Structure manufacturing method and photoresist stripping method

Abstract

The invention relates to a method for manufacturing a structure and a method for peeling off a photoresist. The purpose of the present invention is to solve the technical problem related to the conventional photoresist stripper and to provide a photoresist stripping method capable of implementing a treatment that does not leave a stripping residue in a short time and causes little damage to a structure as a purpose, and a method for manufacturing a structure using the same. In this method for manufacturing a structure, a photoresist having a thickness of 50 [mu] m or more is peeled off using two or more types of treatment liquid in this order.

Description

Technical Field

[0001] The present invention relates to a photoresist stripping method mainly used in a semiconductor device manufacturing step or the like, and a method for manufacturing a structure using the method. Background Art

[0002] Semiconductor integrated circuits are manufactured by coating a photoresist on a substrate and performing exposure and development, then etching and forming a circuit, and then stripping the photoresist from the substrate, or after ashing and removing the photoresist after the circuit is formed, stripping the remaining photoresist residue.

[0003] In addition, printed circuit boards are generally manufactured by laminating dry film photoresists, exposing, developing, etching, forming circuits, and then stripping the photoresists from the substrate. In order to strip the photoresists, a wet method using a photoresist stripping liquid is generally used.

[0004] In the semiconductor field, solder bumps are needed as terminals for wafer-level CSP (chip size package) or flip chip mounting recently, but thick film (about 40 to 150 μm thick) photoresist is often used in the process of forming bumps. The thicker the resist film, the harder it is to peel off. After solder paste is embedded in the photoresist pattern, the heating process (reflow) for forming bumps may apply heat to the photoresist film, making it more difficult to peel off. Therefore, a stripping liquid with high stripping performance is required.

[0005] Even if a sodium hydroxide aqueous solution or a general organic solvent is used alone as a stripping solution, there is a stripping effect, but the stripping property is not sufficient. Therefore, various photoresist stripping solutions for improving the stripping property have been proposed in the past.

[0006] As such a resist stripping solution, for example, a resist stripping solution composition using an alkanolamine is known (see Patent Document 1).

[0007] However, in the stripping liquid composition using alkanolamine, the stripping of the photoresist residue whose inorganic properties have been deteriorated by dry etching, ashing, ion implantation, etc. is not sufficient.

[0008] In addition, the latest submicron processing technology uses metal materials including TiN, TiSi, etc. However, when these metal materials are used, stable byproducts such as titanium oxide are generated during the processing. Titanium oxide cannot be removed by alkanolamines used in the past.

[0009] In addition, there are known techniques for improving the peeling performance by combining a polar organic solvent with a basic organic compound such as an amine or an ammonium salt (see Patent Documents 2, 3, 4, 5, 6, 7, and 8). However, these techniques are not sufficient in terms of peeling properties.

[0010] [Prior art literature]

[0011] [Patent Document]

[0012] Patent Document 1: Japanese Patent Application Laid-Open No. 62-49355

[0013] Patent Document 2: Japanese Patent No. 3302120

[0014] Patent Document 3: Japanese Patent Application Laid-Open No. 11-16882

[0015] Patent Document 4: Japanese Patent Application Laid-Open No. 10-239865

[0016] Patent Document 5: Japanese Patent Application Publication No. 2001-98191

[0017] Patent Document 6: Japanese Patent Application Publication No. 2001-215736

[0018] Patent Document 7: Japanese Patent Application Publication No. 2001-312074

[0019] Patent document 8: Japanese Patent Application Publication No. 2002-12897. Summary of the invention

[0020] [Problems to be solved by the invention]

[0021] The object of the present invention is to solve the above-mentioned technical problems related to the conventional photoresist stripping solution, and to provide a photoresist stripping method that can perform a treatment in a short time without leaving any stripping residue and with little damage to the target structure, and a method for manufacturing a structure using the method.

[0022] [Methods to solve the problem]

[0023] The inventors of the present application have conducted intensive studies to solve the above-mentioned problems and have completed the present invention as a result.

[0024] That is, the present invention relates to the following 1) to 12).

[0025] 1) A method for manufacturing a structure, wherein two or more treatment solutions are used in sequence to peel off a photoresist having a thickness of 50 μm or more.

[0026] 2) The production method as described in 1) above, wherein the step of sequentially using two or more treatment solutions is repeated two or more times.

[0027] 3) The production method according to 1) or 2) above, wherein the two or more treatment liquids are (A) a swelling liquid and (B) a stripping liquid.

[0028] 4) The production method according to 3) above, wherein the (A) is a swelling liquid containing 10% by mass or more of the (A-1) organic solvent.

[0029] 5) The production method according to 3) above, wherein (A) is a swelling liquid containing two or more organic solvents.

[0030] 6) The production method according to 3) above, wherein the (A) is a swelling liquid containing an amine compound (A-2).

[0031] 7) The production method according to 3) above, wherein the (B) is an alkaline aqueous solution.

[0032] 8) The production method according to 3) above, wherein the (B) is a stripping solution containing (B-1) an amine compound.

[0033] 9) The manufacturing method as described in any one of 1) to 8) above, wherein the photoresist comprises a dry film photoresist.

[0034] 10) The manufacturing method as described in 1) to 8) above, wherein the photoresist is a photoresist of stacked multi-layer dry film photoresists.

[0035] 11) The manufacturing method according to any one of 1) to 10) above, wherein the structure is a plurality of columnar conductive structures.

[0036] 12) A photoresist stripping method, wherein two or more treatment solutions are used in sequence to strip a photoresist having a thickness of 50 μm or more.

[0037] [Effects of the invention]

[0038] The method for manufacturing a structure of the present invention can exhibit good stripping properties relative to photoresists such as liquid photoresists and dry film photoresists on the substrate without affecting the insulating layer of the substrate, and has the effect of causing less damage to the target structure. DETAILED DESCRIPTION

[0039] The method for manufacturing a structure of the present invention sequentially uses two or more processing liquids to peel off a photoresist having a thickness of 50 μm or more.

[0040] [About photoresist]

[0041] The present invention is used for a method of manufacturing a columnar conductive structure by obtaining a plated photoresist film by electrolytically plating a metal on a photoresist layer having an opening, and then stripping the plated photoresist film by an immersion method or a shower method using a photoresist stripping solution.

[0042] The photoresist used can be a liquid photoresist or a dry film photoresist. Examples of liquid photoresists include photosensitive photoresists such as epoxy resin compositions, polyimide resin compositions, and acrylic resin compositions. In addition, dry film photoresists are classified into negative and positive types according to the reaction mechanism. The negative type is a type that hardens by photopolymerization through exposure and is insoluble in the developer, while the positive type is a type that is soluble in the developer in the exposed part. Currently, the dry film photoresist mainly uses the negative type. Generally speaking, it is composed of an adhesive polymer such as an acrylic acid series that imparts film-forming ability, an acrylic monomer that performs a free radical polymerization reaction, a photopolymerization initiator, a dye, an adhesive, and other additives.

[0043] Next, the structure obtained by the method of the present invention is a columnar structure formed continuously, preferably having a height of about 50 μm or more. That is, the thickness of the photoresist with the opening is 50 μm or more. The lower limit of the thickness is more preferably 60 μm, 75 μm, 90 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, and particularly preferably 160 μm. In addition, the upper limit is about 500 μm, more preferably 450 μm, 400 μm, 350 μm, 300 μm, and particularly preferably 250 μm.

[0044] When a dry film photoresist is used as the photoresist of the present invention, the thickness of a single layer is preferably 50 μm or more and 120 μm or less, and the above thickness of the photoresist can be achieved by stacking multiple layers.

[0045] [Two or more treatment solutions]

[0046] The present invention is characterized in that two or more treatment liquids are used in sequence. Two or more treatment liquids means that the treatment liquids may have different compositions and the functions may be the same or different.

[0047] However, it is more preferred that one of the two treatment liquids (A) is a swelling liquid having a swelling function, and the other (B) is a stripping liquid having a stripping function. In addition, in addition to the treatment with the two treatment liquids, the use of other treatment liquids or other steps is not excluded as an embodiment of the present invention. For example, between the treatment with one treatment liquid and the treatment with another treatment liquid, a treatment with a rinse liquid or a drying step is also an embodiment of the present invention.

[0048] [(A) Swelling fluid]

[0049] <(A-1) Organic Solvent>

[0050] The composition of the (A) swelling liquid is more preferably a composition containing 10% by mass or more of the (A-1) organic solvent.

[0051] The organic solvent includes, for example, C1-C6 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, etc.; C2-C6 alcohols such as ethylene glycol, diethylene glycol, 1,2-propylene glycol (propylene glycol), 1,3-propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,2-hexanediol, 1,6-hexanediol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, dithiodiglycol, etc. diol; or mono-, oligo-, or poly-alkylene glycol or thioglycol having C2-C6 alkylene units; polyols (triols) such as glycerol, diglycerol, hexane-1,2,6-triol, trimethylolpropane, dimethyl sulfoxide (hereinafter referred to as DMSO), cyclopentane, dimethyl sulfone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone (Methyl pyrrolidone) (hereinafter referred to as NMP), N-vinyl-2-pyrrolidone (Methyl pyrrolidone), ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, tetramethyl urea, hexamethylphosphoric triamide, γ-butyrolactone, δ-valerolactone, ε-caprolactone, acetonitrile, pyridine, dimethoxyethane, carbitols, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, etc., and a more preferred aspect of the present invention is the case where two or more kinds are used in combination.

[0052] The organic solvent is more preferably a glycol solvent such as ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, dithiodiglycol, or an aprotic polar solvent such as DMSO, sulfolane, dimethyl sulfone, DMF, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone (Methyl pyrrolidone) NMP, N-vinyl-2-pyrrolidone (Methyl pyrrolidone), and more preferably a combination of two or more of these, particularly preferably a combination of one glycol solvent and one aprotic polar solvent, and most preferably a combination of one glycol solvent and two aprotic polar solvents. Specifically, the most preferred is a combination of propylene glycol, DMSO, and NMP.

[0053] The content of the organic solvent in the swelling liquid (A) is preferably 10% by mass or more, and the lower limit is preferably 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, 80%, particularly preferably 90% by mass or more. The upper limit may be 100% by mass, but when other components described below are contained, the upper limit may be about 99%, 98%, 97%, or 95% by mass.

[0054] When a diol solvent and an aprotic polar solvent are used in combination, the blending ratio is preferably 1 / 99 to 30 / 70, more preferably 5 / 95 to 25 / 75, and particularly preferably 7 / 93 to 10 / 90. In addition, for example, when DMSO and NMP are used in combination, the blending ratio is preferably 40 / 60 to 90 / 10, more preferably 50 / 50 to 85 / 15, and particularly preferably 60 / 40 to 80 / 20. In addition, in this specification, "to" is set to include the numbers before and after.

[0055] <Amine compounds>

[0056] (A) It is more preferable that the swelling liquid contains an amine compound in addition to the above-mentioned organic solvent.

[0057] Examples of the amine compound include monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N-(2-aminoethyl)ethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-(2-hydroxyethyl)piperidinolamine, N-(2-Hydroxyethyl) Alkanolamines such as phenoxyethylene; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, piperine N-(2-aminoethyl)piperidin Ethylene amines such as triethylenediamine; N,N,N',N'-tetramethylethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N-methylpiperidin N,N,N'-Trimethylaminoethylpiperidin N-alkylethyleneamines such as propanediamine, butanediamine, hexamethylenediamine and other diamines other than ethyleneamine; imidazoles such as imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 1,2,4,5-tetramethylimidazole, 2-ethyl-4-methylimidazole; Monoamines such as phenoxyethanol, cyclohexylamine, 2-ethyl-hexylamine, benzylamine, and aniline; alkylamines such as triethylamine, tripropylamine, and tributylamine; tetramethylammonium hydroxide (hereinafter referred to as TMAH) and tetrabutylammonium hydroxide; tetramethylammonium carbonate and other tetramethylammonium carbonates; tetramethylammonium acetate and other tetramethylammonium acetates; tetramethylammonium citrate and other tetramethylammonium citrates; tetramethylammonium silicate and other tetramethylammonium silicate; trimethyl-2-hydroxyethylammonium hydroxide (choline), trimethyl-2-hydroxyethoxyammonium hydroxide, trimethyl-2-(2-hydroxyethoxy)ethoxyammonium hydroxide and other trialkyl-2-hydroxyalkylammonium hydroxides or trialkyl-2-hydroxyalkoxyalkylammonium hydroxides. These amine compounds may be used in combination of two or more, and the most preferred embodiment is the combination of N-methylethanolamine and TMAH.

[0058] <Other ingredients>

[0059] (A) The swelling agent may contain an anticorrosive agent, a surfactant, and the like in addition to the above-mentioned organic solvent and amine compound.

[0060] (Anti-corrosion agent)

[0061] (A) The corrosion inhibitor that can be contained in the swelling liquid includes, for example, acetic acid, acetone oxime, acrylic acid, alanine, arginine, asparagine, betaine, dimethylglyoxal dioxime, formic acid, glyceric acid, glycerol, glycolic acid, glyoxylic acid, histidine, itaconic acid, lactic acid, leucine, lysine, maleic anhydride, mandelic acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, proline, propionic acid, catechol, quinone, Acid, serine, sorbitol, tyrosine, valine, xylitol, tannic acid, picolinic acid, 1,3-cyclopentanedione, catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid, barbituric acid, 1,3-dimethylbarbituric acid, pyruvic acid, propanethiol, phenylhydroxamic acid, 2,5-dicarboxypyridine, 4-(2-hydroxyethyl) Hemocyanine (HEM), N-aminoethylpiperidin (N-AEP), thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, cysteine, isoleucine, methionine, piperidine N-(2-aminoethyl)piperidin Pyrrolidine, threonine, tryptophan, salicylic acid, p-toluenesulfonic acid, salicylhyroxyamic acid, 5-sulfosalicylic acid, and combinations thereof, but are not limited thereto.

[0062] (Surfactant)

[0063] (A) The surfactant that may be contained in the swelling liquid may include anionic, nonionic, cationic and / or zwitterionic surfactants, such as alginic acid and its salts; carboxymethyl cellulose; polyglucose sulfate and its salts; poly(galacturonic acid) and its salts; homopolymers of (meth)acrylic acid and its salts, maleic acid, maleic anhydride, styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, and acrylamidopropyl sulfonic acid and its salts; copolymers of (meth)acrylic acid and its salts, maleic acid, maleic anhydride, styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, and acrylamidopropyl sulfonic acid and its salts; chitosan; cationic starch; polylysine and its salts; diallyldimethylammonium chloride (DADMAC), dimethicone; Allyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, dimethylallyldimethylammonium chloride, diethylallylammonium chloride, diallyldi(β-hydroxyethyl)ammonium chloride, diallyldi(β-ethoxyethyl)ammonium chloride, dimethylaminoethyl (meth)acrylate acid addition salt and quaternary salt, diethylaminoethyl (meth)acrylate acid addition salt and quaternary salt, (meth)acrylate 7-amino-3,7-dimethyloctyl acid addition salt and quaternary salt, N,N'-dimethylaminopropyl acrylamide acid addition salt and quaternary salt, allylamine, diallylamine, vinylamine, homopolymers of vinylpyridine; and diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallyldimethylammonium Sulfate, diallyldimethylammonium phosphate, dimethylallyldimethylammonium chloride, diethylallylammonium chloride, diallyldi(β-hydroxyethyl)ammonium chloride, diallyldi(β-ethoxyethyl)ammonium chloride, dimethylaminoethyl (meth)acrylate acid addition salt and quaternary salt, diethylaminoethyl (meth)acrylate acid addition salt and quaternary salt, (meth)acrylate 7-amino-3,7-dimethyloctyl acid addition salt and quaternary salt, N,N'-dimethylaminopropyl acrylamide acid addition salt and quaternary salt, allylamine, diallylamine, vinylamine, copolymer of vinylpyridine; coconut oil dimethyl carboxymethyl betaine; lauryl dimethyl carboxymethyl betaine; lauryl dimethyl-α-carboxyethyl betaine; cetyl dimethyl carboxymethyl betaine; lauryl 1-Hydroxy-2-hydroxyethyl) carboxymethyl betaine; 1-Hydroxy-2-hydroxypropyl) carboxymethyl betaine; 1-Oleyl dimethyl-γ-carboxypropyl betaine; 1-Lauryl-2-(2-hydroxypropyl) α-carboxyethyl betaine; 1-Cocoyl dimethyl sulfopropyl betaine; 1-Stearyl dimethyl sulfopropyl betaine; 1-Lauryl-2-(2-hydroxyethyl) sulfopropyl betaine; 1-Sodium lauryl sulfate; 1-Dioctyl sulfosuccinate sodium salt; 1-Sodium lauryl ether sulfate; 1-Polyethylene glycol branched nonylphenyl ether sulfate ammonium salt; 2-Dodecyl-3-(2-sulfophenoxy) disodium; 1-PEG25-PABA; 1-C10-16-polyethylene glycol mono-alkyl ether sulfate sodium salt; 1-(2-butoxyethoxy)acetic acid; 1-Hexadecylbenzenesulfonic acid;Cetyl trimethyl ammonium hydroxide; dodecyl trimethyl ammonium hydroxide; dodecyl trimethyl ammonium chloride; cetyl trimethyl ammonium chloride; N-alkyl-N-benzyl-N,N-dimethyl ammonium chloride; dodecylamine; polyoxyethylene lauryl ether; dodecenyl succinic acid monodiethanolamide; ethylenediamine tetra(ethoxide-block-propoxide); and combinations thereof, but not limited thereto. ;

[0064] <(B) Stripping solution>

[0065] When the other of the aforementioned treatment liquids is the stripping liquid (B), the treatment with the liquid (B) is performed after the treatment with the liquid (A). In addition, although the description is repeated, the method of having other treatment liquids or other steps between the treatment with the liquid (A) and the treatment with the liquid (B) is not excluded from the present invention.

[0066] The composition of the stripping solution (B) is preferably an alkaline aqueous solution. The alkaline aqueous solution preferably contains (B-1) an amine compound and (B-3) water, and may also contain (B-2) an organic solvent having a hydroxyl group.

[0067] ((B-1) Amine compound)

[0068] Examples of the amine compound include monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N-(2-aminoethyl)ethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, triethanolamine sulfate, N-(2-hydroxyethyl)piperidinol, N-(2-Hydroxyethyl) Alkanolamines such as phenoxyethylene; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, piperine N-(2-aminoethyl)piperidin Ethyleneamines such as triethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N-methylpiperidin N,N,N'-Trimethylaminoethylpiperidin N-alkylethyleneamines, etc.; diamines other than ethyleneamine, such as propanediamine, butanediamine, hexamethylenediamine, etc.; imidazoles such as imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 1,2,4,5-tetramethylimidazole, 2-ethyl-4-methylimidazole, Monoamines such as phenoxylin, cyclohexylamine, 2-ethyl-hexylamine, benzylamine, and aniline; alkylamines such as triethylamine, tripropylamine, and tributylamine; tetramethylammonium hydroxide (hereinafter referred to as TMAH), tetrabutylammonium hydroxide, and other tetra(C1 to C6) alkylammonium hydroxides; tetramethylammonium carbonate, and other tetra(C1 to C6) alkylammonium carbonates; tetramethylammonium acetate, and other tetra(C1 to C6) alkylammonium acetates; tetramethylammonium citrate, and other tetra(C1 to C6) alkylammonium citrates; tetramethylammonium silicate, and other tetra(C1 to C6) alkylammonium silicates; trimethyl-2-hydroxyethylammonium hydroxide (choline), trimethyl-2-hydroxyethoxyammonium hydroxide, trimethyl-2-(2-hydroxyethoxy)ethoxyammonium hydroxide, and other trialkyl-2-hydroxyalkylammonium hydroxides or trialkyl-2-hydroxyalkoxyalkylammonium hydroxides, and the like. These amine compounds may be used in combination of two or more, preferably three or more, and most preferably four or more. Specifically, it is most preferable to use TMAH, diethanolamine, N-methylethanolamine, and triethanolamine sulfate in combination.

[0069] ((B-2) Organic solvent having hydroxyl group)

[0070] Examples of the organic solvent having a hydroxyl group include C1-C6 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, and tert-butanol; C2-C6 diols such as ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,2-hexanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, and dithiodiglycol; or mono-, oligo-, or polyalkylene glycols or thioglycols having a C2-C6 alkylene unit; polyols (triols) such as glycerol, diglycerol, hexane-1,2,6-triol, and trimethylolpropane; aromatic alcohols such as benzyl alcohol; polyoxyalkylene alkyl ethers such as polyoxyethylene (3) lauryl ether; and two or more thereof may be used in combination. Among them, a more preferred aspect is an aspect in which benzyl alcohol and polyoxyethylene (3) lauryl ether are used in combination.

[0071] ((B-3) Water)

[0072] The content of water in the stripping liquid (B) is usually 1% by mass to 99% by mass, more preferably 10% by mass to 98% by mass, particularly preferably 20% by mass to 97% by mass, and most preferably 25% by mass to 95% by mass.

[0073] (Other ingredients)

[0074] Other components that may be contained in the alkaline aqueous solution include, for example, anticorrosive agents, surfactants, etc. Usable anticorrosive agents and surfactants are preferably the same as those in the case of (A) the swelling solution.

[0075] (pH)

[0076] (B) The pH of the stripping solution is more preferably 8.0 or higher.

[0077] The pH of the stripping solution (B) is more preferably 10.0 or higher, particularly preferably 12.0 or higher. The upper limit may be about 14.0.

[0078] [Number of processing times]

[0079] In the manufacturing method of the present invention, a sufficient effect can be obtained by using the above-mentioned two or more treatment liquids in sequence, but a significant effect can be confirmed by repeating it more than two times. For example, when the thickness of the photoresist is thicker, sufficient photoresist stripping can be achieved, and the damage to the structure can be suppressed to a low level. For example, the use of two or more treatment liquids in sequence is set as one group, preferably two or more groups, and more preferably three or more groups. In addition, the upper limit can be set while confirming the state of photoresist stripping. When the photoresist exceeds 450μm, it is more preferably about 5 groups.

[0080] In addition, when repeated multiple times, the processing liquids of the first group and the second group and thereafter do not need to be the same, and can be appropriately changed while confirming the photoresist stripping state. However, considering the complexity of modulation, it is more preferred to use the same two or more processing liquids for the first group and the second group and thereafter.

[0081] [Structure]

[0082] The structure obtained by the manufacturing method of the present invention is a columnar conductive structure.

[0083] The columnar conductive structure refers to the columnar part of the Cu column method, which is related to the flip chip mounting technology that has attracted much attention with the high integration of chips in recent years. The columnar conductive structure can be formed by forming a wiring pattern using a photoresist and developing it, forming a Cu column using an electroplating method, and removing the photoresist.

[0084] [Example]

[0085] The present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0086] <Preparation of Drug Solutions 1 to 8>

[0087] The components listed in Table 1 were blended to prepare drug solutions 1 to 8. In Table 1, the blending amounts are parts by mass.

[0088] [Table 1]

[0089]

[0090]

[0091] <Preparation of test pieces>

[0092] Three layers of 100 μm thick acrylic resin dry film photoresist were stacked and formed on the substrate subjected to Cu electroplating. The substrate was cut into 30 mm×30 mm pieces to prepare test pieces.

[0093] <Photoresist peeling evaluation>

[0094] The test pieces were immersed in the chemical solutions listed in Tables 2 and 3 at 60°C.

[0095] The chemical solution used, treatment time, time required for peeling, and the observed color change of Cu after peeling are displayed together.

[0096] [Table 2]

[0097]

[0098] [Table 3]

[0099]

[0100]

[0101] ◎; No discoloration

[0102] ○; Partial discoloration

[0103] △; less than half discolored

[0104] ×: More than half of the color is changed

[0105] ※: No peeling even after immersion for 100 minutes

[0106] As can be seen from Tables 1 to 3, when two or more treatment solutions are used in sequence, it can be confirmed that the stripping time is shortened and the damage to Cu is reduced when the photoresist having a thickness of 50 μm or more is stripped.

[0107] [Industrial Applicability]

[0108] According to the method for manufacturing a structure and the method for stripping a photoresist of the present invention, a process can be performed in a short time without any stripping residue and with little damage to the target structure, so that a semiconductor device or a liquid crystal device can be manufactured more simply and economically.

Claims

1. A method for manufacturing a structure, wherein two or more treatment solutions are used in sequence to peel off a photoresist having a thickness of 50 μm or more.

2. The production method according to claim 1, wherein the step of sequentially using two or more treatment solutions is repeated two or more times.

3. The manufacturing method according to claim 1 or 2, wherein: The two or more treatment liquids are (A) a swelling liquid and (B) a stripping liquid.

4. The manufacturing method according to claim 3, wherein: The aforementioned (A) is a swelling liquid containing 10 mass % or more of (A-1) an organic solvent.

5. The manufacturing method according to claim 3, wherein: The aforementioned (A) is a swelling liquid containing two or more organic solvents.

6. The manufacturing method according to claim 3, wherein: The aforementioned (A) is a swelling liquid containing the (A-2) amine compound.

7. The manufacturing method according to claim 3, wherein: The aforementioned (B) is an alkaline aqueous solution.

8. The manufacturing method according to claim 3, wherein: The above-mentioned (B) is a stripping solution containing (B-1) an amine compound.

9. The manufacturing method according to claim 1 or 2, wherein: The aforementioned photoresist includes a dry film photoresist.

10. The manufacturing method according to claim 1 or 2, wherein: The photoresist is a stacked multi-layer dry film photoresist.

11. The manufacturing method according to claim 1 or 2, wherein: The aforementioned structures are a plurality of columnar conductive structures.

12. A method for stripping a photoresist, wherein two or more treatment solutions are used in sequence to strip a photoresist having a thickness of 50 μm or more.

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