KR101213731B1 - Stripper composition for photoresist - Google Patents

Abstract

The present invention relates to a stripper composition for photoresists, and more particularly to a stripper composition for photoresists comprising an organic amine compound, a polar solvent having a boiling point of at least 150 ℃ and a compound for forming a Self Assembly Monolayer (SAM) will be.

Photoresist, Stripper, SAM

Description

Stripper composition for photoresist {STRIPPER COMPOSITION FOR PHOTORESIST}

The present invention relates to a stripper composition for photoresist, and more particularly, the photoresist film, which is deteriorated and cured by harsh photolithography and wet etching processes, can be easily and cleanly removed in a short time even at a high temperature and a low temperature, and at the same time, an intermediate cleaning liquid. The present invention relates to a stripper composition for photoresist capable of simultaneously minimizing corrosion of conductive metal films such as aluminum, aluminum alloys, copper or copper alloys or insulating films such as silicon films and nitride films without using phosphorus isopropanol.

In the process of manufacturing a semiconductor integrated circuit or a fine circuit of a liquid crystal display device, a photoresist is uniformly applied to an insulating metal, such as an aluminum or aluminum alloy, copper, a copper alloy, or a conductive metal film formed on a substrate, a silicon oxide film, or a silicon nitride film. After selectively exposing and developing the photoresist pattern to form a photoresist pattern, a conductive metal film such as aluminum or an aluminum alloy or an insulating film such as a silicon oxide film or a silicon nitride film is wet or dry by using the patterned photoresist film as a mask. After the fine circuit pattern is transferred to the lower photoresist layer, the process proceeds to the step of removing the unnecessary photoresist layer with a stripper.

Characteristics of the stripper for removing the photoresist for manufacturing the semiconductor device or the liquid crystal display device are as follows.

First, it must be able to peel off the photoresist in a short time at low temperature, and have a good peeling ability not to leave photoresist residue on the substrate after rinsing.

Second, it should have low corrosion resistance that should not damage the metal film or insulating film of the photoresist underlayer.

Third, when the room temperature reaction between the solvent constituting the stripper occurs, the storage stability of the stripper is a problem, and different physical properties may be shown depending on the mixing sequence during the manufacture of the stripper, so there must be non-reactivity and high temperature stability between the mixed solvents.

Fourth, it should be low toxicity in consideration of worker safety or environmental problems in disposal.

Fifth, if a lot of volatilization occurs when the photoresist peeling proceeds at a high temperature process, the composition ratio is changed quickly, and the process stability and work reproducibility of the stripper is reduced, so it must be low volatility.

Sixth, the number of substrates that can be treated with a certain amount of stripper should be large, easy to supply and supply the components constituting the stripper, economical so that the low-cost and used stripper can be recycled through reprocessing.

In order to satisfy the above conditions, various stripper compositions for photoresists have been researched and developed. Examples are as follows.

Japanese Patent Laid-Open Publication No. 51-72503 discloses a stripper composition comprising an alkyl benzene sulfonic acid having 10 to 20 carbon atoms and a non-halogenated aromatic hydrocarbon having a boiling point of 150 ° C. or higher as an initial photoresist stripper composition. Publication No. 57-84456 discloses a stripper composition comprising dimethyl sulfoxide or diethyl sulfoxide and an organic sulfone compound. U.S. Patent 4,256,294 also discloses a stripper composition comprising an alkylaryl sulfonic acid, a hydrophilic aromatic sulfonic acid having 6 to 9 carbon atoms, and a non-halogenated aromatic hydrocarbon having a boiling point of at least 150 ° C.

However, the conventional stripper compositions as described above have a problem in that corrosion to a conductive metal film such as copper or a copper alloy is severe, and there is a problem of environmental pollution due to strong toxicity, making it difficult to use.

In order to solve the above problems, techniques for preparing a stripper composition by mixing a water-soluble alkanol amine as an essential component in various organic solvents have been proposed, for example.

U.S. Patent 4,617,251 discloses organic amine compounds such as monoethanol amine (MEA), 2- (2-aminoethoxy) -1-ethanol (AEE), dimethylformamide (DMF), dimethylacetamide (DMAc), N A two-component stripper composition comprising a polar solvent such as -methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), carbitol acetate, and propylene glycol monomethyl ether acetate (PGMEA) is disclosed. U.S. Patent No. 4,770,713 also discloses organic amine compounds, N-methylacetamide, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-N-ethylpropionamide, diethylacetamide (DEAc), di A two-component stripper composition comprising an amide solvent such as propyl acetamide (DPAc), N, N-dimethylpropionamide, N, N-dimethylbutylamide, and the like is disclosed. In addition, Japanese Patent Laid-Open No. 62-49355 discloses a stripper composition comprising an alkylene polyamine sulfone compound in which ethylene oxide is introduced into alkanol amine and ethylenediamine and a glycol monoalkyl ether. 63-208043 discloses a stripper composition comprising a water soluble alkanol amine and 1,3-dimethyl-2-imidazolidinone (DMI), and Japanese Patent Laid-Open No. 63-231343 discloses an amine compound, a polarity. Disclosed is a stripper composition for a positive photoresist comprising a solvent and a surfactant. In addition, Japanese Laid-Open Patent Publication No. 64-42653 discloses dimethyl sulfoxide (DMSO), diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, gamma butyrolactone, and 1,3-dimethyl-2-imidazolidinone A stripper composition comprising at least one solvent selected from and a nitrogen-containing organic hydroxy compound such as monoethanolamine is disclosed. Japanese Patent Laid-Open No. Hei 4-124668 discloses an organic amine, phosphate ester surfactant, 2- A stripper composition comprising butene-1,4-diol, diethylene glycol dialkyl ether, and aprotic polar solvents is disclosed.

However, the stripper composition for a photoresist as described above has a problem that the corrosion resistance to the copper or copper alloy film is weak, which may cause severe corrosion during the stripper process, and may cause a defect during the deposition of the gate insulating film, which is a later process.

Further, Japanese Patent Laid-Open No. 4-350660 discloses a stripper composition containing 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and a water-soluble organic amine. -281753 relates to a stripper composition comprising an hydroxy compound of an alkanol amine, a sulfone compound or a sulfoxide compound, (C ₆ H ₆ ) _n (OH) _n ( _where n is an integer of 1, 2, or 3). Japanese Patent Laid-Open No. Hei 8-87118 discloses a stripper composition containing N-alkylalkanolamine and dimethyl sulfoxide or dimethylformamide. The stripper composition for photoresist as described above exhibits relatively good characteristics in terms of peeling force and stability. However, in recent years, glass substrates and silicon wafer substrates are treated at high temperatures of 120 ° C. or higher in liquid crystal display devices and semiconductor device manufacturing processes. As the photoresist becomes more post-baked at a high temperature, the degree of deterioration hardening increases, and thus there is a problem in that the conventional stripper composition is not completely removed.

A photoresist stripper composition including water and / or a hydroxylamine compound has been proposed as a composition for removing the photoresist cured through the high temperature process. Specifically, Japanese Patent Application Laid-Open No. 4-289866 discloses a stripper composition containing hydroxyl amines, alkanol amines, and water, and Japanese Patent Application Laid-open No. Hei 6-266119 discloses hydroxyl amines and alkanols. A stripper composition comprising amines, water, and an anticorrosive agent is disclosed. In addition, JP-A-7-69618 discloses polar aprotic solvents such as gamma butyrolactone (GBL), dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and 2-methylamino ethanol (N-MAE). A stripper composition comprising an aminoalcohol comprising a water and water is disclosed. Japanese Unexamined Patent Application Publication No. Hei 8-123043 discloses a stripper composition comprising a glycol alkyl ether such as aminoalcohol, water, and diethylene glycol monobutyl ether. Japanese Patent Application Laid-Open No. 8-262746 discloses a stripper composition comprising alkanol amines, alkoxyalkylamines, glycol monoalkyl ethers, sugar compounds, quaternary ammonium hydroxides, and water. . In addition, Japanese Patent Application Laid-Open No. 9-152721 discloses a stripper composition containing alkanol amine, hydroxyl amine, diethylene glycol monoalkyl ether, a sugar compound (such as sorbitol) as an anticorrosive, and water. Japanese Patent Application Laid-Open No. 9-96911 discloses a stripper composition comprising hydroxyl amines, water, amines having an acid dissociation constant (pKa) of 7.5 to 13, a water-soluble polar organic solvent, and an anticorrosive agent.

However, such stripper compositions are deteriorated by severe high temperature processes, dry etching, etching, and ion implantation processes, and are applied to photoresist etching residues formed by reaction with cross-cured photoresist films and metallic by-products generated in etching processes. It is not sufficient in terms of peel strength and corrosion resistance of the copper or copper alloy film, which is a photoresist conductive underlayer, and has a problem in that the hydroxyl amine compound is unstable at high temperature and decomposes over time.

As described above, various conventional stripper compositions differ greatly in terms of photoresist stripping property, metal corrosion resistance, variety of cleaning process after peeling, work reproducibility, storage stability, and economy depending on the content ratio between components. There is a continuing need for development of economical stripper compositions with optimum performance for a variety of process conditions.

On the other hand, as the liquid crystal display becomes larger and mass-produced, peeling of photoresist using a single wafer treatment method facility that processes sheet by sheet rather than a dipping method that uses a lot of strippers is becoming common. As a stripper composition suitable for the sheet type equipment, Korean Patent Publication No. 2000-8103 discloses a stripper composition comprising 5 to 15 wt% of alkanol amine, 35 to 55 wt% of sulfoxide or sulfone compound, and 35 to 55 wt% of glycol ether. Korean Patent Publication No. 2000-8553 discloses 10 to 30% by weight of a water-soluble amine compound and a total content of diethylene glycol monoalkyl ether, N-alkyl pyrrolidone, and hydroxyalkyl pyrrolidone. Disclosed is a stripper composition comprising from 90% by weight.

Stripper compositions suitable for the sheet type equipment has a problem that the metal corrosion resistance is good, but the low temperature peeling strength is somewhat weak.

In addition, the above-described stripper compositions have a problem that aluminum wiring or copper wiring can be applied to only one metal wiring.

In order to solve the problems of the prior art as described above, the present invention is suitable for both the dip method and the sheet type peeling process, and easily and cleanly deteriorates the photoresist film hardened by the harsh photolithography and wet etching process in high temperature and low temperature within a short time. It is an object to provide a stripper composition for photoresist that can be removed.

Another object of the present invention is to minimize the corrosion of the conductive metal film, such as aluminum, aluminum alloy, copper, copper alloy, or the insulating film, such as silicon oxide film, silicon nitride film, and the like, which is a photoresist underlayer without using isopropanol as an intermediate cleaning solution. It is to provide a stripper composition for photoresist.

Still another object of the present invention is a method of peeling a photoresist that can be easily and cleanly removed in a short time even at a high temperature and a low temperature, a method of manufacturing a liquid crystal display device or a semiconductor device including the method, and a liquid crystal display device manufactured therefrom or It is to provide a semiconductor device.

In order to achieve the above object,

a) 3 to 30% by weight of a water soluble organic amine compound,

b) 65 to 95% by weight of a polar solvent having a boiling point of at least 150 ° C., and

c) 0.01% to 5% by weight of a compound for forming a Self Assembly Monolayer (SAM)

It provides a stripper composition for a photoresist comprising a.

In addition, the present invention provides a method for removing a photoresist comprising the step of etching the photoresist pattern formed on a substrate including a metal wiring as a mask, followed by peeling with the stripper composition for photoresist.

In addition, the present invention provides a liquid crystal display device manufactured by the above method.

In addition, the present invention provides a method of manufacturing a semiconductor device comprising the step of peeling the photoresist using the stripper composition for the photoresist.

The present invention also provides a semiconductor device manufactured by the above method.

The stripper composition for a photoresist according to the present invention can be applied to both a dip method and a single-leaf peeling process, and can be easily and cleanly removed in a short time even at a high temperature and a low temperature by a photolithography and wet etching process. In addition, it is possible to simultaneously minimize the corrosion of the conductive metal film such as aluminum, aluminum alloy, copper, copper alloy and the insulating film such as silicon oxide film and silicon nitride film without using isopropanol as an intermediate cleaning solution.

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

The present invention comprises a) 3 to 30% by weight of a water-soluble organic amine compound, b) 65 to 95% by weight of a polar solvent having a boiling point of at least 150 ° C, and c) 0.01% to 5% by weight of a compound for forming a SAM (Self Assembly Monolayer). It provides a stripper composition for a photoresist comprising a%.

The a) water-soluble organic amine compound preferably includes at least one member selected from the group consisting of primary amino alcohol compounds, secondary amino alcohol compounds and tertiary amino alcohol compounds. Specific examples of the amino alcohol compounds include monoethanol amine (MEA), N-methylethanolamine (N-MEA), 1-aminoisopropanol (AIP), 2-amino-1-propanol, and 2- (2-amino Ethoxy) -1-ethanol (AEE), N-methylaminoethanol (N-MAE), 3-amino-1-propanol, 4-amino-1-butanol, 2- (2-aminoethylamino) -1- It is preferable to use at least one selected from the group consisting of ethanol, diethanol amine (DEA), and triethanol amine (TEA), more preferably N-methylaminoethanol (N-MAE) is a peeling performance, corrosion prevention Excellent in terms of power and economics

The content of the water-soluble organic amine compound is preferably 3 to 30% based on the total weight of the stripper composition for photoresist, more preferably 5 to 20% by weight. When the content of the water-soluble organic amine compound is less than 3% by weight, the peeling force on the modified photoresist is not sufficient, and when the amount of the water-soluble organic amine compound is higher than 30% by weight, the viscosity value is increased and the peeling time is low due to the low photoresist penetration in the lift-off method. In addition, the corrosion resistance of the photoresist underlayer to the conductive metal film can be increased.

B) The polar solvent compound having a boiling point of at least 150 ° C. or more has excellent compatibility with water and organic compounds, serves as a solvent for dissolving the photoresist, and in addition, lowers the surface tension of the stripper to wett the photoresist film. It works to improve the wetting property.

Polar solvent compounds having a boiling point of at least 150 ° C. include N-methyl formamide (NMF), diethylene glycol monobutyl ether (butyl carbitol, BDG), diethylene glycol monomethyl ether (methyl carbitol, MDG), diethylene Group consisting of glycol monoethyl ether (ethyl carbitol, EDG), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), dipropylene glycol monomethyl ether (DPM), dipropylene glycol monoethyl ether (DPE) and the like One or more kinds selected from can be used.

The polar solvent compound having a boiling point of at least 150 ° C preferably has a viscosity of 2 cps or less and a boiling point of at least 150 ° C, more preferably 150 to 300 ° C. When the boiling point of the polar solvent is less than 150 ℃ may be volatilized in a high temperature work process may reduce process safety and work reproducibility.

The polar solvent compound having a boiling point of at least 150 ° C may include 65 to 95% by weight based on the total weight of the stripper composition for photoresist. When the content is less than 65% by weight, the surface tension of the stripper is increased to provide wettability ( wetting) may be lowered, and if it exceeds 95% by weight, the peeling force on the photoresist may be lowered.

C) The compound for forming SAM is to form a SAM so that the conductive layer of the lower layer of the photoresist, such as aluminum or aluminum alloy, copper, copper alloy, or an insulating film such as silicon oxide film, silicon nitride film, etc. Play a role.

As the compound for forming the SAM, an alkane thiol compound and an aromatic thiol compound may be used. Preferably, methanethiol, ethanethiol, hexanethiol, octanethiol, decanethiol, dodecanethiol, 1,3-propanedithiol (1, 3-propanedithiol), 1,4-butanethiol, 1,5-pentanethiol, 1,6-pentanethiol, 1,6-hexanedithiol, 1,7- Heptanedithiol (1,7- heptanedithiol), 1,8-octanedithiol, thiophenol, terphenyl-4-methanethiol, terphenyl- 4-thiol (terphenyl-4-thiol) or anthracene-2-thiol (anthracene-2-thiol) and the like can be used, but is not limited thereto.

The compound for forming the SAM preferably comprises 0.01 to 5% by weight based on the total weight of the stripper composition for photoresist. When the content of the compound for forming the SAM is less than 0.01% by weight, the substrate to be peeled should be contacted with the stripping solution for a long time for the desired degree of peeling. In this case, corrosion may occur in the metal wiring. If the amount of the compound to be formed exceeds 5% by weight, the price is increased, there is a problem in that it is inefficient in terms of price-performance, and is uneconomical.

In general, when washing directly with water without using isopropanol, which is an intermediate cleaning solution, the amine component in the stripper is mixed with water to form highly corrosive alkali hydroxy ions, which is conductive to aluminum, aluminum alloy, copper, or copper alloy. Promotes corrosion of the metal film. However, the SAM-forming compound is adsorbed on the surface of aluminum in an alkaline state to form a protective film to prevent corrosion of metal by hydroxy ions without using isopropanol. In addition, the protective film by SAM of the present invention is significantly improved corrosion protection performance compared to benzotriazole or tolyltriazole, which has been widely used as a corrosion inhibitor of the copper film, copper or copper alloy of the photoresist underlayer even in small amounts It does not cause corrosion of conductive films such as films.

Stripper composition for a photoresist of the present invention consisting of the above components may further comprise one or more of a polar aprotic solvent, a corrosion inhibitor and a water-soluble nonionic surfactant, if necessary.

The polar aprotic solvent may be a compound having excellent solubility in polymer resin and photoactive compound, which are main components of the photoresist, compared to other solvents. In particular, the polar aprotic solvent has high compatibility with water, and can be mixed with the water-soluble organic amine compound and the polar solvent having a boiling point of at least 150 ° C. in all ratios, and preferably a compound having a boiling point of at least 150 ° C. Do.

The polar aprotic solvent is 1 selected from the group consisting of N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylformamide (DMF), tetramethylenesulfone, and the like. More than one species can be used.

The added polar aprotic solvent is preferably included in the stripper composition in excess of 0 to 30% by weight, and can be applied to both organic strippers and aqueous strippers that do not contain water. When the polar aprotic solvent exceeds 30% by weight, a problem may occur that a residue of the cross-cured photoresist remains in the conductive metal film and the insulating film during the severe etching process.

The corrosion inhibitor may be used one or more selected from the group consisting of a compound represented by the formula (1).

In the formula (1)

R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms,

R ₅ and R ₆ are each independently a hydroxyalkyl group having 1 to 4 carbon atoms.

The corrosion inhibitor controls the metal corrosion by the non-covalent pair of electrons of abundant nitrogen atoms present in the triazole ring electronically combined with copper, and the metal and hydroxy group directly substituted in the benzene ring adsorb the aluminum to control the metal corrosion by basic solution do.

The corrosion inhibitor preferably contains 0.01 to 5% by weight, more preferably 0.1 to 1% by weight in the stripper composition. When the content is less than 0.01% by weight, the substrate to be peeled must be brought into contact with the stripping solution for a long time in order to obtain a desired degree of peeling. In this case, partial corrosion may occur in the metal wiring. In addition, when the content exceeds 5% by weight can reduce the peel force of the stripper composition, there is a problem that the price is inefficient in terms of price-performance ratio, it is uneconomical.

The water-soluble nonionic surfactant lowers the surface tension of the stripper when the water content increases, and serves to prevent the phenomenon of redeposition after peeling off the deteriorated photoresist from the substrate.

The water-soluble nonionic surfactant does not cause chemical change even in the highly basic stripper composition, and serves to improve the compatibility of water and the organic solvent usable in the stripper composition and the stripper peelability.

The water-soluble nonionic surfactant may be used one or more selected from the group consisting of compounds represented by the following formula (2).

In the formula (2)

R ₇ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

T is hydrogen, a methyl group, or an ethyl group,

m is an integer of 1 to 4,

n is an integer from 1 to 50.

The water-soluble nonionic surfactant may be used in different amounts depending on the type and content of the components used in the stripper composition, and when water is not included, the water-soluble nonionic surfactant may not be used. When the content of water increases, the water-soluble nonionic surfactant preferably contains more than 0 to less than 1% by weight, more preferably 0.01 to 0.3% by weight. If the content is more than 1% by weight, there is no particular improvement, the viscosity is increased, the low temperature peel force is lowered, there is a problem that the cost of the composition is uneconomical.

In addition, the present invention provides a method for peeling a photoresist comprising the step of etching the photoresist pattern formed on a substrate including a metal wiring as a mask, followed by peeling with the stripper composition for photoresist. do.

The stripper composition for photoresist is a dip method of dipping several sheets of the substrate to be peeled at the same time in a large amount of stripper liquid in order to peel the photoresist from the substrate on which the fine circuit pattern is formed and spraying the stripping liquid onto the substrate one by one. The present invention can be applied to any single sheet type which is sprayed to remove photoresist.

The metal film for forming the metal wiring includes at least one single film, a multilayer film, and the like selected from the group consisting of aluminum, aluminum alloy, copper, copper alloy, and the like used for circuit formation of a semiconductor device or a liquid crystal display device. Here, the at least one single film or multi-layer film selected from the group consisting of aluminum, aluminum alloy, copper or copper alloy may vary in form, and a single film such as aluminum and copper, and a double film or copper such as copper / molybdenum A triple film such as / molybdenum / titanium may be mentioned, but is not limited thereto.

As described above, the photoresist that can be peeled off using the stripper composition for photoresists of the present invention may be a positive photoresist, a negative photoresist, or a positive / negative photoresist, or a dual tone photoresist. A photoresist composed of a novolak-based phenol resin and a photoactive compound composed mainly of diazonaphthoquinone is preferable.

The stripper composition for a photoresist of the present invention comprising the above components may be sprayed by dropping or spraying through a nozzle to remove unnecessary photoresist generated at edges and rear surfaces of the substrate.

The dropping or spraying amount of the photoresist stripper composition can be adjusted and used depending on the kind of photosensitive resin used and the thickness of the film, and it is particularly preferable to select and use in the range of 5 to 100 cc / min. In addition, the present invention may be formed by spraying the stripper composition as described above and then forming a fine circuit pattern through a subsequent photolithography process.

In addition, the present invention provides a method for manufacturing a liquid crystal display device or a semiconductor device, comprising the step of peeling the photoresist using the stripper composition for photoresist, a liquid crystal display device or a semiconductor device manufactured therefrom do.

Processes before and after the peeling step may be performed according to a conventional liquid crystal display device or semiconductor device manufacturing process.

The stripper composition for photoresists of the present invention as described above can be applied to both the dip method and the single-leaf peeling process, and the photoresist film that has been altered and cured by harsh photolithography and wet etching processes can be easily and cleanly in a short time even at high temperature and low temperature. Not only can it be removed, but it also minimizes the corrosion of conductive metal films such as aluminum, aluminum alloys, copper and copper alloys, and insulating films such as silicon oxide films and silicon nitride films without using isopropanol as an intermediate cleaning solution. have.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Example 1

10 wt% of 2- (2-aminoethoxy) -1-ethanol as a water-soluble organic amine compound in a mixing tank equipped with a stirrer, 89.9 wt% of a polar solvent having a boiling point of at least 150 ° C, and a methanethiol as a compound for forming a SAM (Methanethiol) 0.1 wt% was added, and then stirred at a speed of 500 rpm for 1 hour at 70 ° C. to prepare a stripper composition for photoresist.

Examples 2 to 21 and Comparative Examples 1 to 3

The stripper composition for photoresist was prepared in the same manner as in Example 1 by mixing the composition and the content shown in Table 1 below.

Experimental Example

Peeling ability test

After etching, the specimen having the photoresist pattern remaining in the photoresist stripper composition prepared in Examples 1 to 21 and Comparative Examples 1 to 3 at a temperature of 50 ° C. and 70 ° C. was immersed for 10 minutes, and then the specimen was removed from the stripping solution. After rinsing with ultrapure water for 1 minute, the mixture was dried using nitrogen gas. Then, the removal property of the photoresist pattern was evaluated using a scanning electron microscope, and the results are shown in Table 2 below.

How to Display Removability Assessment Results

◎: Good O: Good △: Normal X: Poor

Corrosion Resistance Test

After leaving the stripper composition for photoresist prepared in Examples 1 to 21 and Comparative Examples 1 to 3 for 24 hours at 60 ° C., the Mo / Al and Cu / MoTi bilayer specimens were immersed in the stripper for 30 minutes. The specimen was removed from the stripping solution, rinsed with ultrapure water for 1 minute, and dried using nitrogen gas. And the degree of corrosion of aluminum (Al) and copper (Cu) was evaluated using a scanning electron microscope, the results are shown in Table 2 below.

How to Display Corrosion Resistance Evaluation Results

◎: Good O: Good △: Normal X: Poor

The scanning electron micrograph of the surface after etching the Cu / MoTi double layer using the stripper composition for photoresists according to Examples 1 to 3 according to the present invention is shown in FIG. 1. In addition, the scanning electron micrograph of the surface after etching the Cu / MoTi double film using the stripper composition for photoresists according to Comparative Examples 1 to 3 is shown in FIG.

division Ingredient (wt%) a) ingredients b) ingredients c) components Formula 1 Kinds amount Kinds amount Kinds amount Kinds amount Example #One AEE 10 NMF 89.9 Methanethiol 0.1 BTA 0 #2 MEA 10 NMF 89.9 Methanethiol 0.1 BTA 0 # 3 NMEA 10 NMF 89.9 Methanethiol 0.1 BTA 0 #4 AEE 10 DMSO 89.9 Methanethiol 0.1 BTA 0 # 5 MEA 10 DMSO 89.9 Methanethiol 0.1 BTA 0 # 6 NMEA 10 DMSO 89.9 Methanethiol 0.1 BTA 0 # 7 AEE 10 DMAc 89.9 Methanethiol 0.1 BTA 0 #8 MEA 10 DMAc 89.9 Methanethiol 0.1 BTA 0 # 9 NMEA 10 DMAc 89.9 Methanethiol 0.1 BTA 0 # 10 AEE 10 NMF 89.9 Methanethiol 0.1 BTA 0 # 11 MEA 10 NMF 89.9 Methanethiol 0.1 BTA 0 # 12 NMEA 10 NMF 89.9 Methanethiol 0.1 BTA 0 # 13 AEE 10 MDG 89.9 Methanethiol 0.1 BTA 0 # 18 NMEA 10 EDG 89.9 Methanethiol 0.1 BTA 0 # 19 AEE 10 BDG 89.9 Methanethiol 0.1 BTA 0 # 20 MEA 10 BDG 89.9 Methanethiol 0.1 BTA 0 # 21 NMEA 10 BDG 89.9 Methanethiol 0.1 BTA 0 Comparative example #One AEE 10 NMF 89.9 Methanethiol 0 BTA 0.5 #2 MEA 10 NMF 89.9 Methanethiol 0 BTA 0.5 # 3 NMEA 10 NMF 89.9 Methanethiol 0 BTA 0.5

AEE: 2- (2-aminoethoxy) -1-ethanol

MEA: Monoethanol Amine

NMEA: N-methylethanolamine

NMF: N-methylformamide

DMSO: Dimethyl Sulfoxide

DMAc: Dimethylacetamide

MDG: Diethylene Glycol Monomethyl Ether

EDG: diethylene glycol monoethyl ether

BDG: Diethylene Glycol Monobutyl Ether

BTA: Benzotriazole

division evaluation corrosion Peeling Al Cu 50 ℃ 70 ℃ Example #One ◎ ◎ ◎ ◎ #2 ◎ ◎ ◎ ◎ # 3 ◎ ◎ ◎ ◎ #4 ◎ ◎ ◎ ◎ # 5 ◎ ◎ ◎ ◎ # 6 ◎ ◎ ◎ ◎ # 7 ◎ ◎ ◎ ◎ #8 ◎ ◎ ◎ ◎ # 9 ◎ ◎ ◎ ◎ # 10 ◎ ◎ ◎ ◎ # 11 ◎ ◎ ◎ ◎ # 12 ◎ ◎ ◎ ◎ # 13 ◎ ◎ △ ○ # 14 ◎ ◎ △ ○ # 15 ◎ ◎ △ ○ # 16 ◎ ◎ △ ○ # 17 ◎ ◎ △ ○ # 18 ◎ ◎ △ ○ # 19 ◎ ◎ △ ○ # 20 ◎ ◎ △ ○ # 21 ◎ ◎ △ ○ Comparative example #One △ × ◎ ◎ #2 × × ◎ ◎ # 3 × △ ◎ ◎

1 is a photograph taken after scanning the surface of the copper / MoTi double layer using a photoresist stripper composition according to Examples 1 to 3 of the present invention, using a scanning electron microscope.

FIG. 2 is a photograph taken after scanning the copper / MoTi double layer using the stripper composition for photoresist according to Comparative Examples 1 to 3, using a scanning electron microscope.

Claims (21)

a) 3 to 30% by weight of a water soluble organic amine compound, b) 65 to 95% by weight of a polar solvent having a boiling point of at least 150 ° C., and c) 0.01 to 5% by weight of a compound for forming a Self Assembly Monolayer (SAM) / RTI > Compounds for forming the SAM is methanethiol, ethanethiol, hexanethiol, hexanethiol, octanethiol, decanethiol, dodecanethiol, 1,3-propane Dithiol (1,3-propanedithiol), 1,4-butanedithiol (1,4-butanethiol), 1,5-pentanethiol (1,5-pentanethiol), 1,6-hexanedithiol (hexanedithiol) , 1,7-heptandithiol (1,7- heptanedithiol), 1,8-octanedithiol (1,8-octanetdihiol), thiophenol, terphenyl-4-methanethiol ), Terphenyl-4-thiol (terphenyl-4-thiol) and anthracene-2-thiol (anthracene-2-thiol) is at least one compound selected from the group consisting of stripper composition for photoresist. The stripper composition for photoresist according to claim 1, wherein the a) water-soluble organic amine compound is at least one compound selected from the group consisting of a primary amino alcohol compound, a secondary amino alcohol compound, and a tertiary amino alcohol compound. The method of claim 2, wherein the alcohol compound is monoethanol amine (MEA), N-methylethanolamine (N-MEA), 1-aminoisopropanol (AIP), 2-amino-1-propanol, 2- (2-amino Ethoxy) -1-ethanol (AEE) N-methylaminoethanol (N-MAE), 3-amino-1-propanol, 4-amino-1-butanol, 2- (2-aminoethylamino) -1-ethanol And at least one compound selected from the group consisting of diethanol amine (DEA) and triethanol amine (TEA). The method of claim 1, wherein b) the polar solvent compound having a boiling point of at least 150 ℃ N-methylformamide (NMF), diethylene glycol monobutyl ether (butyl carbitol, BDG), Diethylene glycol monomethyl ether (methyl carbitol, MDG), diethylene glycol monoethyl ether (ethyl carbitol, EDG), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), dipropylene glycol monomethyl ether (DPM) And at least one compound selected from the group consisting of dipropylene glycol monoethyl ether (DPE). delete delete The stripper composition for a photoresist according to claim 1, wherein the stripper composition for photoresist further comprises at least one selected from a polar aprotic solvent, a corrosion inhibitor, and a water-soluble nonionic surfactant. The group of claim 7, wherein the polar aprotic solvent is N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylformamide (DMF), and tetramethylenesulfone Stripper composition for photoresist, characterized in that at least one compound selected from. The stripper composition according to claim 7, wherein the polar aprotic solvent is included in an amount of more than 0 and 30% by weight or less based on the total weight of the stripper composition for photoresist. The stripper composition for photoresist according to claim 7, wherein the corrosion inhibitor is a compound represented by the following Chemical Formula 1. [Formula 1]

In the formula (1) R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, R5 and R6 are each independently a hydroxyalkyl group having 1 to 4 carbon atoms. The stripper composition according to claim 7, wherein the corrosion inhibitor comprises 0.01 to 5 wt% based on the total weight of the stripper composition for photoresist. The stripper composition according to claim 7, wherein the water-soluble nonionic surfactant is a compound represented by the following Chemical Formula 2. [Formula 2]

In the formula (2) R7 is hydrogen or an alkyl group having 1 to 10 carbon atoms, T is hydrogen, a methyl group, or an ethyl group, m is an integer of 1 to 4, n is an integer from 1 to 50. The stripper composition according to claim 7, wherein the water-soluble nonionic surfactant comprises more than 0 and less than 1 wt% based on the total weight of the stripper composition for photoresist. And etching the photoresist pattern formed on the substrate including the metal wiring as a mask, followed by peeling using the stripper composition for photoresist of claim 1. The method of claim 14, wherein the peeling method is a dip method or a single sheet method. 15. The method of claim 14, wherein the substrate is at least one single film or multilayer film selected from the group consisting of aluminum, aluminum alloy, copper and copper alloy. 15. The method of claim 14, wherein the photoresist is a positive photoresist, a negative photoresist, or a positive / negative combination photoresist. A method of manufacturing a liquid crystal display device comprising the step of peeling a photoresist using the stripper composition for photoresist of claim 1. A liquid crystal display device manufactured by the manufacturing method of claim 18. A method of manufacturing a semiconductor device comprising the step of peeling a photoresist using the stripper composition for photoresists of claim 1. A semiconductor device manufactured by the manufacturing method of claim 20.

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