JP2015068844A - Resist remover, and method of resist removal from resist for copper or copper alloy wiring using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist remover which not only exhibits excellent resist removability but also suppresses erosion of copper or copper alloy; and a method of resist removal from a resist for copper or copper alloy wiring using the resist remover.SOLUTION: A resist remover containing water and amine represented by the general formula (1) in the figure is used to remove a resist from a resist for copper or copper alloy wiring. (In the formula, Rand Reach independently represent a methyl group or an ethyl group; Rand Reach independently represent a hydrogen atom, a methyl group or an ethyl group; m and n are each independently 2 or 3; and p is an integer from 2 to 6.)

Description

  The present invention relates to a semiconductor integrated circuit, a printed wiring board, a stripping agent for stripping a photoresist layer in a liquid crystal manufacturing process, and a resist stripping method from a copper or copper alloy wiring resist using the stripping agent.

  In general, 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, or ashing after forming the circuit. After the resist is removed, the remaining resist residue is peeled off. 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 composition containing monoethanolamines, the copper is corroded, and the resist stripping agent is satisfactory. It wasn't.

  On the other hand, as resist strippers using amines, there are disclosed resist strippers containing piperazines such as N- (2-hydroxyethyl) piperazine as essential components, diamines substituted with four hydroxyalkyl groups (patents) References 2-4). 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, demands for corrosion on copper have become more 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 JP 2006-178347 A

  The present invention has been made in view of the above problems, and its object is to provide a resist stripping agent that exhibits excellent resist stripping properties and significantly suppresses corrosiveness to copper, and copper or a copper alloy using the resist stripping agent. An object of the present invention is to provide a resist stripping method from a wiring resist.

  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 remarkably suppresses corrosiveness to copper. It has been found that when a release agent is used, the resist can be removed from the copper or copper alloy wiring resist without corroding the copper or copper alloy, and the present invention has been completed.

  That is, the present invention is a resist stripping agent as shown below, and a resist stripping method from a copper or copper alloy wiring resist using the resist stripping agent.

  [1] A resist stripper containing an amine represented by the following general formula (1) and water.

（式中、Ｒ_１、Ｒ_２はそれぞれ独立してメチル基又はエチル基を表し、Ｒ_３、Ｒ_４はそれぞれ独立して水素原子、メチル基、又はエチル基を表す。ｍ、ｎはそれぞれ独立して２又は３であり、ｐは２〜６の整数である。）
［２］上記一般式（１）で表されるアミンが、３，３’−［［３−（ジメチルアミノ）］プロピル］イミノ］ビス−２−プロパノール、３，３’−［［３−（ジメチルアミノ）］エチル］イミノ］ビス−２−プロパノール、３，３’−［［３−（ジメチルアミノ）］プロピル］イミノ］ビス−２−エタノール、及び３，３’−［［３−（ジメチルアミノ）］エチル］イミノ］ビス−２−エタノールからなる群より選ばれる少なくとも一種であることを特徴とする上記［１］に記載のレジスト剥離剤
［３］さらに水溶性有機溶媒を含有することを特徴とする上記［１］又は［２］に記載のレジスト剥離剤。

(In the formula, R ₁ and R ₂ each independently represent a methyl group or an ethyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, a methyl group, or an ethyl group. M and n are each independently. 2 or 3 and p is an integer of 2 to 6.)
[2] The amine represented by the general formula (1) is 3,3 ′-[[3- (dimethylamino)] propyl] imino] bis-2-propanol, 3,3 ′-[[3- ( Dimethylamino)] ethyl] imino] bis-2-propanol, 3,3 ′-[[3- (dimethylamino)] propyl] imino] bis-2-ethanol, and 3,3 ′-[[3- (dimethyl) Amino)] ethyl] imino] bis-2-ethanol is at least one selected from the group consisting of the resist stripping agent according to the above [1] [3] and further containing a water-soluble organic solvent The resist remover as described in [1] or [2] above, which is characterized in that

  [4] At least one water-soluble organic solvent selected from the group consisting of sulfoxides, sulfones, N, N-dimethylformamide, amides, lactams, imidazolidinones, glycols and glycol ethers. The resist remover as described in [3] above, which is an organic solvent.

  [5] The above-mentioned [1], wherein the content of the amine represented by the general formula (1) is in the range of 0.1% by weight to 50% by weight with respect to the total weight of the resist stripper. ] To [4].

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

  The resist stripper of the present invention is a resist stripper that exhibits excellent resist stripping properties and remarkably suppresses the corrosiveness to copper. The resist can be stripped without corroding the copper alloy.

  The resist remover of the present invention is characterized by containing an amine represented by the general formula (1) and water.

  In the present invention, the amine represented by the general formula (1) is not particularly limited. For example, 3,3 ′-[[3- (dimethylamino)] propyl] imino] bis-2- Propanol, 3,3 ′-[[3- (dimethylamino)] ethyl] imino] bis-2-propanol, 3,3 ′-[[3- (dimethylamino)] propyl] imino] bis-2-ethanol, 3,3 ′-[[3- (dimethylamino)] ethyl] imino] bis-2-ethanol and the like. Of these, 3,3 '-[[3- (dimethylamino)] propyl] imino] bis-2-propanol is particularly preferred because it exhibits excellent resist stripping and extremely low copper corrosion.

  3,3 ′-[[3- (Dimethylamino)] propyl] imino] bis-2-propanol may be commercially available, or can be easily reacted with N, N-dimethylpropylenediamine and propylene oxide. Can be manufactured.

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

  Although it does not specifically limit as a water-soluble organic solvent, For example, what is generally used as a resist remover can be used. Specifically, 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 and the like Amides; lactams such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazo Imidazolidinones such as lydinone; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Lenglycol 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, dipropylene glycol Examples include glycol ethers such as monobutyl ether; These water-soluble organic solvents may be used alone or in combination of two or more.

  Further, the resist stripper of the present invention can be used by containing generally used anticorrosive agents such as benzotriazoles.

  The content of each component of the resist stripper of the present invention is not particularly limited, but from the viewpoint of resist strippability, the amine represented by the general formula (1) is the total weight of the resist stripper. On the other hand, it is preferably in the range of 0.5 to 50% by weight, more preferably in the range of 1 to 40% by weight. Further, water is preferably in the range of 50% by weight to 99.5% by weight and more preferably in the range of 60% by weight to 99% by weight with respect to the total weight of the resist stripper.

  When a water-soluble organic solvent is used, it is preferably used in the range of 20% by weight or more and 99% by weight or less, and 30% by weight or more and 80% by weight or less with respect to the total weight of the resist stripper from the viewpoint of resist stripping property. More preferably, it is used in the following range. If the content of the water-soluble organic solvent is less than 20% by weight, the effect of using the organic solvent may not be observed, and if the amount of the water-soluble organic solvent exceeds 80% by weight, it is represented by the general formula (1). Since the amount of amine and water is small, the resist stripping ability may be reduced.

  If the content of the various components in the resist stripper is within these ranges, not only the strippability and stability of the resist, but particularly the corrosion resistance to copper or a copper alloy will be excellent.

  The resist remover of the present invention includes, for example, (1) a photoresist film coated on an inorganic substrate, (2) a photoresist layer remaining after dry etching the photoresist film coated on an inorganic substrate, or ( 3) The photoresist film applied on the inorganic substrate is dry-etched and then ashed to remove the remaining photoresist residue and the like. Since the resist stripper of the present invention has particularly low corrosiveness to copper metal or copper alloy, it is preferably used for stripping a miniaturized resist for copper wiring.

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

  The temperature at which the resist for copper or copper alloy wiring is stripped using the resist stripping agent of the present invention is not particularly limited, but is preferably in the range of 15 to 80 ° C. Considering the attack, the range of 20 to 60 ° C. is particularly preferable.

  The method of using the resist stripper of the present invention is not particularly limited, and examples thereof include a dipping method and a spray spraying method, but other methods may be used.

  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.

DMAPPA: 3,3 ′-[[3- (dimethylamino] propyl] imino] bis-2-propanol.
DMAEPA: 3,3 ′-[[3- (dimethylamino] ethyl] imino] bis-2-propanol.
DMAEEA: 3,3 ′-[[3- (Dimethylamino] ethyl] imino] bis-2-ethanol.
AEEA: aminoethylethanolamine.
EDAPA: N, N, N ′, N′-tetrakis (hydroxypropyl) ethylenediamine.
TMAEEA: N, N, N′-trimethylaminoethylethanolamine.
MEA: monoethanolamine.
MDG: Diethylene glycol monomethyl ether.
DMSO: dimethyl sulfoxide.
DMAc: dimethylacetamide.

Examples 1-7, Comparative Examples 1-6.
A commercially available positive photoresist (purchased from Advantech) was applied to 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 peelability 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.

A: Less than 0.2 nm / min.
A: 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.
X: 1.0 nm / min or more.

表１から明らかなとおり、全ての実施例は、上記一般式（１）で表されるアミンではないアミンを用いた比較例１〜６と比較して、銅の腐食速度が小さく、銅への耐腐食性が優れていた。

As is clear from Table 1, all the examples have a low copper corrosion rate compared to Comparative Examples 1 to 6 using an amine that is not an amine represented by the general formula (1). Corrosion resistance was excellent.

Claims (6)

A resist stripper containing an amine represented by the following general formula (1) and water.

(In the formula, R ₁ and R ₂ each independently represent a methyl group or an ethyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, a methyl group, or an ethyl group. M and n are each independently. 2 or 3 and p is an integer of 2 to 6.) The amine represented by the general formula (1) is 3,3 ′-[[3- (dimethylamino)] propyl] imino] bis-2-propanol, 3,3 ′-[[3- (dimethylamino). ] Ethyl] imino] bis-2-propanol, 3,3 ′-[[3- (dimethylamino)] propyl] imino] bis-2-ethanol, and 3,3 ′-[[3- (dimethylamino)] The resist stripper according to claim 1, wherein the resist stripper is at least one selected from the group consisting of ethyl] imino] bis-2-ethanol. Furthermore, a water-soluble organic solvent is contained, The resist remover as described in [1] or [2] above. The water-soluble organic solvent is at least one water-soluble organic solvent selected from the group consisting of sulfoxides, sulfones, N, N-dimethylformamide, amides, lactams, imidazolidinones, glycols and glycol ethers. The resist remover according to claim 3, wherein The content of the amine represented by the general formula (1) is in the range of 0.1 wt% to 50 wt% with respect to the total weight of the resist remover. 4. The resist remover according to any one of 4 above. A resist stripping method comprising stripping a resist for copper or copper alloy wiring using the resist stripper according to any one of claims 1 to 5.