JP5321389B2 - Resist stripper and stripping method using the same - Google Patents

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 (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, a resist remover using 2- (N, N-dimethyl-2-aminoethoxy) ethanol as an essential component in a resist remover using an amine is disclosed (Patent Document 2). This stripper was effective for stripping resists used in copper wiring processes because it exhibited excellent resist stripping properties and low corrosion to copper. In recent years, not only such a single layer film made of copper, but also a multilayer film of molybdenum or molybdenum alloy such as molybdenum and tungsten is used. It is also desirable that there be no galvanic corrosion to cause. Conventionally proposed resist stripping agents have not been sufficient in terms of resist stripping properties and corrosiveness to copper and molybdenum.

  Moreover, although the resist stripping agent containing amine compounds, such as alkanolamine, and alkanolamide compounds, such as N-methylol urea, is proposed, the corrosion of Al or Al-Cu was suppressed (patent document 3).

JP 62-49355 A JP 2002-214805 A JP 2003-15320 A

  The present invention has been made in view of the above problems, and provides a resist remover that exhibits excellent resist releasability, has no corrosion on not only copper but also molybdenum, and further suppresses galvanic corrosion between these dissimilar metals. It is to provide.

  As a result of intensive studies on the resist stripper, the present inventors show that the resist stripper containing 2- (N, N-dimethyl-2-aminoethoxy) ethanol, urea and water as essential components exhibits excellent resist stripping properties. At the same time, the present inventors have found that the resist remover does not attack copper and molybdenum and can further suppress galvanic corrosion between these metals, and has completed the present invention.

  That is, the present invention is a resist stripper that exhibits excellent resist stripping property without corroding copper or a copper alloy and molybdenum or a molybdenum alloy, and comprises 2- (N, N-dimethyl-2-aminoethoxy) It is a resist stripper containing ethanol, urea and water as essential components.

  The resist stripper of the present invention contains 2- (N, N-dimethyl-2-aminoethoxy) ethanol (hereinafter abbreviated as “DMAEE”), urea and water as essential components. DMAEE exhibits excellent resist stripping properties and extremely low copper corrosion. A commercially available DMAEE may be used, or it may be produced and used by addition of ethylene oxide to N, N-dimethylethanolamine, addition of dimethylamine to diethylene glycol, or the like.

  Urea itself exhibits little resist strippability, but exhibits excellent resist strippability when used in combination with DMAEE. Furthermore, corrosion of copper and molybdenum can be extremely suppressed, and galvanic corrosion generated between dissimilar metals can be suppressed. Urea that is commercially available can be used.

  The resist stripper of the present invention contains DMAEE, urea and water as essential components, but may further contain a water-soluble organic solvent.

  When using a water-soluble organic solvent, what is generally used as a resist remover can be used. More 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 Amides such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, lactams such as N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2- Imidazolidinones such as imidazolidinone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and other glycols, 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 Examples include glycol ethers such as propylene glycol monobutyl ether. These water-soluble organic solvents may be used alone or in combination of two or more.

  Moreover, generally used anticorrosive agents, such as benzotriazole, can be added and used for the resist stripper of this invention.

  The content of each component of the resist stripper of the present invention is preferably DMAEE of 0.1% by weight to 80% by weight, particularly preferably 0.5% by weight to 50% by weight, and more preferably 3% by weight. Above 30% by weight. If it is less than 0.1% by weight, the resist peelability is small and the corrosion to copper is large. Even if it contains more than 80% by weight, no further effect can be obtained.

  The urea content is in the range of 0.1 wt% to 30 wt%, preferably 1 wt% to 20 wt%, particularly preferably 10 wt% to 20 wt%. If it is less than 0.1% by weight, the effect of inhibiting corrosion to copper and molybdenum is small, and even if it exceeds 30% by weight, no further effect can be obtained, and crystals may be precipitated.

  The water content is in the range of 1 wt% to 70 wt%, preferably 1 wt% to 50 wt%, particularly preferably 1 wt% to 40 wt%. If it is less than 1% by weight, the solubility of urea is lowered and there is a risk of crystal precipitation. When the content exceeds 70% by weight, corrosion of copper and molybdenum increases.

  When a water-soluble organic solvent is used, it is preferably used in the range of 1% by weight to 90% by weight, more preferably 5% by weight to 40% by weight. If it is less than 1% by weight, the effect of adding it is not obtained. If it exceeds 90% by weight, the resist peelability is lowered.

  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.

  The resist stripper of the present invention is composed of the above-described components and contents, but these components may be used by mixing each component when stripping the resist.

  The temperature at which the resist is stripped using the resist stripper of the present invention is usually preferably in the range of 15 to 150 ° C., and in particular, 20 to 50 ° C. is preferable in consideration of resist strippability 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 it has low corrosiveness to metals such as copper and molybdenum, it is suitably 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 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 molybdenum.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The peelability of the resist was evaluated as follows.

○: Good releasability △: Some residue remains ×: Most remains

  The corrosiveness to copper and molybdenum and the respective galvanic corrosion were evaluated as follows.

○: No corrosion △: Partial corrosion ×: Severe corrosion

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

DMAEE: 2- (N, N-dimethyl-2-aminoethoxy) ethanol NMP: N-methylpyrrolidone DMAc: dimethylacetamide DMSO: dimethyl sulfoxide DEGBE: diethylene glycol monobutyl ether MEA: monoethanolamine

Examples 1-9, Comparative Examples 1-4
Etching was performed using a positive photoresist obtained by patterning a substrate in which copper was formed on a silicon substrate and molybdenum was formed thereon as a mask. This substrate was immersed in a release agent shown in Table 1 at 30 ° C. for 2 minutes, then washed with water and dried. The presence or absence of the resist on the substrate was observed with an optical microscope and a scanning electron microscope.

  Each corrosion of copper and molybdenum was immersed in the release agent shown in Table 1 at 50 ° C. for 30 minutes, and the states of copper and molybdenum were confirmed with an optical microscope and a scanning electron microscope. Furthermore, galvanic corrosion between copper and molybdenum was confirmed by the corrosivity and conditions of each metal.

Claims (5)

  A resist stripper comprising 2- (N, N-dimethyl-2-aminoethoxy) ethanol, urea and water.   The resist stripper according to claim 1, comprising 2- (N, N-dimethyl-2-aminoethoxy) ethanol, urea, a water-soluble organic solvent, and water.   The water-soluble organic solvent is at least one selected from the group consisting of sulfoxides, sulfones, N, N-dimethylformamide, amides, lactams, imidazolidinones, glycols and glycol ethers. The resist remover according to claim 2.   The 2- (N, N-dimethyl-2-aminoethoxy) ethanol is 0.1 wt% or more and 80 wt% or less, and urea is 0.1 wt% or more and 30 wt% or less. The resist remover according to the above.   A resist stripping method comprising stripping a copper wiring resist using the resist stripper according to any one of claims 1 to 4.