KR20090041397A - Composition for removal of resist comprising poly(cyanoalkyl)ethyleneamine and method for removal of resist using the composition - Google Patents

Abstract

a composition for removing a resist, which has an excellent resist stripping property and causes less damage to a semiconductor or a flat panel display material; and a method for stripping a resist by using the composition. Specifically disclosed is a resist stripping agent comprising a poly(cyanoalkyl)ethyleneamine, wherein the poly(cyanoalkyl)ethyleneamine is preferably at least one member selected from N,N'-bis(2-cyanoethyl)-ethylenediamine, N,N,N'-tris(2-cyanoethyl)ethylenediamine, N,N,N',N'-tetrakis(2-cyanoethyl)ethylenediamine, N,N'-bis(2-cyanoethyl)piperazine, N,N'-bis(2-cyanoethyl)-N''-(2-aminoethyl)piperazine, N,N',N'-tris(2-cyanoethyl)-N''-(2-aminoethyl)piperazine and the like.

Description

Composition for removing resist containing poly (cyanoalkyl) ethyleneamine and method for removing resist using same TECHNICAL BACKGROUND

This invention relates to the removal agent for removing the photoresist layer in the manufacturing process of a semiconductor integrated circuit, a printed wiring board, and a liquid crystal.

This application is Japanese Patent Application No. 2006-223988, filed August 21, 2006, Japanese Patent Application No. 2007-4208, filed January 12, 2007, and Japan, filed March 16, 2007. Priority is claimed for National Patent Application No. 2007-68529, the content of which is incorporated herein.

The semiconductor integrated circuit is coated with a photoresist on a substrate (i.e., a substrate), subjected to etching after exposure and development, and after forming a circuit, the photoresist is peeled off on the substrate, or ashed after circuit formation. After the removal, the resulting resist residue is prepared by the method of peeling off. Various resist stripping agents have been proposed for peeling photoresist onto a substrate or for stripping resist residues onto a substrate.

Conventionally, the most frequently used resist releasing agent contained ethanol amines such as monoethanolamine (for example, Patent Document 1).

However, the resist stripping ability of monoethanolamine is not only industrially insufficient, but also has a drawback that damage is large for semiconductor and flat panel display materials.

Aluminum is used as a wiring material of a conventional semiconductor integrated circuit, and monoethanolamine could be used without any problems with regard to aluminum wiring. However, in recent years, miniaturization of semiconductor integrated circuits has progressed, and the wiring material has changed from aluminum with high resistance to copper with low resistance. By the way, the monoethanolamine which was the main formulation of the conventional resist releasing agent has large corrosion with respect to copper, and it is difficult to use it for a copper wiring process.

Moreover, in flat panel displays, such as a liquid crystal panel, chromium has been used as a gate material, but also in a flat panel display, it turns into a material of lower resistance than chromium, namely aluminum, molybdenum, and copper. Also about flat panel displays, the monoethanolamine which is the main raw material of the conventional peeling agent was large in damage.

Cyanoethylethyleneamines, such as N- (2-cyanoethyl) ethylenediamine, which are known in the art, are excellent in resist peelability when used as an aqueous solution and have small damage to aluminum and copper, Similarly, when used in an organic solvent, it reacted with an organic solvent and caused decomposition (refer patent document 2).

As described above, a peeling solution having a higher resist peeling ability than monoethanolamine, less damage to semiconductor and flat panel display materials, and lower reactivity with an organic solvent is required.

Patent Document 1: Japanese Unexamined Patent Publication No. 62-49355

Patent document 2: Unexamined-Japanese-Patent No. 2004-155822.

Disclosure of the Invention

Problems to be Solved by the Invention

As mentioned above, the resist release agent conventionally proposed does not have sufficient peelability, and there exists damage to a semiconductor and a flat panel display material. Therefore, the objective of this invention is providing the resist removal composition which shows outstanding resist peeling property and is small in damage to a semiconductor and a flat panel display material, and the peeling method of the resist using the said resist removal composition.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining resist removal, in the resist removal composition which consists of an amine which has two or more cyanoalkyl groups, the resist removal ability is high, and it does not decompose | disassemble by reacting with a solvent, especially an organic solvent, Moreover, it discovered that damage to a semiconductor and a flat panel display material is small, and came to complete this invention.

That is, this invention is a resist removal composition which contains poly (cyanoalkyl) ethyleneamine, and the resist removal method using the same.

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

An essential component of the resist removing composition of the present invention is poly (cyanoalkyl) ethyleneamine.

Poly (cyanoalkyl) ethyleneamine is a compound in which two or more cyanoalkyl groups, such as a cyanoethyl group, were contained in ethyleneamine. When there are less than 2 cyanoalkyl groups, it is easy to decompose the organic solvent to be used, and damage to a semiconductor material and a flat panel display material becomes large.

Examples of the poly (cyanoalkyl) ethyleneamine that can be used in the resist removing composition of the present invention include N, N'-bis (2-cyanoethyl) -ethylenediamine,

N, N-bis (2-cyanoethyl) ethylenediamine,

N, N, N'-tris (2-cyanoethyl) ethylenediamine,

N, N, N ', N'-tetrakis (2-cyanoethyl) ethylenediamine,

N, N'-bis (2-cyanoethyl) piperazine,

N, N'-bis (2-cyanoethyl) -N "-(2-aminoethyl) piperazine,

N, N ', N'-tris (2-cyanoethyl) -N "-(2-aminoethyl) piperazine,

N, N-bis (2-cyanoethyl) -N '-(2-aminoethyl) piperazine,

N, N ', N "-tris (2-cyanoethyl) diethylene triamine and

N, N, N ', N ", N" -pentakis (2-cyanoethyl) diethylenetriamine is at least one member selected from the group consisting of.

Poly (cyanoalkyl) ethyleneamine can be easily manufactured by adding acrylonitrile and methacrylonitrile to ethyleneamines, such as ethylenediamine, diethylenetriamine, and piperazine.

For example, when N, N'-bis (2-cyanoethyl) ethylenediamine mixes 2 or more equivalents of acrylonitrile with ethylenediamine in a solvent, the addition reaction proceeds with the heat of reaction thereof. Bis bodies are obtained. Water and an organic solvent can be used as a solvent. In this reaction, N- (2-cyanoethyl) ethylenediamine (monomer) to which only 1 equivalent of acrylonitrile is added, or N, N, N'-tris (2- added to 3 equivalents or more) is added. Although cyanoethyl) ethylenediamine (tris body), N, N, N ', N'- tetrakis (2-cyanoethyl) ethylenediamine (tetrakis body) may by-produce, in the present invention, poly It is preferable to make content of monobody which is not (cyanoalkyl) ethyleneamine small. The tris and tetrakis bodies do not affect the decomposition of the organic solvent and do not cause any damage to the semiconductor material and the flat panel display material, but the mono-body is at least 20% or less of the entire cyanoalkylamine, especially 5 It is preferable not to contain% or less at all. When the monobody exceeds 20%, the organic solvent used is easily decomposed, and damage to the semiconductor material and the flat panel display material is increased.

Although the organic solvent and water can be used for the resist removal composition of this invention as a solvent, it is especially preferable to use an organic solvent.

In the resist removing composition of the present invention, any organic solvent that can be used is not particularly limited as long as it is miscible with poly (cyanoalkyl) ethyleneamine. Examples of inexpensive organic solvents that are readily available include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylacetamide, dimethyl sulfoxide, sulfolane, hexamethyl phosphate triamide, acetamide, and N. -Methylpyrrolidone, N, N-diethylformamide, N, N'-dimethylethylene urea, N, N'-dimethylpropylene urea, tetramethyl urea, methyl methyl carbamate, acetnitrile, lactose Amide, hydroxybutyric acid amide, 2-pyrrolidone, N-methylpropionamide, dimethylpropylamide, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether And propylene glycol monomethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, ethylene glycol, propylene glycol and the like. Of these organic solvents, for example, N-methylacetamide and the like react with monoethanolamine, N- (2-cyanoethyl) ethylenediamine, and the like to decompose the solvent, but the composition for removing a resist of the present invention The poly (cyanoalkyl) ethyleneamine which can be used for hardly reacts with an organic solvent, and can prevent decomposition of a solvent.

The resist removal composition of this invention shows the outstanding performance regarding the removal of the resist used for manufacture of a semiconductor device, a flat panel display, etc. Especially, it can use for removal of the resist used in manufacture of the semiconductor or flat panel display which uses the at least 1 sort (s) of metal chosen from the group which consists of aluminum, copper, and molybdenum.

The temperature at the time of using the resist removal composition of this invention is 20-180 degreeC, Preferably it is 80-160 degreeC. At temperatures exceeding 180 ° C., poly (cyanoalkyl) ethyleneamine decomposes, and at temperatures below 20 ° C., it is difficult to remove the resist at an industrially acceptable rate.

When removing a resist using the composition for removing a resist of the present invention, an ultrasonic wave or the like may be used to accelerate the removal rate.

Effects of the Invention

According to the composition for removing a resist of the present invention, since the resist can be removed without damaging the semiconductor or flat panel display material, it is possible to manufacture a fine semiconductor and a flat panel display.

Although this invention is demonstrated also in detail by the following example, this invention is not limited to these.

Example 1

N-methylacetamide was added to 10 g of N, N'-bis (2-cyanoethyl) ethylenediamine to make 100 g. This was heated to 70 ° C and the silicon wafer on which the i-line resist was formed was dipped. After 1 minute of washing with water, the rate at which the resist was peeled off was observed, and it was completely peeled off.

Moreover, the silicon wafer which formed copper was immersed in the liquid which heated the solution which added water to 10 g of N, N'-bis (2-cyanoethyl) ethylenediamine and made it 100 g at 70 degreeC. After 1 minute, washing with water and measuring the damage rate of copper from the change in the film thickness of copper were 0.55 nm / min. Similarly, the silicon wafer in which aluminum was formed was immersed in 70 degreeC liquid. After 1 minute, washing with water and measuring the damage rate of aluminum from the film thickness change of aluminum were 0.12 nm / min.

Example 2

The peeling liquid of Example 1 was heated at 70 degreeC for 12 hours. After cooling, the separation solution was analyzed by gas chromatography, and the decomposition of N-methylacetamide was 0.7%.

Example 3

7.9 g of N, N'-bis (2-cyanoethyl) ethylenediamine, N, N, N'-tris (2-cyanoethyl) ethylenediamine 1.7 g and N, N, N ', N'- N-methylacetamide was added to 0.4 g of tetrakis (2-cyanoethyl) ethylenediamine to make 100 g. This was heated to 70 ° C to immerse the silicon wafer on which the i-line resist was formed. After 1 minute of washing with water, the rate at which the resist was peeled off was observed, and it was completely peeled off.

7.9 g of N, N'-bis (2-cyanoethyl) ethylenediamine, 1.7 g of N, N, N'-tris (2-cyanoethyl) ethylenediamine and N, N, N ', N A silicon wafer on which copper was formed was immersed in a solution obtained by adding water to 0.4 g of '-tetrakis (2-cyanoethyl) ethylenediamine and heating it to 70 ° C. After 1 minute, washing with water and measuring the damage rate of copper from the change of the film thickness of copper were 0.48 nm / min. Similarly, the silicon wafer in which aluminum was formed was immersed in 70 degreeC liquid. After 1 minute, washing with water and measuring the damage rate of aluminum from the film thickness change of aluminum were 0.09 nm / min.

Example 4

The peeling liquid of Example 3 was heated at 70 degreeC for 12 hours. After cooling, the separation solution was analyzed by gas chromatography, and the decomposition of N-methylacetamide was 0.5%.

Example 5

0.4 g of N- (2-cyanoethyl) ethylenediamine, 7.6 g of N, N'-bis (2-cyanoethyl) ethylenediamine, N, N, N'-tris (2-cyanoethyl) ethylene N-methylacetamide was added to 1.6 g of diamine and 0.4 g of N, N, N ', N'-tetrakis (2-cyanoethyl) ethylenediamine to make 100 g. This was heated to 70 ° C and the silicon wafer on which the i-line resist was formed was dipped. After 1 minute of washing with water, the rate at which the resist was peeled off was observed, and it was completely peeled off.

 0.4 g of N- (2-cyanoethyl) ethylenediamine, 7.6 g of N, N'-bis (2-cyanoethyl) ethylenediamine, and N, N, N'-tris (2-cyanoethyl ) Copper is formed into a liquid obtained by heating a solution of 1.6 g of ethylenediamine and 0.4 g of N, N, N ', N'-tetrakis (2-cyanoethyl) ethylenediamine to 100 g by heating the solution at 100 ° C. One silicon wafer was immersed. After 1 minute, washing with water and measuring the damage rate of copper from the change of the film thickness of copper were 0.58 nm / min. Similarly, the silicon wafer in which aluminum was formed was immersed in 70 degreeC liquid. After 1 minute, washing with water and measuring the damage rate of aluminum from the film thickness change of aluminum were 0.14 nm / min.

Example 6

The peeling liquid of Example 5 was heated at 70 degreeC for 12 hours. After cooling, analysis of the stripping solution by gas chromatography showed that decomposition of N-methylacetamide was 0.9%, and the decomposition slightly increased as compared with Examples 1 and 4.

Comparative Example 1

0.9 g of N- (2-cyanoethyl) ethylenediamine, 7.7 g of N, N'-bis (2-cyanoethyl) ethylenediamine, N, N, N'-tris (2-cyanoethyl) ethylene N-methylacetamide was added to 1.1 g of diamine and 0.5 g of N, N, N ', N'-tetrakis (2-cyanoethyl) ethylenediamine to make 100 g.

The stripper was heated at 70 ° C. for 12 hours. After cooling, the separation solution was analyzed by gas chromatography, and the decomposition of N-methylacetamide was 2.5%.

When the monomer was 5% or more of the total cyanoethylamine, the degradability of the organic solvent was remarkably increased.

Comparative Example 2

The test was carried out in the same manner as in Example 1 except that monoethanolamine was used instead of N, N'-bis (2-cyanoethyl) ethylenediamine.

As a result, the peeling rate of the resist was 80%, the damage to copper was 1.13 nm / min, and the damage to aluminum was 0.38 nm / min.

Comparative Example 3

The peeling liquid of the comparative example 2 was heated at 70 degreeC for 12 hours. After cooling, the separation solution was analyzed by gas chromatography, and the decomposition of N-methylacetamide was 4.5%.

Example 7

0.4 g N- (2-cyanoethyl) -N '-(2-aminoethyl) piperazine, N, N'-bis (2-cyanoethyl) -N "-(2-aminoethyl) piperazine 9.6 Dimethyl sulfoxide was added to g to make 100 g, which was heated to 40 ° C., and the silicon wafer on which the i-line resist was formed was immersed in. After 9 minutes, the resultant was washed with water to observe the rate at which the resist was peeled off. Furthermore, this composition liquid was heated to 70 degreeC, and the silicon wafer which formed copper was immersed in. After 1 minute, it washed with water and measured the damage rate of copper from the change of the film thickness of copper, 0.06 nm / It was minutes.

Comparative Example 4

Dimethyl sulfoxide was added to 0.4 g of N- (2-cyanoethyl) -N '-(2-aminoethyl) piperazine and 9.6 g of N- (2-aminoethyl) piperazine to make 100 g. This was heated to 40 degreeC and the silicon wafer which formed the i-line resist into a film was immersed. After 15 minutes, the resultant was washed with water, and the rate at which the resist was peeled off was observed. Furthermore, this composition liquid was heated to 70 degreeC, and the silicon wafer which formed the copper film was immersed. After 1 minute, washing with water and measuring the damage rate of copper from the change of the film thickness of copper were 0.31 nm / min.

According to the present invention, it is possible to provide a composition capable of removing a resist without damaging a semiconductor or flat panel display material, and it is possible to manufacture a miniaturized semiconductor and flat panel display, which is very useful industrially.

Claims (6)

A resist removal composition comprising poly (cyanoalkyl) ethyleneamine. The composition for removing a resist according to claim 1, which is formed by using an organic solvent as a solvent. The poly (cyanoalkyl) ethyleneamine according to claim 1 or 2, wherein N- (2-cyanoethyl) ethylenediamine is contained, and the content of the N- (2-cyanoethyl) ethylenediamine is poly (cyanoalkyl) ethyleneamine. Less than 5% of the resist removal composition. The poly (cyanoalkyl) ethyleneamine of claim 1 or 2, wherein N, N'-bis (2-cyanoethyl) -ethylenediamine, N, N-bis (2-cyanoethyl) ethylenediamine, N, N, N'-tris (2-cyanoethyl) ethylenediamine, N, N, N ', N'-tetrakis (2-cyanoethyl) ethylenediamine, N, N'-bis (2-cyanoethyl) piperazine, N, N'-bis (2-cyanoethyl) -N "-(2-aminoethyl) piperazine, N, N ', N'-tris (2-cyanoethyl) -N "-(2-aminoethyl) piperazine, N, N-bis (2-cyanoethyl) -N '-(2-aminoethyl) piperazine, N, N ', N "-tris (2-cyanoethyl) diethylene triamine and N, N, N ', N ", N" -pentakis (2-cyanoethyl) diethylenetriamine is at least one member selected from the group consisting of. The resist removal composition according to claim 1 or 2, wherein the resist used for the manufacture of a semiconductor or flat panel display using at least one metal selected from the group consisting of aluminum, copper and molybdenum is peeled off. . Using the resist removal composition of Claim 1, the process of peeling the resist used for manufacture of the semiconductor or flat panel display using at least 1 sort (s) of metal chosen from the group which consists of aluminum, copper, and molybdenum, Method of peeling resist