JPH09106070A - Positive photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide positive photoresist composition with high sensitivity and resolution, excellent sectional-shape resist patterns can be formed, an obtained resist image is excellent in heat resistance, wide defocusing latitude and property to make small contact holes by using alkali soluble resin and quinone diazide compound with a specified structural formula. SOLUTION: Positive photoresist composition contains quinone diazide sulfonic acid ester of at least one type of polyhydroxy compound selected out of the formula I-III and alkali soluble resin. In the formula I-III, R1 , R2 are hydrogen atoms, halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, acyl groups, alkynyl groups, aralkyl groups or alkoxycarbonyl groups, R3 is hydrogen atoms or alkyl groups, R4 is as shown in the formula IV, (n) is 1-3 integers, (m) is 1 or 2, (x), (y) are 1-3 integers and (z) is 1-3 integers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive positive photoresist composition, and more particularly to a photoresist composition having a high resolving power and sensitivity, a good pattern sectional shape, and a fine contact hole. And a photoresist composition for microfabrication. The positive photoresist according to the present invention is applied on a substrate such as a semiconductor wafer, glass, ceramics, or metal to a thickness of 0.5 to 3 μm by a spin coating method or a roller coating method. 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. Typical fields of application include manufacturing processes for semiconductors such as ICs, manufacturing circuit boards such as liquid crystals and thermal heads, and other photo-ablation processes.

[0002]

2. Description of the Related Art Positive photoresist compositions include:
In general, 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 phenolic resin / naphthoquinonediazide-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 "Introducio
n to Microlithography ”) (A
CS Publishing, No. 219, P112-121). Novolak resin as a binder is soluble in an alkaline aqueous solution without swelling, and is particularly useful in this application because it gives high resistance to plasma etching especially when the generated image is used as a mask for etching. It is. Further, the naphthoquinonediazide compound used in the photosensitive material itself acts as a dissolution inhibitor that reduces the alkali solubility of the novolak resin, but when decomposed by irradiation with light, generates an alkali-soluble substance and rather increases the alkali solubility of the novolak resin. 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 property change to light. From this point of view, many positive photoresists containing a novolak resin and a naphthoquinonediazide type photosensitive material have been developed and put into practical use, and have achieved sufficient results in line width processing up to about 1 μm.

[0003] However, the degree of integration of integrated circuits is increasing more and more, and in the manufacture of semiconductor substrates such as VLSI, one is required.
Processing of ultrafine patterns having a line width of not more than μm, and further not more than 0.5 μm has been required. 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, U.S. Pat. Nos. 3,046,118, 3,106,465 and 31,
48983, Japanese Patent Publication No. 37-18015, 56-2
In reality, it is not possible to deal with the positive type photoresists using 1,2-naphthoquinone diazide sulfonic acid esters of gallic acid esters and polyhydroxybenzophenones as described in JP-A No. 333, 62-28457 and the like. is there.

1,2 of polyhydroxybenzophenones
-A positive photoresist composition having properties suitable for ultrafine processing by using 1,2-naphthoquinone diazide sulfonic acid ester of a specific polyhydroxy compound as a photosensitive component instead of naphthoquinone diazide sulfonic acid ester Many proposals have been made (for example, JP-A Nos. 60-163043, 61-97278, 62-10645, 62-10646, and 62-).
No. 198852, No. 63-220139, and Japanese Patent Publication No. 62
No. 3411, Japanese Patent Publication No. 1-38289, No. 1-459.
No. 01, JP-A-1-291240 and 1-29124.
No. 1, No. 1-291242, No. 1-280748,
JP-A-2-269351, JP-A-2-296248, and JP-A-2-296249).

Further, a large number of 1,2-naphthoquinonediazide compounds, which are polyhydroxy compounds having a specific structure, have been proposed in order to enhance the resolution. For example, JP-A Nos. 57-63526, 60-163043 and 6
No. 2-10645, No. 62-1646, No. 62-1
No. 50245, No. 63-220139, No. 64-76
No. 047, JP-A-1-189644 and JP-A-2-2853.
No. 51, No. 2-296248, No. 2-296249.
No. 3, No. 3-48249, No. 3-48250, No. 3-
No. 158856, No. 3-228057, Special Table 4-5
No. 02519, JP-A-4-365046, US Pat.
957846, 4992356, 515134
No. 0, No. 5178986, and European Patent No. 530148.

On the other hand, the use of a photosensitive material having a hydroxyl group in the molecule makes it possible to obtain a resist having high contrast and high resolution.
015, JP-A-58-150948, JP-A 2-1
No. 9846, No. 2-103543, No. 3-22805
No. 7, 5-323597, European Patent 573056.
No. 3,184,310, U.S. Pat.
No. 3130047, No. 3130048, No. 3130
No. 049, No. 3102809, No. 3061430,
No. 3180733, West German Patent 938233, SPIE P
roceedings Vol. 631, page 210, Vol. 1672, page 231 (1992),
Vol. 1672, p. 262 (1992) and Vol. 1925, p. 227 (1993)
Year). Certainly, the resists containing the photosensitive materials described in these publications have improved performance in forming fine line widths, but there are still insufficient points.

Further, in the manufacture of semiconductor devices, apart from the purpose of forming fine line widths, the size of holes for passing metal for electrodes of semiconductor devices to the semiconductor surface, ie, the form of contact holes, has been miniaturized. A positive photoresist composition suitable for this is required. However, in order to open a minute contact hole,
Nobody knew how to design a resist material. It has been found that a resist suitable for obtaining a fine line width is not necessarily suitable for contact hole use. Japanese Patent Application No. 5-251780 describes a structure similar to the polyhydroxy compound of the present invention.
There was no suggestion of contact holes in these compounds.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a resist pattern having a high sensitivity and a high resolving power and an excellent cross-sectional shape, particularly in the manufacture of semiconductor devices, and the obtained resist image has heat resistance. An object of the present invention is to provide a positive photoresist composition which has excellent defocusing characteristics, a wide defocus latitude, and is suitable for forming fine contact holes.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies while paying attention to the above-mentioned various properties. As a result, the present inventors have found that the above object can be achieved by using an alkali-soluble resin and a quinonediazide compound having a specific structural formula. And completed the present invention on the basis of this finding. That is, the object of the present invention is characterized by containing at least one quinonediazide sulfonic acid ester of a polyhydroxy compound selected from the following general formulas (1), (2) and (3) and an alkali-soluble resin. It was achieved by using a positive photoresist composition.

[0010]

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[0011]

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R ₁ and R _2, which may be the same or different, are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group,
Aryl group, alkoxy group, acyl group, alkenyl group,
It represents an aralkyl group, an alkoxycarbonyl group, an arylcarbonyl group, an acyloxy group, a nitro group, or a cyano group. It represents a hydrogen atom, an alkyl group: R _3. n: an integer of 1 to 3, m: 1 or 2, x, y: an integer of 1 to 3, z: an integer of 1 to 3

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyhydroxy compounds represented by the general formulas (1) to (3) will be described. R ₁ in the general formulas (1) to (3),
In R ₂ , a halogen atom is a chlorine atom, a bromine atom or an iodine atom, and an alkyl group is a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a t-butyl group. Such an alkyl group having 1 to 4 carbon atoms can be used as an alkoxy group such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, isopropoxy group, n-
An alkoxy group having 1 to 4 carbon atoms such as butoxy group, isobutoxy group, sec-butoxy group or t-butoxy group is preferable. The cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group. 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 is a phenyl group, a xylyl group, a toluyl group or a cumenyl group, the aralkyl group is a benzyl group, a phenethyl group or a cumyl group, the alkoxycarbonyl group is a methoxycarbonyl group or an ethoxycarbonyl group, and the arylcarbonyl group is an 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. The alkyl group for R ₃ is preferably the same as the alkyl group described for R ₁ and R ₂ .

Of the compounds represented by the general formulas (1) to (3)
As specific examples, the following [Ia] to [Ip] and [II-
a] to [II-h] and [III-a] to [III-h]
However, the compounds are not limited to these.
It is not something to be done. These polyhydroxy compounds are
They may be used alone or in combination of two or more. An example
For example, among the general formulas (1) to (3), the molecular weight is relatively small.
Saimono (for example, R _FourRepresents a hydrogen atom) and a molecule
Larger amount (eg R_FourIs other than hydrogen atom
Stuff) can be used together.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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The photosensitive material according to the present invention has, for example, part or all of the hydroxyl groups of the polyhydroxy compound described above as 1,2-
It can be obtained by carrying out a usual esterification reaction with naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride in the presence of a basic catalyst. That is, a predetermined amount of a polyhydroxy compound and 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride, a solvent such as dioxane / acetone / methylethylketone / N-methylpyrrolidone, dimethoxyethane, tetrahydrofuran, diglyme, Ethyl acetate, dichloroethane, chloroform, γ-butyrolactone, etc. were charged in a flask and a basic catalyst such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethylamine,
4-dimethylaminopyridine, N-methylmorpholine,
N-methylpiperazine, N-methylpyrrolidine, etc. are added dropwise to condense. The product obtained is purified after washing with water and dried. In the usual esterification reaction, a mixture having different esterification numbers and esterification positions can be obtained.
It is also possible to selectively esterify only certain specific isomers by selecting the synthesis conditions or the structure of the polyhydroxy compound. The esterification rate referred to in the present invention is defined as an 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
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 in an alkali-soluble resin. The blending amount is 100% Novolac resin.
5 to 150 parts by weight of the compound, preferably 2
0 to 100 parts by weight. If the use ratio is less than 5 parts by weight, the residual film rate is remarkably lowered, and if it exceeds 150 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 is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde 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
-Alkoxyphenols such as butoxyphenol, 2
Bisalkylphenols such as -methyl-4-isopropylphenol, hydroxyaromatic compounds such as m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol and naphthol Can be used alone or in combination of two or more.
It is not limited to these.

Examples of 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 its acetal form, such as chloroacetaldehyde diethyl acetal, can be used, and among these, formaldehyde is preferably used. These aldehydes are
They are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, mercaptoacetic acid, methanesulfonic acid, malonic acid, oxalic acid and the like can be used.

Further, JP-A-60-45238 and JP-A-60-45238
-97347, 60-140235, 60-1
89739, 64-14229 and JP-A-1-27.
6131, 2-60915, and 2-275955.
No. 2, No. 2,287,445, No. 4-101147, No. 4-122938, and the like, for example, by a method such as fractional precipitation, fractional dissolution, column chromatography, etc. You may use what removed or reduced the component.

The weight average molecular weight of the thus obtained novolak resin is preferably in the range of 1500 to 20000. If it is less than 1500, the film loss of the unexposed area after development is large, and if it exceeds 20,000, the developing speed becomes small. Particularly preferred is the range of 2500-15000. Here, the weight average molecular weight is defined as a value in terms of polystyrene of gel permeation chromatography.

In the present invention, the above-mentioned photosensitive material should be mainly used, but if necessary, 1,2-naphthoquinonediazide-5- (and / or-4-) sulfonyl chloride of the polyhydroxy compound shown below 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'-pentahydroxy Benzophenone, 2,3,4,2 ', 4'-pentahydroxybenzophenone, 2,3,4,2', 5'-pentahydroxybenzophenone, 2,4,6,3 ', 4 Polyhydroxybenzophenones such as', 5'-hexahydroxybenzophenone, 2,3,4,3 ', 4', 5'-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 ((poly) hydroxyphenyl) alkanes such as bis (2,3,4-trihydroxyphenyl) propane-1, 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 Pentore, 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'-tetrahydroxydiphenylsulfoxide,

Bis (polyhydroxyphenyl) sulfones such as 2,2 ', 4,4'-tetrahydroxydiphenyl 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 ',
Poly "3,4"-octahydroxy-5,5'-diacetyltriphenylmethane, 2,4,6,2 ', 4', 6'-hexahydroxy-5,5'-dipropionyltriphenylmethane, etc. Hydroxytriphenylmethanes,

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-4,5,6,
Polyhydroxyspirobi-indanes such as 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],

Flavono 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 (3,5-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 etc. JP-A-4-25305
The polyhydroxy compound described in JP-A-8,

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.

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

The naphthoquinonediazide ester photosensitive material of these polyhydroxy compounds can be used alone or in combination of two or more kinds in combination with the photosensitive material of the present invention, and usually 50 parts by weight per 100 parts by weight of the photosensitive material of the present invention. Below the section,
It can be preferably mixed in a proportion of 30 parts by weight or less.

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, phloroglucide, 2,4,2', 4'-biphenyl tetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2 ', 4,4'-tetrahydroxydiphenyl ether, 2,2', 4,4'-tetrahydroxydiphenyl 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-hi Rokishifeniru) -1,3,5-triisopropylbenzene, α, α ', α "- tris (4-hydroxyphenyl) -
1-ethyl-4-isopropylbenzene etc. can be mentioned. The blending amount of these polyhydroxy compounds is
Usually 100 per 100 parts by weight of alkali-soluble resin
It may be added in an amount of not more than 10 parts by weight, preferably 5 to 70 parts by weight, more preferably 10 to 60 parts by weight.

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 β-methoxyisobutyrate, methyl α-hydroxyisobutyrate, 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.

Further, N-methylformamide, N, N-
Dimethylformamide, N-methylacetamide, N,
High-boiling solvents such as N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl 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 alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and polyoxyethylene nonyl. Polyoxyethylene alkyl allyl ethers such as phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters such as 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.), Megafask F171, F173 (manufactured by Dainippon Ink Co., Ltd.),
Fluorard FC430, FC431 (Sumitomo 3M Limited)
Made), Asahi Guard AG710, Surflon S-382,
SC101, SC102, SC103, SC104, SC1
05, SC106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based
(Co) polymerization polyflow No. 75, No. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like can be mentioned. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the alkali-soluble resin and the quinonediazide compound in the composition of the present invention. These surfactants may be added alone or in some combination.

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 dimethyl ethanol amine and triethanol amine, quaternary ammonium salts such as tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide choline, cyclic amines such as pyrrole and piperidine, and alkalis such as be able to. Furthermore, alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants can be added to the aqueous solution of the above alkalis in appropriate amounts.

If necessary, the positive photoresist composition of the present invention may contain a light absorber, a cross-linking agent, and an adhesion aid. The light absorbing agent is added as needed for the purpose of preventing halation from the substrate or for enhancing the visibility when applied to a transparent substrate. For example, commercially available light absorbers, such as CI Dis, which are on-board in "Technology and Market of Industrial Dyes" (CMC Publishing) and Dye Handbook (Organic Synthetic Chemistry Association).
perse Yellow 1, 3, 4,5, 7, 8, 13, 23, 31, 49, 50,
51, 54, 56, 60, 64, 66, 68, 79, 82, 88, 90, 93, 10
2, 114 and 124, CI Disperse Orange 1, 5, 13, 25,
29, 30, 31, 44, 57, 72 and 73, CI Disperse Red 1,
5, 7, 13, 17, 19, 43, 50, 54, 58, 65,72, 73, 88, 1
17, 137, 143, 199 and 210, CI Disperse Violet 4
3, CI Disperse Blue 96, CI Fluorescent Bright
ening Agent 112, 135 and 163, CI Solvent Yellow 1
4, 16, 33 and 56, CI Solvent Orange 2 and 45, CI
Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49, CI P
igment Green 10 and CI Pigment Brown 2 can be preferably used. The light absorber is usually 100 parts by weight or less, preferably 5 parts by weight, based on 100 parts by weight of the alkali-soluble resin.
The amount is 0 parts by weight or less, more preferably 30 parts by weight or less.

The crosslinking agent is added within a range that does not affect the formation of a positive image. The purpose of adding the crosslinking agent is mainly
These include sensitivity adjustment, improvement of heat resistance, improvement of dry etching resistance, and the like. Examples of the cross-linking agent include melamine, benzoguanamine, glycoluryl, etc., which are reacted with formaldehyde, or alkyl modified products thereof, epoxy compounds, aldehydes, azide compounds, organic peroxides, hexamethylenetetramine, etc. You can These crosslinking agents can be blended in a proportion of less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the photosensitive agent. If the amount of the crosslinking agent exceeds 10 parts by weight, the sensitivity is lowered, and scum (development residue) is undesirably generated.

The adhesion aid is mainly added for the purpose of improving the adhesion between the substrate and the resist and preventing the resist from being peeled off especially in the etching step. Specific examples include trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chlorosilanes such as chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane,
Alkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, silazanes such as trimethylsilylimidazole, vinyltrichlorosilane, γ-
Silanes such as chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-
Heterocyclic compounds such as mercaptobenzimidazole, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, and urea such as 1,1-dimethylurea and 1,3-dimethylurea, or Thiourea compounds may be mentioned. These adhesion aids are usually added in an amount of 10 parts by weight per 100 parts by weight of the alkali-soluble resin.
It is blended in a proportion of less than 5 parts by weight, preferably less than 5 parts by weight.

A substrate (eg, silicon / silicon dioxide coating, titanium-nitride, titanium-tungsten, amorphous carbon, or other inorganic antireflection film) containing the positive photoresist composition as used in the manufacture of precision integrated circuit devices. Substrate, or an organic antireflection film is applied and dried, and a film substrate, a glass substrate, a transparent substrate such as an ITO substrate, etc.) is spin-coated, roll-coated, flow-coated, dip-coated, spray-coated, After applying a suitable coating method such as a doctor coat method, pre-paking it, exposing it through a predetermined mask, performing post-baking (PEB: Post Exposure Bake) if necessary, developing, rinsing, and drying a good resist. Can be obtained.

[0059]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples. In addition,% indicates weight% unless otherwise specified. Synthesis Example 1 Synthesis of Compound [Im] A mixture of 270 g of phenol and 3 ml of dodecylthiol was heated to 50 ° C. and hydrogen chloride gas was bubbled through the heated mixture for 30 minutes. 1, after 15 minutes
8 g of 30 g of 5-dimethyl-1,4-cyclohexadiene
After adding over minutes and stirring at 50 ° C. for 22 hours, the mixture was diluted with ethyl acetate, washed 3 times with water, dried over magnesium sulphate and the excess phenol removed by vacuum stripping. The brown residue was recrystallized from chlorobenzene to give 1,3-bis (4-hydroxyphenyl) -1,3-dimethylcyclohexane [I-
m] was obtained.

Synthesis Example 2 Synthesis of Compound [In] 270 g of the phenol of Synthesis Example 1 was added to o-cresol 31.
1,3-bis (3-methyl-4-hydroxyphenyl) -1,3-synthesized in the same manner except that the amount was changed to 1.0 g.
21 g of dimethylcyclohexane [In] was obtained.

Synthesis Example 3 Compounds [III-g] and [I-
Synthesis of p] [III-g]; 4- [1- [3- (4-hydroxyphenyl) -4-methylcyclohexyl] -1-methylethyl] -phenol [Ip]; 4,4 '-[ 1-methyl-4- (1-methylethyl) -1,3-cyclohexanediyl] bisphenol

A solution of 2000 g of phenol, 425 g of γ-terpinene, and 200 g of acidic ion exchange resin Amberlyst 31 was heated at 95 to 110 ° C. for 20 hours. After that, the ion exchange resin was filtered off and distilled under reduced pressure to remove residual phenol and to obtain a distillation residue. Chloroform (600 ml) was added to the residue at a temperature of 50 ° C. This residue /
The chloroform mixture was cooled to room temperature over 10 hours to produce a crude tan crystalline [III-g] compound. The crude [III-g] solid was recovered from the chloroform mixture by filtration, thereby leaving behind a filtrate containing the [Ip] compound. The crude [III-g] solid was recrystallized from chloroform to obtain pure [III-g] white crystals (270 g) and another [Ip] filtrate. The two filtrates described above were concentrated in vacuo, then the second white solid was collected by filtration, which was recrystallized from isopropyl alcohol to give the pure [Ip] compound (31
g) was obtained.

Synthesis Example 4 Synthesis of compound [III-h] Synthesis was carried out in the same manner as in [III-h] except that 2000 g of phenol in the synthesis of [III-g] in Synthesis Example (3) was changed to 2300 g of o-cresol. ] 240g of compounds were obtained.

Synthesis Example 5 Synthesis of compound [II-g] [II-g]; 4,4 '-[1-methyl-4- (1-methylethyl) -1,4-cyclohexanediyl] bisphenol phenol 338. 4 g of boron trifluoride / diethyl ether complex (3.4 g) was charged into a 500 ml three-necked flask, 81.6 g of α-terpinene was added dropwise at 80 ° C. over 3 hours, and the mixture was stirred at the same temperature for 2 hours to react. Let Then, the product was washed with distilled water three times, and then heated under reduced pressure to distill away phenol and by-products to obtain a crude [II-g] solid. This was recrystallized from chlorobenzene to give pure [II-g] compound 8
2.0 g were obtained.

Synthesis Example 6 Synthesis of Compound [II-h] Phenol 3 in Synthesis of [II-g] of Synthesis Example 5
63.0 g of the [II-h] compound was obtained in the same manner except that 38.4 g was changed to o-cresol 389.1 g.

Synthesis Example 7 Synthesis of Compound [Ia] Compounds [In] obtained in Synthesis Example 2 19.4 and 37.3
% Formalin 29 g, and 25.0% tetramethylammonium hydroxide 55 g at room temperature for 3 hours
It was added dropwise over 0 minutes. The mixture was reacted at 40 ° C. for 8 hours, diluted with 200 ml of ion-exchanged water, neutralized with 9 g of acetic acid, and then filtered. The obtained solid was put into 400 ml of ion-exchanged water, reslurried, and then filtered again,
It was vacuum dried at 40 ° C. for 48 hours to obtain the following intermediate [A]. 10.6 g of this intermediate [A] and 56.4 of phenol.
g was dissolved in 70 liters of methanol, 0.3 g of concentrated sulfuric acid was added dropwise to this mixed solution at room temperature over 1 hour, and the mixture was refluxed and stirred for 5 hours. After that, 800 ml of ion-exchanged water was added for crystallization, and the supernatant was decanted. After adding 27.4 g of 25% tetramethylammonium and re-dissolving this,
16.0 g of 5% ammonium sulfate was added for salting out, followed by filtration. After adding 600 ml of 0.6% hydrochloric acid to the obtained solid and reslurrying it, the mixture was filtered again, and the obtained pasty solid was vacuum dried at 40 ° C. for 48 hours to give a compound [I-
a] was obtained in an amount of 11.8 g.

[0067]

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Synthesis Example 8 Synthesis of Compound [II-a] 51.1 g of compound [II-h] obtained in Synthesis Example 6 and 37.
Charge 32.5% formalin 72.5g and add 25.0g to it.
% Tetramethylammonium hydroxide 137.5
g was added dropwise at room temperature over 30 minutes. This mixture is 40 ℃
After reacting for 8 hours with, the mixture was diluted with 450 ml of ion-exchanged water, neutralized with 22.5 g of acetic acid, and filtered. The obtained solid was put in 1 liter of ion-exchanged water, reslurried, then filtered again, and vacuum dried at 40 ° C. for 48 hours to obtain the following intermediate [B]. 30.4 g of this intermediate and 282.0 g of phenol were dissolved in 150 ml of methanol, 0.8 g of concentrated sulfuric acid was added dropwise to this mixed solution at room temperature over 1 hour, and the mixture was refluxed and stirred for 5 hours. After that, 2.0 liters of ion-exchanged water was added for crystallization, and the supernatant was decanted. 25% tetramethyl ammonium 68.5
g and redissolved, then 5% ammonium sulfate 4
0.0 g was added and salting out was performed, followed by filtration. After adding 1.5 liters of 0.6% hydrochloric acid to the obtained solid and reslurrying, it was filtered again to obtain a paste-like solid at 40 ° C.
Vacuum dried for 48 hours at 30.4 g of compound [II-a]
I got

[0069]

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Synthesis Example 9 Synthesis of Compound [III-a] 53.4 g and 3 of Compound [III-h] obtained in Synthesis Example 4
Charge 73.0 g of 7.3% formalin, and add 2 to it.
5.0% tetramethylammonium hydroxide 13
7 g was added dropwise at room temperature over 30 minutes. 40 this mixture
After reacting at 8 ° C for 8 hours, the mixture was diluted with 500 ml of ion-exchanged water, neutralized with 23 g of acetic acid, and filtered. The obtained solid was put into 1 liter of ion-exchanged water, reslurried, then filtered again, and vacuum dried at 40 ° C. for 48 hours,
The following intermediate [C] was obtained. 31.5 g of this intermediate [C]
And 141 g of phenol were dissolved in 180 liters of methanol, and 0.75 g of concentrated sulfuric acid was added dropwise to this mixed solution at room temperature over 1 hour, and the mixture was refluxed and stirred for 5 hours. After that, 2 liters of ion-exchanged water was added for crystallization, and the supernatant was decanted. 25% tetramethylammonium 6.9g
And redissolved, 5% ammonium sulfate 40.
0 g was added for salting out, followed by filtration. 0.6 in the obtained solid
% Hydrochloric acid (1.5 liter) was added and reslurried, and then the mixture was filtered again, and the obtained paste-like solid was vacuum dried at 40 ° C. for 48 hours to obtain 29.6 g of compound [III-a].

[0071]

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Synthesis Example 10 Synthesis of Photosensitive Material a <Invention> 15.0 g of the compound [Im] obtained in Synthesis Example 1, 20.2 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 250 ml of acetone were added. It was charged in a three-necked flask and uniformly dissolved. Then
Triethylamine / acetone = 8.7 g / 25 ml was gradually added dropwise, and the mixture was reacted at 25 ° C. for 3 hours. Add 1 reaction mixture
% Hydrochloric acid aqueous solution 750 ml, the precipitate formed is filtered off,
After washing with water and drying (40 ° C.), the compound [Im] 1,
2-6.4 g of 2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive material a) was obtained.

Synthesis Example 11 Synthesis of Photosensitive Material b <Invention> 15.5 g of the compound [II-g] obtained in Synthesis Example 5, 20.2 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 250 ml of acetone were added. It was charged in a three-necked flask and uniformly dissolved. Then
Triethylamine / acetone = 8.7 g / 25 ml was gradually added dropwise, and the mixture was reacted at 25 ° C. for 3 hours. Add 1 reaction mixture
% Hydrochloric acid aqueous solution 750 ml, the precipitate formed is filtered off,
After washing with water and drying (40 ° C.), the compound [II-g]
2-7.8 g of 2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive material b) was obtained.

Synthesis Example 12 Synthesis of Photosensitive Material c <Invention> 16.2 g of the compound [III-g] obtained in Synthesis Example 3, 20.2 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 250 ml of acetone were added. It was charged in a three-necked flask and uniformly dissolved. Then
Triethylamine / acetone = 8.7 g / 25 ml was gradually added dropwise, and the mixture was reacted at 25 ° C. for 3 hours. Add 1 reaction mixture
% Hydrochloric acid aqueous solution 750 ml, the precipitate formed is filtered off,
After washing with water and drying (40 ° C.), 28.7 g of 1,2-naphthoquinonediazide-5-sulfonic acid ester of Compound [III-g] (photosensitive material c) was obtained.

Synthesis Example 13 Synthesis of Photosensitive Material d <Invention> 5.6 g of the compound [Ia] obtained in Synthesis Example 7, 5.4 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 100 ml of acetone were added. It was charged in a three-necked flask and uniformly dissolved. Then
Triethylamine / acetone = 2.1 g / 10 ml was gradually added dropwise, and the mixture was reacted at 25 ° C. for 3 hours. Add 1 reaction mixture
% Aqueous hydrochloric acid solution (450 ml), the precipitate formed is filtered off,
After washing with water and drying (40 ° C.), the compound [Ia] 1
8.3 g of 2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive material d) was obtained.

Synthesis Example 14 Synthesis of Photosensitive Material e <Invention> 5.6 g of the compound [II-a] obtained in Synthesis Example 8, 5.4 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 100 ml of acetone were added. It was charged in a three-necked flask and uniformly dissolved. Then
Triethylamine / acetone = 2.1 g / 10 ml was gradually added dropwise, and the mixture was reacted at 25 ° C. for 3 hours. Add 1 reaction mixture
% Aqueous hydrochloric acid solution (450 ml), the precipitate formed is filtered off,
After washing with water and drying (40 ° C.), the compound [II-a]
8.2 g of 2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive material e) was obtained.

Synthesis Example 15 Synthesis of Photosensitive Material f <Invention> 5.6 g of the compound [III-a] obtained in Synthesis Example 9, 5.4 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 100 ml of acetone were added. It was charged in a three-necked flask and uniformly dissolved. Then
Triethylamine / acetone = 2.1 g / 10 ml was gradually added dropwise, and the mixture was reacted at 25 ° C. for 3 hours. Add 1 reaction mixture
% Aqueous hydrochloric acid solution (450 ml), the precipitate formed is filtered off,
After washing with water and drying (40 ° C.), 7.6 g of 1,2-naphthoquinonediazide-5-sulfonic acid ester of Compound [III-a] (photosensitive material f) was obtained.

Synthesis Example 16 Synthesis of Photosensitive Material g <Comparative Example> 16.2 g of 1,8-diphenyl-p-menthane (compound E below), 20.2 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and acetone 300 ml was charged into a three-necked flask and uniformly dissolved. Then, triethylamine / acetone = 8.0 g / 50 ml was gradually added dropwise, and the mixture was reacted at 25 ° C. for 6 hours. 1% reaction mixture
It was poured into 1200 ml of an aqueous hydrochloric acid solution, the resulting precipitate was filtered off, washed with water and dried (40 ° C.) to give 1,8-diphenyl-p-menthane 1,2-naphthoquinonediazide-5.
29.2 g of sulfonic acid ester (photosensitive material g) was obtained.

[0079]

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Synthesis Example 17 Synthesis of Photosensitive Material h <Comparative Example> 70.5 g of terpene bis-o-cresol (manufactured by Honshu Kagaku Co., Ltd.), 182.3 g of 25% aqueous TMAH solution, 100 ml of distilled water, a stirrer and a reflux condenser. A four-necked flask equipped with a thermometer and a dropping device was charged and heated to 40 ° C. to dissolve terpene bis-o-cresol. To the mixed solution, 97.4 g of 37% aqueous formalin solution was added dropwise over 30 minutes to give 40
The mixture was heated and stirred at 10 ° C for 10 hours. Distilled water 100 in the reaction mixture
ml and hydrochloric acid 50 ml were added to obtain a brown solid. The obtained brown solid was purified by column chromatography to obtain 57.8 g of a compound F as a white powder.

[0081]

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Next, 41.3 g of the obtained compound F, 99.1 g of phenol and 400 ml of methanol were charged into a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and heated to 60 ° C. to give compound F. Dissolved.
When completely dissolved, 1 g of concentrated sulfuric acid was added, and the mixture was heated to reflux and stirred for 5 hours. The reaction mixture was crystallized in 4 liters of distilled water, and the yellow solid obtained after filtration was purified by column chromatography to obtain 28.2 g of the desired product [the following compound G] as a white powder. 28.2 g of compound [G], 30.9 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 375 ml of acetone were charged in a three-necked flask and uniformly dissolved. Then
Triethylamine / acetone = 12.2 g / 50 ml was gradually added dropwise, and the mixture was reacted at 25 ° C. for 3 hours. The reaction mixture was poured into 1500 ml of a 1% aqueous hydrochloric acid solution, the precipitate formed was filtered off, washed with water and dried (40 ° C.) to give compound [G]
4-5.9 g of 2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive material h) was obtained.

[0083]

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Synthesis Example 18 Synthesis of novolac resin A 50 g of m-cresol, 25 g of p-cresol, 28 g of 2,5-dimethylphenol, 53 g of 37% aqueous formalin solution and 0.15 g of oxalic acid were placed in a three-necked flask and stirred. The temperature was raised to 100 ° C. and the reaction was performed for 14 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. Next, the molten novolak resin was returned to room temperature and collected. The resulting novolak resin had a weight average molecular weight of 4,800 (in terms of polystyrene). Next, after completely dissolving 20 g of the novolak resin in 60 g of methanol, 30 g of water was added thereto.
g was added gradually with stirring to precipitate the 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 26 hours to obtain an alkali-soluble novolak resin A. The obtained novolak resin had a weight average molecular weight of 9680 (in terms of polystyrene) and a dispersity of 3.50.

Synthesis Example 19 Synthesis of Novolac Resin B 259.5 g of m-cresol, 9.7 g of p-cresol, 62.3 g of 2,3-dimethylphenol, 218.1 g of 37% aqueous formalin solution were stirred, reflux condenser and temperature. A three-necked flask equipped with a meter was charged and stirred at 90 ° C under oxalic acid dihydrate 1.13.
g was added. After 30 minutes, the bath temperature was raised to 130 ° C., and the contents were further refluxed with stirring for 3 hours and 30 minutes. Next, the reflux condenser was replaced with a Libig condenser, and the bath temperature was raised to 220 ° C. over about 1 hour to remove unreacted formalin, water and the like. After further distillation at normal pressure for 1.5 hours, the pressure was gradually reduced to 1 mmHg to remove unreacted monomers and the like. Two hours were required for distillation under reduced pressure. Next, the molten novolak resin was returned to room temperature and collected. The obtained novolak resin had a weight average molecular weight of 2360 (in terms of polystyrene). Next, 100 g of the novolak resin was completely dissolved in 1000 g of acetone, and then n
-Hexane (1000 g) was added, and the mixture was further stirred at room temperature for 30 minutes, and left to stand for 1 hour. The upper layer was removed by decantation, and the remaining lower layer was distilled off the solvent using a rotary evaporator to obtain a novolak resin B. The obtained novolak resin had a weight average molecular weight of 5730 (in terms of polystyrene) and a dispersity of 2.6.

Synthesis Example 20 Synthesis of Novolac Resin C 25 g of p-cresol, 19 g of o-cresol, 50 g of 2,3-dimethylphenol, 20 g of 2,3,5-trimethylphenol, 50 g of 4.9 g of 2,6-dimethylphenol. The mixture was mixed with the diethylene glycol monomethyl ether in Example 3 and charged into a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer. Next, 85 g of a 37% formalin aqueous solution was added, and the mixture was stirred while heating in an oil bath at 110 ° C. When the internal temperature reached 90 ° C, 6.3 g of oxalic acid dihydrate was added. Then, increase the temperature of the oil bath to 130 for 18 hours.
The reaction was continued while maintaining the temperature at 0 ° C, then the reflux condenser was removed, and the mixture was distilled under reduced pressure at 200 ° C to remove the unreacted monomer.
The obtained novolak resin has a weight average molecular weight of 3420.
The degree of dispersion (in terms of polystyrene) was 2.9.

Preparation and Evaluation of Positive Photoresist Composition Photosensitive Material a of the present invention obtained in Synthesis Examples 10 to 15 above
f, the comparative photosensitive material g obtained in the above Synthetic Examples 16 to 17,
h, the novolac resin obtained in the above Synthesis Examples 18 to 20,
A solvent and, if necessary, a polyhydroxy compound were mixed in the proportions shown in the following Table-A to form a uniform solution, and then the pore size was 0.
A photoresist composition was prepared by filtration using a 1 μm microfilter. This photoresist composition was applied to a silicon wafer using a spinner and dried on a vacuum adsorption type hot plate at 90 ° C. for 60 seconds to obtain resist films having film thicknesses of 0.86 μm and 0.89 μm, respectively. This film was exposed using a reduction projection exposure apparatus (reduction projection exposure apparatus NSR-2005i9C manufactured by Nikon Corporation), and then 1
PEB at 10 ° C. for 60 seconds, develop with 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute,
It was washed with water for 30 seconds and dried.

[0088]

[Table 1]

(* 1) P-1: α, α, α'-tris (4
-Hydroxyphenyl) -1-ethyl-4-isopropylbenzene P-2: tris (4-hydroxyphenyl) methane P-3: 1,1-bis (4-hydroxyphenyl) cyclohexane (* 2) S-1: ethyl Cellosolve acetate S-2: Ethyl 2-hydroxypropionate S-3: Methyl 3-methoxypropionate S-4: Ethyl β-ethoxypropionate

The resist pattern and contact hole shape of the silicon wafer thus obtained were observed with a scanning electron microscope to evaluate the resist. The results are shown in Table-B and Table-C below. In Table-B, the sensitivity is
The exposure amount is shown to reproduce a mask pattern of 0.40 μm. The resolving power represents a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.40 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 represented by the angle (θ) between the resist wall surface and the plane of the silicon wafer in the cross section of the resist pattern of 0.40 μm. Defocus latitude has a line width of 0.35 μm ± 10%
The range of the focus that can be tolerated in the range is shown.

Regarding the evaluation of the contact holes shown in Table-C, the sensitivity was shown by the exposure dose for reproducing the mask pattern of 0.40 μm. The resolution of the contact hole is 0.4
It represents the limiting resolution at an exposure dose that reproduces a mask pattern of 0 μm. Defocus latitude is 0.40μ
The allowable focus width is shown when the bottom dimension of the m contact hole is within ± 10%.

[0092]

[Table 2]

[0093]

[Table 3]

From the above results, Examples 1 to 7 of the present invention
Has high sensitivity and resolution, good heat resistance and resist shape,
It can be seen that it has a wide defocus latitude, and that the sensitivity, resolution, and defocus latitude of the contact hole are all excellent.

[0095]

The positive photoresist composition of the present invention has high sensitivity and resolution, good heat resistance and resist shape, wide defocus latitude, and all of the sensitivity, resolution and defocus latitude of contact holes. Become better.

Claims (1)

[Claims] 1. A positive type which contains at least one quinonediazide sulfonic acid ester of a polyhydroxy compound selected from the following general formulas (1), (2) and (3) and an alkali-soluble resin. Photoresist composition. Embedded image Embedded image R ₁ and R _2, which may be the same or different, are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group,
Alkoxy group, acyl group, alkenyl group, aralkyl group, alkoxycarbonyl group, arylcarbonyl group,
It represents an acyloxy group, a nitro group, or a cyano group. It represents a hydrogen atom, an alkyl group: R _3. n: integer of 1 to 3, m: 1 or 2, x, y: integer of 1 to 3, z: integer of 1 to 3.