Photoresist stripping liquid composition for manufacturing display

Abstract

The present invention relates to a photoresist stripping solution composition for manufacturing a display, and more particularly to a photoresist stripping solution composition capable of being applied to all processes for manufacturing a display. More specifically, the photoresist stripping solution composition for manufacturing a display of the present invention is capable of being applied to all transition metal and oxide semiconductor wires, and has an excellent ability to remove a denatured photoresist generated after a hard baked process, an implant process, and a dry etch process. In particular, a corrosion inhibiting effect is shown further specialized for a copper (Cu) wire pattern edge portion which is easily corroded after dry etching.

Description

TECHNICAL FIELD

[0001] The present invention relates to a photoresist stripper composition for manufacturing a display, and more particularly to a photoresist stripper composition capable of being used in all processes for manufacturing a display. More specifically, the photoresist stripper composition for manufacturing a display of the present invention is capable of being applied to all transition metal and oxide semiconductor wires, and has an excellent ability to remove a denatured photoresist generated after a hard baked process, an implant process, and a dry etch process. In particular, an etch inhibition effect is shown further specialized for a copper (Cu) wire pattern edge portion which is easily etched after a dry etch. BACKGROUND

[0002] In a manufacturing process of a flat panel display (FPD), a photo-lithography process is widely used to form a prescribed pattern on a substrate. The photo-lithography process is mainly composed of a series of processes such as an exposure process, a dry or wet etch process, and ashing, and after a photoresist is coated and exposed on a substrate, a dry or wet etch is performed thereon to form a pattern. Therefore, a photoresist stripper is required to remove the photoresist remaining on a metal wire.

[0003] In the early stage of starting to use a stripper, an organic stripper was generally used, but thereafter, a stronger stripping power was gradually required in the process, and thus an aqueous stripper including water was used. The aqueous stripper provides a strong stripping power, but has a problem that a metal wire or the like is easily etched.

[0004] In particular, a higher corrosion prevention performance is required for a copper wire pattern edge portion which is easily etched after a dry etch, because when an alkyl alcohol amine, which is mainly used, is mixed with water to generate a hydroxyl ion, a significant increase in corrosion of metals including copper and aluminum is caused. Therefore, a special corrosion inhibitor for preventing corrosion of a metal wire is required.

[0005] In order to solve this problem, various corrosion inhibitors have been researched, and among them, a sulfur-based azole compound is most commonly used. However, the sulfur-based azole compound has a tendency that a performance is reduced in a copper wire pattern edge portion after etching, and sulfur has a possibility of being deposited or re-adsorbed.

[0006] In the future, the above-described pattern will be developed into a more fine pattern, and thus a higher corrosion prevention power and an excellent stripping power are required. In particular, due to the above-described problem, a non-sulfur corrosion inhibitor which can replace the sulfur-based azole compound is required.

[0007] The present inventors have found that a compound having a specific chemical structure has the above-mentioned effects in the course of research into a non-sulfur corrosion inhibitor having more excellent corrosion resistance and maintaining excellent peeling force for a pattern edge portion of a copper wire susceptible to corrosion after dry etching, and completed the present invention.

[0008] Prior Art Documents

[0009] Patent Documents

[0010] Patent Document 1: Korean Granted Patent 10-1089211

[0011] Patent Document 2: Korean Published Patent 10-2017-0019871 SUMMARY

[0012] TECHNICAL PROBLEM

[0013] The present invention relates to a photoresist stripping solution composition for manufacturing a display which solves the problems of the aforementioned sulfur-based corrosion inhibitor.

[0014] Another object of the present invention is to provide a photoresist stripping solution composition for manufacturing a display having very excellent corrosion resistance and peeling force regardless of the content of water for copper, aluminum (Al) and oxide metal wires, and in particular, including a non-sulfur corrosion inhibitor applicable to a pattern edge portion of a copper wire susceptible to corrosion after dry etching.

[0015] TECHNICAL SOLUTION

[0016] To achieve the above object, the present invention provides a photoresist stripping solution composition which can replace sulfur-based azole compounds, and at the same time, includes a non-sulfur compound having more excellent corrosion resistance and peeling force than existing photoresist stripping solution compositions.

[0017] Specifically, according to one embodiment of the present invention, the present application provides a photoresist stripping solution composition including:

[0018] (a) 0.01 to 3 weight percent of a transition metal and metal oxide corrosion inhibitor of the following Chemical Formula 1;

[0019] (b) 0.05 to 3 weight percent of a non-sulfur corrosion inhibitor of the following Chemical Formula 2;

[0020] (c) 1 to 10 weight percent of a mixture of primary and secondary amines;

[0021] (d) 1 to 15 weight percent of a cyclic alcohol;

[0022] (e) 1 to 30 weight percent of an aprotic polar organic solvent;

[0023] (f) 1 to 30 weight percent of a protic polar organic solvent; and

[0024] (g) a remaining amount of ultrapure water.

[0025] Chemical Formula 1:

[0026]

[0027] Chemical Formula 2:

[0028]

[0029] Chemical Formula 3:

[0030]

[0031] wherein T 1 or T 2 each independently is -O - NH4 + or -O-H;

[0032] T 3 is -O-R or -R`;

[0033] R and R` each independently is selected from the group consisting of hydrogen, a methyl group, a linear or branched C2-C 12 alkyl group, a linear or branched C2-C 12 alkenyl group, a linear or branched C2-C 12 alkynyl group, a C3-C 12 cycloalkyl group, a heterocycloalkyl group having 3 to 10 nuclear atoms including one or more heteroatoms selected from the group consisting of N, O, and S, a C6-C 20 aryl group, a heteroaryl group having 5 to 20 nuclear atoms including one or more heteroatoms selected from the group consisting of N, O, and S, a C1-C 12 alkoxy group, and a C6-C 12 aryloxy group;

[0034] Ring A of Chemical Formula 2 is one of the structures of Chemical Formula 3;

[0035] R 1 , R 2 , and R 3 are selected from the group consisting of a methyl group, a linear or branched C2-C 12 alkyl group, a linear or branched C2-C 12 alkenyl group, a linear or branched C2-C 12 alkynyl group, a C3-C 12Cycloalkyl groups, heterocyclic alkyl groups having 3 to 10 nuclear atoms containing one or more heteroatoms selected from the group consisting of N, O, and S, C6–C 20 aryl, heteroaryl with 5 to 20 nuclear atoms including one or more heteroatoms selected from the group consisting of N, O and S, C1 to C 12 Alkyl groups and C6-C 12 In the group composed of aryl groups;

[0036] * refers to the carbon atom that forms the pyridine ring of chemical formula 2, which is fused with ring A.

[0037] In a specific embodiment of the present invention, the aforementioned transition metal and metal oxide corrosion inhibitor is selected from monoammonium phosphate, diammonium hydrogen phosphate, triammonium phosphate, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, tert-butylphosphonic acid, pentylphosphonic acid, n-hexylphosphonic acid, triethyl phosphate, octylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, tetradecylphosphonic acid, and octadecylphosphonic acid. It is one or more of the following, but not limited to: acid, hexylphosphate, heptylphosphate, octylphosphate, nonylphosphate, decylphosphate, and dodecylphosphate.

[0038] In one embodiment of the present application, the above-mentioned sulfur-free corrosion inhibitor is one or more selected from the group consisting of imidazo[4,5-b]pyridine, 6-methylimidazo[4,5-b]pyridine, imidazo[4,5-b]pyridine-2-carboxylic acid, 6-methylimidazo[4,5-b]pyridine-2-carboxylic acid, 1H-pyrazolo[3,4-b]pyridine, 3-methyl-1H-pyrazolo[3,4-b]pyridine, 1H-pyrazolo[3,4-b]pyridine-3-carboxylic acid, 5-methyl-1H-pyrazolo[3,4-b]pyridine-3-carboxylic acid, 1H-1,2,3-triazolo[4,5-b]pyridine, 6-methyl-3H-1,2,3-triazolo[4,5-b]pyridine, 3H-1,2,3-triazolo[4,5-b]pyridine-6-carboxylic acid, and 3-methyl-3H-1,2,3-triazolo[4,5-b]pyridine-6-carboxylic acid, but is not limited thereto.

[0039] In one embodiment of the present application, the above-mentioned primary amine is selected from the group consisting of monoethanol amine, monoisopropanol amine, 2-amino-2-methyl-1-propanol, aminoethoxyethanol, and mixtures thereof, but is not limited thereto.

[0040] In one embodiment of the present application, the above-mentioned secondary amine is selected from the group consisting of 2-acetyl ethanolamine, diethanol amine, 2-methylaminoethanol, 2-isopropylaminoethanol, and mixtures thereof, but is not limited thereto.

[0041] In one embodiment of the present application, the content of the primary amine in the mixture of the primary amine and the secondary amine is less than 3% by weight, based on the total weight of the above-mentioned composition.

[0042] In one embodiment of the present application, the above-mentioned cyclic alcohol is selected from the group consisting of tetrahydrofurfuryl alcohol, furfuryl alcohol, isopropylidene glycerol, and mixtures thereof, but is not limited thereto.

[0043] In one embodiment of the present application, the aprotic polar organic solvent is selected from the group consisting of dimethylpropionamide, sulfolane, ethylformamide, 3-methyl-N,N-dimethylpropionamide (Equamide), 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, 1-formylpiperidine, and mixtures thereof, but is not limited thereto.

[0044] In one embodiment of the present application, the protic polar organic solvent is one or more selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (BDG), diethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, and tripropylene glycol monobutyl ether, but is not limited thereto.

[0045] Effects of the Invention

[0046] According to the present application, a stripping solution composition is provided, which uses the sulfur-free compound of the present application instead of a sulfur-based azole compound used as an anticorrosive agent in the past, and has excellent anticorrosive and stripping power for copper, aluminum, and oxide metal wires, regardless of the water content. This composition provides more excellent anticorrosive and stripping power, especially in the pattern edge portion of a copper wire that is easily corroded after dry etching. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 Pictures of (a) three-dimensional images, (b) surface roughness, and (c) line roughness measured using a high-performance roughness measuring instrument (confocal microscope) to confirm the metal corrosion performance of the embodiment of one embodiment of the present application.

[0048] Figure 2Pictures of (a) three-dimensional images, (b) surface roughness, (c) line roughness measured by a high-performance roughness measuring instrument (Confocal) for confirming the metal corrosion performance of the comparative example of the present application. DETAILED DESCRIPTION

[0049] The following examples are provided to more fully illustrate the present application. The examples can be modified in various different forms, and the scope of the present application is not limited to the following examples. The examples are provided to make the present application more complete and comprehensive, and to convey the idea of the present application to those skilled in the art.

[0050] In addition, the thickness or size of each layer in the drawings can be exaggerated for the purpose of explanation or clarity, and the same reference numerals in the drawings denote similar components. As used in the present specification, the term "and / or" means any one or all combinations of one or more of the associated listed items.

[0051] The terms used in the present specification are used to describe particular embodiments, and not to limit the present application. As used in the present specification, the singular form can include the plural form unless explicitly stated otherwise in the context. In addition, the terms "comprise" and / or "comprising," as used in the present specification, indicate the presence of the stated shapes, numbers, steps, operations, components, factors, and / or combinations thereof, and do not exclude the presence or addition of one or more other shapes, numbers, steps, operations, components, factors, and / or combinations.

[0052] In the present application, "alkyl" means a monovalent substituent derived from a straight chain or branched chain saturated hydrocarbon having 1 to 10 carbon atoms. Examples thereof can include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, etc., but are not limited thereto.

[0053] In the present application, "alkenyl" means a monovalent substituent derived from a straight chain or branched chain unsaturated hydrocarbon having 2 to 10 carbon atoms and having one or more carbon-carbon double bonds. Examples thereof can include vinyl, allyl, isopropenyl, 2-butenyl, etc., but are not limited thereto.

[0054] In the present application, "alkynyl" means a monovalent substituent derived from a straight chain or branched chain unsaturated hydrocarbon having 2 to 10 carbon atoms and having one or more carbon-carbon triple bonds. Examples thereof can include ethynyl, 2-propynyl, etc., but are not limited thereto.

[0055] In the present application, "aryl group" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 20 carbon atoms and having a single ring or a combination of two or more rings. In addition, a simple connection (pendant group) or a fused form of two or more rings can also be included. Examples of such aryl group can include phenyl, naphthyl, phenanthryl, anthryl, etc., but are not limited thereto.

[0056] In the present application, "heteroaryl group" means a monovalent substituent derived from a mono- or poly-heterocyclic aromatic hydrocarbon having 5 to 20 nuclear atoms. At this time, one or more carbon atoms, preferably 1 to 3 carbon atoms in the ring, are substituted with a heteroatom such as N, O, S, or Se. In addition, a simple connection (pendant group) or a fused form of two or more rings can also be included. In addition, a form fused with an aryl group can also be included. More specifically, in the present application, a heteroaryl group having 5 to 20 nuclear atoms containing one or more heteroatoms selected from the group consisting of N, O, and S is defined. Examples of such heteroaryl group can include a 6-membered monocyclic ring such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, or triazinyl; a polycyclic ring such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, or carbazolyl; and 2-furyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl, 2-pyrimidyl, etc., but are not limited thereto.

[0057] In the present application, "aryloxy group" means a monovalent substituent represented by RO-, the above R being an aryl group having 6 to 20 carbon atoms. Examples of such aryloxy group can include phenoxy, naphthoxy, diphenyloxy, etc., but are not limited thereto.

[0058] In the present application, "alkoxy group" means a monovalent substituent represented by R'O-, the above R' being an alkyl group having 1 to 10 carbon atoms, and can include a linear, branched, or cyclic structure. Examples of such alkoxy group can include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, etc., but are not limited thereto.

[0059] In the present application, "cycloalkyl group" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 10 carbon atoms. Examples of such cycloalkyl group can include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, etc., but are not limited thereto.

[0060] In the present invention, "heterocyclic alkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 10 nuclear type atoms, one or more carbon atoms, preferably 1 to 3 carbon atoms in the ring are substituted with a heteroatom such as N, O, S, or Se. Examples of such heterocyclic alkyl can include morpholine, piperazine, and the like, but are not limited thereto.

[0061] Hereinafter, preferred embodiments of the present invention will be described in detail.

[0062] As described above, the photoresist stripping solution composition of the present invention is a photoresist stripping solution composition for manufacturing a display, which includes:

[0063] (a) 0.01 to 3 wt% of a transition metal and metal oxide corrosion inhibitor of the following Chemical Formula 1;

[0064] (b) 0.05 to 3 wt% of a sulfur-free corrosion inhibitor of the following Chemical Formula 2;

[0065] (c) 1 to 10 wt% of a mixture of primary and secondary amines;

[0066] (d) 1 to 15 wt% of a cyclic alcohol;

[0067] (e) 1 to 30 wt% of an aprotic polar organic solvent;

[0068] (f) 1 to 30 wt% of a protic polar organic solvent; and

[0069] (g) the remaining amount of ultrapure water.

[0070] Chemical Formula 1:

[0071]

[0072] Chemical Formula 2:

[0073]

[0074] Chemical Formula 3:

[0075]

[0076] wherein T 1 or T 2 each independently is -O - NH4 + or -O-H;

[0077] T 3 is -O-R or -R`;

[0078] R and R' are each independently selected from hydrogen, methyl, straight-chain or branched C2-C. 12 Alkyl, straight-chain or branched C2-C 12 Alkenyl, straight-chain or branched C2-C 12 alkynyl group, C3~C 12 Cycloalkyl groups, heterocyclic alkyl groups having 3 to 10 nuclear atoms containing one or more heteroatoms selected from the group consisting of N, O, and S, C6–C 20 aryl, heteroaryl with 5 to 20 nuclear atoms including one or more heteroatoms selected from the group consisting of N, O and S, C1 to C 12 Alkyl groups and C6-C 12 In the group composed of aryl groups;

[0079] Ring A in chemical formula 2 is one of the structures in chemical formula 3;

[0080] R 1 R 2 and R 3 Choose from methyl, straight-chain or branched C2-C 12 Alkyl, straight-chain or branched C2-C 12 Alkenyl, straight-chain or branched C2-C 12 alkynyl group, C3~C 12 Cycloalkyl groups, heterocycloalkyl groups having 3 to 10 nuclear atoms containing one or more heteroatoms selected from the group consisting of N, O, and S, C6–C6 cycloalkyl groups. 20 aryl, heteroaryl with 5 to 20 nuclear atoms including one or more heteroatoms selected from the group consisting of N, O and S, C1 to C 12 Alkyl groups and C6-C 12 In the group composed of aryl groups;

[0081] * refers to the carbon atoms that form the pyridine ring of chemical formula 2, which are fused with ring A.

[0082] In one specific embodiment of the present invention, an aluminum corrosion inhibitor comprising 0.01 to 3 weight percent of the aforementioned alkali metal phosphate and alkali metal phosphonic acid of Formula 1 as transition metal corrosion inhibitors is used. This corrosion inhibitor is included to further improve the corrosion resistance to Mo, Al, etc., but when the content exceeds 3 weight percent, it enhances the corrosion resistance to copper due to its influence on the stripping agent and alkalinity; therefore, it is unnecessary to use excessive amounts of the aforementioned corrosion inhibitor.

[0083] Specifically, the sulfur-free compounds used in this invention, derived from chemical formulas 2 and 3, are selected from the group consisting of the following compounds:

[0084]

[0085] Among them, R 1, R 2 and R 3 as defined in Chemical Formula 2 and Chemical Formula 3 above.

[0086] In one embodiment of the present application, the photoresist stripping solution uses 0.05 to 3 weight percent of the above-described sulfur-free compound as a transition metal corrosion inhibitor. In the case of containing less than 0.05 weight percent of the corrosion inhibitor, the corrosion prevention effect for the metal wire film is reduced, and depending on the type of amine used, the corrosion prevention effect is not shown.

[0087] In addition, in one embodiment of the present application, when containing more than 3 weight percent of the corrosion inhibitor, it is confirmed that the tendency of the photoresist stripping ability is weakened, but the corrosion prevention force does not greatly change. However, in general, the sulfur-free compound used in the present application is very high in price, and it is not necessary to introduce more than a sufficient amount.

[0088] In one embodiment of the present application, as the primary amine compound used in the present application, one or more selected from the group consisting of monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, and aminoethoxyethanol can be used, but is not limited thereto.

[0089] In one embodiment of the present application, as the secondary amine compound used in the present application, one or more selected from the group consisting of 2-acetyloxyethanolamine, diethanolamine, 2-methylaminoethanol, and 2-isopropylaminoethanol can be used, but is not limited thereto.

[0090] In one embodiment of the present application, preferably, 1 to 10 weight percent of the mixture of the primary amine and the secondary amine used in the present application is used with respect to the entire composition. In addition, in one embodiment of the present application, the content of the primary amine in the mixture of the primary amine and the secondary amine is less than 3 weight percent based on the total weight of the composition.

[0091] In the case of using the above-described primary amine and secondary amine alone, or the content of the primary amine in the above-described amine mixture is 3 weight percent or more based on the total weight of the composition, the tendency that the stripping force is maintained but the corrosion prevention force is reduced is shown.

[0092] Cyclic alcohols are known to reduce the volatilization of the stripping solution, control the evaporation of the alkylol amine, which is one of the important effective components of the composition, and thus play a role in maintaining the efficacy of the composition for a long time. As the cyclic alcohols that can be used in the present application, for example, C4 to C6 cyclic alcohols can be used, and preferably, one or more selected from the group consisting of tetrahydrofurfuryl alcohol, furfuryl alcohol, cyclobutanol, cyclopentanol, cyclohexanol, and isopropylidene glycerol, but are not limited thereto.

[0093] Preferably, 1 to 15 weight percent of the above cyclic alcohol is contained with respect to the entire composition. Generally, such cyclic alcohols are very expensive, and it is not necessary to introduce more than a sufficient amount.

[0094] In a specific example of the present application, the aprotic polar organic solvent used in the present application is known to play a role in weakening the binding force of the high molecular substance to easily remove the denatured photoresist. In the specific example of the present application, as the aprotic polar organic solvent used in the present application, one or more selected from the group consisting of dimethylpropionamide, sulfolane, ethyl formamide, 3-methyl-N,N-dimethylpropionamide (Equamide), 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone, and 1-formylpiperidine, and mixtures thereof, but are not limited thereto.

[0095] Preferably, 1 to 30 weight percent of the above polar organic solvent is contained with respect to the entire composition.

[0096] In a specific example of the present application, one or more glycol compounds can be used in mixture as the protic polar organic solvent, which is known to effectively assist in stripping the photoresist. Also, the glycol compound plays a role in diffusing the dissolved photoresist well into the stripper and contributes to rapid removal thereof.

[0097] In a specific example of the present application, the glycol compound used in the present application can be used alone or in mixture with C1 to C6 alkylene glycols, C1 to C6 alkyl ether compounds of C1 to C6 alkylene glycols, or C1 to C6 alkyl ether acetate compounds of C1 to C6 alkylene glycols, etc., but is not limited thereto. In a specific example of the present application, the C1 to C6 alkylene glycol used in the present application can be used alone or in mixture with ethylene glycol, propylene glycol, or butylene glycol, etc., but is not limited thereto.

[0098] In a specific example of the present application, the C1-C6 alkyl ether compound of the C1-C6 alkylene glycol used in the present application can use ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dibutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, triethylene glycol monoethyl ether, triethylene glycol diethyl ether, triethylene glycol monobutyl ether, or triethylene glycol dibutyl ether, etc., alone or in mixture, but is not limited thereto.

[0099] In a specific example of the present application, the C1-C6 alkyl ether acetate compound of the C1-C6 alkylene glycol used in the present application can be used alone or in a mixture of ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, or the like, but is not limited thereto.

[0100] In a specific example of the present application, more preferably, diethylene glycol monomethyl ether (MDG), diethylene glycol monoethyl ether (EDG), diethylene glycol monobutyl ether (BDG), triethylene glycol ether (TEG), ethylene glycol (EG), or propylene glycol (PG), or the like can be used as a glycol compound.

[0101] Preferably, 1 to 30 weight percent of such a glycol compound is included with respect to the entire composition.

[0102] The photoresist stripping solution composition of the present application is an aqueous solution including water. The aqueous stripping solution including water further activates the basicity of the amine compared to the organic stripping solution. Accordingly, in the manufacturing process of the flat display panel, the removal ability of the denatured photoresist remaining after the hard-baking process, the injection process, and the dry etching process is also remarkably excellent in the low process temperature compared to the stripping solution commonly used for the manufacturing of the organic display.

[0103] The application of the low process temperature can reduce the manufacturing cost of the flat display panel. Also, for the stripping solution composition of the present application, the optimal corrosion inhibitor can be used to be simultaneously applicable to the aluminum wire and the copper wire, and can be introduced into the organic film and the COA process.

[0104] Hereinafter, the present application will be described in more detail through examples. These examples are only for exemplifying the present application, and the scope of the present application should not be construed as being limited to these examples, which will be apparent to those skilled in the art.

[0105] Experimental Example 1.

[0106] Evaluation of metal corrosion and resist stripping

[0107] A test for evaluating the performance of the photoresist stripping liquid composition of the present application was performed by a method as follows. The stripping liquid composition of the present application was prepared by including an inhibitor containing a sulfur-free compound, and the specific composition ingredients and contents are described in Table 1 below. The specific composition ingredients and contents of the composition prepared in the comparative example are described in Table 2.

[0108] More specifically, a metal film wire glass substrate without removing photoresist was manufactured by heat treatment at a temperature of 160°C in an oven. The manufactured stripping liquid composition was maintained at a predetermined temperature, and the manufactured substrate was immersed in the stripping liquid composition for the same time, thereby evaluating the removal degree of the deteriorated photoresist. Also, the stripping liquid composition was maintained at a predetermined temperature, and the Cu metal film wire glass substrate was immersed in the stripping liquid composition for the same time, thereby evaluating whether the Cu wire film was corroded.

[0109] The above experimental result values are described in Table 3 with the following criteria.

[0110] [Stripping force of deteriorated photoresist]

[0111] : Deteriorated photoresist was completely removed

[0112] : Trace of deteriorated photoresist remained

[0113] : Deteriorated photoresist remained 30% or more

[0114] [Corrosion degree of Cu wire]

[0115] : No corrosion was observed on the surface of the metal film material to the same degree as the reference

[0116] : The thickness of the metal film material was not reduced, but abnormal phenomena were observed on the surface

[0117] : The thickness of the metal film material was reduced, and abnormal phenomena were observed on the surface

[0118] The abbreviations of the compounds used in the present application are as follows:

[0119] MIPA: Monoisopropanol amine

[0120] AEE: 2-(2-Aminoethoxy)ethanol

[0121] DEA: Diethanolamine

[0122] NMEA: N-Methylethanolamine

[0123] IPG: 1,2-Isopropylideneglycerol

[0124] EDG: Diethyleneglycolmonoethylether

[0125] DMPA: N,N-Dimethylpropionamide

[0126] NEF: N-Ethylformamide

[0127] BPA: Butylphosphonic acid

[0128] HPA: Hexylphosphonic acid

[0129] PD-A: 5-Methylimidazo[l,2-a]pyridine-2-carboxylic acid

[0130] PD-B: 3-Methyl-lH-pyrazolo[3,4-b]pyridine

[0131] PD-C: l,2,3-Triazolo[4,5-b]pyridine

[0132] MMI: Mercaptomethylimidazole

[0133] MBI: Mercaptobenzimidazole

[0134] MBO: Mercaptobenzoxazole

[0135] Table 1

[0136]

[0137] Table 2

[0138]

[0139] Table 3

[0140]

[0141] As shown in Table 3 above, in the case of the stripping solution containing the sulfur-free compound of the present application as the corrosion inhibitor, the corrosion resistance and the resist stripping power were confirmed to be improved compared to the use of the existing sulfur-based corrosion inhibitor.

[0142] Also, as shown in the results of Examples, Comparative Example 25 and Comparative Example 26, when the primary amine and the secondary amine are used in combination, a better corrosion resistance tendency is shown compared to the use of the primary amine or the secondary amine alone, and as Comparative Examples 23 and 24, in the case where the content of the primary amine in the amine mixture is 3% by weight or more based on the total weight of the composition, a tendency to maintain the stripping power but reduce the corrosion resistance is shown.

[0143] Also, as Comparative Example 21, it was confirmed that in the case where the content of the sulfur-free compound used as the corrosion inhibitor is 0.05% or less, the corrosion resistance is not good.

[0144] Experimental Example 2.

[0145] Roughness evaluation on metal corrosion

[0146] Generally, when evaluating metal corrosion, a field emission scanning electron microscope (FE-SEM) is used to observe the degree of corrosion. In order to more accurately confirm the metal corrosion resistance, a high-performance roughness measuring instrument (confocal microscope) is used for evaluation. A brief description of the analysis device is as follows.

[0147] A confocal microscope is a non-contact analysis device that measures surface roughness with higher resolution than conventional optical microscopes. As an illumination method, it has a reflection type and a projection type, and the type used for industrial purposes is mainly the reflection type. Thus, for a sample surface having concave and convex portions, a high-resolution image focused on the entire field of view can be obtained, and three-dimensional shape measurement can also be performed non-destructively and non-contactly.

[0148] Thus, if the surface roughness of the edge portion of the copper wire pattern susceptible to corrosion after dry etching is measured, the corrosion resistance level can be more accurately confirmed.

[0149] The abbreviations of the above experiments are as follows.

[0150] S-(Sv, Sz, Sa): Surface roughness

[0151] R-(Rv, Rz, Ra): Line roughness

[0152] -v (Sv, Rv): Maximum groove valley height

[0153] - z (Sz, Rz): 10 point average roughness

[0154] - a (Sa, Ra): center line average

[0155] The similar levels of the components of the above-described examples and comparative examples are as follows.

[0156] Table 4

[0157]

[0158] Table 5

[0159]

[0160] Meanwhile, Figure 1 and Figure 2 are images that can be confirmed together when measuring the surface roughness. Figure 1 Corresponding to Example 8, Figure 2 Corresponding to Comparative Example 16.

[0161] As shown in Table 5 above, it can be confirmed that the composition of the example of the present application shows a lower value of the roughness number compared to the composition of the comparative example. Therefore, in the case where the composition of the present application is used as a stripping solution, it can be confirmed that the corrosion prevention power is further improved.

[0162] The present application has been described above centering on preferred examples. It is understood by those skilled in the art to which the present application pertains that the present application can be implemented in modified forms within the scope of the essential characteristics of the present application.

Claims

1. A photoresist stripper composition for manufacturing a display, characterized by, comprising: (a) 0.01 to 3 wt% of a transition metal and metal oxide corrosion inhibitor; (b) 0.05 to 3 wt% of a sulfur-free corrosion inhibitor; (c) 1 to 10 wt% of a mixture of primary and secondary amines; (d) 1 to 15 wt% of a cyclic alcohol; (e) 1 to 30 wt% of an aprotic polar organic solvent; (f) 1 to 30 wt% of a protic polar organic solvent; and (g) the balance of ultrapure water, wherein the transition metal and metal oxide corrosion inhibitor is one or more selected from the group consisting of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, methyl phosphonic acid, ethyl phosphonic acid, propyl phosphonic acid, butyl phosphonic acid, t-butyl phosphonic acid, pentyl phosphonic acid, n-hexyl phosphonic acid, triethyl phosphate, octyl phosphonic acid, decyl phosphonic acid, dodecyl phosphonic acid, tetradecyl phosphonic acid, octadecyl phosphonic acid, hexyl phosphate, heptyl phosphate, octyl phosphate, nonyl phosphate, decyl phosphate, and dodecyl phosphate, wherein the sulfur-free corrosion inhibitor is one or more selected from the group consisting of imidazo[4,5-b]pyridine, 6-methylimidazo[4,5-b]pyridine, imidazo[4,5-b]pyridine-2-carboxylic acid, 6-methylimidazo[4,5-b]pyridine-2-carboxylic acid, 1H-pyrazolo[3,4-b]pyridine, 3-methyl-1H-pyrazolo[3,4-b]pyridine, 1H-pyrazolo[3,4-b]pyridine-3-carboxylic acid, and 5-methyl-1H-pyrazolo[3,4-b]pyridine-3-carboxylic acid, wherein the content of primary amines in the mixture of primary and secondary amines is less than 3 wt% based on the total weight of the composition.

2. The photoresist stripping liquid composition for manufacturing a display according to claim 1, characterized in that, The primary amines are selected from the group consisting of monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, aminoethoxyethanol, and mixtures thereof.

3. The photoresist stripping liquid composition for manufacturing a display according to claim 1, wherein The secondary amines are selected from the group consisting of 2-acetyloxyethanolamine, diethanolamine, 2-methylaminoethanol, 2-isopropylaminoethanol, and mixtures thereof.

4. The photoresist stripping liquid composition for manufacturing a display according to claim 1, wherein The cyclic alcohol is selected from the group consisting of tetrahydrofurfuryl alcohol, furfuryl alcohol, isopropylidene glycerol, and mixtures thereof.

5. The photoresist stripping liquid composition for manufacturing a display according to claim 1, wherein The aprotic polar organic solvent is selected from the group consisting of dimethylpropionamide, sulfolane, ethylformamide, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone, and 1-formylpiperidine, and mixtures thereof.

6. The photoresist stripping liquid composition for manufacturing a display according to claim 1, wherein The protic polar organic solvent is one or more selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, and tripropylene glycol monobutyl ether.

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