Method for processing substrate

Abstract

In one aspect, there is provided a substrate processing method having excellent resin mask removability (peelability), the method including a step of calculating a new index for preparing a reused processing liquid. In one aspect, the present disclosure relates to a method for treating a substrate, comprising the following steps 1, 2, and 3. Step 1: A step of treating a substrate having a resin mask with a treatment liquid obtained by using an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine. Step 2: A step of determining the concentration of carbonate ions (carbonate concentration) in the treatment liquid (liquid C) used in step 1. Step 3: A step of calculating the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in the neutralization of carbon dioxide in Solution C, from the carbon dioxide concentration in the treatment solution (Solution C) determined in Step 2.

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 more energy efficient, faster, and smaller, and the wiring on package substrates mounted on these devices is becoming finer year by year. Until now, the metal mask method has been mainly used to form such fine wiring and connection terminals such as pillars and bumps, but due to its low versatility and the difficulty of responding to the miniaturization of wiring, etc., other new methods are being used.

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

[0004] As an alkaline stripping composition, a mixed solution of an alkali, an organic solvent, etc. is used. It has been reported that such a stripping composition deteriorates due to dissolution of the resist, reaction with carbon dioxide gas in the air, etc., and stripping performance (resin mask removability) decreases. Therefore, various methods for suppressing deterioration of the stripping composition and extending its life have been studied. For example, Patent Document 1 finds that carbon dioxide gas absorbed into a resist stripping solution is the main factor that reduces the resist stripping properties, and proposes a method for managing the resist stripping solution to maintain the carbon dioxide gas concentration in the resist stripping solution at 3% by weight or less. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2003-122029 A 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 stripping agent composition (treatment liquid) is required to have high stripping performance (resin mask removability, 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. In addition, when the stripper composition is recycled, the alkali components in the stripper composition and the carbon dioxide concentration in the stripper composition change, so that the stripper composition needs to be replenished or replaced according to the concentration analysis results. The amount and mixing ratio of the replenished components need to be controlled so that the composition of the stripper composition is appropriately maintained and the resin mask removability (removability) does not decrease. For example, when an aliphatic quaternary ammonium hydroxide such as TMAH is used as one of the components of the treatment liquid, the aliphatic quaternary ammonium hydroxide is consumed to neutralize the carbonate ions dissolved in the stripper composition. In some cases, the supply liquid of the aliphatic quaternary ammonium hydroxide contains some of the other components of the stripping agent, such as alkanolamine. When preparing a reused processing liquid by adding the above-mentioned feedstock liquid to a used processing liquid containing carbon dioxide, a new indicator for use in the preparation is considered to be necessary in order to suppress a decrease in the functionality of the reused processing liquid.

[0007] Therefore, the present disclosure provides a substrate processing method and a resin mask stripping method that are excellent in resin mask removability (peelability), which include a step of calculating a new index for preparing a reused processing liquid. [Means for solving the problem]

[0008] In one aspect, the present disclosure relates to a method for treating a substrate, comprising the following steps 1, 2, and 3. Step 1: A step of treating a substrate having a resin mask with a treatment liquid obtained by using an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine. Step 2: A step of determining the concentration of carbonate ions (carbonate concentration) in the treatment liquid (liquid C) used in step 1. Step 3: A step of calculating the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in the neutralization of carbon dioxide in Solution C, from the carbon dioxide concentration in the treatment solution (Solution C) determined in Step 2.

[0009] In one aspect, the present disclosure relates to a method for treating a substrate, comprising the following steps 1, 2, and 3. Step 1: A step of treating a substrate having a resin mask with a treatment liquid obtained by mixing an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine with an aqueous solution (liquid B) containing an organic solvent and an alkanolamine. Step 2: A step of determining the concentration of carbonate ions (carbonate concentration) in the treatment liquid (liquid C) used in step 1. Step 3: A step of calculating the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in the neutralization of carbon dioxide in Solution C, from the carbon dioxide concentration in the treatment solution (Solution C) determined in Step 2.

[0010] In one aspect, the present disclosure relates to a method for stripping a resin mask, comprising stripping a resin mask from a substrate having the resin mask thereon, using the substrate processing method of the present disclosure. Effect of the Invention

[0011] According to the present disclosure, it is possible to provide a substrate processing method having excellent resin mask removability (peelability), which includes a step of calculating a new index for preparing a reused processing liquid. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic diagram showing an example of the appearance of a substrate surface of a substrate to be cleaned. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] When the stripper composition is recycled, as described above, the concentrations of the alkali component in the stripper composition and the carbonate present in the stripper composition change, and therefore it is necessary to replenish or replace the stripper composition depending on the results of concentration analysis. The carbonic acid in the stripper composition can be neutralized using a strong alkali, aliphatic quaternary ammonium hydroxide. Therefore, when replenishing the aqueous solution of aliphatic quaternary ammonium hydroxide to the stripper composition containing carbonic acid, the replenishing amount of the aqueous solution of aliphatic quaternary ammonium hydroxide includes not only the amount required for the resin mask stripping treatment but also the amount required for neutralizing the carbonic acid. The aqueous solution of aliphatic quaternary ammonium hydroxide to be replenished may contain alkanolamines. As a result of extensive research by the present inventors, it was found that unless the amount of alkanolamine contained in the replenished aqueous solution of aliphatic quaternary ammonium hydroxide is taken into consideration when replenishing the solution, the composition of the stripper composition will not be properly maintained, and the removability (removability) of the resin mask may decrease. Therefore, in one or a plurality of embodiments, the present disclosure is based on the finding that, when replenishing an alkaline stripper composition containing carbonate ions (used processing liquid) (Liquid C) with an aqueous solution containing an aliphatic quaternary ammonium hydroxide and an alkanolamine (Liquid A), the amount of aliphatic quaternary ammonium hydroxide consumed in neutralizing carbon dioxide is calculated from the carbon dioxide concentration in the processing liquid after use in substrate processing, and a reuse processing liquid is prepared in consideration of a new index, that is, the amount of alkanolamine contained in Liquid A that corresponds to the amount of aliphatic quaternary ammonium hydroxide, thereby improving the peelability (removability) of a resin mask.

[0014] That is, 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") including the following steps 1, 2, and 3. Step 1: A step of treating a substrate having a resin mask with a treatment liquid obtained by using an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine. Step 2: A step of determining the concentration of carbonate ions (carbonate concentration) in the treatment liquid (liquid C) used in step 1. Step 3: A step of calculating the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in the neutralization of carbon dioxide in Solution C, from the carbon dioxide concentration in the treatment solution (Solution C) determined in Step 2. In another aspect, the present disclosure relates to a substrate processing method (hereinafter also referred to as the "substrate processing method of the present disclosure") including the following steps 1, 2, and 3. Step 1: A step of treating a substrate having a resin mask with a treatment liquid obtained by mixing an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine with an aqueous solution (liquid B) containing an organic solvent and an alkanolamine. Step 2: A step of determining the concentration of carbonate ions (carbonate concentration) in the treatment liquid (liquid C) used in step 1. Step 3: A step of calculating the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in the neutralization of carbon dioxide in Solution C, from the carbon dioxide concentration in the treatment solution (Solution C) determined in Step 2.

[0015] According to the present disclosure, a substrate processing method excellent in resin mask peelability (removability) can be provided, which includes a step of calculating a new index for preparing a reused processing liquid. Furthermore, by using the substrate processing method of the present disclosure, high-quality electronic components can be obtained with a high yield.

[0016] In the present disclosure, a resin mask is a mask for protecting a material surface 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 steps, a resist layer that has been subjected to at least one of exposure and development (hereinafter also referred to as "exposed and / or developed"), or a hardened resist layer. In addition, in one or more embodiments, the resin mask is formed using a resist whose physical properties such as solubility in a developer change by light, an electron beam, or the like. Resists are broadly classified into negative resists and positive resists according to the reaction method with light or an electron beam. The negative resist has the property that its solubility in the developer decreases when exposed, and in the layer containing the negative resist (hereinafter, also referred to as the "negative resist layer"), the exposed portion is used as the resin mask after exposure and development processing. The positive resist has the property that its solubility in the developer increases when exposed, and in the layer containing the positive resist (hereinafter, also referred to as the "positive resist layer"), the exposed portion is removed after exposure and development processing, and the unexposed portion is used as the resin mask. By using a resin mask having such characteristics, fine connection portions of a circuit board such as metal wirings, metal pillars, and solder bumps can be formed. Examples of the resin material for forming the resin mask include, in one or more embodiments, a film-like photosensitive resin, a resist film, or a photoresist. A general-purpose resist film can be used.

[0017] [Step 1] In one or more embodiments, Step 1 in the substrate processing method of the present disclosure is a step of processing a substrate having a resin mask using a treatment liquid obtained by using an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine. In one or more other embodiments, Step 1 is a step of processing a substrate having a resin mask using a treatment liquid obtained by mixing an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine with an aqueous solution (liquid B) containing an organic solvent and an alkanolamine.

[0018] <Liquid A> Liquid A is an aqueous solution containing an aliphatic quaternary ammonium hydroxide and an alkanolamine, and in one or more embodiments, optionally contains optional components (other components described later). In one or more embodiments, Solution A can be obtained by blending an aliphatic quaternary ammonium hydroxide, an alkanolamine, water, and, if necessary, optional components (other components described below) by a known method. Here, "blending" includes mixing an aliphatic quaternary ammonium hydroxide, an alkanolamine, water, and, if necessary, optional components (other components described below) simultaneously or in any order. As a method for preparing solution A, an aqueous solution containing an aliphatic quaternary ammonium hydroxide and an alkanolamine may be obtained, or an aqueous solution containing an aliphatic quaternary ammonium hydroxide and an alkanolamine may be prepared by oneself. In one or more embodiments, the solution A is a replenisher solution for replenishing the stripper composition component of the processing solution (solution C) that has become low due to use.

[0019] (Aliphatic quaternary ammonium hydroxide in solution A) Examples of the aliphatic quaternary ammonium hydroxide contained in Solution A include quaternary ammonium hydroxides represented by the following formula (II): The aliphatic quaternary ammonium hydroxides 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 a 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 peelability (removability) of the resin mask. The content of the aliphatic quaternary ammonium hydroxide in the A liquid is preferably 2% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more from the viewpoint of improving the peelability (removability) of the resin mask, and from the same viewpoint, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. More specifically, the content of the aliphatic quaternary ammonium hydroxide in the A liquid is preferably 2% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less. When the aliphatic quaternary ammonium hydroxide is a combination of two or more kinds, the content of the aliphatic quaternary ammonium hydroxide in the A liquid is the total content thereof.

[0020] (Alkanolamine in solution A) The alkanolamine (amino alcohol) contained in the solution A may be, for example, a compound 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; R 2 represents a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group, or an ethyl group; 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 the peelability (removability) of the resin mask. When the liquid A contains an alkanolamine, the content of the alkanolamine in the liquid A is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, from the viewpoint of improving the resin mask peelability (removability). And from the viewpoints of improving the resin mask peelability (removability) and substrate damage, it is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 50% by mass or less. More specifically, the content of the alkanolamine in the liquid A is preferably 1% by mass or more and 80% by mass or less, more preferably 3% by mass or more and 75% by mass or less, still more preferably 5% by mass or more and 50% by mass or less. When the alkanolamine is a combination of two or more kinds, the content of the alkanolamine in the liquid A is the total content thereof.

[0021] (Water in liquid A) From the viewpoint of improving the resin mask peelability (removability), the content of water in the liquid A is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more. And from the same viewpoint, it is preferably 95% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less. More specifically, the content of water in the liquid A is preferably 10% by mass or more and 95% by mass or less, more preferably 30% by mass or more and 85% by mass or less, still more preferably 50% by mass or more and 80% by mass or less.

[0022] (Other components in liquid A) In one or more embodiments, the liquid A may further contain other components. Examples of the other components include components that can be used in ordinary detergents, for example, alkali agents other than the above-mentioned alkanolamine and aliphatic quaternary ammonium hydroxide, amines other than the above-mentioned alkanolamine, organic solvents, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymer compounds, solubilizers, antioxidants, preservatives, antifoaming agents, antibacterial agents, etc. In one or more embodiments, the liquid A does not contain an inhibitor.

[0023] <Liquid B> In one or a plurality of embodiments, Solution B is an aqueous solution containing an organic solvent and an alkanolamine, and may further contain optional components (inhibitors, alkali metal hydroxides, and other components) described below as necessary. In one or more embodiments, Solution B can be obtained by blending an organic solvent, an alkanolamine, water, and, if necessary, any of the optional components described below (inhibitor, alkali metal hydroxide, other components) in a known manner. Here, "blending" includes mixing an organic solvent, an alkanolamine, water, and, if necessary, any of the optional components described below (inhibitor, alkali metal hydroxide, other components) simultaneously or in any order. As a method for preparing the solution B, an aqueous solution containing an organic solvent and an alkanolamine may be obtained, or an aqueous solution containing an organic solvent and an alkanolamine may be prepared by oneself. In one or more embodiments, the solution B is a replenisher solution for replenishing the stripper composition component of the processing solution (solution C) that has become low due to use.

[0024] (Organic solvent in solution B) From the viewpoint of improving the peelability (removability) of the resin mask, the organic solvent contained in the solution B is preferably a ketone or an alcohol compound, more preferably a glycol ether, and further preferably butyl diglycol (BDG). The organic solvent may be one type or a combination of two or more types. When the liquid B contains an organic solvent, the content of the organic solvent in the liquid B 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 viewpoint of stability and mixability, and from the same viewpoint, 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 the liquid B 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 the liquid B refers to the total content thereof.

[0025] (Alkanolamine in solution B) Examples of the alkanolamine contained in the solution B include the alkanolamine contained in the solution A described above. From the viewpoints of stability and mixability, the content of alkanolamine in solution B is preferably 15% by mass or more, more preferably 25% by mass or more, and even more preferably 35% by mass or more, and from the same viewpoint, 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 15% by mass or more and 60% by mass or less, more preferably 25% by mass or more and 55% by mass or less, and even more preferably 35% by mass or more and 50% by mass or less. When two or more types of alkanolamine are used in combination, the content of alkanolamine in solution B is the total content thereof.

[0026] (Water in Liquid B) Examples of the water contained in the solution B include ion-exchanged water, RO water, distilled water, pure water, and ultrapure water. From the viewpoints of stability and mixability, the water content in solution B 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 viewpoint, it is preferably 70% by mass or less, more preferably 40% by mass or less, and even more preferably 20% by mass or less. More specifically, the water content in solution B is preferably 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 15% by mass or more and 20% by mass or less.

[0027] (Inhibitors in solution B) In one or more embodiments, the liquid B may further contain an inhibitor. Examples of inhibitors contained in the liquid B include compounds containing heteroatoms, specifically, nitrogen atoms, sulfur atoms, and oxygen atom compounds. More specifically, examples of the inhibitors include azoles, and even more specifically, examples of the inhibitors include at least one selected from pyrazole, methylpyrazole, thiazole, oxazole, triazole, benzotriazole, tolyltriazole, dimethylbenzotriazole, tetrazole, triazine, tetrazine, pentazole, imidazole, methylimidazole, phenylimidazole, and dimethylbenzimidazole. Among these, from the viewpoint of improving the peelability (removability) of the resin mask, the inhibitor is preferably at least one selected from triazole, benzotriazole, tolyltriazole, dimethylbenzotriazole, imidazole, and dimethylbenzimidazole, and more preferably at least one selected from benzotriazole, imidazole, and dimethylbenzimidazole. The inhibitor may be one type or a combination of two or more types. From the viewpoint of etching suppression, the content of the inhibitor in the B solution 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, and 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 the B solution 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 types of inhibitors are used in combination, the content of the inhibitor in the B solution is the total content thereof.

[0028] (Alkali metal hydroxide in solution B) In one or more embodiments, the liquid B may further contain an alkali metal hydroxide. From the viewpoint of improving the peelability (removability) of the resin mask, the alkali metal hydroxide contained in the liquid B 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. When the solution B contains an alkali metal hydroxide, the content of the alkali metal hydroxide in the 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 from the viewpoint of stability and mixability, and from the same viewpoint, 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 the alkali metal hydroxide in the solution B 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 the alkali metal hydroxide is a combination of two or more kinds, the content of the alkali metal hydroxide in the solution B refers to the total content thereof.

[0029] (Other components in solution B) In one or more embodiments, the solution B may further contain other components. Examples of the other components include components that can be used in ordinary cleaning agents, 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, polymeric compounds, solubilizers, antioxidants, preservatives, defoamers, antibacterial agents, etc.

[0030] <Processing solution> In one or a plurality of embodiments, the treatment liquid can be obtained using liquid A, and contains, for example, an aliphatic quaternary ammonium, an alkanolamine, water, and optional components described below as necessary (an inhibitor, an alkali metal hydroxide, an organic solvent, and other components). In one or more other embodiments, the treatment liquid is a mixed liquid obtained by mixing liquid A and liquid B, and contains, for example, an aliphatic quaternary ammonium, an alkanolamine, an organic solvent, water, and optional components described below as necessary (inhibitor, alkali metal hydroxide, and other components). In one or more embodiments, the treatment liquid can be obtained by blending an aliphatic quaternary ammonium, an alkanolamine, water, and, if necessary, any of the optional components described below (inhibitor, alkali metal hydroxide, organic solvent, and other components) by a known method. Here, "blending" includes mixing the alkanolamine, water, and, if necessary, any of the optional components described below (inhibitor, alkali metal hydroxide, organic solvent, and other components) simultaneously or in any order. The mixing method may be a known method, and the mixing conditions may be appropriately set.

[0031] In one or a plurality of embodiments, the treatment liquid 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.

[0032] (Aliphatic quaternary ammonium hydroxide in the treatment solution) Examples of the aliphatic quaternary ammonium hydroxide contained in the treatment liquid include the aliphatic quaternary ammonium hydroxide contained in the above-mentioned Liquid A. The content of the aliphatic quaternary ammonium hydroxide in the treatment liquid 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 improving the peelability (removability) of the resin mask, and 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 hydroxide in the treatment liquid 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 the aliphatic quaternary ammonium hydroxide is a combination of two or more kinds, the content of the aliphatic quaternary ammonium hydroxide in the treatment liquid refers to the total content thereof.

[0033] (Alkanolamines in processing solution) Examples of the alkanolamine contained in the treatment liquid include the aliphatic alkanolamine contained in the above-mentioned liquid A. The content of alkanolamine in the treatment liquid 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 viewpoint of improving the peelability (removability) of the resin mask, and from the same viewpoint, 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 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 types of alkanolamine are used in combination, the content of alkanolamine in the treatment liquid is the total content thereof.

[0034] (Water in the treatment solution) The water content in the treatment liquid can be the remainder obtained by excluding the above-mentioned components (aliphatic quaternary ammonium salt, alkanolamine, organic solvent, inhibitor, alkali metal hydroxide, and other components) from the entire treatment liquid. Specifically, the water content in the treatment liquid is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more from the viewpoint of improving the peelability (removability) of the resin mask, 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.

[0035] (Organic solvent in processing solution) Examples of the organic solvent contained in the treatment liquid include the organic solvents contained in the above-mentioned liquid B. When the treatment liquid contains an organic solvent, the content of the organic solvent in the treatment liquid is preferably 2% by mass or more, more preferably 4% by mass or more, and even more preferably 10% by mass or more from the viewpoint of improving the peelability (removability) of the resin mask, and from the same viewpoint, it is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. More specifically, the content of the organic solvent in the treatment liquid is preferably 2% by mass or more and 25% by mass or less, more preferably 4% by mass or more and 20% by mass or less, and even more preferably 10% by mass or more and 15% 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 thereof.

[0036] (Inhibitors in processing solution) Examples of the inhibitor contained in the treatment liquid include the inhibitors contained in the above-mentioned liquid B. When the treatment liquid contains an inhibitor, the content of the inhibitor in the treatment liquid 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 viewpoint of etching suppression, and from the same viewpoint, it 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 liquid 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 types of inhibitors are used in combination, the content of the inhibitor in the treatment liquid is the total content thereof.

[0037] (Alkali metal hydroxide in the treatment solution) Examples of the alkali metal hydroxide contained in the treatment liquid include the alkali metal hydroxide contained in the above-mentioned liquid B. When the treatment liquid contains an alkali metal hydroxide, the content of the alkali metal hydroxide in the treatment liquid 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 improving the peelability (removability) of the resin mask, and from the same viewpoint, it 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 the alkali metal hydroxide in the treatment liquid 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 kinds of alkali metal hydroxides are combined, the content of the alkali metal hydroxide in the treatment liquid refers to the total content thereof.

[0038] (Other components in the processing solution) In one or more embodiments, the treatment liquid may further contain other components. Examples of the other components include components that can be used in normal cleaning agents (strippers), 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, defoamers, antibacterial agents, etc.

[0039] 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 started to be used for substrate treatment (resin mask stripping treatment). In the present disclosure, the content of each component in the treatment liquid can be regarded as the blending amount of each component in the treatment liquid in one or more embodiments.

[0040] (pH of treatment solution) From the viewpoint of improving peelability (removability) of the resin mask, the pH of the treatment liquid 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, the pH is preferably 15 or less, more preferably 14.7 or less, and even more preferably 14.5 or less. In the present disclosure, the pH of the treatment liquid is a value at 25° C., and can be measured using a pH meter, specifically, by the method described in the Examples.

[0041] <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 is preferably a negative resin mask in terms of the ease with which the effects of the present disclosure can be exhibited. Examples of the negative resin mask include a negative dry film resist that has been exposed and / or developed. In the present disclosure, a negative resin mask is formed using a negative resist, and examples of such a mask include a negative resist layer that has been exposed to light and / or developed. In the present disclosure, a positive resin mask is formed using a positive resist, and examples of such a mask include a positive resist layer that has been subjected to exposure and / or development processing. The resin mask has a thickness of, for example, 5 μm to 35 μm.

[0042] In one or a plurality of embodiments, the substrate having a resin mask (object to be cleaned) 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. The copper plating layer 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. In one or more embodiments, the resin mask may be a resin mask (resin mask layer) present in the form of perforations in the metal layer (see FIG. 1). In one or more embodiments, the sides of the resin mask are surrounded by the metal layer. In one or more embodiments, the shape of the resin mask layer may be a polygonal (square, hexagonal, octagonal, etc.) columnar, cylindrical, approximately cylindrical, etc. The diameter of the resin mask layer (diameter of the circumscribing circle in the case of a polygonal shape) may be, for example, 20 μm or more and 200 μm or less. The thickness of the resin mask layer may be, for example, 5 μm or more and 50 μm or less. Perforation-like resin mask interface ratio (μm - ) (=Interface line length between resin mask and metal layer (μm) / Area of ​​resin mask (μm 2 )) may be 0.01 or more and 0.5 or less, or 0.02 or more and 0.2 or less. Here, the interface line length between the resin mask and the metal layer is, for example, the length of the circumference when the resin mask is a circle when viewed from above. A new problem has been found in that the resin mask of the object to be cleaned having such a structure has poor removability when using a conventional remover. In one or more embodiments, the treatment liquid used in step 1 and the reuse treatment liquid described below can suitably remove the resin mask having such a structure. In one or more embodiments, the object to be cleaned in the present disclosure may be an object to be cleaned having at least one resin mask attached in the form of perforations in a metal layer, as described above.

[0043] In one or a plurality of 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. The copper plating layer 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.

[0044] In one or more other embodiments, the substrate (processing object) 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. The electronic component may be, for example, 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 a resin mask treatment. Specific examples of the object to be treated include electronic components in which wiring, connection terminals, etc. are formed on the surface of a substrate by at least one of soldering using a resin mask and plating (copper plating, aluminum plating, nickel plating, tin plating, etc.). In the present disclosure, soldering refers to providing solder in the resin mask-free portion of the substrate and forming a solder bump by heating. In the present 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 portion of the substrate. The resin mask-free portion refers to a portion in a resist pattern (a resin mask having a pattern shape) formed by subjecting a resin mask laminated to a substrate to a developing process, from which the resin mask has been removed by the developing process.

[0045] In one or more other embodiments, the substrate (processing 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 substrate surface through at least one of exposure and development curing treatments, and then the non-cured resin mask is removed and a circuit pattern is formed through plating treatment. The non-plated portion of the formed circuit pattern has a cured resin mask. In the present disclosure, in one or more embodiments, the gap refers to the distance between circuit patterns (thin line portions) (the interval between adjacent thin line portions), and is also called space (S). Examples of the thickness (plating thickness) of the thin line portions include 3 μm or more and 30 μm or less. The width of the thin line portion is also called line (L). In one or more embodiments, the 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. Examples of the thickness of the resin mask include 5 μm or more and 35 μm or less. Examples of the resin mask in a fine gap include a resin mask that exists in a space with a space width (S) of 4 to 7 μm.

[0046] <Processing> In one or a plurality of embodiments, the step 1 includes a step (treatment step) of treating a substrate (object to be treated) having a resin mask with a treatment liquid. In one or more embodiments, the process 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, the treatment step includes contacting a treatment liquid with an object to be treated.

[0047] In the present disclosure, examples of a method for peeling off a resin mask from a workpiece using a treatment liquid, or a method for bringing a treatment liquid into contact with a workpiece include a method for bringing the workpiece into contact by immersing the workpiece in a cleaning bath containing the treatment liquid, a method for bringing the workpiece into contact by ejecting the treatment liquid in a spray form (shower method), and an ultrasonic cleaning method for 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. The object to be treated may be any of the objects described above. For example, in one or more embodiments, the treatment step includes spraying the treatment liquid obtained in the mixing step onto a substrate (object to be treated) having a resin mask. The time for which the treatment liquid is brought into contact with or immersed in the treatment object (contact time or immersion time) can be, for example, from 1 minute to 10 minutes, and further from 2 minutes to 6 minutes. When the treatment liquid is sprayed and contacted, the spray time can be, for example, from 1 minute to 10 minutes, and further from 2 minutes to 6 minutes.

[0048] In the treatment step, in order to facilitate the exertion of the peeling and cleaning power (resin mask peeling property, resin mask removal property) of the treatment liquid, it is preferable to irradiate ultrasonic waves when the treatment liquid comes into contact with the object to be treated, and it is more preferable that the ultrasonic waves have a relatively high frequency. From the same viewpoint, the irradiation conditions of the ultrasonic waves are, for example, preferably 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

[0049] In the above-mentioned treatment step, in order to facilitate the exertion of the peeling and cleaning power (resin mask peeling ability, resin mask removability) of the treatment liquid, the temperature during use of the treatment liquid (treatment temperature) is preferably 40°C or higher, more preferably 50°C or higher, and from the viewpoint of reducing the effect on the substrate, it is preferably 70°C or lower, more preferably 60°C or lower.

[0050] In one or more embodiments, the treatment step may further include rinsing the object to be treated with water and drying the object after contacting the object with the treatment liquid obtained in the mixing step. Examples of the rinsing method include rinsing with running water. Examples of the drying method include air blow drying. In one or more embodiments, the treatment step may further include rinsing the object to be treated with water after contacting the object with the treatment liquid obtained in the mixing step.

[0051] [Step 2: Carbonate concentration] Step 2 in the substrate processing method of the present disclosure is a step of determining the concentration of carbonate ions (carbonate concentration) in the processing liquid (liquid C) after use in step 1. In one or more embodiments, the method for determining the carbonate concentration includes a method for measuring the carbonate concentration in the treatment liquid after use, a method for calculating from the number of substrates treated, etc. Calculating from the number of substrates treated can be calculated, for example, from the number of substrates treated, the time required to treat one substrate, and the increase in carbonate concentration per unit time.

[0052] (Carbonic acid in liquid C) In one or a plurality of embodiments, the liquid C of the present disclosure is a processing liquid (stripper composition) that contains carbon dioxide (carbonate ions) as a result of carbon dioxide gas being dissolved in the processing liquid during the processing step or circulation. In one or a plurality of embodiments, the carbonic acid (carbonate ions) contained in the treatment liquid (Liquid C) after use in step 1 is derived from carbon dioxide gas in the air, etc. Generally, from the viewpoint of improving the peelability (removability) of the resin mask, it is preferable that the carbonate concentration (content) in the C liquid is as low as possible. For example, from the viewpoint of improving the peelability (removability) of the resin mask, the carbonate concentration (content) in the treatment liquid 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. In the present disclosure, the carbonate concentration in the treatment liquid can be measured using potentiometric titration.

[0053] The molar ratio of the aliphatic quaternary ammonium hydroxide to the carbonate ion in the solution C (aliphatic quaternary ammonium hydroxide / carbonate ion) is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 1 or more, from the viewpoint of improving the peelability (removability) of the resin mask, and from the same viewpoint, is preferably 100 or less, more preferably 30 or less, and even more preferably 10 or less. More specifically, the molar ratio (aliphatic quaternary ammonium hydroxide / carbonate ion) in the solution C is preferably 0.01 or more and 100 or less, more preferably 0.1 or more and 30 or less, and even more preferably 1 or more and 10 or less.

[0054] [Step 3: Calculating the amount of alkanolamine] Step 3 in the substrate processing method of the present disclosure is a step of calculating the amount of alkanolamine contained in the A liquid, which contains the same amount of aliphatic quaternary ammonium hydroxide as the aliphatic quaternary ammonium hydroxide consumed in the C liquid for neutralizing the carbon dioxide, from the carbon dioxide concentration in the processing liquid (C liquid) determined in step 2. In one or more embodiments, this amount of alkanolamine can be said to be the amount of alkanolamine brought from the A liquid to neutralize the carbon dioxide in the C liquid. The unit of this amount of alkanolamine may be concentration or mass. As described later, this amount of alkanolamine can be used when preparing a recycled processing liquid from the C liquid after use.

[0055] Step 3, in one or more embodiments, includes calculating the amount of alkanolamine using formula (I) below: Amount of alkanolamine (mass%) = [carbonate concentration in solution C (mol / L) × C × molar mass of aliphatic quaternary ammonium hydroxide (g / mol)] ÷ amount of aliphatic quaternary ammonium hydroxide in solution A (mass%) × amount of alkanolamine in solution A (mass%) (I) In the above formula (I), the coefficient C is a coefficient determined based on the degree of neutralization, the number of neutralizations added, and a unit conversion coefficient, and is a value in the range of 0.01 to 1. In one or more embodiments, the coefficient C is defined as the degree of neutralization x the number of neutralization additions x unit conversion coefficient. In one or more embodiments, the coefficient C is the number of aliphatic quaternary ammonium ions added to carbonate ions, and can be determined by the valences of carbonic acid and aliphatic quaternary ammonium hydroxide. In one or more embodiments, the degree of neutralization is 0 to 1, and is usually 1. The neutralization addition number is the acid valence divided by the alkali valence of the aliphatic quaternary ammonium hydroxide, and in one or more embodiments, it is 0 to 5, and can usually be 2. The unit conversion factor, for example, when converting g / L to mass %, is 0.1. For example, when the aliphatic quaternary ammonium hydroxide is TMAH, the degree of neutralization is 1, the neutralization addition number is 2, and the unit conversion coefficient (when converting g / L to mass%) is 0.1, and the coefficient C = 0.2 can be used in formula (I).

[0056] [Step 4: Preparation of recycled treatment liquid] In one or more embodiments, the substrate processing method of the present disclosure includes step 4: preparing a reused processing liquid by mixing the liquid A with the liquid C based on the amount of alkanolamine calculated in step 3. In one or more embodiments, the step 4 further includes a step of mixing the liquid B with the liquid C based on the amount of alkanolamine calculated in step 3. In one or more embodiments, the step 4 includes a step of processing a substrate having a resin mask with the reused processing liquid.

[0057] <Recycled processing liquid> In one or more embodiments, the recycled processing liquid is a mixed liquid obtained by mixing liquid A and liquid C, and in one or more other embodiments, is a mixed liquid obtained by mixing liquid A, liquid B, and liquid C. The components contained in the reused treatment liquid include the same components as those in the treatment liquid described above. The preferred content of each component contained in the reuse treatment liquid is the same as the preferred content of each component contained in the treatment liquid described above. In one or a plurality of embodiments, the carbonate ions (carbonic acid) contained in the recycled treatment liquid are derived from carbon dioxide gas in the air, etc. In general, the carbon dioxide concentration (content) in the reused treatment liquid is preferably as low as possible from the viewpoint of improving the peelability (removability) of the resin mask. For example, the carbon dioxide concentration (content) in the reused treatment liquid 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 0.1 mol / L or more, from the viewpoint of improving the peelability (removability) of the resin mask.

[0058] <Mixing conditions> In step 4, the method of mixing the liquid A with the liquid C, the method of mixing the liquid B with the liquid C, and the method of mixing the liquid A, the liquid B, and the liquid C can be any known method. In one or more embodiments, the mixing conditions (the mixing ratio of Liquid C to Liquid A, the mixing ratio of Liquid C to Liquid B, and the mixing ratio of Liquid A to Liquid B to Liquid C) can be set based on the amount of alkanolamine calculated in step 3. In the present disclosure, mixing, in one or more embodiments, includes adding one to the other. For example, the concentration is set so as to minimize the sum of the differences between the target values ​​of the concentrations of the alkanolamine, the aliphatic quaternary ammonium hydroxide, and the organic solvent after mixing. In step 4, in one or a plurality of embodiments, the mixing ratio of liquid C to liquid A, the mixing ratio of liquid C to liquid B, or the mixing ratio of liquid A to liquid B to liquid C can be determined based on the amount of alkanolamine calculated in step 3, and the replenishment amount of liquid A or the replenishment amount of liquid B can be controlled. Here, in one or a plurality of embodiments, “mixing the liquid A with the liquid C based on the amount of alkanolamine calculated in step 3” refers to a method of mixing the liquid C with the liquid A at a ratio between the liquid C and the liquid A that is determined by the difference, ratio, and correction coefficient between the amount of alkanolamine in the treatment liquid (liquid C) after use in step 1 and the amount of alkanolamine calculated in step 3. Furthermore, in one or a plurality of embodiments, "mixing the liquid B with the liquid C based on the amount of alkanolamine calculated in step 3" may refer to a method of mixing the liquid B with the liquid C in an amount containing monoethanolamine obtained by subtracting the amount of alkanolamine calculated in step 3 from the difference between the target concentration of alkanolamine and the concentration of the treatment liquid (liquid C) after use in step 1.

[0059] In one or more embodiments, step 4 can further include changing at least one selected from the time for which the treatment liquid is in contact with or immersed in the object to be treated, and the temperature of the treatment liquid during use, based on the amount of alkanolamine calculated in step 3.

[0060] [Step 5: Recovery] In one or more embodiments, the substrate processing method of the present disclosure may further include step 5 (recovery step). Step 5 in the substrate processing method of the present disclosure is a step of recovering the processing liquid used in step 1. In one or more embodiments, at least a portion of the processing liquid recovered in step 5 can be reused as a recycled processing liquid after undergoing steps 2 to 4. Thus, in one or more embodiments of the substrate processing method of the present disclosure, the processing liquid recovered in step 5 can be recycled and reused.

[0061] [Removal method] In one aspect, the present disclosure relates to a method for stripping a resin mask (hereinafter, also referred to as the "stripping method of the present disclosure"), which includes stripping a resin mask from a substrate (workpiece) having the resin mask by using the substrate processing method of the present disclosure. The workpiece in the stripping method of the present disclosure includes the above-mentioned object to be cleaned. According to the stripping method of the present disclosure, a resin mask stripping method excellent in resin mask removability (stripping ability) can be provided, which includes a step of calculating a new index for preparing a reused processing liquid.

[0062] [Method of managing the treatment liquid (stripper composition)] In one aspect, the present disclosure relates to a method for managing a treatment liquid (stripper composition) used in a process for treating a substrate having a resin mask (subject to be treated) by treating the substrate having a resin mask with a treatment liquid obtained by using an aqueous solution (Liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine (hereinafter also referred to as the "management method of the present disclosure"). In one or more embodiments, the management method of the present disclosure includes a step a of determining a carbon dioxide concentration in a processing liquid (Liquid C) used to process the workpiece (step 2 in the substrate processing method of the present disclosure described above), and a step b of calculating, from the carbon dioxide concentration in the processing liquid (Liquid C) determined in step a, an amount of alkanolamine contained in Liquid A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in neutralization of the carbon dioxide in Liquid C (step 3 in the substrate processing method described above). In one or more embodiments, the management method of the present disclosure includes a step c (step 4 in the above-described substrate processing method) of preparing a reuse processing liquid by mixing the liquid A with the liquid C based on the amount of alkanolamine calculated in the step b. In one or more embodiments, the step c further includes a step of mixing an aqueous solution (liquid B) containing an organic solvent and an alkanolamine with the liquid C based on the amount of alkanolamine calculated in the step b. According to the management method of the present disclosure, when replenishing an alkaline stripper composition containing carbonate ions (used processing liquid) (Liquid C) with an aqueous solution containing an aliphatic quaternary ammonium hydroxide and an alkanolamine (Liquid A), the amount of aliphatic quaternary ammonium hydroxide consumed in neutralizing carbon dioxide is calculated from the carbon dioxide concentration in the processing liquid after use in substrate processing, and the preparation of the reused processing liquid can be managed in consideration of a new index, that is, the amount of alkanolamine contained in Liquid A which corresponds to the amount of aliphatic quaternary ammonium hydroxide, and a reused processing liquid with excellent resin mask stripping properties (removability) can be obtained.

[0063] [Electronic component manufacturing method] In one aspect, the present disclosure relates to a method for manufacturing an electronic component substrate, the method including the substrate processing method of the present disclosure. According to the manufacturing method of electronic components of the present disclosure, the resin mask attached to the substrate can be effectively removed, so that highly reliable electronic components can be manufactured. Furthermore, by using the substrate processing method of the present disclosure, the resin mask attached to the substrate can be easily peeled off, so that the peeling time (processing time) can be shortened, and the manufacturing efficiency of electronic components can be improved. EXAMPLES

[0064] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to these examples in any way.

[0065] Test 1 (Example 1, Reference Example 1) 1-1. Preparation of used processing solution (solution C) Alkanolamine (MEA), a carbonate source (ammonium carbonate), and water were mixed to obtain Solution D shown in Table 1. The carbonate source in Solution D, ammonium carbonate, produces carbonate ions in an aqueous solution. The carbonic acid in Solution D shown in Table 1 represents carbonate ions produced from ammonium carbonate. Aliphatic quaternary ammonium hydroxide (TMAH), alkanolamine (MEA), and water were mixed to obtain Solution A shown in Table 1. Liquid D and Liquid A were mixed for 1 hour in the mixing ratio shown in Table 1 to obtain Liquid C (used treatment liquid) (pH: 11.9) shown in Table 1. In Liquid C, a part of the TMAH reacts with carbonate (ions) to form a neutral salt. Liquid C containing this neutral salt is assumed to be the treatment liquid after use in step 1. The concentration (amount) (% by mass or mol / L, active ingredient) of each component in Solution D and Solution A before mixing is shown in Table 1. The concentrations shown in Table 1 are the active ingredient concentrations (% by mass or mol / L) calculated from the amounts mixed.

[0066] The following materials were used to prepare solutions D and A. MEA: Monoethanolamine [Nippon Shokubai Co., Ltd.] Ammonium carbonate [Fujifilm Wako Pure Chemicals] (carbonate source) TMAH: Tetramethylammonium hydroxide [Resonac Corporation, 25% aqueous solution] Water [Pure water of less than 1 μS / cm produced using Organo Corporation's pure water production system G-10DSTSET]

[0067] [pH of treatment solution] The pH of the treatment solution at 25° C. was measured using a pH meter (Toa Denpa 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.

[0068] 1-2. Amount of alkanolamine (Example 1: Calculation of the amount of alkanolamine using formula (I) (Steps 2-3)) From the carbon dioxide concentration in the solution C, the amount of alkanolamine contained in the solution A containing the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in the neutralization of the carbon dioxide in the solution C was calculated as follows. First, calculate the carbon dioxide concentration in solution C using the following formula. Carbonate concentration in solution C (mol / L) = Carbonate concentration of solution C (mol / L) × Mixing ratio of solution C (%) ÷ 100 Next, using the mass ratio of the aliphatic quaternary ammonium hydroxide to the alkanolamine in the solution A, the amount of alkanolamine contained in the solution A containing the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in the neutralization of carbon dioxide is calculated from the following formula (I). Amount of alkanolamine (mass%) = [carbonate concentration in solution C (mol / L) × C × molar mass of aliphatic quaternary ammonium hydroxide (g / mol)] ÷ amount of aliphatic quaternary ammonium hydroxide in solution A (mass%) × amount of alkanolamine in solution A (mass%) (I) In the above formula (I), the coefficient C is a coefficient determined based on the degree of neutralization, the number of neutralization additions, and the unit conversion coefficient, and is defined as the degree of neutralization (0 to 1, usually 1) × the number of neutralization additions (0 to 2, usually 2) × the unit conversion coefficient (0.1 when converting g / L to mass%). Here, the degree of neutralization is 1, the number of neutralization additions is 2, and the unit conversion coefficient is 0.1, and the coefficient C = 0.2 was used in formula (I).

[0069] (Reference Example 1: Calculation of the amount of alkanolamine by titration) The prepared treatment solution (liquid C) was titrated using an automatic potentiometric titrator (Kyoto Electronics Manufacturing Co., Ltd., AT-710) with a sampling amount of 5 g and water (45 g) as a dilution solvent (dilution ratio: 10 times). A titration curve showing the relationship between the amount of acid dropped by titration and pH was obtained, and three inflection points due to amines that appeared at pH 10 or less were detected. The three inflection points were detected as points where the first-order differential of pH was minimal, and were designated the first, second, and third inflection points in the order of appearance. The concentration of alkanolamine in the treatment solution (liquid C) was then calculated using the formula below. Alkanolamine concentration (mass%) = ((AD x β) + (BD x β)) / 2 / α x M x 100 In the above formula, A represents the number of moles of acid consumed (mol / g) per gram of the treatment liquid (Liquid C) up to the first inflection point, B represents the number of moles of acid consumed (mol / g) per gram of the treatment liquid (Liquid C) up to the second inflection point, D represents the concentration (mol / g) of the alkali other than the alkanolamine in the treatment liquid (Liquid C), α represents the valence of the alkanolamine, β represents the valence of the alkali other than the alkanolamine, and M represents the molar mass (g / mol) of the alkanolamine.

[0070] [Table 1]

[0071] As shown in Table 1, in Example 1, by using formula (I), the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed for the neutralization of the carbon dioxide in Solution C, could be calculated. On the other hand, the titration method in Reference Example 1 could not calculate the amount.

[0072] Test 2 (Example 2) 2-1. Preparation of used processing solution (solution C) Alkanolamine (MEA), organic solvent (BDG), carbonate source (ammonium carbonate), and water were mixed to obtain Solution D shown in Table 2. Ammonium carbonate, which is the carbonate source in Solution D, generates carbonate ions in an aqueous solution. Carbonic acid in Solution D shown in Table 2 indicates carbonate ions generated from ammonium carbonate. Aliphatic quaternary ammonium hydroxide (TMAH), alkanolamine (MEA), and water were mixed to obtain solution A shown in Table 2. Liquid D and Liquid A were mixed for 1 hour in the mixing ratio shown in Table 2 to obtain Liquid C (used processing liquid) (pH: 11.9) shown in Table 2. The pH of the processing liquid was measured in the same manner as in Test 1 above. In Liquid C, a part of the TMAH reacts with carbonate (ion) to form a neutral salt. Liquid C containing this neutral salt is assumed to be the processing liquid after use in Step 1. The concentrations (amounts) (% by mass or mol / L, active ingredient) of each component in Solution D and Solution A before mixing are shown in Table 2. The concentrations shown in Table 2 are the active ingredient concentrations (% by mass or mol / L) calculated from the amounts mixed.

[0073] The following materials were used to prepare solutions D and A. MEA: Monoethanolamine [Nippon Shokubai Co., Ltd.] BDG: Butyl diglycol [Nippon Emulsifier] Ammonium carbonate [Fujifilm Wako Pure Chemicals] (carbonate source) TMAH: Tetramethylammonium hydroxide [Resonac Corporation, 25% aqueous solution] Water [Pure water of less than 1 μS / cm produced using Organo Corporation's pure water production system G-10DSTSET]

[0074] 2-2. Calculation of the amount of alkanolamine using formula (I) (steps 2 to 3) The amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed for neutralization of carbon dioxide in Solution C, was calculated from the carbon dioxide concentration in Solution C in the same manner as in Example 1. The calculation results are shown in Table 2. The amount of alkanolamine in Table 2 is a value converted to mass%.

[0075] 2-3. Preparation of reused treatment liquid (step 4) Based on the amount of alkanolamine calculated using formula (I) in 1-2 above, the mixing ratio of liquid C, liquid A, and liquid B was calculated using the following formula. Based on the calculated mixing ratio, liquid C, liquid A, and liquid B were mixed to prepare a reused treatment liquid. Mixing ratio (mass%) of liquid C used in preparation of reused treatment liquid=[amount of alkanolamine in liquid C (mass%)−amount of alkanolamine calculated using formula (I) (mass%)÷2.5]÷amount of alkanolamine in liquid C (mass%)×100 Mixing ratio (mass%) of solution A used in preparation of the reused treatment solution=amount of alkanolamine calculated using formula (I) (mass%) / amount of alkanolamine in solution A (mass%) / 3.5×100 Mixing ratio (mass%) of water used in preparation of reused treatment liquid=100-mixing ratio (mass%) of solution A used in preparation of reused treatment liquid-mixing ratio (mass%) of solution C used in preparation of reused treatment liquid In the above formula, 2.5 and 3.5 are coefficients set so as to reduce the sum of the differences between the concentrations of the alkanolamine, the aliphatic quaternary ammonium hydroxide, and the organic solvent after mixing and the target values.

[0076] 2-4. Evaluation of processing solution Using the prepared recycled treatment liquid of Example 2, the removability (peelability) of the resin mask was evaluated as follows.

[0077] [Test piece for evaluating peelability] The test piece for evaluating peelability is 50mm x 50mm in size, and has a 15μm thick metal layer 2 formed by copper plating on the surface of a glass epoxy multilayer substrate with a copper thin film, and a 25μm thick resin mask layer 1 made of a negative dry film resist in a circular area with a diameter of 300μm present in the form of perforations in the metal layer 2, with 15μm of the 25μm thick resin mask buried in the metal layer. There are 3000 perforations. [Resin mask removability (peelability)] 3 kg of the stripping composition was added to a 5L stainless steel beaker. This was heated to 50°C, and the test piece was sprayed for 2.5 minutes while circulating with a box-type spray washer equipped with a one-fluid nozzle (full cone-shaped) J020 (Ikeuchi Co., Ltd.) as a spray nozzle (pressure: 0.05 MPa, spray distance: 8 cm). Then, water was poured for 30 seconds to rinse, and then dried by nitrogen blowing. Using a digital microscope (VHX-6000, Keyence Co., Ltd.), the test piece after the above-mentioned spray treatment was visually observed at 300 times magnification, and the occurrence rate of resin mask residue (residue rate) was measured. It can be judged that the lower the value, the better the resin mask removability (peelability). The results are shown in Table 2.

[0078] [Table 2]

[0079] As shown in Table 2, the recycled treatment liquid prepared in Example 2 exhibited good resin mask peeling properties. [Industrial Applicability]

[0080] According to the present disclosure, a substrate processing method having excellent resin mask removability (peelability) can be provided. Furthermore, by using the substrate processing method of the present disclosure, it is possible to improve the performance and reliability of manufactured electronic components, and to improve the productivity of semiconductor devices. [Explanation of symbols]

[0081] 1 Resin mask layer (dry film resist) 2 Metal layer (metal plating layer)

Claims

1. A method for treating a substrate, comprising the following steps 1, 2 and 3. Step 1: A step of treating a substrate having a resin mask with a treatment liquid obtained by using an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine. Step 2: A step of determining the concentration of carbonate ions (carbonate concentration) in the treatment liquid (liquid C) used in step 1. Step 3: A step of calculating the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in the neutralization of carbon dioxide in Solution C, from the carbon dioxide concentration in the treatment solution (Solution C) determined in Step 2.

2. 2. The treatment method according to claim 1, further comprising step 4: mixing the liquid A with the liquid C based on the amount of alkanolamine calculated in step 3 to prepare a reuse treatment liquid.

3. 3. The method according to claim 2, wherein step 4 comprises mixing an aqueous solution (liquid B) containing an organic solvent and an alkanolamine with liquid C based on the amount of alkanolamine calculated in step 3.

4. A method for treating a substrate, comprising the following steps 1, 2 and 3. Step 1: A step of treating a substrate having a resin mask with a treatment liquid obtained by mixing an aqueous solution (liquid A) containing an aliphatic quaternary ammonium hydroxide and an alkanolamine with an aqueous solution (liquid B) containing an organic solvent and an alkanolamine. Step 2: A step of determining the concentration of carbonate ions (carbonate concentration) in the treatment liquid (liquid C) used in step 1. Step 3: A step of calculating the amount of alkanolamine contained in Solution A, which contains the same amount of aliphatic quaternary ammonium hydroxide as the amount of aliphatic quaternary ammonium hydroxide consumed in the neutralization of carbon dioxide in Solution C, from the carbon dioxide concentration in the treatment solution (Solution C) determined in Step 2.

5. The treatment method according to claim 4, further comprising step 4: mixing the liquid A with the liquid C based on the amount of alkanolamine calculated in step 3, to prepare a reuse treatment liquid.

6. The treatment method according to claim 5 , wherein step 4 comprises mixing the solution B with the solution C based on the amount of alkanolamine calculated in step 3 .

7. The method for treating a substrate according to claim 1 or 4, wherein step 3 comprises calculating an amount of the alkanolamine using the following formula (I): Amount of alkanolamine (mass %)=[carbonate concentration in solution C (mol / L)×C×molar mass of aliphatic quaternary ammonium hydroxide (g / mol)]÷amount of aliphatic quaternary ammonium hydroxide in solution A (mass %)×amount of alkanolamine in solution A (mass %) (I) In the above formula (I), the coefficient C is a coefficient determined based on the degree of neutralization, the number of neutralizations added, and the unit conversion coefficient, and is a value in the range of 0.01 to 1.

8. 5. The method for treating a substrate according to claim 1, wherein a molar ratio of the aliphatic quaternary ammonium hydroxide to the carbonate ions in the solution C is 0.01 or more and 100 or less.

9. 5. A method for stripping a resin mask, comprising: stripping the resin mask from a substrate having the resin mask thereon, by using the method for treating a substrate according to claim 1.

10. A method for manufacturing an electronic component substrate, comprising the substrate processing method according to claim 1 or 4.

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