KR20100011472A - A cu-compatible resist removing composition - Google Patents

Abstract

PURPOSE: A Cu-compatible resist removing composition is provided to be applied to a dip type, single type, and spray type stripping processes and to remove a photoresist film hardened by severe photolithography and wet etch processes in a short time. CONSTITUTION: A Cu-compatible resist removing composition comprises (A) 1-10 weight% tertiary alkanolamine represented by chemical formula 1, (B) the remaining amount of solvent including an amide functional group represented by chemical formula 2, and (C) 0.1-5 weight% additive including an azole compound and hydroxy benzene compound. In chemical formulae 1 and 2, R1 and R2 are independently C1-6 alkyl group, C1-6 hydroxy alkyl group or C1-6 amino alkyl group.

Description

Copper resist removal composition {a Cu-compatible Resist removing composition}

The present invention relates to a composition for removing a resist for copper used in the manufacturing process of a semiconductor device or a flat panel display device, and more particularly, a photoresist stripping solution which can prevent corrosion of copper used as wiring when removing a resist. It relates to a composition.

In the process of fabricating an integrated circuit of a semiconductor device or a microcircuit of a flat panel display device, a photoresist is uniformly coated on a conductive metal film such as aluminum or an aluminum alloy, copper or a copper alloy formed on a substrate, or an insulating film such as a silicon oxide film or a silicon nitride film. And selectively exposed and developed to form a photoresist pattern. Thereafter, 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 transferred to the photoresist stripper (stripper) composition. Proceeds to the removal process.

In order to remove the photoresist for manufacturing the semiconductor device or the flat panel display device, the photoresist stripper composition should be capable of peeling the photoresist in a short time at low temperature. In addition, it should have good peeling capacity that should not leave photoresist residues on the substrate after rinse. In addition, it should have low corrosion resistance that does not damage the metal film or the insulating film of the photoresist underlayer. Various photoresist stripper compositions have been researched and developed to satisfy these conditions, and examples thereof are as follows.

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

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

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

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

However, the photoresist stripper composition as described above may cause severe corrosion during the stripping process due to a weak corrosion protection against copper, a multilayer copper film and a copper alloy film, and may cause a defect during deposition of a gate insulating film, which is a later process. There is a problem.

Accordingly, the present inventors have made diligent efforts to solve the above problems. As a result, a photoresist is obtained when the substrate is treated with a composition for removing a resist for copper of the present invention comprising a tertiary alkanolamine compound, a polar compound including an amide functional group, and an additive. The present invention was completed by confirming not only excellent peeling ability to the film but also low corrosiveness of the metal film or the insulating film.

It is an object of the present invention to provide a resist removal composition for copper that can be applied to both dip, single-leaf and spray stripping processes. In addition, the present invention provides a resist removal composition for copper that can easily and cleanly remove a photoresist film deteriorated by harsh photolithography process and wet etching process in a short time even at low temperature. In addition, the present invention provides a composition for removing resist for copper, which can minimize corrosion to conductive metal films such as copper or copper alloy wiring and photoresist such as silicon oxide film and silicon nitride film without using isopropanol as an intermediate cleaning solution. It is.

In order to achieve the above object, the present invention, based on the total weight of the composition, (A) 1 to 10% by weight of the tertiary alkanol amine compound represented by the following formula (1); (B) a residual amount of solvent including an amide functional group represented by the following formula (2); And (C) 0.1 to 5% by weight of an additive containing an azole compound and a hydroxy benzene compound.

<Formula 1>

 <Formula 2>

In Formula 1 and Formula 2, R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms, a hydroxy alkyl group having 1 to 6 carbon atoms or an amino alkyl group having 1 to 6 carbon atoms, wherein R ₂ is condensed with a hydroxy group To form a ring containing nitrogen and oxygen as a hetero atom, n is an integer of 1 to 4, R ₃ and R ₄ are each independently an alkyl group having 1 to 4 carbon atoms or a hydroxy alkyl group having 1 to 4 carbon atoms, R ₅ is hydrogen, an alkyl group having 1 to 5 carbon atoms, wherein R ₄ and R ₅ may be bonded to each other to form a ring having 4 to 6 carbon atoms.

The resist removal composition for copper of the present invention can be applied to both a dip method, a sheet type, and a spray stripping process. In addition, the photoresist film deteriorated by the harsh photolithography process and wet etching process can be easily and cleanly removed in a short time even at low temperature. In addition, corrosion of the conductive metal film such as copper or copper alloy wiring as the photoresist lower layer and the insulating film such as silicon oxide film and silicon nitride film can be minimized without using isopropanol as an intermediate cleaning solution.

Hereinafter, the present invention will be described in detail.

The resist removal composition for copper of the present invention includes (A) a tertiary alkanol amine compound, a solvent containing (B) an amide functional group, and an additive including (C) an azole compound and a hydroxy benzene compound.

The (A) tertiary alkanol amine compound contained in the resist removal composition for copper of this invention is represented by General formula (1).

<Formula 1>

In Formula 1, R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms, a hydroxy alkyl group having 1 to 6 carbon atoms or an amino alkyl group having 1 to 6 carbon atoms, wherein R ₂ is condensed with a hydroxy group as a hetero atom The ring containing nitrogen and oxygen can be formed, and n is an integer of 1-4.

The (A) tertiary alkanol amine compound is included in an amount of 1 to 10% by weight, preferably 1 to 6% by weight, based on the total weight of the composition. When the above-mentioned range is satisfied, the peeling force on the modified photoresist is excellent, and the corrosion of the conductive metal film, which is the lower layer of the photoresist, is prevented. The (A) tertiary alkanol amine compound is preferably one or two or more selected from the group consisting of triethanol amine, dimethylethanol amine, methyldiethanol amine, and N-aminopropylmorpholine.

The solvent (B) contained in the resist removal composition for copper of the present invention includes an amide functional group represented by the following formula (2).

<Formula 2>

In Formula 2, R ₃ and R ₄ are each independently an alkyl group having 1 to 4 carbon atoms or a hydroxy alkyl group having 1 to 4 carbon atoms, R ₅ is hydrogen, an alkyl group having 1 to 5 carbon atoms, wherein R ₄ and R ₅ May combine with each other to form a ring having 4 to 6 carbon atoms.

When the amide functional group represented by the above formula (2) is included, the solubility of the polymer resin and the photoactive compound which are the main photoresist components is superior to other solvents. The solvent (B) includes the remaining amount relative to the total weight of the composition. When the above-mentioned range is satisfied, excellent peeling force can be realized, galvanic phenomenon is prevented, and economy is excellent. The solvent containing an amide functional group represented by the formula (2) is N-methylpinolidon, dimethylacetamide, dimethylformamide, N-methylformamide, acetamide, N-methylacetamide, N- (2-hydroxy Ethyl) acetamide and 2-pyrrolidone are preferably one or two or more selected from the group consisting of.

The additive (C) included in the resist removal composition for copper of the present invention includes an azole compound and a hydroxy benzene compound, and minimizes corrosion of the conductive metal film and the insulating film under the photoresist. It is preferable that the said azole type compound contains a triazole ring. Non-covalent electron pairs of nitrogen atoms present in the triazole ring electronically bond with copper to control metal corrosion. In addition, the hydroxy benzene-based compound is adsorbed with the hydroxy group and the metal directly substituted in the benzene ring to control the metal corrosion by the basic solution. On the other hand, when washing directly with water without using isopropanol, which is generally an intermediate cleaning solution, the amine component in the photoresist stripper composition is mixed with water to generate highly corrosive alkali hydroxy ions, which is conductive to copper or copper alloy. Promotes corrosion of the metal film. However, the (C) additive may form a complex with the metal film in an alkali state, adsorb onto the surface, and form a protective film, thereby preventing corrosion of the metal by hydroxy ions without using isopropanol.

The additive (C) is included in an amount of 0.01 to 5% 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 film, which are lower layers of the photoresist, is minimized, and the economic efficiency is excellent.

The azole compound and the hydroxy benzene compound are included in the additive (C) in a ratio of 1: 1 to 2: 1. If the above range is satisfied, there is an excellent anticorrosive effect on corrosion occurring at the interface of the multiple conductive metal film, and galvanic corrosion is also significantly lowered.

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, benzotriazole-5 It is preferably one or two or more selected from the group consisting of -carboxylic acid, nitrobenzotriazole and 2- (2H-benzotriazol-2-yl) -4,6-di-tet-butylphenol. The hydroxy benzene compound is one selected from the group consisting of catechol, hydroquinone, pyrogarol, gallic acid, methyl gallate, ethyl gallate, n-propyl gallate, isopropyl gallate and n-butyl gallate Or it is preferable that it is 2 or more types.

The resist removal composition for copper of this invention may further contain (D) water. The (D) water refers to deionized water, and is used for the semiconductor process, preferably water of 18 dl / cm or more.

The resist removal composition for copper of the present invention can be applied to both a dip method, a spray type, and a single-leaf peeling process. 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. In addition, it is possible to simultaneously minimize corrosion of the conductive metal film such as copper and copper alloy wiring, and the insulating film such as silicon oxide film and silicon nitride film, which is a photoresist underlayer, without using isopropanol as an intermediate cleaning solution.

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 1  To 7 and Comparative Example 1  To 4: Photoresist Stripper  Preparation of the composition

According to the component and the composition ratio shown in Table 1 below, a composition for removing a resist for copper was prepared.

division Amine compound menstruum additive Kinds amount Kinds amount Kinds amount Kinds amount Kinds amount Kinds amount Example 1 TEA 7 NMP 12 DMAc 40 NMF 40 CAT 0.3 TTA 0.7 Example 2 TEA 3 NMP 15 DMF 30 NMF 50 CAT One BTA One Example 3 DMEA 4 NMP 15 DMAc 50 NMF 30 GA 0.5 BTA 0.5 Example 4 DMEA 4 DMF 15 DMAc 40 NMF 40 CAT 0.5 BTA 0.5 Example 5 DMEA 8 NMP 10 DMAc 50 DMF 30 GA One TTA One Example 6 APM 3 NMP 20 DMAc 50 NMF 26 CAT 0.5 BTA 0.5 Example 7 APM 5 NMP 15 DMAc 40 DMF 38 GA One TTA One Comparative Example 1 MEA 10 BDG 20 DMAc 40 NMF 28 CAT 2 - - Comparative Example 2 MEA 8 TEG 20 DMAc 40 NMP 30 CAT One BTA One Comparative Example 3 NMEA 8 BDG 24 NMP 32 NMF 35 GA One - - Comparative Example 4 DGA 10 BDG 30 DMAc 30 NMF 28 CAT One TTA One

[week]

TEA: triethanolamine, DMEA: diethylethanolamine

APM: N-aminopropylmorpholine, MEA: monoethanolamine

NMAE: N-methylaminoethanol, DGA: diglycolamine

NMP: N-methylpyrrolidone, DMF: dimeformamide

BDG: Butyl diglycol TEG: Triethylene glycol

DMAc: Dimethylacetamide NMF: N-methylformamide

CAT: catechol GA: gallic acid

TTA: tolytriazole BTA: 1,2,3-benzotriazole

BDG: Butyl diglycol

Test Example : Etching  Property evaluation

The peeling force and the degree of corrosion of the copper wirings were measured by the following method using the composition for removing the resist for copper prepared in Examples 1 to 7 and Comparative Examples 1 to 4.

1. Evaluation of copper wiring

In manufacturing TFT circuits of LCDs, a single metal film and a multi-alloy were formed on a glass substrate with 200-500 mW and a Cu layer 3,000 mW on top. Thereafter, a positive photoresist was applied and dried to form a pattern by photolithography, and a specimen was prepared by wet etching.

1) Peeling force

The resist removal composition for copper prepared in Examples 1 to 7 and Comparative Examples 1 to 4 was maintained at 40 ° C., and the prepared specimens were respectively deposited for 10 minutes to remove resist patterns. 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.

2) Corrosion Evaluation-1

The copper resist removal compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were maintained at 40 ° 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. At this time, the degree of corrosion 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 of the specimen to which the composition for removing the resist for copper of Examples 1 to 7 was applied.

3) Corrosion Evaluation-2

The resist removal compositions for copper prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were maintained at 40 ° C., and the prepared specimens were then deposited for 10 minutes. Then, it was 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, 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. At this time, the corrosion degree was evaluated based on the following criteria.

division Peeling force (40 ℃) Corrosion evaluation 1 Corrosion Evaluation 2 Example 1 ○ ◎ ○ Example 2 ○ ◎ ◎ Example 3 ◎ ◎ ◎ Example 4 ◎ ◎ ◎ Example 5 ◎ ◎ ◎ Example 6 ◎ ◎ ○ Example 7 ◎ ◎ ○ Comparative Example 1 ◎ Х Х Comparative Example 2 ◎ Х Х Comparative Example 3 ◎ △ Х Comparative Example 4 ○ △ Х

※ Peeling Evaluation Criteria

◎: excellent peeling performance ○: good peeling performance

△: poor peeling performance Х: poor peeling performance

※ Corrosion Evaluation Criteria

◎: No corrosion on the surface and side of Cu layer, lower metal film and alloy film

○: slight corrosion on the surface and side of Cu layer, lower metal film and alloy film

(Triangle | delta): Partial corrosion on the surface and side of Cu layer, lower metal film, and alloy film

Х: Severe corrosion on the surface and sides of Cu layer, lower metal film and alloy film

Referring to Table 2, the copper resist removal compositions of Examples 1 to 7 according to the present invention were all peeled off from the copper wirings by using tertiary alkanol amine compounds and compared with Comparative Examples 1 to 4 using glycol ethers. It was confirmed that the strength and the corrosion protection is excellent.

Claims (7)

Regarding the total weight of the composition, (A) 1 to 10% by weight of the tertiary alkanol amine compound represented by Formula 1; (B) a residual amount of solvent including an amide functional group represented by the following formula (2); And (C) A resist removal composition for copper, comprising 0.1 to 5% by weight of an additive containing an azole compound and a hydroxy benzene compound. <Formula 1>

 <Formula 2>

In Chemical Formula 1 and Chemical Formula 2, R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms, a hydroxy alkyl group having 1 to 6 carbon atoms or an amino alkyl group having 1 to 6 carbon atoms, wherein R ₂ is condensed with a hydroxy group to contain nitrogen and oxygen as heteroatoms Can form a ring, n is an integer from 1 to 4, R ₃ and R ₄ are each independently an alkyl group of 1 to 4 carbon atoms or a hydroxy alkyl group of 1 to 4 carbon atoms, R ₅ is hydrogen, an alkyl group of 1 to 5 carbon atoms, wherein R ₄ and R ₅ are bonded to each other 4 to 6 rings can be formed. The method according to claim 1, The (A) tertiary alkanol amine compound is one or two or more selected from the group consisting of triethanol amine, dimethyl ethanol amine, methyl diethanol amine and N-aminopropyl morpholine for removing the resist for copper Composition. The method according to claim 1, The solvent containing an amide functional group represented by the formula (2) is N-methylpynolidone, dimethylacetamide, dimethylformamide, N-methylformamide, acetamide, N-methylacetamide, N- (2-hydroxy Ethyl) acetamide and 2-pyrrolidone, the composition for removing a resist for copper, characterized in that at least one selected from the group consisting of. The method according to claim 1, The (C) additive is a composition for removing a resist for copper, characterized in that it comprises an azole compound and a hydroxy benzene compound in a ratio of 1: 1 to 2: 1. The method according to claim 1, 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, benzotriazole-5 Copper, characterized in that one or two or more selected from the group consisting of -carboxylic acid, nitrobenzotriazole and 2- (2H-benzotriazol-2-yl) -4,6-di- tet-butylphenol A composition for removing a resist for use. The method according to claim 1, The hydroxy benzene compound is one selected from the group consisting of catechol, hydroquinone, pyrogarol, gallic acid, methyl gallate, ethyl gallate, n-propyl gallate, isopropyl gallate and n-butyl gallate Or 2 or more types of copper resist removal composition characterized by the above-mentioned. The method according to claim 1, The resist composition for removing a resist for copper further comprises water.