Method for cleaning substrate

Abstract

To prevent copper corrosion when peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on the surface.SOLUTION: The present disclosure, in one aspect, relates to a method for cleaning a substrate, the method comprising a peeling step of using a cleaner composition to peel a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface, wherein the cleaner composition contains an alkanolamine (component A), a quaternary ammonium hydroxide (component B), a thiazole-based corrosion inhibitor (component C), and water (component D).SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a method for cleaning a substrate.

Background Art

[0002] In recent years, in personal computers and various electronic devices, power consumption has been reduced, processing speed has been increased, and miniaturization has progressed. Wiring such as package substrates mounted on these devices has been becoming finer year by year. For forming such fine wiring and connection terminals such as pillars and bumps, the metal mask method has been mainly used so far. However, due to its low versatility and difficulty in coping with the miniaturization of wiring and the like, it is being changed to other new methods.

[0003] As one of the new methods, a method using a resin mask, also called a dry film resist, is known. In this method, an electroless plating is performed on an insulating substrate to form a metal seed layer. Subsequently, the metal seed layer is laminated with a resin mask, a pattern is formed by exposure and development processes, and copper wiring and tin bumps are formed by electroplating. The resin mask remaining on the substrate is finally peeled off and removed, and an alkaline peeling cleaner is used at that time.

[0004] For example, Patent Document 1 proposes a cleaning agent composition containing a quaternary base, an amine, an azole corrosion inhibitor, a reducing agent, and a solvent. Patent Document 2 proposes a composition for removing a resist for copper, which contains a 10 to 30% by weight liquid amine compound containing an alkanolamine, a 10 to 80% by weight glycol solvent, a 9.5 to 79% by weight polar solvent, and a 0.5 to 10% by weight corrosion inhibitor. Patent Document 3 proposes a dry film resist stripping liquid composition containing 10 to 30% by weight of an aqueous solution of a quaternary ammonium salt selected from tetramethylammonium hydroxide, tetramethylammonium pentafluoroxenonate, and mixtures thereof, 30 to 60% by weight of an alkanolamine compound, 10 to 30% by weight of a protic polar organic solvent, and 0.1 to 5% by weight of an azole compound containing sulfur.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] When forming fine wiring on a printed circuit board or the like, in addition to the remaining resin mask, in order to reduce the remaining of auxiliaries and the like contained in solder, plating solutions, etc. used for forming fine wiring and bumps, high detergency is required for the cleaning agent composition. Furthermore, since the corrosion of copper, which is widely used for many wirings and connection terminals, causes a deterioration in the quality and value of the package substrate, high corrosion prevention ability is required for the cleaning agent composition.

[0007] Therefore, the present disclosure provides a method for cleaning a substrate that can suppress copper corrosion when peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface.

Means for Solving the Problems

[0008] In one aspect, the present disclosure includes a peeling step of peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface using a cleaning agent composition. The cleaning composition relates to a method for cleaning a substrate, which contains alkanolamine (Component A), quaternary ammonium hydroxide (Component B), a thiazole-based corrosion inhibitor (Component C), and water (Component D).

Effect of the Invention

[0009] According to the present disclosure, it is possible to provide a method for cleaning a substrate capable of suppressing copper corrosion when peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask.

Embodiments for Carrying Out the Invention

[0010] The present disclosure is based on the finding that copper corrosion can be suppressed when peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface by using a cleaning composition containing alkanolamine (Component A), quaternary ammonium hydroxide (Component B), and a thiazole-based corrosion inhibitor (Component C).

[0011] In one aspect, the present disclosure includes a peeling step of peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface by using a cleaning composition (hereinafter, also referred to as "the cleaning composition of the present disclosure"). The cleaning composition relates to a method for cleaning a substrate (hereinafter, also referred to as "the cleaning method of the present disclosure"), which contains alkanolamine (Component A), quaternary ammonium hydroxide (Component B), a thiazole-based corrosion inhibitor (Component C), and water (Component D).

[0012] According to the present disclosure, it is possible to provide a cleaning method capable of suppressing copper corrosion when peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface. By using the cleaning method of the present disclosure, high-quality electronic components can be obtained with a high yield.

[0013] Although there are still unclear parts in the detailed mechanism of the effect manifestation of the present disclosure, it is presumed as follows. In the present disclosure, a cleaning composition containing an alkanolamine (Component A), a quaternary ammonium hydroxide (Component B), and a thiazole-based corrosion inhibitor (Component C) is used for stripping (cleaning) a resin mask, whereby Component A and Component B penetrate into the resin mask and promote the dissociation of the alkali-soluble resin incorporated in the resin mask. Furthermore, it is considered that the repulsion of charges generated by the dissociation promotes the stripping of the resin mask. On the other hand, it is considered that the alkanolamine (Component A) is also involved in the etching (corrosion) of copper. However, in the present disclosure, it is considered that a protective film is formed by the adsorption of the thiazole-based corrosion inhibitor (Component C) on the copper surface, and the etching (corrosion) of copper due to the coordination of the alkanolamine (Component A) is suppressed. As a result, it is considered that good stripping performance (resin mask removability) is exhibited while suppressing the etching (corrosion) of copper in the presence of the alkanolamine (Component A). In addition, in the suppression of copper etching (corrosion), forming a protective film on the copper surface is generally known as an effective method. The generation of this protective film may generate residues on the substrate and have an adverse effect on the subsequent processes after the stripping process (for example, the metal seed layer removal process). However, since the thiazole-based corrosion inhibitor (Component C) contained in the cleaning composition of the present disclosure can be removed by acid cleaning, it is considered that it is possible to suppress the etching (corrosion) of copper and reduce the residues on the substrate after cleaning, thereby preventing an adverse effect on the subsequent processes after the stripping process (for example, the metal seed layer removal process). However, the present disclosure may not be construed as being limited to this mechanism.

[0014] In the present disclosure, the resin mask is a mask for protecting the surface of a substance from processes such as etching, plating, and heating, that is, a mask formed of a resin that functions as a protective film. As the resin mask, in one or more embodiments, 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 cured resist layer may be mentioned. Also, 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. A negative resist has the property that its solubility in a developer decreases when exposed, and in a layer containing a negative resist (hereinafter, also referred to as a "negative resist layer"), the exposed portion is used as a resin mask after exposure and development processing. A positive resist has the property that its solubility in a developer increases when exposed, and in a layer containing a positive resist (hereinafter, also referred to as a "positive resist layer"), the exposed portion is removed after exposure and development processing, and the unexposed portion is used as a resin mask. By using a resin mask having such properties, fine connection portions of a circuit board such as metal wiring, metal pillars, and solder bumps can be formed. Examples of the resin material for forming the resin mask include a film-shaped photosensitive resin, a resist film, or a photoresist in one or more embodiments. A general-purpose resist film can be used. In one or more embodiments, the resin mask is a copper or tin plating mask for use in copper or tin plating treatment.

[0015] [Peeling step] The cleaning method of the present disclosure includes a step of peeling a resin mask from a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on its surface using the cleaning agent composition of the present disclosure (hereinafter, also simply referred to as the "peeling step"). In one or more embodiments, the peeling step includes bringing the object to be cleaned into contact with the cleaning agent composition of the present disclosure.

[0016] As a method for peeling a resin mask from an object to be cleaned using the cleaning composition of the present disclosure, or a method for bringing the cleaning composition of the present disclosure into contact with the object to be cleaned, for example, a method of bringing them into contact by immersing them in a cleaning bath containing the cleaning composition, a method of injecting the cleaning composition in a spray form to bring them into contact (shower method), an ultrasonic cleaning method of irradiating ultrasonic waves during immersion, etc. may be mentioned. The cleaning composition of the present disclosure can be used for cleaning as it is without dilution. Examples of the object to be cleaned include the objects to be cleaned described later. Examples of the immersion time include, for example, 1 minute or more and 10 minutes or less, and more preferably 3 minutes or more and 6 minutes or less. Examples of the spray time include, for example, 1 minute or more and 10 minutes or less, and more preferably 3 minutes or more and 6 minutes or less.

[0017] From the viewpoint that the detergency of the cleaning composition of the present disclosure is likely to be exhibited, in the cleaning method of the present disclosure, it is preferable to irradiate ultrasonic waves when the cleaning composition of the present disclosure is in contact with the object to be cleaned, 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 preferably, for example, 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

[0018] In the cleaning method of the present disclosure, from the viewpoint that the detergency of the cleaning composition of the present disclosure is likely to be exhibited, the temperature of the cleaning composition is preferably 40°C or higher, more preferably 50°C or higher, and from the viewpoint of reducing the influence on the organic resin-containing substrate, it is preferably 70°C or lower, more preferably 60°C or lower.

[0019] In one or more embodiments, the cleaning method of the present disclosure may perform acid cleaning after bringing the object to be cleaned into contact with the cleaning composition. That is, the cleaning method of the present disclosure may further include a step of acid cleaning the substrate after the peeling step (hereinafter, also referred to as the "acid cleaning step"). In one or more embodiments, the acid cleaning step includes bringing the substrate after the peeling step into contact with a cleaning agent (acid). Examples of the cleaning agent (acid) used for acid cleaning include, for example, sulfuric acid, nitric acid, and aqueous solutions diluted with water thereof. Examples of the pickling cleaning method include immersion cleaning, ultrasonic cleaning, oscillating cleaning, spray cleaning, etc. Examples of the pickling cleaning time include, for example, 1 second or more and 60 seconds or less, and more preferably 10 seconds or more and 30 seconds or less. Examples of the temperature of the cleaning agent (acid) used for pickling include, for example, 20°C or more and 40°C or less, and more preferably 25°C or more and 35°C or less.

[0020] In one or more embodiments, the cleaning method of the present disclosure may further include a step of rinsing with water and drying after bringing the object to be cleaned into contact with the cleaning agent composition of the present disclosure (after the peeling step) or after the pickling step. Examples of the rinsing method include running water rinsing. Examples of the drying method include air blow drying. In one or more embodiments, the cleaning method of the present disclosure may include a step of rinsing the object to be cleaned with water after bringing the object to be cleaned into contact with the cleaning agent composition of the present disclosure (after the peeling step) or after the pickling step.

[0021] [Object to be cleaned] In one or more embodiments, the object to be cleaned is a substrate having a copper-containing metal layer and a resin mask on its surface. In one or more embodiments, the substrate having a copper-containing metal layer and a resin mask on its surface has undergone a process of performing at least one of soldering and plating using a resin mask. In one or more embodiments, the copper-containing metal layer is a copper plating layer. The copper plating layer can be formed, for example, by electroless copper plating. In one or more embodiments, the copper-containing metal layer is used as a metal wiring. Examples of the thickness of the copper-containing metal layer include, for example, 3 μm to 30 μm. Examples of the substrate include an insulator plate, a film, etc.

[0022] In one or more embodiments, the object to be cleaned includes electronic components having copper-containing metal sites and resin masks on their surfaces and intermediate products in the manufacture thereof. Examples of the electronic components include at least one component selected from metal plates such as printed circuit boards, wafers, copper plates, and aluminum plates. The intermediate product is an intermediate product in the manufacturing process of the electronic component and includes the intermediate product after the resin mask treatment. Specific examples of the object to be cleaned include, for example, electronic components such as those in which wirings, connection terminals, etc. are formed on the surface of a substrate through a process of performing at least one of soldering and plating treatments (copper plating, aluminum plating, nickel plating, tin plating, etc.) using a resin mask. In the present disclosure, soldering means causing solder to exist in a resin mask non-existent portion on a substrate and forming solder bumps by heating. In the present disclosure, plating treatment means performing at least one plating treatment selected from copper plating, aluminum plating, nickel plating, and tin plating on a resin mask non-existent portion on a substrate. The resin mask non-existent portion refers to a portion where the resin mask has been removed by a development process in a resist pattern (pattern-shaped resin mask) formed by developing a resin mask laminated on a substrate. Therefore, in one aspect, the present disclosure relates to the use of the cleaning agent composition of the present disclosure as a cleaning agent in the manufacture of electronic components.

[0023] In one or more embodiments, the object to be cleaned is a substrate having a resist pattern (pattern-shaped resin mask) formed by developing a resin mask laminated on the substrate, and has undergone a process of performing at least one of soldering and plating treatments. For example, as the object to be cleaned, there is a substrate having a site that is a resin mask existing portion where a cured resist layer is formed on the substrate and a site where solder bumps or a plating layer is formed in a resin mask non-existent portion.

[0024] As the resin mask, for example, a negative-type resin mask or a positive-type resin mask may be used. In the present disclosure, the negative-type resin mask is formed using a negative-type resist, and examples thereof include a negative-type resist layer that has been exposed and / or developed. In the present disclosure, the positive-type resin mask is formed using a positive-type resist, and examples thereof include a positive-type resist layer that has been exposed and / or developed.

[0025] [Cleaning Agent Composition] In one or more embodiments, the cleaning agent composition of the present disclosure used in the stripping step is a cleaning agent composition containing the following Component A, the following Component B, the following Component C, and the following Component D. In one or more embodiments, the cleaning agent composition of the present disclosure may contain the following Component E. By using the cleaning agent composition of the present disclosure for cleaning a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on its surface, the resin mask can be removed while suppressing copper corrosion. And by using the cleaning agent composition of the present disclosure for cleaning electronic components such as electronic circuit boards having a resin mask, high-quality electronic components can be obtained with a high yield. In one or more embodiments, the cleaning agent composition of the present disclosure can be used for cleaning a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on its surface. In one or more embodiments, the cleaning agent composition of the present disclosure can be used to strip the resin mask from a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on its surface. That is, in one aspect, the present disclosure relates to the use of the cleaning agent composition of the present disclosure for stripping the resin mask from a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on its surface.

[0026] (Component A: Alkanolamine) Examples of the alkanolamine (amino alcohol) (hereinafter also referred to as "Component A") contained in the cleaning agent composition of the present disclosure include compounds represented by the following formula (I). Component A may be one type or a combination of two or more types. [Chemical Formula]

[0027] 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.

[0028] 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, from the viewpoint of improving the resin mask removability, component A preferably contains monoethanolamine (MEA).

[0029] From the viewpoints of improving the resin mask removability and suppressing copper corrosion, the content of Component A in the cleaning composition of the present disclosure is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and still more preferably 7% by mass or more. From the same viewpoints, it is preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less, and still more preferably less than 10% by mass. From the same viewpoints, the content of Component A in the cleaning composition of the present disclosure is preferably 1% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 12% by mass or less, still more preferably 5% by mass or more and 10% by mass or less, and still more preferably 7% by mass or more and less than 10% by mass. When Component A is a combination of two or more kinds, the content of Component A refers to their total content.

[0030] In the present disclosure, "the content of each component in the cleaning composition" refers to the content of each component at the time of cleaning, that is, when starting to use the cleaning composition for cleaning. In one or more embodiments, the content of each component in the cleaning composition of the present disclosure can be regarded as the blending amount of each component in the cleaning composition of the present disclosure.

[0031] (Component B: Quaternary ammonium hydroxide) Examples of the quaternary ammonium hydroxide (hereinafter also referred to as "Component B") contained in the cleaning composition of the present disclosure include, for example, the quaternary ammonium hydroxide represented by the following formula (II). Component B may be one kind or a combination of two or more kinds. [Chemical formula]

[0032] 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.

[0033] The quaternary ammonium hydroxide represented by formula (II) is a salt composed of a quaternary ammonium cation and hydroxide. For example, 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, from the viewpoint of improving the resin mask removability, component B preferably contains tetramethylammonium hydroxide (TMAH).

[0034] From the viewpoints of improving the resin mask removability and suppressing copper corrosion, the content of component B in the cleaning composition of the present disclosure is preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more, and from the same viewpoints, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less. From the same viewpoints, the content of component B in the cleaning composition of the present disclosure is preferably 1% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 10% by mass or less, still more preferably 2% by mass or more and 5% by mass or less. When component B is a combination of two or more kinds, the content of component B refers to their total content.

[0035] (Component C: Thiazole-based corrosion inhibitor) Examples of the thiazole-based corrosion inhibitor (hereinafter also referred to as "Component C") contained in the cleaning agent composition of the present disclosure include thiazole or its derivatives from the viewpoint of copper corrosion inhibition. For example, thiazole, benzothiazole, mercaptobenzothiazole (MBT), aminobenzothiazole (ABT), etc. are included. From the same viewpoint, it is more preferable that Component C contains mercaptobenzothiazole (MBT). Component C may be one kind or a combination of two or more kinds.

[0036] From the viewpoint of copper corrosion inhibition, the content of Component C in the cleaning agent composition of the present disclosure is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more. And from the viewpoints of removability of the corrosion inhibitor by pickling and reduction of residues on the substrate, it is preferably 0.5% by mass or less, more preferably 0.4% by mass or less, still more preferably 0.3% by mass or less. From the viewpoints of copper corrosion inhibition, removability of the corrosion inhibitor by pickling, and reduction of residues on the substrate, the content of Component C in the cleaning agent composition of the present disclosure is preferably 0.05% by mass or more and 0.5% by mass or less, more preferably 0.1% by mass or more and 0.4% by mass or less, still more preferably 0.2% by mass or more and 0.3% by mass or less. When Component C is a combination of two or more kinds, the content of Component C refers to their total content.

[0037] From the viewpoint of copper corrosion inhibition, the mass ratio A / C (content of Component A / content of Component C) of Component A and Component C in the cleaning agent composition of the present disclosure is preferably 200 or less, more preferably 150 or less, still more preferably 100 or less. And from the viewpoints of removability of the corrosion inhibitor by pickling and reduction of residues on the substrate, it is preferably 20 or more, more preferably 40 or more, still more preferably 50 or more. From the same viewpoint, the mass ratio A / C of Component A and Component C in the cleaning agent composition of the present disclosure is preferably 20 or more and 200 or less, more preferably 40 or more and 150 or less, still more preferably 50 or more and 100 or less.

[0038] (Component D: Water) As the water (hereinafter also referred to as "Component D") contained in the cleaning composition of the present disclosure, in one or more embodiments, ion-exchanged water, RO water, distilled water, pure water, ultrapure water, etc. may be mentioned.

[0039] The content of Component D in the cleaning composition of the present disclosure can be the remainder excluding Components A, B, C, and optional components described later. Specifically, from the viewpoints of improving resin mask removability and suppressing copper corrosion, the content of Component D in the cleaning composition of the present disclosure is preferably 60% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, and from the viewpoint of improving resin mask removability, it is preferably 98% by mass or less, more preferably 96% by mass or less, still more preferably 90% by mass or less, still more preferably 85% by mass or less. From the same viewpoints, the content of Component D in the cleaning composition of the present disclosure is preferably 60% by mass or more and 98% by mass or less, more preferably 65% by mass or more and 96% by mass or less, still more preferably 70% by mass or more and 90% by mass or less, still more preferably 80% by mass or more and 85% by mass or less.

[0040] [Organic solvent (Component E)] In one or more embodiments, the cleaning composition of the present disclosure preferably does not contain an organic solvent (hereinafter also referred to as "Component E") or the content of the organic solvent (Component E) is 15% by mass or less from the viewpoint of improving resin mask removability. Component E may be one kind or a combination of two or more kinds. As Component E, in one or more embodiments, at least one solvent selected from glycol ethers and aromatic ketones may be mentioned. As the glycol ether, from the same viewpoints, compounds having a structure in which 1 to 3 moles of ethylene glycol are added to an alcohol having 1 to 8 carbon atoms may be mentioned. Specific examples of the glycol ether include at least one selected from diethylene glycol monobutyl ether (BDG), ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol diethyl ether. As the aromatic ketone, from the same viewpoints, acetophenone and the like may be mentioned.

[0041] When the cleaning composition of the present disclosure contains Component E, from the viewpoint of improving the resin mask removability, the content of Component E in the cleaning composition of the present disclosure is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and from the same viewpoint, it is 15% by mass or less, more preferably 13% by mass or less, and still more preferably 10% by mass or less. More specifically, the content of Component E in the cleaning composition of the present disclosure is preferably 1% by mass or more and 15% by mass or less, more preferably 2% by mass or more and 13% by mass or less, and still more preferably 3% by mass or more and 10% by mass or less. When Component E is a combination of two or more, the content of Component E refers to their total content.

[0042] [Component F: Ammonium salt of organic acid] In one or more embodiments, the cleaning composition of the present disclosure can further contain at least one ammonium salt of an organic acid (hereinafter also referred to as "Component F") from the viewpoint of improving the resin mask removability. As Component F, from the same viewpoint, an ammonium salt of a carboxylic acid having 1 to 5 carbon atoms is preferable, and ammonium formate is more preferable. Component F may be one kind or a combination of two or more kinds.

[0043] When the cleaning composition of the present disclosure contains Component F, from the viewpoint of improving the resin mask removability, the content of Component F in the cleaning composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and from the same viewpoint, it is preferably 2% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1% by mass or less. More specifically, the content of Component F in the cleaning composition of the present disclosure is preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.2% by mass or more and 1.5% by mass or less, and still more preferably 0.3% by mass or more and 1% by mass or less. When Component F is a combination of two or more, the content of Component F refers to their total content.

[0044] In one or more embodiments, the cleaning composition of the present disclosure may further contain at least one selected from Component E and Component F from the viewpoint of improving the resin mask removability.

[0045] (Other Components) In addition to the above Components A to F, the cleaning composition of the present disclosure can further contain other components as needed. Examples of other components include components that can be used in ordinary cleaning agents, such as alkali agents other than Component A and Component B, amines other than Component A, solvents other than Component E, corrosion inhibitors other than Component C, surfactants, chelating agents, thickeners, dispersants, rust preventives, polymer compounds, solubilizers, antioxidants, preservatives, antifoaming agents, antibacterial agents, and the like.

[0046] In one or more embodiments, the cleaning composition of the present disclosure can be substantially free of reducing agents. The content of the reducing agent in the cleaning composition of the present disclosure is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and still more preferably 0% by mass (i.e., not contained).

[0047] From the viewpoints of reducing the drainage treatment load and the impact on the substrate, the total content of organic substances derived from Component A, Component B, Component C, and optional components (Component E, Component F, other components) during the use of the cleaning composition of the present disclosure is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and even more preferably 16% by mass or less. From the viewpoint of improving the resin mask removability, it is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and even more preferably 6% by mass or more. More specifically, the total content of organic substances derived from Component A, Component B, Component C, and optional components (Component E, Component F, other components) during the use of the cleaning composition of the present disclosure is preferably 2% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, still more preferably 4% by mass or more and 20% by mass or less, and even more preferably 6% by mass or more and 16% by mass or less.

[0048] [Method for Producing Cleaning Composition] In one or more embodiments, the cleaning composition of the present disclosure can be produced by blending the above-mentioned components A to D and, if necessary, any of the above-mentioned optional components (component E, component F, and other components) by a known method. For example, the cleaning composition of the present disclosure can be formed by blending at least the above-mentioned components A to D. Accordingly, the present disclosure relates to a method for producing a cleaning composition including a step of blending at least the above-mentioned components A to D. In the present disclosure, "blending" includes mixing components A to D and, if necessary, any of the above-mentioned optional components (component E, component F, and other components) simultaneously or in any order. In the method for producing the cleaning composition of the present disclosure, the preferred blending amount of each component can be the same as the preferred content of each component of the cleaning composition of the present disclosure described above.

[0049] The cleaning composition of the present disclosure may be prepared as a concentrate with a reduced amount of water (component D) within a range that does not cause separation, precipitation, etc. and impair storage stability. From the viewpoints of transportation and storage, the concentrate of the cleaning composition is preferably a concentrate with a dilution ratio of 3 times or more, and from the viewpoint of storage stability, it is preferably a concentrate with a dilution ratio of 30 times or less. The concentrate of the cleaning composition can be diluted with water (component D) so that components A to D and optional components (component E, component F, and other components) have the above-mentioned contents (i.e., the contents during cleaning) during use. Further, the concentrate of the cleaning composition can also be used by adding each component separately during use. In the present disclosure, "during use" or "during cleaning" of the cleaning composition in the concentrated liquid refers to a state in which the concentrate of the cleaning composition is diluted.

[0050] [Method for manufacturing electronic components] In one aspect, the present disclosure relates to a method for manufacturing an electronic component (hereinafter, also referred to as "the method for manufacturing an electronic component of the present disclosure") including a step of cleaning a substrate (object to be cleaned) having a copper-containing metal layer and a resin mask on its surface (hereinafter, also referred to as "cleaning step") using the cleaning method of the present disclosure. Examples of the cleaning method in the cleaning step include the same methods as the cleaning method of the present disclosure described above. Examples of the object to be cleaned include the objects to be cleaned described above. In one or more embodiments, the method for manufacturing an electronic component according to the present disclosure may include, before the cleaning step, performing at least one of soldering and plating on at least one electronic component selected from a printed circuit board, a wafer, and a metal plate using a resin mask. In one or more embodiments, the method for manufacturing an electronic component according to the present disclosure may include, after the cleaning step, etching a copper-containing metal layer. By performing cleaning using the cleaning method of the present disclosure, the resin mask attached to the substrate (electronic component) can be removed while suppressing copper corrosion, enabling the manufacture of highly reliable electronic components. Further, by using the cleaning method of the present disclosure, the removal of the resin mask attached to the electronic component becomes easy, so that the cleaning time can be shortened and the manufacturing efficiency of the electronic component can be improved.

[0051] [Kit] In one aspect, the present disclosure relates to a kit (hereinafter, also referred to as "the kit of the present disclosure") for use in either the cleaning method of the present disclosure or the method for manufacturing an electronic component of the present disclosure. In one or more embodiments, the kit of the present disclosure is a kit for manufacturing the cleaning agent composition of the present disclosure. According to the kit of the present disclosure, a cleaning agent composition capable of suppressing copper corrosion when peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface can be obtained. As one embodiment of the kit of the present disclosure, a solution containing component A (first liquid) and a solution containing component B and component C (second liquid) are included in a state where they are not mixed with each other. At least one of the first liquid and the second liquid further contains a part or all of water (component D), and the first liquid and the second liquid are mixed at the time of use. Examples of the kit (two-component type cleaning agent composition) include this. After the first liquid and the second liquid are mixed, they may be diluted with water (component D) as necessary. Each of the first liquid and the second liquid may contain the above-mentioned optional components as necessary.

Example

[0052] The following specifically describes the present disclosure by way of examples, but the present disclosure is not limited by these examples in any way.

[0053] 1. Preparation of the detergent compositions of Examples 1 to 3 and Comparative Example 1 The detergent compositions of Examples 1 to 3 and Comparative Example 1 were prepared by blending the respective components shown in Table 1 in the blending amounts (mass%, active ingredient) described in Table 1 and stirring and mixing them.

[0054] The following were used for the preparation of the detergent compositions of Examples 1 to 3 and Comparative Example 1. (Component A) MEA: Monoethanolamine [manufactured by Nippon Shokubai Co., Ltd.] (Component B) TMAH: Tetramethylammonium hydroxide [manufactured by Resonac Co., Ltd., 25% aqueous solution] (Component C) MBT: Mercaptobenzothiazole [manufactured by Tokyo Chemical Industry Co., Ltd.] (Non-Component C) MBO: Mercaptobenzoxazole [manufactured by Tokyo Chemical Industry Co., Ltd.] (Component D) Water [pure water of 1 μS / cm or less produced by the pure water apparatus G-10DSTSET of Organo Corporation] (Component E) BDG: Butyl diglycol [manufactured by Nippon Emulsifier Co., Ltd., diethylene glycol monobutyl ether] (Component F) Ammonium formate [manufactured by Toyama Chemical Industry Co., Ltd.]

[0055] 2. Evaluation of the detergent compositions of Examples 1 to 3 and Comparative Example 1 The following evaluations were performed on the prepared detergent compositions of Examples 1 to 3 and Comparative Example 1.

[0056] [Test piece] A test piece (50 mm × 50 mm) made of a solid substrate having a copper plating layer (thickness: 3 μm) on the surface was obtained by electroless plating on an insulating substrate.

[0057] [Evaluation of Cu Etchability (Evaluation of Copper Corrosion)] Prepare 2.5 L of each cleaning agent composition (Examples 1 to 3 and Comparative Example 1), heat it to 60 °C, and circulate it in a box-type spray cleaning machine equipped with a filling conical nozzle (J020, manufactured by Ikeuchi Co., Ltd.) as a spray nozzle. While circulating, copper plating (area: 25 cm per side 2 , 50 cm on both sides 2 ) was applied to the test piece, and sprayed for 4 minutes (pressure: 0.2 MPa, spray distance: 80 mm). The cleaning agent composition circulating in the cleaning machine was sampled, diluted with water, and then the elution amount of copper was measured by ICP analysis (Agilent 5110 ICP-OES manufactured by Agilent Technologies). According to the following formula, with the density of copper being 8.96 g / cm 3 , the Cu etching rate (μm / min) was evaluated from the elution amount. The results are shown in Table 1. The lower the numerical value of the Cu etching rate, the better the copper corrosion inhibition effect can be judged. Cu etching rate (μm / min) = Elution amount of copper (weight) ÷ Density of copper ÷ Plating area ÷ Treatment time

[0058]

Table 1

[0059] As shown in Table 1, it was found that Examples 1 to 3 using mercaptobenzothiazole (Component C) as a corrosion inhibitor had an excellent copper corrosion inhibition effect compared to Comparative Example 1 using mercaptobenzoxazole (non-Component C) as a corrosion inhibitor.

Industrial Applicability

[0060] According to the present disclosure, it is possible to provide a method for cleaning a substrate capable of suppressing copper corrosion when peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface. By using the cleaning method of the present disclosure, it is possible to improve the performance and reliability of the manufactured electronic components and improve the productivity of semiconductor devices.

Claims

1. A cleaning method comprising a peeling step of peeling a resin mask from a substrate having a copper-containing metal layer and a resin mask on its surface using a cleaning agent composition, wherein the cleaning agent composition contains an alkanolamine (Component A), a quaternary ammonium hydroxide (Component B), a thiazole-based corrosion inhibitor (Component C), and water (Component D).

2. The cleaning method of the substrate according to Claim 1, wherein the cleaning agent composition does not contain an organic solvent (Component E) or contains the organic solvent (Component E) in an amount of 15% by mass or less.

3. The cleaning method according to Claim 1 or 2, wherein the content of Component D in the cleaning agent composition is 65% by mass or more.

4. The cleaning method according to any one of Claims 1 to 3, wherein Component A contains monoethanolamine.

5. The cleaning method according to any one of Claims 1 to 4, wherein Component B contains tetramethylammonium hydroxide.

6. The cleaning method according to any one of Claims 1 to 5, wherein Component C contains mercaptobenzothiazole.

7. The cleaning method according to any one of Claims 1 to 6, further comprising a step of pickling the substrate after the peeling step.

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