JP4962254B2 - Resist removing composition and resist removing method using the same - Google Patents

Description

  The present invention relates to a resist removing composition for removing a photoresist layer in a manufacturing process of a semiconductor integrated circuit, a printed wiring board, and a liquid crystal, and a resist removing method using the same.

  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 has been the main component of conventional resist strippers, is highly corrosive to copper and is difficult to use in copper wiring processes.

  On the other hand, in flat panel displays such as liquid crystal panels, chromium has been used as a gate material, but the wiring material of flat panel displays is also changing to materials having a lower resistance than chromium, that is, aluminum, molybdenum, and copper. Therefore, the flat panel display has a problem that the monoethanolamine, which is the main raw material of the conventional release agent, has a large damage.

  Further, conventionally known cyanoethylethyleneamine such as N- (2-cyanoethyl) ethylenediamine is excellent in resist stripping property when used as an aqueous solution, and damage to aluminum and copper is small. When used in the above, there is a problem that it reacts with an organic solvent to cause decomposition. Therefore, there is a demand for a stripping solution that has higher resist stripping ability than monoethanolamine, less damage to semiconductor and flat panel display materials, and low reactivity with organic solvents.

JP 62-49355 A JP 2004-155822 A

  Conventional resist strippers are not sufficiently peelable and have a problem of damage to semiconductors and flat panel display materials. An object of the present invention is to provide a resist removing composition that has excellent resist removability, does not decompose an organic solvent, and has little damage to a flat panel display material.

  As a result of intensive studies on resist removal, the present inventors have found that a resist removal composition comprising N- (cyanoalkyl) -N ′-(2-hydroxyalkyl) ethylenediamine has a high resist removal capability, and an organic solvent. The present invention has been completed by finding that it is not decomposed by reacting with, and that the damage to the semiconductor and flat panel display materials is small.

  The present invention is described in further detail below.

  As N- (cyanoalkyl) -N ′-(2-hydroxyalkyl) ethylenediamine used in the resist removal composition of the present invention, N- (2-cyanoethyl) -N ′-(2-hydroxyethyl) ethylenediamine, N- (2-methyl-2-cyanoethyl) -N ′-(2-hydroxyethyl) ethylenediamine is preferably at least one selected from the group consisting of ethylenediamine.

  N- (Cyanoalkyl) -N ′-(2-hydroxyalkyl) ethylenediamine is easily obtained by adding an unsaturated nitrile (acrylonitrile, methacrylonitrile, etc.) to 2- (2-aminoalkylamino) ethanol. Can be manufactured. For example, N- (2-cyanoethyl) -N ′-(2-hydroxyethyl) ethylenediamine is an addition reaction with its own heat of reaction when 2- (2-aminoethylamino) ethanol is mixed with an equivalent amount of acrylonitrile in a solvent. Can be obtained.

  As the solvent, water or an organic solvent can be used. In this reaction, in addition to N- (2-cyanoethyl) -N ′-(2-hydroxyethyl) ethylenediamine (mono) to which only one equivalent of acrylonitrile is added, N, N′-bis (2- Cyanoethyl) ethylenediamine-N ′-(2-hydroxyethyl) ethylenediamine (bis), N, N-bis (2-cyanoethyl) -N ′-(2-hydroxyethyl) ethylenediamine (bis), N, N, N '-Tris (2-cyanoethyl) -N'-(2-hydroxyethyl) ethylenediamine (tris form) may be by-produced, but the composition of the present invention may contain these bis form and tris form. Even if a bis body or a tris body is generated, it does not affect the decomposition of the organic solvent, and there is no problem because the damage to the semiconductor material and flat panel display material is small.

  Further, even if unreacted 2- (2-aminoethylamino) ethanol remains, the remaining amount is small, or even if the remaining amount is relatively large, unreacted unsaturated nitriles may remain together. Can be used without any problem.

  When unsaturated nitriles do not remain, 2- (2-aminoethylamino) ethanol is preferably not contained, and at least 50% or less, particularly 20% or less of the total amine in the composition, It is preferable that it is 5% or less. If these unreacted substances exceed 50%, the organic solvent to be used tends to be decomposed, and damage to the semiconductor material and flat panel display material tends to increase.

  An organic solvent and water can be used for the solvent of the resist removing composition of the present invention. Addition of an organic solvent and water increases the resist removal capability.

  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 N- (cyanoalkyl) -N ′-(2-hydroxyalkyl) ethylenediamine. Examples of the organic solvent 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, methyldimethylcarbamate, acetonitrile, lactamide, hydroxybutyric acid amide, 2-pyrrolidone, N-methylpropionamide, dimethylpropylamide, 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, N-methylacetamide and the like react with monoethanolamine, 2- (2-aminoethylamino) ethanol, N- (2-cyanoethyl) ethylenediamine and the like, and the solvent is decomposed. The N- (cyanoalkyl) -N ′-(2-hydroxyalkyl) ethylenediamine of the resist removal composition of the invention hardly reacts with these organic solvents and can prevent decomposition of the organic solvent.

  The composition for removing a resist of the present invention not only decomposes these organic solvents, but also exhibits excellent performance for removing resists 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. At temperatures exceeding 180 ° C., N- (cyanoalkyl) -N ′-(2-hydroxyalkyl) ethylenediamine is likely to decompose, and at temperatures below 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.

  The resist removal composition of the present invention has no damage to semiconductors and flat panel display materials, has high resist removal performance, and does not decompose the organic solvent used together. A panel display can be manufactured.

  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- (2-cyanoethyl) -N ′-(2-hydroxyethyl) ethylenediamine to obtain 100 g of a resist removing composition. This was heated to 70 ° C., and a silicon wafer on which an i-line resist was formed was immersed. After 30 seconds, it was washed with water and the state of the resist was observed. As a result, it was completely removed.

  In addition, a silicon wafer on which copper was formed was immersed in a solution obtained by adding water to 10 g of N- (2-cyanoethyl) -N ′-(2-hydroxyethyl) 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 found to be 0.08 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 0.1% or less.

Example 3
N- (2-cyanoethyl) -N ′-(2-hydroxyethyl) ethylenediamine (9.8 g) and 2- (2-aminoethylamino) ethanol (0.2 g) were added with N-methylacetamide to give 100 g of a resist removing composition. It was. This was heated to 70 ° C., and a silicon wafer on which an i-line resist was formed was immersed. After 30 seconds, it was washed with water and the state of the resist was observed. As a result, it was completely removed.

  Further, 9.8 g of N- (2-cyanoethyl) -N ′-(2-hydroxyethyl) ethylenediamine and 0.2 g of 2- (2-aminoethylamino) ethanol were added with water to make 100 g. A silicon wafer on which copper was formed was immersed in the heated liquid. 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 0.53 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 0.11 nm / min.

Example 4
The stripping solution of Example 3 was heated at 70 ° C. for 12 hours. When the composition was analyzed by gas chromatography after cooling, the decomposition of N-methylacetamide was 0.3%.

Comparative Example 1
The test was conducted in the same manner as in Examples except that monoethanolamine was used in place of N- (2-cyanoethyl) -N ′-(2-hydroxyethyl) ethylenediamine.

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

Comparative Example 2
The resist removal composition of Comparative 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 4.5%.

Comparative Example 3
Heating was carried out in the same manner as in Example 2, except that N- (2-cyanoethyl) -ethylenediamine was used instead of N- (2-cyanoethyl) -N ′-(2-hydroxyethyl) ethylenediamine. When the stripping solution was analyzed by gas chromatography after cooling, the decomposition of N-methylacetamide was 4.2%.

Claims (6)

A resist removal composition comprising N- (cyanoalkyl) -N '-(2-hydroxyalkyl) ethylenediamine. The resist removing composition according to claim 1, wherein the N- (cyanoalkyl) -N ′-(2-hydroxyalkyl) ethylenediamine is N- (cyanoalkyl) -N ′-(2-hydroxyethyl) ethylenediamine. N- (cyanoalkyl) -N ′-(2-hydroxyalkyl) ethylenediamine is N- (2-cyanoethyl) -N ′-(2-hydroxyethyl) ethylenediamine and / or N- (2-methyl-2-cyanoethyl) The composition for removing a resist according to claim 1, which is —N ′-(2-hydroxyethyl) ethylenediamine. Furthermore, the composition for resist removal in any one of Claims 1-3 which uses an organic solvent. 5. The 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 is removed. Resist removing composition. The resist used for producing a semiconductor or flat panel display using at least one metal selected from the group consisting of aluminum, copper, and molybdenum is used as the resist removing composition according to any one of claims 1 to 4. Resist removal method.