WO2008023614A1

WO2008023614A1 - Composition for removal of resist comprising poly(cyanoalkyl)ethyleneamine and method for removal of resist using the composition

Info

Publication number: WO2008023614A1
Application number: PCT/JP2007/065865
Authority: WO
Inventors: Yasushi Hara; Fumiharu Takahashi
Original assignee: Tosoh Corporation
Priority date: 2006-08-21
Filing date: 2007-08-14
Publication date: 2008-02-28

Abstract

Disclosed are: 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

Specification

Resist removing composition comprising poly (cyanoalkyl) ethyleneamine and resist removing method using the same

Technical field

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.

This application (April, 2006, August 21, 2006 Japanese Patent Application No. 2006-223988 filed, Japanese Patent Application No. 2007-4208, filed Jan. 12, 2007, and 2007 3 Priority is claimed for Japanese Patent Application No. 2007-68529 filed on May 16, and the contents thereof are incorporated herein.

Background art

[0002] A semiconductor integrated circuit is formed by applying a photoresist on a substrate, exposing and developing, etching, forming a circuit, and then removing the photoresist from the substrate. It is manufactured by removing the resist after performing sashing and then removing the remaining resist residue. Various resist strippers have been proposed for stripping photoresist from a substrate or stripping resist residues from a substrate.

[0003] Conventionally, the most frequently used resist remover contains ethanolamines such as monoethanolamine! /, Etc. (for example, Patent Document 1).

[0004] However, monoethanolamine's resist stripping capability is not only industrially inadequate, but also suffers from a large damage to semiconductor and flat panel display materials.

[0005] Aluminum has been used as a wiring material for conventional semiconductor integrated circuits, and monoethanolamine could be used without any problem 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 was the main component of conventional resist strippers, is difficult to use in copper wiring processes where copper is highly corroded. [0006] In addition, chrome has been used as a gate material in flat panel displays such as liquid crystal panels. Flat panel displays are also changing to materials with lower resistance than chrome, that is, aluminum, molybdenum, and copper. . As for flat panel displays, monoethanolamine, the main raw material of conventional release agents, was severely damaged.

[0007] In addition, conventionally known cyanoethyl ethyleneamines such as N- (2-cyanoethyl) ethylenediamine are excellent in resist releasability when used as an aqueous solution, and the damage to aluminum and copper is small. Like min, when used in an organic solvent, it reacted with the organic solvent and caused decomposition (see Patent Document 2).

[0008] As described above, there is a demand for a stripping solution that is less damaging to semiconductors and flat panel display materials that have a higher resist stripping ability than monoethanolamine and that has low reactivity with organic solvents. ! /

[0009] Patent Document 1: Japanese Patent Laid-Open No. 62-49355

Patent Document 2: JP 2004-155822 Koyuki

Disclosure of the invention

Problems to be solved by the invention

[0010] As described above, the conventionally proposed resist removers have damage to semiconductors and flat panel display materials that have insufficient peelability. Therefore, an object of the present invention is to provide a resist removing composition that exhibits excellent resist stripping properties and has little damage to semiconductors and flat panel display materials, and a resist stripping method using the resist removing composition There is to do.

Means for solving the problem

[0011] 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 reacts with a solvent having high resist stripping ability, particularly an organic solvent, and decomposes. As a result, it was found that the damage to the semiconductor and flat panel display materials was small, and the present invention was completed.

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

[0013] Hereinafter, the present invention will be described in more detail. [0014] An essential component of the resist removal composition of the present invention is poly (cyanoalkyl) ethyleneamine.

[0015] Poly (cyanoalkyl) ethyleneamine is a compound in which two or more cyanoalkyl groups such as a cyanoethyl group are contained in ethyleneamines. 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 flat panel display material increases.

[0016] Examples of poly (cyanoalkyl) ethyleneamine that can be used in the resist removing composition of the present invention include N, N 'bis (2-cyanethinole) monoethylene diamine, N, N bis (2-cyanethyl) ethylene diamine, N , N, N '—Tris (2-cyanoethyl) ethylenediamine, N, N, Ν', Ν, -tetrakis (2-cyanoenoethyl) ethylenediamine, Ν, Ν, monobis (2-cyanoethyl) piperazine, Ν, Ν , Bis (2-Cyanethyl) Ν,, （(2-Aminoethyl) piperazine, Ν, Ν ', Ν, Tris (2-Cyanoethyl) Ν, —Bis (2-cyanethinole) Ν, One (2-aminoethinole) piperazine, Ν, Ν,, Ν, '—Tris (2-cyanethinole) diethylenetriamine, Ν, Ν, Ν', Ν ", Ν", ペンタ "-penta Kiss (2—Shea At least Tanedea selected from the group consisting of ethyl) diethylene tri § Min

[0017] Poly (cyanoalkyl) ethyleneamine can be easily produced by adding acrylonitrile or metathalonitrile to ethyleneamines such as ethylenediamine, diethylenetriamine, piperazine and the like.

[0018] For example, Ν, N 'bis (2 cyanoethyl) ethylenediamine has an addition reaction that proceeds with its own heat of reaction when ethylenediamine is mixed with at least twice the equivalent amount of acrylonitrile in a solvent to obtain a bis-form. . As the solvent, water or an organic solvent can be used. In this reaction, only 1 equivalent of atalonitrile is added! /, Ν- (2-cyanoethyl) ethylenediamine (monomer), or 当量, Ν, N'-tris (2 cyanoethyl) ethylenediamine added with 3 equivalents or more. (Tris body), Ν, Ν, Ν ', Ν,-tetrakis (2-cyanethinole) ethylenediamine (tetrax body) may be a by-product S, in the present invention, a mono-body that is not poly (cyanoalkyl) ethyleneamine The content of is preferably reduced. Tris and tetrakis bodies do not affect the decomposition of organic solvents and damage semiconductor materials and flat panel display materials. However, it is preferable that the mono-form does not contain at least 20% or less, particularly 5% or less of the whole cyanoalkylamine, or even not at all. If the mono-body exceeds 20%, the organic solvent used is likely to be decomposed, and the damage to the semiconductor material and 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. Available and inexpensive organic solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylacetamide, dimethyl sulfoxide, sulfolane, hexamethyl phosphate triamide, acetateamide, N-methyl. Pyrrolidone, N, N-jetylformamide, N, N'-dimethylethyleneurea, N, N'-dimethylpropyleneurea, tetramethylurea, dimethylcananol methyl ester, acetonitrile, lactamide, hydroxybutyramide, 2-pyrrolidone, N—Methylpropionamide, dimethylpropylamide, diethylene glycol, diethylene glycol monomethinoatenoate, diethyleneglycolonemonobutenoatenore, propylene glycolenolemonomethinoatenore, dipropylene glycolenole, dipropylene Examples thereof include ethylene glycol monomethyl ether, ethylene glycol, and propylene glycol. 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. Poly (cyanoalkyl) ethyleneamine that can be used in the reaction 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. In particular, the force S is used to remove a resist used in the manufacture of a semiconductor or flat panel display using at least one metal selected from the group consisting of aluminum, copper and molybdenum.

[0022] The temperature when using the resist removal composition of the present invention is 20 to 180 ° C, preferably 80 to 80 ° C. At temperatures above 180 ° C, poly (cyanoalkyl) ethyleneamine is At temperatures below 20 ° C, it is difficult to remove the resist at an industrially satisfactory rate.

[0023] When the resist removing composition of the present invention is used to remove the resist, an ultrasonic wave or the like may be used to accelerate the removal speed.

The invention's effect

[0024] According to the resist removing composition of the present invention, it is possible to remove the resist without damaging the semiconductor and flat panel display material, and thus it becomes possible to produce a miniaturized semiconductor and flat panel display. .

BEST MODE FOR CARRYING OUT THE INVENTION

[0025] The ability to explain the present invention in more detail with reference to the following examples The present invention is not limited thereto.

[0026] 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 ratio of the resist peeled was observed, it was completely peeled off

Yes

[0027] Further, 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 damage rate of copper was measured from the change in copper film thickness. The result was 0.55 nm / min. Similarly, a silicon wafer with aluminum film was immersed in a 70 ° C solution. After 1 minute, it was washed with water, and the damage rate of the aluminum was measured from the change in the aluminum film thickness. The result was 0.12 nm / min.

[0028] Example 2

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

[0029] Example 3

N, N 'bis (2 cyanoethinole) ethylenediamine 7.9 g, N, N, N' tris (2 cyanoethyl) ethylenediamine 1 · 7 g, and N, N, Ν ', Ν, -tetrakis (2 cyanoethyl) ethylenediamine 0 · 4Methylacetamide was added to 4 g to make 100 g. Add this to 70 ° C The silicon wafer with the i-line resist film was immersed by heating. After 1 minute, it was washed with water and the rate at which the resist was peeled off was observed.

[0030] Also, N, N 'bis (2 cyanoethinole) ethylenediamine 7.9 g, N, N, N' tris (2-cyanoethyl) ethylenediamine 1.7 g, and N, N, Ν ', N'-tetrakis (2 cyanoeth Nole) A silicon wafer on which copper was formed was immersed in a solution obtained by adding water to 0.4 g of ethylenediamine to 100 g by heating to 70 ° C. After 1 minute, it was washed with water, and the copper damage rate was measured from the change in copper film thickness. The result was 0.48 nm / min. Similarly, a silicon wafer with aluminum film was immersed in a 70 ° C solution. 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.

[0031] Example 4

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

[0032] Example 5

N— (2-Cyanethinole) ethylenediamine 0.4 g, N, N, bis (2-Cyanethinole) ethylenediamine 7.6 g, N, N, N'tris (2 Cyanethyl) ethylenediamine 1.6 g, and N, N , Ν ', Ν, -Tetrakis (2-cyanethyl) ethylenediamine 0.4 · g was added with メチル methylacetamide 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 the rate at which the resist was peeled off was observed.

[0033] Also, N— (2 cyanoethyl) ethylenediamine 0 · 4 g, N, N ′ bis (2 cyanoethylene) ethylenediamine 7.6 g, N, N, N′—tris (2 cyanoethyl) ethylenediamine 1 · 6 g, and A silicon wafer having a copper film was immersed in a solution obtained by heating water at 70 ° C. to a solution obtained by adding water to 4 · 4 g of water to make 100 g of ·, Ν, Ν ′, Ν′-tetrakis (2-cyanethyl) ethylenediamine.

After 1 minute, it was washed with water, and the copper damage rate was measured from the change in copper film thickness. The result 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.

[0034] Example 6 The stripping solution of Example 5 was heated at 70 ° C. for 12 hours. When the stripped 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.

[0035] Comparative Example 1

N (2 cyanoethinole) ethylenediamine 0.9 g, N, N, monobis (2 cyanoethinole) ethylenediamine 7.7 g, N, N, N 'tris (2 cyanoethyl) ethylenediamine 1 lg, and N, N, Ν' , Ν, -Tetrakis (2-cyanoethyl) ethylenediamin 0.5 g was added with メチル methylacetamide to make lOOg.

[0036] The stripping solution was heated at 70 ° C for 12 hours. After cooling, the stripper solution was analyzed by gas chromatography. The decomposition of N-methylacetamide was 2.5%.

[0037] When the mono-form was 5% or more of the whole cyanoethylamine, the decomposability of the organic solvent was remarkably increased.

[0038] Comparative Example 2

The test was performed in the same manner as in Example 1 except that monoethanolamine was used instead of N, N′bis (2-cyanethyl) 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.

[0040] Comparative Example 3

The stripping solution of Comparative Example 2 was heated at 70 ° C. for 12 hours. After cooling, the stripped solution was analyzed by gas chromatography. The decomposition of N-methylacetamide was 4.5%.

[0041] Example 7

N- (2-Cyanethinole) N, 1 (2-Aminoethyl) piperazine 0 · 4g, N, N 'Bis (2Cyanethyl) N,' Di (2aminoethyl) piperazine 9 · 6g with dimethylsulfo I made a lOOg with calories. 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 when the ratio of the resist peeled was observed, it was completely peeled off. Further, this composition liquid 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 copper film thickness. The result was 0.06 nm / min. [0042] Comparative Example 4

N- (2-Cyanoethyl) N, mono (2-aminoethyl) piperazine 0.4 g, N- (2-aminoethyl) piperazine 9.6 g was added with dimethyl sulfoxide 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 liquid 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 copper film thickness.

Industrial applicability

[0043] According to the present invention, it is possible to provide a composition capable of removing a resist with no damage to semiconductor and flat panel display materials, and to manufacture a miniaturized semiconductor and flat panel display. It is extremely useful in industry.

Claims

The scope of the claims

[1] A resist removing composition comprising poly (cyanoalkyl) ethyleneamine.

[2] The resist removing composition according to [1], wherein an organic solvent is used as the solvent.

[3] The resist-removing composition according to claim 1 or 2, comprising N— (2 cyanoethyl) ethylenediamine, wherein the content of N— (2 cyanoethyl) ethylenediamine is less than 5% of the whole poly (cyanoalkyl) ethyleneamine. object.

[4] Poly (cyanoalkyl) ethyleneamines S, N, N 'bis (2-cyanethyl) monoethylene diamine, N, N bis (2-cyanethinole) ethylenediamine, N, N, N' tris (2-cyanethinole) Ethylenediamine, N, N, Ν ', N'-tetrakis (2-cyanethinole) ethylene diamine, Ν, N' monobis (2-cyanethinole) piperazine, Ν, Ν, monobis (2-cyanethinole) ,, One (2-aminoethinole) piperazine, Ν, Ν ', Ν, One tris (2-cyanethyl) Ν, One (2-aminoethyl) piperazine, Ν, Ν-bis (2-cyanethinole ) Ν, One (2-Aminoethyl) piperazine, Ν, Ν ', Ν "—Tris (2-Cyanethyl) diethylenetriamine, Ν, Ν, Ν', Ν", Ν,, one pentakis (2— From the group consisting of cyanoethyl) diethylenetriamine At least one a resist removing composition according to claim 1 or 2, in which barrel.

[5] 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 stripped. A resist removal composition.

[6] Using the resist removing composition according to claim 1, 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 stripped. A resist stripping method including the step of: