methyl ethyl ketoxime, erythorbic acid, and salts thereof.

[0091] The alkaline compound, water, and corrosion inhibitor may be the same as those described above for the treatment liquid. For example, in the preparation step, it goes without saying that other components than the alkaline compound, water, and corrosion inhibitor may be mixed as raw materials, if necessary. Commercially available products may be used as raw materials for these treatment liquids. Furthermore, these raw materials may be purified as necessary. The mixing method used in the preparation step is not particularly limited, and the raw materials may be mixed by a known method.

[0092] The dissolved oxygen content one week after preparation of the treatment solution (dissolved oxygen content after one week) is 0.2 mg / L or more and 1.5 mg / L or less. The content of the dissolved oxygen content after one week can be determined as described above for the treatment solution. For example, the lower limit of the dissolved oxygen content after one week is preferably 0.25 mg / L or more, more preferably 0.3 mg / L or more, and even more preferably 0.35 mg / L or more. The upper limit is preferably 1.49 mg / L or less. By keeping the dissolved oxygen content after one week within the above range, the balance between the removability of the metal components and residues to be removed and the corrosion prevention properties of metals containing Cu atoms can be further improved.

[0093] The amount of dissolved oxygen during the preparation process is preferably 0.2 mg / L or more and 6 mg / L or less. This "amount of dissolved oxygen during the preparation process" is the "amount of dissolved oxygen during preparation" described for the treatment solution. Therefore, unless otherwise specified, the above-mentioned "amount of dissolved oxygen during preparation" can be used for matters related to the "amount of dissolved oxygen during the preparation process." For example, the lower limit of the amount of dissolved oxygen during the preparation process is preferably 0.22 mg / L or more, more preferably 0.23 mg / L or more. Furthermore, the upper limit of the amount of dissolved oxygen during the preparation process is preferably 5.8 mg / L or less, more preferably 5.5 mg / L or less. In addition to controlling the amount of dissolved oxygen after one week, controlling the amount of dissolved oxygen during the preparation process to be within the above-mentioned range can further improve the balance between the removability of metal components and residues to be removed and the corrosion prevention of metals containing Cu atoms.

[0094] The treatment solution according to this embodiment is not only excellent in removing the metal components and residues to be removed, but also has excellent corrosion protection against metals containing Cu atoms, and therefore can be suitably used for treating metal layers containing Cu atoms and / or substrates containing Cu atoms. An example of a substrate to be treated with the treatment solution according to this embodiment is described below.

[0095] A semiconductor device has a substrate, a metal wiring layer, an etching stop layer, and an interlayer insulating film laminated in this order, with a protective film (hard mask layer, HM layer) laminated on the interlayer insulating film. The treatment solution according to this embodiment can be used to treat a laminated substrate used to manufacture such a semiconductor device. The structure of the laminated substrate before treatment is not particularly limited, but examples include a substrate having metal layers laminated on the substrate that correspond to a metal wiring layer, an etching stop layer, an interlayer insulating film, etc.

[0096] Examples of the substrate material include silicon, amorphous silicon, polysilicon, and glass.

[0097] Examples of the metal wiring layer include metals such as tungsten (W), molybdenum (Mo), cobalt (Co), ruthenium (Ru), gold (Au), silver (Ag), copper (Cu), iron (Fe), nickel (Ni), aluminum (Al), lead (Pb), zinc (Zn), tin (Sn), tantalum (Ta), magnesium (Mg), bismuth (Bi), cadmium (Cd), zirconium (Zr), antimony (Sb), manganese (Mn), beryllium (Be), chromium (Cr), germanium (Ge), vanadium (V), gallium (Ga), hafnium (Hf), indium (In), niobium (Nb), rhenium (Re), and thallium (Tl), as well as metal oxides, metal nitrides, metal chlorides, and metal fluorides thereof. From the viewpoint of effectively utilizing the advantages of this embodiment, it is preferable that the metal wiring layer contains Cu.

[0098] The metal wiring layer is not limited to wiring-shaped layers, but also broadly includes functional layers such as electrodes, insulating layers, low-dielectric layers, barrier layers, and various conductor layers. It includes layers formed by using the various metals mentioned above, as well as their metal oxides, metal nitrides, metal chlorides, and metal fluorides. Therefore, a substrate having a metal layer also includes a substrate having a metal wiring layer. Examples of functional layers other than metal layers include silicon-based functional layers. Silicon-based layers include SiO2, SiN, SiOCN, and low-k films (SiOC films, SiCOH films, etc.), which will be described later.

[0099] Examples of materials for the etching stop layer include aluminum oxide, SiN, SiON, and SiOCN.

[0100] Examples of materials for the interlayer insulating film include silicon-based materials such as SiO2, SiN, and SiOCN. The interlayer insulating film can be used, for example, as a functional layer that provides insulation between wiring layers in a multilayer wiring structure. In addition, with the recent trend toward miniaturization of wiring, "low-k materials" with low dielectric constants are being used for the interlayer insulating film, such as SiOC and SiOCH.

[0101] The material for the protective film (hard mask layer, HM layer) is not particularly limited as long as it functions as a protective film against etching, and a suitable material can be selected as appropriate taking into consideration manufacturing conditions, etc. Examples of protective film materials include titanium-based materials such as Ti and TiN, silicon-based materials such as SiN, SiO, SiON, and SiCN, and combinations thereof.

[0102] Furthermore, in the manufacturing process of semiconductor devices, resist materials containing a polymer as a main component, filling materials containing an alkoxysilane material as a main component, and the like are also used as needed to form wiring.

[0103] The treatment liquid according to this embodiment can be suitably used as a treatment liquid for treating a substrate having a metal layer. One suitable embodiment of the treatment liquid is a treatment liquid for treating a substrate having a metal layer, in which the substrate and / or the metal layer contains Cu atoms. The treatment liquid according to this embodiment not only excels in removing metal components and residues to be removed, but also excels in corrosion prevention of metals containing Cu atoms. Therefore, in treating a metal layer containing Cu atoms and / or a substrate containing Cu atoms, the treatment liquid can effectively remove resist films, filling materials, and residues, and can effectively prevent damage (corrosion) to the substrate having a metal layer containing Cu atoms or the substrate containing Cu atoms. Therefore, the treatment liquid can be expected to be suitably used in the manufacture of semiconductor devices having such structures.

[0104] Furthermore, a preferred embodiment of the treatment liquid according to the present invention is used to remove residues generated after etching a substrate having a metal layer. Typically, etching residues are removed before the next process in order to improve semiconductor yield and prevent deterioration of electrical characteristics. Furthermore, the treatment liquid according to the present invention is suitable for treating semiconductor substrates after dry etching in a wiring formation process. For example, the treatment liquid according to the present invention can be suitably used to remove residues generated after etching a substrate having a metal layer containing Cu atoms or a substrate containing Cu atoms in a semiconductor device manufacturing process.

[0105] <Substrate processing method>

[0106] The treatment solution according to this embodiment can be suitably used as a method for treating a semiconductor substrate. A suitable example of the method for treating a substrate according to this embodiment includes, for example, the steps of: (1) preparing a substrate having a metal layer; (2) etching the metal layer; and (3) removing impurities from the substrate after etching by contacting the substrate with the treatment solution. The following describes, as an example, the treatment of a laminated substrate used in the manufacture of semiconductor devices.

[0107] (1) A step of preparing a substrate having a metal wiring layer.

[0108] In step (1), a substrate having at least a metal layer is prepared. The metal layer is not particularly limited as long as it is a layer containing metal, and examples thereof include various metal layers, etching stop layers, interlayer insulating films, and hard mask layers (HM layers) corresponding to protective films. The method for sequentially laminating the metal layer, etching stop layers, interlayer insulating films, and / or hard mask layers (HM layers) corresponding to protective films on the substrate is not particularly limited, and known methods can be used.

[0109] (2) Etching the metal layer

[0110] Next, the metal layer is etched. The etching method is not particularly limited, and may be wet etching or dry etching, but dry etching is preferred. Dry etching is advantageous in that it allows metal wiring at the nano-level and allows control of the gas used.

[0111] In the case of dry etching, plasma can be used. Usually, when plasma etching is performed, there are problems such as the substrate being easily damaged and the plasma etching residue being generated, which needs to be cleaned with a treatment liquid. However, the treatment liquid according to the present embodiment can achieve both the above-mentioned anticorrosion properties and removability, and therefore can effectively suppress such problems.

[0112] (3) After etching, the process of removing impurities from the substrate by contacting the substrate with the above-mentioned treatment liquid.

[0113] The treatment method in step (3) is not particularly limited, and any known treatment method can be used. Examples of the treatment operation include a method in which a treatment solution is continuously applied onto a semiconductor device laminate substrate rotating at a constant speed (spin coating method), a method in which a semiconductor device laminate substrate is immersed in a treatment solution for a certain period of time (dipping method), a method in which a treatment solution is sprayed onto the surface of a semiconductor device laminate substrate (spray method), etc.

[0114] Furthermore, when the treatment liquid is brought into contact with the substrate (laminated substrate) to be treated, the treatment liquid may be diluted 2 to 2000 times to obtain a diluted liquid, and then the treatment may be carried out using this diluted liquid.

[0115] The treatment temperature (temperature of the treatment liquid) is not particularly limited, but is preferably carried out under conditions of 10 to 80°C. The lower limit of the treatment temperature is more preferably 20°C or higher, and even more preferably 40°C or higher. The upper limit of the treatment temperature is more preferably 75°C or lower, and even more preferably 70°C or lower. By setting the lower limit of the treatment temperature within the above range, it is possible to further improve the removability of etching residues while suppressing damage to metals containing Cu atoms. Furthermore, by setting the upper limit of the treatment temperature within the above range, it is possible to more effectively suppress unintended composition changes in the treatment liquid, and it is possible to more efficiently clean substrates from the viewpoints of workability, safety, cost, etc.

[0116] The treatment time can be appropriately selected to be the time required to remove residues, impurities, etc. adhering to the surface of the substrate (laminated substrate) to be treated. The treatment time is not particularly limited, but is preferably 10 seconds to 30 minutes. The lower limit of the treatment time is more preferably 20 seconds or more, and even more preferably 30 seconds or more. The upper limit of the treatment time is more preferably 15 minutes or less, even more preferably 10 minutes or less, and even more preferably 5 minutes or less.

[0117] <Semiconductor device manufacturing method>

[0118] A preferred example of the method for manufacturing a semiconductor device according to this embodiment is a substrate processing method including the steps of preparing a substrate having a metal layer, etching the metal layer, and removing impurities from the substrate by contacting the substrate with the above-described processing liquid after etching. Unless otherwise specified, the details regarding each of these steps can be appropriately adopted from the details described in the above-described substrate processing method.

[0119] The method for manufacturing a semiconductor device according to this embodiment can provide a high-quality semiconductor device in which residues and impurities are sufficiently removed and damage to the metal layer and substrate to be protected is sufficiently suppressed. In particular, since the method can achieve both the removability of the metal components and residues to be removed and the corrosion protection of metals containing Cu atoms, it is suitable for manufacturing semiconductor devices including metal layers and / or substrates containing Cu atoms.

[0120] As described above, the processing solution, substrate processing method, and semiconductor device manufacturing method according to this embodiment can achieve both the removability of metal components and residues to be removed and corrosion protection of metals containing Cu atoms. Therefore, resist films, filling materials, and metal residues can be removed while suppressing corrosion (damage) of metal layers containing Cu atoms or substrates containing Cu atoms. Even when processing substrates with metal layers containing Cu atoms or substrates containing Cu atoms, damage to the metal layers and substrates can be suppressed while sufficiently removing the resist films, filling materials, and other removal targets and residues, thereby enabling the manufacture of high-quality semiconductor devices. [Example]

[0121] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0122] (Preparation of processing solution)

[0123] A treatment liquid was prepared by mixing the components to obtain the composition shown in Table 1. For example, in the case of Comparative Example 1, the treatment liquid contained 0.10 mass % KOH, 12.10 mass % TMAH, 27.00 mass % DMSO, 60.30 mass % DIW, and 0.50 mass % MEA, and did not contain a corrosion inhibitor. The amount of dissolved oxygen at the time of preparation of the treatment liquid was 3.16 mg / L, and the amount of dissolved oxygen one week after preparation of the treatment liquid was 2.3 mg / L. In the case of Example 1, the treatment solution contained 0.10 mass% KOH, 12.10 mass% TMAH, 26.90 mass% DMSO, 60.00 mass% DIW, 0.50 mass% MEA, and 0.50 mass% N,N-diethylhydroxylamine, and the dissolved oxygen content of the treatment solution was 1.07 mg / L at the time of preparation and 0.36 mg / L one week after preparation. The content (mass%) of hydrates such as ammonium sulfite monohydrate and sodium erythorbate monohydrate is shown in Table 1, excluding the water of hydration contained in the hydrate (content of ammonium sulfite or sodium erythorbate).

[0124] The abbreviations and symbols used in Table 1 are as follows: KOH: Potassium hydroxide TMAH: Tetramethylammonium hydroxide DMSO: Dimethyl sulfoxide DIW: Deionized water MEA: Monoethanolamine

[0125] (Amount of dissolved oxygen in the treatment liquid)

[0126] The amount of dissolved oxygen in the treatment liquid to be measured was measured in an air atmosphere at 25° C. using an oxygen concentration meter (manufactured by Samejima Electronics Co., Ltd., "B-506").

[0127] First, the amount of dissolved oxygen in the treatment liquid immediately after preparation was measured by the above method as the amount of dissolved oxygen at the time of preparation of the treatment liquid ("amount of dissolved oxygen (at preparation)").

[0128] Next, the amount of dissolved oxygen one week after preparation ("amount of dissolved oxygen (one week later)") was measured under the following conditions. First, the treatment solution immediately after preparation was placed in a high-density polyethylene bottle, sealed under a nitrogen gas atmosphere, and stored in a dark place at 25°C for one week. Thereafter, the amount of dissolved oxygen was measured using the method described above.

[0129] (Evaluation of residue removal)

[0130] First, a Cu pattern wafer (CuPTW, (Cu substrate / SiN layer / interlayer insulating layer / etching stop layer / Cu layer) having a SiN metal layer, an interlayer insulating layer, an etching stop layer, and a Cu metal layer on a Cu substrate (2 cm × 2 cm) was obtained by CVD, and this was used as a sample. The components contained in the interlayer insulating layer were Si, O x , C y (x and y each independently represent 0 or a natural number), and the components contained in the etching stop layer are Si, O x , C y , N z (x, y, and z each independently represent 0 or a natural number.)

[0131] Then, 100 mL of the treatment solution of each Example and Comparative Example was poured into a cup. The sample was placed therein and immersed at 58°C for 3 minutes. During immersion, the treatment solution was stirred at 1000 rpm. After immersion, the sample was removed from the treatment solution, rinsed with water at room temperature for 30 seconds, and dried with nitrogen blow. The removability of residue was evaluated according to the following criteria. The residue was observed using a scanning electron microscope (20,000x magnification).

[0132] A: No residue was observed on the surface. B: Residue was observed over less than half of the surface area. C: Residue was observed over more than half of the surface area. D: The initial pattern was gone. The evaluation results for all Examples were A. On the other hand, the evaluation result for Comparative Example 1 was D, and the evaluation results for Comparative Examples 2 to 6 were C.

[0133] (Evaluation of corrosion resistance)

[0134] The Cu patterned wafer (CuPTW, (Cu substrate / SiN layer / interlayer insulating layer / etching stop layer / Cu layer)) prepared in the above-mentioned section "(Evaluation of residue removability)" was used as a sample.

[0135] Then, 100 mL of the treatment solution of each Example and Comparative Example was poured into a cup. The sample was placed therein and immersed at 58°C for 3 minutes. During immersion, the treatment solution was stirred at 1000 rpm. After immersion, the sample was removed from the treatment solution, washed with water at room temperature for 30 seconds, and dried with nitrogen blow. The corrosion resistance was evaluated according to the following criteria. The corrosion resistance was observed using a scanning electron microscope (20,000x magnification). A: No corrosion was observed on the surface. B: Corrosion was observed over less than half of the surface area. C: Corrosion was observed over more than half of the surface area.

[0136] Table 1 shows the composition and evaluation results of the treatment liquid for each of the Examples and Comparative Examples.

[0137] [Table 1]

[0138] From the above, it was at least confirmed that the treatment liquid according to this example not only has excellent ability to remove the metal components and residues to be removed, but also has excellent corrosion prevention properties for metals containing Cu atoms.

[0139] This application is based on U.S. Provisional Application No. 63 / 675,921, filed with the U.S. Patent and Trademark Office on July 26, 2024, the contents of which are incorporated herein by reference.

Claims

1. A treatment solution containing an alkaline compound, water, and a corrosion inhibitor, the amount of dissolved oxygen in the treatment solution after one week has elapsed since the preparation thereof is 0.2 mg / L or more and 1.5 mg / L or less; the corrosion inhibitor is at least one selected from the group consisting of N,N-diethylhydroxylamine, 1-thioglycerol, 1-amino-4-methylpiperazine, carbohydrazide, methyl ethyl ketoxime, erythorbic acid, and salts thereof; Processing liquid.

2. further comprising an antioxidant, The treatment liquid according to claim 1 .

3. The content of the alkali compound is more than 10% by mass and not more than 20% by mass. The treatment liquid according to claim 1 .

4. The water content is 50% by mass or more and 85% by mass or less. The treatment liquid according to claim 1 .

5. The content of the corrosion inhibitor is 0.005% by mass or more and 5% by mass or less. The treatment liquid according to claim 1 .

6. The content of the antioxidant is 0.001% by mass or more and 5% by mass or less. The treatment liquid according to claim 2 .

7. The amount of dissolved oxygen in the treatment solution at the time of preparation is 0.2 mg / L or more and 6 mg / L or less. The treatment liquid according to claim 1 .

8. the treatment liquid is a treatment liquid for treating a substrate having a metal layer, the substrate and / or metal layer contains Cu atoms; The treatment liquid according to claim 1 .

9. the processing liquid is used to remove residues generated after etching processing is performed on the substrate having the metal layer; The treatment liquid according to claim 8.

10. A preparation step of preparing a treatment solution by mixing an alkaline compound, water, and a corrosion inhibitor, the amount of dissolved oxygen in the treatment solution after one week has elapsed since the preparation thereof is 0.2 mg / L or more and 1.5 mg / L or less; the corrosion inhibitor is at least one selected from the group consisting of N,N-diethylhydroxylamine, 1-thioglycerol, 1-amino-4-methylpiperazine, carbohydrazide, methyl ethyl ketoxime, erythorbic acid, and salts thereof; A method for producing a processing solution.

11. The amount of dissolved oxygen in the treatment solution during the preparation step is 0.2 mg / L or more and 6 mg / L or less. The method for producing the treatment liquid according to claim 10 .

12. Providing a substrate with a metal layer; Etching the metal layer; a step of removing impurities from the substrate by bringing the processing liquid according to claim 1 into contact with the substrate after the etching; A method for processing a substrate, comprising:

13. Providing a substrate with a metal layer; Etching the metal layer; a step of removing impurities from the substrate by bringing the processing liquid according to claim 1 into contact with the substrate after the etching; A method for manufacturing a semiconductor device, comprising:

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