TW201814035A - Resist removal liquid - Google Patents

Abstract

In a production process for semiconductor devices, etc., curing occurs at a higher temperature than conventional production processes, in order to avoid resist curing defects. As a result, a removal liquid having stronger removal force than conventionally available is required. This resist removal liquid: includes a secondary amine, a propylene glycol (PG) as a polar solvent, N, N-dimethylformamide (DMF), at least either 2-pyrrolidone (2P) or 1-methyl-2-pyrrolidone (NMP), water, and hydrazine; is characterized by the water being at least 10% by mass and less than 31% by mass; is capable of removing a resist baked at high temperature; and does not corrode film surfaces or cross-sections.

Description

   Resist stripping solution   

The present invention relates to a stripping solution for peeling a resist used in the manufacture of a display device such as a liquid crystal, an organic EL, or a semiconductor. More specifically, the resist can be removed even if the resist film is hard-baked. In addition, it can be said that the resist stripping solution does not substantially corrode the aluminum film and the copper film.

Flat screen displays (FPDs) such as liquid crystal or organic EL (Electro-Luminescence) require large screens. On the other hand, as notebook computers, tablet computers, and smartphones, small high-resolution screens are required. On a large screen, a TFT (Thin Film Transistor) using Cu wiring or Cu / Mo laminated wiring (hereinafter, sometimes referred to as "Cu wiring" only) is used. In addition, on a small high-resolution screen, a TFT using Al wiring is used. In the following, Cu is also referred to as copper, Mo is also referred to as molybdenum, and Al is also referred to as aluminum.

Some panel manufacturers produce TFTs using Cu wiring and TFTs with mixed Cu wiring and Al wiring in one factory. When manufacturing TFTs with mixed Cu wiring and Al wiring, if the resist film peeling step can be used, when using Al wiring, the resist stripping solution can be shared with Cu wiring, which can save production costs and equipment.

Water-based positive photoresist stripping solution is generally a combination of alkanolamine, polar solvent, and water. It is used by heating in a resist stripping device at a temperature of 40 ° C to 50 ° C.

The alkanolamine is an essential component that solubilizes a carboxyl group of a DNQ (diazonaphthoquinone) compound of an alkali-insoluble agent in a positive photoresist stripping solution by nucleation. Alkanolamines can be classified into first, second and third order according to the number of substituents other than hydrogen bonded to nitrogen element. Among them, it is known that the smaller the series, the stronger the alkalinity, and the stronger the nucleation property.

Therefore, the smaller the alkanolamine is, the stronger the ability to dissolve the DNQ compound of the alkali-insoluble agent in polar solvents and water, and to exert a strong and powerful peeling performance of the inhibitor.

On the other hand, alkanolamines are known to have a chelating effect on Cu. The chelation of Cu causes corrosion of the Cu film by dissolving Cu. As for the chelation of Cu, similar to the basicity or nucleation, the smaller the number of alkanolamines, the stronger the order. Therefore, the smaller the number of alkanolamines, the stronger the corrosion of the Cu film.

High-resolution analysis of semiconductors such as amorphous silicon (hereinafter, also referred to as "a-Si") or low-temperature polycrystalline silicon (hereinafter also referred to as "LTPS"), oxide semiconductors (hereinafter, also referred to as "IGZO".) In the production process of TFT, in the dry etching step, the resist is damaged and denatured, and it may be difficult to peel off the resist. This is considered to be because the DNQ compound constituting the positive-type resist film was excessively polymerized with the phenol resin.

Al wiring is not affected by alkanolamine corrosion (chelation). Therefore, as a resist for peeling denaturation, a primary alkanolamine having strong peeling properties is generally used.

On the other hand, in the case of Cu wiring, a primary or secondary alkanolamine is generally used, and corrosion of the Cu wiring often occurs to an unacceptable degree. Therefore, there is a proposal for using a tertiary alkanolamine stripper. The tertiary alkanolamine has a weaker chelation effect on Cu, which can control the corrosion of the Cu film in a practically non-problematic range. However, the alkalinity or nucleation property is weak as well as the chelation effect. Compared with a resist stripping solution using a primary or secondary alkanolamine, there is a disadvantage that the resist peeling ability is weak.

Under such a technical background, it is required to have a peeling property composition equal to or higher than that of an Al wiring resist peeling liquid using a primary alkanolamine, and a resist peeling liquid composition that can be used for both Cu wiring and Al wiring.

In addition, Patent Document 1 discloses a resist peeling liquid containing a compound represented by the formula (1) and a solvent. It is considered that this resist stripping solution can be used in common for the resist stripping step of Cu wiring and Al wiring.

In addition, Patent Document 2 discloses a resist peeling solution having a peeling force equivalent to that of an Al wiring resist peeling solution using a primary alkanolamine, although a tertiary alkanolamine is used. This stripping solution contains a tertiary amine, a polar solvent, water, a cyclic amine, a sugar alcohol, and a reducing agent. The five-membered cyclic amine is a combination of pyrrolidine or a pyrrolidine having a substituent at the third position.

[Prior technical literature]

[Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2012-514765 (Patent No. 5279921)

Patent Document 2: Japanese Patent Application Laid-Open No. 2016-085378 (Patent No. 5885041)

The peeling liquid of Patent Document 2 can be used in common for the resist peeling step of Cu wiring (including Cu / Mo laminated wiring) and Al wiring. In addition, the resist film can be peeled off even if the resist film is hard-baked.

However, at the manufacturing site of a semiconductor device using a resist, a larger-scale substrate is processed simultaneously. Therefore, the failure of one lithography step will be related to a large number of defective products at the same time. Therefore, in each step of lithography, the operating parameters are applied on the safe side.

Specifically, in the hardening step of the resist, hardening is performed at a higher temperature to avoid problems such as poor hardening of the resist. However, at the same time, it means that a peeling liquid with a stronger peeling force than before is required.

This invention is made in view of the said subject, and is providing the resist peeling liquid which can peel off even if it is baked at a higher temperature than before. Of course, it is needless to say that not only the peeling force is strong, but also the point of low corrosivity to metals such as Cu, Mo, and Al is required.

More specifically, the resist stripping solution of the present invention is characterized by comprising: a secondary amine; propylene glycol (PG), N, N-dimethylformamide (DMF), and 2-pyrrolidone ( 2P) or at least one of 1-methyl-2-pyrrolidone (NMP); water; and hydrazine as an additive, the water is 10% by mass or more and less than 31% by mass.

Since the resist stripping solution of the present invention uses a secondary amine, it can be reliably peeled even with a resist baked at a higher temperature than before. In addition, the resist stripping solution of the present invention contains at least one of DMF and 2P or NMP as a polar solvent, and although it contains a secondary amine, it can suppress corrosion of metals such as Cu, Mo, and Al.

In addition, the resist stripping solution of the present invention uses a secondary amine having a high boiling point, and thus can be recovered after use.

In addition, the resist peeling liquid of the present invention has excellent liquid bath life. Even if the resist peeling liquid is left in the open air for more than 12 hours and stored in a sealed state for 4 days, the resist peeling ability does not change.

1‧‧‧ substrate

2‧‧‧ membrane department

3‧‧‧ ground floor

4‧‧‧ surface

5‧‧‧taper angle

10‧‧‧ (Between the underlying Mo layer and the Cu layer)

FIG. 1 is a diagram illustrating a taper angle and a Mo undercut of a Cu / Mo laminated film.

Hereinafter, the resist peeling liquid of this invention is demonstrated. In addition, the following description shows an embodiment of the photoresist stripping solution of the present invention, and the following embodiments and examples can be changed without departing from the scope of the present invention. Furthermore, the terms "above" and "below" used in the specification of this book to indicate a range mean "larger inclusive of this value" and "smaller inclusive of this value". In addition, "underfill" means "smaller without this value".

The resist film peeled off by the resist peeling solution of the present invention is a positive resist. The positive resist includes a phenol-based resin as a resin and a diazonaphthoquinone (DNQ) compound as a photosensitizer. When etching is performed, a resist film is formed on the substrate, and exposure is performed via a pattern.

The DNQ compound becomes indenenone by this exposure. When indenenone meets with water, it becomes indenecarboxylic acid and is soluble in water. Phenolic resins are originally soluble in alkaline solutions, but the melting point is protected by DNQ compounds. By exposing the DNQ compound to deterioration, it dissolves in a developer containing water, so that the phenol resin is also dissolved. The formation of the resist film pattern is thus completed.

The substrate with the pattern completed by the resist film is subjected to wet etching or dry etching after post-baking. Post-baking is performed to advance the polymerization of the phenol resin and the DNQ compound in the resist film to a certain extent. It is usually heat-treated at 140 ° C for about 5 minutes. In the present specification, hard roasting means heating at 170 ° C for 30 minutes or more. When the baking temperature rises, the phenolic resin and the DNQ compound rapidly polymerize and firmly adhere to the lower metal film, making it difficult to dissolve. The resist stripping solution of the present invention is directed to such a hard-baking resist film.

The resist stripping solution of the present invention includes a secondary amine, a polar solvent, and a reducing agent. The secondary amine is preferably one having a higher boiling point than water and not azeotropic with water. It can be separated from water only when the peeling liquid is recovered. Such a secondary amine can make good use of N-methylethanolamine (hereinafter, also referred to as "MMA". Boiling point 155 ° C. CAS number 109-83-1), N-ethylethanolamine (hereinafter, also referred to as " EEA ". Boiling point 170 ° C. CAS code 110-73-6). These may be mixed.

In addition, the total amount of these peeling liquids is preferably 0.5% by mass or more, 9.0% by mass or less, more preferably 1.0% by mass or more, 8.0% by mass or less, most preferably 2.0% by mass, or 7.0% by mass or less. If there are few secondary amines, the hard-baking resist cannot be peeled off. On the other hand, if it is too large, the damage to the metal will increase. Furthermore, in terms of performance, it has been confirmed that even if it contains 9.0% by mass, it does not cause a problem with the required performance.

The polar solvent may be any organic solvent having an affinity for water (also referred to as a water-soluble organic solvent). In addition, it is more preferable that the miscibility with the secondary amine is good.

Such a water-soluble organic solvent makes good use of 2-pyrrolidone (hereinafter, also referred to as "2P". CAS number 616-45-5), propylene glycol (hereinafter, also referred to as "PG". CAS number 57-55- 6) A mixed solution with N, N-dimethylformamide (hereinafter, also referred to as "DMF". CAS No. 68-12-2). The polar solvent is composed of a water-soluble organic solvent and water.

In addition, 2-pyrrolidone may be mixed or substituted with 1-methyl-2-pyrrolidone (hereinafter, also referred to as "NMP". CAS No. 872-5-4).

For the polar solvent, the amount of the secondary amine and the reducing agent to be described later is subtracted from the entire amount of the stripping solution. Specifically, it is above 90.60% by mass and below 99.47% by mass.

Each material in a polar solvent has the following preferable ranges. First, water is preferably 10.0% by mass or more and less than 31.0% by mass with respect to the total amount of the resist stripping solution. Too much water may cause Al corrosion when the metal film is Al.

2-Pyrrolidone (or 1-methyl-2-pyrrolidone or a mixture of these) is preferably 10.0% by mass to 30.0% by mass, more preferably 12.0% by mass to 28.0% by mass, and 13.0% by mass to 27.0% by mass The following is best.

In addition, propylene glycol has the effect of stabilizing hydrazine used as a reducing agent. In order to exert this effect, propylene glycol needs to be at least 30.0% by mass. In relation to other polar solvents, it can be increased to 40.0% by mass.

The amount of N, N-dimethylformamide (DMF) may be the balance of the polar solvent.

As an additive, hydrazine (hereinafter, also referred to as "HN". CAS No. 302-01-2) is used as a reducing agent. The addition of a reducing agent can suppress Mo undercutting of secondary amines. The reducing agent is preferably in a range of 0.03 mass% or more and 0.4 mass% or less of the total amount of the resist stripping solution. The range of 0.06 mass% or more and 0.2 mass% or less is more preferable. In addition, from the viewpoint of safe operation, water compounds (hydrazine-water compounds: CAS No. 7803-57-8) can also be used.

Examples

Examples and comparative examples of the resist peeling liquid of the present invention are shown below. The resist stripping solution was evaluated by three points: "resistance peelability", "corrosiveness of metal film", and "liquid bath life".

<Resistant Peelability>

A 100 nm silicon thermal oxide film is formed on a silicon substrate, and a 300 nm thick copper film is formed on the silicon thermal oxide film by sputtering. On this copper film, a positive resist liquid was applied by a spin coating method to prepare a resist film. After the resist film is dried, it is exposed using a mask of a wiring pattern. Then, the developer is used to remove the resist in the photosensitive portion. That is, the state where the resist film with the wiring pattern remains on the copper film and the portion where the copper film is exposed. Thereafter, the entire silicon substrate was post-baked at 170 ° C for 30 minutes.

Next, the exposed copper film was etched and removed using a copper etchant using a hydrogen peroxide system. After the etching of the copper film is completed, the resist film on the pattern of the remaining copper is peeled off using a sample resist stripping solution. The time for peeling treatment was 15 minutes, and the time until peeling was measured. The interference was observed with an optical microscope to determine whether there was peeling.

Even after 15 minutes, if a resist film remains on the copper film, it is judged as "×" (fork), and when no resist film remains, it is judged as "○" (circle). At this time, the time to complete the peeling is also recorded. Furthermore, "○" (circle) means success or pass, and "×" (fork) means failure or fail. The following evaluations are the same.

<Corrosiveness of metal film>

The corrosivity of the metal film was evaluated as follows. First, a silicon thermal oxide film having a thickness of 100 nm is formed on a silicon substrate. Next, a molybdenum film with a thickness of 20 nm was formed on a silicon thermal oxide film on a silicon substrate, and a copper film with a thickness of 300 nm was formed thereon to prepare a Cu / Mo laminated film sample. This is described as "Cu / Mo". In addition, an aluminum film with a thickness of 300 nm was formed on a silicon thermal oxide film on a silicon substrate to prepare an Al film sample. This will be described as "Al".

These evaluation samples were patterned to form a wiring-shaped resist, and used as a base material for corrosion evaluation. That is, the corrosion evaluation substrate is composed of a layer of any one of a Cu / Mo film and an Al film formed on a silicon thermal oxide film on a silicon substrate, and a wiring-shaped resist layer formed thereon.

These base materials for corrosiveness evaluation are etched with an etchant for a copper film or an aluminum film for a period of time just for etching. Then, the substrate for etching the corrosion resistance evaluation was immersed in the sample resist stripping solution for 4 minutes to peel off the resist film. The substrate for corrosiveness evaluation was immersed in the sample resist stripping solution for 4 minutes, and after washing and drying, the film surface was observed. In addition, the wiring portion was cut, and the cut surface was observed.

In addition, the judgment of just the etching is determined from the time when the etching is started until the silicon thermal oxide film can be visually confirmed.

The surface of the film and the cut surface were observed using a scanning electron microscope (SEM) (manufactured by Hitachi: SU8020) under conditions of an acceleration voltage of 1 kv and 30,000 to 50,000 times.

A schematic diagram of the shape of the cut surface is shown in FIG. 1. Fig. 1 (a) shows the shape of the cut surface in the case of "Al". The shape of the cut surface of the portion just etched forms a taper angle 5 of the substrate 1 at an angle of approximately 30 ° or 60 °. The film portion 2 is an Al film.

Fig. 1 (b) shows the case of "Cu / Mo". In the case of "Cu / Mo", at least the upper film portion 2 (Cu) has a taper angle 5. The bottom layer 3 (Mo) is preferably etched along the tapered surface 6 of the film portion 2. However, as shown in FIG. 1 (b), there may be an etching residue in the film portion 2.

The evaluation of the corrosiveness is based on the observation of the shape of the cross section, and any one of the surface portion 4 or the bottom layer 3 of the film portion 2, the film portion 2 is determined to be a fork (×) when corrosion is confirmed, and when no corrosion is observed It is judged as a circle (○).

In particular, in the case of "Cu / Mo", as shown in Fig. 1 (c), there may be cases where the underlayer 3 (Mo) and the film portion 2 (Cu) are corroded. That is, Mo starts to dissolve from the interface between the film portion 2 and the bottom layer 3, and the etching of Mo (bottom layer 3) is selectively faster than that of the copper layer (film portion 2). Therefore, when the gap 10 is confirmed between the bottom layer 3 and the membrane portion 2, it can be evaluated as a cross (×).

<Liquid bath life>

A resist stripping solution, a mixed composition of materials such as amines, organic solvents, and reducing agents. Carbon dioxide in the air will dissolve in the stripping solution and become carbonic acid, bicarbonate ions, or react with amines to form amine carbonate ions, which will reduce the peeling force or damage the metal.

Especially in large-scale factories, a large amount of resist stripping solution is used in the open atmosphere of the atmosphere. In addition, since the resist stripping solution is recycled, there are many opportunities for the resist stripping solution to reconcile with air. Therefore, the bath life is short, and the resist stripping solution needs to be frequently replaced or replenished.

The test method is to prepare each resist stripping solution after it is prepared, and leave it for 0 hours, 6 hours, and 12 hours in a normal-temperature atmosphere to conduct a test of the resist peelability. Observe "Cu / Mo", " Surface and cross-section of Al ". The evaluation method is the same as in the case of <resistance peelability> and <corrosiveness of metal>.

In addition, the resist stripping solution is put into a container and carried in. However, if it cannot be stored in a normal temperature container, the applicability in the factory becomes very poor. Therefore, the changes of the ingredients in airtight storage at room temperature were also investigated.

The evaluation method is to put it in a closed container and leave it at room temperature for 4 days to measure the stability of hydrazine. Compared with hydrazine shortly after preparation, a reduction of 1% or more was judged as "×", and a score of less than 1% was judged as "○".

<Sample resist stripping solution>

Prepare the sample resist stripping solution as follows

(Example 1)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 29.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as the sample resist stripping solution of Example 1.

In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound. Hereinafter, all the examples and comparative examples have the same meaning when hydrazine-water is used.

(Example 2)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

1-methyl-2-pyrrolidone (NMP) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 29.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above was mixed and stirred as the sample resist stripping solution of Example 2.

Example 2 was a composition in which the 2-pyrrolidone (2P) of Example 1 was changed to 1-methyl-2-pyrrolidone (NMP). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Example 3)

N-ethylethanolamine was used as the secondary amine.

N-ethylethanolamine (EEA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 29.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as the sample resist stripping solution of Example 3.

Example 3 The composition of N-methylethanolamine (MMA) of the secondary amine of Example 1 was changed to N-ethylethanolamine (EEA). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Example 4)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 25.9% by mass

Water 24.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist stripping solution of Example 4.

Example 4 is a composition in which the amount of water in Example 1 was increased from 20.0% by mass to 24.0% by mass. The increase in water was adjusted with N, N-dimethylformamide (DMF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 24.036% by mass, including a portion charged as a hydrazine-water compound.

(Example 5)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 23.9% by mass

Water 26.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Example 5.

Example 5 is a composition in which the amount of water in Example 1 was increased from 20.0% by mass to 26.0% by mass. The increase in water was adjusted with N, N-dimethylformamide (DMF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 26.036% by mass, including a portion charged as a hydrazine-water compound.

(Example 6)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 21.9% by mass

Water 28.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above was mixed and stirred as the sample resist peeling liquid of Example 6.

Example 6 is a composition in which the amount of water in Example 1 was increased from 20.0% by mass to 28.0% by mass. The increase in water was adjusted with N, N-dimethylformamide (DMF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 28.036% by mass, including a portion charged as a hydrazine-water compound.

(Example 7)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 2.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 32.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above was mixed and stirred as the sample resist peeling liquid of Example 7.

Example 7 is a composition in which the amount of the secondary amine (N-methylethanolamine (MMA)) in Example 1 was reduced from 5.0% by mass to 2.0% by mass. The reduction of secondary amines was adjusted with N, N-dimethylformamide (DMF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Example 8)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 3.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 31.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as the sample resist stripping solution of Example 8.

Example 8 is a composition in which the amount of the secondary amine (N-methylethanolamine (MMA)) in Example 1 was reduced from 5.0% by mass to 3.0% by mass. The reduction of secondary amines was adjusted with N, N-dimethylformamide (DMF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Example 9)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 4.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 30.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as the sample resist stripping solution of Example 9.

Example 9 is a composition in which the amount of the secondary amine (N-methylethanolamine (MMA)) in Example 1 was reduced from 5.0% by mass to 4.0% by mass. The reduction of secondary amines was adjusted with N, N-dimethylformamide (DMF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Example 10)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 6.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 28.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above was mixed and stirred as the sample resist peeling liquid of Example 10.

Example 10 is a composition in which the amount of the secondary amine (N-methylethanolamine (MMA)) of Example 1 was increased from 5.0% by mass to 6.0% by mass. The increase in secondary amines was adjusted with N, N-dimethylformamide (DMF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Example 11)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 7.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 27.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist stripping solution of Example 11.

Example 11 is a composition in which the amount of the secondary amine (N-methylethanolamine (MMA)) of Example 1 was increased from 5.0% by mass to 7.0% by mass. The increase in secondary amines was adjusted with N, N-dimethylformamide (DMF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Comparative example 1)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

1-ethyl-2-pyrrolidone (NEP: CAS No. 2687-91-4) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 29.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 1.

Comparative Example 1 changed the composition of 2-pyrrolidone (2P) of the polar solvent of Example 1 to 1-ethyl-2-pyrrolidone (NEP). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Comparative example 2)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N-methylformamidine (NMF: CAS No. 123-39-7) 29.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 2.

Comparative Example 2 changed the composition of the polar solvent of Example 1 from N, N-dimethylformamide (DMF) to N-methylformamide (NMF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, which includes a portion charged as a hydrazine-water compound.

(Comparative example 3)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-diethylformamide (DEF: CAS No. 617-84-5) 29.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above was mixed and stirred as a sample resist peeling liquid of Comparative Example 3.

In Comparative Example 3, the composition of N, N-dimethylformamide (DMF) in Example 1 was changed to N, N-diethylformamide (DEF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Comparative Example 4)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

1-methyl-2-pyrrolidone (NMP) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-diethylformamide (DEF) 29.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 4.

Comparative Example 4 changed the 2-pyrrolidone (2P) of Example 1 to 1-methyl-2-pyrrolidone (NMP) and the N, N-dimethylformamide (DMF) to N, N-diethyl Composition of methylformamide (DEF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Comparative example 5)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvents, which contain water, are mixed in three types.

2-pyrrolidone (2P) 25.0% by mass

N, N-dimethylformamide (DMF) 49.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 5.

Comparative Example 5 is a composition obtained by removing propylene glycol (PG), which is the polar solvent of Example 1. In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, the composition ratio of the water described above can be said to be 20.036% by mass, including the portion charged as the hydrazine-water compound.

(Comparative Example 6)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvents, which contain water, are mixed in three types.

1-methyl-2-pyrrolidone (NMP) 25.0% by mass

N, N-dimethylformamide (DMF) 49.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 6.

Comparative Example 6 is a composition in which 2-pyrrolidone (2P) of the polar solvent of Example 1 was changed to 1-methyl-2-pyrrolidone (NMP) and propylene glycol (PG) was removed. In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Comparative Example 7)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Diethylene glycol monobutyl ether (BDG: CAS number 112-34-5) 30.0% by mass

N, N-dimethylformamide (DMF) 29.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 7.

Comparative Example 7 changed the composition of propylene glycol (PG) of the polar solvent of Example 1 to diethylene glycol monobutyl ether (BDG). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Comparative Example 8)

As the amine, N-methyldiethanolamine of a tertiary amine was used.

N-methyldiethanolamine (MDEA: CAS number 105-59-9) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 29.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 8.

Comparative Example 8 changed the composition of N-methylethanolamine (MMA) of the secondary amine of Example 1 to N-methyldiethanolamine (MDEA) of the tertiary amine. In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Comparative Example 9)

As the amine, pyrrolidine of a cyclic amine was used.

Pyrrolidine (PRL: CAS No. 123-75-1) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 29.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above was mixed and stirred as a sample resist peeling liquid of Comparative Example 9.

Comparative Example 9 changed the composition of the secondary amine of Example 1 from N-methylethanolamine (MMA) to pyrrolidine (PRL). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Comparative Example 10)

As the amine, hydroxyethylpiperazine of a cyclic amine was used.

Hydroxyethylpiperazine (OH-PIZ: CAS number 103-76-4) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 29.9% by mass

Water 20.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 10.

Comparative Example 10 changed the composition of the secondary amine of Example 1 from N-methylethanolamine (MMA) to hydroxyethylpiperazine (OH-PIZ). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 20.036% by mass, including a portion charged as a hydrazine-water compound.

(Comparative Example 11)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 30.0% by mass

Water 20.0% by mass

No reducing agent was placed.

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 11. Comparative Example 11 was a composition in which the reducing agent hydrazine (HN) of Example 1 was removed.

(Comparative Example 12)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 29.5% by mass

Water 20.0% by mass

Use sorbitol as an additive

Sorbitol (Stol: CAS number 50-70-4) 0.5% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 12. Comparative Example 12 changed the composition of the additive (reducing agent: hydrazine (HN)) of Example 1 to sorbitol.

(Comparative Example 13)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 29.5% by mass

Water 20.0% by mass

Use of diglycerin as an additive

Diglycerol (CAS No. 627-82-7) 0.5% by mass

The above was mixed and stirred as a sample resist peeling liquid of Comparative Example 13. Comparative Example 13 was a composition in which the additive (reducing agent: hydrazine (HN)) of Example 1 was changed to diglycerin.

(Comparative Example 14)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 29.5% by mass

Water 20.0% by mass

Use saccharin as an additive

Saccharin (CAS No. 81-07-2) 0.5% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 14. Comparative Example 14 changed the composition of Example 1 from the additive (reducing agent: hydrazine (HN)) to saccharin.

(Comparative Example 15)

N-methylethanolamine was used as the secondary amine.

N-methylethanolamine (MMA) 5.0% by mass

Polar solvent, which contains water, mixed 4 kinds.

2-pyrrolidone (2P) 15.0% by mass

Propylene glycol (PG) 30.0% by mass

N, N-dimethylformamide (DMF) 18.9% by mass

Water 31.0% by mass

Hydrazine was used as the reducing agent.

Hydrazine-water compound (HN.H ₂ O) 0.1% by mass

The above mixture was stirred and used as a sample resist peeling liquid of Comparative Example 15.

Comparative Example 15 has a composition in which the amount of water in Example 1 is increased from 20.0% by mass to 31.0% by mass. The increase in water was adjusted with N, N-dimethylformamide (DMF). In addition, 0.1% by mass of hydrazine-water compound is equivalent to 0.064% by mass of hydrazine. The remaining 0.036% by mass of hydrazine-water compound is water. Therefore, it can be said that the composition ratio of the above-mentioned water is 31.036% by mass, including a portion charged as a hydrazine-water compound.

The composition and evaluation results of Examples 1, 2 and Comparative Examples 1 to 7 are shown in Table 1. The compositions and evaluation results of Examples 1 and 3 and Comparative Examples 8, 9, and 10 are shown in Table 2. The composition and evaluation results of Example 1 and Comparative Examples 11 to 14 are shown in Table 3. The compositions and evaluation results of Examples 1, 4 to 6, and Comparative Example 15 are shown in Table 4. The composition and evaluation results of Examples 1, 7 to 11 are shown in Table 5.

[Table 1]     

Table 1 shows the compositions and evaluation results of Examples 1, 2 and Comparative Examples 1 to 7. Refer to Examples 1 and 2. N-methylethanolamine (MMA) using secondary amines, N, N-dimethylformamide (DMF) as a polar solvent, a resist that can be baked at 170 ° C for 30 minutes, at 4 ° C Peel within minutes. In addition, the damage of the films of "Cu / Mo" and "Al" was good.

In addition, the life of the liquid bath when the peeling liquid was left in an open air state did not change the peeling force even after 12 hours had elapsed. Furthermore, even if stored for 4 days, no decrease in hydrazine was seen.

In addition, in Examples 1 and 2, the polar solvents are the difference between 2-pyrrolidone (2P) and 1-methyl-2-pyrrolidone (NMP). However, neither the peeling force nor the liquid bath life changed. That is, 2-pyrrolidone (2P) and 1-methyl-2-pyrrolidone (NMP) are replaceable.

Comparative Example 1 was 2-pyrrolidone (2P) or 1-methyl-2-pyrrolidone (NMP), which substituted a polar solvent, and 1-ethyl-2-pyrrolidone (NEP) was used. However, when 1-ethyl-2-pyrrolidone (NEP) is used in a polar solvent, the hard-baking resist cannot be peeled off. In addition, the surface and cross section of "Cu / Mo" were corroded.

In Comparative Example 2, N, N-dimethylformamide (DMF), which is a polar solvent used in the peeling liquid of Example 1, was replaced with N-methylformamide (NMF). In Comparative Example 2, there were no problems with the peeling force and damage to the "Cu / Mo", "Al" surface and cross section. However, when left open in the atmosphere, the peeling force decreases. In addition, damage to the surface and surface of "Cu / Mo" occurred.

In Comparative Example 3, the polar solvent N, N-dimethylformamide (DMF) used in Example 1 was replaced with N, N-diethylformamide (DEF). In Comparative Example 4, 2-pyrrolidone (2P) used in the polar solvent of Example 1 was substituted with 1-methyl-2-pyrrolidone (NMP), and N, N-dimethylformamide ( DMF), substituted with N, N-diethylformamide (DEF). It can be said that the N, N-dimethylformamide (DMF) of Example 2 was substituted with N, N-diethylformamide (DEF).

In Comparative Examples 3 and 4, the peeling force immediately after the preparation, the damage to the metal film, and the peeling force after standing in the air all showed good properties. However, after 4 days of airtight storage, a decrease in hydrazine was observed.

Comparative Examples 5 and 6 are based on a polar solvent, using N, N-dimethylformamide (DMF) and 2-pyrrolidone (2P) or 1-methyl-2-pyrrolidone (NMP). In the absence of propylene glycol (PG). In the case of this composition, the peeling force and damage to the surface and the fracture surface were good shortly after the preparation.

However, when left in an open atmosphere, damage to the "Cu / Mo" surface and section can be observed over time. In addition, a decrease in hydrazine was observed in a closed storage at 4 days. That is, it is suggested that propylene glycol (PG) is effective for maintaining the performance of hydrazine and a peeling solution.

In Comparative Example 7, diethylene glycol monobutyl ether (BDG) was used instead of propylene glycol (PG). In Comparative Example 5, the peeling force immediately after the preparation was good. However, damage to the "Cu / Mo" surface and section was observed.

As described above, even when N-methylethanolamine (MMA) is used, the effect on the peeling force and the damage to the metal surface varies depending on the type of the polar solvent.

[Table 2]     

Table 2 shows the composition and evaluation results of Example 1, Example 3, and Comparative Examples 8, 9, and 10. Since Example 1 is disclosed again, it is shown in parentheses. Example 3 is a case where a secondary amine is used instead of N-methylethanolamine (MMA) and N-ethylethanolamine (EEA) is used. Example 3 was as good as Example 1 in peeling force, damage to metal, and liquid bath life.

Comparative Examples 8, 9, and 10 are cases where the amine was changed. Comparative Example 8 is a case where N-methyldiethanolamine (MDEA) which is a tertiary amine is used as the amine. Further, Comparative Example 9 is a case where pyrrolidine (PRL) of a cyclic amine is used, and Comparative Example 10 is a case where hydroxyethylpiperazine (OH-PIZ) is used. In Comparative Examples 8, 9, and 10, the hard-baking resist could not be peeled off.

Table 3 shows the composition and evaluation results of Example 1 and Comparative Examples 11 to 14. Since Example 1 is disclosed again, it is shown in parentheses. Comparative Example 11 does not have a composition of hydrazine (hydrazine-water compound (HN.H ₂ O)). In Comparative Example 11, the hard-baking resist cannot be peeled off. Comparative Example 12 uses sorbitol (Stol) as an additive. In addition, Comparative Example 13 uses diglycerin as an additive.

In addition, Comparative Example 14 used saccharin as an additive. In Comparative Examples 12, 13, and 14, the hard-bake resist was not peeled. Therefore, it can be said that hydrazine (hydrazine-water compound (HN.H ₂ O)) is an essential material for the peeling liquid of the present invention.

[Table 4]     

Table 4 shows the composition and evaluation results of Examples 1, 4 to 6, and Comparative Example 15. Since Example 1 is disclosed again, it is shown in parentheses. Table 4 is a study on the amount of water. The amount of water in Example 4 was 24.0% by mass, the amount of water in Example 5 was 26.0% by mass, and the amount of water in Example 6 was 28.0% by mass. On the other hand, Comparative Example 15 increased the amount of water to 31.0% by mass.

The other components are the same as those of the first embodiment. Therefore, there is no problem with any sample regarding peeling force and liquid bath life. However, in Comparative Example 15 in which the amount of water was increased to 31.0% by mass, corrosion occurred on the "Al" surface and section. From the above, it can be seen that the amount of water needs to be less than 31.0% by mass.

[table 5]     

Table 5 shows the composition and evaluation results of Examples 1, 7 to 1. Since Example 1 is disclosed again, it is shown in parentheses. In addition, the table is arranged in such a manner that the amount of amine is small to at most. Table 5 is a sample confirming the range of use of amines. The N-methylethanolamine (MMA) of Example 7 was 2.0% by mass, 3.0% by mass of Example 8 and 4.0% by mass of Example 9. The composition of these amines is smaller than the composition ratio (5.0% by mass) of N-methylethanolamine (MMA) in Example 1.

In the case where the N-methylethanolamine (MMA) of Example 10 is 6.0% by mass and the N-methylethanolamine (MMA) of Example 11 is 7.0% by mass. Examples 10 and 11 have a composition in which the amount of N-methylethanolamine (MMA) is larger than that in Example 1.

In any of the samples of Examples 7 to 11 shown in Table 5, the peeling force, the damage to the metal surface, and the life of the liquid bath were as good as in Example 1. That is, N-methylethanolamine (MMA) is prepared at a high concentration of 7.0% by mass, and there is no problem in performance. That is, in the composition of the present invention, even if the amine deviates from a predetermined blending ratio, there is no problem in performance.

    [Industrial profitability]    

The resist stripping solution of the present invention can reliably peel off a particularly hard-baking resist, and can be suitably used in a situation where a photoresist is used.

Claims (3)

    A resist stripping solution, comprising: a secondary amine; propylene glycol (PG), N, N-dimethylformamide (DMF), 2-pyrrolidone (2P), or 1-methyl- as a polar solvent; At least one of 2-pyrrolidone (NMP); water; and hydrazine as an additive, the water is 10.0% by mass or more and less than 31.0% by mass.         The resist stripping solution according to item 1 of the scope of patent application, wherein the secondary amine includes at least one of N-methylethanolamine (MMA) and N-ethylethanolamine (EEA).         A resist stripping solution, which is a resist stripping solution of a peeling resist, which is characterized by the following: a secondary amine of 0.5% by mass or more and 9.0% by mass or less; 0.03% by mass or more and 0.4% by mass or less of a secondary amine Hydrazine; 10.0% by mass or more, less than 31.0% by mass of water; 2-pyrrolidone (or 1-methyl-2-pyrrolidone, or a mixture of these) of 10.0% by mass or more and 30% by mass or less; 30% by mass Above, 40% by mass or less of propylene glycol; and the rest is N, N-dimethylformamide (DMF).