Treatment solution and method for using same

Abstract

Proposed is a treatment solution that has excellent photoresist releasability and excellent storage stability, particularly storage stability at low temperatures, and that is thus very highly practical. Provided is a treatment solution comprising (A) a quaternary ammonium salt represented by general formula (1), (B) an alkanolamine, and (C) a glycol-based solvent. (1): [NR1R2R3R4]+[OH]- In the formula, R1, R2, R3, and R4 may be the same or different from each other and are each a C1-6 alkyl group, a C7-10 arylalkyl group, or a C6-10 aryl group.

Description

Processing solution and method of use thereof

[0001] The present invention relates to a processing liquid that is used primarily in the manufacturing process of semiconductor devices, liquid crystal devices, and other display panel devices, and a method for using the same.

[0002] The manufacturing process of semiconductor devices such as integrated circuits and large-scale integrated circuits, and the manufacturing process of liquid crystal devices and other display panel devices includes various steps such as lithography, etching, ion implantation, stripping, polishing, etc. The lithography process includes the steps of forming a metal layer or an insulating layer by chemical vapor deposition, forming a uniform photoresist coating on the metal layer or insulating layer, performing necessary exposure and development to form a photoresist pattern, selectively etching a substrate having a metal layer or insulating layer using the photoresist pattern as a mask to form fine circuits, and removing one or more of the unnecessary photoresist layer, etching layer, etching residue, residual photoresist, and photoresist by-products from the substrate with a remover solution.

[0003] Photoresist removers composed of various organic liquids are used to remove unwanted photoresist layers, etching residues, residual photoresist, and photoresist by-products from substrates. In conventional techniques, photoresist removal solutions for removing unwanted photoresist layers often contain compositions containing polar solvents such as dimethyl sulfoxide and N-methyl-2-pyrrolidone. The various processing solutions used in these processes, such as prewet solutions, developer solutions, rinse solutions, removal solutions, and stripping solutions, are referred to herein as "processing solutions." Furthermore, processes typically include a process for treating unwanted organic matter using a processing solution after each process or before moving on to the next process.

[0004] In particular, further improvements are required for photoresist removal solutions used in the manufacturing process of semiconductor devices, methods for removing photoresist using the removal solutions, and methods for manufacturing semiconductor devices by removing photoresist using the removal solutions, as described below.

[0005] Semiconductor substrates and the like have electrode structures with fine wiring, and photoresists are used in the semiconductor manufacturing process. The electrode structures are manufactured, for example, by applying photoresist to a wiring material film or insulating film formed on a substrate, exposing and developing the photoresist to form a photoresist pattern, etching the wiring material film or insulating film formed on the substrate using this photoresist pattern as a mask to form wiring, and then removing the unnecessary photoresist with a photoresist remover. In addition to photoresist stripping performance, photoresist removers are required to cause minimal damage to the insulating film and wiring materials used, and to be storage stable enough to prevent solidification or precipitation even at low temperatures.

[0006] Patent Document 1 describes a resist stripping liquid composition containing an N-alkylalkanolamine and at least one selected from dimethyl sulfoxide and N-methyl-2-pyrrolidone. Patent Document 2 describes a photoresist stripping agent containing at least one selected from γ-butyrolactone, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, at least one selected from aminoalcohols, and water.

[0007] Japanese Patent Publication No. 8-87118 Japanese Patent Publication No. 7-69618

[0008] However, these known photoresist stripping compositions always have the problem of achieving both stripping performance and low damage to device constituent materials (hereinafter also referred to as substrates), and no compositions that are sufficiently effective in both areas have yet been developed. Furthermore, there is also the problem of storage stability. Even if sufficient stripping performance and low damage to substrates were achieved, a treatment solution with low storage stability would be impossible to put into practical use. Recently, there has been a demand for stability even at low temperatures of around -5°C, which is particularly expected during transportation.

[0009] The present invention proposes a highly practical processing liquid that has excellent photoresist stripping properties and excellent storage stability, particularly at low temperatures.

[0010] The present inventors have conducted extensive research to solve the above problems and have completed the present invention. Specifically, the present invention relates to the following 1) to 10): 1) A treatment liquid having (A) a quaternary ammonium salt represented by the following general formula (1), (B) an alkanolamine, and (C) a glycol-based solvent. [NR １ R ２ R ３ R ４ ] ＋ [OH] － ...(1) In the formula, R １ , R ２ , R ３ and R ４ may be the same or different and are an alkyl group having 1 to 6 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 2) The treatment liquid according to 1) above, wherein the quaternary ammonium salt (A) is tetramethylammonium hydroxide, tetraethylammonium hydroxide, or ethyltrimethylammonium hydroxide. 3) The treatment liquid according to 1) or 2) above, wherein the alkanolamine (B) is an N-alkylalkanolamine. 4) The treatment liquid according to any one of 1) to 3) above, wherein the alkanolamine (B) is N-methylethanolamine. 5) The treatment liquid according to any one of 1) to 4) above, wherein the glycol-based solvent (C) is a mixed solvent of two or more glycol-based solvents. 6) The treatment liquid according to any one of 1) to 5) above, wherein the glycol-based solvent (C) contains propylene glycol. 7) The treatment liquid according to any one of 1) to 6) above, wherein the treatment liquid is for semiconductor cleaning. 8) A method for cleaning a substrate, in which a photoresist is stripped using the treatment liquid according to any one of 1) to 7) above.

[0011] The treatment liquid disclosed herein is a treatment liquid that has excellent photoresist stripping properties and excellent storage stability, particularly at low temperatures.

[0012] One embodiment of the present disclosure is a treatment liquid having (A) a quaternary ammonium salt, (B) an alkanolamine, and (C) a glycol-based solvent. [Component (A): Quaternary Ammonium Salt] Component (A): quaternary ammonium salt in the present disclosure is a compound represented by the following general formula (1): [NR １ R ２ R ３ R ４ ] ＋ [OH] － ...(1) (wherein, R １ , R ２ , R ３ and R ４ may be the same or different and are an alkyl group having 1 to 6 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0013] The alkyl group having 1 to 6 carbon atoms may be linear or branched, and is preferably a linear alkyl group having 1 to 6 carbon atoms. Examples of linear alkyl groups having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and preferably a methyl group, an ethyl group, a propyl group, and a butyl group, and more preferably a methyl group and an ethyl group. The arylalkyl group having 7 to 10 carbon atoms may be substituted or unsubstituted. A preferred example of an arylalkyl group having 7 to 10 carbon atoms is a benzyl group. The aryl group having 6 to 10 carbon atoms may be substituted or unsubstituted. Examples of aryl groups having 6 to 10 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group, and preferably a phenyl group.

[0014] Specific examples of the quaternary ammonium salt (A) in the present disclosure include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, and dibutyldipentylammonium hydroxide; trimethylphenylammonium hydroxide; benzyltrimethylammonium hydroxide; and benzyltriethylammonium hydroxide. Among these, preferred are tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and ethyltrimethylammonium hydroxide, more preferred are tetramethylammonium hydroxide, tetraethylammonium hydroxide, and ethyltrimethylammonium hydroxide, and particularly preferred is tetramethylammonium hydroxide. Note that the treatment liquid of the present disclosure may contain one type of quaternary ammonium salt (A) alone, or may contain a combination of two or more types.

[0015] In the total amount of the treatment liquid of the present disclosure, the quaternary ammonium salt of component (A) is preferably contained in an amount of 0.1% by mass to 10.0% by mass. More preferred upper limits are, in order, 9.0% by mass, 8.0% by mass, 7.0% by mass, 6.0% by mass, 5.0% by mass, and 4.0% by mass, and particularly preferably 3.0% by mass. More preferred lower limits are, in order, 0.5% by mass, 1.0% by mass, 1.5% by mass, and 1.8% by mass, and particularly preferably 2.0% by mass. Therefore, the content of the quaternary ammonium salt of component (A) is, in order of preference, 0.5% by mass to 9.0% by mass, 1.0% by mass to 8.0% by mass, 1.5% by mass to 7.0% by mass, 1.8% by mass to 6.0% by mass, 2.0% by mass to 5.0% by mass, 2.0% by mass to 4.0% by mass, and 2.0% by mass to 3.0% by mass. When the treatment liquid of the present disclosure contains two or more types of quaternary ammonium salts of component (A), it is preferable that the total amount of the two or more types of quaternary ammonium salts of component (A) satisfies the above content range.

[0016] [Component (B): Alkanolamine] Component (B): alkanolamine in the present disclosure is a compound having a hydroxy group and an amino group on an alkane skeleton. Examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, monoisopropanolamine, N-(2-aminoethyl)ethanolamine, 2-(aminoethoxy)ethanol, N-propylethanolamine, N-ethylethanolamine, 4-(2-hydroxyethyl)morpholine, N-(3-aminopropyl)diethanolamine, 2-[2-(dimethylamino)ethoxy]ethanol, N-methyldiethanolamine, 3-amino-1 2-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, N,N-dimethyl-2,3-aminomethylpropanediol, 2-amino-1-butanol, aminomethylpropanol, 3-(dimethylamino)-1-propanol, 2-(dimethylamino)-2-methyl-1-propanol, diisopropanolamine, tris(hydroxymethyl)aminomethane, 2-(dimethylamino)ethanol, N-ethyldiethanolamine, etc. As the alkanolamine, N-alkyl alkanolamine is preferred, and N-alkylethanolamine is more preferred. Examples of N-alkyl alkanolamines include N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-methyldiethanolamine, N,N-dimethyl-2,3-aminomethylpropanediol, 3-(dimethylamino)-1-propanol, and 2-(dimethylamino)-2-methyl-1-propanol. Among the alkanolamines, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, and monoisopropanolamine are preferred, monoethanolamine, N-methylethanolamine, diethanolamine, and monoisopropanolamine are more preferred, and N-methylethanolamine is particularly preferred. Note that in the treatment liquid of the present disclosure, the alkanolamine of component (B) may be contained alone or in combination of two or more types.

[0017] In the total amount of the treatment liquid of the present disclosure, the alkanolamine component (B) is preferably contained in an amount of 0.05% by mass or more and 5.0% by mass or less. More preferred upper limits are, in order, 4.5% by mass, 4.0% by mass, 3.5% by mass, 3.0% by mass, and 2.5% by mass, and particularly preferably 2.0% by mass. More preferred lower limits are, in order, 0.1% by mass, 0.2% by mass, 0.3% by mass, and 0.4% by mass, and particularly preferably 0.5% by mass. Therefore, the preferred content of the alkanolamine component (B) is, in order of preference, 0.1% by mass or more and 4.5% by mass or less, 0.2% by mass or more and 4.0% by mass or less, 0.3% by mass or more and 3.5% by mass or less, 0.4% by mass or more and 3.0% by mass or less, 0.5% by mass or more and 2.5% by mass or less, and 0.5% by mass or more and 2.0% by mass or less. When the treatment liquid of the present disclosure contains two or more types of (B) alkanolamines, it is preferable that the total amount of the two or more types of (B) alkanolamines satisfies the above content range. Furthermore, in the treatment liquid of the present disclosure, it is preferable that the ratio of the components (A) to (B) (content of component (A) / content of component (B)) is 1.1 or more and 3.5 or less. More preferred upper limits of the ratio of the components (A) to (B) (content of component (A) / content of component (B)) are 3.3, 3.1, and 2.9, respectively, and particularly preferably 2.5. More preferred lower limits are 1.2, 1.5, and 1.8, and particularly preferably 2.0. Therefore, the ranges of the ratio of the components (A) to (B) (content of component (A) / content of component (B)) are, in order of preference, 1.2 or more and 3.3 or less, 1.5 or more and 3.1 or less, 1.8 or more and 2.9 or less, and 2.0 or more and 2.5 or less. When the treatment liquid of the present disclosure contains two or more types of component (A), the "content of component (A)" refers to the total amount of the two or more types of component (A). Furthermore, when the treatment liquid of the present disclosure contains two or more types of component (B), the "content of component (B)" refers to the total amount of the two or more types of component (B). For example, when the treatment liquid of the present disclosure contains two or more types of component (A) and two or more types of component (B), the ratio of components (A) to (B) refers to the ratio of the total amount of the two or more types of component (A) to the total amount of the two or more types of component (B) (total amount of two or more types of component (A) / total amount of two or more types of component (B)).

[0018] [Component (C): Glycol-Based Solvent] Examples of the glycol-based solvent (C) in the present disclosure include polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin; ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monopentyl ether, propylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monopentyl ether, propylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ... Examples of glycol ethers include ethylene glycol monopentyl ether, diethylene glycol monohexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopentyl ether, dipropylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, and tripropylene glycol monobutyl ether. Among these, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether are preferred, and propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether are more preferred.In the treatment liquid of the present disclosure, the glycol-based solvent (C) may be contained alone or in a mixed solvent of two or more glycol-based solvents. By containing two or more glycol-based solvents, it is possible to adjust solvent properties such as the solubility parameter, which affects the solubility of photoresists, and the dielectric constant, which affects the corrosivity of metals. That is, a mixed solvent containing two or more glycol-based solvents with different solubility parameters may be used. Values ​​described in known literature can be used for the solubility parameter and the dielectric constant. If no values ​​are available in known literature, values ​​measured by known methods can be used. The dielectric constant of the solvent is preferably lower than that of water. Specific examples of solvent combinations include combinations of polyhydric alcohols and glycol ethers, such as propylene glycol and diethylene glycol monomethyl ether, propylene glycol and diethylene glycol monobutyl ether, and propylene glycol and dipropylene glycol monomethyl ether. The combination of propylene glycol and diethylene glycol monobutyl ether is most preferred. Furthermore, the treatment liquid of the present disclosure may contain an organic solvent other than the glycol-based solvent of component (C).

[0019] In the total amount of the treatment liquid of the present disclosure, the glycol-based solvent of component (C) is preferably contained in an amount of 9.0 mass% or more and 99.5 mass% or less. More preferably, the upper limit is, in order, 99.0 mass%, 98.5 mass%, 98.0 mass%, and 97.5 mass%, and particularly preferably 97.0 mass%. More preferably, the lower limit is, in order, 80.0 mass%, 85.0 mass%, 88.0 mass%, 90.0 mass%, and 91.0 mass%, and particularly preferably 93.5 mass%. Therefore, the content of the glycol-based solvent of component (C) is, in order of preference, 80.0 mass% or more and 99.5 mass%, 85.0 mass% or more and 99.0 mass% or less, 88.0 mass% or more and 98.5 mass% or less, 90.0 mass% or more and 98.0 mass% or less, 91.0 mass% or more and 97.5 mass% or less, and 93.5 mass% or more and 97.0 mass% or less. When the treatment liquid of the present disclosure contains two or more glycol-based solvents as component (C), it is preferable that the total amount of the two or more glycol-based solvents as component (C) satisfies the above content range.

[0020] [Other Components] The treatment liquid of the present disclosure preferably contains only the above-described components (A), (B), and (C), but may also contain other components. In addition to the above-described components (A), (B), and (C), examples of other components that may be included include a pH adjuster, a corrosion inhibitor, a surfactant, an organic amine, other organic additives, water, etc.

[0021] <Regarding pH Adjusting Agents> The pH adjusting agent that may be contained in the treatment solution of the present disclosure is not particularly limited as long as it is a component that can adjust the pH to the preferred level described below. Examples of pH adjusting agents include alkali metal hydroxides (e.g., LiOH, NaOH, KOH, RbOH, CsOH), alkaline earth metal hydroxides (e.g., Be(OH)), ２ , Mg(OH) ２ , Ca(OH) ２ , Sr(OH) ２ , Ba(OH) ２ ), choline hydroxide, formula [PR １ R ２ R ３ R ４ ] ＋ [OH] － (In the formula, R １ , R ２ , R ３and R ４ may be the same or different, and include tetraalkylphosphonium hydroxides represented by hydrogen, linear alkyl having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), branched alkyl having 3 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy), substituted aryl having 6 to 10 carbon atoms, and unsubstituted aryl having 6 to 10 carbon atoms (e.g., benzyl), such as tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, and N-propyltriphenylphosphonium hydroxide. In one embodiment of the present disclosure, the pH adjuster comprises KOH. In another embodiment, the pH adjuster comprises choline hydroxide. In another embodiment, the pH adjuster comprises at least one alkali metal hydroxide and at least one other hydroxide listed herein. In another embodiment, the pH adjuster comprises KOH and at least one other hydroxide listed herein. In yet another embodiment, the pH adjuster comprises KOH and choline hydroxide.

[0022] <Regarding Corrosion Inhibitors> Examples of corrosion inhibitors that may be included in the treatment solution of the present disclosure include amino acids. Amino acids are compounds having an amino group and a carboxy group in the molecule. Preferred examples of amino acids include alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, acetylcysteine, cystine, and diacetylcystine. Corrosion inhibitors other than the above-mentioned amino acids are not particularly limited, but include acetic acid, acetone oxime, acrylic acid, betaine (trimethylglycine), dimethylglyoxime, formic acid, glyceric acid, glycerol, glycolic acid, glyoxylic acid, itaconic acid, lactic acid, maleic anhydride, mandelic acid, 2,4-pentanedione, phenylacetic acid, propionic acid, pyrocatechol, quinic acid, sorbitol, xylitol, tannic acid, picolinic acid, 1,3-cyclopentanedione, pyrogallol, and resorcinol. , hydroquinone, cyanuric acid, barbituric acid, 1,3-dimethylbarbituric acid, pyruvic acid, propanethiol, benzohydroxamic acids, 2,5-pyridinedicarboxylic acid, 4-(2-hydroxyethyl)morpholine (HEM), N-aminoethylpiperazine (N-AEP), thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, piperazine, pyrrolidine, salicylic acid, p-toluenesulfonic acid, salicylhydroxamic acid, 5-sulfosalicylic acid, and combinations thereof.

[0023] Furthermore, when the treatment solution of the present disclosure contains an amino acid as a corrosion inhibitor, an amino acid having a mercapto group, an alkylthio group, or a disulfide group in the molecule is particularly suitable. A mercapto group is a substituent represented by -SH, an alkylthio group is a substituent represented by -SR (where R represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms), and a disulfide group is a group represented by -S-S-. Examples of alkyl groups having 1 to 6 carbon atoms include linear groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl, and branched groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, and neopentyl. Examples of cycloalkyl groups having 3 to 6 carbon atoms include cyclopentyl and cyclohexyl. Specific examples of preferred R groups in the alkylthio groups include methyl, ethyl, and n-propyl, with methyl being particularly preferred. Specific examples of amino acids having a mercapto group, an alkylthio group, or a disulfide group in the molecule include acetylcysteine, cysteine, methionine, cystine, and diacetylcystine.

[0024] When the treatment solution of the present disclosure contains an amino acid as a corrosion inhibitor, it is preferable that the amino acid content be 0.01% by mass or more and 5.0% by mass or less relative to the total amount of the treatment solution of the present disclosure. More preferred upper limits are, in order, 4.0% by mass, 3.5% by mass, 3.0% by mass, 2.5% by mass, and 2.0% by mass, and particularly preferably 1.5% by mass. More preferred lower limits are, in order, 0.1% by mass, 0.15% by mass, 0.2% by mass, and 0.25% by mass, and particularly preferably 0.3% by mass. Therefore, the amino acid content is, in order of preference, 0.1% by mass or more and 4.0% by mass or less, 0.15% by mass or more and 3.5% by mass or less, 0.2% by mass or more and 3.0% by mass or less, 0.25% by mass or more and 2.5% by mass or less, 0.25% by mass or more and 2.0% by mass or less, and 0.3% by mass or more and 1.5% by mass or less. When the treatment solution of the present disclosure contains two or more amino acids, it is preferable that the total amount of the two or more amino acids falls within the above content range.

[0025] <Regarding Surfactants> Surfactants that may be contained in the treatment liquid of the present disclosure are not particularly limited, but include anionic, nonionic, cationic, and / or zwitterionic surfactants, for example: alginic acid and salts thereof; carboxymethylcellulose; dextran sulfate and salts thereof; poly(galacturonic acid) and salts thereof; homopolymers or copolymers of (meth)acrylic acid and salts thereof, maleic acid, maleic anhydride, styrene sulfonic acid and salts thereof, vinyl sulfonic acid and salts thereof, allyl sulfonic acid and salts thereof, and acrylamidopropyl sulfonic acid and salts thereof; chitosan; cationized starch; polylysine and salts thereof; diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, diallyldimethylammonium chloride, diethyldiallylammonium chloride, diallyldi(beta- (hydroxyethyl)ammonium chloride, diallyldi(beta-ethoxyethyl)ammonium chloride, 2-(dimethylamino)ethyl(meth)acrylate acid addition salts and quaternary salts, diethylaminoethyl(meth)acrylate acid addition salts and quaternary salts, 7-amino-3,7-dimethyloctyl(meth)acrylate acid addition salts and quaternary salts, N,N'-dimethylaminopropylacrylamide acid addition salts and quaternary salts, homopolymers or copolymers of allylamine, diallylamine, vinylamine, vinylpyridine; cocodimethylcarboxymethylbetaine; lauryldimethylcarboxymethylbetaine; lauryldimethyl-alpha-carboxymethylbetaine Carboxyethyl betaine; Cetyl dimethyl carboxymethyl betaine; Lauryl-bis-(2-hydroxyethyl) carboxymethyl betaine; Stearyl-bis-(2-hydroxypropyl) carboxymethyl betaine; Oleyl dimethyl-gamma-carboxypropyl betaine; Lauryl-bis-(2-hydroxypropyl) alpha-carboxyethyl betaine; Coco dimethyl sulfopropyl betaine; Stearyl dimethyl sulfopropyl betaine; Lauryl-bis-(2-hydroxyethyl) sulfopropyl betaine; Sodium dodecyl sulfate; Dioctyl sulfosuccinic acid sodium salt; Sodium lauryl ether sulfate;Examples of surfactants include polyethylene glycol branched-chain nonylphenyl ether ammonium sulfate, 2-dodecyl-3-(2-sulfonatophenoxy) disodium, PEG25-PABA, polyethylene glycol mono-C10-16-alkyl ether sulfate sodium, (2-N-butoxyethoxy)acetic acid, hexadecylbenzenesulfonic acid, cetyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, N-alkyl-N-benzyl-N,N-dimethylammonium chloride, dodecylamine, polyoxyethylene lauryl ether, dodecenylsuccinic acid monodiethanolamide, ethylenediaminetetrakis(ethoxylate-block-propoxylate), and combinations thereof. When a surfactant is contained, it is preferably present in an amount of about 0.00001% to about 1% by weight, preferably about 0.00001% to about 0.2% by weight, based on the total weight of the treatment solution of the present disclosure.

[0026] <Regarding Organic Amines> The treatment solution of the present disclosure may contain an organic amine other than the above-mentioned alkanolamines; the above-mentioned amino acids; choline hydroxide; cyanuric acid; barbituric acid; 1,3-dimethylbarbituric acid; 4-(2-hydroxyethyl)morpholine (HEM); N-aminoethylpiperazine (N-AEP); thiourea; 1,1,3,3-tetramethylurea; urea; urea derivatives; piperazine; pyrrolidine; cationized starch; polylysine and salts thereof; homopolymers or copolymers of allylamine, diallylamine, vinylamine, and vinylpyridine; dodecylamine; and ethylenediaminetetrakis(ethoxylate-block-propoxylate). Examples of organic amines include alkylamines such as trimethylamine, triethylamine, dipropylamine, isopropylamine, diisopropylamine, cyclohexylamine, and dicyclohexylamine; ether amines such as 3-methoxypropylamine, 3-butoxypropylamine, 3-(2-ethylhexyloxy)propylamine, and morpholine; arylalkylamines such as benzylamine, dibenzylamine, and N-methylbenzylamine; polyamines such as triethylenediamine, tetraethylenepentamine, triethylenetetraamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, pentamethyldiethylenetriamine, and 3,3′-iminobis(N,N-dimethylpropylamine); cyclic aliphatic amines such as hexamethylenetetramine, piperidine, and N-(2-hydroxyethyl)piperidine; and cyclic aromatic amines such as pyrrole, pyridine, pyrazine, oxazole, thiazole, and imidazole.

[0027] <Regarding Other Organic Additives> The treatment liquid of the present disclosure may contain other organic additives in addition to the pH adjuster, corrosion inhibitor, surfactant, and organic amine described above. Examples of other organic additives include, but are not limited to, solvents such as 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone (HEP), 1,4-butanediol, tetramethylene sulfone (sulfolane), and dimethyl sulfone (DMSO); 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 1,5,9-triazacyclododecane-N,N',N''-tris(methylenephosphonic acid) (DOTRP); ), 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetrakis(methylenephosphonic acid) (DOTMP), nitrilotris(methylene)triphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid) (DTPMP), bis(hexamethylenetriaminepenta(methylenephosphonic acid)), 1,4,7-triazacyclononane-N,N',N''-tris(methylenephosphonic acid) (NOTP stabilizers such as hydroxypropyl cellulose, hydroxyethyl cellulose, sodium carboxymethyl cellulose (NaCMC), any polymer prepared using N-vinylpyrrolidone monomers such as polyvinylpyrrolidone (PVP), polyacrylates and analogs of polyacrylates, polyamino acids other than polylysine (e.g., polyalanine, polyleucine, polyglycine), polyamide hydroxyurethanes, polylactones, polyacrylamides, xanthan gum, chitosan, polyethylene oxide, polyvinyl alcohol (PVA), polyvinyl acetate, polyethyleneimine (PEI), esters of sugar alcohols (e.g., sorbitol, xylitol, anhydrosorbitol), secondary alcohol ethoxylates (e.g., TERGITOL™), and combinations thereof.

[0028] <Water> The treatment liquid of the present disclosure may contain water. The content of water is typically 1% by mass or more and 25% by mass or less, more preferably 10% by mass or more and 24% by mass or less, particularly preferably 15% by mass or more and 23% by mass or less, and most preferably 18% by mass or more and 22% by mass or less, based on the total amount of the treatment liquid of the present disclosure. Note that this description is for the case where water is contained, and the best embodiment of the treatment liquid of the present disclosure is one in which the content is 0% by mass, i.e., no water is contained.

[0029] <Regarding pH> The pH of the treatment liquid of the present disclosure is preferably equal to or higher than 8. Depending on the composition of the treatment liquid, no special adjustment may be necessary, and the pH can also be adjusted using the pH adjuster described above.

[0030] <Production Method> The treatment liquid of the present disclosure can be produced, for example, by the following method. However, the production method is not limited to this. First, component (A) and component (C) are mixed and stirred. Heating may be used in combination if necessary. Once component (A) and component (C) have become uniform, component (B) and other components used as necessary are added, and the solution is further stirred and mixed.

[0031] The treatment liquid of the present disclosure can be advantageously used as a photoresist stripper for negative and positive photoresists. Examples of such photoresists include, but are not limited to, (i) a positive photoresist containing a naphthoquinone diazide compound and a novolak resin, (ii) a positive photoresist containing a compound that generates an acid upon exposure, a compound that decomposes in an acid and increases its solubility in an alkaline aqueous solution, and an alkali-soluble resin, (iii) a positive photoresist containing a compound that generates an acid upon exposure and an alkali-soluble resin having a group that decomposes in an acid and increases its solubility in an alkaline aqueous solution, and (iv) a negative photoresist containing a compound that generates an acid upon exposure, a crosslinker, and an alkali-soluble resin.

[0032] Hereinafter, the present disclosure will be described with reference to examples and comparative examples, but the present disclosure is not limited to these examples.

[0033] [Examples 1 to 10, Comparative Examples 1 to 3] Treatment liquid compositions were prepared according to the formulations shown in Tables 1 to 3. In Tables 1 to 3, the blend amounts are shown in parts by mass. Using these as samples, the photoresist stripping properties, metal corrosivity, and stability of the treatment liquid at low temperatures were evaluated according to the following test methods. The results are shown in Tables 1 to 3.

[0034] <Photoresist Removability> A silicon wafer was used with a 1 μm thick positive photoresist film formed thereon. The test piece was immersed in a treatment liquid composition at 60° C., rinsed with pure water, and then the surface condition was observed using a metallurgical microscope. Based on the observation results, the removability was evaluated as follows: ◯: Completely removed within 60 seconds ×: Not removed even after 60 seconds

[0035] <Gold Corrosion> A silicon wafer having a Ti film and an Au film formed thereon was used as a test piece. The test piece was immersed in a treatment liquid composition at 60°C for 30 minutes, washed with pure water, and dried, and then the surface of the Au film was observed with a scanning electron microscope (SEM). Based on the observation results, the damage to Au was evaluated as follows: ◯: No pits were observed on the surface of the Au film after treatment. ×: Pits were observed on the surface of the Au film after treatment.

[0036] <Low temperature stability of treatment solution> 10 mL of each treatment solution was placed in a plastic container and left to stand at -5°C for 1 day, after which the appearance was observed. ◯: Not frozen △: Partially frozen ×: Frozen

[0037]

[0038] As shown in Table 1, Example 1, which used (A) TMAH and (B) N-methylethanolamine, had better storage stability at low temperatures than Comparative Examples 1 to 3, which used only (A) TMAH.

[0039] As shown in Table 2, Examples 2 to 5, which used glycol ethers in addition to propylene glycol, were superior in terms of low corrosion of Au to Example 1, which used only propylene glycol as the glycol solvent (C).

[0040] As shown in Table 3, Examples 6 to 10, in which an amino acid was added, were superior in terms of reducing corrosion of Au compared to Example 1, in which no amino acid was added.

[0041] TMAH: Tetramethylammonium hydroxide DMSO: Dimethyl sulfoxide NMP: N-methyl-2-pyrrolidone

[0042] The results in Tables 1 to 3 confirm that the treatment liquid of the present disclosure has excellent storage stability at low temperatures and excellent photoresist stripping properties, and is therefore highly practical.

[0043] This application is based on Japanese Patent Application No. 2024-111703 filed on July 11, 2024, the contents of which are incorporated herein by reference.

[0044] The treatment liquid of the present disclosure has excellent stripping properties for positive photoresists, and in particular has excellent storage stability at −5° C., which is an issue of the present disclosure, and therefore contributes to easier and more economical production of semiconductor devices and liquid crystal devices.

Claims

1. A treatment solution comprising (A) a quaternary ammonium salt represented by the following general formula (1), (B) an alkanolamine, and (C) a glycol-based solvent. [NR １ R ２ R ３ R ４ ] ＋ [OH] － ...(1) In the formula, R １ , R ２ , R ３ and R ４ may be the same or different and are an alkyl group having 1 to 6 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

2. The treatment liquid according to claim 1, wherein the quaternary ammonium salt (A) is tetramethylammonium hydroxide, tetraethylammonium hydroxide, or ethyltrimethylammonium hydroxide.

3. The treatment liquid according to claim 1 or 2, wherein the alkanolamine (B) is an N-alkylalkanolamine.

4. The processing liquid according to claim 1 or 2, wherein the alkanolamine (B) is N-methylethanolamine or monoethanolamine.

5. The treatment liquid according to claim 1 or 2, wherein the glycol-based solvent (C) is a mixed solvent of two or more types of glycol-based solvents.

6. The treatment liquid according to claim 1 or 2, wherein the glycol solvent (C) contains propylene glycol.

7. The processing solution according to claim 1 or 2, which is used for cleaning semiconductors.

8. A method for cleaning a substrate by stripping off photoresist using the treatment liquid according to claim 1 or 2.

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