JP2000267302A - Remover composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily remove a resist hardened or chemically degenerated by high energy treatment by using a remover composition of a specified pH for a resist containing an organic acid and/or its salt, water and a surfactant. SOLUTION: The remover composition contains an organic acid and/or its salt, water and a surfactant and the pH is <8. The organic acid is, e.g. a carboxylic acid, perchloric acid or periodic acid but a carboxylic acid is preferably used from the viewpoint of the prevention of corrosion of a metallic material. The salt is, e.g. the salt of the organic acid and a basic organic compound such as a primary or secondary amine or a basic inorganic compound such as ammonia or sodium hydroxide. The water is preferably ion exchanged water or pure water having minimized ionic substance and particle contents. The surfactant is, e.g. an anionic or cationic surfactant. The pH of the remover composition is preferably 0.1-7 from the viewpoint of resist removing ability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist stripping composition (hereinafter referred to as a stripping composition). More specifically, the present invention relates to a stripping composition for removing a resist used in a lithography technique in the technical field of a semiconductor device or an LCD.

[0002]

2. Description of the Related Art In the manufacture of semiconductor devices and LCDs,
PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition)
After a conductive film or an insulating film is formed by, for example, a predetermined resist pattern is formed on the thin film by lithography, and this is used as an etching resist to selectively etch and remove the lower layer thin film. A step of peeling and removing is adopted.

[0003] In the stripping of a resist, a stripping composition comprising an amine compound and an organic compound containing a carboxyl group (JP-A-7-219240), an organic acid, benzyl, as a stripping agent having both a corrosion prevention effect and a stripping property. A stripper composition containing alcohols and water as essential components (JP-A-4-361265) has been proposed. However, these stripping agents have sufficient stripping properties for resists that have been altered by high-energy processing such as ultraviolet irradiation after pre-baking or post-baking, plasma processing in the etching step, and dry ashing in the stripping step. However, there is a demand for a release agent having even better releasability.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a release agent composition which can easily and quickly remove even a hardened or chemically altered resist subjected to high energy treatment.

[0005]

Means for Solving the Problems The present invention provides [1]
A resist stripping composition containing (A) an organic acid and / or a salt thereof, (B) water, and (C) a surfactant and having a pH of less than 8, and [2] the resist stripping composition. And a resist stripping method using

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The organic acids used in the present invention include carboxylic acids; peracids such as perchloric acid, periodic acid, formic acid and peracetic acid; and carbonic acids such as diethyl carbonate, methyl ethyl carbonate and dimethyl carbonate. Esters; thiocarboxylic acids such as hexanethioic acid, hexanedithioic acid, and hexanebisthioic acid; sulfonic acids such as methanesulfonic acid and toluenesulfonic acid; sulfinic acids such as benzenesulfinic acid and 1-piperidinesulfinic acid; Sulfenic acid; sulfates such as methylsulfuric acid and ethylsulfuric acid; phosphonic acids such as aminotrimethylenephosphonic acid; and organic acids such as phosphine such as diethylphosphine and triethylphosphine. Of these, carboxylic acids are preferred from the viewpoint of resist stripping properties and corrosion prevention for metal materials.

Examples of the carboxylic acids include linear saturated monocarboxylic acids, linear unsaturated monocarboxylic acids, branched saturated monocarboxylic acids, branched unsaturated monocarboxylic acids, saturated polycarboxylic acids, and unsaturated polycarboxylic acids. , Hydroxycarboxylic acid,
Examples thereof include aminocarboxylic acids, alkoxycarboxylic acids, carboxylic acids having an aromatic ring, and carboxylic acids having an alicyclic or heterocyclic ring.

The carboxylic acid is represented by the formula (IV): B-[(R ⁷ ) _p- (COOH) _q ] _r (IV) wherein R ⁷ is a hydrogen atom, a straight-chain having 1 to 40 carbon atoms; A saturated or unsaturated hydrocarbon group having a branched or cyclic skeleton, which may have 1 to 5 oxygen atoms, nitrogen atoms, or sulfur atoms, and is bonded to the carbon atom of R ⁷ The hydrogen atom is -OH group, -NH ₂ group, -SH group or -N
May be substituted with an O ₂ group, the —COOH group may be bonded to the same carbon atom of R ⁷ one or more times,
Is 0 or 1, q is an integer of 1 to 40, r is an integer of 1 to 3,
B is absent or -O-, -CO-, -NH-
Group, -S- group or

[0009]

Embedded image

A compound represented by the following formula: is preferred.

In the formula (IV), R ⁷ represents a hydrogen atom, a linear saturated hydrocarbon group having 1 to 18 carbon atoms, or a C 3 to 18 carbon atom, from the viewpoints of resist stripping properties and corrosion prevention for metal materials. Branched saturated hydrocarbon group, having 2 to 18 carbon atoms
Linear unsaturated hydrocarbon group, a branched chain unsaturated hydrocarbon group having 3 to 18 carbon atoms, a saturated or unsaturated hydrocarbon group having an alicyclic ring having 3 to 18 carbon atoms, 6 to 18 carbon atoms A saturated or unsaturated hydrocarbon group having an aromatic ring, or having 2 to 2 carbon atoms
It is preferably a saturated or unsaturated hydrocarbon group having 18 heterocycles.

When R ⁷ is a straight-chain saturated hydrocarbon group, it preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. In the case of a branched saturated or unsaturated hydrocarbon group or a saturated or unsaturated hydrocarbon group having an alicyclic ring, the number of carbon atoms is preferably 3 to 12, more preferably 3 to 6. When it is a linear unsaturated hydrocarbon group,
The carbon number is preferably 2 to 12, more preferably 2 to
6. When it is a saturated or unsaturated hydrocarbon group having an aromatic ring, it preferably has 6 to 12, more preferably 6 to 8 carbon atoms. When it is a saturated or unsaturated hydrocarbon group having a heterocyclic ring, the number of carbon atoms thereof is preferably 2 to 1
2, more preferably 2 to 6.

When the hydrocarbon group of R ⁷ has an oxygen atom, a nitrogen atom or a sulfur atom, it is more preferably 1 or 2 each.

In the formula (IV), q is from 1 to 1 from the viewpoint of resist strippability and prevention of corrosion of metal materials.
18 is preferable, 1 to 12 is more preferable, and 1 to 6 is further preferable.

Specific examples of the carboxylic acid represented by the formula (IV) include linear saturated monocarboxylic acids such as formic acid and propionic acid; acrylic acid, crotonic acid, vinyl acetic acid, 4-pentenoic acid and 6-heptene. Acid, 2-octenoic acid, undecylenic acid, linear unsaturated monocarboxylic acids such as oleic acid; isobutyric acid, isovaleric acid, pivalic acid, 2-methylbutyric acid,
Branched-chain saturated monocarboxylic acids such as 2-methylvaleric acid, 2,2-dimethylbutyric acid, 2-ethylbutyric acid, tert-butylbutyric acid, and 2-ethylhexanoic acid; methacrylic acid, tiglic acid, and 3,3-dimethylacrylic Acids, branched unsaturated monocarboxylic acids such as citronellic acid; oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, glutaric acid, Adipic acid, 3-methyladipic acid,
Saturated polycarboxylic acids such as sebacic acid, polyacrylic acid and polymaleic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, cis-aconitic acid and trans-aconitic acid; lactic acid, glucone Hydroxycarboxylic acids such as acid, tartaric acid, malic acid and citric acid; aminocarboxylic acids such as glycine, DL-alanine, 4-aminobutyric acid, DL-3-aminobutyric acid and sarcosine; methoxyacetic acid;
Alkoxycarboxylic acids such as ethoxyacetic acid; carboxylic acids having an aromatic ring such as benzoic acid, terephthalic acid, trimellitic acid, and naphthoic acid; having alicyclic rings such as cyclohexanecarboxylic acid, cyclohexanepropionic acid, cyclohexanebutyric acid, and cyclopentanecarboxylic acid Carboxylic acid; carboxylic acid having a heterocyclic ring such as furic acid, tenic acid, nicotinic acid and the like.

Among them, linear saturated monocarboxylic acids having 1 to 6 carbon atoms such as formic acid, acetic acid and propionic acid; saturated polycarboxylic acids such as oxalic acid, malonic acid and succinic acid; lactic acid and gluconic acid Hydroxycarboxylic acids such as acetic acid, tartaric acid, malic acid and citric acid; aminocarboxylic acids such as glycine, DL-alanine, 4-aminobutyric acid, DL-3-aminobutyric acid and sarcosine; alkoxycarboxylic acids such as methoxyacetic acid and ethoxyacetic acid; Carboxylic acids having an aromatic ring such as benzoic acid are more preferred.

In particular, formic acid, acetic acid, oxalic acid, malonic acid,
Succinic, lactic, gluconic, tartaric, malic, citric and benzoic acids are preferred.

The molecular weight of these carboxylic acids is 46 from the viewpoint of resist strippability and prevention of corrosion of metal materials.
To 400, more preferably 46 to 200.

Examples of the salt of an organic acid include salts of an organic acid with a basic organic compound or a basic inorganic compound. Examples of the basic organic compound include a primary amine, a secondary amine, a tertiary amine, an imine, an alkanolamine, an amide, a basic heterocyclic compound, and a quaternary ammonium hydroxide. Examples of the basic inorganic compound include ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like. Of these, ammonium salts of organic acids and salts of organic acids and basic organic compounds are preferred from the viewpoint of preventing corrosion of metal materials. Such organic acid salts may be used alone or in combination of two or more.

The organic acid or a salt thereof may be used alone or
Mixtures of more than one species may be used.

The content of the organic acid and its salt in the stripping composition is preferably 0.01 to 90% by weight, and more preferably 0.05 to 7% by weight, from the viewpoint of resist stripping properties and prevention of corrosion of metal materials. The content is more preferably 0% by weight, further preferably 0.1 to 50% by weight. The content is 0.01% by weight from the viewpoint of resist strippability.
The above is preferable. Even if the amount is more than 90% by weight, the effect of removing the resist does not change.

The water (B) used in the present invention may be an ionic substance such as ion-exchanged water, pure water or ultrapure water, or particles in consideration of the fact that the release agent is used in the field of manufacturing semiconductor devices and LCDs. It is preferable to minimize such factors as possible.

In the present invention, the use of (B) water promotes the penetration of (A) the organic acid and / or its salt into the hardened surface layer of the resist which has been subjected to the high energy treatment, thereby promoting the resist. The effect of improving the releasability is exhibited. In addition, there is exhibited an effect that the surfactant (C) exhibits sufficient surface activity such as removing minute dirt from the substrate surface, stably dispersing in the release agent, and preventing reattachment. Furthermore, it shows an excellent peeling force even for ionic dirt, which was difficult to peel in a short time with a conventional release agent, and also has an excellent effect of being able to clean the substrate surface. .

The content of (B) water in the stripping agent composition is preferably from 2 to 98% by weight, more preferably from 5 to 90% by weight, and more preferably from 15 to 90% by weight, from the viewpoint of improving the resist stripping property. 80% by weight is more preferred. The content is preferably 2% by weight or more from the viewpoint of resist releasability, and even if it exceeds 98% by weight, the removability of the resist does not change.

The release agent composition of the present invention further contains (C) a surfactant.

In the present invention, by using the surfactant (C), the surface tension of the release agent composition is reduced, and the wettability of the resist obtained by the high energy treatment to the surface hardened layer is improved. The effect of promoting the penetration of the organic acid (A) and / or its salt into the layer and improving the releasability is exhibited. In addition, an effect of removing minute deposits, residues, particles, and the like from the substrate surface, stably dispersing the components in the release agent composition, and preventing reattachment is exhibited. In particular, even in the step of rinsing the stripping composition remaining on the resist with a solvent such as acetone, methyl ethyl ketone, or 2-propanol, or pure water, insolubles do not re-adhere. Further, an effect of maintaining a uniform liquid state without separating the release agent composition is also exerted.

The surfactant (C) includes an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant.

Specific examples of the anionic surfactant include:
Examples thereof include fatty acid salts, alkali salts of alkyl sulfates, alkali salts of polyoxyalkylene alkyl ether sulfates, alkali salts of alkyl sulfosuccinates, and polycarboxylic acid type polymer surfactants. Here, the alkali salt means a neutralized product with sodium, potassium, alkanolamine, ammonia and the like. Specific examples of the anionic surfactant include sodium butylnaphthalene sulfonate, ammonium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, and ammonium polyacrylate. Among these, sodium polyoxyethylene lauryl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, and ammonium polyacrylate are preferred.

Examples of the cationic surfactant include alkylamine acetate and alkyl (mono, di, tri) methylammonium chloride. Specific examples thereof include laurylamine acetate, stearylamine acetate, and trimethyllauryl ammonium chloride. Of these, laurylamine acetate and stearylamine acetate are preferred.

Examples of the amphoteric surfactant include alkyl betaine and alkyl dimethylamine oxide. Specific examples thereof include lauryl betaine and lauryl dimethylamine oxide. Of these, lauryl dimethylamine oxide is preferred.

The nonionic surfactants include those of the formula (I)
And / or formula (II): R ¹ [(X) (AO) _j R ² ] _k (I) R ³ [(X) (AO) _j R ⁴ ] _m (II) (wherein R ¹ is carbon A hydrocarbon group of the formulas 9 to 24, X is -O
— Group, —COO— group, —NH— group, or —N ((AO)
_n H) - group, j is an integer of 0 to 100, n is an integer of 1 to 100, A is an alkylene group having 2 or 3 carbon atoms, R ² is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, k Is an integer of 1 to 8, R ³ is a hydrocarbon group having 1 to 8 carbon atoms, R ⁴ is a hydrocarbon group having at least one having 9 to 24 carbon atoms, and the other is a hydrogen atom or a hydrocarbon group having 1 to 8; m represents an integer of 2 to 8).

In the formula (I), R ¹ is preferably 9 to
18 hydrocarbon groups. R ² is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms. R ⁴ is preferably a hydrogen atom. m is preferably 1 to 6.

Examples of the compound represented by the formula (I) include:
Linear or branched saturated or unsaturated monohydric alcohols, amines and fatty acids having 9 to 24 carbon atoms, polyhydric alcohols having 2 to 15 carbon atoms, 9 to 2 carbon atoms
Compounds obtained by adding ethylene oxide and / or propylene oxide to polyamines and alkylphenols, styrenated phenols, benzylated phenols, naphthols and the like, and compounds in which some or all of the terminal hydroxyl groups have been substituted with alkyl ethers or alkyl esters. can give. Specific examples thereof include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene synthetic alcohol (C11-C13) ether, polyoxyethylene decyl ether, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Oxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid ester and the like can be mentioned. Among these, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether,
Polyoxyethylene glycerin fatty acid esters such as glycerol monooleate are preferred.

These surfactants may be used alone or in combination of two or more.

The content of the surfactant (C) in the release agent composition promotes the penetration of the component (A) into the resist,
From the viewpoint of improving the resist strippability or improving the solubility of the resist, the amount is preferably 0.1 to 80% by weight, more preferably 1 to 60% by weight, and still more preferably 2 to 50% by weight. The content is preferably 0.1% by weight or more from the viewpoint of improving the releasability and solubility of the resist, and the effect does not change even if it exceeds 80% by weight.

The pH of the stripping composition of the present invention is 8 from the viewpoint of resist stripping properties and corrosion prevention for metal materials.
, Preferably 0.1 to 7, more preferably 0.3 to 5, and still more preferably 0.5 to 3.

The stripping composition of the present invention preferably further contains an organic solvent from the viewpoint of promoting the penetration of each component in the stripping agent into the resist and improving the resist strippability.

Examples of the organic solvent include those represented by the following formula (III): R ⁵ [(X) (AO) _s R ⁶ ] _t (III) (wherein, R ⁵ is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; X is -O-, -COO-, -NH-, or-
An N ((AO) uH) _-group , s and u are each independently an integer of 1 to 20, A is an alkylene group having 2 or 3 carbon atoms,
R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and t is 1
Alkylene oxide compounds, alcohols, ethers, carbonyl compounds, esters, phenols, nitrogen-containing compounds and sulfur-containing compounds represented by the following formulas:

In the formula (III), R ⁵ is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ⁶ is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms. t
Is preferably an integer of 1 to 3, and more preferably 1 or 2.

Specific examples of the alkylene oxide compound represented by the formula (III) include methyl ether, ethyl ether, propyl ether, butyl ether, hexyl ether, phenyl ether, benzyl ether, dimethyl ether, diethyl ether, and ethylene glycol.
Butyl methyl ether, ethyl propyl ether, butyl ethyl ether, dipropyl ether, dibutyl ether and the like; corresponding diethylene glycol alkyl ether, triethylene glycol alkyl ether and the like; methyl ether, ethyl ether, propyl ether, butyl ether of tetraethylene glycol, Hexyl ether, phenyl ether, benzyl ether,
Dimethyl ether, diethyl ether and the like; pentaethylene glycol alkyl ether, hexaethylene glycol alkyl ether, propylene glycol alkyl ether, dipropylene glycol alkyl ether, tripropylene glycol alkyl ether and the like corresponding thereto.

[0041] As the alcohol of formula ^{(V): R 7 - (} OH) t (V) ( wherein, R ⁷ and t is the formula (IV), as defined in the formula (III), where, R ⁷ Excluding the case of a hydrogen atom).

The ether is represented by the formula (VI): R ⁷ —O—R ⁷ (VI) (where R ⁷ is the same as defined in the above formula (IV), except that it is a hydrogen atom) Compounds to be used.

The carbonyl compound includes a compound represented by the formula (VII):

[0044]

Embedded image

(Wherein R ⁷ is the same as defined in the above formula (IV), except that it is not a hydrogen atom).

The ester is represented by the formula (VIII): R ⁷ —COOR ⁷ (VIII) (where R ⁷ is the same as defined in the above formula (IV), except that it is a hydrogen atom). Compounds.

As the phenol, a compound represented by the formula (IX):

[0048]

Embedded image

(Wherein, R ⁸ is a saturated or unsaturated hydrocarbon group having a linear, branched or cyclic skeleton having 1 to 9 carbon atoms, and 1 to 5 hydrocarbon groups of R ⁸ ) May have an oxygen atom, a nitrogen atom or a sulfur atom, and the hydrogen atom bonded to the carbon atom of R ⁸ is -OH group, -NH ₂
Group, -SH group or -NO ₂ group may be substituted,
v represents an integer of 0 to 5 and w represents an integer of 1 to 3).

The nitrogen-containing compound and the sulfur-containing compound are not particularly limited as long as they have a molecular weight of 200 or less.

Specific examples of these organic solvents include a new edition solvent pocket book (Ohm Co., Ltd., June 1, 1994).
Compounds described on pages 331 to 761 in Data Edition (published on day 0). Among them, from the viewpoint of permeability, the formula (II
Diethylene glycol monobutyl ether as an alkylene oxide compound represented by I); propanol, butanol, pentanol and benzyl alcohol as alcohols; acrolein and methyl ethyl ketone as carbonyl compounds; nitrile acetoacetate and ethyl formate as esters; benzyl as phenol Phenol; dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and dimethylimidazolidinone, which are nitrogen-containing compounds, and dimethylsulfoxide and sulfolane, which are sulfur-containing compounds, are preferred. These organic solvents may be used alone or in combination of two or more.

Further, the melting point of the organic solvent is preferably 60 ° C. or less from the viewpoint of ensuring the resist stripping property and workability.
The temperature is more preferably 0 ° C or lower, and further preferably 10 ° C or lower.

The organic solvent is used at 25 ° C. from the viewpoint of promoting the penetration of (A) an organic acid and / or its salt, (B) water or (C) a surfactant into the resist, and improving the resist strippability. Preferably, it is soluble in water at 0.5% by weight or more, more preferably at least 4% by weight, and even more preferably at least 7% by weight.

The content of the organic solvent in the release agent composition is preferably 0.5 to 90% by weight, more preferably 5 to 80% by weight, and further preferably 10 to 50% by weight. The content is preferably 0.5% by weight or more from the viewpoint of resist strippability. Even if 90% by weight or more, the effect is not changed.

The release agent composition of the present invention is not particularly limited, but can be obtained by mixing the above compounds.

The release agent composition of the present invention can be used for a semiconductor element or L
Since the resist attached to members such as inorganic members such as CD can be easily removed without damaging those members, the semiconductor device and LCD can be suitably used for peeling the resist in a manufacturing process. is there.

As a method of removing the resist on the substrate by using the remover composition of the present invention, for example, a wafer to be processed is set one by one or a plurality of wafers together and set in a jig. Immersion in a release agent composition of the present invention, a method of performing a release treatment while oscillating a jig or applying mechanical stress such as an ultrasonic wave or a jet to the release agent composition, and a release agent of the present invention on a wafer to be processed A method of spraying or spraying the composition to carry out a peeling treatment is preferred. In this case, the temperature of the release composition is preferably from 10 to 100 ° C, more preferably from 15 to 70 ° C, from the viewpoint of workability. It is preferable that the stripping agent composition remaining on the wafer after these stripping steps be removed by rinsing with a solvent such as water or isopropyl alcohol.

[0058]

EXAMPLES Examples 1 to 10 and Comparative Examples 1 to 6 The thickness of 0.5 was formed on a silicon wafer by a sputtering method.
μm aluminum-silica-copper [98.5: 1.0:
0.5 (weight ratio)], and a positive photoresist for naphthoquinonediazide i-line was applied on the alloy film using a spinner. Next, the wafer was pre-baked at 110 ° C. for 90 seconds using a hot plate to form a photoresist film having a thickness of 1.5 μm.

This photoresist film was exposed through a photomask of a reduction projection exposure apparatus. Thereafter, paddle development was performed for a certain time using a developer (2.38% aqueous solution of tetramethylammonium hydroxide). After the developed photoresist film was rinsed with pure water for 30 seconds, it was dried under a stream of nitrogen. Next, post-baking treatment was performed at 140 ° C. for 20 minutes, and using the resist pattern as a mask, the metal layer in the opening was dry-etched with a chlorine-based gas to form a metal wiring. At the same time, the remaining resist was altered and hardened. Then, about 70% of the remaining resist was removed by dry ashing, and a resist with advanced hardening was formed. This silicon wafer was used for a peel test.

The components were mixed to have the compositions shown in Tables 1 and 2 to obtain a release agent composition. The release agent compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 6 were heated to 60 ° C., the silicon wafer was immersed therein for 20 minutes, taken out, and rinsed with 2-propanol. Rinse again with pure water. After drying, the resulting 2 μm × 2 μm resist pattern was magnified 10,000 times with a scanning electron microscope to form a 1 μm resist pattern.
At 00 locations, the peelability of the resist and the corrosion state of the aluminum-silica-copper metal wiring were evaluated by the peeling rate and the corrosion rate, respectively. The results are shown in Tables 1 and 2.
The peeling rate and the corrosion rate were determined by the following equations.

Peeling rate = (resist is 99% or more (area)
Number of peeled resist patterns / 100) × 100

Corrosion rate = (number of resist patterns in which spots or pits were observed) / 100) × 100

[0063]

[Table 1]

[0064]

[Table 2]

From the results shown in Tables 1 and 2, the release agent compositions obtained in Examples 1 to 10 all have higher release rates and corrosion rates than the release agent compositions obtained in Comparative Examples 1 to 6. Is low.

After immersion in the release agent composition obtained in Example 1 at 60 ° C. for 20 minutes, the obtained silicon wafer was directly rinsed with pure water to obtain a release rate of 100 as in Example 1. %, And the corrosion rate was 0%, which was a good result.

The peeling rate and the corrosion rate were the same as in Example 3 except that the release agent composition of Example 3 was used, the temperature at the time of peeling was 25 ° C., and the time was 5 minutes. As a result of evaluation, good results were obtained with a peeling rate of 100% and a corrosion rate of 0%.

[0068]

The stripping composition of the present invention can easily and quickly strip even a resist which has been modified by high-energy treatment and suppresses corrosion of wiring materials such as aluminum, copper and tungsten. Therefore, there is an effect that it can greatly contribute to improvement in productivity and quality of semiconductor elements, LCDs and the like.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Eiji Kashihara 1334 Minato, Wakayama-shi Kao Research Laboratory F-term (reference) 2H096 AA25 AA28 BA10 CA12 DA01 EA30 GA09 HA01 HA24 LA03 5F046 LB10

Claims (5)

[Claims] (A) an organic acid and / or a salt thereof, (B)
A resist remover composition containing water and (C) a surfactant and having a pH of less than 8. 2. The resist stripping composition according to claim 1, wherein (A) the organic acid is a carboxylic acid. (C) The surfactant is represented by the formula (I) and / or the formula (II): R ¹ [(X) (AO) _j R ² ] _k (I) R ³ [(X) (AO ) _J R ⁴ ] _m (II) (wherein, R ¹ is a hydrocarbon group having 9 to 24 carbon atoms, and X is —O
— Group, —COO— group, —NH— group, or —N ((AO)
_n H) - group, j is an integer of 0 to 100, n is an integer of 1 to 100, A is an alkylene group having 2 or 3 carbon atoms, R ² is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, k Is an integer of 1 to 8, R ³ is a hydrocarbon group having 1 to 8 carbon atoms, R ⁴ is a hydrocarbon group having at least one having 9 to 24 carbon atoms, and the other is a hydrogen atom or a hydrocarbon group having 1 to 8; The resist stripping composition according to claim 1 or 2, wherein m is an integer of 2 to 8. 4. Formula (III): R ⁵ [(X) (AO) _s R ⁶ ] _t (III) (wherein, R ⁵ is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and X is- O-group, -COO- group, -NH- group, or-
An N ((AO) uH) _-group , s and u are each independently an integer of 1 to 20, A is an alkylene group having 2 or 3 carbon atoms,
R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and t is 1
And an alkylene oxide compound represented by the following formula: 1), an alcohol, an ether, a carbonyl compound, an ester, a phenol, a nitrogen-containing compound and a sulfur-containing compound. The resist stripping composition according to any one of claims 1 to 3. 5. A resist stripping method using the resist stripping composition according to claim 1.