JPH09258437A - Positive type photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high resolving power and improved dependency on film thickness without reducing sensitivity and to prevent the generation of standing waves by using quinonediazidosulfonic esters of two kinds of specified polyhydroxy compds. SOLUTION: This compsn. contains an alkali-soluble resin and 1,2- naphthoquinonediazido-5-(and/or -4-)sulfonic esters of polyhydroxy compds. represented by formulae I, II, wherein X is represented by formula III, each of R1 -R6 is H, halogen, etc., each of R7 -R22 is H, hydroxyl, etc., each of R30 -R35 is H, alkyl, etc., each of R40 and R41 is H, halogen, etc., R42 is H, hydroxyl, etc., R43 is H, halogen., etc., each of R51 and R52 is H, halogen, etc., and A is -O-, -S-, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention contains an alkali-soluble resin and a specific 1,2-quinonediazide compound, and emits radiation such as ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays and synchrotron radiation. More specifically, the present invention relates to a positive-type photoresist composition that is sensitive to, and more specifically, a high-resolution positive-type photoresist that does not cause a decrease in sensitivity, has a high resolution regardless of film thickness variations, and does not generate standing waves. It concerns resist.

[0002]

2. Description of the Related Art A positive photoresist is applied on a substrate such as a semiconductor wafer, glass, ceramics or metal to a thickness of 0.5 to 2 .mu.m by a spin coating method or a roller coating method. Thereafter, the film is heated and dried, and a circuit pattern or the like is baked by ultraviolet irradiation or the like through an exposure mask. If necessary, the film is baked after exposure and then developed to form a positive image. As a positive photoresist composition, a composition containing an alkali-soluble resin binder such as novolak and a naphthoquinonediazide compound as a photosensitive material is generally used.

The degree of integration of integrated circuits is increasing, and 0.5 is used in the manufacture of semiconductor substrates such as VLSI.
It is becoming necessary to process an ultrafine pattern composed of a line radiation of μm or less. In such applications, there is a demand for a photoresist that can obtain a particularly high resolution and that has a wide development latitude in order to always maintain a constant processing radiation. In addition, in order to prevent processing defects of the circuit, the resist pattern after development,
It is required that no resist residue is generated.

Further, particularly in the formation of an ultrafine pattern of 0.5 μm or less, for example, even if a certain resolution is obtained with a certain coating thickness, it can be obtained by slightly changing the coating thickness. Phenomenon that resolution deteriorates (hereinafter,
It is known that there is "film thickness dependency"). Surprisingly, the resolution changes greatly when the film thickness changes by only a few hundreds of μm, and more or less than any of the typical positive photoresists currently on the market. I also found that there was a tendency. Specifically, when the thickness of the resist film before exposure changes within a range of λ / 4n (λ is the exposure wavelength, n is the refractive index of the resist film at that wavelength) with respect to the predetermined film thickness, The resolution that is applied varies. The problem of this film thickness dependence is, for example, SPIE Proceedings Vol.
The existence thereof was pointed out, and it is stated that this is caused by the multiple reflection effect of light in the resist film.

In particular, it has been found that this film thickness dependence is often increased when an attempt is made to increase the contrast of the resist so as to obtain a pattern having a high resolution and a rectangular cross section. When actually processing a semiconductor substrate, a pattern is formed by using a resist film applied with a film thickness slightly different depending on the location due to the unevenness on the substrate surface or the unevenness of the coating film thickness. Therefore, this film thickness dependence has been one obstacle in performing fine processing close to the resolution limit using a positive photoresist.

Japanese Unexamined Patent Publication No. 6-167805 and the like disclose that
As a photosensitive material, a selective diester of quinonediazidosulfonic acid, which is a 4- to 5-functional polyhydroxy compound, is disclosed as effective. However, when only this photosensitive material was used, the effect of multiple reflection at the time of exposure could not be sufficiently suppressed, and as a result, a standing wave was easily generated on the wall surface of the resist pattern. The standing wave is generally known to be improved by baking, but the standing wave in the case of the above technique could not be improved even by baking.

[0007]

That is, it has a high resolution and an excellent film thickness dependence without deteriorating the sensitivity,
In addition, it has not been known at all until now how to design the composition of the resist material in order to obtain a material in which no standing wave is generated. Therefore, an object of the present invention is to provide a positive photoresist composition for ultrafine processing, which has high resolution and excellent film thickness dependency without causing a decrease in sensitivity and does not generate standing waves. Especially. In addition,
In the present invention, the "film thickness dependence" means the resolution of the resist obtained by exposure and (baking if necessary) development when the film thickness of the resist before exposure changes in the range of λ / 4n. Say fluctuations.

[0008]

Means for Solving the Invention The inventors of the present invention have conducted extensive studies, paying attention to the above-mentioned characteristics, and as a result, as a photosensitizer, a quinonediazide sulfonate ester of a polyhydroxy compound having a structure represented by the following general formula [II] was used. It was found that the above problem can be solved by using a quinonediazide sulfonic acid ester of a polyhydroxy compound represented by the following general formula [I], and the present invention has been completed based on this finding. That is, the object of the present invention is (1) an alkali-soluble resin, a 1,2-naphthoquinonediazide-5- (and / or-4-) sulfonic acid ester of a polyhydroxy compound represented by the following general formula [I], and Achieved by a positive photoresist composition comprising a 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonic acid ester of a polyhydroxy compound represented by the general formula [II]. .

The general formula [I]

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Where X:

[0011]

[Chemical 6]

R _{1 to} R ₆ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R _{7 to} R _{22 are the} same. Or they may be different, hydrogen atom,
Hydroxyl group, halogen atom, alkyl group having 1 to 4 carbon atoms,
An alkenyl group or a cycloalkyl group having 2 to 5 carbon atoms, R _{30 to} R ₃₅ : which may be the same or different, a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms, R ₃₀ and R ₃₁ , R ₃₂
And R ₃₃ , or R ₃₄ and R ₃₅ may be linked to each other to form a methylene chain having 4 or 5 carbon atoms and form a 5-membered or 6-membered ring with carbon atoms, R ₄₀ , R ₄₁ : The same or different, a hydrogen atom,
Halogen atom or alkyl group having 1 to 4 carbon atoms, R ₄₂ : hydrogen atom, hydroxyl group or alkyl group having 1 to 4 carbon atoms, R ₄₃ : hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, It represents an alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group, an aryl group or an alkoxy group.

General formula [II]

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Here, R ₅₁ and R ₅₂ are the same or different and each is a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, acyl group or cycloalkyl group, a, b: each independently an integer of 0 to 3, A: -C ( _R66 ) ( _R67 )-,- O-, -S-, -C
(= O)-, -C (= O) O-, -S (= O)-, -S
Represents (= O) _2- (wherein _R66 and _R67 may be the same or different and represent a hydrogen atom or an alkyl group);

[0015]

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R _{53 to} R ₆₅ : hydrogen atoms, which may be the same or different,
Halogen atom, alkyl group, alkenyl group, aryl group, alkoxy group or cycloalkyl group, X ₁ , Y: may be the same or different, single bond or-
C (R ₆₈ ) (R ₆₉ )-(wherein R ₆₈ and R ₆₉ may be the same or different and each is a hydrogen atom or an alkyl group), g: an integer of 0 to 3, k: 0 or 1 n: represents 1 or 2.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the above general formula [I], R _{1 to} R ₂₂ , R _{30 to} R ₃₅ , R
_As the alkyl group of _{40 to} R ₄₃ , an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. preferable. More preferred are methyl group, ethyl group, propyl group and isopropyl group.
The cycloalkyl group of R ₇ ~R _22, R ₄₃ cyclopentyl, cyclohexyl is preferred. R _{7 to} R ₂₂ ,
The C 2-5 alkenyl group for R ₄₃ is preferably a vinyl group, a 2-propenyl group or an allyl group. The aryl group of R ₄₃ is preferably a phenyl group, a toluyl group, a xylyl group, a cumenyl group or a mesityl group. As the alkoxy group for R ₄₃ , a lower alkoxy group such as a methoxy group and an ethoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. R ₃₀ and R ₃₁ , R ₃₂ and R ₃₃ , or R ₃₄ and R ₃₅ are linked to each other to form a methylene chain having 4 or 5 carbon atoms,
Examples of the 5- or 6-membered ring formed with a carbon atom include cyclopentane and cyclohexane.

In the general formula [I], R _{1 to} R ₂₂ , R
₄₀ and R ₄₁ are preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group or a halogen atom, particularly preferably a hydrogen atom, a methyl group or a halogen atom. R ₃₀ ~ R ₃₅
Of these, a hydrogen atom and a methyl group are preferable. R ₄₂ is preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a hydroxyl group or a halogen atom, and particularly preferably a hydrogen atom, a methyl group or a hydroxyl group. R ₄₃ is preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, a phenyl group, a methoxy group or an ethoxy group, and particularly preferably a methyl group, an ethyl group or a cyclohexyl group.

Further, as the compound of the general formula [I] in the present invention, it is preferable to use a selective ester produced by the method disclosed in JP-A-3-228057. From the viewpoint of the above-mentioned selective ester, the compound of the general formula [I] has a linear arrangement of the aromatic ring, and the position of the hydroxyl group is at the 2-position or the 2,6-position of the hydroxyl group on the aromatic ring which is not the terminal. By substituting a substituent having an electronic or steric effect that hinders the esterification of
More preferably, it is a selected tetraester. At this time, the area ratio of the tetraester in high performance liquid chromatography is preferably 40% or more, more preferably 50% or more.

Specific examples of the compound represented by the general formula [I] in the present invention are shown below. However, the content of the present invention is not limited to these. These may be used alone or in combination of two or more.

[0021]

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[0022]

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[0023]

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[0024]

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For the compound represented by the above general formula [II],
Will be explained. In the above general formula [II], R₅₁~ R₆₉No
As the alkyl group, a methyl group, an ethyl group, a propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec
1-carbon group such as -butyl group, tert-butyl group
4 alkyl groups are preferred, more preferably methyl
Group, ethyl group, propyl group, isopropyl group,
In particular, a methyl group and an ethyl group are preferable. R₅₁~ R₆₅The halo
As the chlorine atom, chlorine atom, bromine atom and iodine atom are preferred.
And a chlorine atom is particularly preferred. R₅₁~ R₆₅Archeni
As the vinyl group, vinyl group, propenyl group and allyl group are preferable.
Good. R₅₁~ R ₆₅The aryl group of is phenyl
Group, toluyl group, xylyl group, cumenyl group, mesityl group
Is preferred. R₅₁~ R₆₅As the alkoxy group of
A lower alkoxy group such as an oxy group and an ethoxy group is preferable,
A methoxy group and an ethoxy group are more preferable. R₅₁~ R₆₅of
As the cycloalkyl group, a cyclopentyl group, cyclo
Hexyl groups are preferred. R₅₁, R₅₂As the acyl group of
Formyl group, acetoxy group and benzoyl group are preferred.

Further, in the general formula [II], R ₅₁ and R ₅₂ are preferably hydrogen atom, chlorine atom, methyl group, ethyl group, allyl group, phenyl group, methoxy group and cyclohexyl group, and hydrogen atom and chlorine atom. , Methyl group, ethyl group,
An allyl group and a methoxy group are more preferable. A hydrogen atom, a chlorine atom and a methyl group are more preferable, and a hydrogen atom and a chlorine atom are particularly preferable. As R _{53 to} R ₆₀ , a hydrogen atom,
A methyl group, an ethyl group, an allyl group and a cyclohexyl group are preferred. More preferably, it is a hydrogen atom, a methyl group or an allyl group. R ₆₁ is preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group or a cyclohexyl group, and more preferably a hydrogen atom, a methyl group, a phenyl group or a cyclohexyl group. As R _{62 to} R ₆₅ , a hydrogen atom and a methyl group are preferable. -S as the connecting chain A
-, - O -, - CH 2 - are preferred, particularly -CH ₂ - are preferred. A single bond is used as the connecting chains X ₁ and Y, R ₆₈ and R ₆₉
Does not form a ring, -C (R ₆₈ ) (R ₆₉ )-is preferable, and among -C (R ₆₈ ) (R ₆₉ )-, one in which at least one of R ₆₈ and R ₆₉ is a hydrogen atom is preferable. More preferable.

Regarding the substitution position of each substituent, the position of the hydroxyl group on the terminal aromatic ring is preferably para or meta with respect to the connecting chain. The para position is more preferable. At least one of both ortho positions of the hydroxyl group on the terminal aromatic ring is preferably a hydrogen atom so as not to prevent esterification of the hydroxyl group. Further, in the case of a chlorine atom or the like which is thought to promote the esterification, it may be substituted at the 2,6-position of the hydroxyl group. Particularly preferred structures of the terminal aromatic ring include a phenol structure, an o-chloro structure and a 2,6-dichloro structure. It is not preferred that both ortho positions of the hydroxyl group on the internal aromatic ring are hydrogen atoms at the same time. In other words, it is preferable to introduce substituents at both ortho positions of the hydroxyl group that electronically or sterically hinder the esterification of the hydroxyl group.

Further, as the compound of the general formula [II] in the present invention, it is preferable to use a selective ester produced by the method disclosed in JP-A-3-228057. From the viewpoint of the above-mentioned selective ester, the compound of the general formula [II] has a linear arrangement of the aromatic ring, and the position of the hydroxyl group is the 2-position of the hydroxyl group on the aromatic ring which is not the terminal or the 2- or 6-position of the hydroxyl group on the aromatic ring. By substituting a substituent having an electronic or steric effect that hinders the esterification of
More preferably it is a selected diester. At this time,
The area ratio of the diester in high performance liquid chromatography is preferably 40% or more, more preferably 50% or more.

Specific examples of the compound represented by the general formula [II] in the present invention are shown below. However, the content of the present invention is not limited to these. These may be used alone or in combination of two or more.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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The photosensitive material of the present invention includes, for example, the above polyhydroxy compounds and 1,2-naphthoquinonediazide-5-
(And / or -4-) sulfonyl chloride can be obtained by carrying out an esterification reaction in the presence of a base catalyst. That is, a predetermined amount of a polyhydroxy compound and 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride and acetone, methyl ethyl ketone, dioxane, dimethoxyethane, tetrahydrofuran, diglyme, ethyl acetate, dichloromethane, chloroform, A solvent such as γ-butyrolactone or N-methylpyrrolidone is charged into a flask, and a base catalyst such as sodium hydroxide, sodium carbonate, triethylamine, 4-
Dimethylaminopyridine, N-methylmorpholine, N-
Methylpiperazine, N-methylpyrrolidine and the like are added dropwise for condensation. The obtained product was crystallized in water and washed with water,
Further refine and dry.

In the usual esterification reaction, a mixture having different esterification numbers and esterification positions is obtained. However, by selecting the synthesis conditions or the structure of the polyhydroxy compound, only a specific isomer can be selectively selected. It can also be synthesized. The average esterification rate used below is defined as the average value of the esterification rates of those mixtures with different esterification rates.

The esterification rate thus defined can be controlled by the molar ratio of the quinonediazide sulfonyl chloride as a raw material and the polyhydroxy compound to be mixed. That is, since the added quinonediazide sulfonyl chloride undergoes an esterification reaction substantially all, in order to obtain a mixture having a desired average esterification rate, the charging ratio (molar ratio) of the quinonediazide sulfonyl chloride as a raw material and the polyhydroxy compound is obtained. [Mole number of quinonediazide sulfonyl chloride / mol number of polyhydroxy compound] may be adjusted.

For example, when the polyhydroxy compound represented by the general formula [I] is a compound having 6 OH groups in the molecule, 1,2-naphthoquinonediazide-5- (and /
Alternatively, the molar ratio of -4-) sulfonyl chloride and the polyhydroxy compound represented by the general formula [I] is preferably in the range of 2.5 to 5.0, more preferably 3.
It is 0 to 4.8, and more preferably 3.5 to 4.5. That is, the preferable range of the average esterification rate is 42%.
Is 83%, more preferably 50% to 80%, still more preferably 58% to 75%. Further, when the polyhydroxy compound represented by the general formula [I] is a compound having 7 OH groups in the molecule, the preferable molar ratio is 2.45 to 5.6, more preferably 3.15. ~
4.9, more preferably 3.5 to 4.55. That is, the preferable range of the average esterification rate is 35% to 80%.
%, More preferably 45% to 70%, still more preferably 50% to 65%.

The preferred range of the molar ratio of 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride to the polyhydroxy compound represented by the general formula [II] is 1.0 to 3.0. And more preferably 1.2 to 2.8, and even more preferably 1.5 to 2.5. That is, the preferable range of the average esterification rate is 25
% To 75%, more preferably 30% to 70%, still more preferably 37.5% to 62.5%.

In the present invention, 1,2-naphthoquinonediazide-5- (and / or-4-) sulfonic acid ester of the compound represented by the general formula [I] and the general formula [II] are represented. Two or more kinds of 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonic acid ester of the compound may be used together in the resist composition of the present invention.

In the present invention, 1,2-naphthoquinonediazide-5- (and / or-4-) sulfonic acid ester of the compound represented by the general formula [I] and the general formula [II] are represented. The addition ratio of 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonic acid ester of the compound is 5% by weight in the resist composition.
/ 95 to 60/40, preferably 10/90 to 4
It is 0/60.

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 compounding amount is 1
It is 5 to 100 parts by weight, preferably 20 to 60 parts by weight, relative to 00 parts by weight. When the use ratio is less than 5 parts by weight, the residual film rate is remarkably lowered, and when it exceeds 100 parts by weight, the sensitivity and the solubility in a solvent are lowered.

In the present invention, the above-mentioned two types of photosensitive materials should be used, but if necessary, 1,2-naphthoquinonediazide-5- (and // the following polyhydroxy compound is used.
Alternatively, an esterified product with -4-) sulfonyl chloride can be further used in combination. At this time, the ratio of the naphthoquinone diazide ester photosensitive material of these polyhydroxy compounds to the photosensitive material in the present invention is 20/80 to 80/20.
The ratio is preferably (weight ratio). That is, if the photosensitive material of the present invention is less than 20% by weight of the total photosensitive material, the effect of the present invention cannot be sufficiently exhibited.

As the polyhydroxy aromatic compound,
For example, 2,3,4-trihydroxybenzophenone,
2,4,4'-trihydroxybenzophenone, 2,
4,6-trihydroxybenzophenone, 2,3,4
4'-tetrahydroxybenzophenone, 2,2 ',
4,4'-tetrahydroxybenzophenone, 2,4
Polyhydroxybenzophenones such as 6,3 ′, 4 ′, 5′-hexahydroxybenzophenone and 2,3,4,3 ′, 4 ′, 5′-hexahydroxybenzophenone
2,3,4-trihydroxyacetophenone, 2,3
Polyhydroxyphenyl alkyl ketones such as 4-trihydroxyphenylhexyl ketone, bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) Bis ((poly) hydroxyphenyl) alkanes such as propane-1, polyhydroxybenzoic acid esters such as propyl 3,4,5-trihydroxybenzoate and phenyl 3,4,5-trihydroxybenzoate
Bis (polyhydroxybenzoyl) alkanes such as bis (2,3,4-trihydroxybenzoyl) methane, bis (2,3,4-trihydroxybenzoyl) benzene or bis (polyhydroxybenzoyl) aryls, ethylene glycol-di Alkylene-di (polyhydroxybenzoates) such as (3,5-dihydroxybenzoate), 3,5,3 ′, 5′-biphenyl tetrol,
2,4,2 ', 4'-biphenyl tetrol, 2,4
6,3 ', 5'-biphenylbentol, 2,4,6
Polyhydroxybiphenyls such as 2 ′, 4 ′, 6′-biphenylhexol,

4,4 ', 4 "-trihydroxy-3,
5,3 ', 5'-tetramethyltriphenylmethane,
4,4 ', 4 "-trihydroxy-3" -methoxy-
3,5,3 ', 5'-tetramethyltriphenylmethane, 4,4', 2 "-trihydroxy-3,5,3 ',
5'-tetramethyltriphenylmethane, 4,4 ',
2 "-trihydroxy-2,2'-dimethyl-5,5 '
-Dicyclohexyltriphenylmethane, 4,4 ',
2 "-trihydroxy-2,5,2 ', 5'-tetramethyltriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenyl Methane, 4,4 ', 2 ", 3", 4 "-pentahydroxy-3,5,3', 5'-tetramethyltriphenylmethane, 2,3,4,2 ', 3', 4 ', 3 ″,
Polyhydroxytriphenylmethanes such as 4 ″ -octahydroxy-5,5′-diacetyltriphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobi-indane-5,6,6. 5 ', 6'-tetrol,
3,3,3 ', 3'-Tetramethyl-1,1'-spirobi-indan-5,6,7,5', 6 ', 7'-hexool, 3,3,3', 3'-tetra Methyl-1,1 '
-Spirobiindane-4,5,6,4 ', 5', 6'-
Hexool, 3,3,3 ', 3'-tetramethyl-
1,1'-spirobi-indane-4,5,6,5 ',
Polyhydroxyspirobi-indanes such as 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], 2- (3,4-
Dihydroxyphenyl) -3,5,7-trihydroxybenzopyran, 2- (3,4,5-trihydroxyphenyl) -3,5,7-trihydroxybenzopyran, 2
-(3,4-dihydroxyphenyl) -3- (3,4,
5-trihydroxybenzoyloxy) -5,7-dihydroxybenzopyran, 2- (3,4,5-trihydroxyphenyl) -3- (3,4,5-trihydroxybenzoyloxy) -5,7-dihydroxy Polyhydroxybenzopyrans such as benzopyran, 2,4,4-trimethyl-2- (2 ', 4'-dihydroxyphenyl)
-7-hydroxychroman, 2,4,4-trimethyl-
2- (2 ', 3', 4'-trihydroxyphenyl)-
Polyhydroxyphenyl chromanes such as 7,8-dihydroxychroman, 2,4,4-trimethyl-2- (2 ', 4', 6'-trihydroxyphenyl) -5,7-dihydroxychroman, 2,6- Screw (2,3,4-
Trihydroxybenzyl) -4-methylphenol,
2,6-bis (2,4-dihydroxybenzyl) -4-
Methylphenol, 2,6-bis (5-chloro-2,4
-Dihydroxybenzyl) -4-methylphenol,
2,6-bis (2,4,6-trihydroxybenzyl)
-4-Methylphenol, 2,6-bis (2-acetyl-3,4,5-trihydroxybenzyl) -4-methylphenol, 2,4,6-tris (2,3,4-trihydroxybenzyl) Phenol, 2,6-bis (3,5
-Dimethyl-4-hydroxybenzyl) -4-methylphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol, 2,6-bis (2,5-dimethyl-4) -Hydroxybenzyl) -4
-Phenylphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-cyclohexylphenol, 2,6-bis (4-hydroxybenzyl)-
4-cyclohexylphenol, 2,6-bis {3'-
(4 "-hydroxybenzyl) -4'-hydroxy-
5'-methylbenzyl} -4-cyclohexylphenol, 2,6-bis {3 '-(3 "-methyl-4" -hydroxybenzyl) -4'-hydroxy-5'-methylbenzyl} -4-cyclohexylphenol , 2, 4, 6
-Tris (3,5-dimethyl-4-hydroxybenzyl) -phenol, 4,6-bis (3,5-dimethyl-
4-hydroxybenzyl) pyrogallol, 2,6-bis (3-methyl-4-hydroxybenzyl) -4-methylphenol, 2,6-bis (3,5-dimethyl-4-hydroxybenzyl) phloroglucinol, etc. Hydroxybenzylphenols,

2,2'-dihydroxy-5,5'-bis (4 "-hydroxybenzyl) biphenol, 2,2 '
-Dihydroxy-3,3'-dimethoxy-5,5'-bis (4 "-hydroxybenzyl) biphenol, 2,
2'-dihydroxy-3,3'-dimethoxy-5,5 '
-Bis (3 ", 5" -dimethyl-4 "-hydroxybenzyl) biphenol, 2,2'-dihydroxy-3,
3'-dimethoxy-5,5'-bis (3 "-methyl-
4 "-hydroxybenzyl) biphenol, 4,4'-
Dihydroxy-3,3'-dimethyl-5,5'-bis (3 ", 5" -dimethyl-4 "-hydroxybenzyl)
Biphenols such as biphenols, 1,3,3,5-
Tetrakis (4-hydroxyphenyl) pentane, 1,
1-bis {3 '-(4 "-hydroxybenzyl) -4'
-Hydroxy-5'-methylphenyl} cyclohexane, 1,1-bis {3 '-(3 "-methyl-4" -hydroxybenzyl) -4'-hydroxy-5'-methylphenyl} cyclohexane, 1, 1-bis {3'-
(3 ", 6" -dimethyl-4 "-hydroxybenzyl)
-4'-hydroxy-5'-methylphenyl} cyclohexane, 4,4'-methylenebis {2- (4 "-hydroxybenzyl) -3,6-dimethylphenol}, 4,
4'-methylenebis {2- (3 "-methyl-4" -hydroxybenzyl) -3,6-dimethylphenol},
4,4'-methylenebis {2- (3 "-methyl-4"-
(Hydroxybenzyl) -3-cyclohexyl-6-methylphenol}, 4,4'-methylenebis {2-
(2 ", 4" -dihydroxybenzyl) -6-methylphenol}, 1,8-bis {3 '-(4 "-hydroxybenzyl) -4'-hydroxy-5'-methylphenyl} menthane, 1,8 -Bis {3 '-(3 "-methyl-
4 "-hydroxybenzyl) -4'-hydroxy-5 '
Hydroxyphenylalkanes such as -methylphenyl} menthane,

3,3'-bis (4 "-hydroxybenzyl) -4,4'-dihydroxy-5,5" -diallyldiphenylether, 3,3'-bis (4 "-hydroxybenzyl) -4 , 4'-dihydroxy-5,5 "-dimethyldiphenyl thioether, 3,3'-bis (3"-
Methyl-4 ″ -hydroxybenzyl) -4,4′-dihydroxy-5,5 ″ -dimethyldiphenylthioether, 3,3′-bis (3 ″, 6 ″ -dimethyl-4 ″ -hydroxybenzyl) -4,4 ′ -Dihydroxy-5,
5 "-dimethyldiphenyl thioether, 3,3'-bis (3" -methyl-4 "-hydroxybenzyl) -4,
Diphenyl ethers such as 4'-dihydroxy-5,5 "-diallyl diphenyl ether, 2,6-bis (4 '
-Hydroxybenzyl) -4-benzenesulfonamide-phenol, 2,6-bis (3 ', 6'-dimethyl-4'-hydroxybenzyl) -4-benzenesulfonamide-phenol and other sulfonamide phenols or quercetin, Flavono pigments such as rutin,
Furthermore, a low nucleolar form of novolac, or an analogue thereof can be used.

Further, a polymer containing an aromatic hydroxyl group such as an acetone pyrogallol condensation resin or polyvinyl phenol can be used instead of these low molecular weight compounds. Further, it is possible to substitute the hydroxyl group of novolac itself with quinonediazide in an appropriate amount so that it also functions as a photosensitive material or as a binder.

Among these, particularly, a portion having one or more aromatic hydroxyl groups on the same aromatic ring is included, and a total of 3
Those having a structure having one or more hydroxyl groups are preferable.
In addition, 1,2-naphthoquinonediaside-5- (and / or-, which is a known aromatic or aliphatic polyhydroxy compound,
4-) Sulfonic acid ester compounds include, for example, JP-B-56-2333, JP-B-62-3411, JP-B-3-2293, JP-B-3-42656, JP-A-58-150948, and JP-A-58-150948. 60-154249
No. 60-134235, JP-A 62-10646, JP-A 62-
153950, JP60-146234A, JP62-178562A, JP63-113451A, JP64-76047A, JP1-147538A.
No. 1, JP-A 1-189644, JP-A 1-309052, JP-A 2-19
846, JP2-84650, JP2-72363, JP2-1
03543, JP-A-2-285351, JP-A-2-296248, JP-A-2-296249, JP-A-3-48251, JP-A-3-48249, JP-A-3-119358, JP-A-3-144454 No. 3-185447
No. 4-1652, No. 4-60548, No. 5-15823
No. 4, JP-A-5-224410, JP-A No. 5-303198, JP-A No. 5-2
97580, Japanese Unexamined Patent Publication No. 5-323597, Japanese Patent Application No. 5-251781, Japanese Patent Application No. 5-251780, Japanese Patent Application No. 5-233537, U.S. Pat.No. 4,797,34
No. 5, No. 4,957,846, No. 4,992,356, No. 5,151,340,
Examples thereof include compounds described in JP-A-5,178,986, European Patent Nos. 530,148 and 573,056.

Examples of the alkali-soluble resin used in the present invention include novolac resin, acetone-pyrogallol resin, polyhydroxystyrene and derivatives thereof. Of these, novolak resins are particularly preferred,
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 such as -cresol, o-cresol, 2,
Xylenols such as 5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-xylenol, m-ethylphenol, p-ethylphenol, o
Alkylphenols such as -ethylphenol and pt-butylphenol, trialkylphenols such as 2,3,5-trimethylphenol and 2,3,4-trimethylphenol, p-methoxyphenol, m-methoxyphenol and 3,5 Alkoxyphenols such as -dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol; Bisalkylphenols such as methyl-4-isopropylphenol, m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol,
Hydroxy aromatic compounds such as resorcinol and naphthol can be used alone or in combination of two or more, but are not limited thereto.

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, oxalic acid and the like can be used.

In addition, JP-A-60-45238 and 60-
97347, 60-14235, 60-1897
39, 64-14229, JP-A-1-276131,
2-60915, 2-275555, 2-282
745, 4-101147, 4-122938, etc., that is, it is preferable to use a technique in which low-molecular components of novolac resin are removed or reduced.

The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 1500 to 25000. If it is less than 1500, the film loss of the unexposed portion after development is large, and if it exceeds 25,000, the developing speed is reduced. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. Also, the degree of dispersion of the novolak resin (ratio of weight average molecular weight Mw to number average molecular weight Mn, ie, Mw / Mn)
Is preferably 1.5 to 7.0, and more preferably 1.5 to 5.0. If the degree of dispersion exceeds 7, the effects of the present invention may not be sufficiently exhibited. The degree of dispersion is 1.
If it is less than 5, a high-level purification step is required for synthesizing the novolak resin, and thus it lacks practical practicality and is inappropriate. The weight average molecular weight and dispersity of the novolak resin are
It can be set as appropriate depending on the type of novolak resin.

The alkali-soluble resin is a novolak resin synthesized by a condensation reaction of a mixture containing two or more kinds of phenol, cresol, xylenol, and trimethylphenol (provided that m-cresol is essential) with an aldehyde compound. In this case, the weight average molecular weight is 5500.
~ 25,000, more preferably 6
2,000 to 25,000. Further, the novolak resin has a ratio of the weight average molecular weight to the number average molecular weight of 1.5 to 5.0.
It is preferably 0. The alkali-soluble resin is p
It was synthesized by a condensation reaction of a mixture containing at least four of o-cresol, o-cresol, 2,3-xylenol, 2,6-xylenol and trimethylphenol (o-cresol is essential) with an aldehyde compound. If at least one novolak resin,
The ratio between the weight average molecular weight and the number average molecular weight is 1.5 to 5.0, and the weight average molecular weight is preferably 1500 to 6000. As described above, the effect of the present invention becomes more remarkable by setting the weight average molecular weight and the polydispersity within predetermined ranges depending on the type of novolac resin used.

The low molecular weight compound (water-insoluble alkali-soluble low molecular weight compound) having a phenolic hydroxyl group that can be used in the present invention will be described.

The composition of the present invention preferably further contains a water-insoluble alkali-soluble low molecule in order to accelerate the dissolution in the developing solution. Thereby, the development latitude can be improved. Specific examples of the water-insoluble alkali-soluble low molecular weight include polyhydroxy compounds. 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-
Hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene,
1,2,2-tris (hydroxyphenyl) propane,
1,1,2-Tris (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane , 1,1,3-
Tris (hydroxyphenyl) butane, para [α, α,
α ', α'-tetrakis (4-hydroxyphenyl)]
-Xylene and the like.

Among these, as the water-insoluble alkali-soluble low-molecular compound, the total number of carbon atoms in one molecule is 60 or less, and the water-insoluble alkali-soluble low-molecular compound having 2 to 8 phenolic hydroxyl groups in one molecule is used. Compounds are preferred. Further, the water-insoluble alkali-soluble low molecular weight compound has a ratio of phenolic hydroxyl group to aromatic ring of 0.5 to 1.
4, and preferably at least one water-insoluble alkali-soluble low-molecular compound having 12 to 60 phenolic hydroxyl groups in one molecule, having a total carbon number of 12 to 60 in one molecule. . Among these compounds, compounds that increase the alkali dissolution rate of the alkali-soluble resin when added to the water-insoluble alkali-soluble resin are particularly preferable. As a result, the development latitude is further improved. If the compound has more than 60 carbon atoms, the effect of the present invention is reduced. If the number is smaller than 12, new drawbacks such as a decrease in heat resistance occur. In order to exert the effects of the present invention, it is necessary to have at least two hydroxyl groups in the molecule, but if it exceeds 10, the effect of improving the development latitude is lost. On the other hand, when the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the film thickness dependency is large, and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it becomes difficult to obtain high resolution and good film thickness dependence, which is not preferable.

The low molecular weight compound is preferably added in an amount of 1 to 100% by weight, more preferably 2 to 80% by weight, based on the alkali-soluble resin. An addition amount exceeding 100% by weight is not preferable because the development residue deteriorates and a new defect that a pattern is deformed during development occurs. The water-insoluble alkali-soluble low molecular weight compound having an aromatic hydroxyl group used in the present invention is described in, for example,
22938, 2-28531, 2-242973,
2-275959, 4-251849, 5-30
3199, 5-22440, 6-301204, U.S. Pat. Nos. 4,916,210 and 5,210,657,
It can be easily synthesized by those skilled in the art with reference to the methods described in US Pat. No. 5,318,875 and European Patent No. 219294.

As the solvent for dissolving the photosensitive material and the alkali-soluble novolac resin used in the present invention, 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, cyclopentanone, cyclohexanone, 4-methoxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-
Methyl hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, etc. 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,
High-boiling solvents such as N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether can be mixed and used.

The positive photoresist composition of the present invention may contain a surfactant in order to further improve 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 nonylphenol ether. Polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. Sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sol Monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, Eftop EF
301, EF303, EF352 (Shin-Akita Kasei Co., Ltd.)
, MegaFac F171, F173 (Dainippon Ink Co., Ltd.), Florado FC430,431 (Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103,
SC104, SC105, SC106 (Asahi Glass Co., Ltd.)
Manufactured by Shin-Etsu Chemical Co., Ltd., an acrylic acid-based or methacrylic acid-based (co) polymerized polyflow No.
75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The content 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.

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 aqueous solutions of alkali amines such as alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and piperidine. can do. Furthermore, alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants may be added to the aqueous solution of the above alkalis in appropriate amounts.

A light absorber, a cross-linking agent, and an adhesion aid can be added to the positive photoresist composition of the present invention, if necessary. 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-absorbing agents described in “Technologies and Markets of Industrial Dyes” (CMC Publishing) and Dye Handbook (edited by the Society of Synthetic Organic Chemistry), for example, CI Di
sperse 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, 8
8, 117, 137, 143, 199 and 210, CI Disperse Viole
t 43, CI Disperse Blue 96, CI Fluorescent Br
ightening Agent 112, 135 and 163, CI Solvent Yel
low 14, 16, 33 and 56, CI Solvent Orange 2 and 4
5, CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 4
9, CI Pigment Green 10, CI Pigment Brown 2, and the like can be suitably used. The light absorbing agent is usually added in an amount of 100 parts by weight or less, preferably 50 parts by weight or less, and more preferably 30 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin.

The cross-linking 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 (resist 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 auxiliaries are usually mixed in an amount of less than 10 parts by weight, preferably less than 5 parts by weight, based on 100 parts by weight of the alkali-soluble resin.

The positive photoresist composition is spin-coated on a substrate (eg, a silicon / silicon dioxide coating, a glass substrate, a transparent substrate such as an ITO substrate, etc.) that is used for the production of precision integrated circuit devices. , Roll coating method,
After applying by a suitable coating method such as a flow coating method, a dip coating method, a spray coating method, and a doctor coating method, pre-baking is performed, exposure is performed through a predetermined mask, and post-heating (PEB: Post Exposure Bake) is performed as necessary. ,
By developing, rinsing and drying, a good resist can be obtained.

[0070]

The present invention will now be described by way of examples, which should not be construed as limiting the invention. In addition,% indicates weight% unless otherwise specified.

Synthesis Example (1) Synthesis of Compound [I-1] 114 g of bis (3-methyl-4-hydroxyphenyl) methane, 456 g of 25% aqueous solution of tetramethylammonium hydroxide, and 50 mL of distilled water were stirred with stirring under reflux. A 4-necked flask equipped with a tube, a thermometer and a dropping device was charged, stirred at room temperature to completely dissolve bis (3-methyl-4-hydroxyphenyl) methane, and then 242 g of a 37% aqueous formalin solution was added dropwise to the flask. It was stirred for 12 hours. The obtained reaction mixture was neutralized with a 1% aqueous hydrochloric acid solution, and the white solid precipitated was collected by filtration to obtain 103 g of a methylol compound. 91 g of the methylol compound obtained above, 1.32 kg of resorcin, 8 g of paratoluenesulfonic acid monohydrate and 2.4 L of methanol were charged into a similar reaction apparatus, and heated and stirred under reflux conditions to homogenize. The mixed solution was stirred as it was for 8 hours, and then crystallized in 24 L of ice water, and the precipitated white solid was collected by filtration. The obtained white solid was recrystallized with distilled water to obtain 56.7 g of the target compound [I-1].

Synthesis Example (2) Synthesis of Compound [I-2] 2,2-bis (3-methyl-4-hydroxyphenyl) propane was used in place of (3-methyl-4-hydroxyphenyl) methane. In the same manner as in Synthesis Example (1), compound [I-2] was synthesized.

Synthesis Example (3) Synthesis of Compound [I-3] 128 g of bis (2,5-dimethyl-4-hydroxyphenyl) methane, 1 L of ethanol, 450 g of 50% dimethylamine aqueous solution, 450 g of stirrer, reflux condenser and temperature. A four-necked flask equipped with a meter and a dropping device was charged, and after being completely dissolved, 400 g of a 37% aqueous formalin solution was added dropwise over 1 hour and reacted under reflux conditions. The white solid deposited was collected by filtration and washed with water to obtain 176 g of an aminomethyl compound. The same reaction apparatus was charged with 148 g of the aminomethyl derivative obtained above and 1.63 kg of acetic anhydride and reacted for 24 hours under reflux conditions. The obtained reaction mixture was concentrated under reduced pressure, the concentrate was crystallized, and the precipitated brown solid was collected by filtration to obtain 152 g of acetoxy compound. To the same reaction apparatus, 120 g of the acetoxy compound obtained above, 990 g of resorcin, 6 g of paratoluenesulfonic acid monohydrate and 1.8 L of methanol were charged, and heated under stirring under reflux to homogenize. The mixed solution was stirred as it was for 8 hours, then crystallized in 18 L of ice water and the precipitated brown solid was collected by filtration. The obtained solid was recrystallized from distilled water to obtain 45.0 g of the target compound [I-3].

Synthesis Example (4) Synthesis of Compound [I-11] 84 g of bis (hydroxymethylene) -p-cresol, 324 g of O-cresol, 1 L of methanol were attached with a stirrer, a reflux condenser, a thermometer, and a dropping device. The mixture was placed in a 4-necked flask, stirred and homogenized, 5 g of concentrated sulfuric acid was added, and the mixture was heated and stirred for 4 hours under reflux conditions. After completion of the reaction, the reaction solution was crystallized in 10 L of distilled water, and the obtained solid was washed with a mixed solvent of hexane and toluene to give a white solid 3.
143 g of a nuclear body was obtained. To the same reactor, charge 105 g of the trinuclear body obtained above, 410 g of 25% tetramethylammonium hydroxide aqueous solution, 50 mL of distilled water, stir and homogenize, then drop 146 g of 37% formalin aqueous solution and stir for 8 hours. did. The resulting reaction mixture was neutralized with a 1% aqueous hydrochloric acid solution, and the precipitated white solid was collected by filtration to obtain 104 g of a trinuclear methylol body. 82 g of the trinuclear methylol compound obtained above, 660 g of resorcin, and 1.2 L of methanol were charged into the same reaction apparatus, and heated and stirred under reflux conditions to homogenize. The mixed solution was stirred as it was for 8 hours, then crystallized in 12 L of ice water and the white solid deposited was collected by filtration. The obtained white solid was recrystallized from distilled water to obtain 35.6 g of the desired compound [I-11].
I got

Synthesis Example (5) Synthesis of Photosensitive Material a Compound [I-1] 47.3 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 107.5 g, and acetone 1.0 L were charged into a three-necked flask. , Uniformly dissolved. Then
41.7 g of N-methylpiperidine was gradually added dropwise to 25
The reaction was carried out at 3 ° C. for 3 hours. The reaction mixture was poured into 3.2 L of a 1% hydrochloric acid aqueous solution, and the generated precipitate was filtered off, washed with water and dried (4
0 ° C.) to give 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [I-1] (photosensitive material a) 1.
26.1 g were obtained. In high performance liquid chromatography measured with a detector using 254 nm ultraviolet light, the tetraester form of the photosensitivity a was 64% of the total pattern area.
Met. In addition, the measurement of the said high performance liquid chromatography uses the LC-6A chromatograph by Shimadzu Corporation, and Nova-PakC1 by Waters.
8 (4 μm) 8 mmφ × 100 mm column was used, and the carrier solvent was distilled water 68.6%, acetonitrile 3
A solution of 0.0%, 0.7% triethylamine and 0.7% phosphoric acid was applied at a flow rate of 2.0 ml / min.

Synthesis Example (6) Synthesis of Photosensitive Material b Compound [I-2] (50.1 g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (107.5 g) and acetone (1.0 L) were charged in a three-necked flask. , Uniformly dissolved. Then
41.7 g of N-methylpiperidine was gradually added dropwise to 25
The reaction was carried out at 3 ° C. for 3 hours. The reaction mixture was poured into 3.2 L of a 1% hydrochloric acid aqueous solution, and the generated precipitate was filtered off, washed with water and dried (4
0 ° C.) to give 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [I-2] (photosensitive material b) 1.
28.7 g was obtained. In high performance liquid chromatography measured using a detector using 254 nm ultraviolet light, the tetraester form of the photosensitive material b was 65% of the total pattern area.
Met.

Synthesis Example (7) Synthesis of Photosensitive Material c Compound [I-3] (50.1 g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (107.5 g) and acetone (1.0 L) were charged in a three-necked flask. , Uniformly dissolved. Then
41.7 g of N-methylpiperidine was gradually added dropwise to 25
The reaction was carried out at 3 ° C. for 3 hours. The reaction mixture was poured into 3.2 L of a 1% hydrochloric acid aqueous solution, and the generated precipitate was filtered off, washed with water and dried (4
0 ° C.) to give 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [I-3] (photosensitive material c) 1
29.7 g was obtained. In high performance liquid chromatography measured using a detector using 254 nm ultraviolet light, the tetraester form of the photosensitive material c was 66% of the total pattern area.
Met.

Synthesis Example (8) Synthesis of Photosensitive Material d Compound [I-11] 59.3 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 107.5 g, and acetone 1.5 L were charged into a three-necked flask. , Uniformly dissolved. Then
41.7 g of N-methylpiperidine was gradually added dropwise to 25
The reaction was carried out at 3 ° C. for 3 hours. The reaction mixture was poured into 5.0 L of a 1% hydrochloric acid aqueous solution, and the generated precipitate was filtered off, washed with water and dried (4
0 ° C.) to give 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [I-11] (photosensitive material d).
136.9 g was obtained. In high performance liquid chromatography measured with a detector using 254 nm ultraviolet light, the tetraester form of the photosensitivity material d was 58% of the total pattern area.
%Met.

Synthesis Example (9) Synthesis of Compound [II-1] 4-Cyclohexylphenol 176.3 g, tetramethylammonium hydroxide 25% aqueous solution 455.8 g, distilled water 500 mL are stirred, reflux condenser, thermometer, A 4-necked flask equipped with a dropping device was charged, heated at 50 ° C., stirred, and
Cyclohexylphenol was dissolved. To this mixed solution, 483.4 g of a 37% formalin aqueous solution was added dropwise, and the mixture was heated and stirred as it was for 8 hours. The obtained reaction mixture was neutralized with hydrochloric acid, and the precipitated white powder was collected by filtration to obtain 160 g of methylol compound.

118 g of the methylol compound obtained above, 1.2 kg of 2,5-xylenol, 1 L of methanol and 5 g of concentrated sulfuric acid were charged in the same reaction apparatus, and the mixture was stirred under reflux conditions for 6 hours. The obtained reaction mixture was poured into distilled water (10 L), and the precipitated white solid was steam distilled to almost remove excess 2,5-xylenol.
A mixture A of trinuclear bodies was obtained. Further, in a similar reactor, the mixture A obtained above and dimethylamine 50% aqueous solution 900
g and 1 L of ethanol were charged, and after stirring and homogenizing, 810 g of 37% formalin aqueous solution was added dropwise over 1 hour. After completion of dropping, the mixture was stirred under reflux conditions for 10 hours. After completion of the reaction, the precipitated white solid was filtered to obtain 140 g of aminomethyl compound.

In a similar reactor, the aminomethyl derivative 140
g and 1 kg of acetic anhydride were charged, and the mixture was heated with stirring at 150 ° C. After stirring for 15 hours, excess acetic anhydride was distilled off under reduced pressure, dissolved in acetone, crystallized in 1 L of distilled water, and the precipitated white solid was collected by filtration and washed with methanol to obtain 175 g of acetoxy compound. Finally, 175 g of the acetoxy compound obtained above, 500 g of phenol, 500 mL of methanol and 25 g of concentrated sulfuric acid were charged, and the mixture was stirred under reflux conditions for 10 hours, and 25 g of concentrated sulfuric acid was additionally added and stirred for 10 hours. After completion of the reaction, the product was poured into 10 L of distilled water and washed with 5 L of distilled water to obtain a solid (measured by gel permeation chromatography [measurement wavelength: 282 nm]) of the target product having a purity of 87%. Was purified by column chromatography to obtain 80 g of a target compound [II-1] (GPC purity: 97%).

Synthesis Example (10) Synthesis of Compound [II-4] 4 equipped with a stirrer, reflux condenser, thermometer and dropping device
A one-necked flask was charged with 70.5 g of terpene bis-o-cresol (manufactured by Yasuhara Chemical Co., Ltd.), 182.3 g of 25% TMAH aqueous solution and 100 ml of distilled water and heated to 40 ° C. to dissolve terpene bis-o-cresol. .
97.4 g of 37% formalin aqueous solution was added dropwise to the mixed solution over 30 minutes, and the mixture was heated and stirred at 40 ° C. for 10 hours. 100 ml of distilled water and 50 ml of hydrochloric acid were added to the reaction mixture to obtain a brown solid. The obtained brown solid was purified by column chromatography to obtain 57.8 g of a bismethylol derivative of terpene bis-o-cresol as a white powder.

Next, the above-mentioned terpene bis-obtained was placed in a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer.
41.3 g of o-cresol bismethylol compound, 99.1 g of phenol and 400 ml of methanol were charged, and 6
Compound E was dissolved by heating to 0 ° C. 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 [II-4] as a white powder.

Synthesis Example (11) Synthesis of Photosensitive Material e Compound (II-1) 65.7 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 53.7 g, and acetone 900 mL were charged in a three-necked flask and uniformly charged. Dissolved. Then, 20.8 g of N-methylpiperidine was gradually added dropwise, and the mixture was reacted at 25 ° C for 3 hours. 1% reaction mixture
The mixture was poured into 3.2 L of an aqueous hydrochloric acid solution, the resulting precipitate was filtered off, washed with water and dried to give 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [II-1] (photosensitive material e) 1
04.5 g was obtained. In high performance liquid chromatography, which was measured using a detector using ultraviolet rays of 254 nm, the diester form of the photosensitive material e was 44% of the total pattern area.

Synthesis Example (12) Synthesis of Photosensitive Material f 56.4 g of the compound [II-4], 61.8 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 750 ml of acetone were charged in a three-necked flask and homogenized. Dissolved in. Then, triethylamine / acetone = 24.4 g
/ 100 ml was gradually added dropwise and the reaction was carried out at 25 ° C for 3 hours. Pour the reaction mixture into 3000 ml of 1% aqueous hydrochloric acid,
The resulting precipitate was filtered off, washed with water and dried (40 ° C) to give 1,2-naphthoquinonediazide-5-of compound [II-4].
92.3 g of sulfonic acid ester (photosensitive material f) was obtained. Two
In high performance liquid chromatography measured with a detector using 54 nm ultraviolet light, the diester form of the photoconductor f was 44% of the total pattern area.

Synthesis Example (12) Synthesis of Novolac Resin A 43 g of m-cresol, 57 g of p-cresol, 49 g of 37% aqueous formalin solution and 0.13 g of oxalic acid were placed in a three-neck flask and heated to 100 ° C. with stirring. Then, it was reacted for 15 hours. Thereafter, the temperature was raised to 200 ° C. and the pressure was gradually reduced to 5 mmHg to remove water, unreacted monomers, formaldehyde, oxalic acid and the like. Then, the molten alkali-soluble novolac resin was returned to room temperature and recovered. The novolak resin A thus obtained had a weight average molecular weight of 7800 (in terms of polystyrene) and a dispersity of 0.1.
It was 0.

Synthesis Example (13) Synthesis of Novolac Resin B p-cresol 11 g, o-cresol 8 g, 2,3-dimethylphenol 69 g, 2,3,5-trimethylphenol 20 g, 2,6-dimethylphenol 4.9 g Was mixed with 50 g of diethylene glycol monomethyl ether 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, the temperature of the oil bath is 130 ° C for 18 hours
To continue the reaction, then remove the reflux condenser and
The unreacted monomer was removed by distillation under reduced pressure at 00 ° C. The obtained novolac resin has an Mw of 3350 and a dispersity of 2.
55.

Synthesis Example (14) Synthesis of Novolac Resin C 50 g of m-cresol, 3 g of p-cresol, 52.6 g of 2,5-xylenol, 53 g of 37% aqueous formalin solution and 0.15 g of oxalic acid were charged into a three-necked flask. While stirring, 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 obtained novolak resin had a weight average molecular weight of 3500 (in terms of polystyrene). Next, this novolac resin 20
g was completely dissolved in 60 g of methanol, and water 3
0 g was gradually added 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 24 hours to obtain an alkali-soluble novolak resin B. The obtained novolak resin had a weight average molecular weight of 4900 (in terms of polystyrene) and a dispersity of 3.20. Further, the content of each of the monomer, dimer and trimer is 0.
%, 2.1% and 3.3%, and 38% of low molecular weight components were removed by the fractional reprecipitation operation.

Synthesis Example (15) Synthesis of Novolac Resin D m-cresol 60 g, p-cresol 18 g, 2,3,5-trimethylphenol 25 g, 37% formalin aqueous solution 56 g and oxalic acid 0.16 g were placed in a three-necked flask. After charging, the temperature was raised to 100 ° C. with stirring and the reaction was performed for 16 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 obtained novolac resin had a weight average molecular weight of 3900 (in terms of polystyrene). Next, this novolac resin 20
g was completely dissolved in 60 g of acetone, 60 g of hexane was gradually added thereto while stirring, and the mixture was allowed to stand for 2 hours.
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 C. The obtained novolak resin had a weight average molecular weight of 7800 (in terms of polystyrene) and a dispersity of 3.20. The contents of the monomer, dimer and trimer are 0% and 2.
1% and 3.2%, and 52% of low molecular weight components were removed by the fractional reprecipitation operation.

Preparation and Evaluation of Positive Photoresist Composition Photosensitive materials a to f obtained in the above Synthesis Examples (1) to (12),
The novolak resins A to D obtained in the above Synthesis Examples (13) to (15), 22.8 g of ethyl lactate and, if necessary, a polyhydroxy compound were mixed at a ratio shown in Table 1 to form a uniform solution, and then the pore size was measured. The photoresist composition was prepared by filtration using a 0.10 μm Teflon microfilter. This photoresist composition was applied onto a silicon wafer using a spinner while changing the rotation speed, and dried at 90 ° C. for 60 seconds on a vacuum contact hot plate to obtain resists having film thicknesses of 0.76 μm and 0.78 μm, respectively. A film was obtained. 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 20 ° 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. The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist. Table 2 shows the results. The resolving power represents a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.50 μm. Thickness dependence is 0.76
The ratio of the resolution at μm to the resolution at 0.78 μm was used as an index of film thickness dependence. The closer this value is to 1.0, the smaller the film thickness dependence, and the more desirable the result. Standing wave is 0.40 μm at a film thickness of 0.76 μm
No standing wave was observed on the side wall of the line
The one in which the standing wave remained was defined as x.

[0091]

[Table 1]

P-1: 1- [α-methyl-α- (4'-
Hydroxyphenyl) ethyl] -4- [α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene P-2: 1,1-bis (4-hydroxyphenyl) cyclohexane P-3: bis (2,2 5-dimethyl-4-hydroxyphenyl) -2'-hydroxyphenylmethane

[0093]

[Table 2]

Further, the above Examples 1 to 12 and Comparative Examples 1 and 2
As a result of evaluating the sensitivity in Example 1, although Examples 1 to 12 of the present invention and Comparative Example 1 had good sensitivity, Comparative Example 2
Has significantly reduced sensitivity. As can be seen from these, in the resist using the two kinds of photosensitive materials of the present invention, the resolution is good, and the film thickness dependence of the resist performance becomes small,
Furthermore, it was found that no standing wave was generated.

[0095]

According to the present invention, the sensitivity is not lowered.
It is possible to provide a positive photoresist composition for ultrafine processing, which has high resolution and improved film thickness dependence and standing wave.

Claims (1)

[Claims] 1. An alkali-soluble resin, represented by the following general formula [I]:
1,2-naphthoquinonediazide-5- (and / or -4-) sulfonic acid ester of the polyhydroxy compound represented by the following formula and 1,2-naphthoquinonediazide-5 of the polyhydroxy compound represented by the following general formula [II]: A positive photoresist composition comprising (and / or -4-) sulfonic acid ester. General formula [I] Where X: R _{1 to} R ₆ : hydrogen atoms, which may be the same or different,
Halogen atoms, C1-4 alkyl groups or the number 2 to 5 alkenyl group having a carbon carbon, R ₇ to R _22: may be the same or different, a hydrogen atom,
Hydroxyl group, halogen atom, alkyl group having 1 to 4 carbon atoms,
An alkenyl group or a cycloalkyl group having 2 to 5 carbon atoms, R _{30 to} R ₃₅ : which may be the same or different, a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms, R ₃₀ and R ₃₁ , R ₃₂
And R ₃₃ , or R ₃₄ and R ₃₅ may be linked to each other to form a methylene chain having 4 or 5 carbon atoms and form a 5-membered or 6-membered ring with a carbon atom, R ₄₀ , R ₄₁ : The same or different, a hydrogen atom,
Halogen atom or alkyl group having 1 to 4 carbon atoms, R ₄₂ : hydrogen atom, hydroxyl group or alkyl group having 1 to 4 carbon atoms, R ₄₃ : hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, It represents an alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group, an aryl group or an alkoxy group. General formula [II] Here, R ₅₁ and R ₅₂ : may be the same or different and each is a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, acyl group or cycloalkyl group, a, b: each independently an integer of 0 to 3, A: -C ( _R66 ) ( _R67 )-,- O-, -S-, -C
(= O)-, -C (= O) O-, -S (= O)-, -S
Represents (= O) _2- (wherein R ₆₆ and R ₆₇ may be the same or different and represent a hydrogen atom or an alkyl group); R _{53 to} R ₆₅ : may be the same or different, and are a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, aryl group, alkoxy group or cycloalkyl group, X ₁ , Y: may be the same or different, single bond or-
C ( _R68 ) ( _R69 )-(wherein _R68 and _R69 may be the same or different and each is a hydrogen atom or an alkyl group), g: an integer of 0 to 3, k: 0 or 1 n: represents 1 or 2.