JP2000019745A - Release agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily release in a short time even a resist deteriorated by high energy treatment. SOLUTION: This is a release agent composition for a resist containing (A) at least one kind of compound selected from the group of amine compounds, quaternary ammonium salts and acids, and (B) a compound expressed by a general formula (1) (in the formula, R1 represents hydrogen atom, a 1-5C alkyl group, or a 2-5C alkenyl group, AO represents ethylene oxide and/or propylene oxide, X represents a hydrogen atom, a 1-8C hydrocarbon group, or an acyl group, n represents an integer of 0-5, m represents an integer of 0-10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stripping composition for resist, and more particularly, to a stripping composition for removing a resist used in lithography in the field of semiconductor devices and LCDs.

[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 thin film, and then the resist is completely removed. A removing step is performed. This series of steps is repeated to produce a product.

If a strong acid is used in the resist stripping step after the etching of the substrate, the substrate having wiring such as aluminum or copper may be corroded or dangerous. On the other hand, phenol and chlorine solvents have problems in toxicity and waste liquid treatment. To solve these problems, for example,
A release agent comprising a water-soluble amine and a water-soluble propylene glycol derivative (Japanese Patent Publication No. 7-82238), a release agent comprising an amine, a polar solvent and a surfactant (Japanese Patent Laid-Open No.
JP-A-3-231343), a release agent comprising amino alcohols, a polar solvent and water (Japanese Patent Publication No. 7-69618), a release agent comprising monoethanolamine, glycol monoalkyl ether, butynediol and water (Japanese Patent No. 2631849) And the like have been proposed.

However, these stripping agents can be sufficiently stripped from a resist that has been altered by high-energy processing such as irradiation with far ultraviolet rays after pre-baking or post-baking, plasma processing in an etching step, and dry ashing in a stripping step. There is a demand for the development of a release agent that does not have a property and is more excellent in release property.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a resist stripping composition which is excellent in workability and safety, and can easily and quickly remove a resist which has been deteriorated by high energy treatment. The purpose is to provide things.

[0006]

That is, the gist of the present invention is as follows.
(1) (A) at least one compound selected from the group consisting of an amine compound, a quaternary ammonium salt and an acid (hereinafter, referred to as component A), and (B) a general formula (I):

[0007]

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Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, AO is ethylene oxide and / or propylene oxide, X
Is a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms or an acyl group,
n is an integer of 0 to 5 and m is an integer of 1 to 10) (hereinafter, referred to as a B component). (2) Use of the stripping composition for a resist. And a method of removing a resist film on a substrate.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The release agent composition of the present invention contains, as the component A, at least one selected from the group consisting of an amine compound, a quaternary ammonium salt and an acid. The release agent composition of the present invention preferably contains these compounds from the viewpoint of obtaining high releasability from the etched resist. The amine compound, the quaternary ammonium salt and the acid can be used alone or in combination of two or more.

The amine compound has one or more nitrogen atoms in the molecule.
Those having four are preferred. For example, carbon number 1
Amines having one nitrogen atom, such as monoalkylamines, dialkylamines and trialkylamines, and benzylamine, dibenzylamine, tribenzylamine, 1-aminonaphthalene, and alkylbenzylamine; ethylenediamine, triethylenediamine,
Amines having two nitrogen atoms, such as 1,3-diaminopropane, 1,6-diaminohexane, 1,3-diaminoxylene, 1,3-bisaminocyclohexane, and tetramethylhexamethylenediamine; nitrogen atoms such as diethylenetriamine; Amines having three nitrogen atoms; amines having four nitrogen atoms such as triethylenetetramine; amine compounds having one to four nitrogen atoms in the molecule have two to four carbon atoms.
Compounds to which alkylene oxides are added; alkanolamines such as monoethanolamine, monopropanolamine, monoisopropanolamine, diethanolamine, methyl monoethanolamine, butyl monoethanolamine, triethanolamine, dimethyl monoethanolamine, and methyldiethanolamine. Can be Among these, from the viewpoint of obtaining excellent resist stripping properties, amine compounds having 1 to 2 nitrogen atoms in the molecule and compounds obtained by adding alkylene oxides having 2 to 3 carbon atoms to them are more preferable. Is benzylamine, 1,3-diaminopropane, diethylenetriamine, monoethanolamine, monopropanolamine,
Monoisopropanolamine, methyl monoethanolamine, 1,3-diaminoxylene, ethylenediamine, and compounds obtained by adding 1 to 4 mol of alkylene oxide to these compounds are exemplified.

The quaternary ammonium salt is represented by the general formula (I
I):

[0012]

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(R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrocarbon group or hydroxyalkyl group having 1 to 10 carbon atoms, Z is a p-valent acid group or hydroxyl group, and p is 1 to 3 Which represents an integer). In this specification, an acid group refers to a negative atom group in which one or more hydrogen atoms that can be substituted for a metal atom or a positive group are removed from an acid molecule.

In the general formula (II), R ² , R ³ , R ⁴
And R ⁵ are preferably a hydrocarbon group having 1 to 3 carbon atoms and a hydroxyalkyl group because of excellent releasability. Also,
As Z, for example, OH, chlorine atom, bromine atom, iodine atom, CO ₃ , HCO ₃ , NO ₃ , SO ₄ , HS
O ₄ , PO ₄ , HPO ₄ , H ₂ PO _{4 and the} like can be mentioned.
Of these, OH is preferred because it has little effect on the insulating film and the metal film. Compounds represented by the general formula (II) include tetramethylammonium hydroxide,
Examples thereof include tetraethylammonium hydroxide, monomethanoltrimethylammonium hydroxide, and choline hydroxide. Of these, tetramethylammonium hydroxide, tetraethylammonium hydroxide and monomethanoltrimethylammonium hydroxide are more preferred.

The total number of carbon atoms in the molecule of the quaternary ammonium salt is preferably from 4 to 15. These compounds can be used alone or in combination of two or more.

Examples of the acid include inorganic acids such as cyanic acid, carboxylic acids, peracids, carbonates, thiocarboxylic acids, mercaptanic acids, sulfonic acids, sulfinic acids, sulfenic acids, sulfates, phosphonic acids, phosphatidic acids, and phosphates. And phosphine and organic acids such as boric acid ester complex compounds.

When an amine compound and an acid are used in combination as the component A, they may be present in the form of a salt formed therefrom, but in the present invention, they may be present in the form of a salt. .

The content of the component A in the release agent composition is 0.1% by weight in order to exhibit good release performance.
Or more, preferably 0.5% by weight or more, more preferably 2% by weight or more.
It is preferably at least 5% by weight, more preferably at least 5% by weight, and from the viewpoint of suppressing corrosion to metal members, it is at most 95% by weight, preferably at most 80% by weight, more preferably at most 50% by weight. desirable.

In particular, when the amine compound is used alone,
The content is more preferably 2% by weight or more, preferably 5% by weight or more, and more preferably 95% by weight or less, preferably 80% by weight or less. When a quaternary ammonium salt is used alone, its content is more preferably 2% by weight or more, preferably 5% by weight or more, and more preferably 95% by weight or less, preferably 80% by weight or less. . When the acid is used alone, the content is more preferably 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably 95% by weight or less, preferably 50% by weight or less. desirable.

The release agent composition of the present invention has a general formula (I) as component B:

[0021]

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Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, AO is ethylene oxide and / or propylene oxide, X
Is a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms or an acyl group,
n represents an integer of 0 to 5 and m represents an integer of 1 to 10). In the general formula (I), R ¹
From the viewpoint of excellent releasability, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, and a hydrogen atom are preferable, and a hydrogen atom is particularly preferable. X is more preferably a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, and an acyl group having 1 to 2 carbon atoms, from the viewpoint of excellent releasability. n is preferably 0 to 2 from the viewpoint of excellent releasability, and more preferably 0.
To 1 are preferred. As m, from the point of excellent peelability,
1 to 8 are preferable, and 1 to 4 are particularly preferable. The (AO) portion may contain ethylene oxide and propylene oxide at random, or may contain blocks.

The compounds represented by the general formula (I) include phenol, methylphenol, isopropylphenol, isobutylphenol, ethylphenol, vinylphenol, benzyl alcohol, methylbenzyl alcohol, ethylbenzyl alcohol, isopropylbenzyl alcohol, phenylethyl alcohol And compounds obtained by adding ethylene oxide and / or propylene oxide to phenols and alcohols such as phenylbutyl alcohol. From the viewpoint of releasability, more preferred specific examples include ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether,
Pentaethylene glycol monophenyl ether, hexaethylene glycol monophenyl ether, heptaethylene glycol monophenyl ether, octaethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, triethylene glycol monobenzyl ether, tetraethylene glycol mono Benzyl ether, pentaethylene glycol monobenzyl ether, hexaethylene glycol monobenzyl ether,
Heptaethylene glycol monobenzyl ether and octaethylene glycol monobenzyl ether, and their corresponding propylene glycol monophenyl ether and propylene glycol monobenzyl ether; triethylene glycol diphenyl ether, triethylene glycol dibenzyl ether, triethylene glycol benzyl phenyl ether, Examples thereof include triethylene glycol phenyl methyl ether, triethylene glycol benzyl methyl ether and the like; ether compounds obtained by randomly or block-adding ethylene oxide and propylene oxide to phenol or benzyl alcohol, and derivatives thereof.

The content of the component B in the release agent composition is desirably 5% by weight or more, preferably 20% by weight or more from the viewpoint of exhibiting good release performance, and from the viewpoint of exhibiting the function of the component A. , 99.9% by weight or less, preferably 9
It is desirable that the content be 5% by weight or less, more preferably 80% by weight or less.

The release agent composition of the present invention has a boiling point of 5
It may further contain a hydrophilic organic solvent at 0 to 400 ° C. The release agent composition of the present invention has a boiling point of 50-4.
It is preferable to use a hydrophilic organic solvent at 00 ° C. in combination with the component A and the component B from the viewpoint of obtaining better releasability. As a hydrophilic organic solvent having a boiling point of 50 to 400 ° C,
Polyalkylene oxide compounds having a molecular weight of 32 to 300 and a compound obtained by adding an alkylene oxide to a 1 to 6 alcohol, a 1 to 6 alcohol or a carboxylic acid, and a polyalkylene oxide compound having a molecular weight of 60 to 300 and a polarity having a nitrogen atom or a sulfur atom Solvents are preferred.

As the alcohol, a monohydric to hexavalent alcohol is preferable because it has an appropriate viscosity. Further, the molecular weight is preferably from 32 to 300 from the viewpoint of having an appropriate viscosity and excellent releasability. Specific examples thereof include methanol, ethanol, propanol, butanol, hexanol, octanol, hexanediol, octanediol, ethylene glycol, propylene glycol, glycerin, pentaerythritol, sorbit, sorbitan, and benzyl alcohol. Among these, ethanol, propanol, butanol, hexanol, ethylene glycol, propylene glycol, and benzyl alcohol are preferable because of excellent peelability.

The molecular weight of the polyalkylene oxide compound is 6 since it has an appropriate viscosity and is excellent in releasability.
It is preferably from 0 to 300. Specific examples thereof include methanol, ethanol, propanol, butanol, hexanol, octanol, hexanediol,
1- to 6-valent alcohols such as octanediol, ethylene glycol, propylene glycol, glycerin, pentaerythritol, sorbit, and sorbitan, and carboxylic acids corresponding to the alcohols (where the OH group of the alcohol is C
OOH groups) to which alkylene oxides having 2 to 4 carbon atoms have been added, and those compounds in which some or all of the terminal hydroxyl groups or carboxyl groups are etherified with aliphatic hydrocarbon groups having 1 to 10 carbon atoms. And esterified compounds. Among them, compounds having a low viscosity and excellent peeling performance are obtained by adding 1 to 8 moles of ethylene oxide and / or propylene oxide to a monohydric alcohol having 1 to 6 carbon atoms or a compound having 1 to 4 carbon atoms added thereto. Compounds etherified with an alkyl group are preferred. Specific examples thereof include ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether,
Diethylene glycol monobutyl ether, propylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl propyl ether, diethylene glycol butyl ethyl ether, diethylene glycol butyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol Monomethyl ether, ethylene glycol monobutyl ester, diethylene glycol monoethyl ester, diethylene glycol monopropyl ester, diethylene glycol monobutyl ester, propylene glycol monoethyl ester, diethylene glycol diethyl Chiruesuteru, diethylene glycol ethyl propyl ester, diethylene glycol butyl ethyl ester, diethylene glycol butyl methyl ester, diethylene glycol diethyl ester,
Examples thereof include diethylene glycol dipropyl ester, diethylene glycol dibutyl ester, triethylene glycol dimethyl ester, and triethylene glycol monomethyl ester.

As the polar solvent, those containing a nitrogen atom or a sulfur atom are preferred. Specific examples thereof include N, N-dimethylacetamide, N-methylformamide, N, N
-Dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, sulfolane, diethylsulfolane,
Dimethyl sulfone is exemplified. Among these, N-methylformamide, because of its high polarity and excellent peelability,
N-methyl-2-pyrrolidone and dimethylsulfoxide are more preferred.

The boiling point of the hydrophilic organic solvent is 50 to 4
The temperature is desirably 00 ° C, preferably 80 to 300 ° C.

The content of the hydrophilic organic solvent in the release agent composition is desirably 1% by weight or more, preferably 5% by weight or more, and is 90% by weight or less, preferably 70% by weight or less. It is desirable.

A rust preventive or the like may be added to the release agent composition of the present invention in order to reduce corrosion on metal members such as aluminum and copper.

The release agent composition of the present invention can be used for a semiconductor element or L
Since the resist adhering to a metal member such as a CD can be easily peeled off, it can be suitably used as a resist stripping agent when manufacturing a semiconductor element, an LCD or the like.

Examples of the method of removing the resist on the substrate using the release agent composition of the present invention include a method of removing a plurality of substrates collectively and a method of removing a plurality of substrates one by one. There is a peeling method for the treatment.

As a treatment method suitable for a plurality of treatments, an immersion peeling method in which a substrate having a resist to be peeled in a peeling solution is preferably immersed for a predetermined time, and from the viewpoint of shortening the peeling time, a resist stripping agent is sprayed. A spray-type peeling method of supplying is more preferable. From the viewpoint of greatly shortening the stripping time, an ultrasonic stripping method in which ultrasonic waves are applied during immersion stripping is more preferable.

As a peeling method suitable for single-wafer processing, a spraying method, a spin-single-wafer method in which a substrate is fixed on a spinner capable of high-speed rotation, a peeling solution composition is applied from above, and uniformly dispersed to peel off. A peeling method or the like is preferable.

[0036]

EXAMPLES Examples 1 to 22 and Comparative Examples 1 to 48 Positive photoresists were applied to an 8-inch silicon wafer by using a spinner. Then, the wafer was pre-baked at 110 ° C. for 90 seconds using a hot plate to obtain a photoresist film having a thickness of 1.5 μm.

This photoresist film was exposed to a reduction projection exposure apparatus through a photomask. Thereafter, paddle development was performed for a certain period of time using a developing solution (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, a post-baking treatment was performed at 140 ° C. for 20 minutes, and the underlying layer was dry-etched using this resist pattern as a mask to alter and harden the resist. Then, dry ashing was performed as the first stage of the peeling step. The obtained silicon wafer was cut into 2 cm × 2 cm by a diamond cutter to obtain a piece.

A release agent composition having a composition shown in Tables 1 to 3 was heated to 20 to 60 ° C., and the obtained piece was immersed in the composition for 3 to 20 minutes, taken out, and taken out with isopropyl alcohol. Rinsing twice, then once with pure water. afterwards,
The pieces were dried, observed at a magnification of 5000 to 20,000 times with a scanning electron microscope, and the resist peeling performance was examined. The results are shown in Tables 1 to 3. The peeling ratio in the table is the ratio of the locations where the resist pattern was completely removed by observing 100 random 2 μm × 2 μm resist patterns formed on the silicon wafer.
In the table, POE is polyoxyethylene, POP is polyoxypropylene, and the subscripts of (POE) and (POP) indicate the number of moles added.

Examples 12 to 22 and Comparative Examples 1 to 4
The boiling points of the respective hydrophilic organic solvents used in the above are as follows: butanol 118 ° C., ethylene glycol 197
° C, diethylene glycol dibutyl ether 255 ° C,
Dipropylene glycol monopropyl ether 212
° C, propylene glycol monoethyl ether 160
℃, diethylene glycol diethyl ether 189 ℃,
Diethylene glycol butyl ester 230 ° C, N-methyl-2-pyrrolidone 204 ° C, dimethyl sulfoxide 189 ° C, N-methylformamide 198 ° C.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

From the results shown in Tables 1 and 2, Examples 1 to
It can be seen that the stripping composition obtained in No. 22 is made of a substance that is safe for the human body, so that the resist can be safely removed with good workability.

From the results shown in Tables 1-3, Examples 1 to
It can be seen that all of the release agent compositions obtained in Comparative Example 22 were superior to the release agent compositions obtained in Comparative Examples 1 to 4 in terms of releasability from a deteriorated resist.

Further, from the results shown in Tables 1 to 3, the release agent compositions obtained in Examples 1 to 22 were compared with the release agent compositions obtained in Comparative Examples 1 to 4 by 3 pieces. In order to show sufficient release properties even when immersed for a short time of up to 20 minutes, any of the release agent compositions obtained in Examples 1 to 22 can easily and quickly remove a deteriorated resist. You can see that you can do it.

[0046]

According to the present invention, a resist used in the field of lithography in the field of semiconductor devices and LCDs can be removed with good workability and safety by using the resist stripping composition. There is an effect that even a resist that has been deteriorated by high energy processing can be easily and quickly removed.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Mami Shiroda 1334 Minato, Wakayama-shi Kao Research Institute F-term (reference) 2H096 AA25 AA27 LA03 5F043 BB30 CC16 CC20 DD07 DD30 5F046 MA02 MA03

Claims (4)

[Claims] (A) at least one compound selected from the group consisting of an amine compound, a quaternary ammonium salt and an acid;
(B) General formula (I): (Wherein, R ¹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, AO is ethylene oxide and / or propylene oxide, X is a hydrogen atom,
A resist stripping composition comprising a compound represented by the formula: (C) a hydrocarbon group or an acyl group having 1 to 8 carbon atoms, n represents an integer of 0 to 5, and m represents an integer of 1 to 10. 2. The release agent composition according to claim 1, wherein in formula (I), R ¹ is a hydrogen atom and n is 0 or 1. 3. The release agent composition according to claim 1, further comprising a hydrophilic organic solvent having a boiling point of 50 to 400 ° C. 4. A resist stripping method for removing a resist film on a substrate using the stripping composition according to claim 1.