KR20110007828A - Stripper composition for copper or copper alloy interconnection - Google Patents

Abstract

PURPOSE: A stripper composition for copper or copper alloy interconnection is provided to simultaneously minimize the corrosion against a metal layer including copper or copper alloy and an insulating layer such as a silicon oxide layer and a silicon nitride layer without isopropanol. CONSTITUTION: A stripper composition for copper or copper alloy interconnection comprises (A) 0.1-30 weight% of a tertiary amine compound represented by chemical formula 1, (B) 0.01-10 weight% of azole compound, and (C) the remaining amount of organic solvent. In chemical formula 1, R1 is C1~C4 linear or branched hydroxyalkyl group, or C1~C4 linear or branched thiolalkyl group; R2 and R3 are respectively C1~C5 alkyl group, C1~C4 hydroxy alkyl group, C6~C10 aryl or C1~C4 alkoxy alkyl group; and n is a natural number of 0-4.

Description

Stripper composition for copper or copper alloy wiring {STRIPPER COMPOSITION FOR COPPER OR COPPER ALLOY INTERCONNECTION}

The present invention relates to a stripper liquid composition for copper or copper alloy wiring used in a semiconductor device or a flat panel display manufacturing process, and more particularly, to prevent corrosion of preformed copper or copper alloy wiring when removing a photoresist. A peeling liquid composition is related.

In the process of fabricating an integrated circuit of a semiconductor device or a fine circuit of a flat panel display device, a photoresist is uniformly applied, selectively exposed, and developed on a conductive metal film or an insulating film formed on a substrate to form a photoresist pattern. Here, aluminum or an aluminum alloy, copper, a copper alloy, etc. are used as a conductive metal film, and a silicon oxide film, a silicon nitride film, etc. are used as an insulating film. Subsequently, the conductive metal film or the insulating film is etched wet or dry using a 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 with the photoresist stripper composition. Proceeds.

In order to remove the photoresist generated in the microcircuit manufacturing process, the stripping liquid composition should be capable of peeling the photoresist in a short time at low temperature. It should also have good peeling capacity to leave no photoresist residue on the substrate after rinse. In addition, low corrosion resistance that does not damage the metal film or insulating film of the photoresist underlayer is required. Various peeling liquid compositions have been researched and developed to meet these conditions, and specific examples thereof are as follows.

Japanese Laid-Open Patent Publication No. 51-72503 discloses a stripping liquid composition containing 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. Further, Japanese Laid-Open Patent Publication No. 57-84456 discloses a stripping liquid composition containing dimethyl sulfoxide or diethyl sulfoxide and an organic sulfone compound. U.S. Patent 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 peeling liquid compositions as described above have a problem in that corrosion to a conductive metal film such as aluminum, copper, or copper alloy is severe, and there is a problem of environmental pollution due to strong toxicity, which makes it difficult to use. Therefore, in order to solve the above problems, techniques for preparing a photo-peel solution composition by mixing various organic solvents with water-soluble alkanol amines as essential components have been proposed.

U.S. Patent No. 4,617,251 discloses organic amine compounds such as monoethanolamine (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. Japanese Laid-Open Patent Publication No. 62-49355 discloses a peeling liquid composition comprising an alkylene polyamine sulfone compound in which ethylene oxide is introduced into an alkanol amine and ethylenediamine and a glycol monoalkyl ether. Japanese Patent Application Laid-Open No. 64-42653 discloses dimethyl sulfoxide (DMSO), diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, gamma butyrolactone, and 1,3-dimethyl-2-imidazolidinone. Disclosed is a stripper composition comprising at least one selected solvent and a nitrogen-containing organic hydroxy compound such as monoethanolamine. In addition, Japanese Patent Application Laid-Open No. 4-124668 discloses a stripping liquid composition comprising an organic amine, a phosphate ester surfactant, 2-butyne-1,4-diol, diethylene glycol dialkyl ether, and an aprotic polar solvents. It is disclosed.

However, the peeling liquid compositions have a problem of causing corrosion in the peeling process due to a weak corrosion protection against the film quality including copper or a copper alloy, and inferior defects during the deposition of the gate insulating film, which is a later process.

The present invention is to solve the problems of the prior art as described above,

Provides a stripper composition for copper or copper alloy wiring which can minimize corrosion to a metal film containing copper or a copper alloy as a photoresist underlayer and an insulating film such as a silicon oxide film and a silicon nitride film without using isopropanol as an intermediate cleaning solution. It aims to do it.

In addition, it is possible to easily and cleanly remove the photoresist film that has been deteriorated and cured by a harsh photolithography process and a wet etching process in a short time even at low temperature, and can be applied to a dip method, a sheet type, and a spray peeling process. It aims to provide.

The present invention,

Based on the total weight of the composition, (A) 0.1 to 30% by weight of the tertiary amine compound represented by the formula (1), (B) 0.01 to 10% by weight of the azole compounds, and (C) a copper or copper alloy containing the remaining organic solvent A wiring release liquid composition is provided:

Wherein R ₁ is a C ₁ to C ₄ straight or branched hydroxyalkyl group, or C ₁ to C ₄ straight or branched thiolalkyl group; R ₂ and R ₃ are each independently a C ₁ to C ₅ alkyl group, C ₁ to C ₄ hydroxyalkyl group, C ₆ to C ₁₀ aryl group or C ₁ to C ₄ alkoxyalkyl group, R ₂ and R ₃ may combine to form a heterocycle; n is a natural number of 0 to 4.

Since the peeling liquid composition of the present invention minimizes corrosion to an insulating film such as a silicon oxide film, a silicon nitride film, and a metal film containing copper or a copper alloy, which is a photoresist underlayer, without using isopropanol as an intermediate cleaner, It simplifies the removal process and reduces the wiring defect rate. In addition, the photoresist film hardened by the harsh photolithography process and wet etching process can be easily and cleanly removed in a short time even at a high temperature and a low temperature, and it is effective, and can be applied to both a dip method, a spray type, and a sheet type peeling process. Do.

The present invention is based on the total weight of the composition, (A) copper containing 0.1 to 30% by weight of the tertiary amine compound represented by the formula (1), (B) 0.01 to 10% by weight of the azole compound and (C) the remaining amount of the organic solvent Or to a stripper composition for copper alloy wiring:

 [Formula 1]

Wherein R ₁ is a C ₁ to C ₄ straight or branched hydroxyalkyl group, C ₁ to C ₄ straight or branched thiolalkyl group; R ₂ and R ₃ are each independently a C ₁ to C ₅ alkyl group, C ₁ to C ₄ hydroxyalkyl group, C ₆ to C ₁₀ aryl group or C ₁ to C ₄ alkoxyalkyl group, R ₂ and R ₃ may combine to form a heterocycle; n is a natural number of 0 to 4.

In the present invention, "peel or copper alloy wiring stripping liquid composition" means a stripping liquid composition used for forming a wiring formed of a film quality containing copper or copper alloy.

In general, when washing with water without using isopropanol, which is an intermediate cleaning liquid, in the resist removal process, amine components in the stripping liquid composition are mixed with water to generate highly corrosive alkali hydroxy ions, such as copper or copper alloy. It is known to accelerate the corrosion of the conductive metal film. However, the stripper composition of the present invention simultaneously minimizes corrosion of not only a metal film containing copper or a copper alloy, which is a photoresist underlayer, but also an insulating film such as a silicon oxide film and a silicon nitride film, without using an intermediate cleaning solution. Has characteristics.

The tertiary amine compound (A) contained in the stripper composition of the present invention is included in an amount of 0.1 to 30% by weight, preferably 1 to 10% by weight, based on the total weight of the composition. When the above-mentioned range is satisfied, the peeling force with respect to the modified photoresist is excellent, and the corrosion to the conductive metal film which is the photoresist underlayer is prevented.

The tertiary amine compound (A) may be dimethylaminoethoxyethanethiol, diethylaminoethoxypropanethiol, dipropylaminoethoxybutanethiol, dibutylaminoethoxyethanol dimethylaminoethoxyethanol, diethylaminoethoxyethanol , Dipropylaminoethoxyethanol, dibutylaminoethoxyethanol, N- (2-methoxyethanol) morpholine, N- (2-ethoxyethanol) morpholine, N- (2-butoxyethanol) morpholine These etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.

Examples of the (B) azole compounds included in the stripper composition of the present invention include diazoles and triazole compounds, and these may be used alone or in combination of two or more. The azole compound minimizes corrosion of the conductive metal film and the insulating film under the photoresist.

 The azole compounds (B) are included in an amount of 0.01 to 10% by weight, preferably 0.1 to 3% by weight, based on the total weight of the composition. When the above range is satisfied, damage to the conductive metal film and the insulating layer, which are lower layers of the photoresist, is minimized, thereby reducing the wiring defect rate, thereby obtaining excellent economic efficiency.

The azole compound used in the stripper composition of the present invention is particularly preferably a triazole ring. A non-covalent electron pair of nitrogen atoms present in the triazole ring electronically bonds with copper to control metal corrosion. Specific examples of the azole compounds include tolytriazole, 1,2,3-benzotriazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4 -Triazole, 4-amino-4H-1,2,4-triazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, benzotria Sol-5-carboxylic acid, nitrobenzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-di-tet-butylphenol and the like, and these may be used alone or in combination. More than one species may be used together.

(C) The organic solvent contained in the peeling liquid composition of this invention is contained in content (remaining quantity) which makes the composition of this invention containing the said (A) and (B) component 100 weight%. As the organic solvent (C), sulfoxides, sulfones, amides, lactams, imidazolidinones, mono or diethylene glycol monoalkyl ethers, polyhydric alcohols, and derivatives thereof may be used. One kind alone or two or more kinds may be used together.

Examples of the sulfoxides include dimethyl sulfoxide and the like; Examples of the sulfones include dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, tetramethylene sulfone and the like.

Examples of the amides include N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetoamide, N, N-diethylacetoamide, and the like;

Examples of the lactams include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N- Hydroxyethyl-2-pyrrolidone and the like.

Examples of the imidazolidinones include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone Etc. can be mentioned.

In the case of the mono or diethylene glycol monoalkyl ether, alkyl means a lower alkyl group having 1 to 6 carbon atoms, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol. Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether and diethylene glycol monobutyl ether.

In addition, specific examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, and the like.

The stripper composition of the present invention may further include (D) water. The water (D) means deionized water and is used for the semiconductor process, preferably water of 18 dl / cm or more.

The peeling liquid composition of the present invention may further add a conventional additive in addition to the above-mentioned components, such additives include a hydroxy benzene-based compound, a corrosion inhibitor including a reducing agent, a pH adjusting agent, a surfactant, and the like. have.

The peeling liquid composition for copper of this invention can be applied to both a dip method, a spray type, and a single type peeling process.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Examples 1-6 and Comparative Examples 1-8 8: Preparation of Photopeel Composition

The peeling liquid composition for copper was manufactured according to the component and composition ratio of following Table 1.

division Kinds content Kinds content Kinds content Kinds content Kinds content Kinds content Example 1 DMAET 8 NMP 11 DMAc 50 DMF 30.8 TTA 0.2 - - Example 2 DBAET 10 NMP 11 DMAc 48 DMF 30.8 TTA 0.2 - - Example 3 DMAEE 5 NMP 5 - - NMF 89.9 TTA 0.1 Example 4 DBAEE 5 NMP 16 DMAc 48 NMF 30.8 TTA 0.2 - - Example 5 DMAEE 3 BDG 20 DMAc 50 NMF 26 CAT 0.5 BTA 0.5 Example 6 DBAEE 5 BDG 15 DMAc 40 DMF 38 GA One TTA One Comparative Example 1 DGA 10 BDG 30 DMAc 30 NMF 29 - - TTA One Comparative Example 2 MEA 10 BDG 20 DMAc 42 NMF 27.5 CAT 0.5 - - Comparative Example 3 MEA 8 TEG 20 DMAc 40 NMP 30 CAT One BTA One Comparative Example 4 NMEA 8 BDG 24 NMP 32 NMF 35.7 GA 0.3 - - Comparative Example 5 DEA 7 NMP 12 DMAc 40 NMF 40 CAT 0.3 TTA 0.7 Comparative Example 6 HEP 8 NMP 10 DMAc 50 NMF 31.5 TTA 0.5 - - Comparative Example 7 NMEA 65 DBM 0.9 BDG 24 DIW 10 BTA 0.1 - - Comparative Example 8 BDE 30 DMAc 65 DIW 5 - - - - - -

 [week]

DMAET: dimethylaminoethoxyethanethiol, DBAET: dibutylaminoethoxyethanethiol,

DMAEE: dimethylaminoethoxyethanol, DBAEE: dibutylaminoethoxyethanol,

MEA: monoethanolamine, NMEA: N-methylethanolamine,

DEA: diethanolamine, DGA: diglycolamine,

HEP: hydroxyethyl piperazine, DBM: di (butoxymethyl) aminomethane,

BDE: (butoxymethyl) diethylamine, NMP: N-methyl-2-pyrrolidone,

DMF: N, N-dimethylformamide, BDG: butyldiglycol,

TEG: triethylene glycol, NMF: N-methylformamide,

DMAc: N, N-dimethylacetamide, CAT: catechol,

GA: gallic acid, TTA: tolytriazole,

BTA: 1,2,3-benzotriazole

Test Example: Evaluation of Etch Characteristics

The peeling force and the degree of corrosion of the copper wirings were measured using the peeling liquid compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 8 in the following manner.

 [DMAET: Dimethylaminoethoxyethanethiol, DBAET: Dibutylaminoethoxyethanethiol,

DMAEE: dimethylaminoethoxyethanol, DBAEE: dibutylaminoethoxyethanol,

MEA: monoethanolamine, NMEA: N-methylethanolamine,

DEA: diethanolamine, DGA: diglycolamine,

HEP: hydroxyethyl piperazine, DBM: di (butoxymethyl) aminomethane,

BDE: (butoxymethyl) diethylamine, NMP: N-methyl-2-pyrrolidone,

DMF: N, N-dimethylformamide, BDG: butyldiglycol,

TEG: triethylene glycol, NMF: N-methylformamide,

DMAc: N, N-dimethylacetamide, CAT: catechol,

GA: gallic acid, TTA: tolytriazole,

BTA: 1,2,3-benzotriazole

Test Example: Evaluation of Etch Characteristics

The peeling force and the degree of corrosion of the copper wirings were measured using the peeling liquid compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 8 in the following manner.

In manufacturing a TFT circuit of an LCD, a single metal film and a multiple alloy film were formed on the glass substrate, respectively, from 200 to 500 mW, and a Cu film was formed at 3,000 mW on the top. Thereafter, a positive photoresist was applied and dried to form a pattern by photolithography, and a specimen was prepared by wet etching.

Peel force evaluation

After dissolving the solid photoresist (PR) in 3% by weight relative to the total weight of the solution in the release liquid composition prepared in Examples 1 to 6 and Comparative Examples 1 to 8 and maintained at 50 ℃, the prepared specimens were The resist pattern was removed by immersion for 1 minute. Then, it was washed for 60 seconds in ultrapure water and dried with nitrogen. After the completion of drying, each specimen was observed the peeling degree of the photoresist with an electron microscope (FE-SEM) of 40,000 to 80,000 magnification, and the results are shown in Table 2 below.

Corrosion evaluation 1

The peeling liquid compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 8 were maintained at 70 ° C., and the prepared specimens were deposited for 10 minutes, 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 40,000 to 80,000 magnification, and the results are shown in Table 2 below.

Corrosion Evaluation 2

The peeling liquid compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 8 were maintained at 70 ° C., and the prepared specimens were deposited for 1 minute. Thereafter, the mixture was washed with 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, the side, and the cross section of the specimen was observed with an electron microscope (FE-SEM) of 40,000 to 80,000 magnification, and the results are shown in Table 2 below.

division Peeling force (50 ℃) Corrosion evaluation 1 Corrosion Evaluation 2 Example 1 ○ ◎ ◎ Example 2 ○ ◎ ◎ Embodiment Example Example 3 ◎ ◎ ◎ Example 4 ○ ◎ ◎ Example 5 ◎ ◎ ◎ Example 6 ○ ◎ ◎ Comparative Example 1 ◎ Х Х Comparative Example 2 ◎ Х Х Comparative Example 3 ◎ X Х Comparative Example 4 ◎ X X Comparative Example 5 ○ X X Comparative Example 6 ○ X Х Comparative Example 7 ◎ X Х Comparative Example 8 △ ◎ ◎

※ Peeling Evaluation Criteria

◎: excellent peeling performance ○: good peeling performance

△: poor peeling performance Х: poor peeling performance

※ Corrosion Evaluation Criteria

(Double-circle): No galvanic corrosion between the surface and side surfaces of a Cu film, and a Cu film and a lower film.

○: slight galvanic corrosion between Cu film surface, side surface, Cu film and lower film

(Triangle | delta): The galvanic corrosion part between the surface, the side surface of a Cu film | membrane, and a Cu film | membrane and a lower film | membrane is severe.

Х: The galvanic corrosion between the surface and sides of the Cu film and between the Cu film and the lower film is severe.

From the test results shown in Table 2, the peeling liquid compositions of Examples 1 to 6 of the present invention not only had excellent peeling force on the resist, but also caused corrosion due to the galvanic effect of Cu surface, side surfaces, and Cu and lower layers. It could be confirmed that not. On the other hand, although the exfoliating liquid compositions of Comparative Examples 1 to 8 exhibited excellent exfoliation force in some compositions, corrosion was serious due to the galvanic effect of the surface, side, or Cu and the underlying film of Cu in all compositions.

1 is an electron scanning microscope photograph taken after removing the photoresist according to the test example in the stripper composition of Example 3 of the present invention.

Claims (5)

Based on the total weight of the composition, (A) 0.1 to 30% by weight of the tertiary amine compound represented by the formula (1), (B) 0.01 to 10% by weight of the azole compounds, and (C) a copper or copper alloy containing the remaining organic solvent Wiring solution composition for wiring: [Formula 1]

Wherein R ₁ is a C ₁ to C ₄ straight or branched hydroxyalkyl group, or C ₁ to C ₄ straight or branched thiolalkyl group; R ₂ and R ₃ are each independently a C ₁ to C ₅ alkyl group, C ₁ to C ₄ hydroxyalkyl group, C ₆ to C ₁₀ aryl group or C ₁ to C ₄ alkoxyalkyl group, R ₂ and R ₃ may combine to form a heterocycle; n is a natural number of 0 to 4. The method of claim 1, wherein the (A) tertiary amine compound is dimethylaminoethoxyethanethiol, diethylaminoethoxypropanethiol, dipropylaminoethoxybutanethiol, dibutylaminoethoxyethanol dimethylaminoethoxyethanol, di Ethylaminoethoxyethanol, dipropylaminoethoxyethanol, dibutylaminoethoxyethanol, N- (2-methoxyethanol) morpholine, N- (2-ethoxyethanol) morpholine and N- (2-part 1 or 2 or more types selected from the group consisting of oxyethanol) morpholine, a stripping solution composition for copper or copper alloy wiring. The method according to claim 1, wherein the azole compound is tolytriazole, 1,2,3-benzotriazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2 , 4-triazole, 4-amino-4H-1,2,4-triazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, 5-methylbenzotriazole, One or two or more selected from the group consisting of benzotriazole-5-carboxylic acid, nitrobenzotriazole and 2- (2H-benzotriazol-2-yl) -4,6-di- tet-butylphenol Copper or copper alloy wiring stripping solution composition, characterized in that. The method of claim 1, wherein the (C) organic solvent is dimethyl sulfoxide, dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, tetramethylene sulfone, N, N- dimethylformamide, N-methylformamide , N, N-dimethylacetamide, N-methylacetoamide, N, N-diethylacetoamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2- Pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2- Imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono Butyl ether, ethylene glycol and diethylene alone or in combination of two or more characterized in that copper or a copper alloy wiring stripper composition which is a glycol selected from the group true luer. The stripper composition for copper or copper alloy wiring according to claim 1, wherein the stripper composition further comprises water.

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