Processing solution and method of using the same

Abstract

To provide a treatment liquid that is effective in removing photoresist, with minimized damage to polysilicon, and demonstrates superior storage stability, particularly at low temperatures, thus rendering it highly functional.SOLUTION: A treatment liquid includes (A) a compound with a lactone skeleton, and (B) an amine compound with two or more hydroxy groups in one molecule. Preferably, (A) is γ-butyrolactone and (B) is N-alkyldiethanolamine. More preferably, the treatment liquid consists essentially of (A) and (B).SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a processing solution and a method for using it, mainly used in semiconductor device manufacturing processes and liquid crystal device manufacturing processes. [Background technology]

[0002] Semiconductor device manufacturing processes and liquid crystal device manufacturing processes include various steps such as lithography, etching, ion implantation, stripping, and polishing. The lithography process includes steps such as forming a uniform photoresist on a metal layer or insulating layer, performing necessary exposure and development to form a photoresist pattern, using the photoresist pattern as a mask to etch a substrate having a metal layer or insulating layer by dry etching to form a fine circuit, and removing any unwanted photoresist layer, etching residue, residual photoresist, or photoresist byproducts from the substrate using a liquid remover. Various organic liquid photoresist removers are used to remove unwanted photoresist layers, etching residue, residual photoresist, and photoresist byproducts from the substrate. In the prior art, photoresist removers often use compositions containing polar solvents such as dimethyl sulfoxide or N-methyl-2-pyrrolidone to remove unwanted photoresist layers. Furthermore, it is common practice to include a step after each process is completed, or before moving on to the next process, in which unwanted organic matter is treated using a processing solution. In this specification, various processing solutions such as pre-wetting solutions, developers, rinse solutions, and stripping solutions used in the manufacturing process of such semiconductor devices (hereinafter also referred to as "semiconductor manufacturing processing solutions," etc.) are referred to as processing solutions.

[0003] Similar to liquid crystal panel devices and other display panel devices, methods for manufacturing semiconductor devices such as integrated circuits and large-scale integrated circuits include the steps of: forming a uniform photoresist film on a metal layer or insulating layer; performing necessary exposure and development to form a photoresist pattern; using the photoresist pattern as a mask to (selectively) etch a substrate having a metal layer or insulating layer by chemical vapor deposition to form a fine circuit; and removing one or more unwanted photoresist layers, etching layers, etching residues, residual photoresist, and photoresist byproducts from the substrate with a liquid remover. Various organic liquid photoresist removers are used to remove unwanted photoresist layers, etching residues, residual photoresist, and photoresist byproducts from the substrate. In the prior art, photoresist removers often use compositions containing polar solvents such as dimethyl sulfoxide and N-methyl-2-pyrrolidone to remove unwanted photoresist layers.

[0004] In particular, further improvements are needed for chemicals used to remove photoresist in the semiconductor device manufacturing process, methods for removing photoresist using said chemicals, and methods for manufacturing semiconductor devices by removing photoresist using said chemicals, as described below.

[0005] In the semiconductor manufacturing process, semiconductor substrates and other components have electrode structures with fine wiring, and photoresist is used in this manufacturing process. The electrode structure is manufactured, for example, by coating a conductive metal or insulating film formed on a substrate with photoresist, subjecting it to exposure and development to form a resist pattern, using this photoresist pattern as a mask to etch the interlayer insulating film or wiring material film formed on the substrate to form wiring, and then removing the excess photoresist with a photoresist removal solution. In addition to the ability to remove photoresist, the photoresist removal solution is required to cause little damage to the insulating film and wiring material used, and to have storage stability that prevents solidification or precipitation even at low temperatures.

[0006] In photoresist removal solutions, compositions containing polar solvents such as dimethyl sulfoxide and N-methyl-2-pyrrolidone are frequently used. However, although N-methyl-2-pyrrolidone exhibits high cleaning power, its use tends to be avoided from the perspective of environmental concerns and human safety. Patent Document 1 describes a resist stripping solution composition characterized by containing at least one selected from N-alkylalkanolamine, dimethyl sulfoxide, and N-methyl-2-pyrrolidone. Patent Document 2 describes a resist stripping agent composition characterized by containing at least one selected from γ-butyrolactone, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, at least one selected from amino alcohols, and water. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. Hei 8-87118 [Patent Document 2] Tokuhei 7-69618 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] This invention proposes a highly practical processing solution that exhibits excellent photoresist removal properties while causing very little damage to device constituent materials such as polysilicon, and also boasts excellent storage stability, particularly at low temperatures. [Means for solving the problem]

[0009] The inventors diligently conducted research to solve the above problems and have now completed the present invention. In other words, the present invention relates to the following 1) to 8). 1) (A) A compound having a lactone skeleton, and (B) A treatment liquid having an amine compound having two or more hydroxy groups in the molecule. 2) The treatment liquid according to 1) above, wherein (A) is γ-butyrolactone. 3) The treatment liquid according to 1) or 2) above, wherein (B) is a tertiary amine compound having two or more hydroxy groups in the molecule. 4) The treatment liquid according to any one of 1) to 3) above, wherein (B) is N-alkyldiethanolamine. 5) The treatment liquid according to any one of 1) to 4) above, wherein (B) is N-methyldiethanolamine. 6) The treatment liquid according to any one of 1) to 5) above, consisting essentially of only (A) and (B). 7) The treatment liquid according to any one of 1) to 6) above, wherein (A) is 90% by mass or more and (B) is 10% by mass or less. 8) A method for cleaning a substrate for removing a photoresist using the treatment liquid according to any one of 1) to 7) above.

Advantages of the Invention

[0010] The present invention proposes a treatment liquid that is excellent in the stripping property of a photoresist, has extremely little damage to device constituent materials such as polysilicon, and has excellent storage stability, particularly storage stability at low temperatures.

Embodiments for Carrying Out the Invention

[0011] The present invention is a treatment liquid having a component (A) a compound having a lactone skeleton and a component (B) an amine having two or more hydroxy groups in the molecule. [Component (A) A compound having a lactone skeleton] In the present invention, component (A) a compound having a lactone skeleton is a heterocyclic compound consisting of two or more carbon atoms and one oxygen atom, having one or more skeletons in the molecule in which carbonyl groups are substituted on carbon atoms adjacent to the oxygen atoms forming the ring, and preferably a compound having one lactone skeleton. Specific examples of component (A) include, for example, γ-butyrolactone, δ-valerolactone, γ-valerolactone, δ-octanolactone, β-hydroxy-β-methyl-δ-valerolactone, α-methyl-γ-butyrolactone, δ-hexanolactone, γ-hexanolactone, γ-heptanolactone, ε-caprolactone, γ-octanolactone, δ-decanolactone, α-methylene-γ-valerolactone, γ-methyl-γ-decanolactone, α-methylene-γ-butyrolactone, α-acetyl-γ-butyrolactone, and γ-methylene-γ-butyrolactone. Of these, γ-butyrolactone, δ-valerolactone, γ-valerolactone, and α-methyl-γ-butyrolactone are preferred, more preferably γ-butyrolactone, δ-valerolactone, and γ-valerolactone, with γ-butyrolactone being particularly preferred. In the processing solution of the present invention, the content of component (A) is preferably 75.0% by mass or more and 99.8% by mass or less. The upper limit of this content is, in order of increasing preference, 99.5% by mass, 99.3% by mass, 99.1% by mass, 99.0% by mass, 98.8% by mass, 98.6% by mass, and 98.4% by mass, with a particularly favorable 98.2% by mass. The lower limit is, in order of increasing preference, 78.0% by mass, 80.0% by mass, 82.0% by mass, 84.0% by mass, 86.0% by mass, 88.0% by mass, 90.0% by mass, 92.0% by mass, 94.0% by mass, 96.0% by mass, and 97.0% by mass, with a particularly favorable 97.5% by mass. In other words, the most preferred content of component (A) is 97.5% by mass or more and 98.2% by mass or less.

[0012] [Component (B): Amine compound having two or more hydroxyl groups in the molecule] In the present invention, component (B), an amine compound having two or more hydroxyl groups in the molecule, can include amine compounds having multiple alkyl groups having hydroxyl groups, such as dialkanolamines, compounds having multiple hydroxyl groups at locations other than the amino group, and compounds having two or more hydroxyamino groups (-N(OH)-), but dialkanolamine compounds are more preferably used. Specific examples of dialkanolamines include diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-tertiarybutyldiethanolamine, and triethanolamine. Furthermore, it is more preferable that component (B) is a tertiary amine compound. Among the above examples, the tertiary amine compounds are N-alkyldiethanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-tertiarybutyldiethanolamine, and triethanolamine, of which N-methyldiethanolamine is the most preferred. In the processing solution of the present invention, the content of component (B) is preferably 0.20% by mass or more and 15.0% by mass or less. The upper limits of this content are, in order of increasing preference, 12.5% ​​by mass, 11.5% by mass, 10.0% by mass, 8.0% by mass, 6.0% by mass, 4.0% by mass, and 3.5% by mass, with a particularly favorable 3.0% by mass. The lower limits are, in order of increasing preference, 0.40% by mass, 0.60% by mass, 0.80% by mass, and 1.0% by mass, with a particularly favorable 1.5% by mass. In other words, the most preferred content of component (B) is 1.5% by mass or more and 3.0% by mass or less.

[0013] [Content of ingredient (A) and ingredient (B)] In the present invention, the content ratio of component (A) to component (B) [(content of (A) / content of (B))] is preferably 5 or more and 200 or less. As the upper limit of (A) / (B), in order of further preference, they are 180, 150, 120, 100, 80, 60, 55, and 50 is particularly preferred. As the lower limit, in order of further preference, they are 10, 20, 30, 40, and particularly preferably 45. Therefore, the most preferred range of (A) / (B) is 45 or more and 50 or less. In addition, as the most preferred embodiment of the present invention, it is an embodiment that substantially does not contain components other than component (A) and component (B). Here, "substantially" means that the presence of impurities etc. of 0.01% by mass or less is not hindered.

[0014] [Other components] As described above, the treatment liquid of the present invention preferably substantially does not contain components other than component (A) and component (B), but does not exclude the mode of adding components other than component (A) and component (B), and it is also possible to appropriately add them according to the purpose. In addition to the above components (A) and (B), for example, pH adjusters, organic additives, corrosion inhibitors, surfactants, organic solvents, water, etc. can be mentioned.

[0015] [Regarding pH adjusters] The pH adjuster that may be contained in the treatment liquid of the present invention is not particularly limited as long as it is a component that can adjust to the preferred pH described below. For example, alkali metal hydroxides (e.g., LiOH, KOH, RbOH, CsOH), alkaline earth metal hydroxides (e.g., Be(OH)2, Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2), and the formula NR 1 R 2 R 3 R 4 OH (wherein R 1 、R 2 、R 3 and R 4may be the same as or different from each other, and is selected from the group consisting of hydrogen, linear or branched C2-C6 alkyl (e.g., ethyl, propyl, butyl, pentyl and hexyl), C1-C6 alkoxy (e.g., methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy) and substituted or unsubstituted C6-C10 aryl, such as benzyl, and R 1 , R 2 , R 3 and R 4 will not all be methyl groups.) Compounds having such are included. Commercially available tetraalkylammonium hydroxides include tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide, triethylmethylammonium hydroxide, tris(hydroxyethyl)methylammonium hydroxide and combinations thereof, and these can be used. Instead of, or in addition to, at least one quaternary base is of the formula (PR 1 R 2 R 3 R 4 )OH (wherein R 1 , R 2 , R 3 and R 4These may be the same or different from each other and are selected from the group consisting of hydrogen, linear C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), branched C1-C6 alkyl, C1-C6 alkoxy (e.g., methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy), substituted C6-C10 aryl, unsubstituted C6-C10 aryl (e.g., benzyl), and any combination thereof. The compounds may be, for example, tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, and N-propyltriphenylphosphonium hydroxide. In one embodiment, 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.

[0016] <About organic additives> The organic additives that may be included in the treatment solution of the present invention are not particularly limited, but include, for example, 2-pyrrolidinone, 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), glycerol, 1,4-butanediol, tetramethylene sulfone (sulfolane), dimethyl sulfone, ethylene glycol, propylene glycol, dipropylene glycol, tetraglyceride, diglyceride, glycol ethers (for example, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (DEGBE), triethylene glycol monobutyl ether (TEGBE), ethylene glycol monoethyl ether (DEGBE), triethylene glycol monobutyl ether (TEGBE), ethylene glycol monoethyl ether (DEGBE) This includes, but is not limited to, xyl ether (EGHE), diethylene glycol monohexyl ether (DEGHE), ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether (Dwanol PnB), dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether (Dwanol PPh)), and combinations thereof.Alternatively, or in addition, the organic additive may be phosphonic acids and their derivatives, such as 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) (DOTP), nitrilotris(methylene)triphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid) This may include DETAP, aminotri(methylenephosphonic acid), is(is)(hexamethylene)triaminephosphonic acid, 1,4,7-triazacyclononane-N,N',N''-tris(methylenephosphonic acid (NOTP), their salts and derivatives thereof. Alternatively, or in addition, organic additives may include hydroxypropylcellulose, hydroxyethylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose (NaCMC), polyvinylpyrrolidone (P The following can be included: any polymer prepared using VP), N-vinylpyrrolidone monomer, polyacrylic acid esters and analogs of polyacrylic acid esters, polyamino acids (e.g., polyalanine, polyleucine, polyglycine), polyamide hydroxyurethane, polylactone, polyacrylamide, xanthan gum, chitosan, polyethylene oxide, polyvinyl alcohol (PVA), polyvinyl acetate, polyacrylic acid, polyethyleneimine (PEI), sugar alcohols (e.g., sorbitol and xylitol), esters of anhydrosorbitol, secondary alcohol ethoxylates (e.g., TERGITOL), and combinations thereof. In a preferred embodiment, at least one organic additive comprises HEDP. In another preferred embodiment, at least one organic additive comprises at least one glycol ether, including triethylene glycol monobutyl ether or propylene glycol n-butyl ether or propylene glycol phenyl ether.In yet another preferred embodiment, at least one organic additive comprises HEDP and at least one glycol ether, including triethylene glycol monobutyl ether or propylene glycol n-butyl ether or propylene glycol phenyl ether. In yet another preferred embodiment, at least one organic additive comprises HEC, or a combination of HEDP and HEC, or a combination of HEC, HEDP, and at least one glycol ether, including triethylene glycol monobutyl ether or propylene glycol n-butyl ether or propylene glycol phenyl ether, or a combination of HEC and at least one glycol ether, including triethylene glycol monobutyl ether or propylene glycol n-butyl ether or propylene glycol phenyl ether.

[0017] <About corrosion inhibitors> Corrosion inhibitors that may be included in the treatment solution of the present invention include acetic acid, acetone oxime, acrylic acid, alanine, arginine, asparagine, betaine, dimethylglyoxime, formic acid, glyceric acid, glycerol, glycolic acid, glyoxylic acid, histidine, itaconic acid, lactic acid, leucine, lysine, maleic anhydride, mandelic acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, proline, propionic acid, pyrocatechol, quinic acid, serine, sorbitol, tyrosine, valine, xylitol, tannic acid, picolinic acid, 1,3-cyclopentanedione, catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid, barbituric acid, and 1,3-dimethic acid. This includes, but is not limited to, rubarbitulic acid, pyruvate, propanethol, benzohydroxamic acids, 2,5-dicarboxypryidine, 4-(2-hydroxyethyl)morpholine (HEM), N-aminoethylpiperazine (N-AEP), thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, cysteine, isoleucine, methionine, piperazine, N-(2-aminoethyl)piperazine, pyrrolidine, threonine, tryptophan, salicylic acid, p-toluenesulfonic acid, salicylhyroxyamic acid, 5-sulfosalicylic acid, and combinations thereof.

[0018] <About surfactants> The surfactants that may be contained in the processing solution of the present invention are anionic, nonionic, cationic and / or amphoteric surfactants, for example: alginic acid and its salts; carboxymethylcellulose; dextran sulfate and its salts; poly(galacturonic acid) and its salts; homopolymers of (meth)acrylic acid and its salts, maleic acid, maleic anhydride, styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, acrylamidopropyl sulfonic acid and its salts; (meth)acrylic acid and its salts, maleic acid, Copolymers of maleic anhydride, styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, acrylamidopropyl sulfonic acid and its salts; chitosan; cationic starch; polylysine and its salts; diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, dimethallyldimethylammonium chloride, diethylallylammonium chloride, diallyldi(beta-hydroxyethyl)ammonium chloride, diallyldi(beta-ethoxyethyl)ammonium chloride, dimethylaminoethyl (meth)acrylate salts and quaternary salts, diethylaminoethyl (meth)acrylate salts and quaternary salts, 7-amino-3,7-dimethyloctyl (meth)acrylate salts and quaternary salts, N,N'-dimethylaminopropylacrylamidoside salts and quaternary salts, allylamine, diallylamine, vinylamine, vinylpyridine homopolymers;Also, diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, dimethallyldimethylammonium chloride, diethylallylammonium chloride, diallyldi(beta-hydroxyethyl)ammonium chloride, diallyldi(beta-ethoxyethyl)ammonium chloride, dimethylaminoethyl (meth)acrylate addition salts and quaternary salts, diethylaminoethyl (meth)acrylate addition salts and quaternary salts, 7 -amino-3,7-dimethyloctyl (meth)acrylate addition salt and quaternary salt, N,N'-dimethylaminopropylacrylamide addition salt and quaternary salt, allylamine, diallylamine, vinylamine, vinylpyridine copolymer; cocodimethylcarboxymethyl betaine; lauryldimethylcarboxymethyl betaine; lauryldimethyl-alpha-carboxyethyl betaine; cetyldimethylcarboxymethyl betaine; lauryl-bis-(2-hydroxyethyl)carboxymethyl betaine; stearyl-bis-(2-hydroxypropyl)carboxymethyl betaine Boxymethyl betaine; oleyldimethyl-gamma-carboxypropyl betaine; lauryl-bis-(2-hydroxypropyl)alpha-carboxyethyl betaine; cocodimethylsulfopropyl betaine; stearyldimethylsulfopropyl betaine; lauryl-bis-(2-hydroxyethyl)sulfopropyl betaine; sodium dodecyl sulfate; sodium dioctyl sulfosuccinate; sodium lauryl ether sulfate; polyethylene glycol branched chain nonylphenyl ether ammonium sulfate; 2-dodecyl-3-(2-sulfonatopheno Disodium (Xy); PEG-25-PABA; Sodium polyethylene glycol mono-C10-16 alkyl ether sulfate; (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; Monodiethanolamide dodecenyl succinate;Ethylenediaminetetrakis(ethoxylate-block-propoxylate); and combinations thereof are included, but are not limited thereto. When present, at least one surfactant is preferably present in the treatment solution of the present invention 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.

[0019] The organic solvent that may be included in the processing solution of the present invention may be water-soluble or water-insoluble. Examples of water-insoluble solvents include hydrocarbon solvents (toluene, xylene, hexane, cyclohexane, n-heptane, etc.). Examples of water-soluble solvents include C1-C6 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-hexanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, dithiodiglycol, or mono, oligo, polyalkylene glycol, or thioglycol having C2-C6 alkylene units; and polyols (triols) such as glycerin, diglycerin, hexane-1,2,6-triol, and trimethylolpropane. Note that the above water-soluble organic solvents also include substances that are solid at room temperature, such as trimethylolpropane. However, even if these substances are solid, they are water-soluble, and aqueous solutions containing these substances exhibit similar properties to water-soluble organic solvents and can be used with the same expected effects. For this reason, in this specification, for convenience, even such solid substances are included in the category of water-soluble organic solvents as long as they can be used with the same expected effects as described above.

[0020] <Water> The processing solution of the present invention may contain water. The amount of water is usually 1% by mass or more and 25% by mass or less in the processing solution, 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. Note that this description refers to the case in which water is included, but in the best embodiment of the present invention, the amount is 0% by mass, i.e., the embodiment without water.

[0021] <pHについて> The treatment solution of the present invention preferably has a pH of 6.5 or higher and 8.5 or lower. The upper limits of the pH range for the treatment solution, in order of preference, are 8.4, 8.3, 8.2, 8.1, 8.0, 7.9, 7.8, 7.7, 7.6, 7.5, 7.4, and 7.3, with 7.2 being particularly preferred. The lower limits, in order of preference, are 6.6, 6.7, 6.8, 6.9, and 7.0, with 7.1 being particularly preferred. In other words, the most preferred pH range is 7.1 to 7.2. Note that pH may not require special adjustment depending on the composition, and it can also be adjusted using the pH adjusting agent mentioned above.

[0022] <Manufacturing method> The processing solution of the present invention can be manufactured, for example, by the following method. However, the manufacturing method is not limited to this method. First, mix and stir components (A) and (B). Heating may be used at this time if necessary. Once components (A) and (B) are homogeneous, add any other components as needed, and further stir and mix the solution.

[0023] <Method of using the processing solution of the present invention> In one aspect of the present invention, negative and positive photoresists can be advantageously used as a photoresist stripping solution. Examples of such photoresists include, but are not limited to, (i) a positive photoresist containing a naphthoquinone diazide compound and a novolac resin, (ii) a positive photoresist containing a compound that generates acid upon exposure, a compound that decomposes with acid and whose solubility in an alkaline aqueous solution increases, and an alkali-soluble resin, (iii) a positive photoresist containing a compound that generates acid upon exposure, an alkali-soluble resin having a group that decomposes with acid and whose solubility in an alkaline aqueous solution increases, and (iv) a negative photoresist containing a compound that generates acid upon light, a crosslinking agent, and an alkali-soluble resin. [Examples]

[0024] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Note that "Example 4" should be read as "Reference Example 4".

[0025] [Examples 1-5, Comparative Examples 1-2] A treatment solution composition was prepared according to the composition shown in Table 1. Using this as a sample, the peelability of the photoresist, the corrosiveness of the polysilicon, and the low-temperature stability of the treatment solution were evaluated using the test method described below. The results are shown in Table 2. In the table, GBL represents γ-butyrolactone and DMSO represents dimethyl sulfoxide. The numbers in parentheses represent the mass percentage of the total treatment solution composition.

[0026] <Removability of photoresist> A positive-type photoresist film with a thickness of 0.3 μm was deposited on a silicon wafer and used as a test specimen. This specimen was immersed in a treatment solution composition at 40°C, washed with pure water, and then the surface condition was observed using a metallurgical microscope. Based on the observations, the peelability was evaluated as follows: ◎: Completely detached within 90 seconds 〇: Completely detached within 180 seconds ×: Not detached even after 180 seconds

[0027] <Corrosiveness of polysilicon> A substrate was used in which a 100 nm thick thermal oxide layer was formed on a silicon substrate, and a 300 nm thick polysilicon film was formed on top of it. The substrate was then washed with dilute hydrofluoric acid, immersed in a treatment solution composition at 70°C for 24 hours, rinsed with pure water, and the surface of the polysilicon film was observed. Based on the observations, the corrosiveness of polysilicon was evaluated as follows: ○: No surface roughness on the polysilicon film. ×: Surface roughness present on the polysilicon film. Furthermore, the appearance of the liquid used in the evaluation of the corrosiveness of polysilicon was observed. Based on the observation results, the presence or absence of precipitates was evaluated as follows: ○: No precipitates ×: Precipitation present (salting out of reaction products is observed)

[0028] <Low-temperature stability of the treatment solution> Each treatment solution was placed in a 10 mL container and left to stand at 5°C for one day, after which its appearance was observed. ○: Did not coagulate ×: Coagulated

[0029] [Table 1]

[0030] [Table 2]

[0031] The results in Tables 1 and 2 confirm that the processing solution of the present invention is highly practical, exhibiting excellent photoresist peelability, low corrosiveness of polysilicon, appearance of the processing solution after treatment, and low-temperature stability of the processing solution. [Industrial applicability]

[0032] The processing solution of the present invention exhibits excellent peeling properties, particularly for positive-type photoresists, while also causing minimal damage to silicon wafers and demonstrating superior stability over time. Therefore, it contributes to the simpler and more economical manufacturing of semiconductor devices and liquid crystal devices.

Claims

1. A treatment solution comprising (A) a compound having a lactone skeleton, and (B) an amine compound having two or more hydroxyl groups in the molecule, The content of components other than those described in (A) and (B) above is 0.01% by mass or less of the total amount of the treated liquid. The treatment solution wherein (B) is N-alkyldiethanolamine.

2. The treatment solution according to claim 1, wherein (A) is γ-butyrolactone.

3. The treatment solution according to claim 1 or 2, wherein (B) is N-methyldiethanolamine.

4. The processing liquid according to any one of claims 1 to 3, wherein (A) is 90% by mass or more and (B) is 10% by mass or less.

5. A method for cleaning a substrate from which a photoresist is removed, using the processing solution described in any one of claims 1 to 4.

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