JP3255404B2 - Positive photoresist composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel positive photoresist composition.

[0002]

2. Description of the Related Art Conventionally, as a photoresist in a process of manufacturing a semiconductor device such as an IC or LSI or a liquid crystal device such as an LCD, a positive photoresist obtained by combining an alkali-soluble resin for forming a film with a photosensitive component comprising a quinonediazide group-containing compound. Type photoresist compositions have been put to practical use.

As an alkali-soluble resin for forming a film, it can be dissolved without swelling in an aqueous alkali solution as a developing solution and has excellent developing characteristics, and also has excellent heat resistance to plasma etching as a mask at the time of etching. The novolak type resin is useful from the point of having.

The quinonediazide group-containing compound of the photosensitive component has an effect of suppressing the alkali solubility of the novolak type resin, but has a function of preventing ultraviolet rays (g-ray, i-line).
Rays), electromagnetic waves such as deep ultraviolet rays including excimer lasers,
It is unique in that when it receives irradiation or drawing of a particle beam such as an electron beam, it changes to alkali-soluble and has an action of promoting the alkali-solubility of the novolak-type resin. Many positive photoresist compositions containing a quinonediazide group-containing compound having a large property change by receiving radiation such as electromagnetic waves or particle beams and an alkali-soluble novolak resin have been developed and put into practical use (for example, U.S. Pat. No. 4,377,631;
JP-A-62-35349, JP-A-1-142254
8, Japanese Patent Application Laid-Open No. 1-179147,
No. 4897).

However, in recent years, the degree of integration of semiconductor devices and liquid crystal devices has been increasing more and more, and in the production of VLSI, the processing accuracy of ultrafine patterns of submicron and half micron or less is required. The characteristics required for the composition include high resolution, excellent cross-sectional shape, and a resist with excellent heat resistance that does not undergo thermal deformation due to heating operations after dry etching or irradiation, and before development. Being able to form patterns, being highly sensitive in terms of high productivity, and being excellent in the depth of focus characteristics to be able to reproduce a resist pattern that is faithful to the mask pattern without being affected by substrate steps, etc. Excellent halation prevention effect, sufficient exposure margin, and the like.

[0006]

SUMMARY OF THE INVENTION Under such circumstances, the present invention is directed to a positive photoresist composition capable of forming a resist pattern having high resolution and excellent heat resistance and having a sufficient exposure margin. It was made for the purpose of providing goods.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a positive photoresist composition having the above-mentioned preferable properties. As a result, an alkali-soluble resin, naphthoquinone-1,2-diazide sulfone The present inventors have found that a specific positive type photoresist composition containing an acid ester compound and a specific substituted resorcinol derivative can be suitable for the purpose, and have completed the present invention based on this finding.

That is, the present invention relates to an alkali-soluble resin, an ester compound of naphthoquinone-1,2-diazidosulfonic acid and 1,3-dihydroxy-4,6-bis [α-methyl-α- (4′-hydroxy Phenyl) ethyl] benzene; and a positive photoresist composition comprising:

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the composition of the present invention, an alkali-soluble resin is used as a film-forming substance, and a naphthoquinone-1,2-diazidosulfonic acid ester compound is used as a photosensitive substance.

[0010] The alkali-soluble resin is not particularly limited and can be arbitrarily selected from commonly used ones.
Examples include condensation reaction products of aromatic hydroxy compounds such as cresol and xylenol with aldehydes such as formaldehyde or ketones such as acetone, polyhydroxystyrene, and derivatives thereof.

Examples of the aromatic hydroxy compound include phenol, m-cresol, p-cresol, o
Xylenols such as -cresol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3 5-
Trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert
-Butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2
-Tert-butyl-5-methylphenol, 6-te
alkylphenols such as rt-butyl-3-methylphenol, alkoxyphenols such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol and m-propoxyphenol, o- Isopropenylphenol, p-isopropenylphenol, 2
-Methyl-4-isopropenylphenol, isopropenylphenols such as 2-ethyl-4-isopropenylphenol, arylphenols such as phenylphenol, 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, etc. And the like. These may be used alone or in combination of two or more. Among these aromatic hydroxy compounds, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, and 2,3,5-trimethylphenol are particularly preferable.

Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furyl acrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α -Phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde , P-chlorobenzaldehyde And cinnamaldehyde. These may be used alone or in combination of two or more. Among these aldehydes, formaldehyde is preferred from the viewpoint of availability, but it is particularly preferred to use a combination of hydroxybenzaldehydes and formaldehyde for improving heat resistance.

Examples of the ketones include acetone,
Methyl ethyl ketone, diethyl ketone, and diphenyl ketone. These may be used alone,
Also, two or more kinds may be used in combination. In a combination of an aromatic hydroxy compound and a ketone, that of pyrogallol and acetone is preferred.

The condensation reaction product of the aromatic hydroxy compound with the aldehyde or ketone can be produced by a known method in the presence of an acidic catalyst. Hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid and the like can be used as the acidic catalyst at that time. The condensation product obtained in this manner is preferably one obtained by cutting a low-molecular-weight region by subjecting it to a treatment such as fractionation, because it has excellent heat resistance. In the treatment such as separation, the resin obtained by the condensation reaction is dissolved in a good solvent, for example, an alcohol such as methanol or ethanol, a ketone such as acetone or methyl ethyl ketone, ethylene glycol monoethyl ether acetate, or tetrahydrofuran, and then poured into water and precipitated. This is performed by a method such as A suitable weight average molecular weight of the condensation reaction product is 2,000 to 25.
000, preferably in the range of 2,500 to 20,000. Here, the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography.

Examples of the polyhydroxystyrene and its derivatives include a homopolymer of vinylphenol and a copolymer of vinylphenol with a comonomer copolymerizable therewith. Examples of the comonomer include acrylic acid derivatives, acrylonitrile, methacrylic acid derivatives, methacrylonitrile, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene,
Styrene derivatives such as p-methoxystyrene and p-chlorostyrene are exemplified.

In the composition of the present invention, the naphthoquinone-1,2-diazidosulfonic acid ester compound used as a photosensitive substance is not particularly limited, and can be arbitrarily selected from those usually used. Preferred are naphthoquinone-1,2-diazide-
5-sulfonic acid, naphthoquinone-1,2-diazide-4
-Sulfonic acid, naphthoquinone-1,2-diazide-6-
An esterified product of a naphthoquinone-1,2-diazidosulfonic acid such as sulfonic acid and a hydroxy compound is used. The ester compound may be a completely esterified product or a partially esterified product.

Further, as the hydroxy compound,
For example, the following compounds (a) to (d) can be exemplified. (A) polyhydroxybenzophenones; examples of compounds belonging to the group include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone,
2,3,4,4'-tetrahydroxybenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3', 4,4 ', 6-pentahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, 2,2 ' , 3,4,5'-pentahydroxybenzophenone, 2,3 ', 4,5,5'-pentahydroxybenzophenone, 2,3,3', 4
4 ', 5'-hexahydroxybenzophenone and the like.

(B) General formula

Embedded image (Wherein R ^{1 to} R ³ are a hydrogen atom or a lower alkyl group, R ⁴
To R ⁹ are a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxyl group, a lower alkenyl group or a cycloalkyl group, R ¹⁰ and R ¹¹ are a hydrogen atom, a halogen atom or a lower alkyl group, x, y and z are 1 to An integer of 3 and n 'is 0 or 1);
Examples of compounds belonging to this include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5
-Dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane , Bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-
Hydroxyphenylmethane, bis (4-hydroxy-
2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl)- 3,
4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, Bis (4-hydroxyphenyl) -3-methoxy-
4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4- Hydroxyphenyl) -4
-Hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4
-Hydroxy-6-methylphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methyl Phenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3
-Cyclohexyl-6-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-
6-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4
-Methylphenyl) -2-hydroxyphenylmethane,
Bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) -3,4-dihydroxyphenylmethane, 1-
[1- (4-hydroxyphenyl) isopropyl] -4
-[1,1-bis (4-hydroxyphenyl) ethyl]
Examples include benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene.

(C) General formula

Embedded image (Wherein R ¹² and R ¹³ are a hydrogen atom or a lower alkyl group,
x 'and y' are integers from 1 to 3); bis (hydroxyphenyl) alkanes represented by the formula: 2- (2,3,4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl)- 2- (4'-
(Hydroxyphenyl) propane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane and the like.

(D) Hydroxyaromatic compounds: Examples of the compounds belonging to the group include phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, pyrogallol monomethyl ether, pyrogallol-1,3 -Dimethyl ether, gallic acid, partially esterified or partially etherified gallic acid and the like.

The quinonediazide group-containing compound used as the photosensitive component of the composition of the present invention is, for example, naphthoquinone-
The compound can be produced by subjecting 1,2-diazide-4 (or 5) -sulfonyl halide to a condensation reaction with the above-mentioned hydroxy compounds (a) to (d) and subjecting it to complete esterification or partial esterification. This condensation reaction is usually carried out in an organic solvent such as dioxane, N-methylpyrrolidone, dimethylacetamide, triethanolamine,
It is advantageous to work in the presence of a basic condensing agent such as alkali carbonate or alkali hydrogen carbonate.

At this time, the naphthoquinone-1,2-diazide-4 (or 5) has a mole number of 50% or more, preferably 60% or more, based on the total mole number of the hydroxyl groups of the hydroxy compound.
-Sulfonyl halide condensed esters, that is, those having a degree of esterification of 50% or more, preferably 60% or more are preferred because high resolution can be obtained.

In the composition of the present invention, the polyhydroxy compound represented by the general formula (I) or

Embedded image (Wherein R ^{14 to} R ¹⁷ are a hydrogen atom or a lower alkyl group;
¹⁸ to R ²² is a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxyl group, l ', m', p, polyhydroxy compound q is represented by a 1 to 3) of integers (where 1,3 Excluding dihydroxy-4,6-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene).

Examples of the polyhydroxy compound represented by the general formula (III) include 2,6-bis [1- (2,4
-Dihydroxyphenyl) isopropyl] -4-methylphenol, 4,6-bis (3,5-dimethoxy-4-
(Hydroxyphenylmethyl) pyrogallol, 4,6-bis (3,5-dimethyl-4-hydroxyphenylmethyl) pyrogallol, 2,6-bis (3-methyl-4,6
-Dihydroxyphenylmethyl) -4-methylphenol, 2,6-bis (2,3,4-trihydroxyphenylmethyl) -4-methylphenol and the like are preferred.

Examples of the polyhydroxy compound represented by the general formula (I) include bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane and bis (4-hydroxy- 2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl)-
3,4-dihydroxyphenylmethane, 1- [1- (4
-Hydroxyphenyl) isopropyl] -4- [1,1
-Bis (4-hydroxyphenyl) ethyl] benzene,
1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-
Hydroxyphenyl) ethyl] benzene is preferred.

1,3-dihydroxy-4,6-bis [α
-Methyl-α- (4'-hydroxyphenyl) ethyl]
The blending amount of benzene and the polyhydroxy compound represented by the general formula (I) or (III) used as required is 5 to 50 with respect to the alkali-soluble resin component.
%, Preferably in the range of 10 to 35% by weight.

Next, the compounding amounts of the photosensitive components in the composition of the present invention are as follows: the alkali-soluble resin and 1,3-dihydroxy-4,6-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] It is preferable to select from 5 to 100% by weight, preferably from 10 to 50% by weight, based on the total amount of benzene and the polyhydroxy compound optionally added. When the amount is less than 5% by weight, an image faithful to the pattern cannot be obtained, and the transferability decreases. When the amount exceeds 100 parts by weight, the uniformity of the formed resist film decreases,
The resolution deteriorates.

In the composition of the present invention, the following components (A) and (B) can be blended as an antihalation agent, if necessary.

The component (A) is 4,4'-bis (dialkylamino) benzophenone, for example, 4,4 '
-Bis (dimethylamino) benzophenone, 4,4'-
Bis (diethylamino) benzophenone, 4,4'-bis (di-n-propylamino) benzophenone,
4'-bis (di-isopropylamino) benzophenone, 4,4'-bis (dibutylamino) benzophenone, 4-dimethylamino-4'-diethylaminobenzophenone, 4- (N-methyl-N-ethylamino)-
4 '-(N-methyl-N-ethylamino) benzophenone and the like. These may be used alone,
Two or more kinds may be used in combination. Among these, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are particularly preferred.

The component (B) has the general formula

Embedded image (Wherein R ²³ and R ²⁴ are a hydroxyl group or a lower alkoxyl group, n is an integer of 1 or 2, m is an integer of 0 or 1 to 3), and a compound represented by the general formula:

Embedded image Wherein R ²⁵ and R ²⁶ in the formula are a hydrogen atom or a lower alkyl group, and p is an integer of 1 to 3;

Embedded image [Wherein R ²⁷ and R ²⁸ are a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxyl group, a hydroxyalkyl group, a cyano group, a lower alkyl group or a lower alkoxyl group, and R ²⁹ is an aryl group, a lower alkyl group or a dialkyl An aminophenyl group, R ³⁰ is a hydrogen atom or a lower alkyl group, and R ³¹ is a hydroxyl group, an amino group or an OZ (Z is a naphthoquinone-1,2-diazidosulfonyl group). At least one compound.

Examples of the hydroxybenzophenones represented by the general formula (IV) include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,5-trihydroxybenzophenone, , 4,6-trihydroxybenzophenone,
2,2 ', 3,4-tetrahydroxybenzophenone,
2,3,4,4'-tetrahydroxybenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, 2,3 ', 4,4', 6-pentahydroxybenzophenone, 2,3 ' , 4,5,5 ', 6-hexahydroxybenzophenone, 2,3,3', 4,4 ',
5'-hexahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and the like. These may be used alone or in combination of two or more. Of these, 2,4,5-
Trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-
Tetrahydroxybenzophenone, 2,2 ', 3,4
4'-pentahydroxybenzophenone, 2,3
3 ', 4,4', 5'-Hexahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone have high antihalation effects due to their light-absorbing properties, and have excellent sensitivity and exposure margin properties. Is preferred. Among them, 2,2 ', 4,4'-tetrahydroxybenzophenone is particularly preferred.

The benzophenones having a hydroxyl group and an amino group represented by the general formula (V) include, for example, 4-amino-2'-hydroxybenzophenone, 4-amino-4 '
-Hydroxybenzophenone, 4-dimethylamino-
2'-hydroxybenzophenone, 4-dimethylamino-4'-hydroxybenzophenone, 4-diethylamino-2'-hydroxybenzophenone, 4-diethylamino-4'-hydroxybenzophenone, 4-dimethylamino-2 ', 4'-dihydroxybenzophenone , 4
-Diethylamino-2 ', 4'-dihydroxybenzophenone, 4-amino-2', 4 ', 6'-trihydroxybenzophenone, 4-dimethylamino-2', 4 ',
6'-trihydroxybenzophenone, 6-dimethylamino-2 ', 4', 6'-trihydroxybenzophenone and the like. These may be used alone,
Two or more kinds may be used in combination. Of these, 4-dialkylamino-2'-hydroxybenzophenones such as 4-dimethylamino-2'-hydroxybenzophenone, 4-diethylamino-2'-hydroxybenzophenone, and 4-dimethylamino-2 ',
4-dialkylamino-2 ', 4'-dihydroxybenzophenones such as 4'-dihydroxybenzophenone and 4-diethylamino-2', 4'-dihydroxybenzophenone have high antihalation effects due to their light-absorbing properties, and have high sensitivity and exposure. It is particularly preferable because it has excellent margin characteristics.

The pyrazoles having a phenylazo group represented by the general formula (VI) include 4-phenylazo-5
-Aminopyrazoles, 4-phenylazo-5-hydroxypyrazoles and 4-phenylazo-5- (OZ) pyrazoles (Z is naphthoquinone-1,
2-diazidosulfonyl group).

The 4-phenylazo-5-aminopyrazoles include, for example, 5-amino-1-phenyl-4-phenylazopyrazole, 5-amino-3-methyl-1-
Phenyl-4-phenylazopyrazole, 5-amino-
3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole, 5-amino-3-methyl-1-
Phenyl-4- (2-hydroxyphenylazo) pyrazole, 5-amino-3-methyl-1-phenyl-4-
(4-carboxyphenylazo) pyrazole, 5-amino-3-methyl-1-phenyl-4- (3-carboxyphenylazo) pyrazole, 5-amino-3-methyl-
1-phenyl-4- (4-ethylolphenylazo) pyrazole, 5-amino-1-ethyl-3-methyl-4-
(4-nitrophenylazo) pyrazole, 5-amino-
3-methyl-1-phenyl-4- (4-hydroxy-2
-Nitrophenylazo) pyrazole, 5-amino-3-
Methyl-1-phenyl-4- (4-chloro-2-methylphenylazo) pyrazole, 5-amino-3-methyl-
1-phenyl-4- (4-cyanophenylazo) pyrazole, 5-amino-3-methyl-1-phenyl-4-
(4-ethoxyphenylazo) pyrazole, 5-amino-3-dimethylaminophenyl-4-phenylazopyrazole and the like can be mentioned.

The 4-phenylazo-5-hydroxypyrazoles include, for example, 1-phenyl-4-phenylazo-5-hydroxypyrazole, 3-methyl-1
-Phenyl-4-phenylazo-5-hydroxypyrazole, 1-phenyl-4- (2,5-dichlorophenylazo) -5-hydroxypyrazole, 1-ethyl-3-
Methyl-4- (4-chloro-2-methylphenylazo)
-5-hydroxypyrazole, 3-methyl-1-p-tolyl-4- (3-nitrophenylazo) -5-hydroxypyrazole, 3-methyl-1-p-tolyl-4- (4
-Ethylphenylphenylazo) -5-hydroxypyrazole, 3-methyl-1-p-tolyl-4- (2-methoxy-4-nitrophenylazo) -5-hydroxypyrazole, 3-ethyl-1-phenyl-4 -(4-methoxy-
2-nitrophenylazo) -5-hydroxypyrazole, 3-methyl-1-phenyl-4- (4-chloro-2
-Nitrophenylazo) -5-hydroxypyrazole,
1-p-dimethylaminophenyl-3-methyl-4-phenylazo-5-hydroxypyrazole, 1-p-dimethylaminophenyl-3-methyl-4- (4-methyl-
2-chlorophenylazo) -5-hydroxypyrazole, 1-p-dimethylaminophenyl-3-methyl-4
C .- (4-methyl-2-nitrophenylazo) -5-hydroxypyrazole, 1-phenyl-4- (4-methoxyphenylazo) -5-hydroxypyrazole, C.I. I.
Solvent Yellow 16, C.I. I. Sol
vent Yellow 21 and the like.

The 4-phenylazo-5- (OZ) pyrazoles include, for example, the above-mentioned 4-phenylazo-
The hydroxyl group at the 5-position of the exemplified compound of 5-hydroxypyrazoles has a naphthoquinone-1,2-diene such as naphthoquinone-1,2-diazide-4-sulfonic acid or naphthoquinone-1,2-diazide-5-sulfonic acid. Examples include naphthoquinone-1,2-diazidosulfonic acid ester of a predetermined pyrazole compound esterified with azidosulfonic acid. This can improve the contrast of the resist pattern as well as the function as a light absorbing agent, and can form a resist pattern having extremely excellent shape stability and dimensional stability as compared with a conventional resist pattern.

These pyrazoles may be used alone or in combination of two or more. Among these pyrazoles, 5-amino-3-methyl-1-phenyl-4- (4-carboxyphenylazo) pyrazole, 5
-Amino-3-methyl-1-phenyl-4- (3-carboxyphenylazo) pyrazole, 5-amino-3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole, 3-methyl-1 -P-tolyl-4-
(3-Nitrophenylazo) -5-hydroxypyrazole, 3-methyl-1-p-tolyl-4- (4-ethylolphenylazo) -5-hydroxypyrazole is preferred.

When these components (A) and (B) are blended in the composition of the present invention, a positive photoresist composition used as a substrate, for example, an alkali-soluble resin and naphthoquinone-1,2-diazide sulfone Acid ester compound, 1,3-dihydroxy-4,6-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene and optionally used additives, for example, the above general formula (I) or With respect to the composition comprising the polyhydroxy compound represented by (III), the components (A) and (B) used as an antihalation agent are added in a total amount of 0.1 to
It is preferable to add the compound in an amount of 5.0% by weight, preferably 0.5 to 3.0% by weight. When the amount is less than 0.1% by weight, the effect of addition such as prevention of halation is insufficient, and when the amount exceeds 5.0% by weight, resolution, sensitivity and the like are deteriorated.

In the composition of the present invention, the component (A) and the component (B) are further mixed on a weight basis from 1:10 to 10:
It is preferred to mix them in a mixing ratio in the range of 1, preferably 1:10 to 2: 1. If the ratio is out of this range, the sensitivity is degraded and the effect of preventing halation becomes insufficient. In particular, when the amount of the component (A) is too large, the sensitivity is significantly deteriorated.
It is desirably less than 1.0% by weight, preferably less than 1.0% by weight. In addition, as guessed from an Example, (A)
When the total amount of the component and the component (B) is small, it is preferable that the component (A) is large, and when the total amount of the component (A) and the component (B) is large, the component (A) is preferably small. .

The composition of the present invention may further contain, if necessary, a compatible additive such as an additional resin, a plasticizer, a stabilizer or a developed image for improving the performance of the resist film. A commonly used material such as a coloring agent for visualization can be added and contained.

The composition of the present invention comprises an alkali-soluble resin, a naphthoquinone-1,2-diazidesulfonic acid ester compound and 1,3-dihydroxy-4,6-bis [α-methyl-α- (4′-hydroxyphenyl). ) Ethyl] benzene and various optional components used as desired are preferably dissolved in a suitable solvent and used in the form of a solution.

Examples of such a solvent include acetone,
Ketones such as methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether thereof Or polyhydric alcohols such as monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethoxy. Esters such as ethyl propionate can be mentioned. These may be used alone,
You may mix and use 2 or more types.

About the preferred method of using the composition of the present invention,
As an example, first, the alkali-soluble resin component, the photosensitive component, and 1,3-
Dihydroxy-4,6-bis [α-methyl-α- (4 ′
-Hydroxyphenyl) ethyl] benzene, and a solution prepared by dissolving optional components used in an appropriate solvent as described above, are coated with a spinner or the like, dried to form a photosensitive layer, and then emit ultraviolet rays. Using a light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an arc lamp, a xenon lamp, or the like, exposure is performed through a required mask pattern or irradiation is performed while scanning an electron beam. Next, when this is immersed in a developing solution, for example, a weakly alkaline aqueous solution such as a 1 to 10% by weight aqueous solution of tetramethylammonium hydroxide, the exposed portion is dissolved and removed, and an image faithful to the mask pattern can be obtained.

[0044]

As described above, the positive photoresist composition of the present invention comprises:
A resist pattern having high resolution and excellent heat resistance can be formed, has a sufficient exposure margin, and is suitably used as a resist for ultrafine processing in the manufacture of semiconductor devices such as ICs and LSIs.

[0045]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

The physical properties of the photoresist composition were determined as follows. (1) Sensitivity: The sample was applied on a silicon wafer using a spinner and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 1.05 μm. The film is exposed to the light for 0.1 second to 0.01 using a reduction projection exposure apparatus NSR-1755i7B (manufactured by Nikon Corporation, NA = 0.54).
After exposure at intervals of seconds, the film is developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, washed with water for 30 seconds and dried. Milliseconds (m
s) Measured in units.

(2) Resolution: The resolution was shown by the limit resolution at the exposure dose for reproducing a 0.40 μm mask pattern.

(3) Heat resistance: A resist pattern having a pattern line width of 5 μm formed on a silicon wafer
The temperature is raised from 25 ° C by 5 ° C in increments of 130 ° C, 135 ° C,
When baking was performed on a hot plate at each temperature of 40 ° C. for 5 minutes, the temperature at which the resist pattern was deformed was shown.

(4) Pattern shape: The cross-sectional shape of the resist pattern having a width of 0.40 μm was observed by an SEM (scanning electron microscope) photograph, and a rectangular shape was designated as A, and a slightly trapezoidal shape was designated as B. And

(5) Depth of focus width: Reduction projection exposure apparatus NS
Using R-1755i7B (manufactured by Nikon Corporation, NA = 0.54), Eop (exposure amount required to form a 0.40 μm line and space one-to-one) as a reference exposure amount, and the exposure amount Shift the focal point up and down as appropriate,
SEM of resist pattern obtained by exposure and development
A photograph was observed. 0.40 μm from the SEM photograph
The maximum value (μm) of defocus at which the rectangular resist pattern of (1) was obtained was defined as the depth of focus.

(6) Exposure allowance: Eop (0.40 μm
) (The minimum exposure time required for one-to-one line-and-space formation) is Eth (the film thickness of the exposed portion after development is 0%).
The value (Eop / Eth) divided by the value (Eop / Eth) was defined as the exposure margin. The larger this value is, the wider the exposure margin width is, which is preferable.

(7) Halation resistance: A sample is applied to a quartz plate so as to have a thickness of 1.5 μm.
Illuminance 10m using LA-501F (manufactured by Canon)
The sample was irradiated with ultraviolet rays at W / cm ² for 30 seconds, the transmittance of the sample before and after the irradiation of the ultraviolet rays was measured, and the parameters A and B, which were indicators of halation resistance, were calculated by the following equation. The larger the B parameter, the higher the halation resistance of the resist composition, which is preferred. A = (l / d) × lnT∞ / T ⁰ B = (− 1 / d) × lnT∞ d: film thickness of the sample T ⁰ : transmittance before ultraviolet irradiation / 100 T∞: transmittance after ultraviolet irradiation / 100

Example 1 m-cresol and p-cresol were mixed at a weight ratio of 36: 6.
The mixture was mixed at a ratio of 4 and formalin was added thereto. The cresol novolak resin obtained by condensation in a conventional manner using an oxalic acid catalyst was subjected to a fractionation treatment, and a low molecular weight region was cut to obtain a weight average molecular weight of 5,000. A cresol novolak resin was prepared. 100 parts by weight of the resin thus obtained was added to bis (5-cyclohexyl-4-hydroxy-2).
-Methylphenyl) -3,4-dihydroxyphenylmethane 1.0 mol and naphthoquinone-1,2-diazide-5
13 parts by weight of an esterification reaction product with 2.0 mol of -sulfonyl chloride, 1.0 mol of bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane and naphthoquinone-1, 24 parts by weight of an esterification reaction product with 3.0 mol of 2-diazide-5-sulfonyl chloride, 1,3-dihydroxy-
23 parts by weight of 4,6-bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene and 1,3,5-
Tris (4-tert-butyl-3-hydroxy-2,
1.6 parts by weight of 6-dimethylbenzyl) isocyanurate was added to prepare a positive photoresist composition as a substrate. Then, 0.5% by weight of 4,4'-
Bis (diethylamino) benzophenone and 2,2 ',
A mixture of 4,4'-tetrahydroxybenzophenone (2: 1 by weight) was prepared by mixing 9: 1 of ethyl lactate and butyl acetate.
After adding a solution dissolved in 400 parts by weight of the mixed solvent (weight ratio), the solution was filtered using a membrane filter having a pore size of 0.2 μm to prepare a desired positive photoresist composition. Table 1 shows the physical properties of this product.

Examples 2 to 5 In Example 1, 4,4'-bis (diethylamino)
A positive photoresist composition was obtained in the same manner as in Example 1 except that the mixing ratio and the amount of benzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone were changed as shown in Table 1. Table 1 shows the physical properties of this product.

Example 6 In Example 1, 4,4'-bis (diethylamino)
A positive photoresist composition was obtained in the same manner as in Example 1, except that benzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone were not blended. Table 1 shows the physical properties of this product.

Example 7 In Example 1, 2,4'-bis (diethylamino) benzophenone alone was blended in the amount shown in Table 1 without blending 2,2 ', 4,4'-tetrahydroxybenzophenone. Except for the above, a positive photoresist composition was obtained in the same manner as in Example 1. Table 1 shows the physical properties of this product.

Example 8 In Example 1, 4,4'-bis (diethylamino)
A positive photoresist composition was obtained in the same manner as in Example 1, except that benzophenone was not blended and only 2,2 ', 4,4'-tetrahydroxybenzophenone was blended in the amount shown in Table 1. Table 1 shows the physical properties of this product.

[0058]

[Table 1]

Examples 9 to 12 In Example 1, 2,2 ', 4,4'-tetrahydroxybenzophenone was replaced with 4-dimethylamino-2', 4 '
A positive photoresist composition was prepared in the same manner as in Example 1 except that the mixing ratio and the amount of addition were changed as shown in Table 2 in place of -dihydroxybenzophenone. Table 2 shows the physical properties of this product.

Example 13 In Example 8, 2,2 ', 4,4'-tetrahydroxybenzophenone was replaced with 4-dimethylamino-2', 4 '
A positive photoresist composition was obtained in the same manner as in Example 8, except that the composition was used in the amount shown in Table 2 in place of -dihydroxybenzophenone. Table 2 shows the physical properties of this product.
Shown in

[0061]

[Table 2]

Examples 14 to 17 In Example 1, 2,2 ', 4,4'-tetrahydroxybenzophenone was converted to 5-amino-3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole. A positive photoresist composition was prepared in the same manner as in Example 1 except that the mixing ratio and the amount of addition were changed as shown in Table 3. Table 3 shows the physical properties of this product.

Example 18 In Example 8, 2,2 ', 4,4'-tetrahydroxybenzophenone was replaced by 5-amino-3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole. A positive photoresist composition was obtained in the same manner as in Example 8, except that it was blended in the amounts shown in Table 3. Table 3 shows the physical properties of this product.

[0064]

[Table 3]

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hidekatsu Ohara 150 Nakamurako Nakahara-ku, Kawasaki City, Kanagawa Prefecture Inside Tokyo Ohka Kogyo Co., Ltd. JP-A-3-259149 (JP, A) JP-A-4-122938 (JP, A) JP-A-4-178451 (JP, A) JP-A-4-296755 (JP, A A) JP-A-4-299348 (JP, A) JP-A-7-152151 (JP, A) JP-A-2-2560 (JP, A) JP-A-3-200251 (JP, A) JP-A-3 -200255 (JP, A) JP-A-5-72728 (JP, A) JP-A-5-204144 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/004

Claims (1)

(57) [Claims] 1. An alkali-soluble resin, naphthoquinone-
1,2-diazidosulfonic acid ester compound and 1,
3-dihydroxy-4,6-bis [α-methyl-α-
(4'-Hydroxyphenyl) ethyl] benzene.