JP2008191631A - Composition for removing resist - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for removing resist which has an excellent resist stripping property and causes less damage to a semiconductor or a flat panel display material. <P>SOLUTION: In the composition for removing resist, a resist stripping agent which comprises poly(cyanoalkyl) ethyleneamine is used. Therein, the poly(cyanoalkyl)ethyleneamine is preferably at least one 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. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a remover for removing a photoresist layer in a manufacturing process of a semiconductor integrated circuit, a printed wiring board, and a liquid crystal.

  A semiconductor integrated circuit is formed by applying a photoresist on a base, exposing and developing, etching, forming a circuit, and then removing the photoresist from the base, or ashing after forming the circuit. Then, the remaining resist residue is removed. Various resist stripping agents have been proposed for stripping a photoresist from a substrate or stripping a resist residue from a substrate.

  Conventionally, the most frequently used resist stripping agents contain ethanolamines such as monoethanolamine (for example, Patent Document 1).

  However, the resist stripping ability of monoethanolamine is not only industrially inadequate, but also has the disadvantage that the semiconductor and flat panel display materials are severely damaged.

  Aluminum is used as a wiring material for conventional semiconductor integrated circuits, and monoethanolamine can be used without problems for aluminum wiring. However, in recent years, semiconductor integrated circuits have been miniaturized, and the wiring material is changing from aluminum having a high resistance to copper having a low resistance. However, monoethanolamine, which is the main component of conventional resist strippers, is highly corrosive to copper and is difficult to use in copper wiring processes.

  Further, in flat panel displays such as liquid crystal panels, chromium has been used as a gate material. However, flat panel displays are also changing to materials having a lower resistance than chromium, that is, aluminum, molybdenum, and copper. Regarding flat panel displays, monoethanolamine, which is the main raw material of conventional release agents, was very damaged.

  Further, conventionally known cyanoethylethyleneamine such as N- (2-cyanoethyl) ethylenediamine is excellent in resist stripping property when used as an aqueous solution and has little damage to aluminum and copper, but is an organic solvent like monoethanolamine. When used in the above, it reacts with an organic solvent to cause decomposition (see Patent Document 2).

  As described above, there is a demand for a stripping solution that has a higher resist stripping capability than monoethanolamine, causes little damage to semiconductors and flat panel display materials, and has low reactivity with organic solvents.

JP 62-49355 A JP 2004-155822 A

  As described above, the resist stripping agents that have been proposed in the past do not have sufficient stripping properties and damage semiconductors and flat panel display materials. Therefore, an object of the present invention is to provide a resist removing composition that exhibits excellent resist releasability and has little damage to semiconductors and flat panel display materials.

  As a result of intensive studies on resist removal, the present inventors have found that a resist removal composition comprising an amine having a plurality of cyanoalkyl groups has high resist stripping ability and decomposes by reacting with a solvent, particularly an organic solvent. In addition, the present inventors have found that the damage to semiconductors and flat panel display materials is small, and have completed the present invention.

  That is, the present invention is a resist removal composition comprising poly (cyanoalkyl) ethyleneamine.

  The present invention is described in further detail below.

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

  Poly (cyanoalkyl) ethyleneamine is a compound in which ethyleneamines contain two or more cyanoalkyl groups such as cyanoethyl groups. When the number of cyanoalkyl groups is less than 2, the organic solvent to be used is easily decomposed, and the damage to the semiconductor material and the flat panel display material increases.

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

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

  For example, when N, N′-bis (2-cyanoethyl) ethylenediamine is mixed with ethylenediamine in an amount of at least 2 equivalents of acrylonitrile in a solvent, the addition reaction proceeds with its own heat of reaction, and a bis body is obtained. As the solvent, water or an organic solvent can be used. In this reaction, N- (2-cyanoethyl) ethylenediamine (mono) to which only 1 equivalent of acrylonitrile is added, or N, N, N′-tris (2-cyanoethyl) ethylenediamine (tris) to which 3 equivalents or more are added, N , N, N ′, N′-tetrakis (2-cyanoethyl) ethylenediamine (tetrakis) may be produced as a by-product, but in the present invention, the content of a mono-body that is not poly (cyanoalkyl) ethyleneamine may be reduced. preferable. The tris and tetrakis bodies do not affect the decomposition of organic solvents, and there is no problem because the damage to semiconductor materials and flat panel display materials is small. However, the mono body is at least 20% or less, especially 5% of the entire cyanoalkylamine. In the following, it is further preferable not to contain at all. If the mono-body exceeds 20%, the organic solvent to be used is easily decomposed, and the damage to the semiconductor material and the flat panel display material increases.

  In the resist removal composition of the present invention, an organic solvent or water can be used as a solvent, but it is particularly preferable to use an organic solvent.

  In the resist removal composition of the present invention, the organic solvent that can be used is not particularly limited as long as it is miscible with poly (cyanoalkyl) ethyleneamine. Examples of readily available and inexpensive organic solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylacetamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, acetamide, N-methylpyrrolidone, N, N -Diethylformamide, N, N'-dimethylethyleneurea, N, N'-dimethylpropyleneurea, tetramethylurea, methyl dimethylcarbamate, acetonitrile, lactamide, hydroxybutyric acid amide, 2-pyrrolidone, N-methylpropionamide, dimethyl Propylamide, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol, dipropylene glycol Monomethyl ether, ethylene glycol, propylene glycol, and the like. Among these organic solvents, for example, N-methylacetamide and the like react with monoethanolamine, N- (2-cyanoethyl) ethylenediamine and the like, and the solvent is decomposed. However, the organic solvent is used for the resist removing composition of the present invention. The poly (cyanoalkyl) ethyleneamine that can be produced hardly reacts with an organic solvent and can prevent decomposition of the solvent.

  The composition for removing a resist of the present invention exhibits excellent performance for removing a resist used in the production of semiconductor devices, flat panel displays and the like. Among them, in particular, it can be used for removing a resist used in the production of a semiconductor or flat panel display using at least one metal selected from the group consisting of aluminum, copper and molybdenum.

  The temperature at the time of using the resist removing composition of the present invention is 20 to 180 ° C, preferably 80 to 160 ° C. If the temperature exceeds 180 ° C., poly (cyanoalkyl) ethyleneamine decomposes, and if it is less than 20 ° C., it is difficult to remove the resist at an industrially satisfactory rate.

  When the resist removing composition of the present invention is used and the resist is removed, ultrasonic waves or the like may be used to accelerate the removal rate.

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

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

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 a silicon wafer on which an i-line resist was formed was immersed. After 1 minute, it was washed with water, and when the rate at which the resist was peeled was observed, it was completely peeled off.

  In addition, a silicon wafer on which copper was formed was immersed in a solution obtained by adding water to 10 g of N, N′-bis (2-cyanoethyl) ethylenediamine to make 100 g. After 1 minute, it was washed with water, and the copper damage rate was measured from the change in the copper film thickness, which was 0.55 nm / min. Similarly, a silicon wafer on which aluminum was formed was immersed in a liquid at 70 ° C. After 1 minute, it was washed with water, and the damage rate of the aluminum was measured from the change in the film thickness of the aluminum and found to be 0.12 nm / min.

Example 2
The stripping solution of Example 1 was heated at 70 ° C. for 12 hours. When the stripping solution was analyzed by gas chromatography after cooling, the decomposition of N-methylacetamide was 0.7%.

Example 3
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′-tetrakis (2-cyanoethyl) ) N-methylacetamide was added to 0.4 g of ethylenediamine to make 100 g. This was heated to 70 ° C., and a silicon wafer on which an i-line resist was formed was immersed. After 1 minute, it was washed with water, and when the rate at which the resist was peeled was observed, it was completely peeled off.

  Also, 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′-tetrakis (2- A silicon wafer on which copper was formed was immersed in a solution prepared by adding water to 0.4 g of cyanoethyl) ethylenediamine to 100 g. After 1 minute, it was washed with water, and the copper damage rate was measured from the change in the copper film thickness, which was 0.48 nm / min. Similarly, a silicon wafer on which aluminum was formed was immersed in a liquid at 70 ° C. After 1 minute, it was washed with water, and the damage rate of the aluminum was measured from the change in the film thickness of the aluminum, and it was 0.09 nm / min.

Example 4
The stripping solution of Example 3 was heated at 70 ° C. for 12 hours. After cooling, the stripping solution was analyzed by gas chromatography. As a result, the decomposition of N-methylacetamide was 0.5%.

Example 5
N- (2-cyanoethyl) ethylenediamine 0.4 g, N, N′-bis (2-cyanoethyl) ethylenediamine 7.6 g, N, N, N′-tris (2-cyanoethyl) ethylenediamine 1.6 g, and N, N N-methylacetamide was added to 0.4 g of N, N ′, N′-tetrakis (2-cyanoethyl) ethylenediamine to make 100 g. This was heated to 70 ° C., and a silicon wafer on which an i-line resist was formed was immersed. After 1 minute, it was washed with water, and when the rate at which the resist was peeled was observed, it was completely peeled off.

  N- (2-cyanoethyl) ethylenediamine 0.4 g, N, N′-bis (2-cyanoethyl) ethylenediamine 7.6 g, N, N, N′-tris (2-cyanoethyl) ethylenediamine 1.6 g, and N , N, N ′, N′-Tetrakis (2-cyanoethyl) ethylenediamine 0.4 g of water was added to 100 g, and the silicon wafer on which copper was formed was immersed in a solution heated to 70 ° C. After 1 minute, it was washed with water, and the damage rate of copper was measured from the change in film thickness of copper, and it was 0.58 nm / min. Similarly, a silicon wafer on which aluminum was formed was immersed in a liquid at 70 ° C. After 1 minute, it was washed with water, and the damage rate of the aluminum was measured from the change in the film thickness of the aluminum and found to be 0.14 nm / min.

Example 6
The stripping solution of Example 5 was heated at 70 ° C. for 12 hours. When the stripping solution was analyzed by gas chromatography after cooling, the decomposition of N-methylacetamide was 0.9%, which was slightly increased as compared with Examples 1 and 4.

Comparative Example 1
N- (2-cyanoethyl) ethylenediamine 0.9 g, N, N′-bis (2-cyanoethyl) ethylenediamine 7.7 g, N, N, N′-tris (2-cyanoethyl) ethylenediamine 1.1 g, and N, N N-methylacetamide was added to 0.5 g of N, N ′, N′-tetrakis (2-cyanoethyl) ethylenediamine to make 100 g.

  The stripping solution was heated at 70 ° C. for 12 hours. After cooling, the stripping solution was analyzed by gas chromatography. As a result, the decomposition of N-methylacetamide was 2.5%.

  When the mono-form was 5% or more of the entire cyanoethylamine, the decomposability of the organic solvent was remarkably increased.

Comparative Example 2
The test was conducted in the same manner as in the Examples except that monoethanolamine was used instead of N, N′-bis (2-cyanoethyl) ethylenediamine.

  As a result, the resist peeling rate 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 stripping solution of Comparative Example 2 was heated at 70 ° C. for 12 hours. After cooling, the stripping solution was analyzed by gas chromatography. As a result, the decomposition of N-methylacetamide was 4.5%.

Example 7
0.4 g of N- (2-cyanoethyl) -N ′-(2-aminoethyl) piperazine, 9.6 g of N, N′-bis (2-cyanoethyl) -N ″-(2-aminoethyl) piperazine and dimethyl Sulfoxide was added to make 100 g. This was heated to 40 ° C., and a silicon wafer on which an i-line resist was formed was immersed. After 9 minutes, it was washed with water and the rate at which the resist was peeled was observed. Further, this composition solution was heated to 70 ° C., and a silicon wafer on which copper was formed was immersed. After 1 minute, it was washed with water, and the copper damage rate was measured from the change in the copper film thickness, which was 0.06 nm / min.

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 ° C., and a silicon wafer on which an i-line resist was formed was immersed. After 15 minutes, it was washed with water and the rate at which the resist was peeled off was observed. Further, this composition solution was heated to 70 ° C., and a silicon wafer on which copper was formed was immersed. After 1 minute, it was washed with water, and the damage rate of copper was measured from the change in the film thickness of copper, and it was 0.31 nm / min.

Claims (6)

A resist removal composition comprising poly (cyanoalkyl) ethyleneamine. The resist removing composition according to claim 1, wherein an organic solvent is used as the solvent. The resist removal composition according to claim 1 or 2, wherein N- (2-cyanoethyl) ethylenediamine is less than 5% of the whole cyanoalkylethyleneamine. Poly (cyanoalkyl) ethyleneamine is 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-amino) Ethyl) piperazine, N, N ′, N ″ -tris (2-cyanoethyl) diethylenetriamine, N, N, N ′, N ″, N ″ -pentakis (2-cyanoethyl) The resist removing composition according to claim 1 is at least one selected from the group consisting of diethylene triamine. The resist according to any one of claims 1 to 4, wherein the resist used for manufacturing a semiconductor or flat panel display using at least one metal selected from the group consisting of aluminum, copper, and molybdenum is peeled off. Removal composition. A resist used for manufacturing a semiconductor or flat panel display using at least one metal selected from the group consisting of aluminum, copper, and molybdenum, using the resist removing composition according to claim 1. Peeling method.