TW202432817A - Photoresist removal composition and photoresist removal method - Google Patents

Abstract

The present invention is able to provide a composition for removing a photoresist, which is used for the purpose of forming a pattern that contains copper, after the formation of the pattern, the composition containing an alkaline agent, an ammonium ion source and an azole compound, wherein the alkaline agent contains at least one substance that is selected from the group consisting of an alkanolamine, a quaternary ammonium hydroxide and an inorganic alkali.

Description

Photoresist removal composition and photoresist removal method

The present invention relates to a photoresist removal composition, a photoresist removal method using the photoresist removal composition, etc.

In recent years, electronic devices have been miniaturized and highly functionalized, and printed wiring boards used in such electronic devices are also required to be miniaturized and highly functionalized. In order to manufacture printed wiring boards that meet such expectations, the following methods are adopted. For example, a metal layer called a seed layer is formed on an insulating layer having copper wiring in part, a photoresist layer is formed on its surface, and after exposure and development to form a resist pattern, copper plating is performed on the pattern opening, and then the photoresist and seed layer are removed to form a circuit pattern of the connection terminal portion of the copper wiring.

As described above, in the manufacturing method of printed wiring boards, etc., most of them include a step of removing photoresist, and the photoresist removal step usually uses an aqueous solution having various components (Patent Document 1, etc.). [Prior Technical Document] [Patent Document]

[Patent Document 1] International Publication No. 2020/022491

[The problem that the invention wants to solve]

In the manufacturing steps of conventional printed wiring boards, the removal of photoresist may not be performed quickly and sufficiently. If the photoresist can be removed quickly and reliably, the productivity of the printed wiring board can be improved. In addition, in the step of removing the photoresist, if the conventional treatment liquid is used, especially the treatment liquid with high reactivity in order to efficiently remove the photoresist, there is a possibility of damage to the copper-plated components.

Considering the above situation, there is a need for a method that has excellent photoresist removal performance as one of the manufacturing steps of printed wiring boards, etc., and can reliably protect copper-containing components such as copper plating. [Means for solving the problem]

The present invention includes, for example, the following aspects. [1] A composition for removing a photoresist used to form a pattern containing copper after the pattern is formed, comprising: an alkaline agent, an ammonium ion source, and an azole compound, the alkaline agent comprising at least one selected from the group consisting of alkanolamines, quaternary ammonium hydroxides, and inorganic bases. [2] A composition as in [1], wherein the etching rate of the copper is less than 0.05 μm/min. [3] A composition as in [1], wherein the ammonium ion source comprises at least one of ammonia and an ammonium salt of an organic acid. [4] A composition as in [3], wherein the ammonium ion source comprises an ammonium salt of an aromatic organic acid. [5] A composition as described in [3], wherein the ammonium ion source comprises at least one of ammonium benzoate, diammonium phthalate and ammonium formate. [6] A composition as described in [1], wherein the azole compound comprises at least one of an imidazole compound, a benzimidazole compound and a pyrazole compound. [7] A composition as described in [1], further comprising an organic solvent. [8] A composition as described in [1], wherein the composition, based on the total amount of the composition, comprises: 3.0 to 50% by weight of the alkaline agent, 0.1 to 20% by weight of the ammonium ion source, and 0.001 to 1.0% by weight of the azole compound. [9] A composition as described in [1], wherein the composition is water-soluble. [10] The composition of [1], wherein the composition does not contain a chelating agent or a sulfur-containing organic acid. [11] The composition of [1], wherein the pattern is a circuit pattern of a connection terminal portion of a copper wiring formed on at least a portion of an insulating layer having a copper wiring.

[12] A method for removing photoresist, comprising: for a photoresist used to form a pattern containing copper, bringing a composition as described in any one of [1] to [11] into contact and removing the photoresist. [13] A method for removing photoresist as described in [12], wherein the pattern is a circuit pattern of a connection terminal portion of a copper wiring formed on an insulating layer having at least a portion of the copper wiring. [14] A method for manufacturing a printed wiring board, a semiconductor element, or a semiconductor package, comprising: for a photoresist used to form a pattern containing copper, bringing a composition as described in any one of [1] to [11] into contact and removing the photoresist. [15] A method for manufacturing a printed wiring board, a semiconductor element, or a semiconductor package as described in [14], wherein the pattern is a circuit pattern of a connection terminal portion of a copper wiring formed on an insulating layer having at least a portion of the copper wiring. [Effect of the invention]

According to the present invention, a photoresist removal composition is provided which can efficiently remove photoresist and reliably protect copper-containing components such as copper plating in a printed wiring board.

The composition of the present invention is suitable for use in removing photoresist after forming a copper-containing pattern, and contains at least a predetermined alkaline agent, an ammonium ion source and an azole compound. The composition is described in detail below.

[I. Composition] The composition is preferably water-soluble. That is, at least a portion of the composition is preferably soluble in water or can be suspended, and more preferably can be uniformly mixed with water in any proportion. In addition, at least a portion of the components other than water contained in the composition is preferably soluble in water, and more preferably the components other than water contained in the composition can be uniformly mixed with water.

<I-1. (A) Alkaline agent> The composition preferably contains 3.0 to 50% by mass of (A) alkaline agent (hereinafter also referred to as component (A)) based on the total mass. The content of the alkaline agent in the composition is preferably 4.0 to 40% by mass, further preferably 5.0 to 30% by mass or 6.0 to 35% by mass, and particularly preferably 7.0 to 15% by mass, 8.0 to 20% by mass or 9.0 to 12% by mass, etc., based on the total mass of the composition. The composition containing component (A) has good photoresist removal properties and is believed to have the effect of suppressing damage to circuit patterns containing copper, copper alloy, etc., which are connection terminals of copper wiring.

The alkaline agent (A) preferably contains any one selected from (A-1) alkanolamine, (A-2) quaternary ammonium hydroxide and (A-3) an inorganic base, more preferably contains two of them, and most preferably contains all of (A-1) to (A-3).

(A-1) Alkanolamines The types of (A-1) alkanolamines that may be contained as component (A) in the composition are not particularly limited, and examples thereof include monoalkanolamines, dialkanolamines, trialkanolamines, and alkylates (N-alkylates, O-alkylates) thereof. Examples of the alkanolamines (A) include 2-aminoethanol (monoethanolamine), N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, 1-amino-2-propanol (isopropanolamine), N-methylisopropanolamine, N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropane-1-ol, N-methyl-2-amino-propane-1-ol, N-ethyl- 2-amino-propane-1-ol, 1-aminopropane-3-ol, N-methyl-1-aminopropane-3-ol, N-ethyl-1-aminopropane-3-ol, 1-aminobutane-2-ol, N-methyl-1-aminobutane-2-ol, N-ethyl-1-aminobutane-2-ol, 2-aminobutane-1-ol, N-methyl-2-aminobutane-1-ol, N-ethyl-2-aminobutane-1-ol Alcohol, 3-aminobutane-1-ol, N-methyl-3-aminobutane-1-ol, N-ethyl-3-aminobutane-1-ol, 1-aminobutane-4-ol, N-methyl-1-aminobutane-4-ol, N-ethyl-1-aminobutane-4-ol, 1-amino-2-methylpropane-2-ol, 2-amino-2-methylpropane-1-ol, 1-aminopentane-4-ol, 2-amino-4-methyl 1-aminopentane-1-ol, 2-aminohexane-1-ol, 3-aminoheptane-4-ol, 1-aminooctane-2-ol, 5-aminooctane-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(oxymethyl)aminomethane, 1,2-diaminopropane-3-ol, 1,3-diaminopropane-2-ol, 2-(2-aminoethoxy)ethanol, etc. are more ideal. These can be used alone or in combination of two or more. Among these, the alkanolamine is preferably one or more selected from the group consisting of 2-aminoethanol (monoethanolamine) and 1-amino-2-propanol.

The content of the alkanolamine is preferably 1.0-50% by mass, more preferably 1.5-45% by mass, 1.5-42% by mass, 2.0-30% by mass or 2.0-15% by mass, further preferably 3.0-12% by mass, particularly preferably 4.0-8.0% by mass or 5.0-9.0% by mass, etc., based on the total amount of the composition.

(A-2) Quaternary ammonium hydroxide The type of (A-2) quaternary ammonium hydroxide that can be contained in the composition as component (A) is not particularly limited, and examples thereof include tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, triethyl methyl ammonium hydroxide, ethyl trimethyl ammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, and triethyl (2-hydroxyethyl) ammonium hydroxide. These can be used alone or in combination of two or more. Among these, the quaternary ammonium hydroxide is preferably one or more selected from the group consisting of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, and triethyl methyl ammonium hydroxide.

The content of the grade 4 ammonium hydroxide is preferably 0.3-12% by mass, more preferably 0.5-10% by mass, more preferably 1.0-8.0% by mass, and particularly preferably 1.5-5.0% by mass or 2.0-6.0% by mass, based on the total amount of the composition.

(A-3) Inorganic base The type of (A-3) inorganic base that can be contained in the composition as component (A) is not particularly limited, and examples thereof include alkali metal compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate; alkali earth metal compounds such as magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, calcium silicate, magnesium silicate; transition metal compounds such as copper hydroxide and iron hydroxide; ammonia, etc. Among these, the inorganic base is preferably potassium hydroxide, sodium hydroxide, etc.

The content of the inorganic base is preferably 0.001 to 5.0 mass %, more preferably 0.01 to 3.0 mass %, further preferably 0.05 to 2.0 mass %, particularly preferably 0.1 to 0.5 mass % or 0.2 to 1.0 mass %, etc., based on the total amount of the composition.

<I-2. (B) Ammonium ion source> The composition system preferably contains 0.1 to 20 mass % of (B) ammonium ion source (hereinafter also referred to as component (B)) based on the total mass. The content of the ammonium ion source in the composition is preferably 0.15 to 10 mass %, further preferably 0.20 to 5.0 mass %, and particularly preferably 0.25 to 2.5 mass %, 0.50 to 3.0 mass % or 0.25 to 2.0 mass %, etc., based on the total mass of the composition. The composition system containing component (B) is considered to have the effect of improving the removability of the photoresist.

The type of ammonium ion source contained as component (B) in the composition is not particularly limited, and examples thereof include ammonia, ammonium salts of halogenated ammonium salts (ammonium chloride, ammonium bromide, ammonium iodide, etc.), organic acid ammonium salts, inorganic acid ammonium salts, etc. As the ammonium ion source, an organic acid ammonium salt is preferred, and examples of the organic acid ammonium salt include ammonium salts of aromatic organic acids, ammonium salts of fatty acids, etc.

As ammonium salts of aromatic organic acids, for example, mono-, di-, and tri-ammonium salts of aromatic carboxylic acids having 6 to 30 carbon atoms can be cited, and specifically, ammonium salts of benzoic acid, phthalic acid, salicylic acid, etc., that is, ammonium benzoate, (di)ammonium phthalate, ammonium salicylate, etc. can be cited. In addition, as ammonium salts of fatty acids, mono-, di-, and tri-ammonium salts of saturated or unsaturated fatty acids having 1 to 20 carbon atoms can be cited, and specifically, saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, tridecanoic acid, palmitic acid, and stearic acid can be cited; unsaturated fatty acids such as acrylic acid, methacrylic acid, oleic acid, linoleic acid, and perilla acid can be cited; and ammonium salts of the like.

As the ammonium ion source, one kind may be used, or two or more kinds may be used. The component (B) in the composition preferably contains 30% by mass or more of an aromatic organic acid ammonium salt or a fatty acid ammonium salt, more preferably 50% by mass or more of an aromatic organic acid ammonium salt or a fatty acid ammonium salt, further preferably 70% by mass or more of an aromatic organic acid ammonium salt or a fatty acid ammonium salt, and particularly preferably 90% by mass or more of an aromatic organic acid ammonium salt or a fatty acid ammonium salt, based on the total amount of the ammonium ion source. It is more ideal that the composition contains only an aromatic organic acid ammonium salt or a fatty acid ammonium salt as the ammonium ion source.

<I-3. (C) Azole compound> The composition preferably contains 0.001 to 1.0 mass% of (C) azole compound (hereinafter also referred to as component (C)) based on the total mass. The content of the azole compound in the composition is preferably 0.005 to 0.80 mass%, further preferably 0.01 to 0.60 mass% or 0.015 to 0.70 mass%, and particularly preferably 0.02 to 0.40 mass%, 0.025 to 0.50 mass% or 0.03 to 0.30 mass%, etc., based on the total mass of the composition. The composition containing component (C) is believed to have the effect of protecting a metal layer containing copper or a copper alloy and reducing the etching rate of copper.

The azole compound in the composition preferably contains at least one of a triazole compound, an imidazole compound, a benzimidazole compound, and a pyrazole compound. As the triazole compound, there is no particular limitation as long as it is a compound having a triazole ring, and examples thereof include 1,2,3-triazole, 1,2,4-triazole, a triazole having a substituent with a carbon number of 10 or less, a triazole such as tolyltriazole having an aromatic ring condensed to the triazole ring, and triazole salts thereof. As the imidazole compound, there is no particular limitation as long as it is a compound having an imidazole ring, and examples thereof include imidazole, an imidazole derivative having a substituent with a carbon number of 10 or less, for example, 1-alkylimidazoles such as 1-methylimidazole, 4-alkylimidazoles such as 4-methylimidazole, 2-alkylimidazole, and imidazole salts thereof. As the benzimidazole compound, there is no particular limitation as long as it is a compound having a benzimidazole skeleton, and examples thereof include benzimidazole, benzimidazole derivatives having a substituent having a carbon number of 10 or less, such as 1-alkylbenzimidazole, 2-alkylbenzimidazole, 7-alkylbenzimidazole, and benzimidazole salts thereof. In addition, as the pyrazole compound, examples thereof include pyrazole, pyrazole having a substituent having a carbon number of 10 or less, 1-alkylpyrazole such as 1-methylpyrazole, 3-alkylpyrazole such as 3-methylpyrazole, 4-alkylpyrazole such as 4-methylpyrazole, 5-alkylpyrazole such as 5-methylpyrazole, and pyrazole salts thereof.

<I-4. Water> The composition preferably contains water. There is no particular restriction on the type of water contained in the composition. It is preferably water obtained by removing metal ions, organic impurities, particulate particles, etc. through distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc. It is more preferably pure water, and particularly preferably ultrapure water. The water content in the composition is preferably 20% by mass or more, more preferably more than 20% by mass, more preferably in the range of 20 to 99% by mass, further preferably 40 to 97% by mass, further preferably 60 to 95% by mass, and particularly preferably 70 to 95% by mass, based on the total amount of the composition. The composition adjusted to such a water content improves the reactivity to the photoresist and the removal of the photoresist.

<I-5. Other components> The composition may contain other minor components as required within the range that does not hinder the above effects. As for other minor components, solvents, pH adjusters, surfactants, defoamers, etc. can be listed. In addition, carbonate ions, carbonates that generate carbonate ions, bicarbonates, etc. can be added to the composition. If carbonate ions are added to the composition, the corrosion resistance of copper can be improved. As specific examples of carbonates and bicarbonates, salts of ammonium ions, salts of alkali metals or alkali earth metals, etc. can be listed. Ammonium carbonate salts such as tetramethylammonium carbonate can also be added to the composition. The content of the minor components in the composition is preferably 10% by mass or less, more preferably 5.0% by mass or less, further preferably 3.0% by mass or less, further preferably 2.0% by mass or less, or 1.5% by mass or less, based on the total amount of the composition. In addition, the content of each component of the salt that generates carbonate ions in the composition is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, further preferably 2.0% by mass or less, or 1.5% by mass or less. In addition, the composition is preferably a solvent and does not contain solid particles such as abrasive particles.

In the composition, for example, an organic solvent such as an ether compound or alcohol is preferably added. If a predetermined solvent is used, it is believed that the solubility of the photoresist in the composition is improved and the removal property is enhanced. Specific examples of ethers in suitable organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, phenyl glycol = ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, etc. In addition, as specific examples of alcohols in suitable organic solvents, aromatic alcohols can be cited, such as benzyl alcohol, salicylic alcohol, anisyl alcohol, anise alcohol, gentisyl alcohol, protocatechuic alcohol, vanillyl alcohol, veratryl alcohol, syringyl alcohol, cumyl alcohol, phenylethyl alcohol, etc.

The content of the solvent is preferably 0.01-20 mass %, more preferably 0.1-10 mass %, further preferably 0.2-5.0 mass %, particularly preferably 0.3-3.5 mass % or 0.4-4.0 mass %, etc., based on the total amount of the composition.

In addition, it is also considered that there are components that should not be added to the composition. As for the undesirable components in the composition, there are chelating agents and sulfur-containing organic acids. If the photoresist is removed by a composition containing a chelating agent, there is a possibility that the residual chelating agent will cause adverse effects in the subsequent flash etching step of etching copper. This is because if the chelating agent is attached to the surface of copper, it will hinder the etching process. In addition, when an organic acid containing sulfur atoms is used as a component of the composition, the sulfur-containing compound will cause the generation of odor and reduce the stability of the composition. Therefore, in the composition of the present invention, it is preferable that neither the chelating agent nor the sulfur-containing organic acid is contained.

<I-6. Preparation method of composition> The composition of the present invention is prepared by adding (A) component, (B) component, (C) component, water, and other components as needed, and preferably by stirring until it becomes completely uniform. When manufacturing the composition, the order of adding and mixing the components is not particularly limited. For example, a certain amount of water can be added to any of (A) component (A-1) to (A-3), and other components other than water can be prepared as a concentrated liquid, and these can be mixed at the site of using the composition. In this way, any component can be transported in a concentrated state, that is, in a state without water, and water can be added to prepare the composition.

<I-7. Properties of the composition> The pH range of the composition of the present invention is not particularly limited. The pH value of the composition in one embodiment is 8 or more, preferably 10 or more, and more preferably 11 or more. The pH value can be measured by a general method using a pH meter.

According to the composition of the present invention, damage to copper and copper alloys can be suppressed. Therefore, the etching rate of copper evaluated by the method described in detail below in the section of the embodiment can be suppressed to 0.050 μm/min or less. More preferably, the etching rate of copper evaluated by the method described in detail below is 0.040 μm/min or less, more preferably 0.030 μm/min or less, and particularly preferably 0.020 μm/min or 0.015 μm/min or less.

According to the composition of the present invention, photoresist can be effectively removed. Therefore, the value of L.P. (lifting point) of the stripping speed evaluated by the method described in detail later in the section of the embodiment can be 100 seconds or less. More preferably, the value of L.P. evaluated by the method described in detail later is 90 seconds or less, more preferably 85 seconds or less, and particularly preferably 80 seconds or less or 75 seconds or less.

<I-8. Usage form of the composition> There is no particular restriction on the temperature of the composition used for removing photoresist, and the temperature is preferably 10~70℃, more preferably 20~65℃, and further preferably 25~60℃. By using the composition in such a temperature range, the photoresist removal property becomes good, and the composition change of the composition can be suppressed, making it easy to maintain the photoresist removal conditions.

There is no particular restriction on the treatment time of the photoresist made of the composition, and it is preferably 20 to 600 seconds, more preferably 30 to 300 seconds, and can also be 30 to 240 seconds. The treatment time is the time that the composition is in contact with the photoresist, and can be appropriately selected according to various conditions such as the surface state of the photoresist to be removed, the concentration of the composition, the temperature, and the treatment method.

There is no particular limitation on the method of bringing the composition of the present invention into contact with the photoresist. For example, the composition of the present invention may be brought into contact with the photoresist to be removed by dripping (single-wafer spinning process) or spraying, or the photoresist to be removed may be immersed in the composition of the present invention. Any method may be used in the present invention.

<II. Photoresist removal method> The photoresist removal method of the present invention includes: a photoresist removal step of contacting the composition of the present invention with the photoresist used to form a pattern containing copper. The photoresist removal method is described below.

The composition of the present invention is suitable for use, for example, in a case where a photoresist is used to form a circuit pattern containing copper as a connection terminal portion of the copper wiring on an insulating layer having at least a portion of copper wiring, and the photoresist is removed after the circuit pattern is formed. Here, "at least a portion of the insulating layer having copper wiring" is an insulating layer in which copper wiring is buried on the surface or inside without any particular limitation, and examples thereof include a printed wiring board, a semiconductor element mounting package substrate, and a silicon insulating layer of a semiconductor wafer. In addition, "a circuit pattern containing copper as a connection terminal portion of the copper wiring" is, for example, a connection terminal portion of the copper wiring having an insulating layer, which is used to electrically connect to other components. In one embodiment of the present invention, the connection terminal portion is a connection terminal portion of a copper wiring in a printed wiring board. In addition, in one embodiment of the present invention, the connection terminal portion is a connection terminal portion of a copper wiring in a semiconductor element mounting package substrate. In addition, in one embodiment of the present invention, the connection terminal portion is a connection terminal portion of a copper wiring in a semiconductor element.

<III. Manufacturing method of printed wiring, etc.> The manufacturing method of printed wiring, etc. of the present invention includes: a photoresist removal step of bringing the composition of the present invention into contact with a photoresist used to form a copper-containing pattern. In addition to printed wiring boards, the photoresist removal step in the manufacturing method of semiconductor elements and semiconductor packages can also be appropriately used with the composition of the present invention.

For example, the composition of the present invention can be used in the manufacturing step of a printed wiring board (e.g., a semiconductor device mounting package substrate), where a photoresist is used to form a circuit pattern containing copper that becomes a connection terminal portion of the copper wiring on an insulating layer having at least a portion of copper wiring, and the photoresist is removed after the circuit pattern is formed. In addition, the composition of the present invention can be used in the manufacturing step of a semiconductor device, where a photoresist is used to form a circuit pattern containing copper that becomes a connection terminal portion of the copper wiring and at least one selected from the group consisting of tin and tin alloys on an insulating layer having at least a portion of copper wiring, and the photoresist is removed after the circuit pattern is formed.

As a photoresist used for printed wiring boards, for example, there can be mentioned a composition containing an adhesive polymer, a photopolymerizable monomer, a photopolymerization initiator, and other additives. As an adhesive polymer, for example, there can be mentioned a composition obtained by copolymerizing several vinyl monomers such as methacrylate, acrylate, styrene, etc., with at least one of methacrylic acid and acrylic acid as an essential component. As a photopolymerizable monomer, at least one of methacrylate and acrylate can be listed as more desirable. As a photopolymerization initiator, there can be listed at least one selected from the group consisting of benzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-ethylanthraquinone, benzoin, benzoin methyl ether, 9-phenylacridine, benzyl dimethyl ketone, and benzyl diethyl ketone. In addition, a two-molecule system consisting of a hexaarylbiimidazole and a hydrogen donor (2-phenylbenzoxazole, N-phenylglycine) can also be used. In addition, as other additives, thermal polymerization initiators or dyes can be listed.

As photoresists that can be used for semiconductor devices, phenol-formaldehyde resins (collectively referred to as "novolac resins") and combinations of naphthoquinone diazide compounds as photosensitive components are more ideal.

In addition, as the resist disposed between the metal wirings, dry film resists, liquid resists, etc. can be listed. Among these, the resist is preferably a dry film resist. As the dry film resist, there is no particular limitation, and it is preferably formed from a photosensitive resin. As the photosensitive resin, negative photosensitive resins and positive photosensitive resins can be listed.

Negative photosensitive resins are not particularly limited, and examples thereof include diazo-based photosensitive resins, acetylene-based low molecular weight photosensitive resins, vinyl-based low molecular weight photosensitive resins, insoluble high molecular weight photosensitive resins, and chromic acid-based photosensitive resins. These negative photosensitive resins may be used alone or in combination of two or more.

There are no particular limitations on the positive photosensitive resin, and examples thereof include quinonediazide-based photosensitive resins, soluble polymer-based photosensitive resins, etc. These positive photosensitive resins may be used alone or in combination of two or more.

Among these, the dry film resist is preferably formed from a negative photosensitive resin. The negative photosensitive resin is hardened by the exposure treatment during pattern formation and becomes insoluble in the developer, so the exposed portion (the portion of the negative photosensitive resin that has been hardened) remains as a dry film resist. Here, the negative photosensitive resin during exposure is easy to harden, especially at the surface portion exposed by the exposure, and the surface portion of the obtained dry film resist can have a particularly dense structure. Therefore, even if the dry film resist is to be removed depending on the composition, it is sometimes difficult for the composition to penetrate into the interior of the dry film resist. In addition, the dry film resist may not be removed because the resist removal ability of the composition is not sufficient. As a result, it sometimes takes time to remove the dry film resist. In contrast, the composition of the present invention can easily penetrate into the dry film resist, so the dry film resist can be quickly stripped and removed. [Example]

(Preparation of samples for evaluation of peelability) Samples for evaluation of peelability were prepared as follows. First, chemical copper plating was performed on a copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd., CCL-HL832NS (MT-FL) 0.1mmtC/C) to form a copper thin film (thickness: 1.0μm). A dry film resist (Showa Denko Co., Ltd., RD-3025, thickness: 25μm) was attached to the surface of the copper thin film, and a circuit mask pattern was applied thereon, and exposure and development were performed. Electrolytic copper plating (thickness: 17μm) was performed on the opening of the circuit pattern formed by exposure and development of the dry film resist to obtain a sample for evaluation of peelability. The pattern of the dry film resist applied to the samples for peelability evaluation is a dot matrix of 100~300μmφ.

(Preparation of samples for evaluation of copper corrosion resistance) The samples for evaluation of copper corrosion resistance were prepared as follows. That is, electrolytic copper plating (thickness: 35 μm) was performed on the surface of a copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd., CCL-HL832NX) to obtain samples for evaluation of copper corrosion resistance.

(Peeling speed (L.P. (lifting point)))) For the above-mentioned sample for evaluation of peelability, the aqueous composition described in the embodiment and the comparative example was sprayed at a spray pressure of 0.15MPa and 50°C to make it contact. Then, the time from the time of spraying the aqueous composition until the dry film resist completely fell off the substrate of the sample for evaluation of peelability was measured as L.P (seconds). In addition, in the measurement of L.P., the 250μmφ dot matrix pattern part applied to the sample for evaluation of peelability was visually observed and used as the time when the dry film resist was removed.

(Corrosion resistance of copper (Cu ER (etching rate))) The above copper corrosion resistance evaluation sample cut into 4 cm × 4 cm square was sprayed with the aqueous composition described in the embodiment and the comparative example at a spray pressure of 0.15 MPa and 50°C for 5 minutes. Then, the copper corrosion resistance evaluation sample was washed with pure water, cleaned with 5 mass% sulfuric acid, and washed with pure water, and then fully dried. The value of Cu ER (μm/min) was calculated as follows. That is, the mass of the copper corrosion resistance evaluation sample before and after the spray treatment of the aqueous composition was measured, and the etched thickness was calculated from the mass difference and the density of copper (8.93 g/cm ³ ), and the sample size (treatment area [cm ² ], and the back of the copper corrosion resistance evaluation sample was protected by a masking tape, so the treatment area was the area of the sample surface), and the etching amount per minute was calculated by the following formula (I). [Figure 1]

(Releasability) For the samples for evaluating the releasability, the aqueous composition described in the embodiment and the comparative example was sprayed at a spray pressure of 0.15 MPa and 50°C for 3 minutes to make it contact. Then, it was washed with pure water, cleaned with 5 mass% sulfuric acid, and washed with pure water, and then fully dried. The evaluation of the releasability was carried out as follows. That is, using an optical microscope (MX-61L objective lens 50 times manufactured by Olympus Corporation), the residue of the dry film resist of the sample for evaluating the releasability after the spray treatment of the aqueous composition was confirmed, and the evaluation was carried out according to the following criteria. Very good: The residue of the dry film resist of 100~300μmφ is less than 2 Good: The residue of the dry film resist of 100~300μmφ is less than 110 Poor: The residue of the dry film resist of 100~300μmφ exceeds 110

[Example 1] An aqueous composition was prepared by adding monoethanolamine (MEA) to 323g of pure water to a final amount of 6 mass% (75% MEA aqueous solution is 32g), tetramethylammonium hydroxide (TMAH) to a final amount of 2 mass% (25% TMAH aqueous solution is 32g), ammonium benzoate to a final amount of 1.0 mass% (4.0g), and 4-methylimidazole to a final amount of 0.09 mass% (0.36g). The L.P. of the obtained aqueous composition was 47sec, and the Cu E.R. was 0.03μm/min, and the stripping property was good. The properties and evaluation results of the aqueous composition are shown in Table 1 below.

[Examples 2 to 16 and Comparative Examples 1 to 7] As shown in Table 1 below, the types and amounts of the components in the composition of Example 1 were arbitrarily changed, and additional components were added to some of the Examples and Comparative Examples. A water-based composition was prepared in the same manner as Example 1 and an evaluation test was performed. The properties and evaluation results of the water-based composition of each Example and Comparative Example are shown in Table 1 below. In addition, tetramethylammonium bicarbonate (TMBC) added to the water-based composition of Example 12, etc. is produced as a decomposition product of tetramethylammonium hydroxide, which reduces the stripping performance of the dry film resist caused by the water-based composition. Therefore, in order to evaluate the stripping treatment of the aqueous composition that has produced tetramethylammonium bicarbonate after long-term use, the bicarbonate was added to the aqueous composition of this example. [Table 1]

As can be clearly seen from the above results, it is confirmed that the aqueous composition of the embodiment containing a predetermined ammonium ion source has a shorter time indicated by the L.P. (lifting point) value than the aqueous composition of the comparative example, can quickly strip the photoresist, and can suppress the generation of resist residue. In addition, the embodiment has a tendency to have a lower Cu E.R. (etching rate) value than the comparative example, and can obtain excellent results of copper corrosion resistance. In addition, if Example 1 using ammonium benzoate as an ammonium ion source and Comparative Example 3 adding potassium benzoate are compared, Example 1 has a shorter L.P. (lifting point) time and a better photoresist stripping speed. In addition, even if Example 7 using diammonium phthalate as an ammonium ion source and Comparative Example 4 adding phthalic acid are compared, the same tendency is also considered. From these results, in the aqueous composition containing a predetermined ammonium ion source, the stripping property of the photoresist is confirmed, and the stripping speed is especially improved.

Claims (15)

A composition for removing a photoresist used to form a pattern containing copper after the pattern is formed, comprising: an alkaline agent, an ammonium ion source, and an azole compound, wherein the alkaline agent comprises at least one selected from the group consisting of alkanolamine, quaternary ammonium hydroxide, and an inorganic base. The composition of claim 1, wherein the copper has an etching rate of less than 0.05 μm/min. The composition of claim 1, wherein the ammonium ion source comprises at least one of ammonia and an ammonium salt of an organic acid. The composition of claim 3, wherein the ammonium ion source comprises an ammonium salt of an aromatic organic acid. The composition of claim 3, wherein the ammonium ion source comprises at least any one of ammonium benzoate, diammonium phthalate and ammonium formate. The composition of claim 1, wherein the azole compound comprises at least any one of an imidazole compound, a benzimidazole compound and a pyrazole compound. The composition of claim 1 further contains an organic solvent. The composition of claim 1, wherein the composition, based on the total amount of the composition, contains: 3.0-50 mass % of the alkaline agent, 0.1-20 mass % of the ammonium ion source, and 0.001-1.0 mass % of the azole compound. The composition of claim 1, wherein the composition is water-soluble. The composition of claim 1, wherein the composition does not contain a chelating agent or a sulfur-containing organic acid. The composition of claim 1, wherein the pattern is a circuit pattern of a connection terminal portion of a copper wiring formed on at least a portion of an insulating layer having the copper wiring. A method for removing photoresist comprises: contacting a photoresist used for forming a pattern containing copper with a composition as described in any one of claims 1 to 11 to remove the photoresist. A method for removing a photoresist as claimed in claim 12, wherein the pattern is a circuit pattern of a connection terminal portion of a copper wiring formed on at least a portion of an insulating layer having the copper wiring. A method for manufacturing a printed wiring board, a semiconductor element, or a semiconductor package comprises: for a photoresist used to form a pattern containing copper, bringing a composition as described in any one of claims 1 to 11 into contact with the photoresist to remove the photoresist. A method for manufacturing a printed wiring board, a semiconductor element, or a semiconductor package as claimed in claim 14, wherein the pattern is a circuit pattern of a connecting terminal portion of a copper wiring formed on at least a portion of an insulating layer having the copper wiring.