KR100544888B1 - Photoresist Stripper Composition for Copper Wiring - Google Patents

Abstract

The present invention relates to a copper resist photoresist stripper composition used in the manufacture of semiconductor devices and liquid crystal display devices, and more specifically, a) 5 to 50 parts by weight of a water-soluble organic amine compound; b) 20 to 95 parts by weight of an organic solvent having a boiling point of at least 150 ° C. or more; And c) relates to a copper resist photoresist stripper composition comprising 0.01 to 5 parts by weight of a corrosion inhibitor.

The present invention can easily remove the modified photoresist film during a photolithography process in a short time even at high temperature and low temperature, and in particular in conductive metal films such as copper and copper alloy films under the photoresist or insulating films such as silicon oxide films and silicon nitride films. It is possible to provide a photoresist stripper composition having excellent corrosion protection.

Photoresist, stripper, corrosion inhibitor, water soluble organic amine compound, organic solvent, copper, copper alloy film

Description

Photoresist stripper composition for copper wiring {PHOTORESIST STRIPPER COMPOSITION FOR COPPER TFT}

1A, 1B and 1C are cross-sectional photographs, 45-degree cross-sectional photographs, and side photographs of Cu / Mo double membranes according to the experimental results of the corrosion evaluation-1 of Example 1 of the present invention, respectively.

2A, 2B and 2C are cross-sectional photographs, 45-degree cross-sectional photographs, and side photographs of Cu / Mo double membranes according to experimental results of corrosion evaluation-1 of the conventional Comparative Example 1, respectively.

3A, 3B, and 3C are cross-sectional photographs, 45-degree cross-sectional photographs, and side photographs of Cu / Mo bilayers obtained by removing photoresist with 40 ° C. acetone, respectively.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist stripper composition for copper wiring used in the manufacture of flat panel display devices, including semiconductor devices and liquid crystal display devices. And a photoresist stripper composition for copper wiring that can be easily removed even at a low temperature within a short time and does not cause corrosion of the conductive film and the insulating film under the photoresist.

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 a conductive metal film such as copper or a copper alloy film formed on a substrate, or an insulating film such as a silicon oxide film or a silicon nitride film, which is selectively exposed to light, After the development process to form a photoresist pattern, the conductive metal film or the insulating film is wet or dry etched using the patterned photoresist film as a mask to transfer the fine circuit pattern to the lower photoresist layer, and then the unnecessary photoresist layer is removed. Proceeds to the step of removing with a stripper (peel).

Basic characteristics of the stripper for removing the photoresist for manufacturing the semiconductor device and the liquid crystal display device are as follows.

First, it should be able to exfoliate the photoresist in a short time at low temperature and have an excellent exfoliation ability that should not leave photoresist residue on the substrate after rinse. In addition, it should have low corrosion resistance that should not damage the metal film or insulating film of the photoresist underlayer. In addition, if a room temperature reaction occurs between the solvents forming the stripper, the storage stability of the stripper may be a problem and different physical properties may be shown depending on the mixing sequence during the production of the stripper. Therefore, there should be non-reactivity and high temperature stability between the mixed solvents. In addition, it should be low toxicity in order to be less toxic in consideration of the safety of the worker or environmental problems during disposal. In addition, when the photoresist stripping proceeds at a high temperature process, if a lot of volatilization occurs, the component ratio changes rapidly and the process stability and work reproducibility of the stripper are lowered. In addition, the number of substrates that can be processed with a certain amount of stripper should be large, the supply of the components constituting the stripper should be easy, low-cost and economical to enable recycling through the reprocessing of the waste stripper.

In order to satisfy these conditions, various stripper compositions for photoresists have been developed, for example, as follows.

As an example of an initially developed photoresist stripper composition, Japanese Patent Laid-Open 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 more. Japanese Patent Application Laid-Open No. 57-84456 describes a stripper composition composed of dimethyl sulfoxide or diethyl sulfoxide, and an organic sulfone compound. In addition, U.S. Patent No. 4,256,294 discloses a stripper composition composed of 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 150 ° C. or higher. It is difficult to use due to severe corrosion on metal film and strong toxicity and environmental pollution.

In order to solve this problem, stripper compositions prepared by mixing various organic solvents with water-soluble alkanolamine as an essential component have been proposed.

U.S. Patent 4,617,251 discloses organic amine compounds such as monoethanol amine (MEA) and 2- (2-aminoethoxy) -1-ethanol (AEE); And polar solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidinone (NMP), dimethyl sulfoxide (DMSO), carbitol acetate, and propylene glycol monomethyl ether acetate (PGMEA). A two-component stripper composition is disclosed. US 4,770,713 discloses organic amine compounds; And N-methylacetamide, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-N-ethylpropionamide, diethylacetamide (DEAc), dipropylacetamide (DPAc), N, N A two-component stripper composition comprising an amide solvent such as -dimethylpropionamide and N, N-dimethylbutylamide is disclosed. Japanese Patent Laid-Open No. 62-49355 discloses a stripper composition composed of an alkylene polyamine sulfone compound in which ethylene oxide is introduced into alkanol amine and ethylenediamine and a glycol monoalkyl ether, and Japanese Patent Laid-Open No. 63-208043 discloses a water-soluble alkanol. A stripper composition containing amine and DMI is disclosed. Japanese Patent Laid-Open No. 63-231343 discloses a stripper composition for a positive photoresist composed of an amine compound, a polar solvent and a surfactant. Japanese Patent Laid-Open No. 64-42653 discloses at least 50% by weight of dimethyl sulfoxide (DMSO), diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, gamma butyrolactone and 1,3-dimethyl-2-imidazolidinone A stripper composition composed of 1 to 50% by weight of one or more solvents selected from (DMI) and a nitrogen-containing organic hydroxy compound such as monoethanolamine (MEA) is disclosed. Japanese Patent Laid-Open No. 4-124668 discloses 20 to 90% by weight of organic amine, 0.1 to 20% by weight of phosphate ester surfactant, 0.1 to 20% by weight of 2-butyne-1,4-diol, diethylene glycol dialkyl ether and aprotic A stripper composition composed of polar solvents is disclosed. 2-butyne-1,4-diol and phosphate ester surfactants were added here to prevent corrosion of the metal layer within a range that does not reduce the peeling properties. However, such a photoresist stripping composition has a weak corrosion protection against copper and copper alloy films, causing severe corrosion during the stripping process, and causing a problem during deposition of the gate insulating film, which is a later process.

In addition, Japanese Patent Laid-Open No. 4-350660 discloses a stripper composition composed of DMI, DMSO, and water-soluble organic amine, and Japanese Patent Laid-Open No. 5-281753 discloses an alkanol amine, a sulfone compound or a sulfoxide compound, (C ₆ H ₆ ). A stripper composition comprising a hydroxy compound of _n (OH) _n ( _where n is an integer of 1, 2 or 3) is disclosed, and Japanese Patent Laid-Open No. 8-87118 discloses N-alkylalkanolamines 50 to 90 A stripper composition comprising 50 wt%, DMSO or DMF 50 wt% is disclosed. However, these photoresist stripper compositions exhibit relatively good characteristics in terms of peeling force and stability. However, in recent liquid crystal display and semiconductor device manufacturing processes, glass substrates and silicon wafer substrates are processed at a high temperature of 120 ° C. or higher. As the conditions become severe, the photoresist is often postbaked at a high temperature, and the degree of deterioration hardening is increased therefrom, so that the stripper composition mentioned above is not completely removed.

A photoresist stripper composition comprising water and / or a hydroxylamine compound has been proposed as a composition for cleanly removing the photoresist cured through the high temperature process. For example, Japanese Patent Laid-Open No. 4-289866 discloses a stripper composition composed of hydroxyl amines, alkanol amines, and water, and Japanese Patent Laid-Open No. 6-266119 discloses hydroxyl amines, alkanol amines, water, and anticorrosion. A stripper composition consisting of zero has been disclosed. In addition, Japanese Patent Laid-Open No. 7-69618 discloses a polar aprotic solvent such as gamma butyrolactone (GBL), DMF, DMAc, NMP, amino alcohols containing 2-methylamino ethanol (N-MAE), and water. Stripper compositions containing in proportions are described. In addition, Japanese Patent Laid-Open No. 8-123043 discloses a stripper composition composed of glycol alkyl ether such as amino alcohol, water, diethylene glycol monobutyl ether (BDG), and the like. Japanese Patent Laid-Open No. 8-262746 discloses a stripper composition composed of alkanol amines, alkoxyalkylamines, glycol monoalkyl ethers, sugar compounds, quaternary ammonium hydroxides, and water. A stripper composition containing sugar compounds such as amines, hydroxyl amines, diethylene glycol monoalkyl ethers, sorbitol and the like as an anticorrosive and water is disclosed. Japanese Patent Laid-Open No. 9-96911 discloses a stripper composition composed of 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, the stripper compositions are deteriorated by harsh high temperature processes, dry etching, ashing, and ion implantation processes, and are peeled off from photoresist etch residues generated by reaction with metallic by-products in the cross-cured photoresist film and etching process. In the corrosion protection performance of the copper and copper alloy film, which is a resist and a photoresist conductive underlayer, is not sufficient. In addition, the hydroxyl amine compound at high temperature conditions is unstable, there is a problem that decomposes over time.

Such various stripper compositions vary considerably in terms of photoresist peelability, metal corrosiveness, variety of cleaning processes after peeling, work reproducibility and storage stability, and economic efficiency, depending on the content ratio between components. There is a continuing need for the development of economical stripper compositions with low performance.

On the other hand, as liquid crystal displays become larger and mass-produced, photoresist stripping using a single wafer treatment method is more common than a dipping method, which uses a lot of strippers. Stripper compositions suitable for the installation are introduced.

For example, Korean Patent Publication No. 2000-8103 discloses a stripper composition comprising 5 to 15% by weight of alkanol amine, 35 to 55% by weight of sulfoxide or sulfone compound, and 35 to 55% by weight of glycol ether. Korean Patent Publication No. 2000-8553 discloses a total content of 10 to 30% by weight of a water-soluble amine compound, diethylene glycol monoalkyl ether and N-alkyl pyrrolidinone, or hydroxyalkyl pyrrolidinone. A stripper composition is presented, characterized in that weight percent. However, the compositions have a disadvantage in that the metal corrosiveness is good but the low temperature peel strength is rather weak.

In view of the problems of the prior art, the present invention is suitable for both the dip method and the single-leaf type peeling process, and the photoresist film deteriorated by the harsh photolithography process can be peeled off at low temperature in a short time, and copper and copper alloy An object of the present invention is to provide a copper resist photoresist stripper composition that does not damage the conductive film and the insulating film.

Another object of the present invention is to provide a method of peeling a photoresist using the stripper composition for photoresist and a liquid crystal display device or a semiconductor device manufactured by the same.

In order to achieve the above object, the present invention

a) 5 to 50 parts by weight of a water-soluble organic amine compound;

b) 20 to 95 parts by weight of an organic solvent having a boiling point of at least 150 ° C. or more; And

c) 0.01 to 5 parts by weight of a corrosion inhibitor selected from the group consisting of compounds represented by formulas (1) and (2)

It provides a photoresist stripper composition for copper wiring comprising:

[Formula 1]

In the formula of Formula 1,

R ₁ is hydrogen or an alkyl group having 1 to 12 carbon atoms,

[Formula 2]

In the formula (2),

R ₂ is hydrogen or an alkyl group having 1 to 5 carbon atoms,

R ₃ is hydrogen, a hydroxy group or a thiol group.

In another aspect, the present invention provides a method for removing a photoresist comprising the step of etching the photoresist pattern formed on a semiconductor substrate including a metal wiring with a mask, and stripping with a stripper composition of the substrate. The metal wiring includes Cu or a Cu alloy film as an upper film.

In another aspect, the present invention provides a liquid crystal display device or a semiconductor device manufactured by including the peeling method of the substrate.

Hereinafter, the present invention will be described in detail.

The present invention is characterized in providing a photoresist stripper composition for copper wiring comprising a water-soluble organic amine compound, an organic solvent having a boiling point above a specific temperature, and a corrosion inhibitor for preventing corrosion on the metal film under the photoresist.

In the stripper composition for photoresists of the present invention, the water-soluble organic amine compound of (a) is at least one selected from the group consisting of primary amino alcohol compounds, secondary amino alcohol compounds, and tertiary amino alcohol compounds. It is preferable that it is an amino alcohol compound. Specific examples of the amino alcohol compounds include monoethanol amine (MEA), 1-aminoisopropanol (AIP), 2-amino-1-propanol, N-methylaminoethanol (NMAE), 3-amino-1-propanol , 4-amino-1-butanol, 2- (2-aminoethoxy) -1-ethanol (AEE), 2- (2-aminoethylamino) -1-ethanol, diethanol amine (DEA), and trie It is preferable to use a compound selected from the group consisting of tanol amines (TEA), more preferably MEA, AIP, NMAE, or AEE is superior in terms of peeling performance and corrosion protection.

The amount of the water-soluble organic amine compound is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight based on the total composition. If the amount of the water-soluble organic amine compound is less than 5 parts by weight, the peeling force on the modified photoresist is insufficient. If the amount of the water-soluble organic amine compound is greater than 50 parts by weight, the corrosion resistance of the conductive metal film of the lower layer of the photoresist is increased.

The organic solvent (b) used in the photoresist stripper composition of the present invention has a boiling point of at least 150 ° C. or more, and the organic solvent has excellent compatibility with water and organic compounds and serves as a solvent for dissolving the photoresist. . In addition, the organic solvent of the present invention, in addition to functioning as a solvent, lowers the surface tension of the stripper to improve the wetting property of the photoresist film.

For example, it is preferable to use a compound selected from the group consisting of alkylene glycols, alkylene glycol monoalkyl ethers and polar aprotic solvents. Specific examples of the alkylene glycols include monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol. Specific examples of the alkylene glycol monoalkyl ethers include diethylene glycol monomethyl ether (methyl carbitol, MDG), diethylene glycol monoethyl ether (ethyl carbitol, EDG), diethylene glycol monobutyl ether (butyl carbitol). , BDG), dipropylene glycol monomethyl ether (DPM), and dipropylene glycol monoethyl ether (DPE). Specific examples of the polar aprotic solvents include N-methylpyrrolidone (NMP), gamma butyrolactone (GBL), 1,3-dimethyl-2-imidazolidinone (DMI), and dimethyl sulfoxide (DMSO). , Dimethylacetamide (DMAc), dimethylformamide (DMF) and tetramethylenesulfone. In the composition of the present invention, the organic solvent is more preferably used diethylene glycol, tetraethylene glycol, diethylene glycol monobutyl ether, or N-methylpyrrolidone.

The amount of the organic solvent is preferably 20 to 95 parts by weight based on the total composition. When the amount of the organic solvent is less than 20 parts by weight, the surface tension of the stripper is increased, so that wetting is lowered. Is lowered.

In the stripper composition for photoresists of the present invention, it is preferable that the corrosion inhibitor of (c) uses a compound such that the conductive metal film and the insulating film of the photoresist underlayer are not damaged. Specific examples of the corrosion inhibitor, for example, it is preferable to use a compound selected from the group consisting of the formula (1) and (2). More preferably, 5-carboxybenzotriazole butyl ester, 5-carboxybenzotriazole octyl ester, 5-carboxybenzotriazole dodecyl ester, 2-mercapto-1-methylimidazole, 1-methylimida Sol.

The anti-corrosion agent is significantly improved in anti-corrosion performance compared to benzotriazole, tolyl triazole, etc., which has been widely used as an anti-corrosion agent of copper films, and does not cause corrosion of the copper or copper alloy film of the photoresist underlayer even in a small amount of visible light. It also works very effectively to remove residues of the cured photoresist.

Therefore, the amount of the corrosion inhibitor is preferably used in 0.01 to 5 parts by weight based on the total composition. When the amount of the corrosion inhibitor is less than 0.01 part by weight, partial corrosion may occur in the metal wiring when the substrate to be peeled is in contact with the stripping solution for a long time, and when used in excess of 5 parts by weight, the peeling force may be reduced. In addition, the additional anti-corrosion performance can not be expected, there is a problem that the cost of the composition is inefficient in terms of price-performance ratio.

In addition, the stripper composition for photoresists of the present invention may further comprise (d) water, and (e) a water-soluble nonionic surfactant to provide an aqueous stripper composition.

The amount of the water (d) is preferably used at most 30 parts by weight based on the total composition, more preferably 10 to 25 parts by weight. At this time, if a certain amount of water is contained more excellent peeling force in the low temperature peeling process below 50 ℃, but if the content of water exceeds 30 parts by weight may corrode the metal wiring of the lower portion of the photoresist, Solving power and photoresist peeling force are lowered.

The (e) water-soluble nonionic surfactant is essentially used to lower the surface tension of the stripper when the water content is increased, and also prevents redeposition after peeling from the substrate of the deteriorated photoresist. In terms of effectiveness.

As the water-soluble nonionic surfactant, it is preferable to use a water-soluble nonionic surfactant represented by the following formula (3). In particular, the surfactant represented by the following formula (3) is excellent in compatibility with water and the organic solvent used in the stripper composition described above, without causing chemical changes even in the highly basic stripper composition, it is possible to improve the stripper peeling properties .

[Formula 3]

(In Chemical Formula 3,

R ₄ is hydrogen or a methyl group; T is hydrogen, methyl group or ethyl group; m is an integer from 1 to 4; n is an integer from 1 to 50.)

The amount of the water-soluble nonionic surfactant depends on the type and ratio of the stripper components and may not be used when water is not included. If the amount of water increases, up to 1 part by weight can be used, more preferably 0.01 to 0.3 parts by weight is effective. If the content of the water-soluble surfactant exceeds 1% by weight, there is no special improvement and the viscosity is increased, and the composition price is high and there is no economy. In general, the lower the viscosity, the better the low temperature peel force.

In addition, the present invention provides a method of peeling a photoresist comprising the step of etching the photoresist pattern formed on a semiconductor substrate including a metal wiring with a mask, and stripping with a stripper composition of the substrate.

The method of peeling photoresist from a substrate engraved with a fine circuit pattern by using the stripper composition for photoresists of the present invention 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 and peeling one by one. Both single-layer methods of spraying (spraying) the liquid onto the substrate to remove the photoresist can be used.

Types of photoresist that can be stripped using the photoresist stripper composition of the present invention include a positive photoresist, a negative photoresist, and a positive / negative dual tone photoresist, and the components are restricted. A photoresist that is not applied, but is particularly effective, is a photoresist film composed of a novolak-based phenol resin and a photoactive compound based on diazonaphthoquinone.

In addition, the present invention can provide a liquid crystal display device or a semiconductor device manufactured by a conventional method including the peeling method of the substrate.

As described above, according to the method of the present invention, the photoresist film modified during the photolithography process can be easily removed within a short time even at a high temperature and a low temperature, and a conductive metal film or a silicon oxide film or silicon such as copper or a copper alloy film on the photoresist is easily removed. The stripper composition for photoresists excellent in the corrosion protection with respect to insulating films, such as a nitride film, can be provided.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are merely to illustrate the invention and the scope of the present invention is not limited to the following examples. In the following Examples and Comparative Examples, unless otherwise indicated, the component ratio of each composition is by weight.

Example 1

100 g of 2- (2-aminoethoxy) -1-ethanol, 400 g of tetraethylene glycol, 497 g of diethylene glycol monobutyl ether, and 3 g of 5-carboxybenzotriazole butyl ester were mixed and stirred at room temperature for 2 hours. And then filtered to 0.1 ㎛ to prepare a stripper solution. For the stripper solution, the photoresist peel force and corrosion characteristics were evaluated in the following manner. At this time, the specimen used in the experiment was a glass substrate which went through the gate process in manufacturing TFT circuit of LCD. After forming Mo layer 300Å and Cu layer 2000Å on the glass, positive photoresist was applied and dried, and then patterned by photolithography. Is formed, and it is the state completed by wet etching.

1) Peel force evaluation

The specimen was immersed in the stripper solution maintained at 70 ° C. for 1 minute, washed with isopropanol for 30 seconds, ultrapure water for 30 seconds, and dried with nitrogen. After completion of drying, the specimen was observed for peeling of the photoresist with an optical microscope of 1,000 × magnification and an electron microscope (FE-SEM) of 5,000 to 10,000 magnification. Peel performance evaluation was evaluated based on the following criteria, the evaluation result was able to obtain a clean pattern without any photoresist foreign material.

◎: excellent peeling performance

○: good peeling performance

△: poor peeling performance

×: Peeling performance poor

2) Corrosion Evaluation-1

The specimen was immersed in the stripper solution maintained at 70 ° C. for 30 minutes, washed with isopropanol for 30 seconds, ultrapure water for 30 seconds, and dried with nitrogen. After completion of drying, the degree of corrosion of the surface, side, and cross section of the specimen was observed with an electron microscope (FE-SEM) of 50,000 to 100,000 magnification. Corrosion performance evaluation was evaluated based on the following criteria, and as a result of the evaluation, it was possible to obtain a clean pattern without any corrosion on the surface, side and cross section.

◎: No corrosion on the surface and side of Cu and Mo wiring

○: slight corrosion on the surface and sides of Cu and Mo wiring

△: partial corrosion on the surface and side of Cu and Mo wiring

X: When severe corrosion occurred to the surface and side of Cu and Mo wiring as a whole

3) Corrosion Evaluation-2

The specimen was immersed in the stripper solution maintained at 70 ° C. for 5 minutes, washed with isopropanol for 30 seconds, ultrapure water for 30 seconds, and dried with nitrogen. After three consecutive strip tests, the surface, sides, and cross-sections of the specimens were corroded with an electron microscope (FE-SEM) at 50,000 to 100,000 magnification. Corrosion performance evaluation was evaluated based on the following criteria, and the evaluation resulted in a clean pattern without any corrosion on the surface, side and cross section.

◎: No corrosion on the surface and side of Cu and Mo wiring

○: slight corrosion on the surface and sides of Cu and Mo wiring

△: partial corrosion on the surface and side of Cu and Mo wiring

X: When severe corrosion occurred to the surface and side of Cu and Mo wiring as a whole

[Examples 2 to 5 and Comparative Examples 1 to 7]

A stripper solution was prepared as in the composition shown in Table 1 below, and the peel force and the corrosion were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

division Ingredients (parts by weight) Properties a) ingredients b-1) Ingredient b-2) ingredients c) ingredients d) water e) ingredients Peel Evaluation Corrosion Evaluation Kinds amount Kinds amount Kinds amount Kinds amount One 2 Example One AEE 10 TEG 40 BDG 49.7 A1 0.3 - - ◎ ◎ ◎ 2 NMAE 10 NMP 30 TEG 59.7 A1 0.3 - - ◎ ◎ ◎ 3 AEE 20 TEG 30 BDG 49.7 A2 0.3 - - ◎ ◎ ◎ 4 AEE 10 NMP 30 TEG 59.7 B1 0.3 - - ◎ ○ ◎ 5 AEE 10 DMSO 30 BDG 59.6 A1 0.3 - - ◎ ◎ ◎ B1 0.1 6 NMAE 20 TMS 30 TEG 49.5 A2 0.3 - - ◎ ○ ◎ B2 0.2 7 NMAE 10 NMP 30 DPM 58 A2 2 - - ◎ ◎ ◎ 8 NMAE 10 DPM 40 TEG 48 A2 2 - - ◎ ◎ ◎ 9 MEA 10 DMAc 30 DPM 30 A2 4 - - ◎ ◎ ◎ BDG 26 10 MEA 10 TEG 60 BDG 25 A2 5 - - ◎ ○ ◎ 11 AIP 10 NMP 40 TEG 45 A2 5 - - ◎ ○ ◎ 12 AIP 10 DMAc 20 TEG 40 A1 3 - 0.1 ◎ ○ ◎ BDG 26.9 13 NMAE 10 NMP 30 BDG 48.9 A2 One 10 0.1 ○ ○ ○ 14 AEE 20 DMAc 20 TEG 35.9 A2 4 20 0.1 ◎ ○ ○ 15 AIP 10 NMP 40 BDG 26.9 A2 3 20 0.1 ◎ ○ ○ B2 One Comparative Example One AEE 10 TEG 40 BDG 50 - - - - ◎ × × 2 NMAE 10 NMP 30 TEG 60 - - - - ◎ × × 3 AEE 20 TEG 30 BDG 49.7 C2 0.3 - - ◎ × × 4 MEA 10 NMP 30 BDG 59 C1 One - - ◎ × △ 5 MEA 5 TEG 45 BDG 49 C2 One - 0.1 ○ △ ○ 6 NMAE 10 NMP 30 BDG 45.9 C1 4 10 0.1 ◎ △ △ 7 AEE 20 DMAc 20 TEG 35.9 C2 4 20 0.1 ◎ ○ ○

week)

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

NMAE: N-methylaminoethanol

MEA: Monoethanolamine

AIP: 1-aminoisopropanol

TEG: Tetraethylene Glycol

DPM: Dipropylene Glycol Monomethyl Ether

BDG: Diethylene Glycol Monobutyl Ether

NMP: N-methylpyrrolidone

DMSO: Dimethyl Sulfoxide

TMS: tetramethylenesulfone

DMAc: Dimethylacetamide

A1: 5-carboxybenzotriazole butyl ester

A2: 5-carboxybenzotriazole octyl ester

B1: 1-methylimidazole

B2: 2-mercapto-1-methylimidazole

C1: benzotriazole

C2: tolyltriazole (4-methylbenzotriazole, 5-methylbenzotriazole mixture)

e) Component: Compound of formula 3a:

As in Table 1, compared to Comparative Examples 1 to 7 in the case of the stripper composition of Examples 1 to 15 including at least one corrosion inhibitor selected from the group consisting of compounds represented by Formulas 1 and 2, It can be seen that the peeling performance and the corrosion protection are very excellent.

Cu / Mo according to the experimental results of Corrosion Evaluation-1 of Example 1 and Comparative Example 1, as compared with the cross-sectional side view of the Cu / Mo double film without corrosion, obtained by removing the photoresist with 40 ° C. acetone of FIG. 3. Mo corrosion results are shown in FIGS. 1 and 2, respectively.

In the results of FIGS. 1 and 2, in the case of FIG. 1 of Example 1, there is no difference from the SEM photograph of FIG. 3 without any corrosion, whereas in FIG. 2 of Comparative Example 1, severe corrosion of the upper copper (Cu) film was observed. It became.

As described above, the stripper composition of the present invention has excellent peeling performance at high and low temperatures with respect to the photoresist film modified by harsh photolithography and wet etching processes, and is particularly a copper or copper alloy film. Corrosion of the conductive film can be minimized.

Claims (12)

a) 5 to 50 parts by weight of a water-soluble organic amine compound; b) 20 to 95 parts by weight of an organic solvent having a boiling point of at least 150 ° C. or more; And c) 0.01 to 5 parts by weight of a corrosion inhibitor which is a compound represented by Formula 1 Copper resist photoresist stripper composition comprising: [Formula 1]

In the formula of Formula 1, R ₁ is hydrogen or an alkyl group having 1 to 12 carbon atoms. The method of claim 1, The photoresist stripper composition for copper wiring wherein the water-soluble organic amine compound of a) is an amino alcohol 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, The amino alcohol compounds are monoethanol amine (MEA), 1-aminoisopropanol (AIP), 2-amino-1-propanol, N-methylaminoethanol (N-MAE), 3-amino-1-propanol, 4- Amino-1-butanol, 2- (2-aminoethoxy) -1-ethanol (AEE), 2- (2-aminoethylamino) -1-ethanol, diethanol amine (DEA), and triethanol amine (TEA) Photoresist stripper composition for copper wiring selected from the group consisting of: The method of claim 1, The organic solvent of b) is monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, alkylene glycol of tetrapropylene glycol; Diethylene glycol monomethyl ether (methyl carbitol, MDG), diethylene glycol monoethyl ether (ethyl carbitol, EDG), diethylene glycol monobutyl ether (butyl carbitol, BDG), dipropylene glycol monomethyl ether (DPM) ), Alkylene glycol monoalkyl ethers of dipropylene glycol monoethyl ether (DPE); And N-methylpyrrolidone (NMP), gamma butyrolactone (GBL), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylacetamide (DMAc), dimethyl A photoresist stripper composition for copper wiring selected from the group consisting of formamide (DMF) and polar aprotic solvents of tetramethylene sulfone. The method of claim 1, The copper resist photoresist stripper composition of c) is selected from the group consisting of 5-carboxybenzotriazole butyl ester, 5-carboxybenzotriazole octyl ester, and 5-carboxybenzotriazole dodecyl ester. The method of claim 1, The stripper composition is a photoresist stripper composition for copper wiring further comprises d) up to 30 parts by weight of water. The method of claim 1, The stripper composition is a copper resist photoresist stripper composition further comprises up to 1 part by weight of a water-soluble surfactant. The method of claim 7, wherein A photoresist stripper composition for copper wiring, wherein the water-soluble surfactant is a compound represented by the following Formula 3: [Formula 3]

In Chemical Formula 3, R ₄ is hydrogen or a methyl group; T is hydrogen, methyl group or ethyl group; m is an integer from 1 to 4; n is an integer from 1 to 50. A photoresist stripping method comprising etching a photoresist pattern formed on a semiconductor substrate including a metal wiring with a mask and stripping the stripper composition of claim 1. The method of claim 9, The peeling method is a peeling method of the photoresist, characterized in that the dip type or single-leaf type. The method of claim 9, The metal wiring is a top layer of the photoresist stripping method comprising a Cu or Cu alloy film. A liquid crystal display device or semiconductor device manufactured by including the method of claim 9.

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