Photoresist stripping composition

Abstract

To provide a photoresist stripping composition which exhibits a high stripping property even with respect to a cured resist, exhibits a small decrease in stripping property at the time of water evaporation even in a composition containing a small amount of water, and can suppress corrosion of substrate constituent metals such as Cu, Al, and Si which are in contact with a liquid.SOLUTION: Provided is a photoresist stripping composition, containing (A) a quaternary ammonium hydroxide, (B) a sugar alcohol, (C) an amine, (D) water, (E) DMSO, and (F) ethylene glycol, wherein the content of (D) water is 1.0 to 10 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] Semiconductor integrated circuits are manufactured using photolithography, which forms metal wiring patterns made of copper or other materials on silicon or glass substrates. Photolithography involves the following steps: (1) applying photoresist to a semiconductor substrate or metal film, (2) transferring the wiring pattern by exposure and development, (3) forming and processing the wiring by etching or plating, and (4) removing the photoresist. Since photoresist is an organic film, a stripper with a low water content or a non-aqueous system is desirable from the viewpoint of resist solubility. However, in the case of a stripper with a low water content, water evaporates during heat treatment, causing the balance of the stripper composition to be lost, resulting in a problem of reduced photoresist stripping ability. Furthermore, a stripper containing even a small amount of water may cause damage to silicon and the like. Therefore, there is a demand for a stripper that reduces the reduction in stripping ability during water evaporation and causes less damage to metal wiring, Si, and other substrates. Furthermore, to efficiently strip resist, it is necessary to fragment the polymer chains and improve their solubility and dispersibility in the solution. Fragmentation is achieved by hydrolyzing the ester bonds in the polymer, so stripping solutions should preferably contain strong bases such as amines or ammonium hydroxides. However, stripping solutions containing strong bases in aqueous compositions can damage silicon and aluminum. Therefore, there is a demand for strippers that are strong basic yet cause minimal damage to silicon and aluminum, and that have low water content or are non-aqueous. Strippers are used to remove unnecessary photoresist films after etching or plating processes, but the photoresist hardens during the etching or plating process, making it difficult to strip. Therefore, there is a demand for strippers that can remove hardened resist.

[0003] Patent Document 1 discloses a composition in which THAH, EG, and DMSO are mixed, and a water-free composition in which THAH, PG, and DMSO are mixed. Patent Document 2 describes a photoresist stripping composition that is substantially water-free and useful for stripping photoresist after an ion implantation step, such as a composition containing a mixture of THAH, EG, and DMSO.

[0004] Patent Document 3 describes a photoresist stripper solution containing DMSO, TMAH, an alkanolamine, a corrosion inhibitor, and water. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2006-317714 [Patent Document 2] Patent Publication No. 2013-500503 [Patent Document 3] Patent Publication No. 2019-113848 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the above-mentioned conventional photoresist removers have had problems such as insufficient stripping ability for excessively hardened photoresist, damage to metal wiring and substrates such as Si, reduced stripping ability upon evaporation when water is present, and high raw material and manufacturing costs. In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a stripper that has high stripping properties even for cured resist, that exhibits little deterioration in stripping properties when water evaporates even when the composition contains a small amount of water, and that causes little damage to metal wiring and substrates such as Si. [Means for solving the problem]

[0007] As described above, a non-aqueous stripper is preferable for high resist solubility, but the quaternary ammonium salts frequently used in strippers are usually manufactured and sold as aqueous solutions, so water must be removed to produce a non-aqueous stripper. One method for this purpose is to use an organic solvent solution of a quaternary ammonium salt, but this has the disadvantage of being more expensive than an aqueous solution, and evaporating water from an aqueous solution of a quaternary ammonium salt requires time and effort during production. In the course of investigations aimed at solving the above-mentioned problems, the present inventors have found that a photoresist stripping composition comprising (A) a quaternary ammonium hydroxide, (B) a sugar alcohol, (C) an amine, (D) water, (E) DMSO, and (F) ethylene glycol, in which the content of (D) water is 1.0 to 10 mass % based on the total mass of the composition, exhibits little deterioration in stripping properties when water evaporates, even in a composition containing a small amount of water, and causes little damage to metal wiring and substrates such as Si, thereby completing the present invention.

[0008] That is, the present invention relates to the following. [1] A photoresist stripping composition comprising: (A) a quaternary ammonium hydroxide; (B) a sugar alcohol; (C) an amine; (D) water; (E) DMSO; and (F) ethylene glycol; wherein the content of (D) water is 1.0 to 10% by mass based on the total mass of the composition. [2] The composition according to [1], wherein the content of (A) is 1.0 to 10 mass% relative to the total mass of the composition, the content of (B) is 0.1 to 20 mass% relative to the total mass of the composition, the content of (C) is 1.0 to 20 mass% relative to the total mass of the composition, the content of (D) is 1.0 to 10 mass% relative to the total mass of the composition, the content of (E) is 20 to 90 mass% relative to the total mass of the composition, and the content of (F) is 1 to 10 mass% relative to the total mass of the composition. [3] The composition according to [1] or [2], wherein (C) the amine is at least one compound selected from monoethanolamine, diethanolamine, triethanolamine, N-methylaminoethanol, 2-(2-aminoethoxy)ethanol, 2-[2-(dimethylamino)ethoxy]ethanol, and diisopropanolamine, or a mixture thereof. [4] The composition according to any one of [1] to [3], wherein (C) the amine is 2-(2-aminoethoxy)ethanol or 2-[2-(dimethylamino)ethoxy]ethanol. [5] The composition according to any one of [1] to [4], which does not contain a compound having a boiling point of 70°C or less at 1 atm. [6] (A) The composition according to any one of [1] to [5], wherein the quaternary ammonium hydroxide is a compound represented by the following general formula or a mixture thereof, and the content thereof is 1 to 5%: (R 1 , R 2 , R 3 , R 4 are each independently an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms.) [ka] [7] (B) The composition according to any one of [1] to [6], wherein the sugar alcohol is at least one compound selected from sorbitol, xylitol, erythritol, mannitol, and glycerin, or a mixture thereof. [8] 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 [7], thereby removing the photoresist. [Effects of the Invention]

[0009] The composition of the present invention, despite being a strongly basic, aqueous composition, can achieve high stripping performance without damaging metal wiring or substrates such as Si, making it applicable to highly difficult processes that require selectivity with metals. Furthermore, because it achieves high stripping performance while simultaneously protecting Si, Al, Cu, etc. from corrosion, it can be applied to even more difficult processes. Furthermore, because there is no decrease in stripping performance due to water evaporation, it can be used for long periods of time, reducing the number of times the solution needs to be changed. Furthermore, compared to conventional non-aqueous stripping solutions containing strong bases, the production cost is lower. This allows for cost reductions and a reduced environmental impact. In particular, when EG was used as an additive in addition to DMSO, strippability was significantly improved compared to when 1,3-PG, etc. was used as an additive. Furthermore, when EG was used as an additive, silicon corrosion protection was significantly improved compared to when 1,3-PG, etc. was used as an additive. [Brief explanation of the drawings]

[0010] [Figure 1] Figure 1 shows the results of evaluating the molar conductivity at 25°C of a composition containing 1% TMAH, 50% to 50% H2O3, and a solvent (the balance). The molar conductivity is positively correlated with the degree of ionization of TMAH. The higher the degree of ionization of TMAH, the more basic the solution is, so the tendency regarding the strength of basicity can be obtained from the molar conductivity. [Figure 2] Figure 2 shows the results of evaluating the molar conductivity at 25°C for compositions containing 1% TMAH, 50% to 50% H2O3, and the remainder DMSO / cosolvent (1:1 mol). The molar conductivity is positively correlated with the degree of ionization of TMAH. The higher the degree of ionization of TMAH, the more basic the solution, so the molar conductivity can provide a trend in the strength of basicity. 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 is a photoresist stripping composition comprising (A) a quaternary ammonium hydroxide, (B) a sugar alcohol, (C) an amine, (D) water, (E) DMSO, and (F) ethylene glycol, and the content of (D) water is 1.0 to 10 mass% based on the total mass of the composition. The low water content results in little deterioration in stripping properties upon water evaporation, and causes little damage to metal wiring and Si. 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. (A) The quaternary ammonium hydroxide is a compound represented by the following general formula or a mixture thereof: [ka] (R 1 , R 2 , R 3 , R 4 each independently represents an alkyl group or a hydroxyalkyl group.

[0013] The quaternary ammonium hydroxide is a compound represented by the following general formula or a mixture thereof: [ka] (R 1 , R 2 , R 3 , R 4 are each independently an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms.)

[0014] Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, choline hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, and monomethyltris(2-hydroxyethyl)ammonium hydroxide. From the viewpoints of solubility, cost, and the like, preferred is one or more selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, choline hydroxide, and ethyltrimethylammonium hydroxide. Tetramethylammonium hydroxide is more preferred. In one embodiment, the quaternary ammonium hydroxide includes tetramethylammonium hydroxide. In one embodiment, the quaternary ammonium hydroxide includes tetramethylammonium hydroxide in an amount of 1% by mass or more based on the total amount of the quaternary ammonium hydroxide. The content of (A) quaternary ammonium hydroxide is not particularly limited, but is preferably 1.0 to 10 mass% relative to the total mass of the composition, more preferably 1.0% to 5.0%, and even more preferably 1.0% to 3.0%, from the viewpoint of suppressing metal damage and suppressing water content.

[0015] (B) Sugar alcohol is a component that serves as an aluminum corrosion inhibitor. Examples of sugar alcohols include sorbitol and glycerin. Preferably, the sugar alcohol is at least one compound selected from the group consisting of sorbitol, xylitol, erythritol, mannitol, and glycerin, or a mixture thereof. The sugar alcohol may be in the d-form, l-form, or racemic form. The content of (B) sugar alcohol is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, relative to the total mass of the composition.

[0016] (C) When amine is mixed, the hydroxy ion (OH) of the ammonium salt -The resist can be decomposed using two active species: the hydroxyl group (-NH2) and the amino group (-NH2), resulting in higher strippability. The content of the (C) amine is not particularly limited, but is preferably 1.0 to 20% by mass, more preferably 1.0 to 15% by mass, relative to the total mass of the composition.

[0017] The amine is preferably an amino alcohol, more preferably at least one compound selected from monoethanolamine, diethanolamine, triethanolamine, N-methylaminoethanol, 2-(2-aminoethoxy)ethanol, 2-[2-(dimethylamino)ethoxy]ethanol, and diisopropanolamine, or a mixture thereof. From the viewpoints of high stripping ability and particularly small damage to Cu, the amine is more preferably 2-(2-aminoethoxy)ethanol or 2-[2-(dimethylamino)ethoxy]ethanol.

[0018] The content of (D) water is 1.0 to 10% by mass relative to the total mass of the composition, and from the viewpoint of resist solubility, etc., it is preferably 1.0 to 6.0% by mass.

[0019] (E) Dimethyl sulfoxide (DMSO) is a component that serves as a solvent. The content of (E) DMSO is not particularly limited, but is preferably 20 to 90% by mass, more preferably 60 to 90% by mass, and even more preferably 60 to 85% by mass, relative to the total mass of the composition. The present inventors have found that when DMSO is mixed with alkylammonium hydroxide, it forms a highly basic solution compared to other commonly used solvents such as N-methyl-2-pyrrolidone (NMP) and diethylene glycol monoethyl ether (EDG), and that high basicity can be achieved with a low concentration of water. Figure 1 shows the molar conductivity of TMAH versus the water concentration of each solvent. The molar conductivity correlates positively with the degree of ionization of TMAH. The higher the degree of ionization of TMAH, the more basic the solution; therefore, the tendency of basicity can be obtained from the molar conductivity. Compared to other solvents, TMAH exhibits a high molar conductivity at low water concentrations in DMSO. Therefore, TMAH is considered to be highly basic at low water concentrations in DMSO, making it suitable for use in combination with small amounts of water. Acetone also showed good results, but its low flash point and boiling point make it unsuitable as a stripper.

[0020] The composition of the present invention contains DMSO as a solvent, but DMSO can also be used in combination with other solvents. Preferred solvents include glycol ether solvents and amide solvents, from the viewpoint of maintaining or improving peeling properties. As shown in Figure 1, when glycol ether-based solvents or amide-based solvents are used alone, the molar electrical conductivity of the TMAH solution is low, resulting in poor stripping properties. Figure 2 shows the molar electrical conductivity of the TMAH solution versus water concentration when the solvents shown in Figure 1 are mixed with DMSO. By mixing with DMSO, the molar electrical conductivity increases in the range of water molar fractions of 0.5 or less compared to the case of glycol ether-based solvents or amide-based solvents alone (Figure 1). This suggests that the basicity of the TMAH solution is enhanced at low water concentrations. Therefore, it is believed that glycol ether-based and amide-based solvents, when mixed with DMSO, become effective stripping solvents. Examples of glycol ether solvents include diethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. Preferred are diethylene glycol monoethyl ether and propylene glycol monomethyl ether. Examples of amide solvents include N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, 1-(2-hydroxyethyl)-2-pyrrolidone, etc. Preferred are N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc.

[0021] The composition of the present invention contains (F) ethylene glycol. The content of (F) ethylene glycol is not limited, but is preferably 1.0 to 10 mass % and more preferably 5.0 to 10 mass % relative to the total mass of the composition.

[0022] In one embodiment, the composition of the present invention does not contain a compound having a boiling point of 70° C. or lower at 1 atm. Examples of compounds having a boiling point of 70° C. or lower at 1 atm include acetone and methanol.

[0023] The composition of the present invention may contain optional components such as a surfactant and a Cu corrosion inhibitor. Examples of surfactants that can be used include polyoxyethylene alkyl ether carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl ethers, tetraalkylammonium halide salts, and alkyl betaines. The surfactant may be contained in an amount of, for example, 0.01 to 3.0% by mass relative to the total mass of the composition. Examples of Cu corrosion inhibitors that can be used include imidazole, benzotriazole, and adenine. The Cu corrosion inhibitor may be contained in an amount of, for example, 0.01 to 3.0 mass % relative to the total mass of the composition.

[0024] Even when the composition of the present invention contains 1.0 to 10% by mass of water, it maintains good strippability even after the water evaporates. While the reason for this is not entirely clear, it is believed that ethylene glycol has the effect of swelling the resist, which is considered to be one of the functions of water. Ethylene glycol has a higher boiling point than water and is less likely to evaporate. Therefore, it is believed that good strippability is maintained as long as ethylene glycol remains even after the water evaporates. Adding too much ethylene glycol reduces the strippability before water evaporation, while adding too little reduces the strippability after water evaporation. Therefore, it is desirable to add ethylene glycol at a mass % similar to the water concentration. Furthermore, it is believed that ethylene glycol not only contributes to maintaining strippability but also improves strippability and further reduces damage to metal wiring and Si.

[0025] The composition of the present invention is a composition for removing a 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.

[0026] 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.

[0027] In some embodiments, the photoresist stripping method includes: (A) providing a semiconductor substrate having a photoresist coating; (B) exposing the semiconductor substrate having the photoresist coating to the stripping composition of the present invention to remove the photoresist; (C) washing the semiconductor substrate from which the photoresist has been removed with ultrapure water, or 2-propanol and ultrapure water, to remove the stripper solution composition from the substrate; 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, cobalt, tungsten, ruthenium, nickel, chromium, molybdenum, palladium, gold, silver, indium tin oxide, IGZO, and the like.

[0028] In some embodiments, the stripping composition may be used at a temperature range of about 25 to about 90°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 70°C. The stripping time may vary depending on the resist type, thermal history, etc. When stripping is performed in a batch process, the preferred time range is usually about 5 to 30 minutes. [Example]

[0029] 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. MEA (monoethanolamine); manufactured by Kanto Chemical Co., Ltd. TMAH (tetramethylammonium hydroxide); manufactured by Kanto Chemical Co., Ltd. D-Sor (D-sorbitol); manufactured by Kanto Chemical Co., Ltd. EG (ethylene glycol); manufactured by Kanto Chemical Co., Ltd. EDG (Diethylene glycol monoethyl ether); manufactured by Kanto Chemical Co., Ltd. DMI (1,3-dimethyl-2-imidazolidinone); manufactured by Kanto Chemical Co., Ltd. NMP (N-methyl-2-pyrrolidone); manufactured by Kanto Chemical Co., Ltd. DEA (diethanolamine); manufactured by Kanto Chemical Co., Ltd. TEA (triethanolamine); manufactured by Kanto Chemical Co., Ltd. MeMEA (N-methylmonoethanolamine); manufactured by Kanto Chemical Co., Ltd. AEE (2-(2-aminoethoxy)ethanol); manufactured by Tokyo Chemical Industry Co., Ltd. DIPA (diisopropanolamine); manufactured by Tokyo Chemical Industry Co., Ltd. THFA (tetrahydrofurfuryl alcohol); manufactured by Kanto Chemical Co., Ltd. TEAH (tetraethylammonium hydroxide); manufactured by Tokyo Chemical Industry Co., Ltd. TBAH (tetrabutylammonium hydroxide); manufactured by Tokyo Chemical Industry Co., Ltd. 1,2-PG (1,2-propanediol); manufactured by Kanto Chemical Co., Ltd. 1,3-PG (1,3-propanediol); manufactured by Tokyo Chemical Industry Co., Ltd. Dimethyl AEE (2-[2-(dimethylamino)ethoxy]ethanol); manufactured by Tokyo Chemical Industry Co., Ltd.

[0030] The stripping compositions were prepared and evaluated as follows.

[0031] Preparation of the Stripping Composition The components were blended at the concentrations shown in the table below to prepare stripping compositions.

[0032] [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 a Si substrate by copper plating. The stripping process was performed by immersing the substrate in a stripping solution at 60°C for 10 minutes. 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.

[0033] The peelability was evaluated on a three-point scale, with ◯, △, and × representing the following meanings. ○: Good peelability (no resist residue) △: Generally good peelability (slight resist residue) ×: Insufficient peelability (resist residue remains)

[0034] [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 60°C for 10 minutes, then rinsed with water overflow for 1 minute and dried by 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.

[0035] The AlCu damage evaluation is divided into two stages, with ○ and × representing the following meanings. ◯: AlCu etching rate ≦ 0.5 nm / min ×: AlCu etching rate > 0.5 nm / min

[0036] [Table 1] The peelability was improved by adding EG as an additive (Example 1, Comparative Example 1). When EDG was used alone as a solvent, the peelability was poor (Comparative Example 2), but good peelability was shown when mixed with DMSO (Example 2). In addition, the solvents that showed good peelability when mixed with DMSO were amide solvents such as DMI and NMP (Examples 2, 3, 4). Among amines, MEA, DEA, TEA, MeMEA, AEE, and DIPA showed relatively good peelability. Among them, AEE had almost the same excellent peelability as MEA (Examples 1, 5, 6, 7, 8, 9). As ammonium salts, in addition to TMAH, TEAH, TBAH, and choline also showed good peelability (Examples 10, 11, 12). As Al corrosion inhibitors other than D-sorbitol, xylitol, D-mannitol, meso-erythritol, glycerin, etc. were effective (Examples 13, 14, 15, 16). When EG was applied as an additive (Example 1), the peelability was greatly improved compared to the case when 1,3-PG was applied (Comparative Example 3).

[0037] [Evaluation of Cu damage] For the evaluation of Cu damage, a Si substrate with a 100-nm Cu sputter film formed thereon was used. After immersing the substrate in the stripping solution at 60 °C for 10 minutes, an overflow rinse with water was performed for 1 minute, and the substrate was dried by nitrogen blowing. The copper film thickness of the dried substrate was analyzed using a wavelength-dispersive fluorescent X-ray device, and the etching rate (nm / min) was calculated. (Evaluation) 〇: Cu etching rate ≤ 0.5 nm / min △: 0.5 nm / min < Cu etching rate ≤ 3.0 nm / min ×: Cu etching rate > 3.0 nm / min

[0038] [Table 2]

[0039] When using AEE or dimethyl AEE, it was possible to suppress Cu damage while maintaining peelability (Examples 17, 18). When using MEA, the peelability was good, and Cu damage suppression was also generally good (Example 19). Other than AEE and dimethyl AEE, Cu damage could also be suppressed with the DEA or TEA addition compositions, and the peelability was also generally good (Examples 20, 21). On the other hand, for the composition without amine addition, the Cu damage was small but the peelability was insufficient (Comparative Example 4).

[0040] [Evaluation of Si damage] For the evaluation of Si damage, an Si substrate was used. After immersing the substrate in a 0.5% HF aqueous solution for 2 minutes at room temperature, an overflow rinse with water was performed for 1 minute and the substrate was dried by nitrogen blowing. The mass of the dried substrate was measured with an analytical balance and taken as the mass before treatment. Then, the substrate was immersed in the stripping solution at 60°C for 1 hour, after which an overflow rinse with water was performed for 1 minute and the substrate was dried by nitrogen blowing. The mass of the dried substrate was measured with an analytical balance and taken as the mass after treatment. The etching rate (nm / min) was calculated from the mass change before and after treatment.

[0041] (Evaluation) 〇: Si etching rate ≤ 1.0 nm / min △: 1.0 nm / min < Si etching rate ≤ 3 nm / min ×: Si etching rate > 3.0 nm / min

[0042] [Table 3]

[0043] By adding EG, high corrosion resistance of Si was obtained (Examples 22, 23, Comparative Example 6). It was found that EG was capable of superior Si corrosion prevention compared to 1,3-PG (Example 22, Comparative Example 7).

[0044] [Removability evaluation when water evaporates] The prepared stripping solution was left open at 90°C for 30 minutes to 1 hour, and the stripping solution was used to evaporate 3 to 4% of the water, and the stripping properties were evaluated in the same manner.

[0045] [Table 4]

[0046] It was confirmed that the composition containing EG (Example 24) could suppress the decrease in stripping property after evaporation of water compared to the composition without EG (Comparative Example 8).It was also found that the addition of EG resulted in superior stripping property compared to the composition with 1,3-PG (Comparative Example 9).

Claims

1. 1. A photoresist stripping composition comprising: the composition comprises (A) a quaternary ammonium hydroxide, (B) a sugar alcohol, (C) an amino alcohol, (D) water, (E) DMSO, and (F) ethylene glycol; (D) A composition having a water content of 1.0 to 10% by mass relative to the total mass of the composition.

2. 2. The composition according to claim 1, wherein the content of (A) is 1.0 to 10% by mass, relative to the total mass of the composition, the content of (B) is 0.1 to 20% by mass, relative to the total mass of the composition, the content of (C) is 1.0 to 20% by mass, relative to the total mass of the composition, the content of (D) is 1.0 to 10% by mass, relative to the total mass of the composition, the content of (E) is 20 to 90% by mass, relative to the total mass of the composition, and the content of (F) is 1 to 10% by mass, relative to the total mass of the composition.

3. 3. The composition according to claim 1 or 2, wherein the amino alcohol (C) is at least one compound selected from monoethanolamine, diethanolamine, triethanolamine, N-methylaminoethanol, 2-(2-aminoethoxy)ethanol, 2-[2-(dimethylamino)ethoxy]ethanol, and diisopropanolamine, or a mixture thereof.

4. The composition according to any one of claims 1 to 3, wherein the amino alcohol (C) is 2-(2-aminoethoxy)ethanol or 2-[2-(dimethylamino)ethoxy]ethanol.

5. The composition according to any one of claims 1 to 4, which does not contain a compound having a boiling point of 70°C or lower at 1 atm.

6. The composition according to any one of claims 1 to 5, wherein (A) the quaternary ammonium hydroxide is a compound represented by the following general formula or a mixture thereof, and the content thereof is 1 to 5%: (R １ , R ２ , R ３ , R ４ each independently represents an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. 【Chemical 1】

7. 7. The composition according to claim 1, wherein the sugar alcohol (B) is at least one compound selected from the group consisting of sorbitol, xylitol, erythritol, mannitol, and glycerin, or a mixture thereof.

8. A method for stripping a photoresist, comprising contacting a photoresist applied to a substrate having metal wiring or a semiconductor substrate containing photoresist residue with the composition according to any one of claims 1 to 7, thereby removing the photoresist.

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