TWI251132B - Remover for photoresist and method for removing photoresist using same - Google Patents

Abstract

The remover for a photoresist of the presentation invention contains (a) hydroxylamines, (b) an aromatic hydroxy compound, (c) benzotriazole or its derivative, (d) amines each having an acid dissociation constant (pKa) of 7.5-13 in an aqueous solution at 25 DEG C and (e) a water-soluble organic solvent and/or (f) water. According to the presentation invention, the photoresist remover is suitable for use particularly in the production of a liquid crystal panel device and excellent in property of preventing the corrosion of a substrate with metallic wiring and an inorganic material layer as well as in ability to remove a photoresist film and a degenerated film and a method for removing a photoresist using the removing solution composition.

Description

1251132 Ministry of Economic Affairs Intellectual Property Office Employees' Consumption Cooperatives A7 B7_ V. OBJECT OF THE INVENTION (1) Field of the Invention The present invention relates to a peeling liquid for a photoresist and a method of peeling the photoresist using the peeling liquid. More specifically, it is excellent in peelability between a photoresist film and a film which are suitable for use in the manufacture of a semiconductor element such as an IC or an LSI, or a liquid crystal panel element, and is excellent in corrosion resistance to a substrate. A method of peeling off the photoresist using the stripping solution and using the stripping solution. 1 - Description of the related art The semiconductor element and the liquid crystal panel element such as IC and LSI are uniform on a conductive metal film such as a tin oxide film formed on a substrate via deposition or the like, and an insulating film such as S 1 0 2 The photoresist is coated and selectively exposed, developed to form a photoresist pattern, and the pattern is used as a mask to selectively etch the metal film and the insulating film to form a fine circuit. It can be manufactured by removing the unnecessary photoresist layer with a stripping solution. The peeling liquid for peeling off the above-mentioned photoresist layer is a photoresist stripping liquid composition containing an alkanolamine in recent years (Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. 6-2 - 4 9 3 5 5 Bulletin No. 3, etc.). However, in the manufacturing process of semiconductor devices and liquid crystal devices of the present day, in addition to the above methods, it is necessary to peel off the photoresist layer for dry etching, polishing, ion implantation, and the like. By this treatment, the treated photoresist layer can be made into a metamorphic film. In recent years, such processing conditions have become more stringent, and since the modified film has changed from an organic film to a film having inorganic properties, the peeling of the modified film by the prior stripping liquid using the alkanolamine is not sufficient.

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 77T ------------------- Order --------- ( Please read the note on the back? Please fill out this page again. 1251132 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 B7 V. Invention Description (2) Relatively, recently, the peeling property of the metamorphic film is more excellent. A peeling liquid composition containing a hydroxylamine-based photoresist has been proposed as a peeling liquid. In addition, in the current optical lithography technique, in order to conform to the miniaturization of the pattern, the multilayering of the substrate and the change in the material formed on the surface of the substrate are required to satisfy more stringent conditions. · In particular, in the manufacture of liquid crystal display devices, it is expected to be developed without using metal wiring, an annealed polyfluorene oxide film, or an inorganic material layer such as an amorphous polysilicon film. Such a metal wiring, a peeling liquid in which both inorganic material layers are corroded and peelable. The composition for the peeling liquid for a hydroxyl group-containing photoresist may, for example, be an amine having a p K a of 7 · 5 to 1 3 , a hydroxylamine, a water-soluble organic solvent, an anticorrosive agent, and water in a specific amount. A compound for stripping liquid for photoresist (Patent No. 2 9 1 1 9 9), which is specific for hydroxylamines, water, specific amines, specific water-soluble organic solvents, and aromatic hydroxy compounds. A composition for a stripping liquid for a photoresist to be blended (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei No. 1 1 1 9 4 4 4). Further, it is also proposed to blend a nitrogen-containing organic hydroxy compound and a specific aromatic hydroxy compound, and a triazole compound as a preferred one, and a stripping solution for a positive-type photoresist of a water-soluble organic solvent (Special Kaiping 7: 1 0 0 3 3 Bulletin No. 7). Although each of the stripping liquid compositions has excellent peeling properties of the resist film and the modified film, and has excellent uranium-preventing effect on corrosion of the metal wiring board using the peeling liquid of the hydroxylamine type, it does not review the formation of the metal. The response of the substrate of the inorganic material layer such as wiring, polysilicon oxide film, or amorphous polyoxynitride film. Therefore, in particular, the use of liquid crystal display elements and the like is used for the Si 2 base----I--^^^------------------ Note on this page. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -5- 1251132 A7 ___ _B7 V. Invention description (3) (Please read the notes on the back first. In the field of the board, it is desirable that the substrate is excellent in corrosion resistance to a substrate on which an inorganic material layer such as a metal wiring or a polyimide film is formed, and a peeling liquid having excellent peelability of the altered layer for the photoresist layer. SUMMARY OF THE INVENTION The present invention is particularly useful for providing a photoresist layer provided on a substrate which is formed particularly on a substrate of an inorganic material such as a gold-based wiring and a polysilicon oxide film, and the releasable film is particularly excellent in peelability. The peeling liquid for photoresists excellent in the anti-cracking property and the method of peeling off the photoresist using the peeling liquid are the objects.

That is, the present invention relates to an acid dissociation constant (p K a ) in an aqueous solution containing (a) a hydroxylamine, (b) an aromatic hydroxy compound, (c) a benzotriazole-based compound, and (d) 25 ° C. A stripping solution for a photoresist composed of an amine of 7 · 5 to 1 3 and (e) a water-soluble organic solvent and/or (f) water. Moreover, the present invention relates to a project comprising (I) providing a photoresist layer on a substrate, (II) a process of selectively exposing the photoresist layer, and printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative (III). After the photoresist layer is used to develop the photoresist pattern, (IV) the photoresist pattern is used as a mask to etch the substrate, and (V) the photoresist pattern after etching A photoresist peeling method using the above-mentioned photoresist stripping solution for peeling off from the substrate. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -6 - 1251132 A7 B7 V. Inventive Note (4) Furthermore, the present invention relates to the inclusion of (I) a photoresist layer on a substrate. Engineering, (please read the precautions on the back and fill out this page) (II) Project to selectively expose the photoresist layer, (III) Display the exposed photoresist layer to form a photoresist pattern Engineering, (IV) The work of etching the substrate with the photoresist pattern as a mask, (V) the plasma pattern of the photoresist pattern, and (VI) the plasma The polished photoresist film is polished by the above-mentioned photoresist stripping method using the stripping solution for the photoresist. DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the peeling liquid for a photoresist of the present invention will be described in detail. The hydroxylamines as the component (a) are represented by the following general formula (II), which is printed by the R6 Ministry of Economic Affairs, Intellectual Property Office, and the employee consumption cooperative) N-〇H (II) R7 (wherein, R 6, R 7 are independently expressed A hydrogen atom, a low alkyl group having 1 to 6 carbon atoms). Here, the alkyl group having 1 to 6 carbon atoms can be exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, t-butyl, pentyl, and the paper size is suitable. China National Standard (CNS) A4 Specification (210 X 297 mm) 1251132 A7 B7 V. Description of Invention (5) Pentoyl neopentyl, third amyl, hexyl 'isohexyl, 3-methylpentyl 2, 2 methyl 3-dimethylbutyl group, etc.

R R 7 may be the same or different.

N. The above hydroxylamines may specifically be hydroxyamines (N Η 2 Ο Η ), Ν, Ν-diethylene

Methylhydroxylamine, N,N-hydroxylamine, and the like. Among them, hydroxylamine-based hydroxylamine or the like is particularly preferred. (above. As a compound of the aromatic effect of component (b), specifically, dimethylhydroxylamine (Ν Η 2 〇.Η) a) component can be used to exemplify phenol, formate, and N. One or for obtaining phenol, dimethyl 2-dihydroxybenzene), t-butyl catechin 2,4-benzenetriol, water p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol, p-hydroxyphenylethanol, Jiaoer tea is divided into resorcinol, hydroquinone, pyrogallol phenol, m-aminophenol, diaminophenol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2, acid, 2,5 — Dihydroxybenzoic acid, 3,4-di-, 5-dihydroxybenzoic acid, gallic acid, and the like. Among them, tributylcatechol, pyrogallol, gallic acid is suitable for anti-corrosive phenol, salicyl-p-amino-resorcinol, 4-dihydroxybenzylhydroxybenzoic acid, 3 with pyrocatechol, First use. (b) Cheng (Please read the phonetic transcription on the back side and then fill out this page.) The Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives can print one or two or more. The benzotriazole compound as the component (c) is the following general formula

(I)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) -8- Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed I251132 A7 ----^___B7 _ V. Invention description (6) Wherein Q is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted carbon number 丄~i 烃 a hydrocarbon group (however, it may have a guanamine bond, an ester bond in its structure), a square group or a formula /Μ R3 — N \ r5 <In the above formula, R3 is an alkyl group having 1 to 6 carbon atoms; and r4 and r5 each independently represent a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group having 1 to 6 carbon atoms or a oxyalkyl group. ); R 1 ' R 2 each independently represents a hydrogen atom, a substituted or unsubstituted carbon number of 1 to 10 hydrocarbon groups, a carboxyl group, an amine group, a hydroxyl group, a cyano 'mercapto group, a sulfoalkyl group The compound represented by sulfo] is preferably used. The "hydrocarbon group" is an organic group composed of a carbon atom and a hydrogen atom. In the present invention, in the definition of the above group Q, R1, R2, the hydrocarbon group may be any of an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and may have a saturated or unsaturated bond, and may also be a linear chain. Any one. The substituted hydrocarbon group can be exemplified by, for example, a hydroxyalkyl group, an alkoxyalkyl group or the like. Further, in the above general formula (I), Q is specifically set by the following formula R4 - R3 - N &lt; r5 ------------------- - (Please read the note on the back and fill out this page.) This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public) -9 - 1251132 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 Inventive Note (7) (in the above formula, R3, R4, and R5 are each as defined above) are preferred. Further, in the above formula, R4 and R5 are each independently selected from a hydroxyalkyl group or an alkoxyalkyl group having 1 to 6 carbon atoms. When at least one of R 4 and R 5 is an alkyl group having 1 to 6 carbon atoms, the physical properties of the benzotriazole-based compound having such a composition are not water-soluble, but are present in the stripping solution. When the compound is dissolved in other components, it is preferably used. Further, in the above general formula (I), Q also preferably uses an alkyl group having 1 to 3 carbon atoms (i.e., methyl group, ethyl group, propyl group, isopropyl group) and a hydroxy group having 1 to 3 carbon atoms. Base, hydroxyl group, etc. Specific examples of the benzotriazole-based compound include benzotriazole '5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, and 1-amino group. Benzotriazole, 1-phenylbenzotriazole, 1 methylbenzotriazole, 1 -benzotriazolecarboxylic acid methyl ester, 5-benzotriazolyl acid, 1-methoxybenzene And triazole, 1-(2,2-dihydroxyethyl)benzotriazole, 1 -3 -dihydroxypropyl)benzotriazole' or "IRUGAMET" system [] by Ciba Specialty Chemicalss 2,2 / - { [(4 -Methyl-1H-benzotriazol-1-yl) methyl]imino}diethanol, 2,2-- { [5-methyl- 1 Η-benzotriazole-1-yl)methyl]imino}diethanol, 2' 2 /1{((4-methyl- 1 Η-benzotriazol-1-yl)methyl] Amino}diethyl, or 2,2 / - { [(4-methyl-1 fluorene-benzotriazol-1-yl)methyl]imino} bispropane. Among them, benzotriazole, 1-hydroxybenzotriazole, 1-methoxybenzotriazole ' 1 -(2,2-dihydroxyethyl)benzotriazole, 1 -1, 2 Second, the paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------.-----------Book--------- (Please read the phonetic on the back? Please fill out this page again) 1251132 A7 B7 V. INSTRUCTIONS (8) Propyl)benzotriazole, 1-(2,3-dihydroxypropyl)-benzotriazine 2,2 &gt; — { 〔 (4 -Methyl-1H-benzotriazole-1-yl (please read the back of the note before refilling this page)) Methyl]imino}diethanol, 2, 2 / - [(5-methyl-1 fluorene-benzotriazole-i-yl)methyl]imino]}diethanol or the like is formed by a substrate of a metal material such as a metal wiring or a polyimide film. The anti-uranium effect 'peeling effect and the like are preferably used. · (c) The component may be used alone or in combination of two or more. The amine as the component (d) is a substrate formed of a metal wiring (for example, C u ' A 1 , an A 1 alloy, etc.) and an inorganic material layer (for example, a polyfluorene oxide film, an amorphous polyoxynitride film, or the like). In terms of the anti-corrosion effect, it is preferred to use an amine having an acid dissociation constant (p K a ) of 7 · 5 to 13 in an aqueous solution at 25 ° C. Such an amine is preferably used by selecting at least one of alkanolamines, polyalkylene polyamines, aliphatic amines, aromatic amines, and cyclic amines. The alkanolamines printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs can be exemplified by monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N. ,N-diethylethanolamine, N,N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diiso The polyalkylene polyamines such as propanolamine and triisopropanolamine can be specifically exemplified by di-ethyltriamine, tri-ethyltetramine, propylenediamine, N,N-diethylethylene. Amine, 1,4-butanediamine, N-ethyl-ethylenediamine, 1,2-propylenediamine, 1,3-dipropylenediamine, 1,6-hexanediamine, and the like. -11 - This paper scale applies to China National Standard (CNS) A4 specification (210 x 297 public) 1251132 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Description of invention (9) Aliphatic amines can be exemplified · 2 Ethyl-hexylamine, dioctylamine, tributylamine 'tripropylamine, triallylamine, heptylamine, cyclohexylamine and the like. Examples of the aromatic amines include benzylamine, diphenylamine and the like. Examples of the cyclic amines include piperization, N-methyl piperization, methyl-piperiding, hydroxyethylpiperidin and the like. · Among them, monoethanolamine, 2-(2-amine ethoxy)ethanol, di-ethyltriamine, tri-ethylidene, cyclohexylamine, piperene, etc. In the case of the peeling liquid for the photoresist, the ignition point is preferably 30 ° C or higher, and particularly preferably 50 ° C or higher. In consideration of this point, it is particularly preferable to use triethylethylene tetraamine, monoethanolamine, diethylethanolamine, 2-(2-aminoethoxy)ethanol, etc. for the safety of the liquid composition when the peeling liquid is continuously used. (d) Ingredients One type or two or more types may be used. The stripping solution of the present invention contains the above-mentioned components (a) to (d), and contains water-soluble organic solvent as the component (e) and/or water as the component (f). The water-soluble organic solvent of the component (e) may be an organic solvent which is miscible with water, and any other components (a), (b), (c) and (d) may be used arbitrarily. . Such a water-soluble organic solvent may, for example, be a subclass of dimethyl hydrazine or the like, a dimethyl hydrazine, a diphenyl sulfonium, a bis(2-hydroxyethyl) fluorene, a ring dynasty or the like; N, N - dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, N,N-diethylacetamide, etc. N-methyl paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -12- ------------------- Order---- ----- (Please read the notes on the back and fill out this page) 1251132 A7 B7 V. Inventions (10) (Please read the notes on the back and fill out this page) 1 - Batch of ketones, N —Ethyl-2—indolyl ketone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, etc.; Dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, imidazolidinone such as 1,3-diisopropyl-2-imidazolidinone; ethylene glycol, B Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether... ethylene glycol monomethyl ether acetate , ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether and other diethylene glycol monoalkyl ether (alkyl Polyols having a low alkyl group such as 1 to 6 carbon atoms, and derivatives thereof. Among them, at least one selected from the group consisting of dimethyl hydrazine, N-methyl-2-pyrrolidone and diethylene glycol monobutyl ether is preferably used in terms of better peeling properties and the like. Among them, dimethyl arsenic is particularly advantageous for the uranium prevention effect of the substrate. The component (e) may be used alone or in combination of two or more. The water as the component (f) is necessarily contained in the other components in the stripping solution of the present invention, but the blending amount thereof may be further adjusted. In the photoresist stripping liquid of the present invention containing the components (a) to (d), and (e) and/or (f), the blending amount of each component is as follows. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives (a) The upper limit of the blending amount is preferably 30% by weight, and particularly preferably 20% by weight. Further, the lower limit is preferably 2% by weight, particularly preferably 5% by weight. The upper limit of the amount of the component (b) is preferably 20% by weight, and particularly preferably 15% by weight. Further, the lower limit is preferably 5% by weight, particularly preferably 1% by weight. -13- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1251132 A7 V. Invention Description (11 (Please read the note on the back and fill in this page) (c) Maximum amount of ingredients Preferably, it is 2% by weight, and particularly preferably 15% by weight. Further, the lower limit is preferably 重量·〇1% by weight, and particularly preferably 0.1% by weight. (d) The upper limit of the compounding amount is 8% by weight is preferred, and particularly preferably 7% by weight. Further, the lower limit is preferably 2% by weight, and particularly preferably 5% by weight. The amount of the above compounding amount corresponds to each inherent acid. The dissociation constant (p K a ) 値 is preferably determined by using the optimum blending amount. (e) The upper limit of the blending amount of the component is preferably 80% by weight, and particularly preferably 7 〇 by weight. Further, the lower limit is 1 5重量% is preferred, and particularly preferably 25 wt%. 尙, (f) component is the remainder. The present invention is by the components (a) to (d), and (e) component and/or When the component (f) is in the above-mentioned range of the ratio, the photoresist stripping property can be achieved, and the inorganic wiring and the inorganic oxide film can be inorganic. The effect of the corrosion resistance of the material layer is further improved. In particular, when the amount of the component (b) and the component (c) is within the above range, the corrosion prevention effect on the metal wiring and the inorganic material layer can be more effectively achieved. The property bureau employee consumption cooperative prints the stripping solution of the present invention in addition to the above components (a) to (d), and the components (e) and/or (f), in order to further improve the permeability of the stripper, for the photoresist film The stripping property, if necessary, can also be combined with the following general formula (III). The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 x 297 public) -14 - 1251132 A7 ______Β7 V. Invention description (12)

(Please read the precautions on the back and fill out this page) (wherein R8 is an alkyl group representing 6 to 20 carbon atoms) · N-alkyl-2-pyrrolidone shown, and acetylene alcohol monoalkylene oxide At least one compound is selected from the adduct. The N-alkyl-2-pyrrolidone and acetylene alcohol alkylene oxide adducts themselves are well known as surfactants. The Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumer Cooperatives, printed the above-mentioned general formula (III), N-hospital base 2 - 吼 院 院 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克 克2-pyrrolidone, N-octyl-2-pyrrolidone, N-mercapto- 2, one 吼略院丽' N-癸基一2 - 吼略院, N -11*院基 - 2 - pyrrolidone, N —dodecyl-2-pyrrolidone, N-tridecyl-2-pyrrolidone, N-tetradecyl-2-pyrrolidone, N-pentadecyl-2-pyrrolidone, N-hexadecyl 2 - pyrrolidone 'N - heptadecyl-2-pyrrolidone, N-octadecyl-2-pyrrolidone and the like. Among them, N-octyl-2-pyrrolidone and N-dodecyl-2-pyrrolidone are sold as "SURFADONE LP100" and "SURFADONE LP300" (all of which are manufactured by ISP Japan). . In the above acetylene alcohol-anaerobic oxygen addition product, the acetylene alcohol forming the adduct is subjected to the following general formula (IV) -15- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1251132 A7 B7 V. INSTRUCTIONS (13) R10 IR9 — C=C— C — OH (IV)R11 (wherein R9 is a hydrogen atom or printed by the Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative

A compound represented by (R1Q, R11, R12, and R13 each independently represent a hydrogen atom and an alkyl group having 1 to 6 carbon atoms) is preferably used. Here, the alkyl group having 1 to 6 carbon atoms can be exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, t-butyl, pentyl, isopentyl, Neopentyl, third amyl, hexyl, isohexyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, and the like. The acetylene alcohol is sold, for example, in the series of "SURFINOL" and "OLFIN" (all manufactured by Air Product and Chemicals Inc.), and is suitable for use. Among them, "SURFINOL 104", "SURFINOL 82" or a mixture thereof is most suitable for use in terms of its physical properties. Others can also use "OLFIN B", "OLFIN P", "OLFIN Y", etc. The alkylene oxide added to the above acetylene alcohol is preferably used as ethylene oxide, propylene oxide or a mixture thereof. In the present invention, the acetylene alcohol-alkylene oxide adduct is in the following general formula (V ----------- loaded------- Please read the notes on the back and fill out this page.) The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -16- 1251132 A7 B7 5. Invention description (14)

R 15

R 14 c = C— C — 〇-(- ch2ch2o-)^· η(V)

R 16 (wherein R14 represents a hydrogen atom or R17 ο- Ι R18 〇-f&quot; CH2CH2〇+-Η Printed by the Intellectual Property Office of the Ministry of Economic Affairs

The compound represented by (Rl5, Rl6, R17, and Rl8 each independently represent a hydrogen atom and an alkyl group having 1 to 6 carbon atoms) is preferably used. Here, (η + m ) is an integer representing from 1 to 30, and the number of addition of ethylene oxide can be subtly changed with respect to properties such as solubility in water and surface tension. The acetylene alcohol monoalkylene oxide adduct is sold under the series "SURFINOL" (made by Air Product and Chemicals Inc.) or "ACETYLENOL" (made by Chuanxiong Fine Chemical Co., Ltd.) series, and is suitable for use. . In the case of considering the solubility in water, the change in surface tension, etc. caused by the addition number of ethylene oxide, "SURFINOL 440" (n + m - 3.5), "SURFINOL 465" (η + m) 2 1 〇), "SURFINOL 485" (η + m 2 3 〇), "ACETYLENOL EL" (n + m = 4), "ACETYLENOL EH" (n + m = 1 〇), or a mixture thereof is suitable for use . In particular, a mixture of "ACETYLENOL EL" and "ACETYLENOL EH" is preferred. Among them, "ACETYLENOL EL" and "ACETYLENOL -------------------- order --------- (please read the precautions on the back and fill in This page applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). -17- 1251132 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 B7 V. Invention Description (15) EH” to 2: Mixing ratios of 8 to 4: 6 (weight ratio) are particularly suitable for use. In the peeling liquid of the present invention, the upper limit of the compounding amount of the compound added to increase the permeability of the peeling liquid is preferably 1% by weight, and particularly preferably 0.5% by weight. Further, the lower limit is preferably 〇 · 〇 1% by weight, and particularly preferably 0 · 0 15 % by weight. The stripper for photoresist of the present invention can be advantageously used as a photoresist which can be imaged by an aqueous alkaline solution containing a negative or positive photoresist. Examples of such a photoresist include (i) a positive photoresist containing a naphthoquinonediazide compound and a phenolic enamel resin, and (ii) a compound containing an acid by exposure, which is decomposed by an acid and is an aqueous alkaline solution. a compound having an increased solubility and a positive photoresist of an alkali-soluble resin, (1 i 1 ) containing a compound which generates an acid by exposure, which is decomposed by an acid and which has an increased solubility in an alkaline aqueous solution. The positive resist of the soluble resin, and (iv) a compound containing a compound which generates an acid via light, a negative resist of a crosslinking agent and an alkali-soluble resin, etc., are not limited thereto. The photoresist stripping method of the present invention is characterized in that a resist pattern is formed according to a lithography method, and the conductive metal film and the insulating film are selectively etched as a mask to form a fine circuit, and then divided into a stripping photoresist pattern. In the case of the type, and 2, the photoresist pattern after the uranium engraving process is subjected to plasma polishing treatment, and the plasma-polished metamorphic film (resistance residue), metal deposit or the like is peeled off. The case of the peeling resist film after the etching process of the former may include (I) a process of providing a photoresist layer on the substrate, ------------------- -------- (Please read the notes on the back and fill out this page.) This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 18- 1251132 Ministry of Economic Affairs Intellectual Property Office staff consumption Cooperatives Printing A7 B7 V. Inventions (16) (II) Project of selectively exposing the photoresist layer, (III) Projecting the exposed photoresist layer to form a photoresist pattern, (IV) The photoresist pattern is used as a mask to etch the substrate, and (V) the photoresist pattern after the etching process is used, and the above-described photoresist stripping solution of the present invention is peeled off from the substrate. The photoresist peeling method. Further, in the latter case, the case where the metamorphic film, the metal deposit or the like is peeled off after the plasma polishing treatment includes (I) a process of providing a photoresist layer on the substrate, and (II) selectively exposing the photoresist layer. Engineering, (III) Projecting the exposed photoresist layer to form a photoresist pattern, (IV) using the photoresist pattern as a mask to etch the substrate, and (V) The photoresist pattern is subjected to plasma polishing, and (VI) the photoresist-degraded film after the plasma polishing is used, and the photoresist stripping method of the above-described photoresist stripping solution of the present invention is peeled off from the substrate. In the present invention, in particular, in the peeling of the photoresist formed on the substrate on which the metal wiring or the metal wiring and the inorganic material layer are formed, the peeling property of the photoresist film and the modified film is excellent, and both of the substrate corrosion resistance are excellent. The unique effect of this paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 19-------------^^农--------Book-- ------- (Please read the notes on the back and fill out this page) 1251132 A7 B7 V. Inventions (17) (Please read the notes on the back and fill out this page) Metal wiring can be listed as aluminum (A 1), aluminum-bismuth (A 1 - S i ), aluminum-bismuth-copper (A 1 - S i - Cu) and other aluminum alloys (A 1 alloy); pure titanium (T 1 ); titanium nitrite (T i N ), titanium alloy (titanium 1 W) or the like (titanium alloy), pure copper (C u ), etc., but is not limited thereto. The inorganic material layer is particularly preferably a layer composed of a semiconductor material such as a polyfluorene oxide film or an amorphous polysilicon oxide film, but is not limited thereto. The conventional peeling liquid is difficult to make the peeling property of the photoresist, and the corrosion resistance of the substrate having the layer composed of the metal wiring and the inorganic material is established. However, the present invention can achieve such effects simultaneously. In the latter peeling method, after the plasma polishing, the metal deposit which occurs on the surface resist residue (photoresist film) of the substrate and the metal film is adhered and remains in a residue type. These residues are brought into contact with the stripping liquid of the present invention, and the residue on the substrate is peeled off. Plasma polishing is originally a method of removing the photoresist pattern, but the plasma polishing is a part of the photoresist pattern remaining in a metamorphic film type, and the present invention is a photoresist film which is particularly effective for completely removing such a film. The Ministry of Economic Affairs, Intellectual Property Office, and the Consumer Cooperatives Printed The formation of the photoresist layer, exposure, imaging, and uranium engraving are common methods and are not particularly limited. The etching may be performed by wet etching or dry etching, and the stripping liquid of the present invention is particularly suitable for use in the peeling of the photoresist film after wet etching. In particular, in a glass substrate or the like used for a liquid crystal panel element or the like, an acid etching solution such as phosphoric acid, nitric acid or acetic acid is preferably used as the etching liquid (etching agent).尙, the above (III) imaging project, (V) or (VI) -20- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1251132 A7 B7 V. Description of invention (18) After the stripping process, it may be treated and dried using conventionally using pure water and lower alcohol. (Please read the precautions on the back and fill out this page.) Also, depending on the type of photoresist, the chemically amplified photoresist can be subjected to heat treatment after exposure and exposure. Further, it is also possible to perform baking after forming a photoresist pattern. • The stripping treatment is usually carried out by a dipping method or a rinsing method. The peeling time is not particularly limited as long as it is sufficiently peeled off, but it is usually about 1 to 20 minutes. Next, the present invention will be described in more detail based on examples, but the present invention is not limited by such examples.配合' compounding amount means weight % unless otherwise specified Ο Examples 1 to 8 and Comparative Examples 1 to 7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed on S 1 0 2 forming A 1 wiring and polysilicon film On the substrate, a positive-type photoresist TFR-89 OPM (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied by a spinner and pre-baked at 110 ° C for 90 seconds to form a film thickness. 2 · 5 // m photoresist layer. The photoresist layer was exposed through a mask and developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) to form a photoresist pattern. Next, baking was carried out at 145 ° C for 240 seconds. Next, the substrate having the photoresist pattern formed by the above conditions was subjected to dry etching. Secondly, although the photoresist pattern is plasma-polished by oxygen, it is a polishing residue (photoresist film). -21 - This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1251132 A7 B7 V. Inventive Note (19) Thereafter, for the above-mentioned processed substrates, the components shown in Table 1 are used. The stripping solution was subjected to a photoresist stripping treatment at 40 ° C for 2 minutes. The substrate after the stripping treatment is sufficiently rinsed with pure water, and at this time, the peeling property of the modified film, the corrosion state of the A 1 wiring, and the corrosion state of the amorphous polyfluorene oxide film are SE Μ (scanning electron display) . Micromirror) The observation of the photo was evaluated. The results are shown in Table 2.尙, the peeling property of the deteriorated film, and the corrosion states of the A 1 wiring and the amorphous polysilicon oxide film were evaluated as follows. [Removal of the photoresist film] A: Peeling residue of the photoresist without deterioration film B: Seeing the peeling residue of the photoresist film (A1 wiring, corrosion state of amorphous polysilicon film) A : Not observed See Corrosion B: See Corrosion nn ·ϋ m I -ϋ ϋ ϋ ϋ n · ϋ I Marne I mammt 1 ϋ^·0, a I an n ϋ ϋ 1 I (Please read the phonetic on the back? Page} Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed on this paper scale Applicable to China National Standard (CNS) A4 Specification (210 x 297 public) 1251132 A7 B7 V. Invention Description (20) Table 1 Ministry of Economic Affairs Intellectual Property Office Staff Consumption Composition of Co., Ltd. Printed photoresist stripping liquid (% by weight) (8) Component (6) Component (C) Component (d) Component (6) Component (f) Component Other components Example 1 HA PCA BT-GL MEA BDG Water - (10 (4.5) (0.5) (5) (60) (20) Example 2 HA PCA BT-IR AEE DMSO Water - (10) (4.5) (0.5) (5) (60) (20) Example 3 HA PCA BT-GL MEA - Water - (15) (5) (1) (64) (15) Example 4 HA PCA BT-IR AEE - Water - (15) (5) (0.5) (64.5) (15) Example 5 HA PCA BT TET DMSO Water - (15) (5) (0.5) (10) (54.5) (15) Example 6 DEHA PCA BT MEA BDG - (10) (5) (1) (64) (20) Example 7 HA PCA BT-GL MEA NMP Water PI (10) (5) (0.5) (5) (59) (20) (0.5) Example 8 HA PCA BT-GL MEA NMP Water AT (15) (4.3) (0.5) (10) (55) ( 15) (0.2) Comparative Example 1 HA PCA - TET DMSO Water - (15) (5) (10) (55) (15) Comparative Example 2 HA PCA _ MEA DMSO Water - (15) (10) (30) ( 30) (15) Comparative Example 3 HA PCA - MEA - Water - (15) (5) (65) (15) Comparative Example 4 HA PCA - AEE - Water - (15) (5) (65) (15) Comparison Example 5 HA PCA _ MEA BDG Water - (10) (5) (5) (60) (20) Comparative Example 6 - PCA BT-GL MEA DMSO Water - (5) (0.5) (9.5) (60) (25 ) Comparative Example 7 HA - BT-GL MEA DMSO Water - (10) (0.5) (9.5) (60) (20) ----------- Packing -------- Order - -------- (Please read the note on the back and fill out this page.) This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -23- 1251132 A7 B7 V. Description of invention (twenty one )

尙, in Table 1, HA is a hydroxylamine; DEHA is N'N-diethylhydroxylamine; EAEA is monoethanolamine (25 t: PKa = 9 · 52 in an aqueous solution); AEE is 2 - ( 2 - Amine ethoxy) ethanol (pKa = 9.42 in 25 〇C aqueous solution); TET is tri-ethyltetramine (PK a = 9 · 7, 4 in aqueous solution at 25 ° C); BDG is digan Alcohol monobutyl ether; DMSO is dimethyl sulphon; NMP is n-methyl-2-pyrrolidone; PCA is pyrocatechol; BT - GL is 1-(1,2-dihydroxypropyl)benzotriene Oxazole, BT-1R is 2,2 / - { [(4-methyl-1H-benzotriazol-1-yl)methyl]imino]diethanol; BT is benzotriazole; PI is Pyrrolidone-based active agent (N-octyl-2-pyrrolidone); AT is a mixture of acetylene alcohol monoalkylene oxide adduct ("ACETYLENOL EL"·· "ACETYLENOL EH" = 3: 7 (mixed weight ratio) ). (Please read the notes on the back and then fill out this page.) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed -24- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1251132 A7 V. Invention Description (22) Table 2 Corrosion state of the photoresist layer of the amorphous polyfluorene oxide A 1 wiring Corrosion state of the film Peeling Example 1 AAA Example 2 AAA . Example 3 AA . A Example 4 AAA Example 5 AAA Example 6 AAA Example 7 AAA Example 8 AAA Comparative Example 1 BAA Comparative Example 2 BAA Comparative Example 3 BAA Comparative Example 4 BAA Comparative Example 5 AAB Comparative Example 6 AAB Comparative Example 7 AC - (Please read the back of the note first) In addition, as for the results of Table 2, it can be confirmed that the examples 1 to 8 are metal wirings, and the inorganic material layers are excellent in corrosion resistance and deterioration of photoresist. The film has excellent peelability. On the other hand, in Comparative Examples 1 to 7, the metal wiring and the inorganic material layer were both excellent in corrosion resistance and peeling property of the photoresist film. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 297 297 mm) 1251132 A7 B7 V. Inventive Note (23) As described in detail above, according to the present invention, the formation of a metal wiring 'inorganic material layer can be provided A peeling liquid for a photoresist having excellent peeling properties of the substrate and the peeling property of the photoresist layer and the modified film, and a method of peeling off the photoresist using the peeling liquid. The present invention is particularly suitable for use in a photoresist layer formed on a substrate used in the manufacture of a liquid crystal panel device or the like, and the release film is peeled off. -----------Install--------Set--------- (Please read the notes on the back and fill in this page) Ministry of Economic Affairs Intellectual Property Office staff consumption The cooperative printed this paper scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -26-

Claims (1)

1251132 A8 B8 C8 D8 VI. Patent Application No. 89 1 27764 Patent Application Revision of Chinese Patent Application Revision of the Republic of China 94 January 1 Revision 1 · A stripping solution for photoresists containing: (a) Hydroxylamines 2 to 3% by weight, (b) aromatic hydroxy compound 〇·5 to 20% by weight, (c) benzotriazole-based compound 〇·~2〇% by weight (d) 2 5 ° C in an aqueous solution The acid dissociation constant (ρ κ a ) is 2 to 80% by weight of the amine of 7 · 5 to 1 3 , and (e ) a water-soluble organic solvent and/or ( ί ) water, wherein the composition is as follows. Formula (Compound R1 R2 NIQN (I) Printed by the Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative [where Q is the chlorinated [hydroxyl, substituted or unsubstituted hydrocarbon group i ~ 1〇 hydrocarbon group (but its The structure may also have a stilbene bond, a vinegar bond, an aryl group, or the formula R3 N R4 FT (in the above formula, R3 is an alkyl group representing a carbon number of 1; R is a paper scale applicable to the Chinese national standard ( CNS ) A4 specification (mm) 1251132 A8 B8 C8 D8 VI. Patent application scope R5 represents a group independently represented by a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group; and R 1, R 2 represents a carbon atom which is independently substituted or unsubstituted. a hydrocarbon group having 1 to 10, a carboxyl group, an amine group, a hydroxyl group, a cyano group, a decyl group, a sulfonyl group or a sulfo group, but when Q is a hydrogen atom, (1) R 1 and R 2 are not hydrogen at the same time. One of the atoms, (ii) R /, R2 is a hydrogen atom, the other is not a carboxyl group, (iii) R1, r2 is not a hydroxypropyl group, and when Q is a hydroxyl group, R1 and R2 are different hydrogen atoms. 2. The stripping solution for a photoresist according to claim 1, wherein in the general formula (I), Q is the following formula 3 γ R4 ~ R3 ^ \r5 (in the above formula 'R 3, R 4, R 5 respectively, as defined in the first paragraph of the patent application scope) The Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed the base 'hydrogen atom, alkyl group with 1 to 3 carbon atoms, and hydroxyalkane with 1 to 3 carbon atoms. A retort for a photoresist as described in claim 1, wherein the component (d) is an alkanolamine, a polyalkylamine, an aliphatic amine And at least one selected from the group consisting of a cyclic amine, wherein the component (e) is a diethylene glycol monoalkyl ether, N-methyl one. 2 - Pyrrole paper size is appropriate (CNS) (210X 297 metric tons) ~~7^ 8 8 8 8 ABCD 1251132 6. At least one of the patented range of alkanones and dimethyl arsenic. 5. The peeling liquid for a photoresist according to the first aspect of the invention, wherein the total amount of the peeling liquid is adjusted to be 15 to 80% by weight of the component (e). 6. The stripping solution for a photoresist according to claim 1, which further comprises the following general formula (I II) 〇(III) R8 (wherein R8 represents a carbon number of 6 to 2 0; An alkyl group of the N-alkyl-2-pyrrolidone and at least one compound selected from the acetylene alcohol-epoxide adducts. 7. The stripping solution for a photoresist according to claim 6, wherein the acetylene alcohol monoalkylene oxide adduct is represented by the following general formula (v). Consumer Cooperatives Print R 14 R15 c = C - C - - - (- CH2CH2 〇 &quot;) ^ H &gt; 16 (V) (wherein R14 is a hydrogen atom or -3- This paper scale applies to Chinese national standards (CNS) A4 specification (210X: Z97 mm) 1251132 A8 B8 C8 _____ D8 VI. Patent application scope R17 H2CH2〇-)^H i —c — o-^c R18 R15, R16,, Rl8 are independent A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and (n+m) is an integer of 1 to 30). The stripping solution for a photoresist according to claim 1, which is used for peeling off a photoresist provided on a substrate on which a metal wiring and an inorganic material layer are formed. 9) A method of stripping a photoresist, comprising the steps of: (I) providing a photoresist layer on a substrate, (II) selectively exposing the photoresist layer, and (III) exposing the photoresist after exposure The step of developing the photoresist pattern for the layer, (IV) the step of etching the substrate with the photoresist pattern, and the step of etching the substrate by the Intellectual Property Office of the Ministry of Economic Affairs (V) after the etching step The photoresist pattern is a step of peeling off the substrate by using a stripping solution for a photoresist according to any one of claims 1 to 8. The method of peeling off the photoresist as described in claim 9, which is to use a substrate which forms a metal wiring and an inorganic material layer. 1 1. A method of stripping a photoresist, comprising the steps of: (I) providing a photoresist layer on a substrate, the paper size is applicable to China National Standard (CNS) A4 specification (210×297 mm) _ 4 _ 1251132 V π, the scope of patent application (1 1 ) The step of selectively exposing the photoresist layer, (1 1 1 ) developing the exposed photoresist layer, and setting a photoresist pattern, the photoresist The pattern is used as a mask, the step of engraving the substrate with uranium, (v) the step of plasma polishing the photoresist pattern, and (ν 1 ) the photoresist of the photoresist after polishing the plasma, using the §f stomach The peeling liquid for photoresists according to items 1 to 8 of the range is peeled off from the substrate. '1 2 · The &lt;&lt;&gt;&gt; of the stripping resist as described in claim 1 of the patent application uses a substrate which forms a metal wiring and an inorganic material layer. (Please read the notes on the back and fill out this page.) Printed by the Intellectual Property Office of the Ministry of Economic Affairs. The paper scale applies to the Chinese National Standard (CNS) A4 Wash (WOX297 mm)