KR100846057B1 - Stripper composition for photoresist - Google Patents

Abstract

The present invention relates to a stripper composition for photoresist, in particular from a water-soluble organic amine compound, a proton alkylene glycol monoalkyl ether compound having a boiling point of at least 150 ° C., a polar aprotic solvent, and a compound represented by the formulas (1) to (3). It relates to a stripper composition for photoresists comprising a mixture of at least one corrosion inhibitor selected from at least one species and at least one corrosion inhibitor selected from the group of compounds represented by the formula (4).

The stripper composition for photoresists according to the present invention can not only easily and cleanly remove the deteriorated and cured photoresist film in a short time even at high temperature and low temperature by harsh photolithography and wet etching process, but also does not use isopropanol which is an intermediate cleaning solution. Corrosion can be minimized simultaneously with conductive metal films such as aluminum, aluminum alloy wirings, copper, and copper wirings, and insulating films such as silicon oxide films and silicon nitride films.

Strippers, photoresists, water soluble organic amine compounds, alkylene glycol monoalkyl ether compounds, polar aprotic solvents, corrosion inhibitors

Description

Stripper composition for photoresist {STRIPPER COMPOSITION FOR PHOTORESIST}

The present invention relates to a stripper composition for photoresist, and more particularly, it is not only able to easily and cleanly remove a photoresist film that has been hardened by a severe photolithography and wet etching process in a short time even at high temperature and low temperature, and at the same time In a stripper composition for photoresist that can minimize corrosion to conductive metal films such as aluminum, aluminum alloy wiring, copper, and copper wiring and insulating films such as silicon oxide film and silicon nitride film without using isopropanol as a cleaning liquid. It is about.

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, 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 photoresist underlayer, and then It proceeds to fixation which removes a photoresist layer with a stripper (peel solution).

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 may exhibit different physical properties depending on the mixing sequence during the stripper production, there should be a non-reactive 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, when the photoresist peeling proceeds at a high temperature process, if the volatilization occurs a lot, the component ratio changes quickly, and thus, the process stability and work reproducibility of the stripper are deteriorated.

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

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. Publication No. 57-84456 discloses a stripper composition comprising dimethyl sulfoxide or diethyl sulfoxide and an organic sulfone compound. US Pat. No. 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 on a conductive metal film such as copper and a copper alloy is severe, and there is a problem of environmental pollution due to strong toxicity, which makes 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 as follows.

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 Disclosed is a two-component stripper composition containing a polar solvent such as methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), carbitol acetate, and propylene glycol monomethyl ether acetate (PGMEA). U.S. Patent No. 4,770,713 also discloses organic amine compounds and N-methylacetamide, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-N-ethylpropionamide, diethylacetamide (DEAc), di Disclosed is a two-component stripper composition comprising an amide solvent such as propyl acetamide (DPAc), N, N-dimethylpropionamide, N, N-dimethylbutylamide, and the like. 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. US Pat. No. 63-208043 discloses a stripper composition comprising a water-soluble alkanol amine and 1,3-dimethyl-2-imidazolidinone (DMI), and Japanese Laid-Open Patent Publication No. 63-231343 discloses an amine compound, Disclosed is a stripper composition for a positive photoresist comprising a polar 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 Unexamined Patent Publication 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 the photoresist as described above has a problem that the corrosion resistance of the copper and 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.

In addition, Japanese Patent Application Laid-Open No. 4-350660 discloses a stripper composition containing 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, 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 that the removal of the conventional stripper composition is not completed.

A photoresist stripper composition including water and / or a hydroxylamine compound has been proposed as a composition for cleanly 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 Laid-Open No. 6-266119 discloses hydroxyl amines and alkanols. A stripper composition comprising amines, water, and an anticorrosive agent is disclosed. In addition, Japanese Patent Application Laid-Open No. 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 high-temperature processes, dry etching, etching, and ion implantation processes, and are applied to photoresist etching residues formed by reacting with metal by-products in the cross-cured photoresist and 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 the hydroxyl amine compound is unstable at high temperature, and may be degraded over time.

Various conventional stripper compositions as described above are significantly different 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. Accordingly, there is a continuing need for development of economical stripper compositions having optimum performance for various process conditions.

On the other hand, as liquid crystal displays become larger and mass-produced, peeling of photoresists using single wafer treatment method equipment is more common than a dipping method in which stripper usage is high. 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 10 to 30% by weight of a water-soluble amine compound and 70 to 90% by weight of diethylene glycol monoalkyl ether, N-alkyl pyrrolidone, and hydroxyalkyl pyrrolidone. A stripper composition comprising% is disclosed.

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 single-leaf type peeling process, and easily change the photoresist film that is deteriorated and cured by a harsh photolithography and wet etching process in a short time even at a high temperature and a low temperature. An object of the present invention is 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 wiring, copper, copper wiring and the insulating film, such as silicon oxide film, silicon nitride film, and the like, the photoresist underlayer without using isopropanol as an intermediate cleaning solution. It is to provide a stripper composition for a 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 semi-assembly device comprising the method, and a liquid crystal display device manufactured therefrom. Another object is to provide a semiconductor device.

In order to achieve the above object, the present invention is a stripper composition for a photoresist,

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

b) 20 to 70 wt% of a protic alkylene glycol monoalkylether compound having a boiling point of at least 150 ° C .;

c) 0.01 to 70 weight percent of a polar aprotic solvent; And

d) i) at least one corrosion inhibitor selected from the group of compounds represented by the following formulas (1) to (3); And

  Ii) at least one corrosion inhibitor selected from the group of compounds represented by the following formula (4);

  Mixture of 0.01 to 5% by weight

It provides a photoresist stripper composition comprising a.

[Formula 1]

In the formula of Formula 1,

R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms,

R ₂ and R ₃ are each independently a hydroxyalkyl group having 1 to 4 carbon atoms;

[Formula 2]

In the formula (2),

R ₄ , R ₅ , R ₆ , and R ₇ are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or a hydroxy group,

[Formula 3]

In the formula (3),

R ₈ and R ₉ are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or a hydroxy group;

[Formula 4]

In the formula (4),

R ₁₀ and R ₁₁ are each independently hydrogen or a hydroxyl group,

R ₁₂ is hydrogen, t-butyl group, carboxylic acid group (-COOH), methylcarboxylic acid group (-COOCH ₃ ), ethylcarboxylic acid group (-COOC ₂ H ₅ ), or propylcarboxylic acid group (-COOC ₃ H ₇ ).

In another aspect, the present invention provides a method of removing a photoresist comprising the step of etching the photoresist pattern formed on a substrate including a metal wiring with a mask, and then peeling the photoresist stripper composition.

In another aspect, the present invention provides a method for manufacturing a liquid crystal display device comprising the step of peeling the photoresist using the stripper composition for the photoresist.

In another aspect, the present invention provides a liquid crystal display device characterized in that the manufacturing method.

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

In another aspect, the present invention provides a semiconductor device characterized in that the manufacturing method.

Hereinafter, the present invention will be described in detail.

Stripper composition for a photoresist of the present invention is 5 to 50% by weight of a water-soluble organic amine compound, 20 to 70% by weight of a protic alkylene glycol monoalkyl ether compound having a boiling point of at least 150 ℃, 0.01 to 70% by weight of a polar aprotic solvent, And 0.01 to 5% by weight of a mixture of a corrosion inhibitor selected from the compounds represented by Formulas 1 to 3 and a corrosion inhibitor which is a compound represented by Formula 4, wherein the stripper composition for a photoresist of the present invention Corrosion to the conductive metal film and the insulating film under the silver photoresist can be minimized.

It is preferable to use amino alcohol compounds, such as a primary amino alcohol compound, a secondary amino alcohol compound, or a tertiary amino alcohol compound, as said water-soluble organic amine compound of said a) used for this invention. Specifically, the amino alcohol compounds include 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), or triethanol amine (TEA) and the like, and in particular, the use of monoethanol amine, 1-aminoisopropanol, N-methylaminoethanol, or 2- (2-aminoethoxy) -1-ethanol is advantageous in terms of peeling performance and economy. It is more preferable.

The water-soluble organic amine compound is preferably included in the stripper composition 5 to 50% by weight, more preferably 10 to 30% by weight. If the content is less than 5% by weight, there is a problem in that the peeling force on the modified photoresist is insufficient. If the content is more than 50% by weight, the corrosion resistance of the conductive metal film, which is the lower layer of the photoresist, is increased. .

The proton alkylene glycol monoalkyl ether compound having a boiling point of at least 150 ° C. used in the present invention is excellent in compatibility with water and organic compounds, and serves as a solvent for dissolving the photoresist. It lowers the surface tension of and improves the wettability of the photoresist film.

The protic alkylene glycol monoalkyl ether compound is 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), dipropylene glycol monoethyl ether (DPE), and the like.

Preferably, the protic alkylene glycol monoalkyl ether compound has a boiling point of at least 150 ° C., and when the boiling point is less than 150 ° C., there is a problem that volatilization occurs in a high temperature working process.

Preferably, the protic alkylene glycol monoalkyl ether compound is included in the stripper composition in an amount of 20 to 70% by weight, and when the content is less than 20% by weight, the surface tension of the stripper is increased to reduce the wettability. There exists a problem that peeling force of a stripper falls when it exceeds 70 weight%.

As the polar aprotic solvent of c) used in the present invention, it is preferable to use a compound having a very high solubility in the polymer resin and the photoactive compound which are the main components of the photoresist. In particular, the polar aprotic solvent has a high compatibility with water, can be mixed with the water-soluble organic amine compound and the protic alkylene glycol monoalkyl ether in any ratio, and it is preferable to use a compound having a boiling point of at least 150 ° C. Do.

The polar aprotic solvent is N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO), dimethylacetamide (DMAc), dimethylformamide ( DMF), tetramethylenesulfone, or the like can be used.

The polar aprotic solvent is preferably included in the stripper composition 0.01 to 70% by weight, especially when applied to an organic stripper containing no water, 20 to 70% by weight in the stripper composition, containing water When applied to an aqueous stripper, it is more preferable to use 10 to 50% by weight of the stripper composition. When the polar aprotic solvent is less than 0.01% by weight, the stripper composition has a problem in that peeling force is lowered. When the polar aprotic solvent is more than 70% by weight, the residue of the crosslinked and cured photoresist during the severe etching process is a conductive metal film and an insulating film. There is a problem that can remain.

The corrosion inhibitor of d) used in the present invention functions to prevent damage to the conductive metal film and the insulating film, which are lower layers of the photoresist.

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, and conductive metal such as aluminum, aluminum alloy, copper, or copper alloy. Although the corrosion inhibitor used in the present invention promotes corrosion of the membrane, the corrosion inhibitor used in the present invention forms a complex compound with aluminum in an alkali state and adsorbs on the surface of aluminum and forms a protective film, thereby preventing metal corrosion by hydroxy ions without using isopropanol. have.

In addition, the corrosion inhibitors have significantly improved corrosion protection compared to benzotriazole, tolyltriazole, etc., which have been commercialized as corrosion inhibitors of conventional copper films, and even when a small amount is added, the photoresist underlayers such as aluminum, aluminum alloy, copper, or copper alloy Not only does it cause corrosion of the conductive metal film, the silicon oxide film, the silicon nitride film, etc., but also is very effective in removing the residue of the cured photoresist.

The corrosion inhibitor is preferably iii) using a mixture of a corrosion inhibitor selected from the compounds represented by Formulas 1 to 3 and ii) a corrosion inhibitor that is a compound represented by Formula 4, and is represented by Formulas 1 to 3 The corrosion inhibitor selected from the compound controls the metal corrosion by the non-covalent pair of electrons of the abundant nitrogen atom present in the triazole ring to the electronic bond with copper, and the corrosion inhibitor represented by the formula (4) is a hydroxyl group directly substituted in the benzene ring Aluminum adsorbs to control metal corrosion by basic solution.

Iv) a corrosion inhibitor selected from the compounds represented by the formulas (1) to (3) and ii) a corrosion inhibitor as a compound represented by the formula (4) is preferably mixed in a ratio of 1: 1 to 1: 20, and when mixed with the formula (4) When the content of the compound is increased, there is a problem that the color of the composition can be changed from colorless to dark yellow.

The corrosion inhibitor is preferably included in the stripper composition 0.01 to 5% by weight, more preferably 0.1 to 1% by weight. If the content is less than 0.01% by weight, there is a problem that 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 it exceeds 5% by weight, the peeling force may be reduced. In addition, there is a problem that the price is rising, inefficient in terms of price-performance ratio, and is uneconomical.

The stripper composition for photoresists of the present invention comprising the above components may be prepared as an aqueous stripper composition further comprising e) water and f) a water-soluble nonionic surfactant, if necessary.

When the water of e) used in the present invention contains a predetermined amount or more, it shows more excellent peeling force in a low temperature peeling process of 50 ° C. or lower, but it is particularly preferably included in the stripper composition at a maximum of 30% by weight, more preferably. It is included in 10 to 25% by weight. When the content is more than 30% by weight, the metal wiring under the photoresist may be corroded, and there is a problem in that the dissolving power and photoresist peeling force of the stripper composition are degraded.

The water-soluble nonionic surfactant of f) used in the present invention lowers the surface tension of the stripper when the water content is increased, and prevents the phenomenon of redeposition after peeling off the deteriorated photoresist from the substrate. It works.

The water-soluble nonionic surfactant does not cause a chemical change even in a highly basic stripper composition, and the water-soluble surfactant represented by the following formula (5) in terms of usability with water and an organic solvent usable in the stripper composition and improvement of stripper peelability It is preferable to use.

[Formula 5]

In the formula (5),

R ₁₃ 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 from 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 amount of water increases, the water-soluble nonionic surfactant is preferably used at a maximum of 1% by weight, more preferably 0.01 to 0.3% by weight. If the content exceeds 1% by weight, there is no particular improvement, the viscosity is increased to lower the low temperature peel force, there is a problem that the cost of the composition is uneconomical.

In another aspect, 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 with a mask, followed by peeling with the stripper composition for photoresist. The method of peeling photoresist from a substrate on which a fine circuit pattern is formed using the stripper composition for photoresist includes a dip method of dipping several substrates at the same time into a stripper liquid and a stripping solution one by one. It can be applied to both single-layer method of spraying (spraying) the substrate to remove photoresist.

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.

Stripper composition for a photoresist of the present invention consisting of the above components is sprayed by dropping or spraying through a nozzle to remove unnecessary photoresist generated on the edge and the rear surface 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 another aspect, 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 the photoresist, a liquid crystal display device or a semiconductor device manufactured therefrom Of course, the steps before and after the peeling step may be performed according to a conventional liquid crystal display device or a 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, which is deteriorated and cured by a harsh photolithography and wet etching process, can be easily carried out within a short time even at a high temperature and a low temperature. Not only can it be removed, but it also minimizes the corrosion of conductive metal films such as aluminum, aluminum alloy wiring, copper and copper wiring, and silicon oxide film and silicon nitride film, without using intermediate cleaning solution isopropanol. can do.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

10 wt% of 2- (2-aminoethoxy) -1-ethanol, 30 wt% of N-methylpyrrolidone, 55 wt% of diethylene glycol monobutyl ether, n-diethanolaminomethyltolyltriazole 2 g of 2.5% by weight of the compound of formula 1 (D1) and 2.5% by weight of the compound of formula 4 (D4), which are methylgallate, are stirred at room temperature for 2 hours, and then filtered to 0.1 µm and stripper. The composition was prepared.

Examples 2 to 17 and Comparative Examples 1 to 7

A stripper composition was prepared in the same manner as in Example 1, except that Example 1 was used as the component and the composition shown in Table 1 below.

division Water Soluble Organoamine Compound Protic alkylene glycol monoalkyl ether compound Polar aprotic solvents Corrosion inhibitor water Water Soluble Nonionic Surfactants Kinds amount Kinds amount Kinds amount Kinds amount Kinds amount Example One AEE 10 BDG 55 NMP 30 D1 2.5 D4 2.5 - - 2 NMAE 10 BDG 57.8 NMP 30 D1 0.2 D4 2.0 - - 3 MEA 10 EDG 56.8 DMSO 50 D2 0.2 D4 3.0 - - 4 AIP 10 DPM 58.4 DMAc 30 D3 0.1 D4 1.5 - - 5 AEE 5 DPM 52.6 TMS 40 D2 0.4 D4 2.0 - - 6 AEE 20 EDG 29.1 DMSO 50 D1 0.2 D4 0.7 - - 7 NMAE 20 BDG 49.7 TMS 30 D3 0.2 D4 0.1 - - 8 MEA 15 BDG 40.4 NMP 40 D2 0.1 D4 4.5 - - 9 MEA 20 BDG 36.9 NMP 40 D1 0.1 D4 3.0 - - 10 MEA 30 BDG 29 DMAc 40 D1 0.1 D4 0.9 - - 11 AEE 10 BDG 55.6 DMAc 30 D2 2 D4 2.4 - - 12 NMAE 10 BDG 54.9 DMAc 30 D3 2 D4 3.0 - 0.1 13 NMAE 10 DPM 47.5 DMAc 30 D3 0.2 D4 2.2 10 0.1 14 AEE 20 DPM 27.7 DMAc 30 D2 0.2 D4 2.0 20 0.1 15 AIP 10 DPM 38.2 NMP 30 D1 0.2 D4 1.5 20 0.1 16 MEA 15 BDG 53.3 NMP 30 D2 0.2 D4 1.5 - - 17 AEE 10 BDG 57.8 NMP 30 D3 0.2 D4 2.0 - - Comparative example One AEE 10 EDG 59 NMP 30 D4 One - - - - 2 NMAE 10 BDG 60 NMP 30 D2 One - - - - 3 AEE 20 BDG 47 NMP 30 D4 3 - - - - 4 MEA 10 BDG 57 NMP 30 D2 3 - - - - 5 AEE 10 BDG 60 NMP 30 - - - - - - 6 NMAE 10 DPM 49.4 DMAc 30 D3 0.5 - - 10 0.1 7 AEE 20 DPM 29.4 DMAc 30 D3 0.5 - - 20 0.1

[Note] · AEE: 2- (2-aminoethoxy) -1-ethanol · NMAE: N-methylaminoethanol · MEA: monoethanolamine · AIP: 1-aminoisopropanol · BDG: diethylene glycol monobutyl ether EDG: diethylene glycol monoethyl ether DPM dipropylene glycol monomethyl ether NMP N-methylpyrrolidone DMSO dimethyl sulfoxide DMAC dimethylacetamide TMS tetramethylene sulfone D1 n-di Ethanolaminomethyltolyltriazole (compound represented by formula 1) D2: tetrahydrobenzotriazole (compound represented by formula 2) D3: benzotriazole (compound represented by formula 3) D4: methylgallate (Compound represented by Formula 4)-Water-soluble nonionic surfactant:

Using the stripper compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 7 were measured the peel force and the corrosion degree for the aluminum wiring and copper wiring in the following manner.

1. Evaluation of aluminum wiring

In the TFT circuit fabrication of LCD, the Al / Nd layer was formed at 2,000 2,000 on the glass substrate after the gate process, and the Mo layer was 200Å at the top, and then the positive photoresist was applied and dried to form a pattern by photolithography. The specimens were prepared by wet etching.

1) Peeling force

The stripper compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 7 were maintained at 70 ° C., and the prepared specimens were immersed and stripped for 1 minute, and then washed in ultrapure water for 30 seconds and dried with nitrogen. After completion of drying, each specimen was observed for peeling degree of the photoresist with an optical microscope at 1,000 magnification and an electron microscope (FE-SEM) at 5,000 to 10,000 magnification, and the results are shown in Table 2 below. At this time, the degree of peeling was evaluated based on the following criteria, the evaluation result was obtained in the case of the specimen to which the stripper composition of Examples 1 to 17 was obtained without a clean photoresist foreign material at all.

Evaluation standard ◎ Excellent peeling performance ○ Good peeling performance △ Peeling performance is not good × Peeling performance poor

2) Corrosion Evaluation-1

The stripper compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 7 were maintained at 70 ° C., and the prepared specimens were immersed and stripped for 10 minutes, and then washed in ultrapure water for 30 seconds and dried with nitrogen. After performing the strip process three times in succession, 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, and the results are shown in Table 2 below. At this time, the corrosion degree was evaluated based on the following criteria, the evaluation result was able to obtain a clean pattern without any corrosion on the surface, side, and cross section of the specimen to which the stripper composition of Examples 1 to 17 were applied.

Evaluation standard ◎ No corrosion on Al / ND layer and Mo layer surface and side ○ Slight corrosion on Al / ND and Mo layers △ Partial corrosion on Al / ND and Mo layers × Severe corrosion on Al / ND and Mo layers

3) Corrosion Evaluation-2

This experiment is an experiment to evaluate the corrosion in the process of washing in ultrapure water after the completion of the strip to deposit the photoresist on the stripper composition, the prepared specimen was immersed in acetone solution maintained at 40 ℃ for 10 minutes, isopropanol Washed 30 seconds in ultrapure water for 30 seconds. Then, the samples were immersed in a mixture of 50 g of the stripper composition prepared in Examples 1 to 17 and Comparative Examples 1 to 7 and 950 g of water at room temperature for 3 minutes, and then washed with 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) at 50,000 to 100,000 magnification, and the results are shown in Table 2 below. At this time, the corrosion degree was evaluated based on the following criteria, the evaluation result was able to obtain a clean pattern without any corrosion on the surface, side, and cross section of the specimen to which the stripper composition of Examples 1 to 17 were applied.

Evaluation standard ◎ No corrosion on Al / ND layer and Mo layer surface and side ○ Slight corrosion on Al / ND and Mo layers △ Partial corrosion on Al / ND and Mo layers × Severe corrosion on Al / ND and Mo layers

2. Evaluation of Copper Wiring

In the TFT circuit fabrication of LCD, the dissimilar metal alloy is formed on the glass substrate which has been gated to 300 Cu and the Cu layer is 2,000 Å on the upper part, and then the positive photoresist is applied and dried to form a pattern by photolithography. The specimen of the state completed by the etching was prepared.

1) Peeling force

The stripper compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 7 were maintained at 70 ° C., and the prepared specimens were immersed and stripped for 1 minute, and then washed in ultrapure water for 30 seconds and dried with nitrogen. After completion of drying, each specimen was observed for peeling degree of the photoresist with an optical microscope at 1,000 magnification and an electron microscope (FE-SEM) at 5,000 to 10,000 magnification, and the results are shown in Table 2 below. At this time, the degree of peeling was evaluated based on the same criteria as the aluminum wiring, and the evaluation result was obtained in the case of the specimen to which the stripper composition of Examples 1 to 17, without any photoresist foreign material clean pattern.

2) Corrosion Evaluation-1

The stripper compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 7 were maintained at 70 ° C., and the prepared specimens were then deposited for 30 minutes, washed with isopropanol for 30 seconds and ultrapure water for 30 seconds, and then with nitrogen. Dried. 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) at 50,000 to 200,000 magnification, and the results are shown in Table 2 below. At this time, the corrosion degree was evaluated based on the following criteria, the evaluation result was able to obtain a clean pattern without any corrosion on the surface, side, and cross section of the specimen to which the stripper composition of Examples 1 to 17 were applied.

Evaluation standard ◎ No corrosion on surface and side of Cu layer and dissimilar metal alloy layer ○ Slight corrosion on the surface and side of Cu layer and dissimilar metal alloy layer △ Partial corrosion on the surface and side of Cu layer and dissimilar metal alloy layer × Severe corrosion on the surface and side of Cu layer and dissimilar metal alloy layer

3) Corrosion Evaluation-2

The stripper compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 7 were maintained at 70 ° C., and the prepared specimens were then deposited for 5 minutes, and then washed with isopropanol for 30 seconds and ultrapure water for 30 seconds, and then with nitrogen. Dried. After performing the strip process three times in succession, the degree of corrosion of the surface, side, and cross section of the specimen was observed with an electron microscope (FE-SEM) at 50,000 to 200,000 magnification, and the results are shown in Table 2 below. At this time, the corrosion degree was evaluated based on the following criteria.

Evaluation standard ◎ No corrosion on surface and side of Cu layer and dissimilar metal alloy layer ○ Slight corrosion on the surface and side of Cu layer and dissimilar metal alloy layer △ Partial corrosion on the surface and side of Cu layer and dissimilar metal alloy layer × Severe corrosion on the surface and side of Cu layer and dissimilar metal alloy layer

division Aluminum wiring Copper wiring Peeling force (70 ℃) Corrosion Evaluation Peeling force (70 ℃) Corrosion Evaluation One 2 One 2 Example 1 ◎ ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ ◎ ◎ Example 5 ○ ◎ ◎ ◎ ◎ ◎ Example 6 ◎ ◎ ◎ ◎ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ ◎ ◎ Example 8 ◎ ◎ ◎ ◎ ◎ ◎ Example 9 ◎ ◎ ◎ ◎ ◎ ◎ Example 10 ◎ ◎ ◎ ◎ ◎ ◎ Example 11 ◎ ◎ ◎ ◎ ◎ ◎ Example 12 ◎ ◎ ◎ ◎ ◎ ◎ Example 13 ○ ◎ ◎ ◎ ◎ ◎ Example 14 ◎ ◎ ◎ ○ ◎ ◎ Example 15 ◎ ◎ ◎ ○ ◎ ◎ Example 16 ◎ ◎ ◎ ◎ ◎ ◎ Example 17 ◎ ◎ ◎ ◎ ◎ ◎ Comparative Example 1 ○ × × ○ × × Comparative Example 2 ○ × × ○ △ ○ Comparative Example 3 ◎ × × △ △ ○ Comparative Example 4 ◎ × × △ ○ ○ Comparative Example 5 ◎ ○ × ○ × × Comparative Example 6 △ ◎ × ◎ × × Comparative Example 7 ◎ ◎ ○ ○ × ×

Through the above Table 2, the stripper composition for photoresists of Examples 1 to 17 including a mixture of a corrosion inhibitor selected from a compound represented by Formulas 1 to 3 and a compound represented by Formula 4 according to the present invention As compared with Comparative Examples 1 to 7 using no corrosion inhibitors or using only one component of the compounds represented by Chemical Formulas 1 to 4, it was confirmed that the peeling strength and the corrosion resistance were excellent in both the aluminum wiring and the copper wiring.

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

Although only described in detail with respect to the described embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, it is natural that such variations and modifications belong to the appended claims. .

Claims (17)

In the stripper composition for photoresist, a) 5 to 50% by weight of a water soluble organic amine compound; b) 20 to 70 wt% of a protic alkylene glycol monoalkylether compound having a boiling point of at least 150 ° C .; c) 0.01 to 70 weight percent of a polar aprotic solvent; And d) i) at least one corrosion inhibitor selected from the group of compounds represented by the following formulas (2) to (3); And   Ii) at least one corrosion inhibitor selected from the group of compounds represented by the following formula (4);   Mixture of 0.01 to 5% by weight A photoresist stripper composition comprising: [Formula 2]

In the formula (2), R ₄ , R ₅ , R ₆ , and R ₇ are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or a hydroxy group, [Formula 3]

In the formula (3), R ₈ and R ₉ are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, or a hydroxy group; [Formula 4]

In the formula (4), R ₁₀ and R ₁₁ are each independently hydrogen or a hydroxyl group, R ₁₂ is hydrogen, t-butyl group, carboxylic acid group (-COOH), methylcarboxylic acid group (-COOCH ₃ ), ethylcarboxylic acid group (-COOC ₂ H ₅ ), or propylcarboxylic acid group (-COOC ₃ H ₇ ). The method of claim 1, The water-soluble organic amine compound of a) is selected from the group of amino alcohol compounds consisting of a primary amino alcohol compound, a secondary amino alcohol compound, and a tertiary amino alcohol compound, for a photoresist. Stripper composition. 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) At least 1 type is selected from the group which consists of a photoresist stripper composition characterized by the above-mentioned. The method of claim 1, The protic alkylene glycol monoalkyl ether compound having a boiling point of b) of at least 150 ° C. is diethylene glycol monomethyl ether (methyl carbitol, MDG), diethylene glycol monoethyl ether (ethyl carbitol, EDG), di Stripper for photoresists, characterized in that at least one selected from the group consisting of ethylene glycol monobutyl ether (butyl carbitol, BDG), dipropylene glycol monomethyl ether (DPM), and dipropylene glycol monoethyl ether (DPE) Composition. The method of claim 1, The polar aprotic solvent of c) is N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), dimethyl At least one selected from the group consisting of formamide (DMF) and tetramethylene sulfone, wherein the stripper composition for a photoresist. The method of claim 1, Wherein d) the corrosion inhibitor is characterized in that i) a corrosion inhibitor selected from the compound represented by the formula 2 to 3 and ii) the compound represented by the formula (4) in a ratio of 1: 1 to 1: 20. Stripper composition for photoresist. The method of claim 1, The stripper composition for a photoresist, characterized in that the stripper composition further comprises e) up to 30% by weight of water. The method of claim 1, The stripper composition for a photoresist, characterized in that the stripper composition further comprises f) up to 1% by weight of a water-soluble nonionic surfactant. The method of claim 8, The stripper composition for a photoresist, characterized in that the water-soluble nonionic surfactant is a compound represented by the following formula (5): [Formula 5]

In the formula (5), R ₁₃ 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 from 1 to 4, n is an integer from 1 to 50. And etching the photoresist pattern formed on the substrate including the metal wiring with a mask, followed by peeling with a stripper composition for photoresist according to claim 1. The method of claim 10, The peeling method of the photoresist, characterized in that the peeling method is a dip method or a single sheet method. The method of claim 10, And the metal wiring comprises an Al-Nd / Mo double layer or a Cu / heterometal alloy layer as a lower layer. The method of claim 10, And the photoresist is a positive photoresist, a negative photoresist, or a dual tone photoresist. A method of manufacturing a liquid crystal display device comprising the step of peeling a photoresist using the stripper composition for photoresist according to claim 1. A liquid crystal display device manufactured by the method of claim 14. A method for manufacturing a semiconductor device, comprising the step of peeling a photoresist using the stripper composition for photoresist of claim 1. A semiconductor device manufactured by the method of claim 16.