JP3054145B1 - Photo-resist stripping composition and photo-resist stripping method using the same - Google Patents

Abstract

An exfoliating solution for a photoresist, which has excellent exfoliation properties of a photoresist layer and a deposition (residue) generated after etching and ashing, and is excellent in anticorrosion of a substrate on which a metal film, an inorganic film and the like are formed. Provided are a composition and a photoresist stripping method using the same. SOLUTION: The color difference (ΔE ^* _ab ) in the L ^* a ^* b ^* color system defined in JIS Z 8730 is 30 to 18.
A photoresist stripping solution composition of 0 (reference value: pure water) and a photoresist stripping method using the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photoresist stripping composition and a photoresist stripping method using the same. More specifically, a photoresist layer and deposition (residues) generated after etching or ashing
The present invention relates to a photoresist stripping composition and a photoresist stripping method using the same, which are excellent in stripping properties and excellent in anticorrosion of a substrate on which a metal film, an inorganic film and the like are formed.
INDUSTRIAL APPLICABILITY The present invention is suitably applied to the manufacture of semiconductor elements such as ICs and LSIs and liquid crystal panel elements.

[0002]

2. Description of the Related Art In semiconductor devices such as ICs and LSIs and liquid crystal panel devices, a photoresist is uniformly formed on a conductive metal layer such as a Nesa film formed on a substrate by CVD or the like, or on an insulating layer such as a SiO ₂ film. To form a resist pattern by selectively exposing and developing the resist pattern, and using the pattern as a mask to selectively etch the conductive metal layer and the insulating layer to form a fine circuit. Is manufactured by removing the photoresist layer with a stripping solution. Here, other examples of the metal layer include aluminum (Al); aluminum-silicon (Al-Si), and aluminum-copper (Al-C).
u), aluminum-silicon-copper (Al-Si-Cu)
Aluminum alloy (Al alloy); titanium (Ti);
Titanium alloys (Ti alloys) such as titanium nitride (TiN) and titanium tungsten (TiW); copper (Cu) and the like. In addition, inorganic films such as an amorphous silicon (a-Si) film and a polysilicon (poly-Si) film are also used. These metal layer, insulating layer, inorganic film,
It is formed on a substrate in a single layer or a plurality of layers.

In recent years, a photoresist stripping composition using alkanolamines has been used as a stripping composition for removing the photoresist layer (Japanese Patent Laid-Open No. Sho 62-62).
49355, JP-A-63-208043,
etc).

However, in today's semiconductor device and liquid crystal device manufacturing processes, in addition to the above-described method, it is also necessary to remove the photoresist layer from which the photoresist layer has been subjected to dry etching, ashing, ion implantation, and the like. I have. By these processes, the photoresist layer after the process becomes a deteriorated film. In recent years, these processing conditions have become more severe, and the deteriorated film has been changed from an organic film to a film having inorganic properties. Therefore, a stripping solution composition using alkanolamines has an adverse effect on the releasability of the deteriorated film. It is enough.

[0005] Recently, a photoresist stripper composition containing hydroxylamines has been proposed as a photoresist stripper composition having more excellent stripping properties of the deteriorated film. For example, JP-A-4-289866 describes a photoresist stripper composition containing hydroxylamine and alkanolamine. Also, JP-A-6
JP-266119 discloses a photoresist stripper composition containing hydroxylamine and alkanolamine and further containing a chelating agent (anticorrosive) such as catechol.

[0006] The stripping solution composition containing these hydroxylamines improves the releasability of the deteriorated film as compared with the stripping solution using the above-mentioned alkanolamines.
There is a problem that corrosion appears on an Al alloy such as l-Si, Al-Cu, or Al-Si-Cu, or on a substrate on which pure titanium (Ti) is deposited.

[0007] To solve the above problems, see, for example, JP-A-9-96.
Japanese Patent Publication No. 911 discloses a photoresist stripping composition containing a specific amount of hydroxylamines, water, amines having a predetermined acid dissociation constant, a water-soluble organic solvent, and an anticorrosive. Excellent, Al and Al alloy,
An excellent anticorrosion effect is also provided for a substrate on which pure titanium (Ti) is formed.

However, none of the above-mentioned photoresist stripper compositions containing hydroxylamines has been examined for the anticorrosion properties of a substrate having an inorganic film such as a polysilicon film.

In recent years, in particular, in the field of liquid crystal devices and the like, a substrate on which an inorganic film such as an amorphous silicon film or a polysilicon film is formed has been widely used. In particular, a polysilicon film has high mobility and is often used for a liquid crystal panel and the like from the viewpoint of miniaturization of a liquid crystal device. Therefore, there is an increasing demand for a photoresist stripper composition that is excellent in the anticorrosion properties of a substrate having an inorganic film such as a polysilicon film.

Therefore, the substrate having various metal layers and various inorganic films used in the fields of semiconductor integrated circuits, liquid crystal panel elements and the like does not cause corrosion and has a deteriorated photoresist film, etching, There has been a demand for the development of a photoresist stripping solution having excellent removability of deposition (residues) generated after ashing.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has excellent exfoliation properties of a photoresist film and a deposition (residue) generated after etching or ashing, and a metal layer. It is an object of the present invention to provide a photoresist stripper composition which is excellent in anticorrosion properties of a substrate on which an inorganic film or the like is formed, and a photoresist stripping method using the same.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the color difference (ΔE ^* _ab ) in the L ^* a ^* b ^* color system is 30 to 180. It has been found that the above problems can be solved by using a photoresist stripping composition, and the present invention has been completed based on this.

In the course of this study, the above-mentioned conventional hydroxylamine-based photoresist stripping compositions all have a color difference of 20 or less, and their light transmittance to light having a wavelength of 500 nm exceeds 70%. It was also found that these conventional stripping compositions did not provide a sufficiently satisfactory effect in terms of anticorrosion on inorganic films such as polysilicon films.

That is, the present invention relates to JIS Z 8730.
Color difference (ΔE ^*) by the L ^* a ^* b ^* color system defined in
_ab ) is 30 to 180 (reference value: pure water).

In the above, the color difference (ΔE ^* _ab ) is 50 to
A value of 140 is preferred.

In the above, it is preferable that the light transmittance for light having a wavelength of 500 nm is 70% or less (cell length = 1 cm).

In the above, it is preferable to contain at least an oxide of an aromatic hydroxy compound.

The present invention also provides a step of providing a photoresist layer on a substrate having a metal layer formed thereon, a step of selectively exposing the photoresist layer, a step of developing the exposed photoresist layer to provide a resist pattern, Selectively etching the substrate using the pattern as a mask, further including, if desired, ashing the resist pattern after the etching step, and removing the resist pattern after the etching step or the ashing step from the substrate. The present invention relates to a photoresist stripping method, which comprises stripping a resist pattern using the photoresist stripper composition of the present invention.

In the above separation method, it is preferable to use a substrate on which an inorganic film is further formed.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The color difference (ΔE ^* _ab ) in the photoresist stripper composition of the present invention is a value calculated based on pure water.

The photoresist stripper composition of the present invention comprises:
The color difference (ΔE ^* _ab ) in the L ^* a ^* b ^* color system defined in JIS Z 8730 is 30 to 180 (reference value:
Pure water), preferably 50 to 140, particularly preferably 70
１２０120.

The L ^* a ^* b ^* color system is based on the International Commission on Illumination (Com
mission Internationale de l'Eclairage (CIE) is 19
This is the color system recommended in 1976.

Defined in JIS Z 8730
L^*a^*b^*Color difference by color system (ΔE^* _ab) Means
Is calculated by the following calculation formula.

[0025]

ΔE ^* _ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δ
b ^* ) ² ] ^1/2

(Where, ΔL ^* , Δa ^* , Δb
^{* Indicates} the difference in CIE1976 lightness L ^{* and} the difference in color coordinates a ^* , b ^* between two object colors in the L ^* a ^* b ^* color system specified in JIS Z 8729)

Here, the respective indices L ^* (lightness), a ^* , b ^* (chromaticity) in the L ^* a ^* b ^* color system are represented by the XYZ color system (C
Using tristimulus values X, Y, and Z in other IE-recommended color systems, it can be obtained from the following formulas 2 and 3 (JIS Z 8729). The formulas shown in Equations 2 and 3 below indicate that X / X _n , Y / Y _n , and Z / Z _n are _equal to 0.
Applied when indicating a value greater than 008856.

[0028]

L ^* = 116 (Y / Y _n ) ^1/3 −16

(Where Y represents the tristimulus value in the XYZ system; Y _n represents the value of Y by the standard light of the perfect diffuse reflection surface)

[0030]

A ^* = 500 [(X / X _n ) ^1/3 − (Y / Y _n ) ^1/3 ] b ^* = 200 [(Y / Y _n ) ^1/3 − (Z / Z _n ) ^1/3 ]

(However, in Equation 3, X, Y, and Z are in the XYZ system.
Indicates the tristimulus value in X;_n, Y_n, Z _nIs perfect diffuse reflection
(Shows tristimulus values in the XYZ system of the surface)

The color difference (ΔE ^* _ab ) can be measured and calculated using various commercially available spectrophotometers and the like.

Specifically, for example, first, the photoresist stripping composition of the present invention is used as a sample solution, and pure water is prepared as a standard solution. These sample solution and pure water were respectively supplied with a self-recording spectrophotometer “UV-3100PC” (Shimadzu Corporation)
(For example, wavelength 3)
Spectral transmittance in the visible light range of 80 to 780 nm) is measured. Using the color measurement software (manufactured by Shimadzu Corporation) attached to the above apparatus, the data was used to calculate the tristimulus values X, Y, and Z (XYZ color system) for the sample solution and water as follows. Calculated by the calculation formula shown in FIG.

[0034]

(Equation 4)

Next, with respect to the sample solution and pure water, the values of X, Y, and Z are used to calculate
A parameter L ^* representing lightness, a parameter a ^* representing chromaticity,
b ^* is calculated, and finally the difference between the color value of the sample solution and the color value of pure water, that is, the color difference (ΔE ^* _ab ) is calculated from the calculation formula shown in Expression 1.

In the present invention, the color difference (ΔE ^* _ab ) is 30 to 1
80, preferably 50 to 140, particularly preferably 70 to
By setting the value to 120, peeling of the photoresist film,
In addition, it is possible to obtain a photoresist stripping liquid composition which is excellent in exfoliation of various depositions (residues) generated by etching and ashing and is also excellent in anticorrosion properties of various metal films and inorganic films formed on a substrate. .

The photoresist stripping composition of the present invention comprises:
In order to further improve the effects of the present invention, 500
The light transmittance for light having a wavelength of nm is 70% or less (cell length =
1 cm), particularly preferably 50% or less.

As the photoresist stripper composition of the present invention having the above-mentioned properties, specifically, those containing at least an oxide of an aromatic hydroxy compound are preferred.

As the aromatic hydroxy compound, phenol, cresol, xylenol, catechol (= 1,
2-dihydroxybenzene), tert-butylcatechol, resorcinol, hydroquinone, pyrogallol,
1,2,4-benzenetriol, p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol,
p-hydroxyphenethyl alcohol, p-aminophenol, m-aminophenol, diaminophenol,
Aminoresorcinol, p-hydroxybenzoic acid, o-
Hydroxybenzoic acid, 2,4-dihydroxybenzoic acid,
Examples thereof include 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid (= protocatechuic acid), and 3,5-dihydroxybenzoic acid.

The oxide of the aromatic hydroxy compound refers to an oxide obtained by oxidizing the aromatic hydroxy compound to convert a part or all of the —OH groups in the compound into ＝ O groups. In the present invention, each oxide of catechol and tert-butyl catechol, that is, 1,2-benzoquinone,
Tert-butyl-1,2-benzoquinone is preferably used. The oxide of the aromatic hydroxy compound may be used alone or in combination of two or more.

The compounding of the oxide of the aromatic hydroxy compound is preferably used because it contributes to maintaining the color difference (ΔE ^* _ab ) of the stripping composition at the high value shown in the present invention.
More preferably, the stripping solution composition for a photoresist of the present invention has a color difference (ΔE ^* _ab ) of 30 to 1 from the viewpoint of the strippability of a photoresist film and the anticorrosion property of an inorganic film such as a polysilicon film.
Most preferably, the oxide of the aromatic hydroxy compound is present in the form of a mixture with the aromatic hydroxy compound as long as the oxide has a value in the range of 80.

The means for incorporating the oxide of the aromatic hydroxy compound into the photoresist stripping composition is not particularly limited. For example, an oxide of the aromatic hydroxy compound is prepared in advance, and this is removed. The aromatic hydroxy compound may be added to the composition or, after the aromatic hydroxy compound is added to the stripping composition, the aromatic hydroxy compound in the composition may be oxidized to generate the oxide.

Specifically, (i) an aromatic hydroxy compound is air-oxidized for a predetermined time to obtain an oxide, which is added to a stripping solution composition; and (ii) an aromatic hydroxy compound is stripped from the stripping solution composition. was added to, by which a predetermined time air oxidation, is contained oxides in the release liquid composition, after addition of (iii) an aromatic hydroxy compound in the stripping liquid composition, O ₂ gas to the composition For example, the aromatic hydroxy compound is forcibly oxidized by blowing in, and the oxide is contained in the stripping solution. In the present invention, it is preferable to use the above-mentioned means (iii).

The stripping solution composition of the present invention may further contain, in addition to the above-mentioned oxide of the aromatic hydroxy compound, other additional components used in a general hydroxylamine-based stripping solution composition. As such additional components,
Examples include, but are not limited to, amines, hydroxylamines, water-soluble organic solvents, water and the like having a specific acid dissociation constant (pKa).

The photoresist stripping composition of the present invention is specifically exemplified by the following system.

[1] Aromatic hydroxy compound and its oxide, and pKa in aqueous solution at 25 ° C. of 7.5 to 1
(3) System containing amines: In addition to the aromatic hydroxy compound and its oxide, the amine having the above-mentioned specific pKa is further blended for further improving the peelability.

Specific examples of such amines include monoethanolamine, diethanolamine, triethanolamine, 2- (2-aminoethoxy) ethanol,
N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine,
Alkanolamines such as N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine; diethylenetriamine, triethylenetetramine, propylenediamine; , N-diethylethylenediamine, N, N′-diethylethylenediamine, 1,4-butanediamine, N-ethyl-ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,6-hexanediamine and the like Alkylene polyamines; aliphatic alkyls such as 2-ethyl-hexylamine, dioctylamine, tributylamine, tripropylamine, triallylamine, heptylamine and cyclohexylamine; Amines; aromatic amines such as benzylamine and diphenylamine; and cyclic amines such as piperazine, N-methyl-piperazine, methyl-piperazine, and hydroxylethylpiperazine. Among these, monoethanolamine, 2- (2-aminoethoxy) ethanol, diethylenetriamine, triethylenetetramine, cyclohexylamine, piperazine, and the like are preferred from the viewpoints of anticorrosion properties and peelability.

The mixing ratio of each component is preferably 2 to 20% by weight, particularly 5 to 15% by weight in terms of the aromatic hydroxy compound in terms of the aromatic hydroxy compound in the stripping solution composition. The amines having a pKa of 7.5 to 13 in an aqueous solution at 25 ° C are preferably at least 2% by weight or more, particularly 5% by weight or more. Further, water may be added for further improving the releasability.

[2] Aromatic hydroxy compound and its oxide, and pKa in aqueous solution at 25 ° C. of 7.5 to 1
System containing amines 3 and hydroxylamines:
In addition to the aromatic hydroxy compound and its oxide, the pKa in the 25 ° C. aqueous solution described in [1] above is 7.
By blending 5 to 13 amines with hydroxylamines, the releasability can be further improved.

Such hydroxylamines are represented by the following general formula (I)

[0051]

Embedded image

(Wherein R ¹ and R ² each independently represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms).

Here, the lower alkyl group having 1 to 6 carbon atoms includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group,
Examples include tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, 3-methylpentyl, 2,2-dimethylbutyl, and 2,3-dimethylbutyl. Is done. R ¹ and R ² may be the same or different.

Specific examples of the above-mentioned hydroxylamines include hydroxylamine (NH ₂ OH), N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine and the like. Among them, hydroxylamine (NH ₂ OH) is preferably used. These hydroxylamines may be used alone or in combination of two or more.

Water is inevitably contained in the hydroxylamines, but the concentration, the releasability and the like may be adjusted by further adding water.

The proportion of the above components is preferably 2 to 20% by weight, particularly 5 to 15% by weight, in terms of the aromatic hydroxy compound in the composition. PKa in aqueous solution at 25 ° C
Is preferably at least 2% by weight, more preferably at least 5% by weight, and the content of hydroxylamines is preferably 2 to 30% by weight, particularly preferably 5 to 25% by weight. The balance is water.

[3] Aromatic hydroxy compound and its oxide, and pKa in aqueous solution at 25 ° C. of 7.5 to 1
3 containing amines and a water-soluble organic solvent: in addition to the aromatic hydroxy compound and its oxide, the pKa in the aqueous solution at 25 ° C. described in the above [1] is 7.5.
By further mixing the water-soluble organic solvent with the amines of Nos. 13 to 13, the releasability can be further improved.

The water-soluble organic solvent may be any organic solvent that is miscible with water, and any water-soluble organic solvent used in conventional organic amine stripping solutions can be used.

Examples of such water-soluble organic solvents include sulfoxides such as dimethyl sulfoxide; dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl)
Sulfones such as sulfone and tetramethylene sulfone;
Amides such as N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, N, N-diethylacetamide;
N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-
Lactams such as pyrrolidone; imidazolidinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone and 1,3-diisopropyl-2-imidazolidinone; ethylene glycol And polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. And its derivatives. These may be used alone or in combination of two or more. Among these, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-
Dimethyl-2-imidazolidinone, diethylene glycol monobutyl ether, and the like are preferable because of excellent releasability of the deteriorated film. Among them, dimethyl sulfoxide is preferable because of its excellent anticorrosion effect on the substrate.

The proportion of the above components is preferably 2 to 20% by weight, particularly 5 to 15% by weight, in terms of the aromatic hydroxy compound in the composition. PKa in aqueous solution at 25 ° C
Is preferably at least 2% by weight or more, particularly 5% by weight or more, and the water-soluble organic solvent is preferably 20 to 80% by weight, particularly 25 to 70% by weight. Further, water may be added for further improving the releasability.

[4] Aromatic hydroxy compound and its oxide, and pKa in aqueous solution at 25 ° C. of 7.5 to 1
3, a system containing an amine, a hydroxylamine and a water-soluble organic solvent: in addition to the aromatic hydroxy compound and its oxide, the pKa in the aqueous solution at 25 ° C. described in the above [1] is 7.5 to 7.5. 13 amines and the above [2]
And the water-soluble organic solvent described in [3] above. The stripper composition containing all of these components has a good balance between strippability and anticorrosion properties, and effectively removes the photoresist film after ion implantation, the photoresist film after ashing, as well as any metal layer, inorganic film, etc. It has an effective anticorrosion effect.

The proportion of the above components is preferably 2 to 20% by weight, particularly 5 to 15% by weight, in terms of the aromatic hydroxy compound in the composition. PKa in aqueous solution at 25 ° C
Is preferably 2 to 40% by weight, more preferably 5 to 35% by weight, and hydroxylamines is preferably 2 to 30% by weight, particularly 5 to 15% by weight.
And the content of the water-soluble organic solvent is preferably 20 to 80% by weight, particularly 25 to 70% by weight. The balance is water.

Further, the photoresist stripper composition of the present invention may contain a benzotriazole compound. The benzotriazole-based compound can be basically used arbitrarily as long as it has a benzotriazole skeleton. Specifically, for example, the following general formula (II)

[0064]

Embedded image

[Wherein R ³ is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms (however, the structure may have an amide bond or an ester bond). Or an aryl group; R ⁴ and R ⁵ each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group, an amino group,
Represents a hydroxyl group, a cyano group, a formyl group, a sulfonylalkyl group, or a sulfo group].

In the above, the substituted hydrocarbon group includes
Examples thereof include a hydroxyalkyl group and an alkoxylalkyl group.

In the general formula (II), R ³ is specifically a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (that is, a methyl group, an ethyl group, a propyl group, an isopropyl group), a carbon atom. Preferred are hydroxyalkyl groups, hydroxyl groups, and the like of formulas 1 to 3. Among them, a hydroxyalkyl group having 1 to 3 carbon atoms is particularly preferred.

Specific examples of the benzotriazole compound include, for example, benzotriazole, 5,6-dimethylbenzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-aminobenzotriazole, 1-phenylbenzotriazole , 1
-Hydroxymethylbenzotriazole, methyl 1-benzotriazolecarboxylate, 5-benzotriazolecarboxylic acid, 1-methoxybenzotriazole, 1-
(2,2-dihydroxyethyl) benzotriazole,
Examples thereof include 1- (1,2-dihydroxypropyl) benzotriazole and 1- (2,3-dihydroxypropyl) benzotriazole. Among these, benzotriazole, 1-hydroxybenzotriazole, 1-methoxybenzotriazole, 1- (2,2-
Dihydroxyethyl) benzotriazole, 1- (1,
2-dihydroxypropyl) benzotriazole, 1-
(2,3-Dihydroxypropyl) benzotriazole and the like are preferably used, and 1- (1,2-dihydroxypropyl) benzotriazole is particularly preferably used. These may be used alone or in combination of two or more.

Benzotriazole-based compounds include copper (C
In the case where u) or a substrate on which an inorganic film such as a polysilicon film is formed is used, corrosion on these can be particularly effectively prevented.

In addition to the above, acetylene alcohol, a carboxyl group-containing organic compound, an anhydride thereof, and the like can be further blended to improve the corrosion resistance.

The acetylene alcohol includes 2-
Butyn-1,4-diol, 3,5-dimethyl-1-hexyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, 3,6
-Dimethyl-4-octyne-3,6-diol, 2,
4,7,9-Tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol and the like can be mentioned, and among them, 2-butyne-1,4
-Diols are preferred. These acetylene alcohols may be used alone or in combination of two or more.

The carboxyl group-containing organic compound and its anhydride include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, benzoic acid and phthalic acid. acid,
1,2,3-benzenetricarboxylic acid, glycolic acid,
Lactic acid, malic acid, citric acid, acetic anhydride, phthalic anhydride,
Maleic anhydride, succinic anhydride, salicylic acid and the like can be mentioned. Among them, formic acid, phthalic acid, benzoic acid, phthalic anhydride and salicylic acid are preferable, and phthalic acid, phthalic anhydride and salicylic acid are particularly preferable. These compounds may be used alone or in combination of two or more.

One or two of these optional additives may be used depending on the resist composition to be used, stripping conditions, conditions for forming a deteriorated resist film by ashing, ion implantation, plasma processing, or the like, or rinsing conditions in the post-process. The above can be used in combination as appropriate.

The photoresist stripper composition of the present invention comprises:
It can be advantageously used for photoresists that can be developed with an aqueous alkaline solution, including negative and positive photoresists. Examples of such a photoresist include (i) a positive photoresist containing a naphthoquinonediazide compound and a novolak resin, (ii) a compound which generates an acid upon exposure, a compound which is decomposed by an acid to increase solubility in an aqueous alkali solution, and an alkali-soluble compound. A positive photoresist containing a resin, (iii) a compound which generates an acid upon exposure, a positive photoresist containing an alkali-soluble resin having a group which is decomposed by an acid and has increased solubility in an alkaline aqueous solution, and (iv) light Examples include, but are not limited to, a negative photoresist containing an acid-generating compound, a crosslinking agent and an alkali-soluble resin.

The photoresist stripping method of the present invention forms a resist pattern obtained by lithography,
Next, there is a case where the photoresist film and the deposition (residue) after the etching step are stripped, and a case where the photoresist film (degraded film) and the deposition (residue) after the ashing step are stripped.

As an example of removing the photoresist film and the deposition (residue) after the former etching step, (I) a step of providing a photoresist layer on a substrate on which a metal layer is formed, and (II) a step of providing the photoresist layer Selectively exposing, (III) developing the exposed photoresist layer to provide a resist pattern, (IV) selectively etching the substrate using the resist pattern as a mask, and (V) after etching. In the method of removing a photoresist pattern from the substrate, a method of removing the etched resist pattern by using the photoresist remover composition of the present invention may be mentioned.

As an example of removing the photoresist film (degraded film) and the deposition (residue) after the latter ashing step, (I) a step of providing a photoresist layer on a substrate on which a metal layer is formed; II) selectively exposing the photoresist layer, (III) developing the exposed photoresist layer to provide a resist pattern, (IV) selectively etching the substrate using the resist pattern as a mask, (V) a step of ashing a resist pattern; and (VI) a method of peeling a resist pattern after ashing from a substrate, wherein the resist pattern after ashing is formed by using the photoresist stripping composition of the present invention. There is a method of peeling.

As the substrate on which the metal layer is formed, aluminum (Al); aluminum-silicon (Al-Si),
Aluminum alloys (A) such as aluminum-copper (Al-Cu) and aluminum-silicon-copper (Al-Si-Cu)
alloy); titanium (Ti); titanium nitride (Ti
N), a titanium alloy (Ti alloy) such as titanium tungsten (TiW); and a substrate on which a metal film such as copper (Cu) is formed. If desired, an inorganic film such as a polysilicon (poly-Si) film may be formed on the substrate.
In the present invention, particularly when a substrate having both a metal layer and a polysilicon film formed on the substrate is used, there is an effect that the corrosion prevention effect of the polysilicon film is extremely excellent.

Coating, drying, exposure, development, etching and ashing are all conventional means and are not particularly limited. The etching may be either wet etching or dry etching, or a combination of both. After the etching, a metal film etching residue (metal deposition) and other etching residue of the insulating film are generated. Ashing is originally a method of removing a resist pattern, but ashing often leaves a resist pattern partially as an altered film.

The present invention is effective for removing a photoresist film, a deteriorated film, a residue (deposition), etc. after the etching and the ashing.

After the developing step (III) and the peeling step (V) or (VI), a rinsing treatment using a conventionally used pure water or a lower alcohol and a drying treatment are carried out. Is also good.

Depending on the type of photoresist, a post-exposure bake, which is a post-exposure bake usually performed on a chemically amplified photoresist, may be performed. Further, post baking after forming the resist pattern may be performed.

The peeling treatment is usually performed by a dipping method or a spray method. Note that the peeling time is not particularly limited as long as it is a sufficient time for peeling, but usually,
It is about 10 to 20 minutes.

[0084]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, the compounding amount is shown by weight% unless otherwise specified.

Example 1 First, a stripper composition comprising 10% by weight of catechol, 30% by weight of monoethanolamine, 15% by weight of hydroxylamine, 30% by weight of dimethyl sulfoxide, and 15% by weight of water was placed at room temperature (25%).
° C.) for 2 hours O ₂ bubbling (stripping liquid composition 200mL
Respect by performing an O ₂ ratio of gas flow 3L / min), at least to a portion thereof with 1,2-benzoquinone by oxidation of catechol in the composition, to prepare a photoresist stripping liquid composition.

[0086] Using the photoresist stripping liquid composition, by the following method, the color difference (ΔE ^* _{a b)} and light transmission (500 nm) was measured. Table 2 shows the results.

[Measurement of Color Difference (ΔE ^* _ab )] The above-mentioned photoresist stripping composition and pure water as a standard solution were each mixed with a self-recording spectrophotometer “UV-3100PC” (manufactured by Shimadzu Corporation) (cell) (Length = 1 cm), the spectral transmittance at a predetermined wavelength (visible light range of wavelength 380 to 780 nm) was measured.

The obtained data was calculated using color measuring software (manufactured by Shimadzu Corporation) attached to the above apparatus to obtain a color difference (ΔE ^* _ab ). Table 2 shows the results.

[Measurement of Light Transmittance (500 nm)] The above-mentioned photoresist stripping composition was subjected to a self-recording spectrophotometer “UV-3”.
100PC "(manufactured by Shimadzu Corporation) (cell length = 1c)
m), the light transmittance at a wavelength of 500 nm was measured. Table 2 shows the results.

Next, THMR-iP3 which is a positive photoresist composition comprising a naphthoquinonediazide compound and a novolak resin is formed on a substrate having an Al-Si layer and a polysilicon (poly-Si) film formed on a silicon wafer.
300 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) using a spinner, pre-baking at 90 ° C. for 90 seconds, and a film thickness of 2.
A 0 μm photoresist layer was formed. This photoresist layer was exposed through a mask pattern using NSR-2005i10D (manufactured by Nikon Corporation) and developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) to form a photoresist pattern. Next, post-baking was performed at 120 ° C. for 90 seconds.

Next, the substrate having the resist pattern formed under the above conditions was subjected to dry etching. This was added to the photoresist stripper composition prepared as described above.
A immersion treatment was performed at 0 ° C. for 20 minutes to perform a photoresist film peeling treatment.

The substrate after the peeling treatment was sufficiently rinsed with pure water, and the peeling property of the photoresist film and the anticorrosion property of the polysilicon film were evaluated by observing an SEM (scanning electron microscope) photograph. Table 3 shows the results.

The peelability of the photoresist film and the anticorrosion of the polysilicon film were evaluated as follows.

[Removability of photoresist film] ：: Good peelability ×: Residue remained

[Corrosion protection of polysilicon film] ：: Almost no corrosion ×: Significant corrosion was observed

Example 2 5% by weight of catechol, 2-
(2-Aminoethoxy) stripping solution composition consisting of 65% by weight of ethanol, 15% by weight of hydroxylamine, and 15% by weight of water was subjected to O ₂ bubbling at room temperature (25 ° C.) for 2 hours (O _{2 with} respect to 200 mL of stripping solution composition). ₂ gas flow 3L /
By doing so, catechol in the composition was oxidized to convert at least a part of the catechol to 1,2-benzoquinone to prepare a photoresist stripping solution composition.

Using this photoresist stripper composition, the color difference (ΔE ^* _ab ) and light transmittance (500 nm) were measured in the same manner as in Example 1. Table 2 shows the results.

Further, using this photoresist stripper composition, a photoresist film was stripped in the same manner as in Example 1.

The substrate after the peeling treatment was sufficiently rinsed with pure water, and the peeling property of the photoresist film and the anticorrosion property of the polysilicon film were evaluated by observing an SEM (scanning electron microscope) photograph. Table 3 shows the results.

Example 3 10% by weight of catechol, 10% by weight of triethylenetetramine, hydroxylamine 1
A stripper composition comprising 5% by weight, 45% by weight of dimethyl sulfoxide, and 20% by weight of water is placed in a container intended to increase the contact area with air, and is brought into contact with air at room temperature. Then, catechol in the composition was oxidized to convert at least a part of the catechol to 1,2-benzoquinone to prepare a photoresist stripper composition.

Using this photoresist stripper composition, the color difference (ΔE ^* _ab ) and light transmittance (500 nm) were measured in the same manner as in Example 1. Table 2 shows the results.

Further, using this photoresist stripper composition, a photoresist film was stripped in the same manner as in Example 1.

The substrate after the peeling treatment was sufficiently rinsed with pure water, and the peeling property of the photoresist film and the anticorrosion property of the polysilicon film were evaluated by observing an SEM (scanning electron microscope) photograph. Table 3 shows the results.

Comparative Examples 1 to 3 Photoresist stripper compositions having the compositions shown in Table 1 were prepared.

Using each of the photoresist stripper compositions, a color difference (ΔE ^* _ab ) and a light transmittance (500 nm) were obtained.
Was measured. Table 2 shows the results.

Further, using each of the photoresist stripping compositions, a photoresist film was stripped in the same manner as in Example 1.

The substrate after the peeling treatment was sufficiently rinsed with pure water, and the peeling property of the photoresist film and the anticorrosion property of the polysilicon film were evaluated by observing SEM (scanning electron microscope) photographs. Table 3 shows the results.

[0108]

[Table 1]

[0109]

[Table 2]

[0110]

[Table 3]

In each of Examples 1 to 3 and Comparative Examples 1 to 3, no corrosion of the Al-Si layer was observed.

In the above examples, the stripping and anticorrosion properties of the stripping composition of the present invention were evaluated after the etching step. However, the stripping composition of the present invention was evaluated in the etching and ashing steps. It has been confirmed that excellent peelability and anticorrosion properties can be obtained in the same manner as described above even when performed later.

[0113]

As described above in detail, according to the present invention, the exfoliation property of a photoresist film and the exfoliation property of a deposition (residue) generated after etching or ashing are excellent.
Provided are a photoresist stripping composition and a photoresist stripping method using the same, which are excellent in the corrosion resistance of a substrate on which a metal layer, an inorganic film, etc. are formed.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-7-219241 (JP, A) JP-A-7-219240 (JP, A) JP-A 5-259066 (JP, A) JP-A 8-219 334905 (JP, A) JP-A-6-222573 (JP, A) JP-A-11-174690 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7 / 42 H01L 21/027

Claims (10)

(57) [Claims] 1. A color difference (ΔE ^* _ab ) in an L ^* a ^* b ^* color system defined in JIS Z 8730 is 30 to 18.
0 (reference value: pure water). A photoresist stripping composition for photoresist. 2. The photoresist stripping composition according to claim 1, wherein the color difference (ΔE ^* _ab ) is 50 to 140. 3. The photoresist stripper composition according to claim 1, further having a light transmittance of 70% or less (cell length = 1 cm) for light having a wavelength of 500 nm. 4. An oxide of at least an aromatic hydroxy compound (provided that phenol in the aromatic hydroxy compound is
In which some or all of the —OH groups have been converted to ＝ O groups
The stripping solution composition for a photoresist according to any one of claims 1 to 3, which comprises: 5. A step of providing a photoresist layer on a substrate on which a metal layer is formed, a step of selectively exposing the photoresist layer, and a step of developing the photoresist layer after exposure to form a resist pattern. 5. A photoresist stripping method comprising: (IV) a step of selectively etching the substrate using the resist pattern as a mask; and (V) a step of stripping the etched resist pattern from the substrate. A photoresist stripping method, comprising stripping a resist pattern after etching using the photoresist stripper composition according to any one of the above. 6. The method according to claim 5, wherein an inorganic film is further formed on the substrate. 7. The method according to claim 6, wherein the inorganic film is a polysilicon (poly-Si) film. 8. A step of providing a photoresist layer on a substrate on which a metal layer is formed, (II) a step of selectively exposing the photoresist layer, and (III) developing the exposed photoresist layer to form a resist pattern. (IV) selectively etching the substrate using the resist pattern as a mask, (V) ashing the resist pattern, and (VI) stripping the ashed resist pattern from the substrate. A photoresist stripping method, comprising: stripping a resist pattern after ashing using the photoresist stripping composition according to any one of claims 1 to 4. 9. The method according to claim 8, wherein an inorganic film is further formed on the substrate. 10. The method according to claim 9, wherein the inorganic film is a polysilicon (poly-Si) film.