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 comprising: an alkaline agent comprising at least one selected from the group consisting of an alkanolamine, a quaternary ammonium hydroxide, and an inorganic base; an organic solvent in which the Hansen solubility parameter coordinates fall within the range of a sphere having a radius of 3.60 MPa 0.5 or less centered on [Delta] d = 16.0, [Delta] p = 8.7, and [Delta] h = 15.5; and an azole compound.

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, miniaturization and high functionality of electronic devices have been developing, and miniaturization and high functionality are also required for printed circuit boards used for such electronic devices.

[0003] In order to manufacture printed circuit boards and the like that meet 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 part, a photoresist layer is formed on the surface thereof, after exposure and development to form a resist pattern, copper plating is performed in 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, in the manufacturing method of printed circuit boards and the like, a photoresist removal step is mostly included, and an aqueous solution having various components is usually used in the photoresist removal step (Patent Document 1, etc.).

[0005] Prior Art Documents

[0006] Patent Documents

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

[0008] Problems to be Solved by the Invention

[0009] In the conventional manufacturing process of printed circuit boards and the like, there are sometimes cases where the removal of the photoresist cannot be performed quickly and sufficiently. If the photoresist can be removed quickly and surely, the productivity of the printed circuit board can be improved.

[0010] In addition, in the photoresist removal step, if a conventional treatment liquid is used, there is also a possibility of damaging components such as copper plating that are necessary at the end.

[0011] From the above viewpoints, a method is being sought that has excellent performance in removing a photoresist as part of a manufacturing process of printed circuit boards and the like and can surely protect copper components such as copper plating.

[0012] Solutions to the Problems

[0013] The present invention includes, for example, the following aspects.

[0014] [1] A composition for removing a photoresist used for forming a copper-containing pattern after the pattern formation, the composition containing:

[0015] An alkali agent comprising at least one selected from the group consisting of alkanolamines, quaternary ammonium hydroxides, and inorganic bases;

[0016] An organic solvent, the coordinates of whose Hansen solubility parameter fall within the range of a sphere with a radius of 3.60 MPa centered at δd = 16.0, δp = 8.7, and δh = 15.5; and 0.5 within; and

[0017] azole compound.

[0018] [2] The composition according to [1] above, wherein the coordinates of the Hansen solubility parameter of the aforementioned organic solvent fall within the range of a sphere with a radius of 3.00 MPa centered at δd = 16.0, δp = 8.7, and δh = 15.5. 0.5 within.

[0019] [3] The composition according to [1] above, wherein the aforementioned organic solvent comprises at least one selected from the group consisting of ethylene glycol monomethyl ether, methyl hydrazine, 2,2,2-trifluoroethanol, glycerol diacetate, 1-chloro-2-propanol, dimethylaminoethanol, ethylenediamine, 1,9-nonanediol, 2-bromoallyl alcohol, 2,3-dichloropropanol, furfuryl alcohol, adipic acid, 2-chloroethanol, N-formylethylamine, ethylene glycol monopropyl ether, 2-chloro-2-propen-1-ol, 1-(2-hydroxyethyl)-2-pyrrolidone, diethylene glycol mono vinyl ether, diethylenetriamine, 1,3-dichloro-2-propanol, 2-ethoxyethanol, 3-chloro-2-propen-1-ol, serotonin, 1,6-hexanediol, 2-cyclopenten-1-ol, methylamine, formic acid, ethylene glycol monoisopropyl ether, 3-azidopropene, 2,3-butadiene-1-ol, allyl alcohol, 2-fluoroacrylic acid, acetic acid, azidoethane, isocyanic acid, n-propanol, (E)-2-butene-1-ol, methyl salicylate, 2-propanol, L-(-)-tyrosine, dipropylene glycol, ethyl carbamate, and 2,2-dimethyl-1-propanol.

[0020] [4] The composition according to [1] above, wherein the etching rate of copper is less than 0.05 μm / min.

[0021] [5] The composition according to [1] above, which is water-soluble.

[0022] [6] The composition according to [1] above, wherein the aforementioned composition contains, based on the total amount of the aforementioned composition:

[0023] 3.0 to 50% by mass of the aforementioned alkali agent,

[0024] 0.1 to 30% by mass of the aforementioned organic solvent, and

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

[0026] [7] The composition according to [1] above, wherein the aforementioned 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 aforementioned copper wirings.

[0027] [8] A method for removing a photoresist, comprising: a photoresist removal step of bringing the composition according to any one of [1] to [7] above into contact with a photoresist for forming a pattern containing copper.

[0028] [9] The method for removing a photoresist according to [8] above, wherein the aforementioned 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 aforementioned copper wirings.

[0029]

[10] A method for manufacturing a printed circuit board, a semiconductor element, or a semiconductor package, comprising: a photoresist removal step of bringing the composition according to any one of [1] to [7] above into contact with a photoresist for forming a pattern containing copper.

[0030]

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

[10] above, wherein the aforementioned 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 aforementioned copper wirings.

[0031] Effects of the Invention

[0032] According to the present invention, it is possible to provide a composition for removing a photoresist that can efficiently remove a photoresist and can surely protect copper-containing members such as copper plating in a printed circuit board. Detailed Description of the Invention

[0033] The composition of the present invention is suitable for removing a photoresist after the formation of a pattern containing copper, and contains at least a specified base agent, an organic solvent, and an azole compound. Hereinafter, the composition will be described in detail.

[0034] [I. Composition]

[0035] 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.

[0036] 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.

[0037] <I-1. (A) Base agent>

[0038] 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.

[0039] In the composition containing component (A), the removability of the photoresist is good, 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.

[0040] (A) The basic agent preferably contains at least any one of (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) all.

[0041] (A-1) alkanolamine

[0042] 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 thereof (N-alkylated products, O-alkylated products).

[0043] 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.

[0044] Among these, as the alkanolamine, one or more selected from the group consisting of 2-aminoethanol (monoethanolamine) and 1-amino-2-propanol are preferred.

[0045] 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.

[0046] (A-2) Quaternary ammonium hydroxide

[0047] The type of (A-2) quaternary ammonium hydroxide that can be contained as the component (A) in the composition is not particularly limited, and examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, triethylmethylammonium hydroxide, ethyltrimethylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide, and triethyl(2-hydroxyethyl)ammonium hydroxide. These can be used alone or in combination of two or more.

[0048] 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.

[0049] The content of the quaternary ammonium hydroxide is preferably 0.3 to 12% by mass, more preferably 0.5 to 10% by mass, still more preferably 1.0 to 8.0% by mass, and particularly preferably 1.5 to 5.0% by mass or 2.0 to 6.0% by mass, etc., based on the total amount of the composition.

[0050] (A-3) Inorganic base

[0051] The types of (A-3) inorganic bases that can be contained as component (A) in the composition are not particularly limited, and examples 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; ammonia, etc.

[0052] Among these, as the inorganic base, potassium hydroxide, sodium hydroxide, etc. are preferred.

[0053] 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.

[0054] <I-2. (B) Organic solvent>

[0055] The composition preferably contains 0.1 to 30% by mass of (B) organic solvent (hereinafter, also referred to as component (B)) based on its total mass. The content of the organic solvent in the composition is more preferably 0.5 to 25% by mass, still more preferably 1.0 to 20% by mass or 1.5 to 15% by mass, and particularly preferably 2.0 to 10% by mass, 2.2 to 5.0% by mass, or 2.5 to 4.0% by mass, etc., based on the total amount of the composition.

[0056] The composition contains at least an organic solvent (hereinafter, also referred to as a specific organic solvent) whose Hansen solubility parameter (HSP) coordinates fall within a sphere with a radius of 3.60 MPa centered at the point where δd = 16.0, δp = 8.7, and δh = 15.5 (hereinafter, also referred to as the center point), that is, the distance from the center point in the HSP coordinates is 3.60 MPa 0.5 or less. 0.5The following organic solvents. Thus, a composition containing an organic solvent having an HSP value with a small distance from the center point in the coordinates is considered to have the effect of improving the removability of a photoresist, particularly the performance of efficiently peeling the photoresist from the metal layer rather than dissolving it in an aqueous solution. It should be noted that the calculation formula for the distance from the center point is as follows.

[0057]

[0058] As the reason for the considered stripping and removing effect of the resist, the following reasons can be cited. A specific organic solvent having an HSP value with a short distance from the above center point in the HSP coordinates has a tendency to have low compatibility with photoresist components such as dry film in the following specific cases, and is considered to have little effect of dissolving the photoresist. However, the specific organic solvent promotes the contact of the alkali agent and water with the photoresist such as dry film, and can facilitate the reaction of the alkali agent with the terminal carboxyl group of the photoresist. Through the action of such a specific organic solvent, a neutralization reaction occurs between the terminal carboxyl group of the photoresist and the alkali agent, and the aqueous solution is impregnated between the photoresist and the metal layer, and a state where the photoresist swells can be easily generated. As a result, the swollen photoresist is easily peeled from the metal layer covering the surface.

[0059] Accordingly, a specific organic solvent having a characteristic HSP value is an organic solvent having a different HSP value, and it is considered that the photoresist can be removed more efficiently than an organic solvent having the effect of dissolving the photoresist. This is because it takes a relatively long time to dissolve the photoresist in the solution, and a composition that can easily impregnate into the gap between the metal layer covered with the photoresist and the photoresist can act on a more limited range of the photoresist only and can be removed by peeling.

[0060] As the specific organic solvent, the distance from the center point in the HSP coordinates is preferably 3.30 MPa 0.5 Hereinafter, more preferably 3.00 MPa 0.5 Hereinafter, even more preferably 2.70 MPa 0.5 Hereinafter. As the specific organic solvent, an organic solvent having a distance from the center point in the HSP coordinates of 2.50 MPa 0.5 Hereinafter, 2.30 MPa 0.5 Hereinafter, 2.00 MPa 0.5 Hereinafter, 1.50 MPa 0.5 Hereinafter, or 1.00 MPa 0.5 Hereinafter can also be used. In addition, as the specific organic solvent, an organic solvent having a distance from the center point in the HSP coordinates of, for example, 0.70 MPa 0.5 ~3.50 MPa 0.5 of the organic solvent, 1.00 MPa0.5 ~3.30 MPa 0.5 of an organic solvent, 1.50 MPa 0.5 ~3.00 MPa 0.5 of an organic solvent, 2.00 MPa 0.5 ~2.70 MPa 0.5 of an organic solvent, etc.

[0061] As preferred specific examples of the specific organic solvent, the following organic solvents can be cited. The names of these compounds, the HSP coordinates, and the values of the distances from the center point are shown in Table 1.

[0062] First, as specific organic solvents with a distance from the center point in the HSP coordinates of 1.50 MPa 0.5 or less, ethylene glycol monomethyl ether, methylhydrazine, trifluoroethanol such as 2,2,2-trifluoroethanol, glycerol diacetate, chloropropanol such as 1-chloro-2-propanol, etc. can be cited.

[0063] As specific organic solvents with a distance from the center point in the HSP coordinates exceeding 1.50 MPa 0.5 and being 3.00 MPa 0.5 or less, dimethylaminoethanol, ethylenediamine, nonanediol such as 1,9-nonanediol, bromoallyl alcohol such as 2-bromoallyl alcohol, dichloropropanol such as 2,3-dichloropropanol, furfuryl alcohol, adipic acid, 2-chloroethanol, N-formylethylamine, ethylene glycol monopropyl ether, chloroallyl alcohol such as 2-chloroallyl alcohol (2-chloro-2-propene-1-ol), 2-pyrrolidone having 2-hydroxyethyl such as 1-(2-hydroxyethyl)-2-pyrrolidone, diethylene glycol mono vinyl ether, diethylenetriamine, dichloropropanol such as 1,3-dichloro-2-propanol, ethoxyethanol such as 2-ethoxyethanol, chloroallyl alcohol such as 3-chloro-2-propene-1-ol, serotonin, hexanediol such as 1,6-hexanediol, cyclopentenol such as 2-cyclopenten-1-ol, methylamine, formic acid, ethylene glycol monoisopropyl ether, azidopropene such as 3-azidopropene, 2,3-butadiene-1-ol, allyl alcohol, fluoroacrylic acid such as 2-fluoroacrylic acid, acetic acid, azidoethane, isocyanic acid, propanol such as n-propanol, butenol such as (E)-2-butene-1-ol, methyl salicylate, propanol such as 2-propanol, L-(-)-tyrosine, dipropylene glycol, ethyl carbamate, 2,2-dimethyl-1-propanol, etc. can be cited.

[0064] Furthermore, as specific organic solvents with a distance from the center point in the HSP coordinates exceeding 3.00 MPa 0.5 and being 3.60 MPa 0.5Examples of the following organic solvents include 4'-hydroxyacetanilide, 1-butanol, 1-methoxymethanol, diethylene glycol monomethyl ether, 3-hydroxytetrahydrofuran, isobutanol, 2-butanol, ethyl lactate, triethylene glycol monomethyl ether, tetrahydrofurfuryl alcohol, 2-pentanol, glycerol formal, 1-aminocyclopropanecarboxylic acid, 1-pentanol, glycidol, 2-propyn-1-ol, 1,2-cyclohexanediol, diethylene glycol monoethyl ether, isooctanol, 3-chloro-1-propanol, 2-methyl-2-butanol, salicylic acid, 3-methoxy-3-methylbutanol, coniferyl alcohol, sinapyl alcohol, acetone cyanohydrin, crotonic acid, etc.

[0065] [Table 1]

[0066]

[0067] As the specific organic solvent contained in the composition, from the viewpoint of ease of acquisition, etc., ethylene glycol monopropyl ether (distance from the center point is 2.00 MPa 0.5 ), n-propanol (distance from the center point is 2.69 MPa 0.5 ), etc. in the above specific examples are more preferable.

[0068] As the specific organic solvent, 1 kind can be used, and in addition, 2 or more kinds can also be used. In addition, the organic solvent as component (B) in the composition may also contain an organic solvent other than the specific organic solvent. Among them, the organic solvent in the composition preferably contains 30% by mass or more of the specific organic solvent based on the total amount of the organic solvent, more preferably contains 50% by mass or more of the specific organic solvent, further preferably contains 70% by mass or more of the specific organic solvent, particularly preferably contains 90% by mass or more of the specific organic solvent, and it is more preferable that only the specific organic solvent is contained as the organic solvent in the composition.

[0069] <I-3. (C) Azole compound>

[0070] The composition preferably contains 0.001 to 1.0% by mass of (C) azole compound (hereinafter also referred to as component (C)) based on its total mass. The content of the azole compound in the composition is more preferably 0.005 to 0.80% by mass, further preferably 0.01 to 0.60% by mass or 0.015 to 0.70% by mass, particularly preferably 0.02 to 0.40% by mass, 0.025 to 0.50% by mass or 0.03 to 0.30% by mass, etc.

[0071] The composition containing component (C) is considered to protect the metal layer containing copper or copper alloy and has the effect of reducing the etching rate of copper.

[0072] As the azole compound in the composition, it is preferable to contain at least any one of triazole compounds, imidazole compounds, benzimidazole compounds, and pyrazole compounds.

[0073] As a triazole compound, there is no particular limitation as long as it is a compound having a triazole ring. Examples include any of 1,2,3-triazole and 1,2,4-triazole, triazoles having substituents with 10 or less carbon atoms, triazoles such as tolyltriazole in which an aromatic ring is fused to the triazole ring, and triazole salts thereof.

[0074] As an imidazole compound, there is no particular limitation as long as it is a compound having an imidazole ring. Examples include imidazole, imidazole derivatives having substituents with 10 or less carbon atoms, such as 1-alkylimidazoles like 1-methylimidazole, 4-alkylimidazoles like 4-methylimidazole, mercaptoimidazoles like 2-mercaptoimidazole, and imidazolium salts thereof.

[0075] As a benzimidazole compound, there is no particular limitation as long as it is a compound having a benzimidazole skeleton. Examples include benzimidazole, benzimidazole derivatives having substituents with 10 or less carbon atoms, such as 1-alkylbenzimidazoles, 2-alkylbenzimidazoles, 7-alkylbenzimidazoles, and benzimidazolium salts thereof.

[0076] In addition, as a pyrazole compound, examples include pyrazole, pyrazoles having substituents with 10 or less carbon atoms, 1-alkylpyrazoles like 1-methylpyrazole, 3-alkylpyrazoles like 3-methylpyrazole, 4-alkylpyrazoles like 4-methylpyrazole, 5-alkylpyrazoles like 5-methylpyrazole, and pyrazole salts thereof.

[0077] <I-4. Water>

[0078] The composition preferably contains water. There is no particular limitation on the type of water contained in the composition. Water obtained by removing metal ions, organic impurities, particles, etc. through distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc. is preferred, pure water is more preferred, and ultrapure water is particularly preferred.

[0079] The content of water in the composition is preferably 20% by mass or more based on the total amount of the composition, more preferably more than 20% by mass, more preferably in the range of 20 - 99% by mass, further preferably 40 - 97% by mass, still further preferably 60 - 95% by mass, and particularly preferably 70 - 95% by mass. The composition with the water content adjusted in this way improves the reactivity with the photoresist and the removability of the photoresist.

[0080] <I-5. Other Components>

[0081] Within the range that does not interfere with the above effects, other minor components may also be contained in the composition as needed. Examples of other components include pH adjusters, surfactants, defoamers, etc. Organic acids (organic acid ions), ammonium ions, etc. may also be added. When an organic acid or an organic acid ion is added to the composition, the affinity of the composition for the dry film resist can be improved. In addition, when an ammonium ion is added to the composition, the reactivity of the composition with respect to the carboxyl group of the dry film resist is improved.

[0082] In addition, carbonate ions, carbonates that generate carbonate ions, bicarbonates, etc. may also be added to the composition. When carbonate ions, etc. are added to the composition, the corrosion resistance of copper can be improved. Specific examples of the carbonate and bicarbonate include salts of ammonium ions, salts of alkali metals or alkaline earth metals, etc.

[0083] The above components may also be combined, and ammonium benzoate and other organic acid ammonium salts, tetramethylammonium carbonate and other ammonium carbonate salts, etc. may be added to the composition.

[0084] 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.

[0085] In addition, the content of each of the organic acid (organic acid ion), ammonium ion, and 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.

[0086] It should be noted that the composition is preferably a solution and preferably does not contain solid particles such as abrasive particles.

[0087] <I-6. Preparation method of the composition>

[0088] For the composition of the present invention, component (A), component (B), component (C), water, and other components as needed 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 may 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 the composition is used. It is also possible to transport any component in a concentrated state, that is, in a water-free state, and add water to prepare the composition.

[0089] <I-7. Properties of the composition>

[0090] The pH range of the composition of the present invention is not particularly limited. In one embodiment, the pH value of the composition is 8 or more, preferably 10 or more, more preferably 11 or more. The pH value can be measured by a general method using a pH meter.

[0091] 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 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 below 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.

[0092] 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 after the examples can be 100 seconds or less. More preferably, the value of L.P. evaluated by the specific method described below is 90 seconds or less, further preferably 85 seconds or less, and particularly preferably 80 seconds or less or 75 seconds or less.

[0093] <I-8. Mode of use of the composition>

[0094] There is no particular limitation on the temperature of the composition used to remove the photoresist. 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 within such a temperature range, the removability of the photoresist becomes good, and the compositional change of the composition can be suppressed, making it easy to maintain the photoresist removal conditions.

[0095] There is no particular limitation on the treatment time of the photoresist based on the composition. It is preferably 20 to 600 seconds, more preferably 30 to 300 seconds, and may also be 30 to 240 seconds. The treatment time is the time for the composition to contact 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.

[0096] 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 dropping (single-wafer spin processing) or spraying atomization to bring the composition of the present invention into contact with the photoresist to be removed, or immersing the photoresist to be removed in the composition of the present invention can be used. Any method can be adopted in the present invention.

[0097] <II. Method for removing photoresist>

[0098] The method for removing a photoresist of the present invention includes a photoresist removal step of bringing the composition of the present invention into contact with a photoresist for forming a copper-containing pattern. Hereinafter, the method for removing a photoresist will be described.

[0099] The composition of the present invention is, for example, suitable for removing a photoresist for forming a copper-containing circuit pattern that forms a connection terminal portion of a copper wiring on at least a part of an insulating layer having a copper wiring after forming a circuit pattern.

[0100] Here, the "insulating layer having a copper wiring at least in part" is not particularly limited as long as it is an insulating layer in which a copper wiring is embedded in the surface or inside, and examples thereof include a printed circuit board, a package substrate for mounting semiconductor elements, and a silicon insulating layer of a semiconductor wafer.

[0101] In addition, the "copper-containing circuit pattern that forms a connection terminal portion of a copper wiring" means, for example, a connection terminal portion of a copper wiring included in an insulating layer and is used for electrically connecting to other components.

[0102] In one embodiment of the present invention, the connection terminal portion is a connection terminal portion of a copper wiring in a printed circuit 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 package substrate for mounting semiconductor elements. 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.

[0103] <III. Manufacturing method of printed wiring, etc.>

[0104] 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 for forming 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.

[0105] For example, the composition of the present invention is suitable for removing a photoresist for forming a copper-containing circuit pattern that forms a connection terminal portion of a copper wiring on at least a part of an insulating layer having a copper wiring after forming a circuit pattern in the manufacturing process of a printed circuit board (for example, a package substrate for mounting semiconductor elements).

[0106] In addition, the composition of the present invention is suitable for removing a photoresist for forming a circuit pattern 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 at least a part of an insulating layer having a copper wiring after forming a circuit pattern in the manufacturing process of a semiconductor element.

[0107] Examples of the photoresist for a printed circuit board include, for example, a composition containing a binder polymer, a photopolymerizable monomer, a photoinitiator, and other additives.

[0108] 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.

[0109] Examples of the photopolymerizable monomer preferably include at least one of methacrylate and acrylate.

[0110] Examples of the photoinitiator 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 hexaarylbisimidazole and a hydrogen donor (2-mercaptobenzoxazole, N-phenylglycine) can also be used.

[0111] In addition, examples of other additives include a thermal polymerization initiator, a dye, and the like.

[0112] Examples of the photoresist that can be used for semiconductor elements 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] Among these, the dry film resist is preferably formed of a negative photosensitive resin. The negative photosensitive resin is cured by the exposure treatment during pattern formation and becomes insoluble in the developer, so 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 during exposure, especially the surface part exposed during exposure, is easy to carry out, and the surface part of the obtained dry film resist can 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, so there are cases where the dry film resist is not removed. As a result, it sometimes takes time to remove the dry film resist.

[0117] In contrast, the composition of the present invention is easily penetrated into the dry film resist, so the dry film resist can be quickly peeled off and removed.

[0118] Examples

[0119] (Preparation of samples for peelability evaluation)

[0120] The samples for peelability evaluation were prepared in the following manner. 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 this copper thin film, a circuit mask pattern was applied thereon, and exposure and development were performed. Electroplating copper (thickness: 17 μm) was performed on the circuit pattern opening formed by exposing and developing the dry film resist to obtain a sample for peelability evaluation. The pattern of the dry film resist applied to the sample for peelability evaluation was dots.

[0121] (Preparation of samples for copper corrosion resistance evaluation)

[0122] The samples for copper corrosion resistance evaluation were prepared in the following manner. That is, electroplating copper (thickness: 35 μm) was performed on the surface of a copper-clad laminate (manufactured by Mitsubishi Gas Chemical Company, Inc., CCL-HL832NX) to obtain a sample for copper corrosion resistance evaluation.

[0123] (Peel rate (L.P. (peeling start point)))

[0124] 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 and brought into contact with the above-mentioned samples for peelability evaluation.

[0125] 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). It should be noted that in the measurement of L.P., instead of observing the dot pattern portion applied on the sample for peelability evaluation, the solid portion around it is visually observed as the time when the dry film resist is removed.

[0126] (Corrosion resistance of copper (Cu E.R. (etch rate)))

[0127] 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 and brought into contact with the above-mentioned sample for evaluating the corrosion resistance of copper cut into a square of 4 cm × 4 cm. 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 thoroughly dried.

[0128] 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 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 back 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).

[0129]

[0130] (Peelability)

[0131] 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 3 minutes and brought into contact with the above-mentioned sample for peelability evaluation. Then, after washing with pure water, cleaning with 5% by mass sulfuric acid, and washing with pure water, it was thoroughly dried.

[0132] 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 on the sample for peelability evaluation after the spray treatment of the above aqueous composition was confirmed and evaluated according to the following criteria.

[0133] Especially good: The residues of the dry film resist are all 5 or less

[0134] Good: The residues of the dry film resist are all 110 or less

[0135] Poor: The residue of the dry film resist exceeds 110

[0136] [Example 1]

[0137] Prepare an aqueous composition by adding the following substances to 243 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 4% by mass (64 g of a 25% TMAH aqueous solution), potassium hydroxide (KOH) in an amount that finally becomes 0.3% by mass (2.4 g of a 50% KOH aqueous solution), ethylene glycol monopropyl ether in an amount that finally becomes 2% by mass (8.0 g), tolyltriazole in an amount that finally becomes 0.09% by mass (0.36 g), ammonium benzoate in an amount that finally becomes 1.5% by mass (6.0 g), and tetramethylammonium bicarbonate salt (TMBC) in an amount that finally becomes 11% by mass (44 g). The obtained aqueous composition has an L.P. of 60 sec, a Cu E.R. of 0.007 μm / min, and particularly good peelability.

[0138] It should be noted that tetramethylammonium bicarbonate salt can be generated as a degradation product of tetramethylammonium hydroxide, which will reduce the peelability of the dry film resist caused by the aqueous composition. Therefore, in order to evaluate the peeling treatment caused by the aqueous composition in the case of long-term use and generation of tetramethylammonium bicarbonate salt, this bicarbonate is added to the aqueous composition of this example.

[0139] The properties and evaluation results of the aqueous composition are shown in Table 2 below.

[0140] [Examples 2 - 5 and Comparative Examples 1 - 8]

[0141] As shown in Table 2 below, any one of the types and amounts of the respective components in the composition of Example 1 was changed, and otherwise, an aqueous composition was prepared in the same manner as in Example 1, and an evaluation test was conducted. The properties and evaluation results of the aqueous compositions of each example and comparative example are shown in Table 2 below.

[0142] Table 2 shows the distances from the center point (δd = 16, δp = 8.7, δh = 15.5) in the Hansen solubility parameter coordinates of the organic solvents contained in the aqueous compositions of each example and comparative example, and Table 3 shows the positions in the Hansen solubility parameter coordinates of the organic solvents in more detail.

[0143] [Table 2]

[0144]

[0145] [Table 3]

[0146]

[0147] As shown by the above results, for the aqueous composition of the example of an organic solvent close to the center point (δd = 16, δp = 8.7, δh = 15.5) in the coordinates containing Hansen solubility parameters (refer to the column of "[Distance from the center point [MPa 0.5 " in Table 2 and Table 3), it was confirmed that, compared with the aqueous composition of the comparative example, the time represented by the value of L.P. (peeling start point) was short, the photoresist could be peeled quickly, and the generation of resist residues could be suppressed. In addition, in the examples, compared with the comparative examples, the value of Cu E.R. (etching rate) tended to be lower, and a result with excellent corrosion resistance of copper was obtained.

Claims

1. A composition for removing a photoresist used to form a pattern containing copper after the pattern is formed, the composition comprising: an alkali agent comprising at least one selected from the group consisting of alkanolamines, quaternary ammonium hydroxides, and inorganic bases; An organic solvent, the coordinates of whose Hansen solubility parameter fall within the range of a sphere with a radius of 3.60 MPa centered on δd = 16.0, δp = 8.7, and δh = 15.5 0.5 and; Azole compounds.

2. The composition according to claim 1, wherein, The coordinates of the Hansen solubility parameter of the organic solvent fall within the range of a sphere with a radius of 3.00 MPa centered on δd = 16.0, δp = 8.7, and δh = 15.

5. 0.5 inside.

3. The composition according to claim 1, wherein, The organic solvent comprises ethylene glycol monomethyl ether, methyl hydrazine, 2,2,2-trifluoroethanol, diacetin, 1-chloro-2-propanol, dimethylaminoethanol, ethylenediamine, 1,9-nonanediol, 2-bromoallyl alcohol, 2,3-dichloropropanol, furfuryl alcohol, adipic acid, 2-chloroethanol, N-formylethylamine, ethylene glycol monopropyl ether, 2-chloro-2-propene-1-ol, 1-(2-hydroxyethyl)-2-pyrrolidone, diethylene glycol monovinyl ether, diethylenetriamine, 1,3-dichloro-2-propanol, 2 - At least one of the group consisting of ethoxyethanol, 3-chloro-2-propene-1-ol, serotonin, 1,6-hexanediol, 2-cyclopentene-1-ol, methylamine, formic acid, ethylene glycol monoisopropyl ether, 3-azidopropene, 2,3-butadiene-1-ol, allyl alcohol, 2-fluoroacrylic acid, acetic acid, azidoethane, isocyanic acid, n-propanol, (E)-2-butene-1-ol, methyl salicylate, 2-propanol, L-(-)-tyrosine, dipropylene glycol, ethyl carbamate and 2,2-dimethyl-1-propanol.

4. The composition according to claim 1, wherein, The etching rate of copper is less than 0.05 μm / min.

5. The composition according to claim 1, which is water-soluble.

6. The composition according to claim 1, wherein The composition comprises, based on the total amount of the composition: 3.0 to 50% by mass of the alkali agent, 0.1 to 30% by mass of the organic solvent, and 0.001 to 1.0 mass % of the azole compound.

7. The composition according to claim 1, wherein The pattern is a circuit pattern that is formed on an insulating layer having a copper wiring at least partially and serves as a connection terminal portion of the copper wiring.

8. A method for removing a photoresist, comprising: A photoresist removal step of bringing the composition according to any one of claims 1 to 7 into contact with a photoresist for forming a pattern containing copper.

9. The method for removing a photoresist according to claim 8, wherein, The pattern is a circuit pattern that is formed on an insulating layer having a copper wiring at least partially and serves as a connection terminal portion of the copper wiring.

10. A method for manufacturing a printed circuit board, a semiconductor component, or a semiconductor package, comprising: A photoresist removal step of bringing the composition according to any one of claims 1 to 7 into contact with a photoresist for forming a pattern containing copper.

11. The manufacturing method of a printed circuit board, semiconductor element or semiconductor package according to claim 10, wherein, The pattern is a circuit pattern that is formed on an insulating layer having a copper wiring at least partially and serves as a connection terminal portion of the copper wiring.

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