KR102572751B1 - Resist stripper composition and method of stripping resist using the same - Google Patents

Abstract

A resist stripper composition according to the present invention includes a compound represented by Formula 1 below; aprotic organic compounds; primary alcohol compounds; and an organic alkali compound.
[Formula 1]

In Formula 1, R is a hydrocarbon group having 4 to 12 carbon atoms.

Description

Resist stripping composition and resist stripping method using the same {RESIST STRIPPER COMPOSITION AND METHOD OF STRIPPING RESIST USING THE SAME}

The present invention relates to a resist stripping composition used for resist stripping and a resist stripping method using the same.

Recently, with the miniaturization of electronic devices, high integration and multilayering of semiconductor devices are rapidly progressing, and as a result, miniaturization of photoresist (PR) patterns is progressing, and technology for stably forming microcircuits of 0.5 μm or less is in progress. it became necessary

A microcircuit of a semiconductor device or a liquid crystal display device is implemented through a photolithography process. In the photolithography process, a photoresist is uniformly coated on a conductive metal film such as aluminum, aluminum alloy, copper, copper alloy, molybdenum, or molybdenum alloy, or an insulating film such as silicon oxide film or silicon nitride film, formed on a substrate, and selectively exposed to light. , Development treatment to form a photoresist pattern, and then, using the patterned photoresist film as a mask, wet or dry etch the conductive metal film or insulating film to transfer the fine circuit pattern to the photoresist lower layer, which becomes unnecessary after the photoresist layer It proceeds to the process of removing with a stripper (stripper).

As a photoresist peeling method, a wet peeling method using a peeling solution is adopted, and the peeling solution used at this time should be able to completely peel the photoresist, which is the object to be removed, and should not leave residue on the substrate after rinsing. do. In addition, it should have low corrosion resistance that should not damage the metal film or the insulating film of the photoresist lower layer. In addition, if a mutual reaction occurs between the compositions constituting the stripping solution, the storage stability of the stripping solution becomes a problem and different physical properties may be exhibited depending on the order of mixing during preparation of the stripping solution. In addition, it is preferable that the stripper is easy to handle, has low toxicity, is safe, and can be used for recycling. In addition, the number of substrates that can be treated with a certain amount of stripping solution should be large, and the supply and demand of components constituting the stripping solution should be easy.

Among the various conditions described above, the most important item is to have excellent removal performance for the target photoresist and to have low corrosion resistance that does not damage the metal film or insulating film of the photoresist lower layer. To meet this, photoresist stripper compositions having various compositions are being researched and developed.

Republic of Korea Patent Publication No. 2013-0008106 (2013.01.22.) Republic of Korea Patent Publication No. 2014-0132271 (2014.11.17.) Republic of Korea Patent Publication No. 2006-0117667 (2006.11.17.) Republic of Korea Patent Publication No. 2006-0045957 (2006.05.17.)

The present invention is to solve the above problems, and an object of the present invention is to provide a resist stripper composition that exhibits a strong anti-corrosion effect even in a composition such as strong alkali or strong base, and a method for stripping a resist using the same.

In addition, an object of the present invention is to provide a method for manufacturing a flat panel display substrate including a step of cleaning the flat panel display substrate using the above-described resist stripper composition, and a flat panel display substrate manufactured using the same.

The present invention relates to a compound represented by Formula 1; aprotic organic compounds; primary alcohol compounds; and an organic alkali compound.

[Formula 1]

In Formula 1, R is a hydrocarbon group having 4 to 12 carbon atoms.

In addition, the present invention comprises the steps of forming a resist pattern on the substrate on which the metal layer is formed; patterning the metal layer with the resist pattern; and a resist stripping method comprising the step of stripping the resist using the above-described resist stripping liquid composition.

Further, the present invention relates to a method for manufacturing a flat panel display substrate including a step of cleaning the flat panel display substrate using the resist stripper composition described above.

In addition, the present invention relates to a flat panel display substrate manufactured by the above-described flat panel display substrate manufacturing method.

Even when the resist stripper composition according to the present invention has a composition having high nucleophilicity or a strong base, it has an advantage of having strong anti-corrosion ability by including the compound represented by Formula 1. In addition, there is an advantage in that the performance is maintained even over time at high temperatures.

In addition, the resist stripper composition according to the present invention has an advantage of having an effect of preventing stains that may occur in the process.

The resist stripping method using the resist stripper composition according to the present invention has the advantage of reducing manufacturing cost and process cost because a strong anti-corrosion effect can be imparted even when a small amount of the compound represented by Chemical Formula 1 is included. .

Hereinafter, the present invention will be described in more detail.

In the present invention, when a member is said to be located “on” another member, this includes not only a case where a member is in contact with another member, but also a case where another member exists between the two members.

In the present invention, when a part "includes" a certain component, it means that it may further include other components, not excluding other components unless otherwise stated.

< resist Stripper Composition>

One aspect of the present invention is a compound represented by Formula 1; aprotic organic compounds; primary alcohol compounds; and an organic alkali compound.

[Formula 1]

In Formula 1, R is a hydrocarbon group having 4 to 12 carbon atoms.

Compound represented by Formula 1

The resist stripper composition of the present invention includes a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, R is a hydrocarbon group having 4 to 12 carbon atoms.

When the compound represented by Chemical Formula 1 is included in the resist stripper composition, it may serve to prevent corrosion of the metal surface.

In Formula 1, when R is a hydrocarbon group having 4 to 12 carbon atoms, it is preferable in terms of anticorrosive force. When R is hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, it may be difficult to prevent corrosion of the underlying metal in a strong amine or alkali solution. In Formula 1, when R is a hydrocarbon group having more than 12 carbon atoms, the compound of Formula 1 is mixed with other constituents included in the resist stripper composition, such as an aprotic organic compound, a primary alcohol compound, or an organic alkali compound Since this may be somewhat difficult, it is preferable that the above R is a hydrocarbon group having 4 to 12 carbon atoms.

The hydrocarbon group may be specifically an aliphatic hydrocarbon group.

More specifically, R may be a straight-chain or branched-chain alkyl group having 4 to 12 carbon atoms, preferably a straight-chain alkyl group having 4 to 12 carbon atoms.

In addition, since the benzotriazole-based compound represented by Formula 1 of the present invention is connected to the benzene ring rather than the triazole ring, there is an advantage that more excellent anti-corrosion ability can be imparted.

Furthermore, when the compound represented by Chemical Formula 1 is included in the resist stripper composition, it is possible to impart excellent corrosion protection even in a very small amount, so it is possible to include a strong amine or alkali in the resist stripper composition, Due to this, there is an advantage that the peeling force can also be increased. As described above, the compound represented by Chemical Formula 1 can have a great advantage in terms of overall cost reduction because it is possible to impart strong corrosion protection even when a small amount is added.

In addition, even when the compound represented by Chemical Formula 1 is included in the resist stripper composition, the color change of the stripper composition is not caused.

In one embodiment of the present invention, the compound represented by Formula 1 is 5-butyl-1H-benzotriazole, 5-hexyl-1H-benzotriazole, 4-n-octylbenzotriazole, 5-n- It may be at least one selected from the group consisting of octylbenzotriazole and 5-dodecyl-1H-benzotriazole, but is not limited thereto.

In another embodiment of the present invention, the compound represented by Chemical Formula 1 may be included in an amount of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, based on 100% by weight of the total resist stripper composition.

When the compound represented by Formula 1 is included in the above range with respect to 100% by weight of the total resist stripper composition, it is preferable from the viewpoint of economy or corrosion prevention. When the compound represented by Formula 1 is included in less than 0.001% by weight, corrosion of the metal layer may cause some damage to the device, and if it exceeds 5% by weight, economic loss may occur due to an increase in price, As the overall viscosity of the resist stripping solution increases slightly, the resist stripping solution remains on the substrate or stains may occur due to the remaining stripping solution, so it is preferable to satisfy the above range.

aprotic organic compounds

The resist stripper composition of the present invention includes an aprotic organic compound.

The aprotic organic compound may dissolve or disperse components included in the resist stripping liquid composition to perform a role of allowing a resist removal reaction to proceed more smoothly. In addition, when the resist stripper composition includes the aprotic organic compound, it is advantageous to exhibit performance in removing a resist polymer that has been altered or crosslinked by etching, and at the same time increases the number of treated materials.

The aprotic organic compound may specifically be an aprotic polar compound, and it is preferable that the boiling point of the aprotic polar compound is not too high or too low for proper peelability. Specifically, the aprotic organic compound preferably has a boiling point of 130 °C to 250 °C.

Examples of the aprotic organic compound include, but are not limited to, pyrrolidone compounds such as 1-acetylpyrrolidine, 2-pyrrolidone, N-methylpyrrolidone, and N-ethylpyrrolidone; imidazolidinone compounds such as 1,3-dimethyl-2-imidazolidinone and 1,3-dipropyl-2-imidazolidinone; sulfoxide compounds such as dimethyl sulfoxide and sulfolane; phosphate compounds such as triethyl phosphate and tributyl phosphate; N-methylformamide, N-ethylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetoacetamide, N,N-tertbutylformamide, acetamide, N-methylacetamide, N-ethylacetamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-(2-hydroxyethyl)acetamide, N,N-dimethylpropionamide, 3 -Methoxy-N,N-dimethylpropionamide, N,N-dimethylbutylamide, 3-(2-ethylhexyloxy)-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropion amide compounds such as amide; and the like, and these may be used alone or in combination of two or more.

In another embodiment of the present invention, the aprotic organic compound is 40 to 95% by weight, preferably 50 to 95% by weight, more preferably 60 to 80% by weight based on 100% by weight of the total resist stripper composition % can be included.

When the aprotic organic compound is included within the above range with respect to 100% by weight of the total resist stripper composition, there is an advantage in exhibiting excellent performance in removing the resist polymer altered or crosslinked by etching. When the aprotic organic compound is included in less than 40% by weight, the removal ability of the crosslinked resist and the overall process capacity may be slightly lowered, and when the aprotic organic compound exceeds 95% by weight, the relatively Since the content of other components included in the resist stripper composition is reduced, the performance of the resist stripper composition may be adversely affected, and the price of the product may increase, resulting in a problem in which overall benefits cannot be obtained.

primary alcohol compounds

The resist stripper composition of the present invention contains a primary alcohol compound.

The primary alcohol compound serves to dissolve the solidified resist polymer, and facilitates the removal of the stripping solution by water in the deionized water rinse process after resist stripping, thereby adsorbing the resist dissolved in the stripping solution and It can play a role in minimizing re-precipitation.

The primary alcohol compound is, for example, tetrahydrofurfuryl alcohol, hydroxymethylcyclopentene, 4-hydroxymethyl-1,3-dioxolane, 2-methyl-4-hydroxymethyl-1,3-dioxolane , 2,2-dimethyl-1,3-dioxolane-4-methanol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methoxyethanol, polyethylene glycol, diethylene glycol, Diethylene glycol monomethyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono Butyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like, and these may be used alone or in combination of two or more, but are not limited thereto.

In another embodiment of the present invention, the primary alcohol compound is included in an amount of 3 to 55% by weight, preferably 5 to 50% by weight, based on 100% by weight of the entire resist stripper composition.

When the primary alcohol compound is included within the above range, there is an advantage in that the stripper is easily removed by water in a pure water rinse process. When the primary alcohol compound is included in less than 3% by weight, when the decomposed resist polymer remains on the metal layer, the solubility in water is lowered, which may cause some staining, and the primary alcohol mixture exceeds the above range. Due to the high viscosity, the peeling solution may remain on the substrate, and a phenomenon in which stains may be somewhat severe may occur. In addition, since the content of other components is relatively reduced, the peeling ability, removability, and solubility of the crosslinked photoresist may be slightly lowered, and a problem of reducing the number of substrates that can be treated with a certain amount of peeling solution may occur. there is.

organic alkali compounds

The resist stripper composition of the present invention contains an organic alkali compound. The organic alkali compound strongly penetrates the polymer matrix of the resist that has been altered or crosslinked under various processes such as dry or wet etching, ashing, or ion implant processing, thereby breaking bonds existing within or between molecules. It serves to break the resist remaining on the substrate and forms an empty space in the structurally weak part of the resist remaining on the substrate to transform the resist into an amorphous polymer gel mass so that the resist attached to the top of the substrate can be easily removed. carry out

When the organic alkali compound is included in the resist stripper composition, the photoresist removal ability and the corrosiveness of the metal under the substrate are both enhanced, and when the removal ability is excellent, the corrosion resistance to the lower metal is also increased, so damage to the metal layer may become severe, and when the corrosion resistance is lowered in order to minimize the damage of the metal, there is a problem of causing an anti-interaction that reduces the peeling rate and the solvency together because the removal ability is lowered.

Therefore, since the resist stripper composition of the present invention includes the compound represented by Formula 1, it has a strong anti-corrosion effect even when the organic alkali compound has a strong removal ability. Of course, since it is possible to impart a strong anti-corrosion effect even when it is included in a small amount, there is an advantage in that even a low cost effect can be exerted.

The organic alkali compounds are not limited thereto, but examples of organic alkali compounds mainly used in strippers for thin film transistors (TFTs) include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and amines. Examples of the amines include primary amines such as methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, and pentylamine; Secondary such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, and methylisobutylamine amine; tertiary amines such as diethyl hydroxyamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine; choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monomethylethanolamine, 2-aminoethanol, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylaminoethanol, 2-(2-aminoethylamino)-1-ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino alkanolamines such as -1-propanol, 4-amino-1-butanol, dibutanolamine, and aminoethylethanolamine; (butoxymethyl)diethylamine, (methoxymethyl)diethylamine, (methoxymethyl)dimethylamine, (butoxymethyl)dimethylamine, (isobutoxymethyl)dimethylamine, (methoxymethyl)diethanolamine , (hydroxyethyloxymethyl)diethylamine, methyl(methoxymethyl)aminoethane, methyl(methoxymethyl)aminoethanol, methyl(butoxymethyl)aminoethanol, 2-(2-aminoethoxy)ethanol, etc. of alkoxyamines, and the like.

In some embodiments of the present invention, the organic alkali compound is included in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on 100% by weight of the resist stripper composition.

When the organic alkali compound is included in the above content range, it is preferable in terms of peeling force or anti-corrosion force. When the organic alkali compound is included in an amount of less than 0.1% by weight, a problem in which resist foreign substances remain may occur due to a decrease in resist peeling force, and when the organic alkali compound exceeds 20% by weight, control of corrosion rate for metal wiring This is rather difficult and can cause problems.

additive

In another embodiment of the present invention, the resist stripper composition may further include one or more additives selected from the group consisting of a corrosion inhibitor and deionized water.

(1) corrosion inhibitor

The anti-corrosion agent may be additionally used when the photoresist to be removed is severely denatured, so that it is in contact with the stripping solution for a long time or repeatedly, or when process conditions are severe.

The corrosion inhibitor includes, but is not limited to, benzotriazole, tolytriazole, methyl tolytriazole, 2,2'-[[[benzotriazole]methyl]imino]bisethanol, 2,2' -[[[methyl-1hydrogen-benzotriazol-1-yl]methyl]imino]bismethanol, 2,2'-[[[ethyl-1hydrogen-benzotriazol-1-yl]methyl]imino ]bisethanol, 2,2'-[[[methyl-1hydrogen-benzotriazol-1-yl]methyl]imino]bisethanol, 2,2'-[[[methyl-1hydrogen-benzotriazole- 1-yl]methyl]imino]biscarboxylic acid, 2,2'-[[[methyl-1hydrogen-benzotriazol-1-yl]methyl]imino]bismethylamine, 2,2'-[[[ Amine-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol, 4-methyl-1 hydrogen-benzotriazole, 5-methyl-1 hydrogen-benzotriazole, 4-methyl-4,5 ,6,7-tetrahydro-1H-benzo[1,2,3]triazole, 5-methyl-4,5,6,7-tetrahydro-1H-benzo[1,2,3]triazole, 4 ,6-dimethyl-4,5,6,7-tetrahydro-1H-benzo[1,2,3]triazole 5,6-dimethyl-4,5,6,7-tetrahydro-1H-benzo[1 2,3] azole compounds such as triazole and 2-methylphenol, 2,6-dimethylphenol, 2,4,6-trimethylphenol, 2-ethylphenol, 2,6-diethylphenol, 2,6 -Diethyl-4-methylphenol, 2-propylphenol, 2,6-dipropylphenol, 2,6-tripro-4-methylphenol, 2-t-butylphenol, 2,6-di-t-butyl Phenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,4-dimethyl-6-t-butylphenol, t-butyl-4-methylphenol Phenolic compounds such as oxyphenol, monocarboxylic acids such as formic acid, acetic acid, and propionic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutanic acid, adipic acid, pimelic acid, maleic acid, furmic acid, and glutaconic acid tricarboxylic acids such as boxylic acid, trimellitic acid, tricarballylic acid, and organic acids such as hydroxyacetic acid, lactic acid, salicylic acid, malic acid, tartaric acid, citric acid, gluconic acid, and oxycarboxylic acid; Succinic amide ester, malic amide ester, maleic amide ester, fumaric amide ester, oxalic amide ester, malonic amide ester, glutaric amide ester, acetic amide ester, lactic amide ester, citric amide ester, tar organic acid amide esters such as taric amide ester, glucolic amide ester, formic amide ester, and uric amide ester, and the like, which may be used alone or in combination of two or more.

The corrosion inhibitor may be included in an amount of 0.001 to 3% by weight, preferably 0.005 to 0.5% by weight, based on 100% by weight of the resist stripper composition. Economic efficiency is excellent when the corrosion inhibitor is included within the above range, and since the corrosion inhibitor can be used in a smaller amount than conventionally used, various problems caused by the use of the corrosion inhibitor can be solved.

(2) deionized water

The deionized water may be further included in the resist stripper composition. When the deionized water is further included, the activation of the alkali compound can be improved to increase the peeling rate, and mixing with the primary alcohol compound and the aprotic polar solvent is easy, so that in the rinse process with deionized water after the peeling process, the peeling rate can be increased. There is an advantage in that the resist stripper composition does not remain and can be completely removed in a short time.

In another embodiment of the present invention, the deionized water may be included in an amount of 0.01 to 30% by weight, preferably 0.1 to 10% by weight, based on 100% by weight of the total resist stripper composition, but is not limited thereto. However, when the deionized water is included within the above range, it is preferable in terms of peeling rate.

Preparation of the photoresist stripper composition described above is not particularly limited in the present invention. For example, it can be prepared by sufficiently mixing the aforementioned components and contents in a stirrer or a circulator.

The photoresist stripper composition may be used in a selective stripping process of a photoresist film for forming fine patterns in semiconductor device manufacturing.

Since the photoresist stripper composition of the present invention includes the compound represented by Formula 1, an aprotic organic compound, a primary alcohol compound, and an organic alkali compound, even if the composition has high nucleophilicity or strong basicity, the lower portion It is possible to impart strong anti-corrosion power to the metal used in the film, and there is an advantage in that the performance is maintained even after a high temperature elapses.

In particular, when the compound represented by Formula 1 and primary or secondary amine are used together, it has a strong peeling force against the resist, and at the same time, even when a small amount of the compound represented by Formula 1 is included, a strong anti-corrosion effect appears. Therefore, it has the advantage of being able to exert a low cost effect.

In addition, the photoresist stripper composition of the present invention can be used in the manufacturing process of not only semiconductor devices but also display devices, MEMS devices, and wiring boards including the same.

< of resist Peeling method>

Another aspect of the present invention includes forming a resist pattern on a substrate on which a metal layer is formed; patterning the metal layer with the resist pattern; and a resist stripping method comprising the step of stripping the resist using the above-described resist stripping liquid composition.

Specifically, after applying a photoresist on the metal layer formed on the substrate, a photoresist pattern is formed, and the metal layer is etched and patterned using the photoresist pattern formed thereon as a mask. After that, the photoresist may be stripped using the photoresist stripper composition according to the present invention.

The photoresist includes a positive-type photoresist, a negative-type photoresist, and a positive/negative dual-tone photoresist, and is not limited to components, but a photoresist that is particularly effectively applied is a novolak-based phenolic resin and a photoactive compound based on diazonaphthoquinone.

The metal layer may specifically be a conductive metal layer, and may be, for example, a single film or a multilayer film of two or more layers made of a metal such as aluminum, copper, neodymium, or molybdenum or an alloy of these metals. More preferably, it is a single film or a multilayer film of two or more layers containing aluminum, copper, or an alloy thereof, or a single film containing aluminum, copper, or an alloy thereof, and neodymium, molybdenum, or an alloy thereof, or a multilayer film of two or more layers. can

The method of stripping a photoresist from a substrate on which a fine circuit pattern is engraved using the photoresist stripper composition of the present invention is a dip method in which several substrates to be stripped are simultaneously immersed in a large amount of the stripper composition. Both the single-wafer method of removing the photoresist by spraying (spraying) the stripper onto the substrate can be used. In this case, the application time and temperature of dipping, spraying (spraying) or dipping and spraying can be easily or appropriately selected by a person skilled in the art.

< flat Panel Display Device>

In addition, the present invention provides a method for manufacturing a flat panel display substrate including a step of cleaning or peeling the flat panel display substrate using the resist stripper composition described above.

In addition, the present invention relates to a flat panel display substrate manufactured using the above-described flat panel display substrate manufacturing method.

The present invention also provides a flat panel display device including the flat panel display substrate described above.

The flat panel display substrate manufactured by the above-described manufacturing method and the flat panel display device including the same are perfectly cleaned during the manufacturing process, and corrosion of metal wires including aluminum and/or copper hardly occurs, so they have excellent quality. has the advantage of having

The photoresist stripper composition according to the present invention can be applied to manufacture not only the flat panel display described above but also various image display devices.

Hereinafter, examples will be described in detail in order to specifically describe the present specification. However, embodiments according to the present specification may be modified in many different forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present specification to those skilled in the art. In addition, "%" and "parts" indicating content below are based on weight unless otherwise specified.

Example 1 to 9 and comparative example 1 to 9: resist Preparation of stripper composition

A resist stripper composition was prepared according to the ingredients and compositions shown in Table 1 below. At this time, in order to measure the corrosion strength of the compound of Formula 1, primary or secondary strong amines were used, and in the case of tertiary amines, deionized water to increase activation was added.

compound of formula 1 aprotic organic compounds primary alcohol compounds organic alkali compounds DIW type ingredient
(weight%) type ingredient
(weight%) type ingredient
(weight%) type ingredient
(weight%) ingredient
(weight%) Example 1 A1 0.18 B1 62 C1 32.82 MIPA 5 - Example 2 A2 0.16 B3 90 C2 6.84 MEA 3 - Example 3 A3 0.15 B3 61 C3 32.85 AEEA 6 - Example 4 A3
A2 0.05
0.05 B3 70 C2 22.9 MMEA 7 - Example 5 A1 0.22 B1 85 C1 6.78 DEA 8 - Example 6 A2 0.13 B2 77 C1 7.87 MDEA 10 5 Example 7 A4 0.005 B3 60 C1 37.995 AEEA 2 - Example 8 A4 0.02 B1 75 C2 14.98 MMEA 10 - Example 9 A1 4 B2 69 C3 24 MEA 3 - Comparative Example 1 - - B1 55 C2 43 MEA 2 - Comparative Example 2 A1 0.1 - - C3 91.9 AEEA 8 - Comparative Example 3 A1 0.1 B3 92.9 - - MMEA 7 - Comparative Example 4 A1 0.1 B2 70 C3 29.9 - - - Comparative Example 5 A5 0.1 B1 53 C1 43.9 MEA 3 - Comparative Example 6 A6 0.1 B3 65 C2 27.9 MIPA 7 - Comparative Example 7 A7 0.1 B1 45 C1 49.9 AEEA 5 - Comparative Example 8 A8 0.1 B1 55 C3 42.9 MEA 2 - Comparative Example 9 A9 0.1 B2 66 C2 30.9 MEA 3 - A1: 5-hexyl-1H-benzotriazole
A2: 4-n-octylbenzotriazole
A3: 5-dodecyl-1H-benzotriazole
A4: 5-n-octylbenzotriazole
A5: Benzotriazole
A6: Tolytriazole
A7: 2,2'-[(1H-benzotriazol-1-ylmethyl)imino]bisethanol
A8: 2-octyl-2H-benzotriazole
A9: 6-methyltetrahydrobenzotriazole
B1: N-methylpyrrolidone
B2: N-ethylformamide
B3: N,N-diethylformamide
C1: 4-hydroxymethyl-1,3-dioxolane
C2: diethylene glycol monomethyl ether
C3: diethylene glycol monoethyl ether
MIPA: 1-amino-2-propanol
MEA: Monoethanolamine
AEEA: aminoethylethanolamine
DEA: Diethanolamine
MMEA: monomethylethanolamine
MDEA: N-methyldiethanolamine
DIW: deionized water

Experimental example One : resist of the stripper composition Peel force evaluation

In order to confirm the peeling effect of the resist stripping composition according to Examples and Comparative Examples, a photoresist was uniformly coated on a 10 × 10 cm glass with a film thickness of 1.2 μm using a spin coater, and then baked at 150 ° C. for 10 minutes After going through, a substrate was prepared by cutting into 2 × 2 cm.

Thereafter, after maintaining the resist stripper compositions of Examples and Comparative Examples at a constant temperature of 60° C., the object was immersed at different immersion times to evaluate the stripping force.

Thereafter, cleaning was performed with pure water for 1 minute to remove the stripper remaining on the substrate, and after cleaning, the specimen was completely dried using nitrogen to remove the pure water remaining on the substrate.

The ability to remove denatured or cured resist and dry etching residues of the substrate was confirmed using a scanning electron microscope (SEM, Hitachi S-4700), and the results are shown in Table 2 below, and the removal time in the glass substrate is shown. .

Experimental example 2: After time lapse resist of the stripper composition Peel force evaluation

After leaving the resist stripper compositions of Examples and Comparative Examples at a high temperature (60° C.) for one week, the resist stripper composition was evaluated in the same manner as in Experimental Example 1.

Experimental example 3: resist Regarding the metal wiring of the stripper composition anticorrosion evaluation

In order to evaluate the anticorrosiveness of the resist stripper composition on metal wiring, a substrate with Cu wiring and Mo-X wiring exposed was prepared. Thereafter, after maintaining the resist stripper composition according to Examples and Comparative Examples at a constant temperature of 60° C., the substrate with exposed Cu wiring and Mo-X wiring was immersed in the resist stripper composition for 30 minutes, followed by washing And after drying, it was evaluated using a scanning electron microscope (SEM, Hitachi S-4700). The results are shown in Table 2 below.

Experimental Example 4: Evaluation of anticorrosive force on metal wiring of resist stripper composition after lapse of time

After leaving the resist stripper compositions according to Examples and Comparative Examples for one week at a high temperature (60° C.), corrosion resistance was evaluated in the same manner as in Experimental Example 3, and the results are shown in Table 2 below.

Experimental example 5: evaluation of staining

In order to confirm the anti-staining effect of the resist stripper composition, a substrate in which a Cu layer was formed on a Mo-X layer was prepared on a glass substrate using a thin film sputtering method according to a conventional method. The resist required for the experiment was prepared by baking a photoresist (Dongwoo Fine-Chem, DWP-520) at a high temperature of 115° C. for 3 days to remove all solvents and solidify the resist.

After adding 0.5% by weight of the prepared solidified photoresist to the photoresist stripper compositions of Examples and Comparative Examples, it was sufficiently dissolved at room temperature, and the temperature was kept constant at 50°C. Then, after immersing the substrate on which the Cu layer is formed on the Mo-X layer for 2 minutes, take it out and remove the stripper and resist remaining on the substrate to some extent using nitrogen at a constant pressure, then place it on a flat surface and pour deionized water using a pipette After dropping 5 drops at different locations, it was left for 1 minute.

Thereafter, the substrate was rinsed with deionized water for 1 minute, and then the deionized water remaining on the substrate was completely removed using nitrogen. This is to determine the degree of staining in the actual TFT process, and the entire surface was inspected and evaluated using a halogen lamp, a digital camera, and an electron microscope to determine the degree of staining of the substrate.

At this time, the evaluation criteria for anticorrosion and staining are as follows.

◎: Very good (no surface and crevice corrosion or staining of Cu wiring and Mo-X wiring)

○: Good (Almost no surface and/or crevice corrosion or staining of Cu wiring and Mo-X wiring)

△: Normal (Corrosion on the surface and crevices of Cu wiring and/or Mo-X wiring, change in surface roughness, or slight staining)

×: Bad (etching of the surface and/or crevice of Cu wiring and Mo-X wiring or many stains)

division Peel force Peel strength after aging at high temperature for 1 week metal anticorrosion Metal corrosion resistance after 1 week at high temperature spotting Example 1 <10sec <10sec ◎ ◎ ◎ Example 2 <10sec <10sec ◎ ◎ ◎ Example 3 <10sec <10sec ◎ ◎ ◎ Example 4 20sec 20sec ◎ ◎ ◎ Example 5 20sec 20sec ◎ ◎ ◎ Example 6 30sec 30sec ◎ ◎ ◎ Example 7 20sec 20sec ◎ ◎ ◎ Example 8 <10sec <10sec ◎ ◎ ◎ Example 9 <10sec <10sec ◎ ◎ ◎ Comparative Example 1 <10sec <10sec × × × Comparative Example 2 3min 3min ◎ ◎ × Comparative Example 3 20sec 20sec ◎ ◎ × Comparative Example 4 >10min >10min ◎ ◎ × Comparative Example 5 <10sec <10sec × × △ Comparative Example 6 <10sec <10sec △ △ △ Comparative Example 7 <10sec <10sec △ △ △ Comparative Example 8 <10sec <10sec × × × Comparative Example 9 <10sec <10sec × × ×

As can be seen from Table 2, the resist stripper composition according to the embodiment has excellent peeling and anticorrosiveness for Cu wiring and Mo-X wiring, as well as excellent peeling and anticorrosiveness for Cu wiring and 1 It can be seen that the performance is maintained even after aging at a high temperature for a week. In addition, it was confirmed that no residual or contamination problems occurred after the peeling process.

On the other hand, it can be seen that the resist stripper composition according to Comparative Example did not have excellent peeling force or anticorrosive force for the Cu wiring and/or the Mo-X wiring, and also caused residual and contamination problems after the stripping process.

Claims (12)

A compound represented by Formula 1 below;
aprotic organic compounds;
primary alcohol compounds; and
A resist stripper composition containing an organic alkali compound for preventing staining,
The compound represented by Formula 1 is 5-butyl-1H-benzotriazole, 5-hexyl-1H-benzotriazole, 4-n-octylbenzotriazole, 5-n-octylbenzotriazole and 5-dodecyl It is at least one selected from the group consisting of -1H-benzotriazole,
A resist stripper composition for preventing stain generation, further comprising 5% by weight or less of deionized water based on 100% by weight of the total resist stripper composition:
[Formula 1]

In Formula 1, R is a hydrocarbon group having 4 to 12 carbon atoms. delete According to claim 1,
The resist stripper composition of claim 1, wherein the compound represented by Formula 1 is included in an amount of 0.001 to 5% by weight based on 100% by weight of the total resist stripper composition. According to claim 1,
The resist stripper composition of claim 1, wherein the aprotic organic compound is included in an amount of 40 to 95% by weight based on 100% by weight of the total resist stripper composition. According to claim 1,
The resist stripper composition of claim 1, wherein the primary alcohol compound is included in an amount of 3 to 55% by weight based on 100% by weight of the total resist stripper composition. According to claim 1,
The resist stripper composition of claim 1 , wherein the organic alkali compound is included in an amount of 0.1 to 20% by weight based on 100% by weight of the total resist stripper composition. According to claim 1,
A resist stripper composition further comprising a corrosion inhibitor. delete forming a resist pattern on the substrate on which the metal layer is formed;
patterning the metal layer with the resist pattern; and
A resist stripping method comprising the step of stripping a resist using the resist stripper composition according to any one of claims 1 to 7. A method of manufacturing a flat panel display substrate comprising a step of cleaning the flat panel display substrate using the resist stripper composition according to any one of claims 1 and 3 to 7. A flat panel display substrate manufactured using the method of manufacturing a flat panel display substrate according to claim 10 . A flat panel display device comprising the flat panel display substrate of claim 11 .