JP2014010185A - Resist release agent and releasing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist release agent showing excellent resist detachability and also suppressing corrosion of copper.SOLUTION: The resist release agent comprising N-(2, 3-dihydroxypropyl)piperazine expresses excellent resist detachability, and can suppress corrosion of copper. Preferably the weight of the N-(2,3-dihydroxypropyl)piperazine is 0.5 to 50 wt.%.

Description

  The present invention relates to a release agent 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. Accordingly, various resist stripping agents have been proposed in the past in order to strip the photoresist from the substrate or strip the resist residue from the substrate.

  For example, a resist stripping composition using monoethanolamines is disclosed (see Patent Document 1). However, for example, in a copper wiring process using a copper wiring resist, if the resist is stripped with a stripping liquid composition containing monoethanolamines, the copper is corroded and is not satisfactory as a resist stripper. There wasn't.

  On the other hand, in resist strippers using amines, resist strippers containing piperazines such as N- (2-hydroxyethyl) piperazine as essential components are disclosed (see Patent Documents 2 and 3). Since these stripping agents showed excellent resist stripping properties and low corrosiveness to copper, they were effective for stripping resists used in copper wiring processes. However, in recent years, corrosion of copper has become severe due to miniaturization of wiring and the like, and conventionally proposed resist strippers have not been sufficient in terms of corrosiveness to copper.

JP 62-49355 A JP 2002-244310 A Japanese Patent Laid-Open No. 2004-205673

  This invention is made | formed in view of said subject, and while providing the outstanding resist peelability, it is providing the resist remover which suppresses the corrosivity to copper remarkably.

  As a result of intensive studies on the resist stripper, the present inventors have found that a resist stripper containing a specific amine is an excellent resist stripper and is a resist stripper that does not attack copper. It has come to be completed.

  That is, as shown below, the present invention is a resist stripper that exhibits excellent resist stripping properties without corroding copper or a copper alloy.

  [1] A resist stripper comprising an amine represented by the following general formula.

(In the formula, R ₁ and R ₂ each independently represent hydrogen, a methyl group, or an ethyl group.)
[2] The amine is N- (2,3-dihydroxypropyl) piperazine, N- (2-hydroxy-3-methoxypropyl) piperazine, N- (2-hydroxy-3-ethoxypropyl) piperazine, N- (2- Methoxy-3-hydroxypropyl) piperazine, N- (2-hydroxy-3-ethoxypropyl) piperazine, the resist stripping agent [3] according to the above [1], further comprising a water-soluble organic solvent and / or The resist remover according to [1] or [2] above, which contains water.

  [4] The water-soluble organic solvent is at least one selected from the group consisting of sulfoxides, sulfones, amides, lactams, imidazolidinones, glycols, and glycol ethers. ] The resist remover described in the above.

  [5] The resist remover according to any one of [1] to [4], wherein the amine content is 0.1 wt% or more and 50 wt% or less.

  [6] A resist stripping method comprising stripping a resist for copper wiring using the resist stripper according to any one of [1] to [5].

  The resist stripper of the present invention is extremely useful industrially as a resist stripper that exhibits excellent resist stripping properties and does not corrode copper and copper alloys.

  The resist stripper of the present invention contains amine and water represented by the following general formula as essential components.

(In the formula, R ₁ and R ₂ each independently represent hydrogen, a methyl group, or an ethyl group.)
Specific examples of amines used in the resist stripper of the present invention include N- (2,3-dihydroxypropyl) piperazine, N- (2-hydroxy-3-methoxypropyl) piperazine, and N- (2-hydroxy). -3-ethoxypropyl) piperazine, N- (2-methoxy-3-hydroxypropyl) piperazine, N- (2-hydroxy-3-ethoxypropyl) piperazine and the like, and N- (2,3-dihydroxypropyl) Piperazine and N- (2-hydroxy-3-methoxypropyl) piperazine are preferable, and N- (2,3-dihydroxypropyl) piperazine is particularly preferable.

  Particularly preferably used N- (2,3-dihydroxypropyl) piperazine exhibits excellent resist releasability and extremely low copper corrosion. N- (2,3-dihydroxypropyl) piperazine may be commercially available, or can be easily produced by reacting piperazine with 1-chloro-2,3-dihydroxypropane.

  The resist stripper of the present invention may further contain water and / or a water-soluble organic solvent.

  When using a water-soluble organic solvent, what is generally used as a resist remover can be used. Specifically, for example, sulfoxides such as dimethyl sulfoxide; sulfones such as dimethyl sulfone and diethyl sulfone; N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide Amides such as: lactams such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2- Imidazolidinones such as imidazolidinone; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol mono Chill ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, di And glycol ethers such as propylene glycol monobutyl ether. These water-soluble organic solvents may be used alone or in combination of two or more.

  In addition, the resist stripper of the present invention can be used by containing generally used anticorrosives such as benzotriazoles.

  The content of each component of the resist remover of the present invention is preferably 0.5 to 50% by weight of the amine of the present invention and 50 to 99.5% by weight of water, more preferably from the viewpoint of resist releasability. Inventive amine is 1 to 40% by weight, water is 60% to 99% by weight.

  In the case of using a water-soluble organic solvent, it is preferably 99% by weight or less, more preferably 80% by weight or less from the viewpoint of resist releasability.

  If the content of various components in the resist remover is within this range, not only the resist releasability and stability but also the corrosion resistance to various metals will be excellent.

  It is preferable to strip the copper wiring resist using the resist stripper of the present invention (resist stripping method). The temperature at which the resist is peeled is preferably 15 to 80 ° C., and particularly preferably 20 to 60 ° C. in consideration of the peelability of the resist and attack on the wiring material.

  The resist remover of the present invention is a photoresist film coated on an inorganic substrate, a photoresist layer remaining after dry etching of a photoresist film coated on an inorganic substrate, or a photo resist remaining after ashing after dry etching. Used to remove resist residue and the like. In particular, since the corrosiveness with respect to copper metal is small, it is preferably used for peeling a miniaturized resist for copper wiring.

  When using the resist stripper of the present invention, stripping may be accelerated by heating, ultrasonic waves, or the like.

  The resist stripper of the present invention may be used by dipping, spraying, or other methods.

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

  In order to simplify the notation, the following abbreviations were used.

DHPP: N- (2,3-dihydroxypropyl) piperazine HMPP: N- (2-hydroxy-3-methoxypropyl) piperazine BDG: diethylene glycol monobutyl ether MDG: diethylene glycol monomethyl ether DMSO: dimethyl sulfoxide DMAc: dimethylacetamide MEA: monoethanol Amine HEP: N- (2-hydroxyethyl) piperazine AEP: N- (2-aminoethyl) piperazine Examples 1-9, Comparative Examples 1-4
A commercially available positive photoresist (purchased from Advantech) was applied on a silicon substrate in a thickness of 2 μm and prebaked. Subsequently, it exposed through the mask pattern and developed with tetramethylammonium hydroxide. The time until the resist was removed from the silicon substrate at 40 ° C. in the stripping solution shown in Table 1 was measured. Further, the corrosion of copper was immersed in a silicon substrate (film thickness 500 nm) obtained by depositing copper on the release agent shown in Table 1 for 30 minutes at 50 ° C., and the film thickness of copper was measured by a sheet resistance value. The corrosion rate for copper was examined from the difference in film thickness of copper before and after immersion.

  The resist removal property was evaluated by the resist removal time as follows.

○: Less than 2 min Δ: 2 min or more and less than 5 min Copper corrosivity was evaluated by the copper corrosion rate as follows.

◎: Less than 0.2 nm / min ○: 0.2 or more and less than 0.4 nm / min Δ: 0.4 or more and less than 0.7 nm / min ▲: 0.7 or more and less than 1.0 nm / min ×: 1.0 nm / min or more

  In Comparative Examples 1-4, since the amine which is not the amine represented by this invention general formula was used, it was inferior to copper corrosivity.

Claims (6)

A resist remover comprising an amine represented by the following general formula.

(In the formula, R ₁ and R ₂ each independently represent hydrogen, a methyl group, or an ethyl group.) The amine is N- (2,3-dihydroxypropyl) piperazine, N- (2-hydroxy-3-methoxypropyl) piperazine, N- (2-hydroxy-3-ethoxypropyl) piperazine, N- (2-methoxy-3) The resist remover according to claim 1, which is -hydroxypropyl) piperazine or N- (2-hydroxy-3-ethoxypropyl) piperazine. The resist stripper according to claim 1 or 2, further comprising a water-soluble organic solvent and / or water. The water-soluble organic solvent is at least one selected from the group consisting of sulfoxides, sulfones, amides, lactams, imidazolidinones, glycols and glycol ethers, Item 4. The resist remover according to Item 3. The resist stripping agent according to any one of claims 1 to 4, wherein the amine is 0.5 wt% or more and 50 wt% or less. A resist stripping method comprising stripping a resist for copper wiring using the resist stripper according to claim 1.