JP3474127B2 - Release agent composition - Google Patents

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 for resists (hereinafter referred to as stripping composition), and more specifically, it removes a resist used in lithography technology in the technical field of semiconductor devices and LCDs. The present invention relates to a stripping liquid composition.

[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 forming a conductive film or an insulating film by a method such as lithography, form a predetermined resist pattern on the thin film by lithography, and use this as an etching resist to selectively etch and remove the lower thin film, and then completely remove the resist. A step of removing is taken. In this step, an amine compound is often used as a release agent.

However, in a release agent containing an amine-based release agent, when the content of the amine-based compound or water increases, the pH of the release agent increases, and the metal wiring such as aluminum / tungsten or the metal thin film on the substrate is subjected. On the other hand, there is a drawback that corrosion is likely to occur and the metal surface is discolored or dissolved.

As a stripping agent for solving these drawbacks, a stripping solution composition obtained by adding a carboxyl group-containing organic compound to an amine compound (JP-A-7-219240), organic acid / benzyl alcohol / 75 to 99 weight Although a stripping solution composition containing 100% of water as an essential component (Japanese Patent Application Laid-Open No. 4-361265) and the like have been proposed, all of them have insufficient corrosion prevention effects.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a stripping agent composition and a resist stripping method which are excellent in resist stripping property and have an excellent effect of preventing corrosion of various members such as semiconductor elements and metal wirings on LCDs and metal thin films. The purpose is to provide.

[0006]

The present invention provides (1) (a) an organic acid and / or a salt thereof in an amount of 0.01-90.
%, (B) water 2 to 74% by weight , (c) organic solvent 0.5 to 90% by weight, and (d) Si atom in molecule.
A fluorine-containing compound-free release agent composition containing a compound and having a pH of less than 8, and (2) (a) an organic acid and / or a salt thereof in an amount of 0.01 to 60
Wt%, (b) water 30-74 wt% and (c) organic solvent
Agents (however, N-methylpyrrolidone and alkyl-substituted amino
(Excluding compounds having no group) 0.5 to 60% by weight
However, it does not contain fluorine-containing compounds and has a pH of less than 8.
Resist stripping composition, and to resist peeling method using the same, et al.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the organic acid used in the present invention include carboxylic acid, peracid, carbonic acid ester, thiocarboxylic acid, mercaptan, sulfonic acid, sulfinic acid,
Examples thereof include organic substances such as complex compounds of sulfenic acid, sulfuric acid ester, phosphonic acid, phosphatidic acid, phosphoric acid ester, phosphine, and boric acid ester. Among these, carboxylic acids are preferable from the viewpoints of resist peelability and corrosion prevention of metal materials. As carboxylic acid,
Linear saturated monocarboxylic acid, linear unsaturated monocarboxylic acid,
Branched chain saturated monocarboxylic acid, branched chain unsaturated monocarboxylic acid, saturated polyvalent carboxylic acid, unsaturated polyvalent carboxylic acid, hydroxycarboxylic acid, aminocarboxylic acid, alkoxycarboxylic acid, carboxylic acid having an aromatic ring, alicyclic or Examples thereof include carboxylic acids having a heterocycle.

Further, the formula (II): B-[(R ³ ) _p- (COOH) _q ] _r (II) (wherein R ³ is a hydrogen atom, a straight chain having 1 to 40 carbon atoms, a branched chain) A saturated or unsaturated hydrocarbon group consisting of a cyclic or cyclic skeleton, the hydrocarbon group of R ³ may have 1 to 5 oxygen atoms, nitrogen atoms or sulfur atoms, and the carbon atom of R ³ The hydrogen atom bonded to is -OH group, -NH ₂
Group, may be substituted by -SH group or -NO ₂ group,
One or more q-COOH groups may be bonded to the same carbon atom of R ³ , p is 0 or 1, and q is 1 to 40.
, R is an integer of 1 to 3, B does not exist or -O
-Group, -CO- group, -NH- group, -S- group or

[0009]

[Chemical 1]

A group is shown. ) The carboxylic acid represented by

In the formula (II), R ³ is a hydrogen atom, from the viewpoints of resist peeling property and corrosion prevention for metal materials.
Straight-chain saturated hydrocarbon group having 1 to 18 carbon atoms, 3 to 3 carbon atoms
18 branched chain saturated hydrocarbon group, C 2-18 straight chain unsaturated hydrocarbon group, C 3-18 branched chain unsaturated hydrocarbon group, C 3-18 fat A saturated or unsaturated hydrocarbon group having a ring and a saturated or unsaturated hydrocarbon group having an aromatic ring having 6 to 18 carbon atoms are preferable. Furthermore, R
³ is a linear saturated hydrocarbon group having 1 to 12 carbon atoms, a branched saturated hydrocarbon group having 3 to 12 carbon atoms, and 2 to 12 carbon atoms.
A straight-chain unsaturated hydrocarbon group, a C3-C12 branched unsaturated hydrocarbon group, a C3-C12 alicyclic saturated or unsaturated hydrocarbon group, a C6-C12 The saturated or unsaturated hydrocarbon group having an aromatic ring of is more preferable. In particular, R ³ is a straight chain saturated hydrocarbon group having 1 to 6 carbon atoms, a branched chain saturated hydrocarbon group having 3 to 6 carbon atoms, and 2 to 6 carbon atoms.
A linear unsaturated hydrocarbon group, a C 3-6 branched unsaturated hydrocarbon group, a C 3-6 alicyclic saturated or unsaturated hydrocarbon group, a C 6-8 Most preferred are saturated or unsaturated hydrocarbon groups having an aromatic ring. Also, R ³
When the hydrocarbon group of 1 has an oxygen atom, a nitrogen atom or a sulfur atom, each is more preferably 1 or 2.

Further, in the formula (II), q is 1 to 1 from the viewpoint of resist peelability and corrosion prevention of metal materials.
An integer of 8 is preferable, an integer of 1 to 12 is more preferable,
An integer of 1 to 6 is more preferable.

Specific examples of the carboxylic acid represented by the formula (II) include formic acid, acetic acid and propionic acid having 1 to 1 carbon atoms.
8 linear saturated monocarboxylic acids; acrylic acid, crotonic acid, vinyl acetic acid, 4-pentenoic acid, 6-heptenoic acid, 2
-Linear unsaturated monocarboxylic acids such as octenoic acid, undecylenic acid, oleic acid; isobutyric acid, isovaleric acid, pivalic acid, 2-methylbutyric acid, 2-methylvaleric acid, 2,
2-dimethylbutyric acid, 2-ethylbutyric acid, tert-butylbutyric acid, 2,2-dimethylpentanoic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid,
2,4-dimethylhexanoic acid, 2-methylheptanoic acid,
2-propylpentanoic acid, 3,5,5-trimethylhexanoic acid, 2-methyloctanoic acid, 2-ethylheptanoic acid, 2-ethyl-2,3,3-trimethylbutyric acid, 2,
Branched chain saturated monocarboxylic acids such as 2,4,4-tetramethylpentanoic acid and 2,2-diisopropylpropionic acid;
Methacrylic acid, tiglic acid, 3,3-dimethylacrylic acid, 2,2-dimethyl-4-pentenoic acid, 2-ethyl-
Branched chain unsaturated monocarboxylic acids such as 2-hexenoic acid and citronellic acid; oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, glutaric acid Acid, adipic acid, 3-methyladipic acid, sebacic acid, hexadecanedioic acid, 1,2,3-propanetricarboxylic acid,
Saturated polycarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, polyacrylic acid, polymaleic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, cis-aconitic acid, trans-aconitic acid, etc. Unsaturated polycarboxylic acids; hydroxycarboxylic acids such as lactic acid, gluconic acid, tartaric acid, malic acid, citric acid; glycine, DL-alanine, 4
-Aminocarboxylic acid such as aminobutyric acid, DL-3-aminobutyric acid and sarcosine; alkoxycarboxylic acid such as methoxyacetic acid and ethoxyacetic acid; carboxylic acid having an aromatic ring such as benzoic acid, terephthalic acid, trimellitic acid and naphthoic acid; Examples thereof include alicyclic carboxylic acids such as cyclohexanecarboxylic acid, cyclohexanepropionic acid, cyclohexanebutyric acid, and cyclopentanecarboxylic acid; and heterocyclic carboxylic acids such as fulic acid, tenic acid, and nicotinic acid.

Of these, straight chain 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 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. More preferable. In particular, formic acid, acetic acid, oxalic acid, malonic acid, succinic acid, lactic acid, gluconic acid, tartaric acid,
Malic acid and citric acid are preferred.

Although the molecular weight of the carboxylic acid is not particularly limited, it is preferably 46 to 400, more preferably 46 to 200, from the viewpoint of resist strippability and prevention of corrosion of metal materials.

Examples of such salts of organic acids include salts of organic acids with basic organic compounds or basic inorganic compounds. Examples of the basic organic compound include primary amines, secondary amines, tertiary amines, imines, alkanolamines, amides, basic heterocyclic compounds and quaternary ammonium hydroxides. As the basic inorganic compound, ammonia, sodium hydroxide, potassium hydroxide,
Examples thereof include calcium hydroxide. Among these, ammonium salts of organic acids and salts of organic acids with basic organic compounds are preferable from the viewpoint of avoiding contamination with metal ions.
The salts of organic acids may be used alone or in admixture of two or more.

The organic acids and / or salts thereof may be used alone or in admixture of two or more.

The content of such an organic acid and / or its salt in the stripper composition is required to be 0.01 to 90% by weight from the viewpoint of obtaining excellent resist strippability. From the perspective of preventing corrosion against
0.05 to 70% by weight is preferable, 0.1 to 50% by weight
Is more preferable.

The water used in the present invention is an ionic substance such as ion-exchanged water, pure water or ultrapure water, or particles, considering that the release agent composition is used in the field of manufacturing semiconductor devices and LCDs. It is preferable to reduce the above as much as possible.

The content of water in the stripper composition is required to be 2 to 74% by weight from the viewpoint of improving the resist strippability. In the present invention, one of the great features is that the content of water is 2 to 74% by weight. By adjusting the content of water in such a range, excellent resist strippability and corrosion prevention effect on metal materials can be obtained. It is possible to obtain a release agent composition having Further, the content of water is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, and further preferably 15 to 50% by weight from the viewpoint of resist releasability and corrosion prevention for metal materials.

The organic solvent used in the present invention has the formula (I): R ¹ [(X) (AO) _k R ² ] _m (I) (wherein R ¹ is a hydrogen atom or a carbon number of 1 to 1). 8 hydrocarbon groups, X is -O-, -COO-, -NH-, or -N
((AO) _n H) -group, k and n are 1 to 20, 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, and m is 1 to 8 Indicates. ), Alkylene oxide compounds, alcohols, ethers, carbonyls, esters, phenols, nitrogen-containing compounds, sulfur-containing compounds and the like.

In the formula (I), R ¹ is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ² is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom or a carbon atom. The hydrocarbon group of the number 1 or 2 is more preferable, and m is 1
3 are preferable, and 1 or 2 is more preferable.

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

Alcohols used in the present invention are represented by the formula (III): R ^3- (OH) _m (III) (wherein R ³ and m are defined in the formula (II) and the formula (I). And the same as) respectively.

Examples of the ethers include compounds represented by the formula (IV): R ³ —O—R ³ (IV) (wherein R ³ is the same as the definition of the formula (II)).

The carbonyls are represented by the formula (V):

[0027]

[Chemical 2]

The compound represented by the formula (wherein R ³ is the same as the above-mentioned formula (II)) can be mentioned.

Examples of the esters include compounds represented by the formula (VI): R ³ —COOR ³ (VI) (wherein R ³ is the same as the definition of the formula (II)).

Phenols have the formula (VII):

[0031]

[Chemical 3]

(In the formula, R ⁴ is a saturated or unsaturated hydrocarbon group having a linear, branched or cyclic skeleton having 1 to 9 carbon atoms, and the hydrocarbon group of R ⁴ is 1 to 5 May have an oxygen atom, a nitrogen atom or a sulfur atom, and the hydrogen atom bonded to the carbon atom of R ⁴ is —OH group, —NH ₂
It may be substituted with a group, —SH group or —NO ₂ group.
s shows 0-5, t shows 1-3. ) Refers to a compound represented by.

The nitrogen-containing compound is not particularly limited as long as it is a compound containing a nitrogen atom having a molecular weight of 200 or less. The sulfur-containing compound is not particularly limited as long as it is a compound containing a sulfur atom having a molecular weight of 200 or less.

Specific examples of such an organic solvent include the compounds described on pages 331 to 761 of data edition of New Edition Solvent Pocket Book (Ohm Co., Ltd., published June 10, 1994). Among them, from the viewpoint of permeability, diethylene glycol monobutyl ether and diethylene glycol monohexyl ether which are alkylene oxide compounds represented by the formula (I); propanols, butanols and pentanols which are alcohols; trioxane and methylal which are ethers; Carbonyls, acrolein and methyl ethyl ketone; esters, acetoacetic nitrile and ethyl formate; phenols, benzylphenol; nitrogen-containing compounds, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and dimethylimidazolidinone; The sulfur-containing compounds dimethylsulfoxide and sulfolane are preferred.
You may use these organic solvents individually or in mixture of 2 or more types.

Further, the melting point of the organic solvent is preferably 60 ° C. or lower from the viewpoints of ensuring resist peeling property and workability, and 3
0 ° C or lower is more preferable, and 10 ° C or lower is further preferable.

The organic solvent used in the present invention accelerates the permeation of the organic acid and / or its salt or water into the resist and, as a result, improves the resist releasability. It is preferably 5% by weight or more, more preferably 4% by weight or more, still more preferably 7% by weight or more.

The content of the organic solvent in the stripper composition must be 0.5 to 90% by weight from the viewpoint of obtaining excellent resist strippability and high penetrating power.
80% by weight is preferable, and 10 to 50% by weight is particularly preferable.

The pH of the release agent composition of the present invention containing the above three components is required to be less than 8. In the present invention, the stripping agent composition has a pH of less than 8, which is also one of the major characteristics. By adjusting the pH to less than 8, the resist stripping property is sufficient and the corrosion of metal materials is suppressed. As a result, the excellent effect of contributing to the improvement of the productivity and the quality of the semiconductor element is exhibited. Therefore, the release agent composition contains (a) an organic acid and / or
Alternatively, 0.01 to 90% by weight of a salt thereof and 2 to 7 of (b) water.
Even if it contains 4% by weight and 0.5 to 90% by weight of the organic solvent (c), when the pH is 8 or more, excellent resist strippability and corrosion resistance to metal materials cannot be obtained. The pH is preferably less than 8, more preferably 0.1 to
7, more preferably 0.3 to 5, particularly preferably 0.
5 to 3.

The release agent composition of the present invention preferably further contains (d) a compound containing a Si atom in the molecule. In the present specification, the “compound containing a Si atom in a molecule” means a compound having one or more Si atoms in one molecule, and preferably has 1 to 100 Si atoms. It is more preferable to have one piece. The content of Si atoms in the release agent composition can be quantified by plasma emission analysis. From the viewpoint of the corrosion prevention effect, the content of Si atoms is preferably 0.1 ppm or more and 100,000 ppm or less, more preferably 1 ppm or more and 10,000 ppm or less, still more preferably 5 ppm or more and 5000 ppm or less.

As the compound containing a Si atom in the molecule,
For example, inorganic silicon compounds such as silicic acid and silicates and Aldrich Structure Index [Aldrich St
ructure Index] (1992-1993 edition) 425-432
Organosilicon compounds containing Si atoms described on the page are mentioned. As the inorganic silicon compound and the organic silicon compound,
Those having the following Si-Y bond in the molecule are preferable.

In the Si--Y bond, Y is Cl, Br,
A halogen atom such as I, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a sulfur atom, an amino group, a hydrogen atom, an oxygen atom or an OM group is shown. In addition,
M represents an atom or group which can be a cation, for example, L
Alkali metal atoms such as i, Na, K; Mg, Ca, Ba
Alkaline earth metal atom such as; ammonium ion; 1 to 4 hydrogen atoms of ammonium ion have 1 to 10 carbon atoms
1 to 4 quaternary alkylammonium ions substituted with a hydrocarbon group and / or a hydroxyalkyl group. Among the above Ys, an alkoxy group or an OM group is preferable, and among them, an alkoxy group having 1 to 6 carbon atoms is more preferable, and an alkoxy group having 1 to 2 carbon atoms is particularly preferable.

The number of Si--Y bonds in one molecule is 1
-15 are preferable, and 1-4 are more preferable.

As the compound having a Si--Y bond in the molecule, an organosilicon compound is preferable because it has excellent compatibility with other components in the release agent composition. The molecular weight of the organosilicon compound is preferably 45 to 10,000, more preferably 80 to 2,000, further preferably 100 to 1,000.
Particularly preferred is 00 to 500. Among these, from the viewpoint of high corrosion prevention effect, formulas (VIII) to (X):

[0044]

[Chemical 4]

(In the formula, R ^{5 to} R ⁹ are each independently a hydrocarbon group having 1 to 20 carbon atoms, R ¹⁰ is a hydrocarbon group having 1 to ¹⁰ carbon atoms, and R ^{5 to} R ¹⁰ are hydrocarbon groups. It may have 1 to 5 oxygen atoms, nitrogen atoms or sulfur atoms, and is —OH.
It may be substituted with a group, —NH ₂ group or —SH group.
The hydrocarbon group of R ^{5 to} R ¹⁰ is preferably substituted with an —NH ₂ group. Y ^{1 to} Y ¹² are the same as Y described above, and may be the same or different. Z represents a u-valent acid group or hydroxyl group, and u represents an integer of 1 to 3. ) Organosilicon compound represented by hexamethyldisilathian, tetramethylorthosilicate, tetraethylorthosilicate, 1,2-bis (trimethylsilyloxy) ethane, 1,7-dichlorooctamethyltetrasiloxane,
Tris (trimethylsilyl) amine and the like are preferable. In the present specification, the acid group refers to a negative atomic group in which one or more hydrogen atoms capable of substituting a metal atom or a positive group are removed from the acid molecule.

In the formula (VIII), R ⁵ has 2 to 1 carbon atoms.
A hydrocarbon group having 8 carbon atoms is preferable, a hydrocarbon group having 2 to 12 carbon atoms is more preferable, and a hydrocarbon group having 2 to 8 carbon atoms is particularly preferable. Specific examples thereof include ethyl group, vinyl group, propyl group, isobutyl group, hexyl group, octyl group and phenyl group. Moreover, as for Y < ¹ > -Y < ³ >, a C1-C6 alkoxy group is more preferable, and a C1-C2 alkoxy group is especially preferable.

Specific examples of the compound represented by the formula (VIII) include propyl, vinyl, aminopropyl, mercaptopropyl, hexyl, phenyl, decyl, phenylaminopropyl, octadecyl trimethoxysilane and the like; Examples thereof include triethoxysilane, alkyltrihydroxysilane, alkyltriaminosilane, alkyltrichlorosilane, alkyltribromosilane, alkyltriiodosilane and the like. Among these, aminoalkyltrimethoxysilane and aminoalkyltriethoxysilane are more preferable, and aminopropyltrimethoxysilane and aminopropyltriethoxysilane are particularly preferable.

In the formula (IX), Y ^{4 to} Y ⁹ may be the same as the above Y, and may be the same or different. Further, R ⁶ is preferably a hydrocarbon group having 2 to 18 carbon atoms, and more preferably a hydrocarbon group having 2 to 12 carbon atoms. Specific examples of the compound represented by the formula (IX) include 1,6
Examples include -bis (trimethoxysilyl) hexane, 1,6-bis (trichlorosilyl) hexane, 1,8-bis (trihydroxysilyl) octane, and 1,10-bis (triaminosilyl) decane.

In the formula (X), R ⁷ , R ⁸ and R ⁹ are each independently preferably a hydrocarbon group having 6 to 18 carbon atoms. R ¹⁰ is preferably a hydrocarbon group having 2 to 6 carbon atoms.
Y ¹⁰ , Y ¹¹ and Y ¹² may be the same as Y described above, and may be the same or different. Specific examples of Z include Cl, Br, I, CO ₃ , and HC as acid groups.
O ₃ , NO ₃ , SO ₄ , HSO ₄ , PO ₄ , HPO ₄ ,
H ₂ PO ₄ etc. and a hydroxyl group can be mentioned. Among these, OH has the least influence on the insulating film and the metal film.
Is preferred. Among the organosilicon compounds, the compound of formula (VIII) is preferable from the viewpoint of corrosion inhibition.

The content of the compound having Si atoms in the molecule in the release agent composition is preferably 0.001 to 10% by weight, more preferably 0.05 to 5% by weight,
It is more preferably 0.01 to 1% by weight. The lower limit of the content is preferably 0.001% by weight or more from the viewpoint of corrosion prevention effect, and the upper limit is 1 from the viewpoint of releasability of the release agent.
It is preferably 0% by weight or less.

The stripping agent composition of the present invention having the above-mentioned constitution can easily strip the resist adhered on the members such as the semiconductor element and the inorganic member such as LCD without damaging the members. Since it is obtained, the semiconductor element, LCD, or the like can be suitably used for stripping resist in the manufacturing process.

As a method for removing the resist on the substrate using the release agent composition of the present invention, for example, one wafer or a plurality of wafers to be processed are set in a jig and the present invention is used. Of the peeling agent composition of the present invention on a wafer to be treated, or a method of performing a peeling treatment by immersing the jig in a peeling agent composition or rocking a jig or applying a mechanical force such as ultrasonic waves or jet to the peeling solution. Preferable is a method of spraying or spraying with. The temperature of the peeling composition at that time is preferably 10 ° C. to 100 ° C. from the viewpoint of workability.
It is more preferably 5 to 70 ° C. After these stripping steps, the stripping agent composition remaining on the wafer is preferably removed by rinsing with water or a solvent such as isopropyl alcohol.

[0053]

EXAMPLES Examples 1 to 19 and Comparative Examples 1 to 6 (Note that the actual
(Examples 1, 2, 4, and 8 are reference examples) A thickness of about 0.
5 μm aluminum-silica-copper [98.5: 1.
0: 0.5 (weight ratio)], and then a naphthoquinonediazide-based positive photoresist for i-line was coated on the metal films using a spinner. Then, using a hot plate, this wafer was pre-baked at 110 ° C. for 90 seconds to form a photoresist film having a film thickness of 1.5 μm.

This photoresist film was exposed through a photomask of a reduction projection exposure device. Then, paddle development was performed for a certain period of time using a developing solution (2.38% tetramethylammonium hydroxide aqueous solution). The developed photoresist film was rinsed with pure water for 30 seconds and then dried under a nitrogen stream. Then, post-baking treatment was performed at 140 ° C. for 20 minutes, and the metal layer in the opening was dry-etched with chlorine-based gas using this resist pattern as a mask to form metal wiring, and at the same time, the residual resist was denatured and cured. Then, about 70% of the remaining resist was removed by dry ashing to prepare a resist that had undergone deterioration hardening. This silicon wafer was used for the peel test.

Examples 1 to 1 having the compositions shown in Tables 1 to 3
9 and the release agent compositions obtained in Comparative Examples 1 to 6 were each heated to 60 ° C.
After soaking for 0 minute, it was taken out, rinsed with isopropyl alcohol, and rinsed again with pure water. After drying, it was magnified about 10,000 times with a scanning electron microscope and formed into 2 μm x 2
A 100 μm resist pattern was observed, and the peelability of the resist and the corrosion state of the aluminum-silica-copper alloy wiring were evaluated by the peeling rate and the corrosion rate, respectively.
The results are shown in Tables 1 to 3. The peeling rate and the corrosion rate were calculated by the following formulas. Peeling rate = (99% or more of resist (area) number of resist patterns peeled / 100) x 100 Corrosion rate = (number of resist patterns with stains or pitting corrosion) / 100) x 100

Further, in Tables 1 and 2, the water solubility “∞” indicates that water and the organic solvent can be freely mixed,
The physical properties of the organic solvent used in Examples 7 and 8 are those of the two types of mixed solvents. Further, in Table 2, "Si atom-containing compound" means a compound containing Si atoms in the molecule.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

From the results of Tables 1 to 3, the release agent compositions obtained in Examples 1 to 19 have higher release rates and corrosion rates than the release agent compositions obtained in Comparative Examples 1 to 6. It turns out that it is low.

Further, the stripping rate and the corrosion rate were evaluated in the same manner as in Example 1 except that the release agent composition obtained in Example 1 was used and the obtained silicon wafer was directly rinsed with pure water. Good results were obtained with a peeling rate of 100% and a corrosion rate of 0%.

The peeling rate and corrosion rate were determined in the same manner as in Example 1 except that the peeling agent composition obtained in Example 3 was used and the peeling temperature was 25 ° C. for 5 minutes. As a result of evaluation, good results were obtained with a peeling rate of 100% and a corrosion rate of 0%. Further, from the comparison between Examples 13 and 15 to 19 in which a compound containing a Si atom is present in the molecule and Examples 3 and 6 in which the compound is absent, the compound containing a Si atom is present in the molecule. It can be seen that the corrosion inhibition effect is further improved.

[0063]

EFFECTS OF THE INVENTION The resist stripper composition of the present invention can easily strip even a resist which has been altered by high energy treatment in a short time, and suppresses corrosion of wiring materials such as aluminum and tungsten. it can.
As a result, it can greatly contribute to improvement in productivity and quality of semiconductor devices, LCDs and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Eiji Nagoshi 1334 Minato Minato, Wakayama City Kao Corporation Research Center (56) References JP-A-11-52588 (JP, A) JP-A-9-22122 (JP, A ) JP 4-359257 (JP, A) JP 9-197681 (JP, A) JP 10-55993 (JP, A) JP 7-271056 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42 C08D 9/00 H01L 21/027

Claims (5)

(57) [Claims] 1. An (a) organic acid and / or its salt is added to 0.0
1-90% by weight, (b) water 2-74% by weight , (c) organic solvent 0.5-90% by weight, and (d) Si raw material in the molecule.
A stripper composition for a resist, which contains a compound containing a child and has a pH of less than 8, which does not contain a fluorine-containing compound. 2. The resist stripper composition according to claim 1, wherein the organic acid (a) and / or its salt is a carboxylic acid and / or its salt. 3. The organic solvent (c) has the formula (I): R ¹ [(X) (AO) _k R ² ] _m (I) (wherein R ¹ is a hydrogen atom or a group having 1 to 8 carbon atoms). Hydrocarbon group, X is -O-, -COO-, -NH-, or -N
((AO) _n H) -group, k and n are 1 to 20, 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, and m is 1 to 8 Indicates. The alkylene oxide compound represented by), alcohols, ethers, carbonyls, esters, phenols, nitrogen-containing compounds, and one or more selected from the group consisting of sulfur-containing compounds according to claim 1 or 2. A stripper composition for resist. 4. The (a) organic acid and / or its salt is added to 0.0
1 to 60% by weight, (b) 30 to 74% by weight of water and
(C) Organic solvent (however, N-methylpyrrolidone and al
0.5 to 6 (excluding compounds having a kill-substituted amino group)
Fluorine-containing compound containing 0% by weight and having a pH of less than 8
A stripper composition for a resist which does not contain 5. A resist stripping method using the resist stripping composition according to claim 1.