JP2002278092A - Release agent composition - Google Patents

Abstract

(57) [Problem] To provide a release agent composition having low corrosiveness of a wiring layer and further excellent in removing residue generated by dry etching or ashing. (A) The following general formula (I) ... (I) (wherein, R ₁ and R ₂ each independently represent a hydrogen atom, or represent a hydroxyl group, a carboxyl group, or an optionally substituted alkyl group, and Z represents oxygen A) a cyclic urea compound represented by an atom or a sulfur atom), (b) an organic amine, (c) a salt of an organic amine or an inorganic amine with an acid, and (d) water and / or a water-soluble organic solvent. A release agent composition comprising:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a release agent composition.

[0002]

2. Description of the Related Art In recent years, high-density integrated circuits have required high-precision fine pattern formation. For this reason, semiconductor element processes such as dry etching using a halogen-based gas or the like, ashing with oxygen plasma, and ion implantation, which are suitable for forming a fine pattern, are performed. After dry etching and ashing,
A sparingly soluble residue is formed, and a stripping composition has conventionally been used to remove the residue.

For example, Japanese Patent Application Laid-Open No. 2001-183850 discloses a release agent composition comprising a cyclic urea compound and an organic amine. However, although a wiring layer such as a copper layer has low corrosiveness, dry etching is difficult. There is still room for improvement in the removability of residues generated by ashing and ashing.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a release agent composition having a low corrosiveness of a wiring layer and further excellent in removing residues generated by dry etching or ashing. .

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to find a release agent composition free from the above-mentioned problems, and as a result, in addition to a cyclic urea compound and organic amines, That the release agent composition containing a salt of a compound or an inorganic amine with an acid has a low corrosiveness of the wiring layer and is more excellent in removing residues generated by dry etching or ashing. Thus, the present invention has been completed.

That is, the present invention relates to (a) a compound represented by the following general formula (I): ... (I) (wherein, R ₁ and R ₂ each independently represent a hydrogen atom, or represent a hydroxyl group, a carboxyl group, or an optionally substituted alkyl group, and Z represents oxygen A) a cyclic urea compound represented by an atom or a sulfur atom), (b) an organic amine, (c) a salt of an organic amine or an inorganic amine with an acid, and (d) water and / or a water-soluble organic solvent. It is intended to provide a release agent composition containing the same.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The release agent composition of the present invention comprises (a) the above-mentioned general formula (I)
A cyclic urea compound represented by: (b) an organic amine,
It comprises (c) a salt of an organic amine or an inorganic amine with an acid, and (d) water and / or a water-soluble organic solvent.

(A) The cyclic urea composition will be described. In the cyclic urea compound represented by the general formula (I),
R ₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, a carboxyl group, or an optionally substituted alkyl group. Z represents an oxygen atom or a sulfur atom.
Examples of the alkyl group which may be substituted by the following general formula _{(II) - (CH 2)} n -X ····· (II) ( wherein, n stands for an integer of 1 or more, X Represents a hydrogen atom or represents an alkoxy group having 1 to 10 carbon atoms such as a hydroxyl group, a methoxy group, and an ethoxy group).

From the viewpoint of the performance of removing the resist film and the etching residue, R ₁ and R ₂ are preferably a hydrogen atom or an optionally substituted alkyl group represented by the general formula (II), N in the general formula (II) is preferably from 1 to 4, more preferably from 1 to 2. Further, from the viewpoint of raw material circumstances, it is preferable that R ₁ and R ₂ represent the same group.

The cyclic urea compound represented by the general formula (I) includes, for example, 4,5-dihydroxy-2-imidazolidinone, 4,5-dihydroxy-1,3-dimethyl-
2-imidazolidinone, 4,5-dihydroxy-1,3
-Bis (hydroxymethyl) -2-imidazolidinone,
4,5-dihydroxy-1,3-bis (methoxymethyl) -2-imidazolidinone and the like.

The cyclic urea compound represented by the general formula (I) is prepared by reacting a corresponding urea compound or thiourea compound with glyoxal by a conventional method, or a reaction product of urea or thiourea with glyoxal (general reaction). (R ₁ = R ₂ = H in the formula (I)) by introducing an N-substituent in a usual manner.

The content of the cyclic urea compound in the release agent composition is preferably 0.1 to 20% by weight, more preferably 0.1 to 15% by weight, and further preferably 1 to 15% by weight.
It is.

When the content of the cyclic urea compound is 0.1% by weight
If the amount is less than the above range, the removal of the etching residue tends to be insufficient. On the other hand, if the added amount or the content exceeds 15% by weight, the removability of the etching residue tends to be insufficient.

(B) The organic amines will be described. Organic amines used in the present invention include alkanolamines, alkyl ammonium hydroxides, or mixtures thereof. As alkanolamines,
For example, monoethanolamine, diethanolamine,
Triethanolamine, 2- (2-aminoethoxy) ethanol and the like. Examples of the alkyl ammonium hydroxide include, for example, tetramethyl ammonium hydroxide,
And tetraethylammonium hydroxide. These organic amines may be used alone or in combination of two or more.

The content of the organic amine in the release agent composition is preferably 0.1 to 30% by weight, more preferably 1 to 30% by weight.
-30% by weight, more preferably 5-30% by weight. When the content of the organic amine exceeds 30% by weight, the wiring layer and the insulating film on the substrate tend to be corroded,
If the content is less than 0.1% by weight, the removal of the etching residue tends to be insufficient.

(C) A salt of an organic amine or an inorganic amine with an acid will be described. Examples of the organic amines include hydroxylamines having a substituted alkyl group such as N, N-diethylhydroxylamine, in addition to the above-mentioned alkanolamines, alkylammonium hydroxides, and mixtures thereof. Here, examples of the alkyl group which may be substituted include an alkyl group represented by the general formula (II). Examples of the inorganic amines include hydroxylamine. Examples of the acid include hydrochloric acid, nitric acid,
Sulfuric acid, carboxylic acids, and the like. Examples of the carboxylic acids include formic acid, acetic acid, oxalic acid and the like. Examples of the salt of an organic amine or an inorganic amine with an acid include monoethanolamine hydrochloride, hydroxylamine hydrochloride, hydroxylamine sulfate and the like. These may be used alone or in combination of two or more.

The content of a salt of an organic amine or an inorganic amine with an acid in the release agent composition is 0.01 to 30% by weight.
Is preferably, more preferably 0.1 to 30% by weight, and still more preferably 1 to 30% by weight. When the content of the salt is less than 0.01% by weight, the performance of removing the etching residue tends to decrease. When the content exceeds 30% by weight, the solubility of the salt in the release agent composition decreases, Corrosion of the upper wiring layer tends to occur.

(D) The water and / or water-soluble organic solvent will be described. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, t-butyl alcohol, pentanol, ethylene glycol, and glycerin; N-methylformamide, N, N -Dimethylformamide, N, N-dimethylacetamide, N-methyl-
Amides such as 2-pyrrolidone; lactones such as γ-butyrolactone; esters such as propyl acetate, butyl acetate, butyl propionate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate; acetone, methyl ethyl ketone, acetylacetone, methyl butyl Ketones such as ketones; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Glycol ethers such as diethylene glycol monobutyl ether and triethylene glycol monomethyl ether; furan compounds such as tetrahydrofuran, furaldehyde and tetrahydrofurfuryl alcohol; sulfolane such as sulfolane; sulfoxides such as dimethyl sulfoxide; urea compounds such as dimethylimidazolidinone. And the like. Among these, a water-soluble organic solvent having a solubility in water of 8% or more is preferable, and N-methyl-2-pyrrolidone, methanol, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, and ethylene glycol monobutyl ether are more preferably used.
These water-soluble organic solvents may be used alone or in combination of two or more.

The content of water and / or water-soluble organic solvent in the release agent composition is preferably 20 to 99.8% by weight, more preferably 30 to 80% by weight, and further preferably 40 to 60% by weight. is there. When the content of water and / or the water-soluble organic solvent is less than 20% by weight, the solubility of the salt of the organic amine or inorganic amine with the acid in the stripping composition is reduced, and the etching residue is removed. The performance tends to decrease, and if it exceeds 99.8% by weight, the ability to remove etching residues tends to decrease.

Furthermore, the release agent composition of the present invention preferably contains an additive. As the additive, a metal corrosion inhibitor such as a reducing agent or a chelating agent can be used, and examples thereof include an aromatic hydroxy compound, a triazole compound, polyethyleneimine, and thioglycerol. These may be used alone or in combination of two or more.

Here, as the aromatic hydroxy compound, for example, hydroquinone, catechol, resorcinol, pyrogallol and the like can be mentioned, among which catechol is preferably used. Examples of the triazole compound include benzotriazole, carboxybenzotriazole, 1-hydroxybenzotriazole,
Examples include aminotriazole, and among them, benzotriazole is preferably used.

The content of the additive in the release agent composition is 0.1%.
It is preferably 001 to 20% by weight, more preferably 0.01 to 20% by weight, and even more preferably 0.1 to 20% by weight.
20% by weight. If the content of the additive is less than 0.001% by weight, the wiring layer on the substrate tends to corrode, and if it exceeds 20% by weight, the etching residue tends to remain on the substrate after the release agent treatment. There is.

The release agent composition of the present invention comprises the aforementioned (a)
Production by mixing a cyclic urea compound, (b) an organic amine, (c) a salt of an organic amine or an inorganic amine with an acid, and (d) water and / or a water-soluble organic solvent. Can be. The mixing method and order are not particularly limited, and various known methods can be applied to mix in any order. For example,
To a solution obtained by adding (a) the cyclic urea compound to (d) water and / or a water-soluble organic solvent, add (b) a salt of an organic amine, (c) an organic amine or an inorganic amine to an acid. Method (a) containing a cyclic urea compound (d)
A method of adding (b) an organic amine or (c) a salt of an organic amine or an inorganic amine to an acid to water and / or a water-soluble organic solvent may be used.

The stripping agent composition of the present invention is excellent in removing residues generated during dry etching and ashing, particularly in removing residues generated during dry etching, and constitutes a semiconductor device. Corrosion to materials such as an insulating film and a wiring layer can be suppressed, and is suitably used in a cleaning process of a semiconductor element such as an LSI element or a liquid crystal panel element.

As a method for removing residues generated during dry etching or ashing, for example, 10
In a temperature range of １００100 ° C., the release agent composition of the present invention is used for LS
What is necessary is just to wash an I element and a liquid crystal panel element. Further, the stripping composition of the present invention can be suitably applied to removal of a resist film obtained from a photoresist or the like. As a method for removing the resist film, the same method as the above-described method for removing the residue can be used.

The release agent composition of the present invention can be used in a manufacturing process of a semiconductor device such as an LSI device or a liquid crystal panel device, in a process of manufacturing a semiconductor device such as an insulating film or a wiring layer made of aluminum, tungsten, copper, platinum or the like. Is extremely low in corrosiveness, and is suitably used especially for a semiconductor element having a wiring layer made of copper or aluminum.

[0027]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited to the examples.

Examples 1 to 3 and Comparative Example 1 Titanium nitride (Ti) was used as a first layer on a silicon wafer.
N) layer, an aluminum layer as a second layer on the first layer, and an insulating film (silicon oxide (Si) as a third layer on the second layer).
Via holes were formed on the substrate having the O ₂ )) layer by dry etching using the resist film as a mask, and subsequently, the resist film was removed by ashing using oxygen plasma. Residues that could not be removed by oxygen plasma existed in the upper part of the insulating film, the side wall part of the via hole, and the bottom part of the via hole.

The wafer was immersed in the release agent compositions shown in Tables 1 and 3 under the processing conditions shown in Tables 2 and 4, rinsed with ultrapure water and dried, and then scanned with a scanning electron microscope (SEM). ). Table 2 shows the results of evaluation of the removability of the residue and the corrosiveness to the aluminum layer.
And Table 4. The evaluation criteria in the SEM observation are as follows. (Removability) A: Completely removed. Δ: Partial residual was observed. ×: Most of the sample remained. (Corrosiveness) A: No corrosion was observed. Δ: Partial corrosion was observed. X: Severe corrosion was observed.

[0030]

[Table 1] A: 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone MEA: monoethanolamine EGB: ethylene glycol monobutyl ether BTA: benzotriazole HAS: hydroxylamine sulfate

[0031]

[Table 2]

[0032]

[Table 3] THFA: tetrahydrofurfuryl alcohol DMSO: dimethyl sulfoxide HAS: hydroxylamine sulfate

[0033]

[Table 4]

[0034]

According to the present invention, it is possible to provide a release agent composition having a low corrosiveness of a wiring layer and further excellent in removing residues generated by dry etching and ashing.

Claims (7)

[Claims] (1) The following general formula (I) ... (I) (wherein, R ₁ and R ₂ each independently represent a hydrogen atom, or represent a hydroxyl group, a carboxyl group, or an optionally substituted alkyl group, and Z represents oxygen A) a cyclic urea compound represented by an atom or a sulfur atom), (b) an organic amine, (c) a salt of an organic amine or an inorganic amine with an acid, and (d) water and / or a water-soluble organic solvent. A release agent composition comprising: 2. The release agent composition according to claim 1, wherein the organic amine is an alkanolamine, an alkyl ammonium hydroxide, or a mixture thereof. 3. The method according to claim 1, wherein the salt of the organic amine or inorganic amine with an acid is at least one organic amine or inorganic amine selected from the group consisting of alkanolamines, alkylammonium hydroxides and hydroxylamines. The stripping composition according to claim 1 or 2, which is a salt with at least one acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and carboxylic acids. 4. The release agent composition according to claim 1, further comprising a metal corrosion inhibitor. 5. The release agent composition according to claim 4, wherein the metal corrosion inhibitor is an aromatic hydroxy compound, a triazole compound, or a mixture thereof. 6. A method for removing residues generated during ashing or dry etching using the stripping composition according to claim 1. 7. A method for removing a resist film using the stripping composition according to claim 1.