JPH07104465A - Positive photoresist composition - Google Patents

Abstract

PURPOSE:To improve resolution, the repeatability of mask sizes, sensitivity, development capability, heat resistance or the like by containing the naphthoquinone diazide-sulfonic acid ester of the specified polyhydroxy compound and alkali soluble resin. CONSTITUTION:This composition contains 1,2-naphthoquinone diazide-5- (and/or -4-) sulfonic acid ester, and alkali soluble resin expressed by the formula. In the formula, R1 to R10 stand for a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alcoxy group, an acyl group, an alkenyl group, a nitro group or a ciano group, (a) to (d) for 1 or 2 (provided that a+c=b+d) and (n) for 4 or 5. Novolac resin, acetone-pyrogallol resin or the like can be mentioned as the alkali soluble resin, and the weight average molecular weight of the novolac resin is preferably between 2000 and 30000, and the range of 6000 to 20000 is particularly pertinent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation sensitive photoresist composition, and more particularly to a photoresist composition for microfabrication having a high resolution and sensitivity and a good pattern cross-sectional shape. It is a thing. The positive type photoresist according to the present invention is a semiconductor wafer,
It is applied to a substrate of glass, ceramics, metal or the like by spin coating or roller coating to a thickness of 0.5 to 3 μm. Then, it is heated and dried, and a circuit pattern or the like is printed through an exposure mask by ultraviolet irradiation or the like and developed to form a positive image. Further, by etching with this positive image as a mask, the pattern can be processed on the substrate. IC is a typical application field
And other semiconductor manufacturing processes, liquid crystal, circuit board manufacturing such as thermal heads, and other photo-ablation processes.

[0002]

2. Description of the Related Art As a positive photoresist composition,
Generally, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. For example, US Pat. No. 3,666,473 as “Novolak type phenol resin / naphthoquinone diazide substituted compound”.
No., USP-4,115,128 and USP-4,17
No. 3,470, etc., and the most typical composition is "cresol-formaldehyde novolak resin /
An example of "trihydroxybenzophenone-1,2 naphthoquinone diazide sulfonate" is Thompson "Introduction Tou Microlithography".
(LF Thompson "Intro-ductio
n to Microlitho-graphy ”)
(ACS publication, No. 219, P112 to 121). Novolac resin as a binder is particularly useful for this application because it can be dissolved in an aqueous alkaline solution without swelling, and when it is used as a mask for etching, it gives high resistance to plasma etching. Is. Further, the naphthoquinonediazide compound used for the photosensitive material acts as a dissolution inhibitor which lowers the alkali solubility of the novolak resin by itself, but when it is decomposed by light irradiation, an alkali-soluble substance is produced and rather the alkali solubility of the novolak resin is reduced. It is unique in that it acts to enhance it, and is particularly useful as a photosensitive material for a positive photoresist because of its large change in properties with respect to light. From this point of view, many positive photoresists containing a novolak resin and a naphthoquinonediazide photosensitive material have been developed and put to practical use from the viewpoint of 1.5 μm to 2 μm.
We have achieved sufficient results in line width processing up to about μm.

However, the degree of integration of integrated circuits is increasing more and more, and in the manufacture of semiconductor substrates such as VLSIs,
It is becoming necessary to process an ultrafine pattern having a line width of μm or less. In such applications, particularly high resolution, a photoresist having a high sensitivity from the viewpoint of high pattern shape reproducibility that accurately copies the shape of the exposure mask and high productivity is required, and a conventional naphthoquinonediazide-based photosensitive material, for example, US Patent 3046118
No. 3106465, No. 3148983, Japanese Patent Publication No. 37-18015, No. 56-2333, No. 62-2.
In reality, the positive photoresists using gallic acid esters and 1,2-naphthoquinonediazide sulfonic acid esters of polyhydroxybenzophenones as described in Japanese Patent No. 8457 and the like cannot be used.

On the other hand, in place of 1,2-naphthoquinone diazide sulfonic acid ester of polyhydroxybenzophenones, 1,2-naphthoquinone diazide sulfonic acid ester of a specific polyhydroxy compound is used as a photosensitive component for ultrafine processing. A number of positive photoresist compositions having suitable properties have been proposed (for example, JP-A-60-163043 and 61-97278,
62-10645, 62-10646, 62-1
98852, 63-220139, Japanese Examined Patent Publication No. 62-34.
11, Japanese Patent Publications 1-38289, 1-45901, JP-A-1-291240, 1-291241, 1-29.
1242, 1-280748, and JP-A-2-26935.
1, each of JP-A-2-296248 and JP-A-2-296249).

However, it cannot be said that positive photoresist compositions using these photosensitive materials have been sufficiently improved practically, and when they are stored in a solution, photosensitive components are likely to precipitate. , Storage stability often caused problems.

[0006]

Therefore, the object of the present invention is to (1) particularly in the manufacture of semiconductor devices.
A positive photoresist composition having high resolution,
(2) A positive photoresist composition that accurately reproduces mask dimensions over a wide range of photomask line width,
(3) A positive photoresist composition capable of forming a resist pattern having a cross-sectional shape having a high aspect ratio in a pattern having a line width of 1 μm or less, (4) a pattern having a shape in which the side wall of the pattern cross section is nearly vertical. A positive photoresist composition to be obtained, (5) A positive photoresist composition having a wide development latitude, (6) A positive photoresist composition in which the resulting resist image has excellent heat resistance, (7) Excellent storage stability Another object of the present invention is to provide a positive photoresist composition.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies with the above characteristics in mind, and as a result, can achieve the above object by using an alkali-soluble resin and a quinonediazide compound having a specific structural formula. Based on this finding, they have completed the present invention. That is, the object of the present invention is 1,2-naphthoquinonediazide-5- (and / or a polyhydroxy compound represented by the following general formula (I).
Or -4-) sulfonic acid ester and an alkali-soluble resin.

[0008]

[Chemical 2]

R _{1 to} R ₁₀ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acyl group, an alkenyl group, a nitro group or a cyano group, a, b, c, d: 1 or 2 (however, a + c = b + d = 4), and n: 4 or 5. Hereinafter, the present invention will be described in detail.

In R _{1 to} R ₁₀ of the above general formula (I),
The halogen atom is a chlorine atom, a bromine atom or an iodine atom, and the alkyl group is a methyl group, an ethyl group,
An alkyl group having 1 to 4 carbon atoms such as a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a t-butyl group, an alkoxy group is a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, An alkoxy group having 1 to 4 carbon atoms such as a hydroxypropoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group or a t-butoxy group is preferable. The alkenyl group is preferably a C2-C4 alkenyl group such as a vinyl group, a propenyl group, an allyl group or a butenyl group.

The aryl group includes a phenyl group, a xylyl group, a toluyl group and a cumenyl group, the aralkyl group includes a benzyl group, a phenethyl group and a cumyl group, the alkoxycarbonyl group includes a methoxycarbonyl group and an ethoxycarbonyl group, and the arylcarbonyl group. The group is preferably a benzoyloxy group, the acyloxy group is preferably a butyryloxy group or an acetoxy group, and the acyl group is preferably a formyl group, an acetyl group, a butyryl group, a benzoyl group, a cyanamoyl group or a valeryl group.

Specific examples of the compound represented by the general formula (I) include the compounds represented by the following [I-1] to [I-10], but are not limited thereto. Absent. These polyhydroxy compounds are used alone or in combination of two or more.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

The compound of the present invention comprises, for example, some or all of the hydroxyl groups of the polyhydroxy compound described above in the presence of 1,2-naphthoquinonediazide-5- (and / or-4-) sulfonyl chloride and a basic catalyst. And can be obtained by carrying out a usual esterification reaction. That is, a predetermined amount of polyhydroxy compound and 1,2-naphthoquinonediazide-5-
A solvent such as (and / or -4-) sulfonyl chloride, dioxane, acetone, methylethylketone, N-methylpyrrolidone, etc. is charged into the flask, and a basic catalyst such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethylamine, etc. is added dropwise. And condense. The obtained product is washed with water, purified, and dried. In the usual esterification reaction, a mixture having different numbers of esterifications and esterification positions can be obtained. However, if a synthesis condition or a structure of a polyhydroxy compound is selected, only a specific isomer is selectively esterified. You can also The esterification rate in the present invention is defined as the average value of this mixture.

The esterification rate thus defined can be controlled by the mixing ratio of the raw material polyhydroxy compound and 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride. That is, the added 1,
2-naphthoquinonediazide-5- (and / or -4-)
Substantially all of the sulfonyl chloride undergoes an esterification reaction, so the molar ratio of the raw materials may be adjusted in order to obtain a mixture having a desired esterification rate. If necessary,
It is also possible to use 1,2-naphthoquinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazide-4-sulfonic acid ester in combination. The reaction temperature in the above method is usually -20 to 60 ° C, preferably 0 to 4
It is 0 ° C.

When the photosensitive compound of the present invention synthesized by the above-mentioned method is used as a resin composition, it may be used alone or as a mixture of two or more kinds thereof by blending it with an alkali-soluble resin. The blending amount is 100% Novolac resin.
5 to 100 parts by weight of the compound, preferably 1
It is 0 to 50 parts by weight. If the usage ratio is less than 5 parts by weight, the residual film rate is remarkably lowered, and if it exceeds 100 parts by weight, the sensitivity and the solubility in a solvent are lowered.

Examples of the alkali-soluble resin used in the present invention include novolak resin, acetone-pyrogallol resin, polyhydroxystyrene and derivatives thereof. Among these, novolak resin is particularly preferable,
It can be obtained by addition-condensing an aldehyde with a predetermined monomer as a main component in the presence of an acidic catalyst. As the predetermined monomer, phenol, m-cresol, p
-Cresols, cresols such as o-cresol, 2,
Xylenols such as 5-xylenol, 3,5-xylenol, 3,4-xylenol, and 2,3-xylenol,
alkylphenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol, pt-butylphenol, 2,3,5-trimethylphenol,
Trialkylphenols such as 2,3,4-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol , M-propoxyphenol, p-propoxyphenol, m-butoxyphenol, p-butoxyphenol, and other alkoxyphenols, 2-methyl-4-isopropylphenol, and other bisalkylphenols, m-chlorophenol, p-chlorophenol. , O-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol,
Hydroxy aromatic compounds such as resorcinol and naphthol may be used alone or in combination of two or more, but are not limited thereto.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p. -Hydroxybenzaldehyde, o-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural,
Chloroacetaldehyde and acetals thereof such as chloroacetaldehyde diethyl acetal can be used, and of these, formaldehyde is preferably used. These aldehydes are
They may be used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or the like can be used.

Further, Japanese Patent Laid-Open Nos. 60-45238 and 60-
97347, 60-140235, 60-1897.
39, 64-14229, JP-A-1-276131,
2-60915, 2-275955, 2-282
745, 4-101147, 4-122938, etc., that is, a technique in which low-molecular components of novolac resin are removed or reduced may be used.

The weight average molecular weight of the thus obtained novolak resin is preferably in the range of 2,000 to 30,000. If it is less than 2000, the film loss of the unexposed area after development is large, and if it exceeds 30,000, the developing speed becomes slow. Particularly preferred is the range of 6000 to 20000. Here, the weight average molecular weight is defined as having a polystyrene conversion value of gel permeation chromatography.

In the present invention, the photosensitive material should be mainly used, but if necessary, the following polyhydroxy compound 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride may be used. The esterification product of can be used together.

Examples of polyhydroxy compounds include 2,
3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2 '
-Methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,4,6,3', 4'- Pentahydroxybenzophenone, 2,3,4,2 ', 4'-pentahydroxybenzophenone, 2,3,4,2', 5'-pentahydroxybenzophenone, 2,4,6,3 ' , 4 ', 5'-Hexahydroxybenzophenone, 2,3,4,3', 4 ', 5'
-Polyhydroxybenzophenones such as hexahydroxybenzophenone,

2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenyl pentyl ketone, polyhydroxyphenyl alkyl ketones such as 2,3,4-trihydroxyphenylhexyl ketone,

Bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane-1, bis (2,3) , 4-trihydroxyphenyl) propane-1, bis ((poly) hydroxyphenyl) alkanes such as nordihydroguaiaretic acid,

Propyl 3,4,5-trihydroxybenzoate Phenyl 2,3,4-trihydroxybenzoate 3,
Polyhydroxybenzoic acid esters such as phenyl 4,5-trihydroxybenzoate,

Bis (2,3,4-trihydroxybenzoyl) methane, bis (3-acetyl-4,5,6-trihydroxyphenyl) -methane, bis (2,3,4-trihydroxybenzoyl) benzene, Bis (polyhydroxybenzoyl) alkanes such as bis (2,4,6-trihydroxybenzoyl) benzene or bis (polyhydroxybenzoyl) aryls,

Ethylene glycol-di (3,5-dihydroxybenzoate), ethylene glycol-di (3,5
Alkylene-di (polyhydroxybenzoates) such as 4,5-trihydroxybenzoates),

2,3,4-biphenyltriol, 3,4,
5-biphenyltriol, 3,5,3 ', 5'-biphenyl tetrol, 2,4,2', 4'-biphenyl tetrol, 2,4,6,3 ', 5'-biphenyl pentol, 2 ,
4,6,2 ', 4', 6'-biphenylhexol, 2,3,4,
Polyhydroxybiphenyls such as 2 ′, 3 ′, 4′-biphenylhexol,

Bis (polyhydroxy) sulfides such as 4,4'-thiobis (1,3-dihydroxy) benzene,

Bis (polyhydroxyphenyl) ethers such as 2,2 ', 4,4'-tetrahydroxydiphenyl ether,

Bis (polyhydroxyphenyl) sulfoxides such as 2,2 ', 4,4'-tetrahydroxydiphenyl sulfoxide,

Bis (polyhydroxyphenyl) sulfones such as 2,2 ', 4,4'-diphenyl sulfone,

Tris (4-hydroxyphenyl) methane, 4,4 ', 4 "-trihydroxy-3,5,3', 5'-tetramethyltriphenylmethane, 4,4 ', 3", 4''-Tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4 ', 2'',3'',4''-pentahydroxy-3,5,3',5'- Tetramethyltriphenylmethane, 2,3,4,2 ', 3', 4'-hexahydroxy-5,5 '
-Diacetyltriphenylmethane, 2,3,4,2 ', 3',
4 ', 3 ", 4"-octahydroxy-5,5'-diacetyltriphenylmethane,2,4,6,2', 4 ', 6'-hexahydroxy-5,5'-dipropionyltrif Polyhydroxytriphenylmethanes such as enylmethane,

3,3,3 ', 3'-tetramethyl-1,1'-
Spirobi-indan-5,6,5 ', 6'-tetrol,
3,3,3 ', 3'-Tetramethyl-1,1'-spirobi-indane-5,6,7,5', 6 ', 7'-hexool, 3,3,
3 ', 3'-tetramethyl-1,1'-spirobi-indane-4,5,6,4', 5 ', 6'-hexool, 3,3,3',
3'-tetramethyl-1,1'-spirobi-indane-
Polyhydroxyspirobi-indanes such as 4,5,6,5 ', 6', 7'-hexool,

3,3-bis (3,4-dihydroxyphenyl) phthalide, 3,3-bis (2,3,4-trihydroxyphenyl) phthalide, 3 ', 4', 5 ', 6'- Polyhydroxyphthalides such as tetrahydroxyspiro [phthalide-3,9′-xanthene],

Flavonoid pigments such as morin, quercetin, rutin,

Α, α ', α "-tris (4-hydroxyphenyl) 1,3,5-triisopropylbenzene,
α, α ′, α ″ -tris (3,5-dimethyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (3,5-diethyl-4-)
Hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (3,5-di-n-propyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α , Α ', α "-Tris (3,5-
Diisopropyl-4-hydroxyphenyl) 1,3,5
-Triisopropylbenzene, α, α ', α "-tris (3,5-di-n-butyl-4-hydroxyphenyl)
1,3,5-triisopropylbenzene, α, α ′,
α ″ -tris (3-methyl-4-hydroxyphenyl)
1,3,5-triisopropylbenzene, α, α ′,
α ″ -tris (3-methoxy-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,
α ', α "-tris (2,4-dihydroxyphenyl)
1,3,5-triisopropylbenzene, 1,3,5-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Benzene, 1,3,5-tris (5-methyl-2-hydroxyphenyl) benzene, 2,4,6-tris (3,3
5-Dimethyl-4-hydroxyphenylthiomethyl) mesitylene, 1- [α-methyl-α- (4'-hydroxyphenyl) ethyl] -4- [α, α'-bis (4 "-hydroxyphenyl) ) Ethyl] benzene, 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -3-
[Α, α'-bis (4 "-hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (3 ', 5'-
Dimethyl-4'-hydroxyphenyl) ethyl] -4-
[Α, α′-bis (3 ″, 5 ″ -dimethyl-4 ″ -hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (3′-methyl-4′-hydroxyphenyl) ethyl ] -4- [α ', α'-bis (3 "-methyl-4"
-Hydroxyphenyl) ethyl] benzene, 1- [α-
Methyl-α- (3′-methoxy-4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (3 ″ -methoxy-4 ″ -hydroxyphenyl) ethyl] benzene,
1- [α-methyl-α- (2 ', 4'-dihydroxyphenyl) ethyl] -4- [α', α'-bis (4 "-hydroxyphenyl) ethyl] benzene, 1- [α- Methyl-α- (2 ′, 4′-dihydroxyphenyl) ethyl] -3- [α ″ α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene and the like described in JP-A-4-253058. Hydroxy compounds,

P-bis (2,3,4-trihydroxybenzoyl) benzene, p-bis (2,4,6-trihydroxybenzoyl) benzene, m-bis (2,3,4-trihydroxybenzoyl) benzene , M-bis (2,4,6-
Trihydroxybenzoyl) benzene, p-bis (2,
5-dihydroxy-3-bromobenzoyl) benzene,
p-bis (2,3,4-trihydroxy-5-methylbenzoyl) benzene, p-bis (2,3,4-trihydroxy-5-methoxybenzoyl) benzene, p-bis
(2,3,4-trihydroxy-5-nitrobenzoyl)
Benzene, p-bis (2,3,4-trihydroxy-5-
Cyanobenzoyl) benzene, 1,3,5-tris (2,
5-dihydroxybenzoyl) benzene, 1,3,5-tris (2,3,4-trihydroxybenzoyl) benzene, 1,2,3-tris (2,3,4-trihydroxybenzoyl) benzene, 1,2 , 4-Tris (2,3,4-trihydroxybenzoyl) benzene, 1,2,4,5-tetrakis (2,3,4-trihydroxybenzoyl) benzene, α, α′-bis (2,3, 4-trihydroxybenzoyl) -p-xylene, α, α ′, α′-tris (2,
3,4-trihydroxybenzoyl) mesitylene,

2,6-bis- (2'-hydroxy-
3 ', 5'-dimethyl-benzyl) -p-cresol,
2,6-bis- (2'-hydroxy-5'-methyl-benzyl) -p-cresol, 2,6-bis- (2'-hydroxy-3 ', 5'-di-t-butyl-benzyl) −
p-cresol, 2,6-bis- (2'-hydroxy-
5'-ethyl-benzyl) -p-cresol, 2,6-
Bis- (2 ', 4'-dihydroxy-benzyl) -p-
Cresol, 2,6-bis- (2'-hydroxy-3 '
-T-butyl-5'-methyl-benzyl) -p-cresol, 2,6-bis- (2 ', 3', 4'-trihydroxy-5'-acetyl-benzyl) -p-cresol,
2,6-bis- (2 ', 4', 6'-trihydroxy-
Benzyl) -p-cresol, 2,6-bis- (2 ',
3 ', 4'-trihydroxy-benzyl) -p-cresol, 2,6-bis- (2', 3 ', 4'-trihydroxy-benzyl) -3,5-dimethyl-phenol,
4,6-bis- (4'-hydroxy-3 ', 5'-dimethyl-benzyl) -pyrogallol, 4,6-bis-
(4'-Hydroxy-3 ', 5'-dimethoxy-benzyl) -pyrogallol, 2,6-bis- (4'-hydroxy-3', 5'-dimethyl-benzyl) -1,3,4-
Trihydroxy-phenol, 4,6-bis- (2 ',
4 ', 6'-trihydroxy-benzyl) -2,4-dimethyl-phenol, 4,6-bis- (2', 3 ',
4'-trihydroxy-benzyl) -2,5-dimethyl-phenol and the like can be mentioned.

Further, it is also possible to use a low-nuclear substance of a phenol resin such as a novolak resin.

The naphthoquinonediazide ester photosensitive materials of these polyhydroxy compounds are used alone or in combination of two or more kinds. The ratio of the photosensitive material to the alkali-soluble resin used is 100 parts by weight of the resin,
-100 parts by weight, preferably 10-50 parts by weight.
If the usage ratio is less than 5 parts by weight, the residual film rate is significantly reduced, while if it exceeds 100 parts by weight, the sensitivity and the solubility in a solvent are reduced.

The composition of the present invention may further contain a polyhydroxy compound in order to accelerate the dissolution in the developing solution. Preferred polyhydroxy compounds include phenols, resorcin, phloroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3 ', 4 ', 5'
-Hexahydroxybenzophenone, acetone-pyrogallol condensation resin, phlorogluside, 2,4,2 ', 4'-
Biphenyl tetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2 ', 4,4'-tetrahydroxydiphenyl ether, 2,2', 4,4'-tetrahydroxydiphenyl Nyl sulfoxide, 2,2 ', 4,
4'-tetrahydroxydiphenyl sulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4
-Hydroxyphenyl) cyclohexane, 4,4'-
(Α-methylbenzylidene) bisphenol, α, α ′,
α "-tris (4-hydroxyphenyl) -1,3,5-
Triisopropylbenzene, α, α ', α "-tris (4-
Examples thereof include hydroxyphenyl) -1-ethyl-4-isopropylbenzene and the like. These polyhydroxy compounds can be added in an amount of usually 100 parts by weight or less, preferably 5 to 50 parts by weight or less, based on 100 parts by weight of the quinonediazide compound.

Solvents for dissolving the photosensitive material and the alkali-soluble novolak resin of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol. Methyl ether acetate, propylene glycol propyl ether acetate, toluene,
Xylene, methyl ethyl ketone, cyclohexanone, 2
-Ethyl hydroxypropionate, 2-hydroxy-2
-Ethyl methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid Methyl, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate and the like can be used. These organic solvents are used alone or in combination of two or more.

Furthermore, N-methylformamide, N, N-
Dimethylformamide, N-methylacetamide, N,
A high-boiling solvent such as N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether can be mixed and used.

A surfactant may be added to the positive photoresist composition of the present invention in order to further improve the coating properties such as striation. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonyl Polyoxyethylene alkyl allyl ethers such as phenol ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristea Sorbitan fatty acid esters such as oleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sol Monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc., polyoxyethylene sorbitan fatty acid esters nonionic surface active agents such as, Efutotsupu EF
301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.),
Megafacs F171, F173 (Dainippon Ink Co., Ltd.)
Manufactured by Sumitomo 3M Co., Ltd., Asahi Guard AG710, Surflon S
-382, SC101, SC102, SC103, SC10
4, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), fluorine-based surfactant, organosiloxane polymer KP341
(Manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymerized Polyflow No. 75, No. 95
(Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and the like can be mentioned. The blending amount of these surfactants is 100% by weight of the alkali-soluble resin and the quinonediazide compound in the composition of the present invention.
It is usually 2 parts by weight or less, preferably 1 part by weight or less, per part by weight. These surfactants may be added alone or in some combinations.

The developer for the positive photoresist composition of the present invention includes sodium hydroxide, potassium hydroxide,
Inorganic alkalis such as sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, triethylamine and methyldiethylamine. Tertiary amines such as
Use an aqueous solution of alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, cyclic amines such as pyrrole and piperidine, and alkalis such as You can Further, an appropriate amount of alcohols and surfactants may be added to the above aqueous solution of alkalis for use.

If necessary, a dye, a plasticizer and an adhesion aid can be added to the positive photoresist composition of the present invention. Specific examples thereof include dyes such as methyl violet, crystal violet and malachite green, stearic acid, acetal resins, phenoxy resins, plasticizers such as alkyd resins, and adhesion promoters such as hexamethyldisilazane and chloromethylsilane. is there.

The above positive photoresist composition is applied on a substrate (eg, silicon / silicon dioxide coating) used for the production of precision integrated circuit devices by a suitable coating method such as a spinner or coater, and then prebaked. Exposure through a specified mask and post-heating (PEB: Post
A good resist can be obtained by performing Exposure Bake), and developing, rinsing, and drying. Examples of the present invention will be shown below, but the present invention is not limited thereto. In addition,% indicates weight% unless otherwise specified.

[0050]

【Example】

(1) Synthesis of Photosensitive Material a Compound [I-1] (50.8 g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (67.2 g) and acetone (750 ml) were charged into a three-necked flask and uniformly dissolved. Then, triethylamine / acetone = 26.6
g / 100 ml was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was poured into 3000 ml of a 1% aqueous hydrochloric acid solution, the precipitate formed was filtered off, washed with water and dried (40 ° C.) to obtain 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [I-1]. (Photosensitive material a) 94.4 g was obtained.

(2) Synthesis of Photosensitive Material b 53.6 g of compound [I-3], 61.8 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 750 ml of acetone were charged in a three-necked flask and uniformly dissolved. did. Then triethylamine / acetone = 24.4
g / 100 ml was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was poured into 3000 ml of a 1% aqueous hydrochloric acid solution, the precipitate formed was filtered off, washed with water and dried (40 ° C.) to obtain 1,2-naphthoquinonediazide-5-sulfonate of compound [I-3]. (Photosensitive material b) 93.1 g was obtained.

(3) Synthesis of Photosensitive Material c Compound [I-9] 49.2 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 67.2 g, and acetone 750 ml were charged in a three-necked flask and uniformly dissolved. did. Then, triethylamine / acetone = 26.6
g / 100 ml was gradually added dropwise and reacted at 25 ° C. for 6 hours. The reaction mixture was poured into 3000 ml of a 1% hydrochloric acid aqueous solution, the resulting precipitate was filtered off, washed with water and dried (40 ° C.) to obtain 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [I-9]. (Photosensitive material c) 94.4 g was obtained.

(4) Synthesis of Photosensitive Material d 2,3,4,4'-Tetrahydroxybenzophenone 1
2.3 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 40.3 g, and acetone 300 ml 3
It was charged in a single-necked flask and uniformly dissolved. Then, triethylamine / acetone = 15.2 g / 50 ml was gradually added dropwise, and the mixture was reacted at 25 ° C. for 3 hours. 1% of reaction mixture
It was poured into 1500 ml of hydrochloric acid aqueous solution, the precipitate formed was separated by filtration, washed with water and dried (40 ° C.), and then 2, 3, 4, 4′-
1,2-naphthoquinonediazide-5-sulfonic acid ester of tetrahydroxybenzophenone (photosensitive material d) 3
9.7 g was obtained.

(5) Synthesis of Photosensitive Material e α, α, α'-Tris (4-hydroxyphenyl) -1
-Ethyl-4-isopropylbenzene 42.5 g, 1,
2-naphthoquinonediazide-5-sulfonyl chloride 6
1.8 g and 650 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then, triethylamine / acetone = 24.4 g / 80 ml was gradually added dropwise at 25 ° C.
And reacted for 4 hours. The reaction mixture is 1% aqueous hydrochloric acid solution 25
Pour into 00 ml, filter the resulting precipitate, wash with water and dry
(40 ° C.) to obtain 1,2-naphthoquinonediazide-5-sulfonic acid ester of α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (photosensitive material e) 83. 1 g was obtained.

(6) Synthesis of Photosensitive Material f 2,2-bis [4-hydroxy-3,5di (4-hydroxybenzyl) phenyl] propane 30.8 g, 1,2
-Naphthoquinonediazide-5-sulfonyl chloride 5
3.8 g and 600 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then, triethylamine / acetone = 21.3 g / 50 ml was gradually added dropwise at 25 ° C.
And reacted for 6 hours. The reaction mixture is 1% aqueous hydrochloric acid solution 25
Pour into 00 ml, filter the resulting precipitate, wash with water and dry
(40 ° C.) to give 2,2-bis [4-hydroxy-
67.2 g of 1,2-naphthoquinonediazide-5-sulfonic acid ester of 3,5-di (4-hydroxybenzyl) phenyl] propane (photosensitive material f) was obtained.

(7) Synthesis of Novolac Resin A m-cresol 40 g, p-cresol 60 g, 37%
Formalin aqueous solution (49 g) and oxalic acid (0.13 g) were charged into a three-necked flask, and the temperature was raised to 100 ° C. with stirring to react for 15 hours. Then raise the temperature to 200 ° C,
The pressure was gradually reduced to 5 mmHg to remove water, unreacted monomers, formaldehyde, oxalic acid and the like. Then, the molten alkali-soluble novolak resin was returned to room temperature and recovered. The obtained novolak resin A had a weight average molecular weight of 7100 (in terms of polystyrene).

(8) Synthesis of Novolac Resin B m-cresol 50 g, p-cresol 25 g, 2,5
-Xylenol 28 g, 37% formalin aqueous solution 53 g
Further, 0.15 g of oxalic acid was charged into a three-necked flask, the temperature was raised to 100 ° C. with stirring, and the reaction was carried out for 12 hours. Thereafter, the temperature was raised to 200 ° C., and the pressure was gradually reduced to 1 mmHg to distill off water, unreacted monomers, formaldehyde, oxalic acid and the like. Then, the molten novolak resin was returned to room temperature and recovered. The obtained novolak resin had a weight average molecular weight of 4,300 (in terms of polystyrene). Next, 20 g of this novolak resin was completely dissolved in 60 g of methanol, and then 30 g of water was gradually added thereto with stirring to precipitate a resin component. The upper layer was removed by decantation, the precipitated resin component was recovered, heated to 40 ° C., and dried under reduced pressure for 24 hours to obtain an alkali-soluble novolak resin B. The obtained novolak resin had a weight average molecular weight of 8920 (in terms of polystyrene), and the contents of the monomer, dimer and trimer were 0% and 2.3, respectively.
% And 3.5%.

(9) Preparation and Evaluation of Positive Photoresist Composition Photosensitive materials a to f obtained in the above (1) to (6), novolak resin obtained in the above (7) and (8), solvent and If necessary, polyhydroxy compounds were mixed in the proportions shown in Table 1 to form a uniform solution, which was then filtered using a microfilter having a pore size of 0.2 μm to prepare a photoresist composition. This photoresist composition was applied to a silicon wafer using a spinner, and a vacuum adsorption type hot plate
It was dried at 0 ° C. for 60 seconds to obtain a resist film having a thickness of 1.0 μm. After exposing this film using a reduction projection exposure apparatus (reduction projection exposure apparatus NSR-2005i9C manufactured by Nikon Corporation),
PEB was carried out at 110 ° C. for 60 seconds, followed by development with a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute, washing with water for 30 seconds and drying. The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist. The results are shown in Table 2. The sensitivity was defined as the reciprocal of the exposure amount for reproducing a mask pattern of 0.60 μm, and shown as a relative value with respect to the sensitivity of Comparative Example 1. The residual film rate was expressed as a percentage of the ratio of the unexposed area before and after development. The resolving power represents a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.60 μm. The heat resistance was a temperature at which a resist-patterned silicon wafer was baked on a hot plate for 4 minutes and the deformation of the pattern did not occur. The shape of the resist is
It is represented by the angle (θ) formed by the resist wall surface and the plane of the silicon wafer in the 0.50 μm resist pattern cross section. Regarding the storage stability, the solution of the positive photoresist composition was allowed to stand at room temperature and the presence or absence of precipitates in the solution was examined after 3 months. The thing which precipitation was not observed was represented by (circle), and the thing observed was represented by x.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

The positive photoresist using the photosensitive material of the present invention is excellent in sensitivity, developability, heat resistance and storage stability, especially in resolution, and is suitably used as a photoresist for fine processing.

Claims (1)

[Claims] 1. A 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonic acid ester of a polyhydroxy compound represented by the following general formula (I) and an alkali-soluble resin. A positive type photoresist composition. [Chemical 1] Here, R _{1 to} R ₁₀ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acyl group, an alkenyl group, a nitro group or a cyano group, a, b, c, d. : 1 or 2 (however, a + c = b + d
= 4), and n: 4 or 5.