Photoresist stripping composition

Abstract

To provide a photoresist stripping composition which exhibits a high stripping property even with respect to a cured resist, suppresses corrosion of substrate constituent metals, such as Cu and Al, in contact with a liquid, and can suppress excessive oxidation of the metals such as Cu during a stripping process.SOLUTION: Provided is a photoresist stripping composition, containing (A) a quaternary ammonium hydroxide, (B) diethylene glycol monoethyl ether, (C) glycerin, and (D) water, wherein the content of (A) is 0.5-5 mass% based on the total mass of the composition, the content of (B) is 50-95 mass% based on the total mass of the composition, the content of (C) is 0.5-20 mass% based on the total mass of the composition, and the content of (D) is less than 20 mass% based on the total mass of the composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photoresist stripping composition. [Background technology]

[0002] Photoresist stripping compositions are used to strip unnecessary photoresist coatings after etching or plating processes in photolithography, which forms metal wiring patterns such as Cu on silicon or glass substrates. In the etching or plating processes, resist polymers are hardened by crosslinking, so stripping agents that can remove hardened resist are required. Furthermore, Cu and Al are commonly used as metals for wiring, and a stripping agent with excellent corrosion resistance against Cu and Al is desired. Therefore, in order to improve corrosion resistance against Al, compositions containing added Al corrosion inhibitors have been developed, but the addition of the Al corrosion inhibitor can lead to a decrease in strippability, which has been a problem. Therefore, there is a demand for a stripping agent that has corrosion protection and stripping properties against Cu and Al.

[0003] On the other hand, a method using ultrasonic waves is used to strip hardened photoresist. The cavitation effect of ultrasonic waves causes the stripping solution to penetrate between the underlying film and the resist, and the shock waves pulverize and strip the resist. While N-methylpyrrolidinone (NMP) is an effective stripping solution for this method, its use is restricted due to its environmental impact and human toxicity. Furthermore, its low resist solubility increases the frequency of solution changes and raises concerns about the re-adhesion of the resist to the substrate.

[0004] Patent Document 1 discloses a photoresist stripping solution containing tetramethylammonium hydroxide (TMAH), diethylene glycol monoethyl ether (EDG), sorbitol, alkanolamine, and water. Patent Document 2 discloses a processing liquid for semiconductor devices that contains a hydroxylamine compound, an organic basic compound, an alcohol-based solvent, a surfactant, and the like. Patent Document 3 discloses a composition containing TMAH, an alcohol solvent, an Al corrosion inhibitor, and water, and describes that it can strip thick-film positive or negative resists. Patent Document 4 discloses a composition containing TMAH, glycerin, EDG, and carboxybenzotriazole, and describes that the composition can strip positive photoresists and negative photoresists. Patent Document 5 discloses a composition containing TMAH, EDG, and water, and describes that the composition can effectively remove photoresist film residues and etching residues from a substrate on which at least a metal layer containing tantalum is formed as a conductive metal film. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] WO2021 / 020410 [Patent Document 2] WO2019 / 187868 [Patent Document 3] Special Publication 2018-503127 [Patent Document 4] Special Publication 2013-527992 [Patent Document 5] Patent Publication No. 2008-58625 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the above-mentioned conventional photoresist stripper has the problem that it is insufficient to strip excessively hardened photoresist, and the corrosion inhibition of Cu or Al is insufficient.In view of the above-mentioned conventional problems, the object of the present invention is to provide a photoresist stripping composition that shows high stripping ability even to hardened resist, inhibits the corrosion of substrate metals such as Cu and Al that contact with the liquid, and can inhibit excessive oxidation of metals such as Cu during the stripping process. [Means for solving the problem]

[0007] In the course of investigations aimed at solving the above-mentioned problems, the present inventors discovered that a photoresist stripping composition comprising (A) a quaternary ammonium hydroxide, (B) diethylene glycol monoethyl ether, (C) glycerin, and (D) water, wherein the content of (A) is 0.5 to 5 mass % relative to the total mass of the composition, the content of (B) is 50 to 95 mass % relative to the total mass of the composition, the content of (C) is 0.5 to 20 mass % relative to the total mass of the composition, and the content of (D) is less than 20 mass % relative to the total mass of the composition, exhibits high stripping properties even for cured resist, inhibits corrosion of metals such as Cu and Al, and can inhibit excessive metal oxidation during the stripping process, thereby completing the present invention.

[0008] That is, the present invention relates to the following. [1] A photoresist stripping composition, the composition comprises (A) a quaternary ammonium hydroxide, (B) diethylene glycol monoethyl ether, (C) glycerin, and (D) water; The composition, wherein the content of (A) is 0.5 to 5 mass% relative to the total mass of the composition, the content of (B) is 50 to 95 mass% relative to the total mass of the composition, the content of (C) is 0.5 to 20 mass% relative to the total mass of the composition, and the content of (D) is less than 20 mass% relative to the total mass of the composition. [2] The composition according to [1], wherein the composition does not contain hydroxylamine or a hydroxylamine salt. [3] (D) The composition according to [1] or [2], wherein the water content is 5% by mass or less based on the total mass of the composition. [4] The composition according to any one of [1] to [3], further comprising (E) ethylene glycol, the content of which is 1 to 10 mass % relative to the total mass of the composition. [5] The composition further comprises (F) an alkanolamine, and the content thereof is 1 to 20% by weight of the total weight of the composition. quality %. [6] (F) The composition according to [5], wherein the alkanolamine is monoethanolamine, diethanolamine, or 2-(2-aminoethoxy)ethanol. [7] The composition according to any one of [1] to [6], further comprising (G) at least one selected from the group consisting of 4-carboxybenzotriazole and 5-carboxybenzotriazole, and the total content of (G) is 0.05 to 1.00 mass% relative to the total mass of the composition. [8] (A) The composition according to any one of claims [1] to [7], wherein the quaternary ammonium hydroxide is one or more selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline hydroxide, and ethyltrimethylammonium hydroxide. [9] The composition according to any one of [1] to [8], wherein the composition does not contain dimethyl sulfoxide or N-methylpyrrolidone.

[10] The composition according to any one of [1] to [9], wherein the composition does not contain sodium hydroxide or potassium hydroxide.

[11] The composition according to any one of [1] to

[10] , wherein the composition does not contain a triazine compound.

[12] A method for stripping a photoresist, comprising contacting a semiconductor substrate containing a photoresist or a photoresist residue applied to a substrate having metal wiring with the composition according to any one of [1] to

[11] , thereby removing the photoresist. [Effects of the Invention]

[0009] The photoresist stripping composition of the present invention exhibits high stripping properties even for cured resist, and can inhibit corrosion of metals such as Cu and Al and excessive metal oxidation during the stripping process. Excessive metal oxidation can cause device failure. Under ultrasonic application conditions, in particular, water is thermally decomposed at hot spots generated by ultrasonic application, generating hydroxyl radicals, which then oxidize the metal, resulting in excessive metal oxidation. The photoresist stripping composition of the present invention can inhibit corrosion and excessive oxidation of Cu, Al, and other metals even under such ultrasonic application conditions.

[0010] The compositions of the present invention do not require highly toxic solvents. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below based on preferred embodiments of the present invention. The photoresist stripping composition of the present invention comprises: 1. A photoresist stripping composition comprising: the composition comprises (A) a quaternary ammonium hydroxide, (B) diethylene glycol monoethyl ether, (C) glycerin, and (D) water; The composition contains 0.5 to 5% by mass of (A), 50 to 95% by mass of (B), 0.5 to 20% by mass of (C), and less than 20% by mass of (D). It exhibits high strippability even against cured resist, inhibits corrosion of metals such as Cu and Al, and inhibits excessive oxidation of metals such as Cu during the stripping process. In this specification, the numerical range "a to b" means "not less than a and not more than b."

[0012] Each component contained in the composition of the present invention will be described below. The composition of the present invention comprises (A) a quaternary ammonium hydroxide. Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltriethylammonium hydroxide, benzyltrimethylammonium hydroxide, ethyltrimethylammonium hydroxide, choline hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, monomethyltris(2-hydroxyethyl)ammonium hydroxide, etc. From the viewpoints of purity, solubility in solvents, etc., the quaternary ammonium hydroxide is preferably one or more selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline hydroxide, and ethyltrimethylammonium hydroxide. The content of the quaternary ammonium hydroxide is 0.5 to 5 mass % relative to the total mass of the composition, and preferably 0.5 to 3 mass % relative to the total mass of the composition.

[0013] The composition of the present invention comprises (B) diethylene glycol monoethyl ether (EDG). The content of diethylene glycol monoethyl ether is 50 to 95% by mass relative to the total mass of the composition. In one embodiment, the content of diethylene glycol monoethyl ether is preferably 60 to 95%, 65 to 95%, 70 to 95%, 75 to 95%, 80 to 95%, 85 to 95%, or 90 to 95% by mass relative to the total mass of the composition, from the viewpoints of resist strippability, resist solubility, and suppression of metal corrosiveness.

[0014] The composition of the present invention contains (C) glycerin. Surprisingly, the inclusion of glycerin improves both the corrosion prevention and strippability of metals such as aluminum by quaternary ammonium salts and the like. Commonly used aluminum corrosion inhibitors include sorbitol and xylitol, but these have low solubility in EDG, which causes the problem of precipitation. In addition, sorbitol and xylitol have low solubility in isopropyl alcohol (IPA), which is used in subsequent cleaning, making IPA rinsing impossible. Glycerin is preferred because of its high solubility in EDG and IPA. The content of (C) glycerin is 0.5 to 20 mass% relative to the total mass of the composition. From the viewpoints of sufficient Al corrosion prevention and high releasability, the content of glycerin is preferably 1 to 15 mass%, 5 to 15 mass%, or 10 to 15 mass% relative to the total mass of the composition.

[0015] The composition of the present invention comprises (D) water. The content of water is less than 20% by mass based on the total mass of the composition. From the viewpoints of resist solubility and metal corrosion inhibition, the content of water is preferably 0.1% by mass based on the total mass of the composition. quality % or more and less than 15% by mass, and more preferably 0.1 quality % or more and less than 10% by mass, and more preferably 0.1 quality % or more and 5% by mass or less.

[0016] In one embodiment, the composition of the present invention does not contain hydroxylamine or hydroxylamine salts. Hydroxylamine or hydroxylamine salts are often contained in conventional stripping compositions to remove residues of Ti metal or Al metal, but they can cause metal corrosion and may even pose an explosion, so in one embodiment, the composition of the present invention does not contain them.

[0017] Preferably, the composition of the present invention further comprises (E) ethylene glycol. In one embodiment, the content of (E) ethylene glycol is 1 to 10% by mass relative to the total mass of the composition. That is, in one embodiment, the release agent of the present invention relates to a composition further comprising ethylene glycol (E), the content of which is 1 to 10% by mass relative to the total mass of the composition.

[0018] In certain embodiments, the compositions of the present invention further comprise (F) an alkanolamine. (F) Alkanolamines include, for example, monoethanolamine, diethanolamine, triethanolamine, 2-(methylamino)ethanol, 2-(dimethylamino)ethanol, 2-(2-aminoethoxy)ethanol, 2-(2-aminoethylamino)ethanol, 3-amino-1-propanol, 3-(dimethylamino)-1-propanol, and 1-amino-2-propanol, and are preferably monoethanolamine, diethanolamine, or 2-(2-aminoethoxy)ethanol.

[0019] In one embodiment, the content of (F) alkanolamine is 1 to 20% by weight based on the total weight of the composition. quality That is, in one embodiment, the composition of the present invention further comprises (F) an alkanolamine, and the content thereof is 1 to 20% by weight based on the total weight of the composition. quality %, preferably 5 to 20 quality %, 10-20 quality %, 15-20 quality %.

[0020] In some embodiments, the composition of the present invention further comprises an antioxidant. Examples of antioxidants include benzotriazole (BTA), adenine, 4-carboxybenzotriazole, 5-carboxybenzotriazole, 5-methylbenzotriazole, and 5-amino-1H-tetrazole. However, 4-carboxybenzotriazole (4-CBTA) and 5-carboxybenzotriazole (5-CBTA) are particularly preferred because they leave less organic residue from the antioxidant after cleaning. Therefore, in some embodiments, the composition of the present invention further comprises at least one selected from the group consisting of (G)BTA, adenine, 4-carboxybenzotriazole, and 5-carboxybenzotriazole, preferably 4-carboxybenzotriazole or 5-carboxybenzotriazole. In one embodiment, the total content of (G)BTA, adenine, 4-carboxybenzotriazole, or 5-carboxybenzotriazole is 0.05 to 1.00% by mass relative to the total mass of the composition.

[0021] In some embodiments, the compositions of the present invention contain an aprotic polar solvent in an amount of 35 quality % or less, preferably 25 quality % or less, more preferably 15 quality Most preferably, the compositions of the present invention are free of aprotic polar solvents. Aprotic polar solvents are, for example, dimethyl sulfoxide, N-methylpyrrolidone, sulfolane, 1,3-dimethyl-2-imidazolidinone, etc. Preferably, the composition of the present invention does not contain dimethyl sulfoxide or N-methylpyrrolidone.

[0022] From the viewpoint of suppressing device defects due to remaining metal residues, in one embodiment, the composition of the present invention preferably does not contain sodium hydroxide or potassium hydroxide. In some embodiments, the compositions of the present invention do not contain triazine compounds, such as 6-phenyl-2,4-diamino-1,3,5-triazine or 6-methyl-2,4-diamino-1,3,5-triazine.

[0023] The composition of the present invention may optionally contain a surfactant, for example. Examples of surfactants that can be used include polyether-modified silicones, sulfonic acid surfactants, phosphate ester surfactants, quaternary ammonium surfactants, polyoxyethylene alkyl ethers, and acetylene surfactants. The surfactant may be contained in an amount of, for example, 0.05 to 2% by mass relative to the total mass of the composition.

[0024] The photoresist stripping composition of the present invention is a composition for removing photoresist applied to a substrate having metal wiring. In the Cu bump formation process, a photoresist is applied to a substrate, and then resist patterning is performed by exposure and development. The resist openings are filled with Cu plating, and the resist is then stripped to form Cu bumps. The photoresist stripping composition of the present invention can be used in this process to strip the photoresist by a wet process. In addition, in the Cu wiring formation process by etching, after a Cu film is formed on a substrate, a photoresist is applied, and resist patterning is performed by exposure and development. After Cu etching is performed, the remaining photoresist that was layered on the Cu wiring can be peeled off using a wet process.

[0025] In one embodiment, the present invention also relates to a method for stripping photoresist, which comprises contacting a semiconductor substrate containing photoresist or photoresist residue with a composition of the present invention to remove the photoresist or photoresist residue. The photoresist-containing substrate refers to, for example, a photoresist applied onto a substrate having metal wiring such as Cu and Al formed in the Cu bump forming process or wiring forming process. The photoresist residue is the photoresist remaining after a photoresist removal process prior to contact with the composition of the present invention. Therefore, examples of substrates containing photoresist residue include substrates on which resist remains after rough removal (ashing) of the resist with oxygen plasma.

[0026] In some embodiments, a method for stripping photoresist includes the steps of: (A) providing a semiconductor substrate having a photoresist coating; (B) exposing the semiconductor substrate having the photoresist coating to a stripping composition of the present invention to remove the photoresist; (C) rinsing the stripper composition with water or IPA; and (D) drying. The semiconductor substrate is not particularly limited, but is usually made of silicon, silicon oxide, silicon carbide, titanium oxide, aluminum oxide, gallium oxide, gallium nitride, indium phosphide, gallium arsenide, or the like. Metals and metal alloys for the wiring materials, contact materials, and electrode materials constituting the substrate are not limited, but include copper, aluminum, aluminum alloyed with copper, aluminum alloyed with silicon, titanium, tungsten, cobalt, ruthenium, nickel, chromium, molybdenum, palladium, gold, silver, indium tin oxide, IGZO, and the like.

[0027] In some embodiments, the stripping composition may be used at a temperature range of about 25 to about 80° C. In some embodiments, the stripping composition may be used at a temperature range of about 40 to about 80° C. In some embodiments, the stripping composition may be used at a temperature range of about 50 to about 80° C. The stripping time may vary depending on the type of resist, the substrate structure, the stripping device, etc. When stripping Cu bump resist in a batch process, the preferred time range is usually about 5 to 30 minutes. [Example]

[0028] The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The following solvents and reagents were used: DMSO (dimethyl sulfoxide); manufactured by Kanto Chemical Co., Ltd. BDG (diethylene glycol monobutyl ether); manufactured by Kanto Chemical Co., Ltd. NMP (N-methylpyrrolidinone); manufactured by Kanto Chemical Co., Ltd. BnOH (benzyl alcohol); manufactured by Kanto Chemical Co., Ltd. GBL (gamma-butyrolactone); manufactured by Kanto Chemical Co., Ltd. HEP (1-(2-hydroxyethyl)-2-pyrrolidone); manufactured by Tokyo Chemical Industry Co., Ltd. THFA (tetrahydrofurfuryl alcohol); manufactured by Kanto Chemical Co., Ltd. PhDG (diethylene glycol monophenyl ether); manufactured by Tokyo Chemical Industry Co., Ltd. BnDG (diethylene glycol monobenzyl ether); manufactured by Kanto Chemical Co., Ltd. EDG (Diethylene glycol monoethyl ether); manufactured by Kanto Chemical Co., Ltd. Glycerin; manufactured by Kanto Chemical Co., Ltd. EG (ethylene glycol); manufactured by Kanto Chemical Co., Ltd. AEE (2-(2-aminoethoxy)ethanol); manufactured by Kanto Chemical Co., Ltd. MEA (monoethanolamine); manufactured by Kanto Chemical Co., Ltd. DEA (diethanolamine); manufactured by Kanto Chemical Co., Ltd. 5-CBTA (5-carboxybenzotriazole); manufactured by Tokyo Chemical Industry Co., Ltd.

[0029] Example 1 [Evaluation of wettability] In order to select a solvent that is effective for ultrasonic processing, the contact angle between copper and various solvents was evaluated. It can be inferred that the smaller the contact angle, the higher the wettability to copper and the better the stripping ability. Since copper exists in various oxidation states in the stripping solution, the contact angle was measured for three copper films: CuO, Cu2O, and Cu. In addition, assuming stripping on an aluminum film, the contact angle was also measured for an AlCu film. Measurements were performed at 25°C by dropping 1 μL of solvent onto the metal film and waiting 60 seconds.

[0030] [Table 1] (evaluation) CuO: Contact angle less than 20° = O, 20° or more = X Cu2O: Contact angle less than 20° = O, 20° or more = × Cu: Contact angle less than 10° = O, 10° or more = X AlCu: Contact angle less than 10° = Good, 10° or more = Bad DMSO: dimethyl sulfoxide, BDG: diethylene glycol monobutyl ether, NMP: N-methylpyrrolidone, BnOH: benzyl alcohol, GBL: γ-butyrolactone, HEP: 1-(2-hydroxyethyl)-2-pyrrolidone, THFA: tetrahydrofurfuryl alcohol, PhDG: diethylene glycol monophenyl ether, BnOH: diethylene glycol monobenzyl ether, EDG: diethylene glycol monoethyl ether

[0031] The smaller the contact angle, the higher the wettability with the metal film. EDG showed high wettability with all films, followed by DMSO, NMP, and GBL, which showed relatively good wettability.

[0032] Examples 2 to 9, Comparative Examples 1 to 13 A stripping solution was prepared using the solvent whose wettability was evaluated in Example 1, and its stripping ability and metal damage were evaluated.

[0033] [Removability evaluation] To evaluate strippability, an alkaline developing negative resist was applied to a copper sputtered film, patterned, and then copper bumps were formed on the Si substrate by copper plating. The stripping process was performed by immersing the substrate in a stripping solution at 65°C for 10 minutes while applying ultrasonic waves of 110 W and 40 kHz. After immersion in the stripping solution, the substrate was rinsed with water overflow for 1 minute and then dried with nitrogen blow. Strippability was evaluated by observing the dried substrate with an optical microscope. (evaluation) ○: Good peelability (no resist residue) △: Generally good peelability (slight resist residue) ×: Insufficient peelability (resist residue remains)

[0034] [Evaluation of Cu damage] To evaluate Cu damage, a Si substrate with a 100 nm sputtered Cu film was used. The substrate was immersed in a stripping solution at 65°C for 10 minutes while applying 110 W, 40 kHz ultrasonic waves. After rinsing with water overflow for 1 minute, the substrate was dried by nitrogen blowing. The copper film thickness on the dried substrate was analyzed using a wavelength-dispersive X-ray fluorescence spectrometer, and the etching rate (nm / min) was calculated. (evaluation) ◎: Cu etching rate is less than 1.0 nm / min ○: Cu etching rate is 1.0 to less than 1.5 nm / min △: Cu etching rate is 1.5 to less than 5.0 nm / min ×: Cu etching rate is 5.0 nm / min or more

[0035] [AlCu damage evaluation] To evaluate AlCu damage, a Si substrate with a 100 nm AlCu sputtered film was used. The substrate was immersed in a stripping solution at 65°C for 10 minutes while applying 110 W, 40 kHz ultrasound, followed by a 1 minute water overflow rinse and drying with nitrogen blow. The AlCu film thickness on the dried substrate was analyzed using a wavelength dispersive X-ray fluorescence spectrometer, and the etching rate (nm / min) was calculated. (evaluation) ◎: AlCu etching rate is less than 1.0 nm / min ○: AlCu etching rate is 1.0 to less than 1.5 nm / min △: AlCu etching rate is 1.5 to less than 5.0 nm / min ×: AlCu etching rate is 5.0 nm / min or more

[0036] [Table 2] TMAH: tetramethylammonium hydroxide

[0037] There was a tendency for good stripping properties to be obtained with chemical solution compositions using solvents with high Cu wettability. The EDG solvent composition (Example 2), which had the best wettability, exhibited high stripping properties and good metal damage suppression performance equivalent to the NMP composition, demonstrating sufficient performance as a replacement for NMP. The DMSO composition (Comparative Example 1) had high stripping properties but resulted in significant Cu damage.

[0038] [Table 3]

[0039] A water concentration of about 10% in the EDG solvent composition allows for good stripping properties and metal damage suppression (Example 3). Furthermore, the addition of ethylene glycol allows for even greater metal damage suppression and improved stripping properties (Examples 4 and 5). TMAH and glycerin are essential components because compositions that do not contain them cannot reduce stripping properties or suppress metal damage (Comparative Examples 11 and 12). Furthermore, a water concentration of 20% or higher reduces stripping properties and causes AlCu corrosion, so a water concentration of less than 20% is desirable (Comparative Example 13).

[0040] [Table 4] AEE: 2-(2-aminoethoxy)ethanol, MEA: 2-aminoethanol; DEA: Diethanolamine

[0041] Even with the chemical composition containing amine, good stripping properties and metal damage suppression performance were obtained (Examples 6 to 9). The amine-containing composition increases the alkaline component, which is expected to improve stripping properties and extend the life of the solution.

[0042] Examples 10 to 11, Comparative Examples 14 to 16 The amount of copper oxidation during the stripping solution process was evaluated.

[0043] [Evaluation of Cu oxidation inhibition] The amount of Cu oxidation during the stripping process was evaluated using a Si substrate with a 100 nm Cu sputtered film deposited. After immersion in the stripping solution at 65°C for 10 minutes while applying 110 W and 40 kHz ultrasound, the substrate was rinsed with water overflow for 30 minutes and then dried by nitrogen blowing. The atomic ratio of oxygen atoms to copper atoms (oxygen atoms / copper atoms) of the dried Cu film was determined using X-ray photoelectron spectroscopy (XPS). The increase in the atomic ratio of the Cu film before and after the stripping process was calculated to provide a measure of the increase in the amount of copper oxide.

[0044] [Removability evaluation] Resist strippability was evaluated in the same manner as in Examples 2 to 9 and Comparative Examples 1 to 13.

[0045] [Table 5]

[0046] In the composition using DMSO solvent instead of EDG solvent (Comparative Example 14), the generation of copper oxide was significantly promoted, which may cause device failure when used in an actual process. In the composition using EDG solvent (Example 10), the generation of copper oxide was reduced to about half of that in the DMSO solvent composition (Comparative Example 14).

[0047] The addition of an antioxidant further suppressed the generation of copper oxide (Example 11). Furthermore, if a large amount of organic matter remains on the Cu surface, it can cause poor device characteristics. However, when CBTA was used as the antioxidant, no organic matter derived from the antioxidant remained on the Cu surface after rinsing. Examples 12-13 The stripping liquid compositions used in Examples 2 and 4 were evaluated for stripping ability and metal damage under the condition that ultrasonic waves were not applied.

[0048] [Removability evaluation] To evaluate strippability, an alkaline development negative resist was applied to a copper sputtered film, patterned, and then copper bumps were formed on a Si substrate by copper plating. The stripping process was performed by immersing the substrate in a stripping solution at 65°C for 30 minutes while stirring at 300 rpm. After immersion in the stripping solution, the substrate was rinsed with water overflow for 1 minute and then dried with nitrogen blow. Strippability was evaluated by observing the dried substrate with an optical microscope. (evaluation) ○: Good peelability (no resist residue) △: Generally good peelability (slight resist residue) ×: Insufficient peelability (resist residue remains)

[0049] [Evaluation of Cu damage] To evaluate Cu damage, a Si substrate with a 100 nm Cu sputtered film was used. The substrate was immersed in the stripper solution at 65°C for 10 minutes while stirring at 300 rpm, followed by a 1 minute water overflow rinse and drying with nitrogen blow. The copper film thickness on the dried substrate was analyzed using a wavelength dispersive X-ray fluorescence spectrometer, and the etching rate (nm / min) was calculated. (evaluation) ◎: Cu etching rate is less than 1.0 nm / min ○: Cu etching rate is 1.0 to less than 1.5 nm / min △: Cu etching rate is 1.5 to less than 5.0 nm / min ×: Cu etching rate is 5.0 nm / min or more

[0050] [AlCu damage evaluation] To evaluate AlCu damage, a Si substrate with a 100 nm AlCu sputtered film was used. The substrate was immersed in the stripper solution at 65°C for 10 minutes while stirring at 300 rpm, followed by a 1 minute water overflow rinse and drying with nitrogen blow. The AlCu film thickness on the dried substrate was analyzed using a wavelength dispersive X-ray fluorescence spectrometer, and the etching rate (nm / min) was calculated. (evaluation) ◎: AlCu etching rate is less than 1.0 nm / min ○: AlCu etching rate is 1.0 to less than 1.5 nm / min △: AlCu etching rate is 1.5 to less than 5.0 nm / min ×: AlCu etching rate is 5.0 nm / min or more

[0051] [Table 6] Although it takes longer to complete the stripping process than when ultrasonic waves are applied, it is possible to perform the stripping process while suppressing metal damage. Therefore, even in the absence of an ultrasonic wave emitting device, the stripping composition of the present invention exhibits excellent stripping properties while suppressing metal corrosion and excessive metal oxidation during the stripping process.

Claims

1. 1. A photoresist stripping composition comprising: The composition comprises: (A) a quaternary ammonium hydroxide, (B) diethylene glycol monoethyl ether, (C) glycerin, (D) water, and (F) an alkanolamine; The composition, wherein the content of (A) is 0.5 to 5% by mass, based on the total mass of the composition, the content of (B) is 50 to 95% by mass, based on the total mass of the composition, the content of (C) is 0.5 to 20% by mass, based on the total mass of the composition, the content of (D) is less than 20% by mass, based on the total mass of the composition, and the content of (F) is 1 to 20% by mass, based on the total mass of the composition.

2. The composition of claim 1 , wherein the composition does not contain hydroxylamine or a hydroxylamine salt.

3. The composition according to claim 1 or 2, wherein the content of (D) water is 5% by mass or less based on the total mass of the composition.

4. The composition according to any one of claims 1 to 3, further comprising (E) ethylene glycol, the content of which is 1 to 10 mass% relative to the total mass of the composition.

5. The composition according to any one of claims 1 to 4, wherein the alkanolamine (F) is monoethanolamine, diethanolamine, or 2-(2-aminoethoxy)ethanol.

6. The composition according to any one of claims 1 to 5, further comprising (G) at least one selected from the group consisting of 4-carboxybenzotriazole and 5-carboxybenzotriazole, and the total content of (G) is 0.05 to 1.00 mass% based on the total mass of the composition.

7. The composition according to any one of claims 1 to 6, wherein the (A) quaternary ammonium hydroxide is at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline hydroxide, and ethyltrimethylammonium hydroxide.

8. The composition of any one of claims 1 to 7, wherein the composition does not contain dimethyl sulfoxide or N-methylpyrrolidone.

9. The composition of any one of claims 1 to 8, wherein the composition does not contain sodium hydroxide or potassium hydroxide.

10. The composition of any one of claims 1 to 9, wherein the composition does not contain a triazine compound.

11. A method for stripping a photoresist, comprising contacting a photoresist applied to a substrate having metal wiring or a semiconductor substrate containing a photoresist residue with the composition according to any one of claims 1 to 10, thereby removing the photoresist.

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