Substrate processing method

Abstract

A substrate processing method is provided that allows a substrate to have a clean surface condition. The present disclosure relates to a method for treating a substrate, including the following steps I and II: Step I: A step of obtaining a treatment solution by mixing a composition (liquid A) containing an inhibitor, carbon dioxide, and water with a composition (liquid B) containing an aliphatic quaternary ammonium salt, an alkanolamine, and water. Step II: A step of treating a substrate having a resin mask with the treatment liquid obtained in Step I.

Description

[Technical Field]

[0001] The present disclosure relates to a method for processing a substrate. [Background technology]

[0002] In recent years, personal computers and various electronic devices have become increasingly power-efficient, faster, and more compact, and the wiring on the package substrates and other components they are equipped with has been getting finer every year. Until now, metal masking has been the primary method used to form such fine wiring and connection terminals such as pillars and bumps, but due to its limited versatility and the difficulty of adapting to the miniaturization of wiring, new methods are being adopted.

[0003] One new method is to use a dry film resist as a thick resin mask instead of a metal mask. This resin mask is finally stripped and removed, and an alkaline stripping agent composition (strip cleaner) is used for this purpose.

[0004] For example, Patent Document 1 proposes a method for cleaning a substrate, which includes a step of peeling off a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface, using a cleaning agent containing a specific quaternary ammonium hydroxide, a specific amine, a reducing agent, and water. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2022 / 050386 Summary of the Invention [Problem to be solved by the invention]

[0006] When forming fine wiring on a printed circuit board or the like, a stripper composition (treatment liquid) is required to have high stripping performance (resin mask removability and cleaning ability) in order to reduce not only the residue of the resin mask but also the residue of auxiliary agents contained in the solder, plating solution, etc. used in the formation of the fine wiring and bumps. However, as wiring becomes finer, even slight foreign matter is no longer acceptable in order to maintain the quality and value of package substrates, and a stripper composition (treatment liquid) is required to have not only the ability to remove resin masks in fine gaps, but also the ability to achieve a cleaner surface state. When an alkaline stripping composition (treatment liquid) is used in a circulated state, it will contain carbonate ions due to reaction with carbon dioxide gas in the air, for example. It has been found that when a processing solution containing carbonate ions is used, crystalline foreign matter often occurs on the surface of the substrate after processing.

[0007] Therefore, the present disclosure provides a substrate processing method that can obtain a substrate with a clean surface condition. [Means for solving the problem]

[0008] In one aspect, the present disclosure relates to a method for treating a substrate, including the following steps I and II: Step I: A step of obtaining a treatment solution by mixing a composition (liquid A) containing an inhibitor, carbon dioxide, and water with a composition (liquid B) containing an aliphatic quaternary ammonium salt, an alkanolamine, and water. Step II: A step of treating a substrate having a resin mask with the treatment liquid obtained in Step I.

[0009] In one aspect, the present disclosure relates to a method for manufacturing an electronic component, including the method for processing a substrate of the present disclosure. [Effects of the Invention]

[0010] According to the present disclosure, it is possible to provide a substrate processing method that can obtain a substrate with a clean surface condition. DETAILED DESCRIPTION OF THE INVENTION

[0011] In one or more embodiments, the present disclosure is based on the finding that the cause of crystalline foreign matter contamination on a substrate surface after treatment using an alkaline stripper composition containing carbonate ions is an inhibitor that is more likely to precipitate due to the influence of carbonate ions and an aliphatic quaternary ammonium salt, and that the occurrence of contamination is affected by the method of mixing the aliphatic quaternary ammonium salt, carbonate ions, and inhibitor.

[0012] In one aspect, the present disclosure relates to a substrate processing method (hereinafter also referred to as "the substrate processing method of the present disclosure") that includes the following steps I and II. Step I: A step of obtaining a treatment solution by mixing a composition (liquid A) containing an inhibitor, carbon dioxide, and water with a composition (liquid B) containing an aliphatic quaternary ammonium salt, an alkanolamine, and water. Step II: A step of treating a substrate having a resin mask with the treatment liquid obtained in Step I.

[0013] According to the present disclosure, a substrate processing method that can obtain a substrate with a clean surface state can be provided, and by using the substrate processing method of the present disclosure, high-quality electronic components can be obtained with a high yield.

[0014] Although the details of the mechanism of action by which the effects of the present disclosure are manifested are still unclear, it is presumed as follows. Generally, a stripper composition (treatment liquid) for removing a resin mask present in the gaps of a fine metal pattern contains an alkanolamine, an aliphatic quaternary ammonium salt, an inhibitor, and water. On the other hand, because the stripper composition (treatment solution) is alkaline, as mentioned above, it has been reported that carbon dioxide (carbon dioxide gas) in the air dissolves as carbonate ions during use, and these ions accumulate, resulting in the solution containing a large amount of carbonate ions. Furthermore, in the presence of a certain amount or more of an aliphatic quaternary ammonium salt and a certain amount or more of carbonate ions, the solubility of the inhibitor decreases, which is thought to result in the formation of aggregates (foreign matter), and if these aggregates adhere to the substrate, they may contaminate the substrate surface. However, in the present disclosure, a composition (Liquid B) containing an aliphatic quaternary ammonium salt, an alkanolamine, and some water is prepared in advance, and then mixed with a composition (Liquid A) containing an inhibitor and carbonic acid, which is believed to prevent aggregation of the inhibitor and contamination of the substrate, and to result in a substrate with a clean surface condition. However, the present disclosure need not be construed as being limited to this mechanism.

[0015] In the present disclosure, a resin mask is a mask for protecting the surface of a material from treatments such as etching, plating, and heating, that is, a mask that functions as a protective film. In one or more embodiments, the resin mask may be a resist layer after exposure and development processes, a resist layer that has been subjected to at least one of exposure and development processes (hereinafter also referred to as "exposed and / or developed"), or a hardened resist layer. In one or more embodiments, the resin mask is formed using a resist whose physical properties, such as solubility in a developer, change when exposed to light, an electron beam, or the like. Resists are broadly classified into negative and positive types based on how they react with light or an electron beam. Negative resists have the property of decreasing their solubility in a developer when exposed to light, and the exposed portion of a layer containing negative resist (hereinafter also referred to as a "negative resist layer") is used as a resin mask after exposure and development. Positive resists have the property of increasing their solubility in a developer when exposed to light, and the exposed portion of a layer containing positive resist (hereinafter also referred to as a "positive resist layer") is removed after exposure and development, and the unexposed portion is used as a resin mask. By using a resin mask with such properties, fine connections on a circuit board, such as metal wiring, metal pillars, and solder bumps, can be formed. In one or more embodiments, the resin material for forming the resin mask may be a film-like photosensitive resin, a resist film, or a photoresist. A general-purpose resist film may be used.

[0016] [Process I: Mixing process] Step I in the substrate processing method of the present disclosure is a step (mixing step) of obtaining a processing liquid by mixing a composition (liquid A) containing an inhibitor, carbon dioxide, and water with a composition (liquid B) containing an aliphatic quaternary ammonium salt, an alkanolamine, and water. In one or more embodiments, step I further comprises mixing a composition (liquid C) containing an alkanolamine, an inhibitor, and water. That is, in one or more embodiments, step I is a step of mixing liquid A, liquid B, and liquid C to obtain a treatment liquid. The mixing method in the step I can be a known method. The mixing conditions in the step I may be set appropriately. In one or more embodiments, the mixing conditions in step I include continuously mixing about 2 to 200 L of liquid B per hour on a scale of 500 to 5000 L of liquid A. For example, in one or more embodiments, the mixing conditions in step I are preferably such that the mixing ratio (A / B) of liquid A to liquid B is 2 to 2000 and liquid B and liquid A are mixed over 1 hour, more preferably such that the mixing ratio (A / B) is 3 to 1000 and liquid A and liquid B are mixed over 1 hour, and even more preferably such that the mixing ratio (A / B) is 50 to 600 and liquid A and liquid B are mixed over 1 hour. For example, in one or more embodiments, the mixing conditions for liquid A, liquid B, and liquid C in step 1 are preferably such that the mixing ratio (B / C) of liquid B to liquid C is 0.1 to 10 and liquid B and liquid C are mixed over one hour, more preferably the mixing ratio (B / C) is 0.3 to 5 and liquid B and liquid C are mixed over one hour, and even more preferably the mixing ratio (B / C) is 0.5 to 3 and liquid B and liquid C are mixed over one hour. Also, in one or more embodiments, the mixing ratio (A / C) of liquid A to liquid C is preferably 2 to 2000 and liquid A and liquid C are mixed over one hour, more preferably the mixing ratio (A / C) is 3 to 1000 and liquid A and liquid C are mixed over one hour, and even more preferably the mixing ratio (A / C) is 50 to 600 and liquid A and liquid C are mixed over one hour. As the mixing conditions in the step I, in one or more other embodiments, the mixing ratio (A / B) of the liquid A and the liquid B may be set based on the mass ratio (inhibitor / aliphatic quaternary ammonium salt) of the content of the inhibitor in the liquid A and the content of the aliphatic quaternary ammonium salt in the liquid B. For example, it is preferably mentioned that the liquid A and the liquid B are mixed so that the mass ratio (inhibitor / aliphatic quaternary ammonium salt) of the inhibitor and the aliphatic quaternary ammonium salt mixed per hour is 0.005 or more and 60 or less. Alternatively, as the mixing conditions in the step I, in one or more embodiments, the liquid A, the liquid B, and optionally the liquid C may be mixed so that each component in the treatment liquid after mixing is within the range described below.

[0017] <Liquid A> The liquid A is a composition containing an inhibitor, carbonic acid, and water. In one or more embodiments, the liquid A further contains at least one of an organic solvent and an alkanolamine. In one or more embodiments, the liquid A can further contain an alkali metal hydroxide and / or other components. In one or more embodiments, the liquid A is a release agent composition in which carbon dioxide gas has dissolved in the treatment liquid during the treatment process or during circulation to contain carbonic acid (carbonate ions). In one or more embodiments, the liquid A can be obtained by blending an inhibitor, carbonic acid, water, and optionally an organic solvent, an alkanolamine, an alkali metal hydroxide, and other components, etc. by a known method. Here, "blending" includes mixing an inhibitor, carbonic acid, water, and other components, etc. simultaneously or in any order. In one or more embodiments, the preferred blending amount of each component in the liquid A can be the same as the preferred content of each component in the liquid A described below.

[0018] (Inhibitor in Liquid A) Examples of inhibitors contained in Solution A include compounds containing heteroatoms, specifically compounds containing nitrogen atoms, sulfur atoms, and oxygen atoms. More specifically, azoles are included, and even more specifically, at least one selected from pyrazole, methylpyrazole, thiazole, oxazole, triazole, benzotriazole, tolyltriazole, dimethylbenzotriazole, tetrazole, triazine, tetrazine, pentazole, imidazole, methylimidazole, phenylimidazole, and dimethylbenzimidazole is included. Among these, from the viewpoint of substrate surface cleanliness, at least one inhibitor selected from triazole, benzotriazole, tolyltriazole, dimethylbenzotriazole, imidazole, and dimethylbenzimidazole is preferred, and at least one selected from benzotriazole, imidazole, and dimethylbenzimidazole is more preferred. The inhibitor may be one type or a combination of two or more types. From the viewpoint of substrate cleanliness, the content of the inhibitor in Solution A is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. From the same viewpoint, it is preferably 6% by mass or less, more preferably 3% by mass or less, and even more preferably 1.5% by mass or less. More specifically, the content of the inhibitor in Solution A is preferably 0.01% by mass or more and 6% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less, and even more preferably 0.1% by mass or more and 1.5% by mass or less. When two or more inhibitors are used in combination, the content of the inhibitor in Solution A is the total content of those inhibitors.

[0019] (Carbonate in solution A) In one or more embodiments, the carbonic acid (carbonate ions) contained in the solution A is derived from carbon dioxide gas in the air, etc. In general, from the viewpoint of resin mask removability, the carbonate concentration (content) in Solution A is preferably as low as possible, and from the viewpoint of resin mask removability, it is preferably 10 mol / L or less, more preferably 5 mol / L or less, even more preferably 1.1 mol / L or less, and even more preferably 1 mol / L or less, and is 0.2 mol / L or more. In one or more embodiments, the carbon dioxide concentration (content) in solution A is 0.2 mol / L or more and 10 mol / L or less, 0.2 mol / L or more and 5 mol / L or less, 0.2 mol / L or more and 1.1 mol / L or less, or 0.2 mol / L or more and 1 mol / L or less. In the present disclosure, the carbon dioxide concentration in the liquid can be measured using potentiometric titration.

[0020] (Water in Solution A) Examples of water contained in the solution A include ion-exchanged water, RO water, distilled water, pure water, and ultrapure water. From the viewpoints of stability and miscibility, the water content in Solution A is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, and from the same viewpoints, it is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. More specifically, the water content in Solution A is preferably 5% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 90% by mass or less, and even more preferably 15% by mass or more and 85% by mass or less.

[0021] (organic solvent in solution A) In one or more embodiments, Solution A may further contain an organic solvent. From the viewpoint of improving the removability of the resin mask, the organic solvent is preferably a ketone or an alcohol compound, more preferably a glycol ether, and even more preferably butyl diglycol (BDG). The organic solvent may be one type or a combination of two or more types. From the viewpoints of stability and miscibility, the content of the organic solvent in Solution A is preferably 2% by mass or more, more preferably 4% by mass or more, and even more preferably 10% by mass or more, and from the same viewpoints, it is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. More specifically, the content of the organic solvent in Solution A is preferably 2% by mass or more and 50% by mass or less, more preferably 4% by mass or more and 45% by mass or less, and even more preferably 10% by mass or more and 40% by mass or less. When two or more organic solvents are used in combination, the content of the organic solvent in Solution A refers to the total content thereof.

[0022] (Alkanolamine in solution A) In one or more embodiments, Solution A may further contain an alkanolamine. When Solution A contains an alkanolamine, examples of the alkanolamine include the alkanolamine contained in Solution B described below. When Solution A contains an alkanolamine, the content of the alkanolamine in Solution B is preferably 2% by mass or more, more preferably 4% by mass or more, and even more preferably 6% by mass or more, from the viewpoint of resin mask removability, and from the same viewpoint, is preferably 20% by mass or less, more preferably 17% by mass or less, and even more preferably 15% by mass or less. More specifically, the content of the alkanolamine in Solution B is preferably 2% by mass or more and 20% by mass or less, more preferably 4% by mass or more and 17% by mass or less, and even more preferably 6% by mass or more and 15% by mass or less. When two or more alkanolamines are used in combination, the content of the alkanolamine in Solution A is the total content of the alkanolamines.

[0023] (Alkali metal hydroxide in solution A) In one or more embodiments, Liquid A may further contain an alkali metal hydroxide. From the perspective of resin mask removability, the alkali metal hydroxide is preferably at least one selected from lithium hydroxide, sodium hydroxide, and potassium hydroxide, more preferably at least one of sodium hydroxide and potassium hydroxide, and still more preferably potassium hydroxide. The alkali metal hydroxide may be one type or a combination of two or more types. From the perspectives of stability and miscibility, the content of the alkali metal hydroxide in Liquid A is preferably 0.3% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and from the same perspectives, preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less. More specifically, the content of the alkali metal hydroxide in Liquid A is preferably 0.3% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 8% by mass or less, and still more preferably 2% by mass or more and 5% by mass or less. When the alkali metal hydroxide is a combination of two or more types, the content of the alkali metal hydroxide in Liquid A refers to their total content.

[0024] (Other components in Liquid A) In one or more embodiments, Liquid A may further contain other components. Examples of the other components include components that can be used in ordinary detergents, such as alkali agents other than the above-mentioned alkanolamines and alkali metal hydroxides, amines other than the above-mentioned alkanolamines, organic solvents other than the above-mentioned organic solvents, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymer compounds, solubilizers, antioxidants, preservatives, antifoaming agents, antibacterial agents, and the like.

[0025] <Liquid B> Liquid B is a composition containing an aliphatic quaternary ammonium salt, an alkanolamine, and water. In one or more embodiments, Liquid B may optionally contain optional components (other components described later) as needed. In one or more embodiments, Solution B can be obtained by blending an aliphatic quaternary ammonium salt, an alkanolamine, water, and, if necessary, other components, etc., using a known method. Here, "blending" includes mixing an aliphatic quaternary ammonium salt, an alkanolamine, water, and, if necessary, other components, etc., simultaneously or in any order. In one or more embodiments, the preferred blend amounts of each component in Solution B can be the same as the preferred contents of each component in Solution B described below.

[0026] (Aliphatic quaternary ammonium salt in solution B) Examples of the aliphatic quaternary ammonium salt contained in Solution B include quaternary ammonium hydroxides represented by the following formula (II): The aliphatic quaternary ammonium salts may be one type or a combination of two or more types. [ka] In the above formula (II), R 4 , R 5 , R 6 and R 7 are each independently at least one selected from a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group. The quaternary ammonium hydroxide represented by formula (II) is a salt consisting of a quaternary ammonium cation and hydroxide, and examples thereof include at least one selected from tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, diethylbis(2-hydroxyethyl)ammonium hydroxide, dipropylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, tris(2-hydroxyethyl)propylammonium hydroxide, tetrakis(2-hydroxyethyl)ammonium hydroxide, and tetrakis(2-hydroxypropyl)ammonium hydroxide. Among these, tetramethylammonium hydroxide (TMAH) is preferred from the viewpoint of improving the removability of the resin mask. The content of the aliphatic quaternary ammonium salt in Solution B is preferably 0.5% by mass or more, more preferably 1.5% by mass or more, and even more preferably 3% by mass or more, from the viewpoint of resin mask removability, and is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of reducing waste liquid load. More specifically, the content of the aliphatic quaternary ammonium salt in Solution B is preferably 0.5% by mass or more and 40% by mass or less, more preferably 1.5% by mass or more and 35% by mass or less, and even more preferably 3% by mass or more and 30% by mass or less. When two or more types of aliphatic quaternary ammonium salts are combined, the content of the aliphatic quaternary ammonium salts in Solution B is the total content of these salts.

[0027] (Alkanolamine in solution B) Examples of the alkanolamine (amino alcohol) contained in Solution B include compounds represented by the following formula (I): The alkanolamine may be one type or a combination of two or more types. [ka] In the above formula (I), R 1 represents a hydrogen atom, a methyl group, an ethyl group, or an aminoethyl group, and R 2 represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group, or an ethyl group, and R 3 represents a hydroxyethyl group or a hydroxypropyl group. Examples of component A include at least one selected from monoethanolamine (MEA), monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethylmonoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N-(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, and N-(β-aminoethyl)diisopropanolamine. Among these, monoethanolamine (MEA) is preferred from the viewpoint of improving resin mask removability. From the viewpoints of stability and miscibility, the content of alkanolamine in Solution B is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. From the same viewpoints, it is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less. More specifically, the content of alkanolamine in Solution B is preferably 1% by mass or more and 60% by mass or less, more preferably 2% by mass or more and 55% by mass or less, and even more preferably 3% by mass or more and 50% by mass or less. When two or more alkanolamines are used in combination, the content of alkanolamine in Solution B is the total content of these alkanolamines.

[0028] In one or more embodiments, the ratio of the contents (mass%) of the aliphatic quaternary ammonium salt to the alkanolamine in solution B (aliphatic quaternary ammonium salt / alkanolamine) may be 10 / 90 to 30 / 70, 40 / 60 to 60 / 40, or 80 / 20 to 98 / 2.

[0029] (Water in Solution B) From the viewpoint of substrate cleanliness, the water content in Solution B is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, and from the viewpoint of improving resin mask removability, it is preferably 95% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. More specifically, the water content in Solution B is preferably 5% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 85% by mass or less, and even more preferably 20% by mass or more and 80% by mass or less.

[0030] (Alkali metal hydroxide in solution B) In one or more embodiments, Solution B may further contain an alkali metal hydroxide. From the viewpoint of resin mask removability, the alkali metal hydroxide is preferably at least one selected from lithium hydroxide, sodium hydroxide, and potassium hydroxide, more preferably at least one of sodium hydroxide and potassium hydroxide, and even more preferably potassium hydroxide. The alkali metal hydroxide may be one type or a combination of two or more types. From the viewpoints of stability and miscibility, the content of alkali metal hydroxide in Solution B is preferably 0.3% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, and from the same viewpoints, it is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less. More specifically, the content of alkali metal hydroxide in Solution A is preferably 0.3% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 8% by mass or less, and even more preferably 2% by mass or more and 5% by mass or less. When two or more alkali metal hydroxides are used in combination, the content of alkali metal hydroxides in Solution B refers to the total content of these.

[0031] (Other ingredients in solution B) In one or more embodiments, Solution B may further contain other components. Examples of the other components include components that can be used in ordinary cleaning agents, such as the above-mentioned aliphatic quaternary ammonium salts, alkali agents other than alkanolamines and alkali metal hydroxides, amines other than the above-mentioned alkanolamines, organic solvents, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymeric compounds, solubilizers, antioxidants, preservatives, antifoaming agents, and antibacterial agents. In one or more embodiments, Solution B does not contain the inhibitor of Solution A. (Carbonated acid in solution B) In one or more embodiments, the liquid B may contain carbonic acid (carbonate ions) derived from carbon dioxide gas in the air. Generally, from the viewpoint of improving the removability of the resin mask, it is preferable that the carbonate concentration in Solution B is as low as possible. For example, in one or more embodiments, the carbonate concentration (content) in Solution B is preferably less than 0.2 mol / L, more preferably 0.15 mol / L or less, even more preferably 0.1 mol / L or less, even more preferably 0.05 mol / L or less, and even more preferably 0.01 mol / L or less. In one or more embodiments, the carbonate concentration (content) in Solution B may be 0 mol / L. Incidentally, the carbonic acid concentration in Liquid B can be controlled within a predetermined concentration range by manufacturing it in an inert gas environment such as nitrogen or by treating it with an ion exchange resin. From the viewpoint of preventing contact with carbon dioxide gas, Liquid B is preferably stored in a sealed container until immediately before use. An inert gas may be enclosed in the container.

[0032] <Liquid C> In one or more embodiments, Liquid C is a composition containing alkanolamine, an inhibitor, and water. In one or more embodiments, Liquid C can further contain components described later as necessary. In one or more embodiments, Liquid C can be obtained by blending an aliphatic quaternary ammonium salt, water, and other components as necessary by a known method. Here, "blending" includes mixing an aliphatic quaternary ammonium salt, water, and other components as necessary simultaneously or in any order. In one or more embodiments, the preferred blending amount of each component in Liquid C can be the same as the preferred content of each component in Liquid C described later.

[0033] (Alkanolamine in Liquid C) Examples of the alkanolamine contained in Liquid C include the alkanolamine in Liquid B described above. From the viewpoints of stability and miscibility, the content of alkanolamine in Liquid C is preferably 15% by mass or more, more preferably 25% by mass or more, still more preferably 35% by mass or more, and from the same viewpoints, preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less. More specifically, the content of alkanolamine in Liquid C is preferably 15% by mass or more and 60% by mass or less, more preferably 25% by mass or more and 55% by mass or less, still more preferably 35% by mass or more and 50% by mass or less. When the alkanolamine is a combination of two or more kinds, the content of alkanolamine in Liquid C is the total content thereof.

[0034] (Inhibitor in Liquid C) Examples of inhibitors contained in Solution C include the inhibitors contained in Solution A described above. From the viewpoint of substrate cleanliness, the content of the inhibitor in Solution C is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. From the same viewpoint, it is preferably 6% by mass or less, more preferably 3% by mass or less, and even more preferably 1.5% by mass or less. More specifically, the content of the inhibitor in Solution C is preferably 0.05% by mass or more and 6% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, and even more preferably 0.5% by mass or more and 1.5% by mass or less. When two or more inhibitors are used in combination, the content of the inhibitor in Solution C is the total content of the inhibitors.

[0035] (Water in liquid C) From the viewpoints of improving resin mask removability and substrate cleanliness, the water content in Liquid C is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, and from the same viewpoints, it is preferably 95% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. More specifically, the water content in Liquid C is preferably 5% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 85% by mass or less, and even more preferably 15% by mass or more and 80% by mass or less.

[0036] (Alkali metal hydroxide in solution C) In one or more embodiments, Solution C may further contain an alkali metal hydroxide. From the viewpoint of resin mask removability, the alkali metal hydroxide is preferably at least one selected from lithium hydroxide, sodium hydroxide, and potassium hydroxide, more preferably at least one of sodium hydroxide and potassium hydroxide, and even more preferably potassium hydroxide. The alkali metal hydroxide may be one type or a combination of two or more types. From the viewpoints of stability and miscibility, the content of alkali metal hydroxide in Solution C is preferably 0.3% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more. From the same viewpoints, it is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less. More specifically, the content of alkali metal hydroxide in Solution C is preferably 0.3% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 8% by mass or less, and even more preferably 2% by mass or more and 5% by mass or less. When two or more alkali metal hydroxides are used in combination, the content of alkali metal hydroxides in Solution C refers to the total content of these.

[0037] (organic solvent in solution C) In one or more embodiments, Liquid C may further contain an organic solvent. From the viewpoint of improving the removability of the resin mask, the organic solvent is preferably a ketone or an alcohol compound, more preferably a glycol ether, and even more preferably butyl diglycol (BDG). The organic solvent may be one type or a combination of two or more types. From the viewpoints of stability and miscibility, the content of the organic solvent in Liquid C is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. From the same viewpoints, it is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less. More specifically, the content of the organic solvent in Liquid C is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 55% by mass or less, and even more preferably 20% by mass or more and 50% by mass or less. When two or more organic solvents are used in combination, the content of the organic solvent in Liquid C refers to the total content of the organic solvents.

[0038] (Other components in Solution C) In one or more embodiments, Solution C may further contain other components. Examples of the other components include components that can be used in ordinary cleaning agents, such as alkaline agents other than the above-mentioned alkanolamines and alkali metal hydroxides, amines other than the above-mentioned alkanolamines, organic solvents other than the above-mentioned organic solvents, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymeric compounds, solubilizers, antioxidants, preservatives, antifoaming agents, and antibacterial agents.

[0039] (Carbonate in liquid C) In one or more embodiments, the liquid C may contain carbonic acid (carbonate ions) derived from carbon dioxide gas in the air. Generally, from the viewpoint of improving the removability of the resin mask, it is preferable that the carbonate concentration in Solution C is as low as possible. For example, in one or more embodiments, the carbonate concentration in Solution C is preferably less than 0.2 mol / L, more preferably 0.15 mol / L or less, even more preferably 0.1 mol / L or less, even more preferably 0.05 mol / L or less, and even more preferably 0.01 mol / L or less. In one or more embodiments, the carbonate concentration in Solution C may be 0 mol / L. The carbon dioxide concentration in Solution C can be controlled within a predetermined concentration range by producing it in an inert gas environment such as nitrogen. To prevent contact with carbon dioxide, Solution C is preferably stored in a sealed container until immediately before use. An inert gas may be sealed in the container.

[0040] <Processing liquid> In one or more embodiments, the treatment liquid obtained in step I (hereinafter also referred to as "treatment liquid of the present disclosure") is a mixed liquid obtained by mixing liquid A and liquid B, or a mixed liquid obtained by mixing liquid A, liquid B, and liquid C. In one or more embodiments, the treatment liquid of the present disclosure is a treatment liquid for use in treating a substrate having a resin mask, a cleaning composition for stripping a resin mask for cleaning a substrate having a resin mask, or a stripper composition for stripping a resin mask from a substrate having a resin mask. In one or more embodiments of the present disclosure, Liquid A is a stripper composition that contains carbon dioxide (carbonate ions) as a result of carbon dioxide gas dissolving in the treatment liquid during the treatment step or circulation, and Liquids B and C are replenisher liquids for replenishing the stripper composition components of Liquid A that have become reduced due to use.

[0041] (Alkanolamine in processing solution) From the viewpoint of improving resin mask removability, the content of alkanolamine in the treatment liquid of the present disclosure is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more. From the same viewpoint, it is preferably 18% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less. More specifically, the content of alkanolamine in the treatment liquid of the present disclosure is preferably 3% by mass or more and 18% by mass or less, preferably 5% by mass or more and 15% by mass or less, and more preferably 8% by mass or more and 12% by mass or less. When two or more alkanolamines are used in combination, the content of alkanolamine in the treatment liquid is the total content of these alkanolamines.

[0042] (Inhibitors in processing solution) From the viewpoint of substrate cleanliness, the content of the inhibitor in the treatment solution of the present disclosure is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.05% by mass or more. From the same viewpoint, the content of the inhibitor in the treatment solution of the present disclosure is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. More specifically, the content of the inhibitor in the treatment solution of the present disclosure is preferably 0.01% by mass or more and 3% by mass or less, more preferably 0.02% by mass or more and 1% by mass or less, and even more preferably 0.05% by mass or more and 0.5% by mass or less. When two or more inhibitors are used in combination, the content of the inhibitor in the treatment solution is the total content of the inhibitors.

[0043] (Aliphatic quaternary ammonium salts in the processing solution) From the viewpoint of improving resin mask removability, the content of the aliphatic quaternary ammonium salt in the treatment liquid of the present disclosure is preferably 0.5% by mass or more, more preferably 1.5% by mass or more, and even more preferably 3% by mass or more. From the same viewpoint, it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less. More specifically, the content of the aliphatic quaternary ammonium salt in the treatment liquid of the present disclosure is preferably 0.5% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 10% by mass or less, and even more preferably 3% by mass or more and 7% by mass or less. When two or more types of aliphatic quaternary ammonium salts are used in combination, the content of the aliphatic quaternary ammonium salts in the treatment liquid refers to the total content of these salts.

[0044] (organic solvent in processing solution) From the viewpoint of improving resin mask removability, the content of the organic solvent in the treatment liquid of the present disclosure is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. From the same viewpoint, it is preferably 20% by mass or less, more preferably 17% by mass or less, and even more preferably 14% by mass or less. More specifically, the content of the organic solvent in the treatment liquid of the present disclosure is preferably 2% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 17% by mass or less, and even more preferably 5% by mass or more and 14% by mass or less. When two or more organic solvents are used in combination, the content of the organic solvent in the treatment liquid refers to the total content of the organic solvents.

[0045] (carbon dioxide in processing solution) In one or more embodiments, the carbonic acid (carbonate ions) contained in the treatment liquid of the present disclosure are derived from carbon dioxide gas in the air, etc. In general, the carbonate concentration (content) in the treatment solution of the present disclosure is preferably as low as possible from the viewpoint of resin mask removability. From the viewpoint of resin mask removability, the carbonate concentration is preferably 10 mol / L or less, more preferably 5 mol / L or less, and even more preferably 1 mol / L or less, and is 0.1 mol / L or more. The carbonate concentration in the treatment solution of the present disclosure can be measured using potentiometric titration.

[0046] (Water in the treatment solution) The water content in the treatment solution of the present disclosure can be the remainder obtained by subtracting the above-mentioned components (alkanolamine, inhibitor, aliphatic quaternary ammonium salt, alkali metal hydroxide, organic solvent, and other components) from the entire treatment solution. Specifically, from the viewpoint of resin mask removability, the water content in the treatment solution of the present disclosure is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, and from the same viewpoint, is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0047] (Alkali metal hydroxide in the treatment solution) When the treatment liquid of the present disclosure contains an alkali metal hydroxide, the content thereof is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of resin mask removability, and from the same viewpoint, is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1.5% by mass or less. More specifically, the content of alkali metal hydroxide in the treatment liquid of the present disclosure is preferably 0.1% by mass or more and 3% by mass or less, more preferably 0.2% by mass or more and 2% by mass or less, and even more preferably 0.5% by mass or more and 1.5% by mass or less. When two or more alkali metal hydroxides are used in combination, the content of alkali metal hydroxides in the treatment liquid refers to the total content of these.

[0048] In the present disclosure, the "content of each component in the treatment liquid" refers to the content of each component at the time of use, i.e., at the time when the treatment liquid is first used for substrate treatment (resin mask removal treatment). In one or more embodiments, the content of each component in the treatment liquid of the present disclosure can be considered to be the blend amount of each component in the treatment liquid of the present disclosure. In one or more embodiments, the content of each component in Liquid A, Liquid B, and Liquid C can be considered to be the blend amount of each component in Liquid A, Liquid B, and Liquid C, respectively.

[0049] (pH of treatment solution) From the viewpoint of improving resin mask removability, the pH of the treatment solution of the present disclosure is preferably 10 or more, more preferably 11 or more, and even more preferably 12 or more, and from the viewpoint of suppressing damage to the substrate resin, it is preferably 15 or less, more preferably 14.7 or less, and even more preferably 14.5 or less. The pH of the treatment solution is the value at 25°C and can be measured using a pH meter, specifically, by the method described in the Examples.

[0050] [Step II: Treatment Step] Step II in the substrate processing method of the present disclosure is a step (processing step) of processing a substrate (processing object) having a resin mask with the processing liquid obtained in Step I (processing liquid of the present disclosure). In one or more embodiments, the processing includes cleaning the substrate having the resin mask, stripping the resin mask from the substrate having the resin mask, and removing the resin mask from the substrate having the resin mask. In one or more embodiments, step II includes contacting the treatment liquid of the present disclosure with the object to be treated.

[0051] Methods for peeling a resin mask from a workpiece using the treatment liquid of the present disclosure, or methods for bringing the treatment liquid of the present disclosure into contact with the workpiece, include, for example, a method of contacting the workpiece by immersing the workpiece in a cleaning bath containing the treatment liquid, a method of contacting the workpiece by spraying the treatment liquid in a spray form (shower method), and an ultrasonic cleaning method of irradiating the workpiece with ultrasonic waves while the workpiece is immersed in the treatment liquid. The treatment solution of the present disclosure can be used for cleaning as is without dilution. Examples of the object to be treated include the objects to be treated described below. For example, in one or more embodiments, step II includes spraying the treatment liquid (treatment liquid of the present disclosure) obtained in step I onto a substrate (object to be treated) having a resin mask. The time for which the treatment solution of the present disclosure is brought into contact with or immersed in the treatment object (contact time or immersion time) may be, for example, from 1 minute to 10 minutes, or from 2 minutes to 6 minutes. When the treatment liquid of the present disclosure is sprayed and brought into contact, the spray time may be, for example, from 1 minute to 10 minutes, or from 2 minutes to 6 minutes.

[0052] In Step II, in order to facilitate the exertion of the peeling and cleaning power (resin mask peeling ability and resin mask removal ability) of the treatment liquid of the present disclosure, it is preferable to irradiate the treatment liquid with ultrasonic waves when the treatment liquid contacts the treatment object, and it is more preferable that the ultrasonic waves have a relatively high frequency. From the same viewpoint, the ultrasonic irradiation conditions are, for example, preferably 26 to 72 kHz and 80 to 1500 W, more preferably 36 to 72 kHz and 80 to 1500 W.

[0053] In Step II, the temperature of the treatment liquid during use is preferably 40°C or higher, more preferably 50°C or higher, so that the treatment liquid of the present disclosure can easily exhibit its peeling and cleaning power (resin mask peeling ability, resin mask removal ability), and from the viewpoint of reducing the impact on the substrate, the temperature is preferably 70°C or lower, more preferably 60°C or lower.

[0054] In one or more embodiments, step II of the substrate processing method of the present disclosure may further include rinsing the object to be processed with water and drying it after contacting the object with the processing liquid (processing liquid of the present disclosure) obtained in step I. Examples of the rinsing method include rinsing with running water. Examples of the drying method include air blow drying. In one or more embodiments, step II of the substrate processing method of the present disclosure may further include rinsing with water after contacting the object to be processed with the processing liquid obtained in step I (the processing liquid of the present disclosure).

[0055] <Item to be processed> In one or more embodiments, the workpiece is a substrate having a resin mask. Examples of the substrate include a printed circuit board, a wafer, a copper plate, and an aluminum plate. The resin mask may be, for example, a negative resin mask or a positive resin mask, and a negative resin mask is preferred in terms of the ease with which the effects of the present disclosure can be exerted. Examples of negative resin masks include negative dry film resists that have been exposed and / or developed. In the present disclosure, a negative resin mask is formed using a negative resist, and examples thereof include a negative resist layer that has been subjected to exposure and / or development treatment. In the present disclosure, a positive resin mask is formed using a positive resist, and examples thereof include a positive resist layer that has been subjected to exposure and / or development treatment. The thickness of the resin mask is, for example, 5 μm to 35 μm or less.

[0056] In one or more embodiments, the substrate (processing object) having a resin mask may be a substrate having a metal layer and a resin mask on its surface. In one or more embodiments, the metal layer is a copper plating layer, which can be formed by, for example, an electrolytic copper plating method. The thickness of the metal layer is, for example, 3 μm or more and 30 μm or less. In one or more embodiments, the metal layer is used as a metal wiring or a wiring connection portion.

[0057] In one or more other embodiments, the substrate (workpiece) having the resin mask may be, for example, an electronic component having a metal layer and a resin mask on its surface, or a manufacturing intermediate thereof. Examples of the electronic component include at least one component selected from a printed circuit board, a wafer, and a metal plate such as a copper plate or an aluminum plate. The manufacturing intermediate is an intermediate product in the manufacturing process of an electronic component, and includes an intermediate product after resin mask treatment. Specific examples of the workpiece include electronic components in which wiring, connection terminals, etc. are formed on the surface of a substrate by undergoing at least one of soldering using a resin mask and plating (copper plating, aluminum plating, nickel plating, tin plating, etc.). In this disclosure, soldering refers to applying solder to the resin mask-free areas of the substrate and forming solder bumps by heating. In this disclosure, plating refers to performing at least one plating process selected from copper plating, aluminum plating, nickel plating, and tin plating on the resin mask-free areas of the substrate. The resin mask-free areas refer to areas in a resist pattern (patterned resin mask) formed by developing a resin mask laminated to a substrate, where the resin mask has been removed by the developing process.

[0058] In one or more other embodiments, the substrate (processed object) having the resin mask may be a substrate having a resin mask in a fine gap. For example, the substrate having a resin mask in a fine gap may be a substrate on which a non-cured resin mask is applied to the surface of the substrate by at least one of exposure and development, and then the non-cured resin mask is removed and a circuit pattern is formed by plating. The non-plated portions of the formed circuit pattern have a cured resin mask. In the present disclosure, in one or more embodiments, a gap refers to the distance between circuit patterns (thin line portions) (the spacing between adjacent thin line portions), and is also called a space (S). The thickness (plating thickness) of the thin line portions is, for example, 3 μm or more and 30 μm or less. The width of the thin line portion is also called a line (L). In one or more embodiments, a resin mask in a fine gap refers to a resin mask that exists in a space with a space width (S) of 10 μm or less. The thickness of the resin mask is, for example, 5 μm or more and 35 μm or less. An example of a resin mask in a fine gap is a resin mask that exists in a space with a space width (S) of 4 to 7 μm.

[0059] [Process III (recovery process)] In one or more embodiments, the substrate processing method of the present disclosure may further include step III (recovery step). Step III in the substrate processing method of the present disclosure is a step of recovering the processing liquid after step II. In one or more embodiments, at least a portion of the processing liquid recovered in step III can be used (reused) as liquid B in step I. Thus, in one or more embodiments of the substrate processing method of the present disclosure, the processing liquid recovered in step III can be recycled and reused.

[0060] [Electronic component manufacturing method] In one aspect, the present disclosure relates to a method for manufacturing an electronic component, including the substrate processing method of the present disclosure. According to the method for manufacturing electronic components of the present disclosure, the resin mask adhered to the substrate can be effectively removed, and a substrate with a clean surface condition can be obtained, thereby enabling the manufacturing of highly reliable electronic components. Furthermore, by using the method for treating electronic components of the present disclosure, the resin mask adhered to the substrate can be easily peeled off, and a substrate with a clean surface condition can be obtained, thereby improving the manufacturing efficiency of electronic components. [Example]

[0061] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to these examples in any way.

[0062] 1. Preparation of Carbonate Source Aqueous Solution Carbon dioxide is blown into a 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) until the pH of the aqueous solution at 25°C reaches 8, thereby preparing an aqueous solution of tetramethylammonium hydrogencarbonate with a carbonate concentration of 2.7 mol / L. The concentration of tetramethylammonium hydrogencarbonate in the aqueous solution obtained by the above procedure was calculated on the assumption that all of the tetramethylammonium in the 25% by mass TMAH aqueous solution used was converted to tetramethylammonium carbonate. The amount of tetramethylammonium cation in the aqueous carbonate source solution is omitted in Table 1 below, but is the same as the amount of carbonate ion.

[0063] 1. Preparation of Treatment Liquids of Example 1 and Comparative Example 1 (Mixing Step) Example 1 Inhibitors (DMBI, BTA), an organic solvent (BDG), the aqueous carbonate source solution, and water were mixed to obtain Solution A shown in Table 1. This Solution A is intended to be a composition (treatment solution) that contains carbon dioxide gas as it dissolves during the treatment process or circulation. An aliphatic quaternary ammonium salt (TMAH), an alkanolamine (MEA), and water were mixed to obtain Solution B shown in Table 1. This Solution B is intended to be a composition that does not contain carbon dioxide (carbonate concentration: 0 mol / L). Solution B is stored sealed to avoid contact with carbon dioxide gas until it is mixed with Solution A. Liquid A and liquid B were mixed in the mixing ratio shown in Table 1 over a period of 1 hour to obtain the treatment liquid (pH: 12.1) of Example 1 shown in Table 2. The concentrations (amounts) (% by mass or mol / L, active ingredient) of each component in solutions A and B before mixing are shown in Table 1. The concentrations shown in Table 2 are the active ingredient concentrations (% by mass or mol / L) calculated from the amounts mixed. (Comparative Example 1) Inhibitors (DMBI, BTA), organic solvent (BDG), aliphatic quaternary ammonium salt (TMAH), alkanolamine (MEA), the aqueous carbonate source solution, and water were simultaneously mixed to obtain a treatment solution for Comparative Example 1. Specifically, raw materials (DMBI, BTA, BDG, TMAH, MEA, the aqueous carbonate source solution, and water) equivalent to 3 kg of treatment solution were simultaneously placed in a 5-L stainless steel beaker and mixed by stirring to prepare the treatment solution for Comparative Example 1 (pH: 12.1) shown in Table 2.

[0064] The treatment solutions of Example 1 and Comparative Example 1 were prepared using the following materials. MEA: Monoethanolamine (MEA) [Nippon Shokubai Co., Ltd.] TMAH: Tetramethylammonium hydroxide [Resonac Corporation, 25% aqueous solution] BDG: Dibutyldiglycol [Nippon Nyukazai Co., Ltd.] DMBI: 5,6-dimethylbenzimidazole [Fujifilm Wako Pure Chemical Industries, Ltd.] BTA: Benzotriazole [Fujifilm Wako Pure Chemical Industries, Ltd.] Carbonate source [tetramethylammonium bicarbonate aqueous solution with a carbonate concentration of 2.7 mol / L] Water [pure water of less than 1 μS / cm produced using the Organo Corporation G-10DSTSET water purification system]

[0065] [pH of treatment solution] The pH of the treatment solution at 25°C was measured using a pH meter (Toa Dempa Kogyo Co., Ltd., HM-30G), and was the value measured 3 minutes after the electrode of the pH meter was immersed in the treatment solution.

[0066] [Table 1]

[0067] 2. Evaluation of the treatment solutions of Example 1 and Comparative Example 1 The prepared treatment solutions of Example 1 and Comparative Example 1 were evaluated as follows.

[0068] [Evaluation board] The test piece for evaluating peelability was 50 mm x 50 mm in size, and consisted of a 15 μm-thick metal layer (copper plating layer, thin line portion) formed by copper plating on the surface of a copper substrate and a 25 μm-thick resin mask layer (negative dry film) alternately arranged in a linear pattern (circuit pattern). The line width of the metal layer (thin line portion) of the circuit pattern / the width of the resin mask layer (L / S) was 8 μm / 7 μm. The negative dry film was a cured resin mask. [Substrate surface condition] (Processing process) 3 kg of each treatment solution was added to a 5 L stainless steel beaker, which was heated to 60°C and sprayed onto the test pieces for 120 seconds (pressure: 0.03 MPa, spray distance: 8 cm) while circulating through a box-type spray washer equipped with a one-fluid nozzle (full cone type) J020 (manufactured by Ikeuchi Co., Ltd.). (Post-processing process) The test piece was then rinsed with water for 30 seconds. Furthermore, a box-type spray washer equipped with a J020 (Ikeuchi Co., Ltd.) single-fluid nozzle (full cone shape) was used to spray 10% sulfuric acid (Fujifilm Wako Pure Chemical Industries, Ltd.) onto the test piece for 10 seconds while circulating it (pressure: 0.03 MPa, spray distance: 8 cm). The test piece was then rinsed with water for 30 seconds and dried with a nitrogen blower. The test pieces after the above treatment were visually observed at 2500x magnification using a scanning electron microscope (SEM, manufactured by JEOL Ltd.), and the surface cleanliness was evaluated according to the following criteria. The results are shown in Table 2. <Surface cleanliness criteria> Clean surface: No contamination on copper Contaminated with crystalline foreign matter: Crystalline contaminants are observed

[0069] [Table 2]

[0070] As shown in Table 2, Example 1, which was obtained by mixing liquids A and B, was found to produce a substrate with a cleaner surface condition than Comparative Example 1, which was obtained by mixing all of the components simultaneously.

[0071] 3. Preparation of Treatment Solution of Example 2 Inhibitors (DMBI, BTA), organic solvent (BDG), the aqueous carbonate source solution, water, and alkanolamine (MEA) were mixed to obtain Solution A shown in Table 3 below. The obtained Solution A was colorless and transparent, with no precipitation of foreign matter even in the presence of 3% by mass of alkanolamine. This Solution A is intended to represent a composition (treatment solution) that contains carbon dioxide gas as it dissolves during the treatment process or circulation. Aliphatic quaternary ammonium salt (TMAH), alkanolamine (MEA), and water are mixed to obtain Solution B shown in Table 3. This Solution B is assumed to be a composition that does not contain carbon dioxide (carbonate concentration: 0 mol / L). Solution B is stored sealed to avoid contact with carbon dioxide gas until it is mixed with Solution A. Liquid A and liquid B are mixed for 1 hour in the mixing ratio shown in Table 3 to obtain the treatment liquid of Example 2. The treatment liquid of Example 2 can be used to treat substrates in the same manner as in Example 1.

[0072] [Table 3]

[0073] 4. Preparation of Treatment Solution of Example 3 Solution A was obtained in the same manner as solution A in Example 2. Solution B is obtained in the same manner as Solution B in Example 2. Solution C was obtained by mixing MEA, DMBI, BTA, and water. The contents of each component in Solution C were 16% by mass of MEA, 0.4% by mass of DMBI, 0.4% by mass of BTA, and the remainder was water. Liquids A, B, and C are mixed at a mixing ratio of Liquid A / Liquid B / Liquid C of 50 / 25 / 25 over one hour to obtain the processing liquid of Example 3. The processing liquid of Example 3 can be used to process substrates in the same manner as in Example 1. [Industrial Applicability]

[0074] According to the present disclosure, a substrate processing method can be provided that can obtain a substrate with a clean surface condition. Furthermore, by using the substrate processing method of the present disclosure, it is possible to improve the performance and reliability of manufactured electronic components, thereby improving the productivity of semiconductor devices.

Claims

1. A method for treating a substrate, comprising the following steps I and II: Step I: A step of mixing a composition (Solution A) containing an inhibitor, carbon dioxide, an organic solvent, and water, wherein the inhibitor contains an azole, the organic solvent contains a glycol ether, and the carbon dioxide concentration is 0.2 mol / L or more and 1.65 mol / L or less, with a composition (Solution B) containing an aliphatic quaternary ammonium salt, an alkanolamine, and water, and the carbon dioxide concentration is 0.01 mol / L or less, to obtain a treatment solution. Step II: A step of treating a substrate having a resin mask with the treatment liquid obtained in Step I.

2. 2. The method according to claim 1, wherein the organic solvent in solution A is butyl diglycol.

3. The processing method according to claim 1 , wherein the content of the organic solvent in the solution A is 2% by mass or more and 50% by mass or less.

4. 2. The treatment method according to claim 1, wherein the content of the aliphatic quaternary ammonium salt in solution B is 3% by mass or more and 30% by mass or less.

5. 5. The treatment method according to claim 4, wherein the content of alkanolamine in solution B is 2% by mass or more and 16% by mass or less.

6. 2. The processing method according to claim 1, wherein step II comprises spraying the processing liquid obtained in step I onto the substrate having the resin mask.

7. 2. The method of claim 1, further comprising the following step III: Step III: A step of recovering the treatment liquid after step II

8. 2. The treatment method according to claim 1, wherein step I further comprises mixing a composition (liquid C) containing an alkanolamine, an inhibitor, and water and having a carbonate concentration of 0.01 mol / L or less.

9. A method for manufacturing an electronic component, comprising the substrate processing method according to any one of claims 1 to 8.

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