JP2003114540A - Release agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a release agent composition excellent in power to remove residue produced by via hole formation by etching a interlayer dielectric film on a metallic film using a resist above a highly integrated substrate as a mask, subsequent ashing of the remaining resist, etc., excellent also in property of preventing corrosion of the metallic film and reducing damage to the quality of the interlayer dielectric film, particularly a low dielectric constant film to a practical level. SOLUTION: The release agent composition comprises at least one of alcohols having an intramolecular ether bond as a component (a) and an anticorrosive as a component (b), wherein furfuryl alcohol or tetrahydrofurfuryl alcohol is preferably used as the component (a).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stripper composition for removing unnecessary substances such as a resist and an etching residue remaining after etching in a semiconductor device.

[0002]

2. Description of the Related Art In a process of forming a hole, a wiring groove, etc. in a semiconductor device manufacturing process, after a resist pattern is formed by using a lithography technique, dry etching is performed using this as a mask, and then a resist pattern used as a mask. Is carried out in the process of removing. To remove the resist pattern, a wet process using a stripping solution is generally performed after ashing with plasma or the like. As such a stripping solution, various types have been developed and put into practical use, for example, an organic sulfonic acid-based stripping solution containing alkylbenzene sulfonic acid as a main component, and amines such as monoethanolamine as a main component. Organic amine-based stripping solutions, hydrofluoric acid-based stripping solutions containing hydrofluoric acid or a salt thereof as a main component are known.

However, needless to say, the peeling performance is improved by further increasing the integration density and increasing the density of semiconductor devices.
A low resistance material such as copper is often used as a wiring material. When a via hole or the like is formed in the interlayer insulating film on the copper wiring, the etching residue mainly containing silicon and its oxide remains on the bottom or side wall of the via hole when the interlayer insulating film is etched. It is necessary to remove the barrier film, which is formed in the process, because it hinders the film forming property. However, if a conventionally known stripping solution is used to remove the copper wiring, the copper wiring exposed at the bottom of the via hole will also melt, which is a serious problem. Therefore, from the viewpoint of preventing corrosion of a metal material such as copper wiring due to a stripping solution, a stripping solution in which a composition having an anticorrosive property is added to the composition has been proposed.

On the other hand, it is necessary to reduce the capacitance between adjacent wirings in order to take advantage of the low resistance characteristics of copper wirings, and it is common to use a material having a low dielectric constant for the interlayer insulating film formed around the wirings. is there. For example, SiOC (carbon-containing S
inorganic materials such as iO ₂ ) or polyorganosiloxanes such as MSQ (methylsilsesquioxane), HSQ (hydrogensilsesquioxane) and MHSQ (methylated hydrogensilsesquioxane),
Examples thereof include aromatic-containing organic materials such as polyaryl ether (PAE) and divinylsiloxane-bis-benzocyclobutene (BCB). Such a low dielectric constant material has low ashing resistance and has a problem that the dielectric constant rises when exposed to plasma. Therefore, the ashing time can be shortened as much as possible and the ashing condition can be controlled. It is desired to be as gentle as possible, but in that case, treatment with a stripping solution having a strong stripping action is indispensable.

A composition containing a fluorine-containing compound such as hydrofluoric acid is often used as a photoresist stripping solution or a deteriorated film removing solution after ashing, especially for removing residues mainly containing silicon and its oxide. However, as such an example, for example, a semiconductor device cleaning agent containing a specific quaternary ammonium salt and a fluorine compound, and further an organic solvent (Japanese Patent Laid-Open No. 7-201794), a base containing no metal ion. And a salt of hydrofluoric acid, and a water-soluble organic solvent,
A resist stripper composition having a system pH of 5 to 8
No. 197681), a fluorine compound, a water-soluble organic solvent, and a cleaning agent for semiconductor devices each containing a specific amount of water (Japanese Patent Laid-Open No. 11-67632), a specific quaternary ammonium hydroxide, and a redox potential. A stripping solution containing a nucleophilic amine compound, a saccharide and / or a sugar alcohol, and water each having a specific compounding ratio (JP-A-9-283).
No. 507) is known.

[0006] As a stripping composition having a function of preventing corrosion of metal wiring, US Pat. No. 5,417,877 discloses
Mainly composed of amide and amine, having a 5- or 6-membered ring structure in the molecule, and having a plurality of heteroatoms that form a coordination complex of a 5- or 6-membered ring by coordinating with the metal of the wiring material Japanese Patent Application Laid-Open No. 10-171130 discloses a stripping agent composition containing a component as a corrosion inhibitor and an organic amine and a nitrogen-containing compound having a specific structure. However, these have not been studied for application to fine and multilayer wiring processes that employ copper wiring and a low dielectric constant film, and although corrosion of metal wiring can be achieved, removal of substrate surface deposits is incomplete. There was a problem that the low dielectric constant film was damaged.

However, in the conventional stripping solution and cleaning solution described in each of these publications, a low dielectric constant film has not been studied first, and it has been formed on a recently highly integrated and high density substrate. It has not been possible to prevent corrosion of metal wiring to a practical level.

Further, the stripping solution and the cleaning solution containing a fluorine compound such as hydrofluoric acid have a problem that the copper film is likely to be corroded and the film quality of the low dielectric constant film material is easily damaged. .

Further, in order to improve the removability of unnecessary residues such as precipitates deposited on the bottoms and sidewalls of the via holes, even if the amine content is increased, the film quality of the low dielectric constant film material is greatly damaged. The present inventors have found that there is a problem.

As described above, if the residue of the bottom and side walls of the via hole and the residue containing silicon and its oxide as the main component are sufficiently removed, the metal wiring is corroded and the low dielectric constant film material is used. There was a problem that the damage to

[0011]

SUMMARY OF THE INVENTION In order to solve these problems of the prior art, the inventors of the present invention consisted of a stripping agent, particularly an alkanolamine, a solvent and an anticorrosive agent, and the anticorrosive agent contains a nitrogen atom. A heterocyclic compound having a ring, particularly a purine, purine derivative, uric acid, or a uric acid derivative, was invented, and an application was previously filed (Japanese Patent Application No. 2001-19).
6512). However, even when the release agent composition of the invention of the prior application was used, it was confirmed that some types of low dielectric constant film cause damage or that removal of substrate surface deposits was incomplete.

Up to now, the resist stripping solution has been developed as a means for improving the anticorrosion performance for the wiring material. However, in the situation where the low dielectric constant film is used as the interlayer insulating film, the resist stripping solution is used during the stripping process. It has become necessary to remove the ashing residue and the resist residue with the low dielectric constant film exposed. Therefore, it is necessary to consider the stripper from a viewpoint different from the conventional one.

The present invention has been made in view of the above circumstances, and particularly, the formation of via holes by etching the interlayer insulating film on the metal film using the resist as a mask on the recent highly integrated substrate, and then remaining. It excels in the ability to remove residues generated by resist ashing treatment, etc., as well as residues containing silicon and its oxide as the main component, and also has excellent corrosion resistance to metal films and an interlayer insulating film, especially low. An object of the present invention is to provide a peeling composition in which damage to the film quality of a dielectric constant film is reduced to a practical level.

[0014]

Means for Solving the Problems In order to solve the above problems, the present inventors have studied in detail the components constituting the stripping solution by function. First, the anticorrosive component is adsorbed to the wiring metal surface by a coordinate bond and exerts its anticorrosion function by keeping corrosive ions in the liquid away from the metal surface, so the solubility of the solvent in the anticorrosive agent is too strong. And the anticorrosive does not work effectively. Therefore, the selection of the solvent is important for the effective functioning of the anticorrosive agent. Furthermore, it is important to select a solvent that does not damage the low dielectric constant film. In particular, it has been found that it is desirable that the solvent has low permeability to the low dielectric constant film. In addition, addition of hydrofluoric acid (HF) is effective for removing (peeling) SiO ₂ -based substrate surface deposits, and amine, particularly alkanolamine, is effective for removing (peeling) resist residues. is there. However, it has been found that damage is generated depending on the type of the low dielectric constant film when the pH of the release agent composition is 6 or less or 12 or more by adding more than these components that enhance the release function. Desirable liquidity is weakly alkaline, and when a component having pH buffering ability, that is, weak acid, preferably organic acid, more preferably lactic acid is added to the stripper composition, liquidity control in weakly alkaline is improved and stable. Peeling performance was obtained.

As a result of the above detailed examination, a stripping agent composition was found which can simultaneously achieve high residue removal performance, high corrosion protection performance, and low damage to a low dielectric constant film.
The present invention has been completed.

That is, the present invention comprises (I) a release agent composition comprising (a) at least one alcohol having an ether bond in the molecule as a component and (b) a corrosion inhibitor. object. (II) The release agent composition according to (I), wherein the component (a) is an alcohol having a cyclic ether structure in the molecule. (III) The stripper composition according to (II), wherein the alcohol having a cyclic ether structure in the molecule is represented by the following formula. X- (A-OH) _n (In formula, X is a cyclic ether structure, A is a C1-C8 hydrocarbon chain, n is 1 or more and represents the number of substitutions to a cyclic ether structure.) ( IV) The stripper composition according to (II) or (III), wherein the alcohol having a cyclic ether structure in the molecule is furfuryl alcohol or tetrahydrofurfuryl alcohol. (V) The release agent composition according to (I), wherein the component (a) is a mixture of alcohols having a cyclic ether structure in the molecule and alcohols having a glycol ether structure in the molecule. . (VI) The release agent composition according to any one of (I) to (V), which contains at least one organic or inorganic weak acid as the component (c). (VII) The stripper composition according to (VI), wherein the component (c) is lactic acid. (VIII) (I) to (VI) containing water as a component (d)
The release agent composition according to any one of I). (IX) The water content is less than 70% by mass (VIII)
The release agent composition according to. (X) The component (b) is (1) a purine derivative, (2)
A compound having at least one carboxyl group and capable of forming a chelate with a metal, which is dibasic or more and has a hydrophobic group, (3) a mixture of the purine derivative and quinaldic acid, or (4) A mixture of the compound of (2) and quinaldic acid, (5) a mixture of the purine derivative of (1) and the compound of (2), and (6) a purine derivative of (1), the compound of (2). And the anticorrosive agent selected from a mixture of quinaldic acid and the stripper composition according to any one of (I) to (IX). (XI) The compound of (2) above is o-phthalic acid (X)
Stripping agent composition. (XII) The stripper composition according to (X), wherein the purine derivative according to (1) above is adenine or a derivative thereof. (XIII) The release agent composition according to any one of (I) to (XII), which further contains at least one kind of amines as the component (e). (XIV) The amines are alkanolamines (XII
The release agent composition described in I). (XV) The stripper composition according to (XIII), wherein the base equivalent value of the amines is larger than the equivalent value of the acid component in the system. 0.001 to 15 mass% of (XVI) (b) component, (c)
0 to 15 mass% of component, 2 mass% or more of component (d) 70
The release agent according to any one of (XIII) to (XV), characterized by containing less than 1% by mass of the component (e) and 1 to 40% by mass of the component (a) and 30% by mass or more of the component (a) as the balance. Composition.

As component (XVII) (a), at least one alcohol having an ether bond in the molecule,
A release agent composition comprising (c ') component at least one of hydrofluoric acid and a salt thereof, and (d) component water. (XVIII) The component (a) is an alcohol having a cyclic ether structure in the molecule (XVI
The release agent composition of I). (XIX) The stripper composition according to (XVIII), wherein the alcohol having a cyclic ether structure in the molecule is furfuryl alcohol or tetrahydrofurfuryl alcohol. (XX) Further, at least one kind of amines is contained as the component (e) (XVII) to (XIX)
The release agent composition according to any one of 1. (XXI) The amines are alkanolamines (X
The release agent composition described in X). 0.01 to 15 mass% of (XXII) (c ') component, (d)
5 to 30 mass% of component, 10 to 40 mass% of component (e)
The release agent composition according to (XX) or (XXI), which contains 20% by mass or more of the component (a) as the balance. (XXIII) Contains a corrosion inhibitor as component (b) (XVI
The release agent composition according to any one of I) to (XXII). (XXIV) The component (b) is (1) a purine derivative,
(2) a compound having at least one carboxyl group and having a ability to form a chelate with a metal, which is dibasic or more and has a hydrophobic group, (3) a mixture of the purine derivative and quinaldic acid, or (4) A mixture of the compound of (2) and quinaldic acid, (5) a mixture of the purine derivative of (1) and the compound of (2), and (6) a purine derivative of (1), the above (2). The stripping agent composition of (XXIII), which is an anticorrosive selected from the mixture of the compound) and quinaldic acid. (XXV) The compound of (2) above is o-phthalic acid (XXI
V) release agent composition. (XXVI) The stripper composition according to (XXIV), wherein the purine derivative according to (1) above is adenine or a derivative thereof. (XXVII) Any one of (XXIII) to (XXVI), wherein the component (b) is contained in an amount of 0.001 to 15% by mass.
The release agent composition according to item.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The first release agent composition of the present invention comprises, as the component (a), at least one of alcohols having an ether bond in the molecule.
A release agent composition containing a seed and an anticorrosive agent as a component (b).

The alcohol as the component (a) is not particularly limited as long as it is compatible with water, but it is characterized by having an ether bond in the molecule. Such compounds include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether,
Glycol ethers such as triethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, and diethylene glycol monoisobutyl ether, cyclic alkoxy groups,
For example, cyclobutoxy, cyclopentoxy, alcohols having an alicyclic oxy group such as cyclohexyloxy group, alcohols having a heterocyclic oxy group containing nitrogen as a hetero atom, sulfur, at least oxygen as a hetero atom. Alcohols having a cyclic ether structure having Of these, alcohols having a cyclic ether structure are preferable. The alcohol having a cyclic ether structure is preferably represented by the following formula. X- (A-OH) _n (In formula, X is a cyclic ether structure, A is a C1-C8 hydrocarbon chain, n is 1 or more and represents the number of substitutions to a cyclic ether structure.)

In the above formula, the hydrocarbon chain having 1 to 8 carbon atoms of A is a straight chain, branched or cyclic alkylene group having 1 to 8 carbon atoms, a straight chain, branched chain or cyclic group having 2 to 8 carbon atoms. Examples thereof include an alkenylene group and a linear or branched alkynylene group having 2 to 8 carbon atoms, a linear alkylene group having 1 to 8 carbon atoms is preferable, and a methylene group is more preferable. X is a cyclic ether structure having a 3-membered ring or more, preferably a 5-membered ring or a 6-membered ring structure. Further, as the cyclic ether structure represented by X,
It may contain a nitrogen atom, a sulfur atom, or the like with a carbon atom interposed between it and an oxygen atom, and may have a polycyclic structure. Examples thereof include compounds derived from heterocyclic compounds containing nitrogen atoms, sulfur atoms and the like as hetero atoms in addition to oxygen atoms such as morpholine, and polycyclic structure compounds such as thienofuran.

Specifically, alcohols having the following 5-membered cyclic ether structure

[0022]

[Chemical 1]

(In the formulas (a1) to (a3), A _{1 to} A ₁₂ are each independently H, OH, halogen, amino, cyano,
Nitro, SH, SO ₃ H, COOH, alkyl of 1 to 8 carbon atoms, (shown in A the same meanings as defined _{above.) -A-OH, COOCH 3} , COOC 2 H 5, CH 3, CH 2 N
_{H 2, CONH 2, NHCH 3} , N (CH 3) 2, NHCH 2
CH ₃ , N (CH ₂ CH ₃ ) COCH ₃ , N (CH ₃ ) CO
CH ₃ , COCH ₃ , CON (CH ₂ CH ₃ ) ₂ , CH ₂ OC
H ₃ , CH ₂ Cl, OCH ₃ , CHO, OCH ₂ CH ₃ , S
COCH ₃ , O (CH ₂ ) ₄ Cl, CH ₂ SH, COCl,
COCH ₂ COCF ₃ , CH = CHCHO, CH = CHC
_{OOH, CH = CH 2, C} (OH) (CH 3) 2, = C
H ₂ , CH = NNHCONH ₂ , OCH ₂ CH ₂ NH ₂ , O
CH ₂ CH ₂ NO ₂ , selected from each formula (a1), ~ (a
At least one substituent in 3) is a substituent represented by -A-OH. )

Alcohols having the following 6-membered cyclic ether structure

[0025]

[Chemical 2]

(In the formulas (b1) to (b6), B ₁ to
B ₂₇ is independently H, OH, halogen, amino,
Nitro, cyano, SH, SO ₃ H, COOH, carbon number 1
8 alkyl, -A-OH (A is as defined _{above.), COOCH 3, COOC 2} H 5, CH 2 NH 2,
CONH ₂ , NHCH ₃ , N (CH ₃ ) ₂ , NHCH ₂ C
H ₃ , N (CH ₂ CH ₃ ) COCH ₃ , N (CH ₃ ) COC
_{H 3, COCH 3, CON (} CH 2 CH 3) 2, CH 2 OCH
₃ , CH ₂ Cl, OCH ₃ , CHO, OCH ₂ CH ₃ , SC
OCH ₃ , O (CH ₂ ) ₄ Cl, CH ₂ SH, COCl, C
OCH ₂ COCF ₃ , CH = CHCHO, CH = CHCO
_{OH, CH = CH 2, C} (OH) (CH 3) 2, = CH 2,
CH = NNHCONH ₂ , OCH ₂ CH ₂ NH ₂ , OCH ₂
At least one substituent selected from CH ₂ NO ₂ in each of formulas (b1) and (b6) is a substituent represented by —A—OH. ) And the like.

A solvent in which a bulky cyclic ether structure and an alcohol hydroxyl group are linked by a hydrocarbon chain, that is, at least one of the substituents in the above (a1) to (a3) and (b1) to (b6) is -A-. A solvent that is OH is preferred. In particular, the dissolving power of other components constituting the release agent composition,
From the balance of the peeling force of the deposit on the wafer surface and the permeability to the low dielectric constant film, furfuryl alcohol (FF
A), tetrahydrofurfuryl alcohol (THFA)
Is preferred. Further, such a solvent may be used alone as an alcohol having a cyclic ether structure within a range where damage to a low dielectric constant is slight, and may be used as a mixture with an alcohol having a glycol ether structure. For example, tetrahydrofurfuryl alcohol (THFA) can be used as the alcohol having a cyclic ether structure, and diethylene glycol monobutyl ether can be used as the alcohol having a glycol ether structure. When a mixed solvent is used, the mixing ratio of alcohols having a cyclic ether bond is 1 when the total amount of the solvent in the release agent composition is 100% by mass.
0 mass% or more is desirable, and 30 mass% or more is more desirable.

A resist stripping solution containing furfuryl alcohol is described in Japanese Patent Application Laid-Open No. 9-22122, but it is used in combination with an anticorrosive agent such as that of the present invention or the second fluorine of the present invention described later. It is not used as an acid-based stripping solution, and an example using furfuryl alcohol is not described in that example.
In particular, there is no description or suggestion that damage to the low dielectric constant film is small.

As the anticorrosive agent of the component (b) in the release agent composition of the present invention, conventionally known anticorrosive agents can be used. Examples thereof include aromatic hydroxyl compounds, acetylene alcohols, carboxyl group-containing organic compounds, and heterocycle-containing compounds such as triazole compounds and purine compounds. In particular, in the present invention, (1) a purine derivative, (2) a compound having at least one carboxyl group, a dibasic or more basic compound capable of forming a chelate with a metal, and having a hydrophobic group, (3) A mixture of the purine derivative and quinaldic acid, or (4) the above (2)
A mixture of the compound of claim 1 and quinaldic acid, (5) a mixture of the purine derivative of (1) and the compound of (2), and (6) a purine derivative of (1), the compound of (2) and quinaldic acid. Anticorrosion agents selected from the mixture are preferred.

Here, as the purine derivative of (1),
Preferred examples include adenine represented by the following general formula (1) and its derivatives.

[0031]

[Chemical 3] (In the formula, R ¹ and R ² are each independently a hydrogen atom, a hydroxyl group,
An alkyl group or an amino group having 1 to 5 carbon atoms is shown. )

The compound of (2) above is a dibasic or higher compound having a chelating ability with a metal, especially copper, together with at least one carboxyl group in a hydrophobic group such as a benzene ring. It has a structure represented by formula (2).

[0033]

[Chemical 4] (In the formula, A is a hydrophobic group, R ³ represents a hydroxyl group, a carboxyl group, an amino group or the like, and n represents an integer of 1 or more, preferably an integer of 1 to ^3. )

In particular, the compound (2) immediately forms a chelate with the metal upon contact with the metal surface, and the hydrophobic groups are arranged on the outside to form a uniform film on the surface of the metal surface. Exhibits the effect of suppressing oxidation. As the compound of the above (2), phthalic acid, particularly o-phthalic acid is preferable.

The first release agent composition of the present invention essentially contains the above-mentioned components (a) and (b), but as the component (c), an organic or inorganic weak acid,
Water may be contained as the component (d), and amines may be contained as the component (e).

The weak acid as the component (c) is an inorganic or organic weak acid. Examples of the organic acid include monocarboxylic acids such as formic acid, acetic acid and propionic acid, oxalic acid, malonic acid, succinic acid and glutan. Acid, dicarboxylic acid such as adipic acid, pimelic acid, maleic acid, fumaric acid, trimellitic acid, tricarboxylic acid such as tricarballylic acid, hydroxyacetic acid, lactic acid, salicylic acid, malic acid, tartaric acid,
Examples thereof include oxycarboxylic acids such as citric acid, gluconic acid, 2-deoxy-gluconic acid, and mucus acid. Among them, lactic acid and citric acid, oxycarboxylic acids such as gluconic acid are preferable, and lactic acid is particularly preferable.

The water as the component (d) may be added separately, or may be the water entrained in the above components. The water content is preferably less than 70%.

Examples of the amines as the component (e) include tetramethylammonium hydroxide (TMAH), quaternary ammonium salts such as choline ((CH ₃ ) ₃ N ⁺ CH ₂ CH ₂ OH), hydroxylamine and alkanolamines. , And the like. Specific examples of the alkanolamines include monoethanolamine, diethanolamine, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, dimethylaminoethanol, 2- (2-aminoethoxy). Examples include ethanol, 1-amino-2-propanol, triethanolamine, monopropanolamine, dibutanolamine and the like. Of these, monoethanolamine and 2- (methylamino) ethanol are particularly preferable.

Since alkanolamines such as monoethanolamine and 2- (methylamino) ethanol show good biodegradability, when these are selected as the stripping agent component, the safety of the stripping agent composition of the present invention is improved. It is possible to further enhance biodegradability.

In using the first release agent composition of the present invention, the treatment conditions may be room temperature (low temperature) without heating, or heating to about 50 to 100 ° C. (B)
Depending on the type of the component anticorrosion agent, sufficient anticorrosion properties may not be achieved under low temperature conditions, but under such low temperature conditions, the compounds of (1) and (2) above are mixed as component (b). Excellent corrosion resistance and residue removability can be achieved at the same time by using a compound of the above (1) or (2) or a mixture of these compounds or a mixture with quinaldic acid.

The composition ratio of each component is 0.00 for the component (b).
1 to 15% by mass, component (c) 0 to 15% by mass, (d)
2 mass% or more and less than 70 mass% of the component, and (e) the component is 1 to
40% by mass is included, and the balance contains 30% by mass or more of the component (a), and the total amount is 100% by mass. When the composition ratio of the component (a) is less than 30% by mass, the releasability may not be sufficient, and even if it exceeds 90% by mass, the releasability is lowered and at the same time, the anticorrosion property is lowered and the low dielectric constant is low. Damage to the film may increase. Further, when the water content of the component (d) is less than 2% by mass, the releasability may decrease, and it is desirable that the water content of 2% by mass or more, more preferably 5% by mass or more is contained. When the water content of the component (d) is 70% by mass or more, the composition ratio of the component (a) of 30% by mass cannot be ensured, so that the peelability is lowered as described above.

In the first release agent composition of the present invention,
It is desirable to prepare the composition so that the pH when used is 6-12. It is preferable to adjust the base equivalent of the amines as the component (e) to be larger than the acid equivalent in the system so that the amine is neutral (pH 7) to weakly basic (pH 10). Furthermore, in the release agent composition of the present invention, in the range that does not deteriorate its performance,
It is possible to mix other ingredients. For example, an aminocarboxylic acid-based or phosphonic acid-based chelating agent, an anion-based, cation-based, or nonionic surfactant can be added.

The second release agent composition of the present invention is a hydrofluoric acid type composition, and is particularly effective for removing the silicon oxide type residue.

The second stripping agent composition of the present invention comprises, as the component (a), at least one alcohol having an ether bond in the molecule, and as the component (c '), at least one of hydrofluoric acid and salts thereof. It is characterized by containing a seed and water as the component (d).

Here, the alcohols having an ether bond in the molecule of the component (a) are the same as those of the component (a) of the first stripping agent composition, and the alcohols having a cyclic ether structure in the molecule. And furfuryl alcohol or tetrahydrofurfuryl alcohol is particularly preferable.

The hydrofluoric acid and its salts as the component (c ') include hydrofluoric acid (HF), its ammonium salt (for example, ammonium fluoride and ammonium acid fluoride), and amine salt (for example, methyl). Amine hydrofluoride,
Examples thereof include ethylamine hydrofluoride and propylamine hydrofluoride. Those containing ions such as sodium salts and calcium salts which adversely affect the semiconductor element are not preferable. When ammonium fluoride or the like is used, it is preferable to remove ammonium ions from the system. The ammonium ion can be removed by preparing the stripping solution and then leaving it at room temperature for a long time, but it may be removed by heating. Especially in the presence of alkanolamine, it is effectively removed.

In using the second release agent composition of the present invention, the treatment conditions may be room temperature (low temperature) without heating, or heating to about 50 to 100 ° C.

Further, in the second stripping agent composition of the present invention, the amines described in the first stripping agent composition as the component (e), and the first stripping agent as the component (b). The anticorrosive agent described in the composition may be added.

Depending on the type of the component (b) anticorrosion agent, sufficient anticorrosion properties may not be achieved under low temperature conditions, but under such low temperature conditions, the compounds of (1) and (2) above are mixed. Excellent corrosion resistance and residue removability can be achieved by using either the compound of (1) or (2) or the mixture of these compounds or mixture with quinaldic acid. .

The composition ratio of each component is 0.0 for the component (c ').
1 to 15% by mass, (d) component 5 to 30% by mass, (e)
The composition contains 10 to 40% by mass, and the balance contains the component (a), and the total amount is 100% by mass. When the composition ratio of the component (a) is less than 20% by mass, the releasability may not be sufficient, and even if it exceeds 90% by mass, the releasability is deteriorated and, at the same time, the anticorrosive property is deteriorated and the low dielectric constant Damage to the film may increase. Therefore, the component (a) is 2
The content is preferably 0% by mass or more, and more preferably 50% by mass to 90% by mass. Further, when the component (b) is contained, it is desirable that the content is 0.001 to 15% by mass. Furthermore, also in the second release agent composition of the present invention, other components can be mixed in a range that does not deteriorate the performance. For example, an aminocarboxylic acid-based or phosphonic acid-based chelating agent, an anion-based, cation-based, or nonionic surfactant can be added.

The first and second stripping agent compositions of the present invention can be used for stripping various resists, and can be applied to KrF resists composed of aromatic compounds and ArF resists such as alicyclic acrylic polymers. Can be applied. For example, (i) a positive resist containing a naphthoquinonediazide compound and a novolak resin, (ii) a compound that generates an acid upon exposure, a compound that decomposes with an acid and has increased solubility in an aqueous alkaline solution, and a positive resist that contains an alkali-soluble resin. Type resist, (iii) a compound that generates an acid upon exposure to light, a positive resist that contains an alkali-soluble resin having a group that is decomposed by an acid and has increased solubility in an alkaline aqueous solution, (iv) a compound that generates an acid by light, It can be used for negative resists containing a crosslinking agent and an alkali-soluble resin.

The release agent composition of the present invention is for removing unwanted substances on a semiconductor substrate. The unwanted substances on the semiconductor substrate are various unwanted substances generated during the manufacturing process of the semiconductor device, and include a resist film, an etching residue after dry etching, and a chemically altered resist film. Particularly, it is more effective when the object to be peeled is a resist film and / or an etching residue on the semiconductor substrate including the exposed surface of the metal film. Furthermore, when the metal film is a copper film, the anticorrosive action of the release agent composition of the present invention is more effectively exhibited.

The present invention is effective when applied to the removal of the resist film and / or the etching residue on the semiconductor wafer including the exposed surface of the metal film, but the metal film is made of copper or copper containing copper as a main component. As an alloy, and as an interlayer insulating film,
It is particularly effective when a low dielectric constant film is used. The copper alloy containing copper as a main component is an alloy containing 90 mass% or more of copper, and is Sn, Ag, Mg, Ni, Co, Ti, S.
i, a copper alloy containing different elements such as Al. While these metals have low resistance and improve high-speed operability of the element, they are likely to be corroded by chemicals such as dissolution and alteration, so that the application effect of the present invention becomes remarkable. Further, as the low dielectric constant film, due to the difference in the film forming method, a liquid in which a resin for forming the low dielectric constant film is dissolved in a solvent in advance is applied onto the rotated semiconductor wafer to form the film. A spin coating method of forming a film by baking it and vaporizing a monomer solution or the like by heating or bubbling, or decomposing and recombining a gaseous monomer at room temperature with plasma or thermal energy to form a wafer. It is divided into a CVD method and the like for forming a thin film. The type of film formed by the spin coating method is M
Polyorganosiloxane thin films such as SQ (methyl silsesquioxane), HSQ (hydrogen silsesquioxane), MHSQ (methylated hydrogen silsesquioxane), PAE (polyaryl ether), BCB (divinyl) Aromatic-containing organic thin films such as siloxane-bis-benzocyclobutene).
The type of film formed by the CVD method is FSG.
Examples thereof include a system-based thin film, a SiON-based thin film, and a SiOC-based thin film. The stripping agent of the present invention does not depend on the method of forming the low dielectric constant film or the type of the film, but is particularly effective for the organosiloxane thin film, the aromatic-containing organic thin film, and the SiOC thin film.

Next, as an application example of the release agent composition of the present invention, an example of forming an interlayer connection plug on a copper wiring by a single damascene process will be shown.

First, as shown in FIG. 1A, a silicon oxide film 1, a silicon nitride film 2, and a silicon oxide film 3 are formed on a semiconductor substrate (not shown) on which elements such as transistors are formed, and then chemicals are formed. Mechanical Polishing (Chemical Mechanical P
A copper wiring consisting of the barrier metal film 4 and the copper film 5 is formed by using a known damascene process utilizing a polishing process (CMP), and a silicon nitride film 6 having a film thickness of about 50 to 100 nm and a film thickness of 250 to A low dielectric constant film 7 such as MSQ having a thickness of about 500 nm is formed,
A silicon oxide film 8 having a thickness of about 0 nm is formed. Although the thickness of the copper film 5 is arbitrarily selected, it is preferable to set the thickness to, for example, 350 nm or less from the viewpoint of reducing the parasitic capacitance between adjacent wirings. When the thickness of the copper wiring is reduced, the thickness of the corrosion layer relative to the entire copper wiring layer becomes relatively large, and an increase in wiring resistance due to corrosion of the copper surface becomes a particular problem, but the release agent composition of the present invention is used. If used, it is possible to reduce the film thickness while solving such a problem. Although the silicon nitride film 6 has a thickness of about 50 to 100 nm in the present embodiment, it may be thicker to enhance the function as an etching stop film.

Next, a resist film 9 patterned into a predetermined shape is provided on the silicon oxide film 8 (see FIG. 1).
(B)).

Next, the silicon oxide film 8 and the low dielectric constant film 7 are dry-etched using the resist film 9 as a mask until the silicon nitride film 6 is exposed to form a via hole 10 (FIG. 1C). At this time, the etching residue 11 adheres to the inner wall of the via hole 10. The opening diameter of the via hole is, eg, about 0.2 μm. As the etching gas, it is preferable to use a gas that can etch the silicon oxide film faster than the silicon nitride film.

After the etching is completed, a part of the resist film 9 is removed by oxygen plasma ashing or N ₂ —H ₂ gas plasma, and then a stripping treatment is carried out using the stripping agent composition according to the present invention. By this peeling process, the resist film and the etching residue 11 which cannot be completely removed by ashing are removed. As described above, after etching, the copper film 5 may be exposed in a via hole having a large opening area. In such a case, the release agent composition requires corrosion protection against copper. By using the material, the resist film and the etching residue 11 can be effectively removed without damaging the copper film 5. A state in which the peeling process is completed is shown in FIG.

After that, the etching gas is changed from the above etching, and the silicon nitride film 6 is etched. At this time, the etching residue 12 adheres to the inner wall of the via hole 10 (FIG. 2B). In order to remove the etching residue 12 by peeling, the peeling treatment is performed again using the above-described peeling agent composition. At the stage of performing the stripping process, the copper film 5 is exposed at the bottom of the via hole 10. However, by using the stripping agent composition of the present invention, the etching residue 12 can be removed without damaging the copper film 5 ( Figure 2
(C)).

Then, Ti and T are placed inside the via hole.
An interlayer connection plug can be formed by forming a barrier metal film 13 and a tungsten film 14 in which iN is laminated in this order, and then performing planarization by CMP (FIG. 2D).

[0061]

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. An example of the first release agent composition is Example 1,
3 and 4, examples of the second release agent composition are shown in Example 2 and Examples 5 to 9, respectively. Moreover, "%" is based on mass unless otherwise specified.

Example 1 The first release agent composition according to the present invention was applied to the process for forming via holes on copper wiring, and the release properties and anticorrosion properties were evaluated.

The samples used for evaluation were prepared according to the process shown in FIGS. First, after forming copper wiring on a silicon wafer, a film thickness of 90 nm is formed on it.
A silicon nitride film, a low dielectric constant film having a film thickness of 450 nm, and a silicon oxide film having a film thickness of 450 nm were formed. The film formation is
All were performed by the plasma CVD method. Next, a positive resist film was applied by spinner to form a resist film.
As the resist film material, “PEX4” (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a positive resist material for KrF, was used. This resist film was exposed through a mask pattern and developed using a tetramethylammonium hydroxide aqueous solution to obtain a resist pattern.

Using the resist film as a mask, the silicon oxide film and the low dielectric constant film were dry-etched until the silicon nitride film was exposed to form a via hole having an opening diameter of 0.2 μm. A fluorocarbon-based gas was used as the etching gas. After the etching was completed, a part of the resist film was removed by oxygen plasma ashing, and then a stripping treatment was performed using the stripping agent composition shown in Table 1.

Next, the etching gas was changed and the silicon nitride film was etched to expose the copper wiring at the bottom of the via hole. In order to remove the etching residue generated by this etching, the above-mentioned stripping agent composition was used to perform stripping treatment at room temperature (23 ° C.) for 10 minutes of immersion time.

The same treatment was carried out using the No. 2 to No. 11 release agent compositions in Table 1 to prepare 11 kinds of samples in total.

The wafer treated as described above is rinsed with pure water, and then cross-sectional observation is performed with an SEM (scanning electron microscope) to remove the resist film and the etching residue at the via bottom and the via bottom. The corrosion resistance of the exposed copper film and the damage of the exposed low dielectric constant film (SiOC) surface were evaluated. The evaluation criteria are as follows.

(Peelability) The residual state of the resist film and the bottom of the via of the etching residue was observed and evaluated according to the following four grades. A: No residual was observed at all. O: Almost no residual was observed. Δ: Small residual amount. X: A large amount remains.

(Corrosion resistance) The corrosion state of the copper film surface exposed at the bottom of the via was observed and evaluated according to the following four grades. A: No corrosion of the copper film was observed. O: Corrosion of the copper film was slightly observed. B: Corrosion of the copper film was observed. C: Corrosion of the copper film was remarkable.

(Damage to Low Dielectric Constant Film) The state of the surface of the low dielectric constant film when a SiOC type film was used as the low dielectric constant film was observed and evaluated according to the following four grades. A: No damage was observed. ○ ... Slight damage was observed. Δ: Damage was observed. X: The damage was remarkable.

[0071]

[Table 1] THFA: Tetrahydrofurfuryl alcohol DEGB: Diethylene glycol monobutyl ether 2MAE: 2- (Methylamino) ethanol

As described above, the pH was adjusted from neutral (pH 7) to weakly basic (pH 1) by adding alkanolamine and lactic acid.
By controlling the content to be around 0) and adjusting the water content to less than 70%, sufficient corrosion resistance can be obtained even with the addition of an extremely low concentration anticorrosion agent. In the release agent composition of the present invention, if the anticorrosive is 0.01% or more, sufficient anticorrosion performance for Cu can be obtained, but if it is 0.03% or more, stable performance can be obtained. That is, the anticorrosive agent can be added in the range of 0.01% or more. However, if added at a high concentration, foreign matter may be generated on the wafer surface after the peeling process. Further, since the anticorrosive agent is more expensive than the other constituents of the release agent, it is desirable to keep the addition amount to a necessary and sufficient amount. In the examples described in JP-A-2000-162788 and JP-A-2001-83712, the concentration of benzotriazole and its derivative is 0.1 to 1% as an anticorrosive agent for Cu. The corrosion inhibitor concentration in the composition is remarkably low. The stripping agent composition of the present invention exhibits good anticorrosion properties at low concentrations, and also exhibits good performance with respect to low damage to the low dielectric constant film which is another subject of the present invention. There is. Further, the water content is preferably 2% or more, but when it is 5% or more, the release performance which is an essential function of the release agent composition, particularly the release performance of the via bottom is excellent.

Example 2 As in Example 1, a sample using a SiOC-based low dielectric constant film in which copper wiring was exposed at the bottom of the via hole was used.
Sample No. 12 and No. 13 were immersed in the stripper composition at room temperature (23 ° C.) for 10 minutes and then rinsed directly with pure water, and evaluated in the same manner as in Example 1. Furthermore, for the sample before peeling treatment,
Unlike Example 1, continuous deposition of silicon oxide deposits was observed on the device surface, but the removability of this deposit was also evaluated. In addition, as a reference, Example 1
No. used in The results of using the release agent composition of 2 are also shown.

[0074]

[Table 2]

As can be seen from Table 2 above, in order to remove the silicon oxide deposits adhering to the device surface, the addition of the fluorine component is indispensable. Inflicts damage. By adjusting the amount of alkanolamine or HF added and controlling the pH to around neutrality, excellent corrosion resistance and removal of silicon oxide deposits on the device surface are achieved even with the addition of an extremely low concentration anticorrosion agent. In addition, it is possible to obtain a release agent composition which hardly damages the SiOC-based low dielectric constant film.

Example 3 In order to confirm the effect of the anticorrosive agent, a representative composition (No. 2) of the release agent composition of Example 1 was used, and the anticorrosive agent was changed.
Removal characteristics such as deposit removal and Cu corrosion resistance were evaluated. BT
Sufficient stripping properties can be obtained even by using a general anticorrosive agent such as A. However, purine and its derivative, adenine, are biological substances and are excellent in biodegradability, so they can be used safely. Moreover, it is easy to treat wastewater and has excellent environmental friendliness.

[0077]

[Table 3]

Example 4 It is sufficient to remove the surface residue if the chemical action of the release agent composition acts on the outermost surface of the substrate and the surface residue. However, if the release agent composition has the property of penetrating into the low dielectric constant film, the chemical action of the release agent composition extends inside the film and damages the film. Selecting a solvent having low permeability to the low dielectric constant film as the solvent which is the main component of the release agent composition is effective in suppressing the permeability of the release agent composition. Therefore, a solvent is dropped onto the SiOC-based and HSQ-based low dielectric constant films, and the contact angle changes with time (the contact angle decreases when the solvent penetrates into the film because the low dielectric constant film is porous). Thus, the permeability of the solvent to the low dielectric constant film was evaluated. The results are shown in Table 4. Further, each solvent was dropped on the surface of the low dielectric constant film of the MSQ-based thin film so that the diameter of the droplet was 1 mm, and 30 seconds after that, the contact angle between the film and the droplet was spread for 5 minutes and then spread. The diameter of the droplet was measured. Furthermore, the discoloration of the film around the droplet was evaluated. The results are shown in Table 5.

[0079]

[Table 4]

[0080]

[Table 5] FFA: Furfuryl alcohol DMSO: Dimethyl sulfoxide NMP: N-methyl-2-pyrrolidone

As described above, THFA is an inorganic Si
Almost no permeation is observed for low dielectric constant films of OC and organic HSQ. Further, both the THFA and FFA had a low contact angle with MSQ and had good wettability, but the droplets did not spread even when left standing. On the other hand, with other solvents, the contact angle is equal to or higher than that of THFA, etc., and the liquid spreads to the surface of the film when left standing and permeates into the inside, causing the color of the film to change. confirmed.

The damage of the low dielectric constant film is considered to be because the peeling agent composition penetrates into the film and attacks the skeleton constituting the film, and THFA is used as the main solvent of the peeling agent.
It is considered that, when FFA or FFA is used, since it does not penetrate into the inside of the film, it does not damage the low dielectric constant film, and because it has good wettability, only the deposit remaining on the film can be efficiently peeled off.

Example 5 The second stripper composition according to the present invention was applied to the process for forming via holes on copper wirings, and the strippability and corrosion resistance were evaluated.

The samples used for evaluation were prepared according to the process shown in FIGS. First, after forming copper wiring on a silicon wafer, a film thickness of 90 nm is formed on it.
A silicon nitride film, a low dielectric constant film having a film thickness of 450 nm, and a silicon oxide film having a film thickness of 450 nm were formed. The film formation is
All were performed by the plasma CVD method. Next, a positive resist film was applied by spinner to form a resist film.
This resist film was exposed through a mask pattern and developed using a tetramethylammonium hydroxide aqueous solution to obtain a resist pattern.

Using the resist film as a mask, the silicon oxide film and the low dielectric constant film were dry-etched until the silicon nitride film was exposed to form a via hole having an opening diameter of 0.2 μm. A fluorocarbon-based gas was used as the etching gas. After the etching is completed, a part of the resist film is removed by oxygen plasma ashing, and then a stripping treatment is performed using a stripping agent composition containing 1% of benzotriazole shown in Table 6 (No. 16 in Table 6). It was

Next, the etching gas was changed and the silicon nitride film was etched to expose the copper wiring at the bottom of the via hole. In order to remove the etching residue generated by this etching, the stripping agent composition containing 1% of benzotriazole used in the above stripping treatment was used and the temperature was set to 8
The peeling treatment was performed at 0 ° C. for 10 minutes.

The same treatment was carried out using No. 17 to No. 20 release agent compositions shown in Table 6 (1% benzotriazole was added in each case) to prepare 5 kinds of samples in total.

The wafer treated as described above is immersed in isopropyl alcohol (IPA), rinsed with pure water, and then cross-sectional observation is performed with an SEM (scanning electron microscope) to remove the resist film and etching residue. Detachability on the via bottom and device oxide film surface, corrosion resistance to the copper film exposed on the via bottom, exposed low dielectric constant film (HS
Q and MSQ) surface damage was evaluated. The evaluation criteria are as follows.

(Peelability) The residual state of the resist film and the etching residue was observed on the via bottom and the device oxide film surface,
The following four grades were evaluated. A: No residual was observed at all. O: Almost no residual was observed. Δ: Small residual amount. X: A large amount remains.

(Corrosion resistance) The corrosion state of the copper film surface exposed at the bottom of the via was observed and evaluated according to the following four grades. A: No corrosion of the copper film was observed. O: Corrosion of the copper film was slightly observed. B: Corrosion of the copper film was observed. C: Corrosion of the copper film was remarkable.

(Damage to Low Dielectric Constant Film) The state of the surface of the low dielectric constant film when HSQ or MSQ was used as the low dielectric constant film was observed and evaluated according to the following four grades. A: No damage was observed. ○ ... Slight damage was observed. Δ: Damage was observed. X: The damage was remarkable.

[0092]

[Table 6]

In Table 6, THFA is tetrahydrofurfuryl alcohol FFA is furfuryl alcohol BE is butoxyethanol NMP is N-methyl-2-pyrrolidone DMAC is dimethylacetamide 2MAE is 2- (methylamino) ethanol BTA is benzotriazole (-) Indicates that evaluation observation has not been performed. Are shown respectively.

As described above, the release agent composition (N
16-18) has excellent peeling performance and anti-corrosion performance of Cu, has little damage to the low dielectric constant film, and is especially THFA which is a cyclic ether structure alcohol.
Or a release agent composition containing FFA as a main component (No. 16 or 1
It turns out that 7) is particularly preferable. Although the present embodiment applies the present invention to a single damascene process, the present invention can also be applied to a so-called dual damascene process.

Example 6 Using a sample in which copper wiring was exposed at the bottom of the via hole in the same process as in Example 5, the concentrations of THFA and alkanolamine were changed and evaluated. No. of Table 7 The stripper composition obtained by adding 1% of benzotriazole to each of compositions 21 to 23 was immersed at 80 ° C. for 10 minutes to prepare three types of samples. The sample was observed using the same evaluation method and evaluation criteria as in Example 5.

[0096]

[Table 7]

As described above, it is possible to reduce the damage to the low dielectric constant film by adding the alkanolamine as the component (e), but the component (a) is reduced by using a large amount (No). .23), the peelability tends to decrease.

Example 7 For samples similar to those in Examples 5 and 6, as shown in Table 8, the application composition (mainly water content) and the treatment temperature were changed, and adenine was added at 1% as an anticorrosive component. The same evaluation was performed using the added release agent.

[0099]

[Table 8]

As described above, the water content (moisture content) of the component (d) has a proper range, and when evaluated further,
It was confirmed that the range of 5 to 30 mass% is preferable.

Example 8 For treatment temperature of 80 ° C., THFA 68% by mass, HF
With respect to the composition of 1% by mass and 2% by mass of 2MAE, 1% by mass of the anticorrosive component shown in Table 8 was added, and 100% by adding water.
Stripping treatment was performed using the stripping agent composition which was made to be mass%. For a treatment temperature of 23 ° C., 1% by mass of the anticorrosive component shown in Table 4 was added to a composition of 55% by mass of THFA, 4% by mass of HF and 20% by mass of 2MAE, and 100% by mass of water was added. A release treatment was performed using the release agent composition. Further, when two components were mixed and used as the anticorrosive component, the upper component and the lower component were mixed in a ratio of 9: 1. Similar to Example 5, the peelability of the via bottom and the Cu corrosion resistance were evaluated. The results are also shown in Table 9.

[0102]

[Table 9]

As described above, a benzotriazole-based anticorrosive agent can be used without problems at a high temperature (80 ° C.), but at a low temperature (23 ° C.), a residue was generated on the bottom of the via. At low temperatures, adenine and o-phthalic acid are the main components, and they are used either as a mixture or by adding quinaldic acid to each of them, thereby achieving both excellent corrosion resistance and residue removability. You can

Example 9 Ammonium fluoride was added to 2MAE so that the fluorine content was 2.5%, and the mixed solution was treated under the conditions shown in Table 10. Furthermore, 1% by mass of benzotriazole and 69% by mass of THFA were added so that this mixed solution would be 20% by mass of the whole.
And the balance water was added to prepare a stripper composition. Wafer slices having an HSQ film formed on the entire surface thereof were treated with this composition at 80 ° C. for 10 minutes to prepare three types of samples.

The film thickness of these samples was measured by an ellipsometer to obtain the etch rate. Further, the FT-IR measuring device was used to measure the IR spectra of SiH and SiO of the HSQ film, and the value obtained by dividing the SiH-derived peak intensity by the SiO-derived peak intensity was used as the amount of change in the SiH film quality. The results are also shown in Table 10. In addition, reference (ref)
As the release agent composition, HF was added so that the fluorine concentration was the same, and the etch rate and the change in film quality were evaluated in the same manner.

[0106]

[Table 10]

As described above, after mixing ammonium fluoride with the alkanolamine, by heating treatment or leaving it at room temperature for a long time to remove ammonium ions from the system, the etching rate can be suppressed and at the same time HSQ It can be seen that film quality damage is suppressed. According to this embodiment, ammonium fluoride is used instead of dangerous hydrofluoric acid, and the same effect as that of hydrofluoric acid is obtained. Therefore, workability is significantly improved.

[0108]

As described above, according to the present invention, it is possible to provide a stripper composition having excellent removability of unnecessary substances such as etching residues.
In particular, it has become possible to provide an excellent release agent composition with less damage to the low dielectric constant film.

In particular, the release agent composition of the present invention can provide sufficient anticorrosion property even if the composition of the expensive anticorrosive component is minimized.

[Brief description of drawings]

FIG. 1 is a process cross-sectional view showing an example of a manufacturing process of a semiconductor device using a release agent composition of the present invention.

FIG. 2 is a process cross-sectional view showing an example of a manufacturing process of a semiconductor device using the release agent composition of the present invention, showing the process following FIG.

[Explanation of symbols]

1 silicon oxide film 2 silicon nitride film (SiN (SiCN)) 3 silicon oxide film (SiO ₂ (LowK)) 4 barrier metal film 5 copper film 6 silicon nitride film (SiN (SiCN)) 7 low dielectric constant film 8 silicon oxide Film 9 Resist film 10 Via hole 11 Etching residue 12 Etching residue 13 Barrier metal film 14 Tungsten film

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 2, 2002 (2002.10.
2)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0101

[Correction method] Change

[Correction content]

Example 8 For treatment temperature of 80 ° C., THFA 68% by mass, HF
With respect to the composition of 1% by mass and 2% by mass of 2MAE, 1% by mass of the anticorrosive component shown in Table 9 was added, and 100% by adding water.
Stripping treatment was performed using the stripping agent composition which was made to be mass%. For a treatment temperature of 23 ° C., 1% by mass of the anticorrosive component shown in Table 9 was added to a composition of 55% by mass of THFA, 4% by mass of HF and 20% by mass of 2MAE, and 100% by mass of water was added. A release treatment was performed using the release agent composition. Further, when two components were mixed and used as the anticorrosive component, the upper component and the lower component were mixed in a ratio of 9: 1. Similar to Example 5, the peelability of the via bottom and the Cu corrosion resistance were evaluated. The results are also shown in Table 9.

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) H01L 21/027 H01L 21/30 572B (72) Inventor Keiji Hirano 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation In-house (72) Inventor Kenichi Tokioka 5-7-1, Shiba, Minato-ku, Tokyo NEC Corporation In-company (72) Hidemitsu Aoki 5-7-1, Shiba, Minato-ku, Tokyo NEC Corporation Company (72) Inventor Masayuki Takashima 4-5-3 Kitahama, Chuo-ku, Osaka-shi, Osaka Sumitomo Chemical Co., Ltd. F-term (reference) 2H096 AA25 LA03 4H003 BA12 DA14 DA15 EA05 EB04 EB07 EB14 EB20 ED02 ED28 ED29 5F046 MA02

Claims (27)

[Claims] 1. A stripping composition comprising: (a) at least one alcohol having an ether bond in the molecule and (b) an anticorrosive agent. 2. The stripper composition according to claim 1, wherein the component (a) is an alcohol having a cyclic ether structure in the molecule. 3. The stripper composition according to claim 2, wherein the alcohol having a cyclic ether structure in the molecule is represented by the following formula. X- (A-OH) _n (In formula, X is a cyclic ether structure, A is a C1-C8 hydrocarbon chain, n is 1 or more and represents the number of substitutions to a cyclic ether structure.) 4. The stripper composition according to claim 2, wherein the alcohol having a cyclic ether structure in the molecule is furfuryl alcohol or tetrahydrofurfuryl alcohol. 5. The release agent according to claim 1, wherein the component (a) is a mixture of alcohols having a cyclic ether structure in the molecule and alcohols having a glycol ether structure in the molecule. Composition. 6. The release agent composition according to claim 1, which contains at least one organic or inorganic weak acid as the component (c). 7. The stripper composition according to claim 6, wherein the component (c) is lactic acid. 8. The method according to claim 1, wherein the component (d) contains water.
The release agent composition according to any one of items 1 to 7. 9. The stripper composition according to claim 8, wherein the content of the water is less than 70% by mass. 10. The component (b) is (1) a purine derivative, (2) a dibasic or more compound having at least one carboxyl group and capable of forming a chelate with a metal, and having a hydrophobic property. A compound having a group, (3) a mixture of the purine derivative and quinaldic acid, or (4) the above (2)
A mixture of the compound of claim 1 and quinaldic acid, (5) a mixture of the purine derivative of (1) and the compound of (2), and (6) a purine derivative of (1), the compound of (2) and quinaldic acid. The stripper composition according to any one of claims 1 to 9, which is an anticorrosive selected from a mixture. 11. The stripper composition according to claim 10, wherein the compound (2) is o-phthalic acid. 12. The stripper composition according to claim 10, wherein the purine derivative (1) is adenine or a derivative thereof. 13. The stripper composition according to claim 1, further comprising at least one kind of amines as the component (e). 14. The stripper composition according to claim 13, wherein the amines are alkanolamines. 15. The base equivalent value of the amine is larger than the equivalent value of the acid component in the system.
The release agent composition according to. 16. The component (b) is 0.001 to 15% by mass, the component (c) is 0 to 15% by mass, the component (d) is 2% by mass or more and less than 70% by mass, and the component (e) is 1 to 1% by mass. The release agent composition according to any one of claims 13 to 15, wherein the release agent composition contains 40% by mass and the remaining component (a) is 30% by mass or more. 17. The component (a) is at least one alcohol having an ether bond in the molecule, the component (c ′) is at least one hydrofluoric acid and a salt thereof, and the component (d) is water. A release agent composition comprising: 18. The stripper composition according to claim 17, wherein the component (a) is an alcohol having a cyclic ether structure in the molecule. 19. The stripper composition according to claim 18, wherein the alcohol having a cyclic ether structure in the molecule is furfuryl alcohol or tetrahydrofurfuryl alcohol. 20. The stripping composition according to claim 17, further comprising at least one kind of amines as the component (e). 21. The stripper composition according to claim 20, wherein the amines are alkanolamines. 22. The component (c ') is 0.01 to 15% by mass, the component (d) is 5 to 30% by mass, and the component (e) is 10 to 10% by mass.
The release agent composition according to claim 20 or 21, wherein the release agent composition contains 40% by mass and the balance of the component (a) is 20% by mass or more. 23. The release agent composition according to claim 17, further comprising an anticorrosive agent as the component (b). 24. The component (b) is a dibasic or higher compound having (1) a purine derivative, (2) at least one carboxyl group and capable of forming a chelate with a metal, and having a hydrophobic property. A compound having a group, (3) a mixture of the purine derivative and quinaldic acid, or (4) the above (2)
A mixture of the compound of claim 1 and quinaldic acid, (5) a mixture of the purine derivative of (1) and the compound of (2), and (6) a purine derivative of (1), the compound of (2) and quinaldic acid. 24. The stripper composition of claim 23, which is an anticorrosive agent selected from a mixture. 25. The stripper composition according to claim 24, wherein the compound (2) is o-phthalic acid. 26. The stripper composition according to claim 24, wherein the purine derivative (1) is adenine or a derivative thereof. 27. The release agent composition according to claim 23, which contains the component (b) in an amount of 0.001 to 15% by mass.