Release agent composition and method for forming pattern using release agent composition

Abstract

The invention relates to a release agent composition and a method for forming a pattern using the release agent composition. The stripper composition includes an amine compound, a diol compound, an aprotic polar solvent other than N-methyl-2-pyrrolidone and N-methylformamide, and a first corrosion inhibitor represented by Formula 1 in set content ranges. The release agent composition according to an embodiment can be used in a process for removing a photoresist pattern formed on a lower film, and can provide excellent release ability to a photoresist and characteristics of preventing or reducing damage to the lower film.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2023-0151021 filed in the Korean Intellectual Property Office on November 3, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] Embodiments of the present disclosure herein relate to a stripper composition and a method of forming a pattern using the stripper composition, and, for example, to a stripper composition for removing a photoresist and a method of forming a pattern using the stripper composition. Background Art

[0004] A photolithography process using a photoresist is performed in a semiconductor manufacturing process or a panel process of a display device. For example, a photoresist pattern may be formed by forming a photoresist layer on a substrate, and exposing and developing the photoresist layer.

[0005] Stripper compositions are used to remove photoresist patterns in photoetching processes. Some environmental control materials are included in general stripper compositions. Accordingly, it is necessary to develop a technology for stripper compositions that do not include these environmental control materials and have excellent photoresist pattern removal capabilities. Summary of the invention

[0006] Embodiments of the present disclosure provide a stripper composition having improved stripping ability of a photoresist pattern and improved performance of dissolving the photoresist pattern while minimizing or reducing corrosion of an underlying film of the photoresist pattern.

[0007] Embodiments of the present disclosure also provide a method for forming a pattern using the above-mentioned stripper composition.

[0008] Embodiments of the present disclosure provide a stripper composition, which includes, relative to the total weight of the stripper composition, about 1 wt % to about 30 wt % of an amine compound, about 5 wt % to about 60 wt % of a diol compound, about 20 wt % to about 70 wt % of an aprotic polar solvent other than N-methyl-2-pyrrolidone and N-methylformamide, and about 0.001 wt % to about 20 wt % of a first corrosion inhibitor represented by Formula 1.

[0009] Formula 1

[0010]

[0011] In Formula 1, n is an integer of 1 to 6.

[0012] In an embodiment, the amine compound may include monoethanolamine, methylethanolamine, diethanolamine, triethanolamine, propanolamine, aminoethanol, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, N-methyldiethanolamine, N,N-dimethylethanolamine, 2-diethylaminoethanol, 2-(2-aminoethylamino)ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, N-(methoxymethyl)diethylamine, (isobutoxymethyl)dimethylamine, 2-(2-aminoethoxy)ethanol, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine Gutin, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, diethylenetriamine, triethylenetetramine, propylenediamine, tetraethylenepentamine, N,N-diethylethylenediamine, 1,4-butanediamine, N-ethylethylenediamine, 1 , at least one of 2-propylenediamine, 1,3-propylenediamine, adipic acid amide, piperazine, N-methylpiperazine, N-ethylpiperazine, N-propylpiperazine, N-butylpiperazine, 1-pentylpiperazine, 1-hexylpiperazine, acryloylpiperazine, N-acryloyl-N'-methylpiperazine, hydroxyethylpiperazine, N-(2-aminoethyl)piperazine, N,N'-dimethylpiperazine, aniline, benzylamine, N,N-dimethylaniline and diphenylamine.

[0013] In an embodiment, the amine compound may include a primary amine compound.

[0014] In an embodiment, the amine compound may include at least one of an alkanolamine compound and an alkoxyamine compound, and a weight ratio of the alkanolamine compound to the alkoxyamine compound is about 1:0.5 to about 1:5.

[0015] In an embodiment, the amine compound may be included in an amount of greater than about 5 wt % to about 30 wt % with respect to the total weight of the stripper composition.

[0016] In an embodiment, the glycol compound may include at least one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether.

[0017] In an embodiment, the aprotic polar solvent may include an amide-based solvent.

[0018] In an embodiment, the aprotic polar solvent may include at least one of formamide, N-ethylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylpropionamide, dimethyl sulfoxide, diethyl sulfoxide, dipropylene sulfoxide, cyclopentane, 2-pyrrolidone, N-ethyl-2-pyrrolidone and N-(2-hydroxyethyl)-2-pyrrolidone.

[0019] In an embodiment, the first corrosion inhibitor represented by Chemical Formula 1 may be included in an amount of about 5 wt % to about 10 wt % with respect to the total weight of the stripper composition.

[0020] In an embodiment, in Chemical Formula 1, n may be an integer of 1 to 4.

[0021] In an embodiment, the first corrosion inhibitor represented by Formula 1 may include at least one of glycerol, threitol, ribitol, xylitol, sorbitol, mannitol, and galactitol.

[0022] In an embodiment, the stripper composition may further include an additive, wherein the additive may include at least one of a surfactant, an antioxidant, and a stabilizer.

[0023] In embodiments, the stripper composition may not include water.

[0024] In an embodiment, the stripper composition may have a specific gravity of about 1.01 or more.

[0025] In an embodiment disclosed in the present invention, a method for forming a pattern includes: forming a photoresist pattern on a substrate having a lower film formed thereon, forming a line pattern using the photoresist pattern, and removing the photoresist pattern by providing a stripper composition, and the above-mentioned stripper composition is used to remove the photoresist pattern.

[0026] In an embodiment, the lower film may include a metal film including aluminum (Al), copper (Cu), or an alloy thereof, a non-metal oxide film including a silicon oxide film and / or a silicon oxynitride film, or a combination thereof.

[0027] In an embodiment, the lower film may be a single film or a plurality of films. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The accompanying drawings are included to provide a further understanding of the subject matter of the present disclosure and are incorporated in and constitute a part of this specification. The accompanying drawings illustrate embodiments of the present disclosure and, together with the description, serve to explain the principles of the present disclosure. In the drawings:

[0029] Figure 1 A flowchart for explaining a method for forming a pattern according to an embodiment; and

[0030] Figure 2 to Figure 6 Each is a cross-sectional view schematically illustrating a method for forming a pattern according to an embodiment of the present disclosure. DETAILED DESCRIPTION

[0031] In the embodiments of the present disclosure, various suitable modifications can be made, and various suitable forms can be applied, and example embodiments will be explained in the drawings and described in more detail in the text. However, this is not intended to limit the present disclosure to a specific disclosure form, and it should be understood to include all changes, equivalents and alternatives included in the spirit and scope of the present disclosure.

[0032] When describing each figure, similar reference numerals have been used for similar elements. In the attached drawings, for the clarity of the subject matter of the present disclosure, the dimensions of the structure may be enlarged and shown instead of showing the actual size. Terms such as first and second can be used to describe various components, but the components should not be limited by these terms. These terms are only used to distinguish the purpose of one component from another component. For example, without departing from the scope of the present disclosure, the first component may be referred to as the second component, and similarly, the second component may be referred to as the first component. Unless the context clearly indicates otherwise, the singular expression includes the plural expression.

[0033] In the present application, terms such as "include" or "have" are intended to mark the presence of features, quantities, steps, actions, components, parts or combinations thereof described in the specification. It should be understood that the possibility of the presence or addition of one or more other features, quantities, steps, actions, components, parts or combinations thereof is not precluded.

[0034] In the present application, when a component such as a layer, film, region or plate is referred to as being "on" ... "on" or "on" another component, this includes not only being "directly on" another component but also being in the middle (e.g., between the component and the other component). Conversely, when a component such as a layer, film, region or plate is referred to as being "under" ... "under" or "under" another component, this includes not only being "directly under" another component but also being in the middle (e.g., between the component and the other component). In the present application, the term "above" may include the case where it is provided not only on the top but also on the bottom.

[0035] Hereinafter, a stripper composition according to an embodiment of the present disclosure will be described.

[0036] The stripper composition according to the embodiment can be used to strip the photoresist pattern formed on the lower film thereof. The stripper composition according to the embodiment can be used to strip the photoresist pattern formed on the metal film and / or the non-metal oxide film. In an embodiment, the stripper composition can be used to strip the photoresist pattern on the lower film which is a combination of a metal film and a non-metal oxide film. The lower film of the photoresist pattern may include a metal film, a non-metal oxide film, or a combination thereof, and may be a single film or a plurality of films.

[0037] The stripper composition according to an embodiment of the present disclosure may include an amine compound, a diol compound, an aprotic polar solvent, and a first corrosion inhibitor. The stripper composition according to an embodiment may further include an additive. However, the stripper composition according to an embodiment may not include N-methyl-2-pyrrolidone and N-methylformamide.

[0038] The amine compound included in the stripper composition according to the embodiment can be used to weaken the bonding force of the photoresist pattern. For example, the intermolecular bonding in the cured photoresist resin can be destroyed or reduced by the amine compound. Accordingly, the stripper composition including the amine compound can have the characteristic of being able to easily strip the photoresist pattern.

[0039] In an embodiment, the amine compound may include at least one hydroxyl group, or may include an oxygen group. For example, the amine compound may include an alkanolamine compound including one hydroxyl group. The hydroxyl group in the alkanolamine compound may be located at the end or side chain of the amine compound. In an embodiment, the amine compound may include an alkoxyamine compound including an alkoxy group. However, embodiments of the present disclosure are not limited thereto, and the amine compound according to the embodiment may include a cyclic amine compound.

[0040] The amine compound according to the embodiment may include at least one of an alkanolamine compound and an alkoxyamine compound. For example, the amine compound may include an alkanolamine compound or an alkoxyamine compound. In an embodiment, the amine compound may include both an alkanolamine compound and an alkoxyamine compound. When the stripper composition according to the embodiment includes both an alkanolamine compound and an alkoxyamine compound, the alkanolamine compound and the alkoxyamine compound may be included in a weight ratio of 1:0.5 to 1:5. For example, the alkanolamine compound and the alkoxyamine compound may be included in a weight ratio of 1:1 to 1:3.

[0041] In this specification, an oxy group may mean a group in which an oxygen atom is bonded to an alkyl group or an aryl group. The oxy group may include an alkoxy group and an aryloxy group. The alkoxy group may be linear, branched or cyclic. The carbon number of the alkoxy group is not particularly limited, but, for example, may be 1 to 20 or 1 to 10. Examples of the oxy group are methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, octyloxy, nonyloxy, decyloxy, benzyloxy, etc., but are not limited thereto.

[0042] In the present specification, the alkyl group may be linear, branched or cyclic. The carbon number of the alkyl group is 1 to 50, 1 to 30, 1 to 20, 1 to 10 or 1 to 6. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n- Undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, and the like, but are not limited thereto.

[0043] In this specification, aryl means any functional group or substituent (for example, any suitable functional group or substituent) derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. The ring carbon number of the aryl group may be 6 to 30, 6 to 20 or 6 to 15. Examples of aryl groups may be phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, quaterphenyl, pentaphenyl, hexaphenyl, triphenylene, pyrenyl, benzofluoranthenyl, 1,2-triphenylenyl, etc., but are not limited thereto.

[0044] In the present specification, the cyclic amine compound means an amine compound derived from a ring including at least one nitrogen (N) atom as a ring-forming atom. The cyclic amine compound may be derived from an aliphatic heterocycle or an aromatic heterocycle including at least one nitrogen (N) atom as a ring-forming atom. The aliphatic heterocycle and the aromatic heterocycle may be monocyclic or polycyclic.

[0045] In an embodiment, the amine compound may include monoethanolamine, methylethanolamine, diethanolamine, triethanolamine, propanolamine, aminoethanol, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, N-methyldiethanolamine, N,N-dimethylethanolamine, 2-diethylaminoethanol, 2-(2-aminoethylamino)ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, N-(methoxymethyl)diethylamine, (isobutoxymethyl)dimethylamine, 2-(2-aminoethoxy)ethanol, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine Gutin, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, diethylenetriamine, triethylenetetramine, propylenediamine, tetraethylenepentamine, N,N-diethylethylenediamine, 1,4-butanediamine, N-ethylethylenediamine, 1 , at least one of 2-propylenediamine, 1,3-propylenediamine, adipic acid amide, piperazine, N-methylpiperazine, N-ethylpiperazine, N-propylpiperazine, N-butylpiperazine, 1-pentylpiperazine, 1-hexylpiperazine, acryloylpiperazine, N-acryloyl-N'-methylpiperazine, hydroxyethylpiperazine, N-(2-aminoethyl)piperazine, N,N'-dimethylpiperazine, aniline, benzylamine, N,N-dimethylaniline and diphenylamine.

[0046] The amine compound included in the stripper composition according to the embodiment may include a primary amine compound. For example, the stripper composition may include at least one of monoethanolamine and 2-(2-aminoethoxy)ethanol as the amine compound. However, the embodiments of the present disclosure are not limited thereto. For example, at least one of a secondary amine compound, a tertiary amine compound, and a cyclic amine compound may be further included.

[0047] In an embodiment, the content of the amine compound may be from about 1 wt % to about 30 wt % relative to the gross weight of the stripper composition. For example, the amine compound may be included in the stripper composition according to the embodiment in an amount greater than about 5 wt % to about 30 wt %, about 5 wt % to about 20 wt %, or about 5 wt % to about 15 wt %. When the content of the amine compound is less than about 1 wt %, the stripper composition may be difficult to fully demonstrate stripping performance, and substrate stains may be generated due to poor rinsing. When the content of the amine compound exceeds about 30 wt %, the lower film of the photoresist pattern may be damaged.

[0048] The stripper composition according to an embodiment of the present disclosure may include a diol compound. The stripper composition may include at least one (e.g., two) types (or species) of diol compounds. The diol compound may improve the wettability to the photoresist, and may improve the solubility of the stripped photoresist. In an embodiment, the diol compound may be used to prevent or reduce the stripped photoresist from being adsorbed again on the lower film. Accordingly, the stripper composition according to an embodiment including the diol compound may provide excellent stripping ability and excellent rinsing ability for the photoresist.

[0049] For example, the glycol compound may include at least one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (EDG), diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether.

[0050] The stripper composition according to the embodiment may include at least one of diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether as the diol compound. For example, the stripper composition according to the embodiment may include diethylene glycol monoethyl ether or dipropylene glycol monomethyl ether as the diol compound. In an embodiment, the diol compound may include both diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether.

[0051] When the stripper composition according to the embodiment includes both diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether as the glycol compound, the content of diethylene glycol monoethyl ether included in the stripper composition may be the same as or greater than the content of dipropylene glycol monomethyl ether. In an embodiment, the stripper composition may include diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether in a weight ratio of 1:1 to 3:1. For example, the stripper composition may include diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether in a weight ratio of 2:1 to 3:1. When diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether are included in the stripper composition in such a weight ratio, the stripping ability and the washing ability of the photoresist may be improved.

[0052] In an embodiment, the content of the diol compound may be about 5% by weight to about 60% by weight relative to the gross weight of the stripper composition. For example, the diol compound may be included in the stripper composition according to the embodiment in an amount of about 10% by weight to about 50% by weight, about 15% by weight to about 40% by weight, about 20% by weight to about 40% by weight, or about 25% by weight to about 40% by weight. When the diol compound is included in the stripper composition in the above-mentioned content range, the surface tension of the stripper composition may be reduced, thereby improving the wettability of the photoresist, the stripping ability of the photoresist, and the solubility of the stripped photoresist. When the content of the diol compound is less than about 5% by weight, the stripper composition may be difficult to exhibit stripping performance, and substrate stains may be generated due to poor rinsing. When the content of the diol compound is greater than about 60% by weight, the solubility of the photoresist may be degraded or reduced.

[0053] The stripper composition according to the embodiment may include a non-protonic polar solvent. The non-protonic polar solvent can be used to improve the solubility of the stripped photoresist pattern. In an embodiment, the non-protonic polar solvent can help improve the specific gravity of the stripper composition. Accordingly, the stripper composition according to the embodiment including the non-protonic polar solvent can easily remove the photoresist pattern modified by curing, thereby maximizing or increasing the stripping ability and cleaning ability of the photoresist pattern.

[0054] As long as it has excellent solubility for the stripped photoresist pattern, the aprotic polar solvent can be used without any particular limitation, but may not include harmful materials. For example, the aprotic polar solvent may not include N-methyl-2-pyrrolidone and N-methylformamide, which are harmful to the environment and human body. For example, the stripper composition according to the embodiment can improve the performance of dissolving the stripped photoresist pattern without using N-methyl-2-pyrrolidone and N-methylformamide, which are harmful materials, as the aprotic polar solvent.

[0055] For example, the aprotic polar solvent may include at least one of N-ethylformamide, formamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylpropionamide, dimethyl sulfoxide, diethyl sulfoxide, dipropylene sulfoxide, cyclopentane, 2-pyrrolidone, N-ethyl-2-pyrrolidone and N-(2-hydroxyethyl)-2-pyrrolidone. These may be used alone or in combination of two or more types (or species).

[0056] In an embodiment, the stripper composition may include an amide solvent as an aprotic polar solvent. For example, the aprotic polar solvent may include N-ethylformamide, but the embodiments of the present disclosure are not limited thereto. For example, the stripper composition according to the embodiment may further include formamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylpropionamide, dimethyl sulfoxide, diethyl sulfoxide, dipropylene sulfoxide, cyclopentane, 2-pyrrolidone, N-ethyl-2-pyrrolidone and at least one of N-(2-hydroxyethyl)-2-pyrrolidone.

[0057] In an embodiment, the content of the aprotic polar solvent may be about 20 wt % to about 70 wt % relative to the gross weight of the stripper composition. For example, the content of the aprotic polar solvent may be about 30 wt % to about 70 wt %, about 40 wt % to about 70 wt %, or about 40 wt % to about 60 wt %. When the aprotic polar solvent is included in the stripper composition in the above-mentioned content range, the excellent stripping ability of the cured and / or modified photoresist and the solubility of the stripped photoresist can be maximized or increased. In an embodiment, the specific gravity of the stripper composition may be equal to or greater than about 1.01. When the content of the aprotic polar solvent is less than about 20 wt %, the ability to remove the modified photoresist may be insufficient. When the content of the aprotic polar solvent is greater than about 70 wt %, the stripping performance may be degraded or reduced due to the reduction of the wettability of the stripper composition.

[0058] The stripper composition according to the embodiment may include a straight-chain corrosion inhibitor. The straight-chain corrosion inhibitor may be represented by the following formula 1. The straight-chain corrosion inhibitor represented by formula 1 can well maintain the stripping ability of the stripper composition while effectively inhibiting or reducing the corrosion of the lower film (such as a metal film (e.g., aluminum wire)). In this specification, the straight-chain corrosion inhibitor may be referred to as a "first corrosion inhibitor".

[0059] Formula 1

[0060]

[0061] In Formula 1, n may be an integer of 1 to 6. For example, n may be an integer of 1 to 4. The first corrosion inhibitor represented by Chemical Formula 1 includes all racemates and stereoisomers thereof.

[0062] In an embodiment, the first corrosion inhibitor may include at least one of glycerol, threitol, ribitol, xylitol, sorbitol, mannitol, and galactitol. For example, the stripper composition according to the embodiment may include glycerol, threitol, ribitol, xylitol, sorbitol, mannitol, and galactitol as the first corrosion inhibitor. Threitol may include D-threitol and L-threitol. However, embodiments of the present disclosure are not limited thereto.

[0063] In an embodiment, the first corrosion inhibitor content may be about 0.001 wt % to about 20 wt % relative to the total weight of the stripper composition. For example, the first corrosion inhibitor may be included in the stripper composition in an amount of about 0.01 wt % to about 10 wt %, about 0.1 wt % to about 10 wt %, about 0.01 wt % to about 5 wt %, about 0.01 wt % to about 3 wt %, about 5 wt % to about 10 wt %, or about 3 wt % to about 5 wt %. The first corrosion inhibitor may inhibit or reduce the corrosion of the lower film while providing sufficient stripping ability to the photoresist pattern within the above content range. For example, a stripper composition according to an embodiment including the first corrosion inhibitor within the above content range may selectively only rapidly strip the photoresist pattern without leaving stains and / or damage on the lower film. When the content of the first corrosion inhibitor is less than about 0.001 wt %, the corrosion inhibition ability of the metal film and the non-metal oxide film as the lower film may not be fully demonstrated. When the content of the first corrosion inhibitor is greater than about 20 wt %, stripping ability of the photoresist pattern may be deteriorated or reduced.

[0064] The stripper composition according to the embodiment may include an additive, an amine compound, a diol compound, an aprotic polar solvent, and a first corrosion inhibitor. The additive may further include at least one of a surfactant, an antioxidant, and a stabilizer.

[0065] Surfactants may be included in the stripper composition to improve the wettability and bubble characteristics of the stripper composition and to increase the solubility of the components included in the stripper composition. The surfactant may include at least one of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. The surfactant may be used without any particular limitation as long as it does not deteriorate or reduce (or substantially does not deteriorate or reduce) the performance of the stripper composition according to the embodiment.

[0066] In an embodiment, the surfactant may be added in an amount of greater than about 0.0005 wt % to less than about 5 wt % relative to the total weight of the stripper composition. For example, the surfactant may be added to the stripper composition according to the embodiment in an amount of about 0.001 wt % to about 2 wt % relative to the total weight of the stripper composition. When the content of the surfactant is equal to or less than about 0.0005 wt % relative to the total weight of the stripper composition, the effect of improving the wettability of the stripper composition, etc., may not be expected, and when the content of the surfactant is equal to or greater than about 5 wt %, solubility limitations and / or process limitations caused by generating too many bubbles may occur.

[0067] An antioxidant may be included in the stripper composition according to the embodiment in order to protect the metal and / or metal compound used as the material of the semiconductor element. The antioxidant may be used without any limitation as long as it is used in the technical field of the stripper composition, and may be added in an amount of about 0.01 wt % to about 10 wt % relative to the total weight of the stripper composition.

[0068] Stabilizers may be included to inhibit or reduce the generation of side reactions and / or byproducts that may result from unwanted reactions in the subject of application.

[0069] The stripper composition according to an embodiment of the present disclosure may not include water. For example, the stripper composition according to an embodiment may be a non-aqueous stripper composition. The water may include deionized water (ultrapure water).

[0070] The stripper composition according to the embodiment can be used in a process for manufacturing an electronic device, for example, a process for removing a photoresist pattern thereof. As an example, the electronic device may include a display device, and the stripper composition according to the embodiment can be used in a process for manufacturing an array substrate in a process for manufacturing a display device, and can be used in a process for removing a photoresist pattern formed on a metal film and / or a non-metal oxide film.

[0071] In an embodiment, the photoresist pattern can be removed by any appropriate stripping equipment using the stripper composition. Polyvinyl butyral can be used as a glass adhesive in the stripping equipment. When polyvinyl butyral is exposed to the stripper composition for a long time, during the process, the polyvinyl butyral may melt and fall on the substrate on which the lower film is formed. In this case, when the polyvinyl butyral has a larger specific gravity than the stripper composition, the polyvinyl butyral may be adsorbed on the substrate to be generated as a foreign matter.

[0072] In order to prevent or reduce the generation of polyvinyl butyral as a foreign matter, the stripper composition according to an embodiment of the present disclosure may have a greater specific gravity than polyvinyl butyral. For example, the stripper composition according to the embodiment may include a protic polar solvent and the above-mentioned non-protic polar solvent to have a greater specific gravity than polyvinyl butyral. For example, because polyvinyl butyral has a specific gravity of about 1.00, the stripper composition according to the embodiment may have a specific gravity of about 1.01 or greater. Accordingly, when using the stripper composition according to the embodiment, the adsorption of polyvinyl butyral on a substrate on which a lower film is formed during the process can be prevented or reduced, thereby reducing the risk of product failure due to the generation of foreign matter.

[0073] Hereinafter, a method of manufacturing an array substrate according to an embodiment of the present disclosure will be described with reference to the accompanying drawings. The method of manufacturing an array substrate may use the above-described stripper composition according to an embodiment.

[0074] Figure 1 The flowchart schematically illustrates a method for forming a pattern according to an embodiment. Figure 2 to Figure 6 A method for forming a pattern according to an embodiment is schematically explained. Figure 2 to Figure 6 The configurations illustrated in the drawings may be illustrated exaggeratedly and may have sizes different from their actual sizes.

[0075] refer to Figure 1 , the method for forming a pattern according to an embodiment may include an operation of forming a photoresist pattern on a lower film (S100), an operation of forming a line pattern from the lower film (S200), and an operation of removing the photoresist pattern by providing a stripper composition (S300).

[0076] refer to Figure 1 and Figure 2 , a lower film BL may be formed on the substrate BS, and a photoresist film P-PR may be formed on the lower film BL. The substrate BS may be a member providing a base surface on which the lower film BL is provided. The substrate BS may be a glass substrate, a metal substrate, and / or a plastic substrate, etc. However, the embodiments of the present disclosure are not limited thereto, and the substrate BS may be an inorganic layer, an organic layer, or a composite material layer. In an embodiment, the substrate BS may include a semiconductor substrate such as a silicon wafer.

[0077] The lower film BL may include a metal film, a non-metal oxide film, or a combination thereof. For example, the metal film may include a metal such as aluminum (Al), copper (Cu), and / or an alloy thereof. For example, the non-metal oxide film may be a silicon oxide film and / or a silicon oxynitride film, etc., but the embodiments of the present disclosure are not limited thereto.

[0078] The photoresist film P-PR can be formed by applying and drying a photoresist composition on the lower film BL. In this embodiment, as an example, a negative photoresist composition is applied to the lower film BL, and the exposed portion EP (see FIG. Figure 3 ), the polymer in the negative photoresist composition is cured in the exposed portion EP (see FIG. 1 ), but the embodiments of the present disclosure are not limited thereto, and the photoresist film P-PR may be formed by applying a positive photoresist composition to the lower film BL. Figure 3 ) is formed by polymer softening.

[0079] refer to Figure 3, an exposure process of the photoresist film P-PR may be performed using the mask MK. The mask MK may be spaced apart from the substrate BS on which the photoresist film P-PR is formed. The mask MK may include a transmission area MK1 and a light-blocking area MK2 to selectively transmit light (e.g., UV light) incident from the top of the mask MK. Accordingly, an exposed portion EP of the photoresist film P-PR overlapping with the transmission area MK1 of the mask MK may be exposed to light for crosslinking / curing. In an embodiment, a non-exposed portion NEP of the photoresist film P-PR overlapping with the light-blocking area MK2 of the mask MK may not be cured.

[0080] Also refer to Figure 3 and Figure 4 , the non-exposed portion NEP of the photoresist film P-PR may be removed using a developer. For example, due to the light blocking region MK2 of the mask MK, the non-exposed portion NEP of the photoresist film P-PR that is not light-transmitted (or not exposed to light) may be completely removed by the developer, and thus the surface of the lower film BL may be exposed. In an embodiment, the exposed portion EP of the photoresist film P-PR may remain on the lower film BL to form a photoresist pattern PR.

[0081] In an embodiment, the photoresist pattern PR may be used as an etching mask for patterning the lower film BL. For example, an etchant may be provided on the lower film BL, and the lower film BL may be etched using the provided etchant. The lower film BL may not be etched due to the photoresist pattern PR in the region where the photoresist pattern PR is provided, and the lower film BL may be etched in the region where the photoresist pattern PR is not provided, so that a lower film BL may be formed as shown in FIG. Figure 5 For example, the line pattern FC is formed from the lower film BL by an etching process. The etchant used in the process of etching the lower film BL is not limited to any one embodiment and can be applied to the subject matter of the present disclosure without any particular limitation as long as it is capable of etching a film including a metal film, a non-metal oxide film, or a combination thereof.

[0082] refer to Figure 5-6 , the photoresist pattern PR on the line pattern FC may be removed by providing the stripper composition SC according to the above-described embodiment.

[0083] For example, in the operation of removing the photoresist pattern PR, the photoresist pattern PR may be stripped by using a stripper composition SC according to an embodiment. As described above, the stripper composition SC according to an embodiment may include an amine compound, a diol compound, an aprotic polar solvent, and a first corrosion inhibitor. In an embodiment, the stripper composition may further include an additive including at least one of a surfactant, an antioxidant, and a stabilizer. The aprotic polar solvent may not include N-methyl-2-pyrrolidone and N-methylformamide. The first corrosion inhibitor may be represented by Formula 1.

[0084] Formula 1

[0085]

[0086] In Formula 1, n may be an integer of 1 to 6, but the embodiments of the present disclosure are not limited thereto.

[0087] In the stripper composition SC according to the embodiment, the amine compound can quickly contact the photoresist pattern without loss (or substantially without loss) due to volatilization, and the removed photoresist component can be quickly dissolved. Accordingly, the stripper composition SC according to the embodiment can appropriately or fully swell and remove the photoresist pattern PR, and the photoresist pattern PR can be removed from the substrate BS. Because the above-mentioned stripper composition SC has improved solubility for the photoresist, the stripper composition SC according to the embodiment can be used to perform a stripping process without substantially leaving a residue of the photoresist pattern PR on the line pattern FC and without damaging the line pattern FC.

[0088] In the method for forming a pattern according to an embodiment, the operation of removing the photoresist pattern PR may include a cleaning process for cleaning the substrate BS on which the wire pattern FC is formed. The cleaning process may be a process for cleaning the substrate BS on which the wire pattern FC is formed with water. For example, after the photoresist pattern PR is stripped from the substrate BS on which the wire pattern FC is formed using the above-mentioned stripper composition SC, the substrate BS may be cleaned with water. The method for forming a pattern according to an embodiment may be performed without leaving residues of the photoresist pattern PR and residues of the stripper composition SC on the wire pattern FC through a cleaning process. In the method for forming a pattern according to an embodiment, the above-mentioned stripper composition SC may be used to remove the photoresist pattern PR, and the stripper composition SC may have excellent water substitutability, thereby preventing or reducing the generation of stains on the substrate BS on which the wire pattern FC is formed.

[0089] The line pattern FC capable of using the stripper composition SC according to an embodiment of the present disclosure is not particularly limited and may be a single film or a plurality of films. The line pattern FC may be a line for a gate electrode, a source electrode, or a drain electrode constituting a thin film transistor of a display device.

[0090] The stripper composition according to the embodiment of the present disclosure can remove the photoresist in a short time by showing excellent stripping ability to the photoresist without damaging the lower film including the metal film, the non-metallic oxide film or a combination thereof. In an embodiment, the stripper composition has excellent dissolving ability to the photoresist, thereby improving economic benefits by increasing the processing volume, and has excellent cleaning ability, so that no residual solution and / or surface impurities are left after stripping the photoresist pattern. Due to these effects, the stripper composition according to the embodiment of the present disclosure can contribute to the increase in yield in the process of manufacturing semiconductors and display devices.

[0091] Hereinafter, with reference to examples and comparative examples, the stripper composition according to the embodiment of the present disclosure and the wire manufactured using the stripper composition will be further described. In addition, the examples described later in the following are examples for helping to understand the subject matter of the present disclosure, and the scope of the present disclosure is not limited thereto.

[0092] Example

[0093] 1. Manufacturing stripping agent composition

[0094] Stripper compositions of Examples 1 to 16 and Comparative Examples 1 to 9 according to embodiments of the present disclosure were manufactured according to the compositions and contents described in the following Table 1. The unit representing the content of each component in Table 1 is weight percentage relative to 100 wt % of the total weight of the stripper composition.

[0095] Table 1

[0096]

[0097]

[0098] 2. Evaluation of the performance of the stripping agent composition

[0099] 1) Evaluation of stripping ability

[0100] The stripping ability of the stripper compositions of Examples 1 to 16 and Comparative Examples 1 to 9 for photoresist was evaluated. After applying a photoresist (AZEM, DTR-300) of about 1.5 μm on a glass substrate, an experimental sample was prepared by hard baking (H / B) at about 160° C. for about 10 minutes. Under a spray pressure of about 0.4 kgf, the time required for complete stripping by each stripper composition of the embodiments and comparative examples was measured using a single wafer spray type stripping device maintained at a temperature of about 60° C., and the evaluation results are shown in Table 2. In this case, it is confirmed whether the photoresist is stripped by irradiating ultraviolet light on the glass substrate and observing whether the photoresist remains.

[0101] 2) Solubility evaluation

[0102] The solubility of the stripper compositions of Examples 1 to 16 and Comparative Examples 1 to 9 to the photoresist was evaluated. Photoresist powder was prepared by drying the photoresist (AZEM, DTR-300) on a hot plate at about 160°C for about 4 hours. The dry photoresist powder was added to each stripper composition maintained at a temperature of about 60°C by adding about 2% by weight of solid content, and stirred for about 20 minutes under stirring conditions of about 300 rpm, and dissolved through a filter of about 10 μm (PTFE with a pore of about 10 μm) to evaluate the solubility. The results are shown in Table 2.

[0103] In the case where the photoresist is completely dissolved within about 20 minutes and the remaining amount thereof is not measured after filtration, the weight percentage of the photoresist is set to 100 weight percent. Here, since a high weight percentage value means that a larger amount of photoresist can be dissolved, it can be said that a high weight percentage value means a greater amount of processing.

[0104] The solubility can be calculated by the following equation.

[0105] Equation 1

[0106] Solubility (wt%) = [(weight of photoresist used at about 2 wt% solid content - weight of photoresist remaining in the filter) / weight of photoresist used at about 2 wt% solid content] × 100

[0107] Herein, the solid content is about 2 wt % based on the total weight of the photoresist and each stripper composition.

[0108] 3) Evaluation of flushing capacity

[0109] The stripper compositions of Examples 1 to 16 and Comparative Examples 1 to 9 were evaluated for their rinsing ability on substrates. The substrates immersed in each of the stripper compositions of Examples 1 to 16 and Comparative Examples 1 to 9 for about 1 minute were taken out and dried for about 1 minute using an air knife. After rinsing the overdried substrate with water, the stains of the substrate were visually confirmed. The stripper composition with good water substitutability also had good rinsing ability, so that the degree of stains was weaker. The evaluation results of the rinsing ability are shown in Table 2 below, and the evaluation criteria for the rinsing ability are as follows.

[0110] Evaluation Criteria

[0111] ◎: Very good

[0112] ○: Good

[0113] △: stains are generated

[0114] ×: Severe stains

[0115] 4) Evaluation of aluminum damage

[0116] The extent of damage to aluminum on a substrate by the stripper composition solutions of Examples and Comparative Examples diluted to about 90 wt % with deionized water (DI) was evaluated.

[0117] Table 2

[0118]

[0119] Referring to Table 2, it can be confirmed that the stripper compositions of Examples 1 to 16 have excellent stripping ability, solubility, and washing ability without causing any damage to aluminum.

[0120] On the other hand, Comparative Example 1 including no diol compound showed deteriorated rinsing ability.

[0121] It can be seen that aluminum as the lower film was damaged in Comparative Example 2 and Comparative Example 5 not including the first corrosion inhibitor (straight-chain corrosion inhibitor). In addition, it can be confirmed that the stripper composition of Comparative Example 2 has deteriorated solubility to the photoresist than the stripper composition of the example.

[0122] It can be seen that the stripper composition of Comparative Example 3 not including an amine compound has further deteriorated stripping ability and solubility than the stripper composition of the example.

[0123] It can be confirmed that the stripper compositions of Comparative Examples 4 and 6 not including the aprotic polar solvent and the linear corrosion inhibitor have deteriorated stripping ability and solubility, and more aluminum damage than the stripper compositions of Examples.

[0124] It can be seen that the stripper composition of Comparative Example 7 excessively includes an aprotic polar solvent (i.e., equal to or greater than about 85 wt % of an aprotic polar solvent) and includes less than about 1 wt % of an amine compound, and therefore, has deteriorated stripping ability and provides more aluminum damage than the stripper composition of the embodiment.

[0125] It can be seen that the stripper composition of Comparative Example 8 including more than about 30 wt % of the amine compound provides more aluminum damage than the stripper composition of the embodiment. In addition, the stripper composition of Comparative Example 9 including about 4.5 wt % of the diol compound has deteriorated stripping ability and provides more aluminum damage than the stripper composition of the embodiment.

[0126] The stripper composition according to the embodiment can show excellent stripping ability for the photoresist without causing any damage to the underlying film to remove the photoresist in a short time. In addition, the stripper composition according to the embodiment can have excellent solubility for the photoresist and excellent rinsing ability, so that no residual solution or surface impurities are left after stripping the photoresist.

[0127] The method for manufacturing a pattern according to an embodiment may use the above-mentioned stripper composition, thereby improving the rate and efficiency of stripping a photoresist.

[0128] In the above, reference has been made to the description of example embodiments of the present disclosure, but those skilled in the art or ordinary technicians in the relevant art will understand that various modifications and changes may be made to the subject matter of the present disclosure within the spirit and scope of the present disclosure as defined in the claims and their equivalents.

[0129] Therefore, the technical scope of the present disclosure is not limited to the contents described in the detailed description of the specification, but should be determined by the claims and their equivalents.

Claims

1. A stripping agent composition comprising: Relative to the total weight of the stripper composition, 1 to 30 wt % of an amine compound; 5 to 60 wt% of a diol compound; 20 to 70 wt % of an aprotic polar solvent other than N-methyl-2-pyrrolidone and N-methylformamide; and 0.001 wt % to 20 wt % of a first corrosion inhibitor represented by Formula 1: Formula 1 In Formula 1, n is an integer of 1 to 6.

2. The stripper composition according to claim 1, wherein the amine compound comprises monoethanolamine, methylethanolamine, diethanolamine, triethanolamine, propanolamine, aminoethanol, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, N-methyldiethanolamine, N,N-dimethylethanolamine, 2-diethylaminoethanol, 2-(2-aminoethylamino)ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, N-(methoxymethyl)diethylamine, (isobutoxymethyl)dimethylamine, 2-(2-aminoethoxy)ethanol, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5 -triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-hydroxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, diethylenetriamine, triethylenetetramine, propylenediamine, tetraethylenepentamine, N,N-diethylethylenediamine, 1,4-butanediamine, N-ethylethyl At least one of diamine, 1,2-propylenediamine, 1,3-propylenediamine, adipic acid amide, piperazine, N-methylpiperazine, N-ethylpiperazine, N-propylpiperazine, N-butylpiperazine, 1-pentylpiperazine, 1-hexylpiperazine, acryloylpiperazine, N-acryloyl-N'-methylpiperazine, hydroxyethylpiperazine, N-(2-aminoethyl)piperazine, N,N'-dimethylpiperazine, aniline, benzylamine, N,N-dimethylaniline and diphenylamine. The stripper composition according to claim 1 , wherein the amine compound comprises a primary amine compound. 4 . The stripper composition according to claim 1 , wherein the amine compound comprises at least one of an alkanolamine compound and an alkoxyamine compound. 5 . The stripper composition according to claim 4 , wherein a weight ratio of the alkanolamine compound to the alkoxyamine compound is 1:0.5 to 1:

5. 6 . The stripper composition according to claim 1 , wherein the amine compound is included in an amount of greater than 5 wt % to 30 wt % with respect to the total weight of the stripper composition.

7. The stripper composition according to claim 1, wherein the glycol compound comprises at least one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether. The stripper composition according to claim 1 , wherein the aprotic polar solvent comprises an amide-based solvent.

9. The stripper composition according to claim 1, wherein the aprotic polar solvent comprises at least one of formamide, N-ethylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylpropionamide, dimethyl sulfoxide, diethyl sulfoxide, dipropylene sulfoxide, cyclopentane, 2-pyrrolidone, N-ethyl-2-pyrrolidone and N-(2-hydroxyethyl)-2-pyrrolidone. 10 . The stripper composition according to claim 1 , wherein the first corrosion inhibitor represented by Formula 1 is included in an amount of 5 wt % to 10 wt % with respect to the total weight of the stripper composition. The stripper composition according to claim 1 , wherein in Formula 1, n is an integer of 1 to 4. 12 . The stripper composition according to claim 11 , wherein the first corrosion inhibitor represented by Formula 1 comprises at least one of glycerol, threitol, ribitol, xylitol, sorbitol, mannitol, and galactitol. 13 . The stripper composition according to claim 1 , further comprising an additive, wherein the additive comprises at least one of a surfactant, an antioxidant, and a stabilizer.

14. The stripper composition according to claim 1, wherein the stripper composition does not include water. 15 . The stripper composition according to claim 1 , wherein the stripper composition has a specific gravity of 1.01 or more.

16. A method for forming a pattern, the method comprising: forming a photoresist pattern on the substrate on which the lower film is formed; forming a line pattern using the photoresist pattern; as well as removing the photoresist pattern by providing a stripper composition, The stripper composition is the stripper composition according to any one of claims 1 to 15.

17. The method according to claim 16, wherein the lower film comprises: Metal films including aluminum, copper or alloys thereof; A non-metal oxide film including a silicon oxide film and / or a silicon oxynitride film; or Its combination. The method according to claim 16 , wherein the lower film is a single film or a plurality of films.

19. The method of claim 16, wherein the aprotic polar solvent comprises N-ethylformamide.

20. The method of claim 16, wherein the amine compound comprises at least one of monoethanolamine and 2-(2-aminoethoxy)ethanol.

Images