WO2011008051A2

WO2011008051A2 - Composition for removing resists used with copper or copper alloy

Info

Publication number: WO2011008051A2
Application number: PCT/KR2010/004671
Authority: WO
Inventors: 홍형표; 홍헌표; 김병묵; 김태희; 이승용
Original assignee: 동우 화인켐 주식회사
Priority date: 2009-07-17
Filing date: 2010-07-16
Publication date: 2011-01-20
Also published as: WO2011008051A3; KR20110007828A; CN102472984A; TW201109868A; CN102472984B

Abstract

The present invention relates to a composition for removing resists used with copper or copper alloy, comprising: (a) from 0.1 to 30 wt.% of an amine compound; and a (b) balance of an organic solvent.

Description

Composition for removing resist for copper or copper alloy

The present invention relates to a composition for removing a resist for copper or copper alloy. The present invention claims the benefit of the filing date of Korean Patent Application No. 10-2009-0065464 filed with the Korean Intellectual Property Office on July 17, 2009, the entire contents of which are incorporated herein.

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 stripper 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 Disclosed is 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). 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 resistance to the film quality including copper or a copper alloy, and causing defects during the deposition of the gate insulating film, which is a later process.

It is an object of the present invention to provide a resist removal composition that can be applied to both dip, single-leaf and spray stripping processes.

An object of the present invention is to provide a resist removal composition that can easily and cleanly remove a photoresist film deteriorated and cured by a harsh photolithography process and a wet etching process in a short time even at low temperature.

It is also an object of the present invention to provide a resist removal composition capable of simultaneously minimizing corrosion of an insulating metal such as a conductive metal film, a silicon oxide film, and a silicon nitride film, which is a photoresist underlayer without using isopropanol as an intermediate cleaning solution.

The present invention (a) 0.1 to 30% by weight of an amine compound represented by any one of Formulas 1 to 5; And (b) provides a composition for removing a resist for copper or copper alloy comprising a residual amount of the organic solvent:

In Chemical Formulas 1 to 5,

R ₁ , R ₄ , and R ₅ are each independently a C ₁ to C ₁₀ linear or branched alkylene group,

R ₂ , R ₃ , and R ₆ are each independently hydrogen, a C ₁ to C ₁₀ straight or branched alkyl group,

R _7, R _8, R ₁₀ are each independently hydrogen, C ₁ ~ C ₁₀ straight-chain or branched-chain alkyl group, C ₆ ~ C ₁₀ aryl group, C ₁ ~ a C ₁₀ linear or branched alkyl group, C ₁ and - a C ₁₀ straight or branched chain hydroxyalkyl group, C ₁ ~ C ₁₀ straight or branched chain of an alkyl benzene group or an amino group,

R ₉ and R ₁₁ are hydrogen, a C ₁ to C ₁₀ straight or branched alkyl group, C ₆ to C ₁₀ aryl group, C ₁ to C ₁₀ straight or branched chain alkylamino group or amino group,

R ₁₂ is a C ₁ to C ₄ straight or branched hydroxyalkyl group, or C ₁ to C ₄ straight or branched thiolalkyl group,

R ₁₃ and R ₁₄ are each independently a C ₁ to C ₅ straight or branched chain alkyl group, C ₁ to C ₄ straight or branched chain hydroxyalkyl group, C ₆ to C ₁₀ aryl group or C ₁ to C ₄ An alkoxyalkyl group, R ₁₃ and R ₁₄ may combine to form a heterocycle,

n ₁ and n ₃ are each independently an integer of 0 or 1,

n ₂ and n ₄ are each independently an integer of 0 to 4,

n ₅ is an integer of 1 or 2,

n ₆ is an integer from 1 to 4,

n ₇ is an integer of 0 to 4,

X ₁ is S, O or N,

X ₂ is N,

X ₃ is CH or N,

X ₄ is CH ₂ , S, O or NH,

Y is a hydroxyl group or an amino group.

The resist removal composition for copper or copper alloy of the present invention can be applied to both a dip method, a spraying type, and a sheet type peeling 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 a high temperature and a low temperature. On the other hand, when washing with water without using isopropanol, which is generally an intermediate cleaning liquid, the amine component in the photoresist stripping liquid composition is mixed with water to generate highly corrosive alkali hydroxy ions, such as copper or a copper alloy. Promotes corrosion of the conductive metal film. However, the resist removal composition for copper or copper alloy according to the present invention can simultaneously minimize corrosion of an insulating metal such as a silicon oxide film and a silicon nitride film and a conductive metal film such as copper and copper alloy wiring, which is a photoresist underlayer, without isopropanol. Can be.

1 is an electron scanning microscope photograph taken after removing the photoresist according to the test example with the stripper composition of Example 15 of the present invention.

Hereinafter, the present invention will be described in detail.

The resist removal composition for copper or copper alloy of this invention contains the (a) amine compound and (b) organic solvent.

The (a) amine compound included in the resist removal composition for copper or copper alloy of the present invention is represented by any one of the following Chemical Formulas 1 to 5.

In Chemical Formulas 1 to 5,

n ₁ and n ₃ are each independently an integer of 0 or 1,

n ₂ and n ₄ are each independently an integer of 0 to 4,

n ₅ is an integer of 1 or 2,

n ₆ is an integer from 1 to 4,

n ₇ is an integer of 0 to 4,

X ₁ is S, O or N,

X ₂ is N,

X ₃ is CH or N,

X ₄ is CH ₂ , S, O or NH,

Y is a hydroxyl group or an amino group.

The (a) amine compound 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 of the conductive metal film which is the photoresist underlayer is prevented.

Compound represented by the formula (1) is N- (2-hydroxypropyl) morpholine, N- (2-hydroxyethyl) morpholine, N-aminopropylmorpholine, hydroxyethylpiperazine, hydroxypropylpiperazine And it is preferably selected from the group consisting of 1- (N-methylpiperazine) ethanol.

The compound represented by the formula (2) is preferably selected from the group consisting of 1-piperazineethanamine, 1-piperazinepropanamine, 1-pyrazine isopropanamine and 1- (2-hydroxyethyl) piperazine. .

Compound represented by the formula (3) is N- (2-hydroxyethyl) -ethylene urea, N- (3-hydroxypropyl) -2-pyrrolidone, hydroxymethylpyrrolidone and hydroxyethylpyrrolidone It is preferably selected from the group consisting of.

The compound represented by Formula 4 is preferably selected from the group consisting of N-piperidineethanol and 1,4-dimethylpiperazine.

The compound represented by the formula (5) is dimethylaminoethoxyethanethiol, diethylaminoethoxypropanethiol, dipropylaminoethoxybutanethiol, dibutylaminoethoxyethanol, dimethylaminoethoxyethanol, diethylaminoethoxyethanol , Dipropylaminoethoxyethanol, dibutylaminoethoxyethanol, N- (2-methoxyethanol) morpholine, N- (2-ethoxyethanol) morpholine and N- (2-butoxyethanol) morpholine It is preferably selected from the group consisting of.

(B) The organic solvent contained in the resist removal composition for copper or copper alloy of the present invention is contained in the remaining amount such that the total weight of the composition of the present invention is 100% by weight. The organic solvent (b) is one or two selected from the group consisting of sulfoxides, sulfones, amides, lactams, imidazolidinones, diethylene glycol monoalkyl ethers, polyhydric alcohols, and derivatives thereof. It is preferable that it is a species or more. In the case of diethylene glycol monoalkyl ether here, alkyl refers to a lower alkyl group having 1 to 6 carbon atoms.

Examples of the sulfoxides include dimethyl sulfoxide and the like, and examples of the sulfones include dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, and tetramethylene sulfone. Examples of the amides include N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetoamide, N, N-diethylacetoamide and the like. Examples of the class include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone and N-hydroxy Ethyl-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. Examples of diethylene glycol monoalkyl ethers include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether are mentioned.

The resist removal composition for copper or copper alloy of the present invention may further include an additive. It is preferable that the said (c) additive contains 1 type (s) or 2 or more types chosen from the group which consists of an azole compound, a hydroxy benzene type compound, a reducing agent, and a complex compound. The additive (c) minimizes corrosion of the conductive metal film and the insulating film under the photoresist.

The additive (c) is 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 film, which are lower layers of the photoresist, is minimized, and the economic efficiency is excellent.

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 adsorbs the hydroxy group and the metal directly substituted in the benzene ring to control the metal corrosion by the basic solution.

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 reducing agent is preferably one or two or more selected from the group consisting of elisorbic acid, vitamin C and alpha tocopherol.

The complex compound is sodium titanium malate, sodium zirconium glycolate, sodium zirconium lactate, potassium zirconium lactate, potassium zirconium lactate, potassium zirconium glyconate, potassium zirconium glycolate It is preferable that it is one or two or more selected from the group consisting of nium maleate (potassium titaniummalate).

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

Hereinafter, the present invention will be described in detail through examples. However, the following examples and the like are provided to explain the present invention in more detail, and the scope of the present invention is not limited thereto.

Examples 1 to 5 and Comparative Examples 1 to 7: Preparation of Photoresist Stripping Liquid Composition

To prepare a composition for removing a resist for copper or copper alloy according to the components and composition ratios shown in Table 1.

Table 1

division

Amine Compound (wt%)

Solvent (% by weight)

Additive (% by weight)

Kinds

sheep

Kinds

sheep

Kinds

sheep

Kinds

sheep

Kinds

sheep

Kinds

sheep

Example 1

NPE

8

NMP

11

DMAc

50

DMF

30.8

TTA

0.2

-

Example 2

NPE

5

NMP

25

-

NMF

69.9

TTA

0.1

Example 3

HEM

5

NMP

20

DMAc

30

NMF

44.5

TTA

0.5

-

Example 4

APM

3

NMP

20

DMAc

50

NMF

26

CAT

0.5

BTA

0.5

Example 5

APM

5

NMP

15

DMAc

40

DMF

38

GA

One

TTA

One

Comparative Example 1

MEA

10

BDG

20

DMAc

42

NMF

27.5

CAT

0.5

-

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

35.7

GA

0.3

-

Comparative Example 4

TEA

7

NMP

12

DMAc

40

NMF

40

CAT

0.3

TTA

0.7

Comparative Example 5

DMEA

8

NMP

10

DMAc

50

DMF

30

GA

One

TTA

One

Comparative Example 6

DGA

10

BDG

30

DMAc

30

NMF

28

CAT

One

TTA

One

NPE: 1- (N-methylpiperazine) ethanol, HEM: N- (2-hydroxyethyl) morpholine

TEA: triethanolamine, DMEA: diethylethanolamine

APM: N-aminopropylmorpholine, MEA: monoethanolamine

NMEA: N-methylethanolamine, DGA: diglycolamine

NMP: N-methyl-2-pyrrolidone DMF: N, N-dimethylformamide

BDG: Butyl diglycol TEG: Triethylene glycol

NMF: N-methylformamide DMAc: N, N-dimethylacetamide

CAT: catechol GA: gallic acid

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

Test Example 1: Evaluation of Etch Characteristics

Using the composition for removing a resist for copper or copper alloy prepared in Examples 1 to 5 and Comparative Examples 1 to 6, the peel force and the degree of corrosion of the copper wiring were measured in the following manner.

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 compositions for copper or copper alloys prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were maintained at 50 ° C., and the prepared specimens were 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 resist removal composition for copper or copper alloy prepared in Examples 1 to 5 and Comparative Examples 1 to 6 was maintained at 70 ° C., and the prepared specimen was deposited for 10 minutes, washed with ultrapure water for 30 seconds, and then nitrogen. Dried over. 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 corrosion degree was evaluated based on the following criteria.

3) Corrosion Evaluation-2

The resist removal compositions for copper or copper alloys prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were maintained at 70 ° C., and the prepared specimens were then deposited for 10 minutes. 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. At this time, the corrosion degree was evaluated based on the following criteria.

TABLE 2

division	Peeling force (40 ℃)	Corrosion evaluation 1	Corrosion Evaluation 2
Example 1	○	◎	○
Example 2	○	◎	◎
Example 3	◎	◎	◎
Example 4	◎	◎	◎
Example 5	◎	◎	◎
Comparative Example 1	◎	Х	Х
Comparative Example 2	◎	Х	Х
Comparative Example 3	◎	X	Х
Comparative Example 4	○	△	△
Comparative Example 5	○	△	△
Comparative Example 6	○	X	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, it can be seen that a clean pattern can be obtained without any corrosion on the surface, side, and cross section of the specimen to which the resist removal composition for copper or copper alloy of Examples 1 to 5 is applied.

Examples 6-12 and Comparative Examples 7-12: Preparation of Photoresist Stripping Liquid Composition

To prepare a composition for removing a resist for copper or copper alloy according to the components and composition ratios shown in Table 3.

TABLE 3

division	Amine Compound (wt%)		Solvent (% by weight)						Additive (% by weight)
division	Kinds	sheep	Kinds	sheep	Kinds	sheep	Kinds	sheep	Kinds	sheep	Kinds	sheep
Example 6	HEP	8	NMP	10	DMAc	50	DMF	32	-	-	-	-
Example 7	NPE	5	NMP	20	DMAc	30	NMF	45	-	-	-	-
Example 8	HEP	8	NMP	10	DMAc	50	DMF	31	TTA	One	-	-
Example 9	HEP	5	NMP	25	-	-	NMF	69.9	TTA	0.1
Example 10	NPE	5	NMP	20	DMAc	30	NMF	44.5	TTA	0.5	-	-
Example 11	HPP	3	NMP	20	DMAc	50	NMF	26	CAT	0.5	BTA	0.5
Example 12	HMP	5	NMP	15	DMAc	40	DMF	38	GA	One	TTA	One
Comparative Example 7	MEA	10	BDG	20	DMAc	40	NMF	28	CAT	2	-	-
Comparative Example 8	MEA	8	TEG	20	DMAc	40	NMP	30	CAT	One	BTA	One
Comparative Example 9	NMEA	8	BDG	24	NMP	32	NMF	35	GA	One	-	-
Comparative Example 10	TEA	7	NMP	12	DMAc	40	NMF	40	CAT	0.3	TTA	0.7
Comparative Example 11	DMEA	8	NMP	10	DMAc	50	DMF	30	GA	One	TTA	One
Comparative Example 12	DGA	10	BDG	30	DMAc	30	NMF	28	CAT	One	TTA	One

HEP: hydroxyethylpyrrolidone NPE: N-piperidineethanol

HPP: N- (3-hydroxypropyl) -2-pyrrolidone HMP: hydroxymethylpyrrolidone

TEA: triethanolamine DMEA: diethylethanolamine

MEA: monoethanolamine NMEA: N-methylethanolamine

DGA: Diglycolamine NMP: N-methylpyrrolidone

DMF: Dimeformamide BDG: Butyldiglycol

TEG: triethylene glycol DMAc: dimethylacetamide

NMF: N-methylformamide CAT: Catechol

GA: gallic acid TTA: tolytriazole

BTA: 1,2,3-benzotriazole BDG: Butyldiglycol

Test Example 2: Evaluation of Etch Characteristics

The peeling force and the degree of corrosion of the copper wiring were measured using the composition for removing the resist for copper or copper alloy prepared in Examples 6 to 12 and Comparative Examples 7 to 12 as follows.

1. Evaluation of copper wiring

In the manufacture of 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 compositions for copper or copper alloys prepared in Examples 6 to 12 and Comparative Examples 7 to 12 were maintained at 50 ° C., and the prepared specimens were deposited for 10 minutes to remove resist patterns. Then, it was washed for 60 seconds in ultrapure water and dried with nitrogen. After completion of drying, each specimen was observed for 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 4 below.

2) Corrosion Evaluation-1

The resist removal composition for copper or copper alloy prepared in Examples 6 to 12 and Comparative Examples 7 to 12 was maintained at 70 ° C., and the prepared specimen was deposited for 10 minutes, washed with ultrapure water for 30 seconds, and then nitrogen. Dried over. 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 4 below. At this time, the corrosion degree was evaluated based on the following criteria.

3) Corrosion Evaluation-2

The resist removal compositions for copper or copper alloys prepared in Examples 6 to 12 and Comparative Examples 7 to 12 were maintained at 70 ° C., and the prepared specimens were respectively deposited for 10 minutes. 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 4 below. At this time, the corrosion degree was evaluated based on the following criteria.

Table 4

division	Peeling force (50 ℃)	Corrosion evaluation 1	Corrosion Evaluation 2
Example 6	◎	◎	○
Example 7	◎	◎	◎
Example 8	○	◎	○
Example 9	○	◎	◎
Example 10	◎	◎	◎
Example 11	◎	◎	◎
Example 12	◎	◎	◎
Comparative Example 7	◎	Х	Х
Comparative Example 8	◎	Х	Х
Comparative Example 9	○	X	X
Comparative Example 10	○	△	△
Comparative Example 11	○	△	△
Comparative Example 12	○	X	Х

※ Peeling Evaluation Criteria

◎: excellent peeling performance ○: good peeling performance

△: poor peeling performance Х: poor peeling performance

※ Corrosion Evaluation Criteria

Х: severe corrosion on the surface and sides of the Cu layer, underlying metal and alloy films

Referring to Table 4, a clean pattern was obtained without any corrosion on the surface, side, and cross section of the specimen to which the resist removal composition for copper or copper alloy of Examples 6 to 12 was applied.

Examples 13-18 and Comparative Examples 13-18: Preparation of Photoresist Stripping Liquid Composition

The peeling liquid composition for copper was manufactured according to the component and composition ratio of following Table 5.

Table 5

division	Kinds	content	Kinds	content	Kinds	content	Kinds	content	Kinds	content	Kinds	content
Example 13	DMAET	8	NMP	11	DMAc	50	DMF	30.8	TTA	0.2	-	-
Example 14	DBAET	10	NMP	11	DMAc	48	DMF	30.8	TTA	0.2	-	-
Example 15	DMAEE	5	NMP	5	-	-	NMF	89.9	TTA	0.1
Example 16	DBAEE	5	NMP	16	DMAc	48	NMF	30.8	TTA	0.2	-	-
Example 17	DMAEE	3	BDG	20	DMAc	50	NMF	26	CAT	0.5	BTA	0.5
Example 18	DBAEE	5	BDG	15	DMAc	40	DMF	38	GA	One	TTA	One
Comparative Example 13	DGA	10	BDG	30	DMAc	30	NMF	29	-	-	TTA	One
Comparative Example 14	MEA	10	BDG	20	DMAc	42	NMF	27.5	CAT	0.5	-	-
Comparative Example 15	MEA	8	TEG	20	DMAc	40	NMP	30	CAT	One	BTA	One
Comparative Example 16	NMEA	8	BDG	24	NMP	32	NMF	35.7	GA	0.3	-	-
Comparative Example 17	DEA	7	NMP	12	DMAc	40	NMF	40	CAT	0.3	TTA	0.7
Comparative Example 18	NMEA	65	DBM	0.9	BDG	24	DIW	10	BTA	0.1	-	-

DMAET: dimethylaminoethoxyethanethiol, DBAET: dibutylaminoethoxyethanethiol,

DMAEE: dimethylaminoethoxyethanol, DBAEE: dibutylaminoethoxyethanol,

MEA: monoethanolamine, NMEA: N-methylethanolamine,

DEA: diethanolamine, DGA: diglycolamine,

DBM: di (butoxymethyl) aminomethane, 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 3: 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 13 to 18 and Comparative Examples 13 to 18 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, at 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.

1) 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 13 to 18 and Comparative Examples 13 to 18 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 completion of drying, each specimen was observed for the degree of peeling 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 stripper compositions prepared in Examples 13 to 18 and Comparative Examples 13 to 18 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.

3) Corrosion Evaluation 2

The peeling liquid compositions prepared in Examples 13 to 18 and Comparative Examples 13 to 18 were maintained at 70 ° C., and the prepared specimens were each 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 6 below.

Table 6

division	Peeling force (50 ℃)	Corrosion Evaluation 1	Corrosion Evaluation 2
Example 13	○	◎	◎
Example 14	○	◎	◎
Example 15	◎	◎	◎
Example 16	○	◎	◎
Example 17	◎	◎	◎
Example 18	○	◎	◎
Comparative Example 13	◎	X	X
Comparative Example 14	◎	X	X
Comparative Example 15	◎	X	X
Comparative Example 16	◎	X	X
Comparative Example 17	○	X	X
Comparative Example 18	◎	X	X

※ 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 6 above, the stripper composition of Examples 13 to 18 of the present invention not only had excellent peeling force on the resist, but also caused corrosion by the galvanic effect of Cu surface, side surfaces, and Cu and lower layers Could not be confirmed. On the other hand, although the exfoliating solution compositions of Comparative Examples 13 to 18 showed excellent exfoliation force in some compositions, corrosion was serious due to the galvanic effect of the surface, side, or Cu and underlying films of Cu in all compositions.

Claims

(a) 0.1 to 30% by weight of an amine compound represented by any one of Formulas 1 to 5; And

(b) a composition for removing resist for copper or copper alloy, comprising a residual amount of organic solvent:

<Formula 1>

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

In Chemical Formulas 1 to 5,

R 1 , R 4 , and R 5 are each independently a C 1 to C 10 linear or branched alkylene group,

R 2 , R 3 , and R 6 are each independently hydrogen, a C 1 to C 10 straight or branched alkyl group,

R 7, R 8, R 10 are each independently hydrogen, C 1 ~ C 10 straight-chain or branched-chain alkyl group, C 6 ~ C 10 aryl group, C 1 ~ a C 10 linear or branched alkyl group, C 1 and - a C 10 straight or branched chain hydroxyalkyl group, C 1 ~ C 10 straight or branched chain of an alkyl benzene group or an amino group,

R 9 and R 11 are hydrogen, a C 1 to C 10 straight or branched alkyl group, C 6 to C 10 aryl group, C 1 to C 10 straight or branched chain alkylamino group or amino group,

R 12 is a C 1 to C 4 straight or branched hydroxyalkyl group, or C 1 to C 4 straight or branched thiolalkyl group,

R 13 and R 14 are each independently a C 1 to C 5 straight or branched chain alkyl group, C 1 to C 4 straight or branched chain hydroxyalkyl group, C 6 to C 10 aryl group or C 1 to C 4 An alkoxyalkyl group, R 13 and R 14 may combine to form a heterocycle,

n 1 and n 3 are each independently an integer of 0 or 1,

n 2 and n 4 are each independently an integer of 0 to 4,

n 5 is an integer of 1 or 2,

n 6 is an integer from 1 to 4,

n 7 is an integer of 0 to 4,

X 1 is S, O or N,

X 2 is N,

X 3 is CH or N,

X 4 is CH 2 , S, O or NH,

Y is a hydroxyl group or an amino group.
The method according to claim 1,

Compound represented by the formula (1) is N- (2-hydroxypropyl) morpholine, N- (2-hydroxyethyl) morpholine, N-aminopropylmorpholine, hydroxyethylpiperazine, hydroxypropylpiperazine And 1- (N-methylpiperazine) ethanol. The composition for removing a resist for copper or copper alloy, which is selected from the group consisting of:
The method according to claim 1,

The compound represented by the formula (2) is characterized in that it is selected from the group consisting of 1-piperazine ethanamine, 1-piperazinepropanamine, 1-pyrazine isopropanamine and 1- (2-hydroxyethyl) piperazine A composition for removing a resist for copper or copper alloy.
The method according to claim 1,

Compound represented by the formula (3) is N- (2-hydroxyethyl) -ethylene urea, N- (3-hydroxypropyl) -2-pyrrolidone, hydroxymethylpyrrolidone and hydroxyethylpyrrolidone The resist removal composition for copper or copper alloy, characterized in that selected from the group consisting of.
The method according to claim 1,

The compound represented by the formula (4) is a composition for removing a resist for copper or copper alloy, characterized in that selected from the group consisting of N- piperidine ethanol and 1,4-dimethyl piperazine.
The method according to claim 1,

The compound represented by the formula (5) is dimethylaminoethoxyethanethiol, diethylaminoethoxypropanethiol, dipropylaminoethoxybutanethiol, dibutylaminoethoxyethanol, dimethylaminoethoxyethanol, diethylaminoethoxyethanol , Dipropylaminoethoxyethanol, dibutylaminoethoxyethanol, N- (2-methoxyethanol) morpholine, N- (2-ethoxyethanol) morpholine and N- (2-butoxyethanol) morpholine The resist removal composition for copper or copper alloy, characterized in that selected from the group consisting of.
The method according to claim 1,

The organic solvent (b) 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, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether and die Glycol monobutyl one member selected from the group consisting of ether or two or composition for removing resist characteristics for copper or copper alloy with not less than.
The method according to claim 1,

The composition for removing a resist for copper or copper alloy is, based on the total weight of the composition, (c) an additive comprising one or two or more selected from the group consisting of azole compounds, hydroxy benzene compounds, reducing agents and complex compounds The resist removal composition for copper or copper alloy, characterized in that it further comprises 0.01 to 10% by weight.
The method according to claim 8,

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 Or a resist removal composition for copper alloy.
The method according to claim 8,

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 resist removal composition for copper or copper alloy characterized by two or more types.
The method according to claim 8,

The reducing agent is a composition for removing a resist for copper or copper alloy, characterized in that one or two or more selected from the group consisting of elisorbic acid, vitamin C and alpha tocopherol.
The method according to claim 8,

The complex compound is sodium titanium malate, sodium zirconium glycolate, sodium zirconium lactate, potassium zirconium lactate, potassium zirconium lactate, potassium zirconium glyconate, potassium zirconium glycolate The composition for removing a resist for copper or copper alloy, characterized in that one or two or more selected from the group consisting of nium maleate (potassium titaniummalate).
The method according to claim 1,

The composition for removing a resist for copper or copper alloy is characterized in that it further comprises water.