Composition for removing photoresist and method for removing photoresist

Abstract

According to the present invention, it is possible to provide a composition for removing a photoresist for forming a copper-containing pattern after the formation of the pattern, the composition containing an alkaline agent and an azole compound, the alkaline agent being one or more selected from the group consisting of an alkanolamine, a quaternary ammonium hydroxide, and an inorganic base, and the azole compound being one or more selected from the group consisting of at least one or more selected from the group consisting of at least one or more selected from the group consisting of at least one or more selected from the group consisting of at least one or more selected from the group consisting of at least one or more selected from the group consisting of the azole compound is one or more compounds selected from the group consisting of compounds represented by formulae (1)-(3), and the pH of the composition is 10 or more. (In formulae (1) to (3), each of R1-R14 independently represents a hydrogen atom, an optionally substituted alkyl group having 1-7 carbon atoms, or an optionally substituted amino group. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a composition for removing a photoresist, a method for removing a photoresist using the composition for removing a photoresist, and the like. Background Art

[0002] In recent years, electronic devices have been miniaturized and advanced in functionality, and printed circuit boards used in these electronic devices are also required to be miniaturized and advanced in functionality.

[0003] In order to manufacture a printed circuit board or the like that meets such expectations, the following method is adopted. For example, a metal layer called a seed layer is formed on an insulating layer having copper wiring in a part, a photoresist layer is formed on the surface, exposure and development are performed to form a resist pattern, copper plating is performed on the pattern opening, and then the photoresist and the seed layer are removed to form a circuit pattern that becomes a connection terminal portion of the copper wiring.

[0004] As described above, the manufacturing method of a printed wiring board or the like often includes a photoresist removal step, and the photoresist removal step generally uses an aqueous solution having various components (Patent Document 1, etc.).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2020 / 022491 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] In the conventional process of removing photoresist, if a conventional treatment liquid, especially a highly reactive treatment liquid for efficiently removing photoresist, is used, there is a possibility of damaging copper-containing components such as copper plating. In addition, for example, in the copper-containing components, the residue of the treatment liquid for removing photoresist may have an adverse effect.

[0010] From the above viewpoints, a method is being sought that has excellent performance in protecting copper-containing members and does not generate residues adhering to the photoresist during photoresist removal as part of a manufacturing process of a printed wiring board or the like.

[0011] Solutions for solving problems

[0012] The present invention includes the following aspects, for example.

[0013] [1] A composition for removing a photoresist used to form a pattern containing copper after the pattern is formed, the composition comprising:

[0014] Alkaline agents and azole compounds,

[0015] The foregoing alkali agent is one or more selected from the group consisting of alkanolamines, quaternary ammonium hydroxides, and inorganic bases.

[0016] The foregoing azole compound is one or more selected from the group consisting of compounds represented by the following formulas (1) to (3).

[0017] The pH of the foregoing composition is 10 or more.

[0018]

[0019] (In the foregoing formulas (1) to (3), R1 to R 14 are each independently a hydrogen atom, an alkyl group having 1 or more and 7 or less carbon atoms optionally having a substituent, or an amino group optionally having a substituent.)

[0020] [2] The composition according to [1] above, wherein the etching rate of copper is less than 0.05 μm / min.

[0021] [3] The composition according to [1] above, wherein the foregoing azole compound includes at least any one of 4-methylimidazole, 2-methylimidazole, 5-methylbenzimidazole, 2-aminobenzimidazole, and 3-methylpyrazole.

[0022] [4] The composition according to [1] above, which further contains an organic solvent.

[0023] [5] The composition according to [1] above, wherein the foregoing composition contains, based on the total amount of the composition:

[0024] 3.0 to 50% by mass of the foregoing alkali agent, and

[0025] 0.001 to 1.0% by mass of the azole compound.

[0026] [6] The composition according to [1] above, wherein the foregoing composition is water-soluble.

[0027] [7] The composition according to [1] above, wherein the composition does not contain a thiol compound.

[0028] [8] The composition according to [1] above, wherein the foregoing pattern is a circuit pattern formed on at least a part of an insulating layer having a copper wiring and serving as a connection terminal portion of the foregoing copper wiring.

[0029] [9] A method for removing a photoresist, which includes: a photoresist removal step of bringing the composition according to any one of [1] to [8] above into contact with a photoresist for forming a pattern containing copper.

[0030]

[10] The method for removing a photoresist according to [9] above, wherein the foregoing pattern is a circuit pattern formed on at least a part of an insulating layer having copper wirings and serving as a connection terminal portion of the foregoing copper wirings.

[0031]

[11] A method for manufacturing a printed circuit board, a semiconductor element, or a semiconductor package, which includes: a photoresist removal step of bringing the composition according to any one of [1] to [8] above into contact with a photoresist for forming a pattern containing copper.

[0032]

[12] The method for manufacturing a printed circuit board, a semiconductor element, or a semiconductor package according to

[11] above, wherein after the foregoing photoresist removal step, a cleaning step of cleaning a photoresist-containing substrate containing the foregoing photoresist is further included.

[0033]

[13] The method for manufacturing a printed circuit board, a semiconductor element, or a semiconductor package according to

[12] above, wherein in the foregoing cleaning step, sulfuric acid and / or water having a concentration of 40% by mass or less is used to clean the foregoing photoresist-containing substrate.

[0034]

[14] The method for manufacturing a printed circuit board, a semiconductor element, or a semiconductor package according to

[11] above, wherein the foregoing pattern is a circuit pattern formed on at least a part of an insulating layer having copper wirings and serving as a connection terminal portion of the foregoing copper wirings.

[0035] Effects of the Invention

[0036] According to the present invention, a composition for removing a photoresist, etc., which can efficiently remove a photoresist, has excellent properties for protecting members containing copper, etc., and does not generate residues on the surface of the photoresist, can be provided. Detailed Description of Embodiments

[0037] The composition of the present invention is, for example, suitable for removing a photoresist after the formation of a pattern containing copper, and contains at least a specified base agent and an azole compound. Hereinafter, the composition will be described in detail.

[0038] [I. Composition]

[0039] The composition is preferably water-soluble. That is, it is preferred that at least a part of the composition is soluble in water or can be suspended in water, and more preferably, it can be uniformly mixed with water in any proportion.

[0040] In addition, it is preferred that at least a part of the components other than water contained in the composition is soluble in water, and more preferably, the components other than water contained in the composition can be uniformly mixed with water.

[0041] <I-1. (A) Base Agent>

[0042] The composition preferably contains 3.0 to 50% by mass of an (A) basic agent (hereinafter also referred to as component (A)) based on the total mass of the composition. The content of the basic agent in the composition is more 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.

[0043] In the composition containing component (A), it has good removability of the photoresist, and in addition, it is considered to have an effect of suppressing damage to a circuit pattern containing copper, a copper alloy, etc. in a connection terminal portion of a copper wiring.

[0044] (A) The basic agent preferably contains any one selected from (A-1) alkanolamine, (A-2) quaternary ammonium hydroxide, and (A-3) inorganic base, more preferably contains two of these, and particularly preferably contains (A-1) to (A-3).

[0045] (A-1) Alkanolamine

[0046] The type of (A-1) alkanolamine that can be contained as component (A) in the composition is not particularly limited, and examples thereof include monoalkanolamine, dialkanolamine, trialkanolamine, and alkylated products (N-alkylated products, O-alkylated products) thereof.

[0047] As the alkanolamine (A), for example, 2-aminoethanol (monoethanolamine), N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, 1-amino-2-propanol (isopropanolamine), N-methylisopropanolamine, N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-aminopropan-1-ol, N-ethyl-2-aminopropan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutan-2-ol, 2-aminobutan-1-ol, N-methyl-2-aminobutan-1-ol, N-ethyl-2-aminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutan-4-ol, N-methyl-1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpentan-1-ol, 2-aminohexan-1-ol, 3-aminoheptan-4-ol, 1-aminooctan-2-ol, 5-aminooctan-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(oxymethyl)aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2-(2-aminoethoxy)ethanol, etc. can be preferably cited. These can be used alone or in combination of two or more.

[0048] Among these, as the alkanolamine, one or more selected from the group consisting of 2-aminoethanol (monoethanolamine) and 1-amino-2-propanol are preferred.

[0049] The content of the alkanolamine is preferably 1.0 to 50% by mass, more preferably 1.5 to 45% by mass, 1.5 to 42% by mass, 2.0 to 30% by mass or 2.0 to 15% by mass, further preferably 3.0 to 12% by mass, and particularly preferably 4.0 to 8.0% by mass or 5.0 to 9.0% by mass, etc., based on the total amount of the composition.

[0050] (A-2) Quaternary ammonium hydroxide

[0051] The types of (A-2) quaternary ammonium hydroxide that can be contained as the component (A) in the composition are not particularly limited, and for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, triethylmethylammonium hydroxide, ethyltrimethylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide, triethyl(2-hydroxyethyl)ammonium hydroxide can be cited. These can be used alone or in combination of two or more.

[0052] Among these, as the quaternary ammonium hydroxide, one or more selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and triethylmethylammonium hydroxide are preferred.

[0053] The content of the quaternary ammonium hydroxide is preferably 0.3 to 10% by mass, more preferably 0.5 to 8.0% by mass, still more preferably 0.7 to 9.0% by mass, and particularly preferably 0.8 to 4.0% by mass or 0.9 to 5.0% by mass, etc., based on the total amount of the composition.

[0054] (A-3) Inorganic base

[0055] The type of the (A-3) inorganic base that can be contained as the component (A) in the composition 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, and potassium silicate; alkaline earth metal compounds such as magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, calcium silicate, and magnesium silicate; transition metal compounds such as copper hydroxide and iron hydroxide; and ammonia.

[0056] Among these, as the inorganic base, potassium hydroxide, sodium hydroxide, etc. are preferred.

[0057] The content of the inorganic base is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, still more preferably 0.05 to 2.0% by mass, and particularly preferably 0.1 to 0.5% by mass or 0.2 to 1.0% by mass, etc., based on the total amount of the composition.

[0058] <I-2. (B) Azole compound>

[0059] The composition preferably contains 0.001 to 1.0% by mass of the (B) azole compound (hereinafter also referred to as component (B)) based on its total mass. The content of the azole compound in the composition is more preferably 0.005 to 0.80% by mass, still more preferably 0.01 to 0.50% by mass or 0.02 to 0.60% by mass, and particularly preferably 0.02 to 0.40% by mass, 0.02 to 0.30% by mass, 0.25 to 0.40% by mass, 0.25 to 0.30% by mass, or 0.03 to 0.20% by mass, etc., based on the total amount of the composition.

[0060] The composition containing the component (B) is considered to protect the metal layer containing copper or copper alloy and has the effect of reducing the etching rate of copper.

[0061] The azole compound in the composition preferably contains at least any one of an imidazole compound, a benzimidazole compound, and a pyrazole compound.

[0062] (B-1) Imidazole compound

[0063] As an imidazole compound, there is no particular limitation as long as it is a compound having an imidazole ring. It is preferred to use at least the compound of the following formula (1) as one component of the composition.

[0064]

[0065] In formula (1), R1 to R4 are each independently selected from a hydrogen atom, an alkyl group having 1 or more and 7 or less carbon atoms which may have a substituent, and an amino group which may have a substituent.

[0066] The carbon number of the alkyl group is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and further preferably 1 or 2, or 1.

[0067] Examples of the above-mentioned substituents include a hydroxyl group, a halogen, a vinyl group, a carboxyl group, a cyano group, a nitro group, a (meth)acryloyloxy group, a glycidyloxy group, a mercapto group, an amino group, etc. In addition, when any one of R1 to R4 is an alkyl group, the substituent also includes an amino group, for example, an amino group optionally containing an alkyl group having 10 or less carbon atoms, and when any one of R1 to R4 is an amino group, the substituent also includes an alkyl group, for example, an alkyl group having 10 or less carbon atoms.

[0068] It should be noted that when the imidazole compound of formula (1) contains an alkyl group or an amino group having a substituent, the above carbon number is the total number of carbon atoms including the carbon of the substituent.

[0069] Preferred specific examples of the imidazole compound include imidazole, imidazole derivatives having the above-mentioned substituents, such as 1-alkylimidazoles such as 1-methylimidazole, 2-alkylimidazoles such as 2-methylimidazole, 4-alkylimidazoles such as 4-methylimidazole, and imidazolium salts thereof.

[0070] (B-2) Benzimidazole compound

[0071] As the benzimidazole compound, there is no particular limitation as long as it is a compound having a benzimidazole skeleton. It is preferred to use at least the compound of the following formula (2) as one component of the composition.

[0072]

[0073] In formula (2), R5 to R 10 are each independently selected from a hydrogen atom, an alkyl group having 1 or more and 7 or less carbon atoms which may have a substituent, and an amino group which may have a substituent.

[0074] The carbon number of the alkyl group is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and further preferably 1 or 2, or 1.

[0075] Examples of the above substituents include a hydroxyl group, a halogen, a vinyl group, a carboxyl group, a cyano group, a nitro group, a (meth)acryloyloxy group, a glycidyloxy group, a mercapto group, an amino group, etc. In addition, when any one of R5 to R 10 is an alkyl group, the substituent also includes an amino group, for example, an amino group optionally containing an alkyl group having 10 or less carbon atoms. When any one of R5 to R 10 is an amino group, the substituent also includes an alkyl group, for example, an alkyl group having 10 or less carbon atoms.

[0076] It should be noted that when the benzimidazole compound of formula (2) contains a substituted alkyl group or amino group, the above carbon number is the total number of carbon atoms including the carbon of the substituent.

[0077] Preferred specific examples of the imidazole compound include benzimidazole, benzimidazole derivatives having the above substituents, such as 1-alkylbenzimidazoles such as 1-methylbenzimidazole, 2-alkylbenzimidazoles such as 2-methylbenzimidazole, 5-alkylbenzimidazoles such as 5-methylbenzimidazole, 1-aminobenzimidazole, 2-aminobenzimidazole, 5-aminobenzimidazole, benzimidazolium salts thereof, etc.

[0078] (B-3) Pyrazole compound

[0079] As the pyrazole compound, there is no particular limitation as long as it is a compound having a pyrazole ring. It is preferred to use at least the compound of the following formula (3) as one component of the composition.

[0080]

[0081] In formula (3), R 11 to R 14 are each independently selected from a hydrogen atom, an alkyl group having 1 or more and 7 or less carbon atoms optionally having a substituent, and an amino group optionally having a substituent.

[0082] The carbon number of the alkyl group is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and further preferably 1 or 2, or 1.

[0083] Examples of the above substituents include a hydroxyl group, a halogen, a vinyl group, a carboxyl group, a cyano group, a nitro group, a (meth)acryloyloxy group, a glycidyloxy group, a mercapto group, an amino group, etc. In addition, when any one of R 11 to R 14 is an alkyl group, the substituent also includes an amino group, for example, an amino group optionally containing an alkyl group having 10 or less carbon atoms. When any one of R 11 to R 14 is an amino group, the substituent also includes an alkyl group, for example, an alkyl group having 10 or less carbon atoms.

[0084] It should be noted that when the pyrazole compound of formula (3) contains an alkyl group or an amino group with a substituent, the above carbon number is the total number of carbon atoms including the carbon of the substituent.

[0085] As preferred specific examples of the pyrazole compound, pyrazole, pyrazole having the above-mentioned substituent, 1-alkylpyrazoles such as 1-methylpyrazole, 3-alkylpyrazoles such as 3-methylpyrazole, 4-alkylpyrazoles such as 4-methylpyrazole, 5-alkylpyrazoles such as 5-methylpyrazole, and pyrazole salts thereof can be cited.

[0086] <I-3. Water>

[0087] The composition preferably contains water. There is no particular limitation on the type of water contained in the composition. It is preferably obtained by removing metal ions, organic impurities, particles, etc. through distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc. More preferably, it is pure water, and particularly preferably, it is ultrapure water.

[0088] The content of water in the composition is preferably 20% by mass or more, more preferably more than 20% by mass, more preferably in the range of 20 - 99% by mass, further preferably in the range of 50 - 97% by mass, still further preferably in the range of 60 - 95% by mass, and particularly preferably in the range of 70 - 95% by mass, based on the total amount of the composition. The composition with the water content adjusted in this way improves the reactivity with the photoresist and the removability of the photoresist.

[0089] <I-4. Other components>

[0090] Within the range that does not hinder the above effects, the composition may also contain other components as needed. As other components, solvents, ammonium salts, pH regulators, surfactants, antifoaming agents, etc. can be cited.

[0091] In addition, carbonate ions, carbonates that generate carbonate ions, bicarbonates, etc. can also be added to the composition. If carbonate ions, etc. are added to the composition, the corrosion resistance of copper can be improved. As specific examples of the carbonate and bicarbonate, salts of ammonium ions, salts of alkali metals or alkaline earth metals, etc. can be cited, and ammonium carbonate salts such as tetramethylammonium carbonate can also be added to the composition.

[0092] 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, still further preferably 2.0% by mass or less, or 1.5% by mass or less, based on the total amount of the composition.

[0093] 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.

[0094] In addition, the composition is preferably a solution, and preferably does not contain solid particles such as abrasive particles.

[0095] In the composition, for example, organic solvents such as ether compounds and alcohols are preferably added. When using a specified solvent, it can be considered that there is an effect of improving the solubility of the photoresist in the composition and enhancing the removability.

[0096] Specific examples of ethers in the preferred 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.

[0097] In addition, specific examples of alcohols in the preferred organic solvents include aromatic alcohols such as benzyl alcohol, salicyl alcohol, anisyl alcohol, anise alcohol, gentisyl alcohol, catechol, vanillyl alcohol, veratryl alcohol, syringyl alcohol, cumyl alcohol, phenethyl alcohol, etc.

[0098] The content of the solvent is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, further preferably 0.2 to 5.0% by mass, and particularly preferably 0.3 to 3.5% by mass or 0.4 to 4.0% by mass, etc., based on the total amount of the composition.

[0099] In the composition, an ammonium ion source such as an ammonium salt which is preferably a quaternary ammonium salt is preferably contained. When using a specified ammonium ion source, it can be considered that there is an effect of enhancing the removability of the photoresist.

[0100] The types of ammonium ion sources that can be contained in the composition are not particularly limited, and examples include ammonium salts such as ammonia and ammonium halide 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 as the organic acid ammonium salt, ammonium salts of aromatic organic acids and ammonium salts of fatty acids, etc. can be cited.

[0101] As the 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. Specific examples include ammonium salts of benzoic acid, phthalic acid, salicylic acid, etc., that is, ammonium benzoate, diammonium phthalate, ammonium salicylate, etc.

[0102] In addition, examples of the fatty acid ammonium salt include mono-, di- and tri-ammonium salts of saturated or unsaturated fatty acids having 1 to 20 carbon atoms, and specific examples include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, tridecanoic acid, palmitic acid, stearic acid; ammonium salts of unsaturated fatty acids such as acrylic acid, methacrylic acid, oleic acid, linoleic acid, linolenic acid, etc.

[0103] As the ammonium ion source, one or more than two kinds can be used. Based on the total amount of the ammonium ion source in the composition, it is preferably contained 30% by mass or more of the aromatic organic acid ammonium salt or fatty acid ammonium salt, more preferably contained 50% by mass or more of the aromatic organic acid ammonium salt or fatty acid ammonium salt, further preferably contained 70% by mass or more of the aromatic organic acid ammonium salt or fatty acid ammonium salt, and particularly preferably contained 90% by mass or more of the aromatic organic acid ammonium salt or fatty acid ammonium salt. It is more preferable that only the aromatic organic acid ammonium salt or fatty acid ammonium salt is contained as the ammonium ion source in the composition.

[0104] Based on the total mass of the composition, the content of the ammonium ion source is preferably 0.1 to 20% by mass, more preferably 0.15 to 10% by mass based on the total amount of the composition, further preferably 0.20 to 5.0% by mass, and particularly preferably 0.25 to 2.5% by mass, 0.50 to 3.0% by mass or 1.0 to 2.0% by mass, etc.

[0105] In addition, there are also components that are preferably not added to the composition. Examples of the components not desired in the composition include, for example, thiols, organic acids containing sulfur atoms, chelating agents, etc.

[0106] If a composition containing a chelating agent is used to remove the photoresist, then in the flash etching process of etching copper, etc., there is a possibility that the remaining chelating agent will cause adverse effects. This is because if a chelating agent adheres to the surface of copper, it will interfere with the etching treatment.

[0107] In addition, when an organic acid containing a sulfur atom is used as a component of the composition, sulfur-containing compounds will cause the generation of odor and a decrease in the stability of the composition.

[0108] Therefore, in the composition of the present invention, it is preferably not to contain the above-mentioned compounds.

[0109] <I-5. Preparation method of the composition>

[0110] For the composition of the present invention, the components (A), (B), water and other components as required are added, and it is preferably prepared by stirring until it becomes completely uniform. When manufacturing the composition, the order of addition and mixing of each component is not particularly limited. For example, a certain amount of water can be added to any of the components (A) such as (A-1) to (A-3), and other components except water are prepared as a concentrated solution, and they are mixed when using the composition. It is also possible to transport any component in such a concentrated state, that is, in a water-free state and add water to prepare the composition.

[0111] <I-6. Properties of the composition>

[0112] The pH value of the composition of the present invention is 10 or more, preferably 10.5 to 13.8, more preferably 11.0 to 13.6, and further preferably 11.3 to 13.3. As described in detail later, the pH value can be measured using a pH meter.

[0113] According to the composition of the present invention, damage to copper and copper alloys can be inhibited. Therefore, the etching rate of copper evaluated by the specific method described later after the examples can be inhibited to 0.050 μm / minute or less. More preferably, the etching rate of copper evaluated by the specific method described later is 0.040 μm / minute or less, further preferably 0.030 μm / minute or less, and particularly preferably 0.020 μm / minute or 0.015 μm / minute or less.

[0114] According to the composition of the present invention, the photoresist can be effectively removed. Therefore, the value of L.P. (lifting point) regarding the stripping speed evaluated by the specific method described later after the examples can be 100 seconds or less. More preferably, the value of L.P. evaluated by the specific method described later is 90 seconds or less, further preferably 85 seconds or less, and particularly preferably 80 seconds or less or 75 seconds or less.

[0115] <I-7. Mode of use of the composition>

[0116] There is no particular limitation on the temperature of using the composition for removing the photoresist, and a temperature of 10 to 70 °C is preferred, more preferably 20 to 65 °C, and further preferably 25 to 60 °C. By using the composition in such a temperature range, the removability of the photoresist becomes good, and the compositional change of the composition can be inhibited and the removal conditions of the photoresist can be easily maintained.

[0117] There is no particular limitation on the treatment time for the composition-based photoresist, preferably 20 to 600 seconds, more preferably 30 to 300 seconds, and it can also be 30 to 240 seconds. The treatment time is the time for the composition to contact the photoresist, and it 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.

[0118] There is no particular limitation on the method of bringing the composition of the present invention into contact with the photoresist. For example, methods such as bringing the composition of the present invention into contact with the photoresist to be removed by dropping (single-wafer spin processing) or spraying atomization, or immersing the photoresist to be removed in the composition of the present invention can be adopted. Any method can be adopted in the present invention.

[0119] <II. Method for Removing Photoresist>

[0120] The method for removing the photoresist of the present invention includes a photoresist removal step that brings the composition of the present invention into contact with the photoresist used to form a copper-containing pattern. Hereinafter, the method for removing the photoresist will be described.

[0121] The composition of the present invention is, for example, suitable for removing the photoresist of a copper-containing circuit pattern that is used to form a connection terminal portion of the copper wiring on at least a part of an insulating layer having copper wiring after the formation of the circuit pattern.

[0122] Here, the "insulating layer having copper wiring at least in part" is not particularly limited as long as it is an insulating layer in which the copper wiring is buried in the surface or inside, and examples thereof include printed circuit boards, package substrates for mounting semiconductor elements, and silicon insulating layers of semiconductor wafers.

[0123] In addition, the "copper-containing circuit pattern that becomes the connection terminal portion of the copper wiring" means, for example, a connection terminal portion of the copper wiring of the insulating layer that is used for electrical connection with other components.

[0124] In one embodiment of the present invention, the connection terminal portion is the connection terminal portion of the copper wiring in a printed circuit board. In addition, in one embodiment of the present invention, the connection terminal portion is the connection terminal portion of the copper wiring in a package substrate for mounting semiconductor elements. In addition, in one embodiment of the present invention, the connection terminal portion is the connection terminal portion of the copper wiring in a semiconductor element.

[0125] <III. Manufacturing Method of Printed Wiring, etc.>

[0126] The manufacturing method of printed wiring, etc. of the present invention includes a photoresist removal step, in which the composition of the present invention is brought into contact with a photoresist used to form a copper-containing pattern. In addition to printed circuit boards, the photoresist removal step in the manufacturing methods of semiconductor elements and semiconductor packages can also suitably use the composition of the present invention.

[0127] For example, the composition of the present invention can be suitably used for removing a photoresist containing a copper-containing circuit pattern that forms a connection terminal portion of a copper wiring on an insulating layer having copper wiring in at least a part thereof, in the manufacturing process of a printed circuit board (for example, a package substrate for mounting a semiconductor element), after the formation of a circuit pattern.

[0128] In addition, the composition of the present invention can be suitably used for removing a photoresist containing copper and at least one selected from the group consisting of tin and tin alloys that forms a connection terminal portion of a copper wiring on an insulating layer having copper wiring in at least a part thereof, in the manufacturing process of a semiconductor element, after the formation of a circuit pattern.

[0129] The manufacturing method of printed wiring, etc. preferably further has a cleaning step, which cleans a substrate containing a photoresist that is the object of the photoresist removal step. In the cleaning step, for example, it is preferable to use sulfuric acid, water, etc. at a concentration of 40% by mass or less to clean the substrate containing the photoresist, and it is more preferable to clean with water, such as pure water, after cleaning with sulfuric acid. The concentration of sulfuric acid can be, for example, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 2% by mass or less, 1% by mass or less, etc. The temperature of the cleaning liquid such as sulfuric acid and water is preferably a temperature of 10 to 70°C, more preferably 15 to 50°C, and further preferably about 20 to 30°C at room temperature.

[0130] There is no particular limitation on the method of cleaning a substrate containing a photoresist with a cleaning liquid, and methods such as a method of bringing the above cleaning liquid into contact with the substrate as the object to be cleaned by dropping (single wafer spin processing) or spray atomization, or a method of immersing the substrate as the object to be cleaned in the cleaning liquid can be adopted.

[0131] When the cleaning liquid is sprayed onto the substrate by spraying in the cleaning step, the spraying time is, for example, 5 seconds to 5 minutes, preferably 10 seconds to 3 minutes, more preferably 15 seconds to 1 minute, and further preferably 20 seconds to 45 seconds. In addition, the spraying pressure in spray atomization is, for example, 0.03 to 1.0 MPa, preferably 0.05 to 0.50 MPa, and more preferably 0.10 to 0.30 MPa or 0.10 to 0.20 MPa.

[0132] Examples of the photoresist for a printed circuit board include, for example, a composition containing a binder polymer, a photopolymerizable monomer, a photopolymerization initiator, and other additives.

[0133] Examples of the binder polymer include, for example, a polymer obtained by copolymerizing at least one of methacrylic acid and acrylic acid as an essential component and various vinyl monomers such as methacrylate, acrylate, and styrene.

[0134] Examples of the photopolymerizable monomer preferably include at least one of methacrylate and acrylate.

[0135] Examples of the photopolymerization initiator include 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, benzil dimethyl ketal, and benzil diethyl ketal. In addition, a two-component system composed of hexaarylbiimidazole and a hydrogen donor (2-mercaptobenzoxazole, N-phenylglycine) can also be used.

[0136] In addition, examples of other additives include a thermal polymerization initiator, a dye, and the like.

[0137] Examples of the photoresist that can be used for a semiconductor element preferably include a combination of a phenol-formaldehyde resin (collectively referred to as "novolak resin") and a naphthoquinone diazide compound as a photosensitive component, and the like.

[0138] In addition, examples of the resist disposed between metal wirings include a dry film resist, a liquid resist, and the like. Among these, the resist is preferably a dry film resist. There is no particular limitation on the dry film resist, and it is preferably formed of a photosensitive resin. Examples of the photosensitive resin include a negative photosensitive resin and a positive photosensitive resin.

[0139] There is no particular limitation on the negative photosensitive resin, and examples thereof include an azide-based photosensitive resin, a diazo-based photosensitive resin, an acetylenic low-molecular-weight photosensitive resin, an olefinic low-molecular-weight photosensitive resin, an insolubilizing high-molecular-weight photosensitive resin, and a chromic acid-based photosensitive resin. These negative photosensitive resins can be used alone or in combination of two or more.

[0140] There is no particular limitation on the positive photosensitive resin, and examples thereof include a quinone diazide-based photosensitive resin, a solubilizing high-molecular-weight photosensitive resin, and the like. These positive photosensitive resins can be used alone or in combination of two or more.

[0141] Among these, the dry film resist is preferably formed of a negative photosensitive resin. Since the negative photosensitive resin is cured by the exposure treatment during pattern formation and becomes insoluble in the developer, the exposed part (the part where the negative photosensitive resin is cured) remains as the dry film resist. Here, the curing of the negative photosensitive resin, especially the surface part exposed during exposure, is likely to proceed, and the surface part of the obtained dry film resist may particularly have a dense structure. Therefore, depending on the composition, there are cases where even if it is desired to remove the dry film resist, the composition is difficult to penetrate into the interior of the dry film resist. In addition, depending on the composition, the resist removal ability is insufficient, and thus the dry film resist is not removed. As a result, it sometimes takes time to remove the dry film resist.

[0142] In contrast, the composition of the present invention easily penetrates into the dry film resist, and thus the dry film resist can be quickly peeled off and removed.

[0143] Examples

[0144] (pH)

[0145] The pH of the aqueous compositions described in the examples and comparative examples was measured using a pH meter (manufactured by Horiba, Ltd., D-53).

[0146] (Preparation of Samples for Evaluating Corrosion Resistance of Copper)

[0147] Samples for evaluating the corrosion resistance of copper were prepared as follows. That is, electroplating copper (thickness: 35 μm) was applied to the surface of a copper-clad laminate (manufactured by Mitsubishi Gas Chemical Company, Inc., CCL-HL832NX) to obtain samples for evaluating the corrosion resistance of copper.

[0148] (Cleanability)

[0149] The aqueous compositions described in the examples and comparative examples were sprayed and atomized at a spray pressure of 0.15 MPa at 50°C for 5 minutes to bring them into contact with the above-described samples for evaluating the corrosion resistance of copper cut into a square of 4 cm × 4 cm. Then, after cleaning by any of the following methods, the samples for evaluating the corrosion resistance of copper were dried.

[0150] Water spray: Atomized with pure water at a spray pressure of 0.15 MPa at 25°C for 30 seconds

[0151] 5% sulfuric acid spray: Atomized with 5 mass% sulfuric acid at a spray pressure of 0.15 MPa at 25°C for 30 seconds, and then washed with pure water

[0152] 5% sulfuric acid immersion: Immersed in 5 mass% sulfuric acid at 25°C for 30 seconds, and then washed with pure water

[0153] 20% sulfuric acid spray: Using 20% by mass sulfuric acid, spray atomization is carried out at a spray pressure of 0.15 MPa and at 25 °C for 30 seconds, and then washed with pure water.

[0154] The N element of the obtained sample for evaluating the corrosion resistance of the treated copper was measured using an X-ray photoelectron spectroscopy device (manufactured by Thermo Fisher Scientific Co., Ltd., K-Alpha).

[0155] Regarding the cleanability, the maximum peak intensity of the N element of the sample for evaluating the corrosion resistance of copper before treatment was set to 100, and the evaluation was carried out according to the following criteria.

[0156] Cleanable (good): The maximum peak intensity of the N element of the sample for evaluating the corrosion resistance of the treated copper is 120 or less.

[0157] Not cleanable (bad): The maximum peak intensity of the N element of the sample for evaluating the corrosion resistance of the treated copper exceeds 120.

[0158] (Corrosion resistance of copper (Cu E.R. (etch rate)))

[0159] The aqueous compositions described in the examples and comparative examples were spray atomized at a spray pressure of 0.15 MPa at 50 °C for 5 minutes to bring them into contact with the above-mentioned sample for evaluating the corrosion resistance of copper cut into a 4 cm × 4 cm square. Then, after washing with pure water, cleaning with 5% by mass sulfuric acid, and washing with pure water, the sample for evaluating the corrosion resistance of copper was sufficiently dried.

[0160] The value of Cu E.R. (μm / min) was calculated as follows. That is, the mass of the sample for evaluating the corrosion resistance of copper before and after the spray treatment of the above-mentioned aqueous composition was measured, and the etched thickness was calculated from the mass difference, the density of copper (8.93 g / cm 3 ) and the sample size (treatment area [cm 2 , it should be noted that the reverse side of the sample for evaluating the corrosion resistance of copper was protected with masking tape, so the treatment area was the area of the sample surface), and the etching amount per minute was obtained by the following formula (I).

[0161]

[0162] [Example 1]

[0163] An aqueous composition prepared by adding the following substances to 321 g of pure water respectively: monoethanolamine (MEA) in an amount that finally becomes 6% by mass (32 g of a 75% MEA aqueous solution), tetramethylammonium hydroxide (TMAH) in an amount that finally becomes 2% by mass (32 g of a 25% TMAH aqueous solution), ethylene glycol monophenyl ether (PhGE) in an amount that finally becomes 2.25% by mass (9.0 g), 4-methylimidazole in an amount that finally becomes 0.09% by mass (0.36 g), diethylene glycol monobutyl ether (DGBE) in an amount that finally becomes 1.35% by mass (5.4 g). Cleaning of the sample for evaluating the corrosion resistance of copper treated with the obtained aqueous composition was carried out by water spraying. The pH of the obtained aqueous composition was 13.3, the cleaning was good, and the Cu E.R. was 0.01 μm / min.

[0164] The properties and evaluation results of the aqueous composition are shown in Table 1 below.

[0165] [Examples 2 to 12 and Comparative Examples 1 to 5]

[0166] As shown in Table 1 below, any of the types, amounts of the respective components in the composition of Example 1 and the cleaning method of the sample for evaluating the corrosion resistance of copper were changed, and further components were added in some of the examples and comparative examples. Except for this, the aqueous composition was prepared in the same manner as in Example 1, and the evaluation test was carried out. The properties and evaluation results of the aqueous compositions of the respective examples and comparative examples are shown in Table 1 below.

[0167] It should be noted that the tetramethylammonium hydrogencarbonate salt (TMBC) added to the aqueous composition in Example 6 etc. can be generated as a degradation product of tetramethylammonium hydroxide (TMAH), which will reduce the stripping performance of the dry film resist caused by the aqueous composition. Therefore, in order to evaluate the stripping treatment caused by the aqueous composition in the case of long-term use and generation of tetramethylammonium hydrogencarbonate salt, this hydrogencarbonate was added to the aqueous composition of this example.

[0168] [Table 1]

[0169]

[0170] As shown by the above results, according to the aqueous compositions of the examples containing the specified azole compounds, it was confirmed that the cleaning results were good compared with the aqueous compositions of the comparative examples, that is, the amount of N element remaining on the surface of the copper-containing sample could be suppressed. Furthermore, in the examples, compared with the comparative examples, a lower value of Cu E.R. (etching rate) and excellent corrosion resistance of the copper of the composition were obtained.

[0171] Although not shown in Table 1, supplementary evaluation tests were also conducted for some of the embodiments as described below. The evaluation methods and results are shown below.

[0172] (Preparation of Samples for Peelability Evaluation)

[0173] Samples for peelability evaluation were prepared as follows. First, electroless copper plating was performed on a copper-clad laminate (manufactured by Mitsubishi Gas Chemical Company, Inc., CCL-HL832NS(MT-FL) 0.1 mm tC / C) to form a copper thin film (thickness: 1.0 μm). A dry film resist (manufactured by Showa Denko K.K., RD-3025, thickness: 25 μm) was attached to the surface of the copper thin film, and a circuit mask pattern was applied thereon, followed by exposure and development. Electroplated copper (thickness: 17 μm) was performed on the circuit pattern openings formed by exposure and development of the dry film resist to obtain samples for peelability evaluation. The pattern of the dry film resist applied to the samples for peelability evaluation was dots.

[0174] (Peelability)

[0175] The aqueous compositions used in Examples 6 to 8 (hereinafter referred to as aqueous composition A), the aqueous compositions used in Examples 10 to 12 (hereinafter referred to as aqueous composition B), and the aqueous composition used in Comparative Example 5 were each spray atomized at a spray pressure of 0.15 MPa at 50 °C for 3 minutes to bring them into contact with the above-mentioned samples for peelability evaluation. Then, washing with pure water, cleaning with 5 mass% sulfuric acid, and washing with pure water were performed, followed by thorough drying.

[0176] The peelability was evaluated as follows. That is, using an optical microscope (manufactured by Olympus Corporation, MX-61L, objective lens 50 times), the residue of the dry film resist of the samples for peelability evaluation after the spray treatment of the above-mentioned aqueous composition was confirmed, and the evaluation was carried out according to the following criteria.

[0177] Particularly good: The residues of the dry film resist were all 2 or less

[0178] Good: The residues of the dry film resist were all 110 or less

[0179] Poor: The residues of the dry film resist exceeded 110

[0180] The results of the above peelability evaluation test are as follows.

[0181] Aqueous composition A

[0182] Good

[0183] The residue of the dry film resist is 1

[0184] The residue of the dry film resist is 3

[0185] None The residue of the dry film resist

[0186] The residue of the dry film resist is 7

[0187] None The residue of the dry film resist

[0188] Aqueous composition B

[0189] Particularly good

[0190] None The residue of the dry film resist

[0191] None The residue of the dry film resist

[0192] The residue of the dry film resist is 1

[0193] None The residue of the dry film resist

[0194] None The residue of the dry film resist

[0195] The aqueous composition of Comparative Example 5

[0196] Poor

[0197] None The residue of the dry film resist

[0198] None The residue of the dry film resist

[0199] None The residue of the dry film resist

[0200] None The residue of the dry film resist

[0201] The residue of the dry film resist is 113

[0202] (Peeling speed (L.P. (peeling start point)))

[0203] The aqueous composition A of the example, the aqueous composition B of the example, and the aqueous composition of Comparative Example 5 were respectively atomized by spraying at a spraying pressure of 0.15 MPa at 50 °C and brought into contact with the above-described sample for peelability evaluation.

[0204] Then, the time from the start of spraying the aqueous composition until the dry film resist completely peels off from the substrate of the sample for peelability evaluation is measured as L.P. (seconds). In the measurement of L.P., the dot pattern portion applied to the sample for peelability evaluation is visually observed as the time when the dry film resist is removed.

[0205] The results of the above evaluation test of the peel rate are as follows.

[0206] Aqueous composition A: 90 (seconds)

[0207] Aqueous composition B: 90 (seconds)

[0208] Aqueous composition of Comparative Example 5: 110 (seconds)

[0209] As shown by the results of the above supplementary test, for the aqueous compositions of the examples containing a specified azole compound, it was confirmed that, compared with the aqueous compositions of the comparative examples, they have excellent performance in suppressing the generation of resist residues, and the time indicated by the value of L.P. (peeling start point) is short, enabling rapid peeling of the photoresist.

Claims

1. A composition for removing a photoresist used for forming a copper-containing pattern after the pattern formation, the composition comprising: a base agent and an azole compound, the base agent being at least one selected from the group consisting of alkanolamines, quaternary ammonium hydroxides, and inorganic bases, the azole compound being at least one selected from the group consisting of compounds represented by the following formulas (1) to (3), the pH of the composition being 10 or more, In the formulas (1) to (3) above, R1 to R 14 are each independently a hydrogen atom, an alkyl group having 1 to 7 carbon atoms which may optionally have a substituent, or an amino group which may optionally have a substituent.

2. The composition according to claim 1, wherein the etching rate of copper being less than 0.05 μm / min.

3. The composition according to claim 1, wherein The azole compound includes at least any one of 4-methylimidazole, 2-methylimidazole, 5-methylbenzimidazole, 2-aminobenzimidazole, and 3-methylpyrazole.

4. The composition according to claim 1, further comprising an organic solvent.

5. The composition according to claim 1, wherein, The composition contains, based on the total amount of the composition: 3.0 to 50% by mass of the base agent, and 0.001 to 1.0% by mass of the azole compound.

6. The composition according to claim 1, wherein, The composition is water-soluble.

7. The composition according to claim 1, wherein The composition does not contain a thiol compound.

8. The composition according to claim 1, wherein, The pattern is a circuit pattern formed on an insulating layer having copper wirings in at least a part thereof and serving as a connection terminal portion of the copper wirings.

9. A method for removing a photoresist, comprising: A photoresist removing step of bringing the composition according to any one of claims 1 to 8 into contact with a photoresist used for forming a copper-containing pattern.

10. The method for removing a photoresist according to claim 9, wherein, The pattern is a circuit pattern formed on an insulating layer having copper wirings in at least a part thereof and serving as a connection terminal portion of the copper wirings.

11. A method for manufacturing a printed circuit board, a semiconductor component, or a semiconductor package, comprising: A photoresist removing step of bringing the composition according to any one of claims 1 to 8 into contact with a photoresist used for forming a copper-containing pattern.

12. The manufacturing method of a printed circuit board, semiconductor element or semiconductor package according to claim 11, wherein, After the photoresist removing step, a cleaning step is further included, the cleaning step cleaning a photoresist-containing substrate containing the photoresist.

13. The manufacturing method of a printed circuit board, a semiconductor element, or a semiconductor package according to claim 12, wherein, In the cleaning step, sulfuric acid and / or water having a concentration of 40% by mass or less is used to clean the photoresist-containing substrate.

14. The manufacturing method of a printed circuit board, semiconductor element or semiconductor package according to claim 11, wherein, The pattern is a circuit pattern formed on an insulating layer having copper wirings in at least a part thereof and serving as a connection terminal portion of the copper wirings.

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